US EPA

7500706 

Journal Article 

The Reactions of Vinyl Chloroformate and Oxime Chloroformates with Silver Salts 

Beak, P; Babron, JA 

1973 

Yes 

Journal of Organic Chemistry
ISSN: 0022-3263
EISSN: 1520-6904 

38 

16 

2771-2775 

English 

10.1021/jo00956a007 

Vinyl chloroformate (1) reacts with silver acetate in chlorobenzene at 60° to give 17% vinyl acetate (2) and 65% divinyl carbonate (3). Under the same conditions 1 reacts with silver trifluoroacetate to give 77% vinyl trifluoroacetate (4). The latter reaction is shown on the basis of 180 labeling to proceed with retention of the carbon-oxygen bond and is considered to involve a carbonate intermediate. In the presence of tetramethylurea, vinyl chloroformate reacts with silver hexafluoroantimonate in chlorobenzene to give 0-(carboxy vinyl) tetramethyluronium hexafluoroantimonate (7) in 80% yield. The reaction of phenyl chloroformate with silver hexafluoroantimonate in chlorobenzene at 100° in the presence of tetramethylurea to give phenyl N,N-dimethyl carbamate is suggested to involve a uronium salt 9 similar to 7. The oxime chloroformates of benzophenone, fluorenone, and syn- and anti-4-methylbenzophenone react with silver tetrafluoroborate to give amides by the normal Beckmann rearrangement. Cationic intermediates with sp-sp2-hybridized carbon and nitrogen do not appear to be involved in these reactions. © 1973, American Chemical Society. All rights reserved.