Organic Reactions and Their Mechanisms

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Half Title
Organic Reactions and Their Mechanisms
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Preface to the Second Edition
Preface to the First Edition
Contents
Organic Reactions and Their Mechanisms
	1. Introduction
	2. Fundamental concepts
		2.1 Equations involved in organic reaction
		2.2 Chemical Bonds
			2.2.1 Ionic Bonds
			2.2.2 Covalent Bonds
			2.2.3 Hybridisation
				2.2.3.1 sp3 Hybridization
				2.2.3.2 sp2 Hybridization
				2.2.3.3 sp Hybridization
		2.3 Representation of a Chemical Reaction
		2.4 Mechanism of Organic Reactions
			2.4.1 Electron Availability
				2.4.1.1 Inductive Effect
				2.4.1.2 Electromeric Effect
				2.4.1.3 Mesomeric Effect
				2.4.1.4 Hyperconjugative Effect
				2.4.1.5 Resonance
			2.4.2 Breaking and Formation of Bonds
				2.4.2.1 Bond Fission
					2.4.2.1.1 Homolytic Bond Fission
					2.4.2.1.2 Hetrolytic Bond Fission
				2.4.2.2 Bond Formation
			2.4.3 Reaction Intermediates
				2.4.3.1 Carbocations
					Reactions of Carbocations
					Generation of Carbocations
					Reactions Involving Carbocations
						Friedel-Crafts Reaction
						Friedel-Crafts Alkylation
						Friedel-Crafts Acylation
						Baeyer-Villiger Oxidation
						Pinacol-Pinacolone Rearrangement
						Wagner-Meerwein Rearrangement
						Beckmann Rearrangement
				2.4.3.2 Carbanions
					Structure of Carbanions
					Generation of Carbanions
					Reactions of Carbanions
						Addition Reactions
						Elimination Reactions
						Displacement Reactions
						Rearrangement Reaction
						Decarboxylation
						Oxidation of Carbanions
					Reactions Involving Carbanions
						Aldol Condensation
						Acid-Catalysed Aldol Condensation
						Crossed Aldol Condensation
						Perkin Reaction
							Claisen Condensation
							Dieckmann Condensation
							Michael Addition
				2.4.3.3 Free Radicals
					Stability of Free Radicals
					Generation of Free Radicals
						Photolysis
						Thermolysis
						Redox Reactions
					Reactions of Free Radicals
						Recombination of Free Radicals
						Disporportionation
						Reaction with Olefins
						Reaction with Iodine and Metals
						Rearrangements
					Reactions Involving Free Radicals
						Sandmeyer reaction
						Gomberg reaction
						Wurtz reaction
						Hunsdiecker reaction
						Kolbe electrolytic reaction
					Halogenation
						Conversion of methane into carbon tetrachloride
						Conversion of benzene into benzene hexachloride
						Conversion of toluene into benzyl chloride
						Conversion of propene into n-propyl bromide
						Vinyl Polymerisation
				2.4.3.4 Carbenes
					Generation of Carbenes
						From alkyl halides
						From Ketenes
						From Epoxides
						From diazirines
						From aliphatic diazo compounds
					Reactions of Carbenes
						Addition reactions
						Insersion into C—H bonds
						Reaction with hydrazine: Formation of Diazomethane
						Reaction with primary amines (synthesis of isonitriles)
						Synthesis of nitriles
						Reaction with Alcohols
						Reaction with aldehydes: synthesis of mandelic acids
						Rearrangements
						Ring expansion
						Ring contraction
						Synthesis of allenes
						Synthesis of spiro comounds
					Reactions Involving Carbenes
						Carbylamine reaction
						Wolff rearrangement
						Reimer-Tiemann reaction
				2.4.3.5 Nitrenes
					Generation of Nitrenes
						From azides
						From Sulfinylamines
						From N-benzenesulfonoxy carbamates
					Reactions of Nitrenes
						Insersion
						Dimerisation
						Abstraction of Hydrogen
					Reactions Involving Nitrenes
						Hofmann rearrangement
						Curtius rearrangement
						Lossen arrangement
				2.4.3.6 Benzyne
					Generation of Benzynes
						From aryl halides
						From o-Aminobenzoic acid
						From phthaloyl Peroxide
						From Benzothiazoate 1, 1-dioxide
						From benzenetrifluoromethane sulfonate
					Reactions of Benzynes
						Reaction with nucleophiles
						Synthesis of t-butyloxyphenol, o-phenyl cyclohexanone and phenyl benzoate
						Reaction with anthracene, furan and aniline
						Dimerisation
						Reaction with olefins
		2.5 Types of Reagents Used in a Chemical Reaction
			2.5.1 Electrophilic Reagents
			2.5.2 Nucleophilic Reagents
		2.6 Type of reactions involved in a chemical reaction
			2.6.1 Addition Reactions
				2.6.1.1 Electrophilic Addition Reactions
					Electrophilic addition of halogen halides (Hydrohalogenation)
					Addition of Water (Hydration)
					Addition of Halogen (Halogenation)
					Addition of HO–Cl (Formation of Halohydrins)
					Addition to Conjugated Dienes
				2.6.1.2 Free Radical Addition Reactions
				2.6.1.3 Concerted Addition Reactions
					2.6.1.3.1 Hydroboration
					2.6.1.3.2 Diels-Alder Reaction
					2.6.1.3.3 Ozonolysis
					2.6.1.3.4 Hydroxylation
				2.6.1.4 Nucleophilic Additions to Carbonyl Compounds
					2.6.1.4.1 Reaction with Hydrogen Cyanide
					2.6.1.4.2 Reaction with Sodium Hydrogen Sulphite
					2.6.1.4.3 Reaction with Alcohols
					2.6.1.4.4 Reaction with Amines
					2.6.1.4.5 Reaction with Grignard Reagents
					2.6.1.4.6 Wittig Reaction
					2.6.1.4.7 Aldol Condensation
					2.6.1.4.8 Perkin Condensation
					2.6.1.4.9 Claisen Condensation
					2.6.1.4.10 Knoevenagel Condensation
					2.6.1.4.11 Cannizzaro Reaction
					2.6.1.4.12 Michael Addition
			2.6.2 Elimination reactions
				2.6.2.1 Bimolecular Elimination Reactions (E2)
					2.6.2.1.1 Stereochemistry of E2 Reactions
				2.6.2.2 Unimolecular Elimination Reaction (E1)
				2.6.2.3 E1cB Mechanism
			2.6.3 Substitution Reactions
				2.6.3.1 Free Radical Substitution
					Allylic Substitution
					Vinylic Substitution
				2.6.3.2 Ionic Substitution
					2.6.3.2.1 Electrophilic Substitution Reactions (SE)
						2.6.3.2.1.1 Aromatic Electrophilic Substitution
							Nitration
							Halogenation
							Sulphonation
							Alkylation and Acylation
						2.6.3.2.1.2 Orientation and Reactivity in Aromatic Electrophilic Substitution
						2.6.3.2.1.3 Electrophilic Substitution in Heteroaromatic Compounds
					2.6.3.2.2 Nucleophilic Substitutions
						2.6.3.2.2.1 Bimolecular Nucleophilic Substitutions (SN2) Reactions
						2.6.3.2.2.2 Unimolecular Nucleophilic Substitution (SNI) Reactions
						2.6.3.2.2.3 Nucleophic Substitutions Involving Neighbouring Group Participation
						2.6.3.2.2.4 Nucleophilic Substitution Internal (SNi)
						2.6.3.2.2.5 Nucleophilic Substitution on Alcohols–An Indirect Method
						2.6.3.2.2.6 Nucleophilic Substitution Reactions in Relatively Non-polar Aprotic Solvents by Phase-Transfer Catalysts
						2.6.3.2.2.7 Nucleophilic Aromatic Substitutions
						2.6.3.2.2.8 Nucleophilic Heteroaromatic Substitution
			2.6.4 Rearrangement reactions
				2.6.4.1 Carbon-Carbon Rearrangements
					Pinacol Rearrangement
					Benzil Benzilic Acid Rearrangement
				2.6.4.2 Carbon-Nitrogen Rearrangements
					Hofmann Rearrangement
				2.6.4.3 Carbon-Oxygen Rearrangements
					Baeyer-Villiger Oxidation
					Claisen Rearrangement
				2.6.4.4 Isomerisations
					Conversion of n-propylbromide into isopropyl bromide
					Conversion of butane to isobutane
					Conversion of 1,1,1-triphenyl-2-bromoehtane into 1,1,2-triphenylethane
					Cope Rearrangement
					Electrolytic Reactions
			2.6.5 Photochemical reactions
				2.6.5.1 Free Radical Chlorination
				2.6.5.2 Photoreductive Dimerisation
				2.6.5.3 Photomerisation of cis- and trans-1,2-diphenylethene (Stilbene)
				2.6.5.4 Photochemical Cyclo Addition Reactions
				2.6.5.5 Photo chemical Erndt-Eistert Synthesis
				2.6.5.6 Barton Reaction
				2.6.5.7 Photonitrosation
				2.6.5.8 Paterno-Bϋchi Reaction
				2.6.5.9 Formation of Vitamin D2 from Ergosterol
			2.6.6 Oxidations
				2.6.6.1 Oxidation of Hydrocarbons
					2.6.6.1.1 Oxidation of Alkanes
					2.6.6.1.2 Oxidation of Alkenes
					2.6.6.1.3 Oxidation of Alkynes
					2.6.6.1.4 Oxidation of Aromatic Hydrocarbons
				2.6.6.2 Oxidation of Alcohols
					Oxidation of primary alcohols
					Oxidation of secondary alcohols
				2.6.6.3 Oxidation of Phenols
				2.6.6.4 Oxidation of Aldehydes
				2.6.6.5 Oxidation of Ketones
				2.6.6.6 Oxidation of Amines
			2.6.7 Reductions
				2.6.7.1 Reduction of Unsaturated Compounds
					2.6.7.1.1 Reduction of Alkenes
					2.6.7.1.2 Reduction of Alkynes
					2.6.7.1.3 Reduction of Aromatic Hydrocarbons
				2.6.7.2 Reduction of Alcohols and Phenols
				2.6.7.3 Reduction of Aldehydes and Ketones
					2.6.7.3.1 Reduction to Alcohols
					2.6.7.3.2 Reduction of Aldehydes and Ketones to Hydrocarbons
						Clemmensens Reduction
						Wolff-Kishner Reaction
					2.6.7.3.3 Reduction of Carboxylic Acids and its Derivatives
						Reduction of carboxylic acids to aldehydes
						Reduction of Carboxylic acids to alcohols
						Reduction of Derivatives of Carboxylic Acids
					2.6.7.3.4 Reduction of Cyanides
					2.6.7.3.5 Reduction of Aromatic Nitro Compounds
	Multiple Choice Questions
	Fill in the Blanks
	Short Answer Questions
Index