Carbon Dioxide → 6-((Tert-butoxycarbonyl)amino)-2,3-dimethoxybenzoic acid

HRID 525954ノート

反応式

HRID 525954 の反応式
[Li+].CCC[CH2-].[CH3:6][O:7][C:8]1[CH:9]=[C:10]([NH:16][C:17](=[O:23])[O:18][C:19]([CH3:22])([CH3:21])[CH3:20])[CH:11]=[CH:12][C:13]=1[O:14][CH3:15].[C:24](=[O:26])=[O:25]>O1CCCC1>[C:19]([O:18][C:17]([NH:16][C:10]1[C:9]([C:24]([OH:26])=[O:25])=[C:8]([O:7][CH3:6])[C:13]([O:14][CH3:15])=[CH:12][CH:11]=1)=[O:23])([CH3:20])([CH3:22])[CH3:21]

参加物

5

反応物 3

HCID 280Carbon DioxideHCID 61028n-Butyl lithiumHCID 13731037tert-Butyl (3,4-dimethoxyphenyl)carbamate

生成物 1

HCID 144163466-((Tert-butoxycarbonyl)amino)-2,3-dimethoxybenzoic acid収率 48.5%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

N-butyllithium (232 mL, 464 mmol) was added slowly to a solution of tert-butyl (3,4-dimethoxyphenyl)carbamate (50 g, 193 mmol) in Tetrahydrofuran (THF) (500 mL) under N2 at −20° C. After being stirred for 2 h at −10° C. to −20° C., the mixture was cooled to −78° C. and diluted with Tetrahydrofuran (THF) (500 mL), followed by addition of solid carbon dioxide. The mixture was allowed to warm up to r.t. and was then partitioned between water and Et2O. The aqueous layer was acidified with 6N HCl to pH 1-2 and extracted with Et2O. The organic layer was separated, dried over Na2SO4 and evaporated. The crude product was purified by recrystallization from i-Pr2O to afford 6-((tert-butoxycarbonyl)amino)-2,3-dimethoxybenzoic acid (27.9 g, 94 mmol, 48.5% yield) as a white solid. LCMS: (M+H)+: 319.9.

後処理

  1. temperatureto warm up to r.t.
  2. customwas then partitioned between water and Et2O
  3. extractionextracted with Et2O
  4. customThe organic layer was separated
  5. dry with materialdried over Na2SO4
  6. customevaporated
  7. customThe crude product was purified by recrystallization from i-Pr2O

出典と根拠

ORDレコード
ord-b0e5d6aa0b0a4a1dab86c23eb6759c8d
出典データセット
uspto-grants-2016_05
特許番号
US09340556B2

反応ノート

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