5,5-dimethylcyclohex-2-en-1-one

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

Procedure: Dissolve 3-methoxy-5,5-dimethyl-cyclohex-2-enone (Tetrahedron 57 (2001) 217-225) (10.6 g, 68.7 mmol) in ether (500 ml) cool to 0° C., add dropwise a 1.5M solution of diisobutyl aluminum hydride (68.7 ml, 103 mmol), and stir for 30 minutes. Add saturated aqueous ammonium chloride (25 ml), stir 1 hour, add anhydrous magnesium sulfate (10 g), stir 1 hour. Filter through celite and concentrate. Dissolve the residue in ether (500 ml), add toluene-4-sulfonic acid monohydrate (650 mg, 3.44 mmol) and water (6.2 ml), and stir 1 hour. Wash with saturated aqueous sodium bicarbonate, brine, dry and concentrate to give the title compound as a clear oil (5.0 g, 58%): 1H NMR (CDCl3) δ 6.89-6.84 (m, 1H), 2.28 (s, 2H), 2.26-2.24 (q, 2H), 1.06 (s, 6H). stir 1 hour Filter through celite and concentrate Dissolve the residue in ether (500 ml) stir 1 hour Wash with saturated aqueous sodium bicarbonate, brine dry concentrate

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

Procedure: A solution of 3-methoxy-5,5-dimethyl-cyclohex-2-enone (80 g, 0.52 mol) in anhydrous tetrahydrofuran (270 mL) was treated dropwise with a 1 M solution of LiAlH4 in tetrahydrofuran (182 mL), under argon atmosphere and keeping the temperature of the reaction between 0° C. and 5° C. The temperature was allowed to rise to 25° C. and the mixture was stirred for 4 hours. The resulting slurry was cooled with an ice bath, quenched with ethyl acetate (30 mL) and poured with caution into a cooled 2 M H2SO4 solution. The aqueous solution was then extracted with diethyl ether (300 mL×3), dried on Na2SO4 and evaporated under reduced pressure to remove most of the solvent. The crude material contained the title compound as a low boiling point oil that was used in the next step without further purification. the temperature of the reaction between 0° C. and 5° C to rise to 25° C. The resulting slurry was cooled with an ice bath quenched with ethyl acetate (30 mL) poured with caution into a cooled 2 M H2SO4 solution The aqueous solution was then extracted with diethyl ether (300 mL×3) dried on Na2SO4 evaporated under reduced pressure to remove most of the solvent was used in the next step without further purification

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

Procedure: Activated zinc dust (15.0 g) was added to a stirred solution of 3-chloro-5,5-dimethylcyclohex-2-enone (9.0 g) and potassium iodide (7.5 g) in methanol (50 ml). After stirring for a period of 18 hours the mixture was filtered and the filtrate concentrated by evaporation under reduced pressure. The residue was mixed with dilute (8% w/v) hydrochloric acid and extracted with diethyl ether (2 × 100 ml). The combined ethereal extracts were washed with water and dried over anhydrous magnesium sulphate. After removal of the ether by evaporation under reduced pressure the residual oil was purified by distillation. 5,5-Dimethylcyclohex-2-enone was obtained as a pale yellow oil, b.p. 75° C./17 mm Hg. was filtered the filtrate concentrated by evaporation under reduced pressure The residue was mixed with dilute (8% w/v) hydrochloric acid extracted with diethyl ether (2 × 100 ml) The combined ethereal extracts were washed with water dried over anhydrous magnesium sulphate After removal of the ether by evaporation under reduced pressure the residual oil was purified by distillation

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

Procedure: (a') A catalytic hydrogenation of 3,3-dimethyl-cyclohex-5-en-1-one was carried out according to the usual techniques in the presence of palladium on charcoal and yielded 3,3-dimethyl-cyclohexanone. The subsequent ethylination by means of acetylene in a basic medium gave 1-ethynyl-1-hydroxy-3,3-dimethyl-cyclohexane in about 50% yield.

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

Procedure: 8 g of a 14% solution of butyl-lithium in diethylether were added under nitrogen within 15 min. to a suspension of 7 g of the above said phosphonium bromide in 80 ml ether. To the red resulting solution, cooled to 5°-10°, 2.1 g of 3,3-dimethyl-cyclohex-5-en-1-one in 10 ml ether, were added, whereupon, the reaction mixture was stirred for 3 h, filtered and the clear filtrate was washed with water until neutrality. On evaporation and distillation in a bulb apparatus, 1.5 g (50% yield) of (3,3-dimethyl-cyclohex-5-en-1-yliden-)-pent-4-ene were obtained. To the red resulting solution, cooled to 5°-10° filtered the clear filtrate was washed with water until neutrality On evaporation and distillation in a bulb apparatus

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

Procedure: Dissolve 3-methoxy-5,5-dimethyl-cyclohex-2-enone (Tetrahedron 57 (2001) 217-225) (10.6 g, 68.7 mmol) in ether (500 ml) cool to 0° C., add dropwise a 1.5M solution of diisobutyl aluminum hydride (68.7 ml, 103 mmol), and stir for 30 minutes. Add saturated aqueous ammonium chloride (25 ml), stir 1 hour, add anhydrous magnesium sulfate (10 g), stir 1 hour. Filter through celite and concentrate. Dissolve the residue in ether (500 ml), add toluene-4-sulfonic acid monohydrate (650 mg, 3.44 mmol) and water (6.2 ml), and stir 1 hour. Wash with saturated aqueous sodium bicarbonate, brine, dry and concentrate to give the title compound as a clear oil (5.0 g, 58%): 1H NMR (CDCl3) δ 6.89-6.84 (m, 1H), 2.28 (s, 2H), 2.26-2.24 (q, 2H), 1.06 (s, 6H). stir 1 hour Filter through celite and concentrate Dissolve the residue in ether (500 ml) stir 1 hour Wash with saturated aqueous sodium bicarbonate, brine dry concentrate

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

Procedure: Dissolve 3-methoxy-5,5-dimethyl-cyclohex-2-enone (Tetrahedron 57 (2001) 217-225) (10.6 g, 68.7 mmol) in ether (500 ml) cool to 0° C., add dropwise a 1.5M solution of diisobutyl aluminum hydride (68.7 ml, 103 mmol), and stir for 30 minutes. Add saturated aqueous ammonium chloride (25 ml), stir 1 hour, add anhydrous magnesium sulfate (10 g), stir 1 hour. Filter through celite and concentrate. Dissolve the residue in ether (500 ml), add toluene-4-sulfonic acid monohydrate (650 mg, 3.44 mmol) and water (6.2 ml), and stir 1 hour. Wash with saturated aqueous sodium bicarbonate, brine, dry and concentrate to give the title compound as a clear oil (5.0 g, 58%): 1H NMR (CDCl3) δ 6.89-6.84 (m, 1H), 2.28 (s, 2H), 2.26-2.24 (q, 2H), 1.06 (s, 6H). stir 1 hour Filter through celite and concentrate Dissolve the residue in ether (500 ml) stir 1 hour Wash with saturated aqueous sodium bicarbonate, brine dry concentrate

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

Procedure: A solution of 3-methoxy-5,5-dimethyl-cyclohex-2-enone (80 g, 0.52 mol) in anhydrous tetrahydrofuran (270 mL) was treated dropwise with a 1M solution of LiAlH4 in tetrahydrofuran (182 mL), under argon atmosphere and keeping the temperature of the reaction between 0° C. and 5° C. The temperature was allowed to rise to 25° C. and the mixture was stirred for 4 hours. The resulting slurry was cooled with an ice bath, quenched with ethyl acetate (30 mL) and poured with caution into a cooled 2 M H2SO4 solution. The aqueous solution was then extracted with diethyl ether (300 mL×3), dried on Na2SO4 and evaporated under reduced pressure to remove most of the solvent. The crude material contained the title compound as a low boiling point oil that was used in the next step without further purification. the temperature of the reaction between 0° C. and 5° C to rise to 25° C. The resulting slurry was cooled with an ice bath quenched with ethyl acetate (30 mL) poured with caution into a cooled 2 M H2SO4 solution The aqueous solution was then extracted with diethyl ether (300 mL×3) dried on Na2SO4 evaporated under reduced pressure to remove most of the solvent was used in the next step without further purification

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

Procedure: (a') A catalytic hydrogenation of 3,3-dimethyl-cyclohex-5-en-1-one was carried out according to the usual techniques in the presence of palladium on charcoal and yielded 3,3-dimethylcyclohexanone. The subsequent ethylination by means of acetylene in a basic medium gave 1-ethynyl-1-hydroxy-3,3-dimethyl-cyclohexane in about 50% yield.

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

Procedure: 8 g of a 14% solution of butyl-lithium in diethylether were added under nitrogen within 15 min. to a suspension of 7 g of the above said phosphonium bromide in 80 ml ether. To the red resulting solution, cooled to 5°-10°, 2.1 g of 3,3-dimethyl-cyclohex-5-en-1-one in 10 ml ether, were adde, whereupon, the reaction mixture was stirred for 3 h, filtered and the clear filtrate was washed with water until neutrality. On evaporation and distillation in a bulb apparatus, 1.5 g (50% yield) of (3,3-dimethyl-cyclohex-5-en-1-yliden-)-pent-4-ene were obtained. To the red resulting solution, cooled to 5°-10° filtered the clear filtrate was washed with water until neutrality On evaporation and distillation in a bulb apparatus

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

Procedure: A solution of 3-methoxy-5,5-dimethyl-cyclohex-2-enone (80 g, 0.52 mol) in anhydrous tetrahydrofuran (270 mL) was treated dropwise with a 1M solution of LiAlH4 in tetrahydrofuran (182 mL), under argon atmosphere and keeping the temperature of the reaction between 0° C. and 5° C. The temperature was allowed to rise to 25° C. and the mixture was stirred for 4 hours. The resulting slurry was cooled with an ice bath, quenched with ethyl acetate (30 mL) and poured with caution into a cooled 2 M H2SO4 solution. The aqueous solution was then extracted with diethyl ether (300 mL×3), dried on Na2SO4 and evaporated under reduced pressure to remove most of the solvent. The crude material contained the title compound as a low boiling point oil that was used in the next step without further purification. the temperature of the reaction between 0° C. and 5° C to rise to 25° C. The resulting slurry was cooled with an ice bath quenched with ethyl acetate (30 mL) poured with caution into a cooled 2 M H2SO4 solution The aqueous solution was then extracted with diethyl ether (300 mL×3) dried on Na2SO4 evaporated under reduced pressure to remove most of the solvent was used in the next step without further purification

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

Procedure: (a') A catalytic hydrogenation of 3,3-dimethyl-cyclohex-5-en-1-one was carried out according to the usual techniques in the presence of palladium on charcoal and yielded 3,3-dimethylcyclohexanone. The subsequent ethylination by means of acetylene in a basic medium gave 1-ethynyl-1-hydroxy-3,3-dimethyl-cyclohexane in about 50% yield.