Ebook Organic chemistry (6th edition) Part 2

(BQ) Part 2 book Organic chemistry has contents: Functional derivatives of carboxylic acids, enolate anions and enamines; benzene and the concept of aromaticity; reactions of benzene and its derivatives; catalytic carbon carbon bond formation; carbohydrates,...and other contents.

Outline 18.1 Structure and Nomenclature 18.2 Acidity of Amides, Imides, and Sulfonamides 18.3 18.4 Chapter 18 Characteristic Reactions Functional Derivatives of Carboxylic Acids Reaction with Water: Hydrolysis 18.5 18.6 Reaction with Alcohols 18.7 Reaction of Acid Chlorides with Salts of Carboxylic Acids 18.8 Interconversion of Functional Derivatives 18.9 Reactions with Organometallic Compounds Reactions with Ammonia and Amines 18.10 Reduction Colored scanning electron micrograph of Penicillium s fungus The stalklike objects are condiophores to which are attached numerous round condia The condia are the fruiting bodies of the fungus Inset: a model of amoxicillin See Chemical Connections: “The Penicillins and Cephalosporins: b-Lactam Antibiotics.” © SCIMAT/Science Source/Photo Researchers, Inc I n this chapter, we study five classes of organic compounds, each related to the carboxyl group: acid halides, acid anhydrides, esters, amides, and nitriles Under the general formula of each functional group is an illustration to show you how the group is formally related to a carboxylic acid Formal loss of !OH from a carboxyl group and H! from H!Cl, for example, gives an acid chloride Similarly, loss of !OH from a carboxyl group and H! from ammonia gives an amide For illustrative purposes, we show each of these reactions as a formal loss of water However, as we will see in this chapter, some actual mechanisms not involve a step in which an H2O molecule is lost O O O RCCl RCOCR9 RCOR9 RCNH2 RC # N An acid chloride An acid anhydride An ester An amide A nitrile 2H2O O RC!OH Online homework for this chapter may be assigned in OWL for Organic Chemistry 2H2O O H!Cl O O 2H2O O RC ! OH H ! OCR9 O RC ! OH H ! OR9 2H2O O RC ! OH H ! NH2 2H2O HO H RC " N The enol of an amide 680 Copyright 2010 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 18.1 Structure and Nomenclature A Acid Halides The functional group of an acid halide (acyl halide) is an acyl group (RCO!) bonded to a halogen atom Acid chlorides are the most common acid halides O RC– O O CH3CCl Acyl group An RCO! or ArCO! group O Cl Cl Cl O An acyl group Ethanoyl chloride (Acetyl chloride) Benzoyl chloride Hexanedioyl chloride (Adipoyl dichloride) Acid halides are named by changing the suffix -ic acid in the name of the parent carboxylic acid to -yl halide Similarly, replacement of !OH in a sulfonic acid by chlorine gives a derivative called a sulfonyl chloride Following are structural formulas for two sulfonic acids and the acid chloride derived from each O O CH3SOH CH3SCl H3C O SOH O O Methanesulfonic acid O SCl O O Methanesulfonyl chloride (MsCl) H3C p-Toluenesulfonyl chloride (Tosyl chloride, TsCl) p-Toluenesulfonic acid B Acid Anhydrides Carboxylic Anhydrides The functional group of a carboxylic anhydride is two acyl groups bonded to an oxygen atom These compounds are called acid anhydrides because they are formally derived from two carboxylic acids by the loss of water An anhydride may be symmetrical (two identical acyl groups), or it may be mixed (two different acyl groups) Anhydrides are named by replacing the word acid in the name of the parent carboxylic acid with the word anhydride O O O O COC CH3COCCH3 Acetic anhydride Benzoic anhydride Cyclic anhydrides are named from the dicarboxylic acids from which they are derived Here are the cyclic anhydrides derived from succinic acid, maleic acid, and phthalic acid O O O Succinic anhydride O O O O Maleic anhydride O O Phthalic anhydride 18.1 Structure and Nomenclature Copyright 2010 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 681 Phosphoric Anhydrides Because of the special importance of anhydrides of phosphoric acid in biological chemistry, we include them here to show their similarity with the anhydrides of carboxylic acids The functional group of a phosphoric anhydride is two phosphoryl groups bonded to an oxygen atom Here are structural formulas for two anhydrides of phosphoric acid and the ions derived by ionization of each acidic hydrogen O O HO ! P ! O ! P ! OH OH OH Diphosphoric acid (Pyrophosphoric acid) O O O 2O ! P ! O ! P ! O2 O2 O O O OH OH O2 OH Triphosphoric acid Diphosphate ion (Pyrophosphate ion) O 2O ! P ! O ! P ! O ! P ! O2 HO ! P ! O ! P ! O ! P ! OH O2 O O2 O2 Triphosphate ion C Esters Esters of Carboxylic Acids The functional group of a carboxylic ester is an acyl group bonded to !OR or !OAr Both IUPAC and common names of esters are derived from the names of the parent carboxylic acids The alkyl or aryl group bonded to oxygen is named first, followed by the name of the acid in which the suffix -ic acid is replaced by the suffix -ate O O CH3COCH2CH3 EtO Ethyl ethanoate (Ethyl acetate) O OEt Diethyl propanedioate (Diethyl malonate) Lactones: Cyclic Esters Lactone A cyclic ester Cyclic esters are called lactones The IUPAC system has developed a set of rules for naming these compounds Nonetheless, the simplest lactones are still named by dropping the suffix -ic acid or -oic acid from the name of the parent carboxylic acid and adding the suffix -olactone The location of the oxygen atom in the ring is indicated by a number if the IUPAC name of the acid is used, or by a Greek letter a, b, g, d, e, and so forth, if the common name of the acid is used O O O O H3C (S)-3-Butanolactone 4-Butanolactone ((S )- -Butyrolactone) ( -Butyrolactone) O O 6-Hexanolactone ( -Caprolactone) Esters of Phosphoric Acid Phosphoric acid has three !OH groups and forms mono-, di-, and triesters, which are named by giving the name(s) of the alkyl or aryl group(s) bonded to oxygen followed by the word phosphate, as for example dimethyl phosphate In more complex phosphoric esters, it is common to name the organic molecule and then indicate the presence of the phosphoric ester using either the word phosphate or 682 Chapter 18 Functional Derivatives of Carboxylic Acids Copyright 2010 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 From Cocaine to Procaine and Beyond Chemical Connections Cocaine is an alkaloid present in the leaves of the South American coca plant Erythroxylon coca It was first isolated in 1880, and soon thereafter its property as a local anesthetic was discovered Cocaine was introduced into medicine and dentistry in 1884 by two young Viennese physicians, Sigmund Freud and Karl Koller Unfortunately, the use of cocaine can create a dependence, as Freud himself observed when he used it to wean a colleague from morphine and thereby produced one of the first documented cases of cocaine addiction After determining cocaine’s structure, chemists could ask, “How is the structure of cocaine related to its anesthetic effects? Can the anesthetic effects be separated from the habituation effect?” If these questions could be answered, it might be possible to prepare synthetic drugs with the structural features essential for the anesthetic activity but without those giving rise to the undesirable effects Chemists focused on three structural features of cocaine: its benzoic ester, its basic nitrogen atom, and something of its carbon skeleton This search resulted in 1905 in the synthesis of procaine, which almost immediately replaced cocaine in dentistry and surgery Lidocaine was introduced in 1948 and today is one of the most widely used local anesthetics More recently, other members of the “caine” family of local anesthetics have been introduced, for example etidocaine All of these local anesthetics are administered as their watersoluble hydrochloride salts CH3 N O OCH3 O O Cocaine Et O H N N O H Et O Procaine (Novocain) Lidocaine (Xylocaine) Cocaine reduces fatigue, permits greater physical endurance, and gives a feeling of tremendous confidence and power In some of the Sherlock Holmes stories, the great detective injects himself with a 7% solution of cocaine to overcome boredom N O Et H2N Pr N N Et Et Etidocaine (Duranest; racemic) Thus, seizing on clues provided by nature, chemists have been able to synthesize drugs far more suitable for a specific function than anything known to be produced by nature itself the prefix phospho- On the right are two phosphoric esters, each of special importance in the biological world CHO O CH3O — P — O2 OCH3 Dimethyl phosphate H C OH O CH2 ! O ! P ! O2 O2 Glyceraldehyde 3-phosphate CHO O CH2O P O2 HO O2 H3C N Pyridoxal 5-phosphate COO2 O C O P O2 H2C O2 Phosphoenolpyruvate Glyceraldehyde 3-phosphate is an intermediate in glycolysis, the metabolic pathway by which glucose is converted to pyruvate Pyridoxal phosphate is one of the metabolically active forms of vitamin B6 Each of these esters is shown as it is ionized 18.1 Structure and Nomenclature Copyright 2010 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 683 Chemical Connections From Moldy Clover to a Blood Thinner In 1933, a disgruntled farmer delivered a pail of unclotted blood to the laboratory of Dr Karl Link at the University of Wisconsin and tales of cows bleeding to death from minor cuts Over the next couple of years, Link and his collaborators discovered that when cows are fed moldy clover, their blood clotting is inhibited, and they bleed to death from minor cuts and scratches From the moldy clover they isolated the anticoagulant dicoumarol, a substance that delays or prevents blood clotting Dicoumarol exerts its anticoagulation effect by interfering with vitamin K activity Within a few years after its discovery, dicoumarol became widely used to treat victims of heart attack and others at risk for developing blood clots Dicoumarol is a derivative of coumarin, a lactone that gives sweet clover its pleasant smell Coumarin, which does not interfere with blood clotting, is converted to dicoumarol as sweet clover becomes moldy In a search for even more potent anticoagulants, Link developed warfarin (named for the Wisconsin Alumni Research Foundation), now used primarily as a rat poison When rats consume it, their blood fails to clot, and they bleed to death Warfarin is also used as a blood anticoagulant in humans The S enantiomer shown here is more active than the R enantiomer The commercial product is sold as a racemic mixture The synthesis of racemic warfarin is described in Problem 19.59 O OH O O (S)-Warfarin (a synthetic anticoagulant) OH HO as sweet clover becomes moldy O O OO O O Dicumarol (an anticoagulant) Coumarin (from sweet clover) at pH 7.4, the pH of blood plasma; the two hydroxyl groups of these phosphoryl groups are ionized giving each a charge of 22 The molecular backbones of both DNA and RNA contain phosphoric diesters in each repeating unit D Amides and Imides The functional group of an amide is an acyl group bonded to a nitrogen atom Amides are named by dropping the suffix -oic acid from the IUPAC name of the parent acid, or -ic acid from its common name, and adding -amide If the nitrogen atom of an amide is bonded to an alkyl or aryl group, the group is named, and its location on nitrogen is indicated by N- Two alkyl or aryl groups on nitrogen are indicated by N,N-di- N,NDimethylformamide (DMF) is a widely used polar aprotic solvent (Section 9.3D) O O CH3CNH2 CH3C N H 684 Chapter 18 CH3 H9C9N CH3 Acetamide (a 1∘ amide) O N-Methylacetamide (a 2∘ amide) CH3 N,N-Dimethylformamide (DMF) (a 3∘ amide) Functional Derivatives of Carboxylic Acids Copyright 2010 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 Cyclic amides are given the special name lactam Their names are derived in a manner similar to those of lactones, with the difference that the suffix -lactone is replaced by -lactam O NH O NH H3C (S )-3-Butanolactam ((S )- -Butyrolactam) Lactam A cyclic amide 6-Hexanolactam ( -Caprolactam) The functional group of an imide is two acyl groups bonded to nitrogen Both succinimide and phthalimide are cyclic imides O Imide A functional group in which two acyl groups, RCO! or ArCO!, are bonded to a nitrogen atom O NH NH O O Succinimide Phthalimide Example 18.1 Write the IUPAC name for each compound O (a) O OMe (b) O OEt O (c) H2N O NH2 (d) Ph O O Ph O Solution Given first is the IUPAC name and then, in parentheses, the common name (a) Methyl 3-methylbutanoate (methyl isovalerate, from isovaleric acid) (b) Ethyl 3-oxobutanoate (ethyl b-ketobutyrate, from b-ketobutyric acid) (c) Hexanediamide (adipamide, from adipic acid) (d) Phenylethanoic anhydride (phenylacetic anhydride, from phenylacetic acid) Problem 18.1 Draw a structural formula for each compound (a) N-Cyclohexylacetamide (b) 1-Methylpropyl methanoate (c) Cyclobutyl butanoate (d) N-(1-Methylheptyl)succinimide (e) Diethyl adipate (f) 2-Aminopropanamide 18.1 Structure and Nomenclature Copyright 2010 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 685 The Penicillins and Cephalosporins: b-Lactam Antibiotics Chemical Connections The penicillins were discovered in 1928 by the Scottish bacteriologist Sir Alexander Fleming As a result of the brilliant experimental work of Sir Howard Florey, an Australian pathologist, and Ernst Chain, a German chemist who fled Nazi Germany, penicillin G was introduced into the practice of medicine in 1943 For their pioneering work in developing one of the most effective antibiotics of all time, Fleming, Florey, and Chain were awarded the 1945 Nobel Prize in medicine or physiology The mold from which Fleming discovered penicillin was Penicillium notatum, a strain that gives a relatively low yield of penicillin It was replaced in commercial production of the antibiotic by P chrysogenum, a strain cultured from a mold found growing on a grapefruit in a market in Peoria, Illinois The structural feature common to all penicillins is a b-lactam ring fused to a five-membered thiazolidine ring effective penicillins Among those developed are ampicillin, methicillin, and amoxicillin Another approach is to search for newer, more effective b-lactam antibiotics At the present time, the most effective of these are the cephalosporins, the first of which was isolated from the fungus Cephalosporium acremonium The cephalosporins differ in the group bonded to the acyl carbon and the side chain of the thiazine ring O H NH2 H N H O β-lactam S N Me COOH Cephalexin (Keflex) The penicillins differ in the group bonded to the acyl carbon HO O H H NH NH2 S N O COOH β-lactam Amoxicillin (a β-lactam antibiotic) The penicillins owe their antibacterial activity to a common mechanism that inhibits the biosynthesis of a vital part of bacterial cell walls Soon after the penicillins were introduced into medical practice, penicillin-resistant strains of bacteria began to appear and have since proliferated One approach to combating resistant strains is to synthesize newer, more The cephalosporin antibiotics have an even broader spectrum of antibacterial activity than the penicillins and are effective against many penicillin-resistant bacterial strains However, resistance to the cephalosporins is now also widespread A common mechanism of resistance in bacteria involves their production of a specific enzyme, called a b-lactamase, that catalyzes the hydrolysis of the b-lactam ring, which is common to all penicillins and cephalosporins Several compounds have been found that inhibit this enzyme, and now drugs based on these compounds can be taken in combination with penicillins and cephalosporins to restore their effectiveness when resistance is known to be a problem The commonly prescribed formulation called Augmentin is a combination of a b-lactamase inhibitor and a penicillin It is used as a second line of defense against childhood ear infections when resistance is suspected Most children know it as the white liquid with a banana taste E Nitriles Nitrile A compound containing a !C # N (cyano) group bonded to a carbon atom 686 Chapter 18 The functional group of a nitrile is a cyano (C # N) group bonded to a carbon atom IUPAC names follow the pattern alkanenitrile: for example, ethanenitrile Common names are derived by dropping the suffix -ic or -oic acid from the name of the parent carboxylic acid and adding the suffix -onitrile Functional Derivatives of Carboxylic Acids Copyright 2010 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 CH3C C N Ethanenitrile (Acetonitrile) CH2C N Benzonitrile N Phenylethanenitrile (Phenylacetonitrile) 18.2 Acidity of Amides, Imides, and Sulfonamides Following are structural formulas of a primary amide, a sulfonamide, and two cyclic imides, along with pKa values for each O O O SNH2 CH3CNH2 NH O Acetamide pKa 15–17 Benzenesulfonamide pKa 10 O NH O Succinimide pKa 9.7 O Phthalimide pKa 8.3 Values of pK a for amides of carboxylic acids are in the range of 15–17, which means that they are comparable in acidity to alcohols Amides show no evidence of acidity in aqueous solution; that is, water-insoluble amides not react with aqueous solutions of NaOH or other alkali metal hydroxides to form watersoluble salts Imides (pK a 8–10) are considerably more acidic than amides and readily dissolve in 5% aqueous NaOH by forming water-soluble salts We account for the acidity of imides in the same manner as for the acidity of carboxylic acids (Section 17.4), namely the imide anion is stabilized by delocalization of its negative charge The more important contributing structures for the anion formed by ionization of an imide delocalize the negative charge on nitrogen and the two carbonyl oxygens O O N N O O N O O A resonance-stabilized anion Sulfonamides derived from ammonia and primary amines are also sufficiently acidic to dissolve in aqueous solutions of NaOH or other alkali metal hydroxides by forming water-soluble salts The pKa of benzenesulfonamide is approximately 10 We account for the acidity of sulfonamides in the same manner as for imides, namely the resonance stabilization of the resulting anion O O O – S ! N ! H OH S!N O O H Benzenesulfonamide H – – S " N H2O O H A resonance-stabilized anion 18.2 Acidity of Amides, Imides, and Sulfonamides Copyright 2010 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 687 Example 18.2 Phthalimide is insoluble in water Will phthalimide dissolve in aqueous NaOH? Solution Phthalimide is the stronger acid, and NaOH is the stronger base The position of equilibrium, therefore, lies to the right Phthalimide dissolves in aqueous NaOH by forming a water-soluble sodium salt O O NH N2Na1 NaOH H2O pKeq 27.4 Keq 2.5 107 O O pKa 8.3 (stronger acid) (weaker base) (stronger base) pKa 15.7 (weaker acid) Problem 18.2 Will phthalimide dissolve in aqueous sodium bicarbonate? Connections to Biological Chemistry The Unique Structure of Amide Bonds resonance hybrid indicates the presence of a restricted bond rotation about the C!N bond The measured C!N bond rotation barrier in amides is approximately 63–84 kJ (15–20 kcal)/mol, large enough so that, at room temperature, rotation about the C!N bond is restricted In addition, because the lone pair on nitrogen is delocalized into the p bond, it is not as available for interacting with protons and other Lewis acids Thus, Amides have structural characteristics that are unique among carboxylic acid derivatives In the late 1930s, Linus Pauling discovered that the bond angles about the nitrogen atom of an amide bond in proteins are close to 120°; the amide nitrogen is trigonal planar and sp2 hybridized We know that amides are best represented as a hybrid of three resonance contributing structures (see Section 1.9C) O C R O H N O C R H H N H C R H N H This contributing structure places a double bond between C and N The fact that the six atoms of an amide bond are planar with bond angles of 120° means that the resonance structure on the right makes a significant contribution to the hybrid, and that the hybrid looks very much like this third structure Inclusion of the third contributing structure explains why the amide nitrogen is sp2 hybridized and therefore trigonal planar Also, the presence of a partial double bond (p bond) in the 688 Chapter 18 amide nitrogens are not basic In fact, in acid solution, amides are protonated on the carbonyl oxygen atom, rather than on the nitrogen (review Example 4.2) Finally, delocalization of the nitrogen lone pair reduces the electrophilic character (partial positive charge) on the carbonyl carbon, thus reducing the susceptibility of amides to nucleophilic attack Functional Derivatives of Carboxylic Acids Copyright 2010 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 Amides protonate here Less electrophilic than other carbonyls O H H C H Large rotation barrier due to partial double bond H C N N atom is sp hybridized and non-basic H All of the atoms in the box are in the same plane The amide !NH group is a good hydrogen bond donor, while the amide carbonyl is a good hydrogen bond acceptor, allowing both primary and secondary amides to form strong hydrogen bonds As we will see in Chapter 27, the ability of amides to participate in both intermolecular and intramolecular hydrogen bonding is an important factor in determining the three-dimensional structure of polypeptides and proteins H N H3C C CH3 O H Hydrogen bond Hydrogen bond N H3C C CH3 O 18.3 Characteristic Reactions In this and subsequent sections, we examine the interconversions of various carboxylic acid derivatives All these reactions begin with formation of a tetrahedral carbonyl addition intermediate (make a new bond between a nucleophile and an electrophile) A Nucleophilic Acyl Addition The first step of this reaction is exactly analogous to the addition of alcohols to aldehydes and ketones (Section 16.7B) This reaction can be carried out under basic conditions, in which a negatively charged nucleophile adds directly to the carbonyl carbon The tetrahedral carbonyl addition intermediate formed then adds a proton from a proton donor, HA The result of this reaction is nucleophilic acyl addition Nucleophilic acyl addition (basic conditions): O O Nu– C R Y A carboxylic acid derivative – OH H9A C R Y Nu Tetrahedral carbonyl addition intermediate A– C R Nu Y Addition product 18.3 Characteristic Reactions Copyright 2010 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 689 3-Methyl-2-butanone, 474, 477 2-Methyl-1-butene, 356 2-Methyl-2-butene, 159, 197t, 246t, 276, 356, 357, 406 3-Methyl-1-butene, 227, 357, 406 3-Methyl-3-buten-2-one, 993 (3-Methyl)butyl acetate, 664 3-Methylbutyl benzoate, 708 3-Methyl-1-butyne, 267 Methylcyclohexane, 85, 85, 87 1-Methylcyclohexanol, 224, 399 2-Methylcyclohexanol, 131 cis-3-Methylcyclohexanol, 131 cis-4-Methylcyclohexanol, 130–131, 131 trans-3-Methylcyclohexanol, 131 trans-4-Methylcyclohexanol, 130–131, 131 2-Methylcyclohexanone, 783 3-Methylcyclohexanone, 791 3-Methyl-2-cyclohexanone, 779 1-Methylcyclohexene, 224, 568 3-Methylcyclohexene, 264 N-Methylcyclohexylamine, 622 Methylcyclopentane, 548 3-Methylcyclopentane, 193 1-Methylcyclopentanol, 413 2-Methylcyclopentanol, 406 cis,trans-2-Methylcyclopentanol, 129 cis,trans-3-Methylcyclopentanol, 130 1-Methylcyclopentene, 231, 237, 356, 406 3-Methylcyclopentene, 406 Methyldiazonium cation, 663 2-Methyl-1,3-dioxolane, 646 p-Methyldiphenhydramine, 944 2-Methyl-1-dodecene, 567 Methylene, 569, 569–570 Methylene chloride, 302 Methylene group, 191 reduction of carbonyl group to, 622–624 Methylenecyclohexane, 594, 974, 976 Methylenecyclopentane, 356, 492, 572 1-Methyl-1,2-epoxycyclohexane, 453 2-Methylethanol, 437 6-Methyl-1,5-heptadiene, 839 2-Methylheptane, 99 heat of combustion, 100t 2-Methyl-2-heptene, 596 6-Methyl-5-hepten-2-one, 851 5-Methylhexanenitrile, 434 5-Methylhexanoic acid, 678 4-Methyl-1-hexene, 191 3-Methyl-5-hexen-2-one, 765 Methylidenecyclohexane, 224 Methylmagnesium chloride, 60 2-Methyl-4-(1-methylethyl)heptane, 70 N-Methylmorpholine, 991 2-Methylnaphthalene, 879 2-Methyl-1,4-naphthoquinone, 879 (Z)-2-Methyl-7-octadecene, 640 4-Methyloctane, 68 Methyloxirane, 448, 454, 455, 565 Methylparaben, 991 2-Methylpentanal, 559 2-Methylpentane, 68, 98t, 303, 435 3-Methylpentane, 98t 2-Methyl-3-pentanone, 435, 583 3-Methyl-2-pentanone, 583 4-Methyl-2-pentanone, 559, 583 2-Methyl-2-pentene, 243 3-Methyl-1-pentene, 263 3-Methyl-2-pentene, 571 4-Methyl1-pentene, 434 4-Methyl-1-pentene, 678 4-Methylpent-3-en-1-ol, 444 4-Methyl-3-penten-2-one, 775 2-Methylphenol, 925 3-Methylphenol, 871, 925 4-Methylphenol, 876, 935, 987 3-Methyl-1-phenyl-1-butanone, 757 4-Methyl-2-phenyl-3-penten-2-ol, 775 2-Methyl-2-phenylpropane, 912, 916 2-Methyl-1-phenyl-1-propanone, 915 2-Methylpiperidine, 736 2-Methylpropanal, 244, 411 N-Methylpropanamide, 488 2-Methylpropane (isobutane), 65, 68, 72, 101, 224, 233, 302, 304 chlorination and bromination of, 311–312, 311t, 312 2-Methylpropane (isobutylene), 191 2-Methyl-1,2-propanediol, 411 2-Methyl-1-propanethiol, 421 2-Methyl-2-propanethiol, 421 2-Methylpropanoic acid, 525 2-Methyl-1-propanol, 391, 402 2-Methyl-2-propanol, 224, 391, 396, 397t, 399, 400, 406, 916 2-Methylpropanoyl chloride, 915 2-Methylpropene (isobutylene), 221, 320–321, 358, 406, 440, 676, 935, 1181, 1182 1-Methylpropyl hydrogen phthalate, 709 2-Methylpropylbenzene, 806 trans-1-Methyl-2-propylcyclopropane, 579 Methyl(S)-2-phenylpropanoate, 716 (S)-2-Methylsulfanylbutane, 354 1-Methylsulfanyldecane, 460 Methyltriphenylphosphonium iodide, 595 2-Methyl-2-vinyl oxirane, 515, 515 Metolachlor, 735 Mevalonate, 395, 758, 1084 Mevalonic acid, 653 Mevastatin, 759 Micelles, 1075, 1075 Michael, Arthur, 772 Michael reactions, 772–776, 773t Miconazole, 939, 940 Microscopic reversibility, principle of, 409, 698–699 Millipedes, 593 Mineralocorticoid hormones, 1083t Minoxidil, 740 Mioton, 872 Mirror image, 114 Misoprostol, 1080 M,M + peak, 544–545 MO See Molecular orbital (MO) theory Moclobemide, 471, 736 Moderate nucleophiles, 350 Molar absorptivity (e), 821 Molecular dipole moment (m), 24 Molecular formula, using mass spectra to determine, 546 Molecular ions, 540 fragmentation of, 545–546 Molecular mass number average, 1160 of polymers, 1160–1161 using mass spectra to determine, 546 weight average, 1160 Molecular orbital (MO) theory, 29–31, 30 combining with valence bond theory, 37–41 delocalized systems and, 48–49 frontier, 825–827, 826 hybridization and, 49–50 Molecular orbitals antibonding, 31 in benzene, 855, 855–856 bonding, 30 conjugated systems and, 813–814 for delocalized systems, 48–50 formation of, 30–31, 31 highest occupied, 826 lowest unoccupied, 826 pi, 40 sigma, 30 Molecular oxygen, 1051 Molecular spectroscopy, 475–476 Molecular structure and acidity, 169–174 Molecular vibrations, 478–479 Molecular weight See Molecular mass Molecules See also Chiral molecules handedness of, 114–116 how enzymes distinguish between enantiomers and, 138–139 Lewis structures for, 11–13, 12t linear, 23, 23t nonpolar, 24–26 polar, 24–26 shapes of, 21–24 tetrahedral, 22, 23t Molina, Mario, 309 Molozonide, 243 Monascus ruber (fungi), 758 Monensin, 803 Monodisperse, 1161 Monomers, 1159 Monosaccharides, 1038–1042, 1038t, 1040t amino sugars, 1041–1042 conformation representations, 1044–1045 cyclic structure of, 1042–1046 d-, 1039–1041, 1040t Fischer projections, 1038–1039 formation of glycosides (acetals), 1046–1047 glucose testing, 1051 Haworth projections, 1042–1044 l-, 1039–1041 mutarotation, 1046 nomenclature, 1038 oxidation by periodic acid, 1050–1052 oxidation of, to aldonic acids (reducing sugars), 1048–1049 oxidation of, to uronic acids, 1049 physical properties of, 1042 reactions of, 1046–1052 reduction of, to alditols, 1047–1048 structure of, 1038 Monosubstituted benzenes, 867–868, 917t Monosubstituted carbon-carbon double bonds, 245 Monounsaturated fatty acids, 199–200 Montelukast, 473 Montreal Protocol, 309 Morphinan, 942 Morphine, 801, 941–942, 942, 947, 984 Morpholine, 736, 760, 960, 986 Morpholinium chloride, 761 Morpholinium ion, 986 Moths, 640, 642 Moxisylyte, 993 MRI See Magnetic resonance imaging (MRI) mRNA See Messenger RNA (mRNA) mRNA codons, 1147t MS-MS See Tandem mass spectrometer (MS-MS) Index Copyright 2010 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-21 MTBE See tert-Butyl methyl ether (MTBE) Muscalure, 561, 567–568, 568 Mustard gases, 372–376 Mutarotation, 1046 Myeloperoxidase, 467 Mylar, 677, 1165 Myoglobin, 1122 Myrcene, 197, 198 Myristic acid, 652t, 1072t N n- prefix, 70 (n + 1) rule, 508–510, 509 physical basis for, 512 2n2 electrons, Nabumetone, 941 NAD+ See Nicotinamide adenine dinucleotide (NAD+) NADH, 419, 621, 621 Nadolol, 457 NADPH, 758 Naja naja (cobras), 1087 Nanotubes, 25, 25 Naphthalene, 858, 869, 869–870, 881, 1177 b-Naphthol, 901 Naproxen, 137, 142–143, 151, 252, 654 Napthalene, 889 1-Napthol, 901 Natta, Giulio, 1173 Natural gas, 63, 101–102 NBS See N-Bromosuccinimide (NBS) n-doping, 1172 Near ultraviolet radiation, 820, 820t Neighboring group participation, 372–376 Neon, 4t, Neopentane, 70 Neopentyl alcohol, 401–402 Neopentyl bromide, 344 Neoplastic diseases, mustard gases and treatment of, 375–376 Nepata cataria (catnip), 205 Nepetalactone, 205 Nephila clavipes (spiders), 1123 Neurotoxins See Poisons New York strain of European corn borer, 196 Newman, Melvin, 75 Newman projection, 75–76, 76 Niacin, 731 Nickel, 280 Nicolson, G., 1087 Nicotinamide, 190, 731 Nicotinamide adenine dinucleotide (NAD+), 418, 418–419, 419, 621 oxidation of alcohols by, 418–419 Nicotine, 948 Nicotinic acid, 418, 731 Niemann-Pick disease, 1069 Nifedipine, 797 Ninhydrin, 1105 Nirenberg, Marshall, 1146 Nitration of anisole, 920–921, 921 of benzene, 906, 909–911 of benzoic acid, 921, 921–922 orientation of monosubstituted benzenes, 917t Nitric acid, 909 Lewis structure for, 14 pKa value, 161t Nitriles, 680, 686–687 I-22 hydrolysis of, 705–707 infrared spectra of, 489t, 490 reduction of, 721 Nitrite ion, 43 Nitro groups, 749 3-Nitroaniline, 957 4-Nitroaniline, 949, 955t, 957 p-Nitroaniline, 949 o-Nitroanisole, 917 p-Nitroanisole, 917 Nitrobenzene, 906, 919 m-Nitrobenzenesulfonic acid, 920 2-Nitrobenzoic acid, 868 4-Nitrobenzoic acid, 656, 910 m-Nitrobenzoic acid, 918, 919 o-Nitrobenzoic acid, 868, 918 p-Nitrobenzoic acid, 918, 919 Nitrogen as chiral center, 119 ground-state electron configuration, 4t isotopes of, 543t in organic chemistry, Nitrogen mustards, 373, 376 Nitrogen nucleophiles, 606–612 Nitrogen rule, 546 Nitromethane, 749, 750 1-(Nitromethyl)cyclohexanol, 750 Nitronium ion, 909 m-Nitrophenol, 874 p-Nitrophenol, 874 3-Nitropyridine, 932 2-Nitropyrrole, 932 4-Nitrosalicylic acid, 993 N-Nitrosamines, 967–968 N-Nitrosodimethylamine, 968 N-Nitrosopiperidine, 967, 988 N-Nitrosopyrrolidine, 968 Nitrosyl cation formation of, 966 reaction of, with secondary amine, 967 4-Nitrotoluene, 987 Nitrous acid, reactions of, with amines, 966–974 NMR spectroscopy See Nuclear magnetic resonance (NMR) spectroscopy Nodal plane, 27, 29, 31 Node, 27 NOE See Nuclear Overhauser enhancement (NOE) Nomenclature of acid anhydrides, 681–682 of acid halides, 681 of aldehydes, 582–585 of alkanes, 67–72 of alkenes, 190–196 of alkyl groups, 69t of alkynes, 267–268 of amides, 684–685 of amines, 948–951 of benzene, 867–869 of carboxylic acids, 650–653, 652t of chiral centers, 120–123 of cycloalkanes, 72–73 of epoxides, 447–448 of esters, 682–684 of ethers, 437–438 of imides, 685 IUPAC system, 67, 71–72 of ketones, 582–585 of monosaccharides, 1038 of nitriles, 686–687 of phenols, 870–871 of polymers, 1159–1160 R,S system of, 120–123 of sulfides, 459 of thiols, 420–421 Nomex, 1190 Nonadecane, 65t Nonane, 65t infrared spectrum of, 492 physical properties of, 97t Nonbonding electrons, 12 Non-Markovnikov addition, radical-initiated, 321–322 Non-Markovnikov hydration, 236, 237 Nonpolar covalent bonds, 10, 10t Nonpolar molecules, 24–26 Nonpolar side chains, 1100t Nonpolar solvent, 346 Nonsteroidal antiinflammatory drugs (NSAIDs), 654, 1079 Norbornane, 74 Norbornene, 194, 1182 1-Norbornene, 384 2-Norbornene, 384 Norepinephrine, 961, 1129 Norepinephrine hydrochloride, 961 Norethindrone, 1082 Notation, polymer, 1159–1160 Noyori, Ryoji, 451 NSAIDs See Nonsteroidal antiinflammatory drugs (NSAIDs) N-terminal amino acids, 1107, 1111–1112 cleavage of, 1111–1112 Nuclear magnetic “resonance,” 498, 498–500 Nuclear magnetic resonance (NMR) spectrometer, 500, 500–501 Nuclear magnetic resonance (NMR) spectroscopy, 495–538 13 C-, 495, 499, 521–523 chemical shifts and, 504–508 equivalent hydrogens and, 501–503 Fourier transform, 500 interpretation of, 523–528 (n + 1) rule and, 508–510 nuclear magnetic resonance and, 498–500 nuclear spin states and, 495–496 orientation of nuclear spins in an applied magnetic field, 496–497 signal areas and, 503–504 signal splitting and, 508–517 solving spectral problems, 526–528 Nuclear Overhauser enhancement (NOE), 525 Nuclear spin See Spin (nuclear) Nuclear spin quantum number, 496, 496t Nucleic acids, 1134–1157 DNA, 1134–1135, 1137–1143 genetic code and, 1146–1148 nucleosides and nucleotides in, 1135–1137 RNA, 1134–1135, 1143–1146, 1143t sequencing of, 1148–1153 Nucleophiles, 176, 213–214, 217, 219, 331–332 carbon, 588–594 moderate, 350 nitrogen, 606–612 oxygen, 598–606 strong, 350 structure of, 348–351, 369–370 weak, 350 Nucleophilic acyl additions, 586, 689–690 Index Copyright 2010 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 carbenes, 1017 ring-closing alkene metathesis using, 1018–1019 Nucleophilic ring opening, 454–55 Nucleophilic substitution reactions, 331–332 acyl, 690, 713 by addition-elimination, 926–927 aliphatic, 334–337 analysis of, 353–355 aromatic, 924–927 b-elimination vs., 366–370 in haloalkanes, 332–334, 333t in halohydrins, 448–449 ring opening, 454–455 Nucleophilicity, 348–351, 349t effect of shape on, 351 solvation effects on, 350–351 Nucleosides, 1135–1137 Nucleotides, 1135–1137 coding sequence, 1113 Nucleus, atomic, 1, Number average molecular weight (Mn), 1160 Nylon 6, 1164, 1164 Nylon 6,10, 1191 Nylon 66, 651, 738, 1158, 1163, 1163–1164 O Oblivon, 292 Observed rotation, 135 b-Ocimene, 202 Octadecane, 65t Octadecanoic acid, 652t 9-Octadecenoic acid, 567 9-Octadecynoic acid, 291 Octanal, 277 Octanamide, 718 1-Octanamine, 718 Octane boiling point of, 99 formulas for, 65t heat of combustion of, 100, 100t mass spectrum of, 547 octane rating of, 103 physical properties of, 97t Octane rating, 103 2,7-Octanedione, 750 Octanoic acid, 652t (R)-2-Octanol, 708, 734 (S)-2-Octanol, 152, 403, 404, 734 4-Octanol, 646 2-Octanone, 551 4-Octanone, 779, 780 (3E,5E)-1,3,5,7-Octatetraene, 824t 6-Octen-1-amine, 721 1-Octene, 317, 975 trans-2-Octene, 975 trans-4-Octene, 281 6-Octenenitrile, 721 Octet rule, exceptions to, 16 Octyl acetate, 664 2-Octyl acetate, 152, 405 2-Octyl p-toluenesulfonate, 708 (R)-2-Octyl tosylate, 708 (S)-2-Octyl tosylate, 152, 404, 405 2-Octylcyanoacrylate, 1179 1-Octyne, 276, 277 infrared spectrum of, 483, 483 physical properties of, 269t 4-Octyne, 281 Odor of carboxylic acids, 655 thiols and, 421 -oic acid suffix, 71 Oils, 1073, 1073t, 1074 cis double bonds in, 199–200 essential, 197–198, 198 trans fatty acids, 247 tropical, 1073 -ol suffix, 71 Oleic acid, 199, 200, 1072t, 1073t Oligopeptides, 1107 Oligosaccharides, 1052–1055 Olive oil, 200 1,4-addition, 814–819 1,2-addition, 814–819 -one suffix, 71 1,2-shift, 216, 226, 239 Opium poppy, 941 OPSIN, 608 Optical activity, 134–137 Optical brighteners/optical bleaches, 1076 Optical purity, 136–137 Optically active, 134 Orbitals, antibonding, 169, 169 atomic, carbon-carbon double bond, 188–190 degenerate, distribution in shells, 2t hybrid, 32 hybridization of, 32–36 molecular (See Molecular orbitals) phasing of, 837 sp hybrid, 35, 35–36, 41t sp2 hybrid, 34, 34–35, 41t sp3 hybrid, 32–34, 33, 41t in wave function, 27–28 Order of precedence of functions, 584 Organic chemistry, Organic chemistry roadmap, 265 Organic synthesis, 282–285 See also Biosynthesis; Drugs of acetic acid, 660 acetoacetic-ester, 763–67 of alkyl-aryl ethers, 875–876 of alkynes, 270–272, 282–285 of amines, 964–966 of carboxylic acids, 659 Claisen condensations and, 757–759 epichlorohydrin in, 455–457, 456, 457 of epoxides, 448–452 of esters, 682–684 of ethers, 439–442 ethylene oxide in, 455–457, 456 Fischer esterification and, 661–662 of haloalkanes, 302–305, 399–403 of hormones, 1084–1085 mass spectrometry and, 554 of Nylon 66, 1163 of organolithium compounds, 563 oxirane in, 448, 466, 1165 of phenol, 330 of polypeptides, 1113–1117, 1118 of poly(vinyl chloride), 274 of progesterone, 293, 737 of prostaglandin, 835–836 reactions of functional groups in complex molecules and, 284–285 retrosynthetic analysis and, 282–284 of salicylic acid, 877 of soaps, 1074–1075 solid-phase, 1116–1117, 1118 of sulfides, 459–460 of thiols, 422–423 of vitamin A, 799 Williamson ether, 439–440, 448 Organohalogens, coupling with, 567–568 Organolithium compounds, 561–566 addition of, to aldehydes and ketones, 590–591 reactions of, with carboxylic acid derivatives, 715 Organomagnesium compounds (Grignard reagents), 561–566 Organometallic catalysts, 1002 ruthenium-containing, 1000 Organometallic compounds, 561–580 carbenes, 569–573 carbenoids, 573 lithium diorganocopper (Gilman) reagents, 566–569 organolithium compounds, 561–566 organomagnesium compounds (Grignard reagents), 561–566 Organometallic compounds, reactions with, 713–716 Organopalladium reagents in the Heck reaction, 1003–1004 in Suzuki coupling, 1014 Orgyia pseudotsugata (moth), 642 Orlon, 1170t l-Ornithine, 1101 Ortho, 868 Orthogonal, Ortho-para directing, 917 Osmates, 241 Osmium tetroxide, 241–242, 250 Out of phase addition, 30, 37, 38 Oxalic acid, 650, 651 Oxaloacetic acid, 148 Oxalosuccinic acid, 666 Oxanamide, 798 Oxane, 437 2-Oxepane, 807 Oxetane, 437 Oxidation reactions, 240 See also Reduction of alcohols, 412–420 of aldehydes, 616–617 of alkanes, 99–100 of alkenes, 240–244, 449–450 at benzylic positions, 880–881 of fatty acids, 1077–1078 hydroboration, 236–239 of ketones, 617 of monosaccharides, 1048–1052 with ozone, 243–244 of phenols, 877–879 of sulfides, 460 of thiols, 423–424 with transition metal oxides, 245–246 Oxidative addition reactions, 1002 Oxidizing agents chromic acid, 413–414 ozone, 243–244 periodic acid, 416–420, 1050–1052 potassium dichromate, 413 pyridinium chlorochromate, 415 Tollens’ reagent, 616 Oxime, 612t Index Copyright 2010 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-23 Oxirane hydrolysis of, 452 nomenclature of, 437 in organic synthesis, 448, 466, 1165 reactions with, 565–566, 568–569 3-Oxobutanoic acid, 584t, 652, 665, 667 5-Oxohexanal, 244 5-Oxohexanoic acid, 650, 661 Oxolane, 437 Oxonium ion, 215, 216, 225 4-Oxo-4-phenylbutanoic acid, 935 5-Oxo-5-phenylpentanoic acid, 661 2-Oxopropanoic acid, 656 3-Oxopropanoic acid, 584t Oxyacetylene torch, 266 Oxygen electronegativity of, 170 ground-state electron configuration, 4t isotopes of, 543t molecular, 1051 in organic chemistry, Oxygen nucleophiles, addition of, to aldehydes and ketones, 598–606 Oxygenates, 442 Oxymercuration, 207t Oxymercuration-reduction reactions, 233–236, 234 Ozone, as oxidizing agent, 243–244 Ozone layer, 308 Ozonide, formation of, 243–244 Ozonolysis, 243–244 P p orbitals, 28–30, 29 PAHs See Polynuclear aromatic hydrocarbons (PAHs) Paired spins, lone, Palladium, 280 Palladium catalysts, in Heck reaction, 1003–1004, 1005 Palladium-catalyzed cross-coupling reactions, 1012–1017 general mechanism for, 1012 Sonagashira coupling, 1016–1017 Stille coupling, 1015–1016 Suzuki coupling, 1013–1015, 1014t Palladium(II) acetate, 1003, 1005 Palmitic acid, 652t, 1072t, 1073, 1073t, 1094 Palmitoleic acid, 1072t Papaver somniferum (opium poppy), 941 Para, 868 Paraffin wax, 96, 1159 Parkinson’s disease, 541 Paroxetine (Paxil), 435 Parr shaker-type hydrogenation apparatus, 245 Particles in motion, wave properties and, 27 Parts per million (ppm), 499 Pascal’s triangle, 512, 512 Pauli exclusion principle, 3, 30 Pauling, Linus, 7, 32, 42, 688, 1117, 1119, 1120 Pauling scale, 7t PCC See Pyridinium chlorochromate (PCC) p-doping, 1172 Peak intensities, predicting, 511–512 Pectic acid, 1068 Pedersen, Charles, 458 Penicillins, 686 Penicillium chrysogenum (fungi), 686 Penicillium citrinum (fungi), 758 Penicillium notatum (fungi), 686 I-24 Penicillium s fungus (fungi), 680 penta- prefix, 68 Pentadecane, 65t 1,2-Pentadiene, 811 1,3-Pentadiene, 264, 811 1,4-Pentadiene, 195, 811, 811t, 975 trans-1,3-Pentadiene, 811t Pentaerythrityl palmitate, 1094 Pentanal, 653t Pentane, 64, 65t, 70, 97t, 116, 394t, 544, 585t, 586 Pentanedinitrile, 381 Pentanedioic acid, 650 1,5-Pentanediol, 396 2,4-Pentanedione, 184, 185, 614, 615 2-Pentanethiol, 405 Pentanoic acid, 617, 652t infrared spectrum of, 488 odor of, 655 (R)-2-Pentanol, 405 1-Pentanol, 394t, 396, 438t, 653t 2-Pentanol, 559 3-Pentanol, 399 2-Pentanone, 277, 806, 824 3-Pentanone, 277, 511, 527 Pentanoyl chloride, 715 Pentapeptides, 1107 1-Pentene, 116, 197t, 260, 272, 811t 2-Pentene, 160 cis,trans-2-Pentene, 197t 2-Pentene-2-ol, 277 2-Pentene-3-ol, 277 3-Penten-2-ol, 203 4-Penten-1-ol, 260 3-Penten-2-one, 824 Pentobarbital (Nembutal), 732 Pentonoic acid, 71 Pentorex, 995 Pentyl, 300t Pentylmagnesium bromide, 567 1-Pentyne, 272 mass spectrum of, 549 physical properties of, 269t 2-Pentyne, 277 4-Pentyn-1-ol, 445, 445–446, 447 Penultimate carbon, 1039 Peptide bonds, 1106, 1106 cleavage of, 1109–1110 formation of, 1115–1116 geometry of, 1117–1119 hydrolysis of, 1110–1111 Peracetic acid, 450 Percarboxylic acids, 450 Percent s character, 174 Percent transmittance, 821 Perchloroethane, 298 Perchloroethylene, 297, 298 Perfluoroalkanes, 301 Perfluoropropane, 298 Perfumes, 421 Perhaloalakanes, 297 Perhaloalkenes, 297 Pericyclic reactions, 824–827 cycloaddition, 825, 827 Diels-Alder reaction as, 827–836 frontier molecular orbital theory, 825–827 sigmatropic shifts, 836–841 Periodic acid, 416 as glycol-oxidizing agent, 416–420 as monosaccharide-oxidizing agent, 1050, 1050–1052 Periodic Table, trends in electronegativity values, 7–8, 7t Perkin condensation, 793 Permethrin, 663 Peroxides, 306, 318 Peroxy radical, 318, 319, 320 Peroxyacetic acid, 450 Peroxycarboxylic acids, 449–450 Perutz, Max F., 1121 Pesticides bifenthrin, 663 carbamate, 184 DDT, 935 2,4-dichlorophenoxyacetic acid, 938 naphthalene, 858, 869, 881, 1177 nicotine, 948 permethrin, 663 pyrethrins, 204, 205, 663, 663 PET See Poly(ethylene terephthalate) (PET) Petrolatum, 96 Petroleum, 102–103 Petroleum refining, 102, 102 PGE1, 732, 1080 PGF2a, 1080 PGG2, 1079 PGH2, 1079 pH, physiological, 164 Phasing, 28 Phenanthrene, 858, 869 Phenobarbital (Luminal), 732 Phenols, 165, 870–879 acid-base reactions of, 875, 987 acidity of, 161t, 871–874, 872t antioxidants and, 318 bisphenol A from, 935 from cumene hydroperoxide, 643 Kolbe carboxylation of, 877 nomenclature of, 867, 870–871 oxidation to quinones, 877–879 preparation of alkyl-aryl ethers and, 875–876 structural formula of, 433 structure of, 870–871, 871 synthesis of, 330 synthesis of Bakelite and, 1168, 1169 Phenoxide ion, 165 Phenoxy radical, 318 2-Phenoxypropane, 876 Phensuximide, 800 Phentermine, 995 Phenyl isothiocyanate, 1111 Phenyl lithium, 775 Phenyl (Ph—) groups, 187, 868, 868 Phenyl 2-propenyl ether, 876 Phenylacetaldehyde, 596, 608, 781 Phenylacetamide, 711 N-Phenylacetamide, 701, 934 Phenylacetic acid, 705, 720 Phenylacetonitrile, 687, 705, 801 Phenylacetylene, 732 Phenylalanine, 1100t, 1102t 2-Phenylbutanamide, 701 2-Phenylbutanoic acid, 701 1-Phenyl-2-butanol, 635 2-Phenyl-2-butanol, 590 3-Phenyl-2-butanone, 624 4-Phenyl-2-butanone, 766 4-Phenylbutanoyl chloride, 913 (E)-1-Phenyl-2-butene, 596 (E)-2-Phenyl-2-butene, 977 (Z)-1-Phenyl-2-butene, 596 (Z)-2-Phenyl-2-butene, 868 Index Copyright 2010 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 2-Phenyl-2-butene, 977 1-Phenyl-3-buten-1-ol, 569 4-Phenyl-3-buten-2-one, 806 Phenylcyclohexane, 916 3-Phenylcyclohexanone, 779 1-Phenylcyclohexene, 1023 3-Phenylcyclohexene, 1023 p-Phenylenediamine, 1164 N-Phenylethanamide, 701 (S)-1-Phenylethanamine, 949 Phenylethanenitrile, 687 (S)-1-Phenylethanol, 455 Phenylethene, 1003 (R,S)-1-Phenylethylamine, 141 (E)-4-Phenyl-2-hexene, 1008 (Z)-3-Phenyl-3-hexene, 1008 Phenylhydrazine, 612t Phenylhydrazone, 612t Phenylisocyanate, 738 Phenyllithium, 590 Phenylmagnesium bromide, 562, 565, 589 8-Phenylmenthol, 835, 836 Phenyloxirane, 455 1-Phenyl-1,3-pentadiene, 636 1-Phenyl-1-pentanone, 582, 868 2-Phenylpropanal, 897 (R)-2-Phenyl-1-propanamine, 720 1-Phenyl-2-propanamine, 987 1-Phenyl-1,2-propanediol, 897 3-Phenylpropanoic acid, 770 (R)-2-Phenyl-1-propanol, 720 (S)-2-Phenyl-1-propanol, 716 1-Phenyl-2-propanol, 565 2-Phenyl-2-propanol, 589 1-Phenyl-1-propanone, 937, 992 trans-3-Phenyl-2-propenal, 582 trans-3-Phenylpropenoic acid, 650 Phenylthiohydantoin, 1112 Phosgene, 1165, 1166 Phosphatidic acid, phospholipids derived from, 1086, 1087 Phosphatidylcholine, 1086t Phosphatidylethanoamine, 1086t Phosphatidylinositol, 1086t Phosphatidylserine, 1086t Phosphine, 594 Phosphodiester group, ionization of, 164 Phosphoenolpyruvate, 683 Phosphoesters, 37 Phospholipases, snake venom, 1087 Phospholipids, 1085–1088 in lipid bilayers, 1086–1087, 1088 structure of, 1085–1086 Phosphonoester, 596–597 (R)-3-Phospho-5-pyrophosphomevalonate, 759 Phosphoric acid, 36, 36, 874 anhydrides from, 682 esters from, 682–684 pKa value, 161t Phosphoric anhydrides, 682 Phosphorous acid, 402 Phosphorus tribromide, 402 Phosphorus, 594 as chiral center, 119 compounds containing, 36 ground-state electron configuration, 4t Photolysis, 569 Photons, 475 Photosynthesis, 1041 Phthalic acid, 651, 881 Phthalic anhydride, 681, 709, 1191 Phthalimide, 685, 687–688 Phyllobates terribilis (poison dart frogs), 953 Physical properties of alcohols, 393–397, 394t of aldehydes, 585–586, 586t of alkanes, 96–99, 97t of alkenes, 196, 197t of alkynes, 269 of amines, 952–954, 954t of carboxylic acids, 653–655, 653t of cycloalkanes, 96–99 of ethers, 438–439, 438t of haloalkanes, 298–301 of ketones, 585–586, 586t of monosaccharides, 1042 of thiols, 421–422, 422t of triglycerides, 1073–1074, 1074t Physiological pH, 164 Pi bonding molecular orbitals, 40, 40 Pi bonds in alkenes, 188, 188–189, 206 in alkynes, 266, 267 in amides, 688–689 on anion, 49 arrows indicating interconversion of, 211 in benzene, 855–856, 856 Brønsted-Lowry bases and, 159–160 of carbonyl groups, 586–587 conjugation and, 487 diamagnetic effects from, 507–508, 507–508 electrophilic addition and, 217 formation of, 37–41 hybridization and, 49–50 Pi systems, 1172 conjugation of, 615 Picometers, Picric acid, 874 Pinacol, 410, 410–411 Pinacol rearrangement, 410–412 Pinacolone, 410 Pinane, 75 a-Pinene, 74, 198, 261, 262 Piperidine, 112, 608, 948, 957, 967 Piperonal, 939 pKa, 160–162, 161t Planar configuration converting to chair, 90 Planarity of amino groups on aromatic rings, 958–959 Planck’s constant, 27 Plane of symmetry, 115 Plane-polarized light, 134, 134 Plants See also Fungi catnip, 205 chrysanthemum, 663 coca, 683 ephredra, 148 foxglove, 1037, 1068 opium poppy, 941 poison ivy, 871 thyme, 871 vanilla, 871 willow, 651 wormwood, 204 Plasmid DNA, 1134 Plastics, 1159 See also Polymers PLP (See Pyridoxal phosphate (PLP)) PMP (See Pyridoxine phosphate (PMP)) recycling of, 1184–1185 thermo-, 1159 thermosetting, 1159 Platinum, 280 Plexiglass, 1170t PLP See Pyridoxal phosphate (PLP) PMP See Pyridoxine phosphate (PMP) Poison dart frogs, 953 Poison ivy, 871 Poisons absinthe, 204 amygdalin, 1067 batrachotoxin, 953 coniine, 948 enanthotoxin, 290 mustard gases, 372–376 snake venom, 1087 tetrodotoxin, 95, 95 warfarin, 684, 799 Polar aprotic solvents, 346, 346t, 348, 351 Polar covalent bonds, 7, 9–11, 10t Polar molecules, 24–26 Polar protic solvents, 346–347 Polar side chains, 1100t Polar solvent, 345 Polarimeters, 134–136, 135 Polarity, of haloalkanes, 298–299 Polarizability, 299 Polyacetylene, 1172, 1183 Polyacrylonitrile, 594, 1170t Polyamides, 1162–1165 Polyatomic anions, 13 Polyatomic cations, 13 Polyatomic ions, Lewis structures for, 11–13 Polycarbonates, 1165–1166, 1191 Poly(1,1-dichloroethylene), 1170t Polydispersity index, 1161 Polyenes, 195 cis,trans isomers, 195–196 Polyesters, 1165 Dacron, 651, 677, 1058, 1165 Nylon 66, 651, 738, 1158, 1163, 1163–1164 Poly(ethyl acrylate), 1170t Polyethylene, 206, 207, 1159, 1169, 1170t, 1173 high-density, 1173–1174 Poly(ethylene adipate), 1162 Poly(ethylene phenylurea), 1191 Poly(ethylene terephthalate) (PET), 1161, 1161, 1165, 1190 recycled, 1184, 1184, 1185 synthesis of, 1165 Polyhalogenation, 627 Poly(3-hydroxybutanoic acid), 1192 Poly(3-hydroxybutanoic acid-3-hydrocyoctanoic acid) copolymer, 1192 Polyisoprene, 1193 Polymerization average degree of, 1159 chain-growth, 1169–1185 coordination, 1174 living, 1178 ROMP, 1182–1185 step-growth, 1162–1169 Polymers, 1158–1194, 1159 architecture of, 1159 atactic, 1175 chain-growth of, 1169–1185 condensation of, 1162–1169 elastic, 1162 isotactic, 1175 living, 1178 molecular weights of, 1160–1161 morphology of, 1161–1162 nomenclature of, 1159–1160 Index Copyright 2010 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-25 notation, 1159–1160 recycling of, 1184–1185 step-growth of, 1162–1169 stereochemistry of, 1175–1176 syndiotactic, 1175 telechelic, 1180 that conduct electricity, 1172 thermosetting, 1168–1169 Poly(methyl methacrylate), 1170t Poly(2-methyl-1,3-butadiene), 1193 Polynuclear aromatic hydrocarbons (PAHs), 869–870 carcinogenic, 870 Polypeptides, 1106–1107 mass spectrometry of, 553 primary structure of, 1107–1113 quaternary structure of, 1124, 1124t secondary structure of, 1119–1121 shapes of, 1117–1124 synthesis of, 1113–1117, 1118 tertiary structure of, 1121–1124 Poly(phenylene vinylene) (PPV), 1183 Polypropylene, 1170t, 1193 recycled, 1184, 1185 Polysaccharides, 1052, 1055–1058 acidic, 1058 cellulose, 1056, 1056–1058 glycogen, 1056 starch, 1055–1056, 1056 textile fibers from cellulose, 1057–1058 Polystyrene (PS), 1160, 1169, 1170t, 1178 recycled, 1184, 1185 Polysubstituted benzenes, 868–869 Polysubstitution, 917–924 Poly(tetrafluoroethylene) (PTFE), 1170t Polythene, 1170t Polyunsaturated fatty acid esters, 319 Polyunsaturated fatty acids, 199, 1072, 1072t Polyunsaturated triglyceride, 1074, 1074 Polyurethanes, 1166 Poly(vinyl chloride) (PVC), 274, 274–275, 330, 1160, 1170t recycled, 1184, 1185 Porthetria dispar (gypsy moth), 640 Potassium dichromate, 413 Potassium permanganate, 458–459 Potassium sorbate, 672 Potassium tert-butoxide, 356, 398, 439, 570 Potential energy, 5, 77, 166 ppm See Parts per million (ppm) PPV See Poly(phenylene vinylene) (PPV) Precess, 498, 498 Prefixes IUPAC system, 67t, 71 racemic mixture, 136 Prelog, V., 120 Preservatives, food, 319 Primary alcohols, 17, 18, 392 acid-catalyzed dehydration of, 408 addition to formaldehyde gives, 588–589 conversion to haloalkane, 399–400 dehydration of, 405 dehydration of, acid-catalyzed, 441 oxidation of, 412–413 reaction with phosphorus tribromide, 402 reduction of ester to, 718 SN2 reactions with, 400–401 Primary alkyl groups, 369 Primary amines, 18 aliphatic, 606, 968–971 aromatic, 606, 971–974 I-26 basicity of, 955t physical properties of, 954t Primary carbons, 72 Primary hydrogen, 72 Primary structure of DNA, 1137–1138 of polypeptides and proteins, 1107–1113, 1109–1113 Primer, 1149 Principal quantum numbers, Principle of microscopic reversibility, 409 Priority rules, for naming chiral centers, 120–121 Procaine (Novocaine), 456, 683, 733 Prochiral, 518 Progesterone, 803, 1082, 1083 specific rotation of, 136 synthesis of, 293, 737 Proline, 1100t, 1102t, 1105 1,2-Propadiene (allene), 201, 272 Propanal, 243, 244, 294, 653t 2-Propanamine, 949 Propane, 63 bromination of, 303 carbons in, 72, 388 chlorination of, 303 conversion of, 678 fluorination of, 327 formulas for, 65t in natural gas, 101 oxidation of, 99, 240 physical properties of, 97t, 394t structure of, 64 1,3-Propanediamine, 991 Propanedioic acid, 650, 667 1,2-Propanediol, 240, 242, 393 1,3-Propanediol, 393 2,2-Propanediol, 598 2-Propanethiol, 421 1,2,3-Propanetriol, 199, 393, 469, 1075, 1191 Propanoic acid, 481, 585t, 652t, 656, 962 1-Propanol, 391, 397, 434, 588 conversion of, 579 in Fischer esterification, 662 NMR spectrum of, 524 physical properties of, 394t, 653t 2-Propanol, 216, 224, 242, 264, 391, 397t, 701 Propanone See Acetone Proparacaine, 946 Propargyl cation, 549 Propenal, 829 2-Propenal, 582 Propene See also Propylene in acid-catalyzed dehydration, 264 allylic bromination of, 315 allylic halogenation of, 313, 314, 457 in cumene synthesis, 915, 916 in epichlorohydrin synthesis, 470 in half-reaction, 242 halohydrin synthesis and, 448 heat of hydrogenation, 246t in hexylcaine synthesis, 994 hydration of, 224, 225 hydrohydrin synthesis and, 231 nomenclature of, 191 oxidation of, 240 physical properties of, 197t in regioselective reaction, 218, 221 structural formula for, 71 structure of, 187 in tridemorph synthesis, 991 Propenenitrile, 594 Propenoic acid, 259, 650 Propen-2-ol, 278 2-Propen-1-ol, 481 2-Propenyl cation, 264 2-(2-Propenyl)phenol, 883 Propionaldehyde, 586t Propionic acid, 652t Propiophenone, 992 Propofol, 992, 1049 Propoxyphene (Darvon), 984, 992 Propranolol, 901, 902 Propyl, 300t Propyl acetate, 662 Propyl alcohol, 391 Propyl cation, 221 1-Propyl cation, 264 Propyl propanoate, 678, 739 Propylamine, 954t Propylene, polymers derived from, 1170t Propylene glycol, 393 Propylene oxide, 448, 565, 1192 4-Propyl-4-heptanol, 739 2-Propylpentanoic acid, 707 Propyne, 268, 269t, 273, 278 3-Propynyl cation, 549 Prostacyclin, 1080 Prostaglandin C2, 389 Prostaglandins, 1078–1081 synthesis of, 835–836 Prostanoic acid, 1078 Protecting groups, 446 amino-, 1114–1115 BOC-, 1133 carboxyl, 1115 silyl ethers as, 445–447 Protein Data Bank, 1152 Protein-derived amino acids, 1099–1101 Proteins, 141, 1106–1107 common amino acids in, 1100t hydrogen bonding in, 1122 primary structure of, 1107–1113 quaternary structure of, 1124, 1124t secondary structure of, 1119–1121 sequencing from coding nucleotide sequence, 1113 shapes of, 1117–1124 tertiary structure of, 1121–1124 Protic acids, 176 Protic solvents, 346, 346t Proton acids, 564–565 Proton transfer steps, 213, 216 Protonolysis, 280–281 Proton-transfer reactions, 156, 175 PS See Polystyrene (PS) Pseudoionone, 642 PTFE See Poly(tetrafluoroethylene) (PTFE) Puffer fish, 95, 95 Pulegone, 640, 791 Purcell, Edward, 495 Purine, 864, 865, 949, 1135, 1139t Purine bases, 1047, 1135 Purple benzene, 459 PVC See Poly(vinyl chloride) (PVC) Pyramidal inversion, 952 Pyramidal molecules, 22, 23t Pyran, 1043 Pyranose, 1043 Pyranoside, 1052 Pyrene, 870 Index Copyright 2010 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 Pyrethrins, 663 I, 663 II, 204, 205 Pyrethrosin, 204, 205 Pyridine acidity of, 957 basicity of, 955t electrophilic aromatic substitution of, 932 as heterocyclic aromatic compound, 864, 958 in paroxetine synthesis, 435 physical properties of, 954t in preparation of pyridinium chlorochromate, 415 in reactions with alcohols, 708 structural formula for, 889, 948 structure of, 959, 959 UV transition and, 846 Pyridine-4-carboxylic acid, 732 Pyridine-4-carboxylic acid hydrazide, 732 Pyridinium acetate, 950 Pyridinium chloride, 708 Pyridinium chlorochromate (PCC), 415 Pyridinium ion, 846, 958 2-Pyridone, 896 Pyridoxal 5-phosphate, 683 Pyridoxal phosphate (PLP), 610 Pyridoxamine, 986 Pyridoxine, 610, 610–611 Pyridoxine phosphate (PMP), 610, 611 Pyridoxine (vitamin B6), 418, 610, 610–611, 986 Pyrimidine, 864, 1135, 1139t Pyrimidine bases, 1047 Pyrophosphate ion, 682 Pyrophosphoric acid, 682 Pyrrole, 864, 932, 948, 960 Pyrrolidine, 760, 948, 993 Pyruvate, 418, 610, 621 Pyruvic acid, 656 Q Quadrupole mass analyzer, 541 Quantization, Quantum mechanics (wave mechanics), 27–30 Quantum numbers electron spin, 496 nuclear spin, 496, 496t Quartet, 509 Quaternary ammonium ion, 951–952 Quaternary carbons, 72 Quaternary structure, of polypeptides and proteins, 1124, 1124t Quats, 1094 Quiana, 1190 Quinoline, 949 o-Quinone, 878 p-Quinone, 878, 879 Quinones, 877–879 Quinuclidine, 987 R R configuration, 120–123 R enantiomer, 135 Racemethorphan, 942 Racemic mixtures, 136 Racemization, 339–340, 624–625 Radiation See also Electromagnetic radiation; Ultraviolet radiation near ultraviolet, 820, 820t visible, 820t Radical, 301 Radical autoxidation, 317–320 Radical cations, 540 Radical chain reactions, 306–308, 308 Radical chain-growth polymerizations, 1169–1172 Radical coupling, 1171 Radical inhibitors, 319 Radicals, 208 allylic, 316–317 autoxidation of, 317–320 formation of, 305–306 Raffinose, 1066 Ramakrishnan, Venkatraman, 1144 Raman spectroscopy, 478 Rate-determining step, 208 Rattlesnakes, 1087 Rayon, 1057, 1058 RCD See Reaction coordinate diagrams (RCD) Reaction coordinate, 166 Reaction coordinate diagrams (RCD), 166–169, 167, 207–208, 208 Reaction mechanisms, 165–169, 215–216 developing, 209–210 E1, 358, 360–365 E2, 359–365 predicting what will occur in, 212–215 SN1, 336–337, 337 SN2, 334–336, 335 Reactions of acid chlorides with salts of carboxylic acids, 712 acid-base (See Acid-base reactions) addition (See Addition reactions) of alcohols, 708–710 of aldehydes, 586–588 of alkanes, 99–101 of alkenes, 206–265 allylic halogenation, 313–317 at a-carbon, 624–627 of amines, 710–712, 961–964 of ammonia, 710–712 anti addition, 281 of benzenes, 906–946 at benzylic position, 879–882 beta elimination, 332, 356–357 bimolecular, 334 bond formation, 1000–1036 BrØnsted acid-base, 213 of carboxylic acid derivatives, 689–694 catalytic hydrogenation, 245 catalytic reduction, 245–246 chain-transfer, 1171 of chiral molecules, 248–252 Claisen condensation, 751–753, 757–759 cleavage (See Cleavage reactions) Clemmensen, 622–623 conjugate addition, 772–780 Cope elimination, 976–977 crossed aldol, 748–750 crossed Claisen, 754–755 crossed enolate, 780–784 decarboxylation, 665–668 dehydration, 405–410 dehydrohalogenation, 270–272, 356 Dieckmann condensation, 753–754 Diels-Alder, 264–265, 548, 827–836 diol formation, 240–244 dissolving metal, 281–282 electrophilic, 273–275 electrophilic aromatic substitution, 907–916 elimination, 215 of enamines, 760–763 endergonic, 168 endothermic, 168 of enolate anions, 742–744 of epoxides, 452–455 of esters, 709–714 of ethers, 443–445 exergonic, 168 exothermic, 168 of functional groups in complex molecules, 284–285 halogenation (See Halogenation reactions) halohydrin formation, 231–233 Heck, 1002–1008 Hofmann elimination, 974–976 hydration, 207t, 224–226, 275, 277–279 hydroboration-oxidation, 236–239, 275–277 hydroboration-protonolysis, 280–281 hydrogenation (See Hydrogenation reactions) hydrohalogenation, 270 hydrolysis (See Hydrolysis) intramolecular aldol, 750 of ketones, 586–588 Michael, 772–776, 773t of monosaccharides, 1046–1052 nucleophilic substitutions (See Nucleophilic substitution reactions) organometallic compounds, 713–716 oxidation (See Oxidation reactions) oxidative addition, 1002 of oxiranes, 565–566, 568–569 peptide-bond forming, 1115–1116 pericyclic, 824–841 of proton acids, 564–565 radical addition, 320–323 radical chain, 306–308 reduction (See Reduction) reductive elimination, 1002 regioselective (See Regioselective reactions) ring-opening, 1182–1185 Robinson annulation, 777–778 Sandmeyer, 971, 972 Schieman, 971, 972 Sonogashira coupling, 1016–1017 stereospecific, 249 Stille coupling, 1015–1016 substitution, 302 Suzuki coupling, 1013–1015 syn addition, 280 syn stereoselective, 237 Tiffeneau-Demjanov, 970 unimolecular, 336 Wittig, 594–597 Wolff-Kishner, 622–623 Reactive intermediates, 207–216, 208 Reagents Gilman, 566–569, 580 Grignard, 561–566, 577 for Michael reactions, 773t Simmons-Smith, 572 Tollens’, 616 Rearrangements of carbocations, 226–228, 226–228 Claisen, 837, 838–839 Cope, 837, 839–840 McLafferty, 550–551, 551 pinacol, 410–412 Recycling chemical, 1185 plastic, 1184–1185 Index Copyright 2010 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-27 Reducing agents diisobutylaluminum hydride, 718, 731 dimethyl sulfide, 460 lithium aluminum hydride, 455, 618, 659–661, 716–721 sodium borohydride, 234, 455, 618, 618–619, 717–718 sodium naphthalide, 1177–1178 Reducing sugars, 1048–1049 Reduction, 240 of aldehydes, 617–624 of alkenes, 244–248 of alkynes, 280–282 of amides, 718–720 of carboxylic acid derivatives, 716–721 of carboxylic acids, 659–661 catalytic, 245, 280, 619 Clemmensen, 622–623 dissolving metal, 281–282 of esters, 716–718 of fatty acid chains, 1074 of ketones, 617–624 metal hydride, 618–619 of monosaccharides, 1047–1048 of nitriles, 721 oxymercuration, 233–236, 234 reductive amination, 620–622 selective, 619–620 Wolff-Kishner, 622–623 Reductive amination, 620–622 Reductive elimination, 1002 Reformatsky, Sergei, 793 Regiochemical issues, in catalytic allylic alkylation, 1011–1012 Regioselective reactions, 218 of bromination vs chlorination, 303–304, 310–313 of E1 reactions, 360 of E2 reactions, 360–361 in haloalkane formation, 303–304 stabilities of carbocations and, 221–222 Relative reactivity, 690–692 Repeat unit, 1159 Resolution, 140–144 of enantiomers, 140–144 enzymes and, 142–143 of mass spectra, 542–543 by means of chromatography on a chiral substrate, 143–144 by means of diastereomeric salts, 140–142 Resonance, 42–47, 211 delocalization and, 48 estimating relative importance of contributing structures, 44–47 hybridization considerations in light of, 49–50 nuclear magnetic, 498, 498–500 rules for writing acceptable contributing structures, 44 theory of, 42–44 Resonance contributors, 42 Resonance energy, 857 of benzene, 856–858, 857, 857–858 Resonance hybrid, 42 Resonance structures, 42 Resorcinol, 871 Restriction endonucleases, 1148–1149 11-cis-Retinal, 581, 608, 1089 11-trans-Retinal, 1089 all-trans-Retinal, 1089 I-28 Retinol (vitamin A), 196, 198, 1088, 1088–1089 Retrosynthetic analysis, 282–284 of acetoacetic ester synthesis, 765–767 of aldol reactions, 750–751 of Claisen condensation, 755 of enamine reactions, 763 of malonic ester synthesis, 769–771 of Michael reactions, 776–777 R-group, 368 Rhodopsin, 608, 1089 a-d-Ribofuranose, 1043 Ribonuclease A, 1121 Ribonucleic acids See RNA Ribose, 644 d-Ribose, 644–645, 645, 1040t, 1041 Ribosomal RNA (rRNA), 1143t, 1145 Ribosome, 1144 Rimantadine, 291 Ring current, 508, 508 Ring opening acid-catalyzed, 452–454 nucleophilic, 454–455 Ring-closing alkene metathesis, 1018–1019 Ring-opening metathesis polymerizations (ROMP), 1019, 1182–1185 Ritter synthesis, 991 RNA, 1134–1135, 1143–1146 messenger, 1143t, 1145–1146 pyrimidine and purine bases of, 1047 ribosomal, 1143t, 1145 transfer, 1143t, 1145 types found in E coli, 1143t Robinson annulation, 777–778 Rod cells, 581 ROMP See Ring-opening metathesis polymerizations (ROMP) Rotation, optical muta-, 1046 observed, 135 specific, 135 Roundworms, 204 Rowland, Sherwood, 309 rRNA See Ribosomal RNA (rRNA) R,S system, 120–123, 1099 RSH, 422 Ruthenium chloride, 252 Ruthenium-containing organometallic catalyst, 1000 S s atomic orbitals, 28–30, 29 S configuration, 120–123 S enantiomer, 135 Saccharin, 1054t Saint-Hilaire, Bon de, 1123 Salicin, 654 Salicyl alcohol, 654 Salicylic acid, 651, 654, 709, 943, 944 synthesis of, 877, 877 Salix, 651 Salt linkages, 1122 Salts of carboxylic acids, 657–658, 712 conversion of alcohols to, 398 Sandmeyer reaction, 971, 972 Sanger, Frederick, 1109, 1132, 1148 Sanger’s reagent, 1132 a-Santonin, 204 Saponification, 699–701, 756, 1074 Saran Wrap, 1170t Saturated fatty acids, 199–200, 1072t, 1073t Saturated hydrocarbons, 63, 64, 304t See also Alkanes Scent, thiols and, 421 Schieman reaction, 971, 972 Schiff base, 606 Schrock, Richard, 1017 Schrödinger, Erwin, 27 Schrödinger equation, 27, 28, 29 s-cis conformation, 829–830 Sea lions, 1071 Secondary alcohols, 17, 18, 392 addition to aldehyde gives, 589 conversion to haloalkane, 399 dehydration of, 405 oxidation of, 412, 413 Secondary aliphatic amines, 967–968 Secondary alkyl groups, 369 Secondary amines, 18, 760 basicity of, 955t physical properties of, 954t Secondary aromatic amines, 967–968 Secondary carbons, 72 Secondary hydrogen, 72 Secondary structure of DNA, 1138–1142 of polypeptides and proteins, 1119–1121 Selective reduction, 619–620 Selective serotonin reuptake inhibitors (SSRIs), 435 Semicarbazide, 612t Semicarbazone, 612t Sequence analysis, 1109–1113, 1148–1153 Serine, 1086t, 1100t, 1102t, 1106 l-Serine, 390, 391 Serotonin, 864, 983, 1129 Ser-Phe-Asp, 1107 Sertraline (Zoloft), 435 Serum glutamate oxaloacetate transaminase (SGOT), 610 Serum glutamate pyruvate transaminase (SGPT), 610 Serylalanine, 1106 SGOT See Serum glutamate oxaloacetate transaminase (SGOT) SGPT See Serum glutamate pyruvate transaminase (SGPT) Shapes atomic s and p orbitals, 28–30 effect on nucleophilicity, 351 of molecules, 21–24 of peptide bond, 1117–1119 of polypeptides and proteins, 1117–1124 Sharpless, Barry, 451 Sharpless asymmetric epoxidation, 451–452 Sharpless epoxidation, 473 Sheep, 1144 Shells, distribution of orbitals in, 2t valence, Shielding, 499 Shifts, chemical See Chemical shifts Side chains, 1100t Sigma (s) anti-bonding molecular orbital, 31 Sigma (s) bonding molecular orbital, 30, 37–41 Sigma (s) bonds in alkenes, 188, 188–189, 206 arrows indicating formation/breaking of, 211 nuclear shielding and, 499 Sigma (s) electrons, ionization potential for, 541 Index Copyright 2010 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 Sigmatropic shifts, 836–841 Signal splitting, 508–510, 509 origins of, 510, 510–517, 512 Signals, NMR, 498 areas under, 503–504 Silane, 446 Sildefanil (Viagra), 995 Silicon, 4t, 119, 446 Silicon dioxide, 446 Silkworms, 195 Silver oxide, 974 Silvered mirror, 616 Silver-mirror test, 616 Silyl ethers, as protecting groups, 445–447 Simmons, Howard, 572 Simmons-Smith reaction, 572–573, 578 Simmons-Smith reagent, 572 Simvastatin (Zocor), 759 Singer, S J., 1087 Skeletal rearrangement, 351–353 Small ring strain, 81 Smalley, Richard, 25 Smith, Ronald, 572 SN1 reaction mechanisms, 336–337, 337 analysis of competitions between substitutions and eliminations, 370–372 differences between SN2 and, 337 E1 reactions vs., 366, 368t effect of solvent on, 345–347 ester hydrolysis and, 702 experimental evidence for, 338–353 kinetics of, 338 leaving group and, 345, 372 skeletal rearrangement in, 351–353 stereochemistry of, 339–340 steric hindrance, 341–343 with tertiary alcohol, 400 SN2 reaction mechanisms, 331, 334–336, 335 analysis of competitions between substitutions and eliminations, 370–372 differences between SN1 and, 337 E2 reactions vs., 366–367, 368t effect of solvent on, 345–346, 347–348 of enamines, 760–762 enolate anions in, 743 ester hydrolysis and, 702 experimental evidence for, 338–353 kinetics of, 338–339 leaving group and, 345, 372 with primary alcohols, 400–401 skeletal rearrangement in, 351–353 stereochemistry of, 340–341 steric hindrance, 343–345 Wittig reaction and, 594, 597 SN2 substitution reaction, acetoacetic ester synthesis and, 765 Snake venom phospholipases, 1087 Soap micelles, 1075, 1075 Soaps, 1074–1078 preparation of, 1074–1075 Sodium formation of ion, 8–9 ground-state electron configuration, 4t reduction of alkyne by, 281–282 Sodium acetate, 152, 405, 701 Sodium acetylide, 182, 270, 591 Sodium amide, 174, 269, 271 Sodium azide, 348 Sodium benzilate, 674 Sodium benzoate, 657, 701, 712, 987 Sodium bicarbonate, 875, 987 Sodium borate, 239 Sodium borodeuteride, 625 Sodium borohydride, 234, 455, 618, 618–619, 717–718 Sodium bromide, 333 Sodium butanoate, 658 Sodium butynide, 270 Sodium cyanide, 388 Sodium 1-decanethiolate, 460 Sodium 2,4-dinitrophenoxide, 926 Sodium 4-dodecylbenzenesulfonate, 1076 Sodium ethoxide, 185, 359, 398, 764, 768 Sodium fluoride, 8–9 Sodium hydride, 174, 182, 183, 269, 398 Sodium hydrosulfide, 422 Sodium hydroxide, 875 Sodium iodoacetate, 422 Sodium isopropoxide, 439, 440 Sodium mercaptoacetate, 422 Sodium methoxide, 333, 398, 440, 454 Sodium naphthalide, 1177–1178 Sodium nitrate, 968 Sodium perborate tetrahydrate, 1076 Sodium phenoxide, 875, 877, 924 Sodium salicylate, 877 Sodium (S)-lactate, 658 Sodium thioglycolate, 422 Sodium undecanoate, 706 Solid-phase synthesis of polypeptides, 1116–1117, 1118 Solubility of alcohols, 394t, 396 of amines, 954, 954t of carboxylic acids, 653t, 655 of ethers, 438t Solvents, 345–348 aprotic, 346, 346t effect on SN1 reactions, 346–347, 348 effect on SN2 reactions, 347–348, 348, 349t in Heck reaction, 1004 nonpolar, 346 polar, 345 polar aprotic, 346, 346t, 348, 351 polar protic, 346–347, 351 protic, 346, 346t Solvolysis, 336 Sondheimer, Franz, 860 Sonogashira coupling, 1016–1017, 1027 d-Sorbitol, 1048, 1048 Sotalol (Betapace), 999 sp hybrid orbitals, 35, 35–36, 41t sp2 hybrid orbitals, 34, 34–35, 41t sp3 hybrid orbitals, 32–34, 33, 41t sp hybridized, 36 sp2 hybridized, 34 sp3 hybridized, 33 Spartan (computer program), 78, 114 Spasmolytol, 471, 944 Specific rotation, 135 mutarotation and, 1046 Spectrometers electron ionization mass, 540 mass, 539–542, 540 nuclear magnetic resonance, 500, 500–501 tandem mass, 553 Spectrometry, mass, 539–560 Spectroscopy Fourier transform NMR, 500 infrared (See Infrared (IR) spectroscopy) molecular, 475–476 nuclear magnetic resonance, 495–538 Raman, 478 UV-visible, 820–824 Spider silk, 1098, 1123 Spiders, 1123 Spidroin and 2, 1123 Spin (electron), paired, Spin (nuclear), 495–496, 496t in applied magnetic fields, 496–497, 496–497 (n + 1) rule and, 508–510 Spin-spin coupling, 510, 510–517 bond rotation and, 513–515 coincidental overlap and, 515–516 complex, in flexible molecules, 516 fast exchange and, 516–517 geminal, 514 peak intensities and, 511–512 physical basis for (n + 1) rule and, 512 splitting patterns, complex, 513 vicinal, 510, 510–511 Spiro [2,2] pentane, 577 Spiro[4,5]decan-6-one, 412 Spiro[4,2]heptane, 572 Squalene, 1084 SSRIs See Selective serotonin reuptake inhibitors (SSRIs) Stachyose, 1067 Staggered conformations, 75, 77 anti conformation, 78 gauche conformation, 78 Stanozolol, 1083, 1084 Starch, 1055–1056, 1056 Statins, 758–759 Stearic acid, 199, 652t, 1072t, 1073t Steitz, Thomas A., 1144 Step-growth polymerizations, 1162–1169 Stereocenters, 89–90, 117 acyclic molecules with two or more, 123–129 cyclic molecules with two or more, 129–132 Stereochemical issues, in catalytic allylic alkylation, 1011–1012 Stereochemistry, 114 of Cope rearrangement, 840–841 of Diels-Alder reaction, 835–836 of polymers, 1175–1176 of radical halogenation, 313 of SN1 reactions, 339–340 of SN2 reactions, 340–341 topicity and, 517–520 Stereoisomers, 88–96, 89, 116–120, 132, 133, 134 See also Chirality Stereoselective reactions anti, 229–233 in E2 reactions, 361–365 syn, 237 Stereospecific reactions, 249 Steric hindrance, 341, 343–345 Steric strain, 75, 78 diaxial (axial-axial) interaction, 85 Steroid hormones, 94, 1082–1084, 1083t synthesis of, 1036 Steroids, 94, 94, 1081–1085 anabolic, 1083–1084 structure of major classes of, 1081, 1081–1084 trans-Stilbene, 1006 Stille coupling, 1015–1016 Stitches, dissolving, 1168 Stoichiometry, base, 781 Index Copyright 2010 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-29 Stork, Gilbert, 760 Stork enamine reaction, 760 Strain, 75 angle, 78 small ring, 81 steric, 78 torsional, 76–77 Strain energy, 101, 101 s-trans conformation, 829 Streptomyces, 1030 Streptomyces cinamonensis (fungi), 803 Streptomyces orientalis (fungi), 1032 Stretching frequencies, 480t Stretching vibrations, 479 Strong nucleophiles, 350 Structure of acid anhydrides, 681–682 of acid halides, 681 of alcohols, 391 of aldehydes, 581–582 of alkanes, 63–65 of alkynes, 266–267 of allyl radical, 316, 316–317 of amides, 684–685 of amines, 947–948 of amino acids, 1098–1099 of benzene, 854, 854–858 of carboxylic acids, 649 of cycloalkanes, 72–73 of DNA, 1137–1143 of epoxides, 447–448 of esters, 682–684 of ethers, 436 of haloalkanes, 296 of imides, 685 of ketones, 581–582 of lithium diorganocopper reagents, 566–567 of monosaccharides, 1038 of nitriles, 686–687 of organomagnesium compounds, 562 of phenols, 870–871 of phospholipids, 1085–1086 of polypeptides, 1109–1113 of proteins, 1109–1113 of steroids, 1081–1084 of thiols, 420 Styrene, 330, 469, 867, 1003, 1160, 1194 polymerization of, 1170t, 1176, 1176t Styrene oxide, 455, 569 Styrofoam, 1170t Subshells, Substituent groups effects of, on further substitution, 917–920, 918t effects of, on reaction rate, 830–831 meta-directing, 917 ortho-para-directing, 917 Substituents endo, 832 exo, 832 Substitution reactions, 215, 302, 917–924 electrophilic aromatic, 907–916 nucleophilic acyl, 690, 713 nucleophilic aromatic, 924–927 Succinic acid, 650, 674 Succinic anhydride, 681, 935, 945 Succinimide, 314, 685, 687, 882 Sucrose, 1052, 1052–1053, 1054t I-30 Suffixes, 71 Sugar amino, 1041–1042 Sugars disaccharides, 1052–1055 monosaccharides, 1038–1042 oligosaccharides, 1052–1055 polysaccharides, 1052, 1055–1058 reducing, 1048–1049 2-Sulfanylethanol, 421 Sulfhydryl (—SH) group, 390, 420, 584t Sulfides, 459–460 nomenclature of, 459 oxidation of, 460 preparation of, 459–460 Sulfonamides, acidity of, 687–689 Sulfonates, conversion of alcohols to, 403–405 Sulfonation, 907, 909–911, 911 Sulfonyl chloride, 403–404, 404, 681 Sulfonylureas, 734 Sulfur compounds containing, 36 ground-state electron configuration, 4t isotopes of, 543t M + peaks, 545 Sulfur dioxide, 847 Sulfur mustard, hydrolysis of, 373–374 Sulfuric acid, 278–279, 909 Lewis structure for, 36, 36 pKa value, 161t Supercoiling, 1142–1143, 1143 Superglue, 1179 Superhelical twist, 1142–1143 Suprafacial interaction, 826 Surfynol, 641 Suzuki, Akira, 1013 Suzuki coupling, 1013–1015, 1014t Sweeteners, 1053–1054, 1054t high-fructose corn syrup, 1057 Symmetry center of, 115 plane of, 115 Syn addition reactions, 280 Syn stereoselective reactions, 237 Syndiotactic polymers, 1175, 1175 Synthesis gas, 103 Synthetic detergents, 1076 T d-Talose, 1040t Tamoxifen, 742, 794, 904 Tanaka, Koichi, 553 Tandem mass spectrometer (MS-MS), 553 Tartaric acid, 114, 125, 125–126, 435 Newman projections, 128 as resolving agent, 142, 143 stereoisomers of, 127t Tautomers, 276–277 keto-enol, 277, 612–615, 705 Tay-Sachs disease, 1069 Tay-Sachs ganglioside, 1069 TBDMS group See tert-Butyldimethylsilyl (TBDMS) group TCA See Tricarboxylic acid (TCA) cycle Teflon, 301, 1170t See also Poly(tetrafluoroethylene) (PTFE) Telechelic polymers, 1180 Telomeres, 1144 Temperature, balance between SN2 and E2 reactions and, 367 Terephthalic acid, 651, 677, 738, 881, 1164, 1165 Terminal alkynes, 268 Terpenes, 197–200 Terpin, 260 Tertiary alcohols, 17, 392 addition to ketone, 589 conversion to haloalkane, 399 dehydration of, 405 oxidation of, 412, 413 SN1 reaction with, 400 Tertiary aliphatic amines, 967 Tertiary alkyl groups, 369–370 Tertiary amines, 18 basicity of, 955t physical properties of, 954t Tertiary aromatic amines, 967 Tertiary butyl ethers, 443–444 Tertiary carbons, 72 Tertiary halide, 18 Tertiary hydrogen, 72 Tertiary structure of DNA, 1142–1143 of polypeptides and proteins, 1121–1124 TES See Triethylsilyl (TES) group Tesla (T), 496 Testosterone, 1083, 1084 specific rotation of, 136 tetra- prefix, 69 2,2,3,3-Tetrabromobutane, 273 Tetrabutylammonium fluoride, 447 Tetrachloromethane, 302 Tetracyclic ring system, 1081, 1081 Tetradecane, 65t Tetradecanoic acid, 652t cis-11-Tetradecenyl acetate, 196 trans-11-Tetradecenyl acetate, 196 Tetradecylpyridinium chloride, 951 Tetraethyllead, 60 Tetrafluoroethylene, 57 polymers derived from, 1170t Tetrahedral shape, 22, 23t Tetrahydrocannabinol, 560 Tetrahydrofuran (THF), 237, 346t, 437, 562, 659, 1189 Tetrahydrofurfuryl alcohol, 431 Tetrahydroisoquinoline, 960 Tetrahydro-6-methyl-2-pyranone, 678 Tetrahydropyran, 437 Tetrahydropyranyl (THP) ethers, 605–606 Tetrahydrothiophene, 459 Tetrahydrothiopyran, 460 a-Tetralone, 913 Tetramethylammonium chloride, 951 Tetramethylammonium hydroxide, 987 2,2,3,3-Tetramethylbutane, 100t Tetramethyloxirane, 467 Tetramethylsilane (TMS), 446, 499 Tetraodontidae (puffer fish), 95, 95 Tetrapeptides, 1107 Tetrasubstituted carbon-carbon double bonds, 245 Tetrodotoxin, 95, 95 Textile fibers, 1057–1058 Textiles Dacron, 651, 677, 1058, 1165 Kevlar, 738, 1164, 1164–1165 Nylon 6, 1164, 1164 Nylon 6,10, 1191 Nylon 66, 651, 738, 1158, 1163, 1163–1164 rayon, 1057, 1058 Index Copyright 2010 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 Theory of resonance, 42–44 Thermal reactions, 166 Thermochemistry, 165–169 of acid-base reactions, 169 reaction coordinate diagrams and, 166–169 Thermodynamic enolates, 783–784 Thermodynamic (equilibrium) control, 775, 783, 817 of electrophilic addition, 816–820, 818 Thermodynamics, 167 of addition reactions, 209 Thermolysis, 569 Thermoplastics, 1159 Thermosetting plastics, 1159 Thermosetting polymers, 1168–1169 THF See Tetrahydrofuran (THF) Thiane, 460 Thiazolidine, 686 Thiazolinone, 1111–1112 Thioethers, 459–460 See also Sulfides 6-Thioguanine, 1155 Thiol groups, 140 Thiolane, 459 Thiolate anion, 367 Thiolates, 424 Thiols, 390, 420–424 acidity of, 423 in biological molecules, 422 nomenclature of, 420–421 oxidation of, 423–424 physical properties of, 421–422, 422t preparation of, 422–423 structure of, 420 Thionyl bromide, 403 Thionyl chloride, 403, 665 Thiophene, 864 Thomson, J J., 539, 854 THP See Tetrahydropyranyl (THP) ethers THP group, 605 Threonine, 140, 1100t, 1102t Threose, 124 d-Threose, 1040t, 1041 l-Threose, 1041 Thromboxane A2, 1080, 1081 Thromboxane B2, 808 Thujane, 75 Thyme (Thymus vulgaris), 871 Thymine, 959 Thymine (T), 1047, 1135, 1155 Thymol, 871, 993 Thymus vulgaris (thyme), 871 l-Thyroxine (T4), 1101 Tietze, Lutz, 1036 Tiffeneau-Demjanov reaction, 970 TIPS group See Triethylsilyl (TES) group Titration, of amino acids, 1103–1104, 1104 TMS See Tetramethylsilane (TMS) Tobacco mosaic virus protein disc, 1124t a-Tocopherol (vitamin E), 318, 1044, 1091 Tolazamide, 734 Tolbutamide, 734 Tolciclate, 850 Tollens’ reagent, 616 Toluene as aprotic solvent, 346t bromination of, 327 conversion of benzyl group to, 882 halogenation of, 881–882 in hydrogenolysis of Z-protecting group, 1115 infrared spectrum of, 483, 484 mass spectrum of, 552, 554 in miconazole synthesis, 940 nomenclature of, 867, 868 oxidation of, 880 in radical chain mechanism, 896 2,6-Toluene diisocyanate, 1166 Toluene radical cation, 553 p-Toluenesulfonate anion, 404 Toluenesulfonate (Ts—) groups, 152 p-Toluenesulfonic acid, 161t, 681 p-Toluenesulfonyl chloride, 404, 681, 708 m-Toluic acid, 732 m-Toluidine, 925, 926 o-Toluidine, 973, 1051 p-Toluidine, 925, 949, 987 Topicity, 517–520 Toremifene, 905 Torsional strain, 75, 76–77 Tosyl chloride See p-Toluenesulfonyl chloride Toxins See Poisons trans- prefix, 89 trans diaxial conformations, 231 trans diequatorial conformations, 231 Trans fatty acids, 247 Transaminases, 610 Transamination, 610–611 Transesterification, 709 Transfer RNA (tRNA), 1143t, 1145 Transition metals, as catalysts, 245–246, 246, 247, 280, 660 Transition states (TS), 166, 208 Transmetallation, 1012 Trehalose, 1066 tri- prefix, 69 Triacontyl palmitate, 1073 Triacylglycerols, 1071–1074 Trialkenylborane, 275, 280–281 Trialkylborane, 236, 236, 238–239 Trialkylborate, 239 2,4,6-Tribromophenol, 869 Tricarboxylic acid (TCA) cycle, 138, 666 Trichloroacetaldehyde, 935 Trichloroacetic acid, 655 2,4,6-Trichloroaniline, 973 1,3,5-Trichlorobenzene, 973 2,4,6-Trichlorobenzenediazonium chloride, 973 1,1,1-Trichloroethane, 297 Trichloroethylene (trichlor), 297 Trichlorofluoromethane, 309 Trichloromethane, 297, 302, 570 Trichloromethide anion, 571 Tridecane, 65t (E)-5-Tridecene, 567 Tridemorph, 991 Trienes, 195 cis,trans isomers, 195–196 Triethylamine, 708, 950, 954t, 955t, 987 Triethylammonium chloride, 403, 446, 950, 987 Triethylsilyl chloride (TESCI), 446 Triethylsilyl (TES) group, 446 4,4,4-Trifluoro-1-butanol, 173 2,2,2-Trifluoroethanol, 172, 173 Trifluoroethoxide ion, 173 Trifluoromethanesulfonate, 1004 Trifluoromethanesulfonyl chloride, 1004 Trifluoromethyl benzene, 938 3,3,3-Trifluoro-1-propanol, 173 Trifluralin B, 936 Triglycerides, 199–200, 247, 1071–1074 fats, 1073 fatty acids, 1072–1073, 1073t oils, 1073 physical properties of, 1073–1074, 1074t polyunsaturated, 1074, 1074 reduction of fatty acid chains, 1074 2,3,4-Trihydroxybutanal, 124, 129 Triidoaromatics, 996 L-Triiodothyronine (T3), 1101 Triisopropylsilyl chloride (TIPSCI), 446 Triisopropylsilyl (TIPS) group, 446 Trimethylamine, 18, 947, 954t, 955t, 974 1,2,4-Trimethylcyclohexane, 87, 87–88, 92 3,5,5-Trimethyl-2-cyclohexanone, 798 2,2,4-Trimethylpentane (isooctane), 72, 99, 103, 547 2,4,6-Trimethylphenol, 900 Trimethylphosphine, 36, 36 Trimethylphosphite, 596, 597 Trimethylsilyl chloride (TMSCI), 446 2,4,6-Trinitrophenol, 874 Triols, 392 Trioses, 1038 Tripeptides, 1107 Triphenylmethyl chloride, 897 Triphenylphosphine, 594, 595, 1005 Triphenylphosphine oxide, 594, 595 Triphosphate ion, 682 Triphosphoric acid, 682 Triple bonds, 9, 12, 40, 41 Trisaccharides, 1052 Tristearin, 1073 Trisubstituted carbon-carbon double bonds, 245 Trityl chloride, 897 tRNA See Transfer RNA (tRNA) Tropical oils, 1073 Tropylium ion, 552–553, 866, 866 Tryptophan, 1100t, 1102t TS See Transition states (TS) Turmeric, 810 Twist-boat conformation, 83, 83–84 Tyrosine, 1100t, 1102t U Ultraviolet radiation See also Electromagnetic radiation wavelengths and energies of, 820t Ultraviolet visible radiation, 475t Unconjugated dienes, 810 Undecane, 65t Undecanenitrile, 706, 707 Undecanoic acid, 706, 707 Unimolecular reaction, 336 Unlike charges, contributing structures and, 45 Unoprostone, 1095 Unsaturated alcohols, 393 a,b-Unsaturated carbonyl, 751 a,b-Unsaturated carbonyl compounds, conjugate addition to, 771–780 Unsaturated fatty acids, 1072t, 1073t Unsaturated hydrocarbons, 63, 64, 186–187 See also Alkenes; Alkynes; Arenes Upfield shifts, 501 Uracil (U), 1047, 1135 Urea, 712, 733 Urethane, 738 See also Carbamates Uridine, 1135 Index Copyright 2010 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-31 Uronic acids, 1049 Urushiol, 871 UV-visible spectroscopy, 820–824 V Valence bond (VB) theory, 29–30, 31–36, 32 combining with molecular orbital theory, 37–41 Valence electrons, Valence shells, contributing structures and, 45 Valence-shell electron-pair repulsion (VSEPR), 21–22 Valeric acid, 652t Valine, 1100t, 1102t Valnoctamide, 803 Valproic acid, 707 van der Waals, J D., 299 van der Waals forces, 299 van der Waals radius, 299, 299t Vancomycin, 1032, 1033 Vancomycin aglycon, 1033 Vanilla pompona (vanilla), 871 Vanillic acid, 616 Vanillin, 616, 624, 871 VB See Valence bond (VB) theory Venlafaxine, 941 Verapamil (Effexor), 801, 802 Vibrational infrared region, 476–478 Vicinal coupling, 510, 510–511 Vicinal diols, 241, 410–412 Vicinal hydrogens, 510 Vinyl acetate, 291, 523 Vinyl chloride, 274, 275, 330, 1160 polymers derived from, 1170t Vinyl ethers, 1176t Vinyl group (ethenyl), 191 Vinyl thioethers, 1176t Vinylacetylene, 268 Vinylic carbocation, 274 Vinylic halide, 296, 567 Vinylic hydrogens, 506–508, 506t, 507 Visible light color-wavelength correlation, 822 I-32 Visible radiation, 820t Visual purple, 608 Vitamins A, 196, 198, 203, 799, 1088, 1088–1089 A acetate, 642 B6, 418, 610, 610–611, 986 C, 1044 D, 1089–1091 E, 318, 1044, 1091, 1091 K1, 1090, 1090 K2, 879, 879 von Euler, Ulf, 1078 VSEPR See Valence-shell electron-pair repulsion (VSEPR) W Wacker process, 660 Warburganal, 848 Warfarin, 684, 799 Water, 160, 215, 216 in acid-base reactions of phenols, 875 acidity of, 161t, 174t, 397t addition of, to aldehydes and ketones, 598 addition of, to alkenes, 224–226 in crossed aldol reactions, 749 electrostatic potential map of, 26 hydrolysis, 694–707 Lewis structure for, 12, 22, 22 orbital overlap in, 34 as polar molecule, 25 as reactant, 154 shape of, 22, 22 as solvent, 347, 347t Watson, James D., 1138, 1139 Watson-Crick model, 1139 Wave equation, 27 Wave functions, 27 Wave mechanics See Quantum mechanics Wave properties, moving particles and, 27 Wavelength (l), 474, 475t units of, 475t Wavenumbers, 476–477 Waxes, 96 Weak nucleophiles, 350 Weight average molecular weight (Mw), 1160 Wilkins, Maurice, 1138, 1139 Williamson ether synthesis, 439–440, 448 Willow, 651 Willow bark, 654 Wine, 390 Wittig, Georg, 594 Wittig reaction, 594–597 Wolff, L., 622 Wolff-Kishner reduction, 622–623 Wormwood, 204 X X-ray contrast media, 996 X-ray diffraction patterns, 1139 m-Xylene, 868, 880 p-Xylene, 881, 1165 Xylitol, 1048, 1048 d-Xylose, 1040t Y Yellow gas, 663 -yl suffix, 68, 69 Ylides, 594 -yn-, 71, 267 Yomogi alcohol, 432 Yonath, Ada E., 1144 Z Z configuration, 192 Zaitsev elimination, 357 Hofmann elimination and, 976 Zaitsev’s rule, 357 Zidovudine (AZT), 1140 Ziegler, Karl, 1173 Ziegler-Natta chain-growth polymerizations, 1173–1175 Zinc 10-undecenoate, 672 Zinc-copper couple, 572 Zostrix, 872 Zwitterion, 1098–1099 Index Copyright 2010 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 Copyright 2010 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 NH2 NH N Amine, primary Amine, secondary Amine, tertiary O CH CH2 (CH3CH2)3N (CH3CH2)2NH CH3CH2NH2 CH3CNH2 HC CH2 CH3CH3 CH3CH Triethylamine Diethylamine Ethylamine Ethanamide (Acetamide) Ethyne (Acetylene) Ethene (Ethylene) Ethane Ethanal (Acetaldehyde) Ethanol (Ethyl alcohol) Ethanoyl chloride (Acetyl chloride) Ethanoic anhydride (Acetic anhydride) IUPAC Name Thiol Sulfide Phenol Nitro Nitrile Ketone Haloalkane Ether Ester Epoxide O C C H O CH2 S S H O N1 O2 OH CH3CH2SH CH3SCH3 CH3NO2 CH3 C # N CH3CCH3 C 9C#N O CH3CH2Cl CH3OCH3 CH3COCH3 H2C O CH3SSCH3 CH3COH O Example O OH X F, Cl, Br, I X O C O C S S Disulfide O O C Carboxylic acid O Functional Group* * Where bonds to an atom are not specified, the atom is assumed to be bonded to one or more carbon or hydrogen atoms in the rest of the molecule C Amide N C C Alkyne O C C H Alkene Alkane C O O Aldehyde CH3CH2OH CH3CCl O CH3COCCH3 OH C Alcohol Cl O O O C O C O Example Acid chloride Acid anhydride O Functional Group* Some Important Organic Functional Groups Ethanethiol (Ethyl mercaptan) Dimethyl sulfide Phenol Nitromethane Ethanenitrile (Acetonitrile) Propanone (Acetone) Chloroethane (Ethyl chloride) Dimethyl ether Methyl ethanoate (Methyl acetate) Oxirane (Ethylene oxide) Dimethyl disulfide Ethanoic acid (Acetic acid) IUPAC Name Copyright 2010 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 Period number Group number, U.S system IUPAC system K Rb 37 39.0983 Y Ac (227) Actinium Db 105 180.9479 Tantalum Ta 73 92.9064 Niobium Nb 41 50.9415 Actinides (261) 24 Cr 8B (8) 8B (9) Ru 44 55.847 Nd 60 (262) Bohrium Bh 107 186.207 Rhenium Re 75 (98) Pm 61 (265) Hassium Hs 108 190.2 Osmium Os 76 101.07 27 Co 8B (10) 1B (11) 92 91 Pa 90 Th 238.0289 232.0381 231.0359 Protactinium Uranium Thorium U 144.24 140.9076 Sm 62 (266) Ds 110 195.08 Platinum Pt 78 106.42 Palladium Pd 46 58.693 94 93 Am 95 151.965 Europium Eu 63 (271) (237) (244) (243) Neptunium Plutonium Americium Pu 150.36 (145) Np 28 Ni Nickel 29 Cu Rg 111 196.9665 Gold Au 79 107.8682 Silver Ag 47 63.546 Copper (247) Curium Cm 96 157.25 Gadolium Gd 64 (277) Meitnerium Darmstadtium Roentgenium Mt 109 192.22 Iridium Ir 77 102.9055 Rhodium Rh 45 58.9332 Cobalt Praseodymium Neodymium Promethium Samarium 59 (263) Seaborgium Sg 106 183.85 Tungsten W 74 95.94 Pr 140.115 Tc 43 54.9380 26 Iron Fe Molybdenum Technetium Ruthenium Mo 42 51.9961 58 Cerium 25 Mn Chromium Manganese Ce (262) Rutherfordium Dubnium Rf 104 178.49 Lanthanides Numbers in parentheses are mass numbers of radioactive isotopes 227.0278 (223) 89 88 Ra Radium 87 Fr Francium 138.9055 137.327 132.9054 72 Hafnium Hf 57 Lanthanum La 56 Ba Barium 55 Cs 91.224 88.9059 Zirconium 87.62 Cesium 85.4678 40 39 Yttrium 38 Sr Strontium Zr 47.88 44.9559 40.078 Vanadium V 23 22 Ti Titanium 21 Sc Scandium 20 Ca 5B (5) 4B (4) Calcium 24.3050 22.9898 19 12 Mg Magnesium 11 Na Sodium 2B (12) Ga Cf 98 162.50 Dysprosium Dy 66 204.3833 Thallium Tl 81 114.82 Indium In 49 69.723 Gallium Es 99 164.9303 Holmium Ho 67 (285) — — 114 207.2 Lead Pb 82 118.710 Tin Sn 50 72.61 Germanium Ge 32 28.0855 26.9815 31 14 Si Silicon 13 Al Aluminum (247) (251) (252) Berkelium Californium Einsteinium Bk 97 158.9253 Terbium Tb 65 (277) Copernicium Cn 112 200.59 Mercury Hg 80 112.411 Cadmium Cd 48 65.39 Zinc Zn 30 12.011 10.811 9.0122 Carbon C 4A (14) 6.941 Boron B 3A (13) 7B (7) Nonmetals Be 6B (6) An element Metals Semimetals Beryllium Rubidium Gold 196.9665 Atomic number Symbol Name Atomic mass 3B (3) 79 Au Li 2A (2) Lithium Potassium 1.0079 Hydrogen H 1A (1) KEY Periodic Table of the Elements Md 101 168.9342 Thulium Tm 69 (289) — — 116 (209) Polonium Po 84 127.60 Tellurium Te 52 78.96 Selenium Se 34 32.066 Sulfur S 16 15.9994 Oxygen O 6A (16) (257) (258) He 36 No 102 173.04 Ytterbium Yb 70 (210) Astatine At 85 126.9045 Iodine I 53 79.904 (259) (260) Lawrencium Lr 103 174.967 Lutetium Lu 71 (222) Radon Rn 86 131.29 Xenon Xe 54 83.80 Krypton Kr 35 Bromine Br 39.948 Argon Ar 18 20.1797 Neon Ne 10 4.0026 Helium 35.4527 Chlorine Cl 17 18.9984 Fluorine F 7A (17) Fermium Mendelevium Nobelium Fm 100 167.26 Erbium Er 68 208.9804 Bismuth Bi 83 121.757 Antimony Sb 51 74.9216 Arsenic As 33 30.9738 Phosphorus P 15 14.0067 Nitrogen N 5A (15) 8A (18) 7 Chemical Connections and Connections to Biological Chemistry Essays Section 1.4 Chemical Connections: Fullerene— A New Form of Carbon Section 2.6 Chemical Connections: The Poisonous Puffer Fish Chemical Connections: Octane Rating—What Those Numbers at the Pump Mean Section 2.8 Section 3.8 Section 3.8 Connections to Biological Chemistry: Amino Acids Conn to Bio.Chem: Chiral Drugs Section 4.5 Connections to Biological Chemistry: The Ionization of Functional Groups at Physiological pH Section 5.3 Chemical Connections: The Case of Iowa and New York Strains of the European Corn Borer Connections to Biological Chemistry: The Importance of cis Double Bonds in Fats Versus Oils Section 5.4 Section 6.6 Connections to Biological Chemistry: Trans Fatty Acids: What They Are and How To Avoid Them Section 8.5 Section 8.7 Chemical Connections: Freons Connections to Biological Chemistry: Antioxidants Section 9.9 Connections to Biological Chemistry: Mustard Gases and the Treatment of Neoplastic Diseases Section 10.2 Connections to Biological Chemistry: The Importance of Hydrogen Bonding in Drug-Receptor Interactions Chemical Connections: Blood Alcohol Screening Connections to Biological Chemistry: The Oxidation of Alcohols by NAD1 Section 10.8 Section 13.10 Chemical Connections: Magnetic Resonance Imaging Section 14.3 Connections to Biological Chemistry: Mass Spectra of Biological Macromolecules Connections to Biological Chemistry: Pyridoxine (Vitamin B6), a Carrier of Amino Groups Section 16.11 Conn to Bio.Chem: NADH— The Biological Equivalent of a Hydride Reducing Agent Section 18.1 Chemical Connections: From Cocaine to Procaine and Beyond Chemical Connections: From Moldy Clover to a Blood Thinner Chemical Connections: The Penicillins and Cephalosporins: b-Lactam Antibiotics Connections to Biological Chemistry: The Unique Structure of Amide Bonds Section 19.4 Chemical Connections: Drugs That Lower Plasma Levels of Cholesterol Chemical Connections: Ibuprofen— The Evolution of an Industrial Synthesis Section 19.7 Section 20.3 Chemical Connections: Curry and Cancer Section 21.3 Chemical Connections: Carcinogenic Polynuclear Aromatic Hydrocarbons and Smoking Chemical Connections: Capsaicin, for Those Who Like It Hot Section 21.4 Section 23.4 Chemical Connections: The Poison Dart Frogs of South America Section 23.5 Connections to Biological Chemistry: The Planarity of !NH2 Groups on Aromatic Rings Section 24.7 Chemical Connections: Singlet Oxygen Section 25.2 Chemical Connections: l-Ascorbic Acid (Vitamin C) Chemical Connections: Testing for Glucose Chemical Connections: A, B, AB, and O Blood Group Substances Chemical Connections: High-Fructose Corn Syrup Section 25.3 Section 25.4 Section 25.5 Section 26.2 Connections to Biological Chemistry: FAD/ FADH2: Agents for Electron Transfer in Biological Oxidation–Reductions: Fatty Acid Oxidation Section 26.5 Chemical Connections: Snake Venom Phospholipases Chemical Connections: Vitamin K, Blood Clotting, and Basicity Section 26.6 Section 16.9 Section 17.3 Section 17.7 Section 17.9 Chemical Connections: From Willow Bark to Aspirin and Beyond Chemical Connections: The Pyrethrins: Natural Insecticides of Plant Origin Chemical Connections: Esters as Flavoring Agents Chemical Connections: Ketone Bodies and Diabetes Mellitus Section 27.6 Chemical Connections: Spider Silk Section 28.2 Chemical Connections: The Search for Antiviral Drugs Chemical Connections: The Fountain of Youth Chemical Connections: DNA Fingerprinting Section 28.3 Section 28.5 Section 29.5 Section 29.6 Chemical Connections: Stitches That Dissolve Chemical Connections: Organic Polymers That Conduct Electricity Chemical Connections: The Chemistry of Superglue Chemical Connections: Recycling of Plastics Copyright 2010 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 ... world CHO O CH3O — P — O2 OCH3 Dimethyl phosphate H C OH O CH2 ! O ! P ! O2 O2 Glyceraldehyde 3-phosphate CHO O CH2O P O2 HO O2 H3C N Pyridoxal 5-phosphate COO2 O C O P O2 H2C O2 Phosphoenolpyruvate... (Pyrophosphoric acid) O O O 2O ! P ! O ! P ! O2 O2 O O O OH OH O2 OH Triphosphoric acid Diphosphate ion (Pyrophosphate ion) O 2O ! P ! O ! P ! O ! P ! O2 HO ! P ! O ! P ! O ! P ! OH O2 O O2 O2 Triphosphate... reaction O R C O O H H3O C R H2O H O H O H 1R9OH R 2R9OH O II F O C O R1 O H H R9 O 2H2O 1H2O R V5C C O H2O IV D H R9 H3O1 H III E H O O H H R9 C R H3O1 O I5G H2O R9 C H O O H2O H3O1 VI B R C R9 O VII