Diethyl Oxalate → HCID 135980894, compound

HRID 720276Notes

Reaction equation

HRID 720276 reaction equation
[C:1]([O:8][CH2:9][CH3:10])(=[O:7])[C:2](OCC)=O.[CH3:11][O:12][CH2:13][C:14]([O:16]C)=O.[H-].[Na+].[O-]CC.[Na+].S(O)(O)(=O)=O.[CH3:29][S:30][C:31](=[NH:33])[NH2:32]>O1CCCC1.C(O)C.C(O)(=O)C>[CH2:9]([O:8][C:1]([C:2]1[N:32]=[C:31]([S:30][CH3:29])[NH:33][C:14](=[O:16])[C:13]=1[O:12][CH3:11])=[O:7])[CH3:10]

Participants

9

Reactant 5

HCID 7268Diethyl OxalateHCID 24758Sodium hydrideHCID 752702-Methyl-2-thiopseudourea sulfateHCID 80507Methyl methoxyacetateHCID 2723922Sodium ethoxide

Product 1

HCID 135980894HCID 135980894, compoundYield 26.5%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
22 °C

Procedure

A solution of diethyl oxalate (27.2 g, 0.186 mol) and methyl methoxyacetate (19.38 g, 0.186 mol) in dry tetrahydrofuran (250 ml) was treated at 22° C. with sodium hydride (8.15 g of a 60% dispersion in mineral oil, 0.203 mol) and the resulting mixture was stirred at 22° C. for 18 h. The tetrahydrofuran was then evaporated under reduced pressure and the residual orange syrup was dissolved in a solution of sodium ethoxide (0.189 mol, prepared from 4.35 g of sodium) in ethanol (300 ml). Then powdered 2-methyl-2-thiopseudourea sulfate (25.9 g, 0.093 mol) was added and the resulting mixture was stirred at 22° C. for 1 h and then heated at 60° C. for 2 h. Acetic acid (5 ml) was then added to the gel like reaction mixture and the ethanol was evaporated under reduced pressure. The residual paste was partitioned between water and dichloromethane and the aqueous phase was extracted five times with dichloromethane. The combined organic phases were washed with brine and dried over anhydrous magnesium sulfate. Evaporation of the solvent gave a semi-solid residue which was triturated with ethyl acetate (100 ml). The light yellow solid formed was collected (10.02 g) and chromatographed on silica gel. Elution with a mixture of dichloromethane and ethanol (98:2) gave 6.02 g (13% yield) of the title ester as white needles; mp 171–173° C. (ethyl acetate). 1HNMR 400 MHz (CDCl3) δ (ppm): 1.42 (3H, t, J=7.1 Hz, CH3), 2.62 (3H, s, SCH3), 3.99 (3H, s, OCH3), 4.43 (2H, q, J=7.1 Hz, CH2), 11.8 (1H, broad s, NH). Anal. Calcd for C9H12N2O4S: C 44.25; H, 4.95; N, 11.47. Found: C 44.22; H, 5.04; N, 11.46.

Workup

  1. customThe tetrahydrofuran was then evaporated under reduced pressure
  2. stirringthe resulting mixture was stirred at 22° C. for 1 h
  3. temperatureheated at 60° C. for 2 h
  4. customthe ethanol was evaporated under reduced pressure
  5. customThe residual paste was partitioned between water and dichloromethane
  6. extractionthe aqueous phase was extracted five times with dichloromethane
  7. washThe combined organic phases were washed with brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customEvaporation of the solvent
  10. customgave a semi-solid residue which
  11. customwas triturated with ethyl acetate (100 ml)
  12. customThe light yellow solid formed
  13. customwas collected (10.02 g)
  14. customchromatographed on silica gel
  15. washElution
  16. additionwith a mixture of dichloromethane and ethanol (98:2)

Sources & evidence

ORD record
ord-fdf9eccd52534d1f8226144bec2a8143
Source dataset
uspto-grants-2006_11
Patent number
US07135467B2

Reaction notes

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