IIT-JEE | CBSE

IMPORTANT NAMED REACTIONS

(IN ALPHABETICAL ORDER) NCERT
1. Arndt Eistert Synthesis is an important method for homologation of acids. It consists of converting a carboxylic acid into it’s
acid chloride. By treating the acid chloride with diazomethane and reacting the resulting diazo ketone with colloidal silver to form
higher carboxylic acid.
SOCl22 CH2N2 Ag/H2O
RCOOH RCOCl RCOCHN2 RCH2COOH
Carboxylic acid Acid chloride Diazoketone carboxylic acid

2. Aromatisation. It is a process of converting an alkane with six or more carbon atoms into corresponding aromatic hydrocarbon
under suitable conditions. The process which involves cyclisation and dehydrogenation is called aromatisation. It is generally
carried by heating the alkane at high temperature ( 770K) at high pressure (10-20 atomosphere) in the presence of catalyst such as
oxides of chromium. Vanadium etc. For example n-hexane gives benzene when passed over chromium oxide supported over
alumina at 730 K.

CH2H CH2

CH2 CH2H H2C CH2

Al2O3 – Cr2O3, 770 K Dehydrogenation
– H2 – 3 H2
CH2 CH2 H2C CH2
CH2 CH2 Benzene
n-Hexane Cyclohexane

3. Allylic Substitution Reaction. Alkenes (except ethylene) also show substitution reaction. In most of these reactions.
Substitution occurs at the allylic carbon. When propene is treated with chlorine at 773 K. 3-Chloropropene is formed.
773 K
CH3 – CH = CH2 + Cl2 ClCH2 – CH = CH2 + HCl
Propene 3-Chlororpropene
This type of reaction where substitution occurs at the α-position (w.r.t. double bond) is called Allylic substitution.
4. Aldol Condensation. Two molecules of aldehydes or ketones containing α-hydrogen atoms on treatment with a dilute base (dil.
NaOH. Na2CO3. Ba(OH)2 etc.) undergo condensation to form β-hydroxyldehydes or β-hydroxy ketones. This reaction is called
aldol condensation. For example,

CH3 OH
α NaOH 4 3 2 1
C = O + H – CH2CHO CH3 – C – CH2 – CHO
H
H
Ethanal or acetaldehyde 3-Hydroxybutanal
(Two molecules) (Aldol)
CH3 OH
α Ba(OH)2 5 4 3 2 1
C = O + H – CH2 COCH3 CH3 – C – CH2 – CO – CH3
CH3
CH3
Propanone or Acetone 4-Hydroxy-4-methyl-2-pentanone
(Two molecules) (Diacetone alcohol)

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 The products of aldol condensation when heated with dilute acids undergo dehydration leading to the formation of α. Β-
unsaturated aldehydes or ketones. For example,

OH H
H+. H2O 4 3 2 1
CH3 – CH – CH – CHO ∆ CH3 CH = CH – CHO + H2O
Aldol 2-Butenal
(Crotonaldehyde)

CH3 HO H CH3
H+. H2O
C CH –COCH3 ∆ C = CHCOCH3 + H2O
CH3 CH3
Diacetone alcohol 4-Methylpent-3-en-2-one
(Mesityl oxide)
Aldehydes such as formaldehyde. α. α- dimethylpropionaldehyde (or 2. 2-dimethylpropanal). Benzaldehyde etc. which do not
contain α-hydrogen do not undergo aldol condensation.
5. Asymmetric Synthesis. The process of synthesis of an optically active compound form an optically inactive compound. in the
presence of suitable Chiral molecule. is called as Asymmetric synhesis.

O OH
LiAlH4
H3C – C – CH2CH3 Ether H3C – CH – CH2 – CH3
Butanone-2 Lithium aluminium Butanol-2
hydride (dl form)

O OH
LiAlH4/Ether
H3C – C – CH2 – CH3 Chiral molecule H3C – CH – CH2 – CH3
Butanol-2
d- or l-
6. Benzoin Condensation. On heating with an ethanolic solution of KCN, two molecules of aromatic aldehydes undergo
condensation to form benzoin. This reaction is called benzoin condensation. For example,
O O OH O
Alc. KCN
C6H5 – C – H + H – C – C6H5 C6H5 – CH – C – C6H5
Benzoin

7. Bimolecular Reduction. This reaction involves the reduction of acetone to pinacol by magnesium amalgam and water.
CH3 CH3 CH3 CH3
Mg – Hg/H2O
H3C–C + 2[H] + C – CH3 H3C– C– – – –C – CH3

O O OH OH
Acetone Acetone Tetramethyl ethylene glycol
or
2, 3- Dimethyl-butane-2.3-diol
(Pinacol)
8. Beckmann Rearrangement involves the treatment of aldoxime or ketoximes with acidic reagents like Conc. H2SO4,.P2O5.,PCl5
etc., to form amides.
(1) Conc. H2SO4
C6H5 – C –– C6H5 (2) H2O C6H5 – C – OH C6H5– C = O

N – OH N – C6H5 HN – C6H5
Benzophenoneoxime (Unstable) (Benzanilide)

9. Benzil – Benzilic Acid Rearrangement. When α – diketones (benzils) are treated with alkali, they are transformed into
hydroxy carboxylic acids.
C6H5 – CO – C O – C6H5 + NaOH (C6H5)2C – COONa
Benzil

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 OH
Sodium salt benzilic acid
10. Baeyer Villiger Oxidation involves the oxidation of ketones (both cyclic and acyclic) to esters Lactones by means of peracids
such as perbenzoic acid (PBA). Per acetic acid (PAA). Trifluoroperacetic acid (TFPAA) etc. For Example,
RCOR’ + RCO OOH RCOOR’ + RCOOH
Ketone Per carboxylic acid Ester Carboxylic acid
11. Berthelot’s Synthesis. It is a method of synthesis of ethyne from its elements by striking an electric arc between carbon
electrodes in an atmosphere of hydrogen.

Electric arc
2 C + H2 H–C≡C–H
3300 K
12. Birch Reduction. A terminal double bond may be reduced by sodium in liquid NH 3 in presence of ethanol or methanol to form
alkane.
Na/liquid NH3
R – CH = CH2 + ethanol R – CH2 – CH3

13. Curtius Rearrangement is a general reaction useful for the conversion of a carboxylic acid into primary amine containing one
carbon atom less than the parent acid. It involves the following sequence of reactions.
(1) SOCl2 Heat H2O/H+
RCOOH (2) NaN3 RCON3 R–N=C=O R – NH2

Carboxylic Acylazide Alkyl isocyanate (1o – Amine)

acid
14. Cannizzaro Reaction. Aldehydes which do not contain α-hydrogen atom, when treated with concentrated alkali solution
undergoes disproportionation i.e., self oxidation-reduction. As a result, one molecule of the aldehyde is reduced to the
corresponding alcohol at the cost of the other which is oxidised to the corresponding carboxylic acid. This reaction is called
Cannizzaro reaction. For example, formaldehyde on treatment with conc. NaOH solution gives methyl alcohol and sodium formate
whereas benzaldehyde gives benzyl alcohol and sodium benzoate.

O O

2 H – C – H + NaOH CH3 – OH + H – C – ONa

Formaldehyde (50%) Methyl alcohol Sodium formate
2 C6H5CHO + NaOH C6H5CH2OH + C6H5COONa
Benzaldehyde (50%) Benzyl alcohol Sodium benzoate
Similarly.
CH3 CH3 CH3
50% NaOH
CH3 – C – CHO CH3 – C – CH2OH + CH3 – C – COONa

CH3 CH3 CH3

2.2-Dimethylpropanal 2.2-Dimethylpropanol Sodium 2.2-Dimethylpropanoate
15. Carbylamine Reaction. When a primary amine (alphatic or aromatic) is warmed with chloroform and alcoholic KOH. it forms
an isocyanide or carbylamine having offensive smell. This reaction is called carbylamine reaction. For example,

CH3CH2NH2 + CHCl3 + 3 KOH ∆ CH3CH2N →

C + 3 KCl + 3 H2O
Ethylamine (alc.) Ethyl isocyanide or
Ethyl carbylamine

NH2 N →C
+ CHCl3 + 3 KOH ∆ + 3 KCl + 3 H2O
(alc.)
Aniline Phenyl isocyanide
or Phenyl carbylamine
Since secondary and tertiary amines (aliphatic or aromatic) do not give this reaction. it is used as a test for primary amines and also
for the distinction of primary amines from secondary and tertiary amines.
16. Claisen Condensation. The self condensation of two molecules of an ester containing alpha-hydrogens in presence of a strong
base such as sodium ethoside to form a β-keto ester is called claisen condensation. For example,
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 O O O O
C2H5ONa
CH3 – C – OC2H5 + H – –CH2 – – C – OC2H5 CH3– – C – CH2 – C – OC2H5 + C2H5OH
Ethyl acetate Ethyl acetate Ethyl acetoacetate
(A β- keto ester)

17. Claisen Rearrangement.

O – CH2 – CH – CH2 OH
CH2 – CH = CH2
∆
200oC

Allyl arylether α-Allyl phenol

18. Claisen-Schmidt Reaction. The condensation of benzaldehyde with alphatic aldehyde or ketone having α-hydrogen in the
presence of dilute alkali to form α, β-unsaturated carbonyl compound is known as Claisen-Schmidt reaction or Claisen reaction.
NaOH
e.g., (i) C6H5CH O + H2 CH.CHO 373 K C6H5CH = CH.CHO + H2O
Benzaldehyde Acetaldehyde Cinnamaldehyde
NaOH
(ii) C6H5CH O + H2 CH.CO.CH3 373 K C6H5CH = CHCOCH3 + H2O
Benzaldehyde Acetone Benzalacetone
(4-Phenyl-3-butene-2-one)
19. Clemmensen Reduction. The reduction of aldehydes and ketones to the corresponding hydrocarbons with amalgamated zinc
and concentrated hydrochloric acid is called Clemmensen reduction. For example.,
Zn/Hg + Conc. HCl
CH3COCH3 + 4[H] ∆ CH3CH2CH3 + H2O
Acetone Propane
Zn/Hg + Conc. HCl
C6H5COCH3 + 4[H] ∆ C6H5CH2CH3 + H2O
Acetophenone Ethylbenzene
This reduction works better with ketones than with aldehydes.
20. Coupling Reaction. The reaction of diazonium salts with phenols and aromatic amines to form azo compounds of the general
formula. Ar – N = N – Ar is called coupling reaction. In this reaction. the nitrogen atoms of the diazo group are retained in the
product. The coupling with phenols takes place in mildly alkaline medium while with amines it occurs under faintly acidic
conditions. For example,

–N+ ≡ NCl– + H– OH 273-278 K, OH– N=N OH + HCl

(pH 9-10)

Benzenediazonium Phenol p-Hydroxyazobenzene

Chloride (Orange dye)
21. Corey House Synthesis of alkanes involves reacting of an alkyl halide (preferably primary) with Lithium dialkyl copper
(R2CuLi) itself prepared by the interaction of an alkyl lithium and cuprous halide

Li CuX
2 R’X 2 R’ – Li R2’ CuLi
Alkyl halide Alkyl lithium Lithium dialkyl copper
R – X + R2’CuLi R – R’ + R’Cu + LiX
This reaction is particularly. useful for the preparation of unsymmetrical alkanes containing odd number of carbon atoms and
for the synthesis of higher alkanes.
Corey house reaction proceeds via nuclephilic substitution reaction. The nucleophile is furnished by the organometallic
compound.

22. Crossed Cannizzaro Reaction.

NaOH
HCHO + C6H5 CHO Re flux HCOONa + C6H5 – CH2OH
23. Dow’s Process. This process involves the treatment of chlorobenzene with aqueous sodium hydroxide solution (6-8%) at 633 K
under 300 atmospheres to form sodium phenoxide. which on acididfication gives phenol.
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 Cl ŌNa+ OH

633 K. 300 atm. HCl

+ NaOH –HCl + NaCl
Chlorobenzene 6-8% Sodium Phenoxide Phenol
24. Diazotisation Reaction. When a cold solution of a primary aromatic amine in a dilute mineral acid (HCl or H 2SO4) is treated
with a cold solution of nitrous acid (generated by the action of dil. HCl or dil. H 2SO4 on NaNO2) at 273-278 K. arenediazonium salt
is formed. This reaction is called diazotisation reaction. For example,
NaNO2 + HCl HONO + NaCl

NH2 N+ ≡ NCl

273-278 K
+ HONO + HCl + 2 H 2O

Aniline Benzenediazonium
(1 Aromatic Amine) chloride
25. Diel-Alder Reaction. The reaction between α, β-unsaturated carbonyl compound (dienophile) and a conjugated diene to form an
addition product (adduct). is known as Diel-Alder reaction.
CH2 CH2
CH CH2 CH CH2
+ 373 K or
CH CH2 CH CH2
CH2 CH2
1, 3-Butadiene Ethene Cyclohexene
(Conjugated diene) (Dienophile) (Adduct)
26. Esterification Reaction. Alcohols react with carboxylic acids in oresence of dry HCl gas or a few drops of conc. H 2SO4 as
catalyst to form esters. For example,
O O
Conc. H2SO4
R – C – OH + HO – R’ R – C – OH + HO – R’
Carboxylic acid Alcohol Ester
O O
Conc. H2SO4
e.g., CH3 – C – OH + HO – CH2CH3 CH3 – C – OCH2CH3 + H2O
Acetic acid Ethyl alcohol Ethyl acetate
This reaction which is show and reversible is called esterification reaction. When dry HCl gas is used as a catalyst, the reaction
is commonly known as Fischer-speier esterification.

27. Dehydrohalogenation. (1. 2-Elimination or β-elimination).

This reaction involves the treatment of an alkyl halide with concentrated alcoholic solution of a strong base like potassium
hydroxide to form alkene.
∆
R – CH2 – CH2 – Br + KOH R – CH = CH2 + KBr + H2O
Alkyl bromide Conc. Alkene
(alc.)
e.g., C2H5 – Br + KOH H2C = CH2 + KBr + H2O
Ethyl bromide Ethylene
Saytzeff’s Rule. If the structure of an alkyl halide is such that it can undergo dehydrohalogenation in two different ways, the preferred
product is that alkene which contains least number of hydrogen atoms on doubly bonded carbon atoms. This is due to the fact that more
substituted alkene being more stable is formed more readily.
Br
∆
e.g., CH3 – CH - CH2 – CH3 + KOH CH3 – CH = CH – CH3 + CH2 = CH – CH2 – CH3
2-Bromobutane (alc.) Butene-2 Butene-1
(80%, more substituted) (20%, less substituted)
28. Etard Reaction. The oxidation of toluene with chromyl chloride (CrO2Cl2) in CCl4 or CS2 to give benzaldehyde is called Etard
reaction. In this reaction, the chromyl chloride first forms a brown complex with Toluene which is separated and then decomposed
with H2O to give benzaldehyde. For example,
OCr(OH)Cl2
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 CH3 CH CHO
OCr(OH)Cl2
2 CrO2Cl2 H2O
CCl4
Toluene Brown complex Benzaldehyde
29. Fries Rearrangement. Phenyl ester undergoes rearrangement in the presence of anhydrous aluminium chloride to form o- or p-
hydroxyketone. or a mixture of both. This rearrangement in which acyl group migrates from phenolic oxygen to ortho or para
position is known as Fries rearrangement.
OCOR OH OH
COR
AlCl3 +

Phenyl ester o-Hydroxyketone COR

p-Hydroxyketone
OCOCH3 OH OH
COCH3
AlCl3 +

Phenyl acetate o-Hydroxyacetophenone COCH3

p- Hydroxyacetophenone
Generally low temperatures (333 K or less) favour the formation of p-isomer. Whereas high temperature (above 433 K) favour
the o-isomer.
30. Fittig Reaction. This reaction is a useful variation of Wurtz reaction. It involves the reaction between two molecules of an aryl
halide with sodium in presence of dry ether to form a diaryl. For example,
Dry ether
Cl + 2 Na + Cl + 2 NaCl

Chlorobenzene (Two molecules) Diphenyl or Biphenyl

31. Friedel-Crafts Reaction. This reaction is used for introducing an alkyl or an acyl group into an aromatic compound in presence
of a Lewis acid catalyst. The most commonly used Lewis acid catalyst is anhydrous AlCl 3 while other catalysts which have been
used are BF3. FeCl3 SnCl4 etc.
(a) Friedel-Crafts Alkylation. Benzene (and other aromatic compounds) reacts with alkyl halides in presence of anhydrous
aluminium chloride to form alkylbenzenes. For example,
CH3

Anhyd. AlCl3
+ CH3Cl + HCl
Methyl chloride
Benzene Toluene

CH2CH3

Anhyd. AlCl3
+ CH3CH2Br + HBr
Ethyl bromide
Benzene Ethylbenzene

The Friedel-Crafts alkylation of benzene with olefins and alcohols is usually carried out in presence of protonic acids such as HF,
H2SO4 or H3PO4. For example,
CH

H3PO4 CH3
+ CH3CH = CH2 CH
Propene CH3
Benzene
Isopropylbenzene or Cumene
(b) Friedel-Crafts Acylation. Benzene (and other aromatic compounds) reacts with acid chlorides or anhydrides in presence of
anhyd. AlCl3 to form ketones. For example,

Anhyd. AlCl3
+ CH3COCl COCH3 + HCl

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 Acetic anhydride
Benzene
Acetophenone

Anhyd. AlCl3
+ (CH3CO)2O COCH3 + CH3COOH
Acetic anhydride
Benzene
Acetophenone

Anhyd. AlCl3
+ CIOC CO HCl

Benzene Benzoyl chloride Benzophenone

32. Fermentation. It is the process of decomposition or organic compounds under the influence of enzymes which are complex
nitrogenous organic substances. For example,
Invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose Glucose Fructose
(in molasses)
Zymase
C6H12O6 2 C2H5OH + 2 CO2
Ethyl alcohol
(18%)
The fermented liquor obtained by the above method is known as ‘was’ and contains upto 18% ethanol. It can be concentrated by
fractional distillation.
33. Gattermann Aldehyde Reaction.
OH OH OH
CH = NH CHO
AlCl3 H2O/H–
+ HCN + HCl

Salicylaldehyde
34. Gattermann Aldehyde Synthesis.
H – C ≡ N + H – Cl H – C = NH

Cl
H CH = NH
AlCl3
+ Cl – CH = NH –HCl

O HH
CH = NH CHO

H–
+ H2O NH3 +
35. Garbriel phthalimide Synthesis. In this reaction phthalimide is converted into its potassium salt by treating it with alcoholic
potassium hydroxide. Then potassium phthalimide is heated with an alkyl halide to yield an N-alkylphthalimide which is
hydrolysed to phthalic acid and a primary amine by heating with HCl or KOH solution.

CO CO CO

NH KOH (alc.) NK C2H5l NC 2H5

–H2O –Kl
CO CO CO
Phthalimide Pot. Phthalimide N-Ethylphthalimide
COOH
H2O/H+
+ C2H5NH2
COOH Ethyl amine
Phthalic acid

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 This is synthesis is very useful for the preparation of pure aralkyl and aliphatic primary amines. However aromatic primary amines
cannot be prepared by this method.
36. Gattermann Koch Reaction. This reaction consists of passing carbon monoxide mixed with hydrogen chloride gas under 70
atm. into benzene at 298 K in the presence of anhydrous aluminium chloride and a small amount of cuprous chloride. Benzaldehyde
is produced.
CO + HCl HCOCl
Formyl chloride
O CHO
AlCl3
+ Cl – C – H + HCl

Benzene Formyl Benzaldehyde

Chloride
This reaction is used to introduce aldehyde group into the benzene ring.

37. Hydroboration Oxidation. Hydroboration oxidation of alkene results in the formation of alcohol. Alcohol formed from
unsymmetrical alkene in this reaction is in accordance with antimarkownikoff rule. The reaction involves two steps.
(i) Hydroboration. In this step. diborane (B2H6) reacts with an alkene to form trialkylborane. Consider its reaction with propane.

6 CH3 – CH = CH2 + B2H6 2 (CH3 – CH2 – CH2)3 B

Tri-n-propyl borane
(ii) Oxidation. In this step. trialkyl borane is treated with alkaline hydrogen peroxide to form trialkoxy borane. It is then hydrolysed to
alcohol.
OH–
(CH3 – CH2 – CH2)3B+ 3 H2O2 3 CH3 – CH2 – CH2OH + H3BO3
n-propyl alcohol
38. Haloform Reaction (Iodoform Reaction). All compounds containing the grouping CH3CHOH – (i.e. methylcarbinols such as
Ethanol. 2-Propanol. 2-Butanol etc.) or CHCO – (i.e. methyl ketones such as Propanone. Butanone. 2-Pentanone. Acetophenone
etc.) when treated with a halogen and excess of alkali (i.e. sodium hypohalite. NaOX) form haloforms. If the halogen used is iodine.
yellow precipitates of iodoform are formed and the reaction is called iodoform reaction. For example,

CH2CH2OH + 4 I2 + 6 NaOH CHI3 + HCOONa + 5 NaI + 5 H2O

Ethanol Iodoform
CH3CHOHCH3 + 4 I2 + 6 NaOH CHI3 + CH3COONa + 5 NaI + 5 H2O
2-Propanol Iodoform
CH3COCH3 + 3 I2 + 4 NaOH CHI3 + CH3COONa + 3 NaI + 3 H2O
Propanone Iodoform
CH3COCH2CH3 + 3 I2 + 4 NaOH CHI3 +CH3CH2COONa + 2 NaI + 3 H2O
2-Butanone Iodoform
C6H5COCH3 + 2 I2 + 4 NaOH CHI3 +C6H5COONa + 3 NaI + 3 H2O
Acetophenone Iodoform
Iodoform reaction is widely used for the distinction of methylcarbinols and methyl ketones from other alcohols and ketones.
39. Hell-Volhard Zelinsky Reaction. The reaction of an aliphatic carboxylic acid containing α-hydrogens with Cl2 or Br2 in
presence of a small amount of red phosphorous to give α-haloacid is called Hell-Volhard Zelinsky (H.V.Z.) reaction. With excess
of halogen, all the α-hydrogen atoms of an aliphatic carboxylic acid are replaced by halogen atoms. For example,
α Cl2/P Cl2/P Cl2/P
CH3COOH –HCl ClH2COOH –HCl Cl2CHCOOH –HCl Cl3COOH
Acetic acid Monochloro Dichloro- Trichloroacetic acid
acetic acid acetic acid

β Br2.P α Br2.P
CH3CH2COOH –HBr CH3CHBrCOOH –HBr CH3CBr2COOH
Propionic acid α-Bromopropionic acid α. α-Dibromopropionic acid

Br2.P
No further substitution
40. Hoffmann Elimination. When a quaternary ammonium halide is treated with , silver hydroxide. silver. Halide precipitates and a
halogen free solid quaternary ammonium hydroxide is formed which on heating forms a 3 o amine and an alkene.
This reaction is an example of nucleophilic β – elimination reaction.

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 R(R’)3N+ X– + AgOH  R(R’3N+) OH–  AgX + R (R’3N+) OH– ∆ Alkene + R’3N+ H2O
Quarternary Quarternary Quarternary 3o - amine
ammonium ammonium ammonium
halide hydroxide hydroxide
∆
For example. CH3CH2CH2CH2N+ (CH3)3OH– (CH3)3N + H2O + CH3CHCH = CH2
Trimethyl-n- butyl 3o Amine 1-Butene
Ammonium hydroxide
This degradation reaction. when applied to an unknown amine involves exhaustive methylation, treatment with AgOH and
pyrolysis of quarternary ammonium hydroxide. The identification of the alkene formed during degradation can give an idea about the
structure of unknown amine.
41. Hoffmann Bromide Reaction or Hoffmann Degradation of Amides or Hoffmann’s Rearragnement. The conversion
of a primary amide to a primary amine containing one carbon atom less than the original amide on heating with mixture of Br2 in
presence of NaOH or KOH (i.e. NaOBr or KOBr) is called Hoffmann bromomide reaction or Hoffmann degradation of amides. For
example,
∆
CH3CONH2 + Br2 + NaOH CH3NH2 + 2 NaBr + Na2CO3 + 2 H2O
Acetamide Methylamine
∆
C2H5CONH2 + Br2 + 4 KOH CH3CH2NH2 + 2 KBr + K2CO3 + 2 H2O
Propionamide Ethylamine
∆
C6H5CONH2 + Br2 + 4 KOH C6H5NH2 + 2 KBr + K2CO3 + 2 H2O
Benzamide Aniline
This reaction is extremely useful for converting a higher homologue to the next lower homologue. i.e., for stepping down or
descending a homologous series.
42. Hoffmann’s Method for the Separation of Amines. The mixture of amines is treated with diethyloxalate
(a) The primary amine forms a crystalline solid (a substituted oxamide)

COOC2H5 COOCHR
+ 2 R – NH2 + + 2 C2H5OH
COOC2H5 COOCHR
(Diethyl oxalate) Substituted
oxamide (Solid)
(b) The secondary amine forms a liquid dialkyl oxamic ester

COOC2H5 CONR2
+ R2NH2 + 2 C2H5OH
COOC2H5 2o-Amine COOC2H5
(Diethyl oxalate) Dialkyloxamic
ester (liquid)
(c) The tertiary amines do not react.
The mixture containing substituted oxamide, oxamic ester is distilled. Unreacted 3o-amine is distilled over. The residual mixture
contains substituted oxamide (solid) and oxamic ester (liquid) and the two can be separated by simple filteration. Both the oxamide and
oxamic ester. when treated separately with a strong alkali regenerates the corresponding amines.
CONHR COOK
+ 2 KOH + 2 RNH2
CONHR COOK 1o-Amine
(Substituted oxamide) Potassium oxalate

CONR2 COOK
+ 2 KOH + R2NH
COOC2H5 COOK 2o-Amine
Oxamic ester (Potassium oxalate)
43. Hunsdiecker Reaction or Borodine Hunsdiecker Reaction. The decomposition of the silver salt of a carboxylic acid with
Br2 in refluxing CCl4 to form an alkyl or aryl bromide with one carbon less than the original acid is called Hunsdiecker reaction.
For example,
CCl4. 350 K
RCOOAg + Br2 R – Br + CO2 + AgBr
Reflux
CCl4. 350 K

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 CH3CH2COOAg + Br2 CH3CH2 – Br + CO2 + AgBr
Silver propionate Reflux Ethyl bromide

CCl4. 350 K
C6H5COOAg + Br2 C6H5 – Br + CO2 +AgBr
Silver benzoate Reflux Bromobenzene
Like Hoffmann bromamide reaction. Hunsdiecker reaction is also used for stepping down the homologous series.
44. Internal Cannizzaro’s Reaction.

CHO COONa
NaOH
CHO Reflux CH2OH
45. Kolbe Electrolytic Reaction. This reaction is used to prepare some alkanes and alkynes by electrolysis of aqueous solution of
sodium or potassium salt of suitable acids. For example,
(a) Ethane is produced when an aqueous solution of potassium acetate is electrolysed
2 CH3COOK 2 CH3COO– + 2 K+ (Ionization)
Potassium acetate
2 H 2O 2 OH– + 2 H+ (Ionization)
– -
At anode : 2 CH3COO – 2 e CH3–CH3 + 2 CO2
Ethane
At cathode : Both+ and H+ are present but H+ ions are preferentially discharged due to their lower discharge potential.
2 H+ + 2 e - 2H H2
(b) Ethylene is produced when potassium salt of succinic acid is electrolysed.

CH2COOK CH2COO
+ 2 K+ (Ionization)
CH2COOK CH2COO
Potassium succinate
2 H 2O 2 OH– + 2 H+ (Ionization)
CH2COO– CH2COO CH2
At anode : – 2 e- + 2 CO2
–
CH2COO CH2COO CH2
(Unstable) Ethylene
At cathode : H2 is produced as above
2 H+ + 2 e - H2
(c) Acetylene is produced when potassium maleate or fumarate is electrolysed.

CHCOOK CHCOO–
+ 2 K+ (Ionization)
–
CHCOOK CHCOO
Potassium maleate
2 H 2O 2 OH– + 2 H+ (Ionization)
CHCOO– CHCOO –
CH
At anode : – 2 e- + 2 CO2
–
CHCOO CHCOO– CH
(Unstable) Ethyne
At cathode : H2 is produced as above.
46. Kolbe-Reaction or Kolbe-Schmidt Reaction. Sodium phenoxide reacts with carbon dioxide under pressure (4-7
atmospheres) at 400 K to form sodium salicylate which upon acidification with mineral acids gives salicyclic acid. This reaction is
called Kolbe reaction.
ONa OH OH
COONa COOH
4-7 atm H+
+ CO2 400 K H2O

Sodium phenoxide Sodium salicylate Salicylic acid

(Major product)
A small amount of p-hydroxybenzoic acid is also formed. But the two isomers are readily separated by steam distillation. The o-
isomer being more volatile steam distils leaving behind the p-isomer.

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 47. Koop Synthesis. Α-keto acids are treated with ammonia to form the corresponding amine which on catalytic reduction forms an
amino acid.

O NH NH2

CH3 – C – COOH + NH3 CH3 – C – COOH H2/Pd CH3 – CH – COOH

–H2O or Na/EtOH
2-Ketopropanoic acid Alanine
Pyruvic acid
48. Koch Reaction.
H3PO4
H2C = CH2 + CO + H2O 573-623 K H3C – CH2 – COOH
49. Liebermann Nitroso Reaction. Both aliphatic and aromatic 2o amines react with nitrous acid (generated, in situ ,by the action
of dil. HCl on NaNO2) to give N-nitrosoamines which are generally yellow neutral oily compounds and are insoluble in dilute
mineral acids.
R2 NH + HO – N = O R2N – N = O + H2O
2o Amine N-Nitrosodialkylamine
Nitrosoamines on warming with a crystal of phenol and conc. H 2SO4 form a green solution which when made alkaline with aqueous
NaOH turns deep blue and then red on dilution. This reaction is called Liebermann nitroso reaction and is used as a test for secondary
amines.
50. Luca’s Reaction. This reaction affords a test for distinguishing primary, secondary and tertiary alcohol. It consists in treating an
alcohol with Luca’s reagent which is an equimolar mixture of conc. HCl and anhydrous ZnCl2. Appearance of cloudiness indicates
the conversion of alcohol into alkyl chloride.
Anhd.
R – OH + HCl ZnCl2 R – Cl + H2O
Alcohol Alkylchloride
(Cloudiness)
(i) If cloudiness appears immediately then tertiary alcohol is present.
(ii) If cloudiness appears within five to ten minutes, then secondary alcohol is present.
(iii) If no cloudiness appears at room temperature, but cloudiness appears only upon heating, then primary alcohol is present.
51. Michael Condensation. The addition reaction between α, β-unsaturated carbonyl compound and a compound containing active
methylene group such as malonic ester, acetoacetic ester is known as Michael condensation. For example,
O O
Piperidine or
C6H5 – CH = CH – C – CH3 + CH2(COOC2H5)2 C2H5ONa (Base) C6H5 – CH – CH2 – C – CH3
Benzalacetophenone Malonic ester
CH(COOC2H5)2
Addition product
52. Meerwein-Ponndorf-Verley Reduction. The reduction of carbonyl compounds (aldehydes or ketones) to alcohols by
aluminium isopropoxide in isopropyl alcohol is known as Meerwein-Ponndorf-Verley reduction. The reagent aluminium
isopropoxide is specific as it does not affect the reducible groups such as double bond or a nitro group.
CH3 CH3
[(CH3)2 CHO]3Al
C=O CHOH

CH3 CH3
Acetone Isopropyl alcohol
53. Oxo Pocess. In this process, alkenes are treated with carbon monoxide and hydrogen at high temperature and pressure and in the
presence of cobalt carbonyl [Co(CO)4] as catalyst to get aldehydes. These are converted into primary alcohols by catalytic
hydrogenation. For example,
[Co(CO)4] H2/Ni
CH2 = CH2 + CO + H2 CH3 – CH2 – CHO CH2 – CH2 – CH2OH
Ethene Propanal Propanol
54. Ozonolysis of alkenes. On bubbling ozone through alkene solution in an inert solvent like CCl 4 at low temperature. ozonide (a
viscous oily liquid) is formed which on decomposition with water in the presence of zinc dust as a reducing agent forms carbonyl
compound (aldehyde and/or ketone). The complete process of preparing the ozonide and decomposing it is known as ozonolysis.

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 O
CCl4 H2O/Zn
C=C + O3 – C –– – C  C C –H2O2 C=O+O=C

O O O O

O
Alkene Molozonide Ozonide Carbonyl compounds
O
CCl4 H2O/Zn
e.g., H2C = CH2 + O3 H2C – CH2  H2C CH2 –H2O2 HCHO + HCHO

O O O O

O
Ethylene Molozonide Ozonide Formaldehyde
55. Perkin Reaction. When an aromatic aldehyde is heated with some aliphatic acid anhydride in presence of sodium salt of the same
acid. the product thus obtained on acid hydrolysis gives an α, β-unsaturated acid. This reaction is called Perkin reaction. For
example, when benzaldehyde is heated with acetic anhydride in presence of sodium acetate the product thus formed on hydrolysis
gives cinnamic acid.
H2CHO C6H5CH = CHCO
C6H5 – CH = O + O CH3COONa. 453 K O
Benzaldehyde CH3CO –H2O2 CH3CO
Acetic anhydride
H2O. Boil
(Hydrolysis) C6H5CH = CHCOOH + CH3COOH
Cinnamic acid
56. Pyrolysis or Cracking. Alkanes when subjected to high temperature (770 – 790 K) in the presence of catalyst are decomposed
into smaller molecules. This process of decomposition of big molecules into a number of simpler molecules by the application of
heat is called Pyrolysis or Cracking. The cracking of alkanes involves the cleavage of C – C and C – H bonds. For example butane
decompose as follows at about 770 K.
C2H6 + C2H4
Ethane Ethene
Cracking CH4 + C3H6
C4H10 770 K Methane Propene
C4H8 + H2
Butene
The products formed during cracking depends upon
(i) Structure of starting alkane. (ii) The pressure applied and (iii) Use of Catalyst.
57. Pinacol Pinacolone Rearrangement involves the acid catalyzed dehydration of 1.2-glycols (Pinacols) followed by a
rearrangement of the carbon skeleton to form ketones. For example,
CH3 CH3 CH3

CH3 ––– C ––––– C –– –– CH3 H+ CH3 ––– C ––––– C –– –– CH3

OH OH O CH3
(Pinacol) (Pinacolone)
Such rearrangements are known as Pinacol-pinacolone rearrangements or simply Pinacol rearrangements.
58. Reimer-Tiemann Reaction. Treatment of phenol with chloroform in presence of aqueous sodium or potassium hydroxide at
340 K followed by hydrolysis of the resulting poduct gives 2-hydroxybenzaldehyde (salicylaldehyde). This reaction is called
Reimer-Tiemann reaction*.
OH ONa ONa
CHCl2 CH(OH)2
NaOH, 340 K 2 NaOH
+ CHCl3 –NaCl, –H2O –2 NaCl –H2O

ONa OH
CHO CHO
dil. HCl
–NaCl (Salicylaldehye)
A small amount of p-hydroxybenzaldehyde is also formed.
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 If instead of chloroform. Carbon tetrachloride is used, salicylic acid is formed.
OH ONa ONa
CCl3 CH(OH)3
NaOH 3 NaOH
+ CCl4 340 K –3 NaCl –H2O

ONa ONa OH
COOH COONa COOH
NaOH dil. HCl
–H2O –2 NaCl

59. Rosenmund Reduction. Catalytic reduction of acid chlorides to the corresponding aldehydes is called Rosenmund reduction.
This reaction is carried out by passing H2 gas through boiling o-xlene solution of the acid chloride in presence of Pd catalyst
supported over BaSO4 (partially poisoned by addition of sulphur or quinoline).
O O
Pd/BaSO4. S
R––– C –– Cl + H2 Boiling Xylene R– C –– H + HCl
Acid chloride Aldehyde

O O
Pd/BaSO4. S
CH3–– C –– Cl + H2 Boiling Xylene CH3 – C –– H + HCl
Acetyl chloride Acetaldehyde

O O
Pd/BaSO4. S
C6H5–– C –– Cl + H2 Boiling Xylene C6H5 – C –– H + HCl
Benzoyl chloride Benzaldehyde
The function of BaSO4 and S (or quinoline) is to poison the catalyst so that it does not allow the further reduction of aldehydes to
alcohols.
60. Reductive Amination. The reaction of carbonyl compounds (aldehydes or ketones) with ammonia followed by reduction with
hydrogen in the presence of nickel as catalyst at 373 K and 150 atmosphere to form primary amine is known as Reductive
amination. For example,
H H
H2
CH3 ––– C = O + NH3 CH3 ––– C = NH Ni CH3CH2NH2
Acetaldehyde –H2O Ethylamine
CH3 CH3 CH3
H2
CH3 ––– C = O + NH3 CH3 ––– C = NH Ni CH3 –– CH––NH2
Acetone –H2O Isopropylamine
61. Reformatsky Reaction. It consists in treating an aldehyde or a ketone with an α-bromoester and metallic zinc in the presence of
dry ether or benzene. This addition product initially formed is decomposed by dilute mineral acids to yield β-hydroxy esters.
H H
Ether
CH3 ––– C = O + BrCH2COOC2H5 + Zn CH3 ––– C –– OZnBr
Acetaldehyde
CH2COOC2H5
Addition product
H
HCl Cl
CH3 ––– C –– OH + Zn
Br
CH2COOC2H5
Ethyl-β-hydroxybutyrate
62. Sandmeyar Reaction. The conversion of benzenediazonium chloride to chlorobenzene, bromobenzene and benzonitrile on
treatment with CuCl/HCl. CuBr/HBr or CuCN/KCN respectively is called Sandmeyer reaction.
N+ ≡ NCl– Cl–

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 CuCl/HCl + N2
∆

Benzenediazonium chloride Chlorobenzene

N+ ≡ NCl– Br

CuBr/HBr + N2 + Cl
∆

Benzenediazonium chloride Bromobenzene

N+ ≡ NCl– CN

CuCN/KCN + N2 + Cl
∆

Benzenediazonium chloride Benzonitrile

It may be noted that in this reaction. it is the halogen attached to copper which actually enters the benzene ring.
63. Schmidt’s Reaction involves the reaction of hydrozoic acid (N3H) with a carboxylic acid in presence of H 2SO4 leading to the
formation of a primary amine containing one carbon atom less than the parent acid.
H2SO4
R – COOH + HN3 R – NH2 + CO2 + N2
Carboxylic Hydrazoc Primary amine
acid acid
64. Tischenko Reaction. In the presence of aluminium ethoxide, aldehydes (with or without α-hydrogen) form esters. This is known
as Tischenko reaction.
Like Cannizzaro reaction, one molecule of aldehyde gets oxidized to the corresponding acid whereas another molecule gets
reduced to alcohol. However these acid and alcohol appear as an ester.
H2SO4
e.g., (i) 2 CH3CHO –H2O [H3C – COOH + C2H5OH] CH3COOC2 H5
Acetaldehyde Ethyl acetate
Al(OEt)3
(ii) 2 CH2 = CH – CHO –H2O CH2 = CH – COOCH2CH = CH2
Acraldehyde Allyl acrylate
65. Ullmann Reaction. When iodobenzene is heated with copper powder in a sealed tube, diphenyl is produced. This reaction is
called Ullmann reaction.

∆
I + 2 Cu + I Sealed tube + 2 CuI

Iodobenzene Diphenyl
Aryl chlorides and aryl bromides usually do not react unless an electron-withdrawing group is present at o-and/or p-position w.r.t.
the halogen atom. For example,
NO2 NO2 NO2 NO2

∆
Cl + 2 Cu + Cl Sealed tube + 2 CuI

o-Chloronitrobenzene 2.2’ – Dinitrodiphenyl

66. Victor Mayer’s Reaction. The reaction affords a test for distinguishing primary, secondary and tetiary alcohols and consists of
the following steps :
Primary alcohol (1o) Secondary alcohol (2o) Tertiary alcohol (3o)

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 R – CH2OH R R
CHOH R––––– C –– OH
R R

P + I2 P + I2 P / I2

R – CH2 I R R
Iodo derivative CHI R––––– C –– I
R R
Iodo derivative Iodo derivative

AgNO2 AgNO2 AgNO2

R – CH2 – NO2 R R
Nitroalkane (1’) CH – NO2 R––––– C –– NO2
R R
Nitroalkane (2’) Nitroalkane (3’)

O = NOH HONO HONO

R
R – C – NO2 C –– NO2 No action
R
NOH NO
Nitrolic acid Pseudonitrol

aq. NaOH aq. NaOH aq. NaOH

Red colour Blue colour Colourless solution

67. Wittig Reaction. On treating carbonyl compounds (aldehydes or ketones) with an ylide. the carbonyl oxygen is replaced by the
group = CRR’. This reaction is known as Wittig reaction. For example,
C6H5CHO + (C6H5)3 P = CH2 C6H5 –– CH = CH2 + (C6H5)3 PO
Benzaldehyde Methylenetriphenyl Styrene Triphenyl
Phosphorane Phosphine
(ylide) oxide
C6H5 C6H5
C = O + (C6H5)3 P = CH2 C = CH2 + (C6H5)3 PO
C6H5 C6H5
Benzophenone 1, 1-Diphenylethylene
68. Williamson synthesis. The reaction of alkyl halides with sodium alkoxide or sodium phenoxide to form ethers is called
Williamson synthesis. For example,
R––X + R’––ONa R––O––R’ + NaX
Alkylhalide Sod. alkoxide Ether
CH3I + CH3CH2ONa CH3––O–– CH2 CH3 + NaI
Methyl iodide Sod. ethoxide Ethyl methyl ether
CH3CH2I + CH3CH2ONa CH3CH2––O–– CH2 CH3 + NaI
Ethyl iodide Sod. ethoxide Diethyl ether

PhONa + CH3I PhOCH3+ NaI

Sod. Phenoxide Methyl iodide Anisol
This is one of the best methods for the preparation of both simple and mixed ethers.
69. Wolff-Kishner Reduction. The reduction of aldehydes and ketones to the corresponding hydrocarbons by heating them with
hydrazine and KOH or potassium tart-butoxide in a high boiling solvent such as ethylene glycol is called Wolf-Kishner reduction.
NH2NH2 KOH. glycol
R – CH = O –H2O R – CH = NNH2 453-473 K R – CH3 + N2
Aldehyde Hydrazone

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 NH2NH2/KOH glycol
CH3COCH3 453-473 K CH3 CH2 CH3
Acetone Propane CH2 CH3

COCH3
NH2NH2/KOH glycol
453-473 K
Acetophenone Ethylbenzene
70. Wurtz Reaction. It involves the interaction of two molecules of an alkyl halide (preferably bromide or iodide) with metallic
sodium in presence of dry ehter to form symmetrical alkanes containing double the number of carbon atoms present in the alkyl
halide. For example,
Dry ether
R – X + 2 Na + X – R R – R + 2 NaX
Alkyl halide Alkane
Dry ether
e.g., CH3 – Br + 2 Na + Br – CH3 CH3CH3 + 2 NaBr
Methyl bromide Ethane
Dry ether
CH3CH2 – I + 2 Na + I – CH2CH3 CH3CH2CH2CH3 + 2 NaI
Ethyl iodide Butane
Thus, Wurtz reaction is a convenient method for the preparation of symmetrical alkanes (R-R), i.e. alkanes containing even number
of carbon atoms.
However, if two different alkyl halides are used, a mixture of three alkanes is actually obtained. For example.
Dry ether
CH3 – I + 2 Na + I – CH2CH3 CH3CH2CH3 + 2 NaI
Methyl iodide Ethyl iodide Propane
Dry ether
CH3 – I + 2 Na + I – CH3 CH3CH3 + 2 NaI
Methyl iodide Ethane
Dry ether
CH3CH2 – I + 2 Na + I – CH2CH3 CH3CH2CH2CH3 + 2 NaI
Ethyl iodide Butane
The boiling points of these alkanes are very close and hence cannot be separated by fractional distillation. That is why Wurtz
reaction is only useful for the preparation of symmetrical alkanes and not for the preparation of unsymmetrical alkanes, i.e., alkanes
containing odd number of carbon atoms.
71. Wurtz-Fittig Reaction. This is a variation of Wurtz reaction and is used for preparing homologues of benzene by warming a
mixture of an aryl halide and an alkyl halide with metallic sodium in presence of dry ether. For example,

Dry ether
(i) PhBr + 2 Na + Br––CH3 ∆ Ph-CH3 + 2 NaBr

Bromobenzene Methyl bromide Toluene

Biphenyl and ethane are obtained as by-products

Dry ether
(ii) PhBr + 2 Na + Br–– CH2CH3 ∆ Ph- CH2CH3 + 2 NaBr

Bromobenzene Ethyl bromide Ethylbenzene

Biphenyl and n-butane are obtained as by-products.

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