B gio dc v o to

k thi chn hc sinh gii quc gia

lp 12 !" n#$ 2%%&
!ng d'n ch($ ) thi ch*nh th+c
,-n. ho hc h/u c0 1 B2ng 3
45u 6 (4 im): 1. 1,25 im ; 2. 1 im ; 7. 1,75 im
1. 3-metylbuten-1 tc dng vi axit clohidric to ra cc sn phm trong !" c" #
l$ %-clo-3-metylbutan v$ & l$ %-clo-%-metylbutan. &'ng c( ch) phn *ng h+y
gii th,ch s- to th$nh hai sn phm # v$ &.
2. %-metylbuten-% phn *ng vi axit clohidric. .r/nh b$y c( ch) c0a phn *ng
cho bi)t sn phm ch,nh v$ gii th,ch1
7. .rong phn *ng clo ho nh2 ch3t x4c tc 5e6l
3
7h n8ng phn *ng t(ng !9i :
cc v; tr, 7hc nhau trong cc ph<n t= biphenyl v$ ben>en nh sau?
790 790
1
1
1 1
1 1
0 250
0 250
250 0
250 0
a@ .r/nh b$y c( ch) phn *ng clo ho biphenyl theo hng u tiAn nh3t.
b@ .9c !B monoclo ho biphenyl v$ ben>en h(n 7Cm nhau bao nhiAu lDn1
c@ .rong mBt phn *ng clo ho biphenyl thu !Ec 1F gam %-clobiphenyl sG thu !-
Ec bao nhiAu gam H-clobiphenyl1
H ng dn gii:
H
+
CH
3
-CH-CH-CH
3
CH
3
CH
3
-CH-CH
2
-CH
2
CH
3
I
I
chuyJn v;
KL@
KLL@ KLLL@
%-6lo-%-metylbutan %-6lo-3-metylbutan
CH
3
-C-CH
2
-CH
3
CH
3
I
6l
-
6l
-
CH
3
-CH-CH=CH
2
CH
3
CH
3
-CH-CH-CH
3
CH
3
6l
CH
3
-C-CH
2
-CH
3
CH
3
6l
1.
Mo cacbocation bNc hai KLL@ c" 7h n8ng chuyJn v; hi!rua to th$nh cacbocation
bNc ba KLLL@ nAn to th$nh hai sn phm # &.
2.
H
+
6l
-
CH
3
-C-CH
2
-CH
3
CH
3
I
KL@
CH
3
-C-CH-CH
3
CH
3
I
KLL@
%-6lo-%-metylbutan
CH
3
-C=CH-CH
3
CH
3
6l
-
CH
3
-C-CH
2
-CH
3
CH
3
6l
%-6lo-3-metylbutan
CH
3
-CH-CH-CH
3
CH
3
6l
%-6lo-%-metylbutan l$ sn phm ch,nh.
1 6.O6

Mo cacbocation bNc ba KL@ bPn h(n cacbocation bNc hai KLL@ mQt 7hc do
cacbocation bNc hai KLL@ c" 7h n8ng chuyJn v; hi!rua to th$nh cacbocation
bNc ba KL@ nAn sn phm %-clo-%-metylbutan l$ sn phm ch,nh.
7.
a@ 6( ch) R
S
% u tiAn v$o v; tr, cacbon s9 H.
6l
%
I 5e6l
3
6l
I
5e6l
H
-
.9c !B monoclo ho c0a
biphenyl h(n ben>en H3F
lDn.
c@ TQt x l$ s9 gam H-clobiphenyl ta c"?
45u 66 (4,75 im): 1. 1 im ; 2. 1 im ; 7. 2,75 im
1. .U etilen v$ propilen c" x4c tc axit platin v$ !iPu 7iVn cDn thi)t h+y vi)t s(
!W tXng hEp isopren.
2. 6ho s( !W sau?
Yi)t cZng th*c cc sn phm h[u c( # & 6 v$ M.
7. .U axetilen v$ cc ho ch3t vZ c( cDn thi)t h+y vi)t cc ph(ng tr/nh phn
*ng to ra p-K!imetylamino@a>oben>en?
N CH
3
N
N
CH
3
Hng dn gii:
1.

CH
2
=CH
2
H
+
CH
3
-CH
2
+
cacbocation n$y al7yl ho propen
CH
2
=CH-CH
3
CH
3
-CH
2
-CH
2
-CH-CH
3
+
CH
3
-CH
2
+
CH
3
-CH
2
-CH=CH-CH
3
CH
3
-CH
2
-CH-CH
2
+
CH
3

- H
+
- H
+
CH
3
-CH
2
-C=CH
2
CH
3
(II)
Xiclohexanol
HBr
A
Br
3.
1. i
2. C!I
B
(NB")
C
N
2
H
#
$%
2
&
'%H
C
2
H
5
%H
CH
2
CH
2
C
%
C
%
NBr

% 6.O6
7
biphenyl
K%\F H@ I K]^F %@ H3F
7
ben>en
1 _
1
x ]^F % ]^F % 1F
1F %\F H 1FFF
x
15,8 (g)
I
6l
I
6l
- O
I

nhanh
chNm
6l
O
I
89
H
+
CH
3
-CH=CH
2

CH
3
-CH-CH
3
CH
3
-CH
2
-CH
2
+
+
CH
2
=CH
2
CH
2
=CH
2
(I()
CH
3
-CH
2
-CH
2
-CH-CH
2

+
CH
3
-CH-CH
2
-CH
2
CH
3
+
- H
+
- H
+
CH
3
-CH
2
-CH
2
-CH-CH
2

+
CH
3
-CH
2
-CH
2
-CH=CH
2

CH
3
-CH-CH=CH
2
CH
3
CH
3
-CH-CH
2
-CH
2
CH
3
+
.ch KLL@ v$ KLY@ ra 7h`i han hEp?
(II)
(I() CH
3
-CH-CH=CH
2
CH
3
CH
3
-CH
2
-C=CH
2
CH
3
)* + *
o
- H
2
CH
2
=CH-C=CH
2
CH
3
Br Br
Br
2.
# & 6 M
3.
CH CH
,00
0
C+ X-
3
(I)
.
(III)
HN%
3
+ H
2
"%
#
!
/e$HCl
(II)
N%
2
NH
2
H
2
%
H0
2+
CH
3
CH%
A0
2
%$NH
3
CH
3
C%%H
CH
3
C%%Na
Na%H
CH
#
Ca%.Na%H
*
0
CH
#

Cl
2
+ a.1
(I()

CH
3
Cl + HCl
CH CH
6ho (III) phn *ng v i KLY@
NH
2
+
2CH
3
Cl
2Na%H
N
CH
3
CH
3
+
2NaCl + 2 H
2
%
NH
2
NaN%
2
HCl
0-5
0
C
N
2
+
N
2
+
CH
3
C
,
H
5
N=N-C
,
H
#
N(CH
3
)
2
CH
3
N
3 6.O6
45u 666 (3,5 im): 1. 0,75 im ; 2. 1,25 im ; 7. 0,75 im ; 4.
0,75 im
bonosaccarit # K!Qt l$ glico>( #@ c" tAn l$ K%R3c HR \c@d
%3H\_d
dpentahi!roxihexanal. ehi !un n"ng ti 1FF
F
6 # b; tch nc sinh ra sn
phm & c" tAn l$ 1_danhi!roglicopirano>(. Mdgluco>( 7hZng tham gia phn
*ng n$y. .U # c" thJ nhNn !Ec cc sn phm S K6
\
O
1F
f
\
@ v$ g K6
\
O
h
f
]
@
theo s( !W phn *ng?

A
Br
2
H
2
%
C
CaC%
3
HN%
3
2
3
&
H
2
%
2
1. Yi)t cZng th*c 5is( c0a # v$ &.
2. # tWn ti : H dng gh) KM-glicopirano>(@. Yi)t cZng th*c c0a cc dng !" v$
cho bi)t dng n$o bPn h(n c1
7. Ming cZng th*c c3u dng biJu dijn phn *ng chuyJn ho # th$nh &. Y/
sao
Mdgluco>( 7hZng tham gia phn *ng tch nc nh #1
&. Yi)t cZng th*c c3u tr4c c0a S v$ g. O+y cho bi)t ch4ng c" t,nh kuang
hot hay 7hZng1
H ng dn gii:
1.
CH%
%H
%H
H%
H%
CH
2
%H
100
0
C
%H
CH
H%
H%
%-CH
2
%
+ H
2
%
2
%
%
H%
H %
%H
%H
%H
H%
H%
%H
%H
%H
C1 -

1 C -

%
%
H%
H %
%H
%H
H%
H%
%H
%H
1 C -
H %
%H

C1 -

1 6 - &Pn nh3t v/ s9 liAn 7)t e d fO nhiPu nh3t

H 6.O6
%
H%
H%
%H
%H
%H
%
H%
H%
%H
%
+ H
2
%
100
0
C
3.
M- gluco>( 7hZng phn *ng tch nc v/ cc nh"m d fO : 61 v$ 6_ luZn : xa
nhau.
CH%
%H
%H
H%
CH
2
%H
C%%H
%H
%H
H%
C%%H
4.
luang hot ehZng kuang hot
45u 6: (4 im): 1. 2,5 im ; 2. 1,5 im
1. .U nh-a thZng ng2i ta tch !Ec xabinen v$ chuyJn ho theo s( !W sau?
1) %
3
. 2) 4n$HCl
(1)
A
'5n%
#
+H
+
(2)
B
H
2
$ Ni + *
0
(3)
H
2
N
%H
)
2
%
5 (5)
(#)




C
1 +
C
2 +
C
3
&
3
# c" cZng th*c 6
^
O
1H
f.
a@ Yi)t cZng th*c c3u to c0a cc sn phm h[u c(? # & 6
1
6
%
6
3
M S
.
b@ Rn phm n$o c" to th$nh !Wng ph<n v$ chm rn s9 lEng !Wng ph<n c0a
mai sn phm.
2. oirol l$ mBt hEp ch3t d; vpng vi c3u tr4c nAu trong h/nh vG. oirol phn *ng
vi axit
nitric 7hi c" mQt anhi!rit axetic to th$nh sn phm q
vi hiVu su3t cao .
a@ Yi)t ph(ng tr/nh phn *ng to th$nh q .
b@ ohn *ng n$y thuBc loi phn *ng g/ 1 gii th,ch
d-a trAn c3u to c0a pirol.
N
H
H
H
H
H
c@ gii th,ch v; tr, c0a pirol b; t3n cZng 7hi ti)n h$nh phn *ng n$y b'ng
cc ch3t trung gian v$ !B bPn c0a ch4ng.
d@ Ro snh phn *ng nAu trAn vi phn *ng nitro ho c0a ben>en v$ toluen
b'ng han hEp Orf
3
sO
I
.
H ng dn gii:
1.
\ 6.O6
C%%H
C%%H
C3
C%%H
C%%H
C2
C%%H
C%%H
C1
C%%H
C%%H
B
O
A
&
3
H%N
C
C
%
%
%
63 c" % !Wng ph<n kuang htc.
6% c" H !Wng ph<n kuang htc.
M c" !Wng ph<n S u.
2. a@
N H
N
N%
2
H
Anhi6ri* axe*ic
HN%
3
+ CH
3
C%%H
b@ T<y l$ phn *ng th) electrophin v/ pirol l$ mBt hEp ch3t d; vpng c" t,nh
th(m do c" % cQp electron

v$ cQp electron cha tham gia liAn 7)t c0a nit(.

N H N H N H N H
N H
c@ ohn *ng th) electrophin c0a pirol v$ v; tr, ortho !9i vi nguyAn t= nit(
t*c l$ : cacbon cnh nguyAn t= nit( do cacbocatron trung gian bPn h(n nh2 3
c3u tr4c liAn hEp

N H
N%
2
H
N
H
N%
2
H N
N%
2
H
H
r)u nh"m rf
%
I
t3n cZng : cacbon s9 3 so vi nit( chm c" % c3u tr4c liAn hEp
7Cm bPn v$ 7hZng u tiAn.
N
H
H
N%
2
N
H
H
N%
2
d@
_ 6.O6
+ HN%
3
+ H
+

N%
2
CH
3
+ HN%
3
+ H
+

N%
2
CH
3
CH
3
N%
2
OoQc
Mo hiVu *ng liAn hEp c0a !Zi electron 7hZng liAn 7)t trAn nit( c0a pirol nAn
vpng pirol c" mNt !B electron cao h(n so vi vpng ben>en v/ vNy phn *ng
th) electrophin c0a pitrol dj h(n c0a ben>en.
Ypng ben>en c0a toluen c" thAm nh"m d6O
3
!y electron !;nh hng nh"m
rf
%
v$o v; tr, ortho nh pirol hoQc c" thJ !;nh hng v$o para.
45u : (3,75 im): 1; 1,75 im v 2; 2 im
1. 6c aminoaxit phn *ng vi nhau to th$nh
polipeptit. O+y cho bi)t c3u tr4c c0a cc
!ipeptit to th$nh tU leuxin
K6O
3
@
%
6O6O
%
6OKrO
%
@6ffO v$ histi!in
Kh/nh bAn@.
N
N
CH
2
CH C%%H
NH
2
H Hi1*i6in
2; gti # & l$ cc -aminoaxit : mZi tr2ng axit ba>( t(ng *ng v$ q l$ ion lwng
c-c.
a@ qc !;nh tm s9 nWng !B c0a # v$ & : !iJm !xng !iVn.
b@ Y)t alanin chuyJn vP c-c n$o 7hi pO y \ v$ pO z h1
c@ qc !;nh h$m lEng t(ng !9i c0a ion lwng c-c q c0a alanin : !iJm !xng
!iVn bi)t r'ng h'ng s9 axit c0a alanin? pe
1
{ %3\ !9i vi c<n b'ng #
q I O
I

pe
%
{ ^_^ !9i vi c<n b'ng q & I O
I
.
H ng dn gii:
1. 63u tr4c c0a cc !ipeptit ?
( CH
3
)
2
CH - CH
2
- CH(NH
2
) - C% - NH - CH - CH
2

C%%H
N
N
H
H - e! - Hi1 - %H
NH
N
CH
2
- CH(NH
2
) - C% - NH - CH
C%%H
- CH
2
- CH(CH
3
)
2
H - Hi1 - e! - %H
Hi1-e!
%
%
H
H
N
NH
CH
2 N
N
CH CH
2
CH
3
CH
3
] 6.O6
N
N
H
2
C
H
N
N
H
CH
2
- CH - C% - NH - CH -
C%%H NH
2
Hi1 - Hi1
e! - e! ( CH
3
)
2
CH - CH
2
- CH - C% - NH - CH - CH
2
- CH(CH
3
)
2

NH
2
C%%H
%.
a@ Y)t c0a aminoaxit : !iJm !xng !iVn 7hZng d;ch chuyJn vP ph,a catot
c|ng nh anot nAn nWng !B cc ion tri d3u phi b'ng nhau ?
}#~ { }&~ nAn tm s9 b'ng !(n v;v K1@
b@ Np biJu th*c t,nh cc h'ng s9 axit
e
1
{ v }O
I
~ { K%@ e
%
{ v }O
I
~ {
K3@
}O
I
~
%
{ tU K1@ K%@ K3@ c" }O
I
~ { Ke
1
e
%
@
1s%
pO
L
{ v T9i vi alanin? pO
L
{ { _F%

Y/ !iJm !xng !;An c0a alanin l$ _F% nAn v)t di chuyJn vP
ph,a c-c <m 7hi pO y \ v$ theo hng c-c d(ng 7hi pO z h
c@ .U K%@?
[ ]
[ ]
#,70
10
10
'
'
A
X
,9 + 9
35 + 2
2
1
= = =

rh vNy nWng !B t(ng !9i c0a }q~ l$? { {

F^^^_ 1
% I 1
...........................................
h 6.O6
[A]
[B]
{ 1

[X]
[A] +[B] +[X]
1

[A]
[X]
[B] [H
+
]
[X]
K
2
[X]
[B]
K
1
[A]
[X]
[X] [H
+
]
[A]
K
1
K
2
[A] [X]
[X] [B]
pK
1
+pK
2

2
2,35 +
9,69
2
[X]
[A] +[B] +[X]
1

[A]
[X]