Trimethyl orthoformate → HCID 66937371、化合物

HRID 408701ノート

反応式

HRID 408701 の反応式
[Cl:1][C:2]1[C:3]([O:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:4][C:5]([N+:9]([O-])=O)=[C:6]([NH2:8])[CH:7]=1.[CH3:19]OC(OC)OC.S(S([O-])=O)([O-])=O.[Na+].[Na+].C(=O)(O)[O-].[Na+]>CN(C=O)C.C(O)(=O)C>[Cl:1][C:2]1[C:3]([O:12][C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)=[CH:4][C:5]2[N:9]=[CH:19][NH:8][C:6]=2[CH:7]=1

参加物

7

反応物 4

HCID 9005Trimethyl orthoformateHCID 24489Sodium Dithionite2 回HCID 516892Sodium BicarbonateHCID 669372525-Chloro-2-nitro-4-phenoxyphenylamine

生成物 1

HCID 66937371HCID 66937371、化合物収率 76%

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒2 回HCID 6228Dimethylformamide溶媒

反応条件

温度
100 °C

実験手順

To a solution of 5-chloro-2-nitro-4-phenoxyphenylamine (0.810 g, 3.06 mmol) in DMF (12 mL) was added trimethylorthoformate (12 mL) followed by sodium dithionite (2.66 g, 15.3 mmol), and glacial acetic acid (1.5 mL). The reaction mixture was heated in a sealed tube at 100° C. for 14 h. Additional sodium dithionite (0.5 g) and acetic acid (1 mL) were added and heating was continued at 120° C. for an additional 3 h. The reaction flask was cooled in ice, added cautiously to half-saturated sodium bicarbonate solution (300 mL) and extracted with EtOAc. Combined organic layers were washed with 5% NaHCO3, brine, dried, filtered, and concentrated under reduced pressure. The residue was purified (FCC) (hexanes:EtOAc, 0% to 5% over 20 minutes) to yield the titled compound as a yellow amorphous solid (0.57 g, 76%) as a mixture of tautomers. MS (ESI/CI): mass calcd. for C13H9ClN2O, 244; m/z found, 245 [M+H]+. 1H NMR (500 MHz, CDCl3): 9.55 (s, 1H), 8.06 (s, 1H), 8.0-7.2 (m, 2H), 7.32 (t, J=7.9 Hz, 2H), 7.09 (t, J=7.3 Hz, 1H), 6.96 (d, J=8.3 Hz, 2H).

後処理

  1. temperatureheating
  2. temperatureThe reaction flask was cooled in ice
  3. extractionextracted with EtOAc
  4. washCombined organic layers were washed with 5% NaHCO3, brine
  5. customdried
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe residue was purified (FCC) (hexanes:EtOAc, 0% to 5% over 20 minutes)

出典と根拠

ORDレコード
ord-a392a6830fca4dcbbd3cd1011e7a2139
出典データセット
uspto-grants-2014_06
特許番号
US08759345B2

反応ノート

読み込み中…