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

HRID 1505111Notes

Reaction equation

HRID 1505111 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9]([F:12])([F:11])[O:8][C:7]([F:14])([F:13])[C:6]=2[CH:15]=1>CO.CC#N.CCN(CC)CC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:7][O:8][C:9]([C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9]([F:12])([F:11])[O:8][C:7]([F:14])([F:13])[C:6]=2[CH:15]=1)=[O:10]

Participants

6

Reactant 1

HCID 27734106-Bromo-2,2,4,4-tetrafluoro-1,3-benzodioxane

Product 1

HCID 591661662,2,4,4-tetrafluoro-4H-benzo[1,3]dioxine-6-carboxylic acid methyl esterYield 169.8%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 887MethanolSolventHCID 6342AcetonitrileSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
75 °C

Procedure

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).

Workup

  1. customThe cooled reaction mixture
  2. filtrationwas filtered
  3. concentrationthe filtrate was concentrated
  4. customThe residue was purified by silica gel column (Petroleum Ether)

Sources & evidence

ORD record
ord-b4a6d55ab9704c3e9ff53217d220a313
Source dataset
uspto-grants-2015_12
Patent number
US09216969B2

Reaction notes

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