Methoxydiphenylphosphine

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

Procedure: To a stirred, refluxing solution of 3.00 g of 3,6-dichloropyridazine in 50 ml of o-dichlorobenzene under nitrogen was added dropwise 10.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 7 hours and then cooled. The cooled mixture was mixed with excess hexane; the oil which formed slowly crystallized. The resultant solid was separated by filtration, washed with hexane, and recrystallized twice from ethanol with decolorizing charcoal treatment to give 0.93 g of 3,6-bis(diphenylphosphinyl)pyridazine (shown by formula in claim 7) as slightly off-white crystals, mp 248°-251.5° C. Anal. Calcd for C28H22N2O2P2 : C, 70.00; H, 4.62; N, 5.83; P, 12.89. Found: C, 69.72; H, 4.92; N, 5.78; P, 12.82. After the addition the mixture was refluxed for 7 hours cooled the oil which formed slowly crystallized The resultant solid was separated by filtration washed with hexane recrystallized twice from ethanol with decolorizing charcoal treatment

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

Procedure: To a stirred, refluxing mixture of 5.00 g of 1,4-dichlorophthalazine in 50 ml of o-dichlorobenzene under nitrogen was added dropwise 15.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 6 hours and then allowed to stand at room temperature for 13 days. The resulting solid was separated by filtration, washed with benzene and with hexane, recrystallized from 125 ml of toluene with decolorizing charcoal treatment, and dried at 100° C./0.1 mm (13 Pa) to give 6.41 g of 1,4-bis(diphenylphosphinyl)phthalazine (shown by formula in claim 6) as a light-yellow solid, mp 225°-228.5° C. Anal. Calcd for C32H24N2O2P2 : C, 72.45; H, 4.56; N, 5.28; P, 11.68. Found: C, 72.49; H, 4.62; N, 5.36; P, 11.95. To a stirred, refluxing After the addition the mixture was refluxed for 6 hours The resulting solid was separated by filtration washed with benzene and with hexane recrystallized from 125 ml of toluene with decolorizing charcoal treatment dried at 100° C./0.1 mm (13 Pa)

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

Procedure: To a stirred, refluxing mixture of 5.00 g of 2,4,6-trichloropyrimidine in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 26.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 6.5 hours and then allowed to stand overnight at room temperature. The next day a small amount of the solvent was removed by boiling, and the solution was allowed to stand again overnight. The next day the resulting solid was separated by filtration, washed twice with benzene and three times with hexane, recrystallized from 650 ml of toluene, and dried at 100° C./0.1 mm (13 Pa) to give 11.35 g of 2,4,6-tris(diphenylphosphinyl)pyrimidine as a white solid, mp 235°-236° C. Anal. Calcd for C40H31N2O3P3 : C, 70.59; H, 4.59; N, 4.12; P, 13.65. Found: C, 70.72; H, 4.90; N, 3.92; P, 13.61. To a stirred, refluxing After the addition the mixture was refluxed for 6.5 hours The next day a small amount of the solvent was removed to stand again overnight The next day the resulting solid was separated by filtration washed twice with benzene and three times with hexane recrystallized from 650 ml of toluene dried at 100° C./0.1 mm (13 Pa)

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

Procedure: To a stirred, refluxing mixture of 5.00 g of 2,4,6-trichloropyrimidine in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 26.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 6.5 hours and then allowed to stand overnight at room temperature. The next day a small amount of the solvent was removed by boiling, and the solution was allowed to stand again overnight. The next day the resulting solid was separated by filtration, washed twice with benzene and three times with hexane, recrystallized from 650 ml of toluene, and dried at 100° C./0.1 mm (13 Pa) to give 11.35 g of 2,4,6-tris(diphenylphosphinyl)pyrimidine as a white solid, mp 235°-236° C. Anal. Calcd for C40H31N2O3P3 : C, 70.59; H, 4.59; N, 4.12; P, 13.65. Found: C, 70.72; H, 4.90; N, 3.92; P, 13.61. To a stirred, refluxing After the addition the mixture was refluxed for 6.5 hours The next day a small amount of the solvent was removed to stand again overnight The next day the resulting solid was separated by filtration washed twice with benzene and three times with hexane recrystallized from 650 ml of toluene dried at 100° C./0.1 mm (13 Pa)

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

Procedure: To a stirred, refluxing mixture of 5.00 g 4,6-dichloropyrimidine in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 17.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 6.5 hours and then allowed to cool. The cooled mixture was added to 750 ml of n-hexane, and the white solid that formed was separated by filtration, washed with n-hexane, recrystallized from 150 ml of toluene, and dried at 100° C./0.1 mm (13 Pa) to give 13.64 g of 4,6-bis(diphenylphosphinyl)pyrimidine as cream-colored crystals, mp 213°-215° C. Anal. Calcd for C28H22N2O2P2 : C, 70.00; H, 4.62; N, 5.83; P, 12.89. Found: C, 69.80; H, 4.65; N, 5.65; P, 12.89. To a stirred, refluxing After the addition the mixture was refluxed for 6.5 hours to cool the white solid that formed was separated by filtration washed with n-hexane recrystallized from 150 ml of toluene dried at 100° C./0.1 mm (13 Pa)

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

Procedure: To a stirred, refluxing mixture of 5.00 g of 2,3-dichloroquinoxaline in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 14.00 g of methyl diphenylphosphinite. The mixture was refluxed for 6 hours after the addition was completed and then allowed to stand overnight at room temperature. The next day the mixture was admixed with 500 ml of n-hexane, and the resulting solid was separated by filtration, washed with hexane, recrystallized from 100 ml of chlorobenzene, and dried at 100° C./0.1 mm (13 Pa) to give 9.87 g of 2,3-bis(diphenylphosphinyl)quinoxaline (shown by formula in claim 5) as a very slightly yellowish-white solid, mp 258°-272° C. with decomposition. Anal. Calcd for C32H24N2O2P2 : C, 72.45; H, 4.56; N, 5.28; P, 11.68. Found: C, 72.38; H, 4.23; N, 5.18; P, 11.39. To a stirred, refluxing The mixture was refluxed for 6 hours after the addition the resulting solid was separated by filtration washed with hexane recrystallized from 100 ml of chlorobenzene dried at 100° C./0.1 mm (13 Pa)

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

Procedure: To a stirred, refluxing mixture of 5.00 g of 2,3-dichloroquinoxaline in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 14.00 g of methyl diphenylphosphinite. The mixture was refluxed for 6 hours after the addition was completed and then allowed to stand overnight at room temperature. The next day the mixture was admixed with 500 ml of n-hexane, and the resulting solid was separated by filtration, washed with hexane, recrystallized from 100 ml of chlorobenzene, and dried at 100° C./0.1 mm (13 Pa) to give 9.87 g of 2,3-bis(diphenylphosphinyl)quinoxaline (shown by formula in claim 5) as a very slightly yellowish-white solid, mp 258°-272° C. with decomposition. Anal. Calcd for C32H24N2O2P2 : C, 72.45; H, 4.56; N, 5.28; P, 11.68. Found: C, 72.38; H, 4.23; N, 5.18; P, 11.39. To a stirred, refluxing The mixture was refluxed for 6 hours after the addition the resulting solid was separated by filtration washed with hexane recrystallized from 100 ml of chlorobenzene dried at 100° C./0.1 mm (13 Pa)

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

Procedure: To a stirred refluxing solution of 5.00 g of 4,6-dichloro-2-methylthiopyrimidine in 150 ml of o-dichlorobenzene under nitrogen was added dropwise 15.00 g of methyl diphenylphosphinite over 35 minutes. The mixture was refluxed for 5.5 hours after the addition was completed and then allowed to cool, at which time it was added to 850 ml of n-hexane. The resulting solid was separated by filtration, washed with n-hexane, and recrystallized from 100 ml of ethanol to give 11.00 g of 4,6-bis(diphenylphosphinyl)-2-methylthiopyrimidine as white crystals, mp 221°-222° C. Anal. Calcd for C29H24N2O2P2S: C, 66.15; H, 4.59; N, 5.32. Found: C, 65.59, 65.59; H, 4.54, 4.75; N, 5.04, 5.01. The mixture was refluxed for 5.5 hours after the addition to cool, at which time it The resulting solid was separated by filtration washed with n-hexane recrystallized from 100 ml of ethanol

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

Procedure: To a stirred, refluxing mixture of 3.56 g of 5-bromo-4-chloro-2-methylthiopyrimidine in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 10.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 6 hours and then allowed to cool. Volatiles were removed from the mixture under vacuum, and the residue was recrystallized from 30 ml of 1-chlorobutane and dried at 50° C./0.1 mm (13 Pa) to give 2.97 g of 5-bromo-4-diphenylphosphinyl-2-methylthiopyrimidine as white crystals, mp 124°-127° C. Anal. Calcd for C17H14BrN2OPS: C, 50.39; H, 3.48; N, 6.91. Found: C, 50.54; H, 3.67; N, 6.84. To a stirred, refluxing After the addition the mixture was refluxed for 6 hours to cool Volatiles were removed from the mixture under vacuum the residue was recrystallized from 30 ml of 1-chlorobutane dried at 50° C./0.1 mm (13 Pa)

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

Procedure: To a stirred, refluxing mixture of 3.56 g of 5-bromo-4-chloro-2-methylthiopyrimidine in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 10.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 6 hours and then allowed to cool. Volatiles were removed from the mixture under vacuum, and the residue was recrystallized from 30 ml of 1-chlorobutane and dried at 50° C./0.1 mm (13 Pa) to give 2.97 g of 5-bromo-4-diphenylphosphinyl-2-methylthiopyrimidine as white crystals, mp 124°-127° C. Anal. Calcd for C17H14BrN2OPS: C, 50.39; H, 3.48; N, 6.91. Found: C, 50.54; H, 3.67; N, 6.84. To a stirred, refluxing After the addition the mixture was refluxed for 6 hours to cool Volatiles were removed from the mixture under vacuum the residue was recrystallized from 30 ml of 1-chlorobutane dried at 50° C./0.1 mm (13 Pa)

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

Procedure: To a stirred, refluxing solution of 5.00 g of 2,3-dicyano-5,6-dichloropyrazine in 100 ml of o-dichlorobenzene under nitrogen was added dropwise 10.00 g of methyl diphenylphosphinite. After the addition was completed, the mixture was refluxed for 4 hours and then allowed to stand overnight. The resulting solid was separated by filtration, washed with benzene and twice with hexane, recrystallized from 200 ml of o-dichlorobenzene, and dried at 80° C./0.1 mm (13 Pa) to give 8.08 g of 2,3-dicyano-5,6-bis(diphenylphosphinyl)pyrazine (shown by formula in claim 4) as a white solid, decomposition beginning at 210° C. Anal. calcd for C30H20N4O2P2 : C, 67.93; H, 3.80; N, 10.56; P, 11.68. Found: C, 67.77; H, 3.92; N, 10.48; P, 11.18. After the addition the mixture was refluxed for 4 hours The resulting solid was separated by filtration washed with benzene and twice with hexane recrystallized from 200 ml of o-dichlorobenzene dried at 80° C./0.1 mm (13 Pa)

Conditions: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 648 parts of methoxydiphenylphosphine are added slowly to 547.5 parts of 2,4,6-trimethylbenzoyl chloride at 50°-95° C. in a stirred apparatus equipped with a reflux condenser and dropping funnel. The mixture is then stirred for 4-5 hours at 50° C., the contents of the flask are dissolved in ether at 30° C., and petroleum ether is added until the mixture starts to turn cloudy. On cooling, 910 parts (87% of theory) of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide crystallize. Pale yellow crystals, melting point 89°-92° C. equipped with a reflux condenser On cooling 910 parts (87% of theory) of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide crystallize