Hydrochloric Acid → HCID 54242913, compound

HRID 1758035Notes

Reaction equation

HRID 1758035 reaction equation
Cl[CH2:2][C:3]([C:5](=[N:11][O:12][CH3:13])[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[O:4].[SH:14][CH2:15][CH2:16]O.Cl.C1(C)C=CC(S(O)(=O)=O)=CC=1>C(Cl)(Cl)Cl.C1(C)C=CC=CC=1.C(N(CC)CC)C>[O:4]1[C:3]([C:5](=[N:11][O:12][CH3:13])[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:2][S:14][CH2:15][CH2:16]1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 15672-MercaptoethanolHCID 6101p-Toluenesulfonic acidHCID 3017525Ethyl 4-chloro-2-(methoxyimino)-3-oxobutanoate

Product 1

HCID 54242913HCID 54242913, compoundYield 29%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolvent2×HCID 6212ChloroformSolvent2×HCID 8471TriethylamineSolvent

Procedure

A solution of ethyl 2-chloroacetyl-2-methoxyiminoacetate (65 g.) in dry chloroform (130 ml.) was added to a stirred mixture of 2-mercaptoethanol (25 g.), triethylamine (35 g.) and dry chloroform (70 ml.) at 20° C. over 30 minutes, and stirred at the same temperature for 2.5 hours. After the solution was adjusted to pH 1.0 with 10% hydrochloric acid under ice cooling, the chloroform layer was separated, washed with water twice and dried over magnesium sulfate. The solution was concentrated in vacuo at 40° C. to give yellow oil. The oil was dissolved in toluene (600 ml.), and then p-toluenesulfonic acid (5.5 g.) was added to the toluene solution. The solution was heated under reflux for 2 hours while removing the produced water. The resultant solution was allowed to cool at room temperature and filtered. The filtrate was washed with water (100 ml.) three times, a saturated aqueous solution of sodium bicarbonate (100 ml.) twice and water (100 ml.) twice in turn, and then dried over magnesium sulfate. The solution was concentrated under reduced pressure. The residue was subjected to column chromatography on silica gel "Kieselgel 60" [Trademark: manufactured by E. Merck] (1 kg.) and eluted with benzene. After the eluate was concentrated under reduced pressure, the residue was washed with diisopropyl ether and dried to give ethyl 2-(2,3-dihydro-1,4-oxathiin-6-yl)-2-methoxyiminoacetate (syn isomer, 21 g.), pale yellow crystals, mp. 64° to 66° C.

Workup

  1. customthe chloroform layer was separated
  2. washwashed with water twice
  3. dry with materialdried over magnesium sulfate
  4. concentrationThe solution was concentrated in vacuo at 40° C.
  5. customto give yellow oil
  6. temperatureThe solution was heated
  7. temperatureunder reflux for 2 hours
  8. customwhile removing the produced water
  9. filtrationfiltered
  10. washThe filtrate was washed with water (100 ml.) three times
  11. dry with materiala saturated aqueous solution of sodium bicarbonate (100 ml.) twice and water (100 ml.) twice in turn, and then dried over magnesium sulfate
  12. concentrationThe solution was concentrated under reduced pressure
  13. washeluted with benzene
  14. concentrationAfter the eluate was concentrated under reduced pressure
  15. washthe residue was washed with diisopropyl ether
  16. customdried

Sources & evidence

ORD record
ord-fb2b2270580247e99712126ec8e7e5a1
Source dataset
uspto-grants-1983_02
Patent number
US04371531

Reaction notes

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