N,N-Dimethylaniline → 4-(Dimethylcarbamoyloximino)-1,3-oxathiolane

HRID 1076405Notes

Reaction equation

HRID 1076405 reaction equation
[N:1](=[C:3]1[CH2:7][O:6][CH2:5][S:4]1)[OH:2].[C:8](Cl)(Cl)=[O:9].[CH3:12][N:13](C)[C:14]1C=CC=CC=1>CCOCC>[CH3:12][N:13]([CH3:14])[C:8]([O:2][N:1]=[C:3]1[CH2:7][O:6][CH2:5][S:4]1)=[O:9]

Participants

5

Reactant 3

HCID 949N,N-DimethylanilineHCID 6371PhosgeneHCID 85838761HCID 85838761, compound

Product 1

HCID 536842654-(Dimethylcarbamoyloximino)-1,3-oxathiolane

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Conditions

Temperature
-10 °C

Procedure

A quantity of 6 grams of 4-oximino-1,3-oxathiolane dissolved in 100 ml of anhydrous ether was added over 30 minutes to a solution of 10 grams of phosgene in 100 ml of anhydrous ether maintained at -10°C. A quantity of 6 grams of N,N-dimethylaniline dissolved in 200 ml of anhydrous ether was then added dropwise to the cooled phosgene/oxime solution over a 30 minute period. The heterogeneous mixture was stirred at -10° for 2 hours, filtered in an inert atmosphere and the filtrate concentrated under a vacuum to about 250 ml. The concentrated solution was cooled to 10° in a stirring vessel, 12 ml of 40 percent aqueous dimethylamine was added dropwise, and the mixture stirred for 1 hour at 10°. A volume of 100 ml of water was added, the phases separated, and the organic phase washed with two 50 ml portions of saturated brine. The three aqueous solutions were extracted sequentially with a volume of 300 ml of ether. The combined ether solutions were dried over magnesium sulfate, filtered, and evaporated. Recrystallization of the crude 4-(dimethylcarbamoyloximino)-1,3-oxathiolane afforded pure product, mp 87.5°-88.0°.

Workup

  1. filtrationfiltered in an inert atmosphere
  2. concentrationthe filtrate concentrated under a vacuum to about 250 ml
  3. temperatureThe concentrated solution was cooled to 10° in a stirring vessel
  4. addition12 ml of 40 percent aqueous dimethylamine was added dropwise
  5. stirringthe mixture stirred for 1 hour at 10°
  6. additionA volume of 100 ml of water was added
  7. customthe phases separated
  8. washthe organic phase washed with two 50 ml portions of saturated brine
  9. extractionThe three aqueous solutions were extracted sequentially with a volume of 300 ml of ether
  10. dry with materialThe combined ether solutions were dried over magnesium sulfate
  11. filtrationfiltered
  12. customevaporated
  13. customRecrystallization of the crude 4-(dimethylcarbamoyloximino)-1,3-oxathiolane afforded pure product, mp 87.5°-88.0°

Sources & evidence

ORD record
ord-fb242824cced4e1e9c329bcefc19cb30
Source dataset
uspto-grants-1976_05
Patent number
US03956500

Reaction notes

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