2-chloro-4-methylcyclohexene-1-carbaldehyde

反応条件: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 769 mg of the crude 2-chloro-4-methyl-cyclohex-1-enecarbaldehyde obtained in step a) were dissolved in DMF (10 ml). Then 837 mg (6.06 mmol) of potassium carbonate and 440 μl (4.85 mmol) of methyl thioglycolate were added and the mixture was heated to 100° C. for 16 h. After cooling to RT, the solvent was removed in vacuo. Water was added to the remaining residue and the mixture was extracted with ethyl acetate. The organic extracts were then washed with 50% sodium chloride solution, dried (MgSO4) and concentrated to give 704 mg of 6-methyl-4,5,6,7-tetrahydro-benzo[b]thiophene-2-carboxylic acid methyl ester (containing 10% of 4-methyl-4,5,6,7-tetrahydro-benzo[b]thiophene-2-carboxylic acid methyl ester) as dark brown oil. MS (ISP) 211.1 (M+H)+. After cooling to RT the solvent was removed in vacuo Water was added to the remaining residue the mixture was extracted with ethyl acetate The organic extracts were then washed with 50% sodium chloride solution dried (MgSO4) concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 446 μl (5.80 mmol) of DMF in 5 ml trichloroethylene were added 449 μl (4.90 mmol) of phosphorus oxychloride at 4° C. The mixture was then allowed to warm to RT and a solution of 500 mg (4.46 mmol) of 3-methyl-cyclohexanone in 5 ml trichloroethylene was added dropwise. After heating to 60° C. for 4 h, the reaction mixture was cooled to RT and 10 ml of a cold sodium acetate solution were added. The organic layer was separated and the aqueous phase was extracted with dichloromethane. The combined organic layers were then washed with brine, dried (MgSO4) and concentrated to yield 769 mg of crude 2-chloro-4-methyl-cyclohex-1-enecarbaldehyde (containing 10% of 2-chloro-6-methyl-cyclohex-1-enecarbaldehyde) as a light yellow oil. After heating to 60° C. for 4 h the reaction mixture was cooled to RT The organic layer was separated the aqueous phase was extracted with dichloromethane The combined organic layers were then washed with brine dried (MgSO4) concentrated

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 446 μl (5.80 mmol) of DMF in 5 ml trichloroethylene were added 449 μl (4.90 mmol) of phosphorus oxychloride at 4° C. The mixture was then allowed to warm to RT and a solution of 500 mg (4.46 mmol) of 3-methyl-cyclohexanone in 5 ml trichloroethylene was added dropwise. After heating to 60° C. for 4 h, the reaction mixture was cooled to RT and 10 ml of a cold sodium acetate solution were added. The organic layer was separated and the aqueous phase was extracted with dichloromethane. The combined organic layers were then washed with brine, dried (MgSO4) and concentrated to yield 769 mg of crude 2-chloro-4-methyl-cyclohex-1-enecarbaldehyde (containing 10% of 2-chloro-6-methyl-cyclohex-1-enecarbaldehyde) as a light yellow oil. After heating to 60° C. for 4 h the reaction mixture was cooled to RT The organic layer was separated the aqueous phase was extracted with dichloromethane The combined organic layers were then washed with brine dried (MgSO4) concentrated