bis(prop-2-enyl) propanedioate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of sodium hydride (4.35 g, 0.18 mol) in freshly distilled THF (100 mL) was cooled to 0° C. and treated with diallyl malonate (35 g, 0.19 mol) over 40 min via a dropping funnel. After stirring at room temperature for 30 min, N-(2-bromoethyl)phthalimide (43.9 g, 0.17 mol) was added to the solution in one portion and the mixture was heated to reflux. After 48 h the solution was cooled to 0° C., quenched with 2N HCl and concentrated to about 20% of its original volume. The concentrate was diluted with ethyl acetate (300 mL) and washed successively with satd. aq. K2CO3 and NaCl. The organic layer was dried over MgSO4, filtered and concentrated under reduced pressure. Purification by flash column chromatography (5-25% ethyl acetate:hexanes) provided diallyl (2-phthalimidoethyl)malonate (41.2 g, 67%) as a colorless oil. 1H NMR (300 MHz, CDCl3) d 7.82 (m, 2H), 7.72 (m, 2H), 5.85 (m, 2H), 5.30 (m, 2H), 5.22 (m, 2H), 4.60 (m, 4H), 3.80 (t, J=6.6 Hz, 2H), 3.46 (t, J=7.2 Hz, 1H), 2.30 (dd, J=13.8, 6.9 Hz, 2H). the mixture was heated to reflux After 48 h the solution was cooled to 0° C. quenched with 2N HCl concentrated to about 20% of its original volume The concentrate was diluted with ethyl acetate (300 mL) washed successively with satd The organic layer was dried over MgSO4 filtered concentrated under reduced pressure Purification by flash column chromatography (5-25% ethyl acetate:hexanes)

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: At room temperature, 61.9 g (190.02 mmol) of cesium carbonate are added to a solution of 10 g (54.3 mmol) of diallyl malonate and 47.25 g (purity 80%, 130.3 mmol) of methyl 4-(2-iodoethyl)benzoate in 100 ml DMF, and the mixture is then stirred at room temperature overnight. After the reaction has gone to completion, the reaction solution is evaporated to dryness and the residue is taken up in 100 ml of water and 100 ml of diethyl ether. The aqueous phase is extracted five times with diethyl ether and the combined organic phases are washed with saturated sodium chloride solution and dried over magnesium sulfate. After filtration, the solvent is removed under reduced pressure and the residue is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 10:1→5:1). This gives 22.64 g (44.52 mmol, 82% of theory) of a yellowish oil. the reaction solution is evaporated to dryness The aqueous phase is extracted five times with diethyl ether the combined organic phases are washed with saturated sodium chloride solution dried over magnesium sulfate After filtration the solvent is removed under reduced pressure the residue is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 10:1→5:1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: At room temperature, 61.9 g (190.02 mmol) of cesium carbonate are added to a solution of 10 g (54.3 mmol) of diallyl malonate and 47.25 g (purity 80%, 130.3 mmol) of methyl 4-(2-iodoethyl)benzoate in 100 ml DMF, and the mixture is then stirred at room temperature overnight. After the reaction has gone to completion, the reaction solution is evaporated to dryness and the residue is taken up in 100 ml of water and 100 ml of diethyl ether. The aqueous phase is extracted five times with diethyl ether and the combined organic phases are washed with saturated sodium chloride solution and dried over magnesium sulfate. After filtration, the solvent is removed under reduced pressure and the residue is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 10:1→5:1). This gives 22.64 g (44.52 mmol, 82% of theory) of a yellowish oil. the reaction solution is evaporated to dryness The aqueous phase is extracted five times with diethyl ether the combined organic phases are washed with saturated sodium chloride solution dried over magnesium sulfate After filtration the solvent is removed under reduced pressure the residue is purified by flash chromatography on silica gel (mobile phase: petroleum ether/ethyl acetate 10:1→5:1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A solution of sodium hydride (4.35 g, 0.18 mol) in freshly distilled THF (100 mL) was cooled to 0° C. and treated with diallyl malonate (35 g, 0.19 mol) over 40 min via a dropping funnel. After stirring at room temperature for 30 min, N-(2-bromoethyl)phthalimide (43.9 g, 0.17 mol) was added to the solution in one portion and the mixture was heated to reflux. After 48 h the solution was cooled to 0° C., quenched with 2N HCl and concentrated to about 20% of its original volume. The concentrate was diluted with ethyl acetate (300 mL) and washed successively with satd. aq. K2CO3 and NaCl. The organic layer was dried over MgSO4, filtered and concentrated under reduced pressure. Purification by flash column chromatography (5-25% ethyl acetate:hexanes) provided diallyl 2-phthalimidoethylmalonate (41.2 g, 67%) as a colorless oil. 1H NMR (300 MHz, CDCl3) d 7.82 (m, 2H), 7.72 (m, 2H), 5.85 (m, 2H), 5.30 (m, 2H), 5.22 (m, 2H), 4.60 (m, 4H), 3.80 (t, J=6.6 Hz, 2H), 3.46 (t, J=7.2 Hz, 1H), 2.30 (dd, J=13.8, 6.9 Hz, 2H). ##STR222## Step 3 the mixture was heated to reflux After 48 h the solution was cooled to 0° C. quenched with 2N HCl concentrated to about 20% of its original volume The concentrate was diluted with ethyl acetate (300 mL) washed successively with satd The organic layer was dried over MgSO4 filtered concentrated under reduced pressure Purification by flash column chromatography (5-25% ethyl acetate:hexanes)