Diethyl Ether → 2-[4,5-Bis-(p-methoxyphenyl)-thiazol-2-ylthio]-acetaldehyde-dimethylacetal

HRID 544654Notes

Reaction equation

HRID 544654 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:13]([C:14]3[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=3)[S:12][C:11](=[S:22])[N:10]=2)=[CH:5][CH:4]=1.[CH3:23][O:24][CH:25]([O:28][CH3:29])[CH2:26]Br.[H-].[Na+].C(OCC)C>CN(C)P(=O)(N(C)C)N(C)C>[CH3:23][O:24][CH:25]([O:28][CH3:29])[CH2:26][S:22][C:11]1[S:12][C:13]([C:14]2[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=2)=[C:9]([C:6]2[CH:7]=[CH:8][C:3]([O:2][CH3:1])=[CH:4][CH:5]=2)[N:10]=1

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 24758Sodium hydrideHCID 816722-Bromo-1,1-dimethoxyethaneHCID 132096564,5-Bis-(p-methoxyphenyl)-thiazoline-2-thione

Product 1

HCID 132096712-[4,5-Bis-(p-methoxyphenyl)-thiazol-2-ylthio]-acetaldehyde-dimethylacetal

Reagents, catalysts & solvents 1

HCID 12679HexamethylphosphoramideSolvent

Procedure

20.0 g of 4,5-bis-(p-methoxyphenyl)-thiazoline-2-thione are dissolved in 100 ml of hexamethylphosphoric acid triamide at 35°. The mixture is allowed to cool to 20°, first 11.2 g of 2-bromoacetaldehyde-dimethylacetal and then, in portions, 2.9 g of 50% strength sodium hydride suspension (in mineral oil, de-oiled with hexane) are added, the reaction temperature being maintained at 25°-30° by cooling. The mixture is then stirred at room temperature for 1 hour, poured onto ice, the oil which separates is brought into solution with diethyl ether, and the organic phase is removed. The aqueous phase is extracted by shaking again with 200 ml of diethyl ether. The organic phases are combined, washed with 200 ml of 2 N sodium hydroxide solution, dried over magnesium sulphate and concentrated by evaporation. The oily crude product is crystallised from hexane and made into a slurry with methanol. 2-[4,5-bis-(p-methoxyphenyl)-thiazol-2-ylthio]-acetaldehyde-dimethylacetal having a melting point of 60°-61° is obtained.

Workup

  1. temperatureto cool to 20°
  2. temperaturethe reaction temperature being maintained at 25°-30°
  3. temperatureby cooling
  4. additionpoured onto ice
  5. customthe organic phase is removed
  6. extractionThe aqueous phase is extracted
  7. stirringby shaking again with 200 ml of diethyl ether
  8. washwashed with 200 ml of 2 N sodium hydroxide solution
  9. dry with materialdried over magnesium sulphate
  10. concentrationconcentrated by evaporation
  11. customThe oily crude product is crystallised from hexane

Sources & evidence

ORD record
ord-9660521e5740458fa2c68e5d3d384916
Source dataset
uspto-grants-1984_05
Patent number
US04451471

Reaction notes

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