2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 60204504, compound

HRID 507604Notes

Reaction equation

HRID 507604 reaction equation
[Li]C(C)(C)C.CCCCC.[C:11]1([CH:17]([O:23][Si:24]([CH3:27])([CH3:26])[CH3:25])[C:18]2[S:19][CH:20]=[CH:21][N:22]=2)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[Br:28][C:29]1[CH:30]=[N:31][C:32]([Cl:35])=[N:33][CH:34]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>C1COCC1.C([O-])([O-])=O.[Na+].[Na+]>[Br:28][C:29]1[C:30]([C:20]2[S:19][C:18]([CH:17]([C:11]3[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=3)[O:23][Si:24]([CH3:27])([CH3:26])[CH3:25])=[N:22][CH:21]=2)=[N:31][C:32]([Cl:35])=[N:33][CH:34]=1

Participants

9

Reactant 6

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 8003PentaneHCID 6066655-Bromo-2-chloropyrimidineHCID 13032473HCID 13032473, compoundHCID 23667548Sodium AscorbateHCID 178418306HCID 178418306, compound

Product 1

HCID 60204504HCID 60204504, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 10340Sodium CarbonateSolvent

Conditions

Temperature
-78 °C

Procedure

A 1.7 M solution of tBuLi in pentane (1.8 mL, 3.0 mmol) was added to a stirred solution of 0.80 g (3.0 mmol) of 2-[phenyl(trimethylsilyloxy)methyl]thiazole in 25 mL of THF at −78° C. The solution was stirred for 10 min at −78° C. before 0.59 g (3.0 mmol) of 5-bromo-2-chloropyrimidine was added. The reaction solution was stirred for 30 min at −78° C., then quenched by addition of 1 mL of AcOH in 4 mL of MeOH. Solid 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (1.4 g, 6.1 mmol) was added and the reaction solution was warmed to 0° C. and stirred for 10 min. The reaction solution was then poured into 50 mL of a 0.5 M solution of sodium ascorbate, diluted with 100 mL of a 1 M aqueous solution of Na2CO3. The aqueous solution was extracted four times with CHCl3 and the combined organic extracts dried over MgSO4, filtered and concentrated to give the crude product which was purified by flash chromatography eluting with a linear gradient of 30% EtOAc in hexane to neat EtOAc to deliver the title compound. MS (M+H)+ 456.

Workup

  1. additionwas added
  2. customquenched by addition of 1 mL of AcOH in 4 mL of MeOH
  3. temperaturethe reaction solution was warmed to 0° C.
  4. stirringstirred for 10 min
  5. extractionThe aqueous solution was extracted four times with CHCl3
  6. dry with materialthe combined organic extracts dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-275878c6fbd342a9ac8ecde6bd60bb5c
Source dataset
uspto-grants-2010_08
Patent number
US07786132B2

Reaction notes

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