Diethyl (ethoxymethylene)malonate → Diethyl 2-(4-methoxy-phenylsulfanylmethylene)-malonate

HRID 324586Notes

Reaction equation

HRID 324586 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([SH:9])=[CH:5][CH:4]=1.CCO[CH:13]=[C:14]([C:20]([O:22][CH2:23][CH3:24])=[O:21])[C:15]([O:17][CH2:18][CH3:19])=[O:16].O.S([O-])(O)(=O)=O.[Na+]>>[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([S:9][CH:13]=[C:14]([C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:5][CH:4]=1

Participants

4

Reactant 3

HCID 6871Diethyl (ethoxymethylene)malonateHCID 127654-MethoxybenzenethiolHCID 23673662Sodium bisulfate monohydrate

Product 1

HCID 15512566Diethyl 2-(4-methoxy-phenylsulfanylmethylene)-malonate

Conditions

Temperature
166 °C

Procedure

4-Methoxybenzenethiol (X-1; 5 g, 0.0357 mol), diethyl ethoxymethylene malonate (7.3 ml) and sodium hydrogen sulfate monohydrate (100 mg) were heated with stirring in an oil bath at 166° C. for 2 h. After cooling, ice water was added to the reaction mixture and extracted with ether. The crude product was purified by silica gel (250 g) and ethyl acetate/hexane (1:4) to give compound (XI-1) (5.7 g, 51%) as an oil. NMR(CDCl3):1.29(3H,t, J=7.1), 1.38(3H, t, J=7.1), 3.83(3H, s), 4.23(2H, q, J=7.1), 4.35(2H, q, J=7.1), 6.93, 7.45(4H, AB, J=8.8), 8.30(1H,s)

Workup

  1. temperatureAfter cooling
  2. extractionextracted with ether
  3. customThe crude product was purified by silica gel (250 g) and ethyl acetate/hexane (1:4)
  4. customto give compound (XI-1) (5.7 g, 51%) as an oil

Sources & evidence

ORD record
ord-082a0c1f8d404c62a4f16f89ea74f112
Source dataset
uspto-grants-2001_04
Patent number
US06218427B1

Reaction notes

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