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TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP.

HI DNG
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CHUYN : TNG HP HU C
Trng THPT chuyn H Ni - Amsteram

A. MT S VN L THUYT:
I. Cc phng php lm tng mch Cacbon:
1. Cc phng php ankyl ha bng hp cht c magie (RMgX):
+
' R X
R-R
+
2
3
1)
2)
CO
H O
+
RCOOH
+ 1)
O
RCH
2
CH
2
OH

RMgX +
3
1)
2)
HCHO
H O
+
RCH
2
OH
+
3
1) '
2)
R CHO
H O
+
RCH(OH)R
+
3
1) ' ''
2)
R COR
H O
+
R(R)C(OH)R
+
3
1) ' hoac ' ''
2)
R COOH R COOR
H O
+
RCOR (R)
2
C(OH)R
* Hc sinh cn lu :
+ Hp cht c magie RMgX rt d phn ng vi cc hp cht c hidro linh ng (H
2
O, NH
3
, ancol,
amin) bo qun v tin hnh phn ng trong ete khan.
+ Lp th ca phn ng cng RMgX vo hp cht cacbonyl: quy tc Crammer




2. Phng php anky ha ion axetilua:
R C CH
2 3
/
long
NaNH NH
R C C

Na
+

' R X
R C C R
3. Cc phng php ankyl v axyl ha hp cht thm:
a) Cc phn ng ankyl ha:

R
+ anken/ xt: HCl/AlCl
3
hoc axit protonic (HF > H
2
SO
4
> H
3
PO
4
)
+ ancol/ xt: axit protonic hoc Al
2
O
3
.
b) Cc phn ng axyl ha:

R

2) H
3
O
+
O
R
L
tb
N
R
-

O
-

R
L
tb
N
R
+ dn xut halogen/ xt: axit Lewis (AlCl
3
> FeCl
3
> BF
3
> ZnCl
2
)
+ dn xut ca axit cacboxylic (RCOX > (RCO)
2
O > RCOOR)/ xt: AlCl
3

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A Mt s phn ng formyl ha (thng dng gn nhm CHO vo phenol, ete thm hoc nhn thm
giu electron)
-
CO + HCl
AlCl
3
R R CHO
(Phn ng Gatterman Koch)
-
HCN + HCl/ AlCl
3
H
2
O
R R CHO
(Phn ng Gatterman)
-
HCO-N(R)
2
POCl
3
hoac COCl
2
R R CHO
(Phn ng Vilsmeier)
-
CHCl
3
NaOH
O H O H
OHC
(Phn ng Reimer Tiemann)
* Hc sinh cn lu :
+ C ch ca cc phn ng ankyl v axyl ha nhn thm l c ch S
E
2(Ar); trong ch c ch
to tc nhn electronfin.
+ Cc phn ng ankyl ha thng to thnh hn hp mono v poliankyl mun thu c sn phm
mono cn ly d cht phn ng.
+ Hng chnh ca phn ng khi th vo cc dn xut ca benzen.
4. Cc phng php ankyl v axyl ha cc hp cht c nhm metylen hoc nhm metyn linh ng:
a) Cht phn ng c dng X C

H
2
Y hoc X C

H(R) Y; vi X, Y l COR, -COOR, -CN, -


NO
2

Do X, Y l cc nhm ht electron mnh nguyn t H
o
rt linh ng dng baz tch H
+
, to
thnh cacbanion.

H
2
C
Y
X
C
2
H
5
ONa
- C
2
H
5
OH
-
CH
Y
X
Na
+
RBr
R HC
Y
X
1) C
2
H
5
ONa
2) RBr
R
2
C
Y
X
1) C
2
H
5
ONa
2) R'Br
R(R') C
Y
X
RCOCl
RCO HC
Y
X

* Hc sinh cn lu :
+ Khi th 2 nhm ankyl R v R khc nhau, nhm ankyl c kch thc nh hn hoc c hiu ng +I
nh hn s c a vo trc
+ Sn phm ca phn ng axyl ha cng c nguyn t H
o
linh ng, c th d dng b tch H
+
bi
chnh cacbanion
-
CH
Y
X

c phn ng cnh tranh:
-
CH
Y
X
RCO HC
Y
X
+ RCO
-
C
Y
X
+ H
2
C
Y
X

TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
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ngn phn ng ph ni trn, ngi ta dng baz mnh (mnh hn cacbanion) vi lng d.
b) Cht phn ng c dng R CH
2
X hoc R
2
CH X; vi X l COR, - COOR, - CN, - NO
2

Cc phn ng c tin hnh tng t, nhng phi s dng xc tc l baz rt mnh (NaNH
2
;
C
2
H
5
ONa) do nguyn t H
o
km linh ng hn so vi trng hp c 2 nhm X, Y ht electron.
5. Cc phng php ngng t:
a) Phn ng andol croton ha ca anehit v xeton:

C C
H
H
O
C C
H
H
O
+ C C C C
H
H
OHH
H
O
C C C C
H
H H
O
H
+
hoac OH
-
H
+
hoac OH
-

* Hc sinh cn lu :
+ C ch ca giai on cng andol: A
N

+ Giai on croton ha c th xy ra theo c ch E
1
hoc E
1
cb (khi c H

linh ng, xt baz mnh)


+ Khi thc hin phn ng andol croton ha t 2 cu t khc nhau c th to ra hn hp sn phm,
trong sn phm chnh l sn phm ngng t gia:
- cu t cacbonyl c tnh electrophin cao hn
- cu t metylen c H

linh ng hn.
b) Phn ng ngng t ca anehit, xeton vi cc hp cht c nhm metylen hoc metyn linh ng:
H
2
C
Y
X
-
CH
Y
X
B
-
- BH
C O
C HC
O
- Y
X
BH
- B
-
C HC
OH
Y
X
C C
Y
X
- H
2
O

* Hc sinh cn lu :
+ Xc tc dng trong cc phn ng ny thng l cc baz hu c yu, c th ngn chn c phn
ng t ngng t vi nhau ca cc anehit, xeton.
+ Phn ng ngng t anehit thm vi anhidrit axit to thnh axit , khng no (phn ng ngng
t Perkin) cng c c ch tng t nh trn.
C
6
H
5
CH=O + (CH
3
CO)
2
O
3
3
OO
OOH
khan
CH C Na
CH C
C
6
H
5
CH= CH COOH
c) Phn ng cng Micheal - cng cc hp cht c nhm metylen hoc metyn linh ng vo hp cht
cacbonyl-,-khng no:
H
2
C
Y
X
-
CH
Y
X
B
-
- BH
H
2
C CH CH O
H
2
C
-
CH CH O
CH
Y
X
BH
- B
-
H
2
C CH
2
CH O
CH
Y
X

* Hc sinh cn lu :
+ Xc tc baz c th l C
2
H
5
ONa (nhit phng); piperidin (nhit cao hn).
+ C th thay th hp cht cacbonyl-,-khng no bng cc hp cht nitro (NO
2
) hoc nitril (CN)-,-
khng no.
d) Phn ng ngng t Claisen ngng t este vi cc hp cht c nhm metylen linh ng:
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+ Phn ng ngng t gia cc este vi nhau:
CH
3
COOC
2
H
5
+ CH
3
COOC
2
H
5

2 5
C H ONa
CH
3
COCH
2
COOC
2
H
5
+ C
2
H
5
OH
C ch phn ng:
H CH
2
C OC
2
H
5
O
C
2
H
5
O
O
OC
2
H
5
CH
2
C
-C
2
H
5
OH
CH
3
C
O
OC
2
H
5
CH
3
C OC
2
H
5
O
CH
2
COOC
2
H
5
CH
3
C CH
2
COOC
2
H
5
O
- C
2
H
5
O

+ Phn ng ngng t este vi hp cht nitril:
CH
3
COOC
2
H
5
+ RCH
2
CN
2 5
C H ONa
CH
3
COCH
2
(R)CN + C
2
H
5
OH
+ Phn ng ngng t este vi anehit hoc xeton:
CH
3
COOC
2
H
5
+ CH
3
COCH
3

2 5
C H ONa
CH
3
COCH
2
COCH
3
+ C
2
H
5
OH
II. Cc phng php lm gim mch Cacbon:
1. Phn ng ecacboxyl ha bi nhit: xy ra khi nhm COOH gn vi nhm c kh nng ht electron
mnh
2. Phng php vi ti xt: RCOONa + NaOH
o
CaO
t
RH + Na
2
CO
3

3. Phn ng Hunzdicker: RCOOAg + Br
2

4
o
CCl
t
RBr + CO
2
+ AgBr
4. Phn ng halofom:RCOCH
3
+ 3X
2
+ 4NaOH RCOONa + CHX
3
+ 3NaX + 3H
2
O
5. Phn ng thoi phn Hoffman: R CO NH
2

2
2
, ,
o
Br NaOH t
CO
RNH
2

6. Cc phn ng oxi ha lm gy mch Cacbon:
a) Cc phn ng lm gy lin kt lin kt i C=C:
+
4
,
o
KMnO t
CH
3
COOH + CH
3
COCH
3


HC
O
O
C
O
CH
3
CH
3
H
3
C

b) Cc phn ng lm gy lin kt C C vic-iol:
C C
OH OH
C
O
C
O
+
HIO
4
hoac Pb(OOCCH
3
)

c) Phn ng oxi ha ankyl, ankenyl hoc dn xut ca benzen:
KMnO
4
hoac K
2
Cr
2
O
7
H
+
R COOH

* Hc sinh cn lu :
+ Nu v tr ca mch bn khng cn H th phn ng oxi ha hu nh khng xy ra.
+
3
O

2
/ , H O H Zn
+
CH
3
CH=O + CH
3
COCH
3

2 2
/ H O H
+
CH
3
COOH + CH
3
COCH
3
CH
3
CH= C(CH
3
)
2

TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
HOAHOC.ORG NG XUN QUNH
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+ Nu dng Na
2
Cr
2
O
7
(khng c H
+
) s to thnh xeton m khng b ct mch

CH
2
R C R
O
Na
2
Cr
2
O
7
250
o
C, p

+ Nu v tr ca mch bn ch cn 1 nguyn t H th phn ng s to ra ancol bc 3 (khng ct mch
cacbon)

CH R
2
C R
2
OH

III. Cc phng php to vng:
1. Cc phng php ankyl, axyl ha v ngng t ni phn t: nguyn tc tng t nh cc phn ng
ankyl, axyl ha v ngng t nu trn.
2. Phn ng cng Diels Alder:

+

ien ienophin
* Hc sinh cn lu :
+ ien phi cu dng s-cis; dng s-trans (V d: ) khng phn ng.
+ Cc nhm th v tr cis u mch ien gy cn tr khng gian kh phn ng.
+ ien c nhm th y electron (khng gy cn tr khng gian) tng kh nng phn ng.
+ ienophin c nhm th ht electron tng kh nng phn ng.
+ Cu hnh ca sn phm ging vi cu hnh ca ienophin.
+ Hng ca phn ng:

R
+
X X
R



R
+
X
R X


R
+
X
R
X



R
+
R
X
X

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IV. Cc phn ng oxi ha v kh trong tng hp hu c:
1. Cc phn ng oxi ha:
a) Cc phn ng oxi ha anken
b) Phn ng oxi ha nguyn t H v tr allyl:
Tc nhn oxi ha: Pb
4+
, SeO
2


C C CH
2
C C CH
O H

c) Cc phn ng oxi ha ankyl, ankenyl hoc dn xut ca benzen
d) Cc phn ng oxi ha ancol:
+ Ancol bc I
[ ] O
anehit
+ Ancol bc II
[ ] O
xeton
(Qu trnh oxi ha ancol bc I thnh anehit cn khng ch cn thn khng chuyn thnh axit).
+ vic-iol
4
HIO
cacbonyl.
e) Cc phn ng oxi ha anehit, xeton:
+ Anhit
[ ] O
axit cacboxylic
Tc nhn oxi ha: O
2
/xt, [Ag(NH
3
)
2
]
+
, KMnO
4
/H
+
, K
2
Cr
2
O
7
/H
+


+ Xeton
[ ] O
b ct mch thnh axit cacboxylic v xeton
Tc nhn oxi ha: KMnO
4
/H
+
, HNO
3

2. Cc phn ng kh:
a) Phng php hidro ha xc tc:
Tc nhn kh:
+ H
2
/ Ni, Pt, Pd:

C C C C
C C

RCOCl RCH=O
RCH=O RCH
2
OH
R-CO-R R-CH(OH)-R
R-COO-R RCH
2
OH + ROH
RX RH
RNO
2
RNH
2

R-CN R-CH
2
NH
2

R-CO-NHR RCH
2
NHR
+ H
2
/ Pd/ BaSO
4
, BaCO
3
(xc tc Lindlar): kh la chn lin kt ba v lin kt i

C C C C

+ H
2
/ [(C
6
H
5
)
3
P]
3
RhCl: kh la chn lin kt i C=C ch cha 1 hoc 2 nhm th.
Tc nhn oxi ha: CuO, K
2
Cr
2
O
7
/H
+
, CrO
3
/H
+

TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
HOAHOC.ORG NG XUN QUNH
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* Hc sinh cn lu : c th lp th ca cc phn ng ny u l cng syn
b) Phng php kh bng hidrua kim loi:
Tc nhn kh: thng dng LiAlH
4
, NaBH
4

RCOCl RCH
2
OH
RCH=O RCH
2
OH
R-CO-R R-CH(OH)-R
RCOOH RCH
2
OH
R-COO-R RCH
2
OH + ROH
Epoxit 1,2-iol
RX RH
RNO
2
RNH
2

R-CN R-CH
2
NH
2

R-CO-NHR RCH
2
NHR
* Hc sinh cn lu : phn ng kh xy ra theo c ch cng A
N
.
c) Cc phng php kh bng kim loi ha tan:
Tc nhn kh:
+ Na/NH
3
lng:
C C C C
(lp th: cng trans)
+ Na/ C
2
H
5
OH: RCOOH RCH
2
OH
R-COO-R RCH
2
OH + ROH
+ Zn (Hg)/ HCl: R-CO-R R-CH
2
-R
V. Bo v nhm chc:
* iu kin ca nhm bo v:
+ c to ra trong iu kin nh nhng
+ n nh trong sut qu trnh phn ng cc trung tm phn ng khc.
+ D ti sinh nhm chc ban u.
1. Bo v nhm ancol:
a) Chuyn thnh nhm ete:

C OH C O R
...
C OH
HI

b) Chuyn thnh nhm este (nhm este tng i bn trong mi trng axit):

C OH C OCO R
...
C OH
NaOH

c) Chuyn thnh nhm axetal hoc xetal (bo v cc iol):

C
C
OH
OH
+
O C
R
R
C
R
R C
C
O
O
...
H
+ C
C
OH
OH

Khng kh c bng NaBH
4

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2. Bo v nhm cacbonyl:
To thnh axetal hoc xetal tng t nh bo v cc iol; thng s dng etilen glycol.
3. Bo v nhm cacboxyl:
Chuyn thnh nhm este; thng to thnh tert-butyl este (d loi bng H
+
) hoc benzyl este (d loi
bng hidro phn)
4. Bo v nhm amino:

NH
RCOCl hoac (RCO)
2
O
N CO R
OH
-
NH
Ph-CH
2
-OCOCl
N OCO-CH
2
-Ph
H
2
/Pd
Ph
3
-CCl
N C-Ph
3
CH
3
COOH
khan
...
...
...

B. MT S BI LUYN TP:
Bi 1: Cho s chuyn ha:
OH
1) CH
3
MgBr
A
D
H
2
SO
4
H
2
/ Ni
(p sut)
H
2
O
CrO
3
OH H
3
C
C
E
(H
3
C)
2
C= CH
2
B
2) H
2
O
H
+
, t
0
1) O
3
2) H
2
O/Zn

a) Hy vit cu to cc cht t A n E
b) Hy vit c ch phn ng t phenol to thnh A.
Bi 2: Khi cho isobutilen vo dung dch H
2
SO
4
60%, un nng ti 80
0
C thu c mt hn hp gi tt l i -
isobutilen gm hai cht ng phn ca nhau A v B. Hiro ho hn hp ny c hp cht C (quen gi l
isooctan). C l cht c dng nh gi cht lng nhin liu lng.
C cng c th c iu ch bng phn ng trc tip ca isobutilen vi isobutan khi c mt axit v
c lm xc tc.
Hy gi tn C theo IUPAC v vit cc phng trnh phn ng gii thch s to thnh A, B, C.
Bi 3: Tin hnh phn ng ime ho trimetyletilen c H
+
xc tc thu c hn hp sn phm l cc ng
phn c cng thc phn t C
10
H
20
. Cho bit cc sn phm to thnh da vo c ch phn ng.
Khi ozon ho hn hp thu c sau phn ng ime ho trn , ngoi cc anehit v xeton ca sn
phm d kin cn thu c mt lng ng k butan -2-on, gii thch c ch hnh thnh butan-2-on trong
cc phn ng trn.
Bi 4: un nng Stiren vi axit H
2
SO
4
ta thu c hp cht:

Hy gii thch qu trnh hnh thnh sn phm trn.
TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
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Bi 5:
T isopren hy vit cc phng trnh phn ng iu ch trans - 2 - metylxiclohexanol.
Bi 6: Vit cc phng trnh phn ng( dng cu to) to thnh A, B, C, D, M, N theo s sau:
a) BrCH
2
CH
2
CH
2
CH=O
0
dd NaOH, t
A
3
CH OH,HCl khan
B
b) BrCH
2
CH
2
CH
2
COOH
0
1) ,
2)
ddNaOH t
ddHCl

C
0
, H t
+
D
c) HOCH
2
(CHOH)
4
CH=O
2
2
Br ,H O
M
0
, H t
+
N
Bi 7: Cho s chuyn ha:
OH
OCH
3
A B C
H
OCH
3
COOC
2
H
5
(D)
E
F
G
(COOC
2
H
5
)
2
HCOOC
2
H
5
(C
2
H
5
O)
2
CO
C
2
H
5
OH
KCN PBr
3 H
+
H
+

a) Cho bit cu to ca cc cht t A n G.
b) Gii thch s hnh thnh cc cht E, F, G.
Bi 8: T propilen v cc cht v c cn thit, vit s phn ng iu ch:
a) Axit 2,5-imetyladipic b) Axit hept-2-inoic
Bi 9: T xiclopentanol iu ch axit 2-oxoxiclopentancacboxylic.
Bi 10: T benzen v cc hp cht s 2 C, hy tng hp:
a)
CH
2
CH
2
NH CH
3
b)
CH CH
OH NHCH
3
CH
3
c)
NH C O C
2
H
5
O
CH
3

d)
Cl
SO
2
NH
2
N H
2
e)
NH C
4
H
9
COO CH
2
CH
2
N(CH
3
)
2

f)
CH CH
2
NH
2
O H
O H
OH
g)
CH
2
CH
2
NH
2
O H
O H
h)
CH CH CH
3
O H
O H
OH NH
2

Bi 11: T benzen v cc cht s 3 C, tng hp:
a)
C H
3
CH
3
b)
O
O
O
c)
O H C(CH
3
)
2
OH

Bi 12: T CH
3
CH
2
CH
2
CH
2
OH v cc cht v c, tng hp
C H
3
CH
3
CONH
2
O

C2H5ONa
TI LIU LUYN THI & BI DNG KIN THC NM 2011
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Bi 13:
T
H
3
CO
H
3
CO
OH
C H
3
C H
3
COOH
v cc cht v c, iu ch
H
3
CO
H
3
CO
O
CH
3
CH
3

Bi 14: T H
2
N-CH
3
v CH
2
=CH-COOC
2
H
5
, tng hp
N O C H
3

Bi 15: Khi cho isobutanal tc dng vi axit malonic c mt piriin thu c hp cht A. un nng A trong
mi trng axit thc hin phn ng ecacboxyl ho thu c hai sn phm A
1
v A
2
l ng phn ca
nhau.
(A
5
bn hn) A
5
, A
6
H
3
PO
4
A
4
HCl
A
1
A
3
LiAlH
4
A
1
(hp cht no)

Bit rng A
2
khi b oxi ho to thnh axit oxalic. A
1
l lacton.
Xc nh cu to ca A
1
, ...,A
6
v vit cc phng trnh phn ng.
Bi 16: C mt s dn xut gc CH
3
ca axit axetic biu hin hot tnh tng trng cy trng.

CH
2
COOH OCH
2
COOH
OCH
2
COOH
Cl
Cl
OCH
2
COOH
Cl
Cl
Cl
(A) (B) (C)
(D)

1. Gi tn A, B, C.
2. A c iu ch t naphtalen v axit cloaxetic c mt cht xc tc 180 - 215
0
C. Vit phng trnh phn
ng v gi tn c ch ca phn ng.
3. B cng c iu ch t nguyn liu trn qua cht trung gian l 1 - naphtol. Vit s cc phn ng v
nu c ch.
4. C cng c iu ch t phenol v axit axetic. Vit s phn ng.
5. Khc vi C, D c iu ch t mt dn xut tetraclobenzen(X) theo s :
X
NaOH
metanol
ClCH
2
COOH
H
+
1.
2.
D

a) Hon thnh s trn.
b) Trong qu trnh sn xut D sinh ra mt lng nh ioxin l cht cc k c c cng thc:
O
O
Cl
Cl
Cl
Cl

Gii thch s to thnh ioxin.


TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
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C. BI GII:
Bi 1:
a)
(A)
CH
3
OH
CH
3
H
3
C

(B)
CH
3
OH
CH
3
H
3
C

(C)
CH
3
O
CH
3
H
3
C

(D)
CH
3
CH
3
H
3
C
CH
3

(E)
CH
3
O
CH
3
H
3
C
CH
3
O

b)

H
+
C
+
OH
OH
H
+
- H
+
OH


Bi 2:

+
CH
3
CH
3
C CH
3
H
CH
3
CH
2
C CH
3
(1)

CH
3
CH
3
C CH
2
CH
3
CH
3
C CH
3
+
CH
3
CH
3
C CH
3
CH
3
CH
2
C CH
3
(2)

CH
3
C
CH
3
CH
3
CH
2
C CH
3
CH
3
CH
3
C CH C CH
3
CH
3
CH
3
CH
3
(A) (> 80%)
(< 20%) (B)
CH
3
CH
3
CH
3
CH
2
CH
2
C C
CH
3
Zaixep
- H

(A)
CH
3
CH
3
CH
3
CH
3
C CH C
CH
3
H
2
/Ni
CH
3
C
CH
3
CH
3
CH
2
CH CH
3
CH
3
Isooctan(C)
2,2,4 - trimetylpentan
(Qui c c ch s octan l 100)

* Isobutilen vi isobutan khi c mt axit v c lm xc tc cng to ra C:
C ch ca qu trnh tng t phn ng trn trong giai on (1) v (2), sau :
o
-
o
+
TI LIU LUYN THI & BI DNG KIN THC NM 2011
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CH
3
CH
3
C CH
2
CH
3
CH
3
C CH
3
CH
3
C
CH
3
CH
3
CH
2
CH CH
3
CH
3
CH
3
CH CH
3
CH
3
+
(C)
+ CH
3
C
CH
3
CH
3
H
3
C
CH
3
C
CH
3
sinh ra li lp li (2). C nh vy.


Bi 3: * Sn phm to thnh khi ime ha trimetyletilen:
CH
2
CH
3
C CH
3
CH
3
H
+
CH
3
CH
3
CH C CH
3

CH
3
CH
3
CH
3
C CH
CH
3
CH
3
C CH
2
CH
3 CH
3
C CH CH
3
CH
3
+
CH
3
CH
3
C CH
3
CH
2


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

* Ozon phn hn hp trn thu c:
v HCHO
O C
CH
3
CH
3
O
CH
3
CH
3
C CH
CH
3
CH
3
C CH
2
CH
3
CH
3
CH
2
C
CH
3
CH
3
C O
CH
3
ozon phn
CH
3
CH
2
C
CH
3
CH
3
CH C
CH
2
CH
3
CH
3
CH
3
CH
3
CH
3
C C
CH
3
CH
3
C CH
2
CH
3

* S to thnh mt lng ng k butanon - 2 l do c s ng phn ha trimetyletilen, to thnh sn
phm ph:
TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
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CH
3
C CH CH
3
CH
3
H
+
CH
3
CH
3
C CH
3
CH
2
CH
2
CH
2
C CH
3
CH
3
H
+
-
CH
2
CH
3
C CH
3
CH
3
CH
3
CH
3
C CH
2
CH
2
+
CH
3
CH
2
C CH
2
C CH
2
CH
3
CH
3
CH
3
CH
3

CH
3
CH
2
C CH C CH
2
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
2
C CH
2
C CH
2
CH
3
H
+

Khi :
CH
3
CH
3
CH
3
CH
2
CCHO
CH
3
O C CH
2
CH
3
CH
3
CH
3
CH
2
C CH C CH
2
CH
3
CH
3
CH
3
CH
3
+
v HCHO
ozon
phn
CH
3
C CH
2
CH
2

Bi 4:
CH = CH
2
H
+ CH
+
CH
3
CH = CH
2
C
CH
2
CH
3
C H
+

Bi 5:
H
3
C
+
CH
2
CH
2
CH
2
CH
2
H
3
C
t
0
,p

CH
3
H
2
B
H
CH
3
H
BH
2
CH
3
H
3
B
H
2
O
2
/OH
- H
3
BO
3
CH
3
H
OH
Hiu sut 75%

o
+
o
-
o
-
o
+
TI LIU LUYN THI & BI DNG KIN THC NM 2011
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Bi 6:
a)

Br-(CH
2
)
3
-CH=O
NaOH
HO-(CH
2
)
3
-CH=O
O
t
0
OH
H
CH
3
OH
HCl khan
O
OCH
3
H
(A)
(B)

b)
Br-(CH
2
)
3
-COOH
NaOH
HO-(CH
2
)
3
-COONa
O
(D)
(C)
ddHCl
HO-(CH
2
)
3
-COOH
H
+
O

c)
HOBr
O
(N)
H
+
O
CH
2
OH
CH
OH 4
CH =O CH
2
OH
CH
OH 4
COOH
(M)
HO-CH
2
-CH
OH


Bi 7:
a)
(A)
Br
OMe

B r
OMe
B r
OMe (B)
CN
OMe

(C)
COOH
OMe

(E)
OMe
C
2
H
5
O
2
C C
C
O
O
OC
2
H
5

(F)

OMe
C
2
H
5
O
2
C C
O
H

(G)

OMe
C
2
H
5
O
2
C C
O
OC
2
H
5

b) Gii thch s hnh thnh ca:
E:
COOC
2
H
5
H
OCH
3
C
2
H
5
ONa
C H
-
COOC
2
H
5
OCH
3
C
C
O H
5
C
2
O
O H
5
C
2
O
o+
H
5
C
2
OOC
OCH
3
C
COOC
2
H
5
O
-
OC
2
H
5
H
5
C
2
OOC
OCH
3
COOC
2
H
5
O
- C
2
H
5
O
-

Tng t, gii thch c s hnh thnh F v G.
TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
HOAHOC.ORG NG XUN QUNH
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Bi 8:
a) CH
2
= CH CH
3

2
0
450
Cl
C
CH
2
= CH CH
2
Cl
0
, Na t
CH
2
= CH CH
2
CH
2
CH = CH
2

HBr

CH
3
CH(Br) CH
2
CH
2
CH(Br) CH
3

ete
Mg
CH
3
CH(MgBr) CH
2
CH
2
CH(MgBr) CH
3

2
3
1)
2) H
CO
O
+
HOOC CH(CH
3
) CH
2
CH
2
CH(CH
3
) COOH
b) CH
2
= CH CH
3

2
0
450
Cl
C
CH
2
= CH CH
2
Cl
0
, Na t
CH
2
= CH CH
2
CH
2
CH = CH
2

2
1:1
Br

CH
2
Br CH(Br) CH
2
CH
2
CH = CH
2

2
/ H Pd
CH
2
Br CH(Br) CH
2
CH
2
CH
2
CH
3

2
1) / tan
2)
KOH e ol
KNH
HC C CH
2
CH
2
CH
2
CH
3

3
CH MgCl
ClMgC C CH
2
CH
2
CH
2
CH
3

2
3
1)
2) H
CO
O
+

HOOC - C C CH
2
CH
2
CH
2
CH
3
Bi 9:
OH Br
MgBr
COOH
COOH
Cl
COOH
OH
COOH
O
HBr Mg/ ete khan
1) CO
2
2) H
3
O
+
Cl
2
/ P
t
o
NaOH, t
o
CuO, t
o

Bi 10:
a)
C
2
H
5
CH CH
2
CH
2
CH
2
Br
CH
2
=CH
2
H
+
Pd, t
o
HBr, peoxit
CH
2
CH
2
NHCH
3
CH
3
NH
2

b)
CHO CH C
2
H
5
OH
CH = CH - CH
3
CO, HCl 1) C
2
H
5
MgBr KOH/etanol
AlCl
3
2) H
3
O
+
HOCl
CH CH
O H
CH
3
Cl
CH
3
NH
2
CH CH
O H
CH
3
NHCH
3

c)
NO
2
HNO
3
Fe, HCl
C
2
H
5
Cl
H
2
SO
4
d
to
NaNO
2
+HCl
NH
2
NHCOCH
3
CH
3
COCl
HNO
3
H
2
SO
4
NHCOCH
3
O
2
N
Fe, HCl
NHCOCH
3
N H
2
NHCOCH
3
O H NHCOCH
3
O C
2
H
5
d)
NO
2
HNO
3
Cl
2
NaHCO
3
H
2
SO
4
d
NH
3
NO
2
Cl
NH
2
Cl
Fe, HCl
NH
3
+
HO
3
S
Cl
PCl
5
AlCl
3
H
2
SO
4
d
HSO
4
-
NH
3
+
ClO
2
S
Cl
HSO
4
-
NH
3
+
H
2
NO
2
S
Cl
HSO
4
-
NH
2
H
2
NO
2
S
Cl

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e)
CH
3
HNO
3
CH
3
Cl
H
2
SO
4
d
C
4
H
9
Cl
NO
2
H
3
C
Fe, HCl
PCl
5
AlCl
3
KMnO
4
, t
o
NHC
4
H
9
HOOC
NO
2
HOOC
NH
2
HOOC
NHC
4
H
9
ClOC
(CH
3
)
2
- N - H +
O
o+
o+
o
o
(CH
3
)
2
-N-CH
2
-CH
2
-OH
(CH
3
)
2
-N-CH
2
-CH
2
-OH
H
9
C
4
HN COO-CH
2
-CH
2
-N(CH
3
)
2

f)
OH
Cl
2
NaNO
2
+ HCl
AlCl
3
HNO
3
2) H
+
Fe, HCl
t
o
1) NaOH,t
o
,p
CO + HCl
Cl
OH
NH
2
OH
NO
2
OH
OH
O H
O H
CHO
AlCl
3
O H
O H
CH
O H
CN
HCN H
2
/ Pd
O H
O H
CH
O H
CH
2
NH
2

g)
KOH/ etanol
H
2
/ Pd
O H
O H
CH
O H
CH
2
NH
2
O H
O H
CH CH NH
2
O H
O H
CH
2
CH
2
NH
2

h)
O H
O H
CHO
OH
-
Fe, HCl
O H
O H
CH
O H
CH CH
3
NO
2
CH
3
CH
2
NO
2
O H
O H
CH C CH
3
NO
2
H
2
O/H
+
O H
O H
CH
OH
CH CH
3
NH
2


Bi 11:
a)
CH
2
-CH=CH
2
Mg/ ete
1) (CH
3
)
2
CO
H
2
SO
4
2) H
3
O
+
CH
2
=CH-CH
2
Cl
AlCl
3
HBr/ peoxit
CH
2
-CH
2
-CH
2
-Br
CH
2
-CH
2
-CH
2
-MgBr CH
2
C OH
CH
3
CH
3
3

TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
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b)
CH
3
Mg/ ete
Cl
2
NaOH
2) H
3
O
+
CH
3
Cl
AlCl
3
COCl
2
CH
2
-CH
2
-CH
2
-OH
Cl
2
, as
CH
2
Cl CH
2
MgCl
O
1)
CHCl-CH
2
-CH
2
-OH CH(OH)-CH
2
-CH
2
-OH
O
O
O

c)
OH
Cl
2
AlCl
3
2) H
+
1) NaOH,t
o
,p
Cl
H
3
C C CH
3
O
H
+
H
3
C C
+
CH
3
OH
OH CH
3
CH
3
O H OH
H
+
- H
2
O
CH
3
C
+
CH
3
O H
OH
CH
3
C
CH
3
OH O H

Bi 12:
OH O
CuO, t
0
H
+
CHO
COOH
CONH
2
CONH
2
O
NH
3
, t
0
Ag
2
O
Br
2
, H
2
O

Bi 13:
CH
3
CH
3
O
H
CH
3
CH
3
O
COOH
O
OH
o
o+
o+
+
H
+
CH
3
CH
3
O
O
LiAlH
4
CH
3
CH
3
O
OH
CH
3
CH
3
O
H
2
SO
4
,t
o

Bi 14:
CH
3
NH
2
O
OC
2
H
5
o+
o
CH
3
NH CH
2
CH
2
COOC
2
H
5
O
OC
2
H
5
o+
CH
3
N CH
2
CH
2
COOC
2
H
5
CH
2
CH
2
COOC
2
H
5
C
2
H
5
ONa
N CH
3
O
COOC
2
H
5
H
+
, t
o
N CH
3
O

(S dng phn ng cng Micheal v ngng t Claisen)
TI LIU LUYN THI & BI DNG KIN THC NM 2011
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Bi 15:
(A) OH
Piriin
CH
3
CH
CH
3
CH CH
COOH
COOH
+
COOH
COOH
CH
2
CHO
CH
3
CH
CH
3

OH
CH
3
CH
CH
3
CH CH
COOH
COOH
COOH CH
2
CH
CH
3
CH
CH
3
OH
-CO
2
t
0

H
+
,t
0
OH
CH
3
CH
CH
3
CH CH
2
COOH
-H
2
O
COOH CH CH
CH
3
CH
CH
3
CH
3
C
CH
3
CH CH
2
COOH
(A
2
)

+ COOH HOOC
COOH
CH
3
CH
CH
3
[O]
CH
3
CH
CH
3
CH CH COOH


CH
3
C
CH
3
CH CH
2
COOH
(A
1
)
H
+
C
O C
CH
2
CH
2
O
CH
3
CH
3

C
O C
CH
2
CH
2
O
CH
3
CH
3
(A
3
)
OH OH
CH
2
CH
2
CH
2
CH
3
C
CH
3
LiAlH
4

O
(HCl)
C
O C
CH
2
CH
2
O
CH
3
CH
3
(A
4
)
Cl OH
C CH
2
CH
2
CH
3
C
CH
3
H
+
CH
3
CH
3
OH
C
O C
CH
2
CH
2
Cl


CH
3
C
CH
3
CH
2
CH
2
CH
2
OH OH
(A
3
)
H
3
PO
4
OH
CH
2
CH
2
CH
CH
3
C
CH
3
(A
6
)
+ H
2
O
CH
2
CH
2
H
2
C
C
O
CH
3
CH
3
(A
5
)
H
2
O +

o
+
o
-
TT LUYN THI & BI DNG KIN THC NGY MI 18A/88 INH VN T - TP. HI DNG
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Bi 16:
1. A: Axit (1 - naphtyl)axetic. B: Axit (1 - naphtoxi)axetic.
C: Axit (2,4 - iclophenoxi)axetic. [2,4 - D] D: Axit (2,4,5 - triclophenoxi)axetic. [2,4,5 - T]
ClCH
2
COOH
t
0
, xt
S
E
+
CH
2
COOH
+ HCl
2.

ClCH
2
COOH
3.
H
2
SO
4
-H
2
SO
4
OSO
3
H
H
2
O
OH
Kim, S
N
2
-HCl
OCH
2
COONa
OCH
2
COOH
H
+
-Na
+

OH
Cl
2
/CCl
4
-HCl
OH
Cl
Cl
ONa
Cl
Cl
-H
2
O
NaOH
4.

CH
3
COOH
Cl
2
, P
-HCl
CH
2
COOH
Cl
NaOH
-H
2
O
Cl
CH
2
COONa

-NaCl
ONa
Cl
Cl
Cl
CH
2
COONa
+
OCH
2
COONa
Cl
Cl
H
+
OCH
2
COOH
Cl
Cl

Cl
OCH
2
COOH
Cl
Cl
Cl
OCH
2
COONa
Cl
Cl
S
N
2
ClCH
2
COOH
Cl
ONa
Cl
Cl
S
N
2Ar
NaOH
5.
(X)
Cl
Cl
Cl
Cl
H
+

S to ioxin:
Cl
ONa Cl
Cl
Cl
NaO Cl
Cl
+
O
O
Cl
Cl
Cl
Cl
+ 2NaCl

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