1-bromo-3,3-dimethylbut-1-yne

Conditions: temp:0.00; pressure:0.00; stir:

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:; See reaction.notes.procedure_details.

Procedure: A methanol solution (7.5 ml) of 0.75 ml of propargyl bromide was added dropwise to 6 ml of a 70% aqueous solution of ethylamine with stirring and ice cooling, and the mixture was stirred for 1.5 hours. 120 mg of copper(I) chloride and 100 mg of hydroxylamine hydrochloride were added, and to this solution, a methanol solution(3 ml) of 5.6 mg of 1-bromo-3,3-dimethyl-1-butyne [synthesized by a bromination of lithiated tert-butylacetylene with bromine ] was added dropwise under ice cooling. The mixture was stirred at room temperature for 2 hours, and then the solvent was evaporated. The residue was worked up in a customary manner, and the product was treated with a methanol solution of hydrogen chloride to give 0.94 g of the captioned hydrochloride as a white crystalline powder. ice cooling, and the mixture was stirred for 1.5 hours was added dropwise under ice cooling The mixture was stirred at room temperature for 2 hours the solvent was evaporated the product was treated with a methanol solution of hydrogen chloride

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.