โ Scribed by Wataru Ando; Hajime Miyazaki; Kenji Ito; Daikan Auchi
No coin nor oath required. For personal study only.
Photosensitized oxygenation of 2-diaso-3-butanone at -78OC in CH Cl 2 2 bicycle [2,1,01 pentane which has a long enough life time to allow chemical and characterization. gave trioxaspectroscopic Despite extensive investigation of 1,2-dioxetanes, in photosensitized oxygenation of olefin, the four membered ring peroxide containing linkage to a small heterocyclic ring remain hypothetical intermediates. These compounds may possess inherent interest because of their high energy content and may be important intermediates in chemiluminescent systems. Recently, chemienergized benzoic anhydride has been claimed in the low temperature ozonation of diphenyl acetylene and the trioxabicyclo [2,1,01 pentane ( 1 ) has been assumed to be a precursor of anhydride.
๐ SIMILAR VOLUMES
As part of a study on additions to strained olefins and synthesis of strained nitrogen heterocycles, we have found that addition of methoxycsrbonylnitrene to 1,2dimethylcyclobutene, 2, and l-methylcyclobutene, 2, provides a convenient synthesis of the corresponding 5-azabicyclo[2.l.O]pentanes 2a and
Table 1. Selected physical properties of ( 5 a ) and (56) "C-NMR (in CDCl3, T M S internal) c-1 109.2 C-CN 97.4, 98.9, 102.0 c-4 108.9 c -5 c-1 ' 124.5 c -2 , c-3' 131.1 IR ( K B r ) [cm-'1 C=N 2210 Cyclopropene [5] 1898, 1550 UV(CH3CN) [ n m l (log&) 240 (4.61), 278 (4.23) 'H-NMR (100 MHz, CDClj, T
The triplet sensitized irradiation of 3-allyl-diaryl-substituted cyclopropenes to m.l.O]hex-2-enes proceeds via an intramolecular [2+2]-cycloaddition followed by a subsequent rearrangement of the initially formed tricycl0[2.2.0.0~~~]hexane skeleton. Previous work from this laboratory has shown that