Basic Concepts of Organic Chemistry for Competitive Examinations

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Cover Title Copyright Contents Preface CHAPTER 1 _Organic Chemistry CLASSIFICATION OF ORGANIC COMPOUNDS HYDROCARBONS Acyclic Hydrocarbons Alicyclic Hydrocarbons Aromatic Hydrocarbons NOMENCLATURE Trivial System IUPAC system Steps in Naming IUPAC Naming Diff erent types of formulae TETRAVALENCY OF CARBON AND STRUCTURE OF ORGANIC COMPOUNDS Hybridization Hybrid Orbitals of Carbon Quick Reference Tables P R O B L E M S O B J E C T I V E - T Y P E Q U E S T I O N S CHAPTER 2_Isomerism STRUCTURAL ISOMERISM Chain isomerism Ring–chain Isomerism Position Isomerism Functional group isomerism Metamerism Tautomerism PROJECTION FORMULAE Perspective Projection Formulae Newman Projection Fisher Projection Formula STEREOISOMERISM Geometrical Isomerism Optical Isomerism CONFORMATIONAL ISOMERISM Conformational Isomers P R O B L E M S CHAPTER 3_Electron Shift PERMANENT POLARIZATION TEMPORARY POLARIZATION Resonance Hyperconjugation Electromeric Eff ect (E Eff ect) Steric Eff ects P R O B L E M S CHAPTER 4_Organic Acids and Bases BRONSTED–LOWRY THEORY (1923) CONJUGATE ACID–BASE PAIR STRENGTH OF ACIDS Polyprotic Acid Electronegativity and Acid Strength Solvent and Acid Strength Structure and Acid Strength Resonance and Acid Strength Inductive Eff ect and Acid Strength SIMPLE CARBOXYLIC ACIDS SUBSTITUTED ACIDS DICARBOXYLIC ACIDS pKa of Some Dicarboxylic Acids Phenols BENZOIC ACID AND ITS DERIVATIVES H-Bonding and Acid Strength Hybridization and Acid Strength BASES Base Strength Electron-Donating Group and Base Strength Electron-Attracting Groups and Base Strength Steric Factor and the Base Strength PROBLEMS CHAPTER 5_Reaction Mechanism BREAKING OF A COVALENT BOND Homolytic Cleavage Heterolytic Cleavage REAGENTS Electrophiles Nucleophiles Free Radicals REACTION INTERMEDIATES Carbocation Carbanion Carbon-Free Radicals Carbene TYPES OF ORGANIC REACTIONS Addition Reactions Substitution Reactions Elimination Reactions Rearrangement ADDITION TO CARBON–CARBON MULTIPLE BONDS ADDITION OF BR2 TO C=C MECHANISM OF ADDITION Eff ect of the Substituent at Unsaturated Carbon Atoms and the Rate of Addition Addition of HX and Markownikoff ’s Rule Addition of HCl to Vinyl Chloride Addition of HBr to C6H5–CH=CH2 Structure and Reactivity of Aldehydes and Ketones Conjugated >C=O and Reactivity Electron-Attracting Groups and Reactivity Size of the Nucleophile and Reactivity ALIPHATIC NUCLEOPHILIC SUBSTITUTION SN2 Reactions SN1 Reactions Problem FACTORS AFFECTING SN REACTION Structure of the Alkyl Group SN1 Reactivity SN1 Reaction and Nucleophiles SN2 Reactions and Entering of Nucleophiles THE NATURE OF THE SOLVENT SN1 Reactions and Solvent SN2 Reactions and Solvents ELIMINATION REACTIONS `-Elimination a- (or 1,2) Elimination E1-Eliminations E2 Reactions DIRECTION OF ELIMINATION Saytzeff ’s Rule Hofmann’s Rule STRUCTURAL EFFECTS ON DIRECTION OF ELIMINATIONS Branching in Substrate DEHALOGENATION Problem COMPETITION BETWEEN SUBSTITUTION AND ELIMINATION REACTIONS REACTIONS OF –COOH GROUP AND ITS DERIVATIVES Reaction of COOH Group Derivatives of COOH Group Mechanism of Alkaline Hydrolysis P R O B L E M S CHAPTER 6_Name Reactions REIMER–TIEMANN REACTION CANNIZZARO REACTION ALDEHYDES WITHOUT a-H ATOMS CROSSED CANNIZZARO REACTION INTRAMOLECULAR CANNIZZARO REACTION HALOFORM REACTION Scope Uses CLAISEN CONDENSATION Mechanism CONDENSATION OF ESTERS HAVING ONLY ONE a-H ATOM CROSSED CLAISEN CONDENSATION Crossed Claisen condensation in which one ester has no a-H atom DIECKMANN REACTION ALDOL CONDENSATION Dehydration of condensation product CONDENSATION OF CYCLIC KETONES INTRAMOLECULAR ALDOL CONDENSATION PERKIN REACTION VINYLOGS OF CINNAMIC ACID KOLBE REACTION BENZOIN CONDENSATION WURTZ–FITTIG REACTION MOLECULAR REARRANGEMENTS Carbonium ion rearrangements PINACOL–PINACOLONE REARRANGEMENT DEMJANOV REARRANGEMENT (EXPANSION AND CONTRACTION OF RINGS) HOFFMANN REARRANGEMENT OR (HOFFMANN BROMAMIDE REACTION) FRIES REARRANGEMENT CLAISEN REARRANGEMENT BECKMANN REARRANGEMENT BENZILIC ACID REARRANGEMENT (MIGRATION TO CARBONYL CARBON) P R O B L E M S CHAPTER 7_Benzene NAMING Structure of Benzene Valence Bond Structure Resonance Energy of Benzene Aromaticity Isomerism NITRATION ALKYLATION Friedel–Crafts Alkylation Acylation of Benzene HALOGENATION Chlorination and Bromination Iodination of Benzene Fluorobenzene Sulphonation DEUTERATION Orientation and Reactivity ARENES Industrial Source of Alkylbenzene Reactions to Prepare Arenas Physical Properties Chemical Properties ARYL HALIDES Reactions of Activated Aryl Halides Reactions of Simple Aryl Halides (Benzyne Mechanism) AROMATIC SULPHONIC ACIDS Properties and Reactions AROMATIC NITRO COMPOUNDS Synthesis Physical Properties Chemical Properties Polynitro Compounds CHARGE-TRANSFER COMPLEXES AROMATIC AMINES Aniline PHENOLS Synthesis of Phenol Properties Chemical Reactions Tests of Phenol QUINONES Addition Reactions of Quinones Naturally Occurring Quinones Tropolones and Related Compounds AROMATIC ALDEHYDES, KETONES AND ACIDS Aromatic Aldehydes Benzaldehyde Derivatives AROMATIC KETONES Preparation Properties and Reactions BENZOPHENONE (DIPHENYL KETONE) Properties and Reactions AROMATIC CARBOXYLIC ACIDS Preparations Properties and Reaction Some Important Derivatives of Benzoic Acid Important Derivatives of Salicylic Acid PROBLEMS CHAPTER 8_FORMATION OF RING INTERNAL WURTZ REACTION RING COMPOUNDS FROM DICARBOXYLIC ACIDS DIECKMANN CYCLIZATION INTERNAL ALDOL CONDENSATION AND CYCLIZATION ACYLOIN CONDENSATION RING FORMATION THROUGH FRIEDEL–CRAFTS ACYLATION ACID-CATALYSED CYCLIZATION DIELS–ALDER REACTION AND RING FORMATION IMPORTANT POINTS MECHANISMS PROBLEM CHAPTER 9_Alkanes ISOMERS OF PENTANE AND HEXANE Pentane Hexane PREPARATION Decarboxylation of the Salts of Carboxylic Acid Wurtz Reaction Kolbe’s Electrolytic Method Reduction of Alkenes and Alkynes Action of Grignard Reagent with Active Hydrogen Compounds Reduction of Alkyl Halides, Aldehydes and Ketones PROPERTIES AND REACTIONS MELTING POINTS AND BOILING POINTS OF STRAIGHT-CHAIN ALKANES, PROBLEMS CHAPTER 10_Alkenes Isomerism in Alkenes Stability of Alkenes Preparation Properties and Reactions Addition Reactions Oxidation Polymerization ANALYTICAL TESTS OF ALKENES PROBLEMS CHAPTER 11_Alkynes PREPARATION Dehydrohalogenation of Vicinal Dihalides (1,2-Dihalides) Dehydrohalogenation of Gem-Dihalides HIGHER ALKYNES PROPERTIES CHEMICAL REACTION Hydrogenation Electrophilic Addition Nucleophilic Addition to CóC Acidity of Alkynes P R O B L E M S CHAPTER 12_Aliphatic Halogen Compounds ALKYL HALIDES Dihalides Polyhalides Vinyl halide Allyl halide Polyhalogen compounds Trihalo compounds Organometallic compounds Grignard reagents P R O B L E M S CHAPTER 13_Alcohols and Ethers DISTINCTION AMONG 1°, 2° AND 3° ALCOHOLS Victor–Meyer Test Dehydrogenation PREPARATION OF ALCOHOLS Hydration of alkenes Hydrolysis of alkyl halides Grignard synthesis of alcohols Hydroboration of alkenes Reduction of carbonyl compounds ETHYL ALCOHOL AND METHYL ALCOHOL Methyl alcohol (Methanol) Ethyl alcohol (Ethanol) Absolute alcohol Methylated spirit Power alcohol PROPERTIES CHEMICAL REACTIONS Reaction of O–H bond Reactions of the C–OH bond ETHERS PREPARATION Williamson’s synthesis Dehydration of alcohols PROPERTIES REACTIONS Ethers as Base Reactions involving C–O bond Reaction with alkali metal alkyls P R O B L E M S CLASSIFICATION Classifi cation on the basis of the number of –OH groups Classifi cation on the basis of the nature of C atom bearing the –OH group CHAPTER 14_Aldehydes and Ketones ALDEHYDES KETONES Simple Ketones Mixed Ketones Preparation of Aldehydes Preparation of Ketones PROPERTIES AND REACTIONS Solubility Boiling Points Reactions REACTIONS OF >C=O GROUP Nucleophilic addition FORMATION OF ALCOHOLS Reduction of >C=O to >CH2 (that is formation of alkane) Oxidation ALDEHYDES Tollen’s reagents Fehling’s solution KETONES Diff erent aspects of the oxidation Reaction of aldehydes and ketones with NH3 and its derivatives Reaction with R–NH2 (1°C amine) Reaction with R2NH (2° amine) Reaction with some other NH3 derivatives Reductions due to acidity of a-H-atom Polymerization CHARACTERIZATION OF ALDEHYDES AND KETONES DISTINCTION BETWEEN ALDEHYDES AND KETONES Unsaturated Carbonyl Compounds KETENES DICARBONYL COMPOUND DIKETONES P R O B L E M S CHAPTER 15_Carboxylic Acids and Derivatives PREPARATION OF CARBOXYLIC ACIDS Oxidation of primary alcohols or aldehydes From Grignard reagents Hydrolysis of nitriles (or cyanides) Malonic ester synthesis Hydrolysis of ester, amides and acid chlorides to carboxylic acids PHYSICAL PROPERTIES Boiling points and melting points of carboxylic acids Water solubility Odour (Smell) DISSOCIATION OF CARBOXYLIC ACIDS REACTIONS OF CARBOXYLIC ACIDS Salt formation Decarboxylation Reduction Reactions at the a- (or 2–) position of carboxylic acids Formation of acid derivatives PHYSICAL PROPERTIES Chemical Reaction Displacement reactions of acid derivatives Reduction Dicarboxylic acids Eff ect of heat on dicarboxylic acids P R O B L E M S CHAPTER 16_Organic Compounds of Nitrogen AMINES Classifi cation Isomerism Stereochemistry of amines Separation of amines Preparation of amines Preparation of primary amines Preparation of secondary amines Preparation of tertiary amines Physical properties of amines Acylation of amines Reaction of amines with nitrous acid Carbylamine reaction Reaction with carbon disulphide Distinction among 1°, 2° and 3° amines P R O B L E M S CHAPTER 17_Carbohydrates CLASSIFICATION AND NOMENCLATURE Monosaccharides Oligosaccharides (in Greek, oligos means few) Polysaccharides SUGARS AND NON-SUGARS REDUCING AND NON-REDUCING SUGARS Monosaccharides Reaction of D(+) glucose Osazone from Fructose Confi guration of D(+) glucose Reaction of D-glucose with dilute NaOH (Lobry–de Bruyn–van Ekenstein Rearrangement) Epimerization Glucoside formation Reactions of D(–) fructose ASCENDING (OR CHAIN LENGTHENING) SUGAR SERIES DESCENDING SUGAR SERIES (CHAIN SHORTENING) Ruff Degradation Wohl’s Degradation Ring structures of a- and b-D(+) glucose Glycosides, aglycone and N-glycosides Disaccharides Maltose Polysaccharides CELLULOSE Cellulose ether (Sodium carboxymethyl cellulose) Cellulose as food P R O B L E M S CHAPTER 18_Amino Acids, Proteins and Nucleic Acids CONFIGURATION OF NATURAL AMINO ACIDS NOMENCLATURE OF AMINO ACIDS Classifi cation of amino acids ESSENTIAL AND NON-ESSENTIAL AMINO ACIDS Synthesis of amino acids Properties of amino acids Test of amino acids Naming of peptides PROTEINS Some characteristics of proteins Classifi cation of proteins Structure of proteins Functions of protein Nucleic Acids Structure Chain conformation of nucleic acids DNA RNA P R O B L E M S CHAPTER 19_Polymers POLYMERS Polymerization Classifi cation Stereochemistry of polymer Free radical addition polymerization Vinyl polymerization Cationic Addition Polymerization Anionic Addition Polymerization Condensation Polymerization POLYESTERS Synthesis of Dacron and Lexan Glyptal Resin Polyamides Nylon-66 Nylon-6 e-caprolactum Phenol–Formaldehyde Resins (Bakalite) Melamine–Formaldehyde Resin RUBBERS Natural Rubber Synthetic Rubbers SILK WOOL BIODEGRADABLE POLYMERS Polyhydroxybutyrate-Co-β-Hydroxyvalerate (PHBV) Nylon-2–Nylon-6 Poly (Glycolic Acid) and Poly (Lactic Acid) Monodispersity and Polydispersity Mass of Polymers Polydispersity Index (PDI) P R O B L E M S CHAPTER 20_Column Matching Problems COLUMN MATCHING CHAPTER 21_Short Answer Problems S H O R T - A N S W E R P R O B L E M S CHAPTER 22_Problems on Structure Determination