[ I n d e x ]

A Brønsted–Lowry acids and bases, Acyl substitution, 771, 784–786, 822 Absolute configuration, 228–230 105–106 by nucleophilic addition–elimination, Absorption spectrum, 599 opposite charges attract, 135 784–786 Acetaldehyde, 10, 72, 76, 78, 372, 723 predicting the outcome of, 118–120 Acyl transfer reactions, 784 Acetaldehyde enolate, 53 and the synthesis of deuterium and Acylation, 839–840 physical properties, 10 tritium-labeled compounds, Acylation reaction, 678 Acetals, 738–740 134–135 Acylium ions, 437 Acetic acid, 73–74, 76, 78, 113, 118–119, water solubility as the result of salt Adamantane, 180 126, 128, 145, 772 formation, 119–120 Addition polymers, 483, 808 physical properties, 78 Acidic hydrolysis of a nitrile, 801 Addition reaction, 337–390 Acidity: and pKa , 114 of alkenes, 338–340 Acetoacetic ester synthesis, 835–840 effect of solvent on, 130 Adduct, 608 acylation, 839–840 effect of the solvent on, 130 Adenosine diphosphate (ADP), 431 dialkylation, 836 hybridization, 122–123 Adenosine triphosphate (ATP), 273, 431, substituted methyl ketones, 836–837 inductive effects, 123 981–982 Acetone, 14, 57, 72, 79, 720 relationships between structure and, Adenylate cyclase, 1110 Acetonides, 993, 1023 120–123 Adipic acid, 776 Acetonitrile, 75 Acidity constant (Ka ), 113–114 Adipocytes, 1032 Acetyl-coenzyme A, 784 Acids: Adrenaline, 273, 906 Acetyl group, 722 alcohols as, 509 Adrenocortical hormones, 1046 Brønsted–Lowry, 105–106, 137 Acetylcholine, 897–898, 908 Adriamycin, See Doxorubicin Lewis, 102–104 Acetylcholinesterase, 908, 1096 Aggregation compounds, 161 in nonaqueous solutions, 133–134 Acetylenes, 7, 57, 159, 159fn, 292, 326 Aglycone, 989–990 relative strength of, 115 structure of, 40–42 Aklavinone, 955 in water, 106 Acetylenic hydrogen atom, 159, 313 Alanine, 909, 1063, 1066 Acne medications, chemistry of, 459 of terminal alkynes, substitution of, isolectric point of, 1066 Acrylonitrile, anionic polymerization of, 313–314 titration curve for, 1067 486 Achiral molecules, 192, 195, 198, 212, Albrecht, Walther, 618 Actin, 166 471 Albuterol, 501 Acid anhydrides, reactions of, 810–811 Activating groups, 685–686 Alcohol dehydrogenase, 548 Acid-base reactions, 105–109 meta directors, 685–686 Alcohols, 55, 67–68, 130, See also Primary of amines, 917 ortho–para directors, 685 alcohols; Secondary alcohols; curved arrows, 107 Activation energies, 471 Tertiary alcohols mechanism for, 107–108 Active hydrogen compounds, 844 acid-catalyzed dehydration of, 303–309 Acid-catalyzed aldol condensations, Active methylene compounds, 844 as acids, 509 867–868 COPYRIGHTEDActive site, 1091 MATERIAL Acid-catalyzed aldol enolization, 826 of enzyme, 1070 addition of: Acid-catalyzed dehydration, of alcohols, Acyclovir, 1113 acetals, 738–740 303–309 Acyl chlorides (acid chlorides), 679, hemiacetals, 735–736 Acid-catalyzed esterification, 790–792 725–726, 777, 785–786, 786–788 thioacetals, 741 Acid-catalyzed halogenation, of aldehydes aldehydes by reduction of, 725–727 alcohol carbon atom, 499 and ketones, 828 esters from, 791 from alkenes through hydroboration– Acid-catalyzed hemiacetal formation, 736 reactions of, 787–788, 810 oxidation, 349–352 Acid-catalyzed hydration, of alkenes, 354, synthesis of, 786–787 from alkenes through oxymercuration– 505–506 using thionyl chloride, 787 demercuration, 349–350 Acid chlorides, See Acyl chlorides Acyl compounds: boiling points, 501 Acid derivatives, synthesis of, 786 relative reactivity of, 785–786 conversion of, into a mesylate, 516 Acid strength, 113 spectroscopic properties of, 779–781 conversion of, into alkyl halides, 510 Acid–base reactions, 120–123 Acyl groups, 678 dehydration of, 296–297 acids and bases in water, 106–107 Acyl halide, 678 acid-catalyzed, 303–308

I-1

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Alcohols (cont.) spectroscopic properties of, 753–756 Alkene diastereomers, (E )–(Z ) system for carbocation stability and the summary of addition reactions, designating, 292–293 transition state, 309–312 756–757 Alkenes, 56, 57, 143 ethanol, 499, 502, 503–504 synthesis of, 724–729 addition of sulfuric acid to, 338, 346 as a biofuel, 504 Tollens’ test (silver mirror test), 753 addition of water to, 346–349 ethylene, 504 UV spectra, 756 mechanism, 338 polymerization of, 484 Alder, Kurt, 608, 617–618 addition reaction, 338–340 hydrogen bonding, 502 Alditols, 999 alcohols from, through infrared (IR) spectra of, 93–94 Aldol addition product, dehydration of, oxymercuration–demercuration, intermolecular dehydration, ethers by, 867 349–350 517–518 Aldol addition reactions, 865–866 aldehydes by ozonolysis of, 725 mesylates, 514–516 Aldol additions, 866–867 anti 1,2-dihydroxylation of, 528–530 methanol, 502, 503, 509 Aldol condensation reactions, 859 defined, 292 nomenclature, 152–153, 499–500 Aldol condensations, 865, 867 dipole moments in, 63–64 oxidation of, 551–556 acid-catalyzed, 867–868 electrophilic addition: physical properties of, 501–503 crossed, 871–876 of bromine and chlorine, 359–363 primary, 67 cyclizations via, 876–877 defined, 339 propylene glycols, 502, 504 Aldol reactions, synthetic applications of, of hydrogen halides, 340–345 reactions of, 507–508 868–869 functional group, 64 reactions with hydrogen halides, alkyl Aldonic acids, synthesis of, 995–996 halohydrin formation from, 364–366 halides from, 510–513 Aldose, 982, 994–995, 999, 1000–1002 heat of reaction, 293–295 reactions with PBr3 or SOCI2 , alkyl Aldose, d-family of, 1002–1003 how to name, 156–158 halides from, 513–514 Aldotetrose, 982–984, 1001 hydrogenation of, 181–182, 318–319 by reduction of carbonyl compounds, Aliphatic aldehydes, 721 ionic addition to, 343 ketones from, 729–730 546–551 nomenclature of, 721 spectroscopic evidence for, 556 Markovnikov additions, 341 Aliphatic amines, reactions with nitrous structure, 499–500 regioselective reactions, 344 acid, 918 synthesis/reactions, 498–541 Markovnikov’s rule, 340–345 Aliphatic compounds, 627, See also tert-butyl ethers by alkylation of, 520 defined, 341 Aromatic tosylates, 514–515 theoretical explanation of, 341–342 Aliphatic ketones, nomenclature of, 722 triflates, 514–515 mechanism for syn dihydroxylation of, Alkadienes, 591 Aldaric acids, 995–996 368–369 Alkaloids, 849, 894, 907 Aldehyde hydrates, 551 in natural chemical syntheses, 381–382 Alkanedioic acids, 775 Aldehydes, 55, 71–72, 720–770 oxidation of, 369, 781 Alkanes, 56–57, 143 a,b -unsaturated, additions to, environmentally friendly methods, bicyclic, 179–180 877–881 530 acid-catalyzed halogenation of, 828 branched-chain, 147 oxidative cleavage of, 371–373 Baeyer-Villiger oxidation, 751–753 nomenclature of, 145–147 physical properties of, 292 base-promoted halogenation of, 827 chemical reactions of, 180 preparation of carboxylic acids by carbonyl group, 543, 721 chlorination of, 464–465 oxidation of, 781 chemical analyses for, 753 combustion of, 490 properties/synthesis, 291–336 from esters and nitriles, 727–729 cycloalkanes, 143 radical addition to, 481–483 IR spectra of, 753–754 defined, 143 radical polymerization of, 483–487 mass spectra of, 756 halogenation of, 463–464, 475–476 rearrangements, 348–349 NMR spectra of, 754–755 IUPAC nomenclature of, 145–147 relative stabilities of, 293–295 nomenclature of, 721–723 multiple halogen substitution, 463–464 stereochemistry of the ionic addition to, nucleophilic addition to the carbon– no functional group, cause of, 64 327–328 oxygen double bond, 732–735 nomenclature and conformations of, stereospecific reactions, 363–364 oxidation of, 751 146–153 synthesis of alcohols from, 505–508 by oxidation of 1° alcohols, 724–725 petroleum as source of, 143 use in synthesis, 533–534 oxidation of primary alcohols to, 551 physical properties, 159–162 Alkenyl, 241, 274 by ozonolysis of alkenes, 725 polycyclic, 179–1809 Alkenylbenzenes, 700, 702–704 in perfumes, 724 reactions of, with halogens, 463–465 additions to the double bond of, 703 physical properties, 723–724 shapes of, 144–146 conjugated, stability of, 702–704 preparation of carboxylic acids by sources of, 143–144 oxidation of the benzene ring, 704 oxidation of, 781–784 “straight-chain,” 144 oxidation of the side chain, 703–704 reduction by hydride transfer, 548 synthesis of, 180–182 Alkenyne, 591 by reduction of acyl chlorides, esters, unbranched, 146–147 Alkoxide ions, 134 and nitriles, 725–727 Alkanide shift, 310 Alkoxides, 276, 509 relative reactivity, 734 Alkatrienes, 591 Alkoxyl group, 74

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Alkoxyl radicals, 458 oxidative cleavage of, 375 lactams, 802 Alkoxymercuration–demercuration, physical properties of, 292 nitriles: synthesis of ethers by, 520 synthesis of, 291–336 from the dehydration of, 800 Alkyl alcohols, 500 by elimination reactions, 314–316 hydrolysis of, 800–801 Alkyl aryl ethers, cleavage of, 952–953 laboratory application, 314–316 reactions of, 811–812 Alkyl chlorides, 272 terminal: reducing to amines, 913–914 Alkyl chloroformates, 803–805 acidity of, 313 synthesis of, 796 Alkyl groups, 256 substitution of the acetylenic Amine salts, 901–908 branched, nomenclature of, 149–150 hydrogen atom of, 313–314 Amines, 71 and the symbol R, 64–65 Alkynide anions, 316–317 acylation, 917 unbranched, 147 Allenes, 232–233, 592 alkylation, 917 nomenclature of, 147 Allotropes, 185 amides vs., 903 Alkyl halides, 65–66, 239–244 Allyl cation, 586–587 amine salts, 901–908 alcohol reactions with hydrogen halides, Allyl group, 157, 582 aminium salts, 904 510–513 Allyl radical, 582 analysis of, 929–931 alcohol reactions with PBr3 or SOCI2 , molecular orbital description of, 582 in aqueous acids, solubility of, 904–905 513–514 resonance description of, 584–585 arenediazonium salts: conversion of alcohols into, 510 Allylic bromination, 585 coupling reactions of, 924–926 dehydrohalogenation of, 275–276, with N-bromosuccinimide, 476–477 replacement reactions of, 920–923 296–297, 297–303 Allylic carbocations, 582 aromatic, 902–903 bases used in, 276 Allylic chlorination (high temperature), preparation of, through reduction of defined, 275–278 475–476 nitro compounds, 911 favoring an E2 mechanism, 297 Allylic group, 475 basicity of, 901–908 less substituted alkene, formation of, Allylic halides, 263 biologically important, 906–908 using bulky base, 300 in nucleophilic substitution reactions, antihistamines, 907 mechanisms, 276 708–709 neurotransmitters, 908 orientation of groups in the Allylic hydrogens, 475 2-phenylethylamines, 907 transition state, 301–302 Allylic position, 475 tranquilizers, 907 Zaitsev’s rule, 298–300 Allylic radicals, 475–478 vitamins, 907 elimination reactions of, 275–276 defined, 476 chemical analysis, 929 nomenclature of, 151 resonance delocalization of, 478 conjugate addition of, 879, 896 simple, 262–263, 282 stabilization of, by electron diazotization, 918 tertiary, 271, 288 delocalization, 477–478 heterocyclic, 899 Alkyl radicals, geometry of, 471 Allylic substitution, 475–478 basicity of, 902–903 Alkylation, of alkynide anions, 317–318, defined, 475 infrared (IR) spectra of, 94–95 323–324, 336 Alpha (a) carbon atom, 275 monoalkylation of, 914 Alkylbenzenes: a-amino acids, 1062, 1066 additions to the double bond of, 703 synthesis of, 1068–1070 nomenclature, 898–899 conjugated, stability of, 702–703 from potassium phthalimide, 1068 oxidation of, 917–918 preparation of carboxylic acids by resolution of dl-amino acids, physical properties of, 899–900 oxidation of, 782 1069–1070 preparation of, 908–916 reactions of the side chain of, 699–702 Strecker synthesis, 1069 through Curtius rearrangement, 916 reactivity of, and ortho–para direction, a anomer, 985 through Hofmann rearrangement, 698–699 a carbon, 822 914–916 Alkylboranes: a helices, 1086, 1089, 1092 through nucleophilic substitution oxidation/hydrolysis of, 353–355 a hydrogens, 822, 837 reactions, 908–911 regiochemistry and stereochemistry, a-keratin, 1061, 1088–1089 through reduction of nitriles, oximes, 356–357 a substituents, 1041 and amides, 913–914 protonolysis of, 359 Altman, Sidney, 1091 through reduction of nitro Alkyllithium, 134 Aluminum chloride, 109 compounds, 911 Alkyloxonium ion, 130, 243 Amides, 75, 777–778, 796–802 through reductive amination, Alkylpotassium compounds, 557 from acyl chlorides, 796 911–913 Alkylsodium compounds, 557 amines vs., 903 primary, 912 Alkynes, 56–57, 143, 292 from carboxylic acids and ammonium oxidation of, 917–918 addition of hydrogen halides to, carboxylates, 798 preparation of, through Curtius 374–375 from carboxylic anhydrides, 797 rearrangement, 916 addition reaction, 337–390 DCC-promoted amide synthesis, 798 preparation of, through Hofmann functional group, 64 from esters, 797 rearrangement, 914–915 hydrogenation of, 181–182, 321–323 hydrolysis of, 798–800 preparation of, through reduction of nomenclature of, 158–159 by enzymes, 800 nitriles, oximes, and amides, 911

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Amines (cont.) Ammonium ion, 12 replacement reactions of, 920–923 preparation of, through reductive Ammonium salts, 709, 901 salts, instability of, 919 amination, 911–913 Ammonolysis, 797 Arenes, 699 quaternary ammonium salts, 904 Ampelopsin D, 712 ketones from, 729–730 reactions of, 917–920 Ampelopsin F, 712 Arenium ion, 671–677, 690–699 oxidation, 917–918 Ampelopsin G, 712 Arginine, 488, 1001, 1065, 1068, primary aliphatic amines with nitrous Amphetamine, 70, 99, 906 1077–1078, 1084 acid, 918 Amylopectin, 1010–1011 Aromatic amines, 902–903 primary arylamines with nitrous acid, Amylose, 979, 1010 preparation of, through reduction of 918–919 Anderson, C. D., 1112 nitro compounds, 911 secondary amines with nitrous acid, Androsterone, 162, 1044 Aromatic anion, 641 920 Aneshansley, D., 958 Aromatic compounds, 56, 626–668 tertiary amines with nitrous acid, 920 Anet, F. A. L., 422 13C NMR spectra, 653–655 reactions with sulfonyl chlorides, Anethole, 498 benzene, 58 926–929 Angle strain, 167 discovery of, 627–628 as resolving agents, 905–906 Angular methyl groups, 1041 halogenation of, 673–674 secondary, 898–900 Angular shape, of a molecule of water, 45 Kekulé structure for, 58 oxidation of, 918 Aniline, 136, 628, 687 modern theories of the structure of, preparation of, through reduction acetylation of, 929 634–636 of nitriles, oximes, and amides, Anionic polymerization, 528 nitration of, 673–675, 674–675 913–914 Annulenes, 638–639 nomenclature of benzene derivatives, preparation of, through reductive Anomeric carbon atom, 985 628–630 amination, 911–913 Anomeric effect, 988 reactions of, 630–631 spectroscopic analysis, 929–931 Anomers, 985 sulfonation of, 675–676 structure of, 900 Anthracene, 646 thermodynamic stability of, 632–633 summary of preparations and reactions Anti 1,2-dihydroxylation, of alkenes, benzenoid, 645–646 of, 932–935 528–530 in biochemistry, 650–652 tertiary, 913–914 Anti addition: Birch reduction, 710–711 oxidation of, 918 defined, 321 defined, 643 preparation of, through reduction of of hydrogen, 322–323 electrophilic aromatic substitution nitriles, oximes, and amides, 913 Anti conformation, 165, 184 reactions, 670 preparation of, through reductive Anti coplanar conformation, 301 general mechanism for, 671–673 amination, 911–913 Anti-Markovnikov addition, 345 Friedel–Crafts acylation, 678–680 Aminium salts, 904 of water to an alkene, 346 Clemmensen reduction, 683–684 Amino acid sequencers, 1073 Anti-Markovnikov addition of hydrogen synthetic applications of, 683–684 Amino acids, 2–3, 98, 1060 bromide, 481–483 Wolff-Kishner reduction, 684 a-amino acids, 1062, 1066 Anti-Markovnikov hydration of a double Friedel–Crafts alkylation, 676–678, synthesis of, 1068–1070 bond, 352 701 as dipolar ions, 1065–1068 Anti-Markovnikov regioselectivity/syn Friedel–Crafts reactions, limitations of, dl-amino acids, resolution of, stereoselectivity, 506 680–682 1069–1070 Anti-Markovnikov syn hydration, 352 fullerenes, 647 essential, 1065–1068 Antiaromatic compounds, 638, 643–644 1H NMR spectra, 652–653 l-amino acids, 1063–1065 Antibiotic X-206, 525 heterocyclic, 648–650 structures and nomenclature, 1062 Antibodies, 531, 873, 1016–1017, 1060 Hückel’s rule, 637 Amino cyclitol, 1019 Antibonding molecular orbital, 31, 43 infrared spectra of substituted benzenes, Amino sugars, 1015, 1019 Anticodon, 1124–1125 655–656 Aminobenzene, 628 Antigens, 531, 1016 mass spectra of, 657–658 a-Aminonitrile, formation of, during Antihistamines, and vitamins, 907 nonbenzenoid, 647–648 Strecker synthesis, 1069 Antimetabolites, 927–928 nucleophilic substitution reactions, Ammonia: Antioxidants, 489 allylic and benzylic halides in, reaction of, with alkyl halide, 243 Antisense oligonucleotides, 1131 708–709 reactions of aldehydes and ketones with Aprotic solvents, 266–267 reactions of, 669–719 derivatives of, 745–746 Arbutin, 1023 reduction of, 710–712 shape of a molecule of, 45 Arbuzov reaction, 751 spectroscopy of, 652–658 and water, 13 Arenediazonium salts: synthetic applications: Ammonium compounds, eliminations coupling reactions of, 924–926 orientation in disubstituted benzenes, involving: replacement by i F, 922 707–708 Cope elimination, 932 replacement by i I, 922 protecting and blocking groups, use Hofmann elimination, 931 replacement by i OH, 922 of, 706–707 Ammonium cyanate, 3 replacement by hydrogen, 922–923 Aromatic cyclodehydration, 711, 713

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Aromatic ions, 640–642 Bases: in nucleophilic substitution reactions, Aromaticity, 632 Brønsted–Lowry, 105–106, 137 708–709 Artificial sweeteners, 236, 1008–1009 Lewis, 102–104 Benzylic halogenation, 480 Aryl halides, 240, 681, 919, 944–978 in nonaqueous solutions, 133–134 of the side chain, 701–702 C NMR spectra, 967 predicting the strength of, 116 Benzylic hydrogen atoms, 700 defined, 240 relative strength of, 115 Benzylic hydrogens, 479 1H NMR spectra, 966–967 in water, 106 Benzylic radicals, 478–479, 700–702 infrared spectra, 966 Basic hydrolysis of a nitrile, 801 halogenation of the side chain, as insecticides, 967–968 Basic principles, applications of, 47, 97, 701–702 mass spectra, 967 135–136, 184–186 Benzylic substituent, 700 and nucleophilic aromatic substitution, Basicity: Benzyne, 947, 962–965 959–978 nucleophilicity vs., 265–266 elimination–addition mechanism, 962 by addition–elimination (SN Ar order of, 265 Berg, Paul, 1129 mechanism), 960–962 and polarizability, 280, 281 Bergman cycloaromatization, 491 through an elimination–addition Beer’s law, 600 Bergman, R. G., 491 mechanism (benzyne), 962–965 Bends, 18 Bernal, J. D., 1067fn physical properties of, 241 Benedict’s reagents, 994–995, 1019 Bertrand, J. A., 1094 properties of, 944 Bent shape, of a molecule of water, 45 Beryllium hydride, linear geometry of, 46 spectroscopic analysis of, 966–967 Benzaldehyde, 720, 722 Beta (b) carbon atom, 275 Arylamines, basicity of, 902 Benzene, 56, 58–59, 241, 274, 626–628, b eliminations, 275 Arylamines, tertiary, 920 644 b hydrogen atom, 275 Ascorbic acid (vitamin C), 200 discovery of, 627–628 b-anomer, 985–987 Ashworth, Linda, 1106 halogenation of, 673–674 b bends, 1088 Asparagine, 1064, 1084, 1089 Kekulé structure for, 58, 631–632 b-carotene, 855 Aspartame (NutraSweet), 1008 meta-disubstituted, 656 b-dicarbonyl compounds: Aspartic acid, 1008, 1064 modern theories of the structure of, by acylation of ketone enolates, Asymmetric atoms, See Chirality centers 634–636 864–865 Atomic force microscopy (AFM), 648 molecular orbital explanation of the enolates of, 834–835 b Atomic number (Z), 4, 202 structure of, 635–636 -dicarboxylic acids, 806 b Atomic orbitals (AOs), 28, 30–32, 37 monosubstituted, 655 -keto acids, 805 b hybrid, 32 nitration of, 674–675 -pleated sheets, 1086, 1088, 1092 b Atomic structure, 3–4 nomenclature of benzene derivatives, substituents, 1041 and quantum mechanics, 27 628–630 Bhopal, India, methyl isocyanate accident, Atoms, 3–4 ortho-disubstituted, 656 804 Atropisomers, 227, 232 para-disubstituted, 656 BHT (butylated hydroxytoluene), 489 reactions of, 630–631 Bicyclic alkanes, 179–1809 Attractive electric forces, summary of, 85 resonance explanation of the structure Bicyclic cycloalkanes, naming, 155–156 Aufbau principle, 29, 47 of, 634–635 Bicycloalkanes, 156 Aureomycin, 955 sulfonation of, 675–676 Bijvoet, J. M., 230 Automated peptide synthesis, 1084–1086 thermodynamic stability of, 632–633 Bimolecular reaction, 246 Autoxidation, 488–489, 504 Benzene ring, 478 BINAP, 217, 232 Axial bonds, of cyclohexane, 171–172 oxidation of, 704 Biochemistry: Azo dyes, 925 preparation of carboxylic acids by aromatic compounds in, 650–652 B oxidation of, 782 intermolecular forces in, 85 Benzene substitution, 631 Biological methylation, 273 B chains, 1079 Benzenoid aromatic compounds, Biologically active natural products, 362 Bacterial dehalogenation of a PCB 645–646 Biologically important amines, 907–908, derivative, 961–962 Benzenoid polycyclic aromatic 938 Baeyer-Villiger oxidation, 751–753 hydrocarbons, 645–646 2-phenylethylamines, 907 Baker, B. R., 1112 Benzoic acid, 73 antihistamines, 907 Baker, J. T., 525 Benzoyl peroxide, 459 functional groups in, 77 Ball-and-stick models, 14–16, 45 Benzyl, 630 neurotransmitters, 908 Balzani, V., 170 Benzyl chloroformates, 803 tranquilizers, 907 Barger, G., 717 Benzyl groups, 65 vitamins, 907 Barton, D.H.R., 171 Benzylic carbocations, 708 Biomolecules, mass spectrometry (MS) Base-catalyzed hemiacetal formation, 737 Benzylic cations, 700–702 of, 444 Base peak, 432 Benzylic chlorination of methylbenzene, Biphenyl, 716 Base-promoted halogenation, of aldehydes 479 Birch, A. J., 710 and ketones, 827 Benzylic groups, 478–479 Birch reduction, 710–711 Base strength, 116 Benzylic halides, 263 Black biting, 484

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Bloch, Felix, 392 Brønsted–Lowry acid-base chemistry, 318 amino sugars, 1015 Blocking groups, 707 Brønsted–Lowry acids and bases, carbohydrate antibiotics, 1018–1019 Boat conformation, 168–169 105–106, 137 classification of, 980–981 Boduszek, B., 1094 strength of, 120 defined, 980 Boiling points, 81–83, 97, 947 acidity and pKa , 114–116 disaccharides, 980, 1005–1009 alcohols, 501 acidity constant (Ka ), 113–114 Fischer’s proof of the configuration of ethers, 501 predicting the strength of bases, d-(+)-glucose, 1003–1005 intermolecular forces (van der Waals 116–117 glycolipids and glycoproteins of the cell forces), 81–83 Brønsted–Lowry theory, 109 surface, 1016–1017 ionic compounds, 78 Brown, Herbert C., 353 glycoside formation, 988–990 of ionic compounds, 78 Buckminsterfullerene, 142, 186, 647 glycosylamines, 1014–1015 neopentane, 81 1,3-Butadiene, 592–594 as a major chemical repository for solar nonpolar compounds, 82 bond lengths, 592–594 energy, 981 unbranched alkanes, 160 conformations of, 593 monosaccharides, 980, 1003, 1009, Bombardier beetle, 958 molecular orbitals of, 593–594 1016–1017, 1019 Bond angles, 16 Butane, 144, 146, 294 mutarotation, 987–988 Bond breaking, as endothermic process, conformational analysis of, 166 oligosaccharides, 980 460 Butanoic acid, 772 photosynthesis and carbohydrate Butanone, synthesis of 2-butanol by the Bond dissociation energies, 460–463 metabolism, 981–982 nickel-catalyzed hydrogenation Bond length, 30 polysaccharides, 980, 1009–1013 of, 214 Bond-line formulas, 16, 18–19, 501 summary of reactions of, 1019 Butenandt, Adolf, 1044 drawing, 18–19 trisaccharides, 980 Butlerov, Alexander M., 627 Bond rotation, 162–164 Carbolic acids, See Phenols Butyl alcohol, 132, 502 Bonding molecular orbital, 31, 31–35, 37 Carbon, 6, 8 Bonding pairs, 44 Butyric acid, 772 origin of, 2 Bone growth, organic templates Carbon-13 NMR (carbon-13) NMR engineered to mimic, 86 C spectroscopy, 396, 422–427 Born, Max, 28 13 C NMR (carbon-13) NMR broadband (BB) proton decoupled, 423 Borneol, 571 Spectroscopy, See Carbon-13 C chemical shifts, 423–425 Boron trifluoride, 62 NMR (carbon-13) NMR chemical shifts, 408–411 trigonal planar structure of, 45–46 spectroscopy: DEPT 13C NMR spectra, 425–427 Bovine chymotrypsinogen, 1079 C-terminal residues, 1070, 1075 interpretation of, 422 Bovine ribonuclease, 1079 Cahn, R. S., 202 one peak for each magnetically distinct Bovine trypsinogen, 1079 Cahn–Ingold–Prelog system of naming carbon atom, 422–423 Boyer, Paul D., 532 enantiomers, 202–206, 204, 234, spin decoupling, 420–421 Bradsher, C. K., 610 292 Carbon atom, 242–243, 247–248, 248 Bradsher reaction, 713 Calicheamicin g1 l, 491–492 Carbon compounds: Branched alkyl groups, how to name, Camphene, 311 alkyl halides (haloalkanes), 65–66 149–150 Camphor, 571 amides, 75 Branched-chain alkanes: Cannizzaro reaction, 854 carboxylic acids, 73–74 how to name, 147–149 Cantharidin, 817 esters, 74 nomenclature of, 145–147 Capillary electrophoresis, 1130 Breathalyzer alcohol test, 555 Capillin, 57 families of, 55–103 Breslow, R., 233 Capsaicin, 48–49, 969 functional groups, 62–64 Bridge, 155 Carbaldehyde, 721 hydrocarbons, 56–59 Bridgeheads, 155 -carbaldehyde, suffix added to nitriles, 75 Bromides, 272 aldehydes, 721 polar and nonpolar molecules, 61–63 Bromination, of phenols, 953 Carbamates (urethanes), 804 polar covalent bonds, 59–61 Bromine, 465 Carbanion 3, 964 Carbon dating, 4 addition to cis- and trans-2-butene, Carbanions, 121–123, 544 Carbon dioxide, 46–47 359–360 relative acidity of, 123 Carbon tetrachloride, 241 electrophilic addition of bromine to relative basicity of, 123 Carbon–carbon double bond, 7, 56, 64, alkenes, 359–363 Carbenes, 366–368 92 reaction with alkanes, 463 Carbenoids, 368 Carbon–carbon single bond, 7 selectivity of, 471 Carbocations, 131, 163, 256–258 Carbon–carbon triple bond, 7 Bromine water, 1002, 1007, 1019 relative stabilities of, 256–258 Carbonic acid, derivatives of, 802–803 2-Bromobutane, 363 structure of, 256 Carbonic anhydrase, 1088–1090, 1094 Bromoform, 828–829 Carbohydrates, 283, 979–1026, See also Carbon–oxygen double bond: Bromohydrin, 365 Disaccharides; Monosaccharides; nucleophilic addition of ketones to, Bromonium ion, 361 Polysaccharides 732–735

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reversibility of nucleophilic additions lactones, 794–795 racemic forms (racemic mixture), to, 734 nitriles, 778–779 213–214 Carbonyl compounds, 821–857 nomenclature, 772–773 stereoselective reactions, 214–215 acetoacetic ester synthesis, 835–840 oxidation of primary alcohols to, 551 synthesis of, 213–215 acidity of the a hydrogens of, 822–823 physical properties, 772–773 Chiral object, defined, 192 alcohols by reduction of, 546–551 polyamides, 808 Chiral templates, 206 alcohols from, 542–580 polyesters, 807–808 Chirality: condensation and conjugate addition preparation of, 781–784 biological significance of, 193, reactions of, 858–896 reactions of, 809 199–200 defined, 543 Carboxylic anhydrides, 777 importance of, 193 enamines, synthesis of, 844–850 Carboxypeptidase A, 1091 in molecules, 193, 196 haloform reaction, 828–829 Carboxypeptidases, 1075–1076 and stereochemistry, 192–193 halogenation at the a carbon, 827–828 Carcinogenic compounds, 652 testing for, 201 Hell–Volhard–Zelinski (HVZ) reaction, Carcinogens, and epoxides, 534 Chirality centers, 196–199, 471 830–831 Carotenes, 1039 compounds other than carbon with, lithium enolates, 831 Carrier ionophore, 532 232 oxidation and reduction of, 544 Carvone, 72, 199, 211 molecules with multiple, 220–223 racemization via enols and enolates, Catalytic antibodies, 1096–1097 meso compounds, 220–221 825–827 Catalytic asymmetric dihydroxylation, naming compounds with, 222–223 reactions at the a carbon of, 821–857 370–371 molecules with one, 196–199 reactions of Grignard reagents with, Catalytic cracking, 143–144 proceeding with retention of 560–561 Catalytic hydrogenation, 318–319 configuration, 227–228 reactions with nucleophiles, 544 Catalytic triad, 1094–1095 Chitin, 1015 substituted acetic acids, synthesis of, Catenanes, 170, 171 Chloracne, 968 840–843 Cation-anion forces, 85 Chlordiazepoxide, 907 Carbonyl dichloride, 802–803 Cation-exchange resins, 1071–1072 Chloride ion, 105, 246–247, 254–255, Carbonyl functional groups, 542 Cationic carbon, 255 279, 785–787 infrared (IR) spectra of, 92–93 Cationic oxygen atom, 949 Chlorination: Carbonyl groups, 71–72, 721 Celera Genomics Company, 1135 of alkanes, 464, 469 nucleophilic addition to, 544 Cellobiose, 1008 of benzene, 674 stereoselective reductions of, 550–551 Cellulose, 1009, 1012–1013 of chlorobenzene, 688 structure of, 543–544 Cellulose derivatives, 1013 of isobutane, 464 Carbowaxes, 528 Cellulose trinitrate, 1013 of methane: Carboxyl group, 73 Chain branching, 484, 484–485 activation energies, 471 activation of, 1082–1083 Chain-growth polymers, 483–485 mechanism of reaction, 465–468 Carboxyl radicals, decarboxylation of, 806 Chain-initiating step, in fluorination, 466, of pentane, 471 Carboxylate anion, 753, 773–774, 829, 490 of water, 829 1034 Chain mechanism, 468 Chlorine, 6, 247, 251, 255, 279, 284, Carboxylate salts, 773 Chain-propagating steps, 466, 476, 490 425 Carboxylic acid anhydrides, 788–789 Chain reaction, 466, 482 electrophilic addition of bromine to reactions of, 789 Chain-terminating (dideoxynucleotide) alkenes, 344 synthesis of, 788–789 method, 1128–1131 reaction with alkanes, 463 Carboxylic acid derivatives, 772, 786 Chain-terminating steps, 467, 476 Chlorine selectivity, lack of, 464–465 Carboxylic acids, 73–74, 771–820 Chair conformation, 168–169 Chlorobenzene, 959, 962, 967–968 a-halo, 830–831 Chair conformational structures, drawing, electrophilic substitutions of (table), acidity of, 127, 773–775 172 688 acyl chlorides, 777 Chaires, J. B., 217 hydrolysis of (Dow Process), 947 acyl compounds: Chargaff, Erwin, 1115 Chloroethane, 151, 408–409 chemical tests for, 807 Chemical Abstracts Service (CAS), 179 physical properties, 78 relative reactivity of, 785–786 Chemical bonds, 5 Chlorofluorocarbons (CFCs), 490–491 spectroscopic properties of, 779–781 Chemical energy, defined, 124 Chloroform, 241, 828 acyl substitution, 784–786 Chemical exchange, 420–421 dipole moment, 63 amides, 777–778 Chemical shift, 393–394, 423–425 in drinking water, 830 carboxylic anhydrides, 777 parts per million (ppm) and the d scale, Chlorohydrin, 365 decarboxylation of, 805–807 394, 919 Chloromethane, 245–248, 250–251, 261 dicarboxylic acids, 775–776 Chemotherapy, 934–935 physical properties, 78 esterification, 789–792 Chiral drugs, 215–217 Chloromethane molecule, net dipole esters, 776–777 Chiral molecules, 193 moment, 62 infrared (IR) spectra of, 94 Fischer projections, 223–224 Chloromethylation, 819 lactams, 802 not possessing chirality center, 232–233 Chlorophyll, 48–49

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Chloroplasts, 981 Coenzymes, 651, 1091, 1110 allylic substitution, 582 Chlorpheniramine, 907 Coenzymes Q (CoQ), 957–958 1,3-butadiene/z0, 592–594 Cholesterol, 217, 499, 1042–1044 Cofactor, 1091 conjugated dienes: chemistry of, 505 Collagen, 86 electrophilic attack on, 604–607 Cholic acid, 1048 Collision-induced dissociation (CID), stability of, 595–596 Choline, 273 1076 defined, 582 Cholinergic synapses, 908 Combination bands, 90 Diels–Alder reaction, 611–618 Chromate ester, formation of, 554 Combustion of alkanes, 490 electron delocalization, 592–594 Chromate oxidations, mechanism of, 554 Common names, for compounds, 145 resonance theory, 587–591 Chromatography using chiral media, 231 Competitive inhibitor, 505, 1091 ultraviolet–visible spectroscopy, Chromic acid oxidation, 554–555 Complete sequence analysis, 1075–1076 598–600 Chylomicrons, 1043 Compounds, 3 Connectivity, 14–16 Chymotrypsin, 800, 1079, 1091, Concept maps, 49, 54, 103, 190 Constitutional isomers, 14–16, 145, 195, 1094–1096 Concerted reaction, 248 206 Chymotrypsinogen, 1094 Condensation reactions, 808, 858–859 Constructive interference, 27 Cialis, 457, 488 Condensed formula, 15–17 Cope elimination, 932, 934 Cinnamaldehyde, 720 Condensed structural formulas, 17–18 Cope rearrangement, 957 Cis, 292 condensed, 17–18 Corey, E. J., 324, 369, 525, 617, 667, cis-1-chloro-3-methylcyclopentane, 251 Configurations: 1057 Cis–trans isomerisers, of cyclohexane (R) and (S ), 228–230 Corey, Robert B., 1087 derivatives, 225 inversion of, 272 Corpus luteum, 1045 Cis–trans isomerism, 175–179 relative and absolute, 228–230 COSY spectrum, 428–430 cis 1,2-disubstituted cyclohexanes, Conformational analysis, 162, 163–164 Coulson, C. A., 637 178–179 of butane, 166 Couper, Archibald Scott, 627 cis 1,3-disubstituted cyclohexanes, 178 of ethane, 163–164 Coupling, 1133 cis 1,4-disubstituted cyclohexanes, hyperconjugation, 163 Coupling constants, 413, 416–420 176–177 of methylcyclohexane, 173–174 dependence on dihedral angle, 416–417 and conformational structures of performing, 162–163 reciprocity of, 416 cyclohexanes, 176–179 Conformational isomers, 232 Coupling reactions, of arenediazonium trans 1,2-disubstituted cyclohexanes, Conformational stereoisomers, 166, 227 salts, 924–926 178–179 Conformations, 162 Coupling (signal splitting), 396–398 trans 1,3-disubstituted cyclohexanes, eclipsed, 163 Covalent bonds, 5 177–178 staggered, 163 formation of, 6 trans 1,4-disubstituted cyclohexanes, Conformer, 162 homolysis and heterolysis of, 458 176, 292 Conjugate acid, 116–117, 829, 832 and Lewis structures, 6–7 Cis–trans isomers, 39 of ammonia, 117 multiple, 7 physical properties, 62 of methylamine, 117 Citrus-flavored soft drinks, chemistry of, Conjugate acid, of water, 105 and potential energy (PE), 124–125 366 Conjugate acid–base strengths, summary Cracking, 143–144 Civetone, 162, 724 and comparison of, 129 Crafts, James M., 676 Claisen condensation: Conjugate addition, 858 Cram, D., 965 crossed, 862–863 of amines, 879, 896 Cram, Donald J., 531 defined, 859 of enolates, 879–881 Cresols, 945 examples of, 859 example of, 859 Crick, Francis, 1114–1115, 1120 intramolecular, 862 of HCN, 879 Crixivan, 323 mechanism for, 860–861 Conjugate addition reactions, 859, 869 Cross peaks, 428–430 synthesis of b-keto esters, 846, Conjugate addition, to activate drugs, 881 Crossed aldol condensations, 871–876 859–864 Conjugate base, 116 using strong bases, 874–876 Claisen rearrangement, 944–945, 956, Conjugated dienes: using weak bases, 872–874 957, 978 electrophilic attack on, 604–607 Crossed aldol reaction, 872–873 Claisen–Schmidt condensations, 872 stability of, 595–596 Crossed Claisen condensation, 862–863 Cleavage: Conjugated double bonds: Crown ethers, 531–532 of ethers, 522–523 alkadienes, 591–592 defined, 531 with hot basic potassium permanganate, polyunsaturated hydrocarbons, as phase transfer catalysts, 531 371–372 591–592 and transport antibiotics, 532 with ozone, 372–373 Conjugated proteins, 1096 Crutzen, P. J., 490 Clemmensen reduction, 683–684, 741 Conjugated unsaturated systems, Cumene hydroperoxide, 948–949 Clostridium botulinum, 919 581–625 Cumulated double bonds, 591 Codeine, 571 allyl cation, 586–587 qus, 592 Codon, 1124 allyl radical, 584–585 Curl, R. F., 647

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Curtius rearrangement, preparation of Cyclopentane, 161, 167, 168 mechanism for, 302 amines through, 916 derivatives, 225 mechanisms of, 276 alkylation of ammonia, 908–909 Cyclopropane, 57, 167 orientation of groups in the alkylation of azide ion and reduction, Cysteine, 1062, 1064 transition state, 301–302 909 Cytochrome P450, 535 Zaitsev’s rule, 298–300 alkylation of tertiary amines, 911 Cytosine methylation, 1139 bases used in, 276 Gabriel synthesis, 909–910 Cytosine–guanine base pair, 1120 defined, 275 Curved arrows, 22 mechanisms of, 276 illustrating reactions with, 107 D of vic-dibromides to form alkynes, 315 Cyanohydrins, 746–747 d-Fructose, 283 Delocalization: preparation of carboxylic acids by d-Glucaric acid, 996, 1005 and acidity of carboxylic acids, 127 hydrolysis of, 782–783 d-Glucosamine, 1015 of a charge, 127 Cyclamate, 1008–1009 d-Tubocurarine, 897–898, 908 of electrons, 137 Cycles per second (cps), 597 D vitamins, 1046–1047 Delocalization effect, 128 39,59-Cyclic adenylic acid (cyclic AMP), Dacron, 808 Deoxy sugars, 1014 1110 Dactylyne, 57, 337–338, 362 Deoxyribonucleic acid (DNA), 1106, See Cyclic anhydrides, 788 D’Amico, Derin C., 854 also DNA sequence Cyclic compounds, stereoisomerism of, Darvon (dextropropoxyphene), 216 defined, 1106 225–227 Darzens condensation, 892 determining the base sequence of, Cyclic guanosine monophosphate Dash structural formulas, 6–7, 16–17, 49 1128–1131 (cGMP), 488 Daunomycin, 955 DNA sequencing, 1106, 1129, 1130 Cyclizations, via aldol condensations, Daunorubicin, 217 by the chain-terminating method, 876–877 De Broglie, Louis, 28 1129–1131 Cycloalkanes, 143 Deactivating groups, 685–686 heterocyclic bases, 1107–1108, 1110, angle strain, 167 meta directors, 688 1113 bicyclic, naming, 155–156 ortho–para directors, 688 microchips, 1135 defined, 143 Deacylases, 1070 primary structure of, 1113–1114 disubstituted, 175–179 Debye, 60 replication of, 1118–1120 higher, conformations of, 171 Debye, P. J. W., 60 secondary structure of, 1114–1118 13 naming, 153–155 Decalin, 179–180 DEPT C NMR spectra, 425–427, 717, nomenclature of, 153–154 Decane, 146 755, 765, 819 physical constants, 161 Decarboxylation, 744 DEPT spectra, 653 physical properties, 159–162 of carboxyl radicals, 806–807 Deshielding, protons, 406–407 ring strain, 167 of carboxylic acids, 805–807 Designer catalysts, 1017 synthesis of, 180–182 Deconvolution, 1109–1100 Destructive interference, 27 torsional strain, 167 Decyl alcohol, 84 Detritylation, 1133 Cycloalkenes, 296 Degenerate orbitals, 29 Deuterium atoms, 4 retro-Diels–Alder reaction, 439 Degree of unsaturation, use of term, Dextrorotary, 208, 229 Cycloalkyalkanes, 154 182fn Diacyl peroxide, 483 Cyclobutadiene, 59, 639, 643–644 Dehydration, 734 Dialkyl carbonate, 803–804 Cyclobutane, 167 of alcohols, 296–297, 297, 346 Dialkyl ethers, 522 Cycloheptane, 171 carbocation stability and the transition Dialkylation, 836 Cycloheptatriene, 642–643 state, 306–308 Dialkylcarbodiimides, 798 Cyclohexane, 184 defined, 297 Diamond, 142 conformations of, 168–169 of primary alcohols, 312 Diamox, 1094 substituted, 171–175 mechanism for, 308 Dianeackerone, 762 Cyclohexane derivatives, 224–225 rearrangement after, 312 Diastereomeric recrystallization, 231 1,2-dimethylcyclohexanes, 226–227 of secondary alcohols, 304–311 Diastereomers, 194–195, 219, 225, 472, 1,3-dimethylcyclohexanes, 226 mechanism for, 305–306 473 1,4-dimethylcyclohexanes, 225 rearrangements during, 309–311 Diastereoselective, use of term 214 cis–trans isomerisers of, 225 of tertiary alcohols, 303–307 Diastereoselective reactions, 550 Cyclohexene, 360, 367, 633 mechanism for, 305–306 Diastereotopic hydrogens, 472 Cyclononane, 171 Dehydrobenzene, See Benzyne Diatomic molecules, 61 Cyclooctadecane, 171 Dehydrohalogenation: 1,3-Diaxial interaction, 174–175 Cyclooctane, 171 of alkyl halides, 275–276, 297–303 of a tert-butyl group, 173 Cyclooctatetraene, 632, 637–638, 644 bases used in, 276 Diazo coupling reaction, 924 Cyclooxygenase, 1050 defined, 275 Diazonium salts, 918, 920 Cyclopentadiene, 611, 640–641 favoring an E2 mechanism, 297 syntheses using, 921 Cyclopentadienyl anion, 640–642, 644, less substituted alkene, formation of, Diazotization, 918–919 647 using bulky base, 300–301 deamination by, 922–923

solom_index_I01-I26hr.indd 9 11/19/12 3:16 PM I-10 Index

Diborane, 353 Diprotic acid, 106 Electromagnetic spectrum, 597–598 Dibromobenzenes, 628 Dirac, Paul, 27 Electron deficient, 462 2,3Dibromopentane, 217–218 Direct alkylation: Electron-deficient atoms, as Lewis acids, Dicarboxylic acids, 776–777 of esters, 833, 848 110 Dichlorocarbene, sysnthesis of, 367 of ketones, via lithium enolates, 833 Electron delocalization, 592–594 Dicyclohexano-18-crown-6, 531 Directed aldol reactions, 871 Electron density surfaces, 36, 257, 263, Dicyclohexylcarbodiimide, 798, 1110 and lithium enolates, 874–876 268, 277 Dieckmann condensation, 862 Directive effect, 694 Electron-donating resonance effect, 692, Dielectric constants, 267 Disaccharides, 980, 980–1009 696 Diels, Otto, 608, 617–618 artificial sweeteners, 1008–1009 Electron impact (EI) ionization, 432, Diels–Alder reaction, 439, 581, 593, cellobiose, 1008–1009 434–435 611–618, 1060, 1097 defined, 980 Electron probability density, 28 factors favoring, 609–610 lactose, 1002, 1009 Electron-withdrawing effect of a phenyl molecular orbital considerations maltose, 980–981, 1006–1008 group, 902 favoring an endo transition state, sucrose, 283, 980–981, 1005–1006, Electron-withdrawing substituents, 621–622 1008 690–691 predicting the products of, 614–615 Dispersion forces, 80–81, 85, 88–89, 166 Electronegative groups, deshielding, 423 retrosynthetic analysis, using in, Dispersive IR spectrometers, 87 Electronegativity, 5, 49, 60 615–616 Dissolving metal reduction, 322 Electronegativity differences polarize Diels–Alder reaction, stereochemistry of, Disubstituted benzenes, orientation in, bonds (principle), 135 610–614 707–708 Electronic factors, in aldehydes and Diene, 608 Disubstituted cycloalkanes, 175–179 ketones, 734 Dienophile, 608 Divalent carbon compounds, 366–367 Electronic spectra, 600 Diethyl ether, 499–505, 517, 522 dl-amino acids, resolution of, Electrons, 3–4 physical properties, 82 1069–1070 configurations, 29–30 Difference bands, 90 DNA, See Deoxyribonucleic acid (DNA) delocalization of, 137 Digitoxigenin, 1048 DNA polymerase, 1133 donating, as inductive effect, 123 1,2 dihalides, 314 DNA sequence, 1076–1077, 1077, 1106, energy of, 43 Dihalocarbenes, 367 1131, 1135–1136 sharing, 6 Dihedral angle, 163, 190, 416–417 DNA sequencing, by chain-terminating withdrawing, as inductive effect, 123 1,2-Dihydroxylation, 368 (dideoxynucleotide) method, Electrophiles, 112–113, 318, 339, Diisobutylaluminum hydride 1129–1131 339–340 (DIBAL-H), 726 Dodecane, 146 as Lewis acids, 340 Diisopropyl ester, 524 Doisy, Edward, 1044 Electrophilic addition: Diisopropylcarbodiimide, 798, 1083– Domagk, Gerhard, 935 of bromine and chlorine to alkenes, 1084 Dopamine, 70, 744 359–363 Diisopropylphosphofluoridate (DIPF), Double-bond character, 959 defined, 339 1096 Double bonds, 21, 274, 277, 279 of hydrogen halides to alkenes, 1,2-Dimethoxyethane (DME), 502 Double-headed arrows (4), 23–24 340–345 Dimethoxytrityl (DMTr) group, 1133 Doublets, 397, 412 Electrophilic aromatic substitutions Dimethyl ether, 69, 502–503 Dow process, 947 (EAS), 718, 917, 920, 924, 929 intermolecular forces, 80 Downfield, use of term, 399 effect of substituents on, 690–699 Dimethylbenzenes, 629 Doxorubicin, 954–955, 1052 electron-releasing and electron- 1,2-Dimethylcyclohexane, 226–227 Dyes, 925 withdrawing groups, 690–691 2,4-Dinitrofluorobenzene, 1074 inductive and resonance effects, 2,4-Dinitrophenylhydrazones, 743, 753 E 691–692 Diols, 153 E1 reactions, 276, 278–280 meta-directing groups, 693–694 Diosgenin, 1048 mechanism for, 279 ortho–para-directing groups, 1,4-Dioxane, 500–501, 502 SN1 reactions vs., 282 694–698 Dipeptides, 1070, 1075–1077, 1080 E2 elimination, 302, 317 ortho–para direction and reactivity of Dipolar ions: E2 reactions, 275–278 alkylbenzenes, 698–699 amino acids as, 1065–1068 mechanism for, 276–277 table, 689 defined, 1065 SN2 reactions vs., 280–282 and thyroxine biosynthesis, 670, 674 Dipole, 60 stereochemistry of, 301–303 Electrospray ionization (ESI), 444–445, Dipole moments, 60 Eclipsed conformation, 163 1099 in alkenes, 63 Edman degradation, 1073–1074 mass spectrometry (MS) with permanent, 79 Edman, Pehr, 1073 (ESI-MS), 1100 and physical properties of molecules, 97 Ehrlich, Paul, 935 Electrostatic potential, 110 simple molecules, 61 Eicosane, 146 maps, 23, 60–61, 121–128, 318 Dipole–dipole forces, 85 Eisner, T., 958 Elements, 3–4

solom_index_I01-I26hr.indd 10 11/19/12 3:16 PM Index I-11

defined, 3–4 Enthalpy change, 125, 135 bond length, 36 electronegativities of, 5 Entropy change (DS), 125 carbon–carbon bond of, 57 periodic table of, 2, 4, inside front cover Environmentally friendly alkene oxidation conformational analysis of, 163–164 Eleutherobin, 362 methods, 530 physical properties, 78 Elimination reactions, 276, 281, 734 Enzyme-substrate complex, 1090 radical halogenation of, 468 of alkyl halides, 275–276 Enzymes, 193, 214–215 sp2 hybridization, 30 defined, 296 defined, 1090 Ethane, structure of, 35–36 synthesis of alkenes via, 296–297 resolution by, 221 Ethanoic acid, 145, 772 synthesis of alkynes by, 314–316 Epichlorohydrin (1-(chloromethyl) Ethanol, 499, 502, 503–504 Eliminations: oxirane), 527, 538 as a biofuel, 504 b eliminations, 275 Epimerization, 826–827, 857, 1019 as an hypnotic, 504 1,2 eliminations, 275 Epimers, 826, 1000 miscibility of, 84, 503 Elion, Gertrude, 1113 Epoxidation: Ethanoyl group, 722 Enal, 867 alkene epoxidation, 524 Ethene (ethylene), 7, 57 Enamines, 741, 744–745, 746, 757, 844 Sharpless asymmetric epoxidation, anionic polymerization of, 483 synthesis of, 844–847 524–525 bond length, 36 Enantiomeric excess, 212–213, 217, 524 stereochemistry of, 525 physical properties, 36–40, 78 Enantiomerically pure, use of term, 253 Epoxides, 523–530 radical polymerization of, 483–485 Enantiomerism, 231 acid-catalyzed ring opening of, Ethers, 69, See also Epoxides Enantiomers, 194–196, 202, 206 525–526 boiling points, 501 and chiral molecules, 195 anti 1,2-dihydroxylation of alkenes via, cleavage of, 522–523 naming, 202–206 528–530 crown, 531–532 optical activity, 206–211 base-catalyzed ring opening of, 526 cyclic, naming, 500 origin of, 211–213 carcinogens and biological oxidation, dialkyl, 522 plane-polarized light, 207–208 534 diethyl ether, 82, 502, 504–505, 522 polarimeter, 208–209 defined, 523 as general anesthetics, 69 specific rotation, 209–211 epoxidation, 523–525 hydrogen bonding, 502 Pasteur’s method for separating, 231 hidden, 534–535 by intermolecular dehydration of properties of, 206–207 polyethers from, 528 alcohols, 518 resolution, methods for, 231 reactions of, 525–528 nomenclature, 500–501 selective binding of drug enantiomers synthesis of, 523–525 oxygen atom, 499 to left- and right-handed coiled Equatorial bonds, of cyclohexane, physical properties of, 501–503 DNA, 217 171–172 protecting groups, 520–521 separation of, 231 Equilibrium, 23 silyl, 521 Enantioselective, 214 Equilibrium constant (Keq ), 113 reactions of, 522–523 Enantioselective reactions, 214, 550 Erythromycin, 795, 955 synthesis of, 517–521 Enantiotopic hydrogen atoms, 472 Eschenmoser, A., 323, 617 by alkoxymercuration– Endergonic reactions, 248–249 Essential amino acids, 650, 1065 demercuration, 520 Endo, 611 Essential nutrients, 927–928 synthesis/reactions, 498–541 Endothermic reactions, 125, 460 Essential oils, 1037 trimethylsilyl, 521 Energies of activation, 471 Esterifications, 789–792 Williamson synthesis of, 518–519 Energy, 27 Fischer, 790 Ethinyl estradiol, 57 defined, 123 transesterification, 792 Ethyl acetate, 74 Energy changes, 123–125 Esters, 74, 726, 771–820 physical properties, 78 Energy state, 27 from acyl chlorides, 791 Ethyl alcohol, 67, 153 Enol form, 823 aldehydes by reduction of, 727–729 physical properties, 78 Enol tautomers, 861 amides from, 797 Ethyl bromide, 378 Enolate anions, 822–823 from carboxylic acid anhydrides, Ethyl group, 65 Enolate chemistry, summary of, 847–848 791–792 Ethyl methyl ether, 502 Enolates: direct alkylation of esters, 833, 848 Ethylamine, 70 of b-dicarbonyl compounds, 834–835 esterification, 789 Ethylbenzene, 699, 701 defined, 822 acid-catalyzed, 790–792 Ethylene, 504 racemization via, 825–827 reactions of, 811 polymerization of, 483–484 reactions via, 825–834 saponification, 792–794 Ethylene oxide, 501 regioselective formation of, 832–833 synthesis of, 789–792 Ethyllithium, 134 Enols (alkene alcohols), 821–822 Estradiol, 200, 946, 1044–1046 Ethyne (acetylene), 7, 57 racemization via, 834–836 Estrogens, 1044 bond length, 30 reactions via, 825–834 synthetic, 1045 physical properties, 78 Enone, 867 Ethanal, 721 sp2 hybridization, 40–42 Enthalpies, 125 Ethane, 7, 115, 146 structure of, 40–42

solom_index_I01-I26hr.indd 11 11/19/12 3:16 PM I-12 Index

Ethynyl group, 159 Fourier transform NMR spectrometers, location of, for diseases on chromosome Ethynylestradiol, 1045 403–404 19 (schematic map), 1107 Eucalyptol, 381–382 Fourneau, Ernest, 935 Genetic code, 1077, 1102, 1121, 1123, Eugenol, 70, 627, 946 [4+2] cycloaddition, 609 1124–1126 Exchangeable protons, 421 Franklin, Rosalind, 1114 Genetics, basics of, 1106 Excited states, 32 Free energy of activation, 248 Genomics, 1100 Exergonic reactions, 248 Free energy change: Gentamicins, 1019 Exhaustive methylation, 992 for the reaction, 248 Geometric specificity, 1091 Exo, 611 relationship between the equilibrium Geranial, 385 Exons, 1121 constant and, 125–126 Gibbs free-energy change, 125fn Exothermic reactions, 125, 460 Free-energy diagrams, 248–249 Gibbs, J. W., 125fn Extremozymes, 550 Free induction decay (FID), 404 Globular tertiary structures, 1089 (E )–(Z ) system for designating, 292–293 Free radicals, See Radicals Glucan, 1009 Freons, 490 Glucoside, 988 F Frequency (n), 88–89, 597 Glutamic acid, 977, 1064, 1068, 1072 Frequency of radiation, 88 Glutamine, 1064, 1089, 1102 Faraday, Michael, 627 Friedel, Charles, 676 Glutathione, 1077 Farnesene, 385 Friedel–Crafts acylation, 678–680 Glycans, See Polysaccharides Fat substitutes, 1032–1033 Clemmensen reduction, 683–684 Glyceraldehyde entantiomer, 229–230 Fats, 1028–1029 synthetic applications of, 683–684 Glyceraldehyde-3-phosphate trans, 1032 Wolff-Kishner reduction, 684 dehydrogenase (GAPDH), 651 Fatty acids, 75, 319, 1028–1037 Friedel–Crafts alkylation, 676–678, 701 Glycerol, 502 composition, 1029, 1031 Friedel–Crafts reactions, limitations of, Glycidic ester, 892 omega-3, 1029–1030 680–682 Glycine, 139, 1062 reactions of the carboxyl group of, Fructose, 980 Glycogen, 1009, 1011–1012 1035–1036 Fructosides, 988 Glycolipids, 1016–1017 saturated, 1029 Fullerenes, 647–648 lipids, 1054 unsaturated, 1029 Fumaric acid, 386, 789 Glycols, 153, 368 reactions of the alkenyl chain of, Functional class nomenclature, 151 Glycolysis, 821, 870 1036 Functional groups, 60, 62–64 Glycoproteins, 1017–1018 Fehling’s solution, 994 defined, 62 Glycosides: Fibrous tertiary structures, 1089 interconversion (functional group defined, 988 First-order spectra, 420 transformation), 271–272 formation, 988–990 Fischer, Emil, 984, 984fn, 1090 Furan, 649–650 hydrolysis of, 989 Fischer esterifications, 790 Furanose, 986, 1006, 1019 Glycosylamines, 1014–1015 Fischer projections, 984–985 Furchgott, R. F., 487 Glycylvalylphenylalanine, 1071 defined, 223–224 Goodman, L., 1112 drawing/using, 223–224 G Gramicidin, 532 Fleet, G.W. J., 1025 Gabriel synthesis of amines, 910, 932, Graphene, 185 Fleming, Alexander, 444 1068 Graphite, 185 Floss, H., 1025 Galactan, 1009 Grignard reaction, mechanism for, 561 Fluoride anion, 268 Gamma globulin, 1079 Grignard reagents, 558 Fluorination, chain-initiating step in, 466 Garfield, S., 137 alcohols from, 561–569 Fluorine, 674 Gas chromatography (GC), 350, 443, 521 Grignard synthesis, planning, 564–565 electronegativity of, 5 Gates, M., 617 preparation of carboxylic acids by reaction with alkanes, 463 Gauche-butane, 174 carbonation of, 783–784 Fluorobenzene, 681–682 Gauche conformations, 165 reactions with carbonyl compounds, Fluorocarbons, chemistry of, 82 Gauche interaction, 174 560–561 Fokt, I., 217 GC/MS (gas chromatography with mass reactions with epoxides (oxiranes), 560 Folic acid, 927–928, 1091 spectrometry), 392 restrictions on the use of, 567–568 Formal charges, 49 analysis, 443 Grignard, Victor, 558 calculating, 12–13 Gel electrophoresis, 1098–1099, 1105, Ground state, 32 summary of, 13 1130–1131 Group numbers, atoms, 4 Formaldehyde, 25, 720, 723 Gelb, M. H., 1080fn bond angles, 72 gem-diols, 737 H Formic acid, 73, 145, 772 Geminal dihalide (gem-dihalide), 316 1H–1H correlation spectroscopy, 428 Formyl group, 722 General statement of Markovnikov’s rule, Half-chair conformations, 169 Fourier transform, 87, 404, 431 343–344 Halo alcohol, 364 Fourier transform infrared (FTIR) Genes: a-Haloalcohols, 539 spectrometer, 87 defined, 1106 Haloalkanes, 65, 76

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Haloform reaction, 785, 828–829 Heteronuclear correlation spectroscopy Human hemoglobin, 1079 Halogen addition, mechanism of, (HETCOR, or C–H HETCOR), Hund’s rule, 29, 47, 637 360–363 428–430 Hybrid atomic orbitals, 32, 43 Halogen atoms, 240, 243, 274–275, 458 Heteropolysaccharides, 1009 Hybrid of resonance structures, 22 Halogen molecules, 458 Heterotopic atoms, 408–409 Hybridization, and acidity, 122–123 Halogen substituents, 688 Hexadecane, 146 Hydrate formation, 737 Halogenation at the a carbon, 831–834 Hexane isomers, physical constants of, Hydrating ions, 83 Halogens: 146 Hydration, of alkenes, 346, 505 compounds containing, 183 Hexanoic acid, 772 Hydrazones, 743 reactions of alkanes with, 463–465 Hexose, 982, 1006 Hydride ions, 119, 544 Halohydrin: High-density lipoproteins (HDLs), 1043 Hydride shift, 310 defined, 365 High-performance liquid chromatography Hydroboration: (HPLC), 231, 603, 1072–1073 defined, 352 formation, 364–366 High-resolution mass spectrometry, mechanism of, 353–354 mechanism for, 365–366 442–443 stereochemistry of, 355 Halomon, 362 Highest occupied molecular orbital synthesis of alkylboranes, 353–355 Halonium ions, 363 (HOMO), 247, 471, 594, 601, Hydroboration–oxidation, 505–506, 506 Haloperoxidases, 362 625 alcohols from alkenes through, 352 Halothane, 505 Hinsberg test, 926–927, 929 as regioselective reactions, 356–357 Hammond–Leffler postulate, 263–264, Hirst, E. L., 985fn Hydrocarbons, 56–59, 92, 143, 292 299 Histamine, 744, 907 IR spectra of, 91–92 Haptens, 1097 Histidine, 1065, 1075 relative acidity of, 123 Harington, C., 717 Histrionicotoxin, 897, 908 Hydrogen, 6 Hassel, O., 171 Hitchings, George, 1113 anti addition of, 322–323 Haworth formulas, 984–985 Hodgkin, Dorothy Crowfoot, 444 atomic number, 202 Haworth, W. N., 765fn Hofmann elimination, 904, 931, 934 syn addition of, 321–322 HCN, conjugate addition of, 896 Hofmann product, 302 Hydrogen abstraction, 458–459 Heat contents, 125 Hofmann rearrangement, preparation of Hydrogen atoms, 256, 262, 266–267, Heat of hydrogenation, 294–295 amines through, 914–916 275–276 Heat of reaction, 294–295 Hofmann rule, 300, 931 classification of, 150 Heisenberg uncertainty principle, 30 Homogeneous catalysis, 318 Hydrogen bonds, 79–84, 97, 502–503, Heisenberg, Werner, 27 Homologous series, 159 723 Hell–Volhard–Zelinski (HVZ) reaction, Homologues, 159 formation of, 85 830–831 Homolysis, 458 Hydrogen bromide, 106, 275, 374–375, Heme, 657, 1096 Homolytic bond dissociation energies 703 Hemiacetals, 735–736, 985–988 (DH°), 460–463 anti-Markovnikov addition of, 481–483 acid-catalyzed formation, 736 calculating, 460 Hydrogen chloride, 106 base-catalyzed formation, 737 defined, 460 Hydrogen halides, 510 essential structural features of, 735 using to determine the relative addition to alkynes, 340 formation of, 735 stabilities of radicals, 460–461 electrophilic addition to alkenes, Hemicarcerand, 965 Homopolysaccharides, 1009 339–340 Hydrogen peroxide, 485, 487 Hemoglobin, 85, 1061, 1079, 1090, Homotopic hydrogen atoms, 464 Hooke’s law, 88 Hydrogenases, 215 1096, 1098, 1128 Horner–Wadsworth–Emmons reaction, Hydrogenation, 294–295 Henderson–Hasselbalch equation, 1066 750–751, 763 of alkenes, 181–182, 318–319, 338 Heparin, 1015 Host-guest relationship, 531 of alkynes, 181–182, 321–323 Heptadecane, 146 Hot basic potassium permanganate, in the food industry, 319 Heptane, 146 cleavage with, 371–372 function of the catalyst, 320–321 Hertz, H. R., 597fn HSQC, 428 Hydrogenolysis, 765 Hertz (Hz), 405, 416, 597 Hückel’s rule, 640, 643–645, 646, 660 Hydrolysis, 215 Heteroatoms, 60 annulenes, 638–639 acetals, 738 Heterocyclic amines, 899 aromatic ions, 640–642 acid-catalyzed, 525, 529–530, 533 basicity of, 902–903 diagramming the relative energies of of alkylboranes, 355–358, 506 Heterocyclic aromatic compounds, orbitals in monocyclic conjugated regiochemistry and stereochemistry, 648–650 systems based on, 637 356–358 Heterogeneous catalysis, 318 NMR spectroscopy, 639–640 of amides, 798–800 Heterogeneous catalyst, 321 Huffman, D., 647 by enzymes, 800 Heterolysis, 111, 135 Hughes, Edward D., 246 Hydronium ion, 106 Heterolytically, use of term, 132, 133, Human Genome Project, 1106, 1130 Hydrophilic, use of term, 84, 1034 305, 458 Human genome, sequencing of, 1100 Hydrophobic effect, 84

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Hydrophobic group, 84 in biochemistry, 85 Isobutylene, polymerization of, 485 Hydrophobic, use of term, 84, 1034 boiling points, 81–83 Isoelectric focusing, 1100 Hydroquinone, oxidation of, 957 dipole–dipole forces, 79 Isoelectric point, 1065–1066, 1098, 1100 Hydroxide ion, 106 dispersion forces, 80–81 Isolable stereoisomers, 227 Hydroxybenzene, 628, 945 hydrogen bonding, 79–80 Isolated double bonds, 591–592 3-Hydroxybutanal, 865, 867, 869, 871 organic templates engineered to mimic Isoleucine, 1088, 1102 Hydroxyl group, alcohols, 67 bone growth, 86 Isomaltose, 1022 Hydroxyproline, 1062, 1072, 1089 solubilities, 83–84 Isomers, 14 4-Hydroxyproline, 1064 International Union of Pure and Applied subdivision of, 195 Hyperconjugation, 163, 256–257, 263 Chemistry (IUPAC), 15fn, Isooctane, 144 145–146 Isopentane, 145 I system for naming alkanes, 146–147 Isoprene units, 1037 Ibuprofen, 215 Intramolecular Claisen condensation, 862 Isopropyl, 150 Ignarro, L. J., 487 Introns, 1121 Isopropyl alcohol, 499, 502 Imines, 741–742, 742 Inversion, 247, 744 condensed structural formula for, 17 Index of hydrogen deficiency (IHD): Inversion of configuration, 272 equivalent dash formulas for, 16 calculating for compounds, 183–184 Iodide, 265–266 Isopropyl group, 149 defined, 182 Iodination, 674, 828 Isopropylamine, 71 gaining structural information from, Iodine, reaction with alkanes, 475 Isopropylbenzene, 699 182–184 Iodomethane, 240, 265, 939 Isotope-coded affinity tags (ICAT), 1102 Indole system, 650 Ion sorting, 443 Isotopes, 4 Induced field, 406–407, 640, 652–653 Ion trapping, 532 IUPAC system, for naming alkanes, Induced fit, 1090 Ion–dipole forces, 83, 85 145–147 Inductive effects, 123, 135, 609–610, 695 Ionic bonds, 5 and acidity of carboxylic acids, Ionic compounds, 6 J boiling points, 78 127–128 Jones reagent, 554–555 ion–ion forces, 78–79 of other groups, 129 Joule (J), 125fn Ionic reactions, 106, 230–284, 458 Inductive electron-withdrawing effects, Jung, Michael E., 854fn 128 carbocations, 131, 163, 256–258 Industrial styrene synthesis, 701 relative stabilities of, 256–258 K Infrared (IR) spectroscopy, 54, 86–90 structure of, 256 alcohols, 93–94 E1 reaction, 276, 278–280 Kam, C. M., 1094 amines, 94–95 E2 reaction, 275–278 Kanamycins, 1019 carbonyl functional groups, 92–93 free-energy diagrams, 248–249 Karplus correlation, 416 carboxylic acids, 94 leaving groups, 245 Karplus, Martin, 416 defined, 86 nucleophiles, 242–245 Katz, T., 660 dispersive IR spectrometers, 87 organic halides, 263, 557, 567, 708, Kekulé, August, 58, 631–632 Fourier transform infrared (FTIR) 751 Kekulé structures, 58 spectrometer, 87 SN1 reaction, 246–248 for benzene, 632 functional groups containing mechanism for, 247–248 Kekulé–Couper–Butlerov theory of heteroatoms, 92–93 rate-determining step, 246–247 valence, 627–628 hydrocarbons, 91–92 SN2 reaction, 245–248 Ketene, 819 interpreting IR spectra, 90–95 measuring, 245–246 Keto form, 823–824 phenols, 93–94 mechanism for, 246–248 Keto tautomers, 861 wavenumbers, 87 stereochemistry of, 272 Ketone enolates, b-dicarbonyl compounds Infrared spectra, of substituted benzenes, transition state, 247–251 by acylation of, 864–865 655–656 temperature and reaction rate, Ketones, 55–56, 71–72, 720–770 Ingold, Christopher K., 202, 246 249–250 a,b -unsaturated, additions to, 865, Inhibitors, aromatase, 1046 Ionization, 432 877–878 Initial ozonides, 373 Ionophore antibiotics, 532 acid-catalyzed halogenation of, Initial rates, 246 Ionophores, 532 827–828 Insulin, 1078–1079 Ions, 5 from alkenes, arenes, and 2° alcohols, Integration of signal areas, 396 Ipatiew, W., 855 729–730 Interferogram, 87 Ipecacuanha, 934 Baeyer-Villiger oxidation, 751–753 Intermediates, 104, 254 Iron(III) halides (ferric halides), 110 base-promoted halogenation of, Intermolecular dehydration: Isoborneol, 311, 571 827–828 of alcohols, ethers by, 517–518 Isobutane, 145 carbonyl group, 543, 721 complications of, 517–518 Isobutyl, 150 chemical analyses for, 753 Intermolecular forces (van der Waals Isobutyl alcohol, 502 direct alkylation of, via lithium forces), 79–80, 85 Isobutyl bromide, 287 enolates, 833

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IR spectra of, 753–754 Left-handed coiled DNA, selective regioselective formation of enolates, mass spectra of, 756 binding of drug enantiomers to, 832 from nitriles, 730–731 217 Lithium reagents, use of, 568 NMR spectra of, 754–755 Lehn, Jean-Marie, 531 Lithium tri-tert-butoxyaluminum hydride, nomenclature of, 721–723 Less substituted alkene: 726 nucleophilic addition to the carbon– defined, 300 Lobry de Bruyn–Alberda van Ekenstein oxygen double bond, 732–735 formation of, using bulky base, 300– transformation, 990 oxidation of, 761 301 Lock-and-key hypothesis, 1090 oxidation of secondary alcohols to, 551 Leucine, 1088, 1102 London forces, See Dispersion forces in perfumes, 724 Leveling effect, 115fn Lone pairs, 38 physical properties, 723–724 of a solvent, 313 Loop conformations, 1086, 1088 relative reactivity, 734 Levitra, 457, 488 Loschmidt, Johann Josef, 631fn spectroscopic properties of, 753–756 Levorotary, 208 Lovastatin, 48–49, 505 summary of addition reactions, 756– Lewis acid–base reactions, 135, 137 Low-density lipoproteins (LDLs), 1043 757 Lewis acid–base theory, 109 “Low-resolution” mass spectrometers, synthesis of, 729–731 Lewis acids, 102–104 442 Tollens’ test (silver mirror test), 753 as electrophiles, 110, 340 Lowest occupied molecular orbital UV spectra, 756 Lewis acids and bases, 109–111 (LOMO), 601 Ketopentose, 982, 984 Lewis bases, 102–104 Lowest unoccupied molecular orbital Ketose, 982, 994 as nucleophiles, 112 (LUMO), 247 Kharasch, M. S., 481 Lewis, G. N., 5, 109–111 Lucas, H. J., 539 Kiliani–Fischer synthesis, 747, Lewis structures, 22, 49 Lucite, 426, 485 1000–1004 and covalent bonds, 6–7 Lycopene, 601 Kilocalorie of energy, 125 defined, 7 Lycopodine, 894 Kinetic control, 299 rules for writing/drawing, 7–8 Lysine, 870, 1067–1068, 1072 defined, 605 Ligands, BINAP, 217, 232 isolectric point of, 1068 thermodynamic control of a chemical Light, as electromagnetic phenomenon, Lysozyme, 1061, 1076 reaction vs., 605–607 207 mode of action, 1092–1094 Kinetic energy (KE), 123 Like charges repel (principle), 47, 184 Kinetic enolate, 832–833 Limonene, 199, 385 M Linalool, 853 formation of, 832, 864 Macrocyclic lactones, 795 Kinetic products, 605 Lindlar’s catalyst, 322 Linear polymers, 1070 Macromolecules, 483 Kinetic resolution, 215 Magnetic resonance, 392 Kinetics, defined, 245 Linoleic acid, 489 Lipase, 215 Magnetic resonance imaging (MRI), 391, Knowles, William S., 216, 370, 524 431 Kolbe reaction, 956 Lipid bilayers, 1051 Lipids, 532, 820, 1027–1059 MALDI mass spectrometry, 444 Kössel, W., 5 defined, 1028 MALDI (matrix-assisted laser desorption Krätschmer, W., 647 fatty acids, 75, 319, 1035–1036 ionization, 1100 Kroto, H. W., 647 glycolipids, 1054 Maleic acid, 386 Kumepaloxane, 362 in materials science and bioengineering, Malonic acids, 806 Malonic ester synthesis, 955 L 1036–1037 phosphatides, 1051–1053 of substituted acetic acids, 840–843 l-amino acids, 233, 1063–1065, 1069 phospholipids, 1050–1055 Maltose, 980–981, 1006–1008 Lactams, 802 prostaglandins, 1049–1050 Mannich bases, 882 Lactones, 102, 794–795 sphingosine, derivatives of, 1053–1054 Mannich reaction, 882 Lactose, 1002, 1009 steroids, 1040–1049 Mannosides, 988 Ladder sequencing, 1076 terpenes, 1037 Map of electrostatic potential (MEP), 53, Langmuir–Blodgett (LB) films, terpenoids, 1037 60–61 1036–1037 triacylglycerols, 1028–1035 Markovnikov additions, 341 Laqueur, Ernest, 1044 waxes, 1054 anti-, 345 (3E)-Laureatin, 337–338, 362 Lithium aluminum hydride, 547 exception to, 345 LCAO (linear combination of atomic overall summary of, 548–549 regioselective reactions, 344 orbitals) method, 31 Lithium diisopropylamide (LDA), 831, Markovnikov regioselectivity, 505–506 Le Bel, J. A., 20, 231, 1003 864, 875 Markovnikov, V., 341 Leaving groups, 241–242 Lithium, electronegativity of, 5 Markovnikov’s rule, 340–345, 481 defined, 241–242, 245 Lithium enolates, 831–834 defined, 341 ionization of, 263–264 direct alkylation of ketones via, 832– general statement of, 343–344 nature of, 269–271 833 theoretical explanation of, 341–342 Lecithins, 1051 and directed aldol reactions, 874–876 Masamune, S., 1009

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Mass spectrometry (MS), 426–443, mechanism of reaction, 465–468 gaining structural information from, 1127 orbital hybridization, 32 182–184 base peak, 432 physical properties, 78 Molecular handedness, 199 of biomolecules, 444 structure of, 32–34 Molecular ion: determining molecular formulas and tetrahedral structure of, 20 depicting, 432–433 molecular weights using, 442–443 valance shell of, 44–45 and isotopic peaks, 440 electron impact (EI) ionization, 432, Methanide ion, 121 Molecular orbitals (MOs), 30–32, 43, 434–435 Methanide shift, 310 47, 49 electrospray ionization (ESI), 444–445, Methanogens, 56 antibonding, 43 1099 Methanoic acid, 772 bonding, 31 electrospray ionization with mass Methanol, 242, 246, 260, 265, 267, 276, explanation of the structure of benzene, spectrometry (ESI-MS), 1100 503, 509 635–636 fragmentation by cleavage of two miscibility of, 84, 503 theory, 47 bonds, 439–440 physical properties, 502 Molecular oxygen, 487 fragmentation to form resonance- Methanolysis, 260–261 Molecular recognition, 531 stabilized cations, 437–439 Methanoyl group, 722 Molecular structure determines properties GC/MS (gas chromatography with Methionine, 273, 1054, 1088 (principle), 97 mass spectrometry), 443 synthesis of, 1068 Molecularity, 246 high-resolution, 442–443 Methoxide anion, 265 Molecules: ion sorting and detection, 443 Methyl alcohol (methanol), 67, 153 composition of, 6 ion trap mass analyzers, 532 Methyl carbocation, 257, 263 with Nobel Prize in synthetic lineage, matrix-assisted laser desorption– Methyl cyanoacrylate, 487 617 ionization (MALDI), 444 Methyl group, 65 Molina, M. J., 490 molecular formula, determining, Methyl halides, 261–262, 836 Molozonides, 373 442–443 Methyl ketones, 755 Monensin, 532 molecular ion, 432–433 converting to carboxylic acids, 829 Monoalkylation, of an amines, 914 and isotopic peaks, 440 synthesis of, 836–837 Monomers, 483 peptide sequencing using, 1076–1077 Methyl salicylate, 627, 946 Mononitrotoluenes, 686 polypetides/proteins, 1076–1077 Methylaminium ion, 117 Monosaccharides, 283, 1009, 1016–1017, quadrupole mass analyzer, 444 Methylbenzene, 479, 628 1019 time-of-flight (TOF) mass analyzer, 444 Methylcyclohexane, 184 aldaric acids, 995–996 Matrix-assisted laser desorption– conformational analysis of, 173–174 alditols, 999 ionization (MALDI), 444, 1100 Methyldopa, 215 aldonic acids, synthesis of, 995–996 Mauveine, 136–137 Methylene chloride, 241 bromine water, 995–996, 1002, 1007 Maxam, A., 1129 Methylene group, 65 carbohydrate synthesis, use of Mayo, F. R., 481 Methylene, structure and reactions of, 367 protecting groups in, 991 McLafferty rearrangement, 440 1-methylethyl, 149 classification of, 980–981 Meisenheimer intermediate, 960 Methylheptadecane, 161 conversion to cyclic acetals, 993 Melting point, 63, 77 2-methylhexane, retrosynthetic analysis conversion to esters, 993 Menthol, 498 for, 326 d and l designations of, 983–984 Mercapto group, 650 Methyloxirane, 526 deoxy sugars, 1014 6-Mercaptopurine, 650, 1113 2-methylpropene, addition of HBr to, enolization, 990–991 Merrifield, R. B., 820, 1084 343 ethers, formation of, 991–993 Mescaline, 906–907 Mevalonate ion, 505 isomerization, 990 Meso compounds, 213–214 Micelles, 1033–1034 Kiliani–Fischer synthesis, 747, Messenger RNA (mRNA) synthesis, Michael additions, 845, 879–881 1000–1004 1121, 1124–1125 Michael, Arthur, 879 nitric acid oxidation, 995–996 synthesis-transcription, 1121 Michelson interferometer, 87 oxidation reactions of, 994–998 Mesylates, 514–516 Micrometers, 87 Benedict’s reagents, 994–995 meta-Chloroperoxybenzoic acid Micron, 597 Tollens’ reagents, 994–995 (MCPBA), 523 Miller, S., 233 oxidative cleavage of polyhydroxy Meta directors, 688 Millimicron, 597 compounds, 997–998 activating groups, 685–686 Mirror planes of symmetry, 201, 234 periodate oxidations, 997–998 deactivating groups, 688 Mitomycin, 881, 1127 reducing sugars, 994–995 Meta-disubstituted benzenes, 656 Mitscherlich, Eilhardt, 627 Ruff degradation, 1002 Metarhodopsin, 328 Mixed triacylglycerold triacylglycerol, structural formulas for, 984–987 Meth-Cohn, O., 137 1029 tautomerization, 990–991 Methane, 6, 143, 146 Molar absorptivity, 600 uronic acids, 1013 chlorination of: Molecular formulas,14 Monosaccharides derivatives, 1009–1110 activation energies, 471 determining, 442–443 Monosubstituted benzenes, 655

solom_index_I01-I26hr.indd 16 11/19/12 3:16 PM Index I-17

Montagnon, T., 137 Neighboring-group effects, 539 Novestrol, 1045 Montreal Protocol, 491 Neighboring-group participation, 289 Noyori, R., 216, 370, 524 Moore, S., 1072 Neomycins, 1019 Nuclear magnetic resonance (NMR) Morphine, 617, 906–907 Neopentane, 145–146, 151, 465 spectrometry, 385–426, 1127 MRI (magnetic resonance imaging) scan, boiling point, 81 13C NMR (carbon-13) NMR 391, 431 Neopentyl group, 150 Spectroscopy, 422–427 MOs, See Molecular orbitals (MOs) Neopentyl halides, 262, 265 broadband (BB) proton decoupled, MudPIT (multidimensional protein Neurotransmitters, 908 423 identification technology), 1100 Neutrons, 3–4 chemical shifts, 423–425 Mullis, Kary B., 1133 Newman projection formula, 162 DEPT 13C NMR spectra, 425–427 Multidimensional FTNMR spectroscopy, Newman projections, 162–163 interpretation of, 422 428 Niacin (nicotinic acid), 101, 907, 1091 one peak for each magnetically Multiple covalent bonds, 7 Nicolaou, K. C., 491, 525, 609, 617, 623, distinct carbon atom, 422–423 Multiple halogen substitution, 463–464 759, 813, 970 chemical shift, 393–394, 423–425 Murad, F., 487 Nicotinamide adenine dinucleotide, parts per million (ppm) and the d Murchison meteorite, 233 651–652 scale, 394, 405 Muscalure, 161, 326 Nicotine, 70, 907 chemical shift equivalent, 408–411 Muscle action, chemistry of, 166 Ninhydrin, 1072 heterotopic atoms, 408–409 Muscone, 724 Nitrate ion, 12 homotopic hydrogens, 408–409 Mutagens, 1120 Nitrates, 919 complex interactions, analysis of, Mutarotation, 987–988 Nitric acid, 10, 674–675 418–420 Mycomycin, 387 oxidation, 995–996 conformational changes, 421–422 Myelin, 1054 Nitric oxide, 457, 488 coupling (signal splitting), 396–398 Myelin sheath, 1027 Nitriles, 75, 726 defined, 391 Mylar, 808 acidic hydrolysis of, 801 diastereotopic hydrogen atoms, 410–411 Myoglobin, 1089–1090 aldehydes by reduction of, 728 enantiotopic hydrogen atoms, Myosin, 166, 1088 basic hydrolysis of, 801 410–411, 472 Myrcene, 385 ketones from, 729–730 first-order spectra, 420 preparation of carboxylic acids by Fourier transform NMR spectrometers, N hydrolysis of, 782–783 403–404 reactions of, 812 N-acetyl-d-glucosamine, 1015 1H NMR spectra, 412, 416, 417–420, Nitrites, 919 N-acetylglucosamine, 1015, 1017, 1092 422 N Nitrogen, compounds containing, 184 -acetylmuramic acid, 1015, 1092 magnetic resonance imaging (MRI), N-acylamino acids, 1070 Nitrogen inversion, 901 391, 431 N-bromosuccinimide (NBS), 479, 712 Nitrous acid, reactions of amines with, multidimensional FTNMR N-methylmorpholine N-oxide (NMO), 918–920 spectroscopy, 428 369 primary aliphatic amines, 918 nuclear spin, 401–403 N-nitrosoamines, 919 primary arylamines, 918–919 proton NMR spectra: N-terminal, 1070, 1073–1074 secondary amines, 920 complicating features, 417–418 NAD+, 651–652 tertiary amines, 920 interpreting, 398–401 NADH, 651–652 Nitrous oxide (laughing gas), 69 and rate processes, 420–422 Naming enantiomers, 202–206 Noble gas structure, 25 Nanoscale motors and molecular switches, Nodes, 27, 43 protons, shielding/deshielding, 170 Nonactin, 532 406–407 Nanotubes, 185, 648 Nonadecane, 146 second-order spectra, 420 Naphthalene, 646 Nonane, 146 signal areas, integration of, 396 Naphthols, 945 Nonaqueous solutions, acids and bases in, signal splitting, 396–398 Naproxen, 216 133–134 spin decoupling, chemical exchange as Natta, Guilio, 484 Nonaromatic compounds, 643–644 cause of, 420–421 Natural products, and treatment of Nonaromatic cyclohexadienyl carbocation, spin–spin coupling, 411–420 disease, 48–49 678 coupling constants, 416–420 Natural products chemistry, 3 Nonbenzenoid aromatic compounds, origin of, 411 Natural rubber, 1040 647–648 splitting tree diagrams, 412–416 Naturally occurring phenols, 946 Nonbonding pairs, 44 vicinal coupling, 411–412 Nature prefers disorder to order Nonivamide, 969 splitting patterns, recognizing, 415 (principle), 136 Nonpolar compounds, boiling point, 82 two-dimensional NMR (2D NMR) Nature prefers states of lower potential Nonpolar molecules, 61–63 techniques, 428–431 energy (principle), 135–136, 184 Nonreducing sugars, 994 1H-1H COSY spectrum, 428–430 Nature tends toward states of lower Noradrenaline, 906–907 heteronuclear correlation cross-peak potential energy (principle), 47 Norethindrone, 68, 1045 correlations, 430–431

solom_index_I01-I26hr.indd 17 11/19/12 3:16 PM I-18 Index

Nuclear magnetic resonance (NMR) polarimeter, 207, 208–209, 219, 231 Organic synthesis, 323–329 spectrometry (cont.) racemic forms (racemic mixture), defined, 323 heteronuclear correlation 212–214 planning, 324 spectroscopy (HETCOR, or C–H and enantiomeric excess, 212–213 retrosynthetic analysis, 324–325 HETCOR), 428–430 specific rotation, 209–211 Organic templates, engineered to mimic Nuclear magnetic resonance (NMR) Optical purity, 213 bone growth, 86 spectrum, 392–398 Optical rotatory dispersion, 210 Organic vitamin, 3 Nuclear spin, 401–403 Optically active compounds, 207 Organolithium compounds, 557–561 Nucleic acids, 1105–1139 Orange II, 925 reactions of, 557 water solubility, 85 Orbital hybridization, 32 Organomagnesium compounds, 558–561 Nucleophiles, 241, 242–245, 318, 508, Orbital overlap stabilized molecules reactions of, 558–561 511–512, 522, 799, 831 (principle), 47 Organometallic compounds, 556–557 in acylation reactions, 917 Orbitals, 28 Orientation, 611–613, 685, 696 defined, 242 Organic chemistry: Orlon, 485 reactions of carbonyl compounds with, defined, 2 Ortho-disubstituted benzenes, 656 544 development of the science of, 3 Orthogonal protecting groups, 1084 Nucleophilic addition, 544 oxidation–reduction reactions in, Ortho–para direction, and reactivity of Nucleophilic substitution, 239 545–546 alkylbenzenes, 698–699 reaction, 273–274 structural formulas, writing/ Ortho–para directors, 685, 688, 694–698, substrates for, 515 interpreting, 15–18 917 Nucleophilic substitution reactions, Organic compounds: Osazones, 999–1000 273–274 as bases, 130–131 Osmium tetroxide, 368, 368–369, 371 allylic and benzylic halides in, 708–709 families of, 76–77 Oxetane, 500 Nucleophilicity, 265–266 ion–ion forces, 78–79 Oxidation, 1133 basicity vs., 265–266 molecular structure, 77–85 of alcohols, 551–556 Nucleosides, 1014–1015 physical properties, 77–85 of alkenes, 369, 781 Nucleotides/nucleosides, 1106 Organic halides, 263, 557, 708, 751 environmentally friendly methods, laboratory synthesis, 1110–1113 analogous, 567 530 medical applications, 1113 as herbicides, 968 of alkylboranes, 355–358 silyl–Hilbert–Johnson nucleosidation, Organic molecules, 4 regiochemistry and stereochemistry, 1110, 1137 Organic reactions, 104–141 356–358 Number of double-bond equivalencies, acid–base reactions, 120–123 defined, 551 use of term, 182fn predicting the outcome of, 118–120 oxidation states in organic chemistry, Nylon, 808 and the synthesis of deuterium 545–546 and tritium-labeled compounds, Swern, 552–553, 724–725 O 134–135 Oxidation–reduction reaction, 276 Octadecane, 146 acidity, effect of the solvent on, 130 Oxidative cleavage, 371–372, 376 Octadecanoic acid, 772 acids and bases in nonaqueous of alkenes, 371–373 Octane, 146 solutions, 133–134 of alkynes, 375 Octet rule, 5 Brønsted–Lowry acids and bases, Oxidizing agents, 545, 703, 706, 715 exceptions to, 11–12 105–106 Oximes, 743, 913–914 Oils, 1029, 1031 carbanions, 111–113 Olah, George A., 256 carbocations, 111–113 reducing to amines, 933 Olefiant gas, 292 carboxylic acids, acidity of, 127–128 Oxirane, 500, 502 Olefins, 292 covalent bonds: Oxonium cation, 733 Oleksyszyn, J., 1094 homolysis and heterolysis of, 453 Oxonium ion, 130 Olestra, 1032–1033 and potential energy, 124–125 Oxonium salts, 522 Oligonucleotides, laboratory synthesis of, electrophiles, 112–113 Oxygen: 1131–1133 eliminations, 275 atomic number, 202 Oligopeptides, 443, 1070 energy changes, 123–125 compounds containing, 184 Oligosaccharides, 980 illustrating using curved arrows, 107 as a radical, 487 Olympiadane, 171 intermediates, 104 Oxymercuration–demercuration, 506 Omega-3 fatty acids, 1029–1030 Lewis acids and bases, 109–111 alcohols from alkenes from, 349–352 Opposite charges attract (principle), 47, mechanisms, 104–141 defined, 349, 353, 505 97, 135 nucleophiles, 112–113 mechanism of oxymercuration, and acid–base reactions, 110 reaction mechanism, 104 350–352 Optical activity: rearrangements, 104 rearrangements, 350 origin of, 211–213 relationship between the equilibrium regioselectivity of, 349–350 plane-polarized light, 207, 212, 231, constant and the standard free- Oxytocin, 1077–1078 234, 238 energy change, 125–126 Ozone, cleavage with, 372–373

solom_index_I01-I26hr.indd 18 11/19/12 3:16 PM Index I-19

Ozone depletion and chlorofluorocarbons Petroleum: Phospholipids, 1050–1055 (CFCs), 490–491 refining, 143–144 Phosphoramidite, 1132 Ozonides, 373 as source of alkanes, 143 Phosphoranes, 748 Ozonolysis, 372 typical fractions obtained by distillation Phosphoric acid, 1050 of an alkene, 373 of, 144 Phosphorus pentoxide, 800 Pettit, R., 639 Phosphorus tribromide, 510 P Pfizer, 48–49 Phosphorus ylides, 748 Phase sign, 27 P-2 catalyst, 321 Photons, 597 Phase transfer catalysts, 531 p-Aminobenzoic acid, 928 Photosynthesis and carbohydrate Phenacetin, 818 p-Nitrophenol, 953–954 metabolism, 981–982 Phenanthrene, 645–647 p orbitals, 29 Phthalic acid, 776 Phenanthrols, 945 p53 (anticancer protein), 1079–1080 Phthalimide, 797, 909–910 Phenols, 68, 499, 628, 687, 740, 773, Paclitaxel (Taxol), 370 Phytostanols, 1044 807, 944–978 Palindromes, 1129 Phytosterols, 1044 as acids, reactions of, 949–952 Pallidol, 711 Pi (p) bonds (p bonds), 37, 44 boiling point, 947 Pantothenic acid, 938, 1091 Picric acid, 951 bromination of, 953 Para-disubstituted benzenes, 656 Pitsch, S., 1111 defined, 945 Paraffins, 180 Plane of symmetry (mirror plane), 201 distinguishing/separating from alcohols Parent compound, 152 Plane-polarized light, 207–208, 210–212, and carboxylic acids, 951–952 Partial hydrolysis, 1075 231, 234, 238 1H NMR spectra, 966–967 and sequence comparison, 1076–1077 Plaskon, R. R., 1094 industrial synthesis, 947–949 Pasteur, Louis, 231 Plasmalogens, 1051 infrared (IR) spectra of, 93–94 method for separating enantiomers, 231 Plexiglas, 426, 485 Kolbe reaction, 956 Pauli exclusion principle, 29, 31, 47 Polar aprotic solvents, 266–267 laboratory synthesis, 947 Polar bonds, electronegativity differences Pauling, I., 1117 mass spectra, 967 as causes of, 97 Pauling, Linus, 1087 monobromination of, 953 Polar covalent bonds, 59–61 Pedersen, Charles J., 531 naturally occurring, 946 maps of electrostatic potential (MEP), Penicillamine, 215 nitration of, 953–954 60–61 Penicillinase, 802 nomenclature of, 945–946 as part of functional groups, 60 Penicillins, 802, 812–813 physical properties of, 946 Polar molecules, 61–63 Pentadecane, 146 properties of, 947 Polar protic solvents, 266, 267 Pentalide, 162 reactions of the benzene ring of, Polarimeter, 207, 208–209, 219, 231 Pentane, 144, 146 953–954 Polarizability, 268, 280 insolubility in water, 503 reactions with carboxylic acid and basicity, 281 radical chlorination of, 471 anhydrides and acid chlorides, 952 stereochemistry of chlorination at C2 spectroscopic analysis of, 966–970 Polarized bonds underlie inductive effects of, 472 strength of, as acids, 969–971 (principle), 135 Pentanoic acid, 371, 772, 781, 783 structure of, 945–946 Polyacrylonitrile, 485 Pentose, 982, 1114 sulfonation of, 954 Polyamides, 808, 1061 Pentyl alcohol, 140 synthesis of, 947–949 Polybrominated biphenyls and biphenyl Peptide bonds, 1070 in the Williamson synthesis, 952 ethers (PBBs and PBDEs), 968– Peptide linkages, 1061, 1070 Phenyl groups, 65, 629 969 Peptide synthesizers, 820, 1085 Phenyl halides, 241 Polybromodiphenyl ethers (PBDEs), 969 Peptides, 98, 191, 443, 778, 798, 908, unreactivity of, 274–275 Polychlorinated biphenyls (PCBs), 961, 1070 Phenylalanine, 650, 1008, 1063 968 chemical synthesis of, 820 Phenylalanine hydroxylase, 650 Polycyclic alkanes, 179–1809 defined, 820 Phenylation, 965–966 Polycyclic aromatic hydrocarbons (PAH), synthesis of, 798, 803, 813, 820 Phenylethanal, infrared spectrum of, 754 645–646 Perfumes: Phenylethene, 485, 700 Polyesters, 807–808 aldehydes in, 724 2-Phenylethylamines, 907 Polyethers, from epoxides, 528 ketones in, 724 Phenylhydrazones, 743 Polyethylene, 457, 483–485 Pericyclic reactions, 608–609, 957 Phenylosazones, 999, 1021 Polyethylene glycol (PEG), 501 Periodic table of the elements, 2, 4 Pheromones, 161–162 Polyethylene oxide (PEO), 501 Perkin, Jr., W., 852 Phillips, S. E., 1090 Polyhydroxy compounds, oxidative Perkin, William Henry, 136–137 Phosgene, 803 cleavage of polyhydroxy Permanent dipole moment, 79 Phosphatides, 1051–1053 compounds, 997–998 Peroxides, 458 Phosphatidic acid, 1050 Polyketide anticancer antibiotic Peroxy acid (peracid), 523 Phosphatidylserines, 1051 biosynthesis, 954–955 Perspex, 485 Phosphodiesterase V (PDE5), 488 Polymer polypropylene, 57

solom_index_I01-I26hr.indd 19 11/19/12 3:16 PM I-20 Index

Polymerase chain reaction (PCR), mechanism for, 308 Sanger N-terminal analysis, 1133–1135 rearrangement after, 312 1075–1076 Polymerizations, 483–485 preparation of carboxylic acids by proteomics, 1076, 1100–1102 Polymers, defined, 483 oxidation of, 781–782 purification of, 1098–1100 Polymethyl methacrylate, 485 Primary alkyl halide, 65 quaternary structure, 1090 Polypeptides, 1070–1086, 1098–1100 Primary amines: secondary structure, 1086–1089 analysis of, 1098–1100 addition of, 741–746 synthesis of, 1080–1086 hydrolysis, 1071–10734 preparation of: activation of the carboxyl group, as linear polymers, 1070 through Curtius rearrangement, 1082–1083 primary structure of, 1073–1077 932–933 protecting groups, 1081–1082 C-terminal residues, 1075 through Hofmann rearrangement, tertiary structure, 1089–1090 complete sequence analysis, 914–915 water solubility, 85 1075–1076 through reduction of nitriles, oximes, Proteome, 1100–1102, 1107 Edman degradation, 1073–1074 and amides, 916 Proteomics, 443, 1076, 1100–1102, 1136 examples of, 1077–1080 through reductive amination, Protic solvent, 130, 267–268 peptide sequencing using mass 911–913 Proton NMR spectra: spectrometry and sequence Primary carbocations, 257, 263 complicating features, 417–418 databases, 1076–1077 Primary carbon, 67, 151 interpreting, 398–401 Sanger N-terminal analysis, Primary carbon atom, 65 and rate processes, 420–422 1074–1076 Primary halide, 287 Protonated alcohol, 130, 132–133, 259, purification of, 1098 Primary structure: 305, 307, 508, 511, 512, 736 synthesis of, 1080–1086 of polypeptides and proteins, Protonolysis, of alkylboranes, 359 activation of the carboxyl group, 1073–1077 Protons, 3–4 1082–1083 of a protein, 1061, 1077–1080, 1086 shielding/deshielding, 406–407 automated peptide synthesis, Primer, 1129–1130 Pseudoephedrine, 120 1084–1086 Prochirality, 550–551 Purcell, Edward M., 392 peptide synthesis, 1083–1084 Progesterone, 571, 1045 Purine–purine base pairs, 1115 protecting groups, 1081–1082 Progestins, 1044–1045 Pyramidal inversion, 901 Polypropylene, 485 Proline, 1062, 1064, 1072, 1089, 1091 Pyranose, 986, 988 Polysaccharides, 1009–1013 Propane, 146 Pyrene, 646 cellulose, 1009, 1012–1013 Propene (propylene), 36, 56–57, 156, 340 Pyridine, 648–649 cellulose derivatives, 1013 Propyl alcohol, 502 Pyridinium chlorochromate (PCC), 555 defined, 1009 structural formulas for, 15 Pyridoxal phosphate (PLP), 744 glycogen, 1009, 1011–1012 Propyl group, 149 Pyridoxine (vitamin B6 ), 744 heteropolysaccharides, 1009 Propylene glycols, 502, 504 Pyrimidine, 650, 899, 903, 927, 1108 homopolysaccharides, 1009 Pyrimidine–pyrimidine base pairs, 1115 starch, 1009–1011 Propylene oxide alginates, 14 Prostaglandins, 1049–1050 Pyrolysis, 1040 water solubility, 85 Pyrrole, 648–649 Polystyrene, 485, 701 Prosthetic group, 1091, 1096 Protecting groups, 570, 706–707 Polytetrafluoroethene, 485 Q Polyunsaturated fats/oils, 488, 1029 acetals, 739–740 Qu, X., 217 Polyunsaturated hydrocarbons, 591–592 amino acids, 1081–1082 Quadrangularin A, 711 Polyvinyl chloride (PVC), 485 ethers, 520–521 Quadrupole mass analyzer, 444 Positive entropy change, 136 orthogonal, 1084 Quanta, 597 Potassium dichromate, 136 tert-butyl ethers, 520 Potassium permanganate, 368, 371, 555 Proteins, 1060, 1094–1102 Quantum mechanics, and atomic Potential energy diagram, 164 analysis of, 1098–1100 structure, 27 Potential energy (PE): conjugated, 1096–1098 Quaternary ammonium hydroxides, 931 and covalent bonds, 124–125 defined, 1070 Quaternary ammonium salts, 901, 904 defined, 123–124 prenylated, 1080 Quaternary structure, of a protein, Powers, J. C., 1094 primary structure of, 1061, 1086–1090 Precursors, identifying, 325 1077–1080, 1086 Quinine, 136–137, 444, 906, 934 Pregnenolone, 571 C-terminal residues, 1070 Quinones, 957–958 Prelog, V., 202 complete sequence analysis, Prenylated proteins, 1080 1075–1076 R Presnell, S., 1094 Edman degradation, 1097–1098 Racemic forms (racemic mixture), Priebe, W., 217 examples of, 1077–1080 212–214, 471 Primary alcohols, 67 peptide sequencing using mass and enantiomeric excess, 212–213 chemical test for, 555 spectrometry and sequence and synthesis of chiral molecules, dehydration of, 303–304 databases, 1076–1077 213–214

solom_index_I01-I26hr.indd 20 11/19/12 3:16 PM Index I-21

Racemization, 258–260 oxymercuration–demercuration, 350 messenger RNA (mRNA) synthesis, partial, 258 Receiver coil, 403 1121 via enols and enolates, 825–831 Reducing agent, 545 and protein synthesis, 1080–1086 Radical addition to a p bond, 459 Reducing sugars, 994–995 ribosomes, 1122–1123 Radical addition, to alkenes, 481–483 Reduction, 319 RNA polymerase, 1121 Radical anion, 322 defined, 544 transcription, 1121 Radical cation, 432–434 dissolving metal reduction, 322 transfer RNAs (tRNAs), 1121–1125, Radical chain reaction, 481, 948 Reductive amination: 1127–1128 Radical halogenation, 463–465 mechanism for, 912 translation, 1126–1128 Radical polymerization, of alkenes, preparation of primary, secondary, and Ribosomal RNA (rRNA), 1121–1123 484–485 tertiary amines through, 911–913 Ribosomes, 1122–1123 Radical reactions, homolytic bond Regioselectivity, of oxymercuration– Ribozymes, 1091, 1122 dissociation energies (DH°), demercuration, 349–350 Right-handed coiled DNA, selective 460–463 Reinforcing effect, 28 binding of drug enantiomers to, Radicals, 457–497 Relative configuration, 228–230 217 alkanes: Relative potential energy, 124 Ring current, 639 chlorination of, 464–465 Relative probability, 27 Ring flip, 172 combustion of, 490 Relative reactivity, aldehydes vs. ketones, Ring fusion, 645 alkyl radicals, geometry of, 471 734 Ring strain, 167 antioxidants, 489 Relative stability, 123 (R )-lactic acid, 289 autoxidation, 488–489 Relaxation process, 431 RNA, 3, See Ribonucleic acid (RNA) bromine, selectivity of, 471 Relaxation times, 431 RNA polymerase, 1121 chain reaction, 466–467 Replacement nomenclature, defined, 500 Roberts, J. D., 420, 963 chlorination: Replacement reactions, of arenediazonium Robertson, A., 666 of alkanes, 464 salts, 920–923 Robinson annulation, 881, 890 of methane, 465–468 Resolution, 901, 905–906 Robinson, Robert, 444, 666 chlorine selectivity, lack of, 464–465 by enzymes, 221, 231 Rotaxanes, 170 formation/production of, 458 kinetic, 215 Rowland, F. S., 490 homolytic bond association energies, Resonance, 23 R,S-system of naming enantiomers, calculating, 460 Resonance contributors, 634 202–206 methane chlorination, 465–468 Resonance effects, 136, 692, 694 assigning (R ) and (S ) configurations, activation energies, 471 Resonance energy, 633, 635 202–203 molecular oxygen and superoxide, 487 Resonance stabilization, 24–25, 588–590 Ruff degradation, 1002 multiple halogen substitution, 463–464 Resonance structures (resonance Ruff, Otto, 1002fn nitric oxide, 457, 488 contributors), 22 Ruh-Pohlenz, C., 1111 radical halogenation, 463–465 estimating the relative stability of, Ruthenium, 217, 232, 318 radical polymerization of alkenes, 597–598 484–485, 496 rules for writing, 24–25, 595–597 S reactions of, 459 Resonance theory, 22, 58, 587–591 S-adenosylmethionine, 273–274 tetrahedral chirality centers, 614, 1043 Restricted rotation, and the double bond, (S )-BINAP, 217, 232 using homolytic bond dissociation 39 s-bond framework, 37 energies to determine the relative Restriction endonucleases, 1129 s orbitals, 28 stabilities of, 460–461 Resveratrol, 711 S prefix, 273fn Random coil arrangement, 1089 Retention times, 443 Saccharin, 1008–1009 Raney nickel, defined, 741 Retinal, 72, 328 Salicylic acid, 48–49 Ras proteins, 1080 Retro-aldol reaction, 866–867 Salt formation, water solubility as a result Rate constant, 246 in glycolysis, 870 of, 119–120 Rate-determining step, 254, 341 Retrosynthetic analysis, 324–325, Salts, 6 Rate-limiting step, 269 377–378 Sandmeyer reaction, 921–922 (R )-carvone, 720 disconnections/synthons/synthetic Sanger, Frederick, 1074, 1079, 1129 Reaction coordinate, 248 equivalents, 378–379 Sanger N-terminal analysis, 1074, 1115 Reaction mechanism, defined, 104 key to, 377 Saponification, 792–794 Rearrangements, 104 stereochemical considerations, 378–382 of triacylglycerols, 1033–1035 alkenes, 348–349 Retrosynthetic arrow, 324 Saturated compounds, 56, 319 during dehydration of primary alcohols, Reverse turns, 1088 Saturated fatty acids, 1029 312 Rhodium, 232, 318, 320 Sawhorse formula, 162 during dehydration of secondary Ribonucleic acid (RNA): Schardinger dextrins, 1022 alcohols, 309–311 defined, 1106 Schoenberg, B. P., 1090 McLafferty rearrangement, 440 genetic code, 1077, 1102, 1121, 1123, Schrödinger, Erwin, 27 organic reactions, 104, 107, 109–111 1124–1126 Schultz, Peter G., 1097

solom_index_I01-I26hr.indd 21 11/19/12 3:16 PM I-22 Index

SDS–PAGE (sodium dodecyl Simmons–Smith cyclopropane synthesis, Solvolysis, 243, 245, 260–261 sulfate–polyacrylamide gel 368 Solvomercuration–demercuration, 352, electrophoresis), 1099 Simple addition, 878 520 sec-butyl, 150 Simple triacylglycerols, 1029 sp orbitals, 41, 44 sec-butyl alcohol, 502 Single-barbed curved arrows, 458 sp2 hybridization: Second chirality center, in a radical Single bonds, 34 alkanes/cycloalkanes, 144 halogenation, generation of, Singlets, 397 ethane, 36–37 472–473 Site-specific cleavage, of peptide bonds, ethyne, 40–42 Second-order spectra, 420 1076 sp2 orbitals, 36–38, 43 Secondary alcohols, 67 Skeletal formulas, 18 sp3 orbitals, 35, 43, 122, 167 chemical test for, 555 Skou, Jens, 532 Spackman, D. H., 1072 dehydration of, 304–311 Smalley, R. E., 647 Specific rotation, 209–211 mechanism for, 305–306 Smith, D.C.C., 1024 Spectator ions, 106, 244 rearrangements during, 309–311 Smith, M., 137 Spectroscopic evidence, for alcohols, 556 Secondary alkyl halide, 65–66, 271–272 Smith, R. D., 368 Spectroscopy, See Carbon-13 NMR Secondary amines: SN1 reactions, 254 (carbon-13) NMR spectroscopy; addition of, 741–746 E1 reactions vs., 282 Infrared (IR) spectroscopy; preparation of: effect of the concentration and strength Multidimensional FTNMR through reduction of nitriles, oximes, of the nucleophile, 265–266 spectroscopy; NMR spectroscopy; and amides, 913–914 effect of the structure of the substrate, Nuclear magnetic resonance through reductive amination, 261–262 (NMR) spectrometry 911–913 mechanism for, 254–256 defined, 392 Secondary carbocations, 257, 263 rate-determining step, 254 Sphingolipids, defined, 1053 Secondary carbon, 65, 67, 151 reactions involving racemization, Sphingosine, derivatives of, 1053–1054 Secondary halides, 264, 280 258–260 Spin decoupling, chemical exchange as 2 Secondary structure: SN reactions vs., factors favoring, 271 cause, 420–421 of DNA, 1114–1118 solvent effects on, 266 Spin–lattice relaxation, 431 of a protein, 1087 solvolysis, 243, 245, 260–261 Spin–spin coupling, 411–420 Self-assembled monolayers (SAMs), stereochemistry of, 272 coupling constants, 416–420 1036–1037 SN2 reactions, 245–248 dependence on dihedral angle, Semicarbazone, 763 E2 reactions vs., 280–282 416–417 Sequence databases, peptide sequencing effect of the structure of the substrate, reciprocity of, 416 using, 1076–1077 261–262 origin of, 411 Serine, 1063, 1089 functional group interconversion using, splitting tree diagrams, 412–416 Serine proteases, 1094–1096 271–272 vicinal coupling, 411–412 Serotonin, 744, 906–907 measuring, 245–246 Spin–spin relaxation, 431 Sevin, 804 mechanism for, 246–248 Spiranes, 187 Sex hormones, 1044–1046 reactions involving racemization, Splenda, 284 Sharing electrons, 6 258–260 Splitting patterns, recognizing, 415 Sharpless asymmetric epoxidation, solvent effects on, 266 Splitting tree diagrams, 412–416 524–525 stereochemistry of, 272 splitting analysis for a doublet, 413 Sharpless, Barry, 216 SN Ar mechanism, 960–961 splitting analysis for a quartet, 413–414 Sharpless, K. B., 370, 524, 1009 Sodioacetoacetic ester, 835, 860 splitting analysis for a triplet, 413 Sheehan, John C., 812 Sodium acetate, physical properties, 78 Squalestatin S1, 525 Shells, 4 Sodium alkynides, 568–569 Square planar configuration, 44 Shielding, protons, 406–407 Sodium amide, 314 Stability, 123 1,2 shift, 310 Sodium borohydride, 547 Stachyose, 1023 Shikimic acid, 1025 overall summary of, 548–549 Staggered conformations, 163 Sialyl Lewis x acids, 979, 1016, 1018 Sodium ethynide, 378 Starch, 1009–1011 Sickle-cell anemia, 1079 Sodium hydride, 134, 242, 276, 839– Staudinger, Hermann, 618 Side chain: 840, 952 STEALTH® liposomes, 1052 defined, 700 Sodium nitrite, 918 Stein, W. H., 1072 halogenation of, 701–702 Solid-phase peptide synthesis (SPPS), Step-growth polymers, 808 Sigma bonds (sbonds), 34–35, 44 1084 Stereocenters, See Chirality centers and bond rotation, 162–164 Solubilities: Stereochemistry, 166, 191–238, 272 Signal splitting, 396–398 of substances, 83–85 and chirality, 192–193 Silyl ether protecting groups, 521 in water, 502, 528, 723 constitutional isomers, 206 silyl–Hilbert–Johnson nucleosidation, water solubility guidelines, 85–86 defined, 194 1110, 1137 Solvating ions, 83 diastereomers, 194–195 Simmons, H. E., 368 Solvent effects, 266 enantiomers, 194–195

solom_index_I01-I26hr.indd 22 11/19/12 3:16 PM Index I-23

of epoxidation, 525 Substituted acetic acids, synthesis of, Template, 1133 of hydroboration, 355 840–843 Terelene, 808 of the ionic addition, to alkenes, 343 Substituted benzenes, infrared spectra of, Terminal alkynes, 133 of SN 1 reaction, 258–261 655–656 acidity of, 313–314, 509 of SN 2 reaction, 251, 253, 272 Substituted cyclohexanes, 167–168 conversion to nucleophiles for carbon- stereoisomers, defined, 194, 195 Substituted methyl ketones, 836–837 carbon bond formation, 316–318 Stereogenic atoms, See Chirality centers Substitution reactions, 132, 508, 515, 632 substitution of the acetylenic hydrogen Stereogenic carbon, 197 electrophilic aromatic, 670–673 atom of, 313–314 Stereogenic centers, 197, 225 Substrate, 241, 243 Terminal hydrogen atom, 147 Stereoisomerism, of cyclic compounds, Subtractive effect, 27 Terminal residue analysis, 1073 225–227 Sucralose, 284, 1008 Terminus, 18 Stereoisomers, 39, 166, 175, 194 Sucronic acid, 1009 Terpenes, 1037 defined, 195 Sucrose, 283, 980–981, 1005–1006, 1008 Terpenoids, 1037 Stereoselective reactions, 214–215, 380 Suddath, F. L., 1094 Terramycin, 955 Stereoselective reductions, of carbonyl Suicide enzyme substrate, 859, 879, 883 tert-butyl, 150 groups, 550–551 Sulfa drugs: tert-butyl alcohol, 132, 253, 499, 502 Stereospecific reactions, 380, 525 origin of, 934–935 tert-butyl chloride, 253 alkenes, 363–364 synthesis of, 928–929 tert-butyl ethers Sulfacetamide, 935, 936 Stereospecific, use of term, 525 by alkylation of alcohols, 520 Sulfadiazene, 936 Steric effect, 262, 482, 707 protecting groups, 520 Sulfanilamides, synthesis of, 928–929 Steric factors, 184 Tertiary alcohols: Sulfapyradine, 936, 946 in aldehydes and ketones, 734 dehydration of, 303–307 Sulfonamides, 926–927 Steric hindrance, 164–165, 184, 262– mechanism for, 305–306 Sulfonyl chlorides, 514, 926–927 263, 280, 297 Tertiary amine oxides, 918, 932 Sulfur dioxide, dipole moment, 61 Tertiary amines, 70, 94, 744 Steroids, 895, 1027, 1040, 1040–1049 Sulfuric acid, 106, 131 alkylation of, 911 adrenocortical hormones, 1046 addition to alkenes, 338 nomenclature, 898 cholesterol, 1042–1044 Sunscreens, 656–657 oxidation of, 918 cholic acid, 1048 Superacids, 115 preparation of: D vitamins, 1046–1047 Superglue, 487 through reduction of nitriles, oximes, defined, 1040 Supernovae, 2 and amides, 913–914 digitoxigenin, 1047 Superoxide, 487 through reductive amination, diosgenin, 1048 Superposable, use of term, 39, 192 911–913 reactions of, 1048–1049 Swern oxidation, 552–553, 724–725 reactions of, with nitrous acid, 920 sex hormones, 1044–1046 Syn 1,2-dihydroxylation, 368–370 Tertiary carbocations, 256–257, 263 stigmasterol, 1048 Syn addition, 368–369 Tertiary carbon, 65–66, 68, 151 structure and systematic nomenclature defined, 320–321 Tertiary halides, 253, 262, 263 of, 1041–1042 of hydrogen, 321–322 Tertiary structure, of a protein, 1088, Stigmasterol, 1048 Syn coplanar transition state, 300 1089 Stoddart, J. F., 170, 171 Syn dihydroxylation, 370 Tertiary substrates, 262 Stork enamine reactions, 844–847, 849 Synapses, 908 Testosterone, 1044–1046 Stork, Gilbert, 817, 845, 856, 894 Synthesis, planning, 324–328 Tetrachloroethene, dipole moment, 62 “Straight-chain” alkanes, 144 Synthetic detergents, 1034–1035 Tetrachloromertensene, 362 Strecker synthesis, 1069 Synthetic equivalent, 378, 837 Tetracyclines, 946 Streptomycin, 237, 1018 Synthetic estrogens, 1045 Tetradecane, 146 Strong acids, 733 Synthons, 378 Tetraethyllead, 557 Structural formulas, 14 Tetrahedral carbon atoms, 144 condensed, 17–18 T Tetrahedral chirality centers, 614, 1043 dash, 16–17 Table sugar, substituting the calories of, Tetrahedral geometry, 21, 34 writing/interpreting, 16–18 283–284 Tetrahedral intermediate, 733, 742, 744, Structural formulas, bond-line formula, Tandem mass spectrometry (MS/MS), 752, 768, 784–785, 790, 1095, 18 1076 1122 Structural isomers, 15fn Taq polymerase, 1135 Tetrahedral vs. trigonal stereogenic Stupp, S. I., 86 Tartaric acid, 231 centers, 199 Styrene, 485, 700 Tautomerization, 990–991 Tetrahydrofuran (THF), 500–501, 502, Substituent effect, 129 Tautomers, 861 519 Substituents: Taxol, 609 Tetramethylsilane, 405 classification of, 689 Teflon, 485 Tetrose, 982 effect on electrophilic aromatic chemistry of, 82 Thalidomide, 200 substitution, 689 Temperature and reaction rate, 249–250 Thermal cracking, 143–144

solom_index_I01-I26hr.indd 23 11/19/12 3:16 PM I-24 Index

Thermodynamic enolate, 875 Trigonal stereogenic centers, tetrahedral Urethanes, 803 formation of, 832 stereogenic centers vs., 199 Urey, H., 233 Thermodynamic (equilibrium) control, Trimethylene glycol, 502 Uronic acids, 1013 607 Trimethylsilyl ethers, 521 Urushiols, 945 Thermodynamic (equilibrium) products, 2,4,6-Trinitrophenol, 949, 951 UV-A, UV-B, and UV-C regions, 656 605, 607 Trinitrotoluene (TNT), 669 Thermophilic bacteria, 550 Triose, 824, 982 V Tripeptides, 1070 Thiele, Johannes, 618 Valence electrons, 4, 7, 12 Triple bonds, 7, 21, 88 Thioacetals, 741 Valence shell, 4–5 Triplets, 414 Thiols, 268, 741, 1062 Valence shell electron pair repulsion of nucleotides, 1124 Thionyl chloride, 510 (VSEPR) model, 44, 47 Trisaccharides, 980 Thiophene, 649–650 Valeric acid, 772 Tritium, 4 Three-dimensional formulas, 20–21 Valine, 1063, 1075, 1079, 1102, 1113, Trivial names, for compounds, 145 Threonine, 1063, 1079 1126 Tropylium bromide, 643 Thymol, 68, 946 Valinomycin, 532 Tryptophan, 650, 1063, 1089 Thyroxine, 669 Valium, 907 Tscherning, Kurt, 1044 Thyroxine biosynthesis, 674 van der Waals forces, 79–81 d-Tubocurarine chloride, 897, 908 iodine incorporation in, 670 van der Waals radii, 166 Tumor suppressor, 1080 Tifluoromethanesulfonate ion, 270 van der Waals surface, 36, 61 Two-dimensional NMR (2D NMR) Time-of-flight (TOF) mass analyzer, 444 Vanillin, 498, 501, 720 techniques, 428–431 Toliprolol, 971 Vanomycin, and antibiotic resistance, 1H-1H COSY spectrum, 428–430 Tollens’ reagent, 753, 854, 994–995, 97–98 heteronuclear correlation cross-peak 1019 van’t Hoff, J. H., 20, 231, 164, 230, 231, correlations, 430–431 Tollens’ test (silver mirror test), 753, 764, heteronuclear correlation spectroscopy 1003 854 (HETCOR, or C–H HETCOR), Vasopressin, 1077–1078 Toluene, 90, 628, 686, 699 428–430 Vedejs, E., 748 Tomasz, Maria, 1137 Two-dimensional polyacrylamide gel Viagra, 457, 488 Tool Kit for Organic Synthesis, 377 electrophoresis (2D PAGE), 1100 Vibrational absorption, 87 Torsional barrier, 164 [2+2] cycloaddition, 609 Vicinal coupling, 411, 430 Torsional strain, 164–165, 167 Tyrosine, 650, 670, 870, 977, 1063, 1089 Vicinal dihalide (vic-dihalide), 314, 359 Tranquilizers, 907 defined, 946, 976 Vinyl chloride, 360, 485–486, 590, 622, Trans, 292 959 trans-Cycloheptene, 296 U Vinyl group, 157, 204–205 trans-Cyclohexene, 296 Vinylic anion, 322 Ubiquinones, 957 trans-Cyclooctene, 296 Vinylic halides, 681, 240 Ultraviolet–visible (UV–Vis) spectroscopy, Transaminations, 744 unreactivity of, 274–275 598–600 Transannular strain, 171 Vitalism, 3 absorption maxima for nonconjugated Transcription, 1121 Vitamin A, 1040 and conjugated dienes, 600–602 gene, 534 Vitamin B12 , 323 analytical uses of, 602–604 Transesterification, 792 Vitamin C, 48–49, 200, 795 electromagnetic spectrum, 597–598 Transfer RNAs (tRNAs), 1121–1125, Vitamin D, 1046–1047 UV–Vis spectrophotometer, 598–600 Vitamin E, 489 1127–1128 Unbranched alkanes, 146–147 Vitamin K1, 958 Transition state, 247–251 boiling points, 160 Vitamins, 907, 927, 1032 orientation of groups in, 301–303 density, 161 organic, 3 Translation, 1126–1128 melting points, 160 water-soluble, 1091–1092 Transport antibiotics, and crown ethers, solubilities, 161 Voet, D., 532, 981, 1016, 1043, 1086, 532 Unbranched alkyl groups, how to name, 1092, 1131 Trent, J. O., 217 147 Voet, J. G., 532, 981, 1016, 1043, 1086, Triacylglycerols, 1028–1035 Undecane, 146, 161 1092, 1131 biological functions of, 1032–1033 Under equilibrium control, use of term, Volatize, defined, 81 hydrogenation of, 1032 118 Volume, atoms, 4 mixed, 1029 Unfavorable entropy change, 84 saponification of, 1033–1035 Unimolecular reactions, 254 von Hofmann, August W., 136, 931 simple, 1029 Unsaturated compounds, 56, 319 Vorbrüggen, H., 1111 Trialkylboranes, oxidation of, 356 Unsaturated fatty acids, 1029 Vulcanization, natural rubber, 1040 Trichloromethane, dipole moment, 63 reactions of the alkenyl chain of, 1036 Tridecane, 146 Unshared pairs, 44 W Triflate ion, 270 Upfield, use of term, 399 Walden inversions, 247fn Trigonal pyramid, 45 Urea, 3, 803 Walden, Paul, 247fn, 289

solom_index_I01-I26hr.indd 24 11/19/12 3:16 PM Index I-25

Walker, John E., 532 Weak nucleophiles, 733 X Warmuth, R., 965 Whitmore, F., 305 X-ray crystallography, 1086, 1102 Water: Wieland, Heinrich, 1042 X-rays, 597 acid-catalyzed addition of, to alkenes, Wilkins, Maurice, 1114 Xylenes, 629 346 Wilkinson’s catalyst, 318 and ammonia, 13 Wilkinson’s catalyst bromine, 1002, 1007 tris(triphenylphosphine)rhodium Y miscibility of, 84 chloride), 318 Yates, John, 1100, 1102 tetrahedral structure for the electron Williams, L. D., 1094 Ylides: pairs of a molecule of, 45 Williamson ether synthesis, 518–519, addition of, 747–751 Water solubility: 956, 978 phosphorus, 748 guidelines for, 84–85 Williamson synthesis, phenols in, 952 as the result of salt formation, 119–120 Willstätter, Richard, 632 Z Watson, James, 1114–1116, 1130, 1135 Windaus, Adolf, 1042 Z-Ala, 820 Wave function (y), 27 Winstein, S., 539 - and + signs of, 29 Withers, Stephen, 1093 Zaitsev, A. N., 298 Wave mechanics, 27 Wittig reaction, 747–749 Zaitsev’s rule, 298–300, 302, 310, 931 Wavelength (l), 87, 597 Horner–Wadsworth–Emmons reaction, Zaragozic acid A (squalestatin S1), 525 Wavenumbers, 87, 597fn 750–751 Ziegler, Karl, 484 Waxes, 1054 Wittig synthesis, how to plan, 749–750 Ziegler–Natta catalysts, 484–485 Weak bases, 71, 117, 269–270, 282–283, Wöhler, Friedrich, 3, 325 Zinc, 110 510, 515, 785 Wolff-Kishner reduction, 684, 741, 743 crossed aldol condensations using, Wood alcohol, See Methanol 871–876 Woodward, R. B., 323, 444, 616

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