(Z)-tetradec-11-enal

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

実験手順: The Grignard solution is then added to a mixture of 1-penten-3-yl isobutyrate ester (84 g, 0.538 mol) and LiCuBr2 reagent (1 M/THF, 63 mL) at a rate that maintains the reaction temperature between 25-30° C., with cooling as necessary. The mixture is stirred for 15 minutes then quenched with aqueous citric acid solution (1 L). The layers are separated and the organic portion is washed with water (2×) and dilute sodium hydroxide solution (until pH basic). The crude organic portion is then stripped of solvent and distilled to afford 98.1 g of the 11E-tetradecenal DEA product (b.p. 150° C., 0.1 mm Hg, Yld. 64%, m/z 284), which is subsequently deprotected using formic acid in heptane at room temperature to give 11-tetradecenal (67.3 g, Yld. 67%, E/Z 83:17). at room temperature

反応条件: temp:5.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 0.48 gm of magnesium in a thoroughly dried flask equipped with condensor and magnetic stirrer was added 2 mls of anhydrous tetrahydrofuran and 0.3 ml of butyl chloride. The mixture was stirred and heated at reflux until reaction initiated (approximately 10 minutes). After 5 minutes, portionwise addition of 3.5 gms of 1,1-diethoxy-9-chloro nonane in 10 ml of tetrahydrofuran was begun. When the addition was complete (15 minutes) the mixture was stirred and heated for 2 hours. It was then cooled to 5° C. in an ice bath and 30 gms of a mixture of 3-chloro-1-pentene (approximately 40%) and 1-chloro-2-pentene (approximately 60%) was added all at once. The mixture was heated slowly and stirred, whereupon it became cloudy. Heating was continued at reflux temperature for 2 hours. The mixture was then cooled, poured into 100 ml of 3 N-hydrochloric acid and diluted with 100 ml of tetrahydrofuran and 150 ml of acetone. The resulting solution was stirred and heated for 30 minutes. It was then concentrated on rotary evaporator and extracted twice with 100 mls of hexane. The organic layer was dried over sodium sulphate, evaporated and distilled. The majority distilled at 110° C. at 0.35 torr and yielded 2.11 gms of 11-tetradecenal. heated at reflux until reaction (approximately 10 minutes) When the addition (15 minutes) was stirred heated for 2 hours The mixture was heated slowly stirred, whereupon it Heating at reflux temperature for 2 hours The mixture was then cooled The resulting solution was stirred heated for 30 minutes It was then concentrated on rotary evaporator extracted twice with 100 mls of hexane The organic layer was dried over sodium sulphate evaporated distilled The majority distilled at 110° C. at 0.35 torr

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

実験手順: To 0.85 gm of magnesium in a thoroughly dried flask equipped with condensor and magnetic stirrer was added 5 mls of anhydrous tetrahydrofuran and 0.5 ml of dibromo ethane. A solution of 4.5 gms of 1,1-dimethoxy-9-chlorononane in 40 mls of toluene was added dropwise. When addition was half complete, a few drops of bromoethane were added and the addition was continued. The temperature was maintained at 75°±5° for two hours. The Grignard reagent was decanted into another flask and 100 mgs of cuprous chloride (CuCl) catalyst was added, followed by dropwise addition of 3.0 gms of a mixture (approximately 60:40) of 1-chloro-2-pentene and 3-chloro-1-pentene dissolved in 15 mls of toluene. The reaction flask was cooled in a water bath at 20°±5°. Magnesium chloride began to precipitate after ten minutes. The reaction stood overnight at room temperature. 50 mls of 3 N hydrochloric acid was added and the reaction mixture was stirred and heated at reflux for 1 hour. The aqueous layer was separated and washed two times with toluene. The organic layer and the toluene washes were combined and dried over sodium sulphate. The solvents were removed on the rotary evaporator and the residue was distilled at 83° at 0.10 torr yielding 2.3 gms of crude 11-tetradecenal. GLC analysis showed that the contaminating 10-ethyl-11-dodecenal was present in only 11.5%. For physical constants see Example 5. When addition the addition The temperature was maintained at 75°±5° for two hours The Grignard reagent was decanted into another flask 100 mgs of cuprous chloride (CuCl) catalyst was added followed by dropwise addition of 3.0 gms of a mixture (approximately 60:40) of 1-chloro-2-pentene and 3-chloro-1-pentene dissolved in 15 mls of toluene The reaction flask was cooled in a water bath at 20°±5° to precipitate after ten minutes 50 mls of 3 N hydrochloric acid was added heated at reflux for 1 hour The aqueous layer was separated washed two times with toluene dried over sodium sulphate The solvents were removed on the rotary evaporator the residue was distilled at 83° at 0.10 torr

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 0.85 gm of magnesium in a thoroughly dried flask equipped with condensor and magnetic stirrer was added 5 mls of anhydrous tetrahydrofuran and 1.06 mls of butyl chloride and 5 mls of dry toluene. This mixture was heated with stirring at 70° C. for about two hours. A solution of 4.44 gms of 1,1-dimethoxy-9-chloro nonane in 50 mls of toluene was added all at once. The temperature was maintained at 75°±5° for one and one quarter hours. The Grignard reagent was decanted into another flask and 3.12 gms of a mixture (approximately 60:40) of 1-chloro-2-pentene and 3-chloro-1-pentene was added. The reaction was maintained at 75°±5° with stirring. The reaction mixture became cloudy within one-half to three-quarters of an hour indicating the initiation of the coupling reaction. This was confirmed by GLC of a hydrolysed aliquot of reaction mixture. The reaction was allowed to continue until a test for Grignard reagent was negative (approximately 2 hours). 50 mls of 3 N hydrochloric acid was then added, the reaction mixture was then stirred and heated at reflux for 1 hour. The aqueous layer was separated, washed two times with toluene. The organic layer and the toluene washes were combined and dried over sodium sulphate. The solvents were removed on the rotary evaporator and the residue was distilled. The majority of the material distilled at 95° at 0.35 torr yielding 2.48 gms of crude 11-tetradecenal. For physical constants see Example 5. This mixture was heated The temperature was maintained at 75°±5° for one and one quarter hours The Grignard reagent was decanted into another flask 3.12 gms of a mixture (approximately 60:40) of 1-chloro-2-pentene and 3-chloro-1-pentene was added The reaction was maintained at 75°±5° with stirring to three-quarters of an hour the initiation of the coupling reaction This was confirmed by GLC of a hydrolysed aliquot of reaction mixture (approximately 2 hours) the reaction mixture was then stirred heated at reflux for 1 hour The aqueous layer was separated washed two times with toluene dried over sodium sulphate The solvents were removed on the rotary evaporator the residue was distilled The majority of the material distilled at 95° at 0.35 torr