2-乙氧基-2-环己烯-1-酮

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

实验步骤: A stirred solution of 8.70 g (51.8 mmol) of 1,2,3-trimethoxybenzene and 8.25 mL (54.7 mmol) of tetramethylethylenediamine in 40 mL of THF was cooled in an ice bath and 24.0 mL of 2.5 molar n-BuLi in hexanes (60.0 mmol) was added dropwise over 20 min. The cooling bath was removed and the mixture was stirred at room temperature for 2 h. The mixture was cooled to -70° C. and a solution of 6.95 g (49.6 mmol) of 2-ethoxycyclohex-2-en-1-one in 30 mL of THF was added dropwise over 45 min. The cooling bath was removed and the mixture was stirred at room temperature for 2 days. The mixture was poured into 150 mL of 5% aqueous HCl and allowed to stand for 2 h. The mixture was extracted with two 80 mL portions of ether. The combined ether extracts were washed with 50 mL of saturated aqueous NaHCO3, and dried over MgSO4. Removal of the solvent left 13.56 g of an oil which was purified by flash chromatography on a column of 100 g of silica gel eluted successively with 250 mL portions of 0, 8, 16, 24, 40, 60, 80 and 100% ether in hexanes to furnish 7.08 g of 2-hydroxy-2-(2,3,4-trimethoxyphenyl)cyclohexanone as a solid, mp 88°-91° C. 1H-NMR (CDCl3) d 1.5-1.8 (4H), 2.0 (m, 1H), 2.5 (m, 2H), 2.9 (m, 1H), 3.7 (s, 3H), 3.88 (s, 3H), 3.92 (s, 3H), 4.6 (s, 1H), 6.75 (d, 1H), 7.25 (d, 1H). The cooling bath was removed The mixture was cooled to -70° C. The cooling bath was removed the mixture was stirred at room temperature for 2 days The mixture was poured into 150 mL of 5% aqueous HCl to stand for 2 h The mixture was extracted with two 80 mL portions of ether The combined ether extracts were washed with 50 mL of saturated aqueous NaHCO3 dried over MgSO4 Removal of the solvent left 13.56 g of an oil which was purified by flash chromatography on a column of 100 g of silica gel eluted successively with 250 mL portions of 0, 8, 16, 24, 40, 60, 80 and 100% ether in hexanes

反应条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3.4 g (0.02 mmol) of 2-ethoxycyclohex-2-en-1-one were dissolved in 30 mL of dry dimethylformamide and 30 mL (0.05 mmol) of dimethylformamide dimethyl acetale were added. The solution was stirred at 60° C. for 2 hours. The solvent was then evaporated under vacuum, the residue triturated with diethyl ether and collected by filtration to give 6.6 g of the title compound (80% yield). The solvent was then evaporated under vacuum the residue triturated with diethyl ether collected by filtration

反应条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3.4 g (0.02 mmol) of 2-ethoxycyclohex-2-en-1-one were dissolved in 30 mL of dry dimethylformamide and 30 mL (0.05 mmol) of dimethylformamide dimethyl acetale were added. The solution was stirred at 60° C. for 2 hours. The solvent was then evaporated under vacuum, the residue triturated with diethyl ether and collected by filtration to give 6.6 g of the title compound (80% yield). The solvent was then evaporated under vacuum the residue triturated with diethyl ether collected by filtration

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

实验步骤: 41.40 g (0.29 mol) of 2-ethoxycyclohex-2-en-1-one were dissolved in 310 mL of diethyl ether and 325 mL of 1M LiN(TMS)2 in tetrahydrofuran were added dropwise at −50° C. After 30 minutes at the same temperature, 44.2 mL of diethyloxalate were also added under stirring. The solution was kept at room temperature overnight (TLC chloroform). 300 mL of water were then added, the pH adjusted to 4-5 by adding 1 N HCl and the resulting solution extracted with ethyl acetate. The organic layer was dried over Na2SO4 and evaporated to dryness. The crude was purified by chromatography on a silica gel column eluted by chloroform (76% yield as an oil). the resulting solution extracted with ethyl acetate The organic layer was dried over Na2SO4 evaporated to dryness The crude was purified by chromatography on a silica gel column eluted by chloroform (76% yield as an oil)

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

实验步骤: 41.40 g (0.29 mol) of 2-ethoxycyclohex-2-en-1-one were dissolved in 310 mL of diethyl ether and 325 mL of 1M LiN(TMS)2 in tetrahydrofuran were added dropwise at −50° C. After 30 minutes at the same temperature, 44.2 mL of diethyloxalate were also added under stirring. The solution was kept at room temperature overnight (TLC chloroform). 300 mL of water were then added, the pH adjusted to 4-5 by adding 1 N HCl and the resulting solution extracted with ethyl acetate. The organic layer was dried over Na2SO4 and evaporated to dryness. The crude was purified by chromatography on a silica gel column eluted by chloroform (76% yield as an oil). the resulting solution extracted with ethyl acetate The organic layer was dried over Na2SO4 evaporated to dryness The crude was purified by chromatography on a silica gel column eluted by chloroform (76% yield as an oil)

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

实验步骤: 50 g (0.45 mol) of 1,2-dicyclohexandione were dissolved in a mixture of 1 L of toluene and 0.5 L of ethanol. 10 g of p-toluenesulfonic acid were added and the solution heated at reflux for 2 days. (TLC chloroform/methanol 6/1). The solvent was then evaporated, the residue redissolved with dichloromethane and washed with a saturated solution of NaHCO3. The organic layer was dried over Na2SO4 and concentrated. The crude was purified by chromatography on a silica gel column by eluting with a mixture of cyclohexane/ethyl acetate 98/2 (66° A) yield as an oil). the solution heated at reflux for 2 days The solvent was then evaporated the residue redissolved with dichloromethane washed with a saturated solution of NaHCO3 The organic layer was dried over Na2SO4 concentrated The crude was purified by chromatography on a silica gel column by eluting with a mixture of cyclohexane/ethyl acetate 98/2 (66° A) yield as an oil)

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

实验步骤: A stirred solution of 8.70 g (51.8 mmol) of 1,2,3-trimethoxybenzene and 8.25 mL (54.7 mmol) of tetramethylethylenediamine in 40 mL of THF was cooled in an ice bath and 24.0 mL of 2.5 molar n-BuLi in hexanes (60.0 mmol) was added dropwise over 20 min. The cooling bath was removed and the mixture was stirred at room temperature for 2 h. The mixture was cooled to -70° C. and a solution of 6.95 g (49.6 mmol) of 2-ethoxycyclohex-2-en-1-one in 30 mL of THF was added dropwise over 45 min. The cooling bath was removed and the mixture was stirred at room temperature for 2 days. The mixture was poured into 150 mL of 5% aqueous HCl and allowed to stand for 2 h. The mixture was extracted with two 80 mL portions of ether. The combined ether extracts were washed with 50 mL of saturated aqueous NaHCO3, and dried over MgSO4. Removal of the solvent left 13.56 g of an oil which was purified by flash chromatography on a column of 100 g of silica gel eluted successively with 250 mL portions of 0, 8, 16, 24, 40, 60, 80 and 100% ether in hexanes to furnish 7.08 g of 2-hydroxy-2-(2,3,4-trimethoxyphenyl)cyclohexanone as a solid, mp 88°-91° C. 1H-NMR (CDCl3) d 1.5-1.8 (4H), 2.0 (m, 1H), 2.5 (m, 2H), 2.9 (m, 1H), 3.7 (s, 3H), 3.88 (s, 3H), 3.92 (s, 3H), 4.6 (s, 1H), 6.75 (d, 1H), 7.25 (d, 1H). The cooling bath was removed The mixture was cooled to -70° C. The cooling bath was removed the mixture was stirred at room temperature for 2 days The mixture was poured into 150 mL of 5% aqueous HCl to stand for 2 h The mixture was extracted with two 80 mL portions of ether The combined ether extracts were washed with 50 mL of saturated aqueous NaHCO3 dried over MgSO4 Removal of the solvent left 13.56 g of an oil which was purified by flash chromatography on a column of 100 g of silica gel eluted successively with 250 mL portions of 0, 8, 16, 24, 40, 60, 80 and 100% ether in hexanes

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

实验步骤: A stirred solution of 8.70 g (51.8 mmol) of 1,2,3-trimethoxybenzene and 8.25 mL (54.7 mmol) of tetramethylethylenediamine in 40 mL of THF was cooled in an ice bath and 24.0 mL of 2.5 molar n-BuLi in hexanes (60.0 mmol) was added dropwise over 20 min. The cooling bath was removed and the mixture was stirred at room temperature for 2 h. The mixture was cooled to -70° C. and a solution of 6.95 g (49.6 mmol) of 2-ethoxycyclohex-2-en-1-one in 30 mL of THF was added dropwise over 45 min. The cooling bath was removed and the mixture was stirred at room temperature for 2 days. The mixture was poured into 150 mL of 5% aqueous HCl and allowed to stand for 2 h. The mixture was extracted with two 80 mL portions of ether. The combined ether extracts were washed with 50 mL of saturated aqueous NaHCO3, and dried over MgSO4. Removal of the solvent left 13.56 g of an oil which was purified by flash chromatography on a column of 100 g of silica gel eluted successively with 250 mL portions of 0, 8, 16, 24, 40, 60, 80 and 100% ether in hexanes to furnish 7.08 g of 2-hydroxy-2-(2,3,4-trimethoxyphenyl)cyclohexanone as a solid, mp 88°-91° C. 1H-NMR (CDCl3) d 1.5-1.8 (4H), 2.0 (m, 1H), 2.5 (m, 2H), 2.9 (m, 1H), 3.7 (s, 3H), 3.88 (s, 3H), 3.92 (s, 3H), 4.6 (s, 1H), 6.75 (d, 1H), 7.25 (d, 1H). The cooling bath was removed The mixture was cooled to -70° C. The cooling bath was removed the mixture was stirred at room temperature for 2 days The mixture was poured into 150 mL of 5% aqueous HCl to stand for 2 h The mixture was extracted with two 80 mL portions of ether The combined ether extracts were washed with 50 mL of saturated aqueous NaHCO3 dried over MgSO4 Removal of the solvent left 13.56 g of an oil which was purified by flash chromatography on a column of 100 g of silica gel eluted successively with 250 mL portions of 0, 8, 16, 24, 40, 60, 80 and 100% ether in hexanes

反应条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3.4 g (0.02 mmol) of 2-ethoxycyclohex-2-en-1-one were dissolved in 30 mL of dry dimethylformamide and 30 mL (0.05 mmol) of dimethylformamide dimethyl acetale were added. The solution was stirred at 60° C. for 2 hours. The solvent was then evaporated under vacuum, the residue triturated with diethyl ether and collected by filtration to give 6.6 g of the title compound (80% yield). The solvent was then evaporated under vacuum the residue triturated with diethyl ether collected by filtration

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

实验步骤: 41.40 g (0.29 mol) of 2-ethoxycyclohex-2-en-1-one were dissolved in 310 mL of diethyl ether and 325 mL of 1M LiN(TMS)2 in tetrahydrofuran were added dropwise at 50° C. After 30 minutes at the same temperature, 44.2 mL of diethyloxalate were also added under stirring. The solution was kept at room temperature overnight (TLC chloroform). 300 mL of water were then added, the pH adjusted to 4-5 by adding 1N HCl and the resulting solution extracted with ethyl acetate. The organic layer was dried over Na2SO4 and evaporated to dryness. The crude was purified by chromatography on a silica gel column eluted by chloroform (76% yield as an oil). the resulting solution extracted with ethyl acetate The organic layer was dried over Na2SO4 evaporated to dryness The crude was purified by chromatography on a silica gel column eluted by chloroform (76% yield as an oil)

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

实验步骤: 50 g (0.45 mol) of 1,2-dicyclohexandione were dissolved in a mixture of 1 L of toluene and 0.5 L of ethanol. 10 g of p-toluenesulfonic acid were added and the solution heated at reflux for 2 days. (TLC chloroform/methanol 6/1). The solvent was then evaporated, the residue redissolved with dichloromethane and washed with a saturated solution of NaHCO3. The organic layer was dried over Na2SO4 and concentrated. The crude was purified by chromatography on a silica gel column by eluting with a mixture of cyclohexane/ethyl acetate 98/2 (66% yield as an oil). the solution heated at reflux for 2 days The solvent was then evaporated the residue redissolved with dichloromethane washed with a saturated solution of NaHCO3 The organic layer was dried over Na2SO4 concentrated The crude was purified by chromatography on a silica gel column by eluting with a mixture of cyclohexane/ethyl acetate 98/2 (66% yield as an oil)

反应条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 3.4 g (0.02 mmol) of 2-ethoxycyclohex-2-en-1-one were dissolved in 30 mL of dry dimethylformamide and 30 mL (0.05 mmol) of dimethylformamide dimethyl acetale were added. The solution was stirred at 60° C. for 2 hours. The solvent was then evaporated under vacuum, the residue triturated with diethyl ether and collected by filtration to give 6.6 g of the title compound (80% yield). The solvent was then evaporated under vacuum the residue triturated with diethyl ether collected by filtration