Dimethyl Sulfoxide → HCID 13557279, compound

HRID 231409Notes

Reaction equation

HRID 231409 reaction equation
C([O-])(=[O:3])C.[Na+].[OH:6][N:7]1[C:11](=[O:12])[C:10]2=[CH:13][CH:14]=[CH:15][CH:16]=[C:9]2[C:8]1=[O:17].Br[CH2:19][CH2:20][C:21]([CH3:28])(C)[C:22]([O:24][CH2:25][CH3:26])=S.[CH3:29][S:30](C)=O>C(OCC)(=O)C>[CH3:28][C:21]([S:30][CH3:29])([CH2:20][CH2:19][O:6][N:7]1[C:8](=[O:17])[C:9]2=[CH:16][CH:15]=[CH:14][CH:13]=[C:10]2[C:11]1=[O:12])[C:22]([O:24][CH2:25][CH3:26])=[O:3]

Participants

6

Reactant 4

HCID 679Dimethyl Sulfoxide2×HCID 10665N-HydroxyphthalimideHCID 517045Sodium AcetateHCID 54203470HCID 54203470, compound

Product 1

HCID 13557279HCID 13557279, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Sodium acetate (53.0 g, 0.647 mole) was added to a stirred solution of N-hydroxyphthalimide (95.9 g, 0.588 mole) in dimethyl sulfoxide (600 ml) under a nitrogen atmosphere. The resulting mixture was stirred for two hours at ambient temperature, then ethyl 4-bromo-2-methyl-2-methylthiobutanoate (150.0 g, 0.588 mole) in dimethyl sulfoxide (400 ml) was added. The reaction mixture was heated at 70°-80° C. for four days. Upon cooling, the reaction mixture was poured into crushed ice and stirred. A solid precipitate was removed by filtration (50 g). The aqueous filtrate was then extracted with ether (500 ml) and methylene chloride (2×250 ml). The extracts were combined, dried and concentrated under reduced pressure to yield a brown oil. The brown oil and the solid precipitate were combined, dissolved in ethyl acetate, and washed with a 1N aqueous solution of sodium hydroxide (3×100 ml) to remove unreacted N-hydroxyphthalimide and dimethyl sulfoxide. The dried organic extract was concentrated under reduced pressure to yield a brown residue. The residue was subjected to column chromatography on silica gel. Elution was accomplished with ethyl acetate:heptane (1:9). Appropriate fractions were combined and concentrated under reduced pressure to yield 93.0 g of ethyl 2-methyl-2-methylthio-4-(phthalimidooxy)butanoate. The NMR spectrum was consistent with the proposed structure.

Workup

  1. temperatureThe reaction mixture was heated at 70°-80° C. for four days
  2. temperatureUpon cooling
  3. additionthe reaction mixture was poured
  4. custominto crushed ice
  5. stirringstirred
  6. customA solid precipitate was removed by filtration (50 g)
  7. extractionThe aqueous filtrate was then extracted with ether (500 ml) and methylene chloride (2×250 ml)
  8. customdried
  9. concentrationconcentrated under reduced pressure
  10. customto yield a brown oil
  11. washwashed with a 1N aqueous solution of sodium hydroxide (3×100 ml)
  12. customto remove unreacted N-hydroxyphthalimide and dimethyl sulfoxide
  13. extractionThe dried organic extract
  14. concentrationwas concentrated under reduced pressure
  15. customto yield a brown residue
  16. washElution
  17. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-f37f2995df5a45719871607c630e231c
Source dataset
uspto-grants-1989_07
Patent number
US04846875

Reaction notes

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