2-烯丙基环己酮

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Into a 2 liter round bottom flask, equipped with Dean-Stark water separator, cyclohexanone (186 g, 1.90 moles, Aldrich) was dissolved in 1 liter toluene, and then pyrrolidine (292 g, 4.1 moles) was added. The mixture was brought to reflux overnight, during which 55 mL of water was collected. After switching to a distillation head, excess pyrrolindine and toluene were distilled off (1.2 liter). When most of the volatiles had been removed, aspirator vacuum was applied to assist in removal of residual toluene. In the same flask, the residue was dissolved in 1.2 liter of acetonitrile. Allyl bromide (305 g, 2.5 moles) was added dropwise. The mixture was heated slowly to gentle reflux overnight. After distilling off most of the acetonitrile and cooling, 1.2 liter of water was added and heated to reflux for 30 minutes. Extracted with ether after the mixture was cooled (200 mL×3). Combined ether layer was dried over sodium sulfate. The crude product, after removing the solvent, was purified by vacuum distillation: 73-78° C., 6.7 mmHg, Yield: 156 grams (59% for two steps). See also, Stork et al., J. American Chem. Soc., 85:207-222 (1963), and Johnson et al., J. American Chem. Soc., 88:149-159 (1966). was collected were distilled off (1.2 liter) When most of the volatiles had been removed to assist in removal of residual toluene In the same flask, the residue was dissolved in 1.2 liter of acetonitrile The mixture was heated slowly to gentle reflux overnight After distilling off most of the acetonitrile cooling 1.2 liter of water was added heated to reflux for 30 minutes Extracted with ether after the mixture was cooled (200 mL×3) Combined ether layer was dried over sodium sulfate The crude product, after removing the solvent was purified by vacuum distillation 73-78° C., 6.7 mmHg, Yield: 156 grams (59% for two steps)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The chlorination of 2-allylcyclohexanone takes place in a manner similar to that described above for the preparation of 2-tert-butyl-6-chloro-cyclohexanone. The title compound is reacted as a crude product without further characterization.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Into a 2 liter round bottom flask, equipped with Dean-Stark water separator, cyclohexanone (186 g, 1.90 moles, Aldrich) was dissolved in 1 liter toluene, and then pyrrolidine (292 g, 4.1 moles) was added. The mixture was brought to reflux overnight, during which 55 mL of water was collected. After switching to a distillation head, excess pyrrolindine and toluene were distilled off (1.2 liter). When most of the volatiles had been removed, aspirator vacuum was applied to assist in removal of residual toluene. In the same flask, the residue was dissolved in 1.2 liter of acetonitrile. Allyl bromide (305 g, 2.5 moles) was added dropwise. The mixture was heated slowly to gentle reflux overnight. After distilling off most of the acetonitrile and cooling, 1.2 liter of water was added and heated to reflux for 30 minutes. Extracted with ether after the mixture was cooled (200 mL×3). Combined ether layer was dried over sodium sulfate. The crude product, after removing the solvent, was purified by vacuum distillation: 73-78° C., 6.7 mmHg, Yield: 156 grams (59% for two steps). See also, Stork et al., J. American Chem. Soc., 85:207-222 (1963), and Johnson et al., J. American Chem. Soc., 88:149-159 (1966). was collected were distilled off (1.2 liter) When most of the volatiles had been removed to assist in removal of residual toluene In the same flask, the residue was dissolved in 1.2 liter of acetonitrile The mixture was heated slowly to gentle reflux overnight After distilling off most of the acetonitrile cooling 1.2 liter of water was added heated to reflux for 30 minutes Extracted with ether after the mixture was cooled (200 mL×3) Combined ether layer was dried over sodium sulfate The crude product, after removing the solvent was purified by vacuum distillation 73-78° C., 6.7 mmHg, Yield: 156 grams (59% for two steps)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: The chlorination of 2-allylcyclohexanone takes place in a manner similar to that described above for the preparation of 2-tert-butyl-6-chloro-cyclohexanone. The title compound is reacted as a crude product without further characterization.

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of potassium t-butoxide (200 g, 1.78 mol) in toluene which was cooled to 0° C. in an ice bath under N2 was treated with cyclohexanone (157 g, 1.60 mol). To the reaction mixture was slowly added allyl bromide (194 g, 1.60 mol) over a 2 hour period. The reaction was warmed to room temperature over 5 hours. The reaction was then poured into EtOAc (400 mL) and washed once with 10% potassium hydrogen sulfate (250 mL). The organic solution was then washed with brine (3×200 mL), dried over magnesium sulfate, and evaporated under reduced pressure. The resulting oil was then chromatographed to yield 158.4 g (71.6%) of 2-allyl cyclohexanone as an oil. 1H NMR (CDCl3, 300 MHz) d 1.2-2.5 (m, 10H), 2.59 (m, 1H), 5.0 (dd, 2H), 5.75 (m, 1H). 13C NMR (CDCl3, 75 MHz) d 25.04, 28.03, 33.46, 33.86, 42.12, 50.35, 116.3, 136.6, 212.5. over a 2 hour The reaction was warmed to room temperature over 5 hours washed once with 10% potassium hydrogen sulfate (250 mL) The organic solution was then washed with brine (3×200 mL) dried over magnesium sulfate evaporated under reduced pressure The resulting oil was then chromatographed

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A suspension of potassium t-butoxide (200 g, 1.78 mol) in toluene which was cooled to 0° C. in an ice bath under N2 was treated with cyclohexanone (157 g, 1.60 mol). To the reaction mixture was slowly added allyl bromide (194 g, 1.60 mol) over a 2 hour period. The reaction was warmed to room temperature over 5 hours. The reaction was then poured into EtOAc (400 mL) and washed once with 10% potassium hydrogen sulfate (250 mL). The organic solution was then washed with brine (3×200 mL), dried over magnesium sulfate, and evaporated under reduced pressure. The resulting oil was then chromatographed to yield 158.4 g (71.6%) of 2-allyl cyclohexanone as an oil. 1H NMR (CDCl3, 300 MHz) d 1.2-2.5 (m, 10H), 2.59 (m, 1H), 5.0 (dd, 2H), 5.75 (m, 1H). 13C NMR (CDCl3, 75 MHz) d 25.04, 28.03, 33.46, 33.86, 42.12, 50.35, 116.3, 136.6, 212.5. over a 2 hour The reaction was warmed to room temperature over 5 hours washed once with 10% potassium hydrogen sulfate (250 mL) The organic solution was then washed with brine (3×200 mL) dried over magnesium sulfate evaporated under reduced pressure The resulting oil was then chromatographed

反应条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of diisopropylamine (6.60 mL, 46.6 mmol) in THF (200 mL) at −10° C., was added a solution 2.22M of n-butyllithium (20.4 mL, 44.4 mmol). The solution was stirred 15 min at −10° C., cooled down to −78° C. and tert-butyl 2-trimethylsilylacetate (9.7 mL, 44.4 mmol) in 1 mL of THF was added dropwise. The solution was stirred 15 min at −78° C., and 2-allylcyclohexanone (3.3 mL, 22.2 mmol) was added dropwise. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C. It was then quenched with saturated NH4Cl, extracted with ethylacetate, washed with brine, dried and concentrated. Purification by flash chromatography (cyclohexane) gave tert-butyl 2-(2-allylcyclohexylidene)acetate (5.06 g, 96%) as a colorless liquid. 1H NMR (400 MHz, CDCl3) 5.62 (1H, m), 5.41 (1H, s), 4.89 (2H, m), 3.83 (1H, m), 2.16 (3H, m), 1.90 (1H, m), 1.73 (1H, m), 1.61 (1H, m), 1.47-1.22 (4H, m), 1.36 (9H, s). cooled down to −78° C. The solution was stirred 15 min at −78° C. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C It was then quenched with saturated NH4Cl extracted with ethylacetate washed with brine dried concentrated Purification by flash chromatography (cyclohexane)

反应条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of diisopropylamine (6.60 mL, 46.6 mmol) in THF (200 mL) at −10° C., was added a solution 2.22M of n-butyllithium (20.4 mL, 44.4 mmol). The solution was stirred 15 min at −10° C., cooled down to −78° C. and tert-butyl 2-trimethylsilylacetate (9.7 mL, 44.4 mmol) in 1 mL of THF was added dropwise. The solution was stirred 15 min at −78° C., and 2-allylcyclohexanone (3.3 mL, 22.2 mmol) was added dropwise. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C. It was then quenched with saturated NH4Cl, extracted with ethylacetate, washed with brine, dried and concentrated. Purification by flash chromatography (cyclohexane) gave tert-butyl 2-(2-allylcyclohexylidene)acetate (5.06 g, 96%) as a colorless liquid. 1H NMR (400 MHz, CDCl3) 5.62 (1H, m), 5.41 (1H, s), 4.89 (2H, m), 3.83 (1H, m), 2.16 (3H, m), 1.90 (1H, m), 1.73 (1H, m), 1.61 (1H, m), 1.47-1.22 (4H, m), 1.36 (9H, s). cooled down to −78° C. The solution was stirred 15 min at −78° C. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C It was then quenched with saturated NH4Cl extracted with ethylacetate washed with brine dried concentrated Purification by flash chromatography (cyclohexane)

反应条件: temp:-10.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To a solution of diisopropylamine (6.60 mL, 46.6 mmol) in THF (200 mL) at −10° C., was added a solution 2.22M of n-butyllithium (20.4 mL, 44.4 mmol). The solution was stirred 15 min at −10° C., cooled down to −78° C. and tert-butyl 2-trimethylsilylacetate (9.7 mL, 44.4 mmol) in 1 mL of THF was added dropwise. The solution was stirred 15 min at −78° C., and 2-allylcyclohexanone (3.3 mL, 22.2 mmol) was added dropwise. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C. It was then quenched with saturated NH4Cl, extracted with ethylacetate, washed with brine, dried and concentrated. Purification by flash chromatography (cyclohexane) gave tert-butyl 2-(2-allylcyclohexylidene)acetate (5.06 g, 96%) as a colorless liquid. 1H NMR (400 MHz, CDCl3) 5.62 (1H, m), 5.41 (1H, s), 4.89 (2H, m), 3.83 (1H, m), 2.16 (3H, m), 1.90 (1H, m), 1.73 (1H, m), 1.61 (1H, m), 1.47-1.22 (4H, m), 1.36 (9H, s). cooled down to −78° C. The solution was stirred 15 min at −78° C. The reaction mixture was stirred 1 h at −78° C. and 3 h at −25° C It was then quenched with saturated NH4Cl extracted with ethylacetate washed with brine dried concentrated Purification by flash chromatography (cyclohexane)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Ex-6a) A suspension of potassium t-butoxide (200 g, 1.78 mol) in toluene which was cooled to 0° C. in an ice bath under N2 was treated with cyclohexanone (157 g, 1.60 mol). To the reaction mixture was slowly added allyl bromide (194 g, 1.60 mol) over a 2 hour period. The reaction was warmed to room temperature over 5 hours. The reaction was then poured into EtOAc (400 mL) and washed once with 10% potassium hydrogen sulfate (250 mL). The organic solution was then washed with brine (3×200 mL), dried over magnesium sulfate, and evaporated under reduced pressure. The resulting oil was then chromatographed to yield 158.4 g (71.6%) of 2-allyl cyclohexanone as an oil. over a 2 hour The reaction was warmed to room temperature over 5 hours washed once with 10% potassium hydrogen sulfate (250 mL) The organic solution was then washed with brine (3×200 mL) dried over magnesium sulfate evaporated under reduced pressure The resulting oil was then chromatographed

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of cyclohexanone (98.1 g, 1 mol), allyl alcohol (127.8 g, 2.2 mol), dimethoxypropane (114.6 g, 1.1 mol), and PTSA.H2O (0.1 g, 0.5 mmol) in toluene (0.51) was heated at reflux in a flask equipped with a microdistillation column (30×2.5 cm, filled with Raschig rings). After collecting the fractions distilling at 25-60° C. and 60-110° C., the residue (120 g) was distilled using a 10 cm-Vigreux-column (0.07-0.06 mbar, head temperature: 57° C.) giving 2-allylcyclohexanone (99.1 g, 72%). at reflux in a flask equipped with a microdistillation column (30×2.5 cm, filled with Raschig rings) After collecting the fractions distilling at 25-60° C. and 60-110° C. the residue (120 g) was distilled a 10 cm-Vigreux-column (0.07-0.06 mbar, head temperature: 57° C.)

反应条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: EX-6a) A suspension of potassium t-butoxide (200 g, 1.78 mol) in toluene which was cooled to 0° C. in an ice bath under N2 was treated with cyclohexanone (157 g, 1.60 mol). To the reaction mixture was slowly added allyl bromide (194 g, 1.60 mol) over a 2 hour period. The reaction was warmed to room temperature over 5 hours. The reaction was then poured into EtOAc (400 mL) and washed once with 10% potassium hydrogen sulfate (250 mL). The organic solution was then washed with brine (3×200 mL), dried over magnesium sulfate, and evaporated under reduced pressure. The resulting oil was then chromatographed to yield 158.4 g (71.6%) of 2-allyl cyclohexanone as an oil. over a 2 hour The reaction was warmed to room temperature over 5 hours washed once with 10% potassium hydrogen sulfate (250 mL) The organic solution was then washed with brine (3×200 mL) dried over magnesium sulfate evaporated under reduced pressure The resulting oil was then chromatographed