b go dc v o to k th chn hc snh g quc ga

p 12 thpt nm hc 2002-2003

Hng dn chm thi chnh thc Mn Ho Hc
Bng B. Ngy th: 13/3/2003
Cu I (4,5 Om):
1. (2,75 im). Kh c mt enzm acontaza, axt acontc b hrat ho
to thnh axt A khng quang hot v axt B quang hot theo mt cn
bng:
HOOC COOH
B C=C
A
(C
6
H
8
O
7
) H CH
2
COOH
(C
6
H
8
O
7
)
6% Axt acontc 4%
90%
a) (2,25 im). Vt cng thc cEu to ca A v B, gh tn y ca
chng v ca axt acontc theo danh php IUPAC. Axt A c pKa: 3,1 ; 4,8
; 6,4. Gh cc g tr pKa bn cnh nhm chc thYch hp.
b) (0,5 im). Vt s Ou ch A t axeton v cc chEt v c cn
tht.
2. (1,75 im). Ozon phn mt tecpen A (C
10
H
16
) thu c B c cEu to
nh sau:
CH
3
CCH
2
CHCHCH
2
CH=O . Hro ho A v xc tc km o to ra
hn hp sn
O C phEm X gm cc ng phn c cng
thc phn t
H
3
C CH
3
(B) C
10
H
20
.
a) (1,0 im). Xc nh cng thc cEu to ca A.
b) (0,75 im). Vt cng thc cc ng phn cEu to trong hn hp X.
!i gi"i#
1. a)
$B%
$A%
COOH
CH
2
COOH
HOOC
C C
H
Axt (Z)-3-cacboxpentendoc
HOOC CH CH
CH
2
COOH
COOH OH
H
2
O
HOOC-CH
2
C
(3,1)
CH
2
COOH
COOH
OH
4,8(6,4) 6,4(4,8)
Axt 3-cacbox-2-hdroxpentadoc
Axt 3-cacbox-3-hdroxpentandoc
H
2
O

b)

CH
3
CH
3
C O
C
2
CH
3
COOH
CH
2
C
CH
2
C
C O
CH
2
CN
H
3
O
+
C CN
CH
2
COOH
HO C HO
COOH
CH
2
COOH
CH
2
CN
CH
2
C
C CN HO
CH
2
C
HCN KCN
1

H
2
O

H
2
O
*
2.a)
(vng
7 cnh km bOn hn vng 6 cnh)

Cu II (4,0 Om):
1. (2,5 im). T benzen hoc touen v cc chEt v c tng hp cc
dc chEt sau: Axt 4-
-amno-2-hroxbenzoc; axt 5-amno-2,4-hroxbenzoc.
2. (1,5 im). Dng cng thc cEu to, hy hon thnh s tng hp
sau y:
COC
2
+ CH
3
OH C
2
H
3
O
2
C B C
8
H
8
O
4
NSC
D
C
6
H
8
O
2
N
2
S. (B, & cc hp chEt hu c)
!i gi"i#
1.
HNO
3
H
2
SO
4
, t
0
NO
2
NO
2
Sn/ HC
NH
2
NH
2
OH
NH
2
HNO
2
OH
NH
2
CO
2
,OH
-
t
0
,p
COOH
HNO
3
H
2
SO
4
, t
0
NH
2
NH
2
OH
OH
HNO
2 CO
2
,HO
t
0
, p
OH
OH
COOH
OH
OH
COOH
O
2
N
OH
OH
Sn /HC
COOH
H
2
N
Hoc:
2
b)
+2H
2
;
;
C
6
H
5
NH
2
HOSO
2
C NH
3
H
3
O
+
+

H
2
O
HNO
3
H
2
SO
4
, t
0
NO
2
NO
2
K
2
Cr
2
O
7
NO
2
NO
2
NH
2
NH
2
Sn / HC
CH
3
CH
3
H
+
COOH COOH
OH
OH
HNO
2
COOH
OH
OH
HNO
3
COOH
H
2
SO
4
O
2
N
OH
OH
COOH
H
2
N
Sn / HC
2. a) COC
2
+ CH
3
OH CH
3
O-COC
CH
3
OCOC
C
6
H
5
NH
2
NHCOOCH
3
HOSO
2
C
NHCOOCH
3
SO
2
C
NH
2
SO
2
NH
2
d
NH
3
NHCOOCH
3
SO
2
NH
2
H
3
O
+
$B%
$'% $&% $(%
Cu III (4,0 Om):
1. (2,0 im). Anco tert-butyc cng nh iso-buten kh un nng v
metano c H
2
SO
4
xc tc Ou cho sn phEm chYnh A (C
5
H
12
O). Ngo
ra, tu thuc chEt u anco tert-butyc hay iso-buten m cn to ra
cc sn phEm ph khc nh B (C
8
H
18
O), ' (C
9
H
20
O), & (C
8
H
16
)... Kh cho A,
B, ', & tc dng v CH
3
MgI Ou khng thEy khY thot ra.
a) Hy xc nh cng thc cEu to ca A v g thYch v sao A sn
phEm chYnh trong c ha trng hp cho.
b) Dng cng thc cEu to O vt s phn ng g thYch s hnh
thnh sn phEm ph trong trng hp dng anco tert-butyc v trng hp
dng iso-buten.
2. (2,0 im). Hp chEt A (C
5
H
9
OBr) kh tc dng v dung dch t trong
kOm to kt ta mu vng. A tc dng v dung dch NaOH to ra 2
xeton B v ' cng c cng thc phn t C
5
H
8
O.
B) ' Ou khng m mEt mu dung dch kapemanganat nh, ch c
B to kt ta mu vng v dung dch t trong kOm.
3
a) Xc nh cng thc cEu to ca A, B, '.
b) Cho B, ' n t tc dng v CH
3
MgBr r v H
2
O. Vt phng trnh
phn ng v g tn sn phEm to thnh theo danh php IUPAC.
!i gi"i#
1
(CH
3
)
3
C - OH
H
+
- H
2
O
CH
3
CH
3
CH
3
+
C
H
+
CH
2
CH
3
CH
3
C
CH
3
OH
CH
3
CH
3
CH
3
C O CH
3
$A%
H
+
- H
2
O
CH
3
OH
$B%
(CH
3
)
3
C
+
bOn hn
+
CH
3
; (CH
3
)
3
C - OH cng kOnh hn CH
3
- OH
V vy, phn ng chYnh :
(CH
3
)
3
C
H
+
CH
3
CH
3
CH
3
+
C
H
+
CH
2
CH
3
CH
3
C
CH
3
OH
CH
3
CH
3
CH
3
C O CH
3
$A%
H
+
CH
3
OH
$B%
+
(CH
3
)
3
C
+
+
OH CH
3
CH
3
CH
3
C O
CH
3
C
CH
3
CH
3
(CH
3
)
3
C
+
+ (CH
3
)
3
C
+
CH
2
CH
3
CH
3
C
H
+
(CH
3
)
3
C CH
CH
3
CH
3
C
$&%
$'% CH
3
CH
3
CH
3
C CH
2
O-CH
3
C
CH
3
CH
3
2.
OH
Br
CH
3
CH
2
C CH
3
Br
CH
2
CH
2
O
H
2
O
CH
2
C CH
3
Br
CH
2
CH
O
CH
2
C CH
2
Br
CH
2
CH
2
O
C
O
Br
O
$B %
$'%
4
CH
3
+
CH
3 C CH
3
OH
CH
3
C
O
1) CH
3
MgBr
2) H
2
O
(D )
O
$'%
CH
3
OH
$*%
1) CH
3
MgBr
2) H
2
O
Tn g : D : 2 - xcopropy - 2 - propano E: 1-mety
xcopentano

Cu IV (3,0 Om):
TRF tn vt tt mt homon Ou khOn hot ng ca tuyn
gp. Thu phn hon ton 1 mo TRF thu c 1 mo m chEt sau:

NH
3
; COOH ; HOOC-CH
2
-CH
2
-CH-COOH ;
N (Pro) NH
2
(Gu)
H
Trong hn hp sn phEm thu phn khng hon ton TRF c peptt
Hs-Pro. Ph kh ng cho bt phn t kh ca TRF 362 vC. Phn
t TRF khng cha vng n hn 5 cnh.
1. (2,0 im). Hy xc nh cng thc cEu to v vt cng thc Fs
ca TRF.
2. (1,0 im). v Hs ng ta cho pKa
1
= 1,8 ; pKa
2
= 6,0 ; pKa
3
= 9,2.
Hy vt cc cn bng n v gh cho m cn bng mt g tr
pKa thYch hp. Cho 3 bOu thc: pH
I
= (pKa
1
+ pKa
2
+ pKa
3
) : 3, pH
I
=
(pKa
1
+ pKa
2
) : 2, pH
I
= (pKa
2
+ pKa
3
) : 2; bOu thc no ng v Hs, v
sao?
!i gi"i#
1. * T d kn thy phn suy ra 2 cng thc Gu-Hs-Pro v Hs-Pro-Gu
(Ou c 1 nhm
-CO - NH
2
)
* T M = 362 vC suy ra c to ra amd vng (o H
2
O)
* T d kn vng 5 cnh suy ra Gu amnoaxt u N v to actam
5 cnh, cn Pro amnoaxt u C v to nhm - CO - NH
2
.
5
N CH
2
-CH-COOH
NH
2
(Hs)
N
H
Vy cEu to ca TRF:

HN CH
O
CO-NH CH CO N CH CO-NH
2
CH
2
N
NH
Cng thc Fs:

NH
CO
CO
CO
CH
2
NH
2
H
H
H
O
N
NH
N
NH
2. Cn bng n y ca Hs:
COOH
H H
3
N
CH
2
N H
NH
+
+
COO
H H
3
N
CH
2
N H
NH
+
+
COO
H H
3
N
CH
2
N
NH
+
COO
H
CH
2
N
NH
H
2
N
-H
+
-H
+
-H
+
(+2) (+1)
(0)
(-1)
(1)
(2) (3)
1,8 6,0
(hoc vt 3 cn bng rng r; khng cn cng thc Fs)
* pH
I
= (pKa
2
+ pKa
3
) : 2 ng,
v phn t Hs trung ha n (n tYch = 0) nm ga 2 cn
bng (2) v (3)
Cu V (4,5 Om) :
1. (2,0 im). saccart X (C
12
H
22
O
11
) khng tham ga phn ng trng
bc, khng b thu phn b enzm mantaza nhng b thu phn b
enzm emusn. Cho X phn ng v CH
3
I r thu phn th ch c
2,3,4,6-tetra-O-mety-D-guoz.
Vt cng thc p thO ca X. Bt rng: D-guoz ng phn
cEu hnh C
3
v C
4
ca D-gucoz; mantaza xc tc cho s thu phn
ch n kt -gcozt, cn emusn xc tc cho s thu phn ch n
kt -gcozt.
2. (2,5 im). Deox-D-guoz A (C
6
H
12
O
5
) c chuyOn ho theo 2 hng
sau:
6
HIO
4
H
3
O
+
' & gxern,
3-hroxpropana
A B
C
6
H
11
BrO
4
(() C
6
H
10
O
4
(*)
hn hp +
(B, ', &, (, * ,- cc h./ cht h01 c2).
a) Xc nh cng thc cEu to ca A.
b) Vt cng thc cEu to ca B, ', &, (, *.
!i gi"i#
1.
* T D-gucoz suy ra cEu hnh ca D-guoz. X khng kh nn c n
kt 1,1-gcozt.
* S thy phn ch b emusn chng t tn t n kt 1

-1

-gcozt.

O
CH
2
OH
HO
OH OH
O
O
HOCH
2
OH
HO HO

hoc:
O
CH
2
OH
CH
2
OH
OH
OH
HO
O
O
OH
HO
OH
2.
a) b) T hng chuyOn ha th nhEt xc nh c cng thc cEu to ca
A
CH
2
OH CH
2
OH
HO HO
$'%
7
CH3OH, H
+
1) LAH
4
2) H
2
O
HBr
KOH H
2
O/ DC
C
6
H
12
O
5
CH
2
OH, H
+
OH
OCH
3
OH $A% OH $B%
$(%

O
CH
2
OH
HO
OH
Br
O
CH
2
OH
OCH
3
$'%
LAH
4
O
CH
2
OH
HOCH
2
HOCH
2
OCH
3
$&%
H
3
O
+
KOH
O
CH
2
OH
HO
OH
$*%
H
2
O/ DC
$+%
CH
2
OH
CHOH
CH
2
OH
+
CHO
CH
2
CH
2
OH
HOC
HOC
$(%
.....................................................
8