US EPA

7501166 

Journal Article 

Mechanism of reaction of phosphorus pentachloride with carboxylic acid amides 

Kirsanov, AV 

1954 

1 

Bulletin of the Academy of Sciences of the USSR. Division of Chemical Science
ISSN: 0568-5230 

Kluwer Academic Publishers-Plenum Publishers 

3 

4 

551-558 

English 

10.1007/BF01172698 

1. The scheme. of Wallach for the reaction of unsubstituted carboxylic acid amides with phosphorus pentachloride, generally accepted at the present day. is e roneous. Amidochlorides are not formed in the action of phosphorus pentachloride on unsubstituted carboxylic acid amides. 2. The reaction of unsubstituted amides of carboxylic acids with phosphorus pentachloride actually proceeds with formation of trichlorophosphazoacyls and two molecules of hydrogen chloride. e. 3. When heated or when exposed to the catalytic action of hydrogen chloride at room temperature, triclrlreophosphazoacyls break down to phosphorus oxychloride and nitriles. 4. The structure of the produt of reaction of phosphorus pentachloride with benzamide was established, as that of trichlosophosphazobenzoyl by a chemical method. 5. Trichlorophosphazoacyls are extremely reactive and can serve as starting substances for the preparation of the most diverse derivatives of phosphoric acid. 6. Reaction of phosphorus pentachloride with ethyl carbamate gives the ethyl ester of trichlorophospha o-carbonic acid which at 45° cleaves to ethyl chloride and isocyanophosphoryl chloride, 7. Reaction of phosphorus pentachloride with ethyl oxamate gives at first dichloroetboxyacetamide and then trichlo ophosphazo-dichloroethoxyaceyl. © 1954 Consultants Bureau, Inc.