2-CHLORO-3-CYANOQUINOLINE

A suspension of 2-chloroquinoline-3-carbaldehyde (0.01 mol) in30percent aqueous ammonia (30 mL) was stirred for 5 min at room temperature, resulting in formation of a turbid solution. To this, cericammonium nitrate (0.01 mol) was added with constant stirring at0 C. After completion of the reaction (monitored by TLC, 10–15 min), the mixture was extracted with chloroform–ethyl acetate(5:3), dried with anhydrous sodium sulfate, and concentrated underreduced pressure to give a crude product, which was crystalized inethanol to give pure 2-chloroquinoline-3-carbonitrile as pale yellowcrystals. Yield: 82percent.General procedure: To an oven-dried 2 ml reaction vial equipped with a stir bar wasadded the aldehyde 3a (0.136 g, 1 mmol, 1 equiv) and pyridine(0.474 g, 6.0 mmol, 6 equiv), followed by acetonitrile (2 ml, 0.5M in 3a). The vial was then charged with Ru(bpy)3(PF6)2 (0.017g, 0.02 mmol, 0.02 equiv), 2 (0.043 g, 0.20 mmol, 0.20 equiv), (NH4)2S2O8(0.501 g, 2.2 mmol, 2.2 equiv), and activated 3 Åmolecular sieves (ca. 0.2 g), sealed with a cap, and irradiated inblue LED reactor for 24 h. In the absence of fan cooling, the temperatureof the reaction mixture plateaued at approximately 50°C . After the irradiation was complete, the reaction mixturewas quenched with EtOAc and transferred to a separatoryfunnel. Further EtOAc (30 ml) was added, followed by 0.5 MHCl(aq) (30 ml). The layers were separated, and the aqueous layerwas extracted with EtOAc (3 × 20 ml). The organic layers werethen combined and washed with 0.5 M 0.5 M HCl(aq) (2 × 20 ml), saturated aqueous sodium bicarbonate (2 × 20 ml), and finallybrine (20 ml). The organic layer was then dried over sodiumsulfate and the solvent removed in vacuo to afford the crudeproduct. The resulting crude mixture was adhered to silica gelusing 1.5 weight equivalents of SiO2(relative to the theoreticalyield). The dry-packed material was gently added on top of asilica gel plug. The plug was washed with an excess of hexanes(ca. 5 column volumes). The desired product was eluted off theplug via a 90:10 by volume mixture of hexanes/EtOAc (3–4column volumes). The solvent was removed in vacuo by rotaryevaporation affording the pure nitrile 3c (0.066 g, 50percent) as awhite solid.General procedure: A mixture of General procedure: To a mixture of 1 (1 mmol) and binucleophile 2 (1 mmol) in 2-3 mL of EtOH was added t-BuOK (0.5 mmol), reaction mixture was stirred at 90 C. After completion of the reaction, mixture poured into ice-cold water, solid product filtered and washed with water (3×5 mL) and further purified by column chromatography on silica gel (60-120 mesh) using EtOAc/hexane as eluent in 4:6 ratio to yielded pure product 3.EXAMPLE 6 A mixture of 50 g of 3-cyano-2(1H)-quinolinone and 250 ml of phosphoryl chloride was heated at reflux for 18 hours. Volatile material was evaporated from the mixture under reduced pressure and the resulting residue was carefully added to water. The solid which formed was separated by filtration, washed with water and dried to give crude product. This was dissolved in methylene chloride and the resulting solution was treated with silica gel and filtered to give a pale yellow solution. Hexane was added to the solution which was then placed on a steam bath until crystallization occurred. The solid was then separated by filtration to give

Molecular Weight:188.61
XLogP3:2.9
Hydrogen Bond Acceptor Count:2
Exact Mass:188.0141259
Monoisotopic Mass:188.0141259
Topological Polar Surface Area:36.7
Heavy Atom Count:13
Complexity:232
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes