A Guidebook to Mechanism in Organic Chemistry

Index

Nucleophilic substitution—continued

stereochemistry, 66-72

steric effects, 62, 64

triphenylmethyl chloride, 63

vinyl halides, 64

Nucleophilic substitution, aromatic,

130-136

activated phenyl halides, 132

benzyne intermediates, 135

diazonium salts, 132

intermediates, 133

nitrobenzene, 131

phenyl halides, 64,132

pyridine, 131

Orbitals

atomic, 1

bonding, 4

co-linear, 7

. delocalised, 8
! hybridisation, 3
localised, 4
molecular, 4
.: overlapping, 3, 6
6
: plane trigonal, 5
' Ortho/para-directing groups, 120
Ortho/para ratios, 125
Osmic esters, cyclic, 145

• Overlapping,orbitalj, 3

ox^es^7 Tr ,•

assignment of configuration, 96

formation, 164

Oxygen

as diradical, 243, 252,260

. migration to electron-deficient, 99
Ozonides, decomposition, 149
Ozonolysis of alkenes, 147
'f Panetn,238
Pentaerythritdl, 174 .„ _
Perbenzoic acid, 253

• Perkin reaction, 176
  Perlon,98<
  Peroxide effect, 244
  Peroxides, 236, 240, 244, 247
  rearrangement, 100"
  . Phenanthrene, delocalisation energy, 13
  Phenonium ion, 83
  (8-Phenylethyl cation, stability, 83
  Photo dimerisation, 258
  Photo oxidation, 254

• bonds, 6
  it orbitals, 6 '
  Pinacol/pinacolone conversion, 90
  Pinacols, formation, 169, 237
  pKa, 39
  pAf*,48

Polymerisation

isobutene, 144

oriented, 248

vinyl, 247

Propane, AlBr,-catalysed rearrange­

ment, 86

n-Propylamine, reaction with HNOs, 85

Proton acceptors, 38

Proton donors, 38

Prototropy, 215

Pseudo-acids, 215,220

Racemisation, 6fc|l^fi

in SATI, 68

Radicals, 14,27, 231-260 *

addition reactions, 242-248

alkyl, 234,240

allyl, 234,251

apocamphyl, 239

benzoate, 236,240

benzoyl, 237, 253

benzyl, 234,244, 251

carboxyl, 237

detection, 238

dimerisation, 235,237,247

displacement reactions, 248-257

disproportionation, 236

from electrolysis, 237

„ oxidation/reduction, 237, 254

„ photochemical fission, 235,242

„ thermal fission, 235, 240

half-life, 238

hydroxyl, 237, 260

in arylation, 255

„ autoxidation, 252

„ halogenation, 248

„ polymerisation, 247

long-lived, 232

methylene, 236, 258

pentachloro-ethyl, 242,243

perbenzoate, 253

peroxy, 243, 252

phenyl, 241,255,257

rearrangement, 1

short-lived, 234-!

ereochemistry,

ti%henylmethyl,

Rati "