(1S,5S)-4,6,6-trimethylbicyclo[3.1.1]hept-3-en-2-one

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (−)-α-pinene (136.2 g, 1 mole) was oxidised by bubbling in O2 in the presence of cobalt stearate (0.5 g), which is added portionwise, maintaining the temperature at approximately 5-55° C., for at least 50-60 hours. When the reaction was complete, the peroxide index was approximately 27-29%. After cooling to room temperature, the excess of peroxides was decomposed by adding to the reaction mixture an equal quantity of a hot aqueous solution (˜50° C.) of 5% ferrous sulphate and 1% sulphuric acid; the peroxide index was approximately 0 within approximately 2 hours. The organic phase was then separated and washed 2-3 times with water until a pH of 5-6 is obtained. The non-reacted (−)-α-pinene was removed by column distillation at a temperature of approximately 100° C. and at a pressure of 20-25 mmHg (2.6×10−2−3.3×10−2 bar). The distillation residue was constituted by a mixture of terpenes which was characterized by oxygenated functions (alcohol, ketone and aldehyde functions). A Bertagnini reaction was then carried out by adding to the reaction mixture a solution containing sodium sulphite (120 g, 0.954 mole), while maintaining the temperature at 55-60° C. Because the pH of the mixture gradually moved to basic values, a 50% acetic acid solution was added until the pH is neutral. When the pH remained stable at ˜7, the reaction, might be regarded as complete. The organic phase (containing the alcohols PINOCARVEOL, MIRTENOL, VERBENOL) was separated and the aqueous phase was counter-extracted 2-3 times with hexane. The aqueous solution was alkalinised to pH ˜14 and then extracted with hexane, thus obtaining the fraction containing carbonyl products (MIRTENAL AND VERBENONE). The hexane extract, washed 2-3 times with water, was concentrated to obtain a high-boiling oily residue constituted to the extent of more than 80% by VERBENONE. The residue was dissolved with methanol; the methanol solution was cooled to −5 to −1° C. and, while maintaining this temperature, sodium borohydride was added until the MIRTENAL was undetectable (monitoring by TLC). The reduction was then stopped by the addition of a small amount of acetic acid, until the solution was neutral. The methanol solution was concentrated to ⅔ the volume, then diluted with water and extracted with hexane. The hexane solution was evaporated under vacuum and the residue is distilled at 80° C./1.5 mm Hg (1.9×10−3 bar) to give VRBENONE (25 g, yield 16.6%) with [α]D2b=−217° (c=10 in ethanol). by bubbling in O2 in the presence of cobalt stearate (0.5 g), which is added portionwise for at least 50-60 hours After cooling to room temperature by adding to the reaction mixture an equal quantity of a hot aqueous solution (˜50° C.) of 5% ferrous sulphate and 1% sulphuric acid within approximately 2 hours The organic phase was then separated washed 2-3 times with water until a pH of 5-6 is obtained The non-reacted (−)-α-pinene was removed by column distillation at a temperature of approximately 100° C. and at a pressure of 20-25 mmHg (2.6×10−2−3.3×10−2 bar) The distillation residue was constituted by a mixture of terpenes which by oxygenated functions (alcohol, ketone and aldehyde functions) A Bertagnini reaction by adding to the reaction mixture a solution while maintaining the temperature at 55-60° C the reaction was separated the aqueous phase was counter-extracted 2-3 times with hexane extracted with hexane thus obtaining the fraction The hexane extract washed 2-3 times with water was concentrated to obtain a high-boiling oily residue was added until the MIRTENAL The methanol solution was concentrated diluted with water extracted with hexane The hexane solution was evaporated under vacuum the residue is distilled at 80° C./1.5 mm Hg (1.9×10−3 bar) to give

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (−)-α-pinene (136.2 g, 1 mole) was oxidised by bubbling in O2 in the presence of cobalt stearate (0.5 g), which is added portionwise, maintaining the temperature at approximately 5-55° C., for at least 50-60 hours. When the reaction was complete, the peroxide index was approximately 27-29%. After cooling to room temperature, the excess of peroxides was decomposed by adding to the reaction mixture an equal quantity of a hot aqueous solution (˜50° C.) of 5% ferrous sulphate and 1% sulphuric acid; the peroxide index was approximately 0 within approximately 2 hours. The organic phase was then separated and washed 2-3 times with water until a pH of 5-6 is obtained. The non-reacted (−)-α-pinene was removed by column distillation at a temperature of approximately 100° C. and at a pressure of 20-25 mmHg (2.6×10−2−3.3×10−2 bar). The distillation residue was constituted by a mixture of terpenes which was characterized by oxygenated functions (alcohol, ketone and aldehyde functions). A Bertagnini reaction was then carried out by adding to the reaction mixture a solution containing sodium sulphite (120 g, 0.954 mole), while maintaining the temperature at 55-60° C. Because the pH of the mixture gradually moved to basic values, a 50% acetic acid solution was added until the pH is neutral. When the pH remained stable at ˜7, the reaction, might be regarded as complete. The organic phase (containing the alcohols PINOCARVEOL, MIRTENOL, VERBENOL) was separated and the aqueous phase was counter-extracted 2-3 times with hexane. The aqueous solution was alkalinised to pH ˜14 and then extracted with hexane, thus obtaining the fraction containing carbonyl products (MIRTENAL AND VERBENONE). The hexane extract, washed 2-3 times with water, was concentrated to obtain a high-boiling oily residue constituted to the extent of more than 80% by VERBENONE. The residue was dissolved with methanol; the methanol solution was cooled to −5 to −1° C. and, while maintaining this temperature, sodium borohydride was added until the MIRTENAL was undetectable (monitoring by TLC). The reduction was then stopped by the addition of a small amount of acetic acid, until the solution was neutral. The methanol solution was concentrated to ⅔ the volume, then diluted with water and extracted with hexane. The hexane solution was evaporated under vacuum and the residue is distilled at 80° C./1.5 mm Hg (1.9×10−3 bar) to give VRBENONE (25 g, yield 16.6%) with [α]D2b=−217° (c=10 in ethanol). by bubbling in O2 in the presence of cobalt stearate (0.5 g), which is added portionwise for at least 50-60 hours After cooling to room temperature by adding to the reaction mixture an equal quantity of a hot aqueous solution (˜50° C.) of 5% ferrous sulphate and 1% sulphuric acid within approximately 2 hours The organic phase was then separated washed 2-3 times with water until a pH of 5-6 is obtained The non-reacted (−)-α-pinene was removed by column distillation at a temperature of approximately 100° C. and at a pressure of 20-25 mmHg (2.6×10−2−3.3×10−2 bar) The distillation residue was constituted by a mixture of terpenes which by oxygenated functions (alcohol, ketone and aldehyde functions) A Bertagnini reaction by adding to the reaction mixture a solution while maintaining the temperature at 55-60° C the reaction was separated the aqueous phase was counter-extracted 2-3 times with hexane extracted with hexane thus obtaining the fraction The hexane extract washed 2-3 times with water was concentrated to obtain a high-boiling oily residue was added until the MIRTENAL The methanol solution was concentrated diluted with water extracted with hexane The hexane solution was evaporated under vacuum the residue is distilled at 80° C./1.5 mm Hg (1.9×10−3 bar) to give

Conditions: temp:30.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: (−)-α-pinene (136.2 g, 1 mole) was oxidised by bubbling in O2 in the presence of cobalt stearate (0.5 g), which is added portionwise, maintaining the temperature at approximately 5-55° C., for at least 50-60 hours. When the reaction was complete, the peroxide index was approximately 27-29%. After cooling to room temperature, the excess of peroxides was decomposed by adding to the reaction mixture an equal quantity of a hot aqueous solution (˜50° C.) of 5% ferrous sulphate and 1% sulphuric acid; the peroxide index was approximately 0 within approximately 2 hours. The organic phase was then separated and washed 2-3 times with water until a pH of 5-6 is obtained. The non-reacted (−)-α-pinene was removed by column distillation at a temperature of approximately 100° C. and at a pressure of 20-25 mmHg (2.6×10−2−3.3×10−2 bar). The distillation residue was constituted by a mixture of terpenes which was characterized by oxygenated functions (alcohol, ketone and aldehyde functions). A Bertagnini reaction was then carried out by adding to the reaction mixture a solution containing sodium sulphite (120 g, 0.954 mole), while maintaining the temperature at 55-60° C. Because the pH of the mixture gradually moved to basic values, a 50% acetic acid solution was added until the pH is neutral. When the pH remained stable at ˜7, the reaction, might be regarded as complete. The organic phase (containing the alcohols PINOCARVEOL, MIRTENOL, VERBENOL) was separated and the aqueous phase was counter-extracted 2-3 times with hexane. The aqueous solution was alkalinised to pH ˜14 and then extracted with hexane, thus obtaining the fraction containing carbonyl products (MIRTENAL AND VERBENONE). The hexane extract, washed 2-3 times with water, was concentrated to obtain a high-boiling oily residue constituted to the extent of more than 80% by VERBENONE. The residue was dissolved with methanol; the methanol solution was cooled to −5 to −1° C. and, while maintaining this temperature, sodium borohydride was added until the MIRTENAL was undetectable (monitoring by TLC). The reduction was then stopped by the addition of a small amount of acetic acid, until the solution was neutral. The methanol solution was concentrated to ⅔ the volume, then diluted with water and extracted with hexane. The hexane solution was evaporated under vacuum and the residue is distilled at 80° C./1.5 mm Hg (1.9×10−3 bar) to give VRBENONE (25 g, yield 16.6%) with [α]D2b=−217° (c=10 in ethanol). by bubbling in O2 in the presence of cobalt stearate (0.5 g), which is added portionwise for at least 50-60 hours After cooling to room temperature by adding to the reaction mixture an equal quantity of a hot aqueous solution (˜50° C.) of 5% ferrous sulphate and 1% sulphuric acid within approximately 2 hours The organic phase was then separated washed 2-3 times with water until a pH of 5-6 is obtained The non-reacted (−)-α-pinene was removed by column distillation at a temperature of approximately 100° C. and at a pressure of 20-25 mmHg (2.6×10−2−3.3×10−2 bar) The distillation residue was constituted by a mixture of terpenes which by oxygenated functions (alcohol, ketone and aldehyde functions) A Bertagnini reaction by adding to the reaction mixture a solution while maintaining the temperature at 55-60° C the reaction was separated the aqueous phase was counter-extracted 2-3 times with hexane extracted with hexane thus obtaining the fraction The hexane extract washed 2-3 times with water was concentrated to obtain a high-boiling oily residue was added until the MIRTENAL The methanol solution was concentrated diluted with water extracted with hexane The hexane solution was evaporated under vacuum the residue is distilled at 80° C./1.5 mm Hg (1.9×10−3 bar) to give