FUNDAMENTALSOF

ORGANIC CHEMISTRYA Textbook for +2, Intermediate,

Engineering and Medical Entrance Examinations

S. NAFIS HAIDER (M.Sc.)

Reader and Head of the Department of ChemistryOriental College, Patna

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© 1982, S. Nafis HaiderAll rights reserved. No part of this publication may be reproduced or copied in any material form (including photocopying or storing it in any medium in form of graphics, electronic or mechanical means and whether or not transient or incidental to some other use of this publication) without written permission of the copyright owner. Any breach of this will entail legal action and prosecution without further notice.Jurisdiction : All disputes with respect to this publication shall be subject to the jurisdiction of the Courts, Tribunals and Forums of New Delhi, India only.

First Edition 1982 Subsequent Editions and Reprints 1983, 1987, 1990, 1993, 1994, 1995, 1996, 1998, 1999, 2000, 2002, 2003, 2004, 2005, 2006, 2007, 2008, 2010

Eighteenth Revised Edition 2014

ISBN : 81-219-0767-5 Code : 04B 010printed in india

By Rajendra Ravindra Printers Pvt. Ltd., 7361, Ram Nagar, New Delhi -110 055 and published by S. Chand & Company Pvt. Ltd., 7361, Ram Nagar, New Delhi -110 055.

Dedicated to the Memory of My Mother

whose sacrifices and blessings have always inspired

andencouraged me to work

and work hard

PREFACE TO THE EIGHTEENTH REVISED EDITION This edition of the book has been thoroughly revised and enlarged according to the

new syllabuses of different State Boards of India for Intermediate Examinations, CBSE, and also useful for ISC students. A very interesting chapter on nomenclature of “Bridged Hydrocarbons” with a large numbers of examples has been introduced in this edition and a number of exercises and objective type questions have been added at the end of each chapter. Several examples of types of reactions, Isomerism, Nomenclature and current examination questions and answers have been included for students preparing for NEET -UG medical, JEE and other competitive engineering entrance examinations. A new chapter an “Organic Problems” has also been added with some rules of conversions of organic compounds which makes the “organic conversions” and “what happens when” more easier. Thus the present edition has become more and more useful for readers because new chapters on “Hydrogen Bond” Environmental Chemistry, Biomolecules and Chemistry in your Daily Life for classes XI and XII have also been introduced.

I am deeply grateful to Dr. Shahnawaz Mahmood and all those teachers, friends and students who have sent their suggestions, criticisms and comments for further improvement of this book.

I wish to thank my daughters Dr. Naz Khalid W/o Mr. Khalid Bin Jamal, I.A. & A.S., Accountant General, Delhi, Mrs. Mehnaz Firoze W/o Mr. Firoze Zia Hussain, B.E., Superin-tendent of Police, Pondicherry, Mrs. Shazia Haider W/o Mr. Md. Irshad Haider, Dy. Commis-sioner of Police, Delhi, Mrs. Sana Babar W/o Captain Babar Saleem, Indian Army and my sons Mr. Saquib Haider and Mr. Nasir Haider for their outstanding services and help in the prepa-ration of this edition.

In this edition, special care has been taken regarding the syllabus of Tamil Nadu Board to accommodate the topics which were missing in the earlier edition. For this, credit goes to Mr. F.Z. Hussain, S.P., Pondicherry.

Finally, I wish to thank again Mr. Firoze Zia Hussain, B.E., Former S.P. of Pondicherry who after having very busy schedule encouraged and insisted me to complete my another book on “Organic Chemistry for Competitions” and cooperating with suggestions of recent examples. The new book is available in the market.

AUTHOR

Disclaimer : While the author of this book have made every effort to avoid any mistake or omission and have used their skill, expertise and knowledge to the best of their capacity to provide accurate and updated information. The author and S. Chand does not give any representation or warranty with respect to the accuracy or completeness of the contents of this publication and are selling this publication on the condition and understanding that they shall not be made liable in any manner whatsoever. S.Chand and the author expressly disclaim all and any liability/responsibility to any person, whether a purchaser or reader of this publication or not, in respect of anything and everything forming part of the contents of this publication. S. Chand shall not be responsible for any errors, omissions or damages arising out of the use of the information contained in this publication.Further, the appearance of the personal name, location, place and incidence, if any; in the illustrations used herein is purely coincidental and work of imagination. Thus the same should in no manner be termed as defamatory to any individual.

PREFACE TO THE FIRST EDITION I feel genuine pleasure in placing before you “Fundamentals of Organic Chemistry”.

In this book, the subject matter of organic chemistry has been discussed and described very vividly covering most of the quantum of organic chemistry needed for Intermediate students. If fulfils the standards of (10 + 2) classes, Senior Cambridge and Central School Examina-tions, Medical, Engineering, Veterinary and Agriculture Admission Tests.

The book consists of many valuable chapters as well as illustrative summary charts which help in learning and memorisation. The treatment of the subject matter of this book is done on physico-chemical basis, which will be very useful to students.

Finality and completion are something ideal which can be conceived of, but can never be realised in science. No doubt, I have made by best efforts to reach them but it will be unwise on my part to claim finality. I request my readers and critics to kindly inform me of the deficiencies which they find in this effort of mine. As an humble student of chemistry, I am always and ever ready to seek and find tit-bit of knowledge concerning my subject which has not been covered in the preview of this presentation.

I feel this will be unjust on my part if I do not acknowledge thanks to an ever-increasing encouragement of my brother S. Mohsin Minto and S. Anis Haider, IAS. I am also thankful to my teachers, friends and colleagues like Dr. Eqbal Bahadur Singh, Head of the Deptt. of Chemistry, Magadh University, Bodh-Gaya; Dr. S. Sahay; Dr. N.M. Sahay, Mr. Justice S. Sarwar Ali; S. Shakil Ahsan; Masooma Minto and Prof. Md. Ali Khan who helped me with their valuable suggestions in the preparation and presentation of this book.

In this regard, I am indebted to my wife Shahnaz Parween for her patience and cooperation while I was engaged in writing this book.

I would also like to thank Shri R.K. Gupta, Director, S. Chand & Company Ltd., New Delhi for his keen interest in publishing this book in a nice form at a short period of time.

AUTHOR

(vii)

CONTENTS Chapter Pages

1. Introduction 1–9

2. Formulae of Compounds 10 – 33

3. Nomenclature 34 – 77

4. Isomerism 78 – 116

5. Composition of Organic Compounds 117 – 122

6. Purification of Organic Compounds 123 – 127

7. Structure and Shape of Organic Molecules 128 – 153

8. Different Types of Reaction 154 – 193

9. Reaction Mechanism 194 – 231

10. Hydrocarbons 232 – 270

11. Petroleum 271 – 275

12. Halogen Derivatives 276 – 288

13. Aliphatic Alcohols 289 – 315

14. Ethers 316 – 325

15. Aldehydes and Ketones 326 – 366

16. Aliphatic Carboxylic Acids 367 – 388

17. Derivatives of Aliphatic Carboxylic Acids 389 – 394

18. Amines 395 – 400

19. Environmental Chemistry 401 – 415

20. Biomolecules 416 – 443

21. Chemistry in Daily Life 444 – 481

22. Aromatic Compounds 482 – 508

23. Orientation 509 – 515

24. Important Conversions 516 – 526

25. Important What Happens When 527 – 533

26. Important Synthesis 534 – 541

27. Important Notes 542 – 551

28. Empirical and Molecular Formulae 552 – 561

29. Important Tests 562 – 566

(viii)

30. Organic Problems (Rules of Conversions) 567 – 572

Identification of the End Product(C) in each of the following 573 – 585 Sequences of Reactions

Expected Objective Solved Questions Including Admission 586 – 618 Tests Questions (Up-to-date)

ITI Questions and Answers 619 – 636

IIT Examination 2007 637 – 641

IIT Examination 2009 642 – 644

AIEEE 2011 645

AIEEE 2012 (with Answers) 646 – 647

JEE 2013 (with Answers) 648 – 651

NEET UG 2013 (with Answers) 652 – 654

Bihar Intermediate Council (Examination) Class – XII 655 – 656 Chimistry Paper II, 2003

Bihar Intermediate Council (Examination) 657 – 659 Chemistry Paper – II, 2004

Bihar Intermediate Council (Examination) 660 – 662 Chemistry Paper – II, 2005

Bihar Intermediate Council (Examination) 663 – 664

Chemistry Paper – II, 2006

Bihar Intermediate Council (Examination) 2007 665 – 667

Intermediate Council Examination 2009 668 – 669

BCECE Examination 2007 670 – 671

Historical Introduction. Lemery in 1675, divided compounds from natural sources into three classes : mineral, vegetable and animal. But Lavoisier showed that all compounds obtained from vegetable and animal sources always contain at least Carbon and Hydrogen. Now it was found that in a number of cases the same compound could be obtained from both vegetable and animal sources. Thus no difference existed between these two classes of compounds and this led to the reclassifica-tion of compounds into two groups : 1. Those compounds which could be obtained from vegetable animals, i.e. substances which

were obtined from living organisms, were classified as Organic. 2. Those compounds which were not prepared from the living organism were classified as

Inorganic. Vital Force Theory. Berzelius thought that the organic compounds differ from inorganic in

two respects. 1. They did not obey the law of chemical combination. 2. They were the products of a vital force and could not be synthesised in the laboratory.

Berzelius’s views were also confirmed by the following facts. Scheele isolated oxalic acid from cane sugar and from sorrel plant, citric acid from lemon, malic acid from apples, lactic acid from sour milk, uric acid from urine and glycerine from olive oil. Marggrof obtained fromic acid from redants.

Therefore J.J. Berzelius suggested “vital force theory” regarding the formation of carbon com-pounds. According to this theory “Organic compounds were produced under the influence of vital force, and that they could not be prepared artificially.”

However, Wholer a German chemist student of Berzelius accidently synthesised urea from inorganic compound ammonium sulphate and potassium cyanate without using any living organism.

4 2 4 4 2 4(NH ) SO + 2KCNO 2NH CNO + K SO→ Amm. cyanate

NH4CNO → NH2CONH2

Later on Kolbe synthesised acetic acid from the elements and Berthelot synthesised methane.These experiments proved that in the synthesis of plant and animal substances i.e. living organ-

isms no vital force is essential and so belief in a vital force disappeared.Thus the name “Organic” lost its original significance. Since carbon is the essential constitu-

ent of all organic compounds and therefore Organic chemistry is defined as the chemistry of carbon

1

1chapter

Introduction

2 Fundamentals of Organic Chemistry

compounds except the oxides, sulphides, hydrogen cyanides, carbonates and bicarbonates of carbon. The oxides, sulphides, carbonates and bi-carbonates of carbon occur chiefly in the inorganic kingdom and they are described in the textbook of inorganic chemistry.

Organic Compounds. Organic compounds are the compounds of carbon except oxides, sul-phides, hydrogen cyanides, carbonates and bi-carbonates of carbon.

Organic Chemistry. Organic chemistry is defined as the study of the compounds of carbon or the study of hydrocarbons and their derivatives.

Differences between Organic and Inorganic Compounds

1. They are compounds of Carbon, Hydro-gen, Oxygen, Nitrogen, Halogen and Sulphur.

2. Number of organic compounds exceeds a million and constantly increasing each year.

3. They are mostly covalent. 4. Organic compounds are mostly isomers. 5. Organic compounds having low Melting

points and Boiling points. 6. Organic reactions are slow and complex

because they are molecules. 7. Organic compounds are mostly inflam-

mable. 8. Organic compounds are represented by

structural formula. 9. Organic compounds are mostly soluble in

organic solvents and insoluble in water. 10. Organic compounds are mostly homolo-

gous. 11. Long chain molecules are common.

1. They are compounds of different elements.

2. Number of inorganic compounds are less than organic compounds.

3. They are mostly ionicy. 4. Inorganic compounds are rarely isomers. 5. Inorganic compounds having high Melting

points and Boiling points. 6. Inorganic reactions are rapid and simple

because they are ionic. 7. Inorganic compounds are rarely inflam-

mable. 8. Inorganic compounds are represented by

molecular formula. 9. Inorganic compounds are insoluble in

organic solvents and soluble in water. 10. Inorganic compounds are not homologous.

11. Long chain molecules are rare.

Why a Separate Branch for Organic Chemistry. Due to the unique property of carbon, over a million carbon compounds are known. About 40,00,000 organic compounds are recorded while about 4,00,000 inorganic compounds are known. And thus it is not possible to study organic compounds in the textbook of inorganic chemistry which are ten times the inorganic compounds. Besides that, there are similarities between carbon compounds and differences between the composition, structure and properties of organic and inorganic compounds. This justifies that the separate study of organic compounds is more convenient and therefore the need for a separate branch of chemistry is genuine.

Unique Property of Carbon. The number of organic compounds exceeds one million and the number of carbon compounds is constantly increasing. No other single element forms such a large number of compounds. The existence of such a large number of carbon is due to the unique property of carbon which are as following :

Introduction 3

(i) the tetra valency of carbon. C

(ii) Carbon can unite with carbon by a double or multiple bonds e.g.

C C, C C, C C, C O, C O, C N,

(iii) existence of strong covalent bonds between carbon and carbon and between carbon and N, O, P, S, X2 etc.

(iv) Carbon can unite with carbon to form stable straight and branched chain compounds.

C C C C C, C C C C ,

C

Iso-pentaneNor-pentane

C C C

C

C

Neo-pentane

(v) Carbon can unite with carbon and other elements to form stable ring compounds.

C C

C

C C

C C

C C

C C

C

ring of cyclo propane ring of cyclo butane ring of cyclo pentane.

Heterocyclic rings are given below :

C C

C C

C C

C C

C

S

C C

C C

ON

C C

C C

C

C

C

C

C

N

4 Fundamentals of Organic Chemistry

(vi) existence of a large number of isomers.Organic Compound

Carbocyclic Heterocyclic

HeterocyclicAlicyclic Compound

Cyclic or Ring CompoundAcyclic open chainor Aliphatic Compound

Acyclic Compound. The compound whose molecules are open chained are known as open chain or acyclic compound. For example; Ethane, Propane, Butane, Propyne, Acetaldehyde, Form-aldehyde, Acetic acid, Ethers etc. are acyclic compounds or aliphatic compounds having open chain of carbon atoms.

Cyclic Compounds. The compounds which contains one or more rings of atoms are called cyclic compounds or ring compounds.

Carbocyclic or Homocyclic Compound. The cyclic compounds which have rings made of carbon atoms are called carbocyclic or Homocyclic compounds.

For Example :Cyclohexane, Benzene etc. are Carbocyclic Compounds.

Heterocyclic Compounds. The cyclic compounds which have rings made of carbon atom in-cluding one or more different atoms such as Oxygen, Nitrogen and Sulphur are called heterocyclic compounds.

For Example :Pyridine, Furon, Thiophene, Pyrrole, Quinoline etc. are Heterocyclic Compounds.

Introduction 5

CH CH

CH CH

CH

NPyridine

CH CH

CH CH

O

CH CH

CH CH

S

CH CH

CH CH

NHFuron Thiophene Pyrrole

CH

CH C

CH

CH

Quinoline.

CH

CH

CH

N

C

Alicyclic Compounds. The compounds in which the carbon atoms of the ring are joined by single covalent bonds and resemble aliphatic compounds are called Alicyclic compounds.

For Example : Cyclopropane, Cyclobutane, Cyclopentane, Cyclohexane etc. are alicyclic compounds.

CH

CH

CH CH

CH CH

CH

2

2

2

2

2

2

2

Cyclopropane or

Trimethylene

Cyclobutane or

Tetramethylene.

CH CH

CH CH

CH

CH

2

22

22

2

CH CH

CH CH

CH2

22

22

Cyclopentane or

Pentamethylene

Cyclohexane or

Hexamethylene

Aromatic Compounds. The carbocyclic compounds which contain one or more benzenoid ring is called Aromatic compounds. But their properties are totally different from those of alicyclic compounds.

6 Fundamentals of Organic Chemistry

Examples :

Polynuclear Hydrocarbon. Carbocyclic compound containing more than one benzene ring is called polynuclear hydrocarbon.

Anthracene is polynuclear hydrocarbon.Source of Organic Compounds. Organic compounds may be obtained from natural sources

as well as artificial methods as follows :

Living Organism

Plant Animal

Organic CompoundSynthesis

Petroleum

Applications of Organic Chemistry. Organic compounds play a unique role in our daily life. The essential need of living organism are Food, Clothing, Medicine etc. which are the gifts of organic chemistry. They are summarised as follows :

Organic Chemistry

food

stuff

pro

tein

s

carb

ohy

dra

tes

oils

vegetab

le

fats

fuels

dru

gs

dyes

pig

ments

cotto

n

wo

ol

syn

thetic

fibre

s

pain

ts

vitam

ins

ho

rmo

nes

perfu

mes

paper

e.g., Nylon, Terylene

rub

ber

plastic

exp

losiv

e

fertilizers

cosm

etic

s

Fundamental Of Organic Chemistry

Publisher : SChand Publications ISBN : 9788121907675 Author : Nafis Haider

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