tert-Butanol → Tert-butyl 4-amino-2-methylbenzoate

HRID 446519ノート

反応式

HRID 446519 の反応式
[CH3:1][C:2]1[CH:10]=[C:9]([N+:11]([O-])=O)[CH:8]=[CH:7][C:3]=1[C:4]([OH:6])=[O:5].[C:14]1([CH3:24])[CH:19]=CC(S(Cl)(=O)=O)=C[CH:15]=1.C(O)(C)(C)C>N1C=CC=CC=1>[NH2:11][C:9]1[CH:8]=[CH:7][C:3]([C:4]([O:6][C:14]([CH3:24])([CH3:19])[CH3:15])=[O:5])=[C:2]([CH3:1])[CH:10]=1

参加物

5

反応物 3

HCID 6386tert-Butanol2 回HCID 73974-Toluenesulfonyl chlorideHCID 747904-Nitro-o-toluic acid

生成物 1

HCID 45089772Tert-butyl 4-amino-2-methylbenzoate収率 104.4%

試薬・触媒・溶媒 1

HCID 1049Pyridine溶媒

反応条件

温度
0 °C

実験手順

2-Methyl-4-nitrobenzoic acid (700 mg, 3.86 mmol) was dissolved in pyridine (8 mL), p-toluenesulfonyl chloride (1.47 g, 7.74 mmol) was added, then tert-butanol (0.369 mL, 3.86 mmol) was added under ice cooling, and the mixture was stirred at 0° C. for 2 hours and at room temperature for 2 hours. tert-Butanol (0.369 mL, 3.86 mmol) was further added, and the mixture was stirred overnight at room temperature. The solvent was evaporated under reduced pressure, water was added, then the mixture was extracted with ethyl acetate (×3), and the organic layer was washed with 1 N hydrochloric acid, a 1 N aqueous sodium hydroxide solution, water, and saturated sodium chloride solution. The organic layer was dried with anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, a solution of the resulting residue in ethyl acetate (40 mL) was added to 10% palladium-carbon (dry; 222 mg), the atmosphere in the system was replaced with a hydrogen atmosphere, and then the mixture was stirred at room temperature for 2 hours. The atmosphere in the system was replaced with a nitrogen atmosphere, and then the mixture was filtered through celite. The solvent was evaporated under reduced pressure to give the title compound (835 mg; yield, 100%) as a brown solid.

後処理

  1. stirringthe mixture was stirred overnight at room temperature
  2. customThe solvent was evaporated under reduced pressure, water
  3. additionwas added
  4. extractionthe mixture was extracted with ethyl acetate (×3)
  5. washthe organic layer was washed with 1 N hydrochloric acid
  6. dry with materialThe organic layer was dried with anhydrous sodium sulfate
  7. customthe solvent was evaporated under reduced pressure
  8. additiona solution of the resulting residue in ethyl acetate (40 mL) was added to 10% palladium-carbon (dry; 222 mg)
  9. stirringthe mixture was stirred at room temperature for 2 hours
  10. filtrationthe mixture was filtered through celite
  11. customThe solvent was evaporated under reduced pressure

出典と根拠

ORDレコード
ord-e9d438dafee74dd4a97d0a47eb861d4e
出典データセット
uspto-grants-2013_07
特許番号
US08476253B2

反応ノート

読み込み中…