Water → HCID 66851084, compound

HRID 1466612Notes

Reaction equation

HRID 1466612 reaction equation
FC(F)(F)S(O[C:7]1[CH:12]=[CH:11][C:10]([Cl:13])=[CH:9][C:8]=1[C:14]1[N:18]([CH2:19][O:20][CH2:21][CH2:22][Si:23]([CH3:26])([CH3:25])[CH3:24])[N:17]=[CH:16][C:15]=1[N+:27]([O-:29])=[O:28])(=O)=O.[CH:32]1(B(O)O)[CH2:34][CH2:33]1.P([O-])([O-])([O-])=O.[K+].[K+].[K+].[Br-].[Na+].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.C1(C)C=CC=CC=1>[Cl:13][C:10]1[CH:11]=[CH:12][C:7]([CH:32]2[CH2:34][CH2:33]2)=[C:8]([C:14]2[N:18]([CH2:19][O:20][CH2:21][CH2:22][Si:23]([CH3:26])([CH3:25])[CH3:24])[N:17]=[CH:16][C:15]=2[N+:27]([O-:29])=[O:28])[CH:9]=1

Participants

8

Reactant 5

HCID 962WaterHCID 62657Potassium Phosphate, TribasicHCID 253881Sodium BromideHCID 2760897Cyclopropylboronic acidHCID 86668383HCID 86668383, compound

Product 1

HCID 66851084HCID 66851084, compoundYield 53.1%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

To a mixture of 4-chloro-2-(4-nitro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazol-5-yl)phenyl trifluoromethanesulfonate (72.4 mg, 0.144 mmol), cyclopropylboronic acid (55.0 mg, 0.640 mmol), tetrakis(triphenylphosphine)palladium(0) (79.2 mg, 0.685 mmol), potassium phosphate (152.7 mg, 0.7194 mmol), and sodium bromide (149.2 mg, 1.450 mmol) was added water (13.0 μL, 0.722 mmol) and toluene (3.0 mL). The reaction mixture was heated at 90° C. for 72 hours. The reaction mixture was partitioned between ethyl acetate and water, and the organic layer washed with brine, dried over magnesium sulfate, and evaporated in vacuo. The crude product was purified via flash chromatography on silica gel (0 to 30% ethyl acetate in heptanes) to yield 30.1 mg (53%) of 5-(5-chloro-2-cyclopropylphenyl)-4-nitro-1-((2-(trimethylsilyl)ethoxy)methyl)-1H-pyrazole. LCMS (ESI) m+Na=416.2.

Workup

  1. customThe reaction mixture was partitioned between ethyl acetate and water
  2. washthe organic layer washed with brine
  3. dry with materialdried over magnesium sulfate
  4. customevaporated in vacuo
  5. customThe crude product was purified via flash chromatography on silica gel (0 to 30% ethyl acetate in heptanes)

Sources & evidence

ORD record
ord-84e6efe39d064d34a6d8dae809c0e0e8
Source dataset
uspto-grants-2015_04
Patent number
US08999998B2

Reaction notes

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