Reaction Of Phenylphosphine Research Articles

Organo–Phosphorus–Sulfur Heterocycles by Reactions of Phenylphosphine with Ketones

The reaction of phenylphosphine (PhPH2) with ketones showed conversion into a 5-membered heterocyclic ring of the type P2SOC if 2–2.5 equivalents of sulfur (S8) were used. X-Ray data and 31P, 13C, 1H NMR spectra proved the formation of the (Z) diastereomer of 1,3,2,4-oxathiadiphospholane 1 ((PhPS)2SOCMe2) if acetone is used. Mechanistic studies displayed that small changes in the reaction pathway lead toward the formation and characterization of intermediates including 1,3,2,4,5-dithiatriphospholane, 2,4,5-triphenyl-2-sulfide (PhP)3S3 and 1,3,2,4-oxathiadiphospholane, and 5,5-dimethyl-2,4-diphenyl-2-sulfide ((PhPS)(PhP)SOCMe2), which undergo reactions with acetone, subsequently yielding the abovementioned heterocyclic ring.

Synthesis of C-(N,N-dialkylamino)phosphaalkenes

New C-(N,N-dialkylamino)phosphaalkenes were synthesized by the reaction of phenylphosphine with amidacetals. Such compounds may also be synthesized by the reaction of bis(trimethylsilyl)phenylphosphine with amidacetals.

Reaction of bis(hydroxymethyl)phenylphosphine with dimethylformamide dimethylacetal

1. The reaction of bis(hydroxymethyl)phenylphosphine with dimethylformamide dimethylacetal gave 2-dimethylamino-5-phenyl-1,3,5-dioxaphosphorinane as the major product and dimethylaminomethylenephenylphosphine. The reaction of phenylphosphine and bis(dimethylamino)methoxymethane is indicated for the preparation of dimethylaminomethylenephenylphosphine. 2. Dimethylaminomethylenephenylphosphine adds tetrachlorocyclopentadienone dimethylacetal at room temperature to give 1,4,5,6-tetrachloro-7,7-dimethoxy-3-dimethylamino-2-phenyl-2-phospha-5-norbornene in quantitative yield.

Synthesis of triethylammonium l,4-diphenyl-3-o-hydroxyphenyl-2,8,9-trioxa-1-borata-4-phospha-6,7-benzenobicyclo[3.3.1]nonane

The reaction of phenylphosphine with salicylaldehyde and phenylboric acid anhydride in the presence of triethylamine proceeds with the formation of triethylammonium 1,4-diphenyl-3-o-hydroxypheny1-2,8,9-trioxa-1-borata-4-phospha-6,7-benzenobicyclo[3.3.1]nonane.

Reactions of 1,3,2,5-dioxaborataphosphoniarinanes with aldehydes and nitriles

1. In the reaction of phenylphosphine with aldehydes and isobutyl diphenylborate, 2,2,5-triphenyl-4,6-di-R-5-a-hydrozyalkyl-1,3,2,5-dioxaborataphosphoniarinanes were obtained. 2. The reaction of 2,2,5-triphenyl-4,6-di-R-l,3,2,5-dioxaborataphosphoniarinanes with aliphatic aldehydes leads to a displacement of aldehydic fragments with retention of the structure of the molecule. 3. In the reaction of 2,2,5-triphenyl-4,6-di-R-l,3,2,5-dioxaborataphosphoniarinane and ammonium 1,3,2,5-dioxaborataphosphorinanes with nitriles, only one aldehyde fragment is displaced, and diphenylboryloxyalkyl (imidoyl)phenylphosphines are formed.

Structure of product of reaction between phenylphosphine and phenyldichloroarsine and phenylarsine oxide

In the reaction of phenylphosphine with phenyldichloroarsine and phenylarsine oxide, 1,2,3,4,5,6-hexaphenyl-1,3,5-triphospha-2, 4,6-triarsacyclohexane is formed.

Reaction of phenylphosphine with p-quinones

The reaction of phenylphosphine with p-quinones gives the corresponding hydroquinones and diphenyldiphosphine.

Synthesis of polyphosphinoboranes by the reaction of secondary bisphosphines with triethylamineborane

Secondary bisphosphines of general formula, H(C 6H 5)PRP(C 6H 5)H R = (CH 2) 10; ▪; (CH 2) 3O(CH 2) 3; CH 2CH 2(CH 3) 2SiOSi(CH 3) 2CH 2CH 2 have been synthesized by the reaction of phenylphosphine with divinyl compounds. The corresponding polymeric phosphinoboranes have been prepared by heating bisphosphines with triethylamineborane. Polymer properties and molecular chain structures have been discussed. The patents of Hoffmann and Burg and Wagner 1,2 describe the synthesis of polyphosphino boranes from bisphosphines and a diborane and propose a polycyclic structure for the former, but the corresponding data for polymer structure and properties are not given. The present study therefore reports on the reaction of some secondary bisphosphines with triethylamine borane and the investigation of the resulting polymers. It is probable that the molecules of such polymers have a linear structure composed of phosphine borane chains bonded with cross-linking units, rather than a polycyclic structure: ▪