1,4-Dioxane → methyl 4-(1-(4-(perfluoroethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzoate

HRID 2207008Notes

Reaction equation

HRID 2207008 reaction equation
CC1(C)C(C)(C)OB([C:9]2[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][CH:10]=2)O1.Br[C:21]1[N:25]=[CH:24][N:23]([C:26]2[CH:31]=[CH:30][C:29]([O:32][C:33]([F:39])([F:38])[C:34]([F:37])([F:36])[F:35])=[CH:28][CH:27]=2)[N:22]=1.C([O-])(O)=O.[Na+].O1CCOCC1>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.O>[F:39][C:33]([F:38])([O:32][C:29]1[CH:30]=[CH:31][C:26]([N:23]2[CH:24]=[N:25][C:21]([C:9]3[CH:10]=[CH:11][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:17][CH:18]=3)=[N:22]2)=[CH:27][CH:28]=1)[C:34]([F:37])([F:36])[F:35]

Participants

7

Reactant 4

HCID 312751,4-DioxaneHCID 516892Sodium BicarbonateHCID 2773500Methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoateHCID 893818873-bromo-1-(4-(perfluoroethoxy)phenyl)-1H-1,2,4-triazole

Product 1

HCID 90402708methyl 4-(1-(4-(perfluoroethoxy)phenyl)-1H-1,2,4-triazol-3-yl)benzoateYield 63.2%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
140 °C

Procedure

A microwave vial was charged with methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (147 mg, 0.561 mmol), 3-bromo-1-(4-(pentafluoroethoxy)phenyl)-1H-1,2,4-triazole (200 mg, 0.559 mmol), NaHCO3 (94 mg, 1.2 mmol), and Pd(PPh3)4 (39 mg, 0.034 mmol). Dioxane (3.8 mL) and water (1.2 mL) were added, the reaction vial was capped, and the reaction was heated at 140° C. for 30 min in a Biotage Initiator® microwave reactor with external IR-sensor temperature monitoring from the side of the vessel. The reaction mixture was cooled to RT, and allowed to stand overnight. A white solid formed, which was filtered and air-dried to give the title compound as a white solid (146 mg, 62%): mp 192-195° C., 1H NMR (400 MHz, CDCl3) δ 8.61 (s, 1H), 8.28 (d, J=9.0 Hz, 2H), 8.19-8.12 (d, J=9.0 Hz, 2H), 7.82 (d, J=9.0 Hz, 2H), 7.45-7.38 (m, 2H), 3.95 (s, 3H); 19F NMR (376 MHz, CDCl3) δ −85.90, −87.86; ESIMS m/z 414 ([M+H])+.

Workup

  1. customthe reaction vial was capped
  2. temperatureThe reaction mixture was cooled to RT
  3. customA white solid formed
  4. filtrationwhich was filtered
  5. customair-dried

Sources & evidence

ORD record
ord-4be3843e013c45bf952a81bebc16a1da
Source dataset
uspto-grants-2016_06
Patent number
US09376401B2

Reaction notes

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