Cesium carbonate → 2,3-Dimethoxy-6-[1,2,3]triazol-2-yl-benzoic acid

HRID 243870

Reaktionsgleichung

Reaktionsgleichung von HRID 243870
Br[C:2]1[CH:10]=[C:9]([O:11][CH3:12])[C:8]([O:13][CH3:14])=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[C:15](=[O:18])([O-])[O-:16].[Cs+].[Cs+].[NH:21]1[CH:25]=[CH:24][N:23]=[N:22]1.CN[C@@H]1CCCC[C@H]1NC>CCOCC.O.[Cu](I)I.CN(C=O)C>[CH3:15][O:18][C:7]1[C:8]([O:13][CH3:14])=[CH:9][CH:10]=[C:2]([N:22]2[N:23]=[CH:24][CH:25]=[N:21]2)[C:3]=1[C:4]([OH:6])=[O:5].[CH3:12][O:11][C:9]1[C:8]([O:13][CH3:14])=[CH:7][CH:3]=[C:2]([N:21]2[CH:25]=[CH:24][N:23]=[N:22]2)[C:10]=1[C:15]([OH:16])=[O:18]

Komponenten

10

Edukt 4

HCID 10796Cesium carbonateHCID 2229632-Bromo-4,5-dimethoxybenzoic acidHCID 2733821trans-N,N'-dimethyl-1,2-cyclohexanediamineHCID 178418936HCID 178418936, Verbindung

Produkt 2

HCID 670869032,3-Dimethoxy-6-[1,2,3]triazol-2-yl-benzoic acidAusbeute 60 %HCID 670869252,3-Dimethoxy-6-[1,2,3]triazol-1-yl-benzoic acidAusbeute 20 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 83717Copper iodideKatalysatorHCID 962WaterLösungsmittelHCID 3283Diethyl EtherLösungsmittelHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
120 °C

Versuchsvorschrift

To a 20 ml microwave vial containing 2-bromo-4,5-dimethoxybenzoic acid (3 g, 11.5 mmol), copper iodide (0.04 g, 0.5 mol %), cesium carbonate (7.5 g, 23 mmol), triazole (1.33 mL, 23 mmol) and finally (R,R)-(−)-N,N′-dimethyl-1,2-cyclohexanediamine ligand (0.36 mL, 2.3 mmol) was added DMF (12 mL). The resulting clumpy yellow slurry was stirred until evenly dispersed then heated to 120° C. for 10-20 min using a microwave. At this point the reaction mixture appeared as a blue slurry which was then diluted with 20 mL ether and 20 mL H2O. The resulting solution was thoroughly stirred and transferred to a separatory funnel then the RBF was subsequently rinsed with 20 mL ether and H2O each. The aqueous layer was separated from the organic layer and acidified to pH 1 with 6 mL conc. HCl. The now brown/lime green aqueous layer was extracted twice with EtOAc. The bright yellow organic layers were combined and dried with Na2SO4 and then conc. into a yellow powder under reduced pressure which was purified by FCC (0-5% MeOH in DCM w/0.5% AcOH) to afford 2,3-dimethoxy-6-[1,2,3]triazol-2-yl-benzoic acid (60%) and 2,3-dimethoxy-6-[1,2,3]triazol-1-yl-benzoic acid (20%). Data for 2,3-dimethoxy-6-[1,2,3]triazol-2-yl-benzoic acid, MS (ESI): mass calculated for C11H11N3O4, 249.23; m/z found 250.3 [M+H]+. 1H NMR (400 MHz, CD3OD): 7.87 (s, 2H), 7.47 (s, 1H), 7.18 (s, 1H), 3.94 (s, 3H), 3.91 (s, 3H).

Aufarbeitung

  1. additionuntil evenly dispersed
  2. stirringThe resulting solution was thoroughly stirred
  3. customtransferred to a separatory funnel
  4. washthe RBF was subsequently rinsed with 20 mL ether and H2O each
  5. customThe aqueous layer was separated from the organic layer
  6. extractionThe now brown/lime green aqueous layer was extracted twice with EtOAc
  7. dry with materialdried with Na2SO4
  8. customconc. into a yellow powder under reduced pressure which was purified by FCC (0-5% MeOH in DCM w/0.5% AcOH)

Quellen und Nachweise

ORD-Eintrag
ord-1721d72c2d0446589d90ffe388cc4912
Quelldatensatz
uspto-grants-2014_02
Patentnummer
US08653263B2

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