Ethyl Acetate → 2-(1-Methyl-1h-imidazol-4-yl)-4-[(6-nitro-3-pyridinyl)oxy]pyridine

HRID 1049254ノート

反応式

HRID 1049254 の反応式
Cl[C:2]1[CH:7]=[C:6]([O:8][C:9]2[CH:10]=[N:11][C:12]([N+:15]([O-:17])=[O:16])=[CH:13][CH:14]=2)[CH:5]=[CH:4][N:3]=1.[CH3:18][N:19]1[CH:23]=[C:22]([Sn](CCCC)(CCCC)CCCC)[N:21]=[CH:20]1.[F-].[K+].CCOC(C)=O>C1(C)C=CC=CC=1.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>[CH3:18][N:19]1[CH:23]=[C:22]([C:2]2[CH:7]=[C:6]([O:8][C:9]3[CH:10]=[N:11][C:12]([N+:15]([O-:17])=[O:16])=[CH:13][CH:14]=3)[CH:5]=[CH:4][N:3]=2)[N:21]=[CH:20]1

参加物

7

反応物 4

HCID 8857Ethyl AcetateHCID 522689Potassium FluorideHCID 219011411-Methyl-4-(tributylstannyl)-1H-imidazoleHCID 593227792-Chloro-4-((6-nitropyridin-3-yl)oxy)pyridine

生成物 1

HCID 904032142-(1-Methyl-1h-imidazol-4-yl)-4-[(6-nitro-3-pyridinyl)oxy]pyridine収率 91%

試薬・触媒・溶媒 2

HCID 178418397HCID 178418397、化合物触媒HCID 1140Toluene溶媒

反応条件

温度
110 °C

実験手順

A mixture of Example A1 (1.5 g, 5.96 mmol), N-methyl-4-(tributylstannyl)imidazole (3.32 g, 8.94 mmol) and Pd(PPh3)4 (0.344 g, 0.298 mmol) in toluene (30 mL) sparged with Ar and heated at 110° C. overnight. The mixture was cooled to RT, treated with 10% KF and EtOAc, stirred at RT for 2 h, the solids removed via filtration through diatomaceous earth and washed with 5% MeOH/DCM. The layers of the filtrate were separated and the organic layer was washed with brine, dried over Na2SO4, concentrated to dryness and purified via silica gel chromatography (MeOH/DCM). The material was washed with a small amount of Et2O and dried to afford 2-(1-methyl-1H-imidazol-4-yl)-4-((6-nitropyridin-3-yl)oxy)pyridine (1.61 g, 91%). 1H NMR (400 MHz, Acetone-d6): δ 8.54 (d, J=2.8 Hz, 1H), 8.50 (d, J=5.6 Hz, 1H), 8.44-8.43 (m, 1H), 7.98 (dd, J=8.9, 2.8 Hz, 1H), 7.69 (d, J=1.4 Hz, 1H), 7.62 (d, J=2.6 Hz, 1H), 7.55 (s, 1H), 6.97 (dd, J=5.6, 2.6 Hz, 1H), 3.81 (s, 3H); MS (ESI) m/z: 298.1 (M+H+).

後処理

  1. temperatureThe mixture was cooled to RT
  2. customthe solids removed via filtration through diatomaceous earth
  3. washwashed with 5% MeOH/DCM
  4. customThe layers of the filtrate were separated
  5. washthe organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. concentrationconcentrated to dryness
  8. custompurified via silica gel chromatography (MeOH/DCM)
  9. washThe material was washed with a small amount of Et2O
  10. customdried

出典と根拠

ORDレコード
ord-0ea9ed9e2e094ef69082d8c5163fd34a
出典データセット
uspto-grants-2016_07
特許番号
US09382228B2

反応ノート

読み込み中…