1-cyclohexylprop-2-yn-1-one

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

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1.6 liters 0.5M 9-borabicyclo[3.3.1]nonane in tetrahydrofuran and 122.6 g (-)-α-pinene was heated at reflux under nitrogen for 4 hr., at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil. The contents of the flask were cooled to 0° C. and 80 g of 1-cyclohexyl-2-propyn-1-one, prepared according to Preparation 4, was added with stirring. The resulting mixture was allowed to warm to 23° C. and it was stirred at that temperature for 16 hr. Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde and stirring at 23° C. for 1 hr. The liberated (-)-α-pinene was removed by vacuum distillation. The resulting mixture was diluted with 400 ml tetrahydrofuran followed by 300 ml 3N sodium hydroxide. To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr. The mixture was heated at 40° C. for 3 hr. After cooling, the mixture was extracted with diethyl ether and this extract was dried over magnesium sulfate. Evaporation of the solvent and purification of the residue by silica gel flash chromatography using 5% ethyl acetate-hexane gave 56 g of (S)-3-cyclohexyl-1-propyn-3-ol, which by nmr analysis was shown to be 90% e.e. was heated at reflux under nitrogen for 4 hr , at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil according to Preparation 4 was added to warm to 23° C. it was stirred at that temperature for 16 hr Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde stirring at 23° C. for 1 hr The liberated (-)-α-pinene was removed by vacuum distillation The resulting mixture was diluted with 400 ml tetrahydrofuran To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr The mixture was heated at 40° C. for 3 hr After cooling the mixture was extracted with diethyl ether this extract was dried over magnesium sulfate Evaporation of the solvent and purification of the residue by silica gel flash chromatography

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

Procedure: A solution of chromic acid was prepared by dissolving 106.88 g chromium trioxide in 400 ml water and then adding 92 ml concentrated sulfuric acid. This solution is added in dropwise fashion over a 3 hr. period to an ice cooled, stirred solution of 120 g 3-cyclohexyl-1-propyn-3-ol in 175 ml acetone. The resulting mixture was diluted with 500 ml water and the product was extracted into 1 liter of diethyl ether. The ether extract was washed with 250 ml saturated sodium bisulfite solution and was dried over sodium sulfate. The diethyl ether was removed by distillation under nitrogen atmosphere and the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg) to give 84.9 g of 1-cyclohexyl-2-propyn-1-one as an oil: MS m/z=136 (M+) Caled. for C9H12O:C, 79.37; H, 8.88. Found:C, 79.24; H, 8.6. This solution is added in dropwise fashion over a 3 hr the product was extracted into 1 liter of diethyl ether The ether extract was washed with 250 ml saturated sodium bisulfite solution was dried over sodium sulfate The diethyl ether was removed by distillation under nitrogen atmosphere the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1.6 liters 0.5 M 9-borabicyclo[3.3.1]-nonane in tetrahydrofuran and 122.6 g (-)-α-pinene, 99%+pure, was heated at reflux under nitrogen for 4 hr., at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil. The contents of the flask were cooled to 0° C. and 80 g of 3-cyclohexylprop-1-yn-3-one, prepared as shown in Preparation 2, was added with stirring. The resulting mixture was allowed to warm to 23° C. and was stirred at that temperature for 16 hr. Excess reagent was destroyed by adding 44 ml propionaldehyde and stirring at 23° C. for 1 hr. The liberated (-)-α-pinene was removed by vacuum distillation. The resulting mixture was diluted with 400 ml tetrahydrofuran followed by 300 ml 3N sodium hydroxide. To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr. The mixture was heated at 40° C. for 3 hr. After cooling, the mixture was extracted with diethyl ether and this extract was dried over magnesium sulfate. Evaporation of the solvent and purification of the residue by silica gel flash chromatography using 5% ethyl acetate hexane gave 56 g of (S)-3-cyclohexyl prop-1-yn-3-ol, which by nmr analysis was shown to be 90% e.e. Recrystallization from hexane gave 45 g of the pure S isomer, mp 56°-58°, [α]D25 =-11.1°(C=0.53, Et2O) was heated at reflux under nitrogen for 4 hr , at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil as shown in Preparation 2 was added to warm to 23° C. was stirred at that temperature for 16 hr Excess reagent was destroyed by adding 44 ml propionaldehyde stirring at 23° C. for 1 hr The liberated (-)-α-pinene was removed by vacuum distillation The resulting mixture was diluted with 400 ml tetrahydrofuran To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr The mixture was heated at 40° C. for 3 hr After cooling the mixture was extracted with diethyl ether this extract was dried over magnesium sulfate Evaporation of the solvent and purification of the residue by silica gel flash chromatography

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1.6 liters 0.5 M 9-borabicyclo[3.3.1]-nonane in tetrahydrofuran and 122.6 g (-)-α-pinene, 99%+pure, was heated at reflux under nitrogen for 4 hr., at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil. The contents of the flask were cooled to 0° C. and 80 g of 3-cyclohexylprop-1-yn-3-one, prepared as shown in Preparation 2, was added with stirring. The resulting mixture was allowed to warm to 23° C. and was stirred at that temperature for 16 hr. Excess reagent was destroyed by adding 44 ml propionaldehyde and stirring at 23° C. for 1 hr. The liberated (-)-α-pinene was removed by vacuum distillation. The resulting mixture was diluted with 400 ml tetrahydrofuran followed by 300 ml 3N sodium hydroxide. To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr. The mixture was heated at 40° C. for 3 hr. After cooling, the mixture was extracted with diethyl ether and this extract was dried over magnesium sulfate. Evaporation of the solvent and purification of the residue by silica gel flash chromatography using 5% ethyl acetate hexane gave 56 g of (S)-3-cyclohexyl prop-1-yn-3-ol, which by nmr analysis was shown to be 90% e.e. Recrystallization from hexane gave 45 g of the pure S isomer, mp 56°-58°, [α]D25 =-11.1°(C=0.53, Et2O) was heated at reflux under nitrogen for 4 hr , at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil as shown in Preparation 2 was added to warm to 23° C. was stirred at that temperature for 16 hr Excess reagent was destroyed by adding 44 ml propionaldehyde stirring at 23° C. for 1 hr The liberated (-)-α-pinene was removed by vacuum distillation The resulting mixture was diluted with 400 ml tetrahydrofuran To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr The mixture was heated at 40° C. for 3 hr After cooling the mixture was extracted with diethyl ether this extract was dried over magnesium sulfate Evaporation of the solvent and purification of the residue by silica gel flash chromatography

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

Procedure: In like manner, but replacing the 3-cyclohexylprop-1-yn-3-ol with oct-1-yn-3-ol, oct-1-yn-3-one was prepared. C. Similarly, but starting with other appropriate 3-hydroxy-1-alkynes, prepared as shown above, the following 3-oxo-1-alkynes are prepared: was prepared prepared are prepared

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

Procedure: A solution of chromic acid was prepared by dissolving 106.88 g chromium trioxide in 400 ml water and then adding 92 ml concentrated sulfuric acid. This solution was added in dropwise fashion over a 3 hr. period to an ice cooled, stirred solution of 120 g 3 cyclohexyl-1-propyn-3-ol, prepared as shown in Preparation 1, in 175 ml acetone. The resulting mixture was diluted with 500 ml water and the product was extracted into 1 liter of diethyl ether. The ether extract was washed with 250 ml saturated sodium bisulfite solution and was dried over sodium sulfate. The diethyl ether was removed by distillation under nitrogen atmosphere and the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg) to give 84.9 g of 3-cyclohexylprop-1-yn-3-one as an oil: MS m/z=136 (M+) Calcd. for C9H12O: C, 79.37; H, 8.88. Found: C, 79.24; H, 8 60. This solution was added in dropwise fashion over a 3 hr prepared the product was extracted into 1 liter of diethyl ether The ether extract was washed with 250 ml saturated sodium bisulfite solution was dried over sodium sulfate The diethyl ether was removed by distillation under nitrogen atmosphere the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg)

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

Procedure: A solution of chromic acid was prepared by dissolving 106.88 g chromium trioxide in 400 ml water and then adding 92 ml concentrated sulfuric acid. This solution was added in dropwise fashion over a 3 hr. period to an ice cooled, stirred solution of 120 g 3 cyclohexyl-1-propyn-3-ol, prepared as shown in Preparation 1, in 175 ml acetone. The resulting mixture was diluted with 500 ml water and the product was extracted into 1 liter of diethyl ether. The ether extract was washed with 250 ml saturated sodium bisulfite solution and was dried over sodium sulfate. The diethyl ether was removed by distillation under nitrogen atmosphere and the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg) to give 84.9 g of 3-cyclohexylprop-1-yn-3-one as an oil: MS m/z=136 (M+) Calcd. for C9H12O: C, 79.37; H, 8.88. Found: C, 79.24; H, 8 60. This solution was added in dropwise fashion over a 3 hr prepared the product was extracted into 1 liter of diethyl ether The ether extract was washed with 250 ml saturated sodium bisulfite solution was dried over sodium sulfate The diethyl ether was removed by distillation under nitrogen atmosphere the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1.6 liters 0.5M 9-borabicyclo[3.3.1]nonane in tetrahydrofuran and 122.6 g (-)-α-pinene, 99%+ pure, was heated at reflux under nitrogen for 4 hr., at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil. The contents of the flask were cooled to 0° C. and 80 g of 3-cyclohexylprop-1-yn-3-one, prepared according to Preparation 8, was added with stirring. The resulting mixture was allowed to warm to 23° C. and was stirred at that temperature for 16 hr. Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde and stirring at 23° C. for 1 hr. The liberated (-)-α-pinene was removed by vacuum distillation. The resulting mixture was diluted with 400 ml tetrahydrofuran followed by 300 ml 3N sodium hydroxide. To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr. The mixture was heated at 40° C. for 3 hr. After cooling, the mixture was extracted with diethyl ether and this extract was dried over magnesium sulfate. Evaporation of the solvent and purification of the residue by silica gel flash chromatography using 5% ethyl acetate-hexane gave 56 g of (S)-3-cyclohexyl prop-1-yn-3-ol, which by nmr analysis was shown to be 90% e.e. Recrystallization from hexane gave 45 g of the pure S isomer, mp 56°-58°, [α]D25 =-11.1° (C=0.53, Et2O) was heated at reflux under nitrogen for 4 hr , at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil according to Preparation 8 was added to warm to 23° C. was stirred at that temperature for 16 hr Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde stirring at 23° C. for 1 hr The liberated (-)-α-pinene was removed by vacuum distillation The resulting mixture was diluted with 400 ml tetrahydrofuran To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr The mixture was heated at 40° C. for 3 hr After cooling the mixture was extracted with diethyl ether this extract was dried over magnesium sulfate Evaporation of the solvent and purification of the residue by silica gel flash chromatography

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1.6 liters 0.5M 9-borabicyclo[3.3.1]nonane in tetrahydrofuran and 122.6 g (-)-α-pinene, 99%+ pure, was heated at reflux under nitrogen for 4 hr., at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil. The contents of the flask were cooled to 0° C. and 80 g of 3-cyclohexylprop-1-yn-3-one, prepared according to Preparation 8, was added with stirring. The resulting mixture was allowed to warm to 23° C. and was stirred at that temperature for 16 hr. Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde and stirring at 23° C. for 1 hr. The liberated (-)-α-pinene was removed by vacuum distillation. The resulting mixture was diluted with 400 ml tetrahydrofuran followed by 300 ml 3N sodium hydroxide. To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr. The mixture was heated at 40° C. for 3 hr. After cooling, the mixture was extracted with diethyl ether and this extract was dried over magnesium sulfate. Evaporation of the solvent and purification of the residue by silica gel flash chromatography using 5% ethyl acetate-hexane gave 56 g of (S)-3-cyclohexyl prop-1-yn-3-ol, which by nmr analysis was shown to be 90% e.e. Recrystallization from hexane gave 45 g of the pure S isomer, mp 56°-58°, [α]D25 =-11.1° (C=0.53, Et2O) was heated at reflux under nitrogen for 4 hr , at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil according to Preparation 8 was added to warm to 23° C. was stirred at that temperature for 16 hr Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde stirring at 23° C. for 1 hr The liberated (-)-α-pinene was removed by vacuum distillation The resulting mixture was diluted with 400 ml tetrahydrofuran To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr The mixture was heated at 40° C. for 3 hr After cooling the mixture was extracted with diethyl ether this extract was dried over magnesium sulfate Evaporation of the solvent and purification of the residue by silica gel flash chromatography

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

Procedure: A solution of chromic acid was prepared by dissolving 106.88 g chromium trioxide in 400 ml water and then adding 92 ml concentrated sulfuric acid. This solution was added in dropwise fashion over a 3 hr. period to an ice cooled, stirred solution of 120 g 3-cyclohexyl-1-propyn-3-ol in 175 ml acetone. The resulting mixture was diluted with 500 ml water and the product was extracted into 1 liter of diethyl ether. The ether extract was washed with 250 ml saturated sodium bisulfite solution and was dried over sodium sulfate. The diethyl ether was removed by distillation under nitrogen atmosphere and the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg) to give 84.9 g of 3-cyclohexylprop-1-yn-3-one as an oil: MS m/z=136 (M+) Calcd. for C9H12O: C, 79.37; H, 8.88. Found: C, 79.24; H, 8.60. This solution was added in dropwise fashion over a 3 hr the product was extracted into 1 liter of diethyl ether The ether extract was washed with 250 ml saturated sodium bisulfite solution was dried over sodium sulfate The diethyl ether was removed by distillation under nitrogen atmosphere the resulting residue was purified by Kugelrohr distillation (65° C., 0.1 mm Hg)

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 1.6 liters 0.5M 9-borabicyclo[3.3.1]nonane in tetrahydrofuran and 122.6 g (-)-α-pinene was heated at reflux under nitrogen for 4 hr., at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil. The contents of the flask were cooled to 0° C. and 80 g of 1-cyclohexyl-2-propyn-1-one, prepared according to Preparation 4, was added with stirring. The resulting mixture was allowed to warm to 23° C. and it was stirred at that temperature for 16 hr. Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde and stirring at 23° C. for 1 hr. The liberated (-)-α-pinene was removed by vacuum distillation. The resulting mixture was diluted with 400 ml tetrahydrofuran followed by 300 ml 3N sodium hydroxide. To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr. The mixture was heated at 40° C. for 3 hr. After cooling, the mixture was extracted with diethyl ether and this extract was dried over magnesium sulfate. Evaporation of the solvent and purification of the residue by silica gel flash chromatography using 5% ethyl acetate-hexane gave 56 g of (S)-3-cyclohexyl-1-propyn-3-ol, which by nmr analysis was shown to be 90% e.e. was heated at reflux under nitrogen for 4 hr , at which time the excess (-)-α-pinene and tetrahydrofuran were removed under vacuum to leave a thick oil according to Preparation 4 was added to warm to 23° C. it was stirred at that temperature for 16 hr Excess S-Alpine borane was destroyed by adding 44 ml propionaldehyde stirring at 23° C. for 1 hr The liberated (-)-α-pinene was removed by vacuum distillation The resulting mixture was diluted with 400 ml tetrahydrofuran To this stirred mixture was added in dropwise fashion 300 ml 30% hydrogen peroxide over 1 hr The mixture was heated at 40° C. for 3 hr After cooling the mixture was extracted with diethyl ether this extract was dried over magnesium sulfate Evaporation of the solvent and purification of the residue by silica gel flash chromatography