(4-Fluoro-2-methylphenyl)boronic acid → 3-(4-Methylthiophenyl)-4-(2-methyl-4-fluorophenyl)thiophene

HRID 2298122Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2298122
[CH3:1][S:2]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:12]([C:16]3[CH:21]=[CH:20][C:19]([F:22])=[CH:18][CH:17]=3)=[CH:13][S:14][CH:15]=2)=[CH:7][CH:6]=1)(=O)=O.[CH3:23]C1C=C(F)C=CC=1B(O)O>C1(C)C=CC=CC=1.C(=O)([O-])[O-].[Na+].[Na+].C(O)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH3:1][S:2][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:12]([C:16]3[CH:21]=[CH:20][C:19]([F:22])=[CH:18][C:17]=3[CH3:23])=[CH:13][S:14][CH:15]=2)=[CH:7][CH:6]=1

Komponenten

7

Edukt 2

HCID 2734665(4-Fluoro-2-methylphenyl)boronic acidHCID 104268843-(4-Methylsulfonylphenyl)-4-(4-fluorophenyl)thiophene

Produkt 1

HCID 545620343-(4-Methylthiophenyl)-4-(2-methyl-4-fluorophenyl)thiopheneAusbeute 74,2 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 702EthanolLösungsmittelHCID 1140TolueneLösungsmittelHCID 10340Sodium CarbonateLösungsmittel

Versuchsvorschrift

The mono-substituted thiophene from Example 14 (1.8 mmol, 520 mg) was combined with the 2-methyl-4-fluorophenyl boronic acid (2 eq, 3.6 mmol, 562 mg) in 8.0 ml of toluene, 4.3 ml of 2 M sodium carbonate, 10 ml of ethanol and tetrakis(triphenylphosphine)-palladium(0) (1.0 g) and was stirred at reflux overnight. The reaction was concentrated in vacuo and the residue was partitioned between toluene and water. The toluene layer was dried (MgSO4) and reconcentrated in vacuo. The residue was purified via silica chromatography (Waters, LC-2000) in 97% hexane/ethyl acetate to give 3-(4-methylthiophenyl)-4-(2-methyl-4-fluorophenyl)thiophene (420 mg) as a semi-solid, NMR (CDCl3) δ 1.90(s, 3H), 2.43(s, 3H), 6.8-6.9(m, 2H), 7.05(q, J=8 Hz, 4H), 7.12-7.18(m, 2H), 7.33(d, J=2 Hz, 1H).

Aufarbeitung

  1. temperatureat reflux overnight
  2. concentrationThe reaction was concentrated in vacuo
  3. customthe residue was partitioned between toluene and water
  4. dry with materialThe toluene layer was dried (MgSO4)
  5. customThe residue was purified via silica chromatography (Waters, LC-2000) in 97% hexane/ethyl acetate

Quellen und Nachweise

ORD-Eintrag
ord-debf4b3ddf21493ca89c656688c09c20
Quelldatensatz
uspto-grants-2002_12
Patentnummer
US06492413B2

Notizen zur Reaktion

Wird geladen…