DN XUT HALOGEN

HALOGEN

1. Gi tn
CH3 CH CH2 I CH3 1-iodo-2-methylpropan
CH2 CH CH2 Cl

CHCl2

Cl C CH2 CH3 1-chloro-1-methyleten

3-chloropropen

Benzaldichlorid Phenyldichloromethan

CH3 CH CH2 CH CH2 CH CH CH2

Cl Cl
I C 2H 5 Br

C6H5

Br

CH2CH2CH3

4-bromo-2-phenyl-6-vinylnonan

3,3-dichlorobicyclo [4.3.0]nonan

3-bromo-4-ethyl5-iodocyclohexen
CH CH3 Cl

1-chloro-1-cyclohexylethan
CH3 CCl3 Cl Cl F H3C CH CCl3 Cl

3-chloro-6-fluoro1-methylnaphtalen

4-methylphenyl trichloromethan

2,2-di-(4,4-dichlorophenyl)-1,1,1-trichloroethan
2

HALOGEN

2. Vit cng thc

a. 2,3-Dibromo-3-ethylheptan
C2H5 CH3 CH C CH2CH2CH2CH3 Br Br

e. Benzylchlorid
CH2Cl

b. cis-2-Bromochloromethylcyclohexan
CH 2Cl Br

f. o-Phenylenchlorid
Cl Cl

c. 1-Bromo-2-iodocyclopentan
Br I

g. 4-Bromo-4-methyl-2-hexen
CH3 CH3 CH CH C CH2 Br CH3

d. Chloral
Cl3C CHO

h. Propylidenchlorid
Cl CH3 CH2 CH Cl
3

HALOGEN

3. Vit phn ng ca 1-bromobutan vi :

CH3

CH2

CH CH2

Mg/Et2O

C4H9MgBr

KOH/alcol

dd KOH

C4H9OH

CH3CH2CH2CH2Br

Na

C 4H 9 C 4H 9

AlCl3 C6H5CH3

C2H5ONa

C 4H 9

OC2H5

CH3

CH CH2CH3 CH3

HC C Na

HC C C4H9

HALOGEN

4. Sp xp theo kh nng th SN2

a. CH3CH2CH2-I > CH3CH2CH2-Br > CH3CH2CH2-Cl

b. CH3

CH CH3 I

>

CH3

CH CH3 Br

>

CH3

CH CH3 Cl

5. Sp xp theo kh nng th SN1

CH3
a. H3C C Cl

>

CH3

CH2

CH Cl CH3

>

CH3CH2CH2CH2

Cl

CH3
CH3 CH3 I >

CH3 > H3C C Cl CH3

5

b. H3C C
CH3

H3C C Br CH3

HALOGEN

6. Gii thch tc dng xc tc ion Iodid

C4H9Cl + I

C 4H 9I

Cl

d hn

OH

C 4H 9OH

7. iu ch t alken
a. 2-Iodo-2-methylpentan

CH3

CH2

CH2

C CH2 CH3 HI
I CH3 CH2 CH2 C CH3 CH3
6

CH3

CH2

CH

C CH3 CH3

HALOGEN

7. iu ch t alken
b. 1-Bromo-3-methylbutan

CH3

CH CH CH2 CH3

HBr
CH3 CH CH2 CH2 Br CH3

c. 1-Chloro-1-methylcyclohexan

CH3 HCl CH2

CH3 Cl

HALOGEN

8. iu ch t allylbromid

(CH3)2CH MgBr

CH2

CH CH2

CH CH3 CH3

4-Methylpenten
Br2 CH2 Br
CH2 CH CH2 Br

CH CH2 Br

Br

1,2,3-tribromopropan
HBr peroxyd CH2 Br CH2 CH2 Br

1,3-dibromopropan
2 HBr Br CH3 C CH3 Br

KOH/alcol

CH2

C CH2

2,2-dibromopropan
8

HALOGEN

10. Cho 3 sn phm ca phn ng chlor ha mch nhnh toluen tc dng vi dd kim :
OH

C 6H5 CH2OH

C6H5

CH2Cl

C6H5

CHCl2

OH

C 6H 5 CHO

C6H5 CCl3

OH

C6H5 CCl2 OH

OH

C6H5 C Cl O

OH

C6H5 C OH O

HALOGEN

11. iu ch cc dn xut halogen : a. Ethanol 2-bromobutan

CH3CH2OH PCl5 CH3CH2Cl Na CH3CH2CH2CH3 Br2 h CH3CH2CH CH3 Br

b. Acetylen 1,2-dibromobutan
HC CH H2 Pd/BaCO3 H 2C CH 2 HCl CH 3CH 2Cl

HC CH

Na

HC C Na

HC C C2H5

H2 Pd/BaCO3

H2C C C2H5 Br2 H 2C C C 2H 5 Br Br

10

HALOGEN

12. Hon thnh chui phn ng :

a. CH3CH2CH2CH2Br
KOH/EtOH
HBr

CH3CH2CH CH2 A

CH3CH2CH CH3 B Br

KOH EtOH CH CH CH3 C

CH3

C C CH3 E
SO3H

KOH EtOH

CH3

CH CH CH3 Br Br D

Br2

CH3

SO3H Br2 Br Br B
H 2O to , P Br C Br

b.

H 2SO4

NaOH o 300 C 200 atm

HO D

11 OH

HALOGEN

12. Cho bit iu kin phn ng

Br C 2H 5 C2H5Cl AlCl3 Br2 Fe Br C 2H 5 Br2 h Br CH CH3 KOH alcol Br CH CH2

12

HALOGEN

14. Hon thnh chui phn ng :

CH3 Cl2 CH2Cl KCN CH2CN 2 H2O CH2COOH

a.

b. CH3 CH CH2 CH3

Br

KOH alcol

CH3

CH CH

CH3

Br2

CH3

CH CH Br Br

CH3

Cl CH3 C CH2 Cl CHI3 I2/NaOH CH3 PCl5

2 KOH alcol

CH3

C CH2 O

CH3

H2O Hg
++

CH3

C C

CH3

13

DN CHT NITRO & SULFONIC

14

NITRO, SULFONIC

1. Toluen acid p-toluensulfonic v vit phn ng :

COOH
[O]

SO3H

CH3
H2SO4

CH3
NaOH

CH3 + Na 2SO3 + 2H2O ONa

SO3H

CH3
KCN

+ KHCO3 CN
15

NITRO, SULFONIC

2. B tc dy phn ng :
Br Br
H2SO4
KO H

Br
KOH 300 C
o

Br

a.

SO3H A

SO 3K B

OK C

16

NITRO, SULFONIC

2. B tc dy phn ng :

SO3H

SO3H
Br2/Fe
KOH toC

OK

b.

H2SO4

Br A B

Br C
KCN
tC
o

OH
H2O/H+

OK

COOH E

CN D
17

NITRO, SULFONIC

2. B tc dy phn ng :
SO3H
Cl2/Fe

SO3H

SO3H
HNO3

H2O/H+

c.

NO2 A

Cl B

NO2

100 C

Cl C

NO2

18

NITRO, SULFONIC

3. Dng tc nhn no :
CH3 COOH
KMnO4 H2SO 4/SO3

COOH
PCl5

COCl

a.

SO3H
Cl Cl
H2SO 4 PCl5

SO2Cl
Cl

Cl

b.

NH3/toC

SO3H

SO2Cl

SO2NH2

CH3

CH3
ClSO 2OH

CH3

c.

CH3OH NaOH
SO2Cl SO2OCH3
19

NITRO, SULFONIC

4. Toluen Ester metyl ca acid p-toluensulfonic :

H2SO4
PCl5

CH3

CH3

SO3H

CH3

SO2Cl
CH3OH OH

CH3
CH3 SO2OCH3

SO2OCH3

OH

OCH3 + CH3

SO3H

CH3

SO2OCH3

NH2

NHCH3 + CH3

SO3H
20

NITRO, SULFONIC

5. Benzen Saccharin :
CH3Cl AlCl3 khan

CH3

HOSO2Cl

CH3 SO2Cl
NH3

COOH SO2NH2
- H2O

KMnO4

CH3 SO2NH2

O C NH S O O
21

NITRO, SULFONIC

6. iu ch t Carbur calci :
CaC2 + 2H2O HC CH
t,P
o

+ Ca(OH)2

Br
Br2/Fe
HNO 3 H2SO4

NO2

HNO 3 H2SO4

Cl2/Fe

Br

NO2

Cl

NO2
22

NITRO, SULFONIC

7. Phn ng kh ha p-nitrotoluen :
CH3 [H]
CH3

CH3

CH3

H+ N O NH OH NH2

ONO 2

CH3 [H]
OH

+ N N

CH3

[H]
Zn/NH4Cl

CH3

N N

CH3

CH3

CH3
NH OH

NH NH

CH3

23

NITRO, SULFONIC

8. Thc hin chuyn ha

CH3
ClSO2OH

CH3
NH3

CH3
NaOCl

CH3

1 ml

SO2Cl (I)

SO2NH2 (II)
H2O

SO2NHCl (III) Cloramin T

NaOCl

CH3

Cl SO2N Cl (IV) 24 Dicloramin T

NITRO, SULFONIC

9. Thc hin chuyn ha vi iu kin khng to ng phn

NHCOCH3 O2N NH2 NO2

H 2SO4

H 2O
NHCOCH 3

NHCOCH3 2 HNO3 H
+

t o, P

O2N

NO2

SO3H

SO3H

25

HP CHT C MAGNESI

26

HP CHT C MAGNESI

1. iu ch hc c magnesi t ethanol v ha cht v c

a. C2H5OH
H2SO4 t
o

CH2

CH2

O3

[H] H CHO

CH3OH

PBr3

CH3Br Mg Et2O

b. C2H5OH
PCl5 C2H5Cl

[O]

CH3MgBr Methylmagnebromid
CH3 C H O
+

CH3
Mg Et2O C2H5MgCl

CH C2H5 OMgCl

H2O/H

CH3

CH C2H5 OH

- MgClOH

PBr3 CH3 CH C2H5 Mg Et2O CH3 CH C2H5 Br

MgBr sec-Butylmagnebromid

27

HP CHT C MAGNESI

2. iu ch t acetylen v ha cht v c
a. Acid acetylen dicarboxylic
HC CH H2O Hg
++

[H] CH3CHO C2H5OH

PBr3

C2H5Br

Mg Et2O

C2H5MgBr
HC CH - C 2H 6

HOOC C C COOH

1) CO2 2) H2O

BrMg

C C MgBr

b. Dimethylcarbinol
HC CH H2 CH2 CH2 O3 H2O/Zn [H] HCHO CH3OH
1) HBr 2) Mg/Et2O

CH3MgBr
CH 3CHO

Pd/BaSO4

CH3

CH CH 3 OH

H 2O/H

CH 3

CH CH 3 OMgBr
28

HP CHT C MAGNESI

3. iu ch t propylen v ha cht v c
a. 2-Methyl-2-pentanol
CH3 CH CH 2 HBr peroxyd Mg CH 3 CH2 CH2 Br Et2O CH 3 CH2 CH2 MgBr

H2O/H CH3

CH2CH2CH3
CH CH3 OH [O] CH3 C CH3 O

CH3

CH CH3 OMgBr H2O/H

CH2CH2CH3 CH3 CH CH3 OH

29

HP CHT C MAGNESI

3. iu ch t propylen v ha cht v c
b. Acid 2,5-dimethyl adipic
CH3 CH CH2 Cl2 500 C
o

CH2 Cl

CH CH2

Na

CH2

CH CH2

CH2

CH CH2

2 HBr CH3 CH CH2 Br Mg Et2O

1) CO2 2) H2O/H +

CH2

CH CH3 Br

CH3

CH CH2 COOH

CH2

CH CH3 COOH

CH3

CH CH2 MgBr

CH2

CH CH3 MgBr

30

HP CHT C MAGNESI

4. Tng hp cc alcol bc 1 t ROH qua con ng c magnesi

PCl5 Mg Et2O HCHO H2O/H
+

ROH

RCl

RMgCl

RCH2OMgCl

RCH2OH

ROH

PCl5

RCl

Mg Et2O

RMgCl O

RCH2CH2OMgCl

H2O/H

RCH2CH2OH

ROH

PCl5

RCl

Mg Et2O

1)

RMgCl

O
2) H2O/H +

RCH2CH2CH2OH

31

HP CHT C MAGNESI

5. iu ch t ROH v hp cht c 1C :
ROH PCl5 RCl KCN
CH3MgX

R C N

R C N MgX CH3

H2O/H

R C NH CH3

H2O/H
[H] R CH OH CH 3
1) 2)

R C O CH3

CH3MgBr H2O/H
+

CH3 R C OH CH3

32

HP CHT C MAGNESI

6. Hon thnh chui phn ng

a. CH3 C CH
C2H5MgBr CH3 C C MgBr A
CH(OC2H5)3 CH3 C C CH(OC2H5)2 B

H2O/H
OH CH3 C C CH CH3 E
C 2H 2

H2O/H

OMgI CH3 C C CH CH3 D

CH3MgI

CH3

C C CHO C

b. BrMgC CMgBr

HC C MgBr A

1) CH3COCH3 2)

CH3 HC C C CH3 B OH
C 2H 5MgBr

H3O

CH3 HOOC C C CH3 D OH

1) 2)

CO2 H 3O
+

CH3 BrMg C C C CH 3 C OH
33

HP CHT C MAGNESI

6. Hon thnh chui phn ng

CH3 CH2Cl Cl2 as A Mg ether B CH2MgCl
1) 2)

CH2 CH3CHO H 3O
+

CH CH3 OH

c.

[O]

CH 2
CH3 CH2 OH E CH3 OH
1) 2)

C CH 3 O

BrMgC CMgBr H 3O
+

C C C C CH2

34

HP CHT C MAGNESI

6. Hon thnh chui phn ng

d.
CH 3 Cl2 as A B CH2Cl Na ether C6H 5CH2CH 2C 6H 5
1) (C6H5)2CO 2)

Mg ether

C6H5 C6H5 CH2 D H2SO4 180 C C 6H 5 C6H5 CH E C C6H5

o

C6H5CH2MgCl C

H 3O

C C6H5 OH

35