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Pharmaceutical Organic Chemistry -E-Book

Pharmaceutical Organic Chemistry -E-Book

S.K. Bhasin | Reena Gupta

(2013)

Additional Information

Book Details

Abstract

Pharmaceutical Organic Chemistry has been written keeping in mind the severe need for a comprehensive text to meet the curriculum needs of the undergraduate pharmacy students. It not only provides all the curriculum topics to the students but also contains all the vital reactions/mechanisms that the students look for in an organic chemistry book.

  1. Entire subject matter has been written in a systematic and lucid style in simple language.
  2. All the basic concepts and fundamentals of organic chemistry have been explained with well-chosen examples.
  3. For better understanding of the subject matter, important points have been highlighted in the form of the textboxes titled as Remember, Learning Plus and Noteworthy Points, wherever required.
  4. Summary of the topics in the form of Memory Focus has been given at relevant places to help the students to revise the subject matter quickly.
  5. Stepwise mechanism of the reactions as per the syllabus has been illustrated, laying emphasis on the reactive intermediates involved.
  6. At the end of each chapter, Revision Questions including descriptive questions and short answer questions have been given for the students to practice.

Multiple Choice Questions with answers have been included at the end of each chapter.


Table of Contents

Section Title Page Action Price
Front Cover \r Front Cover
Front Matter \r i
Copyright \r iv
PREFACE v
Dedication \r vii
Contents ix
Chapter 1 - Structure and Properties\r 1
Introduction 1
Wave Mechanical Model of Atom (Atomic Orbitals) 2
Physical significance of Wave Function 4
Quantum Numbers 5
Principal quantum number (n) 5
Magnetic quantum number (m) 7
Shapes of Orbitals 11
Shapes of s Orbitals 11
Difference between 1s and 2s Orbitals 11
Shapes of p Orbitals 12
Shapes of d Orbitals 13
Signs of Wave Functions 14
s Orbitals 14
p Orbitals 14
d Orbitals 15
Rules for Filling of Orbitals or Electronic Configuration of Atoms 16
Aufbau Principle 16
n+l rule or Bohr Bury's rule 17
Pauli's Exclusion Principle 17
Applications 17
Hund's Rule of Maximum Multiplicity 19
Explanation 20
Extra Stability of Half-Filled and Completely Filled Subshells 21
Part - BFormation of Molecules 29
Introduction 29
Valence Bond (VB) Theory 30
Application of VB Theory: Formation of Hydrogen Molecule 30
Limitations of Valence Bond Theory 31
Molecular Orbital (MO) Theory 33
Molecular Orbitals 32
Conditions of Formation of Molecular Orbitals 34
Differences Between Atomic and Molecular Orbitals 36
Formation oF Bonding and Antibonding Molecular orbitals (LCAO Method) 37
Bonding and Antibonding Molecular Orbitals in Terms of Wave Functions 38
Differences between Bonding and Antibonding Molecular Orbitals 39
Combination of Atomic Orbitals-Sigma (σ) and PI (π) Molecular Orbitals 40
Difference between σ and π Molecular Orbitals 41
comparison of Valence Bond Theory and Molecular Orbital Theory 42
Hybridization 43
Conditions for Hybridization 43
Characteristics of Hybridization 43
Types of Hybridization 44
Intermolecular Forces 53
Hydrogen Bonding 56
Factors Responsible for the Formation of Hydrogen Bond and Strength of Hydrogen Bond 55
Consequences of Hydrogen Bonding 57
Types of Hydrogen Bonds 59
Hydrogen Bonding in Ice in Water 60
Density of Water is Maximum at 4C 61
Importance of Hydrogen Bonding 62
Bond Dissociation Energies 63
PART - CAcids and Bases 71
INTRODUCTION 71
ARRHENIUS CONCEPT OF ACIDS AND BASES 71
BRONSTED–LOWRY CONCEPT OF ACIDS AND BASES 73
LEWIS CONCEPT OF ACIDS AND BASES 77
Dissociation Constants of Acids and Their Strength 70
Conjugate Acid-Base Pairs 73
Relative Strength of Acids and Bases 74
Advantages of Bronsted-Lowry Concept Over Arrhenius Concept 74
Limitations of Bronsted-Lowry Concept 75
Limitations of Lewis Concept 76
Effect of Substituents on the Strength of Lewis Acids and Bases 103
Inductive effect of the substituents 103
Resonance effect of the substituents 78
Steric effects of the substituents 79
Chapter 2 - Nomenclature of Organic Compounds\r 91
Introduction 91
Iupac Nomenclature of Organic Compounds 92
General Rules of IUPAC System 93
Nomenclature of Hydrocarbons 97
Nomenclature of Saturated Branched Chain Acyclic Hydrocarbon 97
Nomenclature of Unsaturated Hydrocarbons 101
Nomenclature of Cyclic (Alicyclic) Hydrocarbons 103
Nomenclature of Polycyclic Hydrocarbons 105
IUPAC Nomenclature of Compounds Containing One Functional Group, Multiple Bonds and Substituent 105
Nomenclature of Polyfunctional Compounds 108
Some Additional Rules for Solving Complex Compounds 111
Specific Classes of Organic Compounds 112
Nomenclature of Substituted Alicyclic Compounds Having some Functional Group Along with other Substituents 115
Nomenclature of Aromatic Compounds 116
Chapter 3 - Stereochemistry\r 133
Introduction 133
Isomerism 133
Structural Isomerism 134
Stereoisomerism 138
Optical Isomerism 138
Polarized light 139
Optical activity 139
Specific rotation 140
Concept of Chirality 140
Chiral structures 140
Achiral structures 141
Chirality in organic compounds 712
Types of Optical Isomers 143
Enantiomerism 143
Essential Condition for Enantiomerism 145
Characteristics of Enantiomers 145
Planar Representation of Three-Dimensional Formulae: Fischer Projection Formulae 145
Diastereomerism: Compounds Having More Than One Chiral Carbon 148
Meso Compounds 150
Number of Possible Stereoisomers in Compounds Containing Different Number of Chiral Centres 152
Racemization 153
Internal and External Compensation 153
Internal Compensation 153
External Compensation 154
Resolution of Racemic Modifications 155
Specification of Configuration 156
Specification of Configuration by R and S Notations 161
Configuration on the Basis of Projection Formulae 164
Configuration of Compounds Containing More Than One Chiral Centre 164
GEOMETRICAl ISOMERISM 166
Configuration of Geometrical Isomers on the Bases of Properties 168
Geometrical Isomerism of Carbon-Nitrogen (C N) Double Bond and N N Double Bond 171
E and Z system of Nomenclature 172
Geometrical Isomerism in alicyclic Compounds 174
Conformation of Alkanes 175
Conformation of Ethane 175
Relative stabilities of conformations of ethane 176
Conformations of Propane 177
Conformations of n-Butane 178
Relative stabilities of conformations of n-butane 179
Chapter 4 - Alkanes\r 189
Introduction 189
Structure of Alkanes 189
Structural Isomerism 191
General Methods of Preparation of Alkanes 192
Physical Properties of Alkanes 202
Mechanism of Halogenation 208
Evidences in Support of Free Radical Mechanism 209
Chapter 5 - Alkenes\r 217
Introduction 217
Structure of Alkenes (Structure of Carbon-Carbon Double Bond) 217
Nomenclature of Alkenes 219
Common System 219
IUPAC System 219
Isomerism in Alkenes 220
Method of Preparation of Alkenes 221
Dehydration of Alcohols 221
Mechanism 221
Relative stabilities of carbonium ions 222
Orientation in dehydration of alcohols 223
Rearrangements of carbonium ions 224
Dehydrohalogenation of Alkyl Halides 225
E2 (elimination, bimolecular or second-order) reaction 226
E1 (elimination, unimolecular or first-order) reaction 227
Orientation of E2 and E1 reactions (Saytzeff's rule) 227
Reactivities of alkyl halides in dehydrohalogenation 228
By Partial or Selective Reduction of Alkynes 229
Electrolysis of Sodium or Potassium Salts of Dibasic Acids (Kolbe's Electrolytic Method) 229
Dehalogenation of Vicinal Dihalides 230
Physical Properties of Alkenes 230
Chemical Properties of Alkenes 231
Addition Reactions 231
Addition of hydrogen (hydrogenation) 231
Heat of hydrogenation and stability of alkenes 232
Addition of Halogens 233
The two-step ionic mechanism 233
Anti-Markownikoff's addition 236
Addition of Sulphuric Acid 238
Mechanism 238
Addition of Water (Hydration of Alkenes) 239
Mechanism of hydration 239
Halohydrin Formation: Addition of Hypohalous Acids 239
Mechanism 240
Ozonolysis 240
Mechanism of ozonization 241
Application of ozonolysis in determining the position of double bond 242
Mechanism of hydroboration 244
Mechanism of oxidation of trialkyl boranes to alcohols 244
Mechanism for the hydroboration of unsymmetrical alkene 245
Hydroxylation of Alkenes with Osmium Tetra Oxide 247
Stereochemistry of hydroxylation or OsO4 247
Oxidation with Hot Alkaline KMnO4 (Oxidative Cleavage of Alkenes) 248
Chapter 6 - Alkynes\r 257
Introduction 257
Structure of Alkynes (Carbon-Carbon Triple Bond) 257
Isomerism in Alkynes 258
Structural Isomerism in Alkynes 259
Nomenclature of Alkynes (Acetylenes) 259
Classification of Alkynes 260
Commercial Methods of Preparation of Acetylene 261
General Methods of Preparation of Alkynes 261
Physical Properties of Alkynes 263
Chemical Properties of Alkynes 263
Low Reactivity of Alkynes Towards Electrophilic Addition Reactions 264
Addition Reactions 264
Addition of Hydrogen 264
Exhaustive Hydrogenation of Alkynes 265
Controlled Reduction of Alkynes 265
Electrophilic Additions 266
Nucleophilic Addition Reactions 271
Acidity of Acetylenic Hydrogen 272
Oxidation Reaction of Alkynes 274
Polymerization 276
Distinction Between Alkane, Alkene and Alkyne 277
Chapter 7 - Cycloalkanes\r 285
Introduction 285
Nomenclature of Cycloalkanes 285
Preparation of Cycloalkanes 289
Physical Properties 295
Chemical Properties 296
Relative Stability of Cycloalkanes (Baeyer's Strain Theory) 298
Heat of Combustion and Stability of Cycloalkanes 299
Sachse-Mohr Theory of Strainless Rings 300
Chapter 8 - Dienes\r 307
Introduction 307
Nomenclature 308
Methods of Preparation of Conjugated Dienes 308
Relative Stability of Conjugated Dienes 309
Resonance Structure of Conjugated Dienes 310
Orbital Picture of Conjugated Dienes 310
Conformations of 1,3-butadiene 311
Chemical Properties of Conjugated Dienes 312
Electrophilic Addition Reactions 312
Free Radical Addition to Conjugated Dienes 316
Diels-Alder Reaction 168
Reduction 319
Chapter 9 - Benzene and Polynuclear Compounds 325
Introduction 325
Nomenclature of Aromatic Compounds 325
Isomerism of Benzene Derivatives 328
Preparation of Benzene 329
Commercial Preparation of Benzene 329
Laboratory Methods of Preparation of Benzene 329
Properties of Benzene 331
Structure of Benzene 337
Kekule Ring Structure of Benzene 354
Resonance Structure of Benzene 338
Molecular Orbital Structure of Benzene 339
Aromatic Electrophilic Substitution (Characteristic Aromatic Reaction) 339
Electronic Mechanism of Electrophilic Mono-Substitution in Benzene Ring 340
Mechanisms of Some Electrophilic Substitution Reactions of Benzene 341
Theory of Reactivity 345
Directive Influence of Groups in Electrophilic Substitution 347
Orientation 349
Theory of Orientation Based on Stability of Carbonium Ion 349
Chapter 10 - Arenes\r 359
Introduction 359
Structure and Nomenclature of Arenes 359
Isomerism in Arenes 363
The Aromatic Character (Aromaticity) 364
Huckel Rule 364
Aromatic, Antiaromatic and Nonaromatic Compounds 364
Preparation of Arenes 367
Physical Properties 370
Chemical Properties 370
Ortho-Para Ratio in the Formation of Disubstitution Derivatives 378
Orientation in Disubstituted Benzene (Introduction of a Third Group in Benzene Ring) 380
Some Individual Members 382
Toluene, Methylbenzene, Phenylmethane (C6H5CH3) 382
Methods of preparation 382
Physical properties 382
Chemical properties 382
Styrene (an Alkenyl Benzene), 2-Phenyl Ethane, Phenylethylene, Vinylbenzene 385
Methods of preparation 385
Chemical properties 386
Xylene, Dimethylbenzene (C6H4(CH3)2) 388
Mesitylene, 1,3,5-Trimethylbenzene (C6H2(CH3)3) 388
Chapter 11 - Alkyl Halides\r 393
Introduction 393
Classification 393
Nomenclature of Halogen Derivatives 395
Isomerism in Alkyl Halides 396
General Methods of Preparation of Alkyl Halides 397
Polar Nature of Alkyl Halides 402
Physical Properties 403
Chemical Properties 404
Nucleophilic Substitution Reactions 408
Types of Nucleophilic Substitution Reactions 409
Kinetics of nucleophilic substitution reactions 409
Mechanisms of SN2 (Substitution Nucleophilic Bimolecular) 409
Transition state of a SN2 reaction 410
Factors which infuence SN2 reactions 410
Stereochemistry of SN2 Reaction 412
SN1 Reaction 412
Factors which infuence SN1 reactions 412
Elimination Reactions 414
Mechanism 415
E2 (Elimination bimolecular) 415
E1 (Elimination unimolecular) 415
Miscellaneous Reactions 416
Wurtz Reaction (Formation of Higher Alkanes) 416
Limitations 416
Ionic mechanism 417
Corey-House Reaction 417
Reaction with Magnesium (Formation of Grignard Reagent) 418
Formation of TEL 418
Reduction (Formation of Alkanes) 419
Rearrangement on Heating (Isomerization) 419
Uses Of Alkyl Halides 420
Chapter 12 - Alcohols\r 427
Introduction 427
Classification of Alcohols 427
Monohydric Alcohols 428
Classification of monohydric alcohols 428
Nomenclature of monohydric alcohols 428
Isomerism 429
General Methods of Preparation of Alcohols 431
Structure of Alcohol 438
Physical Properties 439
Chemical Properties 440
Distinction Between 1, 2 And 3 Alcohols 452
Ethylene Glycol 456
Preparation of Ethylene Glycol 456
Physical Properties 458
Chemical Properties 458
Glycerol (1,2,3-Propanetriol) 465
Preparation 465
Physical Properties 467
Chemical Properties 467
Summary 474
Chapter 13 - Phenols\r 483
Introduction 483
Classification and Nomenclature Of Phenols 484
Monohydric Phenols 484
Dihydric Phenol 484
Preparation of Phenols 485
Physical Properties 487
Chemical Properties 488
Reactions of the Phenolic - OH Group 489
Explanation of the acidic nature of phenol 489
Reactions Due to Benzene Ring 493
Special Reactions 497
Uses of Phenol 501
Distinction Between Alcohols and Phenols 502
Effects of Phenol on Human Health 502
Chapter 14 - Ethers and Epoxides\r 509
Introduction 509
Nomenclature 510
Common System 510
IUPAC System 510
Special Names 511
Isomerism 511
Chain Isomerism 511
Position Isomerism 512
Functional Isomerism 512
Metamerism 512
Structure of Ethers 512
Preparation of Ethers 513
Physical Properties 516
Chemical Properties 517
Uses of Ether 519
Epoxide 519
Structure of Epoxides 520
Preparation of Epoxides 520
Reactions of Epoxides 521
Physiological Effects of Ethylene Oxide 524
Acid-Catalysed Cleavage 525
Base-Catalysed Cleavage 526
Orientation Cleavage 526
Chapter 15 - Amines\r 533
Introduction 533
Classification Of Amines 533
Structure Of Amine 535
Nomenclature Of Amines 535
Isomerism Of Amines 538
Preparation of Amines 540
Industrial Preparation 543
Separation of Primary, Secondary and Tertiary Amines 544
Physical Properties 546
Stereochemistry of Amines 547
Chemical Properties 547
Some Important Reactions of Benzene Diazonium Chloride 559
Distinction Between Primary, Secondary and Tertiary Amines 561
Tests for Amines 561
Uses 562
Chapter 16 - Aldehydes and Ketones\r 569
Introduction 569
Nomenclature 569
Isomerism 571
Structure of Carbonyl Group 572
Polar Nature of Carbonyl Group 572
Similarities and differences between C C and C O bonds 572
Methods of Preparation 573
From Alcohols 573
From Calcium Salts of Fatty Acids 575
From Acid Chlorides 575
From Alkynes 576
From Cyanides 577
From Alkenes 577
Oxo Process 577
Wacker's Method 578
From Gem Dihalides 578
Methods of Preparation of Aromatic Aldehydes and Ketones 578
Physical Properties of Carbonyl Compounds 580
Chemical Properties of Carbonyl Compounds 581
Distinction Between Aldehydes and Ketones 596
Uses of Aldehydes and Ketones 596
Chapter 17 - Carboxylic Acids\r 605
Introduction 605
Nomenclature of Carboxylic Acids 606
IUPAC System 606
Isomerism 608
Structure of Carboxyl Group 609
Methods of Preparation 610
Physical Properties of Carboxylic Acids 612
Chemical Properties 613
Effect of Substituents on Acidity 620
Some Commercially Important Carboxylic Acids 622
Chapter 18 - Functional Derivatives of Carboxylic Acid 631
Introduction 631
Nomenclature and Isomerism in Acid Derivatives 632
Preparation and Reactions of Acid Chlorides 635
Acid Chlorides 635
Methods of Preparation 636
Physical Properties of Acid Chlorides 637
Chemical Reactions of Acid Chlorides 637
Preparation and Reactions of Acid Amides 641
Acid Amides 641
Preparation 642
Physical properties of acid amides 643
Chemical reactions of acid amides 643
Preparation and Reactions of Acid Anhydrides 645
Acid Anhydrides 645
Preparation 645
Physical properties 646
Chemical reactions of anhydrides 646
Preparation and Reactions of Acid Esters 647
Esters 647
Preparation 648
Physical properties of esters 649
Chemical reactions of esters 649
Nucleophilic Acyl Substitution 651
Role of Carboxylic Group 651
Acid derivatives undergo nucleophilic substitution reactions 652
Order of reactivity of different acid derivatives 655
Role of acid catalysis in nucleophilic acyl substitution 656
Acidic and Alkaline Hydrolysis of Acid Derivatives 656
Mechanism of Acidic Hydrolysis 656
Mechanism of Alkaline Hydrolysis 656
Hydrolysis of Esters 657
Alkaline Hydrolysis of Esters 657
Chapter 19 - Active Methylene Compounds\r 667
Introduction 667
Preparation of Malonic Ester 668
Properties of Malonic Ester 668
Physical Properties 668
Chemical Properties 669
Acetoacetic Ester 677
Preparation of Acetoacetic Ester 677
Properties of Acetoacetic Ester 678
Keto-Enol Tautomerism 684
Relative Stabilities of Keto-Enol Forms 685
Keto-Enol Tautomerism in Acetoacetic Ester 686
Chemical Behaviour of Tautomers 686
Chapter 20 - Mechanism of Organic Reactions\r 691
Introduction 691
Cleavage of Bond 692
Types of Reagents 693
Electronic Effects in Covalent Bonds 694
Inductive Effect or Transmission Effect 694
Electromeric Effect 697
Resonance Effect or Mesomeric Effect 699
Hyperconjugation Or No-Bond Resonance 705
Application of the Hyperconjugation Effect 706
Distinction Between Resonance Effect and Inductive Effect 708
Reaction Intermediates 710
Carbocation or Carbonium Ions 709
Free Radicals 712
Carbanions 714
Classification Of Organic Reactions 717
Substitution Reactions 718
Nucleophilic Substitution Reactions 717
Electrophilic Substitution Reaction 718
Free-Radical Substitution 719
Addition Reactions 721
Elimination Reactions 723
Mechanism of Elimination Reaction 723
Rearrangement Reactions 724
Chapter 21 - Electrocyclic and Sigmatropic Rearrangements\r 731
Introduction 731
Stereochemistry of Electrocyclic Reactions 732
Conrotatory and Disrotatory Motions (Ring-Opening and Ring-Closing Reactions) 735
Sigmatropic Rearrangement 739
Classification of Sigmatropic Rearrangements 740
Naming of the Rearrangements 740
Suprafacial and Antarafacial Sigmatropic Shift 741
Cope and Claisen Rearrangement 742
Cope Rearrangement 742
Claisen Rearrangement 743
Migration of Carbon in Sigmatropic Rearrangement 744
Chapter 22 - Biomolecules\r 751
Introduction 751
Carbohydrates 751
Monosaccharides 752
Disaccharides 756
Sweetness of Sugars 758
Polysaccharides 758
Difference between Monosaccharides, Disaccharides and Polysaccharides 760
Functions of Carbohydrates 761
Proteins 762
Structure of Amino Acids 764
Polypeptide Formation 766
Physical Properties of Amino Acids 767
Chemical Properties of Amino Acids 767
Biologically Important Peptides 768
Structure of Proteins 768
Various Interactions of Forces which Stabilize Protein Structures 770
Classification of Proteins 771
Biological Functions or Role of Proteins 772
Denaturation of Proteins 773
Enzymes 774
Properties of Enzymes 774
Mechanism of Enzyme 775
Applications of Enzymes 775
Comparison of Catalysts and Enzymes: Similarities 776
Nucleic Acids 777
Nucleosides and Nucleotides 778
Biological Functions of Nucleic Acids 780
Distinction Between DNA and RNA 781
Mutation 782
Lipids 783
Fats (Triglycerides) 784
Waxes 785
Functions of Fats 785
Characteristics of chemical properties of the lipids 786
Index 793
A 793
B 794
C 794
D 794
E 795
F 795
G 795
H 795
I 796
K 796
L 796
M 796
N 797
O 797
P 797
Q 798
R 798
S 798
T 799
U 799
V 799
W 799
X 800
Z 800