B GIO DC V O TO

K THI CHN HC SINH GII QUC GIA

LP 12 THPT NM 2011
P N THI CHNH THC
Mn: HO HC
Ngy thi th hai: 12/01/2011
(Gm 06 trang)

Cu 1
1
(2,25
im)

a) - Cu to phn t xitral tun theo qui tc isoprenoit:

CH3-C=CH-CH2-CH2-C=CH-CH=O
CH3

CH3
O

- Hai ng phn ca xitral l:

ng phn a
(E)-3,7-imetylocta-2,6-ienal

ng phn b
(Z)-3,7-imetylocta-2,6-ienal
a v b l hai ng phn hnh hc (cis/trans).

b) Tch ring hai ng phn a v b:

Xitral-a + Xitral-b
H2NCONHNH2

NNHCONH2
+
NNHCONH2
Xitral-b semicacbazon

Xitral-a semicacbazon

Kt tinh phn on
Xitral-a semicacbazon

Xitral-b semicacbazon

H3O+

H3O
Xitral-a

Xitral-b

c) Cng thc cu to ca A, B, C. Gii thch qu trnh chuyn ha to thnh C:

Xitral

LiAlH4

CH2OH

H+

CH2+

-H2O

- H+

4
6

7
6
5

2
(1,5
im)

S cc phn ng chuyn ha t A n I v gi tn cc hp cht hu c:

CH3OCH2CH2CH2CH3

HI

CH3I + CH3CH2CH2CH2I + H2O

A
B

Trang 1/6

NaOC2H5

CH3CH2CH2CH2I
B
+
D
H3O
C KMnO4

CH3CH2CH=CH2 + HI
C

F
E

HBr

I (C11H24O)

Mg

H
H3O+

CH3CH2CH=CH2

CH3CH2CH(OH)CH3
D
KMnO4
CH3CH2COOH + HCOOH
CH3CH2CH=CH2
H+ E
CH3CH2COOCH(CH3)C2H5
CH3CH2CH(OH)CH3 + CH3CH2COOH
F
HBr
Mg
CH3CH2CHBrCH3
C2H5CH(CH3)MgBr
CH3CH2CH=CH2
ete khan
G
H
1. + F
CH
CH
C(OH)[CH(CH
)C
H
]
I
(C
H
O)
H
3
2
3 2 5 2
11 24
+
2. H2O, H

3
(0,75
im)

A: Metyl ioua, B: n-Butyl ioua, C: But-1-en, D: sec-Butanol, E: Axit propionic,

F: sec-Butyl propionat, G: 2-Brombutan, H: sec-Butylmagie bromua,
I: Etyl i-sec-butyl cacbinol.
Ch : Nu giai on to G s dng HBr/peoxit (hiu ng Kharat) th cc sn phm s l: G:
n-BuBr, H: n-BuMgBr, I: EtC(OH)(n-Bu)2.
4-Metylxiclohexanon: khng quang hot
CH3
H

CH3
O

O
3-Metylxiclohexanon: quang hot

CH3
O

H
O

CH3

2-Metylxiclohexanon: quang hot

CH3

CH3
O H *
Trong mi trng baz tnh quang hot ca 2-metylxiclohexanon s mt i do s
raxemic ha theo c ch sau y:
O

O-

OH-

CH3
H

Cu 2
1
(1,5
im)

O
- H2O

CH3
H-OH

OH-

CH3

S chuyn ha:
C2H5
C2H4 / H+
o

COOH

COOH
o

1. KMnO4 / H2O, t

HNO3

2. H3O

H2 / Ni

Fe / HCl

H2SO4

COO-

COOH

NO2

to
NH2

NH3+

So snh nhit nng chy v so snh lc axit ca cc cht A, B, C, D. Gii thch:

Lc axit: B > A > C > D (C khng dng ion lng cc, ch c D dng ion lng
cc).
Nhit nng chy: D > C > B > A. D dng ion lng cc, b phn hy trc khi

Trang 2/6

2
(1,5
im)

nng chy nhit > 200 oC; B v C u c khi lng ln hn v nhiu lin kt
hiro lin phn t hn A nn tonc ca C, B cao hn ca A. Mt khc, nhm NH2 C va
lm tng momen lng cc, va to lin kt hiro lin phn t nhiu hn so vi nhm
NO2 B v vy tonc ca C (178-180 oC) cao hn ca B (139-141 oC).
a) Cng thc cc ng phn lp th ca cis-1-ecyl-2-(5-metylhexyl)etilenoxit (hay
disparlure):
CH2[CH2]3CH(CH3)2

CH3[CH2]8CH2
H

CH2[CH2]8CH3

(CH3)2CH[CH2]3CH2
O

(u bi cho ng phn cis nn ch v 2 i quang ca n nh trn).

b) S tng hp dispalure t axetilen, cc cht v c, hu c (cha khng qu 5
cacbon):
BrCH2CH2CH2CH=CH2

CH3[CH2]3CH2MgBr

BrCH2CH=CH2

(CH3)2CHCH2MgBr
NaC CH
RCOOOH

3
(1,5
im)

NaNH2

H2/Pd, PbCO3

CH3[CH2]8CH2Br (A)

Peoxit
HBr
Peoxit

(CH3)2CHCH2CH2CH=CH2

HBr

CH3[CH2]7CH=CH2

ete

(CH3)2CH[CH2]3CH2Br (B)

CH3[CH2]8CH2 C
H

CH2[CH2]3CH(CH3)2
C H

Disparlure

Xc nh cng thc lp th ca K, M, N v v cu dng bn ca K:

D kin ca u bi cho php xc nh c cu trc ca M, ri suy ra cu trc ca hp
phn gluxit trong K; N phi l mt anken cu hnh trans v phn ng vi KMnO4 cho
sn phm l mt cp threo:
OH
Me

OMe

OH

Me

OH OH

C6 H 5

H
C

KMnO4/H2O

COOH

OH

OMeOMe
M

H
H
C
H
6
5
C
C COOH +
HO
OH
(cp threo, C9H10O4)

C6 H 5
H C
HO

COOH
C H
OH

Cng thc lp th ca K:
O
OH
Me

O C

H
C C

C6H5

OH OH

Cu dng bn ca K:
O
O C
Me
HO

O
HO

H
C

C
C6H5

OH

Trang 3/6

Cu 3
1
(2,0
im)

S chuyn ha:
O 2N

H2N

NO2

N N

NO2

(NH4)2S/H2O
(hoac Na2S/H2O)

HO

NaNO2 /

NO2

NH2

NH

H3C

CH3

1:1

2
(1,5
im)

2. OH

HO

O
NH

G
N

CH3

J (C9H13ON)

Gii thch c ch ca cc phn ng:

O

a)

OH O H

H+

OH
H

b)
OH-

O
O

- H2O

OO

SP

H2O
- OH-

O
OHO

OH
O

O
O-

OH-

COOH

- H2O

H+

OH-

OH
O

COOH

OH
O

H+
O H

COOH

Cu 4
1
(2,0
im)

1.H+ / H2O

H3C

H3C

CH3I

Ac2O

H3C

NH2

NO2

H2O

- N2

Zn / HCl

Zn(Hg)/HCl

0-5

HO

NO2

oC

HO

H+,

O
O

H+

O
OO

OOC

OOC

T xiclohexen v 4-clorobutan-1-ol, tng hp

HOOC

OCH3

Trc ht phi tng hp cht trung gian xiclohexen-1-cacbanehit t xiclohexen:

Br

HBr

MgBr

Mg/ete

2.

COOH

COOH

1. CO2

Br2, xt

H3O+

Br

COOH

1. KOH / EtOH
2. H3O+

CH2OH
COOH

PCC

LiAlH4

COCl

SOCl2

CHO
Xiclohexen-1-cacbanehit

LiAlH(OC4H9-t)3

Sau , t xiclohexen-1-cacbanehit v 4-clorobutan-1-ol tng hp cht m u bi yu cu

theo s sau:
OH

Cl
1.

2. H3O+

PCC

Cl

CHO

OH O

HO

OH

Cl

H+

Mg/ete

ClMg

OH

CH3OH

OCH3

H+

Trang 4/6

2
(1,5
im)

Cc tc nhn (a), (b), (c), (f), (g): (a): (CH3)2C=O/ H+ , (b): KMnO4 , (c): H2O/H2SO4 ,
(f): C6H5NHNH2 (d), (g): C6H5CH=O/ H+
Cng thc lp th ca cc hp cht hu c D-galactopiranoz, A, B, F, H:
OH OH

OH
HO

HO

OH

CH3

CH3

O
O

CH3
CH3

OH

CH3

HO
HO

N-NHC6H5
N-NHC6H5

OH
CN

HO

OH

OH

OH

H
H

CN
OH

Phng trnh cc na phn ng xy ra trn catot v anot:

Cc qu trnh c th xy ra trn catot:
Cu2+ + 2e Cu (1)
2H+ + 2e H2
Co2+ + 2e Co
Qu trnh xy ra trn anot: 2H2O O2 + 4H+ + 4e (2)
0,0592
E 2+ = 0,337 +
lg 0, 02 = 0,287 V
Cu /Cu
2
E 2+ = E 0 2+ = - 0,277 V
Co

E
V E

Cu 2+ /Cu

>E

2H + /H 2

/Co

2H + /H 2

>E

Co

/Co

0,0592
lg (0, 01) 2 = - 0,118 V
2
nn th t in phn trn catot l: Cu2+, H+, Co2+.

Co 2+ /Co

Khi 10% Cu2+ b in phn, E

3
(1,0
im)

OH
B

OH

HO

CH3

2
(1,25
im)

Cu 5
1
(0,75
im)

OH

CH3

CH3

OH

OH

OH

OH

Cu 2+ /Cu

= 0,285 V (khi H2 cha thot ra), nu ngt

mch in v ni on mch 2 cc s hnh thnh pin in c cc dng (catot) l cp

O2/H2O v cc m (anot) l cp Cu2+/Cu. Phn ng xy ra:
trn catot:
O2 + 4H+ + 4e 2H2O
trn anot: 2 Cu
Cu2+ + 2e
+
2Cu + O2 + 4H 2Cu2+ + 2H2O
Pin phng in cho ti khi th ca 2 in cc tr nn bng nhau.
tch hon ton c Cu2+ th catot cn t l: E + < Ec < E 2+ . Khi Cu2+ b
2+

2H /H 2

Cu

/Cu

-6

in phn hon ton th [Cu ] = 0,02.0,005% = 1.10 M

0,0592
E 2+ = 0,337 +
lg106 = 0,159 V
Cu /Cu
2
[H+] = 0,01 + 2(0,02 - 10-6) 0,05 M
0,0592
=
E +
lg (0, 05) 2 = - 0,077 V.
2H /H 2
2
Vy trong trng hp tnh khng k n qu th ca H2 trn in cc platin th th catot
cn khng ch trong khong - 0,077 V < Ec < 0,159 V, khi Cu2+ s b in phn hon ton.
Trang 5/6

4
(1,0
im)

0,5.25.60
= 1,943.103 (mol).
4.96500
Th tch kh oxi thot ra trn anot (ktc) l: VO2 = 1,943.103.22,4 = 0,0435 (L).
T (2) ta c s mol ca oxi gii phng ra: n O2 =
Theo (1), s mol ion ng b in phn sau 25 pht:
n Cu 2 + =

0,5.25.60
= 3,886.103 (mol) < 0,02.200.103 = 4.103 (mol).
2.96500

Nh vy Cu2+ cha b in phn ht. Nng Cu2+ cn li l:

[Cu2+] =
Khi th catot Ec = E

Cu

(4.10-3 - 3,886.10-3 ). 1000

= 5,7.104 (M)
200
2+

/Cu

= 0,337 +

0,0592
lg (5,7.10-4 ) = 0,24 (V).
2

----------- HT -----------

Trang 6/6