Page 1186 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

of hydrogen halides, 1026–1028 aluminum trichloride 1173
substituent effects on rates, 1004–1006 in Friedel-Crafts reaction, 809–813
of thiols and thiocarboxylic acids, 1033 as Lewis acid catalyst, 354 Index
relative reactivity of, summary, 531–535 AM1 MO method, 32
with trifluoroacetic acid, 484–485 amides
with trifluoromethanesulfonic acid, 484 hydrolysis, 662–664
selenenylation, 497, 498, 500–503 mechanism of, 327
relative reactivity of, 501 protonation of, 663–664
silver complexes of, 520–521 resonance in, 320–322
stabilization by substituents, 52 amine oxides
sulfenylation, 497–500 allyl, [2,3]-sigmatropic rearrangements of, 941
relative reactivity of, 501 amines
alkoxyl radicals alkylation by S RN 1 substitution reactions, 1047
formation from alkyl hypochlorites, 1015 bifunctional, intramolecular catalysis by, 675
fragmentation of, 1114–1116 bond energies in, 317, 1054
alkylboranes, see boranes, alkyl configuration and inversion of, 129
alkyl groups diazotization of, 405
as electron donating groups, 13 hyperconjugation in, 315, 1054
electronegativity of, 13, 102–103 N-allyl, aza Wittig rearrangement of, 944
alkyl halides synthesis using organoboranes, 528–529
bridgehead, reactivity of, 435 aminolysis
S RN 1 substitution reactions, 1051 of esters, 659–662
S RN 1 substitution reactions of, of salicylate esters, 673
1048–1052 anhydrides, see carboxylic acid anhydrides
synthesis annulenes, 715–718
using organoboranes, 529 [10]annulene, 728–730
1,3-allylic strain, definition, 147 [12]annulene, 730
in alkylidene cyclohexanes, 161 dianion of, 742
alkyl radicals Mobius topology, 737
disproportionation of, 966 [14]annulene, 730–732
halo-substituted [16]annulene, 732–733
Structure of, 981–982 Mobius topology, 737
structure of, 980–984 [18]annulene, 733–734
alkynes [20]annulene, 734
Acidity of, 584 Mobius topology, 737
electrophilic addition reactions of, 537–545 [22]annulene, 734
halogenation, 540–544 [24]annulene, 734
hydration of, 538, 544 Hückel MOs for, 30
hydrohalogenation of, 539–540 large ring, 734–735
mercuration of, 545 NICS values for, 735
allenes anomeric effect, see also hyperconjugation
chirality of, 129 in acyclic molecules, 81–85
electrophilic addition reactions of, 545–546 computational analysis of, 231–232
hybridization in, 6 in conformation of disubstituted methanes, 81–85
allyl cation in cyclic ethers, 227–233
cycloaddition with alkenes, 48 electrostatic effects in, 230–231
from cyclopropyl cation, 907–908 hyperconjugation in, 230–231
MOs of, 48 MO interpretation, 82
stabilization of, 302 role in nucleoside conformation, 233–234
allyl phenyl ethers solvent effects on, 231–232
Claisen rearrangement of, 934 in tetrahydropyrans, 228–233
allyl radical anthracene, 749
resonance in, 312–313, 985 Diels-Alder reaction with tetracyanoethene, 859
structure of, 985 electrophilic aromatic substitution in, 793
substituent effects on, 986–987 antiaromatic, definition, 714
allyl vinyl ether antioxidants, 994–995
Claisen rearrangement of, 273, 933–934 ARCS, see aromatic ring current shielding
AlpineHydride ® aromatic compounds
in enantioselective reduction of ketones, 193 fused ring systems, 745–758