Erythrina Alkaloids. XIV. Isolation and Characterization of Erysothiovine and Erysothiopine, New Alkaloids Containing Sulfur1a

Journal of the American Chemical Society
1944.0

Abstract

The condensation product from ketene acetal and benzoquinone is shown to be 2-ethoxy-5 hydroxycoumarone instead of 7-ethoxy-2,5-diketobicyclo[4,2,0]octadiene-3,6 as previously reported. Xyloquinones and 1,4-naphthoquinone are much less reactive than benzoquinone toward ketene acetal. The temperatures necessary to produce reaction appear to polymerize most of the initial reaction products so that only small yields of coumarones corresponding to the one obtained with benzoquinone are isolated. Duroquinone does not react with ketene acetal. Bromoquinones are much more reactive toward the acetal than are the methyl-substituted quinones. With bromobenzoquinones the reaction takes place at one of the unsubstituted ring carbons. With the bromonaphthoquinones a bromine substituent is replaced with the evolution of ethyl bromide; 2-bromonaphthoquinone yields xanthopurpurin diethyl ether and 2,3-dibromonaphthoquinone yields ethyl 3-bromo-1,4-naphthoquinon-2-ylacetate. Studies on the combined alkaloidal fractions of several species of Erythrina led to the isolation and characterization of two new crystalline compounds containing sulfur. Microanalytical data showed that one compound had the formula, C20H23NO7S, and the other, C19H21NO7S. They yielded erysovine (C18H21NO3) and erysopine (C17H19NO3), respectively, on hydrolysis. For correlation of names and to designate the sulfur atom present, they were named erysothiovine and erysothiopine. Since the hydrolytic reaction yielded one mole of sulfoacetic acid in each case, erysothiovine and erysothiopine are alkaloidal esters of sulfoacetic acid with erysovine and erysopine. Apparently, they are sulfonic esters. Erysothiovine and erysothiopine are highly active for curare-like paralysis in frogs and they are three to four times more active than the corresponding alkaloids erysovine and erysopine.

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