26 SYNTHETIC POLYMERS

Establishing an international standard of naming compounds is the purpose of the IUPAC system.

To correlate each name with a unique and unambiguous structure is the goal of the system.

IUPAC refers to a molecule's longest chain of carbons connected by single bonds, whether in a continuous chain or in a ring.

All deviations are indicated by a specific set of priorities.

Alkanes are the family of saturated hydrocarbons that are composed of carbon and hydrogen.

The molecule can be in continuous chains or in rings.

The root names of organic compounds are alkanes and cycloalkanes.

The Greek or Latin prefix indicates the number of carbons in the chain.

The IUPAC system is updated frequently.

The 1993 guidelines place the position number close to the functional group designation, however, you should be able to use and recognize names in either the old or the new style.
Ask your instructor which system to use.

The substituents within Group C have the same priority.

Methoxy is what CH3O is.

The names for complex substituents are given in brackets.

The following examples show how organic compounds containing substituents from Group C are named.

Determine the root name of the chain.

The smaller number is the position number of the first substituent.

If the first substituents have the same number, then the second substituent has a smaller number.

Determine the position of each substituent.

The position numbers and names of the substituent groups should be placed in alphabetical order.

Always include a position number for each substituent.
If there is a tie, the carbon with the substituent whose name is earlier in the alphabet could be used to begin the numbering.

Because it has a higher priority than any other substituents, the C " C has a lower position number.

A substituent name is used when the chain cannot include an alkene.

Numbering can only be done on either a ring or a chain.

The alkyne has the lower position number.

The alkene takes the lower number if each has the same position number.

The group of highest priority is indicated by the name of the molecule, with priority equivalent to any other substituents.

Now that the functional groups and substituents from Groups A, B, and C have been described, a modified set of steps for naming organic compounds can be applied to all simple structures.

Name the longest continuous carbon chain that includes this group.

The lower number is assigned to the highest priority functional group.

The position of the multiple bond should be determined by the number of the first carbon.

If the molecule includes Group A functional groups, replace the last "e" with the highest prior ity functional group, and include its position number just before the name of the highest priority functional group.

The number 1 is usually omitted from the name because an aldehyde can only be on carbon 1.

The six groups derived from carboxylic acids are in decreasing priority after carboxylic acids, salts, anhydrides, esters, acyl halides, amides, and nitriles.

The alkyl name comes first, followed by the name of the carboxylate anion.

"Aromatic" compounds are derived from benzene and similar ring systems.

The process of determining the root name of the parent ring, priority, and position number of substituents, and assembling the name in alphabetical order is similar to the aliphatic nomenclature described earlier.

The root name of the ring can be changed.

A group of aromatic compounds called ketones are attached to at least one benzene ring.

phenones are compounds that are named after the group on the other side of the carbonyl.

Bicyclic compounds have two rings.

Four possible arrangements of two rings are dependent on how many atoms are shared by the two rings.
The first arrangement in which the rings do not share any atoms does not require a method to designate how the rings are put together.
Functional groups and substituents follow standard rules once the ring system is named.

The standard rules of choosing one parent ring system and describing the other ring as a substituent are followed.

The highest priority functional group is phenyl.

Benzene is larger than cyclopentane and has three substituents.

The ring system in spiro compounds is indicated by the word "spiro", followed by brackets indicating how many atoms are contained in each path around the rings, and an alkane name describing how many carbons are in the ring systems.

Numbering goes through the spiro carbon and around the second ring.

In the usual way, functional groups are indicated.

Spiro ring systems are numbered smaller before larger in order to give the highest priority functional group the lower position number.

A fused ring is a pair of rings that share a common atom.

The ring system and bridged rings are the same type.
There are three paths between the two bridgehead atoms.
The shortest path in a fused ring is always zero.
Numbering begins at a bridgehead, continues around the largest ring, and then goes through the other bridgehead and around the shorter ring.

In the usual way, functional groups are indicated.

The highest priority functional group the lower position number is given the highest priority by the numbered fused ring systems.

Two rings that share more than two atoms are called bridged rings.

There are three paths between the two bridgehead atoms in the ring system.
The medium and shortest path are counted first.
Numbering starts at a bridgehead, continues around the largest ring, goes through the other bridgehead, and ends with the shortest path numbered from the original bridgehead atom.

A simple system called "replacement nomenclature" has been devised to replace the name of the location where Heteroatoms appear.

The principle is to name a compound as if it contained only carbons in the skeleton, plus any functional groups or substituents, and then indicate which carbons are "replaced" by Heteroatoms.

The compound is named if it still has carbons.

The replacement system is useful in polycyclic compounds.

This example uses a reagent that is commercially available.

Systems to designate relative and absolute orientation of the groups are required for compounds that exhibit stereoisomerism.

The systems have been discussed in the text.

hydrogen bonds with water can be formed by these four plus.

The bond angle is compressed by two lone pairs.

C erism about the C " N double bond is shown in CH3.

There are no cis-trans 3)3 6 CH3 CH2C( CH3)2 CH2 CH3 6 octane on the C " N carbon atom.

Trans is more stable.

The cis isomers are mostly cis isomers.
You should convert some structures to Lewis structures.

The second and fifth structures are made of but-1-ene.

The last structure is 2-methylpropene.

The third and fourth are the same as the first and second.

2, 2-dimethylbutane is the third and fifth structure.

The 60deg bond angle of cyclopropene is better than the 109.5% bond angle of 2,2,6-trimethylheptane.

The lone second cyclohexane ring is located in equatorial positions.

The catalyst is hybridized and Platinum.

The bond dipole moments do not cancel when hybridized and bent.

Stability: 1-dodecyne; (e) N-methylpyridinium iodide; (f) CH3CCH2CH2NH2;

The low conc is provided by the NBS.

The sample should beDiluted.

2,3-dimethylbut-2-ene is more asymmetric.

Only (e) has asymmetric carbons.
The others may have a stable cold.

Water forms the lower layer because it is denser than hexane.

Chloroform is denser than water.
Water and hydride shift first.
The Zaitsev product is against the rule.

1-bromo-1-methylcyclohexane, 1,1-dibromo-3-fluorocycloheptane, and cyclohexene are included.

The mixture should be treated with bromomethylcyclohexane and 1-chloro-2-methylpropane.

NH3 + NaOCH3 are the answers to selected problems.
NaNH2, oxidation, C3 reduction, and isobutyl halide are unfavorable.

CH3I, then NaNH2, then CH3 CH2CHO, then chromic acid, add G.

An alcoholic has more dehydrogenases.

More dehalogenate to the alkyne, Na, NH3 is needed to tie up the larger amount of enzyme.

Excess tosylate with bromide; excess tosylate with ammonia; excess tosylate with cyanide.

F is stabilizing the alkoxide.

H; 1642 C " C will go into a liquid.

2@methylhexan@3@one + NaBH4.

There are two substances: -dimethoxybenzene and (c) 1,2-dibromo-2-methylpropane.

The CH2 groups have diastereotopic hydrogens.

The other two are not aromatic.

The anion is anti-aromatic and the cation is aromatic.

Intermolecular condensation might work.

The Williamson can be used for chloride.
The aromatic cyclopen is deprotonated to the second.
It's best for (c).

ethylene oxide and dibromobenzene are created by the oxidation of it.

Charge on two 2deg cars and one 3deg carbon, compared with three 2deg carbons in benzene.

Then ethyl 2-nitrophenol and 3-ethyl-4-nitrophenol.

There are overalkylation products withmethylanisole.

There are butylbenzene and others; (b) OK; (c) +disub, 6 hexa@1,5@diene 6 hexa@1,3@triene; trisub; (d) No, deactivated.

The F bond is made of 2-bromo-1-methylenecyclohexane.

Both have the same allylic carbanion.

A reactivity ratio of 40% alpha and 60% alpha is calculated.

The answers to selected problems are cyclopentyl ketone and benzylacetaldehyde.

2-chlorobenzene-1,4- and methylamine; butan-2-one and ammonia; acetaldehyde dicarboxylic acid; and 2-chloroterephthalic acid.
Broad acid OH ylhydrazine; (d) cyclohexanone and 2,4-DNP; (e) 4-(o-aminophenyl) centered around 3000.

R]+ could lose a pro heat, then H ton from a CH 3O+.

The center is butan-2-one.

Aniline 6 pyridine 6 piperidine; (c) pyrrole 6 1-amine; (b) cyclohexylethylamine.

acetic anhydride is cheap and easy to use.
N-nitrosopiperidine and benzenediazonium PhNH2 are warm.

Add water to hydrolyzeacetic acid.

The only pair on the indole N is part of the aro.

The free group of the deacylated l enantiomer should be aldehyde.

The N-terminus is effectively blocked by the N-terminal Glu.

C-terminal Pro is a amide.

Alkylate the enamine of cyclohexanone.

Estradiol is a phenol in water.

The benzylic hydrogens are more likely to be enantiomers.

The more highly substituted pairs of enantiomers are given by them all.

The cation at the end of a chain is different from the one at the beginning.

It should have "-oside" ending because Glycerol allows cross-linking.

H2N(CH2)9NH2 is a-d-glu.

Melibiose is a base catalyst.
Poly is an addition.
The bonds are made of ester.
The aldehyde is not stable.

1309 is a sulfate of dodexyl sulfate.

Not all of these abbreviations are used in this text, but they are provided for reference.

All chemical shifts are affected by neighboring substituents.

The numbers assume that alkyl groups are the only other substituents present.
Appendix 1 has a more complete table of chemical shifts.

C O can be seen in ethers, esters, and alcohols.

Appendices 2A and 2B have more complete tables of IR frequencies.

Document Outline

Cover

Title Page 1

About the Authors 3

Contents 5

Preface 25

1 STRUCTURE AND BONDING 37 1-1 The Origins of Organic Chemistry 37 1-2 Principles of Atomic Structure 39 1-3 Bond Formation: The Octet Rule 43 1-4 Lewis Structures 44 1-5 Multiple Bonding 45 Summary: Common Bonding Patterns (Uncharged) 45 1-6 Electronegativity and Bond Polarity 46 1-7 Formal Charges 47 1-8 Ionic Structures 49 1-9 Resonance 50 PROBLEM-SOLVING STRATEGY: Drawing and Evaluating Resonance Forms 54 1-10 Structural Formulas 58 1-11 Molecular Formulas and Empirical Formulas 61 1-12 Wave Properties of Electrons in Orbitals 63 1-13 Molecular Orbitals 64 1-14 Pi Bonding 67 1-15 Hybridization and Molecular Shapes 68 1-16 Drawing Three-Dimensional Molecules 72 1-17 General Rules of Hybridization and Geometry 73 Summary: Hybridization and Geometry 73 1-18 Bond Rotation 78 1-19 Isomerism 80 Essential Terms 83 Study Problems 86

2 ACIDS AND BASES; FUNCTIONAL GROUPS 91 2-1 Polarity of Bonds and Molecules 92 2-2 Intermolecular Forces 96 2-3 Polarity Effects on Solubilities 100 2-4 Arrhenius Acids and Bases 103 2-5 Bronsted-Lowry Acids and Bases 104 2-6 Strengths of Acids and Bases 105 2-7 Equilibrium Positions of Acid-Base Reactions 109 PROBLEM-SOLVING STRATEGY: Predicting Acid-Base Equilibrium Positions 111 2-8 Solvent Effects on Acidity and Basicity 112 Summary: Acidity and Basicity Limitations in Common Solvents 114 2-9 Effects of Size and Electronegativity on Acidity 114 2-10 Inductive Effects on Acidity 116 2-11 Hybridization Effects on Acidity 117 2-12 Resonance Effects on Acidity and Basicity 119 2-13 Lewis Acids and Bases 122 2-14 The Curved-Arrow Formalism 124 2-15 Hydrocarbons 126 2-16 Functional Groups with Oxygen 129 2-17 Functional Groups with Nitrogen 132 Essential Terms 134 Study Problems 137

3 STRUCTURE AND STEREOCHEMISTRY OF ALKANES 143 3-1 Classification of Hydrocarbons (Review) 144 3-2 Molecular Formulas of Alkanes 144 3-3 Nomenclature of Alkanes 146 Summary: Rules for Naming Alkanes 151 3-4 Physical Properties of Alkanes 153 3-5 Uses and Sources of Alkanes 154 3-6 Reactions of Alkanes 157 3-7 Structure and Conformations of Alkanes 158 3-8 Conformations of Butane 162 3-9 Conformations of Higher Alkanes 165 3-10 Cycloalkanes 165 3-11 Cis-trans Isomerism in Cycloalkanes 167 3-12 Stabilities of Cycloalkanes; Ring Strain 168 3-13 Cyclohexane Conformations 172 PROBLEM-SOLVING STRATEGY: Drawing Chair Conformations 174 3-14 Conformations of Monosubstituted Cyclohexanes 176 3-15 Conformations of Disubstituted Cyclohexanes 179 PROBLEM-SOLVING STRATEGY: Recognizing Cis and Trans Isomers 179 3-16 Bicyclic Molecules 182 Essential Terms 184 Study Problems 188

4 THE STUDY OF CHEMICAL REACTIONS 191 4-1 Introduction 191 4-2 Chlorination of Methane 192 4-3 The Free-Radical Chain Reaction 193 4-4 Equilibrium Constants and Free Energy 197 4-5 Enthalpy and Entropy 199 4-6 Bond-Dissociation Enthalpies 201 4-7 Enthalpy Changes in Chlorination 202 4-8 Kinetics and the Rate Equation 205 4-9 Activation Energy and the Temperature Dependence of Rates 207 4-10 Transition States 208 4-11 Rates of Multistep Reactions 210 4-12 Temperature Dependence of Halogenation 211 4-13 Selectivity in Halogenation 212 4-14 Hammond's Postulate 218 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 219 4-15 Radical Inhibitors 222 4-16 Reactive Intermediates 223 Summary: Reactive Intermediates 230 Essential Terms 230 Study Problems 233

5 STEREOCHEMISTRY 237 5-1 Introduction 237 5-2 Chirality 238 5-3 (R) and (S) Nomenclature of Asymmetric Carbon Atoms 244 5-4 Optical Activity 249 5-5 Biological Discrimination of Enantiomers 254 5-6 Racemic Mixtures 255 5-7 Enantiomeric Excess and Optical Purity 256 5-8 Chirality of Conformationally Mobile Systems 257 5-9 Chiral Compounds Without Asymmetric Atoms 260 5-10 Fischer Projections 262 Summary: Fischer Projections and Their Use 266 5-11 Diastereomers 266 Summary: Types of Isomers 268 5-12 Stereochemistry of Molecules with Two or More Asymmetric Carbons 269 5-13 Meso Compounds 269 5-14 Absolute and Relative Configuration 271 5-15 Physical Properties of Diastereomers 273 5-16 Resolution of Enantiomers 274 Essential Terms 277 Study Problems 280

6 ALKYL HALIDES; NUCLEOPHILIC SUBSTITUTION 283 6-1 Introduction 283 6-2 Nomenclature of Alkyl Halides 284 6-3 Common Uses of Alkyl Halides 286 6-4 Structure of Alkyl Halides 288 6-5 Physical Properties of Alkyl Halides 289 6-6 Preparation of Alkyl Halides 291 Summary: Methods for Preparing Alkyl Halides 295 6-7 Reactions of Alkyl Halides: Substitution and Elimination 296 6-8 Bimolecular Nucleophilic Substitution: The SN2 Reaction 297 6-9 Generality of the SN2 Reaction 299 Summary: SN2 Reactions of Alkyl Halides 300 6-10 Factors Affecting SN2 Reactions: Strength of the Nucleophile 301 Summary: Trends in Nucleophilicity 302 6-11 Reactivity of the Substrate in SN2 Reactions 305 6-12 Stereochemistry of the SN2 Reaction 309 6-13 Unimolecular Nucleophilic Substitution: The SN1 Reaction 311 6-14 Stereochemistry of the SN1 Reaction 315 6-15 Rearrangements in SN1 Reactions 317 6-16 Comparison of SN1 and SN2 Reactions 320 Summary: Nucleophilic Substitutions 322 Summary: Reactions of Alkyl Halides 323 Essential Terms 324 Study Problems 327

7 STRUCTURE AND SYNTHESIS OF ALKENES; ELIMINATION 332 7-1 Introduction 332 7-2 The Orbital Description of the Alkene Double Bond 333 7-3 Elements of Unsaturation 335 7-4 Nomenclature of Alkenes 337 7-5 Nomenclature of Cis-Trans Isomers 339 Summary: Rules for Naming Alkenes 341 7-6 Commercial Importance of Alkenes 342 7-7 Physical Properties of Alkenes 344 7-8 Stability of Alkenes 346 7-9 Formation of Alkenes by Dehydrohalogenation of Alkyl Halides 354 7-10 Unimolecular Elimination: The E1 Reaction 355 Summary: Carbocation Reactions 359 7-11 Positional Orientation of Elimination: Zaitsev's Rule 360 7-12 Bimolecular Elimination: The E2 Reaction 362 7-13 Bulky Bases in E2 Eliminations; Hofmann Orientation 364 7-14 Stereochemistry of the E2 Reaction 365 7-15 E2 Reactions in Cyclohexane Systems 368 7-16 Comparison of E1 and E2 Elimination Mechanisms 370 Summary: Elimination Reactions 371 Summary: Substitution and Elimination Reactions of Alkyl Halides 374 PROBLEM-SOLVING STRATEGY: Predicting Substitutions and Eliminations 376 7-18 Alkene Synthesis by Dehydration of Alcohols 377 7-19 Alkene Synthesis by High-Temperature Industrial Methods 380 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 382 Summary: Methods for Synthesis of Alkenes 385 Essential Terms 386 Study Problems 389

8 REACTIONS OF ALKENES 395 8-1 Reactivity of the Carbon-Carbon Double Bond 395 8-2 Electrophilic Addition to Alkenes 396 8-3 Addition of Hydrogen Halides to Alkenes 398 8-4 Addition of Water: Hydration of Alkenes 406 8-5 Hydration by Oxymercuration-Demercuration 408 8-6 Alkoxymercuration-Demercuration 411 8-7 Hydroboration of Alkenes 412 8-8 Addition of Halogens to Alkenes 418 8-9 Formation of Halohydrins 421 8-10 Catalytic Hydrogenation of Alkenes 425 8-11 Addition of Carbenes to Alkenes 427 8-12 Epoxidation of Alkenes 429 8-13 Acid-Catalyzed Opening of Epoxides 431 8-14 Syn Dihydroxylation of Alkenes 434 8-15 Oxidative Cleavage of Alkenes 436 8-16 Polymerization of Alkenes 439 8-17 Olefin Metathesis 443 PROBLEM-SOLVING STRATEGY: Organic Synthesis 446 Summary: Reactions of Alkenes 448 Summary: Electrophilic Additions to Alkenes 451 Summary: Oxidation and Cyclopropanation Reactions of Alkenes 452 Essential Terms 453 Study Problems 457

9 ALKYNES 464 9-1 Introduction 464 9-2 Nomenclature of Alkynes 465 9-3 Physical Properties of Alkynes 467 9-4 Commercial Importance of Alkynes 467 9-5 Electronic Structure of Alkynes 469 9-6 Acidity of Alkynes; Formation of Acetylide Ions 470 9-7 Synthesis of Alkynes from Acetylides 472 9-8 Synthesis of Alkynes by Elimination Reactions 475 Summary: Syntheses of Alkynes 477 9-9 Addition Reactions of Alkynes 477 9-10 Oxidation of Alkynes 486 PROBLEM-SOLVING STRATEGY: Multistep Synthesis 488 Summary: Reactions of Alkynes 490 Summary: Reactions of Terminal Alkynes 491 Essential Terms 492 Study Problems 493

10 STRUCTURE AND SYNTHESIS OF ALCOHOLS 496 10-1 Introduction 496 10-2 Structure and Classification of Alcohols 496 10-3 Nomenclature of Alcohols and Phenols 497 10-4 Physical Properties of Alcohols 502 10-5 Commercially Important Alcohols 504 10-6 Acidity of Alcohols and Phenols 506 10-7 Synthesis of Alcohols: Introduction and Review 510 Summary: Previous Alcohol Syntheses 510 10-8 Organometallic Reagents for Alcohol Synthesis 511 10-9 Reactions of Organometallic Compounds 514 Summary: Grignard Reactions 520 10-10 Side Reactions of Organometallic Reagents: Reduction of Alkyl Halides 522 10-11 Reduction of the Carbonyl Group: Synthesis of 1deg and 2deg Alcohols 525 Summary: Reactions of LiAIH4 and NaBH4 527 Summary: Alcohol Syntheses by Nucleophilic Additions to Carbonyl Groups 528 10-12 Thiols (Mercaptans) 530 Summary: Synthesis of Alcohols from Carbonyl Compounds 533 Essential Terms 533 Study Problems 535

11 REACTIONS OF ALCOHOLS 541 11-1 Oxidation States of Alcohols and Related Functional Groups 542 11-2 Oxidation of Alcohols 543 11-3 Additional Methods for Oxidizing Alcohols 547 11-4 Biological Oxidation of Alcohols 549 11-5 Alcohols as Nucleophiles and Electrophiles; Formation of Tosylates 551 Summary: SN2 Reactions of Tosylate Esters 553 11-6 Reduction of Alcohols 554 11-7 Reactions of Alcohols with Hydrohalic Acids 555 11-8 Reactions of Alcohols with Phosphorus Halides 560 11-9 Reactions of Alcohols with Thionyl Chloride 561 11-10 Dehydration Reactions of Alcohols 563 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 567 11-11 Unique Reactions of Diols 570 11-11 Unique Reactions of Diols 570 11-12 Esterification of Alcohols 572 11-13 Esters of Inorganic Acids 573 11-14 Reactions of Alkoxides 576 PROBLEM-SOLVING STRATEGY: Multistep Synthesis 579 Summary: Reactions of Alcohols 582 Summary: Reactions of Alcohols: O!H Cleavage 584 Summary: Reactions of Alcohols: C!O Cleavage 584 Essential Terms 585 Study Problems 587

12 INFRARED SPECTROSCOPY AND MASS SPECTROMETRY 592 12-1 Introduction 592 12-2 The Electromagnetic Spectrum 593 12-3 The Infrared Region 594 12-4 Molecular Vibrations 595 12-5 IR-Active and IR-Inactive Vibrations 597 12-6 Measurement of the IR Spectrum 598 12-7 Infrared Spectroscopy of Hydrocarbons 601 12-8 Characteristic Absorptions of Alcohols and Amines 606 12-9 Characteristic Absorptions of Carbonyl Compounds 607 12-10 Characteristic Absorptions of C!N Bonds 612 12-11 Simplified Summary of IR Stretching Frequencies 614 12-12 Reading and Interpreting IR Spectra (Solved Problems) 616 12-13 Introduction to Mass Spectrometry 620 12-14 Determination of the Molecular Formula by Mass Spectrometry 623 12-15 Fragmentation Patterns in Mass Spectrometry 626 Summary: Common Fragmentation Patterns 632 Essential Terms 633 Study Problems 635

13 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 643 13-1 Introduction 643 13-2 Theory of Nuclear Magnetic Resonance 644 13-3 Magnetic Shielding by Electrons 646 13-4 The NMR Spectrometer 648 13-5 The Chemical Shift 649 13-6 The Number of Signals 656 13-7 Areas of the Peaks 658 13-8 Spin-Spin Splitting 661 PROBLEM-SOLVING STRATEGY: Drawing an NMR Spectrum 666 13-9 Complex Splitting 670 13-10 Stereochemical Nonequivalence of Protons 673 13-11 Time Dependence of NMR Spectroscopy 676 PROBLEM-SOLVING STRATEGY: Interpreting Proton NMR Spectra 679 13-12 Carbon-13 NMR Spectroscopy 684 13-13 Interpreting Carbon NMR Spectra 692 13-14 Nuclear Magnetic Resonance Imaging 694 PROBLEM-SOLVING STRATEGY: Spectroscopy Problems 695 Essential Terms 699 Study Problems 701

14 ETHERS, EPOXIDES, AND THIOETHERS 708 14-1 Introduction 708 14-2 Physical Properties of Ethers 709 14-3 Nomenclature of Ethers 713 14-4 Spectroscopy of Ethers 716 14-5 The Williamson Ether Synthesis 718 14-6 Synthesis of Ethers by Alkoxymercuration-Demercuration 720 14-7 Industrial Synthesis: Bimolecular Condensation of Alcohols 720 Summary: Syntheses of Ethers (Review) 721 14-8 Cleavage of Ethers by HBr and HI 722 14-9 Autoxidation of Ethers 724 Summary: Reactions of Ethers 725 14-10 Thioethers (Sulfides) and Silyl Ethers 725 14-11 Synthesis of Epoxides 729 Summary: Epoxide Syntheses 732 14-12 Acid-Catalyzed Ring Opening of Epoxides 732 14-13 Base-Catalyzed Ring Opening of Epoxides 736 14-14 Orientation of Epoxide Ring Opening 738 Summary: Orientation of Epoxide Ring Opening 739 14-15 Reactions of Epoxides with Grignard and Organolithium Reagents 740 14-16 Epoxy Resins: The Advent of Modern Glues 741 Essential Terms 743 Study Problems 746 Summary: Reactions of Epoxides 743

15 CONJUGATED SYSTEMS, ORBITAL SYMMETRY, AND ULTRAVIOLET SPECTROSCOPY 752 15-1 Introduction 752 15-2 Stabilities of Dienes 753 15-3 Molecular Orbital Picture of a Conjugated System 754 15-4 Allylic Cations 759 15-5 1,2- and 1,4-Addition to Conjugated Dienes 760 15-6 Kinetic Versus Thermodynamic Control in the Addition of HBr to Buta-1,3-diene 762 15-7 Allylic Radicals 764 15-8 Molecular Orbitals of the Allylic System 766 15-9 Electronic Configurations of the Allyl Radical, Cation, and Anion 768 15-10 SN2 Displacement Reactions of Allylic Halides and Tosylates 769 15-11 The Diels-Alder Reaction 770 15-12 The Diels-Alder as an Example of a Pericyclic Reaction 779 15-13 Ultraviolet Absorption Spectroscopy 782 15-14 Colored Organic Compounds 788 15-15 UV-Visible Analysis in Biology and Medicine 790 Essential Terms 792 Study Problems 795

16 AROMATIC COMPOUNDS 800 16-1 Introduction: The Discovery of Benzene 800 16-2 The Structure and Properties of Benzene 801 16-3 The Molecular Orbitals of Benzene 805 16-4 The Molecular Orbital Picture of Cyclobutadiene 808 16-5 Aromatic, Antiaromatic, and Nonaromatic Compounds 809 16-6 Huckel's Rule 810 16-7 Molecular Orbital Derivation of Huckel's Rule 812 16-8 Aromatic Ions 813 16-9 Heterocyclic Aromatic Compounds 819 16-10 Polynuclear Aromatic Hydrocarbons 823 16-11 Aromatic Allotropes of Carbon 825 16-12 Fused Heterocyclic Compounds 827 16-13 Nomenclature of Benzene Derivatives 828 16-14 Physical Properties of Benzene and Its Derivatives 830 16-15 Spectroscopy of Aromatic Compounds 832 Essential Terms 834 Study Problems 836

17 REACTIONS OF AROMATIC COMPOUNDS 845 17-1 Electrophilic Aromatic Substitution 845 17-2 Halogenation of Benzene 847 17-3 Nitration of Benzene 849 17-4 Sulfonation of Benzene 850 17-5 Nitration of Toluene: The Effect of Alkyl Substitution 853 17-6 Activating, Ortho, Para-Directing Substituents 855 Summary: Activating, Ortho, Para-Directors 858 17-7 Deactivating, Meta-Directing Substituents 858 Summary: Deactivating, Meta-Directors 861 17-8 Halogen Substituents: Deactivating, but Ortho, Para-Directing 862 Summary: Directing Effects of Substituents 863 17-9 Effects of Multiple Substituents on Electrophilic Aromatic Substitution 863 17-10 The Friedel-Crafts Alkylation 866 17-11 The Friedel-Crafts Acylation 871 Summary: Comparison of Friedel-Crafts Alkylation and Acylation 873 17-12 Nucleophilic Aromatic Substitution 875 17-13 Aromatic Substitutions Using Organometallic Reagents 879 17-14 Addition Reactions of Benzene Derivatives 885 17-15 Side-Chain Reactions of Benzene Derivatives 888 17-16 Reactions of Phenols 892 PROBLEM-SOLVING STRATEGY: Synthesis Using Electrophilic Aromatic Substitution 895 Summary: Reactions of Aromatic Compounds 899 Summary: Electrophilic Aromatic Substitution of Benzene 902 Summary: Substitutions of Aryl Halides 902 Essential Terms 903 Study Problems 906

18 KETONES AND ALDEHYDES 912 18-1 Carbonyl Compounds 912 18-2 Structure of the Carbonyl Group 913 18-3 Nomenclature of Ketones and Aldehydes 914 18-4 Physical Properties of Ketones and Aldehydes 916 18-5 Spectroscopy of Ketones and Aldehydes 918 18-6 Industrial Importance of Ketones and Aldehydes 924 18-7 Review of Syntheses of Ketones and Aldehydes 925 18-8 Synthesis of Ketones from Carboxylic Acids 929 18-9 Synthesis of Ketones and Aldehydes from Nitriles 929 18-10 Synthesis of Aldehydes and Ketones from Acid Chlorides and Esters 931 Summary: Syntheses of Ketones and Aldehydes 933 18-11 Reactions of Ketones and Aldehydes: Introduction to Nucleophilic Addition 934 18-12 Hydration of Ketones and Aldehydes 938 18-13 Formation of Cyanohydrins 940 18-14 Formation of Imines 942 18-15 Condensations with Hydroxylamine and Hydrazines 945 Summary: Condensations of Amines with Ketones and Aldehydes 946 18-16 Formation of Acetals 947 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 951 18-17 Use of Acetals as Protecting Groups 952 18-18 The Wittig Reaction 954 18-19 Oxidation of Aldehydes 957 18-20 Reductions of Ketones and Aldehydes 958 Summary: Reactions of Ketones and Aldehydes 961 Summary: Nucleophilic Addition Reactions of Aldehydes and Ketones 963 Essential Terms 964 Study Problems 967

19 AMINES 977 19-1 Introduction 977 19-2 Nomenclature of Amines 978 19-3 Structure of Amines 981 19-4 Physical Properties of Amines 983 19-5 Basicity of Amines 984 19-6 Factors that Affect Amine Basicity 986 19-7 Salts of Amines 988 19-8 Spectroscopy of Amines 990 19-9 Reactions of Amines with Ketones and Aldehydes (Review) 994 19-10 Aromatic Substitution of Arylamines and Pyridine 994 19-11 Alkylation of Amines by Alkyl Halides 998 19-12 Acylation of Amines by Acid Chlorides 999 19-13 Formation of Sulfonamides 1001 19-14 Amines as Leaving Groups: The Hofmann Elimination 1003 19-15 Oxidation of Amines; The Cope Elimination 1006 19-16 Reactions of Amines with Nitrous Acid 1009 19-17 Reactions of Arenediazonium Salts 1011 Summary: Reactions of Amines 1014 19-18 Synthesis of Amines by Reductive Amination 1016 19-19 Synthesis of Amines by Acylation-Reduction 1018 19-20 Syntheses Limited to Primary Amines 1020 Summary: Synthesis of Amines 1024 Essential Terms 1025 Study Problems 1028

20 CARBOXYLIC ACIDS 1038 20-1 Introduction 1038 20-2 Nomenclature of Carboxylic Acids 1039 20-3 Structure and Physical Properties of Carboxylic Acids 1042 20-4 Acidity of Carboxylic Acids 1043 20-5 Salts of Carboxylic Acids 1047 20-6 Commercial Sources of Carboxylic Acids 1049 20-7 Spectroscopy of Carboxylic Acids 1051 20-8 Synthesis of Carboxylic Acids 1055 Summary: Syntheses of Carboxylic Acids 1057 20-9 Reactions of Carboxylic Acids and Derivatives; Nucleophilic AcylSubstitution 1058 20-10 Condensation of Acids with Alcohols: The Fischer Esterification 1060 20-11 Esterification Using Diazomethane 1064 20-12 Condensation of Acids with Amines: Direct Synthesis of Amides 1064 20-13 Reduction of Carboxylic Acids 1065 20-14 Alkylation of Carboxylic Acids to Form Ketones 1067 20-15 Synthesis and Use of Acid Chlorides 1067 Summary: Reactions of Carboxylic Acids 1070, 1071 Summary: Reactions of Carboxylic Acids 1070, 1071 Essential Terms 1072 Study Problems 1073

21 CARBOXYLIC ACID DERIVATIVES 1079 21-1 Introduction 1079 21-2 Structure and Nomenclature of Acid Derivatives 1080 21-3 Physical Properties of Carboxylic Acid Derivatives 1087 21-4 Spectroscopy of Carboxylic Acid Derivatives 1089 21-5 Interconversion of Acid Derivatives by Nucleophilic Acyl Substitution 1096 21-6 Transesterification 1105 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1106 21-7 Hydrolysis of Carboxylic Acid Derivatives 1109 21-8 Reduction of Acid Derivatives 1114 21-9 Reactions of Acid Derivatives with Organometallic Reagents 1117 21-10 Summary of the Chemistry of Acid Chlorides 1119 21-11 Summary of the Chemistry of Anhydrides 1121 21-12 Summary of the Chemistry of Esters 1124 21-13 Summary of the Chemistry of Amides 1127 21-14 Summary of the Chemistry of Nitriles 1130 21-15 Thioesters 1131 21-16 Esters and Amides of Carbonic Acid 1133 Essential Terms 1135 Summary: Reactions of Acid Chlorides 1136 Study Problems 1139

22 CONDENSATIONS AND ALPHA SUBSTITUTIONS OF CARBONYL COMPOUNDS 1148 22-1 Introduction 1148 22-2 Enols and Enolate Ions 1150 22-3 Alkylation of Enolate Ions 1153 22-4 Formation and Alkylation of Enamines 1155 22-5 Alpha Halogenation of Ketones 1157 22-6 Alpha Bromination of Acids: The HVZ Reaction 1163 22-7 The Aldol Condensation of Ketones and Aldehydes 1164 22-8 Dehydration of Aldol Products 1168 22-9 Crossed Aldol Condensations 1169 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1170 22-10 Aldol Cyclizations 1172 22-11 Planning Syntheses Using Aldol Condensations 1173 22-12 The Claisen Ester Condensation 1175 22-13 The Dieckmann Condensation: A Claisen Cyclization 1178 22-14 Crossed Claisen Condensations 1179 22-15 Syntheses Using b-Dicarbonyl Compounds 1182 22-16 The Malonic Ester Synthesis 1184 22-17 The Acetoacetic Ester Synthesis 1187 22-18 Conjugate Additions: The Michael Reaction 1190 22-19 The Robinson Annulation 1194 PROBLEM-SOLVING STRATEGY: Proposing Reaction Mechanisms 1195 Summary: Enolate Additions and Condensations 1197 Summary: Reactions of Stabilized Carbanions 1199 Essential Terms 1199 Study Problems 1202

23 CARBOHYDRATES AND NUCLEIC ACIDS 1208 23-1 Introduction 1208 23-2 Classification of Carbohydrates 1209 23-3 Monosaccharides 1210 23-4 Cyclic Structures of Monosaccharides 1214 23-5 Anomers of Monosaccharides; Mutarotation 1218 23-6 Reactions of Monosaccharides: Reduction 1221 23-7 Oxidation of Monosaccharides; Reducing Sugars 1222 23-8 Nonreducing Sugars: Formation of Glycosides 1224 23-9 Ether and Ester Formation 1226 23-10 Chain Shortening: The Ruff Degradation 1229 23-11 Chain Lengthening: The Kiliani-Fischer Synthesis 1230 Summary: Reactions of Sugars 1232 23-12 Disaccharides 1234 23-13 Polysaccharides 1239 23-14 Nucleic Acids: Introduction 1242 23-15 Ribonucleosides and Ribonucleotides 1244 23-16 The Structures of RNA and DNA 1246 23-17 Additional Functions of Nucleotides 1250 Essential Terms 1252 Study Problems 1255

24 AMINO ACIDS, PEPTIDES, AND PROTEINS 1258 24-1 Introduction 1258 24-2 Structure and Stereochemistry of the a-Amino Acids 1259 24-3 Acid-Base Properties of Amino Acids 1263 24-4 Isoelectric Points and Electrophoresis 1265 24-5 Synthesis of Amino Acids 1267 Summary: Syntheses of Amino Acids 1270 24-6 Resolution of Amino Acids 1270 24-7 Reactions of Amino Acids 1271 Summary: Reactions of Amino Acids 1274 24-8 Structure and Nomenclature of Peptides and Proteins 1274 24-9 Peptide Structure Determination 1278 24-10 Laboratory Peptide Synthesis 1283 24-11 Classification of Proteins 1289 24-12 Levels of Protein Structure 1290 24-13 Protein Denaturation 1292 Essential Terms 1295 Study Problems 1297

25 LIPIDS 1301 25-1 Introduction 1301 25-2 Waxes 1302 25-3 Triglycerides 1302 25-4 Saponification of Fats and Oils: Soaps and Detergents 1306 25-5 Phospholipids 1309 25-6 Steroids 1311 25-7 Prostaglandins 1314 25-8 Terpenes 1315 Essential Terms 1318 Study Problems 1319

26 SYNTHETIC POLYMERS 1322 26-1 Introduction 1322 26-2 Chain-Growth Polymers 1323 26-3 Stereochemistry of Polymers 1329 26-4 Stereochemical Control of Polymerization: Ziegler-Natta Catalysts 1330 26-5 Natural and Synthetic Rubbers 1331 26-6 Copolymers of Two or More Monomers 1333 26-7 Step-Growth Polymers 1333 26-8 Polymer Structure and Properties 1337 26-9 Recycling of Plastics 1339 Essential Terms 1340 Study Problems 1342

APPENDICES 1344 1A NMR: Spin-Spin Coupling Constants 1344 1B NMR: Proton Chemical Shifts 1345 1C NMR: 13C Chemical Shifts in Organic Compounds 1347 2A IR: Characteristic Infrared Group Frequencies 1348 2B IR: Characteristic Infrared Absorptions of Functional Groups 1351 3A Methods and Suggestions for Proposing Mechanisms 1353 3B Suggestions for Developing Multistep Syntheses 1355 4 pKa Values for Representative Compounds 1356 5 Summary of Organic Nomenclature 1358 Brief Answers to Selected Problems 1368 Photo Credits 1374 Index 1375