1-(2-Chlorophenyl)imidazole → methyl 2-(1-(2-chlorophenyl)-1H-imidazol-2-yl)-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepine-10-carboxylate

HRID 1498148

반응식

HRID 1498148 반응식
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N:8]1[CH:12]=[CH:11][N:10]=[CH:9]1.C([Li])CCC.I[C:19]1[N:20]=[C:21]2[C:27]3[CH:28]=[C:29]([C:32]([O:34][CH3:35])=[O:33])[CH:30]=[CH:31][C:26]=3[O:25][CH2:24][CH2:23][N:22]2[CH:36]=1>CCCCCC.O1CCCC1.CCOC(C)=O.[Cl-].[Cl-].[Zn+2].C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[N:8]1[CH:12]=[CH:11][N:10]=[C:9]1[C:19]1[N:20]=[C:21]2[C:27]3[CH:28]=[C:29]([C:32]([O:34][CH3:35])=[O:33])[CH:30]=[CH:31][C:26]=3[O:25][CH2:24][CH2:23][N:22]2[CH:36]=1

참가 물질

9

반응물 3

HCID 1428581-(2-Chlorophenyl)imidazoleHCID 58204419Methyl 2-iodo-5,6-dihydroimidazo[1,2-d][1,4]benzoxazepine-10-carboxylateHCID 178418339Butyllithium

생성물 1

HCID 58204585methyl 2-(1-(2-chlorophenyl)-1H-imidazol-2-yl)-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepine-10-carboxylate

시약·촉매·용매 5

HCID 3007855Zincchloride촉매2회HCID 178418397HCID 178418397, 화합물촉매HCID 8028Tetrahydrofuran용매4회HCID 8058Hexane용매HCID 8857Ethyl Acetate용매

반응 조건

온도
-78 °C

실험 절차

To a solution of 1-(2-chlorophenyl)-1H-imidazole (0.133 g, 0.743 mmol) in tetrahydrofuran (5.43 mL, 66.9 mmol) at −78° C. was added 1.60 M of n-Butyllithium in Hexane (0.464 mL) dropwise. The reaction mixture was stirred at −78° C. for 1 h then 0.50 M of Zinc dichloride in Tetrahydrofuran (1.48 mL) was added. The reaction mixture was warmed to RT 30 min then added Tetrakis(triphenylphosphine)palladium(0) (0.0780 g, 0.0675 mmol), solution of methyl 2-iodo-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepine-10-carboxylate (0.250 g, 0.675 mmol) in 2 ml THF. The reaction was reflux for 2 h followed by treating with additional 0.50 M of Zinc dichloride in Tetrahydrofuran 2.2 ml and refluxed 3 h. The mixture was diluted with EtOAc then washed with sat. Na2CO3, and brine. The organic layer was dried over Na2SO4, concentrated in vacuo. The crude product, methyl 2-(1-(2-chlorophenyl)-1H-imidazol-2-yl)-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepine-10-carboxylate, was purified by chromatography. MS: (ESI+)=421.2

후처리

  1. temperatureThe reaction mixture was warmed to RT 30 min
  2. temperatureThe reaction was reflux for 2 h
  3. temperaturerefluxed 3 h
  4. washthen washed with sat. Na2CO3, and brine
  5. dry with materialThe organic layer was dried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customThe crude product, methyl 2-(1-(2-chlorophenyl)-1H-imidazol-2-yl)-5,6-dihydrobenzo[f]imidazo[1,2-d][1,4]oxazepine-10-carboxylate, was purified by chromatography

출처 및 근거

ORD 기록
ord-3e67fecdd4834e468d9455b38347e4af
출처 데이터셋
uspto-grants-2015_12
특허 번호
US09198918B2

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