2,2'-Bipyridine-4,4'-dicarboxylicacid

white to white-grey powder

1.0 g of 4, 4-dimethyl-2, 2-bipyridine(5.4mmol) was added to the reaction flask, 18mL concentrated sulfuric acid was slowly added dropwise and stirred, the process a lot of heat until the solution was cooled to room temperature and then added potassium dichromate 3.3g (11.3mmol), then the solution becomes dark green, Then reacted at 65 ° C for 6 h. The reaction was completed and cooled to room temperature, the reaction was added to 1000mL of water, a large number of white flocculent precipitate was generated at this time, suction filtration, and then washed with water and methanol to the filtrate was white precipitate was clarified, and then dried in a vacuum oven at 60 18h, Yield 98percentIn a four-necked flask equipped with a thermometer, a magnet and a reflux condenser, 3.7 g (0.02 mol) of analytically pure 4, 4'-dimethyl-2, 2'-bipyridine was added, Was dissolved in a mixed system of 40 mL of water and 0.4 mL of nitric acid and heated to 80 ° C with stirring, And the temperature was maintained five times by adding potassium permanganate solid (12.6 g, 0.08 mol)Until the previous addition of potassium permanganate reaction to dissolve, then add the next batch of potassium permanganate, The reaction was stopped after 6 hours. After cooling to room temperature, the reaction solution is decompressed under reduced pressure, and after the insoluble matter is to be filtered out, Concentrate hydrochloric acid was added to the filtrate to adjust the pH to 1.Static crystallization, a white crystal precipitation.After crystallization was complete, the filtrate was decompressed under reduced pressure and the resulting white crystals were washed with deionized water.The product was then dried in vacuo to give 4.69 g of the desired product, 2, 2'-bipyridyl-4, 4'-dicarboxylic acid, in 96percent yield.To a 125 ml of sulfuric acid (98percent), 5.0 g (0.021 mol) of 4, 4’-dimethyl-2, 2’-bipyridine was added. The obtained mixture was stirred for about 15 min, and a clarified solution with a light pink color was achieved. Then 24 g (0.082 mol) of potassium dichromate was addedcarefully in small portions. And the temperature was held consistently between 70 and 80 °C during this process. After all the dichromate was added, the reaction was stirred for another one hour. The deep green mixture was then poured over 1000 mL of ice H2O and filtered. The solid was washed with H2O and allowed to dry. The resulting light yellow solid was thenrefluxed in 170 mL of 50percent HNO3 for 4h. This reaction solution was poured into into 1 L ofice water. A white powder was isolated by suction filtration and washed with H2O (6.1 g, 95percent).A solution of 4, 4'-dimethyl-2, 2'-bipyridine (2.00 g, 10.9 mmol) in concentratedsulfuric acid (50 mL) was heated to 70 C. Potassium dichromate(9.63 g, 32.6 mmol) was added very slowly. Heating and stirring was maintained for 1 h, and then the hot solution was poured onto ice (300 g) and stirred for 1 h. A fine yellow solid formed. This was filtered and washed with water. The crude product was suspendedin 50percent aqueous nitric acid (50 mL) and heated to 120 C for 4 h. Thesuspension was allowed to cool to room temperature and then poured onto ice (300 g). The suspension was allowed to sit overnight, and the resulting white solid was collected by vacuum filtrationand washed with water. The solid was then thoroughly dried in a flask under vacuum to yield a white solidApproximately 1 gram (5.43 mmol) 4, 4'-dimethyl-2, 2'-bipyridine was added to 40 ml of concentrated H4, 4'-Dicarboxy-2, 2'-bipyridine was synthesized via oxidation of4, 4'-dimethyl-2, 2'-bipyridine. The procedure outlined below ismodified from that previously reported [110]; however, NMR peakassignments are consistent with the literature [110]. Seleniumoxide (5.27 g, 0.0475 mol) was added to 4, 4'-dimethyl-2, 2'-bipyridine(2.04 g, 0.0111 mol) in 135 mL of 1, 4-dioxane. The reactionmixture was heated to reflux with stirring for 3.5 h. After coolingto room temperature, black solid byproduct was removed by vacuumfiltration; the solvent was removed from the filtrate by rotaryevaporation, yielding a red solid. The resulting red solid was dissolvedin 35 mL of concentrated nitric acid. The solution wasslowly heated to reflux with stirring for 4 h. Red fumes were producedupon the addition of the nitric acid and throughout thereflux. The solution was cooled to room temperature and pouredover 180 mL of ice water to crystallize the yellow solid. The productwas isolated from the solution by vacuum filtration. Yield:0.92 g, 34percent. 1H NMR (CDCl3/TMS, 60 MHz): δ/ppm = 8.62 (d, 2H), 8.22 (s, 2H), 7.27 (d, 2H).

Used as an organic chemical synthesis intermediate

Molecular Weight:244.20
XLogP3:0.5
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:6
Rotatable Bond Count:3
Exact Mass:244.04840674
Monoisotopic Mass:244.04840674
Topological Polar Surface Area:100
Heavy Atom Count:18
Complexity:302
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes