Ammonia → HCID 178469844, compound

HRID 1930419Notes

Reaction equation

HRID 1930419 reaction equation
[O:1]=[C:2]([CH2:7][C:8](O)=O)[CH2:3][C:4](O)=[O:5].[CH:11]([O:18]CC)([O:15][CH2:16][CH3:17])OCC.C(OC(=O)C)(=O)C.[NH3:28]>C(Cl)Cl>[OH:1][C:2]1[C:7]([C:11]([O:15][CH2:16][CH3:17])=[O:18])=[CH:8][N:28]=[C:4]([OH:5])[CH:3]=1

Participants

6

Reactant 4

HCID 222AmmoniaHCID 7918Acetic AnhydrideHCID 31214Ethyl orthoformateHCID 68328Acetonedicarboxylic acid

Product 1

HCID 178469844HCID 178469844, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
120 °C

Procedure

3-Oxo-pentanedioic acid (101 g, 0.5 mmol), diethyl ester, 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 (1000 mL). 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 (2×1000 mL). Then the aqueous layer was acidified to pH 5 with cone 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, 1 H), 4.23 (q, J=6.8, 14.0 Hz, 2 H), 1.25 (t, J=7.2 Hz, 3 H). 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 (2×1000 mL)
  5. filtrationThe precipitate was collected by filtration

Sources & evidence

ORD record
ord-f9f1659f03e14a30ad8a5709c6390080
Source dataset
uspto-grants-2012_05
Patent number
US08188113B2

Reaction notes

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