Hydrochloric Acid → Ethyl 2-amino-5-chloronicotinate

HRID 2392721Notes

Reaction equation

HRID 2392721 reaction equation
[NH2:1][C:2]1[N:12]=[CH:11][CH:10]=[CH:9][C:3]=1[C:4]([O:6][CH2:7][CH3:8])=[O:5].[ClH:13].OO.C([O-])(O)=O.[Na+]>O>[NH2:1][C:2]1[N:12]=[CH:11][C:10]([Cl:13])=[CH:9][C:3]=1[C:4]([O:6][CH2:7][CH3:8])=[O:5]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 516892Sodium BicarbonateHCID 12433260Ethyl 2-aminopyridine-3-carboxylate

Product 1

HCID 18980364Ethyl 2-amino-5-chloronicotinate

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Ethyl 2-aminonicotinate (121, Example 4) (0.1626 g, 0.9906 mmol) was placed in a 10 mL round-bottom flask. Conc. HCl (35%, 1 mL) was added and the mixture stirred. When all of the ester had dissolved, H2O2 (30%, 0.10 mL, d=1.110, 0.98 mmol) was added. The resulting solution was heated at 55°-60° C. for 2 h. The solution was cooled to room temperature, diluted with water (10 mL), and basified to pH 8 (pH paper) with solid NaHCO3. The mixture was filtered, washed with water (2×10 mL) and dried at 45° C. for 2 h to leave the title compound as a white solid, 0.186 g (93.7%), mp 119.5°-121.5° C.; 1H NMR (CDCl3): δ1.39 (t, J=7.05, 3, CH3 CH2), 4.35 (q, J=7.05, 2, CH3CH2O), 6.44 (bm, 2, NH2), 8.11 (d, J=2.40, 1, py), 8.16 (d, J=2.4, 1, py); IR (KBr): 3448, 3441, 3284, 3161, 1709, 1641, 1402, 1307, 1232, 1150, 1109, 796; HPLC: 100%; LRMS (m/z) 202 (30), 200 (M+, 100), 172 (15), 156 (20), 155 (30), 154 (60) 130 (15), 129 (20), 128 (50), 127 (45), 126 (15), 100 (15), 92 (10), 73 (20) 65 (15), 64 (15); HRMS Calcd: 200.0352. Found: 200.0355.

Workup

  1. temperatureThe resulting solution was heated at 55°-60° C. for 2 h
  2. filtrationThe mixture was filtered
  3. washwashed with water (2×10 mL)
  4. customdried at 45° C. for 2 h

Sources & evidence

ORD record
ord-826f283b80d741308871faf7420225bb
Source dataset
uspto-grants-1998_09
Patent number
US05801183

Reaction notes

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