Cesium carbonate → HCID 66729277, compound

HRID 1098603Notes

Reaction equation

HRID 1098603 reaction equation
Cl[C:2]1[C:7]([N+:8]([O-])=O)=[CH:6][C:5]([C:11]([F:14])([F:13])[F:12])=[CH:4][N:3]=1.[CH3:15][N:16]1[CH:20]=[C:19](B2OC(C)(C)C(C)(C)O2)[CH:18]=[N:17]1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C=O)C.O.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>[CH3:15][N:16]1[CH:20]=[C:19]([C:2]2[C:7]([NH2:8])=[CH:6][C:5]([C:11]([F:14])([F:13])[F:12])=[CH:4][N:3]=2)[CH:18]=[N:17]1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 27739871-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazoleHCID 47369502-Chloro-3-nitro-5-(trifluoromethyl)pyridine

Product 1

HCID 66729277HCID 66729277, compoundYield 5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
90 °C

Procedure

2-Chloro-3-nitro-5-(trifluoromethyl)pyridine (406 mg, 1.79 mmol), 1-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole (559 mg, 2.69 mmol), cesium carbonate (1752 mg, 5.38 mmol) and palladium tetrakis (207 mg, 0.179 mmol) were combined in DMF (3 mL) and water (1 mL). The headspace was evacuated and back-filled with nitrogen (4×). The mixture was heated to 90° C. overnight. The mixture was poured into EtOAc (40 mL) and washed with water (3×20 mL) and satd brine (3×20 mL). The organics were concentrated in vacuo and purified by silica gel chromatography to provide 2-(1-methyl-1H-pyrazol-4-yl)-5-(trifluoromethyl)pyridin-3-amine (21 mg, 5% yield). 1H NMR (400 MHz, DMSO-d6): δ 8.29 (s, 1 H), 8.13 (br s, 1 H), 7.98 (s, 1 H), 7.40 (d, J=2.0 Hz, 1 H) 5.55 (s, 2 H), 3.91 (s, 3 H); MS (ESI): m/z 473.0 (M+H+).

Workup

  1. customThe headspace was evacuated
  2. additionback-filled with nitrogen (4×)
  3. additionThe mixture was poured into EtOAc (40 mL)
  4. washwashed with water (3×20 mL) and satd brine (3×20 mL)
  5. concentrationThe organics were concentrated in vacuo
  6. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-135c47b2b42d4df8b8ef7e9f44591a1d
Source dataset
uspto-grants-2012_03
Patent number
US08143293B2

Reaction notes

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