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

HRID 869022

Reaktionsgleichung

Reaktionsgleichung von HRID 869022
[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]

Komponenten

8

Edukt 4

HCID 10796Cesium carbonateHCID 675161H-1,2,3-TriazoleHCID 11275066(1R,2R)-N1,N1-Dimethylcyclohexane-1,2-diamineHCID 223203083-Fluoro-2-iodobenzoic acid

Produkt 1

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

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 962WaterLösungsmittel2×HCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

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).

Aufarbeitung

  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%)

Quellen und Nachweise

ORD-Eintrag
ord-9bef943801574c0c9548f24bf3b6d421
Quelldatensatz
uspto-grants-2015_03
Patentnummer
US08969352B2

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