cyclohexylphosphane

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: Following the procedure of Example 2, 150 parts of monocyclohexyl phosphine are reacted with 190 parts of 40% aqueous glyoxal solution to give 207 parts (92% yield) of 1,4-dicyclohexyl-2,3,5,6-tetrahydroxy-1,4diphosphorinane, m.p. 182°-215° C.

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 2, 150 parts of monocyclohexyl phosphine are reacted with 190 parts of 40% aqueous glyoxal solution to give 207 parts (92% yield) of 1,4-dicyclohexyl-2,3,5,6-tetrahydroxy-1,4diphosphorinane, m.p. 182°-215° C.

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

実験手順: A stirred solution of 23 g. (0.2 mol) of cyclohexylphoshine, 17 g. (0.2 mol) of vinyl acetate and 0.1 g. of azobis-isobutyronitrile in 100 ml. of benzene is prepared and irradiated with ultraviolet light as in Example 1. The temperature is maintained at 25°-30°C. The course of the reaction is followed by observation of the disappearance of the infrared absorption for the vinyl group at 1650 cm.-1After three hours this absorption has disappeared completely and the P-H absorption has shifted from 2450 to 2425 cm.-1 indicating conversion of the primary ##EQU7## absorption to the secondary >P--H. Thus: ##EQU8## To this secondary phosphine intermediate product there is added 18 g. (0.21 mol) of methyl acrylate plus an additional 0.1 g. of azo-bis-isobutyronitrile and irradiation continued under the above conditions for another two hours at which point a scan of the infrared absorption spectrum of the reaction mixture shows the disappearance of the P-H absorption. Removal of the benzene by distillation leaves behind the cyclohexyl-2-acetoxyethyl-2-carbomethoxy ethylphosphine as a colorless, viscous oil. irradiated with ultraviolet light as in Example 1 The temperature is maintained at 25°-30°C The course of the reaction is followed by observation of the disappearance of the infrared absorption for the vinyl group at 1650 cm -1After three hours this absorption the P-H absorption -1 indicating conversion of the primary ##EQU7## absorption to the secondary >P--H Thus: ##EQU8## To this secondary phosphine intermediate product there is added 18 g a scan of the infrared absorption spectrum of the reaction mixture the disappearance of the P-H absorption Removal of the benzene by distillation

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

実験手順: 319 g (1.05 mol) of a 38 wgt % monocyclohexylphosphine solution in toluene was added dropwise at 25° C. to a suspension of 436 g PCl5 (2.1 mol) in 1 liter toluene. After the strongly exothermal reaction was complete, the reaction mixture was filtered using a reverse frit. 5 g orange colored solid matter remained behind. The clear solution (31P-NMR; δ P: 195 ppm, C6H11PCl2, 95 mol %) was distilled under vacuum. After the strongly exothermal reaction the reaction mixture was filtered The clear solution (31P-NMR; δ P: 195 ppm, C6H11PCl2, 95 mol %) was distilled under vacuum

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

実験手順: 4-Bromo-2-nitroaniline (2.17 g, 10 mmol), cyclopropylboronic acid (1.12 g, 1.30 mmol), potassium phosphate (7.42 g, 35 mmol), palladium (II) acetate (120 mg, 0.5 mmol), and cyclohexylphosphine (280 mg, 1 mmol) were combined in toluene (40 mL) and water (2 mL) and heated on an oil bath at 100° C. for 16 hours. The mixture was cooled, and the mixture was triturated with dichloromethane and water. The resulting mixture was filtered through a pad of celite. The organic layer of the filtrate was separated and dried over anhydrous sodium sulfate. Concentration gave an oil that was chromatographed over silica gel (30% v/v diethyl ether in hexanes). The faster moving compound was collected and the solvent was concentrated to give an orange oil. The oil was dissolved in hot hexanes/ethyl acetate and cooling gave 4-cyclopropyl-2-nitroaniline as orange needles (333 mg, 1.87 mmol, 19% ). The mixture was cooled the mixture was triturated with dichloromethane and water The resulting mixture was filtered through a pad of celite The organic layer of the filtrate was separated dried over anhydrous sodium sulfate Concentration gave an oil that was chromatographed over silica gel (30% v/v diethyl ether in hexanes) was collected the solvent was concentrated to give an orange oil cooling

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

実験手順: 4-Bromo-2-nitroaniline (2.17 g, 10 mmol), cyclopropylboronic acid (1.12 g, 1.30 mmol), potassium phosphate (7.42 g, 35 mmol), palladium (II) acetate (120 mg, 0.5 mmol), and cyclohexylphosphine (280 mg, 1 mmol) were combined in toluene (40 mL) and water (2 mL) and heated on an oil bath at 100° C. for 16 hours. The mixture was cooled, and the mixture was triturated with dichloromethane and water. The resulting mixture was filtered through a pad of celite. The organic layer of the filtrate was separated and dried over anhydrous sodium sulfate. Concentration gave an oil that was chromatographed over silica gel (30% v/v diethyl ether in hexanes). The faster moving compound was collected and the solvent was concentrated to give an orange oil. The oil was dissolved in hot hexanes/ethyl acetate and cooling gave 4-cyclopropyl-2-nitroaniline as orange needles (333 mg, 1.87 mmol, 19% ). The mixture was cooled the mixture was triturated with dichloromethane and water The resulting mixture was filtered through a pad of celite The organic layer of the filtrate was separated dried over anhydrous sodium sulfate Concentration gave an oil that was chromatographed over silica gel (30% v/v diethyl ether in hexanes) was collected the solvent was concentrated to give an orange oil cooling

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 2, 150 parts of monocyclohexyl phosphine are reacted with 190 parts of 40% aqueous glyoxal solution to give 207 parts (92% yield) of 1,4-dicyclohexyl-2,3,5,6-tetrahydroxy-1,4-diphosphorinane, m.p. 182°-215° C.

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 2, 150 parts of monocyclohexyl phosphine are reacted with 190 parts of 40% aqueous glyoxal solution to give 207 parts (92% yield) of 1,4-dicyclohexyl-2,3,5,6-tetrahydroxy-1,4-diphosphorinane, m.p. 182°-215° C.

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 2, 150 parts of monocyclohexyl phosphine are reacted with 190 parts of 40% aqueous glyoxal solution to give 207 parts (92% yield) of 1,4-dicyclohexyl-2,3,5,6-tetrahydroxy-1,4-diphosphorinane, m.p. 182-215° C.

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 2, 150 parts of monocyclohexyl phosphine are reacted with 190 parts of 40% aqueous glyoxal solution to give 207 parts (92% yield) of 1,4-dicyclohexyl-2,3,5,6-tetrahydroxy-1,4-diphosphorinane, m.p. 182°-215° C.

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 2, 150 parts of monocyclohexyl phosphine are reacted with 190 parts of 40% aqueous glyoxal solution to give 207 parts (92% yield) of 1,4-dicyclohexyl-2,3,5,6-tetrahydroxy-1,4diphosphorinane, m.p. 182°-215° C.