5-propylcyclohexane-1,3-dione

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of (S)-3-amino-but-2-enoic acid [1-(4-methoxy-phenyl)-ethyl]-amide (10 g), 3-bromo-5-ethoxy-4-hydroxy-benzaldehyde (10.4 g) and 5-propylcyclohexane-1,3-dione (6.5 g) in ethanol (150 ml) was stirred at 80° C. for 18 hr. The mixture was concentrated in vacuo. The residue was dissolved in toluene (100 ml) and dichloromethane (50 ml) and evaporated until a precipitated formed. The solid obtained was then crystallized in EtOAc. The mixture was concentrated in vacuo The residue was dissolved in toluene (100 ml) dichloromethane (50 ml) and evaporated until a precipitated formed The solid obtained was then crystallized in EtOAc

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The title compound was prepared according to the method described in example 1b starting from 3-bromo-5-ethoxy-4-hydroxy-benzaldehyde (6 g), 3-aminocrotonitrile (2.01 g) and 5-propylcyclohexane-1,3-dione (3.8 g). The reaction mixture was cooled (0° C.) and the title compound was filtered off and washed with ethanol (cold). Yield: 6.3 g. MS-ESI: [M+H]+=445/447 the title compound was filtered off washed with ethanol (cold)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of the product of step c (59 mg), 3-aminocrotonitrile (12.3 mg) and 5-propylcyclohexane-1,3-dione (23.1 mg) in ethanol (5 ml) was stirred at 80° C. for 17 h. The reaction mixture was concentrated in vacuo and the residue was purified by preparative HPLC (Method B). Yield: 57 mg. MS-ESI: [M+H]+=591.3/593.3; HPLC: Rt=18.43 min. Diast. ratio: 9:1 The reaction mixture was concentrated in vacuo the residue was purified by preparative HPLC (Method B)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of the product of step c (59 mg), 3-aminocrotonitrile (12.3 mg) and 5-propylcyclohexane-1,3-dione (23.1 mg) in ethanol (5 ml) was stirred at 80° C. for 17 h. The reaction mixture was concentrated in vacuo and the residue was purified by preparative HPLC (Method B). Yield: 57 mg. MS-ESI: [M+H]+=591.3/593.3; HPLC: Rt=18.43 min. Diast. ratio: 9:1 The reaction mixture was concentrated in vacuo the residue was purified by preparative HPLC (Method B)

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of the product of step d (61 mg), 3-aminocrotonitrile (12.3 mg) and 5-propylcyclohexane-1,3-dione (23.1 mg) in ethanol (5 ml) was stirred at 80° C. for 17 h. The reaction mixture was concentrated in vacuo and the residue was purified by preparative HPLC (Method B). Yield: 57 mg. MS-ESI: [M+H]+=607.3/609.3; HPLC: Rt=16.51 min. (diast. 1) Rt=16.83 min. (diast. 2) (method 1). Diast. ratio: 9:1 The reaction mixture was concentrated in vacuo the residue was purified by preparative HPLC (Method B)

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

実験手順: A mixture of 1-methyl-2-nitro-vinylamine (1 g), 5-propylcyclohexane-1,3-dione (1.61 g) and 3-bromo-5-ethoxy-4-hydroxy-benzaldehyde (2.57 g) in ethanol (50 ml) was stirred at reflux for 17 h. The reaction mixture was concentrated in vacuo. The residue was dissolved in dichloromethane. A precipitate formed, which was collected by filtration. The solid was chromatographed on silicagel in heptane/EtOAc (from 1/0 to 0/1) as eluent. Yield: 2.8 g. MS-ESI: [M+H]+=465.0/467.0 at reflux for 17 h The reaction mixture was concentrated in vacuo The residue was dissolved in dichloromethane A precipitate formed which was collected by filtration The solid was chromatographed on silicagel in heptane/EtOAc (from 1/0 to 0/1) as eluent

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

実験手順: A mixture of 1-methyl-2-nitro-vinylamine (1 g), 5-propylcyclohexane-1,3-dione (1.61 g) and 3-bromo-5-ethoxy-4-hydroxy-benzaldehyde (2.57 g) in ethanol (50 ml) was stirred at reflux for 17 h. The reaction mixture was concentrated in vacuo. The residue was dissolved in dichloromethane. A precipitate formed, which was collected by filtration. The solid was chromatographed on silicagel in heptane/EtOAc (from 1/0 to 0/1) as eluent. Yield: 2.8 g. MS-ESI: [M+H]+=465.0/467.0 at reflux for 17 h The reaction mixture was concentrated in vacuo The residue was dissolved in dichloromethane A precipitate formed which was collected by filtration The solid was chromatographed on silicagel in heptane/EtOAc (from 1/0 to 0/1) as eluent

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of the product of step b (1.06 g), 3-aminocrotonitrile (221 mg) and 5-propylcyclohexane-1,3-dione (415 mg) in ethanol (20 ml) was stirred at 80° C. for 17 h. The reaction mixture was concentrated in vacuo and the residue was chromatographed on silica gel in heptane/EtOAc=1/1 (v/v) as eluent. Yield: 750 mg. MS-ESI: [M+H]+=594.4/596.4 The reaction mixture was concentrated in vacuo the residue was chromatographed on silica gel in heptane/EtOAc=1/1 (v/v) as eluent

反応条件: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of the product of step b (1.06 g), 3-aminocrotonitrile (221 mg) and 5-propylcyclohexane-1,3-dione (415 mg) in ethanol (20 ml) was stirred at 80° C. for 17 h. The reaction mixture was concentrated in vacuo and the residue was chromatographed on silica gel in heptane/EtOAc=1/1 (v/v) as eluent. Yield: 750 mg. MS-ESI: [M+H]+=594.4/596.4 The reaction mixture was concentrated in vacuo the residue was chromatographed on silica gel in heptane/EtOAc=1/1 (v/v) as eluent

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

実験手順: The reaction of 3-bromo-4-hydroxy-benzaldehyde (13.07 g) with 3-aminocrotonitril (5.34 g) and 5-propylcyclohexane-1,3-dione (10.02 g) was performed according to the method described in example 1a. Yield: 20.25 g. MS-ESI: [M+H]+=401/403

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

実験手順: The reaction of 3-bromo-4-hydroxy-benzaldehyde (13.07 g) with 3-aminocrotonitril (5.34 g) and 5-propylcyclohexane-1,3-dione (10.02 g) was performed according to the method described in example 1a. Yield: 20.25 g. MS-ESI: [M+H]+=401/403