dodeca-5,7-diyne-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:; See reaction.notes.procedure_details.

実験手順: In a glass reaction vessel, a suspension of 120 milligrams of sodium hydride was prepared in 10 milliliters dry DMF and 972 milligrams of 5,7-dodecadiyn-1,12-diol (HO(CH2)4C≡C—C≡C(CH2)4OH), was added. After stirring for 5 minutes 1.31 grams of CH3(CH2)11Br was added and the resulting mixture was stirred for 15 hours. The mixture was then quenched by addition of saturated NH4Cl solution and diluted with 100 milliliters of diethyl ether. The organic layer was separated and washed 3 times with brine, dried over MgSO4, filtered and the solvent was removed to yield a yellow oil. The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexanes gradient) to yield 606 milligrams of HO(CH2)4C≡C—C≡C(CH2)4O(CH2)11CH3 as a white solid. In a glass reaction vessel was added The mixture was then quenched by addition of saturated NH4Cl solution diluted with 100 milliliters of diethyl ether The organic layer was separated washed 3 times with brine dried over MgSO4 filtered the solvent was removed to yield a yellow oil The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexanes gradient)

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

実験手順: In a glass reaction vessel, a suspension of 120 milligrams of sodium hydride was prepared in 10 mL dry DMF and 972 milligrams of 5,7-dodecadiyn-1,12-diol (HO(CH2)4C≡C—C≡C(CH2)4OH), was added. After stirring for 5 minutes, 1.31 grams of CH3(CH2)11Br was added and the resulting mixture was stirred for 15 hours. The mixture was then quenched by addition of saturated NH4Cl solution and diluted with 100 milliliters of diethyl ether. The organic layer was separated and washed 3 times with brine, dried over MgSO4, filtered and the solvent was removed to yield a yellow oil. The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexane gradient) to yield 606 milligrams of HO(CH2)4C≡C—C≡C(CH2)4O(CH2)11CH3 as a white solid. In a glass reaction vessel the resulting mixture was stirred for 15 hours The mixture was then quenched by addition of saturated NH4Cl solution diluted with 100 milliliters of diethyl ether The organic layer was separated washed 3 times with brine dried over MgSO4 filtered the solvent was removed to yield a yellow oil The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexane gradient)

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

実験手順: In a glass reaction vessel, a suspension of 120 milligrams of sodium hydride was prepared in 10 mL dry DMF and 972 milligrams of 5,7-dodecadiyn-1,12-diol (HO(CH2)4C≡C—C≡C(CH2)4OH), was added. After stirring for 5 minutes, 1.31 grams of CH3(CH2)11Br was added and the resulting mixture was stirred for 15 hours. The mixture was then quenched by addition of saturated NH4Cl solution and diluted with 100 milliliters of diethyl ether. The organic layer was separated and washed 3 times with brine, dried over MgSO4, filtered and the solvent was removed to yield a yellow oil. The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexane gradient) to yield 606 milligrams of HO(CH2)4C≡C—C≡C(CH2)4O(CH2)11CH3 as a white solid. In a glass reaction vessel the resulting mixture was stirred for 15 hours The mixture was then quenched by addition of saturated NH4Cl solution diluted with 100 milliliters of diethyl ether The organic layer was separated washed 3 times with brine dried over MgSO4 filtered the solvent was removed to yield a yellow oil The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexane gradient)

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

実験手順: In a glass reaction vessel, a suspension of 120 milligrams of sodium hydride was prepared in 10 milliliters dry DMF and 972 milligrams of 5,7-dodecadiyn-1,12-diol (HO(CH2)4C≡C—C≡C(CH2)4OH), was added. After stirring for 5 minutes 1.31 grams of CH3(CH2)11Br was added and the resulting mixture was stirred for 15 hours. The mixture was then quenched by addition of saturated NH4Cl solution and diluted with 100 milliliters of diethyl ether. The organic layer was separated and washed 3 times with brine, dried over MgSO4, filtered and the solvent was removed to yield a yellow oil. The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexanes gradient) to yield 606 milligrams of HO(CH2)4C≡C—C≡C(CH2)4O(CH2)11CH3 as a white solid. In a glass reaction vessel was added The mixture was then quenched by addition of saturated NH4Cl solution diluted with 100 milliliters of diethyl ether The organic layer was separated washed 3 times with brine dried over MgSO4 filtered the solvent was removed to yield a yellow oil The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexanes gradient)

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

実験手順: 5,7-Dodecadiyn-1,12-diol (1) (4 g, 20.6 mmol) and imidazole (2.8 g, 41 mmol) were dissolved in dimethylformamide (15 ml). To the solution, tert-butyldimethylsilylchloride (2.38 g, 18.8 mmol) was added at once. The solution was stirred for 20 hours at room temperature under a nitrogen atmosphere. At this point, the reaction mixture was transferred into a separatory funnel along with dichloromethane (100 ml) and washed with saturated sodium bicarbonate solution and water successively. The organic layer was died (MgSO4) and concentrated followed by purification of the residue by flash column chromatography (silica gel, 7% acetone in dichloromethane) affording 3.17 g of a pale yellow oil (55% yield) of the title compound. washed with saturated sodium bicarbonate solution and water successively concentrated followed by purification of the residue by flash column chromatography (silica gel, 7% acetone in dichloromethane)

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

実験手順: 5,7-Dodecadiyn-1,12-diol (1) (4 g, 20.6 mmol) and imidazole (2.8 g, 41 mmol) were dissolved in dimethylformamide (15 ml). To the solution, tert-butyldimethylsilylchloride (2.38 g, 18.8 mmol) was added at once. The solution was stirred for 20 hours at room temperature under a nitrogen atmosphere. At this point, the reaction mixture was transferred into a separatory funnel along with dichloromethane (100 ml) and washed with saturated sodium bicarbonate solution and water successively. The organic layer was died (MgSO4) and concentrated followed by purification of the residue by flash column chromatography (silica gel, 7% acetone in dichloromethane) affording 3.17 g of a pale yellow oil (55% yield) of the title compound. washed with saturated sodium bicarbonate solution and water successively concentrated followed by purification of the residue by flash column chromatography (silica gel, 7% acetone in dichloromethane)

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 mixture of 40 parts 5,7-dodecadiyne-1,12-diol, 215 parts 1,2-dimethoxyethane, 1 part dibutyltin-di-2-ethylhexanoate and 15 parts triethylamine was prepared and the resulting mixture was stirred vigorously. A solution of 133 parts n-octadecylisocyanate in 44 parts of 1,2-dimethoxyethane was added dropwise over a period of 60 min. The reaction temperature rose to 42° C. from 18° C. within 50 min. and then subsided. After the addition, 80 parts of 1,2-dimethoxyethane was then added to the reaction mixture and the mixture was stirred for an additional 2 hrs. To this mixture was added 1390 parts of heptane. The precipitate was collected by filtration, washed with petroleum ether (bp 30°-60° C.) and dried, giving 154.6 parts (99% yield) of desired product, mp 118°-119° C. was prepared was then added to the reaction mixture the mixture was stirred for an additional 2 hrs The precipitate was collected by filtration washed with petroleum ether (bp 30°-60° C.) dried

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

実験手順: A mixture of 40 parts 5,7-dodecadiyne-1,12-diol, 215 parts 1,2-dimethoxyethane, 1 part dibutyltin-di-2-ethylhexanoate and 15 parts triethylamine was prepared and the resulting mixture was stirred vigorously. A solution of 133 parts n-octadecylisocyanate in 44 parts of 1,2-dimethoxyethane was added dropwise over a period of 60 min. The reaction temperature rose to 42° C. from 18° C. within 50 min. and then subsided. After the addition, 80 parts of 1,2-dimethoxyethane was then added to the reaction mixture and the mixture was stirred for an additional 2 hrs. To this mixture was added 1390 parts of heptane. The precipitate was collected by filtration, washed with petroleum ether (bp 30°-60° C.) and dried, giving 154.6 parts (99% yield) of desired product, mp 118°-119° C. Anal: calculated C50H92N2O4, C, 76.47%; H, 11.81%; N, 3.57%; found: C, 75.57%; H, 11.65%; N, 3.43%. IR (KBr pellet): 3330 cm-1 (N--H stretching), 2920+2850 cm-1 (C--H stretching), 1680 cm-1 (C=O), 1530 cm-1 (N--H bending), 1470 cm-1 (C--H), 1260 cm-1 (C--O--C stretching). Upon exposure to light, the crystals changed to blue, indicating the compound was solid state polymerizable. was prepared was then added to the reaction mixture the mixture was stirred for an additional 2 hrs The precipitate was collected by filtration washed with petroleum ether (bp 30°-60° C.) dried

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

実験手順: A mixture of 40 parts 5,7-dodecadiyne-1,12-diol, 215 parts 1,2-dimethoxyethane, 1 part dibutyltin-di-2-ethylhexanoate and 15 parts triethylamine was prepared and the resulting mixture was stirred vigorously. A solution of 133 parts n-octadecylisocyanate in 44 parts of 1,2-dimethoxyethane was added dropwise over a period of 60 min. The reaction temperature rose to 42° C. from 18° C. within 50 min. and then subsided. After the addition, 80 parts of 1,2-dimethoxyethane was then added to the reaction mixture and the mixture was stirred for an additional 2 hrs. To this mixture was added 1390 parts of heptane. The precipitate was collected by filtration, washed with petroleum ether (bp 30°-60° C.) and dried, giving 154.6 parts (99% yield) of desired product, mp 118°-119° C. Anal: calculated C50H92N2O4, C, 76.47%; H, 11.81%; N, 3.57%; found: C, 75.57%; H, 11.65%; N, 3.43%. IR (KBr pellet): 3330 cm-1 (N-H stretching), 2920+2850 cm-1 (C-H stretching), 1680 cm-1 (C=O), 1530 cm-1 (N-H bending), 1470 cm-1 (C-H), 1260 cm-1 (C-O-C stretching). Upon exposure to light, the crystals changed to blue, indicating the compound was solid state polymerizable. was prepared was then added to the reaction mixture the mixture was stirred for an additional 2 hrs The precipitate was collected by filtration washed with petroleum ether (bp 30°-60° C.) dried

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

実験手順: In a glass reaction vessel, a suspension of 120 milligrams of sodium hydride was prepared in 10 milliliters dry DMF and 972 milligrams of 5,7-dodecadiyn-1,12-diol (HO(CH2)4C≡C—C≡C(CH2)4OH), was added. After stirring for 5 minutes 1.31 grams of CH3(CH2)11Br was added and the resulting mixture was stirred for 15 hours. The mixture was then quenched by addition of saturated NH4Cl solution and diluted with 100 milliliters of diethyl ether. The organic layer was separated and washed 3 times with brine, dried over MgSO4, filtered and the solvent was removed to yield a yellow oil. The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexanes gradient) to yield 606 milligrams of HO(CH2)4C≡C—C≡C(CH2)4O(CH2)11CH3 as a white solid. In a glass reaction vessel was added The mixture was then quenched by addition of saturated NH4Cl solution diluted with 100 milliliters of diethyl ether The organic layer was separated washed 3 times with brine dried over MgSO4 filtered the solvent was removed to yield a yellow oil The oil was purified over silica gel (25%-35% by volume of ethyl acetate in hexanes gradient)