Diisopropylethylamine → HCID 68413353, compound

HRID 2194696Notes

Reaction equation

HRID 2194696 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N:9]1[C:13](OS(C(F)(F)F)(=O)=O)=[CH:12][C:11]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=[N:10]1.[SH:27][CH2:28][CH2:29][C:30]([O:32][CH2:33][CH:34]([CH2:39][CH3:40])[CH2:35][CH2:36][CH2:37][CH3:38])=[O:31].C(N(C(C)C)C(C)C)C.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C.O>[F:1][C:2]1[CH:7]=[CH:6][C:5]([F:8])=[CH:4][C:3]=1[N:9]1[C:13]([S:27][CH2:28][CH2:29][C:30]([O:32][CH2:33][CH:34]([CH2:39][CH3:40])[CH2:35][CH2:36][CH2:37][CH3:38])=[O:31])=[CH:12][C:11]([C:22]([O:24][CH2:25][CH3:26])=[O:23])=[N:10]1

Participants

9

Reactant 4

HCID 81531DiisopropylethylamineHCID 926402-Ethylhexyl 3-mercaptopropionateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 86644415HCID 86644415, compound

Product 1

HCID 68413353HCID 68413353, compoundYield 53%

Reagents, catalysts & solvents 4

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
110 °C

Procedure

A solution of ethyl 1-(2,5-difluorophenyl)-5-{[(trifluoromethyl)sulfonyl]oxy}-1H-pyrazole-3-carboxylate (3.4 g), 2-ethylhexyl 3-mercaptopropionate (2.4 g) and N-ethyldiisopropylamine (1.9 g) in toluene (30 mL) was sufficiently deaerated, tris(dibenzylideneacetone)dipalladium (0) (342 mg) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (432 mg) were added, and the mixture was further deaerated. Under an argon atmosphere, the reaction mixture was stirred at 110° C. for 2 hr, and allowed to cool to room temperature. Water and ethyl acetate were added, and the mixture was filtered through celite. The organic layer of the filtrate was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=19:1→7:1) to give the title compound as a yellow oil (yield 1.8 g, yield 53%).

Workup

  1. temperatureto cool to room temperature
  2. filtrationthe mixture was filtered through celite
  3. washThe organic layer of the filtrate was washed with saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (eluent:hexane-ethyl acetate=19:1→7:1)

Sources & evidence

ORD record
ord-38a314c8d33f46af9f5b61222babe958
Source dataset
uspto-grants-2012_12
Patent number
US08334301B2

Reaction notes

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