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HuagongsheHuagongshe Chemistry Print Report · For research reference only
HRID 429806Generated: October 30, 2026

Toluene → Methyl 3-difluoromethoxy-thiophene-2-carboxylate

https://huagongshe.com/reaction/429806

Reaction equation

Participants

RoleNameHCIDCharge
ReactantTolueneHCID 1140—
ReactantChlorodifluoromethaneHCID 6372—
ReactantSodium HydroxideHCID 14798—
Reactant3-Hydroxy-thiophene-2-carboxylic acid methyl esterHCID 581127—
CatalystTetrabutylphosphonium bromideHCID 76564—
SolventWaterHCID 962—
ProductMethyl 3-difluoromethoxy-thiophene-2-carboxylateHCID 1537648131.3%

Reaction Conditions

Temperature90 °C

Reaction Steps

At room temperature, a mixture of 10 g (0.063 mol) of methyl 3-hydroxy-thiophene-2-carboxylate and 90 ml of toluene is admixed with a solution of 5.1 g (0.127 mol) of sodium hydroxide in 8 ml of water. The reaction mixture is heated with stirring to 90° C., 1.1 g of tetrabutyl-phosphonium bromide are added and 16.4 g (0.189 mol) of chlorodifluoromethane are introduced over a period of 30 minutes. The mixture is then stirred at 90° C. for one hour. The reaction mixture is subsequently cooled to room temperature and admixed with water. The organic phase is separated off, dried over sodium sulphate and then concentrated under reduced pressure at 50° C. The residue that remains is chromatographed over silica gel using cyclohexane:ethyl acetate=3:1 as mobile phase. Concentration of the eluate gives 4.1 g (31.3% of theory) of methyl 3-difluoromethoxy-thiophene-2-carboxylate in the form of an oil.

Provenance & Evidence

DOI10.6084/m9.figshare.5104873.v1
Patent numberUS06319940B1
Source datasetuspto-grants-2001_11
ORD IDord-232a9a77598b4a1d970274b92001e3c5
Source noteuspto-grants-2001_11