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

HRID 2396561

반응식

HRID 2396561 반응식
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

참가 물질

8

반응물 4

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

생성물 1

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

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 176Acetic Acid용매2회HCID 962Water용매2회

실험 절차

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)]

후처리

  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)

출처 및 근거

ORD 기록
ord-a951888c422d49768afa6ca3cd75704c
출처 데이터셋
uspto-grants-1996_02
특허 번호
US05492929

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