Hydrochloric Acid → 2-(4-Chloro-2-nitro-phenyl)-3-hydroxy-but-2-enoic acid methyl ester

HRID 250253Notes

Reaction equation

[H-].[Na+].[CH3:3][O:4][C:5](=[O:10])[CH2:6][C:7]([CH3:9])=[O:8].[Cl:11][C:12]1[CH:17]=[CH:16][C:15](F)=[C:14]([N+:19]([O-:21])=[O:20])[CH:13]=1.Cl>O.CN(C=O)C>[CH3:3][O:4][C:5](=[O:10])[C:6]([C:15]1[CH:16]=[CH:17][C:12]([Cl:11])=[CH:13][C:14]=1[N+:19]([O-:21])=[O:20])=[C:7]([OH:8])[CH3:9]

Participants

Conditions

Temperature: 0 °C

Procedure

A mixture of sodium hydride (60% in mineral oil, 2.60 g, 65.0 mmol) and DMF (52 mL) is stirred in an ice bath and methylacetoacetate (6.46 mL, 59.9 mmol) is added via a syringe over 10 minutes. The mixture is stirred for an additional 10 minutes and the ice bath is removed. The solution is stirred at ambient temperature for 30 minutes and transferred via cannula into a flask containing 4-chloro-1-fluoro-2-nitrobenzene (5.00 g, 28.5 mmol) cooled to 0° C. via an ice bath. The reaction is allowed to warm slowly and is stirred for two days at room temperature. The black mixture is acidified with 2 N HCl, turning it yellow. The resulting solution is diluted with water and extracted with ether. The combined ether layers are washed with water and brine and dried over MgSO4 to give the crude title compound (8.26 g), which contains a small amount of mineral oil. The material is used without purification in the next step.

Workup

stirringThe mixture is stirred for an additional 10 minutes
customthe ice bath is removed
stirringThe solution is stirred at ambient temperature for 30 minutes
customtransferred via cannula into a flask
temperatureto warm slowly
stirringis stirred for two days at room temperature
extractionextracted with ether
washThe combined ether layers are washed with water and brine
dry with materialdried over MgSO4

Sources & evidence

ORD record: ord-e53e013eb4704720bff1fbe06a9985d6
Source dataset: uspto-grants-2011_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07863302B2

Reaction notes

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