6,6-dimethylhepta-2,4-diyn-1-ol

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: A solution of lithium aluminum hydride (11.4 mmol; 1M solution in tetrahydrofuran, (hereafter THF) was added to a stirred suspension of sodium methoxide (1.23 g, 22.8 mmol) in 18 ml of dry THF and the mixture was stirred at room temperature for 1/2 hour. 6,6-Dimethyl-2,4-heptadiyn-1-ol (777 mg, 5.71 mmol) was added and the mixture stirred at room temperature overnight. The mixture was cooled to 0° C. and dry ethyl acetate (1.0 g, 11.4 mmole) was added dropwise. Hexachloroethane (4.05 g, 17.13 mmole) was then added and the mixture was allowed to warm to room temperature. After 4.5 hours, additional hexachloroethane (1.35 g, 5.71 mmol) was added to the reaction mixture which was then stirred for 68 hours. The mixture was partitioned between ether and dilute aqueous hydrochloric acid, and the aqueous layer was extracted 3 times with ether. The combined ethereal extract was washed with water an brine, dried over anhydrous sodium sulfate and concentrated in vacuo to afford 3.43 g of crude product. This mixture was purified by chromatography on a column (2.5×47 cm) of silica gel eluting with ethyl acetate-hexane, 5/95. Combination and concentration of the appropriate fractions afforded 404 mg of the desired (Z)-3-chloro-6,6-dimethyl- 2-hepten-4-yn-1-ol. the mixture stirred at room temperature overnight The mixture was cooled to 0° C. to warm to room temperature After 4.5 hours was then stirred for 68 hours The mixture was partitioned between ether and dilute aqueous hydrochloric acid the aqueous layer was extracted 3 times with ether The combined ethereal extract was washed with water an brine dried over anhydrous sodium sulfate concentrated in vacuo to afford 3.43 g of crude product This mixture was purified by chromatography on a column (2.5×47 cm) of silica gel eluting with ethyl acetate-hexane, 5/95

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

Procedure: Nitrogen was bubbled through a mixture of cupric chloride (154 mg), NH2OH.HCl (0.45 g), and 70% aqueous diethylamine (9 ml) in 11 ml of water and 23 ml of methanol, for a few minutes. Propargyl alcohol (3.8 g, 0.068 mol) was added with stirring under nitrogen whereupon a yellow precipitate formed immediately. The mixture was warmed to 35°-40° C. for 15 minutes and 1-bromo-2-t-butyl-acetylene (8.57 g, 0.053 mmol) was added over 15 minutes. The mixture was stirred at 35°-40° C. for 45 minutes, then at room temperature for 1 hour. Aqueous potassium cyanide (0.45 g in 45 ml of water) was added and the mixture was stirred for one minute. The mixture was poured into 50 ml of water and extracted 5 times with ether. The combined organic phase was washed with water and dried over magnesium sulfate. The solvents were removed and the residue was distilled under reduced pressure through a column packed with glass helices. 6,6-Dimethyl-2,4-heptadiyne-1-ol (3.63 grams) was collected at 85° C. and 0.5 mm of mercury. Nitrogen was bubbled through a mixture of cupric chloride (154 mg), NH2OH.HCl (0.45 g), and 70% aqueous diethylamine (9 ml) in 11 ml of water and 23 ml of methanol, for a few minutes formed immediately The mixture was warmed to 35°-40° C. for 15 minutes The mixture was stirred at 35°-40° C. for 45 minutes the mixture was stirred for one minute extracted 5 times with ether The combined organic phase was washed with water dried over magnesium sulfate The solvents were removed the residue was distilled under reduced pressure through a column 6,6-Dimethyl-2,4-heptadiyne-1-ol (3.63 grams) was collected at 85° C.

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

Procedure: Nitrogen was bubbled through a mixture of cupric chloride (154 mg), NH2OH.HCl (0.45 g), and 70% aqueous diethylamine (9 ml) in 11 ml of water and 23 ml of methanol, for a few minutes. Propargyl alcohol (3.8 g, 0.068 mol) was added with stirring under nitrogen whereupon a yellow precipitate formed immediately. The mixture was warmed to 35°-40° C. for 15 minutes and 1-bromo-2-t-butyl-acetylene (8.57 g, 0.053 mmol) was added over 15 minutes. The mixture was stirred at 35°-40° C. for 45 minutes, then at room temperature for 1 hour. Aqueous potassium cyanide (0.45 g in 45 ml of water) was added and the mixture was stirred for one minute. The mixture was poured into 50 ml of water and extracted 5 times with ether. The combined organic phase was washed with water and dried over magnesium sulfate. The solvents were removed and the residue was distilled under reduced pressure through a column packed with glass helices. 6,6-Dimethyl-2,4-heptadiyne-1-ol (3.63 grams) was collected at 85° C. and 0.5 mm of mercury. Nitrogen was bubbled through a mixture of cupric chloride (154 mg), NH2OH.HCl (0.45 g), and 70% aqueous diethylamine (9 ml) in 11 ml of water and 23 ml of methanol, for a few minutes formed immediately The mixture was warmed to 35°-40° C. for 15 minutes The mixture was stirred at 35°-40° C. for 45 minutes the mixture was stirred for one minute extracted 5 times with ether The combined organic phase was washed with water dried over magnesium sulfate The solvents were removed the residue was distilled under reduced pressure through a column 6,6-Dimethyl-2,4-heptadiyne-1-ol (3.63 grams) was collected at 85° C.

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: A solution of 5.0 g (37.3 mmole) of 1-hydroxy-6,6-dimethyl-2,4-heptadiyne and 14.8 g (44.7 mmole) of carbon tetrabromide in 250 mL of H2CCl2 was cooled to 0°-5° C. and 12.7 g (48.4 mmole) of triphenylphosphine was added thereto. The so formed mixture was stirred for 2 hours at 0°-5° C. The reaction mixture was concentrated to about 50 ml and poured into 1 liter of petroleum ether. The mixture was stirred 15 min. and the petroleum ether was removed by decantation. The oily residue was stirred for 15 min. with another 1 liter of petroleum ether which was decanted off. The combined petroleum ether extracts were concentrated to an oil which was chromatographed on silica gel, eluting with petroleum ether to give 6.87 g of the title compound, M/e, M+ 200. The so formed mixture The reaction mixture was concentrated to about 50 ml poured into 1 liter of petroleum ether The mixture was stirred 15 min. the petroleum ether was removed by decantation The oily residue was stirred for 15 min. with another 1 liter of petroleum ether which was decanted off The combined petroleum ether extracts were concentrated to an oil which was chromatographed on silica gel eluting with petroleum ether

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

Procedure: A solution of 5.0 g (37.3 mmole) of 1-hydroxy-6,6-dimethyl-2,4-heptadiyne and 14.8 g (44.7 mmole) of carbon tetrabromide in 250 mL of H2CCl2 was cooled to 0°-5° C. and 12.7 g (48.4 mmole) of triphenylphosphine was added thereto. The so formed mixture was stirred for 2 hours at 0°-5° C. The reaction mixture was concentrated to about 50 ml and poured into 1 liter of petroleum ether. The mixture was stirred 15 min. and the petroleum ether was removed by decantation. The oily residue was stirred for 15 min. with another 1 liter of petroleum ether which was decanted off. The combined petroleum ether extracts were concentrated to an oil which was chromatographed on silica gel, eluting with petroleum ether to give 6.87 g of the title compound, M/e, M+ 200. The so formed mixture The reaction mixture was concentrated to about 50 ml poured into 1 liter of petroleum ether The mixture was stirred 15 min. the petroleum ether was removed by decantation The oily residue was stirred for 15 min. with another 1 liter of petroleum ether which was decanted off The combined petroleum ether extracts were concentrated to an oil which was chromatographed on silica gel eluting with petroleum ether

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

Procedure: A solution of 5.0 g (37.3 mmole) of 1-hydroxy-6,6-dimethyl-2,4-heptadiyne and 14.8 g (44.7 mmole) of carbon tetrabromide in 250 mL of H2CCl2 was cooled to 0°-5° C. and 12.7 g (48.4 mmole) of triphenylphosphine was added thereto. The so formed mixture was stirred for 2 hours at 0°-5° C. The reaction mixture was concentrated to about 50 ml and poured into 1 liter of petroleum ether. The mixture was stirred 15 min. and the petroleum ether was removed by decantation. The oily residue was stirred for 15 min. with another 1 liter of petroleum ether which was decanted off. The combined petroleum ether extracts were concentrated to an oil which was chromatographed on silica gel, eluting with petroleum ether to give 6.87 g of the title compound, M/e, M+ 200. The so formed mixture The reaction mixture was concentrated to about 50 ml poured into 1 liter of petroleum ether The mixture was stirred 15 min. the petroleum ether was removed by decantation The oily residue was stirred for 15 min. with another 1 liter of petroleum ether which was decanted off The combined petroleum ether extracts were concentrated to an oil which was chromatographed on silica gel eluting with petroleum ether

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

Procedure: A solution of lithium aluminum hydride (11.4 mmol; 1M solution in tetrahydrofuran, (hereafter THF) was added to a stirred suspension of sodium methoxide (1.23 g, 22.8 mmol) in 18 ml of dry THF and the mixture was stirred at room temperature for 1/2 hour. 6,6-Dimethyl-2,4-heptadiyn-1-ol (777 mg, 5.71 mmol) was added and the mixture stirred at room temperature overnight. The mixture was cooled to 0° C. and dry ethyl acetate (1.0 g, 11.4 mmole) was added dropwise. Hexachloroethane (4.05 g, 17.13 mmole) was then added and the mixture was allowed to warm to room temperature. After 4.5 hours, additional hexachloroethane (1.35 g, 5.71 mmol) was added to the reaction mixture which was then stirred for 68 hours. The mixture was partitioned between ether and dilute aqueous hydrochloric acid, and the aqueous layer was extracted 3 times with ether. The combined ethereal extract was washed with water an brine, dried over anhydrous sodium sulfate and concentrated in vacuo to afford 3.43 g of crude product. This mixture was purified by chromatography on a column (2.5×47 cm) of silica gel eluting with ethyl acetate-hexane, 5/95. Combination and concentration of the appropriate fractions afforded 404 mg of the desired (Z)-3-chloro-6,6-dimethyl- 2-hepten-4-yn-1-ol. the mixture stirred at room temperature overnight The mixture was cooled to 0° C. to warm to room temperature After 4.5 hours was then stirred for 68 hours The mixture was partitioned between ether and dilute aqueous hydrochloric acid the aqueous layer was extracted 3 times with ether The combined ethereal extract was washed with water an brine dried over anhydrous sodium sulfate concentrated in vacuo to afford 3.43 g of crude product This mixture was purified by chromatography on a column (2.5×47 cm) of silica gel eluting with ethyl acetate-hexane, 5/95

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

Procedure: Nitrogen was bubbled through a mixture of cupric chloride (154 mg), NH2OH.HCl (0.45 g), and 70% aqueous diethylamine (9 ml) in 11 ml of water and 23 ml of methanol, for a few minutes. Propargyl alcohol (3.8 g, 0.068 mol) was added with stirring under nitrogen whereupon a yellow precipitate formed immediately. The mixture was warmed to 35°-40° C. for 15 minutes and 1-bromo-2-t-butyl-acetylene (8.57 g, 0.053 mmol) was added over 15 minutes. The mixture was stirred at 35°-40° C. for 45 minutes, then at room temperature for 1 hour. Aqueous potassium cyanide (0.45 g in 45 ml of water) was added and the mixture was stirred for one minute. The mixture was poured into 50 ml of water and extracted 5 times with ether. The combined organic phase was washed with water and dried over magnesium sulfate. The solvents were removed and the residue was distilled under reduced pressure through a column packed with glass helices. 6,6-Dimethyl-2,4-heptadiyne-1-ol (3.63 grams) was collected at 85° C. and 0.5 mm of mercury. Nitrogen was bubbled through a mixture of cupric chloride (154 mg), NH2OH.HCl (0.45 g), and 70% aqueous diethylamine (9 ml) in 11 ml of water and 23 ml of methanol, for a few minutes formed immediately The mixture was warmed to 35°-40° C. for 15 minutes The mixture was stirred at 35°-40° C. for 45 minutes the mixture was stirred for one minute extracted 5 times with ether The combined organic phase was washed with water dried over magnesium sulfate The solvents were removed the residue was distilled under reduced pressure through a column 6,6-Dimethyl-2,4-heptadiyne-1-ol (3.63 grams) was collected at 85° C.