Ammonia → 2,2-Dimethyl-6-trifluoromethylthio-2H-1-benzopyran

HRID 1656465Notes

Reaction equation

HRID 1656465 reaction equation
[SH:1][C:2]1[CH:3]=[CH:4][C:5]2[O:10][C:9]([CH3:12])([CH3:11])[CH:8]=[CH:7][C:6]=2[CH:13]=1.N.[F:15][C:16](I)([F:18])[F:17]>C(OCC)(=O)C>[CH3:12][C:9]1([CH3:11])[CH:8]=[CH:7][C:6]2[CH:13]=[C:2]([S:1][C:16]([F:18])([F:17])[F:15])[CH:3]=[CH:4][C:5]=2[O:10]1

Participants

5

Reactant 3

HCID 222AmmoniaHCID 16843TrifluoroiodomethaneHCID 150360126-mercapto-2,2-dimethyl-2H-1-benzopyran

Product 1

HCID 147482442,2-Dimethyl-6-trifluoromethylthio-2H-1-benzopyranYield 59.6%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

1.45 g of 6-mercapto-2,2-dimethyl-2H-1-benzopyran (prepared as described in Preparation 6) was suspended in 30 ml of liquid ammonia, and 8.23 g of trifluoromethyl iodide were then added to the suspension at -60° C. in an atmosphere of nitrogen. The resulting mixture was then irradiated at -65° C. for 2 hours and then at 25° C. for 2 hours, using a low pressure mercury lamp. At the end of this time, the reaction mixture was diluted with ethyl acetate and washed with dilute aqueous hydrochloric acid, with water, with an aqueous solution of sodium hydrogencarbonate and with a saturated aqueous solution of sodium chloride, in that order. The organic layer was then dried over anhydrous sodium sulfate and concentrated by distillation under reduced pressure. The resulting residue was purified by column chromatography through silica gel, using a 20:2:1 by volume mixture of cyclohexane, chloroform and ethyl acetate as the eluent, to afford 1.17 g of the title compound as an oil.

Workup

  1. additionwere then added to the suspension at -60° C. in an atmosphere of nitrogen
  2. customThe resulting mixture was then irradiated at -65° C. for 2 hours
  3. washwashed with dilute aqueous hydrochloric acid, with water, with an aqueous solution of sodium hydrogencarbonate and with a saturated aqueous solution of sodium chloride, in that order
  4. dry with materialThe organic layer was then dried over anhydrous sodium sulfate
  5. concentrationconcentrated by distillation under reduced pressure
  6. customThe resulting residue was purified by column chromatography through silica gel
  7. additionby volume mixture of cyclohexane, chloroform and ethyl acetate as the eluent

Sources & evidence

ORD record
ord-b466f57a47be4a01b90bbd588d9412a7
Source dataset
uspto-grants-1993_10
Patent number
US05254578

Reaction notes

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