Methyl iodide → HCID 18005446, compound

HRID 1700400Notes

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 THEF 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-49f1d25a97aa490780da7c02ba7d91f0
Source dataset: uspto-grants-2002_02
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06350771B1

Reaction notes

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