Phenyl chlorosulfite

Nitriles. Aldoximes can be converted into nitriles in high yield by reaction with phenyl chlorosulfite in ether containing 1 eq. of pyridine at 5°. On standing at 25° the phenyl oxime-O-sulfonate decomposes to a nitrile. Carbonates of oximes also decompose to nitriles, but only at temperatures above 100°. ... 

Phenyl-2-amino-l, 3-propanediol, 386 Phenylation, 28, 104 Phenylazomalondialdehyde, 417 3-Phenylbutanoic acid, 416 7-Phenylbutyric acid, 20, 21, 127 S-Phenyl-y-butyrolactone, 20-21, 127 Phenyl chlorosulfite, 456... 

Dehydration Alumina (see also Dihydropyrane, preparation). Boric acid. Boron triSuoride. N-Bromoacetamide-Pyridine-SOj. Dicyclohexylcarbodiimide. Diketene. Dimethylform-amide-Thionyl chloride. Dimethyl sulfoxide. Ethylene chlorophosphite. Florisil. Girard s reagent. Hydrobromic acid. Iodine. Mesyl chloride-Sulfur dioxide. Methyl chlorosulfite. Methylketene diethylacetal. Naphthalene-d-sulfonic acid. Oxalic acid. Phenyl isocyanate. Phosgene. Phosphorus pentoxide. Phosphoryl chloride. Phthalic anhydride. Potassium bisulfate. Pyridine. Thionyi chloride. Thoria. p-Toluenesulfonic acid. p-Toluenesulfonyl chloride. Triphenylphosphine dibromide. 

Eligh yields of esters are obtained from both acid-sensitive (cyanoacetic acid) and base-sensitive carboxylic acids (3-phenyl-propionic acid and trichloroacetic acid) and, in these latter cases, use of 4-(dimethylamino)pyridinium chlorosulfite chloride is much more effective than use of thionyl chloride alone. The esterification process has been claimed to be independent of the steric environment of the carboxyl function, though this reagent may be of more limited value with heavily substituted benzoic acids. Carboxyl activation, in the presence of a primary amine, leads to the corresponding amide in excellent yield (eq 2). In both the esterification and amidation processes and the oxime dehydration reaction discussed below, recovery of DMAP is straightforward. 

---