6,6'-Dibromo-2,2'-bipyridyl

6,6'-Dibromo-2,2'-bipyridyl Property

Melting point:

220-223 °C(lit.)

Boiling point:

369.4±37.0 °C(Predicted)

Density 

1.809±0.06 g/cm3(Predicted)

storage temp. 

Inert atmosphere,Room Temperature

form 

powder to crystal

pka

-0.44±0.22(Predicted)

color 

White to Light yellow

λmax

304nm(EtOH)(lit.)

InChI

InChI=1S/C10H6Br2N2/c11-9-5-1-3-7(13-9)8-4-2-6-10(12)14-8/h1-6H

InChIKey

WZVWSOXTTOJQQQ-UHFFFAOYSA-N

SMILES

C1(C2=NC(Br)=CC=C2)=NC(Br)=CC=C1

Safety

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

26-36

WGK Germany 

3

HS Code 

29333990

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.

6,6'-Dibromo-2,2'-bipyridyl Chemical Properties,Usage,Production

Uses

6,6''-Dibromo-2,2''-bipyridine is used as a catalyst for the preparation of iodoesters through copper-catalyzed [2,3]-and [1,2]-rearrangements of diazoesters and allylic iodides.

Synthesis

GENERAL STEPS: Example 42 Synthesis of 6,6'-dibromo-2,2'-bipyridine 52b. In a dry three-necked round-bottomed flask, 2,6-dibromopyridine (42) (2.32 g, 10 mmol) was dissolved in 250 mL of anhydrous diethyl ether and cooled to -78°C. The solution was prepared in a dry, three-necked round-bottomed flask. The apparatus was equipped with a solid charging funnel for pre-dried copper(II) chloride (2 g, 14.9 mmol). Butyllithium (2.4 M hexane solution, 4.6 mL, 11 mmol) was slowly added dropwise at -78 °C and the reaction mixture was stirred for 2 h at this temperature. Subsequently, copper (II) chloride was added slowly over 30 minutes and stirring was continued at -78 °C for 30 minutes. The reaction system was bubbled through dry oxygen at -78 °C for 1 h, then raised to room temperature and continued to bubble for 1 h. The reaction system was then purged with 200 mL of dry oxygen. Upon completion of the reaction, the reaction was quenched with 200 mL of water and 50 mL of 1 M HCl solution and a precipitate was observed to form. The reaction mixture was filtered and the solid product was collected and recrystallized with THF. The brown solid obtained was dissolved in THF and filtered through Millipore filter. The filtrate was concentrated in vacuum to afford the target product 6,6'-dibromo-2,2'-bipyridine as a white powder in 79% yield. The product characterization data were as follows: 1H NMR (CDCl3) δ (ppm): 7.50 (dd, J = 0.6, 8.1 Hz, 2H, Hpyridine), 7.66 (t, J = 7.8 Hz, 2H, Hpyridine), 8.37 (dd, J = 0.6, 8.4 Hz, 2H, Hpyridine). 13C NMR (CDCl3) δ (ppm): 119.71, 128.15, 138.86, 141.15, 155.16. mass spectrum (MS), m/z (relative abundance): 314 (M++2, 100%), 312 (M+, 45%), 233 (M+-Br, 54%), 153 (M+-2Br, 32%).

References

[1] Patent: US2010/298562, 2010, A1. Location in patent: Page/Page column 48
[2] Dalton Transactions, 2013, vol. 42, # 45, p. 16006 - 16013
[3] Heterocycles, 2005, vol. 65, # 2, p. 293 - 301
[4] Organometallics, 2012, vol. 31, # 10, p. 3825 - 3828
[5] Synthesis, 2005, # 3, p. 458 - 464