The photochemical isomerization and fragmentation of dehydronorcamphor
β Scribed by David I. Schuster; Michael Amelrod; Joseph Auerbach
- Publisher
- Elsevier Science
- Year
- 1963
- Tongue
- French
- Weight
- 275 KB
- Volume
- 4
- Category
- Article
- ISSN
- 0040-4039
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β¦ Synopsis
In connection with studies of the mechanism of a numbsr of photochemical reactions, particularly of structu&.ly interesting asaturated ketones, we have studied the photolysis of dehgdronomae@W, blcyclo[2.2.l]bept-5-en-2-one (I). We were led to at&y this partictim compomd in order to determiue what role the highly stradned bicyClo[2.2.1~ heptyl skeleton would play in Influencing the course of reaatiou foll*g
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Recently Adam and Schreiber (l), on attempting to apply the Hofmann-L8ffler reaction (2) to the N-chloro compound I, diecovered a new type of fragmentation, the main products obtained on UV irradiation being the 20(R) and 20(S)-chloro-5a-pregnane-3!3-ol (II). We have now shown that this same type of
## Abstract The reaction mechanism of photoisomerization of isoxazoles to oxazoles through azirine intermediates is investigated theoretically by means of __ab initio__ MO CI calculations. Azirine intermediates in __S__~1~ state [(__n__ β\*) state of the carbonyl chromophore] cause the Cο£ΏN bond rup