6533b7dbfe1ef96bd12713ec

RESEARCH PRODUCT

Phosphororganische Verbindungen, 64: Allyl‐Propenyl‐Umlagerungen Das elektrochemische Verhalten einiger Propenylverbindungen

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Allyl-aryl-sulfone, Allyl-diphenyl-phosphinoxid, Allylphosphonsaure-diathylester, Allyl-triphenyl-phosphoniumbromid und Allyl-triphenyl-arsoniumbromid lagern sich an basischem Al2O3 in die entsprechenden 1-Propenyl-Verbindungen um. Allyl-diphenyl-phosphin und Diallyl-phenyl-phosphin isomerisieren sich unter Mitwirkung von Natriumathylat zu den entsprechenden 1-Propenyl-Verbindungen. Die Allyl- und 1-Propenyl-Verbindungen werden IR- und NMR-spektroskopisch sowie polarographisch charakterisiert. — Bei der kathodischen Spaltung von 1-Propenyltriphenyl-phosphoniumbromid entstehen 92% Triphenylphosphin und Propen. 1-Propenyl-phenyl-sulfon wird elektrochemisch in Propen und Benzol-sulfinsaure aufgespalten. Organic Phosphorus Compounds, 64. Allyl-Propenyl Rearrangements. The Electrochemical Behaviour of some Propenyl Compounds Allyl aryl sulfones, allyldiphenylphosphine oxide, diethyl allylphosphonate, allyltriphenylphosphonium bromide and allyltriphenylarsonium bromide undergo rearrangement on basic Al2O3 (the last-named allyl compound only to a limited extent) to give the corresponding 1-propenyl compounds. Allyldiphenylphosphine and diallylphenylphosphine also rearrange on treatment with sodium ethoxide to give the corresponding 1-propenyl compounds. The allyl and 1-propenyl compounds are characterised by i.r. and n.m.r. spectroscopy as well as polarographically. — Cathodic cleavage of (1-propenyl)triphenylphosphonium bromide, affords triphenylphosphine and propene in 92% yield. 1-Propenyl phenyl sulfone is cleaved electrochemically to propene and benzenesulfinic acid.