Sodium hydride → 1-(3,7-dimethyl-2,6(E)-octadienyl)-6-methoxy-1H-1,3-benzimidazole

HRID 1030581노트

반응식

HRID 1030581 반응식
[H-].[Na+].[CH3:3][O:4][C:5]1[CH:6]=[CH:7][C:8]2[NH:12][C:11](S)=[N:10][C:9]=2[CH:14]=1.[CH2:15](Cl)/[CH:16]=[C:17](/[CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])\[CH3:18]>CN(C)C=O.C(Cl)Cl>[CH3:18]/[C:17](/[CH2:19][CH2:20][CH:21]=[C:22]([CH3:24])[CH3:23])=[CH:16]\[CH2:15][N:10]1[C:9]2[CH:14]=[C:5]([O:4][CH3:3])[CH:6]=[CH:7][C:8]=2[N:12]=[CH:11]1

참가 물질

6

반응물 3

HCID 24758Sodium hydrideHCID 6372219Geranyl chlorideHCID 178488140HCID 178488140, 화합물

생성물 1

HCID 867457041-(3,7-dimethyl-2,6(E)-octadienyl)-6-methoxy-1H-1,3-benzimidazole수율 77%

시약·촉매·용매 2

HCID 6228Dimethylformamide용매2회HCID 6344Dichloromethane용매

실험 절차

To a suspension of sodium hydride (0.25 g, 11 mmol) in dimethylformamide (10 mL) at 0° C. under nitrogen was added 6-methoxy-2-mercaptobenzimidazole (1.98 g, 11 mmol) in dimethylformamide (20 mL). The solution was allowed to stir to ambient temperature, then geranyl chloride (1.9 g, 11 mmol) was added and the reaction mixture stirred at 90° C. overnight. Evaporation of the solvent gave a residue which was dissolved in CH2Cl2, washed with H2O and dried over Na2SO4. Evaporation and flash chromatography (Merck Kieselgel, 5% MeOH/CH2Cl2) gave 1-(3,7-dimethyl-2,6(E)-octadienyl)-6-methoxy-1H-1,3-benzimidazole (free base) (2.4 g, 77%) as a 1:1 mixture of 5- and 6-methoxy isomers. Conversion to the oxalate salt in diethyl ether filtration 10 minutes after addition of oxalic acid gave 500 mg of the title compound as a white solid (pure 6-methoxy by 400 MHz NMR with NOE). m.p. 90°-94° C. NMR (DMSO-d6)δ8.3(s,1H), 7.68(d,J=2 Hz,1H), 7.63(d,J=9 Hz,1H), 7.23(m,1H), 5.3 d,J=7 Hz, 1H), 5.0(m,1H), 4.90(d,J=8 Hz,2H), 2.0(m,4H), 1.70(s,3H), 1.58(s,3H), 1.55(s,3H).

후처리

  1. stirringthe reaction mixture stirred at 90° C. overnight
  2. customEvaporation of the solvent
  3. customgave a residue which
  4. washwashed with H2O
  5. dry with materialdried over Na2SO4
  6. customEvaporation and flash chromatography (Merck Kieselgel, 5% MeOH/CH2Cl2)

출처 및 근거

ORD 기록
ord-d688696dbefe43d2881f47497b3f4259
출처 데이터셋
uspto-grants-1992_04
특허 번호
US05106863

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