2-(TRIBUTYLSTANNYL)PYRIDINE

Uses

Building block in an efficient, palladium-catalyzed synthesis of 2-pyridylazaazulene, a bidentate ligand showing pH and cationic-metal dependent emission spectra.

Synthesis

General procedure for the preparation of 2-tributylmethyltin alkylpyridine by the reaction of 2-bromopyridine with tributyltin chloride: butyllithium (2.5 M hexane solution, 6.33 mmol) was added dropwise to a solution of freshly distilled 2-bromopyridine (1 g, 6.33 mmol) in tetrahydrofuran (12 mL) at -78 °C and degassed. After stirring for 30 minutes, tributyltin chloride (1.7 mL, 6.33 mmol) was added to the slightly reddish solution and stirring was continued at -78 °C for 1 hour, then brought to room temperature and stirred for 1 hour. Upon completion of the reaction, the reaction was quenched with saturated ammonium chloride solution and extracted with diethyl ether. The organic phase was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluent: hexane/ethyl acetate = 20/1) to afford the target product 2-tributylmethylstannylpyridine in 94% yield.1H NMR (CDCl3) δ (ppm): 8.73 (dtd, J = 4.9,1.9,1.0,1H,H6), 7.48 (dt, J = 7.4,1.8,1H,H5). 7.39 (dt, J = 7.4,1.6,1H, H3), 7.10 (ddd, J = 6.9,4.9,1.7,1H, H4), 1.70-1.05 (m, 18H, CH2), 0.85 (t, 9H, J = 7.3, CH3).

References

[1] Patent: US2013/296302, 2013, A1. Location in patent: Paragraph 0592
[2] Patent: US2014/194441, 2014, A1. Location in patent: Paragraph 0455
[3] Inorganic Chemistry, 2013, vol. 52, # 9, p. 5570 - 5580
[4] Patent: US9219237, 2015, B1. Location in patent: Page/Page column 11
[5] European Journal of Inorganic Chemistry, 2002, # 3, p. 573 - 579