Methanesulfonic Acid → 3-amino-8-bromo-1,5-dimethyl-1,3-dihydro-2H-1,4-benzodiazepin-2-one

HRID 30311ノート

反応式

HRID 30311 の反応式
[Br:1][C:2]1[CH:26]=[CH:25][C:5]2[C:6]([CH3:24])=[N:7][CH:8]([NH:13]C(=O)OCC3C=CC=CC=3)[C:9](=[O:12])[N:10]([CH3:11])[C:4]=2[CH:3]=1.CS(O)(=O)=O.[OH-].[NH4+]>C1(OC)C=CC=CC=1>[NH2:13][CH:8]1[N:7]=[C:6]([CH3:24])[C:5]2[CH:25]=[CH:26][C:2]([Br:1])=[CH:3][C:4]=2[N:10]([CH3:11])[C:9]1=[O:12]

参加物

5

反応物 3

HCID 6395Methanesulfonic AcidHCID 14923Ammonium HydroxideHCID 21941566benzyl 8-bromo-1,5-dimethyl-2-oxo-2,3-dihydro-1H-1,4-benzodiazepin-3-ylcarbamate

生成物 1

HCID 219415543-amino-8-bromo-1,5-dimethyl-1,3-dihydro-2H-1,4-benzodiazepin-2-one収率 82.1%

試薬・触媒・溶媒 1

HCID 7519Anisole溶媒

反応条件

温度
40 °C

実験手順

162c (0.831 g, 2.00 mmol) was dissolved in anhydrous anisole (16 ml) and then methane sulfonic acid (3.84 g, 40 mmol) was added in one portion, and then the reaction was heated to 40° C. for 30 minutes with stirring. The reaction was cooled to 0° C. in an ice bath then basified to pH=10 with concentrated ammonium hydroxide. The aqueous solution was then extracted with chloroform (3×50 ml) and the organic layers combined, dried over magnesium sulfate, filtered and the filtrate concentrated to give a residue. The residue was purified to silica gel column chromatography eluting with 10% methyl alcohol in chloroform to give the title compound 162d (0.463 g, 82%). 1H NMR (CDCl3, 300 MHz): δ 7.32-7.23 (m, 3H), 4.12 (d, 1H, J=1.1 Hz), 3.27 (s, 3H), 2.30 (d, 3H, J=1.5 Hz) ppm.

後処理

  1. temperatureThe reaction was cooled to 0° C. in an ice bath
  2. extractionThe aqueous solution was then extracted with chloroform (3×50 ml)
  3. dry with materialdried over magnesium sulfate
  4. filtrationfiltered
  5. concentrationthe filtrate concentrated
  6. customto give a residue
  7. customThe residue was purified to silica gel column chromatography
  8. washeluting with 10% methyl alcohol in chloroform

出典と根拠

ORDレコード
ord-5e6fcef6213c4ba4b337bfb85bd6aa0a
出典データセット
uspto-grants-2008_09
特許番号
US07423033B2

反応ノート

読み込み中…