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

HRID 1030581ノート

反応式

HRID 1030581 の反応式
[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

参加物

6

反応物 3

HCID 24758Sodium hydrideHCID 6372219Geranyl chlorideHCID 178488140HCID 178488140、化合物

生成物 1

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

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide溶媒2 回HCID 6344Dichloromethane溶媒

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-d688696dbefe43d2881f47497b3f4259
出典データセット
uspto-grants-1992_04
特許番号
US05106863

反応ノート

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