triethyl ethane-1,1,2-tricarboxylate

反応条件: temp:0.00; pressure:0.00; stir:

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: To a solution of 1.8 g of 2-chloro-3-nitro-5-(trifluoromethyl)pyridine in 8 mL of tetrahydrofuran, 2.0 mL of triethyl 1,1,2-ethanetricarboxylate and 0.63 g of 60% sodium hydroxide were added under cooling with ice, and the mixture was stirred at room temperature for 2 hours. Thereto were added water and ethyl acetate, the organic layer was separated, and washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 3.5 g of triethyl 1-(3-nitro-5-(trifluoromethyl)pyridin-2-yl)ethane-1,1,2-tricarboxylate as a brown oily substance. under cooling with ice the organic layer was separated washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure

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

実験手順: Sodium hydride (21 gram, 0.482 mole) was added to 200 ml dimethylformamide at 20° C. under nitrogen atmosphere. Then 80 grams (0.325 mole) of triethyl ethane-1,1,2-tricarboxylate (compound [3] made in example I) was added to the solution at a temperature of below 30° C. The reaction mixture was maintained at room temperature for 4 hours and 52 ml (0.482 mole) of isobutyl bromide (R2-X) was added drop wise after which the reaction mixture was stirred for another 20 hours at room temperature. When the reaction was complete 1 liter of cold water was added and the organic materials were extracted with dichloromethane (500 ml). The organic extracts were dried over sodium sulfate filtered and evaporated to give an oily substance, which was vacuum distilled to give 88 gram (89% of the theoretical maximum yield) triethyl 4-methylpentane-1,2,2-tricarboxylate, compound [4]. was added the organic materials were extracted with dichloromethane (500 ml) The organic extracts were dried over sodium sulfate filtered evaporated to give an oily substance, which distilled to give 88 gram (89% of the theoretical

反応条件: temp:15.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium metal (23 gram, 1 mole) was dissolved in dry ethanol (500 ml) with stirring. To this 160 gram (1 mole) of diethyl malonate (compound [2]) was added in 30 minutes. The reaction mixture was cooled to 15° C. and ethyl chloroacetate (compound [1], 117 gm, 0.095 mole) was then added drop wise in 30 minutes. On completion of addition the reaction mass was refluxed for 6 hours and then poured in 2 liters of water. The organic materials were extracted with dichloromethane (three times with 500 ml). Next, the organic extracts were dried over sodium sulfate, filtered and evaporated to give an oily substance which was then vacuum distilled to give 220 gm (89% of the theoretical maximum yield) of triethyl ethane-1,1,2-tricarboxylate, compound [3]. On completion of addition the reaction mass was refluxed for 6 hours The organic materials were extracted with dichloromethane (three times with 500 ml) Next, the organic extracts were dried over sodium sulfate filtered evaporated to give an oily substance which vacuum distilled to give 220 gm (89% of the theoretical

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

実験手順: To a solution of triethyl 1,1,2-ethanetricarboxylate (1.36 g) in 3 ml of methanol, a freshly prepared solution of sodium methoxide (from 0.126 g of sodium and 6 ml of absolute methanol) is added. The mixture is heated to 80°. A solution of dimethyl trans-(3-methyl-3-hydroxy-1-octenyl)cyclopropane-1-1-dicarboxylate (1.7 g) is gradually added and the resulting mixture stirred for an additional 15 min. The methanol is removed by distillation at reduced pressure. The residue is then heated at 100° for 45 min. Thereafter the mixture is cooled in an ice bath and rendered neutral with acetic acid. The mixture is extracted with ether. The extract is dried (Na2SO4) and concentrated. Chromatography of the residue on silica gel using ethyl acetate-benzene (1:4) as eluant gives the title compound, νmaxfilm 3350, 1727 cm-1. The mixture is heated to 80° The methanol is removed by distillation at reduced pressure The residue is then heated at 100° for 45 min Thereafter the mixture is cooled in an ice bath The mixture is extracted with ether The extract is dried (Na2SO4) concentrated

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

実験手順: A reaction mixture comprising 49.2 g of triethyl 1,1,2-ethanetricarboxylate, 135 ml of 5N sodium hydroxide and 65 ml of water was stirred at 100° C. for 3 hours, then cooled and concentrated to about 150 ml. A 50 ml portion of cold concentrated hydrochloric acid was added and the mixture was extracted three times with ether. The ether extracts were combined, dried and evaporated, giving 12.5 g of 1,1,2-ethanetricarboxylic acid, mp 169°-170° C. cooled concentrated to about 150 ml A 50 ml portion of cold concentrated hydrochloric acid was added the mixture was extracted three times with ether dried evaporated

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

実験手順: A reaction mixture comprising 49.2 g of triethyl 1,1,2-ethanetricarboxylate, 135 ml of 5N sodium hydroxide and 65 ml of water was stirred at 100° C. for 3 hours, then cooled and concentrated to about 150 ml. A 50 ml portion of cold concentrated hydrochloric acid was added and the mixture was extracted three times with ether. The ether extracts were combined, dried and evaporated, giving 12.5 g of 1,1,2-ethanetricarboxylic acid, mp 169°-170° C. cooled concentrated to about 150 ml A 50 ml portion of cold concentrated hydrochloric acid was added the mixture was extracted three times with ether dried evaporated

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

実験手順: To a solution of sodium ethoxide [prepared from sodium metal (1.6 g) and ethanol] was added thiourea (5.28 g) and triethyl 1,1,2-ethane tricarboxylate (17 g). The mixture was heated under reflux for 8 hours. The solution was cooled to room temperature and the solid collected by filtration, washed with a little ether. The solid was dissolved in water (100 ml) and the pH adjusted to 6-7 by the addition of hydrochloric acid. No solid was precipitated therefore the solution was lyophilised to give a pink solid (8.1 g) The mixture was heated under reflux for 8 hours the solid collected by filtration washed with a little ether The solid was dissolved in water (100 ml) the pH adjusted to 6-7 by the addition of hydrochloric acid No solid was precipitated

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

実験手順: To a solution of triethyl 1,1,2-ethanetricarboxylate (1.36 g) in 3 ml of methanol, a freshly prepared solution of sodium methoxide (from 0.126 g of sodium and 6 ml of absolute methanol) is added. The mixture is heated to 80°. A solution of dimethyl trans-(3-methyl-3-hydroxy-1-octenyl)cyclopropane-1-1-dicarboxylate (1.7 g) is gradually added and the resulting mixture stirred for an additional 15 min. The methanol is removed by distillation at reduced pressure. The residue is then heated at 100° for 45 min. Thereafter the mixture is cooled in an ice bath and rendered neutral with acetic acid. The mixture is extracted with ether. The extract is dried (Na2SO4) and concentrated. Chromatography of the residue on silica gel using ethyl acetate/benzene (1:4) as eluant gives the title compound, νmaxfilm 3350, 1727 cm-1. The mixture is heated to 80° The methanol is removed by distillation at reduced pressure The residue is then heated at 100° for 45 min Thereafter the mixture is cooled in an ice bath The mixture is extracted with ether The extract is dried (Na2SO4) concentrated

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

実験手順: To a solution of triethyl 1,1,2-ethanetricarboxylate (1.36 g) in 3 ml of methanol, a freshly prepared solution of sodium methoxide (from 0.126 g of sodium and 6 ml of absolute methanol) is added. The mixture is heated to 80°. A solution of dimethyl trans-(3-methyl-3-hydroxy-1-octenyl)cyclopropane-1-1-dicarboxylate (1.7 g) is gradually added and the resulting mixture stirred for an additional 15 min. The methanol is removed by distillation at reduced pressure. The residue is then heated at 100° for 45 min. Thereafter the mixture is cooled in an ice bath and rendered neutral with acetic acid. The mixture is extracted with ether. The extract is dried (Na2SO4) and concentrated. Chromatography of the residue on silica gel using ethyl acetate/benzene (1:4) as eluant gives the title compound, νmaxfilm 3350, 1727 cm-1. The mixture is heated to 80° The methanol is removed by distillation at reduced pressure The residue is then heated at 100° for 45 min Thereafter the mixture is cooled in an ice bath The mixture is extracted with ether The extract is dried (Na2SO4) concentrated

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

実験手順: To a solution of 1.8 g of 2-chloro-3-nitro-5-(trifluoromethyl)pyridine in 8 mL of tetrahydrofuran, 2.0 mL of triethyl 1,1,2-ethanetricarboxylate and 0.63 g of 60% sodium hydroxide were added under cooling with ice, and the mixture was stirred at room temperature for 2 hours. Thereto were added water and ethyl acetate, the organic layer was separated, and washed with a saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 3.5 g of triethyl 1-(3-nitro-5-(trifluoromethyl)pyridin-2-yl)ethane-1,1,2-tricarboxylate as a brown oily substance. under cooling with ice the organic layer was separated washed with a saturated aqueous sodium chloride solution dried over anhydrous magnesium sulfate the solvent was distilled off under reduced pressure