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HuagongsheHuagongshe Chemistry Print Report · For research reference only
HRID 1505111Generated: November 1, 2026

6-Bromo-2,2,4,4-tetrafluoro-1,3-benzodioxane → 2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine-6-carboxylic acid methyl ester

https://huagongshe.com/reaction/1505111

Reaction equation

Participants

RoleNameHCIDCharge
Reactant6-Bromo-2,2,4,4-tetrafluoro-1,3-benzodioxaneHCID 2773410—
CatalystHCID 178418397HCID 178418397—
SolventMethanolHCID 887—
SolventAcetonitrileHCID 6342—
SolventTriethylamineHCID 8471—
Product2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine-6-carboxylic acid methyl esterHCID 59166166169.8%

Reaction Conditions

Temperature75 °C

Reaction Steps

A suspension of 6-bromo-2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine (4.75 g, 16.6 mmol) and Pd(PPh3)4 (950 mg, 8.23 mmol) in MeOH (20 mL), MeCN (30 mL) and Et3N (10 mL) was stirred under carbon monoxide atmosphere (55 psi) at 75° C. (oil bath temperature) overnight. The cooled reaction mixture was filtered and the filtrate was concentrated. The residue was purified by silica gel column (Petroleum Ether) to give 2,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine-6-carboxylic acid methyl ester (3.75 g, 85%). 1H NMR (CDCl3, 300 MHz) δ 8.34 (s, 1 H), 8.26 (dd, J=2.1, 8.7 Hz, 1 H), 7.22 (d, J=8.7 Hz, 1 H), 3.96 (s, 3 H).

Provenance & Evidence

DOI10.6084/m9.figshare.5104873.v1
Patent numberUS09216969B2
Source datasetuspto-grants-2015_12
ORD IDord-b4a6d55ab9704c3e9ff53217d220a313
Source noteuspto-grants-2015_12