Pseudohalogen chemistry—VI

Reactions of thiocyanogen and thiocyanogen halides with unsaturated compounds

“…In addition to the adduct 19 (21%), (E)-hex-3-en-2yl isothiocyanate 134 (48%) is formed as a mixture of (AE)-and meso-diastereoisomers. 79 A somewhat different ratio of the products of this reaction is given by Maxwell et al 48 Compounds 134 and 19 were isolated in 45% and 39% yield, respectively, upon thiocyanation of a cis-alkene, and in 60% and 33% yields upon thiocyanation of a trans-alkene. In addition, insignificant amounts of adducts with the isothiocyano group were obtained (6.5% and 14.5%, respectively, for trans-and cis-hex-3-enes).…”

“…A comparison of the results of reactions of thiocyanogen with aliphatic and alicyclic alkenes under homolytic 79 and heterolytic 40 conditions was carried out. The yields of the products are higher in a radical reaction even after shorter reaction times.…”

“…The reaction of cis-and trans-2,5-dimethylhex-3-enes resulted only in products of the substitution of hydrogen at the allylic position, trans-2,5-dimethylhex-3-en-2-yl isothiocyanate and 2,5dimethylhex-4-en-3-yl isothiocyanate, in *29% total yield. 79 Unsaturated compounds of the type 135a ± c are formed as the main products in reactions of (SCN) 2 with cyclohexene and 4-methyl-and 4-tert-butylcyclohexenes (yields 40% ± 50%). 79 Compounds 135b,c were obtained as a mixture of isomers, and their structure was not fully determined.…”

“…79 Unsaturated compounds of the type 135a ± c are formed as the main products in reactions of (SCN) 2 with cyclohexene and 4-methyl-and 4-tert-butylcyclohexenes (yields 40% ± 50%). 79 Compounds 135b,c were obtained as a mixture of isomers, and their structure was not fully determined. 79 The reaction with trans-D 2 -octalin 29 occurs similarly to give a mixture of isomeric compounds of the type 136 (the structure was not determined, yield 45%) and the adduct 30 (40%).…”

“…79 Compounds 135b,c were obtained as a mixture of isomers, and their structure was not fully determined. 79 The reaction with trans-D 2 -octalin 29 occurs similarly to give a mixture of isomeric compounds of the type 136 (the structure was not determined, yield 45%) and the adduct 30 (40%).…”