Ammonia → HCID 178469844, compound

HRID 1430469Notes

Reaction equation

HRID 1430469 reaction equation
C([O:3][C:4](=O)[CH2:5][C:6](=[O:13])[CH2:7][C:8](OCC)=O)C.[CH:15]([O:22]CC)([O:19][CH2:20][CH3:21])OCC.C(OC(=O)C)(=O)C.[NH3:32]>C(Cl)Cl>[OH:13][C:6]1[C:7]([C:15]([O:19][CH2:20][CH3:21])=[O:22])=[CH:8][N:32]=[C:4]([OH:3])[CH:5]=1

Participants

6

Reactant 4

HCID 222AmmoniaHCID 7918Acetic AnhydrideHCID 31214Ethyl orthoformateHCID 66045Diethyl acetonedicarboxylate

Product 1

HCID 178469844HCID 178469844, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
120 °C

Procedure

3-Oxo-pentanedioic acid diethyl ester (101 g, 0.5 mmol), triethyl orthoformate (81.4 g, 0.55 mol) and acetic anhydride (102 g, 1 mol) were combined and heated to 120° C. for 2 h. The resulting mixture was cooled to RT and dissolved in DCM (1 L). After further cooling to 0° C., ammonia (30%, 80 mL) was added and the reaction mixture was allowed to warm to RT overnight. The product was extracted with water (2×) and the aqueous layer was acidified to pH 5 with conc. HCl. The precipitate was collected by filtration to afford ethyl 4,6-dihydroxynicotinate (60.0 g, 60% yield). 1H NMR (400 MHz, DMSO-d6): δ 7.99 (s, 1H), 5.58 (s, 1H), 4.23 (q, J=6.8, 14.0 Hz, 2H), 1.25 (t, J=7.2 Hz, 3H); MS (ESI) m/z: 184.1 [M+H]+.

Workup

  1. temperatureThe resulting mixture was cooled to RT
  2. temperatureAfter further cooling to 0° C.
  3. temperatureto warm to RT overnight
  4. extractionThe product was extracted with water (2×)
  5. filtrationThe precipitate was collected by filtration

Sources & evidence

ORD record
ord-8c0a99a31c8749b38856bf5c20aa804e
Source dataset
uspto-grants-2015_01
Patent number
US08940756B2

Reaction notes

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