Tai Lieu Boi Duong Hoc Sinh Gioi 12 Mon Hoa Huu Co PDF

I.
OLYMPIC HO HC VIT NAM:

OLYMPIC HA HC SINH VIN TON QUC 2003:
1) Nh my kh Dinh C x l kh thin nhin thnh hai sn phm: kh ha lng cha trong cc
bnh thp v kh cung cp cho khu in - m Ph M.
a) Hy cho bit thnh phn ha hc chnh ca mi sn phm .
b) V sao khng sn xut ch kh ha lng.
2) Di y cho bit nhit v entanpi ca cc phn ng thun (t tri sang phi)
Phn ng
H(kJ)
2CH4
CH4 + 2O2
CH4 + 1/2O2
CH4 + H2O
CO + H2O
1500oC
500oC
900oC
900oC
900oC
o
400 C
C2H2 + 3H2O
CO2 + 2H2O
CO + 2H2
CO + 3H2
+380,4 (1)
-890,0 (2)
-33,4 (3)
+204,8 (4)
CO2 + H2
-46,0
(5)
CH3OH
-110,8 (6)
CO + 2H2
a) sn xut axetilen theo (1) v sao ngi ta thm mt lng nh oxy vo hn hp phn
ng?
b) c cht u cho sn xut metanol theo phn ng (6) ngi ta nhit phn hn hp metan v
hi nc theo phn ng (4). V sao trong sn xut ngi ta ly t l mol CH4 : H2O = 1 : 2 m
khng phi l 1 : 1? Hn hp sn phm thu c gm nhng kh no?
c) Hy vit phng trnh phn ng ca ankan nhit xp x 900oC vi oxy v vi nc.
d) Theo d n nh my phn m Ph M, hydro c sn xut t kh thin nhin. Trong cc
phn ng to ra hydro cho trn, nn s dng nhng phn ng no?. Khng s dng
nhng phn ng no?, v sao?
e) C hn hp CO + H2 (sn phm phn ng (3) v (4)). Hy ngh phng php tinh ch H2
c th a vo phn ng vi N2 to kh NH3.
BI GII:
1) a) Kh ha lng: propan v butan.
Kh cho in m: metan
b) Metan c nhit ha lng rt thp. Mun ha lng phi lm lnh su, nn p sut cao s
khng kinh t bng dng kh dn bng ng ng cung cp cho nh my in m.
2) a) Phn ng (1) thu nhit mnh, ngoi vic cung nhit t bn ngoi cn t chy mt t CH4 theo
phn ng (3) lun t c v duy tr nht cao 1500oC.
b) Tng nng (p sut ring phn) ca H2O chuyn dch cn bng v pha to thnh sn
phm. Nc r tin hn metan. Nc cn c tc dng gim CO, tng H2 (phn ng 5). Hn hp
sn phm thu c gm CO, H2, H2O (d) v CH4 (d t).
c)
CnH2n + 2 + (n/2)O2 nCO + (n + 1)H2
CnH2n + 2 + nH2O nCO + 2(2n + 1)H2
d) Khng nn dng phn ng (1), ga thnh s rt cao v:
- Tn nng lng thit b chu nhit cao (t, mau hng)
- 2 mol CH4 mi thu c 3 mol H2 (so vi phn ng 3 v 4 u km). Axetilen tuy l nguyn
liu qy, t nhng nu khng c nh my ha cht s dng ti ch th ch dng lm nhin
liu m thi, s lng ph.
Nn s dng kt hp ng thi 3 phn ng (3); (4) v (5), tc l CH4; H2O; O2 s c li v
cc phn ng thu nhit (4) v to nhit (3); (5) b sung cho nhau, u thc hin 900oC tn
nng lng v trang thit b. T 2 mol CH4, mt cch gn ng cho n 6 mol H2.
e) Thm mt lng H2O (c tnh theo thnh phn ca hn hp CO + H2) thc hin phn ng (5)
900oC bin CO thnh CO2, sau lm lnh tch CO2.
1) Ngi ta tin hnh cc phn ng sau y xc nh cng thc cu to ca hp cht thm A
(C9H10O):
- Oxy ha mnh cht A vi KMnO4 m c thu c hai axit C7H6O2 v C2H4O2.
- Cho A phn ng vi metyl magie bromua ri thu phn thu c ancol bc ba (B) c mt
nguyn t cacbon bt i.
a) Vit cng thc cu to v gi tn A.
b) Hy cho bit gc quay mt phng nh sng phn cc ca ancol B bng 0 hay khc 0, v sao?
2) Cho A tc dng vi metyl iodua d trong mi trng baz mnh ngi ta c lp c C (C11H14O).
Hy cho bit tn c ch phn ng. Vit cng thc cu to v gi tn C.
3) Cho ancol B phn ng vi H2SO4 c nng thu c sn phm chnh l E (C10H12). Dng cng thc
khng gian thch hp biu din c ch phn ng to thnh E v gi tn E.
BI GII
1)
a) Ta c:
[O ]
A c nhn benzen, mt mch nhnh, c 1O v mt lin kt i
A C7 H 6O2 + C2 H 4O2
axit benzoic axit axetic
CH3
C6H5
CH2CH3
1) CH3MgBr
2) H3O+
C6H5
CH2CH3 (B)
OH
A: etylphenylxeton
b) B = 0 v CH3MgBr tn cng nh nhau vo hai pha nhm C = O to ra hn hp raxemic.
2)
Ta c:
CH3
OH-
C6H5COCH2CH3
CH3I
SN2
C6H5
CH3
CH3
(C)
tert-butylphenylxeton
3)
C ch:
H 2O +
OH
CH3
CH3
C 6H 5
H + (H 2 S O 4 ); t o
CH3
-H 2 O
H
C 6H 5
CH3
CH3
CH3
C 6H 5
-H +
C 6H 5
C
H 3C
H
C 6H 5
C
CH3
E -2 -p h en y lb u t-2 -en
CH3
CH3

1) Thc hin dy bin ha sau:
+ o
,t o
Ac 2 O
3O ,t
2-metylpropanal HCN
A NH
3
B H
C
C7 H11O2 N
2) Hon chnh cc phng trnh phn ng v gi tn sn phm:
a) Xiclopentadien + HCl kh:
b) Pent-1-en + NBS, a,s
c) Hexa-1,3,5-trien + Br2 (1: 1)
d) 1-(Brommetyl)-2-metylxiclopenten, un nng trong CH3OH
BI GII:
1) Cng thc cu to cc cht l:
A: H3C
C: H3C
H
C
H
C
CH3
H
C
H
C
OH
CH3
NH2
H
C
H
C
H
C
H
C
CH3
OH
CH3
CN
COOH
B: H3C
D: H3C
CN
O
C
O
C
CH3
2) Cng thc cu to cc sn phm:

a)
Cl
3-cloxiclopenten
b) CH3CH2CHBrCH=CH2 (3-brompent-1-en) + CH3CH2CH=CHCH2Br (1-brompent-2-en)
c) CH2=CH-CH=CH-CHBr-CHBr: (5,6-dibromhexa-1,3-dien)
CH2=CH-CHBr-CH=CH-CH2Br: (3,6-dibromhexa-1,4-dien)
BrCH2-CH=CH-CH=CH-CH2Br: (1,6-dibromhexa-2,4-dien)
d)
CH2OCH3
CH2
OCH3
CH3
CH3
1-(metoximetyl)-2-metylxiclopenten
1-metoxi-1-metyl-2-metylenxiclopentan
Hp cht A(C6H12N2O2) quang hot, khng tan trong axit long v baz long, phn ng vi
HNO2 trong nc to thnh B (C6H10O4). 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 nc to thnh D (C4H12N2), hp cht
ny phn ng vi HNO2 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:
C6H12N2O2
NH2
Br2; OH-
CONH2
C4H8
C4H8
H2O
CONH2
NH2
D
D l diamin, deamin ha khi phn ng vi HNO2 v chuyn v ging nh pinacolin. Nh vy c
th vit nh sau:
H
H
H
H
HNO2
H+
H3C C
CH3
C
CH3
H3C C
C
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.
CH3
H
CH3
CONH2
H2NOC
HNO2
CH3
COOH
HOOC
tC
-H2O
H3C
H3C
O
C
O
C
CH3
CH3
H
O
anhydrit-2,3-dimetyl
sucxinic
2) Cng thc Fis:

CH3
H
CH3
CONH2
H2NOC
H
CH3
H2NOC
CONH2
CH3

1) Trong khu cng nghip lc ha du tng lai, d kin c c nh my sn xut PVC.
a) Hy ngh hai s phn ng lm c s cho vic sn xut vinylclorua t sn phm
crackinh 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 vinylclorua nh xc tc TiCl4-Al(C2H5)3 s thu c PVC iu ho lp th c
bn c nhit cao. Hy cho bit trong mch polime y c trung tm bt i khng?.
Vit cng thc lp th mt on mch polime y.
2) T toluen hy vit phng trnh iu ch phlorogluxinol (1,3,5-trihidroxibenzen)
3) Hy tng hp axit glutamic t axit -xetoglutaric.
4) Hy tng hp prolin t axit adipic.
BI GII:
o
C
C2 H 2 + 3H 2 HCl
CH 2 = CH Cl
1) a) A: 2CH 4 1500
Cl2 + H 2 2 HCl
NaCl + H2O dpmn
o
C
C
ClCH 2CH 2Cl 500
CH 2 = CH Cl
B: CH 2 = CH 2 Cl2 ;500
b) Phng php B cn phi x l HCl thu Cl2 v trnh nhim.
o
1
; xt
2 HCl + O2 t
Cl2 + H 2O
2
Chn phng php B v phn ng (1) ca phn ng A hiu sut thp, tiu tn nhiu nng lng
v ga thnh sn phm s cao hn.
c) C nguyn t C bt i:
Cl
Cl H
C
C
H2
CH2
CH2
2) Qa trnh tng hp nh sau:
Cl H
CH2
Cl
CH2
CH3
CH3
COOH
O2N
NO2
O2N
NO2
KMnO4
HNO3
1)Sn + HCl
2) OH-
H2SO4
NO2
NO2
COOH
H2N
COOH
NH2
HN
COOH
NH
+H2O
NH2
NH
HO
OH
-CO2
OH

CH2COOH
H2C
H2SO4
HN3
H2C
CH2COOH
H2C
H2C
COOH
C
H2
(A)
OH-
CH2NH3+
CH2NH2
H+
P, Br2
H2C
H2C
COOH
CH
Br
(B)
NH
COOH
1) SOCl 2
) NH 3
KOH
H 2 NCO(CH 2 ) 4 COOH Br
2 /
A ri tip tc nh trn
hoc: HOOC(CH 2 ) 4 COOH 2

COOH
HCN
CO
(CH2)2
COOH
NH3
COOH
CN
C
NH2
(CH2)2
COOH
COOH
C
-CO2
NH2
to
(CH2)2
H3O+
COOH
COOH
COOH
CHNH2
CH2
CH2
COOH

1) Phn ng ca ancol anlylic vi nc clo to ra C3H7ClO2 (A). Phn ng ca anlyl clorua vi
nc clo th to ra C3H6Cl2O (B). A v B khi ch ha vi dung dch NaOH u to thnh
glixerol nhng A to thm sn phm C3H6O2(D). B to ra sn phm ph C3H5ClO (E). Trn ph
hng ngoi ca D v E u khng c vn hp th vng 1500 1800 cm-1, nhng ph ca D
c vn hp th mnh v t 3100 3400 cm-1 cn ph ca E th khng c:
a) Vit phng trnh phn ng to thnh A, B v cho bit tnh quang hot ca chng.
b) A c 2 nhm OH, hydro nhm OH no linh ng hn.
c) Xc nh cng thc cu to ca D v E.
d) D, E c to thnh t A v B tng ng nh th no, c quang hot khng?
2) T du m, ngi ta tch c cc hydrocacbon A(C10H16); B(C10H18) v C(C10H18). C ba u
khng lm mt mu dung dch brom v ch cha C bc hai v ba. T l gia s nguyn t CIII : s
nguyn t CII A l 2 : 3; cn B v C l 1 : 4. C ba u ch cha vng 6 cnh dng gh.
a) Hy xc nh cng thc cu to v vit cng thc lp th ca A, B v C.
b) So snh nhit nng chy ca A, B, C v nu nguyn nhn.
BI GII:
1) a) CH2 = CHCH2OH + HOCl CH2Cl C*HOH CH2OH (A): hn hp raxemic.
CH2 = CHCH2Cl + HOCl CH2Cl CHOH CH2Cl (B): khng quang hot
b) H ca nhm OH gia linh ng hn v chu hiu ng I mnh hn.
c) Do E khng hp th vng 1500 1800cm-1 chng t chng khng cha lin kt C=C v
C=O suy ra chng c cu to vng. D c vn mng 3100 3400cm-1 cha nhm OH, E th
khng.
So snh thnh phn A vi D, B vi E thy u gim + HCl v ch ha vi NaOH to ra
glixerol (qa th) nn y l iu kin cho phn ng th ch khng pho l cho phn ng tch
HCl (cn iu kin phn cc v un nng). Nh vy chng c cng thc cu to:
*CHCH OH
*CHCH Cl
H2C
H C
2
2
D
E
d) C ch ca cc phn ng nh sau:
H
C
H2C
Cl
CH2OH
H
C
Cl
H2
C
Cl
H
C
-H2O
OH
H2C
OH-
H2
C
Cl
-Cl-
CH2Cl
H
C
H2C
O
O-
raxemic
2) A, B, C khng lm mt mu dung dch brom khng cha lin kt bi m cha vng no.
A c 4 CIII, 6 CII; B v C c 2CIII v 8CII.
Cng thc cu to ca chng:
B, C
A
Cng thc lp th:
C
B
A
A > B > C v tnh gn gng gim theo chiu
1. Vit cng thc Newman v cng thc phi cnh (dng nt m, nt chm ca cc hp cht sau):
tonc:
H
H3C
CH3
C
HO
OH
Br
C
Cl
Br
CH3
Cl
CH3
Br
Cl
(II)
(I)
(III)
2. Vit cc ng phn lp th ca 1 metyl 2,3 dicloxiclopropan.
3. Dng cng thc cu to hon thnh s phn ng sau:
Cl 2 , as
(1)
Cl 2 , Fe
( 2)
KOH / EtOH
( 3)
CH2OH
raxemic
H
C
-H2O
OH
H
C
H2C
O-
OH-
CH2Cl
-Cl-
CH2OH
Mg / ete
( 4)
1) EtMeCHCHO
2) H 3O +
( 5)
CH3
CH3
Cl
H
H OH
(IV)
n C3 H 7C6 H 5 B C
D E F
Cc phn ng u xy ra theo t l 1 : 1, cc cht t B n F u l sn phm chnh. Vit k hu
hoc gi tn c ch cc phn ng (1); (2); (3); (5). Vit tn gi hp cht F v cho bit s
ng phn lp th ca F.
CH2Cl
BI GII:
1. Cng thc Newman v cng thc phi cnh ca cc hp cht (I); (II); (III) v (IV):
H
HO
H3C
Br
CH3
H
H
HOH
H
Br
Cl
Br
C
Cl
CH3 H3C
H
C
CH3
Cl
H3C
Cl
OH
(III)
(IV)
(II)
(I)
2. Cc ng phn lp th ca 1- metyl 2,3 dicloxiclopropan c 4 ng phn.
Nu hai nguyn t clo v tr trans th c hai i quang, cn nu hai nguyn t clo v tr cis th
tu theo v tr ca nhm CH3- m ch c thm hai ng phn (cc ng phn ny c nh qua
gng phng trng vi chng, meso):
Cl
Cl
CH3
H
H3C
Cl
Cl
Cl
Cl
Cl
CH3
H
H
H
3. Cc phng trnh phn ng:
Cl
H
CH3
H2
C
H3C
H2
C
hv
+ Cl2
H2
C
H3C
H
C
+ HCl
(B)
Cl
H2
C
H3C
H
C
H2
C
H 3C
C
H
H
C
Cl
Cl + KOH
C2H5OH
H3C
C
H
C
H
(C)
Cl
(D)
Cl + Mg
C
H
ete
H3C
C
H
+ KCl + H2O
C
H
(D)
MgCl
(E)
O
H 3C
C
H
C
H
H
C
+ C 2H 5
MgCl
(E)
C
H
CH3
OMgCl
H3C
C
H
C
H
H
C
C
H
(E)
C2H5
CH3
OMgCl
H3C
C
H
C
H
C
H
H
C
C2H5 + H+
CH3
OH
H3C
C
H
C
H
C
H
(F)
H
C
CH3
C2H5
+ HCl
(C)
Cl
H
C
Cl
H2
C
H3C
(B)
Cl
H3C
Fe
+ Cl2
+ Mg2+ + Cl-
Cc phn ng xy ra theo c ch:

1) SR hoc th gc t do
2) SE2 hoc th electrophin lng phn t.
3) E1 hoc tch n phn t.
4) AN hoc cng nucleophin.
Tn gi ca F: 2 Metyl 1 - [4 (prop 1 enyl)phenyl]butan 1 ol.
S ng phn lp th ca cht F: 8
1) Hp cht X (C10H16) c th hp th ba phn t hydro. Ozon phn kh ha X thu c axeton,
andehit fomic v 2 oxopentadial.
a) Vit cng thc cu to ca X tho mn tnh cht trn.
b) Hydrat ha hon ton 2,72g cht X ri ly sn phm cho tc dng vi I2/NaOH thu c
15,76g kt ta mu vng. Dng cng thc cu to ca cc cht X vit cc phng trnh
phn ng (ch dng cc sn phm chnh, hiu sut coi nh 100%, C = 12; H = 1; O = 16).
2) T benzen v cc ho cht v c cn thit khc vit s phn ng iu ch naphtalen bng 5
giai on.
3) T 1 amino 1,2 diphenylpropan hy iu ch 1,2 diphenylpropen (c s dng cc ha
cht cn thit).
BI GII:
1. Cht X (C10H16) cng 3H2; sn phm phi c cng thc C10H22. Theo cc sn phm ozon phn
suy ra X c mch h, c 3 lin kt i v to ra 2 mol CH2O nn c hai nhm CH2 = C.
a) Cc cht X tha mn:
H3C
C
CH3
C
H
(CH2)2
(X1)
CH2
HC
CH2
H3C
C
CH3
H3C
CH3 HC
C
H
(CH2)2C
H
(CH2)2
C
H
CH2
(X2)
CH2
CH2
(X2)
b) Hydrat ha X to ra ancol c phn ng iodofom.

MX = 272 nn s mol X l 0,01 mol. S mol CHI3 = 0,04mol. Vy sn phm hydrat ha
X phi c hai nhm CH3-CHOH-. Suy ra ch c cht X2 trn tha mn. Cc phng trnh phn
ng:
CH2
OH
H3C
(CH2)2
C
H
CH2
+ 3HOH
H2SO4 H3C
CH2
CH3 HC
CH3 HC
(X2)
OH
H3C
H
C
(CH2)2
CH3
(CH2)2
H
C
CH3
OH
CH3
OH
OH
H
C
CH3
+12NaOH + 8I2
CH3 HC
H
C
H3C
H
C
CH3
COONa
(CH2)2
COONa
OH
+2CHI3 + 10NaI + 10H2O
OH
2. iu ch naphtalen:
O
O2; V2O5; 400 - 500oC

(1)
C6H6; AlCl3
(2)
HOOC
(3)
HF
H2N - NH2/OH-
Pd,to
(5)
(4)
3. iu ch dn xut propen:
C6H5
H
C
H
C
CH3
NH2
C6H5
CH3I du
C th tin hnh theo s sau:
C6H5
H
C
H
C
CH3
N(CH3)3I
C6H5
Ag2O; to C6H5
C
CH3
C
H
C6H5
C6H5
H
C
H
C
CH3
NH2
C6H5 HNO ; H O
2
2
C6H5
H
C
H
C
CH3
OH
C6H5
H2SO4; to C6H5
C
H
C6H5
CH3

1. Hp cht Y (C6H9Obr) phn ng vi metanol trong mi trng axit sinh ra Z (C8H15O2Br). Cho
Z phn ng vi Mg trong ete khan sau cho phn ng tip vi andehit fomic thu c cht L.
Thy phn L trong mi trng axit thu c M. Dehydrat ha M thu c 2
vinylxiclopentanon.
a) Hy xc nh cng thc cu to ca Y v vit cc phng trnh phn ng.
b) Nu mun iu ch M i t Y, c nht thit phi qua cc giai on nh trn khng?. V sao?
2. Cho bit cng thc cu to v gii thch s to thnh sn phm trong cc phn ng sau:
a) N axetylalanin + SOCl2 C5H7NO2 +
b) Tos NH CH2COOCOOC2H5 + NaOH C18H18N2O6S2 +
BI GII:
1. Cht Z c cha nhiu hn cht Y hai nguyn t C, 6 nguyn t H v 1 nguyn t O, suy ra cht
Y phn ng vi 2CH3OH v tch loi 1 phn t H2O dn n s hnh thnh axetal metylic t Y.
Cht M sau khi dehydrat ha to ra 2 vinylxiclopentanon. Vy M phi c cng thc cu to:
O
H2C
H2
C
suy ra
OH
a) Cc phng trnh phn ng:
Y:
H2C
Br
OMe
O
+ 2CH3OH
+ H2O
OMe
H2C
H2C
Br
OMe
OMe
ete
+ Mg
OMe
H2C
Br
(Z)
(Y)
OMe
Br
H2C
OMe
MgBr
OMe
+ CH2O
OMe
H2C
OMe
MgBr
H2C
H2
C
OMgBr
(L)
OMe
+ 2H2O + H+
+2CH3OH + Mg2+ + Br-
OMe
H2C
H2
C
OMgBr
H2C
H2
C
Al2O3; to
O
H2C
OH
(M)
H2
C
OH
HC
+ H2O
CH2
b) Khi iu ch M i t Y nht thit phi i qua cc giai on trn. V:

Nu khng i qua giai on to ra Z th hp cht c magie s phn ng vi nhm
C = O.
Nu a thm 1C qua phn ng vi KCN th nhm C = O cng c th tham gia
phn ng vi KCN.
2. a) Hp cht C5H7NO2 thuc loi azalacton c cng thc cu to nh sau:
O
O
H3C
CH3
CH
N
S to thnh:
O
H3C
H
C
NH
-SOCl2
H3C
-HCl; SO2
H
C
NH
OH
CH3
H3C
Cl
CH3
O
O
OH
-HCl
CH3
CH
Cl
H3C
CH3
CH
N
b) Hp cht C18H14N2O6S2 phi thuc loi dn xut dixetopiperazin. Cng thc cu to ca cht l:
O
H3C
H2
C
O
O
C
H2
CH3
S to thnh hp cht trn nh sau:

O
Tos
H
N
H2
C
O
Tos
Et
H2
C
C
O
O
C
-H2O
Et + OH
Tos
H2
C
O
H2
C
C
O
C
H2
C
Et
Tos
C
O
O
C
Tos
N
C
H2
+2EtO- + 2CO2
Tos
Et
K THI CHN HC SINH GII QUC GIA NM 2002:

1. Khi xiclotrime ho 1,3-butatrien vi s c mt ca cht xc tc c kim, ngi ta iu ch c
(Z, E, E)-1,5,9-xiclododecatrien. y l mt phng php n gin iu ch hidrocacbon vng
ln. Khi dng cht xc tc thch hp l cc phc -alyl ca kim loi chuyn tip ngi ta iu ch
c (E, E, E)-1,5,9-xiclododecatrien v (Z, Z, E)-1,5,9-xiclododecatrien. Hy vit cng thc cu
to ca 3 hp cht trn.
2. Sp xp s tng dn tnh baz (c gii thch) ca cc cht trong tng dy sau:
(a) CH3-CH(NH2)-COOH, CH2=CH-CH2-NH2, CH3-CH2-CH2-NH2, CHC-CH2-NH2 .
-NH-CH3 ,
-CH2-NH2 , C6H5-CH2-NH2, p-O2N-C6H4-NH2
BI GII:
1. Cng thc cu to ca ba cht :
Z, Z, E
E, E, E
Z, E, E
2. Trt t tng dn tnh baz :

(a) CH3-CH-COOH < CHC-CH2-NH2 < CH2=CH-CH2-NH2 < CH3-CH2-CH2-NH2
NH2
Tn ti dng
ion lng cc
(b) O2N(A)
m in CSP >
-NH2 <
CSP2
-CH2-NH2 <
(B)
>
CSP3
-CH2-NH2 <
(C)
-NH-CH3
(D)
Nhm p-O2N-C6H4- Nhm -C6H4-CH2- Nhm -CH2- Nhm C6H11ht electron mnh do ht e yu
y e, lm tng
v -CH3 y e,
c nhm -NO2 (-I -C)
mt e trn
- Amin bc II
lm gim nhiu mt
nhm NH2
e trn nhm NH2
1. Vit cc phng trnh phn ng theo s chuyn ho sau (cc cht t A, ... G2 l cc hp cht hu
c, vit dng cng thc cu to):
Fe
Cl2 (1 mol) Mg
1) Etilen oxit H 2SO4
Br2 (1 mol)
E1 + E2
C6H5-CH3
A
B
C
D
(1 mol) a.s.
ete khan 2) H2O/H+
15OC (1 mol)
a.s. G1 + G2
2. (3,5 im). Vit s phn ng iu ch cc hp cht sau y, ghi r cc iu kin phn ng (nu
c):
a) T etanol v cc ho cht v c cn thit, iu ch:
(A) Propin (khng qu 8 giai on).
(B) 1,1-dicloetan (qua 4 giai on).
b) T benzen v cc cht v c, hu c (cha khng qu 3 nguyn t cacbon), iu ch:

(C)
(D)
BI GII:
1. Cc phng trnh phn ng:
C6H5-CH3
a.s
+ Cl2 (1 mol)
C6H5-CH2Cl + HCl
ete khan
C6H5-CH2Cl + Mg
C6H5-CH2MgCl
1) CH2_ CH2
C6H5-CH2MgCl
C6H5
H2
C
H2
C
2) H2O/H+
C6H5-CH2-CH2-CH2-OH
H2SO4; 15OC
CH2OH
+ HBr
Fe
+
Br
Br2
+
Br
HBr
Br
+ HBr
as
+
H2O
Br2
Br +
HBr
2. a)
CH3CH2OH
-H2O
H2C CH2
1) O3
2) Zn
HCHO
HX
CH3CH2X
Mg
CH3CH2MgX
HCHO
CH3CH2CH2OH
-H2O
CH3CH=CH2
Br2
CH3CHBrCH2Br
1) NaNH2 hay KOH/ancol

H3C C CH
2) H2O
CH3CH2OH
-H2O
H2C CH2
Br2
CH2BrCH2Br
1) NaNH2 hay KOH/ancol

2) H2O
HC CH
2HCl
CH3CHCl2
b)
OH
CH3Cl
AlCl3
1) HBr
2) Mg/ete
CH3
H2/Ni
Cl2/as
C6H5CH2CH2CH2MgBr
OH
[O]
CuO
CH2Cl
Mg/ete
1) CH3COCH3
2) H3O+
CH2OHCH2OH
H+
CH2MgCl
O
O
(C)
1) etylenoxit
2) H2O
H2 H2 H2 CH3
H2SO4
C C C C CH3
OH
C6H5CH2CH2CH2OH
(D)

Hp cht hu c A c cng thc phn t C7H9N. Cho A phn ng vi
C2H5Br (d), sau vi NaOH thu c hp cht B c cng thc phn t C11H17N. Nu cng
cho A phn ng vi C2H5Br nhng c xc tc AlCl3 (khan) th to ra hp cht C c cng cng thc phn
t vi B (C11H17N). Cho A phn ng vi H2SO4 (c) 180oC to hp cht D c cng thc phn t
C7H9O6S2N, sau khi ch ho D vi NaOH 300oC ri vi HCl s cho sn phm E (E c phn ng mu
vi FeCl3). Mt khc, nu cho A phn ng vi NaNO2 trong HCl 5oC, ri cho phn ng vi -naphtol
trong dung dch NaOH th thu c sn phm c mu G.
Xc nh cng thc cu to ca A, B, C, D, E, G v vit cc phng trnh phn ng (nu c) minh
ho.
BI GII:
Hp cht hu c A c cng thc phn t C7H9N, s nguyn t C ln hn 6 v gn bng s
nguyn t H. Vy A c vng benzen.
A phn ng vi NaNO2 trong HCl 5oC, ri cho phn ng vi -naphtol trong dung dch NaOH
th thu c sn phm c mu G, chng t A c nhm chc amin bc I v A cn c nhm metyl.
A phn ng vi H2SO4 (c) 180oC to hp cht D c cng thc phn t C7H9O6S2N, y l
phn ng sunfo ho nhn thm, c 2 nhm -SO3H nn nhm metyl s v tr para v ortho so vi nhm
amin.
Sau khi ch ho D vi NaOH 300oC ri trung ho bng HCl s cho sn phm c nhm chc
phenol E (E c phn ng mu vi FeCl3).
A phn ng vi C2H5Br nhng c xc tc AlCl3 (khan) to ra hp cht C c cng cng thc phn
t vi B (C11H17N), l sn phm th vo nhn benzen, v v tr para so vi nhm -NH2 c nhm CH3 nn nhm -C2H5 s th vo v tr ortho.
Cc amin bc I rt d tham gia phn ng th nguyn t nit bng cc dn xut halogen to
ra cc amin bc II hoc bc III (sau khi x l bng kim). A phn ng vi C2H5Br (d) nn sn phm
B c cng thc phn t C11H17N s l N,N-dietylanilin.
Cng thc cu to ca A, B, C, D, E, G v cc phng trnh phn ng:

1) C2H5Br d
2) NaOH
NH2
CH3
(A)
H3C
C2H5Br/ AlCl3 khan
H5C2
H2SO4 c/180 C HO3S
N(C2H5)2 (B)
NH2
C2H5
CH3
NH2
(C)
SO3H1) NaOH, 300 C HO

2) H+
CH3 (D)
ONa
NH2
OH
CH3 (E)
NaNO2 + HCl, 5OC

H3C
N=N
-naphtol/NaOH
(G)
Thu phn mt protein (protit) thu c mt s aminoaxit c cng thc v
pKa nh sau:
Ala CH3CH(NH2)COOH (2,34; 9,69);
Pro
COOH (1,99; 10,60);
Ser HOCH2CH(NH2)COOH (2,21; 9,15);
N
Asp HOOCCH2CH(NH2)COOH (1,88; 3,65;9,60); H
Orn H2N[CH2]3CH(NH2)COOH (2,10; 8,90; 10,50);
Arg H2NC(=NH)NH[CH2]3CH(NH2)COOH (2,17; 9,04; 12,48);
1. Vit tn IUPAC v cng thc Fis pHI ca Arg, Asp, Orn. Trn mi cng thc hy ghi (trong
ngoc) gi tr pKa bn cnh nhm chc thch hp. Bit nhm -NHC(=NH)NH2 c tn l guanidino.
2. Ala v Asp c trong thnh phn cu to ca aspactam (mt cht c ngt cao hn saccaroz ti 160
ln). Thu phn hon ton aspactam thu c Ala, Asp v CH3OH. Cho aspactam tc dng vi 2,4dinitroflobenzen ri thu phn th c dn xut 2,4-dinitrophenyl ca Asp v mt sn phm c cng
thc C4H9NO2. Vit cng thc Fis v tn y ca aspactam, bit rng nhm -COOH ca Asp
khng cn t do.
3. Arg, Pro v Ser c trong thnh phn cu to ca nonapeptit bradikinin. Thu phn bradikinin sinh ra
Pro-Pro-Gly ; Ser-Pro-Phe ; Gly-Phe-Ser ; Pro-Phe-Arg ; Arg-Pro-Pro ; Pro-Gly-Phe ; Phe-Ser-Pro.
a) Dng k hiu 3 ch ci (Arg, Pro, Gly,...), cho bit trnh t cc aminoaxit trong phn t bradikinin.
b) Vit cng thc Fis v cho bit nonapeptit ny c gi tr pHI trong khong no? ( 6; <6; << 6; > 6;
>> 6).
BI GII:
1. Aminoaxit sinh ra t protein u c cu hnh L
COO (2,17)
COO (1,88)
H2N
H
H3N
H
(9,04)
(9,60)
[CH2]3-NH"C"NH2
CH2COOH
NH2
(3,65)
(12,48)
Axit (S)-2-amino-5Axit (S)-2-aminoguanidinopentanoic
butandioic
COO (2,10)
H2N
H
(8,90)
[CH2]3-NH3
(10,50)
Axit (S)-2,5-diaminopentanoic
COOCH3
2. Aspactam H2N-CH C NH CH-COOCH3

CH2COOH CH3
3. Bradikinin
O=C NH
H
H2N
H
CH3
Metyl N-(L--aspactyl) L-alaninat CH2COOH
Arg-Pro-Pro-Gly-Phe-Ser-Pro-Phe-Arg
pHI >> 6 v phn t cha 2 nhm guanidino, ngoi ra cn c 3 vng piroliddin
COOH
CO-NHH
CO-NHH [CH2]3NHC(=NH)NH2
CO-N H CH2C6H5
CO-NHH
CO-NH-CH2-CO-NHH CH2OH
CH2C6H5
CON H
CO-N H
NH2H
[CH2]3NHC(=NH)NH2
1. Oxi ho 150 mg amiloz bi NaIO4 thu c 0,0045 mmol axit fomic.
(a) Tnh s lng trung bnh cc gc glucoz trong phn t amiloz; bit rng khi
CHO
oxi ho 1 mol amiloz bng NaIO4, s gc glucoz u mch to ra 1 mol axit
H
OH
H
HO
fomic, s gc glucoz cui mch to ra 2 mol axit fomic.
O
H
H
(b) Vit s cc phng trnh phn ng xy ra.
H
HO
2. Vit s cc phng trnh phn ng chuyn D-glucoz thnh L-guloz c cng
C H 2O H
thc bn.
L -g u lo z a
BI GII:
1. (a) S lng trung bnh cc gc glucoz trong phn t amiloz :
4
3HCOOH
(C6H10O5)n HIO
1
3
n amiloz = n HCOOH =
0,0045
= 0,0015( mmol)
3
150
= 100000
0,0015
100000
617
n=
162
(b) Phng trnh phn ng:
M amiloz =
CH2OH
O
OH
CH2OH
O
OH
OH
O
n-2
OH
OH
CH2OH
O
OH
OH
OH
+ (n+4) HIO4
- 3 HCOOH
HCHO
(n+4) NaIO3
OHC
CH2OH
O
CH2OH
O
OHC
CH HC
O
O
CHO
O
n-2
CHO
2. S chuyn ha :
H
HO
H
H
- H2O
CHO
OH
+ HNO3
H
OH
OH
CH2OH
CH2OH
H
OH
H
H
OH
H
OH
CO
H
HO
H
H
COOH
OH
H
OH
OH
COOH
+ Na(Hg)
pH = 7
- H2O
H
HO
H
H
H
HO
H
H
CO
CH2OH
OH
OH
H
O
H
H
+ Na(Hg) HO
H
OH
OH
H
OH
COOH
COOH
CH2OH
OH
H
OH
OH
CHO

1. Khi c mt enzim aconitaza, axit aconitic b hidrat ha to thnh axit A khng quang hot v axit B
quang hot theo mt cn bng:
COOH
H2O
HOOC
H2O
A
B
C
C
(C6H8O7)
(C6H8O7)
CH2COOH
H
6%
90%
Axit aconitic
4%
a) Vit cng thc cu to ca A v B, ghi tn y ca chng v ca axit aconitic theo danh php
IUPAC. Axit A c pKa: 3,1 ; 4,8 ; 6,4. Ghi cc gi tr pKa bn cnh nhm chc thch hp.
b) Vit s iu ch A t axeton v cc cht v c cn thit.
2. Ozon phn mt tecpen A (C10H16) thu c B c cu to nh sau:
. Hidro ha A vi xc tc kim loi to ra hn hp sn
CH3 C CH2 CH
CH CH2 CH O phm X gm cc ng phn c cng thc phn t
C10H20.
C
O
H3C
CH3
a) Xc nh cng thc cu to ca A.
b) Vit cng thc cc ng phn cu to trong hn hp X.
c) Vit cng thc lp th dng bn ca cc ng phn trong hn hp X.
BI GII:
1. a)
HOOC CH CH CH2COOH HOOC
COOH
C
OH COOH
(3,1) COOH
H2O
HOOC-CH2 C CH2COOH
4,8(6,4)
OH 6,4(4,8)
(B)
Axit (Z)-3-cacboxipentendioc
(A)
Axit-3-cacboxi-2-hidroxipentadioic
Axit-3-cacboxi-3-hidroxipentadioic
H2O
CH2COOH
b)
CH3
C O
CH2Cl
Cl2
CH3COOH
HCN
C O
CH2Cl
CH3
2.a)
CH2Cl
HO C CN
KCN
CH2CN
HO C CN
CH2Cl
H3O+
CH2COOH
HO C COOH
CH2COOH
CH2CN
b)
+2H2
(vng 7 cnh km bn hn vng 6 cnh)

c) ng phn lp th dng bn:
4
;
1
1
(e e > a a)
(e e > a a)
3
4
;
1
(a e > e a)
(a e > e a)
(e e > a a)
3
1
(a e > e a)

1. Hp cht A (C5H11O2N) 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 HNO2 thu c hn hp gm ancol C quang hot v
ancol tert-amylic (2-metyl-2-butanol).
Xc nh cng thc cu to ca A. Dng cng thc cu to, vit phng trnh cc phn ng to
thnh B, C v ancol tert-amylic t A.
2. Hp cht A (C5H9OBr) khi tc dng vi dung dch iot trong kim to kt ta mu vng.
A tc dng vi dung dch NaOH to ra 2 xeton B v C cng c cng thc phn t C5H8O. B, C u
khng lm mt mu dung dch kalipemanganat lnh, ch c B to kt ta mu vng vi dung dch iot
trong kim. Cho B tc dng vi CH3MgBr ri vi H2O th c D (C6H12O). D tc dng vi HBr to ra
hai ng phn cu to E v F c cng thc phn t C6H11Br trong ch c E lm mt mu dung dch
kali pemanganat lnh.
Dng cng thc cu to, vit s phn ng t A to thnh B, C, D, E, F. Vit tn A v D theo
danh php IUPAC.
BI GII:
*
1.
CH3 CH CH2 CH3
CH3 CH CH2 CH3
CH2NO2
CH2NH2
H2/ Ni
CH3 CH CH2 CH3

+
HNO2
CH2
CH3 CH CH2 CH3

CH2OH
H2O
(A)
*
CH3 CH CH2 CH3
CH2
chuyn v
CH3
+
C
CH2 CH3
OH
H2O
CH3 C
CH3
CH2 CH3
CH3
2.
CH3
C CH2 CH2 CH2

O
Br
H2O
CH3
OH
C CH
O
CH2
2) H2O
CH3
C
OH
(B )
C CH2 CH2 CH2
(C)
Br
Br
CH3
1) CH3MgBr
CH3 C
Br
CH3 C
Br
CH2 CH2
CH3
H2O
CH3
HBr
(E )
C
Br
(D )
+
CH3
CH3 C
CH
CH2 CH2
Br
(F )
OH
CH3
H2O
CH3
+
+H
CH3
Tn gi :
Br
+
C
CH3 C
CH3 chuyn v
A : 5-brom 2 pentanol ;
CH2 CH2
CH
CH3
Br
D : 2 xiclopropyl 2 propanol

1. Hy ngh s phn ng vi y iu kin :
a) t etylen v cc cht v c tng hp cc hp cht sau v sp xp chng theo th t tng dn nhit
si:
C2H5OCH2CH2OCH2CH2OH (Etylcacbitol) ;
O
O
O
NH
b) T benzen hoc toluen v cc cht v c tng
hp
Dioxan
Mopholin
c cc dc cht sau: Axit 4-amino-2hidroxibenzoic; axit 5-amino 2,4 dihidroxibenzoic.
2. a) Dng cng thc cu to, hy hon thnh s tng hp sau y:
2
6 5
2
C8H8O4NSCl
B
COCl2 + CH3OH
C2H3O2Cl
HOSO Cl
C H NH
NH 3
H 3O
C6H8O2N2S.
b) Gii thch hng ca phn ng to thnh C8H8O4NSCl v C6H8O2N2S.

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

COOH
NO2
HNO3
NH2
Sn/ HCl
OH
HNO2
H2SO4, t0
b)
OH
CO2,OH
t ,p
NO2
NH2
NH2
NH2
COOH
NH2
OH
HNO2
OH
CO2,HO
OH
OH Sn /HCl
HNO3
H2SO4, t0
t,p
NH2
COOH
COOH
OH
H2N
O2N
OH
OH
OH
hoc
CH3
CH3
COOH
NO2
COOH
NO2
K 2Cr2O7
H+
HNO3
H2SO4, t0
NH2
Sn / HCl
NO2
COOH
OH
HNO2
NO2
NH2
OH
COOH
COOH
OH
HNO3
OH
Sn / HCl
H2SO4
O2N
H2N
OH
OH
2. a) COCl2 + CH3OH
CH3O-COCl
NHCOOCH3
C6H5NH2
CH3OCOCl
HOSO2Cl
NHCOOCH3
NH3
NHCOOCH3
NH2
H3O
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.
NHCOOCH3 este-amit thy phn thnh CO2 , cn SO2NH2 bn hn.

TRF l tn vit tt mt homon iu khin hot ng ca tuyn gip. Thy phn hon ton 1 mol
TRF thu c 1 mol mi cht sau:
N
CH2-CH-COOH
NH3 ;
; HOOC-CH2-CH2-CH-COOH ;
NH2
COOH
NH2
N
N
(Pro)
(His)
(Glu)
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 pKa1 = 1,8 ; pKa2 = 6,0 ; pKa3 = 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 = (pKa1+pKa2+pKa3) : 3 ; pHI = (pKa1+pKa2) : 2 ; pHI = (pKa2+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 amit vng (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:
NH2
CO
N
CO
NH
O
NH
CO
H
CH2
N
NH
2. Cn bng in ly ca His:
COOH
+
COO
+
H3 N
-H
CH2
H3 N
-H
H
CH2
(2)
HN
H3 N
CH2
(1)
HN
1,8
H2N
CH2
N
NH
(+2)
-H
(3)
NH
COO
COO
NH
NH
6,0
(+1)
(-1)
(0)
(hoc vit 3 cn bng ring r; khng cn cng thc Fis)

* pHI = (pKa2 + 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
HCN, NH3
2
NC CH2 CH2 CH=O
NC CH = CH2
xt, t 0
CO, H
C CH2 CH2 CH C N
1) H2O, OH
+
2) H3O
HOOC CH2 CH2 CH COOH
NH2
NH2
Disaccarit X (C12H22O11) khng tham gia phn ng trng bc, khng b thy phn bi enzim
mantaza nhng b thy phn bi enzim emulsin. Cho X phn ng vi CH3I ri thy phn th ch c
2,3,4,6-tetra-O-metyl-D-guloz. Bit rng: D-guloz l ng phn cu hnh C3 v C4 ca D-glucoz;
mantaza xc tc cho s thy phn ch lin kt -glicozit, cn emulsin xc tc cho s thy phn ch lin
kt -glicozit.
1. Vit cng thc lp th ca X.
2. Deoxi- D-guloz A (C6H12O5) c chuyn ha theo 2 hng sau:
HIO4
+
CH3OH, H
1) LiAlH4
2) H2O
H3O+
Glixerin, 3-hidroxipropanal
B
HBr
C6H11BrO4 (E)
KOH
C6H10O4 (F)H2O/ DCl hh
a) Xc nh cng thc cu to ca A.
b) Vit cng thc cu to ca B, C, D, E, F.
c) Xc nh cng thc cu to cc cht c trong hn hp G, bit phn t khi ca chng u ln hn 160
v nh hn 170 vC.
BI GII:
1. *T D-glucoz suy ra cu hnh ca D-guloz. X khng kh nn c lin kt 1,1-glicozit.

* S thy phn ch bi emulsin chng t tn ti lin kt 1 -1 -glicozit.
CH2OH
O
HO
OH
HO
HO
HOCH2
O
OH
OH
CH2OH
HO
OH
O
HO
O
CH2OH
O OH
OH
OH
hoc
2. *a) b) T hng chuyn ha th nht xc nh c cng thc cu to ca A.
CH2OH
O
CH2OH
CH2OH
HO
OH
CH3OH
HO
HIO4
OH
HOC
OCH3
OH
HOC
(C)
CH2OH
O
HBr HO
OH
Br
(B)
(A)
OH
CH2OH
CH2OH
O
LiAlH 4
OCH3
HOC
HOC
HOCH2
(C)
OCH3
HOCH2
CH2OH
Br
CH2OH
CHOH
CH2OH
(D)
CHO
+ CH2
CH2OH
KOH
HO
H2O/ DCl
(E)
OH
H3O+
CH2OH
HO
(E)
OH
(G)
(F)
c) H2O + DCl HOD + HCl

V H+ hoc D+ u c th tn cng electrophin, sau H2O hoc HOD tn cng nucleophin nn
thu c c 4 cht:
CH2OH
CH2OH
O
HO
HO
HO
OD
OD
CHD
CH2
HO
OH
OH
CHD
CH2
OH
OH
CH2OH
CH2OH
OH
OH
(G4) 166
(G1) 164
(G2) 165
(G3) 165
K THI CHN HC SINH GII QUC GIA NM 2004 (Bng A):
1. 3-metylbuten-1 tc dng vi axit clohidric to ra cc sn phm, trong c A l 2-clo-3-metylbutan
v B l 2-clo-2-metylbutan. Bng c ch phn ng, hy gii thch s to thnh hai sn phm A v B.
2. 2-metylbuten-2 phn ng vi axit clohidric. Trnh by c ch ca phn ng, cho bit sarn phm chnh
v gii thch?
3. Trong phn ng clo ho nh cht xc tc FeCl3 , kh nng phn ng tng i cc v tr khc nhau
trong cc phn t biphenyl vad benzen nh sau:
0
250
250
790
1
790
250
250
1
1
a) Trnh by c ch phn ng clo ho biphenyl theo hng u tin nht.

b) Tc monoclo ho biphenyl v benzen hn km nhau bao nhiu ln?
c) Trong mt phn ng clo ho biphenyl thu c 10 gam 2-clobiphenyl, s thu c bao nhiu gam 4clobiphenyl?
BI GII:
1.
CH3
CH3
CH3-CH-CH=CH2
+
CH3-CH-CH2-CH2 (I)
CH3
CH3-CH-CH-CH3 (II)
+
Cl
CH3
chuyn v
CH3
CH3-C-CH2-CH3 (III)
+
Cl CH3
CH3-CH-CH-CH3
CH3-C-CH2-CH3
Cl
2-Clo-3-metylbutan
Cl
2-Clo-2-metylbutan
Do cacbocation bc hai (II) c kh nng chuyn v hidrua to thnh cacbocation bc ba (III) nn to

thnh hai sn phm A, B.
2.
CH3
CH3
CH3-C=CH-CH3
CH3-C-CH2-CH3
+
H+
(I)
CH3
Cl -
CH3-C-CH2-CH3
Cl
CH3
CH3-C-CH-CH3
+
(II)
2-Clo-2-metylbutan
CH3
CH3-CH-CH-CH3
Cl
2-Clo-3-metylbutan
Cl -
2-Clo-2-metylbutan l sn phm chnh.

Do cacbocation bc ba (I) bn hn cacbocation bc hai (II), mt khc do cacbocation bc hai (II) c kh
nng chuyn v hidrua to thnh cacbocation bc ba (I) nn sn phm 2-clo-2-metylbutan l sn phm
chnh.
3.
a) C ch SE2 , u tin vo v tr cacbon s 4.
Cl2 + FeCl3
Cl+FeCl4-
b)
Cl +
chm
Cl
kbiphenyl
c)
kbenzen
(250 4) + (790 2)
16
430
1
790 2
250 4
x
10
nhanh
-
Cl
H+
Tc monoclo ho ca biphenyl hn
benzen 430 ln.
t x l s gam 4-clobiphenyl, ta c:
790 2 10
1000
15,8
(g)

1. T etilen v propilen c xc tc axit, platin v iu kin cn thit, hy vit s tng hp isopren.
2. Cho s sau:
O
Xiclohexanol HBr
1. Li
2. CuI
3.
Br
CH2
CH2
NBr
O
N H /O
B (NBS) C 2 4 2
D KOH
C2H5OH
Vit cng thc cc sn phm hu c A, B, C v D.

3. T axetilen v cc ho cht v c cn thit, hy vit cc phong trnh phn ng tajo ra p(dimetylamino)azobenzen:
CH3
N
BI GII:
1.
CH3
H+
CH2=CH2
+
CH3-CH2
CH3-CH2
CH2=CH-CH3
CH3-CH=CH2
H+
cacbocation ny alkyl ha propen
+
CH3-CH2-CH2-CH-CH3
- H+
+
CH3-CH2-CH-CH2
CH3
- H+
CH3-CH2-CH=CH-CH3
CH3-CH2-C=CH2 (II)
CH3
+
CH3-CH2-CH2
CH2=CH2
+
CH3-CH2-CH2-CH-CH2
+
CH3-CH-CH3
CH2=CH2
+
CH3-CH-CH2-CH2
CH3
+
CH3-CH2-CH2-CH-CH2
- H+
+
CH3-CH-CH2-CH2
CH3
CH3-CH2-CH2-CH=CH2
-H
CH3-CH-CH=CH2
CH3
(IV)
Tch (II) v (IV) ra khi hn hp:
CH3-CH2-C=CH2
CH3
(II)
Pt , to
CH2=CH-C=CH2
CH3
- H2
(IV)
CH3-CH-CH=CH2
CH3
(Nu hc sinh lm theo cch khc cng ra sn phm th cho na s im theo biu im)
2.
Br
Br
Br
A
B
C
D
Monosaccarit A (t l glicoz A) c tn l (2S,3R , 4S , 5R)2,3,4,5,6
pentahidroxihexanal. Khi un nng ti 1000C, A b tch nc sinh ra sn phm B c tn l 1,6
anhidroglicopiranoz. Dglucoz khng tham gia phn ng ny. T A c th nhn c cc sn phm E
(C5H10O5) v G (C5H8O7) theo s phn ng:
Br2
H2O
CaCO3
H2O2
HNO3
1. Vit cng thc Fis ca A v B.

2. A tn ti 4 dng gh (D-glicopiranoz). Vit cng thc ca cc dng v cho bit dng no bn
hn c?
3. Dng cng thc cu dng biu din phn ng chuyn ho A thnh B. V sao
Dglucoz khng tham gia phn ng tch nc nh A?
4. Vit cng thc cu trc ca E v G. Hy cho bit chng c tnh quang hot hay khng?
BI GII:
3.
NH2
NO2
6000C, XT
3 CH CH
HNO3 + H2SO4
;
(I)
CH CH
H2O
Hg
2+
CH3CHO
(III)
(II)
Ag2O/NH3
Cl2, a.s
CH4
Fe/HCl
CH3COOH
CH3Cl
NaOH
CH3COONaCaO.NaOH
t0
HCl
(IV)
Cho (III) phn ng v i (IV)

NH2
CH3
N
CH3
+ 2CH3Cl 2NaOH
NH2
2NaCl
2 H2O
N 2+
NaNO2 HCl
0-50C
CH3
N CH3
N 2+
Cu III (3,5 im):

1.
CHO
HO
OH
HO
OH
C6H5 N=N-C6H4 N(CH3)2
1. 0,75 im ; 2. 1,25 im ; 3. 0,75 im ; 4. 0,75 im
CH
HO
OH
100 C
HO
+ H2O
CH2OH
O-CH2
HO OH
OH
O
OH
OH
C1 -
OH
O
HO
HO
OH 1 C -
CH4
HO
OH
HO OH
OH
O
C1 -
HO
OH
HO
HO
HO
3.
1 C - Bn nht v s lin kt e OH nhiu nht

O
OH
O
OH
OH
1C-
HO
1000C
HO
OH
OH
+ H2O
HO
HO
D- Glucoz khng phn ng tch nc v cc nhm OH C1 v C6 lun xa nhau.
CHO
COOH
4.
OH
OH
HO
HO
OH
OH
COOH
CH2OH
Quang hot
Khng quang hot
.
Cu IV (4 im):
1. T nha thng ngi ta tch c xabinen v chuyn ho theo s sau:
1) O3 ; 2) Zn/HCl
(1)
H2N
A
OH (4)
KMnO4 ,H+
(2)
B
P2O5
H2/ Ni , t0
(5)
(3)
C1 , C2 , C3
A c cng thc C9H14O.

a) Vit cng thc cu to ca cc sn phm hu c: A , B , C1 , C2 , C3 , D , E .
b) Sn phm no c to thnh ng phn v ch r s lng ng phn ca mi sn phm.
2. Pirol l mt hp cht d vng vi cu trc nu trong hnh v. Pirol phn ng vi axit
nitric khi c mt anhidrit axetic to thnh sn phm X vi hiu
H
H
sut cao .
a) Vit phng trnh phn ng to thnh X .
H
H
N
b) Phn ng ny thuc loi phn ng g ? Gii thch da trn cu
to ca pirol.
H
c) Gii thch v tr ca pirol b tn cng khi tin hnh phn ng ny bng cc cht trung gian v bn
ca chng.
d) So snh phn ng nu trn vi phn ng nitro ha ca benzen v toluen bng hn hp HNO3 /H+.
BI GII:
1.
O
COOH
COOH
C1
COOH
COOH
C2
COOH
COOH
O
C O
C3
HON
COOH
COOH
C3 c 2 ng phn quang hc.

C2 c 4 ng phn quang hc.
D c ng phn E, Z.
2. a)
Anhidrit axetic
HNO3
H N
N H
NO2 + CH3COOH
b) y l phn ng th electrophin v pirol l mt hp cht d vng c tnh thm do c 2 cp electron

v cp electron cha tham gia lin kt ca nit.
N H
N H
N H
H N
H N
c) Phn ng th electrophin ca pirol v v tr ortho i vi nguyn t nit, tc l cacbon cnh

nguyn t nit do cacbocatron trung gian bn hn nh 3 cu trc lin hp
NO2
NO2
N H H
N
H
NO2
N
H
Nu nhm NO2 tn cng cacbon s 3 so vi nit ch c 2 cu trc lin hp km bn v khng u
tin.
+
NO2
NO2
d)
NO2
+ HNO3 + H+
CH3
CH3
CH3
NO2
+ HNO3 + H
Ho
c
NO2
Do hiu ng lin hp ca i electron khng lin kt trn nit ca pirol nn vng pirol c mt
electron cao hn so vi vng benzen v vy phn ng th electrophin ca pirol d hn ca benzen.
Vng benzen ca toluen c thm nhm CH3 y electron nh hng nhm NO2 vo v tr ortho nh
pirol hoc c th nh hng vo para.
1. Cc aminoaxit phn ng vi nhau to thnh
NH2
polipeptit. Hy cho bit cu trc ca cc dipeptit to N
CH2 CH COOH
thnh t leuxin (CH3)2CHCH2CH(NH2)COOH v
N
histidin (hnh bn).
H
Histidin
2. Gi A, B l cc -aminoaxit mi trng axit, baz tng ng vi X l ion lng cc.

a) Xc nh t s nng ca A v B im ng in.
b) Vt alanin chuyn v cc no khi pH < 5 v pH > 8?
c) Xc nh hm lng tng i ca ion lng cc X ca alanin im ng in, bit rng hng s
axit ca alanin: pK1 = 2,35 i vi cn bng A
X + H+
pK2 = 9,69 i vi cn bng X
B + H+ .
BI GII:
1. Cu trc ca cc dipeptit :
( CH3)2CH - CH2 - CH(NH2) - CO - NH - CH - CH2

H - Leu - His - OH
COOH
N
HN
CH2 - CH(NH2) - CO - NH - CH - CH2 - CH(CH3)2
N
NH
H - His - Leu - OH
COOH
H
N
O
CH2
N
H
NH
CH2 CH CH3
CH3
O
His-Leu
Leu - Leu ( CH3)2CH - CH2 - CH - CO - NH - CH - CH2 - CH(CH3)2

N
His - His
COOH
NH2
CH2 - CH - CO - NH - CH - H2C
N
H
COOH
NH2
N
HN
2.
a) Vt ca aminoaxit im ng in khng dch chuyn v pha catot cng nh anot nn nng
cc ion tri du phi bng nhau :
[A]
[A] = [B] nn t s bng n v;
(1)
=1
[B]
b) Lp biu thc tnh cc hng s axit

K1 =
[X ][H + ]
[A]
pHI =
; [H+] =
K1[A]
(2) K2 =
[X ]
[H+]2 =
K1K 2 [A][ X ]
[X ][B]
pK1 + pK 2
2
[B][H + ] ;
[X ]
[H+] =
K 2 [X ]
[B]
(3)
t (1) , (2) , (3) c [H+] = (K1K2)1/2
i vi alanin: pHI =
2,35 + 9,69
2
= 6,02
V im ng in ca alanin l 6,02 nn vt di chuyn v pha cc m khi pH < 5, v

theo hng cc dng khi pH > 8
c) T (2):
[X ] =
[A ]
K1
10 2,35
=
= 4680
K2
10 9, 69
Nh vy nng tng i ca [X] l:
[X ]
1
=
= 0,9996
[A] + [B] + [X ] 2 [A] + 1
[X ]
~1
K THI CHN HC SINH GII QUC GIA NM 2004 (Bng B):

Phn tch nguyn t mt hp cht hu c A ch cha C, H v O c 70,97% C v 10,12% H.
a) Xc nh cng thc phn t ca A, bit khi lng mol ca A l 340 gam.

b) Thc nghim cho bit: A tc dng vi axit to este; hidro ho A c xc tc Pd to hp cht X; X cng
tc dng vi axit to este; oxi ho X bng KMnO4 to thnh CO2 v mt axit dicacboxylic mch di.
Da vo cc tnh cht ho hc trn, hy a ra mt cu to ph hp c th c ca X, A vi cu trc i
xng v mch cacbon khng phn nhnh. Vit cc phng trnh phn ng (dng cng thc thu gn).
gii thch.
BI GII:
a) Lng C chim 70,97%, trong 340 g A c 241,3 g S nguyn t C 20
Lng H chim 10,12%, trong 340 g A c 34,4 g S nguyn t H 34
Lng O trong 340 g A c 64,3 g S nguyn t O 4.
Vy cng thc phn t gn ng ca A l: C20H34O4 (M = 338)
b) A v X tc dng vi axit to este. Suy ra A v X trong phn t c nhm OH.
Hidro ho A c xc tc Pd to hp cht X. Suy ra A trong phn t c lin kt bi.
Oxi ho X bng KMnO4 to thnh CO2 v mt axit dicacboxylic mch di. Suy ra A v X trong phn t
c 4 nhm OH, hoc 2 nhm OH v 2 nhm CHO, hoc 2 nhm OH v 2 nhm C=O.
Cu to ph hp c th c ca A, X l:
A: HOCH2-CH(OH)-C16H24-CH(OH)-CH2OH
X: HOCH2-CH(OH)-C16H32-CH(OH)-CH2OH
(hoc A: HOCH2-CO-C16H24-CO-CH2OH ; OHC-CHOH -C16H24-CHOH-CHO. C th vit cng thc
cu to ca mch cacbon - C16H24- trong c cc lin kt bi phn b i xng).
Cc phng trnh phn ng:
Th d: A l HOCH2-CH(OH)-C16H24-CH(OH)-CH2OH
H+
4 CH3COOH
(CH3COO)CH2-CH(OCOCH3)-C16H24-CH(OCOCH3)-CH2(OOCCH3)
4 CH3COOH
H+
(CH3COO)CH2-CH(OCOCH3)-C16H32-CH(OCOCH3)-CH2(OOCCH3)
3 H2
Pt
HOCH2-CH(OH)-C16H32-CH(OH)-CH2OH
KMnO4
HOOC-C16H32- COOH + 2 CO2

1. Hy gi tn cc sn phm to thnh khi ankyl ho benzen bng 1-dodexen vi xc tc axit.
2. Atropin c trong cy Atropa belladonna. N kt tinh di dng hnh lc lng, nng chy 1150C.
Nh c tc dng lm gin ng t nn n c dng trong khoa mt. Atropin l mt este c cu trc
nh hnh v.
a) Hy nh du sao (*) vo nguyn t cacbon bt i v cho

bit s ng phn lp th.
b) Khi thy phn atropin trong mi trng axit nhn c
tropin v axit (R, S)tropic. Vit phng trnh phn ng.
CH3
H
OCOCH
Atropin
BI GII:
1.
C6H6 + CH2=CH-(CH2)9-CH3
(I): 1-Phenyldodecan (hoc dodexylbenzen)

2.
N
C6H5
CH2OH
C6H5-CH2-(CH2)10-CH3
(I)
C6H5-CH(CH3)-(CH2)9-CH3
(II)
; (II): (R,S)-2-phenyldodecan
CH3
H
OCOCH
Atropin
C6H5
Atropi n c 3 cacbon bt i,
c 2 ng phn quang hc.
CH2OH
Thu phn atropi n trong mi trng axit

N
CH3
H
HOOC-CH-CH2OH
C6H5
OH
Tropin
Axit (R,S)-tropic

Mt disaccarit A khng c tnh kh. Khi thu phn trong mi trng axit, A cho sn phm duy nht l
pentoz B. Cng c th thy phn A nh enzim -glicozidaza song khng dng c -glicozidaza.
T B c th to ra D-glucoz bng cch cho tc dng vi HCN ri thu phn (xc tc axit) v kh.
1) Vit cng thc Fis v gi tn B theo danh php h thng.
2) Vit s cc phn ng chuyn ho B thnh D-glucoz.
3) Vit cng thc cu trc ca A dng vng 6 cnh phng.
4) khng nh cu trc vng 6 cnh ca A, ngi ta cho A tc dng vi CH3Br trong mi
trng baz ri thy phn (xc tc H+). Dng cng thc cu trc, vit s cc phn ng.
BI GII:
1) B c 3C bt i ging nh 3C bt i cui cng D glucoz
H
HO
H
H
CHO
OH
HSuy ra
OH
OH
CH2OH
D-Glucoz
HO
H
H
CHO
H
OH
OH
CH2OH B
(2S, 3R, 4R)-tetrahidroxipentanal
2)
HO
H
H
H
HO
H
H
CHO
H
OH
OH
CH2OH
HO
HO
H
H
CN
H
H
OH
OH
CH2OH
H
HO
H
H
CN
OH
H
OH
OH
CH2OH
HCN
COOH
OH
H
OH
OH
CH2OH
-H2O
COOH
OH
H
OH
OH
CH2OH
CHO
OH
H
OH
OH
CH2OH
H
HO
H
H
H2O/H+
O C
H
OH
HO
H
H
OH
H
O
CH2OH
H
HO
H
H
kh
3) T cc d kin ca bi, suy ra A do hai phn t B lin kt -1,1 glycozit nn:

OH
O
OH
OH
OH
hay
OH
OH
OH
OH
OH
OH
4)
OH
OCH3
OH
O
CH3Br
OH
OH
OH
baz
OH
OCH3
O
2
OCH3
OCH3
OCH3
OH
H3CO
H
H
OCH3
OCH3
OCH3
OH
H3O+
OH
CHO
H
OCH3
OCH3
CH2OH
OCH3
1. Vit s iu ch cc axit sau y:

a) Axit: benzoic, phenyletanoic, 3-phenylpropanoic t benzen v cc ha cht cn thit khc.
b) Axit:xiclohexyletanoic, 1-metylxiclohexan-cacboxylic t metylenxiclohexan v cc ha cht cn thit
khc.
2. Sp xp (c gii thch) theo trnh t tng dn tnh axit ca cc cht trong trong dy sau:
a) Axit: benzoic, phenyletanoic, 3-phenylpropanoic, xiclohexyletanoic,
1-metylxiclohexan-cacboxylic.
COOH
b)
N
COOH
;
N
(A)
CH2COOH
COOH
(D)
(C)
(B)
3. Sp xp (c gii thch) theo trnh t tng dn nhit nng chy ca cc cht sau:
COOH
COOH
COOH
;
;
N
(A)
(C)
(B)
BI GII:
1. a)
C6H6
Br2/Fe
C6H5Br
CH3Br
Zn
C6H5CH3
C6H5MgBr
2. H3O+
KCN
C6H5CH2Br
[O]
Mg
1. CO2
Br2/h
C6H5CH2CN
CH2(COOC2H5)2/NaOEt
H3O+
C6H5COOH C6H5CH2CH(COOC2H5)2
1. OH2. H3O+
3. to
C6H5CH2COOH
C6H5CH2CH2COOH
b)
CH3
CH2
Br
HBr
CH3
MgBr
H3O+
CH2Br
1. KCN
2. H3O+
2. a)
H3C COOH
CH2COOH
<
<
+I 1
<
+I 2
CH2COOH
(ho
c 1. Mg/ ete )
2. CO2
3. H3O+
+I 2
+I 1
COOH
1. CO2
Mg/ ete
HBr/peoxit
CH3
-I1CH2CH2COOH
CH2COOH
-I 2
<
<
-I 1
<
-I 2
Cc gc hidrocacbon c hiu ng +I ln th Ka gim v -I ln th Ka tng
<
-I 3
COOH
-I 3
b)
-I 1
CH2COOH
COOH
-I 2
<
(D)
V:
C O
H O
(A)
-C3 N -I 3
<
(C)
COOH
-I 4
<
N -C4
(B)
- I1 < - I2 nn (C) c tnh axit ln hn (D).

(A) v (B) c N nn tnh axit ln hn (D) v (C)
(A) c lin kt hidro ni phn t lm gim tnh axit so vi (B).
3. Tng dn nhit nng chy ca cc cht:
COOH
COOH
<
COOH
S
(A)
(C)
V
MC < MA.
(B) c thm lin kt hidro lin
phn t vi N ca phn t khc.
<
N
(B)

L-Prolin hay axit (S)-pirolidin-2-cacboxylic c pK1 = 1,99 v pK2 = 10,60. Pirolidin (C4H9N) 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 ho H2A+ v dng trung ho HA ca prolin
pH = 2,50.
3. Tnh gn ng t l dng deproton ho A v dng trung ho HA ca prolin
pH = 9,70.
4. T metylamin v cc ho cht cn thit khc (benzen, etyl acrilat, natri etylat v cc cht v c), hy
vit s iu ch N-metyl-4-phenylpiperidin.
BI GII:
1.
COOH
NH
H
pHI = 1,99 + 10,60 = 6,30

2
COOH
H
H
2. p dng phng trnh Henderson - Hasselbalch
H2A+
lg
K1
HA + H+
[HA]
[H A ]
+
K1 =
[HA][H+]
[ H2A+]
; Suy ra:
= pH - pK1 = 2,50 - 1,99 = 0,51
[HA]
= 3,24
[H2A+]
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 1/3,24 = 0,309
3.
K2
[ A]
[HA]
H+ + A
HA
= pH pK2 = 9,70 10,60 = 0,90
lg
[ A]
= 0,126
[HA]
1
8
Vy pH = 9,7 t l gia dng deproton ho v dng trung ho l 1/8

4.
2 CH2=CH-COOC2H5
CH3NH2
CH3-N
CH2-CH2-COOC2H5
CH2-CH2-COOC2H5
C2H5ONa
COOC2H5
CH3
CH3
OH
2. H3O+
CH3
Br
Mg
ete
MgBr
C6H5
C6H5
1. C6H5MgBr
2. H3O+, to
+Br2/Fe, to
1. OH
C6H5
H2, Ni, to
H2SO4, 170oC
CH3
CH3
CH3

Hp cht hu c A cha 79,59 % C; 12,25 % H; cn li l O ch chim mt nguyn t trong phn t.
Ozon phn A thu c HOCH2CH=O ; CH3[CH2]2COCH3 v CH3CH2CO[CH2]2CH=0. Nu cho A tc
dng vi brom theo t l mol 1:1 ri mi ozon phn sn phm chnh sinh ra th ch thu c hai sn
phm hu c, trong s c mt xeton. un nng A vi dung dch axit d dng thu c sn phm B
c cng cng thc phn t nh A, song khi ozon phn B ch cho mt sn phm hu c duy nht.
1. Xc nh cng thc cu to v gi tn A.
2. Tm cng thc cu to ca B v vit c ch phn ng chuyn ha A thnh B.
BI GII:
1.
79,59 : 12,25:
8,16= 13 : 24 : 1
12
16
A c cng thc phn t C13H24O.

T sn phm ozon phn tm ra 2 cng thc cu to c th ph hp:
CH3CH2CH2C=CH CH2CH2C=CHCH2OH
CH3
CH2CH3
(A1)
CH3CH2CH2C = CCH2CH2CH=CHCH2OH
H3C CH2 CH3
(A2)
T phn ng brom ha ri ozon phn suy ra (A1) ph hp, v:

Br2
1:1
CH3CH2CH2C=CH CH2CH2C=CHCH2OH
(A1)
CH3
CH2CH3
CH3CH2CH2CBrCHBrCH2CH2C=CHCH2OH
CH3
CH2CH3
ozon phn
CH3CH2CH2C = CCH2CH2CH=CHCH2OH
(A2)
H3C CH2CH3
CH3CH2CH2CBrCBrCH2CH2CH=CHCH2OH
H3C CH2CH3
xeton + O=CHCH2OH
Br2
1:1
ozon phn
andehit + O=CHCH2OH
Tn ca A: 3-Etyl-7-metyldeca-2,6-dien-1-ol
2. B phi l hp cht mch vng c cha 1 ni i trong vng. B sinh ra t A do phn ng ng vng:
CH2OH
H+, to
- H2O
HOH
- H+
+ CH2
OH
(A)
(B)
1. D-Galactoz l ng phn cu hnh v tr s 4 ca D-glucoz. Trong dung dch nc D-galactoz
tn ti 5 dng cu trc khc nhau trong mt h cn bng. Hy dng cng thc cu hnh biu din h
cn bng v cho bit dng no chim t l cao nht.
2. D-Galactoz l sn phm duy nht sinh ra khi thy phn hp cht A (C12H22O11). thc hin phn
ng ny ch c th dng cht xc tc l axit hoc enzim -galactozidaza.
A khng kh c dung dch Fehling, song tc dng c vi CH3I trong mi trng baz cho sn
phm ri em thy phn th ch thu c 2,3,4,6-tetra-O-metyl-D-galactoz.
Hy tm cu trc ca A, vit cng thc vng phng v cng thc cu dng ca n.
3. un nng D-galactoz ti 165oC sinh ra mt hp hp sn

phm, trong c mt lng nh hp cht B. Cho B tc
dng vi CH3I (c baz xc tc) ri thy phn sn phm
sinh ra th thu c hp cht C l mt dn xut tri-O-metyl
ca D-galactoz. Hy gii thch qa trnh hnh thnh B v
vit cng thc Fis ca C.
BI GII:
1. 5 dng cu trc ca D-galactoz:
OH
O
HO
OH
CH 2OH
O OH
HO
OH
O
OH
OH
OH
CH=O
OH
HO
HO
OH
OH
-Galactopiranoz
CH 2OH
HO
CH 2OH
-Galactofuranoz
O
OH
CH2OH
OH
OH
OH
OH
OH
OH
OH
CH 2OH
Galactofuranoz
Galactopiranoz
Chim t l cao nht l -Galactopiranoz.

2. Cc d kin ln lt cho bit A l disaccarit do 2 n v D-galactoz lin kt -1,1 vi nhau, c hai
u dng vng piranoz. T vit cng thc vng phng:
CH 2OH
HO
CH 2OH
OH
HO
HO HOCH 2
OH
OH
hoc
OH
OH
OH
OH
HO
HOCH 2
OH
Cng thc cu dng:
HO
OH
HO
OH
O
HO
HO
O
HO
ho
c
HO
OH
OH
OH
OH
O
O HO
HO
OH
OH
3.
O
4
OH
OH
OH
OH
5
HO
CH2OH
3
O
1
OH
HO
5
6
OH
OH
OH
- H2O
HO
OH
HO
6
HO O
3
2
OH
T cng thc cu trc trn suy ra rng 3 nhm -OH b metyl ho l cc v tr 2, 3, 5. Do

cng thc Fis ca C:
CH=O
OCH3
O
CH3O
CH3O
HO
CH(OH)
OCH3
OCH3
OCH3
CH2OH
CH2OH
2, 3, 5-Tri-O-metyl-D- galactoz.
2-(1-Hidroxipentyl)xiclopentanon (A) l cht trung gian trong qu trnh tng hp mt cht dng
lm hng liu l metyl (3-oxo-2-pentylxiclopentyl)axetat (B).
1. Vit cng thc cu to ca A v s cc phn ng tng hp A t axit adipic (hay axit hexandioic)
vi cc cht khng vng v cc cht v c khc.
2. Vit cng thc cu to ca B v s cc phn ng tng hp B t A v cc ha cht cn thit khc.
3. B c tt c bao nhiu ng phn cu hnh? Hy vit cng thc lp th ca ng phn c cu hnh ton
l R.
BI GII:
1.
1. Ca(OH)2
HOOC COOH
Axit aipic
2. t
CH2[CH2] 3CH=O
OH-
2.
CH[CH2] 3CH3
B:
OH
(A)
COOCH 3
O
H+
- H2O
O OH
(A)
H+
Chuyn v
O
CH(COOC2H5)2
CH2(COOC2H5)2
NaOEt
O
CH2COOH
H3O+/ to
- CO2
COOCH3
CH3OH
H+
3. B cha 2 nguyn t Cnn c 4 ng phn quang hc.

ng phn c cu hnh ton R l:
COOCH3
CH3
H
O
(B)

1. Dng c ch phn ng gii thch cc kt qu thc nghim sau:
a) Hng s tc dung mi phn 3-metylbut-2-enyl clorua trong etanol ln hn dung mi phn anlyl
clorua 6000 ln.
b) Sau khi ho tan but-3-en-2-ol trong dung dch axit sunfuric ri yn mt tun th thu c c but-3en-2-ol v but-2-en-1-ol.
c) X l but-2-en-1-ol vi hidro bromua th thu c hn hp 1-brombut-2-en v
3-brombut-1-en.
d) X l but-3-en-2-ol vi hidro bromua cng thu c hn hp 1-brombut-2-en v
3-brombut-1-en.
2. Cho bit sn phm no l sn phm chnh trong mi hn hp sau khi x l but-2-en-1-ol, but-3-en-2-ol vi hidro bromua trn? V sao?
BI GII:
1. a) Dung mi phn (CH3)C=CHCH2Cl trong etanol xy ra theo c ch SN1 v to cacbocation trung
gian:
(CH3)C=CHCH2Cl
(CH3)2C=CH-CH2+
- Cl -
(CH3)2C+-CH=CH2
C+ bc ba bn hn C+ bc mt CH2-CH=CH2 nn hng s tc ln hn.

b) C s chuyn v anlylic nn tn ti 2 sn phm:
H2SO4
CH2=CH-CH-CH3
OH
CH2=CH-CH-CH3
- H2O
- H2O
OH 2
CH2-CH=CH-CH3
OH
CH2=CH - CH-CH3
H2O
- H+
CH2-CH=CH-CH3
c) C s chuyn v anlylic nn tn ti 2 sn phm:

+
H
CH3- CH=CH-CH2OH
- H2O
CH3- CH=CH-CH2
Br-
Br-
CH3- CH=CH-CH2Br
d) Tng t c):
H+
CH3- CHOH-CH=CH2
- H2O
CH3- CH-CH=CH2
CH3- CH-CH=CH2
Br
CH3- CH-CH=CH2
Br-
CH3-CH-CH=CH2
CH3- CH=CH-CH2
Br-
CH3-CH=CH-CH2Br
Br
3. Sn phm chnh l CH3-CH=CH-CH2Br v: dn xut bc mt cn i hn dn xut bc hai v dn
xut bc mt l anken c nhiu nhm th hn nn bn hn anken u mch.

1. Vit cng thc chiu Fis ca dng mch h cc cht sau:
HOCH2
OH
CH2OH
OH
OH
OH
H2C
OH
OH HO OH
(B)
(A)
O
HO
H3C
OH
OH
OH
OH
CH2OH
OH HO OH
(C)
(D)
2. Trong cc cht (A), (B), (C), (D) trn, cht no:

a) thuc dy L? b) l ng deoxi? c) l ng c mch nhnh?
d) thuc loi xetoz? e) c dng furanoz? g) c cu hnh nhm anomeric?
BI GII:
Cng thc chiu Fis ca (A), (B), (C), (D):
CH2OH
CHO
HO
HO
OH
HO
CH2OH
(A)
CHO
OH
OH
OH
CH2OH
(B)
CHO
H3C
HO
OH
OH
CH2OH
(C)
C=O
OH
OH
OH
OH
CH2OH
(D)
2. Trong cc cht (A), (B), (C), (D) trn:

a) (A), (C) l ng thuc dy L
b) (B) l ng deoxi.
c) (C) l ng c mch nhnh.
d) (D) thuc loi xetoz.
e) (B) c dng furanoz.
f) (D) c cu hnh nhm anomeric.
II.
OLYMPIC HA HC QUC T:
OLYMPIC HA HC QUC T 1996:
Hai hydrocacbon ng phn A v B cha 85,7% cacbon theo khi lng.
1) Vit cng thc tng qut (khng phi cng thc thc nghim tho iu kin ny).
Hydrocacbon A v B c nhng tnh cht sau: Phn ng ca mi cht vi ozon v x l tip theo
vi bt km trong axit to sn phm hu c duy nht C. S oxy ha hp cht C cho ra sn phm duy
nht l axit cacboxylic D. S liu ph cho thy tt c cc nguyn t hydro trong hp cht D, tr hydro
ca nhm cacboxyl u thuc nhm metyl. Khi lng ring ca hi D quy v iu kin tiu chun (0oC
v 1atm) l 9,1g/L (th tch mol bng 22,4L ti 0oC v 1atm).
Khi phn ng vi kali pemanganat trung tnh trong nc, hp cht A phn ng d hn hp cht
B. Trong phn ng ny A to thnh mt hp cht F duy nht cn B to thnh mt hn hp ng phn
G1 v G2 theo t l 1:1.
Phi vit v cn bng mi phng trnh phn ng. Khng i hi vit c ch phn ng.
2) Vit cng thc cu to ca hp cht D khi trong dung dch nc v khi pha hi.
3) Vit cng thc cu to ca hp cht C.
4) Vit cng thc cu to cc ng phn A v B.

5) a) Vit cc phng trnh phn ng ca qa trnh chuyn A hoc B thnh C v D.
b) Vit cc phng trnh phn ng ca qa trnh chuyn ha A thnh F, B thnh G1 v G2.
6) Cc hp cht G1 v G2 phn ng d dng vi axeton c mt axit to cc hp cht H1 v H2.
Vit cng thc cu to ca H1 v H2.
7) Cc hp cht A v B phn ng vi brom. Mt trong cc sn phm ca phn ng ny l khng
cc (momen lng cc ca phn t ny coi nh bng 0) v khng c tnh quang hot. Vit cng
thc ha hc lp th ca sn phm ny v phng trnh to thnh cht y. Hy xc nh cu hnh
tuyt i ca cc nguyn t c tnh i xng gng trong phn t ny (nu c) v nh du
chng theo quy tc c tn R v S bng cch ch nh ng R v S ti mi tm lp th.
Anken phn ng vi peaxit (peoxiaxit) dn n s cng hp mt nguyn t oxy vo lin kt i
to mt vo ba cnh c cha oxy. Phn ng epoxy ha ny c tnh lp th c th r rt dn n s
l gi cc v tr tng i ca cc nhm th trn lin kt i m nguyn t oxy gn vo.
S epoxy ha hp cht A bng axit peaxetic to thnh mt hp cht duy nht K. Trong cng iu
kin B to thnh mt hn hp hai ng phn L1 v L2 (theo t l 1:1).
8) Hp cht K c tnh quang hot khng? Vit cng thc ha hc lp th ca K v ch r ha hc
lp th ca n. Mi hp cht L1 v L2 c tnh quang hot khng? Vit cng thc ha hc lp th
ca L1 v L2 v ch r ha hc lp th ca n.
BI GII:
1) Cng thc tng qut: CnH2n.
2) Trong dung dch nc: (CH3)3CCOOH
trng thi hi:
O
OH
Cu to nh hp pha hi c d on nh tr s khi lng ring.

Khi lng mol phn t pha hi bng 9,1.22,4 = 204 gn gp i khi lng mol phn t ca
(CH3)3CCOOH. Nh cc axit bo n gin khc, axit ny cng c th dime ha dng hi.
3) Hp cht C: (CH3)3CCHO
4) Cng thc cu to ca A v B:
Me3C
CMe3
CMe3
Me3C
A
5) Cc phn ng chuyn ha A C D
Me3C
Me3C
CMe3
B
O
CMe3
Zn/H+/H2O
O3
O
Cc phn ng chuyn ha A F:
2Me3CCHO
[O]
Me3CCOOH
Me3C
CMe3
Me3C
CMe3
KMnO4
HO
OH
H
Cc phn ng chuyn ha B G1, G2.

CMe3
Me3C
CMe3
KMnO4
Me3C
CMe3
Me3C
HO
OH
HO
OH
hh triet quang
6) Cng thc cu to ca H1 v H2
CMe3
Me3C
CMe3
Me3C
H2
H1
7) Sn phm brom ha khng phn cc:
Br
Br
C M e3
CM e3
C M e3
hay H
Br
hay
M e3C
Br
Br
M e 3C
Br
CM e3
M e3C
M e3C
C M e3
B r2
C M e3
Br
8) Ta c:
Me3C
CMe3
: Phn t khng c tnh quang hot
O
Me3C
CMe3
: Phn t c tnh quang hot.
O
Me3C
CMe3
: Phn t c tnh quang hot
Br

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-2,3dicacboxylic, 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 X1, 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 vi axit
clohydric th chuyn chm thnh A.
Phi vit v cn bng mi phng trnh phn ng. Khng cn vit c ch phn ng.
1) nh du (*) cc nguyn t cacbon phi i xng (asymmetric) trong axit 5-norbonen-2,3dicacboxylic.
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
COOH
OC
O
C
COOH
O
COOH
C
O
COOH
COOH
COOH
COOH
3) Phn ng ca mt ng phn lp th ca X vi NaOH:

COONa
COOH
+ 2H2O
+ 2NaOH
COONa
COOH
Phn ng ca mt ng phn lp th ca Y vi NaOH:

O
C
COONa
O
+ H2O
+ 2NaOH
COONa
C
O
4) MA = 0,3913/(12,7.0,100/1000) = 308 (g/mol-1)

Cc phn ng t X n A:
I
COONa
COONa
I2
-NaI
HCl
COONa -NaCl
O
CO
COOH
O
CO
5) Chuyn ha A thnh C:
I
COOH
O
CO
CO
+ HI
CO
Phn ng ca C vi nc:
O
O
CO
2H2O
OH
CO
OH
COOH
COOH
6) Cu to ca X:
COOH
COOH
7) Chuyn ha B thnh A:
I
+H2O
-H2O
COOH
CO
O
COOH
OH
COOH
COOH
O
CO
8) Khng, A v B khng phi l cc ng phn khng i quang.

Hp cht X l mt ng ba (tri saccarit) c ch yu trong cc thc n lm t ht bng. Hp
cht X khng phn ng vi dung dch Benedict cng nh khng i quang. S thu phn xc tc axit
to ra ba ng D hexoz khc nhau A, B v C. Tt c cc hp cht A v B cng nh hp cht I (xem
di y) u cho cng mt osazon khi phn ng vi lng d phenylhydrazin trong mi trng axit.
Hp cht C phn ng vi axit nitric to thnh mt hp cht D khng c tnh quang hot (khng trit
quang). thit lp quan h gia cu hnh gia D glyxerandehit v C, cht ng andehit 4 cacbon
(andotetroz) trung gian khi b oxy ha bi axit nitric khng to thnh 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 (diastereoisomer) 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.
O
C
O
C
H
HO
HO
H
OH
H
OH
OH
CH2OH
D-glyxerandehit
CH2OH
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 hot 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:
COOH
CHO
H
OH
OH
meso
H
CHO
H
OH
COOH
CH2OH
OH
COOH
CHO
CH2OH
D-glyxerandehit
OH
HO
HO
OH
OH
doi xung
guong
COOH
CH2OH
D-threoza
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 khng ging 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
H
CHO
H
OH
OH
CH2OH
HO
CHO
CH2OH
OH
H
HO
HO
H
H
OH
OH
HO
OH
OH
CH2OH
CH2OH
B
A
(D-glucoza)
(D-fructoza)
Metyl ha X ri thu phn k tip to thnh E, F v G di y:
OH
OH
CH2OH
C
(D-galactoza)
CHO
CH2OH
H
OCH3
H3CO
OCH3
OH
OH
H
H
OCH3
OCH3
H
OCH3
CH2OH
E chuyn ha t A
CH2OH
O
CH2OCH3
HO
H
H
OH
OCH3
OH
CH2OCH3
H
H
OH
OCH3
CH2OH
F chuyn ha t B
CHO
CH2OCH3
H
OCH3
O
H
H3CO
H3CO
H
OCH3
OCH3
H
OH
OH
H
OCH3
CH2OCH3
G chuyn ha t C
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
th saccarit X c th c biu th l C6 A6 B5
Mt trong 4 cu to khc nhau c th c ca X c cho di y:

CH2OH
O
OH
H
H
OH
CH2
C
H
OH
H
H
OH
Tri-saccarit X
CH2OH
OH
H
OH
OH
CH2OH
B
OH
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.
Cc nh ha hc ca cng ty Merck Frosst Cnda Montral pht trin mt dc phm rt c
trin vng v hu hiu tr bnh suyn. Cu to ca MK-0476 nh sau.
H
COOH
CH3
H3C
OH
Cl
MK-0476
Trong qa trnh kim tra, h pht minh mt qa trnh tng hp n gin v hiu qa, 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) LiAlH4
2) H3O+
C6H5COCl
Pyridin
1) CH3-SO2Cl/(C2H5)3N
C (C12H14O3)
2) NaCN
D(C12H13O2N)
COOC2H5
1) KOH(aq)
2) CH2N2
COOH 1) NaOH(aq)
2) H3O+
F(C9H14O3S)
1) CH3-SO2Cl/(C2H5)3N
E
2) CH3COS-Cs+
SH
Mt trong nhng giai on cui ca qa trnh tng hp MK 0476, mui diliti ca thiol axit (G)
trn c ghp vi mch ca phn t nu di y:
H3C
CH3
S
O
Cl
H3C
OH
H
1)
CO2-Li+
- +
S Li
2) H+
COOH
CH3
H3C
OH
Cl
MK-0476
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.
BI GII:
1) Cng thc cu to ca cc cht:
O
O
CH2O
CH2O
CH2OH
H2C
CH2OH
CH2OH
D
CH2S
CH2OH
CH3
O
CH2CO2CH3
CH2CO2CH3
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
CH2CO2H
Vi mt ng lng baz:
CH2SH
CH2CO2CH2CH3
5) Cng thc Lewis ca sn phm dime:
CH2S
SCH2
H2C
CH2
HO
OH

Nm Aspergillus nidulans to ra hai lacton (este vng) thm A v B (C10H10O4) 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 kt\ 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
H3C
H3C
CO2CH3
O
HO
I
E
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. Thc hin phn ng Diels Alder
hp cht H vi dimetyl but 2 indioat J to thnh K (C15H20O6) 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:
OCH3
OCH3
OCH3
H3C
H3C
H3C
HO
H3CO
B
O
OH
OH
O
HO
C
OCH3
OCH3
H3C
H3C
H3C
H3C
HO
H3CO
H3CO
O
H3CO
OCH3
G
OCH3
CO2CH3
H3C
H3C
CO2CH3
H3C
CO2CH3
H3CO
CO2CH3
O
H3CO
CO2CH3
OCH3
OCH3
H3C
CO2CH3
H3C
OCH3
CO2H
H3C
O
H3CO
CO2CH3
CO2H
L
OCH3
H3C
O
H3CO
H3CO
O
O
H3CO
N
O
2) Cng thc khc ca B:

OH
H3C
O
H3CO
O

Glycozit A (C20H27NO11) c trong ht Rosaceae khng phn ng vi dung dch Benedict cng
nh nc Fehling. S thu phn bng enzym ca A cho (-)B (C8H7NO) v C ( C12H22O11) nhng s
thu phn hon ton bng axit to thnh cc sn phm hu c (+) D (C6H12O6) v (-) E (C8H8O3).
C c mt lin kt - glycozit v cho phn ng vi dung dch Benedict cng nh nc Fehling.
Metyl ha C vi MeI/Ag2O to thnh C20H38O11 m khi thu phn trong mi trng axit cho 2,3,4-tri-Ometyl-D-glucopyranoz.
() B c th c iu ch t benzandehit v NaHSO3, tip theo vi NaCN. Thu phn () B
trong mi trng axit cho () E (C8H8O3).
1) Vit cc cu to ca A D vi ha hc lp th ph hp theo cng thc chiu Haworth tr cht B.
Glycozit A c c tnh v c cho l do hp cht F rt c, c gii phng trong iu kin
thy phn. S kh c ca hp cht F trong cy ci c th km theo cc phn ng (khng trnh by ha
hc lp th).
O
F + H2N
CH
O
OH
enzym
G +
H (C4H6N2O2)
enzym
H2N
CH
CH2
CH2
SH
L - cystein
OH
NH2
L - asparagin
Mt lng nh hp cht F trong c th ngi c gii c bng mt phn ng trc tip vi
cystin cho L cystein v hp cht I (C4H6N2O2S) c bi tit theo nc tiu (khng trnh by ha hc
lp th).
NH2
H2
C
H2
C
F +
NH2
C
H
H
C
NH2
c y stin
COOH
COOH
enzym
HS
H2
C
C
H
COOH
L - c y s te in
I (C 4 H 6 N 2 O 2 S )
Hp cht I cho thy khng b hp th ti 2150 2250cm-1 trong ph IR ca n nhng quan st

thy mt di ti 1640cm-1 v cc di ng vi nhm cacboxyl.
2) Hy vit cng thc phn t ca cc hp cht F v G v cc cng thc cu to ca cc hp cht H
v I. Ch r ha hc lp th ca H.
(-) 1 Phenyletan 1 d C6H5CHDCH3 c th c iu ch dng quang hot v kh nng
trin quang kh mnh []D = -0,6.
CH3
C8H10O
(-)N
C6H5SO2Cl
Pyridin
1) LiAlD4/ete
2) H3O+
H
C6H5
(-) - 1 - phenyletan -1 -d
Cu hnh tuyt i ca (-) 1 phenyletan 1 d lin h vi (-) E theo cc phn ng sau:
Ag2O
1) LiAlH4/ete
C8H8O3
C10H14O2
C12H16O3
H
I
C
2) H3O+
2 5
(-) E
(-) J
(-) K
1) LiAlH4/ete C H CHCH (OC H )
C6H5SO2Cl
6 5
3
2 5
L
2) H3O+
Pyridin
(-) M
Hp cht (-) M cng c th thu c t hp cht M nh sau:
1)K
C6H5CHCH3(OC2H5)
C8H10O
(-) M
(-) N 2) C2H5I
3) Suy ra cu hnh tuyt i ca (-) E v cu to vi cu hnh ca mi cht trung gian ( J O) trong

qa trnh.
4) Cho bit c ch c lin quan trong s chuyn hp cht O thnh 1 phenyletan 1 d.
BI GII:
CH2OH
O
CH2
H
OH
H
O
H H
OH
H
H
OH
OH
H
H
OH
H
OH
H
C
CN
HO
H
C
CH2OH
CN
CH2
H
H
OH
H H
OH
OH
H
H
OH
OH
OH
H
CH2OH
OH
C
O
OH
H
H
OH
OH
H
D
2) Cng thc phn t F: HCN
Cng thc phn t G: H2S
H
N
HOOC
COOH
H2N
OH
HOOC
hay
NH
H
3) Cng thc cu to ca cc cht t E n O:
COOC2H5
COOH
OH
NH2
CH2CN
OC2H5
C6H5
C6H5
(-) E
(-) J
CH2OSO2C6H5
CH2OH
H
OC2H5
C6H5
(-) K
OC2H5
C6H5
CH3
CH3
CH3
CH3
R
H
OC2H5 H
C6H5
OH
S
C6H5
OSO2C6H5 D
C6H5
H
C6H5
(-) M
O
(-) N
(-)1 - phenyletan - 1 -d
4) C ch ph hp: SN2.
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 DNP aminoaxit chun.
2) Khi x l B1 vi DNFB ri thu phn k tip bng axit to thnh mt sn phm l DNP Asp.
iu ny cho thy B1 c axit aspartic ti N cui. Hy vit cu to y ca DNP Asp ti
im ng in ca n (khng cn ha hc lp th).
K , aminoaxit c C cui c xc nh bng cch un nng peptit ti 100oC 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
O2N
OH
OH
N
H
NO2
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.
Shikonin l hp cht c mu c tm thy r ca cy Lithospermum erythorizon

mc Chu . Mt on r c s dng trong nhiu th k lm bi thuc dn gian v
ngy nay c s dng lm thuc m cha cc vt bng. Shikonin c cng thc cu to nh
sau:
OH
OH
OH
1. Shikonin c bao nhiu ng phn lp th?

2. C phi cc ng phn lp th ca Shikonin c cng nhit nng chy khng?
y l mt phn trong qa trnh tng hp Shikonin:
OCH3
OH
OH
+A
B (xt)
OCH3
OH
+C
OH
OH
OH
3. Vit cng thc cu to A.

4. Gi tn A.
5. Vit cng thc cu to C
Lng ln nhng hp cht tng t Shikonin c tng hp nhn c cc cht c
hiu lc hn. Mt chui phn ng c dn ra di y
Shikonin
SOCl2
C6H15ClO4
KOH/EtOH
70oC
C16H14O4
6. Vit cng thc cu to ca E.

7. E c th c bao nhiu ng phn lp th.
Mt cch khc iu ch nhng dn xut c ch ca Shikonin l:
OCH3
OCH3
HBr
F
C21H29BrO5
OCH3
OCH3
OCH3
1) Mg/(C2H5O)2
2) CO2
3) HCl(dd)
G
C22H30O7
8. Vit cng thc cu to F.

9. Vit cng thc cu to G.
BI GII:
1. C 2 ng phn.
2. Tt c cc ng phn lp th ca Shikonin u c cng nhit nng chy.
3. A c cng thc cu to nh sau:

O
Cl
4. Tn IUPAC ca A: 4-Metyl-3-pentanoylclorua.
5. Cng thc ca C: NaBH4 (LiAlH4 cng c th c chp nhn).
6. Cng thc cu to ca E:
OH
O
OH
O
7. E c th c 2 ng phn lp th .
8. Cng thc cu to ca F :
OCH3 OCH3
OCH3
Br
OCH3 OCH3
9. Cng thc cu to ca G:
OCH3 OCH3
OCH3
COOH
OCH3
OCH3
Hp cht thin nhin A cha C, H, O c % mi nguyn t theo khi lng nh sau: C:

63,2%; H: 5,3%; O: 31,5%.
Ph khi ca A:
1. Xc nh cng thc nguyn ca A.
2. Vit cng thc phn t cht A.

Dung dch cht A trong ete c lc vi dung dch NaOH trong ete. Sau phn ng thy A
khng cn trong ete. Li lc k dung dch A trong ete vi dung dch NaHCO3 ri yn thy A
vn cn trong ete.
3. A c th c nhng nhm chc no?
A phn ng c vi thuc th Tollens.
4.4. A c nhm chc no?
Ph HNMR ca A ghi tn s 300MHz cho hnh sau (dung mi CDCl3). Cho vch
7,27ppm v 3 vch n 3,9; 6,3 v 9,8ppm.
Hnh sau l s c th ha hnh ph trong khu vc t 6,9 n 7,6ppm:
Tn hiu 6,3ppm mt i khi nh D2O vo:

5. Thng tin no sau y ng:
+ Trao i lin kt gia C v H.
+ Trao i lin kt gia O v H.
+ Hiu ng pha long.
+ S thy phn.
Khi them CDCl3 th vch ny xut hin tn hiu thp hn.
6. Thng tin no sau y ng:
+ Tng mc lin kt hydro.
+ Gim mc lin kt hydro.
+ C lin kt hydro lin phn t.
+ C lin kt hydro ni phn t.
+ Khng c lin kt hydro.
7. Vit 4 cng thc cu to c th c ca A.
8. Mnh no bin mt ti pic c khi lng 137 v 123.
9. Hai trong s 4 ng phn vit c pKa thp hn hai ng phn cn li. Xc nh chng.
BI GII:
1.
2.
3.
4.
5.
6.
C8H8O3.
C8H8O3.
Nhm phenol.
Nhm andehit.
Trao i lin kt O-H.
Gim mc lin kt hydro v c s to thnh lin kt hydro lin phn t
7.
CHO
CHO
OCH3
HO
OCH3
CHO
CHO
OH
OH
OH
OCH3
OCH3
8. CH3 v HC=O
9
CHO
OCH3
CHO
OH
OH
OCH3

R gng (Zingiber officinale) c bit nhiu v mt dc tnh v nhng tnh cht ca hng
liu. Ti Ayurveda (Ni c truyn thng v thuc n ), rt nhiu ng thuc c s dng gng nh
l mt v thuc tr cc bnh lin quan n rut, cm lnh thng thng v mt s bnh khc. Mt vi
hp cht c coi nh l nguyn nhn gy ra v cay ca gng. Rt nhiu trong s l nhng dn xut
th n gin ca vng thm vi di mch c khc nhau. Ba trong s l Zingeron; (+)[6] Gingerol
v Shogaol l quan trng nht.
Cng thc phn t ca cc cht ny l:
+ Zingeron: C11H14O3.
+ Gingerol: C17H26O4.
+ Shogaol: C17H24O3.
1) Zingeron cho phn ng dng tnh vi FeCl3 v 2,4 DNP (2,4 dinitrophenylhydrazin). N
khng cho phn ng vi thuc t Tollens. Vy c th kt lun n c nhng nhm chc no?
Brom ha Zingeron bng dung dch nc brom ch thu c duy nht mt sn phm monobrom.
Ph IR ca zingeron cho bit c s xut hin ca lin kt hydro lin phn t (yu). iu tng t cng
xut hin khi kt thc phn ng kh ha Zingeron theo Clemensen.
2) T cc thng tin trn cho bit:
Mch chnh ca Zingeron
(i)
(ii)
Cc nhm th vo vng thm.
(iii) V tr ca tt c cc nhm th.
3) Vit cng thc cu to ca Zingeron.
4) Hon thnh quy trnh tng hp sau:
+ H2/to
dd NaOH
Zingerol
A +
B
C
xt
(C
11H14O3)
(C3H6O)
Bit A c CTCT:
CHO
HO
OCH3
5) Zingeron c th d dng chuyn ha thnh Gingerol bng cc phn ng sau:

Zingeron 1) Me3SiCl/(Me3Si)2NH D 1) hexanal
Gingerol
(C11H14O3) 2) LDA; -78oC
(C17H26O4)
2) H3O+
Ch :
(1) Me3SiCl/(Me3Si)2NH c s dng chuyn nhm OH thnh nhm SiMe3; nhm
-SiMe3 d b thu phn trong mi trng axit cho tr li nhm OH ban u.
(2) LDA: liti diisopropylamit l mt baz mnh nhng rt cng knh (v mt cu to).
Vit CTCT D.
(ii)
(iii) Vit CTCT ca Gingerol.
Vit cng thc chiu Fischer ng phn (R) ca Gingerol.
(iv)
Ngoi Gingerol ta cn c th nhn c sn phm E ( 2 3%) l ng phn ca
(v)
Gingerol. Vit CTCT E
Thng tin no sau y ng v s hnh thnh E?
(vi)
a) Sn phm ca phn ng iu ch Gingerol l mt cp ng phn i quang.
b) Thu c hn hp cc ng phn quang hc khng i quang.
c) Thu c hn hp ca cp ng phn i quang v ng phn meso.
(vii) Loi nc ca Gingerol bng cch un n vi KHSO4 thu c Shogaol. Vit CTCT
ca Shogaol.
7) C ngh (Curcuma Longa) l mt loi gia v trong thc phm ca ngi n. N cng c s
dng nhiu trong cc n thuc vng Ayurvedic. Curcumin (C21H20O6) l thnh phn chnh
ca c ngh c cu trc tng t nh Gingerol. N c cn bng xeto enol. Curcumin lin quan
n mu vng ca c ngh v cng gp phn to ra v cay.
Ph 1H NMR ca hnh dng xeto trong Curcumin cho tn hiu vng thm tng t Gingerol. N
cng cho mt vch n chuyn dch = 3,5 (2H) v hai vch i (mi 2H l mt vch vng =67 vi J = 16Hz. N c th c tng hp bng cch ngng t hai mol A (cu 4) vi 1 mol pentan2,4dion.
Vit CTCT ca Curcumin.
(i)
Vit CTCT dng enol ca Curcumin.
(ii)
(iii) Curcumin c mu do:
a) C vng thm.
b) C nhm cacbonyl.
c) C h lin hp.
d) C nhm hydroxyl.
BI GII:
1) Cc nhm chc c th c: xeton, hydroxiphenolic
2) Ta c:
Cu to mch chnh ca Zingeron: CH2CH2COCH3.
(i)
Nhm th vo vng thm: OH, CH3.
(ii)
(iii) Cc v tr c nhm th: 1, 2, 4.
3) Cu to ca Zingeron:
CH2CH2COCH3
HO
OCH3
4) Cc phn ng:
H
C
CHO
dd NaOH
H3C
CHC
O
CH3
HO
HO
O
OCH3
OCH3
H2; to/xt
CH2CH2COCH3
HO
OCH3
zingeron
5) Ta c:
(i)
Cng thc cu to D:
O
H3CO
CH2CH2C
CH2-Li+
(H3C)3SiO
(ii)
Cng thc cu to ca Gingerol:

O
H3CO
CH2CH2C
H2
C
H
C
OH
(H3C)3SiO
(iii)
Cng thc chiu Fischer ng phn R ca Gingerol:
(CH2)4CH3
CH3
CH2COR
HO
(CH2)4CH3
H
(iv)
Cng thc cu to ca E:
O
H2
C
H3CO
(H3C)3SiO
H
C
CH3
HC
(CH2)4CH3
OH
(v)
Cu b ng.
6) (i) Cng thc cu to ca Curcumin:
O
O
H2
C
H3CO
OCH3
H
HO
OH
(ii) Cng thc cu to dng enol ca curcumin:

OH
H3CO
HO
H
C
C
H
O
C
H
C
H
H
C
OCH3
OH
(iii) Cu c ng
1. Dng gp np ca protein:
Protein (polipeptit) c nhiu loi khung c cu dng khc nhau. mt cu dng khung trng
thi b ko cng hu nh hon ton ( dng song song hay dng i song trong dng gp np ) v mt
cu dng khc xy ra s xon hon ton ( cu trc xon ).
1) Khong cch gia hai ui mch trong mt hexapeptit trong cu dng xon hon ton l:
a) 10
b) 15
c) 20
d) 25
2) Gi s rng hexapeptit cho c cu trc xon , v mt mi lin kt ni gia nguyn t oxy v
hydro ca nhm NH nu c lin kt hydro tn ti gia hai nguyn t .
O
+
R2
H3N
R4
R6
O-
N
R1
R3
R5
3) Hai hexapeptit (A v B) biu din hai cu dng tng phn trong nc ti pH = 7,0, c bit l
nhm hydro serin c photphoryl ha. A c s xon va phi v s xon tr nn mnh
hn khi serin c photphoryl ha. B c s xon rt yu v hon ton tr nn ri lon khi
serin c photphoryl ha. V cc mi tn ch s nh hng gia cc phn cn li ph hp
vi s khc nhau nu.
Ser
Leu
Phe
Glu
Arg
COOCH3
CH3CONH Lys
Ser
Leu
Phe
Arg
Glu
COOCH3
CH3CONH Lys
2. - lactamaza v tnh khng thuc.
Penixilin l mt dc phm c hu lc chng li s nhim khun. Tuy nhin thnh trjang vi
khun khng thuc tr nn ng bo ng. Xut hin s khng penixilin trong vi khun c quy kt
cho mt enzym cha bit gi l - lactamaza (hay cn gi l penixilinaza), n lm gim hot tnh ca
vng penixilin bng cch m vng - lactam. C ch ca phn ng m vng - lactam lin quan n
s tn cng nucleophin bng nhm OH ca serin hng tn cng ca enzym.
C ch qa trnh ny c trnh by nh sau:
R
N
COO
E nz - Ser - O H
COO
E n z -S e r-O H
N
O
HO
COO
OH
E nz - Ser
HO
HN
O
+ E nz - Ser - O H
+ H 2O
COO
+
O
E nz - S er
HN
O
COO
H 2O
Cc nh khoa hc c gng xc nh c enzym - lactamaza t Staphylococcus aureus.

Khi enzym tinh khit c nh du bng ng v 32P th ta ch nh du mt mnh Serin. Trong phn
tch th serin ch chim 0,35% v khi lng ca enzym - lactamaza. Bit MSerin = 105 Da (n v khi
lng nguyn t).
4) c lng Menzym.
5) S lng aminoaxit cn li hin din trong protein ca mch ny s l:
a) 100
b) 150
c) 275
d) 375
6) nh du u hot ng, - lactamaza c phn ct bi tripsin. Hexapeptit ban u (P1)
cha cc aminoaxit sau: Glu, Lys, Met, Phe v Ser
S dng phng php Edman ta bit c aminoaxit u N l Phe v dy peptit P2.
S dng BrCN ct mch P1 thu c dipeptit P4 v tetrapepetit P3
S dng 1 flo 2,4 dinitrobenzen sau thu phn hon ton ta thu c N2,4
dinitrophenylGlu .
Bit P1; P2; P3 u cha Ser. Hy xc nh v tr cc aminoaxit trong P1; P2; P3; P4.
7) Tnh M(P3) bit MPhe = 165Da; MGlu = 147Da; MHms = 119Da (Hms: Homoserin); Mnc = 18Da.
8) Ch vi mt lng nh enzym - lactamaza th phn ng s xy ra nhanh hn so vi serin t do.
Khi s dng enzym - lactamaza lm xc tc th hng s tc phn ng k1 = 350s-1 cn nu
khng s dng enzym th k1 = 0,5s-1.
T nhng thng tin cho trn, tnh nng hiu lc ca tc nhn nucleophin lin kt vi
trung tm hot ng ca enzym. Cho bit trong trng hp khng s dng enzym th nng Ser OH
t do trong dung dch l 1M.
9) Khi cho cht c ch lin kt vi trung tm hot ng ca - lactamaza th c th c ch c
enzym. Hng s phn ly ca phc cht c ch - lactamaza i vi ba cht c ch khc nhau c
cho nh sau:
Cht c ch
Hng s phn ly (KD)
A
2,0.10-3
B
1,0.10-6
C
5,0.10-9
Trong ba cht A, B, C cht no c hiu qa bo v penixilin khi enzym - lactamaza
Cng thc cu to ca cht c ch:
H2C
Br
N
O
COO-
c th lin kt vi trung tm hot ng ca enzym th nhm OH ca Serinsex tn cng

nucleophin v kt qa dn n s m vng v tch Br- ra khi cht c ch. Tc nhn electrophin mnh
s c sinh ra v s tn cng vo trung tm hot ha ca enzym lm mt hot tnh ca enzym.
10) Vit s cc phn ng xy ra.
BI GII:
1) Cu d ng.
2) Ta c:
O
+
R2
H3N
R4
O-
R6
N
R1
R3
3) Ta c:
CH3CONH
Lys
Ser
Leu
Phe
Glu
Arg
COOCH3
CH3CONH
Lys
Ser
Leu
Phe
Arg
Glu
COOCH3
4) 30000Da.
5) Cu c ng
6) P1: Phe Glu Ser Met Leu Lys.
P2: Glu Ser Met Leu Lys.
P3: Phe Glu Ser Hms/Met.
P4: Leu Lys.
7) 482Da
8) 700M
9) Cu c ng
10) S phn ng:
R5
Br
H2C
Enz - Ser - OH
+
O
COO-
CH2
N
hay
O
O
COO-
Enz - Ser
Enz - Ser
COO-
H2C
HN
O
O
Enz - Ser
COO-

Phn ng Diels Alder l phn ng ng vng [4 + 2] gia mt olefin v mt dien to thnh
xiclohexen c khm ph bi gio s Otto Diels v ng s Kurt Alder khi h trn benzoquinon vi
lng d xiclopentadien v nhn c kt qa sau:
A
(C11H10O2)
1) Vit CTCT A (khng cn ch n mt lp th)

Phn ng Diels Alder l ng b, mt giai on v c tnh c th lp th cao. V d: ch mt
ng phn C c to thnh t phn ng sau:
H
CN
CN
+
CN
CN
CN
m khng to thnh:
CN
H
H
CN
Nu s dng (E) 1,2 dixianmetylen th thu c hai ng phn lp th D1 v D2

2) Vit CTCT D1; D2.
CN
H
phn ng ban u (to ra B t xiclopentadien v benzoquinon). Diels v Alder thu c

mt trong 6 ng phn lp th ca B.
O
6
4
5
3) Hy cho bit l ng phn no?
Sau khi un nng lu (15h, 120oC) th t B (tonc = 157oC), Diels v Alder thu c hai ng phn
lp th mi l E(tonc = 153oC) v F (tonc = 163oC). Di tc dng ca xc tc 25oC ta thu c ng
phn lp th G (tonc = 184oC).
B E + F
10%
20% 70%
B G
60%
40%
Khng cn thit phi bit E, F, G l cht no trong s 6 ng phn lp th trn
4) Cc cu khng nh sau l ng hay sai hoc khng d kin chng minh:
Phn ng Diels Alder l thun nghch.
B bn nhit ng hn E.
E km bn nhit ng hn F.
G l ng phn quang hc khng i quang ca B.
G bn nhit ng hn F.
5) Cho s phn ng:
OMe
O
CO2Me
bazo manh
+
MeO
CO2Me
bazo manh
I
K
(C12H16O5)
(C11H12O4)
OMe
CO2
-MeOH
OMe
CO2Me
Xc nh I, K, L. Bit K ch c mt nhm metyl v L l sn phm cng Diels Alder ca K v

anken cho trc.
BI GII:
1) Cng thc cu to ca A:
O
2) Cng thc cu to ca D1 v D2:

H
H
CN
D1:
CN
D2:
CN
H
CN
H
D1 v D2 l hai ng phn i quang.

3) Cu trc 2 (chnh) v cu trc 1 (ph). Theo bi th cu trc tho mn s l 2
Phn ng Diels Alder cho sn phm c ha hc lp th endo. Vn ny c cp n
cu 2, cu trc C. Nh ch ra cu trc C th cu dng endo c c trng bi 2 nguyn t H v
nhm CH2 ca h hai vng cng pha so vi mt phng vng. Ch c cu trc 1 v 2 trong s 6 cu
trc cho l c ha lp th endo, endo. Tt c cc cu trc khc u c t nht mt nhm th theo
hng exo. Trong cu trc 1, 3 vng to ra phn t c hnh dng ch U b nh hng khng gian nhiu
hn so vi cu trc 2 c dng phn t hnh zig zag.
4) Cu ng: 1, 4.
Cu sai: 2, 3.
Cha d kin: 5
5) Cu trc ca I, K, L:
OMe
O
CO2Me
CO2Me
CO2Me
CO2Me

Quy tc Cahn Ingold Prelog (CIP) c s dng xc nh ha lp th ca phn t.
1) Da vo quy tc CIP hy xc nh hn cp ca cc nhm th sau:
a) -SCH3 v P(CH3)2
b) CCl3 v CH2Br.
c) Gia
O
CH3
Pseudoephedrin (1) l cht hay gp trong cc loi thuc thng thng chng cm lnh. N c
cng thc cu to:
OH
CH3
NHCH3
1
2) nh du * vo cc trung tm lp th v cho bit n l R hay S.
3) V cng thc Newman hay cng thc phi cnh ca (1) v v cng thc chiu Fischer ca 1.
un nng 1 vi KMnO4 trong iu kin nh nhng thu c Methcanthinon 2
OH
CH3
MnO4-/H+
NHCH3
4) Vit cng thc cu to 2 (c xt lp th) v cn bng phng trnh phn ng xy ra. Ch r s

thay i s oxy ha ca tt c cc nguyn t c s thay i s oxy ha.
un nng 2 vi LiAlH4 thu c 3. Cht ny ch khc 1 tonc.
OMe
5) a) Vit cng thc lp th ca 3

b) Pht biu no sau y ng?
1 v 3 l cc ng phn lp th.
1 v 3 l cp i quang.
1 v 3 l hai ng phn lp th khng i quang.
1 v 3 l hai ng phn cu dng.
c) Vit cng thc ca trng thi chuyn tip trong phn ng 2 3
BI GII:
1) Nhm c hn cp cao hn s l: -SCH3; -CCl3 v
O
CH3
2) Ta c:
OH
*
S
CH3
NHCH3
3) Cng thc chiu Newman hay cng thc phi cnh ca 1:

CH3
CH3
HO
H3CHN
H3CHN
hay
HO
Ph
Ph
Cng thc chiu Fischer ca 1:

Ph
H
CH3
OH
NHCH3
hay
H3CHN
H
CH3
4) Phng trnh phn ng:
HO
H
Ph
OH
+0
+2
CH3
+ 2 MnO4
+7
Ph
6H
CH3
5 Ph
+2
+ 2 Mn2+ +
NHMe
NHMe
5) a) Cng thc cu to ca 3 ( xc nh lp th):

OH
CH3
NHCH3
b) Cu ng: 1, 3
Cu sai: 2, 4
c) Cu trc ca cc sn phm trung gian:
CH3
CH3
H3C
H
Li
Li
1) H+
H3CHN
2) H2O
HO
Ph
Ph
H
-
H
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
N
CH3
1.
2.
CH3
CH3
N
CH3
Xp cc cht N,N-dimetylfomamit (A). N-metylaxetamit (B) v propanamit (C) theo th t tng

dn nhit si.
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
8 H2 O
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 Gly Gly
Gly 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: L alanin v D alanin l hai enantiome. Nh vy i vi 3 peptit glyxin, L alanin v D
alanin ta c th thu c bao nhiu tripeptit?
O
H2N
H2N
H2N
OH
H
OH
OH
H
H3C
CH3
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 polyamit 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 tnh n khng c mu cn trong dung dch baz
n c mu tm (pH: 8,3 10,0)
HO
OH
H2SO4 dac; 180oC, 5h
G +2
O
OH
phenolphtalein
OH
H+
7.
8
Vit cng thc cu to ca H.

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
(a)
(b)
(c)
OH
H
O
O
O
(d)
(e)
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.
H
hay
N
H
OH
O
Gly - Gly - Gly

O
H3N
N
N
H
O
4.
27
5 Trong s th 26 tripeptit c ng phn quang hc
Aminoaxit khng c tnh quang hot: 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.
HO
8 Cht e
Cc cacbohydrat thin nhin u c to thnh t phn ng quang hp trong thc vt. Tuy
nhin 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
CO2Me
O
HO
100oC
ong han kin
CO2Me
OsO4
HO
CO2Me
CO2Me
Me2C(OMe)2
H+, CH3COCH3
CO2Me
O
enzym pig liver
D (spc)
CO2Me
CO2H
CO2Me
F
+
O3; MeOH
CO2Me
O
O
MeO2C
CO2H
O
O
O
E (spp)
CO2Me
MCPBA
CO2Me
O
O
CH2OH
HO
O
H3O+
1) MeOH/H+
CO2Me
2) LiAlH4
sau do H2O
OH
OH
I
1. Hp cht A c cng thc phn t C10H10O5. Vit cng thc cu to A.

2. Trong cc mnh lin quan n vic chuyn ho t A thnh C sau y th mnh no ng,
mnh no sai?
a) OsO4 l tc nhn oxy ha trong phn ng chuyn A thnh B.
b) MeOH l sn phm ph trong phn ng chuyn ha B thnh C.

c) Proton ng vai tr xc tc trong phn ng chuyn ha B thnh C.
d) C c th c to thnh vi hiu sut thp khi khng c Me2C(OMe)2.
Enzym pig liver esteraza c th thy phn este thnh axit cacboxylic. Thu phn C bng enzym
pig liver esteraza sinh ra hn hp D v E trong E l sn phm chnh. Gc quay cc ca hn hp l:
[]D20 = -37,1o cn ca E tinh khit l []D20 = -49,0o.
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 C9H16O5. Cc ga tr ph NMR ca H cho di y: 1HNMR
(CDCl3) 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).
a) Vit cng thc cu to ca H.
b) Xc nh cu hnh tuyt i ca C1; C2; C3: C4 ca hp cht I.
c) 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
U
CH2OH
Disaccarit l hp cht c to thnh t hai n v monosaccarit bi lin kt glycozit.

Polisaccarit cha t 10 n vi ngn n v monosaccarit. V d v disaccarit cho di y:
H OH
H
HO
H
H
H
OH
OH
H OH
O
H
lien ket glycozit
O
OH
H
H
OH
OH
H
d) 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
H
O
O
H
H
OH
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
6. C1, 2, 4: S
7.
C3: R
OH
H
CHO
HO
HO
HO
H
CH2OH
8. 2
Ete crown c th to c lin kt vi cc ion kim loi kim. V d cc hng s lin kt ca hai
azacrown (ete vng cha nit) vi Na+, K+, Cs+ c cho bng di:
Hng s lin kt (lg10K)
Ion km loi
Bn knh (pm)
Hp cht A
Hp cht B
+
Na
98
2,49
3,57
K+
133
1,83
5,00
Cs+
165
1,37
3,39
Antraxen cho s pht quang mnh vi bc sng pht x trung tm l 325nm. Kt hp vi s
lin kt chn lc ca cc azacrown i vi ion kim loi kim v s pht quang mnh ca antraxen, mt
ion kim loi pht quang chn lc E c pht trin.
O
O
O
N
H2C
O
N
CH2
A
B
1. Cho bit cc cht C v D trong qa trnh tng hp sau:
1) NaBH4
2) PCl5/benzen
HO
pyridin
O
N
- +
2) t - BuO K
HO(CH2)2NH(CH2)2OH
SO2Cl
1)
OH
CH2
so snh, th dn xut th antraxen ca F v G cng c tng hp. Cc hp cht E, F, G

u khng c tnh pht quang cc iu kin trung tnh do hiu ng chn s di chuyn ca electron
(photoinduced electron transfer PET) do cp electron khng phn chia ca nguyn t nit nm pha
hot ng ca antraxen:
O
OH
OH
N
N
H2C
O
H2C
G
F
2. Khi thm dung dch HCl hp cht no s pht quang?
a) Khng c.
b) E v F.
c) Ch G
d) Tt c.
3. Khi thm mt lng tng ng kali axetat vo dung dch long ca E, F v G trong metanol th
hp cht no s pht quang mnh nht?
a) E
b) F
c) G
4.
Khi thm mt lng tng ng axetat kim loi vo dung dch long ca F th axetat kim loi
no s pht quang mnh nht?
a) CH3COONa
b) CH3COOK
c) CH3COOCs
d) Khng c.
Trong qa trnh chiu x vi tia cc tm trans stinben chuyn ho thnh mt cht trung gian H,
H chu s vng ho quang ho sinh ra dihydrophenantren I. Oxy ho tip I cho ta phenantren.
hv
nhiet
hv
nhiet
H
H
oxy hoa
3.5. Vit cng thc cu to H

3.6. Ho lp th ca hai nguyn t H trong hp cht I l g (cis hay trans)?
Dn xut ca Dihydroazulen J c tnh cht quang ho hc rt th v. Khi chiu x th th cht J
khng mu s chuyn v thnh vinylheptafulven K. un nng K th ta li thu c J:
CN
CN
CH3
CN
CH3
CN
hv
10
nhiet
6
9
8
J
7. Hp cht no hp th nh sng bc sng di hn?
a) J
b) K
8. Hp cht K c th phn ng vi mt lng tng ng CF3CO2H to thnh h thm bn vng.
Nguyn t no cacbon no ca K d b proton ha nht?
a) C 2
b) C 3
c) C 4
d) C 5
BI GII:
1.
N
H
Cl
H2C
O
O
2. d
3. e
4. a
5. Cng thc cu to ca H:
6. trans
7. K
8. C3
III.
BI TP CHUN B CHO OLYMPIC HA HC QUC T:
Cht ong cha Q cha 65,2% cacbon v 6,75% hydro v khng c nguyn t no thm na
tr oxy. Q c bit c tnh cht axit v chun 43,7mg cht ny cn 23,7mL dung dch nc ca
natri hydroxit 0,0100M t n im tng ng. Khi lng phn t ca Q nh hn 200.
a) Cng thc phn t ca Q l g v nhng nhm chc no gy nn tnh axit ca hp cht?
Q phn ng vi hydro c mt bt mn platin to thnh hp cht mi A. Kh A vi natri bohydrua
trong etanol cho cht B. Hp cht B d dng loi nc khi un nng vi axit sunfuric to anken C.
Ph NMR 13C ca C cho thy s c mt ca mt nhm metyl gn vo lin kt i.
b) Nhng nhm chc no ph hp vi nhng phn ng trn?
Phn ng ozon phn cht C ri oxy ha k tip ch cho hai phn l axit etanoic v mt axit
dicacboxylic mch thng D. S phn chia tng t ca Q to thnh axit oxalic (axit etandioic) v cht E
c cha mt nhm chc axit cacboxylic.
c) Suy ra cu to ca D v E, t hy xc nh cng thc cu to c th c ca Q.
BI GII:
Cng thc thc nghim: C10H16O3 (M = 184,13). Do MQ xp x 200 nn cng thc phn t ca Q
trng vi cng thc thc nghim (C10H16O3).
Q c tnh axit nn c th cha mt nhm CO2H (do ch c 3 nguyn t oxy trong phn t). Vy
Q l axit n chc, phn ng vi NaOH theo t l mol 1:1
R CO2H + NaOH = R CO2-Na+ + H2O
43,7mg 43,7.10-3g Q phn ng vi 23,7mL dung dch NaOH 0,0100M
Vy nNaOH = 23,7.10-3.0,0100 (mol)
Nu 43,7.10-3g Q phn ng vi 23,7.10-3.0,0100mol NaOH th 43,7.10-3.(103/23,7.0,01)g Q phn
ng vi 1 mol NaOH, ngha l 184,3g Q phn ng vi 1 mol NaOH. iu ny chng t rng 1 mol Q
phn ng vi 1 mol NaOH v nh th cho php ta kt lun Q l axit n chc dng R CO2H.
K tip ta cn xc nh nguyn t oxy cn li trong C10H16O3. (hay C9H15O CO2H)
C th l:
ete:
R O R.
ru: R O H.
xeton: R CO R.
andehit: R CHO.
S lin kt i trong Q = 3. R rng cha xc nh c hai trong s ba lin kt i nhng
xc nh c 1 (ca nhm CO2H).
Mt khc, theo cc th nghim:
+
/
2 / Pt
4 / EtOH
Q H
A NaBH
B H
C + H 2O
C l mt anken nn B l ru v B loi nc cho ra anken C khi un nng vi H+
Ngoi ra, C cn c mt nhm metyl gn vo ni i cho nn ta d on:
H3C
H
C
H2
C
H3C
OH
Nu iu ny ng th A phi l mt xeton
H3C
H2
C
NaBH4
H2
C
H
C
H3C
H3C
OH
C
A
B
Cn bit rng nhm andehit v xeton b kh bng NaBH4 cho ru bc 1 v ru bc hai.
Nu A cha nhm xeton v nhm chc axit cacboxylic th A c cng thc cu to:
H3C
H2
C
(CH2)7 CO2H
v gii thch c 2 trong s cc lin kt i tng ng. Mt trong nhm chc axit v mt
trong nhm xeton.
C ngha l trong Q cn mt lin kt i na v do Q phn ng cng vi hydro nn c im cu
to cn li phi l mt lin kt i. Vn l v tr ca lin kt i trong Q.
H3C
H2
C
H2
C
H
C
H3C
(CH2)7 CO2H
(CH2)7 CO2H
CH3CH=CH(CH2)6CO2H
OH
C
B
A
v gi thit c xc nhn do C b ph v bi ozon v mt cht oxy ha to thnh axit axetic v mt axit
dicacboxylic mch khng nhnh.
H3C
CH3CH=CH(CH2)6CO2H
C(CH2)6CO2H
OH
OH
iu ny cho php khng nh C duy nht v t khng nh A

Q ny chc chn ch n gin l mt phn t c cha nhm chc xeton (tng t A) v axit
cacboxylic (tng t A) v mt lin kt i.
Nhng Q khi ozon phn v oxy ha to thnh HOOC COOH cng vi E.
Khng quan tm n E v mt mnh nh ch c th xut pht t phn t c dng tng qut:
R
R - CH=CH - CO2H
C
OH
OH
OH
Nh vy xc nh c Q duy nht l:
H3C
(CH2)5C
H
C
H
CO2H
Vn cui cng cn li l s ng phn ha cis trans ca lin kt i:
H3C
H3C
C
O
O
(H2C)5
(H2C)5
CO2H
trans
CO2H
cis
Vn ny khng th kt lun c vi cc gi thit cho.
Axit crisophanic c trong sc t antraquinon thin nhin c lp c t r cy i hong vi cu
to di y. Mt phng php tng hp phn t ny do Khoa Nghin Cu Ha Hc thuc i Hc
Quc Gia Australia ngh:
OH
OH
CH3
O
a)
b)
c)
d)
e)
axit crisophanic
3-metylanisol (3-metyl-metoxybenzen) c kh bng kim loi liti trong hn hp amoniac ha lng
khan nc, tetrahydrofuran v t-butanol to B (C8H12O). X l B vi kali amidua trong amoniac
lng khan nc ri x l tip trong dung dch nc dn n s ng phn ha B thnh C. Hy vit
ba cng thc cu to c th c ca C.
Ph NMR 1H ca C cho thy c hai proton ca lin kt i khng k cn nhau. Ngoi ra, cn cho
bit c hai nhm metylen cnh nhau, mt trong hai nhm ny k cn mt proton ca lin kt i.
Hy vit cc cng thc cu to ca C tho mn iu kin trn.
Phn ng ca C vi 5-hydroxi-naphtalen-1,4-dion to sn phm ghp Diels Alder D(C18H18O4).
Ph NMR 1H ca D cho thy mt cng hng 10,5 thng nht vi mt proton v l ch nh ca
mt nhm hydroxyl lin kt ni phn t. Hy ngh ba cng thc cu to c th c ca hp cht D.
Enol ha D bng cch x l vi kali cacbonat trong metanol nng ri oxy ha k tip vi kali
nitrosodisunfonat (mui Fremy) to mt sn phm kiu quinon mu vng E (C18H16O4). Ph NMR
13
C ca E cha tng cng 9 cng hng c th quy cho nhng cacbon bc 4. Nhit phn E ti 180oC
trong 15 pht li phng thch eten bng phn ng ngc Diels Alder ng thi to thnh F
(C16H12O4). Ph NMR 1H ca F cho thy ba vch n, mi vch tng ng vi mt proton (vch
thp nht ti 11,00) v hai vch n 3 proton, mt vch ti 4,01 v mt vch ti 2,25ppm. Cn c
trn cc chng c ny, ngh cc cng thc cu to c th c ca cc hp cht E v F.
Khi cho F tc dng vi bo triclorua trong diclometan ti 10oC ri x l tip thu c mt cht rn
mu cam, khi ph cho m/e = 245. Tr s ny ging nh axit crisophanic thin nhin. Vit ton b
cng thc cu to ca qa trnh tng hp axit crisophanic.
BI GII:
Ton b qa trnh tng hp axit crisophanic ca cu hi din ra nh sau:
OCH 3
OCH 3
OCH 3
OH
CH 3
OH
OH
OH
OH
OH
OCH 3
OCH 3
CH 3
CH 3
O
OH
OH
OCH 3
OH
OCH 3
OH
CH 3
OH
OCH 3
O
OH
O
axit crisophanic
Hp cht B l sn phm kh Birch d kin
C l mt ng phn lin hp (tip cch) ca B, c th c bt c cu to no: C1; C2; C3.

CH3
OCH3
OCH3
CH3
CH3
CH3
C1
C2
C3
Trong nhng cu to ny, ch c hai cu to C1 v C2 tho cc s liu NMR. Nh vy loi C3.
Bt k ba sn phm Diels Alder no xut pht t C1 n C3 cng chp nhn c cho li gii
ca phn th ba do chng u cha nhm hydroxyl c lin kt hydro ni phn t. Tuy nhin phi
ngh cn thn xc nh li gii ng.
thi im ny, cha th xc nh C1 hay C2 l cu to ng ca C. Tuy nhin phn cui c
th thy r li gii xut pht t D1 hoc D11, sn phm cng vng ca C1 l khng th chp nhn c
do khng b kh metyl vi BCl3. -10oC y l tc nhn chn lc ct nhm ete peri vi mt nhm
cacbonyl; v mt ny th BCl3 chn lc hn BBr3
OH
OH
CH3
OH
OCH3
O
CH3
D1
D11
Tuy nhin ngay c y c th c mt kt qa khc nhng khng phi cht c th to axit
crisophanic. Ha hc vng ca s cng vng nu trn thc t c th c c, nhng phn ng cng
Diels-Alder c th tip din to mt ng phn khc nu di y. ng phn ny khng dn n
axit crisophanic v do cu to ny c cho trong cu hi nn c th d dng on c li gii. Cng
cn thit thy rng xt v mt tng hp cht th y cng khng thc s l cch khng c sai lm v
khng th dng nh l mt chng c cho cu to ca axit crisophanic. Vi chi tit y, c th tr li
cu hi d vi ha hc vng ca s cng vng C2 v 5-hidroxinaphtalen-1,4-dion.
OH
OH
OH
CH3
CH3
OH

Phn ng chuyn v kiu Claisen (Claisen type rearrangement) l mt cng c thun li cho cc
nh ha hc trong tng hp cht hu c. Tuy nhin vi hc sinh th phn ng ny thng kh nhn bit
v i hi suy ngh. Mt v d in hnh ca phn ng c ghi di y:
R
OMe
OMe
Nm 1977 mt sesquiterpen furan (K) c tch t mt loi san h mm Australia l Sinularia

gonatodes. Hp cht ny c kh nng v hiu ha nc c ca ong v s kin mt cht n gin nh th
li phn ng c nh mt tc nhn chng vim gy ch ng k n cc nh ha tng hp. Mt qa
trnh tng hp nh th c m t di y.
Axit (A) c este ha vi 2(-trimetylsilyl)etanol [Me3SiH2CH2OH] v xeto-este sinh ra c
kh mt cch chn lc ti nhm cacbonyl ca xeton vi NaBH4/CeCl3 to mt hp cht B
(C14H22O4Si).
HO2C
O
O
A
X l B vi 1,1,1 trimetoxyetan vi s c mt ca mt vt (lng rt nh) axit khan nc to
mt cht trung gian C c th chuyn v kiu Claisen khi nung nng to cht C. Phn tch ph ca C
cho thy s hin din ca mt nhm este trimetylsilyletyl v mt nhm este metyl
a) Suy ln cc cu to ca cc hp cht B v C v cht trung gian dn n C.
Kh C vi liti bo hydrua to thnh ru bc nht D(C16H26O4Si) c th b oxy ha vi pyridin
clocromat chuyn thnh F. Phn ng ca F vi tc nhn Wittig G to thnh hai ng phn H v I. Sn
phm chnh H c ha hc lp th E.
Ph3P
CHO
G
b) Nu cu to ca cc hp cht D I, cn thn ch r ha hc lp th chnh xc ca cc ng
phn H v I.
Phn ng Wittig sau cng vi ylid chuyn ha t metyl triphenylphotphoni iodua to thnh J.
Cht ny sau khi ct este trmetylsilyletyl vi tetra n butyl amoniflorua to hp cht mong mun K.
c) Nu cc cu to hon chnh s ca qa trnh tng hp.
BI GII:
Lu :
Khng cn qa quan tm n c ch phn ng do cu hi c gi kh c th.
S oxy ha vi pyridin clocromat ng ch ch trong iu kin khan nc ru bc 1 ch
b oxy ha thnh andehit ch khng to thnh axit cacboxylic.
S chuyn i C thnh D phi gm c s kh este metyl do D vn cn cha silic. Nu nh
este trimetylsililetyl b kh s khng cn silic.
Cui cng, cng cn lu rng bi ny s dng cch k hiu cho tc nhn Wittig, ngha l
cu to vi mt lin kt i hnh thc thay v cu to lng cc thng dng cho ylid. Mt
khc tc nhn G cng cho php lm tng mch cacbon ca mt andehit.
Cc phn ng xy ra nh sau:
M e 3 H 2 S iH 2 C C O 2 C
M e 3 H 2 S iH 2 C C O 2 C
OH
M e 3 H 2 S iH 2 C C O 2 C
M e 3 H 2 S iH 2 C C O 2 C
C H 2O H
C O 2M e
OH
M e 3 H 2 S iH 2 C C O 2 C
OH
M e 3 H 2 S iH 2 C C O 2 C
CHO
OH
OH
H O 2C
M e 3 H 2 S iH 2 C C O 2 C
O
OH
Cc sn phm v qa trnh trung gian:
OH
CHO
Me3H2SiH2CCO2C
CHO
Me3H2SiH2CO2CC
Me3H2SiH2CO2CC
CH3
H+
CH3
H
H3CO
OCH3
CH3
CH3
OCH3
Me3H2SiH2CO2CC
Me3H2SiH2CO2CC
H
CH3
OCH3
H3C
O
H
CHT TRUNG GIAN CHO PHN NG KIU CHUYN V CLAISEN

S KH:
(vi)
Li/NH3/t-BuOH
(i)
CO2Me
OCH3
O
(vii)
Na/NH3/EtOH
(ii)
HN NH
Ghi ch: Di-imit: NH=NH c to

thnh do s oxy ha hydrazin
LiAlH4/AlCl3
CO2H
O
(viii)
Zn-Hg/H+
(iii)
O
NaBH4
(iv)
CHO
NH2NH2/OH-
(v)
CO2Me
H2/Pd
S OXY HA:
(ix)
(xiv)
axit m-clopebenzoic
CH2Cl2
KMnO4/H2O/OHto
(xv)
(i) B2H6
(ii) H2O2/OH-
(x)
H+/Cr2O72-/axeton
(xvi)
OsO4/Me3NO
OH
(xi)
OH
piridin clocromat(PCC)
CH2Cl2
(xii)
(i) O3
(ii) Me2S
(xiii)
(i) O3
(ii) KMnO4
CC PHN NG KHC:
(xvii)
(xxiii)
CO2H
to
+
to
CO2H
O
(xviii)
CO2H
HO2C
(xix)
to
CHO
(xxiv)
Ph3P CH2CH3
OH
CH3C O CCH3/piridin
O
O
(xxv)
OH
(xx)
O
axit axetic/H+
(xxvi)
HPh3P+ C CO2Me
PhS-
(xxi)
CHO
OCH3
(EtO)2PCH2CO2Et/NaH
(xxvii)
OCH3O
CO2Me
(xxii)
BBr3/CH2Cl2
to
+
O
CO2Me
OCH3
(xxviii)
CO2H
H3C
anhydrit axetic/to
CO2H
Ghi ch thm: Tr trng hp (xiii), (xvi), cn li hc sinh phi bit c tn ca cht ban u theo
danh php IUPAC. Tr trng hp (xiii), (xiv), (xx), (xxii), (xxiii), (xvii) cn li th hc sinh phi bit
c tn ca sn phm cng theo IUPAC.
BI GII:
S KH:
(i)
(ii)
CO2H
OCH3
(iii)
(iv)
(v)
CO2Me
(vi)
CO2Me
Nh: Cht kh XS c th
kh anken phn cc
OH
(viii)
(vii)
S OXY HA:
(ix)
COOH
(x)
CO2H
COOH
(xi)
(xii)
O
CHO
H
(xiv)
(xiii)
O
O
+ CO2
(xvi)
HO
HO
(xv)
H
H
OH
CC PHN NG KHC:
(xvii)
O
O
O
(xviii): Khng phn ng tr khi nhit rt cao

CO2Me
(xix)
(xx)
(xxi)
(xxii)
CO2Me
O
CO2Me
CO2Me
(xxiii)
(xxiv)
O
O
O
O C CH3
(xxv)
(xxvi)
O
CH3
O
OH
(xxvii)
(xxviii)
OH O
O
O
H3C
O
OH

a) Xystin (C6H12N2O4S2) l mt axit diamino dicacboxylic, l sn phm nh hp ca L xystein.
Sn phm nh hp ny c th c tch i khi x l vi mt thiol nh mercaptoetanol
(HOCH2CH2SH) cho L xystein (C3H7NO2S).
Vit cng thc cu to ca xystin vi cu hnh tuyt i
(i)
Vai tr ca mercaptoetanol trong phn ng ny l g?
(ii)
1 mol xystin c th c tch i nh x l vi axit pefomic HCOO2H to thnh 2 mol axit
xysteic C3H7NO5S l mt axit mnh.
(iii) Vit cu to ca axit xysteic ti im ng in
Khi mt peptit gm 2 mch A v B lin kt nh mt lin kt n disunfua gia hai gc
(iv)
xystein trong mi mch c x l vi axit pefomic thu c hai peptit mi A v B ti pH
7,0 vi in tch tng cng theo th t bng +5 v -3. Hy tnh in tch tng cng ca peptit
ban u ti cng pH.
b) Khi peptit C (M = 465) c thu phn hon ton bng dung dch HCl trong nc th trong dung
dch sau thy phn thu c cc lng c s mol bng nhau ca glyxin (Gly), phenylalanin
(Phe); axit aspactic (Asp), axit Glutamic (Glu) v mt ng lng amoniac (NH3).
Khi x l C vi enzym cacboxipeptidaza thu c axit glutamic v mt tripeptit. Thu phn mt
phn tripeptit trong axit cho mt hn hp sn phm, trong c hai cht c xc nh l axit
glyxilaspactic (Gly Asp) v aspactilphanylalanin (Asp Phe).
T cc thong tin trn hy suy ra trt t ca ton b peptit C.
(i)
im ng in gn ng ca peptit C (pH < 7; pH 7; pH > 7) l bao nhiu?
(ii)
BI GII:
a) (i)
NH3+
CO2-
S
-
O2 C
S
NH3+
(ii) tc nhn kh
(iii)
Cng thc cu to
NH3+
SO3-
HO2C
(iv)
+4
b) (i) Gly Asp Phe Glu.
(iii) pH < 7
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:
CH2OH
O
HO
HO
OH
CH2OH
(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
1) NaCN / H+
HO
2) H3O+/to
OH
CH2OH
(D) - arabinoz
c) Khi mt disaccarit (c tnh kh) l turanoz c em thy phn, thu c D glucoz v D
fructoz 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 2,3,4,6 tetra O metyl D fructoz.
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
OH (CH2OH)
OH (CH2OH)
OH
CH2OH (OH)
OH
b) Cc phn ng xy ra:
CHO
HO
H
1) NaCN/H+
H
OH
H
OH
CH2OH
H
HO
H
H
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
+
CHO
OH
H
OH
OH
CH2OH
H
HO
H
H
CHO
OH
H
OH
OH
CH2OH
COOH
OH
H
OH
OH
CH2OH
+
COOH
OH
H
OH
OH
CH2OH
H
HO
H
H
H3O+/to
H
HO
H
H
HO
HO
H
H
CHO
H
H
OH
OH
CH2OH
-H2O
CH2OH
O
H
H
OH
OH
H
-H2O
OH
CH2OH
O
H
OH
OH
OH
H
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

a) Hy cho bit cch tng hp cc hp cht c nh du bng cch dng bt k vt liu hu c no
nu ban u khng nh du. c php dng bt k cht v c cn thit no d c nh du hay
khng
(i)
1 D etanol
(S) CH3CHDCH2CH3
(ii)
b) Clobenzen phn ng vi dung dch NaOH m c trong nc di nhit v p sut cao (350oC,
4500psi), nhng phn ng ca 4 nitroclobenzen xy ra d dng hn (NaOH 15%, 160oC). 2,4
Dinitroclobenzen thu phn trong dung dch nc ca natri cacbonat ti 130oC v 2,4,6
trinitroclobenzen thu phn ch cn nc un nng. Sn phm ca tt c cc phn ng trn l cc
phenol tng ng.
Xc nh loi phn ng trn v ch r c ch tng qut ca phn ng ny.
(i)
3 nitroclobenzen phn ng vi dung dch hydroxit trong nc nhanh hn hay chm
(ii)
hn so vi 4 nitroclobenzen?
(iii) 2,4 Dinitroclobenzen phn ng vi N metylanilin cho mt amin bc ba, hy vit
cng thc cu to ca amin ny.
(iv)
Nu 2,4 dinitroflobenzen phn ng vi cc cht c tnh nucleophin nhanh hn 2,4
dinitroclobenzen th c th thm chi tit g vo c ch phn ng trn?
BI GII:
a)
(i)
OH
1) LiAlD4 hay NaBD4

C
H3C
H3C
2) H3O+
1 - D - etanol
axetandehit
(ii)
C
H
H3C
1) C6H5SO2Cl/piridin
C
CH2CH3
HO
2) LiAlD4
3) H3O+
H3C
CH2CH3
(S) - 2 -deuterobutan
(R) - 2 - butanol
b)
(i) Phn ng th nucleophin trn nhn thm
C ch tng qut:
X
X
+ Nu-
(ii) Chm hn
(iii) Cng thc cu to:
(1)
Nu-
Nu
(2)
+ XE
X = Cl
E = NO2 (1 3 nhm)
NO2 CH3
N
O2N
(iv) Theo c ch phn ng cu (i), bc (1) chm hn bc (2) nn bc (1) l bc quyt nh tc

phn ng.

a) Xt hai phn ng cng di y:
Z
R
I)
H+
(CH2)n
Nu:
Z = O; Nu: = C; N; O; S; n = 2, 3, 4
H+
II) (CH2)n
Nu:
Z = N; Nu: = C; N; O; S; n = 2, 3, 4
(i)
T hai phn ng c th thu c cc ng phn lp th no ca sn phm?
Trong phn ng (I), nu Z = O v Nu: = NH2 th cu to ca sn phm cui cng nh th
(ii)
no?
b) D on (mt hay nhiu) sn phm t phn ng:
HO
HCHO
NHCH3
BI GII:
a) (i)
Z-
ZH
(CH2)n
Z
R
I)
(CH2)n
Nu:
(CH2)n
Nu
Nu
-
H+
ZH
(CH2)n
Nu
(CH2)n
Nu
ng phn i quang (nh) hay anome
H
Z
(CH2)n
(CH2)n
Nu
II) (CH2)n
Nu
H+
Z-
Nu:
ZH
(CH2)n
(CH2)n
Nu
Nu
ng phn khng i quang (syn & anti)
(ii)
OH
R
(CH2)n
O
NH
H+
(CH2)n
OH
NH2
+ H2 O
(CH2)n
(CH2)n
NH
b)
HCHO HO
HO
+
N
NHCH3
CH3
CH3
OH

a) Tnh baz ca mt s hp cht cha nit c cu to tng quan c nu nh sau:
Hp cht
Cu to
Hp cht
Cu to
pKa
NH2
Piridin
5,17
Anilin
Pirol
N
H
N
0,40
Xiclohexylamin
NH2
pKa
4,58
10,64
Pirolidin
11,20
H
N
p-Aminopiridin
NH2
9,11
NH2
6,03
Morpholin
8,33
NH
m-Aminopiridin
N
Piperidin
11,11
NH
So snh v gii thch s khc bit trong tnh baz ca mi cp sau:

Piperiin / piriin
(i)
(ii)
Piridin / pirol
(iii) Anilin / xiclohexylamin
p aminopiridin / piridin
(iv)
(v)
morpholin / piperidin
b) S khc bit trong tnh cht vt l ca hn hp trit quang (raxemic) axit cis 2 aminoxiclohexan
1 cacboxylic v axit 2 aminobenzoic c nu trong bng
Axit cis-2-aminoxiclohexan-1Axit 2 - aminobenzoic
cacboxylic
im nng chy (oC)
240
146 147
Tnh tan trong: nc (pH = 7)
tan
Khng tan
HCl 0,1M
rt d tan
Khng tan
NaOH 0,1M
rt d tan
Khng tan
Et2O
Khng tan
rt d tan
-1
Di hp th IR (th rn, cm )
1610 - 1550
1690
pKa1
3,56
2,41
pKa2
10,21
4,85
(i)
ngh cc cu to hp l ca axit cis 2 aminoxiclohexan -1 cacboxylic v axit 2 aminobenzoicti cc pH axit, trung tnh v baz.
Nu im ng in c nh ngha l pH m ti phn t c in tch tng cng bng 0
(ii)
th hy tnh im ng in gn ng ca axit 2 aminoxiclohexan 1 cacboxylic.
BI GII:
a)
(i) Piridin c tnh baz yu hn piperidin v i electron gy tnh baz ca piridin thuc obitan sp2;
n b gi cht v khng sn sang cho cp electron nh trng hp piperidin vi obitan sp3.
(ii) Piridin c i electron (thuc 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.
(iii) 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
(iv)
C th xy ra s phn tn cc electron khng lin 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
N
(v)
NH2
NH2
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.
b)
(i)
CO2H
NH3+
Tnh axit
CO2-
CO2NH3
NH2
trung tnh
tnh baz
CO2-
CO2-
(ii)
CO2H
NH3+
NH3+
NH2
Tnh axit
trung tnh tnh baz
(iii) im ng in = (pKa1 + pKa2)/2 = 6,88
(-)-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
(-)-Atractyligenin
Br
B
C5H10O
C
C5H8O
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).
a) Hy vit cng thc cu to ca hp cht B
Khi cho hp cht B tc dng vi kali dicromat trong dung dch nc ca axit sunfuric thu c
C (C5H8O).
b) Hy vit cng thc cu to ca hp cht C
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.
H
C7H12O2
c) Hy vit cng thc cu to ca hp cht D

d) Hp cht D c ng phn lp th khng? Nu c, hy cho bit c bao nhiu ng phn lp th?
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
e) Hy vit cng thc cu to ca hp cht E.
f) Hp cht F c ng phn lp th khng? Nu c, hy cho bit c bao nhiu ng phn lp th?
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.
g) 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.
h) Hy vit cng thc cu to sn phm I (khng xt ng phn)
i) Hy tr li cc cu hi sau
S ng phn lp th c lp c ca sn phm I l 2, 4, 6 hay 8?
(i)
(ii)
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?
(iii) 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
F
* OH
OH
G
Br
H
I
Cht D c 2 ng phn i quang

Cht F c hai ng phn hnh hc
(i)
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
(ii)
(iii) Cp ng phn khng i quang c im nng chy khc nhau. Cp ng phn i quang
c im nng chy bng nhau.
Trong s iu ch mt dc cht, c ba cht trung gian c iu ch trong cc phn ng ring
bit m t di y:
a) Hy vit cng thc v tn IUPAC ca sn phm thu c trong phn ng sau:
NH2
NO2
1) HNO2 + H2SO4
2) CuCN + KCN
b) Hy vit cng thc theo cch khng th nhm ln v mt ha lp th v tn IUPAC y ca

sn phm thu c khi (2S) 2 clorobutan phn ng vi natri metoxit trong mt phn ng kiu
SN2.
c) Hy vit cc cng thc ca cc sn phm thu c trong ba giai on phn ng sau y v cho
bit s ng phn lp th thu c giai on cui:
O
1) H+ + HOCH2CH2OH
O
O
2) D CH3MgI trong ete, ri thm nc

3) H3O+
BI GII:
a)
NH2
N2+
HNO2 + H2SO4
CN
CuCN + KCN
NO2
NO2
NO2
b)
Cl
CH3
CH2CH3
H
Na+OCH3-
CH3
OCH3
H
(2R) - 2 - Metoxibutan
H3CH2C
c)
O
H++ HOCH2CH2OH
CH3MgI (du)
OMgI H O
2
OH
ete
H3O+
O
OH
Ch mt cu to lp th duy nht
Mt thnh phn S ca du hoa hng dng c cu to sau:
cis
H2C
OOC(CH2)7
C
H
HC
OOC(CH2)7
C
H
H2C
cis
C
H
C
H
(CH2)7CH3
H2
C
cis
C
H
C
H
(CH2)4CH3
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.
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.
d) 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?
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.
f) 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
H2C
HC*
H2C
OOC(CH2)7
C
H
OOC(CH2)7
C
H
cis
C
H
C
H
(CH2)7CH3
cis
H2
C
C
H
C
H
(CH2)4CH3
OOC(CH2)18CH3
b) Cc cng thc cu to v tn gi ca este metyl l:

O
(Z) - metyloctadec-9-enoat
O
O
(9Z;12Z) - metyloctadec-9,12-dienoat
O
O
metyl octadecanoat
c) Ozon phn S ri tc dng vi Zn cho cc andehit sau:

O
O
nonal
hexanal
O
O
metan dicacbadehit
O
O
O metyl nonalat
d) S mol KOH dng nhiu gp 3 ln s mol triglixerit S

n(S) = 10,0/885.402 = 11,29 (mmol)
V(KOH) = 3 . n/V = 34,0mL
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
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 phm nhum. Ngoi ra n cng l mt cht trung gian quan trng trong cc 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 xitric 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
HO
H2C
COOH
COOH
H2C
COOH
H2C
H2SO4
C
H2C
COOH
O
H2O
CO
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 CO CH2 COOH
V c cng thc phn t C12H12O5
Do c s cn tr khng gian ca cc nguyn t hydro trong anisol nn nhm th 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
H
Br
HOOCH2C
Br
COOH
Br
H
Br
CH2COOH
OCH3
OCH3
2
Hai cht ny l enantiome

e) Cu hnh tuyt i ti cc trung tm lp th
H
HOOCH2C
COOH
S
Br
R
Br
COOH
R
Br
H
S
Br
CH2COOH
OCH3
OCH3
2
f) Cng thc cu to cc cht B v C

CH2COOH
O
B
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
3
2
OH
Nh vy th trong cng iu kin phn ng th lng sn phm C lun nhiu hn B

Etylen c rt nhiu ng dng quan trng trong vic sn xut polyme v cc monome quan trng
khc. N c sn xut mt lng ln bng phng php crackinh nhit v crackinh xc tc cc ankan
nhn c t kh thin nhin v du m.
Trong s c mt ca xc tc bc, etylen phn ng vi oxy to thnh cht P. Cht P khi un
nng vi H3O+ s chuyn thnh cht Q. Ph cng hng t proton ca P ch c duy nht mt tn hiu
cn Q th li cho 2 tn hiu
a) Xc nh v hy v cng thc cu to hai cht P v Q
Cht R nhn c khi P v Q phn ng vi nhau. R phn ng c vi SOCl2 thu c cht
S. Khi un nng vi KOH trong ancol th S to thnh T.
b) Xc nh cng thc cu to ca ba cht R, S v T
Mt hp cht khc l benzen-1,4-bis(axetat) c th c tng hp t p xylem. Qa trnh tng
hp benzen-1,4-bis(axetat) i qua nhiu hp cht trung gian khc nhau v s dng nhiu tc nhn khc
nhau v c c th s di y:
CH 3
CH 3
p - xilen
COOH
CH 2
CH 2CN
CH 2Br
COOCH3
CH 2
CH 2Br
CH 2CN
CH 2
COOH
CH 2
COOCH3
Dimetybenzen-1,4bisaxetat
c) Xc nh cc tc nhn s dng trong qa trnh tng hp trn

d) C bao nhiu pic m ta c th nhn ra c trong ph 1H NMR ca dimetylbenzen 1,4
bisaxetat.
Khi detylbanzen 1,4 bisaxetat (c tng hp t p xylen) v hp cht R (nhn c t
etylen) c un nng cng nhau th mt polyme mi c hnh thnh.
e) V cng thc ca polyme mi ny
f) Khi x l polyme ny vi cc cht: i) KOH(aq); to, sau H+/H2O; ii) LiAlH4 th chuyn g s
xy ra?
g) Khi v tnh un nng lng d dimetylbenzen 1,4 bis(axetat) vi glyxerol th ta thu c
mt polyme khc. Xc nh cng thc cu to ca polyme ny v cho bit n c th dng ko
si c khng?
BI GII:
a)
H 2 C CH 2
+ 1/2O2
H 2C CH 2
O
+ H2 O
xt Ag
250 oC
H 2C CH 2
O
P
H+
OH
HO
Q
b)
H 2C CH 2
+
O
P
SOCl2
OH
Cl
KOH/ancol
CH3
EtOH/H 2O
CH2 Br
COOCH 3
CH2
H +/H 2O, to
CH3 OH, to
hay: i) NaOH/H2 O
ii) H+ / H 2O
CH2 CN
CH2
H+
KCN
peroxit
CCl4
COOH
CH2
CH2 CN
CH2 Br
NBS
Cl
Cl
c)
O
S
Cl
OH
CH3
HO
Q
O
HO
OH
HO
COOH
p - xilen
CH2
COOCH 3
Dimetybenzen-1,4-bisaxetat
d) Ba tn hiu: ca nhm CH3; -CH2 v proton ca vng thm

e) Cu trc ca polyme:
H3C
O
H2
H2 H2
C C O C C O
H2
C
H2 H2
C C O H
f) Cc phn ng:
Polyme
i) KOH/H 2O/to
ii) H + / H 2O
HOOCH 2C
CH2 COOH + HO
HOH2 CH 2 C
CH 2CH2 OH + HO
LiAlH4
Polyme
OH
OH
g) Nu ta s dng glyxerol (mt triol) sth lin kt gia cc mch tng ln. Nhm hydroxyl
bc hai s to nn mt h mng khng gian ba chiu vi cu trc c th nh sau:
H2 C
OH
HC
OH
H2 C
OH
Glyxerol
O
H2
C C
C
H2
H
H2
O C C
H2
C O
O
C
O
C
C
H2
CH2
CH2
C
Polyme ny khng th s dng ko si c do cu trc ca n c qa nhiu lin kt gia cc

on mch. Tnh cht c trng ca n l tnh cht khng.
Mt trong s nhng vn nan gii ca ha hu c l s tng hp cc dn xut benzen hai ln
th thng qua phn ng th electrophin vo dn xut benzen mt ln th. Bi ny s cp n s tng
hp Tramadol, mt loi dc phm dng gim au c m t di y. Bc u tin ca qa trnh
ny l:
HSbF6
Phenol
A
halogen
A cho hai pic c cng nh nhau im c khi lng phn t tng ng l 172 v 174
trong ph khi lng. N to ra mt hn hp ba dn xut mononitro ng phn khi ta nitrat ha trong
nhng iu kin m du.
a) Vit cng thc cu to A. u l s chn lc hng phn ng trong phn ng chuyn t phenol thnh
A? u l im mu cht ca phn ng?
CH 3 ) 2 so4 / NaOH
THF / toluen
B Mg
/
C
Xt chui phn ng sau: A (
Ph khi lng ca B ch ra hai pic c cng nh nhau im c khi lng phn t tng
ng l 186 v 188.
b) Xc nh cng thc cu to ca B v C. Kh nng phn ng ca cht B thay i nh th no khi
n chuyn thnh cht C?
Mt cht trung gian D cn thit trong qa trnh tng hp Tramadol nhn c qua s sau:
parafomandehit
Xiclohexanon
dimetylamin
[E]
thy phn
D (C 9H 17 NO)
(tan trong HCl)
Tramadol
c) Cho bit cng thc ca cht D v sn phm Tramadol

d) Cho bit cu hnh cc trung tm lp th c th c ca Tramadol
BI GII:
a) T cc thng tin v ph khi lng m bi cho th sn phm nhn c khi halogen ha
phenol vi xc tc HSbF6 l m bromphenol. S brom ha trc tip vo phenol s cho cc dn
xut v tr ortho v para v nhm OH l nhm th loi I
b)
Cc phn ng xy ra:
OCH 3
OH
OH
(CH 3 )2 SO 4
xt HSbF6
Br 2
Mg/THF/toluen
NaOH
Br
OCH3
Br
MgBr
Hp cht B c th tham gia c phn ng th nucleophin cacbon mang nguyn t brom. Cn hp

cht C th li c s tn ti ca cacbanion nn s tham gia phn ng th electrophin. Nh vy s
chuyn hp cht B sang hp cht C s dn n s nghch o li kh nng phn ng.
c)
O
O
CH 2O
CH3
CH3
(CH 3 )2 NH
D
OH
OH
+
MgBr
C
CH 3
OH
CH 3
CH3
CH3
Tramadol
d)
HO
PhOCH3
N(CH3 )2
H
HO
PhOCH3
H
N(CH3 )2
HO
PhOCH3
H
N(CH3 )2
HO
PhOCH3
N(CH3 )2
H
Tramadol c hai nguyn t cacbon bt i nn c hai cp ng phn lp th

Cc xetoeste l nhng phn t c hai nhm chc cc k hot ng v l nhng tc nhn quan
trng trong s tng hp cc hp cht c tnh c th lp th cng nh cc hp cht d vng.
a) Xetoeste c cng thc phn t C5H8O3 c hai ng phn X v Y. Xc nh cc cng thc phn t
c th c ca chng.
Mi este ny u u tin cho phn ng vi benzoyl bromua trong s c mt ca CH3ONa v
sn phm thu c c un nng vi 1 hay 2 ng lng baz mnh (v d nh liti diisopropylamit
LDA) v tip theo l mt ng lng CH3I
Sn phm ca bc th hai ny u c thy phn trong mi trng HCl
b) Vit cc phn ng xy ra
c) Sn phm cui ca xetoeste X l mt hp cht trung tnh (c cng thc phn t C11H14O) cn
xetoeste Y cho mt xetoaxit (c cng thc phn t C12H14O3). Hy gii thch s khc nhau ny.
d) Xetoeste X cho cc phn ng khc nhau ty thuc vo lng LDA s dng. Hy gii thch kt
qa thu c khi:
S dng mt ung lng LDA
(i)
(ii)
S dng hai ng lng LDA
BI GII:
a) Cng thc phn t ca cc xetoeste l C5H8O3. V X v Y l xetoeste nn chng buc phi c
nhm chc xeton (C CO ) v nhm chc este (C COO ). Tng s nguyn t ca c hai
n v ny l C4O3. Nh vy ch c th c hai nhm nh vi u este : metyl hoc etyl.
Nh vy xetoeste ban u c th c mt trong ba cng thc cu to sau:
H3 C
H2
C
O
O
CH3
H3 C
O
H2
C
II
H3 C
b) Phn ng ca cc xetoeste tng ng:
III
H2
C
CH 3
CH 3
H 3C
H2
C
CH3
CH3ONa
PhCH2Br
H
C
H3 C
CH 3
CH 2Ph
Xetoeste C12H 14O3

1 equiv LDA
H3 C
MeI
CH 3
CH 3
CH 3
H+/H 2O/to
H3 C
CH 2Ph
H2
C
CH3
CH 2Ph
Xetoaxit C12H14O3
H 3C
H2
C
CH 3
III
CH3ONa
PhCH2Br
H2 C
H2
C
CH3
CH2 Ph
CH3
1 equiv LDA
HC
MeI
O
C
CH2 Ph
i vi cht II:
O
C
CH3
O
H2
C
H+/H2O/t o
CH3
HC
CH2 Ph
Xetoeste C11H12O3
O
H3 C
O
H2
C
NaOMe
H3 C
CH3
CH 3
PhCH2Br
2 equiv LDA
MeI
O
H
C
1 equiv LDA
MeI
CH 2Ph
O
H2 C
CH 3
O
H
C
CH 3
H3 C
CH 3
CH 2Ph
H2 C
CH 3
H+/H2O/to
O
H
C
H 3C
CH3
-xetoaxit
- CO2
- CO2
CH 3
H2
C
H2
C
CH2 Ph
CH 2Ph
-xetoaxit
H2 C
CH 3
CH 2Ph
H+/H2O/to
O
Ph
H 3C
CH3
C
H
H2
C
Ph
(C11H14O)
(C11H14O)
Cht I cho sn phm cui cng l mt xetoaxit c cng thc phn t l C12H14O3 ng vi cng
thc ca xetoaxit nhn c t cht Y. Vy cng thc cu to ca cht Y l cng thc I.
Cht II cho sn phm cui cng l mt cht c tnh cht trung tnh vi cng thc phn t l
C11H14O ng vi cng thc ca cht nhn c t X. Vy cng thc cu to ca cht X l cng
thc II.
Cht III cho sn phm cui cng l mt xetoaxit c cng thc C11H12O3 khng h ng vi mt
trong cc cng thc no trn.
c) Cht - xetoeste nhn c d b thy phn trong mi trng axit ra - xetoaxit, cht ny d
tham gia phn ng decacboxyl ha qua trng thi chuyn tip vng 6 trung tm cho ra sn phm
trung tnh.
H
H2 C
H2
C
CH2 Ph
+ CO2
CH
CH3
H3 C
H
CH2 Ph
O
H 3C
H2
C
H2
C
CH 2Ph
d) i) Khi s dng mt ng lng LDA th hp cht X s to ra monoanion nh hnh v:

O
H3 C
O
H2
C
O
O
CH3
1 equiv LDA
H3 C
O
H
C
CH 3
CH 3
ii) Khi s dng hai ng lng LDA th s to ra dianion nh hnh v:

O
H3 C
O
H2
C
O
O
CH 3
2 equiv LDA
H 2C
O
H
C

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.
OH
CH 2OH
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 thnh 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 lactoloz (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
HO
H
H
OH
H
OH
OH
CH 2OH
D glucoz
H
HO
HO
H
OH
H
H
OH
CH 2OH
D galactoz
2)
a
CH 2OH
O
OH
c
OH
OH
OH
OH
O
3)
OH
OH
CH 2OH
CH 2OH
H
HO
H
H
OH
H
OH
OH
CH 2OH
H
HO
HO
H
OH
H
H
OH
CH 2OH
Sorbitol (hot ng quang hc) Galactitol (khng hot ng quang hc)
4)
CH 2OH
O
OH
OH
O
OH
OH
CH 2 OH
O
OH
CH 2OH
OH
OH
OH
OH
OH
OH
OH
Lactitol
CH 2OH
O
OH
OH
OH
OH
CH 2OH
CH 2 OH
Lactolose (f uranose)
OH
CH2 OH
O
OH
Lactolose (pyranose)

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 hop bng cch vit cng thc cu to cc cht A, B, C, D v E
O
OH HNO3
HO
n-C 3H 7 Cl
baz
SOCl2
HOCH 2CH2 N(C 2H 5) 2

C
H 2 /Pd(C)
D
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 C3H7Cl 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 SE
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
H3 CH 2 CH 2CO
B
O2 N
OH
OH
HO
H 3CH2 CH 2 CO
C
O
O2 N
O
OCH2 CH 2N(C 2 H5 )2
H 3 CH 2CH 2CO
H 2N
OCH 2CH2 N(C2 H 5) 2
H3 CH2 CH 2 CO
D
Cl
2) Cng thc cu to cc sn phm:

NO2 O
O
OH
OH
+
O2 N
OH
OH
3) c
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.
Ph
H2 N
CH3
H 2N
COOH
F
COOH
A
H 2N
COOH
G
H2N
COOH
L
Trong phng php phn tch cu trc peptit th vic nhn din aminoaxit u N v ui C ng
vai tr cc k quan trng. Phng php Sanger gip ta nhn din c aminoaxit u N bng cch x l
aminoaxit vi 2,4-dinitroflobenzen trong mi trng kim yu, sau l thu phn ton b chui peptit
vi xc tc axit. Aminoaxit u N s to ra kt ta mu vng v d dng c nhn din bng phng
php sc k giy. Sanger c trao gii thng Nobel nm 1958 v 1980.
2. Vit phn ng xy ra khi ta s dng tc nhn Sanger ( cho gn ta vit aminoaxit u N c cng
thc l 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
H
N
H2 N
O
OH
H
N
H 2N
O
AF
O
FA
Ph
O
OH
H
N
H 2N
O
FF
Ph
O
OH
Ph
2. Phn ng xy ra:
F
O
OH
O
AA
NO 2
NO 2
O 2N
H 2N
H
N
2H 2NR
O 2N
NHR +
RNH 3+F-
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.

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.
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)
Hp cht Cistus L c mi thm, c trong cc nhnh cy bi v l thnh phn chnh ca hoa Hy
Lp. N hay c tm thy i v cc sn dc , ngoi ra n cn c tm thy cc rng thng.
Trong y hc dn gian, nhnh hoa ca Citrus monospeliensis c dng tr bnh suyn cn l c
dng thay th tr. Flavonoid c phn lp rt rng ri t thc vt di dng glycozit hay dng t do
aglycon (hp cht sinh ra khi thu phn glycozit). Chng c mt ng dng rng ri trong cc tnh cht
dc l bao gm: khng vi sinh vt, khng u, khng c, c ch enzym v tng cng cc hot ng
mch mu.
Apigenin l mt loi flavonoid hay gp v c cng thc cu to nh sau:
1) Vit cng thc cu to ca cc sn phm B v C
excess: lng d
2) Apigenin c to thnh mt lin kt hydro gia nhm hydroxyl phenolic ca C5 v nhm cacbonyl
ca C4. Ph 1H NMR ca proton phenolic C5 s b dch chuyn do lin kt hydro v pha:
a) trng yu
b) trng mnh
c) khng b dch chuyn
3) Khi un nng vi dung dch NaOH 2M, apigenin sinh ra hai sn phm D v E.
Hp cht D (C6H6O3) cho phn ng dng tnh vi FeCl3 v ph 1H NMR ch gm mt pic duy nht
ca h thm (ph I). Hp cht E (C9H12O2) cng cho phn ng dng tnh vi FeCl3. Trong ph 1H
NMR th phn khng thm cho hai vn ba v mt pic nhiu vn trong khi phn khng thm ch gm
mt vn i (ph II). Vit cng thc cu to ca D v E
4) S dng mi tn hy ch ra ba nguyn t cacbon cng thc C s cho ra ba pic c trng trong ph
13
C NMR khc vi ph 13C NMR ca B.
BI GII:
1)
2) Trng yu, bi v ph 1H NMR ca proton phenolic lun dch chuyn v pha trng yu khi
proton ny chu nh hng ca lin kt hydro.
3) Cng thc cu to ca cc cht nh sau:
4) Cc nguyn t cacbon tho mn yu cu bi l:

Peptit l cc polyamit mch thng sinh ra bng cc lin 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 L alanin v L phenylalanin? 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 Nit) dn
n s thay th nguyn t N - th trc khi n v k tip c gn vo. Dn xut th thng c
s dng l cc nhm ankoxy cacbonyl ROCO v dn xut cacbamat ca n.
Hy gii thch l do ti sao s hin din ca nhm th (nhm bo v) ca nguyn t nit amin
lm tr ngi vic to lin kt amit vi nhm cacboxyl.
a) V nit by gi ch cn c 1H
b) V nhm bo v c mt electron t hn nguyn t nit.
c) V nhm bo v chn s tn cng ca nhm cacbonyl
d) V s khng tnh in
e) V n vn l mt amit.
3) V cc cng thc cng hng ca mt na nhm amit. S dng cc k hiu lp th v cc mi tn
ch r s chuyn dch electron.
4) Tc nhn no di y s c s dng gn nhm benzylcacbamat vo mt amin (nhm
Bergmann Zervas). Vit phn ng.
a. C6H5CH2OCONH2, b. C6H5CH2OCO2CH3, c. C6H5CH2OCO2C(CH3)3,
d. C6H5CH2OCOCl, e. C6H5OCOCl
5) Vic loi nhm bo v ankoxycacbonyl thng km theo phn ng ct mch di tc dng ca cc
axit theo s :
Xp kh nng tng dn tnh hot ng ca cc cacbamat sau y di tc dng ca axit:
BI GII:
1. Cng thc cu to cc peptit c th c:
Cc dipeptit vng (dixeto piperazin) cng c chp nhn:
2. Cu tr li tt nht l 5 v 2
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

Oleuropein (A) c cng thc cu to nh sau vi R l nhm ankylpolyphenolic:
1) S thu phn c xc tc axit ca oleuropin cho ra glucoz v hai hp cht khc gm: polyphenolic
(A1) v mt monoterpenoid (A2). Hy s dng mi tn ch vo cng thc ca oleuropin.
a) Nguyn t oxy s b proton ha trong phn ng thu phn xc tc axit to ra polyphenolic A1.
b) Lin kt C O b phn ct to ra glucoz.
2) ph khi ca A1, pic tng ng vi ion phn t c m/z = 154. Ph 1H NMR ca (A1) cho di
y. Nhm proton hydroxyl tham gia phn ng trao i nn khng c mt trong cc pic trn.
Vi nhng thng tin trn hy ch ra A1 l cht no trong ba cht sau?
3) T cng thc cu to ca A1 hy ch ra proton no ca A1 ph hp vi cc tn hiu trn ph 1H

NMR.
BI GII:
Cng thc cu to ng l C
Ngi ta cho bit rng s cng hp brom vo ni i xy ra theo hng lp th anti
Vit sn phm phn ng khi ta tin hnh phn ng cng brom vo cc anken sau. Hy s dng
cng thc chiu Fischer vit cu to sn phm. nh du * vo cc nguyn t cacbon bt i:
BI GII:
Yes: c tnh quang hot

No: khng c tnh quang hot

Mt ankin A quang hot c %C = 89,5% v 10,4%H. Sau khi hydro ha hon ton bng Pd/C
thu c 1 metyl 4 propylxiclohexan. Khi cho A phn ng vi CH3MgBr ta khng thu c sn
phm kh. Hydro ha A trn xc tc Lindlar tip theo l ozon phn v phn ng vi KMnO4 sinh ra B,
cht ny cho mt pic 207ppm trong ph 13C NMR. Sn phm B phn ng vi I2/NaOH cho ra kt
ta mu vng. Lc kt ta, axit ha dch lc thu c sn phm C quang hot khng c pic 175ppm
trong ph 13C NMR. Xc nh cng thc cu to A, B, C.
BI GII:

Lipaza l cc enzym thu phn cc lin kt este trong phn t triaxylglyxerol trong khi cc
proteaza ch thu phn cc lin kt amin trong protein v peptit. Hp cht hn ch c s thu phn
cc triaxylglyxerol v peptit c th c ch trong vic iu tr nhiu loi bnh tt khc nhau.
Chng ta s tip cn s pht trin ca vic hn ch hiu qa ca enzym serin proteaza bao gm
s thay th lin kt amit b t bng nhm cacboxyl c hot ha. Kt qa l nhm hydroxyl pha
hot ha ca enzym s phn ng vi nhm cacbonyl c hot ha sinh ra sn phm cng bn vng
axyl enzym v cht ny khng b thu phn tip na.
1. Sp xp cc nhm sau y theo th t gim dn hot tnh phn ng vi nhm hydroxyl ca serin
2. Tetrahydrolipsatin l mt cht khng protein ca loi enzym lipaza tiu ha (trong y hc n c s

dng chng bo ph). Ch ra bng mi tn nhm cacbonyl ca tetrahydrolipsatin b tn cng bi
tm hot ng ca serin lipaza.
3. Este v amit c th b thu phn di tc dng ca axit hay baz. Xp kh nng thu phn ca hp
cht ny theo th t gim dn khi ta thu phn trong mi trng baz.
BI GII:

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

2) Xc nh cc mnh sau c lin quan n axit salixilic l ng, sai hay khng c s kt lun?
a) ASS tan nhiu trong nc c pH = 2 hn l pH = 9
b) Phn ng th electrophin c th xy ra v tr ortho ca nhm COOH
c) Baz lin hp ca n kh tan trong nc hn axit.
d) Ph NMR ca hp ch ny ch cho ta thy c hai tn hiu ca nhm CH vng thm.
e) Ph 1H NMR trong D2O/DMSO cho ta mt hn hp gm 5 tn hiu.
Mt trong nhng loi dc phm u tin c tng hp l phenacetin, cht ny tr nn thng
dng bt u t nm 1888 l mt loi thuc gim au nh. Do c phn ng ph nn n b cm lu
hnh trn th trng t nm 1986. Phenancetin E c th c tng hp t s sau:
Ph 1H NMR ca E c dng nh sau:
3) Vit cng thc cu to cc cht t A n E v ch ra cc proton no ca E tng ng vi cc vch

ph cho.
4) By gi chng ta s so snh axit axetylsalixilic ASS v phenancetin E, cc mnh sau y l ng
hay sai hay khng c s quyt nh?
a) pH = 9 th phenacetin phn cc hn ASS.
b) C hai cht ny u c th b deproton ho bng NaHCO3
c) Khng c cht no quang hot c.
d) Trong phng php sc k bn mng bng silicagel vi dung mi l 5% axit axetic trong etyl
axetat th ga tr Rf ca phenacetin ln hn so vi ASS.
BI GII:
1) 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.
2) a.; b.; c.; d.: sai;

e: ng
3) Cc phn ng xy ra nh sau: kh nhm nitro thnh amin (A), axyl ha (B) v tin hnh phn ng
sunfo ha v tr para thu c C (da trn ph NMR th sn phm to thnh khng phi l th ortho
v iu s dn n 4 tn hiu CH (xem ph). Phn ng vi NaOH di iu kin khc nghit s dn
n s hnh thnh phenol D v s ete ha theo Williamson s dn n s to thnh cht E.
Ph NMR:
4) a,b: sai;
c, d, e: ng
Nhm cacbonyl C=O l mt nhm chc c kh nng tham gia nhiu phn ng ha hc. N c
th tham gia cc phn ng hnh thnh lin kt C C. Phn ng tch loi proton v tr dn n s to
thnh enolat v s tn cng ca mt nhm nucleophin vo nguyn t C ca nhm cacbonyl l hai phn
ng quan trng nht ca nhm C=O.
Mt s lng ln cc phn ng chn lc lp th v chn lc vng c nghin cu da trn

hai phn ng ny, c bit l khi nhm cacbonyl khng i xng. Trong phn ng ankyl ha chn lc
vng ca 2 metylxiclohexan (ch xem xt phn ng monoankyl ha).
LDA: liti diisopropylamit; Pr2NLi: mt baz mnh nhng khng mang tnh nucleophin
Room temperature: nhit phng
1) Vit cng thc cu to ca A, B, A, B (khng cn ch n mt lp th) v di cc iu kin
phn ng cho hy gii thch kt qa thu c.
2) Ti sao ta khng th s dng butylliti (BuLi) lm tc nhn loi proton.
Phn ng ankyl ha trc tip cc enolat th thng khng c s dng ankyl ha hp cht
cacbonyl v dn n cc sn phm ph l cc dn xut hai hay ba ln th. Chnh v vy cc enamin
c s dng.
3) Vit c ch phn ng hnh thnh C v hy ch ra s chn lc hng phn ng y.

4) Hy gii thch l do enamin phn ng vi cc tc nhn electrophin bng cc cu trc cng hng.
5) Vit cng thc cu to ca cht D (khng cn ch n mt lp th)
y l phn ng tng hp dn xut ca cumarin vi xc tc axit
6) Hy vit cng thc cu to E

BI GII:
1)
S deproton ha l thun nghch, chu s khng ch nhit ng hc v to nn dn xut enolat

nhiu ln th.
S deproton ha khng thun nghch, khng ch ng hc, proton no c tnh axit cao hn b
loi ra v to nn dn xut t ln th hn.
2) BuLi cng c th phn ng nh l mt tc nhn nucleophin vo nguyn t C ca nhm cacbonyl,
chnh v vy mt baz khng c tnnh nucleophin nh LDA c chn.
3) 5) S hnh thnh ca enamin:
Enamin c tnh nucleophin do cp electron khng lin kt trn nguyn t nit c th y electron
sang nguyn t cacbon - (xem cu trc cng hng)
chu nh hng khng gian = khng tn ti dng phng
6)

A to thnh B khi cho A phn ng vi mt baz mnh m khng c tnh nucleophin, B phn ng
vi brom to thnh raxemic C. Sn phm cui S (sn phm chnh) v E (sn phm ph) c to
thnh bi phn ng gia C vi mt baz mnh m khng c tnh nucleophin
1) Vit cng thc lp th ca A cu dng bn nht. Hy khoanh trn cc nguyn t c th chuyn ha

thnh B
2) Vit cng thc cu to B
3) Vit cng thc lp th ca C (ch cn v mt i quang) cu dng bn nht. Khoanh trn cc
nguyn t c th chuyn ha thnh D v E.
4) Vit cng thc cu to ca D v E
BI GII:
1) Dng gh l cu dng bn nht ca vng xiclohexan. Kch thc nhm th ln l thun li cho phn
ng tch.
Trong cc phn ng tch kiu E2 th cc nhm b tch ra buc phi khng cng trn mt mt
phng v khng cng hng v mt pha. iu ny ch c th xy ra i vi cu dng gh nu mi
nhm chc u v tr axial.
2 - 4:
Bi v cc nhm gy ra hiu ng cm ng m l brom nn nguyn t hydro ca nguyn t

cacbon lin kt trc tip vi nguyn t brom tr nn c tnh axit. Proton ny d dng b tch ra di tc
dng ca baz nn D s l sn phm chnh.
C nhiu hp cht c cng thc phn t C4H8O nhng mt s t trong chng mi c hot tnh
quang hc.
1) Cht no c t nht mt trung tm bt i? Hy v cu trc khng gian ca chng vi cc trung tm
bt i c nh du *.
2) Vi cht trong s chng cho cu hnh (S) hu ht cc trung tm bt i. V cu dng tng ng.
3) Nu c hp cht meso ng vi cng thc ny th hy v ra cu dng ca n.
BI GII:
C 5 phn t ng vi iu kin cho, ba trong s chng c mt trung tm bt i v hai cht
cn li c hai trung tm bt i. Mt trong s chng l i xng nn c hp cht meso tn ti
1)
2)
3)

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 hot.
1. V cng thc cu to ca A, B v C bng cch s dng cng thc chiu Fischer.
2. Xc nh cu hnh cu hnh tuyt i ca cc cht t A n C bng cch s dng h danh php CIP
(Cahn Ingold Prelog).
3. Hy xc lp mi quan h v mt lp th gia cc ng phn quang hc ca B.
BI GII:
1 2.
Mt monosaccarit c cng thc 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.

Epibatidin l mt hot cht c phn lp t mt loi cc nhit i v c hiu lc gim au gp
200 ln so vi morphin v khng gy nghin. Trong qa trnh tng hp epibatidin th A s chuyn ha
thnh B bng phn ng SN2 ni phn t.
B l tin cht ca epibatidin

1) nh du * vo cc trung tm bt i ca phn t A
2) Xc nh cu hnh tuyt i ca nhng v tr bng danh php CIP.
3) V cng thc lp th ca A v hy ch ra hng phn ng bng mi tn gia cc trung tm phn ng.
4) V cng thc lp th ca B
BI GII:
1 2.
3
4
Trong phn ng th nucleophin ni phn t (SN2), s tc nhn nucleophin tn cng vo trung

tm phn ng t pha sau ngc vi pha ca nhm i ra. c th tip cn c trung tm phn ng
th nhm nucleophin (nhm amino) phi c v tr axial v phi tn cng vo nguyn t brom pha xa
nht so vi nhm nucleophin.
Aminoancol B l mt cht trung gian quan trng tng hp Crixvan, cht ny c kh nng c
ch tim tng proteaza ca HIV. Cc nh ha hc ca Merck mun s dng epoxit A nh l vt liu ban
u trong qa trnh tng hp.
major: sn phm chnh

minor: sn phm ph
1) Sau khi x l A vi benzyl amin trong s c mt ca axit yu lm cht xc tc, h nhn c sn
phm chnh l aminoancol C cng vi sn phm ph D, cht ny c th s dng nh l tin cht ca
B. Vit cng thc cu to C v hy ngh c ch ca phn ng ny. Hy ch ra hng phn ng v
ha lp th ca n.
2) Sau khi x l A vi H2SO4 c v CH3CN di cc iu kin khng ch nhit ng hc, ch c E
sinh ra v sau ta thu phn E thu c B. Vit cng thc cu to E v c ch to thnh cht ny.
Hy ch ra hng phn ng v ha hc lp th ca n.
BI GII:
1)
S hnh thnh cht C (c ch SN2): s tn cng t pha sau i vi nhm benzyl; in tch dng
trng thi chuyn tip ca trung tm phn ng c n nh ha nh nhm phenyl.
S hnh thnh C v D (c ch SN1): hng phn ng lc ny ph thuc vo nhm benzyl do cc
cng thc cng hng ch ra s n nh ca cacbocation bi nhm phenyl.
2)
Cht F khng th c to thnh v iu dn n s bin dng vng

Nm 2001, gio s R. Noyori nhn c gii thng Nobel cho cc cng trnh v s kh ha
chn lc lp th ca cc ni i C=C v C=O.
By gi chng ta s xem xt cc phn ng n gin hiu ra mt s cc nguyn t c bn c
th iu khin c s hydro ha chn lc lp th nh th no.
V d: - xetoeste A (raxemic) c th b kh bng hydro to thnh raxemic B vi kh nng
chn lc s to thnh ng phn dia (diastereoselectivity) cao trong s c mt ca xc tc kim loi ch
vi phn ng chn lc ha hc tn cng vo lin kt C=C. ng phn tinh khit quang hc - xetoeste
C b kh chn lc lp th to ra raxemic B. Thm vo mt ng lng LiCl cc k quan trng
hng phn ng theo hng to ra ng phn lp th chn.
1. Vit cng thc cu to ca raxemic B

2. C hai ng phn lp th khng i quang ca hp cht cho cu 1 c th to thnh hp cht
raxemic B trong iu kin ny. Hy vit cng thc cu to ca chng.
3. Xy dng c ch cho thy rng phn ng m t trn ch to ra B (khng sinh B)
BI GII:
1.
Cc ng phn i quang ca B:
2. Cc ng phn i quang ca B
3 S chn lc lp th ca phn ng dehydro ha
A v C phi b kh bi mt trng thi chuyn tip khng i xng, ch C b raxemic ha trong

qa trnh ny. S raxemic ha C c th c hiu l do s to thnh enolat D1 c kh nng tn ti lu
hn D2 do hiu ng to phc chelat cao Li+ hin din trong hn hp phn ng. S nhn nguyn t
hydro bng kim loi bng cch ny (cng syn) t nh hay t y ca cht D1 dn n s to thnh hn
hp raxemic E1/E2 nh l cc ng phn dia n nht. S thy phn chng dn n vic hnh thnh
raxemic B.
Cacbocation l cc trng thi trung gian ca phn ng, chng mang in tch +1 trn nguyn t
cacbon trung tm. Trung tm cacbocation l trung tm thiu electron v c cu to phng. Cng hng
t proton (H-NMR) l mt trong nhng phng php cng c u tin c dng xc nh cu trc
v tnh cht ca cacbocation. Trong mi trng axit mnh, nh l SbF5, cacbocation bn c th hnh
thnh v c trc tip theo di bng NMR. SbF5 l mt axit Lewis mnh m c th to phc vi mt
baz yu nh l F- hnh thnh SbF6-.
1) Cho bit sn phm A trong phn ng sau y?
F
H3C
H3C
SbF5
CH3
2)
Hai ph H-NMR ca (CH3)3CF c thu c khi ln lt dng (CH3)3CF tinh khit v

(CH3)3CF trong SbF5. Mt ph, k hiu l ph I, cho thy mt vch n ti 4.35, v ph kia
(ph II), cho thy mt vch i ti 1,30 vi hng s tng tc J = 20 Hz. Ph no l ca
(CH3)3CF trong SbF5?
3) Ion tropylium B l mt trong nhng cacbocation bn nht. C bao nhiu electron trong ion
tropylium?
H
H
H
H
H
B
4)
Ion tropylium B c phi l cu trc thm hay khng? Gii thch.
5)
dch chuyn ha hc ca benzen trong ph 1H NMR l 7.27. Ph H-NMR ca B s l:
6)
(a)
Mt vch n ti 9.17.
(b)
Mt vch n ti 5.37
(c)
Mt vch ba ti 9.17.
(d)
Mt vch ba ti 5.37.
4-Isopropyltropolon C l v d u tin ca mt hp cht thm khng ging benzen. N c

gio s T. Nozoe, trng i Hc Quc Gia i Loan tch t cc cy bch ti i Loan do vo
nm 1938. V cu trc cng hng minh ha tnh thm ca C.
O
OH
7)
Proton ca nhm OH trong tropolon c tnh axit. Ba mol tropolon C c th tc dng vi mt mol
tris(2,4-pentanedionato) st(III) [Fe(acac)3] hnh thnh mt phc c mu D. Cho bit cu
trc ca D?
BI GII:
1) (CH3)3C+SbF62) Ph 1: (CH3)3CF trong SbF5
3) 6e
4) C tnh thm
5) A
6)
7) Cng thc cu to cht D:
1,3,5-Hexatrien tri qua qu trnh khp vng quang ha hnh thnh 1,3-xyclohexadien. Phn ng
quang ha ny thun nghch v c c th lp th. V vy, chiu sng (2E,4Z,6E)-octatrien (A) bng tia
cc tm th hnh thnh nn xyclohexadien (B). S la chn di sng nh sng ph thuc vo cc i
hp th ca hp cht c chiu sng, v cc i hp th c lin quan n s lin kt i lin hp trong
mt mch.
chiu s ng
CH3
H3C
H3C
1)
CH3
Cho bit tn gi ca hp cht trien ban u (C) trong phn ng di y?

chiu s ng
C
H3C
CH3
Mt c ch phn ng tng t lin quan n qu trnh tng hp cc phn t hot ng sinh hc.
V d, di tc dng ca nh sng mt tri, 7-dehydrocholesterol (E) tri qua phn ng m vng in
vng to ra tin vitamin D3 (F), cht ny sau chuyn ha qua [1,7]-hydrogen to ra vitamin D3
(G).
H3C
H3C
CH2)3
(
CH3
H3C
H3C
CH3
H3C
CH3
CH3
nh s ng
H
CH2)3
(
tin vitamin D3 (F)
[1,7] H-shift
H
HO
7-dehydrocholesterol (E)
vitamin D3 (G)
HO
2)
Trong hai hp cht 7-dehydrocholesterol (E) v vitamin D3 (G), hp cht no bn ngh rng s
hp th nh sng vi nng lng cao hn? (E hay G)
Cho bit cu trc ha hc ca F?
Nguyn l ny c nghin cu k lng pht trin nhng vt liu thay i mu theo nh

sng. V d, chiu sng hp cht khng mu H vi tia cc tm to nn hp cht c mu. S bin i mu
din ra ngc li di tc dng ca nh sng kh kin.
4)
Cho bit cu trc ca hp cht mu I.

CH3
CH3
H3C
O
tia t ngoi
I h p cht c mu
O
nh s ng kh kin
khng mu
Cc hydrocacbon thm thng pht hunh quang mnh. Tuy nhin, mt nhm th amino ln cn
c th lm tt hnh quang ny. C ch s dp tt ny da vo s chuyn electron kh quang (PET Photoinduced Electron Transfer) m n c minh ha r rng bi cc gin obitan phn t ch ra
di y. Da vo s chiu sng vi nh sng c di sng thch hp (bc 1) th nhm mang mu
thm ban u (trng thi a) s y mt electron t HOMO n LUMO (trng thi b). Khi c mt mt
nhm amoni ln cn, mt trong s cc electron t do trn nguyn t ni s di chuyn n HOMO ca
nhm mang mu b kch thch (bc 2), v nh vy s kha con ng pht hunh quang thng thng
(trng thi c). S phi tr ca cc electron t do amin n proton hoc cc ion kim loi, ngn cn qu
trnh PET v ti lp hunh quang ca nhm mang mu thm (bc 3).
LUMO
LUMO
LUMO
HOMO
(c)
(b)
(a)
amine
lone-pair
electrons
PET
(1)
(2)
HOMO
HOMO
no fluorescence
M+ (3)
(d)
LUMO
HOMO
N M
Nhiu b cm bin hunh quang cc ion kim loi hoc proton nhy v rt ng quan tm c
pht trin da trn s vn dng qu trnh PET. V d, hp cht J c dng lm b cm bin pH.
N
Cl
5) Theo bn th hp cht J c pht hunh quang trong dung dch kim (pH = 10.0) hay khng?
BI GII:
1) (2E, 4Z, 6Z) octatrien
2) E
3) Cu trc ha hc ca F:
4) Cu trc ha hc ca I:
5) Khng

Ngi ta dng cng thc chiu Fischer m t s sp xp khng gian ba chiu ca cc nhm
c lin kt vi mt tm cacbon trn khng gian hai chiu. Trong loi cng thc ny, giao im ca hai
ng thng vung gc biu th mt tm sp3. ng nm ngang ni lin B v D qua tm cacbon th
hin lin kt ngoi mt phng giy (gn ngi quan st). ng thng ng ni hai im A v C qua
tm cacbon th hin lin kt nm trong mt giy (xa ngi quan st).
A
D
into plane
A
B
out of plane
B
C
1) Gio s Kagan pht trin hp cht ChiraPhos, mt cht c nhiu ng dng trong tng hp bt i.
Da trn cng thc chiu Fisher di y, hy cho bit cu hnh tuyt i R/S ca cc trung tm bt
i trong ChiraPhos theo quy tc hn cp Cahn-Ingold-Prelog.
CH3
H 2 PPh2
Ph2P 3 H
CH3
ChiraPhos
2) Mt trong nhng ng phn lp th ca ChiraPhos l mt hp cht meso. Xc nh X v Y trong

cng thc chiu Fischer di y.
H
X
H3C
2
3
Y
PPh2
H
meso-ChiraPhos
Lp th ca cc hp cht cacbohydrat thng c biu th bng cc cng thc chiu Fischer. V

d, cng thc chiu Fischer di y biu th cu trc ca D-glucoz. Mt iu th v l glucoz mch
h c th chuyn ha thnh cu trc vng qua s hnh thnh hemiaxetal gia hai nhm C5-OH v C1andehit.
O
H
HO
H
H
CH
2 OH
3 H
4 OH
5 OH
CH2OH
D-glucose
(open chain)
OH
HO C
H
OH
HO
H
H
OH
H
O
CH2OH
H C
H
OH
HO
H
H
OH
H
O
CH2OH
-anomer
or
-anomer
(cyclic structures)
S hnh thnh hemiaxetal sinh ra hai ng phn lp th, c gi l cc anome. -anome

nguyn cht ca D-glucoz c gc quay cc ring l +112.2o, trong khi -anome c gc quay cc ring
l +18.7o. Trong nc th -anome hay -anome u to ra mt hn hp cn bng vi gc quay cc
ring bng +52.6o.
3)
Tnh phn trm cc ng phn -anome trong hn hp cn bng ca D-glucoz trong nc.
4)
Gia -anome v -anome, anome no bn hn trong nc? ( hay )
5)
V cu dng gh ca ng phn -anome.
6)
Cho bit hp cht trung gian thng thng ca s chuyn ha ln nhau gia - v -anome?
Phn ng cng HCN vo mt andehit to ra mt xyanohydrin, cht ny sau c th b kh

thnh mt -hydroxyandehit.
O
R
OH
HCN
H
OH
reduction
CN
cyanohydrin
Cc ng ng cao ca cacbohydrat, nh l D-talos, c th c tng hp t D-glyxerandehit

bng s lp li ba ln iu kin phn ng ging nh di y.
CHO
OH
CH2OH
CHO
HO
H
H
OH
CH2OH
1. HCN
2. reduction
D-glixerandehit
HO
HO
HO
H
v i quang
CHO
H
H
H
OH
CH2OH
D-talose
+ i quang
7)
Trong hn hp sn phm cui cng c bao nhiu cp cht ng phn i quang?
Enzim l mt cht xc tc sinh hc rt ng quan tm, chng kim sot m hnh chuyn ha ha
hc trong c th sng. Bi v kh nng v c trng xc tc tt ca chng, nn ng dng enzim trong
tng hp hu c tr thnh mt trong nhng lnh vc ln mnh nhanh nht cho s pht trin ca phng
php tng hp mi. Sau y l d liu cho phn gii ng hc xc tc men ca raxemic xiclohexanon
cha nhm th v tr s 2 theo cc phn ng Baeyer Villiger (Bng 1).
Bng 1. Phn gii ng hc xc tc men ca raxemic xiclohexanon cha nhm th v tr s 2 theo cc
phn ng Baeyer - Villiger
O
O
R
men
O
R
+
R
hn h p raxemic
O
R
STT
Hiu sut (%)
ee%
Hiu sut (%)
ee%
Et
79
95
69
98
n-Pr
54
97
66
92
Allyl
59
98
58
98
ee: lng d ng phn i quang

8)
9)
Cho bit t l ng phn (R)/(S) ca 6-allycaprolacton trong d kin s 3?

AMCPB (axit meta-cloperbenzoic) l mt tc nhn oxi ha thng thng cho cc phn ng Baeyer
Villiger. S dng AMCPB nh mt tc nhn oxi ha cho phn ng trn, thay v men. Cho bit
phn trm lng d ca sn phm caprolacton?
BI GII:
1) (2S, 3S)
2) X = CH3; Y = PPh2
3) 36%
4)
5) Cng thc cu trc:
6) Cng thc chiu Fischer:
7) Khng
8) 99:1
9) 0
Mt trong nhng yu cu ban u cho s pht trin cc diot pht x nh sng hu c (OLED) l
s tm kim vt liu pht quang c hiu qu cao m c th l nhng phn t nh hoc nhng hp cht
cao phn t. V d nh floren, mt biphenyl cu ni metylen, c hiu sut lng t hunh quang cao
hn biphenyl.
3
2
7
8
1
9
Biphenyl
Fluoren
Nhiu dn xut floren c pht trin, chng c tim nng ng dng trong cng ngh mn
hnh phng. trnh s tng tc gia cc phn t, cc nhm th ln c a vo v tr C9 ca
fluoren. Mt v d ca trng hp ny l hp cht C, mt pht minh v vt liu pht x nh sng xanh
c hiu qu cao rt th v v b ch. Di y l gin phn ng tng hp cht ny.
NH2
1) NaNO2, HCl
0-5 oC
1) Mg, Et2O
A
2)
2) KI
HOAc, HCl
ng- c dng
C (C25H16)
3) H2O
1) Xc nh cu to ca A, B, v C.
Tinh th lng tr thnh mt phn cuc sng hng ngy ca chng ta, t nhng ng h eo
tay, my tnh b ti, n mn hnh phng mu. Cc phn t tinh th lng thng cha mt trung tm
cng nhc v ui l mt mch ankyl linh hot nh c trnh by di y.
CN
phn m ch
ankyl linh ho t
trung tm
cng nhc
Biphenyl v terphenyl l nhng cu trc c bn cho trung tm cng nhc ca cc tinh th lng.
y l loi cu trc c th c tng hp c hiu qu qua phn ng ghp mt aryl bromua hoc iodua
vi axit arylboronic c xc tc paladi (phn ng ghp mch Suzuki).
Terphenyl
Mt v d c trng ca phn ng ghp mch Suzuki c biu din di y. Brombenzen tc

dng vi axit phenylboronic c mt xc tc paladi to ra biphenyl.
Br
B(OH)2
Pd(0) catalyst
Di y s tng hp hai phn t tinh th lng, 4-xyano-4-pentylbiphenyl v G.
NC
C5H11
CuCN
DMF
Br2
D
C4H9COCl
AlCl3
NH2NH2
F
KOH, t
F
C8H17O
F
B(OH)2
Pd(PPh3)4
Na2CO3
MeOCH2CH2OMe, H2O
G
2) Cho bit cu trc ca D, E, F, v G?

BI GII:
1) Cng thc cu to ca A, B, C:
2) Cng thc cu to ca D, E, F v G
Cc polyme hu c c nh hng rt ln i vi cuc sng hng ngy ca chng ta. Hng nghn
tn cc loi cao phn t khc nhau c sn xut mi nm. Tng hp cc polime hu c c s dng
trn nhiu lnh vc, t nguyn liu dt cho n cc con chip my tnh, v n c van tim nhn to.
Chng c s dng rng ri nh cht do, keo dn, vt liu xy dng, cht do c kh nng phn hy
v sn. Poly (vinyl ancol) (PVA) l mt v d quan trng ca mt polyme c kh nng ha tan trong
nc. Gin 1 di y tm tt mt phng php tng hp PVA.
Gin 1
Monome A
polyme ha
Polyme B
Poly(vinyl ancol) (PVA)
Polyme B trn cng l thnh phn chnh trong ko cao su. Phn tch nguyn 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
110
100
3503
1434
3094
849
90
977
1295
Transmittance (%T)
951 876
80
1021
1372
70
1648
60
1138
50
1761
1217
40
30
4000
3500
3000
2500
2000
1500
1000
-1
wavenumber (cm )
Ph IR ca Monome A
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.
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
2697 2587
3107
2062
2856
35533445
1945
Transmittance (%T)
3632
80
2999
662
854
60
2955
1634
40
988
1069
1439
1404
1279
1205
1731
20
4000
3500
3000
2500
2000
1500
-1
wavenumber (cm )
Ph IR ca Monome C
1000
812
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+
dung dch
Ca( OH) 2
Br2
vn c
H (khng mu)
Xc nh cu to E, F, G v H?
8)
Trn polyme D vi cht quang sinh axit (PAG - a photo acid-generator) to vt liu quang nh.
Sau khi c ph ln trn cht nn v em ra ngoi sng, PAG sinh proton lm xc tc cho phn ng
ha hc trong khun polyme. Nu chiu sng qua mt tm mng to hnh (Hnh 1), mt nh ca tm
mng s hnh thnh trn khun polyme. Sau khi sy v ra cc vt liu c tnh axit bng nc ra nh
thng thng to ra nn c trang tr I.
nh s ng
m ng t o hnh
Polyme D + PAG
Cht nn
Hnh 1
17-9
(a)
Gin no di y minh ha tt nht cho cht nn c trang tr I?

(b)
(c)
(d)
mu sm th hin cu trc b bin i so vi ban u:

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:
9) hnh d
Charles Pederson khm ph ra ete vng nm 1967. Jean-Marie Lehn, Donald Cram v Charles
Pederson cng nhn Nobel Prize nm 1987 cho s ng gp ca h vo ha hc siu phn t.
S phn ng di y biu din mt phng php tng hp diol A. Tuy nhin, do c mt ca
catechol trong cc cht tham gia m sn phm gm hn hp ca A v sn phm ph B.
OH
OH
Cl
+
O
O
c t p cht l
catechol (cng
thc d- i)
Cl
O
1) NaOH
2) H3O+
OH
HO
O
O
O
A
+
B
OH
Catechol
B c thnh phn nguyn t C:H:O = 66.5:6.7:26.6 v khi lng phn t bng 360. Ph 1H NMR
ca B cho thy bn tp tn hiu proton. Hai trong c thu c ti 7,0-7,5 v tn hiu kia ti
3,7-4,2. T l tch phn ca bn tp tn hiu l 1:1:2:2. Hp cht B lin kt bn vi ion kali. Mt v d
thuyt phc cho iu ny l vic dng B gip ha tan KMnO4 trong benzen to ra mt cht nhum
mu tm.
1)
Xc nh cu to ca B.
2)
Cho bit vai tr chnh ca H3O+ trong phn ng trn.
(a) hot ha ClCH2CH2OCH2CH2Cl.

(b) trung ha NaOH.
(c) tch nhm tetrahydropyran.
(d) hot ng nh mt h m kim sot pH ca dung dch.
Di y l con ng tng hp [2.2.2]cryptand:
O
O
SOCl2
O
OH
HO
O
LiAlH4
H2N
NH2
high dilution
1, B2H6
F
O
N
2. H2O
O
[2.2.2]Cryptand
3)
Xc nh cu trc cc cht t C-F.
4)
Ti sao qu trnh tng hp D t C yu cu iu kin rt long?

(a)
Do phn ng gia C v diamin th ta nhit mnh, dung dch long c dng

hp th nhit thot ra t phn ng.
(b) iu kin long cao c p dng ngn chn s hnh thnh polyme v oligome.
(c) Cn bng nhit c u tin to ra D trong iu kin rt long.
(d) tan ca nguyn liu ban u nh.
i lc vi mt cation kim loi c kim sot bi mt s yu t nh s tng ng v kch thc
gia khong trng ca cht mang l ete vng v ca cation khch; s nguyn t phi tr ca cht mang.
Bng 1 di y cho bit bn knh ca cc cation kim loi kim v ng knh khong trng ca mt s
ete vng.
O
15-C-5
18-C-6
Cavity
O
12-C-4
21-C-7
Bng 1. Bn knh ca cc cation kim loi kim v ng knh khong trng ca mt s ete vng.
Cation (bn knh, pm)
Li+ (68)
Na+ (98)
K+ (133)
Cs+ (165)
Khong trng ca ete vng (ng knh, pm)

12-C-4 (120-150)
15-C-5 (170-220)
18-C-6 (260-320)
21-C-7 (340-430)
5)
Da vo c s d liu ny, hy la chn ng cong thc nghim trong Hnh 1 tng ng vi

cc ete vng xiclohexyl t G n I.
log Kf
6.0
III
4.0
5.0
O
O
O
G
O
O
II
3.0
I
2.0
O
I
1.0
Na
Cs
Bn knh cation
Hnh 1: Kh nng to phc ca cc ete vng vi cc ion kim loi trong methanol
BI GII:
1) Cng thc cu to ca B:
2) cu c ng
3) Cng thc cu to ca C, D, E v F:
4) Cu b ng
5) ng cong I cho cht I; ng cong II cho cht G; ng cong III cho cht H

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I.

OLYMPIC HO HC VIT NAM:

OLYMPIC HA HC SINH VIN TON QUC 2004:

2) Cng thc cu to cc sn phm:

2) Cng thc Fis:

OLYMPIC HA HC SINH VIN TON QUC 2004:

ClCH 2CH 2Cl 500

2) Qa trnh tng hp nh sau:

3) Qa trnh tng hp nh sau:

4) Qa trnh tng hp nh sau:

OLYMPIC HA HC SINH VIN TON QUC 2004:

3. Cc phng trnh phn ng:

Cc phn ng xy ra theo c ch:

b) Hydrat ha X to ra ancol c phn ng iodofom.

+2CHI3 + 10NaI + 10H2O

O2; V2O5; 400 - 500oC

C th tin hnh theo s sau:

OLYMPIC HA HC SINH VIN TON QUC 2005:

a) Cc phng trnh phn ng:

+2CH3OH + Mg2+ + Br-

b) Khi iu ch M i t Y nht thit phi i qua cc giai on trn. V:

S to thnh hp cht trn nh sau:

K THI CHN HC SINH GII QUC GIA NM 2002:

2. Trt t tng dn tnh baz :

b) T benzen v cc cht v c, hu c (cha khng qu 3 nguyn t cacbon), iu ch:

1) NaNH2 hay KOH/ancol

1) NaNH2 hay KOH/ancol

K THI CHN HC SINH GII QUC GIA NM 2002:

Cng thc cu to ca A, B, C, D, E, G v cc phng trnh phn ng:

C2H5Br/ AlCl3 khan

H2SO4 c/180 C HO3S

SO3H1) NaOH, 300 C HO

NaNO2 + HCl, 5OC

2. Aspactam H2N-CH C NH CH-COOCH3

K THI CHN HC SINH GII QUC GIA NM 2003:

c) Vit cng thc lp th dng bn ca cc ng phn trong hn hp X.

(vng 7 cnh km bn hn vng 6 cnh)

K THI CHN HC SINH GII QUC GIA NM 2003:

CH3 CH CH2 CH3

CH3 CH CH2 CH3

CH3 CH CH2 CH3

CH3 CH CH2 CH3

C CH2 CH2 CH2

C CH2 CH2 CH2

K THI CHN HC SINH GII QUC GIA NM 2003:

b) Gii thch hng ca phn ng to thnh C8H8O4NSCl v C6H8O2N2S.

Nhit si: A > C > B.

K THI CHN HC SINH GII QUC GIA NM 2003:

1. Hy xc nh cng thc cu to v vit cng thc Fis ca TRF.

1. *T d kin thy phn suy ra 2 cng thc Glu-His-Pro v His-Pro-Glu (u c 1 nhm

Cng thc Fis:

(hoc vit 3 cn bng ring r; khng cn cng thc Fis)

HOOC CH2 CH2 CH COOH

C6H10O4 (F)H2O/ DCl hh

1. *T D-glucoz suy ra cu hnh ca D-guloz. X khng kh nn c lin kt 1,1-glicozit.

c) H2O + DCl HOD + HCl

a) Trnh by c ch phn ng clo ho biphenyl theo hng u tin nht.

Do cacbocation bc hai (II) c kh nng chuyn v hidrua to thnh cacbocation bc ba (III) nn to

2-Clo-2-metylbutan l sn phm chnh.

K THI CHN HC SINH GII QUC GIA NM 2004 (Bng A):

Vit cng thc cc sn phm hu c A, B, C v D.

cacbocation ny alkyl ha propen

Tch (II) v (IV) ra khi hn hp: