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-R
R ' X
1) CO2
2) H O
+
RCOOH
3

+
RMgX

1)

RCH2CH2OH

2) H3O+

1) HCHO
2) H 3O

RCH2OH

1) R ' CHO
2) H 3O

RCH(OH)R

1) R ' COR ''

2) H 3O

R(R)C(OH)R

1)R ' COOH hoac R ' COOR ''

2)H 3O

RCOR

(R)2C(OH)R

* Hc sinh cn lu :
+ Hp cht c magie RMgX rt d phn ng vi cc hp cht c hidro linh ng (H2O, NH3,
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
L
L R
RR
R
N
tb
O
2. Phng php anky ha ion axetilua:
NaNH 2 / NH 3long
R C CH
R C C Na+

3. Cc phng php ankyl v axyl ha hp cht thm:

a) Cc phn ng ankyl ha:

tb
R' X

O-

R C C R

+ dn xut halogen/ xt: axit Lewis (AlCl3 > FeCl3 > BF3 > ZnCl2)
+ anken/ xt: HCl/AlCl3 hoc axit protonic (HF > H2SO4 > H3PO4)
+ ancol/ xt: axit protonic hoc Al2O3.
b) Cc phn ng axyl ha:
R

+ dn xut ca axit cacboxylic (RCOX > (RCO)2O > RCOOR)/ xt: AlCl3

Mt s phn ng formyl ha (thng dng gn nhm CHO vo phenol, ete thm hoc nhn
thm giu electron)
CO + HCl

AlCl 3

HCN + HCl/ AlCl 3

H2 O

HCO-N(R)2
POCl 3 hoac COCl 2

HO

* Hc sinh cn lu :

CHCl 3
NaOH

CHO

(Phn ng Gatterman Koch)

R

CHO

(Phn ng Gatterman)
R

CHO

(Phn ng Vilsmeier)
HO
OHC

(Phn ng Reimer Tiemann)

1

+ C ch ca cc phn ng ankyl v axyl ha nhn thm l c ch SE2(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 CH2 Y hoc X CH(R) Y; vi X, Y l COR, -COOR, -CN,
-NO2
Do X, Y l cc nhm ht electron mnh nguyn t H rt linh ng dng baz tch H+,
to thnh cacbanion.
X
H2C

C2H5ONa
- C2H5OH

+-

Na CH

RBr

HC

1) C2H5ONa

2) RBr

R2

1) C2H5ONa

R(R')

2) R'Br
RCOCl

RCO HC

X
Y
C

X
Y

X
Y

* 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 linh ng, c th d dng b tch H+ bi
-

X
CH

chnh cacbanion

Y
RCO HC

+ CH

RCO

X
+ H 2C

Y
Y
Y
Y
c phn ng cnh tranh:
ngn phn ng ph ni trn, ngi ta dng baz mnh (mnh hn cacbanion) vi lng d.
b) Cht phn ng c dng R CH2 X hoc R2 CH X; vi X l COR, - COOR, - CN, - NO2
Cc phn ng c tin hnh tng t, nhng phi s dng xc tc l baz rt mnh (NaNH2;
C2H5ONa) do nguyn t H 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:
H
C C
H O

H
C C
H O

+
H hoac OH

H
H
C C C C
H OH H O

+
H hoac OH

H
H
C C C C
H
O

* Hc sinh cn lu :
+ C ch ca giai on cng andol: AN
+ Giai on croton ha c th xy ra theo c ch E1 hoc E1cb (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:
X
H 2C

- BH

X
CH

C O
C HC
O

BH
-B

X
C HC
OH

X
- H 2O

* 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.
2

3COONakhan
CH CH
C6H5 CH=O + (CH3CO)2O
C6H5 CH= CH COOH
3COOH
c) Phn ng cng Micheal - cng cc hp cht c nhm metylen hoc metyn linh ng vo hp cht
cacbonyl-,-khng no:

X
H2 C

- BH

X
CH

H2C CH CH O H2 C

CH CH O

BH

CH X

-B

H2C CH2 CH O
CH X
Y

* Hc sinh cn lu :
+ Xc tc baz c th l C2H5ONa (nhit phng); piperidin (nhit cao hn).
+ C th thay th hp cht cacbonyl-,-khng no bng cc hp cht nitro (NO2) hoc nitril (CN)-,khng no.
d) Phn ng ngng t Claisen ngng t este vi cc hp cht c nhm metylen linh ng:
+ Phn ng ngng t gia cc este vi nhau:
CH3COOC2H5 + CH3COOC2H5 C2 H5ONa CH3COCH2COOC2H5 + C2H5OH
C ch phn ng:
O

CH3
H

CH2

OC2H5

O O
CH3

C2H5O
-C2H5OH

CH2 C

C
OC2H5

OC2H5

OC2H5

- C2H5O
CH2COOC2H5

CH3

CH2

COOC2H5

+ Phn ng ngng t este vi hp cht nitril:

CH3COOC2H5 + RCH2CN C2 H5ONa CH3COCH2(R)CN + C2H5OH
+ Phn ng ngng t este vi anehit hoc xeton:
CH3COOC2H5 + CH3COCH3 C2 H5ONa CH3COCH2COCH3 + C2H5OH
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
CaO
2. Phng php vi ti xt:
RCOONa + NaOH t o
RH + Na2CO3
4
3. Phn ng Hunzdicker:
RCOOAg + Br
RBr + CO2 + AgBr
2
to
4. Phn ng halofom:RCOCH3 + 3X2 + 4NaOH
RCOONa + CHX3 + 3NaX + 3H2O

CCl

5. Phn ng thoi phn Hoffman: R CO NH

2
6. Cc phn ng oxi ha lm gy mch Cacbon:
a) Cc phn ng lm gy lin kt lin kt i C=C:
o
+ KMnO4 ,t
CH3COOH + CH3COCH3
CH3CH= C(CH3)2
O O
CH3
O3
+H
C
C
HC

3
O

Br2 , NaOH ,t o
CO2

RNH2

CH3COOH + CH3COCH3

CH3

CH3CH=O + CH3COCH3

b) Cc phn ng lm gy lin kt C C vic-iol:

C C
OH OH

HIO 4 hoac Pb(OOCCH 3)

C + C
O
O

c) Phn ng oxi ha ankyl, ankenyl hoc dn xut ca benzen:

R

KMnO 4 hoac K2Cr 2O 7

+
H

COOH

* Hc sinh cn lu :
+ Nu v tr ca mch bn khng cn H th phn ng oxi ha hu nh khng xy ra.
+ Nu dng Na2Cr2O7 (khng c H+) s to thnh xeton m khng b ct mch
3

CH2 R

Na2Cr2O 7
o
250 C, p

C
O

+ 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)
C R2
OH

CH R2

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
* Hc sinh cn lu :

ienophin

+ 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

R
+

X
R

R
+
X
R

+
X

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: Pb4+, SeO2
C C CH2

C C CH
HO

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 Tc nhn oxi ha: CuO, K2Cr2O7/H+, CrO3/H+

+ Ancol bc II

[O ] xeton
4

(Qu trnh oxi ha ancol bc I thnh anehit cn khng ch cn thn khng chuyn thnh
axit).
+ vic-iol HIO4 cacbonyl.
e) Cc phn ng oxi ha anehit, xeton:
+ Anhit
[O ] axit cacboxylic
Tc nhn oxi ha: O2/xt, [Ag(NH3)2]+, KMnO4/H+, K2Cr2O7/H+
+ Xeton
[O ] b ct mch thnh axit cacboxylic v xeton
Tc nhn oxi ha: KMnO4/H+, HNO3
2. Cc phn ng kh:
a) Phng php hidro ha xc tc:
Tc nhn kh:
+ H2/ Ni, Pt, Pd:
C C

RCOCl

RCH=O

R-CO-R

R-COO-R

RX

RNO2

R-CN

R-CO-NHR
+ H2/ Pd/ BaSO4, BaCO3 (xc tc Lindlar):
C C

C C

C C

RCH=O
RCH2OH
R-CH(OH)-R
RCH2OH + ROH
RH
RNH2
R-CH2NH2
RCH2NHR
kh la chn lin kt ba v lin kt i
C C

+ H2/ [(C6H5)3P]3RhCl: kh la chn lin kt i C=C ch cha 1 hoc 2 nhm th.

* 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 LiAlH4, NaBH4
RCOCl

RCH2OH
RCH=O

RCH2OH
R-CO-R

R-CH(OH)-R
RCOOH

RCH2OH
R-COO-R

RCH2OH + ROH
Epoxit

1,2-iol
Khng kh c bng NaBH4
RX

RH
RNO2

RNH2
R-CN

R-CH2NH2
R-CO-NHR
RCH2NHR
* Hc sinh cn lu :
phn ng kh xy ra theo c ch cng AN.
c) Cc phng php kh bng kim loi ha tan:
Tc nhn kh:
C C
C C
+ Na/NH3 lng:
(lp th: cng trans)
+ Na/ C2H5OH:
RCOOH

RCH2OH
R-COO-R

RCH2OH + ROH
+ Zn (Hg)/ HCl:
R-CO-R

R-CH2-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:
5

a) Chuyn thnh nhm ete:

C O

C OH

...

HI

C OH

b) Chuyn thnh nhm este (nhm este tng i bn trong mi trng axit):
... NaOH
C OCO R
C OH
C OH
c) Chuyn thnh nhm axetal hoc xetal (bo v cc iol):
C OH
C OH

R
+

O C

C O
C O

...

C OH
C OH

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:
RCOCl hoac (RCO)2O

Ph-CH 2-OCOCl

NH

N CO R
N OCO-CH2-Ph

Ph3-CCl

OH

...

H 2/Pd

...

N C-Ph3

...

NH

CH 3COOH khan

B. MT S BI LUYN TP:
Bi 1: Cho s chuyn ha:
OH
(H3C)2C=CH2
H2SO4

H3C

H2 / Ni
(p sut)

CrO3

1) CH3MgBr
2) H2O

OH
H+, t0
H2O

1) O3
2) H2O/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 H2SO4 60%, un nng ti 800C 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 C10H20. 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 H2SO4 ta thu c hp cht:

Hy gii thch qu trnh hnh thnh sn phm trn.

Bi 5:
T isopren hy vit cc phng trnh phn ng iu ch trans - 2 - metylxiclohexanol.
6

Bi 6: Vit cc phng trnh phn ng( dng cu to) to thnh A, B, C, D, M, N theo s sau:
0
a) BrCH2CH2CH2CH=O
A
CH3OH,HCl khan B
dd NaOH, t
b) BrCH2 CH2CH2COOH

1) ddNaOH ,t 0
2) ddHCl

c) HOCH2(CHOH)4CH=O
Bi 7: Cho s chuyn ha:

H ,t 0

Br2 ,H 2 O

H ,t 0

OH

D
N
COOC2H5
(COOC2H5)2

PBr3

KCN

H+

C2H5OH

C2H5ONa

H+

HCOOC 2H5

(D)

OCH3

OCH3

(C2H5O)2CO

E
F
G

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 2 C, hy tng hp:
O

CH

CH2 CH2 NH CH3

a)

CH CH3

C2 H5 O

OH NHCH3

b)

NH

C CH3

c)

Cl
C4H9 NH

SO 2NH2

H2N

d)

COO CH2CH2N(CH3)2

e)
HO

CH

HO

CH2 NH2

HO

CH2 CH2 NH2

f)
g)
Bi 11: T benzen v cc cht 3 C, tng hp:

h)

HO

CH3

OH NH2

OH
HO

CH

CH
HO

O
H3C

HO

CH3

OH

C(CH3)2

a)
b)
c)
Bi 12: T CH3CH2CH2CH2OH v cc cht v c, tng hp
O

O
H3C

CH3
CONH2

Bi 13:
H3CO

T H3CO

OH

H3C
H3C

H3CO
COOH

v cc cht v c, iu ch
H3C N

CH3
CH3

H3CO

Bi 14: T H2N-CH3 v CH2=CH-COOC2H5, tng hp

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 A2 l ng
phn ca nhau.

A1

LiAlH4

A1 HCl

A3

H3PO4

A5, A6 (A5 bn hn)

A4(h p cht no)

Bit rng A2 khi b oxi ho to thnh axit oxalic. A1 l lacton.

Xc nh cu to ca A1, ...,A6 v vit cc phng trnh phn ng.
Bi 16: C mt s dn xut gc CH3 ca axit axetic biu hin hot tnh tng trng cy trng.
CH2COOH

OCH2COOH

OCH2COOH

OCH2COOH

Cl

Cl

Cl
(A)

(B)

Cl

Cl

(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 0C. 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 :
NaOH
1. ClCH2COOH
D
X
metanol
2. H+
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:
Cl

Cl

Cl

Cl

Gii thch s to thnh ioxin.

C. BI GII:
Bi 1:
a)
(A)

(B)

OH

(C)

(D)
O

OH

(E)
CH3

CH3
O
O

H3C

CH3
CH3

H3C

CH3
CH3

H3C

CH3
CH3

H3C

CH3
CH3

H3C

CH3
CH3

b)
H

OH
+

OH

-H

OH

Bi 2:
CH3

C
CH3

CH2 + H

CH3

CH3

(1)

CH3


CH3 + CH3
+

CH3

CH2

CH3

Zaixep

CH3

CH

CH3

CH3

CH3
CH

CH3

H2/Ni

CH3

CH2

CH3

CH2

CH3
(B) (<20%)

CH CH3
CH3

CH3

CH3

(A)

CH2 C

CH3

CH3

CH3 (2)

CH3
CH3
CH3 (A) (>80%)

-H

CH3

CH3
CH3

CH3

CH3

CH2

CH3

CH3
C

CH3

CH2

CH3

CH3

CH3

CH3

Isooctan(C)
2,2,4 - trimetylpentan
(Qui c c chs 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 :
CH3
CH3
CH3

CH2

CH3 + CH3

CH3

CH3

CH3

CH3

CH

CH2

CH3

CH3

CH3

(C)

CH3
H3C

CH CH3
CH3

+ CH3 C

CH3 sinh ra li lp li (2). C nh vy.

CH3

Bi 3: * Sn phm to thnh khi ime ha trimetyletilen:

CH3

CH3

CH

H+

CH3

CH3

CH3

CH3

CH2 CH3

CH3

CH2 CH3 + CH3

CH

CH3

CH3

CH2

CH

CH3

CH3 CH3 CH3

CH3

CH3

CH3
CH3

CH3
CH3

CH2

CH

CH3

CH3 CH3 CH3

CH2

CH3

CH3 CH3 CH3

-H+

CH3
CH3

CH2

CH

CH2

CH3 CH3 CH3

* Ozon phn hn hp trn thu c:

9

CH3
CH3
CH3

CH2

CH3
C

CH3
CH2

CH3

ozon ph
n
CH2

CH2

CH3 CH3
CH3

CH

CH3

CH3 CH3 CH3

CH3

CH2

CH

CH3 CH3 CH3

CH3 CH3 CH3

O C

CH3 v HCHO

CH3
* S to thnh mt lng ng k butanon - 2 l do c s ng phn ha trimetyletilen, to thnh
sn phm ph:
H+
CH3 C CH CH3
CH3 C CH2 CH3 - + CH2 C CH2 CH3
H
CH3 CH3
CH3
CH
3

CH3 C

CH2 CH3 + CH2 C

CH3 CH2

CH2 CH3

CH2 C CH2 CH3

CH3

H+

CH3 CH2 C

CH3

CH

CH3

CH2 CH3

CH3
CH3

CH3

CH2

CH3

CH3

Khi :
CH3 CH2 C

CH2

CH3

CH3
CH2 C

CH2 C

CH3

CH3

CH3
CH3

CH

CH3
CH3
CH2 CH3

CH2 CH3 ozon

ph
n

CH3CH2CCHO
CH3 CH2 C
CH3

O+

CH3
v HCHO

CH3

Bi 4:

10

CH = CH2
CH = CH2

CH3
C
CH2

CH CH3

HC

Bi 5:

CH2

H3C

+ H2B

t0,p

H3C

CH2

CH2

CH2

CH3

CH3

CH3

BH2
CH3

H2O2/OH

- H3BO3

Hiu sut 75%

OH

Bi 6:
a)
Br-(CH2)3-CH=O

NaOH

HO-(CH2)3-CH=O

t0

H
OH

CH3OH

HCl khan

(A)

(B)

b)
Br-(CH2)3-COOH

NaOH

HO-(CH2)3-COONa

ddHCl

OCH3

H+
HO-(CH2)3-COOH

O
O

(C)

(D)

c)
CH2
OH

CH
OH 4

CH =O

HOBr

CH2

CH

OH

OH 4

COOH
+

(M)

HO-CH2-CH
OH

(N)

Bi 7:
a)

11

(A)

B r

OMe

Br

OMe

(B)

(C)

Br

(E)

CN

COOH

O
C2H5O2C

C
C

OC2H5

O
OMe

OMe

OMe
OMe

(F)

(G)
O
C2H5O2C

O
C2H5O2C

OC2H5

OMe

OMe

b) Gii thch s hnh thnh ca:

OC2H5

COOC2H5

COOC2H5

HC

H5C2OOC

H 5 C 2O C O
H 5 C 2O C O

C 2H5ONa

OCH3
E: OCH3
t, gii thch c s hnh thnh F v G.
Bi 8:
450Cl02C CH2 = CH CH2Cl
a) CH2 = CH CH3

ete
CH3 CH(Br) CH2 CH2 CH(Br) CH3

Mg

1) CO2
2) H 3O

C O
COOC2H5

- C 2H 5O

COOC2H5

OCH3

OCH3

Na ,t 0

H5C2OOC

Tng

CH2 = CH CH2 CH2 CH = CH

2

HBr

CH3 CH(MgBr) CH2 CH2 CH(MgBr) CH3

HOOC CH(CH3) CH2 CH2 CH(CH3) COOH

2
450Cl02C CH2 = CH CH2Cl Na ,t 0 CH2 = CH CH2 CH2 CH = CH2
Br
b) CH2 = CH CH3
1:1
CH2Br CH(Br) CH2 CH2 CH = CH2
CH2Br CH(Br) CH2 CH2 CH2 CH3
H 2 / Pd
1) KOH / e tan ol
CH
3 MgCl

HC C CH2 CH2 CH2 CH3

ClMgC C CH2 CH2 CH2 CH3
2) KNH 2

1) CO2
2) H 3O

HOOC - C C CH2 CH2 CH2 CH3

Bi 9:
OH

Br

HBr

MgBr

Mg/ ete khan

1) CO 2
2) H3O

NaOH, t

COOH
OH

CuO, t

COOH

COOH

Cl 2/ P
o
t

Cl

COOH
O

Bi 10:
a)

12

CH 2=CH 2
+
H

Pd, t

C2 H5

CH 3NH 2

CH CH2

HBr, peoxit

CH2CH2Br

CH2CH2NHCH3

b)
CO, HCl

CHO

AlCl3

CH 3NH 2

CH CH CH3
HO

OH
CH C2H5

1) C 2H5MgBr
+
2) H 3O

KOH/etanol

HOCl

CH = CH - CH3

CH CH CH3

Cl

HO

NHCH3

c)
HNO 3
H 2SO 4d
Fe, HCl

Fe, HCl

NO2

NHCOCH3

H2N
HNO 3
H 2SO 4 d

NH2

NaNO 2+HCl

NHCOCH3

NO 2

Fe, HCl

Cl
PCl5

NH3HSO4

ClO 2S

C 2H 5Cl

NHCOCH3

HO

to

Cl2
AlCl3

NO 2

CH3COCl

NH2

HNO 3

C 2H 5 O
H 2SO 4d

NHCOCH3

Cl
+

NH3 HSO 4

H2NO 2S

Cl

d)

+
NH3 HSO4

HO 3S

Cl

NH3

NHCOCH3

O2N

H 2SO 4

NaHCO 3

NH2

H2NO 2S

Cl

Cl

e)

(CH3)2 - N - H +

CH 3Cl

CH3

AlCl3

NH2

HOOC

(CH3) 2-N-CH2-CH2-OH

(CH 3)2-N-CH 2-CH 2-OH

HNO 3
H 2SO 4d

C 4H 9Cl

NO2

H3 C

NHC4H9

HOOC

KMnO4, t

PCl5

Fe, HCl

NO2

HOOC

NHC4H9

ClOC

COO-CH2-CH2-N(CH3) 2

H9C4HN

f)
o
1) NaOH,t ,p
+
2) H

Cl2

Cl

AlCl 3

OH

HNO 3

OH

Fe, HCl

NH2

NO 2
NaNO 2 + HCl
o
t

OH

CO + HCl
AlCl3

OH
HO
HO

HO
HO

CHO

HCN

HO
HO

OH

CH CN

H 2/ Pd

HO

CH CH2 NH2
HO

g)

13

HO

KOH/ etanol

CH CH2 NH2

HO

HO

HO

CH CH

NH2

H 2 / Pd

HO

HO

CH2 CH2 NH2

HO

h)
HO

CH 3CH 2NO 2
OH

CHO

HO

HO

CH

HO
HO

CH

CH CH3

OH

NH2

HO

NO 2

HO

Fe, HCl

H 2O/H

C CH3

CH
HO

HO

CH CH3
NO 2

Bi 11:
a)
CH2=CH-CH 2Cl

CH2-CH=CH2

AlCl3

HBr/ peoxit

1) (CH 3)2CO

CH2-CH2-CH2-MgBr

2) H 3O

CH2-CH2-CH2-Br

CH2

CH3
C OH
3 CH3

Mg/ ete

H 2SO 4

b)
CH 3Cl

Cl2, as

CH3

AlCl3

CH2Cl

Mg/ ete

CH2MgCl

1) O
2) H 3O

CH2-CH2-CH2-OH
COCl2

Cl 2

CHCl-CH2-CH2-OH

NaOH

CH(OH)-CH2-CH2-OH

O
O
O

c)
o
1) NaOH,t ,p
Cl
+
2) H

Cl2
AlCl3

H3C C CH3

OH

OH

CH3

H3C C CH3

HO
CH3

OH
OH

CH3
+
C
CH3

HO

OH

CH3
C
CH3

HO

+
H
- H 2O

OH

Bi 12:
OH
NH 3, t

CuO, t

Br 2, H 2O

CHO

COOH

Ag2O

CONH2

CONH2

Bi 13:

14

CH3

CH3

OH

CH3

CH3

CH3

LiAlH 4

CH3
CH3

H 2SO 4,t

CH3

CH3

COOH

CH3

OH

Bi 14:
O

NH2

O
OC2H5
CH3

CH3

NH CH2 CH2 COOC2H5

OC2H5
CH3

CH2 CH2 COOC2H5

CH2 CH2 COOC2H5

C 2H 5ONa

CH3 N

+ o
H ,t

CH3 N

COOC2H5

(S dng phn ng cng Micheal v ngng t Claisen)

Bi 15:
CH3

CH

CHO +CH2

COOH
COOH

CH3

CH3
CH
CH3

CH

CH

t0
COOH -CO2

OH

CH
CH3

CH CH2

COOH

OH (A)

CH

CH

CH3

H+,t0

COOH

CH CH
(A2)

CH3
CH3

COOH
-H2O

CH2

OH

CH

CH3

CH

CH3

CH3

OH

CH

COOH

CH2 COOH

CH3

CH3
CH

CH

CH

COOH

[O]

CH3

CH3

CH

COOH + HOOC

COOH

CH3
CH3

CH3
C

CH

CH2 COOH

H+

CH3

CH3

CH2

CH3
CH3

COOH

CH
CH3

COOH

CH

CH3

Piriin

C
O

CH2

CH2
C

LiAlH4
O

CH2
C

O (A1)

CH3
C
CH3

OH

CH2

CH2 CH2
(A3)

OH

15

CH3
CH3

CH3

CH2

CH2

H+ CH3
(HCl)
O

+ 2
CH

CH2
C

Cl
OH

O -

CH3

O
C

CH2

CH2 C

CH3

Cl

CH

CH2 CH2 + H2O

OH

(A4)

CH3
C

CH3
C
CH3

OH

CH2

CH2 CH2
(A3)

H3PO4

OH

CH3
CH3

(A 6)
H2C

CH2

CH2

CH3

2.

CH2COOH

t0, xt
SE

+ HCl
OH

OSO3H
H2O

ClCH2COOH

-H2SO4

Kim, SN2
-HCl

H2SO4

3.

+ H2O

(A 5)

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]

+ ClCH2COOH

OH

OCH2COONa

OCH2COOH

H+
-Na+
OH

OH
4.

ONa
Cl

Cl2/CCl4
-HCl

Cl

NaOH
-H2O

Cl
CH3COOH

Cl2, P
-HCl

CH2COOH
Cl

Cl
NaOH
-H2O

CH2COONa
Cl

16

ONa

OCH2COONa
Cl

Cl
+ CH2COONa

Cl

H+

-NaCl

Cl

Cl

OCH2COOH

Cl

Cl

Cl

Cl
Cl

5.

OCH2COONa

ONa
ClCH2COOH

NaOH
SN2Ar Cl

Cl

Cl

Cl (X)
Cl

SN2

Cl
Cl

Cl
OCH2COOH

H+
Cl
Cl
S to ioxin:

Cl

Cl

NaO

Cl

Cl

Cl

Cl

Cl

+
Cl

ONa

Cl
+ 2NaCl

Cl

17

18