JOURNAL O F THE AMERICAN CHEMICAL SOCIETY Registered in U . S . Pafenl O f i c e .
@ Copyright, 1963, b y lhe American Chemical Society
VOLUME 85, NUMBER16
AUGUST20, 1963
PHYSICAL A N D INORGANIC C H E M I S T R Y [CONTRIBUTION FROM THE
DEPARTMENT OF CHEMISTRY, UNIVERSITY
The Reactions of Sulfur Atoms.
O F ALBERTA,
EDMONTON, ALBERTA,CANADA]
111. The Insertion in Carbon-Hydrogen Bonds of Paraffinic Hydrocarbons
BY A. R. KNIGHT,0. P. STRAUSZ AND H. E. GUNNING RECEIVED APRIL 5 , 1963
S(ID) atoms, produced in the in situ photolysis, a t 25" in a static system, of gaseous carbonyl sulfide in the wave length region 2290-2550 A., were found to react with paraffinic hydrocarbons. The following substrates were examined: methane, ethane, propane, cyclopropane, and isobutane, and in each case t h e sole primary product was the corresponding mercaptan. I n the methane system, secondary decomposition of the mercaptan occurred giving rise t o a number of additional products. With propane and isobutane, t h e isomeric distribution of mercaptans, n-PrSHli-PrSH = 2.85 f 0.05 and i-BuSHlt-BUSH = 8.8 f 0.1, demonstrates the indiscriminate nature of t h e attack on C-H bonds. With increasing paraffin pressures, R
