ChemicalBook CAS DataBase List 4,4'-bis(trifluoromethyl)-2,2'-bipyridine

4,4'-bis(trifluoromethyl)-2,2'-bipyridine synthesis

4synthesis methods

Product Name:4,4'-bis(trifluoromethyl)-2,2'-bipyridine
CAS Number:142946-79-0
Molecular formula:C12H6F6N2
Molecular Weight:292.18

81565-18-6 Synthesis

81565-18-6
339 suppliers
$8.00/1g

4,4'-bis(trifluoromethyl)-2,2'-bipyridine

142946-79-0
63 suppliers
$20.00/250mg

Yield:142946-79-0 89%

Reaction Conditions:

with nickel(II) chloride hexahydrate;triphenylphosphine;zinc in N,N-dimethyl-formamide at 80; for 72 h;Inert atmosphere;Reagent/catalyst;Solvent;Temperature;

Steps:

I. Preparation of 4,4'-bis(trifluoromethyl)-2,2'-bipyridine (2).
In a screw capped tube, NiCl2·6H2O, (238 mg, 1mmol) and PPh3, (524 mg, 2 mmol) were dissolved in 2 mL reagent grade DMF. This blue solution was sparged with argon for 30 min. Activated¹ zinc dust (98 mg, 1.5 mmol) was added and the mixture was stirred with argon sparging for 1 h. To the resulting red-brown slurry, 2-chloro-4-(trifluoromethyl)pyridine (1) (183 mg, 1 mmol) was added. The tube was capped and heated in an 80 °C oil bath for 72 h at which time GC-MS showed full consumption of 1. The reaction mixture was then poured into a beaker containing 2 mL ammonia (24% aq) and 20 g ice. The mixture was extracted with diethyl ether. The diethyl ether phase was dried over MgSO4, filtered, and evaporated. The crude product was purified on a silica gel column (4:1 hexane/CH2Cl2) giving 129 mg (89%) of 2 as a white solid; mp 79-80 °C. ¹H NMR (500 MHz, CDCl3) δ 8.87 (d, J = 5.0 Hz, 2 H), 8.71 (s, 2 H), 7.57 (d, J = 5.0 Hz, 2 H); ¹³C NMR (125 MHz, CDCl3) δ 156.1, 150.3, 139.6 (q, J = 34 Hz), 122.8 (q, J = 273 Hz), 119.9 (q, J = 3.5 Hz), 117.1 (q, J = 3.8 Hz); ¹⁹F NMR (470 MHz, CDCl3) δ -64.9.

References:

Li, Hao;Oppenheimer, Jossian;Smith, Milton R.;Maleczka, Robert E. [Tetrahedron Letters,2016,vol. 57,# 21,p. 2231 - 2232] Location in patent:supporting information

FullText

175205-81-9 Synthesis