Accession Number:

ADA128770

Title:

Synthesis and Reactivity of Some P-Mesityl Substituted Phosphorus Compounds.

Descriptive Note:

Technical rept.,

Corporate Author:

TEXAS CHRISTIAN UNIV FORT WORTH DEPT OF CHEMISTRY

Personal Author(s):

Report Date:

1983-05-25

Pagination or Media Count:

22.0

Abstract:

The preparation and characterization of a series of P-mesityl substituted phosphorus compounds containing the Si-N-P andor Si-C-P linkages are described. The reaction of RPC12 R 2,4,60Me3C6H2 with one equivalent of Me3Si2NLi affords the thermally unstable chlorophosphine Me3Si2NPRCl compound 1 in nearly quantitative yield. Substitution reactions of compound 1 are used to prepare the stable derivatives Me3Si2NPRX compound 2, X Me compound 3, X H compound 4, X CH2SiMe3, while treatment with Me3SiN3 yields the unstable axidophosphine Me3Si2NPRN3 compound 5. The methylphosphine compound reacts smoothly with CC14 via elimination of CHCl3 with a 1,3-silyl shift to form the chlorophosphinimine Me3SiNPR CH2SiMe3Cl compound 6, which is readily converted to the P-Me analogue compound 7 by reaction with MeLi. Depending on the reaction stoichiometry, treatment of RPCl2 with Me3SiCH2MgCl gives either the chlorophosphine Me3SiCH2PRCl compound 8 as an unstable product from which compound 4 is produced by reaction with Me3Si2NLi, or the stable disubstituted phosphine Me3SiCH22PR compound 9. Decomposition of the azidophosphine compound 5 proceeds with elimination of nitrogen and formation of the dimeric forms of the diiminophosphorane RP double bondNSiMe32 compound 5 a. Either the cis compound 10 or trans compound 11 four-membered ring dimer can be isolated under appropriate conditions. Proton, C13, P31 NMR data are reported for the new compounds. Author

Subject Categories:

  • Organic Chemistry
  • Plastics

Distribution Statement:

APPROVED FOR PUBLIC RELEASE