Tng hp hu c

TRNG THPT CHUYN V NGUYN GIP

MT S PHN NG TNG HP
ANCOL PHENOL ANDEHIT
XETON AXIT CACBOXYLIC N
CHC BNG PHNG PHP TNG,
GIM MCH CACBON

OH

OH
OH

OH
OH

ng B Hng Trng THPT Chuyn V Nguyn Gip

Tng hp hu c

I. TNG HP ANCOL - PHENOL.

1. Tng hp ancol.
a. Tng hp t dn xut c Mg:
Victor Grignard pht hin v m rng ng dng hp cht c magie trong
tng hp hu c. Nh thnh cng ng c nhn gii Nobel nm 1912.
Tc nhn Grignard dng nhiu nht trong tng hp to thnh lin kt
C-C do s cng hp vo lin kt i, c bit l lin kt i cacbonyl. Trong
mi trng hp, Mg di chuyn t C ti nguyn t m in hn. Phn ng xy
ra theo c ch cng nucleofin.
+

MgX

MgX

Hiu sut ca sn phm cng thng cao vi s ln hp cht cacbonyl.

S thy phn sn phm cng thu c ancol tng ng. Vi andehit fomic th
ta thu c ancol bc 1 c s nguyn t C trong mch hn tc nhn Grignard
mt nguyn t C, vi ng ng ca andehit fomic ta thu c ancol bc 2, vi
xeton, este, clorua axit th cho ancol bc 3.
Vi xeton:
R''
R

MgX

R'

R''

OMgX

R'

MgX

R'

OR''

O
R

MgX

R'

H3O+
OMgX

R'

OH

R'

Vi clorua axit:
R

MgX

R'

Cl

O
R
R

MgX

C
R'

OMgX

R'
R

H3O+
R

OH

R'

Th d:

ng B Hng Trng THPT Chuyn V Nguyn Gip

C
R'

Vi este:
R

R''

H3O+

OH

Tng hp hu c
CH2O

H3C

CH3CH2OMgI

C6H5CHO

MgI

H2O,H+

CH3CH2OH

H2O,H+

C6H5 CH OMgI

C6H5 CH OH
CH3

CH3
C2H5

C6H5COC2H5

H3C C

C2H5

H2O,H+

OMgI

H3C C

C6H5

OH

C6H5

C th thay tc nhn R-MgX bng R-Li, phn ng xy ra theo c ch

AN.
+

Li

R''

R''

R'

R''

Li

R'

OH

R'

Th d:
O
CH3CH2CH2CH2Li

H2O

CH3CH2CH2CH2

(74%) H

H
O

2CH3Li

OCH3

OH

CH3

H2O

THF

(70%)

OH

CH3

Nu dng axetylua hay ankinyl liti hoc ankinyl magie tc dng vi

andehit hoc xeton th thu c ancol cha no:
CH3
HC

Li + H3C C CH3

HC

C C CH3

H2O,H+

HC

C C CH3

OLi

OH

CH3
H3 C C

CH3

MgBr + H3C C H

H3C

C C OMgBr

H2O,H+

CH3
H3C

C C OH
H

Nu cho dn xut Grignard tc dng vi etylen oxit th ta thu c sn

phm l ancol bc 1 tng thm 2 nguyn t C; vi propylen oxit th ta thu c
sn phm l ancol bc 1 tng thm 3 nguyn t C, phn ng din ra theo c ch
SN2:
R

MgX + H2C

CH2

CH2CH2OMgX

H2O,H+

CH2CH2OH

O
R

MgX

H3O+

CH2CH2CH2OMgX

ng B Hng Trng THPT Chuyn V Nguyn Gip

CH2CH2CH2OH

Tng hp hu c

Ch :
Nu dng tc nhn l hp cht c ng liti hoc c cadimi tc dng vi
clorua axit th sn phm ch dng li s to thnh andehit do tnh chn lc
cao ca cc tc nhn ny.
+

R2CuLi

R'

Cl

CdCl2

MgCl +

CdCl +

R'

Cl

CdCl +

MgCl2

R'
MgCl2

R'

b. Hidrobo ha cacbonyl ha oxi ha anken:

Phng php ny i t sn phm triankyl bo ca anken v boran, cho
phn ng vi CO sau cho phn ng vi H 2O2 trong mi trng kim thu
c triankyl cacbinol, phn ng ny xy ra nhanh v dng iu ch
triankyl cacbinol i xng.
C

BH3

H C

H2O2

CO

H C

OH-

COH

Th d:
CH3CH

BH3

CH2

BH3

CO

1000C

BH3

B
3

H2O2

CO

(CH3CH2CH2)3B

H2O2

COH

OH-

CO
1000C

(CH3CH2CH2)3COH

OH-

1000C

(85%)

H2O2

COH

OH-

2. Tng hp phenol.
Phenol l sn phm ch yu thu c t qu trnh chng ct than .
Trong cng nghip, phenol c tng hp cng vi axeton t sn phm du m
cumen:
C6H5CH(CH3)2

C6H5C(CH3)2

O2

C6H5C(CH3)2
O

C6H5CH(CH3)2

C6H5C(CH3)2
O

C6H5C(CH3)2

OH

ng B Hng Trng THPT Chuyn V Nguyn Gip

Tng hp hu c
CH3
C

CH3

CH3

H+

OH

O
CH3

nhanh

CH3

CH3

nhanh

CH3

-H2O

OH2

CH3

O
CH3

H2O

CH3

OH2
CH3

-H+

CH3

CH3

-H+

OH

CH3

OH

phn ng xy ra qua c ch gc, trong qu trnh chuyn v gi l chuyn v

hidroperoxit.
II. TNG HP ANDEHIT - XETON.
1. Phn ng ca hp cht Grignard:
* Phn ng ca hp cht Grignard vi hp cht c nhm cacbonyl:
- S ha hp ca tc nhn Grignard vi clorua axit thng x ra theo hai
giai on:
+

OMgX
MgX

Cl

Cl

Sn phm trung gian l cht km bn n phn hy tc thi thnh xeton

v MgXCl, sau xeton to thnh tip tc phn ng nhanh vi tc nhn
Grignard cho mui ca ancol bc 3, s thy phn mui ny cho ancol bc 3
tng ng.
OMgX
R

+ R MgX

OH
H2O, H+

Vi l do trn nn trong thc t ngi ta khng dng phn ng cng ca

tc nhn Grignard vi clorua axit khng dng tng hp xeton.
Nu dng tc nhn l hp cht c ng liti hoc c cadimi tc dng vi
clorua axit th sn phm ch dng li s to thnh andehit do tnh chn lc
cao ca cc tc nhn ny.
+

R2CuLi

R'

Cl

O
R

MgCl +

CdCl +

R'

CdCl2

C
O

Cl

MgCl2

R'
CdCl + MgCl2
C

R'

- Vi amit c hai nhm th theo t l 1:1 to ra xeton:

ng B Hng Trng THPT Chuyn V Nguyn Gip

Tng hp hu c
OMgX
R

MgX

R'

N(CH3)2

O
H2O, HCl

N(CH3)2

R'
O

(CH3)2NH2Cl

R'

- Vi nitrin:
MgX +

R'

H3O+

MgX

R'

R'

Phn ng ch dng li xeton.

- Phn ng vi cc andehit, xeton ,-khng no:
+
C

tng t nh ankadien-1,3 c phn ng cng 1,2 v

cng 1,4.
S cnh tranh gia phn ng cng 1,2 v cng 1,4 chu s chi phi rt
mnh ca hiu ng khng gian. Nu cacbon ca andehit ,-khng no c t
nht mt nhm th th c phn ng cng 1,2 tc l phn ng cng vo nhm
cacbonyl (C=O).
Th d:
OH

O
H3C

CH CH C

C2H5

MgX

H3C

CH CH CH C2H5

i vi penten-3-on-2 th t l sn phm cng 1,4 v 1,2 l 3:1.

OH
H3C

O
H3C

+ C2H5

CH CH C

MgBr

CH CH C
25%

CH3

CH3
H3C

C2H5

CH CH2
C2H5

CH3

75%

Nu c thm mt nhm CH3 cacbon , tc trong trng hp 4Metylpenten-3-on-2 th hon ton c sn phm cng 1,2 tc ch xy ra phn
ng ca hp cht Grignard vi xeton:
OH

O
H3C

C
CH3

CH C

+ C2H5

MgBr

H3C

CH3

ng B Hng Trng THPT Chuyn V Nguyn Gip

C
CH3

CH C
CH3

C2H5

Tng hp hu c

2. Phn ng Reimer-Tiemann:
iu ch andehit thm c nhm OH nh v tr octo so vi nhm
CHO. Cho phenol tc dng vi clorofom trong mi trng kim, un nng:
OH

OH
CHO
NaOH, H2O

+ CHCl3

60-700C

(phn ng cng nghip sn xut Salixylandehit).

3. Phn ng Gattermann:
L phn ng fomyl ha hp cht thm c kh nng phn ng cao trong
phn ng SE nh phenol, este ca phenol v hidrocacbon khc. Tc nhn c
s dng l hidroxianua, hidroclorua v xc tc l ZnCl 2 hay AlCl3 khan hoc
ci tin bng cch dng Zn(CN)2 v hidroclorua. Thy phn cc sn phm s
to ra cc andehit.
CHO
OH

OH
+ HCN + HCl

1) ZnCl2, ete

+ NH4Cl

2) H2O

4. Phn ng Friedel-Crapts:
Axyl ha vng thm dng clorua axit c xc tc axit lewis, hay dng
nht l AlCl3 khan.
O
C
+

Cl

AlCl3

+ HCl

Phn ng ny thng tin hnh trong dung mi CS 2 hoc nitrobenzen,

thng phi dng xc tc nhiu hn do xeton to phc vi xc tc. Phn ng
dng li giai on th mt ln.
5. Phn ng Gattermann-Koch:
L phn ng iu ch andehit thm bng cch cho oxit cacbon CO tc
dng vi hidrocacbon thm khi c mt Hidroclorua v Nhm clorua khan.
Phn ng xy ra p sut thng ch cn dng thm CuCl, nu p sut cao
th khng cn CuCl.
Th d:
H3C
CH
H3C

+ CO

AlCl3, HCl
35at, 25-300C

H3C
CH
H3C

ng B Hng Trng THPT Chuyn V Nguyn Gip

CHO
60%

Tng hp hu c

+ CO

AlCl3, HCl

CHO

Cu2Cl2, 35-400C
73%

6.Phn ng ankyl ha Haller-Bauer:

Xeton c cha hidro tc dng vi alkyl halogenua khi c mt ca bazo
mnh nh NaNH2, KNH2 to ra xeton c nhm ankyl cacbon . Phn ng ny
iu ch cc ng ng ca xeton.
O
R

CH3

NaNH2

R'-X

(-NH3)

CH2

R'

CH2

Phn ng ny c s cnh tranh ca phn ng O-ankyl ha do s chuyn

ha gia hai dng cng hng ca anion trung gian trn:
O
R

CH2

CH2

CH2

Nu dn xut ankylhalogenua c hot ng ha hc cao th sn phm

O-ankyl ha l sn phm chnh, ngc li nu dn xut ankylhalogenua c
hot ng ha hc yu th sn phm C-ankyl ha l sn phm ch yu.
O
R

CH3

NaNH2

(-NH3)

OR'
R'-X

CH2

CH2

Phn ng ankyl ha theo Haller-Bauer t c p dng tng hp cc

dn xut ca cc xeton n gin, tr khi cn tng hp xeton c nhiu nhm th
l cc gc ankyl m cc dn xut loi ny iu ch bng cc phng php khc
rt kh khn.
Th d:
O
(H3C)3C

O
CH3

+ 3CH3I + 3NaNH2

(H3C)3C

C(CH3)3 + 3NaI + 3NH3

7. Phn ng cng Diels-Alder:

Khi tc dng vi butadien, andehit hay xeton cha no ng vai tr ca
mt dienophin:
CHO

CHO
0

100 C

y l phn ng cng vng vi s electron (4n+2).

8. Mt s phn ng gim mch cacbon:
a. Phn ng oxi ha:
Tc nhn thng dng ct t ni i cacbon-cacbon l ozon. Phn
ng ny c thc hin theo hai giai on: u tin, s cng ozon vo ni i
ng B Hng Trng THPT Chuyn V Nguyn Gip

Tng hp hu c

cacbon-cacbon cho hp cht ozonit; sau , s thy phn hp cht ozonit cho
sn phm ct t l hp cht cacbonyl, trong phn ng ny ngi ta thng
dng cht kh l Zn kh sn phm ph l H 2O2 trnh phn ng oxi ha
nhm andehit thnh nhm axit cacboxylic. Phn ng ny c dng xc
nh v tr lin kt i trong phn t anken.
R CH

CH

R'

R1

R3
C

R2

O3

H2O,Zn

O3

H2O,Zn

R CHO

CHO

R3

R1
C

R2

R4

+ R'
C

R4

i vi phn ng ozon ha ngi ta cho ozon i qua dung dch anken

trong dung mi tr nh CCl4 sau lm bay hi dung mi thu c hp cht
ozonit di dng du st. Cht ny khng bn, d n do khng c tinh
ch m ch ha trc tip vi nc c mt ca cht kh ta thu c andehit
hoc xeton.
Th d:
O3, CH2Cl2

Zn

CHO + HCHO

CH3COOH

-78 C

62%

b. Phn ng Decacboxyl ha axit:

Cho hi axit i qua MnO hay ThO 3000C:
2 R

MnO, 3000C

OH

+ CO2 + H2O

O
R

OH

MnO, 3000C

+ HCOOH

+ CO2 + H2O

c th dng mui axit:

(RCOO)2Ca

t0C

+ CaCO3

O
(RCOO)2Ca + (HCOO)2Ca

t0 C

2R

+ 2CaCO3

Decacboxyl ha diaxit to thnh xeton vng:

COOH
COOH

Ba(OH)2

2950C

ng B Hng Trng THPT Chuyn V Nguyn Gip

Tng hp hu c

III. TNG HP AXIT CACBOXYLIC.

1. Phng php cacbonyl ha:
a. Tng hp t hp cht Grignard:
Phn ng ca tc nhn Grignard vi CO2 cho sn phm l mui ca axit
cacboxylic, sau thy phn mui ny thu c axit cacboxylic.
-

MgX

H3O+

O MgX

OH

Tuy nhin, sn phm mui ca axit cacboxylic cha ni i C=O do

tip tc phn ng vi tc nhn Grignard.
+

OMgX
MgX

OMgX

OMgX

Trong thc nghim c th loi b phn ng ny bng cch dung dch

Grignard vo CO2 rn mn (nc kh).
Phng php Grignard ny dng thch hp cho dn xut halogen khng
c kh nng phn ng theo c ch S N2. Phn ng u vit hn vi dn xut
halogen bc 1 hoc bc 2 do nh hng ca hiu ng khng gian.
- Ta c th iu ch axit cacboxylic t hp cht c kim khc nh c liti:
R

H3O+

Li + CO2

COOH

Th d:
COO-Li+

Li

COOH

H3O+

+ CO2

- Mui ca axit cacboxylic cng thu c khi cho oxit cacbon CO phn
ng vi kim hay ancolat di p sut 6atm 120-130 0C, sau thy phn
mui ny thu c axit cacboxylic tng ng:
6atm,
NaOH +

CO

120-1300C

ONa

H3O+

O
ONa +

CO

120-1300C

OH

6atm,
R

ONa

H3O

OH

b. Phn ng Reppe:
Cho kh etylen hay olefin tc dng vi kh CO v H2O khi c xc tc
cacbonyl niken Ni(CO)4:

ng B Hng Trng THPT Chuyn V Nguyn Gip

Tng hp hu c

Ni(CO)4

CO

H2O

COOH

C
O

Th d:
H2C

CH2 +

Ni(CO)4

CO

H2C

CH2

H2O

H3C CH2

COOH

C
O

- C th cho kh etylen hay olefin tc dng vi kh CO trong dung dch

axit sunfuric c:
C

CO

H2SO4

+ H2O

COOH

Th d:
R

CH2 +

CH

CO

+ H2O

H2SO4

CH2 CH2

COOH

2. Phn ng vi cc este ,-khng no:

+
C

Phn ng ny tng t nh ankadien-1,3 c phn ng cng 1,2 v cng

1,4.
Cc este khng no ca axit ,-khng no khi phn ng vi hp cht
Grignard cho sn phm cng 1,4:
+
C

OR'
C

O
R

H3O+

+ R

+
MgX

R
C

OR'
C

OMgX

OH
CH C

S cnh tranh gia phn ng cng 1,2 v cng 1,4 chu s chi phi rt
mnh ca hiu ng khng gian.
3. Tng hp Arndt-Eister:
Clorua axit tc dng vi diazometan, phn hy sn phm bng cch un
nng vi Ag2O to ra xeten, cho xeten tc dng vi nc c axit c s
nguyn t cacbon tng 1 so vi clorua axit ban u:

ng B Hng Trng THPT Chuyn V Nguyn Gip

10

Tng hp hu c

+ 2CH2N2

-(CH3Cl, N2)

Cl
H2O

R CH2

+ Ag2O

CH C

- N2

92% CHN2

80%

OH

4. Tng hp malonic :
RX

CH
2(COOC
2H5)2

C2H5ONa
C2H5OH

R - CH

COOH

R - CH
t

COOC
2H5

H3O

COOC
2H5

R - CH2 - COOH +

COOH

CO
2

Phn ng c dng iu ch cc axit ankyl axetic R CH 2COOH,

diankyl axetic RRCHCOOH hoc cc diaxit kiu HOOC (CH2)n COOH.
5. Phn ng oxi ha ct mch:
a. Phn ng halofom:
Cc -halogenandehit hay xeton c tnh axit cao hn andehit v xeton
ban u do hiu ng I ca halogen nn d thu c dn xut trihalogen trong
mi trng kim. Dn xut trihalogen ny d b tn cng bi kim lm phn ct
lin kt C-C to thnh sn phn halofom (clorofom, bromofom, iodofom).
O
H3C

OH-

CBr3

H3C

CBr3

OH
O
H3C

+ CBr3

OH

H3C

+ CHBr3

Phn ng ny ngoi vic iu ch cc axit cacboxylic t andehit cn

nh tnh cc metylxeton, nht l phn ng iodofom.
O
R

1) Br2, OH-,H2O

CH3

2) H+

O
R

OH

Th d:
O
C

1) Br2, OH-,H2O

CH3

2) H+

H3C
C

CH

CH3

H3C

1) Cl2, OH-,H2O
2) H+

O
C

OH

(85%)
O

H3C
C

CH C

H3C

OH

(50%)

So vi ankyl haogenua, cc -halogenandehit v -halogenxeton t ra

tr vi c ch SN1 nhng li linh ng trong phn ng SN2.
b. Oxi ha anken:
ng B Hng Trng THPT Chuyn V Nguyn Gip

11

Tng hp hu c

Cc lin kt i C=C d b oxi ha ct mch bi cc tc nhn oxi ha

mnh to thnh axit cacboxylic:
OH
R

CH

CH R'

1) O3
2) H2O

HO
+

C
O

R'

tc nhn thng dng cho phn ng ny l ozon O3.

Hoc oxi ha anken bng KMnO4 c, nng:
RCH = CHR'

[O]

RCOOH

R'COOH

c. Oxi ha ankylbenzen:
Cc ankylbenzen b oxi ha ct mch bi cc tc nhn oxi ha mnh ti
C khi phn t cn H to thnh axit benzoic. Cc tc nhn oxi ha thng
dng l dung dch KMnO4 v un nng.
R

[O]

COOH

ng B Hng Trng THPT Chuyn V Nguyn Gip

12

Tng hp hu c

TI LIU THAM KHO

[1] PGS.TSKH Phan nh Chu Cc qu trnh c bn tng hp hu c
NXB KH&KT 2005.
[2] Nguyn Minh Tho Tng hp hu c NXB HQG H Ni 2005.
[3] PGS.TS Thi Don Tnh C s Ha hc hu c - Tp 1 NXB KH&KT
2005.
[4] PGS.TS Thi Don Tnh C s l thuyt Ha hu c - Tp 2 NXB
KH&KT 2005.
[5] Nguyn Ngc Sng C s Ha hc hu c Phn 2 NXB HQG TP
HCM 2000.
[6] Nguyn Ngc Sng C s Ha hc hu c Phn 3 NXB HQG TP
HCM 2000.
[7] Mt s chuyn ha hc bi dng hc sinh gii THPT (ti liu dng cho
lp bi dng gio vin THPT chuyn h 2005) - H Ni 2005.
(PGS.TS Trn Thch Vn - Chuyn Mt s phn ng hu c mang tn
ngi H Ni 2005).

ng B Hng Trng THPT Chuyn V Nguyn Gip

13