ABSTRACT
Species, and Determination of Fit ............................ 479 8.3 Early Examples of Experimental Reactivity
vs. Theoretical Prediction .......................................... 480 8.4 Reactivity Criteria in the Type B Rearrangement
of Substituted Cyclohexenones.................................. 483
8.5 The Type-B Bicyclic Rearrangement ....................... 486 8.6 Dimorphs, Crystal Morphology, and Pseudo
Crystal Disorder ......................................................... 489 8.7 The Inert Atomic Shell Model ................................... 492 8.8 Treatment of Host-Guest Lattice Reactions............ 494 8.9 The Phenomenon of Reactions Proceeding
in Stages ........................................................................ 497 8.10 The Type-C Rearrangement ...................................... 501 8.11 Conclusion................................................................... 507 Acknowledgment ................................................................. 507 References............................................................................ 507
8.1 INTRODUCTION
It has long been known that the photochemistry of crystalline compounds proceeds differently than upon irradiation in solution; one of the best examples is that of the cinnamic acids and the research of Ciamician and Silber in 1902.1 Control of solid-state reactions was postulated by Cohen and Schmidt2 in 1964 to involve minimum molecular motion in the crystal. This approach has been termed the “topochemical principle,” perhaps otherwise known as least motion. Cohen and Schmidt also advanced the idea of a molecule reacting in a cavity created by surrounding neighbors.
