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KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3

B mn Ha Hu Co L Vn Dng
Trang 1
HA HC HU CO
Chuong 9
AXIT CACBOXYLIC
V DAN XUT CUA AXIT CACBOXYLIC
A-AXIT CACBOXYLIC
9.1-D|nh nghia v phn loi:
D|nh nghia: Axit cacboxylic l lo ai hop chat hu co m trong phn t u c
chua nhm cacboxyl -COOH lin kt voi goc hidrocacbon.
Cng thuc chung cua axit cacboxylic: R(COOH)
a
Trong d: a = 1, 2, 3, ... l s nhm cacboxyl
R l gc hidrocacbon.
R
C
O
OH
Phn loi:
* Ty theo dc dim cu to cua gc hidrocabon R ta c cc loai axit
cacboxylic khc nhau:
-Axit cacboxylic no don chuc:
C
n
H
2n+1
COOH (n 0) hay C
n
H
2n
O
2
(n 1).
-Axit cacboxylic chua no don chuc c 1 ni di:
C
n
H
2n - 1
COOH (n 2) hay C
n
H
2n - 2
O
2
(n 3).
-Axit cacboxylic vng no don chuc:
C
n
H
2n - 1
COOH (n 3) hay C
n
H
2n - 2
O
2
(n 4).
-Axit cacboxylic thom don chuc Ar-COOH :
C
n
H
2n - 7
COOH (n 6) hay C
n
H
2n - 8
O
2
(n 7).
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 2
* Ty theo s luong nhm cacboxyl trong phn tu ta c cc axit don chuc (c 1
nhm COOH), a xit da ch uc (c tu 2 nhm COOH tr o l n: nhu axit
dicacboxylic R(COOH)
2
...)
9.2-Tn gi:
- Nguyn tc goi tn thng thuong: axit + tn lich su tm ra axit d.
- Nguyn tc goi tn quc t IUPAC: axit + s thu tu cua nhm th + tn
nhm th (theo vn A, B, C) + tn ankan cua mach chnh + oic:
OOH C C C C C C C
1

2 3 4 5 6 7
Cng thuc Tn thng thuong Tn quc t IUPAC
HCOOH axit fomic axit metanoic
CH
3
COOH axit axetic axit etanoic
CH
3
CH
2
COOH axit propionic axit propanoic
CH
3
CH
2
CH
2
COOH axit n-butyric axit butanoic
(CH
3
)
2
CHCOOH axit isobutyric xit 2-metylpropanoic
CH
3
CH
2
CH
2
CH
2
COOH axit n-valeric axit pentanoic
(CH
3
)
2
CHCH
2
COOH axit isovaleric axit 3-metylbutanoic
CH
3
(CH
2
)
4
COOH axit n-caproic axit hexanoic
CH
3
(CH
2
)
5
COOH axit n-caprylic axit heptanoic
CH
3
(CH
2
)
8
COOH axit n-capric axit decanoic
CH
3
(CH
2
)
10
COOH axit n-lauric axit dodecanoic
CH
3
(CH
2
)
12
COOH axit n-miristic axit tetradecanoic
CH
3
(CH
2
)
14
COOH axit n-panmitic axit hexadecanoic
CH
3
(CH
2
)
16
COOH axit n-stearic axit octadecanoic
CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOH
C
17
H
33
COOH
axit oleic axit (Z)-octadec-9-enoic
CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOH
C
17
H
33
COOH
axit elaidic axit (E)-octadec-9-enoic
C
17
H
31
COOH axit linoleic
axit (9Z,12Z)-octadeca-
9,12-dienoic
C
17
H
29
COOH axit linolenic
axit (9Z,12Z,15) Zoctadeca-
9,12,15-trienoic
C
6
H
11
COOH Axitxiclohexancacboxylic axit xiclohexancacboxylic
ClCH
2
COOH axit monocloaxetic axit 2-cloetanoic
Cl
2
CHCOOH axit dicloaxetic axit 2,2-dicloetanoic
Cl
3
CCOOH axit tricloaxetic axit 2,2,2-tricloetanoic
C
6
H
5
CH
2
COOH axit phenyl axetic axit phenyletanoic
C
6
H
5
COOH axit benzoic axit benzoic
o-CH
3
C
6
H
4
COOH axit o-toluic axit 2-metylbenzoic
p-CH
3
C
6
H
4
COOH axit p-toluic axit 4-metylbenzoic
m-CH
3
C
6
H
4
COOH axit m-toluic axit 3-metylbenzoic
o-ClC
6
H
4
COOH axit o-clorobenzoic axit 2-clobenzoic
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 3
p-ClC
6
H
4
COOH axit p-clorobenzoic axit 4-clobenzoic
m-ClC
6
H
4
COOH axit m-clorobenzoic axit 3-clobenzoic
o-BrC
6
H
4
COOH axit o-bromobenzoic axit 2-brombenzoic
p-BrC
6
H
4
COOH axit p-bromobenzoic axit 4-brombenzoic
m-BrC
6
H
4
COOH axit m-bromobenzoic axit 3-brombenzoic
o-NO
2
C
6
H
4
COOH axit o-nitrobenzoic axit 2-nitrobenzoic
p-NO
2
C
6
H
4
COOH axit p-nitrobenzoic axit 4-nitrobenzoic
m-NO
2
C
6
H
4
COOH axit m-nitrobenzoic axit 3-nitrobenzoic
o-CH
3
OC
6
H
4
COOH axit o-metoxibenzoic axit 2-metoxibenzoic
p-CH
3
OC
6
H
4
COOH axit p-metoxibenzoic axit 4-metoxibenzoic
m-CH
3
OC
6
H
4
COOH axit m-metoxibenzoic axit 3-metoxibenzoic
o-C
6
H
4
(COOH)
2
axit phtalic axit benzen-1,2-dicacboxylic
m-C
6
H
4
(COOH)
2
axit isophtalic axit benzen-1,3 dicacboxylic
p-C
6
H
4
(COOH)
2
axit terephtalic axit benzen-1,4-dicacboxylic
o-HOC
6
H
4
COOH
axit salixylic
(axit o-hidroxibenzoic)
axit 2-hidroxibenzoic
p-HOC
6
H
4
COOH axit p-hidroxibenzoic axit 4-hidroxibenzoic
m-HOC
6
H
4
COOH axit m-hidroxibenzoic axit 3-hidroxibenzoic
o-H
2
NC
6
H
4
COOH
axit antranilic
(axit o-aminobenzoic)
axit 2-aminobenzoic
p-H
2
NC
6
H
4
COOH axit p-aminobenzoic axit 4-aminobenzoic
m-H
2
NC
6
H
4
COOH axit m-aminobenzoic axit 3-aminobenzoic
HOOC-COOH axit oxalic axit etandioic
HOOC-CH
2
-COOH axit malonic axit propandioic
HOOC-(CH
2
)
2
-COOH axit sucxinic axit butandioic
HOOC-(CH
2
)
3
-COOH axit glutaric axit pentandioic
HOOC-(CH
2
)
4
-COOH axit adipic axit hexandioic
CH
3
CH(OH)COOH axit lactic axit 2-hidroxi-propannoic
CH
2
=CH-COOH axit acrilic axit propenoic
CH
2
=CH-CH
2
COOH axit vinylaxetic axit but-3-enoic
CH
2
=C(CH
3
)COOH axit metacrilic axit 2-metylpropenoic
C
6
H
5
CH=CH-COOH axit xinamic axit 3-phenylpropenoic
CHC-COOH axit propiolic axit propinoic
CH
3
-CC-COOH axit tetrolic axit but-2-inoic
2,4,6
-(CH
3
)
3
C
6
H
2
COOH axit mezitoic axit 2,4,6-trimetylbenzoic
Cng thuc cu tao cua mt s axit thuong gp:
COOH
axit benzoic
axit p-nitrobenzoic
O
2
N COOH
axit salixilic
COOH
OH
axit phenylaxetic
CH
2
COOH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 4
COOH
Br
axit para-bromobenzoic
axit t erephtalic
COOH
COOH
COOH
COOH
axit i sophtalic
axit phtalic
COOH
COOH
NO
2
axit m-toluic axit p-toluic
COOH
NO
2
axit 2,4-dinitrobenzoic
CH
3
COOH
COOH
CH
3
axit o-toluic
COOH
CH
3
CH
2
CH
2
COOH
axit 3-phenylpropanoic
axit 3-(p-clophenyl)butanoic
CHCH
2
COOH Cl
CH
3
axit fumaric
H
H
HOOOC
COOH
C C
(E-trans) (Z-cis)
C C
COOH HOOOC
H H
axit maleic
C C
(CH
2
)
7
COOH
CH
3
(CH
2
)
7
H H
axit oleic
axit elaidic
H
H
CH
3
(CH
2
)
7
(CH
2
)
7
COOH
C C
(trans)
(cis)
CH=C-COOH
CH
3
axit metacrilic axit lactic
OH
CH
3
-CH-COOH
H
3
C
C C
COOH
H H
axit i zocrotonic axit crotonic
H
H
H
3
C
COOH
C C
(cis)
(trans)
COOH
CH
2
OH
H
HO
axit L-glixeric axit D-glixeric
OH
H
CH
2
OH
COOH COOH
COOH
HO
H
H
HO
axit meso-tactric axit L-tactric axit D -tactric
COOH
COOH
HO
H
H
OH HO
H
H
OH
COOH
COOH
CH
2
=C-CH=CH-COOH
CH
3
CH
2
CH
2
axit 4-propylpenta-2,4-dienoic axit butan-1,2,3-tricacboxylic
CH
3
CH CH CH
2
COOH
HOOC COOH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 5
axit xiclohexancacboxylic
COOH
COOH
HOOC-CH
2
-C-CH
2
-COOH
axit xitric
OH
COOH
COOH HOOC
axit bezen-1,3,5-tricacboxylic
C th goi theo danh php hop l c cc chi s vi tr: , , , , , ,...:
... OOH C C C C C C C



Th du:
CH
3


CH
3
CH
2
CHCOOH
axit -metylbutyric

axit , -dimetylvaleric
CH
3
CH-CH-CH
2
-COOH
CH
3
CH
3
CH
2
CH
2
CH
2
COOH
axit -phenylbutyric

Cl
Cl

Br
Cl
axit , -diclo- -phenylbutyric
CH-CH-CH
2
-COOH
CH
3
CH
3
CH-CH-CH
2
-COOH
axit -brom- -metylvaleric axit -clo- -metylbutyric
CH
2
CH
2
CHCOOH

CH
3


Tn mui cua cc axit cacboxylic: Tn cation + tn cua axit voi dui -ic di
thnh dui -at.
Th du:
CH
3
COOK: Kali axetat ; (CH
3
COO)
2
Ca: Canxi axetat
HCOONH
4
: Amoni fomiat ; C
17
H
35
COONa: Natri stearat
(Liti-4-clo-2-metylbutanoat) (Natri-4-brom-3-metylpentanoat)

Br
Cl
CH
3
CH
3
CH-CH-CH
2
-COONa
Natri -brom- -metylvalerat Liti -clo- -metylbutyrat
CH
2
CH
2
CHCOOLi

CH
3
COOK
Kali benzoat
Mt s axit cacboxylic trong t nhin v di sng :
Axit formic C trong cn trng nhu kin, su rm,
Axit axetic C trong dm n.
Axit caprilic C trong dua v sua me.
Axit lauric (axit dodecanoic) C trong dua v x phng rua tay
Axit myristiic (axit tetradecanoic) C trong nhuc du khu.
Axit panmitic (axit hexandecanoic) C trong du co.
Axit stearic (axit octadecanoic) c trong socola, sp, x phng,
cc loai du.
Axit arachidic (ax it eicosanoic CH
3
(CH
2
)
18
COOH) C trong
du du phng.
Cc axt cacboxylic khc bao gm:
Chui cc axit chua no monocarboxylic
o Acrilic acid (axit 2-propenoic) CH
2
= CHCOOH, duoc su dung
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 6
trong tng hop polime
Axt bo Trung bnh dn chui di bo h a v chua no c ua axit
monocacboxylic, thm ch voi s luong cacbon lon.
o Axit docosahexaenoic Dinh dung b sung
o Axit eicosapentaenoic Dinh dung b sung
Amino axit Vic xy dung cc khi protein
Xeto axit Axit nghia sinh ha c chua mt nhmxeton
o Axit axetoacetic
o Axit pyruvic
Axit cacboxylic thom
o Axit benzoic C
6
H
5
COOH; natri benzoat, mui natri cua ax it
benzoic duoc su dung nhu mt cht bao quan thuc phm.
o Axit mandelic Mt loai alpha hidroxi.
o Axit Salicylic acid C trong nhiu san phmchm sc da.
Axit dicarboxylic C chua hai nhm cacboxyl.
o Axit adipic L monome duoc su dung d san xut nylon.
o Axit aldaric Mt loai cua cc axit duong.
o Axit fumaric
o Axit glutaric
o Axit maleic
o Axit malic Tm thy trong qua to.
o Axit malonic
o Axt oxalic Tm thy trong nhiu loai thuc phm.
o Axit suxinic
o Axit tartronic
Axit tricarboxylic C chua ba nhm cacboxyl
o Acid xitric - Tm thy trong qua chanh.
o Axit isoxitric
o Axit aconitic
o Axit propan-1,2,3-tricacboxylic (ax it tricacballylic, ax it
cacballylic).
Alpha hidroxi axit C chua mt nhm hidroxi.
o Axit glixeric
o Axit glycolic
o Axit lactic (axit 2-hidroxipropanoic) duoc t m thy trong s ua
chua.
o Axit tartaric Tm thy trong ruou vang.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 7
9.3-Diu ch:
9.3.1-Phuong php oxi ha:
Oxi ha ankan c ao (t u 25 dn 30 nguyn tu cacbon) bng oxi khng kh o
nhit d 80 - 120
0
C c mt xc tc cc mui mangan, voi luong kim nho, be
gy mach cacbon thnh hn hop cc axit bo (tu 2 dn 25 nguyn tu cacbon),
phan ung ny ung dung trong cng nghip x phng.
Qa trnh phan ung: tao thnh peoxit xeton axit cacboxylic:
RCH-CH
2
R
RCH
2
CH
2
R +
/
RCOOH RCOOH
/
CH
2
R
C R
O
H
2
O
OH O
xt
O
2
+
/
/
xeton
hiropeoxit
axit cacboxylic
Oxi ha anke n: b ng cc ch t oxi ha manh nhu hn hop sufocromic
(K
2
Cr
2
O
7
+ H
2
SO
4
), hoc hn hop sunfo-pemanganat (KMnO
4
+ H
2
SO
4
) b e
gy ni di tao thnh hn hop axit cacboxylic hoc xeton:
5RCH=CHR
/
+ 8KMnO
4
+ 12H
2
SO
4

5RCOOH + 5R
/
COOH + 8MnSO
4
+ 4K
2
SO
4
+ 12H
2
O
Th du:
5CH
3
CH
3
CH=CHCH
3
+ 8KMnO
4
+ 12H
2
SO
4

5CH
3
CH
2
COOH + 5CH
3
COOH + 8MnSO
4
+ 4K
2
SO
4
+ 12H
2
O
Oxi ha hidrocacbon thom (aren) c mach nhnh :
Cc cht oxi ha: KMnO
4
hoc K
2
Cr
2
O
7
...
A r-R
7 2 2 4
O Cr K hoac KMnO
Ar-COOH
Th du:
COOK + 2MnO
2
+ KOH + H
2
O + 2KMnO
4
CH
3
Toluen
Kalibenzoat
COOH + KCl COOK + HCl
Axit benzoic
axit benzoic axit axetic n-propylbenzen
CH
2
CH
2
CH
3
1/ + KMnO
4
COOH + CH
3
COOH
2/ + HCl
p-nitrotoluen
CH
3
O
2
N
O
2
N COOH
axit p-nitrobenzoic
K
2
Cr
2
O
7
, H
2
SO
4
, t C
o
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 8
COOH
Br
axit o-brombenzoic o-bromtoluen
Br
CH
3
o
KMnO
4
, OH , t C 1/
2/HCl
Diu ch axit benzoic bng cch cho khng kh di qua toluen o 100
o
C, p
sut 6 atm c xc tc mui coban naphtalenat; oxi ha o-xilen hoc naphtalen
bng oxi khng kh c mt xc tc V
2
O
5
tao ra axit phtalic:
Than a
hoa c da u mo
(rifoming xu c ta c)
, O
2
+
axit phtalic
axit benzoic
COOH
COOH
COOH
O
2
, V
2
O
5
+
CH
3
CH
3
CH
3
t
o
C, p , xt
C
o
t
Oxi ha ancol bac mot hoc andhit:
Oxi ha ruou:
RCH
2
OH + [O] RCOOH + H
2
O
RCH
2
OH
4
KMnO
RCOOH
Th du:
CH
3
CH
2
OH + O
2

giam Men
CH
3
COOH + H
2
O
axit 2-metylbutanoic 2-metylbutanol-1
CH
3
CH
2
CHCOOH
CH
3
KMnO
4
CH
3
CH
3
CH
2
CHCH
2
OH
axit isobutyric
r u isobutylic
CH
3
CHCOOH
CH
3
KMnO
4
CH
3
CH
3
CHCH
2
OH
Oxi ha andehit:
RCH=O + [O] RCOOH
RCH=O
4
KMnO
RCOOH
Th du: 2CH
3
CH=O + O
2

+
C t
o
Mn
2
,
2CH
3
COOH
2CH
2
=CH-CH=O + O
2

+
C t
o
Mn
2
,
2CH
2
=CH-COOH
CH
3
CH
2
CH=O
4
KMnO
CH
3
CH
2
COOH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 9
, men gia m O
2
+
CH
3
COOH
2
Mn
O
2
+
CH
3
CH=O
300 C
o
CuO,
o
H
2
O, HgSO
4
, H
2
SO
4
,80 C
CH
3
CH
2
OH
CH CH
Di voi ruou bc hai hoc xeton phai dng cht oxi ha manh nhu HNO
3
hoc KMnO
4
+ H
2
SO
4
, mach cacbon bi be gy tao ra hn hop axit cacboxylic
c mach cacbon nho hon ban du:
CH
3
CH
2
CH
2
CHCH
3
OH
O
CH
3
CH
2
CH
2
C CH
3
[O] [O]
a b
a
b
CH
3
CH
2
COOH CH
3
COOH
CH
3
CH
2
CH
2
COOH
+
CO
2
+
H
2
O
+
9.3.2-Phuong php thuy phn: Thuy phn cc dn xut cua axit: clorua axit,
anhidrit axit, est e, amit, nitrin,...khi dem thuy phn bng cch dun si voi dung
dich kim hoc dung dich axit v co lm xc tc:
H
+
OH
R C
O
Y
OH hoa c H
H
2
O +
Y
O
C R
Trong d -Y: -Cl : clorua axit
-OCOR
/
: anhidrit axit
-OR
/
: este
-NH
2
: amit
Th du:
CH
3
COCl + H
2
O
+
C t
o
H ,
CH
3
COOH + HCl
axetylclorua axit axetic
(CH
3
CO)
2
O + H
2
O
+
C t
o
H ,
2CH
3
COOH
anhidrit axetic axit axetic
CH
3
COC
2
H
5
+ H
2
O
+
C t
o
H ,
2CH
3
COOH + C
2
H
5
OH
etyl axetat axit axetic ruou etylic
CH
3
CONH
2
+ H
2
O + HCl
C t
o
CH
3
COOH + NH
4
Cl
axetamit axit axetic
Thuy phn dn xut nitrin:
R-Cl + KCN R-CN + KCl
RCN + 2H
2
O
+
C t
o
OH hoac H
-
,
RCOOH + NH
3
hoc: Ar-Cl + KCN Ar-CN + KCl
Ar-CN + 2H
2
O
+
C t
o
OH hoac H
-
,
Ar-COOH + NH
3
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 10
Th du:
h CH
3
CH
2
CH
2
CH
2
Cl + KCN CH
3
CH
2
CH
2
CH
2
CN + KCl
n-butyl clorua n-valeronitrin (pentannitrin)
n-
C
4
H
9
CN + 2H
2
O + HCl
C t
o
CH
3
CH
2
CH
2
CH
2
COOH + NH
4
Cl
axit n-valeric
n-
C
4
H
9
CN + 2H
2
O + NaOH
C t
o
CH
3
CH
2
CH
2
CH
2
COONa + NH
3

natri n-valerat
CH
3
CH
2
CH
2
CH
2
COONa + HCl CH
3
CH
2
CH
2
CH
2
COOH + NaCl
axit n-valeric
h
CH
2
CN + NaCl CH
2
Cl + NaCN
benzyl clorua phenylaxetonitrin
CH
2
CN + 4H
2
O + H
2
SO
4
CH
2
COOH + (NH
4
)
2
SO
4
2
2
phenylaxetonitrin axit phenylaxetic
So d diu ch axit thom qua giai doan tao mui diazoni:
ArH ArNO
2
ArNH
2
ArN
2
+
ArCN ArCOOH
h/c nitro amin ion diazoni nitrin axi t
Th du:
HCl
H
2
O
CuCN
HCl
NaNO
3
Fe + HCl
[H]
H
2
SO
4
HNO
3
NO
2
NH
2 CN COOH
N
2
+
Cl
-
benzen axit benzoic nitrobenzen anilin phenyldiazoni
clorua
benzo
nitrin
h Ngoi ra cn thuy phn dn xut gem-trihalogen :
KOH
H
2
O
+
OH
OH
OH
R C 3
Cl
Cl
Cl
C R + H
2
O
O
C R
OH
Th du: thuy phn clorofom CHCl
3
:
CHCl
3
+ 4NaOH HCOONa + 3NaCl +2H
2
O
clorofom natri fomiat
HCOONa + HCl HCOOH + NaCl
natri fomiat axit fomic
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 11
axit benzoic
benzotriclorua toluen
2/ + HCl
COOH
1/+ H
2
O, OH
Cl
Cl
Cl
C
askt
+ Cl
2 CH
3
9.3.3-Di t hp cht co magi:
RBr + Mg
khan ete
RMgBr
O
MgBr
O C R O=C=O
MgBr R +
OH
Br
Mg
O
MgBr
O C R
OH
R C
O
H
H
2
O
+ +
Th du:
C
2
H
5
C
CH
3
CH
3
Cl
ter t-penty lclorua
+ Mg
MgCl
CH
3
CH
3
C C
2
H
5
COOMgCl
CH
3
CH
3
C C
2
H
5
+ CO
2
+ H
+
C
2
H
5
C
CH
3
CH
3
COOH
axit etyldimetylaxetic
(2,2-dimetylbutanoic)
+ Mg
r u ter t-butylic
(CH
3
)
3
C-OH
+ HCl
(CH
3
)
3
C-Cl (CH
3
)
3
C-MgCl
ter t-butylclorua
+ H
+
+ CO
2
(CH
3
)
3
C-MgCl (CH
3
)
3
C-COOMgCl
(CH
3
)
3
C-COOH
axit trimetylaxetic
Hoc diu ch cc axit thom:
ArBr + Mg
khan ete
ArMgBr
ArMgBr + CO
2
ArCOOMgBr
ArCOOMgBr + H
2
O
+
H
ArCOOH + Mg(OH)Br
Th du:
CH
3
C
2
H
5
p-brom-sec-butylbenzen
+ Mg
+ CO
2
+ H
+
Br
CH
CH
MgBr
C
2
H
5
CH
3
CH
3
C
2
H
5
COOMgBr
CH
axit p-sec-butylbenzoic
CH
COOH
C
2
H
5
CH
3
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 12
CH
3
COOH
CH
3
CH
3
COOMgBr
CH
3
CH
3
MgBr
CH
3
CH
3
Br
+ H
+
+ CO
2
+ Mg
CH
3
CH
3 CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
+ Br
2
mezitilen bromomezitilen
axit mezitoic
9.3.4-Phuong php cacbonyl ha:
Tuong t c cacbon oxit v oi ki m ho c voi ancolat k im o nhi t do 120-
130
o
C v duoi p suat cao:
t
o
C, p cao
R O Na
+
CO
R
C ONa
O
H
R
C OH
O
O
OH C H
H
O
ONa C H
CO + Na O H
t
o
C, p cao
Tuong t c c ua cacbon oxit v nuoc voi cc anken, c m t c ua nike n
cacboxyl lm xc tc:
Tng hop Reppe:
H
2
O
O
C
CH
2
CH
2
+CO
C OH
O
CH
2
=CH
2
CH
2
CH
3
Ni(CO)
4
Cai bin phuong php trn bng cch cho CO tc dung voi olefin trong
dung dich H
2
SO
4
dc (tng hop Haffe-Koch):
CH
3
CHCH
3
C OH
O
CH
3
CH=CH
2
+ H
+
CH
CH
3
CO + H
2
O
CH
3
9.3.5-Phuong php tng hp malonic:
Di tu axit malonic: Phuong php ny diu ch axit c mach cacbon tng ln
2C so voi dn xut halogen ban du v c th tng ln nua nu lp lai ln nua
(v axit malonic c 2 hidro c th thay th 2 nhm ankyl).
COOH
COOH
CH
2
C
2
H
5
OH
H
2
SO
4
2
CH
2
COOC
2
H
5
COOC
2
H
5
Na
hoa c C
2
H
5
ONa
COOC
2
H
5
COOC
2
H
5
CH Na
RX
axit malonic
dietylmalonat
RX
COOC
2
H
5
COOC
2
H
5
CH R
RCH
COOH
COOH
H
2
O,H
t
CO
2
o
RCH
2
COOH
Nu lp lai ln nua:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 13
RCR
COOC
2
H
5
COOC
2
H
5
NaCR
COOC
2
H
5
COOC
2
H
5
Na
RX
COOC
2
H
5
COOC
2
H
5
CH R
hoa c C
2
H
5
ONa
CH-COOH
R
R
RCR
COOH
COOH
H
2
O,H
t
CO
2
o
COOC
2
H
5
COOC
2
H
5
RCR
Hoc:
hoac C
2
H
5
ONa
2CH
2
COOC
2
H
5
COOC
2
H
5
Na
COOC
2
H
5
COOC
2
H
5
2NaCH
2NaCH
COOC
2
H
5
COOC
2
H
5
CHCH
2
CH
COOC
2
H
5
COOC
2
H
5
C
2
H
5
OOC
C
2
H
5
OOC
I-CH
2
-I
H
2
O, H
+
C
2
H
5
OOC
C
2
H
5
OOC
COOC
2
H
5
COOC
2
H
5
CHCH
2
CH
-CO
2
HOOCCH
2
CH
2
CH
2
COOH
axit glutaric
Th du:
CH
2
(COOH)
2

+
+ H OH H C /
5 2
CH
2
(COOC
2
H
5
)
2

+ ONa H C
5 2
NaCH(COOC
2
H
5
)
2

+ Cl H C
5 2
C
2
H
5
CH(COOC
2
H
5
)
2


+ OH O H ,
2
C
2
H
5
CH(COO
-
)
2

+
+H
C
2
H
5
CH(COOH)
2

C t
o
CH
3
CH
2
CH
2
COOH
axit butyric
CH
2
(COOH)
2

+
+ H OH H C /
5 2
CH
2
(COOC
2
H
5
)
2

+ ONa H C
5 2
NaCH(COOC
2
H
5
)
2

+ Cl H C
5 2
C
2
H
5
CH(COOC
2
H
5
)
2

+ ONa H C
5 2
[C
2
H
5
C(COOC
2
H
5
)
2
]
-
Na
+

+ Cl CH
3
C
2
H
5
C(CH
3
)(COOC
2
H
5
)
2


+ OH O H ,
2
C
2
H
5
C(CH
3
)(COO
-
)
2

+
+H
C
2
H
5
C(CH
3
)(COOH)
2

2
, CO C t
o
-
CH
3
CH
2
CH(CH
3
)COOH
axit 2-metylbutanoic
9.4-Tnh cht l hc:
9.4.1-Nhit d si cua axit cacboxylic:
Nhit d si cua cc axit cacboxylic cao hon nhit d si cua cc ancol do
lin kt hidro cua axit bn hon lin kt hidro cua ruou: boi 2 l do: thu nht lin
kt O-H tr ong axit phn cuc manh hon trong ancol, thu hai nguyn tu oxi trong
C=O cua axit giu mt d din tch m; di voi ruou chi c lin kt hidro dang
mach thng, di voi axit ngai lin kt hidro dang thng cn c lin kt hidro
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 14
dang dime mach vng:
Lin kt hidro dang dime:

O
C R
H O
O H
R
C
O
Lin kt hidro dang polime:
C
O O H
R
C
O O H
R
R
O H O
C
Nng luong lin kt hidro cua axit l 7kcal, cua ancol l 5kcal.
9.4.2-Nhit d nng chay:
Tt ca cc monoaxitcacboxylic du l nhung cht long hoc rn, cc axit
thom du l cht rn.
Trong khi nhit d si cua cc mono axit cacboxylic mach thng khng
phn nhnh (axit n-ankanoic) tng du theo s luong nguyn tu cacbon, th
nhit d nng chay cua chng lai tng mt cch lun phin theo duong rng
cua zic-z c, t uc l dng dng c s cacbon chn c nhit d nng chay cao
hon dng dng dng c s cacbon le truoc v sa u n o 2 bn. Su lun phin
nhu th l do su khc nhau v c u tr c tinh th cua ax it. Axit c s cacbon
chn di xung hon do d tinh th sp xt cht kht hon, nn nhit d nng chay
cao hon axit c s cacbon le.
COOH
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
CH
2 COOH
CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
COOH CH
2
CH
2
CH
3
D thi biu thi su bin thin nhit d nng chay cua axit n-ankanoic:
-50
0
50
100
5 10 15
20
C
1
C
2
C
3
C
4
C
5
C
6
C
7
C
8
C
9
C
10
C
11
C
12
C
13
C
14
C
15
C
16
C
17
C
18
C
19
C
20
t C
o
So C
Gian do biu thi su bin thin nhit do nng chay
cua dy dong dng axit n-ankanoic.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 15
9.4.3-V d tan:
Cc dng dng thp: axit fomic, axit axetic, axit propionic tan v han trong
nuoc, cn cc axit bo cao khi mach cacbon trong gc R t ng, tnh ki nuoc
tng, d ta n giam dn, dn muc d no d n hon to n khng tan (t u C
12
tro
ln).
Giai thch d tan trong nuoc cua cc axit l do su tao thnh lin kt hidro
cua axit voi nuoc:
H
H
O H
O H
O
C
R
O H
H O
R C
O

a n c
k n c
a n c
k n c
Khi mach cacbon tng, d tan giam do phn ki nuoc tng (gc -R lon dn),
trong khi d phn ua nuoc l nhm -COOH l khng di.
M hnh biu thi d tan cua axit n-ankanoic:
H
2
O H
2
O
l
l
l
l
l
l
l
k n c (-R)
(-COOH) a n c
M hnh biu thi do tan trong nuoc cua
axit n-ankanoic khi mach cacbon tng
9.5-Tnh cht ha hc cua axit cacboxylic:
9.5.1-Ban cht, d}c dim nhm cacboxyl v kha nng phan ng cua axit
cacboxylic:
Ar
C
O
O H
Axit cacboxylic co ca u ta o: O H
O
C R
C
H
H

Tnh cht ha hoc co ban cua axit th hin o nhm COOH, d l su t hop
cua nhm C=O v nhm OH: xut hin hiu ung lin hop giua electron tu do o
nguyn tu oxi trong -O-H voi cc electron trong -C=O:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 16
O
C
O H

..
O H
C
O

hoa c co the vie t


Do hiu ung lin hop C (lin hop p-) ni trn dn toi 2 kt qua:
-Lin kt O-H ban thn n d phn cuc manh v pha O do oxi c d m
din lon hon H, lai c ng phn cuc manh hon do c hiu ung lin hop -C cua
nhm C=O, nn su phn cuc cua nhm O-H manh hon so voi O-H tr ong ruou
R-O-H, d l nguyn nhn co ban giai thch tnh axit cua cc axit cacboxyl ic .
-Nhm C=O trong axit khng cn giu nguyn nhung dc dim nhu nhm
cacbnyl trong adehit v xeton: n khng tham gia duoc nhiu phan ung dc
trung nhu di voi andehit v xeton.
-Ngoi ra, su c mt cua nhm COOH cn anh huong toi su phn cuc cua
lin kt C-H o cacbon anpha (H

) , lm cho cc nguyn tu H

linh dng hon so


voi cc nguyn tu H khc trong gc R.
Dua vo dc dim ni trn ta c th qui cc phan ung cua axit cacboxylic v
4 loai phan ung sau:
1) R C
O H
O
Phan ung lm dut lin kt O-H, d l cc phan ung: phn
li axit, tao mui voi cc kim loai...
O
OH
R C 2)

+
Y:
Phan ung vo nhm cacbonyl C=O: da s l nhung phan
ung voi tc nhn nucleophin Y, lm dut lin kt C-OH.
O
O H
R C 3)
Phan ung dcacboxyl ha hay l tch nhm cacboxyl.
O
OH
R C 4)
Phan ung o goc hidrocacbon bao gm nhung phan ung th
o vi tr v phan ung th o gc thom.
9.5.2-Tnh axit cua axit cacboxylic:
Su phn li trong nuoc :
O
H
H
2
O R C
O
O
C R H
3
O
O
+
+
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 17
Axit cacboxylic l nhung axit yu, v vy cn bng trn thuong lch v bn
tri. Hng s cn bng cung goi l hng s phn li axit K
a
duoc tnh bng h
thuc:
] [
] ][ [
3
RCOOH
O H RCOO
K
a
+
=
Sau khi phn li, anion gc axit c dang cu tao nhu sau :
1
2
2
1
hoa c co the vie t

O
C
O
C
O
O
R R
Bng phuong php do tia Roentgen, trong anion gc axit focmic HCOO
-
nguoi ta d xc dinh duoc d di 2 lin kt C-O l h on ton bng nhau v
bng 1,27A
o
= d di tr ung gian giua d di lin kt don C-O (1, 42A
o
) v lin
kt di C=O (1,21A
o
). Diu d chung to, 2 lin kt C-O tr ong anion gc axit
RCOO
-
l hon ta n tuong duong, din tch m duoc phn b du ca 2 nguyn
tu oxi. Nng luong lin hop trong gc axit RCOO
-
lon hon trong axit RCOOH,
lm cho anion c d bn lon hon, diu d kch thch su phn li cua a xit
cacboxylic d tao ra anion cacboxylat RCOO
-
. So snh d phn li giua axit v
ruou, ta thy d phn li cua r uou km hon nhiu, mt phn chnh l v trong
anion ankoxilat RO
-
c ua r uou khng c hiu ung lin hop nhu trong anion
cacboxylat RCOO
-
, l m cho a nion RO
-
km bn hon. S u chnh lch v mt
nng luong giua su phn li cua axit cacboxylic v ruou tuong ung vo khoang
10kcal/mol.
+Axit cacboxylic no: Khao st hng s phn li cua cc axit cacboxylic no sau:
Tn axit Cng thuc cu tao Hng s p/li K
a
.10
5
axit fomic HCOOH 17,7
axit axetic CH
3
COOH 1,75
axit propionic CH
3
CH
2
COOH 1,33
axit monocloaxetic
ClCH
2
COOH 136
axit dicloaxetic Cl
2
CHCOOH 5 530
axit tricloaxetic Cl
3
CCOOH 23 200
axit butyric CH
3
CH
2
CH
2
COOH 1,52
axit -clobutyric
CH
3
CH
2
CHClCOOH 139
axit -clobutyric
CH
3
CHClCH
2
COOH 8,9
axit -clobutyric
CH
2
ClCH
2
CH
2
COOH
2,96
axit monofloaxetic FCH
2
COOH 260
axit monobromaxetic BrCH
2
COOH 125
axit monoiotaxetic ICH
2
COOH 67
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 18
axit phenylaxetic C
6
H
5
CH
2
COOH 4,9
axit p-nitrophenylaxetic
p-O
2
NC
6
H
4
CH
2
COOH
14,1
axit benzoic C
6
H
5
COOH 6,3
Dua vo bang hng s phn li cc axit, ta rt ra nhung nhn xt sau:
i Trong dy dng dng cua axit no don chuc, tnh axit giam dn khi mach
cacbon tng, do su tng dn hiu ung cam ung duong +I cua gc ankyl R:
HCOOH > CH
3
COOH > CH
3
CH
2
COOH
i Vi tr cua clo cng gn nhm COOH tnh axit cng manh:
Nguyn nhn do dc dim cua hiu ung cam ung m -I cua clo giam dn khi
mach cacbon ko di:
CH
3
CH
2
CHClCOOH > CH
3
CHClCH
2
COOH > CH
2
ClCH
2
CH
2
COOH
i S luong clo cng nhiu th tnh axit cng tng, do hiu ung cam ung m
-I cng lon:
Cl
3
CCOOH > Cl
2
CHCOOH > ClCH
2
COOH > CH
3
COOH
i Dn xut axit halogen th giam dn khi d m din cua halogen giam, do
halogen c din tch hat nh n cng nho, d m din cng lon th kha nng ht
electron bng hiu ung cam ung m -I cng lon:
FCH
2
COOH > ClCH
2
COOH > BrCH
2
COOH > ICH
2
COOH
i Nhn phenyl cng gn nhm -COOH tnh axit cng tng, do nhm phenyl
l nhm th ht electron.
p-O
2
NC
6
H
4
CH
2
COOH > C
6
H
5
COOH > C
6
H
5
CH
2
COOH > CH
3
COOH
+Axit cacboxylic chua no:
So snh giua hng s axit no v axit chua no tuong ung, thy cc axit chua
no c hng s phn li lon hon:
Tn axit cng thuc cu tao hng s phn li K
a
.10
5
axit propionic CH
3
CH
2
COOH 1,33
axit butyric CH
3
CH
2
CH
2
COOH 1,52
axit acrylic CH
2
=CH-COOH 5,56
axit vinylaxetic CH
2
=CH-CH
2
COOH 4,62
axit crotonnic (trans)
CH
3
CH=CH-COOH 2,04
axit tetrolic
CH
3
-CC-COOH
222,8
Khao st cc du liu trn, ta thy r:
-Cc lin kt C=C v CC du l nhung nhm c hiu ung cam ung m -I, lin
kt ba ht electron manh hon lin kt di:
CH
3
-CC-COOH > CH
3
CH=CH-COOH > CH
3
CH
2
CH
2
COOH
-Lin kt chua no cng o gn nhm -COOH, axit phn li cng manh, o xa hon
mt nguyn tu C, hng s phn li giam di:
CH
2
=CH-COOH > CH
2
=CH-CH
2
COOH > CH
3
CH=CH-COOH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 19
H
H
H
C CH CH C O
OH
OH
O C CH
CH
2
OH
O
C
CH
CH
2
CH
2
+I, H
-I
-I
COOH
R
Ha ng so pha n li cu a mo t so axit benzoic the :
(trong n c, 25 C)
o
K
a
.
10
5
R CH
3
H OH OCH
3
NO
2
F Cl
orth 12,4 6,3 105 8,2 670 54,1 120
meta 5,4 6,3 8,3 8,2 32,0 13,6 15,1
para 4,2 6,3 2,6 3,3 36,0 7,2 10,3
Tu bang trn, khi nghin cuu anh huong cua cc nhm th o cc vi tr meta
v para dn hng s phn li cua cc axit benzoic - t h ta rt ra nhung nhn xt
sau:
-Cc nhm th dy electron nhu gc ankyl c hiu ung +I, +C lm giam tnh
axit cua axit thom; khi nhm th o vi tr para, tnh axit giam nhiu hon so voi o
vi tr meta. D l do hiu ung siu l in hop c ua nhm CH
3
lm tng mt d
electron o vi tr para nhiu hon so voi vi tr meta.
COOH
COOH
CH
3
COOH
CH
3
COOH
CH
3
+I
+I
+C
-Cc nhm th ht electron c hiu ung -I, -C nhu NO
2
lm tng tnh axit
ln rt manh, nhm NO
2
o vi tr para lm tng tnh axit nhiu hon so voi vi tr
meta. D l do hiu ung -C cua nhm NO
2
lm giam mt d electron nhiu nht
o vi tr orth v para, khi o vi t r meta nhm NO
2
chi pht huy tc dung hiu
ung -I nn anh huong yu hon.
-C
-I
-I
NO
2
COOH
NO
2
COOH
NO
2
COOH
COOH
-Cc nhm th c hiu ung -I nhung +C nhu -OH, -OCH
3
, -F khi chng o vi
tr meta th lm tng tnh axit, nhung khi chng o vi tr para lai lm giam tnh
axit, tru tr uong hop F khi o vi tr para, tnh axit vn hoi tng. Tnh axit t ng
khi cc nhm th ny o vi tr meta l do hiu ung -I pht huy tc dung; cn tnh
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 20
axit giam khi chng o vi tr para l do hi u ung +C lc ny pht huy tc dung.
Ring F, do hiu ung -I r t manh, nn d khi o vi tr para, hi u ung +C vn
khng thng duoc hiu ung -I nn tnh axit vn hoi tng.
COOH
COOH
OH
COOH
OH
COOH
OH
-I -I
+C
+C
-I
-I
OCH
3
COOH
OCH
3
COOH
OCH
3
COOH
COOH
COOH
COOH
F
COOH
F
COOH
F
-I
-I
+C
+C
-I
-I
Cl
COOH
Cl
COOH
Cl
COOH
COOH
-Cc axit orth-benzoic th c hng s phn li lon hon hn so voi khi nhm
th o vi tr para v meta l do hiu ung orth. Hiu ung orth l su t hop cua
nhiu hiu ung:
+hiu ung khng gian b ac nhat: do tuong tc tr uc ti p giua nhm th voi
nhm COOH, khng qua c c l in kt m q ua kh ng gian, hiu ung ny cn
duoc goi l hiu ung truong.
+Hiu ung khng gian b ac hai : l lm ri lo an tnh cht c ng trn mt
phng cua nhm cacbonyl v vng benzen, do p l uc cua nhm th bn canh
gy ra, hi u ung d lm giam mt p hn hoc trit tiu hon tan su lin hop
cua nhm cacbonyl voi vng benzen.
+Su hnh thnh li n kt moi giua nhm th voi nhm cabonyl: c th hnh
thnh lin kt cng ha tri, hoc lin kt phi tr, hoc lin kt hidro:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 21
O
H
C
O
O H
lie n ke t hiro
axit salixylic
K
a
=105.10
-
5
Ta cng thy r anh huong cua su tao thnh lin kt hidro dn su phn li
axit, khi xt tnh axit cua axit 2,6-dihidroxibenzoic: l axit manh do tao thnh 2
lin kt hidro ni phn tu :
axit 2,6 dihidroxibenzoic: K = 500
a
lie n ke t hiro
H O
O
C
H
O
O
H
lie n ke t hiro
Tc dung voi kim loai hoat dong :
2RCOOH + 2Na 2RCOONa + H
2

2CH
3
COOH + Mg (CH
3
COO)
2
Mg + H
2

6HCOOH + 2Al 2(HCOO)


3
Al + 3H
2

Tc dung voi bazo v oxit bazo :


RCOOH + NH
3
RCOONH
4
RCOOH + NH
2
R
/
RCOONH
3
R
/
RCOOH + NaOH RCOONa + H
2
O
2RCOOH + Cu(OH)
2
(RCOO)
2
Cu + 2H
2
O
2RCOOH + CaO (RCOO)
2
Ca + H
2
O
Th du:
HCOOH + NH
3
HCOONH
4
axit fomic amoni fomiat
CH
3
COOH + C
6
H
5
NH
2
CH
3
COONH
3
C
6
H
5
axit axetic anilin phenylaminaxetat
CH
3
(CH
2
)
10
COOH + NaOH CH
3
(CH
2
)
10
COONa + H
2
O
axit lauric natri laurat
2CH
3
COOH + Cu(OH)
2
(CH
3
COO)
2
Cu + 2H
2
O
axit axetic dng (II) axetat
2CH
3
COOH + CuO (CH
3
COO)
2
Cu + H
2
O
Tc dung voi muoi cacbonat:
2RCOOH + Na
2
CO
3
2RCOONa + CO
2
+ H
2
O
RCOOH + NaHCO
3
RCOONa + CO
2
+ H
2
O
2RCOOH + CaCO
3
(RCOO)
2
Ca + CO
2
+ H
2
O
Th du:
2 CH
3
COOH + Na
2
CO
3
2CH
3
COONa + CO
2
+ H
2
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 22
CH
3
COOH + NaHCO
3
CH
3
COONa + CO
2
+ H
2
O
axit axetic natri axetat
C
6
H
5
COOH + NaHCO
3
C
6
H
5
COONa + CO
2
+ H
2
O
axit benzoic n atri benzoat
2CH
3
COOH + CaCO
3
(CH
3
COO)
2
Ca + CO
2
+ H
2
O
axit axetic canxi axetat
9.5.3-Cc phan ng o nguyn tu cacbon cacboxyl:
phan ung tao clorua axit:

'

+
+
+

'

+
HCl POCl
PO H
HCl SO
RCOCl
PCl
PCl
SOCl
RCOOH
3
3 3
2
5
3
2
n-C
17
H
35
COOH + SOCl
2
n-C
17
H
35
COCl + SO
2
+ HCl
axit stearic thionyl clorua stearoyl clorua
3CH
3
COOH + PCl
3

C
o
50
3CH
3
COCl + H
3
PO
3
axit axetic axetyl clorua
COOH + PCl
5
100 C
o
COCl + POCl
3
+ HCl
axit benzoic
photpho
pentaclorua
benzoyl clorua
Phan ung tao amit:
So d phan ung chung:
RCOOH
3
NH
RCOONH
4

C t O H
o
,
2
RCONH
2
mui amoni amit
RCOOH
2
SOCl
RCOCl
3
NH
RCONH
2
cloruaxit amit
Th du:
CH
3
COOH
3
NH
CH
3
COONH
4

C t O H
o
,
2
CH
3
CONH
2
amoni axetat axetamit
C
6
H
5
CH
2
COOH
2
SOCl
C
6
H
5
CH
2
COCl
3
NH
C
6
H
5
CH
2
CONH
2
axit phenylaxetic phenylaxetyl clorua phenylaxetamit
Phan ung khu :
O
C R H O
R CH
2
OH
LiAlH
4
H
, H
2
O
Qa trnh phan ung xay ra nhu sau :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 23
O
C R H O
OAlH
3
Li R C
O
+
+
LiAlH
4
H
2
COO R
CH=O R
LiAlH
4
LiAlH
4
R CH
2
OH
Phan ung tng qut xay ra nhu sau :
+
O
C R
H
O
R
H
2
O HCl
O)
4
Al]Li [(R C
O
LiCl
+ LiAlO
2
+
+
AlCl
3
LiAlH
4
H
2
CH
2
OH
4
+
,
Th du:
r u m-metylbenzylic axit m-toluic
CH
2
OH
CH
3
CH
3
COOH
LiAlH
4
Tc nhn khu c hiu qua hon so voi liti nhm hidrua (LiAlH
4
) l diboran
(B
2
H
6
). Diboran khu duoc ca este, nhung chm hon.
Tnh tro trong cc phan ung cong vo nhm cacbonyl:
RCOOH + R
/
-MgBr RCOO
-
Mg
+
Br + R
/
-H
Khi bi thuy phn, mui RCOO
-
Mg
+
Br lai tao ra axit cacboxylic ban du:
2RCOO
-
Mg
+
Br + 2HCl 2RCOOH + MgCl
2
+ MgCl
2
Phan ung este ha:
Phan ung este ha l phan ung thun nghich xay ra nhu sau:
18
18
H
2
O
H O R O H R C
O
+ +
O
C R O R
Co ch phan ung :
-Phan ung xay ra rt chm theo ca hai huong, nu khng c mt cua mt
axit v co manh:
O
C R O
R
H
R
OH R C
O
O
O
H
2
O
H O R
O H R C
O
+
O H
C R OH
R
..
-Khi c xc tc axit v co manh th proton kt hop voi cp electron tu do
cua axit cacboxylic hoc cua ancol:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 24
H
O
C R
H
O
+
H
R O
OH
C R H O
..
H +
H
O R H hoa c
la m gia m kha na ng pha n ng cu a r u
ve pha nguye n t cacbon cacbonyl.
S tao thanh
H R O
H
Nu luong axit v co khng nhiu, th proton chi kt hop voi oxi cua nhm
cacbonyl trong RCOOH, v luc kt hop proton cua n guyn tu oxi ny manh
hon trong ruou. Kt qua lm cho phan ung este ha xay ra nhanh hon do tng
cuong kha nng electrophin cua cacbon cacbonyl:
R
OH R C
O
OH
2
H
O
H R
C
OH
+R O
OH
C R H O
..
OH
O H
C R OH
R
R
OH R C
O
OH
2
H
3
O
OH
O C
R
R R
R
C O
O
+
H
2
O
H
2
O
Phan ung este ha c tnh cht thun nghich. Mun chuyn ha hon tan
axit v r uou voi nhung luong dng phn tu thnh este th phai tch este hoc
tch nuoc tao thnh ra khoi hn hop phan ung. Mun cho mt t rong hai cht
du l axit hoc ruou chuyn hon ton thnh este, th ti l nng d hai cht d
trong hn hop phan ung phai gp hon nhau khoang 8 ln (
8
1
) .
Tc d phan ung este phu thuc rt nhiu vo dc dim cu tao cua ruou v
cua axit. Nhn chung, nu gc R v R
/
cng cng knh n ngu khng gian cng
lon, th tc d phan ung cng chm v gioi han phan ung cng nho.
Di voi mt axit nht dinh, so snh kha nng phan ung este ha gia cc
bac r uou, th r uou bac I m anh hon r uou bac II , v r uou bac II manh hon
ruou bac III:
C
I
-OH > C
II
-OH > C
III
-OH
Di voi mt ruou nht dinh, so snh kha nng phan ung este cua cc axit
cacboxylic giam dan theo trat tu sau:
HCOOH > CH
3
COOH > RCH
2
COOH > R
2
CHCOOH > R
3
C-COOH
Th du mt s phan ung este ha:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 25
metyl benzoat
axit benzoic
COOCH
3
+ H
2
O
H
+
COOH + CH
3
OH
CH
2
OH + CH
3
COOH
H
+
+ H
2
O
r u benzylic
CH
3
COOCH
2
bezylaxetat
axit axetic
axit axetic isoamylaxetat
CH
3
COOCH
2
CH
2
CHCH
3
+ H
2
O
r u isoamylic
H
+
CH
3
CHCH
2
CH
2
OH + CH
3
COOH
CH
3
CH
3
HOOC(CH
2
)
4
COOH + 2C
2
H
5
OH
H
+
C
2
H
5
OOC(CH
2
)
4
COOC
2
H
5
+ 2H
2
O
axit adipic
r u etylic
dietyladipat
9.5.4-Phan ng d cacboxyl ha:
-Nhit phn mui natri cua axit cacboxylic tao ra hidrocacbon:
C
n
H
2n + 1
COONa + NaOH
C t CaO
o
,
C
n
H
2n + 2
+ Na
2
CO
3
R(COONa)
a
+ aNaOH
C t CaO
o
,
R(H)
a
+ aNa
2
CO
3
Th du:
CH
3
COONa + NaOH
C t CaO
o
,
CH
4
+ Na
2
CO
3
natriaxetat
2C
6
H
5
COONa + 2KOH
C t CaO
o
,
2C
6
H
6
+ Na
2
CO
3
+ K
2
CO
3
natri benzoat
CH
2
(COONa)
2
+ 2NaOH
C t CaO
o
,
CH
4
+ 2Na
2
CO
3
natri malonat
-Nhiu axit bi dcacboxyl ha d dng khi dun nng :
axit malonic
O
140-160
CO
2
+
CH
3
COOH
COOH
CH
2
COOH
COOH
NO
2
NO
2
O
2
N O
2
N
NO
2
NO
2
H
2
O, H
+
, t C
o
+ CO
2
axit 2,4,6-trintrobenzoic 1,3,5-trintrobenzen
2KOOC-CH-CH-COONa + 4NaOH CH
2
-CH
2
+ K
2
CO
3
+ 3Na
2
CO
3
OH OH OH OH
CaO
t C
o
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 26
Dc bit cc axit c nhm th ht din tu (-I) o nguyn tu cacbon anpha di
voi nhm cacboxyl bi d cacboxyl ha d dng, nhu:
O
2
N-CH
2
-COOH (axit nitroaxetic)
NC-CH
2
-COOH (axit xianoaxetic)
CH
3
CO-CH
2
-COOH (axit axetoaxetic)
Cl
3
C-COOH (axit tricloaxetic) ...
Cc axit ny bi dcacboxyl ha o nhit d 100-150
o
C.
-Khi nhit phn mui natri hoc mui canxi cua axit axetic tao ra xeton:
2CH
3
COONa
C t CaO
o
,
(CH
3
)
2
C=O + Na
2
CO
3
natriaxetat axeton
CH
3
-C-CH
3
+ CaCO
3
o
t C
Ca
CH
3
COO
CH
3
COO
O
canxi axetat
axeton
Dng ch l mui bac cua axit cacboxylic d dng bi dcacboxyl ha khi
c mt cua brom hoc clo tao ra dn xut halogen tuong ung: d l phan ng
Huzdincko:
C
6
H
5
CH
2
COOAg + Br
2

C CCl
o
76 ,
4
C
6
H
5
CH
2
Br + CO
2
+ AgBr
-Cung c th thuc hin phan ung dcacboxyl ha khi cho hoi axit di qua xc
tc oxit kim loai o nhit d cao:
2CH
3
COOH
C t CaO
o
,
(CH
3
)
2
C=O + CO
2
+ H
2
O
axit axetic axeton
-Khi din phn cc mui natri cua axit cacboxylic:
O
C R Na O +
O
Na
R C
O
Catot ( )
Ano t (+)
COO R
,
H
2
O
Na
,
H
2
O
R COO
R COO 1e
R COO R
+
CO
2
R R
+ R R
H
2
O
+ e H
2
+
OH 2 2
2
2R-C-ONa + 2H
2
O R-R + H
2
+ 2CO
2
+ 2NaOH
O
pdd
Th du: Din phn dung dich natri axetat:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 27
2CH
3
COONa + 2H
2
O
pdd
2C
2
H
6
+ 2NaOH 2CO
2
+ H
2

natri axetat etan


9.5.5-Phan ng o nguyn tu cacbon anpha cua gc ankyl ho}c th vo gc
aryl cua nhn thom:
-Phan ung voi halogen c nh sng khuych tn (X
2
/ h), phan ung s thay
th ln luot H bng cc halogen, t ao ra c c axit mono-, di- v tr i-halogen
cacboxylic:
ClCH
2
COOH
HCl
CH
3
COOH
+ Cl
2
+
h
axit axetic
axit cloaxetic
h
h
ClCH
2
COOH
Cl
2
CHCOOH Cl
3
CCOOH
Cl
2
Cl
2
axit cloaxetic
axit dicloaxetic axit tricloaxetic
Phan ung halogen ha ny xay ra theo co ch gc tu do nhu khi halogen ha
ankan, nhung d dng hon. Halogen ha halogenua axit d dng hon so voi khi
halogen ha axit.
-Phan ung voi halogen c mt cua photpho - Phan ung Hen-Fonhac-
Zelinxki:
( X
2
= Cl
2
, Br
2
)
X
P
+
X
2
+
RCH
2
COOH
HX RCHCOOH
Th du : ClCH
2
COOH
HCl
CH
3
COOH
+ Cl
2
+
P
P
P
ClCH
2
COOH Cl
2
CHCOOH
Cl
3
CCOOH
Cl
2
Cl
2
P
CH
3
CHCH
2
COOH + Br
2
CH
3
CH
3
CH
3
CHCHCOOH + HBr
Br
axit isovaleric
axit -bromisovaleric
Co ch phan ung halogen ha axit cacboxylic c mt cua P:
2P + 3Br
2
2PBr
3
RCH
2
COOH + PBr
3
RCH
2
COBr + POBr + HBr
RCH
2
C=O
Br Br
RCH=C-OH
H
+
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 28
Br
RCH=C-OH + Br-Br
RCH-C=O + HBr
Br
Br
Br
RCH
2
C=O RCH-C=O + RCH
2
COOH
Br
Br
Br
OH
RCH-C=O +
Cc phan ung cua dn xut halogen th:
Phan ung tao aminoaxit:
R-CH-COOH
Br
NH
2
R-CH-COOH
+ NH
3
Cc phan tao hidroxiaxit:
+ 2NaOH
R-CH-COONa + NaBr + H
2
O
OH
Br
R-CH-COOH
R-CH-COONa
OH
OH
R-CH-COOH + NaCl
+ HCl
Cc phan ung tao diaxit:
R-CH-COONa
Br
CN
R-CH-COONa + NaBr
+ NaCN
R-CH-COONa
CN
COOH
R-CH-COOH + NaCl + NH
4
Cl
+ 2H
2
O + 2HCl
Ngoi ra cn c phan ung th vo nhn thom cua axit thom.
Th du: nitro ha axit benzoic:
axit benzoic
COOH
+ HNO
3
H
2
SO
4
COOH
NO
2
+
H
2
O
axit m nitrobenzoic
t C
o
9.6.-Nhng axit no don chc tiu biu:
9.6.1-Axit fomic HCOOH:
Axit fomic c chua trong loi su rm, kin lua trong cy gai, thng. Hi
th ky 17 nguoi ta tm thy axit ny trong co th loi kin Formica rufai.
iu ch:
C nhiu cch diu ch axit fomic: Thuy phn clorofom CHCl
3
, a xit
xianhidric, oxi ha metamol, fomandehit, nhit phn axit oxalic trong
glixerin.... T rong cng nghip diu ch HCOOH tu monoxit cacbon v natri
hidroxit.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 29
CHCl
3
+ 4KOH HCOOK + 3KCl + 2H
2
O
HCN + 2H
2
O HCOONH
4

HCl
HCOOH
KH + CO
2
HCOOK
+ CO
2
HCOOH
O
HOOC COOH
glixerin
100
axit oxalic
axit fomic
CH
3
OH + 3[O] HCOOH + H
2
O
HCH=O + [O] HCOOH
+
CO NaOH
HCOONa
O
6-8 atm
120-150
+ HCl
HCOOH
Tnh chat : Axit fomic khan l cht long trong sut, linh dng, n da v gy
phong da rt manh, c mi tuong tu kh sunfuro. Axit fomic voi nuoc tao thnh
hn hop dng ph (77% axit fomic) c dim si cuc dai 107
o
C, a xit fo mic
nguyn cht nng chay 8,6
o
C, si 101
o
C. ax it fomic duoc dng nhiu trong
cng nghip dt (thay axit axetic), cng nghip da v ca trong cng nghip thuc
phm nua.
L axit manh nht trong dy dng dng cua axit no don chuc. Axit fomic
khc t t c a cc dng dng cua n l c chua nhm -CH=O, nn c tnh cht
cua a ndehit, nh u tham gia ph an ung trng guong, tc dung voi Cu(OH)
2
t ao
Cu
2
O mu do gach, tc dung voi dung dich KMnO
4
:
HCOOH + 2[Ag(NH
3
)
2
]OH (NH
4
)
2
CO
3
+ 2Ag + 2NH
3
+ H
2
O
HCOONa + 2[Ag(NH
3
)
2
]OH NaHCO
3
+ 2Ag + 4NH
3
+ H
2
O
HCOOH + 2Cu(OH)
2
+ 2NaOH Cu
2
O + Na
2
CO
3
+ 4H
2
O
HCOOH + 2KMnO
4
+ 4NaOH K
2
MnO
4
+ Na
2
MnO
4
+ Na
2
CO
3
+ 3H
2
O
dung dich tu mu tm chuyn thnh mu xa nh do phan ung tao thnh ion
MnO
4
2--
.
Khi dun nng axit fomic c mt H
2
SO
4
, c ung nhu khi dun nng nhanh
fomiat kim o 400
o
C phan ung xay ra nhu sau:
HCOOH
4 2
SO H
H
2
O + CO
2HCOONa
C
o
400
H
2
+ NaOOC-COONa
9.6.2-Axit axetic CH
3
COOH:
iu ch:
Phan ung ln me n gi am: Vi khun mycoderma a ceti c kha nng bin dung
dich ruou e tylic long (6-9%) th nh axit long (gim) c 2 phuong php ln
men gim:
Phuong php Oc-l-ng (Orleana): Cho men gim vo ruou etylic v d lu
o ch nng. Ruou s bi oxi ha thnh axit axetic nho oxi khng kh c mt xc
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 30
tc men.
Phuong php Suytzeenbc (Schwtzenbach): Cung theo nguyn tc nhu trn,
nhung cho nng sut cao hon: Cho dung dich ruou long chay chm tu tu trn
xung qua nhung lop vo bo c chua men gim, dng thoi cho dng khng kh
di nguoc duoi ln. Ruou ti p x c voi khng kh, bi oxi ha nhanh thnh axit
axetic nho tc dung xc tc cua men.
CH
3
CH
2
OH + O
2

giam Men
CH
3
COOH + H
2
O
Cat khan g o: Bng cch ct khan g thu duoc luong lon axit axetic cng voi
mt s san phm khc nhu metanol, axeton ...Ch ha voi Ca(OH)
2
cho axetat
canxi kt tua; sau d ch ha voi axit sunfuric:
(CH
3
COO)
2
Ca + H
2
SO
4
CH
3
COOH + CaSO
4
i tu axetylen:
kk
O
2
+
Mn(CH
3
COO)
2 H
2
SO
4
HgSO
4
O
80
CH
CH
CH
3
COOH H
2
O CH
3
CH=O
+
i tu n-butan:
CH
3
CH
2
CH
2
CH
3
+ O
2

atm C
o
70 , 180
2CH
3
COOH
Tnh ch at: Axit axetic khan nguyn cht l mt cht long trong sut c mi
kch thch, dng dc o +16
o
C thnh nhung tinh th tuong tu nhu nuoc d, nhit
d si +118
o
C.
Axit axetic rt bn vung voi cht oxi ha, ngay ca nhung cht oxi ha manh
nhu axit cromic v kalipemaganat.
Axit axetic dng d n (gim), tng hop nuoc hoa, ch cht mu, axeton,
ch xenluloaxetat v cc mui, d nhum v in, dng lm dung mi tt.
CH
3
COONa khan duoc dng lm tc nhn ngung tu v dng lm san sut
anhidrit axetic.
Nhm axetat (CH
3
COO)
3
Al l mui tan duoc dng trong cng nghip
nghip nh um lm cht c m mu v tao thnh cht khng tan trong nuoc l
monobazic (CH
3
COO)
2
AlOH v dibazic CH
3
COOAl(OH)
2
(tuong tu nhu crom
axetat v st axetat).
Ch axetat ngm nuoc Pb(CH
3
COO)
2
.3H
2
O l cht dc v c v i ng ot
(duong ch).
Dung dich ch axetat bazic goi l gim ch duoc dng trong y hoc lm cht
chua bong v bong gn. Axit monocloaxetic ClCH
2
COOH duoc diu ch bng
cch clo ha axit axetic nho xc tc I
2
, S...:
CH
3
COOH + Cl
2

XT
ClCH
2
COOH + HCl
Axit ny l cht rn, nng chay o 63
o
C, d tan trong nuoc. Axit tu do cung
nhu mui natri monoaxetat duoc dng d tng hop nhung cht tr u co dai quan
trong nhu 2,4-D; 2,4,5-T;.... Chnh natri monoaxetat cung l mt cht tru co v
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 31
cht lm rung l v dng trong nng nghip.
(2,4,5-T)
(2,4-)
Cl
OCH
2
COOH
Cl
Cl
axit 2,4,5-triclophenoxiaxetic
axit 2,4-diclophenoxiaxetic
Cl
Cl
OCH
2
COOH
9.6.3-Axit bo cao: Axit stearic (C
17
H
35
COOH), axit panmitic (C
15
H
31
COOH)
v a xit oleic (C
17
H
33
COOH) d l nhung axit bo cao quan trong nht. Cc
este glixeric c ua c c axit bo cao trn l th nh phn chnh cua du m dng
thuc vt v c th diu ch bng phuong php x phng ha:
CH
2
CH
CH
2
OCOC
17
H
35
OCOC
17
H
35
OCOC
17
H
35
+
3H
2
O
C
17
H
35
COOH
CH
2
CH
CH
2
OH
OH
OH
+
hoa c mem lipaz
3
tristearin glixerin
axit stearic
H
+
hoa c OH
-
Sau khi x phng ha du m ri axit ha thuong duoc hn hop cc axit
bo trong d thnh phn chnh l ax it stearic, ax it panmitic (rn), axit oleic
(long), dem p s duoc hn hop axit st earic v axit pa nmitic o dang khi rn,
cn axit oleic o dang long.
Nhung mui kim cua chng (mui Na, K) dng lm x phng.
Chng dng lm nn, d l hn hop axit stearic v panmitic c thm parafin
d ngn su kt tinh v giam tnh gin.
9.7-Axit cacboxylic chua no:
Axit cacboxylic khng no l nhung axit c ni di C=C hoc ni ba CC
trong phn tu.
Th du cc axit cacboxylic chua no:
CH
2
=CH-COOH: axit acrilic
CH
2
=CH-CH
2
-COOH: axit vinylaxetic
CH
3
CH=CH-COOH: axit crotonic
CH
2
=C(CH
3
)COOH: axit metacrilic
C
6
H
5
-CH=CH-COOH axit xinamic
CHC-COOH: axit propiolic
HOOC-CC-COOH: axit axetylendicacboxylic
C=C
H H
CH
3
(CH
2
)
7
(CH
2
)
7
COOH
COOH
HOOC
H H
C=C
C=C
H
H
HOOC
COOH
axit oleic
axit maleic
axit fumaric
9.7.1-Diu ch:
hidrohalogen ha axit halogen th:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 32
CH
2
=CHCOOH
HCl
o
t C
CH
2
=CHCOOK
CH
2
CHCOOH
Br
Br
CH
2
CH
2
COOH
2KOH/ r u
kali acrylat
axit actylic
o
t C
CH
2
=CHCOOH + ZnBr
2
CH
2
CHCOOH + Zn
Br
Br
CH
3
OH
axit acrylic
ehidat ha:
o
t C
+
H
2
O
CH
2
=CHCOOH
CH
2
CHCOOH
OH
OH
CH
2
CH
2
COOH
H
2
SO
4

axit acrylic
OH
o
axit acrylic
acrilonitrin
NH
3
2
CH
2
=CHC N
CH
3
CHC N
CH
2
=CHCOOH
H
2
O (H ) t
H
2
O
i tu andehit chua no:
2
1
axit metacrilic
CH
2
=C CH=O
CH
3
CH
3
CH
2
=C COOH
+
O
2
Mn
2
* CH
3
-CH=CH-CH=O
3 2
/ NH O Ag
CH
3
-CH=CH-COOH
* CH
2
=CHCH=O
+HCl
ClCH
2
CH
2
CH=O
] [O
ClCH
2
CH
2
COOH

HCl
CH
2
=CH-COOH.
* CH
3
CH=CH-COCH
3

NaOH I /
2
CH
3
CH=CH-COCI
3

+ ] NaOH
CH
3
CH=CH-COONa
+
+H
CH
3
CH=CH-COOH.
i tu este chua no :
H
C
2
H
5
OH + CH
3
CH=CHCOOH H
2
O
+
CH
3
CH=CHCOOC
2
H
5
Phuong php ngung tu:
Khi cho andehit ngung tu voi anhidrit axetic (phan ung Pekin) hoc axit
malonic (phan ung Knuevenagen) s thu duoc axit khng no.
Th du: Phan ung ngung tu giua andehit crotonic voi axit malonic:
CH
3
-CH=CH-CH=O + CH
2
(COOH)
2

piridin
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 33
CH
3
-CH=CH-CH=CH-COOH + H
2
O + CO
2

Axeton cung tham gia phan ung nhu trn:


(CH
3
)
2
CH=O + CH
2
(COOH)
2

piridin
(CH
3
)
2
CH=CH-COOH + H
2
O + CO
2

Thuy phn dan xuat nitrin:


CH
2
=CH-CN + 2H
2
O + HCl CH
2
=CH-COOH + NH
4
Cl
acrilonitrin axit acrilic
H
2
O, H
+
CH CH + HCN CH
2
=CH-C N
acrilonitrin
o
axit acrilic
CH
2
=CH-COOH
CuCl, NH
4
Cl
80-90 C
H
2
O, H
+
CH
2
=CH-CH
3
+ O
2
+ NH
3
CH
2
=CH-C N
acrilonitrin
o
axit acrilic
CH
2
=CH-COOH
xt ho n h p
400-500 C, P cao
CH
2
=CHCOOH
axit actylic
HOCH
2
CH
2
Cl + KCN
CH
2
CH
2
+ HCN
O
HOCH
2
CH
2
CN
+ H
2
O
H
2
SO
4
H
2
SO
4
+ H
2
O
axit metactylic
CH
2
=C-COOH
CH
3
CH
3
C=O + HCN C CN
CH
3
CH
3
OH
CH
3
Cacbonyl ha ( tong hop Reppe):
H
2
O
O
C
CH=CH
+CO CH CH
Ni(CO)
4
CH
2
=CH-COOH
CH
2
=CH-COOC
2
H
5
CH
2
=CH-CONH
2
C
2
H
5
OH
NH
3
axit acrilic
etyl acrilat
acrilamit
t C
o
9.7.2-Tnh cht:
Tnh ch at ho h oc c ua axit cacboxy lic ch ua no bao g om tnh c hat c ua
nhm COOH v tnh ch at cua lin k t di C=C (ho c in kt ba C C). Di
voi cc axit ,-chua no, c su lin hop giua lin kt di C=C v li n kt di
C=O, mt d elctron di chuyn v pha cacbonyl.
Th du axit acrilic: CH
2
=CH-COOH

O H
O C CH
CH
2
Cho nn khi tin hnh phan ung voi hidro halogenua, phan ung tin hnh
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 34
tri voi qui tc Maccopnhicop (Markovnikov) tao ra cac axit -halogen
cacboxylic:
CH
2
CH C O
O H


+ HBr
O H
OH C CH
CH
2
Br
Br
CH
2
CH
2
C OH
O
Su phn li axit:
Tn axit cng thuc cu tao hng s p/li K
a
.10
5
axit propionic
CH
3
CH
2
COOH 1,33
axit butyric CH
3
CH
2
CH
2
COOH 1,52
axit acrylic
CH
2
=CH-COOH 5,56
axit vinylaxetic
CH
2
=CH-CH
2
COOH 4,62
axit isocrotonnic (cis)
CH
3
CH
2
=CH-COOH 4,16
axit crotonnic (trans)
CH
3
CH
2
=CH-COOH 2,04
axit tetrolic
CH
3
CHCH-COOH
222,8
Axit khng no c tnh axit manh hon axit no tuong ung, v ni di C=C v
ni ba CC c hiu ung cam ung m -I.
Ni di (v ni ba) cng gn nhm cacboxyl, hiu ung -I cng tng do d
axit cng manh.
Tuy vy ni di o vi tr , di voi nhm COOH th ngoi hiu ung -I cn
c hiu ung lin hop +C. Hi u ung lin hop +C d lm giam tnh axit, do d
axit , -khng no tuy manh hon axit no tuong ung nhung khng manh bng
dng phn , -khng no.
Ta bit rng axit khng no, cung nhu nhu cc hop cht khc chua ni di
C=C, c th c dng phn cis-trans, di voi axit , -khng no dng phn cis
c tnh axit manh hon dng phn trans, v o dng phn cis c hiu ung khng
gian, tuong tu hiu ung orth o cc axit thom.
Th du: axit isocrotonic (cis) manh hon axit cr otonic (trans) v nhm metyl
gy hiu ung khng gian loai hai, l m giam su lin hop giua ni di v nhm
cacbxyl:
C=C
H
H
COOH
CH
3
hai nho m the
a y nhau
(cis) (trans)
C=C
H
H
H
3
C COOH
axit isocrotonic axit crotonic
COOH
H
3
C
H
H
C=C
Di voi cc axit etylen-1,2-dicacboxylic nu xt theo (k
a
)
1
dng phn cis
(axit maleic) cung manh hon dng phn trans (axit fumaric. Nguyn nhn chu
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 35
yu c l l li n kt hi dro ni phn tu lm cho lin kt O-H t rong mt nhm -
COOH c ua a xit maleic yu h on axit fu maric v io n maleat a xit sinh ra b n
vung hon ion fumarat axit:
axit maleic
C=O
H-O-C
H
H
O
HO
...
C C
C C
...
HO
O
H
H
C=O
anio maleat axit
O=C
C C
...
HO
O
H
H
H-O-C
C=O
C=C
H
H
HOOC
COOH
axit maleic axit fumaric
Dng ch l cc axit thuc dy axetylen cacboxylic c tnh axit manh hon
cc axit tuong ung voi ni di C=C v ni ba CC c hiu ung -I manh hon ni
di C=C.
So d phan ung cua axit cacboxylic khng no:
CH
2
=CHCOOH
CH
3
CH
2
COOH
CH
2
CH
2
COOH
Br
CH
2
CHCOOH
Br
Br
OH OH
CH
2
CHCOOK
COOH
CH
2
CH
n
CH
2
=CHCOONa
+
H
2
O
H
2
+
(CH
2
=CHCOO)
2
Mg
(CH
2
=CHCOO)
2
Ca
+ CO
2
+
H
2
O
qu i ho a o
+
qu i tm
+
Mg
+
NaOH
+ CaO
(CH
2
=CHCOO)
2
Ca
+H
2
O
+
CaCO
3
+
H
2
/Ni,t
+
HBr
+Br
2
+
KMnO
4
t, xt
o
(tru ng h p)
+
MnO
2
+
KOH
axit acrylic
(axit propenoic)
o
Phan ung cng electrophin vo ni di:
CH
2
=CH-COOH + HBr Br-CH
2
-CH
2
-COOH
CH
2
=CH-COOH + H
2
O
+
H
HO-CH
2
-CH
2
-COOH
Co ch phan ung cng electrophin:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 36
Br-CH
2
-CH
2
-C
O
OH
OH
OH
Br-CH
2
-CH=C
OH
OH
CH
2
CH C CH
2
=CH-C
OH
OH
H
O
OH
CH
2
=CH-C
Nguoi ta thy rng cc phan ung trn dy xay ra tuong tu phan ung cng
halogen hay hidrohalogenua vo butadien-1,3 v acrolein. Cu th l: o giai
doan du proton cng vo nguyn tu oxi cua nhm C=O v giai doan sau anion
nucleophin cng vo nguyn tu cacbon thiu hut electron (nhu cng 1, 4).
Cc axit chua no c th tn tai duoi dang dng phn hnh hoc:
C
C
CH
3
COOH
H H
axit i socrotonic (cis)
t
o
nc
s
o
t
=
=
14,5
172,9
180
72
=
=
t
o
s
nc
o
t
axit crotonic (trans)
H
H
COOH
CH
3
C
C
o
C
C
o
C
o
C
o
100
o
tia t ngoa i
Br
2
(a s) , HCl
C
C
HOOC COOH
H H
axit maleic
t
o
nc
=
130
301 =
nc
o
t
axit fumaric
H
H
COOH
HOOC
C
C
o
C
C
o
9.8- Axit da chc:
Nhung axit dicacboxylic mach thng:
HOOC-COOH axit oxalic
HOOC-CH
2
-COOH axit malonic
HOOC-(CH
2
)
2
-COOH axit sucxinic
HOOC-(CH
2
)
3
-COOH axit glutaric
HOOC-(CH
2
)
4
-COOH axit adipic
Nhung axit dicacboxylic thom:
COOH
COOH
COOH
COOH
COOH
COOH
axit o-phtalic
axit i sophtalic axit ter ephtalic
9.8.1-Diu ch:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 37
axit glutaric
HOOC(CH
2
)
3
COOH
HNO
3
CH
2
CH
2
CH
2
CH
2
C=O
xiclopentanon
C
5
H
8
O + 6HNO
3
HOOC(CH
2
)
3
COOH + 6NO
2
+ 3H
2
O
xiclohexanon
HNO
3
HOOC(CH
2
)
4
COOH
axit adipic
CH
2
CH
2
C=O
CH
2
CH
2
CH
2
C
6
H
10
O + 6HNO
3
HOOC(CH
2
)
4
COOH + 6NO
2
+ 3H
2
O
axit dodecandicacboxylic
HOOC(CH
2
)
10
COOH
HNO
3
xiclododecanon
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
C=O
C
12
H
22
O + 6HNO
3
HOOC(CH
2
)
10
COOH + 6NO
2
+ 3H
2
O
+
O
2
, V
2
O
5
t C
o
+ H
2
O
C
C
H
H
H
H
C
C
+ H
2
, t C
O
O
O
o
COOH
COOH
C
C
axit maleic
anhidrit maleic
axit sucxinic
COOH CH
2
CH
2
COOH
benzen
CH
3
CH
3 COOH
COOH
o-xylen
axit phtalic
KMnO
4
COOH
COOH
KMnO
4
axit i zophtalic
m-xylen
CH
3
CH
3
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 38
CH
3
CH
3
p-xylen axit ter ephtalic
KMnO
4
COOH
COOH
CH
3
CH
3
mezitilen
axit trimezinic
KMnO
4
CH
3
HOOC
COOH
COOH
axit o,o-diphenyldicacboxylic
phenantren
COOH
COOH
K
2
Cr
2
O
7
CH
3
CH
3
+
O
2
, V
2
O
5
t C
o
anhidrit phtalic
axit phtalic
C
C
COOH
COOH
O
O
O
+ H
2
O
Oxi ha than ch cho ta axit benzenhexacacboxylic:
HOOC
COOH
COOH
HOOC
COOH
COOH
HNO
3
axit benzen-hexacacboxylic
Phuong php thuy phn:
ClCH
2
COONa + KCN NC-CH
2
COONa + KCl
CNCH
2
COONa + 2H
2
O + 2HCl HOOC-CH
2
COOH + NaCl + NH
4
Cl
ClCH
2
CH
2
Cl + 2KCN NC-CH
2
CH
2
-CN + 2KCl
NC-CH
2
CH
2
-CN + 4H
2
O + 2HCl HOOC(CH
2
)
2
COOH + 2NH
4
Cl
Cl(CH
2
)
3
CCl
3
+ NaCN NC(CH
2
)
3
CCl
3
+ NaCl
NC(CH
2
)
3
CCl
3
+4H
2
O HOOC(CH
2
)
3
COOH + NH
4
Cl + 2HCl
NaOOC COONa + 3NaCl + NH
3
+ H
2
O
CCl
3
+ 5NaOH
NC
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 39
HOOC
COONa + 2HCl COOH + 2NaCl HOOC
Cl(CH
2
)
3
CCl
3
+ 5NaOH HO(CH
2
)
3
COONa + 4NaCl+ 2H
2
O
HO(CH
2
)
3
COONa + HCl HO(CH
2
)
3
COOH + NaCl
5HO(CH
2
)
3
COOH + 4KMnO
4
+ 6H
2
SO
4

5HOOC(CH
2
)
2
COOH + 2K
2
SO
4
+ 4MnSO
4
+ 11H
2
O
HCl
+ 2H
2
O
CH
3
COOH
+ CuCN
CH
3
CN
NaNO
2
+ HCl
CH
3
CH
3
[N N
+
]Cl
-
NH
2
COOH COOK
CH
3
COOK
+ 2KMnO
4
+ 2MnO
2
+ 2H
2
O
COOK COOH
COOK
COOH
+ 2HCl
+ 2KCl
9.8.2-Tnh cht vt l:
Tt ca cc diaxitcacboxylic du l cht rn, nhit d nng chay cua cc axit
n-ankandicacboxylic (HOOC(CH
2
)
n
COOH) bin di lun phin. C c axit voi
s chn nguyn tu cacbon nng chay o nhit d cao hon 2 axit dng dng 2 bn
voi s le nguyn tu cacbon. Mach cacbon cng di, nhit d nng chay cua axit
voi cacbon chn cng thp v su chnh lch ni trn cng t. Nguyn nhn cua
su lun phin v nhit d nng chay c lin quan voi su lun phin v su phn
b 2 nhm cacboxyl trong phn tu.
COOH
HOOC
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
COOH CH
2
CH
2
HOOC
COOH
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
HOOC
CH
2
D thi biu thi su bin thin nhit d nng chay cua axit dicacboxylic:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 40
o
t C
10
8
12 4
100
160
140
120
180
200
0
2 6
n
so nho m metylen n
Gian do biu thi su bin thin nhit do nng chay
cua cc axit HOOC-(CH
2
)
n
-COOH
D tan trong nuoc cua cc axit ankandicacboxylic cung c tnh lun phin:
axit c s cacbon le tan nhiu hon axit c cacbon chn. S nguyn tu cacbon
trong phn tu cng tng th d tan trong nuoc cng giam.
Cung nhu monoaxitcacboxylic, diaxitcacboxylic cng kt voi nhau bng lin
kt hidro; chnh su khc nhau v diu kin tao thnh lin kt hidro o axit c s
cacbon chn v le d gy su khc nhau v nhit d nng chay v d tan.
Truong hop don gian nht, axit oxalic c 2 dang tinh th: dang c c u
trc mang luoi, dang c cu trc mach di, ca 2 dang v du l nhung
dang phng:
H
O
C
O
H
O
O
C
C
O
H
O
O
H
O
C
C
O
H
O
O
H
O
C
C
O
O
H
O
C
O
H H
O
C
O
H
O
O
C
Da ng Da ng
C
O
H
O
O
H
O
C
C
O
H
O
O
H
O
C
C
O
H
O
O
H
O
C
9.8.3-Tnh cht ha hc:
Su phn li axit:
Axit dicacboxylic phn li theo 2 nc:
HOOC(CH
2
) COOH + H
2
O
n
n
HOOC(CH
2
) COO + H
3
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 41
OOC(CH
2
) COO + H
3
O
n
n
HOOC(CH
2
) COO + H
2
O
Hng s phn li (K
a
)
1
cua axit dicacboxylic no bao gio cung lon hon o axit
monocacboxylic no tuong ung, v hai nhm cacboxyl c anh huong ht electron
bng hiu ung cam ung m -I ln nhau. Hai nhm d cng o xa nhau (n- cng
lon) anh huong d cng yu, do d tnh axit cng giam.
Hng s phn li axit nc thu hai (k
a
)
2
lun lun nho hon (k
a
)
1
v nhm
cacboxyl thu 2 chiu anh huong +I cua nhm COO
-
thu nht:
(k
a
)
1
> (k
a
)
2
Ti l:
2
1
) (
) (
a
a
K
K
giam nhanh khi n tng.
Th du:
925
) (
) (
2
1
=

,
_

COOH HOOC
a
a
K
K
735
) (
) (
2
2
1
=

,
_

COOH CH HOOC
a
a
K
K
19
) (
) (
2 2
2
1
=

,
_

COOH CH CH HOOC
a
a
K
K
Di voi axit dicacboxylic thom ta cung thy (K
a
)
1
lon hon axit
monocaboxylic tuong ung, cn (K
a
)
2
cung nho hon (K
a
)
1
, nht l tr ong truong
hop axit o-dicacboxylic.
Tc dung cua nhit:
Cc axit c 2 n hm COOH o vi tr 1,2 hoc 1,3 bi nhit phn s dcacboxyl
ha:
HOOC-COOH
C
o
200
HCOOH + CO
2
axit oxalic axit fomic
HOOC-CH
2
-COOH
C
o
160 140
CH
3
COOH + CO
2
axit malonic axit axetic
Nu 2 nhm COOH o vi tr 1,4 v 1, 5, t h su nhit phn s lm cho axit
dng vng thnh anhidrit ni:
COOH CH
2
CH
2
COOH
300 C
o
C CH
2
CH
2
C
O
O
O
+ H
2
O
axit sucxinic
andirit sucxinic
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 42
300 C
o
O
O
O
+ H
2
O
CH
2
COOH
CH
2
COOH CH
2
C CH
2
CH
2
CH
2
C
axit glutaric
anhidrit glutaric
Tuong tu nhu vy cc axit cis-xiclopropan-1,2-dicacboxylic, axit phtalic v
axit maleic cung tao thnh anhidrit tuong ung:
axit ci s-xiclopropan-1,2-dicacboxylic
+ H
2
O
o
t C
C C
O
O
O
H
H
H H
H
H
H
H
COOH
COOH
anhidrit phtalic axit phtalic
C
C COOH
COOH
230 C
o
O
O
O
+ H
2
O
Axit maleic khi nhit phn tao thnh anhidrit maleic, cn axit fumaric (dng
phn trans) lai khng tao thnh anhidrit duoc:
anhidrit maleic
axit maleic
C
C
COOH
COOH
t C
o
O
O
O
+ H
2
O
C
C
H
H H
H
C
C
C
C
H
H
H
H
C
C
+ H
2
O
O
O
O
o
t C
COOH
HOOC
C
C
axit fumaric
Nhung axit c 2 n hm COOH o vi tr 1,6 v 1, 7 hoc xa hon nua nhu axit
adipic, axit pimelic khi bi nhit phn cung dng vng nhu tao thnh xeton vng
v c su dcacboxyl ha:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 43
xiclopentanon
axit adipic
CH
2
COOH CH
2
CH
2
CH
2
COOH
300 C
o
CH
2
CH
2
CH
2
CH
2
C=O
+ CO
2
+ H
2
O
xiclohexanon
axit pimelic
CH
2
COOH CH
2
300 C
o
CH
2
CH
2
C=O
+ CO
2
+ H
2
O CH
2
CH
2
CH
2
CH
2
COOH CH
2
CH
2
Phan ung trng ngung tao polime:
Phan ung trng ngung giua a xit a dipic v ax it adipic tao polime amit l to
nilon-6,6:
nHOOC(CH
2
)
4
COOH + nH
2
N(CH
2
)
6
NH
2

[-HN(CH
2
)
6
NHOC(CH
2
)
4
CO-]
n
+ 2nH
2
O
Phan ung trng ngung giua axit terephtalic voi etilenglycol tao ra to polieste:
nHOOCC
6
H
4
COOH + nHO(CH
2
)
2
OH
[-O(CH
2
)
2
OOCC
6
H
4
CO-]
n
+ 2nH
2
O
COOH + nHOCH
2
CH
2
OH HOOC
-OCH
2
CH
2
-O-C C-
O O
n
n
H
+
+ 2nH
2
O
Phan ung trng ngung giua anhidrit v glixerin tao thnh polime Gliptal
(nhua alkyd):
anhidrit phtalic + glixerin polime gliptal (nhua ankyd)
anhidrit phtalic
C
C
O
O
O
+ CH
2
-CH-CH
2
OH
OH
OH
glixerin
H
2
O
polime Glyptal (nh a alkyd)
Khc voi cc dng dng cao, axit oxalic c tnh khu: Phan ung oxi ha axit
oxalic bng dung dich KMnO
4
duoc dng trong phn tch d xc dinh d chun
cho dung dich ny:
5HOOC-COOH + 2KMnO
4
+ 3H
2
SO
4

K
2
SO
4
+ 2MnSO
4
+ 10CO
2
+ 8H
2
O
Phan ung tao este:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 44
etyl hidro glutarat
CH
2
COOC
2
H
5
CH
2
COOH CH
2
O
O
O
+ C
2
H
5
OH
C CH
2
CH
2
CH
2
C
anhidrit glutaric
Phan ung tao amit:
andirit sucxinic
+2NH
3
O
O
O
C CH
2
CH
2
C
CONH
2
CH
2
CH
2
COONH
4
amonisuxinamit
H
+
axit sucxinamic
CONH
2
CH
2
CH
2
COOH
Phan ung th electronphin vo nhn thom:
O
O
O
C
C
anhidrit phtalic
+
AlCl
3
t C
o
C
O
COOH
axit o-benzoylbenzoic
COOH
O
C
o
t C
AlCl
3
+
C
C
O
O
O
CH
3
CH
3
Phan ung tao thnh thuc thu phenolphtalein:
phenolphtalein
O
C
HO
OH
O
C o
t C
ZnCl
2
anhidrit phtalic
C
C
O
O
O
OH HO
H H
phenol
phenol
+ H
2
O
Su chuyn ha cua phenolphtalein trong mi truong axit v bazo:
kho ng mau
kho ng ma u ma u o
OH
H H
OH
C
O O
COO
phenolphtalein
C
O O
COO
OH
O
C
HO
OH
O
C
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 45
Phan ung tao phtalimit:
O
O
O
C
C
anhidrit phtalic Amoni phtalamat
CONH
2
COONH
4
axit phtalamic
CONH
2
COOH
+2NH
3 + H
300 C
NH
3
, t C t C
o
o
o
C
C
NH
O
O
phtalimit
Phan ung Gbriel - phan ung diu ch amin bc nht tu phtalimit:
ion phtalat
COO
-
COO
-
+KOH
+ RX
t C
o
C
C
NH
O
O
phtalimit kali phtalimat
O
O
NK
C
C C
C
NR
O
O
N-ankylphtalimit
+ H
2
O
OH
-
,
+RNH
2
amin
ba c 1
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 46
B-DAN XUT CUA AXIT CACBOXYLIC
Cc dn xut axit bao gm :
Hal: F, Cl, Br, I
O
Hal
R C
R C
O
R C
O
O R C
NH
2
O
R C
OR
O
R, R : ankyl; aryl
hlogenua axit anhidrit
amit
este
Tn goi mt s dn xut cua axit:
O
R C Nho m axyl:
O
CH
3
C
OH
axit axetic
OH
C
O
axit etanoic
axit benzoic
O
CH
3
C
Cl
axetyl clorua
Cl
C
O
etanoyl clorua
benzoyl clorua
o i:
-ic cu a axit tha nh -yl clorua
C
C
O
O
O
CH
3
C
O
O
O
o i: axit tha nh anhidrit
anhdrit benzoic
anhidrit etanoic
anhidrit axetic
CH
3
C
-ic cu a axit tha nh -amit
o i:
benzamit
etanamit
O
C
NH
2
axetamit
NH
2
CH
3
C
O
hay -oic cu a axit thanh -amit
-ic cu a axit tha nh -at
o i:
etyl benzoat
etyl etanoat
O
C
OCH
5
etyl axetat
OC
2
H
5
CH
3
C
O
Kha nng phan ung axyl ha cua clorua axit, anhidrit axit, este, amit v
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 47
amit th:
RCOCl > (RCO)
2
O > RCOOR
/
> RCONH
2
> RCONHR
/
9.9-Halogenua axit :
R C
Hal
O
Hal: F, Cl, Br, I
Halogenua axit:
9.9.1-Danh php: Tn goi axit cacboxylic tuong ung, thay dui ic thnh thnh
yl + halogenua.
CH
3
CH
2
COOH CH
3
CH
2
COCl
Tn thuong axit propionic propionyl clorua
Tn IUPAC a xit propanoic propananoyl clorua
Cng thuc Tn thng thuong Tn quc t IUPAC
HCOCl fomyl clorua metanoyl clorua
CH
3
COCl axetyl clorua etanoyl clorua
CH
3
CH
2
COCl propionyl clorua propanoyl clorua
CH
3
CH
2
CH
2
COCl n-butyryl clorua butanoylclorua
(CH
3
)
2
CHCOCl isobutyryl clorua 2-metylpropanoyl clorua
CH
3
CH
2
CH
2
CH
2
COCl n-valeryl clorua pentanoyl clorua
(CH
3
)
2
CHCH
2
COCl isovaleryl clorua 3-metylbutanoyl clorua
CH
3
(CH
2
)
14
COCl n-panmityl clorua hexadecanoyl clorua
CH
3
(CH
2
)
16
COCl n-stearyl clorua octadecanoyl clorua
CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COCl
C
17
H
33
COCl
oleyl clorua cis-octadeca-9-enoyl clorua
C
6
H
5
COCl benzoyl clorua benzoyl clorua
C
6
H
4
(COCl)
2
naphtalyl clorua
ClOC-COCl oxalyl clorua
C
6
H
5
CH
2
COCl phenyl axetyl clorua
9.9.2-Diu ch:

'

+
+
+

'

+
HCl POCl
PO H
HCl SO
RCOCl
PCl
PCl
SOCl
RCOOH
3
3 3
2
5
3
2
n-
C
17
H
35
COOH + SOCl
2

n-
C
17
H
35
COCl + SO
2
+ HCl
axit stearic thionyl clorua stearoyl clorua
3CH
3
COOH + PCl
3

C
o
50
3CH
3
COCl + H
3
PO
3
axit axetic axetyl clorua
COOH + PCl
5
100 C
o
COCl + POCl
3
+ HCl
axit benzoic
photpho
pentaclorua
benzoyl clorua
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 48
9.9.3-Tnh cht: Halogenua axit t hp l nhung cht long c mi xc kch thch
mng nhy manh, halogenua axit cao l nhung cht rn.
Cc phan ung dc trung l t h nguyn tu halogen bng nguyn tu hoc gc
khc:
Kha nng phan ung ankyl ha cua ankyl halogenua duoc sp xp theo trt
tu giam dn:
R I
R Br R Cl R F
Kha nng phan ung axyl ha cua halogenua axit duoc sp xp theo trt tu
giam dn:
R C
I
O
R C Br
O
R C
Cl
O O
F
C R
Cc phan ung cua halogenua axit:
Phan ung chung tng qut:
O
Hal
R C + H-Z + H-Hal R C
Z
O
+Tc dung voi nuoc tao axit:
RCOCl + H
2
O RCOOH + HCl
Th du:
COCl + H
2
O COOH + HCl
benzoyl clorua axit benzoic
+Tc dung voi ruou tao este:
RCOCl + HOR
/
RCOOR
/
+ HCl
Th du:
COCl + C
2
H
5
OH
COOC
2
H
5
+ HCl
benzoyl clorua etyl benzoat r u etylic
Clorua axit tc dung voi phenol trong mi truong bazo, thuc cht l clorua
axit tc dung voi mui natri phenolat:
C
O
Cl
HO +
+
O
O
C NaOH + NaCl + H
2
O
+Tc dung voi amoniac tao amit:
RCOCl + NH
3
RCONH
2
+ HCl
RCOCl + NH
2
R
/
RCONHR
/
+ HCl
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 49
Th du:
COCl + 2NH
3
CONH
2
+ NH
4
Cl
benzoyl clorua benzamit amoniac
+ Phan ung th electrophin vo nhn thom - phan ung Friedel-Crafts:
O
R C Ar + H-Cl
+ Ar-H R C
Cl
O
AlCl
3
axit liuyt
xeton
Th du:
n-butyrophenon
O
C-CH
2
CH
2
CH
3
+ HCl
O
CH
3
CH
2
CH
2
-C-Cl +
AlCl
3
t C
o
(phenyl n-propyl xeton)
butanoyl clorua
+Phan ung voi thuoc thu Griganrd:
RMgX
RCOCl
ArCOCl
R C R
O
O
R C Ar
Th du:
C
2
H
5
MgX
CH
3
COCl
C
6
H
5
COCl
CH
3
C C
2
H
5
O
O
CH
3
C C
6
H
5
etyl metylxeton
axetophenon
+Tc dung voi kalixianua: RCOCl + KCN RCOCN + KCl
9.10-Anhidrit:
9.10.1-Tn goi:
CH
3
CH
2
COOH (CH
3
CH
2
CO)
2
O
Tn thuong axit propionic anhidrit propionic
Tn IUPAC axit propanoic anhidrit propanoic
Cng thuc Tn thng thuong Tn quc t IUPAC
(CH
3
CO)
2
O anhidrit axetic anhidrit etanoic
(CH
3
CH
2
CO)
2
O anhidrit propioic anhidrit propanoic
(CH
3
CH
2
CH
2
CO)
2
anhidrit n-butyric anhidrit butanoic
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 50
((CH
3
)
2
CHCO)
2
O anhidrit isobutyric anhidrit 2-metylpropanoic
(CH
3
CH
2
CH
2
CH
2
CO)
2
O anhidrit n-valeric anhidrit pentanoic
((CH
3
)
2
CHCH
2
CO)
2
O anhidrit isovaleric anhidrit 3-metylbutanoic
(CH
3
(CH
2
)
14
CO)
2
O anhidrit panmitic anhidrit hexadecanoic
(CH
3
(CH
2
)
16
CO)
2
O anhidrit stearic anhidrit octadecanoic
(CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
CO)
2
O
(C
17
H
33
CO)
2
anhidrit oleic anhidrit cis-
octadeca-9-enoic
(C
6
H
5
CO)
2
O anhidrit benzoic anhidrit benzoic
O
CH
2
-CO
CH
2
-CO
anhidrit sucxinic
O
O
O
C
C
anhidrit phtalic
H
H
C
C
O
O
O
C
C
anhidrit maleic
Tru HC OOH, cn tt c a cc axit k hc k hi loai 1 phn tu nuoc tao thnh
anhidrit axit:
O
C R
O
R C
O
O
C R
H
O
O
H
R C
O
H
2
O +
AlPO
4
t C
o
Qa trnh phan ung tao xeten CH
2
=C=O do tch nuoc o nhit d cao:
CH
3
COOH
C AlPO
o
700 ,
4
CH
2
=C=O + H
2
O
O
C CH
3
O
CH
3
C
O
CH
2
=C=O + CH
3
COOH
xeten axit axetic
anhidrit axetic
9.10.2-Phuong php diu ch:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 51
+Tch nuoc tu axit ca cboxylic: Dng cht h t nuoc nhu: P
2
O
5
, POCl
3
,
AlPO
4
...di khi dng ngay anhidrit ax etic d tch nuoc tu cc phn tu axit
khc.
Th du:
2CH
3
CH
2
COOH
C t O P
o
,
5 2
(CH
3
CH
2
CO)
2
O + H
2
O
C
O
O H
O
C
C
O
O
C
O H
O
o
+ H
2
O
axit benzoic
anhidrit benzoic
(CH
3
CO)
2
O, t C
+Axyl ha mui kim cua axit cacboxylic:
RCOCl + NaOOC-R
/
R-CO-O-OC-R
/
+ NaCl
Th du:
CH
3
COCl + CH
3
COONa
C t
o
(CH
3
CO)
2
O + NaCl
CH
3
COCl + F
3
C-COONa
C t
o
CH
3
CO-O-COCF
3
+ NaCl
+Tu ahidrit ny tao thnh anhidrit hn tap khc:
HCOOH + (CH
3
CO)
2
O
C t
o
HCO-O-COCH
3
+ CH
3
COOH
Dy l ph an ung fomyl ha tha y cho anhidrit fomic khng bn d diu ch
nhiu este khc nhau cua axit fomic.
9.10.3-Tnh cht cua anhidrit:
Phan ung chung tng qut:
(RCO)
2
O + H-Z RCOZ + RCOOH
+Phan ung voi nuoc tao axit:
(CH
3
CO)
2
O + H
2
O 2CH
3
COOH
anhidrit axetic axi t axetic
+Tc dung voi hidrohalogenua khan tao axit cacboxylic v halogenua axit:
(CH
3
CO)
2
O + HCl CH
3
COOH + CH
3
COCl
anhidrit axetic axit axetic axetyl clorua
+Phan ung Tao amit:
(CH
3
CO)
2
O + 2NH
3
CH
3
CONH
2
+ CH
3
COONH
4
anhidrit axetic axe tamit amoni axetat
(CH
3
CO)
2
O + 2C
6
H
5
NH
2
CH
3
CONHC
6
H
5
+ CH
3
COONH
3
C
6
H
5
anhidrit axetic anilin axetanilit
+Phan ung tao este:
(CH
3
CO)
2
O + C
2
H
5
OH CH
3
COOC
2
H
5
+ CH
3
COOH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 52
anhidrit axetic etanol etyl axetat axit axeic
+ Phan ung th electrophin vo nhn thom - phan ung Friedel-Crafts:
O
C R
O
R
C
O
anhidrit
xeton
axit liuyt
AlCl
3
+ Ar-H
+ RCOOH R C Ar
O
Th du:
axit liuyt
AlCl
3
+
+ RCOOH CH
3
C
O
anhidrit axetic
O
C CH
3
O
CH
3
C
O
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
mezitylen
antraquinon axit o-benzoyl benzoic
anhidrit phtalic
H
2
SO
4
O
C
O
C
OH
C
O
C
O
axit liuyt
AlCl
3
+
O
C
O
C
O
Anhidrit cung nhu cc halogenua axit l nhung cht axyl ha, nhung mnh
lit hon.
9.11-Este:
Este l san phm este ha giua ruou v axit v c cng thuc tng qut l:
R
n
(COO)
nm
R
/
m
.
nghia cua cng thuc:

'

axit lan so La : m
ru lan so La : n
ru goc La : R
axit goc La : R
R (COO) R
/
/
m n.m n
Phan ung este ha tng qat:
m
n.m
n
n
m
nR(COOH) + mR(OH) R (COO) R + n.mH
2
O
Phan ung thuy phn este tng qat trong mi truong axit v bazo:
H
n
m
n.m n
m
R (COO) R + n.mH
2
O nR(COOH) + mR(OH)
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 53
R
n
(COO)
n.m
R
/
m
+ n.mNaOH nR(COONa)
m
+ mR
/
(OH)
n
9.11.1-Diu ch:
+Tu mui bac hay mui kim cua axit cacboxylic v ankyl halogenua:
RCOOAg + I-R
/
RCOOR
/
+ AgI
RCOONa + Cl-R
/
RCOOR
/
+ NaCl
Th du:
CH
3
CH
2
COOAg + I-CH
3
CH
3
CH
2
COOCH
3
+ AgI
CH
3
COONa + Cl-C
2
H
5
CH
3
COOC
2
H
5
+ NaCl
CH
3
COOAg + Cl-CH
2
C
2
H
5
C
2
H
5
+ AgCl
CH
3
COO-CH
2
p-etylbenzyl clorua p-etylbenzyl axetat
Di tu axit v ruou-phan ung este ha:
xa pho ng ho a
este ho a
+
O
R C
O
O R
H
H
H
2
O +
R
O
C R
O
Phan ung este ha c tnh cht thun nghich. Hng s cn bng:
] ].[ [
] ].[ [(
/
2
/
OH R RCOOH
O H RCOOR
K =
Th du:
(CH
3
)
2
CHCH
2
CH
2
OH + CH
3
COOH CH
3
COOCH
2
CH
2
(CH
3
)
2
+ H
2
O
ruou izoamylic axit axetic izoamyl axetat
+Tu clorua axit v ruou hoc phenol:
RCOCl + HOR
/
RCOOR
/
+ HCl
Th du:
CH
3
COCl + (CH
3
)
3
C-OH CH
3
COO-C(CH
3
)
3
+ HCl
axetyl clorua ruou tert-butylic tert-butylaxetat
CH
3
COCl + C
6
H
5
-OH + NaOH CH
3
COC
6
H
5
+ NaCl + H
2
O
axetyl clorua phenol axetophenon
+Tu anhidrit axit v ruou hoc phenol:
(RCO)
2
O + R
/
OH RCOOR
/
+ RCOOH
Th du:
(CH
3
CO)
2
O + HOC
6
H
5
CH
3
COOC
6
H
5
+ CH
3
COOH
anhidrit axetic phenol phenyl axetat axit axetic
(CH
3
CO)
2
O + HOC
2
H
5
CH
3
COOC
2
H
5
+ CH
3
COOH
anhidrit axetic ruou etylic etyl axetat axit axetic
+Tu xeten v ruou hoc phenol:
CH
2
=C=O + HOR
/
CH
3
COOR
/
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 54
+Tu axit v diazometan:
RCOOH + CH
2
N
2
RCOOCH
3
+ N
2

Th du:
CH
2
COOH + CH
2
N
2
CH
2
COOCH
3
+ N
2
axit xiclopropyl axetic metyl xiclopropyl axetat
+Tu hop cht ntrin v ruou:
RCN + HOR
/
+ H
2
O
+
H
RCOOR
/
+ NH
3
Th du:
CH
3
CN + HOC
2
H
5
+ H
2
O
+
H
CH
3
COOC
2
H
5
+ NH
3
9.11.2-Tnh cht:
Este c mi thom d chiu, t tan trong nuoc.
+Phan ung thuy phn hay x phng ha:
Thuy phn trong mi truong axit l phan ung thun nghich:
RCOOR + H
2
O RCOOH + ROH
H
Co ch phan ung thuy phn este xc tc axit:
hay
OH
R C OR
H
R C OR
O
O
R C OR + H
H
R C O H + ROH
O
OH
2
H
R C OR
O
+

+
H
H O
O
R C OR
H
H
R C O H
O O
R C O H + H
axit cacboxylic
Th du:
CH
3
COOC
2
H
5
+ H
2
O CH
3
COOH + C
2
H
5
OH
H
+
etyl axetat axit axetic r u etylic
Thuy phn trong mi truong kim l phan ung bt thun nghich:
RCOOR
/
+ NaOH RCOONa + R
/
OH
Co ch thuy phn este xc tc bng kim :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 55

O
R C R O
+ HO
O
H
R
C
OH
+
R
O
O
O
C R O
R C
O
OH
R
R
O
Nhung phan ung thuy phn trn du l nhung phan ung lung phn tu kiu
S
N
2. Phn tu este bi thuy phn l lin kt C-OR
/
:
R C O R
O
Diu d d duoc thuc nghim xc minh bng phuong php dng vi dnh
du d ng H
2
O
18
khi thuy phn izoamyl axetat, t ao ra a xit a xetic c chua oxi
dng vi 18:
H 18
CH
3
C O H + C
5
H
11
OH
O
18
O
CH
3
C O C
5
H
11
+
H
H O
Hoc nguoc lai thuy phn etylpropionat c chua oxi dng vi 18 voi nuoc,
tao ruou etylic c chua oxi dng vi 18:
H
H O
H
CH
3
CH
2
C O C
2
H
5
+
O
18
O
CH
3
CH
2
C O H + C
2
H
5
OH
18
C mt s truong hop dc bit xay ra theo co ch th don phn tu S
N
1- co
ch phn ct axyl - oxi don phn tu v ankyl - oxi don phn tu:
O
R C O R
O
R C O R
va
Th du:
(raxemic: D, L)
CH
3
O
OH
CH CH
3
O
H
2
O
CH
3
O
CH
H
2
O
CH
O
C=O
COOH
p-metoxibenzhidylphtalat
(quang hoa t)
p-metoxibenzhidrol
Co ch ny duoc chung minh xc nhn bng dng vi dnh du
18
O:
CH
3
C O C CH
3
C CH
3
O
CH
3
CH
3
CH
3
CH
3
H
2
O
18 18
H
2
O
CH
3
CH
3
H O C CH
3
18
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 56
+Phan ung chuyn este :
+
O
R
C
R
O R
R
ROH
O
R
C
+
R O
O
O
Co ch phan ung:
R
O
O R C
O
O
R
+
OR
C
R
O
RO
R

O
R
C
R
O
Th du:
CH
2
=CHCOOCH
3
+ CH
3
CH
2
CH
2
CH
2
OH
C
4
H
9
ONa
CH
2
=CHCOOCH
2
CH
2
CH
2
CH
3
+ CH
3
OH
n-butylacrilat r u metylic
+Phan ung tao amit:
NH
3
+ RCOOR
/
RCONH
2
+ R
/
OH
O
R
+
C
R
O O
R
C
NH
3
R
O
H
3
N
ONH
4
R
NH
2
C
R
O
H
3
N
O R NH
4
O
+ R C NH
2
+
OH R NH
3
O
+ R C NH
2
+
Th du:
NH
3
+ CH
3
COOCH
3
CH
3
CONH
2
+ CH
3
OH
+Phan ung khu: Este khng nhung khu duoc bng LiAlH
4
m cn dng hidro
moi sinh duoc t ao ra do tc dung cua nat ri kim loai voi ruou si - phan ung
Buvon-Blng (Buoveault-Blanc), hoc H
2
/dng cromit:
+
/
ROH RCH
2
OH
[H]
/
RCOOR
Th du: Khu ha e ste n-butyloleat bng hidro moi sinh do natri kim loai tc
dung voi ruou etylic ta duoc ruou khng no oleylic:
CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOC
4
H
9
+ 2[H]

+Na OH H C
5 2
C
4
H
9
OH + CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
CH
2
OH
ruou n-butylic r uou oleylic
(nho r ng ph an ung kh u b ng hi dro moi sinh ho c LiAlH
4
, n oi di C=C
trong phn tu duoc bao ton!)
+Phan ung voi nhm metylen linh dng:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 57
H CHCOOC
2
H
5
R
R C O C
2
H
5
+
O
O
R C CH COOC
2
H
5
+ C
2
H
5
OH
R
C
2
H
5
ONa
Th du:
H CH
2
COOC
2
H
5
CH
3
C O C
2
H
5
+
O O
CH
3
C CH COOC
2
H
5
+ C
2
H
5
OH
C
2
H
5
ONa
Co ch phan ung:
H CH
2
COOC
2
H
5
C
2
H
5
O +
C
2
H
5
OH + CH
2
COOC
2
H
5

CH
3
C + CH
2
COOC
2
H
5
O
OC
2
H
5

OC
2
H
5
O
CH
3
C CH
2
COOC
2
H
5
O
CH
3
C CH
2
COOC
2
H
5
+ C
2
H
5
O CH
3
C CH
2
COOC
2
H
5
O
OC
2
H
5
O
CH
3
C CH COOC
2
H
5
+ C
2
H
5
OH CH
3
C CH
2
COOC
2
H
5
+ C
2
H
5
O
O
Phan ung ngung tu Claizen giua 2 est e khc nhau thuong cho hn hop cc
san phm. Tuy vy, nu mt tr ong 2 este d khng c hidro o vi tr , th chi
tao ra mt san phm m thi.
Th du:
+Phan ung giua etylfomiat voi etylphenylaxetat:
etyl -fomylphenylaxetat
etyl phenylaxetat etylfomiat
H-C CH-COOC
2
H
5
+ C
2
H
5
OH
O
C
2
H
5
ONa
O
H-C-OOC
2
H
5
+ H-CH-COOC
2
H
5
+Phan ung giua dietyloxalat voi etyl-n-bytyrat:
O=C-OOC
2
H
5
C
2
H
5
C
2
H
5
O=C-OOC
2
H
5
O=C-OOC
2
H
5
+ H-CH-COOC
2
H
5
C
2
H
5
ONa
O=C CH-COOC
2
H
5
+ C
2
H
5
OH
dietyloxalat
etyl n-butyrat etyl -oxalyl-n-butyrat
Mt s ung dung cua este:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 58
Este thp: etylaxetat, n-butyl axetat, a myl axetat .. .duoc dng lm dung
mi, dc bit l d ung mi pha son nitroxenlulozo, mt s este thp duoc dng
lm cht thom v chng c mi thom th du: etyl fomiat c mi to, mi do;
benzyl axetat v benzyl propionat c mi hoa nhi; izoamyl axetat c mi chui
chn...
Este cua axit bo cao c nhiu trong sp nhu sp ong c mirixyl panmitat
C
15
H
31
COOC
30
H
61
. Es te cua gli xerin voi axit bo cao no l th nh phn chnh
cua m dng vt, e ste cua gli xerin voi axit bo cao khng no l th nh phn
chnh cua du thuc vt....
San phm trng hop cc vinyleste l nhung polime c th dng vo muc
dch khc nhau: d tao hnh v ko soi, d tm vo giy hoc cc mt hng soi,
lm h dn v l m cht kt d nh cho son mu, polivinyl axetat t am duong v
chat thom duoc ch bin thnh keo gm.
Mt luong lon polivinyl axetat duoc thuy phn thnh polivinyl ancol:
polivinyl ancol
polivinyl axetat
o
t C
(-CH
2
=CH-) + nCH
3
COONa
OH
n
n
OCOCH
3
(-CH
2
=CH-) + nNaOH
Polivinyl ancol khng tan trong da s cc dung mi huu co v tan trong nuoc.
N duoc dng lm cht gy nhu tuong ha, lm h dn, d cho thm vo muc
vit, vo muc in....Tu polivinyl ancol c th ch tao cc tm mng mong.
Trong cng nghip cao phn tu nguoi ta cn dng este cua axit metacrilic d
tng hop ra vt liu goi l thuy tinh huu co:
(-CH
2
C-)
COOCH
3
n
CH
3
polimetyl metacrilat
metyl metacrilat
o
t C
CH
3
n
COOCH
3
CH
2
=C
Polieste tng hop tu daxitcacboxylic v -glicol l nhung cht cao phn tu
dng lm soi tng hop, chng han soi tetrilen l polieste cua axit terephtalic v
etilenglicol:
O O
(-C C-O-CH
2
CH
2
O-) + 2nH
2
O
COOH + nHOCH
2
CH
2
OH nHOOC
n
Polieste cua cc axit dicacboxylic (phtalic, maleic) v glixerin l nhung cht
deo m t rong cng nghip th uong goi l nhua alkyd. Chng han nhua alkyd
glixero-phtaic hay glyptal l nhua diu ch tu axit phtalic v glixerin c cu tao
nhu sau:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 59
O
O
OCH
2
-CH-CH
2
-C
O
C-OCH
2
-CH-CH
2
O-C
O
O
C=O
O
C
C=O
O
C
O
O
...
...
...
O
C-OCH
2
-CH-CH
2
O-C
O
OCH
2
-CH-CH
2
-C
O
...
Nhua glyptal duoc dng rng ri d lm son v cc vt liu cch din.
Trong linh vuc nng nghip nguoi ta dng nhiu este cua cc axit khc nhau
lm cht phng tru dich hai v k ch thch t sinh truong cho cy trng, quan
trong hon ca l nhm este tu nhin:
Pretrin: l nhm cc este phuc tap c hoat tnh tru su manh nht c cng thuc
cu tao nhu sau:
CH
3
-C=CH-CH-CH-C-O
CH
3
R
O
C
CH
3
CH
3
CH
3
O
R: -CH
2
CH=CHCH
3
: xinerin-1
R: -CH
2
-CH=CH-CH-CH=CH
2
: Piretrin-1
Giberelin: l n hm mono este ni c tc dung diu tit sinh truong thuc vt.
Hoat tnh sinh truong cao nht l axit giberelic c cng thuc cu tao l:
OH
CH
2 COOH
CH
3
OH
CO
H
9.12-Amit:
9.12.1-Tn goi:
CH
3
CH
2
COOH CH
3
CH
2
CONH
2
Tn thuong axit propionic propionamit
Tn IUPAC a xit propanoic propanamit
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 60
Cng thuc Tn thng thuong Tn quc t IUPAC
HCONH
2
fomamit metanamit
CH
3
CONH
2
axetamit etanamit
CH
3
CH
2
CONH
2
propionamit propanamit
CH
3
CH
2
CH
2
CONH
2
n-butyramit butanamit
(CH
3
)
2
CHCONH
2
isobutyramit 2-metylpropanamit
CH
3
CH
2
CH
2
CH
2
CONH
2
n-valeramit pentanamit
(CH
3
)
2
CHCH
2
CONH
2
isovaleramit 3-metylbutanamit
CH
3
(CH
2
)
4
CONH
2
n-capramit hexanoamit
CH
3
(CH
2
)
5
CONH
2
n-caprylamit heptanamit
CH
3
(CH
2
)
10
CONH
2
n-lauramit dodecanamit
CH
3
(CH
2
)
12
CONH
2
n-miristamit tetradecanamit
CH
3
(CH
2
)
14
CONH
2
n-panmitamit hexadecanamit
CH
3
(CH
2
)
16
CO NH
2
n-stearamit octadecanamit
CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
CONH
2
C
17
H
33
CO NH
2
oleamit cis-octadeca-9-enamit
C
6
H
5
CONH
2
b enzamit benzamit
H
2
NOC-CONH
2
o xamit oxamit
CH
2
-CO
CH
2
-CO
NH
sucxinimit
C
C
NH
O
O
phtalimit
C
C
NH
O
O
C
C
H
H
maleinimit
9.12.2-Diu ch:
-RCOONH
4
RCONH
2
+ H
2
O
Th du:
CH
3
COONH
4

C
o
220
CH
3
CONH
2
+ H
2
O
-RCOCl + NH
3
RCONH
2
+ HCl
Th du:
COCl + 2NH
3
CONH
2
+ NH
4
Cl
benzoyl clorua benzamit amoniac
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 61
-(RCO)
2
O + 2NH
3
RCONH
2
+ RCOONH
4
(CH
3
CO)
2
O + 2NH
3
CH
3
CONH
2
+ CH
3
COONH
4
anhidrit axetic axe tamit amoni axetat
-RCN + H
2
O RCONH
2
Th du:
CH
3
CN + H
2
O CH
3
CONH
2
9.12.3-Tnh cht:
+Tc dung voi axit nitro:
RCONH
2
+ HO-NO RCOOH + N
2
+ H
2
O
+Thuy phn:
RCONH
2
+ H
2
O
+ -
OH hoac H
RCOOH + NH
3
+Khu thnh amin:
R-C
NH
2
O
H
2
, xt, p
hoa c LiAlH
4
R-CH
2
NH
2
amit
amin
Th du:
CH
3
-C
NH
2
O
H
2
, xt, p
hoa c LiAlH
4
CH
3
-CH
2
NH
2
axetamit etylamin
+Tc dung voi ankyl halogen:
RCONH
2
+ I-CH
3
RCONHCH
3
+ HI
+Phan ung tch nuoc thnh nitrin:
nitrin amit
R-C N
H
2
O
P
2
O
5
O
NH
2
R-C
Th du:
NH
2
O
P
2
O
5
H
2
O
isobutyramit
(CH
3
)
2
CH-C (CH
3
)
2
CH-C N
isobutyronitrin
+Phan ung thoi phn Hofmann :
RCONH
2
+ Br
2
+ 4NaOH RNH
2
+ Na
2
CO
3
+ 2NaBr + 2H
2
O
Qa trnh phan ung din ra nhu sau:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 62
RCONHBr
NaOH
RCONH
2
R CO N +
Br
2
+
H
2
O
HBr NaBr
Na
2
CO
3
RNH
2
R CO N
R N=C=O
+
+ NaOH 2 c/v
izoxyanat
Th du:
C che phan ng Hofmann nh sau :
CH
3
CONH
2
+ Br
2
+ 4NaOH CH
3
NH
2
+ Na
2
CO
3
+ 2NaBr + 2H
2
O
Br
2
+ 2NaOH NaOBr + NaBr + H
2
O
NaOBr Na
+
+ OBr
-
1) CH
3
-C-NH
2
+ OBr
O
CH
3
-C-NHBr + OH
O
2) CH
3
-C-NHBr + OH
O
CH
3
-C-NBr + H
2
O
O
CH
3
-N=C=O 4) CH
3
-C-N:
O
3) CH
3
-C-NBr + H
2
O
O
CH
3
-C-N: + Br
O
5) CH
3
-N=C=O + 2OH CH
3
-NH
2
+ CO
3
2-
O
O
NH
C
C
NaOH
COOH
CONH
2
Br
2
+ NaOH
NH
2
COOH
axit antranilic
phtalimit
Diu ch saccarin, l cht ngot gp 500 ln duong saccarozo:
sacccarin o-sunfamit cu a
axit benzoic
o-toluensufamit
o-toluensufo
clorua
toluen
NH
SO
2
CO
H
2
O SO
2
NH
2
COOH
KMnO
4 CH
3
SO
2
NH
2
NH
3
SO
2
Cl
CH
3
HSO
3
Cl
CH
3
9.13-Nitrin:
9.13.1-Tn gi:
CH
3
CH
2
COOH CH
3
CH
2
CN
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 63
Tn thuong axit propionic propionitrin (etyl xianua)
Tn IUPAC axit propanoic propanitrin (xianetan)
Cng thuc Tn thng thuong Tn quc t IUPAC
HCN
fomonitrin
(axit xianhidric)
metanitrin
CH
3
CN
axetonitrin etanitrin
CH
3
CH
2
CONH propionitrin propanitrin
CH
3
CH
2
CH
2
CN
n-butyronitrin butanitrin
(CH
3
)
2
CH-CN
isobutyronitrin 2-metylpropanitrin
CH
3
CH
2
CH
2
CH
2
CN
n-valeronitrin pentanitrin
(CH
3
)
2
CHCH
2
CN
isovaleronitrin 3-metylbutanitrin
CH
3
(CH
2
)
14
CN
n-panmitonitrin hexadecanitrin
CH
3
(CH
2
)
16
CN
n-stearonitrin octadecanitrin
C
6
H
5
CN
benzonitrin benzonitrin
CH
2
=CH-CN
acrilonitrin propenitrin
9.13.2-Diu ch:
+Phan ung tch nuoc cua amit thnh nitrin:
nitrin amit
R-C N
H
2
O
P
2
O
5
O
NH
2
R-C
Th du:
propionitrin
CH
3
-CH
2
-C N
CH
3
-CH-C
propionamit
H
2
O
P
2
O
5
O
NH
2
+ Tu dn xut ankylhalogenua hoc diankylsunfat:
R-Hal + KCN R-CN + K-Hal
R
2
SO
4
+ 2KCN 2RCN + K
2
SO
4
Th du:
CH
3
CH
2
CH
2
CH
2
Br + KCN CH
3
CH
2
CH
2
CH
2
CN + KBr
(CH
3
)
2
SO
4
+ 2NaCN 2CH
3
CN + Na
2
SO
4
+Tu mui diazoni:
NH
2
[N N
+
]Cl
-
CH
3
CH
3
NaNO
2
+ 2HCl
+ CuCl + N
2
+CuCN
CH
3
CN
+Tu axetylen:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 64
CHCH + HCN CH
2
=CH-CN
+Tu oxit etylen:
CH
2
CH
2
+ HCN
O
60 C
o
HO-CH
2
CH
2
CN
170 C
H
2
O
o
CH
2
=CH-C N
+Tu propilen v NH
3
:
4CH
2
=CHCH
3
+ 3O
2
+ 4NH
3

xt C t
o
,
4CH
2
=CH-CN + 6H
2
O
9.13.3-Tnh cht ha hc:
-Thuy phn theo hai giai doan:
RCN + H
2
O
+ O H
2
RCONH
2

+ O H
2
RCOOH + NH
3
Th du:
CH
3
CN + H
2
O
+ O H
2
CH
3
CONH
2

+ O H
2
CH
3
COOH + NH
3
-Khu hop chat nitrin lun lun tao ra amin bac mot:
RCN + 4[H] RCH
2
NH
2
( Cht khu [H] : Sn + HCl ; H
2
/Ni ; Na + C
2
H
5
OH ; LiAlH
4
).
Th du:
C
6
H
5
CH
2
CN + 4[H] C
6
H
5
CH
2
CH
2
NH
2
CH
3
CH
2
CH
2
CN + 4[H]
ete ,
4
AlLiH
CH
3
CH
2
CH
2
CH
2
NH
2
C
6
H
5
CH
2
CN + 4[H]
6 2
H B
C
6
H
5
CH
2
CH
2
NH
2
CH
3
CH
2
CN + 2H
2

C t Ni
o
,
CH
3
CH
2
CH
2
NH
2
NC(CH
2
)
4
CN
C t Ni H
o
, ,
2
H
2
N(CH
2
)
6
NH
2
adiponitrin hexametylendiamin
-Phan ung cong nucleophin cua acrilonitrin:
C
6
H
5
NH
2
+ CH
2
=CH C N
C
6
H
5
NHCH
2
CH
2
C N
-Phan ung trng hop:
t C
p, xt
o
nCH
2
=CH-C N
(-CH
2
-CH-)
CN
n
acrilonitrin poliacrilonitrin
C-LIPIT (CHT BO)
Khi nim : Lipit l tn chung bao gm cc cht cht bo tuc l m dng thuc
vt l est e cua glixer in voi axit bo cao, khng tan trong nuoc tan trong cc
dung mi huu c
9.14.Cu to cua cc cht bo:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 65
Cht bo l este cua glixerin v axit bo cao khc nhau c tn chung l
glixerit v c cng thuc cu tao:
CH
2
O C R
O
O
CH
2
O C R
O
CH O C R
Th du:
OCO C
17
H
35
OCO C
17
H
35
OCO C
17
H
35
CH
2
CH
CH
2
tristearin
triolein
CH
2
CH
CH
2
OCO C
17
H
33
OCO C
17
H
33
OCO C
17
H
33
OCO C
17
H
35
OCO C
15
H
31
OCO C
17
H
33
CH
2
CH
CH
2
oleo panmito stearin
Mt s axit bo quan trong d tch tu cht bo thin nhin:
Axit butyric : CH
3
(CH
2
)
2
COOH
Axit caproic : CH
3
(CH
2
)
4
COOH
Axit caprilic : CH
3
(CH
2
)
6
COOH
Axit caprinic : CH
3
(CH
2
)
8
COOH
Axit lauric : CH
3
(CH
2
)
10
COOH
Axit miristic : CH
3
(CH
2
)
12
COOH
Axit panmitic : CH
3
(CH
2
)
14
COOH
Axit stearic : CH
3
(CH
2
)
16
COOH
Axit dodexenic: CH
3
CH
2
CH=CH(CH
2
)
7
COOH
Axit tetradexenic : CH
3
(CH
2
)
3
CH=CH(CH
2
)
7
COOH
Axit panmiteleic : CH
3
(CH
2
)
5
CH=CH(CH
2
)
7
COOH
Axit oleic: CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOH (cis)
Axit linoleic: CH
3
(CH
2
)
4
CH=CHCH
2
CH=CH(CH
2
)
7
COOH
Axit linolenic:CH
3
CH
2
CH=CHCH
2
CH=CHCH
2
CH=CH(CH
2
)
7
COOH
9.15-Tnh cht cua cht bo :
9.15.1-Tnh cht l hc:
+Lipit khng chung ct duoc, v chng bi phn huy, ngay ca khi ct duoi p
sut thp.
+Du m dng thuc vt khng c nhit d nng chay xc dinh (gioi han
rng), v chng l hn hop phuc tap cc glixerit.
Cc du m chua nhiu axit no nng chay o nhit d cao hon cc du m
chua nhiu axit bo chua no.
M dng vt chu yu l este cua glixerin voi axit bo cao no, o diu kin
thuong l th rn; cn du thuc vt chu yu l este cua glixerin voi axit bo cao
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 66
chua no (chu yu l a xit ole ic v a xit ch ua no khc), o th long o nhit d
thuong.
+cht bo khng tan trong nuoc, tao duoc dung dich keo hay nhu tuong bn
khi c thm cht hoat dng b mt (cht nhu tuong ha) nhu x phng, protit....
Mt tr ong cc nhu tuong thin nhin bn cua ch t bo l sua, nhu tuong d
duoc n dinh do su c mt cua protit .
9.15.2-Tnh cht ha hc:
-Thuy phn (hay x phng ha) chat bo :
Khi dun nng cht bo voi axit s thu duoc glixerin v axit bo, dun voi xt
s thu duoc glixerin v mui natri cua axit bo (x phng). Phan ung thuy phn
cht bo tin hnh trong ng tiu ha c ua c o th nguoi v dng vt n ho tc
dung xc tc cua men lipazo :
H
RCOOH
RCOOH
CH
2
CH
CH
2
OCOR
OCOR
OCOR
+
3
H
2
O RCOOH
CH
2
CH
CH
2
OH
OH
OH
+
mem lipaz
hoa c
xa pho ng
RCOONa
RCOONa
CH
2
CH
CH
2
OCOR
OCOR
OCOR
+
3
NaOH
RCOONa
CH
2
CH
CH
2
OH
OH
OH
+
-Phan ung cong hidro v cong halogen vo chat bo :
triolein
+
OCOC
17
H
33
OCOC
17
H
33
OCOC
17
H
33
CH
2
CH
CH
2
CH
2
CH
CH
2
OCOC
17
H
35
OCOC
17
H
35
OCOC
17
H
35
tristearin
3H
2
Ni
t
o
3I
2
OCOC
17
H
33
I
2
OCOC
17
H
33
I
2
OCOC
17
H
33
I
2
CH
2
CH
CH
2
CH
2
CH
CH
2
OCOC
17
H
33
OCOC
17
H
33
OCOC
17
H
33
+
triolein
-Phan ung tu oxi ha v trng hop:
Mt s cht bo d lu ngoi khng kh c mi kh chiu, c mi i: cht bo
bi thuy phn, mt s axit bo chua no duoc giai phng ra bi oxi ha tip theo
boi oxi khng kh tao thnh hidropeoxit bn canh nguyn tu cacbon mang ni
di, hidropeoxit tao thnh c th bi phn huy thnh andehit v xeton hoc nuoc
v xeton hoc ancol v epoxit :
CH
2
CH=CH CH
2
O
2
+
CH
2
CH=CH CH
O O H
men
R
2
R
1
R
2
R
1
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 67
CH
2
CH=CH CH
O O H
R
2
OH
R
2
R
1
R
1
CH
2
CH=CH CH=O +
R
1
-CH
2
-CH=CH-CO-R
2
H
2
O
+
+
CH
2
CH=CH CH
OH
R
2
R
1
O
CH CH CH=CH
Mi i cua cht bo c th do su tao thnh mt s andehit hoc xeton.
O ngoi khng kh mt s du thuc vt nhu du lanh cung bi ha rn boi su
trng hop v oxi ha phuc tap, nho tnh cht ny m mt s du thuc vt duoc
dng lm dung mi pha son.
-Phuong php nhan bit chat bo :
+ Cch 1: Do tnh cht khng bay hoi cua cht bo nn khi nho trn to giy s
d lai vt trong mo d d lu cung khng bin mt, nho d c th nhn bit cht
bo d dng.
+ Cch 2 : Cung c th nhn bit cht bo bng th nghim tao acrolein: Khi
dun nng cht bo voi cht ht nuoc nhu KHSO
4
, mt t g ixerin duoc giai
phng do nhit d s bi tch loai nuoc tao acrolein c mi kht dc trung :
KHSO
4
H
2
O CH
2
=CH CH=O CH
2
OHCHOHCH
2
OH
t
o
+
acrolein
2
-Mot so dai luong dc trung cua chat bo :
*Chi so axit :
Chi s axit l biu thi bng s mg KOH dng d trung ha 1g cht bo. Chi
s axit ni ln su c mt nhiu hay t cua axit tu do trong du m.
*Chi so x phng ha : Bi u t hi bng s mg KOH dng d x phng ha hon
ton 1g cht bo. Chi s x p hng ha ni ln thnh phn tng cng cc axit
bo. Chi s x phn g ha ca o chung to su c mt cua c c axit phn tu nho ;
nguoc l ai chi s x phng ha nho chung to su c mt c mt cua nhung axit
bo cao hoc c chua nhiu cht khng x phng ha duoc.
*Chi so iot: Biu thi s gam it c th kt hop voi 100g cht bo. Chi s it l
d do tnh cht chua no cua cc axit bo trong du m.
9.15.3-X phng:
+inh nghia: X phng l nhng hon hop muoi natri ho c kali cua cc axit
bo cao.
+Nguyn liu: Hu ht du m dng thuc vt du c th lm nguyn liu ch x
phng, s ong phai han ch toi muc t i da v du m l thuc phm cho nguoi.
Axit lauric (CH
3
(CH
2
)
10
COOH) lm x phng c kha nng tao bot v t y sach
tt, v vy khi ch x phng nguoi ta t huong thm du dua hoc du co vo v
giu a xit la uric. Axit ol eic cung cho x phng c cht luong cao. Axit stearic
(CH
3
(CH
2
)
16
COOH) lm x phng c tnh tan v kha nng tao bot km.
+San xuat x phng : Du, m dun nng bng hoi nuoc o 100
o
C r i cho dung
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 68
dich NaOH vo bt du voi luong nho d tao nhu tuong; dang ny lm tng
din tch tip xc cua du m voi NaOH v thuy phn nhanh (trong thoi gian
khoang 12-14 gi o) khi cho luong NaOH vua du. Khi du m thuy phn ht,
cho dung dich NaCl dm dc vo tch duoc x phng nng chay tao thnh lop
ni ln trn, cn lop duoi l dung dich glixerin v NaCl. D l giai doan mui
tch. L op nuoc ny c th dng d san sut g lixerin. X phn g git thuong
chua 62 -64% axit bo. Mu n san sut x phn g thom cn dng nguyn liu
tinh khit hon, c thnh phn axit bo 80-85% v cho thm huong liu.
+Tnh chat c ua x phng: Dung dich x p hng c suc cng b mt nho hon
nhiu so voi nuoc nguyn cht. dung dich x phng l mt h keo, khi dm dc
c d nhot ca o. X phng dc tr ung boi phn tu cua chng ko di, voi mt
nhm -COO

o mot dau c tnh ua nuoc, v mt goc hidrocacbon di ki nuoc.


Cc anion RCOO
-
c khuynh huong tch luy trn b mt dung dich v duoc
dinh huong boi cc nhm COO
-
v pha truoc. Tnh ch t n y g y kha nng
tham uot nhanh cua dung dich x phng. Ban cht tay rua cua x phng l qa
trnh nhu tuong ha, x phng dng vai tr l cht nhu ha, lm giam suc cng
b mt cua du m boi gc hidrocacbon, chng chuyn thnh nhung giot nho
khi lc hoc v s t v phn b vo dung dich x p hng tao thnh nhu tuong v
tri theo nuoc.
* Uu - nhuoc dim cua x phng :
+Uu dim :
-Khng gy nhim mi truong v km bn, d bi vi sinh vt ph huy.
+Nhuoc dim:
-Nu ch bin tu du m dng thuc vt, n n vi pham ngun thuc phm cua
nguoi.
-Khng git duoc trong nuoc cung (nuoc cung l n uoc c chua ion Ca
2+
v
Mg
2+
) v tao kt t ua (RCOO)
2
Ca v (RCOO)
2
Mg, nn vua t n x phng, vua
lm qun o chng rch do kt tua bm vo to vai soi:
2C
17
H
35
COONa + Ca
2+
(C
17
H
35
COO)
2
Ca + 2Na
+
2C
17
H
35
COONa + Mg
2+
(C
17
H
35
COO)
2
Mg + 2Na
+
9.15.4-Cc chat tay rua tong hop (cc chat hoat dong b mt tong hop) :
+inh nghia: Chat t ay rua tong hop l nhng chat khng phai l muoi natri
cua axit bo cao nhung cng c nh ng tnh chat giong nhu x phng nhu c
kha nng tham uot cao, c tnh chat lm gi am suc cng b mt, c tc dung
tay rua .
+Cc chat tay rua tc nhn l anion :
-ROSO
3
Na : sunfat axit cua ancol cao duoi dang mui natri.
Th du: C
18
H
37
OSO
3
Na: sunfat c ua a ncol octadexilic hay tn ki thut goi l
bacdnol ,inferol .
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 69
-RSO
3
Na : Mui natri cua sunfoaxit mach thng cao:
Th du: cc ankan sufoaxit cao tu du mo, tn ki thut goi l meczolat .
-R
2
C
10
H
5
SO
3
Na: Sunfoaxit cua diankylnaptalen (diizopropyl, disecbutyl, hoc
damyl).
-R-C
6
H
4
SO
3
Na : Ankyl aryl sunfonat natri:
Th du : dodexyl benzen sunfonat natri : C
12
H
25
-C
6
H
4
SO
3
Na .
-ROOC-CH
2
-CH(COOR)-SO
3
Na : e ste cua a xit sunfosucxinic c tn ki thut
l aerozol.
-RCOOCH
2
CH
2
SO
3
Na : este cua axit bo cao voi oxi sunfoaxit :
Th d u : CH
3
(CH
2
)
7
CH=CH(CH
2
)
7
COOCH
2
CH
2
SO
3
Na, tn ki thut g oi l
Igepon A .
+Cc chat tay rua tc nhn l cation :
-[R-NR
/
3
]
+
X
-
: Mui amni bc bn, tr ong d R l g c ankyl cao mach thng
C
12
-C
18
, R
/
l nhung ankyl thp :
Th du : [R-N(CH
3
)
2
C
2
H
5
]
+
Cl
-
tn ki thut l rfirol .
-[R-O-CH
2
NR
/
3
]
+
X
-
: Diu ch tu dn xut th clo cua ete c gc ankyl cao
ROCH
2
Cl + NR
/
3
hoc voi piridin NC
5
H
5
:
Th du: [R-O-CH
2
NC
5
H
5
]
+
X
-
tn ki thut l Vlan , Textin , slan".
+Cc chat tay rua khng ion ha :
Cc cht ty rua loai ny c chua nhm khng ion ha, khng phn cuc
gm mt s nguyn tu oxi ete voi OH du mach. Do cc hop cht ny khng c
din tch, t c dung ty rua cua chng khng phu thuc vo pH cua dung dich
hoc su c mt cua ion khc:
-RO(CH
2
CH
2
O)
X
-CH
2
CH
2
OH: ete cua ancol cao voi polietylenglycol
.R=C
18
H
37
, x=10 .igepal .
-Ar-O(CH
2
CH
2
O)
X
-CH
2
CH
2
OH : Ar = phenyl d duoc ankyl ha.
-RCOO(CH
2
CH
2
O)
X
-CH
2
CH
2
OH: este cua axit bo cao (nhu axit oleic) .
*-Uu - nhuoc dim cua chat tay rua tong hop:
+Uu dim:
-Duoc ch bin tu du mo, nn re tin, khng vi pham ngun thuc phm cua
nguoi.
-Git duoc trong nuoc cung.
+Nhuoc dim: Mt s cht t y r ua rt bn vung (nht l nhung cht c gc
sunfat), khng bi vi sinh vt ph huy, nn gy nhim mi truong.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 70
Chuong 10
AMIN-MUI DIAZONI
A-AMIN
10.1-Khi nim v phn loi:
Khi ni m : Amin c th coi l d an xuat c ua NH
3
, trong d cc nguyn tu
hidro d duoc thay th bng cc goc hidrocacbon :
RNH
2
R
2
NH R
3
N
R
4
N
+
X
-
amin ba c
mo t
hai
amin ba c
ba
amin ba c
ba c bo n
h p cha t amoni
Phn loai:
Ty theo dc dim gc R ta c amin tuong ung, nhu amin bo no, amin bo
chua no, amin thom, amin vng no, ...
10.2-Tn gi:
Cng thuc Tn thng thuong
CH
3
NH
2
metylamin
CH
3
NHCH
3
dimetylamin
(CH
3
)
3
N trimetylamin
CH
3
CH
2
NH
2
etylamin
(CH
3
CH
5
)
2
NH dietylamim
(CH
3
CH
5
)
3
N trietylamim
CH
3
CHCH
2
NH
2
n-propylamin
(CH
3
CH
2
CH
2
)
2
NH di-n-propylamin
(CH
3
CH
2
CH
2
)
3
N tri-n-propylamin
(CH
3
)
2
CHNH
2
isopropylamin
CH
3
CH
2
CH
2
CH
2
NH
2
n-butylamin
(CH
3
)
2
CH
2
CH
2
NH
2
isobutylamin
CH
3
CH
2
CH
2
(CH
3
)NH
2
sec-butylamin
(CH
2
)
3
CNH
2
tert-butylamin
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 71
C
6
H
11
NH
2
xiclohexylamin
C
6
H
5
CH
2
NH
2
benzylamin
CH
3
(C
6
H
5
)CHNH
2
-phenyletylamin
C
6
H
5
CH
2
CH
2
NH
2
-phenyletylamin
H
2
NCH
2
CH
2
NH
2
etylendiamin
H
2
NCH
2
CH
2
CH
2
NH
2
trimetylendiamin
H
2
N(CH
2
)
4
NH
2
tetrametylendiamin
H
2
N(CH
2
)
6
NH
2
hexametylendiamin
C
6
H
5
NH
2
anilin
C
6
H
5
NHCH
3
metylanilin
(C
6
H
5
)
2
NH diphenylamin
(C
6
H
5
)
3
N triphenylamin
o-H
3
C-C
6
H
4
NH
2
o-toludin
p-H
3
C-C
6
H
4
NH
2
p-toludin
m-H
3
C-C
6
H
4
NH
2
m-toludin
o-CH
3
OC
6
H
4
NH
2
o-anisidin
p-CH
3
OC
6
H
4
NH
2
p-anisidin
m-CH
3
OC
6
H
4
NH
2
m-anisidin
o-BrC
6
H
4
NH
2
o-bromanilin
p-BrC
6
H
4
NH
2
p-bromanilin
m-BrC
6
H
4
NH
2
m-bromanilin
o-O
2
NC
6
H
4
NH
2
o-nitroanilin
p-O
2
NC
6
H
4
NH
2
p-nitroanilin
m-O
2
NC
6
H
4
NH
2
m-nitroanilin
2,4-(O
2
N)
2
C
6
H
3
NH
2
2,4-dinitroanilin
2,4,6-(O
2
N)
3
C
6
H
2
NH
2
2,4,6-trinitroanilin
o-C
6
H
4
(NH
2
)
2
o-phenylendiamin
m-C
6
H
4
(NH
2
)
2
m-phenylendiamin
p-C
6
H
4
(NH
2
)
2
p-phenylendiamin
m-HOC
6
H
4
COOH axit m-hidroxibenzoic
o-H
2
N-C
6
H
4
COOH
axit anthranilic
(axit o-aminobenzoic)
p-H
2
N-C
6
H
4
COOH axit p-aminobenzoic
m-H
2
N-C
6
H
4
COOH axit m-aminobenzoic
p-H
2
N-C
6
H
4
SO
3
H axit sunfanilic
p-H
2
N-C
6
H
4
SO
2
NH
2
sunfanilamit
C
6
H
5
NHCOCH
3
axetanilit
C
6
H
5
NHCO C
6
H
5
benzanilit
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 72
o-CH
3
C
6
H
4
NHCOCH
3
axeto-o-toludin
m-CH
3
C
6
H
4
NHCOCH
3
axeto-m-toludin
p-CH
3
C
6
H
4
NHCOCH
3
axeto-p-toludin
o-O
2
NC
6
H
4
NHCOCH
3
o-nitroaxetanilt
m-O
2
NC
6
H
4
NHCOCH
3
m-nitroaxetanilt
p-O
2
NC
6
H
4
NHCOCH
3
p-nitroaxetanilt
Tn goi thng thuong:
Tn gc hidrocabon (theo vn A, B, C) + amin
Th du :
CH
3
-NH
2
CH
3
-NH-CH
3
CH
3
-N-CH
3
CH
3
H
2
N-CH
2
-CH
2
-NH
2
metylamin dimetylamin trimetylamin etylendiamin
CH
3
-N-CHCH
2
CH
3
CH
3
sec-butyldimetyllamin
CH
3
CH
2
-N-CH
3
H
etylmetylamin ter t-butylamin
NH
2
CH
3
CH
3
-C-CH
3
CH
3
CH
3
N-CH
2
-CH
2
-CH
3
CH
3
CH
2
CH
2
CH
2
-
n-butylmetyl-n-propylamin sec-butyletylmetylamin
CH
3
CH
2
CHCH
3
N-CH
2
CH
3
CH
3

NH
2
anilin N-metylanilin
NHCH
3
N(CH
3
)
2
N,N-dimetylanilin -phenyletyamin
CH
3
CHNH
2
-phenyletyamin
CH
2
CH
2
NH
2
NH
2
NH
2
NH
2
CH
3
CH
3
CH
3
p-toluidin
m-toluidin o-toluidin
-naphtylamin
NH
2
N
triphenylamin diphenylamin
NH
NH
2
-naphtylamin

H
2
NCH
2
CH
2
CH
2
CH
2
CH
2
CH
2
NH
2
H
2
NCH
2
CH
2
CH
2
NH
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 73
hexametylendiamin trimetylendiamin
Tn goi quoc t IUPAC:
S thu tu + tn gc hidrocacbon (theo vn A, B, C) + tn ankan tuong ung
voi mach chnh + s thu tu (cua amin) + amin.
Th du :
CH
3
NH
2
CH
3
CH
2
NHCH
3
CH
3
NH(CH
3
)
2
metanamin N-metyletanamin N,N-dimetylmetanamin
CH
3
CH
2
NH
2
CH
3
CH
2
CH
2
NH
2
CH
3
CH
2
CH
2
CH
2
NH
2
etanamin propanamin butanamin
CH
3
N-CH
2
CH
3
CH
3
CH
2
CHCH
2
CH
3
N-etyl-N-metylpentan-3-amin 3-etyl-N-metylpentan-2-amin
CH
3
CH
2
CHCH
2
CH
3
CH-NH-CH
3
CH
3
H
2
N-CH
2
CH
2
CH
2
CH
2
-NH
2
butan-1,4-diamin pentan-1,4-diamin
H
2
N-CH-CH
2
CH
2
CH
2
-NH
2
CH
3
NH
2
H
2
N
xiclopentan-1,3-diamin
NH
2
H
2
N
benzen-1,3-diamin
H
2
N NH
2
naphtalen-2,7-diamin
Cc tn thuong duoc IUPAC luu dng:
anilin
NH
2
o-toluidin
CH
3
CH
3
m-toluidin
H
3
C
p-toluidin
NH
2
NH
2
NH
2
10.3-Diu ch:
-Ankyl ha NH
3
bng ankylhalogenua :
HX
+
RNH
2
[RNH
3
]X
NH
3
+
RX
RX
+
RNH
2
[R
2
NH
2
]X
R
2
NH
+
HX
HX
+
R
3
N
[R
3
NH]X
R
2
NH
+
RX
[R
4
N]X
R
3
N
+
RX
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 74
Th du:
NH
3
CH
3
Cl
CH
3
NH
2
(CH
3
)
2
NH (CH
3
)
3
N
amoniac metylamin dietylamin
trimetylamin
tetrametylamoniclorua
(CH
3
)
4
N
+
Cl
-
CH
3
Cl
CH
3
Cl CH
3
Cl
2CH
3
Cl
NH
3
CH
2
Cl
CH
2
NH
2
CH
2
N(CH
3
)
2
benzyl clorua
benzylamin benzyldimetylamin
* Phuong php ny thuong cho hn hop amin cc bc v mui amoni bc bn.
* Bng cch tha y di t i l mol cc cht dua vo hn hop phan ung ta c th
diu khin phan ung uu tin tao ra san phm no l chu yu:
nhu :
-Du NH
3
cho san phm amin bc 1 l chu yu, sau d l amin bc hai.
-Du RXcho san phm amin bc 3 v mui amoni bc bn.
* Vic tch ring cc san phm amin ra khoi hn hop phan ung nguoi ta dng
clorua a xit cua axit benzensunfonic: ClSO
2
C
6
H
5
(xem phn ha tnh s trnh
by sau).
Phuong php ny duoc su dung rng ri d diu ch cc N-ankyllanilin tu
anilin:
NH
2
+ CH
3
I
NHCH
3
anilin metylioua
N-metylanilin
+ HI
+ CH
3
I
NHCH
3
metylioua N-metylanilin
+ HI
N,N-dimetylanilin
N(CH
3
)
2
+ CH
3
I
N(CH
3
)
2
metylioua N-metylanilin phenyltrimetylamoniioua
N(CH
3
)
3
+
I
-
-Tc dung cua ruou voi NH
3
:
Cho hn hop hoi ruou + amoniac di qua xc tc Al
2
O
3
(Th
2
O
3
) dun nng
o nhit d cao s cho amin cc bc:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 75
NH
3
+
ROH
RNH
2
+
H
2
O
t
0
xt
xt
0
t
H
2
O
+
R
2
NH
ROH
+ RNH
2
xt
0
t
H
2
O
+ R
3
N
ROH
+
R
2
NH
Th du:
trimetylamin
dietylamin
metylamin
amoniac
o
450 C
Al
2
O
3
CH
3
OH
(CH
3
)
3
N
(CH
3
)
2
NH
CH
3
OH
Al
2
O
3
450 C
o
CH
3
NH
2
o
450 C
Al
2
O
3
CH
3
OH
NH
3
Khi dng dn xut halogen thom d aryl ha NH
3
thuong phai tin hnh
phan ung o nhit d cao v p sut cao.
Th du:
+ NH
4
Cl
o
300 atm
340 C
NH
2
anilin phenyl clorua amoniac
Cl
+ 2NH
3
Nhung nu nguyn tu halogen duoc hoat ha boi nhm th ht electron bng
hiu ung -C o vi tr o- hoc p-th phan ung xay ra d dng hon nhiu.
Th du:
+ 2NH
3
Cl
p-nitroanilin
NH
2
200 C
o
NO
2
NO
2
+ NH
4
Cl
1-clo-4-nitrobenzen
+ 2NH
3
Cl
2,4-dinitroanilin
NH
2
20 C
o
NO
2
NO
2
1-clo-2,4-dinitrobenzen
+ NH
4
Cl
NO
2
NO
2
C
2
H
5
OH
-i tu phtalimit + RX :
Phan ung ny duoc su dung d diu ch ra amin bc mt:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 76
_
N
axit phtalic
ankyl phtalimit kali phtalimit phtalimit
RNH
2
+
H
2
O
COOH
COOH
RI
C
C
O
O
NR
C
C
O
O
NK
KOH
C
C
O
O
NH
-Tu amit diu ch amin bac 1 (Phan ung thai phn Hofmann):
Phan ung ny duoc su dung d diu ch ra amin bc mt giam mt cacbon
so voi mach cacbon cua amit ban du:
RCONH
2
+ Br
2
+ 4NaOH RNH
2
+ Na
2
CO
3
+ 2NaBr + 2H
2
O
Qa trnh phan ung din ra theo nhu sau:
RCONHBr
NaOH
RCONH
2
R CO N +
Br
2
+
H
2
O
HBr NaBr
Na
2
CO
3
RNH
2
R CO N
R N=C=O
+
+ NaOH 2 c/v
izoxyanat
Th du:
C che phan ng Hofmann nh sau :
CH
3
CONH
2
+ Br
2
+ 4NaOH CH
3
NH
2
+ Na
2
CO
3
+ 2NaBr + 2H
2
O
Br
2
+ 2NaOH NaOBr + NaBr + H
2
O
NaOBr Na
+
+ OBr
-
1) CH
3
-C-NH
2
+ OBr
O
CH
3
-C-NHBr + OH
O
2) CH
3
-C-NHBr + OH
O
CH
3
-C-NBr + H
2
O
O
CH
3
-N=C=O 4) CH
3
-C-N:
O
3) CH
3
-C-NBr + H
2
O
O
CH
3
-C-N: + Br
O
5) CH
3
-N=C=O + 2OH CH
3
-NH
2
+ CO
3
2-
CH
3
(CH
2
)
4
CONH
2
+ Br
2
+ 4NaOH
CH
3
(CH
2
)
4
-NH
2
+ Na
2
CO
3
+ 2NaBr + 2H
2
O
C
6
H
5
CONH
2
+ Br
2
+ 4NaOH C
6
H
5
-NH
2
+ Na
2
CO
3
+ 2NaBr + 2H
2
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 77
-Khu dan xuat nitro:
Phuong php diu ch ra amin bc mt, dc bit l amin thom:
ArNO
2
+ 6[H] ArNH
2
+ 2H
2
O
Cht khu: Kim loai (Fe, Sn , Zn ) + HCl ; H
2
S ; (NH
4
)
2
S, NH
4
SH...
Cht khu thuong dng ph bin nht l Fe + HCl:
ArNO
2
+ 3Fe + 6HCl ArNH
2
+ 3FeCl
2
+ 2H
2
O
Chi cn mt luong nho HCl: Khoang 1/40 luong HCl tnh theo phuong trnh
phan ung:
1) Fe + 2HCl FeCl
2
+ H
2

2) 2FeCl
2
+ [O] + H
2
O 2Fe(OH)Cl
2
3) 6Fe(OH)Cl
2
+ Fe + 2H
2
O 2Fe
3
O
4
+ FeCl
2
+ 10HCl.
HCl tao thnh giai doan 3 tip tuc phan ung giai phng hidro d khu hop
cht nitro.
C th vit phuong trnh phan ung tng qut chung:
4ArNO
2
+ 9Fe + 4H
2
O 4ArNH
2
+ 3Fe
3
O
4
.
Th du:
NO
2
+ 3(NH
4
)
2
S
+ 6NH
3
+ 3S + 2H
2
O
NH
2
Trong diu kin phng th nghim nguoi ta thuong khu hop cht nitro bng
thic v axit clohidric:
NO
2
+ 3Sn + 7HCl
+ 3SnCl
2
+ 2H
2
O
NH
3
+
Cl
-
Trong diu kin san xut, cung dng duoc phng th nghim nguoi ta
thuong khu hop cht nitro bng st v axit clohidric:
NH
3
+
Cl
-
+ 3FeCl
2
+ 2H
2
O
+ 3Fe + 7HCl
NO
2
Trong phuong php hin dai thun tin trong phng th nghim l dng
hidrazin voi cht xc tc l Ni:
NO
2
+ 3H
2
N-NH
2
+ 3N
2
+ 4H
2
O
NH
2
Ni
Theo phuong php ny c th thu duoc amin sinh ra m chi chung ct don
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 78
gian, chu khng phai chung cht li cun hoi nuoc nhu phuong php khu bng
Sn + HCl hoc Fe + HCl.
Di voi truong hop dinitro, ty theo cht khu ta s thu duoc nitroamin hay
diamin:
-Nu dng cht khu l Fe + HCl hay Sn + HCl th 2 nhm NO
3
bi khu dng
thoi.
-Nu dng cht khu l NH
4
HS hay (NH
4
)
2
S th 2 nhm NO
2
chi bi khu mt
nhm.
Th du:
NO
2
Sn + HCl
+ (NH
4
)
2
S
NH
2
NO
2
NO
2
NH
2
NH
2
m-dinitrobenzen
m-nitroanilin
m-phenylendiamin
3-nitro-4-metylanilin
2,4-dinitrotoluen
NH
2
NO
2
CH
3
+ NH
4
SH
CH
3
NO
2
NO
2
NO
2
NO
2
NHCH
3
+ NH
4
SH
NHCH
3
NH
2
NO
2
N-metyl-2,4-dinitroanilin 2-amino-4-nitro-N-metylanilin
-Khu mot so hop chat chua nito khc:
-Khu hop chat nitrin:
RCN + 4[H] RCH
2
NH
2
( Cht khu [H] : Sn + HCl ; H
2
/Ni ; Na + C
2
H
5
OH ; LiAlH
4
).
Th du:
C
6
H
5
CH
2
CN + 4[H]
ete ,
4
AlLiH
C
6
H
5
CH
2
CH
2
NH
2
CH
3
CH
2
CH
2
CN + 4[H]
ete ,
4
AlLiH
CH
3
CH
2
CH
2
CH
2
NH
2
C
6
H
5
CH
2
CN + 4[H]
6 2
H B
C
6
H
5
CH
2
CH
2
NH
2
CH
3
CH
2
CN + 2H
2

C t Ni
o
,
CH
3
CH
2
CH
2
NH
2
Cl(CH
2
)
4
Cl
NaCN
NC(CH
2
)
4
CN
C t Ni H
o
, ,
2
H
2
N(CH
2
)
6
NH
2
1,4-diclobutan adiponitrin hexametylendiamin
-Khu hop chat oxim:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 79
RCH=NH-OH + 4[H] RCH
2
NH
2
+ H
2
O
Cht khu : Na + C
2
H
5
OH ; H
2
/Ni ; LiAlH
4
.
(C
6
H
5
)
2
C=N-OH + 4[H]
ete ,
4
AlLiH
(C
6
H
5
)
2
CH-NH
2
N-OH
+ 2H
2
NH
2
Ni
90 C
o
-Khu izonitrin:
RNC + 4[H] RNHCH
3
Th du: CH
3
CH
2
NC + 4[H] CH
3
CH
2
NHCH
3
-Khu hop chat amit:
CH
3
(CH
2
)
10
CONH
2
+ 2H
2

C t xt
o
,
CH
3
(CH
2
)
10
CH
2
-NH
2
+ H
2
O
lauramit dodexylamin
N-etyl-N-metylanilin N-metylaxetanilit
AlLiH
4
N CH
2
CH
3
+ H
2
O
CH
3
O
CH
3
N C CH
3
+ 4[H]
-Khu - amoniac ha hop chat cacboyl:
>C=O + NH
3
+ H
2

C t Ni
o
,
>CH-NH
2
+ H
2
O
>C=O + RNH
2
+ H
2

C t Ni
o
,
>CH-NH-R + H
2
O
>C=O + R
2
NH + H
2

C t Ni
o
,
>CH-NR
2
+ H
2
O
Th du:
(CH
3
)
2
C=O + H
2
+ NH
3

C t Ni
o
,
(CH
3
)
2
CH-NH
2
+ H
2
O
axeton isopropyllamin
CH
3
CH
2
CH
2
CH=O + C
6
H
5
NH
2
+ H
2

C t Ni
o
,
C
6
H
5
NHCH
2
CH
2
CH
2
CH
3
+ H
2
O
N-n-butylanilin
CH
3
CH=O + (CH
3
)
2
NH + H
2

C t Ni
o
,
(CH
3
)
2
NCH
2
CH
3
+ H
2
O
andehit axetic dimetylamin etyldimetylamin
2HCH=O + 2HCOOH + C
6
H
5
CH
2
CH
2
NH
2

C
6
H
5
CH
2
CH
2
N(CH
3
)
2
+ 2CO
2
+ 2H
2
O
(CH
3
)
2
C=O + 2[H] + n-C
4
H
9
NH
2

6 2
H B
(CH
3
)
2
CH-NHC
4
H
9
+ H
2
O
axeton n-butylisopropylamin
Khi dun nng NH
4
Cl voi dung dich HCH=O ty theo ti l cc cht rong hn
hop phan ung v nhit d ta s duoc clohidrat cua:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 80
metylamin, dimetylamin, hay trimetylamin:
3HCHO + 2NH
4
Cl 2CH
3
NH
2
.HCl + CO
2
+ H
2
O
3HCHO + NH
4
Cl (CH
3
)
2
NH.HCl + CO
2
+ H
2
O
6HCHO + 2NH
4
Cl 2(CH
3
)
3
N.HCl + 3CO
2
+ H
2
O
Tm tt so d diu ch amin:
kho ng o i
ma ch C
ta ng 1C
gia m 1C
RCH
2
NH
2
H
2
, Ni
o
CuO, t C
HBr
o
H
2
, NH
3
, Ni, t C
RCH=O
RCH
2
NH
2
NH
3
RCH
2
CH
2
NH
2
RCH
2
CN
NaCN
RCH
2
Br
R-NH
2
OBr
-
R-C
NH
2
O
NH
3
R-C
Cl
O
SOCl
2
O
OH
R-C
KMnO
4
RCH
2
OH
10.4-Tnh cht vt l:
Metylamin, etylamin, trimetylamin l nhung cht kh, nhung amin thp l
nhung cht long, chng c mi ging mi amoniac, tan trong nuoc v tao dung
dich c tnh bazo. Khi khi luong phn tu tng th khi luong ring tng, nhit
d nng chay tng, t nh tan giam. Cc amin cao l cht rn o du kin thuong,
khng c mi v khng tan trong nuoc. Giua cc amin c lin kt hidro:
N-H N-, nhung yu hon lin kt hi dro giua cc phn tu ruou, song nhit
d si cua n tuong di cao v tan nhiu trong nuoc do tao lin kt hidro giua
amin voi nuoc.
10.5-Tnh cht ha hc:
10.5.1-D}c dim cu to v kha nng phan ng :
H
H
H
H
N
C
R
-Hai lin kt N-C v N-H du l lin kt cng ha tri phn cuc, nhung so
voi lin kt C-O v O-H th t phn cuc hon v d m din cua N (x
N
= 3,0) nho
hon d m din cua O (x
O
= 3,5).
-Nguyn tu nito cn cp e tu do v n tuong di tu do hon cp e tu do trong
oxi cua ruou v phenol, do d d dng nhn proton, nn c tnh bazo r rt.
-Trong amin bo R-NH
2
c mt d elect ron o N t ng ln nho R dy e bng
hiu ung +I cua gc R.
-Trong amin thom ArNH
2
, nhu trong anilin mt d electron o N giam do c
su ht e cua vng benzen bng hiu ung C, mt khc mt d e o nhn benzen
tng ln dc bit t ng nhiu o vi tr orth v para do c hiu ung +C cua nhm
NH
2
:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 81
NH
2

10.5.2-Ha tnh cua nhm amino:


-Tnh bazo:
RNH
2
HOH RNH
3
OH
+
+
(NH
3
HOH
NH
4
OH
+
+ )
Hng s phn li trong nuoc cua amin cung l hng s bazo duoc tnh bng
h thuc :
]
b
[RNH
2
]
[RNH
3
][OH
=
k
Hng s k
b
cng lon tnh bazo cng manh.
Amin c tnh bazo l do nguyn tu nito c cp e tu do c th kt hop voi
proton tao ra ion amoni tuong tu nhu amoniac:
N R
H
H
+
H
H
H
R N
H
H
N R
H
R
H
+
R
H
R N
H
N R
R
R
H
+
R
R
R N
Trong cc amin thng, cn cu vo hng s phn li cua chng, ta nhn thy:
Trong dung mi phn cuc, nhu nuoc chng han amin c tnh bazo lon hon
so voi amoiac, a min bc hai c tnh bazo lon hon amin bc mt, nhung amin
bc ba lai c tnh bazo nho hon amin bc hai :
13,1 9,42 4,75
4,20 3,38
3,23
b
pK
(CH
3
)
3
N C
6
H
5
NH
2
NH
3
(CH
3
)
2
N
CH
3
NH
2
(C
6
H
5
)
2
NH (C
6
H
5
)
3
N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 82
Su bin thin tnh bazo giua amin cc bc duoc giai thch nhu sau: Su tng
tnh bazo tu amoniac dn amin bc hai l do hiu ung cam ung +I cua cc gc
ankyl. Hi u ung ny lm tng mt d din tu chung quanh nguyn tu nito, v
do d lm tng kha nng kt hop voi prton cua nguyn tu nito, c nghia l tnh
bazo tng.
Cn su giam tnh bazo tu amin bc hai dn amin bc ba l do su giam nng
luong sonvat ha (hi drat ha) c ua c c ion amoni boi cc phn tu nuoc, kha
nng sonva t ha cua ion a moni giam lm cho d bn cua chng gi am v s u
phn li bazo cua amoni cung giam. Ngoi ra cung c th do trong amin bc ba
chua nhi u gc ankyl hon amin bc hai v bc mt, n ngu khng gian chung
quanh nito lon, lm giam kha nng cua nito kt hop voi prton:
R
R
N
H
H
+
H
2
O
H
N
R
R
+
OH
ion sonvat ho a
R
R
N
H
H
O
H
H
H
H
O
R
R
R
N
+ H
2
O N
R
R
R
H
+
OH
H
H
O
ion sonvat ho a
H
R
R
R
N
So snh d bn cua 2 ion:
H
H
O H
R
R
R
N
O
H
H
H
H
O
H
H
N
R
R
Nu tin hnh xc dinh luc bazo trong nhung dung mi khng c kha nng
sonvat ha nh u clobenzen chng han, th amin bc ba l ai c tnh bazo manh
hon amin bc hai.
Th du:
trong nuoc : (C
4
H
9
)
2
NH > C
4
H
9
NH
2
> (C
4
H
9
)
3
N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 83
trong clobenzen: (C
4
H
9
)
3
N > (C
4
H
9
)
2
NH > C
4
H
9
NH
2
Nu thay th cc hidro trong ankyl bng cc nhm th ht electron bng
hiu ung cam ung m -I th lm cho tnh bazo giam di r rt:
Cng thuc pK
b
CH
3
CH
2
CH
2
NH
2
3,37
CH
3
OCH
2
CH
2
NH
2
4,55
NC-CH
2
CH
2
NH
2
6,30
CH
2
=CH-CH
2
-NH
2
4,31
Nhung nhm th ht electron bng hiu ung -I hoc -C truc tip lin kt voi
nito c th lm cho tnh bazo cua nguyn tu nito gn nhu khng cn nua.
Th du:
F
3
C N CF
3
CF
3
CH
3
C NH
2
O
peflotrimetylamin axetamit
O
C NH
2
: benzamit
10
10
.
b
K
o
(trong n c, 25 C)
Ha ng so pha n li cu a mot so anilin the :
R
NH
2
R CH
3
H CH
3
O NH
2
NO
2
Cl
orth 2,5 4,2 3 3,2 0,00035 0,05
meta 4,9 4,2 2 7,6 0,032 0,3
para 12 4,2 15 110 0,001 1,5
Trong cc amin thom, tnh bazo cua amin thom ni chung du km xa so
voi cc amin thng. D l do hiu ung lin hop +C c ua nhm amino di voi
nhn benzen, mt d din tu o nguyn tu nito giam di nhiu v kha nng kt
hop voi prton tt nhin cung giam theo. Khi trong nhn benzen, o cc vi tr
meta v para, c mt cua nhm dy din tu lm tnh bazo tng ln; nguoc lai,
khi c mt cua nhm th ht din tu s lm tnh bazo giam di.
Trt tu tnh bazo giam dn trong mi truong hop:
NH
2
O
O
N
NH
2
C
H
H
H
NH
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 84
+C
+I
+I
CH
3
NH
2
CH
3
NH
2
CH
3
NH
2
NH
2
NH
2
NH
2
OCH
3
NH
2
OCH
3
NH
2
OCH
3
-I
-I
+C
NH
2
NH
2
Cl
NH
2
Cl
NH
2
Cl
-I
-I
+C
NH
2
NH
2
NO
2
NH
2
NO
2
NH
2
NO
2
-I
-I
-C
Cc amin thng c tnh bazo kh manh nn lm doi mu qi tm thnh
xanh v phenolphtal ein khng mu thmh mu h ong; tri l ai cc amin thom
khng lm doi mu qi tm v phenolphtalein.
Khi tc dung voi axit, cc amin tao thnh mui:
CH
3
NH
2
+
HCl
CH
3
NH
3
Cl
C
6
H
5
NH
3
Cl
HCl
+
C
6
H
5
NH
2
CH
3
NH
2
+
CH
3
COOH
CH
3
COONH
3
CH
3
C
6
H
5
NH
2
+
CH
3
COOH
CH
3
COONH
3
C
6
H
5
Cc mui clorua cua amin du khng tan trong ete, du hoa, benzen, cung
khng tan trong metanol, etanol. Axit axetic chi tao duoc voi amin nhung mui
t bn, nhung amin tao duoc mui bn voi axit oxalic. Mui cua cc amin khi
tc dung voi kim du giai phng ra amin tu do:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 85
NH
3
+
Cl
-
+ NaOH
NH
2
+ NaCl + H
2
O
[C
2
H
5
NH
3
]Cl
+
NaOH
C
2
H
5
NH
2
+ NaCl H
2
O +
Nhu vy cc amin l nhung bazo yu hon cc hidoxit kim. Tri lai, cc
hidroxit tetraankyl amoni [R
4
N]
+
OH
-
tao thnh tu cc mui amoni bc bn khi
tc dung voi AgOH, lai l nhung bazo manh, trong dung dich nuoc chng phn
li hon ton nhu NaOH v KOH.
-Su axyl ha nhm amino:
C th axyl ha amin bc 1, amin bc 2 bng halgennua axit, anhidrit cua
axit cacboxylic.
+ HCl
Ar-SO
2
N
H
R
O
R
H
N
R-C
ArSO
2
Cl
RCOCl
RNH
2
+ HCl
+ HCl
+ HCl
Ar-SO
2
N
R
R
O
R
R
N
R-C
ArSO
2
Cl
RCOCl
R
2
NH
R
3
N
RCOCl
ArSO
2
Cl
Kho ng pha n ng
Kho ng pha n ng
Th du:
C
6
H
5
SO
2
Cl
(CH
3
CO)
2
O
N
NH
2
C
H
CH
3
O
H
N O
2
S
Anilin
axetanilit
benzensunfonanilit
+ CH
3
COOH
+ HCl
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 86
piridin
+
Benzoyl clorua
Cl
C=O
Benzanilit
Anilin
O
H
C
NH
2
N
+ HCl
+ HCl
N
C
CH
3
C
2
H
5
O
H
piridin
C
2
H
5
NCH
3
N-etyl-N-metylbenzamit Etylmetylamin
COCl +
+ HCl
H
SO
2 C
2
H
5
NCH
3
dd NaOH
H
3
C
C
2
H
5
CH
3
N
N-etyl-N-metylp-toluensunfonamit
Etylmetylamin
SO
2
Cl +
CH
3
N NH
2
C
H
O
p-toludin
axeto-p-toludit
CH
3
-C-O-C-CH
3
+
H
3
C
CH
3
CH
2
COONa
H
3
C
O O
anhidrit taxetic
+ CHCOOH
o-tuludin
CH
3
CH
3
NH
2
+ CHCOOH
anhidrit taxetic
O O
CH
2
COONa
CH
3
+
CH
3
-C-O-C-CH
3
axeto-o-toludit
O
H
C N
C
2
H
5
NH
2
+ CH
3
COCl C
2
H
5
NHCOCH
3
etylamin axetyl clorua N-etylaxetamit
Etylmetylamin
N
CH
3
C
2
H
5
C
2
H
5
NCH
3
+ CH
3
CH
2
CH
2
COCl CH
3
CH
2
CH
2
C
H
O
N-etyl-N-metylbutaramit
butanoyl clorua
Khi dun nng cc amin bc nht, bc nh voi axit cacboxylic s xay ra phan
ung loai nuoc v tao ra cc dn xut axyl cua amin:
C
6
H
5
NH
2
+ CH
3
COOH C
6
H
5
NH-COCH
3
+ H
2
O
anilin axit axetic axetanilit
C
6
H
5
NH
2
+ HCOOH C
6
H
5
NH-CH=O + H
2
O
anilin axit fomic f omanilit
Axyl ha c th dng d tinh ch amin, ngoi ra cn duoc dng d bao v
nhm amin khng bi oxiha khi tc dung voi cc tc nhn oxiha manh, axyl
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 87
ha cn duoc dng d tch bit hn hop cc amin bc I, II, III nhu hn hop sau
phan ung RX v oi NH
3
. T t n ht l dng clorua c ua axit bezensunfonic
C
6
H
5
SO
2
Cl: Chi ami n bc I v b c II tha m gia ph an ung cn amin bc III
khng phan ung:
RNH
2
+ ClSO
2
C
6
H
5
RNHSO
2
C
6
H
5
+ HClR
2
NH + ClSO
2
C
6
H
5

R
2
NSO
2
C
6
H
5
+ HCl
Cc sunfamit thu duoc khng tan trong axit. Sunfamit cua amin bc I cn
nguyn tu H n i voi N c th th bng kim loai tao thnh mui [RN-
Na]SO
2
C
6
H
5
khi cho hn hop sunfa mit t c dung voi kim, mui ny tan trong
kim, nho d tch duoc amin bc II. Thuy phn sunfamit s thu duoc amin bc
I v II.
+ H
2
O
O
2
S N
Na
+ NaOH
H
N O
2
S
benzensunfonanilit
Thuy phn cc amit th:
+ NaOH
N C
CH
3
O
N-metylbenzanilit
t C
o
N-metylanilin
O
CH
3
C N H + NaO
natribenzoat
t C
o
NHCOCH
3
Br
+ H
2
O + HCl
Br
NH
3
+
Cl
-
+ CH
3
COH
p-bromaxetamit
p-bromanilin clorua axit axetic
-Tc dung voi axit nitro HNO
2
:
+Voi amin thng bc I s cho ruou:
C
2
H
5
NH
2
+ HNO
2
C
2
H
5
OH + N
2
+ H
2
O
San phm trung gian l mui diazoni, mui ny bi loai N
2
tao ra cacbocation,
ion ny bi thuy phn thnh ruou.
RNH
2
+
HONO
+
HX
[RN N]X + 2H
2
O
N]X [RN
R
+
N
2
+ X
R
+
H
2
O
ROH
+
H
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 88
C che p han ng : RNH
2
+ HNO
2
ROH + N
2
+ H
2
O
HCl H + Cl
H + H
2
O H
3
O
H-O-N=O + H
3
O H-O-N=O + H
2
O
H
H-O-N=O
H
NO + H
2
O
RNH
2
+ NO + H
2
O R-N-N=O + H
3
O
H
R-N=N-OH + H
3
O R-N N + 2H
2
O
R + H
2
O R-O-H
H
R-N-N=O
H
R-N=N-OH
R-O-H
H
+ H
2
O R-OH + H
3
O
R-N N
R + N
2
C che p han ng : CH
3
NH
2
+ HNO
2
CH
3
OH + N
2
+ H
2
O
H-O-N=O + H
3
O
H + H
2
O H
3
O
H-O-N=O + H
2
O
H
H-O-N=O
H
NO + H
2
O
CH
3
NH
2
+ NO + H
2
O CH
3
-N-N=O + H
3
O
H
CH
3
-N-N=O
H
CH
3
-N=N-OH
CH
3
-N=N-OH + H
3
O CH
3
-N N + 2H
2
O
CH
3
-N N
H
3
C + N
2
H
3
C
+ H
2
O
CH
3
-O-H
H
CH
3
-O-H
H
+ H
2
O CH
3
-OH + H
3
O
HCl H + Cl
Voi amin thom bc mt, o nhit d 0
o
- 5
o
C, s tao ra mui diazoni bn
vung duy tr duoc:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 89
o
C 5 - 0
H
2
O
2
+
N]Cl [C
6
H
5
N
HCl +
HONO
+
C
6
H
5
NH
2
anilin phenyldiazoni clorua
Dun nng dung dich ny s tao ra phenol v kh nito bay ra, tuong tu san
phm cui cng nhu truong hop amin thng:
HCl
+
N
2
+
t C
H
2
O +
N]Cl
[C
6
H
5
N
C
6
H
5
OH
o
+Voi amin thng v thom bc hai tc dung d dng voi HNO
2
cho nitrozomin:
imetyl ntrozamin
H
2
O + (CH
3
)
2
N NO HNO
2
+
(CH
3
)
2
NH
Nitrozamin d dng thuy phn trong mi truong axit v co ti tao amin ban
du; tc dung voi cht khu chuyn thnh dn xut hidzazin th 2 ln, nu l
cht khu manh s tao ra amin bc hai ban du v amoniac.
metylphenylamin metylphenylhirazin metylphenylnitrozamin
[H]
2 [H]
2
NH
3
+
CH
3
C
6
H
5
NH
CH
3
C
6
H
5
N NH
2
N NO
C
6
H
5
CH
3
Trong cc nitrozamin thom d xay ra su di chuyn nhm nitrozo tu nguyn
tu nito toi nhn, phan ung ny xay ra khi tc dung voi HCl lanh :
nitrozometylanilin p
ON
NHCH
3
H
CH
3
C
6
H
5
N NO
c/v
O nhit d thp axit nitro khng tc dung voi amin bc ba. Di voi amin
thom bc ba s tao ra dn xut th p-nirozo o nhn thom:
imetylanilin
H
2
O
+
NO
CH
3
CH
3
N
N
CH
3
CH
3
p
nitrozoimetylanilin
HONO
+
-Tc dung voi dan xuat co-magi:
R-NH
2
+ 2CH
3
-MgI R-N (MgI)
2
+ 2CH
4

Loi dung phan ung ny d phn bit cc bc amin dua vo th tch kh CH


4
.
-Phan ung tao cabilamin (hay izonitrin):
Khi cho amin bc I tc dung voi clorofom trong mi truong kim (dung dich
kim - ruou) s tao thnh cacbilamin hay izonitrin:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 90
+
HCl 3
+
C N R
KOH
Cl
H
C
Cl
Cl
H
H
N R
: co ng th c electron cu a pha n t izonitrin .
.
.
.
. .
.
.
.
.
C N R
Izonitrin l cht c mi tanh c m rt kh chiu, dc, nhn ra d dng, do d
phan ung ny dng d nhn bit amin bc mt; n bn trong mi truong kim,
nhung d bi thuy phn trong mi truong axit ti tao amin v axit fomic:
H
HCOOH +
H
2
O 2
+
C N R
H
H
N R
10.5.3-Ha tnh cua nhn thom di vi amin thom:
-Phan ung th: Tuong tu nhu nhm OH tr ong phenol, nhm NH
2
trong amin
thom, do c hiu ung lin hop duong +C, l m d dng cho vic th vo nhn
benzen v dinh huong cho cc nhm th moi vo cc vi tr orth v para.
-Tc dung voi halogen: Nhu tc dung voi nuoc brom voi anilin o ngay nhit
d thuong tao ra 2.4,6-tribromanilin o dang kt tua mu trng:
HBr 3
+
Br
Br Br
3 Br
2
+
NH
2
NH
2
Mun diu ch dn xut monobrom, monoclo th truoc ht cn axetyl ha
nhm amino, sau d halogen ha, cui cng thuy phn:
CH
3
COOH
bromanilin p
H
2
O +
Br
Br
NH
2
Br
2
NHCOCH
3
NHCOCH
3
+ (CH
3
CO)
2
O
NH
2
+
Tuong tu nhu trn di voi dn xut p-toluidin:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 91
Br
2
H
+
H
2
O
Br
2
(CH
3
CO)
2
O
NH
2
CH
3
Br
Br
CH
3
NHCOCH
3
NHCOCH
3
CH
3
Br
Br
NH
2
CH
3
CH
3
NH
2
-Tc dung voi axit nitric (Phan ung nitro ha):
Nhm amino l nhm th loai I (nhm th lin kt don). Khi nitro ha truc
tip anilin bng HNO
3
hoc hn hop HNO
3
+ H
2
SO
4
dc s thu duoc san phm
l o- v p-nitroanilin. So di nhu vy l v, mt mt cc nhm amin thom rt d
bi oxi h a boi tc dung cua HNO
3
s t ao ra cc san phm oxiha v cc san
phm ngung tu tip theo chng. Mt khc, tc dung cua axit manh voi cc amin
tao ra c c mui amoni, nhm amino chuyn thnh nhm amoni: H
3
N
+
-, R-
NH
2
+
-, R
2
NH
+
- l nhm th loai II nn dinh huong cho nhm th moi vo vi tr
mta-.
Th du:
+
NH
2
NO
2
NaOH
NO
2
HSO
4
H
2
SO
4
HNO
3
HSO
4
H
2
SO
4
NH
2
NH
3
NH
3
+
m
nitroanilin
Mun nitro ha anilin vo vi tr o- v p-, cn truoc ht ax yl ha nhm
amino, nh m axylamino s lm cho nhn benzen km hoat dng ha hon v
dinh huong nhm nitro vo vi tr p- , nu vi tr p- d bi chim th n th vo vi
tr o-
% %
8 92
+
NO
2
NO
2
C
0
5
-
0
3
H
2
SO
4
HNO
3
+
NH
2
+ (CH
3
CO)
2
O
NHCOCH
3
NHCOCH
3
NHCOCH
3
Thuy phn nitroaxetanilit bng axit hoc bng kim s thu duoc o- v p-
nitroanilin.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 92
p-nitroamnilin
+ CH
3
COONa
NO
2
NH
2
NHCOCH
3
NO
2
+ NaOH
o-nitroanilin
+ CH
3
COONa
NO
2
NH
2
NHCOCH
3
NO
2
+ NaOH
Mun diu ch m-nitroanilin ta phai khu m-dinitrobenzen
-Phan ung sunf ha :
NH
3
SO
3
c/v
anilin anilin sunfat
H
2
SO
4
NH
2
axit sufanilic
axit octanilit
axit sunfamic
c
100 C
0
0
190 - 180
SO
3
H NH NH
3
HSO
4
H
2
SO
4
SO
3
H
NH
2
SO
3
H
NH
2
H
2
O
180-190 C
o
o
Tuong tu anilin, -naphtylamin bi sunfo ha cho ta naphtionic:
NH
2
NH-SO
3
H
NH
3
HSO
4
o
H
2
O
SO
3
H
H
2
SO
4
t C
NH
2
H
2
SO
4
c/v
Khi sunfo ha bng mt luong du H
2
SO
4
dm dc hoc oleum, s xay ra
phan ung sufo ha tr uc tip vo vng benzen. Khi y nhm th -NH
2
o dang -
NH
3
+
dinh huong nhm sunfo vo vi tr meta-:
H
2
SO
4
NH
2
NH
3
H
2
SO
4
SO
3
H
NH
3
Trong diu kin nhu trn -naphtylamin tao ra 1 ,5 v 1,6
naphtalenaminosunfonic.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 93
Axit sunfanilic bt du c nghia quan trong trong y hoc tu nm 1934 khi
m nguoi ta pht hin thy rng nhiu amit cua n (cc sunfamit) c tnh khng
sinh cao duoc dng d tri bnh.
Th du:
SO
2
NH
2
H
2
N
streptoxit sunfaguanidin
H
2
N SO
2
NHC
NH
NH
2
sufadiazin
H
2
N SO
2
NH
N
N
-Phan ung khu :
p
,
o
t
NH
2
H
2
3 + NH
2
-Phan ung oxi ha : Cc amin thom bc mt r t nhay cam voi tc nhn oxi
ha. Phan ung oxi ha amin thom rt phuc tap, Tuy theo cht oxi ha v diu
kin tin hnh phan ung (mi truong axit, kim, tr ung tnh) c th tao ra nhiu
san phm oxi ha khc nhau.
10.5.4-Nhng amin tiu biu:
-Cc loai metylamin :
Ca ba du l cht kh, c mi tuong tu mi amoniac.
+Metylamin (CH
3
NH
2
): CH
3
NH
2
duoc dng trong tng hop huu co, th du tng
hop ra adrenalin, ephedrin:
CH
3
CHCH-NHCH
3
OH
Ephedrin Adrenalin
OH
CHCH
2
NHCH
3
HO
OH
Diu ch bng cch metyl ha NH
3
, ho c bng cch thai phn axetamit
(CH
3
CONH
2
) khi tc dung voi Br
2
trong dung dich NaOH dc:
CH
3
CONH
2
+ Br
2
+ 4NaOH CH
3
NH
2
+ Na
2
CO
3
+ 2NaBr + 2H
2
O
Hoc c th diu ch CH
3
NH
2
bng phuong php dc bit thuong dng l
cho amoniclorua tc dung voi fomalin:
3HCH=O + 2NH
4
Cl 2[CH
3
NH
3
]Cl + CO
2
+ H
2
O
Tnh cht ha hoc cua metylamin hon ton ging tnh cht ha hoc cua
amoniac NH
3
:
CH
3
NH
2
+ HCl CH
3
NH
3
Cl
Ta c th nhn bit metylamin nho phan ung ny: ly 2 dua thuy tinh, mt
dua t huy tinh nhng vo dung dich HCl dc, mt dua thuy tinh cn lai nhng
vo dung dich metylamin, dua h ai du dua th uy tinh lai gn, thy c khi
trng. Khi trng l nhung tinh th mui CH
3
NH
3
Cl duoc tao thnh nhung
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 94
tinh th nho liti.
Hoc c th nhn bit metylamin bng Phan ung t ao cabilamin (hay
izonitrin): Khi cho metylamin tc dung voi clorofom trong mi truong kim
(dung dich kim - ruou) s tao thnh cacbilamin hay izonitrin:
CH
3
N
H
H
Cl
Cl
C
H
Cl
KOH
CH
3
N C
+
3HCl
+
CH
3
N C
.
.
.
.
. .
.
.
.
.
co ng th c electron cu a pha n t izonitrin:
Izonitrin l cht c mi ta nh c m rt kh chiu, dc, nhn ra d dng, do d
phan ung ny dng d nhn bit d dng; n bn trong mi truong kim, nhung
d bi thuy phn trong mi truong axit ti metylamin v axit fomic:
N
H
H
N C
+
2 H
2
O
+ HCOOH
H
CH
3
CH
3
Metylamin lm kt tua cc mui kim loai:
2CH
3
NH
2
+ MgCl
2
+ 2H
2
O Mg(OH)
2
+ 2CH
3
NH
3
Cl
3CH
3
NH
2
+ Al
2
(SO
4
)
3
+ 3H
2
O 2Al(OH)
3
+ 3(CH
3
NH
3
)
2
SO
4
3CH
3
NH
2
+ Fe
2
(SO
4
)
3
+ 3H
2
O 2Fe(OH)
3
+ 3(CH
3
NH
3
)
2
SO
4
Metylamin tao phuc voi hidroxit cc kim loai dng (II), km, bac,...:
* Tc dung voi dung dich mui dng (II) clorua:
2CH
3
NH
2
+ CuCl
2
+ 2H
2
O Cu(OH)
2
+ 2CH
3
NH
3
Cl
Cu(OH)
2
+ 4CH
3
NH
2
[Cu(CH
3
NH
2
)
4
](OH)
2
Dung dich phuc [Cu(CH
3
NH
2
)
4
](OH)
2
c mu x anh thm ging nhu dung
dich phuc [Cu(NH
3
)
4
](OH)
2
.
* Tc dung voi dung dich mui km clorua:
2CH
3
NH
2
+ ZnCl
2
+ 2H
2
O Zn(OH)
2
+ 2CH
3
NH
3
Cl
Zn(OH)
2
+ 4CH
3
NH
2
[Zn(CH
3
NH
2
)
4
](OH)
2
Dung dich phuc [Zn(CH
3
NH
2
)
4
](OH)
2
khng mu g ing nhu phuc dung
dich phuc [Zn(NH
3
)
4
](OH)
2
* Tc dung voi dung dich mui bac nitrat:
CH
3
NH
2
+ AgNO
3
+ H
2
O AgOH + CH
3
NH
3
NO
3
2AgOH Ag
2
O + H
2
O
2CH
3
NH
2
+ Ag
2
O [Ag(CH
3
NH
2
)
2
](OH)
Dung dich phuc [Ag(CH
3
NH
2
)
2
](OH) khng mu ging nhu dung dich phuc
[Ag(NH
3
)
2
](OH).
+imetylamin {(CH
3
)
2
NH}: C cng voi metylamin trong nuoc mm v sinh ra
trong su thi rua c v cc pr otit. C th diu ch dimetylamin bng tc dung
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 95
cua metylamin voi amoniclorua: mui metylamoniclorua tc dung voi fomalin
s tao ra dimetylamoniclorua:
2 [CH
3
NH
3
]Cl + 3 HCH=O 2 [(CH
3
)
2
NH
2
]Cl + CO
2
+ H
2
O .
Nguoi ta cn dng phuong php khc l thuy phn p-nitrozodimetylanilin
trong mi truong kim:
ON-C
6
H
4
-N(CH
3
)
2
+ H
2
O ON-C
6
H
4
-OH + (CH
3
)
2
NH.
+Trimetylamin(CH
3
)
3
N: C tr ong nuoc mm, c mi gn ging amoniac,
nhung dung dich long c mi rt kh chiu nhu mi tanh, mi du c.
Diu ch bng cch metyl ha NH
3
khi cho metylamin (du) tc dung voi
NH
3
:
3CH
3
Cl
(du)
+ NH
3
(CH
3
)
3
N + 3HCl
Ngoi ra cung c th diu ch trimetylamin tu fomalin v amoniclorua:
9HCH=O + 3NH
4
Cl 2[(CH
3
)
3
NH]
+
Cl
-
+ 3CO
2
+ 3H
2
O
+Anilin (C
6
H
5
NH
2
): Anilin duoc diu ch ln du tin nm 1826 bng phuong
php chung ct khan chm voi vi sng (CaO).
Tnh cht vt l: L cht l ong khng mu, D
o
nc
=184
o
C, d lu ngoi khng kh
anilin s bi oxi ha t u tu, mu dn dn chuyn thnh mu vng, mu nu r i
mu den. Anilin t ta n trong nuoc, nhung tan v han trong ete, ruou, benzen.
Anilin d ba y hoi li cun cng voi hoi nuoc. N c mi hi kh chiu v r t
dc. Tinh ch anilin bng cch chung ct anilin voi bt km, anilin lai tro thnh
khng mu.
D pht hin (dinh tnh) anilin ta c th dng cc phan ung sau:
-Cho anilin phan ung voi clorua vi hoc nuoc javen tao ra dung dich mu
tm.
-Cho anilin tc dung voi vi giot dung dich hn hop H
2
SO
4
v K
2
Cr
2
O
7
long, tao ra dung dich xanh l cy hoc mu xanh thm.
-Cho anilin tc dung voi HNO
2
(t ao ra tu (NaNO
2
+ HCl) tao ra
phenyldiazoni clorua [C
6
H
5
NN]
+
Cl
-
(phan ung diazo ha) r i thuc hin phan
ung ghp voi -naphtol (trong kim) tao cht mu azo l -naphtol da cam - c
mu vng da cam sng.
-Cho anilin phan ung voi lignin cua g, tre, nua... c mt cua HCl, lm cho
mu vng xut hin trn g, tre, nua...
-Hoc cho anilin tc dung voi clorofom trong kim, tao thnh cacbilamin c
mi tanh ca m rt kh chiu.
Ung dung cua anilin: Lm nguyn liu ch phm nhum, lm cht xc tin luu
ha cao su, lm cht phan oxi ha, lm nhin liu tn lua, lm nguyn liu ch
duoc phm, dng diu ch plime nhu khi trng ngung anilin voi fomandehit
tao nhua anilin-fomandehit.
10.5.5-Mui v hiroxit tetra-ankylamoni:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 96
-Muoi teta-ankylamonihalogennua: Mui tetra-ankylamoni l cht kt tinh,
trung tnh, phn li manh trong nuoc.
Diu ch mui tetra-ankylamoniclorua:
RNH
2
+ 3RI + 2NaOH [R
4
N
+
]I
-
+ 2NaI + 2H
2
O
Th du:
CH
3
NH
2
+ 3CH
3
I + 2NaOH [(CH
3
)
4
N]
+
I
-
+ 2NaI + 2H
2
O
metylamin te tametylamoniiodua
-Hidroxit-tetraankylamoni: Hidroxit-tetraankylamoni o trang thi rn tuong
tu hidroxit kim loai kim.
Diu ch: Khi cho teta-ankylamoniiodua t c dung voi AgOH tao ra hidroxit-
tetraankylamoni:
[R
4
N]
+
I
-
+ AgOH [R
4
N]
+
OH
-
+ AgI
Th du:
[(CH
3
)
4
N]
+
I
-
+ AgOH [(CH
3
)
4
N]
+
OH
-
+ AgI
Tetraankylamoni hidroxit khng bn di voi tc dung nhit. Khi dun nng
tetrametylamoni hidroxit bi ph huy tao thnh tetrametylamin v ruou metylic:
o
CH
3
OH
+ (CH
3
)
3
N
OH
[(CH
3
)
4
N]
130-150 C
Nhung hidroxit tetraankylamoni trong d c gc R lon hon CH
3
, tuc l cc
nguyn tu H o vi tr di voi nguyn tu N, t h khi nhit ph n din ra s tao
thnh amin bc ba, anken v hoi nuoc:
Th du:

(CH
3
)
3
N + CH
2
=CH-R + H
2
O
o
130-150 C
CH
3
CH
3
CH
3
N CH
2
CH
2
R OH
Nho phan ung nhit phn hidroxit tetraankylamoni tao thnh anken, ta c
th xc dinh duoc cu tao cua amin no d chua r cu tao. Mun vy, ta cho
amin d tc dung voi CH
3
I du d tao thnh mui tetra-ankylamoni. Phn tch
luong CH
3
I tham gia phan ung c th suy r a bc cua amin. Nu l a min bc I,
n tip nhn 3 nhm CH
3
, amin bc II tip nhn 2 nhm CH
3
, cn amin bc III
chi c t h nhn 1 nhm CH
3
. Cho mui tetraankylamoni iodua t c dung voi
AgOH d chuyn thnh dang hidroxit. Nhit phn dang hidroxit d s thu duoc
mt t rong cc s an phm l a nken. X c dinh duoc c u t ao cua anken sinh ra
trong phan ung nhit ph n, s suy ra duoc cu tao cua gc ankyl trong amin
bc ban du v bi t duoc cu t ao cua a min. So d cc ph an ung din ra nhu
sau:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 97
RCH
2
CH
2
NH
2
+ 3CH
3
I
[RCH
2
CH
2
N(CH
3
)
3
]I
AgI +
AgOH +
[RCH
2
CH
2
N(CH
3
)
3
]I
[RCH
2
CH
2
N(CH
3
)
3
]OH
H
2
O + (CH
3
)
3
N
+
RCH=CH
2
o
t
[RCH
2
CH
2
N(CH
3
)
3
]OH
Nu mt ankyl khc c th tip nhn 2 phn tu CH
3
I v a nken sinh r a l
pentadien-1,4 th amin d phai l piperidin, khi y ta c so d phan ung:
H
2
O
o
120 C
CH
3
N
H
3
C H
3
C
N
CH
3
OH
AgOH
I
CH
3
2CH
3
I
N
H
3
C
piperidin
H
N
I
AgOH
OH
o
120 C
CH
3
N
H
3
C
CH
3
I
H
3
C
N
CH
3
CH
3
CH
3
CH
3
N
H
3
C
CH
3
CH
3
H
3
C
N
+
H
2
O
Cc nghin cuu trn duoc p dung d xc dinh cau tao cua nhiu ankaloit
tu nhin.
Co ch phan ung nhit phn tetraankylamoni v qui tc tch cua
Hopmann:
Phan ung nhit phn tetrankylamoni hidroxit tao ra anken v amin bc 3
thuc cht l phan ung tch hidro :
R C C R
R R
+
HNR
3 o
OH
t C
NR
3
H
R R
R C C R
Phan ung tch trn xay ra theo co ch E1 hoc co ch E2.
Th du phan ung tch theo co ch E1:
CH
3
C C CH
3
H
CH
3
H
CH
3
C C CH
3
H CH
3
H
NR
3
t C
OH
o NR
3
+
+ H
CH
3
C C CH
3
H
CH
3
H
CH
3
C C CH
3
H CH
3
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 98
Th du phan ung tch theo co ch E2:
+NR
3
H
2
O
H C C CH
2
CH
3
CH
3
H

HO
NR
3
H
CH
3
H
H C C CH
2
CH
3
H C C CH
2
CH
3
H CH
3
H
NR
3
t C
OH
o
...
Nu phan ung din ra theo co ch E1 huong tch cua phan ung s tun theo
qui tch Zaixep, ng hia l nhm
+
NR
3
bi tch cng voi nguyn tu -hidro o
cacbon bc ca o nht. Tri lai trong truong hop phan ung din ra theo co ch
tch E2 (truong hop ny ph bin hon ca), huong tch cua phan ung tun theo
qui tc Hopmann, nghia l nhm
+
NR
3
bi tch ra cng voi nguyn tu -hidro
o cacbon bc thp hon.
Th du:
o
OH
t C
N(CH
3
)
3
H
CH
3
H
H C C CH
2
CH
3
H
CH
3
H C C CH
2
CH
3
HN(CH
3
)
3
+
+HN(CH
3
)
3
H C C CHCH
3
CH
3
H
H
74%
26%
E2
D giai thch qui tc Hopmann ta c t h dua vo yu t khng gian. Ta
bit rng phan ung E2 xay ra t heo kiu trans, nghia l nhm X nhu nhm
+
NR
3
bi t ch ra c ng voi nguyn tu H o v i tr anti (tuc l k hc pha) di voi n.
Nhm
+
NR
3
c kch thuoc kh c ng knh. Nu phan ung xay ra theo qui tc
Zaixep th xut pht tu cu dang t bn cua hop cht amoni v di qua trang thi
chuyn tip km n dinh. Cn nu phan ung xay ra t heo qui tc Hopmann th
c th xut pht t u cu dang bn hon v di qua tr ang thi chuyn tip n dinh
hon .
Th du khi nhit phn:
OH
N(CH
3
)
3
(CH
3
)
2
CH-CH-CH
2
CH
3
Ta thy rng chi c mt cu dang o trang thi (I) l thch hop voi qui tc
Zaixep; cu dang (I) ny tuong di t bn v tr ang thi chuyn tip (Ia) tuong
ung cung vy, v c su dy ln nhau giua nhm
+
NR
3
v hai nhm CH
3
.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 99
H
H
H
3
C
CH
2
CH
3
CH
3
N(CH
3
)
3
N(CH
3
)
3
CH
3
CH
2
CH
3
H
3
C
H
H

HO
-
H CH
2
CH
3
CH
3
H
3
C
HOH +
+ N(CH
3
)
3
(I)
(Ia)
Trong khi d nu phan ung xay ra theo qui tc Hopman ta c cu dang (II)
v (III):
(II)
N(CH
3
)
3
H
CH(CH
3
)
2
H
3
C
H
H
H
H
H
CH(CH
3
)
2
CH
3
N(CH
3
)
3
(III)
Cu dang (II) bn hon cu dang (I) v trang thi chuyn tip (IIa) tuong ung
cung n dinh hon o trang thi chuyn tip (Ia):
(IIa)
(II)
+ N(CH
3
)
3
HOH +
H
3
C
H
CH(CH
3
)
3
H
-
HO

H
H
H
3
C
CH(CH
3
)
2
H
N(CH
3
)
3
N(CH
3
)
3
H
CH(CH
3
)
2
H
3
C
H
H
Ngoi cch giai thch trn nguoi ta cn giai thch qui tc Hopmann dua
vo hiu ung electron.
p dung qui tc Hopmann, cp di quang duoi dy khi thuc hin phan ung
nhit ph n tetrankylamoni hidroxit c ua chng tao ra s an phm c cu hnh
trans:
(1R,2R)-1,2-
iphenylpropan-1-amin
( 1S,2S)-1,2-
iphenylpropan-1-amin
C
6
H
5
H H
2
N
CH
3
H
C
6
H
5
C
6
H
5
NH
2
H
H CH
3
C
6
H
5
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 100
C
6
H
5
H H
2
N
CH
3
H
C
6
H
5
C
6
H
5 H
N(CH
3
)
3
CH
3
C
6
H
5
H
C
6
H
5
H I (CH
3
)
3
N
CH
3
H
C
6
H
5
CH
3
I d
C
6
H
5
H HO (CH
3
)
3
N
CH
3
H
C
6
H
5
AgOH t
o
C
H
2
O
(CH
3
)
3
N
C
C
C
6
H
5
CH
3
H
C
6
H
5
(1) (2) (3)
C
6
H
5
NH
2
H
H CH
3
C
6
H
5
H
C
6
H
5
N(CH
3
)
3
C
6
H
5
CH
3
H
C
6
H
5
N(CH
3
)
3
OH H
CH
3
H
C
6
H
5
CH
3
I d AgOH t
o
C
H
2
O
(CH
3
)
3
N
C
C
H
C
6
H
5
C
6
H
5
CH
3
(1) (2) (3)
C
6
H
5
N(CH
3
)
3
OH H
CH
3
H
C
6
H
5
Trans
Trans
Tuong t u, cp di quang cn lai cua 1,2-diphenylpropan-1-amin khi thuc
hin phan ung nhit phn tetrankylamoni hidroxit cua chng tao ra san phm c
cu hnh cis (Sinh vin tu vit qu trnh phan ung xay ra).
Qui tc Hopmann khng nhung p d ung cho phan ung E2 cua c c hop
cht a moni, m cn dng cho ca cc hop cht khc m nhm X cung c kch
thuoc lon, nhu
+
SR
2
, SO
2
R, OTs ,....
B-MUI DIAZNI
Cng thuc cu tao cua mui diazoni nhu sau :
X
] [
N N
Ar
trong d Ar l gc thom , X l gc axit v co.
Cation diazoni c th tn tai duoi cc dang cng thuc cu tao sau dy:
Ar
N N
[ ]
] [
N N
Ar
] [
N N
Ar
...
] [
N N
Ar
...
...
Cation diazoni thom bn vung hon cation dazoni thng R-N
2
+
l do su giai
toa din tch duong nho hiu ung lin hop giua nhm diazo voi nhn benzen:
N N
Tn goi mui diazoni: Tn nhn thom + diazoni + tn anion:
p-toluendiazoni bromua
benzendiazoni clorua
CH
3
N NBr N NCl
N NBF
4
O
2
N
p-nitrobezendiazoni floborat
p-nitrobezendiazoni nitrat
O
2
N N NNO
3
10.6-Diu ch:
Phuong php co ban d diu ch cht diazoni l diazo ha amin.
Amin thom trong dung dich axit du tc dung d dng voi HNO
2
t ao th nh
mui diazoni:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 101
o
H
2
O 2 +
Cl
tha p t
HCl
+
HNO
2
+ ArNH
2
Ar
N N
[ ]
0 - 5 C
o
Phan ung xay ra theo 2 giai doan :
HNO
2
2
cha m
N
2
O
3
+
H
2
O
NH Ar
ArNH
2
+
N
2
O
3
nhanh
NO + HNO
2
NO
Ar NH
Ar N=N OH
H
+
-H
2
O
Ar N N
ion diazoni
Th du:
o
0 - 5 C
]
[
N N
C
6
H
5
NH
2
+ HNO
2
+
HCl
t tha p
Cl
+2H
2
O
o
C
6
H
5
Co ch phan ung din ra qua cc giai doan sau :
H
2
O +
N=O N=O H
2
O
H
+
N=O HO
NH N=O
C
6
H
5
NH
2
+
H
3
O
N=O
N=O H
2
O
(hoa c )
C
6
H
5
C
6
H
5
N NH OH
H
2
O
H
N N
C
6
H
5
OH NH N
C
6
H
5
Phan ung diazo ha cn diu kin nht dinh: ha tan amin thom trong HCl
dc du vua d t ao mui voi amin vua d t c dung voi NaNO
2
t ao HNO
2
tc
nhn, nhi t d phan ung 0
o
5
o
C, phan ung trong 3 5 pht r i thu bng giy
tm KI - h tinh bt thy xut hin mu xanh l phan ung d hon thnh v axit
du d phan ung :
2HNO
2
+ 2KI + 2HCl 2KCl + I
2
+ 2NO + 2H
2
O
Nu trong nhn thom cua anilin c nhm th voi hiu ung C v I nhu
NO
2
, CN, ....tnh bazo cua amin giam, do d phan ung diazo ha tr o nn kh
khn hon (v giai doan quyt dinh tc d phan ung l nitrozo ha). Nguoc lai
cc nhm th th c hiu ung +C > I nhu OCH
3
, N(CH
3
)
2
,...lm tng tnh
bazo cua amin nn phan ung diazo ha d dng hon.
V l trn cc nitroanilin chi bi diazo ha trong axit sunfuric dm dc v c
khi phai dng nhung tc nhn nitrozo ha manh. Xt theo luc electrophin ta c
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 102
th sp xp cc tc nhn nitrozo ha theo thu tu:
NO
+
ClO
4
-
> HOSO
2
ONO > CF
3
COO-NO > H
2
O
+
-NO > Cl-NO >
ON-ONO > HO-NO > RONO
10.7-Tnh cht:
Tnh chat l h oc: Cc mui diazoni du ta n trong nuoc v p hn li hon ton
thnh cc cation diazoni v anion v co, khng tan trong ete cung nhu cc dung
mi huu co khc.
Tnh chat ha hoc:
10.7.1-Tc dng vi bazo:
Mui diazoni tc dung voi kim hoc voi AgOH tao thnh hdroxit diazoni:
AgCl +
[Ar N N]OH AgOH +
[Ar N N]Cl
Hidroxit diazoni l mt bazo manh tuong duong NaOH, KOH v c tnh
dn din. Tuy nhin, t nh bazo v tnh dn din giam di nhanh chng, d l do
su dng phn ha t u dang hidroxit diazoni thnh dang diazohidrat, cht ny c
tnh axit yu:
iazonihirat
H +
Ar N N O Ar N N OH
[Ar N N]OH
Khi tc dung voi kim, cn bng chuyn ha nhanh v pha phai tao ra mui
cua dazohidrat goi l diazotat :
natri iazotat
H
2
O + [Ar N N]ONa NaOH
+
[Ar N N]OH
Cc diazotat k im tn tai duoi 2 d ang dng phn lp th: syn-diazotat kim
(km bn) v antidazotat (bn vung hon) :
Ar N
NaO N
Ar N
N ONa
syn-iazotat
anti-diazotat
Nguoc lai khi tc dung voi axit v co du, cc diazotat s chuyn ha cc mui
diazoni qua dang diazohidrat:
+ +
HCl
Ar N N OH
HCl
Ar N N ONa
H
2
O
+ [Ar N N]Cl
10.7.2-Cc phan ng loi bo nhm nito:
Phan ung tng qut:
[Ar N N]Cl
Y
X
Ar Y + N
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 103
trong d Y: OH, OR, SH, SR, CN, Hal, NO
2
, HgCl, ....Th du:
[C
6
H
5
N N]Cl
+
H
2
O
C
6
H
5
OH
+
N
2
+
HCl
Nhung phan ung th d xay ra trong nhung diu kin m diu, diu d chu
yu l phan ung d giai phng ra kh N
2
rt tro v mt ha hoc.
V mt co ch, phn lon l phan ung th nucleophin, s t cn lai l phan
ung th gc tu do.
phan ung th nucleophin xay ra khi dun nng mui diazoni, sinh ra ca tion
phenyl C
6
H
5
+
cuc ky km bn v c kha nng phan ung rt cao, n chuyn ha
ngay th nh s an phm C
6
H
5
-Y, ph an ung ny thuc loai phan ung th
nucleophin don phn tu S
N
2:
N N
cha m
N
2
nhanh
+ Y
Y
Phan ung th theo co ch gc tu do thuong xay ra khi c mt dng ha tri
mt (Phan ung Xanmayo) hoc khi c mt Cu kim loai (phan ung Gattecman):
N N Cl + CuCl
+ N
2
+ CuCl
2
+ CuCl
2
Cl + CuCl
Trn dy l phan ung th theo co ch gc tu do, nhung khng phai l phan
ung dy truyn v n khng dn toi su hnh thnh gc tu do moi d bt du lai
phan ung. Giai doan thu nht l g iai doan chm, giai doan quyt dinh tc d
chung cua c a qa t rnh v nguoi ta d ch ung minh duoc rng v =
k[C
6
H
5
N
2
Cl][CuCl].
-Tao thnh phenol: Khi dun nng mui diazoni trong mi truong axit , s tao
thnh phenol:
[C
6
H
5
N N]Cl
+
H
2
O
C
6
H
5
OH
+
N
2
+
HCl
Tu nitrobenzen c th diu ch duoc m-bromphenol bng cc phan ung sau:
m-bromanilin
m-bromnitro-
Nitro-
NaNO
2
NH
2
NO
2
Sn
HCl
Fe
Br
2
NO
2
Br Br
HCl H
+
Br
N
2
+
Cl
-
H
2
O
Br
OH
m-bromphenol
-benzen -benzen
-Phan ung voi ruou :
+Phan ung voi ruou khan:
Mui diazoni tc dung voi ruou khan tao ra hidrocacbon thom v andehit:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 104
CH
3
CH=O
C
2
H
5
OH
HCl
+ N
2
+ C
6
H
6
+
+
[C
6
H
5
N N]Cl
Ap dung tnh cht ny d diu s mt s cht:
* Mun diu ch 2,4,6-tribrombenzen tu benzen ta t in hnh cc buoc nhu sau
:
HCl + NaNO
2
Br
2
3
[H]
6
H
2
SO
4
HNO
3
Br
Br Br
NH
2
NH
2
NO
2
Br
Br Br
N N
Cl
+ +
N
2
+ HCl
CH
3
CH=O
Br
Br Br
N N
Cl
Br
Br Br C
2
H
5
OH
khan
t
0
* Tu benzen ta c th diu ch duoc 1,4-dinitrobenzen theo cc buoc phan ung
nhu sau:
NO
2
HNO
3
H
2
SO
4
H
2
SO
4
HNO
3
NO
2
NO
2
NH
4
SH
(CH
3
O)
2
O
NH
2
NO
2
NO
2
NH
2
COCH
3
NH
2
COCH
3
NO
2
HNO
3
H
2
SO
4
NO
2
NH
2
COCH
3
NO
2
H
2
O, H
+
NO
2
NO
2
NH
2
HNO
2
HCl
0-5 C
o
N NCl
NO
2
NO
2
N NCl
NO
2
NO
2
+ C
2
H
5
OH
NO
2
NO
2
+ N
2
+ CH
3
CH=O + HCl
* Tu toluen c th diu ch m-bromtoluen bng cc buoc phan ung nhu sau:
CH
3
HNO
3
H
2
SO
4
HCl
Fe
CH
3
NO
2
NH
2
CH
3
NHCOCH
3
CH
3
Br
2
Toluen p-nitrotoluen p-toludin
axeto-p-toludin
(CH
3
CO)
2
O
CH
3
NHCOCH
3
Br
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 105
H
2
O
m-bromtoluen
Br
CH
3
Br
N
2
+
Cl
-
CH
3
CH
3
NH
2
Br
Br
NHCOCH
3
CH
3
H
+
H
2
O
NaNO
2
HCl
H
3
PO
2
3-brom-4-aminotoluen
* Tu p-nitroanilin c th diu ch duoc 1,2,3-tribrombenzen bng cc qa trnh
bin di sau:
-clorua
2,6-dibrom-4-nitro-
Br
Br
-nitrobenzen
3,4,5-tribrom-
Br
O
2
N
O
2
N
N
2
+
Cl
-
-benzendiazoni-
Br
Br
Br
Br
-anilin
2,6-dibrom-4-nitro-
NH
2
O
2
N O
2
N
NH
2
p-nitroanilin
NaNO
2 CuBr
Br
2
HCl
Sn
O
2
N
Br
3,4,5-tribrom-
-nitrobenzen
Br
Br Br
Br
-anilin
3,4,5-tribrom-
Br
H
2
N
HCl HCl
-
Cl
+
N
2
Br
3,4,5-tribrom-
-benzendiazoni
Br
Br
NaNO
2 H
2
O
Br
Br
-benzen
3,4,5-tribrom-
Br
H
3
PO
2
clorua
+ Phan ung voi ruou-nuoc (dung dich ruou):
Mui diazoni tc dung voi ruou-nuoc tao ete thom:
[C
6
H
5
N N]
+
Cl
-
+ C
2
H
5
OH C
6
H
5
-O-C
6
H
5
+ N
2
+ HCl
Phan ung tao thnh cc dan xuat halogen thom (p/u Sandmeyer):
[C
6
H
5
N N]
+
Cl
-
C
6
H
5
Cl + N
2
Cu
2
Cl
2
t C
o
[C
6
H
5
N N]
+
Cl
-
+ KI C
6
H
5
I + N
2
+ HCl
[C
6
H
5
N N]
+
BF
4
-
C
6
H
5
F + N
2
+ BF
3
t C
o
+ N
2
NH
2
CH
3
NaNO
2
HCl
N
2
+
Cl
-
CH
3
CuCl
Cl
CH
3
p-toludin p-toluendiazoni p-clotoluen
clorua
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 106
+ N
2
NH
2
CH
3
NaNO
2
H
2
SO
4
N
2
+
HSO
4
-
CH
3
CuBr
Br
CH
3
p-toludin
p-toluendiazoni-
p-bromtoluen
-hidrosunfat
-hidrosunfat
p-iottoluen
p-toluendiazoni-
p-toludin
CH
3
I
KI
CH
3
N
2
+
HSO
4
-
H
2
SO
4
NaNO
2
CH
3
NH
2
+ N
2
* Tu toluen c th diu ch cc dn xut th halogen cua toluen:
+ N
2
CH
3
HNO
3
H
2
SO
4
HCl
Fe
CH
3
NO
2
NH
2
CH
3
NaNO
2
HCl
N
2
+
Cl
-
CH
3
CuCl
Cl
CH
3
Toluen p-nitrotoluen p-toludin
p-toluen-
p-clotoluen
-diazoniclorua
-diazoniclorua
o-bromtoluen o-toluen-
o-toludin o-nitrotoluen Toluen
CuBr
HCl
NaNO
2
NO
2
CH
3
Fe
HCl
H
2
SO
4
HNO
3
CH
3
CH
3
NH
2
CH
3
N
2
+
X
-
CH
3
Br
-Phan ung tao thnh dan xuat xian v sunfoxian :
Cu
2
(CN)
2
CN
[ N N]BF
4
+ KCN
+ N
2
+ KBF
4
CH
3
HNO
3
H
2
SO
4
HCl
Fe
CH
3
NO
2
NH
2
CH
3
NaNO
2
HCl
N
2
+
Cl
-
CH
3
CuCN
C N
CH
3
H
2
O
H
+
COOH
CH
3
axit p-toluic Toluen p-nitrotoluen p-toludin
p-toluen-
p-tolunitrin
-diazoniclorua
+ N
2
+ KCl
N N]Cl + KSCN [
Cu
2
(SCN)
2
SCN
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 107
-Phan ung th nhm diazo bng goc thom :
+ N
2
+ KCl
N N]Cl + [
-Th nhm diazoni bng goc halogen kim loai ha tri hai :
+ N
2
+ CuCl
2
N N]Cl + HgCl
2
+ Cu [ HgCl
10.7.3-Cc phan ung khng giai phng nito : Cht mu azo: Ar-N=N-Ar
/
O
2
N N=N
p-nitroazobenzen
azobenzen
N=N
N=N
4,4-dibroazobenzen 2-metyl-4-hidroxiazobenzen
N=N HO
Br
Br
1
2
3
4
5 6
6
5
4
3 2
1
CH
3
N=N
axit-(phenylazo)benzensunfonic
SO
3
H OH
p-(phenylazo)phenol
N=N
N(CH
3
)
2
p-(p-nitrophenylazo)-N,N-dimetylanilin
N=N O
2
N
-Phan ung ghp (p/u tip vi):
Mui diazoni l mt tc nhn electrophin v nhm diazo mang din tch
duong, do d c th tc dung voi cc hop cht thom c tnh cht nucleophin
tuong di cao (nhu amin, phe nol, n phtol....) v v oi cc cation cua axit C-H
(nhu axit malonic, este axetoaxetic....)
Th du:
+ N N=N
R
R R
R
N [ N N]Cl
Luc electrophin cua ion diazoni khng cao lm, v din tch duong o nguyn
tu nito bi giai toa mt phn do hiu ung C cua vng benzen.
Phan ung ghp giua ion diazoni v hop cht thom thuc cht l phan ung th
electrophi o nhn th om. Trong phan ung ny ion diazoni duoc goi l cau t u
diazo, amin (hoc phenol) goi l cau tu azo, cn san phm sinh r a c nhm -
N=N- l hop chat azo (cht mu azo). Ta c th m ta co ch phan ung ghp
qua th du sau dy:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 108
+ N N=N
CH
3
CH
3
CH
3
CH
3
N [ N N]Cl
ca u t diazoni ca u t azo h p cha t ma u azo
co ch phan ung th elctrophin Ar
E
:
N N]Cl [
N
CH
3
CH
3
CH
3
CH
3
N=N
N
+
H +
H
ph c
N
CH
3
CH
3
N=N
h p cha t azo ph c
H
+
N=N
CH
3
CH
3
N
+Tc dung voi amin thom bac mot, bac hai:
[ N N]Cl
p-(phenylazo)anilin
+
NH
2
N=N NH
2
NHCH
3
N=N NHCH
3
+
p-(phenylazo)-N-metylanilin
N N]Cl [
+Tc dung voi amin thom bac 3 v phenol :
p-(phenylazo)-N,N-dimetylanilin
+ N N=N
CH
3
CH
3
CH
3
CH
3
N [ N N]Cl
(ma u o trong axit, va ng trong baz)
metyl dacam
NaO
3
S N
CH
3
CH
3
CH
3
CH
3
N=N
N +
Na
+ -
O
3
S [ N N]Cl
N N]Cl
N
CH
3
CH
3
CH
3
CH
3
N=N N +
p-(p-nitrophenylazo)-N,N-dimetylanilin
O
2
N O
2
N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 109
[ N N]Cl
p-(phenylazo)phenol
+
OH N=N OH
p-hidroxiazobenzen
benzendiazoni clorua phenol
CH
3
N=N OH
+
N N]Cl [ H
3
C
OH
-naphtol
N N]Cl [
N=N
+
HO HO
NaOH
+ HCl
phenylazo- -naphtol
4-(phenylazo)-1-naphtol
+ HCl
NaOH
OH
+
N=N
[ N N]Cl
OH
1-naphtol
-naphtol
N N]Cl [
N=N
+
HO
HO
NaOH
+ HCl
-naphtol dacam
Na
+ -
O
3
S
[NaO
3
S
O
2
N

-naphtol
[
N=N
+
HO HO
+ HCl

O
2
N
-(p-nitrophenylazo)- -naphtol
N N]Cl

* Diu ch thuc thu Cng g do:


NH NH
Zn, NaOH
2 NO
2
(hidrazobenzen)
Chuyn vi bezilidic thuc chuyn vi ni phn tu:
c/v
H
+
H
2
N NH
2
(benzidin) NH NH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 110
HNO
2
NH
2
H
2
N
HCl
Cl
-+
[N N
N N]
+
Cl
-
Cl
-+
[N N N N]
+
Cl
-
SO
3
H
NH
2
NH
2
SO
3
H
+ +
axit naphthionic axit naphthionic
SO
3
H
NH
2
NH
2
SO
3
H
N=N N=N
Co ng go o
(ma u xanh trong axit, o trong baz)
Trong cc phan ung trn, cation diazoni tn cng vo vi tr para, nhung nu
vi tr para d c nhm th ri t h n s th vo vi t orth . Phan ung ghp thuc
chat l phan ung th electrophin vo nhn thom, nhung cation diazoni l mt
tc nhn yu, nn chi tn cng vo nhn thom tuong di giu mt d electron,
d l nhung nhn thom d c nh m th hoat ha nhn thom l c c nhm th
lin kt don, tuc l nhung nhm th loai I-l nhung nhm th dy electron manh
nhu nhm amino -NH
2
, nhm hidroxil -OH trong phenol,... Mi truong thch
hop cho phan ung ghp voi amin l mi truong axit, voi phenol l bazo yu.
Phan ung ghp duoc su dung d tng hop ra ch t mu az lm co so cho cng
nghip pham nhuom. Cuong d mu cua cht mu azo phu thuc vo muc d
lin hop trong phn tu.
Su phu thuc vo mi truong phan ung qua cc th du sau:
pH=8
pH=6
diimetylaminophenol
N=N
N=N
N(CH
3
)
2
OH
N(CH
3
)
2
OH
ClN N
N NCl
OH
N(CH
3
)
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 111
H
2
N
Axit H
HSO
3
HSO
3 SO
3
H
H
2
N
SO
3
H
OH
HSO
3
SO
3
H
pH=8-10
pH=5-7
N=N
N=N
OH
OH
ClN N N NCl
H
2
N
-Phan ung khu:
Khi khu hop cht diazoni ta s duoc cc hidrazin thom:
[ N N]Cl + 4H
2
NH-NH
2
+ HCl
phenylhirazin
Phenylhidrazin l nhung tinh th mong, nng chay 23
o
C; o 240
o
C d bi oxi
ha o ngoi khng kh ha nu lai; c tnh bazo; duoc su dung nghin cuu cc
andehit, xton, gluxit (tao thnh phenylhidrazon v ozazon).
Ar-N=N-Ar
Zn, NaOH
SnCl
2
, H
+
Ar-NH-NH-Ar
Ar-NH
2
+ Ar-NH
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 112
o
C
6
H
5
N N X
H
2
O, t C
o
C
6
H
5
OH
ROH
C
6
H
5
OR
ROH
C
6
H
6
KHS
C
6
H
5
SH
C
6
H
5
SCH
2
COOH
HSCH
2
COOH
X: BF
4
, t C
o
C
6
H
5
F
C
6
H
5
Cl
C
6
H
5
Br
C
6
H
5
I
C
6
H
5
CN
C
6
H
5
N
2
C
6
H
5
NO
2
C
6
H
5
HgX
C
6
H
5
C
6
H
5
C
6
H
5
CH=CHCN
HCl+CuCl (hoa c Cu)
pha n ng Xanmay
HBr+CuBr (hoa c Cu)
pha n ng Xanmay
KI, t C
CuCN (p/ Xanmay)
HNO
2
(Cu
2
O; Cu, X=BF
4
)
NaN
3
Hg hoa c X=ClHgCl
3
, Cu
C
6
H
6
, NaOH
CH
2
=CHCN (Cu )
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
ArH ArNO
2
ArNH
2
ArN
2
+
X
-
Ar-F
Ar-Cl
Ar-Br
Ar-I
Ar-CN
Ar-OH
Ar-H
Ar-COOH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 113
Chuong 11
HP CHT DJ VNG V ANKALOIT
A- HP CHT DJ VNG
11.1-Khi nim v phn loi:
-Khi ni m: Hop chat di vng l lo ai hop chat hu co c vng, trong vng
d ngoi cacbon ra cn ch ua mot hoc nhi u nguyn t u khc k hng phai l
cacbon v goi l di tu hay di to. Cc di to thuong gp l O, S, N.
-Phn loai: 2 loai: no v khng no
* Di vng no, vng b t quan trong:
O
etilensunfo etilenimin oxit etilen
S
CH
2
CH
2
NH
CH
2
CH
2
CH
2
CH
2
N
O
O
H
piperidin
ioxan tetrahirofuran
piroliin
thiophan
O
N
H
S
Ni chung tnh cht cua di vng no khng khc g nhung tnh cht cua cc
hop cht thng no tuong ung.
* Cc hop chat di vng chua no: c 3 loai: Di vng 5 canh ; Di vng 6 canh ;
Di vng ngung tu.
* Di vng 5 canh:
5
4
3
2
1
5
4
3
2
1
5
4
3
2
1
O S
N
H
Furan thiophen pirol
D vo ng ca nh mo t d to : 5
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 114
1
2
3 4
5
1
2
3 4
5
1
2
3
4
5
D vo ng ca nh hai d to : 5
thiazol pirazol imidazol o xazol
N
S
N
N
H
N
H
N
N
O
5
4
3
2
1
N
N
H
N
triazol
N
N
N
H
N
tetrazol
5 D vo ng ca nh ba d to tr le n:
* Di vng 6 canh:
H
5
4
3
2
1
piperidin
N
6
6
6
6
N
O
S
piridin
piran
thiopiran
D vo ng 6 ca nh mo t d to :
1
2
3
4
5
5
4
3
2
1
5
4
3
2
1
5
4
3
2
1
6
6
6
N
N
pirazin
D vo ng 6 ca nh hai d to :
5
4
3
2
1
5
4
3
2
1
oxazin
pirimidin
N
N
O
NH
* Di vng ngung tu:
1
2
3
4
5
6
7
8
7
6
5
4
3
2
1

S
(benzothiophen) (benzofuran)
cumaron
O
NH
Indol
(benzopirol) ( , -benzopiridin)
quinolin
N
1
2
3
4
5
6
7
7
6
5
4
3
2
1
N
isoquinolin
( , -benzopiridin)

1
2
3
4
5
6
7
8
7
6
5
4
3
2
1
N
N
N
N
purin
8
9
H
(a nh so ngoa i le )
1
2
3
4
5
6
7
8
quinazolin
N
N
N
N
N
N
pteridin
8
7
6
5
4
3
2
1
Mt s cht quan trong chua cc di vng:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 115
quinin
N
CH=CH
2
CH
2
CH
2
OH
CH
CH
3
O
N
(Thuo c cho ng so t re t)
N
N
N
N
N
N
N
N
Cu
o ng (II) phthalocianin
ph c ma u xanh
( Ca 2 cha t thuo c loa i ma tu y nguy hie m)
(Co trong ca y thuo c phie n)
CH
2
CH
2
AcO
AcO
he roin
mocphin
CH
3
N
CH
2
O
1
2
11
10
9
6
7
8
14
13
12
5
4
3
3
4
5
12
13
14
8
7
6
9
10
11
2
1
O
HO
CH
2
N
HO
CH
3
(Thuo c gia m au)
N
CH
3
O-C-CH-
CH
2
OH O
Atropin
(Thuo c te thuo c loa i ma tu y)
N
CH
3
O-C--
COOCH
3
O
Cocain
C
6
H
5
CH
2
C
O
N
H
N
S
H
H
O
COOH
H
CH
3
CH
3
Penicilin G
(Thuo c kha ng sinh)
N
N
S
N
H
3
C
CH
2
NH
3
Cl
CH
2
CH
2
OH
CH
3
Thiamin (Vitamin B
1
)
Cl
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 116
CH
3
(Ankaloit co trong ca y thuo c la )
Nicotin
N
N
Resepin (Thuo c gia m au)
H
OCH
3
OCH
3
OCH
3
O
O-C
H
OCH
3
H
O
CH
3
O-C
CH
3
O
H
H H
H
N
N
(ca 2 cha t na y ch a trong die p lu c to cu a ca y xanh)
Mg
clorophin a
CH=CH
2
H
3
C
CH
3
C
2
H
5
H
H
3
C
N
N
N
N
O
C
O
C
20
H
39
O
H
H
C
CH
3
O
O
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
O
CH
3
O
C
H
H
C
20
H
39
O
O
C
O
N
N
N
N
H
3
C
H
C
2
H
5
CH=O
H
3
C
CH=CH
2
clorophin b
Mg
11.2-Tnh cht thom cua d| vng chua no:
-Biu hin tnh thom:
Cc di vng chua no c tnh thom th hin o ch: bn voi tc nhn oxiha,
d tham gia phan ung th, kh tham gia phan ung cng:
thiophen
S
..
thiophan
S
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 117
-Khng bi oxiha boi KMnO
4
,
khng tao duoc cc sunfoxit v
sunfon .
-D bi oxi ha b oi KMnO
4
, ta o
thnh cc sunfoxit v sunfon :
sunfon sunfoxit
O
O
S
O
S
-Phan ung th d dng hon
benzen (p/u nitro ha, p/u
sunfonic ha, p/u halogen ha.
-Nguyn tu S c kha nng cng
thm 2 nguyn tu Br d tao thnh
dibromthiofon:
S
Br
Br
dibromthiofon
-Giai thch:
-Diu kin l mt hop cht thom:
Phai l h lin hop vng kn, phng v thoa mn voi cng thuc cua Hucken
(Huychken) = (4n + 2) electron ( trong d n = 0 , 1 , 2 , ... ) .
-Di voi benzen: Su tao thnh 6e lin hop vng kn - goi l luc tu thom.
-Di voi di vng cung giai thch nhu vy: cung tao thnh luc tu thom: trong
d 4e l cua C, cn 2e l 2e tu do cua di tu (di voi vng 5 canh 1 di t):
pirol thiofen Furan
S
H
H
H
H
..
.
.
.
.
.
.
.
.
..
H
H
H
H
O
.
.
.
.
..
H
H
H
H
N
H
(2e tu do + 4e = 6e
-Di voi vng 6 canh:
piridin :
H H
H
H
H
.
.
.
.
.
.
N
(5e cua C + 1e cua N = 6e)
-Di voi di vng 2 di t cung vy:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 118
H
O
N
S
N
S
N
H
H
H
H
H
.
.
.
.
.
.
.
.
.
.
.
.
.
.
oxazol
thiazol
.
.
O
N
;
Biu din cng thuc ging benzen :
piridin
pirol
H
N
O
furan
S
thiophen
N
Nhng d kin vat l moi:
-Nng luong lin kt: Nng luong lin hop:
cht benzen furan pirol thiophen pirydin
nng luong
(kcal/mol)
36 22 24 28 37
-D di lin kt:
. D di lin kt C-C trong cc di vng = 1,39 A
o
dn 1,4 A
o
. D di lin kt C-C trong ankan = 1,54 A
o
. D di lin kt C-C trong benzen = 1,40 A
o
. D di lin kt C=C trong anken = 1,34 A
o
. D di lin kt C-N trong pirol = 1,42 A
o
. D di lin kt C-N trong amin = 1,47 A
o
. D di lin kt C-C trong thiophen = 1,74 A
o
. D di lin kt C-C trong thioete = 1,82 A
o
11.3-Cc phuong php diu ch:
Mi mt loai di vng c mt phuong php diu ch ring, khng c phuong
php chung p dung cho d diu ch cho tt ca cc di vng. Sau dy chi gioi
thiu mt s phuong php diu ch ring.
11.3.1-Diu ch cc d| vng 5 cnh furan, pirol, thiophen:
pirol
H
N
O
S
thiofen
,
0
400
_ 0
0
450 400
NH
3
H
2
S/Al
2
O
3
H
2
O
NH
3
/Al
2
O
3
H
2
S
H
2
O
furan
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 119
-Tu n-butan diu ch thiophen:
CH
3
CH
2
CH
2
CH
3
+ S
0
S
+ H
2
S
560 C
n-butan
Thiophen
-Tu axetilen v andehit fomic diu ch pirol:
N
H
pirol
HC CH + HCH=O HOCH
2
C CCH
2
OH
Cu
2
Cl
2
1,4-butindiol
NH
3
, xt
-Tu pentosan diu ch furan:
furan
xt
CH=O
-3H
2
O
pentoz
pentosan
CH
2
OH
(CHOH)
3
CH=O
n
(C
5
H
8
O
4
)
H
2
O, H
+
furfural
400 C
O
O
0
11.3.2-Di t 1,4-ixeton d diu ch furan v pirol:
(2,5-hexadion hay 1,4-dixeton)
axetonylaxeton
O
CH
3
CH
3
CH
3
CH
3
H
N
H
2
O
_
+
NH
3
H
2
SO
4
, - dimetylfuran
dimetylpirol -
,
H
2
C CH
2
H
3
C C C CH
3
O
O
OH HO
C CH
3
H
3
C C
HC CH
11.3.3-Di t axetilen:
S
pirol
NH
o
H
2
+
qua o ng nung o
NH
3
+
+
qua o ng nung o :
t
N HC
N
400-500 C
Al
2
O
3
,
H
2
S
+
CH CH
thio phen
piriin
axe tilen
o
11.3.4-Chung ct nha than d:
Than d qua l cc nung o nhit d 1000
o
C tao thnh than cc v nhua than
d, dem chung ct nhua than d duoc thiofen, piridin v cc hop cht huu co
khc .
11.4-Tnh cht ha hc:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 120
11.4.1-Phan ng th:
-Phan ung halogen ha:
+ 4HI
tetraiotpirol
NH
I
+ 4I
2
pirol
NH
KOH
I I
I
NH
pirol
+ SO
2
Cl
2
Cl
NH
-clopirol
+ HCl + SO
2
cloruasunfuril
,
- diclothio phen
clothio phen -

thio phen
S
+
Cl
2
S
Cl
+ Cl
2
S
Cl
Cl
+ Cl
2
S
Cl
Cl
Cl
Cl
tetraclothiophen
o
3-brompiridin
300 C
Br
2
+
N
N
Br
+ HBr
-Phan ung nitro ha:
-Furan v pirol khng th nitro ha truc tip bng HNO
3
hoc hn hop H
2
SO
4
-
HNO
3
v chng ki axit, khi gp a xit ch ng ha n hua, m d ng axetylnitrat
CH
3
COONO
2
trong piridin:
piridin
+ CH
3
COOH

-nitrofuran
O
NO
2
+ CH
3
COONO
2
furan
O
NH
pirol
+ CH
3
COONO
2
NO
2 NH
-nitropirol
+ CH
3
COOH
piridin
-Thiophen bi nitro ha mt cch kh khn:
S t C
o
thiophen
+ HNO
3
(a c bo c kho i)
NO
2 S
-nitrothiophen

+ H
2
O
-Piridin cung tham gia phan ung nitro ha mt kh khn:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 121
piridin
N
N
+
HNO
3
NO
2
+
H
2
O
H
2
SO
4
_
nitropiridin
300 C
o
-Phan ung sunfoha:
-furan v pirol khng th sunfoha truc tip bng H
2
SO
4
dc duoc m dng san
phm cng cua anhidritsunfuric voi piridin:
+ C
6
H
5
N

axit -pirolsunfonic
NH
SO
3
H
+ C
6
H
5
N.SO
3
pirol
o
t C
NH
O
t C
o
furan
+ C
6
H
5
N.SO
3
SO
3
H
O
axit -furansunfonic

+ C
6
H
5
N
-thiophen c th sunfoha d dng, cn d hon ca khi sunfo ha benzen:

axit -thiophensunfonic
S
SO
3
H
+ H
2
SO
4
thiophen
o
t C
S
Loi dung tnh cht ny d tch benzen ra khoi hn hop voi thiophen: Hn
hop thiophen + benzen tc dung voi axit sunfuric dc thiophen s sunfoha
truoc tao thnh axit -thiophensunfonic, trong khi d benzen khng phan ung
tao lop mng o pha trn.
-Phan ung sunfo ha piridin:
o
axit 3-piridinsunfonic
350 C
H
2
SO
4
+
N
N
SO
3
H
+ H
2
O
-Phan ung axyl ha, diazo ha v phan ung fomyl ha:
+ CH
3
COOH

-axetylfuran
O
COCH
3
+ (CH
3
CO)
2
O
furan
O
0 C
o
(C
2
H
5
)
2
O:BF
3
+ HCl

-benzoylthiophen
S
COC
6
H
5
+ C
6
H
5
COCl
furan
S
SnCl
4
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 122
muo i diazoni
NH
pirol
+ C
6
H
5
N N
+
Cl
-
N=NC
6
H
5 NH
2-(phenylazo)pirol
+ HCl
+ 3KCl + 2H
2
O
2-pirolcacboxandehit
N
CH=O
+ CHCl
3
+ 3KOH
pirol
N
H
H
-Phan ung th nucleophin doi voi pridin:
N
N
+
NaOH
OH
400 C
hidroxipiridin
_
o
N
N
NH
2
NaNH
2
+

_
aminopiridin
o
130-150 C
o
2-aminopiridin
200 C
N
+ HBr
Br
+ NH
3
NH
2 N
2-brompiridin
o
4-aminopiridin
200 C
N
+ HCl
+ NH
3
NH
2
N
4-clopiridin
Cl
piridin
N
C
6
H
5
+ C
6
H
5
Li
+ LiH
N
200 C
2-phenylpiridin
o

-
+
piridin
N
NH
2
+ Na
+
NH
2
-
+ NaH
N
2-aminopiridin
11.4.2-Tnh bazo cua pirol v piridin:
-Piridin v pirol c tnh bazo rt yu, hng s phn li bazo (k
b
)
piridin
=
5,6.10
-10
, tr ong khi d (k
b
)
anilin
= 6, 27.10
-10
, cn (k
b
)
trimetylamin
= 5,5. 10
-5
, do d
tnh bazo cua pir idin cn yu hon tnh bazo cua anilin. Nguoi ta giai thch tnh
bazo cua piridin l do nhm N t rong vng c tr ang thi lai ha s p
2
chu khng
phai c di e tu do. Piridin c th t ao mui voi axit manh nhung mui ny rt
d bi thuy phn:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 123
sunfat axit piriin
HSO
4
H
N
N
H
2
SO
4
+
-Di voi pirol tnh bazo rt yu v cp e tu do cua N tham gia lin hop trong
h lin hop, do d cp e tu do ny khng duoc tu do nhu trong amin bo no,
nn lm giam kha nng kt hop voi proton, do d tnh bazo giam.
11.4.3-Tnh axit cua pirol:
-Pirol vua c tnh bazo yu vua th hin tnh axit yu, lin kt N-H trong
nhn pirol phn cuc manh, nn H linh dng c th thay th bng kim loai khi
tc dung voi K, Na, hoc KOH:
COR
R
t C cao
o
o
t C cao
+ ClCOR
+ IR
N
H
N
H
N
COR
N
R
N
K
H
N
KOH
(K;Na)
11.5-Nhng hp cht d| vng tiu biu:
11.5.1-furan:
-So do diu ch:
axit piro muxic
O
COOH
furan
o
O
CH
2
OH
(CHOH)
4
CH=O
HOOC
CH
CHOH
CH
COOH
OH
HO
HOCH
[O]
ca t
khan
275 C
galacto z
-Tnh chat:
L tnh: Furan l c ht l ong khng mu D
S
o
= 32
o
C, c mi ging clorofom,
khng tan trong nuoc, c tnh cht trung tnh.
Ha tnh: furan th hin tnh thom phn no tuong tu benzen. Trong phan
ung voi brm n khng cho phan ung cng vo ni di m cho phan ung th.
Tuy nhin furan khng bn voi tc dung cua axit. Furan cung c th cho phan
ung cng voi 4 nguyn tu hidr tao thnh tetrahidrfuran:
tetrahidrofuran
O
+ 2H
2
furan
o
t C
O
Ni
11.5.2-Furfural ( -fomil furan ):
-iu ch: Furfural duoc diu ch bng cch dun cm hoc tru voi H
2
SO
4
long, ri ct li cun hoi nuoc.
-Tnh chat:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 124
L tnh: l m t cht nhu du, khng mu, D
S
o
= 162
o
C, c mi ging mi
bnh m khi c luong nho, nhung luong lon c mi kh chiu kch thch mng
nhy, d ngoi khng kh n bi nu lai nhanh chng.
Ha tnh: Furfural rt ging cc andhit thom nhu benzandhit:
O
CH=O
xt
t C
o
furfural
+ [O]
COOH
O
axit piro muxic
furfural
o
t C
xt
CH=O
O
O
+
CO
Furfural dng trong cng nghip nhua cao phn tu thay th cho HCH=O
san xut cc chat deo t uong t u loai phenolfomandhit; n cn duoc su dung
lm dung mi trong tng hop huu co .v.v..
Phan ung trng ngung giua furfural v phenol:
nh a phenolfurfurandehit
phenol
+ (n + 1)H
2
O
n
OH OH
CH
O O
CH
OH
(n + 2)
+ (n + 1)
OH
O
CH=O
xt
t C
o
furfural
11.5.3-Benzfuran (hay cumaron):
O
cumaron
Cumaron thuc nhm di vng ngung tu c chua trong nhua than d, l cht
long nhu du, khng mu, D
S
o
= 174
o
C, c th cng mt phn tu Cl
2
hay Br
2
vo ni di, bn vung voi kim v NH
3
, nhung d bi oxi ha boi KMnO
4
, duoi
tc dung cua H
2
SO
4
n trng hop th nh nhua p aracumaron v tnh cht ny
duoc ung dung trong cng nghip cht deo.
11.5.4-Pirol:
Pirol c trong nhua than d v trong cht du thu duoc khi ct khan xuong
d loai ht m.
Pirol l cht du, khng mu, c mi ging mi clorofom, D
S
o
= 131
o
C, ha
nu khi d lu ngoi khng kh do bi oxi ha, it tan trong nuoc, d tan trong
ruou v trong ete.
Pirol th hin tnh thom dc trung, ngoi ra tham gia phan ung cng H
2
:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 125
2
[H]
2[H]
pirol piroli piroliin
NH
NH NH
Pirolidin c chua trong phn tu cht nicotin (l ancalit c chua trong cy
thuc l), chua tr ong hmglbin (hng huyt cu), c trong clorphin (sc t
trong cy xanh)....
N
N
N
N
N
N
N
N
Cu
o ng (II) phthalocianin
ph c ma u xanh
Mg
clorophin b
CH=CH
2
H
3
C
CH=O
C
2
H
5
H
H
3
C
N
N
N
N
O
C
O
C
20
H
39
O
H
H
C
CH
3
O
O
CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
O
CH
3
O
C
H
H
C
20
H
39
O
O
C
O
N
N
N
N
H
3
C
H
C
2
H
5
CH
3
H
3
C
CH=CH
2
clorophin a
Mg
11.5.5-Quinolin v isoquinolin:
Quinolin
10
9 N
1
2
3
4
5
6
7
8
Isoquinolin
10
9
N
1
2
3
4
5
6
7
8
Diu ch quinolin:
anilin
NH
2
+ C
6
H
5
NH
2
+ H
2
O
o
t C
H
2
SO
4
, FeSO
4
+ C
6
H
5
NO
2
CH
2
OH
CHOH
CH
2
OH
glixerin
+
N
Quinolin
Qa trnh phan ung xay ra gm cc buoc nhu sau:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 126
B
1
: glixerin tch nuoc tao thnh acrolein:
t C
0
CH
2
-CH-CH
2
OH OH OH
H
2
SO
4

CH
2
=CHCH=O + H
2
O
glixerin
acrolein
B
2
: Phan ung th nucleophin cua nhm amin:
-(phenylamino)propionandehit acrolein
anilin
H
C
CH
2
CH
2
O
NH
O
+
NH
2
CH
2
CH
C
H
B
3
: Phan ung th electrophin (ni phn tu) vo nhn benzen cua nhm
cacbonyl:
H
+
H
2
O
N
H
H
OH
N
H
+ H
+
NH
OH
CH
2
CH
2
C
H
H
C
CH
2
CH
2
O
NH
B
4
: Phan ung oxi ha boi nitrobenzen:
+ C
6
H
5
NO
2
H
N
H
+
N
+ C
6
H
5
NH
2
+ 2H
2
O
3 3
1,2-dihidroquinolin
quinolin
Diu ch dn xut cua isoquinolin:
N
+ H
2
CH
2
CH
2
NH
O=C
CH
3
P
2
O
5
, t C
o
CH
3
o
t C
CH
3
N
N-(2-phenyletyl)axetamit
1-metyl-2,3-dihidroisoquinolin
1-metylisoquinolin
Phan ung oxi ha quinolin, isoquinolin v cc dn xut cua chng:
Quinolin bi oxi ha boi dung dich KMnO
4
tao axit quinolinic. Trong phn
tu quinlin, vng benzen bi ph v, nhn piridin duoc bao ton, diu ny chung
minh rng nhn piridin bn hon nhn benzen:
o
t C
quinolin
axit qunolinic
(axit 2,3-piridindicacboxilic)
KMnO
4
+ 9[O]
+ 2CO
2
+ H
2
O
COOH
COOH
N
N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 127
Isoquinolin bi oxiha boi dung dich KMnO
4
tao ra h n hop ax it phta lic
(phu) v axit 3,4 piridindicacboxilic (chnh):
axit 3,4-piridindicacboxylic
(B)
N
N
N
(E)
(F)
N
COOH
COOH
o
t C
isoquinolin
KMnO
4
, OH
-
COOH
COOH
N
KMnO
4
OH
N
COOH
COOH
COOH
N
COOH
N
t C
o
quinolin
axit 2,3-piridindicacboxylic
o
t C
N
COOH
N
COOH
COOH
N
OH
KMnO
4
N
COOH
isoquinolin
axit 3,4-piridindicacboxylic
Cc dn xut cua quinolin v isoquinolin bi oxi ha boi selen oxit:
dioxan
N
CH=O
SeO
2
CH
3
N
dioxan
N
CH=O
SeO
2
CH
3
N
N
CH
3
SeO
2
CH=O
N
dioxan
Th du :
N
CH
3
SeO
2
CH=O
N
xylen
OH OH
dioxan N
CH=O
SeO
2
CH
3
N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 128
N
CH
3
COOH
N
OH OH
[O]
11.5.6-Dn xut 8-hiroxiquinlin:
Tnh cht ha hoc quan trong nht cua 8-hidroxiquinolin l c kha nng tao
phuc voi cc kim loai, do d duoc su dung rng ri trong ha hoc phn tch.
Trong phn tu 8-hidroxiquinolin c su tao thnh lin kt hidro ni phn tu
giua nguyn tu hidro cua nhm OH voi cp electron tu do cua nguyn tu nito:
10
9
H
N
O
1
2
3
4
5
6
7
8
Lin kt hidro ni phn tu cua 8-hidroxiquinolin.
Ta bit rng nhiu dn xut cua quinolin trong d c 8-hidroxiquinolin c
kha nng tao phuc voi mt s kim loai, A.K.Bapko cho rng nhung thuc thu
huu co c kha nng tao phuc selat trong cu tr c phn tu phai c t hop cua
nhm OH-phenol hay xtn v nguyn tu N. 8-hidroxiquinolin v dn xut cua
chng c h lin hop trung tm tao phuc:
C
C
N
O
H
..
H ny l co so tao ra hop cht ni phuc voi nhiu kim loai khc nhau. 8-
hidroxiquinolin tao phuc voi nhiu ion cua cc kim loai:
la ho a tr
: n
la kim loa i
:
M
n
2
M
n
M
2
n
+
N
O OH
N
Th du : tc dung voi MgCl
2
v FeCl
3
:
N
O H
M g C l
2
2 N a O H
N
N
O
O
M g
+
N a C l +
H
2
O
2
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 129
3
3 H
2
O +
N a O H
N
O H
F e C l
3
N
N
N
F e
O
O O
+ N a C l 3
Dung dich 8-hidroxiquinolin trong ruou etilic-nuoc tc dung voi dung dich
st III clorua (FeCl
3
) cho mu xanh.
Khi cho thm mui nhm clorua trong amoniac c chua mui cua axit
tactric v dung dich 8-hidroxiquinolin trong ruou etilic, s tao thnh cc hat kt
tua mu vng tuoi.
Ung dung cua 8-hidroxiquinolin tc dung voi mt s nguyn t (voi mi
nguyn t c pH x c dinh) tao thnh nhung mui ni phuc kh tan. C c mui
ni phuc ny duoc ung dung rng ri trong thuc t d tch, phn tch trong
luong, phn tch th tch (theo phuong php brom ha gin tip bng bromua,
bromat) cc nguyn t.
Trong dung dich axit axetic-axetat v voi cc diu kin khc nhau nguoi ta
dng 8-hidroxiquinolin d xc dinh Cu , Zn , Cd , Al , In , Ti , Zr , Nb , Bi ,
Mo , W , Mn , Fe , Co , Ni , v.v...
Phan ung ngung tu andol-croton ha tao ra cc xtn ,-khng no:
O
C
+
X
CH
3
HO
N
N
HO C
O
CH=CH
X
X
: p NO
2
,
m
_
NO
2
_
(
)
O=HC
X
N CH=O
OH
+ CH
3
C
O
X
O
C
OH
CH=CH
N
H
+
H
2
O
X : H OCH
3
,
_
CH
3
,
So d chuyn ha cua 8-hidrxiquinlin tao ra cc xtn ,-khng no :
HCl
HCl
-p + CH
3
COC
6
H
4
OCH
3
-p
+CH
3
COC
6
H
5
OH
N
CH=CHCOC
6
H
4
OCH
3
OH
N
CH=CHC
6
H
5
HCl
+CHCl
3
CH=O
N
OH
OH
N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 130
B-ANKALOIT
11.6.1-D|nh nghia:
Ankaloit l nhng hop chat hu co c c hua di vng nit o, c tnh baz o,
thuong gp o trong nhi u loi thuc vat v di khi cn tm th ay trong mot vi
dong vat.
c bit cua ankaloit l c tc dung hoat tnh sinh l cao doi voi co th
nguoi v dong vat, nhat l doi voi h than kin. Voi mt luong nho, c ankaloit
l cht dc gy cht nguoi, nhung n c khi lai l thn duoc tri bnh dc hiu.
11.6.2-Thnh phn nguyn t v cu to cua ankaloit:
-Thnh phn nguyn t cua ankaloit: C 3 loai ankaloit:
+ Loai chua 3 nguyn t : C, H, N.
+ Loai chua 4 nguyn t : C, H, N, O hoc C, H, N, S
+ Loai chua 5 nguyn t : C, H, N, O, S loai ny c dc tnh rt cao
trong cc loi nm dc.
-Cu tao cua ankaloit:
+ Cc ancaloit thuong c cu tao khc nhau, nhung ni chung du c chua
nhn di vng c nito nhu:
NH NH
N
pirol pirolidin piridin
NH
N
N
piperidin indol quinolin
N
N
CH
3
Th du:
nicotin
N
CH
3
O
CH
OH
CH
2
CH
2
CH=CH
2
N
quinin
,
+ Cc ankaloit trong cng mt cy hoc trong cng mt ho thuc vt thuong
c cng thuc cu tao gn ging nhau.
+ Cc ankaloit trong cy thuong kt hop voi cc axit nhu axit oxalic
(HOOC-COOH), axit tactr ic (HOOCCHOHCHOHCOOH), axit lactic
(CH
3
CHOHCOOH), ax it malic (HOOCCH
2
CHOHCOOH)... d tao thnh
dang mui.
+ Thnh phn cua cc ankaloit trong cy phu thuc nhiu vo tung vng,
kh hu, dia l, cc m a v c c nm. Ankaloit th uong chua t rong mt s b
phn nhu: l, hat, r, vo ...
11.6.3-Phuong php tch bit ankaloit t thc vt v dng vt:
Nghin b phn cy c chua ankaloit cho tc dung voi HCl (hoc H
2
SO
4
),
tao thnh mui c ua a nkaloit, t ch dung dich mui ra r i cho tc dung voi
NaOH (hoc Ca(OH)
2
ha y NH
3
), a nkaloit duoc tch ra d uoi dang tu do tan
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 131
trong nuoc, sau d dng dung mi thch hop d chit ankaloit, sau cng l ct
dui dung mi thu duoc ankaloit:
Nghie n bo pha n ca y co ch a ankaloit
+
HCl
hoac H
2
SO
4
muo i cu a ankaloit
NaOH
Ca(OH)
2
hay NH
3
ankaloit
chie t
dmo i ete
ankaloit trong dung mo i
ca t uo i dmo i
ankaloit
-Trong mt s truong hop: nghin b phn cua c y ri ch ha truc tip voi
kim, ri chit ly ankaloit tu do.
-Trong mt s truong hop khc c th tch ankaloit bng cc phan ung tao kt
tua hoc mui don gian khng tan ...
Trong cc truong hop tch trn thuong duoc hn hop cc ankaloit, vic tch
ring cc ankaloit khoi hn hop cua chng l vic kh khn, hin nay phuong
php sc k duoc coi l phuong php tt nht.
11.6.4-Tnh cht chung cua ankaloit:
-V trang thi: tn tai 2 dang: long v rn.
Ankaloit chua oxi thuong o trang thi rn; ankacloit khng chua oxi thuong
o trang thi long.
-Tnh tan: Cc ankaloit khng tan trong nuoc (tru nicotin & cnin), hu ht
tan trong dung mi huu co: nhu benzen, ete, clorofom, axeton ...
-Tnh bazo manh:
-Cc ankaloit thuong c tnh bazo manh c th lm xanh qu tm.
-Cc ankaloit c th tao mui voi cc axit.
-Mt s ankaloit lm lm kt tua Fe(OH)
3
, Al(OH)
3
trong dung dich.
-Mt s ankaloit c tnh bazo manh dy duoc cc bazo trung bnh ra khoi
mui cua chng.
-Tc dung cua nh sng:
Mt s ankaloit thuong khng bn o ngoi nh sng mt troi, tia tu ngoai;
c mt s bi thoi ha khi chiu tia nh sng c buoc sng nht dinh.
-Hoat tnh sinh l cao:
Cc ankaloit c tc dung vo h thn kinh rt manh v c tc dung l ha
di voi co th nguoi v dng vt. Con nguoi d s u dung cc ankaloit voi liu
luong nho d chua bnh hay giai kht nhu ca cao, c ph,....
Nhiu ankaloit l cht gy nghin cuc ky nguy him di voi con nguoi nhu
thuc phi n, heroin....chng l nhung cht ma tu cuc ky nguy him, cn phai
xa lnh chng.
Cc ankaloit c chua S thuong c dc tnh rt manh, nguoi ta thy cc
ankaloit ny trong cc loai nm dc.
11.6.5-Thuc thu cua ankaloit: C 2 loai thuc thu: c loai 2 loai thuc thu:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 132
loai tao kt tua, loai tao phuc mu.
-Loai tao kt tua t tan hoc khng tan: rt nhay, c th pht hin vt:
-HgCl
2
1/20 trong H
2
O hoc trong C
2
H
5
OH
-Tamin trong ruou - nuoc.
-Bi(NO
3
)
3
- KI
-BiI
3
, SbI
3
/ ete-ruou.
-Axit phophomolipdic, Axit silicotungstic.
-AuCl
3
10%, PtCl
3
10%; dung dich dm axit picric
-Triphamic (trinitrorezoxinol).
Cc dung dich ny c th kt tua duoc ankaloit c nng d 10
-3
dn 10
-1
(mt phn ngn 1
0
/
00
dn mt phn trm 1%).
-Cc cht tao phuc mu:
Cc loai sunfomolidic, sunfovanidat, sunfoseleno, sunfotitanic, sunfopara-
metyl-benzaldehit
11.6.6-Mt s ankaloit quan trng:
-Nicotin: CTPT: C
10
H
14
N
2
. Nicotin thuc ankaloit ho piridin, c CTCT:
piridin pirolidil) -

-
metyl
-
(N
_

CH
3
N
N
Trong cu tao gm 1 nhn piridin kt hop voi nhn N-metyl-pirolidin .
-Nicotin o trong cy thuc l duoi dang mui kt hop voi axit li monic, luong
nicotin trong thuc l l 3%.
-Nicotin l cht l ong nhu du, khng mu, si 247
o
C, n nu l ai nhanh chng
trong khng kh do bi oxi h a, n d bay hoi c mi thuc l, d tan trong
nuoc, dung dich c tnh bazo manh.
-Nicotin l mt ankaloit rt dc, chi c vi mg nhuc du, i mua, voi luong lon
hon n km hm hoat dng cua h thn kinh, lm ngung h hp, lm t lit hoat
dng cua tim, do d khng nn ht thuoc l.
Mt s kt qua diu tra cho thy nhung nguoi nghin thuc l du bi nm
phi, mt s dng k bi ung thu phi v dn dn tu vong.
-Nicotin cung rt dc voi cn trng, lm thuc tru su trong nng nghip -
khng gy nhim mi truong.
Mt s dn xut quan trong chua nhn piridin:
Piridoxin (Vitamin B
6
)
CH
2
OH
HO
CH
3
N
CH
2
OH
nicotinamit (Vitamin PP) Axit nicotinic
O
N
C-NH
2 COOH
N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 133
Axit nicotinic, nicotinamit l amit cua axitnicotinic chnh l vitamin PP c
tc dung chng si da, Piridoxin (Vitamin B
6
) :
-Quinin: CTPT: C
20
H
24
O
2
N
2
. Quinin l ankaloit ho quinolin v c CTCT:
N
CH
3
O
CH
OH
CH
2
CH
2
CH=CH
2
N
quinin
Quinin cng voi cc ancaloit khc chua trong vo cy quinquina thuong moc
o xu nhit doi. Thnh phn quinin trong vo cy chim 2-3%.
-L cht rn, nng chay 177
o
C, n c th kt tinh ngm 3 phn tu nuoc v nng
chay l 57
o
C, d tan trong ruou v ete, dung dich quinin c vi dng v c tnh
bazo.
Quinin dng trong y hoc duoi dang mui chohidrat hoc sunfat: l thu thuc
chng bnh st r t v h a st, n tc dung truc tip dn cc vi rtng st rt v
dit chng, voi liu luong lon m kh dc .
-Mocphin: C
17
H
19
O
2
N:
CH
3
HO
N
CH
2
HO
O
1
2
11
10
9
6
7
8
14
13
12
5
4
3
3
4
5
12
13
14
8
7
6
9
10
11
2
1
O
HO
CH
2
N
CH
3
O
CH
3
3
4
5
12
13
14
8
7
6
9
10
11
2
1
O
CH
2
N
CH
3
mocphin
co e in he roin
AcO
AcO
CH
2
CH
2
CH
2
Mocphin c chua trong cy thuc phin khoang 8-12% cng voi cc
ankaloit khc.
-L mt cht kt tinh, t
o
nc
=230
o
C ( dng thoi phn huy); t ta n trong nuoc, kt
tinh ngm 1 phn tu nuoc, t an trong kim v c nhm phnol; mocphin vua c
tnh bazo, vua c tnh axit yu (tnh lung tnh).
-L thu thuc c gi tri dng trong y hoc: lm giam dau, thuc ngu.
-Mocphin d gy nghin, nu lam dung l cht ma tu cuc ky nguy him.
-Gi tri qu ga cua mocphin l t c dung giam dau theo kiu tiu cam gic dau,
tc dung ln trung tm xc dinh cua bn cu no: su tc dung ln trung tm ny
l cuc k qu b u, v voi liu luong nho lm giam dau m khng lm xo trn
thuc. Ngay nhung liu luong rt nho cung duoc tc dung dn trung tm tho, tn
s tho bi giam xung, su ha thp cua nhip tho tuc khc duoc tng ln cho dn
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 134
khi ph bo cc con ho tuc khc. Nu luong mocphin lon s c hai, l m nguoi
cht qua t nh trang t lit tr ung tm tho. Su dung tri liu cua mocphin bi han
ch v tnh thch nghi v gy nghin nguy him.
Cn phai nhn manh quan trong l su nguy him cua chu nghia mocphin, su
biu hin dc hai mocphin kinh nin - tc dung khoan khoi khng gp o moi
nguoi. Yu cu v mocphin dn dn l s gam ngy cng tng nhiu ln - kt
qua ny dn cui cng cua ci cht l b nh ngu, giam trong luong co th, xut
hin cc nt do trn da v mt ht suc luc co th v suc luc tinh thn. Su chng
lai diu tri l tro nn kh khn hon v lu di hon.
Chung nghin o codein l r rng t hon, o dy loi th cho n trong liu
php duoc dua ra. Tc dung giam dau. Tc dung giam dau v tnh yn r rng
l t hon nhiu so voi mocphin. Codein c th tc dung kch thch (tnh b
dung) cua cc duoc liu khc duoc tng ln. Cung nhu tc dung chua ho cua
codein yu h on mocphin nhiu, nh ung n c nhiu ci tt hon nho tnh cht
khng bi quen dn v tnh khng bi nghin.
Mocphin duoc Axetyl ha voi anhidrit axetic tao thnh heroin.
-Atropin: CTPT: C
17
H
23
O
3
N v c CTCT:
Atropin
O CH
2
OH
CH
3
N
N CH
3 O C
O
CH
2
OH
CH
O-C-CH
-C chua trong cy Atropabelladonna-thuc ho c chua khoang 0,1-0,3%.
-N l mt este do su kt hop cua ancol tropin & axit D,L-tropic .
-L cht kt tinh nng chay o 115-117
o
C , c vi dng.
-L c ht dc manh nht, voi liu lon lm ngung ngay su h hp, t rong y hoc
dng luong nho d mo rng con nguoi mt, lm giam su tit m hi, nuoc bot,
lm thc gian dau, thuc ngu.
-Ccain: CTPT: C
17
H
21
O
4
N v c CTCT:
cocain
O
C O
CH
3
N
COOCH
3
O
COOCH
3
CH
3
N
O-C
-Ccain l ankaloit cua l cy coca moc o nam M (vng pru, xry).
-L cht kt t inh c tinh th hnh lng tru D
o
nc
=98
o
C, kh tan trong nuoc d tan
trong ruou, ete.
-N l t huoc t tung phn rt manh, l t huc gy m manh, song l thuc dc
gy mt nhoc, suy nhuoc co th, mt s truong hop c th thay th cocain bng
novocain mt thu thuc tng hop:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 135
C
2
H
5
C
2
H
5
N COOCH
2
CH
2
H
2
N
MT S DIEU CAN BIET VE VN DE MA TY
A-Ma ty l g ?
Ma ty l tn goi chung cua mot so thao moc (ankaloit), duoc chat m nu
lam dung s e gy nghin. Mot so loai ma ty thuong gp trn thi truong l:
Mocphin, Hrin, Ccain, thuoc phin, can sa, v.v.
a)c tnh cua ma ty: c tnh nguy hi m cua chat ma ty l k ha nng gy
nghin cho mot nguoi chi sau mot vi lan su dung. Mot khi d nghin th co
th cua nguoi nghi n c nhu cau duoc cung cap thuong xuyn chat ma ty,
khin cho nguoi d bi l thuoc vo chat ma ty.
b)Triu chung cua nguoi nghin ma ty (c 2 cap do):
-Nghin nhe: Thuong hay ngp, u oai, lu du, mt moi.
-Nghin nng: Co th vat v, dau nhuc, cam thay nhu c hng triu con gii
b trong xuong tuy.
-Nguoi bi nghin nu khng c thu oc se vat v, tr o nn hung d v sn sng
lm bat cu vic g d thoa mn con nghin.
c)Nguoi ta c th dng ma ty duoi cc dang: Ht, chch, uong hoc kt hop
vua uong vua chch.
d)Tc hai cua ma t y rat gh g om: Lm b ng hoai v dao duc, tiu tn ti
san, trom cp, cuop, gy n mang d c tin ht, chch v l nguyn nhn chu
vu cua cn bnh th kv HIV/ AIDS.
e)Nguoi nghin ma tu c trch nhim:
-Tu khai bo v t nh t rang nghi n ma ty cua mnh voi to chuc noi lm vic,
hoc tap hoc chnh quyn co so noi cu tr v tu dng k hnh thuc cai nghin.
-Tun thu nghim ngt cc qui dinh v cai ghin ma ty.
-Trong thoi gian cai nghin bt buoc th nguoi nghin ma ty phai:
+Tun thu n oi qui v chiu s u qu an l gio d uc c ua c o s o cai nghi n bt
buoc.
+Lao dong, hoc tap, cha bnh d cai nghin v gp phan dam bao doi song
trong thoi gian cai nghin.
-Cc hnh thuc cai nghin: C 3 hnh thuc: cai nghin tap trung tai trung tm
cai nghin; cai nghin tai gia dnh; cai nghin tai cong dong.
-Nguoi cai nghi n ma ty t u nguyn lm don xin cai nghi n th duoc nhan
vo cai nghin tai co so cai nghin bt buoc v khng coi l bi xu l vi pham
hnh chnh.
-Nguoi cai nghin ma t y tu 18 tuoi t ro ln d duoc cai nghin tai gia dnh,
cong dong hoc d duoc gio duc nhiu lan tai x, ph uong, thi tran m v an
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 136
cn nghin hoc khng c n oi cu tr nhat dinh phai duoc dua vo co so cai
nghin bt buoc.
Vic dua nguoi nghin ma ty vo co so cai nghin bt buoc duoc thuc hin
theo qui dinh cua chu t ich UBND huyn, quan voi thoi han t u 1 n m dn 2
nm.
-Nguoi nghi n ma ty t u du 12 tu oi dn duoi 18 tu oi d duoc cai nghi n tai
gia dnh, cong dong, d duoc gio duc nhiu lan tai x, phuong m van cn
nghin hoc khng c n oi cu tr nh at dinh hoc duoc gia dnh lm don xin
cai nghi n t h duoc nhan vo cai nghin tai co so cai nghin bt buoc dnh
ring cho ho v khng coi l vic xu l hnh chnh.
B-Gia dnh c ngui nghin ma ty c trch nhim:
-Bo co cho chnh quyn co so v nguoi nghin ma ty trong gia dnh mnh
v tnh trang nghin cua nguoi d.
-Gip nguoi nghi n ma ty c ai nghin tai gia dnh theo s u huong dan, gim
st cua cn bo y t v chnh quyn co so.
-Theo di, gim st, phng ngua, ngn chn nguoi nghin su dung tri php
chat ma ty hoc c hnh vi gy mat trat tu, an ton x hoi.
-Ho tr o c o quan c th am quy n dua ng uoi nghi n ma ty vo c o s o cai
nghin tap trung v dng gp kinh ph cai nghin theo qui dinh cua php luat.
C-Ma ty v cc qui d|nh cua php lut nuc ta lin quan dn ma
ty:
Qui dinh cua bo luat hnh su v toi pham ma ty:
-iu 194: Toi tng tr, van chuyn chat ma ty tri php ho c chim doat
chat ma ty: Phat t tu 2 nm dn tu hnh.
-iu 196: T oi s an xu at, tng tr, v an c huyn, mua bn cc phuong ti n,
dung cu dng vo vic san xuat hoc su dung chat ma ty tri php: Phat t
tu 1 nm dn 10 nm, phat tin tu 5 triu dn 500 triu dong.
-iu 198: T oi chua chap vi c su dung tr i php ch at ma ty: Phat t tu 2
nm dn 15 nm, phat tin tu 50 triu dn 200 triu dong.
-iu 199: Toi su dung tri php chat ma ty: Phat t tu 2 thng dn 5 nm.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 137
Chuong 12
GLUXIT
-Khi nim, phn loai v nghia cua gluxit :
-Gluxit c n goi l cacbonhidrat c cng thuc chung C
x
(H
2
O)
y
, l m t tr ong
nhung thnh phn co ban cua t bo v m trong co th sinh vt, nht l thuc
vt.
-Thnh phn cua gluxit trong co th dng thuc vt:
. Thuc vt: 70-89% (tnh theo trong luong kh): o trong cc b phn cua
thuc vt: cu , qua , l , thn , cnh.
. Dng vt: 2%: o trong gan , co , mu cua dng vt .
-Ngun gc gluxit: Gluxit duoc hnh thnh tu trong l xa nh cua thuc vt nho
qa trnh quang hop cua nh sng mt troi v cht sc t xanh clorophin :
2 5 10 6 2 2
2 5 10 6 2 6 12 6
2 6 12 6 2 2
6 ) (
,
6 6
6 ) ( 6
6
,
6 6
.
nO O H C
asmt
O nH nCO
nO O H C O nH O H C n
O O H C
asmt
O H CO
n
n
n
+ +

'

+ +
+ +
+
4 3 4 2 1
4 3 4 2 1 43 4 2 1
) (xenluloz bot Tinh
to luc diep
) (xenluloz bot Tinh Glucoz
to luc diep
(Phan ung tng qut:
xCO
2
+
2
y
H
2
O
to luc diep , asmt
C
x
(H
2
O)
y
+ (x-
4
y
)O
2
)
-Gluxit c vai tr cuc k quan trong di voi doi sng con nguoi: Cung cp nng
luong cho qa tr nh hoat dng (khoang 60%-70%) nhung lai khng tng hop
duoc m phai ly tu thuc vt: l ngun cung cp luong thuc, thuc phm.
-Gluxit c vai tr quan trong trong thuc t, tr ong cng nghip ha hoc: nhu l
nguyn liu lm nh ..., cung cp nguyn liu cho cng nghip dt may, cng
nghip giy...
-Phn loai :
-Monosaccarit: l guluxit don gian, khng th thuy phn duoc nua nhu:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 138
glucozo, manozo, fructozo...
-Disaccarit: l nhung gluxit c hai monosaccarit kt hop voi nhau, khi thuy
phn s thu duoc hai phn tu monosaccarit: saccarozo, mantozo, lactozo,
xenlobiozo,... chng c vi ngot v tan trong nuoc.
-Trisaccarit: Gentianozo (Tn goi: -glucopiranozido-saccarozo hay : 6-(-
glucopiranozido)- -glucopiranozido--fructofuranozit). Rafinozo (Tn goi: -
galactozo-saccarozo hay 6-(-galactopiranozido)- -glucopiranozido--
fructofuranozit),...
-Polisaccarit: L nhung gluxit khi thuy phn dn cng cho monosaccarit:
tinh bt, xenlulozo chng du khng c vi ngot, khng tan trong nuoc.
-Heterosaccarit: l nhung gluxit khi thuy phn cho cc monosaccarit v
nhung cht khng phai l gluxit.
A-MONOSACCARIT
12.1-D|nh nghia v phn loi:
-inh nghia:
Monosaccarit thuoc loai hop chat hu co tap chuc, theo c au tao ha h oc
thng thuong, chng l nhng loai hop chat polihidroxicacbonyl.
-Phn loai:
-Dua vo cu tao nhm cacbonyl:
-CH=O : andozo C=O: xetozo
-Ty thuc vo s nguyn tu cacbon trong phn tu:
3C: triozo 4C: tetrozo 5C: pentozo 6C: hexozo.
Andozo Xetozo
n
1
2
3
4
5
CH
2
-(CH)
4
-C-CH
2
OH
OH OH
O
xetoheptoz
CH
2
(CH)
4
-CH=O
OH OH
andohexoz
CH
2
-(CH)
3
-C-CH
2
OH
OH
OH
O
xetohexoz
andopentoz
CH
2
(CH)
3
-CH=O
OH OH
CH
2
-(CH)
2
-C-CH
2
OH
OH
OH O xetopentoz
CH
2
-CH-CH-CH=O
OH OH OH
andotetroz
xetotetroz
CH
2
-CH-C-CH
2
OH
OH OH O
CH
2
-CH-CH=O
OH OH
andotrioz
HO-CH
2
-C-CH
2
OH
O
xetotrioz
andodioz
HO-CH
2
-CH=O
CH
2
(CH)
n
OH OH O
C CH
2
OH CH
2
(CH)
n
CH=O
OH OH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 139
12.2-Cu to ha hc thng thung :
Cu tao ha hoc thng thuong cua cc monosaccarit duoc thit lp trn co
so cc du kin v kt qua nghin cuu tnh cht ha hoc cua chng:
* Glucozo : C
6
H
12
O
6
So d tm tt mt s tnh cht ha hoc quan trong nht cua (+)glucozo cung
nhu cc andozo:
glucoz
+
C
6
H
5
NHNH
2
CH
2
OH
CH=NNHC
6
HH
5
(+ )
(CHOH)
4
(CHOH)
4
CH=O
CH
2
OH
Glucoz phenylhidrazon
CH
2
OH
COOH
(CHOH)
4
axit gluconic
COOH
COOH
(CHOH)
4
axit glucaric
CH
2
OAc
CH=O
(CHOAc)
4
Penta-O-axetylglucoz
CH
2
OH
CH
2
OH
(CHOH)
4
gluxitol
(sorbitol)
(CHOAc)
4
CH
2
OAc
CH
2
OAc
hexa-O-axetylglucoz
(hexa-O-axetylsorbitol)
(CH)
3
CHI
CH
3
CH
3
2-iothexan
+ (Br
2
+ H
2
O)
+ HNO
3
+ Ac
2
O
+ H
2
, Ni, t
o
C
+ Ac
2
O
+ HI
axit heptanoic
COOH
CH
3
CH
2
(CH)
4
1) HCN
2) H
2
O/H
+
3) HI
Thit lap cng thuc cau tao :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 140
(CH
3
CO)
2
O +
C
6
H
12
O
6
+ dd felinh
+ [Ag(NH
3
)
2
]
+ 1 )
HCN , t
2
)
H
2
O,OH
3 )
HI , t
Cu
2
O
o ga ch
Ag
_
CH=O
C
6
H
7
O(OCOCH
3
)
5
co
5
nho m
OH
CH
3
(CH
2
)
3
CHICH
3
C C C
C C C
CH
3
(CH
2
)
5
COOH
axit enantoic
C C C
C C
CH=O
+ NH
2
OH
hp chat oxim
+ C
6
H
5
NHNH
2
h p cha t phenylhidrazon
C
_
O
1)H
2
, Ni; 2)HI
o
o
+ (Br
2
+ H
2
O)
+ HNO
3
(C
5
H
11
O
5
)COOH
HOOC(C
4
H
8
O
4
)COOH
-CH
2
OH & -CH=O
+
Tu cc du kin trn c th cho php ta di toi kt lun v cu tao cua glcozo :
OH OH
OH OH OH
CH
2
CH CH CH CH CH=O
*Fructozo : C
6
H
12
O
6
:
- Khi nghin cuu fructozo cung c 5 nhm OH .
- Khi oxi ha manh fructozo duoc 2 axit : mt axit 4C v mt axit 2C :
[O]
+ COOH C COOH
_
C C
C
_
_ _
_ _ _ _
_
O
C
C C C
C C
-Khi cng voi HCN, ri thuy phn, sau d khu bng HI duoc axit -
metylcaproic:
H
2
O
CH
2
OH
C=O
CHOH
CHOH
CHOH
CH
2
OH
CH
2
OH
CHOH
CHOH
CHOH
C(OH)CN
CH
2
OH
CH
2
OH
CHOH
CHOH
CHOH
C(OH)COOH
CH
2
OH
CH
3
CH
2
CH
2
CH
2
CHCOOH
CH
3
HCN
H
+
HI
fructoz
xianhidrin
(2 o ng pha n)
hidroxi axit axit -metyl caproic

(2 o ng pha n)
Tu cc du kin d ta suy ra cng thuc cu tao cua fructozo:
CH
2
CH CH CH C CH
2
O OH OH OH
OH
OH
12.3-Cc dng phn lp th cua monosaccarit :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 141
* * * *
1 2 3
4 5
6
OH OH
OH OH OH
CH
2
CH CH CH CH CH=O
Trong phn tu andohexozo c 4C
*
, nn c s dng phn l = 2
n
=2
4
=16 = 8
cp di quang, trong d c 8 dng phn D v 8 dng phn L .
12.3.1-Dy D v L ; cu hnh R,S:
-Cau hnh tuong doi - danh php cau hnh D-L:
So d dng phn dy D cua cc monosaccarit
CH=O
CH
2
OH
OH H
D-glixerandehit
CH=O
CH
2
OH
OH
OH
H
H H
H
OH
HO
CH
2
OH
CH=O
H OH
HO
H
H
OH
OH
CH
2
OH
CH=O
CH=O
CH
2
OH
OH
H
H
OH H
H OH
H
H
HO
CH
2
OH
CH=O
CH=O
CH
2
OH
OH
HO
H
H
HO
OH H
tetroz
pentoz
CH
2
OH
CH=O
OH
OH
H
H
OH H
H OH OH H
H OH
H
H
OH
HO
CH=O
CH
2
OH
CH
2
OH
CH=O
HO
HO
H
H
OH H
H OH OH H
H OH
H
HO
OH
CH=O
CH
2
OH
H
H
CH
2
OH
CH=O
OH
HO
H
HO H
H OH OH H
H HO
H
H
HO
HO
CH=O
CH
2
OH CH
2
OH
CH=O
HO
OH
H
H
HO
H
H OH OH H
H HO
H
H
OH
OH
CH=O
CH
2
OH
D-riboz D-arabioz D-xiloz D-lixoz
D-guloz D-idoz D-taloz
D-antroz D-glucoz D-mannoz D-galactoz
D-anloz
hexoz
Mt cht quang hoat c tri s quay cuc ring (k hiu l []
D
20
), quay tri k
hiu l du (-), qua y phai bng du (+). Du khng lin quan dn cu hnh cua
cht, c hng han axit lac tic c gc quay phai []
D
20
= +3, 82, kh i este n l
metyllactat c gc quay cuc l []
D
20
= -8,25, mc du cu hnh khng di.
C th biu din tnh khng trng anh vt bng cu hnh cua chnh n: Cu
hnh tuong di v cu hnh tuyt di.
Cu hnh tuong di duoc xc dinh theo qui tc Fischer. Qui tc Fischer d
chon andehit glixeric lm cht chun:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 142
CH=O
OH
CH
2
OH
H
H
CH
2
OH
CH=O
HO
anehit-D(+)-glixeric anehit-L(-)-glixeric
Cu hnh cua cc cht khc dua vo cht chun andehit glixeric.
Hop cht dy D c cu hnh ging andehit D-glixeric, cn dy L ging cu
hnh cua andehit L-glixeric. Qui tc Fischer dng nhiu cho cc hop cht duong
gluxit, lipit cht bo v aminoaxit. Cc aminoaxit tu nhin c cu hnh L :
H
H
2
N
COOH
CH
2
OH
L(-)-serin
CH
3
COOH
H
2
N
H
H OH
L(-)-treonin D(-)-treoz
OH H
H
HO
CH=O
CH
2
OH CH
2
OH
CH=O
H
H OH
D(+)-glucoz
HO
H
H
OH
OH
L (+) alanin
H
2
N
COOH
CH
3
H
Do d khng c lin quan truc tip giua du quay cuc v cu hnh.
Khi dng qui tc Fischer cho cc hop cht duong, protit, aminoaxit th
khng c g kh khn nhung nhung hop cht c nhm th khc nhiu voi
andehit glixeric th p dung qui tc khng duoc r rng. Chng han, loai hop
cht Cabxy v Cabxz c 3 nhm th ab x xung quanh trung tm bt di dinh
huong ging nhau di voi nhm th thu tu th cung c mt cu hnh theo Ficher
:
H
D
CH
3
C
2
H
5
H
OCH
3
CH
3
C
2
H
5
H
OH
CH
3
C
2
H
5
C
2
H
5
CH
3
Br
H
-Cau hnh tuyt doi - danh php cau hnh R-S:
Thay cho cu hnh tuong di, nguoi ta dng cu hnh tuyt di theo qui tc
Cahn-Ingold-Prelog, cn goi l h thng danh php R-S.
Tnh khng trng vt anh l do c trung tm bt di xung nn cn xc dinh
cu hnh tuyt di cua t rung tm bt di xung hay nguyn tu bt di xung d.
Danh php R-S cung dua tr n tnh hon cp nhu d dng cho h danh php E-Z
d trnh by o trn.
Nu nguyn tu cacbon bt di xung lin kt voi 4 nhm th a, b, c, d c tnh
hon cp l a > b > c > d, s u phn b cc nhm th no d nhm th nho nht
(nhm d) nm o xa nguoi quan st t h thu tu phn b 3 nhm th cn lai (a, b,
c) xc dinh cu hnh:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 143
Tnh hn ca p cu a
nho m the ng c
chie u kim o ng
ho (ca u hnh S).
ho (ca u hnh R).
chie u kim o ng
nho m the theo
Tnh hn ca p cu a
(S)
(R)
o
o
(S) (R)
c
a d
b
b
d a
c
C
a
b
c
d
d
c
b
a
C
(R)
(S)
Nu su giam tnh hon cap cua cc nhm th d theo chiu kim dong ho th
ung voi cau hnh R (rectus-quay phai), nu theo chi u nguoc kim dong ho th
ung voi cau hnh S (sinister-quay tri).
Th du: cu hnh R, S cua andehit glixeric:
Thu tu uu tin cua cc nhm th:
-OH > -CH=O > -CH
2
OH > -H
Biu din cu hnh cua andehit glixeric trong khng gian ba chiu v bng
cng thuc chiu Fiso (Ficher)
S-glixeranehit R-glixeranehit
C C
OH
CH
2
OH
CH=O
H
HO
CH=O
CH
2
OH
H
(anehit D(+)-glixeric)
(anehit L(-)-glixeric)
R-glixeranehit S-glixeranehit
(anehit D(+)-glixeric)
H
CH
2
OH
CH=O
HO
H
CH=O
CH
2
OH
OH
(anehit L(-)-glixeric)
Cu hnh S cua alanin:
Thu tu uu tin cc nhm th : -NH
2
> -COOH > -CH
3
> -H:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 144
CH
3
COOH
H
2
N
H
NH
2
COOH
CH
3
H
C
S-alanin
(L(+)-alanin)
(L(+)-alanin)
S-alanin
Cu hnh cua axit tactric:
axit-(2S, 3R)-tactric
COOH
COOH
OH
H
HO H H
HO H
OH
COOH
COOH
(axit meso tactric)
(axit L tactric)
(axit D tactric)
COOH
COOH
OH
H HO
H
H
HO
H
OH
COOH
COOH 1
2
3
4
1
2
3
4
axit-(2R, 3R)-tactric axit-(2S, 3S)-tactric
axit-(2R, 3S)-tactric
1
2
3
4
1
2
3
4
R
R
S
S
R
S
S
R
Cu tao cua 16 dng phn quang hoc cua monosaccarit du duoc thit lp
trn co so so snh di chiu voi cu hnh cua cp chun D,L-glixerandehit
CH=O
CH
2
OH
OH H
D-glixerandehit L-glixerandehit
HO H
CH
2
OH
CH=O
Nhung monosaccarit c cu hnh o nguyn tu C
*
xa nh at so v oi nhm
cacbonyl nu ung voi cu hnh D-glixerandehit: thuc dy D; nu ung voi cu
hnh L-glixerandehit: thuc dy L . cn kha nng quay cuc thuc su cua
monosaccarit biu thi bng (+) (quay phai) hay (-) (quay tri) :
L xiloz
D xiloz
CH
2
OH
CH=O CH=O
CH
2
OH
CH
2
OH
CH=O CH=O
CH
2
OH
D lixoz L lixoz L riboz
D riboz L arabinoz
CH=O
CH
2
OH CH
2
OH
CH=O
D arabinoz
CH=O
CH
2
OH CH
2
OH
CH=O
L anloz D anloz
CH=O
CH
2
OH CH
2
OH
CH=O CH=O
CH
2
OH
CH
2
OH
CH=O
D galactoz L galactoz
CH=O
CH
2
OH
CH
2
OH
CH=O
D mannoz L mannoz L glucoz D glucoz
CH=O
CH
2
OH CH
2
OH
CH=O
L guloz Dguloz
CH=O
CH
2
OH
CH
2
OH
CH=O CH=O
CH
2
OH
CH
2
OH
CH=O
DIdoz L Idoz
CH=O
CH
2
OH
CH
2
OH
CH=O
Dtaloz Ltaloz L antroz Dantroz
CH=O
CH
2
OH
CH
2
OH
CH=O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 145
Cau hnh cua andopentozo:
L xiloz
D xiloz
CH
2
OH
CH=O CH=O
CH
2
OH
CH
2
OH
CH=O CH=O
CH
2
OH
D lixoz L lixoz L riboz
D riboz L arabinoz
CH=O
CH
2
OH CH
2
OH
CH=O
D arabinoz
CH=O
CH
2
OH CH
2
OH
CH=O
S
R
R
R
S
S R
R
R
S
S
S
R
S
S
S
R
R
R
S
R
S
R
S
Cau hnh cua andohexozo:
L anloz Danloz
CH=O
CH
2
OH CH
2
OH
CH=O CH=O
CH
2
OH
CH
2
OH
CH=O
Dgalactoz L galactoz
CH=O
CH
2
OH
CH
2
OH
CH=O
Dmannoz L mannoz L glucoz
Dglucoz
CH=O
CH
2
OH CH
2
OH
CH=O
R
S
R
R S
S
R
S
R
R
S
S
S
S
R
R
R
S
S
R
S
R
R
S
R
R
R
R
S
S
S
S
S
R
R
R S
S
S
R
R
S
S
S
S
R
R
R
R
S
R
S
S
R
S
R
R
S
R
R
S
R
S
S
CH=O
CH
2
OH
CH
2
OH
CH=O
Dantroz L antroz Ltaloz Dtaloz
CH=O
CH
2
OH
CH
2
OH
CH=O
L Idoz DIdoz
CH=O
CH
2
OH
CH
2
OH
CH=O CH=O
CH
2
OH
CH
2
OH
CH=O
Dguloz L guloz
12.3.2-Dng phn epime v dng phn dia:
-ong phn epime : 2 monosaccarit l oai andozo c dng phn epime di voi
nhau khi chng chi khc nhau v cu hnh cua nguyn tu C
*
o s t bn canh
nhm CH=O , cn tt ca cc nguyn tu C
*
cn lai du hon tan ging nhau:
D(+)glucozo & D(+)mannozo L(-)g lucozo & L(-)mannozo
D(+)galactozo & D(+)talozo L(-)galactozo & L(-)talozo
D(+)anlozo & D(+)antrozo L(-)anlozo & L(-)antrozo
D(+)Idozo & D(+)gulozo L(-)Idozo & L(-)gulozo .
-ong phn dia : L loai dng phn quang hoc thuong. Trong 16 dng phn
lp th cua a ndhexxzo chi c 1 cht l D(+ )glucozo; dng phn di quang
cua n l L(-) glucozo, cn 14 dng phn lp th khc diu duoc goi l dng
phn dia di voi D(+)glucozo. Cc dng phn dia c cu hnh khc nhau v c
nng sut qua y cuc c th cng du hoc khc du nhung tri s tuyt di cua
gc quay khc nhau.
12.4-Cu to dng vng cua monosaccarit:
12.4.1-Mt s d kin thc nghim di vi glucozo:
-Khng cho phan ung voi thuc thu sip (dung dich axit fucsinsunfuro) v
khng tao san phm cng voi natribisufit.
-C hin tuong quay h bin: dung dich glucozo c su thay di nng sut quay
cuc sau vi ting dng h moi n dinh. Khi moi pha D(+)glucozo, lc du nng
sut quay cuc l []
D
= + 112
o
, lc n dinh l []
D
= + 52,7
o
.
-Glucozo tc dung voi CH
3
OH c mt cua hidroclorua (HCl) khan lm xc tc
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 146
tao ra metylglucozit. Metylglucozit c tnh cht tuong tu axetal hon ton,
khng cho phan ung no cua andehit, khi thuy phn metylglucozit voi dung
dich axit tao thnh andehit v CH
3
OH.
-Khi metyl ha dn cng metyl glucozit bng CH
3
I & A gOH th duoc
tetrametylmetylglucozit. Khi thuy phn san phm ny chi c mt nhn CH
3
lc
du metyl ha bi tch ra, cn 4 nhm metyl sau ny vn tn tai khng bi tch ra
tao thnh tetrametylglucozo. tetrametylglucozo c tnh cht dc trung cua
nhm andehit nhu glucozo.
Nhu vy D(+)glucozo c mt nhm OH dc bit khc voi 4 nhm OH cn
lai, goi l OH semiaxetal (hay OH hemiaxetal hoc OH bn axetal).
M ta su tao thnh glucozit:
CH
OR
OR
axetal
+ HOR
semiaxetal
h p cha t cacbonyl
OH
OR
CH
+ HOR
CH=O
-C 2 cht metyl glucozit :
Dng phn -D-meylglucozit : D
o
nc
= 165
o
, []
D
= + 158
o
.
Dng phn -D-metylglucozit : D
o
nc
= 107
o
, []
D
= -33
o
.
Hai cht dng phn trn khng cho hin tuong quay h bin v khng cho
phan ung voi thuc thu felinh & dung dich Ag[NH
3
]
2
+
.
12.4.2-Cc kiu cng thc vng cua monosaccarit:
Haworth e ngh cong thc vong cua gluxit xuat phat t cong
thc cua d vong piran va furan :
Neu gluxit ton tai d vong 6 canh th goi la piranoz, con vong 5
canh goi la furanoz.
Khi viet cau dang cua monosaccarit ngi ta da tren cau
dang cua xiclohexan. Xiclohexan thng ton tai chu yeu 2
dang cau dang : cau dang ghe va cau dang thuyen.
Cau dang ghecua xiclohexan :
Furan Piran
O O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 147
a
a
a
a
a
a a
a
a
a
a
a
e
e
e
e
e
e
e
e
e
e
e
e
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
6 nguyen t H v tr lien ket truc (axi al ), k hieu la a.
6 nguyen t H lien ket vanh hay lien ket bien (equator i al ),
k hieu la e.
Cau dang thuyen cua xiclohexan :
H
H H
H
H
H H
H
H
H
H
H
H
H H
H
H
H H
H
H
H
H
H
H
H H
H
H
H H
H
H
H
H
H
H
H H
H
H
H H
H
H
H
H
H
Theo kiu Tolen (Tolen
/
s) hoc Havooc (Haworth)
Cu dang gh bn cua cc monosaccarit d nhu sau:
Da ng vo ng Haworth
-L-Glucopiranoz -L-Glucopiranoz
L-Glucoz
CH=O
CH
2
OH
H H
HO H
HO H
HO H
H OH
HO H
HO H
H OH
-L-Glucoz
HO H
-L-Glucoz
H OH
HO H
HO H
dang vong Tolen
/
s

CH
2
OH
O
H
CH
2
OH
O
H
HO
H
HO
O
H
OH
H
OH
H
H
CH
2
OH
HO
H
HO
O
H
OH
H
OH
H
H
CH
2
OH


-D-Glucopiranoz -D-Glucopiranoz
O
H
HO
HO
H
H
H
OH
OH
H
CH
2
OH
O
H
HO
HO
H
H
H
OH
H
OH
CH
2
OH

da ng vo ng Tolen
/
s
H OH
H OH
HO H
CH
2
OH
O
H
-D-Glucoz
H OH
-D-Glucoz
CH
2
OH
O
H
HO H
H OH
H OH
HO H
H OH
H OH
H OH
HO H
CH=O
CH
2
OH
D-Glucoz
HO
O
OH
H
OH
H
H
OH
H
CH
2
OH
H
HO
H
CH
2
OH
H
OH
H
OH
H
H
OH
O
-D-Glucopiranoz -D-Glucopiranoz
Da ng vo ng Haworth
C/thc Fischer
C/thc Fischer
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 148
12.4.3-Cc dng phn anome & giai thch cc hin tung:
Hai dng phn & -D(+)glucozo khng phai l dng phn di quang cua
nhau, chng l c c dng phm dia. Cc cp dng phn dia t uong tu cua cc
monosaccarit ch i khc nhau v cu hnh cua C
1
goi l c c dng ph n anome
(nghia l chi khc nhau v vi tr cua nhm OH semiaxetal trong khng gian).
Cc dng phn & -D(+)glucozo l nhung semiaxetal rt d thuy phn.
Trong dung dich nuoc, mi dng phn d du chuyn ha qua dang andehit
khng vng (dang ho) th nh hon hop cn b ng c c hua c a hai d ang dong
phn & mach vng.
Hin tuong quay h bin c th giai thch boi su d dng mo vng v khp
vng cua cc dang semiaxetal cua D(+)glucozo:
Su hnh thnh 2 dng phn -D(+)metylglucozit v -D(+)metylglucozit
khi metyl ha bng CH
3
OH c mt cua hidroclor ua l su metyl ha nhm OH
semiaxetal cua & -D(+)glucozo. S o di chi c nhm OH semiaxetal duoc
metyl ha t rong diu ki n d l do vi tr dc bit cua nhm OH ny khc hn
cc nhm OH cn lai; n guyn tu H trong nhm OH semiaxetal tro nn linh
dng hon (do anh huong cua hiu ung anome) v d metyl ha hon :
CH
2
OH
OH H
OH H
OH
CH=O
H
HO H
O
H
HO
HO
H
H
H
OH
OH
H
CH
2
OH
O
H
HO
HO
H
H
H
OH
H
OH
CH
2
OH
H
CH
2
OH
H
OH
H
H
H
OH
O
HO
OH
H
CH
2
OH
H
OH
H
OH
H
H
OH
O
HO


CH
2
OH
OH H
OH H
OH
CH=O
H
HO H


-D-Glucopiranoz -D-Glucopiranoz D-Glucoz
Hay :
D-Glucoz -D-Glucopiranoz -D-Glucopiranoz
= +
20 o
D
[ ] 112 = +
20 o
D
[ ] 19
= +
20 o
D
[ ] 112 = +
20 o
D
[ ] 19
= + Can bang :
20 o
D
[ ] 52, 7
-L-Glucopiranoz -L-Glucopiranoz
O
H
H
H
H
OH
OH
HO
HOCH
2
OH
OH
O
H
H
H
H
OH
OH
H
HOCH
2
OH
OH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 149
OCH
3
CH
2
OH
O
HCl khan
CH
3
OH
+
-D(+)glucoz

CH
2
OH
O

-D(+)metylglucozit
O
CH
2
OH

OH semiaxetal
+CH
3
OH
HCl khan

CH
2
OH
O
OCH
3
-D(+)glucoz
-D(+)metylglucozit
hay vit duoi dang cu dang gh bn:

HCl khan
CH
3
OH
O
H
H
H
H
H
CH
2
OH
OH
HO
HO
OH
OH
HO
HO
OCH
3
CH
2
OH
H
H
H
H
H
O
-
D(
+
)
glucoz
-
D(
+
)metylglucozit
+
H
2
O
+

H
2
O
+
HCl khan
CH
3
OH
O
H
H
H
H
H
CH
2
OH
OH HO
HO
OH OH
HO
HO
OCH
3
CH
2
OH
H
H
H
H
H
O
-
D(
+
)
glucoz -

D(
+
)
metylglucozit
+
Cc metylglucozit c th coi tuong ung voi axetal han ton. Chng khng
c kh a nng cho hi n tuong quay h bin v khng cn kha nng khu nhu
D(+)glucozo v chng kh bn trong dung dich nuoc cung nhu voi tc dung cua
bazo. Chng bi thuy phn khi dun nng voi cc dung dich axit t ao thnh cc
dang semiaxetal ban du:
CH=O
CH
2
OH

CH
3
OH
OH
HO
HO
OCH
3
CH
2
OH
H
H
H
H
H
O
-
D(
+
)metylglucozit
+ H
2
O, H
+
gluc )
+
D(
-
O
H
H
H
H
H
CH
2
OH
OH
HO
HO
OH
glucoz )
+
D(
-
O
H
H
H
H
H
CH
2
OH
OH
HO
HO
OH

CH=O
CH
2
OH
CH
3
OH
OH
HO
HO
OCH
3
CH
2
OH
H
H
H
H
H
O
-
D(
+
)metylglucozit
+ H
2
O, H
+
gluc )
+
D(
-
O
H
H
H
H
H
CH
2
OH
OH
HO
HO
OH

glucoz )
+
D(
-
O
H
H
H
H
H
CH
2
OH
OH
HO
HO
OH

KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 150
O
CH
2
OH
-D(+) metylglucozit
OCH
3
+
H
2
O
H
OH
glucoz ) + D(

-
CH
2
OH
O
CH=O
CH
2
OH
O
CH
2
OH
OH
glucoz
)
+
D( -

-
CH
3
OH

O
CH
2
OH
-
D(
+) metylglucozit
OCH
3
+ H
2
O
H
OH
glucoz
) +
D(

-
CH
2
OH
O
CH=O
CH
2
OH
O
CH
2
OH
OH
glucoz ) +
D(

-
CH
3
OH
Cc metylglucozit cung l nhung dng phn anome di voi nhau.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 151
C
C

u
u
h
h

n
n
h
h
c
c
h
h
i
i

u
u
F
F
i
i
s
s
c
c
h
h
e
e
r
r
c
c
u
u
a
a
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
Xetoz
CH
2
OH
O
H OH
H OH
H OH
CH
2
OH
D-Psicoz
CH
2
OH
O H H
H OH
H OH
O
CH
2
OH
D-Fructoz
CH
2
OH
H OH
O H H
H OH
O
CH
2
OH
D-Sorboz
CH
2
OH
O H H
O H H
H OH
O
CH
2
OH
D-Tagatoz
CH
2
OH
H OH
H OH
O
CH
2
OH
D-Ribuloz
CH
2
OH
O H H
H OH
O
CH
2
OH
D-Xyluloz
Andoz
CH=O
CH
2
OH
H OH
H OH
D-Erythroz
CH=O
CH
2
OH
O H H
H OH
D-Threoz
CH=O
CH
2
OH
H OH
H OH
H OH
D-Riboz
CH=O
CH
2
OH
O H H
H OH
H OH
D-Arabinoz
CH=O
CH
2
OH
H OH
O H H
H OH
D-Xyloz
CH=O
CH
2
OH
O H H
O H H
H OH
D-Lyxoz
CH=O
CH
2
OH
H OH
H OH
H OH
H OH
D-Alloz
CH=O
CH
2
OH
O H H
H OH
H OH
H OH
D-Altroz
CH=O
CH
2
OH
H OH
O H H
H OH
H OH
D-Glucoz
CH=O
CH
2
OH
O H H
O H H
H OH
H OH
D-Mannoz
CH=O
CH
2
OH
H OH
H OH
O H H
H OH
D-Guloz
CH=O
CH
2
OH
O H H
H OH
O H H
H OH
D-Idoz
CH=O
CH
2
OH
H OH
O H H
O H H
H OH
D-Galactoz
CH=O
CH
2
OH
O H H
O H H
O H H
H OH
D-Taloz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 152
C
C

u
u
h
h

n
n
h
h
T
T
o
o
l
l
e
e
n
n
/ /
s
s
u
u
-
-
D
D
-
-
f
f
u
u
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Lyxofuranoz
-D-Sorbofuranoz -D-Ribulofuranoz
-D-Threofuranoz
CH
2
OH
OH H
H OH
O H H
H
H OH
O
CH
2
OH
OH H
H OH
H OH
H
H OH
O
CH
2
OH
OH H
O H H
H OH
H
H OH
O
CH
2
OH
OH H
O H H
H OH
H
O
CH
2
OH
OH H
O H H
O H H
H
O
CH
2
OH
OH H
O H H
O H H
H
H OH
O
CH
2
OH
OH HOH
2
C
H OH
H OH
H
O
H
OH HOH
2
C
H OH
H OH
H
O
CH
2
OH
OH HOH
2
C
H OH
O H H
H
O
CH
2
OH
OH HOH
2
C
O H H
O H H
H
O
H
OH H
O H H
H OH
H
O
CH
2
OH
OH H
H OH
O H H
H
O
H
OH HOH
2
C
O H H
H OH
H
O
OH H
H OH
O H H
H
O
CH
2
OH
OH H
OH H
H OH
H OH
H
O
CH
2
OH
OH H
-D-Altrofuranoz -D-Arabinofuranoz
-D-Glucofuranoz -D-Gulofuranoz
-D-Mannofuranoz -D-Psicofuranoz
-D-Xylofuranoz
-D-Tagatofuranoz
-D-Xylulofuranoz
-D-Allofuranoz
-D-Galactofuranoz
H
OH H
H OH
H OH
H
O
CH
2
OH
OH H
H OH
H OH
H
O
CH
2
OH
OH HOH
2
C
O H H
H OH
H
O
OH H
O H H
H OH
H
O
CH
2
OH
OH H
H O H
O H H
O H H
H
O
CH
2
OH
OH H
-D-Erythrofuranoz
-D-Idofuranoz
-D-Ribofuranoz
-D-Fructofuranoz
-D-Talofuranoz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 153
C
C

u
u
h
h

n
n
h
h
T
T
o
o
l
l
e
e
n
n
/ /
s
s

-
-
D
D
-
-
f
f
u
u
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Lyxofuranoz
-D-Sorbofuranoz -D-Ribulofuranoz
-D-Threofuranoz
CH
2
OH
H O H
H OH
O H H
H
H OH
O
CH
2
OH
H O H
H OH
H OH
H
H OH
O
CH
2
OH
H O H
O H H
H OH
H
H OH
O
CH
2
OH
H O H
O H H
H OH
H
O
CH
2
OH
H O H
O H H
O H H
H
O
CH
2
OH
H O H
O H H
O H H
H
H OH
O
CH
2
OH
CH
2
OH O H
H OH
H OH
H
O
H
CH
2
OH O H
H OH
H OH
H
O
CH
2
OH
CH
2
OH O H
H OH
O H H
H
O
CH
2
OH
CH
2
OH O H
O H H
O H H
H
O
H
H O H
O H H
H OH
H
O
CH
2
OH
H O H
H OH
O H H
H
O
H
CH
2
OH O H
O H H
H OH
H
O
H O H
H OH
O H H
H
O
CH
2
OH
OH H
H O H
H OH
H OH
H
O
CH
2
OH
OH H
-D-Altrofuranoz -D-Arabinofuranoz
-D-Glucofuranoz -D-Gulofuranoz
-D-Mannofuranoz -D-Psicofuranoz
-D-Xylofuranoz
-D-Tagatofuranoz
-D-Xylulofuranoz
-D-Allofuranoz
-D-Galactofuranoz
H
H O H
H OH
H OH
H
O
CH
2
OH
H O H
H OH
H OH
H
O
CH
2
OH
CH
2
OH O H
O H H
H OH
H
O
H O H
O H H
H OH
H
O
CH
2
OH
OH H
H O H
O H H
O H H
H
O
CH
2
OH
OH H
-D-Erythrofuranoz
-D-Idofuranoz
-D-Ribofuranoz
-D-Fructofuranoz
-D-Talofuranoz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 154
C
C

u
u
h
h

n
n
h
h
T
T
o
o
l
l
e
e
n
n
/ /
s
s
o
o
-
-
D
D
-
-
p
p
i
i
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Allopiranoz -D-Altropiranoz -D-Arabinopiranoz -D-Galactopiranoz
-D-Glucopiranoz -D-Gulopiranoz -D-Idopiranoz -D-Lyxopiranoz
-D-Mannopiranoz -D-Psicopiranoz -D-Ribopiranoz -D-Sorbopiranoz
-D-Tagatopiranoz -D-Talopiranoz -D-Xylopiranoz -D-Fructopiranoz
CH
2
OH
H OH
H OH
H OH
H
OH H
O
CH
2
OH
O H H
H OH
H OH
H
OH H
O
H
O H H
H OH
H OH
H
OH H
O
CH
2
OH
H OH
O H H
O H H
H
OH H
O
CH
2
OH
H OH
O H H
H OH
H
H OH
O
CH
2
OH
H OH
H OH
O H H
H
OH H
O
CH
2
OH
O H H
H OH
O H H
H
OH H
O
H
O H H
O H H
H OH
H
OH H
O
CH
2
OH
O H H
O H H
H OH
H
OH H
O
H
H OH
H OH
H OH
H
OH HOH
2
C
O
H
H OH
H OH
H OH
H
OH H
O
H
H OH
O H H
H OH
H
OH HOH
2
C
O
H
O H H
O H H
H OH
H
OH HOH
2
C
O
CH
2
OH
O H H
O H H
O H H
H
OH H
O
H
H OH
O H H
H OH
H
OH H
O
H
O H H
H OH
H OH
H
OH HOH
2
C
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 155
C
C

u
u
h
h

n
n
h
h
T
T
o
o
l
l
e
e
n
n
/ /
s
s

-
-
D
D
-
-
p
p
i
i
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Allopiranoz -D-Altropiranoz -D-Arabinopiranoz -D-Galactopiranoz
-D-Glucopiranoz -D-Gulopiranoz -D-Idopiranoz -D-Lyxopiranoz
-D-Mannopiranoz -D-Psicopiranoz -D-Ribopiranoz -D-Sorbopiranoz
-D-Fructopiranoz -D-Xylopiranoz -D-Talopiranoz -D-Tagatopiranoz
CH
2
OH
H OH
H OH
H OH
H
H O H
O
CH
2
OH
O H H
H OH
H OH
H
H O H
O
H
O H H
H OH
H OH
H
H O H
O
CH
2
OH
H OH
O H H
O H H
H
H O H
O
CH
2
OH
H OH
O H H
H OH
H
O H H
O
CH
2
OH
H OH
H OH
O H H
H
H O H
O
CH
2
OH
O H H
H OH
O H H
H
H O H
O
H
O H H
O H H
H OH
H
H O H
O
CH
2
OH
O H H
O H H
H OH
H
H O H
O
H
H OH
H OH
H OH
H
CH
2
OH O H
O
H
H OH
H OH
H OH
H
H O H
O
H
H OH
O H H
H OH
H
CH
2
OH O H
O
H
O H H
O H H
H OH
H
CH
2
OH O H
O
CH
2
OH
O H H
O H H
O H H
H
H O H
O
H
H OH
O H H
H OH
H
H O H
O
H
O H H
H OH
H OH
H
CH
2
OH O H
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 156
C
C

u
u
h
h

n
n
h
h
H
H
a
a
w
w
o
o
r
r
t
t
h
h
o
o
-
-
D
D
-
-
f
f
u
u
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Allofuranoz -D-Altrofuranoz -D-Arabinofuranoz
-D-Glucofuranoz -D-Gulofuranoz
-D-Lyxofuranoz -D-Mannofuranoz -D-Psicofuranoz
-D-Sorbofuranoz
-D-Xylofuranoz
-D-Tagatofuranoz
-D-Galactofuranoz
-D-Threofuranoz
-D-Ribulofuranoz
-D-Xylulofuranoz
O
H
OH
O H
H
H
OH
H
O H
O
H
OH
O H
H
OH
H
H
O H
O
OH
H
OH
H
OH
H
O H OH
O
OH
OH
H
OH
H
H
H
OH
O
OH
OH
H
H
OH
H
O H OH
O
OH
H
O H
H
OH
H
O H OH
O
H
OH
H
O H
OH
H
H
H
O
H
OH
OH
H
H
OH
H
O H
O
OH
H
O H
OH
H
H
H
OH
O
H
OH
OH
H
OH
H
H
OH
OH
O
H
OH
O H
H OH
H
H
OH
OH
O
H
OH
O H
H H
OH
H
OH
OH
O
H
OH
H
O H H
OH
H
O H
OH
O
H
OH
H
OH H
OH
H
OH
OH
O
H
OH
H
OH OH
H
H
O H
OH
-D-Erythrofuranoz
-D-Idofuranoz
-D-Ribofuranoz
-D-Fructofuranoz
-D-Talofuranoz
O
H
OH
H
OH
H
OH
H
H
O
H
OH
H
OH
H
OH
H
O H
O
OH
H
O H
OH
H
H
O H OH
O
H
OH
O H
H OH
H
H
O H
OH
O
H
OH
O H
H H
OH
H
O H
OH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 157
C
C

u
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h

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H
H
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o
o
r
r
t
t
h
h

-
-
D
D
-
-
f
f
u
u
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
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a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
O
H
OH
OH
H
OH
H
H
OH
OH
-D-Allofuranoz
O
H
OH
O H
H OH
H
H
OH
OH
-D-Altrofuranoz
O
H
OH
O H
H
H
OH
H
O H
-D-Arabinofuranoz
O
H
OH
H
OH
H
OH
H
H
-D-Erythrofuranoz
O
H
OH
H
O H H
OH
H
O H
OH
-D-Galactofuranoz
O
H
OH
H
OH H
OH
H
OH
OH
-D-Glucofuranoz
O
H
OH
H
OH OH
H
H
O H
OH
-D-Gulofuranoz
O
H
OH
O H
H OH
H
H
O H
OH
-D-Idofuranoz
O
H
OH
O H
H
OH
H
H
O H
-D-Lyxofuranoz
O
H
OH
O H
H H
OH
H
OH
OH
-D-Mannofuranoz
O
OH
H
OH
H
OH
H
O H
OH
-D-Psicofuranoz
O
H
OH
H
OH
H
OH
H
O H
-D-Ribofuranoz
O
OH
OH
H
O H
H
H
H
OH
-D-Ribulofuranoz
O
OH
OH
H
H
OH
H
O H
OH
-D-Sorbofuranoz
O
OH
H
O H
H
OH
H
O H
OH
-D-Tagatofuranoz
O
H
OH
O H
H H
OH
H
O H
OH
-D-Talofuranoz
O
H
OH
H
O H
OH
H
H
H
-D-Threofuranoz
O
H
OH
OH
H
H
OH
H
O H
-D-Xylofuranoz
O
OH
H
O H
OH
H
H
H
OH
-D-Xylulofuranoz
O
OH
H
O H
OH
H
H
O H
OH
-D-Fructofuranoz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 158
C
C

u
u
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h

n
n
h
h
H
H
a
a
w
w
o
o
r
r
t
t
h
h
o
o
-
-
D
D
-
-
p
p
i
i
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Allopiranoz
O
OH
H
H
H
O H
H
OH OH
H
OH
-D-Altropiranoz
O
OH
OH
H
H
O H
H
OH H
H
OH
O
OH
OH
H
H
O H
H
OH H
H
H
-D-Arabinopiranoz -D-Galactopiranoz
O
OH
H
H
O H
H
OH
H OH
H
OH
O
OH
H
H
H
O H
OH
H OH
H
OH
-D-Glucopiranoz
O
OH
H
H
O H
H
H
OH OH
H
OH
-D-Gulopiranoz
O
OH
OH
H
O H
H
H
OH H
H
OH
-D-Idopiranoz
O
OH
OH
H
H
O H
OH
H H
H
H
-D-Lyxopiranoz
O
OH
OH
H
H
O H
OH
H H
H
OH
-D-Mannopiranoz
O
OH
H
H
H
O H
H
OH OH
H
OH
-D-Psicopiranoz
O
OH
H
H
H
O H
H
OH OH
H
H
-D-Ribopiranoz
O
OH
H
H
H
O H
OH
H OH
H
OH
-D-Sorbopiranoz
O
OH
OH
H
H
O H
OH
H H
H
OH
-D-Tagatopiranoz
O
OH
OH
H
O H
H
OH
H H
H
OH
-D-Talopiranoz
O
OH
H
H
H
O H
OH
H OH
H
H
-D-Xylopiranoz
O
OH
OH
H
H
O H
H
OH H
H
OH
-D-Fructopiranoz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 159
C
C

u
u
h
h

n
n
h
h
H
H
a
a
w
w
o
o
r
r
t
t
h
h

-
-
D
D
-
-
p
p
i
i
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Allopiranoz -D-Altropiranoz -D-Arabinopiranoz -D-Galactopiranoz
-D-Glucopiranoz -D-Gulopiranoz -D-Idopiranoz -D-Lyxopiranoz
-D-Mannopiranoz -D-Psicopiranoz -D-Ribopiranoz -D-Sorbopiranoz
-D-Fructopiranoz -D-Xylopiranoz -D-Talopiranoz -D-Tagatopiranoz
O
H
H
H
H
O H
OH
H OH
OH
OH
O
H
H
H
H
O H
H
OH OH
OH
OH
O
H
OH
H
H
O H
H
OH H
OH
OH
O
H
OH
H
H
O H
H
OH H
OH
H
O
H
H
H
O H
H
OH
H OH
OH
OH
O
H
H
H
O H
H
H
OH OH
OH
OH
O
H
OH
H
O H
H
H
OH H
OH
OH
O
H
OH
H
H
O H
OH
H H
OH
H
O
H
OH
H
H
O H
OH
H H
OH
OH
O
H
H
H
H
O H
H
OH OH
OH
H
O
H
H
H
O H
H
OH OH
OH
H
OH
O
H
H
H
O H
OH
H OH
OH
H
OH
O
OH
H
H
O H
OH
H H
OH
H
OH
O
H
OH
H
O H
H
OH
H H
OH
OH
O
H
H
H
H
O H
OH
H OH
OH
H
O
OH
H
H
O H
H
OH H
OH
H
OH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 160
C
C

u
u
d
d

n
n
g
g
o
o
-
-
D
D
-
-
p
p
i
i
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Allopiranoz -D-Altropiranoz -D-Arabinopiranoz -D-Galactopiranoz
-D-Glucopiranoz
-D-Gulopiranoz -D-Idopiranoz -D-Lyxopiranoz
-D-Mannopiranoz -D-Psicopiranoz -D-Ribopiranoz -D-Sorbopiranoz
-D-Tagatopiranoz -D-Talopiranoz -D-Xylopiranoz -D-Fructopiranoz
O
OH
OH
H
H
H
O H
H
H
O H
OH
O
OH
H
OH
H
H
O H
H
H
O H
OH
O
OH
H
OH
H
H
O H
H
H
O H
H
O
OH
OH
H
H
O H
H
H
O H
H
OH
O
OH
OH
H
H
H
H
H
O H
O H
OH
O
OH
OH
H
H
O H
O H
H H
H
OH
O
OH
H
OH
H
O H
O H
H
H
H
OH
O
OH
H
OH
H
H
H
H
O H
O H
H
O
OH
H
OH
H
H
H
H
O H
O H
OH
O
OH
OH
H
H
H
O H
H
O H
H
OH
O
OH
OH
H
H
H
O H
H
H
O H
H
O
OH
OH
H
H
H
H
O H
O H
H
OH
O
OH
H
OH
H
H
H
O H
O H
H
OH
O
OH
H
OH
H
O H
H
H O H
H
OH
O
OH
OH
H
H
H
H
H
O H
O H
H
O
OH
H
OH
H
H
O H
H
O H
H
OH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 161
C
C

u
u
d
d

n
n
g
g

-
-
D
D
-
-
p
p
i
i
r
r
a
a
n
n
o
o
z
z
o
o
c
c

c
c
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
-D-Allopiranoz -D-Altropiranoz -D-Arabinopiranoz -D-Galactopiranoz
-D-Glucopiranoz -D-Gulopiranoz -D-Idopiranoz -D-Lyxopiranoz
-D-Mannopiranoz -D-Psicopiranoz -D-Ribopiranoz -D-Sorbopiranoz
-D-Fructopiranoz -D-Xylopiranoz -D-Talopiranoz -D-Tagatopiranoz
O
H
OH
H
H
H
O H
OH
H
O H
OH
O
H
H
OH
H
H
O H
OH
H
O H
OH
O
H
H
OH
H
H
O H
OH
H
O H
H
O
H
OH
H
H
O H
H
OH O H
H
OH
O
H
OH
H
H
H
H
OH
O H
O H
OH
O
H
OH
H
H
O H
O H
OH
H
H
OH
O
H
H
OH
H
O H
O H
OH
H
H
OH
O
H
H
OH
H
H
H
OH
O H
O H
H
O
H
H
OH
H
H
H
OH
O H
O H
OH
O
OH
H
H
H
O H
OH
H
O H
H
OH
O
H
OH
H
H
H
O H
OH
H
O H
H
O
OH
H
H
H
H
OH O H
O H
H
OH
O
H
OH
H
H
H
OH
O H
O H
H
OH
O
H
H
OH
H
O H
H
OH
O H
H
OH
O
H
OH
H
H
H
H
OH
O H
O H
H
O
H
OH
H
H
O H
OH H
O H
H
OH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 162
OH
H
H
OH
O
H
HO
OH
H
H
OH
H
OH
H
OH
O
H
HO
OH
H
H
OH
OH
H
HO
H
O
H
HO
OH
H
H
OH
H
OH
HO
H
O
H
HO
OH
H
H
OH
OH
H
H
OH
O
OH
H
OH
H
H
OH
H
OH
H
OH
O
OH
H
OH
H
H
OH
OH
H
HO
H
O
OH
H
OH
H
H
OH
H
OH
HO
H
O
OH
H
OH
H
H
OH
OH
H
H
OH
O
H
HO
H
H
OH
OH
H
OH
H
OH
O
H
HO
H
H
OH
OH
OH
H
HO
H
O
H
HO
H
H
OH
OH
H
OH
HO
H
O
H
HO
H
H
OH
OH
OH
H
H
OH
O
OH
H
H
H
OH
OH
H
OH
H
OH
O
OH
H
H
H
OH
OH
OH
H
HO
H
O
OH
H
H
H
OH
OH
H
OH
H
OH
O
H
OH
H
H
HO
OH
HO
H
OH
H
O
H
OH
H
H
HO
OH
H
OH
OH
H
O
H
OH
H
H
HO
OH
HO
H
H
OH
O
OH
H
H
H
HO
OH
H
OH
H
OH
O
OH
H
H
H
HO
OH
HO
H
OH
H
O
OH
H
H
H
HO
OH
H
OH
OH
H
O
OH
H
H
H
HO
OH
HO
H
H
OH
O
H
OH
OH
H
H
OH
H
OH
H
OH
O
H
OH
OH
H
H
OH
HO
H
OH
H
O
H
OH
OH
H
H
OH
H
OH
OH
H
O
H
OH
OH
H
H
OH
HO
H
H
OH
O
OH
H
OH
H
H
OH
H
OH
H
OH
O
OH
H
OH
H
H
OH
HO
H
OH
H
O
OH
H
OH
H
H
OH
H
OH
OH
H
O
OH
H
OH
H
H
OH
-D-Anloz -D-Antroz -D-Glucoz -D-Mannoz -D-Guloz -D-Ioz -D-Galactoz -D-Taloz
-D-Anloz -D-Antroz -D-Glucoz -D-Mannoz -D-Guloz -D-Ioz -D-Galactoz -D-Taloz
-L-Anloz -L-Antroz -L-Glucoz -L-Mannoz -L-Guloz -L-Ioz -L-Galactoz -L-Taloz
-L-Anloz -L-Antroz -L-Glucoz -L-Mannoz -L-Guloz -L-Ioz -L-Galactoz -L-Taloz
H
OH
HO
H
O
OH
H
H
H
OH
OH
HO
H
H
OH
O
H
OH
OH
H
H
OH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 163
C
C

u
u
h
h

n
n
h
h
,
,
c
c

u
u
d
d

n
n
g
g
a
a
n
n
o
o
m
m
e
e
c
c
u
u
a
a
c
c

c
c
m
m
o
o
n
n
o
o
s
s
a
a
c
c
c
c
a
a
r
r
i
i
t
t
O
OH
H
H
H
O H
H
OH OH
H
OH
-D-Psicopiranoz
O
OH
OH
H
H
O H
H
OH H
H
OH
-D-Fructopiranoz
O
OH
H
H
H
O H
OH
H OH
H
OH
-D-Sorbopiranoz
O
OH
OH
H
H
O H
OH
H H
H
OH
-D-Tagatopiranoz
O
OH
OH
H
H
H
O H
H
O H
H
OH
-D-Psicopiranoz
O
OH
H
OH
H
H
O H
H
O H
H
OH
-D-Fructopiranoz
O
OH
OH
H
H
H
H
O H
O H
H
OH
-D-Sorbopiranoz
O
OH
H
OH
H
H
H
O H
O H
H
OH
-D-Tagatopiranoz
H
H OH
H OH
H OH
H
OH HOH
2
C
O
-D-Psicopiranoz
H
O H H
H OH
H OH
H
OH HOH
2
C
O
-D-Fructopiranoz
H
H OH
O H H
H OH
H
OH HOH
2
C
O
-D-Sorbopiranoz
H
O H H
O H H
H OH
H
OH HOH
2
C
O
-D-Tagatopiranoz
O
H
H
H
O H
H
OH OH
OH
H
OH
-D-Psicopiranoz
O
OH
H
H
O H
H
OH H
OH
H
OH
-D-Fructopiranoz
O
H
H
H
O H
OH
H OH
OH
H
OH
-D-Sorbopiranoz
O
OH
H
H
O H
OH
H H
OH
H
OH
-D-Tagatopiranoz
O
OH
H
H
H
O H
OH
H
O H
H
OH
-D-Psicopiranoz
O
H
OH
H
H
O H
OH H
O H
H
OH
-D-Fructopiranoz
O
OH
H
H
H
H
OH
O H
O H
H
OH
-D-Sorbopiranoz
O
H
OH
H
H
H
OH
O H
O H
H
OH
H
H OH
H OH
H OH
H
CH
2
OH O H
O
-D-Psicopiranoz
H
O H H
H OH
H OH
H
CH
2
OH O H
O
-D-Fructopiranoz
H
H OH
O H H
H OH
H
CH
2
OH O H
O
-D-Sorbopiranoz
H
O H H
O H H
H OH
H
CH
2
OH O H
O
-D-Tagatopiranoz
CH
3
C H
3
-D-Tagatopiranoz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 164
C
C

u
u
h
h

n
n
h
h
F
F
i
i
s
s
c
c
h
h
e
e
r
r
,
,
T
T
o
o
l
l
e
e
n
n
/ /
s
s
,
,
H
H
a
a
w
w
o
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r
t
t
h
h
v
v

c
c

u
u
d
d

n
n
g
g
c
c
u
u
a
a
D
D
-
-
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f
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12.5-Tnh cht cua monosaccarit:
12.5.1-Tnh cht vt l:
Monosaccarit (5C, 6C) l nhung cht kt tinh khng mu, d tan trong
nuoc, khng tan trong ete v clorofom, kh tan trong ruou, khi chung ct bi
phn huy.
Dung dich monosaccarit c tnh cht trung tnh di qi, c d ngot khc
nhau, c tnh quang hoat khc nhau.
12.5.2-Tnh cht ha hc:
monosacarit phan ung voi Cu(OH)
2
tao phuc mu xa nh thm-th hin tnh
cht cua ruou da chuc:
Glucoz
OH OH OH OH OH
CH
2
CH CH CH CH CH=O
CH
2
CH CH CH CH CH=O
OH OH OH
O O
CH
2
CH CH CH CH CH=O
OH OH OH
O O
Cu
H
H
+ Cu(OH)
2
+ 2H
2
O
2
CH
2
OH
O H H
H OH
H OH
O
CH
2
OH
D-Fructoz
CH
2
OH
OH HOH
2
C
O H H
H OH
H
O
-D-Fructofuranoz
CH
2
OH
CH
2
OH O H
O H H
H OH
H
O
-D-Fructofuranoz
O
CH
2
OH
OH
H
O H
OH
H
CH
2
OH
H
-D-Fructofuranoz
O
OH
CH
2
OH
H
O H
OH
H
CH
2
OH
H
-D-Fructofuranoz
O
OH
OH
H
H
O H
H
OH H
CH
2
OH
H
-D-Fructopiranoz
O
CH
2
OH
OH
H
H
O H
H
OH H
OH
H
-D-Fructopiranoz
O
OH
H
OH
H
H
O H
CH
2
OH H
O H
H
-D-Fructopiranoz
O
CH
2
OH
H
OH
H
H
O H
OH
H
O H
H
-D-Fructopiranoz
H
O H H
H OH
H OH
H
CH
2
OH O H
O
-D-Fructopiranoz
H
O H H
H OH
H OH
H
OH HOH
2
C
O
-D-Fructopiranoz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 165
-Phan ung oxi ha :
So d phan ung tng qut:
4HIO
3
axit glucaric
2HCH=O +
4HCOOH
+
HOOC(CHOH)
4
COOH
axit gluconic
axit gluconic
HBr +
CH
2
OH(CHOH)
4
COOH
Ag + CH
2
OH(CHOH)
4
COOH
4HIO
3
HNO
3
Br
2
+ H
2
O
[Ag(NH
3
)
2
]
CH
2
OH(CHOH)
4
CH=O
Cu(OH)
2
NaOH
CH
2
OH(CHOH)
4
COOH
axit gluconic
+
Cu
2
O
glucoz
+ HNO
3
+ (Br
2
+ H
2
O)
axit glycaric
glyconic
COOH
(CHOH)
n
COOH
COOH
(CHOH)
n
CH
2
OH
CH
2
OH
n
(CHOH)
CH=O
-Tc dung voi dung dich Ag[NH
3
]
+
2
:
AgNO
3
+ NH
3
+ H
2
O AgOH + NH
4
NO
4
2AgOH Ag
2
O + H
2
O
Ag
2
O + 4NH
3
+ H
2
O 2[Ag(NH
3
)
2
]OH (bac amoniat)
glucoz
CH
2
OH
CH=O
+ 2[Ag(NH
3
)
2
]OH
COONH
4
CH
2
OH
amonigluconat
+ 2Ag + 3NH
3
+ H
2
O
t C
o
-Tc dung voi dung dich thuc thu felinh khi dun nng:
glucoz
CH
2
OH
CH=O
+ 2Cu(OH)
2
+ NaOH
COONa
CH
2
OH
natri gluconat
+ Cu
2
O + 3H
2
O
t C
o
(ma u o ga ch)
-Tc dung voi dung dich nuoc brom :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 166
glucoz
CH
2
OH
CH=O
+ Br
2
+ H
2
O
COOH
CH
2
OH
axit gluconic
+ 2HBr
-Tc dung voi dung dich HNO
3
:
glucoz
CH
2
OH
CH=O
+ 6HNO
3
COOH
COOH
axit glucaric
+ 6NO
2
+ 4H
2
O
-Tc dung voi dung dich HIO
4
(axit peiodic) .
5HCOOH + HCH=O + 5HIO
3
+ 5HIO
4
CH=O
CH
2
OH
glucoz
(hay:
HOCH
2
(CHOH)
4
CH=O+ 5HIO
4
5HCOOH + HCH=O + 5HIO
3
)
-Phan ung khu :
Khi khu cc monosaccarit tao thnh cc poliancol tuong ung:
CH=O
CH
2
OH
CH
2
OH
CH
2
OH
glucoz sorbit
+ H
2
,Ni, t
o
o
+ H
2
,Ni, t
sorbit
fructoz
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
C=O
+
CH
2
OH
CH
2
OH
mandit
-Phan ung voi hidroxilamin tao oxim v voi phenylhidrazin tao osazon :
* Phan ung voi NH
2
OH:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 167
Osazon
Andoz
CH=O
CHOH
+ NH
2
OH
CHOH
CH=N-OH
+ H
2
O
Tc dung cua andozo v xtzo voi phenylhidrazin truoc tin tao thnh
phenylhidrazon . Nu dng du phenylhidrazin, phan ung din ra tip tuc tao
thnh san ph am r n khng tan trong n uoc goi l ozazon c c hua 2 gc
phenylhidrazin trong phn tu :
Phan ung chung tng qut:
+ C
6
H
5
NH
2
+ NH
3
CH=N-NHC
6
H
5
C=N-NHC
6
H
5
+ 3C
6
H
5
NHNH
2
CHOH
CH=O
Andoz
Osazon
Th du phan ung cua glucozo, manozo v fructozo:
NH
3
)
, (C
6
H
5
NH
2
_
)
(
_
,
NH
3
C
6
H
5
NH
2
C
6
H
5
NHNH
2
+
mannoz
CH
2
OH
CH=O
D(
+
)
D (- )
) + (
D
CH=O
CH
2
OH
3
CH=NNHC
6
HH
5
NNHC
6
H
5
C=
CH
2
OH
CH
2
OH
C=
O
CH
2
OH
C
6
H
5
NHNH
2
+
+
C
6
H
5
NHNH
2
3
glucoz
ozazon
fructoz
Cc dng phn epime cho cng mt san phm ozazon.
Osazon d dng tc dung voi andehit benzoic trong mi truong axit:
+ C
6
H
5
CH=NNHC
6
H
5
CH=N-NHC
6
H
5
C=N-NHC
6
H
5
+ 2C
6
H
5
CH=O
C=O
CH=O
benaldehit phenylhidrazon
Osazon oson
H
+
-Phan ung tng v giam mach cacbon:
-Phan ung tng mach cacbon theo phuong php Kiliani-Fischer:
Phan ung chung tng qut:
CO
2
Na/Hg
CH=O
(CHOH)
4
CH
2
OH
H
2
O
_
O
C
(CHOH)
2
CH O
CHOH
H
2
O/H
HCN
CH
2
OH
(CHOH)
4
COOH
CH
2
OH
CN
CHOH
(CHOH)
3
CH
2
OH
CH
2
OH
(CHOH)
3
CH=O
andopentoz
andohexoz
P
2
O
5

-lacton
xianohidrin axit glyconic
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 168
Th du:
P
2
O
5
P
2
O
5
D-mannoz
D-glucoz
Na/Hg
Na/Hg
CH
2
OH
CH=O
CH
2
OH
CH=O C
CH
2
OH
O
O
O
O
H
2
O
_
H
2
O
_
CH
2
OH
C
+
+
H
2
O/H
H
2
O/H
COOH
CH
2
OH
COOH
CH
2
OH
CN
CH
2
OH
CH
2
OH
CN
+ HCN
CH=O
CH
2
OH
D(+)arabioz
-Phan ung giam mach cacbon theo phuong php Ruff :
+ CO
2
CH
2
OH
D mannoz
CH=O
COOH
CH
2
OH
CaCO
3
(Br
2
+ H
2
O)
CH
2
OH
COO
)
2
Ca
D-arabinoz
CH=O
CH
2
OH
H
2
O
2
axit gluconic canxi gluconat
(CH
3
COO)
3
Fe
-Phan ung giam mach cacbon theo phuong php Wohl (Wall-Remplen):
+ [Ag(NH
3
)
2
]OH
- H
2
O
-HCN
D-arabioz
CH
2
OH
CH=O
CH
2
OH
CN
+ (CH
3
CO)
2
O
+ NH
2
OH
C=NHOH
CH
2
OH
CH=O
CH
2
OH
D-glucoz
-Phan ung Werman: dua theo phuong php thoi phn Hoffmann:
D-glucoz
CH
2
OH
CH=O
CH
2
OH
C=O
+ NH
3
CH
2
OH
CH=O
CH
2
OH
D-arabioz
-NH
3
H
2
N-
+ (Cl
2
+ NaOH)
H
2
N-CH-OH
+ H
+
-Phan ung tao ete v este cua monosaccarit :
* Phan ung tao ete:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 169
+
CH
3
O
NaOH
(CH
3
)
2
SO
4
tetrametylmetylglucozit ) + D(
-
O
H
H
H
H
H
CH
2
OCH
3
OCH
3 CH
3
O
CH
3
O
HCl khan
+ CH
3
OH

O
H
H
H
H
H
CH
2
OH
OH
HO
HO
OH
OH
HO
HO
OCH
3
CH
2
OH
H H
H
H
H
O
-D(+)glucoz
-

D(+)metylglucozit
CH
3
O
CH
3
O
OH
CH
2
OCH
3
H
H
H
H
H
O
-
D(+) tetrametylglucoz
CH
3
O
dd HCl
CH
3
O
tetrametylglucoz ) + D(
-
OH
H
H
H
H
CH
2
OCH
3
CH
3
O
CH
3
O
CH=O
CH
3
O
tetrametylglucoz ) + D(
-
O
H
H
H
H
H
CH
2
OCH
3
OH
CH
3
O
CH
3
O

(Kho ng co tnh kh ,
kho ng co hie n tautome)
(Kho ng co tnh kh ,
kho ng co hie n tautome)
(Co tnh kh , co hie n tautome)
(Co tnh kh , co hie n tautome)
* Phan ung tao este:
CH
3
COO
CH
3
COO
CH
3
CO
CH
3
COONa
(CH
3
CO)
2
O
+

pentaaxetylgluco ) + D(
-
O
H
H
H
H
H
CH
2
OCOCH
3
OCOCH
3

O
H
H
H
H
H
CH
2
OH
OH
HO
HO
OH
-D(
+) glucoz
O
12.6-Mt s monosaccarit tiu biu:
12.6.1-D(+)glucozo:
O
CH
2
OH
glucopirannoz
) +
D(

-
glucopirannoz
) + D(
-
CH
2
OH
O
glucoz ) + D(
CH
2
OH
CH=O
da ng tha ng da ng vo ng OH semiaxetal
Glucozo c duoi dang tu do trong cc qua chn, nhu trong qua nho
(D(+)glucozo cn goi l duong nho) v tr ong cc loai hoa qua cng voi D-
fructozo v saccarozo. Trong mu nguoi v dng vt lun lun c mt ti l D-
glucozo nht dinh; D-glucozo c duoi dang hop cht cng voi D-glucozo hoc
voi monosaccarit khc trong disaccarit (nhu mantozo, lactozo, saccarozo) hoc
trong cc polisaccarit quan trong (nhu tinh bt, xenlulozo).
-iu ch glucozo:
Nguoi ta diu ch glucozo bng cch thuy phn tinh bt c HCl lm xc tc
trong ni hp P = 2atm .
-Tnh chat vat l:
Glucozo l cht kt tinh, tan nhiu trong nuoc, dung dich c vi ngot = 60%
saccarozo. Dung dich glucozo lm quay cuc sang phai: -D-glucozo c []
D
=
+112
o
cn -D-glucozo c []
D
=+19
o
, tt ca s c hin tuong quay h bin dat
toi cn bng : [ ]
D
= +52,7
o
.
-Tnh chat ha hoc:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 170
Nhu d nu o phn tnh cht chung cua monosaccarit: c tnh cht cua mt
andehit.
-Phan ung ln men cua glucozo:
+Phan ung ln men ruou :
C
6
H
12
O
6

ru men
2C
2
H
5
OH + 2CO
2
+Phan ung ln men lactic:
C
6
H
12
O
6

lactoza men
2CH
3
CH(OH)COOH
+Phan ung ln men xitric:
axit xitric
+ H
2
O
men
OH
COOH
HOOC-CH
2
-C-CH
2
-COOH
C
6
H
12
O
6
+Phan ung ln men axetonobutylic :
3C
6
H
12
O
6

men
2C
2
H
5
OH + C
4
H
9
OH + (CH
3
)
2
C=O + 4H
2
+ 7CO
2
Cc phan ung ny c nhiu ung dung trong thuc t cng nghip ha hoc.
- nghia:
Glucozo c nghia dc bit quan trong di voi sinh l dng vt v thuc vt.
Glucozo dng d tip nuoc cho nguoi bnh.
12.6.2-D(-)fructozo:
da ng vo ng
O O
CH
2
OH
O C
CH
2
OH
da ng vo ng
da ng tha ng
CH
2
OH
-D(
-
) frutopiranoz
CH
2
OH
HOCH
2
1
2
3
4
5
6
1
2
3
4
5
6
fructoz )
-
D(
frutofuranoz )
-
D( -
D(-)fructozo l mt xetozo rt ph bin trong thuc vt o trang thi tu do c
nhiu trong qua cng voi D(+)glucozo.
Trong mt ong c chua hn hop dng phn tu cua D(-)fructozo
vD(+)glucozo.
D(-)fructozo cn o trang thi trong cc hop cht nhu disaccarit (saccarozo -
tuc duong ma) .
-Tnh chat vat l:
D(-)fructozo khan c D
o
nc
=102-104
o
, dc trung quay cuc tri manh: [ ]
D
=
-133
o
.
N c hin tuong quay ho bin:
Dung dich lc lc du moi pha c []
D
=-133
o
, khi dat t oi trang thi cn
bng th: [ ]
D
= -92
o
.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 171
Khi cn bng trong dung dich nuoc n c dang vng 5 canh v 6 canh.
D-fructozo c vi ngot nht trong c loai duong monosaccarit, mt ong ngot
chu yu l do D-fructozo.
-Tnh chat ha hoc:
Fructozo cng cho phan ung trng guong khi tc dung voi dung dich bac
nitrat trong amoniac, phan ung voi dung dich thuoc thu felinh tao ra kt tua
do gach Cu
2
O nhu glucozo, mc d trong phn tu khng c nhm CH=O.
Diu d duoc giai thch nhu sau:
Trong mi truong kim, D-fructozo d dng phn ha thnh D-glucozo v
D-mannozo qua d ang trung gian endiol, chnh glucozo v mannozo tham gia
phan ung dc trung cua nhm andehit, t rong qa t rnh phan ung, cn bng s
chuyn dich tu fructozo v pha tao thnh glucozo v mannozo:
endiol
CHOH
CH
2
OH
C OH
O C
CH
2
OH
fructozoz
CH
2
OH
D
(-)
glucoz
CH
2
OH
CH=O
D
(
+
)
mannoz
CH
2
OH
CH=O
D
(
+
)
OH
Nhu vy d phn bit Glucozo voi Fructozo, nguoi ta khng dng phan ung
trng guong, m dng phan ung Selivanov: Cho tinh th rezoxin (m-
dihidroxibenzen) + v i giot dung dich HCl vo mt ng nghim. Lc ng
nghim d ha t an rezoxin v chia thnh 2 phn bng nhau. Nho vo phn thu
nht 2 giot dung dich fructozo, vo phn thu 2 cung 2 giot dung dich Glucozo.
Dun nng ca 2 ng nghim trn ni cch thuy 80
o
C v giu nhit d ny trong
thoi gi an 7 - 8 pht . Theo di v so snh tc d xut hi n mu do ca 2 ng
nghim: Trong diu kin th nghim trn, cc xeton hexozo bin thnh
hidroximetylfurfural nhanh gp 15-20 ln so voi andohexozo. Do vy, trong th
nghim voi fructozo su xut hi n mu nhanh hon v cuong d mu cung lon
hon. Diu d duoc giai thch: Khi dun nng voi axit HCl, hoc H
2
SO
4
, c a
fructozo cung nhu glucozo du sinh ra mt hn hop cc san phm, trong d c
hidroximetylfurfural. Chnh hidroximetylfurfural ngung tu voi rezoxin cho san
phm c mu do sng:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 172
hidroximetylfurfural
hay:
H
2
O
H
2
O
+ H
2
O
H
2
O
CH
2
OH
dd HCl
t C
o
HOCH
2
CH=O
O
CH
CH
2
OH
CH
CH
C
CH=O
O
O
CH=O
CH
CHOH
CHOH
CH
2
OH
CH
OH
OH
CH
CH
2
OH
CHOH
CHOH
CH
CH
O
CH
CH
2
OH
CHOH
CHOH
C
CHOH
O
OH
O
CH
2
OH
C
CHOH
CHOH
CH
2
OH
CH CHOH
CHOH
CHOH
C=O
CH
2
OH
CH
2
OH
CHOH
CHOH
CHOH
CHOH
CHOH CH=O
CHOH
CHOH
CHOH
CHOH
CH
2
OH
hidroximetylfurfural
hay:
H
2
O
H
2
O
+ H
2
O
H
2
O
CH
2
OH
dd HCl
t C
o
HOCH
2
CH=O
O
CH
CH
2
OH
CH
CH
C
CH=O
O
O
CH=O
CH
CHOH
CHOH
CH
2
OH
CH
OH
OH
CH
CH
2
OH
CHOH
CHOH
CH
CH
O
CH
CH
2
OH
CHOH
CHOH
C
CHOH
O
OH
O
CH
2
OH
C
CHOH
CHOH
CH
2
OH
CH CHOH
CHOH
CHOH
C=O
CH
2
OH
B-DISACCARIT
12.7.1-D|nh nghia v phn lai:
-inh nghia: isacarit l nhng gluxit gom 2 goc monosaccarit kt hop voi
nhau. Khi thuy phn disaccarit se thu duoc 2 phn tu monosaccarit.
-Phn lo ai: Tuy theo cch kt h op gi ua 2 gc monosaccarit nguoi ta ch ia
thnh 2 loai:
Loai thu nhat: Disaccarit khng c tnh khu:
(II)
(I)
C
6
H
11
O
5
O
disacarit
H
2
O
+
OH semiaxetal
HO OH C
6
H
11
O
5
O
5
C
6
H
11
+
C
6
H
11
O
5
Cu oxi tao lin kt giua 2 monosaccarit goi l lin kt glucozit. Do 2 nhm
OH semiaxetal tao thnh lin kt glucozit, do d khng chuyn duoc thnh
dang andehit, n n loai ny khng c tnh cht khu: loai disaccarit ny goi l
ozido-ozit
Loai thu hai: Disaccarit c tnh khu :
(II)
(I)
C
6
H
10
O
4
OH O
disaccarit
H
2
O +
OH semiaxetal
HO OH
C
6
H
11
O
5
O
4
C
6
H
10
OH +
C
6
H
11
O
5
OH ancol
OH semiaxetal
OH semiaxetal
Monosaccarit (II) trong disaccarit cn OH semiaxetal, do d c th chuyn
thnh dang andehit t rong dung dich v t h hin tnh cht khu: loai disaccarit c
tnh cht khu ny goi l ozido-ozo.
12.7.2-Mt s disaccarit quan trng:
a. Saccarozo: (Duong ma, duong cu cai , duong tht nt, duong knh).
* Cng thuc phn tu: C
12
H
22
O
11
.
* Cng thuc cau tao:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 173
O
CH
2
OH
HOCH
2
O
CH
2
OH
O

_
glucoz
_
fructoz
te n goi :


( -
D
-
glucopiranogido) -
-
D
-
fructofuranozit 2-
* Trang thi tu nhin:
Saccarozo ph bin trong gioi thuc vt, c trong nhiu loai cy, dc bit l
cy ma (14-26%), trong cu cai duong (16-20%).
* Tnh chat vat l:
Saccarozo d tan trong nuoc, kh tan trong ruou etylic, khi kt tinh tu nuoc
s cho t inh ti nh th lon dang A : D
o
nc
= 185
o
C ; n u kt tinh tu ruou metylic
duoc dang kt t inh tinh th dang B: D
o
nc
= 170
o
C. Dung dich nuoc saccarozo
lm quay cuc sang phai []
D
20
= +65,5
o
v khng cho hin tuong quay h bin.
Nng d saccarozo trong dung dich nuoc c th xc dinh bng phn cuc k,
cung goi l duong k.
* Tnh chat ha hoc:
Saccarozo thuc loai disaccarit khng c tnh cht khu, boi v OH
semiaxetal tu do khng cn, do d khng chuyn thnh dang andehit, nn khng
c tnh cht khu: nhu khng cho phan ung trng guong, khng cho phan ung
voi thuc thu felinh v khng cho phan ung voi phenylhidzazin tao ozazon.
Saccarozo d thuy phn trong mi truong axit yu, ngay ca axit yu CO
2
+
H
2
O tao thnh D-glucozo v D-fructozo .
Do D-fructozo l ch at quay tri m anh, cn D-gluczo l ch at quay ph ai
vu, nn sau khi th uy phn dung dich t ro nn quay tri: [ ]
D
20
= -20
o
, hi n
tuong d goi l su nghich dao duong.
Saccarozo c th tao thnh saccarat kim loai kim th, nht l di voi canxi.
C nhiu lo ai saccarat ca nxi khc n hau v d ha tan trong nuoc:
monosaccarat canxi C
12
H
22
O
11
.CaO.H
2
O v disaccaratcanxi
C
12
H
22
O
11
.2CaO.2H
2
O ta n trong nuoc, cn trisaccaratcanxi
C
12
H
22
O
11
.3CaO.3H
2
O kh tan. Nho tnh tan cua saccaratcanxi nn nguoi ta loi
dung tnh cht ny d tinh ch saccarozo trong cng nghip san xut duong
bng cch ch ha voi Ca(OH)
2
:
Saccaroz
Ca(OH)
2
saccaratcanxi tan , ta p cha t ra n
lo c
saccaratcanxi
CO
2
saccaroz + CaCO
3
lo c
saccaroz tinh khie t
* San xuat duong ma:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 174
Qui trnh san xut duong ma trong nghip theo cc cng doan sau:
Ca y ma r a sa ch , ca t nho
e p lo c Ca(OH)
2
CO
2
CO
2
lo c
than hoa c SO
2
(hoa cNaHSO
3
)
co d i P tha p
li ta m
ng tinh luye n
Cu dang bn cua saccarozo :
H
O
OH
HO
HO
CH
2
OH
H
H
H
H
H
O
O
CH
2
OH
H
HO
H
CH
2
OH
HO
-
2
fructofuranozit -
D
-
- ) glucopiranogido
-
D -
(

te n go i :
b. uong mantozo (Duong mach nha):
* Cng thuc phn tu: C
12
H
22
O
11
* Cng thuc cu tao dang Hvooc (HaWorth) v c u dang gh bn cua mantozo
(c 2 dng phn anome dang v dang ):
O
CH
2
OH
1
2 3
4
5
6
O
O
glucoz
-
4 glucopiranoz -
D
- - ) glucopiranogido -
D
- (
te n go i :
go c D
-
- D go c
glucoz
6
5
4
3
2
1
CH
2
OH

CH
2
OH
1
2
3
4
5
6
glucoz
go c D-
-
D go c
te n go i :


( -
D
-glucopiranogido )- -
D
- glucopiranoz 4
-
glucoz
O
O
6
5
4
3 2
1
CH
2
OH
O

O
O
H
H
H
H
H
CH
2
OH
OH
HO
OH
OH
HO
HO
CH
2
OH
H
H
H
H
H
O O
H
H
H
H
H
CH
2
OH
HO
HO
OH
OH
HO
OH
CH
2
OH
H
H
H
H
H
O
O
o ng pha n o ng pha n

Hai gc monosaccarit trong phn tu mantozo lin kt vo nhau nho lin kt
-1-4-glucozit.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 175
* Trang thi tu nhin:
Mantozo c mt trong nhiu loai cy, nhung chi c mt luong nho, khng c
nghia thuc tin.
Mantozo duoc diu ch khi thuy phn tinh bt chua hon ton nho xc tc
axit.
Mantozo cung duoc hnh thnh khi thuy phn tinh bt bng tc dung cua
men amila c mt t rong mm la trong qa t rnh ln men ruou. Keo mach nha
cung dua trn nguyn tc d.
* Tnh chat ha hoc:
Mantozo thuc loai disaccarit c tnh chat khu (loai ogidozo): Khu duoc
dung dich Ag[NH
3
]
2
+
t ao kt t ua Ag v dung dich thuc thu felinh tao kt tua
do gach Cu
2
O, cung phan ung voi phenylhidzazin c thua t ao kt t ua oza zon
C
12
H
20
O
9
(=N-NHC
6
H
5
)
2
, v bi oxi ha khi tc dung voi dung dich nuoc brom
tao ra axit monocacboxylic matobionic: (C
11
H
21
O
10
)COOH.
Dung dich mantozo tn tai 2 dang anome :

CH
2
OH
1
2 3
4
5
6
glucoz
goc D-
-
D go c

(
- D
-glucopiranogido)- - D
- glucopiranoz 4-
glucoz
O O
6
5
4
3 2
1
CH
2
OH
O
CH
2
OH
1
2 3
4
5
6
glucoz
go c D-
-
D go c


(
-
D
-glucopiranogido)- - D
- glucopiranoz 4-
glucoz
O O
6
5
4
3 2
1
CH
2
OH
O
CH
2
OH
1
2 3
4
5
6
O OH
CH=O
6
5
4
3 2
1
CH
2
OH
O
D ang v c nng sut qua y cuc tuong ung l: []
D
= +168
o
& []
D
=
+112
o
, c c dang ny c hin tuong quay h bin trong dung dich, khi dat toi
cn bng []
D
= +136
o
.
Tt ca cc du kin trn chung to mantozo c chua nhm OH semiaxetal tu
do v tr ong dung dich c th chuyn ha mt ph n thnh dang andehit, n n
mantozo c tnh cht khu nhu d ni o trn.
Khi mantozo bi thuy phn boi tc dung cua axit hoc men manta cho san
phm D-glucozo.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 176
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
OH
HO
OH
CH
2
OH
H
H
H
H
H
O
-
D -
O
te n go i : 4 - ( - glucopiranogido) -glucopirano
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
OH
HO
CH
2
OH
H
H
H
H
OH

Br
2
, H
2
O
( -(+)mantoz)
COOH
Axit D mantoboonic
Axit -D-mantobionic
COOH
O
OCH
3
H
H
H
H
CH
2
OCH
3
CH
3
O
OCH
3
CH
3
O
CH
3
O
CH
3
O
CH
2
OCH
3
H
H
H
H
H
O
O
H
H
H
H
H
CH
2
OCH
3
CH
3
O
CH
3
O
CH
3
O
OCH
3
CH
3
O
CH
2
OCH
3
H
H
H
H
OCH
3
OH
COOH
HO
+
Tetrmetyl metyl -D-glucopiranoz
( -anome)
H
2
O
H
+
(CH
3
)
2
SO
4
/NaOH
c. Lactozo hay duong sa: Cng thuc phn tu: C
12
H
22
O
11
.
Cng thuc cu tao dang vng HaWorth v cu dang gh bn (gm 2 dng
phn anome dang v dang ):
O O
- -

O
CH
2
OH
1
2
3
4
5
6
galatoz
go c D-
-
D go c
te n go i :

(
- D
- galactopiranogido )
-
-
D
- glucopiranoz
4
-
glucoz
6
5
4
3
2
CH
2
OH
1

1
CH
2
OH
2
3
4
5
6
glucoz
-
4
glucopiranoz -
D
-
-
) galactopiranogido -
D -
(

te n go i :
go c D
-
- D go c
galatoz
6
5
4
3
2
1
CH
2
OH
O

- -
O O


O
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
OH
OH
CH
2
OH
H
H
H
H
H
O
H H
O
H
H
H
H
H
CH
2
OH
OH
OH
OH
HO
HO
CH
2
OH
H
H
H
H
H
O
O
o ng pha n
o ng pha n
Lactozo c trong sua nguoi v dng vt c v, sua nguoi c khoang 5-8%
lactozo, cn sua b c khoang 5,5% l actozo. Trong cng nghip nguoi ta thu
duoc lactozo nhu l mt s an phm phu khi san xut pho -mt: l actozo chua
trong cn sua l mt dung dich nuoc cn lai sau khi lm dng tu cc protit cua
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 177
sua. Sua chua l sua tr ong d lactozo bi bin thnh axit l actic duoi tc dung
cua men vi sinh (Lactobacillta bulgaricua).
Lactozo l disaccarit c tnh cht khu, c th tao ozozon v tn tai duoi 2
dang anome v , cho hin tuong quay h bin, nng sut quay cuc lc dat
trang thi cn bng l: []
D
= +52,6
o
, vi ngot cua lactozo km saccarozo toi 4 -
5 ln .
Khi thuy phn c xc tc axit hoc voi men emunsin, lactozo cho D-
galactozo v D-gluc ozo; hai gc lin kt voi nhau nho lin kt -1,4-glucozit,
ca 2 gc monosaccarit du c dang vng pirano:
H
2
O
axit Gluconic
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
D-Galactoz
OH
+
COOH
CH
2
OH
CH
2
OH
C=NNHC
6
H
5
CH=NNHC
6
H
5
H
2
O
+
OH
D-Galactoz
OH
HO
HO
CH
2
OH
H
H
H
H
H
O
Glucosazon
OH
C=NNHC
6
H
5
NNHC
6
H
5
COOH
3C
6
H
5
NHNH
2
Br
2
, H
2
O
Axit lactobionic
O
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
OH
CH
2
OH
H
H
H
H
OH
H
Lactosazon
O
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
CH
2
OH
H
H
H
C
H
-
4
glucopiranoz -
D
- -
)
galactopiranogido -
D -
(

O
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
OH
OH
CH
2
OH
H
H
H
H
H
O
H
d. Xenlobiozo: Cng thuc phn tu: C
12
H
22
O
11
.
Cng thuc cu tao dang vng HaWorth v cu dang gh bn (gm 2 dng
phn anome dang v dang ):
O O
- -

O
CH
2
OH
1
2
3
4
5
6
glucoz
go c D-
-
D go c
te n go i :

(
- D
- glucopiranogido )
-
-
D
- glucopiranoz
4
-
glucoz
6
5
4
3
2
CH
2
OH
1

KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3


B mn Ha Hu Co L Vn Dng
Trang 178

1
CH
2
OH
2
3
4
5
6
glucoz
-
4
glucopiranoz -
D
-
-
) glucopiranogido -
D -
(

te n go i :
go c D
-
- D go c
glucoz
6
5
4
3
2
1
CH
2
OH
O

- -
O O

Xenlobiozo c cu tao tuong tu nhu mantozo, chi khc o ch lin kt


glucozit o xenlobiozo l -1-4-glucozit, trong khi d di voi mantozo l -1-4-
glucozit. xenlobiozo duoc coi l san phm trung gian trong qa trnh thuy phn
xenlulozo.
Khi ch ha xenlulozo trong vi ngy voi axit sunfuric v anhidrit axetic, s
xay r a dng thoi phan ung axetyl ha v ph an ung thuy phn v s thu duoc
octaaxetatxenlobiozo. Thuy phn octaaxetatxenlobiozo s cho xenlobiozo.
Xenlobiozo cung l duong khu nhu mantozo, tao duoc ozozon, tn tai duoi 2
dang v , cho hin tuong quay h bin. Khi thuy phn cho hai phn tu D-
glucozo. C c gc D-glucozo trong phn tu xenlobiozo du c cu tao dang
vng pirano.
Cu dang bn cua xenlobiozo:
H
O
H
H
H
H
H
CH
2
OH
OH
OH
OH
HO
HO
CH
2
OH
H
H
H
H
H
O
O O
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
OH
OH
CH
2
OH
H
H
H
H
H
O
H
o ng pha n o ng pha n

C-TRISACCARIT
a. Gentianozo: L trisaccarit khng c tnh khu, phn tu gm 2 mt xch l -
glucozo v mt mt xch l -fructozo
1
2
3
4
5
6
1
2
3
4
5
6
6
5
4
3
2
1
O
OH
HO
HO
CH
2
OH
H
H
H
H
H
O
O
CH
2
OH
H
HO
H
CH
2
OH
HO
O
CH
2
O
HO
OH
OH
H
H
H
H
H
Tn goi: -glucopiranozido-saccarozo hay : 6-(- glucopiranozido)- -
glucopiranozido--fructofuranozit.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 179
b. Rafinozo : L t risaccarit khng c tnh khu, ph n tu gm 1 mt xch l -
galactozo, 1l -glucozo v 1 mt xch l -fructozo:
H
H
H
H
H
OH
OH
HO
O
O
CH
2
HO
CH
2
OH
H
HO
H
CH
2
OH
O
O
H
H
H
H
H
CH
2
OH
HO
HO
OH
1
2
3
4
5
6
6
5
4
3
2
1
6
5
4
3
2
1
O
Tn goi: -galactozo-saccarozo hay: 6-(-galactopiranozido)- -
glucopiranozido--fructofuranozit:
D-POLYSACCARIT
Khi nim:
Polisaccarit l nhung hop cht cao phn tu, m trong phn tu gm nhung
mt xch l nhung gc monosaccarit .
Cc polisaccarit thuong gp: tinh bt, xenlulozo c cng thuc chung:
(C
6
H
10
O
5
)
n
trong d n = 100-1000
I-TINH BT
cng thuc phn tu : (C
6
H
10
O
5
)
n
12.8.1-Trng thi t nhin:
Tinh bt o duoi dang hat trong thuc vt, kch thuoc cua hat tinh bt khc
nhau, nhu hat tinh bt tr ong gao nho, hat tinh bt tr ong khoai ty lon. Th nh
phn tinh bt trong cc loai thuc vt khc nhau:
Trong gao: 70-80%; trong khoai ty: 16-19%; trong ng: 65-70%.
Ni chung luong tinh bt trong cc loai hat ngu cc chim ty l cao hon
trong cc loai cu nhu khoai, sn, khoai ty, khoai so.
12.8.2-Tnh cht cua tinh bt:
-Tinh bt l cht mu trng, v dinh hnh.
-Khng tan trong nuoc lanh.
-Trong nuoc nng tinh bt truong phng ln, o nhit d cao dn dn tao thnh
dung dich nhot, khi d ngui duoc dung dich mu trng duc goi l h tinh bt.
Qa t rnh h ha khng phai l mt hi n tuong vt l don thun, m n lm
bin di mt phn cu t ao cua tinh bt v l mt qa t rnh bt thun nghich.
Nghia l khng th lm cho h tinh bt tro lai dang tinh bt ban du.
-Tinh bt cho phan ung mu dc trung voi it : dung dich h tinh bt tuong tc
voi i t c ho mu x anh, m u n y mt di khi dun nng , nh ung d ngui l ai c
mu tro lai. Phan ung mu d nhn bit it t u do v nguoc lai d nhn bit tinh
bt.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 180
-Dung dich tinh bt cung c tnh quang hoat, nng sut quay cuc []
D
= 201-
205
o
.
-Tinh bt khng c tnh khu, khng khu duoc dung dich felinh, khng cho phan
ung trng guong, v trong tinh bt hu nhu khng cn nhm OH semiaxetal tu
do, n i chnh xc l c u hng trm gc monosaccarit m oi c 1 nhm OH
semiaxetal tu do.
-O diu kin lanh, tinh bt khng tc dung voi Cu(OH)
2
cho dung dich mu
xanh nhu cc hop cht c nhiu nhm OH.
-Khi dun nng nhanh tinh bt thuong (chua 10-20% nuoc), tinh th tinh bt bi
phn ct th nh nhiu phn tu polisaccarit nho hon goi l cc dextrin c cng
thuc chung l (C
6
H
10
O
5
)
x
, (x < n ). Hin tuong d goi l su dextrin ha. Khi
nuong bnh m, l op vo bnh m bin thnh dextrin, cc dextrin cung cho phan
ung mu voi dung dich it . Ty kch thuoc phn tu cc dextrin ta c cc mu
voi it khc nh au. Mu chuyn tu tm xanh, r i tm, tm do, da cam, dn vng
khi kch thuoc cua dextrin giam dn.
-Tinh bt c th bi thuy phn bng axit hoc bng men tao thnh cc dextrin ri
tao thnh mantozo, cui cng cho D-glucozo:
(C
6
H
10
O
5
)
n
x
(C
6
H
10
O
5
)
C
12
H
22
O
11
C
6
H
12
O
6
tinh bo t
dextrin mantoz
glucoz
D
-
12.8.3-Cu to cua tinh bt:
Tinh bt khng phai l gm nhung phn tu dng nht m l hn hop cua 2
loai polisaccarit: gm amilozo v amilopectin.
-Cau tao cua amilozo:
Cc phn tu amilozo l gm nhung dai phn tu, chu yu l gm nhung
mach khng phn nhnh cua c c gc D-glucozo lin kt voi nhau (n = 600-
1200). Cc gc D-gl ucozo trong phn tu du o dang vng -pirano. Cc gc
D-glucozo lin kt voi nhau bng lin kt -1,4-glucozit:
OH
HO
glucoz
_

2
2
_
n
glucoz
_
glucoz
_

O
HO
OH
CH
2
OH
H
H
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
O
O
O
O
O
OH
HO
OH
CH
2
OH
H
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
O

_
glucoz

1
4
lien ket
1,4
glucozit

KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3


B mn Ha Hu Co L Vn Dng
Trang 181
O
OH
O
HO
CH
2
OH
H
H
H
H
O
H
H
O
H
H
H
H
CH
2
OH
HO
OH
O
O
OH
HO
CH
2
OH
H
H
H
H
O
H
H
O
H
H
H
H
CH
2
OH
HO
OH
O
Tu cng thuc ta thy: chi c gc D-glucozo o du mach l c nhm OH
semiaxetal tu do, c nghia l c u hng trm gc D-glucozo moi c mt gc D-
glucozo c nhm OH semiaxetal tu do, diu d giai thch tinh bt khng c tnh
khu.
Cc dai phn tu amilozo c cu tao hnh xon c v mi vng xon gm 6
gc D-glucozo. Cc vng xon duoc duy tr voi nhau nho lin kt hidro giua
cc nhm OH cua C
2
& C
6
cua vng xon bn canh. Bn trong duong knh cua
vng xon = 0,5A
o
, do d c th dua cc phn tu khc vo thnh hop cht boc,
th du hop cht boc giua it voi amilozo: it chui vo bn trong vng xon cua
amilozo cch du nhau 3,06A
o
, do d l m thay di nng luong hp th u nh
sng, nn c mu.
-Cau tao cua amilopectin :
Khi luong phn tu cua amilppectin khoang 1 000 000 dn 6 000 000 dvC
(n = 6000-36000), nghia l lon hon nhiu ln so voi amilozo. Diu khc nhau
co ban trong cu tao giua amilozo v amilopectin l amipectin c cu tao phn
nhnh nhiu tr ong khi amilozo chu yu c cu t ao thng, mi mach nhnh gm
-26 gc D-glucozo; cc gc D-glucozo lin kt voi nhau bng lin kt -1,4-
glucozit, cn giua cc mach ni voi nhau bng lin kt -1,6-glucozit:
O
HO
OH
CH
2
OH
H
H
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
O
O
O
O
O
OH
HO
OH
CH
2
OH
H
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
O
_
glucoz

glucoz
_

O
HO
OH
CH
2
OH
H
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
OH
O
O
O
O
O
O
HO
OH
CH
2
H
H
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
O

_
glucoz
_
glucoz
lie n ke t 1,4

glucozit
1
4 1
6
glucozit 1,6 lie n ke t
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 182
CH
2
OH
O
OH
HO
CH
2
OH
H
H
H
H
O
H
H
O
H
H
H
H
CH
2
OH
HO
O
OH
O
O
OH
HO
H
H
H
H
O
H
H
O
H
H
H
H
CH
2
OH
HO
OH
O
O
OH
HO
CH
2
H
H
H
H
O
H
H
O
H
H
H
H
CH
2
OH
HO
O
OH
O
-Glicogen ( tinh bot dong vat ) :
Glicozen l polisaccarit du tru cua co th dng vt, thuong tp trung o gan
(20%) v cc co bp (4%). Glicogen duoc goi l tinh bt dng vt.
Glicogen l cht bt mu trng, d tan trong nuoc cho dung dich mo duc,
nhung khng tao duoc th nh h, dung dich ny c nng sut quay cuc []
D
=
+196
o
, t c dung voi it cho mu nu do. Khi thuy phn glicogen bng axit hay
bng men, cui cng cho D-glucozo. Kh i luong cua glicogen khoang 1 000
000. Cu t ao cua glicogen tuong tu nhu amilopectin v dc dim phn nhnh,
nhung o gicogen phn nhnh nhiu hon v cc mach ngn hon.
-Su chuyn ha c ua tinh b ot trong c o th nguoi: Khi di qua ming, tinh bt
bi thuy phn nho men amilaza c trong nuoc bot. Su thuy phn tip tuc xay ra
nho men mantaza c trong rut, cho san phm cui cng lglucozo. Glucozo
duoc hp t hu tr uc ti p vo mu, qua mao tr ang rut r i theo mu v gan. Tu
gan glucoz o duoc ph n phi di cc m trong co th. T ai cc t bo v m
glucozo duoc oxi ha chm bin thnh kh cacbonic v hoi nuoc dng thoi giai
phng giai phng nng luong cho co th hoat dng:
4 3 4 2 1 4 4 3 4 4 2 1
Glucoz bot Tinh
Men
6 12 6 2 5 10 6
) ( O H nC O nH O H C
n
+
+
2 6 12 6
6O O H C
43 4 2 1
Glucoz
6CO
2
+ 6H
2
O + Q
Phn glucozo cn du o trong gan duoc tng hop lai thnh mt loai gluxit c
khi luong phn tu lon goi l glicogen (ha y cn goi l tinh bot dong vat ).
Glicogen duoc du tru trong gan, khi cn lai thuy phn thnh glucozo v chuyn
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 183
toi cc m trong co th.
II-XENLULOZO
12.9.1-Trng thi t nhin:
Cng thuc phn tu cua xenlulozo ging cng thuc phn tu cua tinh bt:
(C
6
H
10
O
5
)
n
, khi l uong phn t u vo khoang 1 000 000-2 000 000 (n = 6000-
12000) .
Xenlulozo thuc loai polisaccarit-hop cht cao phn tu khng c tnh cht
duong, l t hnh phn chnh cua t bo thuc vt; xenlulozo lm cho cc m thuc
vt c t nh bn co hoc, c tnh dn hi v t ao thnh b xuong cho tt ca cc
loai cy. Xenlulozo duoc hnh thnh trong cy nho qa trnh quang hop.
Xenlulozo trong tu nhin o duoi dang soi v khng hon ton nguyn cht,
n thuong lin kt ch t ch voi nhiu thnh phn khc. B ng duoc coi l
xenlulozo gn nguyn cht nht c chua khoang 95% xenlulozo. G chua 40-
60% xenlulozo. Mun duoc xenlulozo nguyn cht: rua bng bng dung dich
x phng, sa u d rua b ng dung dich NaOH, r i ty bng dung dich natri
hipoclorit (NaClO).
12.9.2-Cu to cua xenlulozo:
Tu cc du kin thuc nghim cho bit xenlulozo gm nhung dai phn tu hnh
soi cu t ao boi cc gc D-glucopirano, lin kt voi nhau bng cc lin kt -
1,4-glucozit:
4 1
-1,4-glucozit lie n ke t

glucoz
_
O
HO
OH
CH
2
OH
H
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
O
O
O
O
O
HO
OH
CH
2
OH
H
H
H
H
H
H
H
H
CH
2
OH
OH
HO
O
_
glucoz
_
glucoz
n
_
2
2
_
glucoz
HO
OH
Nu xt toi cu dang cua cc vng D-glucopirano lin kt voi nhau bng
lin kt -1,4-glucozit c th biu din:
O
H
O
H
H
H
H
CH
2
OH
HO
HO
HO
HO
CH
2
OH
H
H
H
H
O
H
O
O
H
O
H
H
H
H
CH
2
OH
HO
HO
HO
HO
CH
2
OH
H
H
H
H
O
H
O
O
HO
HO
CH
2
OH
H
H
H
H
O
H
12.9.3-Tnh cht vt l cua xenlulozo:
-L cht rn, trng, khng mi, khng vi, khng nng chay, bi cacbon ha o
nhit d cao khi khng c khng kh.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 184
-Xenlulozo khng tan trong nuoc l do su hnh thnh mt s lon lin kt
hidro giua cc dai phn tu xenlulozo.
-Tnh bn co hoc cao l dc tnh chu yu cua cc soi xenlulozo, nho d n
l nguyn liu cho cng nghip dt. Tnh bn co hoc cua xenlulozo l do d di
lon cua dai phn t u v huong song song cua chng. C c dai phn tu lin kt
voi nhau t rong cc soi trong khu vuc huong song song bng cc lin kt hidro
giua cc nhm OH. Cc lin kt ny mc d yu, nhung s luong rt l on lm
cho luc tuong tc tng hop manh.
-Xenlulozo khng tan trong trong cc dung mi nhu ete, ruou, benzen ...
trong diu kin thuong n kh bn voi dung dich kim long, dung dich axit
long v cc cht oxi ha yu.
Xelulozo tan duoc trong dung dich Cu(OH)
2
+ NH
4
OH dc (dung dich
Schweitzer - thuong goi l dung dich Svayde), ta n trong H
2
SO
4
dc trn 72%,
trong HCl dc c mt ZnCl
2
. Dung dich xenlulozo trong nuoc Schweitzer bi kt
tua khi cho axit vo. Dung dich xenlulozo trong axit dc cung bi kt tua khi cho
thm nuoc. Kt t ua t ao thnh tu dung dich axit bi it nhum mu xanh. Nguoi
ta loi dung tnh cht ny d pht hin xelulozo.
12.9.4-Tnh cht ha hc cua xenlulozo:
Cng thuc phn tu cua xenlulozo c th vit:
n
OH
OH
OH
(C
6
H
7
O
2
)
hay
n
[C
6
H
7
O
2
(OH)
3
]
-Phan ung thuy phn :
Dun nng xenlulozo trong dung dich axit v co long s thu duoc dung dich
glucozo:
4 3 4 2 1 4 3 4 2 1
Glucoz Xenluloz
H
6 12 6 2 5 10 6
) ( O H nC O nH O H C
n
+
+
-Xenlulozo bi tc d ung cua cc loai vi khu an khc nhau: c vi khun phn
huy xenlulozo thnh H
2
O + CO
2
; cung c vi khun phn huy xenlulozo trong
diu kin ym kh thnh CH
4
. G bi muc nt , mi, mot .. . du do cc men cua
cc vi khun.
-Tc d ung c ua cc chat oxi ha : Tc nh n oxi ha nh ozon (O
3
), peoxit
hidro (H
2
O
2
), natri hipoclorit (Na ClO )... c th oxi ha xe nlulozo thnh hn
hop phuc t ap cc san phm goi l oxi xe nlulozo . Sau khi bi oxi ha, tnh bn
cua xenlulozo bi giam. Th du: vai bng bi ty trng bng nuoc javen s mau
rch hon.
-Tc dung cua kim: Xenlulozo bi tc dung cua kim dc tao thnh san phm
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 185
tuong tu cc ancolat goi l xenlulo-kim:
4 4 4 4 3 4 4 4 4 2 1 4 4 4 3 4 4 4 2 1
kiem - Xenlulo
Xenluloz
n n
ONa OH O H C nNaOH OH O H C )) ( ) ( ( ) ) ( (
2 2 7 6 3 2 7 6
+ + n H
2
O
Xenlulo-kim d bi thuy phn tro lai xenlulozo duoi dang hidrat xenlulo,
dang ny ging xenlulozo v thnh phn ha hoc nhung ho nuoc hon v t bn
hon.
San xuat to visco:
4 4 4 4 3 4 4 4 4 2 1 4 4 4 3 4 4 4 2 1
kiem - Xenlulo
Xenluloz
n n
ONa OH O H C nNaOH OH O H C )) ( ) ( ( ) ) ( (
2 2 7 6 3 2 7 6
+ + n H
2
O
[C
6
H
7
O
2
(OH)
2
ONa]
n
xenlulo
_
kie m
+
nCS
2
O
C S
SNa
C
6
H
7
O
2
(OH)
2
n
xentogenat xenlulo
Xentogenat xenlulo trong kim thnh mt dung dich rt nhot goi l visco.
Cho dung dich visco qua c c l nho ngm trong dung dich H
2
SO
4
, cc tia
xentogenat xenlulozo di vo dung dich axit bi thuy phn thnh hidrat xenlulo,
thuong goi l to visco:
n
[C
6
H
7
O
2
(OH)
3
]
O
C S
SNa
C
6
H
7
O
2
(OH)
2
n
xentogenat xenlulo
+
n
2
H
2
SO
4
_
+
n
_
2
Na
2
SO
4
+
nCS
2
hidrat xenlulo
( t visco )
-Tc dung voi dung dich nuoc Schweitzer (Cu(OH)
2
+ NH
4
OH):
Xenlulozo tc dung voi dung dich nuoc Schweitzer tao thnh mt dung dich
nhot. Cho dung dich nhot d di qua cc l nho ngm trong nuoc th phuc cht
cua xenlulozo voi [Cu(NH
3
)
4
](OH)
2
s b i th uy phn tro l ai th nh hidrat
xenlulozo, loai ny thuong goi l to dng-amoniac.
-Tc dung voi anhidrit axetic:
Xenlulozo c th bi este ha khi tc dung voi anhidrit axetic c mt cua
H
2
SO
4
lm xc tc tao thnh mono, di, triaxetat xenlulozo :
+
4 2
2 3 3 2 7 6
) ( 2 ) ) ( (
SO H
n
O CO CH n OH O H C
4 4 3 4 4 2 1 4 4 4 3 4 4 4 2 1
axetic Anhidrit Xenluloz
4 4 3 4 4 2 1 4 4 4 4 4 3 4 4 4 4 4 2 1
axetic Axit diaxetat xenluloz
COOH nCH OCOCH OH O H C
n 3 2 3 2 7 6
2 ) ) )( ( ( +
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 186
+
4 2
2 3 3 2 7 6
) ( 3 ) ) ( (
SO H
n
O CO CH n OH O H C
4 4 3 4 4 2 1 4 4 4 3 4 4 4 2 1
axetic Anhidrit Xenluloz
4 4 3 4 4 2 1 4 4 4 4 3 4 4 4 4 2 1
axetic Axit triaxetat xenluloz
COOH nCH OCOCH O H C
n 3 3 3 2 7 6
3 ) ) ( ( +
Trong cng nghip thuong dng loai xenlulozo diaxetat v triaxetat lm to
nhn tao v ch tao phim khng chy. Xenlulozo diaxetat t an trong axeton, cn
xenlulozo triaxetat tan trong metylen clorua (CH
2
Cl
2
). Mun san xut to axetat
nguoi ta cho dung dich xenlulozo diaxetat trong axeton di qua nhung l nho
vo mt bu ng khng kh nng, ax eton bay hoi cn lai to diaxetat. To axetat
bn v dep hon to visco v to dng-amoniac, nhung gi thnh cao.
-Tc dung voi axit nitric:
xenlulozo c th nitrat ha bng hn hop HNO
3
+ H
2
SO
4
dc tao thnh hn
hop xenlulozo mono, di, trinitrat (cung thuong goi lnitroxenlulozo):
O nH
n
ONO OH O H C
SO H
nHNO
n
OH O H C
2
))
2
(
2
) (
2 7 6
(
4 2
3
)
3
) (
2 7 6
( + +
4 4 4 4 3 4 4 4 4 2 1 3 2 1 4 4 4 3 4 4 4 2 1
mononitrat Xenluloz nitric Axit Xenluloz
+
4 2
3 3 2 7 6
2 ) ) ( (
SO H
n
nHNO OH O H C
43 4 2 1 4 4 4 3 4 4 4 2 1
nitric Axit Xenluloz
O nH ONO OH O H C
n 2 2 2 2 7 6
2 ) ) )( ( ( +
4 4 4 4 4 3 4 4 4 4 4 2 1
dinitrat Xenluloz
O nH
n
ONO O H C
SO H
nHNO
n
OH O H C
2
3 )
3
)
2
(
2 7 6
(
4 2
3
3 )
3
) (
2 7 6
( + +
4 4 4 3 4 4 4 2 1 43 4 2 1 4 4 4 3 4 4 4 2 1
trinitrat Xenluloz nitric Axit Xenluloz
-Hn hop xenlulozo nitrat trong d ty l nito kh lon (12-13%) (phn lon l
xenlulozo trinitrat) goi l piroxilin. Piroxilin c b ngoi khng khc xenlulozo,
nhung rt d chy, chy manh, v nu dng mt t funminat thuy ngn lm khoi
mo khi dt th piroxilin n manh. V vy piroxilin dng lm cht n cho bom,
mn, luu dan, thuc sng khng khi.
Duoi tc dung cua nhit, su phn huy nitrat xenlulozo giai phng ra mt
luong nhit l on khng cn su tham gia cua oxi khng kh v tao thnh mt th
tch kh rt lon, chng han khi lm n piroxilin:

No
trinitrat Xenluloz
4 4 4 4 3 4 4 4 4 2 1
n
ONO O H C ) ) ( (
3 2 2 7 6
6nCO
2
+ 6nCO + 3nN
2
+ 3nH
2
+ 4nH
2
O
-Hn hop nitrat xenlulozoc ti l nito t hon (khoang 11-12%) tuc phn lon
l mono v dinitrat xenlulozo goi l clxilin. Dung dich clxilin trong ete +
ruou goi l clding. Mt khi luong lon clxin dng ch nhua xelulit, son,
phim anh,.... Nh ua xenl ulit duoc ha deo nho campho (long no) dng san
xut bng bn, d choi tre em. Nhua xelulit c nhuoc dim l d bt lua bc
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 187
chy.
Chuong 13
AMINOAXIT & PROTIT
A-AMINOAXIT
13.1-Khi nim, cng thc cu to v danh php:
-Khi ni m: Aminoaxit thuoc loai hop chat hu co tap chuc, trong phn tu
c mt dong t hoi 2 nhm c huc: nhm amino (-NH
2
) v nhm cacboxyl (-
COOH).
-Cng thuc cau tao v danh php:
CH
3
-CH-C
O
OH
NH
2
NH
2
OH
O
CH
2
-C
Glixin
Alanin
CH
3
CH
3
CH-CH-COOH
NH
2
NH
2
CH-CH
2
-CH-COOH
CH
3
CH
3
NH
2
CH-CH-COOH
CH
3
CH
3
-CH
2
L(+)Valin
L(+)Leuxin
L(+)isoleuxin
axit L(+)glutamic
axit L(+)Asparaginic
HOOC-CH
2
-CH
2
-CH-COOH
NH
2
NH
2
HOOC-CH
2
-CH-COOH
HO-CH
2
-CH-COOH
NH
2
NH
2
CH
3
-CH-CH-COOH
L(+)Xerin
L(-)Treonin
OH
L(-)Tironin
CH
2
-CH-COOH
NH
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 188
NH
2
L(-)Xitin
axit L(+)Metionin
HOOC-CH-CH
2
CH
2
-CH-COOH
NH
2
NH
2
CH
3
SCH
2
-CH
2
-CH-COOH
S
S
H
2
N-(CH
2
)
2
-CH-COOH
NH
2
Ocnintin L(+)Lizin
NH
2
H
2
N-(CH
2
)
3
-CH-COOH
H
H
2
C
H
2
C
H
L(-)prolin L- -hidroxiprolin

CH-COOH
CH
2
HO-HC
N
CH-COOH
CH
2
H
2
C
N
L(-)Triptophan
H
N
L(-)Hitidin
H
2
C CH
CH-CH
2
-CH-COOH H
2
C
N
H
NH
2
NH
2
CH
2
-CH-COOH
COOH
NH
2
NH
2
COOH
NH
2
COOH
axit p-aminobenzoic
axit m-aminobenzoic axit antranilic
Cng thuc Tn lich su Tn hop l
H
2
NCH
2
COOH Glixin (glicocon) axit aminoaxetic
CH
3
CHCOOH
NH
2
Alanin
axit -aminoaxetic
NH
2
(CH
3
)
2
CHCHCOOH
L(+)Valin axit
-aminoisovaleric
(CH
3
)
2
CHCH
2
CHCOOH
NH
2
L(-)Leuxin axit
-aminoisocaproic
NH
2
CH
3
CH
2
CH CHCOOH
CH
3
_ L(+)Isoleuxin
axit -amino-
-metylvaleric
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 189
HOOCCH
2
CHCOOH
NH
2
L(+)Asparaginic axit
-aminosucxinic
NH
2
HOOCCH
2
CH
2
CHCOOH
axit L(+)Glutamic axit
-aminoglutaric
H
2
N(CH
2
)
3
CHCOOH
NH
2
L(+)Lizin
axit
,-diaminocaproic
H
2
N(CH
2
)
6
COOH axit
-aminoenantoic
axit
-aminoheptanoic
13.2-Diu ch:
13.2.1-Thuy phn protit bng axit ho}c bng kim: Thuy phn protit s cho
hn hop cc aminoaxit. Dy l co so cua phuong php san xut x du, magi tu
b kh du phong v nguyn liu protit khc.
13.2.2-Di t axit -halogen-cacboxylic:
* Phuong php Pekin: amin ha a xit a xit -halogen-cacboxylic bng NH
3
du
(d trnh tao thnh amin bc hai v amin bc ba) s thu duoc -amino axit:
(D,L alanin)
aminopropionic - axit - brompropionic axit
NH
4
Br
+
CH
3
CHCOOH
NH
2
Br
CH
3
CHCOOH + 2NH
3
* Phuong php Gapriel (1889):
Di tu phtalimit kali v este cua axit -halogen th:
C
O
C
O
NK
+ ClCH
2
COOR
NCH
2
COOR
O
C
O
C
+
KCl
phtalimit kali
C COOH
axit phtalic
glixin
ROH
+
H
2
NCH
2
COOH
+
COOH
HCl
+ H
2
O
NCH
2
COOR
O
C
O
Phuong php ny cho hiu sut cao hon v trnh kha nng tao thnh amin
bc hai, bc ba.
Phi hop 2 phuong php trn, nguoi ta d dua ra mt phuong php kinh
din tng hop ra cht Ocnitin:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 190
CO
CO
NK + Br-CH
2
-CH
2
-CH
2
-Br
KBr
N-CH
2
-CH
2
-CH
2
-Br
CO
CO
1,3-dibrompropan
NCH
2
CH
2
CH
2
CH(COOC
2
H
5
)
2
+ NaBr
CO
CO
CO
CO
NCH
2
CH
2
CH
2
Br + NaCH(COOC
2
H
5
)
2
Br
CO
CO
NCH
2
CH
2
CH
2
C(COOC
2
H
5
)
2
+ HBr
NCH
2
CH
2
CH
2
CH(COOC
2
H
5
)
2
+ Br
2
CO
CO
o
t C
H
+
NCH
2
CH
2
CH
2
C-COOH + 2C
2
H
5
OH + CO
2
CO
CO
Br
Br
CO
CO
NCH
2
CH
2
CH
2
C(COOC
2
H
5
)
2
+ H
2
O
Br
CO
CO
NCH
2
CH
2
CH
2
C-COOH + 3NH
3
NCH
2
CH
2
CH
2
C-COONH
4
+ NH
4
Br
CO
CO
NH
2
NCH
2
CH
2
CH
2
C-COONH
4
+ 2H
2
O + HCl
CO
CO
NH
2
NH
2
COOH
COOH
+ H
2
NCH
2
CH
2
CH
2
C-COOH + NH
4
Cl
Ocnitin
Bng phuong php ny nu thay 1,3-dibrompropan bng 1,4-dibrombutan
ta thu duoc lizin.
13.2.3-Tng hp mt s aminoaxit ring bit:
* Phuong php ankyl ha este aminomalonic, gm nhiu giai doan, nhung rt
thun loi d diu ch axit -monoaminocacboxylic:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 191
COOC
2
H
5
CH
2
COOC
2
H
5
COOC
2
H
5
C=O
COOC
2
H
5
NaNO
2
CH
3
COOH
Zn + CH
3
COOH
COOC
2
H
5
CHOH
COOC
2
H
5
(CH
3
CO)
2
O
COOC
2
H
5
CHNHCOCH
3
COOC
2
H
5
NH
3
+ (CH
3
CO)
2
O
C
2
H
5
ONa
COOC
2
H
5
CHOH
COOC
2
H
5
COOC
2
H
5
Na-C-NHCOCH
3
COOC
2
H
5
+ RBr
COOC
2
H
5
Na-C-NHCOCH
3
COOC
2
H
5
COOC
2
H
5
R-C-NHCOCH
3
COOC
2
H
5
+ H
2
O
COOH
R-C-NH
2
COOH
t C
o
RCHCOOH
NH
2
* Phuong php tng hop di tu andehit hoc xeton phan ung voi HCN v NH
3
:
+Tng hop ra alanin:
CH
3
CH=O
HCN
CH
3
CH
OH
CN
CN
NH
2
CH
3
CH
NH
3
H
2
O
NH
4
Cl
H
2
O+HCl
CH
3
CH
NH
2
COOH
+Tn hop ra axit D,L-methionin:
tiometylpropionic - andehit
CH
3
SCH
2
CH
2
CH=O
metylmecaptan
CH
3
SH +
acrolein
CH
2
=CHCH=O
OH
N CH
3
SCH
2
CH
2
CHC
HCN
+
CH
3
SCH
2
CH
2
CH=O
andehit -tiometylpropionic
- methionin
axit D,L
OH
N CH
3
SCH
2
CH
2
CHC
1
/
amin ho a
2
/
thu y pha n
CH
3
SCH
2
CH
2
CHCOOH
NH
2
+Tng hop ra axit D,L-glutamic:
o
andehit xiano propionic
N O=CHCH
2
CH
2
C
Ni
2
(CO)
8
p
,
t
H
2
+
CO
+
acrilonitrin
N C
_
CH
2
=CH
dinitrin cu a axit aminoglutaric
C N CHCH
2
CH
2
C
N
NH
2
CN
+
O=CHCH
2
CH
2
C
N
andehit xiano propionic NH
2
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 192
dinitrin cu a axit aminoglutaric
C N CHCH
2
CH
2
C
N
NH
2
axit D,L glutamic
NH
2
HOOCCHCH
2
CH
2
COOH
H
H
2
O
+
Hn hop raxemic cua axit D,L-glutamic d duoc tch bit thnh cng voi
qui m cng nghip thnh cc di quang ring bit bng phuong php kt tinh
lin tuc chon loc.
Trong co th nguoi v dng vt, axit glutamic thuc hin nhiu chuc nng
sinh l quan trong, l s an phm co ban cua qa tr nh sinh ha chuyn amin.
Axit glutamic duoc su dung ph bin duoi dang mui mononatri glutamat (bt
ngot) c cng thuc:
NH
2
HOOCCH
2
CH
2
CHCOONa
mononatri glutamat dng lm d gia vi v chua mt s bnh tm thn, th gioi
cung khuyn co rng khng nn qa lam dung, nht l di voi tre em duoi 6
tui. Nguoi ta cung d dng phuong php vi sinh vt d san xut qui m cng
nghip mt s -aminoaxit nhu lizin, axit glutamic. Trong mt s truong hop
nguoi ta phi hop cc phuong php vi sinh vt v phuong php tng hop, lc
du dng phuong php tng hop diu ch cc hn hop raxemic cua aminoaxit,
sau d bng phuong php ln men, dng cc vi khun tiu thu dng phn D,
nguoi ta t hu duoc dng phn L ( nhung dng phn L-aminoaxit moi c gi tri
dinh dung).
* Tng hop cc - v -aminoaxit:
Axit -aminocaproic l nguyn liu quan trong diu ch to tng hop capron,
c th tng hop tu oxim cua xiclohexanon, cht ny khi dun nng voi anhidit
sunfuric trong axit sunfur ic, s xay ra s u chuyn vi Beckmann bin thnh
caprolactam, sau d thuy phn cho axit -aminocaproic:
oxim cu a xiclohexanon
hiroxilamin xiclohexanon
OH N
H
2
NOH +
O
caprolactam
C=O
NH
chuye n v Becmann
oxim cu a xiclohexanon
OH N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 193
NH
C=O
caprolactam
H
2
N(CH
2
)
5
COOH
axit aminocaproic
-
+ H
2
O
HCl
Axit -aminoenantoic l nguyn liu diu ch to tng hop enang, c th diu
ch tu etylen telme ha c mt CCl
4
tao thnh 1,1,1,7-tetracloheptan, sau d
thuy phn v amin ha:
telo me ho a
3
ClCH
2
(CH
2
)
5
CCl
3
CCl
4
+
CH
2
=CH
2
1,1,1,7-tetracloheptan
cloheptanoic -
axit
Cl(CH
2
)
6
COOH
H
2
SO
4
H
2
O +
1,1,1,7-tetracloheptan
ClCH
2
(CH
2
)
5
CCl
3
H
2
N(CH
2
)
6
COOH
axit
- aminoenantoic
2NH
3
+
Cl(CH
2
)
6
COOH
axit
- cloheptanoic
* Diu ch cc amino axit thom:
COOH
NH
2
NH + NaClO + H
2
O
CO
CO
+ NaCl + CO
2
axit antranilic phtalimit
axit m-nitrobenzoic
+ [H]
NO
2
COOH
COOH
NH
2
Sn + HCl
axit m-aminobenzoic
axit p-nitrobenzoic
+ [H]
NO
2
COOH
COOH
NH
2
Sn + HCl
axit p-aminobenzoic
Hoc:
p-toludin
NH
2
CH
3
CH
3
NHCOCH
3
N-axetyl-p-toludin
(CH
3
CO)
2
KMnO
4
axit-p-axetamido
NHCOCH
3
COOH
COOH
NH
2
axit-p-amino
H
2
O
NaOH
benzoic benzoic
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 194
13.3-Tnh cht:
13.3.1-Tnh quang hc:
Tru glixin, tt ca cc -aminoaxit du c chua t nht 1 nguyn tu cacbon
bt di xung.
Cc -aminoaxit thu duoc bng cch thuy phn prott, tr u glixin, du c
tnh quang hoat.
Cu hnh cua tt ca cc -aminoaxit ny du c cu hnh tuong tu voi cu
hnh cua mt trong hai cht chun l L-glixerandhit:
COOH
H
2
N H
R
CH
2
OH
H HO
CH=O
L
-
glixeranehit L
-

-
aminoaxit
Nhu vy tt ca cc -aminoaxit t hin nhin du c cu hnh thuc dy L,
mc d kha nng quay cuc thuc cua chng c th quay phai (+) hoc quay tri
(-).
Th du:
L(+)alanin (CH
3
CH(NH
2
)COOH), L(-)serin (HOCH(NH
2
)COOH) ...
Cc -aminoaxit t ng hop thuong khng c tnh quang hoat do chng l
nhung hn hop raxemic (chua nhung luong bng nhau cua hai di quang D v
L). C th phn tch cc hn hop raxemic thnh nhung dng phn di quang
ring bit bng nhiu phuong php khc nhau.
Th du phuong php tao mui cua cc este cua D,L-aminoaxit voi cc axit
quang hoat. Cc mui ny c tnh tan khc nhau v dua vo d d tch bit
chng ra khoi nhau. Mt s truong hop c th dng phuong php vi sinh vt:
mt s vi sinh vt do nhu cu hoat dng sinh sng c th tiu thu mt loai di
quang cn d lai di quang kia.
13.3.2-Tnh cht din li lung tnh. Dim dng din cua aminoaxit:
Su c mt dng thoi nhm amino v nhm cacboxyl trong phn tu lm cho
aminoaxit c tnh cht l ung tnh: vua c tnh axit, vua c tnh bazo; nghia l
vua c kha nng cho proton, vua c kha nng nhn proton.
Tri voi cc amin hoc axit cacboxylic, aminoaxit l nhung cht kt tinh
khng bay hoi; chng nng chay dng thoi phn huy o nhit d kh cao. Chng
khng tan trong cc dung mi khng phn cuc nhu ete du hoa, benzen, ete
etylic, .. . , nh ung tan nhiu tr ong nuoc. Dung dich cua chng tuong tu dung
dich cc cht c momen lung cuc cao.
Hng s phn li axit di voi nhm cacboxyl v phn li bazo di voi nhm
amino rt nho.
Th du : di voi glixin K
a
= 1,6. 10
-10
v K
b
= 2,5. 10
-12
, t rong khi d da s axit
cacboxylic c K
a
10
-5
v cc amin thng c K
b
10
-4
.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 195
Tt ca nhung tnh cht trn hon ton ph hop voi cu trc ion lung cuc
cua aminoaxit:
ion l ng c c cu a aminoaxit
H
3
N
CH COO
R
R
COOH CH
H
2
N
Hng s K
a
cua aminoaxit thuc cht th hin tnh axit cua ion amoni:
R
COO CH
H
3
N
ion l ng c c cu a aminoaxit
+
H
2
O
R
COO CH
H
2
N
+
H
3
O
=
a
K
]
[H
3
NCHRCOO
]
[ ]
[H
2
NCHRCOO
H
3
O
Hng s K
b
thuc cht th hin tnh bazo cua anion cacboxylat:
HO
+
H
3
N
CH COOH
R
H
2
O
+
ion l ng c c cu a aminoaxit
H
3
N
CH COO
R
=
b
K
]
[H
3
NCHRCOO
]
[ ]
[H
3
NCHRCOOH HO
Nhu vy nhm axit trong cc aminoaxit khng phai l nhm COOH, m l
nhm NH
3
+
, cn nhm bazo khng phai l NH
2
m l COO
-
.
Khi ion lung cuc cua aminoaxit mang nhung luong din tch duong v m
bng nhau chng s trung ha v din. Cc luong din tch ny phu thuc vo
pH cua mi truong. pH cua dung dich m o d tong so din tch duong v m
cua phn t u aminoaxit bng khng, goi l dim dng din cua aminoaxit, k
hiu l pI . Dim dng din cua a minoaxit c mt nhm amino v mt nhm
cacboxyl c tnh axit yu. Khi dng din chay qua dung dich aminoaxit c pH o
dim dng din, ph n tu aminoaxit s dung im khng di chuyn v catt hoc
ant.
O dim dng din, nng d ion lung cuc l cuc dai (pH = pI).
Khi kim ha dung dich aminoaxit, ion lung cuc bin thnh anion
cacboxylat ( pH > pI ); cn khi axit ha, ion lung cuc bin thnh cation amoni
( pH < pI ):
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 196
H
2
O
+
H
2
N
CH COO
R
OH
+
ion l ng c c cu a aminoaxit
H
3
N
CH COO
R
H
2
O +
H
3
N
CH COOH
R
+
ion l ng c c cu a aminoaxit
H
3
N
CH COO
R
H
3
O
Tng hop lai ta c so d h thng cn bng thun nghich sau :
H
3
N
CH COOH
R
H
3
N CH COO
R
R
COO CH
H
2
N
OH
H
OH
H
pH = pI pH < pI
pH > pI
Mi mt aminoaxit duoc dc trung bng mt dai luong pI ring, dai luong
ny duoc xc dinh boi cu tao gc R.
Ty theo dai luong pI, cc aminoaxit duoc chia thnh cc nhm: trung tnh,
axit v bazo:
-Thuong thuong di voi aminoaxit c mt nhm -NH
2
v mt nhm -COOH,
pI trong m6i truong trung tnh.
Th du : glixin , alanin c pI = 6,1.
-Aminoaxit c 1 nhm NH
2
v 2 nhm COOH, pI trong mi truong axit.
Th du: axit asparaginic (HOOCCH
2
CH(NH
2
)COOH) pI = 3,0.
axit glutamic (HOOCCH
2
CH
2
(NH
2
)COOH) c pI = 3,2.
-Aminoaxit c 2 nhm NH
2
v 1 nhm COOH, pI trong mi truong bazo.
Th du: lizin ( H
2
N(CH
2
)
4
CH(NH
2
)COOH ) c pI = 9,7.
O dim dng din d tan cua aminoaxit l cuc tiu. Tnh cht ny c th
dng d xc dinh dim dng din. Mun vy cn v duong cong v d tan cua
aminoaxit trong cc dung dich axit v kim o cc pH khc nhau. Giao dim cua
hai duong cong ny tuong ung voi dim dng din.
13.3.3-Tc dng cua nhit:
-Khi dun nng, cc -aminoaxit s tuong tc hai phn tu thnh hop cht vng
c 2 lin kt amit:
Th du:
o
H
2
O
+
CH
2
COOH
NH
2
HOOC CH
2
NH
2
+
t
CH
2
NH CH
2
NH C
C
O
O
glixin glixin
dixetopiperazin
-Di voi cc -aminoaxit khi bi dun nng thnh cc axit ,-etylenic:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 197
o
CH COOH
NH
2
R
CH
H
t
CH
R
COOH CH
+
NH
3


axit
,
- etylenic
-Di voi , , -aminoaxit, duoi tc dung cua nhit d, s khp vng trong mt
phn tu tao thnh amit ni hay vng lactam:
Th du:

o
t C
butirolactam
NH
C=O
Axit -aminobutiric
OH
NH
2
CH
2
CH
2
CH
2
C=O
+ H
2
O
13.3.4-Cc phan ng cua nhm cacboxyl :
-Tao muoi voi cc bazo:
-Tc dung voi bazo manh:
glixin
+
NH
2
COOH CH
2
NaOH
CH
2
COONa
NH
2
+
H
2
O
-Tao mui phuc ni voi cation kim loai nng. Cc mui phuc ny rt bn v
rt kh tan.
Th du: glixin c th tao mui phuc ni cua dng c mu xanh thm khng bi
kim phn huy, m chi bi phn huy boi H
2
S:
CH
2
CH
2
NH
2
H
2
N
OOC
COO
Cu
-Tao este voi ancol:
Aminoaxit tc dung voi ancol nhu metanol, etanol c mt cua clorua hidro
s tao thnh cc este cua aminoaxit duoi dang clohidrat.
Th du:
H
2
NCH
2
COOH
+
C
2
H
5
OH
+
HCl
Cl [H
3
NCH
2
COOC
2
H
5
]+
H
2
O
-Tao clorua axit voi PCl
5
:
H
2
N CH COOH
R
+
PCl
5
R
COCl CH H
3
N
Cl [ ] +
POCl
3
-Phan ung dcacboxyl ha:
O trong co th cc aminoaxit c th bi dcacboxyl ha duoi tc dung cua
men cacboxila tao thnh amin.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 198
Th du:
men
CH
3
CHCOOH CH
3
CH
2
NH
2
+ CO
2
NH
2
alanin
etylamin
13.3.5-Cc phan ng cua nhm amino:
-Tao muoi voi cc axit:
SO
4
2
]
[
H
3
N CH COOH
R
H
2
SO
4
+
R
COOH CH H
2
N 2
-Phan ung voi axit nitro:
H
2
N CH COOH
+ COOH CH
HNO
2
HO
+
N
2
+
H
2
O
CH
3
CH
3
alanin
axit lactic
Dua trn phan ung ny c th dinh luong nhm NH
2
: nito giai phng ra
duoc xc dinh bng phuong php th tch.
-Phan ung axyl ha:
COONa CH
2
H
2
N
+
CH
3
COCl CH
3
CO
HN
CH
2
COOH
+
NaCl
Nho phan ung ny, c th loai tru cc cht dc d duoc hp thu vo mu.
Th du: Trong co th axit benzoic l cht dc s kt hop voi glixin thnh axit
hippuric:
C
6
H
5
COOH
+
H
2
NCH
2
COOH
C
6
H
5
CONHCH
2
COOH +
H
2
O
axit benzoic glixin
axit hippuric
axit hippuric s theo nuoc tiu thai ra ngoi.
-Phan ung ngung tu voi andehit:
Aminoaxit d dng tc dung voi andehit tao thnh dn xut ankyliden:
HCH=O + H
2
NCH
2
COOH CH
2
=N-CH
2
COOH + H
2
O
-Phan ung damin ha:
axit piruric
alanin
NH
3
+
CH
3
CCOOH
O
CH
3
CHCOOH
NH
2
[O]
+
anehit axetic
CO
2
+
CH
3
CH=O
CH
3
CCOOH
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 199
-Phan ung voi su quay cau hnh Vanden:
Khi thay nhm ni voi nguyn tu cacbon bt di xung cua aminoaxit thuong
xay ra su quay cu hnh. Th du chu trnh chuyn ha L(+)Alanin:
Nguoi ta thy trong chu trnh trn su quay cu hnh xay ra o giai doan tc
dung giua NH
3
v dn xut halogen cua axit propionic. Nhu vy khng nn cho
rng su q uay cu hn h xay ra o g iai doan lm di du quay cuc (tuc l
(+)alanin axit (-)- -brompropionic), v rng cc hop cht c cu hnh ging
nhau khng nht thi t phai c cng du quay cuc. Su bao tan cu hnh trong
phan ung giua L(+ )alanin v nitrozylbromua (NOBr) c th do phan ung d
xay ra theo co ch th nucleophin don phn tu S
N
1 hoc do hiu ung k.
Chu trnh trn l mt th du v hin tuong quay cu hnh o nguyn tu cacbon
bt di xung. Hin tuong d goi l hin tng nghch o Vanden.
13.3.6-Cc phan ng mu cua aminoaxit:
-Phan ung voi nihdrin:
Dy l phan ung mu dc trung cho tt ca cc -aminoaxit.
Khi dun nng dung dich -aminoaxit voi ninhidrin s duoc dung dich mu
xanh tm:
-
aminoaxit
C
C
O
O
O
C
+
R CH
NH
2
COOH
ninhirin
2
COOH
H NH
2
CH
3
COOH
H Br
CH
3
COOH
Br H
CH
3
COOH
H
2
N H
CH
3
NOBr
NOBr
L(+)Alanin Axit L(-)- -brompropionic
D(-)Alanin Axit D(+)- -brompropionic

NH
3
NH
3
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 200
H
2
O
+
C
C
O
O
C
C
O
O
C
C
H N=
+
h p cha t co ma u xanh tm
+
RCH=O
+
CO
2
Qa trnh phan ung din ra nhu sau:
H
2
O +
C
C
O
O
C
R
CH NH COOH
COOH
NH
2
CH R
+
O
C
C
O
O
C
ninhirin
C
C
O
O
C
R
CH NH COOH
C
C
O
O
C
H
NH=CHR
+ CO
2
NH=CHR
H
C
O
O
C
C
+ RCH=O
C
C
O
O
C
H
NH
2
N=
H
C
O
O
C
C
H
2
O +
C
O
O
C
C
C
C O
O
C
ninhirin
+
O
C
C
O
O
C
H
NH
2
N= C
O
O
C
C
C
O
O
C
C
C
C
O
O
C
C
C
O
O
C
H
N=
H
+
h p cha t co mau xanh tm
-Phan ung Xantoprotic : Phan ung dc trung cua a minoaxit c chua nhn
benzen trong phn tu -thuc cht l ph an ung nitro ha nhn benzen tao ra hop
cht nitro mu vng.
Th du: tizozin tc dung voi HNO
3
:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 201
OH
CH
2
CHCOOH
tirozin
NH
2
+ HNO
3
NH
2
CH
2
CHCOOH
OH
2
NO
2
O
2
N
+ H
2
O 2
-Phan ung tao sunfua ch mu den: Phan ung dc trung cho cc aminoaxit c
chua l uu huynh trong phn tu. Dun nng dung dich aminoaxit d voi mui ch
trong mi truong kim s cho kt t ua ch sunfua (PbS) mu den. Mui ch tc
dung voi sunfua hidro tu aminoaxit c luu huynh tch ra.
Th du:
t
cac san pham khac +
metionin
H
2
S
NaOH
NH
2
CH
3
SCH
2
CHCOOH
o
H
2
S + NaOH Na
2
S + H
2
O
Pb
2+
+ 2OH
-
Pb(OH)
2
Pb(OH)
2
+ 2 NaOH Na
2
PbO
2
+ H
2
O
Na
2
PbO
2
+ Na
2
S + 2 H
2
O PbS + 4 NaOH
-Phan ung Milong:
Phan ung ny dc trung cho aminoaxit c chua nhm phenol, nhu tirozin.
Dun nng dung dich aminoaxit d voi cc mui nitrat v thuy ngn nitrat, s
xut hin mu hng. Ban cht san phm mu o dy giai thch chua r rng.
B-PEPTIT
13.4.1-D|nh nghia , phn loi v tn gi:
-inh nghia: Peptit ( hay polipeptit ) l nhng hop chat tao thnh tu mot so
goc aminoaxit; cc g oc ny kt hop voi nhau nho cc lin kt peptit (hay lin
kt amit):
NH
O
C
Th du: mt peptit gm 3 gc aminoaxit c cu tao nhu sau:
H
2
N CH C
O
NH
CH
R
R
C
O
NH
CH
R
COOH
lie n ke t peptit hay lie n ke t amit
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 202
-Phn loai : Ty theo s gc aminoaxit trong phn tu , ta c :
-dipeptit : chua 2 gc aminoaxit .
-tripeptit : chua 3 gc aminoaxit .
-tetrapeptit : chua 4 gc aminoaxit ...
Cc peptit mach ho lun lun c nhm NH
2
v COOH o hai du mach.
-Tn goi : Tn goi peptit bao gm tn goi cc thnh phn aminoaxit bt du
tu gc aminoaxit c nhm NH
2
. Dui in cua t n mi gc aminoaxit duoc di
thnh dui il; ch i c tn cua g c aminoaxit du c chua n hm COOH giu
nguyn dui in.
Th du :
leuxin valil
alanil
glixil
-
-
i i
C
4
H
9
C
3
H
7
CH
3
H
2
NCH
2
CONHCHCONHCHCONHCHCOOH
13.4.2-Tnh cht cua cc peptit:
Cc peptit thp l nhung tinh th khng mu, d tan trong nuoc, hu nhu
khng tan trong ruou.
Cung nhu aminoaxit, peptit c tnh cht lung tnh; cho nn duoi tc dung
cua din truong, t y the o pH c ua m i tr ung v dc dim cu tao cua cc
aminoaxit thnh phn, peptit c th di chuyn v catt hay ant.
Cc peptit cung tham gia tt ca cc phan ung dc trung cua nhm amino v
nhm cacboxyl.
Phan ung mu dc trung cua peptit, cung l dc trung cho su c mt cua
nhiu lin kt peptit (-CONH-) l ph an ung biur: dung dich kim long cua
peptit khi tc dung voi dung dich CuSO
4
cho mu xa nh tm hoc do tm (ty
theo s luong cc lin kt pe ptit c trong phn tu). Dipeptit cho mu xanh,
tripeptit cho mu tm, polipeptit cho mu do tm hay do.
Mu cua phan ung biur l do tao thnh hop cht phuc sau:
OC
NH
2
NH
NH
2
Na
OH
NaH
2
N
OH
OC
OH OH
H
2
N
HN
CO
CO
Cu
Cc peptit c th bi thuy phn bng axit hoc bng kim khi dun nng tao
thnh cc aminiaxit .
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 203
C-PROTIT
13.5.1-Phn loi:
Protit chia thnh 2 loai:
-Protit don gian hay protein.
-Protit phuc tap hay proteit.
-Protit don gian l loai protit khi thuy phn dn cng chi cho cc san phm l
cc -aminoaxit.
-Protit ph uc t ap l lo ai pr otit khi thuy phn cho cc san phm ngoi cc
aminoaxit c n c nhung thnh phn khc k hng phai l aminoaxit (nhu l
monosaccarit, H
3
PO
4
, cc bazo l di vng).
13.5.2-Cu to ha hc cua phn tu protit:
-Thuyt cc chuoi polipeptit cua Fischer:
Cc phn tu protein duoc cu tao boi mt hoc nhiu chui polipeptit kt
hop voi nhau.
Thuyt cc chui polipeptit v cu tao cua protit dua trn co so thuc nghim
khi nghin cuu cc tnh cht cua protit:
-Cc polipeptit cao c nhung tnh cht vt l tuong tu tnh cht cua protit:
D l nhung tnh cht lung tnh c th tao mui voi axit v bazo v c th kt
tua khi tc dung voi cc mui v co .v.v...
-Cc polipeptit cung c th bi thuy phn bng axit, bng kim v bng cc
men thch hop cho san phm cui cng l cc aminoaxit.
-Khi thuy phn protit mt cch khng hon ton s thu duoc peptit.
-Cc polipeptit cung nhu protit du cho duoc phan ung biur l phan ung
dc trung cho cc lin kt peptit. Cc protit cho mu tm.
-Thuyt cau trc cc cap cua protit:
Khi nghin cuu v cu trc cua protit, cc nh khoa hoc d d ra khi nim
v cc muc d khc nhau cua cu trc protit: Cau trc cap - cau trc cap II,
cau trc cap III.
* Cau trc cap I:
Cu trc cp I l trnh tu sp xp cua cc gc aminoaxit trn mach
polipeptit nho lin kt peptit. Mi phn tu protit khng nhung c thnh phn
aminoaxit x c dinh, m cn c mt t rt tu xc dinh cua cc gc aminoaxit,
nghia l c mt cu trc cp I xc dinh.
Th du: Tu 20 aminoaxit ta c th tao ra v s cc protit khc nhau. Cc protit
d duoc tao ra c th nh phn aminoaxit ging nhau, nhung cu trc cua chng
khc nhau, do d chuc nng cua chng l khc nhau.
Tu kt qua nghin cuu d d lm sng to mt s vn d:
-V di truyn hoc.
-V tin ha hoc.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 204
-Hiu v giai thch duoc mt s bnh l hoc o nguoi v dng vt bc cao.
* Cau trc cap II:
Cu hnh sinh ra do su xon lai mt phn nho cua mach polipeptit cua mt
phn tu protit goi l cu tc cp II cua protit. Cc cu dang xon duoc duy tr
bn vung nho su hnh thnh mt s lon lin kt hidro N-H ... O=C.
-Cau dang xon : L su xon lai cua cng mot chuoi polipeptit. Trong cu
dang xon , lin kt hidro hnh thnh gia hai mt xch cua cng mot chuoi
polipeptit.
Cu dang xon c t h tao thnh dang xon phai (xon theo chiu kim
dng h) cung nhu dang xon tri (xon theo chiu nguoc kim dng h). Kt
qua nghin cuu cc phn tu protit du tn tai cu dang xon phai.
-Cau dang xon : L su xon lai cua nhiu chuoi polipeptit . Trong cu
dang xon , lin kt hi dro hnh thnh gi a hai hay nhi u chuoi polipeptit
trn hai mt phng khc nhau.
Cc nh khoa hoc cho rng c su chuyn ha thun nghich giua cc dang
xon v . Khi chuyn dang xon thnh dang xon th xay ra su be gy
cc lin kt hidro bn trong ng xon v chng duoc th bng cc lin kt hidro
giua c c chui polipeptit canh nhau. S u co co, du i co c lin quan voi su
chuyn ha thun nghich giua cc dang xon v .
* Cau trc cap III:
C=O
...
H N
N H
...
C=O
...
H N
O=C
cau dang xoan

cau dang xoan
.
.
.
.
.
.
.
.
.
.
.
.
N C
O
H
N C
O
H
H
O
C N
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 205
Cau trc sinh ra do su gap lai cua cc chuoi polipeptit c chua cc cau
dang xon v . D l c u tao khng gian ba chiu dc th di voi mi loai
protit. Cu tr c cp III duoc duy tr, t ao nn su bn vung l do tuong tc cua
cc nhm chua trong cc aminoaxit cua cc chui polipeptit, nghia l tao ra cc
lin kt: lin kt disunfua (-S-S-), lin kt este ( -COOR ), l in kt hidro (-H---
O=C), lin kt a mit (-NH- CO ), tr ong d lin kt disunfua dng vai tr quan
trong nht.
13.5.3-Tnh cht ha hc cua protit:
-Hnh dang cua phn tu protit:
Protit tn tai duoi 2 dang co ban: dang hnh soi v dang hnh cau.
-Dang hnh s oi : Cc protit hnh soi c th kt hop voi nhau theo chiu di
tao thnh nhung tp hop lon: Protit hnh soi tham gia t ao thnh cc m chng
d nhu da, t c, lng, mng, sung, xuong, cung nhu cc m hoat dng nht cua
co th nhu m co.
-Dang hnh cau trn: Cc protit dang hnh cu trn chu yu l nhung protit
tan trong nuoc hoc trong dung dich mui long.
Th d u: anbumin v glbumin cua l ng trng trung, c ua huy t tha nh,
hmglbin cua mu, men cua cc dich tiu ha nhu pepsin. Trong mt s diu
kin nht dinh, nhu dun nng, hoc duoi tc dung cua kim, axit, ruou v mt
s tc nhn khc, protit dang hnh cu c th chuyn thnh dang hnh soi.
-khoi luong phn tu protit:
Protit thuc loai hop cht cao phn tu thin nhin.
Phn tu protit gm mt s lon cc gc aminoaxit kt hop lai, do d phn tu
luong cua chng rt cao.
-Trang thi keo c ua dung d ich protit : Cc protit t ao thnh dung dich keo
(trong khi cc phn tu nho khi tan trong nuoc tao thnh dung dich thuc). Trong
dung dich ny, c c phn t u protit ph n tn trong dung mi. Do d dung dich
protit g m hai tuong khng tan ln vo nhau, mt t uong l dung mi goi l
tuong phn tn, tuong thu hai l protit goi l tuong bi phn tn.
-Tnh chat din ha hoc cua phn tu protit:
Cung ging nhu aminoaxit, protit c tnh cht din li lung tnh. Tuy nhin
khc aminoaxit, pr otit chua nhung luong nhm -COOH, -NH
2
tu do lon hon.
Ty theo pH c ua mi truong, din tch cua c c phn tu protit cung thay di.
Khi tong din tch cua protit bng khng th pH lc d l dim dng din cua
protit. O t ai dim dng din, c c ti u phn protit dung im. Trong din truong
khng di, khi thm axit th protit s tng din tch duong, cc tiu phn protit
tch din duong s di chuyn v catt; cn khi thm kim th protit s tng din
tch m, cc tu phn protit tch din m s di chuyn v ant.
Su di chuyn cc tiu phn protit trong din truong goi l hin tuong din
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 206
di. P huong php din di cho php xc dinh dim dng din cua pr otit, nho
phuong php ny c th cho php tch bit cc hn hop protit.
-Tnh tan cua protit:
Protit c th ha tan trong nhiu dung mi khc nhau: c mt s protit tan
trong nuoc, mt s chi tan trong nhung dung dich mui c nng d xc dinh,
mt s tan trong ruou, c mt s protit hon ton khng tan.
Tnh tan cua protit phu thuc thnh phn aminoaxit v trt tu kt hop cua
cc aminoaxit t rong phn tu protit. Tnh tan cua protit cn phu thuc vo dung
mi. O dim dng din, c c protit hu nhu hon ton khng tan, trong truong
hop ny, khi khi thm axit hoc kim c th lm cho protit tan.
O nhit d thp, tnh tan cua protit giam di.
-Su bin tnh cua protit:
Protit thuc loai cht rt khng bn. Rt nhiu yu t bn ngoi c th lm
thay di nhung tnh cht co ban cua chng.
-Khi luc trung, protit cua trung dng dc lai - su bin tnh d c tnh bat
thuan nghich v khi lm lanh n khng tro lai t rang thi long ban du. Cho tc
dung voi kim, pr otit dng dc d lai tan ra, nhung dung dich d han ton
khc protit cua trung lc ban du.
-Ngoi tc dung cua nhit, cn c tc dung cua tia tu ngoai, cua siu m,
cua su dung dng (nhu lc, khuy), cua axit, cua kim, cua cc mui kim loai
nng v cua nhiu tc nhn khc c t h lm thay di tnh cht t u nhin ban du
cua protit. Hin t uong d goi l su bi n tnh c ua protit . Su bi n t nh gy r a
nhung bin di su sc trong cc phn t u protit v lm giam rt nhiu v c khi
lm mt hon t on hoat tnh sinh l cua pr otit. Su bin tnh d ph v cu tr c
cp II, c p III cua c c phn tu protit. Su bin tnh lm dut cc li n kt hidro
trong cc cu dang xon , trong cu trc cp II, dng thoi km theo su giai
phng cc nhm -SH, -S-S -, -C
6
H
4
-OH, v. v....V vy cc protit bin tnh cho
nhung phan ung mu xm hon dc trung cho cc nhm trn.
-Su kt tua cua protit:
Su bin tnh thuong km theo hin tuong kt tua. Trong truong hop ny su
kt t ua t huc dang bt thun nghich. Bi n tnh v kt tua bt thun nghich c
th xay ra duoi tc dung cua cc mui kim loai nng (Fe , Cu , P b , Hg , A g ,
v.v...), c ung c th xay ra duoi tc dung cua nhiu l oai axit, bazo, cung nhu
nhiu tc nhn khc nhu men, phnol, fomandehit .v.v ....
Su kt tua thun nghich cua protit xay ra khi thm vo dung dich protit
nhung luong lon mui trung tnh nhu Na
2
SO
4
, NH
4
SO
4
, v k t t ua bng mui
xay ra tt nht o dim dng din cua protit.
-Nuclprtit v axit nuclic:
Nuclprtit thuc loai protit phuc tap l thnh phn chnh cua hat nhn
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 207
cc t bo sng. Nuclprtit cu tao boi mt phn l prtin v mt phn phi
protit l ax it n ucleic. Axit nucl ic c vai tr v cng quan trong di voi su
sng: chng dam nhim chuc nng duy tr v chuyn giao nhung thng tin di
truyn v dng vai tr quan trong trong qu trnh sinh ha tng hop protit.
Axit nucleic (k hiu l AN) cung l hop cht cao phn tu, khi thuy phn
thu duoc cc san phm l cc mononucltit. Nhu vy axit nuclic duoc coi l
mt polinucltit.
axit nucle ic
H
2
O
mononucle o tit
Mononucltit lai c th thuy phn dn cng thnh 3 loai san phm: axit
phtphoric, duong pentzo v mt bazo di vng.
H
2
O
mononucle o tit H
3
PO
4
+ pento z + baz d vo ng
C 2 loai duong petzo c th tham gia tao thnh axit nuclic, d l D-rib
v D-dezxirib:
O
HOCH
2
1
2 3
4
5

-D-ribo
-D-2-dezoxiribo

5
4
3 2
1
HOCH
2 O
Ty theo cu tao cua petzo c trong thnh phn AN nguoi ta chia thnh 2
loai AN:
-Axit ribnuclic (k hiu ARN).
-Axit dzxiribnuclic (k hiu l ADN).
C 2 loai di vng tham gia tao thnh AN: bazo purin v bazo pirimidin.
Tuy nhin khng phai chnh purin v pirimidin m l cc dn xut cua chng:
N
N
N
NH
purin
NH
N
N
N NH
N
HN
NH
2
O
H
2
N
ae nin
guanin
xito zin
timin
uraxin pirimiin
O
O
NH
2
O
H
3
C
O
O
NH
N
NH
NH
NH
NH
N
N
Duong pentzo v bazo di vng lin kt voi nhau bng lin kt glucozit giua
C
1
cua pentzo v nguyn tu nito N cua di vng tao thnh cc nuclzit:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 208
O
HOCH
2
1
2 3
4
5
5
4
3 2
1
HOCH
2 O
-D-2-dezoxi-andenezin
-D-2-dezoxi-timidin
NH
2
N
N
N
N
N
NH
O
H
3
C
O

13.5.4-S chuyn ha prottit trong co th:


Trong b my tiu ha nho tc dung cua cc cht men pepxin, protit bi thuy
phn thnh cc aminoaxit. Cc aminoaxit duoc hp thu vo mu qua cc mao
trang rut vo mu chuyn di cc m v cc t bo cua co th.
Mt phn co ban cc aminoaxit d duoc dng d tao ra protit cho co th
nguoi. Phn aminoaxit cn lai bi oxi ha chm d cung cp nng luong cho co
th hoat dng. San phm cui cng cua su oxi ha aminoaxit trong co th l kh
cacbonic, nuoc v amoniac. Amoniac chuyn ha thnh ur ( (H
2
N)
2
C=O ) v
co th thai ur theo duong nuoc tiu ra ngoi.
ANDEHITAXIT V XETOAXIT
1. -andehitaxit :
Axit glioxylic O=HC-COOH : Rt ph bin trong tu nhin, nhiu cht o trang
thi tu do trong mt s qua xanh nhu phc bn tu, nho...
Axit glioxilic thuong duoc diu ch bng cch thuy phn dihalogenaxit (axit
dicloaxetic hoc axit dibromaxetic) bng H
2
O o 140
o
C hoc bng cch khu din
ha axit oxalic voi catot bng ch :
H C
Cl
Cl
COOH
H
2
O
140
o
C
H C
O
COOH
HO C
O
COOH
pdd
catot: Pb
Axit icloaxetic Axit glioxilic Axit oxalic
Axit glioxilic thuc loai cht c kha nng phan ung manh, nhm cacbonyl v
nhm cacboxyl tham gia cc phan ung thng thuong v mt s phan ung dc
trung, nhu tc dung voi kim loai hoat dng, tc dung voi mui cua axit yu, phan
ung voi ruou, phan ung cng HCN, phan ung cng NaHSO
3
, phan ung trng
guong, phan ung voi thuc thu Felinh, dc bit tham gia phan ung Cannizaro...
(P/ Cannizaro)
Axit glioxilic
Kali glicolat Kali oxalat
HOCH
2
COOK + KCOO-COOK
KOH
OH
-
H C
SO
3
Na
OH
COOH
NaHSO
3
O=HC-COOH
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 209
2. -xetoaxit :
Phuong php diu ch :
Di tu clorua axit :
CH
3
COCl
KCl
KCN

CH
3
COCN
HCl
O
2
H

CH
3
COCOOH
Axetyl clorua Axit piruvic
Oxi ha -hidroxiaxit :
C
6
H
5
CHOHCOOH + [O]
4
KMnO
C
6
H
5
COCOOH + H
2
O
C
6
H
5
CH=O +
HCN
C
6
H
5
CHOHCN
+

O
3
H ) 2
4
KMnO ) 1
C
6
H
5
COCOOH
Andehit benzoic Axit benzoylcacboxylic
Axit glixeric khi dun nng voi NaHSO
4
tao thnh axit piruvic :
Axit glixeric Axit piruvic
KHSO
4
COOH
CH
2
OH
CH
OH
t
o
C
H
3
C C-COOH + H
2
O
O
Axit tactric khi dun nng voi NaHSO
4
tao thnh axit piruvic :
H
3
C C-COOH + CO
2
+ H
2
O
O
t
o
C
COOH
CH
2
OH
CH
OH
HOOC
KHSO
4
Axit tactric Axit piruvic
Tnh cht : Nhm cacbonyl cung nhu nhm cacboxyl cua -xetoaxit c th tham
gia tt c cc phn ung dc trung cua nhm ny, nhu tao thnh este, oxim ,
hidrazon, ngung tu andol, cng HCN, cng NaHSO
3
.
Phan ung dc trung cua -xetoaxit l phan ung decacboxyl ha.
Axit pir uvic bi phn huy c mt cua men hoc khi dun nng voi axit H
2
SO
4
long
o 150
o
Cthnh axetandehit v CO
2
:
H
3
C CH=O + CO
2
150
o
C
COOH
H
3
C
O
C
H
2
SO
4
loa ng
Axit piruvic Anehit axetic
Axit pir uvic bi phn huy khi dun nng voi axit H
2
SO
4
dc o 60 - 80
o
C thnh axit
axetic v CO :
H
3
C COOH + CO
60-80
o
C
COOH
H
3
C
O
C
H
2
SO
4
a c
Axit piruvic Axit axetic
Axit piruvic khu dung dich thuc thu Tolen cho phan ung :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 210
[Ag(NH
3
)
2
]
+
[O]
Axit piruvic Axit axetic
COOH
H
3
C
O
C
H
3
C COOH + CO
2
3. -xetoaxit :
+ Diu ch -xetoaxit :
Phan ung ngung tu Claizen :
2CH
3
COOC
2
H
5

ONa
5
H
2
C
CH
3
COCH
2
COOC
2
H
5
+ C
2
H
5
OH
Etyl axetat Etyl Axetoaxetat
2CH
3
CH
2
COOC
2
H
5

ONa
5
H
2
C
CH
3
CH
2
COCH(CH
3
)COOC
2
H
5
+ C
2
H
5
OH
Etyl propionat Etyl -metyl--xetovalerat
C
6
H
5
COOC
2
H
5
+ CH
3
COOC
2
H
5

ONa
5
H
2
C
C
6
H
5
COCH
2
COOC
2
H
5
+ C
2
H
5
OH
Etyl benzoat Etyl axetat Etyl benzoylaxetat
C
2
H
5
OOC-COOC
2
H
5
+ CH
3
COOC
2
H
5

ONa
5
H
2
C
Etyl oxa lat Etyl axetat C
2
H
5
OOC-COCH
2
COOC
2
H
5
+ C
2
H
5
OH
Etyl oxaloaxetat
+ Tnh cht -xetoaxit :
Phan ung decacboxyl ha :
* CH
3
COCH
2
COOH CH
3
COCH
3
+ CO
2
* CH
3
COCH
2
COOC
2
H
5

ONa
5
H
2
C
[CH
3
COCHCOOC
2
H
5
]
-

RX
Etyl axetat
CH
3
COCHRCOOC
2
H
5

NaOH
CH
3
COCHRCOOH
C
o
t
CH
3
COCH
2
R
* CH
3
COCHRCOOC
2
H
5

ONa
5
H
2
C
[CH
3
COCRCOOC
2
H
5
]
-

RX
CH
3
COCR
2
COOC
2
H
5

NaOH
CH
3
COCR
2
COOH
C
o
t
CH
3
COCHR
2
Xeton-enol hin tuong tautome ha o cc este etyl xetoaxeat :
Da ng enol Da ng xeton
CH
3
C CH
2
C OC
3
H
5
OH O
CH
3
C CH
2
C OC
3
H
5
O O
CH
3
C CH
2
C OC
3
H
5
O O
CH
3
C
CH
2
C OC
3
H
5
O O
H
Da ng xeton
Da ng ci s-enol
CH
3
C CH
2
C OC
3
H
5
O O
.
.
.
H
.
.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 211
CH
3
C CH
C OC
3
H
5
+ Br
OH O
Br
CH
3
C CH
2
C OC
3
H
5
+ Br
2
OH O
CH
3
C CH
2
C OC
3
H
5
+ HBr
O O
Br
CH
3
C CH
C OC
3
H
5
+ Br
OH O
Br
H
2
O
CH
3
C
CH
C OH
HOOC
O
CH
3
C CH
2
C OH
HOOC
O OH
H
2
O
CH
3
C CH
2
C OC
3
H
5
NC O OH
HCN
CH
3
C CH
2
C OC
3
H
5
O O
Axit metyl maleic
AXIT HIDROXICACBOXYLIC
I-Diu ch :
1. Thuy phn halogenaxit bng NaOH, Na
2
CO
3
v trong mt s tr ung
hp bng H
2
O :
tic monocloaxe Axit
2
COOH ClCH + H
2
O
glicolic Axit
2
COOH HOCH + HCl
ic clopropion - Axit
3
CHClCOOH CH

+ H
2
O
) propionic hiroxi - Axit (
c lacti Axit
3
CHOHCOOH CH

+ HCl
nic bromsucxi Axit
2
CHBrCOOH HOOCCH + H
2
O
c) oxisucxini (Axit hir
malic Axit
2
CHOHCOOH HOOCCH + HBr
2. Khu cc oxoaxit bng hidro mi sinh (hn hng natri) ho}c bng hidro
phn tu c xc tc Ni :
t axetoaxeta Etyl
5 2 2 3
H COOC COCH CH
+ H
2
Ni
atm 100 , C
o
150

butirat hixi - Etyl
5 2 2 3
H COOC CHOHCH CH

t xetovalera - Etyl
5 2 2 2 3
H COOC ) CH ( CO CH

+ H
2
Ni
atm 100 , C
o
150

erat hiroxival - Etyl
5 2 2 2 3
H COOC ) CH ( CHOH CH

Nguoi ta c th diu ch axit glicolic bng cch khu axit oxalic trong din cuc
ch :
HOOC-COOH + 4[H] HOCH
2
COOH + H
2
O
Axit glicolic duoc dng nhiu trong cng nghip in vai hoa.
3. Tc dng cua aminoaxit vi axit nitro :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 212
Alanin -
2 3
COOH CHNH CH

+ HNO
2

) propionic hiroxi - Axit (
c lacti Axit
3
CHOHCOOH CH

+ N
2
+ H
2
O
4. Thuy phn nitrin cua hidroxiaxit :
* CH
3
CH=O + HCN CH
3
CHOHCN
CH
3
CHOHCN + H
2
O + HCl
) propionic hiroxi - Axit (
c lacti Axit
3
CHOHCOOH CH

+ NH
4
Cl
* HCH=O + HCN HOCH
2
CN
HOCH
2
CN + H
2
O + HCl
c glicoli Axit
2
COOH HOCH + NH
4
Cl
5. Phan ng cng axit HCN vo anken oxit :
CH
2
+ HCN HOCH
2
CH
2
CN HOCH
2
CH
2
COOH
O
CH
2
OH
OH
+ H
2
O
HCl
Etilen oxit Axit -hiroxipropionic
6. Tc dng cua andehit hay xeton vi este -halogenaxit :
Axetton Etyl -hiroxiisovalerat
H
2
O
H
3
C
C
H
3
C
OH
CH
2
COOC
2
H
5
H
3
C
C
H
3
C
OZnBr
CH
2
COOC
2
H
5
Zn (Mg)
BrCH
2
COOC
2
H
5
H
3
C
C=O
H
3
C
Qu trnh phan ung xay ra nhu sau :
C
2
H
5
OOC-CH
2
Br + Zn C
2
H
5
OOC-CH
2
ZnBr
C
2
H
5
OOC-CH
2
ZnBr C
2
H
5
OOC-CH
2

+BrZn
+
H
3
C
C
H
3
C
O
CH
2
COOC
2
H
5
H
3
C
C=O + CH
2
COOC
2
H
5
H
3
C
+ OH
Etyl -hiroxiisovalerat
H
3
C
C
H
3
C
OH
CH
2
COOC
2
H
5
+ H
2
O
H
3
C
C
H
3
C
O
CH
2
COOC
2
H
5
7. Ln men sa chua :
C th ln men saccarozo, glucozo, lactozo tao axit lactic.
Phuong trnh ln men sua c th vit :
HOCH
2
(CHOH)
4
CH=O
acidi lactis Bacillus Men
2CH
3
CHOHCOOH
Glucozo Axit lactic
8. Diu ch axit phenolcacboxylic bng phuong php Konbo - Smit:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 213
H
+
H
+
OH
COOH
OH
CCOOH
Axit salixylic
Axit p-hiroxibenzoic
Natri p-hiroxibenzoat
Natrisalixylat
OH
COONa
OH
COONa
200
o
C, 7 atm
125
o
C, 7 atm
+ CO
2
ONa
Natri phenolat
II. Tnh cht ha hc :
1. Phan ng vi ruu to este (phan ng este ha) :
glicolic Axit
2
COOH HOCH +
etylic Ru
2 3
OH CH CH
glicolat Etyl
5 2 2
H COOC HOCH + H
2
O
2. Phan ng vi anhidrit to este :
glicolic Axit
2
COOH HOCH +
axetic Anhirit
2 3
O ) CO CH (
lic axetoglico Axit
2 3
COOH COOCH CH +
axetic Axit
3
COOH CH
3. Phan ng vi axit halogenhidric d}c :
lactic Axit
3
CHOHCOOH CH + HBr
nic brompropio - Axit
3
CHBrCOOH CH

+ H
2
O
4. Phan ng tch nuc to este vng khi dun nng :
+ H
2
O
O
C
O
CH
3
HC
O
H
3
C
C
O
CH
OH
CH
3
HC
O
C
HO
C
O
H
3
C
OH
CH
OH
+
t
o
C
Axit lactic Lactit
-H
2
O
O
C
O
CH
3
HC
O
H
3
C
C
O
CH
OH
CH
3
HC
O
C
HO
C
O
H
3
C
OH
CH
OH
+
t
o
C
C
O
H
3
C CH
OH
O
C
O
HC CH
3
OH
t
o
C
-H
2
O
-H
2
O -H
2
O
C
O
CH
2
OH
O
C
O
OH
CH
2
t
o
C
Axit glicolic Axit glicolylglicolic glicolit
t
o
C
+
C
O
OH
CH
2
OH OH
CH
2
O
C
HO
O
C
O
CH
2
O
C
O
CH
2
5. Phan ng tch nuc cua -hidroxiaxit to axit ,-khng no :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 214
Axit -hiroxibutiric Axit crotonic
H
+
CH
H
3
C CH
COOH + H
2
O CH
2
H
3
C
OH
CH
COOH
t
o
C
6. Tch nuc cua v -hidroxiaxit to thnh lacton :
C=O
CH
2
CH
2
CH
O
R
H
O
H
+ H
+
C=OH
CH
2
CH
2
CH
O
R
H
O
H
C=O
CH
2
CH
2
CH
O
R
H
OH
C=O
CH
2
CH
2
CH
O
R

-Lacton
+ H
2
O
+ H
+
-Lacton
CH
2
H
O
H
R
O
CH
CH
2
CH
2
C=O
CH
2
H
O
H
R
O
CH
CH
2
CH
2
C=OH
CH
2
OH
H
R
O
CH
CH
2
CH
2
C=O
CH
2
R
O
CH
CH
2
CH
2
C=O

7. -Hidroxiaxit khi dun nng c m}t H


2
SO
4
l ng t o thnh axit fomic v
andehit ho}c xeton :
Axit lactic Anehit axetic Axit fomic
H
+
COOH
H
3
C
OH
CH
t
o
C
H
3
C CH=O + HCOOH
H
+
COOH
H
3
C
OH
C
CH
3
t
o
C
H
3
C C=O + HCOOH
CH
3
Axeton
-Hidroxiaxit khi dun nng c mt H
2
SO
4
dc tao thnh CO (do HCOOH phn
huy)
H
3
C CH=O + CO + H
2
O
t
o
C
COOH
H
3
C
OH
CH
H
2
SO
4
a c
Axit lactic Anehit axetic
Di voi axit glixeric khi dun nng voi NaHSO
4
tao thnh axit piruvic :
H
3
C C-COOH + H
2
O
O
t
o
C
COOH
CH
2
OH
CH
OH
KHSO
4
Axit glixeric Axit piruvic
Di voi axit tactric khi dun nng voi NaHSO
4
tao thnh axit piruvic :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 215
Axit tactric Axit piruvic
KHSO
4
COOH
CH
2
OH
CH
OH
HOOC
t
o
C
H
3
C C-COOH + CO
2
+ H
2
O
O
8. To phc vi cc kim loi :
-Hidroxiaxit tao phuc voi mui Fe
3+
(FeCl
3
) c mu vng xanh :
Va ng xanh
+ 3HCl
CH
3
O
O
CH
3
CH
O=C
CH
3
CH
O
Fe
O
O
C=O
O
C=O
CH
H
H
H
COOH + FeCl
3
3H
3
C
OH
CH
Axit salixylic tc dung voi FeCl
3
cho dung dich mu do-tm dm :
COOH
OH + FeCl
3
COOH
O
Fe
6
3
+ 6H + 3Cl
6
Mui kali natri tactrat, CuSO
4
trong dung dich NaOH duoc goi l dung dich
thuc thu Felinh c mu xanh thm :
Moi du CuSO
4
tc dung voi NaOH tao Cu(OH)
2
:
CuSO
4
+ 2NaOH Cu(OH)
2
+ Na
2
SO
4
Cu(OH)
2
duoc t ao ra tc d ung voi mui kali natri tactrat t ao phuc tan mu
xanh thm bn trong mi truong bazo :
COONa
CHOH
CHOH
COOK
COONa
CHO
CHO
COOK
Cu
COOK
OCH
OCH
COONa
H
H
2
+ Cu(OH)
2
+ 2H
2
O
Dung dch ma u xanh tha m Kali natri tactrat
Thuc thu Felinh tn tai trong mi truong bazo, khng bn trong mi truong
axit :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 216
Axit tactric Dung dch thuo c th Felinh
+ CuCl
2
+ 2NaCl + 2KCl
2
COONa
CHO
CHO
COOK
Cu
COOK
OCH
OCH
COONa
H
H
COOH
CHOH
CHOH
COOH
+ 6HCl
Thuc thu Felinh tc dung voi hop cht huu co chua chuc andehit -CH=O cho
kt tua do gach Cu
2
O :
t
o
C
+ Cu
2
O + RCOONa
2
Kali natri tactrat Dung dch Felinh
+ RCH=O + NaOH + H
2
O
4
COONa
CHO
CHO
COOK
Cu
COOK
OCH
OCH
COONa
H
H
COONa
CHOH
CHOH
COOK
9. Tc dng vi dung d|ch thuc tm :
* Axit lactic bi oxi ha trong mi truong axit tao axit axetic :
5CH
3
CHOHCOOH + 4KMnO
4
+ 6H
2
SO
4

5CH
3
COOH + 5CO
2
+ 4MnSO
4
+ 2K
2
SO
4
+ 11H
2
O
Trong mi truong axit H
2
SO
4
, a xit lact ic moi du b i phn huy tao thnh
andehit ax etic v axit fomic; tip theo andehit axetic v axit fomic bi oxi ha
boi KMnO
4
tao axit axetic v CO
2
.
* Axit lactic bi oxi ha trong mi truong trung tnh tao axit piruvic :
3CH
3
CHOHCOOH + 2KMnO
4

2CH
3
COCOOK + 2MnO
2
+ CH
3
COCOOH + 4H
2
O
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 217
Chuong 14
CC CHT PLIME
14.1-Khi nim:
-plime:
Plime l danh tu dng d chi nhung hop cht c phn tu luong cao (hop
cht ca o phn tu) cu t ao tu nhung don vi mt xch nho don gian ging nhau
lp di lp lai nhiu ln.
Nhng hop chat c khoi luong phn tu rat lon (thuong tu hng ngn dn
hng triu don vi cacbon) do nhiu mt xch lin kt voi nhau duoc lp di lp
lai nhiu lan goi l hop chat cao phn tu hay plime.
Th du:
Plime thin nhin: cao su thin nhin, tinh bt, xenlulozo, to tm .v.v..
Plime t ong h op: cao su bun a, cao su bun a-S, cao su bun a-N, cao su
cloropren, PE, PVA, PP, PS, PVC .v.v...
-Mnme:
Mmnme l da nh tu dng d chi nhung phn tu cua cc loai hop cht c
kha nng tng hop thnh plime. Mi mt xch cua plime c th tuong duong
hoc gn tuong duong voi mnme.
Th du: trong cht plivinil clorua (PVC) : (-CH
2
-CHCl-)
n
, mi don vi mt xch
l -CH
2
-CHCl- tuong duong voi mnme l vinilclorua CH
2
=CHCl. H s n
trong cng thuc cua plime xc dinh s mt xch trong mi phn tu plime goi
l h so trng hop. H s n cng lon th plime c phn tu luong cng cao.
14.2-Cu to v tnh cht chung cua cht polime:
14.2.1-Cu to cua cc cht plime:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 218
-Cau tao mach thng (mach khng phn nhnh):
C nhiu plime m phn tu cua chng l mt chui cc mt xch ni tip
nhau t ao thnh mach cacbon - cacbon thng di nhu soi chi, c ung c nhiu
truong hop mach thng di khng phai chi gm cacbon m c cc nguyn t
khc nhu N, O, c ung c truong hop tr ong mach khng c cacbon nhu cao su
silicon gm c Si v O.
Th du:
-Plitilen (PE): (-CH
2
-CH
2
-)
n
: l san phm trng hop cua etilen.
-Plivinilclorua (PVC) : (-CH
2
-CHCl-)
n
: l s an phm trng hop cua
vinilclorua.
-to nilon 6,6: H-[-NH-(CH
2
)
6
NHCO(CH
2
)
4
CO-]
n
-OH: l s an phm trng
ngung cua hexmetilendiamin v axit adipic.
-Lapsan: HO-(-OC-C
6
H
4
COOCH
2
CH
2
-O-)
n
-H: l s an phm trng ngung
cua axit terephtalic v etilenglicol.
- Si
R
R
O
n
cao su silicon :
-xenlulozo : (C
6
H
10
O
5
)
n
.
- :
po limetil metacrilat
n
CH
2
CH
3
COOCH
3
C
-Cau tao phn nhnh:
C nhiu plime c cu tao phn nhnh nhu thnh phn amilopectin trong
tinh bt, n hu glicgen trong gan. Cn ch l n hung nhnh bn hoc nhm
chua cc mt xch lp di lp lai nhiu ln mt cch du ha khng coi l plime
c cu tao phn nhnh. Th du nhu truong hop cht plimetil metacrilat nhu d
ni o trn thuc loai plime c cu tao mach thng.
-Cau tao mang luoi khng gian:
Nhiu plime do su hnh thnh thm nhung cu ni giua cc chui mach
thng tao ra dang cu t ao mang luoi khng gian ba chiu nhu cao su l uu ha,
nhua phenolfomandhit.
Th d u: Nhua phe nol-fomadhit khi diu ch c du luong fomandehit so voi
phenol s tao thnh plime c cu tao mang luoi khng gian ba chiu:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 219
n
OH
CH
2
CH
2
CH
2
CH
2
OH
CH
2
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
CH
2
OH
CH
2
CH
2
CH
2
CH
2
-Cau tao lap th cua plime mach thng :
-Khi cc nhm th trong mach sp xp hn dn v trt tu ta c dang cu tao
lp th atactic.
Th du: Plistiren (PS) diu ch bng phuong trng hop theo co ch gc tu do
c cu tao lp th atactic
-Khi nhm th lun lun o v mt pha cua mach plime ta c cu tao lp
th diu ha iztactic
Th du: Khi trng hop st iren bng cht xc tc Xiglev s tao thnh plistiren
izotactic.
-Kiu cu tao lp th diu ha syndiatactic. Trong kiu ny, nhm th sp
xp diu ha lu n phin, cu mt mt xch cua nhm th o pha bn ny mach,
lai dn mt xch c nhm th o bn kia mach.
C th biu din cc dang cu tao lp th atactic, izotactic v syndiotactic
nhu sau:
H
H
H
H
H
H
H
H H
H H H
H H H H H H
H
R
R
R
R
R
R
R
H
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
dang cau ta o lap the atactic
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
H
R
R R
R
R
R
R
H
H H H
H H
H
H H H
H H
H
H
H H H
H
H
dang cau ta o lap the ie u ho a izotactic
ho}c c th vit:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 220
H
H
H
H
H
H
H
H H
H H H
H
H H
H H H
H
R
R
R
R
R
R
R
H
C
C
C
C
C
C
C
C
C
C
C
C
C
C
H
da ng ca u tao lap the ieu ho a syniotactic
C u t ao lp t h c ua p lime c anh huong r rt dn tnh tnh cht c ua
plime. Plime atactic c th c dim nng chay thp hon nhiu v c th d
tan trong nhiu loai dung mi hon so voi plime iztactic.
Khi trong mach plime c chua lin kt di th c th xut hin hin tuong
tuong tu dng phn hnh hoc (cis-trans). T rong mach plime c th cc mt
xch vn ging nhau, nhung cu t ao lp th tung nhm mt xch lai lp di l
p lai mt cch khc nhau.
Th du: Di voi plibutadien c th c hai dang cis v trans nhu sau:
da ng cis
H
H
H
H
H
H
CH
2
C C
CH
2
CH
2
C C
CH
2
CH
2
C C
CH
2
CH
2
C C
CH
2
CH
2
C C
CH
2
CH
2
C C
CH
2
H
H
H
H
H
H
da ng trans
14.3-Tnh cht chung cua cc plime:
14.3.1-Tnh cht l hc:
Cc cht plime biu hin nhung dc dim chung v tnh cht l hoc nhu sau
:
-O trang thi nhua deo hoc rn khng bay hoi, khng chung ct duoc.
-Chng khng c dim nng chay xc dinh, m nng chay trong mt khoang
nhit d kh r ng; khi nng chay cho dang cht long c d nhot cao. Mt s
plime khi dun nng th bi phn huy chu khng chuyn thnh trang thi long.
-Da s kh tan trong dung mi, mt s tan trong dung mi nht dinh nhung
d tan rt chm v han ch. Cc dung dich plime c d nhot cao.
-C ti khi lon, da s cch din, cch nhit.
-Nhiu loai plime c tnh bn dn, trong thnh phn cua chng ngoi C, H,
O, cn c cc nguyn t khc nhu Al, Ti, Sn, Fe, Cu ....
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 221
-Cc plime c d bn co hoc cao:
+ Nhiu plime c tnh dn hoi. Bin dang dn hi l mt dc t nh cua cc
cht rn c t h tro lai hnh dang v t h tch ban du khi luc tc dung bn ngoi
thi t c dung. Trong truong hop ny suc ko bn ngoi cn nho hon suc co ni
tai. Nu luc bn ngoi lon hon suc co ni tai, plime bi dut, phn tu bi ph huy
v phn tu plime khng tro lai trang thi cu duoc. Dn hi l dc tnh cua cc
loai cao su tu nhin v tng hop.
+ Nhiu plime c tnh qunh
+ Nhiu plime c tnh dai. D l kha nng cua p lime chng lai luc ko
bn ngoi. Tnh dai phu thuc vo su sp xp phn tu, phu thuc vo nhit d
v phu thuc vo h s trng hop.
+ Nhiu plime c tnh deo. Tnh deo l kha nng bin dang cua c c cht
rn trong nhung diu kin nht dinh (nhit d, p sut) v giu nguyn hnh mo
khi tro lai diu kin ban du.
14.3.2-Tnh cht ha hc:
Ha tnh cua plime phu thuc vo thnh phn v cu tao ha hoc cua
chng. Cc chuyn ha ha hoc cua chng c th chia thnh 3 loai:
-Loai thu nhat: Cc phan ung be gy, phn huy mach plime:
-Phan ung dplime ha duoi tc dung cua nhit d. Khi dun nng mt s
plime toi 200-250
0
C th bt du dplime ha thnh cc monome.
Th du: Plimetilmetacrilat khi dun nng 200
0
C s tao thnh metilmetacrilat :
o
po limetil metacrilat
n
CH
2
CH
3
COOCH
3
C
200 C
CH
2
CH
3
COOCH
3
C
metilmetacrilat
n
-Dplime ha duoi tc dung co hoc (nhu dp bng ba, dt mong ,siu m
..)
Th du : Plistiren c th bi depolime ha trong ci xay, phn tu luong cua
chng giam nhiu ln.
-Nhiu plime nhu plieste, pliamit c th bi thuy phn duoi tc dung cua
axit hoc kim, nhu vy plime s bi phn huy.
Thdu: to nilon 6,6 bi phn huy boi axit hoc kim:
H NH(CH
2
)
6
NHCO(CH
2
)
4
CO ]
n
+
(2n - 1)H
2
O
H
nH
2
N(CH
2
)
6
NH
2
+ nHOOC(CH
2
)
4
COOH
nilon-6,6
hexametileniamin
axit aipic
- -
[
-
-
OH
-Nhiu plime bi phn huy duoi tc dung cua cc tc nhn oxi ha: nhu khi
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 222
d lu o ngoi khng kh nhiu plime bi dn, d gy v mu st bin di.
-Loai thu hai: Cc phan ung duy tr mach cacbon:
Gm cc phan ung thuc cc nhm du mach hoc cc phan ung th o giua
mach, hoc phan ung cng vo cc lin k di:
Th du: - PVC c th bi clo ha thnh clorin c ti l clo cao hon PVC:
o
clorin
n
(C
4
H
5
Cl
2
) + 2nHCl
as
t
(-CH
2
-CH-) + nCl
2
Cl
n
polivinylclorua
- PS c th nitro ha hoc sunf ha vo nhn benzen :
H
2
O n 3 + 3
NO
2
O
2
N
NO
2
CH
2
(
_ _
CH
_
)
n
H
2
SO
4
HNO
3
n +
n
)
_
CH
_
_
(
CH
2
- Plivinil axetat (PVA) c th bi thuy phn tao thnh plivinil ancol:
polivinyl ancol
(-CH
2
-CH-) + nCH
3
COOH
OH
n
O
axit axetic
H
2
SO
4
polivinylaxetat
n
O-C-CH
3
(-CH
2
-CH-) + nH
2
O
t
o
-C th axyl ha hay nitro ha xenlulozo:
+
4 2
2 3 3 2 7 6
) ( 2 ) ) ( (
SO H
n
O CO CH n OH O H C
4 4 3 4 4 2 1 4 4 4 3 4 4 4 2 1
axetic Anhidrit Xenluloz
4 4 3 4 4 2 1 4 4 4 4 4 3 4 4 4 4 4 2 1
axetic Axit diaxetat xenluloz
COOH nCH OCOCH OH O H C
n 3 2 3 2 7 6
2 ) ) )( ( ( +
+
4 2
2 3 3 2 7 6
) ( 3 ) ) ( (
SO H
n
O CO CH n OH O H C
4 4 3 4 4 2 1 4 4 4 3 4 4 4 2 1
axetic Anhidrit Xenluloz
4 4 3 4 4 2 1 4 4 4 4 3 4 4 4 4 2 1
axetic Axit triaxetat xenluloz
COOH nCH OCOCH O H C
n 3 3 3 2 7 6
3 ) ) ( ( +
O nH
n
ONO OH O H C
SO H
nHNO
n
OH O H C
2
))
2
(
2
) (
2 7 6
(
4 2
3
)
3
) (
2 7 6
( + +
4 4 4 4 3 4 4 4 4 2 1 3 2 1 4 4 4 3 4 4 4 2 1
mononitrat Xenluloz nitric Axit Xenluloz
+
4 2
3
2 )
3
) (
2 7 6
(
SO H
nHNO
n
OH O H C
3 2 1 4 4 3 4 4 2 1
nitric Axit Xenluloz
O nH
n
ONO OH O H C
2
2 )
2
)
2
)( (
2 7 6
( +
4 4 4 4 3 4 4 4 4 2 1
dinitrat Xenluloz
O nH
n
ONO O H C
SO H
nHNO
n
OH O H C
2
3 )
3
)
2
(
2 7 6
(
4 2
3
3 )
3
) (
2 7 6
( + +
4 4 4 3 4 4 4 2 1 43 4 2 1 4 4 4 3 4 4 4 2 1
trinitrat Xenluloz nitric Axit Xenluloz
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 223
-Loai thu 3: Cc phan ung lm t ng mach plime: (Ko di mach cacbon
thnh cc plime khi, cc plime ghp hoc cu tao mang luoi khng gian) .
Bng phuong php dng trng hop khi, dng trng hop ghp c th tao ra
nhung san phm plime moi c phn tu luong lon hon plime cu dng lm
nguyn liu tt hon rt nhiu.
-Su luu ha cao su l phan ung tao ra cu ni disunfua giua cc mach
plime hnh thnh cu tao mang luoi.
-Su chuyn ha tu dang rrol sang dang rrit cung lm chuyn cu tao tu
mach thng sang cu tao mang luoi cua cua nhua phenol-fomandehit:
+
OH
CH
2
_ _ _
_ _
CH
2
OH
_
OH
n
HCH=O
CH
2
CH
2
CH
2
CH
2
OH
CH
2
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
CH
2
OH
CH
2
nh a re rol
nh a re rit
Nhn chung, da s cc plime tng hop bn vung v mt ha hoc di voi tc
dung cua a xit, ba zo v c c cht oxi ha hon cc plime thin nhin nhu tinh
bt, xenlulozo .v.v...
14.4-Diu ch cc plime:
14.4.1-Nguyn liu:
-Kh t hin nhin: Kh thin nhin thuong tch luy trong cc lop dt dy cua
vo tri dt nm trong nhung vng ring bit. Mu n khai thc nguoi ta khoan
su xung lng dt, kh tu phun ln mt dt nho p sut cao.
Thnh phn chu yu cua kh thin nhin l CH
4
chim 85-98%.
Cc thnh phn khc l nhung dng dng cua CH
4
nhu etan, propan, butan.
kh
thien
nhien
CH
4
1500
0
C
cloropren
butaien
cao su cloropren
cao su buna
cha t de o va t vinilic
cao su buna
N
-
este vinilic
C
2
H
2
acrilonitrin
s o che bien kh thien nhien tha nh cac chat polime
-Than d, d vi:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 224
N
- cao subuna
PVC
vinilclorua
PE
N
-
cao su buna
PS
re rol va re rit
nha
stiren
phenol
lapsan
terephtalic
axit
benzen
xilen
THAN
A
axetilen
cacbua canxi
cao su
cloropren
cloropren
caosu buna
vinil axetilen
etilen
Tu than bo nho qa trnh nhit phn ri chung ct phn doan lop nhua than
d o nhit d cao thu duoc rt nhiu loai hidrocacbon thom v dn xut cua
chng. Tu than gy v vi sng (nhit phn tu d vi) c th san xut cacbua
canxi tr ong l din; v cacbua caxi c th tao ngun kh C
2
H
2
, v t u d c th
tao nhiu loai plime.
-Kh dau mo: Kh du mo nm trong cc t i du mo, mt phn tan trong du
mo, cn mt phn o pha t rn lop du tao thnh lop kh c p sut cao. T rong
thnh phn kh du mo chu yu l butan C
4
H
10
chim khoang 76-86%, cn lai
l cc dng dng cua chng.
DA U
MO
xilen
benzen
axit
terephtalic
lapsan
phenol
stiren
nh a
rerol va rerit
PS
cao su buna
-
N
etilen
PE
vinilclorua PVC
cao subuna -
N
propilen
PP
glixerin
nha gliptal
xiclohexan
caprolactam capron
axit aipic
nilon 6
,6
izopentan izopren
cao su
izopren
butilen butaien
cao su buna
metilmetacilat
thu y tinh h u c
-Dau mo: Du mo l hn hop phuc tap nhiu loai hidrocacbon v cc cht
huu co khc nhau.
-tinh bot, xenlulzo: Thuy phn tinh bt, xenlulozo dn cng ri ln men cho
ta ruou etilic, t u ruou etilic ta c th diu ch ra cao su buna v nhiu plime
khc.
14.4.2-Cc phuong php tong hop plime:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 225a
a-Trng hop:
-inh nghia: Phan ung trng hop l mot qa trnh trong d cc phn tu nho
(mnme) kt hop voi nhau t ao thnh m ot phn t u l on (plime) c phn tu
luong cao. Trong phan ung trng hop ton b o mnme nm hn trong phn
tu plime m k hng gi ai phng m ot phn t u nho no khc . (hay: Phan ung
trng hop l qu trnh cong hop lin ti p nhiu phn t u nho (mnme) thnh
mot phn tu lon (plime) m khng giai phng mot phn tu nho no khc).
Th du:
tru ng h p
n
(A) A n
CH
2
=CH
2
CH
2
_ _
CH
2
_
( )
n
n
tru ng h p
t
o
,
xt
etilen
po lietilen (PE)
-iu kin cau tao cua mnme:
Diu kin co ban di voi cc mnme c kha nng phan ung trng hop l
chng phai l hop chat chua no, trong phn tu c noi di hoc noi ba, dc bit
l cc dn xut c ni di kiu vinil, cc cht c ni di lin hop; cc hop chat
vng khng bn d bi gy ra d tham gia phan ung trng hop.
Khi thay th H trong phn tu CH
2
=CH
2
bng cc nhm th ht electron nhu
-F, -Cl, -Br, -I, -CN, -CH=O, -COOH, - C
6
H
5
. .. lm cho kha nng phan ung
trng hop tng thm. Cc hop cht vinil CH
2
=CH-X v cc hop cht ankiliden
CH
2
=CXY c khuynh huong d tham gia phan ung trng hop, t rong khi d cc
hop cht kiu CHX=CHX hay CHX=CHY khng c kha nng tu trng hop voi
nhau nhung lai c kha nng tham gia dng trng hop voi monme khc. Th du:
CH
2
=CHCl (vinil clorua) hay CH
2
=CCl
2
(viniliden clorua) du c th trng hop
duoc, tr ong khi d CHCl=CCl
2
(tricloetilen) lai khng c kha nng trng hop.
Tru truong hop tetrafloetilen CF
2
=CF
2
v mt s truong hop chua flo.
Cc dilfin lin hop c kha nng phan ung trng hop manh nht, sau khi
trng hop th nh plime, t rong mi mt xch cn mang mt ni di. Cc hop
cht c ni di lin kiu anlen trng hop kh khn hon
-Co ch phan ung trng hop: Phan ung t rng hop c th xay ra theo 3 dang
co ch: co ch trng hop goc tu do , co ch trng h op cation, co ch trng
hop anion:
-Co ch trng hop goc: 3 giai doan:
Giai doan khoi mo:
R
_
O
_
O
_
R O
_
R
.
2
Giai doan pht trin mach:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 226
X
RO + CH
2
=CH RO-CH
2
=CH
X
X
RO-[-CH
2
-CH-]-CH
2
-CH
X X
RO-CH
2
-CH
+ nCH
2
=CH
X
n
Giai doan tt mach: c nhi cch tt mach:
+ Tuong tc voi cht la trong hn hop phan ung :
X
RO-[-CH
2
-CH-]-CH
2
-CH + HZ
X X
RO-[-CH
2
-CH-]-CH
2
-CH
2
+ Z
X
n n
+ Su chuyn mach:
X
RO-[-CH
2
-CH-]-CH=CH +
X
X
RO-[-CH
2
-CH-]-CH
2
-CH
X X
RO-[-CH
2
-CH-]-CH
2
-CH +
X
X
RO-[-CH
2
-CH-]-CH
2
-CH
2
X
n
n
n n
hay :
X
RO-[-CH
2
-CH-]-CH
2
-CH-OR
X X
RO-[-CH
2
-CH-]-CH
2
-CH + OR
X
n
n
-Co ch trng hop cation:
Th du: Phan ung tng hop isobutilen voi cht xc tc l BF
3
+ HX xay ra
theo co ch cation theo 3 giai doan:
Giai doan khoi mo phan ung:
BF
3
+
HX
H
[BF
3
X]
[BF
3
X]
+
(CH
3
)
3
C
CH
2
=C(CH
3
)
2
+
H [BF
3
X]
Giai doan pht trin mach:
+
CH
2
=C(CH
3
)
2
(CH
3
)
3
C (CH
3
)
3
C
CH
2
C(CH
3
)
2
CH
3
CH
3
CH
2
=C(CH
3
)
2
(CH
3
)
3
C CH
2
C(CH
3
)
2
n
C
CH
2
(CH
3
)
3
C
CH
2
C(CH
3
)
2
[
]
n
+
Giai doan tt mach:
+ C th kt hop voi anion phuc:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 227
[BF
3
X]
CH
3
CH
3
n
] [
CH
2
C(CH
3
)
2
(CH
3
)
3
C CH
2
C +
CH
3
CH
3
n
] [ CH
2
C(CH
3
)
2
(CH
3
)
3
C CH
2
C
X
+
BF
3
+ C th do tch H
+
:
CH
3
CH
3
n
] [
CH
2
C(CH
3
)
2
(CH
3
)
3
C CH
2
C
CH
3
CH
3
n
]
[ CH=C(CH
3
)
2
(CH
3
)
3
C CH
2
C
+
H
hay :
CH
3
CH
3
n
] [
CH
2
C(CH
3
)
2
(CH
3
)
3
C
CH
2
C
CH
3
CH
3
n
]
[ CH
2
C=CH
2
(CH
3
)
3
C CH
2
C
+
H
CH
3
-Co ch trng hop anion:
Th d u: Ph an ung trng hop nitroetilen c xc tc kim xay ra theo co ch
anion cung xay ra ba giai doan:
+ Giai doan khoi mo phan ung:
CH
2
=CH NO
2

+ OH HO
_
CH
2
_
CHNO
2
+ Giai doan pht trin mach:
CH
2
=CH NO
2

+
n
+
1
(
)
HOCH
2
CH
NO
2
CH
2
CH
NO
2
[ ]
n
CH
2
CHNO
2
NHOCH
2
-CHNO
2
+ Giai doan tt mach: C th do thuy phn:
HOCH
2
CH
NO
2
CH
2
CH
NO
2
[ ]
n
CH
2
CHNO
2
H
2
O
+
+
OH
CH
2
NO
2
CH
2
n
] [
NO
2
CH
2
CH
NO
2
HOCH
2
CH
hoc :
HOCH
2
CH
NO
2
CH
2
CH
NO
2
[ ]
n
CH
2
CH
2
NO
2
+
H CHNO
2
CH
2
n
] [
NO
2
CH
2
CH
NO
2
HOCH
2
CH
Su trng hop cc dien lin hop nho xc tc co kim cung c th coi thuc co
ch trng hop anion.
-Cc loai phan ung trng hop:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 228
-Trng hop thuong (mt loai mnme): L loai plime do mt mnme tao
nn.
Th d u: Cc p lime nhu PV C, P E, P P, PS, P A, Ca o su buna, p limetil
metacrilat (thuy tinh huu co) .v.v...l do phan ung trng hop thuong tao nn.
Cc don vi mt xch trong phn t u plime c th sp xp trt tu t heo cc
kiu sau dy:
+ Kiu kt hop du voi dui:
R
R
R
CH
2
CH CH
2
CH
CH
2
CH
+ Kiu du voi du, dui voi dui:
R
R R
R
CH CH
2
CH
2
CH
CH CH
2
CH CH
2
+ Kiu sp xp hn dn v trt tu:
CH CH
2
CH CH
2
CH CH
2
CH
2
CH CH
2
CH
R R R
R
R
Kiu trt tu sp xp no l do dc dim cu tao cua mmnme v diu kin
tin hnh phan ung quyt dinh. Cc plime c trt t u sp xp c c don vi mt
xch cua monme theo kiu du voi dui: plivinil axetat, plivinil clorua,
plistiren. Tuy nhin khng th han ton c mt kiu sp xp duy nht, m c
mt kiu no d chim uu th.
-ong trng h op: Dng trng hop l s u trng hop c ua mt h n hop c c
mnme tao thnh plime, trong d cc loai mnme du tham gia phan ung v
nm trong mach cua plime. S an phm trong truong hop ny goi l ch at
cplime , hay cht dng trng hop.
Hai loai mnme A v B khi cho dng trng hop c th tao thnh
cplime (-A-B-)
n
nhu sau:
nA + nB (-A-B-)
n
Th du: -Cao subuna-S l mt loai cplime thu duoc do su dng trng hop
giua butadien-1,3 v stiren:
o
t C, xt
n
nCH
2
=CH-CH=CH
2
+ nCH
2
=CH (-CH
2
-CH=CH-CH
2
-CH-CH
2
-)
-Cht cplime cua vinil clorua v vinil axetat bn vung , dn hi , hon hn
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 229
tnh cht cua PVC v PA :
nCH
2
=CH + nCH
2
=CH (-CH
2
-CH-CH
2
-CH-)
Cl Cl
O-C-CH
3
O
n
t C, xt
o
O
O-C-CH
3
-Dng trng hop giua acrilonitrin v vinylaxetat duoc cplime tt hon cc
plime khi trng hop ring r:
nCH
2
=CH + nCH
2
=CH (-CH
2
-CH-CH
2
-CH-)
CN CN
O-C-CH
3
O
n
t C, xt
o
O
O-C-CH
3
-Esre cua axit malic khng c kha nng tu trng hop duoc nhung sn sng
tham gia dng trng hop voi stien:
+ nCH
2
=CH
n
t C, xt
o
n
C
6
H
5
OOC COOC
6
H
5
H
H
C=C
COOC
6
H
5
C
6
H
5
OOC
(-CH-CH-CH
2
-CH-)
-
ong trng h op khoi (Bloc cplime): plime duoc tao thnh goi l cplime
khi.
Chui mt xch plime gm nhung khi lon cua ring tung loai mnme, cu
mt khi loai mnme ny lai dn mt khi loai mnme khc:
n
B
(
)
n
(
A
)
)
(
B
)
A
(
n
n
Th du:
Cht cplime khi duoc tao thnh khi dng trng hop khi giua cao su
thin nhin v pliclor opren xut hin nhung tnh cht moi qu gi kt hop voi
nhung uu dim cua plime ring bit nhu bn vung trong benzen v trong du:
...
...
CH
3
n
(-CH
2
-CH=CH-CH
2
-) (-CH
2
-CH=CH-CH
2
-)
n
Cl
+
Cl
n
(-CH
2
-CH=CH-CH
2
-) (-CH
2
-CH=CH-CH
2
-)
n
CH
3
-ong trng hop ghp:
Dng trng hop l gn plime thu 2 vo mach chnh cua plime thu nht.
Cht plime chnh c th l plime don gian hoc l mt cplime. Cht plime
duoc tao thnh khi dng trng hop ghp goi l cplime-ghp.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 230
So d cu tao cua cplime-ghp c th biu din nhu sau:
A B
B A
B A B A B A B A
D
D
D D
D
D
D
D
D
Th du: Cplime cua stiren v viniliden clorua l:
Cl
[
]
n
CH
2
C
Cl
CH
2
CH
Tin hnh trng hop ghp voi vinil axetat, tao ra cplime-ghp m cc
mach nhnh l cc don vi mt xch cua vinil axetat:
CH
2
CH
Cl
CH
2
C
OOCCH
3
CH=CH
2
n
]
[
C
6
H
5
+
Cl
Cl
C
6
H
5
CH
2
C CH
2
CH CH
2
CH CH
2
C
C
6
H
5
Cl
CH
2
CH CH
2
C
C
6
H
5
Cl
CH
2
CH CH
2
C
C
6
H
5
Cl
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
OOCCH
3
CH
CH
2
CH
2
CHOOCCH
3
CH
2
CHOOCCH
3
CH
2
CHOOCCH
3bb-
b-Trng ngung:
inh nghia: Qu trnh nhiu phn t u nho (mnme) kt hop voi nhau thnh
phn tu lon (plime) dong thoi giai phng nhng phn t u nho don gian nhu
H
2
O , HCl , NH
3
...goi l phan ung trng ngung.
Th du:
-Phan ung trng ngung cua axit oxiundcanic:
oxiuncano ic axit
H
2
O n +
OH
n
] O(CH
2
)
10
CO
[
H n HOC(CH
2
)
10
COOH
1) (
-Phan ung trng ngung giua hexametilendiamin v axit adipic tao ra to
nilon 6,6:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 231
H NH(CH
2
)
6
NHCO(CH
2
)
4
CO ]
n
+ H
2
O
H
2
N(CH
2
)
6
NH
2
+ HOOC(CH
2
)
4
COOH
nilon-6,6
hexametileniamin axit aipic
- -
[
- -
OH
n n
2n 1) (
iu kin cau tao cua cc mnme:
-Phai c tu 2 nhm chuc c kha nng phan ung tro ln. Hai nhm chuc c
th ging nhau hoc khc nhau.
-Nhung mnme c 2 nhm chuc s tao ra nhung plime c cu tao mach
thng.
-Nhung mnme c 3nhm chuc s tao ra plime c cu tao mang luoi
khng gian 3 chiu.
Th du: glixrin + axit o-phtalic tao ra plime gliptal c cu tao khng gian
3 chiu.
Nhu vy diu kin co ban cua phan ung trng ngung phu thuc vo ban cht
v s nhm chuc cua cc mnme. S nhm chuc cung quyt dinh ca dang cu
tao cua plime hnh thnh: hoc cu tao dang thng hoc cu tao dang khng
gian 3 chiu.
-Cc loai phan ung trng ngung:
-Phan ung trng ngung este ha : tao ra plieste:
n HO-(CH
2
)
x
COOH H-[-O(CH
2
)
x
CO-]
n
-OH + (n-1) H
2
O
nHO-(CH
2
)
x
OH + nHOOC-(CH
2
)
x
COOH
H-[-O-(CH
2
)
x
OOC-(CH
2
)
x
CO-]
n
-OH + (2n-1) H
2
O
CH
2
OHCHOHCH
2
OH + HO OC(CH
2
)
x
COOH pl ime c c u t ao mang
luoi khng gian .
th du: etilenglicol tc dung voi axit terephtalic:
nHOCH
2
CH
2
OH + nHOOCC
6
H
4
COOH
(-O-CH
2
CH
2
OCOC
6
H
4
CO-)
n
+ 4nH
2
O
-Phan ung trng ngung anhidrit ha: tao ra plianhidrit.
n HOOC-(CH
2
)
x
COOH HO-[-OC(CH
2
)
x
COO-]
n
-H + (n - 1)H
2
O
-Phan ung trng ngung amit ha: tao ra pliamit:
n H
2
N-(CH
2
)
x
COOH H-[-NH(CH
2
)
x
CO-]
n
-OH + (n - 1)H
2
O
nH
2
N-(CH
2
)
x
NH
2
+ nHOOC-(CH
2
)
x
COOH
H-[-NH(CH
2
)
x
NHCO-(CH
2
)
x
CO-]
n
-OH + (2n - 1)H
2
O
th du: hexametilendiamin trng ngung voi axit adipic cho nilon 6,6:
nH
2
N-(CH
2
)
6
NH
2
+ nHOOC-(CH
2
)
4
COOH
H-[-NH(CH
2
)
6
NHCO-(CH
2
)
4
CO-]
n
-OH + (2n - 1)H
2
O
-Phan ung trng ngung giua phenol v fomandhit tao ra phenolfomandhit:
+ Nhua rerol c cu tao mach thng:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 232
H
2
O
)
1 + (n +
HCH=O
) (
)
(
2
+ n
1
+
n
+
OH
nh a re rol
n
OH
_
OH
CH
2
_
_ _ _
_
CH
2
OH
+ Nhua rerit c cu tao mang luoi khng gian:
d
nh a re rit
CH
2
OH
CH
2
CH
2
HCH=O
OH
+
+ H
2
O
+
OH
HCH=O
CH
2
CH
2
CH
2
CH
2
OH
CH
2
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
OH
CH
2
CH
2
OH
CH
2
nh a re rit
d
-Phan ung trng ngung giua anilin voi andehit fomic:
Trong mi truong axit yu hoc bazo tao thnh polime c cu tao mach
thng, nhua ny d nng chay:
H
2
O +
n+
2 (
) +
n +
1
(
)
)
( 1 + n
n
CH
2
CH
2
NH
NH
2
NH
NH
2
HCH=O
Trong mi truong axit manh chu yu tao thnh san phm polime c cu tao
khng gian 3 chiu, nhua ny khng nng chay, khng bi ha tan:
HCH=O
NH
2
+
hay:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 233
NH
NH NH
CH
2
CH
2
+H
2
O
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
NH NH
NH
-Ur trng ngung voi fomandhit t ao ra nhua urfomandhit (t ao plime c cu
tao mang luoi khng gian):
H-C=O + H
2
N-C-NH
2
O
H
H
O
HOCH
2
-N-C-NH
2
H
H
HOCH
2
-N-C-NH
2
+ O=C-H
O
H H
O
HOCH
2
-N-C-N-CH
2
OH
O
O
O=C
N-CH
2
-N-C-N
-N-CH
2
-
CH
2
N-CH
2
-N-C-N
CH
2
-CH
2
-N-
H
2
C
HOCH
2
-N-C-N-CH
2
OH
O
H H
+HCHO, ure
Hay c th vit:
t le 1:4
H
2
N
C
O
NH
2
+
HCH=O
n
+
H
2
O
n n n
4 4 CH
2
CH
2
CH
2
N
O
C N
CH
2
N
O
C N
2
-Phan ung trng ngung siloxan tao thnh plisilxan:
+ C cu tao mach thng:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 234
H
2
O n +
n
CH
3
Si
CH
3
OH HO HO
[
Si O ] H
CH
3
CH
3
n
+ C cu tao mang luoi khng gian:
O Si
HO OH
CH
3
Si
CH
3
n +
OH
Si
OH
OH HO
O
O
O
Si O
CH
3
CH
3
CH
3
CH
3
Si
CH
3
CH
3
Si
O
Si
CH
3
CH
3
n
4
+
H
2
O
n
6
n
-So snh gia phan ung trng hop v trng ngung:
TRNG HOP TRNG NGUNG
Cc m nme kt hop voi nhau
theo phan ung dy truyn nhanh.
Cc m nme kt hop voi nhau
thnh dime, tetrame, octame,
v.v...tung buoc chm chap.
Khng c phn tu nho duoc loai
tru ra trong qa trnh phan ung.
C nhung phn tu nho don gian,
nhu H
2
O duoc lo ai tr u ra tr ong
qa trnh phan ung.
Nng d mnme giam dn trong
qa trnh phan ung.
Cc mnme bin ngay trong
trong giai doan du cua phan ung.
Plime tao thnh rt nha nh hu
nhu tuc thoi, khi luong plime
thay di t tr ong qa tr nh phan
ung.
Plime tao thnh chm, ph n tu
luong plime tng ln dn dn.
Ko di thoi gian phan ung, tng
hiu su t plim e, nhung t anh
huong dn phn tu luong.
Ko di thoi gian phan ung, phn
tu luong plime cng tng.
14.5-Cao su:
-Cao su thi n nhin: Trn th gioi c trn 500 loi cy cho cao su. Rung cao
su o nuoc ta hin nay chu yu l loi cy Heva br asiliensis do thuc dn Php
dua sang trng thu ri lp cc dn din o nuoc ta t u nhung nm 70 cua th ki
19 o Nam b.
-Mu cao su v cao su th:
Mu cao su:
Trch cy cao su d thu nhua hay mu cao su, hay latex. Mu cao su l mt h
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 235
phn tn trong nuoc cua c c tiu phn c duong knh 5.10
4
mm (0,5 microng
mt). Khi cho bay hoi, ngoi nuc ra t rong mu cao su c 30-40% thnh phn
rn. Trong cht r n d c 90% l hidrocacbon, 10% l cc thnh phn khc:
prtit, nhua, s p, cht bo, c c mui v co v mt s men. Mu cao su c pH
trong khang 6,4 - 6,8.
Cao su th:
Nguoi ta l m dng tu mu cao su d ly cao su th bng cch xng khi
(cch lm truoc dy), hay dng axit axtic hoc ax it fomic (c ch lm hin
nay).
Cao su moi ly tu mu ra bng cch lm dng tu goi l cao su th hay cao
su song, c mu nu hoi den . Mt dang cua co su h l crp.
Thnh phn trung bnh cua cao su th:
-Hidrcacbon (C
5
H
8
) (cao su): 92-94%
-Nuoc: 0,5-1,2%
-Prtit: 0,15-0,5%
-Cc cht chit duoc bng xeton: 2,5-3,2%
Sau khi tinh ch loai bo tap cht trong cao su th s thu duoc cao su tinh
khit hon.
-Cau tao cua cao su thin nhin:
Nguoi ta xc dinh cu tao cua cao su thin nhin dua vo mt s tnh cht
cua n trn co so cc du kin thuc nghim sau:
-Dua vo kt qua phn tch ngun t, cao su c cng thuc nguyn don gian nht
l C
5
H
8
, c cu t ao dai phn t u (v p sut hoi = 0 v dung dich c dc tnh
keo).
-Khng chung ct duoc, o 300
0
C n bi phn huy cho izpren.
Nhu vy cao su c th coi l l plime izpren: (C
5
H
8
)
n
:
CH
3
o
300 C
n
(C
5
H
8
)
nCH
2
=C-CH=CH
2
-Tham gia phan ung cng : H
2
, Br
2
, HCl , HBr ,.v.v. Trong mi mt xch cua
phn tu cao su c chua 1 lin kt di.
H
2
Ni
+
)
(
n
CH
2
CH
2
CH
3
CH CH
2
)
(
n
CH
2
CHBr
CH
3
CBr
CH
2
+
Br
2
CH
2
CCl
CH
3
CH
2
CH
2
n
(
)
+
HCl
CH
2
CBr
CH
3
CH
2
CH
2 n
(
)
+
HBr
(-CH
2
-C=CH-CH
2
-)
n
CH
3
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 236
-Phan ung voi zn tao thnh znit ri thuy phn cho san phm dicacbonil:
n
n
O O
CH
2
C O
CH
3
C
CH
2
O
3
+
n
(C
5
H
8
)
CH
2
C
CH
3
O C CH
2
O O
n
ane hit levulic
2
CH
3
+ 4nH
2
O 2nO=C-CH
2
-CH
2
-CH=O + 3nH
2
O
2
-Khi luong phn tu khoang: 50 000-3 000 000 dvC, n > 20 000.
-Dua vo kt qua nghin cuu quang ph Roentgen, cao su c cu hnh cis:
ca u hnh cu a pha n t cao su (da ng cis)
H
CH
3
H
CH
3
H
CH
3
CH
2
C C
CH
2
CH
2
C C
CH
2
CH
2
C C
CH
2
-Tnh chat cua cao su thin nhin:
-Trang thi: Cao su c th tn tai duoi 4 tr ang thi: kt tinh, r n v dinh hnh,
dn hi v deo. t rang thi dn hi l t rang thi tr ung gian giua v dinh hnh v
deo. trang thi deo l trang thi cua cht long c d nhot rt cao.
-Tnh tan: Cao su t an trong cc hidrocacbon ( nhu benzen, esxng, du thng )
v trong dn xut halogen (nhu clorofoc); khng tan trong trong cc dung mi
phn cuc (nhu nuoc ruou, a xton). Khi ha ta n cao su th uong phng ln rt
manh. Cc dung dich cao su long c d nhot cao, d nhot ti l voi h s trng
hop.
-Su tu oxi ha: Cao su d lu ngoi khng kh s giam tnh bn co hoc, tnh dn
hi, dng thoi tnh tan cua ca o su tng ln nhiu ngay ca trong dung mi phn
cuc. Cao su d luu ha cung tuong tu. Su tu xi ha cua cao su c l truoc ht
tao ra >CH-O-O-H, sau d chuyn thnh cc nhm: >CHOH v >C=O, dng
thoi xay ra su be gy mach dai phn tu, diu ny giai thch giam d bn, giam
h s trng hop v lm thay di tnh cht co l cua cao su.
-Su luu ha cao su:
Nhuoc dim cua cao su th: c tnh dn hi vu km, vua bi gioi han trong
nhit d hep, khi nng qu n nho v tro nn dnh, nguoc lai khi lanh qu th
cung v tro nn dn. D khc phuc nhuoc dim d cn phai luu ha cao su.
Trong tt ca cc chuyn ha ha hoc cua cao su, quan trong nht l phan
ung voi luu huynh. Phan ung cua cao su voi luu huynh goi l su luu ha cao
su - phan ung bt thun nghich duoc thuc hin o nhit d 130-145
0
C (cao hon
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 237
nhit d nng chay cua l uu huynh (115,5C)) tao ra li n kt sunfua -S - hoc
disufua -S-S- giua cc dai phn tu, hnh thnh cau tao mang luoi :
CH
3
-CH
2
-C=CH-CH
2
- + S
-CH
2
-C=CH-CH-
CH
3
SH
CH
3
-CH
2
-C=CH-CH- +
-CH
2
-C=CH-CH-
CH
3
S
CH
3
-CH
2
-C=CH-CH-
CH
3
SH
-CH
2
-C=CH-CH
2
-
S
S
S
S
CH CH
CH
3
C CH
CH CH
CH
3
C CH
2
CH CH
CH
3
C CH
CH CH
CH
3
C CH
2
-CH
2
-C=CH-CH-
CH
3
S
CH
3
-CH
2
-C=CH-CH-
+ S
C th biu thi tuong trung don gian cu tao cao su th v cao su luu ha
nhu sau:
S
S
S S
S
S
S
S
S
cao su tho cao su lu hoa
Cao su luu ha c nhiu tnh cht moi qu khc voi cao su khng luu ha:
tnh deo giam hoc bin mt; gi oi han nhit d deo mo rng, khi khi dun nng
khng mm ra, khi lanh vn duy tr dn hi, kha nng chng dut tng, chng
mi mn tng, kh tan hoc khng tan trong cc dung mi huu co.
Trong qu trnh luu ha thuong kt hop voi su ch ha voi nhiu thnh phn
khc nhu: cht xc tin luu ha, cht chng lo ha, cht chng xi ha, cht
dn, cht mu, cht l m mm, cht no bot v c c cht phu gia khc tuy theo
yu cu su dung.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 238
-Cht xc tin c tc dung lm cho qu trnh luu ha tro nn nhanh hon, ha
nhit d tr ong qu t rnh luu ha. Cc cht xc ti n v co: MgO , PbO , ZnO ;
cht xc tin huu co: MBT, MBTS:
N
S
SH
mecato benzothiazol
(MBT)
N
S
N
S
S S
dibenzo thiazildisufua
(MBTS)
-Cht chng lo ha: kmhm qa trnh tu oxi ha lm cho cao su giu duoc
bn lu hon, l nhung cht phan xi ha nhu:
naphtilamin
phenil
NH
-Cht dn: Tit kim cao su th, ngoi ra cn c tc dung chng mn, tng
d dai bn, chng du .. ..cc cht dn nhu m hng, bt CaCO
2
, MgCO
3
, cao
lanh, ZnO.
-Cht lm mm: vazolin, farafin, du my.
-Cc cht mu: Fe
2
O
3
cho mu do, m hng cho mu den , ...
-Cht no bot dng ch cao su xp nhe.
-Nhng dan xuat cua cao su thin nhin:
-Cao su-clo ha:
Cao su thin nhin + Cl
2
xay ra phan ung cng vo ni di v ca phan
ung th.
Thnh phn v cu tao cua cao su-clo ha khng nht dinh, n phu thuc
vo diu kin phan ung.
Nu thnh phn c 40% clo th mm, nu 65-68% clo th rt rn v bn ha
hoc.
Ung dung cua cao su-clo ha: ch son, vc ni, thuc v, dn kim loai, lm
vai loc axit v kim, tao mng xp trong thng din phn.
-Cao su-hidroclorua:
Phan ung cng cua cao su thin nhin xay ra theo qui tc cng
Maccpnhicp ( Markovnikov)
+ nHCl
Cl
n
(-CH
2
-C-CH
2
-CH
2
-) (-CH
2
-C=CH-CH
2
-)
n
CH
3
CH
3
Ung dung: ch son chng thm; tao cht tao mng d boc thuc n, hoa qua,
boc my mc d bao quan khi vn chuyn xa hoc luu trong kho.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 239
-Cao su tong hop:
-Cao su Buna (cao su plibutadien):
Cao su buna l san phm trng hop butadien-1,3:
n
(-CH
2
-C=CH-CH
2
-)
nCH
2
=CH-CH=CH
2
Na
divinyl cao su buna
Phan ung xay ra theo co ch gc tu do:
NaCH
2
-CH=CH-CH
2
Na + CH
2
=CH-CH=CH
2
divinyl
go c t do
.
go c t do po lime
go c t do
divinyl
+ n( + 1)CH
2
=CH-CH=CH
2
NaCH
2
-CH=CH-CH
2
NaCH
2
-CH=CH-CH
2
-(CH
2
-CH=CH-CH
2
-)-CH
2
-CH=CH-CH
2
n
n
-(CH
2
-CH=CH-CH
2
-)-CH
2
-CH=CH-CH
2
NaCH
2
-CH=CH-CH
2
go c t do po lime
2
(2NaCH
2
-CH=CH-CH
2
-(CH
2
-CH=CH-CH
2
-)-CH
2
-CH=CH-CH
2
)
2
n
Ung dung: lm vo, rut xe cc loai, giy dp, v cc d dng bng cao su
.v.v...
-Cao su Buna-S: ( cao su plibutadien-stren):
Cao su buan-S l san phm dng trng hop butadien-1,3 v stiren:
o
t C, xt
n
nCH
2
=CH-CH=CH
2
+ nCH
2
=CH (-CH
2
-CH=CH-CH
2
-CH-CH
2
-)
Cao su buna-S l loai cao su tng hop c d bn cao, chiu co st v c tnh
dn hi cao.
-Cao su Buna-N (cao su butadien-acrilnitrin):
Cao su buna-N l san phm dng trng hop butadien-1,3 v acrilnitrin:
(-CH
2
-CH=CH-CH
2
-CH-CH
2
-) nCH
2
=CH-CH=CH
2
+ nCH
2
=CH
n
t C, xt
o
CN CN
divinyl
acilonitrin cao su buna-N
Cao su Buna-N c tnh chng du cao, bn voi tc dung cua san phm du
mo .
-Cao su Cloropren ( hay npren , hay spren ) :
Cao su cloropren l san phm trng hop cua clorpren :
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 240
(-CH
2
-C=CH-CH
2
-)
n
Cl
nCH
2
=C-CH=CH
2
Cl
o
t C, xt
cloropren
policloropren
Cao su Cloropren c tnh cht qi bu nhu dn hi, khng chy, rt bn co
hoc, bn voi du v voi zn.
-Cao su ispren:
Cao su isopen l san phm trng hop cua ispren:
cao su isopren isopren
t C, xt
o
CH
3
nCH
2
=C-CH=CH
2
CH
3
n
(-CH
2
-C=CH-CH
2
-)
-Cao su butil:
Cao su butyl l san phm dng trng hop cua izbutilen voi mt dilfin
nhu izpren:
cao su butyl
isobutylen
t C, xt
o
CH
3
nCH
2
=C-CH
3
+
CH
3
n
(-CH-C-CH
2
-C=CH-CH
2
-)
CH
3
nCH
2
=C-CH=CH
2
CH
3
isopren
CH
3
Phan ung xay ra theo co ch cation voi xc tc electrophin tao phuc c dc
tnh cua mt axit c kha nng prton ha manh:
AlCl
3
+ ROH [ACl
3
(OR)]
(-)
H
(+)
Sau d phan ung din ra qua 3 giai doan:
-Giai doan khoi mo nho H
(+)
tn cng vo mnme tao ra cacbocation:
CH
2
=C-CH
3
CH
3
isobutylen
[AlCl
3
(OR)]
-
H
+
+
CH
3
CH
2
-C-CH
3
+ [AlCl
3
(OR)]
-
cacbocation
-Giai doan pht trin mach cation cng tip voi mnme:
CH
3
isopren
CH
3
CH
2
=C-CH=CH
2
CH
3
CH
3
-C-CH
2
-C=CH-CH
2
CH
3
CH
3
CH
3
-C-CH
3
+
cacbocation
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 241
isobutylen
CH
3
CH
2
=C-CH
3
CH
3
CH
3
-C-CH
2
-C=CH-CH
2
+
CH
3
CH
3
CH
3
CH
3
CH
3
-C-CH
2
-C=CH-CH
2
-CH
2
-C-CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
-C-CH
2
-C=CH-CH
2
-CH
2
-C-CH
3
+
CH
3
CH
3
CH
3
CH
3
nCH
2
=C-CH=CH
2
CH
3
CH
3
-C-CH
2
-C=CH-CH
2
-
n
nCH
2
=C-CH
3
+
CH
3
CH
3
CH
3
(-CH
2
-C-CH
2
-C=CH-CH
2
-)-CH
2
-C-CH
3
CH
3
CH
3
CH
3
-Giai doan tt mach ngung phan ung khi loai tru H
(+)
ra khoi cation:
CH
3
CH
3
CH
3
-C-CH
2
-C=CH-CH
2
-
n
CH
3
CH
3
(-CH
2
-C-CH
2
-C=CH-CH
2
-)-CH
2
-C-CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
(-CH
2
-C-CH
2
-C=CH-CH
2
-)-CH
2
-C=CH
2
+ H
CH
3
CH
3
n
CH
3
-C-CH
2
-C=CH-CH
2
-
CH
3
CH
3
hoc:
CH
3
CH
3
CH
3
-C-CH
2
-C=CH-CH
2
-
n
CH
3
CH
3
(-CH
2
-C-CH
2
-C=CH-CH
2
-)-CH
2
-C-CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
(-CH
2
-C-CH
2
-C=CH-CH
2
-)-CH=C-CH
3
+ H
CH
3
CH
3
n
CH
3
-C-CH
2
-C=CH-CH
2
-
CH
3
CH
3
-Cao su silicn:
Cao su silicon l cao su tng hop moi diu ch bng phan ung trng ngung
siloxan tao thnh plisilxan:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 242
(n - 1)H
2
O
+
n
CH
3
Si
CH
3
OH
HO
HO
[
Si O
] H
CH
3
CH
3
n
Cao su-silicn c dc tnh rt bn voi tc dung cua nuoc, oxi, zon, tia tu
ngoai, a xit, bazo, r uou, du .v.v...v gioi han nhit d su dung rt r ng tu -
80
0
C dn +250
0
C vn duy tr tnh dn hi v tnh cch din.
14.6-Cht deo:
-Dinh nghia: Chat deo l nhng vat liu duoc ch tao tu polime c kha nng
bin dang duoi t c dung cua nhi t do, p su at v van gi nguyn bin dang
d khi thi tc dung.
-Thnh phan chat deo: Cht deo l hn hop nhiu cht:
-Polime: polime thin nhin hoc tng hop l t hnh phn chnh co ban nht cua
cht deo.
-Chat ha deo:
Cht ha deo l cht cho thm vo d tng tnh deo cho polime.
-Chat don:
Cht dn d tit kim polime, dng thoi lm tng thm mt s dc tnh cho
cht deo.
Th du: cht dn l ami ng lm tng tnh chiu nhit, bt Ca CO
3
lm tng tnh
chng mi mn, bt kim loai v t han ch gr aphit lm tng tnh dn din v dn
nhit.
-Cc chat phu gia khc: gm cht mu, cht chng oxi ha cht chng lo ha.
14.7-Mt s polime dng lm cht deo:
-Polietylen (PE): Diu ch bng cch trng hop etylen C
2
H
4
.
po lietilen (PE)
etilen
xt
,
o
t
tru ng h p
n
n
)
(
_
CH
2
_
_
CH
2
CH
2
=CH
2
-Polistiren (PS): Diu ch bng cch trng hop stiren C
6
H
5
CH=CH
2
.
xt
,
o
t
tru ng h p
n
n
)
(
_
CH
_
_
CH
2
CH
2
=CH
stiren
polistiren (PS)
-Polivinyclorua (PVC):
Diu ch bng cch trng hop vinylclorua CH
2
=CHCl.
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 243
xt
,
o
t
tru ng h p
n
n
)
(
_
CH
_
_
CH
2
CH
2
=CH
vinylclorua polivinylclorua (PVC)
Cl Cl
-Polimetyl m etacrylat (thuy tinh huu c o): Diu ch bng cch trng hop
metyl metacylat
CH
2
=C(CH
3
)COOCH
3
.
xt
,
o
t
tru ng h p
n
n
)
(
_
CH
_
_
CH
2
CH
2
=C
COOCH
3
COOCH
3
CH
3
CH
3
metyl metacrilat
polimetyl metacrilat
(thu y tinh h u c)
-Nhua phenolfomandehit: Diu ch bng cch dng trng hop giua phenol v
andehit fomic.
H
2
O
) 1
+ (n +
HCH=O
) (
) ( 2 + n
1 + n
+
OH
n
OH
_
OH
CH
2
_
_ _ _
_
CH
2
OH
nh a phenol fomanehit
14.8-To tng hp:
14.8.1-Phn loai: Cc loai to :
-To thin nhin: C sn trong thin nhin nhu to tm, len, bng.
-To ha hoc: gom to nhn tao v to tong hop:
+To nhn t ao duoc san xuat t u polime thin nhin duoc ch bin thm bng
con duong ha hoc. Th du: nhu to visco, to axetat, t o dng amoniac l nhung
to duoc ch bin tu xenlulozo .
+To tong hop: duoc san xuat tu nhng polime tong hop.
Th du: nhu to poliamit: to enang, to nilon 6,6 ... ; to polieste.
14.8.2-Diu ch to poliamit:
-To nilon 6,6: Duoc trng ngung gua hexametilendiamin voi axit adipic:
nH
2
N(CH
2
)
6
NH
2
+ nHOOC(CH
2
)
4
COOH
[-NH(CH
2
)
6
NHCO(CH
2
)
4
CO-]
n
+ 2nH
2
O
-To nilon 6,10 : Duoc trng ngung gua hexametilendiamin voi sebacoyl
diclorua:
nH
2
N(CH
2
)
6
NH
2
+ nClOC(CH
2
)
8
COCl
[-NH(CH
2
)
6
NHCO(CH
2
)
8
CO-]
n
+ 2nHCl
-To enang: Duoc trng ngung tu axit -aminoenatoic:
nH
2
N-(CH
2
)
6
COOH [-NH(CH
2
)
6
CO-]
n
+ nH
2
O
-To capron (to caprolactam): Duoc diu ch tu monome caprolctam:
KHOA HA DHSP TPHCM GIO TRNH HA HU CO 3
B mn Ha Hu Co L Vn Dng
Trang 244
t capron
n
)
_
O
C
_
(CH
2
)
5
_
NH
_
(
o
p
, t
caprolactam
n
C=O
NH
CH
2
CH
2
CH
2
CH
2
CH
2

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