N-Methylaniline → Methyl 4-{[methyl(phenyl)amino]methyl}benzoate

HRID 1501031Notes

Reaction equation

HRID 1501031 reaction equation
[CH:1]([C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)=O.[CH3:13][NH:14][C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1.C([BH3-])#N.[Na+]>CO.C(O)(=O)C>[CH3:13][N:14]([CH2:1][C:3]1[CH:12]=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[CH:5][CH:4]=1)[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1

Participants

6

Reactant 3

HCID 7515N-MethylanilineHCID 15294Methyl 4-FormylbenzoateHCID 5003444Sodium cyanoborohydride

Product 1

HCID 28829589Methyl 4-{[methyl(phenyl)amino]methyl}benzoateYield 26%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 887MethanolSolvent

Procedure

To a solution of methyl 4-formylbenzoate (1 g, 6.1 mmol) and N-methylbenzenamine (650 mg, 6.1 mmol) in methanol (50 mL) was added acetic acid (2 drops) and the mixture was stirred for 0.5 hour. Then sodium cyanoborohydride (660 mg, 10 mmol) was added in portions. The mixture was stirred at room temperature for 24 hours. The mixture was washed with water (50 mL) and extracted with dichloromethane (50 mL). The organic phase was separated and concentrated to give a residue. The residue was purified by column chromatography (petroleum ether/ethyl acetate=1:1) to give methyl 4-((methyl(phenyl)amino)methyl)benzoate (400 mg, 26%) as a yellow oil. LRMS (M+H+) m/z: calcd 255.13. found 255. 1H NMR (300 MHz, CD3OD): δ 7.96-7.32 (m, 2H), 7.33 (d, J=8.4 Hz, 2H), 7.18-7.12 (m, 2H), 6.74-6.60 (m, 3H), 4.60 (s, 2H), 3.88 (s, 3H), 3.02 (s, 3H).

Workup

  1. stirringThe mixture was stirred at room temperature for 24 hours
  2. washThe mixture was washed with water (50 mL)
  3. extractionextracted with dichloromethane (50 mL)
  4. customThe organic phase was separated
  5. concentrationconcentrated
  6. customto give a residue
  7. customThe residue was purified by column chromatography (petroleum ether/ethyl acetate=1:1)

Sources & evidence

ORD record
ord-6704fba61d7345609aeefa08e5461c73
Source dataset
uspto-grants-2015_12
Patent number
US09206128B2

Reaction notes

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