2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 60204517, compound

HRID 2267396Notes

Reaction equation

HRID 2267396 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]([C:10]2[S:11][CH:12]=[CH:13][N:14]=2)[CH3:9])=[CH:4][CH:3]=1.C([Li])(C)(C)C.[Br:20][C:21]1[CH:22]=[N:23][C:24]([Cl:27])=[N:25][CH:26]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>O1CCCC1.O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+].O>[Br:20][C:21]1[C:22]([C:12]2[S:11][C:10]([CH:8]([C:5]3[CH:6]=[CH:7][C:2]([F:1])=[CH:3][CH:4]=3)[CH3:9])=[N:14][CH:13]=2)=[N:23][C:24]([Cl:27])=[N:25][CH:26]=1

Participants

8

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 6066655-Bromo-2-chloropyrimidineHCID 57428844HCID 57428844, compoundHCID 178418306HCID 178418306, compound

Product 1

HCID 60204517HCID 60204517, compoundYield 46%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 23667548Sodium AscorbateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 2-(1-(4-fluorophenyl)ethyl)thiazole (200 mg, 0.966 mmol) in 5 mL of tetrahydrofuran was cooled to −78° C. and treated with tert-butyllithium (0.622 mL, 1.7 M solution in pentane, 1.06 mmol) added dropwise. 5-Bromo-2-chloropyrimidine (205.5 mg, 1.06 mmol) was added to the reaction mixture and stirred for another 30 min before quenching with 1 mL of acetic acid in 5 mL of methanol. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (468 mg, 2.06 mmol) was added to the reaction after cooling to 0° C., stirred for 20 min, diluted with sodium ascorbate (0.5M, 100 mL) and water (300 mL). The crude product was extracted from the aqueous layer with chloroform (3×75 mL), dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo. The crude product was purified by flash chromatography with 0-40% ethyl acetate in hexane to afford the title compound as a yellow amorphous solid (177 mg,). MS (M+H)+ 398/400.

Workup

  1. additionadded dropwise
  2. custombefore quenching with 1 mL of acetic acid in 5 mL of methanol
  3. stirringstirred for 20 min
  4. extractionThe crude product was extracted from the aqueous layer with chloroform (3×75 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude product was purified by flash chromatography with 0-40% ethyl acetate in hexane

Sources & evidence

ORD record
ord-dc2b29a1180941f49d05b19d9440f852
Source dataset
uspto-grants-2010_12
Patent number
US07858785B2

Reaction notes

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