dimethoxy(phenyl)phosphane

反応条件: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: From a related procedure (Helv. Chim. Acta, 2004, 87, 825) a mixture of methyl 4-bromobenzoate (676 mg, 3.14 mmol), anhydrous NiBr2 (34.3 mg, 0.157 mmol), and PhP(OMe)2 (0.500 mL, 3.14 mmol) was added to a pressure vessel and heated to 160° C. (oil bath temperature) for 2 h. The reaction was cooled, diluted with EtOAc and washed with water (3×), brine, dried (MgSO4) and concentrated to afford ˜800 mg of a clear, colorless oil that solidified upon standing. The product was purified by MPLC (15-50% EtOAc in CH2Cl2) to afford the requisite product: MS: cal'd 291 (MH+), exp 291 (MH+). was added to a pressure vessel The reaction was cooled washed with water (3×), brine dried (MgSO4) concentrated to afford ˜800 mg of a clear, colorless oil that The product was purified by MPLC (15-50% EtOAc in CH2Cl2) to afford the requisite product

反応条件: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: From a related procedure (Helv. Chim. Acta, 2004, 87, 825) a mixture of methyl 4-bromobenzoate (676 mg, 3.14 mmol), anhydrous NiBr2 (34.3 mg, 0.157 mmol), and PhP(OMe)2 (0.500 mL, 3.14 mmol) was added to a pressure vessel and heated to 160° C. (oil bath temperature) for 2 h. The reaction was cooled, diluted with EtOAc and washed with water (3×), brine, dried (MgSO4) and concentrated to afford ˜800 mg of a clear, colorless oil that solidified upon standing. The product was purified by MPLC (15-50% EtOAc in CH2Cl2) to afford the requisite product: MS: cal'd 291 (MH+), exp 291 (MH+). was added to a pressure vessel The reaction was cooled washed with water (3×), brine dried (MgSO4) concentrated to afford ˜800 mg of a clear, colorless oil that The product was purified by MPLC (15-50% EtOAc in CH2Cl2) to afford the requisite product

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 5 grams (29 mmol) of dimethylphenylphosphonite with 7.5 grams (29 mmol) of 3,5-di-tert-butyl-4-hydroxybenzyl chloride (CAS REG #955-01-1) is heated at 110° C. for 1 hour and cooled to obtain a white solid. The resultant solid is crystallized from 100 mL of hexane to give 9 grams (83% yield) of (3,5-di-tert-butyl-4-hydroxy-benzyl)-phenyl-phosphinic acid methyl ester as a white solid mp 112-114° C. cooled to obtain a white solid The resultant solid is crystallized from 100 mL of hexane

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 5 grams (29 mmol) of dimethylphenylphosphonite with 7.5 grams (29 mmol) of 3,5-di-tert-butyl-4-hydroxybenzyl chloride (CAS REG #955-01-1) is heated at 110° C. for 1 hour and cooled to obtain a white solid. The resultant solid is crystallized from 100 mL of hexane to give 9 grams (83% yield) of (3,5-di-tert-butyl-4-hydroxy-benzyl)-phenyl-phosphinic acid methyl ester as a white solid mp 112-114° C. cooled to obtain a white solid The resultant solid is crystallized from 100 mL of hexane

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

実験手順: Methanol (12.8 gm., 0.4 mol.) and triethylamine (40.4 gm., 0.4 mol.) are dissolved in 750 ml. ether and chilled in an ice bath. Phenyl dichlorophosphine (35.8 gm., 0.2 mol.) is added dropwise and the reaction mixture is stirred overnight. The resulting suspension is filtered and the filtrate concentrated to an oil which is distilled in vacuo to give the product, phenylphosphonous acid dimethyl ester, b.p. 100°-105° /10 mm; yield 20 gm. (59%). The resulting suspension is filtered the filtrate concentrated to an oil which is distilled in vacuo

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 5 grams (29 mmol) of dimethylphenylphosphonite with 7.5 grams (29 mmol) of 3,5-di-tert-butyl-4-hydroxybenzyl chloride (CAS REG # 955-01-1) is heated at 110° C. for 1 hour and cooled to obtain a white solid. The resultant solid is crystallized from 100 mL of hexane to give 9 grams (83% yield) of (3,5-di-tert-butyl-4-hydroxy-benzyl)-phenyl-phosphinic acid methyl ester as a white solid mp 112-114° C. cooled to obtain a white solid The resultant solid is crystallized from 100 mL of hexane

反応条件: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a suitable vessel equipped with a stirring means, a temperature measuring means and a material addition means was charged 11 parts dimethylphenylphosphonite, 2.5 parts methyl iodide and 9 parts toluene. The resultant solution was slowly heated. The reaction is exothermic and the temperature increases to about 110° C., the reaction mixture is maintained at a temperature of about 100°-120° C., and an additional 185 parts dimethylphenylphosphonite slowly added. Additional amounts of methyl iodide, in about 1 part increments, are occasionally added during the phosphonite addition. The reaction mixture was maintained at about 110° C. for an additional hour following the addition of components. The reaction mixture was then distilled collecting the portion boiling at 148°-149° C./17 mm. (96 percent yield of methyl phenylmethylphosphinate). [Harwood and Grisley J. Am. Chem. Soc., 82, 423 (1960)]. ##STR3## To a suitable vessel equipped with a stirring means a material addition means the reaction mixture is maintained at a temperature of about 100°-120° C. The reaction mixture was maintained at about 110° C. for an additional hour the addition of components The reaction mixture was then distilled collecting the portion boiling at 148°-149° C./17 mm

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

実験手順: Following the procedure of Example 1, a mixture of 4-(2-chloro-4-trifluoromethylphenoxy)-1,2-dinitrobenzene (2.0 g, 5.52 mmol) and dimethyl phenylphosphonite (1.4 g, 8.28 mmol) in 4 ml of acetonitrile is heated under reflux overnight. The crude product is purified to yield methyl P-phenyl-2-nitro-5-(2-chloro-4-trifluoromethylphenoxy)phenylphosphinate, m/s 471 (M+). is heated under reflux overnight The crude product is purified

反応条件: temp:160.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: From a related procedure (Helv. Chim. Acta, 2004, 87, 825) a mixture of methyl 4-bromobenzoate (676 mg, 3.14 mmol), anhydrous NiBr2 (34.3 mg, 0.157 mmol), and PhP(OMe)2 (0.500 mL, 3.14 mmol) was added to a pressure vessel and heated to 160° C. (oil bath temperature) for 2 h. The reaction was cooled, diluted with EtOAc and washed with water (3×), brine, dried (MgSO4) and concentrated to afford ˜800 mg of a clear, colorless oil that solidified upon standing. The product was purified by MPLC (15-50% EtOAc in CH2Cl2) to afford the requisite product: MS: cal'd 291 (MH+), exp 291 (MH+). was added to a pressure vessel The reaction was cooled washed with water (3×), brine dried (MgSO4) concentrated to afford ˜800 mg of a clear, colorless oil that The product was purified by MPLC (15-50% EtOAc in CH2Cl2) to afford the requisite product