Dimethyl Sulfoxide → 1-(2-Methoxy-6-((4-methoxybenzyl)oxy)phenyl)-3,3-bis(methylthio)prop-2-en-1-one

HRID 1878319Notes

Reaction equation

HRID 1878319 reaction equation
CC(C)([O-])C.[Li+].[CH3:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=2)[C:10]=1[C:25](=[O:27])[CH3:26].[C:28](=S)=[S:29].IC.[CH3:33][S:34]([CH3:36])=O>C(OCC)(=O)C.O>[CH3:7][O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][C:20]([O:23][CH3:24])=[CH:21][CH:22]=2)[C:10]=1[C:25](=[O:27])[CH:26]=[C:33]([S:29][CH3:28])[S:34][CH3:36]

Participants

8

Reactant 5

HCID 679Dimethyl SulfoxideHCID 6328Methyl iodideHCID 6348Carbon DisulfideHCID 236647642-Propanol, 2-methyl-, lithium salt (1:1)HCID 56973356HCID 56973356, compound

Product 1

HCID 583058241-(2-Methoxy-6-((4-methoxybenzyl)oxy)phenyl)-3,3-bis(methylthio)prop-2-en-1-oneYield 77%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of lithium tert-butoxide (602.4 g, 7.52 mol) in anhydrous DMSO (11.0 L) under a nitrogen atmosphere is added 1-(2-methoxy-6-(4-methoxybenzyloxy)phenyl)ethanone (1000.0 g, 3.49 mol). The resulting mixture is stirred 30 min and CS2 (259 mL, 4.296 mol) is slowly added over 1 to 1.5 h while maintaining the internal temperature below 30° C. After stirring for at least one hour at ambient temperature, iodomethane (1000 g, 7.045 mol) is added slowly while maintaining the internal temperature below 30° C. The resulting mixture is stirred at ambient temperature for 30 min to one hour. Reaction completion is confirmed by HPLC. The resulting reaction mixture is cooled, followed by extractive work up with water and ethyl acetate. The resulting organic portion is concentrated to provide a slurry which is filtered and washed with ethyl acetate (1 L), followed by methyl t-butyl ether (2×1 L). The isolated solid is dried at 40° C. in a vacuum oven to provide 1057 g (77%) of the title compound. mp 93-94° C.; ES/MS m/z 391.2 [M+1]+.

Workup

  1. temperaturewhile maintaining the internal temperature below 30° C
  2. stirringAfter stirring for at least one hour at ambient temperature
  3. temperaturewhile maintaining the internal temperature below 30° C
  4. stirringThe resulting mixture is stirred at ambient temperature for 30 min to one hour
  5. customReaction completion
  6. customThe resulting reaction mixture
  7. temperatureis cooled
  8. concentrationThe resulting organic portion is concentrated
  9. customto provide a slurry which
  10. filtrationis filtered
  11. washwashed with ethyl acetate (1 L)
  12. customThe isolated solid is dried at 40° C. in a vacuum oven

Sources & evidence

ORD record
ord-0fa433aebe304e4ba3e021924e83166f
Source dataset
uspto-grants-2012_11
Patent number
US08314108B2

Reaction notes

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