1-bromopent-2-yne

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: By utilizing the procedure of Example 8, by reacting p-[(1,5-dimethylhexyl)oxy]benzoic acid with 1-bromo-2-pentyne, there is obtained p-[(1,5-dimethylhexyl)oxy]benzoic acid-2-pentynyl ester; nD24 = 1.5078.

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

Procedure: Under argon atmosphere a solution of diethyl methylmalonate (20.0 g, 0.114 mol) in anhydrous THF (20 ml) was added dropwise into a stirred solution of sodium hydride (60% mineral oil dispersion, 4.6 g, 0.114 mol) in anhydrous THF (200 ml) over one hour at room temperature. A solution of 1-bromo-2-pentyne (14.0 g, 0.095 mol) in anhydrous THF (15 ml) was then added dropwise over 20 min. at room temperature. To the resulting mixture was added water (30 ml), and the mixture was neutralized with 3N hydrochloric acid, and concentrated. The residue was extracted with ethyl acetate (200 ml×2). The combined ethyl acetate layers were washed with water (50 ml) and with brine (30 ml), dried over anhydrous sodium sulfate, and concentrated to give a crude material of ethyl 2-carboethoxy-2-methyl-4-heptynoate (26.0 g). To a stirred solution of the crude material in ethanol (200 ml) was added 0.994N aqueous NaOH solution (169 ml, 0.168 mol) under ice-cooling and the mixture was stirred for 14 hrs. at room temperature. After dilution with water (30 ml), the resulting mixture was concentrated, neutralized with 6N hydrochloric acid under ice-cooling and extracted with ethyl acetate (100 ml×3). The combined ethyl acetate layers were washed with brine (50 ml), dried over anhydrous sodium sulfate, and concentrated to give a crude material of 2-carboethoxy-2-methyl-4-heptynoic acid (22.1 g). The crude material was heated at 180° C. for 2 hrs., cooled and dissolved in 100 ml of ether. A solution of diazomethane in ether was added to the solution excessively. The resulting mixture was concentrated and distilled in vacuo to give ethyl 2-methyl-4-heptynoate (12.21 g, 0.073 mol, 76%, B.p.: 118°-125° C./56 mmHg) containing methyl 2-methyl-4-heptynoate in an amount of 10% by weight. concentrated The residue was extracted with ethyl acetate (200 ml×2) The combined ethyl acetate layers were washed with water (50 ml) and with brine (30 ml) dried over anhydrous sodium sulfate concentrated

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

Procedure: Under argon atmosphere a solution of diethyl methylmalonate (20.0 g, 0.114 mol) in anhydrous THF (20 ml) was added dropwise into a stirred solution of sodium hydride (60% mineral oil dispersion, 4.6 g, 0.114 mol) in anhydrous THF (200 ml) over one hour at room temperature. A solution of 1-bromo-2-pentyne (14.0 g, 0.095 mol) in anhydrous THF (15 ml) was then added dropwise over 20 min. at room temperature. To the resulting mixture was added water (30 ml), and the mixture was neutralized with 3N hydrochloric acid, and concentrated. The residue was extracted with ethyl acetate (200 ml×2). The combined ethyl acetate layers were washed with water (50 ml) and with brine (30 ml), dried over anhydrous sodium sulfate, and concentrated to give a crude material of ethyl 2-carboethoxy-2-methyl-4-heptynoate (26.0 g). To a stirred solution of the crude material in ethanol (200 ml) was added 0.994N aqueous NaOH solution (169 ml, 0.168 mol) under ice-cooling and the mixture was stirred for 14 hrs. at room temperature. After dilution with water (30 ml), the resulting mixture was concentrated, neutralized with 6N hydrochloric acid under ice-cooling and extracted with ethyl acetate (100 ml×3). The combined ethyl acetate layers were washed with brine (50 ml), dried over anhydrous sodium sulfate, and concentrated to give a crude material of 2-carboethoxy-2-methyl-4-heptynoic acid (22.1 g). The crude material was heated at 180° C. for 2 hrs., cooled and dissolved in 100 ml of ether. A solution of diazomethane in ether was added to the solution excessively. The resulting mixture was concentrated and distilled in vacuo to give ethyl 2-methyl-4-heptynoate (12.21 g, 0.073 mol, 76%, B.p.: 118°-125° C./56 mmHg) containing methyl 2-methyl-4-heptynoate in an amount of 10% by weight. concentrated The residue was extracted with ethyl acetate (200 ml×2) The combined ethyl acetate layers were washed with water (50 ml) and with brine (30 ml) dried over anhydrous sodium sulfate concentrated

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of NaH (60% in mineral oil, 340 mg) in dry DMF (75 ml) at 0° C. was added the preceding pyridinone (1.0 g) and the mixture was stirred at 0° C. for one half hour. To the resulting suspension was added 1-bromo-2-pentyne (750 mg) dropwise. The resulting mixture was kept at 0° C. for one half hour and poured into saturated aqueous ammonium chloride (200 ml). The aqueous suspension was extracted with ether (3×100 ml), the combined ether layers washed with brine and dried, yielding the crude product. Trituration with hexane yielded the product as a yellow solid. The resulting mixture was kept at 0° C. for one half hour The aqueous suspension was extracted with ether (3×100 ml) the combined ether layers washed with brine dried yielding the crude product

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of NaH (60% in mineral oil, 700 mg) in dry DMF (100 ml) at 0° C. was added the preceding quinolinone (2.05 g) and the mixture was stirred at 0° C. for one half hour. To the resulting suspension was added 1-bromo-2-pentyne (1.6 g) dropwise. The resulting mixture was kept at 0° C. for one half hour and poured into saturated aqueous ammonium chloride (200 ml). The aqueous suspension was extracted with ether (3×100 ml), the combined ether layers washed with brine and dried, yielding the crude product. Trituration with hexane yielded the product as a yellow solid (1 g). The resulting mixture was kept at 0° C. for one half hour The aqueous suspension was extracted with ether (3×100 ml) the combined ether layers washed with brine dried yielding the crude product

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of NaH (60% in mineral oil, 200 mg) in dry DMF (50 ml) at 0° C. was added the preceding pyridinone and the mixture was stirred at 0° C. for one half hour. To the resulting suspension was added 1-bromo-2-pentyne dropwise. The resulting mixture was kept at 0° C. during one half hour and poured into saturated aqueous ammonium chloride (200 ml). The aqueous suspension was extracted with ether (3×100 ml) and the combined ether layers washed with brine and dried, yielding the crude product. After column chromatography (silica gel, hexane:ethyl acetate 8:2) the product was obtained as a white amorphous solid. The resulting mixture was kept at 0° C. during one half hour The aqueous suspension was extracted with ether (3×100 ml) the combined ether layers washed with brine dried yielding the crude product

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of NaH (60% in mineral oil, 200 mg) in dry DMF (50 ml) at 0° C. was added the preceding pyridinone and the mixture was stirred at 0° C. for one half hour. To the resulting suspension was added 1-bromo-2-pentyne dropwise. The resulting mixture was kept at 0° C. during one half hour and poured into saturated aqueous ammonium chloride (200 ml). The aqueous suspension was extracted with ether (3×100 ml) and the combined ether layers washed with brine and dried, yielding the crude product. After column chromatography (silica gel, hexane:ethyl acetate 8:2) the product was obtained as a white amorphous solid. The resulting mixture was kept at 0° C. during one half hour The aqueous suspension was extracted with ether (3×100 ml) the combined ether layers washed with brine dried yielding the crude product

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

Procedure: To a suspension of 7.1 g of sodium hydride (50% suspension in oil) in 220 ml of absolute tetrahydrofuran a solution of 31.5 g of 3-methyl-2-oxo-butylphosphonic acid dimethyl ester in 74 ml of absolute tetrahydrofuran is added in drops at 24° C.; the product is stirred for 1.5 hours and then, at 0° C., 111 ml of a 1.6 molar butyl lithium solution in hexane is added drop by drop and stirred for 20 minutes. A solution of 29 g of 1-bromo-2-pentine in 44 ml of absolute tetrahydrofuran is then added to the above solution drop by drop, stirred for 3 hours at 0° C., neutralized with 3N of hydrochloric acid and concentrated in a vacuum. 50 ml of brine is added; extraction is performed three times, each time with 200 ml of methylene chloride; the organic extract is shaken twice, each time with 50 ml of brine; the product is dried with magnesium sulfate and concentrated by evaporation in a vacuum. After distillation of the residue at 0.6 Torr and 125° C., 23 g of the title compound is obtained in the form of a colorless liquid. is added in drops at 24° C. stirred for 20 minutes stirred for 3 hours at 0° C. concentrated in a vacuum 50 ml of brine is added extraction the organic extract is shaken twice the product is dried with magnesium sulfate concentrated by evaporation in a vacuum After distillation of the residue at 0.6 Torr and 125° C.

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of NaH (60% in mineral oil, 340 mg) in dry DMF (75 ml) at 0° C. was added the preceding pyridinone (1.0 g) and the mixture was stirred at 0° C. for one half hour. To the resulting suspension was added 1-bromo-2-pentyne (750 mg) dropwise. The resulting mixture was kept at 0° C. for one half hour and poured into saturated aqueous ammonium chloride (200 ml). The aqueous suspension was extracted with ether (3×100 ml), the combined ether layers washed with brine and dried, yielding the crude product. Trituration with hexane yielded the product as a yellow solid. The resulting mixture was kept at 0° C. for one half hour The aqueous suspension was extracted with ether (3×100 ml) the combined ether layers washed with brine dried yielding the crude product

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a suspension of NaH (60% in mineral oil, 700 mg) in dry DMF (100 ml) at 0° C. was added the preceding quinolinone (2.05 g) and the mixture was stirred at 0° C. for one half hour. To the resulting suspension was added 1-bromo-2-pentyne (1.6 g) dropwise. The resulting mixture was kept at 0° C. for one half hour and poured into saturated aqueous ammonium chloride (200 ml). The aqueous suspension was extracted with ether (3×100 ml), the combined ether layers washed with brine and dried, yielding the crude product. Trituration with hexane yielded the product as a yellow solid (1 g). The resulting mixture was kept at 0° C. for one half hour The aqueous suspension was extracted with ether (3×100 ml) the combined ether layers washed with brine dried yielding the crude product