Problem Solvers eT ie As A Complete Solution Guide Ua lL | * For Homework, Test Preparation, Exams Ce te me ie Ce | Che eg he Mm ee assigned by your instructor or given on a test PS tem Meee he Ces Le enabling you to understand the subject fully me me Ma ate ELCs Research & Education AssociationTHE ORGANIC CHEMISTRY PROBLEM SOLVER’ REGISTERED TRADEMARK A Complete Solution Guide to Any Textbook Staff of Research and Education Association Dr. M. Fogiel, Director Research and Education Association 61 Ethel Road West Piscataway, New Jersey 08854THE ORGANIC CHEMISTRY PROBLEM SOLVER ® Copyright © 1994, 1978 by Research & Education Association. All rights reserved. No part of this book may be reproduced in any form without permission of the publisher. Printed in the United States of America Library of Congress Catalog Card Number 94-67819 International Standard Book Number 0-87891-512-5 PROBLEM SOLVER is a registered trademark of Research and Education Association, Piscataway, New Jersey Il-1WHAT THIS BOOK IS FOR For as long as organic chemistry has been taught in schools, students have found this subject difficult to understand and learn. Despite the publication of hundreds of textbooks in this field, each one intended to provide an improvement over previous textbooks, students continue to remain perplexed, and the subject is often taken in class only to meet school/departmental requirements for a selected course of study. In a study of the problem, REA found the following basic reasons underlying students’ difficulties with organic chemistry taught in schools: (a) No systematic rules of analysis have been developed which students may follow in a step-by-step manner to solve the usual problems encountered. This results from the fact that the numerous different conditions and principles which may be involved in a problem, lead to many possible different methods of solution. To prescribe a set of rules to be followed for each of the possible variations, would involve an enormous number of rules and steps to be searched through by students, and this task would perhaps be more burdensome than solving the problem directly with some accompanying trial and error to find the correct solution route. (b) Textbooks currently available will usually explain a given principle in a few pages written by a professional who has an insight in the subject matter that is not shared by students. The explanations are often written in an abstract manner which leaves the students confused as to the application of the principle. The exrnlanations given are not sufficiently detailed and extensive to make the student aware of the wide range of applications and different aspects of the principle being studied. The numerous’ possible variations of principles and _ their applications are usually not discussed, and it is left for the students to discover these for themselves while doing the exercises. Accordingly, the average student is expected to rediscover that which has been long known and practiced, but lilnot published or explained extensively. (c) The examples usually following the explanation of a topic are too few in number and too simple to enable the student to obtain a thorough grasp of the principles involved. The explanations do not provide sufficient basis to enable a student to solve problems that may be subsequently assigned for homework or given on examinations. The examples are presented in abbreviated form which leaves out much material between steps, and requires that students derive the omitted material themselves. As a result, students find the examples difficult to understand--contrary to the purpose of the examples. Examples are, furthermore, often worded in a confusing manner. They do not state the problem and then present the solution. Instead, they pass through a general discussion, never revealing what is to be solved for. Examples, also, do not always include diagrams/graphs, wherever appropriate, and students do not obtain the training to draw diagrams or graphs to simplify and organize their thinking. (d) Students can learn the subject only by doing the exercises themselves and reviewing them in class, to obtain experience in applying the principles with their different ramifications. In doing the exercises by themselves, students find that they are required to devote considerably more time to organic chemistry than to other subjects of comparable credits, because they are uncertain with regard to the selection and application of the theorems and principles involved. It is also often necessary for students to discover those "tricks" not revealed in their texts (or review books), that make it possible to solve problems easily. Students must usually resort to methods. of trial-and-error to discover these "tricks", and as a result they find that they may sometimes spend several hours to solve a single problem. (e) When reviewing the exercises in classrooms, instructors usually request students to take turns in writing solutions on ivthe board and explaining them to the class. Students often find it difficult to explain in a manner that holds the interest of the class, and does not enable the remaining students to follow the material written on the boards. The remaining students seated in the class are, furthermore, too occupied with copying the material from the boards, to listen to the oral explanations and concentrate on the methods of solution. This book is intended to aid students in organic chemistry to overcome the difficulties described, by supplying detailed illustrations of the solution methods which are usually not apparent to students. The solution methods are illustrated by problems selected from those that are most often assigned for class work and given on examinations. The problems are arranged in order of complexity.to enable students to learn and understand a particular topic by reviewing the problems in sequence. The problems are illustrated with detailed step-by- step explanations, to save the students the large amount of time that is often needed to fill in the gaps that are usually found between steps of illustrations in textbooks or review/outline books. The staff of REA considers organic chemistry a subject that is best learned by allowing students to view the methods of analysis and solution techniques themselves. This approach to learning the subject matter is similar to that practiced in various scientific laboratories, particularly in the medical fields. In using this book, students may review and study the illustrated problems at their own pace; they are not limited to the time allowed for explaining problems on the board in class. When students want to look up a particular type of problem and solution, they can readily locate it in the book by referring to the index which has been extensively prepared. It is also possible to locate a particular type of problem by glancing at just the material within the boxed portions. To facilitate rapid scanning of the problems, each problem has a heavy border around it. Furthermore, each problem is identified with a number immediately above the problem at the right-hand margin.To obtain maximum benefit from the book, students should familiarize themselves with the section, “How To Use This Book," located in the front pages. To meet the objectives of this book, staff members of REA have selected problems usually encountered in assignments and examinations, and have solved each problem meticulously to illustrate the steps which are difficult for students to comprehend. Special gratitude is expressed to them for their efforts in this area, as well as to the numerous contributors who devoted brief periods of time to this work. Gratitude is also expressed to the many persons involved in the difficult task of typing the manuscript with its endless changes, and to the REA art staff who prepared the numerous detailed illustrations together with the layout and physical features of the book. The difficult task of coordinating the efforts of all persons was carried out by Carl Fuchs. His conscientious work deserves much appreciation. He also trained and supervised art and production personnel in the preparation of the book for printing. Finally, special thanks are due to Helen Kaufmann for her unique talents in rendering those difficult border-line decisions and in making constructive suggestions related to the design and organization of the book. Max Fogiel,Ph.D. Program DirectorHOW TO USE THIS BOOK This book can be an invaluable aid to students in organic chemistry as a supplement to their textbooks. The book is subdivided into 35 chapters, each dealing with a separate topic. The subject matter is developed beginning with structure and properties and extending through spectroscopy, stereochemistry , molecular orbital theory, and all of the principal classes of organic compounds. Sections on natural products,photochemistry , and color have also been included. Wherever applicable, topics include nomenclature, preparation, synthesis and reactions, characterization tests, and spectroscopy. TO LEARN AND UNDERSTAND A TOPIC THOROUGHLY 1. Refer to your class text and read the section pertaining to the topic. You should become acquainted with the principles discussed there. These principles, however, may not be clear to you at that time. 2. Then locate the topic you are looking for by referring to the "Table of Contents" in the front of this book, "The Organic Chemistry Problem Solver." 3. Turn to the page where the topic begins and review the problems under each topic, in the order given. For each topic, the problems are arranged in order of complexity, from the simplest to the more difficult. Some problems may appear similar to others, but each problem has been selected to illustrate a different point or solution method. To learn and understand a topic thoroughly and retain its contents, it will be generally necessary for students to review the problems several times. Repeated review is essential in order to gain experience in recognizing the principles that should be applied, and in selecting the best solution technique.TO FIND A PARTICULAR PROBLEM To locate one or more problems related to a particular subject matter, refer to the index. In using the index, be certain to note that the numbers given there refer to problem numbers, not page numbers. This arrangement of the index is intended to facilitate finding a problem more rapidly, since two or more problems may appear on a page. If a particular type of problem cannot be found readily, it is recommended that the student refer to the "Table of Contents" in the front pages, and then turn to the chapter which is applicable to the problem being sought. By scanning or glancing at the material that is boxed, it will generally be possible to find problems related to the one being sought, without consuming considerable time. After the problems have been located, the solutions can be reviewed and studied in detail, For this purpose of locating problems rapidly, students should acquaint themselves with the organization of the book as found in the "Table of Contents." In preparing for an exam, it is useful to find the topics to be covered on the exam in the "Table of Contents," and then review the problems under those topics several times. This should equip the student with what might be needed for the exam. viiiCONTENTS Chapter No. Page No. 1 STRUCTURE AND PROPERTIES l Lewis Structures 1 Structural Formulas 4 Bonding 9 Acids and Bases 14 2 SPECTROSCOPY 23 Line Spectra 23 Infrared Spectroscopy 24 Raman Spectroscopy 33 Ultraviolet Spectroscopy 35 NMR Spectroscopy 42 Mass Spectroscopy 54 Electron Spin Resonance 60 3 ALKANES 64 Combustion and Bond Dissociation Energy Halogenation 86 4 CYCLOALKANES 97 Conformations 105 Angle Strain 109 Stereoisomerism 114 Polycycloalkanes 116 5 STEREOCHEMISTRY 118 Optical Activity 118 Chirality 121 Enantiomerism 128 Diastereomerism 146 Racemization 155 6 ALKENES 167 Geometric Isomerism 174 Addition Reactions 192 Oxidation 204 Polymerization 212 Alkylation 21310 11 12 13 14 15 16 17 18 ALKYNES 226 MOLECULAR ORBITAL THEORY 248 Electrocyclic Reactions 259 Cycloaddition Reactions 266 Resonance Theory 269 ALKADIENES 276 Conjugated Dienes 278 Diels-Alder Reactions 283 1,2 Cycloaddition Reactions 287 Allenes 288 Polymerization 290 BENZENE 302 Aromatic Character and Properties 302 Nomenclature and Structure of Benzene Derivatives 313 ELECTROPHILIC AROMATIC SUBSTITUTION = 335 Nitration 325 Halogenation 337 Friedel-Crafts Reactions 343 Sulfonation 351 Effect of Substituents on Reactivity 354 ARENES = 379 NUCLEOPHILIC DISPLACEMENT 418 2 and Syl Reactions 419 ereochemistry of Reactions 431 Structural and Solvent Effects 434 ELIMINATION REACTIONS 463 E2 and El Reactions 463 Stereochemistry 478 Elimination vs. Substitution 483 ORGANOMETALLIC COMPOUNDS 493 Grignard Reagents 497 Organolithium Compounds 509 Reformatzky Reactions 511 ALCOHOLS 517 Oxidation 551 Hydroboration 570 ETHERS 575 Epoxides (Oxiranes) 599 ALDEHYDES AND KETONES! 615 Carbonyl Reactions with Ammonia Derivatives 64629 30 31 32 33 34 35 ORGANOSILICON, PHOSPHORUS, AND BORON COMPOUNDS 1110 FATS 1139 Fatty Acid Biosynthesis and Oxidation 1140 Detergents 1143 Lipids 1144 Oils 1149 Steroids 1161 CARBOHYDRATES 1165 Derivatives of Glucose 1178 Glycosides 1180 Disaccharides 1186 Polysaccharides 1196 AMINO ACIDS AND PROTEINS 1203 Lactams 1225 Peptide Synthesis and Degradation 1232 Enzymes 1253 Coenzymes 1257 NUCLEIC ACIDS 1260 NATURAL PRODUCTS 1270 Steroids 1297 Terpenes 1306 Aromatic Natural Products 1314 PHOTOCHEMISTRY AND COLOR 1334 Light Absorption, Fluorescence and Phosphorescence Structural Effects 1340 1334 Molecular Orbital Theory 13845 Dyes 1350 Photodissociation 1357 Photochemical Reduction, Isomerism, Reactions 1360 INDEX = 1379 xiiUNITS CONVERSION FACTORS This section includes a particularly useful and comprehensive table to aid students and teachers in converting between systems of units. The problems and their solutions in this book use SI (International System) as well as English units. Both of these units are in extensive use throughout the world, and therefore students should develop a good facility to work with both sets of units until a single standard of units has been found acceptable internationally. In working out or solving a problem in one system of units or the other, essentially only the numbers change. Also, the conversion from one unit system to another is easily achieved through the use of con- version factors that are given in the subsequent table. Accordingly, the units are one of the least important aspects of a problem. For these reasons, a student should not be concerned mainly with which units are used in any particular problem. Instead, a student should obtain from that problem and its solution an understanding of the underlying principles and solution techniques that are illustrated there. For the reverse, multiply by ACTOS voscsscsscsessesseesssseeees Square feet ..ceceuceceeenee | 4.356 x 104 2.296 x 10-5 ACTOS ....ececesseeeee | SQUALe Meters 4047 2.471 x 104 ampere-hours .............. coulombs 3600 2.778 x 10-4 ampere-turns ...........06 gilberts 1.257 0.7958 ampere-turns per cm. .. | ampere-turns per inch 2.54 0.3937 angstrom units wu... | INCHS oes 3.937 x 10-9 2.54 x 108 angstrom units............. | meters {0-10 10!0 atmospheres ................ feet of Watel 0... | Od-90 0.02950 atMOspheles .........0000 inch of mercury at 0°C 29.92 3.342 x 10° atmospheres ................ | kilogram per square meter 1.033 x 104 9.678 x 10° atmospheres ................ | millimeter of mercury at O°C .... | 760 1.316 x 10° atmospheres ................. | pascals 1.0133 x 105 0.9869 x 10-5 atmospheres .................| pounds per square inch 14.70 0.06804 OE ee atmospheres 9.870 x 10°? 1.0133 DalS voiseeesesesssescesesseeses dynes per square cm 108 10-6 bars pascals 105 10-5 DAMS w.eccceecssesseceeseeseeseene pounds per square inch 14.504 6.8947 x 10° 210 1.0548 x 101° 9.486 x 107"! Btu . 778.3 1.285 x 10° Btu joules 1054.8 9.480 x 10-4 Btu oe ceeesecssesesseseeenees kilogram-calories 0.252 3.969 calories, gram .............. 3.968 x 10-3 252 calories, gram ............. foot-pounds occ. | 3.087 0.324 calories, gram... JOUIES vo. cccesscceserereesrerces | 4.185 0.2389 CeISIUS Looe ee eee Fahrenheit (°C x 9/5) + 32 = °F (°F — 32) x §/9 = °C xiiiTo convert Celsius .......csseeese Pte] ty ebenee centimeters ............00 centimeters ........0.. centistokes ............. circular mils ................. circular mils ................. cubic feet ............... cubic feet ................ cubic inches ............... cubic inches ................ cubic inches............ cubic inches ........... cubic meters .......... cubic meters .......... CUTIES occ eceseeree cycles per second .. degrees (angle) ...... degrees (angle) ...... GYNES wo. cceeeeeee ergs per square cm. Fahrenheit ............... ponsee ooeeas seers seeee Fahrenheit ................00. fErMiS oe eeeesceseeree foot candles ............ foot lamberts........... vate eteee foot-pounds ................ foot-pounds ..............04 foot-pounds ............0 foot-pounds ............ foot-pounds uo... gallons (liquid U.S.) ..... gallons (liquid U.S.) ..... JAMMAS ....eeeeeseeeeene QaUSSES vee QaUSSES oo. ceeee QAUSSES 0... eseeeeeeee QaUSSES oo... ceeseeeeee wenae vores square meters per second........ square centimeters ...........cc0 Square MINS occ ccesscceeesseees gallons (liquid U.S.) ... liters... sesenssescsaceases cubic centimeters seeeeeeeseesansneaes CUbIC feet oes ceeeeeseeeee Cubic Meters .........cccesssseeseeseeee gallons (liquid U.S.) 0... CUDIC feet ees seseseseceessreeee CUDIC Yards... eeseesesseeceeteeee coulombs per minute ...........+ TAGIANS 0.0... ceecsesseseseseeeenns POUMAS o.oo. eee cceceeesesseerseseeceene joules .......... FOOt-POUNAS oo... ecesestseseceeee joules ... watts per square CM............. KOIVIN .....ceccesesceeseseecensssseeeesesees Rankine .......ccccessscesssseeversreeess AMpere-hOUls ........cccessseesesesees CENTIMETELS 0.0... seeesssevesseneess MALES 0... ccessccecsescesesesescees candelas per square meter ....... gram-centimeters.............0., horsepower-hours...........0.008 kilogram-meters.........ueesee kilowatt-hours ........ccceseesssees OUNGE-INCHES ..........sesessseseecseeees CUDIC MEETS ....... eee ccesseeeeeceeeee gallons (liquid British Imperial) LS: lines per Square GM. .........0..00. lines per square inch .............. TOSIAS oc cecessscneeeuseneeensneces AMPETES ......essessseesscesessseceneneans FAGIANS 0... ..ccceceocescessecsescsnssesseoes QIAINS ve esseeecsscseees °C + 273.1 =K 1x 108 0.03281 1x 10% 5.067 x 10-6 0.7854 7.481 28.32 16.39 5.787 x 10-4 1.639 x 10-5 4.329 x 10-3 35.31 1.308 1.1 x 10! 1 17.45 1.745 x 10-2 2.248 x 10-6 1.602 x 10-19 7.376 x 10-8 10°? 10°? 10-3 (°F + 459.67)/1.8 °F + 459.67 =°R 26.8 30.48 0.3048 1.2 x 104 190-15 10.764 3.4263 1.383 x 104 5.05 x 10-7 0.1383 3.766 x 10-7 192 3.785 x 103 0.8327 10-9 1.0 6.452 10-4 6.452 x 10-8 0.7958 1.571 x 10-2 0.06480 For the reverse, multiply by K— 273.1 =°C 1x 10° 30.479 1x 106 1.973 x 105 1.273 0.1337 3.531 x 10-2 6.102 x 10-2 1728 6.102 x 104 231 2.832 x 10°? 0.7646 0.91 x 10°" 1 5.73 x 10-2 57.3 4.448 x 10° 0.624 x 10%8 1.356 x 10’ 10? 10’ 10 1.8K — 459.67 °R — 459.67 = °F 3.731 x 10°? 3.281 x 10-2 3.281 8.333 x 10-5 1915 0.0929 0.2918 1.235 x 10-5 1.98 x 108 7,233 2.655 x 108 5.208 x 10-3 264.2 1.201 10° 1.0 0.155 104 1.55 x 107 1.257 63.65 15.432 7000 1.02 x 10-3 6.481 x 10-2To convert QIAMS .....eesesseseseesssnesees horsepower? ........ ee HOrSEPOWET ..........0.0000: NOFSEPOWET ..........00c.000 HOrSePOWET ....... cesses hOrsepOWel .............0006 INCHES oo. .eeeceteetenees JOULES oo eeeereeeeseesenes JOUIES oe eeeeseeeeeee KIOGFAMS ..... ee eeeeeeee KIIOQTAMS .......cceeeeseees Kilogram ..........eeeeeee Kilometers ........ccecseee KJOMetELS vo... eeesseeeeees kilometers per hour...... kilowatt-hours .............. kilowatt-hours .............. kilowatt-hours .............. kilowatt-hours ............. Ce VIROTS ooo lcceseecseeseceenees JIGONS ose seeesssesecsesseseees JCS vc. ceccesscssseseusersserees lumens per square foot lumens per square meter MAXWEIIS 0... cece eee | i]: MELETS 0... ceseesccseanseeeee MELELS oo ecceceeeeeeees MetOLS «ce cecrecceseecceees miles (nautical) ............ miles (nautical) ............ miles (statute) .............. miles (statute) .............. miles (statute) .............. miles per hour .............. miles per hour............. millimeters 0... eee re | attr ounces (avdp) ............... POUNCATS ......... cesses Btu per minute .............. Prrererrery ervevoreree dob veoeceee foot-pounds per minute ........... foot-pounds per second........... horsepower (metric) ..... kilowatts .......csseececneeee canteneroee sareneceeen oeeeoaroees Yard oo .ceceseccesesseesetceecnetecenetoees foot-PpoOuUNdS ....... eee Watt-Nours 0... eee tons (lONG) ...... eee tons (Short) ......... eee Beaeassocee seeneewnnee pounds (AVP) 0... eceeeseeseeees Dave ccceree aoueeowseue eter eenae foot-pounds ......... ee horsepower-hours......... JOUNES wos eeeeeeeeetseeees seco eetene operon eeene waatevevoes feet per SECON .........ecseseees miles per hour............... candles per square cm. ............ candles per square inch cubic centimeters .......... CUDIC INCHES oo... cece eens gallons (liquid U.S.) we pints (liquid U.S.) oe foot-candies .......... foot-candles wu. eestor ensee se venereone fOOt-CANCIES oo... ceeseeesescersesees eeeeroenree ooaareooonr eveipeceas seeeecavece weet eoneces MOTELS... cessscececoecsevsecseecestseeees FOC eee eccecccecesscsseesccessecsensees kilometers vo... cesses miles (nautical) ............cseeee feet per second ou... KNOTS .....csecessecestsersenserceseeneeseees MICTONS ...... see eeecseee 3.527 x 10-2 7.093 x 10-2 2.54 8.333 x 10°? 2.54 x 10° 1.578 x 10°5 108 2.778 x 10°? 0.7376 2.778 x 10-4 9.842 x 10-4 1.102 x 10-3 2.205 3281 3.937 x 104 54.68 3413 2.655 x 10° 1.341 3.6 x 10° 1.688 1.1508 0.3183 2,054 10 61.02 0.2642 2.113 1 0.0929 0.0929 103 10% 3.28 39.37 6.214 x 10-4 1.094 6076.1 1852 5280 1.609 0.869 1.467 0.8684 108 For the reverse, multiply by 28.35 14.4 0.4047 2.357 x 10-2 3.03 x 105 1.182 x 10° 0.9863 1.341 0.3937 12 39.37 6.336 x 104 10° 36 1.356 3600 1016 907.2 0.4536 3.408 x 10-4 2.54 x 10-5 1.829 x 10°? 2.93 x 10-4 3.766 x 10°? 0.7457 2.778 x 107? 0.5925 0.869 3.142 0.4869 10-3 1.639 x 10-2 3.785 0.4732 { 10.764 10.764 108 108 30.48 x 10-2 2.54 x 10°? 1609.35 0.9144 1.646 x 10-4 5.4x 104 1.894 x 10-4 0.6214 1.1508 0.6818 1.152 10° XVMIS 2... .esesensessescetercnesees minutes (angle) ............ minutes (angle)............ NEWRONS .....eeccsrseseeseee NEWONS .......eeceseseeeeeee newtons per sq. meter . NEWIONS ......ssecseseseseseee OeFsteds .........ccesseseeeees ounces (fluid)............... ounces (AVAP) ..........06 pounds per square inch pounds per square inch quarts (U.S. liquid)....... FAdIANS .....eseeeseeesseeceseee FadIANS ......ccseseeesesseeseeee TaGIANS oes sseseeeseseee revolutions per minute . OCNIGENS ....... es eeceereeee SIUQS ....cessescsesseeeesereenss SIUQS .....essesscecceseessreeens square feet wu... square feet ........ccseee square feet ...........ec square incheS..........00 square kilometers......... StOKES oo... cescseccescesees tons (metric) ............... tons (short) ...........00. 0] d | watt-seconds............00 re webers per square meter xvi GOQIOCS 0... cececssecccsesseessetenes FACIANS 00... ssesesesesecerecsnseeersees ANS oo. eecesssssssseesesesrseecsnen ees KIOQFAMS oo... eecsesessseseeteeene PASCAIS 0... cccsesssecseceesereeeerse pounds (aVdp)...........ccessesseeees GYNES veecescccssssesetsceesesseseersessens NEWEONS oo... ec ccssseseeeserceeees dynes per square cm................ PASCAIS oo... eeesecssetecsesseseeseees cubic centimeters..............00. Minutes Of AFC 0.0... esses seconds Of aFC....,.....sccecesseseees radians per second ............0..0. coulombs per kilogram ............ KiOQFAMS .....csscccsescecveeseeesseeesens POUNS (AVAP).......csscescsesseeees square centimeters vc. SQuare INCHES ..........sccssveesseeees SQUAE MILES... cceccccscssseeesrereee square centimeters .................. Square MINAS ...........ccecsseessesesces square meter per second ......... KIIOQFAMS .....esesccesessessecseenes newtons per square meter ....... Btu per hour... cesses foot-pounds per minute ........... NOFSOPOWET ........csssseessesseseresenes JOUIOS 0... ssesesessesseesessereeesecseeee MAXWEIIS oo. .cseccsssecssesesseesersoees QAUSSES vo. eeesseseesetssesteeeeeees 3.438 1.666 x 10-? 2.909 x 10-4 10° 0.1020 1 0.2248 7.9577 x 10 3.125 x 10-2 6.25 x 10°? 0.50 1.383 x 104 3.108 x 10-2 453.6 4.4482 6.8946 x 104 6.895 x 10° 946.4 103 3.438 x 108 2.06265 x 10° 0.1047 2.58 x 10-4 1.459 32.174 929.034 144 3.587 x 10-* 6.452 0.3861 10+ 108 2000 133.32 3.413 44.26 1.341 x 10-3 For the reverse, multiply by 3.94 x 104 0.2909 60 3484 105 9.807 1 4.448 1.257 x 10-2 32 16 2 7.233 x 10-5 32.17 2.205 x 10° 0.2288 1.450 x 10-5 1.45 x 10-4 1.057 x 10-3 103 2.909 x 10-4 4.848 x 10-6 9.549 3.876 x 108 0.6854 3.108 x 10-? 1.076 x 10-3 6.944 x 1073 27.88 x 108 0.155 2.59 10-4 10-8 5x 104 75x 103 0.293 2.26 x 10°? 746 1 10-8 10-4T-6°07- | 7-0T-B1- 040 2-812" Z-6-2%2-] 2-6-1 (Le2) zaporcez| 6zO°BEZ| ESEOtez| TECzezZ or O+ + + SACINILOV D+ 49 t: dn e n p+ eq QL ct f+ L6/E+ 96 t+ €6le+ 6] 5+ 16] %* 06 dON | Z-6-ZE- T-A-1E- z-B-6t- | 2-8-82-| Z-B-Lz- | 28+S7- z8-1z-| Z-8-07- £00°0 F £96°FL1 ZPE6 R91 roger | OS Z9E] HSzZ6'RSI 96IST L.o6'ort| = Z1081 vy] oH Aq aL PO|e. 4 idly. 99 SAJCINVHINVT c+ IZ CH LOTE+ OM) E+ SOI E+ =O LZ gD €+ 6S/e+ gg odo Woo wy jo adoiost 9yquas IsOwW 490 ssoquinu ssvew o1v sosaysuaied ul SIOQUINAL TUTE LOlZE- 7-8-R1- casvo (092)} (092) pSZO'9ZZ HIGON fH} ot Ja ey _ Vv _ Sol vol z+ =o dO-N- | B-BL-ZE- catze | eree-| earze | carze-| raze! z-orze-] estze- zelze-| eteze-| eitze-| ZONE (222) poge's0z| Loz] Le vOz | GS°007| s99e96I| —GO'SGT| = 77'Z61 Loz'98t | S8'esT} SLpeORt| erat S06 ZEL $: OW M el 1H b+ SL {9t Li St ELE OTL So I+ SS ce Ulee 8Hlee OV ge tdlee 4d rH [git+ og}t+ 6z[e+ gzter ae ‘qd £3 bet | p> Ad t+ 868 sgist-| rset] ears | caret | Feret| osrer| rerer ZErRE | etal | zee] e-Oret | cee | BRT | BRT seize} 6vatt| zeeit| teztr| goszor| e901! ssoezor) coor! zoces6| vese| 90676! 72161 6soese| zoze| *29N'se qs|,, US uy Pp? 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Assume that every atom has a complete octet (except hydrogen, of course), and that two atoms may share more than one pair of electrons. (a) H2SO,4 (b) NoHy, (c) COC1 2 (d) HONO (e) HSO,~ (£) CoHe (g) CH202 Solution: The consideration of the structure of molecules requires an understanding of chemical bonds, the forces that hold atoms together in a molecule. One type of chemical bond is the covalent bond, which results from sharing of electrons. The bonding force is electrostatic attraction: this time between each electron and both nuclei. The formation of ammonia serves as an example of this and an electronic structure below depicts how the electrons are shared. H e xe 3Hx + °-N:) ——» 1 =HeNiH (ammonia) Each dot or "x" denotes an electron. (The different symbols for the electron are meant for clarity, and not to suggest a difference.) In writing the electronic struc- tures for the formation of ammonia, one had to realize the number of electrons in the incomplete shell. Each hydrogen atom has one and the nitrogen atom has five. These numbers are obtained from inspection of their electronic configurations. By hydrogen and nitrogen bonding, nitrogen obtains a complete octet (8 electrons surrounding it) for stability and completion of outer shell and each hydrogen atom is now surrounded by 2 electrons for completion of its shell.One can now proceed to write the electronic structures the problem calls for. (a) H2S0,. Consider first the number of electrons in the incomplete shell for each atom. Hydrogen has one, oxygen has six, and sulfur has six. Both sulfur and oxygen must have a complete octet. Hydrogen must have two electrons for a complete shell. To distinguish the electrons for clarity and see how they are arranged in the electronic structure, the following symbols will be used: Hydrogen's electrons will be represented by +,sulfur’sby °, and oxygen's by x.The electronic structure can be written as: xx XO x aM 40 ex H#¥Ox S50 2H xx xXx Ox xx Notice how only this configuration satisfies the requirement that sulfur donates six electrons, oxygen six electrons, and hydrogen one electron. (b) Ne2Hy HH ok HxN:NxH Here, each nitrogen contributes 5 electrons (+) and each hydrogen contributes 1 electron (x). (c) COCl2 The carbon atom can contribute only 4 electrons (this is the number in its incomplete shell - represented by +) and the chlorine atom can contribute 7 (represented by x). Oxygen's electrons are shown as dots (°). xX XC1ly xx +x - XC1LE¥C}H.O. xx + Notice at arrow that two pairs of electrons must be shared for complete octets to be obtained. This denotes the pre- sence of a double bond. (A triple bond would have three pairs of electrons shared between two atoms.) (a4) HONO (Oxygen: +, nitrogen: x, and hydrogen: °) + + WX ++ H +o} nN ®i of ++ (e) HSO,” (Hydrogen: +, sulfur: +, and oxygen by x) xx xOX vx o Mx H*XO,x S x, OX, O " 8 . ~ xx©"\"“this electron accounts for xOx negative charge xx(£) CoHo (Carbon: + and hydrogen: ° ) HtCHtCtH +++ (g) CH20 (Carbon: + , hydrogen: * , and oxygen: x) Htc + OsH ++ xXx @ PROBLEM 1-2 Draw Lewis structures for the following substances. Use distinct, correctly placed dots for the electrons. Mark all atoms which are not neutral with charges of the proper sign. propane . ethylene oxide cyclopropane - sodium acetate (CH 3CO 2nNa®) benzene methylamine methyl bromide acetamide methanol nitromethane Solution: In drawing the Lewis structure of the follow- ing compounds, it should be noted that each element should have a complete octet (eight electrons in its outer shell). The exception to this rule is hydrogen which has a duet Shell. HHH Xe Me Me (a) Propane: C3Hes HzC:C:CxH Xe Xe xe H HH Elements that are in the middle of the periodic table tend to acquire the electrons to complete their octets by sharing electrons. H ° x Me “Cc * + 4H — Hx CxH . Xe H wand - both represent electrons, though from different sources. (b) Cyclopropane: C3H,. In this compound, the 3 carbon atoms mutually share electrons with one another thus form- ing a ring. H 4H yw 4, one HsC : CTH we Ke (c) benzene: CgHe. H H H Me Cc, HRC CRH - . ae Hx _ChH co ye H(a) methyl bromide: CH3Br H Electrons Xe ++ from bromine H*% C $Brt are repre- 4 ++ sented by + H {e) methanol CH 30H H:C:0:H H H (f) ethylene oxide H:C:Cs:H 2. e* H Oe (g) sodium acetate CH;COO7Nat H:C:C H +0'O Na® H (h) methyl amine CH;NH, H:C:N:H H H H O%$ (i) acetamide CH3;CONH2 H:C: C_ H N° H H H “00 “ @y (j) nitromethane CH3NO2 H:C:N H O° STRUCTURAL FORMULAS © PROBLEM 1-3 How many isomers of formula CH,¥ would be possible if methane were a pyramid with a rectangular base? What are they? Solution: Any compound, no matter how complicated, that contains carbon bonded to four other atoms can be considered as a derivative of methane. For any atom Y, only one substance of the formula CH;Y has ever been found. Chlorin- ation of methane yields only one compound of formula CH3Cl; bromination yields only CH;Br. The same holds true even ifY were not only an atom, but a group of atoms (i.e., if the group itself is not too complicated to bring about isomerism). This means that every hydrogen atom in methane is equivalent, so that replacement of one hydrogen as opposed to another always yields the same product. To answer this problem one makes two identical pyramidal models of CH, (with C at the apex), and then re- place, for instance, the upper right-hand H with a differ- ent atom Y; in the other model replace the lower right- hand H. Next determine whether or not, by any manipulations except bending or breaking bonds, the models can be made to coincide in all their parts. If the two models are super- imposable, then they represent two molecules of the same structure;if the models are not superimposable, then they represent molecules of different structures which, since they have the same molecular formula, are by definition isomers. All the possible pyramidal structures of CH3Y are drawn and shown in figures A through D. WN wWOoOA Ww Y “HH H H H H H Y (a) (B) (c) CD) In each of these structures the ¥Y atom has been shifted to each of the four corners of the rectangular base. With close inspection and imagination one can distinguish only two non-superimposable molecules. Figures A and C are the same, as are figures B and D. Thus, only 2 isomers of CH3;Y can be formed if its structure were a pyramid with a rectangular base. @ PROBLEM 1-4 How many isomers of formula CH2Y%Z would be expected from each of the following structures for methane? (a) Carbon at the center of a rectangle; (b) Carbon at the center of a square; (c) carbon at the apex of a square base pyramid; (d) carbon in the center of a tetrahedron. Solution: For any atom Y and for any atom 2, only one substance of the formula CH2YZ has ever been found. Halogen- ation of methane yields only one compound of formula CH.2Cl, only one compound of formula CH2Br2, and only one compound of formula CHeC1Br. To answer this problem one must make molecular models of CH, in the particular shape in question. One then pro- ceeds to replace two hydrogen atoms by a Y and 2 atom. Next determine whether or not, by any manipulation except bend- ing or breaking bonds, the models can be made to coincide in all their parts. If the models are superimposable, thenthey represent molecules of the same structure;if the models are not superimposable, then they represent molecules of different structures which are by definition isomers. (a) Carbon at the center of a rectangle: Draw all the possible structures of CHzYZ in this arrangement. These are shown in figures A through L. H H H HY H @ HZ ¥ ¥ 224 Y Z H Y H H H (A) (B) (c) (D) (E) Y ZH ZH Y H ZY H H H H YH ZY H H z (F) (c) (H) (1) Ca) H YZ H Z H H Y (K) (L) With some intuition one can distinguish only three different structures. Figures A, B, E, and F are the same; figures C, D, G, and H are the same; and figures I, J, K, and L are the same. (b) Carbon at the center of a square: H H H HY HZ H Z@ Y ¥ ZH a od DS DX Dd IX Dd EX Y 22 Y Z H Y HH H H HH Y A’ B‘ c' D' E' F' G' H Y H ZY¥ H H Y @ H See H ZY H H ZZ H H Y H' I' J' K' L'Draw all the possible structures of CH2YZ in this ar- rangement. These are shown in figures A' through L'. With some intuition one can distinguish only two different struc- tures or isomers. Figures A', B', C', D', E', F', G', and H' are the same; and figures I', J', K', and L' are the same. (c) Carbon at the apex of a squarebase pyramid. Draw all the possible structures of CH2YZ in this arrangement. With a little imagination figures A' through L' can be seen as the top view of a pyramid with a square base. However, care must be taken when rotating these structures; their bases must not be removed from the plane of the paper. With some intuition one can distinguish three different struc- tures or isomers. Figures A', C', E', and G' are the same; figures B', D', F', and H' are the same; and figures I', J', K', and L' are the same. These three figures are re- drawn as figures l, 2, and 3, respectively. HS 4H H © 4 W AN } Y Zz H (1) (2) (3) (d) Carbon in the center of a tetrahedron. As stated at the beginning of this problem only one structure of the methane derivative, CH,YZ, has ever been found. This struc- ture is a tetrahedron Sind is shown in figure M. (M) @® PROBLEM 1-5 In the complex ion Co(NH3).67?, the bonds to the central atom can be pictured as utilizing six equivalent sp°d? (or d*sp*) hybrid orbitals. On the basis of maximum separation of orbitals, what geometry would one expect this complex to have? Solution: An understanding of hybridization will be necessary for the solution. Consider the case of beryllium chloride, BeCl.. Beryllium may be pictured as: ls 2s 2p © © 000 S and P represent atomic orbitals. The former is a sphere with its center at the nucleus of the atom, while the latter 7is dumbbell-shaped. It consists of two lobes with the atomic nucleus lying between them. Since the axis of each P orbital is perpendicular to the axes of the other two, they are differentiated by the names Pie PY and Po: An orbital may be defined as the region in space where an electron is likely to be found. An orbital may hold no more than 2 electrons (the Pauli Exclusion Principle). (Electrons are shown as dots.) The coefficients represent energy levels, with 1s as the lowest energy level and 2s and 2p being positioned at the next highest energy levels. Inspection of the picture of beryllium shows it has no unpaired electrons. Hence, to account for beryllium combining with two chlorine atoms, one could promote one of 2s electrons to an empty p orbital: ls 2s 2p ©) o ©00 This procedure creates two unpaired electrons which could theoretically bond to chlorine in two different bonds, one using a p orbital, the other as orbital. How- ever, it is an established fact the two bonds in beryllium are equivalent. Consequently, the orbitals must be combined. The scheme below shows the combination of one s and one p orbitals to produce the mixed (hybrid) orbitals: ls. 2s p Q @ @00 + ls Pp © 00 oo I | sp In sp hybridization, two orbitals are produced that represent a mixture of s and p orbitals. These orbitals are equivalent and much more strongly directed than either the s or p orbital. The sp hybrid orbitals point in exactly opposite directions; this arrangement permits them to get as far away from each other as possible. For note that electrons of like spin tend to get as far away from each other as possible, and it is this that mostly determines the geometry or shapes and properties of molecules. In sp* hybridization, one has three orbitals, so that a trigonal (three-corned) arrangement permits the least contact of the orbitals. It can be visualized as shown: t ° < 120 Sp? hybridization requires a tetrahedral (angle = 109.5°) arrangement for the least possible overlap of orbitals. 8These considerations, then, should provide an important insight into the geometry of Co(NH3),5*°. In this instance, one has the hybridization sp*d*, which indicates that six equivalent orbitals are involved. (The mixture is 3 from p, 2 from d, and 1 from s.) The point is to think of a geometry that will keep these six hybrid orbitals as far apart as possible. The best configuration or geometry would have to be the octahedral as shown: BONDING ® PROBLEM 1-6 Assign all the electrons in acetaldehyde (CH3~CH=0) to their atomic or molecular orbitals. Solution: The formation of covalent bonds by the sharing of electrons results from the overlapping and interaction of partially filled atomic orbitals. The molecular orbitals (bonds) so formed are represented adequately by the summa- tion of the geometrical properties of the individual atomic orbitals. Since bond formation is produced by the interaction of orbitals, which can be highly directional, the most effective bonds will be formed when the relative spatial positions of the atoms are such as to produce the best possible overlap of orbitals. To be able to assign all the electrons in CH3;-CH=O to their orbitals, first set up the electron dot formula: H H H:c}s C7::0: Hq When an atom forms a compound in which it is attached to four neighbouring atoms by single bonds, sp? hybrid orbitals are used to form these bonds. Thus carbon 1 is sp? hybridized. All hydrogen atoms have s orbitals, there- fore, the three carbon-hydrogen bonds on the first carbon atom are sp°*-s bonds. The carbon-carbon bond between the first and the second carbon are sp’-sp? bonds. Sp2 orbitals are utilized only in the formation of molecules containing double bonds. This gives a trigonal arrangement (planar) in space as opposed to the tetrahedral arrangement of the sp? hybrid orbital. Thus the carbon-hydrogen bond on the second carbon atom is an sp*-s bond, while the double bond on the oxygenatom is composed of two different bonds. One bond is the sp*-p bond and the other (weaker) bond is a p-p bond. @ PROBLEM 1-7 Write an expanded structural formula with a line for each bond for each of the substances represented below by a condensed formula: (a) CH;CH(CH;) 5 (e) CH,CONHCH, (b) CH3CCCH; (c) CH»,C1OCH,CHO (£) CH»CH,OCH CHO (d) (CHa), Solution: (a) In 2-methylpropane, CH3;CH(CH3)2, 3 hyd- rogens are joined with the first and third carbons and a fourth bond with the second carbon (thus acquiring the four bonds or eight valence electrons in its outer shell). The second carbon atom is joined together with 3 methyl groups and a hydrogen atom. The methyl group consists of a carbon atom bonded with three hydrogen atoms. H H H on H-C-C-C- 8H fy] H H H-C-H | H (b) CH;CCCH3;: The first carbon has three hydrogen atoms and is bonded to the second carbon. The second carbon is only joined to the first carbon and the third carbon atom. In order to complete an octet around the second carbon it is absolutely necessary for the linkage with the third carbon atom to be triple bonded. The third carbon is attached to a methyl group. I I H-C-CziC- - H 2-butyne H H (c) CH»C1OCH»2CHO The first methyl group has a hydrogen replaced by a chlorine atom and is attached to an oxygen atom. The last carbon is attached toa methylene group and an oxygen atom. Since the oxygen is not linked to any other atom and 10in order to be neutral it must be doubly bonded to the last carbon. ‘H H O | | Hf Cl -C-0O-C- m H H H (a) (CH2), Each carbon atom is attached to two other carbon atoms {in a ving) and two hydrogen atoms: H H (e) CH3;CONHCH;. A methyl group is attached to the middle carbon. The latter has an oxygen atom but since it needs to bond twice more it should be bonded doubly to either nitrogen or oxygen. But since nitrogen (needing 3 bonds) is linked to hydrogen and a methyl group it can only form a single bond with the middle carbon. (£) CH2-CH20CH2CH20 In this compound the two oxygens | are bonded with two -CH2- groups each and the carbon atoms are linked to an oxygen, another -CHg- and two hydrogen atoms. H 0 H NAN Cc Cc / \ zm H,0? > nH,® > HO Acid strength Since HCl is the stronger acid, the HCl in benzene is the more acidic solution. @ PROBLEM 1-12 Account for the fact that nearly every organic compound containing oxygen dissolves in cold concentrated sulfuric acid to yield a solution from which the compound can be recovered by dilution with water. Solution: The solution to this problem can be obtained by a consideration of the Lowry-Brg@gnsted definition of acids and bases. In the Lowry-Br¢gnsted sense, an acid is a substance that gives up a proton, and a base is a substance that accepts a proton. When the cold concentrated sulfuric acid is added to the organic compound containing oxygen, it gives up a proton (hydrogen nucleus) and protonates the oxygen atom, which possesses electron pairs available for sharing. The reaction may be illustrated as shown: | | -O: + H,SO, % -O:H® + HS0.,O The oxygen atom of the organic compound is acting as the base because it accepts the proton from the sulfuric acid. It is thus protonation, which is reversible, that accounts for the organic compound dissolving in the cold concentrated sulfuric acid. The protonation generates (as shown previously) the following: -O: HO and HSO,O A B "A" is the new acid formed because it can donate the proton; "A" is a weak acid (it will tend not to give up the proton readily). "B" is the new base generated, and it is also weak (it will tend not to accept a proton donated). If water is added to this solution, the organic compound 15will be regenerated, because water is a stronger base than HSOW’ so that it will accept the proton from "A", The re- action can be written as: -0:#® + H2O0 -O: + H30® hydronium ion obtained ee organic compound recovered IDENTIFICATION AND STRUCTURE DETERMINATION @ PROBLEM 1-13 A qualitative analysis of Atebrin, an antimalarial drug used extensively by Allied troops during the Second World War, showed carbon, hydrogen, nitrogen, chlorine and oxygen. A quantitative analysis showed 69.1% carbon, 7.5% hydrogen, 10.5% nitrogen, 8.9% chlorine and 4.0% oxygen. What is the empirical formula for Atebrin? Solution: When the percent composition of a compound is given the percents refer to weight percent unless it is stated otherwise. To calculate the empirical formula for a compound from its composition first assume that 100 g of the compound is present and then determine the mass of each component. From these masses the number of moles of each element can be found and from this the empirical formula. In 100 g of Atebrin there will be 69.1 9 C, 7.5 9 H, 10.5 g N, 8.9 g Cl and 4.0 g O. The molecular weights (MW) of these elements are 12, 1, 14, 35.5 and 16 respectively. Solving for the number of moles of each in 100 g of Atebrin: no. of grams MW _ 69.1 _ no. of moles of C = 12 g/mole ~ 5.76 moles = 2-59 _ no. of moles of H I g/mole 7.5 moles no. of moles = 10.5 14 g/mole = 0.75 moles no. of moles of N = 8.9 g no. of moles of Cl = 35.3 g/mole = 0.25 moles _ 4.0 _ no. of moles of O = 6-0 Gomes = 0.25 moles The number of moles of each element in the empirical formula must be integers. The formula that has been derived above is Cs 76 H7,5 No 75 Clo,2s00,25s- There are 0.25 moles of each Cl and O, thus multiplying the number of moles of 16each element by 4 will yield C23H3,9C10, which is the enm- pirical formula. @® PROBLEM 1-14 A gas of molecular weight 58 was found to contain 82.8% C and 17.2% H. What is the molecular formula of this com- pound? Solution: The molecular formula for this compound can be written CH e where x is the number of moles of carbon present in one mole of the compound and y is the number of moles of hydrogen present in each mole of the hydrocarbon. The number of moles of each compound can be determined by multiplying the molecular weight (MW) of the compound by the fraction of the element present divided by its own MW. fraction of C or H ——MW of C or H x 58 g (i) no. of moles MW of C = 12: MW of H=l Substituting into equation (i): 828 no. of moles of C = I? g/mole x 58 g = 4.0 moles no. of moles of H = —~+/4 x 58 g = 10.0 moles . 1 g/mole . The formula for this compound is C,Hio. @ PROBLEM 1-15 A sample of aspirin (acetylsalicylic acid) was determined to be 60.0% carbon, 4.4% hydrogen and 35.6% oxygen. The molecular weight is 180. What is the molecular formula for aspirin? Solution: The molecular formula for a given compound can be calculated from its molecular weight and the percent composition. One mole of aspirin weighs 180 g; 60.0% of this weight is contributed by carbon. After determining the mass of the carbon present, the number of moles of carbon in’one mole of aspirin can be found. (MW of C = 12) mass of carbon in one mole of aspirin = .60 x 180 g= 108 g _ mass) _ 108 = no. of moles = a :~O g/mole ~ 9 moles 17Similar calculations can be made for hydrogen and oxygen to determine the molecular formula. (MW of H = 1) mass of H in 1 mole of aspirin = 0.044 x 180 g=8g _ 8 _ no. of moles = I g/mole ~ 8 moles (MW of O = 16) mass of O in 1 mole of aspirin = .356 x 180 g = 64g _ 64 _ no. of moles = 16 g/mole ~ 4 moles The molecular formula for aspirin is Cs>H,0,. Its structure is shown below. I C -OH Acetylsalicylic Acid (Aspirin) O-C-CH3 @ PROBLEM 1-16 What do the differences in properties between lithium acetylacetone (m.p. very high, insoluble in chloroform) and beryllium acetylacetone (m.p. 108°, b.p. 270°, soluble in chloroform) suggest about their structures? Solution: From their melting and solubility properties, the structures of lithium acetylacetonate and beryllium acetylacetonate are, respectively, ionic or salt-like and non-ionic or covalent. Melting may be considered to be a change from a high- ly ordered arrangement of particles to a more random arrangement. When a temperature is reached at which the thermal energy of the particles is great enough to over- come the forces holding the particles together, melting occurs. An ionic compound or salt forms crystals in which the structural units are ions. These ions are held together by the electrostatic forces that derive from an ion of say positive charge being surrounded by ions of opposite charge (negative charge) in the structure. These powerful forces, which are interionic, can be over- come only at a very high temperature. In a non-ionic compound, the atoms are held together by covalent bonds and form crystals in which the structural units are molecules. For melting to occur, the forces holding these molecules together must be overcome. These intermolecular forces are weak compared to the electrostatic forces, so 18that a much tower temperature is required for melting. Since the melting point of lithium acetylacetonate is very high, and beryllium acetylacetonate relatively low,one expects the former to be ionic with the latter being non- ionic. These same expectations could have been obtained by examination of the solubilities. For something to dis- solve, the structural units-ions or molecules - must become separated from each other, and the spaces in between become occupied by solvent molecules. To dissolve an ionic com- pound, the solvent must be able to form ion-dipole bonds and have a high dielectric constant, that is, possess high insulating properties to lower the attraction between oppositely charged ions once they are solvated (surrounded by a cluster of solvent molecules). Only water or other highly polar solvents possess these properties, and hence can dissolve ionic compounds to a large extent. (A polar molecule has a positive end and a negative end, so that there is an electrostatic interaction between a positive ion and a negative end of a solvent molecule, and between a negative ion and a positive end of a solvent molecule - ion-dipole bonds.) Solubility of non-ionic compounds is determined by their polarity. Non-polar or weakly polar compounds dissolve readily in non-polar or weakly polar solvents, whereas highly polar compounds dissolve in high- ly polar solvents. These facts are often remembered by the "like dissolves like" rule. Chloroform is a non- polar solvent, so that it should dissolve only non-polar compounds. Since beryllium acetylacetonate dissolves in it, one expects its structure to be non-ionic. Likewise, since lithium acetylacetonate is not soluble in it, it is probably ionic or salt -like. POLARITY @ PROBLEM 1-17 What are the characteristics which ionic, ion-dipole, and dipole-dipole bonds have in common? How do they differ? Solution: A bond between two species is defined in terms of the amount of energy liberated because of adduct forma- tion. The strength of the bond increases as the amount of heat generated is increased at the expense of the total energy of the system. An ionic bond is produced when an electropositive and an electronegative element react by transferring electrons. For example, when Na°* and :Cl: react the electropositive sodium transfers one electron to chlorine; Nat and :Cl:” are produced. This ionic bond is non-directional. An ion-dipole bond is generated when one of the ions in an ionic bond is replaced by a highly polar molecule 19ge > such as water: Oo 68” H/ When an ion such as Nat reacts with H20, the positive ion aligns with respect to the polar molecule as shown: Nat + ———> Nat Similarly, if another polar molecule replaces the ion in the ion-dipole bond, the formation of a dipole- dipole bond occurs. If we consider two polar molecules (e.g., two H20 molecules) the alignment of the molecules 6+ H \ 57 6+ is such: JO 77 TEN ; The other 0 6- 6 Hm s+ hydrogen atoms also attract oxygen atoms in other water molecules. Ionic bonds form stronger bonds than ion-dipole bonds, and the latter are stronger than dipole-dipole bonds. ® PROBLEM 1-18 Why does hydrogen fluoride undergo intermolecular self- association while the other hydrogen halides do not? Solution: The fluorine atom is the most electronegative, that is, strongest attractor of electrons, of all the halogen atoms, Since fluorine will tend to attract electrons, the fluorine atom should possess a negative charge and the hydrogen atom a positive charge in HF, That is, HF is a polar molecule with one end (F) electron rich and one end (H) electron deficient. In a solution of HF, the opposite charges can attract each other, that is, one has inter- molecular self-association. When opposite and equal charges are separated by some distance in a molecule (such as HF), a dipole is formed. Hence, the intermolecular self-associa- tion can be considered dipole-dipole interaction, This particular kind of interaction is also referred to as hydrogen bonding, It may be pictured as shown: H-F «++ H-F tayarogen bonding. The tremendous electronegativity of fluorine is what allows the formation of hydrogen bonds in an HF solution. Since the other halogens possess less of a tendency to attract electrons, they will be less able to form hydrogen bonds required for intermolecular self-association. 20@ PROBLEM 1-19 (a) Although HCl (1.27 A) is a longer molecule than HF (0.92 A), it has a smaller dipole moment (1.03 D compared to 1.75 D). How do you account for this fact? (b) The dipole moment of CH3F is 1.847 D, and of CD3F, 1.858 D. (D is 7H, deuterium.) Compared with the C-H bond, what is the direction of the C-D dipole? Solution: (a) Both HCl and HF are polar compounds. This means one end of the bond between the two atoms in the molecule is relatively negative and the other end is rela- tively positive. In other words, there exists a negative pole and a positive pole. A covalent bond will be polar if it joins atoms that differ in their tendency to attract electrons, that is, atoms that differ in electronegativity. The greater the difference in electronegativity, the more polar the bond. The following relates the electronegativity of some common elements: F>O>Cl1,N>Br>C>H. The molecules HF and HCl constitute dipoles because of this difference in electronegativity. A dipole may be defined as a molecule with two equal and opposite charges separated in space. A dipole possesses a dipole moment, uw, which equals the magnitude of the charge, e, multiplied by the distance, d, between the centers of charge: uU=erxwd,. Since HCl is longer than HF, the "d" will be larger for HCl in the computation of its dipole moment. Thus, to ex- plain why HCL's dipole moment is smaller than HF, one must examine the other parameter, "e". The magnitude of the charge will reflect the extent of the difference in electro- negativities of the elements. As previously indicated, the electronegativity of F is greater than Cl by a significant amount. Thus, when both F and Cl are compared with H's electronegativity, the difference is greatest for F. Hence, the magnitude of "e" must be much larger for HF than HCl. Consequently, the dipole moment is larger in HF. In essence, then, the greater electronegativity of F is re- sponsible for the larger dipole moment. (b) The fact that the dipole of CH3;F is less than CD3F means that D must be attracting the electrons less than H does. If one assumes there exists no difference in "d",orthe distance between the charges,when D is substituted for H, then the difference in dipole moment can only stem from magnitude of charge, "e". If the electronegativity of D is less than H, that is, it tends to attract less electrons, then F is more negative so that the magnitude of "e" is increased, which would account for higher dipole moment of CD3F. What this means is that the dipole is less directed toward D than toward H. 21@® PROBLEM 1-20 Predict the direction of polarization of the following bonds, considering only the relative electronegativity of the atoms involved. C-H; B-H; N-Br; I-Cl Solution: The electronegativity of an element is a measure of the ability of an atom of the element to attract electrons to itself in a chemical bond. It is generally found that electronegativity increases from left to right across the periodic table and decreases on on going down any group. The most electronegative elements are therefore found in the top right-hand corner (0, F, Cl) and the least electronegative (most electropositive) in the bottom left-hand corner (Ba, Cs, Rb). A qualitative list of relative electronegativity is given below, but it should be realized that the molecular environment of an atom may affect its electronegativity to a limited extent. The relative electronegativities of some common elements occur in the following order: F>0>Cl1,N>Br>1,S,C>P,H>B>Mg>Li>Na The distribution of electrons in a single covalent bond between two atoms is not equally shared. In a symmetrical molecule A-A (e.g. Hz, Clz) the two nuclei, in whose neighborhood the bonding electrons are found, are indistinguishable, and in the absence of any external effects the electron distribution will be symmetrical. If, however, a molecule such as A-X is considered where A and X are different (e.g. HF, ICl), then the nuclei are distinct and the atoms A and X may differ greatly in electronega- tivity. In these circumstances the distribution of electrons may be asymmetric and the electron density will be greater near the more electronegative element. This electron dis- placement carried to an extreme leads to the production of ions, but in many covalent bonds only causes slight polari- zation of the bond, represented as AX or aot— x6- where X is the more electronegative atom, and 6+, 67 represent small electrical charges produced by polarization. Thus, referring to the relative electronegativities of the individual atoms, and the above definition of polari- zation: é- 6+ 6+ 6- S- d+ 6+ 6- c-H B- H N - Br I- Cl <——_+ _—> <——+ —> 22CHAPTER 2 SPECTROSCOPY LINE SPECTRA ® PROBLEM 2-1 Calculate the energy in kcal which corresponds to the °o absorption of 1 einstein of light of 5893 A (sodium D line) by sodium vapor. Explain how this absorption of light by sodium vapor might have chemical utility. Solution: One einstein of light refers to the change in energy (AE) that occurs from the absorption of electro- magnetic radiation by one gram-atom (or mole) of a monatomic gas such as sodium vapor. The absorption of radiation results in the excitation of the molecule. The energy difference between the excited state and the ground state of the molecule is the change in energy. This change in energy is related to the frequency (v) or wavelength (A) by the equations: he AE = hv = x where h Planck's constant c = velocity of light. Since Planck's constant and the velocity of light are numerical constants, this equation can be written as: Ag = 286,000 joa (A) o where (A) indicates that the wavelength is measured in ° angstrom units (A). Hence we can calculate the energy, in Keal (kilocalories) ,which corresponds to the absorption of one einstein of light at 5893 A by sodium vapor as follows: _ 286,000 AE = Spo kcal AE = 48.5 kcal. 23The energy requirements of many chemical reactions are within the range of 48.5 kcal/mole. Hence when the excited electron in sodium drops to its ground state, the energy transferred (48.5 kcal/mole) can cause a chemical reaction to occur. INFRARED SPECTROSCOPY ® PROBLEM 2-2 Identify the functional groups in each compound from the following infrared spectra. FREQUENCY (CM"') 1800 1800 Le d ea aE aa Mea ERR tay Petes SH a Pe EHH SEA Tr Re RST Cera +4 aT CEL ETe thi 7 HEH Ht th Ht eet tL th GT a Poe z Ht ae Mo ea! aol Tit Fert UP ty Pry) < att FARCE a Poth Ca ah A Spr ee Sec ciae fe has et papers Spee ey He PCP at HHH poet CEST RE CHEE HEHE ar cd <0 3000 3200 ze00 2400 aha Ne 1400 1200 7 Tinto ot ibe te tL LT Ua peed ses tet . HEPETEEEEE EE rE Rete ig PE aw HTH TT HEH Hof ELH Ht faa La fe| in POE TT {il He Hanaano HEHE HR EE Ea te aE Tih tefl HE ROT] i Cy il rf Se CEREAL - iia Pet REE athe ee tit SEE HS eee et eto Capo Aart os Hu IR Hi Habe A | FREQUENCY (CM"') 400 2600 3300 2800 2400 2000 1800 1800 1400 1200 1060 sco 600 40 MH aoe pan (c) pa He eh er Hane ter pceeepetrt TEES ro SS eg d Patino td PA I ett ry HH Ht Hay ee PRA Ratt aoe i hs RH ht rate att rH hin TAANSMITTANCE %& pooan F PPE TELE ESR 24FREQUENCY (CM"') 1800 1600 1400 1200 1000 600 600 400 Thott Mote eT | feta Hieber errr CNA Nagy Lent tit ch tah TR Cott He § § § g- CoN tid ees PCA ictal lik TT Pai EEE a SpE Abed ie Pb bed i 34 1s S {MICRONS} & 8 8 10 41 12:13:14 16 18200 «26 Solution: Infrared (i.r.) spectroscopy is a common technique that is used to identify the major functional groups in a compound. The identification of these groups depends upon the amount of infrared radiation absorbed and the particular frequency (measured in cm7!, wave- numbers) at which these groups absorb. An infrared spectrum measures the degree of the molecular vibration and rotation of the bonds in the molecule. Each type of functionality will absorb at certain characteristic frequencies and with characteristic strengths. With this knowledge at hand, we can identify the major functional groups from the i.r. spectra (a) through (d). (a) This spectrum has a moderate band at 3050 cm~? which is characteristic of the =C-H stretch of a dialkylated alkene: RHC = CHR'. There is also a strong sharp band at approximately 965 cm” !, which is the characteristic absorp- tion of the C-H out-of-plane bending of a trans-1,2- dialkylated alkene: R H \ / c=Cc . / \ H R' (b) The strong sharp band at 3300 cm”! is characteristic = C > H stretch and is suggestive of a terminal alkyne: R-C = C—H. The medium sharp band at 2170 cm! is the characteristic absorption band of the C = C stretch of terminal alkynes. The strong broad band at 630 cm! is the absorption of the = C - H bend of R- C = C - H. We can see from this i.r. spectrum that the compound is con- clusively a terminal alkyne. (c) The broad band centered ay 3350 cm7! is indicative of a bonded O-—H stretch. The complex absorption pattern at 1050 cm ' is the C——O vibrations of a primary alcohol, RCH»OH. (d) The strong sharp bands at 995 cm”! and 905 cm! are characteristic of the C - H out-of-plane bend of mono- alkylated alkenes: RHC = CH,. This is strongly supported by the other spectral evidence. The moderate sharp band at 3080 cm™' is the absorption of the = C - H stretch and the medium sharp band at 1640 cm~! is the C = C stretch absorption, 25@ PROBLEM 2-3 Give a structure or structures consistent with each of the following infrared spectra. Wavelength, » oukq oso Frequency, cm | Wavelength, ya 25 3 4 5 6 t 8 9 fo 12 1s Turd iosqy Frequency, em”! Wavelength, p Frequency, cm Solution: Infrared (i.r.) spectra can reveal the molecular structure of an organic compound. It is based on the fact that a molecule is constantly vibrating. Chemical bonds stretch (and contract) and bend with respect to each other. The absorption of infrared light (that is, light lying beyond the red end of the visible spectrum - lower frequency, longer wavelength, less energy) causes changes in vibrations of a molecule. An infrared spectrum may be referred to by its wavelength or, preferably, by its frequency which is expressed in wavenumbers, cm™*, as can be seen in the 26spectra given in the problem. (Wavenumbers may be defined as the number of waves per centimeter.) Two substances that possess identical infrared spectra are identical in thousands of different physical properties; they must almost certainly be the same compound. The infrared spectrum reveals the molecular structure by indicating what groups are present (or absent) in the molecule. This is based on the fact that a group of atoms gives rise to characteristic absorption bands. In other words, a particular group absorbs light of certain frequencies that are essentially the same from compound to compound. For example, the carbonyl group (C=O) of ketones absorbs at 1710 cm7~!. Now, the absorption band of a particular group of atoms can be shifted by various structural features such as angle strain, van der Waals strain, conjugation, electron withdrawal, and hydrogen bonding. Hence, the interpretation of an infrared spectrum may not be easy. The table provided lists some characteristic infrared absorption frequencies. In solving for the molecular structure, try to correlate the frequencies in the table withthose for bands indicated in the problem. (a) A band is present in the 3000-3100 cm7! region; this indicates an aromatic ring. This can be confirmed by the presence of a band in the 1500, 1600 regionswhich would indicate the stretch of the C=C bond in the ring. Such a band is present. Therefore, one knows that six of the nine carbons in C sH;2 belong to an aromatic portion: a benzene ring. The weak finger-like bands from 2000 cm7? to 1700 cm~‘are characteristic of the absorption of mono- substituted aromatic rings. Hence the remaining three carbons must be part of a single substituent. The aromatic bands account also for five hydrogen atoms, so that the substituent possesses seven hydrogen atoms. There exist two possibilities for an organic structure with three carbons and seven hydrogens: isopropyl (-CH(CH3).2) and propyl (-CH2CH2CH;). That it is isopropyl can be deter- mined from the isopropyl split at about 1400 cm™?. So, CH (CH3) 2 the structure in (a) can bewrittenas The diagram below assigns groups of atoms to each bond for further clarity. Wavelength, & 2.5 3 4 3 6 7 3 9 10 12 is mono substd, benzene aaDUBQsosqgy / ~ CH c-H A | SCH sor'd sretch out-of-plane bend aromatic monosubstd. benzene < 3500 3000 2500 2000 1800 1606 (400 1200 (000 800 600 Frequency, cm~! $ 27(bo) That this is an alkene can be seen from the strong band present in the 1640-1680 cm”! region, due to the c=C stretch. Also, the molecular formula given, CuHe, fits the general formula for an alkene, CiHon: There exists a band in the region of 3020-3080 cm™! which indicates the C-H absorption for alkenes. The diagram below assigns structures to the bands which lead to the conclusion that the structure is (CH;)2C=CH2, isobutylene. Wavelength, u C—H olefinic aoueqiosgy out-of-plane dend (b) 4000 3500 3000 2500 2000 1800 1600 1400 1300 1000 BOO 600 Frequency, cm ~! (c) That the structure is phenylacetylene may be deter- mined by examining two prominent bands. There exist the C-H stretch of aromatics(confirmed by the C====C stretch at 1500, 1600 cm~')at 3000-3100 cm™? and the -C=C- stretch characteristic of alkynes at 2100-2260 cm7!. One concludes therefore, that C,H, represents (O)czcn, phenylacetylene. Other bands are assigned structures in the diagram. Wavelength, 1 2.5 3 4 $ 6 7 8 9 10 12 13 C—H aromatic uwC—H in-plane bend aouequosgy out-of-plane bend 3500 3000 2300 2000 1800 1600 1400 $200 1000 800 600 Frequency, cm~! @ PROBLEM 2-4 Which (if any) of the following compounds could give rise to each of the infrared spectra shown? isobutyraldehyde ethyl vinyl ether 2-butanone cyclopropylcarbinol tetrahydrofuran 3-buten- 2-01MDpSMUsUTs) WIDI” HOBSNUSUCH ddI 0 4000-3600) s-3200-- 2800 «400s 2000 1800 1600 {400 1200 {000 $00 500 (RDC 3877 Frequency, cm”! Wavelength, u ? c) 3 a a = 3 0 “03 n » 3 ooo 3600 «(32002800 20 200 1900 1600 1400 1200 1000 goo 600 ° sRDC 7233 Frequency, cm"! Solution: (a) This infrared spectrum shows a strong absorption near 1720 cm”’. This is the characteristic absorption of a C=O stretch for saturated aldehydes and saturated acyclic ketones. The weak absorption at 3400 cm’ is the C=O overtone and it further supports our conclusion that we are dealing with a carbonyl compound. The C=O overtone is noticeable in the spectrum because the C=O stretch is such an intense absorption. The only given carbonyl compounds are isobutyraldehyde (an aldehyde, O RCHO) and 2-butanone (a ketone, RCR'). The C-H stretch of the aldehyde proton characteristically shows absorptions at 2820 cm”! and 2720 cm”™?. The i.r. spectrum shows only a strong band at 2900 cm7! in this vicinity. Hence the compound is not the aldehyde and must be the ketone, 2- butanone. The band at 2900 cm”! is the characteristic absorption band of the C-H stretch of methyl and methylene groups. 2-Butanone has the structure: O CH 3-C-CH2~CH 3 {b) This i.r. spectrum shows a strong absorption at 291737 cm7!. This is suggestive of the C=O stretch of a saturated aldehyde because the frequency at which aldehydes absorb infrared radiation is greater than that of ketones. The sharp bands at 2820 cm™! and 2740 cm! are the absorp- tions of the C-H stretch of an aldehyde. Hence the compound is an aldehyde and must be isobutyraldehyde. CH 3 0 CH-C-H / / CH3 (c) This spectrum shows a strong broad band at 3400 cm}, which is indicative of a bonded O-H stretch of an alcohol. Our choice is therefore narrowed down to cyclopropylcarbinol ([>-cx, on, a primary alcohol) and 3-buten-2-o0l (CH2= CH-CHOHCH3, a secondary alcohol). The C-O stretch of primary alcohols characteristically absorbs at 1050 cm’ and that of secondary alcohols absorbs at 1100 om~'. Since the spectrum shows a complex absorption pattern in this range, we must look for other clues. There is a weak absorption at 1640 cm~'. This is the characteristic absorption of the C=C stretch of terminal alkenes (RHC=CH2 or R2C=CH,). Hence the compound must be 3-buten-2-o0l because it possesses a Gouble bond whereas cyclopropylcarbinol has none. @ PROBLEM 2-5 The infrared spectra shown in Figures 1 a and Db are for compounds of formula C3HsO0 and C.xHs02, respectively. Deduce a structure for each of these substances from its infrared spectrum. Indicate clearly which lines in the spectra you identify with the groups in your structures. % transmission 3600 3200 2800 2400 2000 2000 +800 1600 1400 -1 frequency, cm 30s ° ec n n oc i iss) 4M 43 we 3660 3200 2800 2400 2000 1800 1600 frequency, cm_ Solution: (a) The most noticeable feature in this infra- red spectrum is the strong broad band at 3400 cm”’?. This absorption is characteristic of the bonded O-H stretch of alcohols. We can furthermore deduce that the compound is a primary alcohol by noticing the strong sharp C-O stretch absorption at 1050 cm7'. The C-O stretch of secondary and tertiary alcohols absorbs at frequencies greater than 1050 cm’. Another significant band in this spectrum is the weak sharp absorption at 1650 cm’. This is the charac- teristic absorption band of the C=C stretch of monoalkylated alkenes (RHC=CH2) and dialkylated terminal alkenes (ReC =CH2). These types of alkenes are distinguished by their methylene C-H out-of-plane bending. The spectrum shows two strong sharp bands at 1010 cm™! and 930 cm~!, the characteristic absorption bands of the C-H out-of-plane bend of monoalkylated alkenes. As if this were not enough proof, the molecular formula of the compound (C3H;,0) re- stricts it to three carbons; the smallest dialkylated terminal alkene requires four carbons: CH; \ C=CH2 . A monoalkylated alkene of three carbons is / CH; CH;CH=CH2. Hence the compound is a monoalkylated alkene and is also a primary alcohol. Since there is only one carbon attached to the -CH=CH2 portion, it must contain the -OH functionality (the sp*-hybridized carbons cannot bear the -OH, for it would not account for the spectrum shown). Hence, the compound is an allyl alcohol and has the structure CH2=CHCH20OH. The principle absorptions of the infrared spectrum are labeled below: 31wavelength, a 3 4 s 5 6 7 a 9 4a 12 \4 % transmission | cae ) c-H stretch C-H out-of-plane. (a) | bonded O-H Catch bend a onde. * te. ae we) We 3600 1200 2400 2400 2000 1900 1800 1600 t400 '200 1900 sco frequency, om} Infrared Spectrum of Allyl Alcohol (b) The major feature of this spectrum is the strong sharp absorption at 1700 cm-!. This is the typical absorption of || the C=O stretch of a carboxylic acid (R-COH). The strong band at 1240 cm-? is the C-O stretch. Further spectral evidence of a carboxylic acid is the strong O-H bend near 1455 cm7™? and 950 cm7!, and the very broad O-H stretch centered at 2800 cm7~!. If we subtract the molecular 0 | formula (M.F.) of the known portion (-COH) from the M.F. of the compound (C,H,02), we will have the M.F. of the unidentified portion of the compound. We find that a C3Hs portion remains to be identified. By manipulating the atoms in various arrangements we see that there are only four possibilities for the structure of a C3Hs group. They are: (1) H»C=CH-CH2- (2) CH 3-CH=CH- CH3 (3) Cc- iA H2C Hee (4) CH- / H2C Structures (1), (2) and (3) each has’ one 7 bond; structure (4) does not due to its cyclic nature. The spectral data show that structure (4) is the C3;H; portion 32of the compound. The methylene C- vi stretch of the cyclo- propyl group absorbs at 3075 cm™*. The methine C-H stretch absorbs at 3000 cm™!. These arnorptiees are difficult to notice because they overlap with the broad band of the O-H stretch. Structures (1), (2) and (3) can be ruled out as the C3Hs group because the i.r. spectrum shows none of the characteristic bands for alkenes. For example, there are no strong sharp bands at 700 cm~', 890 cm-!, 910 cm7! or 990 cm-', which is characteristic of the C-H out-of- plane bending of alkenes. There is, however, a strong broad band at 950 cm™! which is the O-H bend. Hence the compound is cyclopropylcarboxylic acid and has the structure may oO CH-C-OH . The principle absorption bands of the H2C infrared spectrum are labeled below: wavelength, u methine stretch ; % transmission 36090 3200 Sa Teno 24060 2000 1800 1400 1400 frequency, cm Infrared Spectrum of Cyclopropylcérboxylic Acid RAMAN SPECTROSCOPY @ PROBLEM 2-6 Classify the following molecules according to the general characteristics expected for their infrared and Raman spectra: (a) Cleo; (b) HCl; (c) CO; (d) CFs=CH, (double bond stretch only). | Solution: Raman spectroscopy is often used in conjunction with infrared spectroscopy in the identification of organic functionalities. Raman spectra arise from the absorption of monochromatic light by a sample before it is emitted as 33scattered light. As in infrared spectra, Raman spectra are recorded in wavenumbers. Frequently a Raman spectrum will reveal something that was missed in the infrared spectrum. This is because a bond which has no dipole moment (i.e.,is electrically symmetrical) will appear in the Raman spectrum but will not appear in the infrared spectrum. With this information we can predict the general characteristics expected for the infrared and Raman spectra of compounds (a) through (d). (a) The Cl-Cl bond of the chlorine molecule has no dipole moment because, like all other diatomic molecules (Ho, Oo, Bro), the two identical atoms exert equal and opposite electronegative effects upon each other. Hence the infrared spectrum of Cl, will show no absorptions and the Raman spectrum will show a strong Cl1-Cl absorption. (b) The H-Cl bond of hydrogen chloride is fairly polar due to the considerable difference in electronegativity of hydrogen and chlorine, whose electronegativities are 2.1 and 3.0, respectively. As a result, both the infrared and Raman spectrum of HCl will show a strong H-Cl stretch. The dipole moment of HCl is directed toward the chlorine (because of its greater electronegativity) as shown: H —+——+ cl (c) Carbon monoxide is a polar molecule and its structure can be shown by two main resonance structures: TC=2O$ ++ C=0. Note: Resonance structures do not exist independently; they only approximate what the molecule really looks like. That is, the molecule is actually a hybrid of the resonance structures. The principal characteristic of the infrared and Raman spectra will be the strong C=O stretch. (d) The C=C double bond of 1,1-difluoroethylene is polar because of the powerful electron withdrawing effects of the two fluorine atoms: F 4H None J *% F 4H The net result is: Foc +——}+- CH2 The C=C bond will appear as a strong band in both the infrared and Raman spectra. 34ULTRAVIOLET SPECTROSCOPY @ PROBLEM 2-7 The ultraviolet spectrum of 3,6,6-trimethylcyclohex-2- en-l-one, is shown below. The concentration is 1.486 x 10-° g ml~? in ethanol and the path length is 1.0 cm. Calculate ¢€ and compare »max with the value predicted by Woodward's rules. FEE a PECEREP EPA TPE eiieerssesiseetterae pe 7 ABSORBANCE 300 WAVELENGTH INANOMETERS) Empirical Parameters for 7 — 1° Transitions of Conjugated Systems in Ethanol (Woodward's Rules) Parent System Xa ON Substituent Corrections Polyenes No double bond* alkyl group exocyclic C=C double bond (> OR groups Cl, Br a, B-Unsaturated ketones R double bond* alkyl group A, exocyclic C=C double bond “ The double bend must be attached at the end of the < system to produce a linear conjugated system. Solution: Ultraviolet spectroscopy involves the excitation of an electron in its ground state level toa higher energy level. This is accomplished by irradiating a sample with ultraviolet light (electromagnetic radiation with wavelengths in the range of 200 nanometers (nm) to 400 nm). The wavelength of maximum absorption Onax? can be calculated by using Woodward's Rules. Amax has a specific degree of absorbance associated with it. The absorbance at a particular wavelength is 35dependent upon the intensity or molar absorptivity, ¢€, of the incident light. The molar absorptivity is related to the absorbance by the equation 6 = 19g {To/T) where Ip = initial light intensity I = final light intensity c = concentration of sample in moles per liter 2 = path length of sample tube in centimeters Beer's Law relates the absorbance A to I, and I by the equation: A = log (I,/1) Hence the equation for molar absorptivity can be written as: o I Q | 22 where A = absorbance at Anax . To calculate Aan x by Woodward's Rules, we must look a at the parent system of 3,6,6-trimethylcyclohex-2-en-l-one: O CH I CHs CH The parent compound is an o,f-unsaturated ketone, therefore Anax is at least 215 nm. There are two alkyl substituents on the parent system of our compound: CH CH. \CHs nis sp*-hybridized carbon has two alkyl groups attached For each alkyl group substituted on the o,8-unsaturated ketone, a correction of + 10 nm must be made according to Woodward's Rules. Therefore, the calculated Amax [acaie| for 3,6,6-trimethylcyclohex-2-en-l-one is 36R 0 215 nm for the parent system | = | pias 2 (10 nm) or 20 nm for the two alkyl groups substituted on the g-carbon of the o,f-unsaturated ketone. calc _ 915 nm + 20 nm max calc = 235 nm max By looking at the ultraviolet spectrum of our compound, calc we see that \nax is very close to the experimental din ax expl expl . calc, . [age |. The Anax is 233 nm whereas the A max is 235 nm; this discrepancy of 2 nm falls within the experimental margin of error and confirms the validity (and accuracy) of Woodward' Rules. The molar absorptivity (ce) may be calculated by using the aforementioned equation AL cer expl max tl where A absorbance at A c concentration of sample in moles per liter g path length of sample tube in centimeters. By looking at the ultraviolet spectrum, we see that the absorbance at yexPt (233 nm) is 1.0. There are no units for absorbance and the molar absorptivity is ex- pressed in liters per mole per centimeter (liters mole7? cm !). The path length of the sample tube is given as 1.0 centimeter. The concentration of the sample in ethanol is given in grams (g) per milliliter (ml). This must be converted to moles per liter. Since 1 liter = 1000 ml, multiplying the given concentration by 1000 will give us the concentration in grams per liter: 1.486 x 1075 (g/ml) x 10° (ml/liter) = 1.486 x 107% (g/liter) We must now convert grams to moles to give us the proper unit. Since moles = a (MW is the molecular weight of the sample), and the MW of 3,6,6-trimethylcyclohex-2- en-l-one is 138, we can calculate the concentration in moles per liter as shown: 37- ; 1 1.486 x 10 “ (g/liter) < 7393 —(g7moley = 1.08 x 107* (moles/liter) The molar absorptivity may now be calculated as follows: _ 1.0 € “1.08 x 10-* (moles/liter) x 1.0 (em) 9260 liters mole”! em ? ” tl @ PROBLEM 2-8 Calculate the percentage of the incident light which would be absorbed by an 0.010-M solution of acetone in cyclohexane contained in a quartz cell 0.1 cm long at 2800 A and 1900 A. Some Electronic Transitions of Simple Organic Molecules Compound Type Ama A a Solvent” (CH,),C=O n—>a* 2800 IS cyclohexane 7 Fe 1900 1,100 n—o*° 1560 strong CH,=CH, m—> 7* 1620 10,000 vapor CH,=CH—CH=CH, n> rt 2170 20,900 hexane CH,—CH=CH—CH=CH—CH, wa 7* 2270 22,500 hexane €H,—CH—CH,—CH,—_CH=CH, Tw 7 1850 20,000 alcohol CH.—C=CH 7 7* 1865 450 cyclohexane CH,=CH—C=O n—>a* 3240 24 alcohol | n>" 2190 3,600 CH, CH, a—o*" 1219 strong vapor CH,—CH, a—oa* 1350 strong vapor CH,—Cl no or 1725 weak vapor CH,—Br n—oare 2040 200 vapor CH,—I n— ott 2575 365 pentane CH,—O—H a—o* 1835 150 vapor CH.—O—CH, a ot 1838 2,320 vapor (CH,),N a— oat 2273 900 vapor * The molar extinction coeflicient € is a measure of the absorption efficiency at the wavelength Amac- Since the amount of absorption will be proportional to the concentration (¢ moles/liter) and thickness of the sample (/cm), € is obtained fromm the equation _ 1 I i, = a 08.4 7. where ,// is the ratio of intensity of incident light /, to transmitted light /, The per cent trans- mission of a solution is (///,) X 100. Substances for which e is independent of concentration are said to obey Beer's law (or the Beer-Lambert law). "It is necessary to specify the solvent since Ama, and Ema, Vary somewhat with solvent. * These assignments are not certain. * Transitions o —> o* correspond to excitation ofan electron of a single bond (designated 9) to a higher antibonding state (designated o*). * Transitions n> a* correspond to excitation of an electron of an unshared (i.e., nonbonding) pair to an antibonding state (o*) of a o bond in the molecule. Solution: The percentage of light absorbed is related to the percentage of light transmitted by the equation 38$Az= 100 -%T where %$ A = % absorbance %$T = % transmittance The absorbance (A) is related to the initial intensity (Ip) and the final intensity (I) by Beer's Law: A= og { #4] We can therefore relate the transmittance (T) to I, and I as: [Hi T = ! ° The absorbance of the incident light of a sample solution may be calculated by using the equation for molar absorptivity (¢€): _ Io € = oF log F 1 -1 where ¢ = molar absorptivity in liters mole™* cm c = concentration of sample in moles per liter 2 = path length of sample tube in centimeters ° o At a wavelength of 2800 A (Angstrom; 10 A= 1 nm), a solution of acetone in cyclohexane solvent has a molar absorptivity of 15 liters mole~' cm™’. The path length is 0.1 cm and the molar concentration is 0.01. The absorbance can be calculated as follows: ch - il Zo 15 = (ror) (0-1) 109 (F] = To 0.015 = log I To = i 1.04 : I Since T = ho then: = i = _i = . T= To Toa 0.9615 I 39% T= 100 xT $ T= 100 x 0.9615 %T = 96.15 $ A= 100 -&%T $ A= 100 - 96.15 %$ A= 3.85 Hence at 2800 A there is 3.85% absorption of the incident light. At a wavelength of 1900 A the molar absorptivity is 1100 liters mole”! cm™'. The percentage absorbance may be calculated as: € = 1 log F| ce T 1100 = aT OT log [zs 1.10 = log [F2) =e = 12.6 tooo * 0.0794 $ T= 100 x T= 100 x 0.0794 T= 7.94 ae i i 100 - $ T= 100 - 7.94 op hy ll 92.06 o Hence at 1900 A there is 92.06% absorption of the incident light by a 0.01 M solution of acetone in cyclo- hexane. @ PROBLEM 2-9 Compounds A, B and C have the formula CsHs, and on hydro- genation all yield n-pentane. Their ultraviolet spectra show the following values of max? A, 176 nm; B, 211 nm; C, 215 nm. (1-Pentene has Anax 178 nm.) (a) What is a likely structure for A? For B and C? (b) What kind of in- formation might enable you to assign specific structures to B and C? LOSolution: (a) The molecular formula of compounds A, B and C is of the general form CH on-2° This formula indicates that the compounds are hydrocarbons with either one carbon- carbon triple bond (an alkyne), two carbon-carbon double bonds (a diene), two rings, or one ring and one carbon- carbon double bond; that is, the compounds have two units of unsaturation. Since hydrogenation of the compounds yield n-pentane, and hydrogenation of alkynes and dienes ddes not change the carbon skeleton, all the compounds must be straight-chained. Hence the compounds are normal five-carbon alkynes or dienes. Compound A has maximum absorption at a wavelength of 176 nm (A ax)’ Since this is very close to the A max of l-pentene, compound A must have a chromophore similar to that of l-pentene. A chromophore is a functional group that gives rise to an absorption with characteristic dmnax and ¢€ (molar absorptivity) values. Hence compound A's chromophore, like l-pentene, is an isolated double bond. The only struc- ture of a normal five-carbon compound with two units of unsaturation and isolated double bonds is 1,4-pentadiene: H2C=CH—CH2-HC=CH2 1,4-pentadiene (Compound A) Compounds B and C have A nax of 211 nm and 215 nm, respectively. These values are greater than that of com- pound A and are of lower energies (longer wavelength (A), lower frequency, lower energy). One thing that could account for this is if B and C were conjugated dienes. Conjugated dienes are compounds that have two double bonds separated by one single bond (R-CH=CH-CH=CH-R'). The extra stability of conjugated dienes as compared to the analogous non- conjugated dienes is due to electron delocalization in the former. This extra stability lessens the energy difference between the ground state and excited state. Hence the frequency necessary for the maximum absorption of the compound is less than expected and the wavelength QO ax) will be greater. Therefore compounds B and C must be geometric isomers of the conjugated compound, 1,3-pentadiene. These are the "E" and "Z" isomers: H CH3 H H \ 4 \ + C=C C=C J \ / \ CH2=CH H CHo= H CH 3 E isomer Z isomer (b) The E and 2 isomers of the diene can be distinguished by their heats of hydrogenation. The Z isomer is less stable 41than the E isomer because of steric considerations, due to the proximity of the vinyl and methyl groups. This means that the Z isomer will have a higher heat of hydrogenation than the E isomer. Z isomer Energy t AH —------- Z E isomer i a pentane —_—_—_— Reaction coordinate —-> JaH,| > [AH,,| where AH, = heat of hydrogenation for the Z isomer AH, = heat of hydrogenation for the E isomer. NMR SPECTROSCOPY @ PROBLEM 2-10 Deduce the structure corresponding to each of the following nmr spectra: (a) CeH3;Cl 3(b) CoH 3B 4 5.0 PPM (8) 40 4,0 43(e) CoHyBro Po | 5.0 PPM(5} 4.0 Solution: Certain atoms have a nuclear spin similar to the spin of an electron. The spinning of charged particles (the proton(s) in the nucleus bears a positive charge) generates a magnetic field. When an atom is placed in an external magnetic field, the magnetic field generated by the nucleus will be aligned with or against the external magnetic field. At some frequency of electromagnetic radiation, the nucleus will absorb energy and "flip" over so that it reverses its alignment with respect to the external magnetic field. This is known as the nuclear magnetic resonance (nmr) phenomenon. It is generally concerned with the nuclear magnetic resonance of hydrogen atoms and is therefore sometimes called proton magnetic resonance (pmr). It is also standard practice for the frequency of radiation to be kept constant while the strength of the external magnetic field is varied. At some value of the magnetic field strength, the energy required to flip the proton matches the energy of the radiation. Absorption will occur and a signal will be observed. The spectrum that results from all these absorptions is called an nmr spectrum. Absorptions that occur at relatively low field strengths are downfield relative to those that occur at higher field strengths. The field strength at which a proton will absorb energy is called the chemical shift (measured in parts per million, ppm or 6, relative to the absorbance of Si(CH3;),, tetramethylsilane). The chemical shift of a proton depends upon the proton's electronic environment. Electron withdrawing atoms (or groups) that are nearby a proton will decrease the electron density about that proton; this is known as a deshielding effect. The proton's absorption will occur downfield from what is expected. Specifically, the proton will absorb at a smaller field strength than a proton experiencing no deshielding effects. Electron releasing atoms (or groups) that are nearby a proton will increase the proton's electron density; the proton is experiencing a shielding effect. The proton's absorbance will occur upfield (higher magnetic field strength) from what is expected. hbThe signal that arises from a proton's absorption May Occur as a singlet, a doublet, a triplet, etc. The number of peaks in the signal depends upon the neighboring protons. Protons that are in identical electronic environ- ments are equivalent protons; those that are in non- identical electronic environments are non-equivalent protons. A proton that has n non-equivalent adjacent protons will have a signal with n + 1 peaks, called a n+ 1 multiplet. This is the result of spin-spin splitting of the protons. For example, all the protons of ethane (CH3-CH3) are in identical electronic environments and are therefore equivalent. Hence there will be no spin-spin splitting of the protons; the nmr spectrum will contain only singlets (signals with one peak). Furthermore, since all the protons in ethane are equivalent they will have identical chemical shifts, and will occur as one signal. Hence the nmr spectrum of ethane will have one singlet. An example where spin-spin splitting occurs is propane. The methylene protons are non- equivalent to the methyl protons. As a result, the six non- equivalent adjacent methyl protons will split the methylene proton's signal into a heptet (seven peak multiplet). The relative areas under the signals in an nmr spectrum indicate the relative number of protons that give rise to each signal. With our basic understanding of nuclear magnetic resonance, we can now deduce the structures of (a) through (e). (a) The compound's molecular formula (C2H;Cl3) is of the type C2*., where * represents an atom that forms a Single bond with carbon. The formula Co*, is of the form Ci*> n+2 and indicates that the carbon compound is saturated; there are only o bonds in this compound. The nmr spectrum shows a singlet at about 2.7 6. Since the signal is a singlet there is no spin-spin splitting. This means that the three protons in the compound are equivalent. Since the two carbons are adjacent all three protons must be on one carbon for no spin-spin splitting to occur. Hence the compound is 1,1,1-trichloroethane and has the structure: (b) As in part (a), the molecular formula (C2H3Br3) is of the form c.* 2n+2? and is hence a saturated carbon compound. The nmr spectrum has a doublet near 4.2 6 and a triplet near 5.7 6. These multiplets occurred as a result of spin-spin splitting. Since there is a doublet and a triplet in the spectrum, and there are three hydrogen atoms in the compound, we can conclude that there is one hydrogen adjacent to two non-equivalent hydrogens. This means that the carbon with one hydrogen has two bromines 45and the carbon bearing two hydrogens has one bromine. The compound is 1,1,2-tribromoethane: H H Br-C—C-Br Br H The lone -CHBr2 hydrogen split the -CH2Br signal into a doublet; the two -CH2Br hydrogens split the -CHBr2 signal into a triplet. The -CHBr2 signal occurred down- field from the -CH2Br signal because the deshielding effect of two bromine atoms is greater than that of one bromine atom. (c) The molecular formula (C,H ,Br) is of the form Cn on+2 and is therefore a saturated carbon compound. The nmr spectrum has a singlet at 1.7 6; this indicates that there is no spin-spin splitting. Hence, all the hydrogens are equivalent; they are in identical electronic environ- ments. The only manner in which all the hydrogens are equivalent is if there are three methyl (-CH3) groups. This leaves us with a -CBr portion. The only possible structure is: CH 3 CH,-C—Br CH 3 2-bromo-2-methylpropane (d) As in parts (a) through (c) the molecular formula (CyH7Br3) of the compound indicates that the compound is saturated. The nmr spectrum shows a singlet at 3.9 6 and another singlet at 2.0 6, having relative intensities (relative areas) of four and three, respectively. The absence of multiplets means that no spin-spin splitting occurred. If all the protons were equivalent, the spectrum would show only one signal because equivalent protons have identical chemical shifts. The fact that there are two signals indicates that there are two sets of non-equivalent protons. Since there are seven hydrogens in the compound, and the sum of the relative intensities is seven, the relative intensities show the actual number of protons absorbing per molecule. The signal at 2.0 6 with a relative intensity of three must have arisen from the absorption of a methyl group's protons. This is because in a saturated four-carbon compound, a methyl group is the only group that has three equivalent hydrogens. Since no spin-spin splitting occurred the methyl group must be separated from the other hydrogens by a carbon bearing no hydrogens. In order for the four remaining hydrogens to be equivalent (they gave rise to the same signal), they must be part of equivalent groups. The signal that occurs at 3.9 6 is characteristic of an R-CH2-Br chemical shift. With this in mind we can conclude that the four remaining 46hydrogens are part of two -CH2Br groups. The structure of the compound is: BrCH2 CBr-CH 3 BrCHo 2-bromomethy1-1,2-dibromopropane (e) Once again we are dealing with a saturated carbon compound, this one having a molecular formula of C.H,Bro. The nmr spectrum shows a doublet at 2.4 6 and a quartet at 5.8 6, with relative intensities of three and one, respectively. The presence of these multiplets means that spin-spin splitting occurred. The protons that gave rise to the doublet were split by one non-equivalent proton. The proton that gave rise to the quartet was split by three non-equivalent protons. Since we are restricted to two carbons, the only possible compound is 1,1-di- bromoethane: { Br H-C-C-H H Br @ PROBLEM 2-11 (a) On catalytic hydrogenation, compound A, CsH., gave cis-1,2-dimethylcyclopropane. On this basis, three isomeric structures were considered possible for A. What were they? (b) Absence of infrared absorption at 890 cm-' made one of the structures unlikely. Which one was it? (c) The nmr spectrum of A showed signals at 6 2.22 and 6 1.04 with intensity ratio 3:1. Which of the three structures in (a) is consistent with this? (d) The base peak in the mass spectrum was found at m/e 67. What ion was this peak probably due to, and how do you account for its abundance? (e) Compound A was synthesized in one step from open-chain compounds. How do you think this was done? Solution: (a) Catalytic hydrogenation of alkenes (compounds with a carbon-carbon double bond) yields the corresponding alkanes (saturated hydrocarbons). The reaction proceeds with the cis addition of two hydrogen atoms to the double bond; the hydrogens add onto the same side of the double bond. H H H 4H a Cc / / \o 4 —_—_-> ay ec b/ d h a 47Note: = bond coming towards reader |\'"we == bond going away from reader Compound A underwent catalytic hydrogenation to yield cis-1,2-dimethylcyclopropane: catalytic H ““ i CH CsHe hydrogenation H 7 Compound A Hf cu, cis-1,2-dimethylcyclopropane Since compound A's molecular formula (Cs5Hg) contains two less hydrogens than the hydrogenation product's molecular formula (CsHi 9), there must have only been one double bond in compound A because only one mole of hydrogen gas was consumed in the reaction. There are three possible positions for a double bond to be created in cis-1,2-di- methylcyclopropane. There can be a double bond coming off the ring to a methylene group: CH 2 H stam» Hee Hd cH, CH, H LN CH Hd ° There can be a tetrasubstituted alkene: The third possibility is a trisubstituted alkene: min H CH, Catalytic hydrogenation of these three compounds all yield cis-1,2-dimethylcyclopropane. Note that the tetra- substituted alkene yields only the cis product upon catalytic hydrogenation. The other two yield cis and trans products, depending upon which side of the double bond was hydrogenated. (b) Disubstituted terminal alkenes (R2C=CH2) characteris- tically have a strong band at 890 cm~’ in the infrared spectrum. This is the absorption of the C-H out-of-plane bending vibrations. Since the infrared spectrum of compound A has no such band, we can eliminate the terminal alkene 7 H simd, Noe H as a possible structure for A. H CH 48 3(c) Since there are eight hydrogens in compound A, and the sum of the relative intensities is four, the relative intensities represent one half the number of protons absorbed per molecule. Hence for every molecule there are six protons absorbing at 6 2.22 and two protons absorbing at 6 1.04. The presence of two signals in the nmr spectrum indicates that there are two sets of non-equivalent protons (that have different chemical shifts, hence different signals). Of the three possible structures for compound A in part (a), only the tetrasubstituted alkene has two sets of non-equivalent hydrogens. The six methyl hydrogens are non-equivalent to the clny methylene hydrogens: (5 4 methylene 4 methyl hydrogens nethynens { sA SS ye The terminal alkene i was previously suggested as @ possible structure for A has five sets of non-equivalent hydrogens. The trisubstituted alkene that was suggested has four sets of ‘non-equivalent hydrogens. Hence the only struc- ture from part (a) that is consistent with the nmr spectrum is the tetrasubstituted alkene, 1,2-dimethylcyclopropene: CH3 - A. H gy CH3 (d) The base peak in a mass spectrum is the peak which corresponds to the positively charged species of highest stability upon a compound's fragmentation. The cation with molecular weight 67 must be formed by loss of a hydride anion from compound A which has a molecular weight of 68. This cation will be consistent with the proposal that compound A is 1,2-dimethylcyclopropene in that the sub- sequently formed cation will contain two 7 electrons and be aromatic. Its aromaticity is determined by Huckel's rule which states that a cyclic, conjugated 1 system of 4n+ 2n electrons (where n is an integer) is aromatic. Aromaticity and its associated electron delocalization confer stability upon the cation, agreeing with the spectral data. The cyclopropenyl ion has the following structure: CH, + CH; CH, CH3 — — <_— H ch, H; “H 3 H; oH (e) The only way to synthesize this cyclopropene ring from open chain reagents would be through the use of the carbene, methylene (CH2:) and the acetylene derivative, 2-butyne. The carbene is generated via diazomethane's loss of nitrogen upon heating, and its free pair of electrons allow it to be reactive enough to add to sites of unsaturation such as a triple bond. On occasion, it may 4geven add to alkenes. Thus the synthesis would be as follows: CH2N2 = :CHo | CH 3-C=C-CH3 + CH; Hotei Hg CH @ PROBLEM 2-12 The Figure below shows the proton n.m.r. spectrum of (CH3) 2C(OH)CH2COCH3 with tetramethylsilane as standard. The stepped line is an electronic integration of the areas under the signal peaks. (a) List the chemical shift. of each proton signal in ppm, and deduce, from the trace of the integrated areas, the identity of the protons that give rise to each line. (b) List the line positions in cps relative to tetramethylsilane expected at 100 Mcps. (c) Sketch out the spectrum and integral expected for CH3COC(CH3) 2CHO at 60 Mcps. 200 150 4.0 3.0 2.0 1.0 O ppm N.m.xr. spectrum of diacetone alcohol, (CH;) 2C (OH) CH2COCH; at 60 Mcps relative to TMS 0.00 ppm. The stepped line is the integrated spectrum. Solution: (a) To assign the identity of the protons to the spectral lines, we must look at the different types of protons within the molecule. Once we have identified all the non-equivalent protons in the molecule, we must deter- Mine their relative chemical shifts. When we have deduced the relative order of chemical shifts, we can read off the chemical shift of each signal and assign these values to particular protons. Diacetone alcohol has the following structure: 50