BT Hoa Huu Co Tap2

volcmttl@yahoo.com.
vn copyright 2010
Ti liu dnh cho:

Hc sinh chuyn Ha.
Sinh vin cc trng i hc.
Gio vin Ha hc.
02 2010
Bi tp Ha Hc Hu C Tp 2 Ti liu dnh cho sinh vin cc tr ng i hc
L i 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 chuy n 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 tp Ha hc hu c bao gm hai tp:
- Tp 1: Gm by chuyn tng ng vi ni dung thuc phn i c ng
ha hc hu c v phn kin thc ha hu c t bi alkane n cetone
(theo chng trnh ha hc ph thng).
- Tp 2: 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 chuy n .
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 ti liu tham kho. V vy Bi tp Ha hc
hu c khng phi l mt ti liu do mt nhm tc gi bin 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).
Copyright 2010 volcmttl@yahoo.com.vn 1

Part 1: AXIT CACBOXYLIC ESTE
COOH O O HOOC H
C C
HO H3C CH3 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 X1 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 (tiu 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 v i 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 (asym metric) trong axit 5- norbonen-2,3-
dicacboxylic.
2. Vit cng thc ha hc lp th ca tng ng phn lp th 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 X1 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 COONa
+ 2NaOH + 2H2O
COOH COONa
Phn ng ca mt ng phn lp th ca Y vi NaOH:
OC COONa
O + NaOH + H 2O
oc COONa

4. MA = 0,3913/(12,7.0,100/1000) = 308 (g/ mol-1) Cc phn ng t X n A:

I I
I2 HCl
-NaI COONa
COONa -NaCl
COOH
COONa O CO O CO
5. Chuyn ha A thnh C:
COOH O CO + HI
O CO O CO
Phn ng ca C vi nc
O CO + 2 H 2O 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 O COOH H O
2 2
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
CH3
H3 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.
COOC2H5

1.LiAlH 4
2.H O
B
C6 H 5 COCl
Pyridin
C(C12H 14O 3 )
1) CH 3 -SO 2 Cl/(C 2 H 5 )3 N
2.NaCN
D(C12H 13O 2 N)
3
COOC2H5
1. KOH(aq)
2. CH 2N2
COOH
F(C9 H14O 3S) E

1.NaOH
( aq ) 1. CH 3 -SO 2Cl/(C 2 H 5 )3 N
2.H O
3 2.CH COS -Cs +
3
SH
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 n u 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.

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
CH3 O CH3
S CH3 OH
O O
Cl N
-
1. -S+Li CO2+Li
2. H+
COOH
CH3
CH3 OH
S
Cl N
BI GII:
1. Cng thc cu to ca cc cht:
O O
CH 2OH CH 2O CH2O
CH 2OH CH2OH H2C C N
B C
D
CH2OH CH2S C CH3
CH 2CO2CH3 CH2CO2CH3
E F

2. SN2: 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 tng gp 9 ln.
4. Vi hai ng lng baz:
CH2SCH2CH3
CH 2CO2H
Vi mt ng lng baz:
CH 2SH
CH2CO2CH2CH3
5. Cng thc Lewis ca sn phm dime:
CH2S SCH2
CH 2 H2 C
HO O O OH
Bi 3: Nm Aspergillus nidulans to ra hai lacton (este vng) thm A v B (C 10H10O4) mi ng phn tan
trong dung dch NaOH lnh trong nc nhng khng tan trong dung dch NaHCO3 trong nc. C A v B
u cho mu tm vi dung dch FeCl3 trong nc. Phn ng ca A vi CH3I c mt K2CO3 to thnh C
(C11H12O4) m ph 1H 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 BCl3 ri x l k tip trong nc
to ra D l mt ng phn mi ca A. Ph 1H NMR ca hp cht D cho thy r s hin din ca mt
nhm hydroxyl c to lin kt hydro ni phn t ti = 11,8pm
OH
H3 C
H 3C CO2CH3
O
HO
E I

Hp cht D c tng hp nh sau: Phenol E c metyl ha (MeI/K2CO3) to F(C9H12O2) sau F

c kh bng liti kim 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 KNH2 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. Th c hin phn ng Diels Alder hp cht H vi
dimetyl but 2 indioat J to thnh K (C 15H20O6) 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(C11H12O6) m khi un nng trong
chn khng to ra N (C11H10O5). Kh N bng NaBH4 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:
OCH3 OCH3 OCH3

O O
H3 C H3 C H3 C
O O O
HO HO H3CO
A B C
O
OH OCH3
OH
O
H3 C H3 C
H3 C
HO H3 CO
H3CO
D E F
OCH3 OCH3
CO2CH3
CH3 CH3 H3C CO2CH3
H3CO O
H3CO
CO2CH3
G H I J

OCH3 OCH3 OCH3
H3C CO2CH3 H3C CO2CH3 H3C CO2H
H3CO CO2CH3 H3CO CO2CH3 H3CO CO2H

K L M
OCH3 O OCH3
H3C H3C
O O
H3CO H3CO
O O
N O
2. Cng thc khc ca B:
OH
H 3C
H 3CO
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
Br
O

B(C5H10O)
C(C5H 8O)
D
E
G
H
I
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 (C5H10O).
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
(C5H8O). 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 O O
O O
*
Br
A B C D E F
O O * OH
OH O *
G H
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
H2 C OOC(CH2)7 C C (CH2)7CH3
H H
cis H2 cis
HC OOC(CH2)7 C C C C C (CH2)4CH3
H H H H
H2 C OOC(CH2)18CH3
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 (I2) 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
H2 C OOC(CH2)7 C C (CH2)7CH3
H H
cis H2 cis
HC* OOC(CH2)7 C C C C C (CH2)4CH3
H H H H
H2 C OOC(CH2)18CH3
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
metyl octadecanoat
O

c. Ozon phn S ri tc dng vi Zn cho cc andehit sau:
O O O O
nonal hexanal metan dicacbadehit
O O metyl nonalat
d. S mol KOH dng nhiu gp 3 ln s mol triglixerit S

10,0
n (S) = = 11,29.10 -3 (mol) = 11,29 (mmol) ; VKOH = 3.n/V = 34,0 mL
885.402
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(I2) = 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 50oC. 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(C12H12O5).
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 FeCl3 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
H2C COOH H2C COOH
HO C COOH
4

H 2SO 4
C O + H2 O + CO
H2C COOH H2C COOH
axit-1,3-pentadioic
Ch c cc axit - 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 Br2 phn ng vi 118mg A
160mg Br2 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 CH2 COCH2 COOH v c cng thc phn t C12H12O5.
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 OCH3. Nh vy cng thc cu to ca cht A s nh sau:
COOH
H3CO
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
OCH3
COOH
COOH
axit-(E)-3-(2-metoxyphenyl)-2-pentendioic
OCH3
COOH
COOH
axit-(Z)-3-(2-metoxyphenyl)-2-pentendioic

HOOC
H3CO
COOH
axit-(Z)-3-(4-metoxyphenyl)-2-pentendioic
d. Hai sn phm khi cho A tc dng vi brom
COOH COOH
H Br Br H
HOOCH2C Br Br CH2COOH
OCH3 OCH3
1 2
Hai cht ny l enantiome
e. Cu hnh tuyt i ti cc trung tm lp th
COOH COOH
S R
H Br Br H
HOOCH2C Br S
Br CH2COOH
OCH3 OCH3
1 2
f. Cng thc cu to cc cht B v C
CH2COOH CH2COOH
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 OCH3. 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 OCH3. 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.
5
6 4
1 3
OH HO 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
OH HNO3 n-C 3H 7 Cl SO Cl2 HOCH 2CH2 N(C 2H 5) 2 H 2 /Pd(C)

A B C D E
baz
HO
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 C4H9Cl c s dng bc 2 thay cho C 3H7Cl 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 C4H9Cl
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 O
O 2N O 2N O2 N
OH OH Cl
HO H3 CH 2 CH 2CO H 3CH2 CH 2 CO
A B C
O O
O2 N H 2N
OCH2 CH 2N(C 2 H5 )2 OCH 2CH2 N(C2 H 5) 2
H 3 CH 2CH 2CO H3 CH2 CH 2 CO

D E
2. Cng thc cu to cc sn phm:

NO2 O O
OH OH
+
O2 N
OH OH
3. c
Bi 8: Vit c ch ca cc phn ng sau y:

a. C6 H 5COCl CH 3CH 2OH
Base
C6 H 5COOCH 2CH 3
b. CH 3CONH 2 H 2O
acid
CH 3COOH NH 4

BI GII:
a. C ch phn ng:
Cl Cl
+
CH3CH2OH+ Cl C CH3CH2 O C CH3CH2 O C
-
O H O OH
- HCl
CH3CH2 O C
b. C ch:
+
NH2 H
H + OH
2
CH3 C NH2 CH3 C NH2 CH3 C O+
H
+ OH
O OH
NH2 NH3+
+ +
-H H
CH3 C OH CH3 C OH CH3COOH + NH4+
OH OH
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 :

O O NH 2NH 2 1. M e 2SO 4, dd NaOH HNO 3, H 2SO 4
OEt A B C
2. NaOH, H 2O o
50 C, 2 h
O
o
SOCl 2, DM F, toluen, 55 C, 6 h H 2 (50 psi), 5% Pd/C
C o D 0 E
dd NH 3, 20 C, 2 h EtOAc, 50 C, 4 h
O Et O
(N N) 2CO
OH ClSO 3H, SOCl 2 CH 3- N NH , H 2O
G H I
t o phng, 18 h o
10 C , 2 h hi l u, 2 h, - N NH
O CH 3
N
O Et HN N
N NH
I E , EtOAc N
K L
t o phng, 70 h Pr
O2 S N N CH 3
Sildenafil
1. Hy hon chnh dy phn ng trn, bit rng:

o Qu trnh chuyn sang G c to thnh axit sunfonic trung gian sau m i chuyn
thnh sunfonyl clorua.
,
o N,N -cacbonyliimiazol (CDI) l m t 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
O O O
H CH3 CH3
O O NH2NH2
OEt EtO N 1. Me2SO4, dd NaOH HO N HNO3, H2SO4
HO N
N 2. NaOH, H2O N 50oC, 2 h N
O
O 2N
A Pr B Pr C Pr
O O
CH3 CH3
o H 2N N H2 (50 psi), 5% Pd/C H 2N N
SOCl2, DMF, toluen, 55 C, 6 h
C o
N 0
EtOAc, 50 C, 4 h
N
dd NH3, 20 C, 2 h
O 2N H 2N
D Pr E Pr
OEt O OEt O OEt O
OH ClSO3H, SOCl2 OH CH3-N NH , H2O OH

to phng, 18 h o
10 C, 2 h
G SO2Cl H O2 S N N CH3
OEt O O
OEt O
(N N)2CO O N N N NH
H N N
hi l u, 2 h , -N NH
Me
O2 S N N CH3
I K O2 S N N CH3

O CH3
OEt H2N N
O N
K E, EtOAc
to phng, 70 h N
Pr
H
L O2 S N N CH3
2. C ch t [I] sang K
(- )
O
OEt O O OEt O
OEt O
C C
O N N O N N
N N N
HN N +
-H N +H +
+ CO2 + HN N
O2 S O2 S
N N CH3 N N CH3 O2 S N N CH3
Bi 11: Vit cng thc cu to ca sn phm cui (nu c) t cc phn ng sau:
COOH + (I2, KI, NaHCO 3)

A
Br + H2N CH COOH B
CH3
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 v i dietylmalonat?
BI GII:
O
CH(COOEt)2
CH CH2 EtOOC
O COOEt O
O C
O O COOEt Ph
1.OH,H 2O
2.H
O
3.t o
Ph
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?

BI GII:
a. Cc cu trc
H H
O O
O O O O
EtO C OEt
H EtO OEt EtO C OEt
H
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
H H
O O
O O
H2C OEt CH3COCH2COOEt
H3C C OEt
A H
B
H
O O
H3C C OEt
H
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:
O
OH OH O O
C O H OH
COOH COOH CO2 Br Br
2 Br Br
Br2
+ Br +
-H Br + +
-H H
Br
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
Br COOH

Part 2: AMINOAXIT AMIN PROTEIN

O
O O
N
N N
N 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 10 0,372oC; hng s nghim si ca nc l 1,86oC.
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 n o phn ng d hn? Vit cng thc cu to
ca cc sn phm.
BI GII:
74,074 8,642 17,284
1. C : H : N : : 5 : 7 : 1 (C5H7N)n
12 1 14
k.m 3,138 1
M 1,86 100 162g / mol 81n = 162 n = 2; CTPT: C 10H14N2
t 96,862 0,372
2.
E F A
COOH
N
N COOH
CH3
N CH3 N
E sinh ra nhiu hn F
3.
Axit piperidin -2-cacboxilic: B N

N COOH H
N
H anabazin
4.
N N -
Cl- Cl
H
N H3C N

Bi 2: Sp xp c gii thch s tng dn tnh axit ca:

COOH COOH CH2COOH
; ; ;
N COOH N
(A) (B) (C) (D)
BI GII:
CH2COOH COOH COOH
-I 1 -I 2 -I 4
< C O <
< -C3 N -I 3
H O N -C4
(D) (C) (A) (B)
V: - I1 < - I2 nn (C) c tnh axit ln hn (D).
(A) v (B) c N nn tnh axit l n hn (D) v (C)
(A) c lin kt hiro ni phn t lm 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 4H9N) 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 2A+ 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:
1,99 10, 6
1. pHI = = 6,3
2
COOH COOH
COOH
NH H H
NH H COOH
N H N
H H
2. p dng phng trnh Henderson - Hasselbalch

K1
HA + H+ ; [HA][H + ]
H2A+ K1
[H 2 A + ]
[HA] [HA]
lg = pH pK1 = 2,50 1,99 = 0,51 Suy ra: = 3,24
[H 2 A + ] [H 2 A + ]
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
[A ] [A ]
3. H2A+ + A
; suy ra lg = pH pK2 = 9,70 10,60 = 0,90
HA HA

[A ] 1
=> = 0,126
HA 8
1
Vy pH = 9,7 t l gia dng eproton h a v dng trung ho l .
8
4. 2 CH2=CH-COOC2H5 CH2-CH2-COOC2H5
CH3NH2 CH 3-N
CH2-CH2-COOC2H5
C2H5ONa
O O
-
1. OH
COOC2H5 2. H3O+, to
N N
CH3 CH3
O
+Br2/Fe, to Br Mg MgBr
COOC2H5
ete
O N OH C6H5 C6H5 C6H5

1. C6H5MgBr CH3 H2SO4, 170oC H2, Ni, to
N 2. H3O+ N N N
CH3
CH3 CH3 CH3
Bi 4: Hy cho bit cc sn phm ca s thy phn trong mi trng axit ca cc cht CH3CONH2 ,
O
O
N
O CH3 H2O
2. CH3-COOCH3 CH3-COOH + CH3OH
+
H , tO BI GII:
H2O
CH3-CONH2 +
CH3-COOH + NH4+
O
H , t
O
O H2O +
CH3-NH2-CH2-COOH + HOCH2COOH
+
N H , tO
O CH3
.
Bi 5: Hp cht A (C 5H11O2N) l mt cht lng quang hot. Kh A bng H2 c xc tc Ni s c B
(C5H13N) 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. D ng cng thc cu to, vit phng trnh cc phn ng to
thnh B, C v ancol tert-amylic t A.
BI GII:

CH3 CH CH2 CH3 CH3 CH CH2 CH3 CH3 CH CH2 CH3 CH3 CH CH2 CH3
CH2NO2 +
H2/ Ni CH2NH2 CH2 H2O CH2OH
HNO2
(A)
Chuyn v H2O OH
* CH CH
CH3 CH Chuyn v +
2 3 CH3 C CH2 CH3
+ CH3 C CH2 CH3
CH2 CH3
CH3
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:
COOH
NO2 NH2 OH OH
HNO3 Sn/ HCl HNO2 CO2,OH-
H2SO4, t0 t0,p
NO2 NH2 NH2 NH2
COOH COOH COOH

NH2 OH OH OH Sn /HCl OH
HNO2 CO2,HO HNO3
0 0
t,p H2SO4, t
O2N H2N
NH2 OH OH OH OH
hoc
CH3 CH3 COOH COOH COOH
NO2 NO2 NH2 OH
HNO3 K 2Cr2O7 Sn / HCl HNO2
H2SO4, t0 H+
NO2 NO2 NH2 OH
COOH COOH
HNO3 OH OH
Sn / HCl
H2SO4
O2N H2N
OH OH
Bi 7:
a. Dng cng thc cu to, hy hon thnh s tng hp sau y:
C2H3O2Cl
COCl2 + CH3OH 6 5 2
B 2
C8H8O4NSClC H NH HOSO Cl

NH 3
D

H 3O
C6H8O2N2S.
b. Gii thch hng ca phn ng to thnh C8H8O4NSCl v C6H8O2N2S.
BI GII:
a. COCl2 + CH3OH
CH3O-COCl

NHCOOCH3 NHCOOCH3 NHCOOCH3 NH2
C6H5NH2 HOSO2Cl NH3 H3O+

CH3OCOCl
d
SO2Cl SO2NH2 SO2NH2

(B) (C) (D) (E)
b. NHCOOCH3 nh hng o, p; do kch thc ln, tc nhn ln nn vo v tr p.
NHCOOCH 3 este-amit thy phn thnh CO2 , cn SO2NH2 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:
N CH2-CH-COOH
NH3 ; ; HOOC-CH2-CH2-CH-COOH ; NH2
COOH
N NH2 N
(Pro) (Glu) (His)
H H
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:
pHI = (pKa 1+pKa2+pKa3) : 3 ; pH I = (pKa 1+pKa2) : 2 ; pH I = (pKa 2+pKa3) : 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 NH2)
* T M = 362 vC suy ra c to ra amid v ng (loi H2O)
* T d kin vng 5 cnh suy ra Glu l aminoaxit u N v to lactam 5 cnh, cn Pro l aminoaxit
u C v to nhm CO NH2.
Vy cu to ca TRF:
HN CH CO-NH CH CO N CH CO-NH2
CH2
O
N
NH

Cng thc Fis:

CO NH2
CO N H
CO NH H
NH H CH2
O N
NH
2. Cn bng in ly ca His:
COOH COO COO COO

+ + +
H3 N H H3 N H H3 N H H 2N H
+ + +
-H -H -H
CH2 CH2 CH2 CH2
(1) (2) (3)
+ +
HN HN N N
NH NH NH NH
(+2) 1,8 (+1) 6,0 (0) (-1)
(hoc vit 3 cn bng ring r; khng cn cng thc Fis)
* pHI = (pKa 2 + pKa3) : 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 = CH2
CO, H 2
xt, t 0
NC CH2 CH2 CH=O
3
HCN, NH
1) H2O, OH
N C CH2 CH2 CH C N HOOC CH2 CH2 CH COOH
2) H3O+
NH2 NH2
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 H2N-CHR-COOH
AA: Ala Arg Gly Ile Phe Tyr

R : CH3 (CH2)3NHC(=NH)NH 2 H CH(CH3)C2H5 CH2C6H5 p-HOC6H4CH2

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 ln nht: Arg, v c nhm guanidin (c 3 nguyn t N)
I
pH nh nht: Phe, v c nhm phenyl.

I
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 Isoleuxin
0 NH
Br2 t
CH CH3 2
(C H 5 OOC) 2 CH 2 1. KOH
CH3CH2
C2H5ONa 2. HCl
Br
Hy cho bit cng thc cu to ca cc cht A, B, C, D v Isoleuxin.

BI GII:
CH 3CH 2CHBrCH 3 A B
C D Isoleux in
o
(C 2 H 5OOC) 2 CH 2 1.KOH t NH 3
C2 H 5ONa 2.HCl
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, ng i 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:
2,5
Peptit A
Peptit B 1,7
0 1 2 3 n v di

c. Khi thu phn hai peptit A v B bng HCl 6N 110oC, 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 oC 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 CO2 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 HOOC CH2 CH2 CH COOH

CO2
NH2
Vy X : HOOC CH CH2 CH COOH
COOH NH2
Gi tn: Axit 3-aminopropan-1,1,3-tricacboxylic

Bi 12: Hp cht A(C 6H12N2O2) quang hot, khng tan trong axit lo ng v baz long, phn ng vi
HNO2 trong nc to thnh B (C 6H10O4). Khi un nng B d dng mt nc chuyn thnh C (C6H8O3).
Hp cht A phn ng vi dung dch brom v natri hydroxit trong n c to thnh D (C 4H12N2), 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:
CONH2 NH2
Br2; OH-
C6H12N2O2 C 4 H8 C 4H 8
H2 O NH2
CONH2
D
D l diamin, deamin ha khi ph n ng vi HNO 2 v chuyn v ging nh pinacolin.
Nh vy c th vit nh sau:

H H HNO2 H H H+
H3 C C C CH3 H3C C C CH3 CH3COCH2CH3
-H2O
NH2 NH2 OH OH
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.
O
CH3 CH3 CH3
C
H CONH2 H COOH H3C C
HNO2 t oC
-H2O O
H2NOC H HOOC H H3C C
C
CH3 CH3 H
O
anhydrit-2,3-dimetyl
sucxinic
2. Cng thc Fis:
CH3 CH3
H CONH2 H2NOC H
H2NOC H H CONH2
CH3 CH3
Bi 13: Tng hp hu c
1. Hy tng hp axit glutamic t axit -xetoglutaric.
2. Hy tng hp prolin t axit adipic.
BI GII:
1. Qu trnh tng hp nh sau:
CH2COOH CH2NH2 CH2NH3+
H2 C H2 C H2 C
H2SO4 H+
HN3 P, Br2
H2 C H2 C COOH H2 C COOH
CH2COOH C CH
H2
(A) Br
(B)
OH-
NH
COOH

1)SOCl2
hoc: HOOC(CH 2 ) 4 COOH
2) NH3
H 2 NCO(CH 2 ) 4 COOH
Br2 / KOH
A ri tip tc nh trn
2. Qu trnh tng hp nh sau:
COOH COOH COOH COOH
CN COOH
CO C C CHNH2
HCN H3 O+ -CO2
NH2 NH2
NH3 to
(CH2)2 (CH2)2 (CH2)2 CH2
COOH COOH COOH CH2
COOH
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 HCO2OH 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 D NP
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 ti N cui. Hy vit cu to y ca DNP Asp ti im ng in
ca n (khng cn ha hc lp th).
o
K , aminoaxit c C cui c xc nh bng cch un nng peptit ti 100 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 NH2 (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 2N
OH
OH
NH
NO2 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 NH2
6. Cu to iu chnh ca A:
Cys Tyr Ile Gln Asn Cys Pro Leu Gly NH2
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:
O O
CH3 + CH3
H N H N
CH3 CH3
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 (H2N CH2 COOH) l - 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 - 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, L alanin v Dalanin ta c th
thu c bao nhiu tripeptit?
O O O
H2N H2N H2N
OH OH OH
H H H CH3 H3C H
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 lin 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
HO
H2SO4 dac OH-

G + 2 H
180Co C , 5h H
+
O
OH
O
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.

O O O O
H H
O O
H OH
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: 79oC; N- metylaxetamit: 28oC v N,N-dimetylfomamit: -61oC).
2. Cu b
3. Gly-Gly-Gly
H O H O O H O
+
N N H3N N
H N OH N O
H O H O
d ng lng cc.
4. 27
5. Trong s th 26 tripeptit c ng phn quang hc
Aminoaxit khng c tnh quang ho t: H2N GGG OH
Aminoaxit c tnh quang hot: H2NGGLAOH; H2NGGDAOH
6. Kh nng lin kt vi PAGE gim dn theo th t F > D > E.
7. H l
HO
O
O
O
O
OH
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 - - 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.

O O O O
OH OH OH OH
NH2 NH2 NH2 NH2
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 n hn 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 H2NR) 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:
Ph Ph
O O O O
H H H H
N N N N
H2N OH H2N OH H2N OH H2N OH
O O O O
Ph Ph
AA FF FA AF
2. Phn ng xy ra:
NO2 NO2
O2 N F + 2 H2NR O2 N NHR + RNH3F
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. C6H5CH2OCONH 2, 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 h ot 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
NH 3
Xianuramit (melamin)
CH 2 O
B
NH2
N N
H2N N NH2
BI GII:
Cl NH2 NHCH2
NH3 HCHO N N
N N N N
Cl C N
Cl N Cl H2N N NH2 CH2HN N NHCH2
n
Bi 20: Cho s sau:

OH
(-)-Serin
HCl
CH3OH
A
B(C 4 H 9Cl 2 NO 2 ) C(C 4 H 8Cl 2 NO 2 )
NaSH
D(C 4 H 9 NO 2S)
1.H3O
2.OH
E
Vit cng thc Fis ca E v cho bit cu hnh tuyt i (R/S) ca n.

BI GII:
S phn ng
PCl5
HO CH2 CH COOH HO CH2 CH COOCH3 Cl CH2 CH COOCH3
NH2 NH3Cl NH3Cl
Cl CH2 CH COOCH3 HS CH2 CH COOCH3 HS CH2 CH COOH
NH2 NH2 NH2
Cng thc chiu Fischer ca E (cystein) E c cu hnh R v hn cp ca -CH2SH > -COOH

COOH
R
H2N H
CH2SH
Bi 21: Sau khi x l hn hp li ng hoc v tru c cha pentozan (C 5H8O4)n vi dung dch axit
clohiric 12% ri tin hnh chng ct, nhn c cht lng A (C5H4O2) mu vng c mi thm. Cho A
phn ng vi KOH ri axit ha th nhn c B (C5H4O3) v C (C5H6O2).

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 (C5H3NO4).
d. Vit phng trnh phn ng ca D tc dng vi: (I) ; (II).
O O NH
H 2N -N
NH S S
(I) O (II)
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
CHO
(C5H8O4)n HCl 12% - 3H2O
(CHOH)3 CHO
O
CH2OH A(C5H4O2)
2 KOH
CHO CH2OH COOK
O A O C O
H3O+
COOK COOH
O O B
b.
H+
COOH + CH2OH COOCH2
O O O O
c. nitro ho A cn phi bo v nhm anehit bng (CH 3CO)2O
(CH3CO)2O
CHO CH(OCOCH3)2
O O
Thc hin phn ng nitro ho, sau thu phn phc hi nhm -CHO
HNO3 H3O+
CH(OCOCH3)2 O 2N CH(OCOCH3)2 O 2N CHO
O O O
D
d. Phn ng ca D vi I v II

H 2N N O O
O 2N CHO O 2N CH N N
O NH O
D O NH
I O
O
O NH
NH
O 2N CHO O 2N CH S
O S O S
II S
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
COOCH3
O
HOH2C
O
HO O
HO CH2OH
OH
BI GII:
Phn ng thu phn geniposit thu c genipin v D-glucoz
COOCH3
COOCH3 OH
O
HO O
HOH2C +
O O OH
HO
HO HOH2C OH
O OH
HO CH2OH
OH
Gelatin (c trong da) cu to t cc polipeptit, ly i din l mt aminoaxit nh glyxin, ta c

phng trnh:
COOCH3 COOCH3
+ H2N-CH2-COOH
O N-CH2-COOH
HOH2C HOH2C
OH OH
sn phm c mu pht hin du vn tay trong k thut h nh s.

Bi tp Ha Hc Hu C Tp 2 Ti liu dnh cho sinh vin cc trng i hc
Part 3: CACBOHIDRAT - POLYME

O O
O OCH2 CH2
O O
H 2C CH2O
O 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:
O
CHO COOH C
OH OH CH2OH
OH OH
HO HO HO O
Br2 H2O
OH OH O OH O
OH OH
OH
CH2OH CH2OH CH2OH
HNO3 axit gluconic D- -gluconolacton
COOH COOH OH
COOH OH
OH O
OH O
O O
HO O OH HO O O
OH
OH O
OH OH OH
1,4-lacton ca axit glucaric
1,4-lacton ca axit glucaric 1,4:3,6-dilactonca axit glucaric
3,6-dilacton ca axit glucaric
COOH 3,6-lacton ca axit glucaric
3,6-lacton ca axit glucaric
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 th nh mt hp cht D khng c tnh quang ho t (khng trit quang). thit
lp quan h gia cu hnh gia D glyxerandehit v C, cht ng andehit 4 cacbon (andotetro z) 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 HIO4; 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 CO2. 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

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:
CHO COOH
H OH H OH
Meso
H OH H OH
CHO CH2OH COOH
H OH
CH2OH CHO COOH
HO H HO H doi xung
H OH H OH
CH2OH COOH
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 HIO4 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 HIO4 to c 3 mol axit metanoic,
1 mol metanal v 1 mol CO2 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.
CHO CH2OH CHO

CHO H OH O H OH
H OH HO H HO H HO H
H OH H OH H OH HO H
CH2OH H OH H OH H OH
CH2OH CH2OH CH2OH
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
CH2OH
H OCH3
O OH
H
H3CO H H
CH 3O H
H OCH3
OCH3 H
H OH
H OCH3
CH2OH
F chuyn ha t B
CH2OCH3
O
OCH3 H
CH3O H O
H CH 3O
H OCH3
H CH2OCH3
H OCH3 H
OCH 3
CH2OCH3

G chuyn ha t C
CHO
CH2OCH3
H OCH3
O OH
OCH3
H3CO H
OCH3 H
H3CO H
H OH H H
CH 2OCH3 H OCH3
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: A5 biu th dng furanoz (vng 5 cnh) ca cacohydrat A.
A6 biu th dng pyranoz (vng 6 cnh) ca cacbohydrat A.
B5 biu th dng furanoz (vng 5 cnh) ca cacbohydrat B.v.v
B
th saccarit X c th c biu th l C6 A6 B5 Mt trong 4 cu to khc nhau c th c ca X:
CH2OH
OH O H
H
OH H
H O CH2
H OH O H
H
H
OH H
OH O
O CH2OH
H OH OH H
H
HOH2C
H OH
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.

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 th c tng hp nhn to trong phng th nghim.
Sau y s trnh by s iu ch L riboz (hp cht I):
B
MeOOC
O
HO
CO 2Me
O + 100oC
ong han kin A OsO4 HO
CO 2Me
MeOOC
Me2C(OMe)2
H+, CH3COCH3
O O
O CO 2Me O CO 2Me
enzym pig liver
O
O
CO 2Me
D
(spc)
F
+ O3; MeOH O
O CO2Me
O CO2 MeO 2C
H
O
O O
E
CO 2Me
(spp)
MCPBA
CO 2M
e
O
HO O CH2OH H O O CO 2Me
3
+ 1) MeOH/H+ O
H
2) LiAlH4
sau do H2O
OH
OH O O
I

1. Hp cht A c cng thc phn t C10H10O5. Vit cng thc cu to A.

2. D no ng, mnh
Trong cc mnh lin quan n vic chuyn ho t A thnh C sau y th mnh
no sai?
a) OsO4 l tc nhn oxy ha trong ph n 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 Me2C(OMe)2
Enzym pig liver esteraza c th thy phn este thnh

D 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 = -37,1
o
cn ca E tinh khit l []20 o

D = 49 .
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 9H16O5. Cc ga tr ph NMR ca H cho di y: 1HNMR (CDCl 3) 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; C2; C3: C4 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
T U
CH2OH
Disaccarit l hp cht c to thnh t hai n v monosaccarit bi lin kt glycozit. Polisaccarit c ha t

10 n vi ngn n v monosaccarit.

V d v disaccarit cho di y:
H OH
H O
HO
H H
H OH
H OH
OH O
H O
lin kt glycozit
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
OH H
5
BI GII:
1.
O
CO2Me
CO2Me
2. Tt c u ng
3. 12,1 : 87,9
hay 12,2 : 87,8
4. a, b ng;
cu c sai

5.
MeO CH2OH
O O
6. C1, 2, 4: S
C3: R
CHO
7.
HO H
HO H
HO H
CH 2OH
8. 25
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 2OH
HO H
HO H
H OH
CH 2OH
(D) Tagaloz
b) Hai sn phm vi cng cng thc phn t C6H10O6 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
1) NaCN / H+
HO H 2) H3O+/to
H OH
CH 2OH
(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:
CH2OH CH2OH (OH) O OH (CH2OH)
O
OH OH OH
OH
H OH (CH2OH) OH CH 2OH (OH)
H H
H H
b) Cc phn ng xy ra:
CHO CHO
CHO
H OH HO H
HO H +
1) NaCN/H HO H + HO H
HO H
H OH H OH
H OH
H OH H OH
CH2OH
CH2OH CH2OH
CHO COOH CH2OH
H OH H OH O
H
HO H HO H -H2O H
H OH H OH
OH
H OH H OH
H OH
CH2OH H3O+/to CH2OH
+ +
CHO COOH
H OH H OH CH2OH
HO H HO H -H2O H O
H OH H OH OH OH O
H OH
H OH
CH2OH CH2OH OH H H
OH
c) Cng thc cu to c th c ca turanoz (khng ch n mt lp th ti cc v tr anome):

O
HO OH(CH2OH)
HOH2C CH2OH(OH)
OH
O
HO
HO 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 2O H OH
OH O
O
OH
OH OH
O
OH 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 th nh lactoloz, y l mt
loi dc phm dng cha cc bnh v rut. S hydro ha lactoz dn n lactitol, mt poliol C12 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.

BI GII:
1. Cng thc cu to ca D galactoz v D glucoz l:
CHO CHO
H OH H OH
HO H HO H
H OH HO H
H OH H OH
CH 2O H CH 2O H
D glucoz D galactoz
2.
a
c
CH 2O H OH
OH O
O
OH
OH OH
O
b
OH OH
3.
CH 2OH CH 2O H
H OH H OH
HO H HO H
H OH HO H
H OH H OH
CH 2OH CH 2O H
Sorbitol (h ot ng quang hc) Galactitol (khng hot ng quang hc)
4.
CH 2OH OH CH 2 OH
OH O OH O O OH
O
OH
OH CH 2OH OH OH CH 2O H
OH O
OH OH OH CH 2 OH
Lactitol Lactolose (f uranose)

CH 2OH OH
OH O CH2 OH
O OH
OH OH O
OH
Lactolose (pyranose)
Bi 6: Mt monosaccarit A c khi lng phn t l 150Da. Khi x l A vi NaBH4 th sinh ra hai ng
phn lp th B v C khng c tnh quang h ot.
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.

BI GII:
1 2.
CH2OH CH2OH CH2OH
S S S
H OH H OH H OH
S R
O H OH HO H
R R R
H OH H OH H OH
CH2OH CH2OH CH2OH
A B C
Mt monosaccarit c cng t hc chung l Cn(H2O)n. Tt nhin, vi khi lng phn t l 150Da th cng
thc ch c th l C5(H2O)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 CHO
H OH H OH
diastereomers
H OH HO H
H OH H OH
CH2OH CH2OH
diastereomers
diastereomers diastereomers
diastereomers
CHO CHO
HO H H OH
H OH enantiomers H OH
H OH HO H
CH2OH CH2OH
Bi 7: T mt monosaccarit, hy vit cc phng trnh phn ng iu ch cht A v B:
OCOCH3
H 5C 6 O
O
O O O
H
CHO CH3COO OCH3
A 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:
+
1. LiAlH4 H2O/H
2. H2O
D HOCH2-CHO + HOCH2-CH2OH
+
CH3OH/H HIO4
Ara (C5H10O5) B C +
Br2/H2O H2O/H
E CHO-COOH + HOCH2-COOH
V cu trc ca B, C, D v E.
BI GII:
1.
O O
OH OH OH
OCH3
OH H2O OH
OH + OH
-H
CH2OH CH2OH
HOCH2 O CH2OH HOCH2 O OH

H2O
OH OH
OCH3 - H+ CH2OH
OH OH
2.
CHO
CH3OH/H+ O O
HIO4
OMe OMe
CHO
CHO
CH2OH
Ara B C
1. LiAlH4 O
HOH2C OMe H3O+
2. H2O CH2OH-CH2OH + CH2OH-CHO
HOH2C
D
O
Br2/H2O
HOOC OMe H3O+
CH2OH-COOH + CHO-COOH
HOOC
E
Bi 10: Hp cht A (C4H6O3) 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 (C5H10O4). Di tc dng
ca axit v c long, B cho metanol v C (C4H8O4). C tc dng vi anhirit axetic to ra dn xut
triaxetat, tc dng vi NaBH 4 to ra D (C4H10O4) khng quang hot. C tham gia phn ng trng bc to

thnh axit cacboxylic E (C4H8O5). X l amit ca E bng dung dch long natri hipoclorit to ra D-(+)-glyxeranehit
(C3H6O3) v amoniac.
V cu trc ca A, B, C, D v E.
BI GII:
CHO COOH CHO
H OH
CH2OH CH2OH CH2OH

H
D-Glyxeraldehit E eO
M C
MeO
O CH2OH
O MeOH
O
CH2 CH2 CH2OH

A B D
Bi 11: T pentoz, hy vit s chuyn ha thnh axit aipic qua giai on to thnh fufuran
BI GII:
HO OH
-2 OH2 OH2 KMnO4
CHO CHO CHO COOH
OH HO O O
OH HO
o O Cl Cl
t Hidro O HCl 1. KCN COOH
xt 2. H3O+ COOH
CO2
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 C12H22O11
BAI GII:
HOH2C
O
HO
HO O C H2
OH O
HO
HO OH
OH
6 o ( glucopiranozyl) D glucopiranozo (A)

OH OMe
HO
HO O MeO
OH MeO OH
OMe
A
O OH
HO MeO
HO OH MeO OH
OH OMe
Bi 13: Salixin C13H18O7 b thy phn bi elmusin cho D -glucoz v Saligenin C7H8O2. 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 O
H 2O
HO D-Glucose + ROH (Saligenin)
enzim
OH C 7H 8O 2
CH2OH
Salixin
Trong cng thc C7H8O2, ROH xut hin nhn thm. Tch c andehit salixylic, iu chng t qu
trnh oxi ha nhm CH2OH thnh nhm CHO
CHO
HO HOH2C
H2O, H+ O CHO
D-Glucose + HO
HO O
OH
Saligenin l o-(hidroximetyl)phenol. Cng th c cu trc ca salixin l

HOH2C
O CH2OH
HO
HO O
OH

Bi 14: Hp cht thin nhin Y (C7H14O6) khng c tnh kh v khng i tnh quang hot. Y b thy phn
bi dung dch HCl/H 2O thnh K l mt ng kh. Khi b oxi ha bi axit nitric lo ng, K chuyn thnh
axit khng quang hot L (C6H10O8). S thoi phn Ruff dn ti mt ng kh M ; cht ny b oxi ha bi
axit nitric long thnh axit quang ho t N (C5H8O7)
a. Xc nh cu trc ca Y, K, L, M, N
b. C tn ti s khng khng nh n o 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
OCH3
CH
H OH
HO H
H OH
O H
CH2OH
L c th l 1 trong cht sau

COOH COOH
OH OH
OH HO
OH HO
OH OH
COOH COOH
M l:
CHO
HO
HO
OH
CH2OH
N c th l 1 trong cht sau

COOH COOH
HO OH
HO OH
OH HO
COOH COOH

K l mt trong 2 cht sau:

CH2OH
O
OH OH OH
O
OH HO OH
OH
CH2OH OH
Y c th l mt trong 2 cht
O CH2OH
OH OCH3
OH
OH O
OH HO OCH3
CH2OH
OH
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 h ng 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 c hip 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:
Monome A
polyme ha
polyme B
poly(vinylancol) 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 1H NMR ca Monome A
Transmittance (%T)
4000 3500 3000 2500 2000 1500 1000

-1
Ph IR ca Monome A wave number (cm )

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 1H NMR v ph IR c cung cp di y, lp lun xc nh cu to C.
Ph 1H NMR ca Monome C

100
80
Transmittance (%T)
60
40
20
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.
H+
E + F + G
O O dd Ca(OH)2 Br2
O H
D Khng mu
BI GII:
1. C4H6O2
2. Nhm C=O
3. Cng thc cu to A:
4. Cng thc cu to B: In: cht khi mo:

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 LiAlH4.
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 299 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 299/2 = 298
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:
O
C
n NH[CH2]5CO
N n
H
Phn ng th dy chuyn nucleop hin:
Bazo Bazo-CO[CH2]5NH-
C NH
O
Bazo-CO[CH2]5NH- Bazo-CO[CH2]5NHCO[CH2]5NH-
C NH
O \
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 ph ng
trnh phn ng v cho bit iu kin phn ng ng v ng DielsAlder xy ra d dng.
BI GII:
a. Phng trnh phn ng:
to, xt to, xt
+ ; + 2H2
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 : CH3, C2H5,
Bi 5: Khi cyclotrimer ha buta 1,3diene 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 v ng ln.
Khi dng cc cht xc tc thch hp l cc phc allyn ca kim loi chuyn tip, ng i 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 6H12N4. Cht D c kh nng

tc dng vi axit nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l ch t n mnh c dng
trong i chin th gii th II theo s : C6H12N4 + 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
CH3CHO + NH 3
Axetandehit-amoniac (tnc = 97oC) A
OH
CH3 CH
NH2
Axetandehit-amoniac d b tch nc thnh B l CH3CH=NH v B d trime ha thnh hp cht d vng
C loi triazin
OH H 3C NH CH3
CH3 CH -H2O trime ha

CH3CH=NH NH NH
NH2
B CH3 C
Mt khc nu cho amoniac ng ng t vi fomanehit s thu c sn phm D (urotropin) c CTPT l

C6H12N4
6HCHO + 4NH 3
C6H12N4 + 6H2O
N
N N
N
Urotropin
Urotropin c kh nng tc dng vi axit nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l ch t
n mnh c dng trong i chin th gii th II theo phn ng:
NO2
N
C6H12N4 + 3HNO3 + 3HCHO + NH3
N N
O 2N NO2
E
Bi 7: Trong phn ng duy tr mch cacbon vi polime c mt xch c s c cha nhm cacbonyl, ng i
ta thng ch n 2 polime ti u biu l poliacrolein A v poli( metacrolein) B

- A tham gia tt c cc phn ng c trng ca andehit nhng khng t c mc chuyn ha ca o.

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 chuy n 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:
... CH2 CH CH2 CH CH2 CH CH CH2 CH ... CH2 CH

CH(OR)2 CHO CHO CH2(OR)2 CHO
n
C A
CH3 CH3
... CH2 CH CH2 CH CH2 CH ... CH2 C CH2 C
CH CHO CH CN CHO
NOH NOH n n
B
D G
... CH2 CH CH2 CH CH2 CH ... CH3

CH CHO CH CH2 C
NNHC6H5 NNHC6H5 CH
NOH
n
E F
Bi 8: Trong khu cng nghip 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(C2H5)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:

2CH 4 C2 H 2 3H 2 CH 2 CH Cl
o
1500 C HCl
A:
NaCl + H2O
dpmn
Cl 2 H 2 2HCl
o
CH 2 CH 2 ClCH 2CH 2Cl CH 2 CH Cl
o
Cl2 ;500 C 500 C
B:
b. Phng php B cn phi x l HCl thu Cl 2 v trnh nhim.
1
2HCl O 2
t o ;xt
Cl 2 H 2O
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:
H Cl
Cl H
Cl H Cl
C
C CH2 CH2
H2 CH2 CH2
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 o n 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 :
Cl
O
Epiclohirin
BI GII:
Giai on 1:
Cl CH3
Cl
+ HO C OH +
O O
CH3
CH3
Cl CH2 CH CH2 O C O CH2 CH CH2 Cl
OH CH3 OH
Giai on 2:
Trong mi trng kim nhm epi li c to thnh

CH3
Cl CH2 CH CH2 O C O CH2 CH CH2 Cl + 2 NaOH
OH CH3 OH
CH3
O O
CH2 O C O CH2 + 2NaCl + 2H2O
CH3
Diepoxit trn li tip tc phn ng vi bisphenol ri epiclohirin phn ng lp li nhiu ln n khi to

thnh oligome epoxi A
CH3 CH3
O O
CH2 O C O CH2 CH CH2 O C O CH2
CH3 OH CH3
n
vi h s n 50 60 .
************************************************

Part 4: CC HP CHT D VNG

N O S
N O 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:
COOH COOH CH2COOH
; ; ;
N COOH N
(A) (B) (C) (D)
BI GII:
CH2COOH COOH COOH
-I 1 -I 2 -I 4
< C O <
< -C3 N -I 3
H O N -C4
(D) (C) (A) (B)
V: - I1 < - I2 nn (C) c tnh axit ln hn (D).
(A) v (B) c N nn tnh axit l n hn (D) v (C)
(A) c lin kt hiro ni phn t lm gim tnh axit so vi (B).
Bi 2: Sp xp v gii thch theo chiu tng dn nhit nng chy ca c c cht:
COOH COOH COOH
; ;
S
N
(A) (B) (C)
BI GII:
Chiu tng dn nhit nng chy
COOH COOH COOH
< <
S N
(C) (A) (B)
V
MC < MA.
(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 oC; hng s nghim si ca nc l 1,86oC.
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 n o phn ng d hn? Vit cng thc cu to
ca cc sn phm.
BI GII:
74,074 8,642 17,284

1. C : H : N : : 5 : 7 : 1 (C5H7N)n
12 1 14
k.m 3,138 1
M 1,86 100 162g / mol 81n = 162 n = 2; CTPT: C 10H14N2
t 96,862 0,372
2. E sinh ra nhiu hn F
E F A
COOH
N
N COOH
CH3
N CH3 N
3.
Axit piperidin -2-cacboxilic: B N

N COOH H
N
H anabazin
4.
N N -
Cl- Cl
H
N H3C N
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. C2H5OCH2CH2OCH2CH2OH (Etylcacbitol)
2. dioxan 3. mophlin
O O O NH

BI GII:
CH2=CH2 C2H5OH
2 H O, H + ,
t 0 ,p
CH2 CH2
O2/Ag
CH2 CH2 C2H5OH O
CH2 CH2 CH2CH2OH CH2CH2OCH2CH2OH (A)
t0 H3O+ H3O+
O
C2H5O C2H5O
H3O+ H2SO4
CH2 CH2 HOCH2CH2OCH2CH2OH O O (B)
2 0
t
O
NH3 1) H2SO4
CH2 CH2 HOCH2CH2NH-CH2CH2OH O NH ( C)
2 H2O 2) Na2CO3
O
Nhit si: A > C > B.

Bi 5: Cho cc cht sau:
OH CH2OH OH OH
HOCH2 O H2C O OH O O
OH HO CH2OH
OH H3C
OH OH OH HO OH OH HO OH
OH
(A) (B) (C) (D)
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? d) thuc loi xetoz?
b) l ng eoxi? e) c dng furanoz?
c) l ng c mch nhnh? f) c cu hnh nhm anomeric?
BI GII:
1. Cng thc chiu Fis ca (A), (B), (C), (D):
CH2OH
CHO CHO CHO C=O
HO OH OH OH
HO OH OH
OH H3C OH
OH HO OH
HO
CH2OH OH
CH2OH CH2OH CH2OH
(A) (B) (C) (D)

2. Trong cc cht (A), (B), (C), (D) trn:

a) (A), (C) l ng thuc dy L d) (D) thuc loi xetoz.
b) (B) l ng eoxi. e) (B) c dng furanoz.
c) (C) l ng c mch nhnh. 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 pKa Hp cht Cu to pKa
N NH2
Piridin 5,17 Anilin 4,58
N NH2
Pirol 0,40 Xiclohexylamin 10,64
N NH2
Pirolidin 11,20 p-Aminopiridin 9,11
N
NH2
Morpholin O NH 8,33 m-Aminopiridin 6,03

N
N
Piperidin 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 ba z ca piridin thuc obitan s p2;
n b gi cht v khng sn sang cho cp electron nh trng hp piperidin vi obitan sp3.
b. Piridin c i electron (th uc obitan sp2) 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
sp2 ca vng thm, nguyn t cacbon ny c m in mnh hn nguyn t cacbon trng thi
lai sp3 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:

NH2 NH2 NH2 NH2
d. C th xy ra s phn tn cc electron khng li n kt ca nhm NH2 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.
NH2 NH2 NH2 NH2

N N N 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 (C8H10) 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 0C 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 c a
A, B, D, G, E v F.
BI GII:
CH3 O
C
CH3 O
C
O
A B
O O
C C OC2H5
O + C2H5OH
C C OC2H5
O D O
O O
C C
O + NH3 (kh) N H
C C
O O ftalimit F
O O
C NH2 O C
160 C
N H
C OH C
G O F O

Bi 8: LSD l cht gy o gic mnh, c cng thc:

Me
N
Et NH
N C
Et O
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 2H5)2NCH2CH2OCOC6H5NH2(p)
b. Sn phm to thanh khi tc dng vi HCl theo t l 1 : 1
Me
HCl
N
Et NH
Et
N C N CH2 CH2 O C NH2
Et O Et HCl O
c. Thy phn bng HCl

Me
HCl
N
NH-HCl
+ -
Et2NH2 Cl HO C
O
Et2NHCH2CH2OH HOOC NH3+Cl-
Thy phn bng NaOH

Me
N
NH
Et2NH NaO C
O
Et2NHCH2CH2OH NaOOC NH2

Bi 9: Gii thch s khc nhau v nhit si trong d y cc cht sau:

(1) (2) (3) (4)
N N
N
N S N N
H H
115oC 117oC 256oC 187oC
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 2CHCHNH 3+COO bng:
a. Phn ng Hell Volhard Zelinski
b. Amin ha kh
c. Tng hp Gabriel

BI GII:
a. Me 2 CHCH 2 COOH
Br2 / P
Me 2CHCHBrCOOH
NH 3
Me 2CHCH(NH 2 )COOH
d
b. Me 2 CHCOCOOH
NH3
H 2 / Pt
Me 2CHCH(NH 2 )COOH
c. S :
O O
COOH
-KBr H 3O +
NK + Br CH CHMe2 N CH CHMe2 Val +
COOEt COOEt COOH
O O
Bi 11: Hy tng hp:

a. Pirolidin t propan-1,3-diol
b. PhN(C4H9)2 t anilin v butan-1-ol
c. Morpholin t etilen oxit v NH3
BI GII:
a. iu ch pirolidin
HOCH 2CH 2CH 2OH

1 mol SOCl 2
HOCH 2CH 2CH 2Cl
KCN,1:1
HOCH 2CH 2CH 2CN
SOCl 2

ClCH 2CH 2CH 2CN
H 2 / Ni
ClCH 2CH 2CH 2CH 2 NH 2
NaOH
HCl
pirolidin
b. iu ch PhN(C 4H9)2 t anilin v butan-1- ol
C3H 7 CH 2OH
PCC
C3H 7 CHO
PhNH 2
C3H 7 CH NPh
NaBH 4
C 4 H 9 NHPh
C4 H 9 Cl*
PhN(C 4H 9 ) 2
c. iu ch Morpholin t etilen oxit v NH3
2 + NH3 P 2O 5
O HOCH2CH2NHCH2CH2OH O NH
Bi 12: Vit s iu ch izatin (indolin -2,3-dion) t 2-nitrobenzoyl clorua
BI GII:

O O O
C C
Cl C
KCN CN H 3O + COOH 6H
NO2 -HCl -NH3 -H2O
NO2 NO2
O
O
C
COOH o
t
O
NH2 -H2O NH
Bi 13: Cho bit cng thc mch h ca cc cht sau:
a. b. c. d.
C 2H 5
HO O O
CH3 O
O
O OH
O HOCH2
CH3CH2 OH
Brevicomin Talaromicin A
BI GII:
a. CH2OHCH2CH2CH2=CHO 5-hidroxipentanal
b. CHOCH2CH2CHOHCH=CHCH=CH2 4-hidroxiocta-5,7-dienal
c. CH3CH2CHOHCHOH(CH 2)3COCH3 6,7-dihidroxinonan-2-on
d. (HOCH2)2CHCHOHCH 2CO(CH2)2CH(C2H5)CH2OH 2,8-di(hidroxometyl)-1,3-dihidroxidacan-5-on
Bi 14: Hy chuyn thiolacton thnh lactam:
HS
NH2CH2CH2 S O
NH O
BI GII:
.. HS
OH ..
S -
S O NH 1. OH
NH2CH2CH2 S O .. 2. H+
NH2 NH O

Bi 15: Pirol uc kh bng Zn v CH3COOH thnh pirolin C 4H7N

a. Vit 2 cng thc c th c ca pirolin
b. Chn ng phn tha iu ki n sau: Khi ozon phn c C4H7NO4, 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 2NHCH2COOH (C) v ng phn B cho HOOCCH 2CH2NHCOOH

(D). Theo bi th ta chn A. Vy pirolin l ng phn A
Bi 16: Vitamin C (axit L-ascobic) l endiol v c c u 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
O O O
HO C C HO C C HO C C
- H+ -
HO C O C O C
b. S iu ch
NaBH4 [O] 2CH3COCH3

D-Glucose D-Socbitol (A) L-Socbose (B) endiol B' Diaxetonua (C)
enzym
1. KMnO4/OH- H+
(D) axit L-ascobic
2. dd H+ o
t

Trong :
CH2OH CH2OH CH2OH
HO H C O HO C
HO H HO H HO C
H OH H OH H OH
HO H HO H HO H
CH2OH CH2OH CH2OH
A B B'
CH2OH COOH
CH3 O C CH3 O C
C C
CH3 O C CH3 O C
H O CH3 H O CH3
HO H C HO H C
CH3 CH3
CH2 O CH2 O
C D
Bi 17: Cho bit sn phm to thnh t cc phn ng sau v gi tn sn phm :
a. Furan + (CH 3CO)2O + (C2H5)2O: BF3

o
0 C
A
b. Thiophen + C 6H5COCl + SnCl 4
B
c. Pyrol + C6H5N2+Cl
C
d. Pyrol + CHCl 3 + KOH
D
BI GII:
A B C D
COCH3 COC6H5 N=NC6H5 CHO
O S N H N H
2-acetylfuran 2-benzoylthiophen 2-(phenylazo)pyrol 2-pyrolcacboxandehit
Bi 18: Trnh by c ch phn ng tng hp quinolin bng ph ng php Skaraup. iu 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 H2SO4 un nng c aldehyd acrolein

Glyceryl
H 2SO4
to
CH2=CHCHO + 2H2O
Acrolein
Giai on 2: Phn ng cng i nhn ca anilin vi acrolein thu c: (phenyla min o)propionaldehyd
O O
NH2 C H C
H CH2
+ CH
CH2
CH2 N
H
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)
O OH H OH
H C H C
CH2 CH2 - H+ -H2O
+ +
H
CH2 CH2
N N N N
H H H H
1,2-dihydroquinolin
Giai on 4: Oxy ha bi nitrobenzen thu c vng thm
NO2 NH2
+ H+
3 3 + + 2 H 2O
N N
H
1,2-dihydroquinolin quinolin
St (II) sunfat c tc dng lm cho phn ng xy ra t t theo chiu thun
Bi 19: Trong y hc, ngi ta thng dng dung dch polividon 3,5% thay th cho huyt tng 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:
HC CH H 2 O 2 NH 3
HOCH 2CH 2CH 2CH 2OH
Cu,Cr
240o C
A
NH 3
B C
t o ,Polyme ha
polividon
Hon thnh s trn bit cng thc ca polividon l:
CH CH2
O N
n
BI GII:

O O O
O N H N CH CH2
A B C
Bi 20: Hon thnh cc phng trnh phn ng sau:
O
C
ete, 30oC
O + N H A
C
O Br
CH3 F
o
N COOC CH3 + + THF, t si
Mg B + MgBrF
CH3
BI GII:
N COOC(CH3)3
O
O
C
C NH
O
A B
************************************************

Part 5: ALKALOID
OHC O
N
N CH3 O CH2
--------------------------------------------------------------------------------------------------------------------------------
Bi 1: Dng du * nh du nguyn t carbon bt i ca cc alkaloid sau:
a. b. c.
CH3CH2 CH2 CH3
N N
CH3 N CH2CH2CH3 N
N
H
Nicotin Coniin Pilocacpin
BI GII:
a. b. c.
CH3CH2 CH2 CH3
* * *
N N
*
CH3 N CH2CH2CH3 N
N
H
Nicotin Coniin Pilocacpin
Bi 2: Papaverin l alkaloid c tch t nha v qu cy papaver sonniferum (cy thuc phin). l

cht rn nng chy 147 oC, c tc dng dn vnh nn c dng d cha bnh co tht i tr ng, mch
mu. Qu trnh tng hp papaverin C 20H21O4N (G) trong cng nghip c cho bi s sau.

B
3, 4 (CH 3O) 2 C 6H 3CH 2Cl
KCN
A
H 2 / Ni
B
H 3O
to
C
PCl5
D E
P2 O5
F
Pd
to
G
a. ngh cng thc cu trc ca cc cht t A

G
b. Trong papaverin c d vng no.
BI GII:
CH2CN CH2CH2NH2 CH2COOH CH2COCl
OCH3 OCH3 OCH3 OCH3
OCH3 OCH3 OCH3 OCH3

A B C D

OCH3 OCH3
NH N
CH3O O C CH3O
CH2 OCH3 OCH3 CH2
OCH3 OCH3
E F
Papaverin G l:
N OCH3
CH3O
OCH3 CH2 OCH3
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 KMnO4 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 c a thuc l, c th coi l alkaloid loi pyridin hay loi pyrolidin. Nicotin
l cht lng khng mu, trong kh quyn chuyn nhanh sang m u 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 C10H14N2 theo s sau:
CH3 CHO
N -
O EtO
A
N EtOH KMnO4 HCl dac - CO2 OH -
B C D E F G
-EtOH
NaBH4 HI
H I K
to
Xc nh cc cht t A
I trong s trn.
BI GII:
Cng thc ca cc cht t A n I torng s :
A O B CH3 C CH3 D CH3

N N N
N CH3 O O O
-
O N HO N O N

O O O O
E F G
C C C NH2Cl C NHCH3
HC OH CH3
H 2C NH2Cl- N
N CH2 N
CH3 HCl-
HCl - HCl-
H OH I I K
CH CH
N
N N CH3
CH3 NH CH3 NH N
Bi 5: Higrin X C8H15ON 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 C6H11O2N. C th tng hp axit higrinic C6H11O2N bng chui cc phn ng sau:

BrCH 2CH 2CH 2Br A B C(C11H19O 4 ) D E
+
[CH(COOEt) 2 ] Na Br2 CH 3 NH 2 Ba (OH) 2 dd ddHCl
to
E axit higrinic CO 2 +H 2O
o
t
BI GII:
T cc d kin cho chng t higrin c nhm amin b c ba v c nhm acetyl CH 3CO
(CH 3 ) 2 Br2
BrCH 2 CH 2 CH 2 CH(COOEt) 2
BrCH 2CH 2CH 2CBr(COOEt )2
COOEt COO COOH

Ba COOH
N COOEt N COO N N
COOH
CH3 CH3 CH3 CH3
C D E E
Vy Higrin l:
CH3
CH2C=NNHPh
PhNHNH2 N
CH3
CH2COOH + CHI3
CH2COCH3 NaOI N
N
CH3
CH3
CrO3 COOH
N
CH3

Bi 6: T ht tiu ngi ta tch c alkaloid piperin A (C17H19NO3) 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 (C5H11N). 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 =CH CH=
- Thu phn B thu dc OHCCOOH v piperidin, suy ra B c lin k t 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 to:
OHC C N O CHO
O
O
(B) (D)
O CH CH CH CH C N
O
O
(E)
- Trong A c 2 lin kt i, s ng phn hnh hc l 4: ZZ , EE , ZE , EZ
Bi 7: Salixin C13H18O7 l mt alkaloid c tm thy trong cy liu. em thy phn Salixin bng ezym
elmusin cho D-glucoz v Saligenin C7H8O2. Salixin khng kh thuc th Tolen. Oxi ha Salixin bng
HNO3 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 O
H 2O
HO D-Glucose + ROH (Saligenin)
enzim
OH C 7H 8O 2
CH2OH
Salixin

Trong cng thc C7H8O2, ROH xut hin nhn thm. Tch c andehit salixylic, iu chng t qu
trnh oxi ha nhm CH2OH thnh nhm CHO
CHO
HO HOH2C
H2O, H+ O CHO
D-Glucose + HO
HO O
OH
Saligenin l o-(hidroximetyl)phenol. Cng th c cu trc ca salixin l

HOH2C
O CH2OH
HO
HO O
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 kh i 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 Br2 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 8H11N). 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 Br2/CCl4
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 8H17N
2 8 3 1 17
bt bo ha 1
2
V coniin khng lm mt mu Br2/CCl4 nen coniin khng cha ni i m cha vng no.
b. S phn ng:
-3 H2 [O]
N CH2CH2CH3 N CH2CH2CH3 N COOH
o
xt, t
H H H
coniin A B
amin (II) amin (III) 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 9H10O3. (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) C9H8O3 c chc andehit. Axit tropoic c th chuyn ha thnh axit
atropoic C 9H8O2 (D) nh H2SO4 c 170 oC. Hidro ha (D) bng H2/Ni thu c axit hidratropoic (E)
C9H10O2. 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:
2 9 2 10
CTPT ca (A) C9H10O3 c bt bo ha: 5
2
- 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 v o vng benzen)
- A b oxy ha bi oxy khng kh khi c mt Cu nung nng to th nh cht (C) C 9H8O3 c chc
andehit => Mch nhnh cha nhm chc r u bc I l CH2OH
- T d kin bi ra ta c CTCT ca A, B, C, D, E nh sau trong D khng c ng phn hnh hc

COOH
KMnO4
to
B
HOOC CH CH2OH COOH
CH
O2 CHO
Cu, t o
C
A
COOH COOH
C C
H2SO4 d CH2 H2 CH3
o o
H
170 C Ni, t
D 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 + CH2I2 + NaOH
B (C8H6O3)
B + CH3CHO + NaOH
C (C10H8O3)
C + anhidrit axetic + natri axetat
axit piperic (C 12H10O4)
axit piperic + PCl 3
D (C12H9O3Cl)
D + piperidin
piperin (C 17H19O3N)
BI GII:
Piperin l:
O CH CH CH CH C N
O
O
************************************************

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 thin 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 - - - - - - - - - -

BT Hoa Huu Co Tap2

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

BT Hoa Huu Co Tap2

Uploaded by

Copyright:

Available Formats

volcmttl@yahoo.com.

Ti liu dnh cho:

Copyright 2010 volcmttl@yahoo.com.vn 1

Part 1: AXIT CACBOXYLIC ESTE

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

Copyright 2010 volcmttl@yahoo.com.vn 2

3. Phn ng ca mt ng phn lp th ca X vi NaOH:

Phn ng ca mt ng phn lp th ca Y vi NaOH:

Copyright 2010 volcmttl@yahoo.com.vn 3

4. MA = 0,3913/(12,7.0,100/1000) = 308 (g/ mol-1) Cc phn ng t X n A:

8) Khng, A v B khng phi l cc ng phn khng i quang.

Copyright 2010 volcmttl@yahoo.com.vn 4

Bi 2: Cc nh ha hc ca cng ty Merck Frosst Canada Montral pht trin mt dc phm rt c

F(C9 H14O 3S) E

Copyright 2010 volcmttl@yahoo.com.vn 5

5. Qa trnh ghp c th tr nn phc tp do s nh hp oxi ha (dime ha oxy ha ca G). Vit

CH 2OH CH2OH H2C C N

CH2OH CH2S C CH3

Copyright 2010 volcmttl@yahoo.com.vn 6

2. SN2: th nucleophin lng phn t.

5. Cng thc Lewis ca sn phm dime:

Copyright 2010 volcmttl@yahoo.com.vn 7

Hp cht D c tng hp nh sau: Phenol E c metyl ha (MeI/K2CO3) to F(C9H12O2) sau F

OCH3 OCH3 OCH3

Copyright 2010 volcmttl@yahoo.com.vn 8

OCH3 OCH3 OCH3

H3C CO2CH3 H3C CO2CH3 H3C CO2H

H3CO CO2CH3 H3CO CO2CH3 H3CO CO2H

2. Cng thc khc ca B:

Bi 4: (-)-Atractyligenin l mt hp cht hot ng sinh hc c c lp t cy gi l Thistle cht choc.

Copyright 2010 volcmttl@yahoo.com.vn 9

Copyright 2010 volcmttl@yahoo.com.vn 10

Cp ng phn khng i quang c im nng chy khc nhau. Cp ng phn i quang c im

a. C bao nhiu ng phn i quang ca S? Dng du hoa th (*) ch ra cc tm i xng gng

a. Cc phn t ca cht thnh phn S c hai ng phn i quang

Copyright 2010 volcmttl@yahoo.com.vn 11

c. Ozon phn S ri tc dng vi Zn cho cc andehit sau:

d. S mol KOH dng nhiu gp 3 ln s mol triglixerit S

Copyright 2010 volcmttl@yahoo.com.vn 12

H2C COOH H2C COOH

H2C COOH H2C COOH

Ch c cc axit - hydroxy cacboxylic mi tham gia phn ng ny

Copyright 2010 volcmttl@yahoo.com.vn 13

Nh vy th trong cng iu kin phn ng th lng sn phm C lun nhiu hn B

Copyright 2010 volcmttl@yahoo.com.vn 14

Bi 7: S pht trin ca cc loi dc phm mi ph thuc ch yu vo tng hp hu c. Phng php

OH HNO3 n-C 3H 7 Cl SO Cl2 HOCH 2CH2 N(C 2H 5) 2 H 2 /Pd(C)

H 3 CH 2CH 2CO H3 CH2 CH 2 CO

2. Cng thc cu to cc sn phm:

Bi 8: Vit c ch ca cc phn ng sau y:

Copyright 2010 volcmttl@yahoo.com.vn 15

Vit cng thc cu to ca A, B, C v ASS.

Copyright 2010 volcmttl@yahoo.com.vn 16

Bi 10: Sildenafil (mt loi thuc tng lc) c tng hp theo s :

1. Hy hon chnh dy phn ng trn, bit rng:

OH ClSO3H, SOCl2 OH CH3-N NH , H2O OH

Copyright 2010 volcmttl@yahoo.com.vn 17

Bi 11: Vit cng thc cu to ca sn phm cui (nu c) t cc phn ng sau:

COOH + (I2, KI, NaHCO 3)

B khng tn ti v phn ng khng xy ra

Copyright 2010 volcmttl@yahoo.com.vn 18

To thnh xetoaxit torng gian, loi hp cht ny d b decacboxyl ha.

Copyright 2010 volcmttl@yahoo.com.vn 19