二乙基氯化膦

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 20.4 g (0.07 mol) of (4-hydroxyimino-cyclohexa-2,5-dienylidene)-2,4-dichlorphenyl-acetonitrile, 7.1 g (0.07 mol) of triethylamine and a catalytic amount of N,N-dimethylaminopyridine are dissolved in 270 ml of THF. This solution is cooled in an ice bath, and 12.1 g (0.07 mol) of diethylphosphoryl chloride are added dropwise while stirring. When the addition is complete, the orange solution is warmed to room temperature and stirred overnight. Water and ethyl acetate are subsequently added, and the organic layer is washed several times with saturated sodium chloride solution and water and dried over magnesium sulfate. Evaporation of the solvent gives 30.4 g of a viscous yellowish oil, which is further purified by filtration over silica gel (eluent: hexane/ethyl acetate 9:1). Yield: 25.5 g (85%). 31P-NMR (CDCl3; δ relative to H3PO4 as external reference): 0.132 and 0.003 ppm (P(V) of the (E) and (Z)-isomers). 1H-NMR (CDCl3, δ [ppm]): 7.60-7.15 (m, 7H); 7.0-6.55 (m, 2H), 4.35-4.15, (m, 4H-C(1′)); 1.38 and 1.35 (t, 3H-C(2′)). This solution is cooled in an ice bath When the addition stirred overnight the organic layer is washed several times with saturated sodium chloride solution and water dried over magnesium sulfate Evaporation of the solvent

反应条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 8 g (33 mmol) of (5-Hydroxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile are dissolved in 90 ml of tetrahydrofuran (THF) and cooled in an ice bath. After adding 6.3 g (36 mmol) of diethylphosphoryl chloride to the solution, 5.0 g (50 mmol) of triethylamine are added dropwise, keeping the temperature below 50° C. The reaction mixture is stirred at 5° C. for 60 min., then poured into 100 ml of water, and extracted with ethyl acetate. The organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution. The organic phase is dried over MgSO4, the solvent is distilled off, and the residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:1) as eluent. The product is obtained in the form of a yellow solid, melting point 90-91° C. The structure is confirmed by the 1H-NMR spectrum (CDCl3). δ [ppm]: 1.43 (t, 6H), 2.37 (s, 3H), 4.36-4.47 (m, 4H), 6.13 (d, 1H), 6.86 (d, 1H), 7.19-7.39 (m, 4H). cooled in an ice bath are added dropwise the temperature below 50° C extracted with ethyl acetate The organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution The organic phase is dried over MgSO4 the solvent is distilled off the residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:1) as eluent The product is obtained in the form of a yellow solid, melting point 90-91° C

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 0.58 ml (4.20 mmol) of triethylamine and 0.31 ml (2.10 mmol) of diethylphosphoryl chloride were added to 20 ml of a benzene suspension containing 505 mg (2.10 mmol) of 2-(9H-xanthen-9-yl)acetic acid, and then the mixture was stirred for 1 hour. At the end of this time, 5 ml of a benzene solution containing 587 mg (2.09 mmol) of 2-t-butyl-5-(3-phenyl-3-oxopropyl)aniline (prepared by a procedure similar to that described in Preparation 7), followed by 10 mg of 4-pyrrolidinopyridine, were added to the reaction suspension, and the resulting mixture was heated under reflux for 4.5 hours. The reaction mixture was then diluted with ethyl acetate, washed with dilute aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogen carbonate solution and with a saturated aqueous solution of sodium chloride, in that order. The solvent was then removed by distillation under reduced pressure, and the resulting residue was subjected to column chromatography through silica gel. Elution with a 4:1 by volume mixture of methylene chloride and cyclohexane yielded 934 mg (yield 86%) of the title compound as crystals, melting at 116°-118° C. (after crystallization from diisopropyl ether). prepared by a procedure similar to that described in Preparation 7), were added to the reaction suspension the resulting mixture was heated under reflux for 4.5 hours washed with dilute aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogen carbonate solution and with a saturated aqueous solution of sodium chloride, in that order The solvent was then removed by distillation under reduced pressure Elution with a 4:1 by volume mixture of methylene chloride and cyclohexane yielded

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Diethylphosphorylchloride (150 mg, 0.87 mmol) was added to a solution of EtNiPr2 (129 mg, 1.00 mmol), DMAP (10 mg, 0.08 mmol) and N-(2,4-dimethoxybenzyl)-N-phenyl-1,2-dihydro-4-hydroxy-1-methyl-2-oxo-quinoline-3-carboxamide (222 mg, 050 mmol) in CH2Cl2 (3.0 mL). The reaction mixture was stirred for 30 min and was then concentrated at reduced pressure. The residue was purified by silica column chromatography (EtOAc) to give the title compound (196 mg, 68%). was then concentrated at reduced pressure The residue was purified by silica column chromatography (EtOAc)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 0.58 ml (4.20 mmol) of triethylamine and 0.31 ml (2.10 mmol) of diethylphosphoryl chloride were added to 20 ml of a benzene suspension containing 505 mg (2.10 mmol) of 2-(9H-xanthen-9-yl)acetic acid, and then the mixture was stirred for 1 hour. At the end of this time, 5 ml of a benzene solution containing 587 mg (2.09 mmol) of 2-t-butyl-5-(3-phenyl-3-oxopropyl)aniline (prepared by a procedure similar to that described in Preparation 7), followed by 10 mg of 4-pyrrolidinopyridine, were added to the reaction suspension, and the resulting mixture was heated under reflux for 4.5 hours. The reaction mixture was then diluted with ethyl acetate, washed with dilute aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogen carbonate solution and with a saturated aqueous solution of sodium chloride, in that order. The solvent was then removed by distillation under reduced pressure, and the resulting residue was subjected to column chromatography through silica gel. Elution with a 4:1 by volume mixture of methylene chloride and cyclohexane yielded 934 mg (yield 86%) of the title compound as crystals, melting at 116°-118° C. (after crystallization from diisopropyl ether). prepared by a procedure similar to that described in Preparation 7), were added to the reaction suspension the resulting mixture was heated under reflux for 4.5 hours washed with dilute aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogen carbonate solution and with a saturated aqueous solution of sodium chloride, in that order The solvent was then removed by distillation under reduced pressure Elution with a 4:1 by volume mixture of methylene chloride and cyclohexane yielded

反应条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of p-nitrobenzyl α-(3-benzyl-7-oxo-4-thia-2,6-diazabicyclo[3,2,0]hept-2-en-6-yl)-α-(1-hydroxyethylidene)acetate (4.53 g) containing 4-dimethylaminopyridine (0.1 g) in ethyl acetate (50 ml) under a nitrogen atmosphere at 20° C. was added triethylamine (1.53 ml) followed by diethylphosphoryl chloride (1.59 ml) dropwise. The reaction mixture was stirred at 20° C. for 3 hours. Water (40 ml) was added and the organic layer was separated, washed with water (20 ml) and saturated sodium chloride solution (20 ml), dried with magnesium sulphate and carbon treated, filtered and evaporated to give the title compound as a yellow viscous oil in essentially quantitative yield. TLC (silica) Rf 0.17 (dichloromethane/ethyl acetate 15:2). The product was a mixture of geometric isomers (ca. 2:1) about the enol phosphate double bond. NMR δCDCl3 1.11-1.60 (m, 6H), 1.98+2.60 (d, 3H), 3.73-4.65 (m, 6H), 5.22-5.42 (m, 2H), 5.88-6.28 (m, 2H) and 7.25-7.80 and 8.18-8.58 (m, 9H). the organic layer was separated washed with water (20 ml) and saturated sodium chloride solution (20 ml) dried with magnesium sulphate and carbon treated filtered evaporated

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 20.4 g (0.07 mol) of (4-hydroxyimino-cyclohexa-2,5-dienylidene)-2,4-dichlorphenyl-acetonitrile, 7.1 g (0.07 mol) of triethylamine and a catalytic amount of N,N-dimethylaminopyridine are dissolved in 270 ml of THF. This solution is cooled in an ice bath, and 12.1 g (0.07 mol) of diethylphosphoryl chloride are added dropwise while stirring. When the addition is complete, the orange solution is warmed to room temperature and stirred overnight. Water and ethyl acetate are subsequently added, and the organic layer is washed several times with saturated sodium chloride solution and water and dried over magnesium sulfate. Evaporation of the solvent gives 30.4 g of a viscous yellowish oil, which is further purified by filtration over silica gel (eluent: hexane/ethyl acetate 9:1). Yield: 25.5 g (85%). 31P-NMR (CDCl3; δ relative to H3PO4 as external reference): 0.132 and 0.003 ppm (P(V) of the (E) and (Z)-isomers). 1H-NMR (CDCl3, δ [ppm]): 7.60-7.15 (m, 7H); 7.0-6.55 (m, 2H), 4.35-4.15, (m, 4H-C(1′)); 1.38 and 1.35 (t, 3H-C(2′)). This solution is cooled in an ice bath When the addition stirred overnight the organic layer is washed several times with saturated sodium chloride solution and water dried over magnesium sulfate Evaporation of the solvent

反应条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 8 g (33 mmol) of (5-Hydroxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)-acetonitrile are dissolved in 90 ml of tetrahydrofuran (THF) and cooled in an ice bath. After adding 6.3 g (36 mmol) of diethylphosphoryl chloride to the solution, 5.0 g (50 mmol) of triethylamine are added dropwise, keeping the temperature below 50° C. The reaction mixture is stirred at 5° C. for 60 min., then poured into 100 ml of water, and extracted with ethyl acetate. The organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution. The organic phase is dried over MgSO4, the solvent is distilled off, and the residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:1) as eluent. The product is obtained in the form of a yellow solid, melting point 90-91° C. The structure is confirmed by the 1H-NMR spectrum (CDCl3). δ [ppm]: 1.43 (t, 6H), 2.37 (s, 3H), 4.36-4.47 (m, 4H), 6.13 (d, 1H), 6.86 (d, 1H), 7.19-7.39 (m, 4H). cooled in an ice bath are added dropwise the temperature below 50° C extracted with ethyl acetate The organic phase is washed with 0.1N hydrochloric acid solution, water, and sodium chloride solution The organic phase is dried over MgSO4 the solvent is distilled off the residue is purified by flash chromatography on silica gel with ethyl acetate—hexane (1:1) as eluent The product is obtained in the form of a yellow solid, melting point 90-91° C

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 0.58 ml (4.20 mmol) of triethylamine and 0.31 ml (2.10 mmol) of diethylphosphoryl chloride were added to 20 ml of a benzene suspension containing 505 mg (2.10 mmol) of 2-(9H-xanthen-9-yl)acetic acid, and then the mixture was stirred for 1 hour. At the end of this time, 5 ml of a benzene solution containing 587 mg (2.09 mmol) of 2-t-butyl-5-(3-phenyl-3-oxopropyl)aniline (prepared by a procedure similar to that described in Preparation 7), followed by 10 mg of 4-pyrrolidinopyridine, were added to the reaction suspension, and the resulting mixture was heated under reflux for 4.5 hours. The reaction mixture was then diluted with ethyl acetate, washed with dilute aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogen carbonate solution and with a saturated aqueous solution of sodium chloride, in that order. The solvent was then removed by distillation under reduced pressure, and the resulting residue was subjected to column chromatography through silica gel. Elution with a 4:1 by volume mixture of methylene chloride and cyclohexane yielded 934 mg (yield 86%) of the title compound as crystals, melting at 116°-118° C. (after crystallization from diisopropyl ether). prepared by a procedure similar to that described in Preparation 7), were added to the reaction suspension the resulting mixture was heated under reflux for 4.5 hours washed with dilute aqueous hydrochloric acid, with water, with a saturated aqueous solution of sodium hydrogen carbonate solution and with a saturated aqueous solution of sodium chloride, in that order The solvent was then removed by distillation under reduced pressure Elution with a 4:1 by volume mixture of methylene chloride and cyclohexane yielded