ジ-n-アルキルホスフィンオキシドとハロカルボン酸及びそのエステルとの反応

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The reactions of di-n-alkylphosphine oxides (1) with halocarboxylic acids (2) and their esters (3) were carried out in boiling sodium ethoxide and methoxide solutions, respectively. The products were identified by P%, NV, and IR and MS spectra. Di-n-hexylphosphine oxide (1b) was reacted with haloacetic and 3-halopropionic acids X- (CH2) n-CO2H, (2) (X=Cl, Br; n=1, 2) to give di-n-hexylphosphinic and 3- (di-n-hexylphosphinyl) propionic acids ((4b) and (5b)), respectively. The yield increased with increasing the concentration of sodium ethoxide. Reactions of (1) with methyl bromoacetate and 3-bromopropionate ((3a) and (3b)), followed by alkaline (potassium hydroxide) hydrolysis, gave di-n-alkylphosphinic and 3- (di-n-alkylphosphinyl) propionic acids ((4) and (5)), respectively. In the case of (3a), the optimum condition was (1) : (3a) : [NaOMe] =1 : 1 : 1 (mol/mol/mol), but the yield of (5) increased with increasing concentration of sodium methoxide in the reaction with (3b). The reaction of di-n-heptylphosphine oxide (1c) with ethyl 2-bromobutyrate (1 : 1 : 1) gave 93% of di-n-heptylphosphinic acid (4c), but a trace of (4c) was obtained with ethyl acetate. An intermediate ester, methyl 3- (di-n-hexylphosphinyl) propionate (6b), was isolated in the reaction of (1b) with (3b) (1 : 1 : 2.2, t=5h) without the hydrolysis, and was easily hydrolyzed by potassium hydroxide. For the formation of (4) which is a new oxidation reaction of (1), a mechanism involving a nucleophilic attack of the reactive species R2P (O) Na (7) on the carbonyl carbon of (2) (n=1) or (3a) to give an intermediate enol phosphate analog (9) was proposed and discussed. For the formation of (5), a possible mechanism involving a nucleophilic addition of (7) to the activated olefin produced by the ordinary alkoxide promoted 1, 2-elimination of hydrogen halide from (2) (n=2) or (3b) was proposed and discussed.
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ジ-n-アルキルホスフィンオキシドとハロカルボン酸及びそのエステルとの反応

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