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

HRID 381275Notes

Reaction equation

HRID 381275 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 1 L 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-dichloro-bromobenzene in 50-75 mL of anhydrous ether. The reaction was cooled to −90° C. and 96 mL of tert-butyllithium (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. customTo a 1 L 3-neck flask fitted with an addition funnel, N2 inlet, magnetic stir bar
  2. temperaturewhile maintaining the temperature below −70° C
  3. temperatureThe reaction temperature was cooled to −80 to −90° C.
  4. additionwas added
  5. additionwas added slowly
  6. stirringthe mixture was stirred for a 0.5 h
  7. stirringthe mixture stirred for 15 minutes
  8. customthe mixture transferred to a separatory funnel
  9. customThe organic layer was separated
  10. customdried
  11. filtrationfiltered
  12. customevaporated
  13. customThe crude product was chromatographed
  14. washeluted with 30% EtOAc/heptane
  15. customtriturated with Et2O

Sources & evidence

ORD record
ord-b1d93914137d4c9d843ae9da871c1dba
Source dataset
uspto-grants-2001_10
Patent number
US06306866B1

Reaction notes

Loading…