Diethylamine → 6-Hydroxy-3-methyl-4-trifluoromethanesulfonyloxy-phthalic Acid Dimethyl Ester

HRID 33000Notes

Reaction equation

HRID 33000 reaction equation
[CH3:1][O:2][C:3](=[O:27])[C:4]1[C:5](=[C:10]([CH3:26])[C:11]([O:18][S:19]([C:22]([F:25])([F:24])[F:23])(=[O:21])=[O:20])=[CH:12][C:13]=1[O:14]CC=C)[C:6]([O:8][CH3:9])=[O:7].C(NCC)C>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:27])[C:4]1[C:5](=[C:10]([CH3:26])[C:11]([O:18][S:19]([C:22]([F:23])([F:25])[F:24])(=[O:21])=[O:20])=[CH:12][C:13]=1[OH:14])[C:6]([O:8][CH3:9])=[O:7]

Participants

4

Reactant 2

HCID 8021DiethylamineHCID 575048246-Allyloxy-3-methyl-4-trifluoromethanesulfonyloxy-phthalic Acid Dimethyl Ester

Product 1

HCID 597945196-Hydroxy-3-methyl-4-trifluoromethanesulfonyloxy-phthalic Acid Dimethyl EsterYield 55%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 6-allyloxy-3-methyl-4-trifluoromethanesulfonyloxy-phthalic acid dimethyl ester (8.39 g, 20.3 mmol) in toluene (20 mL) was added tetrakistriphenylphosphine palladium (0.47 g, 0.40 mmol) and diethylamine (2.97 g, 40.86 mmol) at room temperature under an atmosphere of nitrogen. Stirring at room temperature was continued until all starting material was consumed. The crude reaction mixture was partitioned between diethyl ether and HCl (0.1N). The organic layer was washed with brine and dried over sodium sulfate. Filtration and evaporation of solvents in vacuo yielded a crude material, which was purified by silica gel chromatography to provide 4.16 g (55%) of the desired product as an off-white solid. 1H NMR (300 MHz, CDCl3): δ=2.20 (s, 3H), 3.93 (s, 3H), 3.95 (s, 3H), 7.01 (s, 1H) ppm; 19F NMR (282 MHz, CDCl3): δ=−74 ppm.

Workup

  1. customwas consumed
  2. customThe crude reaction mixture
  3. customwas partitioned between diethyl ether and HCl (0.1N)
  4. washThe organic layer was washed with brine
  5. dry with materialdried over sodium sulfate
  6. filtrationFiltration and evaporation of solvents in vacuo
  7. customyielded a crude material, which
  8. customwas purified by silica gel chromatography

Sources & evidence

ORD record
ord-17b16660219e49b6844e45d6bf94df3d
Source dataset
uspto-grants-2008_09
Patent number
US07427636B2

Reaction notes

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