2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 11196232, compound

HRID 1859018Notes

Reaction equation

HRID 1859018 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4](Br)[CH:5]=[CH:6][C:7]=1[Cl:8].C([Li])(C)(C)C.[Cl:15][C:16]1[N:21]=[CH:20][CH:19]=[CH:18][N:17]=1.C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>CCOCC.C1COCC1.O.CCOC(C)=O.CC(O)=O>[Cl:1][C:2]1[CH:3]=[C:4]([C:18]2[CH:19]=[CH:20][N:21]=[C:16]([Cl:15])[N:17]=2)[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

10

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 290134-Bromo-1,2-dichlorobenzeneHCID 744042-ChloropyrimidineHCID 178418306HCID 178418306, compound

Product 1

HCID 11196232HCID 11196232, compoundYield 20%

Reagents, catalysts & solvents 5

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-90 °C

Procedure

To a 1L 3-neck flask fitted with an addition funnel, N2 inlet, magnetic stir bar and thermometer was added 15.26 (0.067 mol) of 3,4-dichlorobromobenzene in 50-75 mL of anhydrous ether. The reaction was cooled to -90° C. and 96 mL of tertbutyllithium (1.7 M solution in pentane) slowly was added over a 0.5 hr while maintaining the temperature below -70° C. The reaction temperature was cooled to -80 to -90° C. and 2-chloropyrimidine (9.10 gm, 0.08 mol) dissolved in anhydrous THF was added. The reaction was stirred for about 2 h and 18 gms of DDQ, (0.077 mol) dissolved in anhydrous THF was added slowly, and the mixture was stirred for a 0.5 h. Three mL of H2O containing 1 mL of HOAc in THF was added and the mixture stirred for 15 minutes. The reaction was diluted with 100 mL of H2O and 100 mL of EtOAc and the mixture transferred to a separatory funnel. The organic layer was separated, dried, filtered and evaporated. The crude product was chromatographed and eluted with 30% EtOAc/heptane and triturated with Et2O to yield 3.22 g of a white solid (20%) m.p. 126-127° C.

Workup

  1. temperaturewhile maintaining the temperature below -70° C
  2. temperatureThe reaction temperature was cooled to -80 to -90° C.
  3. additionwas added
  4. additionwas added slowly
  5. stirringthe mixture was stirred for a 0.5 h
  6. stirringthe mixture stirred for 15 minutes
  7. customthe mixture transferred to a separatory funnel
  8. customThe organic layer was separated
  9. customdried
  10. filtrationfiltered
  11. customevaporated
  12. customThe crude product was chromatographed
  13. washeluted with 30% EtOAc/heptane
  14. customtriturated with Et2O

Sources & evidence

ORD record
ord-185e196281794443958c48ef834ae279
Source dataset
uspto-grants-2000_11
Patent number
US06153619

Reaction notes

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