2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 86691487, compound

HRID 576496Notes

Reaction equation

HRID 576496 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:22]3[CH2:21][CH2:20][C:19]4[CH:23]=[CH:24][CH:25]=[CH:26][C:18]=4[C:17]=3[N:16]=[C:15]3[C:10]=2[CH2:11][CH2:12][C:13]2[CH:30]=[CH:29][CH:28]=[CH:27][C:14]=23)=[CH:5][CH:4]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCOCC1>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[C:22]3[CH:21]=[CH:20][C:19]4[CH:23]=[CH:24][CH:25]=[CH:26][C:18]=4[C:17]=3[N:16]=[C:15]3[C:10]=2[CH:11]=[CH:12][C:13]2[CH:30]=[CH:29][CH:28]=[CH:27][C:14]=23)=[CH:5][CH:4]=1

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 180401457366-69-5

Product 1

HCID 86691487HCID 86691487, compoundYield 72%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

In an inert argon atmosphere 17 (4.93 g, 12.7 mmol, 1 eq) was dissolved in abs. 1,4-dioxane (300 mL, dried over sodium) under vigorously stirring at 80° C. 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ, 17.25 g, 76 mmol, 6 eq) was added in portions over a 5 minutes period and the DDQ-vessel was flushed with abs. dioxane (20 mL). The almost black mixture was stirred at 80° C. for two days maintaining the inert atmosphere. After cooling to room temperature the reaction mixture was carefully added to 500 mL of an aqueous saturated sodium carbonate solution and the reaction vessel was flushed with saturated Na2CO3 solution (250 mL) and water (200 mL). After stirring of the mixture at 65° C. for 75 minutes the precipitate was allowed to settle down and the product was isolated by filtration and purified by multiple slurry of the solid in water (overall ca. 1000 mL). After drying of the crude product in vacuo at 40° C. overnight the solid was suspended in methylene chloride (20 mL), stirred for 45 minutes, isolated by filtration and washed with DCM (2×20 mL) and dried overnight. 3.53 g of an ochre solid (72% yield) could be obtained in a 99.5% HPLC purity. Further purification of the material was possible by gradient sublimation (initial amount: 1.00 g, sublimation yield: 67%).

Workup

  1. customthe DDQ-vessel was flushed with abs
  2. temperaturemaintaining the inert atmosphere
  3. temperatureAfter cooling to room temperature the reaction mixture
  4. additionwas carefully added to 500 mL of an aqueous saturated sodium carbonate solution
  5. customthe reaction vessel was flushed with saturated Na2CO3 solution (250 mL) and water (200 mL)
  6. stirringAfter stirring of the mixture at 65° C. for 75 minutes the precipitate
  7. customthe product was isolated by filtration
  8. custompurified by multiple slurry of the solid in water (overall ca. 1000 mL)
  9. dry with materialAfter drying of the crude product in vacuo at 40° C. overnight the solid
  10. stirringstirred for 45 minutes
  11. customisolated by filtration
  12. washwashed with DCM (2×20 mL)
  13. customdried overnight

Sources & evidence

ORD record
ord-1f04583cb2244c7ba53fa7dc75a278db
Source dataset
uspto-grants-2015_05
Patent number
US09040175B2

Reaction notes

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