Carbon Dioxide → 4-Methoxycarbonyl-(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithiole)

HRID 1108170Notes

Reaction equation

HRID 1108170 reaction equation
[CH3:1][C:2]1([CH3:16])[S:6][C:5]2[CH:7]=[C:8]3[S:12][C:11]([CH3:14])([CH3:13])[S:10][C:9]3=[CH:15][C:4]=2[S:3]1.C([Li])CCC.[C:22](=[O:24])=[O:23].[C:25](=O)([O-])[O-].[K+].[K+].CI>CCOCC.CN(C=O)C>[CH3:25][O:23][C:22]([C:15]1[C:4]2[S:3][C:2]([CH3:16])([CH3:1])[S:6][C:5]=2[CH:7]=[C:8]2[S:12][C:11]([CH3:14])([CH3:13])[S:10][C:9]=12)=[O:24]

Participants

8

Reactant 5

HCID 280Carbon DioxideHCID 6328Methyl iodideHCID 11430Potassium CarbonateHCID 111969402,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithioleHCID 178418339Butyllithium

Product 1

HCID 539241844-Methoxycarbonyl-(2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithiole)

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolvent

Procedure

2,2,6,6-Tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dithiole (2.0 g, 6.98 mmol) was dissolved in dry ether (50.0 mL) in a dry, argon filled reaction flask. n-Butyllithium (3.07 mL, 2.5M in hexane) was added and the reaction mixture was stirred for 30 min. The solution was poured onto solid carbon dioxide and, after stirring overnight, the ether was filtered off. The solid residue was washed with chloroform and dried under vacuum. The crude product was mixed with potassium carbonate (0.97 g, 6.98 mmol) in dry DMF (20.0 mL) and was stirred for 1.5 h at 60° C. After cooling to ambient temperature, methyl iodide (0.435 mL, 6.98 mmol) was added. The stirring was continued overnight. The mixture was filtered, the solution evaporated and the residue was dissolved in dichloromethane and water. The organic phase was washed with water (2*30 mL), dried (Na2SO4) and evaporated to give after additional drying under vacuum a bright green-yellow crystalline pure product. Yield 1.56 g (65%).

Workup

  1. additionfilled
  2. customreaction flask
  3. stirringafter stirring overnight
  4. filtrationthe ether was filtered off
  5. washThe solid residue was washed with chloroform
  6. customdried under vacuum
  7. stirringwas stirred for 1.5 h at 60° C
  8. waitThe stirring was continued overnight
  9. filtrationThe mixture was filtered
  10. customthe solution evaporated
  11. dissolutionthe residue was dissolved in dichloromethane
  12. washThe organic phase was washed with water (2*30 mL)
  13. dry with materialdried (Na2SO4)
  14. customevaporated
  15. customto give
  16. customafter additional drying under vacuum a bright green-yellow crystalline pure product

Sources & evidence

ORD record
ord-4267caa3585c4426925b341e6bfe4b5d
Source dataset
uspto-grants-2000_05
Patent number
US06063360

Reaction notes

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