Organic Reaction Mechanism

Through

Problem Solving Approach

Nitin D. Gaikwad (M.Sc., Ph.D.)

Assistant Professor
Department of Chemistry,
K.T.H.M. College, Nashik-422005
Maharashtra, India
email :[email protected]
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 retrieval
system, electronic or mechanical, without the written permission of the
copyright owner.

PREFACE
 This book aims to teach students how to draw organic reaction
mechanism for themselves. Almost all available books, on organic reaction
mechanism describe reactions and their conversions. This book confronts the
student with the organic reaction mechanism by showing how the reagent and
starting molecule act together in the reaction. The reaction mechanism
approach is learnt by students from this book who then teaches themselves
how to use mechanism by solving a series of problems.
It is not a conventional text book with detailed text explanation. In
short this book understand quickly and giving information about reaction
mechanism. Also the student has planned sequence of problems to
demonstrate the use of each new mechanism and to test his understanding of
it. Each problem is followed by possible reaction mechanism and short
explanation, So that if the student fails to solve a problem he will still
understand the answer better for having attempted the problem himself. The
student therefore has the possibility of continuous self assessment through the
use of large number of problems.
There are some excellent books written about organic reaction
mechanism but they mostly present complete synthesis not reaction
mechanism. I have tried in this book to teach student to speak the language of
reaction mechanism themselves. This book is originally written for the first
year students.
The programme aims to allow students to teach themselves but it
shouldn’t mean any less work for them. Because students discover what they
don’t know, they should have more sensible questions to ask when they were
solving reaction mechanism. My aim is to give you more time for real
teaching. The book should do the ground work and you should be able to set
suitable programme and discuss then profitably. The book itself has plenty of
problems of this sort.
 Though the programme may introduce you reaction mechanism, its
main aim is to suggest a mechanistic approach to the organic reactions. You
therefore need to have a reasonable grounding in organic chemistry so that
you are familiar with most basic organic reactions. If you are first year
student with no much experience of organic chemistry or limited knowledge
of organic reactions in practice you will probably be able to work straight
through the book to learn the actual reaction mechanism. The point of book
learning is that you learn at your own pace and that you yourself check on
your own progress.
 Contents
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 SNi
mechanism
31. Aliphatic Nucleophilic Substitution
32. Jacobson’s Reaction
33. NGP by Aryl ring
34. Elimination Reaction by E2 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. 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
49. Dehydration and Epoxidation 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
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 (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
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
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
127. Dehydration and Epoxidation Reaction
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
154. Nitration Reaction
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
 181.
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 SNi
mechanism
31. Aliphatic Nucleophilic Substitution
32. Jacobson’s Reaction
33. NGP by Aryl ring
34. Elimination Reaction by E2 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. 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
49. Dehydration and Epoxidation 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. 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 (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
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
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
127. Dehydration and Epoxidation Reaction
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
154. Nitration Reaction
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. Nitration Reaction
180. Aldol Condensation
181. Crossed Aldol Condensation