* 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.
To 5,5'-dimethyl-2,2'-bipyridine (1.0 g) in water (35 ml), KMnO4 (6.0 g) was added and then, the resultant mixture was refluxed with magnetic stirring for overnight. After TLC analyses showed total consumption of the starting materials, the reaction mixture was filtered to remove MnO2 and the filtrate was concentrated to ca. 5 ml. The resultant mixture was then acidified with 35percent HCl aq to be kept in a refrigerator for overnight. The white precipitate was retrieved through filtration and then washed repeatedly with water to give the title compound (1.0 g, 74percent) as a white powder
54%
With potassium permanganate In water at 80 - 85℃; for 24 h;
A suspension of 5,5′-dimethyl-2,2′-bpy (1.51g, 8.2mmol) was dissolved in 100mL water. Solid KMnO4 (8.57g, 54.2mmol) was added to the initial suspension. Then, the reaction mixture was stirred and heated up to 80–85°C for 24h. The deep black solution was cooled to r.t. and filtered off using frit funnel; the aqueous phase was then neutralized with concentrated HCl, resulting in the formation of white suspension. The solid was then filtered under vacuum. The white powder was collected and dried in vacuum desiccators. Yield: 1.33g, 54percent. 1H NMR (600MHz, [D6] DMSO): δ=9.29 (s, 2H, 6,6′-bpy), 8.57 (m, 2H, 3,3′-bpy), 8.45 (m, 2H, 4,4′-bpy).
Reference：
[1] Dalton Transactions, 2008, # 15, p. 2054 - 2060
[2] Journal of the American Chemical Society, 2012, vol. 134, # 2, p. 968 - 978
[3] Chemistry - A European Journal, 2012, vol. 18, # 23, p. 7030 - 7035
[4] Chemistry - A European Journal, 2013, vol. 19, # 40, p. 13369 - 13375
[5] Dalton Transactions, 2016, vol. 45, # 3, p. 881 - 885
[6] Molecular Crystals and Liquid Crystals, 2010, vol. 519, p. 43 - 53
[7] Dalton Transactions, 2016, vol. 45, # 10, p. 4407 - 4415
[8] Journal of Materials Chemistry A, 2016, vol. 4, # 40, p. 15320 - 15326
[9] Journal of Medicinal Chemistry, 1993, vol. 36, # 24, p. 3853 - 3858
[10] Chemical Communications, 2009, # 41, p. 6237 - 6239
[11] Langmuir, 2012, vol. 28, # 11, p. 5023 - 5030
[12] Synlett, 2013, vol. 24, # 6, p. 765 - 769
[13] Tetrahedron, 2016, vol. 72, # 35, p. 5456 - 5464
[14] Chemistry - A European Journal, 1998, vol. 4, # 11, p. 2237 - 2250
[15] Tetrahedron Letters, 1998, vol. 39, # 22, p. 3689 - 3692
[16] European Journal of Organic Chemistry, 1999, # 7, p. 1745 - 1748
[17] Journal of the American Chemical Society, 2013, vol. 135, # 36, p. 13558 - 13566
[18] Chemistry of Materials, 2017, vol. 29, # 8, p. 3671 - 3677
[19] Tetrahedron Letters, 2011, vol. 52, # 9, p. 995 - 998
[20] Inorganica Chimica Acta, 2018, vol. 473, p. 245 - 254
[21] Gazzetta Chimica Italiana, 1997, vol. 127, # 2, p. 63 - 68
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[23] Journal of the American Chemical Society, 1982, vol. 104, # 26, p. 7519 - 7526
[24] Journal of Organometallic Chemistry, 1988, vol. 355, p. 193 - 196
[25] Tetrahedron Letters, 1995, vol. 36, # 36, p. 6471 - 6474
[26] European Journal of Inorganic Chemistry, 1999, # 9, p. 1507 - 1521
[27] Patent: US2007/290199, 2007, A1,
[28] Dalton Transactions, 2008, # 28, p. 3701 - 3708
[29] Chemistry - A European Journal, 2012, vol. 18, # 1, p. 267 - 276
[30] Organometallics, 2011, vol. 30, # 24, p. 6572 - 6586
[31] Chemical Science, 2013, vol. 4, # 12, p. 4486 - 4493
[32] Chemical Communications, 2014, vol. 50, # 18, p. 2304 - 2307
[33] European Journal of Inorganic Chemistry, 2014, # 12, p. 2029 - 2037
[34] European Journal of Inorganic Chemistry, 2014, vol. 2014, # 12, p. 2029 - 2037
[35] Journal of Organic Chemistry, 2014, vol. 79, # 22, p. 11170 - 11178
[36] Chemistry - A European Journal, 2018, vol. 24, # 54, p. 14539 - 14546
2
[ 5326-23-8 ]
[ 1802-30-8 ]
Yield
Reaction Conditions
Operation in experiment
84%
With hydrogenchloride; sodium hydroxide In methanol; water
Example 2 25 g of 6-chloronicotinic acid and 14 g of sodium hydroxide are dissolved in a mixture of 100 ml of water and 80 ml of methanol. Following the addition of 5 g of palladium (10percent by weight on activated carbon) as catalyst, the mixture is stirred for 24 h at 80-85° C. at 0.1 MPa. The catalyst is then filtered off. Following acidification to pH 1 using hydrochloric acid, the product, 2,2'-bipyridyl-5,5'-dicarboxylic acid, precipitates out as a white solid. This gives 16.3 g (84percent yield).
81%
With hydrogenchloride; sodium hydroxide In water; ethylene glycol
Example 1 25 g of 6-chloronicotinic acid and 14 g of sodium hydroxide are dissolved in a mixture of 100 ml of water and 80 ml of ethylene glycol. Following the addition of 0.56 g of palladium (30percent by weight on activated carbon; corresponds to an addition of 168 mg of pure palladium) as catalyst, the mixture is stirred for 5 h at 80-85° C. at 0.1 MPa. The catalyst is then filtered off. Following acidification to pH 1 using hydrochloric acid, the product, 2,2'-bipyridyl-5,5'-dicarboxylic acid, precipitates out as a white solid. This gives 15.7 g (81percent yield).
79%
With hydrogenchloride; sodium hydroxide In methanol; water
Example 3 25 g of 6-chloronicotinic acid and 14 g of sodium hydroxide are dissolved in a mixture of 100 ml of water and 80 ml of methanol. Following the addition of 10 g of palladium (5percent by weight on activated carbon) as catalyst, the mixture is stirred for 30 h at 80-85° C. at 0.1 MPa. The catalyst is then filtered off. Following acidification to pH 1 using hydrochloric acid, the product, 2,2'-bipyridyl-5,5'-dicarboxylic acid, precipitates out as a white solid. This gives 15.3 g (79percent yield).
Reference：
[1] Journal of Organometallic Chemistry, 1988, vol. 355, p. 193 - 196
[2] Journal of the American Chemical Society, 1982, vol. 104, # 26, p. 7519 - 7526
[3] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
4
[ 1762-46-5 ]
[ 1802-30-8 ]
Reference：
[1] Journal of Medicinal Chemistry, 1993, vol. 36, # 24, p. 3853 - 3858
5
[ 3510-66-5 ]
[ 1802-30-8 ]
Reference：
[1] Chemistry - A European Journal, 1998, vol. 4, # 11, p. 2237 - 2250
[2] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
6
[ 1603-41-4 ]
[ 1802-30-8 ]
Reference：
[1] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
7
[ 1003-68-5 ]
[ 1802-30-8 ]
Reference：
[1] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
8
[ 115185-81-4 ]
[ 1802-30-8 ]
Reference：
[1] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
9
[ 3060-42-2 ]
[ 1802-30-8 ]
Reference：
[1] Journal of the American Chemical Society, 1946, vol. 68, p. 2574,2576
10
[ 1762-34-1 ]
[ 244303-60-4 ]
[ 1802-30-8 ]
Reference：
[1] Patent: JP2005/82511, 2005, A, . Location in patent: Page/Page column 4-6
11
[ 59-67-6 ]
[ 1802-30-8 ]
Reference：
[1] Journal of the Chemical Society, 1956, p. 616,619
12
[ 244303-60-4 ]
[ 1802-30-8 ]
Reference：
[1] Patent: JP2005/82511, 2005, A, . Location in patent: Page/Page column 5
13
[ 64-17-5 ]
[ 1802-30-8 ]
[ 1762-46-5 ]
Yield
Reaction Conditions
Operation in experiment
77%
at 0℃; for 24 h; Reflux
Diethyl 2,2'-bipyridine-5,5'-dicarboxylate Procedure: Bipy55'DC (200 mg, 0.82 mmoles) and EtOH (13 mL) were added to a dried flask and stirred on ice. Thionyl chloride (1.3 mL) was added dropwise on ice, after which the flask was fitted with a reflux condenser and heated at reflux. After 24 hr, the reaction was cooled on ice and quenched by the dropwise addition of saturated Na2CO3 (20 mL). The aqueous layer was extracted with CH2Cl2 (4*20 mL) and the combined organics were dried over Na2SO4(s), and concentrated under reduced pressure. The crude product was then purified by chromatography on silica (3percent acetone in 1:1 DCM/hexanes) to afford the title compound (190 mg, 77percent) as a white solid. 1H NMR (500 MHz, CDCl3) δ 9.32 (dd, J=0.5, 2.0 Hz, 1H), 8.59 (dd, J=0.5, 8.5 Hz, 1H), 8.46 (dd, J=2.0, 8.5 Hz, 1H), 4.47 (q, J=7.5 Hz, 2H), 1.46 (t, J=7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 165.2, 158.3, 150.6, 138.1, 126.6, 121.3, 61.6, 14.3; HRMS (ESI) m/z 301.1193 [calc'd for C16H17N2O4 (M+H)+ 301.1183].
Reference：
[1] Inorganic Chemistry, 2017, vol. 56, # 3, p. 1366 - 1374
[2] Chemistry - A European Journal, 2012, vol. 18, # 23, p. 7030 - 7035
[3] Dalton Transactions, 2016, vol. 45, # 3, p. 881 - 885
[4] Chemical Communications, 2016, vol. 52, # 48, p. 7600 - 7603
[5] Journal of the American Chemical Society, 2017, vol. 139, # 49, p. 17747 - 17750
[6] Chemistry - A European Journal, 2018, vol. 24, # 10, p. 2457 - 2465
[7] Chemistry - A European Journal, 2018,
[8] Patent: US2016/280701, 2016, A1, . Location in patent: Paragraph 0300; 0301; 0302
[9] Journal of the American Chemical Society, 2012, vol. 134, # 2, p. 968 - 978
[10] Journal of Molecular Catalysis A: Chemical, 2010, vol. 331, # 1-2, p. 117 - 124
[11] European Journal of Inorganic Chemistry, 1999, # 9, p. 1507 - 1521
[12] Chemical Communications, 2009, # 41, p. 6237 - 6239
[13] Journal of Heterocyclic Chemistry, 1977, vol. 14, p. 191,193
[14] Journal of the American Chemical Society, 1982, vol. 104, # 26, p. 7519 - 7526
[15] Dalton Transactions, 2008, # 28, p. 3701 - 3708
[16] Physical Chemistry Chemical Physics, 2014, vol. 16, # 28, p. 14874 - 14881
[17] Patent: CN106496113, 2017, A, . Location in patent: Paragraph 0059; 0060; 0066; 0067; 0073; 0074
14
[ 1802-30-8 ]
[ 1762-46-5 ]
Reference：
[1] Chemistry - A European Journal, 2013, vol. 19, # 40, p. 13369 - 13375
15
[ 64-17-5 ]
[ 1802-30-8 ]
[ 1762-46-5 ]
[ 105501-69-7 ]
Reference：
[1] Journal of Medicinal Chemistry, 1993, vol. 36, # 24, p. 3853 - 3858
[2] Journal of Medicinal Chemistry, 1993, vol. 36, # 24, p. 3853 - 3858
With chromium(VI) oxide; sulfuric acid; periodic acid; In water; at 20℃; for 24h;
General procedure: (Table 2, entry 7) H5IO6 (1.37g, 6.0 mmol) was dissolved in the mixture of conc. H2SO4(10 mL) and H2O (5 mL) with stirring at room temperature. CrO 3 (0.10g, 1.0 mmol) was added to the solution and dissolved with stirring. Powdered 4,4?-dimethyl-2,2?-bipyridine 1(0.184g, 1.0 mmol) was added in one portion to the solution. The resulted mixture was stirred vigorously at room temperature for 24h. The solution was poured slowly into ice-water (200 mL) with stirring, and the mixture was stirred for 10 min. White precipitate appeared immediately. The precipitate was collected by filtration, and washed well successively with H 2 O and methanol. Vacuum drying gave 0.243g (99%) 4,4?-dicarboxy-2,2?-bipyridine 2 as white powder.
74%
With potassium permanganate; water;Reflux;
To 5,5'-dimethyl-2,2'-bipyridine (1.0 g) in water (35 ml), KMnO4 (6.0 g) was added and then, the resultant mixture was refluxed with magnetic stirring for overnight. After TLC analyses showed total consumption of the starting materials, the reaction mixture was filtered to remove MnO2 and the filtrate was concentrated to ca. 5 ml. The resultant mixture was then acidified with 35% HCl aq to be kept in a refrigerator for overnight. The white precipitate was retrieved through filtration and then washed repeatedly with water to give the title compound (1.0 g, 74%) as a white powder
54%
With potassium permanganate; In water; at 80 - 85℃; for 24h;
A suspension of 5,5?-dimethyl-2,2?-bpy (1.51g, 8.2mmol) was dissolved in 100mL water. Solid KMnO4 (8.57g, 54.2mmol) was added to the initial suspension. Then, the reaction mixture was stirred and heated up to 80-85C for 24h. The deep black solution was cooled to r.t. and filtered off using frit funnel; the aqueous phase was then neutralized with concentrated HCl, resulting in the formation of white suspension. The solid was then filtered under vacuum. The white powder was collected and dried in vacuum desiccators. Yield: 1.33g, 54%. 1H NMR (600MHz, [D6] DMSO): delta=9.29 (s, 2H, 6,6?-bpy), 8.57 (m, 2H, 3,3?-bpy), 8.45 (m, 2H, 4,4?-bpy).
With potassium dichromate; sulfuric acid; In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; water; nitric acid;
Step 1 5,5'-Dicarboxy-2,2'-bipyridine (M1) To a stirred solution of sulfuric acid (97%, 125 mL), 5.0g (27.1 mmol) of 5,5'-dimethyl-2,2'-bipyridine was added. 24 g (81.5 mmol) of potassium dichromate was then added in small portions, such that the temperature remained between 70 to 80 C. After all the dichromate was added, the reaction was stirred until the temperature fell below 40 C. The reaction mixture was poured into 800 mL of ice water and filtered. The solid was washed with water until the green colour of the filtrate disappeared and allowed to dry. The resulting light yellow solid was then further purified by refluxing it in 170 mL of 50% nitric acid for 4 h. This solution was poured over ice, diluted with 1 L of water and cooled to 5 C. The precipitate was filtered, washed with water, then acetone and allowed to dry at 100 C. under vacuum giving 6.03 g (91.0%) of product as a fine white solid. M. P.>400 C.
Stage #1: methanol; 2,2'-bipyridine-5,5'-dicarboxylic acid With sulfuric acid Reflux; Cooling with ice;
Stage #2: With ammonia In water
25%
With thionyl chloride at 0℃; for 24h; Reflux;
Dimethyl 2,2'-bipyridine-5,5'-dicarboxylate
10298] Procedure:10299] BipySS’DC (200 mg, 0.82 mmoles) and MeOH (13 mE) were added to a dried flask and stirred on ice. Thionyl chloride (1.3 mE) was added dropwise on ice, afier which the flask was fitted with a reflux condenser and heated at reflux. Afier 24 hr, the reaction was cooled on ice and quenched by the dropwise addition of saturated NaHCO3 (20 mE). The aqueous layer was extracted with CHC13 (3x30 mE) and the combined organics were washed with saturated NaHCO3 (1 x30 mE), dried over Na2SO4(s), and concentrated under reduced pressure. The crude product was then purified by chromatography on silica (25-90% EtOAc in hexanes) and recrystallized from CHC13 to afford the title compound (56 mg, 25%) as a pale yellow crystalline solid.‘H NMR (500 MHz, CDC13) ö 9.32 (s, 1H), 8.61 (d, J=8.0 Hz, 1H), 8.47 (dd, J=1.5, 8.0 Hz, 1H), 4.02 (s, 3H); ‘3C NMR (125 MHz, CDC13) ö 165.7, 158.3, 150.6, 138.2, 129.3, 121.4, 52.6; HRMS (ESI) mlz 273.0863 [calc’d for C,4H,3N204 (M+H) 273.0870].
Diethyl 2,2'-bipyridine-5,5'-dicarboxylate Procedure: Bipy55'DC (200 mg, 0.82 mmoles) and EtOH (13 mL) were added to a dried flask and stirred on ice. Thionyl chloride (1.3 mL) was added dropwise on ice, after which the flask was fitted with a reflux condenser and heated at reflux. After 24 hr, the reaction was cooled on ice and quenched by the dropwise addition of saturated Na2CO3 (20 mL). The aqueous layer was extracted with CH2Cl2 (4*20 mL) and the combined organics were dried over Na2SO4(s), and concentrated under reduced pressure. The crude product was then purified by chromatography on silica (3% acetone in 1:1 DCM/hexanes) to afford the title compound (190 mg, 77%) as a white solid. 1H NMR (500 MHz, CDCl3) delta 9.32 (dd, J=0.5, 2.0 Hz, 1H), 8.59 (dd, J=0.5, 8.5 Hz, 1H), 8.46 (dd, J=2.0, 8.5 Hz, 1H), 4.47 (q, J=7.5 Hz, 2H), 1.46 (t, J=7.5 Hz, 3H); 13C NMR (125 MHz, CDCl3) delta 165.2, 158.3, 150.6, 138.1, 126.6, 121.3, 61.6, 14.3; HRMS (ESI) m/z 301.1193 [calc'd for C16H17N2O4 (M+H)+ 301.1183].
With sulfuric acid; at 80℃; for 5h;
4,4-Dicarboxylic acid-2,2-bipyridine (4.88 g) was added to 27.60 g of ethanol, 1.84 g of concentrated sulfuric acid (98%) was added,After reacting for 5 hours at 80 degrees Celsius, 0.75 parts by mass of the solvent was distilled off by distillation under reduced pressure and treated with 10.00 g of water and 74.00 g of bisMethylene chloride was subjected to extraction and separation, and the solvent was separated and evaporated twice to give 5.70 g of the crude product in a yield of 95%.
To 2,2'-bipyridine-5,5'-carboxilic acid (0.08 g), thionyl chloride (5.0 ml) was added and then, the resultant heterogeneous solution was refluxed until it became homogeneous (ca. 5 h). The resultant reaction mixture was evaporated to dryness and dried in vacuo to afford the title compound as a pale-yellow powder. The product was used for the syntheses of bpyLacAc, bpyCelAc, bpyMalAc, and bpyGlcAc without purification.
100%
With thionyl chloride; for 5h;Reflux;
To 2,2-bipyridine-5,5?-dicarboxylic acid, thionyl chloride was added and then, the resultant heterogeneous mixture was refluxed with magnetic stirring until it became homogeneous (ca. 5 h). The resultant reaction mixture was evaporated to dryness and dried in vacuo to afford the title compound as a pale-yellow powder. The product was then used for the synthesis of bpyLacAc, bpyMalAc, bpyIma, bpyPhe, or bpyPhe(OC2H4)2OH without any purification and characterization. The amounts of 2,2-bipyridine-5,5?-dicarboxylic acid and thionyl chloride used to synthesize each of the bpy derivatives were reported in its synthetic procedure.
99.7%
A suspension of 2,2?-bpy-5,5?-dicarboxylic acid (3.50g, 11.6mmol) in SOCl2 (9.0mL, 124.0mmol) was stirred at r.t. under Ar atmosphere. 1-2 drops of N,N?-dimethylformaide (DMF) was added to enhance solubility of the dcbpy ligand. The reaction was heated up to 40C. After several hours, chunks of dcbpy were still insoluble in SOCl2. To ensure complete solubility, a 10mL of tetrahydrofuran (THF) was added. The heating was continued for a total of 6 h. The solution was cooled down to r.t. and the excess SOCl2 was removed by rotary evaporator. The red colored residue was suspended in hexane, and after sonication for 5min, the solution was filtered off, the orange powder was collected and dried in vacuum desiccator. Yield: 3.25g, 99.7%. 1H NMR (600MHz, [D6] DMSO): delta=9.20 (s, 2H, 6,6?-bpy), 8.56 (m, 2H, 4,4?-bpy), 8.47 (m, 2H, 3,3?-bpy). 13C NMR (150.78MHz, [D6] DMSO): delta=169.1 (CO-bpy), 155.0 (C5,5?), 152.3 (C2,2?), 140.2 (C6,6?), 135.2 (C4,4?), 127.0 (C3,3?).
0.83 g (72.4%)
With pyridine; thionyl chloride;
Step 2 2,2'-Bipyridine-5,5'-dicarbonyl dichloride (M3) 1.0 g (4.1 mmol) of 5,5'-dicarboxy-2,2'-bipyridine (white powder) was added to a dried flask under the argon atmosphere. 20 mL of thionyl chloride and 0.1 mL of dried pyridine were added into the flask. The mixture was refluxed under argon atmosphere for 48 h. The excess thionyl chloride was distilled off. The crude product was recrystallized from 100 mL of n-heptane to afford 0.83 g (72.4%) of white needle crystal.
With thionyl chloride; for 12h;Reflux;
General procedure: Mesoporous silica (SiO2) was synthesized according to pre-vious work by Zhao et al. [35]. Two diimine-tricarbonyl Re(I)complexes (4 and 5, Fig. 1) and a dipodal silane coupling agent(EDTMS, denoted ?D?, Fig. 1) were utilized to synthesize hybridRe(I) photocatalysts by grafting the Re(I) complexes on mesoporousSiO2surfaces. The Re(I) complexes feature two derivatized bpyligands, 2,2-bipyridine-4,4-dicarboxylic acid and 2,2-bipyridine-5,5-dicarboxylic acid. In a typical synthesis of hybrid Re(I)photocatalysts, 100 mg of mesoporous SiO2was dried at 100C for2 h and dispersed in 50 ml of dry toluene, to which 75 l EDTMSwere added under constant stirring and refluxed for 48 h undernitrogen. The surface functionalized SiO2was washed with toluene,diethyl ether, and DCM before collected by centrifugation. In aseparate solution, 25 mg 2,2-bipyridine-4,4-dicarboxylic acid or2,2-bipyridine-5,5-dicarboxylic acid were dissolved in 10 ml ofthionyl chloride. This solution was then refluxed for 12 h and driedunder vacuum. The resulting solid was dispersed in 10 ml DCMand was added drop wise under nitrogen to the functionalizedSiO2which was dispersed in 30 ml of DCM. The combined solu-tion was then refluxed for 12 h and washed with toluene, diethylether, and DCM. The resulting product was dispersed in 40 ml of drytoluene, to which 50 mg of pentacarbonylchlororhenium(I) wereadded. This final solution was refluxed for 12 h under nitrogen andagain washed with toluene, diethyl ether, and DCM. The result-ing hybrid photocatalyst, denoted as ?4-D-SiO2? or ?5-D-SiO2?, wasthen collected as a yellow powder.
With thionyl chloride; for 48h;Reflux;Catalytic behavior;
2,2?-Bipyridine-5,5?-dicarboxylic acid (1.22 g, 5 mmol) was suspended in 30 mL of thionylchloride with refluxing for 48 h. After the solvent was removed under reduced pressure, theresidue, as a yellow solid, was dissolved in 50 mL of dry THF at room temperature under anargon atmosphere. To this solution, a solution of TEMPO-NH2 (4.28 g, 25 mmol) and TEA(4.0 mL, 30 mmol) in dry THF was added dropwise. After the reaction mixture was stirred for24 h, the precipitate was collected by filtration, washed with THF and H2O, and dried underreduced pressure to afford the product (2.01 g, yield 73%).
With thionyl chloride; for 5h;Reflux;
To 2,2-bipyridine-5,50-dicarboxylic acid (bpyCOOH), SOCl2 was added andthen, the resultant heterogeneous mixture was refluxed with a magnetic stirring until it became homogeneous (ca. 5 h). The resultant mixture wasevaporated and dried in vacuo to afford the title compound as a pale yellowpowder. The product was then used in Section 4.7. The reaction conditionswere summarized in Section 4.7.1-4.7.3
With amalgamated zinc In ethanol Heating / reflux;
A red mixture of Ru(acac)3 (200 mg, 0.5 mmol) and 5,5'-(COOH)2-2,2'-bpy (122 mg, 0.5 mmol) in 30 ml ethanol was refluxed under argon with several pieces of mossy ZiVHg amalgam overnight. The resulting brown mixture was cooled and the zinc amalgam was removed with tweezers. The brown precipitate was collected and washed with ethanol and diethyl ether. The brown solid was then dissolved in 50 ml 0.1 M NH3 and filtered. The green filtrate was stirred in air overnight to give a red solution. The solution was filtered and then evaporated to dryness. The purple-red precipitate was collected and washed with acetone and diethyl ether and then air dried. Yield: 22%; E0 = 0.18 V vs NHE at pH = 8 (phosphate buffer)
Stage #1: 5,5'-dimethyl-2,2'-bipyridine With potassium permanganate; sulfuric acid In water at -5 - 20℃; for 3 - 18h; Heating / reflux; Irradiation;
Stage #2: With sodium carbonate In water
Stage #3: In water Acidic aqueous solution;
With hydrogenchloride; sodium hydroxide;palladium; In methanol; water;
Example 2 25 g of 6-chloronicotinic acid and 14 g of sodium hydroxide are dissolved in a mixture of 100 ml of water and 80 ml of methanol. Following the addition of 5 g of palladium (10% by weight on activated carbon) as catalyst, the mixture is stirred for 24 h at 80-85 C. at 0.1 MPa. The catalyst is then filtered off. Following acidification to pH 1 using hydrochloric acid, the product, 2,2'-bipyridyl-5,5'-dicarboxylic acid, precipitates out as a white solid. This gives 16.3 g (84% yield).
81%
With hydrogenchloride; sodium hydroxide;palladium; In water; ethylene glycol;
Example 1 25 g of 6-chloronicotinic acid and 14 g of sodium hydroxide are dissolved in a mixture of 100 ml of water and 80 ml of ethylene glycol. Following the addition of 0.56 g of palladium (30% by weight on activated carbon; corresponds to an addition of 168 mg of pure palladium) as catalyst, the mixture is stirred for 5 h at 80-85 C. at 0.1 MPa. The catalyst is then filtered off. Following acidification to pH 1 using hydrochloric acid, the product, 2,2'-bipyridyl-5,5'-dicarboxylic acid, precipitates out as a white solid. This gives 15.7 g (81% yield).
79%
With hydrogenchloride; sodium hydroxide;palladium; In methanol; water;
Example 3 25 g of 6-chloronicotinic acid and 14 g of sodium hydroxide are dissolved in a mixture of 100 ml of water and 80 ml of methanol. Following the addition of 10 g of palladium (5% by weight on activated carbon) as catalyst, the mixture is stirred for 30 h at 80-85 C. at 0.1 MPa. The catalyst is then filtered off. Following acidification to pH 1 using hydrochloric acid, the product, 2,2'-bipyridyl-5,5'-dicarboxylic acid, precipitates out as a white solid. This gives 15.3 g (79% yield).
General procedure: Homogenous Re(I) complexes were synthesized according toprevious work by Wang et al. [36]. The synthesis of 4 started with1 mmol of 2,2-bipyridine-4,4-dicarboxylic acid dispersed in 40 mlof toluene, to which 1 mmol of <strong>[14099-01-5]<strong>[14099-01-5]pentacarbonylchlororhenium</strong>(I)</strong> wasadded. The resulting mixture was refluxed for 6 h under nitrogen,and was then stored at 0C for 1 h. The mixture was purified byfiltration and was concentrated under reduced pressure to give 4.The synthesis of 5 was achieved via the same method by mixing1 mmol 2,2-bipyridine-5,5-dicarboxylic acid in 40 ml of m ethanolwith 1 mmol of <strong>[14099-01-5]<strong>[14099-01-5]pentacarbonylchlororhenium</strong>(I)</strong>.
With hydrogenchloride; In water; at 180℃; under 10343.2 Torr; for 0.75h;Microwave reactor;
To high pressure HP500 reaction vessel containing 800 mg of RuCI3 3H20 and 1.360g of 5,5'H2DCBPy, are added 25ml of H20 and 25ml of 37% HCI. The reactor temperature has been increased at 180C under a pressure of approximately 200 PSI while the reactor power has been set at 800W. These conditions are maintained for a reaction time of 45min under continuous stirring. After slow cooling to room temp., the obtained precipitated has been filtered on porous filter and washed with H2O until to colourless washings. Obtained product has been oven dried (yield 78%) .Figure 3 shows UV-vis spectroscopic characterization of obtained complex. It has not been possible to acquire 1H NMR spectra due to complex high spin.
Al(OH)(2,2'-bipyridine-5,5'-dicarboxylic acid(-2H))[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With acetic acid; In N,N-dimethyl-formamide; at 120℃; for 24h;
MOF-253 was prepared from hydrothermal reaction of AlCl3*6H2O (151 mg, 0.625 mmol), glacial acetic acid (859 L,15.0 mmol), 2,2-bipyridine-5,5-dicarboxylic acid (153 mg,0.625 mmol), and 10 mL N,N-dimethylformamide (DMF) at 120 C for 24 h. The resulting white microcrystalline powder was then filtered and washed with DMF. The solid was washed with methanol via soxhlet extraction for 24 h, and then was collectedby filtration and finally dried at 250 C under vacuum for 12 h.
Zr6(μ3-O)4(OH)4(2,2’-bipyridine-5,5’-dicarboxylate)6[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With trifluoroacetic acid; In N,N-dimethyl-formamide; at 100℃; for 120h;Inert atmosphere; Schlenk technique;
ZrCl4 (30 mg, 0.13 mmol), 2,2?-bipyridine-5,5?-dicarboxylic acid (H2L, 30 mg, 0.12 mmol), DMF (15 mL) and trifluoroacetic acid (0.06 mL) were charged in a vial and heated to 100 C. for 5 days. The resulting solid was collected and washed with DMF to give 40 mg of bpy-UiO (yield 65%). (0161) The bpy-UiO solid showed an identical powder pattern to that simulated from the single crystal structure. See FIGS. 1A and 1G. See also Li et al., Chem. Commun., 2014, 50, 2304. Bpy-UiO exhibited a BET surface area of 2277 m2/g and a pore size of about 7.2 , consistent with the single crystal structure. See FIG. 1D.
Typically, a 2l round bottom flaske quipped with a Schlenk adaptor, glass stoppers and a magnetic stir bar was charged with H2bpydc (6.11 g, 25.0 mmol), benzoic acid (224 g, 2.00 mol), and N,N-dimethylformamide (DMF; 1.00 l) from a newly opened bottle. The resulting mixture was purged with dry Ar for 30 min. Solid ZrCl4 (5.83 g, 25.0 mmol) was then added, after which the mixture was purged with dry Ar for an additional 30 min. Deionized water (820 mul, 45.5 mmol) was added and the mixture was heated with magnetic stirring for 5 days at 120 C under a N2 atmosphere. After allowing the mixture to cool to room temperature, the solvent was decanted and the resulting white microcrystalline powder was washed by soaking three times in 1 l aliquots of fresh DMF for 24 h at 120 C, followed by solvent exchange with tetrahydrofuran (THF) via Soxhlet extraction for 3 days. The THF-solvated powder was filtered under dry Ar, followed by heating at 120 C under dynamic vacuum for 24 h to give fully desolvated 1.
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