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Cesium carbonate → 3-(3'-(Ethylsulfonyl)-4-methyl-3-nitro-5-(trifluoromethyl)biphenyl-2-yl)-2-fluoro-5-methylpyridine

HRID 1642532
ノート
印刷プレビュー

反応式

HRID 1642532 の反応式
Cl[C:2]1[C:7]([C:8]2[C:9]([F:15])=[N:10][CH:11]=[C:12]([CH3:14])[CH:13]=2)=[C:6]([N+:16]([O-:18])=[O:17])[C:5]([CH3:19])=[C:4]([C:20]([F:23])([F:22])[F:21])[CH:3]=1.[CH2:24]([S:26]([C:29]1[CH:30]=[C:31](B(O)O)[CH:32]=[CH:33][CH:34]=1)(=[O:28])=[O:27])[CH3:25].C1(P(C2CCCCC2)C2CCCCC2)CCCCC1.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1>[CH2:24]([S:26]([C:29]1[CH:34]=[C:33]([C:2]2[CH:3]=[C:4]([C:20]([F:23])([F:21])[F:22])[C:5]([CH3:19])=[C:6]([N+:16]([O-:18])=[O:17])[C:7]=2[C:8]2[C:9]([F:15])=[N:10][CH:11]=[C:12]([CH3:14])[CH:13]=2)[CH:32]=[CH:31][CH:30]=1)(=[O:27])=[O:28])[CH3:25]
参加物実験手順後処理出典と根拠反応ノート

参加物

6

反応物 4

HCID 10796Cesium carbonateHCID 75806TricyclohexylphosphineHCID 164271023-Ethylsulfonylphenylboronic acidHCID 588800743-(6-Chloro-3-methyl-2-nitro-4-(trifluoromethyl)phenyl)-2-fluoro-5-methylpyridine

生成物 1

HCID 249640503-(3'-(Ethylsulfonyl)-4-methyl-3-nitro-5-(trifluoromethyl)biphenyl-2-yl)-2-fluoro-5-methylpyridine収率 78.3%

試薬・触媒・溶媒 1

HCID 312751,4-Dioxane溶媒

実験手順

A mixture of 3-(6-chloro-3-methyl-2-nitro-4-(trifluoromethyl)phenyl)-2-fluoro-5-methylpyridine (6.0 g, 17.2 mmol), 3-ethylsulfonylphenylboronic acid (4.79 g, 22.4 mmol), bis(dibenzylidineacetone)Pd(0) (1.48 g, 2.6 mmol), tricyclohexylphosphine (1.45 g, 5.2 mmol), Cs2CO3 (14.0 g, 43 mmol), and dioxane (60 mL) was heated at reflux for 4.5 hr. After completion the reaction was cooled to room temperature, filtered, rinsed with dioxane, and concentrated in vacuo. The resulting oil was reconstituted in EtOAc (75 mL) washed with H2O (1×30 mL) and brine (1×30 mL), dried (MgSO4), and concentrated in vacuo. Purification by silica gel chromatography (4:1 hexanes/EtOAc) gave 6.5 g (78%) of the title compound as a tan solid. 1H NMR (400 MHz, DMSO-d6): δ 8.15 (s, 1H), 8.04 (s, 1H), 7.90-7.93 (m, 1H), 7.80-7.82 (m, 1H), 7.60-7.70 (m, 3H), 3.1-3.2 (m, 2H), 2.49 (s, 3H), 2.25 (s, 3H), 0.85 (t, 3H). MS (ES) [m+H] calc'd for C22H18F4N2O4S, 483; found 483.3.

後処理

  1. temperaturewas heated
  2. temperatureat reflux for 4.5 hr
  3. filtrationfiltered
  4. washrinsed with dioxane
  5. concentrationconcentrated in vacuo
  6. washwashed with H2O (1×30 mL) and brine (1×30 mL)
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customPurification by silica gel chromatography (4:1 hexanes/EtOAc)

出典と根拠

ORDレコード
ord-c410963bc4324ae487eac8d9fb56de5f
出典データセット
uspto-grants-2012_02
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08119655B2

反応ノート

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