CHEMISRY BY R.

N SIR

1.Markonikov’s rule :- According to this addition of Hydrogen halide (HCl, HBr,HI) on

any asymmetric alkene occurs in such a manner that negative atom link to that carbon
which have less number of hydrogen atom.

2. ANTIMARKONIKOV’S RULE In presence of Peroxide the reaction occurs opposite to

markonikov’s i.e negative species get link to that carbon which have more number of
hydrogen this effect is also known as KHRASH EFFECT.

3. Finkelstein reaction (Halogen exchange method) . Alkyl iodides are often prepared
by the reaction of alkyl chlorides/ bromides with NaI in dry acetone. This reaction is
known as Finkelstein reaction.

Note :- NaCl or NaBr thus formed is precipitated in dry acetone. It facilitates the
forward reaction according to Le Chatelier’s Principle.

4. Swarts Reaction :- The synthesis of alkyl fluorides is best accomplished by heating

an alkyl chloride/bromide in the presence of a metallic fluoride such as AgF, Hg 2F2, CoF2
or SbF3. The reaction is termed as Swarts reaction.

5.Wurtz reaction When Alkyl halides react with sodium in dry ether to give
hydrocarbons containing double the number of carbon atoms present in the halide. This
reaction is known as Wurtz reaction
Note :- Only even number of carbon atoms Alkane is formed .

6. Fittig reaction Aryl halides also give analogous compounds when treated with
sodium in dry ether, in which two aryl halides are joined together. It is called Fittig
reaction.

7. Wurtz-Fittig reaction A mixture of an alkyl halide and aryl halide gives an

alkylarene when treated with sodium in dry ether and this reaction is known as Wurtz-
Fittig reaction.

8 Friedel-Crafts Alkylation reaction:- When benzene is treated with an alkyl halide in

the presence of anhydrous AlCl3 , alkyl benzene is formed .
Note : - Aromatic carboxyl acids do not undergo fridel crafts reaction because the
carboxyl group is deactivating and the catalyst aluminium chloride gets bonded to
carboxyl group.

9. Friedel –Crafts acylation reaction When benzene is treated with an acyl halide or
acid anhydride in the presence of anhydrous AlCl3 , acyl benzene is formed .

10. Kolbe’s reaction

Phenoxide ion generated by treating phenol with sodium hydroxide which is even more
reactive than phenol towards electrophilic aromatic substitution. it undergoes
electrophilic substitution in presence of carbon dioxide and Ortho hydroxybenzoic acid
is formed .

11. Reimer-Tiemann reaction On treating phenol with chloroform (CHCl 3 ) in the

presence of sodium hydroxide, a –CHO group is introduced at ortho position of benzene
ring and salicyaldehyde is formed.

Wheras on treatment with CCl 4 in presence of sodium hydroxide a -COOH group is

introduced at ortho position of benzene ring and saliycilicacid is formed .These reaction
is known as Reimer - Tiemann reaction.
12. Reaction of phenol with zinc dust Phenol is converted to benzene on heating with
zinc dust.

13. Oxidation of phenol Oxidation of phenol with chromic acid produces a conjugated
diketone known as benzoquinone. In the presence of air, phenols are slowly oxidised to
dark coloured mixtures containing quinine..

14. dehydration of alcohols Alcohols undergo dehydration in the presence of protic

acids(H 2SO4, H 3PO4). The formation of the reaction product, alkene or ether depends
on the reaction conditions.
 For example, ethanol is dehydrated to ethene at 443 K. and ethoxyethane at 413 K, as
the main product.

15. Williamson synthesis It is an important laboratory method for the preparation of

symmetrical and unsymmetrical ethers. In this method, an alkyl halide is allowed to
react with sodium alkoxide.

R–X + R –O – Na R–O–R + NaX

NOTE The reaction involves SN2 attack of an alkoxide ion on primary alkyl halide.

16. Stephen reaction Nitriles are reduced to corresponding imine with stannous
chloride in the presence of HCl, which on hydrolysis give corresponding aldehyde. This
reaction is called Stephen reaction.

17. Etard reaction Chromyl chloride (CrO2Cl2) oxidizes toluene methyl group to a
chromium complex, which on further hydrolysis gives corresponding benzaldehyde.
This reaction is called Etard reaction.

18. Gatterman – Koch reaction When benzene or its derivative is react with carbon
monoxide and hydrogen chloride in the presence of anhydrous aluminium chloride(AlCl
3) or cuprous chloride(CuCl), it give benzaldehyde .This reaction is known as Gatterman-
Koch reaction.

19. Hell-Volhard-Zelinsky (HVZ) reaction.

Carboxylic acids having an α-hydrogen are halogenated at the a α-position on treatment

with chlorine or bromine in the presence of small amount of red phosphorus to give a-
halocarboxylic acids. The reaction is known as Hell-Volhard-Zelinsky reaction.

20. Cannizzaro reaction Aldehydes which do not have an α-hydrogen atom,

undergo self oxidation and reduction (disproportionation) reaction on heating with 50%
conc.NaOH/KOH In this reaction, one molecule of the aldehyde is reduced to alcohol
while another is oxidised to sodium salt of carboxylic acid .

Cross cannizzaro reaction ;- When cannizzaro reaction occurs between different

aldehyde i.e benzaldehyde and formaldehyde such reaction is known as cross
cannizzaro reaction.

21. Clemmensen reduction The carbonyl group of aldehydes and ketones are reduced
to alkane in presence of Zn-Hg(Zinc amalgam) and con. HCl such reduction of carbonyl
group is known as clemmensen reduction.

22.Wolff-Kishner reduction carbonyl group of aldehydes and ketones are reduced to

alkane in presence of hydrazine followed by heating with sodium or potassium
hydroxide in high boiling solvent such as ethylene glycol.

23. Tollens’ test: On warming an aldehyde with freshly prepared ammoniacal silver
nitrate solution (Tollens’ reagent), a bright silver mirror is produced due to the
formation of silver metal. The aldehydes are oxidised to corresponding carboxylate
anion. The reaction occurs in alkaline medium.

24.Fehling’s test: Fehling reagent comprises of two solutions, Fehling solution A and
Fehling solution B. Fehling solution A is aqueous copper sulphate and Fehling solution B
is alkaline sodium potassium tartarate (Rochelle salt). These two solutions are mixed in
equal amounts before test. On heating an aldehyde with Fehling’s reagent, a reddish
brown precipitate is obtained. Aldehydes are oxidised to corresponding carboxylate
anion.

NOTE:- Aromatic aldehydes do not respond to this test.

25. Aldol condensation: Aldehydes and ketones having at least one α-hydrogen
undergo a reaction in the presence of dilute alkali as catalyst to form β-hydroxy
aldehydes (aldol) or β-hydroxy ketones (ketol), respectively. This is known as Aldol
reaction.

26. Cross aldol condensation: When aldol condensation is carried out between two
different aldehydes or ketones, it is called cross aldol condensation. If both of them
contain α-hydrogen atoms, it gives a mixture of four products. This is illustrated below
by aldol reaction of a mixture of ethanal and propanal.

NOTE:- Ketones can also be used as one component in the cross aldol reaction.
27. Gabriel phthalimide synthesis Gabriel synthesis is used for the preparation of
primary amines. Phthalimide on treatment with alc.KOH forms potassium salt of
phthalimide which on heating with alkyl halide (R-X) followed by alkaline hydrolysis
produces the corresponding primary amine

NOTE:-Aromatic primary amines cannot be prepared by this method because aryl

halides do not undergo nucleophilic substitution with the anion formed by phthalimide.

28. Hoffmann bromamide degradation reaction Hoffmann developed a method for

preparation of primary amines by treating an amide with bromine in an aqueous or
Alc.sodium hydroxide. In this degradation reaction, migration of an alkyl or aryl group
takes place from carbonyl carbon of the amide to the nitrogen atom. The amine so
formed contains one carbon less than that present in the amide.

29. . Carbylamine reaction Aliphatic and aromatic primary amines on heating with
(CHCl3) and Alc. KOH form isocyanides or carbylamines which are foul smelling
substances.

NOTE :-Secondary and tertiary amines do not show this reaction. This reaction is known
as carbylamines reaction or isocyanide test and is used as a test for primary amines.

30. Hinsberg’s reagent, Reaction with Benzenesulphonyl chloride (C 6H 5SO 2Cl), which
is also known as Hinsberg’s reagent, reacts with primary and secondary amines to form
sulphonamides. The reaction of benzenesulphonyl chloride(C 6H 5SO 2Cl), with primary
amine yields N-ethylbenzenesulphonyl amide.

NOTE :-The hydrogen attached to nitrogen in sulphonamide is strongly acidic due to the
presence of strong electron withdrawing sulphonyl group. Hence, it is soluble in alkali.

31. Diazotisation Rection :- Benzenediazonium chloride is prepared by the reaction of

aniline with nitrous acid at 273-278K. Nitrous acid is produced in the reaction mixture by
the reaction of sodium nitrite with hydrochloric acid. The conversion of primary
aromatic amines into diazonium salts is known as diazotisation.

32. Sandmeyer reaction In benzene Diazonium chloride replacement of Halgen ion can
be done by halide or cyanide ion (Cl–, Br– and CN–)in the presence of Cu(I) ion. This
reaction is called Sandmeyer reaction

33. Gattermann reaction chlorine or bromine can also be introduced in the benzene
ring by treating the diazonium salt solution with corresponding halogen acid in the
presence of copper powder. This is referred as Gatterman reaction.

NOTE : The yield in Sandmeyer reaction is found to be better than Gattermann

reaction.

34 .Balz-Schiemann Reaction. When arenediazonium chloride is treated with

fluoroboric acid, arene diazonium fluoroborate is precipitated which on heating
decomposes to yield aryl fluoride.

35. Rosenmund reduction. Acyl chloride is reduced to aldehyde in presence Pd-BaSO4

.This reaction is called Rosenmund reduction.