Hydrochloric Acid → B-(4′-Ethoxy-2′,3′-difluoro[1,1′-biphenyl]-4-yl)boronic acid

HRID 1929250Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1929250
[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][C:13](Br)=[CH:12][CH:11]=2)=[C:6]([F:17])[C:5]=1[F:18])[CH3:2].C([Li])CCC.[B:24](OC)([O:27]C)[O:25]C.Cl>C(OCC)(=O)C.C1COCC1.CCCCCC>[CH2:1]([O:3][C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][C:13]([B:24]([OH:27])[OH:25])=[CH:12][CH:11]=2)=[C:6]([F:17])[C:5]=1[F:18])[CH3:2]

Komponenten

8

Edukt 4

HCID 313Hydrochloric AcidHCID 8470Trimethyl borateHCID 120674514'-Bromo-4-ethoxy-2,3-difluoro-1,1'-biphenylHCID 178418339Butyllithium

Produkt 1

HCID 12067460B-(4′-Ethoxy-2′,3′-difluoro[1,1′-biphenyl]-4-yl)boronic acidAusbeute 131,8 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

The compound (3) (10.0 g) and THF (100 ml) were put in a reaction vessel under a nitrogen atmosphere, and cooled to −74° C. n-Butyllithium (1.57 M in a n-hexane solution; 22.4 ml) was added dropwise thereto in the temperature range of −74° C. to −70° C., and the mixture obtained was stirred for another 2 hours. Subsequently, trimethyl borate (4.0 g) in a THF (50 ml) solution was added dropwise thereto in the temperature range of −74° C. to −65° C., and the mixture was stirred for another 8 hours while allowing the temperature to come to 25° C. Then, the reaction mixture was poured into a vessel containing 1N-hydrochloric acid (100 ml) and ice-water (500 ml), and mixed. Ethyl acetate (300 ml) was added thereto and the mixture was allowed to be separated into organic and aqueous phases, and then an extractive operation was carried out. The organic phase obtained was fractionated, washed sequentially with a saturated aqueous solution of sodium hydrogencarbonate and brine, and then dried over anhydrous magnesium sulfate. The solvent was then distilled off under reduced pressure, giving 11.7 g of 4-ethoxy-2,3-difluoro-1,1′-biphenyl-4′-boronic acid (6). The yield based on the compound (3) was 81.1%.

Aufarbeitung

  1. addition22.4 ml) was added dropwise
  2. customin the temperature range of −74° C. to −70° C., and the mixture obtained
  3. stirringin the temperature range of −74° C. to −65° C., and the mixture was stirred for another 8 hours
  4. customto come to 25° C
  5. additionThen, the reaction mixture was poured into a vessel
  6. additionmixed
  7. customto be separated into organic and aqueous phases
  8. customThe organic phase obtained
  9. washwashed sequentially with a saturated aqueous solution of sodium hydrogencarbonate and brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. distillationThe solvent was then distilled off under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-94d2d8a442e146739238c1360a9e067d
Quelldatensatz
uspto-grants-2012_05
Patentnummer
US08187494B2

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