dichloro(phenyl)phosphane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: P-CARBOXYPHENYL-PHENYLPHOSPHINIC ACID IS ALREADY KNOWN AND HAS BEEN PREPARED BY L. D. Quinn et al. with unsatisfactory yields (L. D. Quinn et al., J. org. Chem. 27, 4120 (1962): ##STR2## In this process, the reaction product of phenyldichlorophosphine and p-cyanophenyl-diazonium-tetrafluoroborate has to be subjected to a reduction with aluminum in order to obtain the p-cyanophenyl-phenylchlorophosphine. The yield is 47 % of the theoretical yield. This process can be carried out only with difficulty on a large scale, and the formation of large amounts of fluorine containing waste secondary products creates the problem of the pollution-free destruction thereof. PREPARED BY L Quinn et al. with unsatisfactory yields (L

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The starting material, butyl phenylphosphonochloridate, was prepared from dichlorophenylphosphine as follows: To a cold, stirred solution of 30.0 g of butanol and 41.4 g of trtiethylamine in about 300 ml of ethyl ether was added dropwise a solution of 34.6 g of dichlorophenylphosphine in about 200 ml of ethyl ether while the temperature was maintained below 0°. When addition was completed, the mixture was allowed to warm to room temperature. Stirring was continued overnight. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The residual oil was distilled under reduced pressure to give 39.5 g of dibutyl phenylphosphonite, b.p. 120°-131°/ca 1.0 mm. Chlorine gas was bubbled into 38.5 g of dibutyl phenylphosphonite for about three hours. The mixture was warmed to 50° under aspirator vacuum to remove butyl chloride. The residual colorless oil was dissolved in 100 ml of benzene, washed with 1% sodium hydroxide and with water, dried over magnesium sulfate, and the dried solution concentrated under reduced pressure to give 30.6 g of pale yellow butyl phenylphosphonochloridate. was maintained below 0° When addition The mixture was filtered the filtrate was concentrated under reduced pressure The residual oil was distilled under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The starting material, butyl phenylphosphonochloridate, was prepared from dichlorophenylphosphine as follows: To a cold, stirred solution of 30.0 g of butanol and 41.4 g of trtiethylamine in about 300 ml of ethyl ether was added dropwise a solution of 34.6 g of dichlorophenylphosphine in about 200 ml of ethyl ether while the temperature was maintained below 0°. When addition was completed, the mixture was allowed to warm to room temperature. Stirring was continued overnight. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The residual oil was distilled under reduced pressure to give 39.5 g of dibutyl phenylphosphonite, b.p. 120°-131°/ca 1.0 mm. Chlorine gas was bubbled into 38.5 g of dibutyl phenylphosphonite for about three hours. The mixture was warmed to 50° under aspirator vacuum to remove butyl chloride. The residual colorless oil was dissolved in 100 ml of benzene, washed with 1% sodium hydroxide and with water, dried over magnesium sulfate, and the dried solution concentrated under reduced pressure to give 30.6 g of pale yellow butyl phenylphosphonochloridate. was maintained below 0° When addition The mixture was filtered the filtrate was concentrated under reduced pressure The residual oil was distilled under reduced pressure

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In the case where X=0 and m=3 in the compounds of the formula (A), the compound is triphenylphosphine oxide, when n=3 in the compounds of the formula (B), the result is phosphorus trichloride. The reaction of triphenylphosphine oxide with phosphorus trichloride initially gives chloro(diphenyl)phosphine oxide (=diphenylphosphinic chloride) and dichloro(phenyl)phosphine: ##STR2## The dichloro(phenyl)phosphine can react with further triphenylphosphine oxide to give chloro(diphenyl)phosphine oxide (=diphenylphosphinic chloride) and chloro(diphenyl)phosphine: ##STR3## The more phenyl groups in the starting compounds (A) and the more Cl in the other starting compounds (B), the better the reaction takes place. No exemplary embodiment of the reaction of, for example, dichloro(phenyl)phosphine oxide (=compound of the formula (A) with X=0 and m=1; =phenylphosphonic dichloride) with chloro(diphenyl)phosphine (=compound of the formula B) with n=1) is contained in the German patent.

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In the case where X=0 and m=3 in the compounds of the formula (A), the compound is triphenylphosphine oxide, when n=3 in the compounds of the formula (B), the result is phosphorus trichloride. The reaction of triphenylphosphine oxide with phosphorus trichloride initially gives chloro(diphenyl)phosphine oxide (=diphenylphosphinic chloride) and dichloro(phenyl)phosphine: ##STR2## The dichloro(phenyl)phosphine can react with further triphenylphosphine oxide to give chloro(diphenyl)phosphine oxide (=diphenylphosphinic chloride) and chloro(diphenyl)phosphine: ##STR3## The more phenyl groups in the starting compounds (A) and the more Cl in the other starting compounds (B), the better the reaction takes place. No exemplary embodiment of the reaction of, for example, dichloro(phenyl)phosphine oxide (=compound of the formula (A) with X=0 and m=1; =phenylphosphonic dichloride) with chloro(diphenyl)phosphine (=compound of the formula B) with n=1) is contained in the German patent.