Formaldehyde → HCID 15451765, compound

HRID 1738349Notes

Reaction equation

HRID 1738349 reaction equation
[BH4-].[Na+].[CH3:3][NH:4][C:5]1[C:6]([CH3:18])=[C:7]([CH:11]=[CH:12][C:13]=1[S:14]([CH3:17])(=[O:16])=[O:15])[C:8]([OH:10])=[O:9].C=O.F[C:22](F)(F)C(O)=O.[OH-].[Na+]>O1CCCC1.O>[CH3:3][N:4]([CH3:22])[C:5]1[C:6]([CH3:18])=[C:7]([CH:11]=[CH:12][C:13]=1[S:14]([CH3:17])(=[O:16])=[O:15])[C:8]([OH:10])=[O:9]

Participants

8

Reactant 5

HCID 712FormaldehydeHCID 6422Trifluoroacetic acidHCID 14798Sodium HydroxideHCID 4311764Sodium borohydrideHCID 15451764HCID 15451764, compound

Product 1

HCID 15451765HCID 15451765, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Procedure

Sodium borohydride (1.4 g, 36 mmol) was carefully added to a suspension of 1.53 g (6.30 mmol) of 3-methylamino-2-methyl-4-methylsulfonylbenzoic acid and 1.8 g (60 mmol) of paraformaldehyde in 75 mL of dry tetrahydrofuran under a nitrogen atmosphere. A 30 mL aliquot of trifluoroacetic acid was then added dropwise over 1 hour. Gas evolution was vigorous at first, but then subsided as the grey-white suspension was allowed to stir at room temperature. After 8 hours, the reaction was found to be complete by high pressure liquid chromatographic analysis (HPLC). The mixture was poured into 90 mL of a 25 percent aqueous sodium hydroxide solution containing ice, diluted with water and washed with ethyl acetate. The aqueous solution was then acidified with concentrated aqueous hydrochloric acid and the resulting mixture was extracted with ethyl acetate. The organic extract was mixed with dilute aqueous sodium bicarbonate solution and the aqueous phase was collected, acidified with 1N aqueous hydrochloric acid, and extracted with ethyl acetate. The organic extract obtained was dried over sodium sulfate and concentrated by evaporation under reduced pressure. The resulting residue was purified by flash column chromatography on silica gel, eluting with a 1:1 mixture of ethyl acetate and petroleum ether containing 1 percent acetic acid, to obtain 1.49 g (92 percent of theory) of the title compound as a yellow syrup which solidified on standing and melted at 113-114° C.

Workup

  1. additioncontaining ice
  2. washwashed with ethyl acetate
  3. extractionthe resulting mixture was extracted with ethyl acetate
  4. extractionThe organic extract
  5. additionwas mixed with dilute aqueous sodium bicarbonate solution
  6. customthe aqueous phase was collected
  7. extractionextracted with ethyl acetate
  8. extractionThe organic extract
  9. customobtained
  10. dry with materialwas dried over sodium sulfate
  11. concentrationconcentrated by evaporation under reduced pressure
  12. customThe resulting residue was purified by flash column chromatography on silica gel
  13. washeluting with a 1:1 mixture of ethyl acetate and petroleum ether containing 1 percent acetic acid

Sources & evidence

ORD record
ord-972dd4fb4f1f46e1b0684fd5e3067c8f
Source dataset
uspto-grants-1999_10
Patent number
US05962690

Reaction notes

Loading…