Dichloromethane → HCID 21933564, compound

HRID 2214407Notes

Reaction equation

HRID 2214407 reaction equation
FC(F)(F)S(O)(=O)=[O:4].N[C:10]1[C:11]([S:16][CH2:17][C:18]([O:20][CH3:21])=[O:19])=[N:12][CH:13]=[CH:14][CH:15]=1.ClCCl.N([O:27][C:28]([CH3:31])(C)C)=O>COCCOC.CCCCC>[C:28]([O:27][C:10]1[C:11]([S:16][CH2:17][C:18]([O:20][CH3:21])=[O:19])=[N:12][CH:13]=[CH:14][CH:15]=1)(=[O:4])[CH3:31]

Participants

7

Reactant 4

HCID 6344DichloromethaneHCID 10906Tert-Butyl nitriteHCID 62406Trifluoromethanesulfonic acidHCID 21933567HCID 21933567, compound

Product 1

HCID 21933564HCID 21933564, compoundYield 15.6%

Reagents, catalysts & solvents 2

HCID 8003PentaneSolventHCID 80711,2-DimethoxyethaneSolvent2×

Procedure

First, 1.92 g of trifluoromethanesulfonic acid was added dropwise to a mixture of 2.54 g of 3-amino-2-(methoxycarbonyl)methylthiopyridine, 6 ml of 1,2-dimethoxyethane, and 2 ml of dichloromethane at −10° C. After stirring at the same temperature for 10 minutes, a solution of 1.59 g of t-butyl nitrite in 1 ml of 1,2-dimethoxyethane was added dropwise to the reaction mixture at −5° C. or lower. After stirring at the same temperature for 30 minutes, n-pentane was poured into the mixture. The lower one of the two layers separated was dissolved in 3 ml of acetic anhydride, and the solution was stirred at 50° C. to 70° C. for 1 hour. The reaction mixture was cooled to room temperature and then poured into water, and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated. The residue was subjected to silica gel chromatography to give 0.48 g of 3-acetoxy-2-(methoxycarbonyl)methylthiopyridine.

Workup

  1. stirringAfter stirring at the same temperature for 30 minutes
  2. customThe lower one of the two layers separated
  3. dissolutionwas dissolved in 3 ml of acetic anhydride
  4. stirringthe solution was stirred at 50° C. to 70° C. for 1 hour
  5. additionpoured into water
  6. extractionthe mixture was extracted with t-butyl methyl ether
  7. washThe organic layer was washed with saturated aqueous sodium hydrogencarbonate solution and saturated aqueous sodium chloride solution
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-9c3277c2cc394ed69917bcbd8bb477be
Source dataset
uspto-grants-2006_09
Patent number
US07109148B2

Reaction notes

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