Methyl acetoacetate → Methyl 3-{[4-(acetylamino)phenyl]amino}but-2-enoate

HRID 2110105Notes

Reaction equation

HRID 2110105 reaction equation
[CH3:1][C:2]([NH:4][C:5]1[CH:10]=[CH:9][C:8]([NH2:11])=[CH:7][CH:6]=1)=[O:3].[C:12]([O:18][CH3:19])(=[O:17])[CH2:13][C:14]([CH3:16])=O>CO>[C:2]([NH:4][C:5]1[CH:10]=[CH:9][C:8]([NH:11][C:14]([CH3:16])=[CH:13][C:12]([O:18][CH3:19])=[O:17])=[CH:7][CH:6]=1)(=[O:3])[CH3:1]

Participants

4

Reactant 2

HCID 7757Methyl acetoacetateHCID 312304-Aminoacetanilide

Product 1

HCID 284013Methyl 3-{[4-(acetylamino)phenyl]amino}but-2-enoateYield 47%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
5 °C

Procedure

A suspension of 4-aminoacetanilide (2) (253 g, 1.68 mol) and methyl acetoacetate (215 g, 1.85 mol) in MeOH (0.75 L) was heated to reflux. The resulting solution was held at reflux for 16 h and then cooled to 5° C. The resulting off-white precipitate was filtered and washed with MTBE (3×200 mL) to give butenoate 3 (195 g, 47% yield). The mother liquor was concentrated in vacuo and filtered to give a second crop of 3 as pale pink solids (141 g, 34% yield, 81% overall yield). 1H NMR (DMSO) δ 10.22 (s, 1 H), 9.97 (s, 1 H), 7.57 (d, 2 H), 7.11 (d, 2 H), 4.65 (s, 1 H), 3.56 (s, 3 H), 2.04 (s, 3 H), 1.94 (s, 3 H); 13C NMR (DMSO) δ 169.64, 168.07, 159.33, 136.48, 133.55, 124.52, 119.44, 84.47, 49.77, 23.81, 19.68.

Workup

  1. temperaturewas heated to reflux
  2. temperatureat reflux for 16 h
  3. filtrationThe resulting off-white precipitate was filtered
  4. washwashed with MTBE (3×200 mL)

Sources & evidence

ORD record
ord-38c92cbabcc24075adb9a7aeafd86b8d
Source dataset
uspto-grants-2009_04
Patent number
US07517890B2

Reaction notes

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