Hydrochloric Acid → (3-Chloropyridin-2-yl)methanol

HRID 615372Notes

Reaction equation

HRID 615372 reaction equation
N([O-])=O.[Na+].N[C:6]1[C:7]([CH2:12][OH:13])=[N:8][CH:9]=[CH:10][CH:11]=1.[ClH:14]>O.S>[Cl:14][C:6]1[C:7]([CH2:12][OH:13])=[N:8][CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 3

HCID 313Hydrochloric Acid2×HCID 15645802(3-Aminopyridin-2-yl)methanolHCID 23668193Sodium Nitrite

Product 1

HCID 10486967(3-Chloropyridin-2-yl)methanol

Reagents, catalysts & solvents 2

HCID 402Hydrogen SulfideSolventHCID 962WaterSolvent3×

Procedure

A solution sodium nitrite (2.38 g) in water (10 ml) was added dropwise to a stirred mixture of 3-amino-2-hydroxymethylpyridine (4.8 g) in aqueous hydrochloric acid (48% 10 ml) and water (5 ml) at 0°-5° C. This solution of the diazonium salt was added to a hot solution of cuprous chloride (2.5 g) in conc. hydrochloric acid and following cessation of nitrogen evolution the mixture was heated on the steam bath for 0.5 hours, diluted with water and saturated with hydrogen sulphide. Filtration, concentration to low bulk and extraction with chloroform yielded 3-chloro-2-hydroxymethylpyridine (3.7 g), m.p. 42°-44° (from n-pentane). This was dissolved in aqueous hydrobromic acid (48% 50 ml), cysteamine hydrochloride (3.22 g) added and the solution obtained was heated under reflux for 6 hours. Concentration, followed by recrystallisation from aqueous ethanol afforded 2-[(2-aminoethyl)thiomethyl]-3-chloropyridine dihydrobromide (6.0 g), m.p. 250°.

Workup

  1. temperaturewas heated on the steam bath for 0.5 hours
  2. filtrationFiltration, concentration
  3. extractionto low bulk and extraction with chloroform

Sources & evidence

ORD record
ord-1e4a0fe0dcdd47e7b0f4202c6a2f5f42
Source dataset
uspto-grants-1985_02
Patent number
US04499101

Reaction notes

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