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

HRID 1679960Notes

Reaction equation

HRID 1679960 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 o 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°.

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-c17c3bbaf499466a97876c1a935a8013
Source dataset
uspto-grants-1981_06
Patent number
US04271169

Reaction notes

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