Sodium Carbonate → 2,2-Difluoro-6-[(4,5-dimethoxy-3-methyl-2-pyridinyl)methylsulfinyl]-5H-1,3-dioxolo[4,5-f]benzimidazole

HRID 845520Notes

Reaction equation

HRID 845520 reaction equation
ClC1C=C(C=CC=1)C(OO)=[O:6].[F:12][C:13]1([F:38])[O:37][C:16]2=[CH:17][C:18]3[NH:22][C:21]([S:23][CH2:24][C:25]4[C:30]([CH3:31])=[C:29]([O:32][CH3:33])[C:28]([O:34][CH3:35])=[CH:27][N:26]=4)=[N:20][C:19]=3[CH:36]=[C:15]2[O:14]1.S([O-])([O-])(=O)=S.[Na+].[Na+].C(=O)([O-])[O-].[Na+].[Na+]>C(Cl)Cl.C(N(CC)CC)C>[F:38][C:13]1([F:12])[O:37][C:16]2=[CH:17][C:18]3[NH:22][C:21]([S:23]([CH2:24][C:25]4[C:30]([CH3:31])=[C:29]([O:32][CH3:33])[C:28]([O:34][CH3:35])=[CH:27][N:26]=4)=[O:6])=[N:20][C:19]=3[CH:36]=[C:15]2[O:14]1

Participants

7

Reactant 4

HCID 10340Sodium CarbonateHCID 24477Sodium ThiosulfateHCID 70297m-Chloroperbenzoic acidHCID 151634832,2-Difluoro-6-[(4,5-dimethoxy-3-methyl-2-pyridyl)methylthio]-5H-[1,3]-dioxolo[4,5-f]benzimidazole

Product 1

HCID 151635012,2-Difluoro-6-[(4,5-dimethoxy-3-methyl-2-pyridinyl)methylsulfinyl]-5H-1,3-dioxolo[4,5-f]benzimidazole

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8471TriethylamineSolvent

Procedure

21 ml of a 0.1N solution of m-chloroperoxybenzoic acid in methylene chloride are added dropwise to a suspension, cooled to -40° C., of 0.80 g of 2,2-difluoro-6[(4,5-dimethoxy-3-methyl-2-pyridyl)methylthio]-5H-[1,3]-dioxolo[4,5-f]-benzimidazole in 10 ml of methylene chloride in the course of 10 minutes. The mixture is stirred for a further 20 minutes, during which the temperature is allowed to rise to -20° C., and 0.5 ml of triethylamine are added and the reaction mixture is poured into 40 ml of 5% strength sodium thiosulfate solution and 5% strength sodium carbonate solution. After phase separation, the aqueous phase is extracted twice more with 20 ml of methylene chloride each time; the combined organic phases are washed with a mixture of 5 ml of sodium thiosulfate solution and 5 ml of sodium carbonate solution, dried and concentrated. The residue is recrystallized from methylene chloride/diisopropyl ether. 0.62 g (75% of theory) of the title compound is obtained; decomp. 189°-190° C.

Workup

  1. customto rise to -20° C.
  2. customAfter phase separation
  3. extractionthe aqueous phase is extracted twice more with 20 ml of methylene chloride each time
  4. washthe combined organic phases are washed with a mixture of 5 ml of sodium thiosulfate solution and 5 ml of sodium carbonate solution
  5. customdried
  6. concentrationconcentrated
  7. customThe residue is recrystallized from methylene chloride/diisopropyl ether

Sources & evidence

ORD record
ord-581b6bbeba2a4e46b82bcea0479b1b24
Source dataset
uspto-grants-1988_07
Patent number
US04758579

Reaction notes

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