Acetonitrile → 2,2'-Ethylenebis(6-(bromomethyl)-4-benzoquinone)

HRID 2119120Notes

Reaction equation

HRID 2119120 reaction equation
[Br:1][CH2:2][C:3]1[C:4]([O:25]C)=[C:5]([CH2:11][CH2:12][C:13]2[CH:18]=[C:17]([O:19]C)[CH:16]=[C:15]([CH2:21][Br:22])[C:14]=2[O:23]C)[CH:6]=[C:7]([O:9]C)[CH:8]=1.C(#N)C.C(OCC)(=O)C>O>[CH2:12]([C:13]1[C:14](=[O:23])[C:15]([CH2:21][Br:22])=[CH:16][C:17](=[O:19])[CH:18]=1)[CH2:11][C:5]1[C:4](=[O:25])[C:3]([CH2:2][Br:1])=[CH:8][C:7](=[O:9])[CH:6]=1

Participants

5

Reactant 3

HCID 6342AcetonitrileHCID 8857Ethyl AcetateHCID 13938539HCID 13938539, compound

Product 1

HCID 1358562,2'-Ethylenebis(6-(bromomethyl)-4-benzoquinone)

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

0.85 g. (1.7 mmole) of 1,2-bis[3-(bromomethyl)-2,5-dimethoxyphenyl]ethane, prepared as described in Example IX above, was dissolved in 50 ml. of hot acetonitrile. This solution was cooled to a temperature just above the point at which it became cloudy and then there was added dropwise thereto a solution of 6.37 g. (11.6 mmole) of ceric ammonium nitrate in 8 ml. of water. Stirring of the mixed solution was continued for ten minutes after the addition of the ceric ammonium nitrate was complete, then the reaction mixture was diluted with water and extracted with methylene chloride. The organic extract was washed with water, dried over sodium sulfate and the solvent removed in vacuo to yield 0.75 g. of a dark brown solid. Trituration of this dark brown solid with a small quantity of ethyl acetate afforded 2,2'-ethylenebis[6-(bromomethyl)-p-benzoquinone] as a yellow-brown solid, the yield being 0.62 g. (83 percent of theoretical). Recrystallization from a mixture of ethyl acetate and hexane gave yellow-brown needles, melting point 146°-147° C. The infrared spectrum of the recrystallized material showed peaks at 1650, 1635 and 1615 cm-1, while the PNMR spectrum in deuterochloroform showed peaks at delta=2.72 (singlet, 4 protons, attributed to methylene protons), 4.25 (doublet, 4 protons, J=1.0 Hz., attributed to bromomethyl protons), 6.59 (doublet, 2 protons, J=2.2 Hz., attributed to protons on the quinone rings) and 6.85 (multiplet, 2 protons, attributed to protons on the quinone rings) ppm. The mass spectrum of the compound showed a peak at m/e 348 (M-80 for the formula C16H12O4Br2).

Workup

  1. dissolutionwas dissolved in 50 ml
  2. temperatureThis solution was cooled to a temperature just above the point at which it
  3. additionthere was added dropwise
  4. waitwas continued for ten minutes
  5. extractionextracted with methylene chloride
  6. extractionThe organic extract
  7. washwas washed with water
  8. dry with materialdried over sodium sulfate
  9. customthe solvent removed in vacuo
  10. customto yield 0.75 g

Sources & evidence

ORD record
ord-a2b7f67228294c6c8724b5d73e923b14
Source dataset
uspto-grants-1987_07
Patent number
US04683087

Reaction notes

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