51

CHEMISTRY
REACTIONS
You Can't Afford to MISS!
1. Aldol condensation 5. Clemmensen Reduction
Two molecules of aldehydes or ketones having a-hydrogen In this method, aldehydes and ketones are reduced with
condense together in presence of base [dil. NaOH, Na2CO3, Zn - Hg amalgam and conc. HCl.
Ba(OH)2] to form b-hydroxyaldehyde or b-hydroxyketone Zn – Hg/HCl
CH3CHO + 4H CH3 – CH3 + H2O
respectively which are collectively known as aldol. Zn – Hg/HCl
O CH3COCH3 + 4H CH3 – CH2 – CH3 + H2O
 dil. NaOH
CH3 C H+H CH2 CHO 6. Corey-House synthesis
Acetaldehyde In this reaction, an alkyl halide (1°, 2° or 3°) is first converted
OH
into lithium dialkyl copper and then reacted with another
CH3 CH CH2 CHO alkyl halide (preferably 1°) to give corresponding alkane.
3-Hydroxybutanal Li CuI
(-Hydroxybutanal or aldol) 2R – X 2R – Li R2CuLi + LiI
Ether
Alkyl halide Lithium dialkyl
2. Birch Reduction cuprate
In case of disubstituted alkynes reduction with sodium in
liq. ammonia gives trans-alkene predominantly. This type 7. Cope elimination
of reduction is known as Birch-reduction. Tertiary amines are not oxidised by KMnO4. Their oxidation
is carried out with Caro’s acid or ozone or hydrogen
peroxide to form amine oxide.

3. Beckmann Rearrangement
Oximes on treatment with catalyst such as conc. H2SO4, Tertiary amine oxide containing a β-hydrogen atom forms
SOCl2, PCl5, etc. undergo rearrangement to form substituted an alkene. This reaction is called Cope reaction or Cope
amides. Reaction is known as ‘Beckmann rearrangement’. elimination.

4. Balz-Schiemann’s reaction
This is the method to prepare fluorobenzene from benzene 8. Carbylamine Reaction
diazonium salt by first converting it to benzene diazonium Primary amines both aliphatic and aromatic on heating with
tetrafluoroborate. chloroform and alcoholic solution of potassium hydroxide
+ + form isocyanides or carbylamines which have an extremely
N NCl– –
N NBF 4 F unpleasant odour.
HBF 4 ∆
–HCl + N2 + BF 3
9. Claisen—Schmidt reactions CH2
It is a base catalyzed crossed aldol condensation in which CH2
CH CH2 CH
an aromatic aldehyde condenses with aliphatic aldehyde  CH2
CH +
or ketone. It is also known as simply Claisen reaction. CH2 CH CH2
O O
CH2 CH2
dil. NaOH
C6H5 C H + CH 3 C CH3 Buta-1, 3-diene Ethylene Cyclohexene
Benzaldehyde Acetone
14. Etard Reaction
OH O Aromatic hydrocarbons on treatment with mild oxidising
C6H5 CH CH2 C CH3 agents such as chromyl chloride CrO2Cl2 yield aldehydes.
CH3 CHO
O CrO2Cl2
C6H5 – CHO
C6H5 CH CH C CH3 + H2O dil. NaOH Toluene Benzaldehyde
Benzylidene acetone
O 15. Frankland Reaction
C6H5 CH CH C CH CH C 6H5 This is similar to Wurtz reaction with the difference that
Dibenzal acetone
instead of sodium, zinc is used here in inert solvent.
R – X + Zn + X – R R – R + ZnX2
10. Cannizzaro Reaction
It is a self oxidation-reduction reaction in which Dialkyl zinc compounds react with tertiary alkyl halides
aldehydes that do not have any a-hydrogen atom undergo to give hydrocarbons with quaternary carbon atoms only.
disproportionation reaction (i.e. self-redox reaction) in the (CH3)2Zn + (CH3)3CCl (CH3)4C + CH3ZnCl
presence of 50% aqueous or ethanolic solution of alkali in 16. Finkelstein reaction
which one of the molecule being reduced to alcohol and Iodoalkanes can be conveniently prepared by treating alkyl
other being oxidised to the salt of corresponding acid. chloride or bromides with sodium iodide in acetone or
2HCHO + NaOH CH3OH + HCOONa methanol. This is known as Finkelstein reaction.
Formaldehyde 50% Methanol Sodium formate Acetone
CH3Cl + NaI CH3I + NaCl
Reduction
Oxidation 17. Friedel-Crafts Reaction
Simple aromatic hydrocarbons can be converted to
11. Claisen condensation substituted hydrocarbons by reaction with alkyl halide in
Esters containing a-hydrogen atoms undergo self presence of Lewis acid like AlCl3 or FeCl3, etc.
-condensation in presence of strong base like sodium
ethoxide to give b-keto esters.

18. Fries Rearrangement
Phenyl esters on heating with anhydrous AlCl3 undergo Fries
rearrangement in which acyl group (acetyl, benzoyl, etc.)
migrates from phenolic oxygen to ortho or para position of
12. Curtius rearrangement benzene ring resulting in the formation of mixture of o- and
In this method an acyl azide (obtained from reaction of p-hydroxyketone.
carboxylic acid chloride and sodium azide), on heating OCOC6H5 OH
in acidic or alkaline medium yields primary amine. The OH
COC6H5
reaction involves an intermediate isocyanate which is Anhyd. AlCl3
hydrolysed to give primary amine. ∆ +
Phenyl benzoate o-Hydroxy
benzophenone
COC6H5
p-Hydroxy
benzophenone
19. Gabriel phthalimide synthesis
13. Diels-Alder Reaction Phthalimide on reaction with caustic potash forms potassium
This reaction involves the addition of a conjugated phthalimide which on treatment with alkyl halide gives
diene (4p-electron system) to an unsaturated compound N-alkyl phthalimide. This N-alkyl phthalimide on hydrolysis
called dienophile (2p-electron system) to yield a cyclic with hydrochloric acid yields primary amines.
system.
 25. Hell-Volhard-Zelinsky reaction
(HVZ reaction - Halogenation)
N Aliphatic carboxylic acids on reaction with bromine or
chlorine in presence of small amount of red phosphorous
20. Gattermann-Koch reaction produce a-haloacids.
Benzene on reaction with a mixture of CO + HCl in
presence of AlCl3 forms benzaldehyde.
CHO

AlCl3
+ CO + HCl + HCl

21. Hydroboration-Oxidation
Alkenes react with diborane to give alkyl boranes which on
oxidation with hydrogen peroxide in presence of hydroxide
forms alcohol.
B 2H6 26. Hofmann-bromamide reaction
R – CH CH2 R – CH2 – CH2 – BH2 Primary amides on reaction with bromine in presence of
RCH CH2 an alkali yield primary amine with one carbon atom less
than the parent amide.
RCH CH2
(RCH2CH2)3B (RCH2CH2)2BH
Trialkyl borane

3H2O2/OH–
3RCH2CH2 – OH + B(OH)3
Alcohol Boric acid 27. Knoevenagel reaction
22. Hunsdiecker reaction In this reaction, aldehydes and ketones condense with
This reaction involves the treatment of silver salt of carboxylic compounds containing active methylene group like acid (e.g.
acid with bromine in refluxing CCl4 to yield alkyl bromide malonic acid), ester (e.g. acetoacetic ester, malonic ester)
with one carbon atom less than the original acid used. or nitrile, etc. leading to the formation of a, b-unsaturated
CCl4
CH3CH2COOAg + Br2 Reflux CH3CH2 compound.
2
CH3 COOH (i) Pyridine/
23. Hofmann Mustard oil Reaction C O + H2C
H COOH (ii) H3O+
This reaction is given by aliphatic and aromatic primary Acetaldehyde Malonic acid
amines only, hence it can be used as a test for primary
amines. H3C – CH CH – COOH + CO2 + H2O
Crotonic acid

28. Kolbe’s Electrolytic Method

Alkyl isothiocyanates have a characteristic unpleasant smell
of mustard oil. Hence, this reaction is known as Hofmann
mustard oil reaction.
24. Haloform reaction
Methyl ketones on oxidation with sodium hypohalite
(NaOX i.e. NaOH + X2) yield haloform along with sodium
salt of carboxylic acid with one carbon atom less than the
starting ketone.
In this method, a concentrated solution of sodium or
potassium salt of a carboxylic acid is electrolysed to give
higher alkanes.
RCOOK + RCOOK Electrolysis
R — R + 2CO2 + H2 + 2KOH
29. Leuckart reaction
An aldehyde or ketone on heating with ammonium formate
or ammonium formamide, undergoes reductive amination
to form formyl derivative of primary amine which on
hydrolysis either with acid or base yields primary amine.
 O
H2 CH C CH3 COONa
C6H5 CH O+ O
Benzaldehyde CH3 C –H2 O, D

O
Acetic anhydride
O
30 Meerwein-Ponndorf-Verley reduction H2 O
C6H5 CH CH C
In this reaction, ketones are reduced to secondary alcohols Hydrolysis O
on heating with iso-propyl alcohol in presence of catalyst CH3 C
aluminium isopropoxide. In the reaction iso-propyl alcohol O
gets oxidised to acetone.
R CH3 [(CH3)2CHO]3Al CH3COOH + C6H5 CH CH COOH
C O+ CH OH Acetic acid Cinnamic acid
R CH3
Ketone Iso -propyl alcohol 35. Reimer-Tiemann reaction
R CH3 Concentrated solution of CHCl3 reacts with phenol in
CH OH + C O presence of alc. KOH to yield salicylaldehyde.
R CH3 OH OH
2° alcohol Acetone
CHO
31. Ozonolysis KOH (alc.)
+ CHCl3
Ozone on passing through a solution of alkenes in an inert dil. HCl
solvent like CCl4 or CHCl3 at low temperature oxidises the Salicylaldehyde
alkene to a cyclic product called ozonide which is unstable
36. Reformatsky reaction
and on reduction with reducing agents like zinc and water
It involves the reaction of zinc and a-halogenated ester,
or hydrogen in presence of palladium gives aldehydes and/
which add to carbonyl compound to yield b-hydroxy ester.
or ketone depending upon structure of alkene, i.e., C O
part of the alkene gets converted to C O.  Zn
O CH3 – C – CH3 + BrCH2COOC2 H5
Zn/H2O
C C + O3 C C 2 C O
–ZnO
O OH OZnBr
O
H2O/H+
CH3 – C – CH2COOC2H5 CH3 – C – CH2COOC2H5
32. Oppenauer’s oxidation
In this reaction, secondary alcohols are oxidised to ketones CH3 CH3
in a good yield using aluminium tert- butoxide in excess Ethyl-3-hydroxy-3-methyl butanoate
of acetone.
O 37. Rosenmund’s reduction
R Acid chlorides are reduced to aldehydes by palladised barium
CH OH + CH3 C CH3
R [(CH3)3CO]3Al
sulphate partially poisoned with sulphur or quinoline.
2° alcohol Acetone (—COCl is reduced to —CHO)
OH
R
C O + CH3 CH CH3
R
Ketone Iso- propyl alcohol
38. Sandmeyer’s reaction
33. Oxo process In this reaction Diazonium salttract with CuX/HX and
In this process, an alkene on heating with water gas respective halide is formed.
(CO + H2) under pressure in the presence of catalyst cobalt Cl
carbonyl hydride [CoH(CO)4] yields aldehyde. +
N NCl– CuCl/HCl
[CoH(CO)4] + N2
C C + CO + H2 C C CHO
100°C, Pressure

34. Perkin condensation Br

It is a condensation reaction in which an aromatic aldehyde
CuBr/HBr
condenses with aliphatic acid anhydride in presence of + N2
sodium salt of same acid to give a condensate which upon
hydrolysis yields a,b-unsaturated acid. 39. Schotten-Baumann reaction
 OH O 45. Williamson’s synthesis
Metal alkoxides on treatment with alkyl halides yield ethers.
Cl C NaOH The reaction is known as Williamson’s synthesis.
+ O
O C
+ HCl 46. Wacker process
Phenyl benzoate Alkenes are directly oxidised by the catalyst palladium
Benzoylation of alcohols or phenols in presence of NaOH chloride-cupric chloride (PdCl2-CuCl2) in the presence
is called Schotten-Baumann reaction. of air or oxygen.
1 PdCl2-CuCl2
40. Stephen’s reduction CH2 CH2 + O 2 CH3 CHO
2 air or O2
Ethene Ethanal
In this reaction cyanides are reduced to aldehyde in pressure
of SnCl2/H4 followed by hydrolysis. 47. Wolff-Kishner Reduction
H
SnCl2 + HCl + H2O
In this method, aldehydes and ketones are reduced with
R C N Ether
R C NH2Cl¯ hydrazine (NH2–NH2) and KOH.
Aldimine O CH3
hydrochloride
NH2 – NH2
RCHO + NH4Cl R – C – CH3 R –C NNH2
Aldehyde
KOH/glycol
41. Schmidt’s reaction or C2H5ONa
Carboxylic acids on heating with hydrazoic acid (HN3) at
50-55°C in presence of conc. H2SO4 produce primary amines R–CH2– CH3 + N 2
with one carbon atom less than original carboxylic acid.
48. Wurtz Reaction
In this reaction, ether solution of alkyl halide is treated
with sodium to form alkane.
Dry ether
42. Sabatier - Senderen’s reaction R –X + 2Na + X – R R– R + 2Na X
The method involves the reduction of unsaturated
hydrocarbons (alkenes and alkynes) with nickel catalyst. 49. Wittig Reaction
Raney nickel is more reactive than supported nickel catalyst. It is an important reaction to change a carbonyl compound
Ni
RCH CH2 + H2 RCH2CH3 into alkene by treating carbonyl compound with a ylide.
200-300°C
Alkene Alkane Ylides are the species which in their ground state have
43. Tischenko reaction negative carbon adjacent to a positive heteroatom like P,
+ –
All aldehydes (with or without a-hydrogen atom) in As, Sb, etc. For example, phosphorus ylide, Ph3P – CHR .
+ – THF or
presence of aluminium ethoxide, [Al(OC2H5)3] undergo RCH O + Ph3P – CHR dry ether RCH CHR + Ph 3PO
simultaneous oxidation (to carboxylic acid) and reduction
(to alcohol) to form an ester. 50. Wohler’s reaction
Al(OC2H5)3 Acetylene is prepared by action of water on calcium carbide.
2RCHO RCH2OH + RCOOH
This method is used for laboratory as well as industrial
Aldehyde Alcohol Carboxylic acid
preparation.
CaC2 + 2H2O CH CH + Ca(OH)2
RCOOCH2 R
Ester
51. Wurtz-Fittig Reaction
44. Ullmann Reaction When a mixture of aryl halide and alkyl halide reacts
Aryl halides especially iodides on reaction with copper with sodium metal in dry ether, substituted arenes are
metal yield biphenyls. obtained.
Sealed Dry
tube ether
I + 2Cu + I + 2CuI Cl + 2Na + Cl CH3 CH3 + 2NaCl
Biphenyl