bis(prop-2-enyl) carbonate

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:

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:

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

実験手順: Preparation of the β-ketoester. To a round bottom flask equipped with an addition funnel and cold water condenser was added, 21.3 grams (0.15 mol.) of diallyl carbonate and 50 mL of tetrahydrofuran and the mixture was stirred. Next, sodium hydride, 8.4 grams (0.21 mol.), was added portion-wise. To the reaction mixture was added, 12.6 grams (0.15 mol.) of cyclopropyl methyl ketone (dissolved in 25 mL of tetrabydrofuran) via the addition funnel. The mixture was heated to relux and heated for an additional 1 hour. Subsequently, the mixture was allowed to cool and the solvent was stripped. Next, cold water (50 mL) and 1N hydrochloric acid (50 mL) were added. The reaction mixture was transferred to a separatory funnel and diethyl ether was added. The organic layer was dried over MgSO4 and stripped under vacuum to yield the β-ketoester, carboallyloxymethyl cyclopropyl ketone. ##STR15## (B) Preparation of aryl β-triketone. To a round bottom flask was added 23.6 grams (0.14 mol.) of the β-ketoester, 16 grams (0.14 mol.) of magnesium ethoxide and 100 mL of tetrahydrofuran. The reaction mixture was then refluxed for 2 hours and the solvent stripped to insure complete removal of the ethanol by-product. The flask was then recharged with 100 mL of tetrahydrofuran and 29.3 grams (0.14 mol.) of the aryl acid chloride. The solution was refluxed for several hours, after which the mixture was stripped under vacuum, extracted with diethyl ether and washed with water. The 46.4 grams of β-triketone product, trifluoromethylbenzoylcarboallyloxy-methyl cyclopropyl ketone were confirmed by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). To a round bottom flask equipped with an addition funnel and cold water condenser was added To the reaction mixture was added The mixture was heated heated for an additional 1 hour to cool The reaction mixture was transferred to a separatory funnel The organic layer was dried over MgSO4

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

実験手順: To a round bottom flask equipped with an addition funnel and cold water condenser was added, 21.3 grams (0.15 mol.) of diallyl carbonate and 50 mL of tetrahydrofuran and the mixture was stirred. Next, sodium hydride, 8.4 grams (0.21 mol.), was added portion-wise. To the reaction mixture was added, 12.6 grams (0.15 mol.) of cyclopropyl methyl ketone (dissolved in 25 mL of tetrahydrofuran) via the addition funnel. The mixture was heated to relux and heated for an additional 1 hour. Subsequently, the mixture was allowed to cool and the solvent was stripped. Next, cold water (50 mL) and 1 N hydrochloric acid (50 mL) were added. The reaction mixture was transferred to a separatory funnel and diethyl ether was added. The organic layer was dried over MgSO4 and stripped under vacuum to yield the β-ketoester, carboallyloxymethyl cyclopropyl ketone. To a round bottom flask equipped with an addition funnel and cold water condenser was added To the reaction mixture was added The mixture was heated heated for an additional 1 hour to cool The reaction mixture was transferred to a separatory funnel The organic layer was dried over MgSO4

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

実験手順: To a round bottom flask equipped with an addition funnel and cold water condenser was added, 21.3 grams (0.15 mol.) of diallyl carbonate and 50 mL of tetrahydrofuran and the mixture was stirred. Next, sodium hydride, 8.4 grams (0.21 mol.), was added portion-wise. To the reaction mixture was added, 12.6 grams (0.15 mol.) of cyclopropyl methyl ketone (dissolved in 25 mL of tetrahydrofuran) via the addition funnel. The mixture was heated to relux and heated for an additional 1 hour. Subsequently, the mixture was allowed to cool and the solvent was stripped. Next, cold water (50 mL) and 1 N hydrochloric acid (50 mL) were added. The reaction mixture was transferred to a separatory funnel and diethyl ether was added. The organic layer was dried over MgSO4 and stripped under vacuum to yield the β-ketoester, carboallyloxymethyl cyclopropyl ketone. ##STR13## (B) Preparation of aryl β-triketone To a round bottom flask equipped with an addition funnel and cold water condenser was added To the reaction mixture was added The mixture was heated heated for an additional 1 hour to cool The reaction mixture was transferred to a separatory funnel The organic layer was dried over MgSO4

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

実験手順: To a round bottom flask equipped with an addition funnel and cold water condenser was added, 21.3 grams (0.15 mol.) of diallyl carbonate and 50 mL of tetrahydrofuran and the mixture was stirred. Next, sodium hydride, 8.4 grams (0.21 mol.), was added portion-wise. To the reaction mixture was added, 12.6 grams (0.15 mol.) of cyclopropyl methyl ketone (dissolved in 25 mL of tetrahydrofuran) via the addition funnel. The mixture was heated to relux and heated for an additional 1 hour. Subsequently, the mixture was allowed to cool and the solvent was stripped. Next, cold water (50 mL) and 1 N hydrochloric acid (50 mL) were added. The reaction mixture was transferred to a separatory funnel and diethyl ether was added. The organic layer was dried over MgSO4 and stripped under vacuum to yield the β-ketoester, carboallyloxymethyl cyclopropyl ketone. ##STR13## (B) Preparation of aryl β-triketone To a round bottom flask equipped with an addition funnel and cold water condenser was added To the reaction mixture was added The mixture was heated heated for an additional 1 hour to cool The reaction mixture was transferred to a separatory funnel The organic layer was dried over MgSO4

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

実験手順: The procedure employed in Example 30 is substantially repeated employing polystyrene-bound benzyl-tri-n-butylphosphonium chloride (2 percent cross-linked with divinylbenzene) as the catalyst. Accordingly, 15 g of the polymeric catalyst, allyl chloride (76.5 g, 1.0 mole), dimethyl carbonate (90.0 g, 1.0 mole) and p-methoxyphenol (0.5 g, 0.004 mole) are combined in a reactor and heated for 6 hours at 150° C. under 600 psi carbon dioxide. The reactor is then cooled to room temperature and vented. After separating the catalyst by filtration, allyl methyl carbonate (23.8 percent yield) and diallyl carbonate (2.0 percent yield) are obtained by distillation. After separating the catalyst

反応条件: temp:150.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The reaction conditions of Example 1 are substantially repeated employing allyl chloride (76.5 g, 1.0 mole), dimethyl carbonate (90.0 g, 1.0 mole), tetra-n--butylphosphonium bromide (6.78 g, 0.02 mole) and p-methoxyphenol (0.5 g, 0.004 mole) polymerization inhibitors. After heating for 7 hours at 150° C. and 600 psi carbon dioxide pressure, the reactor is cooled to room temperature and vented. Distillation gives 29.0 g (25 percent yield) of allyl methyl carbonate having b.p. of 79° C.-80° C. (150 torr) and 4.8 g (3.4 percent yield) of diallyl carbonate having b.p. of 107° C.-108° C. (150 torr). The reaction conditions of Example 1 Distillation