Propyne → 5-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-(prop-1-ynyl)pyrazole

HRID 1383567Notes

Reaction equation

[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1I.C(N(CC)CC)C.[CH:29]#[C:30][CH3:31]>CN(C)C=O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([C:19]#[N:20])[C:3]=1[C:29]#[C:30][CH3:31]

Participants

Conditions

Temperature: -78 °C

Procedure

To a stirred solution of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)4-iodopyrazole (0.904 g, the compound of Example A1) in dimethylformamide(2 ml) and triethylamine (10 ml) contained in a stainless steel bomb was added cuprous iodide (60 mg) and bis(triphenylphosphine)palladium(II) chloride (120 mg). The reaction vessel was cooled to −78° C. and propyne (2 g) condensed into it. The vessel was sealed and then heated at 70° C. for 18 hours and then left at room temperature for 2 days. The reaction mixture was partitioned between ether and water. The organic layer was separated, washed with brine, dried (MgSO4) and evaporated. The residue was purified by column chromatography on silica gel eluted with dichloromethane : hexane (1:1) to provide the title compound as a white solid m.p. 226-8° C.

Workup

customThe vessel was sealed
temperatureheated at 70° C. for 18 hours
customThe reaction mixture was partitioned between ether and water
customThe organic layer was separated
washwashed with brine
dry with materialdried (MgSO4)
customevaporated
customThe residue was purified by column chromatography on silica gel
washeluted with dichloromethane : hexane (1:1)

Sources & evidence

ORD record: ord-cf202389134045f090c0637b93ebefe6
Source dataset: uspto-grants-2001_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06255333B1

Reaction notes

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