2-ethyl-2-methylbutanoyl chloride

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: A procedure similar to that described in Example 4, above, was followed, but using 1.0 g (2.4 mmol) of (4R,6R)-6-{2-[(1S,2S,8S,8aR)-1,2,6,7,8,8a-hexahydro-8-hydroxy-2-methyl-1-naphthyl]ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Japanese Patent Kokai Application No. Sho 59-175450] and 1.4 g (9.4 mmol) of 2-ethyl-2-methylbutyryl chloride, to provide 951 mg of the title compound.

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

実験手順: 0.76 ml (5.4 mmol) of triethylamine, 807 mg (5.4 mmol) of 4-(1-pyrrolidinyl)pyridine and 674 mg (4.5 mmol) of 2-ethyl-2-methylbutyryl chloride were added to a solution of 500 mg (0.91 mmol) of (4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-hexahydro-6-t-butyldimethylsilyloxy-8-hydroxy-2-methyl-1-naphthyl]ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Example B, above] in 10 ml of benzene and the resulting mixture was heated under reflux for 5 hours. At the end of this time, the reaction mixture was diluted with 50 ml of ethyl acetate. The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, in that order. The organic phase was then dried over anhydrous magnesium sulfate, after which this phase was filtered. The filtrate was concentrated by evaporation under reduced pressure and the concentrate was purified by flash column chromatography through silica gel, using a 5:1 by volume mixture of hexane and ethyl acetate as the eluent, to give 601 mg (100% yield) of the title compound. prepared under reflux for 5 hours The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid The organic phase was then dried over anhydrous magnesium sulfate after which this phase was filtered The filtrate was concentrated by evaporation under reduced pressure the concentrate was purified by flash column chromatography through silica gel by volume mixture of hexane and ethyl acetate as the eluent

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

実験手順: A procedure similar to that described in Example 4, above, was followed, but using 1.0 g (2.4 mmol) of (4R,6R)-6-{2-[(1S,2S,8S,8aR)-1,2,6,7,8,8a-hexahydro-8-hydroxy-2-methyl-1-naphthyl]ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Japanese Patent Kokai Application No. Sho 59-175450] and 1.4 g (9.4 mmol) of 2-ethyl-2-methylbutyryl chloride, to provide 951 mg of the title compound.

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

実験手順: 0.76 ml (5.4 mmol) of triethylamine, 807 mg (5.4 mmol) of 4-(1-pyrrolidinyl)pyridine and 674 mg (4.5 mmol) of 2-ethyl-2-methylbutyryl chloride were added to a solution of 500 mg (0.91 mmol) of (4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-hexahydro-6-t-butyldimethylsilyloxy-8-hydroxy-2-methyl-1-naphthyl]ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Example B, above] in 10 ml of benzene and the resulting mixture was heated under reflux for 5 hours. At the end of this time, the reaction mixture was diluted with 50 ml of ethyl acetate. The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, in that order. The organic phase was then dried over anhydrous magnesium sulfate, after which this phase was filtered. The filtrate was concentrated by evaporation under reduced pressure and the concentrate was purified by flash column chromatography through silica gel, using a 5:1 by volume mixture of hexane and ethyl acetate as the eluent, to give 601 mg (100% yield) of the title compound. prepared under reflux for 5 hours The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid The organic phase was then dried over anhydrous magnesium sulfate after which this phase was filtered The filtrate was concentrated by evaporation under reduced pressure the concentrate was purified by flash column chromatography through silica gel by volume mixture of hexane and ethyl acetate as the eluent

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: 0.76 ml (5.4 mmol) of triethylamine, 807 mg (5.4 mmol) of 4-(1-pyrrolidinyl)pyridine and 674 mg (4.5 mmol) of 2-ethyl-2-methylbutyryl chloride were added to a solution of 500 mg (0.91 mmol) of (4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-hexahydro-6-t-butyldimethylsilyloxy-8-hydroxy-2-methyl-1-naphthyl]-ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Example B, above] in 10 ml of benzene and the resulting mixture was heated under reflux for 5 hours. At the end of this time, the reaction mixture was diluted with 50 ml of ethyl acetate. The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, in that order. The organic phase was then dried over anhydrous magnesium sulfate, after which this phase was filtered. The filtrate was concentrated by evaporation under reduced pressure and the concentrate was purified by flash column chromatography through silica gel, using a 5:1 by volume mixture of hexane and ethyl acetate as the-eluent, to give 601 mg (100% yield) of the title compound. prepared under reflux for 5 hours The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid The organic phase was then dried over anhydrous magnesium sulfate after which this phase was filtered The filtrate was concentrated by evaporation under reduced pressure the concentrate was purified by flash column chromatography through silica gel by volume mixture of hexane and ethyl acetate as the-eluent

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

実験手順: 0.76 ml (5.4 mmol) of triethylamine, 807 mg (5.4 mmol) of 4-(1-pyrrolidinyl)pyridine and 674 mg (4.5 mmol) of 2-ethyl-2-methylbutyryl chloride were added to a solution of 500 mg (0.91 mmol) of (4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-hexahydro-6-t-butyldimethylsilyloxy-8-hydroxy-2-methyl-1-naphthyl]-ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Example B, above] in 10 ml of benzene and the resulting mixture was heated under reflux for 5 hours. At the end of this time, the reaction mixture was diluted with 50 ml of ethyl acetate. The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, in that order. The organic phase was then dried over anhydrous magnesium sulfate, after which this phase was filtered. The filtrate was concentrated by evaporation under reduced pressure and the concentrate was purified by flash column chromatography through silica gel, using a 5:1 by volume mixture of hexane and ethyl acetate as the-eluent, to give 601 mg (100% yield) of the title compound. prepared under reflux for 5 hours The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid The organic phase was then dried over anhydrous magnesium sulfate after which this phase was filtered The filtrate was concentrated by evaporation under reduced pressure the concentrate was purified by flash column chromatography through silica gel by volume mixture of hexane and ethyl acetate as the-eluent

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

実験手順: 0.76 ml (5.4 mmol) of triethylamine, 807 mg (5.4 mmol) of 4-(1-pyrrolidinyl)pyridine and 674 mg (4.5 mmol) of 2-ethyl-2-methylbutyryl chloride were added to a solution of 500 mg (0.91 mmol) of (4R,6R)-6-{2-[(1S,2S,6S,8S,8aR)-1,2,6,7,8,8a-hexahydro-6-t-butyldimethylsilyloxy-8-hydroxy-2-methyl-1-naphthyl]-ethyl}tetrahydro-4-t-butyldimethylsilyloxy-2H-pyran-2-one [prepared as described in Example B, above] in 10 ml of benzene and the resulting mixture was heated under reflux for 5 hours. At the end of this time, the reaction mixture was diluted with 50 ml of ethyl acetate. The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid, a saturated aqueous solution of sodium hydrogencarbonate and a saturated aqueous solution of sodium chloride, in that order. The organic phase was then dried over anhydrous magnesium sulfate, after which this phase was filtered. The filtrate was concentrated by evaporation under reduced pressure and the concentrate was purified by flash column chromatography through silica gel, using a 5:1 by volume mixture of hexane and ethyl acetate as the-eluent, to give 601 mg (100% yield) of the title compound. prepared under reflux for 5 hours The diluted mixture was then washed with 30 ml of water, 30 ml of a 10% w/v aqueous solution of citric acid The organic phase was then dried over anhydrous magnesium sulfate after which this phase was filtered The filtrate was concentrated by evaporation under reduced pressure the concentrate was purified by flash column chromatography through silica gel by volume mixture of hexane and ethyl acetate as the-eluent

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

実験手順: A supension of 68 g 2,6-dimethyl-8α-aminoergoline in 1.5 l dichloromethane are pre-cooled to 4° and treated with 78 ml triethylamine. The mixture is treated under stirring dropwise within 25 minutes with 40.5 g 2-methyl-2-ethyl-butyryl chloride. The mixture is stirred for 30 minutes, poured onto 3 l water, the organic phase is dried (Na2SO4) and concentrated. The residue is chromatographed on 800 g silica gel using dichloromethane/methanol (98:2) to yield the title compound, which is crystallised from diethyl ether, m.p. 191°-192°. The mixture is treated the organic phase is dried (Na2SO4) concentrated The residue is chromatographed on 800 g silica gel