Syntheses of Some Phosphino- and Phosphinatoazoles

Abstract

The following N-substituted azoles have been prepared: (a) diphenylphosphine derivatives of pyrazole (la), 3,5,-dimethylpyrazole (lb), 3(5)-methylpyrazole (isomers 2a and 2b), pyrrole (7), imidazole (8), and 1,2,4-triazole (9); (b) diphenylphosphinatopyrazole (46); (c) dichlorophosphinopyrazole (5a) and dichlorophosphino-3,5-dimethylpyrazole (Sb); (c) 1,l-phenylphosphinobis(pyrazo1e) (3); (d) tris (pyrazoly1) 3); ( e ) tris(pyrazoly1)phosphine (6a) et le tris(dimethy1-3,y pyrazoly1)phosphine (6b). Les methodes de synthese font appel aux reactions (i-ic): (i) l'azole avec la chlorophosphine (pour 1-3, 8, 9) ou +,P(O)Cl (4a) dans une solution Ctheree avec la triethylamine comme accepteur d'acide halogene-hydrique; (ii) la trimCthylsilylazole avec le trichlorure de phosphore (5, 6 ) ; (iii) le pyrrolidure de potassium avec la diphtnylchlorophosphine (8); (it.) l'oxydation du soufre de l a (4b). Les attributions spectrales deduites de 1'Ctude r.m.n. sont discutees.[Traduit par le journal]

1-Pyrazolyl phosphazenes and their complexes with palladium(II) chloride and platinum(II) chloride

“…Some typical results for 5 are shown in Table 3. Similar phenomena are observed in the spectra of (trimethylsily1)pyrazoles (13) and in phosphino-and phosphinato-azoles (11). In the former, an intramolecular migration of the Me,Si group has been suggested to account for the coalescence of the 3-and 5-substituent resonances upon increasing the temperature.…”

Aminodiphenylphosphanes: Isotope‐induced chemical shifts 1Δ14/15N(31P), coupling constants 1J(31P,15N), and chemical shifts δ15N and δ31P

“…Diphenylphosphorus chloride, all amines, pyrrole, BuLi (1.6 M in hexane), and 5 were commercially available. Diethylamine, N-methylaniline, pyrrole, N,N-diisopropylamine, and tert-butylamine [11,32], 2e [12], 3b [31a], and 4 [33] has been reported previously. Progress of all reactions was monitored by NMR spectroscopy.…”

Syntheses and properties of phosphino- and phosphinatopyrazoles

“…The mixture was stirred for 12 h, the precipitate filtered off and washed with ether, and the solvent evaporated from the filtrate. The residue was purified by sublimation; yield 85% This is an alternative to the earlier reported method using PC13 and trimethylsilylpyrazole (1).…”