BT Hoa Huu Co Tap2

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Ti liu dnh cho:
+ Hc sinh chuyn Ha.
+ Sinh vin cc trng i hc.
+ Gio vin Ha hc.
02 2010
Bi t p Ha H c H u C T p 2 Ti l i u dnh cho si nh vi n cc t r ng i h c
Copyright 2010 volcmttl@yahoo.com.vn 1
L i ni u
Ha h c h u c l m t trong nh ng b mn r t quan tr ng trong lnh
v c Ha h c ni ring v ph m tr Khoa h c t nhin ni chung. Tuy nhin
hi n nay, cc ti li u tham kh o v bi t p ha h c h u c l khng nhi u. V
v y vi c t ng h p cc t li u c m t ti li u tham kh o b ch v d ti p
thu h n l vi c r t c n thi t.
Bi t p Ha h c h u c l m t ti li u c bin so n d a trn vi c
t ng h p l i t nhi u ngu n t li u khc nhau theo t ng chuyn h c
sinh, sinh vin d n m b t. Ti li u g m hai ph n: Ph n bi t p theo t ng
chuyn v ph n h ng d n gi i. Cc bi t p trong t ng chuyn c
tuy n ch n k l ng nh m m c ch m b o cho cc d ng b i t p khng
trng l p v h c sinh, sinh vin c th ti p c n nhi u h ng ra khc nhau
t cng m t d li u ki n th c.
Bi t p Ha h c h u c bao g m hai t p:
- T p 1: G m b y chuyn t ng ng v i n i dung thu c ph n i c ng
ha h c h u c v ph n ki n th c ha h u c t bi alkane n cetone
(theo ch ng trnh ha h c ph thng).
- T p 2: G m cc ph n t acid carboxylic n cc h p ch t d v ng. Ngoi
ra cn minh h a thm m t s bi t p nng cao t ng h p cc chuyn .
V l ti li u t ng h p l i cc bi t p n m trong cc gio trnh, sch tham
kh o bi t p h u c , cc thi h c sinh gi i nn p n cho t ng bi khng
thay i theo p n c a t ng t i li u tham kh o. V v y Bi t p Ha h c
h u c khng ph i l m t ti li u do m t nhm tc gi bi n so n m ch l
ti li u t ng h p c ch n l a t cc ngu n t li u s n c. (T ng h p t ngu n
Internet copyright volcmttl@yahoo.com.vn).
Part 1: AXIT CACBOXYLIC ESTE
COOH
O H
O O
C H
3
CH
3
C C
H
HOOC
H COOH
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: i khi ho h c l p th c a cc h p ch t h u c c th c xc nh b ng cch kh o st tnh ch t
ha h c c tr ng c a chng. C u t o c a m t trong cc ng phn c a axit 5-norbonen-2,3-dicacboxylic,
h p ch t X (k hi u ~ ch khng nu r ha h c l p th ) c hnh thnh nh cc th nghi m sau:
COOH
COOH
X
Khi un nng X nng ch y v tch n c t o ra h p ch t m i Y. H p ch t Y tan ch m trong l ng d
dung dch n c c a NaOH t o X
1
, cng m t s n ph m nh X t o thnh trong l ng d dung dch
n c c a NaOH. Dung dch thu c c a X
1
trong NaOH c tc d ng v i iot, t o thnh cc h p ch t
c ch a iot. Axit ha dung dch t o m t h n h p hai ch t ng phn tri t quang (ti u tri n hay raxemic) A
v B theo t l 3:1. Chu n 0,3913g h p ch t A v i NaOH 0,1000M c m t phenolphtalein c n dng
12,70mL baz . C n cng m t th tch NaOH 0,1000M NaOH chu n 0,3913g h p ch t B. Khi un
nng, h p ch t A chuy n ch m thnh h p ch t m i C khng ch a iot v c th ph n ng v i n c. Trong
cng i u ki n, h p ch t B khng x y ra chuy n ha ny nh ng khi un nng v i axit clohydric th
chuy n ch m thnh A. Vi t v cn b ng m i ph ng trnh ph n ng. Khng c n vi t c ch ph n ng.
1. nh d u (*) cc nguyn t cacbon phi i x ng (asymmetric) trong axit 5- norbonen-2,3-
dicacboxylic.
2. Vi t cng th c ha h c l p th c a t ng ng phn l p t h c th c c a h p ch t X v c u t o c a
s n ph m tch n c n u c x y ra.
3. Vi t cc ph ng trnh ph n ng c a m t ng phn l p th b t k c a X v h p ch t t ng ng Y
v i l ng d dung dch NaOH trong n c.
4. Tnh kh i l ng mol phn t c a ch t A. Vi t cc ph ng trnh ph n ng t X
1
n A.
5. Vi t ph ng trnh ph n ng t o thnh C t A v ph n ng c a C v i n c.
6. Vi t cng th c ha h c l p th c a h p ch t X tho mn t t c cc d ki n cho.
7. Vi t cc ph ng trnh ph n ng d n t B n A.
8. A v B c ph i l cc ng phn khng i quang (diastereoisomers)?
BI GI I:
1. Cc trung tm b t i c a X:
*
* COOH
*
COOH
*
2. Cng th c c u t o c a cc ng phn l p th c a X c ghi bn tri, c t bn ph i l c u t o c a s n
ph m tch n c t ng ng (n u s n ph m khng t n t i c d u g ch ngang).
COOH OC
O
COOH OC
COOH CO
O
COOH CO
COOH
COOH
COOH
COOH
3. Ph n ng c a m t ng phn l p th c a X v i NaOH:
COOH
COOH
+ 2NaOH
COONa
COONa
+ 2H
2
O
Ph n ng c a m t ng phn l p th c a Y v i NaOH:
OC
O + NaOH
oc
COONa
COONa
+ H
2
O
4. M
A
= 0,3913/(12,7.0,100/1000) = 308 (g/ mol
-1
) Cc ph n ng t X n A:
COONa
COONa
I
2
-NaI
I
O CO
COONa
HCl
-NaCl
I
COOH
O CO
5. Chuy n ha A thnh C:
I
COOH O CO + HI
O CO O CO
Ph n ng c a C v i n c
O CO + 2 H
2
O HO COOH
O CO HO COOH
6. C u t o c a X l:
COOH
COOH
7. Chuy n ha B thnh A
I I I
HOOC
CO + H
2
O COOH H
2
O
O COOH OH COOH O CO
8) Khng, A v B khng ph i l cc ng phn khng i quang.
Bi 2: Cc nh ha h c c a cng ty Merck Frosst Canada Montral pht tri n m t d c ph m r t c
tri n v ng v h u hi u tr b nh suy n. C u t o c a MK-0476 nh sau.
COOH
CH
3
H
3
C OH
S
Cl N
MK 7406
Trong qu trnh ki m tra, h pht minh m t qa trnh t ng h p n gi n v hi u qu , m t d i y cho
s thiol ha m t ph n c a MK 0476 b t u t este dietyl A
1. Hy cho bi t c u t o c a cc s n ph m trung gian B F trong qa trnh t ng h p ny.
6 5 3 2 2 5 3 4
3
C H COCl 1) CH -SO Cl/(C H ) N 1.LiAlH
12 14 3 12 13 2 Pyridin 2.NaCN 2.H O
B C(C H O ) D(C H O N)
+

( aq) 3 2 2 5 3
- +
3 3
1.NaOH 1. CH -SO Cl/(C H ) N
9 14 3
2.H O 2.CH COS Cs
F(C H O S) E
+

M t trong nh ng giai o n cu i c a qa tr nh t ng h p MK 0476, mu i diliti c a thiol axit
(G) trn c ghp v i m ch c a phn t nu d i y (s d i)
2. Cn c trn ha h c l p th quan st c c a ph n ng trn, g i tn c ch c a qa trnh ghp
ny?
3. N u qa trnh ph n ng x y ra theo c ch c ngh nh trn th t c ton ph n (chung)
s thay i nh th no n u n ng c a c mu i thiolat v ch t n n u cng lc tng g p ba?
4. Cc nghin c u m u c ti n hnh v i vi c s d ng brom etan nh l m t ch t n n t i u
ha qa trnh ghp ni trn. V c u t o s n ph m chnh c a ph n ng gi a m t mol ng
l ng brom etan v i:
a. G thm hai mol ng l ng baz .
b. G thm m t mol ng l ng baz .
1. KOH
(aq)
2. CH
2
N
2
COOC
2
H
5
COOH
COOC
2
H
5
SH
5. Qa trnh ghp c th tr nn ph c t p do s nh h p oxi ha (dime ha oxy ha c a G). Vi t
cng th c c u t o Lewis, ch r t t c cc electron khng lin k t c a s n ph m nh h p - oxy
ha trn.
S GHP M CH
BI GI I:
1. Cng th c c u t o c a cc ch t:
CH
2
OH
O
CH
2
O
O
CH
2
OH
B
CH
2
OH
C
H
2
C C N
D
CH
2
OH
CH
2
S C CH
3
CH
2
CO
2
CH
3
E
O
CH
2
CO
2
CH
3
F
Cl
N
S
O
O
CH
3
O
CH
3
CH
3
OH
1.
-
S
+
Li
-
CO
2
+
Li
2. H
+
Cl N
S
COOH
CH
3
CH
3
OH
CH
2
O
2. S
N
2: th nucleophin l ng phn t .
3. v = k[tc nhn][tc ch t nucleophin]
T c chung ty thu c vo n ng c a c tc nhn l n tc ch t nucleophin. Nh v y, g p ba n ng
c a cc ch t tham gia ph n ng s d n n t c chung c a ph n ng t ng g p 9 l n.
4. V i hai ng l ng baz :
CH
2
SCH
2
CH
3
CH
2
CO
2
H
V i m t ng l ng baz :
CH
2
SH
CH
2
CO
2
CH
2
CH
3
5. Cng th c Lewis c a s n ph m dime:
CH
2
S SCH
2
CH
2
H
2
C
HO O O OH
Bi 3: N m Aspergillus nidulans t o ra hai lacton (este vng) th m A v B (C
10
H
10
O
4
) m i ng phn tan
trong dung dch NaOH l nh trong n c nh ng khng tan trong dung dch NaHCO
3
trong n c. C A v B
u cho mu tm v i dung dch FeCl
3
trong n c. Ph n ng c a A v i CH
3
I c m t K
2
CO
3
t o thnh C
(C
11
H
12
O
4
) m ph
1
H NMR c a n th y c ch a ba nhm metyl khng gi ng nhau, m t nhm lin k t
tr c ti p v i vng th m. S tch lo i nhm metyl c ch n l c c a C v i BCl
3
r i x l k ti p trong n c
t o ra D l m t ng phn m i c a A. Ph
1
H NMR c a h p ch t D cho th y r s hi n di n c a m t
nhm hydroxyl c t o lin k t hydro n i phn t t i o = 11,8pm
OH
H
3
C
H
3
C CO
2
CH
3
O
HO
E
I
H p ch t D c t ng h p nh sau: Phenol E c metyl ha (MeI/K
2
CO
3
) t o F(C
9
H
12
O
2
) sau F
c kh b ng liti ki m lo i trong amoniac l ng v 2 metylpropan 2 ol cho m t dien i x ng v
khng lin h p G. C th chuy n dien ny thnh lin h p b ng ph n ng v i KNH
2
trong amoniac l ng
r i x l k ti p trong n c, qa trnh ny ch t o m t s n ph m H. S ozon phn H r i x l khng kh
l ti p t o ra nhi u s n ph m, trong c xetoeste I. Th c hi n ph n ng Diels Alder h p ch t H v i
dimetyl but 2 indioat J t o thnh K (C
15
H
20
O
6
) m khi un nng s lo i eten t o ra m t este th m L.
Th y phn L trong mi tr ng baz r i axit ha dung dch t o thnh M(C
11
H
12
O
6
) m khi un nng trong
chn khng t o ra N (C
11
H
10
O
5
). Kh N b ng NaBH
4
trong dimetylfomamit t o thnh C v m t lacton O
ng phn, O c ng c th thu c nh metyl ha B.
1. Vi t cng th c c u trc c a t t c cc h p ch t t A n O.
2. Hy trnh by m t c u trc khc c a B.
BI GI I:
1. Cng th c c u t o c a cc ch t:
H
3
C
OCH
3
O
H
3
C
OCH
3
H
3
C
OCH
3
O
O
HO
A
OH
O
HO
B
OH
O
H
3
CO
O
O
C
OCH
3
H
3
C
H
3
C
H
3
C
O
H
3
CO
D
HO
H
3
CO
E
F
G H I J
OCH
3
CH
3
H
3
CO
H
3
CO
CH
3
OCH
3
H
3
C CO
2
CH
3
O
CO
2
CH
3
CO
2
CH
3
2. Cng th c khc c a B:
OH
H
3
C
O
H
3
CO
O
Bi 4: (-)-Atractyligenin l m t h p ch t ho t ng sinh h c c c l p t cy g i l Thistle ch t choc.
Ng i Zulu dng n ch a b nh nh ng th ng gy hi m h a ch t ng i. c th t o m t h p ch t
t ng ng c c tnh km h n, nay c nhi u ph ng php t ng h p ha h c:
HO
OH
COOH
5 10 5 8
B(C H O) C(C H O) D E G H I
OCH
3
H
3
C
H
3
CO CO
2
CH
3
CO
2
CH
3
H
3
C
H
3
CO
CO
2
CH
3
CO
2
CH
3
OCH
3
H
3
C
H
3
CO CO
2
H
CO
2
H
OCH
3
K L M
H
3
C
H
3
CO
OCH
3
O
O
O
H
3
C
H
3
CO
OCH
3
O
O
O N
Br
O
A
Trong s t ng h p ch t t ng ng c a (-) Atractyligenin, h p ch t A u c dng lm nguyn li u u.
Tr c h t cho ch t A tc d ng v i dung dch natri hydroxit trong n c t o thnh B (C
5
H
10
O).
1. Hy vi t cng th c c u t o c a h p ch t B
2. Khi cho h p ch t B tc d ng v i kali dicromat trong dung dch n c c a axit sunfuric thu c C
(C
5
H
8
O). Hy vi t cng th c c u t o c a h p ch t C.
3. Ho tan h p ch t C trong toluene r i s c kh hydro bromua qua dung dch cho n khi ton b C
ph n ng h t thu c h p ch t D. Hy vi t cng th c c u t o c a h p ch t D
4. H p ch t D c ng phn l p th khng? N u c, hy cho bi t c bao nhiu ng phn l p th ?
5. Cho h p ch t D tc d ng v i dung dch natri hidroxit trong etanol t o thnh h p ch t E, khi un
nng s chuy n v thnh ch t F Hy vi t cng th c c u t o c a h p ch t E.
6. H p ch t F c ng phn l p th khng? N u c, hy cho bi t c bao nhiu ng phn l p th ?
7. Dung dch h p ch t F tc d ng v i kali pemanganat cho h p ch t G. Cu i cng G c un nng
h i l u trong etanol c m t xc tc axit sunfuric t o thnh h p ch t H.Hy cho bi t tn IUPAC c a
H H p ch t H c cho tc d ng v i 2 metylbutylmagie bromua. Sau khi axit ha, thu c m t
h n h p cc s n ph m ng phn I.
8. Hy vi t cng th c c u t o s n ph m I (khng xt ng phn)
9. Hy tr l i cc cu h i sau
a. S ng phn l p th c l p c c a s n ph m I l 2, 4, 6 hay 8?
b. T t c cc ng phn l p th c l p c c a s n ph m I c t o thnh v i s l ng b ng
nhau, hay m t ph n c s l ng khc nhau hay t t c c s l ng khc nhau?
c. Trong cc ng phn l p th c l p c c a s n ph m I th t t c c cng i m nng ch y hay
t t c c i m nng ch y khc nhau hay m t s c i m nng ch y gi ng nhau?
BI GI I:
Cng th c c u t o cc ch t nh sau:
Br OH
A
B
O O
O
O
*
C
Br
D E
F
O O
OH O
G H
*
OH
*
I
Ch t D c 2 ng phn i quang
Ch t F c hai ng phn hnh h c
- Ch t I c 4 ng phn l p th ring bi t
- C p ng phn khng i quang c l ng khc nhau. C p i quang c l ng b ng nhau
- C p ng phn khng i quang c i m nng ch y khc nhau. C p ng phn i quang c i m
nng ch y b ng nhau
Bi 5: M t thnh ph n S c a d u hoa h ng d ng c c u t o sau:
cis
H
2
C OOC(CH
2
)
7
C C (CH
2
)
7
CH
3
H H
HC
H
2
C
OOC(CH
2
)
7
OOC(CH
2
)
18
CH
3
cis
C C
H H
H
2
cis
C C C
H H
(CH
2
)
4
CH
3
a. C bao nhiu ng phn i quang c a S? Dng d u hoa th (*) ch ra cc tm i x ng g ng
c a phn t , n u c.
b. S tc d ng v i natri metoxit cho h n h p 3 este metyl. ngh tn c a 3 este ny. Dng cch ghi
Z, E n u c n.
c. Cho cc este metyl ch a no tc d ng v i ozon r i v i k m xc nh v tr c a cc lin k t i
trong phn t . Vi t cng th c c u t o c a 4 h p ch t c nhm ch c andehit. Vi t tn IUPAC c a
chng.
d. Ch s x phng ha c a m t ch t bo c nh ngha l s miligam kali hydroxit c n thu
phn 1g ch t bo. Ch s ny c dng so snh cc kh i l ng phn t t ng i c a ch t
bo. Hy tnh th tch c a kali hydroxit 0,996M c n dng x phng ha 10,0g ch t bo S
e. Ch s x phng ha c a S l bao nhiu?
f. Ch s iot c a ch t bo c nh ngha l s gam iot (I
2
) c th tham gia ph n ng c ng v i 100g
ch t bo. Hy tnh ch s iot c a ch t S.
BI GI I:
a. Cc phn t c a ch t thnh ph n S c hai ng phn i quang
cis
H
2
C OOC(CH
2
)
7
C C (CH
2
)
7
CH
3
H H
HC
*
H
2
C
OOC(CH
2
)
7
OOC(CH
2
)
18
CH
3
cis
C C
H H
H
2
cis
C C C
H H
(CH
2
)
4
CH
3
b. Cc cng th c c u t o v tn g i c a este metyl l:
O
(Z) - metyloctadec-9-enoat
O
O
O
(9Z;12Z) - metyloctadec-9,12-dienoat
O
O
metyl octadecanoat
c. Ozon phn S r i tc d ng v i Zn cho cc andehit sau:
nonal
O O
hexanal
O O
metan dicacbadehit
O
O O
metyl nonalat
d. S mol KOH dng nhiu g p 3 l n s mol triglixerit S
-3
(S)
10,0
n = = 11,29.10 (mol) = 11,29 (mmol)
885.402
; V
KOH
= 3.n/V = 34,0 mL
e. Ch s x phng ha = 3,40(mmol/g).56,11(g/ mol) = 191
f. 112,9mmol S c ch a 3 . 112,9mmol lin k t i C = C
V y m(I
2
) = 0,3388(mol) . 253,8(g/mol) = 85,98g Ch s iot = 86
Bi 6: Axit xitric (axit-2-hydroxy-1,2,3-propantricacboxylic) l axit s c p c a cc lo i cy thu c h cam,
chanh v c ng gp ph n lm nn v chua c tr ng c a n. Cch s n xu t th cng nh t c a n l ln men
m t ma hay tinh b t, h s d ng lo i n m Aspergillus niger t i pH = 3,5. Axit xitric c s d ng r ng
ri trong cng nghi p th c ph m, s n xu t n c ng t v lm thu c c n mu trong cng nghi p
ph mnhu m. Ngoi ra n c ng l m t ch t trung gian quan tr ng trong c c qa trnh sinh ha.
a. Ch t no c sinh ra khi ta un nng axit xitric v i axit sunfuric c 45 50
o
C. Hy vi t cng
th c c u t o v c tn c a s n ph m t o thnh theo IUPAC. Lo i axit h u c no tham gia c
ph n ng trn?
Sau khi un nng axit xitr ic v i axit sunfuric, ng i ta thm vo anisol (metoxybenzen) vo h n h p ph n
ng v nh n c ch t A(C
12
H
12
O
5
).
A t o anhydrit khi un nng v i anhydrit axetic
trung ho 118mg A c n 20mL dung dch KOH 0,05N
Cng m t l ng ch t A nh trn c th ph n ng h t c v i 80mg brom t o thnh s n
ph m c ng
b. Xc nh cng th c c u t o A
c. Xc nh cc ng phn c th c c a A sinh ra trong ph n ng trn, hy xc nh c u d ng v vi t
tn IUPAC c a chng.
d. Trong ph n ng brom ha th c bao nhiu ng phn l p th c a A c sinh ra. Hy v cng
th c chi u Fischer c a chng.
e. Xc nh c u hnh tuy t i c a cc trung tm b t i trong cc s n ph m cu d
N u trong ph n ng hnh thnh A ta thay anisol b ng ch t khc nh phenol hay resoxinol th t ng ng ta
thu c cc ch t B v C. B khng cho ph n ng mu khi tc d ng v i FeCl
3
nh ng C th c. Trong cng
i u ki n ph n ng t o thnh 2 ch t B, C th hi u su t t o thnh C cao h n.
f. Xc nh cng th c c u t o c a B v C
g. Ph n ng t o thnh A v B khc nhau i m c b n no?
h. L do t i sao hi u su t t o thnh C cao h n t o thnh B
BI GI I:
a. Ph n ng
H
2
C COOH
4
H
2
C COOH
HO C COOH
2 4
H SO
C O
+ H
2
O + CO
H
2
C COOH
H
2
C COOH
axit-1,3-pentadioic
Ch c cc axit o - hydroxy cacboxylic m i tham gia ph n ng ny
b. - Kh i l ng phn t A = 236
20mL KOH 0,05M ph n ng v i 118mg A
1000mL KOH 1M ph n ng v i 118g A
A ph i l axit 2 ch c
- Kh i l ng phn t A = 236
80mg Br
2
ph n ng v i 118mg A
160mg Br
2
ph n ng v i 236mg A
A c ch a m t lin k t i. Trong phn t A c ch a vng anisol
N l i c hnh thnh t axit HOOC CH
2
COCH
2
COOH v c cng th c phn t C
12
H
12
O
5
.
Do c s c n tr khng gian c a cc nguyn t hydro trong anisol nn nhm t h bu c ph i n m
v tr para so v i nhm OCH
3
. Nh v y cng th c c u t o c a ch t A s nh sau:
H
3
CO
COOH
COOH
V A t o c anhydrit nn hai nhm -COOH bu c ph i cng pha so v i lin k t i.
c. Cc ng phn c a A
OCH
3
COOH
COOH
axit-(E)-3-(2-metoxyphenyl)-2-pentendioic
OCH
3
COOH
COOH
axit-(Z)-3-(2-metoxyphenyl)-2-pentendioic
HOOC
H
3
CO
COOH
axit-(Z)-3-(4-metoxyphenyl)-2-pentendioic
d. Hai s n ph m khi cho A tc d ng v i brom
COOH
COOH
H Br
HOOCH
2
C Br
Br H
Br CH
2
COOH
OCH
3 OCH
3
1 2
Hai ch t ny l enantiome
e. C u hnh tuy t i t i cc trung tm l p th
COOH
H
S
Br
HOOCH
2
C Br
COOH
Br
R
H
Br
S
CH
2
COOH
OCH
3 OCH
3
1 2
f. Cng th c c u t o cc ch t B v C
CH
2
COOH
CH
2
COOH
O O
HO O O
B
C
g. Trong s hnh thnh ch t A t anisol th h ng t n cng l v tr para so v i nhm OCH
3
. Tuy nhin
trong ph n ng t o thnh ch t B t phenol th v tr t n cng l ortho so v i nhm OH. S khc nhau ny
l do s c n tr khng gian c a cc nguyn t hydro trong nhm OCH
3
. Nh v y s t n cng c th x y
ra hai v tr ortho v para nh ng h ng t n cng ortho c u tin h n do s n ph m trung gian c th
vng ha c t o s n ph m b n B.
h. Phenol ch c 1 nhm OH trong vng phenyl cn resoxinol th l i c n 2 nhm OH trong vng
phenyl m hai nhm ny l i v tr meta. i u ny d n n v tr 4 trong resoxinol c m t electron l n
i v i resoxinol.
6
1
OH
HO
5
4
3
2
OH
Nh v y th trong cng i u ki n ph n ng th l ng s n ph m C lun nhi u h n B
Bi 7: S pht tri n c a cc lo i d c ph m m i ph thu c ch y u vo t ng h p h u c . Ph ng php
chnh l i phn t (fine-tuning) c s d ng c th nh n c cc tnh ch t nh mong mu n. Sau y l
qa trnh t ng h p thu c gy m c c b proparacaine (cn c g i l proxymetacaine), ch t ny c s
d ng i u tr cc b nh v m t.
1. Hon thnh qa trnh t ng h p b ng cch vi t cng th c c u t o cc ch t A, B, C, D v E
O
OH
HNO
3
HO
n-C
3
H
7
Cl
A
baz
B
SOCl
2
HOCH
2
CH
2
N(C
2
H
5
)
2
C D
H
2
/Pd(C)
E
T t c u l cc s n ph m chnh
2. Khi ta nitro ha axit - m hydroxybenzoic th thu c nh ng s n ph m no?
3. Khi t C
4
H
9
Cl c s d ng b c 2 thay cho C
3
H
7
Cl th i u ny s d n t i:
a. M t s n ph m t ng t B (n u i u ny ng hy vi t CTCT s n ph m)
b. Khng c ph n ng
c. S phn h y t C
4
H
9
Cl
d. M t ph n ng th S
E
Hy ch n cu tr l i ng
BI GI I:
1. Cng th c c u t o cc ch t t A n E:
O
O
2
N
OH
HO
A
O
O
2
N
OH
H
3
CH
2
CH
2
CO
B
O
O
2
N
Cl
H
3
CH
2
CH
2
CO
C
O
2
N
H
3
CH
2
CH
2
CO
O
OCH
2
CH
2
N(C
2
H
5
)
2
D
H
2
N
H
3
CH
2
CH
2
CO
O
OCH
2
CH
2
N(C
2
H
5
)
2
E
2. Cng th c c u t o cc s n ph m:
NO
2
O
OH
OH
3. c
O
OH
+
O
2
N
OH
Bi 8: Vi t c ch c a cc ph n ng sau y:
a.
Base
6 5 3 2 6 5 2 3
C H COCl CH CH OH C H COOCH CH +
b.
acid
3 2 2 3 4
CH CONH H O CH COOH NH
+
+ +
BI GI I:
a. C ch ph n ng:
CH
3
CH
2
OH+ Cl C
O
CH
3
CH
2
O C
O H
Cl
+
-
CH
3
CH
2
O C
OH
Cl
CH
3
CH
2
O C
O
- HCl
b. C ch :
NH
2
C
CH
3
O
H
+
NH
2
C
CH
3
OH
+
OH
2
CH
3
C
NH
2
OH
O
H
H
H
+
CH
3
C
NH
2
OH
H O
H
+
CH
3
C
NH
3
+
OH
H O CH
3
COOH
NH
4
+
+
+
-
+
Bi 9: Lo i d c ph m c s d ng nhi u nh t trong t t c m i th i i l axit axetylsalixilic (ASS), n
c by bn r ng ri trn th tr ng d i tn th ng m i l aspirin lm thu c ch ng nh c u. Ci tn
aspirin l do m t cng ty c xu t nm 1899. ASS c th c t ng h p b ng con ng sau y:
Vi t cng th c c u t o c a A, B, C v ASS.
BI GI I
Ph n ng u tin l ph n ng Kolbe Schmidt, ti p theo l ph n ng proton ha, sau ph n ng ny th axit
salixilic B c hnh thnh. Ph n ng v i anhydrit axetic s d n n vi c t o thnh axit axetylsalixilic ASS.
Bi 10: Sildenafil (m t lo i thu c tng l c) c t ng h p theo s :
I
Sildenafil
NH
2
NH
2 1. Me
2
SO
4
, dd NaOH
2. NaOH, H
2
O
HNO
3
, H
2
SO
4
50
o
C, 2 h
A
B C
SOCl
2
, DMF, toluen, 55
o
C, 6 h
dd NH
3
, 20
o
C, 2 h
C
OEt
O
O
O
H
hi l u, 2 h,
-
NH N
ClSO
3
H, SOCl
2
t
o
phng, 18 h
G
10
o
C, 2 h
NH , H
2
O N CH
3
-
N)
2
CO (N
EtOAc, 50
0
C, 4 h
H
2
(50 psi), 5% Pd/C
E D
OH
O O
Et
O
O
N N CH
3
S
HN
N
Pr
N
N
Et
O
2
CH
3
K
I
NH N
E, EtOAc
t
o
phng, 70 h
L
1. Hy hon chnh dy ph n ng trn, bi t r ng:
o Qu trnh chuy n sang G c t o thnh axit sunfonic trung gian sau m i chuy n
thnh sunfonyl clorua.
o N,N
,
-cacbonyliimiazol (CDI) l m t lo i tc nhn dng ho t ho axit cacboxylic
cho ph n ng th nucleophin c a nhm cacbonyl.
2. Vi t c ch ph n ng chuy n [I] thnh K.
BI GI I
NH
2
NH
2 HNO
3
, H
2
SO
4
50
o
C, 2 h
C
OEt
O
O
O
EtOAc, 50
0
C, 4 h
SOCl
2
, DMF, toluen, 55
o
C, 6 h
dd NH
3
, 20
o
C, 2 h
H
2
(50 psi), 5% Pd/C
E
C
D
H
2
N
O
N
N
Pr
H
2
N
CH
3
CH
3
H
A
1. Me
2
SO
4
, dd NaOH
2. NaOH, H
2
O
H
2
N
O
N
N
Pr
O
2
N
EtO
O
N
N
Pr
B
CH
3
HO
O
N
N
Pr
HO
O
N
N
Pr
O
2
N
CH
3
ClSO
3
H, SOCl
2
t
o
phng, 18 h
H
Me
hi l u, 2 h ,
-
N)
2
CO (N
K
10
o
C, 2 h
H
I
OEt
OH
O
NH , H
2
O N
CH
3
-
OEt
SO
2
Cl
OH
O
G
OEt
S
OH
O
O
2
N CH
3
N
OEt
S
O
O
O
2
N CH
3
N
O
OEt
S
O
O
2
N CH
3
N
NH N
N N
NH N
N N
K
E, EtOAc
t
o
phng, 70 h
L
OEt
S O
2
N CH
3
N
H
O
O
N
H
2
N
N
N
CH
3
Pr
2. C ch t [I] sang K
- H
+
OEt
S
O
C
O
O
2
N CH
3
N
N N
O
N HN
OEt
S
O
C
O
2
N CH
3
N
N N
O
N
N
O
+ H
+
+ CO
2
+
OEt
S
O
O
2
N CH
3
N
N N
N HN
(-)
Bi 11: Vi t cng th c c u t o c a s n ph mcu i (n u c) t cc ph n ng sau:
+ (I
2
, KI, NaHCO
3
) A
Br
CH
3
H
2
N CH COOH B +
BI GI I
A l
O
O
I
B khng t n t i v ph n ng khng x y ra
Bi 12: S n ph m no c t o thnh khi cho stiren oxit t ng tc v i dietylmalonat?
BI GI I:
O
CH(COOEt)
2
CH CH
2
COOEt
C
O COOEt
O
O
Ph
EtOOC
O
2
o
1.OH,H O
2.H
3.t
+
Bi 13: Vi t cng th c c u trc cc d ng enol c a dietylmalonat (1), Etylaxetoaxetat (2). Trong cc c u

trc c a (2), cho bi t d ng no b n nh t, d ng no km b n. Gi i thch?
COOH
O
Ph
O
BI GI I:
a. Cc c u trc
C
H
OEt
O
H
O
EtO
C
H
OEt
O O
EtO
H
OEt
O O
EtO
b. Trong :
- D ng A t b n do n i i khng li n h p
- D ng B b n nh ng khng c c ng h ng este
- D ng C b n nh t do c n i i li n h p v c ng h ng este
CH
3
COCH
2
COOEt
C H
2
OEt
O
H
O
C
H
C H
3
OEt
O O
C
H
C H
3
OEt
O
H
O
H
A
B
C
Bi 14: Khi x l axit salixylic v i dung dch n c brom d th axit d dng t o thnh tribromphenol.
Vi t c ch . C th ch i ph n ng c a axit m- v p-hidroxibenzoic khng?
BI GI I:
OH
COOH
Br
Br
2
OH
COOH
H
+
O
Br
C O H
O
H
+
CO
2
Br
O
Br
2
H
+
Br
Br
Br
OH
+
-
-
T o thnh xetoaxit | torng gian, lo i h p ch t ny d b decacboxyl ha.
ng phn meta- kh x y ra ph n ng v khng t o thnh xetoaxit |
ng phn para- c th c v h p ch t ny l xetoaxit c n i i , o |
O
COOH
Br
Part 2: AMINOAXIT AMIN PROTEIN
N
O
N
O
N
N
O
N
N
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: H p ch t h u c A c 74,074% C; 8,642% H; c n l i l N. Dung dch A trong n c c n ng %
kh i l ng b ng 3,138%, si nhi t 100,372
o
C; h ng s nghi m si c a n c l 1,86
o
C.
1. Xc nh cng th c phn t c a A.
2. Oxi ha m nh A thu c h n h p s n ph m trong c E (axit piridin -3-cacboxilic) v F
(N-metylprolin). Hy xc nh cng th c c u t o c a A v cho bi t gi a E v F ch t no c sinh ra
nhi u h n, ch t no c tnh axit m nh h n.
3. A c 1 ng phn c u t o l B; khi oxi ha m nh B c ng sinh ra 1 h n h p s n ph m trong c E v
axit piperidin-2-cacboxilic. Xc nh cng th c c u t o c a B.
4. Cho A v B tc d ng v i HCl theo t l mol 1:1, ch t no ph n ng d h n? Vi t cng th c c u t o
c a cc s n ph m.
BI GI I:
1. 1 : 7 : 5
14
284 , 17
:
1
642 , 8
:
12
074 , 74
N : H : C = = (C
5
H
7
N)
n
mol / g 162
372 , 0
1
100
862 , 96
138 , 3
86 , 1
t
m . k
M = =
A
= 81n = 162 n = 2; CTPT: C
10
H
14
N
2
2.
F E
A
N N
COOH
N
COOH
CH
3
N
CH
3
E sinh ra nhi u h n F
3.
B
Axit piperidin -2-cacboxilic:
anabazin
N
N
COOH
H
N
H
4.
Cl
-
N
N
H
N
N
H
3
C
Cl
-
Bi 2: S p x p c gi i thch s tng d n tnh axit c a:
(D)
(A) (B)
(C)
;
N
COOH
;
COOH
;
CH
2
COOH
N COOH
BI GI I:
(D)
<
<
<
-I
1
CH
2
COOH
(C) (A)
-I
2
-I
3
N
H
C
O
O
-C
3
(B)
-C
4
-I
4
N
COOH
COOH
V: - I
1
< - I
2
nn (C) c tnh axit l n h n (D).
(A) v (B) c N nn tnh axit l n h n (D) v (C)
(A) c lin k t hiro n i phn t l m gi m tnh axit so v i (B).
Bi 3: L-Prolin hay axit (S)-piroliin-2-cacboxylic c pK
1
= 1,99 v pK
2
= 10,60. Piroliin (C
4
H
9
N) l
amin vng no nm c nh.
1. Vi t cng th c Fis v cng th c ph i c nh c a L-prolin. Tnh pHI c a h p ch t ny.
2. Tnh g n ng t l d ng proton ha H
2
A
+
v d ng trung ho HA c a prolin pH = 2,50.
3. Tnh g n ng t l d ng eproton ho A
v d ng trung ho HA c a prolin pH = 9,70.

4. T metylamin v cc ha ch t c n thi t khc (benzen, etyl acrilat, natri etylat v cc ch t v c ), hy
vi t s i u ch N-metyl-4-phenylpiperiin.
BI GI I:
1. pH
I
=
1, 99 10, 6
2
+
= 6,3
NH H
COOH
N
COOH
H
H
NH H
COOH
N
COOH
H
H
2. p d ng ph ng trnh Henderson - Hasselbalch
H
2
A+
1
K
HA + H
+
;
+
1 +
2
[HA][H ]
K
[H A ]
=
+
2
[HA]
lg
[H A ]
= pH pK
1
= 2,50 1,99 = 0,51 Suy ra:
+
2
[HA]
[H A ]
= 3,24
V y pH = 2,50 d ng trung ho chi m nhi u h n d ng proton ha 3,24 l n.
Hay t l gi a d ng proton ha v d ng trung ho l 0,309
3. H
2
A
+
+ A
[A ]
HA
; suy ra lg
[A ]
HA
= pH pK
2
= 9,70 10,60 = 0,90
=>
[A ]
HA
= 0,126 ~
1
8
V y pH = 9,7 t l gi a d ng eproton h a v d ng trung ho l
1
8
.
4.
CH
3
NH
2
CH
3
-N
+Br
2
/Fe, t
o
Br
Mg
ete
MgBr
Bi 4: Hy cho bi t cc s n ph m c a s th y phn trong mi tr ng axit c a cc ch t CH
3
CONH
2
,
O
N
O
O
CH
3
BI GI I:
O
N
O
O CH
3
CH
3
-CONH
2
+
CH
3
-NH
2
-CH
2
-COOH + HOCH
2
COOH
CH
3
-COOCH
3
CH
3
-COOH + CH
3
OH
H
2
O
H
+
,
t
O
CH
3
-COOH
+ NH
4
+
H
2
O
H
+
,
t
O
H
2
O
H
+
,
t
O
O
N
O
O CH
3
CH
3
-CONH
2
+
CH
3
-NH
2
-CH
2
-COOH + HOCH
2
COOH
CH
3
-COOCH
3
CH
3
-COOH + CH
3
OH
H
2
O
H
+
,
t
O
CH
3
-COOH
+ NH
4
+
H
2
O
H
+
,
t
O
H
2
O
H
+
,
t
O
2.
.
Bi 5: H p ch t A (C
5
H
11
O
2
N) l m t ch t l ng quang ho t. Kh A b ng H
2
c xc tc Ni s c B
(C
5
H
13
N) quang ho t. Cho B tc d ng v i axit HNO
2
thu c h n h p g m ancol C quang ho t v ancol
tert-amylic (2-metyl-2-butanol).
Xc nh cng th c c u t o c a A. Dng cng th c c u t o, vi t ph ng trnh cc ph n ng t o
thnh B, C v ancol tert -amylic t A.
BI GI I:
N
O
CH
3
CH
2
-CH
2
-COOC
2
H
5
CH
2
-CH
2
-COOC
2
H
5
2 CH
2
=CH-COOC
2
H
5
1. OH
-
CH
3
N
COOC
2
H
5
O
CH
3
N
COOC
2
H
5
O
2. H
3
O
+
, t
o
CH
3
N
O
C
2
H
5
ONa
1. C
6
H
5
MgBr
2. H
3
O
+
CH
3
N
OH
C
6
H
5
CH
3
N
C
6
H
5
H
2
SO
4
, 170
o
C
CH
3
N
C
6
H
5
H
2
, Ni, t
o
*
CH
3
CH
3
CH
2
NO
2
CH
2
CH
(A)
CH
3
CH
3
CH
2
NH
2
CH
2
CH CH
3
CH
3
CH
2
+
CH
2
CH CH
3
CH
3
CH
2
OH
CH
2
CH
H
2
/ Ni HNO
2
H
2
O
CH
3
CH
3
CH
3
CH
2
C
CH
3
CH
3
CH
2
+
CH
2
CH
CH
3
CH
3
CH
3
CH
2
C
Chuyn v
H
2
O +
OH
Bi 6: T benzen ho c toluen v cc ch t v c t ng h p c cc d c ch t sau:
Axit 4-amino-2-hidroxibenzoic; axit 5-amino 2,4 dihidroxibenzoic.
BI GI I:
HNO
3
H
2
SO
4
, t
0
NO
2
NO
2
Sn/ HCl
NH
2
NH
2
OH
NH
2
HNO
2
OH
NH
2
CO
2
,OH
-
t
0
,p
COOH
HNO
3
H
2
SO
4
, t
0
NH
2
NH
2
OH
OH
HNO
2 CO
2
,HO
t
0
, p
OH
OH
COOH
OH
OH
COOH
O
2
N
OH
OH
Sn /HCl
COOH
H
2
N
ho c
HNO
3
H
2
SO
4
, t
0
NO
2
NO
2
K
2
Cr
2
O
7
NO
2
NO
2
NH
2
NH
2
Sn / HCl
CH
3
CH
3
H
+
COOH COOH
OH
OH
HNO
2
COOH
OH
OH
HNO
3
COOH
H
2
SO
4
O
2
N
OH
OH
COOH
H
2
N
Sn / HCl
Bi 7:
a. Dng cng th c c u t o, hy hon thnh s t ng h p sau y:
COCl
2
+ CH
3
OH C
2
H
3
O
2
Cl
6 5 2
C H NH
B
2
HOSO Cl
C
8
H
8
O
4
NSCl
3
NH
D
3
H O
+
C
6
H
8
O
2
N
2
S.
b. Gi i thch h ng c a ph n ng t o thnh C
8
H
8
O
4
NSCl v C
6
H
8
O
2
N
2
S.
BI GI I:
a. COCl
2
+ CH
3
OH CH
3
O-COCl
Chuy n v
CH
3
OCOCl
C
6
H
5
NH
2
NHCOOCH
3
HOSO
2
Cl
NHCOOCH
3
SO
2
Cl
NH
2
SO
2
NH
2
d
NH
3
NHCOOCH
3
SO
2
NH
2
H
3
O
+
(B)
(C) (D) (E)
b. NHCOOCH
3
nh h ng o, p; do kch th c l n, tc nhn l n nn vo v tr p.
NHCOOCH
3
este-amit th y phn thnh CO
2
| , cn SO
2
NH
2
b n h n.
Bi 8: TRF l tn vi t t t m t homon i u khi n ho t ng c a tuy n gip. Th y phn ho n ton 1 mol
TRF thu c 1 mol m i ch t sau:
NH
3
;
N
H
COOH
(Pro)
;
HOOC-CH
2
-CH
2
-CH-COOH
NH
2
(Glu)
;
N
N
H
CH
2
-CH-COOH
(His)
NH
2
Trong h n h p s n ph m th y phn khng hon ton TRF c dipeptit His -Pro. Ph kh i l ng cho bi t
phn t kh i c a TRF l 362 vC. Phn t TRF khng ch a vng l n h n 5 c nh.
1. Hy xc nh cng th c c u t o v vi t cng th c Fis c a TRF.
2. i v i His ng i ta cho pKa
1
= 1,8 ; pKa
2
= 6,0 ; pKa
3
= 9,2. Hy vi t cc cn b ng i n ly v ghi cho
m i cn b ng m t gi tr pKa thch h p. Cho 3 bi u th c:
pH
I
= (pKa
1
+pKa
2
+pKa
3
) : 3 ; pH
I
= (pKa
1
+pKa
2
) : 2 ; pH
I
= (pKa
2
+pKa
3
) : 2 ;
bi u th c no ng v i His, v sao?
3. Hy ngh s ph n ng v i y i u ki n t ng h p axit (D, L) glutamic t hidrocacbon
ch a khng qu 2 nguyn t cacbon trong phn t .
BI GI I:
1. * T d ki n th y phn suy ra 2 cng th c Glu -His-Pro v His-Pro-Glu ( u c 1 nhm CO NH
2
)
* T M = 362 vC suy ra c t o ra amid vng (lo i H
2
O)
* T d ki n vng s 5 c nh suy ra Glu l aminoaxit u N v t o lactam 5 c nh, cn Pro l aminoaxit
u C v t o nhm CO NH
2
.
V y c u t o c a TRF:
HN CH
O
CO-NH CH CO N CH CO-NH
2
CH
2
N
NH
Cng th c Fis :
NH
CO
CO
CO
CH
2
NH
2
H
H
H
O
N
NH
N
NH
2. Cn b ng i n ly c a His:
COOH
H H
3
N
CH
2
N H
NH
+
+
COO
H H
3
N
CH
2
N H
NH
+
+
COO
H H
3
N
CH
2
N
NH
+
COO
H
CH
2
N
NH
H
2
N
-H
+
-H
+
-H
+
(+2) (+1)
(0)
(-1)
(1)
(2) (3)
1,8 6,0
(ho c vi t 3 cn b ng ring r ; khng c n cng th c Fis )
* pH
I
= (pKa
2
+ pKa
3
) : 2 l ng,
v phn t His trung ha i n (i n tch = 0) n m gi a 2 cn b ng (2) v (3)
3. T ng h p axit (D,L)-glutamic
HC CH
HCN
NC CH = CH
2
2
0
CO, H
xt, t
NC CH
2
CH
2
CH=O
3
HCN, NH
HOOC COOH
N
NH
2
C CH
2
CH
2
CH
C N
1) H
2
O, OH
2) H
3
O
+
NH
2
CH
2
CH
2
CH
Bi 9: Th y phn hon ton m t hexapeptit M thu c Ala, Arg, Gly, Ile, Phe v Tyr. Cc peptit E
(ch a Phe, Arg) v G (ch a Arg, Ile, Phe) c t o thnh trong s cc s n ph m th y phn khng ho n
ton M. Dng 2,4-dinitroflobenzen xc nh c amino axit Ala. Th y phn M nh tripsin thu c
tripeptit A (ch a Ala, Arg, Tyr) v m t ch t B.
a. Xc nh th t lin k t c a cc amino axit trong M.
b. Amino axit no c pH
I
l n nh t v amino axit no c pH
I
nh nh t?
Bi t c u t o chung c a cc amino axit l H
2
N-CHR-COOH
AA: Ala Arg Gly Ile Phe Tyr
R : CH
3
(CH
2
)
3
NHC(=NH)NH
2
H CH(CH
3
)C
2
H
5
CH
2
C
6
H
5
p-HOC
6
H
4
CH
2
BI GI I:
a. Hexapeptit M c u N l Ala. Thu phn M nh tripsin xc nh c tripeptit l: Ala Tyr Arg.
Dipeptit E c c u t o Arg-Phe. Tripeptit G c c u t o: Arg-Phe-Ile. Do v y amino axit u C l: Gly.
Ala Tyr Arg
Arg Phe
Arg Phe Ile
Gly
V y c u t o c a M: Ala Tyr Arg Phe Ile Gly.
b. pH
I
l n nh t: Arg, v c nhm guanidin (c 3 nguyn t N)
pH
I
nh nh t: Phe, v c nhm phenyl.
Bi 10: Isoleuxin c i u ch theo dy cc ph n ng sau (A, B, C, D l k hi u cc ch t c n tm):
A B C D
3
NH
Isoleuxin
C2H5ONa 2. HCl
Hy cho bi t cng th c c u t o c a cc ch t A, B, C, D v Isoleuxin.
BI GI I:
o
2 5 2 2 3
2 5
(C H OOC) CH NH 1.KOH t
3 2 3 C H ONa 2.HCl
CH CH CHBrCH A B C D Isoleuxin
Bi 11: Ng i ta phn l p c m t tetrapeptit (peptit A) t prothrombin ng i. C u t o c a peptit A
c ti n hnh xc nh nh sau:
a. B ng ph ng php Edman th nh n c trnh t aminoaxit c a peptit A l Leu-Glu-Glu-Val.
b. ti p t c xc nh c u t o, ng i ta ti n hnh i n di trn gi y pH 6,5 peptit A v m t peptit t ng
h p B (c ng c trnh t aminoaxit l Leu-Glu-Glu-Val) th l i nh n c qung ng di chuy n khng
gi ng nhau, c th nh hnh d i y:
Peptit A
Peptit B
0 1 2 3 n v di
2,5
1,7
CH
Br
CH
3
CH
2
CH
3

2 2 5 2
CH OOC) H (C

KOH . 1

2
Br

0
t
c. Khi thu phn hai peptit A v B b ng HCl 6N 110
o
C, th c A v B u cho Leu(1), Glu(2), Val(1); nh ng khi
thu phn b ng ki m th peptit B cho Leu(1), Glu(2), Val(1) cn peptit A cho Leu(1), X(2), Val(1).
Hy gi i thch cc k t qu th c nghi m xc nh c u t o c a X v g i tn X theo danh php IUPAC.
BI GI I:
Xc nh c u trc c a X
- Ph ng php Edman th c hi n pH th p,bi t c trnh t l Leu-Glu-Glu-Val.
- i n di pH 6,5 cho th y peptit A dch chuy n nhanh h n v pha c c d ng(+), ch ng t A c i n
tch m l n h n B,tnh axit c a A l n h n B.
- Khi thu phn trong mi tr ng HCl 6N 110
o
C th c A v B u thu c Leu(1), Glu(2) v Val(1).
K t h p v i ph ng php Edman trn cho th y cc qu trnh ny th c hi n mi tr ng axit m nh,pH
th p. pH th p phn t X b ecacboxyl ho,lo i CO
2
m t i 1 nhm COOH.
- Khi thu phn b ng ki m peptit A t o ra Leu(1),X(2) v Val(1),trong mi tr ng ki m khng c qu
trnh decacboxyl ho nn nh n c X(2).
- Kt h p cc k t qu trh nghi m cho th y X c th m 1 nhm COOH so v i Glu t c l khi lo i 1 nhm
COO th X chuy n thnh Glu.
X
CO
2
CH
2
CH COOH
NH
2
CH
2
HOOC
HOOC CH
2
CH CH
NH
2
COOH
COOH X
:
Vy
G i tn: Axit 3-aminopropan-1,1,3-tricacboxylic
Bi 12: H p ch t A(C
6
H
12
N
2
O
2
) quang ho t, khng tan trong axit long v baz long, ph n ng v i
HNO
2
trong n c t o thnh B (C
6
H
10
O
4
). Khi un nng B d dng m t n c chuy n thnh C (C
6
H
8
O
3
).
H p ch t A ph n ng v i dung dch brom v natri hydroxit trong n c t o thnh D (C
4
H
12
N
2
), h p ch t
ny ph n ng v i HNO
2
khi c m t axit clohydric cho metyletylxeton.
1. Hy xc nh cng th c c u t o c a A, B, C, D v g i tn cc h p ch t t o thnh.
2. H p ch t A c th c c u trc nh th no? Dng cng th c Fis m t .
BI GI I:
1. A ph i l diamit nn c th vi t nh sau:
C
6
H
12
N
2
O
2
C
4
H
8
CONH
2
CONH
2
Br
2
; OH
-
H
2
O
C
4
H
8
NH
2
NH
2
D
D l diamin, deamin ha khi ph n ng v i HNO
2
v chuy n v gi ng nh pinacolin.
Nh v y c th vi t nh sau:
H
C H
3
C
NH
2
H
C CH
3
NH
2
HNO
2
H
C H
3
C
OH
H
C CH
3
OH
H
+
-H
2
O
CH
3
COCH
2
CH
3
2,3-diaminobutan
Nh v y h p ch t A l diamit c a axit 2,3-dimetylsucxinic c th t n t i d ng quang ho t, ph n
ng v i axit nitr cho ra axit 2,3-dimetylsucxinic.
CH
3
H CONH
2
H
2
NOC H
CH
3
HNO
2
CH
3
H COOH
HOOC H
CH
3
CH
3
C
C
H
H
3
C
H
3
C
C
O
C
O
O
t
o
C
-H
2
O
anhydrit-2,3-dimetyl
sucxinic
2. Cng th c Fis :
CH
3
H CONH
2
H
2
NOC H
CH
3
CH
3
H
2
NOC H
H CONH
2
CH
3
Bi 13: T ng h p h u c
1. Hy t ng h p axit glutamic t axit o-xetoglutaric.
2. Hy t ng h p prolin t axit adipic.
BI GI I:
1. Qu trnh t ng h p nh sau:
H
2
C
H
2
C
CH
2
COOH
CH
2
COOH
H
2
SO
4
HN
3
H
2
C
H
2
C
CH
2
NH
2
C
H
2
COOH
H
+
P, Br
2
H
2
C
H
2
C
CH
2
NH
3
+
CH
COOH
Br
OH
-
NH
COOH
(A)
(B)
ho c:
2
3 2
1)SOCl
2) NH Br / KOH
2 4 2 2 4
HOOC(CH ) COOH H NCO(CH ) COOH A r i ti p t c nh trn
2. Qu trnh t ng h p nh sau:
COOH
CO
(CH
2
)
2
COOH
HCN
NH
3
COOH
C
(CH
2
)
2
COOH
CN
NH
2
H
3
O
+
COOH
C
(CH
2
)
2
COOH
COOH
NH
2
COOH
CHNH
2
CH
2
CH
2
COOH
-CO
2
t
o
Bi 14: Peptit A c kh i l ng phn t 1007. Thu phn hon ton b ng axit cho cc aminoaxit sau v i
s mol b ng nhau: Asp, Cystin, Glu, Gly, Ile, Leu, Pro v Tyr. Oxy ha A v i HCO
2
OH ch cho B ch a
hai g c axit cysteic (k hi u l Cya), l m t d n xu t c a cystein v i nhm thiol b oxy ha thnh axit
sunfonic.
1. C bao nhiu nhm ch a axit sunfonic c t o thnh t s oxy ha m t lin k t disunfua?
Thu phn khng hon ton B cho m t s di v tri-peptit (B1 B6). Tr t t c a m i s n ph m thu phn
c xc nh trong nh ng cch sau. Aminoaxit c N cu i c xc nh b ng cch x l peptit v i
2,4 dinitroflobenzen (DNFB) cho DNP peptit. Sau khi thu phn hon ton DNP peptit b ng axit,
thu c m t DNP aminoaxit, ch t ny c th c xc nh d dng b ng cch so snh v i cc DNP
aminoaxit chu n.
2. Khi x l B1 v i DNFB r i thu phn k ti p b ng axit t o thnh m t s n ph m l DNP Asp. i u
ny cho th y B1 c axit aspartic t i N cu i. Hy vi t c u t o y c a DNP Asp t i i m ng i n
c a n (khng c n ha h c l p th ).
K , aminoaxit c C cu i c xc nh b ng cch un nng peptit t i 100
o
C v i hydrazin, ch t ny b
gy t t c cc lin k t peptit v chuy n t t c tr aminoaxit C cu i thnh hydrazit c a aminoaxit, cn
nhm cacboxyl C cu i cn nguyn v n. Theo cch ny, cc aminoaxit N- v C- cu i c xc nh th
t ton b c a B1 B6 nh sau:
B1: Asp Cya B4: Ile Glu
B2: Cya Tyr B5: Cya Pro Leu
B3: Leu Gly B6: Tyr Ile - Glu.
Thu phn B v i m t enzym t Bacillus subtilis cho B7 - B9 v i thnh ph n nh sau:
B7: Gly NH
2
(glyxinnamit) B8: Cya, Glu, Ile, Tyr
B9: Asp, Cya, Leu, Pro
3. Vi t trnh t c a B8 n u thu c DNP Cya khi x l B8 v i DNFB r i thu phn hon ton sau
b ng axit.
4. N u cc aminoaxit N- v C- cu i c a B9 c xc nh theo th t l Asp v Leu, vi t trnh t c a B9.
5. Vi t c u t o y c a A v ch r v tr c a lin k t disunfua.
Tuy nhin kh i l ng phn t c a A tnh c th l n h n ga tr th c nghi m hai n v. Quan st k
l ng h n h p thu c t s th y phn hon ton b ng axit c a A ngoi cc aminoaxit tm c lc u
cn c 3 ng l ng mol amoniac c ng c t o thnh.
6. ngh c u t o i u chnh c a A v khoanh trn (m t hay nhi u v tr) trn c u t o ny cho th y t t
c cc ngu n t o amoniac c th c.
BI GI I:
1. 2
2. Cng th c c u t o:
O
O
2
N
OH
OH
N H
NO
2
O
3. Trnh t c a B8 l: Cya Tyr Ile Glu.
4. Trnh t c a B9 l: Asp Cya Pro Leu.
5. C u t o y c a A l: Cys Tyr Ile Glu Asp Cys Pro Leu Gly NH
2
6. C u t o i u chnh c a A:
Cys Tyr Ile Gln Asn Cys Pro Leu Gly NH
2
Cc v tr g ch chn l cc v tr t o amoniac.
Bi 15: Ph n ng ng ng t gi a axit cacboxylic v amin sinh ra amit. V d : ng ng t axit fomic v i
dimetylamin sinh ra N,N-dimetylfomamit, n c cc c u trc c ng h ng sau:
N H
CH
3
CH
3
O
N
+
H
CH
3
CH
3
O
1. X p cc ch t N,N-dimetylfomamit (A). N-metylaxetamit (B) v propanamit (C) theo th t tng d n
nhi t si.
2. Nhm cacbonyl th ng c nh n di n b ng d i h p th m nh trong ph h ng ngo i (IR). V tr vn
h p th ph thu c vo b n lin k t C = O. i v i amit th b n c a lin k t C = O c th c xc
nh d a vo hnh v trn. V d : nhm C = O c a xiclohexanon cho vn h p th 1715cm
-1
. so snh
v i xiclohexanon th cc gi tr no sau y l ph h p v i nhm C = O c a propanamit?
a) 1660cm
-1
do di lin k t ng n c a nhm cacbonyl.
b) 1660cm
-1
do di lin k t di c a nhm cacbonyl.
c) 1740cm
-1
do di lin k t ng n c a nhm cacbonyl.
d) 1740cm
-1
do di lin k t di c a nhm cacbonyl.
3. Glyxin (H
2
N CH
2
COOH) l o - aminoaxit. Ba phn t glyxin c th t o ra tripeptit GlyGlyGly
thng qua ph n ng ng ng t t o thnh amit v km theo s tch lo i hai phn t n c. Hy vi t cng
th c c u t o c a tripeptit.
4. Khi o - aminoaxit ch a nhoam th thu lc ny s xu t hi n hi n t ng ng phn quang h c. V d :
Lalanin v Dalanin l hai enantiome. Nh v y i v i 3 peptit glyxin, Lalanin v Dalanin ta c th
thu c bao nhiu tripeptit?
N H
2
OH
H
H
O
N H
2
OH
CH
3
H
O
N H
2
OH
H
C H
3
O
Glyxin (Gly)
L-Alanin (L-Ala) D-Alanin (D-Ala)
5. T ng c ng c bao nhiu ng phn quang h c t cc tripeptit trn?
Hi n nay, polyacrylamide gel with electrophoresis (PAGE) c s d ng r ng ri trong vi c phn tch
protein v axit nucleic. Tuy nhin m t trong s nh ng ng d ng c a keo polya mit l phn l p cc h p ch t
phenol b ng s c k b n m ng. Cc phenol c ch a cc nhm th khc nhau th c tnh axit khc nhau.
Tnh axit khc nhau th lin k t v i keo PAGE cng m nh.
6. S p x p cc ch t sau: phenol (D), 4 metylphenol (E) v 4nitrophenol (F) theo th t gi m d n kh
nng lin k t v i PAGE. Kh nng h p th m t ch t trong ph t ngo i - kh ki n (UV Vis) ph thu c
vo s lin k t i lin h p trong phn t . M t h p ch t c t 5 n i i li n h p tr ln th c xu h ng
h p th nh sng trong vng kh ki n nn k t q a l chng c mu. V d phenolphtalein l m t ch t ch
th axit baz thng d ng. Trong dung dch c tnh axit v trung t nh n khng c mu cn trong dung
dch baz n c mu tm (pH: 8,3 10,0)
OH
H
2
SO
4
C
O
O
OH
O H
OH-
H
+
G + 2
dac
180
o
C , 5h
H
Phenolphtalein
7. Vi t cng th c c u t o c a H.
8. Phenolphtalein c th c i u ch b ng cch cho ch t G ph n ng v i hai mol phenol. G ph i l
ch t no trong s cc ch t d i y ph n ng t hi u su t cao nh t.
H
H
O
O
H
OH
O
O
O
O
O
O
a
b c
d
BI GI I:
1. Th t s p x p cc ch t theo nhi t si: C > B > A.
Gi i thch: T c u trc c ng h ng c a amit cho th y n c m t ph n i n tch m trn nguyn t oxy v
m t ph n i n tch d ng trn nguyn t nit . Amin b c 1 v b c 2 c lin k t hydro m nh h n amin b c
3 (Propanamit: 79
o
C; N- metylaxetamit: 28
o
C v N,N-dimetylfomamit: -61
o
C).
2. Cu b
3. Gly-Gly-Gly
H
N
N
N
OH
H
H
H O O
O
H
3
N
N
N
O
H
H O O
O
+
d ng l ng c c.
4. 27
5. Trong s th 26 tripeptit c ng phn quang h c
Aminoaxit khng c tnh quang ho t: H
2
N GGG OH
Aminoaxit c tnh quang ho t: H
2
NGG
L
AOH; H
2
NGG
D
AOH
6. Kh nng lin k t v i PAGE gi m d n theo th t F > D > E.
7. H l
O
O
O
O H
OH
O
O
O
8. Ch t d
Bi 16: Protein hi n di n trong h u h t cc t bo s ng v ng m t vai tr quan tr ng trong ha h c c a
s s ng. N c t o thnh t cc n v c u trc l cc axit - o - aminocacboxylic. Peptit l cac protein
thu nh v i m t vi aminoaxit. Lin k t peptit l cc lin k t amit c hnh thnh t s ng ng t c a
nhm amin c a aminoaxit ny v i nhm cacboxyl c a aminoaxit k c n.
1. Peptit no nh n c t phenylalanine F v alanin A? Ch ra c u trc c a chng.
NH
2
O
OH
NH
2
O
OH
NH
2
O
OH
NH
2
O
OH
A G L F
Trong ph ng php phn tch c u trc peptit th vi c nh n di n aminoaxit u N v ui C ng vai tr
c c k quan tr ng. Ph ng php Sanger gip ta nh n di n c aminoaxit u N b ng cch x l
aminoaxit v i 2,4-dinitroflobenzen trong mi tr ng ki m y u, sau l thu phn ton b chu i peptit
v i xc tc axit. Aminoaxit u N s t o ra k t t a mu vng v d dng c nh n di n b ng ph ng
php s c k gi y. Sanger c trao gi i th ng Nobel nm 1958 v 1980.
2. Vi t ph n ng x y ra khi ta s d ng tc nhn Sanger ( cho g n ta vi t aminoaxit u N c cng th c
l H
2
NR) nh n di n aminoaxit u N.
V i aminoaxit ui C, ch a nhm ch c COOH t do trong peptit c phn l p b ng cch s d ng
enzym cacboxipeptidaza th y phn, enzym ny ch th y phn aminoaxit cu i m ch. i v i m t
tetrapeptit ch a cac aminoaxit F, A, glyxin G v leuxin L th ph ng php th y phn b ng enzym
cacboxipeptidaza th aminoaxit ui C c nh n di n l F. ph ng php Sanger cho bi t aminoaxit u
N c nh n di n l G.
3. ngh cng th c c u t o c a peptit. Hy vi t cc cng th c c u t o c a chng.
BI GI I:
1. Cng th c c a cc peptit nh n c:
N H
2
N
H
OH
O
O
N H
2
N
H
OH
O
O
Ph
Ph
N H
2
N
H
OH
O
O
Ph
N H
2
N
H
OH
O
O
Ph
AA FF
FA
AF
2. Ph n ng x y ra:
F
NO
2
O
2
N
H
2
NR
NHR
NO
2
O
2
N RNH
3
F
+ 2
+
3. Khng th bi t c th t hai aminoaxit gi a l AL hay LA nn peptit ban u c c th c c u t o
nh sau: GALF ho c GLAF.
Bi 17: Coniin l h p ch t r t c c tm th y trong cy c sm (conium maculatum). Tri t gia c i
ng i Hy L p Socrates b gi t b i ch t ny. Coniin l m t h p ch t ch a nit v l m t ancaloit. Xc
nh ha tnh v ha l p th c a coniin b ng cch hon thnh cc chu i ph n ng sau. V CTCT A, B, C.
Trong :
Hofmann exhaustive methylation: s metyl ha tri t theo Hofmann
Optically active: ho t ng quang h c
BI GI I:
B c oxy ha b ng KMnO
4
tham kh o trong ti li u: A. M. Castano, J.M. Cuerva, A. M. Echavarren,
Tetrahedron Letters, 35, 7435-7438 (1994)
Bi 18: Peptit l cc polyamit m ch th ng sinh ra b ng cc li n k t ui n i v i ui c a cc aminoaxit
c c u hnh L (t c S).
1. Cc dipeptit no c th c t o thnh b ng cch ng ng t Lalanin v Lphenylalanin? S d ng cc
cng th c l p th trong cu tr l i.
2. S ko di t ng ph n m ch peptit h u h t lun b t u t nguyn t C c a cc aminoaxit b c ba (s
d ng d ng este) lin k t v i m i n v aminoaxit k ti p (s d ng d ng d n xu t th Ni t ) d n n
s thay th nguyn t N - th tr c khi n v k ti p c g n vo. D n xu t th th ng c s d ng l
cc nhm ankoxy cacbonyl ROCO v d n xu t cacbamat c a n.
Hy gi i thch l do t i sao s hi n di n c a nhm th (nhm b o v ) c a nguyn t nit amin lm tr
ng i vi c t o lin k t amit v i nhm cacboxyl. a. V nit by gi ch cn c 1H ; b. V nhm b o v c
m t electron t h n nguyn t nit . ; c. V nhm b o v ch n s t n cng c a nhm cacbonyl ; d. V s
khng tnh i n ; e. V n v n l m t amit.
3. V cc cng th c c ng h ng c a m t n a nhm amit. S d ng cc k hi u l p th v cc m i tn
ch r s chuy n dch electron.
4. Tc nhn no d i y s c s d ng g n nhm benzylcacbamat vo m t amin (nhm Bergmann
Zervas). Vi t ph n ng. a. C6H5CH2OCONH2, b. C6H5CH2OCO2CH3, c. C6H5CH2OCO2C(CH3)3,
d. C6H5CH2OCOCl, e. C6H5OCOCl
5. Vi c lo i nhm b o v ankoxycacbonyl th ng km theo ph n ng c t m ch d i tc d ng c a cc
axit theo s :
X p kh nng tng d n tnh ho t ng c a cc cacbamat sau y d i tc d ng c a axit:
BI GI I:
1. Cng th c c u t o cc peptit c th c:
Cc dipeptit vng (dixeto piperazin) c ng c ch p nh n:
2. Cu tr l i t t nh t l b v e
3.
4. Tc nhn e (benzylclofomiat) s ph n ng v i amin theo s sau:
5. N u chng ta gi thi t tr ng thi chuy n ti p c t o thnh ion cacboni th ch t no t o
thnh ion cacboni d dng nh t th tnh b n c ng t l thu n v i kh nng . Trong
ch t D th c s gi i to electron m nh nh t:
v kh nh t A:
Gi i thch t ng t ta th y cation t o thnh t B b n h n C. Nh v y th t s l: D > B > C > A
Bi 19: Cng th c c u t o c a cc ch t A v B trong s i u ch nh a melamin sau:
Xianogen clorua A
3
NH
Xianuramit (melamin)
2
CH O
B
N
N
N
NH
2
NH
2
N H
2
BI GI I:
C N
N
N
N
Cl
Cl Cl
NH
3
N
N
N
NH
2
NH
2
N H
2
HCHO
N
N
N
NHCH
2
NHCH
2
CH
2
HN
n
Cl
Bi 20: Cho s sau:
(-)-Serin
3
3
1.H O HCl OH NaSH
4 9 2 2 4 8 2 2 4 9 2 CH OH 2.OH
A B(C H Cl NO ) C(C H Cl NO ) D(C H NO S) E
+

Vi t cng th c Fis c a E v cho bi t c u hnh tuy t i (R/S) c a n.
BI GI I:
S ph n ng
O H CH
2
CH COOH
NH
2
O H CH
2
CH
NH
3
Cl
COOCH
3
Cl CH
2
CH
NH
3
Cl
COOCH
3
PCl
5
Cl CH
2
CH
NH
2
COOCH
3
S H CH
2
CH
NH
2
COOCH
3
S H CH
2
CH
NH
2
COOH
Cng th c chi u Fischer c a E (cystein) E c c u hnh R v h n c p c a -CH
2
SH > -COOH
COOH
CH
2
SH
H
H
2
N
R
Bi 21: Sau khi x l h n h p li ng ho c v tr u c ch a pentozan (C
5
H
8
O
4
)
n
v i dung dch axit
clohiric 12% r i ti n hnh ch ng c t, nh n c ch t l ng A (C
5
H
4
O
2
) mu vng c mi th m. Cho A
ph n ng v i KOH r i axit ha th nh n c B (C
5
H
4
O
3
) v C(C
5
H
6
O
2
).
a. Vi t ph ng trnh ph n ng thu phn pentozan t o thnh A v cng th c c a A, B, C.
b. Vi t ph ng trnh ph n ng c a B tc d ng v i C khi c
xc tc axit.
c. Hy trnh by i u ki n nitro ho A nh n c D (C
5
H
3
NO
4
).
d. Vi t ph ng trnh ph n ng c a D tc d ng v i: (I) ; (II).
(II)
NH
-N
O
O
H
2
N
(I)
S
NH
S
O
BI GI I:
1. Trong li ng v v tr u c ch a pentozan, khi un nng v i dung dch HCl 12% chuy n
thnh pentoz r i tch n c cho fufurol
A
C
2
O
CHO
(C
5
H
8
O
4
)
n
HCl 12%
CHO
(CHOH)
3
CH
2
OH
- 3H
2
O
A(C
5
H
4
O
2
)
O
CHO
KOH
O
CH
2
OH
O
COOK
B
H
3
O
+
O
COOK
O
COOH
H
+
b.
O
COOH
+
O
CH
2
OH
O
COOCH
2
O
c. nitro ho A c n ph i b o v nhm anehit b ng (CH
3
CO)
2
O
(CH
3
CO)
2
O
O
CH(OCOCH
3
)
2
O
CHO
Th c hi n ph n ng nitro ho, sau thu phn ph c h i nhm -CHO
H
3
O
+
O
CH(OCOCH
3
)
2 CHO
O
O
2
N
O
CH(OCOCH
3
)
2
O
2
N
HNO
3
D
d. Ph n ng c a D v i I v II
D
I
CHO
O
O
2
N
N
O
NH
O
H
2
N
CH
O
O
2
N N N
O
NH
O
II
S
NH
S
O
CHO
O
O
2
N
CH
O
O
2
N
S
NH
S
O
Bi 22: Geniposit (hnh d i) l m t h p ch t c tch ra t qu dnh dnh. Thu phn geniposit
sinh ra hai s n ph m l genipin v D-glucoz . Genipin tham gia ph n ng t o mu v i gelatin (y
l c s pht hi n d u vn tay trong k thu t hnh s ).
Hy vi t s ph n ng t o genipin v ph n ng c a genipin v i m t aminoaxit gi i thch hi n
t ng trn
O
O
O
OH
HO
HO
HOH
2
C
COOCH
3
CH
2
OH
BI GI I:
Ph n ng thu phn geniposit thu c genipin v D-glucoz
O
HOH
2
C
O
COOCH
3
O
HOH
2
C
O
COOCH
3
O
CH
2
OH
OH
HO
HO
H
HO
HO
O
+
OH
OH
OH
Gelatin (c trong da) c u t o t cc polipeptit, l y i di n l m t aminoaxit nh glyxin, ta c
ph ng trnh:
+
O
HOH
2
C
O
COOCH
3
H
H
2
N-CH
2
-COOH
N-CH
2
-
COOH
HOH
2
C
O
COOCH
3
H
s n ph m c mu pht hi n d u vn tay trong k thu t h nh s .
Part 3: CACBOHIDRAT - POLYME
O
O
O
O
O
O
CH
2
O H
2
C
OCH
2 CH
2
n
--------------------------------------------------------------------------------------------------------------------------------
CACBOHIDRAT
Bi 1: Vi t s ph n ng oxi ha D-glucoz t o thnh axit anonic v axit anaric, cng th c Haworth
cc mono v i -lacton c a chng v g i tn cc lacton y.
BI GI I:
CHO
HO
OH
CH
2
OH
Br
2
H
2
O
CH
2
OH
CH
2
OH
OH
OH
OH
OH
OH
HO
HO
COOH
COOH
COOH
HNO
3
OH
OH
OH
OH
HO
OH
O
C
O
O
OH
CH
2
OH
OH
O
O
axit gluconic
D- -gluconolacton
1,4-lacton caaxit glucaric
O
O
OH
OH
COOH
OH
O
O
OH
OH
3,6-lactoncaaxit glucaric
1,4:3,6-dilactoncaaxit glucaric
COOH
OH
O
O
HO OH
O
Bi 2: H p ch t X l m t ng ba (tri saccarit) c ch y u trong cc th c n lm t h t bng. H p ch t
X khng ph n ng v i dung dch Benedict c ng nh khng i quang. S thu phn xc tc axit t o ra ba
ng D hexoz khc nhau A, B v C. T t c cc h p ch t A v B c ng nh h p ch t I (xem d i y)
u cho cng m t osazon khi ph n ng v i l ng d phenylhydrazin trong mi tr ng axit. H p ch t C
ph n ng v i axit nitric t o thnh m t h p ch t D khng c tnh quang ho t (khng tri t quang). thi t
l p quan h gi a c u hnh gi a D glyxerandehit v C, ch t ng andehit 4 cacbon (andotetroz ) trung
gian khi b oxy ha b i axit nitric khng t o th nh c m t h p ch t meso. Khi A c x l b i axit
nitric t o thnh axit aldaric c tnh quang ho t. C A v B u ph n ng v i 5 mol HIO
4
; A t o thnh 5
mol axit metanoic (axit fomic) v 1 mol metanal (fomandehit), trong khi B t o thnh 4 mol axit
metanoic, 1 mol metanal v 1 mol CO
2
. C A v B c lin quan v i 1 andotetroz , andotetroz ny l m t
ng phn khng i quang (diastereoiso mer) c a ch t m C c t ng quan. S metyl ha c a X r i th y
3,6-dilacton c a axit glucaric
1,4-lacton c a axit glucaric
3,6-lacton c a axit glucaric
phn k ti p t o thnh 2,3,4-tri-O-metyl-D-hexoz (E) (chuy n ha t A); 1,3,4,6-tetra-O-metyl-D-
hexoz (F) (chuy n ha t B) v 2,3,4,6-tetra-O-metyl-D-hexoz (G) (chuy n ha t C).
1. Xc nh cng th c chi u Fischer c a A, B, C
v D.
2. V y cng th c chi u Haworth t ng ng
ch r kch th c vng v ha h c l p th
tuy t i c a E, F v G.
3. Vi t cng th c chi u Haworth c a X.
BI GI I:
- H p ch t X l m t tri-saccarit, khng ph n ng v i dung dch thu c th Benedict, khng quang ho t.
i u ny cho th y X l m t ng khng kh v v v y ch c cc lin k t axetal v xetal t n t i t t c
cc cacbon anome.
- Trong ba monosaccarit th A v B cho cng m t osazon nh v y c ha h c l p th nh nhau t i C-3;
C-4 v C-5 (v C-6).
- A v B c ng khc v i h p ch t I (l D-mannoz ) tuy cho cng m t osazon v nh v y m t trong s
ph i l C-2 epime c a D-mannoz (l D-glucoz ) v ch t kia ph i l ng xeton t ng ng C-2 (nh D-
fructoz ) (Suy lu n ny c ki m nh n sau ny b ng cc ph n ng c t m ch oxy ha).
- H p ch t C, sau ph n ng v i axit nitric t o m t axit dicacboxylic khng quang h o t l axit andaric D.
Axit andaric nh v y c th c hai d ng: l AA1 (D) v AA2
- Andotetroz t o thnh tr c C (c ng nh tr c D) khng cho m t h p ch t meso sau ph n ng v i axit
nitric v nh v y bu c ph i l D-threoz :
CH
2
OH
OH H
H OH
CHO
OH H
H OH
COOH
COOH
CH
2
OH
H O H
H OH
CHO
H O H
H OH
COOH
COOH
CH
2
OH
H OH
CHO
Meso
doi xung
Nh v y axit andaric D t o thnh t C nu trn l AA1 v nh v y C ph i l D-galactoz . H p ch t A ph n
ng v i 5 mol axit HIO
4
t o ra 5 mol axit metanoic (axit fomic) v m t mol metanal (fomandehit) cho
php ngh A l m t andohexoz trong khi B ph n ng v i 5 mol HIO
4
t o c 3 mol axit metanoic,
1 mol metanal v 1 mol CO
2
gip d on n l m t xetohexoz .
Cc h p ch t A v B c lin h v i m t tetroz khnggi ng nh C (lin quan v i D erithreoz ). Tetroz
lin quan n A v B v th ph i c c u t o sau y v A l D glucoz cn B l D fructoz .
CH
2
OH
OH H
H OH
CHO
H OH
O H H
H OH
H OH
CHO
CH
2
OH
O
O H H
H OH
H OH
CH
2
OH
CH
2
OH
H OH
O H H
O H H
H OH
CH
2
OH
CHO
D-Glucose
D-Fructose
D-Galactose
- Metyl ha X r i thu phn k ti p t o thnh E, F v G d i y:
E chuy n ha t A
CHO
H OCH
3
H
3
CO H
H OCH
3
H OH
CH
2
OH
CH
2
OH
H
H
CH
3
O
OCH
3
H
O
OH
H
H
OCH
3
F chuy n ha t B
CH
2
OCH
3
O
CH
3
O H
H OCH
3
H OCH
3
CH
2
OCH
3
O
H CH
3
O
H
OCH
3
H
OCH
3
CH
2
OCH
3
H
G chuy n ha t C
CHO
H OCH
3
H
3
CO H
H
3
CO H
H OH
CH
2
OCH
3
Trong s metyl ha, ch cc nhm hydroxyl khng tham gia vo s hnh thnh axetal/xetal (ho c n i phn
t ho c lin phn t ) m i b ete ha. T d ki n metyl ha, ch E c hai nhm hydroxyli t do c th lin
k t v i cc cacbohydrat khc. Nh v y A ph i l cacbohydrat trung tm. Cc k t q a ny ch ra r ng tr t t
c a cc monosaccarit trong X l C-A-B (hay B-A-C).
N u: A
5
bi u th d ng furanoz (vng 5 c nh) c a cacohydrat A.
A
6
bi u th d ng pyranoz (vng 6 c nh) c a cacbohydrat A.
BB
5
bi u th d ng furanoz (vng 5 c nh) c a cacbohydrat B.v.v
th saccarit X c th c bi u th l C
6
A
6
B
5 M t trong 4 c u t o khc nhau c th c c a X:
O
H
O
H
OH
OH
H
H
OH
CH
2
OH
H
CH
2
O
H
OH
OH
H
H
H
OH
H
O
O
OH
H
H
OH
CH
2
OH
H
HOH
2
C
Tri-saccarit X
Ghi ch: B n ch t c a cc lin k t anome l khng thi t y u trong bi. S s p x p cc lin k t c a A v i
B v C c ng c th c o l i (lin k t 1,1 gi a C v A v lin k t 1,6 gi a A v B.
H
CH
2
OCH
3
OH
O
H
OCH
3
OCH
3
OCH
3
H
H
Bi 3: Cc cacbohydrat thin nhin u c t o thnh t ph n ng quang h p trong th c v t. Tuy nhi n
m t s cacbohydrat khng g p trong thin nhin c t h c t ng h p nhn t o trong phng th nghi m.
Sau y s trnh by s i u ch L riboz (h p ch t I):
MeOOC
O +
100
o
C
ong han kin
B
O
HO
A OsO
4
HO
CO
2
Me
CO
2
Me
MeOOC
Me
2
C(OMe)
2
H
+
, CH
3
COCH
3
O
O
CO
2
Me
O
O
O
enzym pig liver
O
CO
2
Me
CO
2
Me
D
(spc)
+
O
3
; MeOH
O
F
O
CO
2
Me
O
O
O
E
(spp)
CO
2
H
CO
2
Me
MeO
2
C
O
O
CO
2
M
e
MCPBA
HO
O
CH
2
OH
H
3
O
+
O
O
1) MeOH/H
+
O
H
2) LiAlH
4
sau do H
2
O
CO
2
Me
OH
OH
O
O
I
G
D
D
1. H p ch t A c cng th c phn t C
10
H
10
O
5
. Vi t cng th c c u t o A.
2. Trong cc m nh lin quan n vi c chuy n ho t A thnh C sau y th m nh no ng, m nh
no sai?
a) OsO
4
l tc nhn oxy ha trong ph n ng chuy n A thnh B.
b) MeOH l s n ph m ph trong ph n ng chuy n ha B thnh C.
c) Proton ng vai tr xc tc trong ph n ng chuy n ha B thnh C.
d) C c th c t o thnh v i hi u su t th p khi khng c Me
2
C(OMe)
2
Enzym pig liver esteraza c th th y phn este thnh axit cacboxylic. Thu phn C b ng enzym pig liver
esteraza sinh ra h n h p D v E trong E l s n ph mchnh. Gc quay c c c a h n h p l:
20
D
[ ] o = -37,1
o
cn c a E tinh khi t l
20
D
[ ] o = 49
o
.
3. Tnh t l D/E (theo s mol) trong h n h p ph n ng.
4. Ph n ng c a F v i axit m clopebenzoic (MCPBA) sinh ra t s n ph m G. Ch ra r ng cc m nh
sau y l ng hay sai:
a) B n ch t c a ph n ng l s oxy ha F.
b) Nguyn t oxy thm vo c ngu n g c t MCPBA.
c) T l c a hai h p ch t C1 (R) v C1 (S) tr c v sau ph n ng khng thay i.
Cng th c phn t c a H l C
9
H
16
O
5
. Cc ga tr ph NMR c a H cho d i y:
1
HNMR (CDCl
3
) o 1,24
(s, 3H); 3,24 (m, 1H); 3,35 (s, 3H); 3,58 (m, 2H); 4,33 (m, 1H); 4,50 (d, J = 6Hz, 1H); 4,89 (s, 1H).
5. Vi t cng th c c u t o c a H.
6. Xc nh c u hnh tuy t i c a C
1
; C
2
; C
3
: C
4
c a h p ch t I.
7. Trong cng th c chi u Fischer c a I (L riboz ) th cc ch ci P, Q, R, S, T v U i di n cho nh ng
nhm ch c no?
CHO
P
Q
R S
CH
2
OH
T U
Disaccarit l h p ch t c t o thnh t hai n v monosaccarit b i lin k t glycozit. Polisaccarit ch a t
10 n vi ngn n v monosaccarit.
V d v disaccarit cho d i y:
H OH
H
O
HO
H
H
OH
OH O
H
H
OH
lin k t glycozit
H
O
H OH
H
OH
OH H
8. C bao nhiu ng phn dia t o thnh t pentasaccarit J n u n c t o thnh t 5 n v D glucoz :
H
OH
H
O
H O
H O H
H
OH
1.
OH H
5
BI GI I:
O
CO
2
Me
CO
2
Me
2. T t c u ng
3. 12,1 : 87,9
hay 12,2 : 87,8
4. a, b ng;
cu c sai
5.
MeO CH
2
OH
O O
6. C1, 2, 4: S
C3: R
7.
CHO
HO H
HO H
HO H
CH
2
OH
8. 2
5
Bi 4:
a) ngh m t hay nhi u c u t o vng v i ha l p th c th c c a (D) Tagaloz trong dung dch b ng
cng th c chi u Harworth:
CH
2
OH
O
HO H
HO H
H OH
CH
2
OH
(D) Tagaloz
b) Hai s n ph m v i cng cng th c phn t C
6
H
10
O
6
thu c khi D arabinoz c cho tc d ng v i
natri xianua trong mi tr ng axit r i th y phn k ti p c ng trong mi tr ng axit. Vi t c u t o km ha
h c l p th c th c c a hai h p ch t v chng c t o thnh nh th no?
CHO
HO H
HO H
1) NaCN / H
+
2) H
3
O
+
/t
o
H OH
CH
2
OH
(D) arabinoz
c) Khi m t disaccarit (c tnh kh ) l turanoz c em th y phn, thu c Dglucoz v Dfructoz
v i s mol b ng nhau v b ng s mol saccarit dng. Metyl ha turanoz v i metyl iodua c m t b c oxit
r i thu phn k ti p t o thnh 2,3,4,6tetraOmetylDfructoz . Hy xu t c u t o c th c c a
turanoz m khng c n xc nh ha h c l p th t i cc v tr anome.
BI GI I:
a) Cc cng th c chi u Harworth c th c c a Tagaloz :
CH
2
OH
O
OH OH
H
H
H
CH
2
OH (OH)
OH (CH
2
OH)
OH
OH
H
O OH (CH
2
OH)
OH
CH
2
OH (OH)
H
b) Cc ph n ng x y ra:
CHO
HO H
1) NaCN/H
H OH
CH
2
OH
CHO
CHO
H OH
HO H
+
H OH
H OH
CH
2
OH
COOH
CHO
HO H
HO H
H OH
H OH
CH
2
OH
CH
2
OH
H OH
HO H
H OH
H OH
CH
2
OH
+
CHO
H
3
O
+
/t
o
H OH
HO H
H OH
H OH
CH
2
OH
+
COOH
-H
2
O
H
O
H
OH
H OH
H OH H OH CH
2
OH
HO H
H O
H OH O
HO
H
H
H
OH
OH
H OH
-H
2
O
OH OH
OH
OH
CH
2
OH CH
2
OH H H
c) Cng th c c u t o c th c c a turanoz (khng ch n m t l p th t i cc v tr anome):
+
HO H
O
HO
OH(CH
2
OH)
HOH
2
C
HO
HO
OH
CH
2
OH(OH)
O
O
OH
Bi 5: Lactoz ( ng s a) c s n xu t h u h t cc trang tr i trn kh p t n c H Lan, n c s n
xu t t vng s a (s n ph m ph trong qa trnh s n xu t phomt). Lactoz c nhi u ng d ng r ng ri
trong th c n cho tr em v trong cc lo i d c ph m. N l m t disaccarit c hnh thnh t m t n v
D galactoz v D glucoz . Cng th c chi u Haworth c a n c ch ra d i y. Pha bn tri c a
cng th c l n v D galactoz .
CH
2
OH
OH
O
O
OH
OH
OH
OH
OH
O
OH
1. Hy v cng th c chi u Fischer cho D galactoz v D glucoz . S th y phn lactoz trong mi
tr ng axit d n n s t o thnh D galactoz v D glucoz .
2. D a vo cng th c c a lactoz hy ch ra:
a) Nguyn t oxy m s c thm proton sau khi lactoz b thu phn
b) Lin k t C- O no b ph v trong ph n ng thu phn
c) Nguyn t cacbon no s b kh khi ph n ng v i thu c th Fehling
S th y phn lactoz c th k t h p c v i ph n ng hydro ha khi ta s d ng xc tc kim lo i, i u ny
d n n s t o thnh ancol a ch c l sorbitol v galactitol, chng c ng c bi t d i hai ci tn t ng
ng l gluxitol v dulcitol.
3. Hy v cng th c chi u Fischer c a hai ancol a ch c ny v cho bi t chng c ho t ng quang h c
hay khng?
Trong cng nghi p, qa trnh s n xu t lactoz chu ph n ng ng phn ha thnh lactoloz , y l m t
lo i d c ph m dng ch a cc b nh v ru t. S hydro ha lactoz d n n lactitol, m t poliol C
12
v i
t calori v c ng t cao. C hai qa trnh ny u c th c hi n H Lan.
4. a) V cng th c Haworth c a lactol oz (l u r ng ph n glucoz trong lactoz
b ng phn ha thnh fructoz ).
b) V cng th c chi u Haworth c a lactitol.
O
BI GI I:
1. Cng th c c u t o c a D galactoz v D glucoz l:
CHO
H OH
HO H
H OH
H OH
CH
2
OH
CHO
H OH
HO H
HO H
H OH
CH
2
OH
D glucoz D galactoz
2.
CH
2
OH
OH
O
OH
OH
a
c
OH
O
OH
OH
O
b
OH
CH
2
OH
H OH
HO H
H OH
H OH
CH
2
OH
CH
2
OH
H OH
HO H
HO H
H OH
CH
2
OH
Sorbitol (ho t ng quang h c) Galactitol (khng ho t ng quang h c)
4.
CH
2
OH
OH
O
O
OH
OH
OH
OH
CH
2
OH
OH
OH
CH
2
OH
OH
O
OH
OH
O
OH
O
CH
2
OH
OH
CH
2
OH
Lactitol
CH
2
OH
Lactolose (f uranose)
OH
OH
O
OH
OH OH
CH
2
OH
O
OH
Lactolose (pyranose)
Bi 6: M t monosaccarit A c kh i l ng phn t l 150Da. Khi x l A v i NaBH
4
th sinh ra hai ng
phn l p th B v C khng c tnh quang ho t.
1. V cng th c c u t o c a A, B v C b ng cch s d ng cng th c chi u Fischer.
2. Xc nh c u hnh c u hnh tuy t i c a cc ch t t A n C b ng cch s d ng h danh php CIP
(Cahn Ingold Prelog).
3. Hy xc l p m i quan h v m t l p th gi a cc ng phn quang h c c a B.
3.
BI GI I:
1 2.
CH
2
OH
H OH
O
OH H
CH
2
OH
CH
2
OH
H OH
OH
OH H
CH
2
OH
H
CH
2
OH
H OH
H
OH H
CH
2
OH
O H
R
S
R
S
S
R
S
R
A
B C
M t monosaccarit c cng t h c chung l C
n
(H
2
O)
n
. T t nhin, v i kh i l ng phn t l 150Da th cng
th c ch c th l C
5
(H
2
O)
5
. Sau ph n ng kh th B v C l hai ng phn duy nh t khng ho t ng
quang h c. Hai s n ph m ny c th c coi l ti n ch t c a A. N u hai nhm ch khc nhau kh nng
quang h c th ng phn R s c kh nng hnh thnh cao h n ng phn S
3.
CHO
CH
2
OH
H OH
H OH
H OH
CHO
CH
2
OH
H OH
HO H
H OH
CHO
CH
2
OH
H OH
H OH
HO H
CHO
CH
2
OH
HO H
H OH
H OH
diastereomers
diastereomers
diastereomers
diastereomers
diastereomers
enantiomers
Bi 7: T m t monosaccarit, hy vi t cc ph ng trnh ph n ng i u ch ch t A v B:
O O
CHO
H
A
O
O
H
5
C
6
O
OCH
3
CH
3
COO
OCOCH
3
B
BI GI I:
i u ch A
Bi 8: Vi t cng th c Fis c a cc ch t C v D trong dy chuy n ha sau:
BI GI I:
Bi 9:
1. Vi t cc ph ng trnh ph n ng thu phn metyl- -D-galactofuranozit (A) v metyl- -D-sobofuranozit (B) trong
mi tr ng axit. (soboz : 2-xetohexoz ; c u hnh C3 c a n v c a galactoz khc nhau).
2. Arabinopyranoz (D-anopentoz c c u hnh 2S, 3R, 4R) c chuy n ha nh sau:
Ara (C
5
H
10
O
5
) B C
CH
3
OH/H
+
HIO
4
H
2
O/H
+
Br
2
/H
2
O
1. LiAlH
4
2. H
2
O
D
E
H
2
O/H
+
HOCH
2
-CH
2
OH HOCH
2
-CHO +
HOCH
2
-COOH CHO-COOH
+
V c u trc c a B, C, D v E.
BI GI I:
1.
O
OH
OH
OH
OCH
3
H
+
H
2
O
-
CH
2
OH
O
OH
OH
OH
CH
2
OH
OH
H
+
H
2
O
-
CH
2
OH HOCH
2
O
OH
OH
OCH
3
HOCH
2
O OH
CH
2
OH
OH
OH
2.
Ara B C
O
OMe
HIO
4
O
OMe
CHO
CH
2
OH
CH
3
OH/H
+
CHO
CHO
E
HOH
2
C
HOH
2
C
O
OMe
HOOC
HOOC
O
OMe
Br
2
/H
2
O
1. LiAlH
4
2. H
2
O
CH
2
OH-CH
2
OH + CH
2
OH-CHO
CH
2
OH-COOH + CHO-COOH
H
3
O
+
H
3
O
+
D
Bi 10: H p ch t A (C
4
H
6
O
3
) quang ho t, khng tham gia ph n ng trng b c, tc d ng v i anhirit axetic
t o ra d n xu t monoaxetat. Khi un nng v i metanol, A chuy n thnh ch t B (C
5
H
10
O
4
). D i tc d ng
c a axit v c long, B cho metanol v C (C
4
H
8
O
4
). C tc d ng v i anhirit axetic t o ra d n xu t
triaxetat, tc d ng v i NaBH
4
t o ra D (C
4
H
10
O
4
) khng quang ho t. C tham gia ph n ng trng b c t o
thnh axit cacboxylic E (C
4
H
8
O
5
). X l amit c a E b ng dung dch long natri hipoclorit t o ra D-(+)-glyxeranehit
(C
3
H
6
O
3
) v amoniac.
V c u trc c a A, B, C, D v E.
BI GI I:
MeOH
M
e
O
H
CHO
CH
2
OH
H OH
C
CH
2
OH
CH
2
OH
CH
2
O
MeO
O
O
CHO
CH
2
OH
D-Glyxeraldehit E
COOH
CH
2
OH
CH
2
A B D
Bi 11: T pentoz , hy vi t s chuy n ha thnh axit aipic qua giai o n t o thnh fufuran
BI GI I:
OH O H
O H OH
CHO
OH
2
OH O H
CHO
OH
2
O
CHO
KMnO
4
O
COOH
CO
2
O
Hidro
xt
O
Cl Cl
H
3
O+
COOH
COOH
-2
o
t
HCl 1. KCN
2.
Bi 12: Gentibioz l ng kh v c kh nng t o ozazon, chu i quay v b th y phn b ng dung
dch n c axit ho c b ng elmusin cho D-glucoz . Metyl ha r i th y phn s cho 2,3,4,6-tetra-O-metyl-
D-glucoz . Vi t CTCT v g i tn Gentibioz C
12
H
22
O
11
BAI GI I:
O HO
HO
OH
O
HOH
2
C
OH HO
HO
OH
O
C
H
2
6 o ( glucopiranozyl) D glucopiranozo | (A)
O HO
HO
OH
OH
OH HO
HO
OH
O
MeO
MeO
OMe
OMe
OH MeO
MeO
OMe
OH
OH
A
Bi 13: Salixin C
13
H
18
O
7
b th y phn b i elmusin cho D-glucoz v Saligenin C
7
H
8
O
2
. Salixin khng
kh thu c th Tolen. Oxi ha Salixin b ng HNO
3
thu c m t h p ch t h u c X m khi th y phn th
cho D-Glucoz v anehit Salixylic. Metyl ha Salixin thu c pentametylsalixin, th y phn h p ch t
ny cho ta 2,3,4,6-tetra-O-metyl-D-Glucoz . Xc nh CTCT c a Salixin
BI GI I:
Salixin l ng khng kh v l glucozit | do b th y phn b i elmuxin
RO H
OH
HO
OH
CH
2
OH
O
H
2
O
enzim
D-Glucose + ROH (Saligenin)
C
7
H
8
O
2
Salixin
Trong cng th c C
7
H
8
O
2
, ROH xu t hi n nhn th m. Tch c andehit salixylic, i u ch ng t qu
trnh oxi ha nhm CH
2
OH thnh nhm CHO
D-Glucose +
CHO
HO
H
2
O, H
+
O HO
HO
OH
O
HOH
2
C
CHO
Saligenin l o-(hidroximetyl)phenol. Cng th c c u trc c a salixin l
O HO
HO
OH
O
HOH
2
C
CH
2
OH
Bi 14: H p ch t thin nhin Y (C
7
H
14
O
6
) khng c tnh kh v khng i tnh quang ho t. Y b th y phn
b i dung dch HCl/H
2
O thnh K l m t ng kh . Khi b oxi ha b i axit nitric lo ng, K chuy n thnh
axit khng quang ho t L (C
6
H
10
O
8
). S thoi phn Ruff d n t i m t ng kh M ; ch t ny b oxi ha b i
axit nitric long thnh axit quang ho t N (C
5
H
8
O
7
)
a. Xc nh c u trc c a Y, K, L, M, N
b. C t n t i s khng kh ng nh no v m t c u trc khng
BI GI I:
a. Y l metylglicozit, l p lu n tm ra K, L, M, N. Y t n t i d ng vng 5 c nh
CH
H OH
HO H
H OH
H
CH
2
OH
O
OCH
3
L c th l 1 trong ch t sau
COOH
OH
OH
OH
OH
COOH
COOH
OH
HO
HO
OH
COOH
M l:
CHO
HO
HO
OH
CH
2
OH
N c th l 1 trong ch t sau
COOH
HO
HO
OH
COOH
COOH
OH
OH
HO
COOH
K l m t trong 2 ch t sau:
O
OH
OH
OH
CH
2
OH
OH
O
OH
OH
OH
CH
2
OH
HO
Y c th l m t trong 2 ch t
O
OH
OH
OH
CH
2
OH
OCH
3
O
OCH
3
OH
OH
CH
2
OH
HO
b. Khng kh ng nh v m t cu trc:
- C u hnh C anome
- Cc yu c u u th a mn c c u hnh D v L
************************************************
POLYMER OLIGOMER
Bi 1: Cc polyme h u c c nh h ng r t l n i v i cu c s ng hng ngy c a chng ta. Hng nghn t n
cc lo i cao phn t khc nhau c s n xu t m i nm. T ng h p cc polime h u c c s d ng trn
nhi u lnh v c, t nguyn li u d t cho n cc con chip my tnh, v n c van tim nhn t o. Chng c
s d ng r ng ri nh ch t d o, keo dn, v t li u xy d ng, ch t d o c kh nng phn h y v s n. Poly
(vinyl ancol) (PVA) l m t v d quan tr ng c a m t polyme c kh nng h a tan trong n c. Gi n 1
d i y tm t t m t ph ng php t ng h p PVA.
Giai o n 1:
polyme ha
Monome polyme poly(vinylancol) A B PVA
Polyme B trn c ng l thnh ph n chnh trong k o cao su. Phn tch nguy n t ch t A cho t l C:H:O =
56:7:37. Thm vo , phn tch nguyn t ch t B cho ra thnh ph n C, H v O g n gi ng nh v y. D i
y l ph IR v 1H NMR c a monome A.
Ph
1
H NMR c a Monome A
4000 3500 3000 2500 2000 1500 1000
Ph IR c a Monome A wavenumber (cm
-1
)
T
r
a
n
s
m
i
t
t
a
n
c
e
(
%
T
)
1. Cho bi t cng th c phn t c a A?
2. Nhm ch c no cho d i h p th IR 1761 cm
-1
?
3. Cho bi t c u t o c a A
4. V m t ph n polyme B. Bi u di n t nh t ba m t xch.
5. ngh m t ph ng php chuy n ha B thnh PVA.
6. C bao nhiu c p ng phn i quang s thu c t polyme B c kh i l ng phn t 8600, gi s
r ng polyme c t t m ch b i s h p th hidro v b qua kh i l ng cc nhm cu i m ch.
7. H p ch t C, m t ng phn c a A, c ng l m t monome quan tr ng trong vi c t ng h p cc polime.
8. D a vo ph
1
H NMR v ph IR c cung c p d i y, l p lu n xc nh c u t o C.
Ph
1
H NMR c a Monome C
20
T
r
a
n
s
m
i
t
t
a
n
c
e
(
%
T
)
4000 3500 3000 2500 2000 1500 1000
Ph IR c a Monome C
Polyme D l m t phn t l n nh y axit. Khi x l D v i m t axit th gi i phng kh E, F v hnh thnh
m t polyme m i G. Kh E lm c dung dch Ca(OH)
2
, cn kh F tc d ng v i brom t o ra m t dung
dch khng mu H.
O
O
O
D
n
H
+
E + F + G
dd Ca(OH)
2
Br
2
H
BI GI I:
1. C
4
H
6
O
2
2. Nhm C=O
3. Cng th c c u t o A:
4. Cng th c c u t o B: In: ch t kh i mo:
100
80
60
40
Khng mu
5. Cc ph n ng h u c c th chuy n nhm axetat thnh ancol nh l ph n ng th y phn b ng axit hay
baz , ph n ng ancol phn hay kh b ng LiAlH
4
.
6. C 100 n v/ phn t tuy nhin n v cu i cng l i khng mang trung tm b t i nn ch c 99
trung tm b t i v m i m t trong s chng l i c c u hnh l R hay S. T ng c ng l i ta c 2
99
ng phn
quang h c bao g m c ng phn l p th i quang l n khng i quang. Nh v y s cc c p ng phn
l p th i quang (enantiomer) s l 2
99
/2 = 2
98
7. Cng th c c u t o C:
8. Cng th c c u t o c a cc ch t E, F, G, H:
Bi 2: Vi t ph ng trnh ha h c minh h a ph n ng polime ha caprolactam trong mi tr ng ki m i u
ch t nilon-6,6. Trnh by c ch ph n ng ny.
BI GI I:
N
C
O
H
NH[CH
2
]
5
CO
n
n
Ph n ng th dy chuy n nucleophin:
C NH
O
Bazo
Bazo-CO[CH
2
]
5
NH
-
Bazo-CO[CH
2
]
5
NH
-
C NH
O
Bazo-CO[CH
2
]
5
NHCO[CH
2
]
5
NH
-
\
Bi 3: D i tc d ng c a nh sng hai phn t butaien -1,3 s ph n ng v i nhau cho cc s n ph m ime
ho c tnh ch t v t l khc nhau. Hy vi t cng th c c u trc cc h p ch t .
BI GI I:
+
,
, ,
,
1.
Bi 4: Khi trng h p Buta1,3dien t o cao su Buna th ng t o ra s n ph m ph l vng 6 c nh ch a
no (ph n ng DielsAlder), khi ph n ng v i H
2
d xc tc Ni th t o ra etylcyclohexan. Vi t cc ph ng
trnh ph n ng v cho bi t i u ki n ph n ng ng vng DielsAlder x y ra d dng.
BI GI I:
a. Ph ng trnh ph n ng:
+
t , xt
o
+ 2H
2
t , xt
o
;
b. i u ki n: H p ch t dien (A) ph i c c u h nh s-cis. Ph n ng ny tr nn d dng h n n u thay H
trong dienophile b ng nhm ht electron nh COOH, COOR, CHO, v thay H trong dien
b ng nhm y electron nh : CH
3
, C
2
H
5
,
Bi 5: Khi cyclotrimer ha buta1,3diene v i s c m t c a ch t xc tc c kim, ng i ta i u ch c
(Z, E, E)cyclodeca1,5,9triene. y l m t ph ng php n gi n i u ch hydrocarbon vng l n.
Khi dng cc ch t xc tc thch h p l cc ph c tallyn c a kim lo i chuy n ti p, ng i ta i u ch c
(E, E, E)cyclodeca1,5,9triene v (Z, Z, E)cyclodeca1,5,9triene. Vi t cng th c c u t o c a cc h p
ch t trn.
BI GI I:
Z, E, E
E, E, E Z, Z, E
Bi 6: Khi cho amoniac ph n ng c ng v i axetanehit thu c s n ph m khng b n A, s n ph m ny
d b tch n c thnh B. B d dng trime ha cho s n ph m C l triazin. M t khc n u cho amoniac
ng ng t v i fomanehit s thu c s n ph m D (urotropin) c CTPT l C
6
H
12
N
4
. Ch t D c kh nng
tc d ng v i axit nitric trong anhirit axetic t o ra E (hexogen hay xiclonit) l ch t n m nh c dng
trong i chi n th gi i th II theo s : C
6
H
12
N
4
+ 3HNO
3
E + 3HCHO + NH
3
. Xc nh A, B, C,
D, E v vi t cc ph ng trnh ph n ng x y ra.
BI GI I:
Andehit bo c th tham gia ph n ng c ng v i amoniac t o th nh s n ph m t b n l Andehit-amoniac
CH
3
CHO + NH
3
Axetandehit-amoniac (t
nc
= 97
o
C) A
CH
3
CH
OH
NH
2
Axetandehit-amoniac d b tch n c thnh B l CH
3
CH=NH v B d trime ha thnh h p ch t d vng
C lo i triazin
CH
3
CH
OH
NH
2
-H
2
O
CH
3
CH=NH
trime ha
NH NH
NH CH
3
CH
3
H
3
C
B C
M t khc n u cho amoniac ng ng t v i fomanehit s thu c s n ph m D (urotropin) c CTPT l
C
6
H
12
N
4
6HCHO + 4NH
3
C
6
H
12
N
4
+ 6H
2
O
N
N
N
N
Urotropin
Urotropin c kh nng tc d ng v i axit nitric trong anhirit axetic t o ra E (hexogen hay xiclonit) l ch t
n m nh c dng trong i chi n th gi i th II theo ph n ng:
C
6
H
12
N
4
+ 3HNO
3
+ 3HCHO + NH
3
N N
N
NO
2
NO
2
O
2
N
E
Bi 7: Trong ph n ng duy tr m ch cacbon v i polime c m t xch c s c ch a nhm cacbonyl, ng i
ta th ng ch n 2 polime ti u bi u l poliacrolein A v poli( metacrolein) o B
- A tham gia t t c cc ph n ng c tr ng c a andehit nh ng khng t c m c chuy n ha cao.
D i tc d ng c a ancol, kho ng 30-35% nhm andehit c a A t o thnh axetal C
- Khi A chu tc d ng c a hidroxiamin ho c phenylhidrazin th kho ng 75% nhm andehit tham gia
ph n ng v t o thnh m t xch oxim D ho c phenylhidrazon t ng ng E
- Khc v i A, B tc d ng v i hidroxiamin s chuyn ha h u nh hon toan thnh oxim polime F
- Khi dehidrat hoa F c th thu c polime G
Cho bi t c u t o c a A, B, C, D, E, F, G
BI GI I:
CH
2
CH
CHO
n
A
CH
2
C
CH
3
CHO
n
B
... ...
C
CH
2
CH CH
2
CH CH
2
CH
CH
NOH
CH
NOH
CHO
... ...
D
CH CH
2
CH
2
CH(OR)
2
CH
CHO
CH
2
CH CH CH
2
CHO
CH
CH
2
(OR)
2
CH
2
CH CH
2
CH CH
2
CH
CH
NNHC
6
H
5
CH CHO
NNHC
6
H
5
... ...
E
CH
2
C
CH
3
CH
NOH
n
F
CH
2
C
CH
3
CN
n
G
Bi 8: Trong khu cng nghi p l c ha d u t ng lai, d ki n c c nh my s n xu t Poli(vinyl clorua)
PVC.
a. Hy ngh hai s ph n ng lm c s cho vi c s n xu t vinyl clorua t s n ph m cracking
d u m v NaCl
b. Hy phn tch cc u nh c i m c a m i s . Nu cch kh c ph c v l a ch n s c l i h n
c. Trng h p vinyl clorua nh xc tc TiCl
4
Al(C
2
H
5
)
3
s thu c PVC i u ha l p th c b n
c nhi t cao. Hy cho bi t trong m ch polime y c trung tm b t i khng? Vi t CT l p th 1
o n m ch polime y
BI GI I:
a. S t ng h p:
A:
o
1500 C HCl
4 2 2 2 2
2CH C H 3H CH CH Cl + =
NaCl + H
2
O
dpmn
2 2
Cl H 2HCl +
B:
o o
2
Cl ;500 C 500 C
2 2 2 2 2
CH CH ClCH CH Cl CH CH Cl = =
b. Ph ng php B c n ph i x l HCl thu Cl
2
v trnh nhi m.
o
t ;xt
2 2 2
1
2HCl O Cl H O
2
+ +
Ch n ph ng php B v ph n ng (1) c a ph n ng A hi u su t th p, ti u t n nhi u nng l ng v ga
thnh s n ph m s cao h n.
c. C nguyn t C b t i:
C
H
C
H
2
Cl
CH
2
CH
2
Cl
H
CH
2
Cl
CH
2
Cl
H
Bi 9: Trong cng nghi p, ng i ta th ng s d ng keo epoxi dn cc v t d ng b ng kim lo i, th y
tinh, g , ch t d oQu trnh t ng h p m t lo i keo epoxit thng d ng A xu t pht t hai monome ban
u l epiclohidrin v bis-phenol (2-bis(4-hidroxiphenylpropan). Trong giai o n u tin c a ph n ng,
oligome epoxit c t o thnh nh ph n ng ng trng ng ng hai monome trn. Sau , trong mi
tr ng ki m, ph n ng bi n i ti p t c x y ra n khi t o th nh oligome epoxi A v i h s n 50 60 ~ .
Xc nh c ch c a qu trnh t ng h p trn bi t cng th c c a epiclohirin l :
O
Cl
Epiclohirin
BI GI I:
Giai o n 1:
O
Cl
+
HO C
CH
3
CH
3
OH
+
O
Cl
Cl CH
2
CH CH
2
OH
O C
CH
3
CH
3
O CH
2
CH
OH
CH
2
Cl
Giai o n 2:
Trong mi tr ng ki m nhm epi l i c t o thnh
+
Cl CH
2
CH CH
2
OH
O C
CH
3
CH
3
O CH
2
CH
OH
CH
2
Cl
2 NaOH
O C
CH
3
CH
3
O CH
2
O
CH
2
O
+ 2NaCl + 2H
2
O
Diepoxit trn l i tip t c ph n ng v i bisphenol r i epiclohirin ph n ng l p l i nhi u l n n khi t o
thnh oligome epoxi A
O C
CH
3
CH
3
O CH
2
O
CH
2
CH
OH
CH
2
O C
CH
3
CH
3
O CH
2
O
n
v i h s n 50 60 ~ .
************************************************
Part 4: CC H P CH T D VNG
N
N O
O
S
N
Indole
Pyridine Dioxan
Thiophene Quinoline
--------------------------------------------------------------------------------------------------------------------------------
Bi 1: S p x p (c gi i thch) theo trnh t tng d n tnh axit c a cc ch t trong d y sau:
(D)
(A) (B)
(C)
;
N
COOH
;
COOH
;
CH
2
COOH
N COOH
BI GI I:
(D)
<
<
<
-I
1
CH
2
COOH
(C) (A)
-I
2
-I
3
N
H
C
O
O
-C
3
(B)
-C
4
-I
4
N
COOH
COOH
V: - I
1
< - I
2
nn (C) c tnh axit l n h n (D).
(A) v (B) c N nn tnh axit l n h n (D) v (C)
(A) c lin k t hiro n i phn t l m gi m tnh axit so v i (B).
Bi 2: S p x p v gi i thch theo chi u tng d n nhi t nng ch y c a cc ch t:
S
COOH
(A)
(C)
;
COOH
(B)
;
N
COOH
BI GI I:
Chi u tng d n nhi t nng ch y
S
COOH
(A) (C)
(B)
COOH
N
COOH
< <
V
M
C
< M
A
.
(B) c thm lin k t hiro lin phn t v i N c a phn t khc.
Bi 3: H p ch t h u c A c 74,074% C; 8,642% H; c n l i l N. Dung dch A trong n c c n ng %
kh i l ng b ng 3,138%, si nhi t 100,372
o
C; h ng s nghi m si c a n c l 1,86
o
C.
5. Xc nh cng th c phn t c a A.
6. Oxi ha m nh A thu c h n h p s n ph m trong c E (axit piridin-3-cacboxilic) v F (N-
metylprolin). Hy xc nh cng th c c u t o c a A v cho bi t gi a E v F ch t no c sinh ra
nhi u h n, ch t no c tnh axit m nh h n.
7. A c 1 ng phn c u t o l B; khi oxi ha m nh B c ng sinh ra 1 h n h p s n ph m trong c E v
axit piperidin-2-cacboxilic. Xc nh cng th c c u t o c a B.
8. Cho A v B tc d ng v i HCl theo t l mol 1:1, ch t no ph n ng d h n? Vi t cng th c c u t o
c a cc s n ph m.
BI GI I:
1. 1 : 7 : 5
14
284 , 17
:
1
642 , 8
:
12
074 , 74
N : H : C = = (C
5
H
7
N)
n
mol / g 162
372 , 0
1
100
862 , 96
138 , 3
86 , 1
t
m . k
M = =
A
= 81n = 162 n = 2; CTPT: C
10
H
14
N
2
2. E sinh ra nhi u h n F
F E
A
N N
COOH
N
COOH
CH
3
N
CH
3
3.
B
Axit piperidin -2-cacboxilic:
anabazin
N
N
COOH
H
N
H
4.
Cl
-
N
N
H
N
N
H
3
C
Cl
-
Bi 4: T etylen v cc ch t v c t ng h p cc h p ch t sau v s p x p chng theo th t tng d n nhi t
si:
1. C
2
H
5
OCH
2
CH
2
OCH
2
CH
2
OH (Etylcacbitol)
2. dioxan
O O
3. mophlin
O NH
BI GI I:
CH
2
=CH
2
+
2
0
H O, H ,
t ,p
C
2
H
5
OH
CH
2
CH
2
CH
2
O
C
2
H
5
OH
O
2
/Ag
t
0
CH
2
H
3
O
+
CH
2
CH
2
OH
C
2
H
5
O
CH
2
CH
2
O
H
3
O
+
CH
2
CH
2
OCH
2
CH
2
OH ( A )
C
2
H
5
O
CH
2
CH
2
O
H
2
SO
4
t
0
H
3
O
+
2
HOCH
2
CH
2
OCH
2
CH
2
OH
O O ( B )
CH
2
CH
2
O
1) H
2
SO
4
H
2
O
2
HOCH
2
CH
2
NH-CH
2
CH
2
OH O NH ( C)
NH
3
2) Na
2
CO
3
Nhi t si: A > C > B.
Bi 5: Cho cc ch t sau:
(C) (D)
OH
(B)
O
H
3
C
OH
OH
OH
HO
OH
O
OH
HO
CH
2
OH
HO
O OH
OH
H
2
CH
2
C
OH OH
(A)
O
OH
OH
HOCH
2
OH
OH
1. Vi t cng th c chi u Fis c a d ng m ch h cc ch t tr n.
2. Trong cc ch t (A), (B), (C), (D) trn, ch t no:
a) thu c dy L?
b) l ng eoxi?
c) l ng c m ch nhnh?
d) thu c lo i xetoz ?
e) c d ng furanoz ?
f) c c u hnh nhm anomeric?
BI GI I:
1. Cng th c chi u Fis c a (A), (B), (C), (D):
CHO
OH
HO
HO
HO
CH
2
OH
OH
OH
CHO
CH
2
OH
HO
H
3
C
OH
OH
CHO
OH
CH
2
OH
OH
OH
C=O
OH
CH
2
OH
OH
CH
2
OH
(A)
(D) (C)
(B)
2. Trong cc ch t (A), (B), (C), (D) trn:
a) (A), (C) l ng thu c dy L
b) (B) l ng eoxi.
c) (C) l ng c m ch nhnh.
d) (D) thu c lo i xetoz .
e) (B) c d ng furanoz .
f) (D) c c u hnh nhm anomeric.
Bi 6: Tnh baz c a m t s h p ch t ch a nit c c u t o t ng quan c nu nh sau:
H p ch t C u t o pK
a
H p ch t C u t o pK
a
Piridin
N
5,17 Anilin
NH
2
4,58
Pirol
N
0,40 Xiclohexylamin
NH
2
10,64
Pirolidin
N
11,20 p-Aminopiridin
N
NH
2
9,11
Morpholin
NH O 8,33 m-Aminopiridin
N
NH
2
6,03
Piperidin
N
11,11
So snh v gi i thch s khc bi t trong tnh baz c a m i c p sau:
a. Piperiin / piriin
b. Piridin / pirol
c. Anilin / xiclohexylamin
d. p aminopiridin / piridin
e. morpholin / piperidin
BI GI I:
a. Piridin c tnh baz y u h n piperidin v i electron gy tnh baz c a piridin thu c obitan sp
2
;
n b gi ch t v khng s n sang cho c p electron nh tr ng h p piperidin v i obitan sp
3
.
b. Piridin c i electron (thu c obitan sp
2
) s n sang dng chung v i axit; trong khi pirol ch c
th k t h p v i proton khi nh i tnh th m c a vng.
c. C hai l do. Th nh t, nguyn t nit trong anilin lin k t v i nguyn t cacbon tr ng thi lai
sp
2
c a vng th m, nguyn t cacbon ny c m i n m nh h n nguyn t cacbon tr ng thi
lai sp
3
c a xiclohexylamin. Th hai, cc electron khng lin k t c th c phn tn trn vng
th m. Cc cng th c c ng h ng ch ra r ng c s gi m m t electron t i nit . V v y
xiclohexylamin c tnh baz m nh h n anilin:
NH
2
NH
2
NH
2 NH
2
d. C th x y ra s phn tn cc electron khng li n k t c a nhm NH
2
vo nhn. H q a l c s
tng m t electron trn nguyn t nit c a d vng, do c s tng tnh baz v tr ny.
NH
2
N
NH
2
N
NH
2
N
NH
2
N
e. Piperidin c tnh baz m nh h n morpholin. Nguyn t oxy trong morpholin c m i n l n
h n nhm metylen ( cng v tr) c a piperidin, v th m t electron trn nguyn t nit c a
morpholin s nh h n so v i piperidin.
Bi 7: Oxi ho hirocacbon th m A (C
8
H
10
) b ng oxi c xc tc coban axetat cho s n ph m B. Ch t B c
th tham gia ph n ng: v i dung dch NaHCO
3
gi i phng kh CO
2
; v i etanol (d ) t o thnh D; un nng
B v i dung dch NH
3
t o thnh E. Thu phn E t o thnh G, un nng G nhi t kho ng 160
0
C t o thnh
F. M t khc, khi cho B ph n ng v i kh NH
3
(d ) c ng t o thnh F. Hy vi t cc cng th c c u t o c a
A, B, D, G, E v F.
BI GI I:
A B
CH
3
CH
3
C
C
O
O
O
D
C
O
C
O
O
C
C
O
O
OC
2
H
5
OC
2
H
5
+ C
2
H
5
OH
ftalimit F
C
C
O
O
O
+ NH
3 (kh)
C
C
O
O
N H
C
C
O
O
NH
2
OH
F
C
C
O
O
N H
160
O
C
G
Bi 8: LSD l ch t gy o gic m nh, c cng th c:
N
Me
C
O
N
Et
Et
NH
a. Vi t CTCT c a Novocain bi t Novocain l 2-(N,N-ietylamino)etyl-4-aminobenzoat
b. Vi t CTCT s n ph m sinh ra khi cho m i ch t tr n tc d ng v i dung dch HCl theo t l mol 1:1
c. Vi t CTCT t ng s n ph m sinh ra khi un nng cc ch t tr n v i dung dch HCl v v i dung dch
NaOH
BI GI I:
a. Novocain (C
2
H
5
)
2
NCH
2
CH
2
OCOC
6
H
5
NH
2
(p)
b. S n ph m t o thanh khi tc d ng v i HCl theo t l 1 : 1
N
Me
C
O
N
Et
Et
NH
HCl
N CH
2
Et
Et
CH
2
O C NH
2
O
HCl
c. Th y phn b ng HCl
N
Me
C
O
HO
NH-HCl
HCl
Et
2
NH
2
+
Cl
-
Et
2
NHCH
2
CH
2
OH
HOOC NH
3
+
Cl
-
Th y phn b ng NaOH
Et
2
NH
N
Me
C
O
NaO
NH
Et
2
NHCH
2
CH
2
OH
NaOOC NH
2
Bi 9: Gi i thch s khc nhau v nhi t si trong d y cc ch t sau:
(1) (2) (3) (4)
N
N
S
N
N
H
N
N
H
115
o
C 117
o
C 256
o
C 187
o
C
BI GI I:
- Ta c nhi t si c a (1) < (2) l do hai ch t ny khng t o c lin k t hydro nn nhi t si
ph thu c vo kh i l ng phn t .
- L i c, nhit si c a (4) < (3) l do m c d c hai ch t u c lin k t hydro lin phn t
nh ng lin k t hydro c a (3) d ng polyme cn c a (4) d ng dime
Bi 10: Hy i u ch valin (Val) Me
2
CHCHNH
3
+
COO
b ng:
a. Ph n ng Hell Volhard Zelinski
b. Amin ha kh
c. T ng h p Gabriel
BI GI I:
a.
3 2
NH Br / P
2 2 2 2 2
Me CHCH COOH Me CHCHBrCOOH Me CHCH(NH )COOH
b.
3
2
NH
2 2 2 H / Pt
Me CHCOCOOH Me CHCH(NH )COOH
c. S :
NK
O
O
CH CHMe
2
COOEt
Br +
-KBr
N
O
O
CH CHMe
2
COOEt
H
3
O
+
Val +
COOH
COOH
Bi 11: Hy t ng h p:
a. Pirolidin t propan-1,3-diol
b. PhN(C
4
H
9
)
2
t anilin v butan-1-ol
c. Morpholin t etilen oxit v NH
3
BI GI I:
a. i u ch pirolidin
2 2
2
1mol SOCl SOCl KCN,1:1
2 2 2 2 2 2 2 2 2
H / Ni NaOH
2 2 2 2 2 2 2 2 HCl
HOCH CH CH OH HOCH CH CH Cl HOCH CH CH CN
ClCH CH CH CN ClCH CH CH CH NH pirolidin

b. i u ch PhN(C
4
H
9
)
2
t anilin v butan-1- ol
4 9 2 4
C H Cl* PhNH NaBH PCC
3 7 2 3 7 3 7 4 9
4 9 2
C H CH OH C H CHO C H CH NPh C H NHPh
PhN(C H )
=
c. i u ch Morpholin t etilen oxit v NH
3
O
2
NH
3
+
HOCH
2
CH
2
NHCH
2
CH
2
OH
P
2
O
5
O NH
Bi 12: Vi t s i u ch izatin (indolin-2,3-dion) t 2-nitrobenzoyl clorua
BI GI I:
d
NO
2
C
O
Cl
KCN
-HCl
NO
2
C
O
CN
H
3
O
+
-NH
3
NO
2
C
O
COOH
6H
-H
2
O
NH
2
C
O
COOH
t
o
-H
2
O
NH
O
O
Bi 13: Cho bi t cng th c m ch h c a cc ch t sau:
O OH
O
HO
O
O
CH
3
CH
2
CH
3
Brevicomin
O
C
2
H
5
O
HOCH
2
OH
Talaromicin A
a.
b.
c. d.
BI GI I:
a. CH
2
OHCH
2
CH
2
CH
2
=CHO 5-hidroxipentanal
b. CHOCH
2
CH
2
CHOHCH=CHCH=CH
2
4-hidroxiocta-5,7-dienal
c. CH
3
CH
2
CHOHCHOH(CH
2
)
3
COCH
3
6,7-dihidroxinonan-2-on
d. (HOCH
2
)
2
CHCHOHCH
2
CO(CH
2
)
2
CH(C
2
H
5
)CH
2
OH 2,8-di(hidroxometyl)-1,3-dihidroxidacan-5-on
Bi 14: Hy chuy n thiolacton thnh lactam:
S O NH
2
CH
2
CH
2
NH O
HS
BI GI I:
S O NH
2
CH
2
CH
2
NH O
HS
S O
NH
2
..
NH
S
OH
..
1. OH
-
2. H
+
..
Bi 15: Pirol u c kh b ng Zn v CH
3
COOH thnh pirolin C
4
H
7
N
a. Vi t 2 cng th c c th c c a pirolin
b. Ch n ng phn th a i u ki n sau: Khi ozon phn c C
4
H
7
NO
4
, ch t ny c t ng h p t 2
mol axit mono cloaxetic v amoniac
BI GI I:
a. Con s trong tn g i ch v tr H c ng h p. Hai ch t c th l :
N H N H
2,5-dihidropirol (A) 2,3-dihidropirol (B)
b. ng phn A cho HOOCCH
2
NHCH
2
COOH (C) v ng phn B cho HOOCCH
2
CH
2
NHCOOH
(D). Theo bi th ta ch n A. V y pirolin l ng phn A
Bi 16: Vitamin C (axit L-ascobic) l endiol v c c u trc nh sau:
a. Hy gi i thch tnh axit c a axit L-ascobic (pK
a
= 4,21) v cho bi t nguyn t H no c tnh axit
b. i u ch L-ascobic t D-glucoz
BI GI I:
a. Anion c hnh thnh b i s tch H enolic l b n v i n tch c gi i t a n O c a C=O qua
lin k t i C=C
C
C HO
HO C
O
H
+
-
C
C
-
O
HO C
O
C
C O
HO C
O
b. S i u ch
D-Glucose
NaBH
4
D-Socbitol (A)
[O]
enzym
L-Socbose (B) endiol B'
2CH
3
COCH
3
Diaxetonua (C)
1. KMnO
4
/OH
-
2. dd H
+
(D)
H
+
t
o
axit L-ascobic
Trong :
CH
2
OH
HO H
HO H
H OH
HO H
CH
2
OH
A
CH
2
OH
C O
HO H
H OH
HO H
CH
2
OH
B
CH
2
OH
C HO
C HO
H OH
HO H
CH
2
OH
B'
CH
2
OH
C
C
H O
HO H
CH
2
O
C
CH
3
CH
3
O
O
C
CH
3
CH
3
C
COOH
C
C
H O
HO H
CH
2
O
C
CH
3
CH
3
O
O
C
CH
3
CH
3
D
Bi 17: Cho bi t s n ph m t o thnh t cc ph n ng sau v g i tn s n ph m :
a. Furan + (CH
3
CO)
2
O + (C
2
H
5
)
2
O: BF
3
o
0 C
A
b. Thiophen + C
6
H
5
COCl + SnCl
4
B
c. Pyrol + C
6
H
5
N
2
+
Cl
C
d. Pyrol + CHCl
3
+ KOH D
BI GI I:
O
COCH
3
2-acetylfuran
A
S
COC
6
H
5
2-benzoylthiophen
B
N
N=NC
6
H
5
H
2-(phenylazo)pyrol
C
N
CHO
H
2-pyrolcacboxandehit
D
Bi 18: Trnh by c ch ph n ng t ng h p quinolin b ng ph ng php Skaraup. i u ch quinolin t
anilin, glyxeryl, nitrobenzen trong mi tr ng axit sunfuric m c xc tc s t (II) sunfat
BI GI I:
C ch ph n ng qua 4 giai o n sau:
Giai o n 1: Dehydrat ha glyceryl b ng H
2
SO
4
un nng c aldehyd acrolein
Glyceryl
2 4
o
H SO
t
CH
2
=CHCHO + 2H
2
O
Acrolein
Giai o n 2: Ph n ng c ng i nhn c a anilin v i acrolein thu c: (phenyla min o)propionaldehyd |
NH
2
+
H
C
O
CH
CH
2 N
H
CH
2
CH
2
C H
O
Giai o n 3: Tc nhn i i n t tc d ng vo vng th m b i nhm carbonyl c a aldehyd c proton
ha (y l giai o n ng vng)
+
N
H
CH
2
CH
2
C H
O
H
+
N
H
CH
2
CH
2
C H
OH
N
H
H
OH
H
+
-H
2
O
N
H
-
1,2-dihydroquinolin
Giai o n 4: Oxy ha b i nitrobenzen thu c vng th m
+
H
+
2 H
2
O
N
H
1,2-dihydroquinolin
3
NO
2 NH
2
3
N
+
+
quinolin
St (II) sunfat c tc d ng lm cho ph n ng x y ra t t theo chi u thu n
Bi 19: Trong y h c, ng i ta th ng dng dung dch polividon 3,5% thay th cho huy t t ng trong
cc tr ng h p m t mu, b ng n ng, s cb ng cch ti m tnh m ch . Qu trnh t ng h p lo i ha ch t
ny th ng i t butan-1,4-diol theo s chuy n ha:
3 2 2 3
o o
NH H O NH Cu,Cr HC CH
2 2 2 2
240 C t ,Polyme ha
HOCH CH CH CH OH A B C polividon
+

Hon thnh s trn bi t cng th c c a polividon l:
N
O
CH CH
2
n
BI GI I:
O
O
A
N
O
H
B
N
O
CH CH
2
C
Bi 20: Hon thnh cc ph ng tr nh ph n ng sau:
O +
C
N
C
H
O
O
ete, 30 C
o
A
N COOC CH
3
CH
3
CH
3
+
Br
F
+
Mg
THF, t si
o
B + MgBrF
BI GI I:
O
C
C
NH
O
O
A
N COOC(CH
3
)
3
B
************************************************
Part 5: ALKALOID
N
N
CH
3
O
O
CH
2
OHC
--------------------------------------------------------------------------------------------------------------------------------
Bi 1: Dng d u * nh d u nguyn t carbon b t i c a cc alkaloid sau:
N
N
CH
3
Nicotin
a.
b.
c.
N
H
CH
2
CH
2
CH
3
Coniin
CH
3
CH
2
CH
2
N
N
CH
3
Pilocacpin
BI GI I:
N
N
CH
3
Nicotin
a.
b.
c.
N
H
CH
2
CH
2
CH
3
Coniin
CH
3
CH
2
CH
2
N
N
CH
3
Pilocacpin
*
*
* *
Bi 2: Papaverin l alkaloid c tch t nh a v qu cy papaver sonniferum (cy thu c phi n). l
ch t r n nng ch y 147
o
C, c tc d ng dn vnh nn c dng d ch a b nh co th t i tr ng, m ch
mu. Qu trnh t ng h p papaverin C
20
H
21
O
4
N (G) trong cng nghi p c cho b i s sau.
3 5 2 5 2
o o
H O PCl P O H / Ni KCN B Pd
3 2 6 3 2
t t
3, 4 (CH O) C H CH Cl A B C D E F G
+
+

a. ngh cng th c c u trc c a cc ch t t A G
b. Trong papaverin c d vng no.
BI GI I:
OCH
3
OCH
3
CH
2
CN
OCH
3
OCH
3
CH
2
CH
2
NH
2
A B
OCH
3
OCH
3
CH
2
COOH
C
OCH
3
OCH
3
CH
2
COCl
D
CH
3
O
OCH
3
NH
C O
CH
2
OCH
3
OCH
3
E
CH
3
O
OCH
3
N
CH
2
OCH
3
OCH
3
F
Papaverin G l:
CH
3
O
OCH
3
N
CH
2
OCH
3
OCH
3
Trong G c ch a d vng isoquinolin
Bi 3: Coniin l h p ch t r t c c tm th y trong cy c sm (conium maculatum). Tri t gia c i
ng i Hy L p Socrates b gi t b i ch t ny. Coniin l m t h p ch t ch a nit v l m t alkaloid. Xc
nh ha tnh v ha l p th c a coniin b ng cch hon thnh cc chu i ph n ng sau. V CTCT A, B, C.
Trong :
Hofmann exhaustive methylation: s metyl ha tri t theo Hofmann
Optically active: ho t ng quang h c
BI GI I:
B c oxy ha b ng KMnO
4
tham kh o trong ti li u: A. M. Castano, J.M. Cuerva, A. M. Echavarren,
Tetrahedron Letters, 35, 7435-7438 (1994)
Bi 4: Nicotin l alkaloid chnh c a thu c l, c th coi l alkaloid lo i pyridin hay lo i pyrolidin. Nicotin
l ch t l ng khng mu, trong kh quy n chuy n nhanh sang mu nu. V i m t l ng nh , nicotin kch
thch th n kinh v lm tng huy t p. Tuy nhin v i li u l ng cao, nicotin ph h y ni m m c c a h h
h p v c th d n t i t vong. Qu trnh t ng h p nicotin K C
10
H
14
N
2
theo s sau:
N
O
CH
3
EtO
-EtOH
-
A
CHO
N
B
EtOH
C
KMnO
4
D
HCl dac
E
- CO
2
F
OH
-
G
NaBH
4
H
HI
t
o
I K
Xc nh cc ch t t A I trong s trn.
BI GI I:
Cng th c c a cc ch t t A n I torng s :
N CH
3
O A
N
O
CH
3
-
O N
B
N
O
CH
3
HO N
C
N
O
CH
3
O N
D
N
HCl
-
C
O
HC
H
2
C
C
OH
O
CH
2
NH
2
Cl
-
CH
3
E
N
HCl
-
C
O
NH
2
Cl
CH
3
F G
N
HCl
-
C
O
NHCH
3
N
CH
OH
NH CH
3
H I
N
CH
NH CH
3
I
N
N
CH
3
K
Bi 5: Higrin X C
8
H
15
ON l m t ankaloid c tm th y trong cy coca. Xc nh CTCT c a X bi t
r ng: X khng tc d ng v i benzensunfoclorua, khng tan trong ki m nh ng tan trong dung dch HCl. X
tc d ng v i phenylhirazin v cho ph n ng iodofom. N u oxi ha X b ng dung dch CrO
3
s t o thnh
axit higrinic C
6
H
11
O
2
N. C th t ng h p axit higrinic C
6
H
11
O
2
N b ng chu i cc ph n ng sau:
+
3 2 2 2 2
o
o
CH NH [CH(COOEt) ] Na Br Ba(OH) dd ddHCl
2 2 2 11 19 4
t
t
2 2
BrCH CH CH Br (C H O )
axit higrinic CO +H O
A B C D E
E

BI GI I:
T cc d ki n cho ch ng t higrin c nhm amin b c ba v c nhm acetyl CH
3
CO
3 2 2 2 2 2 2 2 2 2 2
(CH ) Br BrCH CH CH CH(COOEt) BrCH CH CH CBr(COOEt )
N
CH
3
COOEt
COOEt
C
D
Ba
N
CH
3
COO
COO N
CH
3
COOH
COOH
E
N
CH
3
COOH
E
V y Higrin l:
N
CH
3
CH
2
COCH
3
PhNHNH
2
NaOI
CrO
3
N
CH
3
CH
2
C=NNHPh
CH
3
N
CH
3
CH
2
COOH CHI
3
+
N
CH
3
COOH
Bi 6: T h t tiu ng i ta tch c alkaloid piperin A (C
17
H
19
NO
3
) l ch t trung tnh. Ozon phn A thu
c cc h p ch t: etadial, B, D. Thu phn B thu c OHC-COOH v h p ch t d vng 6 c nh
piperiin (C
5
H
11
N). Cho D tc d ng v i dung dch HI c thu c 3,4-dihydroxibenzandehit. Hy xc
nh cng th c c u t o c a A, B, D. C bao nhiu ng phn l p th c a A?
BI GI I:
- Ozon phn A thu d c etadial ch ng t trong A c nhm =CHCH=
- Thu phn B thu d c OHCCOOH v piperidin, suy ra B c lin k t O=CN
V y N n m trong vng 6 c nh.
- D ph n ng v i HI thu d c 3,4-dihidroxibenzandehit. V y c cc cng th c c u t o:
OHC C
O
N
(B)
O
O
CHO
(D)
O
O
CH CH CH CH C
O
N
(E)
- Trong A c 2 lin k t i, s ng phn hnh h c l 4: ZZ , EE , ZE , EZ
Bi 7: Salixin C
13
H
18
O
7
l m t alkaloid c tm th y trong cy li u. em th y phn Salixin b ng ezym
elmusin cho D-glucoz v Saligenin C
7
H
8
O
2
. Salixin khng kh thu c th Tolen. Oxi ha Salixin b ng
HNO
3
thu c m t h p ch t h u c X m khi th y phn th cho D-Glucoz v anehit Salixylic. Metyl
ha Salixin thu c pentametylsalixin, th y phn h p ch t n y cho ta 2,3,4,6-tetra-O-metyl-D-Glucoz .
Xc nh CTCT c a Salixin
BI GI I:
Salixin l ng khng kh v l glucozit | do b th y phn b i elmuxin
RO H
OH
HO
OH
CH
2
OH
O
H
2
O
enzim
D-Glucose + ROH (Saligenin)
C
7
H
8
O
2
Salixin
Trong cng th c C
7
H
8
O
2
, ROH xu t hi n nhn th m. Tch c andehit salixylic, i u ch ng t qu
trnh oxi ha nhm CH
2
OH thnh nhm CHO
D-Glucose +
CHO
HO
H
2
O, H
+
O HO
HO
OH
O
HOH
2
C
CHO
Saligenin l o-(hidroximetyl)phenol. Cng th c c u trc c a salixin l
O HO
HO
OH
O
HOH
2
C
CH
2
OH
Bi 8: H t c a cy c sm (conium malculatum) th i trung c c dng lm thu c c th c hi n cc
b n n t hnh. c t ch y u c a h t c sm l m t alkaloid c tn l coniin. Coniin c kh i l ng
mol phn t l 127 g.mol
-1
, ch a 75,60% C v 13,38% H v kh i l ng. Coniin lm xanh qu tm, khng
lm m t mu dung dch Br
2
trong dung mi CCl
4
v c ng khng (amin c ngu n g c th c v t) l m m t
mu dung dch KMnO
4
. Khi dehydro ha coniin thu c h p ch t A (C
8
H
11
N). Oxi ha ch t A th thu
c ch t B c c u t o:
N COOH
Bi t trong c 2 ph n ng trn u khng c s ng hay m vng v phn t coniin khng c C b c ba
a. Xc nh CTPT c a coniin v gi i thch t i sao n khng l m m t mu Br
2
/CCl
4
b. Xc nh CTCT c a coniin v cho bi t b c amin c a n, c a A v B. V sao kh i l ng phn t
c a coniin, A, B u l s l .
c. tch coniin t h t c sm v i hi u sut v tinh khi t cao nn dng chi t v i dung mi no
trong cc dung mi sau:
- N c
- R u etylic
- Dung dch NaOH
- Dung dch HCl
BI GI I:
a. CTPT c a coniin C
8
H
17
N
bt bo ha
2 8 3 1 17
1
2
+ +
A = =
V coniin khng lm m t mu Br
2
/CCl
4
nen coniin khng ch a n i i m ch a vng no.
b. S ph n ng:
N
H
CH
2
CH
2
CH
3
-3 H
2
xt, t
o
N
H
CH
2
CH
2
CH
3
coniin
amin (II)
A
amin (III)
[O]
N
H
COOH
B
amin (III)
H p ch t c ch a s l nguyn t N => c kh i l ng phn t l
c. Dng dung dch HCl v t o mu i coniin clohidrat tan t t trong n c. Sau c th dng ki m
thu l i coniin.
Bi 9: T cy Atropabenladona (m t lo i c c d c) thu c h c, ng i ta tch c m t lo i alkaloid
l atropin. Trong cng nghi p, ng i ta th ng dng atropin i u ch axit tropoic (A) C
9
H
10
O
3
. (A) b
oxy ha b i dung dch KMnO
4
nng thnh axit benzoic (B) v b oxy ha b i oxy khng kh khi c m t
Cu nung nng t o thnh ch t (C) C
9
H
8
O
3
c ch c andehit. Axit tropoic c th chuy n ha thnh axit
atropoic C
9
H
8
O
2
(D) nh H
2
SO
4
c 170
o
C. Hidro ha (D) b ng H
2
/Ni thu c axit hidratropoic (E)
C
9
H
10
O
2
. Hy xc nh cng th c c u t o c a A, C, D, E v cho bi t D c ng phn cis/trans hay khng?
BI GI I:
CTPT c a (A) C
9
H
10
O
3
c b t bo ha:
2 9 2 10
5
2
+
A = =
- A b oxy ha b i KMnO
4
t o axit benzoic nn A c ch a vng benzen v nhm ch c COOH
m ch nhnh (khng g n tr c ti p vo vng benzen)
- A b oxy ha b i oxy khng kh khi c m t Cu nung nng t o th nh ch t (C) C
9
H
8
O
3
c ch c
andehit => M ch nhnh ch a nhm ch c r u b c I l CH
2
OH
- T d ki n bi ra ta c CTCT c a A, B, C, D, E nh sau trong D khng c ng phn hnh h c
CH CH
2
OH HOOC
A
KMnO
4
t
o
O
2
Cu,
170 C
o
t
o
H
2
SO
4
d
COOH
B
CH
COOH
CHO
C
C
COOH
CH
2 H
2
Ni, t
o
D
C
COOH
CH
3
H
E
Bi 10: T h t tiu en, ng i ta phn l p c m t lo i alkaloid l piperin. Xc nh cng th c c u t o
c a piperin d a vo s sau:
A + CH
2
I
2
+ NaOH B (C
8
H
6
O
3
)
B + CH
3
CHO + NaOH C (C
10
H
8
O
3
)
C + anhidrit axetic + natri axetat axit piperic (C
12
H
10
O
4
)
axit piperic + PCl
3
D (C
12
H
9
O
3
Cl)
D + piperidin piperin (C
17
H
19
O
3
N)
BI GI I:
Piperin l:
O
O
CH CH CH CH C
O
N
************************************************
TI LI U THAM KH O:
1. Bi t p L thuy t v Th c nghi m, t p 2: Ha H c H u C Cao C Gic NXB Gio D c 2006.
2. Bi t p Ha H u C Tr n Th Vi t Hoa, Tr n Vn Th nh NXB i H c Qu c Gia TP H Ch
Minh 2003.
3. B thi HSG Qu c gia l p 12 THPT.
4. B thi Olympic 30/4 cc tnh pha nam.
5. B thi Olympic ha h c Vi t Nam v Qu c t
6. Bi t p Ha H u C , t p 1 Ng Th Thu n NXB i h c Qu c Gia H N i 1999.
7. Bi t p Ha H u C , t p 2 Ng Th Thu n NXB Khoa h c v K thu t 2008.
8. Bi t p Ha H u C i H c Y D c TP H Ch Minh 2001.
9. T ng h p H u C Nguy n Minh Th o. NXB i h c Qu c Gia H N i 2001.
10. M t s cu h i v bi t p Ho h u c o Vn ch, Tri u Qu Hng NXB i H c Qu c Gia
H N i.
11. Chuyn m t s h p ch t thi n nhin L Vn ng NXB i H c Qu c Gia TP H Ch
Minh 2005.
12. Ha H c H u C t p 2, 3 PGS.TS. nh Rng (CB) NXB Gio D c 2006.
13. Ha h u c D c B mn Ha H u C H D c H N i 1999.
14. Ha H u C - H p ch t n ch c v a ch c PGS. TS. Tr ng Th K NXB Y H c H N i
2006.
15. Organic chemistry Clayden, Greeves, Warren, Wothers Oxford, 2001.
************************************************
LI M U
Part 1: AXIT CACBOXYLIC ESTE ................................ ................................ ......Trang 2
Part 2: AMINOAXIT AMIN PROTEIN ................................ ........................... Trang 20
Part 3: CACBOHIDRAT POLYME ................................ ................................ .........Trang 40
Part 4: CC HP CHT D VNG ................................ ................................ ...........Trang 67
Part 5: ALKALOID ................................ ................................ ................................ .........Trang 80
TI LIU THAM KHO................................ ................................ ................................ ..Trang 88
MC LC................................ ................................ ................................ .............................. Trang 89
- - - - - - - - - - Ht tp 2 - - - - - - - - - -

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Bi 13: Vi t cng th c c u trc cc d ng enol c a dietylmalonat (1), Etylaxetoaxetat (2). Trong cc c u

v d ng trung ho HA c a prolin pH = 9,70.

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