Index Abbreviations receptor sites 202, 211 weak 122 amino acids, Table 500–1 muscarinic 413 weak, pH calculation 147–8 nucleic acids 551 nicotinic 413 Acid–base nucleotides, Table 551 as quaternary ammonium salt 202 catalysis, enzymes 516 peptides and proteins 504 Acetylcholinesterase equilibria 121 phosphates and diphosphates 277 enzyme mechanism 519–21 interactions, predicting 155–7 structural, Table 14 hydrolysis of acetylcholine 279 Acidic reagents, Table 157 ACE (angiotensin-converting enzyme) inhibitors 279 Acidity enzyme action 532 Acetyl-CoA carboxylase, in fatty acid acidity constant 122 inhibitors 532 biosynthesis 595 bond energy effects 125 Acetal Acetyl-CoA (acetyl coenzyme A) definition 121 in etoposide 233 as acylating agent 262 electronegativity effects 125 formation 229 carboxylation to malonyl-CoA 595, hybridization effects 128 polysaccharides as polyacetals 232 609 inductive effects 125–7 as protecting group 230 Claisen reaction 381 influence of electronic and structural Acetal and ketal enolate anions 373 features 125–34 cyclic, as protecting groups 481 in Krebs cycle 585 and leaving groups, Table 189 groups in sucrose 231 from β-oxidation of fatty acids 388 pKa values 122–5 Acetaldehyde, basicity 139 as thioester 262, 373 resonance / delocalization effects 129–34 Acetamide, basicity 139 Acetylene, bonding molecular orbitals 31 Acidity (compounds) Acetaminophen, see paracetamol Acetylenes, acidity 128 acetone 130 Acetoacetyl-CoA, biosynthesis from N-Acetylgalactosamine, in blood group acetonitrile 365 acetyl-CoA 392 antigens 496 acetylacetone 130, 349 Acetobromoglucose N-Acetylglucosamine acetylenes 128 in glucoside synthesis 479 in chitin 495 acrylic acid 128 synthesis 479 in peptidoglycan 495, 538 adenine 450 Acetone Acetylide anion 156 alcohols 125, 127 acidity 130 Acetylides amides 372 basicity 139 formation 205, 240 benzoic acid 128, 130 resonance structures 49 as nucleophile in SN1andSN2 reactions benzoic acids, substituted 131–3 Acetonide 205 carboxylic acids 125 definition 481 as nucleophile with aldehydes and ketones carboxylic acids, halogenated 125 of galactose 482 241 carboxylic acid derivatives, Table 372 of glucose 482 N-Acetylmuramic acid, in peptidoglycan 495, cyclohexanecarboxylic acid 130 Acetonitrile COPYRIGHTED538 MATERIALcyclohexanol 133 acidity 365 Acetylsalicylic acid, see aspirin cyclopentadiene 421 basicity 138 Achiral molecules 74 dicarboxylic acids Acetyl coenzyme A, see acetyl-CoA Aciclovir, structure 559 aliphatic 144 Acetyl nitrate, in nitration reactions 422 Acid aromatic 145 Acetylacetone Brønsted–Lowry definition 121 diethyl malonate 390 acidity 130, 349 conjugate see conjugate acid esters 372 alkylation 357 Lewis definition 121 ethane 128 hydrogen bonding 50 polyfunctional 144 ethyl acetoacetate 380 Acetylcholine strong 122 ethylene 128 hydrolysis via acetylcholinesterase 279, 519 strong, pH calculation 146 glutaric acid 144 Essentials of Organic Chemistry Paul M Dewick © 2006 John Wiley & Sons, Ltd 676 INDEX Acidity (compounds) (continued) Addition in hemiacetal and hemiketal formation guanine 450 1,4-addition, see conjugate addition 224 histidine 434 anti 287 in SN1andSN2 reactions 198 hydrogen cyanide 128 conjugate, see conjugate addition from reduction of carboxylic acid hydrogen halides 125 intramolecular electrophilic 300 derivatives 268 indole 445 radical 321 Aldaric acids, definition 486 malonic acid 144 syn 287 Aldehydes methanesulfonic acid 129 in catalytic hydrogenation 332 acetal formation 229 nitromethane 365 Addition reactions 175 hemiacetal formation nitrophenols 134 to carbonyl group acid-catalysed 224 oxalic acid 144 electrophilic mechanism 221 base-catalysed 225 1,3-pentadiene 129 irreversible 223 hemithioacetal formation 235 phenols 133 nucleophilic mechanism 221 nucleophilic addition reactions 221–48 phenylacetic acid 130 reversible 223 reaction with phosphoric acid 144, 275 electrophilic, see electrophilic addition acetylides 241 picolines 412 nucleophilic, of carbonyl groups 221–48 amines 242 propene 129 radical 328–31 cyanide 238 propiolic acid 128 Addition–dehydration, aldol reaction 360–5 Grignard reagents 240 purine 450 Addition–elimination reactions complex metal hydrides 235 pyridones 416 in imine formation 242 from reduction of carboxylic acid pyrrole 421 in nucleophilic substitution 248 derivatives 268 salicylic acid 133 Adenine thioacetal formation 235 succinic acid 144 acidity 450 Aldehydes and ketones sulfuric acid 144 basicity 449 aldol reaction 360–5 thioesters 372 hydrogen bonding 51 enolization 347 thiols 125 metabolism 451 halogenation 356 uric acid 451 in nucleic acids 550 hydrogen exchange 351 vitamin C (ascorbic acid) 490 structure 478 racemization 352 Aconitase tautomerism 449 relative reactivity 222 in Krebs cycle 586 Adenosine Aldimine, in PLP-dependent reactions 246, stereospecificity 96 as N-glycoside 478 599 cis-Aconitate, in Krebs cycle 586 structure 550 Alditols, definition 473 Acrolein, conjugate addition of thiol 395 triphosphate (ATP), see ATP Aldohexoses, equilibrium proportions Acronyms S-Adenosylmethionine (SAM) pyranose and furanose forms, Table biochemicals, Table 16 in biological methylation reactions 199 470 reagents and solvents, Table 16 biosynthesis 200 Aldol, from acetaldehyde 360 Acrylic acid, acidity 128 as nucleoside 560 Aldol and Claisen reactions, in phenol Activation energy, definition 173 and regeneration of methionine 454 biosynthesis 385 Active site, definition 514 in sterol methylation reactions 295 Aldol reaction 360–5 ACV, as precursor of β-lactam antibiotics 537 Adenylate cyclase, in formation of cyclic in biochemistry 363, 381 Acyclonucleosides, definition 559 AMP 561 citrate synthase 528 Acyl anion equivalents, TPP as carrier 607 Adenylic acid, structure 549 involving enolate anions from carboxylic Acyl carrier protein (ACP), in fatty acid Adrenaline (epinephrine) acid derivatives 379 biosynthesis 597 biosynthesis 602 in glycolytic pathway 363 Acyl chlorides from methylation of noradrenaline 200 with indole 445 in Friedel–Crafts reactions 308 nomenclature 12 intramolecular 364 synthesis 251 Aflatoxins 202, 203 in phenol biosynthesis 385 Acyl halides Aglycone, definition 474 ring size 364 as electrophiles in Claisen reaction 383 Agonist, definition 514 in Knorr pyrrole synthesis 460 ester formation 253 Alanine in Krebs cycle 586 reactivity 250 isoelectric point, calculation 161 mixed/crossed 361 in synthesis of amides 263 structure and pKa values 500 with picolines 412 in synthesis of anhydrides 251 Alcohol dehydrogenase reverse 361, 363 Acylation in glycolysis 584 in glycolysis 581 electrophilic, of aromatic rings 308 stereospecificity 95 in Robinson annulation 398 of enolate anions, see Claisen reaction Alcohols Aldolase of nucleophiles 248 acidity 125, 127 as aldol reaction 363 Acyl-CoA dehydrogenase, in fatty acid from aldehydes and ketones enamine mechanism 368 β-oxidation 591 with acetylides 241 enzyme mechanism 525 Acyl-CoA synthetase, in fatty acid oxidation with Grignard reagents 240 enzyme active site 526 590 by reduction 235 in glycolysis 581 Acylium ions, in Friedel–Crafts reactions 308 basicity 138 Aldol-like reactions, with stabilized anions Acylphosphates, as mixed anhydrides 281 from carboxylic acid derivatives and 365 Acylpyridinium ion Grignard reagents 271 Aldonic acid, definition 485 as nucleophilic catalyst 264 hydrogen bonding 50 Aldose in synthesis of anhydrides 251 as nucleophile definition 464 in synthesis of esters 253 in acetal and ketal formation 229 structures 465 Acylpyridinium salts, formation 408 in ester formation 252–6 Alginic acid, structure 488 INDEX 677 Alkaloid cyclic see lactams from hydrolysis of penicillins 266 biosynthesis, Mannich-like reactions 371 from esters 263 in semi-synthesis of penicillins 266 definition 162 hydrolysis, acid-catalysed 260 stereochemistry and shape 116 opium 162, 186, 343 base-catalysed 260 Aminopurines, tautomerism 449 tropane 370, 375 peptides and proteins 261 Aminopyridines tropane, stereochemistry and shape 117 reduction with complex metal hydrides 269 basicity 418 Alkanes, radical chlorination 324 synthesis, chemical 533 tautomerism 417 Alkenes Amidines, basicity 140 Aminoquinolines 441 from elimination reaction 207 Amines Aminosugars 492–7 catalytic hydrogenation 332 basicity synthesis 492 electrophilic addition 283–92 aliphatic 137 Ammonia, bonding molecular orbitals 34 of halogens 286–92 aromatic 141 Ammonium cation 34, 169 of halogens, stereochemistry 287 aromatic, substituted 142 acidity 136 of hydrogen halides 284–6 methylation via imines 246 formal charge 47 hydration 285 as nucleophile in SN1andSN2 reactions Ammonium salts, quaternary, see quaternary radical addition 321 201 ammonium salts of HBr 328 with aldehydes and ketones, enamine Amoxicillin, functional groups, 4 radical polymerization 331 formation 247 AMP, cyclic, see cyclic AMP Alkyl groups with aldehydes and ketones, imine Amphoteric compounds electron-donating effect 127, 321 formation 242–7 amino acids 159 in alkenes 210 in amide formation 262 definition 159 in carbocations 193 from reduction of amides 269 Amphotericin Alkyl halides, from nucleophilic substitution Amino acid mode of action 294 reactions 198 sequence determination, peptides, 544 structure 256 Alkylation N-terminal, determination 544 Ampicillin, semi-synthesis 266 carboxylic acid derivatives 378 Amino acids 499–503 Amygdalin, structure 239 electrophilic, in steroid side-chain abbreviations, Table 500–1 Amylase 485 biosynthesis 294 α-amino acid 499 Amylopectin of aromatic rings 306–8 configurations 81 as