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 / B0ng B
Ngy thi : 121212%%&
34u 5 (4 im): 1. 1,5 im ; 2. 2,5 im
1. 3-Metylbuten-1 tc dng vi axit clohidric to ra cc sn !h"#$
trong %& c& ' l (-clo-3-#etylbutan v ) l (-clo-(-#etylbutan.
)*ng c+ ch, !hn -ng$ h.y gii th/ch s0 to thnh hai sn !h"# '
v ).
2. 1h2n t/ch nguy3n t4 #5t h6! ch7t h8u c+ ' ch9 ch-a :$ ; v <
c& =>$?=@ : v 1>$1(@ ;.
aA Bc %Cnh cDng th-c !h2n tE cFa '$ bi,t Gh4i l6ng #ol cFa ' l
3H> ga#.
bA Ih0c nghiJ# cho bi,t: ' tc dng vi axit to esteK hi%ro ho ' c&
xLc tc 1d to h6! ch7t BK B cMng tc dng vi axit to esteK oxi ho B
b*ng NMn<
H
to thnh :<
(
v #5t axit %icacboxylic #ch di. O0a
vo cc t/nh ch7t ho hPc tr3n$ h.y %a ra #5t c7u to !hQ h6! c& thR
c& cFa B$ ' vi c7u trLc %4i x-ng v #ch cacbon GhDng !h2n
nhnh. Si,t cc !h+ng trTnh !hn -ng UdQng cDng th-c thu gPnA %R
gii th/ch.
H ng dn gii:
1.
H
+
CH
3
-CH-CH-CH
3
CH
3
CH
3
-CH-CH
2
-CH
2
CH
3
V
V
chuyRn vC
UWA
UWWA UWWWA
(-:lo-(-#etylbutan (-:lo-3-#etylbutan
CH
3
-C-CH
2
-CH
3
CH
3
V
:l
-
:l
-
CH
3
-CH-CH=CH
2
CH
3
CH
3
-CH-CH-CH
3
CH
3
:l
CH
3
-C-CH
2
-CH
3
CH
3
:l
Oo cacbocation bXc hai UWWA c& Gh nYng chuyRn vC hi%rua to thnh
cacbocation bXc ba UWWWA n3n to thnh hai sn !h"# '$ ).
2.
aA Z6ng : chi,# =>$?=@$ trong 3H> g ' c& (H1$3 g [4
nguy3n tE : (>
Z6ng ; chi,# 1>$1(@$ trong 3H> g ' c& 3H$H g [4 nguy3n tE
; 3H Z6ng < trong 3H> g ' c& \H$3 g [4 nguy3n tE < H.
SXy cDng th-c !h2n tE g]n %Lng cFa ' l: :
(>
;
3H
<
H
UM ^ 33_A
1 ct)
bA ' v B tc dng vi axit to este. [uy ra ' v B trong !h2n tE c&
nh&# <;.
;i%ro ho ' c& xLc tc 1d to h6! ch7t B. [uy ra ' trong !h2n tE c&
li3n G,t b5i.
<xi ho B b*ng NMn<
H
to thnh :<
(
v #5t axit %icacboxylic #ch
di. [uy ra ' v B trong !h2n tE c& H nh&# `<;$ hoac ( nh&# <;
v ( nh&# :;<$ hoac ( nh&# <; v ( nh&# :^<.
:7u to !hQ h6! c& thR c& cFa '$ B l:
': ;<:;
(
-:;U<;A-:
1\
;
(H
-:;U<;A-:;
(
<;
B: ;<:;
(
-:;U<;A-:
1\
;
3(
-:;U<;A-:;
(
<;
Uhoac ': ;<:;
(
-:<-:
1\
;
(H
-:<-:;
(
<; K <;:-:;<; -:
1\
;
(H
-:;<;-
:;<. :& thR vi,t cDng th-c c7u to cFa #ch cacbon - :
1\
;
(H
- trong
%& c& cc li3n G,t b5i !h2n b4 %4i x-ngA.
cc !h+ng trTnh !hn -ng:
Ih/ d: ' l ;<:;
(
-:;U<;A-:
1\
;
(H
-:;U<;A-:;
(
<;
': ;<:;
(
-:;U<;A-:
1\
;
(H
-:;U<;A-:;
(
<; V H :;
3
:<<;
U:;
3
:<<A:;
(
-:;U<:<:;
3
A-:
1\
;
(H
-:;U<:<:;
3
A-
:;
(
U<<::;
3
A
B: ;<:;
(
-:;U<;A-:
1\
;
3(
-:;U<;A-:;
(
<; V H :;
3
:<<;
U:;
3
:<<A:;
(
-:;U<:<:;
3
A-:
1\
;
3(
-:;U<:<:;
3
A-
:;
(
U<<::;
3
A
': ;<:;
(
-:;U<;A-:
1\
;
(H
-:;U<;A-:;
(
<; V 3 ;
(
;<:;
(
-:;U<;A-
:
1\
;
3(
-:;U<;A-:;
(
<;
B: ;<:;
(
-:;U<;A-:
1\
;
3(
-:;U<;A- :;
(
<;
;<<:-:
1\
;
3(
-
:<<; V ( :<
(

34u 55 (4,5 im): 1. 1 im ; 2. 0,5 im ; 2. 2 im ; &.
1 im
1. Ib etilen v !ro!ilen c& xLc tc axit$ !latin v %icu GiJn c]n
thi,t$ h.y vi,t s+ %d teng h6! iso!ren.
2. Ib #5t hidrocacbon GhDng no$ n3u cch %icu ch, (-bro#-(-
clo!ro!an.
( ct)
NMn<
H
1t
;
V
;
V
2. Ib axetilen v cc ho ch7t vD c+ c]n thi,t$ h.y %c nghC s+ %d
!hn -ng vi cc %icu GiJn %R teng h6! p
(%i#etyla#inoAafobenfen:
N N N CH
3
CH
3
&. Irong !hn -ng clo ho nhg ch7t xLc tc he:l
3
$ Gh nYng !hn -ng
t+ng %4i i cc vC tr/ Ghc nhau trong cc !h2n tE bi!henyl v
benfen nh sau:
790 790
1
1
1 1
1 1
0 250
0 250
250 0
250 0

aA I4c %5 #onoclo ho bi!henyl v benfen h+n Gj# nhau bao nhi3u
l]nk
bA Irong #5t !hn -ng clo ho bi!henyl thu %6c 1> ga# (-
clobi!henyl$ sl thu %6c bao nhi3u ga# H-clobi!henylk
H ng dn gii:
1.

CH
2
=CH
2
H
+
CH
3
-CH
2
+
cacbocation ny anGyl ho
!ro!en
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)
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
(IV)
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
+
3 ct)
(II)
(IV) CH
3
-CH-CH=CH
2
CH
3
CH
3
-CH
2
-C=CH
2
CH
3
Pt , t
o
- H
2
CH
2
=CH-C=CH
2
CH
3
UN,u hPc sinh l# theo cch Ghc cMng ra sn !h"# thT cho
nEa s4 %iR# theo biRu %iR#A
26
Ib 1-!ro!in$ th0c hiJn cc !hn -ng c5ng h6!:
:;
3
-::; V ;:l :;
3
-
::l^:;
(
1 #ol 1 #ol
:;
3
-::l^:;
(
V ;)r :;
3
-:)r:l-:;
3

3.
CH CH
600
0
C, XT
3
(I)
HNO
3
+ H
2
SO
4
%
NO
2
Fe/HC
NH
2
(II)
(III)
:ho (III) !hn -ng v i UWSA
NH
2
+
2CH
3
C
2N!OH
N
CH
3
CH
3
+
2N!C + 2 H
2
O
H
2
O
H"
2+
CH
3
CHO
#"
2
O/NH
3
CH
3
COOH
CH
3
COON!
N!OH
CH
4
C!O$N!OH
t
0
CH
4

C
2
, !$%
(IV)

CH
3
C + HC
CH CH
U;Pc sinh c& thR %icu ch, WS theo cch Ghc cMng cho %iR#
theo biRu %iR#A
NH
2
N!NO
2
HC
0-5
0
C
N
2
+
H ct)
N
2
+
+
C
6
H
5 N=N-C
6
H
4
N(CH
3
)
2
CH
3
N CH
3
&. aA
I4c %5 #onoclo ho cFa
bi!henyl h+n benfen H3> l]n.
bA mat x l s4 ga# H-clobi!henyl$ ta c&:
34u 555 (4 im): 1. 0,75 im ; 2.1 im ; 2.
2,25 im
1. ;.y gPi t3n cc sn !h"# to thnh Ghi anGyl ho benfen b*ng 1-
%o%exen vi xLc tc axit.
2. 'tro!in c& trong c2y 'tro!a belladonna. N& G,t tinh di dng
hTnh lc lYng$ n&ng chy i 11n
>
:. Nhg c& tc dng l# gi.n %dng
tE n3n n& %6c dQng trong Ghoa #ot. 'tro!in l #5t este c& c7u trLc
nh hTnh vl.
aA ;.y %nh d7u sao UpA vo nguy3n tE
cacbon b7t %4i v cho bi,t s4 %dng !h2n
lX! thR.
bA Nhi thuq !h2n atro!in trong #Di trgng
axit nhXn %6c tro!in v axit Ur$ [A`tro!ic.
Si,t !h+ng trTnh !hn -ng.
#t&o'()
N
CH
3
H
OCOCH C
6
H
5
CH
2
OH
2. Ib nh0a thDng nggi ta tch %6c xabinen v chuyRn ho theo s+
%d sau:
1) O
3
* 2) +)/HC
(1)
#
,-)O
4
,H
+
(2)
.
H
2
/ N( , t
0
(3)




C
1 ,
C
2 ,
C
3
' c& cDng th-c :
?
;
1H
<.
aA Si,t cDng th-c c7u to cFa cc sn !h"# h8u c+: ' $ ) $ :
1
$ :
(
$
:
3
.
bA [n !h"# no c& to thnh %dng !h2n v ch9 rs s4 l6ng %dng
!h2n cFa #ti sn !h"#.
H ng dn gii:
1. :
\
;
n
-:;
(
-U:;
(
A
1>
-
n ct)
G
bi!henyl
U(n> HA V U=?> (A
H3>
G
benfen
1 \
x =?> ( =?> ( 1>
1> (n> H 1>>>
x
1n$_ UgA
:;
3
UWA
:
\
;
\
V :;
(
^:;-U:;
(
A
?
-:;
3
:
\
;
n
-

:;U:;
3
A-
U:;
(
A
?
-:;
3
UWWA

UWA: 1-1henyl%o%ecan Uhoac %o%exylbenfenA K UWWA: Ur$[A-(-
!henyl%o%ecan
2.
+
N
CH
3
H
OH
T&o'() #/(t (0,S)-t&o'(1
Ihuq !h2n atro!in trong #Di tr gng axit
HOOC-CH-CH
2
OH
C
6
H
5
#t&o'( ) c& 3 cacbon b7t %4i$
c& ( %dng !h2n uuang hPc.
#t&o'()
N
CH
3
H
OCOCH C
6
H
5
CH
2
OH
3.
COOH
COOH
C3
COOH
COOH
C2
COOH
COOH
C1
COOH
COOH
.
O
#
:3 c& ( %dng !h2n uuang hPc.
:( c& H %dng !h2n uuang hPc.
' v ) cMng c& %dng !h2n lX! thR.
34u 57 (3,75 im): 1. 1 im ; 2.1,25 im ; 2. 0,5
im ; &. 1 im
M5t %isaccarit ' GhDng c& t/nh GhE. Nhi thuq !h2n trong #Di
trgng axit$ ' cho sn !h"# duy nh7t l !entof+ ). :Mng c& thR thuq
!h2n ' nhg enfi# -glicofi%afa
song GhDng dQng %6c -glicofi%afa. Ib ) c& thR to ra O-glucof+
b*ng cch cho tc dng vi ;:N rdi thuq !h2n UxLc tc axitA v GhE.
1A Si,t cDng th-c his+ v gPi t3n ) theo danh !h! hJ th4ng.
2A Si,t s+ %d cc !hn -ng chuyRn ho ) thnh O-glucof+.
2A Si,t cDng th-c c7u trLc cFa ' i dng vvng \ cnh !hwng.
\ ct)
HA mR Ghwng %Cnh c7u trLc vvng \ cnh cFa '$ nggi ta cho ' tc
dng vi :;
3
)r trong #Di trgng baf+ rdi thuq !h2n UxLc tc ;
V
A.
OQng cDng th-c c7u trLc$ vi,t s+ %d cc !hn -ng.
H ng dn gii:
1A ) c& 3 : b7t %4i gi4ng nh 3 : b7t %4i cu4i cQng i O-glucof+
CHO
OH
OH
CH
2
OH
HO
OH
OH
CHO
HO
CH
2
OH
S23 &!
OH

.
Ib
O-xlucof+ U([$3r$HrA-($3$H$n-
tetrahi%roxi!entanal
2A
OH
CHO
HO
CH
2
OH
OH
CN
OH

CH
2
OH
HO
OH
CN
OH
OH
CH
2
OH
HO
OH
C
O
OH
CH
2
OH
HO
OH
O=
- H
2
O
CHO
OH
OH
CH
2
OH
HO
OH
GhE
COOH
OH
OH
CH
2
OH
HO
OH
COOH
OH
OH
CH
2
OH
HO
OH
H
2
O, H
+
HCN
HO

2A Ib cc d8 GiJn cFa %c bi$ suy ra ' do ( !h2n tE ) li3n G,t -
1$1 glycofit n3n
O
O
O
OH
HO
OH
HO
HO
HO
hoac
O
OH
HO
HO
O
O
HO
HO
OH
&A
= ct)
O
O
O
OH
HO
OH
HO
HO
HO
CH
3
.&
baf+
CH
3
O
O
O
O
CH
3
O
CH
3
O
OCH
3
OCH
3
OCH
3
O
CH
3
O
CH
3
O
OCH
3
OH
H
3
O
+
2 OCH
3
CH
3
O
OCH
3
CHO
CH
2
OH
34u 7 (3,75 im): 1. 1,75 im ; 2. 2 im
1. :c a#inoaxit !hn -ng vi nhau to
thnh !oli!e!tit. ;.y cho bi,t c7u trLc
cFa cc %i!e!tit to thnh tb leuxin
U:;
3
A
(
:;:;
(
:;UN;
(
A:<<; v histi%in
UhTnh b3nA.
N
N
CH
2
CH COOH
NH
2
H H(%t(4()
26 xPi '$ ) l cc -a#inoaxit i #Di trgng axit$ baf+ t+ng -ng v B
l ion lyng c0c.
aA Bc %Cnh t9 s4 ndng %5 cFa ' v ) i %iR# %wng %iJn.
bA S,t alanin chuyRn vc c0c no Ghi !; z n v !; { _k
cA Bc %Cnh h# l6ng t+ng %4i cFa ion lyng c0c B cFa alanin i
%iR# %wng %iJn$ bi,t r*ng h*ng s4 axit cFa alanin: !N
1
^ ($3n
%4i vi c2n b*ng ' B V ;
V

!N
(
^ ?$\? %4i vi c2n b*ng B
) V ;
V
.
H ng dn gii:
1. :7u trLc cFa cc %i!e!tit :
( CH
3
)
2
- CH - CH
2
- CH(NH
2
) - CO - NH - CH - CH
2

COOH
N
N
H
H - 5e2 - H(% - OH
NH
N
CH
2
- CH(NH
2
) - CO - NH - CH
COOH
- CH
2
- CH(CH
3
)
2
H - H(% - 5e2 - OH
H(%-5e2
O
O
H
H
N
NH
CH
2 N
N
CH CH
2
CH
3
CH
3
N
N
H
2
C
H
N
N
H
CH
2
- CH - CO - NH - CH -
COOH NH
2
H(% - H(%
5e2 - 5e2 ( CH
3
)
2
CH - CH
2
- CH - CO - NH - CH - CH
2
- CH(CH
3
)
2

NH
2
COOH
(.
_ ct)
aA S,t cFa a#inoaxit i %iR# %wng %iJn GhDng dCch chuyRn vc
!h/a catot cMng nh anot n3n ndng %5 cc ion tri d7u !hi b*ng
nhau :
|'} ^ |)} n3n t9 s4 b*ng %+n vCK
U1A
bA ZX! biRu th-c t/nh cc h*ng s4 axit
N
1
^ K |;
V
} ^ U(A N
(
^ K |;
V
}
^ U3A
|;
V
}
(
^ tb U1A $ U(A $ U3A c& |;
V
} ^ UN
1
N
(
A
1~(
!;
W
^ K m4i vi alanin: !;
W
^ ^
\$>(
ST %iR# %wng %C3n cFa alanin l \$>( n3n v,t di
chuyRn vc !h/a c0c 2# Ghi !; z n$ v theo hng c0c d+ng Ghi
!; { _
cA Ib U(A:
[ ]
[ ]
4660
10
10
,
,
#
X
69 , 9
35 , 2
2
1
= = =

Nh vXy ndng %5 t+ng %4i cFa |B} l: ^

^ >$???\ 1
(
V 1
...........................................
? ct)
|'}
|)}
^ 1

|B}
|'} V |)} V
|B}
1
|'}
|B}
|)}
|;
V
}
|B}
N
(
|B}
|)}
N
1
|'}
|B}
|B}
|;
V
}
|'} N
1
N
(
|'} |B}
|B} |)}
!N
1
V
!N
(

(
($3n V
?$\?
(