Diacetylene mono substituted

In some derivarization reactions with mono-metallaied bmadiyne, considerable amounts of disubstimted diacetylene are farmed. Their presence can hamper the purification of the desired mono-substitution products, particularly when the boiling point is high and the thermal stability limited. The formation of disubstitution products can be effectively suppressed, however, by using a large excess of butadiyne. The preparation of butadiynvl tributyltin is an illustrative example. 

J.B. Armitage et al, CA 47,1034( 1953)(In the prepn of mono substituted derivs of diacetylene, a small quantity of an expl product corresponding to the formula ... 

Mono- and bis(pentafluorosulfur)diacetylenes, F6SC=C—C=CH and F5SC=C—C==CSF5, are obtained by the addition of F5SBr to diacetylene followed by dehydrobromination. These monomers yield interesting polymers (140). A variety of uses are proposed for several of these pentafluorosulfur-containing alkanes and alkenes, e.g., as dielectric insulators (122, 141), elastomer precursors (142), blood substitutes (143), fumigants (144), and insecticides (145). 

The outline of this article is as follows. After general remarks tUsout the solid-state polymerization process, adopting the view that it is important to develop new types of solid-state polymerization, the polymerization of the following classes of monomers will be discussed diacetylenes, monoacetylenes, vinyl and diene monomers, cyclic systems which ring open, and transition metal systems. It is implicit in the discussion that appropriately substituted forms of the above monomers may be polymerized as mono-layers and multilayers (11-13) as well as in the form of inclusion complexes (14). Emphasis will be placed on topics of current interest. 

Reaction of Pt(PPh3)2(02114) with diacetylenes such as l,4-diphenylbuta-l,3-diyne yields both mono- and di-platinum complexes assigned structures (128) and (129). Reaction with Pt3(CNBu )e yields (130), while treatment of Pta-(CNBu )e with diphenylcyclopropenone results in ring opening to yield (131), which may also be prepared by reaction of (cod)Pt(methylvinylketone)2 with diphenylcyclopropenone followed by substitution of cod with Bu NC. ... 

Dithiins and Related Compounds.—Diacetylenic sulphides react with Na2X (X = S, Se, or Te) to give the mono- and di-substituted heterocycles (24). Other syntheses of 1,4-dithiins from acetylenes are the reactions of amidines of phenylpropiolic acid with sulphur (or selenium) in DMF, and of dimethyl acetylenedicarboxylate with hydrogen bromide in liquid sulphur dioxide. In the latter reaction, sulphuric acid is formed by disproportionation. 

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