Diethyl Carbonate → Ethyl 3-methoxy-5-methylthio-4-propoxy-alpha-cyanobenzeneacetate

HRID 728063Notes

Reaction equation

HRID 728063 reaction equation
[C:1](=[O:8])([O:5][CH2:6][CH3:7])OCC.[CH3:9][O:10][C:11]1[CH:12]=[C:13]([CH2:23][C:24]#[N:25])[CH:14]=[C:15]([S:21][CH3:22])[C:16]=1[O:17][CH2:18][CH2:19][CH3:20]>C1(C)C=CC=CC=1>[CH3:9][O:10][C:11]1[CH:12]=[C:13]([CH:23]([C:24]#[N:25])[C:1]([O:5][CH2:6][CH3:7])=[O:8])[CH:14]=[C:15]([S:21][CH3:22])[C:16]=1[O:17][CH2:18][CH2:19][CH3:20]

Participants

4

Reactant 2

HCID 7766Diethyl CarbonateHCID 150449673-Methoxy-5-methylthio-4-propoxyphenyl acetonitrile

Product 1

HCID 15044969Ethyl 3-methoxy-5-methylthio-4-propoxy-alpha-cyanobenzeneacetateYield 92%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

1.4 g of sodium was dissolved in absolute EtOH with warming to 70° C., then EtOH was removed under vacuum to give a white solid residue of NaOEt. A mixture of 35 ml of diethyl carbonate, 43 ml of toluene, 13.46 g of 3-methoxy-5-methylthio-4-propoxyphenyl acetonitrile was added slowly. The mixture was refluxed for 3 hours. EtOH was removed under vacuum. The solid was filtered and washed with toluene (3×) and ether (3×). The solid was suspended in 200 ml of H2O and acidified with 6N HCl. The solid dissolved and a brown oil formed. The oil was extracted with ether (3×), the combined ether extracts were washed with H2O (2×), saturated NaCl (2×) and finally dried over MgSO4. The ether was removed under vacuum to give 16 g (92% yield) of ethyl 3-methoxy-5-methylthio-4-propoxy-α-cyanobenzeneacetate.

Workup

  1. additionwas added slowly
  2. temperatureThe mixture was refluxed for 3 hours
  3. customEtOH was removed under vacuum
  4. filtrationThe solid was filtered
  5. washwashed with toluene (3×) and ether (3×)
  6. dissolutionThe solid dissolved
  7. customa brown oil formed
  8. extractionThe oil was extracted with ether (3×)
  9. washthe combined ether extracts were washed with H2O (2×), saturated NaCl (2×)
  10. dry with materialfinally dried over MgSO4
  11. customThe ether was removed under vacuum

Sources & evidence

ORD record
ord-f3b1650efba14bb6ba381feb0e256573
Source dataset
uspto-grants-1991_09
Patent number
US05047420

Reaction notes

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