Acetic Acid → ethyl (2Z)-3-(methylamino)-3-phenylacrylate

HRID 1360102Notes

Reaction equation

HRID 1360102 reaction equation
[CH3:1][NH2:2].[C:3]([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])(=O)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.CC(O)=O.CN.CC(O)=O>C1COCC1.CCO>[CH3:1][NH:2]/[C:3](/[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)=[CH:11]\[C:12]([O:14][CH2:15][CH3:16])=[O:13]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 6329MethylamineHCID 7170Ethyl benzoylacetateHCID 13000541Methylamine Acetate

Product 1

HCID 10976613ethyl (2Z)-3-(methylamino)-3-phenylacrylateYield 99%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of methylamine (65.03 mL of a 2M solution in THF, 130.06 mmol) and ethyl benzoylacetate (4.505 mL, 26.01 mmol) in EtOH (26 mL) was added HOAc (7.45 mL, 130.06 mmol). The mixture was then heated to reflux for 15 h. At this time, crude 1H NMR revealed only product and MeNH2—HOAc. The reaction mixture was then cooled to RT, and the solvent was removed in vacuo. The crude reaction was then extracted with 1 N HCl and DCM. The organic layer was then dried over MgSO4, and the solvent was removed in vacuo to yield 5.3 g (99%) of ethyl (2Z)-3-(methylamino)-3-phenylacrylate. The product was used as is in subsequent reactions. 1H NMR (500 MHz, CDCl3) ppm: 8.50 (br s, 1H), 7.40 (m, 3H), 7.35 (m, 2H), 4.59 (s, 1H), 4.15 (q, J=7.0 Hz, 2H), 2.77 (d, J=5.0 Hz, 3H), 2.50 (s, 3H), 1.27 (t, J=7.0 Hz, 3H).

Workup

  1. temperatureThe mixture was then heated
  2. temperatureto reflux for 15 h
  3. customthe solvent was removed in vacuo
  4. customThe crude reaction
  5. extractionwas then extracted with 1 N HCl and DCM
  6. dry with materialThe organic layer was then dried over MgSO4
  7. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-9f6e7b70ac0642568ebf4e8a3e891900
Source dataset
uspto-grants-2011_02
Patent number
US07879797B2

Reaction notes

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