Hypochlorite photolysis

The reactivity of the amino radical has not yet been investigated. Alkaline hypochlorite oxidation, known in the pyridine series to yield azo derivatives (155,156). and photolysis of N,N-dichloro derivatives, which may be obtained by action of sodium hypochlorite on amino derivatives in acidic medium (157). should provide interesting insight on this reactivitv. 

The discovery that photolysis of hypochlorite (14) gave chloroketone (11) directly provided a short cut in this synthesis. The ketone in (11) will need to be protected during reaction with acetylene. 

A closely related procedure results in formation of y-lactones. Amides are converted to AHodoamidcs by reaction with iodine and /-butyl hypochlorite. Photolysis of the AHodoamides gives lactones via iminolactone intermediates.372... 

Experiments designed to utilize spin trapping to monitor free-radical chemistry in the gas phase were first reported by Janzen and Gerlock (1969). In these, radicals generated by photolysis in a stream of carrier gas were passed over solid PBN. The PBN was then dissolved in benzene, and the solution was found to contain spin adducts of radicals present in the gas stream. Photolysis of t-butyl hypochlorite vapour in this way leads to a nitroxide whose spectrum reveals splitting from two chlorine atoms. This proved to be due to butyl nitroxide (Janzen, 1971 Janzen et al., 1970), and recalls the observation of other nitroxides which apparently result from further reaction of the initial spin adducts. 

For the substitution of the angular methyl groups in steroids five methods are known (a) homolysis of N-chloramines [Loffier-Freytag reaction (only C-18)] (b) oxidation of alcohols with lead tetraacetate (c) photolysis of nitrite esters (d) homolysis of hypochlorites (e) the hypoiodite reaction. ... 

B. Photolysis of Methyl Substituted-benzyl Carbinyl Hypochlorites. 907... 

Peroxysulfates, analytical aspects, 744 Peroxysulfenate, superoxide reactions, 1033 Peroxysulfinate, superoxide reactions, 1033-5 Perpendicular effect, methyl substituted-benzyl carbinyl hypochlorite photolysis, 907,... 

Recently, in a discussion of the arrangement of six atomic nuclei in the transition state in the photolysis of hypochlorites (see Part II), Walling and Padwa87 have considered the plausibility of the following transition state... 

Until recently, in the chemistry of hypochlorites, there has been particular emphasis on the chemistry of -butyl hypochlorite. Hypochlorites in general were ignored. However, in their classical paper on the photolysis of organic nitrites,48 Barton et al. adumbrated a photochemical rearrangement of hypohalites of the type (A) —> (B) (X = any halogen). A year later applications of this principle were described... 

Halogens, alkyl nitrites and alkyl hypochlorites also undergo photolysis easily (Scheme 2.30). Alkyl nitrites and alkyl hypochlorites generate alkoxy radicals. 

There has been interest in the photolysis of organic hypochlorites as a source of alkoxyl radicals and as useful intermediates in synthetic work . The hypochlorites show absorption at A 2500-2600 A and at 3000-3200 A. In their rearrangement reactions it is probably the longer wavelength region which is of importance. t-Butyl hypochlorite decomposes in sunlight to methyl chloride and acetone, and a chain mechanism has been proposed for the decomposition... 

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