Hydrochloric Acid → 6-Bromo-4-cyano-7-fluoro-N,N,5-trimethyl-1,3-benzoxazole-2-carboxamide

HRID 17393

反応式

HRID 17393 の反応式
C[Al](C)C.Cl.[CH3:6][NH:7][CH3:8].[Br:9][C:10]1[C:23]([CH3:24])=[C:22]([C:25]#[N:26])[C:13]2[N:14]=[C:15]([C:17]([O:19]CC)=O)[O:16][C:12]=2[C:11]=1[F:27].Cl>ClCCl>[Br:9][C:10]1[C:23]([CH3:24])=[C:22]([C:25]#[N:26])[C:13]2[N:14]=[C:15]([C:17]([N:7]([CH3:8])[CH3:6])=[O:19])[O:16][C:12]=2[C:11]=1[F:27]

参加物

6

反応物 4

HCID 313Hydrochloric AcidHCID 10473Dimethylamine, hydrochlorideHCID 16682925TrimethylaluminumHCID 68584335Ethyl 6-bromo-4-cyano-7-fluoro-5-methyl-1,3-benzoxazole-2-carboxylate

生成物 1

HCID 685849626-Bromo-4-cyano-7-fluoro-N,N,5-trimethyl-1,3-benzoxazole-2-carboxamide収率 48%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

Under nitrogen atmosphere, trimethylaluminium (1.03 M n-hexane solution, 57.9 ml, 59.6 mmol) was dropwise added to a dichloromethane (100 ml) solution of dimethylamine hydrochloride (4.86 g, 59.6 mmol) with cooling in a water bath, taking 30 minutes, and stirred for 65 minutes at room temperature. Subsequently, a dichloromethane (30 ml) solution of ethyl 6-bromo-4-cyano-7-fluoro-5-methyl-1,3-benzoxazole-2-carboxylate (I-126) (6.50 g, 19.9 mmol) was dropwise added and stirred for 30 hours. After the reaction, aqueous 1 N hydrochloric acid solution was added to the reaction liquid with cooling with ice, followed by stirring at room temperature, and the reaction liquid was extracted with chloroform. Next, the obtained organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was subjected to silica gel column chromatography, and the eluate with dichloromethane/methanol (100:1, v/v) gave the entitled compound (3.10 g, 48%) as a pale yellow solid. The fraction containing impurities was recovered and purified twice in the same manner to obtain the entitled compound (362 mg, 591 mg), and 4.05 g (62%) of the entitled compound was obtained in total.

後処理

  1. temperaturewith cooling in a water bath
  2. stirringstirred for 30 hours
  3. additionwas added to the reaction liquid
  4. temperaturewith cooling with ice
  5. stirringby stirring at room temperature
  6. customthe reaction liquid
  7. extractionwas extracted with chloroform
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. concentrationthe filtrate was concentrated under reduced pressure

出典と根拠

ORDレコード
ord-d25f7f671b524bef9b839edaa7c4f18c
出典データセット
uspto-grants-2010_06
特許番号
US07737166B2

関連ノート

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