Hydrochloric Acid → 2-Chloropyridine-3-sulfonyl chloride

HRID 361411Notes

Reaction equation

HRID 361411 reaction equation
N([O-])=O.[Na+].N[C:6]1[C:7]([Cl:12])=[N:8][CH:9]=[CH:10][CH:11]=1.[S:13](=[O:15])=[O:14].[ClH:16]>O.C(O)(=O)C.[Cu]Cl>[Cl:12][C:7]1[C:6]([S:13]([Cl:16])(=[O:15])=[O:14])=[CH:11][CH:10]=[CH:9][N:8]=1

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 1119Sulfur DioxideHCID 805282-Chloro-3-pyridylamineHCID 23668193Sodium Nitrite

Product 1

HCID 102199682-Chloropyridine-3-sulfonyl chloride

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

A solution of sodium nitrite (6.5g) in water (15 ml) was added gradually to a solution of 3-amino-2-chloropyridine (10 g) in acetic acid (100 ml) and concentrated hydrochloric acid (37 ml) at 0°-5° C. This cold solution was then added portion-wise to a stirred and cooled (5° C.) mixture of copper(I) chloride (2.33 g) in acetic acid (160 ml) saturated with sulphur dioxide keeping the temperature below 10° C. After the addition was complete the cooling bath was removed and the mixture was stirred a further 90 minutes at ambient temperature. Volatile material was removed by evaporation and water (300 ml) was added to the residue to give a solid. The water was decanted off and the solid was dissolved in ether (500 ml) and washed with saturated aqueous sodium hydrogen carbonate solution (200 ml), water (200 ml) and saturated sodium chloride solution and was then dried (MgSO4). Volatile material was removed by evaporationto give 2-chloropyridine-3-sulphonyl chloride (12.1 g) as an oil which solidified upon refrigeration and was used without further purification; 1H NMR (CDCl3): 7.5 (dd, 1 H), 8.5 (dd, 1 H), 8.7 (dd, 1 H).

Workup

  1. additionThis cold solution was then added portion-wise to
  2. temperaturecooled
  3. additionAfter the addition
  4. customwas removed
  5. stirringthe mixture was stirred a further 90 minutes at ambient temperature
  6. customVolatile material was removed by evaporation and water (300 ml)
  7. additionwas added to the residue
  8. customto give a solid
  9. customThe water was decanted off
  10. dissolutionthe solid was dissolved in ether (500 ml)
  11. washwashed with saturated aqueous sodium hydrogen carbonate solution (200 ml), water (200 ml) and saturated sodium chloride solution
  12. dry with materialwas then dried (MgSO4)
  13. customVolatile material was removed by evaporationto

Sources & evidence

ORD record
ord-2f50212384904cc89f65870737ae0caa
Source dataset
uspto-grants-1999_02
Patent number
US05866568

Reaction notes

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