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07 BT - Hoa - Huu - Co - Tap2 PDF
07 BT - Hoa - Huu - Co - Tap2 PDF
vn copyright 2010
02 2010
i ni u
Part 1:
COOH
HOOC
H
C
HO
H3C
CH3
COOH
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
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-2,3dicacboxylic.
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
COOH
+ 2H2O
+ 2NaOH
COONa
COOH
OC
O
NaOH
oc
COONa
+ H 2O
COONa
I2
-NaI
COONa
COONa
HCl
-NaCl
CO
COOH
O
CO
5. Chuyn ha A thnh C:
I
COOH
O
CO
CO
+ HI
CO
Phn ng ca C vi nc
CO + 2 H 2O
HO
O
CO
6. Cu to ca X l:
HO
COOH
COOH
COOH
COOH
7. Chuyn ha B thnh A
CO
+H O
COOH
COOH
OH
COOH
HOOC
H O
2
CO
COOH
CH3
H3 C
OH
Cl
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
C6 H 5 COCl
1) CH 3 -SO 2 Cl/(C 2 H 5 )3 N
1.LiAlH 4
B
C(C12H 14O 3 )
D(C12H 13O 2 N)
Pyridin
2.NaCN
2.H O
3
COOC2H5
1. KOH(aq)
2. CH 2N2
COOH
1. CH 3 -SO 2Cl/(C 2 H 5 )3 N
( aq )
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.
CH3
CH3
S
O
Cl
OH
CO2+Li
1. -S+Li
2. H+
COOH
CH3
CH3
OH
Cl
BI GII:
1. Cng thc cu to ca cc cht:
O
O
CH 2O
CH 2OH
CH2O
H2C
CH2OH
CH 2OH
CH2OH
D
CH2S
CH3
O
CH2CO2CH3
CH 2CO2CH3
CH 2CO2H
Vi mt ng lng baz:
CH 2SH
CH2CO2CH2CH3
SCH2
H2 C
CH 2
HO
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
OCH3
OCH3
H3 C
H3 C
H3 C
HO
H3CO
B
O
OH
OH
O
HO
C
OCH3
H3 C
H3 C
H3 C
HO
H3 CO
O
H3CO
OCH3
OCH3
CO2CH3
CH3
CH3
H3CO
H3CO
H3C
CO2CH3
O
CO2CH3
OCH3
OCH3
H3C
OCH3
H3C
CO2CH3
CO2CH3
CO2CH3 H3CO
H3CO
K
H3C
CO2H
CO2CH3 H3CO
CO2H
L
OCH3
M
OCH3
H3C
H3C
O
H3CO
H3CO
O
Br
B(C5H10O)
C(C5H 8O)
D
E
H
I
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
Br
F
* OH
OH
Cp ng phn khng i quang c lng khc nhau. Cp i quang c lng bng nhau
10
OOC(CH2)7
C
H
HC
OOC(CH2)7
C
H
C
H
(CH2)7CH3
cis
H2 C
cis
H2
C
C
H
C
H
C
H
(CH2)4CH3
OOC(CH2)18CH3
C
H
OOC(CH2)7
C
H
C
H
cis
HC*
H2 C
b.
OOC(CH2)7
C
H
(CH2)7CH3
H2
C
cis
C
H
C
H
(CH2)4CH3
OOC(CH2)18CH3
O
O
O
metyl octadecanoat
11
O
nonal
hexanal
O
O
metan dicacbadehit
O
O metyl nonalat
10,0
= 11,29.10 -3 (mol) = 11,29 (mmol) ; VKOH = 3.n/V = 34,0 mL
885.402
b. Xc nh cng thc cu to A
c.
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.
12
f.
Xc nh cng thc cu to ca B v C
Phn ng
HO
H2C
COOH
COOH
H2C
COOH
H2C
H 2SO 4
C
H2C
COOH
O
H2 O
CO
COOH
axit-1,3-pentadioic
13
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
HOOCH2C
Br
Br
Br
OCH3
1
H
CH2COOH
OCH3
2
Br
Br
OCH3
1
COOH
R
H
S
CH2COOH
OCH3
2
CH2COOH
HO
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
OH
HO
OH
14
n-C 3H 7 Cl
baz
HO
SO Cl2
H 2 /Pd(C)
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 2N
O 2N
O
O2 N
OH
OH
H3 CH 2 CH 2CO
HO
H 3CH2 CH 2 CO
O
O2 N
Cl
O
H 2N
OCH2 CH 2N(C 2 H5 )2
H 3 CH 2CH 2CO
H3 CH2 CH 2 CO
D
O
OH
OH
+
O2 N
OH
OH
3. c
Bi 8: Vit c ch ca cc phn ng sau y:
Base
a. C6 H 5COCl CH 3CH 2OH
C6 H 5COOCH 2CH 3
acid
b. CH 3CONH 2 H 2O
CH 3COOH NH 4
15
BI GII:
a. C ch phn ng:
Cl
CH3CH2OH+
Cl
CH3CH2
+
O
Cl
CH3CH2
C
OH
- HCl
CH3CH2
C
O
b. C ch:
+
CH3
NH2
NH2
+ OH
CH3
NH2
CH3
NH2
-H
OH
NH3+
H
CH3
O+
C
OH
OH
CH3
OH
OH
CH3COOH + NH4+
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:
16
O
OEt
NH 2NH 2
1. M e 2SO 4, dd NaOH
2. NaOH, H 2O
O
o
SOCl 2, DM F, toluen, 55 C, 6 h
50 C, 2 h
dd NH 3, 20 C, 2 h
HNO 3, H 2SO 4
EtOAc, 50 C, 4 h
O Et
OH
t o phng, 18 h
CH 3- N
(N
NH , H 2O
10 C , 2 h
hi l u, 2 h, - N
O Et HN
N
NH
E , EtOAc
t o phng, 70 h
NH
CH 3
N
N
N) 2CO
Pr
Sildenafil
O2 S
CH 3
O
OEt
NH2NH2
H
N
EtO
1. Me2SO4, dd NaOH
N 2. NaOH, H2O
CH3
N
HNO3, H2SO4
N 50oC, 2 h
HO
CH3
N
N
HO
O 2N
Pr
CH3
N
N
H 2N
dd NH3, 20 C, 2 h
OEt
EtOAc, 50 C, 4 h
H 2N
Pr
E
OEt
10 C, 2 h
H O2 S N
G SO2Cl
N)2CO
hi l u, 2 h ,
-N
OH
OEt
(N
Pr
OH CH3-N NH , H2O
to phng, 18 h
Pr
CH3
N
N
H 2N
OH ClSO3H, SOCl2
O 2N
D
OEt
Pr
O
O
OEt
N
NH
N CH3
O
N
NH
Me
O2 S N
N CH3
K O2 S N
N CH3
17
OEt
K
E, EtOAc
to phng, 70 h
CH3
N
N
N
H
N
L O2 S
Pr
N CH3
2. C ch t [I] sang K
(- )
OEt
OEt
N
N
+H
+ CO2 + HN
O2 S N
N CH3
N CH3
-H
O2 S
N
OEt
HN
O2 S
N CH3
Br
H2N
CH
COOH
CH3
BI GII
A l
O
O
I
O
CH
CH2
COOEt
O
O
C
O
O
1.OH,H 2O
2.H
EtOOC
COOEt
Ph
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?
18
BI GII:
a. Cc cu trc
O
EtO
H
O
O
OEt
C
H
O
EtO
OEt
EtO
O
OEt
C
H
b. Trong :
-
Dng A t bn do ni i khng li n hp
H
O
O
CH3COCH2COOEt
OEt
H2C
H3C
O
OEt
C
H
B
O
H3C
O
OEt
C
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
Br2
COOH
COOH
Br
O
O
CO2
+
Br
-H
-H
OH
Br Br
2
Br
Br
Br
Br
COOH
19
Part 2:
O
N
----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
k.m
3,138
1
1,86
100
162g / mol 81n = 162 n = 2; CTPT: C 10H14N2
t
96,862
0,372
2.
E
COOH
F
COOH
N
CH3
N
CH3
E sinh ra nhiu hn F
3.
B
N
H
COOH
N
H
N
anabazin
4.
N
N H3C
ClN
N Cl
20
COOH
CH2COOH
COOH
;
;
N
(A)
(C)
(B)
(D)
BI GII:
-I 1
CH2COOH
COOH
-I 2
<
(D)
C O
H O
(A)
-C3 N -I 3
<
(C)
COOH
-I 4
<
N -C4
(B)
1.
BI GII:
1,99 10, 6
pHI =
= 6,3
2
COOH
NH
H
COOH
NH
H
COOH
H
COOH
H
N
H
H
2. p dng phng trnh Henderson - Hasselbalch
K1
HA + H+ ;
H2A+
lg
K1
[HA][H + ]
[H 2 A + ]
[HA]
= pH pK1 = 2,50 1,99 = 0,51
[H 2 A + ]
Suy ra:
[HA]
= 3,24
[H 2 A + ]
3. H2A+ + A
[A ]
HA
; suy ra lg
[A ]
= pH pK2 = 9,70 10,60 = 0,90
HA
21
[A ]
1
= 0,126
HA
8
=>
4.
2 CH2=CH-COOC2H5
CH3NH2
CH 3-N
1
8
CH2-CH2-COOC2H5
CH2-CH2-COOC2H5
C2H5ONa
COOC2H5
1. OH
2. H3O+, to
+Br2/Fe, to
Br
N OH C6H5
1. C6H5MgBr
CH3
CH3
O
Mg
MgBr
COOC2H5
ete
CH3
2. H3O+
CH3
C6H5
C6H5
H2, Ni, to
H2SO4, 170oC
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
O
2.
CH3
CH3-COOCH3
CH3-CONH2
O
O
O
H2O
+
H , tO
H2O
+
H , t
CH3-COOH
CH3-COOH
H2O
+
CH3
H , tO
+ CH3OH
BI GII:
+
NH4+
+
CH3-NH2-CH2-COOH
HOCH2COOH
.
22
H2/ Ni
(A)
Chuyn v
CH2
HNO2
Chuyn v
* CH CH
CH3 CH
2
3
+
C
CH3
CH2
CH2 CH3
H2O
OH
H2O
CH3
CH3
CH2 CH3
CH3
HNO3
NH2
Sn/ HCl
COOH
OH
HNO2
OH
CO2,OHt0,p
H2SO4, t0
NO2
NH2
COOH
NH2
OH
HNO2
HNO3
OH
CH3
OH
COOH
NO2
COOH
NH2
Sn / HCl
NO2
NO2
COOH
OH
H2N
O2N
COOH
K 2Cr2O7
H+
OH
HNO2
NH2
OH
COOH
OH
HNO3
COOH
OH
NO2
H2SO4, t0
OH
CH3
HNO3
COOH
OH Sn /HCl
H2SO4, t
t,p
hoc
NH2
OH
CO2,HO
NH2
NH2
OH
Sn / HCl
H2SO4
O2N
OH
H2N
OH
Bi 7:
a. Dng cng thc cu to, hy hon thnh s tng hp sau y:
6 5
2
C8H8O4NSCl
B 2
COCl2 + CH3OH
C2H3O2Cl
C H NH
HOSO Cl
NH 3
H 3O
C6H8O2N2S.
23
NHCOOCH3
HOSO2Cl
CH3OCOCl
NHCOOCH3
NH2
H3O+
NH3
SO2Cl
(C)
(B)
SO2NH2
(E)
SO2NH2
(D)
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
NH3 ;
N
COOH
CH2-CH-COOH
; HOOC-CH2-CH2-CH-COOH ;
NH2
(Glu)
(Pro)
NH2
N
H
(His)
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
24
NH2
CO
NH
CO
NH
CO
CH2
N
NH
2. Cn bng in ly ca His:
COOH
+
H3 N
COO
+
-H
CH2
-H
HN
H 2N
CH2
(3)
N
NH
1,8
-H
NH
(+2)
H
CH2
(2)
HN
H3 N
CH2
(1)
H3 N
COO
COO
NH
NH
(+1)
6,0
(-1)
(0)
HCN
NC CH = CH2
CO, H 2
xt, t 0
C CH2 CH2 CH C N
1) H2O, OH
NH2
2) H3O+
HCN, NH
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.
Arg
Gly
Ile
R : CH3
(CH2)3NHC(=NH)NH 2
CH(CH3)C2H5 CH2C6H5
Phe
Tyr
p-HOC6H4CH2
25
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
A B C D
CH CH3 2
0
CH3CH2
C2H5ONa
NH
2. HCl
Br
Peptit A
Peptit B
1,7
n v di
26
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
Vy X :
CO2
HOOC CH CH2
COOH
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
C6H12N2O2
C 4 H8
CONH2
Br2; OHH2 O
NH2
C 4H 8
NH2
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:
27
H
C
H
C
NH2
NH2
HNO2
CH3
H3C
H
C
H
C
OH
OH
CH3
H+
-H2O
CH3COCH2CH3
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.
CH3
H
CH3
CONH2
H2NOC
HNO2
COOH
HOOC
CH3
t oC
-H2O
H3C
H3C
C
O
C
CH3
CH3
H
O
anhydrit-2,3-dimetyl
sucxinic
CH3
CONH2
H2NOC
H2NOC
CH3
CONH2
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
H2 C
H2SO4
HN3
H2 C
CH2COOH
H2 C
H2 C
COOH
C
H2
(A)
OH-
CH2NH3+
CH2NH2
H+
P, Br2
H2 C
H2 C
COOH
CH
Br
(B)
NH
COOH
28
2) NH3
Br2 / KOH
hoc: HOOC(CH 2 ) 4 COOH
H 2 NCO(CH 2 ) 4 COOH
A ri tip tc nh trn
HCN
NH3
COOH
CN
C
NH2
(CH2)2
COOH
COOH
H3 O+
COOH
COOH
C
-CO2
NH2
to
(CH2)2
COOH
COOH
CHNH2
CH2
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
29
NO2
NH2
6. Cu to iu chnh ca A:
Cys Tyr Ile Gln Asn Cys Pro Leu Gly NH2
O
N
CH3
CH3
CH3
CH3
30
Khi - aminoaxit cha nhoam th thu lc ny s xut hin hin tng ng phn quang hc. V d:
OH
H2N
H
Glyxin (Gly)
5.
O
H2N
OH
H3C
CH3
L-Alanin (L-Ala)
OH
H
D-Alanin (D-Ala)
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
OH-
H2SO4 dac
G
180Co C , 5h
OH
H
O
O
Phenolphtalein
31
OH
O
O
O
c
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
H
N
H
O
OH
+
H3N
O
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
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.
Copyright 2010 volcmttl@yahoo.com.vn
32
OH
OH
OH
NH2
NH2
A
O
OH
NH2
NH2
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:
H
N
H2N
Ph
H
N
H2N
OH
AA
FF
Ph
O
OH
H
N
H2N
O
OH H2N
O
Ph
H
N
FA
O
OH
Ph
AF
2. Phn ng xy ra:
NO2
O2 N
NO2
2 H2NR
O2 N
NHR
RNH3F
33
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)
Copyright 2010 volcmttl@yahoo.com.vn
34
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 :
BI GII:
1. Cng thc cu to cc peptit c th c:
35
2. Cu tr li tt nht l b v e
3.
v kh nht A:
36
NH2
N
H2N
N
N
NH2
BI GII:
Cl
N
Cl
NH3
N
N
NHCH2
NH2
Cl
N
H2N
Cl
HCHO
N
N
N
CH2HN
NH2
N
N
NHCH2
1.H3O
HCl
OH
NaSH
(-)-Serin
A
B(C 4 H 9Cl 2 NO 2 )
C(C 4 H 8Cl 2 NO 2 )
D(C 4 H 9 NO 2S)
E
CH3OH
2.OH
CH2
CH
COOH
PCl5
HO
CH2
CH
NH2
Cl
CH2
COOCH3
Cl
CH2
NH3Cl
CH
COOCH3
HS
CH2
NH2
CH
COOCH3
NH3Cl
CH
COOCH3
HS
CH2
CH
COOH
NH2
NH2
H2N
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).
Copyright 2010 volcmttl@yahoo.com.vn
37
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
H 2N -N
NH
NH
S
S
(II)
(I) 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
CHO
(C5H8O4)n HCl 12%
(CHOH)3
- 3H2O
CH2OH
2
O A
CHO
KOH
O C
COOK
H3O+
CH2OH
b.
O
A(C5H4O2)
COOK
COOH
B
COOH +
CHO
CH2OH
H+
COOCH2
O
(CH3CO)2O
CHO
CH(OCOCH3)2
Thc hin phn ng nitro ho, sau thu phn phc hi nhm -CHO
CH(OCOCH3)2
HNO3
O 2N
CH(OCOCH3)2
H3O+
O 2N
CHO
O
D
d. Phn ng ca D vi I v II
38
O 2N
CHO
I
O
O
O 2N
NH
O 2N
H 2N N
NH
O
O
NH
CHO
II S
O 2N
N N
CH
O
NH
CH
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
HO
HO
O
OH
CH2OH
BI GII:
Phn ng thu phn geniposit thu c genipin v D-glucoz
COOCH3
COOCH3
OH
O
+
HOH2C
O
HO
HOH2C
HO
OH
HO
OH
OH
CH2OH
HO
OH
O
HOH2C
COOCH3
H2N-CH2-COOH
OH
N-CH2-COOH
HOH2C
OH
39
Part 3:
CACBOHIDRAT - POLYME
O
OCH2
O
CH2
H 2C
CH2O
n
-------------------------------------------------------------------------------------------------------------------------------O
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
COOH
CHO
OH
OH
HO
OH
OH
CH2OH
HNO3
COOH
OH
HO
Br2
COOH
H2O
OH
HO
O
OH
OH
OH
CH2OH
CH2OH
axit gluconic
D- -gluconolacton
OH
COOH
O
COOH
OH
O
CH2OH
OH
O
OH
HO
OH
OH
OH
OH HO
OH
O
O
O
O
O
OH
1,4-lacton
ca
axit
glucaric
1,4:3,6-dilactonca
axit
glucaric
3,6-dilacton ca axit glucaric
1,4-lacton ca axit glucaric
3,6-lacton ca axit glucaric
OH
40
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-Dhexoz (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.
phi l C-2 epime ca D-mannoz (l D-glucoz) v cht kia phi l ng xeton tng ng C-2 (nh Dfructoz) (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.
Andotetroz to thnh trc C (cng nh trc D) khng cho mt hp cht meso sau phn ng vi axit
OH
OH
OH
OH
CHO
H
COOH
CH2OH
COOH
CHO
COOH
Meso
OH
CH2OH
HO
H
H
OH
CH2OH
HO
H
doi xung
OH
COOH
41
CHO
OH
H
HO
HO
H
H
OH
HO
OH
OH
OH
HO
CH2OH
OH
OH
CH2OH
D-Glucose
CHO
CH2OH
CHO
OH
OH
CH2OH
CH2OH
D-Fructose
D-Galactose
E chuyn ha t A
CHO
CH2OH
H
OCH3
H3CO
OCH3
OH
OH
H
H
CH 3O
OCH3
H
OCH3
CH2OH
F chuyn ha t B
CH2OCH3
O
H
OCH3
CH3O
H
H
CH 3O
OCH3
CH2OCH3
H
H
OCH3
OCH 3
CH2OCH3
42
G chuyn ha t C
CHO
CH2OCH3
H
OCH3
H3CO
H3CO
OCH3
OCH3
H
OH
OH
H
H
CH 2OCH3
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
CH2OH
O
OH
H
H
OH
H
H
OH
H
O
H
OH
CH2
O
H
OH
H
H
O
OH
CH2OH
O
OH
H
H
HOH2C
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.
43
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
100oC
ong han kin
CO 2Me
HO
OsO4
CO 2Me
MeOOC
Me2C(OMe)2
H+, CH3COCH3
CO 2Me
CO 2Me
O
CO 2Me
D
(spc)
F
+
O3; MeOH
CO2Me
O
O
MeO 2C
CO2
H
O
E
(spp)
CO 2Me
MCPBA
CO 2M
e
O
O
HO
CO 2Me
CH2OH H O
3
H
1) MeOH/H+
2) LiAlH4
sau do H2O
OH
OH
I
G
Copyright 2010 volcmttl@yahoo.com.vn
44
1.
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
CHO
P
U
CH2OH
45
V d v disaccarit cho di y:
H
OH
H
HO
H
H
H
OH
OH
H OH
O
H
lin kt glycozit
O
OH
H
H
OH
OH
H OH
H
H
O
O
H
H
OH
OH
H
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
Copyright 2010 volcmttl@yahoo.com.vn
46
5.
MeO
CH2OH
6.
C1, 2, 4: S
C3: R
CHO
7.
HO
HO
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
O
HO
HO
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?
Copyright 2010 volcmttl@yahoo.com.vn
47
1) NaCN / H+
HO
2) H3O+/to
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)
OH
OH
H
H
OH (CH2OH)
OH
OH
OH (CH2OH)
CH 2OH (OH)
OH
b) Cc phn ng xy ra:
CHO
HO
H
HO
OH
CH2OH
1) NaCN/H
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
CHO
H
HO
H
H
H
HO
H
H
OH
H
OH
OH
CH2OH
+
CHO
OH
H
OH
OH
H
HO
H
H
H3O+/to
CH2OH
H
HO
H
H
COOH
OH
H
OH
OH
CH2OH
+
COOH
OH
H
OH
OH
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
-H2O
CH2OH
O
H
OH
H
-H2O
CH2OH
O
OH
CH2OH
OH
OH H
OH
OH
48
O
HO
OH(CH2OH)
HOH2C
CH2OH(OH)
OH
O
HO
HO
O
OH
CH 2O H
O
OH
OH
O
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.
Copyright 2010 volcmttl@yahoo.com.vn
49
BI GII:
1. Cng thc cu to ca D galactoz v D glucoz l:
CHO
CHO
H
HO
H
H
OH
H
OH
H
HO
OH
HO
H
OH
CH 2O H
CH 2O H
D glucoz
OH
H
D galactoz
2.
a
CH 2O H
O
OH
c
OH
OH
OH
OH
b
OH
O
OH
3.
CH 2O H
CH 2OH
H
OH
HO
H
H
OH
HO
OH
HO
H
H
OH
OH
CH 2O H
CH 2OH
4.
OH
CH 2OH
O
OH
O
OH
OH
OH
CH 2OH
CH 2 OH
O
OH
OH
OH
O
OH
OH
OH
OH
Lactitol
CH 2OH
O
OH
OH
OH
OH
CH 2O H
CH 2 OH
Lactolose (f uranose)
OH
CH2 OH
O
OH
Lactolose (pyranose)
50
BI GII:
1 2.
OH
O
OH
OH
HO
OH
H
OH
CH2OH
OH
OH
CH2OH
CH2OH
CH2OH
CH2OH
CH2OH
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
OH
HO
OH
diastereomers
OH
H
OH
CH2OH
CH2OH
diastereomers
diastereomers
diastereomers
diastereomers
CHO
CHO
HO
OH
OH
enantiomers
OH
OH
HO
H
CH2OH
CH2OH
CHO
A
OCOCH3
H 5C 6
O
CH3COO
OCH3
51
BI GII:
iu ch A
BI GII:
52
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 (C5H10O5)
CH3OH/H
1. LiAlH4
2. H2O
HIO4
H2O/H
H2O/H
C
Br2/H2O
HOCH2-CHO + HOCH2-CH2OH
CHO-COOH + HOCH2-COOH
V cu trc ca B, C, D v E.
BI GII:
1.
O
OH
OH
O
OH
OCH3
OH
H2O
-H
OH
CH2OH
OH
OH
CH2OH
HOCH2 O
OH
CH2OH
HOCH2 O
OH
H2O
- H+
OCH3
OH
OH
CH2OH
OH
2.
CHO
O
CH3OH/H+
OMe
HIO4
OMe
CHO
CHO
CH2OH
Ara
1. LiAlH4
2. H2O
B
O
HOH2C
D
Br2/H2O
C
OMe
HOH2C
H3O+
CH2OH-CH2OH + CH2OH-CHO
O
HOOC
OMe
HOOC
H3O+
CH2OH-COOH + CHO-COOH
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
Copyright 2010 volcmttl@yahoo.com.vn
53
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:
COOH
CHO
H
CHO
OH
CH2OH
CH2OH
D-Glyxeraldehit
CH2OH
H
eO
M
MeO
O
CH2OH
O
MeOH
CH2
CH2
A
CH2OH
Bi 11: T pentoz, hy vit s chuyn ha thnh axit aipic qua giai on to thnh fufuran
BI GII:
HO
OH
-2 OH2
CO2
CHO
Hidro
KMnO4
OH HO
OH HO
OH2
CHO
CHO
HCl
COOH
O
Cl Cl
1. KCN
2. H3O+
xt
COOH
COOH
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-metylD-glucoz. Vit CTCT v gi tn Gentibioz C12H22O11
BAI GII:
HOH2C
HO
HO
O
O C H2
OH
HO
HO
O
OH
OH
54
OH
OMe
HO
HO
OH
MeO
MeO
OMe
OH
A
OH
O
HO
HO
MeO
MeO
OH
OH
OMe
OH
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
HO
H 2O
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
H2O, H+
D-Glucose +
HOH2C
HO
HO
O
OH
CHO
O
O
OH
CH2OH
O
55
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
OH
H
CH2OH
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
COOH
HO
COOH
56
O
OH
OH
OH
O
OH
HO
OH
HO
OCH3
OH
CH2OH
OH
Y c th l mt trong 2 cht
O
OCH3
OH
CH2OH
OH
O
OH
OH
CH2OH
OH
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:
polyme ha
Monome A
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.
57
Transmittance (%T)
Ph 1H NMR ca Monome A
4000
3500
3000
2500
2000
Ph IR ca Monome A
Copyright 2010 volcmttl@yahoo.com.vn
1500
1000
-1
1.
2.
3.
Cho bit cu to ca A
4.
5.
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.
Ph 1H NMR ca Monome C
59
Transmittance (%T)
100
80
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.
n
H+
E
O
dd Ca(OH)2
Br2
H
Khng mu
BI GII:
1. C4H6O2
2. Nhm C=O
3. Cng thc cu to A:
4. Cng thc cu to B:
60
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:
C
N
O
NH[CH2]5CO
H
Bazo
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
61
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
+
+ 2H2
to, xt
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
Copyright 2010 volcmttl@yahoo.com.vn
62
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
H 3C
OH
CH3
-H2O
CH
CH3CH=NH
NH2
trime ha
NH
NH
CH3
NH
CH3
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
O 2N
+ 3HCHO + NH3
NO2
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
63
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
Cho bit cu to ca A, B, C, D, E, F, G
BI GII:
...
CH2
...
CHO
CH2
CH
CH2(OR)2
CHO
A
CH3
CH3
...
...
CHO
NOH
CH2
CHO
CHO
NNHC6H5
n
B
CN
NOH
CH
CH2
CH
D
...
...
CH
CH3
CH2
NNHC6H5
CH
NOH
n
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:
64
A:
1500 C
HCl
2CH 4
C2 H 2 3H 2
CH 2 CH Cl
o
dpmn
NaCl + H2O
Cl 2 H 2 2HCl
B:
b.
Cl2 ;500 C
500 C
CH 2 CH 2
ClCH 2CH 2Cl
CH 2 CH Cl
o
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
C
C
H2
CH2
CH2
Cl
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:
CH3
Cl
+
HO
Cl
OH
+
O
CH3
CH3
Cl
CH2 CH CH2 O
OH
C
CH3
O CH2 CH CH2 Cl
OH
Giai on 2:
Trong mi trng kim nhm epi li c to thnh
65
CH3
Cl
CH2 CH CH2 O
OH
O CH2 CH CH2 Cl
CH3
OH
CH3
CH2
+ 2 NaOH
O CH2
O
+
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
O
CH3
CH2
CH3
O CH2 CH CH2
CH3
OH
O CH2
CH3
n
vi h s n 50 60 .
************************************************
66
Part 4:
CC HP CHT D VNG
N
Pyridine
Dioxan
S
N
N
Indole
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
COOH
;
;
N
(A)
(D)
(C)
(B)
BI GII:
-I 1
CH2COOH
COOH
-I 2
<
(D)
C O
H O
(A)
-C3 N -I 3
<
(C)
<
COOH
-I 4
N -C4
(B)
COOH
COOH
;
N
(A)
(B)
(C)
BI GII:
Chiu tng dn nhit nng chy
COOH
COOH
<
(C)
S
(A)
<
COOH
N
(B)
V
MC < MA.
(B) c thm lin kt hiro lin phn t vi N ca phn t khc.
Copyright 2010 volcmttl@yahoo.com.vn
67
k.m
3,138
1
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
COOH
F
COOH
N
CH3
N
CH3
3.
N
H
B
N
H
COOH
N
anabazin
4.
Cl-
N H3C
N Cl
3. mophlin
O
NH
68
BI GII:
2
C2H5OH
CH2=CH2
t 0 ,p
H O, H + ,
CH2
CH2
O2/Ag
t0
CH2CH2OH
H3O+
C2H5O
H3O+
CH2
CH2
CH2 C2H5OH
CH2
CH2 CH2
O
H3O+
NH3
CH2
H2O
1) H2SO4
HOCH2CH2NH-CH2CH2OH
(A)
C2H5O
H2SO4
HOCH2CH2OCH2CH2OH
CH2
CH2CH2OCH2CH2OH
2) Na2CO3
(B)
NH ( C)
HOCH2
OH
CH2OH
OH
OH
OH
H2C
OH HO OH
OH
(B)
(A)
O
HO
H3C
OH
OH
OH
OH
CH2OH
OH HO OH
(C)
(D)
b) l ng eoxi?
e) c dng furanoz?
c) l ng c mch nhnh?
CHO
HO
HO
HO
CH2OH
CHO
OH
OH
OH
OH
CH2OH
(A)
CH2OH
(B)
CHO
H3C
HO
OH
OH
CH2OH
(C)
C=O
OH
OH
OH
OH
CH2OH
(D)
69
b) (B) l ng eoxi.
Cu to
pKa
Hp cht
Cu to
pKa
NH2
Piridin
5,17
Anilin
4,58
NH2
Pirol
0,40
Xiclohexylamin
10,64
NH2
Pirolidin
11,20
p-Aminopiridin
9,11
NH2
Morpholin
NH
8,33
m-Aminopiridin
6,03
N
Piperidin
11,11
Piperiin / piriin
b.
Piridin / pirol
c.
Anilin / xiclohexylamin
d.
p aminopiridin / piridin
e.
morpholin / piperidin
a.
BI GII:
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
70
NH2
d.
NH2
NH2
NH2
N
e.
NH2
NH2
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
C
C
CH3
C
C
O +
C OC2H5
C OC2H5
C2H5OH
O
C
C
C
C
+ NH3 (kh)
O
O
C NH2
C OH
G
N H
ftalimit F
O
O
C
C
160 C
N H
71
N
NH
Et
N C
Et
a.
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.
Me
HCl
N
NH
Et
Et
N C
Et
N CH2 CH2
Et HCl
O C
NH2
Et2NH2 Cl
HO
C
O
Et2NHCH2CH2OH
NH3+Cl-
HOOC
Me
N
NH
Et2NH
NaO
C
O
Et2NHCH2CH2OH
NaOOC
NH2
72
(2)
(3)
(4)
256oC
187oC
N
N
115oC
S
117oC
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
73
BI GII:
NH 3
Br2 / P
a. Me 2 CHCH 2 COOH
Me 2CHCHBrCOOH
Me 2CHCH(NH 2 )COOH
d
NH3
b. Me 2 CHCOCOOH
Me 2CHCH(NH 2 )COOH
H 2 / Pt
c. S :
O
O
-KBr
NK + Br
CH CHMe2
CH CHMe2
H 3O +
COOH
Val +
COOEt
COOEt
O
COOH
H 2 / Ni
NaOH
ClCH 2CH 2CH 2CN
ClCH 2CH 2CH 2CH 2 NH 2
pirolidin
HCl
PhN(C 4H 9 ) 2
c. iu ch Morpholin t etilen oxit v NH3
2
NH3
HOCH2CH2NHCH2CH2OH
P 2O 5
NH
74
Cl
-HCl
NO2
COOH
6H
-NH3
NO2
-H2O
NO2
O
C
H 3O +
CN
KCN
O
COOH
-H2O
NH2
NH
b.
c.
HO
d.
CH3
O
O
C 2H 5
OH
HOCH2
O
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
HS
NH2CH2CH2
NH
BI GII:
..
OH
S
NH2CH2CH2
..
NH2
NH
..
1. OH
2. H+
HS
-
NH
75
N H
2,5-dihidropirol (A)
2,3-dihidropirol (B)
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
HO
HO
O
HO
- H+
O
HO
O C
O C
b. S iu ch
D-Glucose
NaBH4
1. KMnO4/OH2. dd H+
[O]
D-Socbitol (A)
(D)
H+
o
enzym
L-Socbose (B)
endiol B'
2CH3COCH3
Diaxetonua (C)
axit L-ascobic
76
Trong :
HO
HO
C O
HO
HO
HO
H
OH
HO
CH2OH
CH2OH
CH2OH
HO
OH
OH
HO
CH2OH
CH2OH
CH2OH
B'
COOH
CH2OH
CH3
C
CH3
O C
C
CH3
O C
H
O CH3
HO
H C
CH3
CH2 O
CH3
O C
O C
H
O CH3
HO
H C
CH3
CH2 O
D
B
b. Thiophen + C 6H5COCl + SnCl 4
c. Pyrol + C6H5N2+Cl
C
d. Pyrol + CHCl 3 + KOH
D
BI GII:
COCH3
O
2-acetylfuran
COC6H5
S
2-benzoylthiophen
N=NC6H5
N H
2-(phenylazo)pyrol
CHO
N H
2-pyrolcacboxandehit
77
Acrolein
Giai on 2: Phn ng cng i nhn ca anilin vi acrolein thu c: (phenyla min o)propionaldehyd
NH2
+
H C
CH
CH2
CH2
CH2
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
H C
N
OH
H C
CH2
CH2
OH
H
- H+
CH2
-H2O
CH2
N
H
H
1,2-dihydroquinolin
NO2
+
NH2
H+
+ 2 H 2O
H
1,2-dihydroquinolin
quinolin
CH CH2
O
N
n
BI GII:
78
N H
N CH CH2
O
C
O
ete, 30oC
N H
C
Br
CH3
N COOC
CH3
Mg
THF, t si
CH3
B + MgBrF
BI GII:
N COOC(CH3)3
O
O
C
O
NH
************************************************
79
ALKALOID
Part 5:
OHC
O
O CH2
CH3
a.
c.
CH3CH2
b.
CH3
CH2
N
N
N
CH3
CH2CH2CH3
H
Coniin
Nicotin
Pilocacpin
BI GII:
a.
c.
CH3CH2
b.
*
N
CH3
CH2
N
*
N
CH3
* *
CH2CH2CH3
H
Coniin
Nicotin
Pilocacpin
H 3O
PCl5
P2 O5
H 2 / Ni
KCN
B
Pd
3, 4 (CH 3O) 2 C 6H 3CH 2Cl
A
B
C
D
E
F
G
to
to
CH2CH2NH2
CH2COOH
OCH3
OCH3
CH2COCl
OCH3
OCH3
OCH3
OCH3
OCH3
OCH3
80
OCH3
CH3O
O C
OCH3
NH
CH3O
CH2
OCH3
OCH3 CH2
OCH3
OCH3
Papaverin G l:
CH3O
OCH3 CH2
OCH3
OCH3
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)
81
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
NaBH4
EtO
-EtOH
HI
to
EtOH
KMnO4
HCl dac
D
- CO2
OH -
Xc nh cc cht t A
I trong s trn.
BI GII:
Cng thc ca cc cht t A n I torng s :
CH3
N
CH3
N
N CH3
CH3
N
HO
82
HC
H 2C
N
HCl
NH2Cl
OH
CH2
CH3
NH2Cl-
CH3
HCl-
HCl-
OH
NHCH3
I
CH
CH
N
N
CH3
NH
CH3
CH3
NH
CH 3 NH 2
[CH(COOEt) 2 ] Na
Br2
Ba (OH) 2 dd
ddHCl
BrCH 2CH 2CH 2Br
A
B
C(C11H19O 4 )
D
E
to
+
t
E
axit higrinic CO 2 +H 2O
o
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
N
COOEt
CH3
C
COO
COOH
Ba
COO
CH3
D
COOH
N
COOH
CH3
E
CH3
E
Vy Higrin l:
CH3
PhNHNH2
CH2C=NNHPh
CH3
N
CH3
CH2COCH3
NaOI
CH2COOH
CHI3
CH3
CrO3
COOH
N
CH3
83
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:
-
CHO
O
(B)
(D)
CH CH CH CH C N
O
O
(E)
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
HO
OH
H 2O
enzim
CH2OH
Salixin
84
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
H2O, H+
D-Glucose +
HOH2C
HO
HO
O
OH
CHO
O
HOH2C
HO
HO
OH
CH2OH
O
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
85
BI GII:
a. CTPT ca coniin C 8H17N
bt bo ha
2 8 3 1 17
1
2
V coniin khng lm mt mu Br2/CCl4 nen coniin khng cha ni i m cha vng no.
b. S phn ng:
N
H
CH2CH2CH3
-3 H2
xt, t
coniin
amin (II)
CH2CH2CH3
[O]
H
A
amin (III)
COOH
H
B
amin (III)
2 9 2 10
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
86
COOH
CH CH2OH
CH
O2
CHO
Cu, t o
C
COOH
C
H2SO4 d
o
170 C
COOH
CH2
H2
Ni, t
CH3
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:
B (C8H6O3)
A + CH2I2 + NaOH
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:
CH CH CH CH C N
O
************************************************
87
88
************************************************
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 - - - - - - - - - -
89