INDEX cycloheptatriene

A reactivity index which accurately predicts the site selectivity of the photoisomerization of cycloheptatrienes to their bicyclic valence tautomers fails with 1//-azepines.237 For example, for methyl 2-methyl-1//-azepine-l-carboxyIatc (14), the 1-methyl isomer 16 is the predicted major product in practice the reverse is true. 

Recently, a new reactivity index has been proposed (80H(14)1717> which predicts accurately the site selectivity of photocyclization of substituted cycloheptatrienes to their bicyclic valence tautomers. Unfortunately, application of the method to substituted lH-azepines is far less successful. For example, for 2-methyl-l-methoxycarbonyl-lH-azepine (37 R = 2-Me) AGrs values for C-2—C-5 and C-4—C-7 cyclization are calculated as 0.093 and 0.040 kJ mol-1, respectively, i.e. predicting the 1-methyl isomer (39) as the major product. Experimentally, however, the reverse is true, the yields being 93.5% for 3-methyl (38 R = Me) and 6.5% for 1-methyl (39 R = Me). The corresponding photoinduced valence isomerizations of 1-benzazepines to 3,4-benz-2-azabicyclo[3.2.0]hepta-3,6-dienes (38a) have been recorded (80JOC462). These isomerizations have also been achieved thermally in the presence of silver ion (80TL3403). 

An index for predicting the reaction course of intramolecular photochemical cyclization of cycloheptatrienes and tropones, based upon the LCAO coefficients at the reaction sites of the HOMO S and LUMO s of the excited states, has been developed. The n.m.r. spectrum of the 8,9-benzobicyclo[5,2,0]nonatetraenyl anion (118) shows the presence of bond fixation and a preference for the dimethyl-enecyclobutene form. ° The rates of one-electron reduction of cyclopropyl-substituted tropylium perchlorates by chromous ion are consistent with the cyclopropyl group preferring a bisected conformation. ... 

---