2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 86647176, compound

HRID 1038509Notes

Reaction equation

HRID 1038509 reaction equation
[Cl:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([NH:8][CH3:9])=[O:7])=[CH:4][N:3]=1.[CH2:12]([Mg]Br)[CH2:13][CH3:14].[Cl-].[NH4+].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>O1CCCC1.C(OC)(C)(C)C.CO>[Cl:1][C:2]1[CH:11]=[C:10]([CH2:12][CH2:13][CH3:14])[C:5]([C:6]([NH:8][CH3:9])=[O:7])=[CH:4][N:3]=1

Participants

8

Reactant 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 25517Ammonium ChlorideHCID 123642306-Chloro-N-methylnicotinamideHCID 178455851HCID 178455851, compound2×

Product 1

HCID 86647176HCID 86647176, compoundYield 75%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

6-Chloro-N-methylnicotinamide (2.00 g, 11.7 mol) was dissolved in tetrahydrofuran (59 mL), added propylmagnesium bromide (46.9 mL, 46.9 mol) under ice-cold conditions, and stirred at room temperature for 4.5 hours. Then, propylmagnesium bromide (46.9 mL, 46.9 mol) was added under ice-cold conditions and the mixture was further stirred at room temperature for 9 hours. The reaction solution was added methanol (140 mL) and ammonium chloride (7.5 g) under ice-cold conditions, and stirred at room temperature for 0.5 hours. The reaction solution was added DDQ (3.19 g, 14.1 mmol) under ice-cold conditions, and stirred at room temperature for 2 hours. The reaction solution was added tert-butyl methylether, and filtered through a pad of celite, concentrated in vacuo, and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated in vacuo. The obtained residue was purified by silica-gel column chromatography (chloroform/methanol). The title compound (1.88 g (yield 75%)) was obtained as a light brown crystal.

Workup

  1. stirringthe mixture was further stirred at room temperature for 9 hours
  2. stirringstirred at room temperature for 0.5 hours
  3. stirringstirred at room temperature for 2 hours
  4. filtrationfiltered through a pad of celite
  5. concentrationconcentrated in vacuo
  6. extractionextracted with ethyl acetate
  7. washThe organic layer was washed with brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customThe obtained residue was purified by silica-gel column chromatography (chloroform/methanol)

Sources & evidence

ORD record
ord-652e6966fd2c429e85db73430e77e19e
Source dataset
uspto-grants-2013_10
Patent number
US08551985B2

Reaction notes

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