Pyridine → N-methyl-N-methoxy-(E)-5-methyl-4-bis(4-fluorophenyl)methylidene-2-hexenamide

HRID 2380643Notes

Reaction equation

HRID 2380643 reaction equation
[CH3:1][CH:2]([CH3:24])[C:3](=[C:9]([C:17]1[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=1)[C:10]1[CH:15]=[CH:14][C:13]([F:16])=[CH:12][CH:11]=1)/[CH:4]=[CH:5]/[C:6]([OH:8])=O.[C:25](Cl)(=[O:29])C(Cl)=O.Cl.CONOOC.[N:38]1C=CC=C[CH:39]=1>C1C=CC=CC=1.C(OCC)C>[CH3:39][N:38]([O:29][CH3:25])[C:6](=[O:8])/[CH:5]=[CH:4]/[C:3](=[C:9]([C:10]1[CH:15]=[CH:14][C:13]([F:16])=[CH:12][CH:11]=1)[C:17]1[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=1)[CH:2]([CH3:1])[CH3:24]

Participants

7

Reactant 4

HCID 1049PyridineHCID 65578Oxalyl chlorideHCID 18954766(E)-5-methyl-4-bis(4-fluorophenyl)methylidene-2-hexenoic acidHCID 22015712N,O-dimethoxyhydroxylamine hydrochloride

Product 1

HCID 19107622N-methyl-N-methoxy-(E)-5-methyl-4-bis(4-fluorophenyl)methylidene-2-hexenamideYield 83.9%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
60 °C

Procedure

To the above carboxylic acid (1.70 g, 5.2 mmol) dissolved in benzene (15 ml) was added under argon atmosphere oxalyl chloride (1.27 g, 0.87 ml, 10.0 mmol) distilled right before use. After stirring at 60° C. for 2 hours, the solvent and excess oxalyl chloride were removed by evaporation at 60° C. under 20 Torr. To the residue dissolved in dichloromethane (25 ml) were added N,O-dimethoxyhydroxylamine hydrochloride (0.52 g, 5.34 mmol) and pyridine (0.85 g, 0.86 ml, 10.7 mmol), and the whole was stirred at room temperature overnight. The mixture was diluted with diethyl ether (100 ml), and the organic layer was washed with saturated ammonium chloride aq solution (100 ml×twice), dried over anhydrous magnesium sulfate, and concentrated in vacuo. The resulting crude product was purified by column chromatography (silica gel, ethyl acetate:hexane=3:7) to give 1.62 g (82% yield) of N-methyl-N-methoxy-(E)-5-methyl-4-bis (4-fluorophenyl)methylidene-2-hexenamide. mp=109° -110° C. Rf =0.48 (hexane:ethyl acetate=2:1) IR (KBr): 3200, 3005, 2960, 1660, 1610, 1515, 1420, 1390, 1235, 1170, 1105, 1070, 1005, 865, 850, 810, 590, 575 cm-1.

Workup

  1. distillationdistilled right before use
  2. customthe solvent and excess oxalyl chloride were removed by evaporation at 60° C. under 20 Torr
  3. dissolutionTo the residue dissolved in dichloromethane (25 ml)
  4. stirringthe whole was stirred at room temperature overnight
  5. washthe organic layer was washed with saturated ammonium chloride aq solution (100 ml×twice),
  6. dry with materialdried over anhydrous magnesium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe resulting crude product was purified by column chromatography (silica gel, ethyl acetate:hexane=3:7)

Sources & evidence

ORD record
ord-b12fae66fbab4e5c80c8afbd7d881bd3
Source dataset
uspto-grants-1994_11
Patent number
US05369109

Reaction notes

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