Reactions of sterically hindered primary phosphines with elemental sulfur or selenium are reviewed. (2, 4, 6-Tri-
t-butylphenyl) phosphine reacted with an excess amount of elemental sulfur in the presence of a catalytic amount of base to give the corresponding dithioxophosphorane via the phosphine sulfide. Dithioxophosphoranes and diselenoxophosphoranes bearing the 2, 4-di-
t-butyl-6- (dialkylamino) phenyl group were prepared by a similar method. These compounds are more stable than the corresponding 2, 4, 6-tri-
t-butylphenyl derivatives. Deselenation reaction of stabilized (selenoxo) (thioxo) phosphoranes and diselenoxophosphoranes afforded thioxophosphines and selenoxophosphines, respectively. On the other hand, reaction of (2, 4-di-
t-butyl-6- methoxyphenyl) phosphine with sulfur gave
trans- and
cis-1, 3, 2, 4-dithiadiphosphetane-2, 4-disulfides via dithioxophosphorane. The monomeric form of dithioxophosphorane, which can be generated from dithiadiphosphetane disulfides by heating, reacted with benzophenone to give thiobenzophenone. (2, 4-Di-
t-butyl-6-methoxyphenyl) phosphine reacted with selenium to give 1, 2, 3, 5, 7-pentaselena-4, 6, 8-triphosphocane, which was used to convert amides into thioamides.
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