ChemInform Abstract: Alkylation of Diphenylchlorophosphine with Alkyl Halogenides.

Abstract

ChemInform Abstract Reaction of the diphenylchlorophosphine aluminum trichloride complex (I) with n-butyl iodide (II) without a solvent followed by aqueous work-up gives the sec-butyl-(III) and the tert-butylphosphine oxide (IV). In the presence of diethyl ether (V) and benzene, however, a mixture of the ethyl-(VI) and the n-butylphosphine oxide (VII) is obtained.

The reaction of GeCl4 with primary and secondary phosphines

“…An authentic sample of this compound has δ = 84.0 ppm (CDCl 3 ), while others have reported it as 78.7 ppm (C 6 H 6 ). 31 From the filtrate of the reaction mixture we have also obtained a product which X-ray crystallography reveals to be [Ph 2 PH 2 ] ϩ [GeCl 3 ] Ϫ (2). Compound 2 appears to have limited stability, as dissolution of the crystals in CDCl 3 yields a 31 P NMR spectrum comprising in excess of a dozen peaks.…”

“…The only data available for comparison relate to that for [Ph 2 PH 2 ] ϩ [AlCl 4 ] Ϫ , which has δ = Ϫ22.8 ppm and J = 508 Hz. 31 While the reaction described above is reproducible in terms of the NMR spectra of the solid precipitate and the filtrate, crystals of 2 have only been obtained from the reaction filtrate on one occasion.…”

“…Reaction of primary and secondary phosphines with GeCl 4 (1 : 1) does not lead to adduct formation. Rather, in each case a complex series of products is formed as evidenced by 31 P NMR and from which rare examples of primary and secondary phosphonium cations can be isolated. When excess GeCl 4 is reacted with CyPH 2 , a single product, Cy(H)PGeCl 3 , is obtained.…”

“…Elemental analyses were performed using an Exeter Analytical CE 440 analyser. 31 P NMR spectra were recorded on a Bruker Avance 300 MHz FT-NMR spectrometer, using saturated CDCl 3 solutions at room temperature. Glancing-angle XRD measurements were made on a Bruker D8 Advance powder diffractometer equipped with Göbel mirror optics.…”

“…The precursor Cy(H)PGeCl 3 (3) was prepared from CyPH 2 and GeCl 4 (1 : 4) in toluene, as described above. After 30 min, the solvent was removed in vacuo and the residue washed with hexane to remove excess GeCl 4 ; the residue was then re-dissolved in toluene (20 ml) and checked by 31 P NMR, which showed only one doublet resonance at Ϫ61.2 ppm (J = 194 Hz). The precursor, which was used immediately after verification by 31 P NMR, was delivered in the gas phase as an aerosol of the compound dissolved in toluene and swept into the reactor using N 2 as the carrier gas.…”