Potassium Phosphate, Tribasic → 1-{3-[(E)-2-(4-Chloro-phenyl)-vinyl]-phenyl}-3,5-diethyl-1H-pyrazole-4-carboxylic acid methyl ester

HRID 1011864Notes

Reaction equation

HRID 1011864 reaction equation
[CH3:1][O:2][C:3]([C:5]1[C:6]([CH2:19][CH3:20])=[N:7][N:8]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14](Br)[CH:13]=2)[C:9]=1[CH2:10][CH3:11])=[O:4].[Cl:21][C:22]1[CH:27]=[CH:26][C:25](/[CH:28]=[CH:29]/B(O)O)=[CH:24][CH:23]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>CN(C=O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][O:2][C:3]([C:5]1[C:6]([CH2:19][CH3:20])=[N:7][N:8]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14](/[CH:29]=[CH:28]/[C:25]3[CH:26]=[CH:27][C:22]([Cl:21])=[CH:23][CH:24]=3)[CH:13]=2)[C:9]=1[CH2:10][CH3:11])=[O:4]

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 642694trans-2-(4-Chlorophenyl)vinylboronic acidHCID 673139921-(3-Bromo-phenyl)-3,5-diethyl-1H-pyrazole-4-carboxylic acid methyl ester

Product 1

HCID 673141011-{3-[(E)-2-(4-Chloro-phenyl)-vinyl]-phenyl}-3,5-diethyl-1H-pyrazole-4-carboxylic acid methyl ester

Reagents, catalysts & solvents 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

2.10 g (5.0 mmol) of 1-(3-bromo-phenyl)-3,5-diethyl-1H-pyrazole-4-carboxylic acid methyl ester and 1.82 g (10.0 mmol) of (E)-2-(4-chlorophenyl)vinyl boronic acid were dissolved in 50 ml of DMF. 12.5 ml of anhydrous potassium phosphate (tribasic, 2 M in water) were added drop by drop below 25° C., followed by 0.29 g (0.2 mmol) of tetrakis-(triphenylphosphine)-palladium. The reaction mixture was then stirred at 80° C. for 20 hours, cooled to RT, poured into crashed ice and extracted twice with CH2Cl2; the organic phases were washed with water, dried over magnesium sulfate, filtered and evaporated. The residue was purified by flash column chromatography (n-heptane:EtOAc 1:0-8:2) to afford the title compound as light yellow solid. MS: 395.0 (MH+, 1 Cl).

Workup

  1. temperaturecooled to RT
  2. additionpoured
  3. extractionextracted twice with CH2Cl2
  4. washthe organic phases were washed with water
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated
  8. customThe residue was purified by flash column chromatography (n-heptane:EtOAc 1:0-8:2)

Sources & evidence

ORD record
ord-e931c22080bb4566aac8b189cc661612
Source dataset
uspto-grants-2011_07
Patent number
US07977358B2

Reaction notes

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