Dimethyl phenylphosphonite

The reactions of dimethyl phenylphosphonite with acid chlorides, a-halogeno-ketones, and iV-(bromomethyl)phthalimide have been used to prepare acyl phos-phinates, /3-keto-alkylphosphinates, and phthalimidomethylphosphinates as intermediates in the synthesis of a-diazophosphinic esters.39 a-Amino-phosphonates have also been prepared by the addition of secondary phosphites to nitriles40 and to isocyanides.41... 

To improve the preparative method of phospha sugars from sugar starting materials [21,22], the Arbzov reaction and Grignard coupling reaction have been applied to a reaction of 1,4-dibromobutane. The reaction of 1,4-dibromobutane (53) with dimethyl phenylphosphonite to give ethyl (4-bromobutyl)phenylphosphinate (54) and successive intramolecular substitution of the 4-bromo substituent with phosphinyl anion affords 1-phenyl -phospholane 1-oxide (56a) in 40% yield. It can also be prepared from... 

At — 50°C, dimethyl phenylphosphonite and the nitro-olefin (101) give the phosphorane (102), which decomposes above 90 °C to give both the phosphinate... 

A 2-nitroalkylphosphinic ester (40) has been obtained by the interaction of dimethyl phenylphosphonite and a-nitroisopentene, although the true nature of the intermediate is open to question. The phosphinate (41) is obtained from p-benzo-quinone and tetramethyldiphosphine disulphide. Conventional reactions have been employed in the preparation of the macrocyclic compounds (42) and the perhydro-1,2-azaphosphorines (43). ... 

The reactions which occur between benzothiete and phosphorus(III) trichloride (followed by alcoholysis), or trialkyl phosphite, or dimethyl phenylphosphonite, lead to the compounds (128)-(130), and the novel heterocyclic compounds... 

Methyl methyl(phenyl)phosphinite 255 Dimethyl phenylphosphonite (100 g) is dropped slowly into a stirred solution of a few drops of methyl iodide in methyl methyl(phenyl)-phosphinite (9 g) at 100-120°. Occasionally a few further drops of methyl idoide must be added later. When the addition is complete, distillation in a vacuum affords the product (100 g, 92%), b.p. 119°/3.5mm, tid25 8 1.5260 (the refractive index decreases sharply on storage in air). 

Related reactions in the oxygen series were first observed only recently as complications in Michaelis-Arbuzov reactions. The 2-halo-alkyl phosphate and phosphonate esters which occur as intermediates in the Michaelis-Arbuzov reaction of certain cyclic phosphites and phos-phonites (cf. Section II-A-1) undergo an internal alkyl exchange reaction (eq. 4) (176). Although reaction of 8-bromoethyl acetate with triethyl phosphite is said to furnish the expected product, diethyl fi-acetoxyethylphosphonate, in 28% yield (220), reaction of this same alkyl halide with dimethyl phenylphosphonite (129) gave the expected methyl phenyl(/9-acetoxyethyl)phosphinate in not greater than 5% yield (eq. 6). Instead, the major products were d-acetoxyethyl phenyl-(methyl)phosphinate (60%) (12) and a mixture of ethylene bi [phenyl-(methyl)phosphinate], [CH20P(0)(Me)Ph]2, (13) and an, ester of... 

A detailed study of the interaction of dimethyl phenylphosphonite (62 R = Ph) and ( )-63 (R = Pr ) initially showed that, at -50 °C only traces of unsaturated phosphinate and dimethyl phenylphosphonate are formed, and that the phosphorane 66 (R = Ph, R = Pr ) is the main produc In outline, the system of observed reactions resembles that observed for trimethyl phosphite, with the formation of the dipolar species 65 in equilibrium with the phosphorane 66 and with the ylide 67 the last acts as the immediate precursor to the methyl [(alk-2-enyl)phenyl]phosphinates 68 (R = Ph). Although hydrolysis of the phosphorane could be expected to yield the methyl [(nitroalkyl)phenyl]phosphinates... 

OgNjCigHig, Acetic acid (1,2-ethanediyl-dinitTilo)tetra-, molybdenum complexes, 29 256,259 OgNiP4C32H44, Nickel(0), Tetrakis(dimethyl phenylphosphonite)-, 28 101... 

Similar nucleophilic substitution at phosphorus with the loss of alkoxide instead of halide vide supra) also occurs readily. Thus, under a nitrogen atmosphere (to avoid oxidation at phosphorus) when four or more equivalents of phenylmagnesium bromide are treated with trimethyl phosphite (Equation 10.75), triphenylphosphine is cleanly obtained. However, if three or fewer equivalents of the same Grignard reagent are used, then dimethyl phenylphosphonite, methyl diphenylphosphinite, and triphenylphosphine are all found (Equation 10.76) with the exact ratio being. 

NiNsP2F,2C2oHj4, Nickel(II), [2,12 methyl-3,l l-bis[l-(methylamino)ethylidene]-1, S,9,13-tetraazacyclohexadeca-1,4,9,12-tetraene- c Af - - - ]-, bis[hexafluoro-phosphate(l —)], 27 266 NiO,P4C32H44, Nickel(0), Tetrakis(dimethyl phenylphosphonite)-, 28 101 NiO Os3C 4H3, Osmium, nonacarbonyl(q -cycIopentadienyl)tri-/i-hydrido-nickeitri-, 26 362... 

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