Nonhomogeneous phase effect on the generation of carbene radical anions in the Birch-type reduction of bis(gem-dihalocyclopropyl)compounds

Abstract

propyl) substrate. The initial reactant and all of the intermediates that will react with solvated electrons protect the electron-free zone until their chemistry is complete. It is after complete reduction that the boundary of the mixing process is advanced with more solvated electrons, and the same chemistry continues at or near the new boundary. The visualization of this in chemical terms is that on the time scale of these reactions the substrate finds it environment as either of two extreme situations, electron-free or electron-rich (see ref 6 and 7).We propose that this may be another example of unusual chemical observations that may be accounted for by distortions in the product distributions that are the result of nonhomogeneous chemistry rather than the intervention of unusual reaction mechanisms or intermediates. [6][7][8] Acknowledgment. We thank Mr. B. Weber for assistance in obtaining 500-MHz NMR spectra and Ms. M. Chan for the GC/MS work. Also we thank Professors J. F. Bunnett and A. Oku for helpful discussions concerning this work.Registry No. I,

Complete destruction of chlorofluorocarbons by reductive dehalogenation using sodium naphthalenide

“…Under the gas-liquid treatment conditions shown in Table II, the amount of unreacted Freon 113 and volatile reduction intermediates trapped in D was very small. This indicates that Freon 113 in the nitrogen stream was efficiently absorbed in the reductant solution probably due to a very rapid, almost diffusion-controlled reaction of the C-Cl bonds (Oku et al, 1983a). A small amount of Freon 113 detected in D may be due to a little imperfect absorption.…”