Diethyl (ethoxymethylene)malonate → Diethyl {[(pyridin-3-yl)amino]methylidene}propanedioate

HRID 1497685Notes

Reaction equation

HRID 1497685 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([NH2:7])[CH:2]=1.C(O[CH:11]=[C:12]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[C:13]([O:15][CH2:16][CH3:17])=[O:14])C>>[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([NH:7][CH:11]=[C:12]([C:13]([O:15][CH2:16][CH3:17])=[O:14])[C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:2]=1

Participants

3

Reactant 2

HCID 6871Diethyl (ethoxymethylene)malonateHCID 100093-Aminopyridine

Product 1

HCID 2313092Diethyl {[(pyridin-3-yl)amino]methylidene}propanedioateYield 95.3%

Procedure

Pyridin-3-amine (9.41 g, 100 mmol) and diethyl 2-(ethoxymethylene)malonate (21.6 g, 100 mmol) were combined in a 250 mL screw capped vessel and this mixture was placed into a preheated oil bath at 80° C. and the resulting light brown solution was stirred for 15 h at which time LCMS analysis indicated the presence of a new spot. Then, the light brown solution was cooled to room temperature and as a result some solids started to form. The mixture was left at room temperature for 2 h. The solids were hard to break, but the big chunks were collected by filtration and washed with hexanes. After air drying, 25.18 g of diethyl 2-((pyridin-3-ylamino)methylene)malonate (24) (95.3% yield) was isolated as a white solid.

Workup

  1. customcapped vessel
  2. customthis mixture was placed into a preheated oil bath at 80° C.
  3. customas a result some solids
  4. customto form
  5. waitThe mixture was left at room temperature for 2 h
  6. filtrationthe big chunks were collected by filtration
  7. washwashed with hexanes
  8. customAfter air drying

Sources & evidence

ORD record
ord-ddc7e05072874abb93ced3b60c042639
Source dataset
uspto-grants-2015_12
Patent number
US09199987B2

Reaction notes

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