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Tris(1,1-dimethylethyl)phosphine → methyl 2-{[3-tert-butyl-1-(2-methylphenyl)-1H-pyrazol-5-yl]amino}-4-ethylbenzoate

HRID 915589
ノート
印刷プレビュー

反応式

HRID 915589 の反応式
[C:1]([C:5]1[CH:9]=[C:8]([NH:10][C:11]2[CH:20]=[C:19](Cl)[CH:18]=[CH:17][C:12]=2[C:13]([O:15][CH3:16])=[O:14])[N:7]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH3:28])[N:6]=1)([CH3:4])([CH3:3])[CH3:2].[CH2:29](B(O)O)[CH3:30].C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.[F-].[K+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].O1CCOCC1>[C:1]([C:5]1[CH:9]=[C:8]([NH:10][C:11]2[CH:20]=[C:19]([CH2:29][CH3:30])[CH:18]=[CH:17][C:12]=2[C:13]([O:15][CH3:16])=[O:14])[N:7]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[CH3:28])[N:6]=1)([CH3:4])([CH3:3])[CH3:2]
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

7

反応物 4

HCID 83681Tris(1,1-dimethylethyl)phosphineHCID 521157Ethylboronic acidHCID 522689Potassium FluorideHCID 58958608methyl 2-{[3-tert-butyl-1-(2-methylphenyl)-1H-pyrazol-5-yl]amino}-4-chlorobenzoate

生成物 1

HCID 58958599methyl 2-{[3-tert-butyl-1-(2-methylphenyl)-1H-pyrazol-5-yl]amino}-4-ethylbenzoate収率 81%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
110 °C

実験手順

To a mixture of methyl 2-{[3-tert-butyl-1-(2-methylphenyl)-1H-pyrazol-5-yl]amino}-4-chlorobenzoate (Example 242, 50 mg, 0.13 mmol), ethylboronic acid (18.56 mg, 0.26 mmol), Pd2(dba)3 (5.8 mg, 0.006 mmol), tris(tert-butyl)phosphine (2.54 mg, 0.013 mmol), and potassium fluoride (14.6 mg, 0.25 mmol) was added dioxane (1 mL). The resulting solution was degassed under argon for 30 min and then heated to 110° C. for 16 h. The reaction mixture was then cooled to rt. The residue was diluted with ethyl acetate and filtered through a silica gel plug. The solvent was removed under reduced pressure, and the crude product was purified by HPLC purification using gradient elution from 30 to 100% acetonitrile in water to afford 39.8 mg (81%) of the title compound. 1H NMR (300 MHz, CD2Cl2) δ 9.23 (s, 1H), 7.74 (d, 1H), 7.23-7.29 (m, 4H), 7.03 (s, 1H), 6.57 (d, 1H), 6.09 (s, 1H), 3.69 (s, 3H), 2.55 (q, 2H), 2.06 (s, 3H), 1.30 (s, 9H), 1.15 (t, 3H). ES-MS m/z 392.2 (MH+); HPLC RT (min) 4.65.

後処理

  1. customThe resulting solution was degassed under argon for 30 min
  2. temperatureThe reaction mixture was then cooled to rt
  3. additionThe residue was diluted with ethyl acetate
  4. filtrationfiltered through a silica gel plug
  5. customThe solvent was removed under reduced pressure
  6. customthe crude product was purified by HPLC purification
  7. washelution from 30 to 100% acetonitrile in water

出典と根拠

ORDレコード
ord-bbd07a0ede884d5d916831f0936821d6
出典データセット
uspto-grants-2007_09
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07265144B2

反応ノート

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