Acetic Acid → Ethyl-alpha-carbethoxy-4-dimethylamino-2-nitrocinnamate

HRID 414697

Reaction equation

HRID 414697 reaction equation
[CH3:1][N:2]([CH3:14])[C:3]1[CH:10]=[CH:9][C:6]([CH:7]=O)=[C:5]([N+:11]([O-:13])=[O:12])[CH:4]=1.[C:15]([O:23][CH2:24][CH3:25])(=[O:22])[CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18].N1CCCCC1.C(O)(=O)C>C1(C)C=CC=CC=1>[CH2:20]([O:19][C:17](=[O:18])[C:16]([C:15]([O:23][CH2:24][CH3:25])=[O:22])=[CH:7][C:6]1[CH:9]=[CH:10][C:3]([N:2]([CH3:14])[CH3:1])=[CH:4][C:5]=1[N+:11]([O-:13])=[O:12])[CH3:21]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7761Diethyl MalonateHCID 8082PiperidineHCID 2913524-Dimethylamino-2-nitrobenzaldehyde

Product 1

HCID 14365894Ethyl-alpha-carbethoxy-4-dimethylamino-2-nitrocinnamateYield 61.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 8.9 grams (g) [50 millimoles (mmol)] of 4-dimethylamino-2-nitrobenzaldehyde [H. Baumann et al, German Pat. No. 2,363,458], 23.7 g (148 mmol) of diethyl malonate, 3.44 g (40.4 mmol) of piperidine and 2.43 g (40.4 mmol) of acetic acid in 400 milliliters (mL) of toluene was refluxed for 16 hours under argon with a Dean Stark trap attached. The solution was cooled to room temperature and washed with 200 mL of 5% aqueous potassium hydroxide (KOH). The organic phase was separated, dried over sodium sulfate (Na2SO4), filtered, and the solvent evaporated. The dark red solid residue was dissolved in 40 mL of methylene chloride (CH2Cl2) and 100 mL of hexane added. After standing for one hour, the solution was filtered to yield 10.4 g of orange crystals. Recrystallization from CH2Cl2 -hexane produced an analytical sample, m.p. 101°-102° C.

Workup

  1. washwashed with 200 mL of 5% aqueous potassium hydroxide (KOH)
  2. customThe organic phase was separated
  3. dry with materialdried over sodium sulfate (Na2SO4)
  4. filtrationfiltered
  5. customthe solvent evaporated
  6. dissolutionThe dark red solid residue was dissolved in 40 mL of methylene chloride (CH2Cl2)
  7. addition100 mL of hexane added
  8. filtrationthe solution was filtered

Sources & evidence

ORD record
ord-f62d6b319d524e269bf1037afda2131e
Source dataset
uspto-grants-1988_12
Patent number
US04794079

Linked notes

Loading…