1,3-Dimethyl-1H-pyrazol-5-amine → 2-({5-Chloro-2-[(1,3-dimethyl-1H-pyrazol-5-yl)amino]-4-pyridinyl}amino)benzoic acid

HRID 62487

反応式

HRID 62487 の反応式
Cl[C:2]1[CH:7]=[C:6]([NH:8][C:9]2[CH:17]=[CH:16][CH:15]=[CH:14][C:10]=2[C:11]([OH:13])=[O:12])[C:5]([Cl:18])=[CH:4][N:3]=1.[CH3:19][N:20]1[C:24]([NH2:25])=[CH:23][C:22]([CH3:26])=[N:21]1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>O1CCOCC1.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]>[Cl:18][C:5]1[C:6]([NH:8][C:9]2[CH:17]=[CH:16][CH:15]=[CH:14][C:10]=2[C:11]([OH:13])=[O:12])=[CH:7][C:2]([NH:25][C:24]2[N:20]([CH3:19])[N:21]=[C:22]([CH3:26])[CH:23]=2)=[N:3][CH:4]=1

参加物

7

反応物 4

HCID 5207211,3-Dimethyl-1H-pyrazol-5-amineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 575168952-[(2,5-Dichloro-4-pyridinyl)amino]benzoic acid

生成物 1

HCID 462147742-({5-Chloro-2-[(1,3-dimethyl-1H-pyrazol-5-yl)amino]-4-pyridinyl}amino)benzoic acid収率 22.6%

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
120 °C

実験手順

A pressure tube was charged with 2-[(2,5-dichloro-4-pyridinyl)amino]benzoic acid (1.0 g, 3.53 mmol), 1,3-dimethyl-1H-pyrazol-5-amine(0.589 g, 5.30 mmol), (±)-2,2′-Bis(diphenylphosphino)-1,1′-binaphthalene (0.330 g, 0.530 mmol), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3, 0.162 g, 0.177 mmol) and sodium tert-butoxide (0.849 g, 8.83 mmol) in 1,4-dioxane (30 mL). The tube was degassed with N2 and sealed and the reaction mixture was heated in an oil bath at 120° C. for 18 hours. The reaction mixture was evaporated to dryness under high vacuum. The residue was taken back in water solution and the pH was adjusted to ˜4 to 5 using 6.0 N hydrochloride acid. The reaction was concentrated to dryness and the resulting solid was dissolved in MeOH and purified by reverse-phase HPLC to give the title compound as a solid (285 mg, 21% yield). MS: M(C17H16ClN5O2)=357.79, (M+H)+=358, 360.

後処理

  1. customThe tube was degassed with N2
  2. customsealed
  3. customThe reaction mixture was evaporated to dryness under high vacuum
  4. concentrationThe reaction was concentrated to dryness
  5. dissolutionthe resulting solid was dissolved in MeOH
  6. custompurified by reverse-phase HPLC

出典と根拠

ORDレコード
ord-b2a2b9b7065649b3b13160a67bf6f11a
出典データセット
uspto-grants-2016_09
特許番号
US09446034B2

関連ノート

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