4-羟基-3-乙基苯甲醛

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: A mixture of the 3-ethyl-4-hydroxy-benzaldehyde (7.8 g, 51.9 mmol) obtained in Example 179.1, K2CO3 (10.8 g, 78 mmol) and isopropyl iodide (7.86 ml, 78 mmol) was heated in DMF (65 ml) for 3 h. to 80° C. and subsequently stirred for 12 h. at room temperature. The mixture was poured into ice-cold 0.5M HCl and extracted with diethyl ether. The organic phase was washed with NaCl solution, dried, filtered and concentrated. The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1). 3-Ethyl-4-isopropoxy-benzaldehyde was obtained as an orange oil (6.12 g, 61%); MS: 192 ([M]+). extracted with diethyl ether The organic phase was washed with NaCl solution dried filtered concentrated The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1)

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

实验步骤: A mixture of the 3-ethyl-4-hydroxy-benzaldehyde (7.8 g, 51.9 mmol) obtained in Example 179.1, K2CO3 (10.8 g, 78 mmol) and isopropyl iodide (7.86 ml, 78 mmol) was heated in DMF (65 ml) for 3 h. to 80° C. and subsequently stirred for 12 h. at room temperature. The mixture was poured into ice-cold 0.5M HCl and extracted with diethyl ether. The organic phase was washed with NaCl solution, dried, filtered and concentrated. The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1). 3-Ethyl-4-isopropoxy-benzaldehyde was obtained as an orange oil (6.12 g, 61%); MS: 192 ([M]+). extracted with diethyl ether The organic phase was washed with NaCl solution dried filtered concentrated The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1)

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

实验步骤: TiCl4 (45.6 g, 238 mmol) was added slowly to a solution of 2-ethylphenol (15 g, 119 mmol) in CH2Cl2 (150 ml) was at 0° C. The mixture was warmed to room temperature and dichloromethyl methyl ether (18.3 ml, 200 mmol) was added (strong HCl evolution). The mixture was stirred for 4 h. at room temperature, subsequently cooled to 0° C. and 1M HCl (119 ml, 119 mmol) was added dropwise. The mixture was stirred for 10 min. and subsequently extracted with diethyl ether. The organic phase was washed with saturated NaHCO3 solution and with NaCl solution, dried, filtered and concentrated. The residue was purified by chromatography (SiO2, CH2Cl2=>CH2Cl2/MeOH 9:1). 3-Ethyl-4-hydroxy-benzaldehyde was obtained as a brown oil (7.97 g, 45%). was at 0° C subsequently cooled to 0° C. The mixture was stirred for 10 min. subsequently extracted with diethyl ether The organic phase was washed with saturated NaHCO3 solution and with NaCl solution dried filtered concentrated The residue was purified by chromatography (SiO2, CH2Cl2=>CH2Cl2/MeOH 9:1)

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

实验步骤: A mixture of the 3-ethyl-4-hydroxy-benzaldehyde (7.8 g, 51.9 mmol) obtained in Example 179.1, K2CO3 (10.8 g, 78 mmol) and isopropyl iodide (7.86 ml, 78 mmol) was heated in DMF (65 ml) for 3 h. to 80° C. and subsequently stirred for 12 h. at room temperature. The mixture was poured into ice-cold 0.5M HCl and extracted with diethyl ether. The organic phase was washed with NaCl solution, dried, filtered and concentrated. The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1). 3-Ethyl-4-isopropoxy-benzaldehyde was obtained as an orange oil (6.12 g, 61%); MS: 192 ([M]+). extracted with diethyl ether The organic phase was washed with NaCl solution dried filtered concentrated The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1)

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

实验步骤: A mixture of the 3-ethyl-4-hydroxy-benzaldehyde (7.8 g, 51.9 mmol) obtained in Example 179.1, K2CO3 (10.8 g, 78 mmol) and isopropyl iodide (7.86 ml, 78 mmol) was heated in DMF (65 ml) for 3 h. to 80° C. and subsequently stirred for 12 h. at room temperature. The mixture was poured into ice-cold 0.5M HCl and extracted with diethyl ether. The organic phase was washed with NaCl solution, dried, filtered and concentrated. The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1). 3-Ethyl-4-isopropoxy-benzaldehyde was obtained as an orange oil (6.12 g, 61%); MS: 192 ([M]+). extracted with diethyl ether The organic phase was washed with NaCl solution dried filtered concentrated The residue was purified by chromatography (SiO2, hexane/EtOAc 4:1)

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

实验步骤: TiCl4 (45.6 g, 238 mmol) was added slowly to a solution of 2-ethylphenol (15 g, 119 mmol) in CH2Cl2 (150 ml) was at 0° C. The mixture was warmed to room temperature and dichloromethyl methyl ether (18.3 ml, 200 mmol) was added (strong HCl evolution). The mixture was stirred for 4 h. at room temperature, subsequently cooled to 0° C. and 1M HCl (119 ml, 119 mmol) was added dropwise. The mixture was stirred for 10 min. and subsequently extracted with diethyl ether. The organic phase was washed with saturated NaHCO3 solution and with NaCl solution, dried, filtered and concentrated. The residue was purified by chromatography (SiO2, CH2Cl2=>CH2Cl2/MeOH 9:1). 3-Ethyl-4-hydroxy-benzaldehyde was obtained as a brown oil (7.97 g, 45%). was at 0° C subsequently cooled to 0° C. The mixture was stirred for 10 min. subsequently extracted with diethyl ether The organic phase was washed with saturated NaHCO3 solution and with NaCl solution dried filtered concentrated The residue was purified by chromatography (SiO2, CH2Cl2=>CH2Cl2/MeOH 9:1)

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

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

实验步骤: 45.5 g of titanium tetrachloride was dropwise added, under stirring with ice, to a solution obtained by dissolving 14.64 g of 2-ethylphenol in 200 ml of dichloromethane. After the completion of the dropwise addition, 22.76 g of α,α-dichloromethyl methyl ether was dropwise added thereto. The ice bath was removed, and the reaction solution was stirred at room temperature for 2 hours. Then, the reaction solution was poured into a 10% hydrochloric acid aqueous solution, and the mixture was stirred for 2 hours. The reaction mixture was extracted with chloroform. The chloroform layer was washed with water, and then extracted with a 10% sodium hydoxide aqueous solution. The alkali extract layer was washed twice with chloroform, and then acidified to a pH of about 2 by gradually adding concentrated hydrochloric acid. Then, the mixture was extracted with ethyl acetate. The extract was washed sequentially with water and a saturated sodium chloride aqueous solution, and dried over sodium sulfate. Then, the solvent was distilled off to obtain a dark reddish purple oily substance. This product was purified by silica gel column chromatography by using benzene-ethyl acetate (16 : 1, v/v) as the developer, whereby 6.90 g of the above identified compound was obtained as a pale red oily substance. obtained was dropwise added The ice bath was removed the reaction solution was stirred at room temperature for 2 hours Then, the reaction solution was poured into a 10% hydrochloric acid aqueous solution the mixture was stirred for 2 hours The reaction mixture was extracted with chloroform The chloroform layer was washed with water extracted with a 10% sodium hydoxide aqueous solution The alkali extract layer was washed twice with chloroform by gradually adding concentrated hydrochloric acid Then, the mixture was extracted with ethyl acetate The extract was washed sequentially with water a saturated sodium chloride aqueous solution, and dried over sodium sulfate Then, the solvent was distilled off to obtain a dark reddish purple oily substance This product was purified by silica gel column chromatography was obtained as a pale red oily substance

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

实验步骤: 45.5 g of titanium tetrachloride was dropwise added, under stirring with ice, to a solution obtained by dissolving 14.64 g of 2-ethylphenol in 200 ml of dichloromethane. After the completion of the dropwise addition, 22.76 g of α,α-dichloromethyl methyl ether was dropwise added thereto. The ice bath was removed, and the reaction solution was stirred at room temperature for 2 hours. Then, the reaction solution was poured into a 10% hydrochloric acid aqueous solution, and the mixture was stirred for 2 hours. The reaction mixture was extracted with chloroform. The chloroform layer was washed with water, and then extracted with a 10% sodium hydoxide aqueous solution. The alkali extract layer was washed twice with chloroform, and then acidified to a pH of about 2 by gradually adding concentrated hydrochloric acid. Then, the mixture was extracted with ethyl acetate. The extract was washed sequentially with water and a saturated sodium chloride aqueous solution, and dried over sodium sulfate. Then, the solvent was distilled off to obtain a dark reddish purple oily substance. This product was purified by silica gel column chromatography by using benzene-ethyl acetate (16 : 1, v/v) as the developer, whereby 6.90 g of the above identified compound was obtained as a pale red oily substance. obtained was dropwise added The ice bath was removed the reaction solution was stirred at room temperature for 2 hours Then, the reaction solution was poured into a 10% hydrochloric acid aqueous solution the mixture was stirred for 2 hours The reaction mixture was extracted with chloroform The chloroform layer was washed with water extracted with a 10% sodium hydoxide aqueous solution The alkali extract layer was washed twice with chloroform by gradually adding concentrated hydrochloric acid Then, the mixture was extracted with ethyl acetate The extract was washed sequentially with water a saturated sodium chloride aqueous solution, and dried over sodium sulfate Then, the solvent was distilled off to obtain a dark reddish purple oily substance This product was purified by silica gel column chromatography was obtained as a pale red oily substance