3.7- dimethyl-10-ethyl carbonyl rhodium

The direct combination of selenium and acetylene provides the most convenient source of selenophene (76JHC1319). Lesser amounts of many other compounds are formed concurrently and include 2- and 3-alkylselenophenes, benzo[6]selenophene and isomeric selenoloselenophenes (76CS(10)159). The commercial availability of thiophene makes comparable reactions of little interest for the obtention of the parent heterocycle in the laboratory. However, the reaction of substituted acetylenes with morpholinyl disulfide is of some synthetic value. The process, which appears to entail the initial formation of thionitroxyl radicals, converts phenylacetylene into a 3 1 mixture of 2,4- and 2,5-diphenylthiophene, methyl propiolate into dimethyl thiophene-2,5-dicarboxylate, and ethyl phenylpropiolate into diethyl 3,4-diphenylthiophene-2,5-dicarboxylate (Scheme 83a) (77TL3413). Dimethyl thiophene-2,4-dicarboxylate is obtained from methyl propiolate by treatment with dimethyl sulfoxide and thionyl chloride (Scheme 83b) (66CB1558). The rhodium carbonyl catalyzed carbonylation of alkynes in alcohols provides 5-alkoxy-2(5//)-furanones (Scheme 83c) (81CL993). The inclusion of ethylene provides 5-ethyl-2(5//)-furanones instead (82NKK242). The nickel acetate catalyzed addition of r-butyl isocyanide to alkynes provides access to 2-aminopyrroles (Scheme 83d) (70S593). 

Low boiling substances are removed from the chilled reactor product by distilling up to a cut point of 80 °C. These low boilers are gaseous dimethyl ether, methyl acetate, acetaldehyde, butyraldehyde, and ethyl acetate. The bottoms are flash-distilled to recover the rhodium catalyst. Flash distilled acid is azeotropically dehydrated. In the final distillation, glacial acid is obtained. Traces of iodine that may remain in the finished acid may be removed by fractional crystallization or by addition of a trace of methanol followed by distillation of the methyl iodide that forms. Somewhere in the carbonylation reaction, a minute amount of propionic acid seems to be made. It typically is found in the residues of the acetic acid finishing system and can be removed by purging the finishing column bottoms. 

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