FORMATION OF SULFENAMIDES AND SULFONAMIDES BEARING THE ORGANO-AMINOMETHYLENE-DIMETHYL PHOSPHINE OXIDE OR SULFIDE GROUP

The reaction of l-N-trimethylsilylaminomethylene-dimethylphosphine oxi de 1 and sulfide 2 with various sulfinyl and sulfonyl chlorides furnis hed, in good yield, a series of phosphorus-containing sulfinamides and sulfonamides, 3-11, bearing the dimethylphosphoryl and thiophosphoryl group, respectively. All sulfinamides (3-8) show a complicated splitt ing pattern for the H-1-n.m.r. resonances of the C (H) under bar(2)P-g roup, due to the presence of a chiral sulfur atom. For the same reason , doubling of the (C (H) under bar(3))(2)P-proton resonances is observ ed for 3, 4, 7 and 8. N.m.r. spectra for the sulfonamides 9-11 are in accord with expectation. N-benzylaminomethylene-dimethylphosphine oxid e 12 was allowed to react with chlorosulfonylacetic acid methyl ester in the presence of triethylamine as a base to form the phosphorus-cont aining sulfonamide 13 in good yield. In the reaction of 5 with air/moi sture, by an unknown reaction course, the phosphorus-containing ammoni um hydrogen sulfate 14 was formed. X-ray crystal structure determinati ons were conducted for 10 and 14. The two independent molecules of 10 are closely similar and show C-N-S-C torsion angles of 89, 83 degrees. In compound 14, hydrogen bonding links two formula units.