Hydrogen Peroxide → 2,3-Dimethoxy-5-methyl-1,4-benzoquinone

HRID 491005

反応式

HRID 491005 の反応式
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH3:13])[CH:6]=[C:7]([O:11]C)[C:8]=1[O:9][CH3:10].OO.[N+]([O-])(O)=[O:17].O>CC(O)=O.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[CH3:10][O:9][C:8]1[C:7](=[O:11])[CH:6]=[C:5]([CH3:13])[C:4](=[O:17])[C:3]=1[O:2][CH3:1]

参加物

7

反応物 4

HCID 784Hydrogen PeroxideHCID 944Nitric AcidHCID 962WaterHCID 809223,4,5-Trimethoxytoluene

生成物 1

HCID 690682,3-Dimethoxy-5-methyl-1,4-benzoquinone収率 175.7%

試薬・触媒・溶媒 2

HCID 521998p-Toluenesulfonic acid monohydrate触媒HCID 176Acetic Acid溶媒

反応条件

温度
75 °C

実験手順

To a round-bottom flask (20 mL) equipped with a reflux condenser was added a solution of commercial 3,4,5-trimethoxy-toluene (0.547 g, 3 mmol) in AcOH (3 mL), followed by para-toluenesulfonic acid monohydrate (57 mg, 0.3 mmol) as catalyst. The oxidant H2O2 (30%, 0.65 mL, 6 mmol) was then added. The reaction mixture was stirred and heated at 75° C. for 30 min. The resulting dark-red solution was cooled to 0-5° C., and concentrated HNO3 (90%, 1.5 mmol) was then slowly added. The cold solution was poured into H2O (50 mL) and extracted with CH2Cl2 (3×50 mL). The combined organic layers were washed with H2O (80 mL) in order to remove traces of AcOH, dried (Na2SO4) and filtered. When the solvent was evaporated under vacuum, the final crude (0.528 g, dark-red oil) was dissolved in boiling hexane (70 mL), filtered, and the solvent was removed to give the pure 2,3-Dimethoxy-5- methyl-[1,4]benzoquinone (0.480 g, 88% yield) as red needles. 1H NMR (400 MHz, CDCl3, ppm): δ2.04 [d, 3H, J=1.6 Hz, CH3], 4.00 [s, 3H, OCH3], 4.02 [s, 3H, OCH3], 6.43-6.44 [q, 1H, Jm=1.6 Hz]. 13C NMR (400 MHz, CDCl3, ppm): δ15.4, 31.1, 61.2, 131.3, 144.0, 144.9, 145.1, 184.1, 184.4. MS m/z (%): 182 (85), 167 (32), 153 (13), 137 (100), 121 (6), 111(23), 96 (12), 83 (67), 69 (31), 53 (15).

後処理

  1. customTo a round-bottom flask (20 mL) equipped with a reflux condenser
  2. temperatureThe resulting dark-red solution was cooled to 0-5° C.
  3. extractionextracted with CH2Cl2 (3×50 mL)
  4. washThe combined organic layers were washed with H2O (80 mL) in order
  5. customto remove traces of AcOH
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. customWhen the solvent was evaporated under vacuum
  9. dissolutionthe final crude (0.528 g, dark-red oil) was dissolved
  10. filtrationfiltered
  11. customthe solvent was removed

出典と根拠

ORDレコード
ord-56c1b381bae7442980b54b9af05539cf
出典データセット
uspto-grants-2009_05
特許番号
US07528271B2

関連ノート

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