Preview Advanced Problems in Organic Chemistry for Engineering and Medical Entrance Examinations Akshay Choudhary Mandakini Choudhary Pearson by Akshay Choudhary Mandakini Choudhary (2017)

Preview Advanced Problems in Organic Chemistry for Engineering and Medical Entrance Examinations Akshay Choudhary Mandakini Choudhary Pearson by Akshay Choudhary Mandakini Choudhary (2017) Preview Advanced Problems in Organic Chemistry for Engineering and Medical Entrance Examinations Akshay Choudhary Mandakini Choudhary Pearson by Akshay Choudhary Mandakini Choudhary (2017) Preview Advanced Problems in Organic Chemistry for Engineering and Medical Entrance Examinations Akshay Choudhary Mandakini Choudhary Pearson by Akshay Choudhary Mandakini Choudhary (2017)

Advanced Problems in Organic Chemistry for Competitive Examinations Akshay Choudhary Mandakini Choudhary Copyright © 2017 Pearson India Education Services Pvt Ltd Published by Pearson India Education Services Pvt Ltd, CIN: U72200TN2005PTC057128, formerly known as TutorVista Global Pvt Ltd, licensee of Pearson Education in South Asia No part of this eBook may be used or reproduced in any manner whatsoever without the publisher’s prior written consent This eBook may or may not include all assets that were part of the print version The publisher reserves the right to remove any material in this eBook at any time ISBN eISBN 978-93-528-6037-1 Head Office: A-8 (A), 7th Floor, Knowledge Boulevard, Sector 62, Noida 201 309, Uttar Pradesh, India Registered Office: Module G4, Ground Floor, Elnet Software City, TS-140, Block & 9, Rajiv Gandhi Salai, Taramani, Chennai 600 113, Tamil Nadu, India Fax:  080-30461003, Phone: 080-30461060 www.pearson.co.in, Email: companysecretary.india@pearson.com Contents   Preface v   Acknowledgements    About the Authors vi vii Chapter General Organic Chemistry1.1–1.78 Chapter Isomerism2.1–2.80 Chapter Hydrocarbons3.1–3.60 Chapter Alkyl Halides, Alcohols and Ethers4.1–4.68 Chapter Carbonyl Compounds and Acid Derivatives5.1–5.68 Chapter ESR Amines and Phenols6.1–6.70 Chapter Biomolecules7.1–7.36 Chapter Organic Reaction Mechanisms and Reagents8.1–8.76 Chapter Practical Organic Chemistry9.1–9.12 Chapter 10 Nomenclature10.1–10.20 This page is intentionally left blank Preface In order to understand a subject, it is important to gain an insight into its guiding principles and proof of concept Theory is beneficial only when it can be successfully applied to solve problems This book presents different types of problems to exemplify each and every theoretical discussion to help the student gain a masterly grasp of the subject As the saying goes, ‘Practice makes a man perfect’, so we set forth in this practice book a multitude of problems to acquaint the student with the different types of questions that could be posed in the subject   This book includes all levels of problems in organic chemistry that every JEE aspirant needs to be skilled at solving We hope this book helps students to achieve their target Readers may send their suggestions to akshaymandakini24@gmail.com Akshay Choudhary Mandakini Choudhary Acknowledgements The editorial team at Pearson Education has been pivotal in encouraging this project, while my wife has very ably and diligently done the proof-reading of the complete manuscript I am indebted to my family members Om Prakash Choudhary, Sita Devi, Hemant Choudhary, Kamla Choudhary, Shivani Choudhary, Ravindra Choudhary, and my uncle Shyam Lal Choudhary who have played a prime role in making me more focused I am grateful to my daughter Sagarika and son Aatish whose joyful faces give me the patience to work   I thank my friends, P B Saxena, Ramashis Paul, Sunil Jangid, Kumud Ranjan, Rakesh Sharma, Mohit Choudhary, and Subkaran Choudhary for their valuable feedback and suggestions I acknowledge the help provided by Sasikant Choudhary and Yogendra Singh Yadav in preparing the Solution Manual of this book   Suggestions for improving the book’s contents, queries, and criticisms are always welcome Akshay Choudhary About the Authors Akshay Choudhary, a renowned faculty of organic chemistry, teaches IIT-JEE aspirants, assisting them to achieve their goal Many students have been successful under his guidance and achieved top ranks in the IIT–JEE exam The author is a postgraduate in chemistry as well as Junior Research Fellow from NCL, Pune   His has keen interest in the subject and strives to present it to students in a lucid style to help them ace the exams effortlessly Mandakini Choudhary, specializes in reaction mechanisms and intermediates She is a dedicated teacher with four years’ experience and is popular among students for her zeal to help them with their board examinations This page is intentionally left blank General Organic Chemistry CHAPTER Question Bank Level Arrange the items in Questions 1–38 in DECREASING ORDER (i.e., greatest, most etc first) with respect to the indicated property Use the following code to indicate your answers The acidity of the protons H in each of the following is O O   (i)   (ii)  H C C C H3C O CH3 H (iii)  H C O (a) i > ii > iii O O C C CH2 CH3 O (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii Rate of reaction of HNO3/H2SO4 with each of the following is   (i)   (a) i > ii > iii OCH3 (ii) (b) ii > iii > i CN (c) i > iii > ii (iii)   CH3 (d) iii > i > ii 1.64 chapter one Exercise Identify the site of electrophilic attack at benzene ring   O   O   O O NH   O NH CH3 H3 C   O   O O N CH3 10 O CH3 H3C O O NH   O O O 11   12   CH3 CH3 CH3 CH3 H3C 13 O– O CH3 14   H3C CH3 CH3 15   H C N+ CH3 CH3 CH3 CH3 O CH3 O CH3 16 CH3 17   18   general organic chemistry O 19 CH3 H3 C 20   O 21   O CH3 H3 C 22 23   CH3 24   H3C CH3 CH3 N O O O HN O CH3 O CH3 25 CH3 26   27   NH CH2 N O – 28 CH2 O 29   O O S 30 O NH O 31   O NH CH3 CH3 CH3 CH3 CH3 32 O NH H2 N O 34 H 3C H3C NH CH3 CH3 CH3 33 O CH3 CH3 CH3 1.65 1.66 chapter one Exercise Identify the correct order of resonance energy for the following pairs of compounds O O     O O O S 11   O H N S 13   10   O CH– CH+ H N O CH– CH+ NH2 14   HN 15 CH+ 12   O CH– 16   S S HN 17 19 NH2 NH2 O O 18   20   H B H2N B H general organic chemistry 21 23 H B H B O N H CH+ CH+2 22 24 27 29 33 35 37 30 32 CH+ CH+2 CH– CH–2 CH+2 28 CH– CH+ 26 CH+ CH+ O 25 31 CH+ 34 36 CH– CH – CH + CH –2 1.67 1.68 chapter one Solution for Workbook Exercises Exercise Acidic Strength of Compounds OH OH OH OH OH OH CH3 Cl CH3 CH3 2>1>3 OH OH Cl Cl 3>2>1 OH OH OH OH F Br Br Br F 3>2>1 OH OH OH O N+ + N O O N − F OH − O CN O CN CN O OH OH OH OH + − 1>3>2 3>2>1 3>1>2 OH OH OH OH OH 2>3>1 OH O F 1>2>3 Cl − + N O OH OH OH NC CH3 H3C H3C OH 2>1 OH 10 H3C T3C D3C 1>2>3 CH3 CN OH general organic chemistry OH OH 11 Br H2N 1>2>3 Cl OH OH OH 12 H3N + H3C NMe3 1>2>3 + OH OH − 14 − HN H3C 3>1>2 OH CH3 OH OH Cl 15 − 16 O N CT3 CD3 3>2>1 OH O Br F OH OH OH OH 13 O OH + OH OH NC 2>1>3 COOH COOH COOH COOH 17 NC H3 C COOH 19 1>2>3 COOH COOH Cl 20 H3 N H2 N HO + + 1>2>3 COOH COOH T3C D3C 1>2>3 COOH COOH 18 Cl F COOH COOH COOH H3 C NMe 2>1>3 COOH COOH COOH COOH Cl 21 – O HN – 22 Cl H3 C Cl 3>1>2 COOH COOH 1>3>2 COOH COOH COOH COOH HO H3 C 23 24 OH H3 C 1>2>3 CH OH 1>3>2 1.69 1.70 chapter one COOH COOH N+ O– H3 C CH O 26 CH O– HO 28 HO 1>2 OH HO B COOH COOH OH OH 1>2 O COOH COOH OH B CH 29 OH HO O N+ CH O– 30 1>2 N+ O– 2>1 MeO Cl 32 1>2 Cl 1>2 OH OH OH O N+ 33 O– O– N + OH N O O– N + O O– N+ 34 O– CH OH OH O– O N+ N O– N+ O O– N+ O CH 3>2>1 COOH O– 36 OMe OMe N+ O 3>1>2 COOH 37 COOH COOH H2 N 38 H3 C H3 C H2 N 2>3>1 OH OH MeO 35 COOH O 3>1>2 OH H3 C OH + O– 3>2>1 OH O– OH + N+ O O OMe O – N+ O O O COOH COOH B B 31 OH HO OH O 2>1 27 HO N+ O– O COOH OH H3 C N+ 2>1 HO N+ CH H3 C CN COOH O– CH H3 C 25 H3 C COOH COOH NH 2>3>1 COOH CH CH CH CH general organic chemistry Exercise Carbocation Stability order + H2C CH3 CH3 H3C + CH C 3>2>1 CH3 CH3 H3C C+ CH3 + CH3 H3C CH3 + C CH + CH3 CH3 HC+ C+ H3C H3 C CH3 1>3>2 CH3 CH3 CH3 CH3 C+ CH+ CH+ 1>3>2 H3C CH3 C+ + CH CH3 H C H2C 1=2>3 H3 C CH3 H3 C CH3 HC+ H3 C CH3 C+ D3 C CD T C D3 C T 3C C+ CT C+ CH+ 1>3>2 3>2>1 CH3 CD CT C+ C+ C+ CH+2 CH3 1>2>3 CH+2 3>2>1 CH+2 CH+2 CH+2 CH3 CN 1>2>3 H3C CH+2 C+ CH3 HC+ CH3 CH3 H3C CH+2 OH CH+2 H3C CH3 1>2>3 CH3 3>2>1 Ph Br CH+ Ph Ph C+ 3>2>1 CH+2 17 CH+2 16 1>2>3 CH+2 H3 C 14 CH+2 CH+2 CH3 CH+2 Cl 15 CH+2 CH+2 CH+2 2>3>1 NH2 CT 1>3>2 CH+2 CD 12 NO 13 CH+2 CH+2 1>2>3 CH+2 CH+2 11 CH3 CH+2 10 CH3 CH+2 CT CD NO CN 1>2>3 CH+2 CH+2 CH+2 H3 C CH+ 18 3>2>1 H3 C CH3 C+ CH3 1.71 1.72 chapter one CH+2 CH+2 CH+2 19 20 CH+2 3>2>1 same stability CH3 CH+2 CH+2 CH+2 H3 C 21 H3 C C+ 22 CH3 1>2>3 CH3 H3 C C+ H3 C C+ CH3 2>1 CH3 H3 C 23 CH3 C+ CH+ 24 H3C CH+ H3C H3C CH+ H3C CH+ H3C 27 CH+ NH O NH O HN HN CH3 CH3 NH NH 3>2>1 C+ C+ 26 O C+ O 29 CH+ HN CH+2 CH+ NH C+ CH+2 3>1>2 31 H 3C CH3 30 C+ CH3 HN CH+ NH C+ CH3 CH3 H 3C H 3C CH3 H3C CH+2 H C C+ CH+ H 3C CH3 3>1>2 CH+ 32 1>3>2 CH+ CH+ 1>3>2 H3 C 33 CH+ CH+ H3C H 3C CH+ CH+ C+ O CH+2 28 CH3 H 3C H 3C CH H3C CH+ CH+ O H3C 2>3>1>4 H 3C CH+ O 4>2>3>1 CH3 CH+ H 3C H 3C O O 4>2>3>1 H 3C O 3>2>1 CH3 CH3 CH3 CH3 1>2>3 25 C+ HC+ CH3 CH3 CH3 CH3 C+ CH3 CH+ 3>2>1 O O 34 O CH+ CH+ CH+ 1>2>3 35 C+ CH+ CH + 1>3>2 general organic chemistry Exercise Identify localised and delocalised 1p in the following examples dl H N l l N N N l H2 N l N N H N N N dl dl l N dl l HN NH2 H2 N 10 l dl N l N N dl H 12 dl H N l O O N dl l 13 14 l O l dl dl O 15 dl dl H dl H N N N l l NH O 16 dl 17 l dl NH HN NH dl NH HN H2 N dl l 20 N CH3 l 21 NH N N H l N dl H3 C dl 18 O O l 19 l dl NH dl NH dl l O dl dl N H2 N N 11 N N H N H dl N dl l dl dl dl NH l 1.73 1.74 chapter one dl 22 HN 24 HB l 23 O N l NH HN N 25 l O N H l dl dl dl dl l 26 NH 27 dl H N NH NH2 H2 N H 28 l dl dl dl dl N N dl 29 NH2 dl l 30 NH NH HN dl NH2 l H3 C l CH3 NH N 31 dl dl 32 NH l H N dl NH HN l dl O l N H NH l NH general organic chemistry Exercise Identify the site of electrophilic attack at benzene ring O O O O O NH O O O N 10 O 11 CH3 O – O 12 CH3 CH3 CH3 CH3 H3 C 14 CH3 CH3 H3 C 15 CH3 + H3 C CH3 CH3 CH3 N CH3 CH3 CH3 O O Note : Major attack represents b arrow ( ) CH3 16 CH3 H3 C O O NH CH3 H 3C 13 O O NH O 17 18 1.75 1.76 chapter one 19 20 O 21 CH3 H3 C O O CH3 H3 C 22 23 24 CH3 CH3 CH3 H3 C N O O O HN O CH3 O CH3 25 26 CH3 O 28 - 27 CH2 30 O NH N 29 CH2 O O O S NH NH CH3 CH3 31 32 O NH O CH3 CH3 CH3 34 H3 C H3 C NH 33 O CH3 CH3 CH3 H2 N O O CH3 CH3 CH3 general organic chemistry Exercise Identify the correct order of resonance energy for the following pairs of compounds O O O O H N O O CH– CH+ CH– CH+ S O NH2 10 CH+ 13 O CH– 10 11 H N S 12 14 O 15 16 HN HN S 18 17 19 20 H2N 22 S CH+ O NH2 NH2 O O CH+ 21 H B B H 23 CH+ CH2+ 24 H B H B O N H CH+ CH2+ 1.77 1.78 chapter one 25 26 27 28 29 30 31 32 CH+ CH– 34 33 CH– 35 37 CH+ CH+2 CH – CH2– 36 CH– CH+ CH–2 .. .Advanced Problems in Organic Chemistry for Competitive Examinations Akshay Choudhary Mandakini Choudhary Copyright © 2017? ?Pearson India Education Services Pvt Ltd Published by Pearson India... order for increasing boiling point of the following compounds O H (i) O O OCH3 OH (ii) (iii) CH3 OH (i) (ii) increasing (a) boiling point (iii) (i) (ii) (iii) increasing (c) boiling point (ii)... their suggestions to akshaymandakini24@gmail.com Akshay Choudhary Mandakini Choudhary Acknowledgements The editorial team at Pearson Education has been pivotal in encouraging this project, while