ON THE VARIOUS MODES OF INTERACTION OF SULFUR WITH PHENYLATED DIYNES

The reaction of elemental sulfur and five diynes of general formula Ph C=C(G)nC=CR has been studied. While 1-(1-propynyl)-2-phenylethynylbenz ene lb reacted at 120-degrees-C to give solely 6-methyl-benz[b]indeno[ 2,1-d]-thiopyran 2b, 1,1'-(1,2-phenylene)bis(3-phenyl-2-propyn-1-one) 4 and 1,8-bis(phenylethynyl)naphthalene 5 yielded the sulfides 11.11'- thiobis-(6-phenyl-5,12-naphthacenedione) 9 and 12,12'-thiobis(7-phenyl benzo[k]-fluoranthene) 13, respectively. as the major products. Diyne 5 gave also a small amount of bis(7-phenylbenzo[k]fluoranthene-12-yl)d isulfide 14. 3.3'-Oxybis(1-phenyl-1-propyne) 6 did not react in the ab sence of a metallic additive, but yielded 4,6-diphenyl-1H,3H-thieno[3, 4-c]furan 15 in the presence of equimolar quantities of RhCl3 . 3H2O a nd Aliquat-336. The reaction of the conjugated diyne 1,1'-(1,3-butadiy ne-1,4-diyl)bisbenzene 7 with sulfur afforded 3,6-diphenyl[1,2]dithiol o[4.3-c]-1,2-dithole 16.