diethyl 2-diazopropanedioate

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

実験手順: To a stirred solution of 24.52 grams (0.15 mole) of diethyl malonate and 34.0 grams (0.15 mole) of 2-naphthalenesulfonyl azide in 100 milliliters of acetonitrile was added 15.49 grams (0.15 mole) of triethylamine, dropwise, with cooling at 0° C.-5° C. On completing the feed the mixture was allowed to warm to room temperature while stirring for an approximate 16-hour period. Volatiles were stripped from the mixture under reduced pressure and the residue was slurried with ethyl ether and the inorganic salt filtered off. The filtrate was evaporated free of ether and purified by silica column chromatography to give 27.03 grams (0.15 mole) of diethyl diazomalonate as a yellow liquid. NMR analysis of the product indicated the following: dropwise, with cooling at 0° C.-5° C the inorganic salt filtered off The filtrate was evaporated free of ether purified by silica column chromatography

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

実験手順: To a stirred solution of 24.52 grams (0.15 mole) of diethyl malonate and 34.0 grams (0.15 mole) of 2-naphthalenesulfonyl azide in 100 milliliters of acetonitrile was added 15.49 grams (0.15 mole) of triethylamine, dropwise, with cooling at 0° C.-5° C. On completing the feed the mixture was allowed to warm to room temperature while stirring for an approximate 16-hour period. Volatiles were stripped from the mixture under reduced pressure and the residue was slurried with ethyl ether and the inorganic salt filtered off. The filtrate was evaporated free of ether and purified by silica column chromatography to give 27.03 grams (0.15 mole) of diethyl diazomalonate as a yellow liquid. NMR analysis of the product indicated the following: dropwise, with cooling at 0° C.-5° C the inorganic salt filtered off The filtrate was evaporated free of ether purified by silica column chromatography

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

実験手順: To a solution of 1,5-cyclooctadiene (5.27 mL, 43.0 mmol) and Rh2(OAc)4 (100 mg, 0.23 mmol) in CH2Cl2 (5 mL) was added dropwise in 3 h a solution of diethyl diazomalonate (1.0 g, 5.37 mmol) in CH2Cl2 (5 mL). This solution was stirred for 24 h at rt. The CH2Cl2 was evaporated and the excess of cyclooctadiene was removed by filtration over a glass filter filled with silica (cluens: heptane). The filtrate was concentrated in vacuo and the residue was purified by column chromatography on silica gel (EtOAc:heptane, 1:10) to afford IIa.8 (1.03 g, 72%). The CH2Cl2 was evaporated the excess of cyclooctadiene was removed by filtration over a glass filter filled with silica (cluens: heptane) The filtrate was concentrated in vacuo the residue was purified by column chromatography on silica gel (EtOAc:heptane, 1:10) to afford IIa.8 (1.03 g, 72%)

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

実験手順: To a solution of 1,5-cyclooctadiene (5.27 mL, 43.0 mmol) and Rh2(OAc)4 (100 mg, 0.23 mmol) in CH2Cl2 (5 mL) was added dropwise in 3 h a solution of diethyl diazomalonate (1.0 g, 5.37 mmol) in CH2Cl2 (5 mL). This solution was stirred for 24 h at rt. The CH2Cl2 was evaporated and the excess of cyclooctadiene was removed by filtration over a glass filter filled with silica (cluens: heptane). The filtrate was concentrated in vacuo and the residue was purified by column chromatography on silica gel (EtOAc:heptane, 1:10) to afford IIa.8 (1.03 g, 72%). The CH2Cl2 was evaporated the excess of cyclooctadiene was removed by filtration over a glass filter filled with silica (cluens: heptane) The filtrate was concentrated in vacuo the residue was purified by column chromatography on silica gel (EtOAc:heptane, 1:10) to afford IIa.8 (1.03 g, 72%)

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

実験手順: To a stirred solution of 24.52 grams (0.15 mole) of diethyl malonate and 34.0 grams (0.15 mole) of 2-naphthalenesulfonyl azide In 100 milliliters of acetonitrile was added 15.49 grams (0.15 mole) of triethylamine, dropwise, with cooling at 0° C.-5° C. On completing the feed the mixture was allowed to warm to room temperature while stirring for an approximate 16-hour period. Volatiles were stripped from the mixture under reduced pressure and the residue was slurried with ethyl ether and the inorganic salt filtered off. The filtrate was evaporated free of ether and purified by silica column chromatography to give 27.03 grams (0.15 mole) of diethyl diazomalonate as a yellow liquid. NMR analysis of the product indicated the following: dropwise, with cooling at 0° C.-5° C the inorganic salt filtered off The filtrate was evaporated free of ether purified by silica column chromatography

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

実験手順: To a stirred solution of 24.52 grams (0.15 mole) of diethyl malonate and 34.0 grams (0.15 mole) of 2-naphthalenesulfonyl azide In 100 milliliters of acetonitrile was added 15.49 grams (0.15 mole) of triethylamine, dropwise, with cooling at 0° C.-5° C. On completing the feed the mixture was allowed to warm to room temperature while stirring for an approximate 16-hour period. Volatiles were stripped from the mixture under reduced pressure and the residue was slurried with ethyl ether and the inorganic salt filtered off. The filtrate was evaporated free of ether and purified by silica column chromatography to give 27.03 grams (0.15 mole) of diethyl diazomalonate as a yellow liquid. NMR analysis of the product indicated the following: dropwise, with cooling at 0° C.-5° C the inorganic salt filtered off The filtrate was evaporated free of ether purified by silica column chromatography

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

実験手順: A mixture of sodium azide (683 mg, 10.5 mmol), p-toluenesulfonyl chloride (2.0 grams, 10.5 mmol), and 70% aqueous ethanol (30 mL) was stirred at room temperature for 1 hour. Diethyl malonate (1.62 mL, 10.0 mmol) and triethylamine (1.46 mL, 10.5 mmol) were added. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into deionized water (200 mL). The mixture was extracted with petroleum ether. The extracts were combined and decanted from the solid that formed. The petroleum ether solution was washed with a saturated aqueous sodium chloride solution. The organic solution was dried using anhydrous magnesium sulfate, filtered, and concentrated to give 1.65 grams of diethyl 2-diazomalonate as a yellow oil. IR (KBr): 2138, 1757, 1735, 1320, 1092 cm-1. Decomposition temperature: 175° C. (by DSC). The reaction mixture was stirred at room temperature for 1.5 hours The mixture was extracted with petroleum ether decanted from the solid that formed The petroleum ether solution was washed with a saturated aqueous sodium chloride solution The organic solution was dried filtered concentrated

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

実験手順: A mixture of sodium azide (683 mg, 10.5 mmol), p-toluenesulfonyl chloride (2.0 grams, 10.5 mmol), and 70% aqueous ethanol (30 mL) was stirred at room temperature for 1 hour. Diethyl malonate (1.62 mL, 10.0 mmol) and triethylamine (1.46 mL, 10.5 mmol) were added. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into deionized water (200 mL). The mixture was extracted with petroleum ether. The extracts were combined and decanted from the solid that formed. The petroleum ether solution was washed with a saturated aqueous sodium chloride solution. The organic solution was dried using anhydrous magnesium sulfate, filtered, and concentrated to give 1.65 grams of diethyl 2-diazomalonate as a yellow oil. IR (KBr): 2138, 1757, 1735, 1320, 1092 cm-1. Decomposition temperature: 175° C. (by DSC). The reaction mixture was stirred at room temperature for 1.5 hours The mixture was extracted with petroleum ether decanted from the solid that formed The petroleum ether solution was washed with a saturated aqueous sodium chloride solution The organic solution was dried filtered concentrated

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

実験手順: A mixture of sodium azide (683 mg, 10.5 mmol), p-toluenesulfonyl chloride (2.0 grams, 10.5 mmol), and 70% aqueous ethanol (30 mL) was stirred at room temperature for 1 hour. Diethyl malonate (1.62 mL, 10.0 mmol) and triethylamine (1.46 mL, 10.5 mmol) were added. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into deionized water (200 mL). The mixture was extracted with petroleum ether. The extracts were combined and decanted from the solid that formed. The petroleum ether solution was washed with a saturated aqueous sodium chloride solution. The organic solution was dried using anhydrous magnesium sulfate, filtered, and concentrated to give 1.65 grams of diethyl 2-diazomalonate as a yellow oil. IR (KBr): 2138, 1757, 1735, 1320, 1092 cm-1. Decomposition temperature: 175° C. (by DSC). The reaction mixture was stirred at room temperature for 1.5 hours The mixture was extracted with petroleum ether decanted from the solid that formed The petroleum ether solution was washed with a saturated aqueous sodium chloride solution The organic solution was dried filtered 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 1,5-cyclooctadiene (5.27 mL, 43.0 mmol) and Rh2(OAc)4 (100 mg, 0.23 mmol) in CH2Cl2 (5 mL) was added dropwise in 3 h a solution of diethyl diazomalonate (1.0 g, 5.37 mmol) in CH2Cl2 (5 mL). This solution was stirred for 24 h at rt. The CH2Cl2 was evaporated and the excess of cyclooctadiene was removed by filtration over a glass filter filled with silica (eluens: heptane). The filtrate was concentrated in vacuo and the residue was purified by column chromatography on silica gel (EtOAc:heptane, 1:10) to afford IIa.8 (1.03 g, 72%). The CH2Cl2 was evaporated the excess of cyclooctadiene was removed by filtration over a glass filter filled with silica (eluens: heptane) The filtrate was concentrated in vacuo the residue was purified by column chromatography on silica gel (EtOAc:heptane, 1:10) to afford IIa.8 (1.03 g, 72%)

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

実験手順: A mixture of sodium azide (683 mg, 10.5 mmol), p-toluenesulfonyl chloride (2.0 grams, 10.5 mmol), and 70% aqueous ethanol (30 mL) was stirred at room temperature for 1 hour. Diethyl malonate (1.62 mL, 10.0 mmol) and triethylamine (1.46 mL, 10.5 mmol) were added. The reaction mixture was stirred at room temperature for 1.5 hours and then poured into deionized water (200 mL). The mixture was extracted with petroleum ether. The extracts were combined and decanted from the solid that formed. The petroleum ether solution was washed with a saturated aqueous sodium chloride solution. The organic solution was dried using anhydrous magnesium sulfate, filtered, and concentrated to give 1.65 grams of diethyl 2-diazomalonate as a yellow oil. IR (KBr): 2138, 1757, 1735, 1320, 1092 cm-1. Decomposition temperature: 175° C. (by DSC). The reaction mixture was stirred at room temperature for 1.5 hours The mixture was extracted with petroleum ether decanted from the solid that formed The petroleum ether solution was washed with a saturated aqueous sodium chloride solution The organic solution was dried filtered concentrated

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

実験手順: To a stirred solution of 24.52 grams (0.15 mole) of diethyl malonate and 34.0 grams (0.15 mole) of 2-naphthalenesulfonyl azide in 100 milliliters of acetonitrile was added 15.49 grams (0.15 mole) of triethylamine, dropwise, with cooling at 0° C.-5° C. On completing the feed the mixture was allowed to warm to room temperature while stirring for an approximate 16-hour period. Volatiles were stripped from the mixture under reduced pressure and the residue was slurried with ethyl ether and the inorganic salt filtered off. The filtrate was evaporated free of ether and purified by silica column chromatography to give 27.03 grams (0.15 mole) of diethyl diazomalonate as a yellow liquid. NMR analysis of the product indicated the following: dropwise, with cooling at 0° C.-5° C the inorganic salt filtered off The filtrate was evaporated free of ether purified by silica column chromatography