Acetic Acid → 3-Chloro-1-(3-cyano-4-methoxyphenyl)-5-[4-(methylthio)phenyl]pyrazole

HRID 429325Notes

Reaction equation

N([O-])=O.[Na+].[C:5]([C:7]1[CH:8]=[C:9]([N:15]2[C:19]([C:20]3[CH:25]=[CH:24][C:23]([S:26][CH3:27])=[CH:22][CH:21]=3)=[CH:18][C:17](N)=[N:16]2)[CH:10]=[CH:11][C:12]=1[O:13][CH3:14])#[N:6].[ClH:29].C(O)(=O)C>O>[Cl:29][C:17]1[CH:18]=[C:19]([C:20]2[CH:25]=[CH:24][C:23]([S:26][CH3:27])=[CH:22][CH:21]=2)[N:15]([C:9]2[CH:10]=[CH:11][C:12]([O:13][CH3:14])=[C:7]([C:5]#[N:6])[CH:8]=2)[N:16]=1

Participants

Conditions

Temperature: 0 °C

Procedure

A solution of sodium nitrite (0.36 g) in water (0.5 ml) was added to an ice cooled mixture of 1-(3-cyano-4-methoxyphenyl)-5-[4-(methylthio)phenyl]pyrazol-3-amine (1.08 g), concentrated hydrochloric acid (15 ml) and acetic acid (35 ml). The mixture was stirred at 0° C. for 30 minutes and added portionwise to a mixture of cuprous chloride (1.37 g) and concentrated hydrochloric acid (10 ml) at ambient temperature. The mixture was refluxed for 1 hour, poured into water and extracted with toluene. The extract was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The resulting residue was purified by column chromatography on silica gel eluting with toluene to give 3-chloro-1-(3-cyano-4-methoxyphenyl)-5-[4-(methylthio)phenyl]pyrazole (0.29 g).

Workup

temperaturecooled
temperatureThe mixture was refluxed for 1 hour
extractionextracted with toluene
washThe extract was washed with water
dry with materialdried over magnesium sulfate
concentrationconcentrated under reduced pressure
customThe resulting residue was purified by column chromatography on silica gel eluting with toluene

Sources & evidence

ORD record: ord-3d7344f94e094ff7b31522fd5400e277
Source dataset: uspto-grants-2001_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06316485B1

Reaction notes

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