Miscellaneous Photoadditions

Several examples of the photoaddition of amines and amine derivatives to olefins have been reported. ° Butylamine adds to 1-octene upon ultraviolet irradiation to produce 4-aminoalkane  

Photolysis of piperidine and 1-octene mixtures similarly leads to 2-octyl-piperidine through the intermediacy of an amine radical RCHNHR. Monochloroamine adds to cyclohexene to produce rrons-dilorocyclo-hexylamine and other products from radical recombination  

In the photoaddition of 2-pyrrolidone the 5-alkyl isomer (69) always predominates, usually in a ratio of 2 1. The formation of anti-Markovnikov 1 1 adducts, telomers, and dehydrodimers of structure (71) supports a free radical mechanism. Similarly, formamide undergoes olefin addition under 

With terminal olefins the principal product corresponds to anti-Markovnikov addition. With nonterminal olefins, mixtures of the two possible amides result  

A free radical chain mechanism is proposed for these reactions  

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In this section the photoaddition of water, alcohols, carboxylic acids, and miscellaneous other small molecules to various substrates will be considered. 

Many other miscellaneous additions of alcohols have been described. Polar addition of methanol to 2//-pyrroles264 and to azepines265 has been observed. Photoaddition of methanol to the 1,3,4-oxadiazole 320 is followed by cycloelimination of methyl benzoate (321) to give the ylid 322.266 An adduct (323) of the ylid and the 1,3,4-oxadiazole has been isolated. Photoaddition of methanol to the quaternary ammonium salt 324 results in ring expansion and the formation of the azonine 325.267... 

Miscellaneous examples of the photoaddition of solvent and other simple molecules to nitrogen-containing systems have been described. Methoxylation, methylation, and hydroxymethylation arising via ionic and radical pathways have been observed on irradiation of dimethyl pyridine-2,4-dicarboxylate in methanol. The photomethoxylation of methyl pyridine-2-carboxylate in acidified methanol is facilitated by added 4-substituted pyridines such as 4-cyanopyridine an excited complex is thought to be involved. 

Other miscellaneous additions have been reported. Novel three-, five-, and six-membered nitrogen-sulphur heterocycles have been prepared by irradiation of sulphur monochloride in the presence of perfluoroazoalkanes. Photoaddition of hydrogen sulphide to the diallylsilane (232) yields the thiol (233), which readily undergoes cyclization to the l-thia-5-silacyclooctane (234). ... 

Other miscellaneous additions reported include the photoaddition of thiocarboxylic acid to 3,4-diallyl-1,6-propano-1H,6H-3a-thia (S )-1,3,4,6-tetraazapentalene-2,5(3H,4H)-dithione, the Paterno-BUchi addition of methyl vinyl sulphides to benzophen-... 

Other miscellaneous reactions arising at least in part by photoaddition have been reported. The photoaddition of primary and secondary amines to... 

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