m-Formylbenzonitrile → HCID 23076531, compound

HRID 2221645Notes

Reaction equation

HRID 2221645 reaction equation
[CH:1]([C:3]1[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=1)[C:6]#[N:7])=[O:2].[CH3:11][C:12](=[N:16]O)[C:13](=O)[CH3:14].[ClH:18].C(OCC)(=O)C>>[Cl:18][CH2:11][C:12]1[N:16]=[C:1]([C:3]2[CH:4]=[C:5]([CH:8]=[CH:9][CH:10]=2)[C:6]#[N:7])[O:2][C:13]=1[CH3:14]

Participants

4

Reactant 3

HCID 90670m-FormylbenzonitrileHCID 63989692-Oxime 2,3-butanedioneHCID 21866389Hydrogen chloride-ethyl acetate

Product 1

HCID 23076531HCID 23076531, compoundYield 27%

Procedure

A mixture of 3-formylbenzonitrile (25.00 g), 2,3-butanedione-2-oxime (19.31 g) and 4N hydrogenchloride-ethyl acetate (300 mL) was stirred at room temperature for 15 hrs. The reaction mixture was concentrated and the obtained oily substance was decanted and washed with diethyl ether. A mixture of the obtained residue, tetrahydrofuran (500 mL) and thionyl chloride (34.14 g) was heated under reflux for 2 hrs. The reaction mixture was concentrated and ethyl acetate was added to the residue. The ethyl acetate layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over anhydrous magnesium sulfate and concentrated. The obtained residue was subjected to silica gel column chromatography and eluted with ethyl acetate-hexane (1:2, v/v) to obtain 3-(4-chloromethyl-5-methyl-1,3-oxazol-2-yl)benzonitrile as colorless crystals (12.01 g, yield 27%). Recrystallization from ethyl acetate-hexane gave colorless prism crystals. melting point: 100-101° C.

Workup

  1. concentrationThe reaction mixture was concentrated
  2. customthe obtained oily substance was decanted
  3. washwashed with diethyl ether
  4. additionA mixture of the obtained residue, tetrahydrofuran (500 mL) and thionyl chloride (34.14 g)
  5. temperaturewas heated
  6. temperatureunder reflux for 2 hrs
  7. concentrationThe reaction mixture was concentrated
  8. additionethyl acetate was added to the residue
  9. washThe ethyl acetate layer was washed successively with saturated aqueous sodium hydrogen carbonate solution and saturated brine
  10. dry with materialdried over anhydrous magnesium sulfate
  11. concentrationconcentrated
  12. washeluted with ethyl acetate-hexane (1:2

Sources & evidence

ORD record
ord-e59fe40a95a347788bc8692553e6a4ac
Source dataset
uspto-grants-2008_05
Patent number
US07368578B2

Reaction notes

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