The Utilization of Sulfur, Sulfenyl, Selenenyl, and Seleninyl Chlorides in the Conversion of Aldoximes to Nitriles

G e o r g e S o s n o v s k y a n d J a m e s A . K r o g h Department of Chemistry, University o f Wisconsin-Milwaukee, Milwaukee, Wisconsin 53201, U S A Z. Naturforsch. 84b , 511-515 (1979); received N o v e m b e r 28, 1978 Sulfur Chlorides and Disulfides, Conversion o f Aldehydes to Nitriles, Selenium Chlorides and Diselenides, Nitriles, A ldox imes The comparat ive usefulness of six sulfur, sulfenyl, selenenyl, and seleninyl chlorides towards aldoximes in the presence of a base were examined under similar reaction conditions. The reactions of aromatic aldoximes with either sulfur dichloride (1), sulfur mono chloride (2), or trichloromethane sulfenyl chloride (3) in either ether or chloroform at 2 3 3 5 °C after one hour resulted in 6 0 8 4 % yields o f nitriles. Under the same conditions, the reactions of aliphatic aldoximes with either 1, 2, or 3 gave mixtures o f products , while at — 4 0 to — 3 0 °C, 1 5 2 2 % yields o f aliphatic nitriles were obtained. The reactions o f aliphatic and aromatic oximes with either benzenesulfenyl chloride (4), benzeneselenenyl chloride (5), or benzeneseleninyl chloride (6) produced after f ifteen minutes to three hours the corresponding nitriles in 7 1 9 6 % yields at 23 -35 °C.