Toluene → Tert-butyl 4-(methoxycarbonyl)-3-nitrobenzoate

HRID 965275ノート

反応式

HRID 965275 の反応式
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[CH:8][C:7]([C:10]([OH:12])=[O:11])=[CH:6][C:5]=1[N+:13]([O-:15])=[O:14].C(Cl)(=O)C(Cl)=O.[C:23]1([CH3:29])[CH:28]=CC=C[CH:24]=1>CN(C=O)C.C(OCC)(=O)C>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[CH:8][C:7]([C:10]([O:12][C:23]([CH3:29])([CH3:28])[CH3:24])=[O:11])=[CH:6][C:5]=1[N+:13]([O-:15])=[O:14]

参加物

6

反応物 3

HCID 1140TolueneHCID 65578Oxalyl chlorideHCID 98592Methyl hydrogen 2-nitroterephthalate

生成物 1

HCID 23291046Tert-butyl 4-(methoxycarbonyl)-3-nitrobenzoate収率 83%

試薬・触媒・溶媒 2

HCID 6228Dimethylformamide触媒HCID 8857Ethyl Acetate溶媒

実験手順

To a stirred suspension of the above acid ((6), 7.0 g, 31 mMol) in toluene (25 mL) was added oxalylchloride (5 mL) followed by one drop of dry DMF. After stirring for 16 h (the solution became clear after ~30 minutes) the reaction was evaporated to dryness and re-evaporated from fresh toluene (2×100 mL). To the resulting acid chloride in CHCl3 (10 mL) with stirring at 0° C. was added t-BuOH (1 mL) followed by pyridine (0.6 mL). The reaction was allowed to warm to room temperature and stirred for 6 h. The resulting reaction was stripped of solvent, taken up in ethyl acetate, washed with aq. 1N NaHCO3, brine, dried (MgSO4) and evaporated under reduced pressure. Purification by flash chromatography on silica gel eluted with 10% ethyl acetate in hexane gave product (7) (7.28 g, 83%) as a clear oil.

後処理

  1. waitbecame clear after ~30 minutes
  2. custom) the reaction was evaporated to dryness
  3. customre-evaporated from fresh toluene (2×100 mL)
  4. stirringTo the resulting acid chloride in CHCl3 (10 mL) with stirring at 0° C.
  5. additionwas added t-BuOH (1 mL)
  6. stirringstirred for 6 h
  7. customThe resulting reaction
  8. washwashed with aq. 1N NaHCO3, brine
  9. dry with materialdried (MgSO4)
  10. customevaporated under reduced pressure
  11. customPurification by flash chromatography on silica gel
  12. washeluted with 10% ethyl acetate in hexane

出典と根拠

ORDレコード
ord-cc3ce8af49464841adb81265b3a8f541
出典データセット
uspto-grants-1998_06
特許番号
US05773512

反応ノート

読み込み中…