Diethyl (ethoxymethylene)malonate → HCID 178469588, compound

HRID 2410149Notes

Reaction equation

HRID 2410149 reaction equation
[CH3:1][O:2][C:3]1[CH:9]=[CH:8][C:6]([NH2:7])=[CH:5][CH:4]=1.C([O:12][CH:13]=[C:14]([C:20](OCC)=O)[C:15]([O:17][CH2:18][CH3:19])=[O:16])C>O(C1C=CC=CC=1)C1C=CC=CC=1>[OH:12][C:13]1[C:8]2[C:6](=[CH:5][CH:4]=[C:3]([O:2][CH3:1])[CH:9]=2)[N:7]=[CH:20][C:14]=1[C:15]([O:17][CH2:18][CH3:19])=[O:16]

Participants

4

Reactant 2

HCID 6871Diethyl (ethoxymethylene)malonateHCID 7732P-Anisidine

Product 1

HCID 178469588HCID 178469588, compoundYield 17%

Reagents, catalysts & solvents 1

HCID 7583Diphenyl EtherSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 4-methoxyaniline (12.3 g, 100 mmol) and diethyl 2-(ethoxymethylene)malonate (21.6 g, 100 mmol) was stirred at 120° C. under nitrogen for 4 hrs. The solution was cooled to room temperature and Ph2O (100 mL) was added. The reaction mixture was refluxed at 260° C. under nitrogen for 8 hrs. The solution was cooled to room temperature and diluted with hexanes. The resultant precipitate was collected by filtration, washed with 25% ethyl acetate in hexanes, and dried under vacuum to give ethyl 4-hydroxy-6-methoxyquinoline-3-carboxylate as a pale-yellow solid (4.21 g, 17%). 1H NMR (400 MHz, DMSO-d6) δ 1.26 (t, J=7.0 Hz, 3H), 3.83 (s, 3H), 4.19 (q, J=7.0 Hz, 2H), 7.32 (dd, J=3.2, 9.6 Hz, 1H), 7.55 (d, J=3.2 Hz, 1H), 7.56 (d, J=9.6 Hz, 1H), 8.47 (s, 1H), 12.27 (s, 1H). MS 248 (MH+).

Workup

  1. temperatureThe solution was cooled to room temperature
  2. temperatureThe reaction mixture was refluxed at 260° C. under nitrogen for 8 hrs
  3. temperatureThe solution was cooled to room temperature
  4. filtrationThe resultant precipitate was collected by filtration
  5. washwashed with 25% ethyl acetate in hexanes
  6. customdried under vacuum

Sources & evidence

ORD record
ord-7a201f51c162447b8459ab36e98f1eca
Source dataset
uspto-grants-2014_08
Patent number
US08815956B2

Reaction notes

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