1,12-dibromododecane

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: A solution of 3-methylbutylmagnesium bromide is prepared by treating 15.1 g. of 3-methylbutyl bromide with 2.7 g. of magnesium turnings in 50 ml. dry tetrahydrofuran. The resultant Grignard reagent is dropwise added to a cold (-10° C.) solution of 36.1 g. of 1,12-dibromododecane and 0.2 g. of Li2CuCl4 in 75 ml. dry tetrahydrofuran. The solution is stirred for 1 hour, evaporated, and fractionally distilled in vacuo to yield 15-methylhexadecyl bromide as a colorless liquid. by treating 15.1 g evaporated fractionally distilled in vacuo

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

実験手順: A solution of 3-methylbutylmagnesium bromide is prepared by treating 15.1 g. of 3-methylbutyl bromide with 2.7 g. of magnesium turnings in 50 ml. dry tetrahydrofuran. The resultant Grignard reagent is dropwise added to a cold (-10° C.) solution of 36.1 g. of 1,12-dibromododecane and 0.2 g. of Li2CuCl4 in 75 ml. dry tetrahydrofuran. The solution is stirred for 1 hour, evaporated, and fractionally distilled in vacuo to yield 15-methylhexadecyl bromide as a colorless liquid. by treating 15.1 g evaporated fractionally distilled in vacuo

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of t-butylmagnesium bromide is prepared by reacting 13.7 g. of t-butyl bromide with 2.67 g. of magnesium turnings in 50 ml. dry tetrahydrofuran. The solution of Grignard reagent is dropwise added to a stirred, cold (-10° C.) solution of 36.1 g. of 1,12-dibromododecane and 0.2 g. of Li2CuCl4 in 75 ml. dry tetrahydrofuran at a rate such that the reaction temperature does not exceed -5° C. After one additional hour of stirring at -10° C., the solvent is evaporated and the resultant liquid is fractionated in vacuo to yield 13,13-dimethyltetradecyl bromide as a colorless liquid. does not exceed -5° C the solvent is evaporated

反応条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of t-butylmagnesium bromide is prepared by reacting 13.7 g. of t-butyl bromide with 2.67 g. of magnesium turnings in 50 ml. dry tetrahydrofuran. The solution of Grignard reagent is dropwise added to a stirred, cold (-10° C.) solution of 36.1 g. of 1,12-dibromododecane and 0.2 g. of Li2CuCl4 in 75 ml. dry tetrahydrofuran at a rate such that the reaction temperature does not exceed -5° C. After one additional hour of stirring at -10° C., the solvent is evaporated and the resultant liquid is fractionated in vacuo to yield 13,13-dimethyltetradecyl bromide as a colorless liquid. does not exceed -5° C the solvent is evaporated

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

実験手順: An acetone solution of 90 m moles(21.8 g) of the above 4'-hydroxybiphenyl-4-carboxylic acid ethyl ester, 0.15 mole(49.2 g) of 1,12-dibromododecane, and 0.4 mole(55.3 g) of potassium carbonate was refluxed for four hours. The reaction sloution was filtered. The filtrate was concentrated, and then purified by column chromatography, to obtain 29.5 g of 4'-(12-bromododecyloxy)biphenyl-4-carboxylic acid ethyl ester [m.p. 88.6°-90.5° C⟧ (yield: 67%) The reaction sloution was filtered The filtrate was concentrated purified by column chromatography

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium hydride (60%, 652 mg, 16.3 mmol) washed with hexane was suspended in toluene (3 ml), 1,12-dodecanediol (1.50 g, 7.41 mmol) was added, 1,12-dibromododecane (6.08 g, 18.5 mmol) was added, and the mixture was stirred at 80° C. for 4 days. The reaction mixture was cooled to room temperature, and pure water (30 ml) was added dropwise thereto in a water bath to quench the reaction. The mixture was extracted with chloroform (100 ml), and washed 3 times with 1N hydrochloric acid (30 ml), 3 times with 5% aqueous sodium hydrogen carbonate solution (30 ml), and once with 20% aqueous sodium chloride solution (30 ml). The organic layer was dried over sodium sulfate and the solvent of the filtrate was evaporated. The residue was isolated and purified by silica gel column chromatography, and precipitated with methanol (50 ml) to give 1,12-bis-(12-bromododecyloxy)-dodecane (yield 56%). The reaction mixture was cooled to room temperature in a water bath to quench the reaction The mixture was extracted with chloroform (100 ml) washed 3 times with 1N hydrochloric acid (30 ml), 3 times with 5% aqueous sodium hydrogen carbonate solution (30 ml) The organic layer was dried over sodium sulfate the solvent of the filtrate was evaporated The residue was isolated purified by silica gel column chromatography precipitated with methanol (50 ml)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium hydride (60%, 652 mg, 16.3 mmol) washed with hexane was suspended in toluene (3 ml), 1,12-dodecanediol (1.50 g, 7.41 mmol) was added, 1,12-dibromododecane (6.08 g, 18.5 mmol) was added, and the mixture was stirred at 80° C. for 4 days. The reaction mixture was cooled to room temperature, and pure water (30 ml) was added dropwise thereto in a water bath to quench the reaction. The mixture was extracted with chloroform (100 ml), and washed 3 times with 1N hydrochloric acid (30 ml), 3 times with 5% aqueous sodium hydrogen carbonate solution (30 ml), and once with 20% aqueous sodium chloride solution (30 ml). The organic layer was dried over sodium sulfate and the solvent of the filtrate was evaporated. The residue was isolated and purified by silica gel column chromatography, and precipitated with methanol (50 ml) to give 1,12-bis-(12-bromododecyloxy)-dodecane (yield 56%). The reaction mixture was cooled to room temperature in a water bath to quench the reaction The mixture was extracted with chloroform (100 ml) washed 3 times with 1N hydrochloric acid (30 ml), 3 times with 5% aqueous sodium hydrogen carbonate solution (30 ml) The organic layer was dried over sodium sulfate the solvent of the filtrate was evaporated The residue was isolated purified by silica gel column chromatography precipitated with methanol (50 ml)

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Sodium hydride (60%, 0.98 g, 24.5 mmol) washed with hexane was suspended in toluene (16 ml), 1-docosanol (4.00 g, 12.2 mmol) was added, 1,12-dibromododecane (8.04 g, 24.5 mmol) was added, and the mixture was stirred at 85° C. for 2 days. The reaction mixture was cooled to room temperature, 1N hydrochloric acid (30 ml) was added dropwise thereto in a water bath to quench the reaction. The mixture was extracted with chloroform (100 ml), and washed 3 times with 1N hydrochloric acid (30 ml), 3 times with 5% aqueous sodium hydrogen carbonate solution (30 ml), and once with 20% aqueous sodium chloride solution (30 ml). The organic layer was dried over sodium sulfate, and the solvent of the filtrate was evaporated. The residue was isolated and purified by silica gel column chromatography and precipitated with methanol (70 ml) to give 12-docosyloxy-dodecyl bromide (yield 78%). The reaction mixture was cooled to room temperature in a water bath to quench the reaction The mixture was extracted with chloroform (100 ml) washed 3 times with 1N hydrochloric acid (30 ml), 3 times with 5% aqueous sodium hydrogen carbonate solution (30 ml) The organic layer was dried over sodium sulfate the solvent of the filtrate was evaporated The residue was isolated purified by silica gel column chromatography precipitated with methanol (70 ml)

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1,12-Dibromododecane (mmol) was added to a solution (30 mL) of isoquinoline, and the solution heated for 24 hours at 65° C. The resulting precipitate was filtered, and the product washed five times with dry diethyl ether. The resulting off-white solid was isolated. 1H NMR (300 MHz, DMSO-D6) δ 10.06 (1H, d, C1-H), 8.78 (1H, d, C3-H), 8.58 (1H, d, C8-H), 8.48 (1H, d, C4-H), 8.35 (1H, d, C7-H), 8.25 (1H, t, C5-H), 8.07 (1H, t, C6-H), 4.70 (2H, t, C′1-CH2), 2.0 (2H, m, C′2-CH2), 1.75 (1H, m, C′3-CH2), 1.15-1.40 (7H, m, C′3-6-CH2). The resulting precipitate was filtered the product washed five times with dry diethyl ether The resulting off-white solid was isolated

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1,12-Dibromododecane (mmol) was added to a solution (30 mL) of dry quinoline, and the solution heated for 24 hours at 65° C. The resulting precipitate was filtered, and the product washed five times with dry diethyl ether. The resulting yellow solid was isolated in a 92% yield. 1H NMR (300 MHz, DMSO-D6) δ 9.58 (1H, d, C2-H), 9.29 (1H, d, C3-H), 8.61 (1H, d, C8-H), 8.50 (1H, d, C4-H), 8.29 (1H, t, C7-H), 8.18 (1H, t, C5-H), 8.04 (1H, d, C6-H), 5.04 (2H, t, C′1-CH2), 1.95 (2H, m, C′2-CH2), 1.2-1.4 (8H, m, C′3-6-CH2); 13C NMR (75 MHz, DMSO-D6) δ 149.5, 147.4, 137.4, 135.6, 130.7, 129.9, 129.7, 122.1, 118.9, 57.3, 29.5, 28.9, 28.8, 28.5, 25.7. The resulting precipitate was filtered the product washed five times with dry diethyl ether The resulting yellow solid was isolated in a 92% yield