In a previous paper we reported that photoexcited SO2 reacts with alcohols, ethers, sulfides and chlorides to form a-substituted alkanesulfinic acids'. Here we report the formation of carbenium ions by reaction of photoexcited SOz with trialkyl orthoformates or benzaldehyde dimethyl acetal :When a 2.0 molar solution of e.g. trimethyl orthoformate in liquid SO, had been irradiated with UV-light' at -75°C for 18 h, ca. 40% of the orthoformate had reacted of which 65% was found back as the trimethoxymethyl cation** as appears from the following evidence.
Bei Bestrahlung der Orthoester (Ia) bzw. (Ib)‐in flüssigem SO2 bei ‐75°C entstehen über die entsprechende Zwischenstufe (II) die Produkte (IIIa) bzw. (IIIb) und daneben die Ester (IVa) bzw. (IVb).
Die UV‐Bestrahlung einer Lösung von Äthanol (I) in flüssigem SO2 bei ‐7 5°C führt zur 1‐Hydroxyäthansulfinsäure (II), deren Natriumsalz (III) stabil ist und durch Sauerstoff zum Sulfonat (IV) oxidiert wird.
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