Glyoxylic Acid → glyoxylic acid-O-[2-[(2,6-dichloro-3-methylphenyl)amino]phenylmethyl] oxime

HRID 343885Notes

Reaction equation

HRID 343885 reaction equation
[Cl:1][C:2]1[C:7]([CH3:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[NH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[CH2:17][O:18][NH2:19].[C:20]([OH:24])(=[O:23])[CH:21]=O>C1COCC1.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>[Cl:1][C:2]1[C:7]([CH3:8])=[CH:6][CH:5]=[C:4]([Cl:9])[C:3]=1[NH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[CH2:17][O:18][N:19]=[CH:21][C:20]([OH:24])=[O:23]

Participants

5

Reactant 2

HCID 760Glyoxylic AcidHCID 67560731O-[2-[(2,6-dichloro-3-methylphenyl)amino]phenylmethyl]hydroxylamine

Product 1

HCID 85040516glyoxylic acid-O-[2-[(2,6-dichloro-3-methylphenyl)amino]phenylmethyl] oximeYield 34.8%

Reagents, catalysts & solvents 2

HCID 311Citric AcidSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A solution in THF of O-[2-[(2,6-dichloro-3-methylphenyl)amino]phenylmethyl]hydroxylamine (0.50 g, 1.71 mmol), prepared as in step 3, and glyoxylic acid (0.18 g, 1.99 mmol) in THF was stirred for 16 hours. The solution was then diluted with aqueous citric acid and extracted with ethyl acetate (100 mL). The extract was washed with brine, dried over MgSO4, filtered, and concentrated in vacuo to yield an off white solid which was purified by chromatography on silica gel (10% methanol-chloroform). The resulting residue was crystallized from EtOAc/hexanes to provide glyoxylic acid-O-[2-[(2,6-dichloro-3-methylphenyl)amino]phenylmethyl] oxime (0.21 g, 33%) as a white solid. mp 185°-187° C. 1H NMR (300 MHz, DMSO-d6) δ2.38 (s, 3 H), 5.17 (s, 2 H), 6.19 (d, J=7.5 Hz, 1 H), 6.82 (t, J=7.5 Hz, 1 H), 6.97 (s, 1 H), 7.09 (t, J=7.5 Hz, 1 H), 7.25 (m, 2 H), 7.44 (m, 2 H). MS (DCI/NH3) m/z 353 (M+H)+. Anal. Calcd for C16H14N2O3Cl2 ×1.0 H2O: C, 51.76; H, 4.34; N, 7.54. Found: C, 51.78; H, 3.69; N, 7.15.

Workup

  1. extractionextracted with ethyl acetate (100 mL)
  2. washThe extract was washed with brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customto yield an off white solid which
  7. customwas purified by chromatography on silica gel (10% methanol-chloroform)
  8. customThe resulting residue was crystallized from EtOAc/hexanes

Sources & evidence

ORD record
ord-8d326c441e2e4b16b60c6cdf4c36b7e6
Source dataset
uspto-grants-1999_01
Patent number
US05863946

Reaction notes

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