3,3-Dimethylbutylamine → Ethyl 2-chloro-4-[(3,3-dimethylbutyl)amino]-6-methyl-3-pyridinecarboxylate

HRID 598223Notes

Reaction equation

HRID 598223 reaction equation
[Cl:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6](Cl)[CH:5]=[C:4]([CH3:14])[N:3]=1.[CH3:15][C:16]([CH3:21])([CH3:20])[CH2:17][CH2:18][NH2:19]>C(O)C.C(OCC)(=O)C>[Cl:1][C:2]1[C:7]([C:8]([O:10][CH2:11][CH3:12])=[O:9])=[C:6]([NH:19][CH2:18][CH2:17][C:16]([CH3:21])([CH3:20])[CH3:15])[CH:5]=[C:4]([CH3:14])[N:3]=1

Participants

5

Reactant 2

HCID 197093,3-DimethylbutylamineHCID 604813Ethyl 2,4-dichloro-6-methylnicotinate

Product 1

HCID 86614972Ethyl 2-chloro-4-[(3,3-dimethylbutyl)amino]-6-methyl-3-pyridinecarboxylateYield 80%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of ethyl 2,4-dichloro-6-methyl-3-pyridinecarboxylate (1.00 g, 4.27 mmol) in ethanol (20.0 mL) was treated with (3,3-dimethylbutyl)amine (0.570 mL, 4.27 mmol). The mixture was refluxed for 2 days, and upon cooling, diluted with ethyl acetate and washed with saturated aqueous sodium bicarbonate. The aqueous layer was extracted twice with ethyl acetate. The combined organic portions were dried over magnesium sulfate, filtered, concentrated in vacuo, and purified via flash column chromatography (20-60% ethyl acetate in hexanes) to afford the title compound as an amber oil (1.02 g, 80%). 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 6.94 (t, J=4.4 Hz, 1H), 6.18 (s, 1H), 4.23 (q, J=7.2 Hz, 2H), 2.82-3.17 (m, 2H), 2.25 (s, 3H), 1.35-1.54 (m, 2H), 1.25 (t, J=7.1 Hz, 3H), 0.84 (s, 9H). MS(ES+) m/e 299 [M+H]+.

Workup

  1. temperatureThe mixture was refluxed for 2 days
  2. temperatureupon cooling
  3. washwashed with saturated aqueous sodium bicarbonate
  4. extractionThe aqueous layer was extracted twice with ethyl acetate
  5. dry with materialThe combined organic portions were dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. custompurified via flash column chromatography (20-60% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-8720ba681d524d7da46f234fc2801101
Source dataset
uspto-grants-2011_03
Patent number
US07897612B2

Reaction notes

Loading…