2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 58129780, compound

HRID 2092931Notes

Reaction equation

HRID 2092931 reaction equation
[CH2:1]([CH:3]([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:4][C:5]1[C:10]([CH2:11][CH:12]([CH2:17][CH3:18])[CH2:13][CH2:14][CH2:15][CH3:16])=[CH:9][C:8]([C:19]2[CH:23]=[CH:22][S:21][CH:20]=2)=[C:7]([C:24]2[CH:28]=[CH:27][S:26][CH:25]=2)[CH:6]=1)[CH3:2].B(F)(F)F.CCOCC.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>CO>[CH2:1]([CH:3]([CH2:29][CH2:30][CH2:31][CH3:32])[CH2:4][C:5]1[CH:6]=[C:7]2[C:24]3[CH:28]=[CH:27][S:26][C:25]=3[C:20]3[S:21][CH:22]=[CH:23][C:19]=3[C:8]2=[CH:9][C:10]=1[CH2:11][CH:12]([CH2:17][CH3:18])[CH2:13][CH2:14][CH2:15][CH3:16])[CH3:2]

Participants

5

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinone7×HCID 8000Boron trifluoride etherate3×HCID 58129777HCID 58129777, compound

Product 1

HCID 58129780HCID 58129780, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
5 °C

Procedure

A dry 500 mL 3-neck flask, flushed with dry nitrogen, was charged with 5 g (10.7 mmol) of 3,3′-(4,5-bis(2-ethylhexyl)-1,2-phenylene)dithiophene. The flask was evacuated and backfilled with nitrogen 3 times. Dry CH2Cl2 (214 mL, 0.05 M) was added to the flask via cannula. The solution was bubbled with nitrogen for 15 min. The solution was then cooled to 5° C. and BF3.Et2O (1.61 mL, 12.9 mmol) was added. DDQ (2.43 g, 10.7 mmol) was added in 0.5 g increments over 30 min. The reaction was monitored by TLC using C18 silica plates in methanol. After DDQ addition was completed, continued to monitor the reaction. At 15 min after DDQ addition, added another 0.1 g of DDQ followed by another 0.1 g addition at 18 min after first DDQ addition. At 30 min after initial DDQ addition, 0.3 mL of BF3.Et2O was added followed by another 1 mL of BF3.Et2O at 40 min. At 1 h after initial DDQ addition was complete, no starting material was noticed by TLC and the reaction was quenched by the adding 3 g of Zn powder followed by stirring of the reaction for 2 h. The mixture was diluted with 200 mL of methanol and stirred for another hour. The mixture was diluted with water and extracted with chloroform (3×500 mL). The organic fractions were dried over MgSO4 and then concentrated. The product was purified by column chromatography using hexane as the eluent to yield the product as pale yellow oil that crystallized upon standing (3.2 g, 64%). 1H NMR (300 MHz, CDCl3): δH 7.90 (d, 2H), 7.37 (d, 2H), 2.77 (m, 4H), 1.72 (m, 16H), 0.89 (m, 12H).

Workup

  1. customA dry 500 mL 3-neck flask, flushed with dry nitrogen
  2. customThe flask was evacuated
  3. additionDry CH2Cl2 (214 mL, 0.05 M) was added to the flask via cannula
  4. customThe solution was bubbled with nitrogen for 15 min
  5. customthe reaction
  6. additionfollowed by another 0.1 g addition at 18 min
  7. additionwas added
  8. customthe reaction was quenched by the adding 3 g of Zn powder
  9. additionThe mixture was diluted with 200 mL of methanol
  10. stirringstirred for another hour
  11. additionThe mixture was diluted with water
  12. extractionextracted with chloroform (3×500 mL)
  13. dry with materialThe organic fractions were dried over MgSO4
  14. concentrationconcentrated
  15. customThe product was purified by column chromatography

Sources & evidence

ORD record
ord-c0e8c550c5cb4b5e8f5f063a166221e4
Source dataset
uspto-grants-2013_05
Patent number
US08440785B2

Reaction notes

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