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Hoffmann Method for Amine Separation

The document discusses organic chemistry reactions involving haloalkanes, haloarenes, alcohols, phenols, ethers, aldehydes, ketones, carboxylic acids, and amines. It provides examples of reactions to increase or decrease carbon chain length as well as aromatic conversions.

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Shashak Mishra
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0% found this document useful (0 votes)
33 views9 pages

Hoffmann Method for Amine Separation

The document discusses organic chemistry reactions involving haloalkanes, haloarenes, alcohols, phenols, ethers, aldehydes, ketones, carboxylic acids, and amines. It provides examples of reactions to increase or decrease carbon chain length as well as aromatic conversions.

Uploaded by

Shashak Mishra
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

2.

Haloalkane and Haloarene


Organic Chemistry
❑ Markovnikov’s rule
❑ Anti- Markovnikov’s rule (Peroxide effect)
SET A: ❑ Dehydrohalogenation
1. Identification of 10, 20 and 30 alcohols by Victor Meyer’s method. ❑ Saytzeff’s rule
2. Separation of 10, 20 and 30 amines by Hoffmann’s method. ❑ Wurtz reaction
3. Distinction of 10, 20 and 30 amines by Nitrous acid test ❑ Fittig reaction
4. Comparison of basic strength of 10, 20 and 30 amines. ❑ Wurtz- Fittig reaction
5. Oxidized product of 10, 20 and 30 alcohols. ❑ Diazotization reaction
6. Chemical properties of Grignard’s reagent. ❑ Sand Meyer's reaction
7. Reduction of Nitrobenzene in different medium. ❑ Gattermann reaction
❑ Reimer-Tiemann reaction
❑ Carbylamine reaction

SET B: Name reactions: 3. Alcohol and Phenol


1. Aromatic Hydrocarbon ❑ Oxo process
❑ Decarboxylation reaction ❑ Hydroboration
❑ Friedel- Craft’s alkylation ❑ Esterification reaction
❑ Friedel- Craft’s acylation ❑ Dow’s process
❑ Liebermann's Test
❑ Carboxylation reaction ( Kolbe’s reaction )
❑ Coupling reaction( preparation of azo dyes)
4. Ether
❑Williamson’s etherification reaction
5. Aldehyde and Ketone
❑Ozonolysis ❑2,4-DNP Test
❑Rosenmund reduction ❑ Action with ammonia
❑Clemmensen reduction ❑Action of Tollen’s reagent
❑Wolf- kishner reduction ❑Action with Fehling’s solution
❑Aldol condensation ❑ Iodoform Test
❑Cannizaro’s reaction
❑Gattermann Koch synthesis 7. Amine
❑Perkins condensation ❑(Hoffmann’s reaction) Bromamide reaction (
❑Benzoin condensation Decarbonylation )
6. Carboxylic acid ❑ Hoffmann’s Ammonolysis reaction
❑ Coupling Reaction
❑Hell- Volhard- Zelinsky (HVZ )
❑(Hoffmann’s reaction) Bromamide reaction ( Decarbonylation )
❑Claisen Condensation reaction.
Conversion
To increase Carbon number in chain
a. Wurtz reaction
b. Reaction with KCN
c. Reaction with Grignard reagent
d. Oxo-process
e. Carboxylation reaction
f. Carbonylation reaction
To decrease Carbon number in chain
a. Decarboxylation reaction [Sodalime (CaO + NaOH)]
b. Decarbonylation reaction [Hoffmann’s bromamide reaction]

3
Aliphatic Conversion
Cl2,hv Cl2,hv KCN
Na/dryether
CH4 CH3-Cl ∆ CH3-CH3 CH3-CH2-Cl CH3-CH2-CN
Alc. KOH [Link]
H2O/H+
Br2/CCl4
Br-CH2-CH2-Br CH2=CH2 CH3-CH2-OH
CH3-CH2-COOH
[Link] H2/Ni [O]
SOCl2
CH2=CH-Br CH3-CH3 CH3-CHO
CH3-CH2-COCl
[Link] Cl2,hv [O]
NH3

CH≡CH CH3-CH2-Cl CH3-COOH


CH3-CH2-CONH2
H2O 42% H2SO4, NaOH + CaO
1% HgSO4, Br2/KOH

CH3-CHO CH4 CH3-CH2-NH2


LiAlH4 HNO2

CH3-CH2-OH CH3-CH2-OH
LiAlH4 SOCl2 KCN
LiAlH4
HCHO CH3-OH CH3-Cl CH3-CN CH3-CH2-NH2
HNO2

CH3-CH2-OH
H H [O]

H2O/H+ KCN
CH3-C-OH CH3-C-OH CH3-CHO

COOH CN [O]

LiAlH4 SOCl2 KCN H2O/H+


(HCOO)2Ca Distill
HCHO CH3-OH CH3-Cl CH3-CN CH3-COOH
NH3

CaO CH3-COO-NH4+
-H2O ∆
[O] [O] HNO2 Br2/KOH
HCOOH HCHO CH3-OH CH3-NH2 CH3-CO-NH2
Aromatic Conversion NO2 NH2 COOH
N2+Cl- CN
COONa
Sn/HCl NaNO2 + HCl H2O/H+
CuCN/HCl

0-50C
Aniline

H2O,Boil
OH CaO+ NaOH Conc. HNO3, N=N NH2
Conc. H2SO4

Zn-Dust Cl OH
i. NaOH,
Cl2, FeCl3 3500C, 300atm BDC
N=N OH
Cl
ii. HCl CHCl3, OH
NaOH
CH3Cl , CHO
Anh. AlCl3 60-70 0C

CH3 CH2-Cl CH2-OH CHO COOH


CH≡CH Cl2,hv Aq. KOH [O] [O]
NO2 NH2 NC NH-CH3
Sn/HCl CN CH2 –NH2
CHCl3/alc. KOH LiAlH4

Warm LiAlH4

CH3 CHO

CeO2/H+ (CH3CO)2O
CH=CH-COOH
CH3 COONa,1800C

KMnO4

COOH COCl CONH2 NH2


SOCl2 NH3
Br2/KOH

NH3
COO-NH4+ CONH2 NH2
-H2O Br2/KOH
7
CuCN/HCl
CN

Cu2Cl2 /HCl
Cl
Or
Cu-powder /HCl

Cu2Br2 /HBr
Br
Or
Cu-powder /HBr
NaNO2 + HCl
NH2 N2+Cl- H2O,Boil
0-50C
OH

Aniline
N=N NH2

Phenol N=N OH
8
Conc. HNO3 Sn/HCl H2/Pd
CHCl3, KOH D
A B C
Conc. H2SO4 60-70 0C

CH3Cl/AlCl3 NH3
KMnO4/ H+ SOCl2 D
A B C

NH2

NaNO2 + HCl NH3


CuCN H2O/H+ D E
A B C ∆
0-50C

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