ISSN:
0947-3440
Keywords:
1,4-H Migration
;
Calculations, ab initio
;
Photochemical interconversion
;
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Broad-band irradiation (λ 〉 370 nm) of 2-hydroxyphenyl azide (1) in Ar at 10K monitored by IR resulted in the formation of at least three major products, all of which were shown to be photointerconvertible under these conditions. The two products showing carbonyl stretching absorption bands were assigned to an E/Z mixture of 6-imino-2,4-cyclohexadien-1-one (3), while the product showing sharp absorption bands in the cumulenic double bond region was assigned to 6-imino-1,3,5-hexatrien-1-one (4). These assignments were fully supported by comparison of the experimental IR spectra with the theoretical data calculated at the HF/6-31G** level of theory. Similar irradiation (λ 〉 350 nm) of 2-aminophenyl azide (6) in Ar at 10 K also afforded three photointerconvertible products, which were assigned to a mixture of (E,E)-(E,Z)- and (Z,Z)-1,2-diimino-3,5-cyclohexadiene (8). The assignments were again supported by ab initio calculations. The reactions are discussed in terms of a 1,4 H shift in the photolytically generated phenylnitrenes (2 and 8) from the azides (1 and 7).
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/jlac.199619961206
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