Page 1187 - Advanced Organic Chemistry Part A - Structure and Mechanisms, 5th ed (2007) - Carey _ Sundberg

1174 aromatic compounds (cont.) azetidinones
Diels-Alder reactions of, 748–749, 857–858 formation by [2+2] cycloadditions of imines,
Index examples of, 746 890–891
halogenation of, 800–804 azides
hardness of, 750, 795 as 1,3-dipoles, 875
heterocyclic, 758–760 aryl, as ambiphilic 1,3-dipoles, 876–878
nitration of, 796–800 frontier orbitals of, 880–881
photochemistry of, 1134–1137 azo compounds
redox potentials of, 990 configuration of, 121
aromaticity as sources of radicals, 978
of charged rings, 32, 738–743 azoisobutyronitrile
examples of, 738 as radical source, 978
criteria for, 714 azomethine imines
bond length alternation, 718–719 as 1,3-dipoles, 875
electronic, 720–724 azomethine ylides
in fused ring systems, 747–748 as 1,3-dipoles, 875
stabililzation energy, 715–718 generation from aziridines, 885
of cyclopropenium ions, 738–739 azulene
of fused ring systems, 745–758 dipole moment of, 753
Huckel rule for, 31, 713 stabilization of, 747, 752
of transition state in Diels-Alder reaction, 851 structure of, 752
aromatic ring current shielding
as a criterion of aromaticity, 721
aromatic stabilization energy, B3LYP computational method, 55
definition, 717 9-BBN, see 9-borabicyclo[3.3.1]nonane
of heteroaromatic compounds, 758 Baeyer-Villiger reaction, 1025
of indacene, 754 basicity function
aromatic substitution, see electrophilic, H − , 580
nucleophilic etc. basis sets, definition, 26–27
Arrhenius equation, 272 abbreviations for, table, 34
aryl halides characteristics of, 33–35
benzyne from, 821–822 Bell-Evans-Polyani relationship, 288–289
S RN 1 substitution reactions, 1048–1052 in 1,3-dipolar cycloaddition reactions of ethene,
examples of, 1051 883
mechanism of, 1049, 1052 for hydrogen abstraction reactions, 1001–1002,
aryl radicals 1056–1057
from N-acyloxypyridine-2-thiones, 980 quadratic, for reaction of hydroxyl radical with
from N-nitrosoacetanilides, 979 halomethanes, 1060
ASE, see aromatic stabilization energy benzaldehyde
aspirin, see salicylic acid esters excited state of, 1118
1,2-asymmetric induction, 171 benzene
Cieplak model for, 180 acidity of, 583
Cram’s rule for, 179 electron density in, 57–58
Felkin-Ahn model for, 179 Hückel MO diagram for, 714
1,3-asymmetric induction photocycloaddition with alkenes, 1135–1137
in hydride reduction of ketones, 181 photoisomerization of, 1135
atomic charge, see also electron density photoproducts of, 1134
distribution radical anion of, 990
definition, 27, 713 ESR spectrum of, 972
atoms in molecules approach, 62–69 resonance in, 18, 62
for aromatic compounds, 723–724 stabilization in, 716–718, 727
atom transfer reactions, definition, 966 benzocyclobutadiene
Aufbau principle, 35 generation of, 751
autoxidation, 1024 properties of, 751–2
of aldehydes, 1025 benzophenone
of ethers, 1026 reductive photodimerization of, 1119–1120
2 6
of hydrocarbons, 995, 1025 benzvalene, see tricyclo[3.1.0.0 ]hex-3-ene
relative rates, 1025 benzyl cation
of isopropylbenzene, 1025 in Friedel-Crafts alkylation reactions, 806, 808