K THI CHN HC SINH GII QUC GIA

LP 12 THPT NM 2006

B GIO DC V O TO
---------------------

HNG DN CHM THI CHNH THC

Mn: HO HC- Bng A
Ngy thi th hai: 24.02.2006
Cu I (3,5 im): 1. 1 im; 2. 1 im; 3. 1,5 im.:
1. Hy cho bit cc sn phm ca s thu phn trong mi trng axit ca cc cht CH3COOCH3,
O
CH3CONH2, O
N

CH3

2. Gi tn cc ng phn i quang nhn c khi monoclo ho metylxiclohexan di tc dng

ca nh sng, gi thit rng vng xiclohexan phng.
3. Axit m-RC6H4COOH v axit p-RC6H4COOH c t l hng s phn li Kmeta/Kpara nh sau:
R

Kmeta/Kpara :

CH3S

CH3O

1,87

2,50

Da vo cc s liu trn, hy so snh (c gii thch):

a. Hiu ng y electron ca cc nhm CH3S- v CH3O- .
b. Tc phn ng thu phn CH3SCH2Cl v CH3OCH2Cl.
c. Tc phn ng cng HCN vo p-CH3SC6H4CHO v p-CH3OC6H4CHO.
Hng dn gii:

1.

CH3-COOCH3
CH3-CONH2
O

O
O

H2O
+

H , tO
H2O
+

H , t

CH3-COOH

CH3OH

CH3-COOH

NH4+

H2O
+

CH3

H , tO

+
CH3-NH2-CH2-COOH

CH3

CH3

HOCH2COOH

2. C 8 ng phn:
CH3
Cl

(1S, 2R)
CH3
Cl
(1S, 3R)

Cl

(1R, 2S)

Cl

(1R, 2R)

CH3

CH3

Cl

CH3

(1S, 2S)
CH3

Cl

Cl (1S, 3S)

Cl
(1R, 3S)

(1R, 3R)

3. a. Cc nhm CH3S v CH3O v tr meta c hiu ng cm ng m l chnh, v tr para

chng c hiu ng lin hp dng. Hiu ng +C cng mnh Kmeta : Kpara cng ln. Suy ra hiu
ng y electron ca CH3O- mnh hn CH3S- .
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b. Nh hiu ng +C ca CH3O- mnh hn CH3S- , tc phn ng thu phn ca CH3OCH2Cl

ln hn CH3SCH2Cl (d theo c ch SN1 hay SN2).
c. Do hiu ng +C ca p-CH3O- mnh hn ca p-CH3S- , tc cng nucleophin HCN vo pCH3SC6H4CH=O ln hn p-CH3OC6H4CH=O.
Cu II (3,75 im): 1. 0,5 im; 2. 0,5 im; 3. 0,75 im; 4. 2,0 im.
Cho s chuyn ho cc cht sau:
Br / P

NH

1. (CH3)2CHCH2COOH 2 B
3 D
NH

H / Pt

2. (CH3)2CHCOCOOH
3 E 2 G
H O+

to , H

C H CO H

6 5
3
3. CH2=CH-CH=CH2

H 2 I 3 K

Cl

4.

AlCl3
-HCl

O
HOO

HO

LiAlH4

H2SO4

-H2O

M1

Cl

MnO4

Cl

M2
Vit cng thc cu to ca cc sn phm hu c B, D, E, G, H, I, K, X, Y v v cu trc
khng gian ca Z, L, M1, M2.
Hng dn gii:
1. (CH3)2CHCH2COOH
2. (CH3)2CHCOCOOH

Br2, P

NH3

(CH3)2CHCHBrCOOH
(B)

NH3

H2, Pt

(CH3)2CHCCOOH
(E) NH2

3. CH2 = CH - CH = CH2 C6H5CO3H

O

H3O+

CH2

4.

(X)
H

HOCH2CH2CH2CH2OH
(K)
CH2

C
O

(Y)

CH2

(CH3)2CHCHCOOH
(G) NH2
O

to, H2

(Z)
H
H

(Z)

(I)

C C

OH

OH

HO
H

C C

CH2 = CH - CH CH2 (H)

O

(CH3)2CHCHCOOH
(D) NH2

(M2)

HO

OH

(M1)

Cu III (3,75 im): 1. 2,0 im; 2. 1,75 im.

1. T ht tiu ngi ta tch c hp cht A (C17H19NO3) l cht trung tnh. Ozon phn A thu
c cc hp cht: etaial, B, D. Thu phn B thu c OHC-COOH v hp cht d vng 6 cnh
piperiin (C5H11N). Cho D tc dng vi dung dch HI c thu c 3,4-ihiroxibenzanehit.
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Hy xc nh cng thc cu to ca A, B, D. C bao nhiu ng phn lp th ca A?

2. Hai hp cht thm a vng X v Y c cng cng thc phn t l C14H10. Oxi ho X bng
K2Cr2O7 /H2SO4 cho sn phm D (C14H10O4), oxi ho X bng oxi c xc tc V2O5 v nhit
340oC n 390oC cho sn phm E (C14H8O2). Khi oxi ho Y ging nh X (bng K2Cr2O7 /H2SO4
hoc oxi c xc tc V2O5 v nhit 340oC n 390oC) th thu c G (C14H8O2).
Hy xc nh cng thc cu to ca X, Y, D, E, G.
Hng dn gii:
1. Ozon phn A thu c etaial chng t trong A c nhm =CH-CH= . Thu phn B thu c
OHC-COOH v piperiin, suy ra B c lin kt O=C-N- v N nm trong vng 6 cnh. D phn
ng vi HI thu c 3,4-ihiroxibenzanehit. Vy c cc cng thc cu to:
C

OHC

(B)
O

CHO
(D)

CH CH CH CH C
O

(E)

Trong A c 2 lin kt i, s ng phn hnh hc l 4: ZZ , EE , ZE , EZ.

2.
K2Cr2O7/H2SO4

HOOC

COOH

(D) C14H10O4

O2 , V2O5

(X) C14H10

340-390 C

(E) C14H8O2
O
K2Cr2O7/H2SO4

(Y) C14H10

O2 , V2O5
o

340-390 C

Cu IV (4,5 im): 1. 2,25 im; 2. 2,25 im.

(G) C14H8O2
HO
H

CHO
H
OH

1. Khi un nng b-D-iopiranoz ti 165oC vi axit long to ra anhiro (1,6) vi

hiu sut hn nhiu so vi b-D-glucopiranoz.
HO
H
H
OH
Hy gii thch iu v biu din cu dng ca 2 hp cht anhiro trn.
CH2OH
2. Khi cho D-glucoz phn ng vi hirazin hirat, u tin glucozylhirazon tn
ti dng mch h, song pH 7 n d dng chuyn thnh dng vng b-D-Iopiranoz
glucozylhirazin.
Hy vit cng thc cu trc cc dng chuyn ho ca glucozylhirazin v gi tn.
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Hng dn gii:

1.
HO
H
HO
H

OH
CH2

CH2OH
OH
O

CHO
H
OH
H
OH
CH2OH

OH

H+ , to

O
b-D-Iopiranoz

1C-I

HO

CHO
OH

CH2OH
OH
O

3
4

OH

CH2OH
H+ , to

OH
OH
CH2OH

b-D-Glucopiranoz

1C-G

6
5

O
4

4
1

cu dng tch 1CI bn hn 1CG do cc nhm OH cc v tr 2,3,4 l lin kt equatorial.

2.

OH
O

HO
HO

HO

HO

NHNH2

CH2OH
OH

HO

-D-Glucopiranozylhirazin

OH
O

HO

CH=N-NH2
OH
OH
OH
CH2OH

OH

NHNH2

OH

b-D-Glucopiranozylhirazin

CH2OH
OH

NHNH2

OH
NHNH2
OH

-D-Glucofuranozylhirazin

OH
b-D-Glucofuranozylhirazin

Cu V (4,5 im): 1. 0,5 im; 2. 2,5 im; 3. 1,5 im.

Kh tng hp (CO v H2) c th thu c t phn ng ca hi nc (H2O kh) v metan.
Metanol (CH3OH) c sn xut trong cng nghip t kh tng hp ny.
Ton b qu trnh sn xut lin tc c minh ho theo s di y (Bc A iu ch kh
tng hp v bc B iu ch metanol):
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(8)
(1)
(2)

B phn iu ch kh
tng hp (Bc A)

(3)

B phn ngng t
(25oC)

(4)

B phn iu ch
metanol (Bc B)

(6)

B phn ngng t
(25oC)

(7)

(5)

Nguyn liu np vo b phn iu ch kh tng hp (Bc A) gm kh metan tinh khit (1)

ti p sut 250kPa, nhit 25oC v hi nc (2) ti p sut 200kPa, nhit 100oC (gi thit
rng hi nc cng tinh khit). Tc np nguyn liu ca (1) v (2) ln lt bng 55 L/s v
150 L/s. (1atm = 101,3kPa).
Thot ra khi bc A l mt hn hp kh tng hp v lng d cc cht phn ng; hn hp
ny qua (3) vo b phn ngng t, cht ngng t s thot ra theo (5) ti 25oC. Nhng cht khng
ngng t qua (4) vo b phn iu ch metanol (bc B). Metanol to thnh v cc cht tham gia
phn ng cn d qua (6) vo b phn ngng t ti 25oC, metanol tinh khit tch ra theo (7), cc
cht d tch ring theo (8).
Gi thit rng cc kh u l kh l tng, cc phn ng trong bc A, B v s tch ring cc
cht u xy ra hon ton.
Cho bng s liu sau:
Khi lng mol
Khi lng ring
Hp cht
tonc (oC)
tos (oC)
-1
phn t (g.mol )
ti 25oC
CH4 kh
16,04
-183
-161
0,718 g.L-1
H2O lng
18,02
0
100
1,000 g.mL-1
CO kh
28,01
-205
-191,5
1,250 g.L-1
H2 kh
2,016
-259,2
-252,8
.
CH3OH
32,04
-98
64,7
0,791 g.mL-1
1. Vit cc phng trnh ha hc trong bc A v B.
2. Tnh s mol cc cht d sau bc A v sau bc B.
3. Tnh tc chuyn cc cht ti cc v tr (5), (7), (8) 25oC v 101,3 kPa.
Hng dn gii:
1.
Bc A: CH4 + H2O
Bc B: CO + 2 H2

CO +
CH3OH

3 H2

2. Cc kh u coi l l tng nn trong 1 giy s mol cc cht d sau Bc A v sau Bc B l:

n CH 4 =
n CH 4
n H 2O

250 55 273
= 5,551 mol ;
101.3 22.4 298
5,551
= 0,57
9,676

n H 2O =

200 150 273

= 9,676
101.3 22.4 373

n CH 4 < n H 2O .

Trong Bc A cn d H2O do phn ng xy ra hon ton v theo t l mol 1 : 1

Bc B: Phn ng bc A xy ra hon ton nn t l CO : H2 = 1:3. Phn ng bc B xy ra
theo t l CO : H2 = 1 : 2 nn d H2.
- Tnh s mol nc d trong Bc A:
Xt trong 1 giy:
CH4
+
H2O

Trc phn ng: 5,551 mol

9,676 mol
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CO

3 H2
5

Sau phn ng:

0
4,125 mol
5.551 mol
n H 2O d = 9,676 5,551 = 4,125 (mol)

- Tnh s mol hiro d trong Bc B:

Xt trong 1 giy:
CO
+
2 H2
Trc phn ng: 5,551 mol
3 5,551 mol
Sau phn ng:
0
5.551 mol

3 5,551 mol

CH3OH
5,551 mol

n H 2 d = 16,653 11,102 = 5,551(mol)

3. - Tc chuyn nc ti v tr (5) 25C v 101,3 kPa.
4,125 x18,02
= 74,33 (ml)
1000
Vy tc chuyn H2O lng bng 74,33 ml/giy.

VH2O (lng)=

- Tc chuyn metanol ti v tr (7) 25C v 101,3 kPa.

V CH3OH (lng) =

5,551 x 32,04
= 224,85 (ml)
0,791

Vy tc chuyn CH3OH lng bng 224,85 ml/giy.

- Tc chuyn hiro ti v tr (8) 25C v 101,3 kPa.
V H2d =

5,551 x 22,4 x 298 x 101,3

= 135,73 (lt)
273 x 101,3

Vy tc chuyn H2 bng 135,73 l/giy.

......................................................
Ghi ch: Nu th sinh lm khc vi Hng dn chm nhng vn ng, gim kho cng
cho im theo biu im.

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