ethoxy(diphenyl)phosphane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2.06 grams (7.84 mmol) of 2-(4-fluoro-3-methyl-phenyl)-4,6-dimethylbenzyl chloride was treated with ethyldiphenylphosphinite (2.08 grams, 9.01 mmol) and heated to 150° C. for 3 hrs. After cooling to room temperature, the crude mixture was purified by silicagel chromatography ((10% acetone/90% methylene chloride) and the appropriate fractions concentrated and recrystallized from ether/hexane to provide the title compound (MP 109-111° C.). After cooling to room temperature the crude mixture was purified by silicagel chromatography ((10% acetone/90% methylene chloride) the appropriate fractions concentrated recrystallized from ether/hexane

Conditions: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2.90 grams (12 mmol) of 2-(4-fluoro-3-methyl-phenyl)-4,6-dimethylbenzaldehyde (prepared according to Stokker, Journ. Med. Chem., Vol. 29 p.170, 1986) was reduced with 0.454 grams (12 mmol) of sodium borohydride in ethanol (20 mL) at 0° C. The reaction was stirred 1 hr, quenched with aqueous ammonium chloride and the mixture extracted with ether. The organic portion was dried (MgSO4) and concentrated to give 2.90 grams of 2-(4-fluoro-3-methyl-phenyl)-4,6-dimethylbenzyl alcohol as an oil which solidified on standing. The crude solid was treated with 1.31 nL of thionyl chloride and heated on a steam bath for 1 hour. After cooling to room temperature, the crude mixture was taken up in water and extracted with ether. The ether was washed with water and dried(MgSO4), and concentrated to give an oily residue which was purified by silica gel chromatography (25% methylene chloride/75% hexane) to give 2.70 grams (85.6%) of 2-(4-fluoro-3-methylphenyl)4,6-dimethylbenzyl chloride as a solid. 2.06 grams (7.84 mmol) of 2-(4-fluoro-3-methyl-phenyl)-4,6-dimethylbenzyl chloride was treated with ethyldiphenylphosphinite (2.08 grams, 9.01 mmol) and heated to 150° C. for 3 hrs. After cooling to room temperature, the crude mixture was purified by silicagel chromatography (10% acetone/90% methylene chloride) and the appropriate fractions concentrated and recrystallized from ether/hexane to provide the above-titled compound. MP 109-111° C. After cooling to room temperature the crude mixture was purified by silicagel chromatography (10% acetone/90% methylene chloride) the appropriate fractions concentrated recrystallized from ether/hexane

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: When a mixture of 0.50 mole of ethyl diphenylphosphinite 0.55 mole of n-butyraldehyde, and 0.25 mole of urea in 150 ml of chlorobenzene is warmed at 110° C. for 3 hr, there is only a slow reaction. The mixture is cooled to room temperature and 0.25 mole of acetic acid is added dropwise in ~10 minutes. The temperature increases to 65° during this addition; the urea dissolves and then a white solid product separates. The addition of another 0.25 mole of acetic acid causes no additional heat of reaction. The reaction mixture is warmed at 65°-80° for 9.5 hr and filtered, giving 44.4g. Recrystallization from ethylene glycol gives 26.5g of a white solid: mp 241°-244°; 31P nmr (CF3CO2H) -44.4 ppm; ms M+ = 316 (theory 316). a slow reaction The mixture is cooled to room temperature The temperature increases to 65° during this addition no additional heat of reaction The reaction mixture is warmed at 65°-80° for 9.5 hr filtered giving 44.4g Recrystallization from ethylene glycol

Conditions: temp:110.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: When a mixture of 0.50 mole of ethyl diphenylphosphinite 0.55 mole of n-butyraldehyde, and 0.25 mole of urea in 150 ml of chlorobenzene is warmed at 110° C. for 3 hr, there is only a slow reaction. The mixture is cooled to room temperature and 0.25 mole of acetic acid is added dropwise in ~10 minutes. The temperature increases to 65° during this addition; the urea dissolves and then a white solid product separates. The addition of another 0.25 mole of acetic acid causes no additional heat of reaction. The reaction mixture is warmed at 65°-80° for 9.5 hr and filtered, giving 44.4g. Recrystallization from ethylene glycol gives 26.5g of a white solid: mp 241°-244°; 31P nmr (CF3CO2H) -44.4 ppm; ms M+ = 316 (theory 316). a slow reaction The mixture is cooled to room temperature The temperature increases to 65° during this addition no additional heat of reaction The reaction mixture is warmed at 65°-80° for 9.5 hr filtered giving 44.4g Recrystallization from ethylene glycol

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of phenylphosphonous dichloride (66 g, 0.37 mol) in dry ether (100 mL) was treated dropwise with a solution of ethanol (21.6 mL, 0.37 mol) and pyridine (29.6 mL) was added slowly. The reaction mixture was filtered, washed with ether, and the ether evaporated to give an oil. The oil was distilled in the Kugelrohr and then through a short Vigreux column at 95°-98° C. (0.05 mmHg); lit. (T. L. Emmick et al., J. Am. Chem. Soc., 1968, 90, 3459) 102103° C. (0.2 mmHg). Yield 44.3 g (70%). 1H NMR (CDCl3) δ 7.57 (d, J=569 Hz, 1 H), 8.0-7.4 (m, 5 H), 4.13 (2 q, JH-H =7 Hz, JP-H =14 Hz, 2 H), 1.35 (t, J=7 Hz, 3 H). was added slowly The reaction mixture was filtered washed with ether the ether evaporated to give an oil The oil was distilled in the Kugelrohr at 95°-98° C. lit. (T. L. Emmick et al., J. Am. Chem. Soc., 1968, 90, 3459) 102103° C. (0.2 mmHg)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of phenylphosphonous dichloride (66 g, 0.37 mol) in dry ether (100 mL) was treated dropwise with a solution of ethanol (21.6 mL, 0.37 mol) and pyridine (29.6 mL) was added slowly. The reaction mixture was filtered, washed with ether, and the ether evaporated to give an oil. The oil was distilled in the Kugelrohr and then through a short Vigreux column at 95°-98° C. (0.05 mmHg); lit. (T. L. Emmick et al., J. Am. Chem. Soc., 1968, 90, 3459) 102103° C. (0.2 mmHg). Yield 44.3 g (70%). 1H NMR (CDCl3) δ 7.57 (d, J=569 Hz, 1 H), 8.0-7.4 (m, 5 H), 4.13 (2 q, JH-H =7 Hz, JP-H =14 Hz, 2 H), 1.35 (t, J=7 Hz, 3 H). was added slowly The reaction mixture was filtered washed with ether the ether evaporated to give an oil The oil was distilled in the Kugelrohr at 95°-98° C. lit. (T. L. Emmick et al., J. Am. Chem. Soc., 1968, 90, 3459) 102103° C. (0.2 mmHg)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of diphenylphosphinous chloride (135 mmol) in dry ether (120 mL) was treated dropwise at 5° C. with a solution of ethanol (200 mmol) and pyridine (134 mmol) in ether (120 mL). After addition was complete, the mixture was warmed to room temperature, filtered under argon, and the solid hydrochloride washed with ether. Evaporation of the solvent gave an oil which was purified by Kugelrohr distillation at 95° C. (0.1 mmHg). Yield: 119 mmol (88%); 1H NMR (CDCl3) δ 7.6-7.2 (m, 10 H), 3.95 (doublet of quartets, JH-H =7 Hz, JP-H =10 Hz, 2 H), 1.30 (t, J=7 Hz, 3 H). After addition filtered under argon the solid hydrochloride washed with ether Evaporation of the solvent gave an oil which was purified by Kugelrohr distillation at 95° C. (0.1 mmHg)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of diphenylphosphinous chloride (135 mmol) in dry ether (120 mL) was treated dropwise at 5° C. with a solution of ethanol (200 mmol) and pyridine (134 mmol) in ether (120 mL). After addition was complete, the mixture was warmed to room temperature, filtered under argon, and the solid hydrochloride washed with ether. Evaporation of the solvent gave an oil which was purified by Kugelrohr distillation at 95° C. (0.1 mmHg). Yield: 119 mmol (88%); 1H NMR (CDCl3) δ 7.6-7.2 (m, 10 H), 3.95 (doublet of quartets, JH-H =7 Hz, JP-H =10 Hz, 2 H), 1.30 (t, J=7 Hz, 3 H). After addition filtered under argon the solid hydrochloride washed with ether Evaporation of the solvent gave an oil which was purified by Kugelrohr distillation at 95° C. (0.1 mmHg)