Triphenylarsine → 6-Hydroxy-3-methyl-4-vinyl-phthalic Acid Dimethyl Ester

HRID 33662

Reaktionsgleichung

Reaktionsgleichung von HRID 33662
[CH3:1][O:2][C:3](=[O:24])[C:4]1[C:5](=[C:10]([CH3:23])[C:11](OS(C(F)(F)F)(=O)=O)=[CH:12][C:13]=1[OH:14])[C:6]([O:8][CH3:9])=[O:7].[Cl-].[Li+].[C:27]1([As](C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C[CH:28]=1.C(C([Sn])=C(CCCC)CCCC)CCC.[F-].[K+]>CN1CCCC1=O.CCOC(C)=O>[CH3:1][O:2][C:3](=[O:24])[C:4]1[C:5](=[C:10]([CH3:23])[C:11]([CH:27]=[CH2:28])=[CH:12][C:13]=1[OH:14])[C:6]([O:8][CH3:9])=[O:7]

Komponenten

8

Edukt 5

HCID 11773TriphenylarsineHCID 433294Lithium ChlorideHCID 522689Potassium FluorideHCID 53438229Tri(butyl)vinyltinHCID 597945196-Hydroxy-3-methyl-4-trifluoromethanesulfonyloxy-phthalic Acid Dimethyl Ester

Produkt 1

HCID 597944986-Hydroxy-3-methyl-4-vinyl-phthalic Acid Dimethyl EsterAusbeute 867,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8857Ethyl AcetateLösungsmittelHCID 13387N-methyl-2-pyrrolidoneLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

To a solution of 6-hydroxy-3-methyl-4-trifluoromethanesulfonyloxy-phthalic acid dimethyl ester (2.17 g, 5.85 mmol) in N-methylpyrolidinone (15 mL) was added lithium chloride (743 mg, 17.5 mmol) and triphenylarsine (179 mg, 0.585 mmol). Tributylvinyltin (2.04 g, 6.43 mmol) was added followed by tris(tribenzylideneacetone)dipalladium(0)-chloroform adduct (90 mg, 0.087 mmol). The reaction was placed under an atmosphere of nitrogen and heated at 60° C. for 18 hrs. The reaction was cooled to room temperature and poured onto a mixture of ice (20 g), EtOAc (40 mL), and potassium fluoride (1 g). Stirring was continued for 1 hr. The aqueous layer was extracted with EtOAc and the organic extracts filtered through Celite. The combined organic layers were washed with water 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 1.27 g (87%) of the product as an off-white solid. 1H NMR (300 MHz, CDCl3): δ=2.16 (s, 3H), 3.91 (s, 3H), 3.92 (s, 3H), 5.46 (dd, J=11.1, 1.2 Hz, 1H), 5.72 (dd, J=17.1, 0.9 Hz, 1H), 6.86 (dd, J=17.1, 11.1 Hz, 1H), 7.14 (s, 1H), 10.79 (s, 1H) ppm.

Aufarbeitung

  1. temperatureThe reaction was cooled to room temperature
  2. extractionThe aqueous layer was extracted with EtOAc
  3. filtrationthe organic extracts filtered through Celite
  4. washThe combined organic layers were washed with water
  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

Quellen und Nachweise

ORD-Eintrag
ord-7b6cd314da244668b108ea21e6930740
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07429565B2

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