《有机化学》课程教学资源（参考书籍）Organic Chemistry II For Dummies 2010, John T. Moore, EdD Richard H. Langley, PhD

xiv Organic Chemistry ll For Dummies Chapter 8:Aromatic Substitution Part ll:Attack of the Nucleophiles and Other Reactions.........................111 Coming back to nucleophilic substitution reactions 111 Mastering the Mechanisms of Nucleophilic Substitution Reactions....112 Losing and Gaining:Mechanisms of Elimination/Addition Reactions 114 Benzyne.... 114 The elimination/addition mechanism. .114 Synthetic Strategies for Making Aromatic Compounds....... 115 Briefly Exploring Other Reactions........ .117 Part 111:Carbonyls:Good Alcohols Gone Bad. .121 Chapter 9:Comprehending Carbonyls 123 Carbonyl Basics........ .123 Considering compounds containing the carbonyl group...........124 Getting to know the acidic carbonyl.. 12 Polarity of Carbonyls Resonance in Donyls Reactivity of th onyl Group Spectros yof Ca bonyls 12 iole ble(el eti e (NMRO opy 12 Mass spectro .134 Chapter 10:Aldehydes and Ketones. .....137 enclature. op Creatin hydes s and Ker tones with Synthesis Reactions 140 eactions 1A Other reactions 142 Taking Them a Step Further:Reactions of Aldehydes and Ketones...146 Nucleophilic attack of aldehydes and ketones 147 Oxidation of aldehydes and ketones. 156 The Baeyer-Villiger reaction. .158 Checking Out Spectroscopy Specs. .160 Chapter 11:Enols and Enolates................................161 Getting to Know Enols and Enolates 161 eady:Structu re of enols and enolates 16 ght I saw a tautom 163 Studying the Synthesis of Enols and Enolates. .164

xiv Organic Chemistry II For Dummies Chapter 8: Aromatic Substitution Part II: Attack of the Nucleophiles and Other Reactions . . . . . . . . . . . . . . . . . . . . . . . . .111 Coming Back to Nucleophilic Substitution Reactions ............................111 Mastering the Mechanisms of Nucleophilic Substitution Reactions ....112 Losing and Gaining: Mechanisms of Elimination/Addition Reactions...................................................................................................114 Benzyne ...............................................................................................114 The elimination/addition mechanism .............................................114 Synthetic Strategies for Making Aromatic Compounds ..........................115 Briefl y Exploring Other Reactions .............................................................117 Part III: Carbonyls: Good Alcohols Gone Bad .............. 121 Chapter 9: Comprehending Carbonyls . . . . . . . . . . . . . . . . . . . . . . . . . .123 Carbonyl Basics ...........................................................................................123 Considering compounds containing the carbonyl group .............124 Getting to know the acidic carbonyl ...............................................127 Polarity of Carbonyls ..................................................................................128 Resonance in Carbonyls .............................................................................129 Reactivity of the Carbonyl Group ..............................................................130 Spectroscopy of Carbonyls ........................................................................130 Infrared spectroscopy .......................................................................130 Ultraviolet-visible (electronic) spectroscopy ................................131 Nuclear magnetic resonance (NMR) spectroscopy.......................132 Mass spectroscopy ............................................................................134 Chapter 10: Aldehydes and Ketones . . . . . . . . . . . . . . . . . . . . . . . . . . . .137 Meeting Alcohol’s Relatives: Structure and Nomenclature ...................137 Defi ning Physical Properties of Aldehydes and Ketones .......................139 Creating Aldehydes and Ketones with Synthesis Reactions ..................140 Oxidation reactions ...........................................................................140 Reduction reactions ..........................................................................142 Other reactions ..................................................................................143 Taking Them a Step Further: Reactions of Aldehydes and Ketones .....146 Nucleophilic attack of aldehydes and ketones ..............................147 Oxidation of aldehydes and ketones ...............................................156 The Baeyer-Villiger reaction .............................................................158 Checking Out Spectroscopy Specs ............................................................160 Chapter 11: Enols and Enolates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .161 Getting to Know Enols and Enolates .........................................................161 Enough already: Structure of enols and enolates ..........................162 I thought I saw a tautomer ................................................................163 Studying the Synthesis of Enols and Enolates .........................................164 02_178157-ftoc.indd xiv 5/28/10 9:44 AM

Table of Contents U Thinking Through Reactions of Enols and Enolates. 166 Haloform r eactions 16G Aldol reactions and condensations 16R Addition reactions to unsaturated aldehydes and ketones... 173 Other enolate-related reactions. 178 Miscellaneous reactions. .180 Chapter 12:Carboxylic Acids and Their Derivatives..............187 se8ahcAcseaaamieatureod 1只8 .188 Checking Out Some Physical Properties of Carboxvlic Acids and Derivatives .193 Carboxylic acids.. .193 Esters. 193 Amides.. .194 Considering the Acidity of Carboxylic Acids194 Determining How Carboxylic Acids and Derivatives Are Synthesized.. Synth zing ca c acids lide s with hal ogen ides cidsand al Uniting acids 00g and bases together to create amides 209 ous carboxvlic acids 90g Simple acyl halide and anhydride reactions. 210 Hydrolvsis of esters .210 Amide reactions ester's cousins 211 Other reactions of carboxvlic acids and derivatives .213 Taking a Look at Spectroscopy and Chemical Tests.. .217 Identifying compounds with spectral data... .218 Using chemical tests... .218 Part IV:Advanced Topics (Every Student's Nightmare)21g Chapter 13:Amines and Friends...... ...221 Breaking Down the Structure and Nomenclature of N unds and tertiary amine 992 (qua erna mon um salts) 224

Table of Contents xv Thinking Through Reactions of Enols and Enolates ...............................166 Haloform reactions ............................................................................166 Aldol reactions and condensations .................................................168 Addition reactions to unsaturated aldehydes and ketones .........173 Other enolate-related reactions .......................................................178 Miscellaneous reactions ...................................................................180 Chapter 12: Carboxylic Acids and Their Derivatives. . . . . . . . . . . . . .187 Seeing the Structure and Nomenclature of Carboxylic Acids and Derivatives ..........................................................188 Structure .............................................................................................188 Nomenclature .....................................................................................188 Checking Out Some Physical Properties of Carboxylic Acids and Derivatives ..........................................................193 Carboxylic acids .................................................................................193 Esters ...................................................................................................193 Amides .................................................................................................194 Considering the Acidity of Carboxylic Acids ...........................................194 Determining How Carboxylic Acids and Derivatives Are Synthesized ...................................................................196 Synthesizing carboxylic acids ..........................................................196 Developing acyl halides with halogen .............................................199 Removing water to form acid anhydrides ......................................200 Uniting acids and alcohols to make esters .....................................202 Bringing acids and bases together to create amides ....................206 Exploring Reactions ....................................................................................208 Generous carboxylic acids ...............................................................209 Simple acyl halide and anhydride reactions ..................................210 Hydrolysis of esters ...........................................................................210 Amide reactions, ester’s cousins .....................................................211 Other reactions of carboxylic acids and derivatives ....................213 Taking a Look at Spectroscopy and Chemical Tests ..............................217 Identifying compounds with spectral data .....................................218 Using chemical tests ..........................................................................218 Part IV: Advanced Topics (Every Student’s Nightmare) ............................................... 219 Chapter 13: Amines and Friends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .221 Breaking Down the Structure and Nomenclature of Nitrogen Compounds ..........................................................................221 Primary amines ..................................................................................222 Secondary and tertiary amines ........................................................223 Quaternary amines (quaternary ammonium salts) .......................223 Heterocyclics ......................................................................................224 02_178157-ftoc.indd xv 5/28/10 9:44 AM

xvi Organic Chemistry ll For Dummies Sizing Up the Physical Properties 225 Understanding the Basicity of Nitrogen Compounds..................226 Synthesizing Nitrogen Compounds.. 422 Nucleophilic substitution reactions Reduction preparations.. Seeing How Nitrogen Compounds React. ons with nitrous acic salts... onyl chloride elimin actions Master ng Multiste 94 Identifving Nitrogen Compounds with Analysis and Spectroscopy 246 Chapter 14:Metals Muscling In:Organometallics...............249 Grignard Reage E gnard reagent reag nts Orga 956 057 258 Chapter 15:More Reactions of Carbonyl Compounds. .261 ondensation and Its Variations. 26 sen col g a bli ssed Othe acetic Ester Defining malonic Ester sv 260 Working with Other Active Hydrogen Atoms 972 Reacting with knoev agel Condensation. 972 Looking at Mannich Reactions.. 275 Creating Enamines:Stork Enamine Synthesis. 277 Putting It All Together with Barbiturates... .279 Chapter 16:Living Large:Biomolecules. 281 Delving into Carbohydrate Complexities )Q9 Introducing carbohydrates 2R2 Examining the many reactions of monosaccharides 2R6 201 Meeting the (Daldose family 293 Checking out a few disaccharides 295 Looking at some polysaccharides. .29 Discovering nitrogen-containing sugars .298 Lipids:Storing Energy Now So You Can Study Longer Later.... 299 Pondering the properties of fats... Soaping up with saponification.... .300

xvi Organic Chemistry II For Dummies Sizing Up the Physical Properties .............................................................225 Understanding the Basicity of Nitrogen Compounds .............................226 Synthesizing Nitrogen Compounds ...........................................................227 Nucleophilic substitution reactions ................................................227 Reduction preparations ....................................................................229 Seeing How Nitrogen Compounds React ..................................................233 Reactions with nitrous acid ..............................................................233 Replacement reactions......................................................................235 Coupling reactions of diazonium salts ............................................239 Reactions with sulfonyl chlorides ...................................................239 Exploring elimination reactions .......................................................241 Mastering Multistep Synthesis ...................................................................244 Identifying Nitrogen Compounds with Analysis and Spectroscopy ........246 Chapter 14: Metals Muscling In: Organometallics . . . . . . . . . . . . . . .249 Grignard Reagents: Grin and Bear It .........................................................249 Preparation of Grignard reagents ....................................................250 Reactions of Grignard reagents........................................................250 Organolithium Reagents .............................................................................256 Formation of Other Organometallics ........................................................257 Putting It Together ......................................................................................258 Chapter 15: More Reactions of Carbonyl Compounds . . . . . . . . . . . . .261 Checking Out the Claisen Condensation and Its Variations ..................262 Doing the two-step: Claisen condensation .....................................262 Circling around: Dieckmann condensation ....................................264 Doubling Up: Crossed Claisen condensation .................................265 Other carbanions ...............................................................................266 Exploring Acetoacetic Ester Synthesis .....................................................267 Defi ning Malonic Ester Synthesis ..............................................................269 Working with Other Active Hydrogen Atoms ..........................................273 Reacting with Knoevenagel Condensation ...............................................273 Looking at Mannich Reactions ...................................................................275 Creating Enamines: Stork Enamine Synthesis ..........................................277 Putting It All Together with Barbiturates .................................................279 Chapter 16: Living Large: Biomolecules. . . . . . . . . . . . . . . . . . . . . . . . .281 Delving into Carbohydrate Complexities .................................................282 Introducing carbohydrates ...............................................................282 Examining the many reactions of monosaccharides ....................286 Synthesizing and degrading monosaccharides..............................291 Meeting the (D-)aldose family ..........................................................293 Checking out a few disaccharides ...................................................295 Looking at some polysaccharides ...................................................296 Discovering nitrogen-containing sugars .........................................298 Lipids: Storing Energy Now So You Can Study Longer Later .................299 Pondering the properties of fats ......................................................299 Soaping up with saponifi cation ........................................................300 02_178157-ftoc.indd xvi 5/28/10 9:44 AM

Table of Contents xvii Bulking Up on Amino Acids and Proteins. 302 201 Perusing the physical properties of amino acids.. 20 Studying the synthesis of amino acids. .304 Part U:Pulling It All Together......309 Chapter 17:Overview of Synthesis Strategies .311 Working with One-Step Synthesis.... .312 Tackling Multistep Synthesis. 312 Practicing Retrosynthetic and Synthetic Analysis. .313 Example 1. .314 Example 2.. .319 Example 3.. ,321 Example 4. .32 Example 5... .324 Chapter 18:Roadmaps and Predicting Products7 Preparing with Roadmap Basics... .327 Practicing Roadmap Problems .328 Problem one. .328 Solution one 328 Problem two .33 Solution two. .330 Problem three.. Solution three Predicting Products… part Ul:The part of Tens337 Chapter 19:Ten Surefire Ways to Fail Organic Chemistry ll.......339 Don W uy a Mo About Fallin Behind with Additional Resources ou.Don't Bother 341 Don't Bother Reading a the Char ter before Attending Class. 241 Attend Class Only When You Feel Like It. .342 Don't Bother Taking Notes-Just Listen (When You Aren't Sleeping or Texting).. 342 Don't Bother Asking Questions. 342

Table of Contents xvii Bulking Up on Amino Acids and Proteins .................................................301 Introducing amino acids ...................................................................302 Perusing the physical properties of amino acids ..........................302 Studying the synthesis of amino acids ............................................304 Part V: Pulling It All Together ................................... 309 Chapter 17: Overview of Synthesis Strategies . . . . . . . . . . . . . . . . . . .311 Working with One-Step Synthesis .............................................................312 Tackling Multistep Synthesis .....................................................................312 Practicing Retrosynthetic and Synthetic Analysis ..................................313 Example 1 ............................................................................................314 Example 2 ............................................................................................319 Example 3 ............................................................................................321 Example 4 ............................................................................................322 Example 5 ............................................................................................324 Chapter 18: Roadmaps and Predicting Products . . . . . . . . . . . . . . . . .327 Preparing with Roadmap Basics ................................................................327 Practicing Roadmap Problems ..................................................................328 Problem one .......................................................................................328 Solution one ........................................................................................328 Problem two .......................................................................................330 Solution two ........................................................................................330 Problem three.....................................................................................332 Solution three .....................................................................................332 Predicting Products ....................................................................................335 Part VI: The Part of Tens ........................................... 337 Chapter 19: Ten Surefi re Ways to Fail Organic Chemistry II . . . . . . .339 Simply Read and Memorize Concepts ......................................................339 Don’t Bother Working the Homework Problems and Exercises ............340 Don’t Buy a Model Kit .................................................................................340 Don’t Worry About Falling Behind ............................................................340 Don’t Bother Learning Reactions ..............................................................341 If Your Textbook Confuses You, Don’t Bother with Additional Resources ......................................................................341 Don’t Bother Reading the Chapter before Attending Class ...................341 Attend Class Only When You Feel Like It .................................................342 Don’t Bother Taking Notes — Just Listen (When You Aren’t Sleeping or Texting) .....................................................................342 Don’t Bother Asking Questions ..................................................................342 02_178157-ftoc.indd xvii 5/28/10 9:44 AM

xviii Organic Chemistry ll For Dummies Chapter 20:More than Ten Ways to Increase Your Score on an Organic Chemistry Exam.....................343 Don't cram the night before a test 343 Try Doing the Problem Sets and Practice Tests Twice. 244 Study the Mistakes You Made on Previous Exams 2A4 Know Precisely Where,Why,and How the Electrons Are Moving........344 Relax and Get Enough Sleep before the Exam.... 345 Think Before You Write. .345 Include Formal Charges in Your Structures When Appropriate..........345 Check That You Haven't Lost Any Carbon Atoms.. ..34 Include E/Z,R/S,cis/trans Prefixes in Naming Organic Structures.. .340 Think of Spectroscopy,Especially NMR,As a Puzzle 34 Make Sure That Each Carbon Atom Has Four Bonds.. .346 Appendix:Named Reactions.37 Index. ..349

xviii Organic Chemistry II For Dummies Chapter 20: More than Ten Ways to Increase Your Score on an Organic Chemistry Exam . . . . . . . . . . . . . . . . . . . . .343 Don’t Cram the Night before a Test ..........................................................343 Try Doing the Problem Sets and Practice Tests Twice ..........................344 Study the Mistakes You Made on Previous Exams .................................344 Know Precisely Where, Why, and How the Electrons Are Moving ..........344 Relax and Get Enough Sleep before the Exam .........................................345 Think Before You Write ..............................................................................345 Include Formal Charges in Your Structures When Appropriate ...........345 Check That You Haven’t Lost Any Carbon Atoms ..................................346 Include E/Z, R/S, cis/trans Prefi xes in Naming Organic Structures ..........346 Think of Spectroscopy, Especially NMR, As a Puzzle .............................346 Make Sure That Each Carbon Atom Has Four Bonds ..............................346 Appendix: Named Reactions ...................................... 347 Index ....................................................................... 349 02_178157-ftoc.indd xviii 5/28/10 9:44 AM