Organic reaction mechanism through problem solving approach

Halo-hydroxylation Reaction and Aliphatic Nucleophilic Substitution 5.. Friedel Craft Acylation and Condensation Reaction 28.. Aromatic Nucleophilic Substitution by Elimination –Addition

Organic Reaction Mechanism

: Through Problem Solving Approach

Assistant Professor

Department of Chemistry, K.T.H.M College, Nashik-422005

Maharashtra, India

Organic Reaction Mechanism:

Through Problem Solving Approach

ISBN : 978-93-5267-423-7

All rights reserved

No part of this book may be reproduced in any form, byphotostat, microfilm,xerography or any other means or incorporated into any information retrievalsystem, electronic or mechanical, without the written permission of thecopyright owner

PREFACE

mechanism for themselves Almost all available books, on organic reactionmechanism describe reactions and their conversions This book confronts thestudent with the organic reaction mechanism by showing how the reagent andstarting molecule act together in the reaction The reaction mechanismapproach is learnt by students from this book who then teaches themselveshow to use mechanism by solving a series of problems.

It is not a conventional text book with detailed text explanation Inshort this book understand quickly and giving information about reactionmechanism Also the student has planned sequence of problems todemonstrate the use of each new mechanism and to test his understanding of

it Each problem is followed by possible reaction mechanism and shortexplanation, So that if the student fails to solve a problem he will stillunderstand the answer better for having attempted the problem himself Thestudent therefore has the possibility of continuous self assessment through theuse of large number of problems

There are some excellent books written about organic reactionmechanism but they mostly present complete synthesis not reactionmechanism I have tried in this book to teach student to speak the language ofreaction mechanism themselves This book is originally written for the firstyear students

The programme aims to allow students to teach themselves but itshouldn’t mean any less work for them Because students discover what theydon’t know, they should have more sensible questions to ask when they weresolving reaction mechanism My aim is to give you more time for realteaching The book should do the ground work and you should be able to setsuitable programme and discuss then profitably The book itself has plenty ofproblems of this sort

main aim is to suggest a mechanistic approach to the organic reactions Youtherefore need to have a reasonable grounding in organic chemistry so thatyou are familiar with most basic organic reactions If you are first yearstudent with no much experience of organic chemistry or limited knowledge

of organic reactions in practice you will probably be able to work straightthrough the book to learn the actual reaction mechanism The point of booklearning is that you learn at your own pace and that you yourself check onyour own progress

1 Nitration Reaction

2 Nucleophilic Substitution by NGP

3 Aromatic Nucleophilic Substitution

4 Halo-hydroxylation Reaction and Aliphatic Nucleophilic

Substitution

5 Neighbouring Group Participation by sigma bond

6 Aromatic Electrophilic Substitution and Diazotization

7 Aromatic Nucleophilic Substitution

8 Addition Reaction

9 Nitration Reaction

10 Aromatic Electrophilic Substitution

11 Neighbouring Group Participation by sigma bond

12 Elimination Reaction with Rearrangement

13 Rearrangement

14 Pyrolytic Elimination Reaction

15 Gattermann Koch Reaction

16 Pinacol Pinacolone Rearrangement

17 Alkylation and Dehydration Reaction

18 Neighbouring Group Participation by heteroatom

19 Aromatic Nucleophilic Substitution and condensation

20 Aromatic Electrophilic Substitution

21 Addition Reaction

22 Methylation and Vilsmeyer Haack Formylation Reaction

23 Elimination and Addition Reaction

24 Aromatic Nucleophilic Substitution

26 Diazotization Reaction with stereochemistry

27 Friedel Craft Acylation and Condensation Reaction

28 Addition Reaction: Bromination

36 Cyclisation by using PTSA

37 Aromatic Nucleophilic Substitution by Elimination –Addition

Mechanism

38 Diazotization Reaction with stereochemistry

39 Neighbouring Group Participation by heteroatom and Aliphatic

Nucleophilic Substitution

40 Friedel Craft Alkylation Reaction and Aromatization Reaction

41 Riemann Tiemann Reaction

42 SN2 Mechanism

43 N-Acylation and Nitration Reaction

44 Addition Reaction

45 Aromatic Nucleophilic Substitution by Elimination –Addition

Mechanism and Diazo coupling reaction

46 Grignard Reaction

47 Halogenation Reaction and amide formation

48 Elimination and Addition Reaction

50 Aliphatic Nucleophilic Substitution and Chlorination by SNi

mechanism and SN2 Mechanism

51 Friedel Craft Acylation and Clemmensons Reduction

52 Nitration ans N-Acylation Reaction

53 Chlorination with stereochemistry and Elimination Reaction by

Saytzeff rule

54 Diazotization Reaction with stereochemistry and oxime formation

55 Hydroboration – Oxidation Reaction

56 SNi Mechanism

57 Nitration and Aromatic Nucleophilic Substitution

58 Halogenation and Nitration Reaction Aromatic Electrophilic

Substitution

59 Vilsmeyer Haack Formylation Reaction

60 Friedel Craft Acylation Reaction

61 Hunds Dicker Reaction

62 Oxidation and Nitration Reaction

63 Aldol Condensation Reaction

64 Epoxidation and Hydrolysis

65 Vilsmeyer Haack Formylation Reaction

66 Halogenation Reaction and Neighbouring Group Participation by

Pi bond

67 Halogenation: Aromatic Electrophilic Substitution

68 Halogenation: Aromatic Electrophilic Substitution

69 Methylation and Nitration Reaction

70 Rearrangement

71 Diazotisation and Diazo coupling Reaction

72 Rearrangement

74 Vilsmeyer Haack Formylation Reaction

75 Dehydration: Elimination Reaction

76 Aliphatic Nucleophilic substitution: Chlorination

77 Cyclisation

78 Aliphatic Nucleophilic substitution

79 Aromatic Electrophilic Substitution

80 Phase Transfer Catalyst

81 Addition and Elimination Reaction

82 Methylation , Oxidation and Hydrolysis

83 Aliphatic Nucleophilic substitution and Reduction

84 Halogenation: addition Reaction with Stereochemistry

85 Elimination Reaction (E2)

86 Alkylation Reaction

87 Iodination Reaction

88 Addition Reaction Through Rearrangement

89 Friedel Craft Alkylation Reaction

90 Aromatic Electrophilic Substitution

91 Friedel Craft Acylation Reaction and Bromination reaction

92 Pyrolytic Elimination Reaction

93 Sulphonation and Nitration Reaction

94 Aromatic Nucleophilic Substitution

95 Nitration and Oxidation Reaction

96 Sandmeyer Reaction

97 Pyrolytic Elimination Reaction

98 Diazotization and Neighbouring Group Participation

99 Dehydration: Elimination Reaction

100 Neighbouring Group Participation with Stereochemistry

102 Ortho Nitration reaction

111 Dehydration and Elimination Reaction

112 Elimination Reaction with Stereochemistry

113 Methylation and o-Nitration

114 Bromination and Elimination Reaction

115 Elimination and Epoxidation Reaction

116 Addition and Cyclisation Reaction

117 Neighbouring Group Participation by Aryl ring

118 Pyrolytic Elimination Reaction

119 Acid Hydrolysis reaction

120 Elimination Reaction: E2

121 Aliphatic Nucleophilic substitution and Catalytic Reduction

122 N-Acylation and Nitration Reaction

123 Friedel Craft Alkylation, Oxidation and Halogenation

124 Addition and Rearrangement Reaction

125 Dehydration and Hydroxylation Reaction

126 Grignard Reagent and Dehydration

128 Elimination and Addition Reaction

129 Aromatic Nucleophilic Substitution

130 Friedel Craft Acylation Reaction

131 Dehalogenation Reaction

132 Aromatic Electrophilic Substitution

133 Aliphatic Nucleophilic Substitution

134 Cyclisation

135 Neighbouring Group Participation by heteroatom

136 Aromatic Electrophilic Substitution

137 Aromatic Nucleophilic Substitution: Elimination Addition

Mechanism

138 Gattermann Koch Reaction

139 Benzyne Formation and [4+2] Cyclisation Reaction

140 Aromatic Electrophilic Substitution

141 Diazotization and Diazo coupling reaction

142 Aromatic Electrophilic Substitution

143 Vilsmeyer Haack Formylation Reaction

144 Benzyne Formation and Aromatic Nucleophilic Substitution

145 Alkylation and selective Reduction

146 Catalytic Reduction and Elimination Reaction

147 Aromatic Electrophilic Substitution

148 Wolf Kishner Reduction and Halogenation Reaction

149 Elimination and Ozonolysis Reaction

150 Neighbouring Group Participation by heteroatom

151 Esterification

152 Aliphatic Nucleophilic Substitution and Reduction

153 Neighbouring Group Participation by Pi bond

155 Nitration, Reduction and N-Acylation Reaction

156 Dehydration, Epoxidation and Grignard reagent

157 Addition Reaction and Cyclisation

158 Dehydrohalogenation Reaction

159 O-Acylation Reaction and Cyclisation

160 Reduction and Sandmeyer Reaction

161 Chlorination and Aliphatic Nucleophilic Substitution Reaction

162 Michael Addition and Hydrolysis

163 Nitration Reaction

164 Friedel Craft Acylation Reaction

165 Halogenation and Amide Formation Reaction

166 Elimiantion and Epoxidation with Stereochemistry

167 Dehydrohalogenation and Bromination Reaction

168 Higher Alkyne Formation and Selective Reduction

169 N-Acylation, Bromination and Deprotection

170 Cyclisation

171 Reduction, Diazotisation and Sandmeyer Reaction

172 Aromatic Electrophilic Substitution

173 Elimination Reaction

174 Halogenation, Alkylation and Elimination Reaction

175 Hydration Reaction and o- alkylation reaction

176 Iodination and Cyclisation

177 Friedel Craft Alkylation Reaction

178 Friedel Craft Acylation Reaction

179 Nitarion Reaction

180 Aldol Condensation

181 Crossed Aldol Condensation

1 Nitration Reaction

2 Nucleophilic Substitution by NGP

3 Aromatic Nucleophilic Substitution

4 Halo-hydroxylation Reaction and Aliphatic Nucleophilic Substitution

5 Neighbouring Group Participation by sigma bond

6 Aromatic Electrophilic Substitution and Diazotization

7 Aromatic Nucleophilic Substitution

8 Addition Reaction

9 Nitration Reaction

10 Aromatic Electrophilic Substitution

11 Neighbouring Group Participation by sigma bond

12 Elimination Reaction with Rearrangement

13 Rearrangement

14 Pyrolytic Elimination Reaction

15 Gattermann Koch Reaction

16 Pinacol Pinacolone Rearrangement

17 Alkylation and Dehydration Reaction

18 Neighbouring Group Participation by heteroatom

19 Aromatic Nucleophilic Substitution and condensation

20 Aromatic Electrophilic Substitution

21 Addition Reaction

22 Methylation and Vilsmeyer Haack Formylation Reaction

23 Elimination and Addition Reaction

24 Aromatic Nucleophilic Substitution

25 Neighbouring Group Participation by sigma bond

26 Diazotization Reaction with stereochemistry

27 Friedel Craft Acylation and Condensation Reaction

28 Addition Reaction: Bromination

29 Rearrangement

30 Aliphatic Nucleophilic Substitution and Chlorination by SN i

mechanism

31 Aliphatic Nucleophilic Substitution

32 Jacobson’s Reaction

33 NGP by Aryl ring

34 Elimination Reaction by E 2 Mechanism

35 Cyclisation by protonation

36 Cyclisation by using PTSA

37 Aromatic Nucleophilic Substitution by Elimination –Addition Mechanism

38 Diazotization Reaction with stereochemistry

39 Neighbouring Group Participation by heteroatom and Aliphatic Nucleophilic Substitution

40 Friedel Craft Alkylation Reaction and Aromatization Reaction

41 Riemann Tiemann Reaction

42 SN 2 Mechanism

43 N-Acylation and Nitration Reaction

44 Addition Reaction

45 Aromatic Nucleophilic Substitution by Elimination –Addition Mechanism and Diazo coupling reaction

46 Grignard Reaction

47 Halogenation Reaction and amide formation

48 Elimination and Addition Reaction

49 Dehydration and Epoxidation Reaction

50 Aliphatic Nucleophilic Substitution and Chlorination by SN i

mechanism and SN 2 Mechanism

51 Friedel Craft Acylation and Clemmensons Reduction

52 Nitration ans N-Acylation Reaction

53 Chlorination with stereochemistry and Elimination Reaction by Saytzeff rule

54 Diazotization Reaction with stereochemistry and oxime formation

55 Hydroboration – Oxidation Reaction

56 SN i Mechanism

57 Nitration and Aromatic Nucleophilic Substitution

58 Halogenation and Nitration Reaction Aromatic Electrophilic Substitution

59 Vilsmeyer Haack Formylation Reaction

60 Friedel Craft Acylation Reaction

61 Hunds Dicker Reaction

62 Oxidation and Nitration Reaction

63 Aldol Condensation Reaction

64 Epoxidation and Hydrolysis

65 Vilsmeyer Haack Formylation Reaction

66 Halogenation Reaction and Neighbouring Group Participation by

Pi bond

67 Halogenation: Aromatic Electrophilic Substitution

68 Halogenation: Aromatic Electrophilic Substitution

69 Rearrangement

70 Methylation and Nitration Reaction

71 Diazotisation and Diazo coupling Reaction

72 Rearrangement

73 Pyrolytic Elimination Reaction

74 Vilsmeyer Haack Formylation Reaction

75 Dehydration: Elimination Reaction

76 Aliphatic Nucleophilic substitution: Chlorination

77 Cyclisation

78 Aliphatic Nucleophilic substitution

79 Aromatic Electrophilic Substitution

80 Phase Transfer Catalyst

81 Addition and Elimination Reaction

82 Methylation , Oxidation and Hydrolysis

83 Aliphatic Nucleophilic substitution and Reduction

84 Halogenation: addition Reaction with Stereochemistry

85 Elimination Reaction (E 2 )

86 Alkylation Reaction

87 Iodination Reaction

88 Addition Reaction Through Rearrangement

89 Friedel Craft Alkylation Reaction

90 Aromatic Electrophilic Substitution

91 Friedel Craft Acylation Reaction and Bromination reaction

92 Pyrolytic Elimination Reaction

93 Sulphonation and Nitration Reaction

94 Aromatic Nucleophilic Substitution

95 Nitration and Oxidation Reaction

96 Sandmeyer Reaction

97 Pyrolytic Elimination Reaction

98 Diazotization and Neighbouring Group Participation

99 Dehydration: Elimination Reaction

100 Neighbouring Group Participation with Stereochemistry

101 Benzyne Formation

102 Ortho Nitration reaction

103 Grignard Reaction

104 Friedel Craft Acylation Reaction and Clemmensons Reduction

105 Elimination Reaction

106 Addition Reaction

107 Neighbouring Group Participation by Hetero atom and Grignard Reagent

108 Elimination Reaction and Neighbouring Group Participation by Aryl ring

109 Cyclisation

110 Nitration Reaction

111 Dehydration and Elimination Reaction

112 Elimination Reaction with Stereochemistry

113 Methylation and o-Nitration

114 Bromination and Elimination Reaction

115 Elimination and Epoxidation Reaction

116 Addition and Cyclisation Reaction

117 Neighbouring Group Participation by Aryl ring