Pyrazole → 3-Fluoro-2-(1H-pyrazol-1-YL)benzoic acid

HRID 2174992

反応式

HRID 2174992 の反応式
[F:1][C:2]1[C:3](I)=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6].[NH:12]1[CH:16]=[CH:15][CH:14]=[N:13]1.CN[C@@H]1CCCC[C@H]1NC.C([O-])([O-])=O.[Cs+].[Cs+]>O.[Cu]I.O1CCOCC1>[F:1][C:2]1[C:3]([N:12]2[CH:16]=[CH:15][CH:14]=[N:13]2)=[C:4]([CH:8]=[CH:9][CH:10]=1)[C:5]([OH:7])=[O:6]

参加物

8

反応物 4

HCID 1048PyrazoleHCID 10796Cesium carbonateHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 223203083-Fluoro-2-iodobenzoic acid

生成物 1

HCID 534097523-Fluoro-2-(1H-pyrazol-1-YL)benzoic acid収率 72.8%

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 962Water溶媒2 回HCID 312751,4-Dioxane溶媒

反応条件

温度
100 °C

実験手順

To a mixture of 3-fluoro-2-iodobenzoic acid (1.4 g, 5.26 mmol), 1H-pyrazole (0.72 g, 10.5 mmol), trans-N,N′-dimethyl-cyclohexane-1,2-diamine (0.17 mL, 1.05 mmol), CuI (50.1 mg, 0.26 mmol), dioxane (50 mL) and water (0.028 mL) was added Cs2CO3 (3.43 g, 10.5 mmol). The reaction mixture was heated to 100° C. for 1 h. The reaction mixture was cooled to ambient temperature then diluted with water. The aqueous layer was acidified to pH 2 and extracted with EtOAc (30 mL) three times. The organic layers were combined, dried over Na2SO4, filtered and concentrated. The residue was purified by FCC (SiO2, gradient DCM to 10% MeOH/1% HOAC/DCM) to the yield the title compound as a colorless oil (790 mg, 72%). 1H NMR (400 MHz, CDCl3): 7.85-7.73 (m, 1H), 7.54-7.44 (m, 1H), 7.44-7.34 (m, 1H), 6.55 (s, 1H).

後処理

  1. temperatureThe reaction mixture was cooled to ambient temperature
  2. extractionextracted with EtOAc (30 mL) three times
  3. dry with materialdried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue was purified by FCC (SiO2, gradient DCM to 10% MeOH/1% HOAC/DCM) to the

出典と根拠

ORDレコード
ord-4a37681f5b8242f9a0c23fb910f94597
出典データセット
uspto-grants-2015_06
特許番号
US09062044B2

関連ノート

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