Bai tap Hoa Hoc nang cao chuyen e Hu C

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Trang: 1

------------------------------------------------------------------------Cu 1: Streptimidon l mt loi cht khng sinh c cng thc nh sau:

a. M t cc trung tm lp th ca Streptimidon bng k hiu E, Z v R, S.

b. Streptimidon c bao nhiu ng phn lp th, trong c bao nhiu ng phn enan v bao nhiu
ng phn dia.
Cu 2: So snh v gii thch:
a. Nhit si ca cc cht sau: xyclopentan, tetrahirofuran v piroliin.
b. mnh tnh baz ca: imetylamin, piperiin v piriin
Cu 3: Cht ()Nicotin l mt loi ankaloit c trong thuc l v c th c tng hp theo cch sau:
o
(1) Axit nicotinic (3-pyridincacboxylic) + SO2Cl2 t
nicotinyl clorua (C6H4ONCl)

(2) Nicotinyl clorua + C2H5OCH2CH2CdCl

G (C11H15ON2), mt xeton
H 2 , xc tc, t o
(3) G + NH3
H (C11H18ON2)
to
(4) H + HBr
I (C9H12N2) + etyl bromua
(5) I + CH3I, NaOH ()nicotin (C10H14N2)
Xc nh cu trc ca ()nicotin v hon thnh cc phng trnh phn ng trn.
Cu 4: Cht hu c (Y) c loi bm m tng hp trong ma giao phi. (Y) cng c th c tng
hp theo cch di y. Hy cho bit tn gi ca hp cht ny v hon thnh cc phng trnh phn ng
xy ra:
(1) Hept-1-in + LiNH2 S (C7H11Li)
(2) S + 1-clo-3-brompropan T (C10H17Cl)
(3) T + Mg, sau cho sn phm ln lt tc dng vi n-C10H21CHO, H+ U (C21H40O)
(4) U + H2 xc tc Lindlar V (C21H42O)
(5) V + CrO3 Y ( C21H40O)
Cu 5: Styryllacton c phn lp t thc vt c cng thc (hnh di).
6
O 5 4
3
7
O
9
8
O
1 2
HO
Vit cng thc cu dng cc cp ng phn i quang v gi tn styryllacton theo danh php IUPAC.
Hng dn gii
Hp cht:
6
O 5 4
3
7
O
9
8
O
1 2
HO
Tn: 8-hiroxi-7-phenyl-2,6-ioxabixiclo[3.3.1]nonan-3-on
Cng thc cu dng:

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Bai tap Hoa Hoc nang cao chuyen e Hu C

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4
2

H 5C 6

HO

O
8

O O
3

O
5

O
1

C 6H 5
OH

H 5C 6

HO

Trang: 2

O
9

C6H5
OH

Cu 6: Dng mi tn cong ch r c ch chuyn 7-ehirocholesterol (I) thnh vitamin D3 (II) v cho bit
cu dng bn ca n. Bit trong cng thc di y: R l: -CH(CH3)-(CH2)3-CH(CH3)2
R

(II)

(I)

HO

HO

Hng dn gii:
2.

R
H

H2C

as
HO

HO

to
R

HO

HO

CuCu
dng
bnbn: S-trans
dng

Cu 7: Hp cht A (C10H18O) c phn lp t mt loi tinh du Vit Nam. A khng lm mt mu

nc brom v dung dch thuc tm long, cng khng tc dng vi hiro c xc tc niken, nhng li tc
dng vi axit clohiric m c sinh ra 1-clo-4-(1-clo-1-metyletyl)-1-metylxiclohexan.
1. Hy xut cu trc ca A.
2. Hp cht B (C10H20O2 ) c trong mt loi tinh du Nam M. T B c th tng hp c A bng
cch un nng vi axit.
a. Vit cng thc cu to v gi tn B.
b. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng
tng hp A.
3. Hp cht B thng c iu ch t C (2,6,6-trimetylbixiclo[3.1.1] hept-2-en) c trong du
thng. Dng cng thc cu to, vit phng trnh phn ng v ch r cc lin kt ca C b t ra.
4. Trong cy long no c hp cht D tn l 1,7,7-trimetylbixiclo[2.2.1]heptan-2-on (hay l campho).
Vit s cc phn ng tng hp D t C v cho bit c ch ca giai on u.
5. V cu to ha hc, cc hp cht A, B, C v D trn c c im g chung nht? Minh ha vn
tt c im trn cc cng thc cu to ca chng.
Hng dn gii:
1. Xc nh cng tc cu trc ca A(C10H18O) 2
- A khng lm mt mu dung dch nc brom v dung dch thuc tm long chng t trong A
khng c ni i hay ni ba;
- A khng tc dng vi hiro trn cht xc tc niken chng t trong A khng c nhm chc
cacbonyl;
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Bai tap Hoa Hoc nang cao chuyen e Hu C

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Trang: 3

A tc dng vi axit clohiric m c sinh ra 1-clo-4-(1-clo-1-metyletyl)-1-metylxiclohexan,

trong A c vng no v c lin kt ete.
=> Suy ra cng thc cu trc ca A
CH3

CH3
O

CH3

H3C

CH3

CH3

2. a.

B (C10H20O2)

- H2O

A (C10H18O)

Suy ra B l mt iol c b khung cacbon nh A

OH
+

H
H2O

OH
B
Gi tn B: 1-hiroxi-4-(-1-hiroxi-1-metyletyl)-1-metylxiclohexan
b. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng.
C 2 dng trans v cis ca B u cu dng gh bn vng, tuy vy cu dng gh khng th tham gia
ng vng m phi i qua dng thuyn km bn. Dng thuyn s tham gia phn ng SN1 ni phn t.
OH

(+)

OH

OH

OH OH

OH

(+)

Cis-B

(+)

OH
OH

OH

OH

OH

Trans-B

OH

(+)
+

3. Lin kt ca C b t cc ng chm chm:

OH
+

2 H2O

OH

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Bai tap Hoa Hoc nang cao chuyen e Hu C

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4.

HO

Cl

H2O

HCl

Trang: 4

D
H+

(+)

Cl-

Chuyn v

chuyn v

(+)

5. c im chung nht v cu to ho hc: mi phn t gm 2 n v isopren (hoc isopentan) ni vi

nhau.
Cu 8: Sau khi x l hn hp li ng hoc v tru c cha pentozan (C5H8O4)n vi dung dch axit clohiric 12%
ri tin hnh chng ct, nhn c cht lng A (C5H4O2) mu vng c mi thm. Cho A phn ng vi KOH ri
axit ha th nhn c B (C5H4O3) v C (C5H6O2).
a. Vit phng trnh phn ng thu phn pentozan to thnh A v cng thc ca A, B, C.
b. Vit phng trnh phn ng ca B tc dng vi C khi c xc tc axit.
c. Hy trnh by iu kin nitro ho A nhn c D (C5H3NO4).
d. Vit phng trnh phn ng ca D tc dng vi: (I) ; (II).

H2N-N

NH

NH

S
S
(II)

(I) O

Hng dn gii:
1. Trong li ng v v tru c cha pentozan,khi un nng vi dung dch HCl 12% chuyn thnh
pentoz ri tch nc cho fufurol
CHO
- 3H2O
(CHOH)3

(C5H8O4)n HCl 12%

CH2OH
2
O A

O
b.
O
c.

CHO

KOH

O C
COOK

H3O+

A(C5H4O2)
COOK

COOH
B

COOH +

CH2OH

CHO

CH2OH

H+

COOCH2

nitro ho A cn phi bo v nhm anehit bng (CH3CO)2O

CHO

(CH3CO)2O

CH(OCOCH3)2

Thc hin phn ng nitro ho, sau thu phn phc hi nhm CHO
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Bai tap Hoa Hoc nang cao chuyen e Hu C

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CH(OCOCH3)2

O
d.

HNO3

O2N

CH(OCOCH3)2

H3O+

O2N

Trang: 5

CHO
D

Phn ng ca D vi I v II
O2N
D

I
O

O2N

H2N N

CHO

CHO

O2N

NH

NH
O2N

CH

N N

CH

O
NH

NH

II S
Cu 9: Geniposit (hnh di) l mt hp cht c tch ra t qu dnh dnh. Thu phn geniposit sinh ra
hai sn phm l genipin v D-glucoz. Genipin tham gia phn ng to mu vi gelatin (y l c s pht
hin du vn tay trong k thut hnh s). Hy vit s phn ng to genipin v phn ng ca genipin vi
mt aminoaxit gii thch hin tng trn.
COOCH3
HOH2C
HO
HO

O
O
O
OH

CH2OH

Hng dn gii:
Phn ng thu phn geniposit thu c genipin v D-glucoz
COOCH3
COOCH3

OH

O
HOH2C

O
HO

HOH2C

OH

HO
HO

O
OH
OH

CH2OH

HO

OH
Gelatin (c trong da) cu to t cc polipeptit, ly i din l mt aminoaxit nh glyxin, ta c phng
trnh:
COOCH3
COOCH3

H2N-CH2-COOH

N-CH2-COOH

HOH2C

HOH2C
OH
OH
sn phm c mu pht hin du vn tay trong k thut hnh s.
Cu 10: Ngi ta phn lp c mt tetrapeptit (peptit A) t prothrombin ngi. Cu to ca peptit A
c tin hnh xc nh nh sau:
a. Bng phng php Edman th nhn c trnh t aminoaxit ca peptit A l Leu-Glu-Glu-Val.

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Bai tap Hoa Hoc nang cao chuyen e Hu C

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Trang: 6

b. tip tc xc nh cu to, ngi ta tin hnh in di trn giy pH 6,5 peptit A v mt peptit tng
hp B (cng c trnh t aminoaxit l Leu-Glu-Glu-Val) th li nhn c qung ng di chuyn
khng ging nhau, c th nh hnh di y:
Peptit A
2,5

Peptit B

0
1
2 1,7
3
n v di
o
c. Khi thu phn hai peptit A v B bng HCl 6N 110 C, th c A v B u cho Leu(1), Glu(2), Val(1) ; nhng
khi thu phn bng kim th peptit B cho Leu(1), Glu(2), Val(1) cn peptit A cho Leu(1), X(2), Val(1).
Hy gii thch cc kt qu thc nghim xc nh cu to ca X v gi tn X theo danh php
IUPAC.
Hng dn gii:
1. Xc nh cu trc ca X
- Phng php Edman thc hin pH thp,bit c trnh t l Leu-Glu-Glu-Val.
- in di pH 6,5 cho thy peptit A dch chuyn nhanh hn v pha cc dng(+), chng t A c in
tch m ln hn B,tnh axit ca A ln hn B.
- Khi thu phn trong mi trng HCl 6N 110oC th c A v B u thu c Leu(1), Glu(2) v Val(1). Kt hp vi phng php Edman trn cho thy cc qu trnh ny thc hin mi trng axit mnh, pH
thp. pH thp phn t X b ecacboxyl ha, loi CO2 mt i 1 nhm COOH.
- Khi thu phn bng kim peptit A to ra Leu(1),X(2) v Val(1),trong mi trng kim khng c qu
trnh decacboxyl ho nn nhn c X(2).
- Kt hp cc kt qu trh nghim cho thy X c thm 1 nhm COOH so vi Glu tc l khi loi 1 nhm
COO th X chuyn thnh Glu.
X
HOOC CH2 CH2 CH COOH
CO2
NH2
Vy X l::
Vy X
HOOC CH CH2 CH COOH
NH2
COOH
Gi tn: Axit 3-aminopropan-1,1,3-tricacboxylic
Cu 11: Vit s phn ng oxi ha D-glucoz to thnh axit anonic v axit anaric, cng thc
Haworth cc mono v i -lacton ca chng v gi tn cc lacton y.
Hng dn gii:
O
COOH

CHO

OH

OH
HO
OH
OH
CH2OH
HNO3

COOH
OH
HO
OH
OH
COOH

Br2

HO

H2O

OH

O
OH

OH
OH

D- -gluconolacton

OH

HO

CH2OH

CH2OH
axit gluconic
COOH
OH
O

CH2OH
OH
O

OH

OH
COOH
O
OH HO

OH
O

O
O

O
O

OH
1,4-lacton ca axit glucaric
1,4:3,6-dilactonca axit glucaric
3,6-lacton
ca
axit
glucaric
3,6-lacton ca axit glucaric
OH

Cu 12: Cho s o phan ng:

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Bai tap Hoa Hoc nang cao chuyen e Hu C

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Trang: 7

CH3C=O
C2H5

1.

H
(A)

C6H5MgBr
2.

H2O

HBr a
c

C3H7

a. Viet c che phan ng va cong thc cau tao cac san pham.
b. Goi ten cac cau hnh cua B v C theo danh phap R, S.
Cu 13: Hay giai thch s hnh thanh nhanh chong 2,4,6-Br 3C6H2NH2 (C) khi cho
p-H2N-C6H4-SO3H (A) hoac p-O2N-C6H4-COOH (D) tng tac vi dung dch nc
brom.
Cu 14: Lam the nao thc hien chuyen hoa sau vi hieu suat tot nhat:
C
NH2

NH2

Cu 15: Hon thnh cc phng trnh phn ng sau:

a. CH3COCH3 + 2 EtOOC-COOEt
NaOEt, HOEt

H O ,t0
E
3

b. CH3COCH2COOEt

+ CH2=CH-CHO
NaOEt, HOEt

c. CH3COCH2COCH3

0
H2N-NH2
t

F (C7H4O6, i xng)

G (C9H12O3)

H (C5H8N2)

d. EtOOCCH2COOEt + 2CH2=CH-COOEt
NaOEt, HOEt
0
e. EtOOCCH2COOEt + H2N-CO-NH2
t

I
NaOEt, HOEt

K (C15H22O7)

L (C4H4N2O3)

Cu 16: Ancaloit c cha h vng piroliziin c gi l ancaloit piroliziin.

Pirolizi
in

C khong 100 ancaloit piroliziin khc nhau c phn lp, trong c

retronexin ln u tin c tch ra t thc vt vo nm 1909, nhng mi n nm
1962 mi c tng hp trong phng th nghim theo s sau:
EtOOC(CH2)2NHCOOEt
B (C14H21O7N)
E (C6H10O2NCl)

H (C10H17O4N)
O
D

ietyl fumarat

1. HCl
2. HOEt, HCl

C (C11H17O5N)

BrCH2COOEt, Na2CO3

1. H2O, OH , t
2. H+

NaOEt

A (C16H27O8N)
NaBH4

F (C10H15O4N)

D
KOEt

1. HOEt, H+
2. LiAlH4, THF
3. H2O

I (C8H11O3N)

O
N COOEt

Na

1. H2O, OH -, t0
2. HCl
H2, Pt

G
HO

CH2OH

HO H COOEt
N

a. Hy vit cng thc cu trc ca A, B, C, E, F, H, I.

b. Hy cho bit cc hp cht trung gian c hnh thnh khi chuyn t F sang G
c. Sn phm cui cng ca s trn c quang hot khng?
Cu 17: Reserpin l mt ancaloit c trong r cy ba gc, c dng cha bnh
huyt p cao. Cch y gn na th k Woodward tng hp ton phn
reserpin. Mt s giai on u ca cng trnh tng hp hu c ny nh sau:

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Bai tap Hoa Hoc nang cao chuyen e Hu C

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Axit (E)-penta-2,4-ienoic
(1)
C H COOOH (3)
B (C11H12O4)
C (C11H12O5) (CH3CO)2O (4)
6 5

p-Benzoquinon (C6H4O2)

NaBH4 (2)

Trang: 8

A (C11H10O4)
D (C11H10O4)

a. Vit phng trnh phn ng (1) v cng thc cu to ca A.

b. L thuyt v thc nghim u cho bit A (sn phm chnh) sinh ra trong phn
ng (1) c t nht 2 nguyn t C* k nhau gi cu hnh S v cc nguyn t H
C* u v tr syn i vi nhau. Hy vit cng thc lp th ca A.
c. Trong phn ng (1), ngoi cht A cn c th sinh ra my ng phn cu hnh?
Ti sao? Dng cc k hiu lp th phn bit cc ng phn .
d. B l sn phm chnh ca phn ng (2), khi un nh B vi anhirit axetic thu c lacton vi hiu sut cao. Vit cng thc cu to v cng thc lp th ca B;
Gii thch. Dng cng thc cu trc vit s cc phn ng (3) v (4).
Cu 18: Hy thc hin dy chuyn ho sau:

0
2-Metylpropanal + piperiin H ,t
C9H17N
C11H20ONCl
MeCOCl
H2O,H
MeCOCMe2CHO

Cu 19: T mt loi thc vt ngi ta tch c cht A (C10H12O2). A phn ng vi

dd NaOH to thnh cht B (C10H11O2Na). B phn ng vi CH3I cho cht C
(C10H11O(OCH3)) v NaI. Hi ca C phn ng vi H 2 nh cht xc tc Ni cho
cht D (C10H13O(OCH3)). D phn ng vi dd KMnO 4 trong H2SO4 to thnh axit
3,4-imetoxibenzoic c cng thc 3,4-(CH3O)2C6H2COOH v axit axetic.
1. Vit cng thc cu to ca A, B, C: bit rng A, B, C khng c ng phn
cis-trans, cc cng thc trong ngoc n trn v cng thc phn t.
2. Vit phng trnh cc phn ng xy ra.
Cu 20: Hp cht A (C18H18O2Br2) phn ng c vi dd NaOH nng. Cho hn hp sau
phn ng tc dng vi dd axit v c long, thu c B (C9H9O2Br) v C (C9H11OBr).
- Oxi ho B hoc C u thu c axit para-brom-benzoic.
- Oxi ho trong iu kin thch hp C chuyn thnh B.
o
Cl2 ,as
- T B thc hin chuyn ho theo s sau: B
D
ddHCl G

ddNaOH,t E
o
H2SO4 ,170 C H
(D cha 1 nguyn t Clo trong phn t, H c ng phn Cis-trans. Cc sn phm
D, E, G, H u l sn phm chnh)
a. Vit cng thc cu to ca A, B, C, D, E, G, H v vit cc phng trnh phn
ng xy ra.
b. So snh nhit nng chy ca B v C. Gii thch.
Cu 21: Hp cht hu c A c cng thc phn t C 7H9N. Cho A phn ng vi C 2H5Br
(d), sau vi NaOH thu c hp cht B c cng thc phn t C 11H17N. 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 (C 11H17N). Cho A phn ng vi H 2SO4 (c) 180oC to hp
cht D c cng thc phn t C 7H9O6S2N, sau khi ch ho D vi NaOH 300 oC ri vi
HCl s cho sn phm E (E c phn ng mu vi FeCl 3). 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.
Cu 22: Amyglain (k hiu l A) c cng thc phn t C20H27O11N l mt isaccarit
thin nhin khng c tnh kh, ch cha lin kt -glicozit.
- Khi thu phn A bng dung dch axit long th thu c glucoz v hp cht B
(C7H6O) lm mt mu nc brom.
- Khi un A vi dung dch axit c th thu c glucoz v hp cht C (C8H8O3).
Oxi ho C bng dung dch KMnO4 ri axit ho th thu c D (C7H6O2) khng lm
mt mu dung dch nc brom.
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Bai tap Hoa Hoc nang cao chuyen e Hu C

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Trang: 9

Cho A tc dng vi CH3I ly d (mi trng kim), thu phn (mi trng axit), ri
cho cc sn phm tc dng vi HIO 4 (d) th thu c 2,3,4,6-tetra-O-metylglucoz
; 2,3-imetoxibutanial v metoxietanal.
a. Hy xc nh cng thc cu to ca A, B, C, D.
b. Hy gii thch s to thnh B khi thu phn A. Hp cht C c quang hot khng?
V sao?
Cu 23: Epiclohidrin la mot epoxit, nguyen lieu chnh e che tao nha epoxi
dung lam keo dan kim loai, knh, sanh s. Epiclohidrin phan ng vi
C6H5MgBr tao thanh C6H5CH2CH(OH)CH2Cl.
a. Xac nh cong thc cau tao cua epiclohidrin.
b. Viet cac phng trnh phan ng khi cho epiclhidrin tac dung vi ru
etylic, dung dch NH3 va khi epiclohidrin b thuy phan trong moi trng
kiem.
c. e ieu che nha epoxi, ngi ta un nong epiclohidrin vi bisphenol-A.
Viet phng trnh phan ng. Bisphenol-A l (2,2-bis-[p-hidroxiphenyl] propan.
d. Khi tron nha epoxi noi tren vi mot amin a chc v du nh vi
N(CH2CH2NH2)3 th se thu c polime mang khong gian. Giai thch.
Cu 24: Axit fumaric v axit maleic c cc hng s phn li nc 1 (k1), nc 2 (k2).
Hy so snh cc cp hng s phn li tng ng ca hai axit ny v gii thch.
Cu 25: Cho cc ancol sau: p-CH 3-C6H4-CH2OH , p-CH3O-C6H4-CH2OH, p-CN-C6H4-CH2OH v
p-Cl-C6H4-CH2OH..
So snh kh nng phn ng ca cc ancol vi HBr v gii thch.
Cu 26: Oxi ho hirocacbon thm A (C8H10) bng oxi c xc tc coban axetat cho sn phm B. Cht B
c th tham gia phn ng: vi dung dch NaHCO 3 gii phng kh CO2; vi etanol (d) to thnh D ; un
nng B vi dung dch NH3 to thnh E. Thu phn E to thnh G, un nng G nhit khong 1600C to
thnh F. Mt khc, khi cho B phn ng vi kh NH3 (d) cng to thnh F.
Hy vit cc cng thc cu to ca A, B, D, G, E v F.
Cu 27: Hp cht 2,2,4-trimetylpentan (A) c sn xut vi quy m ln bng phng php tng hp
xc tc t C4H8 (X) vi C4H10 (Y). A cng c th c iu ch t X theo hai bc: th nht, khi c xc
tc axit v c, X to thnh Z v Q; th hai, hiro ho Q v Z.
a. Vit cc phng trnh phn ng minh ha v tn cc hp cht X, Y, Z, Q theo danh php IUPAC.
b. Ozon phn Z v Q s to thnh 4 hp cht, trong c axeton v fomanehit, vit c ch phn ng.
Cu 28: Cho s cc phn ng sau:
OH
HCHO
OH -

A NaCN
DMF

H2O

Cl

D1 + D2 + E (sn phm ph)

Hy vit cng thc cu to ca A, B, C, D1, D2 v E. Bit E c cng thc phn t C19H22O5N2.

Cu 29: HSCH2CH(NH2)COOH (xistein) c cc pKa: 1,96; 8,18; 10,28. Cc cht tng ng vi n l
HOCH2CH(NH2)COOH (serin), HSeCH2CH(NH2)COOH (selenoxistein), C3H7NO5S (axit xisteic).
a. Hy xc nh cu hnh R/S i vi serin v axit xisteic.
b. Hy qui kt cc gi tr pKa cho tng nhm chc trong phn t xistein. Vit cng thc ca xistein
khi pH = 1,5 v 5,5.
c. Sp xp 4 amino axit trn theo th t tng dn gi tr pHI v gii thch s sp xp .
Cu 30: Thy phn hon ton mt nonapeptit X thu c Arg, Ala, Met, Ser, Lys, Phe 2, Val, v Ile. S
dng phn ng ca X vi 2,4-initroflobenzen xc nh c Ala. Thu phn X vi trypsin thu c
pentapeptit (Lys, Met, Ser, Ala, Phe), ipeptit (Arg, Ile) v ipeptit (Val, Phe). Thu phn X vi BrCN
dn n s to thnh mt tripeptit (Ser, Ala, Met) v mt hexapeptit. Thu phn vi cacboxypeptiaza c
X v hexapeptit u cho Val. Xc nh th t cc amino axit trong X.
Cu 31: Vit cc phng trnh phn ng thu phn metyl--D-galactofuranozit (A) v metyl--D-sobofuranozit
(B) trong mi trng axit. (soboz: 2-xetohexoz; cu hnh C3 ca n v ca galactoz khc nhau).
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Cu 32: Arabinopyranoz (D-anopentoz c cu hnh 2S, 3R, 4R) c chuyn ha nh sau:

Ara (C5H10O5)

CH3OH/H

B HIO4

1. LiAlH4
2. H2O

Br2/H2O

H2O/H

HOCH2-CHO + HOCH2-CH2OH

H2O/H

CHO-COOH + HOCH2-COOH

V cu trc ca B, C, D v E.
Cu 33: Hp cht A (C4H6O3) quang hot, khng tham gia phn ng trng bc, tc dng vi anhirit
axetic to ra dn xut monoaxetat. Khi un nng vi metanol, A chuyn thnh cht B (C5H10O4). Di tc
dng ca axit v c long, B cho metanol v C (C4H8O4). C tc dng vi anhirit axetic to ra dn xut
triaxetat, tc dng vi NaBH4 to ra D (C4H10O4) khng quang hot. C tham gia phn ng trng bc to
thnh axit cacboxylic E (C4H8O5). X l amit ca E bng dung dch long natri hipoclorit to ra
D(+)-glyxeranehit (C3H6O3) v amoniac. V cu trc ca A, B, C, D v E.
Cu 34: Xc nh cc cht t A n G v hon thnh cc phng trnh phn ng trong chui bin ha
sau:
3MgCl

1.CH
2.H O
3

C
6 H12O(A)
H 2SO4 ,t

KMnO (c nng)
4

C6 H10 (B)

H 2SO4 ,t o

C6 H12O(D)

H Pt
2

1. CH MgCl

/
Metyl xiclopentan

C10H16 (G)

2. H3O+

H2SO4 (un nng)

C10H18O (F)

1.Mg,ete
2. Xiclopentanon
3.H 3O

C
5 H 9 Br(E)

HBr

C6 H 5COOOH

C5H8O (C)

Cu 35: Gii thch:

a. Ti sao phn ng sau khng dng tng hp tert-butyl propyl ete.
CH3CH2CH2ONa + (CH3)3CBr
(CH3)3COCH2CH2CH3

Natri propoxit
tert-butyl bromua
tert-butyl propyl ete.
b. Sn phm chnh ca phn ng ny l g.
c. Hy ngh phng php tng hp tert-butyl propyl ete tt hn.
Cu 36: Hy sp xp dy cc cht sau theo th t tng dn tnh baz v gii thch: CO(NH 2)2 ;
(CH3)4NOH ; CH3CH3CH3NH2 ; CH2=CHCH2NH2, p-CH3C6H5NH2 ; C6H5NH2 ; p-NO2C6H5NH2.
Cu 37: Khi un nng 2-metylxiclohexan-1,3-ion vi but-3-en-2on trong dung dch kim ngi ta thu
c mt hp cht hu c (sn phm chnh) c cng thc C 11H14O2. Hy vit cng thc cu to ca sn
phm ny v gii thch qu trnh to ra n
Cu 38: Gii thch ti sao 1,2-imetylxiclohexen ch phn ng cng trans vi HBr trong dung mi khng
phn cc nhng li cho phn ng cng cis v trans vi HBr trong mi trng axit. Cho bit cu trc ca
sn phm.
Cu 39: Qu trnh phn li ca mt aminoaxit n gin nh glyxin nh sau (b qua proton)
+
K11
NH3CH2COO- K22
+

NH3CH2COOH
(A)

K12

(B)

NH2CH2COO-

NH2CH2COOH K21

(C)

(B')
1. Vit phng trnh biu th mi quan h gia cc hng s cn bng
2. Tnh im ng in pHI ca glyxin bit: pK1 = 2,35 ; pK2 = 9,78
3. Biu th mi quan h gia:

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a. K1 vi K11 v K22
b. K2 vi K21 v K22
Cu 40: Hp cht thin nhin X c cng thc phn t C7H14O6 l mt cht khng c tnh kh v khng t
ng phn ha c. Thy phn X bng HCl long thu c cht Y (C6H12O6) l mt monosaccarit c
tnh kh. Oxi ha Y bng HNO3 long, nng thu c mt iaxit M (C6H10O8) khng c tnh quang hot.
Lm gim mch ca monosaccarit Y chuyn nhm CH(OH)CHO thnh nhm CHO (thoi phn
Ruff) th thu c monosaccarit Z (C5H10O5). Z b oxi ha bi HNO3 long, nng cho iaxit N (C5H8O7)
c tnh quang hot. Cho X tc dng vi CH3Br trong mi trng baz sinh ra P. Cht P tc dng vi dung
dch HCl long to ra Q ; cht hu c Q b oxi ha bi HNO 3 long, nng thu c hn hp sn phm
trong c axit 2,3-imetoxibutanioic v axit 2,3-imetoxipropanoic.
Xc nh X, Y, Z, M, N
Cu 41: Xt phn ng th: RCl OH ROH Cl c biu thc tc phn ng l: v = k[RCl] hoc
v k[RCl][OH ]
a. Cho mt v d c th v RCl trong mi trng hp, gii thch
b. S dung mi gii ca tert-Butyl bromua trong axit axetic xy ra theo c ch nh sau:
(CH 3 ) 3 CBr (CH 3 ) 3 C Br
(1)
(CH 3 ) 3 C CH 3COO (CH 3 ) 3 COCOCH 3 (2)
Hy gii thch ti sao, khi tng hm lng Natriaxetat th khng lm tng tc phn ng.
Cu 42: imetyl ha iso-butilen (X) trong dung dch H2SO4 60% thu c hp cht A mch h c cng
thc phn t l C8H16. Hiro ha A thu c B l 2,2,4-trimetylpentan. Nu dng Y l iso-butan tc dng
vi X cng thu c B khi c xc tc HF
a. Vit cc phng trnh phn ng xy ra
b. Trnh by c ch phn ng X A v Y B
c. Thnh phn % ca B trong xng gi l g? ng dng ca B trong xng?
Cu 43: Hp cht A c CTPT C4H8O3 quang hot, tan tt trong nc to dung dch c mi trng axit.
Khi b t nng A to ra cht B c CTPT C4H6O2 khng quang hot, t tan trong nc (dung dch c mi
trng axit). B phn ng vi KMnO4 d hn A. Khi b oxi ha bng dung dch axit cromic long th cht
A bin thnh cht lng C c CTPT l C3H6O. Bit C c nhit si thp, khng lm mt mu dung dch
KMnO4 nhng phn ng vi I2 trong NaOH to ra kt ta mu vng.
Xc nh CTCT ca A, B, C v vit cc phng trnh phn ng xy ra.
Cu 44: Hp cht A (C18H18O2Br2) phn ng c vi dung dch NaOH nng. Cho hn hp sau phn ng
tc dng vi dung dch axit v c long thu c cht B (C9H9O2Br) v C ( C9H11OBr). Oxi ha B hoc C
u thu c axit p-Brombenzoic. Oxi ha C trong iu kin thch hp s chuyn thnh B. T B thc
d
dd NaOH(
H 2SO4(
Cl 2 ,as
)
) c

D

E dd HCl G
H
hin chuyn ha sau: B
to
170o C
Bit D cha mt nguyn t Clo trong phn t. Cc sn phm ghi trn s u l sn phm chnh
Vit CTCT ca A, B, C, D, E, F, G, H v vit cc phng trnh phn ng xy ra. G, H c ng phn hnh
hc khng. So snh nhit nng chy ca B v C. Gii thch
Cu 45: Khi cho amoniac phn ng cng vi axetanehit thu c sn phm khng bn A, sn phm ny
d b tch nc thnh B. B d dng trime ha cho sn phm C l triazin. Mt khc nu cho amoniac
ngng t vi fomanehit s thu c sn phm D (urotropin) c CTPT l C6H12N4. Cht D c kh nng
tc dng vi axit nitric trong anhirit axetic to ra E (hexogen hay xiclonit) l cht n mnh c dng
trong i chin th gii th II theo s : C6H12N4 + 3HNO3 E + 3HCHO + NH3.
Xc nh A, B, C, D, E v vit cc phng trnh phn ng xy ra.
Cu 46: Tch hn hp cc cht sau: hexan-2-on ; hexan-3-on ; axit fomic ; axit trietylaxetic
Cu 47: Vit cc phng trnh phn ng theo s sau:
+X
C (etilen glicol iaxetat)
o
H 2 ,xt
P,t ,xt
Trng
ngng
2HCHO
A
B
D (poliete)

O ,xt
+ CuO, t
E 2
F (axit a chc)
o

Ca(OH )2 (d )

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Cu 48: Khi cho PVC tc dng vi Zn trong ru th tch ra c ZnCl 2 v thu c polime c cha
20,82% clo. Polime khng cha ni i v khng c tnh do nh PVC. Kt qu trn cho bit g v cu
to ca polime mi thu c. Tnh % mc xch vinyl clorua b tch clo bi Zn.
Cu 49: X l - halogen xeton vi baz mnh to thnh cc sn phm chuyn v. S chuyn v ny gi
l phn ng Favorski. - cloxiclohexanon s chuyn v thnh metylxiclopentancacboxilat khi c mt
CH3ONa trong ete. Hy xc nh c ch ca phn ng ny.
O
Cl
CH3ONa

COOCH3

ete

NaCl

Cu 50: Vit s iu ch cc cht sau y:

a. 1,2,3 tribrmbenzen t axtilen v cc ho cht cn thit khc.
b. Axit m toluic t benzen v cc ho cht cn thit khc.
Cu 51: Hy ngh c ch phn ng kh nc (H+) ca
a. Butan1ol to (trans)but 2en
b. 3,3imetylbutan2ol to 2,3imtylbut 2en
Cu 52: Hon thnh cc s :
a. Tm A, B, C v hon thnh s sau:

HIO4
Metyl glucopiranozit
A ddBr2 B H 3O C
b. Tm cc cht A, B, C, D, E, F v vit cc phng trnh phn ng xy ra theo s sau:
Na2Cr2O4
2 ,1mol
Benzen
Cl FeCl
3

H 2O
t o ,P

Fe / HCl
E

F
(1 mol)
Cu 53: Hp cht hu c A c cng thc phn t dng CxHyOz trong oxi chim 29,0909% v khi
lng. Bit A c th phn ng vi dung dch NaOH vi t l 1:2, phn ng vi Br 2 theo t l 1:3. Xc nh
cng thc phn t v cng thc cu to ca A.
Cu 54: So snh tnh baz ca cc cht sau v gii thch: CH 3NH2, NH3, (CH3)2NH, C2H5NH2, C6H5NH2,
(C6H5)2NH, NaOH, C2H5ONa
Cu 55: Vit cng thc cu to ca cc cht hu c c tn gi sau:
a. Spiro-[3,4]-oct-1-en
b. (R)-3-clobut-1-en
Cu 56: Inden co cong thc phan t C9H8 co cac tnh chat sau:
- Lam nhat mau dung dch nc brom, dung dch nc thuoc tm.
- Hap thu nhanh 1 mol H2 tao thanh Indan (C9H10).
- Tac dung vi H2 d (xt Ni, t0) tao hp chat C9H16.
- B oxi hoa bi KMnO4/H2SO4 tao axit Phtalic
Xac nh Cong thc cau tao cua Inden. Viet cac phng trnh phan ng
xay ra.
Cu 57: So sanh kha nang phan ng the electrophin cua Naphtalen vi
Benzen. So sanh kha nang phan ng (co giai thch) the electrophin v
tr va v tr cua naphtalen. Viet cac phng trnh phan ng ieu che
ra cac dan xuat initronaphtalen va axit naphtalenisunfonic t naphtalen.
Cu 58: 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 oxi ho 1 mol amiloz bng NaIO 4, s gc glucoz u mch to ra 1 mol
axit fomic, s gc glucoz cui mch to ra 2 mol axit fomic.
b. Vit s cc phng trnh phn ng xy ra.
Cu 59: T CH4, cc cht v c, xc tc v cc iu kin phn ng cn thit, vit s iu ch cc cht
hu c sau: PPM, PVA, DDT
HNO3 1:1

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Cu 60: Vit s cc phng trnh phn ng chuyn D-glucoz thnh L-guloz c

cng thc di
CHO
OH
H
OH
H
CH2OH
L-galuz

H
HO
H
HO

Cu 61: 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.
Cu 62: Hp cht A (C5H9OBr) khi tc dng vi dung dch it 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 it 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.
Cu 63: Monosaccarit A (t l glicoz A) c tn l (2S,3R , 4S , 5R)-2,3,4,5,6pentahiroxihexanal. Khi un nng ti 100 0C, A b tch nc sinh ra sn phm B c
tn l 1,6anhiroglicopiranoz. 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

a. Vit cng thc Fis ca A v B.

b. A tn ti 4 dng gh (D-glicopiranoz). Vit cng thc ca cc dng v cho
bit dng no bn hn c?
c. 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?
d. Vit cng thc cu trc ca E v G. Hy cho bit chng c tnh quang hot hay
khng?
Cu 64: 2-(1-Hiroxipentyl)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 aipic
(hay axit hexanioic) 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 ho
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.
4. pK ca este metyl ca glyxin l 7,70. y cng l gi tr ca K12. Tnh ba hng s cn bng cn li.
5. Trong mi trng trung tnh th glyxin tn ti di dng ion lng cc hay phn t trung tnh, v sao.
Cu 65 : Hat oc sam co oc to ten la coniin. Coniin co khoi lng phan
t bang 127 .v.C, cha 75,60% C, 13,38% H theo khoi lng. Coniin lamxanh
quy tm am, khong lam mat mau dung dch Br 2/CCl4 cung khong lam
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mat mau dung dch thuoc tm. Khi ehidro hoa coniin th thu c chat A
(C8H11N). Khi oxi hoa A th thu c mot hp chat d vong B co cong thc
C5H4N-COOH.
Biet rang trong ca hai phan ng tren khong co s ong hay m vong
va phan t coniin khong co C bac ba.
a. Xac nh cong thc cau tao cua coniin va cho biet bac amin cua
coniin A, B . V sao khoi lng phan t cua coniin, cua A, B eu la so
le.
b. e tach lay coniin t hat oc sam vi hieu suat va o tinh khiet
cao nen chiet vi dung moi nao sau ay (co giai thch) : Nc, ru
etylic, dung dch NaOH, dung dch HCl.
Cau 66: Hp chat A (C5H9OBr) khi tac dung vi Iod trong moi trng kiem
tao ket tua mau vang. A tac dung vi dung dch NaOH tao ra hai xeton B
va C co cung cong thc phan t la C 5H8O. (B) va (C) eu khong lam
mat mau dung dch KMnO4 lanh, ch co B tao ket tua mau vang khi
tac dung vi Iod trong moi trng kiem. Cho B tac dung vi CH 3MgBr roi
vi nc th thu c D (C 6H12O). D tac dung vi HBr tao ra 2 ong phan
cau tao E va F co cong thc phan t C6H11Br trong o ch co E lam
mat mau dung dch KMnO4 lanh. Dung CTCT, viet s o phan ng t A
tao thanh B, C, D, E, F. Viet ten A va D theo danh phap IUPAC.

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