Page 1189 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1176 bromonium ions hybridization of, 307
in bromination of alkenes, 185, 486, 535 as nucleophiles, 609–619
Index characterization of, 489–491 organometallic compounds, relation to, 588–591
computational modeling, 494–495 phenalenyl, 757
bromotrichloromethane, see halomethanes proton affinity of, 308
Brønsted catalysis law, 348, 602 table, 310
1,3-butadiene and derivatives stabilization by substituents, 307–311, 591–601
2,3-bis-(t-butyl) computation of, 309–311
photoproducts from, 1103 phosphorus-containing, 599
2,3-dimethyl sulfur-containing, 599
photocyclization of, 1101 structure of, 307, 585
2-cyano carbocations
+
photoproducts from, 1103 [C 3 H 7 ] isomers, 441
+
conformation of, 149–51 [C 4 H 7 ] isomers, 453
+
electron density distribution in, 21, 73–74 [C 4 H 9 ] isomers, 441–443
+
electrostatic potential surface of, 73–74 [C 5 H 11 ] isomers, 444–445
excited states for 2-butyl
computational modeling, 1137–1142 rearrangements of, 441–444
photochemical reactions of, 1100–1101 adamantylium, 431
photodimerization of, 1103–4 alkenyl, 435–436
effect of photosensitizers, 1104 allyl
photoisomerization of, 1096–1097 from cyclopropyl cation by ring opening,
resonance in, 20, 62 907–908
stabilization of, 262 stabilization of, 302
but-3-enyl radical aromatic, 303
from ring opening of cyclopropylmethyl radical, aryl, 436
972 benzylic, 302, 439
butane substituent effects on, 432–433
chlorination of, 996 bicyclic, rearrangement of, 446
conformation of, 143–144 bicyclobutonium, 453, 744
rotational barrier in, 80 electron density for, 744
2-butanone bridged, 301, 432, 440, 447–453
conformation of, 149 examples, 452
1-butene t-butly, 430
kinetic isotope effect in bromination, 335 charge distribution in, 306–307, 429–430
kinetic isotope effect in epoxidation, 335 computational characterization of, 305–306
2-butene cycloheptatrienyl, 740
photochemical cycloaddition of, 1109 cyclohexadienyl
t-butyl carbocation Huckel MO diagram for, 775
structure of, 430 observation of, 777–778
t-butyl hydroperoxide role in electrophilic aromatic substitution,
as a radical source, 977 775–776
in Sharpless asymmetric epoxidation, 197 trapping of, 778
t-butyl hypochlorite, 1022 cyclohexyl, rearrangement of, 445–446
cyclooctatrienyl, 743–745
2-butylium cation
cyclopentadienyl, 739–740
rearrangement of, 441–444
cyclopropenyl, 738–739
cyclopropyl, ring opening of, 907–908
Cahn-Ingold-Prelog priority rules, 120, 122 cyclopropylmethyl, 427
capto-dative stabilization of radicals, 316, 987–988 elimination versus substitution, 437–439
carbanions from diazonium ions, 405–407
[12]annulene dianion, 742 hybridization of, 300
additions to carbonyl compounds, 676–682, hydride affinity of, 303, 314
687–692 table, 303, 314
bicyclo[3.2.1]octa-2,6-dienide, 744–745 hyperconjugation in, 301, 305, 307, 429, 432
charge distribution in, 308 as intermediates
cyclononatetraenide, aromaticity of, 741 in electrophilic addition reactions, 479, 480
cyclooctatetraene dianion, aromaticity of, 741 in Friedel-Crafts alkylation, 806, 808
cyclopentadienide, aromaticity of, 740 in nucleophilic substitution, 391–393