Pyridine → 2-[(2,6-dichloro-3-methylphenyl)aminophenyl]benzaldehyde-O-carboxymethyl oxime

HRID 357284Notes

Reaction equation

HRID 357284 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:18]=[CH:17][CH:16]=[CH:15][C:12]=1[CH:13]=O.Cl.[C:20]([CH2:23][O:24][NH2:25])([OH:22])=[O:21].[C:26](CON)(O)=O.N1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1>C(O)C>[C:20]([CH2:23][O:24][N:25]=[CH:33][C:34]1[CH:35]=[CH:36][CH:37]=[CH:26][C:13]=1[C:12]1[CH:15]=[CH:16][CH:17]=[CH:18][C:11]=1[NH:10][C:3]1[C:4]([Cl:9])=[CH:5][CH:6]=[C:7]([CH3:8])[C:2]=1[Cl:1])([OH:22])=[O:21]

Participants

5

Reactant 3

HCID 1049PyridineHCID 2723609Aminooxyacetic acid hemihydrochlorideHCID 150273772-[(2,6-Dichloro-3-methylphenyl)amino]benzaldehyde

Product 1

HCID 1317209532-[(2,6-dichloro-3-methylphenyl)aminophenyl]benzaldehyde-O-carboxymethyl oximeYield 54%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A mixture in ethanol (20 mL) of 2-[(2,6-dichloro-3-methylphenyl)amino]benzaldehyde (1.10 g, 3.9 mmol), prepared as in step 1 above, O-carboxymethyl hydroxylamine hemihydrochloride (0.945 g, 4.3 mmol), and pyridine (8 mL) was stirred at reflux for 18 hours. After cooling the reaction was concentrated and the residue was acidified to pH 2 with 10% aqueous citric acid. The mixture was then extracted with ethyl acetate (4×100 mL), the combined organic layers were washed with water and brine, dried over MgSO4, filtered, evaporated in vacuo. Purification by chromatography on silica gel (9:1 hexane/ethyl acetate, followed by 9:1 CH2Cl2 /CH3OH) and crystallization from ethyl acetate-ether-hexane gave 2-[(2,6-dichloro-3-methylphenyl)aminophenyl]benzaldehyde-O-carboxymethyl oxime (751 mg, 54%). mp 129°-130° C.; 1H NMR (300 MHz, DMSO-d6)δ2.37 (s, 3H), 4.70 (s, 2H), 6.21 (d, J=9 Hz, 1H), 6.83 (t, J=7.5 Hz, 1H), 7.17 (t, J=7.5 Hz, 1H), 7.33 (d, J=9 Hz, 1H), 7.45 (d, J=9 Hz, 1H), 7.50 (d, J=9 Hz, 1H), 8.58 (s, 1H), 8.73 (s, 1H), 12.81 (broad s, 1H); MS (DCI-NH3) m/z 353 (M+H)+, 370 (M+NH4)+. Anal. Calcd for C16H14Cl2N2 O3 : C, 54.41, H, 4.00, N, 7.93. Found: C, 54.13, H, 3.92; N, 7.69.

Workup

  1. temperatureat reflux for 18 hours
  2. temperatureAfter cooling the reaction
  3. concentrationwas concentrated
  4. extractionThe mixture was then extracted with ethyl acetate (4×100 mL)
  5. washthe combined organic layers were washed with water and brine
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. customevaporated in vacuo
  9. customPurification by chromatography
  10. customon silica gel (9:1 hexane/ethyl acetate, followed by 9:1 CH2Cl2 /CH3OH) and crystallization from ethyl acetate-ether-hexane

Sources & evidence

ORD record
ord-75869f7ed53c4f999bf6cc48f521a506
Source dataset
uspto-grants-1998_11
Patent number
US05840758

Reaction notes

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