Methyl 3-isocyanatobenzoate → 3-[3-(2,2-Diethoxyethyl)-3-(4-isopropylphenyl)ureido]benzoic acid methyl ester

HRID 600926

反応式

HRID 600926 の反応式
[CH:1]([C:4]1[CH:9]=[CH:8][C:7]([NH:10][CH2:11][CH:12]([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15])=[CH:6][CH:5]=1)([CH3:3])[CH3:2].[C:19]([C:23]1[CH:24]=[C:25]([N:29]=[C:30]=[O:31])[CH:26]=[CH:27][CH:28]=1)([O:21][CH3:22])=[O:20]>ClCCl>[CH:1]([C:4]1[CH:5]=[CH:6][C:7]([N:10]2[CH:11]=[CH:12][N:29]([C:25]3[CH:24]=[C:23]([CH:28]=[CH:27][CH:26]=3)[C:19]([OH:21])=[O:20])[C:30]2=[O:31])=[CH:8][CH:9]=1)([CH3:2])[CH3:3].[CH3:22][O:21][C:19](=[O:20])[C:23]1[CH:28]=[CH:27][CH:26]=[C:25]([NH:29][C:30]([N:10]([CH2:11][CH:12]([O:13][CH2:14][CH3:15])[O:16][CH2:17][CH3:18])[C:7]2[CH:8]=[CH:9][C:4]([CH:1]([CH3:2])[CH3:3])=[CH:5][CH:6]=2)=[O:31])[CH:24]=1

参加物

5

反応物 2

HCID 2733366Methyl 3-isocyanatobenzoateHCID 196009444-Isopropyl-N-(2,2-diethoxyethyl)aniline

生成物 2

HCID 103140423-[3-(4-Isopropylphenyl)-2-oxo-2,3-dihydroimidazol-1-yl]benzoic acidHCID 666034673-[3-(2,2-Diethoxyethyl)-3-(4-isopropylphenyl)ureido]benzoic acid methyl ester収率 170.4%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

A solution of N-(4-isopropylphenyl)-2,2-diethoxyethylamine (0.50 g, 2.0 mmol) prepared above and 3-carbomethoxyphenyl isocyanate (0.36 g, 2.05 mmol) in dry dichloromethane (10 mL) was stirred at room temperature overnight. The solution was then chromatographed (silica gel, hexanes:ethyl acetate, 8:2) to give the pure urea, 3-[3-(2,2-diethoxyethyl)-3-(4-isopropylphenyl)ureido]benzoic acid methyl ester as a colorless oil (0.73 g, 85.3%). MS (ES−) m/z: 427. This was then stirred with HCl (0.5 M, 50 mL) at 80° C. for 4 h. After cooling to room temperature, the white precipitate formed was collected and purified by chromatography (silica gel, dichloromethane:ethyl acetate, 9:1) to give pure methyl 3-[3-(4-isopropylphenyl)-2-oxo-2,3-dihydroimidazol-1-yl]benzoate as white solid [0.42 g, 73.7%, MS (ES+) m/z: 337]. The solid was then treated with boron tribromide in dichloromethane (1.0 M, 4.0 mL) at room temperature overnight. The volatiles were removed in vacuum and the residue was suspended in water and stirred for 30 min. The solid was collected by filtration and washed with water to furnish 3-[3-(4-isopropylphenyl)-2-oxo-2,3-dihydroimidazol-1-yl]benzoic acid (0.40 g, 100%). m.p. 283-285° C. 1H NMR (CDCl3, 300 MHz) δ (ppm) 1.24 (d, 6H), 2.84-3.00 (m, 1H), 6.69 (d, 1H), 6.74 (d, 1H), 7.26 (d, 2H), 7.45-7.54 (m, 3H), 7.91 (d, 1H), 8.02 (d, 1H), 8.12 (s, 1H). MS (ES−) m/z: 321.

後処理

  1. customThe solution was then chromatographed (silica gel, hexanes:ethyl acetate, 8:2)

出典と根拠

ORDレコード
ord-1a415a6870b04f00b8828f7e50c4512e
出典データセット
uspto-grants-2011_03
特許番号
US07902241B2

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