Chloromethyl Methyl Ether → 3-Acetyl-4-chloromethyl-2,5-dichlorothiophene

HRID 1172137Notes

Reaction equation

HRID 1172137 reaction equation
[C:1]([C:4]1[CH:8]=[C:7]([Cl:9])[S:6][C:5]=1[Cl:10])(=[O:3])[CH3:2].CO[CH2:13][Cl:14]>[Ti](Cl)(Cl)(Cl)Cl.ClCCl>[C:1]([C:4]1[C:8]([CH2:13][Cl:14])=[C:7]([Cl:9])[S:6][C:5]=1[Cl:10])(=[O:3])[CH3:2]

Participants

5

Reactant 2

HCID 7864Chloromethyl Methyl EtherHCID 1189201-(2,5-Dichloro-3-thienyl)ethan-1-one

Product 1

HCID 178628613-Acetyl-4-chloromethyl-2,5-dichlorothiopheneYield 39.7%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 6344DichloromethaneSolvent

Procedure

33 ml of titanium tetrachloride (a 2 moles/liter dichloromethane solution, 66.0 mmoles) was dropwise added, at 10° C. with ice-cooling, to a solution of 5.0 g (32.4 mmoles) of 3-acetyl-2,5-dichlorothiophene dissolved in 26 ml (323.0 mmoles) of chloromethyl methyl ether. The mixture was stirred at room temperature for 2 hours to give rise to a reaction. After the completion of the reaction, the reaction mixture was poured into ice water, followed by extraction with chloroform. The resulting organic layer was washed with sodium bicarbonate, water and an aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate. The resulting solution was subjected to vacuum distillation to remove the solvent contained therein. The residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=9/1) to obtain 2.6 g (yield: 39.7%) of 3-acetyl-4-chloromethyl-2,5-dichlorothiophene as yellow crystals.

Workup

  1. customto give rise
  2. customto a reaction
  3. customAfter the completion of the reaction
  4. extractionfollowed by extraction with chloroform
  5. washThe resulting organic layer was washed with sodium bicarbonate, water
  6. dry with materialan aqueous sodium chloride solution in this order and then dried over anhydrous magnesium sulfate
  7. distillationThe resulting solution was subjected to vacuum distillation
  8. customto remove the solvent
  9. customThe residue was purified by silica gel column chromatography (developing solvent: hexane/ethyl acetate=9/1)

Sources & evidence

ORD record
ord-164ed6f895424c42bde2e22cb777eb37
Source dataset
uspto-grants-2010_11
Patent number
US07833939B2

Reaction notes

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