2,6,6-trimethylbicyclo[3.1.1]hept-2-ene

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

Procedure: A mixture of 31.2 g (0.12 mole) of N,N′-diphenyl-N,N′-p-phenylenediamine, 54.5 g (0.25 mole) of m-iodotoluene, 32.6 g (0.34 mole) of t-butoxy sodium, 59.0 mg (0.6 mmole) of copper (I) chloride, 185 mg (0.6 mmole) of 2-(5,6-diphenyl-2-pyridyl)pyridine (A-8) and 87.6 ml of α-pinene was reacted at 125 to 130° C. for 5 hours under a nitrogen gas stream. After completion of the reaction, 66 ml of toluene and 66 ml of water were added to separate the reaction mixture. Toluene was then concentrated under reduced pressure. The residue was crystallized by the addition of 39 ml of ethyl acetate and 253 ml of isopropanol, whereby 47.8 g (yield: 90.5%) of the target compound was obtained as pale yellow crude crystals. The compound was found to have a melting point of 170 to 171° C. and an HPLC content (column: YMC-A-002, UV detector: 310 nm, eluent having a flow rate of 1.1 ml/min) was 99.5%. was reacted at 125 to 130° C. for 5 hours under a nitrogen gas stream were added to separate the reaction mixture Toluene was then concentrated under reduced pressure The residue was crystallized by the addition of 39 ml of ethyl acetate and 253 ml of isopropanol

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2,5-Dimercapto-1,3,4-thiadiazole (35.0 g, 0.23 mol) was charged into a reaction flask along with alpha-pinene (33.85 g, 0.24 mol). The reaction was heated to 100° C. for 1 hour and then cautiously heated to 120° C. The reaction exothermed and was maintained at 155° C. for 20 min. Dibutyl maleate (53.5 g, 0.55 mol) was added and the reaction was maintained at 155° C. for 3 hours. The reaction product was then cooled, charged with sodium carbonate (about 1 g) and stirred. The product was filtered using a filter aid. cautiously heated to 120° C The reaction exothermed was maintained at 155° C. for 20 min the reaction was maintained at 155° C. for 3 hours The reaction product was then cooled The product was filtered

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

Procedure: A process for producing 2-hydroxy-3-pinanone, comprising the steps of reacting α-pinene with catalytic potassium osmate in solution of pyridine, N-methylmorpholine-N-oxide and aqueous acetone to produce cis-pinanediol; and thereafter oxidizing said cis-pinanediol with DMSO activated by pyridine.SO3 and triethylamine in an appropriate solvent to produce 2-hydroxy-3-pinanone.

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

Procedure: reacting α-pinene with catalytic potassium osmate in a solution of pyridine, N-methylmorpholine-N-oxide and aqueous acetone to form cis-pinanediol;

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

Procedure: Hypochlorite treatment of the α-pinene raised the chloride level to about 100 ppm (as elemental chloride) based on pinene feed. Hydrogenation of this pinene was fast and yielded a good ratio (96.8/3.2). Reuse of the catalyst heel went quickly with a slightly reduced ratio, when used at either the 3% level or 1% level. Repoisoning (1/2% sodium hypochlorite-treated α-pinene) was achieved by mixing hypochlorite-treated feed with fresh α-pinene and yielded pinane with a 97.5/2.5 cis-:trans- ratio. A ratio of 98.1/1.9 was achieved in 30 hours' reaction at a lower temperature of about 30° C. using hypochlorite-treated feed.

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

Procedure: Ruthenium has been found to be a stereoselective catalyst for the hydrogenation of α-pinene to obtain cis-pinane.

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

Procedure: A well stirred solution of benzoyl peroxide (24.0 g), cuprous chloride (0.2 g), cupric benzoate (1.5 g) and alpha-pinene (28.0 g) in acetonitrile (150 ml) is heated on an oil bath at 65° ± 5° for 24 hours. The acetonitrile is removed by evaporation under vacuum (water pressure) at 40°. Excess alpha-pinene is recovered by continuing the evaporation at 75° (3 mm). The resulting blue-green slurry is dissolved in 100 ml ether and the solution filtered to remove the cupric benzoate. The filtrate is washed with 2N HCl (2 × 30 ml), distilled water (3 × 30 ml) and then the ether removed by evaporation. This gives a straw colored oil which is dissolved in a solution of methanol (200 ml), water (50 ml), NaOH (10 g), and hydroylzed by refluxing 1 hour. Removal of the methanol affords an aqueous suspension which is diluted with water (100 ml) and steam distilled. The distillate is extracted with ether (4 × 20 ml). This organic solution is dried over magnesium sulphate and evaporated to yield crude trans-carveol (9.2 g). Distillation affords pure material, b.p. 106°-110°C (10 mm). The acetonitrile is removed by evaporation under vacuum (water pressure) at 40° Excess alpha-pinene is recovered the evaporation at 75° (3 mm) The resulting blue-green slurry is dissolved in 100 ml ether the solution filtered to remove the cupric benzoate The filtrate is washed with 2N HCl (2 × 30 ml) distilled water (3 × 30 ml) the ether removed by evaporation This gives a straw colored oil which hydroylzed by refluxing 1 hour Removal of the methanol affords an aqueous suspension which distilled The distillate is extracted with ether (4 × 20 ml) This organic solution is dried over magnesium sulphate evaporated

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

Procedure: Isovaleraldehyde (2.15 g, 2.68 mL, 25 mmol) in ether (6 mL) was added dropwise to a rapidly stirred solution of B-Isoprenyldiisopinocampheylborane, dIpc2BIpn, maintained in THF/EE (1:2) at -100° C. Stirring was continued for 6 h, when the 11B NMR spectrum of an aliquot showed a peak at δ52 ppm, corresponding to a borinate indicating completion of the reaction. The reaction mixture was warmed to 0° C. and acetaldehyde (2.1 mL, 37.5 mmol) was added when one equiv of α-pinene was eliminated. 11B NMR showed a peak at δ32 ppm corresponding to a boronate. The solvents were removed in vacuo and EE (20 mL) was added, followed by 1.1 equiv. of diethanolamine (2.6 mL, 27.5 mmol). Stirring was continued for 2 h and the precipitated boron components were filtered and the filtrate concentrated. Distillation (92°-94° C./19 mm Hg) provided 2.3 g (60 %) of (+)-ipsenol, [α]D =+18.5° which corresponds to 100% ee. The spectral properties were identical to the sample obtained from example 9. The solvents were removed in vacuo and EE (20 mL) was added Stirring was continued for 2 h the precipitated boron components were filtered the filtrate concentrated Distillation (92°-94° C./19 mm Hg)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Isovaleraldehyde (2.15 g, 2.68 mL, 25 mmol) in ether (6 mL) was added dropwise to a rapidly stirred solution of B-isoprenyldiisopinocampheylborane, lIpc2BIpn, maintained at -78° C. Stirring was continued for 1 h, when the 11B NMR spectrum of an aliquot showed a peak at δ52 ppm corresponding to a borinate indicating completion of the reaction. The reaction mixture was warmed to 0° C. and acetaldehyde (2.1 mL, 37.5 mmol) was added when one equiv of α-pinene was eliminated. 11B NMR showed a peak at δ32 ppm corresponding to a boronate. THF was substituted with EE and 1.1 equiv. of diethanolamine (2.6 mL), 27.5 mmol) was added and stirred for 2 h. The precipitated boron components were filtered and the filtrate was concentrated and distilled (92°-94° C./19 mm Hg) to yield 2.5 g (65%) of (-)-ipsenol. [α]D =-17.67 ° (c 1, MeOH) which corresponds to 96% ee. The spectral properties were identical to the racemic mixture of Example 6. The reaction mixture was warmed to 0° C. was added stirred for 2 h The precipitated boron components were filtered the filtrate was concentrated distilled (92°-94° C./19 mm Hg)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Isovaleraldehyde (2.15 g, 2.68 mL, 25 mmol) in ether (6 mL) was added dropwise to a rapidly stirred solution of B-isoprenyldiisopinocampheylborane, lIpc2BIpn, maintained at -78° C. Stirring was continued for 1 h, when the 11B NMR spectrum of an aliquot showed a peak at δ52 ppm corresponding to a borinate indicating completion of the reaction. The reaction mixture was warmed to 0° C. and acetaldehyde (2.1 mL, 37.5 mmol) was added when one equiv of α-pinene was eliminated. 11B NMR showed a peak at δ32 ppm corresponding to a boronate. THF was substituted with EE and 1.1 equiv. of diethanolamine (2.6 mL), 27.5 mmol) was added and stirred for 2 h. The precipitated boron components were filtered and the filtrate was concentrated and distilled (92°-94° C./19 mm Hg) to yield 2.5 g (65%) of (-)-ipsenol. [α]D =-17.67 ° (c 1, MeOH) which corresponds to 96% ee. The spectral properties were identical to the racemic mixture of Example 6. The reaction mixture was warmed to 0° C. was added stirred for 2 h The precipitated boron components were filtered the filtrate was concentrated distilled (92°-94° C./19 mm Hg)

Conditions: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Isovaleraldehyde (2.15 g, 2.68 mL, 25 mmol) in ether (6 mL) was added dropwise to a rapidly stirred solution of B-isoprenyldiisopinocampheylborane, dIpc2BIpn, maintained at -78° C. Stirring was continued for 1 h, when the 11B NMR spectrum of an aliquot showed a peak at δ52 ppm corresponding to a borinate indicating completion of the reaction. The reaction mixture was warmed to 0° C. and acetaldehyde (2.1 mL, 37.5 mmol) was added when one equiv of α-pinene was eliminated. 11B NMR showed a peak at δ32 ppm corresponding to a boronate. THF was substituted with EE and 1.1 equiv. of diethanolamine (2.6 mL, 27.5 mmol) was added and stirred for 2 h. The precipitated boron components were filtered and the filtrate was concentrated and distilled (92°-94° C./19 mm Hg) to yield 2.3 g (60%) of (+)-ipsenol. [α]D =+17.3° (c 1, MeOH) which corresponds to 93.7% ee. The spectral properties were identical to the racemic mixture of Example 6. The reaction mixture was warmed to 0° C. was added stirred for 2 h The precipitated boron components were filtered the filtrate was concentrated distilled (92°-94° C./19 mm Hg)

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

Procedure: in a first stage, epoxidizing α-pinene with a 15-30% solution of perbenzoic acid in chloroform at a temperature between -1° C. and -10° C. to obtain α-pinene epoxide at a temperature between -1° C. and -10° C.