Page 5 - Mechanism and Theory in Organic Chemistry

vi Contents

Appendix 1 : Derivation of the Transition State Theory Expression for a
Rate Constant 1 13
Appendix 2: The Transition State Theory of Isotope Effects 120
3 ACIDS AND BASES 124
3.1 BR~NSTED ACIDS AND BASES 124
OF WEAK BR~NSTED BASES 129
3.2 STRENGTHS
3.3 STRENGTHS
OF WEAK BRDNSTED ACIDS 138
3.4 SUBSTITUENT EFFECTS ON STRENGTHS OF BR~NSTED ACIDS AND
/' BASES 150
3.5 LEWIS ACIDS AND BASES 163
PROBLEMS 168
4 BIMOLECULAR SUBSTITUTION REACTIONS 170
4.1 SN1 and SN2 SUBSTITUTION MECHANISMS 7 1
1
4.2 STEREOCHEMISTRY THE SN2 REACTION 174
OF
4.3 THE SOLVENT, SUBSTRATE, NUCLEOPHILE, AND LEAVING GROUP
4
177
4.4 BIMOLECULAR NUCLEOPHILIC SUBSTITUTION AT SULFUR 194
4.5 BIMOLECULAR ELECTROPHILIC SUBSTITUTION AT SATURATED CAR-
BON 203
PROBLEMS 210 '

UNIMOLECULAR SUBSTITUTIONS AND RELATED
REACTIONS 213

d INTRAMOLECULAR REARRANGEMENTS 268
6.1 1,2-SHIFTS IN CARBENIUM IONS 268
@ CARBONIUM IONS 288
6.3 MIGRATIONS CARBONYL CARBON 316
TO
@ REARRANGEMENT ELECTRON-DEFICIENT NITROGEN AND OXY-
TO
GEN 318
PROBLEMS 332
7 ADDITION AND ELIMINATION REACTIONS 337
7.1 ELECTROPHILIC ADDITION TO DOUBLE AND TRIPLE BONDS 337
7.2 1 ,2-ELIMINATION REACTIONS 355
7.3 NUCLEOPHILIC ADDITION TO MULTIPLE BONDS 377