Triphenyl phosphite → Chlorine

Reaction equation

[Cl:1][Cl:2].[P:3]([O:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)([O:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)[O:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1>C(Cl)Cl>[Cl-:1].[P:3]([O:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)([O:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[O:4][C:5]1[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=1.[Cl:1][Cl:2]

Participants

Procedure

A solution of triphenyl phosphite-chloride kinetic complex was prepared by adding chlorine and triphenyl phosphite (36.8 ml., 3.5 equivalents per equivalent of cephem sulfoxide used below -22.3 g.) simultaneously to 150 ml. of methylene chloride at about -20° to about -10° C., maintaining a pale yellow color in the reaction mixture throughout the co-addition. With the addition of the last drops of triphenyl phosphite to the mixture, it gave a negative starch-iodide test for chlorine. After cooling the mixture to -25° C., 5.1 ml. of amylene and subsequently 22.3 gm. of 4'-nitrobenzyl 7-phenoxyacetamido-3-hydroxy-3-cephem-4-carboxylate, 1-oxide were added. After stirring 25 minutes at -15° to -10° C., the dropwise addition of 11 ml. (3.4 equivalents per equivalent of cephem sulfoxide) of pyridine in 30 ml. of methylene chloride was begun. Pyridine addition was extended over 53 minutes. Fifteen minutes after pyridine addition was complete, 37 ml. (10 equivalents) of isobutanol was added and HCl was bubbled into the reaction mixture for 6 minutes. The title product crystallized from solution and was isolated by filtration, washed with 100 ml. of methylene chloride and dried in vacuo. Yield--6.4 g. (37%).