Organophosphazenes. 18. Friedel-Crafts Phenylation Reactions of Alkyl and Nimethylamino Fluorocyclotriphosphazenes.
Abstract
The monodimethylamino and monobutylpentafluorocyclotriphosphazenes, N3P3F5R(R = N(CH3)2, n-C4H9, t-C4H9 undergo the Friedel-Crafts phenylation reaction to yield N3P3F4(C6H5)R. A geminal configuration was assigned to each of the phenyl derivatives based on the NMR (1H, 13C, 31P) spectroscopic data. The crystal and molecular structures of N3P3F4(C6H5)(t-C4H9) have been determined; the crystals are orthorhombic, space group P sub nma, with a = 7.264(1)A, b = 12.204(2)A, c = 17.028(3)A, V = 1509.5(7)A, and Z = 4. The final refinement gave R = 0.042 and R sub w = 0.054 for 1087 observed reflections. The molecule, which has a crystallographically-imposed mirror plane of symmetry, has the predicted geminal arrangement of organic groups and P-N distances of 1.618(1), 1.527(2), and 1.565(1)A. The central P-N ring is planar within 0.007A. Bond angles are: C-P-C, 108.9(1) deg; F-P-F, 96.36(9) deg; N-P-N, 114.1(1); 120.91(9) deg; P-N-P, 122.58(9); 118.9(1) deg. The observation of Friedel-Crafts phenylation of the alkylphosphazenes that Pi donation from an exocyclic substituent is not a necessary prerequisite for this reaction. Originator furnished keywords include: cyclophosphazene; Friedel-Crafts Reactions; nmr; x-ray structure.
Document Details
- Document Type
- Technical Report
- Publication Date
- Nov 15, 1984
- Accession Number
- ADA150595
Entities
People
- A. W. Condes
- C. W. Allen
- S. Bedell
- William T. Pennington
Organizations
- University of Vermont