ANILINE, p-CHLORO-N-METHYL-N-NITROSO- → 5-Chloro-1-methyl-3-phenylindole-2-acetic acid

HRID 2396561

反応式

HRID 2396561 の反応式
C([O:3][C:4](=[O:15])[CH2:5][C:6]([CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=O)C.C([O-])(=O)C.[Na+].Cl.[Cl:22][C:23]1[CH:28]=[CH:27][C:26]([N:29]([CH3:31])N)=[CH:25][CH:24]=1.ClC1C=CC(N(C)N=O)=CC=1>C(O)(=O)C.O.[Zn]>[Cl:22][C:23]1[CH:24]=[C:25]2[C:26](=[CH:27][CH:28]=1)[N:29]([CH3:31])[C:6]([CH2:5][C:4]([OH:3])=[O:15])=[C:8]2[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1

参加物

8

反応物 4

HCID 13874ANILINE, p-CHLORO-N-METHYL-N-NITROSO-HCID 225855Ethyl 3-oxo-4-phenylbutanoateHCID 517045Sodium AcetateHCID 189874901-(4-Chlorophenyl)-1-methyl hydrazine hydrochloride

生成物 1

HCID 154107305-Chloro-1-methyl-3-phenylindole-2-acetic acid

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 176Acetic Acid溶媒2 回HCID 962Water溶媒2 回

実験手順

To a solution of γ-phenyl acetoacetic acid ethyl ester (2.88 g) in a mixture of acetic acid (30 ml) and water (10 ml) were added sodium acetate (1.83 g) and 1-(4-chlorophenyl)-1-methyl hydrazine hydrochloride (2.73 g) {prepared from 4-chloro-N-methyl-N-nitroso aniline by subjecting to reduction with zinc powder in a mixture of acetic acid and water [m.p.171°-174° C.; NMR (200 MHz, DMSO-d6) ppm: 3.14(3H,s), 7.20(2H,d,J=9 Hz), 7.29(2H,d,J=9 Hz)]}. The mixture was stirred for 15 minutes at room temperature, then for 20 minutes at 110° C. The reaction mixture was concentrated, which was dissolved in ethyl acetate. The solution was washed with water, dilute hydrochloric acid, water, an aqueous solution of sodium hydrogencarbonate and water, successively, which was then dried, followed by distilling off the solvent. The residue was purified by means of a silica gel (30 g) column chromatography (hexane-ethyl acetate=4:1) to give ethyl ester of 5-chloro-1-methyl-3-phenylindole-2-acetic acid as an oily substance (4.34 g). [NMR (200 MHz, CDCl3) ppm: 10 1.29(3H,t,J=7 Hz), 3.76(3H,s), 3.86(2H,s), 4.24(2H,q,J=7 Hz), 7.17-7.62(8H,m)]

後処理

  1. waitfor 20 minutes at 110° C
  2. concentrationThe reaction mixture was concentrated
  3. dissolutionwhich was dissolved in ethyl acetate
  4. washThe solution was washed with water, dilute hydrochloric acid, water
  5. dry with materialan aqueous solution of sodium hydrogencarbonate and water, successively, which was then dried
  6. distillationby distilling off the solvent
  7. customThe residue was purified by means of a silica gel (30 g) column chromatography (hexane-ethyl acetate=4:1)

出典と根拠

ORDレコード
ord-a951888c422d49768afa6ca3cd75704c
出典データセット
uspto-grants-1996_02
特許番号
US05492929

関連ノート

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