Allyl chloride, photolysis

Photolytic. Distilled water irradiated with UV light (X = 290 nm) yielded the following photolysis products 2-chloro-l-propanol, allyl chloride, allyl alcohol, and acetone. The photolysis half-life in distilled water is 50 min, but in distilled water containing hydrogen peroxide, the half-life decreased to <30 min (Milano et al, 1988). 

Photolysis of DTBP in solution containing allyl chloride/ Allyl chloride DTBP EPR/ 133 H(l, 3,3) 1.40(5) 73Ricl/ 72Edgl... 

Photolysis of a number of low molecular weight model compounds such as allyl chloride [1720], 2,3-dichlorobutane, 2,4-dichloropentane [1511], 4-chloro-2-butane and 2,4-dichloropentane [1269,1270] occurs by the cleavage of the C—Cl bonds. 

In addition to alkyl, aryl and vinylcobalt/radical species, acid chlorides may be converted into acylcobalt species by reaction with the cobalt(I) salens. These generate acyl radicals under photolysis, which participate in similar reactions to the alkyl radicals in most cases (equations 184 and 185). Acylcobalt(III) species bearing an a-aryl or vinyl substituent, on the other hand, undergo concomitant decarbonylation to afford a benzylic or allyl radical, which then may undergo a number of bond-forming processes, including homocoupling361. 

Alternative methods for the deprotection of the allyl group at the anomeric position include Pd(PPh3)4/AcOH [402], in which the reaction proceeds by the formation of a 7r-allyl complex, or PdCl2/CuCl/02 followed by photolysis in the presence of triethylamine [403]. Per-fluoroalkylation with perfluoroalkyl iodide under sodium dithionite and sodium bicarbonate followed by elimination in the presence of zinc powder and ammonium chloride has also been disclosed as an efficient procedure for deprotection of the anomeric allyl group of carbohydrates (O Scheme 73) [404]. The reaction goes through the intermediacy of a radical addition of a perfluoroalkyl iodide to the double bond followed by Zn-mediated reductive -elimination. 

Tin.—Allyltin compounds, especially under rhodium-complex catalysis, react with acyl chlorides to give allyl ketones or with aryl halides to give allylarenes. Bridgehead alkyl bromides are reduced on photolysis with Bu"3SnH, whilst the system (Bu"3Sn)20-Br2 oxidizes sulphides to sulphoxides. )V-(Alkoxycar-bonyl)amino-acids are obtained upon treatment of cyclic anhydrides with Bu3SnN3 and heating in an alcohol. ... 

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