Acetic Acid → HCID 178474510, compound

HRID 390729Notes

Reaction equation

HRID 390729 reaction equation
[CH2:1]=[C:2]1[S:6]/[C:5](=[N:7]\[C:8](=[O:10])[CH3:9])/[N:4]([C:11]2[CH:16]=[CH:15][C:14]([C:17]([F:20])([F:19])[F:18])=[CH:13][CH:12]=2)[CH2:3]1.[C:21]([OH:24])(=[O:23])[CH3:22].ICl.C([O-])(=O)C.[K+]>ClCCl>[C:21]([O:24][CH2:1][C:2]1[S:6]/[C:5](=[N:7]\[C:8](=[O:10])[CH3:9])/[N:4]([C:11]2[CH:16]=[CH:15][C:14]([C:17]([F:20])([F:19])[F:18])=[CH:13][CH:12]=2)[CH:3]=1)(=[O:23])[CH3:22]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 24640Iodine chloride2×HCID 517044Potassium AcetateHCID 178429906HCID 178429906, compound2×

Product 1

HCID 178474510HCID 178474510, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

N-{(2Z)-5-Methylene-3-[4-(trifluoromethyl)phenyl]-1,3-thiazolidin-2-ylidene}acetamide (4.51 g, 15.0 mmol, Intermediate A6) was dissolved into acetic acid (60 mL) and treated with 1 M iodine monochloride in dichloromethane (30 mL) over three minutes. After about 15 minutes more iodine monochloride solution (0.8 mL) was added, and after another ten minutes the solution was partially concentrated, and then concentrated twice from toluene. The residue was triturated with 20% ethyl acetate/toluene and the allyl chloride was collected by filtration. The filtrate was concentrated and redissolved into acetic acid (20 mL), treated with potassium acetate (2.95 g, 30 mmol), stirred 6 hours at room temperature, and concentrated thrice from ethyl acetate. The residue was mixed with a little ethyl acetate and filtered through basic alumina with a 2% methanol/ethyl acetate rinse. The filtrate was concentrated and chromatographed on silica (ethyl acetate/dichloromethane/hexanes) to give the title compound.

Workup

  1. concentrationafter another ten minutes the solution was partially concentrated
  2. concentrationconcentrated twice from toluene
  3. customThe residue was triturated with 20% ethyl acetate/toluene
  4. filtrationthe allyl chloride was collected by filtration
  5. concentrationThe filtrate was concentrated
  6. dissolutionredissolved into acetic acid (20 mL)
  7. concentrationconcentrated thrice from ethyl acetate
  8. additionThe residue was mixed with a little ethyl acetate
  9. filtrationfiltered through basic alumina with a 2% methanol/ethyl acetate
  10. washrinse
  11. concentrationThe filtrate was concentrated
  12. customchromatographed on silica (ethyl acetate/dichloromethane/hexanes)

Sources & evidence

ORD record
ord-b1bd47735cc940ea88b48886a3791441
Source dataset
uspto-grants-2013_02
Patent number
US08383657B2

Reaction notes

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