Page 1208 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

electrophilic versus nucleophilic character of, regioselective, definition, 476 1195
1004 resolution of enatiomers, 136–141
frontier MO interpretation of, 1004–1006 chromatographic, 137 Index
generation of, 976–80 dynamic, 215
from azo compounds, 978–979 enzymatic, 215–227
from boranes, 979 by epoxide hydrolases, 225–226
from N-acyloxypyridine-2-thiones, 979–980 selectivity in, 140–141
from N-nitrosoacetanilides, 979 kinetic, 138–141
from peroxides, 976–978 chemical, 139
group transfer reactions of, 1037–1039 enzymatic, 140–141
halogen bridging in, 1028 resolving agents
hybridization of, 311 examples of, 136–137
long-lived, 968–970 resonance, 18–22
examples of, 969 in 1,3-butadiene, 20, 62
methyl, 967 in allyl radicals, 312–313
structure of, 980–981 in amides, 320–322
nitroxide, 968, 973 in benzene, 18, 62
persistent, 968 in carbocations, 22, 433
reaction with oxygen, 1023 in carbonyl compounds, evaluation of, 320–321
rearrangements of, 1041–1044 in enamines, 22
of acyl groups, 1042 in formamide, 62
of aryl groups, 1042–1043 in formate anion, 62
of cyano groups, 1042–1043 in naphthalene, 18
hex-5-enoyl radical, 1042–1043 natural bond orbital representation, 62
of vinyl groups, 1042 in propenal, 20–21
stabilization of, 312–313, 317, 1052–1055 in substituent effects, role of, 297–298
structure of, 311, 980–982 in vinyl ethers, 21–22
substituent effects on, 317–318 resonance energy, definition, 19
table, 317, 1055 as a criterion of aromaticity, 715–716
trifluoromethyl ring current
structure of, 981–982 as an indicator of aromaticity, 720
triphenylmethyl, 967 rotational barriers, definition, 143
unsaturated, cyclization of, 1008–1013, in butane, 79–80
1037–1039 in ethane, 78–79
vinyl, 986 origin of, 78–81
-amino, 315 Rydberg excited states, 1073
radical stabilization energy, definition, 314 of ethene, 1082
relation to bond dissociation energy, 312–313,
317, 1052–1055
table, 315, 1055 salicylic acid
rate determining step, 276 acetals of
RE, see resonance energy hydrolysis, 668–669
reaction constant, in Hammett equation, 338 acetate ester (aspirin), 352–353
for electrophilic aromatic substitution, 790 esters, hydrolysis of
table of, 341 leaving group effects, 671
reaction cube, see potential energy diagram, mechanism, 669–671
three-dimensional pH-rate profile for, 670
reaction rates, see also kinetics SCF, see self-consistent field
relation to thermodynamic stability, 285–287 Schrödinger equation, 26
reactivity-selectivity relationships selectivity
for electrophilic aromatic substitution, 787–791 in aromatic electrophilic substitution, 787–791
rearrangements selenenylation
of carbocations, 440–447 of alkenes, 500–503
during addition of hydrogen chloride to alkenes, regioselectivity of, 502
448–450 self-consistent field, definition, 26, 32
during chlorination of alkenes, 494 semicarbazones, 646
of radicals, 1041–1044 mechanism of formation, 652
refractive index semidiones, 991–992
relationship to polarizability, 17 semiquinones, 991