Isopropyl 4-amino-6-chloro-5-fluoropicolinate → Methyl 4-amino-6-chloro-5-fluoropicolinate

HRID 244318Notes

Reaction equation

HRID 244318 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH:13](C)C)=[O:11])[CH:3]=1>CO.CC(C)[O-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-]>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([Cl:9])[N:5]=[C:4]([C:10]([O:12][CH3:13])=[O:11])[CH:3]=1

Participants

4

Reactant 1

HCID 71551782Isopropyl 4-amino-6-chloro-5-fluoropicolinate

Product 1

HCID 86668302Methyl 4-amino-6-chloro-5-fluoropicolinateYield 101.1%

Reagents, catalysts & solvents 2

HCID 11026Titanium isopropoxideCatalystHCID 887MethanolSolvent

Procedure

Isopropyl 4-amino-6-chloro-5-fluoropicolinate (1.35 g, 5.80 mmol) was dissolved in anhydrous CH3OH (50 mL), treated with titanium(IV) isopropoxide (300 mg, 2.2 mmol), and heated at reflux for 4 h. After cooling, the volatiles were removed under vacuum, and the residue was taken up in EtOAc (30 mL). This solution was stirred with H2O (1 mL) for 20 min and then filtered through diatomaceous earth. The filtrate was washed with satd aq NaCl (10 mL), dried (Na2SO4), and evaporated to give the title compound (1.2 g, 97%): mp 180-183° C.; 1H NMR (400 MHz, DMSO-d6) δ 7.45 (d, J=6.0 Hz, 1H), 6.93 (s, 2H), 3.83 (s, 3H); 19F NMR (376 MHz, DMSO-d6) δ −131.36, −131.42, −135.47, −135.53; EIMS m/z 204.

Workup

  1. temperatureheated
  2. temperatureat reflux for 4 h
  3. temperatureAfter cooling
  4. customthe volatiles were removed under vacuum
  5. filtrationfiltered through diatomaceous earth
  6. washThe filtrate was washed with satd aq NaCl (10 mL)
  7. dry with materialdried (Na2SO4)
  8. customevaporated

Sources & evidence

ORD record
ord-a496e96a208b4969913fac66432cd1e4
Source dataset
uspto-grants-2014_02
Patent number
US08658568B2

Reaction notes

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