Phn 4

HIROCACBON

Bi s 4.1

t chy hon to n mt hirocacbon A ri h p t h ht s n p h m chy vo mt

bnh ng du n g dch C a (0 H ) 9. S a u th nghim th y khi lng bnh tng
26.24 gam. Lc th u c 20 gam k t ta. un si nc lc m t thi gian li thu
dc 10 gam k t t a na.
Khi cho mt lng A b n g n g lng t chy tr n vi clo 300c th u
dc hn hp c gm 4 s n p h m d n x u t cha clo c a A l ng p h n ca n hau
vi hiu s u t 100%. Hn hp c c t khi hi so vi H n h hn 93.
Xc nh cng th c ca A v tnh th n h p h n % theo khi lng mi c h t trong
hn hp c.

Bi gii
Vn l thuyt lin qu an
Trong phn ng thhalogen ca ankan, thc nghim cho thy, nu coi kh nng phn
ng ca Cj - H l 1 thi kh nng phn ng ca Cj - H v C - H nh sau:

C - H CI r H C - H
Clo ho 27c 1 3,9 5,1
Clo ho 100c 1 4,3 7,0
Clt ho 300c 1 3,3 4,4
Brom ho 127c 1 82 1600

A + 02 > C 0 2 + H 20
Khi d n s n p h m chy vo d u n g dch Ca(OH).> th hi nc ng n g t cn CO
c p hn ng:
C02 + Ca(OH )2 -> C a C 0 3 + H 20 ( 1)
c th c:
53
 2C02 + Ca(OH )2 -> C a (H C 0 3)2 (2)

m binh tng = m C0, +m H:0

un nng nc lc li th u c k t t a chng t c (2). v:

C a ( H C 0 3) 2 C a C 0 3i + C 0 2t + H 20 (3)

(l)'t2)'(3)- - Z > e O : = n CaCO,(l) + 2nCaCO,(3) = + 2X j = 0,4mo1

2 6 , 2 4 - 0 , 4 .4 4 _ n
-> n H20 = ---------^ ------- = 0,48mol

10O-, < n H20 -> A l a n k a n CnH.,n + 9 .

CnH 2n + 2 + ^ - io 2 n C 0 2 + (n + l) H 20
4M

_ n _ = _2i -> n = 5. A : C 5H 12.

n +1 0,48

T a C: C 5H 19 + nCl > C 5H l 2 . nCln + nHCl

J M c _ 72 + 3 4,5n ___

d c / H 2 = = -----~ Y ---- < 9 , 3 - > n = l , 2 , 3.

c 5h 12 n 1 2 3

ch 3- ch 2- c h 2-c h 2-c h 3 3 > 11 > 10

CH 3 c h CH 2 C H 3
S dn x u t clo 4 >6 > 6
ch3

ch3
1
c h 3 c c h 3 1 2 3

ch3

A l:
CH 3 CH CH 2 CH 3 (n = 1 )

CH 3
54
 ------ CH 2 CH CH 2 CI 3
i 1 .
Cl Cl I3
CH3 CCI CH;, CH i

C12,300C L
CH-,
CH, c i l CII2 CH,
1 : 1
ch3
-----

ch3 Cl

------ CH 3 CH CH 2 CH2CI
i
ch3

K h n n g p h n n g vi clo ca H - c 1 : H - c 11 : H - c 111 = 1 : 3,3 : 4.4

% C H 2 C H C H 2 CH 3 = ------ ------------ l00% = 30%

I I ' 6.1 + 2.3,3 + 1.4,4
Cl CH 3

Tng t:
% C II3 CCI CM2 c h , = 22%

CII 3
% CI 3 C H C H C H 3 = 33%

CH3 C1
% c h 3 c h c h 2 c h 2c i = 15%

CH

l % mi c h t v s mol c n g l % v khi lng ca mi c h t do chng c

khi lng p h n t b n g n h a u .

B i s 4 .2

1 . 1 - h e x e n tc d n g vi N BS tro n g CCI 4 c g?

2 . Cho s :
h 3c ch3
CH

Cl2,F e Cl2,a sk t ^ NaOH NaOH

B c i. E
t, p
Cumen(A)
55
 Cc p h n ng u din ra theo t l mol 1 : 1 , cc c h t ghi tr n s d u l sn
phm chnh.
Vit cc phng tr n h p h n ng v cho b it c ch cc p h n ng t A -> B,
B -> c. Gii thch s to th n h s n phm chnh ca hai p h n ng ny.

Bi gii
Vn l thuyt lin qu an

1. NBS.
o o o
// //
c h 2 c c h 2- c CH2 c
OH \ Br 2 \
+ NH, NH NBi
ii /
/
CH 2 c: c h 2 c CH, c
%
o o o
Axit Sucxinic Sucxinimit N - r o m s u c x in im it

N B S brom ho anken cho dn xut alyl m khng ng chm n ni i.

o o
// //
c h 2 c C H , c
\ \
NBr CI I3C 2 Cl 1 = CI 2-------- CH 3CF C 1 = CH2+ NH
/ /
C H , c c h 2 c
Ir
o o

2. Kh n n g p h n n g th h a lo g en c a n g u y n t H m t s hp ch t
- C/o hon isopropylbenzen (Cumen) v toluen 80 c (tng lng).
H3
a ( 1.0) a (3.2
\\ / - - C H 2 H ^ t C H 2 H

H (12,8)

- Cio h o 75 c

c h 3 c h 2 ch2 CH 2 Cl
(1.0) (3 7) (2 . 1 ) ( 0 . 8)
 H ,c CU, 1I3C / CH3
CH CH

+ CI 2 Fe, t
[\ --------- + HC1

,c CH, h 3c CH 3
- /
CH C Cl

+ Cl 2 askt- + HC1

(C)
Cl C1

h 3c c h , h 3c ch3
C Cl C OH

+ NaOH + NaCl

Cl (D)

N g u y n t C1 l i n k t t r c t i p v i v n g b e n z e n k h b t h u p h n d o c s g i i
t o e l e c t r o n c a C1 v o v n g b e n z e n n h h i u n g + c .

H3C CH3 H 3C /C H 3
C OH OH

t p
+ N aO H IL + NaCl

OH (E)

C c h p h n n g A -+ B
P h n n g L h eo c c h t h e l e c t r o p h i n v o n h n t h m S EA R

3C12 + 2Fe 2FeCl 3

6 + S-
FeCl 3 + Cl 2 -------- Cl...FeCl 4

57
 ch3 ch3 CH ch3
V
H
'cl

5+ 8
C1 ... FcC14 + FeC

Cl
H
Phc

H + FeCl - F e C l 3 + HC1

Do gc (C H 3)^CH- c h iu n g +1 l nhm th loi I n n n h hng p h n ng

t h tip theo vo v tr ortho v p a ra . N n giai on to phc a c th c hai phc
sau:
CH3 , c h 3 c h 3 ,c h 3
-cl tl
Cl

(I) H
( l (II)

Cl
H
Do gc (C H 3)CH- c s n ng v k h n g g ia n n n d n n Cl+ kh t n cng
vo v tr ortho n n phc (II) kh h n h t h n h hn. Cho n n s n p h m c h n h l:
ch3 ch3
sc

Cl

C c h p h n n g B - c
P h n n g t h th eo c ch gc S, gm cc cc giai on:
- Khi m o p h n ng:
as
C1 *> 2 C f
58
 P h t tri n m ch
l,c CH, H ,c CH,
cl \

Ci A + HC1

H ,c
C1
CH,
1
C1
h 3c ch3
\ c C1

C1 C1

C1

C n h vv...
- N g t mch.
Cl' + c f- C1

R* + C - R C1

R* + R'
CH
Vi gc t do R : C1
\
CH
Trong giai on p h t tri n m ch c th sin h ra cc gc sau:
H ,c CH 3 h 3c /C H 2
V CH

C1 (I) 1
Gc (I) bn hn do c h iu n g +c ca vng b ezen v h i u n g +H. Gc (II) km
bn hn do ch c h i u n g +H.
Nn s n p h m c h n h l:
HnC CH;
x c C1

C1

9-MSCHVBTHHCd 59
Bi s 4.3

1. Vit p hng tr n h p h n n g khi cho stire n , toluen, xilen, cum en, n - propyl-
benzen tc d n g vi d u n g dch K M n 0 4.
2. T ron g cng n g h ip phenol v axeton c th iu c h b n g p h n ng xi ho
c u m e n bi oxi k h n g kh. H y vit phng tr n h p h n ng. c c h c a p h n ng.

Bi gii

1. R ing s tir e n c k h n n g tc d n g vi d u n g dch KMnO.} n h i t thng.

ch = ch2 ^ C H CH 2

+ 2 K M n 4 + 4H20 -------- 3 QJ OH oh + 2 M n 0 2 + 2K 0H

Cc c h t cn li ch tc d n g k h i u n nng.
CH COOK

+ 2 K M n04 o + 2M n 2 + KOH + H 2

COOK

CH 3 + 4K M n0 4 . COOK + 4 M n 2 + 2 KOH +2H20

H3C ch3
\ / 3
COOK
CH

3 Q I + 18KM n04 + 18 M n 0 2 + 6 K2CO 3 + 3 K O H + 9H">0

COOK
CH 2CH 2CH 3

+ 10K M n0 4

COOK
ch = ch 2

+ 10KM n0 4 0 + 1 0 M n 0 2 + 3K 2C 0 3 + KOH + 4H20

**3

Lu :
- Cc gc h iro cacbo n no hoc k h n g no ni vi vng b e n z e n u b oxi ho ct
m ch bi d u n g dch K M n 0 4 k h i u n nn g to r a a x it benzoic hoc ax it
benzenpolicacboxylic.

60
 Mt s a x it t o t h n h khi oxi ho cc c h t trn :

COOI
COOI COOH COOH

o
o
COOH
COOH
Axit benzoic A\it phta lie Axit isophtalic Axit terephtalic

2. II 3C / CH 3
CH OH

h 2s o 4
+ o + CH 3 CH 3

o
C ch:

H3C ch , h 3c ch3
CH c

+ HOO
o o

H3Cx / CH 3
H,c CH,
CH \ ' / 3
c

Q J + h2o2
h 3c
3\./ ch
3, H ,c
\ /
CH3
c C OO'

+ o
0

H 3C x H 3C x /( h 3c ch3
3 3 \ . / 3
C 0 0 * CH c OOH c

0 * 0 o

61

h 3c ch3 h 3c ch, H3C ch3 CM CH
C OOH c o
H+ ng phn ho

f e o O

c h 3 c c h 3 + f o
OH
l ' ^
o
HOH
-H+ O

Bi s 4.4

Khi cho isobutilen vo d u n g dch H9SO4 60%, un nng ti 80c th u c hn

hp gi t t l i - isobutilen gm h ai c h t ng p h n ca n h a u A v B. Hiro ho
hn hp n y c hp c h t c q uen gi l isooctan. c l c h t c d n g n h gi
nhin liu lng.
c cng c th c iu c h b n g p h n ng trc tip c a isobutilen vi
isobu tan khi c m t a x it v c lm xc tc.
H y gi t n c theo IU PA C v vit cc phng t r n h p h n ng gii thch s to
th n h A, B, c.

Bi gii

H 2S 0 4 - H + + HSO,

+r * r
CH 3-*-C==CH 2 + H * c h 3 c c h 3 (l)

CH 3
L.
CH 3
CH
0 +
c h 3 c c h 3 + CH 3 C c h 2 CH3 C CH 2 C CH 3 (2)
' CH CH
CH3 ch3
H-,
i
CH CH, c CH = c CH,
_
CH, CH2 CH,
Zaixep Ic h 3 ch3
L
- r i CH, (A) (> 80%)
CH;, CH,
CH3 C CH2- C = C H 2
L
CH,
!..
CH}
(B) (< 20%)
62
 0
H sinh ra li quav v (1). Q u trn h xy ra lin tc.

CH CH

C H . , - 9 - C H = C - C H , - i ^ C H 3- - C H , - C H - C H 3

CH 3 CH 3 CH3 CH3
^ Isooclan(C)
2,2,4 - trimetylpentan
(Qui c c ch s octan l 100)

Isobutilen vi iso b u tan khi c m t axit v c lm xc tc cng to ra C: C ch

ca q u trn h tng t tr n n h n g ch khc qu trn h :

ch3

c h 3 c c h 2 C c h 3 + c h 3 c h c h 3 ** CH3 C CH2 C H -C H 3

ch3 ch3 ch, CH3 (Q CH3

3
ch3 I
+ CH5 c
I
I3C C CH3 sinh ra li lp li (2). C nh vy. T
CH,

Bi s 4.5

Tin h n h p h n n g im e ho trim ety letile n c H + xc tc. Cho bit cc s n

phm d kin c to ra da theo c c h p h n ng.
Khi ozon ho hn hp th u c sa u p h n ng im e ho tr n , ngoi cc a n eh it
v xeton ca s n p h m d kin cn th u c mt lng n g k b u ta n o n - 2 . Cho
bit a n k en C 10H 90 tho m n tn h c h t tr n v gii thch c c h to th n h n.

Bi gii

S n p h m d kin:

CH 3 C = C H CH 3 + *. CH3 ? CH^ CH 3
I ' I
ch3 ch3

63
Ozon p hn hn hp tr n th u c:
ch3

CH 3
c h 3 c h 2 c c = o
f c h 3 c h 2 c c = c c h 3 L L
ch3 ch3
L I.. I .
ch3 ch3 ch3 CH,
ozon phn
CH
c h 3 c h 2 c C H c = o
ICH3 c h 2 c c h c = c h 2
CII 3 c h 3 c h 3
T I \
ch3 ch3 ch3
0 = c CH 3 v HCHO

CH3
S to t h n h m t lng n g k h u ta n o n - 2 l do:

CH, C =C H CH, - ! . CH C H j-a , -rz* a v = c Q f-C H ,

L ' I L
CHj Qi OI3 CHj

CH,- CHr-CH, + < S = C CHf-CH, CH3 c h 2 C 0 I2 o2 Gl:

L
CHj
L
CH3
ICH, I
CH,
CH33
CH ch3

CH rfflrLI r?- CH2 CH, C H r - C H c CH = c CH CH

I
CH
I
ch3
H I
ch3
L
ch3

Khi :
 CH* CH,
I

CI I CI I t - C CI I = c CI I CI I3 ozon c h , c h 2c c h o

phn ^ c i l CH C = + ^ ' '1

CH, CII, CH,
CH2= C C H r - C H , CH, Lv HCHO
I
CH,

A nken C 10H 20 th o m a n l:

CH

C H , CH 2 C CH = C C H 2 CH 3

CH CH

Bai so 4.6

H oan t h n h p h n Cfng theo d y bien ho sau:

Propilen

CI
CC1.

B'

Bai gii

C H 2 = CH - C H 3 + Cl 2 400~50QC > C H 2 = CH - C H 2C1 + HCl

(A)

C H 2 = CH - C H 2C1 + N a 2C 0 3 + H 20 - C H 2 = C H -C H 2OH + N a H C 0 3 + N aC l

(A1)

65
c h 2= c h c h 2 + C l 2 c ' 4*" c h 2 C H c h 2

C1 C1 C1 ( R)

CH2- C H = C H + NaCl + H 20

CH 2 - C H C H 2 + NaOHd 1 1
1
C1 1
C1 C11 ^ C H 2- C = C H 2 + NaCI + H20

C1 C1

C H 2- C = C H 2 + Zn C H 2= C = C H 2 + Z n C l2
(B-)
1
C1 I1

CH 2 C H CH + Zn - CH 2= C = C H 2 + Z nC l 2

1 1C1 (B')
C1

c h 3 c h = c h 2 + C l2 ^ C H 3 C H C H ?
1 1
C1 C1

C H , = C H CH,

(CH3)3CX)K _ q (CH,) 3C 0 K 'C H 2= C = C H 2

c h 3 c h c h 2 ------ < CH 3 C H = C H
- (CH3)3COH - (CH3)3CX)H
C H 3 C ^ C H
a a - KC1 C1
CH 3 C CHi

CH 2 C CH 2 AgNO/NH 3 a
- CH 3 C - ^ C A g + CH 2 C = C H 2 t
C -= C H

Bi s 4.7

S u hirocacbon A, B, c, D, E, F u c cng th c p h n t C 4H 8. Cho tng

c h t vo brom tro n g CC14 k h i k h n g chiu s n g th th y A, B, c, D tc d n g r t
n h a n h , E tc d n g c h m hn, cn F th h u n h k h n g p h n ng. Cc s n phm
th u c t B v c l n h n g ng p h n q u a n g hc k h n g i q u a n g (ng p h n lp
th i - a) ca n h a u . Khi cho tc d n g vi H 9(Pd, t) th i A, B, c u cho cng mt
s n p h m G. B c n h i t si cao hn c.
66
 1 . Xc n h cng th c c a 6 hirocacbon trn . G ii thch?

2. So s n h n h i t si ca E v F.
3. Nu c c , D, E, F. H y n u phng p h p ho hc n h h b i t chng.

Bi gii

1 . Cc ng p h n c th c c a C 4H 8:

CH 3 c h 2 c h = c h 2 c h 3 c = c h 2

ch3
CH, CH 3 CH , 3

C H CH CH=CH
ch2 CH
h 2c ch2

h 2c ch2 H2C -------- CH CH 3

V F h u n h k h n g p h n n g vi B r 2/C C l4, n n F l:

H2C ----- CH 2

H2C ----- CH 2

E tc d n g c h m vi B r / c c ^ , n n E l:

CH 2

H ,c CH CH 3

- V A, B, c dc h i ro h o u cho c ng m t s n p h m G c h n g t A, B, c c
k h u n g c n h n h a u , n n cn li D:
CH-, C = C H 2
1
CH-,

- V B, c tc d n g vi B r 0/C C l 4 cho n h n g ng p h n q u a n g hc k h n g i
q u a n g ca n h a u (c t n h t 2 C), n n B v c l ng p h n cis - tra n s c a nhau.
Do B c n h i t si cao hn c n n B l ng p h n cis ( p h n cc hn).
B: CH- ru C: CH3 H
\ _ / UH3 3\
/ c ~ c \ / c ~ c \
H H H CH3

-> A: C H 3 - C H 2 - CH = C H 2
C ch (cng hp tran s):

10-m sch v bth h CUc 67

 H, H
Br - 4

H3cc = = c \ CH 3

Br
Br Br
H H, ,H (2 )
(1) H ,
-* '"C c: " c ------ C'"
'C H 3 / 1 CH-
H 3C Br H 3C Br

l|l
CH

1k C H r3 Br

CH

H- Br

Br H

CH 3 CH 3
I (Threo) II

h 3c h 11
Br- Br

c= c\ TI
11 Br
h' ch3
(c > ch3
III
Erythro meso)
(I, III); (II, III) l n h n g cp ng p h n q u a n g hc k h n g i quang.
2. M e = Mp v d d n g th y n(E) > 0 ; n(F) = 0 nn E c n h i t si cao hn F.
3. N h n bit c , D, E, F.
- D ng du n g dch B r 2 n h n r a F v khng p h n ng.
68
 - Cn li D, E, F cho tc d n g vi du n g dch K M n 0 4 long, ngui. E khng
p h n ng nn n h n ra.
- c, D om hp nc (H*) ri cho hai ru tng n g tc d n g vi (HCldc +
ZnCl2).
C h t n o v n c ngay l ru bc 3 -> s n p h m ca D.
C h t no vn c k h chm l s n phm ca c (ru bc 2).
Cc phng tr n h p h n ng:

CH-\ CH=CH
/ CH' +
- ..
Br2 -------- CH 3 CH CH CH 3
L
(C) Rr
Br Br

CH 2 = C CH 3 + Br2 -------- BrCH 2 CH 3

ch3 ch3
ch2

H2C ----- CH CH 3 + Br2 --------* CH 2 CH 2 C H CH 3

I I
Br Br

3CH3 CH ==CH CH 3 + 2K M n04 + 4H 20 3CH 3 CH CH CH 3

OH OH
+ 2 M n 0 2 + 2KOI
CH 3
1
3CH 2 = C CH 3 + 2 K M n 4 + 4 H 20 3CH2 CH 3 + 2 M n 0 2 + 2KOH
1 i i
ch3 oh h

ch 2

H2C ---------C H C H 3 + K M n 0 4 * khng phn ng

CH3 C H =C H CH3 + HOH CH3 CH2 CH CH3

C H 3 OH
ir
CH3 C = C H 2 + HOH CH3 c OH

CH, CH:

69
 CH,
CH,
1
CH3 c OH + HQ
. . CH, c a + H20(nhanh)

'
ch3 m 0*3
C H i CH> C H C H ! + H a C H - C H - C H - C H , + H;0 ( c h m )
I I
OH

Bi s 4.8

Mt a n k e n sa u khi ozon p h n cho s n p h m hu c duy n h t l a n e h it axetic;

khi cng hp brom trong bnh lm bng v t liu p h n cc ch to ra s n p h m l
mt ng p h n khng quang hot.
H y cho bit cu tr c ca a n k e n v cu trc ca s n ph m to th n h trong
p h n ng cng brom ca anken.

Bi gii
Vn d l th uyt lin quan
1. P h n ng ozon p h n : T hp ca hai giai on oxi ho bng O- ri thu phn -
oxi ho hoc thu phn - kh.
CH3
Zn,C^OOOHm / /

CH^ CH,
/C H3 ~ CH3 0 -0 , CH3 ' h 2 xh ch3
03 \
c
/ V Anehit axetic Axeton
/ C dung
H CH((
YhT 3 (CC14) H o ^ 0 ch3
ozonit o=c
- H 2O x OH CH,
Axit axetic Axeton
+) C ch phn ng to ozonit,

p '
0 0

\ / j O _ L c
c= c + 3 ^ C C \ /
o
Anken
o zo n it

2. Phn ng oxi ho ct mch bng K M n04 hay K2Cr20 7/H 2S 0 4.

Sn phm thu c l axit cacboxylic, xeton, kh C 0 2

70
 5CH, C H = c G i, + 6 KM1O4 + ()H?S04 *. 5 CH3COOH+ 5CB, C CH,

CH, 0
+ 6 M 1SQ4 + 3 K,S04 4 9H20
3CH, C H = C H 2 + 5 K2Cr 20 7 f 20H 2S0 4 ----- 3 CH3COOH+ 3 C p 2 + 5Cr 2(S0 4)3

+ 5K2S04 + 23H2Q
3. Xc nh cu trc ca anken bng phn ng oxi ho ct lin kt i.

Sn p h m ozon p h n Xo b 0 v ni cc c 2 C u to ca anken
sp

............... CH, CH,

C H 3-C H O +(C H 3)2CO CHv CH=f O c>4=c CH,C H = C ^
- ......... ; V CH,
p u

II
V
1,

CT^CHi c==0 0 =f C CH2CH, c h ,ch 2c = cch 2c h ,

X

1 .......* 1 CH, CH,

CH, CH,

ch2
CH 0
/ / \ / CH\
(CH 2)3 ch2 ch2 CH, CH2
\ r.......... 1 1 < /
CH=0 CH=i:0 04=CH CH=CH
< 1
t -------------

H C H O + (C H 3) 2C = 0 +
HCH=fO 0=fCHCH2CH==0 0=j=C(CH,)2 CH2=CHCH2CH=C(CH,)2
0 = C H C H 2CH = 0

ozon phn _ _
Anken----- CH3 C H = 0

-A n k e n l: C H 3 - CH = CH - C H 3.
CH\ CH, CH, H
c= c C=C/
/ \ / \
H H H CH,
I II
Gi s l cis - 2 - b u ten , ta c:

CH\ CH, CH, Br- CH3 Br CH,

Vc __Rr,
= c c c 'c c"
/ \
\\ XH
H H H H H
Br
CH,
H Br
Br- H
CH3
Threo(c tnh quang hot)

71
 Anken l tra n s - 2 - buten.
CH3

CH3 H Br -H
y = c ' B, -H
H CH}
ch3
Erythro( D ng meso k h n g c tn h q u a n g h o t)

Bi s 4.9

Ozon p h n m t hp c h t c tron g t h n h p h n tin h d u hoa hng th u c m t

hn hp gm: H O C H 2 - CH = o , (C H 3)2C = o , C H 3C O C H 2C H 2CH = 0 .
Hy xc n h cu to ca c h t b a n u.

Bi gii

Ta c cc cch sp xp n h sau:

( 1 ): (CH3) 2C== 0 o i c CH 2CH 2 C h 4 = 0 o4=CH H p !!

.............. I ** *.-............4
ch3
-------- A: C H j - C = C CH 2CH 2 C H = C H CH2OH

ch3ch3

( 2 ): (CH 3) 2c 4 o o 4 = C H CH 2CH 2 C = f O o c H CH 2OH

t---------- -4 I .---------- 4
c h 3

---------- B: CH ^ C C H C H 2C H 2 C = C H C H 2O H

L
ch3
L
ch3

Do th n h p h n ca tin h d u l tecpen, m tecpen c b k h u n g c do cc m t

xch isopren C H 2 = c C H = C H 2 k t hp vi n h a u th eo k i u u ni vi ui

c h 3

(quy tc isoprenoi) nn cng thc p h hp l B.

Bi S 4.10

T isopren h y vit cc phng t r n h p h n n g iu c h tra n s - 2 -

metylxiclohexanol.

- 72
v n d l th u y t lin q u a n
1. Phn ng hiro ho xc tc chy theo c ch cng hp CIS
Ni
VAV
A W W W W W

\ / 11

H H \ . i /
: :\ c C ---------------- c Vx
:____ :
.A/wvwwvw x :____ : ------* / w .....// 1
./w w wvw . J \ . . w ww
/ 777/ 77777 H H
Ni Ni 7 7 7 /T
Ni

S tip xc cng d thi phn ng cng d nn chu nh hng bi hiu ng khng gian.
CH 3 CH > C H 2 = C H 2 > C H 3 - CH = C H 2 > (C H 3)2C = C H 2.
2. Quy
uy tc Maccopnhicop

5 -/0 5++ _- S-
; 5
r
CM2
CM 2 CH CH3
CH HC11 -------- CH,
3 + HC CH3 CH CH
CH33
II
Cl
(Qui tc Maccopnhicop)

+
CH2
CH2 CH c
f\ \- + + HHCl- h 2 c
Cl--------- cUH2 h 2 COOH
<JH2 COUH
I
VOH
OH i
CI
(Ngc qui tc Maccopnhicop)

Thc ra hai phn ng trn u c th hiu theo quy tc Maccopnhicop tng qut:" Phn
ng cng electrofin vo ni i ca anken u tin chy qua bc hnh thnh cacbocation bn
vng nht".
H

C H ^ C H - c C1 C1 0 ^ CH 3 CH C1

H Cl

O ch ^ c h ^ h h - ^ O ch ch,

I
C1

3. Phn ng cng HBr, peoxit

C H 3 - CH = C H 2 + H B r peox" > C H 3 - C H 2 - C H 2Br

T r i quy tc Maccopnhicop
C ch cng gc:

73
 Peoxit -* gc t do R
R + H B r - RH + Br
Br + C H 3 - CH = C H 2 -> C H 3 - CH - C H 2Br (bn hn C H 3C H B rC H 2 )
C H 3 - CH - C H 2Br + H B r - CH 3 - C H 2 - C H 2Br + Br

4. Phn ng hiro bo ho
I.BH
C H , C H = C H 2 c h 3 c h 2 c h 2o h
2. H 20 2/Na0H
Phn ng chy qua giai on to phc vngcng hp cis):

CH,- CH CH, CH, CH CH2 *-CH3 C H f- CH2

f t +

___ u
1
bh2
H ------BH2 , 2
Phn ng bn trung tm

H2O 2/OH 0
-------- (CH 3CH 2CH2)3B - CH3 c h 2 c h 2
- H3BO3
OH
5. Phn ng Diel - Alder
ch2

200c
CH 2 300atm
ch2
ien ienophin
- ien tham gia phn ng c cu dng s cis(s - single bond).
- ienophin tham gia phn ng gi nguyn cu hnh sn phm cng.
/ C1 XI

C1
cis - 4 ,5 - ic lo x ic lo h e x a n

Y
.CH
HiC

\
CH

74
 CH

< z x B
H

HPg/OH
Hiu sut 75%
- H 3BO3

Bi s 4.11

1 . Cho s d sau: H exin - 3 - HC1'tU- ^ C 6H 12C12.

Vit c c h p h n ng v cu trc ca s n phm to th n h .

2 . B u tin - 2 A. Xc nh cu trc ca A v gi tn
3. Cho s sau:
KMn 0 4 long
B|

HCOOOH
---- B2
Butiniol - 1,4 K M n0 4 long

' *"c (\HCOOOH r

Na/NH-
*
Vit cng thc c u trc cc s n phm .

Vn l th uyt lin qu a n
1. Phn ng epoxi ho
Tc nhn phn ng l peaxit:

o
//
R c o
\ //
o o H (chng hn C6H 3 C OOH)

hoc c th dng hn hp H 0O 9 + HCOOH:

o
//
H 20 2 + HCOOH

SCJO BTHHUe 75
 o
//
H c
\
OH

OH
" ; CH, H ,c
HiC CH

'C C ' ___ "ccf ' c c 'v

h ; \ / \ h p h I H
H

CH
HO H
(Tlireo - 2,3 - butaniol)
H OH
CH
S thu phn epoxi thng c xc tc bi axit hoc baz cho t r a n s - iol.
2. Phn ng oxi ho anken bng dung dch K M n04 long, ngui

H ,C H , H y CH3
H,
" c l8OH
+ ' Mn w 1 ia + M nO?
c // \ c o / V c 18o h
/ o / \
H \ h ," () H CH3 H CH3

3 M n 0 3 + H 20 -> M n 0 4 + 2MnO 4- 2 0 H
Thu c cis - iol.
ch 3
11 OH

11
Q I _ J Ery thro - 2,3 - b u tan iol(D n g m e so)

CH

Bi gii
C1

1. CH3 CH2 C - = c CH2 CH 3 + 2 HC 1 CH 3CH 2CH2 c CH 2CH 3

a
C ch:

76
 Phn ng tu n theo quy tc M accopnhicop v theo hng cng hp tran s.

Br

I : 1^ C H 3 c = c CH;
2 .C H , C ^ E C C H , + Br->
c n g tr a n s
Br
trans - (h a y E - ) 2 ,3 - ib r o m - 2 - b u te n

Br. ^ Br

B r Br l dP \ B r
/ I __
C H 3 C - = c C H t - c h 3 c = c c h 3 C H 3 c = c CH3
1
Br

H H
P d /P d C 0 3 \
3 . C H 2 c ^ c CH2 + H2 * / \
1 I h o h 2c c h 2o h
H (B )

c h 2o h

3
\ _
c = c ^
/ H
+

2 K M n 0 4 + 4 H 20 3 h
-O H

-O H + 2M n02 + 2KOH
h o h 2c / c h 2o h
C H 2O H
meso - E r it r it o l( B )

cCH
h 2o h C H 2O H
H
H / H 1 O H HO -H
+ HCOOH
+ H ^ H O -------- H + H- -O H
HOH \ XC
CHH,O
,OH
H o OH
C H 2O H C H 2O H
D - Eritritol L - Eritritol
 H c h 2o h
Na/NH 3
CH 2 c ^ c CH 2 + 2H c= c (C)
/ '
h o h 2c H
OH h

H CH2OH CH2OH CH2OH

HOH2C
c
c; H
KM 11O 4 long
** HO
H -O H
-H +
1 i n
111
H
OH
CH2OH c h 2o h
~v----
(Cj)

o
C H 2OH
H C H 2O H H c
OH
'c=c"\ X Q O H , H
H OH
h o h 2c HoO H
C H 2OH
(C 2)

Bi s 4.12

1 . V it ph ng t r n h p h n n g t r n g hp c a b u ta ie n - 1,3 v cho b i t c u tr c ca
s n p h m to th n h .
2. V it c u tr c c a polipropilen syniotactic.

Bi gii

Trng hp
1. nCH 2= C H C H = C H 2 [ C H 2 c h = ch CH2 ]
n
1,4 - polime

[ C H C H = CH CH2 ]
n
1,4 - polime

r H H ~| r H CH 21
V /
\ / c==c\ \
X CH2X N / c~ c^ h
\ CH2X
n n
cis - poli - 1,4 - butaien trans - poli - 1,4 - butaien

78
 Trng hp
n C H i= C I c n 2 H----
I
CH CH, ch= ch2
1 ,2 -polime - n

CH,
Cl U CH,
X r
li = ! \
\ \ _ C H f= C H N II
C I 1= CII 2 C H = C H 2_
n n
poli - 1,2 - butaien isotactic poli - 1,2 - butaien syniotactic
H

CH=CH2
ch2
c h = c h 2

H
CH-
H

ch = ch 2
CH

CH CH
2. Propilen syniotactic:
CH

Bi s 4.13

Hp c h t A c cng th c CgHg c k h n n g to k t t a VI d u n g dch

A g N 0 3/N H 3 v p h n ng vi B r 2 tro n g nc th eo t l mol 1 : 2. u n nng A VI
d u n g dch K M n 0 4 ti kh i h t m u tm ri th m lng d HC1 c vo hn hp, sa u
p h n ng th y to ra k t t a t r n g l a x it benzoic, ng thi gii p hng k h CO v
k h Cl2.
H v cho b it t n gi c a A v v it cc p h ng t r n h p h n n g xy ra.

79
 B i gii

A to k t t a vi d u n g dch A g N 0 3/N H 3 nn A c lin k t ba u m ch.

A tc d n g vi Br<>/H.?0 th eo t l mol 1 : 2 n n A c h a i lin k t n L CO
HC1
A + K M n 0 4 - s n p h m C 6H 5 - COOH + C 0 2 + Cl 2
Vy A l:
c h 2- c ^ c h

3 - Phenylpropin

Ph ng t r n h p h n ng:
C H , C - = C H CH2 C -= C A g

+ A gN 0 3 + N H 3 + NH 4N O 3

C H , C ^ C H COOK

+ 14K M n4 I i + 5K 2C 0 3 + KHCO 3 + 14Mii02 + H20

COOK COOH

HC1 AI + KC1
I

K 2C 0 3 + 2HC1 -> 2KC1 + C 0 2t + H 20

KHCO3 + HC1 -> KC1 + C 0 2t + HoO
M n 0 2 + 4HC1 -> M n C l 2 + Cl2t + 2 H 20
Br

C H , C ^ C H CH 2 c C H Br
I
Br Br
+ 2 Br 2

Bi s 4.14

A v B l h a i hp c h t h u c ng p h n ca n h a u c M < 250 v ch cha hai

nguyn t.
A gN O yN H j A J W , D

8 0
 un nng D vi d u n g dch K M n 0 4 sin h ra s n p h m h u c d u y n h t E c
cng thc cu to.
(CH 3) 3C CH 2 C H C H COCH3

COOH CH2COOH

t chy h on to n m gam B s in h ra n g m gam nc. B k h n g tc d n g vi

B r/Fe. un nng hi B vi Bro c chiu s n g th u c d n x u t m onobrom duy
n h t G.
1. Xc n h cng th c p h n t v cng thc cu t o ca A, B. Gi t n A, B, E.
2. un nng B vi d u n g dch K M n 0 4 ly d th u c d u n g dch X. X tc dng
vi HCl sin h ra Y. u n k h a n Y c s n p h m z (cha h a i n g u y n t).
Vit s p h n n g v cng th c cu to ca X, Y, z.

Bi gii

1. B l hp ch't h u c n n c h a C; B chy cho HO n n B c h a H.

- B : CxHy.

CxHy + (x + ) 0 2 x C0 2 + ^ H 20

( 1 2 x + y)g ,18g

m B = m Hj0 -> 12x + y = 9y h ay X : y = 2 : 3.

B: (C 2H 3)n ; M B = 27n < 2 5 0 -> n < 9,3.

M t khc:

B + B r 0 k h n g p h n ng.

B + B r 2 s n p h m m onobrom d u y n h t.

-> B :

A tc d n g vi dd A g N 0 3/N H 3 to r a c n n A c n h m - c s CH.
A + H 20 ( H g S 0 4) - D n n D c n h m - c o - C H 3 v c s" n g u y n t cacbon
n h A.

81
 E:
(Cl 13) 3C CH , CH----CH COC 3
i .. L .
COOH CH2COOH

Axit 3 - axetyl - 2 - neopentyl - 1,5 - pentanioic.

-> A:
(CH 3)3C CH 2 CH Cl I C -= CM

CH
I I
cn2
% /
CH
3 - N eopentvl - 4 - etinylxiclopenten

2. S p h n ng.
CH3 COOK COOH
ch3 KO(X" CCX)K HOOC COOI1
K M n0 4 d HC1

KOOC' Y ' C(X)K HOOC COOH

COOK
(X)
o

Bi s 4.15

T etanol, ax it axetic, benzen v cc c h t v c cn th i t k h n g cha cacbon

hy vit phng tr n h p h n ng iu ch:
1 . p - ety laxeto pheno n (A).
2. 2,5 - d ietylax etop heno n (B).

V n d l t h u y t l i n q u a n
1. Phn ng cinkyl ho theo Frien Crap

82
 AICU
+ R X + HX

y R X l RCl, RBr hay Rl. Cng c th thay R X bng ancol, anken; khi cht xc
tc l axit c proton.
R
1

+ R OH } r + h 2o
J x 1
h 2s o 4
+ RCH CH R

CH
Nhc im.
- Vic a nhm ankyl (y electron) vo vng benzen lm tng kh nng phn ng ca
vng benzen nn tip tc c ankyl ho tip to sn phm i- hay poliankylbenzen. Do
thu sn phm ankyl ho mt ln th phi dng d lng benzen.
- Thng gy ra s ng phn ho mch ankyl v ng phn ho v tr ankyl nn c
th to ra hn hp sn phm.
H CH
c h 2c h 2c h

+ CH3CH2CH2C1 1C\
- HC1
^ ^ c h n h ) (ph)

c h 3c h 2c h 2 ci : + AICI3 C H 3C H 2C H 2 C l AICI 3

C H 3C H 2C H 2 + AICI 4

H
chuyn v _
CH3 CH
u CH C H 3 C H C H 3 (bn hn)
HiC
3- . / .CH
3 H3C CH3
CH CH
CH3 ch H

ch3
-H

12-MSCHVBTHHtXJC 83
2. Phn ng axyl ho theo Fri en - Crap
Phn ng tng t phn ng ankyl ho; y tc nhn phn ng l cc halogenua
axit, anhirit axit.
// // AICI133
AIC c h 2c h 3
+ CH3CH2 c f + HC1
C1 o

Khc vi phn ng ankyl ho theo Friden - Crap, phn ng axyl ho ch dn ti to

thnh sn phm monoaxyl do nhm axyl ht electron nn lm gim kh nng phn ng;
ng thi cng khng gy hin tng ng phn ho mch.
Qua phn ng axyl ho ri kh ho sn phm thu c dn xut ankyl m phn ng
ankyl ho kh thc hin c.

Bi gii

CH 3C H 2OH + HC1 - Has-Q*tU > C H 3C H 2C1 + H 20

AICI
CH3CH2C1 + CH 2CH 3 + HCl

o
CH3 + PCI, *
cm c + HCl + POCl 3
OH
CI

A ia ,
CH3- < + ( Q - a M i3 CHjCHzc h 3(cQh 2 - C - C H 3 + HO

() o

c h , c h 2^ - c - c h 3 CH,CH2

Q Clemmenxen

cc
COCH 3

C H , c ^ + CH 3CH2 ( ^ - C H a C H j ^ C H j C H 2 C H 2 H 3

Bi tp t gii

Bi s 4.16

Tng hp n - b u ty lb e n ze n t benzen,

84
Bi s 4.17

un nng S tire n vi ax it H 9S 0 4 ta t h u c hp cht:

CH,

0
Hy gii th c h q u t r n h h n h t h n h s n p h m trn.

Bi s 4 .1 8

Hp c h t h u ct E c cng th c p h n t tr n g vi cng thc n gin nht.

M e < 500 vC.
t chy h o n to n 0,144g hp c h t E ch th u c COo v hi nc. Cho sn
phm chy vo b n h d n g lng d CaO th th y khi lng b nh t n g 0,624g.
1. Xc n h cng th c p h n t ca E.
2. un n n g E vi d u n g dch KCro 0 7 /HS 04 th u c F. Cho F tc d n g vi
Io/NaOH, lc b k t t a m u v n g ri a x it ho p h n d u n g dch b n g axit HC1 th u
c G l iax it m ch t h n g c khi lng p h n t ln hn khi lng p h n t ca
E l 50vC.
Xc nh cng th c c u to, gi t n E v vit cc phng tr n h p h n ng xy
ra.
3. H i r a t E c hp c h t H. Oxi ho m n h H b n g K M n 0 4/H S 0 4.
Vit phng t r n h p h n n g v gi t n s n phm h u c to ra.
4. Cho E tc d n g vi Clo (500c, 1 : 1 ); ly sn p h m to ra d u n vi d u n g dch
KOH/C 2H OH. V it phng t r n h p h n n g v gi t n cc hp c h t h u c c th
to th n h .

Bi s 4.19

Vit y cc ph n g tr n h p h n ng theo s sau:

H')S04, c
; > Y
170c
Cc ch ci L, M, N,... ch cc c h t ch a bit.

85
 Phn 5
ANCOL - PHENOL - AMIN

Bi s 5.1

Hy trn h by cch p h n bit:

1. Amin bc 1, bc 2, bc 3.
2. Ru bc 1, bc 2, bc 3.
3. Ru v phenol.
4. Phenol v a x it cacboxylic.

Bi gii

1. C c am in
* C c h 1. Cho p h n n g vi C 6H 5S 0 9C1.
- Am in bc 1.
R - N H 2 + C 6H 5S 0 2C1 - C 6H 5 - S 0 2 - N H R + HC1
- Am in bc 2.
R NH + C6H 5S 0 2CI * C6H5 s o 2 N R I + HC1
R' R
- A m in bc 3.
R N R' + C 6H 5S 0 2C1 ----- khng phn ng.
R"
S au ho t a n h a i s n p h m k t t a b n g d u n g dch N a O H , c h t no ta n l
s n phm ca a m in bc 1 .

QH<| s N R + H20
~ II
o

C c h 2. Cho p h n ng vi H N 0 2/HC1.
- Am in bc 1 (dy bo): Cho kh khng m u th o t ra.

86
 C2H 5 - NH + H N 02 C2H 5OH + N 2t + H 20
A m in thm bc 1 to mui iazoni:

C6H3 NH2 + H N 0 2 + HC1 CC 6H 5 N - N ] c i e + 2H20

Phenvliazoni clorua
un nng u n g dch nc ca mui iazoni th u c phenol v k h No:

c 6H n^ n ] C 10 + H20 - ^ C6H5 OH + N2 t + HC1

- A m in bc 2: K hng c kh th o t ra v to k t t a m u vng.
(C H 3)2NH + HO NO -> (CH 3)2N - N = o i + HoO
im etylnitrozoam in
- A m in bc 3: K h ng c p h n ng xy ra.
2. A n c o l
C c h 1. Cho p h n ng vi (CuO, t); ancol bc 1, bc 2 p h n ng (CuOen -
C uo) cn ancol bc 3 kh n g p h n ng (CuO khng ch u y n mu).
Ly s n p h m c a ancol bc 1, bc 2 cho tc d n g vi d u n g dch A g N 0 3/N H 3
khi u n nng. C h t n o to kt t a m u tr n g l s n p h m ca ancol bc 1. C h t
khng p h n ng l s n p h m ca ancol bc 2.

RCHoOH + CuO -- > RCHO + Cu + H 20

t
R CH OH + CuO +> R c R' + Cu + H20
R l0
R"
I 0
R c OH + CuO khng phn ng.
I
R'

R CHO + 2 A g N 0 3 + 3 N H 3 + H 20 j R C O O N H 4 + 2 A g + 2N H 4N 0 3.

RCOR' + A g N 0 3 + N H 3 + HO - khng p h n ng.

C c h 2. D n g th u c th Lucas (HClc + ZnCl2).

RO H + HC1 ZnC13 > RC1 + H 20

RC1 - kh ng t a n tr o n g nc.
- N u d u n g dch v n c ngay lp tc v t c h th n h h ai lp ri n g bit l ancol
bc 3 (p h n n g n h a n h ).
- N u d u n g dch v n c chm l ancol bc 2 (p h n ng chm).
- K hng c h i n tng g l ancol bc 1 (h u n h kh n g p h n ng).

87
3. P h n b i t p h e n o l v r u
C c h 1. D ng nc brom, phenol p h n ng cho kt t a m u tr n g cn ancol
th khng to k t ta.
OH OH

Bi
+ 3 Br2 + 3 HBr
0

C c h 2. Phenol cho vi st(III) clorua m u tm c trng.

4. P h n b i t p h e n o l v a x i t c a c b o x y l i c
D ng d u n g dch N a H C 0 3.
- Phenol k h n g p h n ng.
C 6H 5OH + N a H C 0 3 -> k hng p h n ng.
- Axit cacboxylic p h n ng to kh th o t ra.
RCOOH + NaHCOg -> RCOONa + C 0 2t + H 20
L u :
Phenol Ka = 1,3.10 10.
K = 4 ,5 .10 7
A xit cacboxylic
K 2 = 4 ,8 .1 0 '"

Cho nn:
C6H5OH + Na 2C 0 3 -> CgHgONa + NaHCOg.

Bi s 5.2

Cho hp c h t A c cng thc cu to:

OFl

NaOH (CH3)2S0 4 H?S0 4c _ 1 . 0 3

1 B ----- ---- c * D i E
2 : 1 2. Zn/CH3COOI

8 8
 B i gii

OH OH

+ NaOH + H20

l o o

%i CH, q / p

OH

H iS 04c
+ HiO
OCH OCH 3

0 0

+ 03
0 CH 3

CHO
Zn/CH3COOH
+ h 2o
c h 2c h 2c h o

Bi S 5.3

Vit phng tr n h p h n ng sa u v cho bit c ch:

Piriin
+ SOCl 2

89
 B i gii

Ancol p h n n g vi thionyl clorua (SOClo) vi s c m t ca baz n h piriin

th p h n ng xy r a theo c ch s ^ 2 (x e m B i s 3.2).
P h n ng tr n khng xy r a v khi p h n ng theo c ch S\-2 vi s quay
cu hnh; trong k h i cu h n h ca hp ch't tr n vi h cu ni kh ng xy ra s
quay cu h n h c.

Bi s 5.4

Hy cho bit s n p h m to th n h khi thc hin p h n ng h i r a t ho cc

c h t sau vi xc tc a x it H +
1 . Prop an - 1,2 - iol.
2 . 2 - M etylpropan - 1,2 - iol.
3. 2 - M e ty lb u ta n - 2,3 - iol.

Bi gii

l.C H CH CH LU*. CH3 CH2 cho + h 2o

I I
OH H
C ch:

C H r - C H CH2 H U . CH, CH CH2 ------- C H , - c h ?H 2

OH OH OH OH2 OH
chuyn v mct^l _ CH CH O H C - C H 2- C H ,
I - - H+
H
CH3 c h c h 2 - H U . CH3 c h CH2 --------CH, CH CH2
I J I ' H2 I
OH OH 0H2 o h OH
chun v hidrua CH3 CH CH---------------- CH,CH2CHO
i H+
H
CH, CH,

2. CH, C CH, H+ , CH, CH CHO + CH, c CHjCH,

I I - h 2o II
OH OH O
CH, H.
_ _ 1
3 . CH, C CH CH, ^ CH, c CH CH, + CH, C CHO
I I - H2 II I I.
OH OH o CH, CH,

90
C h :
T rong tr ng hp mt nguyn t cachn COH c hai nhm th khc n h a u th
nhm no c tn h c h t y electron m n h hn s b chuyn dch.
OCH, (XII, CH,

Bi s 5.5

Hp c h t A (C 7H 140 2) p h n ng vi (CH 3C 0 ) 20 to ra B (C 7H 130 ( 0 C 0 C H 3)).

A khng p h n n g vi hiroxylam in. Khi c h ho A b n g H I 0 4 th u c hp c h t
C(C 7H 190.,)- c p h n ng vi hiroxylam in to r a ioxim. c k h c d u n g dch
Feling. 1 mol c p h n ng vi 4 mol N aO I to ra iodofom v mui ca axit aipic.
Xc n h cng thc cu to ca A v vit phng tr n h p h n ng.

Bi gii

A khng tc d n g vi NHoOH, tc d n g vi H IO 4 n n A c h a i nhm -OH lin

k t vi h ai nguyn t c lin nhau.

A (CH,C0),0+ C 7H 130 ( 0 C 0 C H 3) chng t ch c 1 nhm -OH c este

ho, nn 1 tro ng hai nhm -OH p hi c 1 nhm -OH bc III.
NaOl
C: C 7H 120 2 C H I 3 + NaOOC - (CH 2)4 - COONa
M c p h n ng vi du n g dch Feling, nn c c 1 nhm - C O C H 3 v 1 nhm
chc a n e h it - CHO.
- c : CH 3 - CO - (CH 2)4 - CHO.
Do vy A:

c h 3h

OH OH
( p h n n g vi HIO4 th hai nhm -OH p h i v tr cis)
T h t vy:

13-MSCHVBTHHUC 91
 c h 3 h> + (CH3c o ) 2o CH 3 H / + CH 3COOH

OH OH OH o c CH3
(B) 0

ch 3h h io 4 + h 2o + HIO 3
/ H \
c c
II
H OH
o (C) o
0 = c (CH2)4 CH = 0 + 2NH2OH H O N H =C (CH2)4 C H = N H O H

CH 3 CI 3 ioxim + 2HiO

C H 3CO(CH2)4CHO + [Cu(xitrat)] 2' C H 3C O (C H 2)4C O O H + C u 2O

CH 3CO(CH2)4CHO + 4N aO I - C H Ig + N aO O C - (C H 2)4 - C O O N a + N a i
+ N a O H + H 90

K in thc m rng
Phn ng oxi ho ngt mch ca 1,2 - iol.
Axit peioic hoc chi tetraxetat oxi ho ct lin kt gia hai nguyn t c mang nhm
OH ca 1,2 - iol.
r 2c c r 2 + h o 4 -------2R2c = o + h 2o + HIO,
L LH
H
R2C CR2 + Pb(OCOCH3)4 2 R2C= 0 + 2 CH3COOH + Pb(OCOCH3)2

OH OH
*Phn ng oxi ho 1,2 - iol bng H I0 4 xy ra qua 1 este peioic dng vng:
o
R ,ct-CR 2
R2C CR2 + 0 = 1 OH 2R2C = 0 + HIO
-H20
1 1 II
H H 0 I r OH
0 ^ 0

trans - iol - 1,2 khng c phn ng trn.

OH

+ H I04 *-

92
 'Phn ng oxi ho bng chi tetraxetat xy ra theo c ch tng t:
R 2Cp C R 2
r 2c - c r 2 + R > < o c o c h s)4 _2CHjCOOH- k ^ 0

OH OH
CH3COO OCOCH,
2R 2C = 0 + Pb(OCOCH3)

Tuy nhin tran s - 9,10 - ecaliniol c th b oxi ho bi PbOCOCH^)4.

Bi s 5.6

C m t s d n x u t gc C H 3 c a axit axetic biu h in h o t tn h t n g trng

cy trng.
CHCOOH
C1

(A) (B)

1 . Gi t n A, B, c .

2. A c iu c h t n a p h ta le n v axit cloaxetic c m t c h t xc tc 180 -

215 c . V it p h n g t r n h p h n n g v gi tn c c h ca p h n ng.
3. B cn g c i u c h t n g u y n liu tr n qua c h t t r u n g gian l 1 - naphtol.
Vit s cc p h n n g v n u c ch.
4. c cn g c iu ch t phenol v axit axetic. Vit s p h n ng.
5. Khc vi c , D c iu c h t m t d n x u t tetraclo b en zen (X) theo s :
NaOH l.ClCHoCOOH
-------- . . . --------- -------- D
metanol 2. H+
93
 a. Hon t h n h s trn.
b. Trong q u tr n h s n x u t D sinh ra mt lng nh ioxin l c h t c tnh
ch t cc k c c cng thc:
Cl Cl

cV
TO
^ o Cl
Gii thch s tao t h n h ioxin.

Bi gii

1 . A: Axit (1 - naphtyl)axetic.

B: Axit (1 - naphtoxi)axetic.
C: Axit (2,4 - iclophenoxi)axetic. [2 ,4 - D]
D: Axit (2,4,5 - triclophenoxi)axetic. [2,4,5 - T]
CHiCOOH

t, xt
2. + CiCH2COOH + HC1
Se
OSOi H
c i c h 2c o o h
h 2so.
3. DIO] --H
2S 0 r4 D io; ---------------
Kim, Sm2
-HC1
OCHiCOONa o c h 2c o o h

H'
Na+

OH ONa

CI2/CCI4 r ^ J ^ C1 NaOH r Q
-H 1O

C1
Cl2, P NaOH
CH 3COOH CH2COOH CH2COONa
-HC1 - h 20
Cl C1
ONa OCHiCOONa OCHiCOOH
C1
H+
o + CH2COONa
NaCl
C1
Cl
94


5.
JL
[ A
ONa
ClCH2COO I JL OCH 2CCX)Na

a ^ SN2 A r c | > ^ Sn2 Cl

1
C1
CI (X) CI

o c h 2c o o h
H+

Cl
C1
S to ioxin:

Ck .C1 NaO
+ 2NaCl
Q
C1 ONa

Bi s 5.7

1 . Vit cc phng tr n h p h n ng sau:

CrO,, H+

OH
K M n 4 long

OH
2. Phenol tc d n g vi H N O 3 long to r a hn hp ch a h ai ng p h n nitrophenol.
Vit phng tr n h p h n ng v tr n h by cch tc h rin g h a i ng p h n ny.

Bi gii

H+
1. 2 + 6 C r0 3 2 HOOC CH2 c h , CH2 c COOH
1 I!
OH 0
+ 3 C r 20 , + H20

OH

+ 2 K M n 4 + 4 H 20 + 2 MnT + 2 KOH
OH

95
 + HNO 31oing OH
( 20%)

o + h 2o

no2
ng p h n o - v p - n itro p h e n o l c th tc h rin g b n g cch c h n g c t li cun
hi nc. ng p h n o rth o to c lin k t h i ro ni p h n t n n b hi nc
cun sang.
H.

Bi s 5.8

Sn phm no dc t o t h n h kh i cho cc c h t s a u tc d n g vi NaNOo/HC-1?

1.CH, CH CH2NH2

CH,
2. CH 3 - CH = CH - C H 2N H 2

NH
CH, CH,
1 1 '
4 . CH3_ C c c h ,

n h 2 l ,h

Vn l thuyt lin q u a n
1. Phn ng gia am in v H N 0 2
a. Phn ng ca am in bo bc 1: To ancol tng ng.

C 2H 5N H 2 + HONO HC1 > C 2H 5OH + N 2 + H 20

C ch:
 H+
HO NO = H20 no H

CMU NH, + H20 NO --------- -* C2H5 N N = 0 C 2H S NH N o

-H20 I Nitrozoamin bc 1
H
non
C2I Is N = N OI I C 2H5 N -= N Cl_____*. c 2HjT c ,n so n
- h 2o M r -P n
+
M u i d ia z o n i ' N 2- -<1

b. Phn ng ca aniin thm bc 1: To mui diazoni.

C6H3 NH2 + HN 0 2 + HC1 [ c 6H5 N ^ N ] C 10 + 2H2

Piicnyldiazoni clorua
Dun nng dung dch nc ca mui diazoni thu c phenol v kh N 2:

[ c 6H5 n ^ n ] C 10 + H20 - ^ C6H5 o h + N2 t + HC 1

c. Am in bc 2: To nitrozoamin.
(CH 3)oNH + H O N O -> (C H 3)2N - N = o i + H 20
D im ety ln itro zo a m in
d. Am in bc 3: Khng tc dng vi HNO<2 -
2. Phn ng ca mui diazoni

a. [ C V V - N - ^ N J X 0 + H20 C6II5 OH + N 2 + HX

b. | c 6H5 N - ^ n ] X 0 + R O H -------- C6H5 OR + N 2 + HX

I ILBOl + HFt
c. [ c 6Hv- n -= N ]H SO ? - llQ H , N - = N ] BF4 Q H , F
hoc HBF4 -N 2, -BF3

d. [ q h ^ n - ^ n J x 0 + h 2o + h 3p o 2 -------- c 6h 6 + h 3p o 2 + n 2 + HX

e. [ c 6H < ^ N n ] X 0 + KI Q, H5 I+ N 2 + KX

f. [ Q H 5- N - N J X 0 - - - Ci Q ,n - C 1 + n 2

g. [CfiH, N - = N ] X + CuCN-------- C6H5 CN + N2 + CuX

h. [ c 6H 5 - N - n ] X 0 + C6H6 C6H5 C6H5 + N2 + HX

i. [q V -N ^ N ^ X 0 4 - CH2= ch CN Cu+ C 6H 5 C H = C H CN
+ N2 + HX
k. Phn ng ghcp i to azo:

97
 " O -

Thc cht y l phn ng th electrophin vo vng benzcn. Tuy nhin tnh electrophin
ca ion diazoni [ArN N]khng cao lm vi in tch dng ca nguyn t N b gii to mt
phn do hiu ng +c ca vng benzen. Do mui ciazoni chi tc dng vi hp cht thm
c tnh nucleophin cao n h a m in thm, phenol,...

Bi gii

NaN 0 2/HCl
1 . CHi CH CH2NH2 + HN 0 2 ------- ----- * CH3 CH CH2 CI3+ N, + H20
L T ,
CH, H

Do s ch u y n v c a cacbocation tr u n g gian:

NaNCMICl _
CHj CH CH 2NH 2 - . CH 3 CH CHiNtCI -------------- CH 3 CH CH2
-

I I -N 2,-C1G l' f
CH 3 CH 3 2 CH,

-------- C H . r - CH CH2 CII, 2 M * . C l3 CH CH CI I3

2 3 -H+ I
01

NaNOi/HCl _
2. CH C H = c u CH2NH2------ C H r - C H = C H CH2N2CI --------

C l It - c h c i * - ? ! ! , - C I I, C l I C I 1 = C H , U 2 U - C l 1 H C l f = C l I;
2 2 -H+ - I -
OH

, / \ _ _ NaNOi/HCl / ----- \
3- c ) + HONO ----- / \ + H20
NH N

N= 0

H3H3 H3H3 H,
1 NaN 0 2/HCl I I I
4. CH3 c c C H , --------f CH3 c c c h -------- CH 3 c C CH 3

NH2 OH ^1^2 OH -N2 '- CP c h , oh

h3 h\
I ...............................
CI3 c e n , c h 3 c c h ,
1 , 1 . H+ I J
CH 3 OH CH 3 O

98
Bi s 5.9

Hp c h t A c cng th c p h n t CH n O<)N k h n g t a n tro n g nc v a x it long

nhng ta n tro n g d u n g dch kim.
Ho t a n A c tn h q u a n g h o t vo d u n g dch N aO H , s a u a x it ho th to ra
A di d n g bin th raxem ic. K h A q u a n g h o t b n g H 9/Ni c B c cng thc
C -H 13N q u a n g hot. Cho B tc d n g vi HNOo c hn hp ancol c q u a n g h o t v
mt lng n h ancol t - amylic.
Xc n h cng th c c u to c a A, B, c. G ii thch.

Bi gii

A t a n c tro n g kim n n A c tn h axit. A k h n g t a n tro n g ax it long v A

(C 5H n OoN) b k h th n h n (C 5H 13N) n n A l hp c h t nitro.
A c tn h q u a n g h o t n n A c th l:

0 2N C l *CI I CH 2CH 3 o 2n *CH CH(CH 3)2 o 2n c h CH 2CI12CH 3

1 1
ch3 ch3 ch3
(I) (II) (III)
Xt q u t r n h sau:
H

OH ~\ / 0 OH
R -C -N K M >* -
R --- Crrr.N H
R c = N
G o - h 20 o o
R' R
1
- R' R'
Dng axi
D ng axi vi n g u y n t c lai ho sp 2 t chuyn h o v d n g n itro th ng v H
chuyn v c 2 t h ai p h a ca m t p h n g lin k t i t o b in th raxem ic.

OH o
R C = N R CH N
o o
1
R R'
Bin th raxemic
Vy to b in th ra x e m ic th -NO p h i lin k t tr c ti p vi n g u y n t
cacbon b t i. H n hp r u to ra l do s ch u y n v m c; n n A l (II).
PTP:

o

(CH 3)2CH C H N 0 2 + NaOH (CH 3) 2CH c n / Na + H20
m
o
CH 3 ch3

14-m s c h v b t h h u c 99
 hno2 CH, (C)
(CH3)2CH CH N 0 2-^ t ( C H 3)2CH CH NH2 CH3
CH3 2 CH, (B) c h 3c h 2- c c h 3

OH
(Ancol I - amylic)
S t o t h n h h n h p r u l do:

H N 02 + HC1 _
(CH3)2CH C H NH; (CH3)2CH ch N Cl
-2H20 *
- n 2. -C1
ch3 CH 3
H

C H , V.
C ^ hn
CH,
L H j - QhL (CH 3 ) 2CH C H OH
-H'
c h 3 CH} (C)
C h u y n v h i r u a
CH
_ hoh
c h 3 c h 2 c h 3 - c h 3c h 2 c ch 3

CH OH
(A n co l t - a m y lic)

Bi s 5.10

1 . iu ch p - n itr o a n ilin t a n ilin .

2. T to lu en v cc c h t v c cn th i t h y th i t lp s iu c h a x it m toluic.

Vn l th u y t lin q u a n
Bo v nhm chc amino.
V nhm -NH 2 d b oxi ho bi axit nitric nn trc khi nitro ho cn chuyn amin
thm thnh axetamit th.
Nhm -NH 2 y electron mnh, nn:
 Bi

+ 3Br2 + 3HBr

fu'a nhm axct\l vo lm gim mt clectron trn nguyn t N.

NH2 o nh c ch 3 n h Ac
c h 3 c
Cl
hoc (CH 3CO)20
G b nhm CH 3 - c o - bng cch dng dung dch kim nng.

Bi gii
NH2 NH c CH3
l

+ (CH3C0)20
o + CH3COOH

NH c CH, NH c CH3
l l
0
I2SOkt
o + UNO \! o HoO

OJ + CH 3C 0 0 H

NH c CH3
ch3

NH c CH3 N -,a
101
 COOMgBr

Bi s 5.11

CH2CH2NH;

A c cng thc cu to:

o
CH3O OCH
OCH 3
1 . Gi t n A.
2. Vit phng t r n h p h n n g khi:
a. A + C H 3MgI d.
b. A + p - to lu e n su n o n y l clorua.
CH 3I d Ag20 t r,
c. A B c D

Bi gii

1 . A: 2 - (3,4,5 - trim e to x ip h e n y l)e ty la m in .

2 CH3MgI

CH2CH2NH; OCH3
0

b. 1Q 1+C H , s-a-^cH 3 5-NH(CH2 (XU ,

CHjO" 'Y ' < )C H ' o 0

OCH,
OCH,
+ 2HQ

102
 ci 2ni i2 cM iisp-cH ,
L.
Cl ,
c.
+ 2 C i ihr I0 + 2 HC1
C H /) OCH3
0CH3

CH,
u
c h 2c h 2n - ch3

L
CH,
I0 + H 20 + A g 20 2

CH30
0CH3

a i= c n ,

OH * Q l + Q I , N CII 3 + II20
CHiO CH3O' V ^ och3
ai
OCH, och 3

Bi tp t gii

Bi s 5.12

1 . Cho phng tr n h p h n n g sau:

C 6H 5N H 2 + (CH 3C 0 ) 20 -> C 6H 5N H - C O C H 3 + C H 3CO O H

P h n n g cn xy ra ti p khng, v sao?
2. T b enzen v it cc ph ng t r n h p h n n g iu ch:
a. m - B r 9CgH4.
b. c 6h 5i, c 6h 5f , c 6h 5c n .
3. Axit m n h chu yn 1,1-iphenyletaniol u ti n t h n h c h t A s a u ch m hn
t h n h c h t B. Vit cng th c c u to ca A, B v cho b i t c h t no bn hn, to ra
n h a n h hn.

103
 Phn 6
ANEHIT - XETON

Bi s 6.1

1 . T glixerin, vit cc phng trn h p h n ng iu ch:

CH2 CH CHO
L
H
L
H
2. H on t h n h s p h n ng sau:
NaOH HC
Glixerin A - B - c D

Vn l th uyt lin q u an
1. Anchit khng bn trong mi trng kim
Anehit c H a th xy ra phn ng ngng t Crotonic.
X NaOH
CH, CH 0 + CH3 CH= 0 CH3 CH CH CH= o + H20

OH

CH2 CHO 11,0

I HOH
CH, CH CH2 CHO c h 3 c h c h 2 c h o

p
- OH OH Anol

Anchit khng c H a thi xy ra phn ng Cannizaro.

2 C 6H 5C H O + O H ' -> C 6H 5C H 2OH + C 6H 5COO .

o
h+y&/ //
Q,H c Q H , Q -H M C6H5 c x + h 2c c 6h
I1
OH _
OH ()
QHsCOCP + QH,CH,OH
Nhm chc anehit d b oxi ho bi dung dch K M n04, nc brora:
 RCHO+ B r2 + H 20 - > RCOOH + 2H B r

RC H O + [O] RCOOH
2. Bo v nhm chc anchit
Da nhm chc anehit v dng axetal bng phn ng vi ru vi xc tc axit.
oc 2h 5
H+ /
R CHO + 2C2HsOH R CH + H20
O C 2Hj
Axetal
* Axetal bn trong mi trng trung tnh v mi tring kim.
G b nhm bo v bng cch thu phn axetal trong mi trng axit, khi nhm
anehit v ru ban u c ti to.

Bi gii
KHSO4
I. CH2 CH CH 2 CH, c h c h o + 2H20
I l I <"
OH OH OH Acrolem
OCH,
/
CH2= C H CHO + HCl + 2CH,OH ------- CH2 CH, CH + H,0
I ~ OCH3
C1

............................. C2H5OH _________________

CH CM2 CH + KOH CH2= C H CH + KC1 + H20
I ^O CH , 1 OCH,
CI
OCH, / OCH1
3CH2= C H CH + 2KMn0 4 + 4 HzO ---------3CH2 CH CH
X ()C 1], I I ^OCH ,
OH OH

+ 2KOH + 2Mn0 2
/ OCH3
CH2 CH CH + H20 CH2 CH CHO + 2CH,OH
I I och3 I I
OH OH OH H
M27S0
H 0U4,FeS0.
,re 0U4
2 . C H 2 C H C H 2- - t0 * C H 2= C H c h o + 2 H 20
?
(A )
OH OH OH
CH2= C H CHO + Br2 + 2 H 20 -------- H2 H COOH 3HBr

OH Br (B)
CH2 CH COOH + 2NaOH ------- CH2 CH COONa +2H20 + NaBr
I l \ /
OH Br <c>

105
 CH2 CH COONa + 2 MCI ------- CH, CH c o o n + Na('l
\ / I I
OH Cl (D)

Bi s 6.2

1 . T a x e ta n e h it hy vit cc phng trn h p h n ng ho hc iu c h

spiro[ 2 ,2 ]pentan.
2. Hy cho bit s n p h m chnh ca cc p h n ng sau:

a. CH 3 - CHO + C H 3COCH 3 NaQH

b. HCHO + (C H 3)3C- c h o - 1QH~^

c. HCHO + (C H 3) 2CH- c h o ( a(()H)-

B i gii

v ~ II OH y^HCHO
I . H - C + CH2 c i c i l 2 c CH? CH c
r _ I" H I I I H
OP OH Oil CH OM
c h 2o h o 01,011 CH2Br
HCHO \ _ / LAIH4 I HBr i
- > CH2 C Q ~ CH2 c CH2OH -* CH2 C CH2Br
IH CH2OH
I
OH
L ..
CH OI
iBr L
CH,Br

CH2 ch.
Zn. t"
'c
ch2 ch2

2. a. CH3CH0 + CIljCOCH, CH, CII CTI2 COCH.

OM
b. HCHO + (CH,)3C CHO + N aO H ------- HCOONa + (CH,),C CH2OH
CH,

c. HCHO + (CH ^C H CHQC- OHi 2 c h , C CHO

I .
CH,OH

K i n th c m r n g . Phn ng kh nhm cacbonyl.

1. Phn ng hiro ho xc tc

R c R + H2 Nl1 R CH R
0H
106
 - Axit cacboxylc khng cho phn ng ny.
- Phn ng hiro ho nhm cacbonyl xy ra chm hn phn ng hiro ho lin kt i
c = c v ccirt nhng iu kin khc nghit hn.
2. Cht kh LiAlH. hay NnBH.

4HCH = o + LiAlH, + 4 H 20 -> 4 CH 3OH + LiOH + Al(OH)3.

4HCH = o + N a B H 4 + 3HO - 4 CH 3OH + N a H 2B 0 3.
R\ R R
ru HOH \
C = Q ) + U aih ; Nc-(fu c OI I
R R' R
H H
- LiA lH 4 khng kh lin kt i c = c.
- Axit cacboxylic cng l kh bi L AIH nhng khng b kh bi NciBH.

RCOOH t RCHO R C H 2OH

Este b kh tng t cho hai ru.

RCOOR' > R C H 2OH + R'OH.

Bi s 6.3

Thc hin chuyn ho sau:

HCN H,0/Na()H HNO,
G lix era n eh it A B c
Cho bit c u tr c ca c n u c h t u l L - G h x eran eh it.

Vn li thuyt lin q u a n
Phn ng cng nuclcophin vo nhm cacbonyl.
R
\ s +r v ~ s+ \
c = 0 + HCN c OH
,/
R'
CN
Nu s n ng khng gian nh nhau s to ra bin th raxemic. Nu nhm cacbonyl
lin kt vi nguyn t c bt i s to ra hai nn phm ng phn quang hc khng i
quang theo quy tc Cram: " Nu ba nhm th nguyn t c bt i inh vi nhm cacbonyl
thi tc nhn nuclcophin s tn cng nhm cacbonyl t pha t b n ng khng gian hn".

Hng ph Hng chnh L

X Y R

ox
Sn phm chnh Sn phm ph
XY : HCN.RMgBr.....

15-MSCHVBTHHUC 107
 Lu :
Do s n ng khng gian ca lin kt i c = o m hp cht cacbonyl c cu dng bn
nh trn.
L: nhm th ln.
N: nhm th nh.
TB: nhm tli trung bnh.

Bi gii

CHO li CH,OM

HO

c h 2o h OI
L - Glixerandehit

HO H (ph hp)

CH,OH

O 1 (A) (Sn phm chnh)

cN C(X)Na COOH

H OH H OH
OH NaOH, 1120 H UNO V!
HO H HO H HO H

H2OH H2o n XX)H

(A) M) (C) Dng tireo
Axit (2R, 3R) - tactric

Bi s 6.4

tch ring xiclohexanon r a khi mt hn hp gm xiclohexanon (s = 156C)

v xiclohexanol (s = 160C) ngi ta ti n h n h n h sau: Lc hn hp vi d u n g
dch N a H S 0 3 bo ho tro n g nc. S a u m t thi gian th m ete ctylic v tr n u.
Tch ly rin g p h n ete v p h n nc. T h m d u n g dch N aO H hoc d u n g dch
H .,S 0 4 long vo p h n d u n g dch nc. S a u li c h i t b n g ete n h trn.

108
 P h n dch e tc ln ny em lm k h a n , c t loi b etc ri cat th u ly
xiclohexanon.
1. (ii thch Uxn gon q u trn h . D n g c ht g lm k h a n .
2. Vit cc p hng tr n h p h n n g ho hc* xv r a v gii th ch tc d n g ca
axit v ca kim.

Bi gii
Anchit
Mctylxcton RCCOCH 3 S n p h a 111 c n g d n g m u i k h n g
Nui isoyi 2o
Xe ton vng khng b n --------- :----Z-+. J lan t r o n g c c d u n g m i k h n g
nu p h n c c n h e t e , h i r o c a c b o n
V- khng
c Igian

/ V - O! I v () u ta n t r o n g e t e

P h n t:

OH c P OH Oi o

R C R +^:sONa I I I
R S ONa R c S ONa
o IR' O R' o

S O j N a ( k h n g ta n t r o n g e t c )

+ + N a + + h 2
S 0 3Na

Dng NiioSO. lm kli tn.

C c h tc d n g ca axit:
OH o 1! n OH
p) ^II+ j <-
R c s o p - - R C r - S O H R C + Sj + i20
li II 1
-t
R'
!1
O R'
R' o
-H+
R c = 0
IR'
C ch tc d n g ca bciz:
&
Bi s' 6.5

Cho a n e h it tc d n g vi anilin. H y cho bit c c h p h n n g v cu trc ca

sn phm to th n h .

Bi gii

c 6h 5 - c h = o + h 2n - c 6h 5 -> c 6h 5 - c h = n - c 6 h 5 + h 2o
B e n za n a n ilin (Baz Schiff)
C ch: Cng nucleofin vo nhm cacbonyl to s n p h m t r u n g g ian khng bn
t tch nc to th n h s n p h m ng n g t.
H
L
q h 5 c ^ + h 2n q h 5 Q H , C NH2 QHS -----

H cP H

Q H , C H = N Q H 5 C6H5 N C6H5
-HOH
OH H
B enzanan ilin c h a i ng p h n c is v tr a n s . T rong p h n n g tr n s n phm
to th n h l ng p h n t r a n s bn hn.

\ / CfiH5
C N
c 6m /
P h n t b e n z a n a n ilin k hng dng p h n g do cp electron t do tr n nguyn t
N lin hp vi vng b enzen ca hp p h n a m in lm cho vng b e n z e n lch i mt gc
ra khi m t phng.

Bi s 6.6

A nehit v xeton p h n ng vi cc c h t d n g R - NH to r a cc hp c h t c
nhm cu to ^ C = N R v H O. Phn ng thng dng xc tc l axit v khi
tc phn ng ph thuc vo pH theo th sau:

110
 o 7 pH

V tr cc i cn p h thuc vo cu to ca gc R tro n g p h n t R -NH.,.

C c h p h n ng n h sau:

rn h 2 + ir ^ rn h 3

(CH 3)2C o + H+ ^ (CH 3)2C = 0 H

G
0) CH\ NH2- R 2 CH, N H -R
(CH 3)2C = 0 H +RNH2 ^ Xc X \ /

C H ./ X OH C H ./

|(3)
CH,
\
'C = N R
CH3^
+ H+ + H20

1 . Theo c c h tr n th pH ti u s ri vo k h o n g no?
2 . Cho b it giai o n (1) l ch m n h t th tc p h n ng t cc i ti pH tng
q u t no?
3. G i s hp c h t cacbonyl c h n g s p h n li Kb = 10 ' 14; R - NHo c Kb = 10 ' 11
Nng cc c h t b a n u l IM.
a. T nh pH tc t cc i.
b. Tc p h n ng cc i pH tr n gp bao n h iu l n tc p h n ng
pH = 0 v pH = 7.

Bi gii

1. pH ti u s ri vo k h o n g sao cho nng ca axit lin hp ca hp c h t

cacbonyl ln v am in b an u khng b proton ho hon ton.
2. Tc p h n n g c quyt nh giai on c h m n h t ca p h n ng, nn:

V = k[(C H 3)2C = H ] [ R N H 2]

111
 V giai don chm nht quyt nh tc d chung ca ton h ph.-in ng nn (i
d t tc cc di th pH phi t ho mn ticli s nng

[(CH3)2C = H ] [R N H 2] l rc di.

3. a. K hiu (CH 3) 2CO] l A; (CH 3) 2CO+H] l AH

[RNH2] l B; [RNH+3] l BH.
[H+] l H ; [O H ~]lO H .

R N H 2 + H O H = R N H , + O H ; R N H : + H + ^ R N H 3
RH O H
K. = - vi B + BH = 1 -* BH = 1 - B
b B
Kw
B K b .H + K w | + Kb
Kw

(C H 3)2 C = 0 + HOH ^ (C H 3)2C = OH + 0 H

(CH3)2C = 0 + H+ ^ (C H 3)2C = H
K _ AH_OH vi A + AH _ 1 ^ A _ l AH

k' h
K' = A H Q H = A H K W XH = K 'b H - Kw
b l-A H (l-A H ).H K w + K 'b H
l+ K>H
Kw
thay v o b i u thc V = k . A H .B t a c:

K H K b = 10 "

v = k - % T -----
------K ------- vi
K 'b = 10 14
I + ; b H lf b xH
Kw Kw K w = l() "

H I _, H
v = k . ~ .----- = k . Tr--------T------------
l + H I +10 H I0 H 2 + ( I 0 3 + 1)H + I
Tm H V t cc i.
H
max V
I0 3 H : + ( I 03 + 1)H + 1

= I0 3 H 2 + (1Q3 + 1)H + 1 - H (2 .1 0 3H + I 03 + 1) _ -!() H 2 + 1 _

[O-H 2 + ( I 03 + I)H + 1]2 [ l e r n 2 +(!() -H )H + 1]2 "

-> H = i V r 7
112
 - y max khi H = V H) ' = IO 1 5 -> pH = -lgio' 15 = 1.5.
Vy pH = 1,5 th tc p h n ng l cc i.
b.
* pH = 0 -> H = 1

= ir 1 = *
vpH-0 2 ( 1 0 3 + 1) 2002

* pH = 1,5 -> H = 1 0 1,5

10 ' 15 k. 10 1,5
vH = 1-5 _ lO'Mo- '1 + ( 10 J + 1)10 15 +1 33,65

* pH = 7 -> H = u r 7

, n -7
v pH = 7 = k TT------------~ r % k -10
(1 + 10 7 )(l + 10 4 )

v p H = l .5 1 0 ~ 1,5.2 0 0 2 1 88

v pH=() 3 3-65

v p H - t . 5 = 1 0 ~ ' - 5. 1 0 7 = M 9 8
v ,)H-7 33,65

Bi s 6.7

1 . Hy cho b it s n p h m to th n h t cc phn ng sau:

a. CH3COCH0CH3 + B r2 -

b. CH3COCH0CH3 + B r2 ^ >
2. Ngi ta p ha c h thuc c h a bnh vim hng loi n h trong gia nh theo cch
n gin sau:
Cho nc si vo cc cha N a H C 0 3 ri cho thm d u n g dch cn iot v lc ln,
ngui bt s c cc thuc xc hng.
H y vit cc p h ng tr n h p h n ng xy ra v nu n h n g d u h iu b ngoi
n h n ra mt s p h n ng.

Vn d l thuyt lin q u a n
Phn ng halofom.
Nhm cacbonyl (ca anehit, xeton) ht clcctron mnh lm cho nguyn t H v tr a
i vi nhm ny rt linh ng nn d b th bi halogen nh clo, brom v ngay c iot.

113
 Phn ng halogen ho xcton (v tr ) c bc khng i vi halogen (khng ph thuc
nng halogcn), chi ph thuc nng hp cht ccicbonyl v bng tc cnol ho. C th
phn ng th xy ra qua giai on enol ho hp cht cacbonyl (chm) sau n giai on
cng halogen vo enol nhanh).

/' R\ / R
R c C R' ------*- c = d ----- M_ C + Hllal

l h" h 1
llal
Hal Hal II

Qu trnh halogcn hn c xc tc bng axit hoc baz.

Xc tc axit:
H
H
*c C
R c c R' R .
h R ' ----------------R\ c = c /R'
I r I f V
II V II OM 11 0 11

-Xc tc baz:
H
t OHG o ] ^ r HOI \ /
R c C R' R C C R' c[ o / \
I r || -HOM I c\ u -oH 0 n OH
H <0 H <0

Vi hp cht R - COCH 3 (R: H, ankyl, aryl) trong phn ng halogen ho trong mi

trng kim, dn xut trihalogen b phn hu to mui RCOONa v halofom CHHal3 (phn
ng halofom ho).

R c CH 3 + 3Hal2 + 3NaOH ----- R c CHal 3 + 3NaHal + 3H 20

l '
0 0

R c CHal3+ NaOH -----CHHal 3 + RCOONa

II
0

R cCH 3 + 3H al 2 + 4 N a O H ----- RCOONa + CHHal 3 +3NaHal + 3 H 20

II
O
CHClv clorofom
CHBi'v bromofom

CHIj (iodofom): Cht rn mu vng sng, t tan trong nc v c mi c trng nn

hay dng phn ng iodofom (2 + NaOH) nhn ra hp cht cacbonyl kiu RCOCH3.

114
 B i gii

1. a. C H 3C O C H 9C H 3 + B r 2 C H 3C O C H B rC H 3 + H Br

b. C H 3C O C H 2C H 3 + 3 B r 2 + 4 0 H " CHBr 3 + C H 3C H 2COCT + 3Br

2. Thc ra:

2 H C 0 7 ----- - 7 ------C O i- + C 0 2 + H 20 (1)

-1 nc nng J

CO3 l m cho d u n g dch c tn h kim m nh .

Ban u:
C H 3C H 2OH + I2 -> C H 3CHO + 2H1 (2)
Sau d:
C H 3 - C H O + 3 I 0 + 40H ~ -> C H I 3 + H C O C T + 31" (3)
C hnh C H I 3 c tnh dit k h u n .
- N h n r a ( 1 ) do c bt kh.
- N h n r a (2) do cn iot m t m u.
- P h n n g (3) sinh r a k t t a m u vng.

Bi s 6.8

Trong 5 l k h n g n h n rin g r cha cc hp c h t sau:

C 6H 5C O C H 3, C 6H 5C H (0 H )C H 3, C 6H 5C H 0 , C 6H 5C 0 0 H , C 6H 5C 0 C 2H 5.
Da vo k t q u th nghim sau y cho bit k hiu A, B, c, D, E ng vi c h t no?
1 . Cho vo mi c h t 1 t git hn hp K 2C 10O 7/H 9S O 4 v lc u, s a u vi p h t
th y A v c b in i d u n g dch da cam th n h x a n h lc.
2 . Ch vo mi c h t mt t dung dch N aO H long ri lc m n h th ch thy
ring c h t B ta n c.
3. Khi u n nng vi I 9 trong dung dch NaOH thy A v E cho k t t a m u vng.
4. c, D, E u tc dng vi 2,4 - initrophenylhirazin cho kt ta m u d da cam.

Bi gii

+) Kr,Cr<>07/H S 0 4 oxi ho ru, anehit.

3C 6H 5CHO + K 2C r 20 7 + 4 H 2S 0 4 -> 3C 6H 5COOH + C r 2( S 0 4)3 + K 2S 0 4 + 4H 20
da cam x a n h lc
3C6H 5CH(OH)CH 3 + K 2Cr 20 7 + 4H 2SO -> 3C6H 5COCH3+ Cr 2(S 0 4)3 + K 2S 0 4 + 7H20
+) C h t ta n tro n g d u n g dch N aO H long l axit benzoic.
C 6H 5C 0 0 H + N aO H > C 6H 5COO Na + H 20

16-MSCHVBTHHt!UC 1+5
+) I/NaOH p h n ng c tr n g n h n ra hai nhm chc:
c CH3 v CH CH ,

o
L
OH
P h n ng:
R CH CH, + h ------- R C CH3 + 2HI
r
OH O
R c CH3 +3I 2 + 4NaOH R COONa + Cffl3 + 3 NaI + 3H20
II ' " vng
O
+) 2,4 d in itro p h en y lh id raz in n h n ra hp cht cacbonyl.

c = o + H2N - N H N 02 C = N - N H NO + h 20
R, / ---- R. /
O N o 2n

Do vy: A: C 6H 5 - C H (O H )-C H 3
B: C 6H 5 -COO H
C: C 6 H 5 -C H O
D: C 6H 5 - CO - C 2H 5
E: C 6 H 5 - C O - C H 3

Bi s 6.9

1 . Axeton tc d n g vi clorofom trong s c m t ca KOH to r a 1 , 1 ,1 - triclo - 2 -

m etylpropan - 2 - ol. Hy cho bit c c h phn ng.
2. F o m a n d eh it p h n ng vi N H 3 to ra h e x a m e ty le n te tra m in C 6H 14N 4 v nc.
C h t ny c cu tr c ging n h a d a m a n ta n nh n g ti cc u m t ca cc vng do
cc nguyn t N chim gi. l nh n g c h t bn c im nng chy cao. Cho
h e x a m e ty le n te tra m in tc dng vi H N 0 3 trong C H 3COOH k h a n to ra hexogen
(cht r t ph bin dn g lm cht n trong th chin th hai) ng thi gii phng
3 mol a n e h it fomic v 1 mol N H 3.
Vit cc phng trn h p h n ng.

Bi gii
C1 ch3
C1\ I

c/
1. C1 c H + CHj c CH,

0
X L
H Cl C C CH,

Cl H

116
Cef che:

c ,\ r " e oH
CI C H
/ -HOH
CI CH 3

CI C C CH 3
-OH | |
CI OH
2. 6 HCHO + 4NH3 C 6H 12N 4 + 6 H 20
H e x a m e ty le n te tra m in (U rotropin)
Urotropin:

CH2/ CH;
I CH, !
N -| -N

CH 2 CH

</ no2
c h 2/ I

/ H ; hJ * 3H N O , C
- ^ + NH3+ 3HCHO

c h 2^ ch2 o 2n no2
Hexogen

Bai so 6.10

A n dehit benzoic tc d u n g vi hidroxylam in tao benzandoxim .

1 . Benzandoxim co dong p h n h in h hoc khng? N eu co h y chi r ten goi ca
h a i d a n g dong p h n do.
2 . Hy cho biet s n p h a m v cd che q u tr in h chuyn vi B ecm an ca hai dong
p h n ca benzandoxim .

Bai gii

1. C 6H 5 - CH = O + H 2H - OH -> C 6H 5 - CH = N - O H + H 20
B enzandoxim

117
 Q H 5 C H = N 011

H 0H H
\ / \
C=N C=N
/ / \
CftH5 C OH
syn - B e n z a n o x i m anti - B e n z a n o x i m
D ng syn l (lng c nhm -OH cng p h a vi ng uyn t H lin k t vi
ngu yn t cacbon tro n g nhm c = N, dng a n ti c cu h n h i lp (x e m B i s
1. 4).

2. H OH H
\ / |J+ \
C=N c NH C6H 5
C 6h / o

H
XC =N - u+-+ Q H , c NH,
/ \ II
C J \( OH o

C ch: P h n ng xy ra theo kiu a n ti (hay l kiu tra n s) ng ha l nhm -OH v

n hm th R v tr a n ti chu yn ch cho nhau.

a. H OH H 0H 2
\ / H+ _\ /
'C = N ------ CH = N C6H5
c 6h / :q h /) 1 -H 20
\\ /
/
V s

HOH H\ _______
------------>. HO CH = N Q H , c P4H Q H s
-H+ o

b. H i' h " T \
H+ x \ L \

c 6h / oh q h ,/ 0 H 2' H

H0H*. c 6h 5 c = n h c 6h 5 c n h 2
-H+ 1 II
H o

K i n th c m r n g
Phn ng chuyn v Becman c mt ngha ln, chng hn trong cng nghip c th p
dng phn ng chuyn v Becman iu ch t Capron.

118
 OH O o NH

I 2/Ni Cu. 250c NH,OH

H, - h 2o

Phenol Xiclohexanol Xiclohexanon Xiclohexanonoxim

C (CH2)5 N -
0 ' 1H J n
Caprolactam T Capron

Bi tp t gii

Bi s 6.11

Hp c h t A (C 8H 160 ) cho p h n ng ioofom n h n g kh ng cho p h n ng cng

H. Khi u n nng A vi H 2S 0 4 c 170c th ngoi s n p h m c h n h l B (C 8H 14)
cn th u c 1,2 - im etylxiclohexen. Oxi ho B ri thc h in p h n ng ecacboxyl
ho th th u c m etylxiclopentan. B kh ng c ng p h n h n h hc.
Xc n h cu t o c a A v gii thch s to t h n h 1,2 - imetylxiclohexen.

119
 Phn 7
AXIT CACBOXYLIC - ESTE

Bi s 7.1

T etilen v cc ho c h t v c cn th i t khc h y iu ch:

1. C H 3C H 2COOH.
2. C H 3C H 2C H 2COOH.
3. C H 3C H 2C O C H 3.

Bi gii

1. iu c h C H 3C H 2COOH
CcA :

CH2 = CH2 + HC1 CH 3 - C H 0CI

CHg - C H 2C1 + Mg t- k- an -> CH 3 - CHoMgCl

C H 3C H 2MgCl + NaCN(KCN, HCN) *P-+ C H 3C H 2CN + NaCl(KCl, HC1)

2 C H 3C H 2CN + 4 H 20 + I 2S 0 4 > 2 C H 3C H 2COOH + (N H 4) 2S 0 4

Cch 2:

C H , CH2MgCl - Q 2,t CH CH2COOMgCl CH 3 CH2COOH

-MgCl 2
Ngoi r a cng c th iu c h axit tr n th eo mt s cch sau:

CH 3CH 2C1 c h 3c h 2c h 2c h 3 Crackinl c h 4 + C H , c h = c h 2

-NaCl
. _ I, nh sng _ __ Mg
*) GH CH3CI CH?MgCi
AgoO
2 C H i= C H , + a 2C12-----CHi
300c
CH*-----O 2
HQ [0]
CH3MgCl ------ 2 ------- CH3CH2CH2QMga - L- u . a 3CH2CH2OH V CH3CH2COOH

120
 1 500c
*) 2CH 4 - > C H - = C H + 3H 2

CH = C H - ^ C H = C N a - g j g j ! > CH,CH 2C = C H

3CH 3C H 2ChCH + 8 K M n 0 4 -> 3 C H 3C H 0COOK + M n 0 2 + 2 K 0CO 3 + K H C O 3+ H20

C H 3C H 2CO O K + HC1 - C H 3C H 0COOH + KC1

*) C H , CH = CH 2 C1500 ^ CH 2C H = C H 2^ aQH> c h 2c h = c h 2 m .

Cl OH
[O
CH 3CH 2CH 2 * CH 3CH2COOH

OH
m H O 1/OH' [O]
*) C H = CHi (C H A k O ty jB A - CHjC B C H jOH CHHOOH
-H3BO3

2. iu c h C H 3C H 2C H 2COH
q v ch2

*) C 2= CH 2 ----------------------------------------------------------- *> CH. a ! 2M g C l-- ~ CH 3CH 2CH 2CH2

[O]
-----*> CH 3CH 2CH 2CH2OH V CH,CH 2CH2COOH

*)CH,CH 2CH 2C I - M i L ^ CH,CH 2CH2MgCI - 2,t CH,CH 2CH2COOMgCI HCi

-MgCl 2
----- CH 3CH 2CH2COOH

3. iu c h C H 3C H 2C O C H 3
On, t , XI CH 3CH2MgCl H a
C H t= C H 2 CH 3C H O ------- CH 3CH 2C H OMgCl

C u O , t CH3
c h 3c h 2c h OH - -- c h 3c h 2c c h 3
I li
C H -1 o

K in thc m r n g
Phn ng ca hp cht c magi.

R -X + M g * R - MgX X: H alogen
1. Phn ng vi hp cht c nguyn t H linh ng. Thu c hirocacbon.
5 5+ + 5-
R M gX + H ----- RH + M gX A
HA: H O H , RO H , RCOOH, RC = CH, N H 3,...
2. Phn ng vi halogen. Thu c dn xut halogen khc.
121
 CH c CHIC! - * CH c CH2MgCl -=-*CI-I3 c CH2I
I ete I -MgClI I
ch3 ch3 ch3

3. Phn ng vi oxi. iu ch ru.

CH 3CH2MgBr CH 3CH2OOMgBr C-H - - Mg-S - C2H5OMgBr C\I 1,011

Etyl magi bromua
4. Phn ng vi CO.). iu ch axit tng 1C.
' + +f \ 5 ~ ete H 20 /H +
CHr- MgBr + O c = = 0 CH3 COOMgBr CH3 COOH
-Mg(OH)Br
5. Phn ng vi etylenoxit. iu chancol bc 1 tng 2C,
~ + s+ [ J O / I [+
C H r - M g B r + C H 2------ - r u , ---- CH 3CH 2CH2-OMgBr CH 3CH 2CH2OH
X s v ' -Mg(OH)Br

Vi dn xut ca etylenoxit:
5- + _ "+ +
C H r MgBr + CH2------ CH*CH} CH,CH 2CH OMgBr
X x I
H 0/H + 1
2 *. CH 3CH 2CH OH
-Mg(OH)Br
CH,
6. Phn ng vi anehit, xeton.
R R
5- + \5 + \ HiO/IP I
CH**MgBr + c=b= CH3 OMgBr - - CI OH
Ry I -Mg(OH)Br I
R' R'
H C H O - Ancol bc 1 t n g 1C.
Anehit khc -*Ancol bc 2.
Xeton - A ncl bc 3.
7. Phn ng vi este.
5- R|

S" + l o ______ , ,
R *IVlgX + R> c *. R C O - M g X * R C R 1 + R2OMgX

^ OR v* 2
vi..
Xe ton

dR M *X R OMgX ' w l > R - C - O H

] -MglOIDX I
R R Ancol bc 3
122
 Tng t vi clorua axit:

cP ~ ^
R__M gX + R ' c *- R c o MgX R c R 1 + MgXCl

x c, 4 , i
I Xe ton
R' R
1+
d RMgX R Q OMgX H"0 /H ^ R c OH
I -Mg(OH)X 1
R R Ancol bc 3

Bi s 7 .2

1 . H y so s n h tn h a x it c a a x it 5 - b ro m v aleric v a x it 4 - brombixiclo[2.2.2]
octancacboxylic. G ii thch s so s n h .
2. A, B. c , D. E l n h n g a x it xiclobutan icacboxylic ng p h n ca n h a u . A
d d n g m t nc to a n h i r i t ni p h n t. B t o a n h i r i t k h i u n nng. Khi un
nng, c b t c h loi CO. T ro n g cc diu k in tr n D, E k h n g c h i n tng g.
Xc n h c u tr c c a cc a x it trn.

Bi gii

1 . T n h axit:

Br<-C*CH2^ - C H - ^ C*-COOH > B r ^ - C H ^ C H ^ CH 2^-CHi-*-COOH

Vi hai a x it t r n k h o n g cch t Br ti nhm - C O O H u cch 4 nguyn t c

no. a x it 4 - brom bixiclo[ 2 . 2 . 2 ]octancacboxylic B r h t electro n th eo 3 con ng
m n h hdn a x it 5 - brom valeric, Br h t electron th eo 1 con ng (yu hn).
Ngoi r a a x it 4 - brom bixiclo[ 2 .2 .2 ]oetancacboxylic d n g vng n n c nh, cn
a x it s - b ro m v aleric c c u tr c m ch k h n g p h n n h n h n n t o ra m t c u d n g
m p h n m n g in tch (-) tr n n g u y n t Br c t h g n n h m - CO O H lm k h
n n g p h n li H + gim .

8 s+
^ B r HO
CH 2 V = o

c f2 ch2

2.

A d d n g m t nc to a n h i r i t n n A l:

Hty HVBTHHOUC 123

 H

+ h 2o

Axit cis - xiclobutan - 1.2 - icacboxylic

B to a n h i rit khi u n nng nn B l:

H H

H
H2o
o
o
Axit cis - xiclobutan * 1,3 - icacboxylic o

Khi u n nng c b tch loi C9 nn c l:

COOH

COOH t0
+ c

(C)
Axit xiclobutan - 1,1 - icacboxylic

Do khi c nhm h t electron lin k t vi nhm - COOH th hp c h t d b

ecacboxyl ho (tch loi COo).
D, E kh ng c cc tn h c h t tr n n n l:

COOH COOH

Axit traits - xiclobutan - 1,3 - icacboxylic Axit trans - xiclobutan - 1,2 - icacboxylic

Kin thc m rng

Phn ng ecacboxyl ho.
Axit fomic b phn hu to oxit cacbon v nc khi un vi axit H2S 0 4 m c.

HCO O H H s 4 .t co + H Q

124
 Cc axit no kh b ecacboxyl ho: cn nhit phn mui cacboxylat vi vi ti - xt.

RCO O N a + N aO H -----* R H + N a 2C 0 3
Khi v tr i vi nhm cacboxyl c nhm ht electron nh cc axit CCI3 - COOH,
HOOC - CH2 - COOH,... thi phn ng ecacboxyl ha xy ra mt cch d dng v m du.
ang ch V l mui bc ca axit cacboxylic d b ecacboxyl ho khi c mt ca clo
hoc brom to r dn xut halogen tng ng (P h n n g H unsdiecker).

C6H5 CH2COOAg + Bi 2 .( --4 C6H 5 CH2Br + C02 + AgBr

76c
Phn ng Hunsdiecker ng dng tng hp dn xut halogen hoc tng hp axit c
cha Nc nhm cacboxyl.
Ag2 , ^ Br2 _ M2 _ l4C 0 2
R COQH " R COOAg R Br R MgBr .. -

R - l4COOMgBr R - l4COOH

Bi s 7.3

Cho m t dy axit: C H 3C H 2C H 2CH 2COOH (A)

C H 3C H 2C H B r CH 2COOH (B)

C H 3C H 2C H 2C H B rC O O H (C)

C H 3C H B rC H 2C H 2COOH (D)

C H 3C H 2C H B rC H B rC O O H (E)

C H 3C H 2CH C1CHC1C00H (F)

C H 3C H 2C H C lC H B rC O O H (G)
1 . Sp xp cc a x it tr n theo chiu t n g d n tn h axit.

2. T A h y iu c h cc axit cn li.

Bi gii

1. Clo v bro m u c h iu ng -I v clo th h in h i u ng h t electron m n h hn

brom. H iu n g -I n y gim s t n h a n h khi ko di m ch ch u y n n h hng. Do
chiu t n g tn h axit l:
<A) < (D) < (B) < (C) < (E) < (G) < (F)
2 . iu c h cc axit.

125
 Br,, p
CH3CH2CH2CH2COOH CH3CH2CH2CHBrCOOH
(C)
KOH/ru_ Bri/CCl^ __ , ,|| p i j __f '11__ f ' V"1
(C) ----- CH3CH2CH = CH COOIi - * CH3CII2CH CH CQOH

Br Br (E)
HBr
CH3CH2CH = CH CCX)H * CH3CH2CH C H fCOOH

Br (B)

CH3CH2CH = CH COOH CH3CH2CH CH COOH

CI Br (C.)
CH3CH2CH CH COOH ^ 2 . CH3CH2C H -C H - C O O H

Cl Cl (F)
CH3CH2CH2CH2COOH askt*> CH3CHCH2CH2COOH

Br (D)

Kin thc m rn g
Phn ng halogen ho gc ankyl ca axit cacboxylc.
Cht phn ng l Cl2, Br2 vi s c mt ca p ch xy ra phn ng th v tr a i vi
nhm cacboxyl (c ch ion).

e n g - C H 2 - CM 2 - COOH + B r2 > C H 3 - C H 2 - C H B r - COOH + H B r

Qu trnh phn ng din ra nh sau:

2 P + 3 B r 2 -> 2P B r3

R C H 2CO O H + P B r 3 -> R C H 2C O B r + P O B r + HBr

Axyl b ro m u a

H+
R CH? c Hr R CH = C Br ------ R CH c Br
Il Rr3 I ' HB I i
o Bt O
Br H OL - Bromaxyl bromua

R CH c Br + RCH2COOH R CH c OH + RCH2COBr
i i I
Br O Bro

Phn ng cio ho axit theo c ch gc (tng t phn ng clo ho ankan) xy ra ch yu

cc v tr v Y d o ngu yn t clo c tnh electro fin

126
 5%
--------- * CI C I 12 C I coon
IC1
c I7, askt 64%
CH, C H r C 1 2 c o o i i C H , C H c n 2 C O O I

1
31% Cl
C l 1 , C \2 c\ l COOl l
1
C1

Bi S 7 .4

Axit cacboxylic A (C 5 H 80 9) tn t i h a i d n g ng p h n l p th Aj v A.>.

Ozon p h n A th u c a n e h i t axetic, a x it 2 - oxopropanoic. K hi h i ro ho xc tc
trn c A v Ao u cho a x it B (raxemic).
1 . Xc n h c u tr c c a Aj. Ao v gi t n chng.

2. Vit cng th c chiu Fis c a B v ch r c u h n h .

3. Cho t n g n g p h n Aj, Ao tc d n g vi C1 - Br. V it cng th c c u tr c ca
s n p h m to th n h .
4. T 1 - b u te n h y v it cc phng t r n h p h n n g iu c h B.

Bi gii
ozon phn
1 . A CH3 c h o + 0 = c COOH

CH 3
A c 2 n g u y n t o n n A l a x it dn chc. A l:
C H , C H = c COOH
L
ch3

Aj, Ao l ng p h n h n h hc:

CH 3X cooh CH, CH 3
\ __ /
c = c c = c
/ \ / \
H CH 3 H COOH
A, a2
(2Z) - 2 - metyl - 2 - butenoic (2E) - 2 - metyl - 2 - butenoic
(dng trans) (dng cis)

Ni
2 .CH 3 C H = C COOH + H2 CH, C H y -C H COOH
L 1*
CH, (B)
CH,

127
 CH, COOII H H COOH CI COOH
cu V.

/ c= c v .. + I I - H - ; c - c ; +
H ch3 h c \ M

B in th r a x e m ic

COOH COOH
H < 51 CH 3

c 2h 5 c 2h 5
A x it R-2 - m c ty lb u ta n o ic A xit s - 2 - m ety lb u ta n o ic
Bi
5* j y \ C
V /p 5; +
3. CH3 C H ^ C ^ - C + CI Br ------------ CH3 *CH C COO1
f\ \ cng trans
OH
ch3 C1 CH

COOH COOH
c h 3x cooh
Bi CH3 H3C -B r
c= c + Cl Br -----
/ \ H C1 C1 -H
H CH 3
A, ch3 CH 3
COOH COOH
CH
\ _ / CH Br CH 3 H3C -B r
+ Cl Br
, / c\ C1 H H -C 1
H COOH
^2 CH 3 CH 3

4. CH3 CH2 CH = CH 2 + HBr CH3 CH2 C H Br

CH,

128
 CH, ete
Cl I3 CH2 Cl 1 MgBr + 2 V CH 3 CH 2 C H COOMgBr

CH, H+ CH,
CH , C H C H COOMgBr + 2H20 CH3 CH2 H COOH
I 1
CH, CH, (B)
+ Mg(OH)-> + MgBr 2

Bi s 7.5

Gi tn v vit p h n g t r n h p h n n g xy r a k h i u n n n g h i ro x ia x it mch
th n g c cng th c C j H jqO o.

Bi gii

Cl - CH C 12 CH COOH CH3 CH2 H C H t - c o o h

OH OH
Axit a - h iro xivaleric Axit p - h i ro x iv aleric

c h 3 c h c h c h c o o h c h 2 c h CII 5 C H j - COOH

OH OH
Axit y - h irox ivaleric Axit - hi ro x iv aleric ,
1 . a - h i ro x ia x it khi d u n nng th ng hai p h n t a x it t o e s te vi n h a u gi l
lactit.

C-f-OH HO c -------------- o
/ : .......* \ f0 / \
C3H7 CH + HC-C3H7 ^ C3H7 CH HCC3H7 + H20
X dH oA c/ Xo c
...... l l
o o
2 . - h i ro x ia x it khi b u n nng t o t h n h axit a , p - k h n g no.

c h 3 c h 2 c h c h - c o o h c h 3 c h 2 c h = ch CXX)H + h 20

OH
3. y- hoc 6 - h i rox iaxit k h i b u n nn g to e ste ni p h n t (lacton).
 / c h 2 c h 2 CH 2 c n 2
/ \
CH, CH Nc = 0 CH, CH c = 0 + HiO
\ r;............/
H lio i
I----. . . . . . . . . . -

y - L a cto n

r ......... -
c OH c
UJ .
CH ch2 o
o
I + h 2o
ch2
CH
\ 2 / ChHi 2 /
'H

ch2 ch2
- Lacton

Lu :
Lacton cng d dng c to thnh khi cho axit p, - hoc , - khng no tc dng vi
axit mnh.

Bi s 7.6

Khi cho iso b u ta n a l tc d n g vi axit m alonic khi c m t p iri n th u c hp

c h t A. un nng A tro n g mi trng ax it thc h in p h n n g ecacboxvl ho
th u c hai s n p h m Aj v Ao l ng p h n c a n h a u .

A , H i . A 3 - }- L As, Afi (A5 bn hn)

A| * > A 4( h p c h t no)

Bit r n g A 9 khi b oxi ho to th n h ax it oxalic. Aj l lacton.

Xc nh cu to c a A j......Ag v vit cc phng trn h p h n ng.

Bi gii

CH CH
\ COOH
Piriin \ ............. / C O O H
/ C H CHO + CH2 ^ CH CH CI i r
CH/ ^CO O H
ch/ T COOH
H (A )

CH 3 CH 3
rt0 \
~ .CH CHC11 , c o o n
/ COOH ' LAJ2 /
CM CH/
OH OH

130
 -------
\
CHi CH CH=CH c o o n
\ H+,t CH { (A,)
CH CHCH2 COOH
-h 2o CM3.
CH \
OH c = CH CHj COOH
CH

CH3 ch3
\ [0 ] w \ /
^ V

CH," ch3

CH CH
CH3
\ H+ c CH

c h 3/ o-
o (A.)

c h 3\ ch2
^CH-> CH3
ch3 LAIH4 \
c CH2 CHjCl \2
o /
CH
o OH (A3) OH

\ CH>
0
c< X CH2 n //
CH tfC H 3
^ ' - a ^ - C H r
(HO) o c ^ . Q l/ I I
o-
08 -
(Xc h ^ a (Aj) OH

CH
c = CH C H rCH2 + H20
ch3
\ H 3PO4
^ c CH2 C H t-C H 2
CH<
OH (A 3) OH + H20

18-MSCHVBTHHUC 131
Bi s 7.7

Hp c h t A(C 9H 10O) phn ng vi dung dch N a H C 0 3 gii ph n g k h CO).

A khng lm m t m u dung dch nc brom, kh ng p h n ng vi C H 3OH khi c
m t H 2S 0 4 c. M t kho khi cho H 9S 0 4 c vo A, sau cho h n hp vo
C H 3OH c lm lnh th c hp c h t B (CqHpO). Hy cho b it cng thc
cu to ca A.
Gii thch cc tn h c h t trn ca A v s to ra B.

Bi gii

A: CgHO p h n ng vi N a H C 0 3 gii phng COo nn A c h a nhm - COOH.

A khng lm m t m u dung dch nc brom nn A cha vng benzen.
A l ax it m k h n g p hn ng este ho vi C H 3OH nn A phi c n ng khng
gian nhm - COOH ln, do A l:

S to t h n h B:

o
//
o
on

( c n g m t mt phng)

o
"1/ /

0CH3
(B)

Bi s 7.8

Hp c h t n chc A c cng thc n gin n h t l C 3H 60 v c tn h q u ang

hot. un nng 23,2g A vi mt lng d dung dch NaOH, sa u ngui ri lc
hn hp t h u c vi imetyl ete. Tch ly p h n lp trn ri ch n g ui ete
th th u c 14,8g c h t lng c tn h q uang hot. Lp bn di kh ng c tn h
q u a n g hot.

132
 Gi s h iu s u t p h n ng l 100 %.
1 . Xc n h cu to ca A v vit phng trn h p h n ng.
2. C n c vo kt q u th nghim hv cho b it c ch ca p h n ng.

Bi gii

1. V A c tn h q u a n g h o t n n A phi c cng th c p h n t d n g ^3n^6n^2n

n > 2 (n = 1 th c h t kh ng c tn h q u a n g hot). M t k h c A tc d n g vi d u n g dch
NaOH cho c h t lng t a n tro ng ete v A n chc n n A l este n chc v c h t
lng ta n tro n g e te l ru.
> n 2. A: CgHjoO>>.
23 2
A c dng: RCOOR'. n A = = 0,2 mol.
A 116

RCOOR' + N aO H -> RCOO Na + ROH

0 ,2 mol 0,2

0,2(R' + 17) = 14,8 -> R' = 57(C 4H 9).

R'OH c tn h q u a n g h o t nn A l:

CH, CH 2 CH o c CH 3
1 li
ch3

CH3 CH2 ch o c ch, + NaOH CH3 CH2*CH OH + CH3COONa

1 l 1
CH, 0 ch3

T a n tro n g ete
2. C ch:

CH, CH2 CH l c CH3 +0OH *> CH, CH2 CH O CH3

ch3 0

c h 3 c h 2 c h + c h 3 c c h 3 c h 2 c h O H + C H 3C O (

OH 1
CH

Bi s 7.9

t - B utyl a x e t a t tc d n g vi d u n g dch n a tr i m e ty la t tro n g m etanol bin th n h

m etyl a x etat; p h n n g chy 10 ln ch m hn so vi p h n ng tng t chuyn
etyl a x e ta t t h n h m etyl a x e ta t c tin h n h tro n g iu k in n h n h a u . Ngc li
t - butyl a x e t a t p h n ng n h a n h vi C H 3OH tro n g s c m t ca m t lng nh

133
niro clorua to ra axit axetic v metyl t - butyl ete. Tng t etyl a x e ta t li chuyn
r t chm t h n h etanol v m etyl ax etat.
1. Hy vit c ch p h n ng gii thch Lc h nh t h n h s n p h m .
2. C th s d n g ng v 180 n h t h no k h o s t t n h n g n ca crt
c h c ngh trn .

Bi gii

o5 CH
H} o I 3
X 0 - - C H , + CH,oe ^ - C H , - c ( + % - C - C H , (chm)
on cr nh .3
ch 3
ch3
Do n ng k h n g gian ca gc t - butyl ln.

O ~ /O
C H 3 C ^ + c n 3 o0 - H p C H 3 + C 2H 0 (n h a n h h n )

OC 2H 5 och3

0 CH- o <FH3
c h 3 c ' IH n
x o - c - c h 3 + CH 3OH CH3- c ' + H 3C - - O C H 3

H OH CH 3 (n h an h )

/ //
CH3 Q + C H 3OH HC1" C H 3 + C 2H 50 H (chm )
OC 2H 5 OCH3

C ch:
cO

C H . C
+ c h c P 3 ^
I
c h 3 c ( ^ o r ---- * -C H 3 c C
/
+ RO0
v \ _ _ y /Y ' \
XO R / ' 1' OCH3
CH3 3
N u R l gc t - b u t y l t h c n n g k h n g g ia n l n , p h n n g k h n g x y ra
h o c x y ra c h m . N u R l g c n h n h - C9H5 th c n n g k h n g g ia n n h , p h n
n g x y ra n h a n h .

134
 18 * '
D ng o k h o s t c ch:

// *
1,o t CH3 c RO
\*
O R o
//
Hoc 18O C H 3OH CH, c
\*
OCH,

N u t 180 C H 3O ' th theo c c h tr n nguyn t oxi b n h d u s chi

trong nhm m etoxi ca e ste dc to ra.

.0
__ // # D
CH, c CH3 C CH3 + R
o R oR OH
H
R@ + CH, H = CH3 O R H+ + CH3 O R

H
C acbocation bc cn g cao cn g bn, cng d to ra. Nu R l t - butyl th
cacbocation t o r a bn. R l - C 0H 5 th C H 3CHo+ khng bn kh to ra.

OH OH

_ c '
I ..
CH , + H+ CH3 C / CH , c
R O -R
O R
H H (..OH
L
I A e I .. S
C H j-c T t = = i CHJ - - o - c 2H5 ------ C H , - - o- C 2H5
^ 5 - r I I -H* I
OR H OR
//
c h 3- c ; + RH
OCH3

Bi s 7.10

Cho s p h n ng:

O la C H = C H C O O C H = C H CH3^ -S -2 Bd-d Na c+ D
(A) 1 :1

1. H y cho b it cng thc c u to cc s n p h m tr n v t n gi ca A, B, c, D.

2 . Cho b i t loi c c h ca cc p h n ng trn.

135
 3. Hy ch r cc dng p h n lp th ca A, B, c, D c bao n h i u loi ng p h n
lp th?
4. Nu t cho A c cu h n h bn n h t th cu trc c a B n h t h no?
5. Cng t cho A cu h nh bn n ht. Tin h n h p h n n g gia A vi D/Ni,
L A1H4. Cho bit cu tr c cc s n phm to th n h .

Bi gii

O i. / ae
1.2. CH, C H = = C H *-C ' + Br2
o C H = C H CH3
,0
//
----- CH, C H = C H CN
O CH CH c ,
B
(B) I
Br Br*

O O
// t
CH3C H = c h c ' + 3 NaOH - CH3 C H = CH c '
o CH CHCH3 S" 2(CO) ' ONa
I I (C)
Br Br CH 3 C H -C H O + 2 NaBr + H20

h (D)

A: (1 - propenyl) - 2 - bu ten o at; B: (1,2 - ibrom propyl) - 2 - b u te n o a t;

C: N a tri 2 - b u te n o a t. D: 2 - H iro xipropanal.
3. A c 4 ng p h n h n h hc v c hai lin kt i.

ch3 coo ch3 c h 3. coo h

.> = < >=</ V / Nc = c /
H h h h xh h / n ch3
cis - cis cis - trails

" C^
v C\\ A / =c K/\ f f l l Hw
J^ c = c ' c ; c =-----
= cv_-, ' H
C H3^ H
H UH .1
H rCH
u 3. ^ .. . hs H
CH 3
trails - CIS trails - trails

B: C 8 ng p h n cu hnh;
C: C 2 ng p h n cu hnh;
D: C 2 ng p h n cu hnh.

136
 H coo
4. K kiu gc x l OAc

cur II
Ta c:

II Br
\ H / OAc
Br
c OAc
Br H,c H /\T ~ O A c
CH C -H
cng trans
1
H Br

OAc OAc
H Br Br H
H Bi Bi H
CH CH
--------V -----------

Erythro
5. A + D.,(Ni) - 4 ng p h n cu hnh:
o o o o
o c o o o
D D D D D D D D
D D D D D D D D

CH 3 CH CH CH CH CH CH 3

H coo
\ / \ / H l a ih 4 h c h 2o h
c= c c= c * c= c + CH 3CH2CHO
rH / \ / \
3 H H CH, CH 3 Vh

Bi s 7.11

Vit cc p h ng tr n h p h n ng v gi t n s n p h m cui cng.

K CNd H 20 /H +LiAIH4 d HBrd KCNd

Br (CH2) Br * A B --- c ------------ D
l i hon ton
H 20 /H + C 2H5OH C2H5ONa H 20 /H + L 1AIH4 d
E r G -=1 H I --- J
hon ton H2S 0 4 dc -C 0 2
HiS0 4 m c CH 2N 2
___: L M

137
 B i gii

KCNd J ..................................... 0 /H +
H2O/H
)v Br - i iz . N -=
Br (CH12j)r- S cC- ( C( QHi 2)3
2)3- C -= = N - t fIO I O C -(C J 12) COOI
z hon ton '
(A) (l)
Li AI H4 d
* HRrdir _ K
-CH2 (CH2)3 CH 2 - 1 CH2 (CH2)3 )3 CH2c h 2-KCN d^ NC(CH2)5- CN
1 1 - h 20 1 I
OH (C) H Br (D) Br (E)

H^ 'i H O O C -(C H 2) COOH C^ OH C 2H 5O O C - ( C H 2)5 COOC 2H 5

hon ton ^ HS04 c

C1 CH 2
CH
C2H5ONa 2V
- h 2o / h + H2 c h 2 LiAlH4 d
H ,c c= o -c o 2 h 2c ^ ^c= 0 OH
CH CH

COOC2H5 (H) (I) (J)

H9S04 m c CH2N 2 , nn
___ -- > Bixoclo[4.1.0]heptan
-N2
(!) (M)

Kin thc m rng

1. Phn ng ngng t este (ngng t Claizenj
C2H5ONa
CH3 c OC2H<; + H CH2 c OC2H5 ; ; CH, c CII2 c OC2H5
hoc Na II
o o 0 o
+ C 2H5OH
C ch phn ng ngng t Claizen tng t phn ng cng anol.
(* 0 8 -
_ ___ ^ CH 3 5C/

H CH2 c OC2H 5 ec n 2- c OC 2H5 ---------------- Q

r II -C2H5OH II
Sd e ) 0

CH, c J ^ o c 2H5 CH 3 c c h 2 c o o c 2 5
c 2h , o
c h 2c o o c 2h 5 0

Este cn c th ngng t vi xeton to ra p - ixeton.

C H - C o c ,i + H c h 2 c c 6h 5 C H , - C c h 2 c CftHs
-C2H5OH
o o o o
Axetophenon Axetylaxetophenon
138
2. Phn ng an kyl ho este ca axit m alonic
COOC2H5 _ C00C2H5 c o o c 2h 5
C2H,ONa / RHal /
cu; I 5 . CH R CH
____ hoc Na \ _____ U10 \
COOC2H5 COOC2H5 "Hal COOC2H5
ietyl malonat
Cc este a n kylm a lo n a t d b th u p h n trong mi trng axit, ri b ecacboxyl ho bi
nhit to ra a xit monocacboxylic.
COOCoIs COOH
R CH 2- K - C t < R C H - C O O H
\ \ -CO 2
COOC 2H 5 cooh

Bi s 7.12

T a x it iso b u tir ic hy v i t cc phng tr n h phn ng i u ch

a - m e t o x i is o b u t a r a m it (c h c n g t h m c c c h t v c v c c i u k i n p h n
n g c n th i t).

Bi gii
CH^
o , I 3 O
CH3 CH c + Br2 CH3 C c f + H20
I \ I \
u OH * Br
? " 3 /
CH, C C / + 2CH3O N a----- CH, C c + 2NaBr
I N I \
Br B' OCHj
f < y - 0
I ht/ __ I
CH3 C c n h 3 c h 3 C c + CH3OH

och, M S ^ OCH X n h ^

i u c h C H 3O N a

// 2NaOH
CH3 CH . - CH3 CM2 CH3 + N a 2C 0 3 + H20
I OH C a 0 t0
CH3
c h 3 c h 2 c h 3 -Cracking> c h 4 + c h 2= c h 2

c h 4, ^+ Vyl2
Clo askt t> V
CHoCl
jfl3 + HC1
CH3CI + NaO H -> CH3OH + NaCl

2 C H 3O H + 2Na -> 2 C H 3O N a + H o t

139
19-MSCHVBTHHUC
Bi s 7.13

1 . Xc nh cu to ca E to th n h tron g phn ng sau:

Br,
(CH3)2CHCON 2
NaOH

Cho bit c c h ca p hn ng trn.

2. (S) - 2 - m e ty lb u ta n a m it tc d n g vi Brv> trong N aO H th u c (S) - sec
b u ty lam in. H y gii thch s to t h n h sn phm trn.

Bi gii

O
l.CHy CH c + Br2 + 2NaOH CH3 Cl CH3 + 2NaBr + C 0 2 + 20

I NH2 In h 2 (E)
ch3

C ch: P h n ng Hpm an

CH CH_ C^ C H CH C ^ Q - ~ + C l CU C ^ .
3 ? ^N H H2 I NH 'Bi 1 ^ NI

CH 3 I CH, CH Br
H

n r yO o 0 -,
OH
c h 3 CH c.
- c h 3 c h c '
/
____________
-H20 < K :e N
L 3 0 3 J
CH 3 C H - r C ^ * 0 = C = N CH CH3 0 = c NI CH CH 3
\ ND '
ch3 V 3 ch3 oh ch3
Isoxianat
* CH 3 c h nh2
-co2
ch3

c h 2c h 3 c h 2c h 3
%H
-I 20 *'

o ^ C^ n h 2 o NHBr
(S) - 2 - metylbutanamit

140
 T rong s ch u y n ho c a s n p hm tr u n g gian (I), s t lin k t c - c v s
to t h n h lin kt c - N xy ra ng thi nn cu h n h ca s n p h m c gi
nguyn.

Bi s 7.14

T nhm cac b u a v cc c h t v c cn th i t hy iu ch:

ch3 c o o c 2h 5

Bi gii

1. A14C 3 4- 12H20 -> 4 A 1(0 H)3 + 3C H 4

2CH4 1500c > CH H CH + 3 H 2T

2 CH = CH -... Cu-(-1NH^C1 > CH = c - CH = C H 2

CH = c - CH = C H 2 + H 2 C H 2 = CH - CH = C H 2.

C H 2 = CH - CH = C H 2 + 2 H B r - -pe0Xlt- > Br - C H 2 - C H 2 - C H 2 - C H 2 - Br

B r-C H 2-C H 2-CH 2-CH2-Br + 2 N a C N N C-CH 2-C H 2-C H 2-CH2-CN + 2 N aB r

 o
//
h 2 c h 2 c n CH2 C H
H
+ 4H20
c h 2 c h 2 c n ch 2 d i r - c

o o
c h 2 c h 2 H 2 C H ,
OU \
c= o + co2 + h 2o
OH
C H 2 C H , c c h 2 c h 2
o
Pci
CH = CH + H. ch 2= ch 2
c h 2= c h 2 + h 20 2 CH2 c h 2

OH OH

HO CH2
/ O-
o + + u 20
HO CH O-

askt
2. C H 4 + 3C12 CHCI3 + 3 H Cl
H'
CH2 = CH2 + HOH CH 3C H 2OH
2 C H 3C H 2OH + 2 Na -> 2C 2H 5O N a + H 2t
CH CI 3 + 3C 2H 5O N a -> HC(OC 2H 5)3 + 3NaCl
OC 2H 5 o
/ 2 5 r-A / O C 2h 5 //
o + H c O C2H 5
- X + H \
o c 2h 5 OC 2H 5 O C 2I I 5

3. HOOC - (CHo) - COOH + 2PC1 5 -> 0C1(CH 2) 4C0C1 + 2 POCI 3 + 2HC1

0C 1(C H 2) 4C0C1 + 2 C 2H5ONa -> C 2H 5O CO (C H 2) 4COOC 2H 5 + 2NaCl

c h 2 COOCJH, n c h c o o c 2h 5
/ - CH COOC 2H
CH CH3ONa CH H-)C \

Uf
---- ---- c= o
ch2 -CH3OH ch2 h 2c ^ /
\ _____
CH 2 C O C K 'S
\
cn7c ch 2

OC 2H 5 + C 2H5ONa
COOC2H;
c 2h 5o c o ^ ch 3
/
CH COOC 2H*55 N
I \- c r
HlC \ = o ' CH3Na H2C^ \
c= 0
5
c h 3- * I \c = 0
H->C / CH 3OH /
CH
HiC H2C /
CH CH 2 + Nal
142
 iu c h CHgONa v C H 3 OH

C H 4 + Cl 2 > C H 3CI + HC1

C H 3 CI + N aO H - C H 3 OH + NaCl

C H 3OH + HI -* C H 3I + H 20

2 C H 3OH + 2 Na -> 2 C H 3O N a + H 2t

Bi s 7.15

Hp c h t A l este. A c to bi ax it X v ru Y u l n h n g hp c h t no
mch h. T ron g p h n t A c cha hai vng c lp (t 6 c n h tr ln).
A c cng thc n gin l (C n 25^13 75O 7 5) 11- Xc nh cng th c cu to ca
mt este n g vi X v Y .

Bi gii

A: (^11,25^13,7507 5)n h a y c u 25nH 13 75n0 7 5n

A: c 7 5nH 13 75n(COO )3 75n.

M t k h c X v Y u l no v A cha hai vng c lp nn:

[2(7,5n) + 2 - 2.2] = 13,75n

-> n = 6 . A: C 18H 9<;Or , hay C r ,Ho 2(COO)6.

X : R (C O O H )n
t ; ta c:
Y : R '(O H ) m

m R(CO O H )n + nR'(O H )m -> Rm(COO)mnRn + m n H 20

m n = 6 . Do A c c u to m ch vng nn axit v ru u p h i a chc.

m m = 3
hoc
n n = 2

m = 2
Chng h n , ta c A: R 3(COO) 6R '2
n = 3

3R + 2R' = 166

R 0 14 (C 2) 28 (C 2H 4) 42 (CgHg) 56 (C 4Hs)

R 8 3 ( C 6H n ) 62 (loi) 41 (C 3H 5) 20 (loi) <0

143
 C hng hn, A:(C,H j) 3(COO)fi(C 3H r))o
co o -cn
(CH2)
C O O -C H

COO CH,
(CHj )2
co o -ch 2

C O O -C H
(CH2k
C O O -C H ,

Bi s 7.16

T alyl clorua v cc c h t n g in h y v i t cc p h ng t r n h p h n ng iu
ch hp c h t (I). T glixerin iu ch hp c h t (II).
CH2 OCOCH 3 CH2 OCOC 6Hs

CH OCO QH 5 CH OCOCH 3

c h 2 o c o q h , \2 o c o c 6h 5
(I) (II)

Bi gii
CH2 Cl
HCIO NaOH
1 . CH 2= C 1 I CII 2 CH CH C i2 *> CH
I I - HC1 I /O
Cl Cl OH Cl CH 2 Epiclohirin
Cl 1 Cl CH O COCH 3 C l\2 o c o a i 3
H20 /II+ I CH^COONa I 2C6HsCOC1 I
- CH OH H OH - H OCOC 6H 5
; -NaCl I -2HC1 I
C H j- O H CH5- O H CH 2 OCOC 6H 5
CHj - O H C H ^O CHt- 0
I Q H 5CH0 , H+ I \_ CH^COCl I \
2. CH OH HO CM C H Q H 5 - Cl 1 , 0 0 0 - Cl I Cl IQ] 15
-H20 I / -MCI I /
C H j-O H C H r- O CH o
c n OH c h 2 o c o c 6h 5

CH OCOCH, .2C 6H?CQCi . C H OCOCH^

-C6H 5CHO I -2HC1
C H r- o h CH2 O C O Q 115

144
Bi s 7.17

T rong tin h d u hoa hng (ldng c hp c h t X c cng thc cu to n h sau:

C H OCX) (CH2)7 C H = C H (CH2)t -C H 3

Cl I o c o (CI 12)7 CI 1 = CH CI\ 2 Ci = CI 1 (Cl 12)4 c h 3

CI \ o c o (CI 2) l CI 3
1 . Hy cho b it X c bao n h i u ng p h n cu hnh?

2 . Cho X tc d n g vi Ho d (xc tc Ni). Vit cng thc cu to v gi tn sn

phm.
3. Cho X tc d n g vi C H 3O N a th u c 3 este metylic. Vit cng thc cu trc
v gi tn y 3 e ste .

Bi gii

CI 2 o c o (CI 2)7 CH CH (CH2)7 CH 3

I *CI 1 o c o (CI 2)7 c h = c h c h 2 c i = c h (CII 2)4 CH 3

C 112 o c o (Cl 2) ! c h 3

X c 3 ni i c = c nn c 2 3 ng p h n h n h hc. T rong p h n t c 1 nguyn

t c n n X c 2 ng p h n q u a n g hc.
-* X c 2.8 = 1 6 n g p h n cu hnh.
2 . Sn p hm l:

CH2 o c o (CH2) 1 CH3

CH o c o (CH2)| CH3

c h 2 o c o (c h 2) l( c h 3
Cilixerin trioctadecanoat
3. Ba este l:

CH3 (CH2 ) 1 6 - COOCH3 Metyl octaecanoat

c h 3 (CH 2 ) 7 ( c h 2)7 COOCH3

c=c'
H H (9Z) - Metyl 9 - octaecenoat

CH3 (CH2U CH2 x (CH 2 )7 COOCH3

X
H H H
X H H
(9Z.12Z) - Metyl octaeca - 9,12 - ienoat

145
Kin thc m rng
- Ch s a x it ca mt cht bo l s m iligam KOH cn thit trung ho axit t do
trong mt gam cht bo.
- Ch s x p h n g h o l s m iligam KOH cn x phng ho hon ton gam cht
bo (bao gm c axit t do v hn hp este ca glixerin).
- Ch s iot l s gam iot phn ng vi 100 gam cht bo (dng nh gi hm lng
ca axit bo khng no).
Cch xc nh ch siot
Thm IBr vo cht bo.

> = < + 'Br ------ * / ( _ ( p

I Br
Lng IBr d cho tc dng vi KI.
IB r + KI - KBr + I2
v chun 2 bng dung dch N a 2s 20 3 vi cht ch th h tinh bt.

I 2 + 2 NaS 90 3 - N a 2s 40 6 + 2NaI

Bi tp t gii

Bi s 7.18

Hp c h t A c cng th c p h n t C 4H 80 3 c tn h q u a n g h o t, t a n t t tron g
nc cho mi trng axit. K hi u n n n g m n h A c h u y n t h n h B (C 4H 60 2) k hng
qu ang hot, t t a n tro n g nc n h n g c n g to c d u n g dch c mi tr n g axit. B
p h n ng vi d u n g dch K M n 0 4 d hn A. Khi oxi ho A b n g a x it crom ic long th
A bin th n h c h t lng c (C 3HgO) c n h i t si th p , k h n g p h n n g vi d u n g
dch K M n 0 4 n h n g li p h n n g vi iot tro n g d u n g dch N a O H cho k t t a m u
vng.
H y cho bit cng th c c a A, B, c v vit cc ph n g t r n h p h n ng.

Bi s 7.19

1 . un nng axit 1,1,2 - xiclobutantricacboxylic t h u c h a i s n p h m h u c

A, B; trong A c khi lng p h n t hn B l 18vC.
Hy ch r A, B v v i t ph n g tr n h p h n ng.
2, T ietyl m a lo n a t h y v i t cc ph ng t r n h p h n n g iu c h a x it g lu ta ric
V?. axit sucxinic.

146
 Phn 8
AMINOAXIT

Bi s 8.1

1 . Vit ph ng t r n h p h n n g khi cho a x it a - am inopropionic tc d n g vi :

KOH, HC1, C H aI, etanol c ho ta n HC1, C H 3COCI, (CH 3C 0 ) 20 , H N 0 2, Cu(OH)2.

2. Vit ph ng t r n h p h n n g khi n h i t p h n cc a m in o a x it m ch khng p h n
n h n h c cng th c p h n t c ^OoN.

Bi gii
l.C H i CH COOH + KOH ----- CH, CH COOK + H20

NH: nh2
CH3 CH COOH + HC1 CH, CH COOH
1
nh2 NH3HCI
CHi CH COOH + CH3I CH, CH COOH + HI
I INH CH3
nh2
HC1
CH, CH COOH + C2H5OH CH, CH COOC2H5 + H20

nh2 ... nh2

CH v CH COOH + CH3COCI mCH, CH COOH + HCI

NHi NH COCH}

a - A m in o ax it tc d n g tr c tip vi a n h i r it axetic h a y axetyl clorua to

th n h azlacton.
o o
CH, CH COOH 2S CH, CH c CH, CH c
pH r \ o
nh2 NU
/
o
* / CH,
CH, CH ^c o HO
-H O N />

CH,

20-MSCHVBTHHUCO 147
 CH} CH CQOH + HN0 2 CH3 CH COOH + N2 + H20

NH OH

V - o J ? - c /C H '
C
2CH CH COOH + Cu(OH)2 / \ + 2 H20
/C H -N O -C ^.
nh2 c h 3" H2 ^ 'o
Phc cht m u x a n h ( g i n g nh p h c c a
g lix e r in v i C u ( O H ) 2 )

2. P h n ng n h i t p h n c a a m in o a x it
+) a - A m in o ax it t o ixetop ip erazin.

li
C,
CH,CH2-Hcr 'NH
2CH,CH2CH COOH HN^ ^ C H CH 2CH, + H2
nh2 5

+) p - Aminoacit to a x it cacboxylic a , p - k h n g no.
............................ ........................t
CH3 CHCHj COOH *> CH3 c n = CH COOH + NH3

nh2

+) y-, 6 - A m in oaxit t o lactam .

,0 H2C----------- CH2
CH2CH2CHCOOH - I I + h 20
L
nh2
hn^ ^ h2

l
o - Lactam

Lu :
Phc ng vi glyxin (glicocol) c m u x a n h lam m v k h n g b p h n h u bi
N a O H m ch b p h n h u bi H 2S. p - A m in o ax it c n g t o phc h o n to n tng t
n h n g k m b n hn. -, S- A m in o ax it k h n g to t h n h cc hp c h t n h vy.

Bi s 8.2

1 . T hc h i n d y b in ho sau:
HCN NH3 HC1 long (CH 3C 0 )20
CH3 CH CHO A * B - c ------ D
1
ch3

148
2. Hp c h t A c cng th c C 3H 70 9N c tn h c h t lng tnh.
A p h n n g vi HNO.> gii phng N 2, vi e ta n o l/H C l cho hp c h t CH n 0 2N.
Khi un nng A cho c h t c cng th c C 6H 10OoN9.

Bi gii
HCN _ NH 3
1.H3 CH CHO -* CH3 ch ch CN V r CH3 ch ch CN
-H ,0
CH 3 CH 3 OH CH 3 NH 2
(A) (B) Q
2H 20(HC1) (CH3C 0)20 _ Ar
3 H CH COOH 3 CH3 H CH c f
-NH4CI I I -CHjCOOH I I \
ch3 nh2 -H->0 ch3 n o
(C)

CH 3 (D)

2 . A l hp c h t lng tn h , tc d n g vi HNOo cho No v c p h n n g vi C 2H 5OH

n n A l a m in o ax it.
Khi u n nng:

c 3h 7o 2n ^ 6^ 1002^2
n h vy h a i p h n t k t hp vi n h a u v loi r a h a i p h n t nc n n nhm
-N H 2 p h i v t r a . A l:

_______
CH, CH c '
I OH
NH 2 (Alanin)

/ /
CH 3 CH + HN0 2 ----- CH3 CH + N2 + H20

u " H

CH^ CH c f + C2HsO H ----- CH 3 CH c f + H, o

I \ _ I \ _ 2
I OH I n r.H .
NH 2
o o
CHi CH c
V
OH .0 CH3 H NH
H
r-V -% I
H H HN CH CH3
r if
NH
HO. o
N
S 'C CH CH3 2,5 - Dixetopiperazin
o
149
Bi s 8.3

1. P h n bit cc k h i nim: lin k t peptit, p e p tit, ip ep tit, trip e p tit, oligopeptit,

polipeptit, protein v proteit.
2. Gii thch cc hin tng sa u y:
a. Cho vi git d u n g dch C u S 0 4 v d u n g dch N aO H vo d u n g dch lng tr n g
tr n g th du n g dch ch uyn sa n g m u tm.
b. Cho H N 0 3 c vo du n g dch lng t r n g tr n g th th y x u t hin k t t a
trng, khi un si th k t t a chuy n sa n g m u vng.
c. Khi n u c an h cu a th y cc m n g r u cua ni ln.
3. Ch dng C u(O H )2 v c php u n nng h y p h n b i t cc d u n g dch: A lanin,
Glixerin, Glucoz.

Bi gii

1. P e p tit l n h n g a m it dc h n h th n h b n g cch n g n g t h a i h a y nh iu p hn
t a - am inoaxit.
Lin k t a m it gia hai n v a m in o a x it c gi l lin k t p e p tit.
s i-icil
Lin ktKCl pcpill
peptit >v

H2N CH c r NH CH 1 * NH CH c OH
1 II R" l
R o R' o o
n-2
Aminoaxit u Aminoaxit ui
Tu theo s' lng n v a m in o a x it (n) tr o n g p h n t m c ip e p tit (n = 2),
trip e p tit (n = 3),... O ligopeptit l n h n g p e p tit gm t 4 n 10 n v am inoaxit.
Khi n > 10 ta c polip eptit v th n g gii h n p h n t khi k h o n g 10.000 vC
(n < 50); nu p h n t khi ln hn th gi l p ro te in (hay protit).
Protein cn chia ra gm :
- Protein n gin l n h n g p ro te in k h i th u p h n h o n to n ch cho cc
a - am inoaxit. V d: a n b u m in (c tro n g lng t r n g tr n g , sa,...), g lo b u lin (c trong
m u, sa, lng trng,...), kera tin ca tc v mng,...
- Protein phc t p h a y p rotein lin hp (cn gi l p ro teit) l n h n g protein khi
thu phn, ngoi cc am in o ax it cn c cc t h n h p h n "phi pro tein " gi l nhm
ngoi. V d: nucleoprotein (nhm ngoi l a x it nucleic): p ro tam in ,... crom oprotein
(nhm ngoi l hp c h t c mu): hemoglobin,...

2 . Gii thch:

a. Do ion C u2+ to vi protein tro n g lng t r n g tr n g phc c m u tm bn

trong mi trng kim.

150
 b. H N O 3 lm gim s s o n v a t ho c a p ro tit lm cho n tch ra dng k t ta.
Khi dun nng H N O 3 s n itro ho vng b e n ze n ca cc gc a m in o ax it Phe, Tyr,.. to
dn xut p olin itro c m u vng.
c. Khi u n nng p ro tit b dng t t h n h k t ta.
3. un nng Cu(OH).? th u c CuO. Ch c a la n in tc d n g vi CuO to th n h
phc m u x a n h m . H ai c h t cn li u tc d n g vi Cu(OH).) to d u n g dch mu
lam m, n h n g kh i u n si cc d u n g dch ch c glucoz to k t t a m u gch.

CH2(CH)4CHO + 2Cu(OH )2 - - - CH 2(CH)4COOH + Cu20 + 2H20

o n OH OH OH

Kin thc m rn g
1. P h n n g m u b i u r e l p h n ng c trng ca lin kt peptit, hai nhm peptit to vi
ng (II) trong mi trng kim phc m u tm hoc tm (am inoaxit hay ipeptit khng
cho phn ng ny).

N (

CH /9 U
\ ^ /
c
*/

/
SJ

2. S k t t a p ro te in ; Mt s protein tan c trong nc to thnh dung dch keo l nh

c cc nhm phn cc (- NH<2, - COOH,...) trn b mt hp ph cc phn t nc to lp
v hirat. N hng yu t lm m t lp v hirat hoc lm trung ho in ca phn t protein
s lm cho cc phn t protein kt t li vi nhau v tch ra khi dung dch - l s kt
ta protein.
Kt ta thun nghch: Khi loi b cc yu t gy kt ta, protein li to thnh dung
dch keo nh ban u (chng hn cho dung dch (NH 4)2 ^ 0 4 vo dung dch lng trng trng
thu c kt ta bng ca globulin, khi loi b (NH4)2S 0 4 li thu c dung dch keo).
- Kt ta khng thun nghch: Khi loi b cc yu t'gy kt ta, protein mt kh nng
to dung dch keo ban u (s bin tnh protein).
kt ta khng thun nghch protein c th dng dung dch axit c nng cao hoc
un si dung dch protein...
3. C u tr c c a p r o t e i n
a. Cu trc bc 1: L trnh t sp xp cc n v amioaxit trong mch polipeptit ca
protein.
 b. Cu trc bc 11: L cu dng ca phn t protein gm cu dng xon a v cu dng
gp p c duy tr nh lin kt hiro gia cc nhm peptit khc nhau.
c. Cu trc bc III: L dng cun li trong khng gian ba chiu ca ton mch
polipepetit; cc nhm nguyn t k nc hng vo pha trong, cc nhm nguyn t a nc
nm trn b mt phn t.
d. Cu trc bc IV: Do hai hoc nhiu i phn t protein kt hp vi nhau to thnh
mt t hp protein kh ln.

Bi s 8.4

1 . Gi tn v vit cng thc h n h chiu ca trip ep tit: H - Ala - Cys - S e r - OH

2. H y cho bit cng thc chiu ca pen tap ep tit: 1

H Cys Ile Asn Cys Gly OH

NH 2
s s -

Bi gii

1 . H - Ala - Cys - S e r - OH : A lanylcysteylserin

COOH
o
H

o CH2OH
V ^N H - H

H,N H CH2SH

CH

o
H

2. o

o CHoCONH'
V -N H H

H,N H HCH-,
L
CH 2CH 3

152
Kin thc m rng
Tn gi ca peptit
Xut pht t u cha N, gi tn ln lt cc aminoaxit trong mch di dng gc
axyl v cui cng l tn amnoaxit u tn cng c.
- Gc ca aminoaxit R- CH(NH2)- CO- c gi tn bng cch i ui "in " thnh "yl".
H 2N - C H 2 - COOH HoN - CH 2 - c o -
Glyxin Glyxyl
H O C H 2 - CH(NHo) - COOH H O C H 2 - C H (N H 2) - CO -
S erin Seryl

P h l c 1. Hng s' vt l ca mt s a aminoaxt

--r-
Vit J.U or
STT A m inoax it Cng th c 1 ne* pH,
tt
CH2 COOH
1 Glyxin 1 Gly 233 6,0
nh2
nh2
1 2
2 L(+)-Alanin CH, C COOH Ala 297 6,0
1
H
NH2
c h 3v. I
3 L(+)-Valin ^ CH C COOH Val* 315 6,0
ch3 1
3 H
NH,
CH,V ' 1 2
4 L(-)-Leuxin* I* / CH - CHjC COOH Leu* 293 6,0
CH- 2 1
3 H
nh2
c h 3c h 2^ COOH
5 L(+)-Isoleuxin# Ile* 284 6,0
C H ," V
nh2
Axit 1
6 HOOC CH2
C
1 COOH Asp 270 2,8
L(+)-Aspactic
H
NH,
Axit 1 l
7 HOOC G H z- c h , - C COOH Glu 247 3,2
L(+)-Glutamic 1 2 1
H
H2N - (CH2)3- c h COOH
8 Ornitin Orn 140 9,5
NH2
nh2
1
9 L(+)-Lysin* H2N - (CH2)4- C COOH Lys* 225 9,7
H

153
 HN NH2
10 L(+)-Ariginin X C NH- (CI I C COOH Arg 244 10,8
/ 1
h2n h
H,N - C O - C H ,- CH COOl 1
11 Asparagin 1 Asn 234 5.4
nh2
NH,
1
12 L(-)-Serin CH, C COOH Ser 228 5,7
1 - 1
OH H
NH, H
1 - 1
13 L(-)-Threonin* C H r-C C COOH Thr' 225 5.6
1 1
OH H
NH,
I L
14 L(-)-Cystein CH, C COOH Cys 178 5,1
1 1 1
SH H
NH,
1
15 L(-)-Methionin* (CH,), C COOH Met* 280 5,7
1 1
SCH, H
H,N - CO - CH, CI 1 , - CI I - COOH
16 Glutamin 1 Gin 5,7
nh. 185

/ \ NH2
17 L(-)- ( C y \ C H ,- C COOII Phe* 283 5,5
Phenylalanin* II

18 L(-)-Tyrosin II \ \ ) / CH2 C COOH Tyr 342 5,7

H
nh 2
L(-)- ------- 1 CI hC COOH
19 Trp* 289 5,9
Triptophan*
1
H

\ / COOH
20 L(-)-Prolin N Pro 220 6,3
1
II
NHi
1 '
N ------p CH 2 C -C O O H
1
21 L(-)-Histidin H 1 H His 287 7,6
N
l
H

154
 (Cc a m in o a x it c g h i d u l cc a m in o a x it h h n g th a y th. l cc
aminoaxit ng vai tr quan trng trong c th sng nhng c th khng tng hp c m
phi ly t thc n. Nu thiu, thm ch chi mt arninoaxit ny c th lm cho protein tng
hp t hn protein b phn gii, kt qu dn n cn bng nit m).
i vi axit monoaminoicacboxylic s c ba gc; ten ca gc ho tr 1 cu thnh bng
cch i ui "ic" thnh "yl", gc ho tr 2 th i ui "ic" thnh "oyl"

//
HOOC CH, CHj CH c
I
\

o a - Glutamyl ^2
\\
KXX' CI , CH? CH COOI1 c CH2 CH2 C T COOH
In h 2 Y- Glutamyl NH
o o
Axil Glutamic
\\ //
c CH,
CH,
L CH
I C.\
Glutamoyl sj

Bi s 8.5 (HSGQG 1996 - 1997)

T h u p h n h o n to n 1 mol po lip ep tit X cho ta:

2 mol C H 3C H (N H 9)CO O H (A lanin h ay vit t t l Ala).

1 mol HC - C H 2 - C H 2 - C H (N H 2) - COOH (Axit G lu tam ic h ay Glu)

1 mol H 2N - (C H 2)4 - C H (N H 2) - COOH (Lysin h a y Lys).

NH 2
I l_
mol N CH 2 - C - C O O H (Histidin hay His)
H

N u cho X tc d n g vi 2,4 - (NOr,) - C 6H 3F (k h i u ArF) ri th u p h n th

th u c Ala, Glu, Lys v hp cht:
N ------ TT CH2- ch -C O O H
I
l N H -A r
N
I
H
M t k h c n u th u p h n X nh enzim cacboxipeptidaza th th u c Lys v
mt te tr a p e p tit. Ngoi ra k h i th u p h n k h n g hon to n X cho ta cc ipep tit Ala -
Glu; Ala - Ala v His - Ala.
1 . Xc n h cng th c cu to v t n ca p olipeptit X.

21-MSCHVBTHHUCO 155
 2. Sp xp cc a m in o ax it tr n theo th t t n g d n pHj (pHj c gi l im
ng in, ti pH am in o ax it d n g ion lng cc tr u n g ho v in tch v
khng di chuyn v in cc no). Cho bit cc gi tr pHj l 3,22; 6 ,00 ; 7,59 v 9,74.
3. Vit cng th c cu to d n g ch yu ca mi loi a m in o a x it tr n ti cc pH
bng 1 v 13.
4. Di tc d n g c a enzim th ch hp a m in o ax it c th b ecacboxyl ho (tch
nhm cacboxyl). Vit cng th c c u to cc s n p h m ecacboxyl ho ca Ala v
His. So s n h tn h baz c a nguy n t N tron g p h n t gia h a i s n p h m d. Gii
thch.

Bi gii

1 . T s mol v cng thc c u to ca cc a m in o ax it suy ra X l m t p e n ta p ep tit.

- T k t t a th u p h n s n p h m p h n n g gia X vi A rF suy ra u N (u
cha nhm NH t do) c a X l His.
- T s n p h m th u p h n X nh enzim cacboxipeptidaza su y ra u c (u
cha nhm COOH t do) ca X l Lys.
- Khi thu p h n khng hon ton X cho cc ipeptit His - Ala, Ala - Ala, Ala - Glu.
Suy ra t r t t s p xp cc am in o ax it tro n g m ch l:
His * Ala - Ala - Glu - Lys.
Cng thc c u to c a X:
H2N H c NH CH c NH CH c NH CH NH H COOH
I l I l I l l r
N ] c h 2 o ch, o ch, o (ch )2o <ch 2)4
k NJ ICOOH
. NH2
I
H
(C ng c th vit cng thc c u to trong nhm - c o - NH - gia Glu v Lys
c to r a bi nhm - COOH v tr y ca G lu vi nhm - NH v tr e ca Lys).
2. T h t t n g d n pH |.
G lu < Ala < H is < Lys
pHj 3,22 6,00 7,59 9,74
G ii thch. T n h a x it c a am in o ax it c ng ln th gi tr pH j cn g nh, tn h baz
cng ln th pHj cn g ln.
- Glu c pH j nh n h t (3,22), v s' nhm - COOH n h i u hn s nhm - NH.
M un tn t i d n g H O O C - C H 2 - C H 2 - C H - c o o 0 c n p h i th m H +
I
n h 3
(a v pH thp) nhm - COO H th hai kh n g b p h n li.

156
 - Lys c pHj ln n h t (9,74) v s nhm - NHo n h i u hn s nhm - COOH.
- Ala c pHj = 6,00 v c mt nhm - COOH v mt nhm - NH.
- H is c pHj tr u n g gian gia Ala v Lys v tu y s nhm - COOH v s nhm
- N H 9 b n g n h a u n h n g d vng cha N cng l t r u n g t m baz (tuy yu hn
- N H 2).
3. pH = 1 pH = 13

CH 3 CH COOH C H 3 CH COCP
Ala I
^H 3 NH

HOOC CH -CH2- C H COOH Q

o o c c h 2- c h 2- ch coo
Glu
4 h3 nh2

His
HN

o N'
I
H
c h 2- c h - c o o h
" NH,
N'
11
CH 2- C H -C O (f

NH-

H3N - (CH2)4- ch COOH H2N - (CH2)4- ch c o c p
Lys
nh2

4. (.Xem B i s 2. 5).

Kin thc m rng

1. im ng in ca aminoaxit
Trong dung dch, tu theo p H ca mi trng m aminoaxit c th tn ti dng
anion, cation hay ion lng cc.
H+
H,N CH c o o H ,N -C H -C (x r, ^ r
0
OH 1 OH
R R R
pH cao lon lng cc pH thp
Khi t aminoaxit trong in trng, tu thuc vo p H ca mi trng n c th di
chuyn v catot hoc anot. mt pH no aminoaxit khng di chuyn trong in trng,
ngha l tng in tch trong phn t bng 0 . pH ny c gi l im ng in (k hiu
pHj).
Glyxin: H 3N C H 2 c o o 0 ; pHj = 6,0
Axit monoaminoi (poli) cacboxylic c pH j < 6,0. Khi R khng tch in:
p K a, + p K a2
pH

157
 p K a ( - C O O H ) = 2,35 2.35 + 6.96
Chng hn, alanin c + >p H = + = 6 , 0 2
p K a ( - N H 3) = 9,69 2

Da vo s khc nhau ca pH j c th tch c hn hp aminoaxit mt pH nht nh

bng cch a vo hai in cc, khi y hn hp s tch thnh tng vt (hin tng in di):
pH < pH j aminoaxit di chuyn v cc (-); pH > pH j aminoaxit di chuyn v cc (+). Thuc ln
mu l ninhirin.

a vo
Phn ng mu vi nihirin.
o

\
c \ c;
/ 0H + R C H COOH (, H O H
C + RCHO
Q / \
OH
NH2
NH-, + CO;

L
N H 3 9 NH4
[ u

> H -< (xanh tm)
C
IJ l
O O

Ring Prolin cho mu vng.

2. Phng php xc nh cu trc bc 1 ca peptit.
a. Xc nh u N.

D ng DNFB: 0 2N F 2 ,4 - d in itr o flo b e n z en (P h n g p h p S a n g er).

NO

H 2N - C H R - C O - Q jN N H - CUR ~ 0 0 Fteptit
-HF

J o 2N N H -C H R -C O O H + H 2N - C H R ' - C O O H +

A m in o a x it
n o 2

Tch ly kt ta ri nhn dang.

158
 Dng CHtj - N = c = s (Phenylisothioxianat - Phng php Edman).
Q,| \ c = s i / n Cl IR 1 c o NI! Cl R2 CO Pcptit

C 611, NH c NH CHR 1 c o NH CHR2 c o Peptit

!!
S
R'

UN
Aminoaxit
N CfiH,
o
Phenylthiohiantoin
b. Xc nh u c.
Dng hidrazin HN - NH 2.
~ _ H2N NH2
H2N c h - 0 0 - N H - a i 2- c o - N H - CH - GOOH -------

(Ala - Gly - Phe) c^ 5

-----HiN-
2 CH-0 0 0 HiN-
. 2NHi + H27 N - CH27 0 0 - NH- NHi + HjN- CHCD- NH- NH2

CH, QH5
V-------------------------------------------------------------------------------------------------------v ------------------------------------------------------------------------------------------------------- -

Hidrazit ca aminoaxit
c. S thu phn phn ct chn la.
Dng enzim.
Exopeptidaza: phn ct lin kt peptit u cn.
- Am inopcptidaza: phn ct lin kt peptit ca aminoaxit u N.
- Cacboxipcptidaza: phn ct lin kt peptit ca aminoaxit u c.
Enopeptiaza: phn ct lin kt peptit trong mch to thnh cc on mch ngn hn.
- T ry p sin : Phn ct lin kt peptit sau aminoaxit basic: Ariginin(Arg) v Lysin(Lys).
-C h y m o try p sin : Phn ct lin kt peptit sau aminoaxit thm:
Phenylalanin(Phe), Tyrosin(Tyr) v Triptophan(Trp).
d. S thu phn khng hon ton.
T polipeptit thu c cc i-, tripeptit,... v sp xp chng li.
T rp - Ile
T rp - Ile - T h r
Ile - T h r - Lys
T h r - Lys

159
 T h r - Lys - Glu
Lys - Glu
Glu - Glu
Glu - Glu - Tyr
Glu - Tyr
Glu - T y r - Asp
- T rp - lie - T h r - Lys - Glu - Glu - T yr - Asp

Bi s 8 .6 (HSGQG 2000 - 2001)

1. C mt hn hp p ro tit gm pepsin (pHj = 1 , 1 ); hem oglobin (pHj = 6 ,8) v

prolam in (pH{ = 1 2 ,0 ).
Khi tin h nh in di dung dch protit nu trn th th u c ba vt ch t (xem hnh).

Cc o oi o
A B 1 c
..... -- -1-----
Xut pht
Cho bit mi vt c h t c tr n g cho p ro tit no? Gii thch.
2. Khi th u p h n hon ton mt trip e p tit X th u c 2 mol a x it glutam ic
(HOOC(CH 2) 2C H (N H 2)COOH); 1 moi a lan in (C H 3C H (N H 2)COOH) v 1 mol N H 3.
X khng p h n ng vi 2,4 - initrflobenzen v X ch c 1 n h m -COOH t do. Khi
thu p h n X nh enzim cacboxipeptiaza th u c a la n in v m t ip e p tit Y.
Vit cng thc c u to ca X, Y v gi t n chng.

Bi gii

1 . Vt A l pepsin v pep sin l pro tit c tn h a x it m n h (pHj = 1 , 1 ). pH = 7, pepsin

nhng H + cho mi trng chuyn th n h d n g a n io n n n di ch u y n v cc (+).
- Vt B l hem oglobin(pH | = 6 , 8) v h u n h d n g ion lng cc.
- Vt c l prolam in v prolam in c tn h baz m n h (pH] = 12,0). pH = 7 < pH,
prolam in n h n H + ca mi trng chuyn v d n g c ation n n di chu yn v cc (-).

2 . X + H 20 --c- b0Xli -e-ptK- 2a >A la n in nn u c ca X l Ala.

-> X: Glu - Glu - Ala.

- X khng p h n ng vi 2,4 - initroflobenzen n n X k h n g c nhm - NH t
do. Do vy nhm - NH ca m t n v Glu th n h t (u N) t o lactam vi nhm
- COOH.
Nhm - COOH ca Glu th hai d ng a m it - CONH (do th u p h n to N H 3).

160
Do vy X l:

1 : 'I l
N H C H c 4 - N H C H c - f N H C H CO O H
i l '
(C H 2)2 c o n h 2 c h 3
c h 2- c h 2

G lu ta m o la c ta m - a - y lg lu ta m in y lalan in
Y l:

II II
N U H c N H C H C OH
/
o c (C H 2) 2 c o n h 2
c h 2- c h 2

G lu ta m o la c ta m - a - y lg lu ta m in

Bi s 8.7

Polipetit A gm cc a m in o a x it theo t l Gly, Ala, Valo, L eu 9, Ile, Cys4> Asp2,

G1u 4, Sero, Tyr.,. A c h a m t c u d isu n fu a to vng oeca.
A tc d n g vi phenylisothioxianat to th n h d n x u t hiantoin ca Glyxin. M t
khc thu p h n A di tc d n g ca enzim cacboxipeptidaza th u c axit Aspatic v
mt polipeptit. T h u p h n khng h on ton A th u c cc oligopeptit sau:
Cys - Asp Glu - Cys - Cys
T y r - Cys Glu - Glu - Cys
Cys - Cys - Ala Glu - Leu - Glu
G lu - Asp - T y r Leu - T yr - Glu
S e r - L eu - T y r S e r - Val - Cys
Gly - Ile - Val - Glu - Glu
H y cho b i t t r n h t cc a m in o a x it trong A.

Bi gii

T heo d k i n c a b i th u N ca A l Gly, u c l Asp.

1 . G ly - Ile - V al - G lu - Glu
G lu - G lu - Cys
G lu - Cys - Cys
Cys - Cys - Ala

Cys - Asp

161
-> Glv - Ile - Val - Glu - Glu - Cys - Cys - Ala WWWCys - Asp ( 1)
2. Ser - Leu - Tvr
Leu - T vr - Glu
Glu - Leu - Glu
Glu - Asp - Tyr
T y r - Cys
-> Ser - Leu - T yr - G lu - Leu - Glu - Asp - T yr - Cys (2 )
Cn li: S e r - Val - Cys (3)
A c 4 Cys n n c hai k h nng:
Gly-Ile-Val-Glu-Glu-Cys-Cys-Ala-Ser-Val-Cys-Ser-Leu-Tyr-Glu-Leu-Glu-Asp-Tyr-Cys-Asp
(I)
Gly-Ile-Val-Glu-Glu-Cys-Cys-Ala-Ser-Lou-Tyr-Glu-Leu-Glu-Asp-Tyr-Cys-Ser-Val-Cys-Asp
(II)
Cc p h n t C vstein c k h n n g to c u d isu n fu a - s - s - :
H 2N H COOH
I
ch2
H2N H COOH I
r S
CH 2S,H
------ s
CH2SH
H 2N - C H COOH
H 2N CH COOH
A c c u d isu n fu a to vng oeca nn A l (II), v:
A Tyr Cys Ser V a l Cys Asp

s s
c h 2o h
H o
I
c CH N. CH
AWTyr JSJH C H '' X N7 "C H / '
I COAsp
o CH(CHi);
II II
CH s s CH

Bi s 8.8

1 . T ietyl m a lo n a t h y iu ch:
a. M ethionin(M et), a x it aspactic(Asp).
b. Leuxin(Leu), Tyrosin(Tyr).
2. T PhC H oC H O hy iu c h phenylalanin(Phe).
162
 Bai giai

1. a. Dieu oho M e t va Asp.

COOC 2H 5 COOC2 H5
/ /
CH i + Br2 Br CH + HBr
\
cooc2ns COOC2H 5
(A)
oII
c\ A
c
\ /
COOC2H5
1. EtO
*
: N: K --------> : N CH ---------------------
/ - KBr
CX COOC,H, 2 MeSCH2CH2CI
II
O O (B)
O
II
C / COOC 2H 5 coon
:N
:N C 3 1 , Met +
/X O
cII COOC 2H 5 . C 2H5OH
coon
o c h 2c h 2s c h 3 c0 2
o
ii
cx c o o c 2h<
BrCH2COOEt 5 h 3o
(B) :N C\
y Asp
EtO * Q / c o o c 2h 5
Q CH 2COOC2H5

b. Dieu che Leu, Tyr.

c o o c 2h ,
/ ' HONO COOC2H5 c x x x :2i is
cn 0 = N CH HO N = C
/
\ \
COOC2H5 ' H2 COOC2H 5 c o o c 2h 5
COOC2H5
1 . H^/Pi /
---------------- CH , C NH CH
2. (CH3C 0 )20 II COOC,Hs
O
Dietyl axetamidomalonat (C)
c 2h so 0 c o o c 2h 5 j N a0H
c ------ -------- CH 3 C NH C ---------- Leu
BrCH2CH(CH 3)2 II x - 3
COOC2H 5 2 . H 3O ,t 0
O
CH 2CH(CH3)2
& COOC2Hs . M
/ 1 5 1. NaOH
C C^H- ------ CH 3 c NH C x Tyr
p-AcOC 6H 4CH,Cl COOC2H, 2 . H3( f t"
O
CH2C6H4OAc -p

22-MSCHVBTHHCUCO 163
2 . iu c h Phe.
.CN
HCN /r S v NH3
c h 2_ c h o i. (Q - c2- c<
OH
CN
CH 2 C H ^ H3 I < > CH2 CH COOH
NH2
NH

Bi s 8.9

Hp c h t X ch a 5 loi nguyn t" c cng thc p h n t t r n g vi cng thc n

gin n h t; tro n g c chim 23,166%; H chim 1,4157% v X c ch a o . N u n g nng
1,554 g am c h t X vi N a chuyn cc nguyn t tro n g X t h n h cc hp c h t v c
n gin. S a u ho t a n vo nc c du n g dch A. Ly m t t d u n g dch A cho
p h n n g vi B r 2 th c d u n g dch lm xanh h tin h bt. Ly m t t d u n g dch A
cho p h n ng vi d u n g dch cha mui F e3+ th c k t t a m u x a n h k h n g b
m t i tro n g mi tr ng axit.
Ly d u n g dch A cho p h n ng vi mt lng B r va th s n p h m to ra
p h n n g va h t vi 80m l d u n g dch NaoS 20 3 0,1M.
Khi ly 1,554 gam c h t X p h n ng vi NaNO tro n g s c m t ca HC1 th
c 22,4ml (ktc) m t c h t kh khng m u, k h n g mi, k h ng chy.
1. Xc nh cng th c p h n t ca X.
2. G i s X c vai tr q u a n trng trong c th sng th X c cu to nh
th no?
3. H y tng hp ip e p tit Gly - Ala i t n h n g ho c h t cn thit.

Bi gii

mc = 1, 55 4 . 0 , 36 g + n c = 0 , 03 mol
1. 1,554g X c
m H = 1, 554 . ^ ^ = 0,022g - n H = 0,022mol

A p h n ng vi d u n g dch B r 2 to dun g dch lm x a n h h tin h bt (I9) n n A c

r , v t h X c I.
21" + B r 2 -> 2 Br~ + I 2
I 2 + 2N a 2 S 20 3 -> N a 2 s 4 0 6 + 2 NaI

rij- = n ^ a g o = 0,08.0,1 = 0,008m ol-> n I(X) = 0,008mol

164
 X p h n n g V1 NaNO/HCl cho kh khng m u , kh n g mi, khng chy l N 9
nn X c n h m a m i n b c l .
X: R (N H 2)n.
R(NH.,)n + nN aNOo + nH Cl -> R(OH)n + n N 9t + nHoO + nN aCl

- 2nN = 2. i .' 1 = 0 ,0 0 2 m o l
1000 22,4

1 ,5 5 4 -0 ,3 6 -0 ,0 2 2 -0 ,0 0 2 .1 4 -0 ,0 0 8 .1 2 7 - .
+ n n = ---------------------------------------------------------------= 0 , OOomol
u 16
n c : n H : n 0 : n N : nj = 0,03 : 0,022 : 0,008 : 0,002 : 0,008 = 15 : 11 : 4 : 1 : 4.
X c cng thc p h n t tr n g vi cng th c n gin n h t nn X l
C 15H n 0 4N I4.
2. X c vai tr q u a n trng tro n g c th sng nn X l:

Tng hp ip e p tit Gly - Ala

?
h 2n c h 2
NH CH COOH
L
ch3

Lu :
Khng th cho Gly tc dng trc tip vi Ala v l:
- Nhm - COOH l tc nhn axyl ho rt yu, nhm amino li c tnh baz nn
aminoaxit thng dng ion lng cc, do khi to lin kt peptit cn ph hu dng ion
ldng cc a i electron ca *N H 2 v dng t do.
Nu c phn ng s to ra hn hp cc peptit: Gly - Ala, Ala - Gly
- C th tng kh nng tip nhn s tn cng nucleophin ca nhm - COOH bng cch
a v dng este, clorua axit, anhirit,...
C th tng hp ipeptit Gly - Ala theo cc bc sau.
- Bo v nhm - NH 2 ca Gly. Dng nhm benzyl oxi cacbonyl (k hiu l Z):
0

< 0 ^ c h 2- o4 -

165
 o
N(C2H5)3
OH + COCI-. < CH, O C -C I
0 - * - HCI , ,
Photgen ( Z Cl)
O

Q H , C H 5- 0 C - C I + H , N C H 2 C0 0 e + 2 0 h P * * Z - N H - C H 2 O O c P

+ C l0 + 2 H 20

Z - N H - C H 2- C O C P + H Z - N H C H 2- C O O H

Bo v nhm - c o o H ca Ala.

H 3N C H c c x f + HOCH, H ~ c T H 2N c u C O O C H j

ch3 ch3

- H ot ho nhm - COOH ca Gly.

0 O
n ( c 2h 5)3 J
z - n h - c h 2- c o o h + Cl c q c 2h 5 Hfl Z - N H - C H 2 o
O C o c ,H ,
- To lin kt peptit.
o
//
Z -N H -C H 2- C ^ o + H2N CH COOCH
O c o c 2H5 i
p
------------ z - n h - c h 2- c ~ h n c h c o o c h 2
-co ? ,
- C2H5OH h,

- G b nhm bo v.
o ,___v
// _ H2/pd
z NHCH2 C- HN CH COOCHj \ x _ J /

ch3

--------H2N CH2 ^ + O - C H , + C0 2
NH CH COOH N '

ch3
Ch :
Nu dng nhm z bo v nhm - NH 2 th c th s dng mi nhm hot ho nhm
- COOH, tr dng clorua axit v nhm clorua axit hot ho qu mnh dn ti s to thnh
anhirit ca axit N - cacboxylic (anhirt Leuchs).
166
 o
o HN-------- CUR
V'
C61 C f l - C - NH chr- c' * Q H 5 CH,C1 +
Cl
< A A o
Anhirit Leuchs

Bi tp t gii

Bi s 8.10

1 . iu ch o r n itin (Orn) t 1,3 - ibrom propan.

2 . T phenol h y iu ch Lysin (Lys).

Bi s 8.11

Mt p e n ta p e p tit (A) k h i th u p h n h on ton cho 2 mol Gly, lm o l Ala, lm o l Val

v lm ol Phe. T ro n g p h n n g th u p h n t n g p h n A th y c Ala - Gly, Gly - Ala.
A tc d n g vi HNO<, k h n g th y gii phng No.
H y xc n h cu to ca A.

167
 Phn 9
GLUXIT

Bi s 9.1

Cho m t s gluxit sau:

CHO CHO CHO CH2OH

I l
H -OH HO- -H HO -H c=o
HO -H H -OH HO -H HO- H
H -OH HO -H H -OH H OH
H -OH HO -H H -OH H OH
CH2OH c h 2o h CH2OH CH2OH
A B c D
( - Glucoz) (L - Glucoz) (D - Mannoz) (D - Fructoz)

CH2OH
CHO
c=0 CHO
1
H OH H OH (
O H H OH H OH
H OH H OH H OH
CH2OH CH2OH C2OH
E F G
(D - Soboz) (D - Riboz) (D - 2 - eoxiriboz)

1 . H y v it cng th c dng vng ca cc gluxit trn.

2. H y cho bit:
a. N h n g c h t n o kh c A g N 0 3/N H 3> Cu(OH)o/NaOH?

b. N h n g c h t no kh c nc brom?

c. N h n g c h t no tc dng vi phenylhirazin cho cng mt osazon?

3. D - A rabinoz v D - Lyxoz l cc anopentoz m khi oxi ho b n g H N O 3 u

cho c ng m t a x it saccaric.
H y cho b i t cng thc chiu Fis ca hai anopentoz ny.

168
 B i gii

CHO H 6 CH,OH
H -OH t r.-hing _ CH-.OH
sang phi OH
H
HO -H JOH H S i' _
CH=0
H -OH \ H H \ H h / CB==
OFKJ oa
2
H -OH 2

c h 2o h
H OH H OH
A (D - Glucoz)
CH2OH

H OH
- D - Glucopiranoz a - D - Glucopiranozo
hay p - D - Glucoz hay a - D - Glucoz
Cng thc chiu Havt
Q u trin h vng ho trn l kt q u s tc d n g ca n h m - O H c5vo nh m
- CHO to th n h sem ia xeta l d n g vng. N h m - O H C j gi l O H sem iaxetal.
D ng vng c n h m - O H sem ia xeta l n m c n g p h a vi - O H C 5 gi l d n g a,
d n g p c n h m O H sem ixeta l n m kh c p h a vi * O H C5. D n g a v d n g (3
ch khc n h a u cu h in h C j gi l cc d n g p h n a n o m e .
Ngoi r a cn c d n g vng 5 c n h do s k t hp gia - OH C 4 v C i n h n g
km bn hn.
6 6
CHiOH CH,OH
5
HO HO
<T)H h
T\ OH H 3|
H H I
a - D - Glucofuranozc/** - D - Glucofuranozo

( * Dng vn <; 5 cnh v 6 cnh ca

monosaccnrit c gi l furanoz
v piranozd v tng t vng furan
v piran.
Furan
pPiran

169
Cu dng bn:

Oil

H H

a - D - G lu c o p ir a n o z o - D - G lu c o p ir a n o z o

B (/. - G lu c o z o )

CHO
li II
HO -H

H -O H

HO -H
HO -H
C H 2O H
a - L- G lu c o p ir a n o z o (L- G lu c o z a ) - L - G lu c o p ir a n o z o

C(D - M an n ozo)

C lio
?
HO n
3
HO H
4
H OH
5
H OH
6
C H 2O H
c
a - D - M a n n o p ir a n o z o (D - M a n n o z o ) - D - M a n n o p ir a n o z o

D ( D - F r u c to z )

c h 2o h

a - D - Fructofuranozd - Fructozrt (5 - D F ructofurano zd

170
 E(D - Soboz)

CH2OH

a - D - Sobofuranozd D - Sobozd p - D - Sobofuranozd

{D - Riboz)

CHO
HOH
H OH
H OH
H OH OH OH
X H 2OH
D - Ribozd p - D - Ribofuranoz

CHO o.
HOH OH
H H 4 H
H OH
H
OH H H OI OH H
CH2OH
a - D - DeoxiribofuranozcJ D - 2 - Deoxiribozd p - D - Deoxiribofuranozd

Kin thc m rng

- Cc gluxit chi khc nhau cu hnh mt nguyn t cacbon bt i c gi l cc
epime. Th d, D - glucoz v D mannoz l cc epime c<2 -

- Trong phn t A R N (axit ribonucleic) D - riboz tn ti dng vng p D -

ribofuranoz.

Trong phn t AND (axit eoxiribonuleic), D eoxiriboz tn ti dng ng phn

p D eoxiribofuranoz.

23-MSCHVBTHHUC 171
2. a. N h ng c h t k h c AgNO/NHithuoc th Tolen). Cu(O H )9/N aO H l t t
c, k c cc anoz v cc xetoz v trong mi trng kim cc xetoz chuyn
th n h anoz:
%>H ^)H
R -C -C H P H R -C = H R -< jT H -C H O

O OH OH OH
Xetoz Endiol trung gian Andozo
C hng hn:
CI12 (CH) CHO + 2AgNO, + 3 NH 3 + H ,0 * CCHv
H 2
(( COONH
C IHD) c o 4

OH OH OH OH
+ 2A g| + 2 NH4NO 3
CH2 (CH) CHO + 2Cu(OH )2 + NaOH CH2 (CH)r CONa
(CH)j COONa + Cu 20 |

OH OH OH OH + 3H-,0

CH-, ( C H ) j - c CH2OH + 2 AgNOj + 3 NH3 + H20 C H 2 (CH) CXX)NH4

OH OH O OH OH
+ 2Ag + 2NH 4NO 3

b. Nc brom c th oxi ho nh n h n g cc anoz th n h a x it polihiroxi-

monocacboxylic (axit ando nie).
CM2 (CH) CHO + Br2 + H20 CII2 (CH) COOH + 2HBr

OH OH OH OH
Glucoz Axit gluconic
T m annozd s th u c axit m annonic, t sobozd s th u c a x it sobonic,...
Nc brom khng oxi ho c xetoz v nc brom c tn h a x it n n khng gy ra
s ng p h n ho n h kim.
c. P h n ng c h u n g n h sau:
C6H5NHNH2
H2 (CH)4- C H = 0 ------ 7 7 7 CH2 (CH)4- C H = N N H Q H 5
I -H 2 I
OH OH OH H
Anohexoz Phenylhidrazin

Q H 5NHNH2 d C6H5NHNH2
C I2 (CH)?- c ch= NNHQH,
- q h 5n h 2 I I - II - h 2o
-n h3 oh oh o

CM2 (CH).,- c C I I = NNHQH,

OH OH NNHQH,
Phenylosazon
172
 N h vy n h n g anox v xctoz c cu trc khng gian t nguyn t c 3 tr di
ging n h a u s cho cng mt phenylosazon (vit gn l osazon).
l:
CHO CHO c h 2o h
I l
II - OH HO -II c=o
HO -H HO -n HO -H
II -O H II -O H H -O H
II - OH H -O H II -O H
CH2OH CH2OH CH2OH
L) - Glucoz D - Mannozo D - Fructoz
+3C 6H 5 NHNH 2
+3C 6 H 5NHNH 2 -C6 H 5NH 2
+3Q ,H 5NHNH 2
-Cr,H 5NH 2 -n h 3
-C 6H 5NH 2
-N H 3 -H20
-n h 3
- h 2o CH N - NHC 6H 5
- h 2o
= n - n h c 6h 5
HO -H
H -OH
H -OH
CH2OH Phenylosazon

3. Axit H N O 3 oxi ho cc andoz to th n h a x it polihiroxiicacboxylic (axit

saccaric).
hno3
c h 2 ( C H ) r - c n o * HOOC (CH) f COOH

OH OH OH
Ano?. Axit saccaric
Hai D anopentoz m cho cng mt axit saccaric th a x it p h i l:
COOH
HO-------H
H -------OH
H -------OH
COOH
Hai anopontoz l:
CHO CHO
HO H HO -H
%
H OH v HO -H
H OH H -O H
CH.OH CH2OH
173
 Ph lc 2. Mt s monosaccarit tiu biu thuc dy D

174
Bi s 9.2
N hiu hp c h t c k h n n g lm q u a y m t p h a n g n h s n g p h n cc m t gc a
no d, k h n n g y n h n g iu k in th n g n h t v nng , d u n g mi, n h i t ,
nh s n g c biu th b n g [ci^ . T h d a - D - glucoz c [a]^ = 112, cn - I) -

glucozcj c [ot]^ = 19. C 3 isa c c a rit A, B (thin nhin), c (tng hp) u khng

kh dc A g N 0 3/NH*j. Khi th u p h n s n p h m mi th u c t A l glucoz c

[a] = 112, t B c n g l glucoz n h n g c [a ] = 19; cn c cho h n hp h a i s n
ph m tr n vi s mol b n g n h a u . S a u khi h o n th n h th u p h n m t thi gian c 3
25
dung dch u c [ct]p = 52 (n nh).

1 . Xc n h cu tr c p h n g v gi t n ca A, B, c.
2 . V sao [ a ]2
D5 c a u n g dch s a u khi th u p h n li bin di th eo thi gian? Xc

nh t h n h p h n % c a s n p h m th u c khi xq - 52. Hp c h t n o bn hn?

V sao?
3. Cho A tc d n g vi lng d C H 3I tro n g d u n g dch baz ri u n si s n
phm th u dc vi d u n g dch a x it long. V it s p h n n g v cho bit s n p h m
th u c c tc d n g vi Cu(OH) h a y khng? A c tc d n g vi Cu(OH).> hay
khng? Gii thch.

Bi gii
1 . T heo u bi ta c:

- A to bi h a i don v a - D - Glucoz nh lin k t a - 1,1 - glicozit.

6
h 2o h

H OU H
1 - o - (a - D - glucopiranozyl) - a - D - glucopiranozd
B to bi hai dn v - D - Glucoz lin k t vi n h a u nh lin kt - 1 ,1 - glicozit.

c h 2o h

HO h o h ! 6
5 OH

1 - 0 - ( - D - glucopiranozyl) - p - D - glucopiranoz
175
 - c to bi m t dn v a - I) - glucoz v mt dn v p - 1) - glucox.

C1NOH
II Ov H
H
OM H

H OH

1 - 0 - (a - I) - glucopiranozyl) - p - 1) - gluco[)iranoz
r 1 s
2 . T a c a]jj ca d u n g dch bin i theo thi gian sau th u p hn v hai d n g u v

p a n g h n h th n h c n b n g nn nng ca hai d n g d bin di ko th eo (X;jj

cng bin i theo. n khi t ti tr n g th i cn b n g th lc ap = 52.

Gi % mol ca d n g u v p lc cn b n g ln lt l x% v y%. T a c:

x + y = 100
X = 35,5
112X + 19y
52 y = 64,5
x+ y

Vy d n g a chim 35.5% v d n g ( chim 64,5% d n g i bn hn d n g rt v

nhm -OH se m ia x e ta l lin kt bin bn hn.

11

a - D - Cilucopiranoz [5 - D - Glucopiranoz

H OH
II H
CH,!
3. N^ 10 O l t
o 0 ()1I
o OI
H

176
 A k hng tc n g vi Cu(OH).) v nguyn t c v tr i 1 b kho. v cc
nhm - OH Hn k n h a u u khc pha.

Bi s 9.3

T inh bt, xenlulozd thuc loi polsaccarit thc vt: cn glicogen l polisaccarit
ng vt.
1 . So s n h cu tr c ca ba polisaccarit trn.
2 . T h u p h n h on ton cc polisacearit trn th u c cc s n ph m mi nh
th no. c t h a y i theo thi gian khng?
3. T in h bt c th tc d n g vi I > cho m u xanh, C11 xenlulozd th khng; tri
li xenlulozd c th ko th n h si, cn tin h bt th li khng. Gii thch?
4. T h u p h n cc polisaecarit trn, trc khi to ra s n p h m cui cng n h n
c cc isa cc arit tr u n g gian. H y vit cng thc ca cc isaccarit .

Bi gii
1 . T in h b t (C 6H 10O )n l h n hp ca hai loi polisaccarit: amilozd v
am ilopectin.
- Amilozd c cu to khng p h n n h n h c to bi cc n v a - D -
g lu eo pirano/ k t hp vi n h a u nh cc lin kt a - 1,4 - glicozit.

H OH II OH
' II OH
Cc n v glucoz u cu d n g gh.
H
 - A m ilopectin c cu t o p h n n h n h , gm m t s" m ch am ilozd k t hrti vi
n h a u nh lin k t a - 1,6 - glicozit.

Cc n v glucozd tro n g am ilopoctin c n g t n t i c u d n g gh.

X e n l u l o z (C 6H 10O 5)n c c u tr c kh n g p h n n h n h , gm cc n v - D -
glucozd lin k t vi n h a u nh cc lin k t - 1,4 - glucozit.
cHiOH c h 2o h

. </ 1
H
H OH H OH
Cc n v glucoz c ng tn ti cu d n g gh.

h CH2OH 3
H 11 H
G l i c o g e n (C 6H 10O 5)n (cn gi l tin h bt n g vt). Glicogen c cu to t
cc n v a - D - glucopiranoz nh cc lin k t a - 1,4 - glicozit v lin k t a - 1,6 -
glicozit. P h n t glicogen c cu t o m ch n h n h tng t am ilo p ectin n h n g mc
p h n n h n h cao hn.
2. T hu p h n h o n to n th t in h bt cho a - glucozd, xenlulozd cho - glucozd,
glicogen cho a - glucozd. Cc s n p h m a - glucozd v [ - glucozd ch uyn ho qua
li cho ti khi h n h th n h c n b n g gia h a i dng.
3. tin h bt do cc p h n t amiloz c c u tr c d n g xon th eo kiu l xo, mi vng
xon th n g c 6 n v glucoz. C u tr c xon c gi v n g n h lin kt hiro
gia cc nhm hiroxi.
Khi cho u n g dch lot p h n n g vi tin h bt n h i t phng, cc vng xon
amilozd bao bc cc p h n t iot t o "hp c h t bc" c m u x a n h tm :

Amiloz

178
 Khi u n nng, m u x a n h tm bin m t do lin k t h i ro gia cc vng xon b
ph n ct. m ch p h n t amilox dui th a n g n n cc p h n t iot th o t ra. Khi
ngui m u x a n h li x u t bin.
Cn xenluloz cu to bi cc m ch kh n g p h n n h n h c xu hng dui ra do
to cu lin k t h i ro gia n g u y n t o tro n g vng c a n v n y vi nhm hiroxi
nguyn t C 3 c a dn v glucoz bn c n h n n k h n g c k h n n g to hp c h t
bc vi iot n h tin h bt. C n g nh m xenluloz c k h n n g ko t h n h si.
Tinh bt vi cu to m ch p h n n h n h ca am ilo p ectin v cu tr c d n g xon
ca amiloz nn (lng h t m k hng ko t h n h si c.
4. Cc isaccarit t r u n g gian:
Tinh bt v glieogen u cho:
c h 2o ii c h 2o h c h 2o h

tro ng nc m t xch a - D - glucopiranoz th h a i c s c h u y n ho c n b n g

vi d ng [ - I) - glucopiranoz.
- Xenluoz cho:
1,011
H

OH

(Xenlobioz)
trong nc m t xch p - D - glucopiranoz th h a i c s c h u y n h o cn bng
vi d ng a - D - glucopiranoz:
a - Xenobioz r=i (3 - Xenlobioz

Bi s 9.4

Cho s p h n n g sau:
(CH3C 0)20

n CH,OH/HCl .
a - D - Cilucopiranoz - ----- A
(C2h 5)2s o 4 h 2o / h c i .
A 3 -------- a 4
NaOH 100"c
24-MSCHVBTHHUCO 179
 Vit cc phng trn h phn ng theo s (l trn v cho bit cd ch p hn ng to
r a Aj. Ngoi Aj cn s n phm no na khng? Gi tn Aj.

Bi gii
Do n h hn g ca nguyn t 0X1 trong vng nn nhm - OH sem iaxotal c kh
nng p h n ng cao hn cc nhm - OH khc; c kh n n g phn ng VI aneol c
HC1 k han lm xc tc to ra hp cht glicozit.
ch 2oh
- Ov H
+ H20

ch 2oh

H o. II II OH
H HC (AJ > Metyl a - ) - glucopiranozit
OH H + CH,OH
(Sn phm clIIl)
ch 2h
H OH H OCH,
II
011 H + H,0
OH ' 'A
H OI
Melyl p - D - lucopirano/it
S) phm liliiii
C c h ca p h n ng n h sau:
CH2OH CHiOH CH2OH
H A ---- Ov H
H
ir
OH H
OH
H OH
CHiOH CH-iOH
w / Ov H II ------- c \ H
-H+
\ H H y rH 011 H
/ s O hN +H
OH OCH,
CH3OH ' H OH H
- H OH
CH2OH H
NV H ---- c> V
H CH,
H H
OH H
H OH
CH2OH c h 2o c o c h ,
H J v H H o. H
+ 5(CH,C0)20 OCOCH^ + 5CH,C00H
0 CH3 CH,COO OCH,
H OH H OCOCH,
(A,)
180
 Cl m i I ( H2OC 2H,
ov II ------ o II
(C2 H5 )2 SOj/OH- h 11
OH II O.H, h
Ol o n I, C2I i p X C ,
I! OH 11 OC2H5
(A3)

H 2OC 2ll 5 CH 2OC 2H5

II ------- o II o H
HC1
+ HOH + CH3 0 H
c 2n p 0 CH3 c 2n p
I! OC2 H5

Kin thc m rng

Cc glicozit bn trong mi trng baz, khng c kh nng m vng nn khng c phn
ng trng bc,... nhng d b thu phn trong mi trng axit hoc xc tc bi enzim.
Chang hn, metyl a - D - glucopiranozit un nng vi dung dch axit cho hn hp a - D -
glucopiranoz v - D - glucopiranoz.
Khc vi xc tc axt, mi en zim chi xc tc cho p h n ng th u p h n m t glicozit xc
nh, v d enzim a * glucozidaza (M antaza) ch xc tc cho phn ng thu phn cc
a - glucozit, enzim - glucozidazaCEmunsin) ch xc tc cho phn ng thu phn cc
- glu coz it.

Bi s 9.5

1 . Hon t h n h s sau:
BrVH70 (CH3)2S04d /NaOH H 20/H +
Mantoz - . A ------ - -------- B c +'D
L - E + H20

2. Axit H N O 3 c k h n n g oxi ho c h t h u c theo s :

------H c ---------- ------------------COOII + ------ COOH

I
OCH3 O
xc n h kch thc vng ca m t D - anohexoz (X) thuc loi vng 5 cnh
h ay 6 c n h ngi ta th c h in chui bin ho sau:
xCHHma Y CM'Wtf A IW BHNO^Hnh(?pC

Hn hp c gm: C 0 2, C H 3O C H 2COOH, HO O C - (C H O C H 3)o - COOH,

H O O C -(C H O C H 3) 3-COOH(D).

181
 Hy th i t lp cng thc vng p h n g ca X. b it r n g D c c u trc:
COOH
H OCH3
H 0 CH3
H OCH3
COOH

Bi gii

CH2OH CH2OH

OH + Br2 + H-,0

+ 2HBr

CH2OH CH2OH
Ov H H OH
H (CH 3) 2S(VNaOH
OH H OH H COOH

H OH H OH
CH 2OCH 3 CH 2OCH 3
o. H H ------- OCH 3
1 4 H
OCH 3 H OCH3 COOCH3
o ----

CH (B) H OCH3

CH2OCH3
-----OCH3
H H
OCH3 H COOCH3 + 2 H20

OCM

182
 coon
H OCH-,
CH3O H
H OH
H OCHi
(C. CH OCH., (D)
CHIOCH, CH2OCH3 CHjpCHa
II OCH 3 CH3O HOH IIO CHjO- 11.
o
c = o *>
CH3 II C(K)H - = - OCH3 H OCH, ir > = 0
II 20
OII H H
II 0 CH3
1 OCHj H OCII (E)
(D)
2. Theo s d trn th:
Y: M etvlglicozit.
A: San phm metyl ho cc nhm - OH.
B: Sn phm thu phn nhm - OCH 3 glicozit to ra dng mch h
C: Lin quan ti kch thc vng.
- Nu X cing vng 5 cnh:
H o H o.
V / CH3OH/HCI X CHOCH3 CH'I/()>1'
CHOH --------- .
HOCHICH \ HOCH2' " \ /
unu r ----
HOIIC-----CHOH
HO HU
(X) (Y)

CHO
I
i o. CHOCH COOH
\ I I
CHOCH3 h 2o/h+ h o c h 3 h n o 3 HOC]
hoch, COOH
c h 3o c h 2c h \ / ..L - ... * I I
CHOH CHOCH, + CHOCH3 +...
H ---- CHOCH,
CHOCH^ (B) COOH coon
c l , O C H , (A )
CH2OCH3
-> Khng tho mn.
- Do vy X dng vng 6 cnh,. Tht vy tng t nh trn ta c:
C H O
c h 2o h I
HOCH- co o h
CH o L
CHOCH- Tr_

CHOCH3 COOH
J \ _ I HNO} I I COO1
HOHC CHOH CHOCH3 ^ CHOCH3
LnuLH3 + HOCH3 ++ 1I +1
+CO
\ /
CH CHOH HH HOCH3 HOCH-1 CH2OCH3
_ I I 3
OH (X) CH2OCH3 (B) COOH COOH____________
(C)
183
 Tho mn iu kin u bi. Vi cu trc ca [) nh vy till X I' th l:
CIIO Cl i o
CI 1,011 ('IU )II
OH
OJ 1
OH
OH
c h 2o h c n 2oi
D(+) - Aloz D(+) - Talo/.

Bi s 9.6

Hp c h t th i n n h in X c cng thc p h n t C7H 0 6 l mt c h t khng c

tnh kh v khng t ng p h n ho c, T hu p h n X b n g d ung dch HC1 long
th u c Y (CgHjoOg) l mt monosacccarit c tn h kh. Oxi ho Y b n g H N O 3
long, nng th u dc mt iaxit M (CfiHjoOg) khng c tnh q u a n g hot. Lm gim
mch ca m onosaccarit Y chuyn nhm - C H O H CH O th n h nhm - ('H O
(thoi p h n Ruf f ) th th u dc m onosaccarit z (Cr)H in0 5). z b oxi ho bi H N O 3
long nng cho iaxit N (C 5H s0 7) c tn h q u a n g hot. Cho X tc d n g vi C H 3Br
trong mi trng baz sinh ra p. p tc d n g vi d u n g dch HC1long to ra Q;
Q b oxi ho bi H N O 3 long nng th u c mt hn hp s n ph m tro n g c
axit 2,3 - im etoxibutanioic v ax it 2,3 - im etoxipropanoic.
Xc nh cu tr c ca X. Y, z, M, N.

Bi gii

Cc m onosaccarit th in nhin u thuc dy D. N n m onosaccarit z c dng:

CHO OOH

CHOH UNO, C1OH
-------
CI CHOH
II OH I! -o n

c h 2o h (Z) COOH (N)

N c tn h q u a n g h o t nn N l:
C(X)I I CHO C 10
no H HO H HO -II
noH hoc
HO II II- -OM
H OI n OH II- -OH
COOH (N) CH2OH (Z|) CH L7OH (Z2)

D(-) - Lixoz D(-) - Arahinoz
184
 Tng n g c Y l:
CIIO COOH CIIO

CIIOH
ICHOI li 011 li 011

1IO HO -II Klins c no H n o 11

IIO li IO HO II HO II
II OH II on H 01 H OH
c i O i (V,) COOH(M) COOI CH 20H(Y|)
D - Cialactoz
CHO x )H

CHOH
I
CHOH
HO H HO H Lun c Loi
H OH H OH tnh quang hot

H OH H OH
C H 2OH (Y2) COOH(M)
X khng c tn h k h nn X c cu tr c d n g vng v nhm - OH sem iaxetal
chuyn th n h nhm - O C H 3.
X c dng: C 6H 70 ( 0 H ) 4( 0 C H 3) -> P: C 6H 70 ( 0 C H a V C t y .
Khi y Q: 0 H 7( ) (o c H 3) 4(OH). Oxi ho Q th u c axit 2,3 - imetoxi-
butanioic v a x it 2,3 - dimotoxipropanoi, nn Q l:
CHO
H OCH
CH 3O H COOH
HO H II och3 COOH
HNO,
OCH CH30 H + H -O C H 3
CH 2OCH 3 (Q) COOH CH 2OCH 3
Do vy X d n g vng 5 cnh:

M e t y l a -(P -) D - g a l a c t o f u r a n o z i t

K i n th c m r n g . Phn ng lm gim mch cacbon ca gluxit.

1. T hoi p h n Ruff. Phng php thoi phn Ruf f c dng ngt mch cacbon cho
anohexoz, theo phng php ny s ngt mch cho anopentoz vi hiu sut thp.
185
 Cl O cooil c c x ) 0 - c a 2+
)
l i OH l i OH l i OH
no 11 HrVINO no il Ca(OH )2 no H u202, Fe1+
H Oil l i OH H OH
H on l i OH H OH
c h 2o h C H 2O H CHiOH
D - Glucozo COOH
I
c=o Cl 10

HO- !() -I
------- ** Ji -O H -C (h -OH
ll - -O H II- -OH
CH2OH c h 2o h

D - Arabinozo

2. Thoi p h n VVolh. Phng php ny c dng ngt mch cho c anohexoz v

anopcntoz.

C IIO C H = NHOM = N
H OH II -OH II -OCOCH 3
NH2OH 4(CH 3C 0 )20
H OH - H -OH H -OCOCH,
H 20 4CI 3COOH
li OH il -OH II -OCOCH,
h 2o
c h 2o h c h 2o h
C1I20 C 0 C H 3
D - Riboz C-EEN
CHO
-OH
CI l 3ONa/CHCl 3 H -OI
-on CH,ONa
- NaCN I I - -OH
-OH
-CH3OH c h 2o h
CH 2O H j D - E r y th r o z

3. Thoi phn amit ca axit anonic.

cC
NH-> N =c= 0

H OH H OH CHO
10
i U 11
1 HO H HO H
I ICIO
11 nU i1 I1 -------- 11
11 nDii 11
Ii II OH
Na2CO -HNCO
I11I O Il 1 II 11
11 OH1
VJi
U OH
(: h 2o h CH , 0 1 1 (;u ,O H
D - Giuconamit D - Arabinoz

186
1 . T I) - A rabinoz hy th i t lp s iu ch D - glucoz v D - mannozd.
2. iu ch 3 - O - Etyl - D - glucopiranoz t D - glucoz v cc h o c h t cn thit.

Bi gii

CN o = c CHO

H OH H- OH H OH
o
HO H n p /ir ho H (Na, Hg) HO H

H OH t" H kh H OH

" h -OH II -OH li OH

CH=0 CH2OH CH2OH c h 2o h

HO D - Glucozo
ICN CHO
H -OH CN
II -OI 110 H HO H

c h 2o h f I1 T
I (Na, Hg) HO- H
1
11 n i 1I
wi kh H OH
D - Arabinozo

II OI 1 H OH
(: h 2o h CH2OH c h 2o h
D - Man nozo
(Phng p h p tng hp x ia n h i rin hay tng hp K ila n i - F ischer)
2. iu ch 3 - o - Etyi - D - glucopiranoz.
6 f>
o

CH, c C H ,,H +

- h 2o

CH
3\ _ /
/\1CH,
CH
\ / CH;
/ c\ H
/ \ II
CH { o , OC 2H 5
_ 2 4 ^OH H I (C2H5)2SOVNaOH
H3 o
H3 7 o \ CH
CH3 H o
H o \
\
6 \ CH
ch3
h o -ch 2 CH,OI
H /O H
H20 , HC1 4"
o c 2h 5
- CH ,c o a I OH
H OH

25-MSCHV'BTHHOl!C
187
Bi s 9.8
Khi cho m t s gluxit tc d n g vi H I 0 4, tng ng vi mi p h n t gluxit ta
th u c k t qu sau:

S H I 0 4 SHCOOH S HCH O

Metyl a - D - M an n o zit 2 1 0

Metylglicozit anohexoz 3 2 0

Metylglicozit anohexoz 2 0 1
Hy xc n h kch thc vng ca cc gluxit trn.

Bai gii
Tng t cc iol - 1,2; m onosaccarit d b oxi ho n g t m ch bi a x it peioic
H I 0 4 to th n h ch yu a x it fomic.
CHO
H OH
HO H
H O
+ 51110 5HCO OH + HCI = o + 5 HIO 3

H OH (HCHO to thnh t nhm - C H 2OH)

CH2OI
Cc m etyl glicozit ch b oxi ho ngt m ch cc lin k t - C H O H - C H O H - .
Theo cc d liu ca bi ta c:
-Metyl u - D - Manno/.it:
CH2OH c h 2o h

o
H H
H H + 2HIO3 + h 2o
) + 2 HIO 4----- * HCOOH + 0 = HC
OH HO
HO 0CH3 0 _ HC/ 0CH3

H II

-Metylglicozit anohexoz 1 :

L.
CH OCH 3
OCH
H OH
o H
o
HO H
+ 3 H I0 4----- * 2H C00H + 0=H C H + 3HIO-, + H 2
H OH
H OH 0=-HC H
CHy

188
 -Metylglicozit aiidohexozd 2:

H iO H

HO-H M 0 = C H Q
OCH,
+ 2H IO 3 + 2 H 20

Il 11
o

Bi s 9.9

Gentibiozd l m t ng k h c th to osazon, c th i q uay v b thu p h n

bn g d u n g dch a x it hoc b n g enzim e m u n s in cho D - glucoz. Metyl ho
gentibioz ri th u p h n cho 2,3,4 ,6 - te tra - o - m etyl - D - glucoz v 2,3,4 - tri - 0
- metyl - D - glucozd.
H y cho b it c u to c a gentibioz v gi tn.

Bi gii

Gentibioz l m t ng kh, c th i q uay v to osazon nn c nhm - OH

sem iaxetal.
Gentibioz b th u p h n b n g enzim e m u n s in cho D - glucozd do gentibioz
c lin k t - glicozit v l isa c c a rit cu to bi hai n v I) - glucozd.
Xt cc s n p h m th u p h n s a u khi metyl ho gentibioz:

CH 2O C H 3 c h 2o h

H 0 CH3 H 0 CH3

T ta c s n p h m m etyl ho ca gentibioz l:

c h 2o c h . ch2

H
H
0 CH 3 H OH
CH 3 O

H 0 CH 3 H OCH 3

189
 Vy gentibiozd l:

c h 2o h

H O

H on H OH
6 - o - (P - D - glucopiranozyl) - D - glucopiranozd

Bi s 9.10

Rafinozd l m t ng khng c tn h k h c cng th c C 18H 3o 0 16. Khi thu

p h n rafinoz b n g a x it th u c D - fructozd, D - galactozd, D - glucozd. T hu p h n
b n g enzim a - g alacto d aza th n h n c a - galactozd v saccarozd. Khi thu
p h n b ng in v e rta z a (m en th u p h n saccarozd) th n h n c D - fructoz v mt
isaccarit melibioz.
Metyl ho hon ton rafinozd ri thu p h n cho 1,3,4 ,6 - te tra - o - metyl - D -
fructozd; 2,3,4 ,6 - tetra - o - metyl - D - galactozd v 2,3,4 - tri - o - metyl - D - glucozd.
Xc nh cu tr c ca rafinozd v melibioz v gi tn.

Bi gii

Rafinoz c cu to t 3 m onosaccarit: D - galactoz, D - glucozd,

D - fructoz.

D r . a-galactozidaza . ___ . , ___,

Kannozd ------- ----------- a - galactoz + saccaroz

do rafinozd c lin k t a - glicozit gia a - galactozd v saccarozd.

Rafinozd ycrtaza+ J-J fru c t0Z(j + melibiozd

do rafinoz C a - galactoz lin kt vi vng glucozd trong saccarozd.

Xt cc s n phm :

H 2OCH 3 c h 2o h
c h 2o c h
O ^ H c h 3o o H o H
II

HO
H C H /)
CH 2OCH 3 I H
OCH 3 H

H
OH

CH 3
CH 3O
H
OCH 3 1

H
OH

OCH 3

Cn c vo nhm - O H khng b m etyl ho tr n glucoz th rafinozd c

cu trc:

190
 c i i 2o h
C)
io II
II
KOH II A
n\| / Q CII2
2
c h 2o h
II OM II o II
(X II
V.___________
V
___________ / II
\ OH H/ II FK)
n v D - lctfZt/
o \ /
2
o / 0 H
* 22OH

H OH OH H
n v D - glucoz Oan v I) -fructoz
6 - o - ( - 1) - galactopiran ozyl) - a - D - glucopiranozyl - p - D - fructofuranozit.

M.elibioz l:

CH,OH

HO -------o II
4 H
OH I
---------------CH 2

H OH
V_______ V
_ ________ / "/i \H
Dn v D - >alactoz ' 4K ? H | / OH
Ho\ |
3 2
H OH

Dn v D - gliicozfl
6 - o - ( a - D - galactopiranozyl) - D - glucopiranoz

Bi s 9.11 (Bi tp chun b Olympic Ho Quc t ln th 31)

1. Hy d ngh m t h ay n h i u cu to vng vi ho hc lp th c th c ca
(D) - Tagaloz tro n g d u n g dch b n g cng thc chiu Harvvorth.
c h 2o h
1 *
(: = o
HO H
HO H
H OH
CH 2OH (D) - tagaloz

2. Hai s n p h m vi c ng cng thc p h n t C 6H 10O 6 th u c khi cho

D - arabinoz tc d n g vi n a tri x ia n u a trong mi tr n g a x it ri th u p hn k tip

191
cng trong mi tr n g axit. Vit cc cu to km ho hc lp th c th c ca hai
hp c h t v c h n g c to th n h nh t h no?

(: h o
1 0 II
1. NaCN/H
IV) 1 1

I nUii 1 2. H30 +/t

11

(: ih17, o
V V71h1
(D) - arabinoz

3. Khi mt isa c c a rit (c tnh kh) l turano/. c em th u v ph n, th u dc

D - glucozd v D - fructoz vi s mol b n g n h a u v b n g s mol sa c c a rit d (lng.
Metyl ho tu ran o z vi m etyl ioua c m t bc oxit ri th u p h n k tip to th n h
2,3,4 ,6 - t e t r a - 0 - m etyl - D - fructozd.
x u t cu t o c th c ca turanozd. m khng cn xc n h ho hc lp th
ti cc v tr anome.

Hng dn

HOH2C o CH OIHOII o OH(CH OI)

1. v
OH HO
il 0 1 (CII 2OH) C1I 21I(()II)

II H H II

CN CN
CHO II OH HO II
HO -H HO H HO H
NaCN/II+
2. H -OH H OU H OH
H -OII H OH H OH
CH2OH c h 2o h CH2OH
D - arabinozo

CN COOH
H -OH li -OH
HO -H H 30 +,t c no- -H
------------

H -OH H -OH - h 20
H -OH H -OH
CH, 01 CII2OH

192
 CN COOI CH.OH
IK ) H no H
+ .0
110 II 11,0 . no n
o
II OH II OH n 2o
n OH II OH

c h 2o h

3. T u r a n o z :

Bi s 9.12 (Olympic Ho Quc t ln th 31)

Glicozit A (CoHr^NO y) c tro n g h t Rosaceae khng p h n n g vi dung dch

Benedicts c n g n h nc Feling. S th u p h n b n g enzim ca A cho (-) B,
OsH7NO v c , C j;H . 7.,Ou , nhng s thu phn hon ton bng axit to thnh cc
s n p h m h u c. (+) D, C 6H j .,0 6 v (-) E. CgHgOg.
c c m t lin kt 0 - glicozit v cho p h n ng vi d u n g dch Benedicts hoc
nc Feling. M etyl ho c vi Mel/AgoO to t h n h C.,0H 3gO n , m khi thu p h n
trong mi tr n g a x it cho 2,3,4 - tri o - metyl - D - glucopiranozd v 2,3,4 ,6 - te tr a
- o - m etvl - D - glucopiranozd.
() B c th iu c h t b e n z a n d e h it v N a H S 0 3, tip theo vi NaCN. T hu
p h n () B tro n g mi tr ng a x it cho () E, CgHg03.
Vit cc c u t o c a A - D vi ho hc lp t h p h hp th eo cng thc chiu
H a rw o rth . t r c h t B.

p s

CH2OH
J o o ch2

" w
OH H O ^ Y
OH
(A )

193
 H2Ol 1
I l2O I
o o ------CH-,
o Ol KU)

H(OH)

Bi s 9.13 (HSGQG 2002 - 2003)

1 . isaecarit X (C 19HoOu ) kh ng th a m gia p h n ng t r n g bc. khng b thu

p h n bi enzim m a n ta z a n h n g b thu phn bi enzim em u lsin . Cho X p h n ng
vi CH 3I ri th u p h n th chi c 2,3,4 ,6 - te tra - o - m etyl - D - guloz.
Vit cng thc lp th ca X. Bit rng: D - guloz l ng p h n cu h n h C3
v C4 ca D - glucoz, mantaz xc tc cho s thu phn ch lin kt a - glicozit,
cn e m u lsin xc tc cho s th u p h n ch lin k t - glieozit
2 . Deoxi - D - glucozd A (CgHjoOg) c chuyn ho theo h a i hng sau:
n o 1. LA1H.)
-i-C 4~~~~ * D ' glixerin, 3 - hiroxipropanal
2. II20
4 CH^OH, H+
A -V B
Q H 12O 5
C61i| |Br0 4 (E) K0 1 1 C6H 10O 4 (F )1-1^ -X- l hn hp (

(B, c, D, E, F l cc hp c h t h u c)
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 c h t c tro ng hn hp G. bit p h n t khi
ca c h ng u ln hn 160 v nh hn 170vC.

. Bi gii

1. T D - glucozd suy r a cu hnh ca D - glucozd. X k h ng c p h n ng t r n g bc

n n c lin kt 1,1 - glicozit.
- S th u p h n ch bi em ulsin chng t tn ti lin k t 1/7- i ' - glicozit.
Do vy X l:
H2OH
o X-----
MO O
H H
\ HOH-C
0
OH OH

194
hoc:

2. a., b. T hng c h u y n ho th n h t xc nh c cng thc cu to ca A:

CH2OH c h 2o h

o (C)
HO
CH 3OH/H
OH OCH 3

(D)
OH (A) OH (B)

CH2OH
o
\ + CHiOH c h o
L1AIH4 _ \ H^Cr 1 1 1
OCH 3 - 2 h o h 2c o c h 3- ^ h o h + h 2
1 1 2
c h 2o h c h 2o h
HOH2C-------' (D)

H20/DC1
- (G)

on (E) OH (F)

c. H 20 + D C 1 ^ H 0 D + HC1

V H + v D+ u c k h n n g t n cng electron, sa u HoO v DoO .tn cng

nucleon n n t h u c c 4 cht:

CHiOH

OH (G ,)164 OH (G2)165 OH (G3)165 H ( 4)166

26-MSCHVBTHHOUC 195
Bi s 9.14 (HSGQG 2000 - 2001. Bng B)

1. Vit phng trn h p h n ng iu c h D - fructoz t D - glucozd. bit rn g

D - glucosazon k h i tc d n g VI b e n z a n d e h it to th n h oson ca D - glucozd
(H O CH 2(CHO H) 3COCHO).
2. C hitin (tch t v tm, cua,...) c coi n h l d n x u t ca xenluloz. trong
cc nhm hiroxyl nguyn t c.) dc th a y t h b n g cc nhm axety lam ino
(- NH - CO - C H 3).
a. Vit cng thc c u to mt on m ch c a p h n t chitin.
b. Gi t n m t m t xch ca chitin.
c. Vit phng tr n h p h n ng xy r a khi u n nng c h itin vi d u n g dch HC1
c (d), u n nng chitin vi d u n g dch N aO H c (d).

Bi gii

CHO c h = n - n h c 6h 5
L _
OH c = n - n h c 6h 5
1. HO + 3C 6H 5NHNH; HO + C 6H,NH 2
-O H -O H + NH3 + HiO
OH -O H
CH2OH CH?OH D - Glucosazon

ch= n - n h c 6h 5 CHO
L _
C = N - N H C 6H s c= 0
HO HO
+ 2 C 6HsCHO _ O H + 2 C 6H 5C H = N C 6H 5
-O H
OH OH
CH2OH CH2OH
Oson ca D - glucoz

CHO CH2OH
I __
c=o ^ (nhm - CH = o d b kh
HO Z11/CH 3COOH HO OH
+ 2[H] -------- hn nhm c=0 )
OH
-O H OH
CH2OH CH2OH
D - Fructozo

196
 H NHCOCH, H NHCOCH3

b. N - axetyl - 2 - am in o - 2 - deoxi - p - D - glucopiranoz.

CH2OH
o H -------- o.
c. I Ox + nHOH + nHCl

NHCOCH,
CH2OH

OH + nCH^COOH

I o + nNaOH

+nCH3COOH
NH 2 H nh2
(C h ito san - d n g tro n g cng nghip s n x u t giy v lm sch nc)

Bi s 9.15
V ita m in c (axit L - ascobic) c cu tr c n h sau:
o = c ------ H
^ C H 2OH
HO c o HO c
l
HO c ------

H c
I
HO H
I . ..
JCr
HO OH

CH2OH A xit L-ascobic

 a. H y gii thich tin h axit ca axit L - ascobic (pKa = 4,21).
b. T D - glucozd h y th ie t lp sd d p h a n n g dieu che a x it L - ascobic.

Bi gii
a. Do s h t electron c a nhom cacbonyl lm cho lien k e t - OH endiol p h n cc
m a n h n e n c k h n n g tc h H + the hien tin h axit. H dn na, a n io n tao t h n h diidc
ben v n g ho bi hieu n g -C ca nhom cacbonyl. i

o = c X) c
II
HO C o HO C ) o HO c o
II' 0^ II 1
HO C oc o= c
- H+
H C
I
HO C H HO C H HO C H

CH2OH CH2OH CH2OH

b. D ieu che V itam in C.

CHO c h 2o h CHiOH f H 2OH
H -OH H -OH H OH c= o
HO -H H2/Ni HO- -H oxi ho HO H HO H
H -OH "H -OH enzirn H OH H OH
H -OH H QU Acetobacer xylinum
-O HO- H
c h 2o h CH2OH OH CH2OH
D - Glucozo D - Sobitol L - Soboza
CH2OH COOH
CH:3 O ^ C \ l
C H 3
\ / Uq _ q
\/
2CH,COCH: c [O] C 2H.0,
7 xn o / \
h+ 1 H cm H 2CTlJcCH^
H O CH, H O CH,

o=c
H
X
c h 2o ch3 c h 2o
H
X ch3
o=c
I
o=c O H O -C
I! O
HO -H IT H O -C
H Tautome H
HO H ho HO H
CH2OH CH2OH
Lacton ca axit Vitamin C
2 - xeto - L - gulonic (axit L - ascobic)
198
Bi tp t gii

Bi s 9.16

t chy h o n to n 1,34 gam c h t h u c A ch th u c 2 ,2 g a m CO v

0,9 gam Hr,0. A c cng th c p h n t tr n g vi cng th c n gin n h t. A tc d n g
vi a n h i r it axetic to r a e ste hai ln este. A kh ng p h n ng vi d u n g dch
A g N 0 3/N H 3. Khi tc d n g vi axit v c long th t A ch th u c m etan o l v hp
c h t B, c h t n y va c p h n ng vi d u n g dch A g N 0 3/N H 3 v p h n n g vi
a n h i rit axetic to e ste 3 l n este.
Khi b oxi ho n h n h n g th B ch u y n t h n h a x it cacboxylic c m a m it ca
axit ny p h n ng VI Bro tro n g s c m t ca N aO H to r a N H 3 v g lix e ra n e h it
(C 3H 60 3).
Xc dnh cu to c a A, B, c v vit cc phng t r n h p h n ng bit r n g B v
c c cng s ngu yn t c v u t hn A mt nguvn t c .

Bi s 9.17

C m t hp c h t sa lix in (C 13H 180 7) b th u p h n b n g e m u n s in cho I> - glucozd

v m t hp c h t l sa lig e n in (C 7 H 80 >). S alixin kh ng k h c thuc th Tolen.
Oxi ho salixin bng HNO 3 thu c mt hdp cht m khi thu phn hp cht ny
s n h n c D - glucoz v a n e h it salixylic. M etyl ho salixin t h u c
p e n ta m e ty lsalix in . T h u p h n hp c h t n y cho 2,3,4 ,6 - tetra - o - metyl glucoz.
H y cho bit c u to c a salixin.

199
 Phn 10
HP CHT D VNG

Bi s 10.1

1. Piriin v pirol l h ai d vng thm c tn h c h t ho hc c b n khng ging

n h a u (tri ngc n h a u ). H y cho bit l tn h c h t g? G ii th c h ti sao.
2. C n h n g hp c h t d vng thm n vng k h n g c n hm t h m th n h
p h n ngu yn t n h sau: c (52,94%), H (5,88%), N (41,18%).
a. Xc n h cng thc cu to c a cc hp c h t ny.
b. Gii thch n g u y n n h n tn h baz c a cc hp c h t ny. Vit phng trn h
p h n ng k h i cho cc c h t tc d n g vi HC1 th eo t l mol 1 : 1 v so s n h tnh
bazd ca cc hp c h t .
c. Nu n itro ho mi d vng , p h n ng s u tin xy r a v tr no? Bit
r n g k h n n g p h n ng v hng nitro ho c a m t s hp c h t lin quan n h sau:
ph

chnh

fl

H (II)
d. Gi s l n h n g d vng thm ni c h u n g th c th l n h n g hp c h t
no? N u 1 - 2 v d m in h ho.

Bi gii

o
Pirol
H
- T rong p h n t piriin, nguyn t N cn m t cp electro n khng th a m gia vo
lin hp vi vng thm n n th hin tn h baz.

HC1

N N C1
I
Piriin H

200
 - Khc vi piridin, cp electron ca n guy en til N tro n g p h n tii pirol da th a m
gia lien hdp vo tron g vng tao he thdm . Do d pirol h a u nhuf k h n g th e hien tin h
bazd, ngiidc lai pirol lai c tin h a x it yeu.

+ h 2o

2. a. Goi cng thc p h n tii ca hdp c h a t l CXH VN Z. T a c:

52,94 5,88 41,18 Q , 0
x : y : z = ------- : -------: -------- 3 : 4 : 2 .
12 1 14
Hdp c h a t co d a n g (C 3H 4N 2)n.

P h u luc 3. Cng th c c a m ot so hp c h a t d i vng

r
,a
Di vng 5 O N S
c an h m ot di t" i I
H
Furan Pirol Thiophen

N N N
jJ
O JI s '
H
Oxazol Imidazol Thiazol
Di vng 5
c an h 2 di to
N N
O N
l
H
Isoxazol Pirazol Isothiazol

N N
Di vng 5 II
N
c a n h 3 di to N V N o O
H 1

H H.
1,2,3 - triazol 1,2,4 - triazol l ,2,4 - Oxadiazol
) 1 ] !/\
4Y Y\
N
6 ^
Di vng 6 Ni n - N "N N
c an h Piridin Piridazin Pirimidin Pirazin
( 1,2 - diazin) (1,3 - diazin) (1,4 - diazin)
da Bin bstf linii

201
 V l hp c h t d vng thm n vng k h n g cha nhm t h n n nguyn t N
cng th a m gia t o vng. Cc d vng th m n vng thng gp l 5, 6 cnh, nn
n = 1 . Hp c h t c cng th c p h n t C 3H 4N 9.
m bo tn h thm th s electron 7t(k) tro n g vngphi tho m n h thc:
k = 4n + 2 (Cng thc Hiikeiy, n > 1 , nguyn.
(Tnh n c cp electron c a n g u y n t N th a m gia lin hp).
Do vy C 3H 4N 9 c c u to:
N
N
J N
I
H H
Imiazol Pirazol

b. H ai hp c h t t r n u c tn h baz v u c nguyn t N cn cp electron

khng p h n chia.

NHC!
+ HCl
N
I
H

0
+ HC1 NHC1
N
I
H
T nh baz c a im iazol m n h hn pirazol do nguyn t N th hin tn h baz
ca pirazol (N v tr 3) xa n g u y n t N cn li hn so vi nguyn t N v tr 2
ca pirazol n n c h u n h hng bi h iu n g -I ca nguyn t N cn li yu hn
(tnh baz m n h hn).

202
 c. Imidazol:

Phn hot ho mnh tng

t a ca (I)
\ 4

Phn hot ho tng t p ca (II)+> N

Phn hot ho mnh tung
Phn hot ho tng t p ca (I) t a ca (I)
NI
Hot ho tng t a ca (II) Hot ho tng t a ca (II)
H
V tc n h n electron s t n cng vo v tr h o t ho m n h n h t v p h n h ot
ho yu n h t n n khi n itro ho im iazol s xy ra v tr s 5.

Pirazol.
N
N
I
H
d. Gi s l n h n g d vng thm ni c h u n g th c th l:

NH

v.v...

Bi s 10.2

1 . Cho bit s n p h m ca cc p h n n g sa u

c h 2n 2 c h 3i
b.
'N o OH
I
H

C6H5CHO , 1 : 1
NaOH

2. Thc hin s sau:

a . U r + E tyl o m y la x etat ---- >

b. T h iour + m etyl ioua g Etyl bm ylm etylaxetat dd HBr

HI
(C5h 6o 2n 2).
203
27-MSCHVBTHHUC
 Bi gii

1. a. Q a P i

H ^ A
chuyn v| f| CH 2N 2

I . . - - ,

QH 5CH0 , 1:1
c.
N NaOH

CH 2- C H - O H c h = c h - c 6h 5
L
QHs
o
r..................!
NHH C2H5O H c f NH
2. a. 0 = c
\
/
...... > o= c( \h 2

NH-) 0=H C NH2 H

o
o o
OH
/ NH NH C ^
0=c' CH + 0 = c f yCH
NH 2 ' NH CH
H O ^ h

NH2 .NH NH
b- S = C ^ = HS CH^S c
NH2 NH2 N NH,
(d )

-, / * /
N -jH N f
CH,S c ' + .................. ^C H CH, CH^S V - CH,
N |H 2' x N==y
L....................... H (C)
OH

204
K in thc m rn g
1. Tng hp cc hp cht pirim iin cn 2 cu phn:
- B khung 3C: c - c - c , c th l:
' p - ianehit
1,3 - icacbonyl p *xetoanehit
p - Xetoeste
p - xetonitrin
- Hp phn iam in: N - c - N.
2. Uraxin v th im in l n h n g baz nit c trong thnh p h n cu to ca axit nucleic.
Axit nucleic l nhng hp cht cao phn t (polinucleotit) do nhiu nucleotit kt hp vi
nhau nh cc lin kt photpho ieste. A xit nucleic l thnh phn quan trng nht ca nhn
t bo.
H oO H oO
A x it n u c le ic N u c le o t it N u c le o z it 4* A x it p h o tp h o ric

H 20
I
B a z n it + P e n to z

- Baz nit thng gp trong phn t axit nucleic l dn xut ca pirim iin v purin:
o

'n ^ 5

H H
X ito z in U r a x in T h im in

- Pentoz c m t trong axit nucleic gm c p - D - ribofurancz v p D - 2 -

eoxiribofuranoz.

p - D - rib o fu ra n o zd p - D - 2 - eoxiribofuranoz
- Nucleozit c cu thnh t gc baz nit v gc pentoz nh lin kt N - glicozit gia
Cj ca pentoz v N 3 ca baz pirim iin hoc Ng ca baz purin.

205
 Chng hn:

o nh2

HN K N N

O ^ N
N
HOH

OH H
Uriin Adenozin

Nucleotit (nuclcozit monophotphat), chng hn

NH2

Aenilat

Bi s 10.3

Theo W atson v Grick, cu tr c ADN l chui xon kp gm hai m ch

polinucloetit song song xon u n vi ng k n h vng xon l 20. Hai m ch
c duy tr nh cc lin k t h iro gia cc baz nit lin k t vi gc pento/..
1 . Hy tr n h by lin k t hiro gia X v G, A v T.

2. Gii thch v sao trong ADN k h n g h n h Lhnh cp A - X hoc G - A. Bit G

l guanin, X l xitozin, A l an denin.

Bi gii

1. P h n t ADN gm hai chui polinu cleotit g n vi n h a u nh cc lin k t

hiro gia cc cp baz nit v tr i din n h a u theo n g u y n tc cp i nghim
ngt: A vi T (hai lin k t hiro), G vi X (ba lin k t hiro).
Lin k t gia X v G, A v T:

206
 o - o

2. X - A; G - A k h n g t o t h n h cp c v n u bnh thng A - X (A - G) c
th to c lin k t h iro n h n g m un vy th hai p h n t ng phi cch xa
nh au, do chui xon kp k h n g song song vi n h a u khi A lin k t vi X, G lin
kt vi A k h n g n g c u tr c c a ADN n n khng t n t i cp A - X. G - A trong
ph n t ADN.

K in thc m r n g
Phn bit hai nhm axit nucleic: Nhm axit eoxiribonucleic (ADN) v nhm, axit
ribonucleic (ARN) l khc nhau phn pcntoz trong phn t.
Vi phn t ADN, cc haz nit l aenin (A ), thim in (T), guanin (G) v xitozin (X)
(khng c u (uraxin)). Thnh phn ng l eoxiriboz.
Sacgcip pht hin thy qui lut v s'lng cc gc baz trong phn t ADN:
A = 1

T X

* Bit trt t sp xp cc nucleotit ca mt chui polinucleotit c th thit lp chnh xc

trt t sp xp cc nucleotit ca chui cn li. Trt t chnh xc cc nucleotit (cu trc bc
mt) ca chui polinucleotit l yu t mang thng tin di chuyn.
- Lin kt hiro gia cc cp baz trong phn t ADN:

207
 Vi phn t A R N , thnh phn ng l riboz. Cc baz nit gm acnin (A), xitozin
(X), guanin (G) v uraxin (U) (khng c thimin (77).
Phn t A R N chi c mt chui polinuclcott (tr mt s' vi khun), v cng c cc
vng c chui xon kp vi cc cp A - u, G - X; nn:
A . G .
1 v - = * 1

Bi s 10.4

Khi cho s e m ia x e ta l tc dng vi HBr th nhm - OH b th ay th bng nguyn

t brom. Khi cho cc hp cht c cp electron t do tc dng vi d n x u t halogen
th nguyn t c c p electron th ay th nguyn t brom pha i din VI nguyn
t brom. H y v it cc phng trn h phn ng biu din qu tr n h tng hp 1 - D -
glucozylxitozin th eo s sau:
D I _ HBr A 2,4-dietoxipirimidin r, NH, 1 T~\ 1
-glucoz----- >A------------- ----------- * B * l-D-glucozylxitozin

-
Bi gii

c 2h 5

N:

N OC2H,
-------------

(A
)
OC2H5 NH

C1H2(0H CH-iOH
H / o y 'O o. N ^ O
NH
m H >
) h N - .- s H
H OH H OH
(B)

Bi s 10.5

A tropin l dm xut ca tro p an c trong cy Atropabelladona. c c tn h cao

n h n g vn c si cdng trong y hc lm thuc gim au (gy t cc b) v c bit
d n g trong khoai raiit lm thuc gin ng t mt.

208
 Atropin c cu trc nh sau:

nch3

Oc CH CHiOH
II
o q h 5

1. Hy ghi d u (*) vo cc n g u y n t cacbon b t i.

2. Khi th u p h n a tro p in tro n g mi trng axit t h u c hai s n ph m chnh

l tropin (khng c tn h q u a n g hot) v a x it tropic (cng k h n g c tn h q u a n g hot
nh ng c th t c h th n h h a i h a i i quang). Vit phng t r n h p h n n g v c ch.

3. Khi oxi ho tro pin b n g KoCr 90 7 tro n g axit sinh ra l n l t tripinon v axit
tropinic (CgH 130 4N). Vit s p h n ng di d n g cng thc cu to.

4. Ngi ta iu c h a tro p in b n g cch cho tro p in tc d n g vi axit tropinic

(xc tc H 0SO 4) song hiu s u t th p . V sao?

H y nu cch iu c h tt hn cng x u t p h t t h a i c h t trn.

Bi gii

1. Atropin

o - c CH C H 2O H

O
** L
q h 5

NCH NCH

H 20 / H 2S 0 4
2. H + H O C H 2C H C O O H

o - c C H C H 2O H OH
II I T rop in
o c6h , A x it trop ic

Do tnh b tr ni phn t nn tropin khng c tnh quang hot, cn do tnh b

tr gia hai i quang nn axit tropic cng khng c tnh quang hot.

209
C ch phn ng:

H II

*0 C 6H5 OH C6H 5

HO
* HiO \ *
+ c CH CH2OH - c CH CH2OH
H I
/ 1
HO
0 c 6h 5 c 6h 5
-H+
o
c CH CH2OH
HO
QH5

k 2q-2c v h +

4. P h n ng t h i u s u t th p l d<o:

+ 2 H 20

H7SO4 c
HO c CH CH2OH
II
O
h o c C = CH2 + H20
II
o c 6h 5

210
* Cch iu ch tt hn:

Q- Q 0 Q PC-
HOcCHCH2OH - - HOCCHCH2OCOCH3
o Q,H, o QH,

H
o QH5
o-cCHCH2
II I L
o qh5 *

Bi S 10.6 (Chun b Olympic Ho Quc t ln th 35)

Coniin l m t hp c h t c c tro ng cy c cn (hemlock, tn khoa hc conium

m aculatu m ), c h n h vi c h t ny ngi ta u c Socrates, mt n h tr i t hc Hi
Lp c. Coniin l m t hp c h t cha nit thuc h a n k alo it.
H y tm c u tr c ho hc v ho hc lp th c a coniin b n g cch hon t t
chui p h n ng sau . ng thi, vit cu tr c cc c h t t r u n g gian A, B, c.

i. C H 3I(Mctvl ho Hofmann)
Con i in - A (C | 0H->N) quang hot
2. A g 20 , H 20 , t

1. CHjICMctyl ho Hofmann)
1 ,4 -o cta d ie n + 1,5 -o cta ien
2. A g 2O t H 20 , t

C 6H 5CH2COCl KM n4 H 2/Pd/C
Coniin B axit (S) - 5 - aminooctanoic
NaOH, 0nc

Bi gii

.H
1. CH 3I(c0 d)
Hyk
CH 3CH 2CH2X N 2. Ag 20 , H2 0 CH 3CH 2C J / ;^ S O H
i h 3c ch3

28-MSCHVBTHHUC 211
 1 . CH,1
H - ___ - _____
CH 3CH 2CH2^ N(CH 3)2 2 . Ag 20 , H2 c h 3c h 2c h (CH,),OI
(A)

\
c h 2c h 2c h 3
^ c h c h 2c h 3 - h + 1 ,4 - Octaien

II
\\
c h c h 2c h 3

Q,Hsa 2coci(Z^ci) KMnO

H yk
CH3CH2CH2' y NaOH, 'c y**'
H z

73 N HVR1/C h 2n
CXX)H COOH
CH3CH2CH2^ H CH<CH2CH2^ " h
Axit (S) - 5 - aminooctanoic

Bi tp t gii
Bi s 10.7
Cho hp c h t th i n n h i n A:

OCOCfiHs (Cocain)
un n h A vi d u n g dch N a 18OH long tro n g H ^ o , s a u m t thi gian thu
c s n p h m cui c ng l Ekgonin.
1 . Vit s p h n ng. Cho bit cng th c c u tr c c a E k gon in v s n phm
tr u n g gian .
2. Ngi ta c th iu c h A t hp c h t sau:
H COOH

N -C H ,

Hy th i t lp s p h n ng.

212
 Phn 11
BI TP
TNG HP

Bi s' 11.1 (HSGQG 1997 - 1998)

C phng tr n h p h n ng sau:

(A ) (B ), h i u s u t 5 5 %

1. Vit c ch p h n ng.
2. T hay A bng C 6H 5 - C H (C H 3) - CH2 - CH2 - C(CH 3) 2O H (A 1),
C 6H 5 - CH - CH - C (C H 3)oOH(A9) v tin h n h p h n ng tro n g iu kin tng
t nh trn t h u dc s n p h m hu c tng ng Bj (hiu s u t 86 %), Bo (hiu
s u t 65%).
a. Vit cng th c cu to c a Bj v Bo.
b. T i sao h i u s u t p h n n g to r a Bj v B.) cao hn to r a B?

Bi gii

1. C ch p h n ng:

^ 2 ch m nhanh

-H

213
 II,C CH,
(B), hiu sut 86%.

OH H^ 85
10c

(B-i), hiu sut 65%.

b. P h n ng to th n h ! v B 2 phi i qua giai on to r a cacbocation (b). (c)

v cc s n p h m t r u n g gian (bj), (Cj):

(b|) (C|)

Nh cc nhm C H 3 y electron nn cacbocation (b) v (c) bn hn (a), cc sn

p h m t r u n g gian (bj) v (Cj) c ng bn hn (aj). Do vy (b), (c), (bj), (Cj) dc to ra
d d n g v n hiu hn. iu d n n hiu s u t ca B v Bo cao hn B.

Bi s 11.2 (HSGQG 1999 - 2000)

1 . Tm hp c h t h u c A, B, c,
D, E, G, H, I u ch a 35,56%C; 5,19%H;
59,2 6%Br trong p h n t v u c t khi hi so vi nit l 4,822. un nng A hoc
B vi du n g dch N aO H u th u c a n e h it n - butiric, u n nng c hoc D vi
du n g dch N aO H u th u c etylm etyl xeton. A bn hn B, c bn hn D, E bn
hn G, H v I u c nguyn t c trong p h n t.
a. Vit cc cng thc cu tr c ca A, B, c , D, E, G, H v I.
b. Vit cc phng tr n h p h n ng xy ra.
2. Hai xicloankan M v N u c t khi hi so vi m e ta n b n g 5,25. Khi
monoclo ho (c chiu sng) th M cho 4 hp cht, N ch cho mt hp c h t duy nht.
a. Hy xc n h cng thc cu to c a M v N.

214
 b. Gi t n cc s n p h m to t h n h theo d a n h p h p IUPAC.
c. Cho bit cu d n g bn n h t ca hp c h t to t h n h t N, gii thch.

Bi gii
1. a. M = 28.4,822 = 135(vC).
35,56 . 5, 1 9 59,26
c : H : Br = 4 : 7 : 1
12 1 80
> (C 4H 7B r)n : (12.4 + 7.1 + 80.1)n = 135 -> n = 1.
Cng th c p h n t ca A, B, c, D, E, G, H, I l C 4H 7Br.
So s n h t l s nguyn t c v H suy ra cc hp c h t c m t lin kt i hoc
mt vng no.
T h u p h n d n x u t halogen th u c ancol, khi th u p h n A hoc B th u c
a n e h it n - b u tiric nn A(hoc B) c m ch cacbon k h n g p h n n h n h v c lin kt
c = c d u m ch (v nhm > c = CH - OH s chuy n t h n h nhm > c = CH = 0).
C h t c (hoc D) ph i c lin k t c = c gia m ch cacbon (v nhm
> c = c C H 3 s c h u y n th n h nhm > CH - c C H } ).

H 0
Da vo cc d kin ca u bi suy ra:
CH3CH2 x H CH,CH2. Br CH3 Br
' \ / \ _ /
A: c= c B c= c c c= c
/ \ / \ / \
H Br H H H CH3
CH CH2Br
\ I/
D
/ \
H H

H(hoc I) : I(hoc H ) :

b. Cc ph ng t r n h p h n ng:

CH 3CH2 C H = CHBr + NaOH [ c h 3c h 2 C H = c h OH + NaBr

11. i. _
c h 3c h 2 c h 2 c h = o
CH 3 C H = C CH 3 + NaOH CH3 C H = C CH 3 + NaBr

Br OH

. I
c h 3 c h 2 c c h 3

o
215
 Nu c h t c v D, hoc E v G l n h n g ng p h n cu t o v v tr ca lin kt
i c = c (ng p h n c lin k t i pha trong m ch bn hn ng p h n c lin
kt i u mch, th d C H 3 - CH = CBr - CH 3 l c v C H 3 - CH.) - CBr = CH.) l D).
2. a . M = 5,25.16 = 84.
CnHon : 14n = 84 -> n = 6 .
C T P T c a M(N): C 6H 12.
Theo cc d kin u bi. M v N c cc CTCT:

(ai) (a2) (83) (a.) (a5)

a : 1 - Clo - 2 - m etylxiclopentan.
a 9 : 1 - Clo - 3 - m etylxiclopentan.
a 3 : 1 - Clo - 1 - m etvlxiclopentan.
a 4 : C lom etylxiclopentan.
a 5 : Cloxiclohexan.
c. C u d n g bn n h t ca hp c h t to th n h t N:

v d n g g h b n n h t (bn hn d n g thuyn), nhm t h v tr e (equatorial) bn

hn v t r a (axial).

Bi s 11.3 (HSGQG 1999 - 2000)

COOH
....... ...................................................
1. A x i t x it r ic h a y l a x i t l i m o n i c H O O C C H 2 c C H 2 coon c cc g i
tr pK a l 4,76; 3,13 v 6,40.
H
H y gi t n a x it n y th e o d a n h p hp 1UPAC v ghi (c gii thch) t ng gi tr
pK a vo nhm chc thch hp.
2. un nng a x it ti 170c th u c axit aconitic (CgHgOg). K h axit aconitic
sinh ra a x it tricacbalylic (hay l a x it propan - 1,2,3 - triccacboxylic). Nu tip tc
u n nng axit aconitic s th u c hn hp gm a x it itaconic (C 5 H 60 4, k h n g c
ng p h n h nh hc) v ax it xitraconic (C 5H 60 4, c ng p h n h n h hc); hai a x it ny
chuyn ho ngay th n h cc hp c h t mch vng c cng cng thc p h n t C 5H 4O 3.

216
 Hy vit s cc p h n ng xy ra di d n g cc cng th c c u to, v cho bit
axit aconitic c dng p h n h n h hc hay khng?
3. Ngi ta c th tng hp a x it xitric x u t p h t t ax eto n v cc ho c h t v c
cn thit. Hy v it s (i cc p h n ng xy ra.

Bi gii
3,13
COOI

1 1 0 0 C CI 2 c CI ]2 COOl 1 - C O O I1 C 3 c pKi( nh nht

4.76 6,40 v chu nh hng -1 mnh nhi
(6,40) ()l (4.76) ca 2 nhm -COOl 1 v nhm - o u
Axit 2 - h i ro x ip ro p a n - 1,2,3 - tricacboxylic.
COOH

2. HOOC CH2 C C H 2 COOH Axit xitric(C 6H 80 7)

OH

1 7 0 c -H 2o

COOH COOH
H
HOOC CH, C H COOH HOOC CH 2 ch - CH COOH
Axit aconitic Axit tricacbalylic
(Q W V (C fiH jA .)
Axit aconitic c ng p h n h nh hc v c c iu kin cn v .
Khi u n nng a x it aconitic:
Axit aconitic
(C6H6O)
CO,

1
COOH
HOOC CH2 c h = CH COOH HOOC CH2 c = CH 2
Axit xitraconic Axit itaconic
(C 5HO4) (C 5h 6o 4)

- h 2o h 2o

CH

O ^ O ^ O O ' O' 'O

(C 5H 403)
(C3H4O3)

217
3. Srt phn ng:

O O OH
il CU, x t II J ( 'N __ I
c h 3 C CH 3 - C1CH2 C CH 2C1 - C1CH2 CH 2C1

CN
OH COOl

2KCT NCCH 2 CH,CN HOOC CH 2 c C H , COOH

- 2 KCl
1
CN, L
OU

Bi s 11.4 (HSGQG 2000 - 2001)

Xinconiin(X) c cng thc cu to:

l ng p h n lp th c 9 ca xinconin (Y).
1 . Hy ghi d u * vo mi n g u y n t cacbon b t i v k h o an h vng trn
nguvn t m t c tn h bazd m n h n h t tron g p h n t X.
2. Cho t t d u n g dch H Br vo X n h i t ph ng ri u n nng nh, sin h ra
cc s n phm c h n h l A (C 19H 23B rO N 2), B (C 19H 24B r 2O N 2), c (C 19H 25B r 3O N 2) v
D (C 19H 24B r 4N 2).
Ch ho D vi d u n g dch KOH tro n g ru 90 th u dc E (C 19H.>oNo).
Hy vit cng thc cu to c a A, B, c, D, E. G hi d u * vo mi nguyn t
cacbon b t i tro n g p h n t D v E.
3. Cho CgH5COCl vo X v Y th u c s n p h m u c cng thc
C 96Ho 6BroOoN 9 ( t l F v G). F v G c ng n h t (cng m t cht) h a y khng?
C h ng c n h i t nng chy ging n h a u h ay k h c n h a u ? ti sao?

Bi gii

218
 CH CH3 CH=CH

(E)

F v G l ng p h n cu h n h c9 tng t (X v Y) v p h n ng vi
C 6H 5C0C1 kh n g lm t lin k t c9 - 0 v vy F v G khng ng n h t, chn g l
nh n g ng p h n i q u a n g c a n h a u n n c n h i t nng chy ging n h a u .

Bi s 11.5 (HSGQG 2002 - 2003)

Ozon p h n m t tecpen A (C 10H 16) th u c c h t B c cu to n h sau:

c h 3 c c h 2 c h --------- CH c h 2 c h o

o
CH CH

Hiro ho A vi xc t c kim loi t o ra hn hp s n p h m X c cng thc phn

t C10H20-
1. Xc n h cng th c cu to c a A.
2. Vit cng th c cu to cc ng p h n cu to tro n g hn hp X.
3. Vit cng th c lp th d n g bn c a cc ng p h n tro n g hn hp X.

29-MSCHVBTHHUC 219
 Bi gii

i. CHr C CH2 CH--------

r*rh \ /
i 'c
cH .r

H2, xt
X:

(Vng 6 cnh bn hn vng 7 cnh).

3. C u d n g bn:

CII,
( 1 ): ,
I C
CHI33 I
(eo aa) CH} (ao ea)

(II): = 7 r ! ' T ^ 3 \
: h 3x ch3 I ch3 ch

(ee > aa) (ee > aa)

CH 3

CH 3

Bi s 11.6 (HSGQG 2002 - 2003)

Hp c h t A (C 5HgOBr) khi tc dng vi dun g dch iot trong kim to ra kt t a

m u vng. A tc d n g vi dung dch NaOH to ra 2 xeton B v c cng c cng thc
p hn t C 5H 80 . R, c u khng lm m t m u dun g dch kali p e m a n g a n a t lnh.

220
chi c B to kt t a vng vi dung dch iot trong kim. Cho B tc d n g vi
CH^M gBr ri vi HoO thi thu lie I) (CfiHjoO). 1) tc dng V(3i H B r to ra hai dng
p h n cu to K v F c cng thc phn t CHjjBr, trong ch c E lm m t m u
d u n g dch kali p o m a n g a n a t lnh.
D ng cng th c cu to vit s (l p h n ng t A to th n h B, C. I). K, F. Vit
tn A v D theo d a n h php IPAO.

Bi gii

CI 1 , c CI I CI I2 CI I
II '
II
o Br

0 OH CHi c
Cl I, CI 2 c h 2 I12
i - h 2o -Br , <B)
o (A)
Hr

- h 20

Tn gi: A: 5 - Brom - 2 - pentanon; D: 2 - Xiclopropyl - 2 - propanol.

Bi s 11.7 (HSGQG 2002 - 2003)

1 . D ng cng th c cu to hy hon th n h s tng hp sa u y:

C 6H 5NH 2 H osci NH
COCl2 + CH3OH > C2U30 2C1 * B - . ChHs0 4NSCI *

H 0
-------- D i C 6H80 2N2S
(B, D l cc hp c h t hu c).
2 . Gii th c h hng ca p hn ng to th n h C 8H 80 4NSC1 v C 6H 80 9N 9.
 Bi gii
1.
COCI cu ,O I I C H , 0 - - C Cl + HCI

O
NH c o CH 3 NH c o CH,
Q H 5n h 2
C H , o c C1 -* O h o s o 2ci
I
O
II -H Cl
O (B) (C)

s o 2ci

NH c O CH NH 2
l
NH 3 o

(D)

s o 2n h 2 s o 2n h 2

2 . -N H C O O C H 3 nh hng 0 -, p-; do kch thc ln, tc n h n ln nn vo v tr p

-N H C Q O C H 3 este - a m it th u p h n th n h C O 9 , cn -SO 9N H 9 bn hn.

Bi s 11.8 (HSGQG 1999 - 2000)

1. C 5 l ng ri n g bit cc cht: c u m e n hay isopropylbenzen (A), ancol

benzylic (B), anisol hay m etyl phenyl ete (C), b e n z a n d e h it (D) v a x il benzoic (E).
Bit (A), (B), (C), (D) l c h t lng.
a. H y s p xp th t t n g d n n h it si, gii thch.
b. Trong qu tr n h bo q u n cc c h t trn, c mt l ng c h t lng thy x u t
hin tin h th. H y gii thch hin tng b n g phng trn h p h n ng ho hc.
c. Hy cho bit cc cp c h t no c th p h n ng vi n h a u . V it cc phng
tr n h p h n ng v ghi iu kin (nu c).
2. Trong q u tr n h iu c h m etyl tert - b u ty l ete (MTBE) t ancol, ngi ta th u
c th m hai s n p h m khc.
a. Vit phng tr n h p h n ng iu ch M TBE t hirocacbon.
b. Vit cng th c cu to hai s n p h m ni trn .
c. Vit cng thc cu to cc s n ph m sin h r a v phng t r n h p h n ng khi
cho MTBE tc d n g vi HI.
3. C mt hn hp cc c h t r n gm: p - tolu in p - m etylan ilin), axit benzoic,
n ap h talen .
T rn h by n gn gn phng p h p ho hc tch ring t n g c h t.

222
 Bi gii
1. a. T h t t n g d n n h i t si
(C I 02CHQHs < CJUOCVU < QIUCSI = 0 < O JU 1 1 - OM < QH<COOH
(A ) (C ) (D ) ID) (E )

- Phn cc - Phn cc - Phn cc - Phn cc - Phn cc

(yu hn C). (yu hn D). - Khmg c - C lin kt - C lin kt
- Khn c - Khng c lin kt hiro lin hidro lin
lin kt lin kt hiro. phn t(yu phn t
h i ro . h i ro . h n c a E ). m nh

M t khc A, B, c , IX E c khi lng p h n t xp x nhau.

b. L ng c h t D (C 6H 5CH = 0).
2C 6H 5CH = 0 + O aUhnKkh)-> 2 C 6H 5COOH
(lng) (rn. tin h th)

c. CgHgCOOH + C 6H 5C H 2OH C 6H 5C O O C H 2C 6H 5 + H.,0

c (>iisc i = o + C6H 5CH2OH CfilljCH OC1 2C 6H5 + h 2o

OH
c 6h sc i i = o + 2C 6H 5CH2OH c 6h 5c h o c h 2c 6h 5 + 2H2o

o c h 2c 6h 5

2. a. 2 C H 4 + 02 -> 2 CH3OH

(CH3)2C = C H 2 + HOH lli (CH 3) 3C - O H

(hoc (CH 3)3CH h L...> (CH 3)3C - Br - J ja O f r d d ^ ^ (CH 3) 3Q . OH).

(CH3)3C - OH + C H 3OH M 40^ - 4 (CH 3)3C - O C H 3 + H 20

b. C H 3OH + C H 3OH ch3-0 -ch 3 + h 20

(CH 3)3C - OH + (CH 3)3C - OH - H ^ l-4--c > (C H 3)3C - O C (C H 3)3 + H 20

c. (CH3)3C - 0 C H 3 + HI -> C H 3OH + (C H 3)3C -1
3. K huy u hn hp r n vi lng d d u n g dch NaOH long, ch axit benzoic phn
ng to th n h n a tr i benzoat tan, hai c h t cn li khng p h n ng, lc tch ly hn
hp r n v dung dch. Axit ho dung dch n a tri benzoat b n g d u n g dch HC1 long:
C 6 H 5CO O H + N aO H -> C6H 5COO Na + H 20
(rn) (tan)
C 6H 5C O O N a + HC1 -> C6H 5C O O H + NaCl
- K huy hn hp r n cn li(p - toluin, n a p h ta le n ) vi lng d d u n g dch HC1
long, ch p - toluin p h n ng to mui tan. Lc tch ly n a p h ta le n ; kim ho
d u n g dch mui, th u c p - toluin:

223
 p - C H 3C 6H 4N H 2 + HCl -> p - C H 3C 6H.1N H 3+ C r + H.jO
(ran) (t an)

p - C H 3 0 6 H 4 N H 34' e r + N aO H -> p - CH3C6H.NH2 + N aC l + H 20

* C the tch theo s d sau:

NaOI 1long
p - CH3C615NI l / C I --------- / J - C H . A H 4NH;
MCI long, d (tan)
Hn h p ----------------- Lc
rn NaOl long, dir
Axit benzoic + naphtalen------------------ Lc
V.________________________ __________________________ J

(khng tail) Naplitalen-

(khngtan)
I ICI lona
c 6h 5c o o h QHsCOONa -
(khng tan) (tan)

Bi s 11.9 (HSGQG 2000 - 2001)

1 . X ut p h t t brom benzen cha 1 c v tr 1 v cc ho c h t v cr cn

khng cha 14c, h y diu ch cc hp cht thm cha uc v tr 3:
a. Anilin.
b. Iotbenzen.
c. Axit benzoic.
2. Hon th n h s phn ng sau v gi tn cc sn phm t A n F:
Na2Cr204 2H
c * D
Cl2(l mol) . H20
Benzcn(l mol) --------- A B -----
t .p I INC), l c - 11CI .
E ------- 1'
I moi
3. Khi oxi ho etylenglicol bng H N O 3 th to th n h mt hn hp gm 5 cht.
Hy vit cng thc cu to p h n t ca c h t v s p xp theo tr t t gim dn
n h it si c a c h n g (c gii thch).

Bi gii
Br COOH
H Noyi2s o 4
l.a. -------------
0

14

Nil,

224
 A: Clobcn/en B: Phenol
o
OH C: p - Benzoquinon

OH

OI
t r
INO,
OH OI

Fe, HC1
------------
o n

N0 2 E: p - Nitrophenol N 2 F: p - aminophenol

COOH

CH2 OH [O] Q IO O] C H 2 O H [0] eoQH [Q COOH

3. (B)
CII2 OM CH2 OH CHO COOH
(A) (D) (E)
CHO
(C)
N h i t si: E > R > D > A > c.
(Gii thch b ng h iu ng electron v lin kt hiro).
Bi s' 11.10 (HSGQG 2000 - 2001)

1. Clorofom tip xc vi khng kh ngoi nh sng s b 0 X1 ho thnh photgen

r t c. n g a c, ngi ta bo q un clorofom bng cch cho th m mt lng
nh ancol etylic chuyn photgen th n h c h t k hng c.
Vit phng trn h p h n ng oxi ho clorofom bng oxi khng kh th n h
photgen, p h n n g ca photgcn vi ancol etylic v gi tn s n phm.
2. un nng vi git clorofom vi lng d dung dch NaOH, sa u nh thm
vi git d u n g dch K M n 0 4 thy hn hp x u t hin m u xanh.
Vit cc phng trn h phn ng v gii thch s xut hin m u xanh.
3. Khi ti n h n h iu ch axit lactic t a n eh it axetic v axit xianhiric, ngoi
s n p hm mong m un ta cn thu c hp c h t X (CgHs0 4). Vit cng th c cu to
ca X v cc phng trn h phn ng xy ra.

Bi gii

1. 2C H C I 3+ 0 2 2C O C I 0 + 2HC1

C0C1 2 + 2 CoH5OH - 0 = C (0 C 2H 5)2 + 2HC1

ietyl cacbonat

2. CHCI 3 + 4N aO H HCO ONa + 3NaCl + 2 H 20

HCO ONa + 2 K M n 0 4 + oNaOH - N a 2C 0 3 + K 2M n 0 4 + N a 2M n 0 4 + 2H20
Anion M n 0 42' cho m u xanh.
3. Axit lactic l cx - hiroxiaxit. trong iu kin tin h n h phan ng chuyn
th n h lactit X:
CN
C H r-C H = 0 + HCN ----- CH, c u
CN H COOH
CH3 ch' + 2H20 + H+ - 1- * - CH3 CH + NH4+
OH X ()H
/ COOH co o
2CH3 C H ^ CH3 C / X CH CH, + H20
OH 1 ooc
(X)

Bi s 11.11 (HSGQG 2002 - 2003)

H y ngh s p h n ng vi y iu kin :
1. T etilen v cc c h t v c tng hp cc hp cht sa u v sp xp ch ng theo
th t t n g d n nh it si.

226
 C 2H 5(X r H 2C H 2O C H 2C H 2( ) H ( c t y l c a c h i n o l ) ; {{ o x NH
\ ___ / \ ________________/
ioxan Mopholin
2. T benzen hoc toluen v cc ch t v c tng hp cc dc c h t sau: Axit
4 - am ino - 2 - hidroxibenzoic; a x it 5 -amino -2.4 - ihiroxibenzoic.

Bi gii

1. C H = C H 2 H2Q - *> C2H5OH

t",p C H ;- CH;
0 2/Ag C2H5OH _ \ )
CH2= C H 2 - c h 2------;CH 2 ... . CH2CH2O H --------------
\ / H ,0+ h 3o +
o c 2h 5
CH2CH2OCH2CH2OH (A)

c 2h 5o

2CH2------ CH, HOCH2CH,OCH,CH,OH * (B)

\ / N /
o
NHn 1 H2S0 4 / -----\
2CH2------ CH2 - IIOCH2CH2NHCM2CH2O H ----- Q NI (C)
\ / h 2o 2.Na 2C 0 3 \ ___ /
o
N hit si:A > c > B.
NO- Nil
HNO Sn/HCl HNO-
2.
n 2s o 4, l'

no2 N1I
COOH
OH OH
C 0 2, OH

a T
NH NU,
'OOH
NH- OM
HNO C02, OH
1----- 1
t.p h 2s o 4, t
oh
'OOH 1
COOH
OH OH
Sn/HCl
* I
o 2n ^ Y
h 2n ^ Y
OH OH

30-MSCHVBTHHUCO 227
hoc:

OH

Bi s 11.12 (HSGQG 2002 - 2003)

P h n g tr n h p h n n g io t h o a x e t o n tr o n g d u n g dch c xc tc axit:

CH 3 c CH, + I 2 - - r CH3 c CH2I + HI

3 I 3 2 3 l 2
o (A) (B) o (E) (F)
Thc ngh im cho th y p h n n g l bc n h t i vi a x e to n v i vi H +. M t
k h c , th c n g h i m c n g c h o t h y tr o n g q u tr n h p h n n g c t o r a cc c h t tr u n g
g ia n CH3 c C H j v CH3 - c= C H 2 . T n g i ta n u g i t h i t p h n n g
II
+ OH OH
tr n xy r a q u a 3 giai on.

1. V it phng trn h biu din nh lu t tc ca p h n n g v cho bit n v

(th nguyn) ca h n g s tc p h n ng.

2. Vit biu th c biu din tc p h n ng qua: tc ti u h ao (A), (B); tc

to th n h (E), (F).

3. Vit phng t r n h biu din 3 giai on ca p h n ng. G iai o n no quyt

nh tc p h n ng.
4. m t th nghim , ngi ta ly nng b a n u c a axeton, iot v ion H +
u b n g 0 , 1 M. S a u 30 p h t, nng axeton gim bt 15% so vi n n g b a n u.
Tc to t h n h H I t i thi im 30 p h t l 3,4 7 . 1 CT5 m o l.r 1. p h t -1. H y tnh
h n g s tc p h n ng.

228
 Bi gii

1. Phng t r n h b iu din nh lu t tc p hn ng: V = k [CH 3 - c o - C H 3] [H+].

n v (th nguyn) ca h n g s tc p h n ng:
mol mol mol
V = k[ ? ]xC c h ,.co-CH, xC
lt. p h t lt H lt

mol 1
v[ ] lt.pht pht lt
k ?
C[ ].C[ ] mol moi mol mol.pht
lt lt lt
-> k [lt.m ol.pht].
2. Biu thc b iu d in tc p h n ng qua tc ti u hao v tc to th n h cc
cht.
1 AC
Theo cng th c : v(p) = X -
V At

V,: h s ca c h t 1 trong phng tr n h t lng vi quy c:

+ cho c h t to th n h .
- cho c h t p h n ng.
T phng t r n h t lng:
H+
CH3 c CH3 + I2 CH3 c CH 2I + HI
l
0 0

ta c:
1 A[CH 3 C Q C H 3 ] 1 A[I2 ] = 1 A[CH 3CO C H 2 I] = 1 A[HI
v(p)
1 At 1 At 1 At 1 At
3. Ba giai on c a p h n ng:
K,cb
CH3 c CI 3 + H+ ^ CH3 c CH 3 (1) cn bng thit lp nhanh
l
+OH
K2
CH3 c CH 3 = CH 3 C = C H 2 + H+ (2) (chm), quyt nh tc
chung phn ng.
l .
+OH H
K
CH3 C = C H 2 + I 2 CH, c CH2I + HI (3) (nhanh)
l
OH
C h ng m in h c c h p h hp vi nh lu t tc p h n ng:
v(p)= v(2) = K 2[CH3 c CH3]
+OH

229
 T h ay vo v( 2 ): v(p) = v(2) = K2. Kcb. [CH 3C O C H 3][HI] = K [C H 3C O C H 3]HI].
v(p) = K[CH 3CO C H 3][HI].
3. T nh nng p h n ng ti thi im t = 30 p h t.
[CH 3C O C H 3] = 0,1M - 0,15.0,1M = 0,085M.
[H+] = 0.1M + 0,15.0.1M = 0.115M.

v(p) = K [CH 3C O C H 3][HI] = + = + 3> 4 7 10~5(m ol.lt.pht). T d:

At

k = ------------ ----------- = ------- 3 i 7 -1 0 : Tm L l l - P ^ _ - 3 ,5 4 9 8 7 .10~3 ------ ----

[CH 3C O C H 3 ][HI] 0,085m ol.lt X0,1 l m o l.lt m o i.p h t

Bi s 11.13 (Bi tp chun b Olympic Ho Quc t ln th 32)

ng c t tr n g l saccaroz tin h k h i t c trp n g cy m a v c ci ng.

T ro ng d u n g dch, saccaroz b th u p h n c h m to t h n h d u n g dch D - glucoz
v D - fructoz gi l ng nghch chuyn. P h n n g th u p h n c th theo
di c b n g php o quay cc. D un g ch saccaroz c tn h q u a y phi
(ap1 =+66,53 .cm 3.g_ 1d m _1), tro ng khi d u n g dch ng n g h ch chu yn li

quay triap* ca glucoz b n g +52,7 .cm 3.g 1 .dm _1 v [cx]^ ca fructoz b ng

-9 2 ,4 .cm 3.g' 1 .dm_1). Tc th u p h n tu thu c n h i u vo n n g ion hiro.

1. V it phng tr n h p h n ng th u p h n saccaroz di d n g cng thc
H a rw o rth (vng phng).
2. K ho s t s nghch chuyn ca saccaroz ti 25 c t h u c cc s liu sa u
ca gc q u a y a t theo thi gian t:

t(p ht) 0 10 20 40 80 180 300 00

a() 6,60 6,17 5,79 5,00 3,71 1,40 -0,24 -1,98

a x tng ng vi chuy n i h o n ton. N h vy a t - a gip o nng

saccaroz. D n g s liu cho tr n c h ng t p h n n g l bc n h t theo nng
saecaroz v tn h h n g s tc .
 3. Trong d u n g dch HC1 0 . 1 M khi n h it t n g t 25 dn 3 0 c th tc t n g
gp i. Hv tn h n n g lng h o t ho.

Bi gii
c i OH
CH2OH
H ------V H H
1. OH H c l HO 1 + HiO
HO o \ ________ / (CHiOH

H OH Saccaroz h H
c h 2o h
H
OH H + HOCH2,HO T h
HO
H OH OH H
2 . V th biu din s p h thuc ca ln (a t - a x ) vo thi gian t.

t (pht) 0 10 20 40 80 180 300

ln (a t - a x) 2,15 2 ,1 0 2,05 1,94 1,74 1,22 0,55

H m th eo thi g ian ln (a t - deo) l m t ng th n g , n g h a l p h n n g bc mt.

dc b ng - 0 ,0 0 5 3 p h tf 1 n n k = 0,0053 p h t -1 = 8 ,8 3 x l0 -5 giy-1.

ln(a, - On)

0 50 100 150 200 250 300 350 t(pht)

-E. E,
3. k = A.exp v 2k = A.exp
298R 303R
1 1
ln 2 = -> E a = 1 0 4 k J.m o F 1.
.298 303

(exp(x) = e x, R = 8 ,3 1 4 J .m o r 1.K_1)

231
K in thc m rn g
Phn ng thu phn saccaroz xy ra theo phng trnh:

^12^22^11 + ~ * C g H 120 g + C 6H 120 6

Saccarozd Glucoz Fructozd
Tc phn ng ph thuc vo nng saccarozy nc v ion H + dng lm xc tc.
Lng nc c ly rt ln nn coi nh khng i v nng / / + g i nguyn trong sut
thi gian phn ng, v vy phn ng c coi nh bc mt v tc phn ng c xc nh
theo phng trnh:

v = - = kC ( 1)
dt
Bin i v ly tch phn ta thu c:

= k d t - - l n C = k t + I.
c
H ng s tch p h n I c th xc nh t iu kin ban u: t = 0, c = C q -* I = -IhC q.

- - l n C = k t - lnC 0 h ay k = - l n = l n (2 )
0 t c t c0- c x
Cq: nng ng ban u;
Cx: nng ng tham gia phn ng trong thi gian t;
c = Cq - Cx: nng ng thi im t.
ng saccaroz l mt cht quang hot, c kh nng lm quay m t phang nh sng
phn cc i mt gc a no .
N u gi: Q l gc q u a y l c bt u p h n ng

ctool gc quay lc ng saccaroz chuyn ho hon ton

at l gc quay thi im t.

th (a0 - oc) l bin thin gc quay t lc u ti lc kt thc phn ng t l vi nng

ban u ca ng (Cq).

(at - q) l bin thin gc quay t thi im t ti lc kt thc phn ng t l vi nng

cn li ca rtg(C(.
Thay nhng tr s ny vo phng trnh (2) ta c:

k= hay ln(at - (Xao) = -kt + ln (a 0 - aoo) (3)

t

S ph thuc ca ln(at - oe#) vo t l mt ng bc ln(at-cO

nht c h s gc l -k .
ln(a0- a j
N h vy, bng thc nghim (xy dng th biu
din s ph thuc ca ln(at - ac) vo t) c th xc nh
c hng s tc phn ng.

232
 Phn 12
MT
S CU HI TRC NGHIM

C u 1 . ng p h n no tro n g s cc ng p h n s a u bn v ng hn?
I. cis - hoc t r a n s - 1,4 - ib ro m x i o h e x a n

II. cis - hoc t r a n s - 1,3 - ibrom xiclohexan

a) I cis v II cis b) I cis v II tr a n s

c)I tr a n s v II cis d) I t r a n s v II tr a n s

C u 2. i vi mi c h t no sa u d n g cis bn hn d n g tra n s ?

C u 3. Cu tr c n g c a z - 2 - brom - 3 - m etyl - 2 - p e n te n l:

H3
C H 3 c = c CH 2 CH-CH 2 c CH C H 2 CH 3

Br CH 3 Br
a) b)
CH3 CH3

h 3c = c c h 2 CH3Br c = c CH2 CH3

Br CH 3
c) d)

233
Cu 4 . Cu tr c no sa u y c cu h n h E?
o o C1

HO c c OH H2C F
\ / \ /
c= c c= c
/ \ / \
H J H H3C m C1
C1 CH 2C1 Br C1

H
\ = c
X CH h 3c
X,
\ ____/

I
II IV

a) I, II b) II, III c) III, IV d) II. IV

C u 5 . G eraniol c th c bao n h iu ng p h n cis - tr a n s ?

CH 3

c h 2o h
CI 2 CH

CH2
\
CH
l
H3C CH
a) 2 b) 3 c) 4 ) 6

C u 6. C bao n h iu cu tr c tecpen c th t o t h n h t h a i dn v isopren?

a) 1 b) 2 c) 3 d) 4

Cu 7 . C bao n h i u n v isopren tro n g V ita m in A?

a) 2 ) 8

Cu 8. Tc n h n n o sa u y c k h n n g p h n n g vi a n k e n tro n g p h i ng
cng hp cis?
I. Cl 2 II. B r 2 III. H 2 + P t IV. K M n 0 4
a) I, II b) III, IV c) II, III d) I, IV

234
C u 9. Theo c c h t ra cho p h n ng cng electrop hin ca brom vo anken, hy
d don s n p h m no to th n h khi brom ho 1 - p e n te n trong nc?

OH Br

CH 3CH 2CH 2CHCH2Br CH 3CH 2CH 2CHCH 2OH

I n
Br OH

CH 3CH 2CH 2CHCH2Br CH 3CH 2CH 2CHCH2OH

ra IV

a) I, II b) I, III c) II, IV d) III, IV

C u 1 0 . s n p h m n o l c a p h n n g gia 1 - m etylxiclohexen vi HO (H 2S 0 4)?

CH CH H
\
/ OH
H CH 3
OH OH
a) b) c) d)

C u 1 1 . Hp c h t A c cng th c p h n t CgH 14 v p h n ng vi H 2/P t cho c h t B

C 8H 16. A l :

CH 3

ch3

a) b) d)

C u 12. Hp cht n o l sn phm c h n h c a phn ng gia

1,2 - im etylxiclohexen vi D 2 (Pt)?

CH 3
a) b)
d)

MSCHVBTHHCUC 235
Cu 13. Hp c h t no trong s cc hp ch t sau cho hai ng p h n khi p h n ng
vi clo tro n g cacbontetraclorua?

a) b) c) d)

Cu 14. 2,3 - b u tan d io l c th c bao nhiu ng phn lp th?

a) 1 b) 3 c) 2 d) 4

Cu 15. Cp cu tr c no sau y l ng phn i quang ca n h a u ?

CH- H

....... I. HO ...... NN
OH COOH
\
COOH ch3
C1 p

II
Br CH 3 H3C........ \^ .
Cl
c h 2c h 3
c h 2c h 3
H CH

m.
ch3 I ^ ^ O H
OH H
a) I, II b) II, III c) I, III d) I, II, III

Cu 16. Hai cu trc sau c q u a n h vi nhau nh th no?

NH2 H
H3C nh2
Hvv ^ CH3
c ^

H NH h 2n CH

CH 3 H

a) cu trc ng nht b) ng p h n lp th i q u a n g
c) ng phn lp th khng i quang d) ng p h n cu to

236
C u 17. Nhng hp c h t no sau y l hp cht meso'

c h 2o c h
113 CHO CH2OH CH2 OH
II OH H OH li 0 CH 3 CThO II
c c c

OH II OM H O CH h OCH
II
C C C C

CHO c h 2o h c h 2o h
CH2OH
I. II. m. IV.

a) I, II b) I, III c) II, III d) III, IV

C u 18. Hy ch r a c u h n h R, s tro n g c u tr c sau ca a x it isoxitric?

COOH
HOOCCH H

,1''
HO COOH
7
II

a) 2 - R, 3 - R; b) 2 - R, 3 - S; c) 2 - S . 3 - R ; d) 2 - s, 3 - s

C u 19. Mt hp c h t k h n g tr n g v t - n h C 5Hg, tro n g p h n n g h i ro ho th u

c c h t kh ng t r n g v t - n h C 5H 10. u l c h t kh n g t r n g v t - n h b an
u?
a) 1 - m etylxiclobuten b) 3 - m etylxiclobuten
c) 1 , 2 im etylxiclopropen d) xiclopenten

C u 20. u l s n p h m c h n h t h u c khi thu p h n xiclohexen oxit tro n g mi

trng axit?

a) ( H H b) (O H H c) d)

OHOH H OH

237
C u 21. C ht no l sn phim chnh thu c t phn ng sau?
H H
\ /
)ce' + H 1NCH1CH1NH2
H \ / H
o
/ \ ...
a ) H O C H 2C H 2N H 2 b) 0 NH
Y _y
c ) H O 2 2N H 2 C H 2 OiH d) H O C H : C H :N H C H 2C H 2N H C H 2C H 2O H

Cu 22. C h t no tro ng s ctc cht sau c tn gi ng theo d a n h p h p IUPAC?

a

/L CH
V C H 2 CH 2 CH 3
H CH 3

R - 2 - clopentan R - 4 - f io - 4 - m e t y l x i c l o h e x e r
I n
CH 3
B r C H 3( X M C I ^ T ^ F

H OCH 3 Br
CH2CH
v^n2v.n3
meso - 1,2 - ib r o m - 1 ,2 - im e t o x ie t a n s-2- f io - 2 - c lo b u ta n

m IV

a) I, II b) III, IV c) I, III d) II, IV

Cu 23. iu k in no s a u y l tt nht cho s diu c h isopropylm etyl ete?

a) N f% C H 3 + ( C H 3>2C H B r -------*

b) n* % C H ( C H 3)2 + C H jB r -----
t0
c) 3 OH + (CH3>2CHBr -*-

d) CH3OH + ( C H 3)2 C H O H

Cu 24. H y ch r a s n p h m ehn h t chui phn ng sau?

H 3

CH 3 COCI K ,C n O ?
AICI3 H 2S 0 4

238
 o

COOH

Cu 25. N h n g p h n ng ni tip no sa u y l tt n h t iu c h hp c h t sau

t benzen?
COOH

CH3C1 K2C207 hno3

a)
A1C13 h 2so 4 H2 s o 4
hno3 CH3C1 K2C27
b)
H2s o 4 A1C13 H2 SO4

CH3 0 C1 hno3

A1C13 H2 s o 4
CH3C1 hno3 K2 2O7
d)
A1C13 H2s o 4 H2 SO4

Cu 26. H y ch ra baz m n h n h t tro n g s cc c h t sau:

Cu 27. Cho chui p h n ng sau:

NaBH 4 HC1 Mg
o A ------D ^ c ---------
H ,0 ete

239
 OH /V H0
c)
x
Cu 28. u l s n phm chnh t phn ng sau:

MgBr + CH 3CH 2ND 2

) V - n d c h 2c h 3
a)C ^ D b)0 ^ H
Cu 29. H y ch ra qu trnh tt n h t iu ch c h t sau:

o N

NaBH4 hO
HN NaBH
a) ------ ----------- b)
h 2o h 2o

HN HN
c) d)
HVNi

Cu 30. Cng thc chiu Fia ca L - ioz nh sau:

CHO
HO H
H OH
HO H
HO H
CH2OH
Cng thc chiu Havt ca L - ioz l:
H CH2OH CH2OH H
HO ------ H
c h 2 h \
HHO
oJ O h
H \
H o. on HO q H
a) H HO b) H HO c) H..
OH
-X
H d)
c h 2o h \
H '
H OH H OH HO II H OH
OH H OH H H OH Oll OH

240
C u 31. C hai gluxit cho cng sn phm khi x l vi n a tri bohirua. Hai gluxil
d l:
CHO CHO CHO CHO
10 -H H OH HO H -O H
10 -H H OM H O ll HO -H
CH2OH c h 2o h CH2OH CH2OH
I II III IV

a) I. II b) I. III c) III, IV d) II, IV

C u 32. S n p h m u ti n khi cho 1,6 - xicloecanion tc d n g vi d u n g dch

NaOH u n nng:
OH

a) c)

C)

C u 33. Cho hp c h t sau:

o CH3

S n p h m tr n c to th n h trong p h n ng anol gia cc c h t p h n ng
ch n h sau:
ch3
a) CH 3CH2CHCHO
, II
c) c h 3c h 2c c h 3
c h c h c h 2c h ,
I
OH
_ ch3
L o
+ o b) c h 3c h c h 2c h o +
+ CHO d) CH 3CH 2CH 2CHO + o

CH

C u 34. S n p h m ca chui p h n n g s a u l:
H ,o0 Zn/Hg H
OH
C H 3CH2CHO
HC1 Pt
a) C H 3C H (C H 3)C H (C H 3)2 b) C H 3C H 2C H 3
c) C H 3C H 2C H 2CHCH 2C H 3 c) C H 3C H 2C H 2C H (C H 3)2

241
C u 35. P h n n g sa u cho s n p h m no trong s" cc s n p h m sau:

11 11
HC(CH 2)4CCH 3 + Na OCH 2CH 3 ----------

H ,c o o

11
a) r vy j c c h 3 b) cch3 c) d)
ch3

C u 36. N h ng c h t no sa u y c th s d n g tro n g p h n ng anol to

th n h s n p h m ch a 5 nguyn t c?
I. A x e tan e h it II. Axeton III. B e n za n eh it IV. A xetophenon
a) I, II b) III, IV c) I, III d) II, IV

C u 37. H y ch r a s n p h m chn h t chui p h n ng sau:

o o

NaOCH 2CH 3 H 3O
CH 3CH 2OC(CH 2) 5CO CH 2CH 3

o
o COCH 2CH 3 ^ cch 3
1/ 0 o o o
a) c o c h 2c h 3 b) c)
V ''Y
u )L _ r

C u 38. Cho chui p h n n g sau:

/ CH 2COOCH 2CH 3
NaOCH 2CH 3 H 3Q
Q
CH 2COOCH 2C H 3

S n p h m c h n h th u c l:
CO CH 3

242
C u 39. Sn phm chnh thu c t chui phn ng sau l:

socu CH3CH2OH C H 3C H 2O N a H3c r NH3
nO H --------
C H i COH ' = -; --------------- ---------
C H 3CH2OH

9 9
.............11 1 1 t \ \
a )C H 3CCHCCH 3 b) CH 3CCH 2CNH 2 c) d) C H ,C H = C H C N H
N
NH

C u 40. T h t t n g d n tn h baz ca cc nhm a m in tro n g cc hp c h t sa u l:

NH 2
__I
h n = c n h c h 2c h 2c h 2c h c o o h c h 3c h 2n h 2

nh2
I 111
II
a) I, II, III b) II, III, I c) III, II. I d) I. III. II

MSCHVBTHHOUC 243
 Phn 13
P N CC CU HI TRC NGHIM

Cu 1 c) Cu l i a ) Cu 21 d) C u 31 a)

Cu 2 c) C u 12 b) C u 22 c) C u 32 cl)

C u 3 c) C u 13 c) C u 23 b) C u 33 a )

C u 4 c) Cu 14 b) C u 24 b) C u 34 d)

C u 5 a) C u 15 a) C u 25 d ) C u 35 a)

C u 6 c) C u 16 a) C u 2 6 c) C u 36 a)

C u 7 c) C u 17 c) C u 27 a) C u 37 a)

C u 8 b) C u 18 b) C u 28 a ) C u 38 a )

C u 9 b) C u 19 b) C u 29 c) C u 39 b)

C u 10 b) C u 20 b) C u 30 a) C u 40 b)
 Phn 14
P S PHN BI TP
T GII

Bi s 1.15

1.

COOH
a. /HcSj

CH CH 3
I n r
11 151 Br- H H- Br
b. CH 3 *H H CH 3
111 n r
I LSI H Br Br -H
Br Br CH 3 CH 3 CH 3

COOH COOH HOOC

HOOc ')

HOOC COOH

COOH coon COOH COOH

H -OH HO -H HO -H H on
d. CH 3 C H C H C H C O O H
i i i H -OH HO -H H -OH HO H
H HH
H -OH HO -H H -OH HO H
CH 3 CH 3 CH 3 CH 3
COOH COOH COOH COOH
HO -H H -OH H -OH HO -H
HO -H H -OH HO -H H -OH
H -OH HO -H H -OH HO -H
ch3 CH CH, CH 3

245
 CHO COOH CHO coon
HO -H HO -H HO -H HO -H
2.
H -O H H -O H HO -H HO -H
C H ,OH COOH CH2OH COOH
Axit (-) tactric Axit mcsotactric

3.

b. C H 3 C H 2 H *CHCH 3

OH

CH CH, CH
H OH HO HO H
H T
11
/
\
C2H5 C2H5 C 2H 5

Bi s 1.16

CH CH COOH
Br- H b. HO H H OH c. H -C H 3
H Cl D. H H D H -ch 3
CH 3 CH COOH

246
 CH
b. H2N l
HO II
CH

HO

OH

Bi s 2.14

M = 20 M = 48
1. * P h n t H - F c 2h 5f
fi = 1,91 Dcbye = 1,80Debye

c th to lin k t hiro -H ... F- kh ng to lin k t hiro

Do cc p h n t H - F to lin kt hiro lin p h n t vi n h a u bn vng n n c
n h it si cao hn.

2. CH 3 N CH 3 ; CHyCH CH2 NH 2

ch3
Nhit si: 3c 49c
do gia cc p h n t CH3CH2CH2NH2 c k h n n g to lin k t h iro -N - H ...N - ;
cn gia cc p h n t (C H 3)3N kh ng c lin k t h i ro v p h n t cng knh hn
nn c n h i t si th p hn.

Bi s 2.15

/ H
H N' 'S
N/ V '

I r
H H

T nh axit.

247
Bi s 2.16

CH3CH2CH2CH2CH2CH3 c h 3c h c h 2c h 2c h 3
(l) CH3 ( 2 )
c h 3c h 2c h c h 2c h 3 c h 3 c h c h c h ,
T L
ch3 ch3 ch3

(3) (4)

T h t gim d n n h i t si: ( 1 ) > (3) > (2) > (4). N h i t si gim d n theo
mc p h n n h n h .

Bi s 2.17

CH2 COOH > CHy COOH > CH3-*-COOH

I
no2 Cl

I mnh -I

OH H
n
ch3 o
I J //
H <C H 3CH2 OH < [ Q ] < [(3 < C H .- C c ' <
OH
CH
a CH}
o o .0
II //
< CH c ' < CH, S C H c
OH OH
o

NH NH

3.
ro

o 0
V-c1
pKa: 1,02 4,58

248
Bai so 3.9

Rat kh
vi san
phm
khngtun
theo qui
*a ch3 tc Zaixep
ah
Mentyl clorua Kein ben.
Menten

-H H
%R %R
3 - Menten 2 - Menten
Neomentyl clorua
75% 25%

Bai so 4.16

c h 3c h 2c h 2
HCl

Bai so 4.17

249
Bi s 4.18

CH

l - Metylxiclohexen

Bi s 4.19

(Y)

Bi s 5.12

l . C 6H 5N H o + (C H 3C 0 ) 20 -> C 6H 5N H - C O C H 3 + C H 3COOH
P h n ng khng xy ra tip n a do nguyn t N k h n g cn tn h nucleofin.

NH

h n o 2, MCI

Br

NO NH N.Cl

Fe/HCl H N 0 2, HCl KI
b.

CN

CuCN
N 2HSO. n 2b f 4

h b f4

250
 A km bn hrtn B, A to th n h nhanh hn B.

Bi s 6.11

^ CH, CH,

r- CH CH 3
I
H+
CH CH
H 0H2
(A)

Bi s 7.18

A: CH, CH CH2 COOH

OH
B: CH 3 C H = C H COOH

C: CH3 c CH 3

Bi s 7.19

COOH COOH

COOH
H

COOH

(A)

-MSCHV BTHHX
2. COOC 2H 5 COOC.Hs
2 CU 2 CgHsQNa^ 0 ^ / '1 - C H ,- ^

c o o c 2h 5 x c o o c 2h 5

C* * K \ / COOC 2H , h , o . h *
^ c h c h 2 c i h o o c - c h 2- c h 2- c h 2- c o o h
C 2H5OCO COOC 2H5 2 Axit glutaric
COOC2Hg CC)OC,Hs
r CiH^ONa / C l - C H 2COOC 2H<
CH^ ^ c ,l ---------------------:
c o o c 2h 5 X c o o c 2h 5

/ c o o c 2h 5
C 2H 5OCOCH 2- C H ^ H2O .H HOOC_ CH 2 c h 2 c o o h

COOC 2H, Axit suxinic

Bi so 8.10

co co
\ \
NK + Bi CH 2CH 2CH2 Br N CH 2CH 2CH2Br
O / KBr
Q /
CO
-
CO

CO\ R,
Br?
NaHC(COOR) N CH2CHiC UCH(COOR)i -----1 h
- NaBr O / -HBi-
CO
co
CI IiCH 2CH 2CBr(COOR )2 ^
/ ' -co2
CO
CO
\ NH,
N CH->CH->CH->CHBrCOOH ------ -
O . / - HBr
CO
CO
\ h 2o
/ N CH,CH,CII,CKNH,COOH
. . .
---- =-*

CO

H2N - C I l:CI\2CH2C\ INI I2COOII

Ocnitin

252
h 2so . /
H-iO
ch2 I 2NCH2CI I2a 2C 2CH2COOH
\ NH
c h 2 c h 2-
Q H 5COCI ................................................. B P
- * c 6h sc o - h n c h 2c h 2c h 2c h 2c h 2c o o

C6H5C O -H N C H 2CH 2CH 2CH2CHBrCOOH y 11- ' 1.1:0

H 2NCH 2CH 2CH 2CH2CHCOOH

Lysin

Bi s 8.11

Gly Ala Gly Gly Ala Gly

x . / \ /
Phe Val Val Phe
(0 (2 )

Bi s 9.16

CI3O
\
II

H COOH
X
0
-n

L
CHOH CHOH CHOU
o
HOH CHOU CHOI I
I I
i H , I I
C c h 2o h c h 2o h

(A) (B) (C)

Bi s 9.17

OHC

[O]
HNO

H OH
Salixin
Bai so 10.7

+ 2Hl8OH

+ c 6 h 5c o 18o h + CH3OH
H coon H COOCH3 H COOCH3
A \ CH3CI A \ H2, Ni A
N-CH3 >=0 N-CH3 > = 0 ------- N-CH3 OH
\l / - HC1 \l / \l 7

Hv ^COOCH,

Q H 5COC1 H
- N-CH3
OCOC6 Hs

254
 TI LIU THAM KHO

1. Trn Quc Sn, 1974. C s l thuyt ho hu c, Tp I. Nxb. Gio dc, H Ni.

2. Trn Quc Sn, 1979. C s l thuyt ho hu c, Tp II. Nxb. Gio dc, H Ni.
3. Phan Tng Sn, Trn Quc Sn, ng Nh Ti, 1976. C s ho hc hu c, Tp I.
Nxb. i hc v T ru n g hc chuyn nghip, H Ni.
4. Phan Tng Sn,Trn Quc Sn, ng Nh Ti, 1980. C s ho hc hu c, Tp II.
Nxb. i hc v Trung hc chuyn nghip, H Ni.
5. Ng Th Thun, 1999. Ho hc hu c - Phn bi tp. Nxb. Khoa hc v K thut, H
Ni.
6. ng Nh Ti, 1998. C s ho hc lp th. Nxb. Gio dc, H Ni.
7. ng Nh Ti, Trn Quc Sn, 2001. Ho hc hu c. Nxb. i hc Quc gia H Ni.
8. Nguyn Duy i, Nguyn Tinh Dung, Trn Thnh Hu, Trn Quc Sn, Nguyn Vn
Tng, 2002. Mt s vn chn lc ca ho hc. Tp 3. Nxb. Gio dc, H Ni.
9. Nguyn Minh Tho, 2001. Ho hc cc hp cht d vng. Nxb. Gio dc, H Ni.
10. Nguyn Trng Th, 2000. Olympic ho hc Vit N am v Quc t, Tp 3. Nxb. Gio
dc, H Ni.
11. Hong Minh Chu, Ng Th Thun, H Th ip, o nh Thc (hiu nh ting
c), Trn Thnh Hu, Nguyn Trng Th, Phm nh Hin, 2003. Olympic ho hc
Vit Nam v Quc t, Tp 5. Nxb. Gio dc, H Ni.
12. Nguyn Trng Th, 4 * 2003. Bi tp chun b K thi Olympic Ho hc Quc t ln
th 35. Bn dch.
13. Hong Nhm, Nguyn Vn Tng, 1995. Ti liu gio khoa th im Ho hc 11. Ban
khoa hc t nhin. Nxb. Gio dc, H Ni.
14. Trn Quc Sn. Ti liu gio khoa chuyn Ho hc - Ho hc 11-12. Tp I. Nxb. Gio
dc, H Ni, 2001.
15. L Huy Bc, Nguyn Vn Tng, 1986. Bi tp Ho hu c. Nxb. Gio dc, H Ni.
16. Nguyn Tinh Dung, Hong Nhm, Trn Quc Sn, Phm Vn T, 2002. Ti liu
nng cao v m rng kin thc Ho hc trung hc p h thng. Nxb. Gio dc, H Ni.
17. o Hu Vinh, 1999. C s l thuyt Ho hc trung hc p h thng. Nxb. Gio dc, H
Ni.
18. Estelle K. Meislich, Ph.D. Herbert Meislich, Ph.D. Joseph Sharefkin, Ph.D., 1994.
3000 Solved problems in Organic chemistry. Volume 2 . International Editions.
19. S. Bank & J. Bank, 1997. Test Bank to accompany Introduction to Organic
chemistry. First Edition. William H. Brown.

255
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