What is Different in Photochemical Reactions of Primary and Secondary Alkylcobaloximes with and without Radical Traps?

✍ Scribed by Hartung, Jens ;Hertel, Barbara ;Trach, Frank

• Publisher: Wiley (John Wiley & Sons)
• Year: 1993
• Tongue: English
• Weight: 537 KB
• Volume: 126
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19931260519

✦ Synopsis

Abstract

Photochemical cyclization and halogen abstraction reactions of secondary alkylcobaloximes 1b and 1d compared to their primary counterparts 1a and 1c show an enhanced reactivity of secondary alkylcobaloximes: Thus, cyclohexylcobaloxime 1d reacts 13 times faster with CCl~4~ than __n__1‐hexylcobaloxime 1c, 6‐hepten‐2‐yl‐cobaloxime 1b rearranges 58 times faster to its cyclopentylmethyl isomer 4b than 5‐hexenylcobaloxime 1a. Although free alkyl radicals are reactive intermediates in photolytic conversions of alkylcobaloximes 1 in organic solvents, the presence of BrCCl~3~ or bromobenzene in photoreactions of primary alkylcobaloximes 1a and 1c seems to cause a more efficient homolytic cleavage of the Co – C bond.