Organophosphazenes. 16. The Synthesis and Reactions of 1-Alkoxyvinyl-fluorocyclotriphosphazenes.
Abstract
The reactions of 1-lithioalkoxyethylenes with hexafluorocyclotriphosphazene (N3P3F6) have been examined. In contrast to similar reactions of propenyl lithium with N3P3F6, no evidence for degradation reactions via anionic attack on the olefinic center was observed and the reaction proceeds smoothly to yield N3P3F6-N (C(OR)=CH2n (n=1,2; R=CH3, C2H5). The reaction follows a geminal pathway at the stage of disubstitution. The mixed phenyl/ethoxyvinyl derivative, 2,2-N3P3F4(C6H5) C(OC2H5)=CH2, and dimethylamino/ethoxyvinyl derivatives, 2,4-N3P3F4(N(CH3)2)C(OC2H5)=CH2, have been prepared. Evidence for both incoming group and ring substituent control of product stereochemistry has been observed. A model for ring substituent control is presented. The new alkoxyvinyl phosphazenes are characterized by mass spectrometry and NMR (1H, 13C, 19F, 31P) spectroscopy. Examination of the 13C NMR spectra show that the electron withdrawing effect of the phosphazene results in a significant reduction of the electron rich nature of the parent olefins. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Dec 06, 1982
- Accession Number
- ADA122591
Entities
People
- Christopher W. Allen
- Randall P. Bright
Organizations
- University of Vermont