O-Toluidine → Methyl 4-amino-3-fluoro-5-nitro-2-(2-toluidino)benzoate

HRID 31963

反応式

HRID 31963 の反応式
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([NH2:13])=[C:6]([F:14])[C:5]=1F.[NH2:17][C:18]1[C:19]([CH3:24])=[CH:20][CH:21]=[CH:22][CH:23]=1>C(OCC)C>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[C:7]([NH2:13])=[C:6]([F:14])[C:5]=1[NH:17][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[CH3:24]

参加物

4

反応物 2

HCID 7242O-ToluidineHCID 2759749Benzoic acid, 4-amino-2,3-difluoro-5-nitro-, methyl ester

生成物 1

HCID 22180129Methyl 4-amino-3-fluoro-5-nitro-2-(2-toluidino)benzoate収率 68%

試薬・触媒・溶媒 1

HCID 3283Diethyl Ether溶媒

実験手順

4-Amino-2,3-difluoro-5-nitro-benzoic acid methyl ester 4 (12.0 g, 51.7 mmol) is suspended in xylenes (60 mL) and ortho-toluidine is added (55.2 mL, 517 mmol). The reaction mixture is heated to reflux with stirring under a nitrogen atmosphere. After 36 hours, the reaction mixture is cooled to room temperature, diluted with diethyl ether and washed with 10% aqueous HCl solution. The aqueous washings are extracted with diethyl ether. The combined organic extracts are concentrated under reduced pressure. The residue is dissolved in methylene chloride and filtered through silica gel in a fritted funnel, rinsing with methylene chloride. Three fractions are recovered. The first (2 liter) is nearly clean by HPLC. The second (1 liter) and third (1 liter) fractions are only partially pure. The first fraction is concentrated under reduced pressure and triturated with diethyl ether to give 11.2 g (68%) of clean desired product as a bright yellow solid: MS APCI (−) m/z 318 (M−1) detected.

後処理

  1. temperatureThe reaction mixture is heated
  2. temperatureto reflux
  3. washwashed with 10% aqueous HCl solution
  4. extractionThe aqueous washings are extracted with diethyl ether
  5. concentrationThe combined organic extracts are concentrated under reduced pressure
  6. dissolutionThe residue is dissolved in methylene chloride
  7. filtrationfiltered through silica gel in a fritted funnel
  8. washrinsing with methylene chloride
  9. customThree fractions are recovered
  10. concentrationThe first fraction is concentrated under reduced pressure
  11. customtriturated with diethyl ether

出典と根拠

ORDレコード
ord-a53444372f1942f38ecacce1b185b762
出典データセット
uspto-grants-2008_09
特許番号
US07425637B2

関連ノート

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