JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm SUBJECT INDEX The vast use of transition metal catalysts in organic chemistry makes the citation of every individual metal impractical, so there are limited citations of individual metals. Palladium is one exception where individual citations are common, in keeping with the widespread use of that metal. However, in most cases, the term metal catalyst, or catalyst, metal is used as a heading, usually representing transition metals. A-SE2 mechanism 893 and the steering wheel model acceleration of Diels-Alder reactions 487 151–152 reactions, high pressure A1 mechanism, acetal hydrolysis and universal NMR database 1038 487 155 hydrogen-bonding 1038 A1,3-strain 196 Cahn-Ingold-Prelog system hydrophobic effect 1038 A2 mechanism, acetal hydrolysis 149–152 in water 1038 487 determination 152 ionic liquids 1038 ab initio calculations 36 D/L nomenclature 149 micellular effects 1038 and acidity 346 Kishi’s NMR method 155 microwave irradiation 1038 and antiaromaticity 71 sequence rules 149–152 phosphate 1039 and nonclassical carbocations absolute hardness 64, 359, 361 solid state 1038 427 table 361 ultracentrifuge 1038 norbornyl carbocation 436 absorbents, chiral 168 ultrasound 1038 ab initio studies 248 absorption, and conjugation 317 zeolites 1038 1,2-alkyl shifts in alkyne anions differential, and diastereomers acceleration, Petasis reaction 1349 168 1202 and cubyl carbocation 413 differential, and resolution 169 acenaphthylene, reaction with and SN2 408–409 abstraction, and vinylic DBr 894 cyclopropane ring opening 907 hydrogenation 852 acenaphthylenes 1285 E2 mechanism 1274 benzylic hydrogens, by radicals acenaphthylene, with DBr 894 transition state for radical 852 acenes, hetero see heteroacenes hydrogen abstraction 849 hydrogen atom, photochemical acenes 61, 85 abnormal Beckmann 330 twisted 85 rearrangement 1326, hydrogen, by radicals, rate 848 zigzag 85 1369, 1377 and carbenes 727 acepentalenes, radical ions 265 abnormal Claisen rearrangement by nitrenes 277 acetal formation, and drying 1419 by radicals, ab initio study agents 1101 abrine esters, as catalysts 310 849 azeotropic distillation 1101 absolute aromaticity 39 by radicals, and mechanism 1102 absolute configuration 149 rearrangements 1346 acetaldehyde, and paraldehyde and biochemical methods 153 by radicals, transition state 1259 and circular dichroism 154 848 rational barrier 193 and GC 153 radical, and stereoelectronic acetals, acid catalyzed hydrolysis and glyceraldehyde 148 effects 853 486 and molar rotation 155 COPYRIGHTEDselectivity by radicals 849 MATERIALand enol ethers 1103 and Mosher’s acid 153 stereoselective 851 and Lewis acids 488 and Mosher’s ester 153 of atoms from radicals 263 and microwaves 1103 and NMR 153 radicals, and alkanes 849 and transacetalization 1103 and optical comparison 153 radicals, and alkenes 852 from alcohols and aldehydes optical rotatory dispersion 154 radicals, transition state 845 1101 and specific rotation 155 abstracts 1614 from aldehydes 1102 the SN2 reaction 153 ABX pattern, NMR 155–156 and ketones 1101 March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, Eighth Edition. Michael B. Smith. © 2020 John Wiley & Sons, Inc. Published 2020 by John Wiley & Sons, Inc. 1917 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm 1918 SUBJECT INDEX acetals, acid catalyzed hydrolysis acetylenes, electron density map acidic hydrogen atoms, solvents (Continued) 12 1171 and Eosin Y 1102 excited state 319 acidic Lewis ionic liquids 395 photochemistry 1102 triplet 269 acidity see acid strength from alkynes 918 acetylenic sulfoxides, with acidity scales, and alcohols 353 from amides 720 cuprates 962 and amides 353 from Grignard reagents 570 acetylide ion, with alkyl halides and basic solvents 353 from ketones 1102 596 and calorimetric measurements from ortho esters 570, 1103, with epoxides 596 354 1574 with sulfates 596 and carbon acids 353 from oxidation of hydroxy with sulfonate esters 596 and indicators 353 ethers 866 aci form of nitro compounds, and acidity, solvent see solvent acidity hydrolysis 486 tautomerism 102 acidity, amides versus amines 364 and Brønsted coefficient nitro compounds 1099 acidity, and carborane acids 351 487 nitro compounds, and the Nef and carboxylic acids 21 and SN1 mechanisms 486 reaction 1099 and chloromethylation 656 and isotope labeling 486 acid base reactions, and and conformation 368 rate determining step 487 organometallics 732 and cyclopentadiene 64 ketene see ketene acetals acid catalysis, general 356 and electronegativity 365 labeling 486 alkenes with alcohols 917 and entropy 368, 372 N, Se 924 for the Schmidt reaction 1373 and face strain 366 silyl enol see enol silyl acetals acid catalyzed addition of alkenes and five-membered rings 64 silyl ketene 586, 1180 to alkenes 942 and free energy 373 transetherification 496 addition of water to carbonyls and hybridization 368 with allylic silanes 570 1095 and hydrogen bonding 106, 366 with hydride reagents 1574 aldol condensation 1178 and indicators 352 with silyl enol ethers 570 hydration of aldehydes and and ionic liquids 352 with trialkyl phosphites 501 ketones 1096 and ionic strength 373 acetanilide, nitration 632 hydrocarboxylation 984 and IR 352 acetanilides see anilines, acyl hydrocarboxylation of alkenes and Meldrum’s acid 368 acetate, allylic, with keto acids, 982 and organolithium reagents 247 metal catalyzed 887 hydrolysis 383 and periodic table 365 acetate, as a base 340 Knoevenagel reaction 1187 and phenalene 61 acetate, enol see enol acetates reaction with diketones 1103 and proton transfer 350 acetic acid, cis conformation 192 rearrangement of and resonance 365 dimeric 106 hydrazobenzenes 1422 and s character 368 acetic anhydride, and acyl acid derivatives, with amides and solvent 347, 372 fluoroborate 1025 1248 and solvent effects 371 and dehydration of oximes to acid forms 102 and steric effects 366 nitriles 1325 acid solutions, and the tetrahedral and the Hammett reaction and nitration of aromatic mechanism 1090 constant 372 compounds 631 acid strength 238, 340–345 and the medium 370 conjugate addition 979 and solvent 341–345 benzoic acids, and substituents acetoacetamide, enol content 98 crystallographic scale 346 363 acetoacetic esters, and enol definition 340 carboxylic acids 355 content 98 field effects 362 diketones 368 enol 99 Lewis acids 359 diprotic acids, and statistical enol content and solvent 100 mineral acids 346 effects 366 synthesis 577 resonance effects 363 dithianes 1110 acetohydroxamate buffers 1282 acid–base catalysis 355 esters versus ethers 364 acetolysis see solvolysis acid–base equilibrium 339 F strain 366 rates, table 433 acid–base reaction, formation of gas phase 371 acetone, tautomerism, and homoenolates 242 of alcohols 372 bromination 304 and solvents 576 Hammett acidity function 352 acetoxy ketones, from enols 871 free energy 356 hydrocarbon 238 acetoxy sulfides, by Pummerer HCl and acetate 340 -I effect 362 rearrangement 1603 s rate constant 355 inductive and field effects 21 hydrolysis to aldehydes 1603 acid–base, carbanions + proton intrinsic 372 acetoxy ketones, from ketones 249 kinetic 238 871 acid catalysis, alcohol dehydration Lewis acid, and solvents 372 acetoxylation, of alkenes 1025 495 of active methylene compounds acetyl carbocation 230 acid, normal, definition 350 364, 575 acetylene see ethyne acid, sulfuric see sulfuric acid of ketones or aldehydes 1110 JWST960-SUBIND JWST960-Smith October 25, 2019 9:5 Printer Name: Trim: 254mm × 178mm SUBJECT INDEX 1919 of PCC 1448 sulfonyl, reduction with metals alkylation 575 of protons, and solvent acidity 1270 and the Knoevenagel reaction 352 acids, superacids 225, 229–230, 1187 of solvents 352 346–347, 698 arylation 575, 819–820 phenols 355 and alkenes 724 and radicals 820 pKa of acid types 341–345 and arenium ions 611 enantioselective 820 protons α- to a heteroatom and benzenonium ions 611 structural variations 820 590 and carbocations 226–227, as nucleophiles 566 solvent 355 410, 439, 1345, 1398 conversion to diazo compounds spectrophotometric and diazonium salts 467 712 measurement 352 and hydration of alkynes 914 functional groups 575 statistical effects 366 ionization 414 with acyl halides 1252 substituent effects 362 and nonclassical carbocations with aryldiazonium salts 710 thermodynamic 238 435 with tosyl azides 712 acids see Brønsted-Lowry acids, and oxocarbenium ions 1381 activity, of radicals 856 Lewis acids, solvent acidity cleavage of alkanes 759 acyals, from anhydrides 1104 acids, amino see amino acids coupling of alkenes 724 acyclic compounds, conformation acids, Brønsted-Lowry see sulfur dioxide 226 188 Brønsted-Lowry acids acids, table, delocalization 753 acyclic molecules, and entropy acids, carboxylic see carboxylic type, table of pKa 341–345 284 acids very weak acids 346 acyl addition see addition acids, fatty see fatty acids acoustic cavitation see cavitation acyl addition intramolecular 981 acids, glycidic see glycidic acoustic cavitation, and Grignard reagents 1129 acids, Lewis see Lewis acid sonochemistry 331 organolithium reagents 1129 acids, sulfinic see sulfonic acids acridinium photooxidant 920 syn or anti 1088 acids, sulfonic see sulfonic acids acrolein, canonical forms 47 water 1095 acids, acid strength 341–345 acrylic acids, from with nucleophiles 1087 activity of proton 352 tosylhydrazones 1161 acylals, and silanes 1105 and hydrogen exchange, actinometer, and photochemical formation of, reagents