Cesium carbonate → 1-(cyclopropylmethyl)-5-(6-ethenyl-2-fluoropyridin-3-yl)-4-(trifluoromethyl)-1H-benzotriazole

HRID 2281039Notes

Reaction equation

HRID 2281039 reaction equation
Cl[C:2]1[N:7]=[C:6]([F:8])[C:5]([C:9]2[CH:21]=[CH:20][C:12]3[N:13]([CH2:16][CH:17]4[CH2:19][CH2:18]4)[N:14]=[N:15][C:11]=3[C:10]=2[C:22]([F:25])([F:24])[F:23])=[CH:4][CH:3]=1.[B-](F)(F)(F)[CH:27]=[CH2:28].[K+].C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCCC1.C(OCC)(=O)C.CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C>[CH:17]1([CH2:16][N:13]2[C:12]3[CH:20]=[CH:21][C:9]([C:5]4[C:6]([F:8])=[N:7][C:2]([CH:27]=[CH2:28])=[CH:3][CH:4]=4)=[C:10]([C:22]([F:25])([F:24])[F:23])[C:11]=3[N:15]=[N:14]2)[CH2:19][CH2:18]1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 23679353Potassium vinyltrifluoroborateHCID 867119775-(6-chloro-2-fluoropyridin-3-yl)-1-(cyclopropylmethyl)-4-(trifluoromethyl)-1H-benzotriazole

Product 1

HCID 867119781-(cyclopropylmethyl)-5-(6-ethenyl-2-fluoropyridin-3-yl)-4-(trifluoromethyl)-1H-benzotriazole

Reagents, catalysts & solvents 3

HCID 178418851HCID 178418851, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

5-(6-Chloro-2-fluoropyridin-3-yl)-1-(cyclopropylmethyl)-4-(trifluoromethyl)-1H-benzotriazole (135 mg, 0.37 mmol) was dissolved in degassed tetrahydrofuran (3.3 mL) and treated with potassium trifluoro(vinyl)borate (174 mg, 1.3 mmol, 4 equiv), cesium carbonate (154 mg, 0.47 mmol, 1.3 equiv) and bis(tri-tert-butylphosphine)palladium(0) (56 mg, 0.11 mmol, 0.3 equiv). The mixture was placed into a preheated oil bath at 65° C. for 1.5 hours, cooled to ambient temperature, diluted with ethyl acetate (50 mL) and washed with sodium bicarbonate (2×30 mL, aqueous saturated). The combined organic extracts were dried with sodium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography (100% dichloromethane), providing the titled compound.

Workup

  1. washwashed with sodium bicarbonate (2×30 mL, aqueous saturated)
  2. dry with materialThe combined organic extracts were dried with sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customThe residue was purified by silica gel chromatography (100% dichloromethane)

Sources & evidence

ORD record
ord-66664bfa527b4ae9ab0f42b1c2ce510a
Source dataset
uspto-grants-2015_09
Patent number
US09139576B2

Reaction notes

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