Sodium Hydroxide → 2,4-Dichloro-6-methyl-1-oxy-nicotinic acid methyl ester

HRID 1637691Notes

Reaction equation

HRID 1637691 reaction equation
OO.NC(N)=[O:5].[CH3:7][O:8][C:9](=[O:19])[C:10]1[C:15]([Cl:16])=[CH:14][C:13]([CH3:17])=[N:12][C:11]=1[Cl:18].S([O-])([O-])(=O)=S.[Na+].[Na+].[OH-].[Na+]>FC(F)(F)C(O)=O>[CH3:17][C:13]1[CH:14]=[C:15]([Cl:16])[C:10]([C:9]([O:8][CH3:7])=[O:19])=[C:11]([Cl:18])[N+:12]=1[O-:5]

Participants

6

Reactant 4

HCID 14798Sodium HydroxideHCID 24477Sodium ThiosulfateHCID 31294Carbamide Peroxide2×HCID 15171394Methyl 2,4-dichloro-6-methylnicotinate

Product 1

HCID 248054402,4-Dichloro-6-methyl-1-oxy-nicotinic acid methyl esterYield 93%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

Urea hydrogen peroxide addition compound (98% pure) (3.860 g, 40.9 mmol) was added to a stirring solution of 2,4-dichloro-6-methyl-nicotinic acid methyl ester (3.000 g, 13.6 mmol) in trifluoroacetic acid (15 ml) under nitrogen. The reaction mixture was stirred at room temperature for 18 hr. Additional urea-hydrogen peroxide addition compound (0.640 g, 6.8 mmol) was added and the reaction stirred for an additional 3 hr. Reaction mixture was poured over ice-water and stirred rapidly. The mixture was treated with sodium thiosulfate, adjusted to pH 11 with 2N aqueous NaOH and extracted 3 times with chloroform. The combined chloroform extracts were washed with water, brine, dried over sodium sulfate and concentrated to give 2.98 g (93%) of the title compound of Preparation C. 1H NMR (CDCl3) δ 7.26 (s,1H), 3.98(s,3H), 2.54(s,3H) ppm.

Workup

  1. additionwas added
  2. stirringthe reaction stirred for an additional 3 hr
  3. customReaction mixture
  4. stirringstirred rapidly
  5. extractionextracted 3 times with chloroform
  6. washThe combined chloroform extracts were washed with water, brine
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated
  9. customto give

Sources & evidence

ORD record
ord-c793dbf427664d97941ad873a309fddc
Source dataset
uspto-grants-2000_03
Patent number
US06043260

Reaction notes

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