2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 118006063, compound

HRID 1049624Notes

Reaction equation

HRID 1049624 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH:19]=[C:20]([F:22])[CH:21]=1)[CH2:5][CH:6]([CH2:11][CH:12](OCC)OCC)[C:7]([O:9][CH3:10])=[O:8].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>CO.OS(O)(=O)=O>[Br:1][C:2]1[CH:21]=[C:20]([F:22])[CH:19]=[C:4]2[C:3]=1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5]2

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 118005972HCID 118005972, compound

Product 1

HCID 118006063HCID 118006063, compoundYield 28%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 1118Sulfuric AcidSolvent

Procedure

A solution of 29 (6.1 g, 16.3 mmol) in MeOH (6 mL) was added dropwise to a suspension of dichlorodicyanobenzoquinone (DDQ, 3.8 g, 16.7 mmol) in 80% aqueous H2SO4 (30 mL) at 0° C. After the addition was completed, the ice bath was removed and stirring was continued for 1 h. The mixture was poured in to ice water (100 mL), then the resulting brown precipitate was filtered, dissolved in ethyl acetate, and washed with H2O (100 mL). The organic layer was dried over anhydrous Na2SO4, filtered, concentrated rotary evaporation, and purified by column chromatography to give methyl 5-bromo-7-fluoro-2-naphthoate (30) (28%). 1H NMR (600 MHz, Acetone-d6) δ 8.67 (d, J=1.3 Hz, 1H), 8.31 (d, J=8.8 Hz, 1H), 8.18-8.14 (m, 1H), 7.95 (td, J=8.7, 8.2, 2.5 Hz, 2H), 3.97 (s, 3H). GC-MS (ES) for C12H8BrFO2 [M+1]+ 283.

Workup

  1. additionAfter the addition
  2. customthe ice bath was removed
  3. additionThe mixture was poured in to ice water (100 mL)
  4. filtrationthe resulting brown precipitate was filtered
  5. dissolutiondissolved in ethyl acetate
  6. washwashed with H2O (100 mL)
  7. dry with materialThe organic layer was dried over anhydrous Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated rotary
  10. customevaporation
  11. custompurified by column chromatography

Sources & evidence

ORD record
ord-fbfb44ea92cd47d5a9e553feffe8a6f0
Source dataset
uspto-grants-2016_07
Patent number
US09382245B2

Reaction notes

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