Hydrogen Bromide → (3-Bromopyridin-2-yl)methanol

HRID 2058231Notes

Reaction equation

HRID 2058231 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.[BrH:14]>O.S>[Br:14][C:6]1[C:7]([CH2:12][OH:13])=[N:8][CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 3

HCID 260Hydrogen Bromide2×HCID 15645802(3-Aminopyridin-2-yl)methanolHCID 23668193Sodium Nitrite

Product 1

HCID 14022521(3-Bromopyridin-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 hydrobromic 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 bromide (2.5 g.) in 60% hydrobromic 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-bromo-2-hydroxymethyl-pyridine (4.8 g.). 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)-thiomethyl)-3-bromopyridine dihydrobromide (6.1 g.), m.p. 252°-254°. (Found: C, 23.7; H, 3.4; N, 6.7; S, 7.9. C8H11BrN2S.2HBr requires: C, 23.5; H, 3.2; N, 6.9; S, 7.8)

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-4937ca3c8ba94ed2a15a4d6f17a99b12
Source dataset
uspto-grants-1980_07
Patent number
US04215125

Reaction notes

Loading…