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A series of sulfonium ylides has been prepared by the reaction of 9‐alkylidenethioxanthenes with dimethyl diazomalonate. The e' electron pair on sulfur is more efficient than the a' in trapping the “carbenes” generated by copper(II) catalyzed decomposition of diazo compounds. Consequently, e' ylides are the kineti‐cally‐controlled reaction products. Varying the C2 substituent does not alter this. Sulfides and sulfonium ylides containing the isopropylidene moiety do not undergo rapid ring inversion. Rotation about the S+C− bond occurs in the pseudo‐axial conformation but not the pseudo‐equatorial. The use of the anisochronicity of portions of the malonylide fragment as a criterion for heterocyclic ring inversion is presented. It is suggested that the sulfoxides of phenothiazine, phenoxathiin, thianthrene, and related sulfoxides, undergo rapid ring inversion.

Die Phosphorylierung der organischen Bromide (I) mit dem Ammoniumdibutylphosphat (II) führt zu den Alkyldibutylphosphaten (IIIa), deren selektive Desalkylierung mit Trifluoressigsäure die Monoalkylphosphate (IIIb) ergibt.