dodecane-1,12-diol

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: Compounds (111), (112), (113), (114), (115), (116) and (117) (Table 1) are obtained in analogy to Example 5 using 1-dodecanol, 1-octadecanol, 1-nonadecanol, 1-docosanol, 2-ethylhexanol, 1,6-hexanediol and 1,12-dodecanediol instead of 1-octanol. For the preparation of compounds (116) and (117) only half of an equivalent of 1,6-hexanediol and 1,12-dodecanediol in respect to the compound (109) was used.

反応条件: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a Schlenk flask, 1,12-Dodecandiol (7.96 g, 39.4 mmol, 1 eq) was dissolved in 40 mL of dry DMF under nitrogen. Imidazole (2.63 g, 38.6 mmol, 1 eq) and tert-butylchlorodiphenylsilane (TBDPS) (10.84 g, 39.4 mmol, 1 eq) were added and the reaction mixture was heated to 45° C. After stirring for 48 h, the reaction was quenched with 300 mL of distilled water. The aqueous phase was extracted four times with diethyl ether, the organic phases were collected and washed twice with 2N HCl (2×100 mL), once with saturated NaHCO3 (200 mL), once with saturated NaCl (200 mL) and dried over Na2SO4. Column-chromatography over silica gel using 10/1 hexane/ethyl acetate as eluent yielded 7.98 g (46%) of the desired product as a slightly yellowish oil. 1H NMR (300.13 MHz): δ (ppm)=1.05 (s, 9H, tert-butyl), 1.26 (br, 16H, —O—CH2—CH2—CH2—CH2—CH2—), 1.58 (m, 4H, —O—CH2CH2—), 3.65 (m, 4H, —O—CH2—), 7.40 (m, 6H, phenyl), 7.69 (m, 4H, phenyl). 13C NMR (75.48 MHz): δ (ppm)=19.2, 25.7, 25.8, 25.9, 29.3, 29.4, 29.58, 29.6, 32.6, 32.8, 63.1, 64.0, 127.5, 129.4, 134.1, 135.6. the reaction was quenched with 300 mL of distilled water The aqueous phase was extracted four times with diethyl ether the organic phases were collected washed twice with 2N HCl (2×100 mL), once with saturated NaHCO3 (200 mL), once with saturated NaCl (200 mL) dried over Na2SO4

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

実験手順: To 30.25 g of 1,12-dodecanediol were added 350 ml of toluene and 52 ml of 48% hydrobromic acid and the mixture was heated under reflux under azeotropic condition for 2 hours. The reaction solution was cooled and the starting material precipitated out was filtered off. The filtrate was distilled and recrystallized from hexane to afford 30.2 g of the title compound as a crystal. the mixture was heated under reflux under azeotropic condition for 2 hours The reaction solution was cooled the starting material precipitated out was filtered off The filtrate was distilled recrystallized from hexane

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

実験手順: 1,12-Dodecanediol (50 g, 0.25 mol) in hydrogen bromide 48% (220 ml) was continuously extracted with petroleum ether (b.p. 80-100° C.) (300 ml) for 18 hours. The solvent was evaporated under reduced pressure and the crude oil obtained was filtered through a pad of silica gel. Elution with petroleum ether (b.p. 40-60° C.) gave a colourless fraction containing 1,12-dibromododecane. The silica gel was then eluted with acetone to give the title compound as a pale yellow oil after evaporation of the solvent. The title compound crystallised upon cooling and was recrystallised from petroleum ether (b.p. 40-60° C.). The solvent was evaporated under reduced pressure the crude oil obtained was filtered through a pad of silica gel Elution with petroleum ether (b.p. 40-60° C.) gave a colourless fraction The silica gel was then eluted with acetone

反応条件: temp:45.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a Schlenk flask, 1,12-Dodecandiol (7.96 g, 39.4 mmol, 1 eq) was dissolved in 40 mL of dry DMF under nitrogen. Imidazole (2.63 g, 38.6 mmol, 1 eq) and tert-butylchlorodiphenylsilane (TBDPS) (10.84 g, 39.4 mmol, 1 eq) were added and the reaction mixture was heated to 45° C. After stirring for 48 h, the reaction was quenched with 300 mL of distilled water. The aqueous phase was extracted four times with diethyl ether, the organic phases were collected and washed twice with 2N HCl (2×100 mL), once with saturated NaHCO3 (200 mL), once with saturated NaCl (200 mL) and dried over Na2SO4. Column-chromatography over silica gel using 10/1 hexane/ethyl acetate as eluent yielded 7.98 g (46%) of the desired product as a slightly yellowish oil. 1H NMR (300.13 MHz): δ (ppm)=1.05 (s, 9H, tert-butyl), 1.26 (br, 16H, —O—CH2—CH2—CH2—CH2—CH2—), 1.58 (m, 4H, —O—CH2—CH2—), 3.65 (m, 4H, —O—CH2—), 7.40 (m, 6H, phenyl), 7.69 (m, 4H, phenyl). 13C NMR (75.48 MHz): δ (ppm)=19.2, 25.7, 25.8, 25.9, 29.3, 29.4, 29.58, 29.6, 32.6, 32.8, 63.1, 64.0, 127.5, 129.4, 134.1, 135.6. the reaction was quenched with 300 mL of distilled water The aqueous phase was extracted four times with diethyl ether the organic phases were collected washed twice with 2N HCl (2×100 mL), once with saturated NaHCO3 (200 mL), once with saturated NaCl (200 mL) dried over Na2SO4

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 1,12-dodecanediol (2.2 g, 0.011 mol), anhydrous potassium carbonate (4.1 g, 0.031 mol), 35 ml of dimethylformamide and 5 ml of benzene was heated at reflux under a nitrogen atmosphere for 12 hours. A small quantity of water was collected in a Dean-Stark trap. The benzene was removed by distillation. To the cooled reaction medium was added 4.0 g (0.023 mol) of 4-nitrophthalonitrile, which resulted in an immediate color change to a deep blue. After 10 minutes at room temperature, the reaction medium had turned to a yellowish-orange and remained this color throughout the entire reaction. The mixture was stirred and heated at 100° C. for 16 hours under a nitrogen atmosphere. The cooled reaction mixture was poured into 200 ml of cold dilute hydrochloric acid and extracted with three 75 ml portions of chloroform. The combined extract was washed with water, dried over anhydrous sodium sulfate, charcoaled and concentrated at reduced pressure. Recrystallization of the crude produced from ethanol-water yielded 3.1 g (70%) of 1,12-bis(3,4-dicyanophenoxy) dodecane. was heated at reflux under a nitrogen atmosphere for 12 hours A small quantity of water was collected in a Dean-Stark trap The benzene was removed by distillation To the cooled reaction medium resulted in an immediate color change to a deep blue throughout the entire reaction The cooled reaction mixture extracted with three 75 ml portions of chloroform The combined extract was washed with water dried over anhydrous sodium sulfate concentrated at reduced pressure Recrystallization of the crude produced from ethanol-water

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

実験手順: A mixture of 1,12-dodecanediol (2,2 g, 0.011 mol), sodium hydride (0.91 g. 0.023 mol, 61%) and 25 ml of dry dimethylformamide were stirred under a nitrogen atmosphere at 90°-95° C. for 12 hours. After cooling, 4.0 g (0.23 mol) of 4-nitrophthalonitrile was added to the white salt mixture. The salt dissolved quickly and the mixture was heated at 100°-110° C. for 4 hours. Infrared analysis indicated that a large quantity of 4-nitrophthalonitrile was still present. The temperature was increased to 140°-145° C. and the mixture was stirred at this temperature for 15 hours. The cooled reaction mixture was poured into 200 ml of cold water and the product was extracted into three, 75 ml portions of methylene chloride. The combined extract was washed several times with water, charcoaled, dried over anhydrous sodium sulfate, and concentrated at reduced pressure. Recrystallization of the crude material from ethanol-water yielded 1.7 g (40%) of 1,12-bis(3,4-dicyanophenoxy) dodecane. After cooling The salt dissolved quickly the mixture was heated at 100°-110° C. for 4 hours The temperature was increased to 140°-145° C. the mixture was stirred at this temperature for 15 hours The cooled reaction mixture the product was extracted into three, 75 ml portions of methylene chloride The combined extract was washed several times with water dried over anhydrous sodium sulfate concentrated at reduced pressure Recrystallization of the crude material from ethanol-water

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

実験手順: A mixture of 1,12-dodecanediol (2,2 g, 0.011 mol), sodium hydride (0.91 g. 0.023 mol, 61%) and 25 ml of dry dimethylformamide were stirred under a nitrogen atmosphere at 90°-95° C. for 12 hours. After cooling, 4.0 g (0.23 mol) of 4-nitrophthalonitrile was added to the white salt mixture. The salt dissolved quickly and the mixture was heated at 100°-110° C. for 4 hours. Infrared analysis indicated that a large quantity of 4-nitrophthalonitrile was still present. The temperature was increased to 140°-145° C. and the mixture was stirred at this temperature for 15 hours. The cooled reaction mixture was poured into 200 ml of cold water and the product was extracted into three, 75 ml portions of methylene chloride. The combined extract was washed several times with water, charcoaled, dried over anhydrous sodium sulfate, and concentrated at reduced pressure. Recrystallization of the crude material from ethanol-water yielded 1.7 g (40%) of 1,12-bis(3,4-dicyanophenoxy) dodecane. After cooling The salt dissolved quickly the mixture was heated at 100°-110° C. for 4 hours The temperature was increased to 140°-145° C. the mixture was stirred at this temperature for 15 hours The cooled reaction mixture the product was extracted into three, 75 ml portions of methylene chloride The combined extract was washed several times with water dried over anhydrous sodium sulfate concentrated at reduced pressure Recrystallization of the crude material from ethanol-water