Ethanol → Ethyl 3-amino-5-chloropicolinate

HRID 2392703Notes

Reaction equation

HRID 2392703 reaction equation
[CH3:1][CH2:2]O.OS(O)(=O)=O.[NH2:9][C:10]1[C:11]([C:17]([OH:19])=[O:18])=[N:12][CH:13]=[C:14]([Cl:16])[CH:15]=1>>[NH2:9][C:10]1[C:11]([C:17]([O:19][CH2:1][CH3:2])=[O:18])=[N:12][CH:13]=[C:14]([Cl:16])[CH:15]=1

Participants

4

Reactant 3

HCID 702EthanolHCID 1118Sulfuric AcidHCID 189803533-Amino-5-chloropyridine-2-carboxylic acid

Product 1

HCID 289723Ethyl 3-amino-5-chloropicolinate

Conditions

Temperature
120 °C

Procedure

Absolute EtOH (1.00 mL, d=0.785, 17.0 mmol) and H2SO4 (96%, 0.10 mL, d=1.840, 1.8 mmol) were added to the hydrochloride salt of 3-amino-5-chloropicolinic acid (106) (0.100 g, 0.407 mmol). The mixture was stirred and heated to reflux. The mixture was refluxed (120° C.) for 19 h. The resulting solution was cooled to room temperature, poured over ice (1.0 g), and neutralized to pH 5 with solid Na2 CO3. The resulting mixture was extracted with EtOAc (4×3 mL), the organic layer dried (Na2SO4), and rota-evaporated to dryness, leaving the title compound as an orange solid, 68.6 mg (84.0%), mp 139.5°-142.5° C. (Lit., 165°-6° C., McCaustland and Cheng, J. Heterocycl. Chem. 7:467 (1970)); 1H NMR (CDCl3): δ1.44 (t, J=6.9 Hz, 3H), 4.45 (q, J=6.9 Hz, 3H), 5.84 (bs, 2H), 7.05 (d, J=1.5 Hz, 1H), 7.99 (d, J=1.8 Hz, 1H).

Workup

  1. temperatureheated to reflux
  2. temperatureThe resulting solution was cooled to room temperature
  3. extractionThe resulting mixture was extracted with EtOAc (4×3 mL)
  4. dry with materialthe organic layer dried (Na2SO4)
  5. customrota-evaporated to dryness

Sources & evidence

ORD record
ord-50a6f0e6d300438f81c948a6ef51efcf
Source dataset
uspto-grants-1998_09
Patent number
US05801183

Reaction notes

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