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

HRID 2298122ノート

反応式

HRID 2298122 の反応式
[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

参加物

7

反応物 2

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

生成物 1

HCID 545620343-(4-Methylthiophenyl)-4-(2-methyl-4-fluorophenyl)thiophene収率 74.2%

試薬・触媒・溶媒 4

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 702Ethanol溶媒HCID 1140Toluene溶媒HCID 10340Sodium Carbonate溶媒

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-debf4b3ddf21493ca89c656688c09c20
出典データセット
uspto-grants-2002_12
特許番号
US06492413B2

反応ノート

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