methoxymethyl acetate

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of thymine (100 g, 0.79 mol), trifluoromethanesulfonic acid (2 mL, 20 mmol) and HMDS (418 mL, 1.98 mol) was heated 16 hours with stirring at 90° C. and briefly at reflux and then distilled in vacuo at 80° C. to remove the excess HMDS. The mixture was treated with trifluoromethanesulfonic acid (1.5 mL, 20 mmol) and then methoxymethyl acetate (88 mL, 0.89 mol) was added at a rate such that the reaction temperature did not exceed 95° C. The mixture was heated 20 minutes at 70° C. and then distilled in vacuo to remove the trimethysilyl acetate formed as byproduct. The reaction mixture was poured into isopropanol (800 mL) and stirred 18 hours. The solids were collected, washed with ethyl acetate and dried to give 1-methoxymethyl-5-methyl-2,4(1H,3H)-pyrimidinedione (116 g, 0.68 mol). was heated 16 hours briefly at reflux distilled in vacuo at 80° C. to remove the excess HMDS did not exceed 95° C The mixture was heated 20 minutes at 70° C. distilled in vacuo to remove the trimethysilyl acetate formed as byproduct stirred 18 hours The solids were collected washed with ethyl acetate dried

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under argon, a suspension of 0.5 g of sodium acetate in 60 ml of anhydrous chloroform, 2 ml of distilled phosphorus oxychloride, and 15 ml of methoxymethyl acetate is agitated for 30 minutes at a bath temperature of 60° C. After adding 2.0 g of 17α,21-diacetoxy-4-pregnene-3,20-dione, the mixture is further stirred for 3 hours at 70° C. and worked up analogously to Example 1. The dark crude product is purified on 200 g of silica gel with a hexane-ethyl acetate gradient (0-40% ethyl acetate), yielding 1.15 g of 17α,21-diacetoxy-6-methyl-4,6-pregnadiene-3,20-dione, mp 213°-215° C. the mixture is further stirred for 3 hours at 70° C. The dark crude product is purified on 200 g of silica gel with a hexane-ethyl acetate gradient (0-40% ethyl acetate)

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of 0.5 g of sodium acetate in 60 ml of anhydrous chloroform and 2 ml of distilled phosphorus oxychloride is refluxed under agitation for 30 minutes at a bath temperature of 70° C. After adding 15 ml of methoxymethyl acetate and 2.0 g of 17α-acetoxy-4-pregnene-3,20-dione, the reaction solution is further stirred for 5 hours at 70° C. Subsequently such an amount of a saturated soda solution is added dropwise at room temperature that the aqueous phase remains alkaline. The organic phase is separated, washed with water, and dried over sodium sulfate. After concentration, the crude product is purified on 100 g of silica gel with a hexane-ethyl acetate gradient (0-50% ethyl acetate), thus isolating 1.26 g of 17α-acetoxy-6-methyl-4,6-pregnadiene-3,20-dione, mp 217°-219° C. Subsequently such an amount of a saturated soda solution is added dropwise at room temperature that the aqueous phase The organic phase is separated washed with water dried over sodium sulfate After concentration the crude product is purified on 100 g of silica gel with a hexane-ethyl acetate gradient (0-50% ethyl acetate)

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

実験手順: 50.45 g of 1,3-dipivaloyl glycerol was dissolved in 200 ml of methoxymethyl acetate. After the addition of 2.5 g of p-toluenesulfonic acid monohydrate, the mixture was stirred for 1 hr then diluted with 200 ml of hexane and washed twice with 200 ml saturated aqueous sodium carbonate, once with aqueous NaCl solutions, dried over anhydrous magnesium sulfate and concentrated in vacuo to afford 1,3-dipivaloyl-2-methoxymethyl glycerol as a colorless oil. washed twice with 200 ml saturated aqueous sodium carbonate, once with aqueous NaCl solutions dried over anhydrous magnesium sulfate concentrated in vacuo

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

実験手順: 50.45 g of 1,3-dipivaloyl glycerol was dissolved in 200 ml of methoxymethyl acetate. After the addition of 2.5 g of p-toluenesulfonic acid monohydrate, the mixture was stirred for 1 hr then diluted with 200 ml of hexane and washed twice with 200 ml saturated aqueous sodium carbonate, once with aqueous NaCl solutions, dried over anhydrous magnesium sulfate and concentrated in vacuo to afford 1,3-dipivaloyl-2-methoxymethyl glycerol as a colorless oil. washed twice with 200 ml saturated aqueous sodium carbonate, once with aqueous NaCl solutions dried over anhydrous magnesium sulfate concentrated in vacuo

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of thymine (100 g, 0.79 mol), trifluoromethanesulfonic acid (2 mL, 20 mmol) and HMDS (418 mL, 1.98 mol) was heated 16 hours with stirring at 90° C. and briefly at reflux and then distilled in vacuo at 80° C. to remove the excess HMDS. The mixture was treated with trifluoromethanesulfonic acid (1.5 mL, 20 mmol) and then methoxymethyl acetate (88 mL, 0.89 mol) was added at a rate such that the reaction temperature did not exceed 95° C. The mixture was heated 20 minutes at 70° C. and then distilled in vacuo to remove the trimethysilyl acetate formed as byproduct. The reaction mixture was poured into isopropanol (800 mL) and stirred 18 hours. The solids were collected, washed with ethyl acetate and dried to give 1-methoxymethyl-5-methyl-2,4(1H,3H)-pyrimidinedione (116 g, 0.68 mol). was heated 16 hours briefly at reflux distilled in vacuo at 80° C. to remove the excess HMDS did not exceed 95° C The mixture was heated 20 minutes at 70° C. distilled in vacuo to remove the trimethysilyl acetate formed as byproduct stirred 18 hours The solids were collected washed with ethyl acetate dried

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of thymine (100 g, 0.79 mol), trifluoromethanesulfonic acid (2 mL, 20 mmol) and HMDS (418 mL, 1.98 mol) was heated 16 hours with stirring at 90° C. and briefly at reflux and then distilled in vacuo at 80° C. to remove the excess HMDS. The mixture was treated with trifluoromethanesulfonic acid (1.5 mL, 20 mmol) and then methoxymethyl acetate (88 mL, 0.89 mol) was added at a rate such that the reaction temperature did not exceed 95° C. The mixture was heated 20 minutes at 70° C. and then distilled in vacuo to remove the trimethysilyl acetate formed as byproduct. The reaction mixture was poured into isopropanol (800 mL) and stirred 18 hours. The solids were collected, washed with ethyl acetate and dried to give 1-methoxymethyl-5-methyl-2,4(1H,3H)-pyrimidinedione (116 g, 0.68 mol). was heated 16 hours briefly at reflux distilled in vacuo at 80° C. to remove the excess HMDS did not exceed 95° C The mixture was heated 20 minutes at 70° C. distilled in vacuo to remove the trimethysilyl acetate formed as byproduct stirred 18 hours The solids were collected washed with ethyl acetate dried

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

実験手順: 50.45 g of 1,3-dipivaloyl glycerol was dissolved in 200 ml of methoxymethyl acetate. After the addition of 2.5 g of p-toluenesulfonic acid monohydrate, the mixture was stirred for 1 hr then diluted with 200 ml of hexane and washed twice with 200 ml saturated aqueous sodium carbonate, once with aqueous NaCl solutions, dried over anhydrous magnesium sulfate and concentrated in vacuo to afford 1,3-dipivaloyl-2-methoxymethyl glycerol as a colorless oil. washed twice with 200 ml saturated aqueous sodium carbonate, once with aqueous NaCl solutions dried over anhydrous magnesium sulfate concentrated in vacuo

反応条件: temp:90.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of thymine (100 g, 0.79 mol), trifluoromethanesulfonic acid (2 mL, 20 mmol) and HMDS (418 mL, 1.98 mol) was heated 16 hours with stirring at 90° C. and briefly at reflux and then distilled in vacuo at 80° C. to remove the excess HMDS. The mixture was treated with trifluoromethanesulfonic acid (1.5 mL, 20 mmol) and then methoxymethyl acetate (88 mL, 0.89 mol) was added at a rate such that the reaction temperature did not exceed 95° C. The mixture was heated 20 minutes at 70° C. and then distilled in vacuo to remove the trimethysilyl acetate formed as byproduct. The reaction mixture was poured into isopropanol (800 mL) and stirred 18 hours. The solids were collected, washed with ethyl acetate and dried to give 1-methoxymethyl-5-methyl-2,4(1H,3H)-pyrimidinedione (116 g, 0.68 mol). was heated 16 hours briefly at reflux distilled in vacuo at 80° C. to remove the excess HMDS did not exceed 95° C The mixture was heated 20 minutes at 70° C. distilled in vacuo to remove the trimethysilyl acetate formed as byproduct stirred 18 hours The solids were collected washed with ethyl acetate dried

反応条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Under argon, a suspension of 0.5 g of sodium acetate in 60 ml of anhydrous chloroform, 2 ml of distilled phosphorus oxychloride, and 15 ml of methoxymethyl acetate is agitated for 30 minutes at a bath temperature of 60° C. After adding 2.0 g of 17α,21-diacetoxy-4-pregnene-3,20-dione, the mixture is further stirred for 3 hours at 70° C. and worked up analogously to Example 1. The dark crude product is purified on 200 g of silica gel with a hexane-ethyl acetate gradient (0-40% ethyl acetate), yielding 1.15 g of 17α,21-diacetoxy-6-methyl-4,6-pregnadiene-3,20-dione, mp 213°-215° C. the mixture is further stirred for 3 hours at 70° C. The dark crude product is purified on 200 g of silica gel with a hexane-ethyl acetate gradient (0-40% ethyl acetate)

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A suspension of 0.5 g of sodium acetate in 60 ml of anhydrous chloroform and 2 ml of distilled phosphorus oxychloride is refluxed under agitation for 30 minutes at a bath temperature of 70° C. After adding 15 ml of methoxymethyl acetate and 2.0 g of 17α-acetoxy-4-pregnene-3,20-dione, the reaction solution is further stirred for 5 hours at 70° C. Subsequently such an amount of a saturated soda solution is added dropwise at room temperature that the aqueous phase remains alkaline. The organic phase is separated, washed with water, and dried over sodium sulfate. After concentration, the crude product is purified on 100 g of silica gel with a hexane-ethyl acetate gradient (0-50% ethyl acetate), thus isolating 1.26 g of 17α-acetoxy-6-methyl-4,6-pregnadiene-3,20-dione, mp 217°-219° C. Subsequently such an amount of a saturated soda solution is added dropwise at room temperature that the aqueous phase The organic phase is separated washed with water dried over sodium sulfate After concentration the crude product is purified on 100 g of silica gel with a hexane-ethyl acetate gradient (0-50% ethyl acetate)