Organic chemistry 9e john mcmurry 2

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Organic chemistry 9e john mcmurry 2

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16-8 Oxidation of Aromatic Compounds Analogous side-chain oxidations occur in various biosynthetic pathways The neurotransmitter norepinephrine, for instance, is biosynthesized from dopamine by a benzylic hydroxylation reaction The process is catalyzed by the copper-containing enzyme dopamine b-monooxygenase and occurs by a radical mechanism A copper–oxygen species in the enzyme first abstracts the pro-R benzylic hydrogen to give a radical, and a hydroxyl is then transferred from copper to carbon H H H HO H HO NH2 HO OH HO NH2 HO NH2 HO Dopamine Norepinephrine P rob l em - What aromatic products would you obtain from the KMnO4 oxidation of the following substances? (a) O2N CH(CH3)2 C(CH3)3 (b) H3C Bromination of Alkylbenzene Side Chains Side-chain bromination at the benzylic position occurs when an alkylbenzene is treated with N-bromosuccinimide (NBS) For example, propylbenzene gives (1-bromopropyl)benzene in 97% yield on reaction with NBS in the presence of benzoyl peroxide, (PhCO2)2, as a radical initiator Bromination occurs exclusively in the benzylic position next to the aromatic ring and does not give a mixture of products O H H C N CH2CH3 Propylbenzene Br Br H C O (PhCO2)2, CCl4 CH2CH3 (1-Bromopropyl)benzene (97%) O + N H O The mechanism of benzylic bromination is similar to that discussed in Section 10-3 for allylic bromination of alkenes Abstraction of a benzylic hydrogen atom first generates an intermediate benzylic radical, which then reacts with Br2 in step to yield product and a Br· radical, which cycles back into the reaction to carry on the chain The Br2 needed for reaction with the benzylic radical is produced in step by a concurrent reaction of HBr with NBS Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 511 512 chapter 16 Chemistry of Benzene: Electrophilic Aromatic Substitution Br + H H H C R C Br Br H C R R + HBr O N O Br N O + Br2 H O Reaction occurs exclusively at the benzylic position because the benzylic radical intermediate is stabilized by resonance Figure 16-20 shows how the benzyl radical is stabilized by overlap of its p orbital with the ringed p electron system H C H H C H H C H C H H Figure 16-20  A resonance-stabilized benzylic radical The spin-density surface shows that the unpaired electron is shared by the ortho and para carbons of the ring P rob l em - Refer to Table 6-3 on page 170 for a quantitative idea of the stability of a benzyl radical How much more stable (in kJ/mol) is the benzyl radical than a primary alkyl radical? How does a benzyl radical compare in stability to an allyl radical? P rob l em - Styrene, the simplest alkenylbenzene, is prepared commercially for use in plastics manufacture by catalytic dehydrogenation of ethylbenzene How might you prepare styrene from benzene using reactions you’ve studied? Styrene Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 16-9 Reduction of Aromatic Compounds 16-9 Reduction of Aromatic Compounds Catalytic Hydrogenation of Aromatic Rings Just as aromatic rings are generally inert to oxidation, they’re also inert to catalytic hydrogenation under conditions that reduce typical alkene double bonds As a result, it’s possible to reduce an alkene double bond selectively in the presence of an aromatic ring For example, 4-phenyl-3-buten-2-one is reduced to 4-phenyl-2-butanone using a palladium catalyst at room temperature and atmospheric pressure Neither the benzene ring nor the ketone carbonyl group is affected O O H2, Pd Ethanol 4-Phenyl-3-buten-2-one 4-Phenyl-2-butanone (100%) To hydrogenate an aromatic ring, it’s necessary either to use a platinum catalyst with hydrogen gas at a pressure of several hundred atmospheres or to use a more effective catalyst such as rhodium on carbon Under these conditions, aromatic rings are converted into cyclohexanes For example, o-xylene yields 1,2-dimethylcyclohexane, and 4-tert-butylphenol gives 4-tert-butylcyclohexanol CH3 CH3 H H2, Pt; ethanol 130 atm, 25 °C H CH3 CH3 o-Xylene cis-1,2-Dimethylcyclohexane CH3 H3C C CH3 CH3 H3C C H2, Rh/C; ethanol H atm, 25 °C HO 4-tert-Butylphenol HO CH3 H cis-4-tert-Butylcyclohexanol Reduction of Aryl Alkyl Ketones In the same way that an aromatic ring activates a neighboring (benzylic) C ] H toward oxidation, it also activates a benzylic carbonyl group toward reduction Thus, an aryl alkyl ketone prepared by Friedel–Crafts acylation of an aromatic ring can be converted into an alkylbenzene by catalytic hydrogenation over a palladium catalyst Propiophenone, for instance, is reduced to Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 513 514 chapter 16 Chemistry of Benzene: Electrophilic Aromatic Substitution propylbenzene by catalytic hydrogenation Since the net effect of Friedel– Crafts acylation followed by reduction is the preparation of a primary alkylbenzene, this two-step sequence of reactions makes it possible to circumvent the carbocation rearrangement problems associated with direct Friedel–Crafts alkylation using a primary alkyl halide (Section 16-3) O O C CH3CH2CCl H H C CH2CH3 H2/Pd CH2CH3 AlCl3 Propylbenzene (100%) Propiophenone (95%) H CH2CH2CH3 CH3CH2CH2Cl CH3 C CH3 + AlCl3 Isopropylbenzene Propylbenzene Mixture of two products n ​CH2) The conversion of a carbonyl group into a methylene group (C5O ​ by catalytic hydrogenation is limited to aryl alkyl ketones; dialkyl ketones are not reduced under these conditions Furthermore, the catalytic reduction of aryl alkyl ketones is not compatible with the presence of a nitro substituent on the aromatic ring because a nitro group is reduced to an amino group under reaction conditions We’ll see a more general method for reducing ketone carbonyl groups to yield alkanes in Section 19-9 O O2N C H H CH3 H2N C H2, Pd/C CH3 Ethanol m-Nitroacetophenone m-Ethylaniline P rob l em - How would you prepare diphenylmethane, (Ph)2CH2, from benzene and an acid chloride? 16-10 Synthesis of Polysubstituted Benzenes One of the surest ways to learn organic chemistry is to work synthesis problems The ability to plan a successful multistep synthesis of a complex molecule requires a working knowledge of the uses and limitations of a great many Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 16-10  Synthesis of Polysubstituted Benzenes 515 organic reactions Not only must you know which reactions to use, you must also know when to use them because the order in which reactions are carried out is often critical to the success of the overall scheme The ability to plan a sequence of reactions in the right order is particularly important in the synthesis of substituted aromatic rings, where the introduction of a new substituent is strongly affected by the directing effects of other substituents Planning syntheses of substituted aromatic compounds is therefore a good way to gain confidence in using the many reactions learned in the past few chapters During our previous discussion of strategies for working synthesis problems in Section 9-9, we said that it’s usually best to work a problem backward, or retrosynthetically Look at the target molecule and ask yourself, “What is an immediate precursor of this compound?” Choose a likely answer and continue working backward, one step at a time, until you arrive at a simple starting material Let’s try some examples Synthesizing a Polysubstituted Benzene Wo r k e d E x a m p l e - Synthesize 4-bromo-2-nitrotoluene from benzene Strategy Draw the target molecule, identify the substituents, and recall how each group can be introduced separately Then plan retrosynthetically CH3 4-Bromo-2-nitrotoluene Br NO2 The three substituents on the ring are a bromine, a methyl group, and a nitro group A bromine can be introduced by bromination with Br2/FeBr3, a methyl group can be introduced by Friedel–Crafts alkylation with CH3Cl/AlCl3, and a nitro group can be introduced by nitration with HNO3/H2SO4 Solution Ask yourself, “What is an immediate precursor of the target?” The final step will involve introduction of one of three groups—bromine, methyl, or nitro—so we have to consider three possibilities Of the three, the bromination of o-nitrotoluene could be used because the activating methyl group would dominate the deactivating nitro group and direct bromination to the correct position Unfortunately, a mixture of product isomers would be formed A Friedel–Crafts reaction can’t be used as the final step because this reaction doesn’t work on a nitro-substituted (strongly deactivated) benzene The best precursor of the desired product is probably p-bromotoluene, Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 516 chapter 16 Chemistry of Benzene: Electrophilic Aromatic Substitution which can be nitrated ortho to the activating methyl group to give a single product CH3 CH3 NO2 Br NO2 Br o-Nitrotoluene m-Bromonitrobenzene p -Bromotoluene This ring will give a mixture of isomers on bromination This deactivated ring will not undergo a Friedel–Crafts reaction This ring will give only the desired isomer on nitration Br2 HNO3 FeBr3 H2SO4 CH3 Br NO2 4-Bromo-2-nitrotoluene Next ask, “What is an immediate precursor of p-bromotoluene?” Perhaps toluene is an immediate precursor because the methyl group would direct bromination to the ortho and para positions Alternatively, bromobenzene might be an immediate precursor because we could carry out a Friedel–Crafts methylation and obtain a mixture of ortho and para products Both answers are satisfactory, although both would also lead unavoidably to a product mixture that would have to be separated CH3 CH3 Br2 FeBr3 Toluene CH3Cl AlCl3 Br p-Bromotoluene (+ ortho isomer) Br Bromobenzene “What is an immediate precursor of toluene?” Benzene, which could be methylated in a Friedel–Crafts reaction Alternatively, “What is an immediate precursor of bromo­benzene?” Benzene, which could be brominated The retrosynthetic analysis has provided two valid routes from benzene to 4-bromo-2-nitrotoluene CH3 CH3Cl Br2 FeBr3 AlCl3 CH3 Br Benzene Br2 CH3Cl FeBr3 AlCl3 Br CH3 HNO3 Toluene p-Bromotoluene H2SO4 Br NO2 4-Bromo-2-nitrotoluene Bromobenzene Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 16-10  Synthesis of Polysubstituted Benzenes Synthesizing a Polysubstituted Benzene Wo r k e d E x a m p l e - Synthesize 4-chloro-2-propylbenzenesulfonic acid from benzene Strategy Draw the target molecule, identify its substituents, and recall how each of the three can be introduced Then plan retrosynthetically SO3H 4-Chloro-2-propylbenzenesulfonic acid Cl CH2CH2CH3 The three substituents on the ring are a chlorine, a propyl group, and a sulfonic acid group A chlorine can be introduced by chlorination with Cl2/ FeCl3, a propyl group can be introduced by Friedel–Crafts acylation with CH3CH2COCl/AlCl3 followed by reduction with H2/Pd, and a sulfonic acid group can be introduced by sulfonation with SO3/H2SO4 Solution “What is an immediate precursor of the target?” The final step will involve introduction of one of three groups—chlorine, propyl, or sulfonic acid—so we have to consider three possibilities Of the three, the chlorination of o-propylbenzenesulfonic acid can’t be used because the reaction would occur at the wrong position Similarly, a Friedel–Crafts reaction can’t be used as the final step because this reaction doesn’t work on sulfonic-acid-substituted (strongly deactivated) benzenes Thus, the immediate precursor of the desired product is probably m-chloropropylbenzene, which can be sulfonated to give a mixture of product isomers that must then be separated SO3H SO3H Cl CH2CH2CH3 o-Propylbenzenesulfonic acid This ring will give the wrong isomer on chlorination Cl p-Chlorobenzenesulfonic acid This deactivated ring will not undergo a Friedel–Crafts reaction CH2CH2CH3 m-Chloropropylbenzene This ring will give the desired product on sulfonation SO3 H2SO4 SO3H Cl 517 CH2CH2CH3 4-Chloro-2-propylbenzenesulfonic acid “What is an immediate precursor of m-chloropropylbenzene?” Because the two substituents have a meta relationship, the first substituent placed on the ring must be a meta director so that the second substitution will take place at the proper position Furthermore, because primary alkyl groups such as Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 518 chapter 16 Chemistry of Benzene: Electrophilic Aromatic Substitution propyl can’t be introduced directly by Friedel–Crafts alkylation, the precursor of m-chloropropylbenzene is probably m-chloropropiophenone, which could be catalytically reduced H2 Cl C Pd, C CH2CH3 Cl CH2CH2CH3 O m-Chloropropylbenzene m-Chloropropiophenone “What is an immediate precursor of m-chloropropiophenone?” Propio­phenone, which could be chlorinated in the meta position Cl2 C FeCl3 CH2CH3 Cl C O CH2CH3 O Propiophenone m-Chloropropiophenone “What is an immediate precursor of propiophenone?” Benzene, which could undergo Friedel–Crafts acylation with propanoyl chloride and AlCl3 O CH3CH2CCl AlCl3 C CH2CH3 O Benzene Propiophenone The final synthesis is a four-step route from benzene: O Cl2 CH3CH2CCl AlCl3 C CH2CH3 FeCl3 Cl C O Benzene CH2CH3 O m-Chloropropiophenone Propiophenone H2 Pd, C SO3H SO3 Cl CH2CH2CH3 4-Chloro-2-propylbenzenesulfonic acid H2SO4 Cl CH2CH2CH3 m-Chloropropylbenzene Planning an organic synthesis has been compared with playing chess There are no tricks; all that’s required is a knowledge of the allowable moves (the organic reactions) and the discipline to plan ahead, carefully evaluating Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 16-10  Synthesis of Polysubstituted Benzenes the consequences of each move Practicing may not be easy, but it’s a great way to learn organic chemistry P rob l em - 2 How might you synthesize the following substances from benzene? (a) m-Chloronitrobenzene (b) m-Chloroethylbenzene (c) 4-Chloro-1-nitro-2-propylbenzene (d) 3-Bromo-2-methylbenzenesulfonic acid P rob l em - In planning a synthesis, it’s as important to know what not to as to know what to As written, the following reaction schemes have flaws in them What is wrong with each? (a) CN CN CH3CH2COCl, AlCl3 HNO3, H2SO4 O2N C CH2CH3 O (b) Cl Cl CH3CH2CH2Cl, AlCl3 Cl2, FeCl3 CH3CH2CH2 Cl Something Extra Combinatorial Chemistry Traditionally, organic compounds have been synthesized one at a time This works well for preparing large amounts of a few substances, but it doesn’t work so well for preparing small amounts of a great many substances This latter goal is particularly important in the pharmaceutical industry, where vast numbers of structurally similar compounds must be screened to find an optimum drug candidate To speed the process of drug discovery, combinatorial chemistry has been developed to prepare what are called combinatorial libraries, in which anywhere from a few dozen to several hundred thousand substances are prepared simultaneously Among the early successes of combinatorial chemistry is the development of a benzodiazepine library, a class of aromatic compounds commonly used as antianxiety agents R4 O N R3 N R1 Benzodiazepine library (R1–R4 are various organic substituents) R2 Two main approaches to combinatorial chemistry are used—parallel synthesis and split synthesis In parallel synthesis, each compound is prepared independently Typically, a reactant is first linked to the surface of polymer beads, which are then placed continued Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it 519 chapter 16 Chemistry of Benzene: Electrophilic Aromatic Substitution Something Extra (continued) into small wells on a 96-well glass plate Programmable robotic instruments add different sequences of building blocks to the different wells, thereby making 96 different products When the reaction sequences are complete, the polymer beads are washed and their products are released In split synthesis, the initial reactant is again linked to the surface of polymer beads, which are then divided into several groups A different building block is added to each group of beads, the different groups are combined, and the reassembled mix is again split to form new groups Another building block is added to each group, the groups are again combined and redivided, and the process continues If, for example, the beads are divided into four groups at each step, the number n ​ of compounds increases in the progression 4 ​ 16 ​n ​64 ​n ​256 After 10 steps, more than million compounds have been prepared (Figure 16-21) Of course, with so many different final products mixed together, the problem is to identify them What Figure 16-21  The results of split combinatorial synthesis Assuming that different building blocks are used at each step, 64 compounds result after steps, and more than one million compounds result after 10 steps © 2006 Zinsser Analytic Used with permission 520 Organic chemistry by robot means no spilled flasks! structure is linked to what bead? Several approaches to this problem have been developed, all of which involve the attachment of encoding labels to each polymer bead to keep track of the chemistry each has undergone Encoding labels used thus far have included proteins, nucleic acids, halogenated aromatic compounds, and even computer chips A B1 B2 B3 B4 AB1 AB2 AB3 AB4 C1 AB1C1 AB3C1 C2 AB1C2 AB3C2 AB2C1 AB4C1 AB2C2 AB4C2 D1 AB1C1D1 AB1C2D1 AB1C3D1 AB1C4D1 AB2C1D1 AB2C2D1 AB2C3D1 AB2C4D1 AB3C1D1 AB3C2D1 AB3C3D1 AB3C4D1 C3 AB1C3 AB3C3 AB2C3 AB4C3 D2 AB4C1D1 AB4C2D1 AB4C3D1 AB4C4D1 16 products C4 AB1C4 AB3C4 D3 16 products AB2C4 AB4C4 D4 16 products Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it I-22 Index Malonic ester synthesis, 740–742 intramolecular, 741 Maltose, 1→4-a-link in, 859 molecular model of, 859 mutarotation of, 859 structure of, 859 Manicone, synthesis of, 700–701 Mannich reaction, 783g Mannose, biosynthesis of, 869b chair conformation of, 109 configuration of, 841 molecular model of, 109 Marcaine, structure of, 58 Margarine, manufacture of, 237–238, 910 Markovnikov, Vladimir Vassilyevich, 205 Markovnikov’s rule, 205–206 alkene additions and, 205–206 alkyne additions and, 267 carbocation stability and, 206, 208–211 Hammond postulate and, 213 hydroboration and, 231–232 oxymercuration and, 230 Mass number (A), Mass spectrometer, double-focusing, 357 exact mass measurement in, 357 kinds of, 355 operation of, 355–357 Mass spectrometry (MS), 355 alcohols, 362, 562 aldehydes, 365, 642–643 alkanes, 359–360 a cleavage of alcohols in, 362 a cleavage of amines in, 363 amines, 363, 825–826 base peak in, 356 biological, 367–368 carbonyl compounds, 365 cation radicals in, 355–356 dehydration of alcohols in, 362 electron-impact ionization in, 355–356 electrospray ionization in, 367 fragmentation in, 357–358 halides, 363–364 ketones and, 365, 642–643 MALDI ionization in, 367 McLafferty rearrangement in, 365, 642 molecular ion in, 357 nitrogen rule and, 825–826 parent peak in, 357 soft ionization in, 358 time-of-flight, 367 Mass spectrum, 356 1-butanol, 562 computer matching of, 358 2,2-dimethylpropane, 357–358 ethylcyclopentane, 360 N-ethylpropylamine, 826 hexane, 359 2-hexene, 361 interpretation of, 357–360 lysozyme, 368 methylcyclohexane, 360 5-methyl-2-hexanone, 643 2-methylpentane, 385b 2-methyl-2-pentanol, 366 2-methyl-2-pentene, 361 propane, 357 Maxam-Gilbert DNA sequencing, 954 McLafferty rearrangement, 365, 642 Mechanism (reaction), 151 acetal formation, 626–628 acetylide alkylation, 277 acid chloride formation with SOCl2, 688–689 acid-catalyzed epoxide cleavage, 240–241, 578–581 acid-catalyzed ester hydrolysis, 705–706 alcohol dehydration with acid, 546–547 alcohol dehydration with POCl3, 547–548 alcohol oxidation, 551 aldehyde hydration, 614–615 aldehyde oxidation, 609–610 aldehyde reduction, 617–618 aldol reaction, 754–755 aldolase catalyzed reactions, 777–778, 986 alkane chlorination, 290–291 alkene epoxidation, 239–240 alkene halogenation, 223–224 alkene hydration, 228 alkene polymerization, 249–250 alkoxymercuration, 572 alkylbenzene bromination, 511–512 alkyne addition reactions, 266–267 alkyne hydration, 268–269 alkyne reduction with Li/NH3, 274 allylic bromination, 293–294 a-bromination of ketones, 731–733 a-substitution reaction, 731 amide formation with DCC, 692–693 amide hydrolysis, 710–711 amide reduction, 712 amino acid transamination, 1005–1008 aromatic bromination, 480–481 aromatic chlorination, 482–483 aromatic fluorination, 482–483 aromatic iodination, 483–484 aromatic nitration, 484–485 aromatic sulfonation, 485 base-catalyzed epoxide cleavage, 582 base-catalyzed ester hydrolysis, 704–705 b-oxidation pathway, 972–976 biological hydroxylation, 486–487 biotin-mediated carboxylation, 980 bromohydrin formation, 226 bromonium ion formation, 223 Cannizzaro reaction, 633–634 carbonyl condensation reaction, 753–754 citrate synthase, 901–902 Claisen condensation reaction, 764–765 Claisen rearrangement, 575–576 conjugate carbonyl addition reaction, 635–636 Curtius rearrangement, 805 cyanohydrin formation, 616–617 dichlorocarbene formation, 245 Dieckmann cyclization reaction, 768–769 Diels-Alder reaction, 431 diorganocopper conjugate addition, 638 E1 reaction, 343 E1cB reaction, 345 E2 reaction, 338 Edman degradation, 885–887 electrophilic addition reaction, 160–161, 202–203 electrophilic aromatic substitution, 480–481 enamine formation, 621–622 enol formation, 728–729 ester hydrolysis, 704–706 ester reduction, 707–708 FAD reactions, 973–974 fat catabolism, 972–976 fat hydrolysis, 968–971 Fischer esterification reaction, 690–691 Friedel-Crafts acylation reaction, 490–491 Friedel-Crafts alkylation reaction, 488 glycolysis, 982–989 Grignard carboxylation, 665 Grignard reaction, 618–619 Hell-Volhard-Zelinskii reaction, 734 Hofmann elimination reaction, 807–808 Hofmann rearrangement, 803, 805 hydroboration, 232 hydrogenation, 235–236 imine formation, 620–621 intramolecular aldol reaction, 763–764 isopentenyl diphosphate biosynthesis, 919–922 ketone hydration, 614–616 ketone reduction, 617–618 Koenigs-Knorr reaction, 851 Michael reaction, 770–771 mutarotation, 846 nitrile hydrolysis, 670–671 nucleophilic acyl substitution reaction, 684 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it nucleophilic addition reaction, 610–611 nucleophilic aromatic substitution reaction, 506–507 olefin metathesis polymerization, 1046 organometallic coupling reaction, 301–302 oxidative decarboxylation, 990–993 oxymercuration, 229–230 phenol from cumene, 555–556 polar reactions, 155–158 prostaglandin biosynthesis, 251–252, 253 radical reactions, 151–153 reductive amination, 801 Robinson annulation reaction, 776 Sandmeyer reaction, 814 saponification, 704–705 SN1 reaction, 324–325 SN2 reaction, 313–314 Stork enamine reaction, 774 Suzuki-Miyaura reaction, 302 Williamson ether synthesis, 570–571 Wittig reaction, 630–631 Wolff-Kishner reaction, 624–626 Mechlorethamine, 351–352 Meerwein-Ponndorf-Verley reaction, 648h Meerwein’s reagent, 594k Melatonin, 939–941 Melmac, structure of, 1054d Melphalan, 351 Melt transition temperature (polymers), 1049 Menthene, electrostatic potential map of, 61 functional groups in, 61 Menthol, chirality of, 120 molecular model of, 99 structure of, 99 Menthyl chloride, E1 reaction of, 344 E2 reaction of, 343 Mepivacaine, structure of, 58 Mercapto group, 584 Mercuric trifluoroacetate, alkoxymercuration with, 572 Mercurinium ion, 230 Merrifield, Robert Bruce, 890 Merrifield solid-phase peptide synthesis, 890–893 Meso compound, 133–134 plane of symmetry in, 134 Messenger RNA, 949 codons in, 951–952 translation of, 951–953 Mestranol, structure of, 286k Meta (m) prefix, 454 Meta-directing group, 494–495 Metabolism, 779–780, 964 Index Methacrylic acid, structure of, 655 Methamphetamine, structure of, 181e synthesis of, 831n Methandrostenolone, structure and function of, 930 Methane, bond angles in, 13 bond lengths in, 13 bond strengths in, 13 chlorination of, 290–291 molecular model of, 13, 67 pKa of, 276 reaction with Cl2, 152–153 sp3 hybrid orbitals in, 12–13 structure of, 13 Methanethiol, bond angles in, 19 dipole moment of, 32 electrostatic potential map of, 30, 48, 49, 155, 181a, 528 molecular model of, 19 pKa of, 530 polar covalent bond in, 30 sp3 hybrid orbitals in, 19 Methanol bond angles in, 19 industrial synthesis of, 525 molecular model of, 19 sp3 hybrid orbitals in, 19 toxicity of, 525 uses of, 525–526 1,6-Methanonaphthalene, molecular model of, 477a Methionine, S-adenosylmethionine from, 587 biosynthesis of, 648o molecular model of, 130 structure and properties of, 872 Methoxide ion, electrostatic potential map of, 49 p-Methoxybenzoic acid, pKa of, 663 p-Methoxypropiophenone, 1H NMR spectrum of, 400 Methyl acetate, electrostatic potential map of, 685 13C NMR spectrum of, 389, 390 1H NMR spectrum of, 389 Methyl alcohol, see Methanol, bond angles in Methyl a-cyanoacrylate, polymerization of, 1039 Methyl anion, electrostatic potential map of, 276 stability of, 276 Methyl carbocation, electrostatic potential map of, 210 Methyl 2,2-dimethylpropanoate, 1H NMR spectrum of, 396 Methyl group, 70 chiral, 350m directing effect of, 499 I-23 inductive effect of, 497 orienting effect of, 494–495 Methyl phosphate, bond angles in, 19 molecular model of, 19 structure of, 19 Methyl propyl ether, 13C NMR spectrum of, 590 Methyl salicylate, as flavoring agent, 526 Methyl shift, carbocations and, 215–216 Methyl thioacetate, electrostatic potential map of, 685 9-Methyladenine, electrostatic potential map of, 963a Methylamine, bond angles in, 18 dipole moment of, 32 electrostatic potential map of, 49, 794 molecular model of, 18 sp3 hybrid orbitals in, 18 Methylarbutin, synthesis of, 850–851 p-Methylbenzoic acid, pKa of, 662 2-Methylbutane, molecular model of, 67 2-Methyl-2-butanol, 1H NMR spectrum of, 401 Methylcyclohexane, conformations of, 105–106 1,3-diaxial interactions in, 105–106 mass spectrum of, 360 molecular model of, 105, 119 1-Methylcyclohexanol, 1H NMR spectrum of, 407 2-Methylcyclohexanone, chirality of, 119 molecular model of, 119 1-Methylcyclohexene, 13C NMR spectrum of, 417 N-Methylcyclohexylamine, 13C NMR spectrum of, 824 1H NMR spectrum of, 824 Methylene group, 191 Methylerythritol phosphate pathway, terpenoid biosynthesis and, 918–919 N-Methylguanine, electrostatic potential map of, 963a 6-Methyl-5-hepten-2-ol, DEPT-NMR spectra of, 414 5-Methyl-2-hexanone, mass spectrum of, 643 Methyllithium, electrostatic potential map of, 30, 155 polar covalent bond in, 30 Methylmagnesium iodide, electrostatic potential map of, 299 N-Methylmorpholine N-oxide, reaction with osmates, 241–242 2-Methylpentane, mass spectrum of, 385b 2-Methyl-3-pentanol, mass spectrum of, 366 2-Methyl-2-pentene, mass spectrum of, 361 p-Methylphenol, pKa of, 530 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it I-24 Index 2-Methylpropane, molecular model of, 67 Methyl propanoate, 13C NMR spectrum of, 413 2-Methyl-1-propanol, 13C NMR spectrum of, 415 2-Methylpropene, electrophilic addition of HBr to, 202 Metoprolol, synthesis of, 582 Mevacor, structure of, 436 Mevalonate, decarboxylation of, 922 Mevalonate pathway, terpenoid biosynthesis and, 919–922 Micelle, 912 Michael reaction, 770–772 acceptors in, 772 donors in, 772 mechanism of, 770–771 partners in, 772 Robinson annulation reactions and, 776 Microwaves, electromagnetic spectrum and, 368 Mineralocorticoid, 929 Minor groove (DNA), 946 Mitomycin C, structure of, 831f Mixed aldol reaction, 761–762 Mixed Claisen condensation reaction, 766–767 Molar absorptivity (UV), 440 Molecular ion (M1), 357 Molecular mechanics, 113 Molecular model, acetaminophen, 27a acetylene, 17 adenine, 59a adrenaline, 148b alanine, 27a, 870 alanylserine, 882 a helix, 894 p-aminobenzoic acid, 24 anisole, 568 anti periplanar geometry, 340 arecoline, 66 aspartame, 27b aspirin, 16 b-pleated sheet, 894 p-bromoacetophenone, 411–412 bromocyclohexane, 103 butane, 67 cis-2-butene, 193, 198 trans-2-butene, 193, 198 tert-butyl carbocation, 209 camphor, 112 cellobiose, 859 chair cyclohexane, 100 cholesterol, 928 cholic acid, 654 citrate synthase, 901 citric acid, 27a coniine, 27a cyclobutane, 98 1,3,5,7,9-cyclodecapentaene, 461, 477a cyclohexane ring flip, 103 cyclopentane, 99 cyclopropane, 93, 97 cytosine, 59a cis-decalin, 111, 927 trans-decalin, 111, 927 diethyl ether, 568 dimethyl disulfide, 19 cis-1,2-dimethylcyclohexane, 107 trans-1,2-dimethylcyclohexane, 108 cis-1,2-dimethylcyclopropane, 93 trans-1,2-dimethylcyclopropane, 93 2,2-dimethylpropane, 67 DNA, 55, 946 dopamine, 800 eclipsed ethane conformation, 81 enflurane, 121 ethane, 14, 67 ethylene, 15 fluoxetine, 145 glucose, 101, 109, 835 hexokinase, 178 Hofmann elimination, 808 ibuprofen, 59a, 148 isobutane, 67 isoleucine, 133 lactic acid, 118 lactose, 860 lidocaine, 88 (2)-limonene, 145 (1)-limonene, 145 linolenic acid, 910 maltose, 859 mannose, 109 menthol, 99 meso-tartaric acid, 134 methane, 13, 67 methanethiol, 19 methanol, 19 1,6-methanonaphthalene, 477a methionine, 130 methyl phosphate, 19 methylamine, 18 2-methylbutane, 67 methylcyclohexane, 105, 119 2-methylcyclohexanone, 119 2-methylpropane, 67 naphthalene, 59 Newman projections, 80 norbornane, 112 omega-3 fatty acid, 910 oseltamivir phosphate, 113 pentane, 67 phenylalanine, 88 piperidine, 809 propane, 67 propane conformations, 82 pseudoephedrine, 148b serylalanine, 882 staggered ethane conformation, 81 stearic acid, 909 steroid, 926 sucrose, 860 syn periplanar geometry, 340 Tamiflu, 113 testosterone, 111 tetrahydrofuran, 568 threose, 121 trimethylamine, 790 tRNA, 952 twist boat cyclohexane, 101 vitamin C, 675 Molecular orbital, 20 allylic radical, 294 antibonding, 20, 21, 23 benzene, 458 bonding, 20, 21, 23 1,3-butadiene, 423–424, 1014 conjugated diene, 423–424 conjugated enone, 758 degenerate, 458 ethylene, 1014 1,3,5-hexatriene, 1015 Molecular orbital (MO) theory, 20–21 Hückel 4n rule and, 461 Molecular weight, mass spectral determination of, 357 Molecule(s), condensed structures of, 21–22 electron-dot structures of, Kekulé structures of, line-bond structures of, skeletal structures of, 21–23 Molozonide, 242 Monomer, 247 Monosaccharide(s), 833 anomers of, 844–846 configurations of, 840–842 cyclic forms of, 844–846 essential, 856–858 esters of, 848–849 ethers of, 849 Fischer projections and, 836–837, 843 glycosides of, 849–851 hemiacetals of, 844–846 osazones from, 869i oxidation of, 853–854 phosphorylation of, 851–852 reaction with acetic anhydride, 848–849 reaction with iodomethane, 849 reduction of, 852 see also Aldose(s) Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Monoterpene, 258 Monoterpenoid, 918 Moore, Stanford, 884 Morphine, biosynthesis of, 831h specific rotation of, 122 structure of, 57 MRI, see Magnetic resonance imaging, 417 mRNA, see Messenger RNA MS, see Mass spectrometry Mullis, Kary Banks, 959 Multiplet (NMR), 397 table of, 399 Muscalure, synthesis of, 301 Mustard agents/gas, 351–353 Mutarotation, 846 glucose and, 846 mechanism of, 846 Mycomycin, stereochemistry of, 148i Mylar, structure of, 717 myo-Inositol, structure of, 114g Myrcene, structure of, 257 Myristic acid, catabolism of, 976 structure of, 909 n (normal) alkane, 67 n 1 rule, 398 N-terminal amino acid, 882 Naming, acid anhydrides, 680 acid chlorides, 680 acid halides, 680 acyl phosphate, 682 alcohols, 526–527 aldehydes, 605–606 aldoses, 842 alkanes, 73–77 alkenes, 189–191 alkyl groups, 70, 75–76 alkyl halides, 289–289 alkynes, 263–264 alphabetizing and, 77 amides, 681 amines, 787–789 aromatic compounds, 453 carboxylic acid derivatives, 680–682 carboxylic acids, 655 cycloalkanes, 90–92 cycloalkenes, 190–191 eicosanoids, 916 enzymes, 897 esters, 681 ethers, 569 heterocyclic amines, 789 ketones, 606 new IUPAC system for, 190–191 nitriles, 655–656 old IUPAC system for, 190 phenols, 527 Index prostaglandins, 915–916 sulfides, 586 thioesters, 681 thiols, 584 Naphthalene, aromaticity of, 467–468 electrostatic potential map of, 468 Hückel 4n rule and, 468 molecular model of, 59 13C NMR absorptions of, 473 orbitals picture of, 468 reaction with Br2, 467 resonance in, 467 Naproxen, NSAIDs and, 475 structure of, 27h Natural gas, composition of, 86 Natural product, 217 drugs from, 179 number of, 217 NBS, see N-Bromosuccinimide NDA, see New drug application, 180 Neighboring-group effect, 851 Neomenthyl chloride, E2 reaction of, 342–343 Neopentyl group, 76 SN2 reaction and, 317 Neoprene, synthesis and uses of, 437 New drug application (NDA), 180 New molecular entity (NME), number of, 179 Newman, Melvin S., 80 Newman projection, 80 molecular model of, 80 Nicotinamide adenine dinucleotide, biological oxidations with, 552 biological reductions with, 536–537 reactions of, 634 structure of, 634, 899 Nicotinamide adenine dinucleotide phosphate, biological reductions and, 238 Nicotine, structure of, 27c, 787 Ninhydrin, reaction with amino acids, 884 Nitration (aromatic), 484–485 Nitric acid, pKa of, 45 Nitrile(s), 655 alkylation of, 745–746 from amides, 668–669 amides from, 670–671 amines from, 671 from arenediazonium salts, 812 carboxylic acids from, 664–665, 670–671 electrostatic potential map of, 669 hydrolysis of, 664–665, 670–671 IR spectroscopy of, 673 ketones from, 671 naming, 655–656 I-25 naturally occurrence of, 668 NMR spectroscopy of, 673 pKa of, 736 reaction with Grignard reagents, 671 reaction with LDA, 745–746 reaction with LiAlH4, 671 reduction of, 671 synthesis of, 668–669 Nitrile group, directing effect of, 502 inductive effect of, 497 orienting effect of, 494–495 resonance effect of, 498 Nitrile rubber polymer, structure and uses of, 1042 Nitro compound, Michael reactions and, 772 Nitro group, directing effect of, 502 inductive effect of, 497 orienting effect of, 494–495 resonance effect of, 497 Nitroarene, arylamines from, 798 reaction with iron, 798 reaction with SnCl2, 798 reduction of, 798 Nitrobenzene, aniline from, 484 reduction of, 484–485 synthesis of, 484–485 p-Nitrobenzoic acid, pKa of, 663 Nitrogen, hybridization of, 18–19 Nitrogen rule of mass spectrometry, 825–826 Nitronium ion, 484–485 electrostatic potential map of, 484 p-Nitrophenol, pKa of, 530 Nitrous acid, reaction with amines, 812 NME, see New molecular entity, 179 NMO, see N-Methylmorpholine N-oxide NMR, see Nuclear magnetic resonance Node, Nomenclature, see Naming Nomex, structure of, 1054c Nonbonding electrons, Noncovalent interaction, 54–56 Nonequivalent protons, spin-spin splitting and, 405–406 tree diagram of, 406 Nootkatone, chirality of, 120 Norbornane, molecular model of, 112 Norepinephrine, adrenaline from, 335 biosynthesis of, 511 Norethindrone, structure and function of, 930 Normal (n) alkane, 67 Norsorex, synthesis of, 1048 Novocaine, structure of, 57 Novolac resin, 445–446 Noyori, Ryoji, 644 NSAID, 474 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it I-26 Index Nuclear magnetic resonance spectrometer, field strength of, 388 operation of, 390 Nuclear magnetic resonance (NMR) spectroscopy, 386 acid anhydrides, 720 acid chlorides, 720 alcohols, 560–561 aldehydes, 641–642 allylic protons and, 394–395 amides, 720 amines, 824 aromatic compounds, 471–473 aromatic protons and, 394–395 calibration peak for, 392 carboxylic acid derivatives, 720 carboxylic acids, 673–674 chart for, 392 13C chemical shifts in, 410–411 1H chemical shifts in, 394–395 coupling constants in, 398 delta scale for, 392 diastereotopic protons and, 403 enantiotopic protons and, 403 energy levels in, 389–390 epoxides, 589–590 esters, 720 ethers, 589, 590 field strength and, 387–388 FT-NMR and, 408–409 homotopic protons and, 403 integration of, 396 ketones, 641–642 multiplets in, 397–399 n 1 rule and, 398 nitriles, 673 overlapping signals in, 404 13C peak assignments in, 413–415 1H peak size in, 406 phenols, 561 principle of, 386–388 proton equivalence and, 402–404 pulsed, 408–409 radiofrequency energy and, 387–388 ring current and, 471–472 shielding in, 389 signal averaging in, 408–409 spin-flips in, 387 spin-spin splitting in, 397–400 time scale of, 391 uses of 13C, 416–417 uses of 1H, 407 vinylic protons and, 387–388 13C Nuclear magnetic resonance spectrum, acetaldehyde, 642 acetophenone, 642 anisole, 590 benzaldehyde, 642 p-bromoacetophenone, 410, 411 butanoic acid, 673 2-butanone, 410, 411, 642 crotonic acid, 673 cyclohexanol, 560 cyclohexanone, 642 ethyl benzoate, 419e methyl acetate, 389, 390 methyl propanoate, 479 methyl propyl ether, 590 1-methylcyclohexene, 417 N-methylcyclohexylamine, 824 2-methyl-1-propanol, 415 1-pentanol, 409 propanenitrile, 673 propanoic acid, 673 propionic acid, 673 1H Nuclear magnetic resonance spectrum, acetaldehyde, 642 bromoethane, 397 2-bromopropane, 398 p-bromotoluene, 472 trans-cinnamaldehyde, 405–406 cyclohexylmethanol, 407 dipropyl ether, 589 1,2-epoxypropane, 590 ethyl acetate, 720 p-methoxypropiophenone, 400 methyl acetate, 389 methyl 2,2-dimethylpropanoate, 396 2-methyl-2-butanol, 401 1-methylcyclohexanol, 407 N-methylcyclohexylamine, 824 phenylacetic acid, 674 1-propanol, 561 toluene, 404, 405 Nuclear spin, common nuclei and, 389 NMR and, 386–388 Nucleic acid, 942 see also Deoxyribonucleic acid, Ribonucleic acid Nucleophile(s), 157 characteristics of, 162–164 curved arrows and, 162–164 electrostatic potential maps of, 157 examples of, 157 SN1 reaction and, 330 SN2 reaction and, 317–319 Nucleophilic acyl substitution reaction, 600, 683–684 abbreviated mechanism for, 977, 979 acid anhydrides, 702 acid chlorides, 696–701 acid halides, 696–701 amides, 710–712 carboxylic acids and, 688–696 esters, 704–709 kinds of, 686–687 mechanism of, 684 reactivity in, 685–687 Nucleophilic addition reaction, 598, 610–613 acid catalysis of, 614–615 base catalysis of, 614–615 mechanism of, 610–611 steric hindrance in, 612 trajectory of, 612 variations of, 612 Nucleophilic aromatic substitution reaction, 505–508 mechanism of, 506–507 Nucleophilic substitution reaction, 310–311 biological examples of, 333–334 summary of, 345–346 see also SN1 reaction, SN2 reaction Nucleophilicity, 319 basicity and, 318, 319 table of, 318 trends in, 318, 319 Nucleoside, 942 Nucleotide, 942 39 end of, 945 59 end of, 945 Nucleus, size of, Nylon, 715–716 manufacture of, 715 naming, 715 uses of, 716 Nylon 6, structure of, 716 synthesis of, 1043 Nylon 6,6, structure of, 715 synthesis of, 1043–1044 Nylon 10,10, uses of, 1054c Ocimene, structure of, 219e Octane number (fuel), 87 Octet rule, -oic acid, carboxylic acid name suffix, 654 Okazaki fragments, DNA replication and, 949 -ol, alcohol name suffix, 527 Olah, George Andrew, 224 Olefin, 185 Olefin metathesis polymerization, 1046–1048 Grubbs catalyst for, 1046 kinds of, 1047 mechanism of, 1046 Oleic acid, structure of, 909 Oligonucleotide, 956 synthesis of, 956–959 Olive oil, composition of, 909 Omega-3 fatty acid, 910 molecular model of, 910 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it -one, ketone name suffix, 606 -onitrile, nitrile name suffix, 656 Optical activity, 121–122 measurement of, 121–122 Optical isomers, 124 Optically active, 121 Orbital, energies of, hybridization of, 12–19 shape of, 4–5 d Orbital, shape of, p Orbital, nodes in, shape of, s Orbital, shape of, Organic chemicals, number of, 60 toxicity of, 25–26 Organic chemistry, foundations of, 2–3 Organic compound(s), elements found in, number of, oxidation level of, 304 polar covalent bonds in, 155–156 size of, Organic foods, 25–26 Organic reactions, chirality and, 252–256 conventions for writing, 204 kinds of, 149–150 Organic synthesis, enantioselective, 644–646 strategy of, 279 Organoborane, from alkenes, 230–232 reaction with H2O2, 231 Organocopper reagent, see Diorganocopper reagent, Gilman reagent Organodiphosphate, biological substitution reactions and, 333–334 Organohalide(s), 287 biological uses of, 305–306 naturally occurring, 305–306 number of, 305 reaction with Gilman reagents, 300–301 uses of, 287 see also Alkyl halide Organomagnesium halide, see Grignard reagent Organomercury compounds, reaction with NaBH4, 229–230 Organometallic compound, 299 Organometallic coupling reaction, 300–302 Organopalladium compound, SuzukiMiyaura reaction of, 302 Organophosphate, bond angles in, 19 hybrid orbitals in, 19 Orlon, structure and uses of, 250 Ortho (o) prefix, 454 Index Ortho- and para-directing group, 494–495 Osazone, 869i -ose, carbohydrate name suffix, 834 Oseltamivir phosphate, mechanism of, 865–866 molecular model of, 113 structure of, 27f Osmate, 241 Osmium tetroxide, reaction with alkenes, 241–242 toxicity of, 241 Oxalic acid, structure of, 655 Oxaloacetic acid, structure of, 655 Oxaphosphatane, 630 Oxetane, reaction with Grignard reagents, 594k Oxidation, 239 alcohols, 550–552 aldehydes, 609–610 aldoses, 853–854 alkenes, 239–244 biological, 552 organic, 303 phenols, 558 sulfides, 587 thiols, 585 Oxidation level, table of, 304 Oxidative decarboxylation, pyruvate catabolism and, 990–993 steps in, 991 Oxidoreductase, 897 Oxime, 621 from aldehydes and ketones, 621 Oxirane, 239 Oxo group, 607 Oxycodone, structure of, OxyContin, structure of, Oxyfluorfen, synthesis of, 508 Oxygen, hybridization of, 19 Oxymercuration, 229–230 mechanism of, 229–230 regiochemistry of, 230 Ozone, preparation of, 242 reaction with alkenes, 242–243 reaction with alkynes, 275 Ozonide, 242 danger of, 243 Paclitaxel, structure of, 284 Palmitic acid, structure of, 909 Palmitoleic acid, structure of, 909 PAM resin, solid-phase peptide synthesis and, 892 Para (p) prefix, 454 Paraffin, 78 Parallel synthesis, 519–520 Parent peak (mass spectrum), 357 Partial charge, 29 I-27 Pasteur, Louis, enantiomers and, 123–124 resolution of enantiomers and, 136 Patchouli alcohol, structure of, 918 Paternity, DNA test for, 961–962 Pauli exclusion principle, Pauling, Linus Carl, 12 PCR, see Polymerase chain reaction, 959–961 PDB, see Protein Data Bank, 903–904 PDT, see Photodynamic therapy (PDT) Peanut oil, composition of, 909 Pedersen, Charles John, 583 Penicillin, discovery of, 721 Penicillin V, specific rotation of, 122 stereochemistry of, 147 Penicillium notatum, penicillin from, 721 Pentachlorophenol, synthesis of, 557 1,4-Pentadiene, electrostatic potential map of, 424 Pentadienyl radical, resonance in, 41 Pentalene, 477e Pentane, molecular model of, 67 2,4-Pentanedione, pKa of, 737 2,4-Pentanedione anion, resonance in, 40 1-Pentanol, 13C NMR spectrum of, 409 Pentobarbital, synthesis of, 749 Pentose phosphate pathway, 1012b–1210c Pepsin, pI of, 878 Peptide(s), 870 amino acid sequencing of, 885–887 backbone of, 882 covalent bonding in, 881–883 disulfide bonds in, 883 Edman degradation of, 885–887 reaction with phenylisothiocyanate, 885–886 solid-phase synthesis of, 890–893 synthesis of, 888–893 Peptide bond, 881–883 DCC formation of, 692–693, 889–890 restricted rotation in, 882–883 Pericyclic reaction, 1013 frontier orbitals and, 1015 kinds of, 1013 stereochemical rules for, 1031 Woodward-Hoffmann rules for, 1014–1015 Periodic acid, reaction with 1,2-diols, 243–244 Periplanar, 339 Perlon, structure of, 716 Peroxide, 570 Peroxyacid, 240 reaction with alkenes, 239–240 PET, see Polyethylene terephthalate, 1049 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it I-28 Index Petit, Rowland, 460 Petroleum, catalytic cracking of, 87 composition of, 86 gasoline from, 86–87 history of, 86 refining of, 86–87 reforming of, 87 Pfu DNA polymerase, PCR and, 960 Pharmaceuticals, approval procedure for, 180 origin of, 180 Phenol(s), 525 acidity of, 529–531 from arenediazonium salts, 813 Bakelite from, 1051 from chlorobenzene, 508 from cumene, 555 Dow process for, 555 electrophilic aromatic substitution reactions of, 557 electrostatic potential map of, 496 hydrogen bonds in, 528 IR spectroscopy of, 560 IR spectrum of, 560 mechanism of synthesis of, 555–556 naming, 527 NMR spectroscopy of, 561 oxidation of, 558 phenoxide ions from, 529 pKa of, 530 properties of, 528–532 quinones from, 558 reaction with arenediazonium salts, 816 uses of, 526, 555, 557 Phenolic resin, 1051 Phenoxide ion, 529 electrostatic potential map of, 532 resonance in, 532 Phentermine, synthesis of, 805 Phenyl alkyl ethers, 588 Phenyl group, 453–454 Phenylacetaldehyde, aldol reaction of, 755 IR spectrum of, 382 Phenylacetic acid, 1H NMR spectrum of, 674 Phenylacetylene, IR spectrum of, 383 Phenylalanine, biosynthesis of, 576, 1028–1029 molecular model of, 88 pKa of, 45 structure and properties of, 872 Phenylisothiocyanate, Edman degradation and, 885–886 Phenylthiohydantoin, Edman degradation and, 885–887 Phosphate, electrostatic potential map of, 64 Phosphatidic acid, glycerophospholipids from, 913 Phosphatidylcholine, structure of, 914 Phosphatidylethanolamine, structure of, 914 Phosphatidylserine, structure of, 914 Phosphine(s), chirality of, 140 Phosphite, DNA synthesis and, 958 oxidation of, 958 Phospholipid, 913–914 classification of, 913 Phosphopantetheine, coenzyme A from, 714, 966 Phosphoramidite, DNA synthesis and, 958 Phosphorane, 630 Phosphoric acid, pKa of, 45 Phosphoric acid anhydride, 966 Phosphorus, hybridization of, 19 Phosphorus oxychloride, alcohol dehydration with, 546–548 Phosphorus tribromide, reaction with alcohols, 298, 544 Photochemical reaction, 1016 Photodynamic therapy (PDT), 448–450 Photofrin, 449 Photolithography, 444–446 resists for, 445–446 Photon, 369 energy of, 369–370 Photosynthesis, 833 Phthalates, use as plasticizers, 703 Phthalic acid, structure of, 655 Phthalimide, Gabriel amine synthesis and, 800 Phthalocyanine, 449–450 Phylloquinone, biosynthesis of, 491–492 Pi (p) bond, 15 acetylene and, 17 ethylene and, 15 molecular orbitals in, 21 Picometer, Picric acid, synthesis of, 555 Pinacol rearrangement, 567l Pineapple, esters in, 703 Piperidine, molecular model of, 809 structure of, 789 PITC, see Phenylisothiocyanate, 885–886 pKa, 44 table of, 45 Planck equation, 369–370 Plane-polarized light, 121 Plane of symmetry, 117, 118 meso compounds and, 134 Plasmalogen, structure of, 938c Plastic, recyclable, 1052–1053 see also Polymer(s) Plasticizer, 703, 1049 structure and function of, 1049 toxicity of, 1049 Plavix, structure of, 27f Plexiglas, structure of, 250 Poison ivy, urushiols in, 526 Polar aprotic solvent, 321 SN1 reaction and, 331 SN2 reaction and, 321 Polar covalent bond, 28–29 dipole moments and, 31–32 electronegativity and, 29–30 electrostatic potential maps and, 30 inductive effects and, 30 Polar reaction, 152, 155–158 characteristics of, 155–158 curved arrows in, 157, 162–165 electrophiles in, 157 example of, 159–161 nucleophiles in, 157 Polarimeter, 121 Polarizability, 156 Poly(ethylene terephthalate), structure of, 1049 Poly(glycolic acid), biodegradability of, 1052–1053 uses of, 717–718 Poly(hydroxybutyrate), biodegradability of, 1052–1053 uses of, 717–718 Poly(lactic acid), biodegradability of, 1052–1053 uses of, 717–718 Poly(methyl methacrylate), uses of, 250 Poly(vinyl acetate), uses of, 250 Poly(vinyl butyral), uses of, 1054c Poly(vinyl chloride), plasticizers in, 1049 uses of, 250 Polyacrylonitrile, uses of, 250 Polyalkylation, Friedel-Crafts reaction and, 489 Polyamide, 715 Polybutadiene, synthesis of, 437 vulcanization of, 438 Polycarbonate, 717, 1044 Polycyclic aromatic compound, 467 aromaticity of, 467–468 Polycyclic compound, 110 bridgehead atoms in, 110 conformations of, 110–112 Polycyclic heterocycle, 821–822 Polyester, 715 manufacture of, 717 uses of, 717 Polyethylene, crystallites in, 1048 high-density, 1041 high-molecular-weight, 1041 kinds of, 1041 low-density, 1041 synthesis of, 249–250 ultrahigh-molecular-weight, 1041 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it uses of, 250 Ziegler-Natta catalysts and, 1041 Polyimide, structure of, 726i Polymer(s), 247 atactic, 1040 biodegradable, 717–718, 1052–1053 biological, 247–248 chain-growth, 249–250, 1037–1039 classification of, 1037–1038 crystallites in, 1048 elastomer, 1050 fiber, 1050 glass transition temperature of, 1049 isotactic, 1040 kinds of, 1049 melt transition temperature of, 1049 plasticizers in, 1049 recycling codes for, 1052 representation of, 1037 step-growth, 715–717, 1043–1045 syndiotactic, 1040 table of, 250 thermoplastic, 1049 thermosetting resin, 1051 van der Waals forces in, 1048 Polymerase chain reaction (PCR), 959–961 amplification factor in, 959–960 Pfu DNA polymerase in, 960 Taq DNA polymerase in, 960 Polymerization, anionic, 1038 cationic, 1038 mechanism of, 249–250 Ziegler-Natta catalysts for, 1040–1041 Polypropylene, polymerization of, 1040 stereochemical forms of, 1040 uses of, 250 Polysaccharide(s), 861–862 synthesis of, 862–863 Polystyrene, uses of, 250 Polytetrafluoroethylene, uses of, 250 Polyunsaturated fatty acid, 908–910 Polyurethane, 1044–1045 foam, 1045 kinds of, 1045 stretchable, 1045 Polyynes, occurrence of, 314 Pomalidomide, 183 Posttranslational modification, protein, 956 Potassium nitrosodisulfonate, reaction with phenols, 558 Potassium permanganate, reaction with alcohols, 550 reaction with alkenes, 243 reaction with alkylbenzenes, 510–511 reaction with ketones, 610 Pravachol, structure of, 88e Pravadoline, green synthesis of, 828 Index Pravastatin, statin drugs and, 1010–1011 structure of, 88e Prepolymer, epoxy resins and, 591–592 Prilocaine, structure of, 58 Primary alcohol, 526 Primary amine, 787 Primary carbon, 71 Primary hydrogen, 72 Primary structure (protein), 893 pro-R prochirality center, 142 pro-S prochirality center, 142 Problems, how to work, 27 Procaine, structure of, 27e, 57 Prochirality, 141–143 assignment of, 142 chiral environments and, 146–147 naturally occurring molecules and, 143 re descriptor for, 141–142 si descriptor for, 141–142 Prochirality center, 142 pro-R, 142 pro-S, 142 Progesterone, structure of, 420 structure and function of, 929 Progestin, 929 function of, 929 Proline, biosynthesis of, 802 structure and properties of, 872 Promotor sequence (DNA), 949 Propagation step (radical), 153 Propane, bond rotation in, 82 conformations of, 82 mass spectrum of, 357 molecular model of, 67, 82 Propanenitrile, 13C NMR absorptions in, 673 Propanoic acid, 13C NMR absorptions in, 673 1-Propanol, 1H NMR spectrum of, 561 Propenal, electrostatic potential map of, 432 Propene, see Propylene Propenenitrile, electrostatic potential map of, 432 Propionic acid, see Propanoic acid Propyl group, 71 Propylene, heat of hydrogenation of industrial preparation of, 186 uses of, 186 Prostaglandin(s), 915–917 biosynthesis of, 153–154, 251–252, 253, 916–917 functions of, 153, 915 naming, 915–916 occurrence of, 915 see also Eicosanoid Prostaglandin E1, structure of, 89, 915 Prostaglandin E2, biosynthesis of, 916–917 I-29 Prostaglandin F2a, structure of, 95 Prostaglandin H2, biosynthesis of, 153–154, 916–917 Prostaglandin I2, structure of, 915 Protecting group, 553 alcohols, 553–555 aldehydes, 628 ketones, 628 nucleic acid synthesis and, 956–957 peptide synthesis and, 889–890 Protein(s), 870 a helix in, 893–894 backbone of, 882 biosynthesis of, 951–953 denaturation of, 895 isoelectric point of, 878 mechanism of hydrolysis of, 711 number of, in humans, 951 primary structure of, 893 quaternary structure of, 893 secondary structure of, 893–894 C-terminal amino acid in, 882 N-terminal amino acid in, 882 tertiary structure of, 893, 895 see also Peptide(s) Protein Data Bank (PDB), 903–904 downloading structures from, 903–904 number of structures in, 903 Protic solvent, 321 SN1 reaction and, 331 SN2 reaction and, 321 Proton equivalence, 1H NMR spectroscopy and, 402–404 Protonated methanol, electrostatic potential map of, 155 Protosteryl cation, lanosterol biosynthesis and, 933, 935–936 Prozac, structure of, 145 Pseudoephedrine, molecular model of, 148b PTH, see Phenylthiohydantoin, 885–887 Purine, aromaticity of, 468 electrostatic potential map of, 822 nucleotides from, 943 structure of, 822 Pyramidal inversion, amines and, 790–791 energy barrier to, 790–791 Pyranose, 844–846 glucose and, 844–845 Pyridine, aromaticity of, 464–465, 819–920 basicity of, 793, 819–920 dipole moment of, 820 electrophilic substitution reactions of, 820 electrostatic potential map of, 464 Hückel 4n rule and, 464–465 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it I-30 Index Pyridoxal phosphate, amino acid catabolism and, 1005 imines from, 619 structure of, 27e, 900 Pyridoxamine phosphate, transamination and, 1005 Pyrimidine, aromaticity of, 464–465 basicity of, 793, 820 electrostatic potential map of, 464 Hückel 4n rule and, 464–465 nucleotides from, 943 Pyrrole, aromaticity of, 464, 817–818 basicity of, 793, 817 electrophilic substitution reactions of, 818 electrostatic potential map of, 465, 818 Hückel 4n rule and, 464 industrial synthesis of, 817 Pyrrolidine, electrostatic potential map of, 818 structure of, 789 Pyrrolysine, structure of, 874 Pyruvate, acetyl CoA from, 990–993 catabolism of, 990–993 from glucose, 982–989 glucose from, 998–1004 oxidative decarboxylation of, 990–993 reaction with thiamin diphosphate, 990–991 Pyruvate dehydrogenase complex, 990 Pyruvic acid, structure of, 655 Qiana, structure of, 726h Quantum mechanical model, 4–6 Quartet (NMR), 397 Quaternary ammonium salt, 788 Hofmann elimination and, 807–808 Quaternary carbon, 71 Quaternary structure (protein), 893 Quetiapine, structure of, 27f Quinine, structure of, 468, 821 Quinoline, aromaticity of, 468 electrophilic substitution reaction of, 821–822 Lindlar catalyst and, 272 Quinone(s), 558 hydroquinones from, 558 from phenols, 558 reduction of, 558 R configuration, 126 assignment of, 126 R group, 72 Racemate, 136 Racemic mixture, 136 Radical, 151–152 reactivity of, 152 stability of, 292, 294 Radical chain reaction, 153 initiation steps in, 153 propagation steps in, 153 termination steps in, 153 Radical reaction(s), 151–153 addition, 152 biological example of, 251–252, 253 characteristics of, 153 fishhook arrows and, 151 prostaglandin biosynthesis and, 153–154, 916–917 substitution, 152 Radio waves, electromagnetic spectrum and, 368 Radiofrequency energy, NMR spectroscopy and, 387–388 Rapamycin, discovery of, 218 structure of, 217 Rate equation, 313 Rate-determining step, 323 Rate-limiting step, 323 Rayon, 861 Re prochirality, 141–142 Reaction (polar), 152, 155–158 Reaction (radical), 151–153 Reaction coordinate, 172 Reaction intermediate, 174 Reaction mechanism, 151 Reaction rate, activation energy and, 172–173 Rearrangement reaction, 150 Reducing sugar, 853 Reduction, 235 acid chlorides, 699–700 aldehydes, 535–536, 617–618 aldoses, 852 alkene, 235–238 alkyne, 272–274 amides, 711–712 arenediazonium salt, 814 aromatic compounds, 513–514 carboxylic acids, 537–538, 694 disulfides, 585 esters, 537–538, 707–708 ketones, 535–536, 617–618 lactams, 712 nitriles, 671 organic, 303 quinones, 558 Reductive amination, 801–802 amino acid synthesis and, 880 biological example of, 802 mechanism of, 801 Refining (petroleum), 86–87 Regiospecific, 205 Registry of Mass Spectral Data, 358 Relenza, mechanism of, 865–866 Replication (DNA), 947–949 direction of, 949 error rate during, 949 lagging strand in, 949 leading strand in, 949 Okazaki fragments in, 949 replication fork in, 948 Replication fork (DNA), 948 Residue (protein), 881 Resist, photolithography and, 445–446 Resolution (enantiomers), 135–137, 136 Resonance, 36–40 acetate ion and, 36–37 acetone anion and, 38 acyl cations and, 490–491 allylic carbocations and, 426 allylic radical and, 294–295 arylamines and, 795 benzene and, 37, 457–458 benzylic carbocation and, 328 benzylic radical and, 511–512 carbonate ion and, 40 carboxylate ions and, 659 enolate ions and, 735 Lewis structures and, 36–37 naphthalene and, 467 pentadienyl radical and, 41 2,4-pentanedione anion and, 40 phenoxide ions and, 532 Resonance effect, electrophilic aromatic substitution and, 497 Resonance form, 36 drawing, 39–40 electron movement and, 37–39 rules for, 37–39 stability and, 39 three-atom groupings in, 39–40 Resonance hybrid, 37 Restriction endonuclease, 954 number of, 954 palindrome sequences in, 954 Retin A, structure of, 219j Retinal, vision and, 444 Retrosynthetic analysis, 279 Rhodium, aromatic hydrogenation catalyst, 513 Rhodopsin, isomerization of, 444 vision and, 444 Ribavirin, structure of, 477e Ribonucleic acid (RNA), 942 bases in, 943 biosynthesis of, 949–950 39 end of, 945 59 end of, 945 kinds of, 949 messenger, 949 ribosomal, 949 size of, 944 small, 949 structure of, 944–945 transfer, 949 translation of, 951–953 Ribonucleotide(s), structures of, 944 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Ribose, configuration of, 841 Ribosomal RNA, 949 function of, 949 Ring current (NMR), 471 [18]annulene and, 471–472 Ring-expansion reaction, 752d Ring-flip (cyclohexane), 103 energy barrier to, 103 molecular model of, 103 Ring-opening metathesis polymerization (ROMP), 1047 Risk, chemicals and, 25–26 RNA, see Ribonucleic acid Roberts, Irving, 223 Robinson annulation reaction, 776–777 mechanism of, 776 Rod cells, vision and, 444 Rofecoxib, NSAIDs and, 476 structure of, ROMP, see Ring-opening metathesis polymerization, 1047 rRNA, see Ribosomal RNA Rubber, production of, 437 structure of, 437 vulcanization of, 438 S configuration, 126 assignment of, 126–127 s-cis conformation, 434 Diels-Alder reaction and, 434–435 Saccharin, structure of, 867 sweetness of, 867 Safrole, structure of, 594k Samuelsson, Bengt, 915 Sandmeyer reaction, 812–813 mechanism of, 814 Sanger, Frederick, 890 Sanger dideoxy DNA sequencing, 954–955 Sanger’s reagent, 506 b-Santalene, structure of, 257 Saponification, 704–705, 911 mechanism of, 704–705 Saran, structure and uses of, 1040–1041 Sativene, synthesis of, 752j Saturated, 66 Saturated hydrocarbon, 66 Sawhorse representation, 80 SBR polymer, structure and uses of, 1042 Schiff base, 619, 986 see also Imine(s) Scurvy, vitamin C and, 675 sec-, name prefix, 71 sec-Butyl group, 71 Secobarbital, synthesis of, 749 Second-order reaction, 313 Secondary alcohol, 526 Secondary amine, 788 Secondary carbon, 71 Secondary hydrogen, 72 Index Secondary metabolite, 217 number of, 217 Secondary structure (protein), 893–894 Sedoheptulose, structure of, 834 Selenocysteine, structure of, 874 Semiconservative replication (DNA), 948 Sense strand (DNA), 950 Sequence rules, 124–126 enantiomers and, 124–128 E,Z alkene isomers and, 194–196 Serine, biosynthesis of, 1012d structure and properties of, 873 Seroquel, structure of, 27f Serotonin, 939–941 Serum lipoprotein, table of, 937 Serylalanine, molecular model of, 882 Sesquiterpene, 258 Sesquiterpenoid, 918 Sex hormone, 928 Sharpless, K Barry, 644 Sharpless epoxidation, 646 Shell (electron), capacity of, Shielding (NMR), 389 Si prochirality, 141–142 Sialic acid, 856–857 Side chain (amino acid), 874 Sigma (s) bond, 11 symmetry of, 11 Sigmatropic rearrangement, 1025–1029 antarafacial geometry of, 1026 examples of, 1027–1029 [1,5] hydrogen shift and, 1027 notation for, 1026 stereochemical rules for, 1026 suprafacial geometry of, 1026 vitamin D and, 1031–1032 Signal averaging, FT-NMR spectroscopy and, 408–409 Sildenafil, structure of, 817 Silver oxide, Hofmann elimination reaction and, 807–808 Simmons-Smith reaction, 246–247 Simple sugar, 833 Simvastatin, structure of, 88e Single bond, 14 electronic structure of, 13–14 length of, 13 strength of, 13 see also Alkane(s) Sirolimus, structure of, 217 Skeletal structure, 22 rules for drawing, 22 Skunk scent, cause of, 585 Small RNAs, 949 SN1 reaction, 323 allylic halides in, 329 benzylic halides in, 329 biological examples of, 333–334 I-31 carbocation stability and, 328 characteristics of, 327–332 energy diagram for, 325 epoxide cleavage and, 580 ion pairs in, 326 kinetics of, 323 leaving groups in, 329–330 mechanism of, 324–325 nucleophiles and, 330 racemization in, 325–326 rate law for, 323 rate-limiting step in, 324–325 solvent effects on, 331 stereochemistry of, 325–326 substrate structure and, 328 summary of, 332 SN2 reaction, 313–315 amines and, 799 biological example of, 334, 335 characteristics of, 316–322 crown ethers and, 584 electrostatic potential maps of, 315 energy diagrams for, 322 epoxide cleavage and, 320–321, 580, 582 inversion of configuration in, 313–314 kinetics of, 313 leaving groups and, 319–320 mechanism of, 313–314 nucleophiles in, 317–318 rate law for, 313 solvent effects and, 321 stereochemistry of, 313–314 steric hindrance in, 316–317 substrate structure and, 316–317 summary of, 322 table of, 318 tosylates and, 320 Williamson ether synthesis and, 570–571 Soap, 911–913 history of, 911 manufacture of, 911–912 mechanism of action of, 912–913 micelles of, 912 Sodium amide, reaction with alcohols, 531 Sodium bisulfite, osmate reduction with, 241 Sodium borohydride, reaction with ketones and aldehydes, 535 reaction with organomercury compounds, 229–230 Sodium chloride, dipole moment of, 32 Sodium cyclamate, LD50 of, 25 Sodium hydride, reaction with alcohols, 531 Solid-phase peptide synthesis, 890–893 PAM resin in, 892 Wang resin in, 892 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it I-32 Index Solvation, 321 carbocations and, 331 SN2 reaction and, 321 Solvent, polar aprotic, 321 protic, 321 SN1 reaction and, 331 SN2 reaction and, 321 Sorbitol, structure of, 852 Spandex, synthesis of, 1045 Specific rotation, 122 table of, 122 Sphingomyelin, 913–914 Sphingosine, structure of, 914 Spin density surface, allylic radical, 295 benzylic radical, 511–512 Spin-flip, NMR spectroscopy and, 387 Spin-spin splitting, 397, 398 alcohols and, 561 bromoethane and, 397–399 2-bromopropane and, 398, 399 n 1 rule and, 398 1H NMR spectroscopy and, 397–400 nonequivalent protons and, 405–406 origin of, 397–398 rules for, 400 tree diagrams and, 406 Split synthesis, 519, 520 Squalene, epoxidation of, 930–932 from farnesyl diphosphate, 930–931 steroid biosynthesis and, 930–932 Squalene oxide, cyclization of, 933, 935 Staggered conformation, ethane and, 81 molecular model of, 81 Stannous chloride, reaction with nitroarenes, 798 Starch, 1→4-a-links in, 861 structure of, 861 Statin drugs, heart disease and, 1010–1011 mechanism of action of, 1010–1011 sales of, 88e structure of, 88e Steam cracking, 186–187 Steam distillation, 257 Stearic acid, molecular model of, 909 structure of, 909 Stein, William, 884 Step-growth polymer, 715–717, 1043–1045 table of, 716 Stereocenter, 118 Stereochemistry, 80, 93 absolute configuration and, 128 Diels-Alder reaction and, 433 E1 reaction and, 344 E2 reaction and, 339–341 electrophilic addition reactions and, 252–256 R,S configuration and, 124–128 SN1 reaction and, 325–326 SN2 reactions and, 313–377 Stereogenic center, 118 Stereoisomers, 93 kinds of, 138–139 number of, 130 properties of, 134 Stereospecific, 246, 432 Stereospecific numbering, sn-glycerol 3-phosphate and, 971 Steric hindrance, SN2 reaction and, 316–317 Steric strain, 83 cis alkenes and, 198–199 substituted cyclohexanes and, 105–106 Steroid(s), 926–930 adrenocortical, 929–930 anabolic, 930 androgens, 929 biosynthesis of, 930–936 cis A-B ring fusion in, 927 conformation of, 926 contraceptive, 930 estrogens, 929 glucocorticoid, 929 mineralocorticoid, 929 molecular model of, 926 numbering of, 926 progestins, 929 stereochemistry of, 927–928 synthetic, 930 trans A-B ring fusion in, 927 Stork enamine reaction, 774–775 advantages of, 775 mechanism of, 774 STR loci, DNA fingerprinting and, 961–962 Straight-chain alkane, 67 Strecker synthesis, 831f Structure, condensed, 21–22 electron-dot, Kekulé, Lewis, line-bond, skeletal, 22 Strychnine, LD50 of, 25 Styrene, anionic polymerization of, 1039 Substituent, 73 Substituent effect, additivity of, 503–505 electrophilic aromatic substitution and, 493–495 explanation of, 496–503 summary of, 503 Substitution reaction, 150 Substrate (enzyme), 896 Succinic acid, structure of, 655 Sucralose, structure of, 867 sweetness of, 867 Sucrose, molecular model of, 860 specific rotation of, 122 structure of, 860 sweetness of, 867 Sugar, complex, 833 D, 839 L, 839 simple, 833 see also Aldose(s), Carbohydrate(s) Sulfa drug, 811 synthesis of, 485–486 Sulfanilamide, structure of, 486 synthesis of, 811 Sulfathiazole, structure of, 812 Sulfide(s), 568, 586–588 electrostatic potential map of, 64 naming, 586 oxidation of, 587 reaction with alkyl halides, 587 sulfoxides from, 587 from thiols, 586 Sulfonation (aromatic), 485–486 Sulfone, 587 from sulfoxides, 587 Sulfonium ion(s), 587 chirality of, 140–141 Sulfoxide(s), 587 oxidation of, 587 from sulfides, 587 Sunshine vitamin, 1031–1032 Super glue, structure of, 1039 Suprafacial geometry, 1022 Suture, polymers in, 717–718 Suzuki-Miyaura reaction, 302 mechanism of, 302 Sweeteners, synthetic, 866–867 Swine flu, 865 Symmetry-allowed reaction, 1014 Symmetry-disallowed reaction, 1014 Symmetry plane, 117, 118 Syn periplanar geometry, 339 molecular model of, 340 Syn stereochemistry, 232 Syndiotactic polymer, 1040 Synthase, 977 Synthesis, strategy of, 279 Table sugar, see Sucrose Tagatose, structure of, 834 Talose, configuration of, 841 Tamiflu, mechanism of, 865–866 molecular model of, 113 structure of, 27f Tamoxifen, structure of, 219g synthesis of, 648o Taq DNA polymerase, PCR and, 960 Tartaric acid, stereoisomers of, 133 Tautomer, 268, 728 Taxol, structure of, 284 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Tazobactam, 726e Teflon, structure and uses of, 250 Template strand (DNA), 950 Terephthalic acid, synthesis of, 510 Termination step (radical), 153 Terpene, 257–258 Terpenoid, 257–258, 917–925 biosynthesis of, 257–258, 918–925 classification of, 258, 918 isoprene rule and, 257–258 mevalonate biosynthetic pathway for, 919–922 tert-, name prefix, 71 tert-Amyl group, 76 tert-Butyl group, 71 Tertiary alcohol, 526 Tertiary amine, 788 Tertiary carbon, 71 Tertiary hydrogen, 72 Tertiary structure (protein), 893, 895 Testosterone, conformation of, 111 molecular model of, 111 structure of, 181e structure and function of, 929 Tetracaine, structure of, 831n Tetrahedral geometry, conventions for drawing, Tetrahydrofolate, structure of, 900 Tetrahydrofuran, as reaction solvent, 221 molecular model of, 568 Tetramethylsilane, NMR spectroscopy and, 392 Thalidomide, 182–184 Thermodynamic control, 428–430, 429 1,4-addition reactions and, 428–430 Thermoplastic polymer, 1049 characteristics of, 1049 examples of, 1049 Tg of, 1049 uses of, 1049 Thermosetting resin, 1051 cross-linking in, 1051 uses of, 1051 Thiamin, structure of, 466, 819, 900 thiazolium ring in, 466 Thiamin diphosphate, pKa of, 990 reaction with pyruvate, 990–991 structure of, 990 ylide from, 990 Thiazole, basicity of, 819 thio-, thioester name suffix, 681 Thioacetal, synthesis of, 648g Thioanisole, electrostatic potential map of, 678a -thioate, thioester name suffix, 681 Thioester(s), 680 biological reduction of, 713–714 electrostatic potential map of, 685 Index naming, 681 pKa of, 736 Thiol(s), 568, 584–586 from alkyl halides, 585 disulfides from, 585 electrostatic potential map of, 64 hybridization of, 19 naming, 584 odor of, 585 oxidation of, 585 pKa of, 530 polarizability of, 156 reaction with alkyl halides, 586 reaction with Br2, 585 reaction with NaH, 586 sulfides from, 586 thiolate ions from, 586 Thiolate ion, 586 Thionyl chloride, reaction with alcohols, 298, 544 reaction with amides, 668–669 reaction with carboxylic acids, 688–689 Thiophene, aromaticity of, 466 Thiourea, reaction with alkyl halides, 585 Threonine, stereoisomers of, 130 structure and properties of, 873 Threose, configuration of, 841 molecular model of, 121 Thromboxane B2, structure of, 915 Thymine, electrostatic potential map of, 946 structure of, 943 Thyroxine, biosynthesis of, 484 structure of, 874 Time-of-flight (TOF) mass spectrometry, 367 Titration curve, alanine, 877–878 TMS, see Tetramethylsilane, Trimethylsilyl ether Tollens’ test, 853 Toluene, electrostatic potential map of, 498 IR spectrum of, 469–470 13C NMR absorptions of, 473 1H NMR spectrum of, 404, 405 Toluene-2,4-diisocyanate, polyurethanes from, 1045 p-Toluenesulfonyl chloride, reaction with alcohols, 544–545 Torsional strain, 81 Tosylate, 311 from alcohols, 544–545 SN2 reactions and, 320, 544–545 uses of, 545 Toxicity, chemicals and, 25–26 Trans fatty acid, from vegetable oil, 910–911 from hydrogenation of fats, 237–238 I-33 Transamination, 1005–1008 mechanisms in, 1005–1008 steps in, 1005–1008 Transcription (DNA), 949–950 antisense strand and, 950 consensus sequence and, 949 promoter sequence and, 949 sense strand and, 950 Transfer RNA, 949 anticodons in, 952–953 function of, 952–953 molecular model of, 952 shape of, 952 Transferase, 897 Transition state, 172 Hammond postulate and, 212–213 Translation (RNA), 951–953 Tranylcypromine, synthesis of, 805 Tree diagram (NMR), 406 Triacylglycerol, 908 catabolism of, 968–976 Trialkylsulfonium ion(s), alkylations with, 587 chirality of, 140–141 Tricarboxylic acid cycle, see Citric acid cycle Triethylamine, mass spectrometry of, 363 Trifluoroacetic acid, pKa of, 658 Trifluoromethylbenzene, electrostatic potential map of, 498 Triglyceride, see Triacylglycerol, 908 Trimethylamine, bond angles in, 790 bond lengths in, 790 electrostatic potential map of, 792 molecular model of, 790 Trimethylsilyl ether, from alcohols, 553–554 cleavage of, 554 synthesis of, 553–554 Trimetozine, synthesis of, 699 2,4,6-Trinitrochlorobenzene, electro­static potential map of, 505 Triphenylphosphine, reaction with alkyl halides, 631 Triple bond, 14, 17 electronic structure of, 17 length of, 18 strength of, 18 see also Alkyne(s) Triplet (NMR), 397 Trisubstituted aromatic compound, synthesis of, 514–519 Triterpenoid, 917 tRNA, see Transfer RNA Trypsin, peptide cleavage with, 886 Tryptophan, pKa of, 45 structure and properties of, 873 Turnover number (enzyme), 896 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it I-34 Index Twist-boat conformation (cyclohexane), 100–101 molecular model of, 101 steric strain in, 101 Tyrosine, biosynthesis of, 548 catabolism of, 1012c iodination of, 484 structure and properties of, 873 Ubiquinones, function of, 558–559 structure of, 558 Ultrahigh-molecular-weight polyethylene, uses of, 1041 Ultraviolet light, electromagnetic spectrum and, 368 wavelength of, 438–439 Ultraviolet spectroscopy, 438–441 absorbance and, 440 aromatic compounds, 470 conjugation and, 441–442 HOMO-LUMO transition in, 439 molar absorptivity and, 440 Ultraviolet spectrum, benzene, 442, 470 b-carotene, 442–443 1,3-butadiene, 440 3-buten-2-one, 442 1,3-cyclohexadiene, 442 ergosterol, 447k 1,3,5-hexatriene, 442 Unimolecular, 323 Unsaturated, 187 Unsaturated aldehyde, conjugate addition reactions of, 635–639 Unsaturated ketone, conjugate addition reactions of, 635–639 Unsaturation, degree of, 187 Upfield, (NMR), 392 Uracil, structure of, 943 Urea, from ammonium cyanate, Urethane, 1045 Uric acid, pKa of, 678g Uronic acid, 854 from aldoses, 854 Urushiols, structure of, 526 UV, see Ultraviolet Valence bond theory, 10–11 Valence shell, Valganciclovir, structure and function of, 963d Valine, structure and properties of, 873 Valinomycin, 585 Valsartan, synthesis of, 302 Van der Waals force, polymers and, 1048 van’t Hoff, Jacobus Hendricus, Vegetable oil, 908–911 composition of, 909 hydrogenation of, 237–238, 910–911 Veronal, synthesis of, 748 Vestenamer, synthesis of, 1047–1048 Vicinal, 265, 578 Vinyl group, 191 Vinyl monomer, 249–250 Vinylcyclopropane, rearrangement of, 1033e Vinylic anion, electrostatic potential map of, 276 stability of, 276 Vinylic carbocation, from alkynes, 267 electronic structure of, 267 electrostatic potential map of, 267 stability of, 267 Vinylic halide, alkynes from, 265 SN2 reaction and, 317 Vinylic protons, 1H NMR spectroscopy and, 394–395 Vinylic radical, alkyne reduction and, 274 Vioxx, 1, 476 Visible light, electromagnetic spectrum and, 368 Vision, chemistry of, 443–444 retinal and, 444 Vitalistic theory, Vitamin, 675 Vitamin A, industrial synthesis of, 272 structure of, 56 synthesis of, 631–632 Vitamin B1, structure of, 819 Vitamin B12, structure of, 283 synthesis of, 283 Vitamin C, industrial synthesis of, 675–676 molecular model of, 675 scurvy and, 675 stereochemistry of, 148e structure of, 56 uses of, 675 Vitamin D, sigmatropic rearrangements and, 1031–1032 Vitamin K1, biosynthesis of, 491–492 Viton polymer, structure and uses of, 1042 VLDL, heart disease and, 937 Volcano, chloromethane from, 287 Vulcanization, 438 Walden, Paul, 310 Walden inversion, 310–312 Wang resin, solid-phase peptide synthesis and, 892 Water, acid-base behavior of, 44 dipole moment of, 32 electrostatic potential map of, 46 nucleophilic addition reaction of, 614–615 pKa of, 45 reaction with aldehydes, 614–615 reaction with ketones, 614–615 Watson, James Dewey, 945 Watson-Crick DNA model, 945–946 Wave equation, Wave function, molecular orbitals and, 20 Wavelength (l), 369 Wavenumber, 371 Wax, 908 Whale blubber, composition of, 909 Wieland-Miescher ketone, synthesis of, 783j Williamson ether synthesis, 570–571 carbohydrates and, 849 mechanism of, 570–571 Willstätter, Richard, 460 Wittig reaction, 630–632 mechanism of, 630–631 uses of, 631–632 vitamin A synthesis using, 631–632 Wohl degradation, 855–856 Wöhler, Friedrich, Wolff-Kishner reaction, 624–626 mechanism of, 624–626 Wood alcohol, 525 Woodward, Robert Burns, 283, 1014 Woodward-Hoffmann rules, 1014–1015 X-Ray crystallography, 384 X-Ray diffractometer, 384 X rays, electromagnetic spectrum and, 368 o-Xylene, ozonolysis of, 477d Xylocaine, structure of, 57 Xylose, configuration of, 841 -yl, alkyl group name suffix, 70 -yl phosphate, acyl phosphate name suffix, 682 Ylide, 630 -yne, alkyne name suffix, 314 Z configuration, 194–196 assignment of, 194–196 Zaitsev, Alexander M., 336 Zaitsev’s rule, 336 alcohol dehydration and, 546 E1 reaction and, 344 E2 reaction and, 341–342 Hofmann elimination and, 807–808 proof for, 416–417 Zanamivir, mechanism of, 865–866 Zeisel method, 594l Ziegler-Natta catalyst, 1040 Zinc-copper, Simmons-Smith reaction and, 246–247 Zocor, structure of, 88e Zwitterion, 871 electrostatic potential map of, 871 Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Structures of Some Common Functional Groups Name Alkene (double bond) Alkyne (triple bond) Structure* C Name ending Example -ene H2C P CH2 Ethene -yne HC q CH Ethyne C OCqCO Arene (aromatic ring) None Benzene Halide C X None CH3Cl Chloromethane -ol CH3OH Methanol ether CH3OCH3 Dimethyl ether phosphate CH3OPO322 Methyl phosphate diphosphate CH3OP2O632 Methyl diphosphate -amine CH3NH2 Methylamine (X  5  F, Cl, Br, I) Alcohol Ether C C OH O Monophosphate C O C O Diphosphate P O– O C O P O– Amine C Imine (Schiff base) Thiol C OCqN C O O P O– O– N None N C Nitrile O– SH NH CH3CCH3 C Acetone imine -nitrile CH3CqN Ethanenitrile -thiol CH3SH Methanethiol *The bonds whose connections aren’t specified are assumed to be attached to carbon or hydrogen atoms in the rest of the molecule Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it Structures of Some Common Functional Groups (Continued) Name Sulfide Structure* C S C Disulfide C S C S+ Ketone Carboxylic acid Ester Thioester C C C Amide C -one Acid chloride C Carboxylic acid anhydride C -oic acid C O CH3COH OH Ethanoic acid -oate O O CH3COCH3 C Methyl ethanoate -thioate S C CH3CSCH3 O CH3CNH2 N Ethanamide -oyl chloride O CH3CCl Cl Ethanoyl chloride -oic anhydride O O O Methyl ethanethioate -amide O C O Propanone O C O CH3CCH3 C O C O– + CH3SCH3 CH3CH Ethanal H O C CH3SSCH3 Dimethyl disulfide -al O C disulfide Dimethyl sulfoxide O C CH3SCH3 Dimethyl sulfide C O C sulfide sulfoxide O C Example C O– Sulfoxide Aldehyde S Name ending C C O O CH3COCCH3 Ethanoic anhydride *The bonds whose connections aren’t specified are assumed to be attached to carbon or hydrogen atoms in the rest of the molecule Copyright 2016 Cengage Learning All Rights Reserved May not be copied, scanned, or duplicated, in whole or in part Due to electronic rights, some third party content may be suppressed from the eBook and/or eChapter(s) Editorial review has deemed that any suppressed content does not materially affect the overall learning experience Cengage Learning reserves the right to remove additional content at any time if subsequent rights restrictions require it ... AB3C1 C2 AB1C2 AB3C2 AB2C1 AB4C1 AB2C2 AB4C2 D1 AB1C1D1 AB1C2D1 AB1C3D1 AB1C4D1 AB2C1D1 AB2C2D1 AB2C3D1 AB2C4D1 AB3C1D1 AB3C2D1 AB3C3D1 AB3C4D1 C3 AB1C3 AB3C3 AB2C3 AB4C3 D2 AB4C1D1 AB4C2D1 AB4C3D1... each? (a) CN CN CH3CH2COCl, AlCl3 HNO3, H2SO4 O2N C CH2CH3 O (b) Cl Cl CH3CH2CH2Cl, AlCl3 Cl2, FeCl3 CH3CH2CH2 Cl Something Extra Combinatorial Chemistry Traditionally, organic compounds have... Br2 + HBr (c) Chlorination (Section 16 -2) Cl Cl2, FeCl3 + HCl (d) Iodination (Section 16 -2) I + I2 CuCl2 + HI (e) Nitration (Section 16 -2) NO2 + HNO3 H2SO4 + H2O (f) Sulfonation (Section 16 -2)

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  • Brief Contents

  • Detailed Contents

  • Preface

  • Ch 1: Structure and Bonding

    • 1-1: Atomic Structure: The Nucleus

    • 1-2: Atomic Structure: Orbitals

    • 1-3: Atomic Structure: Electron Configurations

    • 1-4: Development of Chemical Bonding Theory

    • 1-5: Describing Chemical Bonds: Valence Bond Theory

    • 1-6: sp3 Hybrid Orbitals and the Structure of Methane

    • 1-7: sp3 Hybrid Orbitals and the Structure of Ethane

    • 1-8: sp2 Hybrid Orbitals and the Structure of Ethylene

    • 1-9: sp Hybrid Orbitals and the Structure of Acetylene

    • 1-10: Hybridization of Nitrogen, Oxygen, Phosphorus, and Sulfur

    • 1-11: Describing Chemical Bonds: Molecular Orbital Theory

    • 1-12: Drawing Chemical Structures

    • Summary

    • Exercises

  • Ch 2: Polar Covalent Bonds; Acids and Bases

    • 2-1: Polar Covalent Bonds: Electronegativity

    • 2-2: Polar Covalent Bonds: Dipole Moments

    • 2-3: Formal Charges

    • 2-4: Resonance

    • 2-5: Rules for Resonance Forms

    • 2-6: Drawing Resonance Forms

    • 2-7: Acids and Bases: The Bronsted-Lowry Definition

    • 2-8: Acid and Base Strength

    • 2-9: Predicting Acid-Base Reactions from pKa Values

    • 2-10: Organic Acids and Organic Bases

    • 2-11: Acids and Bases: The Lewis Definition

    • 2-12: Noncovalent Interactions between Molecules

    • Summary

    • Exercises

  • Ch 3: Organic Compounds: Alkanes and Their Stereochemistry

    • 3-1: Functional Groups

    • 3-2: Alkanes and Alkane Isomers

    • 3-3: Alkyl Groups

    • 3-4: Naming Alkanes

    • 3-5: Properties of Alkanes

    • 3-6: Conformations of Ethane

    • 3-7: Conformations of Other Alkanes

    • Summary

    • Exercises

  • Ch 4: Organic Compounds: Cycloalkanes and Their Stereochemistry

    • 4-1: Naming Cycloalkanes

    • 4-2: Cis-Trans Isomerism in Cycloalkanes

    • 4-3: Stability of Cycloalkanes: Ring Strain

    • 4-4: Conformations of Cycloalkanes

    • 4-5: Conformations of Cyclohexane

    • 4-6: Axial and Equatorial Bonds in Cyclohexane

    • 4-7: Conformations of Monosubstituted Cyclohexanes

    • 4-8: Conformations of Disubstituted Cyclohexanes

    • 4-9: Conformations of Polycyclic Molecules

    • Summary

    • Exercises

  • Ch 5: Stereochemistry at Tetrahedral Centers

    • 5-1: Enantiomers and the Tetrahedral Carbon

    • 5-2: The Reason for Handedness in Molecules: Chirality

    • 5-3: Optical Activity

    • 5-4: Pasteur's Discovery of Enantiomers

    • 5-5: Sequence Rules for Specifying Configuration

    • 5-6: Diastereomers

    • 5-7: Meso Compounds

    • 5-8: Racemic Mixtures and the Resolution of Enantiomers

    • 5-9: A Review of Isomerism

    • 5-10: Chirality at Nitrogen, Phosphorus, and Sulfur

    • 5-11: Prochirality

    • 5-12: Chirality in Nature and Chiral Environments

    • Summary

    • Exercises

  • Ch 6: An Overview of Organic Reactions

    • 6-1: Kinds of Organic Reactions

    • 6-2: How Organic Reactions Occur: Mechanisms

    • 6-3: Radical Reactions

    • 6-4: Polar Reactions

    • 6-5: An Example of a Polar Reaction: Addition of HBr to Ethylene

    • 6-6: Using Curved Arrows in Polar Reaction Mechanisms

    • 6-7: Describing a Reaction: Equilibria, Rates, and Energy Changes

    • 6-8: Describing a Reaction: Bond Dissociation Energies

    • 6-9: Describing a Reaction: Energy Diagrams and Transition States

    • 6-10: Describing a Reaction: Intermediates

    • 6-11: A Comparison between Biological Reactions and Laboratory Reactions

    • Summary

    • Exercises

    • Practice Your Scientific Analysis and Reasoning I: The Chiral Drug Thalidomide

  • Ch 7: Alkenes: Structure and Reactivity

    • 7-1: Industrial Preparation and Use of Alkenes

    • 7-2: Calculating Degree of Unsaturation

    • 7-3: Naming Alkenes

    • 7-4: Cis-Trans Isomerism in Alkenes

    • 7-5: Alkene Stereochemistry and the E,Z Designation

    • 7-6: Stability of Alkenes

    • 7-7: Electrophilic Addition Reactions of Alkenes

    • 7-8: Orientation of Electrophilic Additions: Markovnikov's Rule

    • 7-9: Carbocation Structure and Stability

    • 7-10: The Hammond Postulate

    • 7-11: Evidence for the Mechanism of Electrophilic Additions: Carbocation Rearrangements

    • Summary

    • Exercises

  • Ch 8: Alkenes: Reactions and Synthesis

    • 8-1: Preparing Alkenes: A Preview of Elimination Reactions

    • 8-2: Halogenation of Alkenes: Addition of X2

    • 8-3: Halohydrins from Alkenes: Addition of HOX

    • 8-4: Hydration of Alkenes: Addition of H2O by Oxymercuration

    • 8-5: Hydration of Alkenes: Addition of H2O by Hydroboration

    • 8-6: Reduction of Alkenes: Hydrogenation

    • 8-7: Oxidation of Alkenes: Epoxidation and Hydroxylation

    • 8-8: Oxidation of Alkenes: Cleavage to Carbonyl Compounds

    • 8-9: Addition of Carbenes to Alkenes: Cyclopropane Synthesis

    • 8-10: Radical Additions to Alkenes: Chain-Growth Polymers

    • 8-11: Biological Additions of Radicals to Alkenes

    • 8-12: Reaction Stereochemistry: Addition of H2O to an Achiral Alkene

    • 8-13: Reaction Stereochemistry: Addition of H2O to a Chiral Alkene

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 9: Alkynes: An Introduction to Organic Synthesis

    • 9-1: Naming Alkynes

    • 9-2: Preparation of Alkynes: Elimination Reactions of Dihalides

    • 9-3: Reactions of Alkynes: Addition of HX and X2

    • 9-4: Hydration of Alkynes

    • 9-5: Reduction of Alkynes

    • 9-6: Oxidative Cleavage of Alkynes

    • 9-7: Alkyne Acidity: Formation of Acetylide Anions

    • 9-8: Alkylation of Acetylide Anions

    • 9-9: An Introduction to Organic Synthesis

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 10: Organohalides

    • 10-1: Names and Structures of Alkyl Halides

    • 10-2: Preparing Alkyl Halides from Alkanes: Radical Halogenation

    • 10-3: Preparing Alkyl Halides from Alkenes: Allylic Bromination

    • 10-4: Stability of the Allyl Radical: Resonance Revisited

    • 10-5: Preparing Alkyl Halides from Alcohols

    • 10-6: Reactions of Alkyl Halides: Grignard Reagents

    • 10-7: Organometallic Coupling Reactions

    • 10-8: Oxidation and Reduction in Organic Chemistry

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 11: Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations

    • 11-1: The Discovery of Nucleophilic Substitution Reactions

    • 11-2: The SN2 Reaction

    • 11-3: Characteristics of the SN2 Reaction

    • 11-4: The SN1 Reaction

    • 11-5: Characteristics of the SN1 Reaction

    • 11-6: Biological Substitution Reactions

    • 11-7: Elimination Reactions: Zaitsev's Rule

    • 11-8: The E2 Reaction and the Deuterium Isotope Effect

    • 11-9: The E2 Reaction and Cyclohexane Conformation

    • 11-10: The E1 and E1cB Reactions

    • 11-11: Biological Elimination Reactions

    • 11-12: A Summary of Reactivity: SN1, SN2, E1, E1cB, and E2

    • Summary

    • Summary of Reactions

    • Exercises

    • Practice Your Scientific Analysis and Reasoning II: From Mustard Gas to Alkylating Anticancer Drugs

  • Ch 12: Structure Determination: Mass Spectrometry and Infrared Spectroscopy

    • 12-1: Mass Spectrometry of Small Molecules: Magnetic-Sector Instruments

    • 12-2: Interpreting Mass Spectra

    • 12-3: Mass Spectrometry of Some Common Functional Groups

    • 12-4: Mass Spectrometry in Biological Chemistry: Time-of-Flight (TOF) Instruments

    • 12-5: Spectroscopy and the Electromagnetic Spectrum

    • 12-6: Infrared Spectroscopy

    • 12-7: Interpreting Infrared Spectra

    • 12-8: Infrared Spectra of Some Common Functional Groups

    • Summary

    • Exercises

  • Ch 13: Structure Determination: Nuclear Magnetic Resonance Spectroscopy

    • 13-1: Nuclear Magnetic Resonance Spectroscopy

    • 13-2: The Nature of NMR Absorptions

    • 13-3: The Chemical Shift

    • 13-4: Chemical Shifts in 1H NMR Spectroscopy

    • 13-5: Integration of 1H NMR Absorptions: Proton Counting

    • 13-6: Spin-Spin Splitting in 1H NMR Spectra

    • 13-7: 1H NMR Spectroscopy and Proton Equivalence

    • 13-8: More Complex Spin-Spin Splitting Patterns

    • 13-9: Uses of 1H NMR Spectroscopy

    • 13-10: 13C NMR Spectroscopy: Signal Averaging and FT-NMR

    • 13-11: Characteristics of 13C NMR Spectroscopy

    • 13-12: DEPT 13C NMR Spectroscopy

    • 13-13: Uses of 13C NMR Spectroscopy

    • Summary

    • Exercises

  • Ch 14: Conjugated Compounds and Ultraviolet Spectroscopy

    • 14-1: Stability of Conjugated Dienes: Molecular Orbital Theory

    • 14-2: Electrophilic Additions to Conjugated Dienes: Allylic Carbocations

    • 14-3: Kinetic versus Thermodynamic Control of Reactions

    • 14-4: The Diels-Alder Cycloaddition Reaction

    • 14-5: Characteristics of the Diels-Alder Reaction

    • 14-6: Diene Polymers: Natural and Synthetic Rubbers

    • 14-7: Ultraviolet Spectroscopy

    • 14-8: Interpreting Ultraviolet Spectra: The Effect of Conjugation

    • 14-9: Conjugation, Color, and the Chemistry of Vision

    • Summary

    • Summary of Reactions

    • Exercises

    • Practice Your Scientific Analysis and Reasoning III : Photodynamic Therapy (PDT)

  • Ch 15: Benzene and Aromaticity

    • 15-1: Naming Aromatic Compounds

    • 15-2: Structure and Stability of Benzene

    • 15-3: Aromaticity and the Huckel 4n + 2 Rule

    • 15-4: Aromatic Ions

    • 15-5: Aromatic Heterocycles: Pyridine and Pyrrole

    • 15-6: Polycyclic Aromatic Compounds

    • 15-7: Spectroscopy of Aromatic Compounds

    • Summary

    • Exercises

  • Ch 16: Chemistry of Benzene: Electrophilic Aromatic Substitution

    • 16-1: Electrophilic Aromatic Substitution Reactions: Bromination

    • 16-2: Other Aromatic Substitutions

    • 16-3: Alkylation and Acylation of Aromatic Rings: The Friedel-Crafts Reaction

    • 16-4: Substituent Effects in Electrophilic Substitutions

    • 16-5: Trisubstituted Benzenes: Additivity of Effects

    • 16-6: Nucleophilic Aromatic Substitution

    • 16-7: Benzyne

    • 16-8: Oxidation of Aromatic Compounds

    • 16-9: Reduction of Aromatic Compounds

    • 16-10: Synthesis of Polysubstituted Benzenes

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 17: Alcohols and Phenols

    • 17-1: Naming Alcohols and Phenols

    • 17-2: Properties of Alcohols and Phenols

    • 17-3: Preparation of Alcohols: A Review

    • 17-4: Alcohols from Carbonyl Compounds: Reduction

    • 17-5: Alcohols from Carbonyl Compounds: Grignard Reaction

    • 17-6: Reactions of Alcohols

    • 17-7: Oxidation of Alcohols

    • 17-8: Protection of Alcohols

    • 17-9: Phenols and Their Uses

    • 17-10: Reactions of Phenols

    • 17-11: Spectroscopy of Alcohols and Phenols

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 18: Ethers and Epoxides; Thiols and Sulfides

    • 18-1: Names and Properties of Ethers

    • 18-2: Preparing Ethers

    • 18-3: Reactions of Ethers: Acidic Cleavage

    • 18-4: Reactions of Ethers: Claisen Rearrangement

    • 18-5: Cyclic Ethers: Epoxides

    • 18-6: Reactions of Epoxides: Ring-Opening

    • 18-7: Crown Ethers

    • 18-8: Thiols and Sulfides

    • 18-9: Spectroscopy of Ethers

    • Summary

    • Summary of Reactions

    • Exercises

    • Preview of Carbonyl Chemistry

  • Ch 19: Aldehydes and Ketones: Nucleophilic Addition Reactions

    • 19-1: Naming Aldehydes and Ketones

    • 19-2: Preparing Aldehydes and Ketones

    • 19-3: Oxidation of Aldehydes and Ketones

    • 19-4: Nucleophilic Addition Reactions of Aldehydes and Ketones

    • 19-5: Nucleophilic Addition of H2O: Hydration

    • 19-6: Nucleophilic Addition of HCN: Cyanohydrin Formation

    • 19-7: Nucleophilic Addition of Hydride and Grignard Reagents: Alcohol Formation

    • 19-8: Nucleophilic Addition of Amines: Imine and Enamine Formation

    • 19-9: Nucleophilic Addition of Hydrazine: The Wolff-Kishner Reaction

    • 19-10: Nucleophilic Addition of Alcohols: Acetal Formation

    • 19-11: Nucleophilic Addition of Phosphorus Ylides: The Wittig Reaction

    • 19-12: Biological Reductions

    • 19-13: Conjugate Nucleophilic Addition to a,B-Unsaturated Aldehydes and Ketones

    • 19-14: Spectroscopy of Aldehydes and Ketones

    • Summary

    • Summary of Reactions

    • Exercises

    • Practice Your Scientific Analysis and Reasoning IV: Selective Serotonin Reuptake Inhibitors (SSRIs)

  • Ch 20: Carboxylic Acids and Nitriles

    • 20-1: Naming Carboxylic Acids and Nitriles

    • 20-2: Structure and Properties of Carboxylic Acids

    • 20-3: Biological Acids and the Henderson-Hasselbalch Equation

    • 20-4: Substituent Effects on Acidity

    • 20-5: Preparing Carboxylic Acids

    • 20-6: Reactions of Carboxylic Acids: An Overview

    • 20-7: Chemistry of Nitriles

    • 20-8: Spectroscopy of Carboxylic Acids and Nitriles

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 21: Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions

    • 21-1: Naming Carboxylic Acid Derivatives

    • 21-2: Nucleophilic Acyl Substitution Reactions

    • 21-3: Reactions of Carboxylic Acids

    • 21-4: Chemistry of Acid Halides

    • 21-5: Chemistry of Acid Anhydrides

    • 21-6: Chemistry of Esters

    • 21-7: Chemistry of Amides

    • 21-8: Chemistry of Thioesters and Acyl Phosphates: Biological Carboxylic Acid Derivatives

    • 21-9: Polyamides and Polyesters: Step-Growth Polymers

    • 21-10: Spectroscopy of Carboxylic Acid Derivatives

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 22: Carbonyl Alpha-Substitution Reactions

    • 22-1: Keto-Enol Tautomerism

    • 22-2: Reactivity of Enols: a-Substitution Reactions

    • 22-3: Alpha Halogenation of Aldehydes and Ketones

    • 22-4: Alpha Bromination of Carboxylic Acids

    • 22-5: Acidity of Alpha Hydrogen Atoms: Enolate Ion Formation

    • 22-6: Reactivity of Enolate Ions

    • 22-7: Alkylation of Enolate Ions

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 23: Carbonyl Condensation Reactions

    • 23-1: Carbonyl Condensations: The Aldol Reaction

    • 23-2: Carbonyl Condensations versus Alpha Substitutions

    • 23-3: Dehydration of Aldol Products: Synthesis of Enones

    • 23-4: Using Aldol Reactions in Synthesis

    • 23-5: Mixed Aldol Reactions

    • 23-6: Intramolecular Aldol Reactions

    • 23-7: The Claisen Condensation Reaction

    • 23-8: Mixed Claisen Condensations

    • 23-9: Intramolecular Claisen Condensations: The Dieckmann Cyclization

    • 23-10: Conjugate Carbonyl Additions: The Michael Reaction

    • 23-11: Carbonyl Condensations with Enamines: The Stork Reaction

    • 23-12: The Robinson Annulation Reaction

    • 23-13: Some Biological Carbonyl Condensation Reactions

    • Summary

    • Summary of Reactions

    • Exercises

    • Practice Your Scientific Analysis and Reasoning V: Thymine in DNA

  • Ch 24: Amines and Heterocycles

    • 24-1: Naming Amines

    • 24-2: Structure and Properties of Amines

    • 24-3: Basicity of Amines

    • 24-4: Basicity of Arylamines

    • 24-5: Biological Amines and the Henderson-Hasselbalch Equation

    • 24-6: Synthesis of Amines

    • 24-7: Reactions of Amines

    • 24-8: Reactions of Arylamines

    • 24-9: Heterocyclic Amines

    • 24-10: Spectroscopy of Amines

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 25: Biomolecules: Carbohydrates

    • 25-1: Classification of Carbohydrates

    • 25-2: Representing Carbohydrate Stereochemistry: Fischer Projections

    • 25-3: D,L Sugars

    • 25-4: Configurations of the Aldoses

    • 25-5: Cyclic Structures of Monosaccharides: Anomers

    • 25-6: Reactions of Monosaccharides

    • 25-7: The Eight Essential Monosaccharides

    • 25-8: Disaccharides

    • 25-9: Polysaccharides and Their Synthesis

    • 25-10: Some Other Important Carbohydrates

    • 25-11: Cell-Surface Carbohydrates and Influenza Viruses

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 26: Biomolecules: Amino Acids, Peptides, and Proteins

    • 26-1: Structures of Amino Acids

    • 26-2: Amino Acids and the Henderson-Hasselbalch Equation: Isoelectric Points

    • 26-3: Synthesis of Amino Acids

    • 26-4: Peptides and Proteins

    • 26-5: Amino Acid Analysis of Peptides

    • 26-6: Peptide Sequencing: The Edman Degradation

    • 26-7: Peptide Synthesis

    • 26-8: Automated Peptide Synthesis: The Merrifield Solid-Phase Method

    • 26-9: Protein Structure

    • 26-10: Enzymes and Coenzymes

    • 26-11: How Do Enzymes Work? Citrate Synthase

    • Summary

    • Summary of Reactions

    • Exercises

  • Ch 27: Biomolecules: Lipids

    • 27-1: Waxes, Fats, and Oils

    • 27-2: Soap

    • 27-3: Phospholipids

    • 27-4: Prostaglandins and Other Eicosanoids

    • 27-5: Terpenoids

    • 27-6: Steroids

    • 27-7: Biosynthesis of Steroids

    • Summary

    • Exercises

    • Practice Your Scientific Analysis and Reasoning VI: Melatonin and Serotonin

  • Ch 28: Biomolecules: Nucleic Acids

    • 28-1: Nucleotides and Nucleic Acids

    • 28-2: Base Pairing in DNA: The Watson-Crick Model

    • 28-3: Replication of DNA

    • 28-4: Transcription of DNA

    • 28-5: Translation of RNA: Protein Biosynthesis

    • 28-6: DNA Sequencing

    • 28-7: DNA Synthesis

    • 28-8: The Polymerase Chain Reaction

    • Summary

    • Exercises

  • Ch 29: The Organic Chemistry of Metabolic Pathways

    • 29-1: An Overview of Metabolism and Biochemical Energy

    • 29-2: Catabolism of Triacylglycerols: The Fate of Glycerol

    • 29-3: Catabolism of Triacylglycerols: B-Oxidation

    • 29-4: Biosynthesis of Fatty Acids

    • 29-5: Catabolism of Carbohydrates: Glycolysis

    • 29-6: Conversion of Pyruvate to Acetyl CoA

    • 29-7: The Citric Acid Cycle

    • 29-8: Carbohydrate Biosynthesis: Gluconeogenesis

    • 29-9: Catabolism of Proteins: Deamination

    • 29-10: Some Conclusions about Biological Chemistry

    • Summary

    • Exercises

  • Ch 30: Orbitals and Organic Chemistry: Pericyclic Reactions

    • 30-1: Molecular Orbitals of Conjugated Pi Systems

    • 30-2: Electrocyclic Reactions

    • 30-3: Stereochemistry of Thermal Electrocyclic Reactions

    • 30-4: Photochemical Electrocyclic Reactions

    • 30-5: Cycloaddition Reactions

    • 30-6: Stereochemistry of Cycloadditions

    • 30-7: Sigmatropic Rearrangements

    • 30-8: Some Examples of Sigmatropic Rearrangements

    • 30-9: A Summary of Rules for Pericyclic Reactions

    • Summary

    • Exercises

    • Practice Your Scientific Analysis and Reasoning VII: The Potent Antibiotic Traits of Endiandric Acid C

  • Ch 31: Synthetic Polymers

    • 31-1: Chain-Growth Polymers

    • 31-2: Stereochemistry of Polymerization: Ziegler-Natta Catalysts

    • 31-3: Copolymers

    • 31-4: Step-Growth Polymers

    • 31-5: Olefin Metathesis Polymerization

    • 31-6: Polymer Structure and Physical Properties

    • Summary

    • Exercises

  • A: Nomenclature of Polyfunctional Organic Compounds

  • B: Acidity Constants for Some Organic Compounds

  • C: Glossary

  • D: Answers to In-Text Problems

  • Index

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