Bài Tập Hóa Học Hữu Cơ Tập 2

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02 2010
Bi tp Ha Hc Hu C Tp 2 Ti liu dnh cho sinh vin cc trng i hc
Copyright 2010 volcmttl@yahoo.com.vn 1
Li ni u
Ha hc hu c l mt trong nhng b mn rt quan trng trong lnh
vc Ha hc ni ring v phm tr Khoa hc t nhin ni chung. Tuy nhin
hin nay, cc ti liu tham kho v bi tp ha hc hu c l khng nhiu. V
vy vic tng hp cc t liu c mt ti liu tham kho b ch v d tip
thu hn l vic rt cn thit.
Bi tp Ha hc hu c l mt ti liu c bin son da trn vic
tng hp li t nhiu ngun t liu khc nhau theo tng chuyn hc
sinh, sinh vin d nm bt. Ti liu gm hai phn: Phn bi tp theo tng
chuyn v phn hng dn gii. Cc bi tp trong tng chuyn c
tuyn chn k lng nhm mc ch m bo cho cc dng b i tp khng
trng lp v hc sinh, sinh vin c th tip cn nhiu hng ra khc nhau
t cng mt d liu kin thc.
Bi tpHa hc hu c bao gm hai tp:
- Tp 1: Gm by chuyn tng ng vi ni dung thuc phn i cng
ha hc hu c v phn kin thc ha hu c t bi alkane n cetone
(theo chng trnh ha hc ph thng).
- Tp2: Gm cc phn t acid carboxylic n cc hp cht d v ng. Ngoi
ra cn minh ha thm mt s bi tp nng cao tng hp cc chuyn .
V l ti liu tng hp li cc bi tp nm trong cc gio trnh, sch tham
kho bi tp hu c, cc thi hc sinh gii nn p n cho tng bi khng
thay i theo p n ca tng t i liu tham kho. V vy Bi tp Ha hc
hu c khng phi l mt ti liu do mt nhm tc gi bi n son m ch l
ti liu tng hp c chn la t cc ngun t liu sn c. (Tng hp t ngun
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 hc lp th ca cc hp cht hu c c th c xc nh bng cch kho st tnh cht
ha hc c trng ca chng. Cu to ca mt trong cc ng phn ca axit 5-norbonen-2,3-dicacboxylic,
hp cht X (k hiu ~ ch khng nu r ha hc lp th) c hnh thnh nh cc th nghim sau:
COOH
COOH
X
Khi un nng X nng chy v tch nc to ra hp cht mi Y. Hp cht Y tan chm trong lng d
dung dch nc ca NaOH to X
1
, cng mt sn phm nh X to thnh trong lng d dung dch
nc ca NaOH. Dung dch thu c ca X
1
trong NaOH c tc dng vi iot, to thnh cc hp cht
c cha iot. Axit ha dung dch to mt hn hp hai cht ng phn trit quang (ti u trin hay raxemic) A
v B theo t l 3:1. Chun 0,3913g hp cht A vi NaOH 0,1000M c mt phenolphtalein cn dng
12,70mL baz. Cn cng mt th tch NaOH 0,1000M NaOH chun 0,3913g hp cht B. Khi un
nng, hp cht A chuyn chm thnh hp cht mi C khng cha iot v c th phn ng vi nc. Trong
cng iu kin, hp cht B khng xy ra chuyn ha ny nhng khi un nng vi axit clohydric th
chuyn chm thnh A. Vit v cn bng mi phng trnh phn ng. Khng cn vit c ch phn ng.
1. nh du (*) cc nguyn t cacbon phi i xng (asymmetric) trong axit 5- norbonen-2,3-
dicacboxylic.
2. Vit cng thc ha hc lp th ca tng ng phn lp t h c th c ca hp cht X v cu to ca
sn phm tch nc nu c xy ra.
3. Vit cc phng trnh phn ng ca mt ng phn lp th bt k ca X v hp cht tng ng Y
vi lng d dung dch NaOH trong nc.
4. Tnh khi lng mol phn t ca cht A. Vit cc phng trnh phn ng t X
1
n A.
5. Vit phng trnh phn ng to thnh C t A v phn ng ca C vi nc.
6. Vit cng thc ha hc lp th ca hp cht X tho mn tt c cc d kin cho.
7. Vit cc phng trnh phn ng dn t B n A.
8. A v B c phi l cc ng phn khng i quang (diastereoisomers)?
BI GII:
1. Cc trung tm bt i ca X:
*
* COOH
*
COOH
*
2. Cng thc cu to ca cc ng phn lp th ca X c ghi bn tri, ct bn phi l cu to ca sn
phm tch nc tng ng (nu sn phm khng tn ti c du gch ngang).
COOH OC
O
COOH OC
COOH CO
O
COOH CO
COOH
COOH
COOH
COOH
3. Phn ng ca mt ng phn lp th ca X vi NaOH:
COOH
COOH
+ 2NaOH
COONa
COONa
+ 2H
2
O
Phn ng ca mt ng phn lp th ca Y vi 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 phn ng t X n A:
COONa
COONa
I
2
-NaI
I
O CO
COONa
HCl
-NaCl
I
COOH
O CO
5. Chuyn ha A thnh C:
I
COOH O CO + HI
O CO O CO
Phn ng ca C vi nc
O CO + 2 H
2
O HO COOH
O CO HO COOH
6. Cu to ca X l:
COOH
COOH
7. Chuyn 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 phi l cc ng phn khng i quang.
Bi 2: Cc nh ha hc ca cng ty Merck Frosst Canada Montral pht trin mt dc phm rt c
trin vng v hu hiu tr bnh suyn. Cu to ca MK-0476 nh sau.
COOH
CH
3
H
3
C OH
S
Cl N
MK 7406
Trong qu trnh kim tra, h pht minh mt qa trnh tng hp n gin v hiu qu, m t di y cho
s thiol ha mt phn ca MK 0476 bt u t este dietyl A
1. Hy cho bit cu to ca cc sn phm trung gian B F trong qa trnh tng hp 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
+

Mt trong nhng giai on cui ca qa tr nh tng hp MK 0476, mui diliti ca thiol axit
(G) trn c ghp vi mch ca phn t nu di y (s di)
2. Cn c trn ha hc lp th quan st c ca phn ng trn, gi tn c ch ca qa trnh ghp
ny?
3. Nu qa trnh phn ng xy ra theo c ch c ngh nh trn th tc ton phn (chung)
s thay i nh th no nu nng ca c mui thiolat v cht nn u cng lc tng gp ba?
4. Cc nghin cu mu c tin hnh vi vic s dng brom etan nh l mt cht nn ti u
ha qa trnh ghp ni trn. V cu to sn phm chnh ca phn ng gia mt mol ng
lng brom etan vi:
a. G thm hai mol ng lng baz.
b. G thm mt mol ng lng 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 phc tp do s nh hp oxi ha (dime ha oxy ha ca G). Vit
cng thc cu to Lewis, ch r tt c cc electron khng lin kt ca sn phm nh hp - oxy
ha trn.
S GHP MCH
BI GII:
1. Cng thc cu to ca cc cht:
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 lng phn t.
3. v = k[tc nhn][tc cht nucleophin]
Tc chung ty thuc vo nng ca c tc nhn ln tc cht nucleophin. Nh vy, gp ba nng
ca cc cht tham gia phn ng s dn n tc chung ca phn ng t ng gp 9 ln.
4. Vi hai ng lng baz:
CH
2
SCH
2
CH
3
CH
2
CO
2
H
Vi mt ng lng baz:
CH
2
SH
CH
2
CO
2
CH
2
CH
3
5. Cng thc Lewis ca sn phm dime:
CH
2
S SCH
2
CH
2
H
2
C
HO O O OH
Bi 3: Nm Aspergillus nidulans to ra hai lacton (este vng) thm A v B (C
10
H
10
O
4
) mi ng phn tan
trong dung dch NaOH lnh trong nc nhng khng tan trong dung dch NaHCO
3
trong nc. C A v B
u cho mu tm vi dung dch FeCl
3
trong nc. Phn ng ca A vi CH
3
I c mt K
2
CO
3
to thnh C
(C
11
H
12
O
4
) m ph
1
H NMR ca n thy c cha ba nhm metyl khng ging nhau, mt nhm lin kt
trc tip vi vng thm. S tch loi nhm metyl c chn lc ca C vi BCl
3
ri x l k tip trong nc
to ra D l mt ng phn mi ca A. Ph
1
H NMR ca hp cht D cho thy r s hin din ca mt
nhm hydroxyl c to lin kt hydro ni phn t ti o = 11,8pm
OH
H
3
C
H
3
C CO
2
CH
3
O
HO
E
I
Hp cht D c tng hp nh sau: Phenol E c metyl ha (MeI/K
2
CO
3
) to F(C
9
H
12
O
2
) sau F
c kh bng liti ki m loi trong amoniac lng v 2 metylpropan 2 ol cho mt dien i xng v
khng lin hp G. C th chuyn dien ny thnh lin hp bng phn ng vi KNH
2
trong amoniac lng
ri x l k tip trong nc, qa trnh ny ch to mt sn phm H. S ozon phn H ri x l khng kh
l tip to ra nhiu sn phm, trong c xetoeste I. Thc hin phn ng Diels Alder hp cht H vi
dimetyl but 2 indioat J to thnh K (C
15
H
20
O
6
) m khi un nng s loi eten to ra mt este thm L.
Thy phn L trong mi trng baz ri axit ha dung dch to thnh M(C
11
H
12
O
6
) m khi un nng trong
chn khng to ra N (C
11
H
10
O
5
). Kh N bng NaBH
4
trong dimetylfomamit to thnh C v mt lacton O
ng phn, O cng c th thu c nh metyl ha B.
1. Vit cng thc cu trc ca tt c cc hp cht t A n O.
2. Hy trnh by mt cu trc khc ca B.
BI GII:
1. Cng thc cu to ca cc cht:
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 thc khc ca B:
OH
H
3
C
O
H
3
CO
O
Bi 4: (-)-Atractyligenin l mt hp cht hot ng sinh hc c c lp t cy gi l Thistle cht choc.
Ngi Zulu dng n cha bnh nhng thng gy him ha cht ngi. c th to mt hp cht
tng ng c c tnh km hn, nay c nhiu phng php tng hp ha hc:
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 tng hp cht tng ng ca (-) Atractyligenin, hp cht A uc dng lm nguyn liu u.
Trc ht cho cht A tc dng vi dung dch natri hydroxit trong nc to thnh B (C
5
H
10
O).
1. Hy vit cng thc cu to ca hp cht B
2. Khi cho hp cht B tc dng vi kali dicromat trong dung dch nc ca axit sunfuric thu c C
(C
5
H
8
O). Hy vit cng thc cu to ca hp cht C.
3. Ho tan hp cht C trong toluene ri sc kh hydro bromua qua dung dch cho n khi ton b C
phn ng ht thu c hp cht D. Hy vit cng thc cu to ca hp cht D
4. Hp cht D c ng phn lp th khng? Nu c, hy cho bit c bao nhiu ng phn lp th?
5. Cho hp cht D tc dng vi dung dch natri hidroxit trong etanol to thnh hp cht E, khi un
nng s chuyn v thnh cht F Hy vit cng thc cu to ca hp cht E.
6. Hp cht F c ng phn lp th khng? Nu c, hy cho bit c bao nhiu ng phn lp th?
7. Dung dch hp cht F tc dng vi kali pemanganat cho hp cht G. Cui cng G c un nng
hi lu trong etanol c mt xc tc axit sunfuric to thnh hp cht H.Hy cho bit tn IUPAC ca
H Hp cht H c cho tc dng vi 2 metylbutylmagie bromua. Sau khi axit ha, thu c mt
hn hp cc sn phm ng phn I.
8. Hy vit cng thc cu to sn phm I (khng xt ng phn)
9. Hy tr li cc cu hi sau
a. S ng phn lp th c lp c ca sn phm I l 2, 4, 6 hay 8?
b. Tt c cc ng phn lp th c lp c ca sn phm I c to thnh vi s lng bng
nhau, hay mt phn c s lng khc nhau hay tt c c s lng khc nhau?
c. Trong cc ng phn lp th c lp c ca sn phm I th tt c c cng im nng chy hay
tt c c im nng chy khc nhau hay mt s c im nng chy ging nhau?
BI GII:
Cng thc cu to cc cht nh sau:
Br OH
A
B
O O
O
O
*
C
Br
D E
F
O O
OH O
G H
*
OH
*
I
Cht D c 2 ng phn i quang
Cht F c hai ng phn hnh hc
- Cht I c 4 ng phn lp th ring bit
- Cp ng phn khng i quang c lng khc nhau. Cp i quang c lng bng nhau
- Cp ng phn khng i quang c im nng chy khc nhau. Cp ng phn i quang c im
nng chy bng nhau
Bi 5: Mt thnh phn S ca du hoa hng dng c cu to 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 ca S? Dng du hoa th (*) ch ra cc tm i xng gng
ca phn t, nu c.
b. S tc dng vi natri metoxit cho hn hp 3 este metyl. ngh tn ca 3 este ny. Dng cch ghi
Z, E nu cn.
c. Cho cc este metyl cha no tc dng vi ozon ri vi km xc nh v tr ca cc lin kt i
trong phn t. Vit cng thc cu to ca 4 hp cht c nhm chc andehit. Vit tn IUPAC ca
chng.
d. Ch s x phng ha ca mt cht bo c nh ngha l s miligam kali hydroxit cn thu
phn 1g cht bo. Ch s ny c dng so snh cc khi lng phn t tng i ca cht
bo. Hy tnh th tch ca kali hydroxit 0,996M cn dng x phng ha 10,0g cht bo S
e. Ch s x phng ha ca S l bao nhiu?
f. Ch s iot ca cht bo c nh ngha l s gam iot (I
2
) c th tham gia phn ng cng vi 100g
cht bo. Hy tnh ch s iot ca cht S.
BI GII:
a. Cc phn t ca cht thnh phn 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 thc cu to v tn gi ca 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 ri tc dng vi Zn cho cc andehit sau:
nonal
O O
hexanal
O O
metan dicacbadehit
O
O O
metyl nonalat
d. S mol KOH dng nhiu gp 3 ln 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 cha 3 . 112,9mmol lin kt i C = C
Vy 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 cp ca cc loi cy thuc h cam,
chanh v cng gp phn lm nn v chua c trng ca n. Cch sn xut th cng nht ca n l ln men
mt ma hay tinh bt, h s dng loi nm Aspergillus niger ti pH = 3,5. Axit xitric c s dng rng
ri trong cng nghip thc phm, sn xut nc ngt v lm thuc cn mu trong cng nghip
phmnhum. Ngoi ra n cng l mt cht trung gian quan trng trong c c qa trnh sinh ha.
a. Cht no c sinh ra khi ta un nng axit xitric vi axit sunfuric c 45 50
o
C. Hy vit cng
thc cu to v c tn ca sn phm to thnh theo IUPAC. Loi axit hu c no tham gia c
phn ng trn?
Sau khi un nng axit xitr ic vi axit sunfuric, ngi ta thm vo anisol (metoxybenzen) vo hn hp phn
ng v nhn c cht A(C
12
H
12
O
5
).
A to anhydrit khi un nng vi anhydrit axetic
trung ho 118mg A cn 20mL dung dch KOH 0,05N
Cng mt lng cht A nh trn c th phn ng ht c vi 80mg brom to thnh sn
phm cng
b. Xc nh cng thc cu to A
c. Xc nh cc ng phn c th c ca A sinh ra trong phn ng trn, hy xc nh cu dng v vit
tn IUPAC ca chng.
d. Trong phn ng brom ha th c bao nhiu ng phn lp th ca A c sinh ra. Hy v cng
thc chiu Fischer ca chng.
e. Xc nh cu hnh tuyt i ca cc trung tm bt i trong cc sn phm cu d
Nu trong phn ng hnh thnh A ta thay anisol bng cht khc nh phenol hay resoxinol th tng ng ta
thu c cc cht B v C. B khng cho phn ng mu khi tc dng vi FeCl
3
nhng C th c. Trong cng
iu kin phn ng to thnh 2 cht B, C th hiu sut to thnh C cao hn.
f. Xc nh cng thc cu to ca B v C
g. Phn ng to thnh A v B khc nhau im c bn no?
h. L do ti sao hiu sut to thnh C cao hn to thnh B
BI GII:
a. Phn 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 mi tham gia phn ng ny
b. - Khi lng phn t A = 236
20mL KOH 0,05M phn ng vi 118mg A
1000mL KOH 1M phn ng vi 118g A
A phi l axit 2 chc
- Khi lng phn t A = 236
80mg Br
2
phn ng vi 118mg A
160mg Br
2
phn ng vi 236mg A
A c cha mt lin kt i. Trong phn t A c cha vng anisol
N li c hnh thnh t axit HOOC CH
2
COCH
2
COOH v c cng thc phn t C
12
H
12
O
5
.
Do c s cn tr khng gian ca cc nguyn t hydro trong anisol nn nhm t h buc phi nm
v tr para so vi nhm OCH
3
. Nh vy cng thc cu to ca cht A s nh sau:
H
3
CO
COOH
COOH
V A to c anhydrit nn hai nhm -COOH buc phi cng pha so vi lin kt i.
c. Cc ng phn ca 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 sn phm khi cho A tc dng vi brom
COOH
COOH
H Br
HOOCH
2
C Br
Br H
Br CH
2
COOH
OCH
3 OCH
3
1 2
Hai cht ny l enantiome
e. Cu hnh tuyt i ti cc trung tm lp 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 thc cu to cc cht B v C
CH
2
COOH
CH
2
COOH
O O
HO O O
B
C
g. Trong s hnh thnh cht A t anisol th hng tn cng l v tr para so vi nhm OCH
3
. Tuy nhin
trong phn ng to thnh cht B t phenol th v tr tn cng l ortho so vi nhm OH. S khc nhau ny
l do s cn tr khng gian ca cc nguyn t hydro trong nhm OCH
3
. Nh vy s tn cng c th xy
ra hai v tr ortho v para nhng hng tn cng ortho c u tin hn do sn phm trung gian c th
vng ha c to sn phm bn B.
h. Phenol ch c 1 nhm OH trong vng phenyl cn resoxinol th li c n 2 nhm OH trong vng
phenyl m hai nhm ny li v tr meta. iu ny dn n v tr 4 trong resoxinol c mt electron ln
i vi resoxinol.
6
1
OH
HO
5
4
3
2
OH
Nh vy th trong cng iu kin phn ng th lng sn phm C lun nhiu hn B
Bi 7: S pht trin ca cc loi dc phm mi ph thuc ch yu vo tng hp hu c. Phng php
chnh li phn t (fine-tuning) c s dng c th nhn c cc tnh cht nh mong mun. Sau y l
qa trnh tng hp thuc gy m cc b proparacaine (cn c gi l proxymetacaine), cht ny c s
dng iu tr cc bnh v mt.
1. Hon thnh qa trnh tng hp bng cch vit cng thc cu to cc cht 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
Tt c u l cc sn phm chnh
2. Khi ta nitro ha axit - m hydroxybenzoic th thu c nhng sn phm no?
3. Khi t C
4
H
9
Cl c s dng bc 2 thay cho C
3
H
7
Cl th iu ny s dn ti:
a. Mt sn phm tng t B (nu iu ny ng hy vit CTCT sn phm)
b. Khng c phn ng
c. S phn hy t C
4
H
9
Cl
d. Mt phn ng th S
E
Hy chn cu tr li ng
BI GII:
1. Cng thc cu to cc cht 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 thc cu to cc sn phm:
NO
2
O
OH
OH
3. c
O
OH
+
O
2
N
OH
Bi 8: Vit c ch ca cc phn 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 GII:
a. C ch phn 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: Loi dc phm c s dng nhiu nht trong tt c mi thi i l axit axetylsalixilic (ASS), n
c by bn rng ri trn th trng di tn thng mi l aspirin lm thuc chng nhc u. Ci tn
aspirin l do mt cng ty c xut nm 1899. ASS c th c tng hp bng con ng sau y:
Vit cng thc cu to ca A, B, C v ASS.
BI GII
Phn ng u tin l phn ng Kolbe Schmidt, tip theo l phn ng proton ha, sau phn ng ny th axit
salixilic B c hnh thnh. Phn ng vi anhydrit axetic s dn n vic to thnh axit axetylsalixilic ASS.
Bi 10: Sildenafil (mt loi thuc tng lc) c tng hp 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
hai l - u, 2 h,
-
NH N
ClSO
3
H, SOCl
2
t
c
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
c
phng, 7O h
L
1. Hy hon chnh dy phn ng trn, bit rng:
o Qu trnh chuyn sang G c to thnh axit sunfonic trung gian sau mi chuyn
thnh sunfonyl clorua.
o N,N
,
-cacbonyliimiazol (CDI) l mt loi tc nhn dng hot ho axit cacboxylic
cho phn ng th nucleophin ca nhm cacbonyl.
2. Vit c ch phn ng chuyn [I] thnh K.
BI GII
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
c
phng, 18 h
H
Me
hai 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
c
phng, 7O 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: Vit cng thc cu to ca sn phmcui (nu c) t cc phn ng sau:
+ (I
2
, KI, NaHCO
3
) A
Br
CH
3
H
2
N CH COOH B +
BI GII
A l
O
O
I
B khng tn ti v phn ng khng xy ra
Bi 12: Sn phm no c to thnh khi cho stiren oxit tng tc vi dietylmalonat?
BI GII:
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: Vit cng thc cu trc cc dng enol ca dietylmalonat (1), Etylaxetoaxetat (2). Trong cc cu
trc ca (2), cho bit dng no bn nht, dng no km bn. Gii thch?
COOH
O
Ph
O
BI GII:
a. Cc cu trc
C
H
OEt
O
H
O
EtO
C
H
OEt
O O
EtO
H
OEt
O O
EtO
b. Trong :
- Dng A t bn do ni i khng li n hp
- Dng B bn nhng khng c cng hng este
- Dng C bn nht do c ni i li n hp v cng hng 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 vi dung dch n c brom d th axit d dng to thnh tribromphenol.
Vit c ch. C th ch i phn ng ca axit m- v p-hidroxibenzoic khng?
BI GII:
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
+
-
-
To thnh xetoaxit | torng gian, loi hp cht ny d b decacboxyl ha.
ng phn meta- kh xy ra phn ng v khng to thnh xetoaxit |
ng phn para- c th c v hp cht ny l xetoaxit c ni i , o |
O
COOH
Br
Part 2: AMINOAXIT AMIN PROTEIN
N
O
N
O
N
N
O
N
N
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Hp cht hu c A c 74,074% C; 8,642% H; c n li l N. Dung dch A trong nc c nng %
khi lng bng 3,138%, si nhit 100,372
o
C; hng s nghim si ca nc l 1,86
o
C.
1. Xc nh cng thc phn t ca A.
2. Oxi ha mnh A thu c hn hp sn phm trong c E (axit piridin -3-cacboxilic) v F
(N-metylprolin). Hy xc nh cng thc cu to ca A v cho bit gia E v F cht no c sinh ra
nhiu hn, cht no c tnh axit mnh hn.
3. A c 1 ng phn cu to l B; khi oxi ha mnh B cng sinh ra 1 hn hp sn phm trong c E v
axit piperidin-2-cacboxilic. Xc nh cng thc cu to ca B.
4. Cho A v B tc dng vi HCl theo t l mol 1:1, cht no phn ng d hn? Vit cng thc cu to
ca cc sn phm.
BI GII:
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 nhiu hn 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: Sp xp c gii thch s tng dn tnh axit ca:
(D)
(A) (B)
(C)
;
N
COOH
;
COOH
;
CH
2
COOH
N COOH
BI GII:
(D)
<
<
<
-l
1
CH
2
COOH
(C) (A)
-l
2
-l
3
N
H
C
O
O
-C
3
(B)
-C
4
-l
4
N
COOH
COOH
V: - I
1
< - I
2
nn (C) c tnh axit l n hn (D).
(A) v (B) c N nn tnh axit l n hn (D) v (C)
(A) c lin kt hiro ni phn t l m gim tnh axit so vi (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 cnh.
1. Vit cng thc Fis v cng thc phi cnh ca L-prolin. Tnh pHI ca hp cht ny.
2. Tnh gn ng t l dng proton ha H
2
A
+
v dng trung ho HA ca prolin pH = 2,50.
3. Tnh gn ng t l dng eproton ho A
v dng trung ho HA ca prolin pH = 9,70.

4. T metylamin v cc ha cht cn thit khc (benzen, etyl acrilat, natri etylat v cc ch t v c), hy
vit s iu ch N-metyl-4-phenylpiperiin.
BI GII:
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 dng phng 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
Vy pH = 2,50 dng trung ho chim nhiu hn dng proton ha 3,24 ln.
Hay t l gia dng proton ha v dng 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
Vy pH = 9,7 t l gia dng eproton h a v dng trung ho l
1
8
.
4.
CH
3
NH
2
CH
3
-N
+Br
2
/Fe, t
c
Br
Mg
ete
MgBr
Bi 4: Hy cho bit cc sn phm ca s thy phn trong mi trng axit ca cc cht CH
3
CONH
2
,
O
N
O
O
CH
3
BI GII:
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: Hp cht A (C
5
H
11
O
2
N) l mt cht lng quang hot. Kh A bng H
2
c xc tc Ni s c B
(C
5
H
13
N) quang hot. Cho B tc dng vi axit HNO
2
thu c hn hp gm ancol C quang hot v ancol
tert-amylic (2-metyl-2-butanol).
Xc nh cng thc cu to ca A. Dng cng thc cu to, vit phng trnh cc phn ng to
thnh B, C v ancol tert -amylic t A.
BI GII:
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
, 17O
c
C
CH
3
N
C
6
H
5
H
2
, Ni, t
c
*
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 hoc toluen v cc cht v c tng hp c cc dc cht sau:
Axit 4-amino-2-hidroxibenzoic; axit 5-amino 2,4 dihidroxibenzoic.
BI GII:
HNO
3
H
2
SO
4
, t
O
NO
2
NO
2
Sn/ HCl
NH
2
NH
2
OH
NH
2
HNO
2
OH
NH
2
CO
2
,OH
-
t
O
,p
COOH
HNO
3
H
2
SO
4
, t
O
NH
2
NH
2
OH
OH
HNO
2 CO
2
,HO
t
O
, p
OH
OH
COOH
OH
OH
COOH
O
2
N
OH
OH
Sn /HCl
COOH
H
2
N
hoc
HNO
3
H
2
SO
4
, t
O
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 thc cu to, hy hon thnh s tng hp 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. Gii thch hng ca phn ng to thnh C
8
H
8
O
4
NSCl v C
6
H
8
O
2
N
2
S.
BI GII:
a. COCl
2
+ CH
3
OH CH
3
O-COCl
Chuyn 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 hng o, p; do kch thc ln, tc nhn ln nn vo v tr p.
NHCOOCH
3
este-amit thy phn thnh CO
2
| , cn SO
2
NH
2
bn hn.
Bi 8: TRF l tn vit tt mt homon iu khin hot ng ca tuyn gip. Thy phn ho n ton 1 mol
TRF thu c 1 mol mi cht sau:
NH
3
;
N
H
COOH
(Prc)
;
HOOC-CH
2
-CH
2
-CH-COOH
NH
2
(Glu)
;
N
N
H
CH
2
-CH-COOH
(His)
NH
2
Trong hn hp sn phm thy phn khng hon ton TRF c dipeptit His -Pro. Ph khi lng cho bit
phn t khi ca TRF l 362 vC. Phn t TRF khng cha vng ln hn 5 cnh.
1. Hy xc nh cng thc cu to v vit cng thc Fis ca TRF.
2. i vi His ngi ta cho pKa
1
= 1,8 ; pKa
2
= 6,0 ; pKa
3
= 9,2. Hy vit cc cn bng in ly v ghi cho
mi cn bng mt gi tr pKa thch hp. Cho 3 biu thc:
pH
I
= (pKa
1
+pKa
2
+pKa
3
) : 3 ; pH
I
= (pKa
1
+pKa
2
) : 2 ; pH
I
= (pKa
2
+pKa
3
) : 2 ;
biu thc no ng vi His, v sao?
3. Hy ngh s phn ng vi y iu kin tng hp axit (D, L) glutamic t hidrocacbon
cha khng qu 2 nguyn t cacbon trong phn t.
BI GII:
1. * T d kin thy phn suy ra 2 cng thc Glu -His-Pro v His-Pro-Glu (u c 1 nhm CO NH
2
)
* T M = 362 vC suy ra c to ra amid vng (loi H
2
O)
* T d kin vng s 5 cnh suy ra Glu l aminoaxit u N v to lactam 5 cnh, cn Pro l aminoaxit
u C v to nhm CO NH
2
.
Vy cu to ca TRF:
HN CH
O
CO-NH CH CO N CH CO-NH
2
CH
2
N
NH
Cng thc Fis:
NH
CO
CO
CO
CH
2
NH
2
H
H
H
O
N
NH
N
NH
2. Cn bng in ly ca 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
(hoc vit 3 cn bng ring r; khng cn cng thc Fis)
* pH
I
= (pKa
2
+ pKa
3
) : 2 l ng,
v phn t His trung ha in (in tch = 0) nm gia 2 cn bng (2) v (3)
3. Tng hp 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: Thy phn hon ton mt hexapeptit M thu c Ala, Arg, Gly, Ile, Phe v Tyr. Cc peptit E
(cha Phe, Arg) v G (cha Arg, Ile, Phe) c to thnh trong s cc sn phm thy phn khng ho n
ton M. Dng 2,4-dinitroflobenzen xc nh c amino axit Ala. Thy phn M nh tripsin thu c
tripeptit A (cha Ala, Arg, Tyr) v mt cht B.
a. Xc nh th t lin kt ca cc amino axit trong M.
b. Amino axit no c pH
I
ln nht v amino axit no c pH
I
nh nht?
Bit cu to chung ca 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 GII:
a. Hexapeptit M c u N l Ala. Thu phn M nh tripsin xc nh c tripeptit l: Ala Tyr Arg.
Dipeptit E c cu to Arg-Phe. Tripeptit G c cu to: Arg-Phe-Ile. Do vy amino axit u C l: Gly.
Ala Tyr Arg
Arg Phe
Arg Phe Ile
Gly
Vy cu to ca M: Ala Tyr Arg Phe Ile Gly.
b. pH
I
ln nht: Arg, v c nhm guanidin (c 3 nguyn t N)
pH
I
nh nht: Phe, v c nhm phenyl.
Bi 10: Isoleuxin c iu ch theo dy cc phn ng sau (A, B, C, D l k hiu cc cht cn tm):
A B C D
3
NH
Isoleuxin
C2H5ONa 2. HCl
Hy cho bit cng thc cu to ca cc cht A, B, C, D v Isoleuxin.
BI GII:
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: Ngi ta phn lp c mt tetrapeptit (peptit A) t prothrombin ngi. Cu to ca peptit A
c tin hnh xc nh nh sau:
a. Bng phng php Edman th nhn c trnh t aminoaxit ca peptit A l Leu-Glu-Glu-Val.
b. tip tc xc nh cu to, ngi ta tin hnh in di trn giy pH 6,5 peptit A v mt peptit tng
hp B (cng c trnh t aminoaxit l Leu-Glu-Glu-Val) th li nhn c qung ng di chuyn khng
ging nhau, c th nh hnh di 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 bng HCl 6N 110
o
C, th c A v B u cho Leu(1), Glu(2), Val(1); nhng khi
thu phn bng kim th peptit B cho Leu(1), Glu(2), Val(1) cn peptit A cho Leu(1), X(2), Val(1).
Hy gii thch cc kt qu thc nghim xc nh cu to ca X v gi tn X theo danh php IUPAC.
BI GII:
Xc nh cu trc ca X
- Phng php Edman thc hin pH thp,bit c trnh t l Leu-Glu-Glu-Val.
- in di pH 6,5 cho thy peptit A dch chuyn nhanh h n v pha cc dng(+), chng t A c in
tch m ln hn B,tnh axit ca A ln hn B.
- Khi thu phn trong mi trng HCl 6N 110
o
C th c A v B u thu c Leu(1), Glu(2) v Val(1).
Kt hp vi phng php Edman trn cho thy cc qu trnh ny thc hin mi trng axit mnh,pH
thp. pH thp phn t X b ecacboxyl ho,loi CO
2
mt i 1 nhm COOH.
- Khi thu phn bng kim peptit A to ra Leu(1),X(2) v Val(1),trong mi trng kim khng c qu
trnh decacboxyl ho nn nhn c X(2).
- Kt hp cc kt qu trh nghim cho thy X c th m 1 nhm COOH so vi Glu tc l khi loi 1 nhm
COO th X chuyn 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
Gi tn: Axit 3-aminopropan-1,1,3-tricacboxylic
Bi 12: Hp cht A(C
6
H
12
N
2
O
2
) quang hot, khng tan trong axit long v baz long, phn ng vi
HNO
2
trong nc to thnh B (C
6
H
10
O
4
). Khi un nng B d dng mt nc chuyn thnh C (C
6
H
8
O
3
).
Hp cht A phn ng vi dung dch brom v natri hydroxit trong nc to thnh D (C
4
H
12
N
2
), hp cht
ny phn ng vi HNO
2
khi c mt axit clohydric cho metyletylxeton.
1. Hy xc nh cng thc cu to ca A, B, C, D v gi tn cc hp cht to thnh.
2. Hp cht A c th c cu trc nh th no? Dng cng thc Fis m t.
BI GII:
1. A phi l diamit nn c th vit 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 phn ng vi HNO
2
v chuyn v ging nh pinacolin.
Nh vy c th vit 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 vy hp cht A l diamit ca axit 2,3-dimetylsucxinic c th tn ti dng quang hot, phn
ng vi 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 thc 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: Tng hp hu c
1. Hy tng hp axit glutamic t axit o-xetoglutaric.
2. Hy tng hp prolin t axit adipic.
BI GII:
1. Qu trnh tng hp 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)
hoc:
2
3 2
1)SOCl
2) NH Br / KOH
2 4 2 2 4
HOOC(CH ) COOH H NCO(CH ) COOH A ri tip tc nh trn
2. Qu trnh tng hp 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 khi lng phn t 1007. Thu phn hon ton bng axit cho cc aminoaxit sau vi
s mol bng nhau: Asp, Cystin, Glu, Gly, Ile, Leu, Pro v Tyr. Oxy ha A vi HCO
2
OH ch cho B cha
hai gc axit cysteic (k hiu l Cya), l mt dn xut ca cystein vi nhm thiol b oxy ha thnh axit
sunfonic.
1. C bao nhiu nhm cha axit sunfonic c to thnh t s oxy ha mt lin kt disunfua?
Thu phn khng hon ton B cho mt s di v tri-peptit (B1 B6). Trt t ca mi sn phm thu phn
c xc nh trong nhng cch sau. Aminoaxit c N cui c xc nh bng cch x l peptit vi
2,4 dinitroflobenzen (DNFB) cho DNP peptit. Sau khi thu phn hon ton DNP peptit bng axit,
thu c mt DNP aminoaxit, cht ny c th c xc nh d dng bng cch so snh vi cc DNP
aminoaxit chun.
2. Khi x l B1 vi DNFB ri thu phn k tip bng axit to thnh mt sn phm l DNP Asp. iu
ny cho thy B1 c axit aspartic t i N cui. Hy vit cu to y ca DNP Asp ti im ng in
ca n (khng cn ha hc lp th).
K , aminoaxit c C cui c xc nh bng cch un nng peptit t i 100
o
C vi hydrazin, cht ny b
gy tt c cc lin kt peptit v chuyn tt c tr aminoaxit C cui thnh hydrazit ca aminoaxit, cn
nhm cacboxyl C cui cn nguyn vn. Theo cch ny, cc aminoaxit N- v C- cui c xc nh th
t ton b ca 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 vi mt enzym t Bacillus subtilis cho B7 - B9 vi thnh phn nh sau:
B7: Gly NH
2
(glyxinnamit) B8: Cya, Glu, Ile, Tyr
B9: Asp, Cya, Leu, Pro
3. Vit trnh t ca B8 nu thu c DNP Cya khi x l B8 vi DNFB ri thu phn hon ton sau
bng axit.
4. Nu cc aminoaxit N- v C- cui ca B9 c xc nh theo th t l Asp v Leu, vit trnh t ca B9.
5. Vit cu to y ca A v ch r v tr ca lin kt disunfua.
Tuy nhin khi lng phn t ca A tnh c th ln hn ga tr thc nghim hai n v. Quan st k
lng hn hp thu c t s thy phn hon ton bng axit ca A ngoi cc aminoaxit tm c lc u
cn c 3 ng lng mol amoniac cng c to thnh.
6. ngh cu to iu chnh ca A v khoanh trn (mt hay nhiu v tr) trn cu to ny cho thy tt
c cc ngun to amoniac c th c.
BI GII:
1. 2
2. Cng thc cu to:
O
O
2
N
OH
OH
N H
NO
2
O
3. Trnh t ca B8 l: Cya Tyr Ile Glu.
4. Trnh t ca B9 l: Asp Cya Pro Leu.
5. Cu to y ca A l: Cys Tyr Ile Glu Asp Cys Pro Leu Gly NH
2
6. Cu to iu chnh ca A:
Cys Tyr Ile Gln Asn Cys Pro Leu Gly NH
2
Cc v tr gch chn l cc v tr to amoniac.
Bi 15: Phn ng ngng t gia axit cacboxylic v amin sinh ra amit. V d: ngng t axit fomic vi
dimetylamin sinh ra N,N-dimetylfomamit, n c cc cu trc cng hng sau:
N H
CH
3
CH
3
O
N
+
H
CH
3
CH
3
O
1. Xp cc cht N,N-dimetylfomamit (A). N-metylaxetamit (B) v propanamit (C) theo th t tng dn
nhit si.
2. Nhm cacbonyl thng c nhn din bng di hp th mnh trong ph hng ngoi (IR). V tr vn
hp th ph thuc vo bn lin kt C = O. i vi amit th bn ca lin kt C = O c th c xc
nh da vo hnh v trn. V d: nhm C = O ca xiclohexanon cho vn hp th 1715cm
-1
. so snh
vi xiclohexanon th cc gi tr no sau y l ph hp vi nhm C = O ca propanamit?
a) 1660cm
-1
do di lin kt ngn ca nhm cacbonyl.
b) 1660cm
-1
do di lin kt di ca nhm cacbonyl.
c) 1740cm
-1
do di lin kt ngn ca nhm cacbonyl.
d) 1740cm
-1
do di lin kt di ca nhm cacbonyl.
3. Glyxin (H
2
N CH
2
COOH) l o - aminoaxit. Ba phn t glyxin c th to ra tripeptit GlyGlyGly
thng qua phn ng ngng t to thnh amit v km theo s tch loi hai phn t nc. Hy vit cng
thc cu to ca tripeptit.
4. Khi o - aminoaxit cha nhoam th thu lc ny s xut hin hin tng ng phn quang hc. V d:
Lalanin v Dalanin l hai enantiome. Nh vy i vi 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. Tng cng c bao nhiu ng phn quang hc t cc tripeptit trn?
Hin nay, polyacrylamide gel with electrophoresis (PAGE) c s dng rng ri trong vic phn tch
protein v axit nucleic. Tuy nhin mt trong s nhng ng dng ca keo polya mit l phn lp cc hp cht
phenol bng sc k bn mng. Cc phenol c cha cc nhm th khc nhau th c tnh axit khc nhau.
Tnh axit khc nhau th lin kt vi keo PAGE cng mnh.
6. Sp xp cc cht sau: phenol (D), 4 metylphenol (E) v 4nitrophenol (F) theo th t gim dn kh
nng lin kt vi PAGE. Kh nng hp th mt cht trong ph t ngoi - kh kin (UV Vis) ph thuc
vo s lin kt i lin hp trong phn t . Mt hp cht c t 5 ni i li n hp tr ln th c xu hng
hp th nh sng trong vng kh kin nn kt qa l chng c mu. V d phenolphtalein l mt cht ch
th axit baz thng dng. 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. Vit cng thc cu to ca H.
8. Phenolphtalein c th c iu ch bng cch cho cht G phn ng vi hai mol phenol. G phi l
cht no trong s cc cht di y phn ng t hiu sut cao nht.
H
H
O
O
H
OH
O
O
O
O
O
O
a
b c
d
BI GII:
1. Th t sp xp cc cht theo nhit si: C > B > A.
Gii thch: T cu trc cng hng ca amit cho thy n c mt phn in tch m trn nguyn t oxy v
mt phn in tch dng trn nguyn t nit. Amin bc 1 v bc 2 c lin kt hydro mnh hn amin bc
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 lng cc.
4. 27
5. Trong s th 26 tripeptit c ng phn quang hc
Aminoaxit khng c tnh quang hot: H
2
N GGG OH
Aminoaxit c tnh quang hot: H
2
NGG
L
AOH; H
2
NGG
D
AOH
6. Kh nng lin kt vi PAGE gim dn theo th t F > D > E.
7. H l
O
O
O
O H
OH
O
O
O
8. Cht d
Bi 16: Protein hin din trong hu ht cc t bo sng v ng mt vai tr quan trng trong ha hc ca
s sng. N c to thnh t cc n v cu trc l cc axit - o - aminocacboxylic. Peptit l cac protein
thu nh vi mt vi aminoaxit. Lin kt peptit l cc lin kt amit c hnh thnh t s ngng t ca
nhm amin ca aminoaxit ny vi nhm cacboxyl ca aminoaxit k cn.
1. Peptit no nhn c t phenylalanine F v alanin A? Ch ra cu trc ca chng.
NH
2
O
OH
NH
2
O
OH
NH
2
O
OH
NH
2
O
OH
A G L F
Trong phng php phn tch cu trc peptit th vic nhn din aminoaxit u N v ui C ng vai tr
cc k quan trng. Phng php Sanger gip ta nhn din c aminoaxit u N bng cch x l
aminoaxit vi 2,4-dinitroflobenzen trong mi trng kim yu, sau l thu phn ton b chui peptit
vi xc tc axit. Aminoaxit u N s to ra kt ta mu vng v d dng c nhn din bng phng
php sc k giy. Sanger c trao gii thng Nobel nm 1958 v 1980.
2. Vit phn ng xy ra khi ta s dng tc nhn Sanger ( cho gn ta vit aminoaxit u N c cng thc
l H
2
NR) nhn din aminoaxit u N.
Vi aminoaxit ui C, cha nhm chc COOH t do trong peptit c phn lp bng cch s dng
enzym cacboxipeptidaza thy phn, enzym ny ch thy phn aminoaxit cui mch. i vi mt
tetrapeptit cha cac aminoaxit F, A, glyxin G v leuxin L th phng php thy phn bng enzym
cacboxipeptidaza th aminoaxit ui C c nhn din l F. phng php Sanger cho bit aminoaxit u
N c nhn din l G.
3. ngh cng thc cu to ca peptit. Hy vit cc cng thc cu to ca chng.
BI GII:
1. Cng thc ca cc peptit nhn 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. Phn ng xy ra:
F
NO
2
O
2
N
H
2
NR
NHR
NO
2
O
2
N RNH
3
F
+ 2
+
3. Khng th bit c th t hai aminoaxit gia l AL hay LA nn peptit ban u c c th c cu to
nh sau: GALF hoc GLAF.
Bi 17: Coniin l hp cht rt c c tm thy trong cy c sm (conium maculatum). Trit gia c i
ngi Hy Lp Socrates b git bi cht ny. Coniin l mt hp cht cha nit v l mt ancaloit. Xc
nh ha tnh v ha lp th ca coniin bng cch hon thnh cc chui phn ng sau. V CTCT A, B, C.
Trong :
Hofmann exhaustive methylation: s metyl ha trit theo Hofmann
Optically active: hot ng quang hc
BI GII:
Bc oxy ha bng KMnO
4
tham kho trong ti liu: A. M. Castano, J.M. Cuerva, A. M. Echavarren,
Tetrahedron Letters, 35, 7435-7438 (1994)
Bi 18: Peptit l cc polyamit mch thng sinh ra bng cc li n kt ui ni vi ui ca cc aminoaxit
c cu hnh L (tc S).
1. Cc dipeptit no c th c to thnh bng cch ngng t Lalanin v Lphenylalanin? S dng cc
cng thc lp th trong cu tr li.
2. S ko di tng phn mch peptit hu ht lun bt u t nguyn t C ca cc aminoaxit bc ba (s
dng dng este) lin kt vi mi n v aminoaxit k tip (s dng dng dn xut th Ni t) dn n
s thay th nguyn t N - th trc khi n v k tip c gn vo. Dn xut th thng c s dng l
cc nhm ankoxy cacbonyl ROCO v dn xut cacbamat ca n.
Hy gii thch l do ti sao s hin din ca nhm th (nhm bo v) ca nguyn t nit amin lm tr
ngi vic to lin kt amit vi nhm cacboxyl. a. V nit by gi ch cn c 1H ; b. V nhm bo v c
mt electron t hn nguyn t nit. ; c. V nhm bo v chn s tn cng ca nhm cacbonyl ; d. V s
khng tnh in ; e. V n vn l mt amit.
3. V cc cng thc cng hng ca mt na nhm amit. S dng cc k hiu lp th v cc mi tn
ch r s chuyn dch electron.
4. Tc nhn no di y s c s dng gn nhm benzylcacbamat vo mt amin (nhm Bergmann
Zervas). Vit phn ng. a. C6H5CH2OCONH2, b. C6H5CH2OCO2CH3, c. C6H5CH2OCO2C(CH3)3,
d. C6H5CH2OCOCl, e. C6H5OCOCl
5. Vic loi nhm bo v ankoxycacbonyl thng km theo phn ng ct mch di tc dng ca cc
axit theo s :
Xp kh nng tng dn tnh hot ng ca cc cacbamat sau y di tc dng ca axit:
BI GII:
1. Cng thc cu to cc peptit c th c:
Cc dipeptit vng (dixeto piperazin) cng c chp nhn:
2. Cu tr li tt nht l b v e
3.
4. Tc nhn e (benzylclofomiat) s phn ng vi amin theo s sau:
5. Nu chng ta gi thit trng thi chuyn tip c to thnh ion cacboni th cht no to
thnh ion cacboni d dng nht th tnh bn cng t l thun vi kh nng . Trong
cht D th c s gii to electron mnh nht:
v kh nht A:
Gii thch tng t ta thy cation to thnh t B bn hn C. Nh vy th t s l: D > B > C > A
Bi 19: Cng thc cu to ca cc cht A v B trong s iu ch nha melamin sau:
Xianogen clorua A
3
NH
Xianuramit (melamin)
2
CH O
B
N
N
N
NH
2
NH
2
N H
2
BI GII:
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
+

Vit cng thc Fis ca E v cho bit cu hnh tuyt i (R/S) ca n.
BI GII:
S phn 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 thc chiu Fischer ca E (cystein) E c cu hnh R v hn cp ca -CH
2
SH > -COOH
COOH
CH
2
SH
H
H
2
N
R
Bi 21: Sau khi x l hn hp li ng hoc v tru c cha pentozan (C
5
H
8
O
4
)
n
vi dung dch axit
clohiric 12% ri tin hnh chng ct, nhn c cht lng A (C
5
H
4
O
2
) mu vng c mi thm. Cho A
phn ng vi KOH ri axit ha th nhn c B (C
5
H
4
O
3
) v C(C
5
H
6
O
2
).
a. Vit phng trnh phn ng thu phn pentozan to thnh A v cng thc ca A, B, C.
b. Vit phng trnh phn ng ca B tc dng vi C khi c
xc tc axit.
c. Hy trnh by iu kin nitro ho A nhn c D (C
5
H
3
NO
4
).
d. Vit phng trnh phn ng ca D tc dng vi: (I) ; (II).
(II)
NH
-N
O
O
H
2
N
(I)
S
NH
S
O
BI GII:
1. Trong li ng v v tru c cha pentozan, khi un nng vi dung dch HCl 12% chuyn
thnh pentoz ri tch nc 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 cn phi bo v nhm anehit bng (CH
3
CO)
2
O
(CH
3
CO)
2
O
O
CH(OCOCH
3
)
2
O
CHO
Thc hin phn ng nitro ho, sau thu phn phc hi 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. Phn ng ca D vi 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 di) l mt hp cht c tch ra t qu dnh dnh. Thu phn geniposit
sinh ra hai sn phm l genipin v D-glucoz. Genipin tham gia phn ng to mu vi gelatin (y
l c s pht hin du vn tay trong k thut hnh s).
Hy vit s phn ng to genipin v phn ng ca genipin vi mt aminoaxit gii thch hin
tng trn
O
O
O
OH
HO
HO
HOH
2
C
COOCH
3
CH
2
OH
BI GII:
Phn 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) cu to t cc polipeptit, ly i din l mt aminoaxit nh glyxin, ta c
phng 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
sn phm c mu pht hin du vn tay trong k thut 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: Vit s phn ng oxi ha D-glucoz to thnh axit anonic v axit anaric, cng th c Haworth
cc mono v i -lacton ca chng v gi tn cc lacton y.
BI GII:
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: Hp cht X l mt ng ba (tri saccarit) c ch yu trong cc thc n lm t ht bng. Hp cht
X khng phn ng vi dung dch Benedict cng nh khng i quang. S thu phn xc tc axit to ra ba
ng D hexoz khc nhau A, B v C. Tt c cc hp cht A v B cng nh hp cht I (xem di y)
u cho cng mt osazon khi phn ng vi lng d phenylhydrazin trong mi trng axit. Hp cht C
phn ng vi axit nitric to thnh mt hp cht D khng c tnh quang hot (khng trit quang). thit
lp quan h gia cu hnh gia D glyxerandehit v C, cht ng andehit 4 cacbon (andotetroz) trung
gian khi b oxy ha bi axit nitric khng to th nh c mt hp cht meso. Khi A c x l bi axit
nitric to thnh axit aldaric c tnh quang hot. C A v B u phn ng vi 5 mol HIO
4
; A to thnh 5
mol axit metanoic (axit fomic) v 1 mol metanal (fomandehit), trong khi B to thnh 4 mol axit
metanoic, 1 mol metanal v 1 mol CO
2
. C A v B c lin quan vi 1 andotetroz, andotetroz ny l mt
ng phn khng i quang (diastereoiso mer) ca cht m C c tng quan. S metyl ha ca X ri thy
3,6-dilacton ca axit glucaric
1,4-lacton ca axit glucaric
3,6-lacton ca axit glucaric
phn k tip to thnh 2,3,4-tri-O-metyl-D-hexoz (E) (chuyn ha t A); 1,3,4,6-tetra-O-metyl-D-
hexoz (F) (chuyn ha t B) v 2,3,4,6-tetra-O-metyl-D-hexoz (G) (chuyn ha t C).
1. Xc nh cng thc chiu Fischer ca A, B, C
v D.
2. V y cng thc chiu Haworth tng ng
ch r kch thc vng v ha hc lp th
tuyt i ca E, F v G.
3. Vit cng thc chiu Haworth ca X.
BI GII:
- Hp cht X l mt tri-saccarit, khng phn ng vi dung dch thuc th Benedict, khng quang hot.
iu ny cho thy X l mt ng khng kh v v vy ch c cc lin kt axetal v xetal tn ti tt c
cc cacbon anome.
- Trong ba monosaccarit th A v B cho cng mt osazon nh vy c ha hc lp th nh nhau ti C-3;
C-4 v C-5 (v C-6).
- A v B cng khc vi hp cht I (l D-mannoz) tuy cho cng mt osazon v nh vy mt trong s
phi l C-2 epime ca D-mannoz (l D-glucoz) v cht kia phi l ng xeton tng ng C-2 (nh D-
fructoz) (Suy lun ny c kim nhn sau ny bng cc phn ng ct mch oxy ha).
- Hp cht C, sau phn ng vi axit nitric to mt axit dicacboxylic khng quang h ot l axit andaric D.
Axit andaric nh vy c th c hai dng: l AA1 (D) v AA2
- Andotetroz to thnh trc C (cng nh trc D) khng cho mt hp cht meso sau phn ng vi axit
nitric v nh vy buc phi 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 vy axit andaric D to thnh t C nu trn l AA1 v nh vy C phi l D-galactoz. Hp cht A phn
ng vi 5 mol axit HIO
4
to ra 5 mol axit metanoic (axit fomic) v mt mol metanal (fomandehit) cho
php ngh A l mt andohexoz trong khi B phn ng vi 5 mol HIO
4
to c 3 mol axit metanoic,
1 mol metanal v 1 mol CO
2
gip d on n l mt xetohexoz.
Cc hp cht A v B c lin h vi mt tetroz khngging nh C (lin quan vi D erithreoz). Tetroz
lin quan n A v B v th phi c cu to 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 ri thu phn k tip to thnh E, F v G di y:
E chuyn 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 chuyn 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 chuyn 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 (hoc ni phn
t hoc lin phn t) mi b ete ha. T d kin metyl ha, ch E c hai nhm hydroxyli t do c th lin
kt vi cc cacbohydrat khc. Nh vy A phi l cacbohydrat trung tm. Cc kt qa ny ch ra rng trt t
ca cc monosaccarit trong X l C-A-B (hay B-A-C).
Nu: A
5
biu th dng furanoz (vng 5 cnh) ca cacohydrat A.
A
6
biu th dng pyranoz (vng 6 cnh) ca cacbohydrat A.
BB
5
biu th dng furanoz (vng 5 cnh) ca cacbohydrat B.v.v
th saccarit X c th c biu th l C
6
A
6
B
5 Mt trong 4 cu to khc nhau c th c ca 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: Bn cht ca cc lin kt anome l khng thit yu trong bi. S sp xp cc lin kt ca A vi
B v C cng c th c o li (lin kt 1,1 gia C v A v lin kt 1,6 gia 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 to thnh t phn ng quang hp trong thc vt. Tuy nhi n
mt s cacbohydrat khng gp trong thin nhin c t h c tng hp nhn t o trong phng th nghim.
Sau y s trnh by s iu ch L riboz (hp cht 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. Hp cht A c cng thc phn t C
10
H
10
O
5
. Vit cng thc cu to A.
2. Trong cc mnh lin quan n vic chuyn ho t A thnh C sau y th mnh no ng, mnh
no sai?
a) OsO
4
l tc nhn oxy ha trong phn ng chuyn A thnh B.
b) MeOH l sn phm ph trong phn ng chuyn ha B thnh C.
c) Proton ng vai tr xc tc trong phn ng chuyn ha B thnh C.
d) C c th c to thnh vi hiu sut thp khi khng c Me
2
C(OMe)
2
Enzym pig liver esteraza c th thy phn este thnh axit cacboxylic. Thu phn C bng enzym pig liver
esteraza sinh ra hn hp D v E trong E l sn phmchnh. Gc quay cc ca hn hp l:
20
D
[ ] o = -37,1
o
cn ca E tinh khit l
20
D
[ ] o = 49
o
.
3. Tnh t l D/E (theo s mol) trong hn hp phn ng.
4. Phn ng ca F vi axit m clopebenzoic (MCPBA) sinh ra t sn phm G. Ch ra rng cc mnh
sau y l ng hay sai:
a) Bn cht ca phn ng l s oxy ha F.
b) Nguyn t oxy thm vo c ngun gc t MCPBA.
c) T l ca hai hp cht C1 (R) v C1 (S) trc v sau phn ng khng thay i.
Cng thc phn t ca H l C
9
H
16
O
5
. Cc ga tr ph NMR ca H cho di 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. Vit cng thc cu to ca H.
6. Xc nh cu hnh tuyt i ca C
1
; C
2
; C
3
: C
4
ca hp cht I.
7. Trong cng thc chiu Fischer ca I (L riboz) th cc ch ci P, Q, R, S, T v U i din cho nhng
nhm chc no?
CHO
P
Q
R S
CH
2
OH
T U
Disaccarit l hp cht c to thnh t hai n v monosaccarit bi lin kt glycozit. Polisaccarit cha t
10 n vi ngn n v monosaccarit.
V d v disaccarit cho di y:
H OH
H
O
HO
H
H
OH
OH O
H
H
OH
lin kt glycozit
H
O
H OH
H
OH
OH H
8. C bao nhiu ng phn dia to thnh t pentasaccarit J nu n c to thnh t 5 n v D glucoz:
H
OH
H
O
H O
H O H
H
OH
1.
OH H
5
BI GII:
O
CO
2
Me
CO
2
Me
2. Tt 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 mt hay nhiu cu to vng vi ha lp th c th c ca (D) Tagaloz trong dung dch bng
cng thc chiu Harworth:
CH
2
OH
O
HO H
HO H
H OH
CH
2
OH
(D) Tagaloz
b) Hai sn phm vi cng cng thc phn t C
6
H
10
O
6
thu c khi D arabinoz c cho tc dng vi
natri xianua trong mi trng axit ri thy phn k tip cng trong mi trng axit. Vit cu to km ha
hc lp th c th c ca hai hp cht v chng c to 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 mt disaccarit (c tnh kh) l turanoz c em thy phn, thu c Dglucoz v Dfructoz
vi s mol bng nhau v bng s mol saccarit dng. Metyl ha turanoz vi metyl iodua c mt bc oxit
ri thu phn k tip to thnh 2,3,4,6tetraOmetylDfructoz. Hy xut cu to c th c ca
turanoz m khng cn xc nh ha hc lp th ti cc v tr anome.
BI GII:
a) Cc cng thc chiu Harworth c th c ca 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 phn ng xy 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 thc cu to c th c ca turanoz (khng ch n mt lp th ti 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 sa) c sn xut hu ht cc trang tri trn khp t nc H Lan, n c sn
xut t vng sa (sn phm ph trong qa trnh sn xut phomt). Lactoz c nhiu ng dng rng ri
trong thc n cho tr em v trong cc loi dc phm. N l mt disaccarit c hnh thnh t mt n v
D galactoz v D glucoz. Cng thc chiu Haworth ca n c ch ra di y. Pha bn tri ca
cng thc l n v D galactoz.
CH
2
OH
OH
O
O
OH
OH
OH
OH
OH
O
OH
1. Hy v cng thc chiu Fischer cho D galactoz v D glucoz. S thy phn lactoz trong mi
trng axit dn n s to thnh D galactoz v D glucoz.
2. Da vo cng thc ca lactoz hy ch ra:
a) Nguyn t oxy m s c thm proton sau khi lactoz b thu phn
b) Lin kt C- O no b ph v trong phn ng thu phn
c) Nguyn t cacbon no s b kh khi phn ng vi thuc th Fehling
S thy phn lactoz c th kt hp c vi phn ng hydro ha khi ta s dng xc tc kim loi, iu ny
dn n s to thnh ancol a chc l sorbitol v galactitol, chng cng c bit di hai ci tn tng
ng l gluxitol v dulcitol.
3. Hy v cng thc chiu Fischer ca hai ancol a chc ny v cho bit chng c hot ng quang hc
hay khng?
Trong cng nghip, qa trnh sn xut lactoz chu phn ng ng phn ha thnh lactoloz, y l mt
loi dc phm dng cha cc bnh v rut. S hydro ha lactoz dn n lactitol, mt poliol C
12
vi
t calori v c ngt cao. C hai qa trnh ny u c thc hin H Lan.
4. a) V cng thc Haworth ca lactol oz (lu rng phn glucoz trong lactoz
b ng phn ha thnh fructoz).
b) V cng thc chiu Haworth ca lactitol.
O
BI GII:
1. Cng thc cu to ca 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 (hot ng quang hc) Galactitol (khng hot ng quang hc)
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: Mt monosaccarit A c khi lng phn t l 150Da. Khi x l A vi NaBH
4
th sinh ra hai ng
phn lp th B v C khng c tnh quang hot.
1. V cng thc cu to ca A, B v C bng cch s dng cng thc chiu Fischer.
2. Xc nh cu hnh cu hnh tuyt i ca cc cht t A n C bng cch s dng h danh php CIP
(Cahn Ingold Prelog).
3. Hy xc lp mi quan h v mt lp th gia cc ng phn quang hc ca B.
3.
BI GII:
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
Mt monosaccarit c cng t hc chung l C
n
(H
2
O)
n
. Tt nhin, vi khi lng phn t l 150Da th cng
thc ch c th l C
5
(H
2
O)
5
. Sau phn ng kh th B v C l hai ng phn duy nht khng hot ng
quang hc. Hai sn phm ny c th c coi l tin cht ca A. Nu hai nhm ch khc nhau kh nng
quang hc th ng phn R s c kh nng hnh thnh cao hn 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 mt monosaccarit, hy vit cc phng trnh phn ng iu ch cht A v B:
O O
CHO
H
A
O
O
H
5
C
6
O
OCH
3
CH
3
COO
OCOCH
3
B
BI GII:
iu ch A
Bi 8: Vit cng thc Fis ca cc cht C v D trong dy chuyn ha sau:
BI GII:
Bi 9:
1. Vit cc phng trnh phn ng thu phn metyl--D-galactofuranozit (A) v metyl--D-sobofuranozit (B) trong
mi trng axit. (soboz: 2-xetohexoz; cu hnh C3 ca n v ca galactoz khc nhau).
2. Arabinopyranoz (D-anopentoz c cu hnh 2S, 3R, 4R) c chuyn 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 cu trc ca B, C, D v E.
BI GII:
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: Hp cht A (C
4
H
6
O
3
) quang hot, khng tham gia phn ng trng bc, tc dng vi anhirit axetic
to ra dn xut monoaxetat. Khi un nng vi metanol, A chuyn thnh cht B (C
5
H
10
O
4
). Di tc dng
ca axit v c long, B cho metanol v C (C
4
H
8
O
4
). C tc dng vi anhirit axetic to ra dn xut
triaxetat, tc dng vi NaBH
4
to ra D (C
4
H
10
O
4
) khng quang hot. C tham gia phn ng trng bc to
thnh axit cacboxylic E (C
4
H
8
O
5
). X l amit ca E bng dung dch long natri hipoclorit to ra D-(+)-glyxeranehit
(C
3
H
6
O
3
) v amoniac.
V cu trc ca A, B, C, D v E.
BI GII:
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 vit s chuyn ha thnh axit aipic qua giai on to thnh fufuran
BI GII:
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 to ozazon, chu i quay v b thy phn bng dung
dch nc axit hoc bng elmusin cho D-glucoz. Metyl ha ri thy phn s cho 2,3,4,6-tetra-O-metyl-
D-glucoz. Vit CTCT v gi tn Gentibioz C
12
H
22
O
11
BAI GII:
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 thy phn bi elmusin cho D-glucoz v Saligenin C
7
H
8
O
2
. Salixin khng
kh thuc th Tolen. Oxi ha Salixin bng HNO
3
thu c mt hp cht hu c X m khi thy phn th
cho D-Glucoz v anehit Salixylic. Metyl ha Salixin thu c pentametylsalixin, thy phn hp cht
ny cho ta 2,3,4,6-tetra-O-metyl-D-Glucoz. Xc nh CTCT ca Salixin
BI GII:
Salixin l ng khng kh v l glucozit | do b thy phn bi 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 thc C
7
H
8
O
2
, ROH xut hin nhn thm. Tch c andehit salixylic, iu chng 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 thc cu trc ca salixin l
O HO
HO
OH
O
HOH
2
C
CH
2
OH
Bi 14: Hp cht thin nhin Y (C
7
H
14
O
6
) khng c tnh kh v khng i tnh quang hot. Y b thy phn
bi dung dch HCl/H
2
O thnh K l mt ng kh. Khi b oxi ha bi axit nitric lo ng, K chuyn thnh
axit khng quang hot L (C
6
H
10
O
8
). S thoi phn Ruff dn ti mt ng kh M ; cht ny b oxi ha bi
axit nitric long thnh axit quang hot N (C
5
H
8
O
7
)
a. Xc nh cu trc ca Y, K, L, M, N
b. C tn ti s khng khng nh no v mt cu trc khng
BI GII:
a. Y l metylglicozit, lp lun tm ra K, L, M, N. Y tn ti dng vng 5 cnh
CH
H OH
HO H
H OH
H
CH
2
OH
O
OCH
3
L c th l 1 trong cht 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 cht sau
COOH
HO
HO
OH
COOH
COOH
OH
OH
HO
COOH
K l mt trong 2 cht sau:
O
OH
OH
OH
CH
2
OH
OH
O
OH
OH
OH
CH
2
OH
HO
Y c th l mt trong 2 cht
O
OH
OH
OH
CH
2
OH
OCH
3
O
OCH
3
OH
OH
CH
2
OH
HO
b. Khng khng nh v mt cu trc:
- Cu hnh C anome
- Cc yu cu u tha mn c cu hnh D v L

************************************************
POLYMER OLIGOMER
Bi 1: Cc polyme hu c c nh hng rt ln i vi cuc sng hng ngy ca chng ta. Hng nghn tn
cc loi cao phn t khc nhau c sn xut mi nm. Tng hp cc polime hu c c s dng trn
nhiu lnh vc, t nguyn liu dt cho n cc con chip my tnh, v n c van tim nhn to. Chng c
s dng rng ri nh cht do, keo dn, vt liu xy dng, cht do c kh nng phn hy v sn. Poly
(vinyl ancol) (PVA) l mt v d quan trng ca mt polyme c kh nng h a tan trong nc. Gin 1
di y tm tt mt phng php tng hp PVA.
Giai on 1:
polyme ha
Monome polyme poly(vinylancol) A B PVA
Polyme B trn cng l thnh phn chnh trong ko cao su. Phn tch nguy n t cht A cho t l C:H:O =
56:7:37. Thm vo , phn tch nguyn t cht B cho ra thnh phn C, H v O gn ging nh vy. Di
y l ph IR v 1H NMR ca monome A.
Ph
1
H NMR ca Monome A
4000 3500 3000 2500 2000 1500 1000
Ph IR ca Monome A wavenumber (cm
-1
)
T
r
a
n
s
m
i
t
t
a
n
c
e
(
%
T
)
1. Cho bit cng thc phn t ca A?
2. Nhm chc no cho di hp th IR 1761 cm
-1
?
3. Cho bit cu to ca A
4. V mt phn polyme B. Biu din t nht ba mt xch.
5. ngh mt phng php chuyn ha B thnh PVA.
6. C bao nhiu cp ng phn i quang s thu c t polyme B c khi lng phn t 8600, gi s
rng polyme c tt mch bi s hp th hidro v b qua khi lng cc nhm cui mch.
7. Hp cht C, mt ng phn ca A, cng l mt monome quan trng trong vic tng hp cc polime.
8. Da vo ph
1
H NMR v ph IR c cung cp di y, lp lun xc nh cu to C.
Ph
1
H NMR ca 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 ca Monome C
Polyme D l mt phn t ln nhy axit. Khi x l D vi mt axit th gii phng kh E, F v hnh thnh
mt polyme mi G. Kh E lm c dung dch Ca(OH)
2
, cn kh F tc dng vi brom to ra mt dung
dch khng mu H.
O
O
O
D
n
H
+
E + F + G
dd Ca(OH)
2
Br
2
H
BI GII:
1. C
4
H
6
O
2
2. Nhm C=O
3. Cng thc cu to A:
4. Cng thc cu to B: In: cht khi mo:
100
80
60
40
Khng mu
5. Cc phn ng hu c c th chuyn nhm axetat thnh ancol nh l phn ng thy phn bng axit hay
baz, phn ng ancol phn hay kh bng LiAlH
4
.
6. C 100 n v/ phn t tuy nhin n v cui cng li khng mang trung tm bt i nn ch c 99
trung tm bt i v mi mt trong s chng li c cu hnh l R hay S. Tng cng li ta c 2
99
ng phn
quang hc bao gm c ng phn lp th i quang ln khng i quang. Nh vy s cc cp ng phn
lp th i quang (enantiomer) s l 2
99
/2 = 2
98
7. Cng thc cu to C:
8. Cng thc cu to ca cc cht E, F, G, H:
Bi 2: Vit phng trnh ha hc minh ha phn ng polime ha caprolactam trong mi tr ng kim iu
ch t nilon-6,6. Trnh by c ch phn ng ny.
BI GII:
N
C
O
H
NH[CH
2
]
5
CO
n
n
Phn ng th dy chuyn 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: Di tc dng ca nh sng hai phn t butaien -1,3 s phn ng vi nhau cho cc sn phm ime
ho c tnh cht vt l khc nhau. Hy vit cng thc cu trc cc hp cht .
BI GII:
+
,
, ,
,
1.
Bi 4: Khi trng hp Buta1,3dien to cao su Buna thng to ra sn phm ph l vng 6 cnh cha
no (phn ng DielsAlder), khi phn ng vi H
2
d xc tc Ni th to ra etylcyclohexan. Vit cc phng
trnh phn ng v cho bit iu kin phn ng ng vng DielsAlder xy ra d dng.
BI GII:
a. Phng trnh phn ng:
+
t , xt
o
+ 2H
2
t , xt
o
;
b. iu kin: Hp cht dien (A) phi c cu h nh s-cis. Phn ng ny tr nn d dng hn nu thay H
trong dienophile bng nhm ht electron nh COOH, COOR, CHO, v thay H trong dien
bng nhm y electron nh: CH
3
, C
2
H
5
,
Bi 5: Khi cyclotrimer ha buta1,3diene vi s c mt ca cht xc tc c kim, ngi ta iu ch c
(Z, E, E)cyclodeca1,5,9triene. y l mt phng php n gin iu ch hydrocarbon vng ln.
Khi dng cc cht xc tc thch hp l cc phc tallyn ca kim loi chuyn tip, ngi ta iu ch c
(E, E, E)cyclodeca1,5,9triene v (Z, Z, E)cyclodeca1,5,9triene. Vit cng thc cu to ca cc hp
cht trn.
BI GII:
Z, E, E
E, E, E Z, Z, E
Bi 6: Khi cho amoniac phn ng cng vi axetanehit thu c sn phm khng bn A, sn phm ny
d b tch nc thnh B. B d dng trime ha cho sn phm C l triazin. Mt khc nu cho amoniac
ngng t vi fomanehit s thu c sn phm D (urotropin) c CTPT l C
6
H
12
N
4
. Cht D c kh nng
tc dng vi axit nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l cht n mnh c dng
trong i chin th gii th II theo s : C
6
H
12
N
4
+ 3HNO
3
E + 3HCHO + NH
3
. Xc nh A, B, C,
D, E v vit cc phng trnh phn ng xy ra.
BI GII:
Andehit bo c th tham gia phn ng cng vi amoniac to th nh sn phm t bn 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 nc thnh B l CH
3
CH=NH v B d trime ha thnh hp cht d vng
C loi 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
Mt khc nu cho amoniac ngng t vi fomanehit s thu c sn phm 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 dng vi axit nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l cht
n mnh c dng trong i chin th gii th II theo phn 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 phn ng duy tr mch cacbon vi polime c mt xch c s c cha nhm cacbonyl, ngi
ta thng ch n 2 polime ti u biu l poliacrolein A v poli( metacrolein) o B
- A tham gia tt c cc phn ng c tr ng ca andehit nhng khng t c mc chuyn ha cao.
Di tc dng ca ancol, khong 30-35% nhm andehit ca A to thnh axetal C
- Khi A chu tc dng ca hidroxiamin hoc phenylhidrazin th khong 75% nhm andehit tham gia
phn ng v to thnh mt xch oxim D hoc phenylhidrazon t ng ng E
- Khc vi A, B tc dng vi hidroxiamin s chuyn ha hu nh hon toan thnh oxim polime F
- Khi dehidrat hoa F c th thu c polime G
Cho bit cu to ca A, B, C, D, E, F, G
BI GII:
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 lc ha du tng lai, d kin c c nh my sn xut Poli(vinyl clorua)
PVC.
a. Hy ngh hai s phn ng lm c s cho vic sn xut vinyl clorua t sn phm cracking
du m v NaCl
b. Hy phn tch cc u nhc im ca mi s . Nu cch khc phc v la chn s c li hn
c. Trng hp vinyl clorua nh xc tc TiCl
4
Al(C
2
H
5
)
3
s thu c PVC iu ha lp th c bn
c nhit cao. Hy cho bit trong mch polime y c trung tm bt i khng? Vit CT lp th 1
on mch polime y
BI GII:
a. S tng hp:
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. Phng php B cn phi x l HCl thu Cl
2
v trnh nhim.
o
t ;xt
2 2 2
1
2HCl O Cl H O
2
+ +
Chn phng php B v phn ng (1) ca phn ng A hiu sut thp, ti u tn nhiu nng lng v ga
thnh sn phm s cao hn.
c. C nguyn t C bt i:
C
H
C
H
2
Cl
CH
2
CH
2
Cl
H
CH
2
Cl
CH
2
Cl
H
Bi 9: Trong cng nghip, ngi ta thng s dng keo epoxi dn cc vt dng bng kim loi, thy
tinh, g, cht doQu trnh tng hp mt loi keo epoxit thng dng A xut pht t hai monome ban
u l epiclohidrin v bis-phenol (2-bis(4-hidroxiphenylpropan). Trong giai on u tin ca phn ng,
oligome epoxit c to thnh nh phn ng ng trng ngng hai monome trn. Sau , trong mi
trng kim, phn ng bin i tip tc xy ra n khi to th nh oligome epoxi A vi h s n 50 60 ~ .
Xc nh c ch ca qu trnh tng hp trn bit cng thc ca epiclohirin l :
O
Cl
Epiclohirin
BI GII:
Giai on 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 on 2:
Trong mi trng kim nhm epi li c to 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 li tip tc phn ng vi bisphenol ri epiclohirin phn ng lp li nhiu ln n khi to
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
vi h s n 50 60 ~ .
************************************************
Part 4: CC HP CHT D VNG
N
N O
O
S
N
Indole
Pyridine Dioxan
Thiophene Quinoline
--------------------------------------------------------------------------------------------------------------------------------
Bi 1: Sp xp (c gii thch) theo trnh t tng dn tnh axit ca cc cht trong d y sau:
(D)
(A) (B)
(C)
;
N
COOH
;
COOH
;
CH
2
COOH
N COOH
BI GII:
(D)
<
<
<
-l
1
CH
2
COOH
(C) (A)
-l
2
-l
3
N
H
C
O
O
-C
3
(B)
-C
4
-l
4
N
COOH
COOH
V: - I
1
< - I
2
nn (C) c tnh axit l n hn (D).
(A) v (B) c N nn tnh axit l n hn (D) v (C)
(A) c lin kt hiro ni phn t l m gim tnh axit so vi (B).
Bi 2: Sp xp v gii thch theo chiu tng dn nhit nng chy ca cc cht:
S
COOH
(A)
(C)
;
COOH
(B)
;
N
COOH
BI GII:
Chiu tng dn nhit nng chy
S
COOH
(A) (C)
(B)
COOH
N
COOH
< <
V
M
C
< M
A
.
(B) c thm lin kt hiro lin phn t vi N ca phn t khc.
Bi 3: Hp cht hu c A c 74,074% C; 8,642% H; c n li l N. Dung dch A trong nc c nng %
khi lng bng 3,138%, si nhit 100,372
o
C; hng s nghim si ca nc l 1,86
o
C.
5. Xc nh cng thc phn t ca A.
6. Oxi ha mnh A thu c hn hp sn phm trong c E (axit piridin-3-cacboxilic) v F (N-
metylprolin). Hy xc nh cng thc cu to ca A v cho bit gia E v F cht no c sinh ra
nhiu hn, cht no c tnh axit mnh hn.
7. A c 1 ng phn cu to l B; khi oxi ha mnh B cng sinh ra 1 hn hp sn phm trong c E v
axit piperidin-2-cacboxilic. Xc nh cng thc cu to ca B.
8. Cho A v B tc dng vi HCl theo t l mol 1:1, cht no phn ng d hn? Vit cng thc cu to
ca cc sn phm.
BI GII:
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 nhiu hn 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 cht v c tng hp cc hp cht sau v sp xp chng theo th t tng d n nhit
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 GII:
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
O
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
O
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
Nhit si: A > C > B.
Bi 5: Cho cc cht 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. Vit cng thc chiu Fis ca dng mch h cc cht tr n.
2. Trong cc cht (A), (B), (C), (D) trn, cht no:
a) thuc dy L?
b) l ng eoxi?
c) l ng c mch nhnh?
d) thuc loi xetoz?
e) c dng furanoz?
f) c cu hnh nhm anomeric?
BI GII:
1. Cng thc chiu Fis ca (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 cht (A), (B), (C), (D) trn:
a) (A), (C) l ng thuc dy L
b) (B) l ng eoxi.
c) (C) l ng c mch nhnh.
d) (D) thuc loi xetoz.
e) (B) c dng furanoz.
f) (D) c cu hnh nhm anomeric.
Bi 6: Tnh baz ca mt s hp cht cha nit c cu to tng quan c nu nh sau:
Hp cht Cu to pK
a
Hp cht Cu to 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 gii thch s khc bit trong tnh baz ca mi cp sau:
a. Piperiin / piriin
b. Piridin / pirol
c. Anilin / xiclohexylamin
d. p aminopiridin / piridin
e. morpholin / piperidin
BI GII:
a. Piridin c tnh baz yu hn piperidin v i electron gy tnh baz ca piridin thuc obitan sp
2
;
n b gi cht v khng sn sang cho cp electron nh trng hp piperidin vi obitan sp
3
.
b. Piridin c i electron (thuc obitan sp
2
) sn sang dng chung vi axit; trong khi pirol ch c
th kt hp vi proton khi nh i tnh thm ca vng.
c. C hai l do. Th nht, nguyn t nit trong anilin lin kt vi nguyn t cacbon trng thi lai
sp
2
ca vng thm, nguyn t cacbon ny c m in mnh hn nguyn t cacbon trng thi
lai sp
3
ca xiclohexylamin. Th hai, cc electron khng lin kt c th c phn tn trn vng
thm. Cc cng thc cng hng ch ra rng c s gim mt electron ti nit. V vy
xiclohexylamin c tnh baz mnh hn anilin:
NH
2
NH
2
NH
2 NH
2
d. C th xy ra s phn tn cc electron khng li n kt ca nhm NH
2
vo nhn. H qa l c s
tng mt electron trn nguyn t nit ca 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 mnh hn morpholin. Nguyn t oxy trong morpholin c m in ln
hn nhm metylen ( cng v tr) ca piperidin, v th mt electron trn nguyn t nit ca
morpholin s nh hn so vi piperidin.
Bi 7: Oxi ho hirocacbon thm A (C
8
H
10
) bng oxi c xc tc coban axetat cho sn phm B. Cht B c
th tham gia phn ng: vi dung dch NaHCO
3
gii phng kh CO
2
; vi etanol (d) to thnh D; un nng
B vi dung dch NH
3
to thnh E. Thu phn E to thnh G, un nng G nhit khong 160
0
C to thnh
F. Mt khc, khi cho B phn ng vi kh NH
3
(d) cng to thnh F. Hy vit cc cng thc cu to ca
A, B, D, G, E v F.
BI GII:
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 ()
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 cht gy o gic mnh, c cng thc:
N
Me
C
O
N
Et
Et
NH
a. Vit CTCT ca Novocain bit Novocain l 2-(N,N-ietylamino)etyl-4-aminobenzoat
b. Vit CTCT sn phm sinh ra khi cho mi cht tr n tc dng vi dung dch HCl theo t l mol 1:1
c. Vit CTCT tng sn phm sinh ra khi un nng cc cht tr n vi dung dch HCl v vi dung dch
NaOH
BI GII:
a. Novocain (C
2
H
5
)
2
NCH
2
CH
2
OCOC
6
H
5
NH
2
(p)
b. Sn phm to thanh khi tc dng vi 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. Thy phn bng 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
-
Thy phn bng NaOH
Et
2
NH
N
Me
C
O
NaO
NH
Et
2
NHCH
2
CH
2
OH
NaOOC NH
2
Bi 9: Gii thch s khc nhau v nhit si trong d y cc cht 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 GII:
- Ta c nhit si ca (1) < (2) l do hai cht ny khng to c lin kt hydro nn nhit si
ph thuc vo khi lng phn t.
- Li c, nhit si ca (4) < (3) l do mc d c hai cht u c lin kt hydro lin phn t
nhng lin kt hydro ca (3) dng polyme cn ca (4) dng dime
Bi 10: Hy iu ch valin (Val) Me
2
CHCHNH
3
+
COO
bng:
a. Phn ng Hell Volhard Zelinski
b. Amin ha kh
c. Tng hp Gabriel
BI GII:
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 tng hp:
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 GII:
a. iu 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. iu 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. iu 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: Vit s iu ch izatin (indolin-2,3-dion) t 2-nitrobenzoyl clorua
BI GII:
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 bit cng thc mch h ca cc cht 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 GII:
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 chuyn thiolacton thnh lactam:
S O NH
2
CH
2
CH
2
NH O
HS
BI GII:
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 uc kh bng Zn v CH
3
COOH thnh pirolin C
4
H
7
N
a. Vit 2 cng thc c th c ca pirolin
b. Chn ng phn tha iu ki n sau: Khi ozon phn c C
4
H
7
NO
4
, cht ny c tng hp t 2
mol axit mono cloaxetic v amoniac
BI GII:
a. Con s trong tn gi ch v tr H cng hp. Hai cht 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 chn A. Vy pirolin l ng phn A
Bi 16: Vitamin C (axit L-ascobic) l endiol v c cu trc nh sau:
a. Hy gii thch tnh axit ca axit L-ascobic (pK
a
= 4,21) v cho bit nguyn t H no c tnh axit
b. iu ch L-ascobic t D-glucoz
BI GII:
a. Anion c hnh thnh bi s tch H enolic l bn v in tch c gii ta n O ca C=O qua
lin kt i C=C
C
C HO
HO C
O
H
+
-
C
C
-
O
HO C
O
C
C O
HO C
O
b. S iu 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 bit sn phm to thnh t cc phn ng sau v gi tn sn phm :
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 GII:
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 phn ng tng hp quinolin bng ph ng php Skaraup. i u ch quinolin t
anilin, glyxeryl, nitrobenzen trong mi tr ng axit sunfuric m c xc tc st (II) sunfat
BI GII:
C ch phn ng qua 4 giai on sau:
Giai on 1: Dehydrat ha glyceryl bng H
2
SO
4
un nng c aldehyd acrolein
Glyceryl
2 4
o
H SO
t
CH
2
=CHCHO + 2H
2
O
Acrolein
Giai on 2: Phn ng cng i nhn ca anilin vi 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 on 3: Tc nhn i in t tc dng vo vng thm bi nhm carbonyl ca aldehyd c proton
ha (y l giai on 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 on 4: Oxy ha bi nitrobenzen thu c vng thm
+
H
+
2 H
2
O
N
H
1,2-dihydroquinolin
3
NO
2 NH
2
3
N
+
+
quinolin
St (II) sunfat c tc dng lm cho phn ng xy ra t t theo chi u thun
Bi 19: Trong y hc, ngi ta thng dng dung dch polividon 3,5% thay th cho huyt t ng trong
cc trng hp mt mu, bng nng, scbng cch ti m tnh mch . Qu trnh tng hp loi ha cht
ny thng i t butan-1,4-diol theo s chuyn 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 bit cng thc ca polividon l:
N
O
CH CH
2
n
BI GII:
O
O
A
N
O
H
B
N
O
CH CH
2
C
Bi 20: Hon thnh cc phng tr nh phn 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 GII:
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 du * nh du nguyn t carbon bt i ca 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 GII:
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 nha v qu cy papaver sonniferum (cy thuc phin). l
cht rn nng chy 147
o
C, c tc dng dn vnh nn c dng d cha bnh co tht i tr ng, mch
mu. Qu trnh tng hp papaverin C
20
H
21
O
4
N (G) trong cng nghi p c cho bi 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 thc cu trc ca cc cht t A G
b. Trong papaverin c d vng no.
BI GII:
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 cha d vng isoquinolin
Bi 3: Coniin l hp cht rt c c tm thy trong cy c sm (conium maculatum). Trit gia c i
ngi Hy Lp Socrates b git bi cht ny. Coniin l mt hp cht cha nit v l mt alkaloid. Xc
nh ha tnh v ha lp th ca coniin bng cch hon thnh cc chui phn ng sau. V CTCT A, B, C.
Trong :
Hofmann exhaustive methylation: s metyl ha trit theo Hofmann
Optically active: hot ng quang hc
BI GII:
Bc oxy ha bng KMnO
4
tham kho trong ti liu: A. M. Castano, J.M. Cuerva, A. M. Echavarren,
Tetrahedron Letters, 35, 7435-7438 (1994)
Bi 4: Nicotin l alkaloid chnh ca thuc l, c th coi l alkaloid loi pyridin hay loi pyrolidin. Nicotin
l cht lng khng mu, trong kh quyn chuyn nhanh sang mu nu. Vi mt lng nh, nicotin kch
thch thn kinh v lm tng huyt p. Tuy nhin vi liu lng cao, nicotin ph hy ni m mc ca h h
hp v c th dn ti t vong. Qu trnh tng hp 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 cht t A I trong s trn.
BI GII:
Cng thc ca cc cht 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 mt ankaloid c tm thy trong cy coca. Xc nh CTCT ca X bit
rng: X khng tc dng vi benzensunfoclorua, khng tan trong kim nh ng tan trong dung dch HCl. X
tc dng vi phenylhirazin v cho phn ng iodofom. Nu oxi ha X bng dung dch CrO
3
s to thnh
axit higrinic C
6
H
11
O
2
N. C th tng hp axit higrinic C
6
H
11
O
2
N bng chui cc phn 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 GII:
T cc d kin cho chng t higrin c nhm amin bc 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
Vy 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 ht tiu ngi ta tch c alkaloid piperin A (C
17
H
19
NO
3
) l cht trung tnh. Ozon phn A thu
c cc hp cht: etadial, B, D. Thu phn B thu c OHC-COOH v hp cht d vng 6 cnh
piperiin (C
5
H
11
N). Cho D tc dng vi dung dch HI c thu c 3,4-dihydroxibenzandehit. Hy xc
nh cng thc cu to ca A, B, D. C bao nhiu ng phn lp th ca A?
BI GII:
- Ozon phn A thu dc etadial chng t trong A c nhm =CHCH=
- Thu phn B thu dc OHCCOOH v piperidin, suy ra B c lin kt O=CN
Vy N nm trong vng 6 cnh.
- D phn ng vi HI thu dc 3,4-dihidroxibenzandehit. Vy c cc cng thc cu 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 kt i, s ng phn hnh hc l 4: ZZ , EE , ZE , EZ
Bi 7: Salixin C
13
H
18
O
7
l mt alkaloid c tm thy trong cy liu. em thy phn Salixin bng ezym
elmusin cho D-glucoz v Saligenin C
7
H
8
O
2
. Salixin khng kh thuc th Tolen. Oxi ha Salixin bng
HNO
3
thu c mt hp cht hu c X m khi thy phn th cho D-Glucoz v anehit Salixylic. Metyl
ha Salixin thu c pentametylsalixin, thy phn hp cht n y cho ta 2,3,4,6-tetra-O-metyl-D-Glucoz.
Xc nh CTCT ca Salixin
BI GII:
Salixin l ng khng kh v l glucozit | do b thy phn bi 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 thc C
7
H
8
O
2
, ROH xut hin nhn thm. Tch c andehit salixylic, iu chng 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 thc cu trc ca salixin l
O HO
HO
OH
O
HOH
2
C
CH
2
OH
Bi 8: Ht ca cy c sm (conium malculatum) thi trung c c dng lm thuc c thc hin cc
bn n t hnh. c t ch yu ca ht c sm l mt alkaloid c tn l coniin. Coniin c khi lng
mol phn t l 127 g.mol
-1
, cha 75,60% C v 13,38% H v khi lng. Coniin lm xanh qu tm, khng
lm mt mu dung dch Br
2
trong dung mi CCl
4
v cng khng (amin c ngun gc thc vt) l m mt
mu dung dch KMnO
4
. Khi dehydro ha coniin thu c hp cht A (C
8
H
11
N). Oxi ha cht A th thu
c cht B c cu to:
N COOH
Bit trong c 2 phn ng trn u khng c s ng hay m vng v phn t coniin khng c C bc ba
a. Xc nh CTPT ca coniin v gii thch ti sao n khng l m mt mu Br
2
/CCl
4
b. Xc nh CTCT ca coniin v cho bit bc amin ca n, ca A v B. V sao khi lng phn t
ca coniin, A, B u l s l.
c. tch coniin t ht c sm vi hiu sut v tinh khit cao nn dng chit vi dung mi no
trong cc dung mi sau:
- Nc
- Ru etylic
- Dung dch NaOH
- Dung dch HCl
BI GII:
a. CTPT ca coniin C
8
H
17
N
bt bo ha
2 8 3 1 17
1
2
+ +
A = =
V coniin khng lm mt mu Br
2
/CCl
4
nen coniin khng cha ni i m cha vng no.
b. S phn 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)
Hp cht c cha s l nguyn t N => c khi lng phn t l
c. Dng dung dch HCl v to mui coniin clohidrat tan tt trong nc. Sau c th dng kim
thu li coniin.
Bi 9: T cy Atropabenladona (mt loi c c dc) thuc h c, ngi ta tch c mt loi alkaloid
l atropin. Trong cng nghi p, ngi ta thng dng atropin iu ch axit tropoic (A) C
9
H
10
O
3
. (A) b
oxy ha bi dung dch KMnO
4
nng thnh axit benzoic (B) v b oxy ha bi oxy khng kh khi c mt
Cu nung nng to thnh cht (C) C
9
H
8
O
3
c chc andehit. Axit tropoic c th chuyn ha thnh axit
atropoic C
9
H
8
O
2
(D) nh H
2
SO
4
c 170
o
C. Hidro ha (D) bng H
2
/Ni thu c axit hidratropoic (E)
C
9
H
10
O
2
. Hy xc nh cng thc cu to ca A, C, D, E v cho bit D c ng phn cis/trans hay khng?
BI GII:
CTPT ca (A) C
9
H
10
O
3
c bt bo ha:
2 9 2 10
5
2
+
A = =
- A b oxy ha bi KMnO
4
to axit benzoic nn A c cha vng benzen v nhm chc COOH
mch nhnh (khng gn trc tip vo vng benzen)
- A b oxy ha bi oxy khng kh khi c mt Cu nung nng to th nh cht (C) C
9
H
8
O
3
c chc
andehit => Mch nhnh cha nhm chc r u bc I l CH
2
OH
- T d kin bi ra ta c CTCT ca A, B, C, D, E nh sau trong D khng c ng phn hnh hc
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 ht tiu en, ngi ta phn lp c mt loi alkaloid l piperin. Xc nh cng thc cu to
ca piperin da 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 GII:
Piperin l:
O
O
CH CH CH CH C
O
N
************************************************
TI LIU THAM KHO:
1. Bi tp L thuyt v Thc nghim, tp 2: Ha Hc Hu C Cao C Gic NXB Gio Dc 2006.
2. Bi tp Ha Hu C Trn Th Vit Hoa, Trn Vn Thnh NXB i Hc Quc Gia TP H Ch
Minh 2003.
3. B thi HSG Quc gia lp 12 THPT.
4. B thi Olympic 30/4 cc tnh pha nam.
5. B thi Olympic ha hc Vit Nam v Quc t
6. Bi tp Ha Hu C, tp 1 Ng Th Thun NXB i hc Quc Gia H Ni 1999.
7. Bi tp Ha Hu C, tp 2 Ng Th Thun NXB Khoa hc v K thut 2008.
8. Bi tp Ha Hu C i Hc Y Dc TP H Ch Minh 2001.
9. Tng hp Hu C Nguyn Minh Tho. NXB i hc Quc Gia H Ni 2001.
10. Mt s cu hi v bi tp Ho hu c o Vn ch, Triu Qu Hng NXB i Hc Quc Gia
H Ni.
11. Chuyn mt s hp cht thi n nhin L Vn ng NXB i Hc Quc Gia TP H Ch
Minh 2005.
12. Ha Hc Hu C tp 2, 3 PGS.TS. nh Rng (CB) NXB Gio Dc 2006.
13. Ha hu c Dc B mn Ha Hu C H Dc H Ni 1999.
14. Ha Hu C - Hp cht n chc v a chc PGS. TS. Trng Th K NXB Y Hc H Ni
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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v dng trung ho HA ca prolin pH = 9,70.

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