Sulfuric Acid → HCID 68808604, compound

HRID 1782618Notes

Reaction equation

HRID 1782618 reaction equation
[NH2:1][C:2]1[CH:7]=[C:6]([C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:9]=2[F:15])[N:5]=[C:4]([C:16]([O:18][CH3:19])=[O:17])[C:3]=1[Cl:20].S(=O)(=O)(O)O.[N+:26]([O-])([O-:28])=[O:27].[Na+]>>[CH3:19][O:18][C:16]([C:4]1[C:3]([Cl:20])=[C:2]([NH2:1])[CH:7]=[C:6]([C:8]2[CH:13]=[C:12]([N+:26]([O-:28])=[O:27])[C:11]([Cl:14])=[CH:10][C:9]=2[F:15])[N:5]=1)=[O:17]

Participants

4

Reactant 3

HCID 1118Sulfuric AcidHCID 24268Sodium NitrateHCID 22677258HCID 22677258, compound

Product 1

HCID 68808604HCID 68808604, compoundYield 84.4%

Conditions

Temperature
0 °C

Procedure

Methyl 4-amino-3-chloro-6-(4-chloro-2-fluorophenyl)pyridine-2-carboxylate (1.0 g, 3.2 mmol) was added as a solid to well stirred concentrated sulfuric acid (16 mL) at 0° C. Sodium nitrate (0.29 g, 3.5 mmol) was added to the mixture and the resulting yellow solution was stirred at 0° C. for 1.5 hours then diluted with a large quantity of ice and allowed to warm to room temperature. The solution was filtered to remove some solids then the filtrate extracted with 3 portions of ethyl acetate and the combined ethyl acetate layers washed with saturated aqueous NaHCO3 and dried (Na2SO4). Filtration and concentration gave 4-amino-3-chloro-6-(4-chloro-2-fluoro-5-nitrophenyl)pyridine-2-carboxylic acid methyl ester (0.96 g, 2.7 mmol) as a yellow solid: mp 161-163° C.: 1H NMR (CDCl3): δ 8.73 (d, 1H), 7.36 (d, 1H), 7.24 (d, 1H), 4.93 (bs, 2H), 4.02 (s, 3H).

Workup

  1. additionthen diluted with a large quantity of ice
  2. temperatureto warm to room temperature
  3. filtrationThe solution was filtered
  4. customto remove some solids
  5. extractionthe filtrate extracted with 3 portions of ethyl acetate
  6. washthe combined ethyl acetate layers washed with saturated aqueous NaHCO3
  7. dry with materialdried (Na2SO4)
  8. filtrationFiltration and concentration

Sources & evidence

ORD record
ord-eeadaa8ae94740c897fe9c4f5f77ce63
Source dataset
uspto-grants-2009_03
Patent number
US07498468B2

Reaction notes

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