ethyl 3-bromo-2-oxocyclohexane-1-carboxylate

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: The compound is prepared by action of thioacetamide on 2-bromo-5-ethoxycarbonyl cyclohexanone (II), as described in Example 1. B.P.0.4 =116°-120° C. B.P.0.4 =116°-120° C.

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

実験手順: The compound is prepared by action of thioacetamide on 2-bromo-5-ethoxycarbonyl cyclohexanone (II), as described in Example 1. B.P.0.4 =116°-120° C. B.P.0.4 =116°-120° C.

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

実験手順: This compound is prepared by action of thioacetamide on 2-bromo-6-carbethoxy-cyclohexanone (II), according to the process described in Example 1. B.p.0.1 =102°-105° C. B.p.0.1 =102°-105° C.

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

実験手順: This compound is prepared by action of thioacetamide on 2-bromo-6-carbethoxy-cyclohexanone (II), according to the process described in Example 1. B.p.0.1 =102°-105° C. B.p.0.1 =102°-105° C.

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

実験手順: The bromination of 2-oxo-cyclohexane carboxylic acid ethyl ester takes place in a manner similar to that described above for the preparation of 2-bromo-4-isopropyl-cyclohexanone. The title compound is reacted as a crude product without further characterization.

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

実験手順: Analogously to the preparation of Example C-01, 3-bromo-2-oxo-cyclohexane carboxylic acid ethyl ester is reacted with 2-imino-4-thiobiuret to produce the title compound.

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: The bromination of 2-oxo-cyclohexane carboxylic acid ethyl ester takes place in a manner similar to that described above for the preparation of 2-bromo-4-isopropyl-cyclohexanone. The title compound is reacted as a crude product without further characterization.

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

実験手順: Analogously to the preparation of Example C-01, 3-bromo-2-oxo-cyclohexane carboxylic acid ethyl ester is reacted with 2-imino-4-thiobiuret to produce the title compound.

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

実験手順: A suspension of [3-methoxy-4-(4-methyl-imidazol-1-yl)-phenyl]-thiourea (131 mg, 0.50 mmol) and of 2-bromo-6-(carbethoxy)-cyclohexanone (137 mg, 0.55 mmol) in ethanol (5 mL) was stirred at room temperature for 2 days and then heated to reflux under an atmosphere of nitrogen over night. After cooling to room temperature the solvent was evaporated under reduced pressure and the residue was purified by column chromatography on silica gel using dichloromethane/methanol (19:1 v/v) as eluent to yield the title compound (180 mg, 87%) as a white solid. MS ISP (m/e): 413.3 (100) [(M+H)+]. 1H NMR (DMSO-D6, 300 MHz): δ (ppm)=10.28 (s, 1H), 7.66 (d, 1H), 7.64 (s, 1H), 7.21 (d, 1H), 7.11 (d, 1H), 7.01 (s, 1H), 4.10 (q, 2H), 3.76 (s, 3H), 3.66 (m, 1H), 2.62 (m, 2H), 2.14 (s, 3H), 1.68-2.09 (m, 4H), 1.19 (t, 3H). heated to reflux under an atmosphere of nitrogen over night was evaporated under reduced pressure the residue was purified by column chromatography on silica gel

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

実験手順: 2-Carbethoxy-cyclohexanone (5.0 g, 29.4 mmol) was dissolved in diethyl ether (30 mL). To this solution bromine (4.93 g, 30.8 mmol) was added drop wise at room temperature. The reaction was stirred for 1 hour at room temperature, quenched with water and the layers were separated. The organic layer was washed with aqueous thiosulfate solution and brine, dried over sodium sulfate and filtered. The solvent was removed under reduced pressure to yield the crude title compound (7.48 g, 100%) which was used directly in the next step without further purification. 1H NMR (CDCl3, 300 MHz): δ (ppm)=4.94 (t, 1H), 4.20 (q, 1H), 2.37 (dt, 1H), 2.25 (m, 1H), 2.09 (m, 2H), 1.74 (m, 2H), 1.24 (t, 3H). quenched with water the layers were separated The organic layer was washed with aqueous thiosulfate solution and brine dried over sodium sulfate filtered The solvent was removed under reduced pressure