Methyl iodide → HCID 18005446, compound

HRID 989236Notes

Reaction equation

[CH3:1][Li].Br[C:4]1[N:8]([C:9]2[C:14]([Cl:15])=[CH:13][C:12]([C:16]([F:19])([F:18])[F:17])=[CH:11][C:10]=2[Cl:20])[N:7]=[C:6]([C:21]#[N:22])[C:5]=1[S:23][CH3:24].CI>C(OCC)C.O1CCCC1>[Cl:20][C:10]1[CH:11]=[C:12]([C:16]([F:19])([F:18])[F:17])[CH:13]=[C:14]([Cl:15])[C:9]=1[N:8]1[C:4]([CH3:1])=[C:5]([S:23][CH3:24])[C:6]([C:21]#[N:22])=[N:7]1

Participants

Conditions

Temperature: 0 °C

Procedure

A 1.4 M solution of methyllithium (31 ml) in ethyl ether was added to a stirred solution of 5-bromo-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylthio-1H-pyrazole-3-carbonitrile (17.67 g) in dry tetrahydrofuran (THF) at −65° C. over 15-minutes and allowed to warm to 0° C. over 3-hours. After recooling to −65° C., methyl iodide (3.06 ml) in THF was added over 3 minutes, the mixture warmed to −20° C. over 1.5 hours, and then partitioned between aqueous ammonium chloride and dichloromethane. The organic phase was dried (magnesium sulfate), evaporated and purified by flash chromatography on silica gel eluting with hexane/methyl tert-butylether to give 1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-methyl-4-methylthio-1H-pyrazole-3-carbonitrile (6.2 g) having a purity of 90.7 area percent by HPLC.

Workup

customAfter recooling to −65° C.
temperaturethe mixture warmed to −20° C. over 1.5 hours
custompartitioned between aqueous ammonium chloride and dichloromethane
dry with materialThe organic phase was dried (magnesium sulfate)
customevaporated
custompurified by flash chromatography on silica gel eluting with hexane/methyl tert-butylether

Sources & evidence

ORD record: ord-de7d8eb329ec45dfa0a947dc251554e2
Source dataset: uspto-grants-2003_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06638956B2

Reaction notes

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