Cesium carbonate → 3-fluoro-2-(1H-1,2,3-triazol-1-yl)benzoic acid

HRID 64213

反応式

HRID 64213 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].C([O-])([O-])=O.[Cs+].[Cs+].[N:18]1[NH:19][N:20]=[CH:21][CH:22]=1.CN(C)[C@@H]1CCCC[C@H]1N>O1CCOCC1.O.[Cu]I>[F:1][C:2]1[C:3]([N:18]2[CH:22]=[CH:21][N:20]=[N:19]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 10796Cesium carbonateHCID 675161H-1,2,3-TriazoleHCID 11275066(1R,2R)-N1,N1-Dimethylcyclohexane-1,2-diamineHCID 223203083-Fluoro-2-iodobenzoic acid

生成物 1

HCID 670871113-fluoro-2-(1H-1,2,3-triazol-1-yl)benzoic acid

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 3-fluoro-2-iodobenzoic acid (4.5 g, 16.9 mmol) dissolved in dioxane (33.8 mL) and H2O (0.09 mL) was added Cs2CO3 (11.02 g, 33.8 mmol), CuI (161 mg, 0.85 mmol), 2H-1,2,3-triazole (1.96 mL, 33.8 mmol), and trans-N,N-dimethyl-1,2-cyclohexanediamine (0.53 mL, 3.38 mmol). The mixture was then heated to 100° C. overnight, cooled to room temperature, diluted with H2O, and extracted with EtOAc. The aqueous layer was then acidified and extracted with EtOAc. The combined organics were dried and concentrated. From this concentrate a solid precipitated to provide intermediate A-33 (285 mg, 8%). MS (ESI) mass calcd for C9H6FN3O2, 207.0. m/z found 208.1 [M+H]+. 1H NMR (500 MHz, Methanol-d4) δ 6.81-6.77 (m, 1H), 6.46-6.40 (m, 2H), 6.30-6.23 (m, 1H), 6.18-6.12 (m, 1H).

後処理

  1. temperaturecooled to room temperature
  2. extractionextracted with EtOAc
  3. extractionextracted with EtOAc
  4. customThe combined organics were dried
  5. concentrationconcentrated
  6. concentrationFrom this concentrate a solid
  7. customprecipitated
  8. customto provide intermediate A-33 (285 mg, 8%)

出典と根拠

ORDレコード
ord-4dea00b4ab2f43b8ac28fd28e2f79abf
出典データセット
uspto-grants-2016_09
特許番号
US09447117B2

関連ノート

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