2,6-Di-tert-butyl-4-methylphenol → N-Methyl-N-propyl-5-vinyl-isophthalamic acid methyl ester

HRID 1436633Notes

Reaction equation

HRID 1436633 reaction equation
[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:16]=[C:15](Br)[CH:14]=[C:6]([C:7]([N:9]([CH3:13])[CH2:10][CH2:11][CH3:12])=[O:8])[CH:5]=1.[C:19](C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)[CH3:20].C(C([Sn])=C(CCCC)CCCC)CCC>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:16]=[C:15]([CH:19]=[CH2:20])[CH:14]=[C:6]([C:7]([N:9]([CH3:13])[CH2:10][CH2:11][CH3:12])=[O:8])[CH:5]=1

Participants

6

Reactant 3

HCID 314042,6-Di-tert-butyl-4-methylphenolHCID 53438229Tri(butyl)vinyltinHCID 57529325Methyl 3-bromo-5-(methyl(propyl)carbamoyl)benzoate

Product 1

HCID 68814555N-Methyl-N-propyl-5-vinyl-isophthalamic acid methyl esterYield 70%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

Dissolve 5-bromo-N-methyl-N-propyl-isophthalamic acid methyl ester (2.7 g, 8.6 mmol) in toluene (16 mL) and place the solution under nitrogen. Add in sequence 2,6-di-tert-butyl-4-methylphenol (a few crystals), tetrakis(triphenylphosphine)palladium (0) (185 mg, 0.16 mmol), and tributylvinyl tin (3 g, 9.5 mmol) and reflux for 4 h. Filter through a filtering agent and concentrate. Add diethyl ether (70 mL) and 20% aqueous potassium fluoride (70 mL) and stir vigorously. Collect the diethyl ether layer and extract with diethyl ether two additional times. Concentrate and purify (silica gel chromatography, eluting with 0:100 to 50:50 ethyl acetate:hexanes) to give the title compound (1.58 g, 70%).

Workup

  1. temperaturereflux for 4 h
  2. filtrationFilter through a filtering agent
  3. concentrationconcentrate
  4. customCollect the diethyl ether layer
  5. extractionextract with diethyl ether two additional times
  6. concentrationConcentrate
  7. custompurify
  8. wash(silica gel chromatography, eluting with 0:100 to 50:50 ethyl acetate:hexanes)

Sources & evidence

ORD record
ord-a55e58ec57a242ab8505823323a06bfd
Source dataset
uspto-grants-2009_11
Patent number
US07618978B2

Reaction notes

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