* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Chemical Communications, 2009, # 45, p. 6949 - 6951
2
[ 67-56-1 ]
[ 6813-38-3 ]
[ 71071-46-0 ]
Yield
Reaction Conditions
Operation in experiment
90%
Reflux
Dimethyl 2,2 '-bipyridine-4,4'-dicarboxylate (I)To a suspension of 2,2'-dipyridyl-4,4'-dicarboxylic acid (2.00 g, 8.10 mmol) in MeOH (150 mL) was added thionyl chloride (1492 μL, 20.48 mmol) dropwise. The mixture was stirred under reflux overnight. Then the solvent was removed under reduced pressure and the residue was partitioned between CH2Cl2 (100 mL) and water (100 mL). The organic phase was washed through saturated NaHCO3(aq) for 3 times, dried over Na2SO4. The solvent was removed under reduced pressure to give the product as a white solid (2.00 g, 90percent).
88%
With sulfuric acid In water at 105℃;
Take the product I obtained 2g and 10mL 98percent H2SO4, 100mL CH3OH into the flask with a stirrer, reflux at 105 ° C overnight, the end of the reaction to a large amount of water appears white flocculent precipitate, slowly adding NaOH solution adjusted to pH 9.0 , With CH2C12 extract to retain the organic phase, anhydrous Na2S04 dry, evaporated to dry the solvent to obtain white crystals, the yield of 88percent.
86%
Stage #1: for 24 h; Reflux Stage #2: With sodium hydroxide In water at 0℃;
General procedure: The 4,4'-bis[C(0)OR]-2,2'-bipyridine ligands (L-COOCi to L-COOC4) were synthesized as described elsewhere for the synthesis of L-COOCi (Liu et al, Polymer 52:3318-3324, 2011), with slight modifications of the procedure. Briefly, concentrated sulfuric acid (20.4 equiv) was slowly added to a suspension of 4,4'-dicarboxylic acid-2,2'- bipyridine (1 equiv) in the desired alcohol (~ 25 ml of alcohol per 1 g of diacid used). Once the heat subsided, the reaction mixture was refluxed for 24 hours. At the end of the reaction, the volume of the resulting bright, hot pink solution was reduced using a rotary evaporator. The crude product was precipitated out in ice water and neutralized with a 40percent NaOH solution. The pure product was obtained by recrystallization in ethanol, unless otherwise noted. L-COOCi [00215] Yield: 86percent. Mp = 210.0°C [lit. mp = 210-211°C (Case, J Am Chem Soc 68:2574-2577, 1946). XH NMR (298 K, 400 MHz, DMSO-): δ (ppm) = 8.94 (d, J= 4.9 1H), 8.85 (d, J= 0.6 Hz, 1H), 7.93 (dd, J= 5.0, 1.7 Hz, 1H), 3.97 (s, 3H)
76%
at 105℃; for 12 h;
Weigh 4,4'-dicarboxy-2,2'-bipyridine 500mg (2.05mmol) was added to the reaction flask, 100mL of methanol was added, 8mL of concentrated sulfuric acid was slowly added dropwise and stirred at 105 for 12h. After the reaction was completed and cooled to room temperature, the reaction was added to 500 mL of water, and the pH was adjusted to 9 using saturated NaOH solution. After the pH was adjusted, 200 mL of dichloromethane solution was added and allowed to stand still. At this time, a white flocculent precipitate was formed and the supernatant was poured out. The lower layer was extracted with dichloromethane and water (3 × 100 mL), the organic phase was extracted and dried to give the product , Yield 76percent.
Reference：
[1] Journal of the American Chemical Society, 2007, vol. 129, # 18, p. 5919 - 5925
[2] Tetrahedron Asymmetry, 2013, vol. 24, # 8, p. 515 - 525
[3] Inorganic Chemistry, 2018, vol. 57, # 15, p. 9316 - 9326
[4] Dalton Transactions, 2018, vol. 47, # 37, p. 13081 - 13087
[5] Journal of the American Chemical Society, 2016, vol. 138, # 51, p. 16815 - 16826
[6] Helvetica Chimica Acta, 2018, vol. 101, # 5,
[7] Journal of Organic Chemistry, 1992, vol. 57, # 11, p. 3046 - 3051
[8] Patent: WO2010/43866, 2010, A2, . Location in patent: Page/Page column 80
[9] ChemMedChem, 2011, vol. 6, # 5, p. 759 - 764
[10] Chemical Communications, 2015, vol. 51, # 53, p. 10746 - 10749
[11] Patent: CN106188151, 2016, A, . Location in patent: Paragraph 0023; 0025; 0028
[12] Tetrahedron Letters, 1990, vol. 31, # 35, p. 5069 - 5072
[13] Chemical Communications, 2010, vol. 46, # 13, p. 2256 - 2258
[14] Patent: WO2016/25742, 2016, A1, . Location in patent: Paragraph 00109; 00214-00215
[15] Tetrahedron Letters, 2002, vol. 43, # 10, p. 1807 - 1811
[16] Journal of Organic Chemistry, 2006, vol. 71, # 1, p. 315 - 319
[17] Chemistry - A European Journal, 2010, vol. 16, # 1, p. 100 - 103
[18] Angewandte Chemie - International Edition, 2013, vol. 52, # 38, p. 9956 - 9960[19] Angew. Chem., 2013,
[20] Chemical Communications, 2015, vol. 51, # 27, p. 5840 - 5843
[21] Chemical Communications, 2016, vol. 52, # 46, p. 7398 - 7401
[22] Patent: CN107417737, 2017, A, . Location in patent: Paragraph 0051; 0053; 0055
[23] Acta Crystallographica Section C: Crystal Structure Communications, 2007, vol. 63, # 6, p. m280-m282
[24] Journal of Heterocyclic Chemistry, 1990, vol. 27, # 2, p. 163 - 165
[25] Journal of Molecular Catalysis A: Chemical, 2010, vol. 331, # 1-2, p. 117 - 124
[26] Journal of Medicinal Chemistry, 2008, vol. 51, # 22, p. 7053 - 7056
[27] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
[28] Tetrahedron, 1995, vol. 51, # 2, p. 389 - 400
[29] Polymer, 2011, vol. 52, # 15, p. 3318 - 3324
[30] Inorganic Chemistry, 2015, vol. 54, # 20, p. 9687 - 9689
3
[ 366-18-7 ]
[ 79-22-1 ]
[ 71071-46-0 ]
Yield
Reaction Conditions
Operation in experiment
98.2%
With phosphotungstic acid; sodium tungstate; titanium(IV) oxide; zirconium(IV) oxide; triethylamine In methanol at 90℃; for 5 h; Inert atmosphere
The 2,2 '-bipyridine, methyl chloroformate, diethylamine, methanol and catalyst were mixed , then passes nitrogen gas and the reaction was carried out at 90 ° C at 3 MPa for 5 hours. In step 1), the molar ratio of 2,2 '-bipyridine, methyl chloroformate, triethylamine is 1: 2: 5; dose ratio of 2,2 '-bipyridine, methanol and catalyst is 1mol: 500ml: 0.3g;the mentioned catalyst was prepared by the following method: The phosphotungstic acid and sodium tungstate were dissolved in water and added a mixture of nanometer titanium dioxide and nano zirconia which is 6 times the weight of phosphotungstic acid (this mixture contained 70percent by weight of titanium dioxide), stirred the reaction at 60 ° C for 30 h, then vacuum dried the moisture , an dried at 160 ° C for 2h; The mass ratio of the phosphotungstic acid, sodium tungstate and water is 1: 0.15: 5;after completion of the reaction, the mixture was filtered to remove insoluble matter, added to water, and extracted with ethyl acetate. After concentration, the product was obtained as a white solid 2,2'-bipyridinyl-4,4'-carboxylic acid methyl ester in a yield of 98.2percent.
Reference：
[1] Patent: CN106946772, 2017, A, . Location in patent: Paragraph 0017
4
[ 186581-53-3 ]
[ 6813-38-3 ]
[ 71071-46-0 ]
Yield
Reaction Conditions
Operation in experiment
85%
With potassium hydroxide In diethyl ether; chloroform at 20℃;
An ether solution (30 mL) of CH2N2 prepared from N-methyl-N-nitrosourea (2.18 g, 21.2 mmol) and 50percent aqueous KOH (10 mL) was added dropwise to stirred suspension of 2,2'-bipyridine-4,4'-dicarboxylic acid 4a (1.00 g, 4.10 mmol) in CHCl3 (80 mL) at ambient temperature. Upon the evolution of nitrogen, the reaction mixture was filtered from minor solid impurities and the solvents were removed under reduced pressure (10 Torr) at 20 S. The residue was washed with n-hexane (30 mL) and filtered off to afford 4b as light beige powder. Yield 0.94 g (85percent), mp 215 S (lit.20 mp 214 C); Rf 0.61 (Silica gel, CH2Cl2/MeOH (19:1)). The 1H NMR spectrum corresponds to reported data.
4-{2-[2-(4,4'-dimethoxytriphenylmethoxy)ethoxy]ethoxymethyl}-4'-{2-[2-O-<(2-cyanoethoxy)-N,N'-diisopropylaminophosphino]ethoxy>ethoxymethyl}-2,2'-bipyridine[ No CAS ]
With water; potassium hydroxide; In tetrahydrofuran; methanol; at 20℃;Cooling with ice;
Weighing (2,2'-bipyridyl)-4,4'-dicarboxylic acid dimethyl ester (0.55 g, 2.0 mmol) in a conical flask, adding tetrahydrofuran: methanol = 1:1 total 40 mL, Stir at room temperature for 15 minutes; then 2 mL/L potassium hydroxide aqueous solution 2 mL under ice bath Drop into the conical flask, Stirring was continued at room temperature overnight. After the reaction is completed, the solvent is evaporated under reduced pressure. Add 50 mL of water to it, Add 1 mol/L of dilute hydrochloric acid to precipitate the solid. Filtering the filter residue,Add 40 mL of dichloromethane to the filter residue. The crude residue of Intermediate 2 was obtained by suction filtration. White solid, yield 18percent.
N<SUP>4</SUP>,N<SUP>4'</SUP>-dibutyl(2,2'-bipyridine)-4,4'-dicarboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
45%
With triethylamine; In dichloromethane; at 45℃; for 24h;Inert atmosphere;
Weigh Dimethyl 4,4'-dicarboxylate-2,2'-bipyridine 200mg (0.74mmol) was added to the reaction flask, evacuated, protected by nitrogen, anhydrous n-butylamine 7.5mL, anhydrous dichloromethane 20mL and Anhydrous triethylamine 1.0mL, at 45 under the conditions of reaction 24h. The reaction was complete, cooled to room temperature and spun dry. After recrystallization from methylene chloride and ether, a white powder was obtained in 45percent yield.
With dihydrogen peroxide; trifluoroacetic acid; In water; at 20℃;
General procedure: 30percent Aqueous H2O2 (2.25 mL, 22.0 mmol) was slowly added to a solution (suspension in the case of 4a) of 4,4'-di-R-2,2'-bipyridine 2 or 4a-d (15.0 mmol) in TFA (10.0 mL). The reaction mixture was stirred at ambient temperature for 2-4 h (TLC monitoring) and diluted with water (60 mL). The precipitated 7a was filtered off, washed successively with water and acetone, dried in air and used in subsequent reactions without further purification. For isolationof 5 and 7b-d, pH of the aqueous solution was carefully adjusted to 7 with 5 M aqueous NaOH and the products were extracted with CHCl3 (320 mL). The combined extracts were dried over anhydrous MgSO4 and evaporated under reduced pressure (10 Torr). Theresidue was washed with n-hexane (5 mL) affording analytically pure samples of 5 and 7 b-d. 4.3.1. 4,40-Dimethyl-2,20-bipyridine, N-oxide (5). Colorless crystals,yield 2.94 g (98percent), mp 94e95 C (lit.15c mp 83e84 C); Rf (Silica gel,eluent CHCl3/MeOH (19:1)) 0.55. The 1H NMR spectra was consistentwith reported data.
77.9%
With 3-chloro-benzenecarboperoxoic acid; In chloroform; at 0 - 20℃;
3-chloroperoxybenzoic acid (mCPBA, 1.33 g, 7.71 mmol) was added slowly to a solution of the corresponding dimethyl 2,2'-bipyridine-4,4'- dicarboxylate (2 g, 7.35 mmol) in CHC13 (100 mL) at 0 °C. The resulting solution was stirred for 1 hr at this temperature and then, the reaction mixture was allowed to warm to r.t. and stirred overnight. After end of the reaction, solvent was evaporated under reduced pressure. The product was purified by column chromatography on silica gel as colorless powder (Rf = 0.5 in MeOH : DCM = 1 : 19, Yield = 1.65 g (77.9 percent)). JH NMR (400 MHz, CDC13) : 9.34 (s, 1H), 8.91 (d, / = 4.8 Hz, 1H), 8.79 (d, J = 2.8 Hz, 1H), 8.35 (d, J = 6.8 Hz, 1H), 7.95 (dd, J = 4.8, 1.6 Hz, 1H), 7.89 (dd, / = 6.8, 2.4 Hz, 1H), 3.98 (s, 3H), 3.97 (s, 3H). MS (GC-EI) : m/z : calcd for Ci2H7BrO : 245.97 ; found : 246.
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