2-Bromo-5-methylpyridine

2-Bromo-5-methylpyridine Property

Melting point:

41-43 °C (lit.)

Boiling point:

95-96 °C/12.5 mmHg (lit.)

Density 

1.4964 (rough estimate)

refractive index 

1.5680 (estimate)

Flash point:

218 °F

storage temp. 

Inert atmosphere,Room Temperature

solubility 

Dimethyl Sulfoxide, Methanol,

form 

Low Melting Crystalline Solid or Crystals

pka

1.08±0.10(Predicted)

color 

White to light yellow or pale brown

BRN 

107323

InChI

InChI=1S/C6H6BrN/c1-5-2-3-6(7)8-4-5/h2-4H,1H3

InChIKey

YWNJQQNBJQUKME-UHFFFAOYSA-N

SMILES

C1(Br)=NC=C(C)C=C1

CAS DataBase Reference

3510-66-5(CAS DataBase Reference)

Safety

Hazard Codes 

Xi,Xn

Risk Statements 

36/37/38-20/21/22

Safety Statements 

26-37/39-36/37/39-36

WGK Germany 

3

HazardClass 

IRRITANT

HS Code 

29333999

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P271Use only outdoors or in a well-ventilated area.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P302+P352IF ON SKIN: wash with plenty of soap and water.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

2-Bromo-5-methylpyridine Chemical Properties,Usage,Production

Structure

The crystal structure of 2-Bromo-5-methylpyridine was reported. The planar molecule lies on a crystallographic plane of symmetry, with a half molecule in the asymmetric unit. The only intermolecular interactions observed are weak tip-to-tail C3—H3···N1 interactions that form infinite chains along[100]. Similar C—H···N interactions have been observed in other5-substituted 2-bromopyridines, though not in the closely related 2,6-dibromo-3,5-dimethylpyridine.There are no other significant intermolecular interactions present[1].

Chemical Properties

2-Bromo-5-methylpyridine is Light Brown Solid

Uses

2-Bromo-5-methylpyridine is used for preparation of [[(triazolylmethyl)pyridyl]phenyl]tetrazoles and related compounds as cardiovascular agents.

Uses

2-Bromo-5-methylpyridine has been used as starting reagent for the synthesis of:

• 5,5′-dimethyl-2,2′-bipyridine
• 5-methyl-2,2′:6′,2″-terpyridine
• 5-bromo-5″-methyl-2,2′:6′,2″-terpyridine

Preparation

Using 5-methylpyridin-2-amine as the raw material, hydrobromic acid and sodium nitrite were reacted at -20°C to obtain 2-Bromo-5-methylpyridine.

Reactions

2-Bromo-5-methylpyridine is stable under proper conditions, it reacts with oxidizing agents.

Health Hazard

2-Bromo-5-methylpyridine can cause skin irritation and serious eye irritation.

Synthesis

General procedure for the synthesis of 2-bromo-5-methylpyridine from 2-amino-5-methylpyridine: Method B Intermediate 7: 2-[[6-morpholin-4-yl]-pyridin-3-yl]ethylamine Step 1: Synthesis of 2-bromo-5-methylpyridine To a stirred 1.5 L 48% hydrobromic acid solution of 2-amino-5-methylpyridine (120 g, 1.10 mol), bromine (160 mL, 498 g, 3.11 mol) was slowly added over a period of 1 h at -20 °C. The addition of bromine (160 mL, 498 g, 3.11 mol) to a stirred solution of 2-amino-5-methylpyridine was completed at -20 °C. After addition, stirring was continued at the same temperature for 2 hours. Subsequently, a solution of sodium nitrite (204 g, 2.95 mol) in 300 mL of water was slowly added to the reaction mixture and stirred at -20 °C for an additional 1 hour. Upon completion of the reaction, the reaction mixture was quenched to -20 °C with aqueous sodium hydroxide (2 kg NaOH dissolved in 2 L of water) and then extracted with ether (3 x 1 L). The organic layers were combined, washed sequentially with water and brine, dried over anhydrous sodium sulfate and concentrated to give the crude product. The crude product was purified by distillation (bath temperature 130 °C, vacuum temperature 85-90 °C, vacuum 0.01 mmHg) to give 172 g of 2-bromo-5-methylpyridine as an off-white low melting point solid in 90% yield. [TLC detection, Rf = 0.8, unfolding agent: ether]

References

[1] Mrittika Roy, David R. Manke, J. Golen. “2-Bromo-5-methyl-pyridine.” IUCrData 26 10 (2016).