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tert-Butylhydrazine monohydrochloride → 1-(1,1-dimethylethyl)-4-(5-fluoro-2-(methyloxy)-3-[{phenylmethyl)oxy]phenyl}-3-methyl-1H-pyrazol-5-amine

HRID 253284
ノート
印刷プレビュー

反応式

HRID 253284 の反応式
[F:1][C:2]1[CH:3]=[C:4]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C:5]([O:14][CH3:15])=[C:6]([CH:8]([C:11](=O)[CH3:12])[C:9]#[N:10])[CH:7]=1.Cl.[C:25]([NH:29][NH2:30])([CH3:28])([CH3:27])[CH3:26]>C(O)C>[CH3:26][C:25]([N:29]1[C:9]([NH2:10])=[C:8]([C:6]2[CH:7]=[C:2]([F:1])[CH:3]=[C:4]([O:16][CH2:17][C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)[C:5]=2[O:14][CH3:15])[C:11]([CH3:12])=[N:30]1)([CH3:28])[CH3:27]
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

4

反応物 2

HCID 81889tert-Butylhydrazine monohydrochlorideHCID 668904882-{5-Fluoro-2-(methyloxy)-3-[(phenylmethyl)oxy]phenyl}-3-oxobutanenitrile

生成物 1

HCID 668909321-(1,1-dimethylethyl)-4-(5-fluoro-2-(methyloxy)-3-[{phenylmethyl)oxy]phenyl}-3-methyl-1H-pyrazol-5-amine収率 98.3%

試薬・触媒・溶媒 1

HCID 702Ethanol溶媒

反応条件

温度
75 °C

実験手順

To a solution of 2-{5-fluoro-2-(methyloxy)-3-[(phenylmethyl)oxy]phenyl}-3-oxobutanenitrile (5.7 g, 18.1 mmol) in ethanol (60 mL) was added t-butylhydrazine hydrochloride (6.8 g, 54 mmol). The mixture was stirred for 2 h at 75° C. before cooling to rt and stirring for an additional 14 h. The volatile materials were removed in vacuo. To the residue was added water, and the resulting aqueous mixture was extracted with ethyl acetate 3 times. The organic extracts were combined and washed with 1 N HCl (aq) followed by aqueous NaHCO3 (sat). The organics were then dried over magnesium sulfate, filtered, and concentrated in vacuo to provide 1-(1,1-dimethylethyl)-4-{5-fluoro-2-(methyloxy)-3-[{phenylmethyl)oxy]phenyl}-3-methyl-1H-pyrazol-5-amine as a pale yellow syrup (6.81 g, 17.8 mmol, 98% yield). 1H NMR (400 MHz, CDCl3): δ 7.45-7.32 (m, 5H), 6.60 (dd, 1H), 6.53 (dd, 1H), 5.10 (s, 2H), 3.91 (br s, 2H), 3.55 (s, 3H), 2.20 (s, 3H), 1.67 (s, 9H); MS (EI) for C22H26FN3O2: 384 (MH+).

後処理

  1. temperaturebefore cooling to rt
  2. stirringstirring for an additional 14 h
  3. customThe volatile materials were removed in vacuo
  4. additionTo the residue was added water
  5. extractionthe resulting aqueous mixture was extracted with ethyl acetate 3 times
  6. washwashed with 1 N HCl (aq)
  7. dry with materialThe organics were then dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-77dd8ce7a56d4542b6ea11f7550b2848
出典データセット
uspto-grants-2011_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07872014B2

反応ノート

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