Irradiation In Methanol Research Articles

773. The chemical action of ionising radiations on simple aliphatic alcohols. Part II. Irradiation of methanol in the absence and in the presence of oxygen in the solid and in the liquid state

The radiation chemistry (Co/sup 60/ gamma rays and 200 kv x rays) of ethanol was studied, particularly as a function of temperature and of the concentration of some selected solutes (oxygen, chloroacetic acid, glycollic acid, acetic acid, 2chloroethanol) with the object of elucidating the primary radiolytic mechanism. It is suggested than ethanol is, to a large extent, ionized into positive and negative polarons. In the presence of solutes with good electron accepting properties, such as oxygen and chlorinated organic compounds, the negative polarons can react directly with them, the mechanism of which is similar to that proposed for aqueous systems. (auth)

Photochemical Transformations of Oxadiazepinones and Related Systems'

The results of our studies on the phototransformations of a few oxadiazepinones are presented. Irradiation of a benzene solution of 2-oxo-7,8-dimethyl-9,9-diphenyt-2,9-dihydro-1,4,5-benzoxadiazepine (1) . gives a mixture of 6,7- dimethyl-2,2- diphenyl-2(H)-1,4,5- bezoxadiazine (4, 8%) and 5,6-dimethyl-2,2-diphenylmethylenebenzo-1,9-dioxole (10, 50%), whereas the irradiation in moist benzene gives 2-hydroxy-4,5-dimethylphenyl diphenylacetate (13). Irradiation of 1 in methanol gives a mixture of 10 (12%), 9,4-dimethylphenol (7, 9%), methyl diphenylacetate (14b, 92%) and 2,9-dimethyl-6-hydroxy-6-methoxy-2-(4,5-dimethyl-2-hydroxyphenylazo)fulvene (17, 14%). Similarly, the irradiation of 2- oxo-9,9- diphenyl-2,9- dihydronaphtho[1,2- b]-1,4, 5- oxadiazepine (18) in benzene gives a mixture of 2-indenylidenenaphtho[1,2-d]-1,9dioxole (22, 4%), indene-9-carboxylic acid (23a, 97%), diphenylacetic acid (14a, 95%) and diphenylacetic anhydride (24, 15%). In contrast, the irradiation of 18 in methanol gives a mixture of 2-methyl diphenylacetate (14b, 61%) and methyl indene-8-carboxylate (23b, 65%). Irradiation of 2,5-dioxo-1,1,4,4-tetraphenylphenanthro[9,10-b] diazetidino[1,2-b]-perhydro-1,4,5-oxadiazepine (25) in benzene gives a mixture of 2,2-diphenylphenanthro[9,10-b]-furan-9(2H)-one (29, 19%) and ,S'-oxo2, 2, 2',2' -tetraphenylphenanthro(9,10-b]-2, 9- dihydrofuran-9-spiro-4'-oxetane (28), whereas the irradiation of 2-oxo-2,5-dihydro-1,4,5-benxoxadiazepine (31) in benzene does not give rise to any product. Irradiation of 31 in methanol, however, gives a mixture of Z-methyl (2-hydrozyphenylhydrazono)glyozalate (34, 12%) and E-methyl (2-hy-droxyphenylhydrazano)glyoxlate (33, 45%). It has been shown that both 33 and 34 undergo interconversion, on irradiation in methanol.

Radiolysis of Methanol and Methanolic Solutions by CO60Gamma-Rays and 1.95 x 106Volt de Graaf Electrons

Yields of hydrogen, formaldehyde, ethylene glycol (determined by means of an improved procedure), methane, and carbon monoxide per 100 ev of absorbed radiation obtained on irradiation of methanol are compared with values reported in ihe literature. The several sets of data are not in good agreement with each other. Initial study of ihe effects of several solutes suggests a variety of modes of intervention in the radiolytic process. (auth)