4,4'-DIMETHOXY-2,2'-BIPYRIDINE

white to light yellow-beige crystalline powder

A mixture of 4, 4′-dimethoxy-2, 2′-bipyridine1, 1′-dioxide (10) (2.50 g, 10.1 mmol), palladium on carbon (5percentPd, 5.16 g, 2.42 mmol, 0.24 equiv), and ethanol (290 mL) was refluxed for 5 min. To the mixture an ethanol solution (170 mL) ofhydrazine monohydrate (39.3 g, 0.785 mol) was added dropwise over 1 h. The reaction mixture wasrefluxed for 18 h and filtered through Celite®. The residue on the Celite was washed with hotethanol. Evaporation of the solvent from the combined filtrate and washings, and recrystallization ofthe residue from methanol gave 7f (0.412 g, 19percent). 7f: pale yellow crystals. 1H NMR (300 MHz, CDCl3) δ 8.48 (d, J = 5.4 Hz, 2H), 7.98 (d, J = 2.4 Hz, 2H), 6.86 (dd, J = 5.4 Hz, 2.4 Hz, 2H), 3.96(s, 6H).Under a nitrogen atmosphere, palladium acetate (11.2 mg, 0.05mmol), 1, 10 - phenanthroline (49.6 mg, 0.25mmol), silver acetate (250 mg, 1.5mmol), (1 ml) was suspended in pyridine (51.1 mg, 0.5mmol) pivalic acid, stirred at 140 °C 26 hours. After the reaction mixture was cooled to room temperature, the insoluble matter was removed by filtration over celite, methylene chloride (10 ml) was washed. The filtrate was concentrated under reduced pressure, 1, 1, 2, 2 - tetrachloroethane (15.8 μl, 0.15mmol) was added as an internal standard substance was obtained residue, Under an argon atmosphere, anhydrous FeCl 2 (76.0 mg, 0.6 mmol) was added to a 50 mL Schlenk bottle, and dissolved in 6 mL of absolute ethanol at 60 C;Further, a solution of 4, 4'-dimethoxy-2, 2'-bipyridine (129.7 mg, 0.6 mmol) in ethanol (4 mL) was added dropwise to the mixture. The reaction was carried out at 60 C for 1 hour. Brown-red complexes are precipitated from the system, Filtered, washed twice with cold ethanol, concentrated to remove solvent, dried in vacuo for 12 h.The dark red solid product 3 was obtained in 47% yield.Anhydrous Fe(acac) 2 (127.0 mg, 0.5 mmol) was added to a 50 mL Schlenk bottle under an argon atmosphere, and dissolved in 6 mL of absolute ethanol at 60 C;Further, a solution of 4, 4'-dimethoxy-2, 2'-bipyridine (108.1 mg, 0.5 mmol) in ethanol (4 mL) was added dropwise to the mixture. The reaction was carried out at 60 C for half an hour, and then returned to room temperature and stirred overnight.The filtrate was collected by filtration, concentrated, washed twice with cold ethanol and dried in vacuo for 12 h.The product 7 was obtained as a dark brown solid, yield 38%.0.25mmol of Cu(NO3)2·3H2O was added to 0.25mmol (37muL) of 4, 4, 4-trifluoro-1-(2-furyl)-1, 3-butanedione (tfa) in acetonitrile (4mL). The solution was stirred for 4h at room temperature. Next, 0.25mmol (0.0540g) of 4, 4-dimethoxy-2, 2-bipyridine (dmb) previously dissolved in acetonitrile was added dropwise. This new mixture was stirred for another 24h. After some days at room temperature, a green precipitate was removed by filtration, washed with acetonitrile and dried under reduced pressure. (0007) MM: 573.92gmol-1. Yield: 85%. Anal. Calc. for (CuC20H16F3N3O8)1.5H2O: C, 41.85; H, 3.34; N, 7.32%. Found: C, 41.89; H, 2.91; N, 8.08%. ATR-FTIR, nu (cm-1): 3128, 3083, 1589, 1567, 1519, 1503, 1474, 1442, 1421, 1375, 1320, 1287, 1265, 1230, 1191, 1132, 1103, 1078, 1040, 955, 912, 879, 843, 835, 780, 687, 591, 578, 434. UV-Vis (methanol), lambdamax (epsilon)=228 (4.7×104M-1 cm-1), 287 (1.9×104M-1 cm-1), 298 (1.9×104M-1 cm-1), 341 (1.8×104M-1 cm-1), 354 (1.9×104M-1 cm-1), 626 (4.3×101M-1 cm-1), 639 (solid state) nm. LambdaM (methanol)=106.20 S cm2mol-1.General procedure: Dried RuCl3 (0.20 g, 0.96 mmol) was dissolvedin dipropylene glycol (10 mL) and deionized water (1 mL).The solution was refluxed until the metal salt was dissolved, obtaining a dark green solution. Bipyridine (0.469 g; 3.0 mmol) wasadded, resulting in a brown solution. Ascorbic acid (0.177 g, 1.0 mmol) was then added and the solution refluxed for 20 min at250 C, the brown colour changing to red. After cooling, the solutionwas diluted to 40 mL and the pH adjusted to 8 by addition of afew drops of NaOH solution (2.5 M). NaBF4 (4.0 g, 36 mmol) wasadded and the solution cooled on ice. After vacuum filtration, washing with cold water, and drying, 0.329 g [Ru(bpy)3](BF4)2product was obtained.

Molecular Weight:216.24
XLogP3:1.4
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:3
Exact Mass:216.089877630
Monoisotopic Mass:216.089877630
Topological Polar Surface Area:44.2
Heavy Atom Count:16
Complexity:191
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes