ORGANIC CHEMISTRYfor

B.Sc., B.Sc. (Honours) & M.Sc. (Prev.) Students

M.K. JAIN M.Sc., Ph.D. (Glasgow)

Former Professor,National Dairy Research Institute(Deemed University), KARNAL

(Haryana)

S.C. SHARMA M.Sc., Ph.D.

Former-Head, Deptt. of ChemistryV.B.R.I. P.G. College,

UDAIPUR (Rajasthan)

VISHAL PUBLISHING CO.Future for WINNERS

Modern

JALANDHAR - DELHI

REVISED EDITION

CONTENTS

(i)

1. INTRODUCTION 1–261.0 Definition and importance of organic chemistry 11.1 Growth of organic chemistry 21.2 Sources of organic compounds 31.3 Purification 3

1.3.1 Crystallization 41.3.2 Fractional crystallization 51.3.3 Sublimation 51.3.4 Extraction with solvent 61.3.5 Continuous extraction, Soxhletting 61.3.6 Distillation at atmospheric pressure 71.3.7 Distillation under reduced pressure 71.3.8 Steam distillation 81.3.9 Fractional distillation 9

1.3.10 Chromatography 11, Column chromatography11,Thin layer chromatography 12, Paper chromato-graphy 13, Gas-Liquid chromatography 14

1.4 Criteria of purity 141.5 Qualitative elemental analysis 151.6 Quantitative elemental analysis 16

1.6.1 Estimation of carbon and hydrogen 161.6.2 Estimation of nitrogen 171.6.3 Estimation of halogens 181.6.4 Estimation of sulphur 191.6.5 Estimation of phosphorus 191.6.6 Estimation of oxygen 19

1.7 Calculation of the empirical formula 201.8 Determination of the molecular weight 201.9 Calculation of molecular formula 23

2. PETROLEUM AND PETROCHEMICALS 27–342.0 Occurrence and composition 272.1 Processing of petroleum (Petroleum refining) 27

2.1.1 Fractional distillation (Straight distillation) 272.1.2 Cracking 28

2.2 Rating of fuels used in internal combustionengines 29

2.2.1 Octane rating (octane number) 292.2.2 Cetane rating (cetane number) 302.2.3 Flash point 30

2.3 Petrochemicals 302.4 Synthetic petroleum 31

2.4.1 Bergius process 312.4.2 Fischer-Tropsch process 32

2.5 Petroleum as a source of aromatics 32

3. REACTION MECHANISM 35–883.0 Introduction 353.1 Polar and non-polar Bonds 353.2 Measurement of the polarity of covalent bond 363.3 Hydrogen Bonds 373.4 Electron displacements in organic

compounds 41

3.4.1 Inductive effect 413.4.2 Electromeric effect 453.4.3 (A) Resonance 463.4.3 (B) Resonance energy 47

3.5 Resonance theory 483.5.1 Application 49

3.6 Resonance effect/mesomeric effect 533.7 Hyperconjugation 543.8 Steric effect 573.9 Acids and bases 60

3.9.1 The Lowry-BrØnsted concept 603.9.2 The Lewis concept 623.9.3 Measurement of acidity (Ka and pKa) and acid

character of carboxylic acids 633.10 Effect of solvation on acidity 633.11 Types of reagents 64

3.11.1 Nucleophilic reagent 643.11.2 Electrophilic reagents 643.11.3 Free radicals 65

3.12 Homolytic and heterolytic cleavage of a covalentbond (formation of reactive intermediates) 65

3.12.1 Free radicals 653.12.2 Carbocation / Carbonium ions 683.12.3 Carbanions 723.12.4 Carbenes 763.12.5 Benzyne 773.12.6 Nitrenes 77

3.13 Energy profiles 793.14 Energy changes during reactions 81

4. TYPES OF ORGANIC REACTIONS, INCLUSIONCOMPOUNDS AND CHARGE TRANSFERCOMPLEXES 89–101

4.0 Introduction 894.1 Types of organic reactions 89

4.1.1 Substitution reactions 894.1.2 Addition reactions 904.1.3 Elimination reactions 914.1.4 Rearrangement reactions 91

4.2 Methods used to determine reaction mechanism92

4.3 Inclusion compounds/complexes 974.4 Charge transfer complexes 98

5. CLASSIFICATION AND NOMENCLATURE OFORGANIC COMPOUNDS 102–125

5.0 Introduction 1025.1 Systems of naming organic compounds 1045.2 Rules of IUPAC system of nomenclature for

acyclic compounds 1065.3 IUPAC system of nomenclature for complex

organic compounds 107

(ii)

5.4 IUPAC nomenclature of bicyclic compounds 1195.5 IUPAC nomenclature of spiro compounds 1205.6 Pitfalls to be avoided in IUPAC names 1205.7 Procedure for writ ing the structure of a

compound with a given IUPAC name 1205.8 Correct way of writing names of organic

compounds 121

6. STEREOCHEMISTRY – I 126–1546.0 Introduction 1266.1 Concept of isomerism and its types 126

6.1.1 Types of structural isomers 1276.1.2 Types of stereoisomers 128

6.2 General stereochemistry 1286.2.1 Concept of chirality 1286.2.2 Tetrahedral carbon 1296.2.3 Chirality and enantiomerism 1296.2.4 Wadge and Dashed bond drawing of organic

molecules 1306.2.5 Asymmetric carbon atom and related terms 1306.2.6 Elements of symmetry 1316.2.7 The asymmetric carbon and molecular chirality

1336.3 Optical activity 1346.4 Acyclic molecule with one asymmetric/chiral

carbon or stereogenic centre 1356.5 Enantiomers and related aspects 136

6.5.1 Properties of enantiomers 1376.5.2 The racemic modification 137

6.6 Racemic forms and enantiomeric excess 1386.7 Configuration 139

6.7.1 Relative specification of Configuration D and Lnotation 139

6.7.2 Specification of configuration R and S notation141

6.8 Compounds with two stereogenic centres or twoasymmetric/chiral carbon 143

6.9 Properties of diastereomers 1456.9.1 Distinction between diastereomers and

enantiomers 1456.10 Fischer Projections 145

6.10.1 Guidelines for writing stereochemically equivalentstructures on Fischer projections 146

6.10.2 Specifying R–S configuration on Fischerprojection 148

6.11 Erythro and Threo nomenclature (notation) ofconfigurations 150

6.12 Resolution 1506.13 Asymmetric (stereogenic centre) synthesis 1526.14 Walden inversion 1526.15 Retention and racemisation 153

7. STEREOCHEMISTRY – II 155–1827.1 Geometric isomerism (cis-trans isomerism) 155

7.1.1 Concept of hindered rotation about a carbon-

carbon double bond and geometric isomerism1557.1.2 Geometric isomers as Diastereomers 1567.1.3 Structure of alkenes and geometric

isomerism 1567.1.4 Extended scope of geometric isomerism 1577.1.5 Assigning configuration to geometric

isomers 1587.1.6 E-Z system of nomenclature for cis- trans

isomers 1587.1.7 Relative stabilities of cis-trans isomers 162

7.2 Conformation of alkanes 1627.2.1 Factors influencing conformational stability 168

7.3 Conformational analysis of cyclohexane 1697.3.1 Ring strain and stabilities of the conformations

of cycloalkanes 1697.3.2 Chair and boat conformations 1707.3.3 Axial and equatorial bonds in cyclohexane 1727.3.4 1,3 and 1,5-Diaxial interactions in cyclohexane

derivatives 1737.3.5 Conformations of disubstituted cyclohexanes

1747.4 Conformational isomers vs. configurational

isomers 1747.5 Assorted topics of stereochemistry 175

7.5.1 Chirality without asymmetric/chiral atoms 175

8. ALKANES 183–2018.0 Introduction 1838.1 General methods of preparation 1838.2 General physical properties 1888.3 General chemical properties 189

9. CYCLIC ALIPHATIC HYDROCARBONS(CYCLOALKANES AND CYCLOALKENES)

202–2289.0 Introduction 2029.1 Nomenclature 2029.2 General methods of preparation 2049.3 General physical properties 2089.4 Spectroscopic properties 2089.5 General chemical properties 2089.6 Relative stabilities of cycloalkanes 209

9.6.1 Baeyer’s strain theory 2109.6.2 Sachse-Mohr theory of strainless rings 211

9.7. Ring strain and stabilities of cycloalkanes 2129.7.1 Orbital picture of angle strain 2129.7.2 Coulson and Moffit ’s concept (Banana

bond) 2139.7.3 Relative stabilities of some cycloalkanes 214

9.8 Condensed (Fused) ring compounds 2169.9 Large ring compounds 217

CYCLOALKENES9.10. Introduction 2199.11 Nomenclature 2209.12 General Methods of preparation/formation 2209.13 Physical properties 2219.14 Chemical properties 221

(iii)

9.15 Stability of cycloalkenes 2259.16 Trans cycloalkenes 2259.17 Conformation of cycloalkenes 225

10. ALKENES 229–25710.0 Introduction 22910.1 Nomenclature 22910.2 General methods of preparation 23010.3 General physical properties 23310.4 General chemical properties 234

10.4.1 Electrophilic additions 23410.4.2 Free radical additions 24810.4.3 Oxidation 24810.4.4 Substitution reactions 25110.4.5 Polymerization 25310.4.6 Addition of hydrogen 254

11. ALKADIENES 258–27511.0 Introduction 25811.1 Classification 25811.2 Nomenclature 25911.3 Isomerism 25911.4 Structure and stability 259

11.4.1 Resonance picture and relative stabilities 25911.4.2 Molecular orbital picture of conjugated dienes

26111.4.3 Structure of allenes 262

11.5 Stereochemistry of allenes 26311.6 General methods of preparation 26311.7 Physical properties 26411.8 Chemical properties 26411.9 Diels-Alder reaction 270

11.9.1 General description 27011.9.2 Stereochemistry 27111.9.3 Diels-Alder reaction between unsymmetrical

reactants 27211.9.4 Mechanism 27311.9.5 Importance 27311.9.6 Diels-Alder reaction as a pericyclic reaction 273

12. ALKYNES 276–29212.0 Introduction 27612.1 Nomenclature 27612.2 Acidity of alkynes 27712.3 General methods of preparation 27812.4 General physical properties 27912.5 General chemical properties 279

12.5.1 Substitution of acetylenic hydrogen in terminalalkynes 279

12.5.2 Addition reactions 28012.5.3 Reduction reactions 28512.5.4 Oxidation reactions 28712.5.5 Polymerization 28812.5.6 Rearrangement 28912.5.7 Miscellaneous reactions 289

12.6 Commercial importance 290

13. SYNTHETIC POLYMERS 293–317(The Giant Molecules)

13.0 Introduction 29313.1 Terminology/definition 29313.2 Types of polymers 29413.3 Orientation or configuration in polymers 29513.4 Polymerization reactions 295

13.4.1 Addition or chain growth polymerization 29513.4.2 Condensation (step growth polymerization) 300

13.5 Physical properties of polymers 30813.6 Some representative synthetic polymers and

their uses 30813.7 Elastomers 311

13.7.1 Synthetic rubbers 31113.7.2 Natural rubber 31213.7.3 Sil icon rubber (organosiloxane polymer or

elastomer) 31313.8 Plasticizers 31413.9 Semisynthetic polymers 314

13.10 Synthetic polymers and environmental pollution314

14. STRUCTURE OF BENZENE, AROMATICITYAND ORIENTATION 318–348

14.0 Introduction 31814.1 Structure of benzene 318

14.1.1 Kekule’s structure 31814.1.2 Resonance model of benzene 32114.1.3 Molecular orbital picture of benzene 32214.1.4 Molecular orbital theory of bonding in organic

compounds 32314.2 Benzene versus cyclobutadiene : MO pictures

32414.3 Frost circ le or inscribed polygon method

(polygon rule) 32514.4 The concept of aromaticity 325

14.4.1 Aromatic, Antiaromatic and non-aromaticcompounds 326

14.4.2 Hückel’s rule 32714.4.3 Application of Hückel’s rule 327

14.5 Orientation effect of substituents on furtherelectrophilic aromatic substitution 333

14.5.1 Effect of activating groups 33414.5.2 Effect of deactivating groups 336

14.6 Steric factors in electrophilic aromatic substitution340

14.7 Ortho-Para ratio in electrophil ic aromaticsubstitution 340

14.8 Introduction of a third substituent into thebenzene ring 341

14.9 Orientation 34215. AROMATIC HYDROCARBONS (ARENES)

349–37515.0 Introduction 34915.1 Nomenclature of benzene derivatives 349

(iv)

15.2 General methods of preparation 35315.3 General physical properties 35615.4 Spectroscopic properties 35615.5 General chemical properties 357

15.5.1 Electrophilic aromatic substitution : A generalpattern 357

15.5.2 Electrophilic aromatic substitution reactions 35915.5.3 Free radical substitution and addition reactions

36615.5.4 Oxidation 370

15.6 Additional arenes 37215.6.1 Styrene (vinylbenzene, phenylethene 37215.6.2 Phenylacetylene (Ethynylbenzene) 373

16. POLYNUCLEAR HYDROCARBONS 376–41916.0 Introduction 37616.1 NAPHTHALENE 376

16.1.1 Nomenclature 37616.1.2 Isomerism 37716.1.3 Isolation 37716.1.4 Structure 37716.1.5 Physical properties 38116.1.6 Spectroscopic properties 38116.1.7 Chemical properties 38116.1.8 Uses 389

16.2 Naphthalene derivatives 38916.2.1 Naphthols 39016.2.2 Naphthylamines 39316.2.3 Nitronaphthalenes 39516.2.4 Naphthalene sulphonic acids 39616.2.5 Naphthaquinones 396

16.3 ANTHRACENE 39716.3.1 Occurrence 39716.3.2 Nomenclature and isomerism 39716.3.3 Structure 39816.3.4 Physical properties 40016.3.5 Spectroscopic properties 40016.3.6 Chemical properties 40016.3.7 Mechanism of electrophilic addition and

substitution reactions 40316.4 Derivatives of anthracene 404

16.4.1 Anthraquinone 40416.5 PHENANTHRENE 406

16.5.1 Structure 40616.5.2 Properties 40716.5.3 Synthesis of phenanthrene and its

derivatives 40816.6 Carcinogenesis 40816.7 Polynuclear hydrocarbons with isolated ring

systems 40916.7.1 Diphenyl (biphenyl), phenylbenzene 40916.7.2 Polyphenyls 41116.7.3 Diphenylmethane 41216.7.4 Triphenylmethane 413

16.8 Stereochemistry of diphenyl system 41316.9 Fluorenes 415

17. ORGANIC HALOGEN COMPOUNDS–I 420–45417.0 Introduction 42017.1 Nomenclature and classification 42017.2 General methods of preparation 42217.3 General physical properties 42417.4 General chemical properties 424

17.4.1 Nucleophilic substitution reactions 42417.4.2 Elimination reactions 42717.4.3 Reduction of alkyl halides 42717.4.4 Reaction with magnesium 427

17.5 Vicinal and geminal dihalides 42717.6 Detailed mechanisms of nucleophilic

substitution 42817.6.1 Alkaline hydrolysis of methyl bromide

(SN2 reaction) 42817.6.2 Alkaline hydrolysis of tert- buty l bromide

(SN1 mechanism) 43017.6.3 Factors influencing rates of nucleophil ic

substitution reactions 43217.6.4 SN1 versus SN2 mechanism 43317.6.5 Mechanism of the reaction of alcohols

(SNi mechanism) 43317.6.6 Neighbouring group participation (anchimeric

assistance) 43417.7 Mechanism of elimination reactions 435

17.7.1 Orientation in elimination reactions 43717.8 Substitution vs elimination 44017.9 ALKENYL HALIDES 440

17.9.1 Classification and nomenclature 44017.9.2 Vinyl halides 44117.9.3 Allyl halides 44317.10 Fluorocarbons 44517.11 Chlorofluoro hydrocarbons (Freons) 446

17.11.1 Preparation 44617.11.2 Nomenclature 44617.11.3 Uses 446

17.12 Polyhalogenated alkanes 44617.12.1 Chloroform 44617.12.2 Iodoform 449

17.13 Tetra haloalkanes 45017.13.1 Carbon tetrachloride 450

17.14 Impact of fluorocarbons on environment 451

18. ORGANIC HALOGEN COMPOUNDS - II(ARYL AND ARALKYL HALIDES) 455–475

18.0 Introduction 45518.1 Isomerism 45618.2 Preparation/Formation 45618.3 Aryl halides vs. Alkyl halides 45818.4 General physical properties 45818.5 General chemical properties 459

18.5.1 Nucleophilic aromatic substitution reactions 45918.5.2 Formation of Grignard reagent 46618.5.3 Wurtz-Fittig reaction 46618.5.4 Ullmann diaryl synthesis 46618.5.5 Reduction 46618.5.6 Formation of DDT 467

(v)

18.5.7 Electrophilic aromatic substitution reactions 46718.6 Aryl versus Vinyl halides 46718.7 Aralkyl halides 468

18.7.1 Preparation 46818.7.2 Chemical properties 471

18.8 Comparison between aryl and aralkyl halides472

18.9 Synthesis of commercially important halogenatedcompounds 472

18.10 Aromatic halogen compounds and their safetyto animals/humans 472

19. ALCOHOLS (ALKANOLS) (MONO-, DI- AND TRI-HYDRIC ALCOHOLS) 476–51119.0 Introduction 47619.1 Classification 47619.2 Monohydric alcohols 477

19.2.1 Nomenclature 47719.2.2 General methods of preparation / synthesis 47819.2.3 General physical properties 48019.2.4 General chemical properties 48119.2.5 Distinction between primary, secondary and

tertiary alcohols 48819.2.6 Ascent and descent in alcohol series 489

19.3 Some important monohydric alcohols 49119.3.1 Methyl alcohol 49119.3.2 Ethyl alcohol 49219.3.3 Allyl alcohol 49519.3.4 Benzyl alcohol 496

19.4 DI- AND TRI-HYDRIC ALCOHOLS 49619.4.1 Ethylene glycol and vicinal diols 49619.4.2 Glycerol 502

20. PHENOLS 512–54120.0 Introduction 51220.1 Classification and nomenclature 51220.2 Preparation 513

20.2.1 Specific methods for the preparation of phenol515

20.3 General physical properties 51620.4 General chemical properties 516

20.4.1 Acidic character of phenols 51620.4.2 Acid strengths of phenols 51720.4.3 Phenols vs alcohols 51720.4.4 Effect of substituents on the acidity of phenol

51820.4.5 Reactions of –OH group similar to alcohols 51920.4.6 Electrophilic aromatic substitution reactions 52220.4.7 Oxidation 52920.4.8 Reactions of analytical importance 52920.4.9 Some specific reactions 531

20.5 Some individual members 53220.5.1 Nitrophenols 53220.5.2 2,4,6-Trinitrophenol 53320.5.3 Catechol 53520.5.4 Resorcinol 53620.5.5 Quinol 537

21. ETHERS, CYCLIC ETHERS AND CROWN ETHERS542–560

21.0 Introduction 54221.1 Nomenclature 54221.2 Isomerism 54221.3 General methods of preparation 54321.4 General physical properties 54521.5 General chemical properties 54621.6 Ziesel method for the estimation of methoxy or

ethoxy group 54921.7 Importance of some individual ethers 550

21.7.1 Anisol and phenetole 55021.7.2 Eugenol 550

21.8 Cyclic ethers 55021.9 Epoxides 551

21.9.1 Preparation 55121.9.2 Properties 55121.10 Crown ethers 454

21.10.1 Synthesis 55521.10.2 Application 555

21.11 Claisen rearrangement 557

22. ALDEHYDES AND KETONES 561–60622.0 Introduction 56122.1 Nomenclature 56122.2 General methods of preparation / synthesis 563

22.2.1 From acid chlorides 56322.2.2 From 1,3-dithianes 56422.2.3 From nitriles 56522.2.4 From carboxylic acids 56522.2.5 Special methods of preparation for aromatic

aldehydes 56522.2.6 Special methods for aromatic ketones 568

22.3 General physical properties 57022.4 Structure and reactivity of carbonyl group 57022.5 Acidity of -hydrogens 57122.6 Relative reactivities of aldehydes and ketones

in nucleophilic additions 57122.7 Nucleophilic additions 57222.8 Condensation reactions 57622.9 Hydride transfer reaction 584

22.10 Condensation reactions with ammonia derivatives585

22.11 Reaction with phosphine derivatives 58722.12 Reduction reactions 58822.13 Oxidation reactions 59122.14 Polymerization 59222.15 Halogenation of enolizable ketones 59322.16 Comparative studies of formaldehyde and

acetaldehyde 59422.17 Comparative properties of aliphatic and aromatic

aldehydes 59522.18 Beckmann rearrangement 59622.19 Benzilic acid rearrangement 59722.20 -unsaturated aldehydes and ketones 59722.21 Some individual members 599

22.21.1 Vanillin 599

(vi)

22.21.2 Acetophenone 60022.21.3 Benzophenone 602

23. CARBOXYLIC ACIDS (ALIPHATIC ANDAROMATIC) 607–65423.0 Introduction 60723.1 Nomenclature 60723.2 Structure of the carboxylic acids and carboxylate

anions 60923.3 General methods of preparation 61023.4 General physical properties 61323.5 General chemical properties 614

23.5.1 Acidic character 61423.5.2 Reaction with alkalies 61823.5.3 Reaction with metals 61923.5.4 Conversion into carboxylic acid derivatives 61923.5.5 Reduction to alcohols 62023.5.6 Degradation to alkyl halides 62023.5.7 Curtius reaction/rearrangement 62123.5.8 Schmidt reaction 62223.5.9 Reaction with organometallics 622

23.5.10 Decarboxylation 62323.5.11 Conversion into aldehydes and ketones 62423.5.12 Substitution in the alkyl groups/side-chains of

carboxylic acids 62423.5.13 Substitution in the benzene ring 625

23.6 Ascent and decent of fatty acids 62623.7 Some individual members 626

23.7.1 Anthranilic acid 62623.7.2 Cinnamic acid 62823.7.3 Coumarins 62923.7.4 Crotonic acid 63023.7.5 Acrylic acid 63223.7.6 Oleic acid 63323.7.7 Lactic acid 63523.7.8 Malic acid 63623.7.9 Tartaric acid 638

23.7.10 Citric acid 64123.7.11 Salicylic acid 64323.7.12 Phthalic acid 64523.7.13 Oxalic acid 64623.7.14 Malonic acid 64723.7.15 Adipic acid 64823.7.16 Maleic acid 64923.7.17 Fumaric acid 650

24. SUBSTITUTED CARBOXYLIC ACIDS 655–66724.0 Introduction 65524.1 Halogen substituted acids 655

24.1.1 Nomenclature 65524.1.2 Preparation 65624.1.3 Physical properties 65824.1.4 Chemical properties 658

24.2 Hydroxy acids 65924.2.1 Nomenclature 65924.2.2 Preparation 660

24.2.3 Physical properties 66124.2.4 Chemical properties 661

24.3 Keto acids 66324.3.1 -Keto acids 66324.3.2 -Keto acids 66424.3.3 -Keto acids 665

25. DERIVATIVES OF CARBOXYLIC ACIDS 668–69325.0 Introduction 66825.1 Nomenclature 66825.2 Structure 66925.3 Nucleophilic acyl substitution 67025.4 Nucleophilic acyl substitution versus nucleophilic

alkyl substitution 67225.5 Acid chlorides 673

25.5.1 Preparation 67325.5.2 Physical properties 67325.5.3 Chemical properties 673

25.6 Acid anhydrides 67725.6.1 Preparation 67725.6.2 Physical properties 67825.6.3 Chemical properties 678

25.7 Amides 67925.7.1 Preparation 67925.7.2 Physical properties 68025.7.3 Chemical properties 680

25.8 Esters 68125.8.1 Occurrence 68125.8.2 Preparation 68125.8.3 Physical properties 68225.8.4 Chemical properties 68225.8.5 Uses 685

25.9 Ingold’s mechanisms of esterification andhydrolysis of esters 685

25.10 Interconversion of acid derivatives 690

26. ORGANIC DERIVATIVES OF INORGANIC ACIDS694–722

26.0 Introduction 69426.1 Derivatives of Nitric acid 694

26.1.1 Alkyl nirtrates RONO2 69426.2 Derivatives of Nitrous acid 695

26.2.1 Alkyl nitrites, RONO 69526.2.2 Nitroalkanes 696

26.3 Derivatives of Sulphuric acid 70126.3.1 Ethyl hydrogen sulphate 70126.3.2 Methyl sulphate 702

26.4 Derivatives of Hydrocyanic acid 703

26.4.1 Alkyl cyanides or nitriles, R–CN 70426.4.2 Alkyl isocyanides or isonitriles 70726.4.3 Distinction between alkyl cyanides and alkyl

isocyanides 70826.5 Derivatives of Cyanic acid 70826.6 Derivatives of Carbonic acid 710

26.6.1 Urea carbamide 71226.7 Assorted compounds 717

(vii)

26.7.1 Cyanamide 71726.7.2 Thiourea (Thiocarbamide) 71826.7.3 Acrylonitrile vinyl cyanide 719

27. ACTIVE METHYLENE COMPOUNDS (ENOLATES)ENAMINES & 1, 3-DITHIANE 723–75327.0 Introduction 72327.1 Malonic ester, ethyl malonate 724

27.1.1 Preparation 72427.1.2 Properties 72427.1.3 Reaction/Synthetic application 726

27.2 Acetoacetic ester 73027.2.1 Preparation 73027.2.2 Properties 73127.2.3 Basis of synthetic applications 73227.2.4 Synthetic application 734

27.3 Claisen condensation and related reactions 73827.3.1 Reverse Claisen condensation 739

27.4 Tautomerism 73927.4.1 Distinction between tautomerism and

resonance 74327.5 Cyanoacetic ester 743

27.5.1 Preparation 74327.5.2 Synthetic importance 74427.5.3 Applications 744

27.6 Enamines 74627.7 1,3-Dithiane 749

28. AROMATIC NITRO COMPOUNDS 754–76628.0 Introduction 75428.1 Preparation 75528.2 Physical properties 75628.3 Chemical properties 757(A) Reduction products of nitrobenzene 757(B) Selective reduction of polynitro compounds 759(C) Electrophilic substitution 759(D) Nucleophilic aromatic substitution 760(E) Effect of the nitro group on other nuclear

substituents 761(F) Formation of charge transfer complexes 764(G) Acidic character 764

28.4 Uses 76428.5 Benzidine rearrangement 764

29. AMINES 767–80829.0 Introduction 76729.1 Structure of amines 76929.2 Nomenclature 76929.3 Isomerism 76929.4 Primary amines 77029.5 Secondary and tertiary amines 775

29.5.1 Preparation 77529.5.2 Some specific methods for the preparation of

secondary and tertiary aryl amines 77629.6 Separation of a mixture of 1°, 2°, 3° amines and

the quaternary ammonium salt 77729.7 General physical properties 779

29.8 Stereochemistry of amines 77929.9 General chemical properties 780

29.9.1 Basic character of amines 78029.9.2 Influence of structure on basic character of

amines 78129.9.3 Alkylation 78829.9.4 Acylation and Benzoylation 78829.9.5 Reaction with nitrous acid 78929.9.6 Reaction with aldehydes 79029.9.7 Carbylamine reaction/test 79129.9.8 Reaction with phosgene 79129.9.9 Electrophilic substitution reactions of arylamines

79129.9.10 Reaction with carbon disulphide 79329.9.11 Oxidation 793

29.10 Quaternary ammonium hydroxide-Hofmannelimination 795

29.11 Cope elimination 79529.12 Demjanov rearrangement 79629.13 Distinction between primary, secondary and

tertiary aliphatic and aromatic amines 79729.14 Quarternary ammonium salts as phase transfer

catalyst 79729.15 Some individual members 799

29.15.1 Aniline 79929.15.2 Nitroanilines 80029.15.3 Diphenylamine 80129.15.4 Phenylene diamines 802

30. DIAZONIUM SALTS AND RELATED COMPOUNDS809–828

30.0 Introduction 80930.1 Structure of Benzenediazonium chloride 80930.2 Relative stabilities of alkyl and aryldiazonium salts

81030.3 Preparation 81030.4 Physical properties 81130.5 Chemical properties and application 81130.6 Some individual related compounds 819

30.6.1 Phenylhydrazine 81930.6.2 Diazo amino benzene 82030.6.3 p-Amino azo benzene (aniline yellow) 82130.6.4 Diazomethane 822

31. ORGANO SULPHUR COMPOUNDS - I 829–84031.0 Introduction 82931.1 Thioalcohols (Mercaptans) 829

31.1.1 Nomenclature 82931.1.2 Structure 83031.1.3 Preparation 83031.1.4 Physical properties 83131.1.5 Chemical properties 83131.1.6 Uses 834

31.2 Thioethers 83431.2.1 Nomenclature 83431.2.2 Preparation 83431.2.3 Physical properties 835

(viii)

31.2.4 Chemical properties 83531.3 Organosulphur compounds versus Organo-

oxygen compounds 83631.4 Sulphonal 83731.5 Mustard gas 837

31.5.1 Preparation 83731.5.2 Properties 837

32. ORGANO SULPHUR COMPOUNDS-II 841–85632.0 Introduction 84132.1 Preparation 84232.2 Physical properties 84332.3 General chemical properties 84432.4 Derivatives of sulphonic acid 847

32.4.1 Aromatic sulphonyl chloride 84732.4.2 Sulphonamides 85032.4.3 Saccharin 85132.4.4 Chloramine-T 85232.4.5 Dichloramine-T 85232.4.6 Sulphanilic acid 853

32.5 Sulpha drugs 854

33. ORGANOMETALLIC COMPOUNDS 857–87833.0 Introduction 85733.1 Grignard reagents (Organomagnesium

compounds) 85733.1.1 Preparation 85833.1.2 Structure 85933.1.3 Reactions and synthetic application 859

33.2 Organolithium compounds 86633.2.1 Preparation 86633.2.2 Properties 867

33.3 Organozinc compounds 87033.3.1 Preparation 87033.3.2 Physical properties 87033.3.3 Chemical properties 87033.3.4 Reformatsky reaction 871

33.4 Lithium dialkyl copper compounds 87233.4.1 Preparation 87233.4.2 Synthetic importance 872

33.5 Organo silicon compounds 87333.5.1 Preparation 87333.5.2 Properties 87433.5.3 Silicones 87533.5.4 Silicon oils and waxes 87533.5.5 Silicon rubber and resins 875

34. HETEROCYCLIC COMPOUNDS – I 879–90234.0 Introduction 87934.1 Nomenclature 880

I. Five membered heterocycles 88134.2 Occurrence 88134.3 General methods of Preparation/formation 88134.4 Individual methods of preparation/synthesis 882

34.4.1 Pyrrole 88234.4.2 Furan 88234.4.3 Thiophene 883

34.5 General physical properties 88334.6 General chemical properties 883

34.6.1 Electrophilic substitution reactions 88434.6.2 Addition reactions 88734.6.3 Acidic character 88834.6.4 Basic character 88934.6.5 Oxidation 89034.6.6 Ring opening 89034.6.7 Conversion of furan into pyrrole and thiophene

89034.7 Structure 890

34.7.1 Pyrrole 89034.7.2 Structures of furan and thiophene 892

34.8 Furfural, furfuraldehyde 893II. Condensed 5-membered heterocycles 894

34.9 Indole 89434.9.1 Nomenclature 89434.9.2 Occurrence 89434.9.3 Synthesis 89434.9.4 Properties 89534.10 Indoxyl 89634.11 Isatin 897

III. Five membered heterocyclics containing twohetero atoms 898

34.12 Introduction 89834.12.1 General methods of preparation 89834.12.2 Physical properties 89934.12.3 Chemical properties 900

35. HETEROCYCLIC COMPOUNDS–II 903–92535.0 Introduction 903

I. Six membered heterocyclics with one heteroatom 903

35.1 Pyridine 90335.1.1 Isolation from coal tar 90335.1.2 Nomenclature 90335.1.3 Synthesis/formation 90435.1.4 Structure 90535.1.5 Physical properties 90735.1.6 Chemical properties 907

II. Condensed heterocyclic compoundscontaining one hetero atom 912

35.2 Quinoline 91235.2.1 Nomenclature 91235.2.2 Occurrence 91235.2.3 Synthesis 91235.2.4 Properties 913

35.3 Isoquinoline 91635.3.1 Synthesis/formation 91635.3.2 Properties 917

III. Heterocyclics containing more than onehetero atom 917

35.4 Purines 91735.4.1 Synthesis of purine 917

35.5 Pyrimidine 91735.5.1 Synthesis 91835.5.2 Physical properties 918

(ix)

35.5.3 Chemical properties 91835.6 Hofmann Exhaustive methylation 92035.7 Importance of heterocyclic compounds 920

36. CARBOHYDRATES 926–96636.0 Introduction 92636.1 Definition 92636.2 Classification 92636.3 Reducing and non reducing sugars 92736.4 Configuration of Aldotriose and aldopentoses 927

Monosaccharides 92836.5 Introduction 92836.6 Glucose 929

36.6.1 Occurrence 92936.6.2 Manufacture 92936.6.3 Physical properties 92936.6.4 Uses 92936.6.5 Structure 92936.6.6 Chemical properties 936

36.7 Configuration of aldotriose 93936.8 Structure of aldopentoses and aldohexoses 94036.9 Fructose 941

36.9.1 Occurrence 94136.9.2 Manufacture 94136.9.3 Physical properties 94136.9.4 Structure 94136.9.5 Chemical properties 94336.10 The Kiliani Fischer synthesis (Ascending the

series of aldoses) 94436.11 The Ruff degradation (Chain shortening) 94636.12 Wohl degradation 94636.13 Epimerisation of an aldohexose 94736.14 Conversion of an aldohexose into ketohexose

94736.15 Conversion of a ketohexose into Aldohexoses

94736.16 Glycosides 948

Disaccharides 94936.17 Introduction 94936.18 Sucrose (cane sugar) 949

36.18.1 Properties 94936.18.2 Uses 95036.18.3 Structure 950

36.19 Maltose 95236.19.1 Structure 952

36.20 (+) Cellobiose 95436.21 Lactose 955

36.21.1 Manufacture 95536.21.2 Structure 956

Polysaccharides 95636.22 Introduction 95636.23 Starch 956

36.23.1 Manufacture 95736.23.2 Properties 95736.23.3 Structure 95736.23.4 Uses 959

36.24 Cellulose 960

36.24.1 Preparation 96036.24.2 Structure 96036.24.3 Industrial uses of cellulose 961

36.25 Analysis of carbohydrates 96236.26 Glycogen 962

37. AMINO ACIDS, PROTEINS AND ENZYMES967–1002

37.0 Introduction 96737.1 Natural -amino acids 968

37.1.1 Essential and non essential amino acids 96837.1.2 Preparation of -amino acids 97037.1.3 Structure of amino acids (isoelectric point /

zwitter ion) 97237.1.4 Physical properties 97437.1.5 Spectroscopic properties 97437.1.6 Chemical properties 974

37.2 Structural relationship of amino acids to peptidesand proteins 975

37.3 Synthesis of peptides 97737.4 Proteins 980

37.4.1 Classification 98037.4.2 General properties 98137.4.3 Analysis / colour reactions of proteins and amino

acids 98337.4.4 Determination of s tructure of proteins/

polypeptides 98537.4.5 Types of structures of protein 987

37.5. Enzymes 99037.5.1 Chemical nature of enzymes 99137.5.2 Nomenclature and classification 99137.5.3 Salient characteristics 99237.5.4 Mode of enzyme action 99337.5.5 Factors influencing enzyme activity 99437.5.6 Iso-enzymes 99737.5.7 Enzyme kinetics 99837.5.8 Uses 998

38. NUCLEIC ACIDS AND PROTEIN SYNTHESIS1003–1013

38.0 Introduction 100338.1 Structure 1003

38.1.1 Purine and Pyrimidine bases 100438.1.2 Nucleosides 100438.1.3 Nucleotides 100538.1.4 Nucleotide polymers 1006

38.2. Structure of DNA and its role in heredity 100838.2.1 DNA replication 1010

38.3 Ribonucleic acid (RNA) vs DNA 101138.4 Types of RNA 1011

38.4.1 Synthesis of mRNA (Transcription) 101138.4.2 Genetic code and biosysnthesis of proteins

(Translation) 1011

39. LIPIDS (OILS, FATS, SOAPS & DETERGENTS)1014–1032

39.0 Introduction 101439.1 Biological functions 1014

(x)

39.2 Classification of lipids 101439.3 Fats and oils 1016

39.3.1 Common fatty acids present in fats and oils1017

39.3.2 Extraction and refining of oils 101839.3.3 General physical properties 101939.3.4 General chemical properties and industrial

importance 101939.4 Analysis (identification of fats and oils) 1021

39.4.1 Acid value 102139.4.2 Saponification value 102139.4.3 Iodine value or number 102239.4.4 Reichert-Meissl value 102339.4.5 Distinction between animal and vegetable fats

102339.4.6. Fat substitutes / Low calorie fats 1023

39.5 Uses 102439.6 Fixed versus volatile oils (Essential oils) 102439.7 Mineral oils 102539.8 Drying oils 102539.9 Soaps 1025

39.9.1 Types of soaps 102639.9.2 Cleansing action of soap 102639.10 Synthetic detergents (syndets) 102739.11 Soaps vs Synthetic detergents 102939.12 Soft vs Hard detergents 1029

40. STEROIDS AND HORMONES 1033–104340.0 Introduction 103340.1 Classification of steroids 103340.2 Diels’ hydrocarbon 103440.3 Biological importance 103440.4 Cholesterol 1034

40.4.1 Occurrence 103540.4.2 Properties 103540.4.3 Test 103640.4.4 Physiological activity of cholesterol 1036

40.5 Sex hormones 103840.6 Adrenocortical Hormones 103940.7 Bile acids 103940.8 Phytosterols 103940.9 Vitamin D 1040

NON STEROID HORMONES40.10 Thyroid gland hormones 104140.11 Adrenal gland hormones 1042

41. VITAMINS 1044–105541.0 Introduction 104441.1 Classification of Vitamins 104441.2 Fat soluble vitamins 1044

41.2.1 Vitamin-A or retinol or Axerophthol 104441.2.2 Vitamin-D 104741.2.3 Vitamin-E 104741.2.4 Vitamin-K 1048

Water soluble vitamins 104941.3 Vitamin-B-Complex 1049

41.3.1 Vitamin B1 (thiamine) 104941.3.2 Vitamin B2 (riboflavin) 104941.3.3 Vitamin B3 105041.3.4 Folic acid (BC) 1050

41.3.5 Pyridoxine (B6) 105141.3.6 Niacin 105141.3.7 Vitamin B12 1052

41.4 Vitamin C or ascorbic acid 105241.5 Biotin (Vitamin H) 1054

42. CHEMOTHERAPY (The life saving agents)1056–1084

42.0 Introduction 105642.1 Classification 105642.2 Drug action 105742.3 Bactericidal 1057

42.3.1 Sulpha drugs 105742.3.2 Antibiotics 1061

42.4 Antimalarials 106542.4.1 Chloroquine 106542.4.2 Primaquine 106542.4.3 Plasmoquine (Pamaquin) 106642.4.4 Proguanil (Paludrine) 106642.4.5 Mepacrine 1066

42.5 Arsenical drugs 106742.5.1 Neoarsphenamine 106742.5.2 Atoxyl 106742.5.3 Tryparsamide 1067

42.6. Antipyretics and analgesics 106742.6.1 Aspirin 106842.6.2 Methyl salicylate 106842.6.3 Paracetamol 106842.6.4 Phenacetin 106842.6.5 Phenylbutazone 106942.6.6 Analgin 106942.6.7 Some additional antipyretics and analgesics 107042.6.8 Narocotics as analgesic 1070

42.7 Antiseptics and disinfectants 107042.7.1 Halo compounds 107142.7.2 Phenolic compound 107142.7.3 Aldehydes and their derivatives 107242.7.4 Surfactants 107242.7.5 Dyes as antiseptics 1072

42.8 Tranquillizers 107242.8.1 Sedatives 107242.8.2 Antidepressants 1074

42.9 Antitubercular drugs 107442.9.1 p-Aminosalicylic acid 107442.9.2 Thiacetazone 107542.9.3 Isonicotinylhydrazide 107542.10 Antileprotic drugs 1075

42.10.1 Dapsone 107542.10.2 Thiambutosine 107642.10.3 Tryparsamide 1076

42.11 Drugs in cancer therapy 107642.12 Assorted simple organic compounds of medicinal

value 107743. TERPENOIDS 1085–1107

43.0 Introduction 108543.1 Structural unity in terpenoids 108543.2 Classification 108643.3 Isolation of terpenoids (essential oils) 108643.4 General properties 108743.5 Spectroscopic properties 108743.6 Monoterpenoids (Acyclic) 1087

(xi)

43.6.1 Myrcene 108743.6.2 Citral 108943.6.3 Geraniol 1092

43.7 Cyclic monoterpenes 109343.7.1 Limonene 109343.7.2 -Terpineol 109543.7.3 Menthol 1098

43.8 Monocyclic sesquiterpenoids 109943.8.1 Zingiberene 1099

43.9 Bicyclic monoterpenes 110043.9.1 -Pinene 110043.9.2 Camphor 110143.10 Triterpenes 110243.11 Tetraterpenes 1102

43.11.1 -Carotene (C40H56) 110243.12 Polyterpenes 1103

43.12.1 Natural rubber (C5H8)n 1103

44. ALKALOIDS 1108–113544.0 Introduction 110844.1 Nomenclature and classification 110844.2 Occurrence 110944.3 General properties 110944.4 Isolation/extraction 111044.5 General structure determination 111044.6 Piperidine alkaloids 1112

44.6.1 Piperine 111244.6.2 Coniine 1114

44.7 Pyrrolidine pyridine alkaloid 111744.7.1 Nicotine 1117

44.8 Tropane alkaloids 111944.8.1 Atropine 111944.8.2 Cocaine 1123

44.9 Quinoline alkaloids 112544.9.1 Quinine 112544.9.2 Cinchonine 113144.10 Phenanthrene alkaloids 1131

44.10.1 Morphine 113144.11 Narcotic drugs (Drug Abuses) 113244.12 Physiological action 1132

45. SPECTROSCOPY 1136–119445.0 Introduction 113645.1 The electromagnetic spectrum 113645.2 Some relevant mathematical relationships 113745.3 Spectroscopic techniques in service of organic

chemists 113745.3.1 Infrared spectroscopy 1138

Basis 1138, Instrumentation 1138, Sampling1139, Stretching and bending vibrations 1139,Vibrational frequency (Hooke’s law) 1140, Fingerprint region in an IR spectrum 1140, Major bandsin the IR spectra of different classes of organiccompounds 1140

45.3.2 Ultraviolet spectroscopy 1148Basis 1148, Instrumentation 1149, Solvents1149,Presentation of a UV spectrum 1149, Transitionin UV spectroscopy 1150, Some terms used inUV spectroscopy 1150, UV spectra ofunsaturated hydrocarbons 1151, UV spectra of

, -unsaturated ketones 1153, UV spectra ofaromatic compounds 1154

45.4 Applications of UV and IR spectroscopy 115645.4.1 Problems based on IR and UV analysis 1156

45.5 Nuclear Magnetic Resonance (NMR)spectroscopy 1160Basis 1160, Instrumentation 1161, The chemicalshift 1163, Relaxation processes in NMR-Spectroscopy 1164, Position of NMRsignals 1165, Number of NMR signals 1165,Factors affecting chemical shift 1166, Peak areaand proton counting 1168, Splitting ofsignals 1168, Coupling constant 1171,Deuterium labelling 1172, Equivalence ofprotons 1172, Applications 1173, Merits of NMRspectroscopy 1175

45.6 Mass spectrometry 1176Basis 1176, Nitrogen rule for the parent ion1177,Fragmentation 1177, Mass spectroscopy oforganic compounds 1178, Applications 1181

45.7 Problems based on Spectroscopy 1181

46. COLOUR AND CHEMICAL CONSTITUTION, DYES1195–1224

46.0 Introduction 119546.1 Colour and chemical constitution 1195

46.1.1 Theories of colour and chemical constitution 119646.1.2 Modern theories of colour 1199

46.2 DYES 120046.2.1 Requirements of a dye 120046.2.2 Chemical nature 120046.2.3 Classification 1200

1. Natural and synthetic dyes 12002. Classification based on structure 12003. Classification based on application 1200

46.2.4 Nomenclature 120246.2.5 Chemistry of representative important dyes 1202

(A) Triphenylmethane dyes 1202(B) Nitro and nitroso dyes 1204(C) Azo dyes 1206(D) Phthalein and xanthen dyes 1210(E) Anthraquinone dyes 1213(F) Indigoid dyes 1214(G) Fluorescent brightening agents 1216

46.3 Pigments (Authocyanins and flavones) 121746.3.1 Anthocyanins 121846.3.2 Flavones 121846.3.3 Phthalocyanines 121846.3.4 Carotenoids 121846.3.5 Chlorophyll 1218

46.4 Food colours 1219

47. PHOTOCHEMICAL REACTIONS 1225–124547.0 Introduction 122547.1 Photochemical Versus Thermal reactions 122547.2 Electronic excitation 122647.3 Modes of dissipation of energy 122847.4 Quantum efficiency / quantum yield () 123247.5 Photochemical reactions 1232

47.5.1 Elimination reactions 1233

(xii)

47.5.2 Photolysis of cyclic ketones 123447.5.3 Photolysis of aldehydes 123547.5.4 Photolysis of compounds containing

nitrogen123547.5.5 Photochemical reduction reactions 123647.5.6 Photocyclo addition reactions 123747.5.7 Photo induced reactions of ,-unsaturated

ketones 123847.5.8 Photochemistry of alkenes 124047.5.9 Photochemical oxidations 1242

48. PERICYCLIC REACTIONS 1246–125648.0 Introduction 124648.1 Salient features of Pericyclic reactions 124648.2 Types of Pericyclic reactions 1246

48.2.1 Electrocyclic reactions 124748.2.2 Cycloaddition reactions (Diels-Alder reaction)

125148.2.3 Sigmatropic rearrangements 1253

48.3 The Frontier orbital method 125548.4 Pericyclic reaction in human body 1256

49. REAGENTS OF SYNTHETIC IMPORTANCE1257–1287

49.0 Introduction 125749.1 Aluminium isopropoxide 125749.2 Baker’s Yeast 125949.3 Crown Ethers 126049.4 Diazoacetic ester 126049.5 Diazomethane 126149.6 Lead Tetra Acetate 126149.7 Lithium aluminium hydride (LiAl H4) 126449.8 Lithium Diisopropyl Amide (LDA) 126749.9 N-Bromosuccinimide 1269

49.10 Osmium tetraoxide 127149.11 Ozone 127349.12 Periodic acid 127549.13 Raney nickel 127749.14 Selenium dioxide and selenious acid 127949.15 Sodamide 128149.16 Sodium borohydride 128249.17 Wilkinson’s Catalyst 128449.18 Ziegler-Natta Catalyst 1286

50. METABOLISM OF CARBOHYDRATE, PROTEINAND LIPID 1288–130250.0 Introduction 128850.1 Carbohydrate metabolism 1288

50.1.1 Anaerobic glycolysis (Embden-MeyerhofPathway) 1288

50.1.2 Aerobic metabolism (Krebs cycle or Tricarboxylicacid cycle) 1293

50.2 Protein metabolism 129550.2.1 Formation of Urea 1297

50.3 Lipid metabolism 129850.3.1 Beta oxidation of fatty acids 129850.3.2 -Oxidation of fatty acids 129950.3.3 Efficiency of fat respiration 129950.3.4 Biosynthesis of fatty acids and fats 130050.3.5 Conversion of fat to carbohydrate - The

glyoxylate cycle 1300

51. MOLECULAR REARRANGEMENTS 1303–130751.0 Introduction 130351.1 Types of molecular rearrangements 1304

52. GREEN CHEMISTRY AND ITS APPLICATIONS1308–1331

52.0. Introduction 130852.1. Twelve principles of green chemistry 1308

52.1.1. It is better to prevent waste than to treat or cleanup waste after its formation 1309

52.1.2. Synthetic methods should be designed tomaximize the incorporation of all the materialsused in the process into the final product 1310

52.1.3. Whenever practicable, synthetic methodologiesshould be designed to use and generatesubstances that possess little or no toxicity tohuman health and the environment 1312

52.1.4. Chemical products should be designed topreserve efficacy of function while reducingtoxicity 1313

52.1.5. The use of auxiliary substances (e.g., Solvents,Separation Agents, etc.) should be madeunnecessary wherever possible and innocuouswhen used 1314

52.1.6. Energy requirements should be recognized fortheir environmental and economic impacts andshould be minimized 1316

52.1.7. A raw material or feed stock should be renewablerather than depleting whenever technically andeconomically practicable 1320

52.1.8. Unnecessary derivatization (blocking group,protection, deprotection, temporary modificationof physical/chemical processes) should beavoided whenever possible 1321

52.1.9. Catalytic reagents (as selective as possible) aresuperior to stoichiometric reagents 1322

52.1.10. Chemical products should be designed in sucha manner that at the end of their function theydo not persist in the environment and breakdown into innocuous degradation products 1323

52.1.11. Analytical methodologies need to be furtherdeveloped to allow the real time, in processmonitoring and control prior to the formation ofhazardous substances 1323

52.1.12. Substances and the form of a substance usedin a chemical process should be chosen so asto minimize the potential for chemical accidentsincluding release, explosions and fires 1324

52.2. Applications 1324

Appendices :1. Structure and Bonding 1332-13402. Correlation tables 1341-13463. Retrosynthetic Analysis 1347-13564. Organophosphorus Compounds 1357-13655. Ureides, Pyrimidines and Purines 1366-1380

Index name reactions 1381-1382Index (General) (i to x)

INDEX

(i)

AAbsolute alcohol 493Absolute configuration 139Absorption spectroscopy 1138Accelerators 313Acetals 575Acetoacetic acid 664Acetoacetic ester 730Acetone dicarboxylic acid 642Acetonylacetone 736Acetonyl carbanion 73Acetophenone 600Acetoxylation 1261Acetylacetone 735Acetylation 748Acetylene 276Acetylide anion 277Acetylides 279Achiral 129Acid anhydrides 677Acids and bases 60Acid chlorides 668, 673Acid hydrolysis 732Acid value 1021Acidic dyes 1201Acid orange-7 1201, 1207Aconitic acid 642Acraldehyde (Acrolein) 597Acriflavin 1072Acromycin 1061Acrylic acid 632Acrylonitrile 719Actinometry 1232Activating groups 333Activation energy 365Activators 995Active methylene compounds 723Active valeric acid 726Acyclic compounds 102Acylation 482, 675, 788Acylating agents 675Acyl cations/acylium ions 70Acyloin 684Adamantane 203, 217Addition 1,2-and 1,4 266Additives 1028Addition Polymerization 295Addition reactions 90Addition reactions-nucleophilic

572, 91Adenine 1004Adenosine 1004Adenosine monophosphate 1006Adenosine triphosphate 1007Adipic acid 648Adrenaline 1042ACTH 967Aerolic metabolism 1293Aglycone 949

Albuminoids 981Alcoholdehydrogenase 1292Alcohols 476Alcoholysis 674Aldehydes and ketones 561Aldimines 706, 790Aldohexoses 940Aldotriose and aldopentoses 927Aldolase 1290Aldol condensation 75, 576Alizarin 531, 1213Alizarin red-S 1214Alizarin aluminium chelate 1201Alkadienes 258Alkaloids 1108Alkanes 183Alkenes 229Alkenyl groups 230Alkenyl halides 440Alkoxymercuration-demercuration

244, 545Alkyd resins 307Alkylation 241, 279, 788Alkyl cyanides 704Alkyl halides 420Alkyl isocyanates 708Alkyl isocyanides or isonitriles 707Alkyl nitrates 694Alkyl nitrites 695Alkyl sulphonate 483Alkynes 276Allenes 262-263Allyl alcohol 289, 495Allylation 748Allyl carbanion 73Allyl cation 49, 70, 445Allyl halides 443Allylic bromination 253, 632, 1268Allylic halogenation 223Allylic substitution 251Allyl radical 253Alternating axis of symmetry 132Aluminium isopropoxide 589, 1257Amadori rearrangement 936Ambident ions 425Amides 679Amidine 706Amination 909Amines 767Amino acids 967p-Amino-azobenzene 821Aminolysis 674Aminonaphthalenes 393Aminopyrine 1070p-Aminosalicylic acid 1074Ammonolysis 674-679Amylopectin 958Amylose 957Anabolism 1288

Anaerobic glycolysis 1288Analgin 1069Analyzer 134Analytical plate 12Anchimeric assistance 434Androsterone 1038Angelica lactone 665Angle strain 169, 210Angular methylation 1285Aniline 799Aniline yellow 821, 1206Anilinium ion 783Anils 595Animal fats 1017Anionic addition 298Anionic detergents 1027Anisol 550Anisotropy 1167Annealing 983Annulenes 327Anomeric carbon 932Anomers 932Anthocyanins 1217Anthracene 397Anthracene peroxide 402Anthracene picrate 403Anthranilic acid 626, 851Antiaromatic 326Anticodon 1011Antirachitic factor 1040Anthraquinone 404Anthraquinol 404Anthraquinone dyes 1213Anthrone 404Antiaromatic compounds 326Antiberiberi factor 1049Antibiotics 1061Antibonding orbitals 261, 323, 1226Antidepressants 1074Antihaemorrhagic 1048Antiknocking agent 30Antiknock value 29Antileprotic drugs 1075Antimalarials 1065Anti-Markovnikov addition 237Antioxidants 1021Antipyretics and analgesics 1067Antipyrine 737Antiredeposition agents 1029Antiseptics 1070Antisterility factor 1047Antitubercular drugs 1074Antrafacial 1252Apoenzyme 991Aprotic solvent 684Arabinose 945Aralkyl amines 768Aralkyl halides 455, 468Arbutin 949

Arenes 349Armstrong-Baeyer’s formula 320Arndt-Eistert reaction 612, 676, 823Aromatic 326Aromatic amines 767Aromatic hydrocarbons 349Aromaticity 325Aromatic nitro compounds 754Aromatic sextet 329Aromatisation 197Aromatic sulphonic acids 841Aromatic sulphonyl chlorides 847Arsenic drugs 1067Arsphenamine 1067Aryl amines 768Arylation 910, 915Aryl diazonium salts 810Aryl halides 455Ascorbic acid 1052Aspartic acid 651Aspirin 526, 645, 1068Asymmetric carbon 130, 133Asymmetric synthesis 152Atebrine 1066Atactic 295Atoxyl 1067Atropic acid 1120Atropine 1119Atropisomerism 414Autoxidation 546, 1020Auxochrome 1150, 1197Aviation gasoline 30Axial bonds 172Azeotropic mixture 493Azobenzene 758Azodyes 1206Azoxybenzene 758Azulene 332

BBactericidal 1057Baeyer’s formula 320Baeyer-strain theory 210Baeyer’s test 249Baeyer-Villiger oxidation 592Bakelite 302Baker and Nathan effect 55Baker’s Yeast 1259Ball and stick model 129, 162Baltz-Schiemann reaction 813Banana bond 213Barbiturates 730, 1073Barbituric acid 715, 1073Barfoed’s reagent 591Barton model 129Bart reaction 815Barton reaction 1235Basic dyes 1201Bathochromic effect 1198Bathochromic shift 1150Beckmann rearrangement 302, 596,

1305Beer-Lambert law 1149

Beilstein test 16Benadryl 1080Benedict solution/reagent 591, 642Benzaldoxime 595Benzedrin 1074Benzene 318Benzene derivatives 349Benzene diazonium chloride 809Benzene hexachloride BHC 472Benzene sulphonamide 849Benzenoid aromatic compounds 103Benzhydrol 602Benzidine 410Benzidine rearrangement 764Benzidine semidine rearrangement

1306Benzilic acid rearrangement 597Benzimidazoles 802Benzocaine 771, 1079Benzoin condensation 580Benzophenone 602Benzopinacol 602p-Benozoquinone 537, 803Benzoylation 788Benzoyl ecgonine 1123Benzyl alcohol 496Benzyl carbanion 73Benzyl cation 50Benzyl radical 469Benzylic hydrogen 371, 469Benzyne intermediate 463, 869Benzyne -complex 465Benzyne trapping 465Bergius process 31Betaine 587Bicyclic compounds 119Bicyclobutane 216Bijvoet’s X-ray analysis 139Bile acids 1039Bimolecular displacement 460Bimolecular elimination (E2) 435Bimolecular reduction 590Biotin 1054Biphenyl 409Birch reduction 286, 369, 888Bisazo dyes 1208Bischler-Napieralski synthesis 916Bismaleimide resin 307Bismarck Brown 804, 1208Biuret test 714, 983Blankophor-R 1216Blankophor WT 1216Blomstrand structure 809Boat conformation 171Bond angle 1313Bond dissociation energy D 1314Bond energy (E) 1314Bonding orbitals 261, 323, 1226Bond length 1313Borneol 1101Bouveault-Blanc method 683Bridged mercuriniumion 243

Brilliant green 1204Bucherer reaction 392Buna rubbers 311Buna-N 269, 311Buna-S 269, 311Butter yellow 1207-Butyrolactone 659

CCahn-Ingold priority sequence 141Calciferol 1047Calculation of molecular formula 23C-Allylation 521C-Alkylation 747Camphor 1101Camphoric acid 1101Camphoronic acid 1101Camphoroquinone 1101Cannizzaro reaction 584-Caprolactone 663Caramel 1221Carbamide 712Carbanions 72Carbenes 76, 1304Carbinol 478Carbobenzoxy chloride 711Carbobenzoxy method 977Carbocations/carbonium ions 68Carbocyclic 102Carbohydrates 926Carbohydrate metabolism 1288Carbonation 611Carbon tetrachloride 450Carbonyl compounds 561Carboxylate anions 609Carboxylic acids 607Carbromal 1078Carbylamine reaction 77, 449, 791Carbylamines 707Carius method 18Carcinogenesis 408Carmic acid 1214Caro’s acid 756-Carotene 1103, 1197Carotenoids 1218Carr-Price reaction 1045Carvone 1094Catabolism 1288Catenation 1Catalytic cracking 28Catalytic dehydrogenation 408Catalytic hydrogenation 184, 254,

370, 683Catalytic reduction 759Catalytic reforming 32, 197Catechol 535Cationic addition 297Cationic detergents 1028Cellobiose 954Cellophane 962Celluloid plastics 962Cellulose 960Cellulose acetate 962

(ii)

Cellulose nitrate 961Cellulose xanthate 962Centre of symmetry 132Cerebroside 1016Cetane number 30Cetylpyridinim chloride 1072Chain growth polymerization 295Chain isomers 127Chair conformation 170, 935Charcoaling 5Channel complexes 98Chargaff’s rule 1009Charge transfer complexes

98, 531, 764Chattaway’s amide-amidine

structure 716Cheilosis 1050Chemical shift 1163Chemotherapy 1056Chichibabin reaction 909, 1281Chiral carbon 129, 135Chirality 128Chloral hydrate 574, 1078Chlorambucil 1076Chloramine-T 852, 1071Chloramphenicol 1062Chloretone 448Chloroform 446, 1079Chlorofluorohydrocarbons 446Chloromethylation 383, 470Chloromycetin 1062Chlorophyll 1218Chloropicrin 448, 531Chloroplatinic salt method 21Chloroquine 1065Chlorotetracycline 1064Cholesterol 1034Chromate ester 484Chromatography 11Chromogen 1196Chromophore 1150, 1196Chromophore auxochrome theory

1196Chromoplate 12Chromoproteins 981Chrysoidine 1207Cincholoipenic acid 1127Cincholoipon 1128Cinchomeronic acid 917Cinchonine 1131Cinnamaldehyde 597Cinnamic acid 628Circular paper chromatography 13cis-trans decalines 157Cis-trans isomerism 155Citraconic acid 642Citral 1089Citric acid 641Civetone 218Claisen condensation 730Claisen ester condensation 74Claisen reaction 579

Claisen rearrangement 94, 521Claisen-Schmidt reaction 578Classificaiton of organic compounds

102Clathrates 98Claus structure 320Clemmensen reduction 590Coaltar distillation 3Cocaine 1070, 1123Coenzyme 991, 996Codeine 1132Codon bases 1012-Collidine 1128Collision frequency 195Collodion 962Column chromatography 11Combustion 197Condensation polymers 294Condensation polymerisation 294Condensed ring compounds 216Configuration 139Configuration in polymers 295Conformational analysis 169Conformation of alkanes 162Conformers 162, 167Conformational diastereomers 167Conformational enantiomers167, 175Coniine 1114Congo red 1209Conjugated dienes 258Conjugated proteins 981Conrotatory 1247Conservation of orbital symmetry 1246Contributing structures 49Conyrine 1115Cooking gas 27Coordination polymerisation 299Cope elimination 795Copolymer 254, 294Copolymerization 294Corey-House synthesis 186Corey-Seebach method 749Coronene 332Cortisol 1039Cortisone 1039Coulson-Moffits concept 213Coumaric acid 630Coumarins 629Coumarinic acid 629Coupling constant 1171Coupling of free radicals 66Coupling reaction 817Cracking 28Cross aldol condensation 578Cross Cannizzaro reaction 585Cross claisen condensation 738Crotonaldehyde 597Crotonic acid 630, 735Crown ethers 555, 1260Crystallization 4Crystallizing 4Crystal Violet 1203

Cubane 203, 216Cumene 515Cumulated dienes 258Curtius rearrangement 77, 621, 774Curved arrow 46Cyanamide 713, 717Cyanic acid 714Cyanides 704Cyanoacetic ester 743Cyanocobalamine 1052Cyanoethylation 719, 748Cyanomethylation 465, 707Cyanuric acid 714Cyclic acetal 501Cyclic bromonium ion 240Cyclic ethers 550Cyclic ketal 501, 576Cyclic sulphone 270Cyclic ureides 7154+2 cycloaddition 270Cycloaddition reactions 1251Cycloalkanes 202Cycloalkenes 219Cyclodehydrogenation 1280Cycloheptatrienyl cation 331Cyclo-octatetraene 328Cyclopentadienyl anion 74, 331Cyclopentadienyl cation 331Cyclopropenium salts 330Cyclopropane 1079Cyclopropenyl cation 330p-Cymene 1090Cynidin chloride 1217Cytosine 1004Cytidine 1005

D2, 4-D 521Dacron 301Dakin reaction 515, 535Dapsone 1075Dashed bond 130Darzens glycidic ester synthesis

583, 1282D and L notation 139DDT 476Deactivating groups 333Deamination 1296Debye unit 36Decalin 217, 387Decarbonylation 1284Decarboxylation 187, 205, 623, 659Decomposition 66Dehalogenation 231, 278Dehydration 232, 263, 487Dehydroacetic acid 737Dehydrogenation 484Dehydrohalogenation 230, 278, 1281Delocalization 47Delocalization energy 49, 260Delphinidin chloride 1217Demerol 1132Demjanov rearrangement 796

(iii)

Denaturation 982Deoxythymidine 1005Deoxythymidine-5-phosphate 1006Depression in freezing point 20Derived names 104Desulphuration 1278Desulphonation 356, 845, 1285Detergents 1027Determinaiton of mol. wt. 20Dettol 1071Deuterium labelling 1172Developed or ingrain dyes 1201Dewar structure 320Dextrin 957Dexorubicin 1077Dextrorotatory 1349, 10-Dianthracene 402Dianthracene 404Diastase 493Diastereomers 143, 156Diaxial interactions(1,3 & 1,5) 173Diazepam 1073Diazoacetic ester 1260Diazoamino benzene 820-Diazoketone 612, 823Diazomethane 822, 1261Diazonium hydroxide 818Diazonium salts 809Diazotates 810Diazotization 789, 810Dichloramine-T 852Dicoumarol 630Dicyclohexyl carbodiimide (DCC)979Dieckmann condensation 75, 204Diels-Alder reaction 270, 399, 402, 888Diels’ hydrocarbon 1034Dienone-phenol rearrangement 1304Dienophile 270Diagonal hybridization 1311Dihedral angle 164Dihydroxy acetone 5061, 3-Diketohydrindene 397Dimedone 730Dimerization 288, 6292,4-Dinitrofluorobenzene 9862,4-Dinitrophenylhydrazine 820Diphenic acid 407Diphenyl 409Diphenyl amine 801Diphenyl methane 4121, 3-Dipolar addition 247, 899Dipole-dipole interactions 168Dipole moment 36, 344Direct or substantive dyes 1200Disaccharides 949Disinfectants 1070Dispensable amino acids 968Disperse dyes 1202Disproportionation 67Disrotatory 1247Dissipation of energy 1228Distillation at atmospheric pressure 7

Distillation under reduced pressure 71,3-Dithianes 564DNA 1007DNA replication 1010Dow’s process 515, 749Dragendroff’s reagent 1109Drugs 1056Drying oils 1025Dumas method 17Durene 352Dyes 1195, 1200

EE2 mechanism 435E1 mechanism 436Ecgonine 1123Eclipsed Conformation 162, 164Edman’s degradation method 986Elaidic acid 634Elastomers 311Elbs persulphate oxidation 529Electrocyclic reactions 268, 1247Electrolytic reduction 758Electromagnetic spectrum 1136Electromeric effect 45Electronegativity 35Electron displacements 41Electronic excitation 1226Electron withdrawing groups 337Electrophilic reagents 64Electrophilic aromatic substitution

333, 357Electrophilic substitution 394, 401Electrophilic addition 91, 234, 264, 280Electrovalent bond 36Elemental analysis 15Element effect 436Elements of symmetry 131Elevation in boiling point 20-Elimination 76Elimination addition mechanism 463Elimination reactions 91, 435, 1233Elution 11Embden-Meyerhof Pathway 1288Emde degradation 1111Empirical formula 20Emulsin 955Enamines 746Enantiomeric excess 138Enantiomerism 129Enantiomers 129Endo rule 272Endothermic reaction 82Energy of activation 79, 365Energy profiles 79Enfleurage process 1086Enolizable ketones 593Enolates 723Envelope conformation 215, 225Enzymes 990Eosin 1212Epimer and epimerisation 936, 947Epoxidation 224, 251, 551

Epoxides 551Epoxy resins 306Equanil 1073Equatorial bonds 172Equilenine 1038Equivalence of protons 1072Equivalent protons 1165Erdmann’s reagent 1109Ergosterol 1047Erlenmeyer structure 378Erlenmeyer azlactone synthesis 971Erythro and threo configuration 150Erythrosin 1212ESR 79Essential amono acids 968Essential oils 1024, 1086Esters 681Esterases 992Estimations 16-19Estrogens 1038Etard’s reaction 372, 566Ethambutol 1075Ethane sulphonic acid 833Etherates 546Etherification 520Ethers 542Ethinylation 289Ethosuccinimide 1080Ethyl alcohol 492Ethyl anion 277Ethylene glycol 496Ethylene oxide 551Ethyl hydrogen sulphate 701Eugenol 550, 599Exocyclic double bond 1151Explosives 764External compensation 145Extraction with a solvent 6Exothermic reaction 81E-Z system of nomenclature 158

FFast green O 1205Fats and oils 1016Favorskii rearrangement 1306Fehling reagent 591, 639Fehling solution 591Fenac 473Fenthion 473Fenton’s reagent 506Fermentation 493, 944, 999Ferric ferrocyanide 15Ferrocene 331Fibrous proteins 980Filtering 4Finger print region 1138Fischer-Indole synthesis 894Fischer projections 145Fischer-Tropsch process 32Fischer-Speir modification 681Fitting reaction 410Flash photolysis 1232Flash point 30

(iv)

Flavinadenine dinucleotide 996Flavones 1218Fluorene 415Fluorenone 415, 1285Fluorescein 531Fluorescence 1211, 1230Fluorescent brightening agent 1216Fluorocarbons 445Folic acid 1050Food colours 1219Formylation 401, 411Fractional crystallization 5Fractional distillation 9Fractionating columns 10Fragmentation 1177Frankland-Duppa formula 741Frankland’s reagent 870Franck-condon transition 1230Free radicals 65Free radical additions 91, 248, 267Free radical substitution 89, 189, 366Freons 446Freund’s method 204Friedel crafts alkylation 353, 362Friedel-Crafts acylation 363Friedlander’s synthesis 913Fries rearrangement 519, 569, 789Frohde’s reagent 1109Frontier orbital method 1255Frost circle 325Fructose 941Fructosides 943Fuchsine/magenta 1204Fumarase 1295Fumaric acid 616, 650Functional isomers 127Furan 882Furanose structure 943Furfural 893

GGabriel’s phthalimide reaction

425, 774, 970Gallic acid 660Gas chromatogram 14Gas-liquid chromatography 14Gasoline or petrol 29Gatta-percha 313Gattermannaldehyde synthesis 566Gattermann-Koch aldehyde synthesis

411Gatterman reaction 812Gatterman synthesis 527Gauche conformation 166Gem-diols 574Geminal dihalides 427Geminal protons 1171Genetic code 1011Geometric isomerism 155Geranic acid 1089Geranial 1090Geraniol 1092Gerber method 493

Geronic acid 1103Geuther formula 741Gilman reagent 186, 872Glass temperature 307, 308Globular proteins 980Globulins 981Glucaric acid 938Glucosazone 936Glucose 9291,4-Glucosidic linkage 958Glutamic acid 969Glutaric acid 735Glycerol 502Glycerides 504, 1080Glyceryl trinitrate 504Glycogen 962Glycolases enzymes 992Glycolipids 1015Glycolysis 1288Glycone 949Glycollic acid 661Glycoproteins 981Glycosides 948Glycosidic bond 948Glyoxalic acid 661Glyoxylate cycle 1300Glyptal 307Golay detector 1139Gomberg reaction 410, 815Grating 1138Griess method 342Griess structure 809Grignard reagents 857Guaiacol 549Guanidine 1004Guanine 1004Guanosine 1005Guanosine-5-phosphate 1006Gutta-percha 1104

HHagers reagent 1109Half chair conformation 171Halide exchange 423Haloform reaction 591Haloform test 485Halogenation 189, 360, 381Halothane 1079Halozone 1071Hantzsch synthesis 904Hard soaps 1026Haworth projection formulae 935Haworth synthesis 379, 399, 408HDPE 300Heat of combustion 211, 321Heat of hydrogenation 260, 321Hell-volhard zelinsky reaction

625, 656Hemiacetal 575Herbicides 473Heroin 1070Herzig-Meyer method 1110

Hetaryne 910Heteroannular diene 1152Heterocyclic compounds 103, 879,

903Heterolytic cleavage 65Heteronuclear substitution 386Heteropolysaccharides 927Heumann’s synthesis 12154n-Hexylresorcinol 1071High temperature cracking 33Hinsberg’s method 778Hinsberg’s reagent 778Hippuric acid 974Histones 981Hofmann ammonolysis 772Hofmann reaction/degradation

77, 680, 772Hofmann elimination

231, 233, 437, 795, 1110Hofmann exhaustive methylation 233Hofmann’s method of separation 777Hofmann mustard oil reaction 793Holoenzyme 991Homoannular diene 1152Homologous series 104Homolytic cleavage 65HOMO 1239, 1255Homonuclear substitution 385Homopolymers 294Homopolysaccharides 927Hooke’s law 1140Hopkins-Cole reaction 984Houben-Hoesch reaction 528, 885Houben-Hoesch synthesis 569Hückel M.O. 1249Hückel rule 327Hunsdiecker reaction 423, 457, 620Hybrid bond 50Hybridization 1308Hydration 283Hydroboration oxidation222, 244, 282Hydrocracking 29Hydrodealkylation 377Hydroforming 32Hydrogen bonds 37Hydrogenation 206, 224, 1019Hydrogenerator 1019Hydrogenolysis 184, 683, 1020Hydrolytic enzymes 992Hydroquinone 537Hydroxamic acid 684Hydroxylation 224, 249Hygrinic acid 1117Hyperchromic shift 1150Hyperconjugation 54Hypobromite method 714Hypochromic effect 1150Hypsochromic effect 1198Hypsochromic shift 1150

IIdentity 131Imidazole 898

(v)

Imine-enamine tautomerism 128, 740Imminium salt 748Improper axis of symmetry 132Inclusion compounds 97Inclusion of carbene 198Indispensable amino acids 968Indigoid dyes 1214Indigo 1214Indigotin 894Indole 894Indolenine 896Indoxyl 896Induction period 1020Inductive effect 41Infra red spectroscopy 1138Ingold’s mechanism of

esterification and hydrolysis 685Ingrain dyes 1201Inhibitors 297, 997Insecticides/pepsticides 472Intermediates 80Intermolecular H-bonds 37, 38, 516Internal bond angle 210Internal compensation 144Internal conversion (IC) 1229Intersystem crossing (ISC) 1229Intramolecular H-bond 38, 516Intrinsic basicity 61Inulin 941Inversion of configuration 429Invertase 492Invert sugar 950Iodex 644Iodoform 449, 1071Iodoform test 484, 592Iodol 1071Iodine value 1022Iodometric method 741-Ionone 1102Isatin 897Isatoic anhydride 628Isocitric acid 641Isoelectric point 973Isoenzymes 997Isoeugenol 550Isolated dienes 258Isolation of intermediates 93Isomerisation 197, 542Isomerism 126, 769Isoniazid 1075Isoprene 1085Isoprene rule 1085Isoquinoline 916Isotactic 295Isothiazole 898Isothiocyanate 793Isotope effect 364, 366, 435Isotope exchange 689Isotope labelling 94Isourea 716Isovalent hyperconjugation 57Isoxazole 898

Itaconic acid 642IUC & IUPAC names 106

JJablonski diagram 1229

KKa and pKa 63Kb and pKb 781Kekule structure 318Ketene 612, 731Keto acids 663Keto-enol tautomerism 128, 740Ketonic hydrolysis 731-Ketovaleric acids 736Kharasch effect 237Kiliani-Fischer Synthesis 944Kinetic studies 95Kjeldahl method 17Knocking 29Knoevenagel reaction 581, 735Knorr’s method 741Kohler ring expansion 824Kolbe’s electrolysis 187Kolbe-Smidt reaction 525Korner’s absolute method 342Korner’s structure 906Krebs Cycle 1293Kurt Meyer method 741

LLactic acid 635Lactide 636, 662Lactose 955Ladenberg prism formula 320Laevorotatory 134Laevulaldehyde 1104Lanosterol 1102Lassaigne’s test 15LDPE 300Leaded gasoline 30Lead tetra acetate 498, 1261Lederer-Manase reaction

302, 526, 599Leucart reaction 775Levine and Hauser reaction 707Levodopa 1080Levulinic acid 665, 938Lewis concept of acids and bases 62Lewisite 289Libermann-Burchard reaction 1036Liebermann nitroso reaction 529Liebig’s combustion method 16Lignocaine 1080Limonene 1093Lindlar’s catalyst 232, 285Lipases 1019Lipidine 1125Lipid metabolism 1298Lipids 1014Lipoproteins (HDL & LDL) 981, 1036Lithium aluminium hydride 588, 1264Lithium dialkyl copper 186, 872Lithium disopropylamide (LDA) 1267Lithium tri-tert-butoxy aluminium

hydride 563, 676Lithium triethoxyaluminium hydride706Livodopa 1080Lobry de Bruyn and Alberda van-Ekenstein rearrangement 937Loiponic acid 1125Lossen rearrangement 78, 1305Low calorie fats 1023Lowest sum rule 109Lowry-Brønsted concept 60LPG 183Lucas test/reagent 489Lumisterol 1047LUMO 1255Lutidine 904Lycopene 1221

MMadelung synthesis 895Malachite green 1203Malaprade reaction/reagent 498Malathion 473Maleic acid 616, 649Malic acid 636Malic synthetase 1300Malonic acid 647Malonic ester 724Malonyl urea 715Malt 493Maltase 493Maltonic acid 952Maltose 493, 952Mannich base 586Mannich reaction 586, 701Mannose 937Marquis reagent 1109Martius yellow 1205Markovnikov’s rule 234Mash 493Mass Spectrometry 1176Mathedrine 1074Mayer’s reagent 1109Mc Lafferty rearrangement 1180Mechanical hindrance 58Meerwein-Pondorf verley reduction

589, 1257Meerwein reaction 816Medicated soaps 1026Melamine 718Melamine Formaldehyde resin 306Menadione 389Menthol 1098Mepacrine 1066Mercaptans 829Mercaptides 833Mercaptols 832Mercerised cotton 960Mercuration 370, 528, 645Mercurochrome 1212Merophan 1076Meroquinene 1127Merrifield method 978Mesaconic acid 642

(vi)

Mesityl oxide 597Meso compound 144Mesomeric effect 53Mesoxalic acid 506Metamers 127Methadone 1132Methotrexate 1061Methoxyflurane 1079Methyl alcohol 491Methylating agent 703, 823Methyl isocyanate (MIC) 791Methyl iso-oxazolone 737Methyl orange 854, 1206Methyl red 1206Methyl salicylate 1068Methyl sulphate 7024-Methyl uracil 715, 737Michael addition 76, 599, 701Michaeli’s theory 998Michler’s Ketone 1203Millon’s test 984Mineral oils 1025Molar absorptivity 1149Molasses 492Molecular chirality 133Molecular depression constant 20Molecular dissymmetry 133Molecular orbital theory 323, 1199Molecular rearrangements 1303Molecular rotation 135Molisch test 962Monohydric alcohols 447Monosaccharides 926, 928Mordant dyes 1201Morphine 1070, 1131Mulliken’s test 758Muscone 218Mustard gas 837Mutarotation 931, 933Myrcene 1087

NNaphthalene 376Naphthalene sulphonic acids 383Naphthaquinones 396Naphthoic acid 383Naphthol green Y 1205Naphthols 390Naphthol blue black B 1210-Naphtholorange 854Naphthol yellow S 1205Naphthylamines 393Narcotics 1070, 1132Natural gas 27Natural polymers 293Natural rubber 312, 1103N-Bromosuccinimide (NBS) 1269Nef carbonyl synthesis 700Neighbouring group participation 434Neoarsphenamine 1067Neopentyl rearrangement 71Neoprene 311Nernst glower 1138

Neutralisation equivalent 618Newmann projection 164Nickel boride 285Nicol prism 134Nicotine 1117Nicotine adenine dinucleotide 996Nicotinic acid/Niacin 904, 1051Nikethamide 1051, 1080Ninhydrin test 983Nitration 196, 360, 382, 755Nitrenes 77Nitriles 704Nitro-aci tautomerism 128, 740Nitro alkanes 696Nitro and nitroso dyes 1204Nitro anilines 800Nitrobenzene 755Nitro compounds 754Nitrogen rule of the parent ion 1177Nitrolic acid 699Nitromethane 696Nitromethyl carbanion 73Nitronaphthalenes 395Nitronium ion 755Nitrophenols 532Nitroprusside test 984Nitrosation 526p-Nitrostilbene 762NMR-spectroscopy 1160No bond resonance 54Nomenclature 106Nonactin 557Nonaromatic 326Nonbenzenoid aromatic compounds

332Non bonding orbitals 261Non equivalent proton 1165Nonessential amino acids 968Non ionic detergents 1028Non reducing sugars 927Norris-type reaction 1233Novolak 302Nuclear halogenation 456Nuclear Magnetic resonance 1160Nucleic acids 1003Nucleophilic acyl substitution 670Nucleophilic additions 91, 283, 572Nucleophilic aromatic substitution

459, 760Nucleophilic reagents 64Nucleophilic substitutions 90,424,428Nucleoproteins 981Nucleosides 1004Nucleotide polymers 1006Nucleotides 1005Nujol 1139Nylon-6 302Nylon-66 302Nylon salt 302

OO-allylation 521Octane number 29

Oleic acid 633Olestra 1024Oligosaccharides 927Optical activity 134Optical brighteners 1029Optical inversion 152Optical isomerism 136Oppeneur oxidation 1258Optimum temperature 994Organic halogen compounds 420Organo cadmium compounds 584Organolithium compounds 866Organomagnesium compounds 857Organometallic compounds 857Organosilicon compounds 873Organosulphur compounds 829, 841Organosodium compound 186Organozinc compound 870Orientation 342Orientation effect 333Orientation in halogenation 193Orinithine cycle 1297Orlon 297Ortho effect 618, 785Osazone 936Osmium tetraoxide 1271Oxalacetic acid 638Oxalic acid 646Oxaloacetic acid 1294Oxazole 898Oxidation reactions 287, 370Oxidative cleavage 498, 1263Oxidative enzymes 992Oxidative hydroxylation 249, 250-Oxidization 1299Oxime-nitroso tautomerism 128, 740Oxonium salts 546Oxo process 874Oxyacetylene flame 289Oxymercuration-demercuration

242, 479Oxyphenyl butazone 1070Oxytane 1237Oxytocin 967Ozone 1273Ozonolysis 248, 287

PPaal-Knorr synthesis 881Paal-Knorr cyclization 899Paludrine 1066Pantothenic acid 1050Papaverine 1133Paper chromotography 13Paracetamol 523, 1068Para red 1208Parathion 473Partially recimised 97, 153Paterno-Buchi reaction 1237Pechmann condensation 532Penicillins 1062Peptide linkage 976Peptides 975, 977

(vii)

Pentothal 1074Peptones 981Peraformaldehyde 1072Pericyclic reactions 1246Periodate oxidation 498Periodic acid 498, 1275Perkin reaction 579Perlon-L 302Permanganate oxidation 287Peroxide effect 237Peroxy fluoroacetic acid 756Petrochemicals 30Petroleum and petrochemicals 27Petroleum as a source of aromatics32Petroleum refining 27Phase transfer catalyst 555, 797Phenacetin 523, 10689,10-Phenanthraquinone 407Phenanthrene 406Phenetole 550Phenol coefficient 1071Phenol formaldehyderesin 302Phenols 512Phenolphthalein 1210Phenothiazine 801Phenyl acetylene 373Phenylbutazone 1069Phenylenediamines 802Phenyl hydrazine 819Phenyl sulphone 849Phosphofructokinase 1290Phosphoglucoisomerase 1290Phospholipids 1015Phosphoproteins 981Phosphorescence 1230Phosphorylation 1290Phthalein reaction 530Phthalic acid 645Photochemical oxidations 1242Photochemical reactions 1225Photochemical rearrangement 1239Photochemical reduction 1236Photocycloaddition 1237Photocyclodimerisation 1239Photosensitisation 1241Photolysis 1234Phthalein dyes 1210Phthalocyanines 1218Phthalonic acid 389Phthalyl sulphathiazole 1060Phytosterols 1039Picolines 904Picolinic acid 904Picramide 534Picrate 531Picric acid 533, 1072, 1204Picryl chloride 534-complex 283-diastereomers 155Pictet-Spengler Synthesis 916Pigments 1217Pimelic acid 645

Pinacol pinacolone rearrangement71, 500

Piperic acid 1114Piperidine 908Piperine 1114Piperonyl chloride 1114-Pinene 1100Piperonylic acid 1114pKa value 43pKb 43Plane of symmetry 130Plane polarized light 134Planck’s constant 1137Plasmaquin 1066Plasticizers 314Polar and non-polar bond 35Polarimeter 134Polarity of covalent bonds 36Polarizer 134Polychloroprene (neoprene) 268Polyesters 301Polygon rule 325Polyhalogenated alkanes 446Polyisoprene 268Polymerization 253, 293, 592Polynuclear hydrocarbons 332, 376Polyphenyls 411Polysaccharides 956Polystyrene 310Polyurethane 305Polyvinyl chloride (PVC) 310Pomeranz-Fritsch Synthesis 916Position isomers 127Primaquine 1065Primary structure of protein 987Primary suffix 106Principal functional group 116Prismane 203, 216Procaine 1080Procion red 1208Product analysis 92Progesterone 1038Proguanil 1066Prontosil 1059Propandid 1079Propargyl alcohol 289Proper axis of symmetry 131Prosthetic group 991Proteinases 992Proteins 980Protein metabolism 1295Protocatechualdehyde 600Proton magnetic resonance 1162Pruflavin 1072Pschorr’s synthesis 816Pseudo nitrole 699Puckered conformations 212Pulegone 1098Purification 3Purine bases 1004Purines 917Pyranose structure 933

Pyrazine 918Pyrazole 825, 898, 920Pyrene 332Pyridazine 918Pyridine 903Pyridoxine 1051Pyrimidine 918Pyrimidine bases 1004Pyroligneous acid 491Pyrolysis 196Pyroxylines 962Pyrrole 882Pyrryl salts 889Pyruvic acid 663

QQualitative elemental analysis 15Quaternary ammonium salt 768Quanacrine 1066Quanalbar (Seconal) 1073Quantitative elemental analysis 16Quantum efficiency 1232Quantum yield 190, 1232Quaternary structure 990Quercitin 1218Quinine 1125Quininic acid 1126Quininone 1125Quinol 537Quinoline 912Quinolinic acid 914Quinonoid structure 1198Quinone 537Quinoxaline 802Quinuclidine 59

RRacemic modification 137Racemisation 153Rancidity 1020Raney nickel 1277Raschig process 458, 515Rating of fuels 29Rayon 960Reaction mechanism 35Reactive intermediates 65Rearrangement 67, 71, 91, 289Rectified spirit 493Reducing sugars 927Reduction reactions 588Reductive amination 774Reformatsky reaction 582, 661, 871Regioselectivity 231Reichert-Meissl Value 1023Reimer-Tiemann reaction77, 524, 567Relative configuration 139Renaturation 983Resolution 150Resonance 46, 321Resonance effect 53Resonance energy 47Resonance hybrid 47, 48Resonance theory 48, 1198Resorcinol 536

(viii)

Resorcin yellow 1207Retinal 1044Retention of configuration 153Retinol 1044Retro claisen condensation 739Retrosynthetic analysis 863, 1323Rf Value (Retention factor) 13Rhodamine-N (Basic violet-10) 1213Rhodopsin 1045Riboflavin 1049Rickets 1047Rideal-Walker value 1071Ring fission 208Ritarders 297Ritter reaction 771RNA 1007Rosaniline 1204Roschelle salt 639Rosenmund reduction 563, 675Rotation axis 131R.S. configurations 148R-S-notation 141Ruff degradation 946

SSabatier-Senderen’s reaction 184Saccharification 493Saccharin 851Sachse-Mohr theory 211Sacrificial hyperconjugation 55Salacrin 1072Salicin 949Salicylic acid 643Salkowski reaction 1036Salol 644, 1072Salvarsan ‘606’ 1067Sandmeyer reaction 812Sanger’s method 986Sanger’s reagent 986Saponification 1019Saponification value 1021Saran 308Sawhorse representations 164Saytzeff elimination 71, 231, 438Saytzeff orientation 438Schiff bases 790Schiff’s reagent 595Schmidt reaction 78, 622, 773Schotten-Baumann reaction 788Schotten-Baumann technique 788Schweitzer’s reagent 960Secondary structure 988Sedatives 1072Secondary suffix 107Selective reduction 629, 759Selenium dioxide 1279Semicarbazide 714Semisynthetic polymers 294, 314Sex hormones 1038Sheehan method 978Shielding effect 1164Sigma complex 357Sigmatropic rearrangement 1253

Silicon oils and waxes 875Silicones 875Silicon rubber 313, 875Siloxane 875Silver salt method 21Simmon-Smith reaction 207, 247Simmon-Smith reagent 247Singlet and Triplet carbene 76Singlet and Triplet Nitrene 79Singlet and Triplet states 1228Siwolowoff’s method 14Skew conformations 162Skraup synthesis 912SN

1 mechanism 430

SNi mechanism 433SN

2 mechanism 428Soaps 1025Sodamide 1281Sodium borohydride 588, 1282Sodium cyanoborohydride 774Sodium thionitroprusside 15Soft soaps 1026Solvation 782Sommelet’s reaction 568Sorberol 1100Sorbitol 930Sorensen’s titration 975Source of organic compounds 2Sour gasoline 28Soxhlet extractor/soxhletting 6, 1110Specific rotation 135, 931Spectroscopy 1136Spent lye 502Spent wash 493Sphingolipids 1015Sphingosine 1015Sphingomyelin 1015Spin-spin coupling 1169Spin-spin relaxation 1164Spin-spin splitting 1171Spiro compounds 120Spirodienone 94Spurious colours 1221Squalene 1102Staggered conformation 162Starch (amylum) 956Steam cracking 29Steam distillation 8Steering wheel projection 142Stephen’s reaction 565, 706Sterculic acid 219Stereochemistry 126Stereochemistry of amines 779Stereochemistry of diphenyls 413Stereochemistry of spirocompounds

133Steric effect/inhibition/hindrance 57Stereochemical studies 95Stereogenic atom 130Stereoisomers 128Steric factors in electrophilic aromatic

Substitution reactions 89, 340Stereoselective reduction 232Stereoselective reaction 243, 286Stereoselective oxidations 250Stereospecific 137, 246Steric repulsion 262Steric strain 168Steroids 1033Stieglitz rearrangement 79Stobbe condensation 581Stork syntheses 748Strecker’s synthesis 970Streptomycin 1064Stretching vibrations 1139Structural isomerism 127Structural theory 2Stuart model 129Styphnic acid 523Styrene 372Sublimation 5Substitution reactions 89Succinic acid 727Succinic acid dehydrogenase 1295Succinyl sulphathiazole 1060Sucrose 949Sulphacetamide 1058Sulphadiazine 1059Sulpha drugs 1057Sulphaguanidine 1058Sulphamerazine 1057Sulphamethoxazole 1059Sulphanil amide 1058Sulphanilic acid 853Sulphapyridine 1059Sulphathiazole 1059Sulphisoxazole 1059Sulphonal 837Sulphonamides 850, 1058Sulphonating agents 842Sulphonation 196, 361, 382, 793Sulphones 836Sulphonium salts 835Sulphoxides 836Suprafacial 1252Surfactants 1072Sweet gasoline 28Sweet water 503Syndets 1027Syndiotectic 295Synthetic musks 764Synthetic petroleum 31Synthetic polymers 293Synthetic rubber 311

TTartar emetic 639Tartaric acid 638Tartornic acid 506Tautomers 127, 743Tautomerism 284, 739, 897Teflon 310Terebic acid 1096

(ix)

Termination codon 1012Terpenoids 1085Terpenylic acid 1096Terpin 1095-Terpineol 1095Terpinolene 1095Tertiary structure 989Terylene 301Testosterone 1038Tetracyclines 1064Tetrahaloalkanes 450Tetrahedral carbon 129-Tetralone 379Tetramerization 288Tetraethyl lead 861Tetrahedral hybridization 1309Tetramethyl silane 861, 1162Tetraphenyl hydrazine 801Tetronal 837Thallation 457, 514Thermal reactions 1225Thermoplastic and thermosettingplastic 295Thiacetazone 1075Thiambutosine 1076Thiamine 1049Thiazole 898Thiele’s structure 320Thin layer chromatography 12Thioalcohols 829Thioethers 834Thioketals 832Thiokols 312Thiophene 883Thiophenols 847Thiourea 718Thiuronium salts 719Thorpe nitrile condensation 706Thorpe-Ziegler reaction 206Thymine 1004Thymol 1098Thyroxine 1041Tincture of iodine 1071Tinopal BV 1217Tischenko reaction 595Titanous chloride 770Tocopherols 1047Tollen’s reagent 591p-Toluene sulphonic acid 844Torsional energy 163Torsional strain 163Tosylation 849Tosyl chloride 789, 848Tracer experiments 464, 686Tranquillizers 1072Trans amination 1296Transcription 1011Trans estrification 681, 1020Transition state 79Transition state theory 137Translation 1011Transmission effect 41

Transparent soaps 1026Trichloroethylene 1079Trichloroethanol 1078Trimerization 288Trinitrotoluene 762Trinitrophenyl styrene 762Trigonal hybridization 1310Trional 837Triphenyl methane 413Triphenyl methane dyes 1202Triphenyl methyl carbanion 74Triphenyl methyl cation 50Triphenyl methyl radical 53Triptycene 403Triton K-12 1072Trivial axis 131Trivial names 104Tropic acid 1120Tropine 1120Tropinic acid 1121Tropinone 1121, 1124Tropylium ion 331Truxillic acid 629Truxinic acid 629Tryparsamide 1067, 1076Twist boat conformation 171Tyrian purple 1216Tyrosine 969

UUllmann reaction 410, 801, 466, 777-Unsaturated aldehydesand ketones 597Uranine 1211Urea-formaldehyde resin 304, 715Urea 712Ureide 714Urethanes 709, 710Uridine 1005Uridine-5-phosphate 1006Urotropine 586, 1072U.V. Spectra 1151U.V. spectroscopy 1148

VValene-bond theory 1199-Valerolactone 663Vanaspati ghee 1019Van der Waals deshielding 1168Vander waals forces 1316Vanillin 549, 599Van slyke method 974Variable transition state theory 438Vat dyes 1202Vegetable oils 1017Veratraldehyde 600Verberol 1100Verbenone 1100Vicinal dihalides 427Vicinal protones 1171Victor Meyer’s method 20Victor Meyer’s test 489Vilsmeyer reaction 567Vinyl anion 277

Vinylation 284Vinyl ether 544, 1078Vinyl halides 441Vinyon 310Vital force theory 1, 2Vitamin-A 1044Vitamin-B Complex 1049Vitamin-C 1052Vitamin-D 1047Vitamin-E 1047Vitamin-H 1054Vitamin-K 1048Vitamins 1044Vulcanization 312

WWagner-Meerwein rearrangement

71, 1304Wagner’s reagent 1109Walden inversion 152Warburg’s enzyme 1050Water gas 491Wave length 1137Wave number 1137Watson-Crick model for DNA 1009Waxes 1015Wedge bond 130Weedicide 521Whitening agents 1029Wilkinson’s catalyst 1284Williamson Synthesis 424, 520, 544Willstatter’s synthesis 1122Wittig reaction 587Wittig rearrangement 869Witt’s Chromphore-auxochrome

theory 1196Wohl degradation 946Wolff-Kishner reduction 589Wolff rearrangement 612, 823Wood distillation 3Woodward’s rules 1151Woodward and Fieser rules 1152Wurtz-Fittig reaction 354, 466Wurtz reaction 185, 426

XXanthen dyes 1210Xanthoproteic test 984Xerophthalmia 1045X-ray Crystallography 988

YYeast 949Ylide 587

ZZaitsev elimination 231, 437Zemplen’s modification 946Zerevitinov method 481, 860Ziegler high dilution technique 207Ziegler Natta Catalyst 268, 299, 1286Ziegler-Thorpe reaction 206Ziesel method of estimation549, 1111Zingiberene 1099Zwitterion 853, 972Zymase 492

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