Sulfamic Acid → 2,4-Dichloronicotinic Acid

HRID 1791100Notes

Reaction equation

HRID 1791100 reaction equation
[Cl:1][C:2]1[C:7]([CH:8]=[O:9])=[C:6]([Cl:10])[CH:5]=[CH:4][N:3]=1.Cl([O-])=[O:12].[Na+].S(=O)(=O)(O)N>C1COCC1.O.[OH-].[Na+]>[Cl:1][C:2]1[N:3]=[CH:4][CH:5]=[C:6]([Cl:10])[C:7]=1[C:8]([OH:12])=[O:9]

Participants

7

Reactant 3

HCID 5987Sulfamic AcidHCID 150539852,4-Dichloropyridine-3-carbaldehydeHCID 23668197Sodium Chlorite

Product 1

HCID 105838872,4-Dichloronicotinic AcidYield 50.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 14798Sodium HydroxideSolvent

Procedure

A solution of 0.40 g of the aldehyde from Step B was dissolved in 6 mL of THF and then added to a solution of 0.27 g of sodium chlorite and 0.29 g of sulfamic acid in 6 mL of water. The reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with 1 N sodium hydroxide (10 mL) and extracted with diethyl ether (1×). The aqueous layer was then acidified with concentrated HCl, extracted with methylene chloride (2×), and the combine methylene chloride extracts were dried over magnesium sulfate. The methylene chloride was removed under vacuum to give 0.22 g of a solid. 1H NMR (CDCl3; 300 MHz) δ 7.38 (d, 1H J is 5.4 Hz), 8.40 (d, 1H, J is 5.5 Hz), 8.60 (bs, 1H).

Workup

  1. extractionextracted with diethyl ether (1×)
  2. extractionextracted with methylene chloride (2×)
  3. dry with materialthe combine methylene chloride extracts were dried over magnesium sulfate
  4. customThe methylene chloride was removed under vacuum

Sources & evidence

ORD record
ord-2d0e35ce77454d3dba4f66033a8045cb
Source dataset
uspto-grants-2006_07
Patent number
US07074742B2

Reaction notes

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