NAMED REACTIONS

HALOALKANES AND HALOARENES

1. Finkelstein's Reaction (RCl → RI)
When alkyl chlorides or bromides are treated with sodium iodide (NaI)
in the presence of dry acetone yields alkyl iodides. This reaction is called
Finkelstein's reaction.

2. Swartz Reaction (RCl → RF)

The reaction in which alkyl fluorides are prepared by heating alkyl bromides or
chlorides in presence of metallic fluorides like AgF, CoF2, SbF3 or Hg2F2 are
called Swarts reaction.

3. Wurtz Reaction (RX → R-R)

When alkyl halides react with sodium metal in dry ether medium to
give higher alkanes the reaction is called Wurtz reaction.

4. Fittig Reaction
Aryl halides when treated with sodium metal in dry ether, two aryl
halides are joined together. This is called Fittig reaction. The reaction is quiet
useful for preparing diphenyl.

5. Wurtz–Fittig Reaction
When the mixture alkyl and aryl halide is treated with Na metal in dry ether
 medium alkyl benzene is obtained. This is called Wurtz-Fittig reaction.

6. Sandmeyer Reaction (Aniline → Chloro or bromo benzene)

The Sandmeyer reaction is a chemical reaction used to synthesise aryl halides from
aryl diazonium salts.
Aniline (aryl amines) is first converted to its diazonium salt (Ar—N2Cl)
using nitrous acid (HCl + NaNO2).
s

ALCOHOLS, PHENOLS AND ETHERS

7. Kolbe's Reaction
When sodium phenoxide is heated with CO2 at 400 K and at a pressure
of 4-7 atm sodium salicylate is formed as the major product. This on acidification
yields salicylic acid. This is called Kolbe's reaction.

8. Reimer–Tiemann Reaction (phenol → salicaldehyde)

Treatment of phenol with chloroform in the presence of aqueous alkali
at 340 K results in the formation of o-hydroxybenzaldehyde (salicylaldehyde)
and p- hydroxybenzaldehyde, the ortho isomer being the major product. This
reaction is called Reimer-Tiemann reaction.
 9. Williamson's Synthesis (alcohol → ether)
When sodium alkoxide is heated with alkyl halide, ethers are formed.
This reaction is called Williamson's synthesis.
Sodium alkoxide is prepared by the action of sodium on alcohol.

R—OH + Na RONa + ½H2

Alcohol sodium sodium alkoxide

R—X + NaOR' R—OR' + NaX

Alkyl halide sodium alkoxide Ether

It is important to note that, the alkyl halide to be used in the

Williamson's synthesis should be 1 . This is because 3 alkyl halides have a strong
tendency to undergo elimination which results in the formation of alkene and
not ether (refer page 338 for details).

ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

10. Rosenmund's Reduction

Rosenmund’s reaction involves hydrogenation of acyl chloride (acid
chloride) over catalyst palladium on barium sulphate (Pd/BaSO4) to yield
aldehydes.

11. Stephen's Reaction

Nitriles are reduced to corresponding imine hydrochloride by stannous
chloride (SnCl2) in presence of dil. HCl which on further acid hydrolysis gives
corresponding aldehyde. This reaction is called Stephen's reaction.

12. Etard's Reaction

Benzaldehyde can be prepared from toluene from this reaction. Etard's
 reaction involves the oxidation of toluene with chromyl chloride (CrO2Cl2)
in CCl4 or CS2.

13. Gattermann–Koch Reaction

This reaction involves the treatment of diazonium salts with Cu/HCl or
Cu/HBr to yield aryl chlorides or bromides respectively.

14. Cannizzaro's Reaction

Aldehydes which do not have α-hydrogen atom, such as formaldehyde
and benzaldehyde, when heated with concentrated (50%) alkali solution give
a mixture of alcohol and salt of carboxylic acid.

• In this reaction, the aldehyde undergoes disproportionation. One

molecule of aldehyde is oxidized to (salt of) carboxylic acid while other

one is reduced to alcohol.
• Ketones DO NOT give this reaction.

15. Clemmensen's Reduction

The carbonyl group (>C=O) can be reduced to methylene (>CH 2) group
resulting in formation of alkanes by zinc amalgam and concentrated HCl (Zn-
Hg/HCl). This reaction is called is Clemmensen's reduction.
16. Wolff–Kishner's Reduction
The carbonyl group (>C=O) can be reduced to methylene (>CH 2) group
resulting in formation of alkanes by hydrazine followed by heating with
sodium or potassium hydroxide in ethylene glycol. This reaction is called is
Wolff-Kishner reduction.

17. Hell–Volhard–Zelinsky (HVZ) Reaction

When carboxylic acids are treated with Cl 2 or Br2 in the presence of red
phosphorus, the α-hydrogen atoms of carboxylic acids are replaced by chlorine
and bromine.

AMINES
18. Gabriel–Phthalimide Synthesis
In this method phthalimide is first converted into potassium
phthalamide by reaction with KOH which on further treatment with alkyl halide
gives N-alkyl phthalimide. This on alkaline hydrolysis gives primary (1˚)
amine.
 By using this method, we can prepare only 1˚ aliphatic amines. Aromatic,
2˚ or 3˚ amines CANNOT be prepared by this method.

19. Hoffmann Bromamide Degradation

Primary (1˚) amides on reaction with Br2 in the presence of alkalis give
1˚ amines. It may be noted that the amine formed by this method has one
carbon less than the parent compound.

R—CONH2 + Br2 + 4NaOH R—NH2 + 2NaBr + Na2CO3 +

H2O
Amide 1˚ amine

20. Gattermann Reaction

This reaction involves the treatment of diazonium salts with Cu/HCl or Cu/HBr to
yield aryl chlorides or bromides respective

21. Mendius Reaction

RCN+2H2 (Na/C2H5OH) RCH2NH2

22. Balz – Schiemann Reaction

23. Borodine Hunsdiecker Reaction

24. Friedel Craft Alylation Reaction

25. Friedel Craft Acylation Reaction

Miscellaneous Reactions

1. Aldol Condensation
Two molecules of an aldehyde or a ketone having at least one α-
hydrogen atom condense in the presence of dilute alkali to give β-hydroxy
aldehyde (aldol) or β- hydroxy ketone (ketol). This reaction is called aldol
condensation.
2. Crossed Aldol Condensation
When aldol condensation takes place between two different aldehydes or
ketones
then it is called crossed aldol condensation or mixed aldol condensation.

Crossed aldol condensation can also occur when one of the carbonyl
molecule do not contain α-hydrogen, with other molecule possessing α-H
atom.
3. Coupling Reactions
Benzene diazonium chloride when reacts with compounds like phenol
and aniline form azo compounds. This reaction is called coupling reaction or azo
coupling.
The azo compounds are coloured and many of them are used
as dyes and indicators.

4. Diazotization
Aryl amines (such as aniline) react with nitrous acid, HNO2 (HCl +
NaNO2) at low temperature to give diazonium salts. This reaction is known as
diazotisation.
Nitrous acid being unstable is prepared in situ by the reaction of sodium
nitrite and dilute hydrochloric (mineral) acid.

5. Hydroboration–Oxidation Reaction
In this reaction alkene is treated with diborane (B2H6) followed by
the treatment with water in the presence of H2O2. Alcohol is obtained as a
product.

3 CH3-CH=CH2 + (BH3)2 ———→ 3 CH3CH2CH2OH + B(OH)3 or H3BO3

Propene diborane propanol boric acid