Carbenes in constrained systems, 3. Solid-State photolysis of cycloheptane- and cyclooctanespirodiazirine within cyclodextrins and zeolites
✍ Scribed by Kupfer, René ;Brinker, Udo H.
- Publisher
- John Wiley and Sons
- Year
- 1995
- Tongue
- English
- Weight
- 476 KB
- Volume
- 1995
- Category
- Article
- ISSN
- 0947-3440
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✦ Synopsis
Abstract
Inclusion complexes of cycloheptanespirodiazirine (1) and cyclooctanespirodiazirine (8) in α‐, β‐, and γ‐cyclodextrin, and faujasite type zeolites (NaX and NaY), have been prepared. The guest‐host complexes (1‐ and 8@CD and 1‐ and 8@zeolite) were irradiated with UV light in the solid state and the reaction products were separated from the host and analyzed. Product ratios from photolysis of complexes were compared with those obtained from pure compounds and in solution. Cycloheptanespirodiazirine (1) gives cycloheptene (2), bicyclo[4.1.0]heptane (3), and methylenecyclohexane (4). Photolysis products from cyclooctanespirodiazirine (8) are cyclooctene (9), bicyclo[3.3.0]octane (10), and bicyclo‐[5.1.0]octane (11). 10 results from a 1,5‐C–H insertion reaction of the carbene derived from 8. As the cavity size of the cyclodextrins becomes larger, the formation of 10 seems to increase. In β‐cyclodextrin and in non‐polar solvents substantial amounts of azine were found. In addition to hydrocarbons, photolyses in zeolites afforded alcohols and small amounts of the corresponding ketones.