New, useful reactions of novel haloformates and related reagents

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Abstract
Uses of the a -chloroalkyl chloroformates 2 obtained by the C1- catalyzed addition of phosgene to aldehydes are reported. The best known compound of t his type, a-chloroethyl c hloroformate (ACE-Cl), is a mild reagent for the selective N-dealkylation of tertiary amines with commer- cial value. Both ACE-C1 and its congener from chloral are protecting groups for alcohols The derived carbonates are efficient precursors to fluoroformates including the important t-butyl fluoroformate. Appl ica- tions in which fluoroformates a re s uperior to chloroformates are outlined. The elimination of HC1 from the carbamates/carbonates easily formed from - 2 is described. (From the s urprising carbonate elimination mechanism, a simple synthesis of aldehyde enolates under preparatively useful condi- tions has been discovered.) The product vinylic carbamates and carbon- ates are monomer precursors to vinyl polymers with urethan and carbonate branches. 2,2-Dihalovinyl c hloroformates also have been made and con- verted to carbamate and carbonate monomers. Finally, 3- and 4-carbon synthons available by extensions of the above chemistry are i ntroduced. Some years ago, together with Senet and coworkers at le Bouchet Research Center of SNPE in

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