tert-butyl 4-methyl-3-oxopentanoate

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Meldrum's acid (80 g, 555 mmol) was dissolved in 600 mL of CH2Cl2 and cooled to 0° C. Freshly distilled pyridine (87.8 g, 1.11 mol) was added to the CH2Cl2 solution and then iso-butyryl chloride (65.0 g, 610.5 mmol) was added to the mixture via a pressure equalizing addition funnel. The reaction was stirred at 0° C. for 1 hr and then warmed to rt and stirred for 2 hr. Then, the reaction was quenched with water (200 mL) and washed with 0.5 M HCl (×2), water (×1), and brine (×1). The organize layer was dried over MgSO4 and concentrated in vacuo. The crude product was azeotropically dried with benzene (250 mL), and then dissolved in 200 mL of benzene and 200 mL of tert-butanol was added. The resultant reaction was heated at reflux for 4 hr. After this period, the volatiles were removed in vacuo and the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg). The desired β-keto ester 1E was obtained (58.6 g, 315.5 mmol) in 57% yield as a clear, colorless, light oil. addition funnel warmed to rt stirred for 2 hr Then, the reaction was quenched with water (200 mL) washed with 0.5 M HCl (×2), water (×1), and brine (×1) The organize layer was dried over MgSO4 concentrated in vacuo The crude product was azeotropically dried with benzene (250 mL) dissolved in 200 mL of benzene 200 mL of tert-butanol was added The resultant reaction was heated at reflux for 4 hr After this period the volatiles were removed in vacuo the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Meldrum's acid (80 g, 555 mmol) was dissolved in 600 mL of CH2Cl2 and cooled to 0° C. Freshly distilled pyridine (87.8 g, 1.11 mol) was added to the CH2Cl2 solution and then iso-butyryl chloride (65.0 g, 610.5 mmol) was added to the mixture via a pressure equalizing addition funnel. The reaction was stirred at 0° C. for 1 hr and then warmed to rt and stirred for 2 hr. Then, the reaction was quenched with water (200 mL) and washed with 0.5 M HCl (×2), water (×1), and brine (×1). The organize layer was dried over MgSO4 and concentrated in vacuo. The crude product was azeotropically dried with benzene (250 mL), and then dissolved in 200 mL of benzene and 200 mL of tert-butanol was added. The resultant reaction was heated at reflux for 4 hr. After this period, the volatiles were removed in vacuo and the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg). The desired β-keto ester 1E was obtained (58.6 g, 315.5 mmol) in 57% yield as a clear, colorless, light oil. addition funnel warmed to rt stirred for 2 hr Then, the reaction was quenched with water (200 mL) washed with 0.5 M HCl (×2), water (×1), and brine (×1) The organize layer was dried over MgSO4 concentrated in vacuo The crude product was azeotropically dried with benzene (250 mL) dissolved in 200 mL of benzene 200 mL of tert-butanol was added The resultant reaction was heated at reflux for 4 hr After this period the volatiles were removed in vacuo the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg)

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

実験手順: Through a solution of 240 g of t-butyl isobutyrylacetate in 500 ml of methanol was passed 70 g of ammonia in 2 hours, maintaining the temperature at below 25° C. The resulting solution was sitrred at room temperature for 18 hours, after which the methanol was removed in vacuo. Methylene chloride was added and the suspension was filtered. The filtrate was concentrated on a rotary evaporator to give 180 g t-butyl 3-amino-4-methyl-2-pentenoate as an oil. in 2 hours maintaining the temperature at below 25° C after which the methanol was removed in vacuo Methylene chloride was added the suspension was filtered The filtrate was concentrated on a rotary evaporator

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

実験手順: Through a solution of 240 g of t-butyl isobutyrylacetate in 500 ml of methanol was passed 70 g of ammonia in 2 hours, maintaining the temperature at below 25° C. The resulting solution was stirred at room temperature for 18 hours, after which the methanol was removed in vacuo. Methylene chloride was added and the suspension was filtered. The filtrate was concentrated on a rotary evaporator to give 180 g t-butyl 3-amino-4-methyl-2-pentenoate as an oil. in 2 hours maintaining the temperature at below 25° C after which the methanol was removed in vacuo Methylene chloride was added the suspension was filtered The filtrate was concentrated on a rotary evaporator

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Meldrum's acid (80 g, 555 mmol) was dissolved in 600 mL of CH2Cl2 and cooled to 0° C. Freshly distilled pyridine (87.8 g, 1.11 mol) was added to the CH2Cl2 solution and then iso-butyryl chloride (65.0 g, 610.5 mmol) was added to the mixture via a pressure equalizing addition funnel. The reaction was stirred at 0° C. for 1 hr and then warmed to rt and stirred for 2 hr. Then, the reaction was quenched with water (200 mL) and washed with 0.5 M HCl (×2), water (×1), and brine (×1). The organize layer was dried over MgSO4 and concentrated in vacuo. The crude product was azeotropically dried with benzene (250 mL), and then dissolved in 200 mL of benzene and 200 mL of tert-butanol was added. The resultant reaction was heated at reflux for 4 hr. After this period, the volatiles were removed in vacuo and the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg). The desired β-keto ester 1E was obtained (58.6 g, 315.5 mmol) in 57% yield as a clear, colorless, light oil. addition funnel warmed to rt stirred for 2 hr Then, the reaction was quenched with water (200 mL) washed with 0.5 M HCl (×2), water (×1), and brine (×1) The organize layer was dried over MgSO4 concentrated in vacuo The crude product was azeotropically dried with benzene (250 mL) dissolved in 200 mL of benzene 200 mL of tert-butanol was added The resultant reaction was heated at reflux for 4 hr After this period the volatiles were removed in vacuo the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Meldrum's acid (80 g, 555 mmol) was dissolved in 600 mL of CH2Cl2 and cooled to 0° C. Freshly distilled pyridine (87.8 g, 1.11 mol) was added to the CH2Cl2 solution and then iso-butyryl chloride (65.0 g, 610.5 mmol) was added to the mixture via a pressure equalizing addition funnel. The reaction was stirred at 0° C. for 1 hr and then warmed to rt and stirred for 2 hr. Then, the reaction was quenched with water (200 mL) and washed with 0.5 M HCl (×2), water (×1), and brine (×1). The organize layer was dried over MgSO4 and concentrated in vacuo. The crude product was azeotropically dried with benzene (250 mL), and then dissolved in 200 mL of benzene and 200 mL of tert-butanol was added. The resultant reaction was heated at reflux for 4 hr. After this period, the volatiles were removed in vacuo and the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg). The desired β-keto ester 1E was obtained (58.6 g, 315.5 mmol) in 57% yield as a clear, colorless, light oil. addition funnel warmed to rt stirred for 2 hr Then, the reaction was quenched with water (200 mL) washed with 0.5 M HCl (×2), water (×1), and brine (×1) The organize layer was dried over MgSO4 concentrated in vacuo The crude product was azeotropically dried with benzene (250 mL) dissolved in 200 mL of benzene 200 mL of tert-butanol was added The resultant reaction was heated at reflux for 4 hr After this period the volatiles were removed in vacuo the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg)

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Meldrum's acid (80 g, 555 mmol) was dissolved in 600 mL of CH2Cl2 and cooled to 0° C. Freshly distilled pyridine (87.8 g, 1.11 mol) was added to the CH2Cl2 solution and then iso-butyryl chloride (65.0 g, 610.5 mmol) was added to the mixture via a pressure equalizing addition funnel. The reaction was stirred at 0° C. for 1 hr and then warmed to rt and stirred for 2 hr. Then, the reaction was quenched with water (200 mL) and washed with 0.5 M HCl (×2), water (×1), and brine (×1). The organize layer was dried over MgSO4 and concentrated in vacuo. The crude product was azeotropically dried with benzene (250 mL), and then dissolved in 200 mL of benzene and 200 mL of tert-butanol was added. The resultant reaction was heated at reflux for 4 hr. After this period, the volatiles were removed in vacuo and the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg). The desired β-keto ester 1E was obtained (58.6 g, 315.5 mmol) in 57% yield as a clear, colorless, light oil. addition funnel warmed to rt stirred for 2 hr Then, the reaction was quenched with water (200 mL) washed with 0.5 M HCl (×2), water (×1), and brine (×1) The organize layer was dried over MgSO4 concentrated in vacuo The crude product was azeotropically dried with benzene (250 mL) dissolved in 200 mL of benzene 200 mL of tert-butanol was added The resultant reaction was heated at reflux for 4 hr After this period the volatiles were removed in vacuo the product then distilled on the high vacuum pump (bp 62-63° C., 0.1 mm Hg)

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

実験手順: Through a solution of 240 g of t-butyl isobutyrylacetate in 500 ml of methanol was passed 70 g of ammonia in 2 hours, maintaining the temperature at below 25° C. The resulting solution was sitrred at room temperature for 18 hours, after which the methanol was removed in vacuo. Methylene chloride was added and the suspension was filtered. The filtrate was concentrated on a rotary evaporator to give 180 g t-butyl 3-amino-4-methyl-2-pentenoate as an oil. in 2 hours maintaining the temperature at below 25° C after which the methanol was removed in vacuo Methylene chloride was added the suspension was filtered The filtrate was concentrated on a rotary evaporator

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

実験手順: Through a solution of 240 g of t-butyl isobutyrylacetate in 500 ml of methanol was passed 70 g of ammonia in 2 hours, maintaining the temperature at below 25° C. The resulting solution was sitrred at room temperature for 18 hours, after which the methanol was removed in vacuo. Methylene chloride was added and the suspension was filtered. The filtrate was concentrated on a rotary evaporator to give 180 g t-butyl 3-amino-4-methyl-2-pentenoate as an oil. in 2 hours maintaining the temperature at below 25° C after which the methanol was removed in vacuo Methylene chloride was added the suspension was filtered The filtrate was concentrated on a rotary evaporator

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

実験手順: Through a solution of 240 g of t-butyl isobutyrylacetate in 500 ml of methanol was passed 70 g of ammonia in 2 hours, maintaining the temperature at below 25° C. The resulting solution was sitrred at room temperature for 18 hours, after which the methanol was removed in vacuo. Methylene chloride was added and the suspension was filtered. The filtrate was concentrated on a rotary evaporator to give 180 g t-butyl 3-amino-4-methyl-2-pentenoate as an oil. in 2 hours maintaining the temperature at below 25° C after which the methanol was removed in vacuo Methylene chloride was added the suspension was filtered The filtrate was concentrated on a rotary evaporator

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

実験手順: Through a solution of 240 g of t-butyl isobutyrylacetate in 500 ml of methanol was passed 70 g of ammonia in 2 hours, maintaining the temperature at below 25° C. The resulting solution was sitrred at room temperature for 18 hours, after which the methanol was removed in vacuo. Methylene chloride was added and the suspension was filtered. The filtrate was concentrated on a rotary evaporator to give 180 g t-butyl 3-amino-4-methyl-2-pentenoate as an oil. in 2 hours maintaining the temperature at below 25° C after which the methanol was removed in vacuo Methylene chloride was added the suspension was filtered The filtrate was concentrated on a rotary evaporator

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

実験手順: To a solution of 240 g of t-butyl isobutyrylacetate in 500 mL of methanol was passed 70 g of ammonia in 2 hours, maintaining the temperature at below 25° C. The resulting solution was stirred at room temperature for 18 hours, after which methanol was removed in vacuo. Methylene chloride was added and the suspension was filtered. The filtrate was concentrated on a rotary evaporator to give 180 g of t-butyl 3-amino-4-methyl-2-pentenoate as an oil. in 2 hours maintaining the temperature at below 25° C after which methanol was removed in vacuo Methylene chloride was added the suspension was filtered The filtrate was concentrated on a rotary evaporator