Ethanol → HCID 67499446, compound

HRID 1484731Notes

Reaction equation

HRID 1484731 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Cl[C:11]1[C:15]([N+:16]([O-:18])=[O:17])=[CH:14][N:13]([C:19]2[CH:20]=[N:21][CH:22]=[CH:23][CH:24]=2)[N:12]=1.C(O)C.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.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>[N+:16]([C:15]1[C:11]([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)=[N:12][N:13]([C:19]2[CH:20]=[N:21][CH:22]=[CH:23][CH:24]=2)[CH:14]=1)([O-:18])=[O:17]

Participants

7

Reactant 4

HCID 702EthanolHCID 11430Potassium CarbonateHCID 66827Phenylboronic AcidHCID 675001483-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine

Product 1

HCID 67499446HCID 67499446, compoundYield 125.6%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
110 °C

Procedure

To a suspension of phenylboronic acid (0.546 g, 4.47 mmol) in toluene (6.63 ml) was added 3-(3-chloro-4-nitro-1H-pyrazol-1-yl)pyridine (0.335 g, 1.492 mmol) followed by ethanol (3.31 ml) and 2 M aqueous potassium carbonate (1.492 ml, 2.98 mmol). The solution was degassed by applying vacuum and then purging with nitrogen (3 times). To the reaction mixture was added palladium tetrakis (0.086 g, 0.075 mmol) and the flask was heated at 110° C. under nitrogen for 16 hours. The aqueous layer was removed and the organic layer was concentrated. The crude product was purified via silica gel chromatography (0-100% ethyl acetate/hexanes) to give 3-(4-nitro-3-phenyl-1H-pyrazol-1-yl)pyridine (499 mg, 1.874 mmol, 80%) as a yellow solid: mp 144.0-146.0° C.; 1H NMR (400 MHz, CDCl3) δ 9.09 (d, J=2.3 Hz, 1H), 8.82 (s, 1H), 8.71 (dd, J=4.8, 1.4 Hz, 1H), 8.16 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.82-7.74 (m, 2H), 7.55-7.48 (m, 4H); EIMS m/z 266.

Workup

  1. customThe solution was degassed
  2. custompurging with nitrogen (3 times)
  3. customThe aqueous layer was removed
  4. concentrationthe organic layer was concentrated
  5. customThe crude product was purified via silica gel chromatography (0-100% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-706bf95ef497400e9ac54be31c0023fb
Source dataset
uspto-grants-2016_08
Patent number
US09422278B2

Reaction notes

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