2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 60204508, compound

HRID 2267387Notes

Reaction equation

HRID 2267387 reaction equation
[Li]C(C)(C)C.[F:6][C:7]1[CH:12]=[CH:11][C:10]([N:13]([CH3:19])[C:14]2[S:15][CH:16]=[CH:17][N:18]=2)=[CH:9][CH:8]=1.[Cl:20][C:21]1[N:26]=[CH:25][C:24]([F:27])=[CH:23][N:22]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.[OH-].[Na+]>CCCCCCC.C1COCC1.O.CCOC(C)=O>[Cl:20][C:21]1[N:26]=[C:25]([C:16]2[S:15][C:14]([N:13]([C:10]3[CH:9]=[CH:8][C:7]([F:6])=[CH:12][CH:11]=3)[CH3:19])=[N:18][CH:17]=2)[C:24]([F:27])=[CH:23][N:22]=1

Participants

10

Reactant 5

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 14798Sodium HydroxideHCID 5834662-Chloro-5-fluoropyrimidineHCID 60204507HCID 60204507, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 60204508HCID 60204508, compound

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 8900HeptaneSolvent

Conditions

Temperature
-78 °C

Procedure

8.4 mL (13 mmol) of a 1.6 M solution of tBuLi in heptane was added to a rapidly stirred suspension of 2.5 g (12 mmol) of N-(4-fluorophenyl)-N-methylthiazol-2-amine in 50 mL of THF at −78° C. The solution was stirred for 1 min at −78° C. before 1.3 mL (13 mmol) of 2-chloro-5-fluoropyrimidine was added. The reaction solution was stirred for 1 h at −78° C., then quenched by addition of 2 mL of MeOH. Solid 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (5.5 g, 24 mmol) was added and the reaction solution was stirred for 1 h and then 25 mL of 10% (w/v) aqueous NaOH was added. The reaction solution was warmed to rt and stirred 2 h, then poured into 500 mL of EtOAc and 200 mL of water, separated and the organic layer washed twice with saturated aqueous NaHCO3, once with brine, dried over MgSO4, filtered and concentrated. The residue was purified by C-18 prep MPLC to give the title compound. MS (M+H)+ 339.

Workup

  1. additionwas added
  2. customquenched by addition of 2 mL of MeOH
  3. stirringthe reaction solution was stirred for 1 h
  4. temperatureThe reaction solution was warmed to rt
  5. stirringstirred 2 h
  6. customseparated
  7. washthe organic layer washed twice with saturated aqueous NaHCO3, once with brine
  8. dry with materialdried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe residue was purified by C-18 prep MPLC

Sources & evidence

ORD record
ord-5e20645df24a415ab3833757e63c0745
Source dataset
uspto-grants-2010_12
Patent number
US07858785B2

Reaction notes

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