Hydrochloric Acid → HCID 22221161, compound

HRID 1794342Notes

Reaction equation

HRID 1794342 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([C:8]2[O:12][N:11]=[CH:10][C:9]=2[C:13](OCC)=O)[S:5][C:6]=1[Cl:7].[H-].C([Al+]CC(C)C)C(C)C.[ClH:28]>O1CCCC1>[Cl:28][CH2:13][C:9]1[CH:10]=[N:11][O:12][C:8]=1[C:4]1[S:5][C:6]([Cl:7])=[C:2]([Cl:1])[CH:3]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 21225700DiisobutylaluminumhydrideHCID 22221187HCID 22221187, compound

Product 1

HCID 22221161HCID 22221161, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of ethyl 5-(4,5-dichloro-2-thienyl)isoxazole-4-carboxylate (3.30 g) in tetrahydrofuran (60 ml) was gently added diisobutylaluminum hydride (0.95 M hexane solution, 29.7 ml) at 0° C. and the mixture was stirred at room temperature for 2 hr. The reaction mixture was poured into dilute hydrochloric acid, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated. The residue was dissolved in toluene (60 ml), thionyl chloride (2.02 g) was added dropwise at 0° C., and the mixture was stirred at room temperature for 1 hr. The reaction mixture was concentrated, saturated aqueous sodium hydrogencarbonate was added to the residue, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated. The residue was subjected to silica gel column chromatography, and 4-chloromethyl-5-(4,5-dichloro-2-thienyl)isoxazole (2.41 g, yield 79%) was obtained as crystals from a fraction eluted with ethyl acetate-hexane (1:9, volume ratio) and recrystallized from hexane to give a colorless prism. melting point: 60–61° C.

Workup

  1. customat 0° C.
  2. extractionthe mixture was extracted with ethyl acetate
  3. washThe ethyl acetate layer was washed with saturated brine
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. dissolutionThe residue was dissolved in toluene (60 ml)
  7. additionthionyl chloride (2.02 g) was added dropwise at 0° C.
  8. stirringthe mixture was stirred at room temperature for 1 hr
  9. concentrationThe reaction mixture was concentrated
  10. additionsaturated aqueous sodium hydrogencarbonate was added to the residue
  11. extractionthe mixture was extracted with ethyl acetate
  12. washThe ethyl acetate layer was washed with saturated brine
  13. dry with materialdried (MgSO4)
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-44d35e08bb9d4f22a4309b1a2b8e309d
Source dataset
uspto-grants-2006_04
Patent number
US07022725B2

Reaction notes

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