Water → 1,8-diethyl-4-(5-hexenyl)-2,3,4,9-tetrahydro-1H-carbazole-1-acetic acid methyl ester

HRID 477053

반응식

HRID 477053 반응식
[CH3:1][O:2][C:3](=[O:20])[CH2:4][C:5]1([CH2:18][CH3:19])[CH2:10][CH2:9][CH:8]([CH2:11][CH2:12][CH2:13][CH2:14][CH:15]=[CH2:16])[CH2:7][C:6]1=O.[CH2:21]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][C:24]=1[NH:29]N)[CH3:22].O.B(F)(F)F.CCOCC>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:20])[CH2:4][C:5]1([CH2:18][CH3:19])[C:6]2[NH:29][C:24]3[C:25](=[CH:26][CH:27]=[CH:28][C:23]=3[CH2:21][CH3:22])[C:7]=2[CH:8]([CH2:11][CH2:12][CH2:13][CH2:14][CH:15]=[CH2:16])[CH2:9][CH2:10]1

참가 물질

6

반응물 4

HCID 962Water2회HCID 8000Boron trifluoride etherateHCID 2733210(2-Ethylphenyl)hydrazineHCID 146499081-Ethyl-4-(5-hexenyl)-2-oxocyclohexaneacetic Acid Methyl Ester

생성물 1

HCID 146499091,8-diethyl-4-(5-hexenyl)-2,3,4,9-tetrahydro-1H-carbazole-1-acetic acid methyl ester수율 64%

시약·촉매·용매 1

HCID 1140Toluene용매

실험 절차

A solution of 1-ethyl-4-(5-hexenyl)-2-oxocyclohexaneacetic acid methyl ester isomer B (4.24 g, 15.14 mmol) and 2-ethylphenylhydrazine (2.27 g, 16.7 mmol) in 30.3 mL of toluene was refluxed under nitrogen for 22 hours with azeotropic removal of water. The toluene was then removed in vacuo and replaced with 10.8 mL of acetic acid. The solution was treated with borontrifluoride etherate (2.79 g, 19.7 mmol, 2.42 mL) and refluxed for 20 minutes under nitrogen. The reaction mixture was poured into 120 mL of water and extracted with 4×80 mL of 2.5N NaOH. Drying (MgSO4) and flash chromatography (75 mm diameter column, 8% ethyl acetate in petroleum ether eluent) afforded 3.72 g (9.73 mmol, 64%) of 1,8-diethyl-4-(5-hexenyl)-2,3,4,9-tetrahydro-1H-carbazole-1-acetic acid methyl ester. Of this, 3.68 g (9.66 mmol) were refluxed in a solution of ethanol (30.9 mL) and 2.5N NaOH (7.7 mL) for 45 minutes under nitrogen. The ethanol was then removed in vacuo and the residue was suspended in 120 mL of 1N HCl. It was extracted with 4×40 mL of ether and the pooled extracts were dried over MgSO4. Flash chromatography (50 mm diameter column, 10% ethyl acetate in petroleum ether eluent, 2% H3PO4 in MeOH treated silica gel) afforded 3.41 g (9.18 mmol, 95%) of a light yellow solid which was recrystallized from 85:15 petroleum ether:benzene. This resulted in 1.98 g of a white powder which were dried at 84° C. for 31 hours followed by recrystallization from 85:15 petroleum ether:benzene once again. Drying at 84° C. for 24 hours resulted in 1.41 g of a white powder, m.p. 96°-97° C.

후처리

  1. customThe toluene was then removed in vacuo
  2. temperaturerefluxed for 20 minutes under nitrogen
  3. extractionextracted with 4×80 mL of 2.5N NaOH
  4. dry with materialDrying (MgSO4) and flash chromatography (75 mm diameter column, 8% ethyl acetate in petroleum ether eluent)

출처 및 근거

ORD 기록
ord-1a4d46eea2e14ff48833d25633fd9fbe
출처 데이터셋
uspto-grants-1989_12
특허 번호
US04886826

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