Cesium carbonate → Methyl 4-[(4-cyclohexylphenyl)amino]-5-methylthiothiophene-2-carboxylate

HRID 2298668

反応式

HRID 2298668 の反応式
Br[C:2]1[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[S:9])[S:5][C:6]=1[CH3:7].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH:64]1([C:70]2[CH:76]=[CH:75][C:73]([NH2:74])=[CH:72][CH:71]=2)[CH2:69][CH2:68][CH2:67][CH2:66][CH2:65]1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1>[CH:64]1([C:70]2[CH:71]=[CH:72][C:73]([NH:74][C:2]3[CH:3]=[C:4]([C:8]([O:10][CH3:11])=[S:9])[S:5][C:6]=3[CH3:7])=[CH:75][CH:76]=2)[CH2:65][CH2:66][CH2:67][CH2:68][CH2:69]1

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 807644-CyclohexylbenzenamineHCID 634876Binap, (A+-)-HCID 86583861Methyl 4-bromo-5-methylthiothiophene-2-carboxylate

生成物 1

HCID 86758686Methyl 4-[(4-cyclohexylphenyl)amino]-5-methylthiothiophene-2-carboxylate収率 46.7%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒

実験手順

The same procedure as in Example 197, step (a) was followed using 122 mg (0.457 mmol) of methyl 4-bromo-5-methylthiothiophene-2-carboxylate (as prepared in Example 241, step (a)), 9.9 mg (9.7 mol %) of palladium (II) acetate, 42.3 mg (14.9 mol %) of racemic-BINAP, 206 mg (0.632 mmol) of cesium carbonate, 102 mg (0.582 mmol) of 4-cyclohexylaniline and 913 μL of toluene, and chromatographed as before using 20-40% CH2Cl2-hexane to afford 73.8 mg (45%) of the title compound as a light green resin: 1H-NMR (CDCl3, 400 MHz) δ7.74 (s, 1H), 7.15 (d, 2H, J=8.4 Hz), 6.98 (d, 2H, J=8.4 Hz), 6.12 (s, 1H), 3.88 (s, 3H), 2.48 (m, 1H), 2.39 (s, 3H), 1.87 (m, 4H), 1.76 (br d, 1H, J=12.5 Hz), 1.41 (m, 4H) and 1.28 (m, 1H). Mass spectrum (ESI, m/z): Calcd. for C19H23NO2S2, 362.1 (M+H), found 362.4.

後処理

  1. customchromatographed as

出典と根拠

ORDレコード
ord-b048170fd45a4ba0a1a109ea8a40e31e
出典データセット
uspto-grants-2002_12
特許番号
US06492403B1

関連ノート

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