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Structure of 366-18-7 * Storage: {[proInfo.prStorage]}
* 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] Yakugaku Zasshi, 1955, vol. 75, p. 733,735[2] Chem.Abstr., 1956, p. 3436
6
[ 366-18-7 ]
[ 15862-19-8 ]
Yield
Reaction Conditions
Operation in experiment
45%
Stage #1: at 100℃; for 24 h; Stage #2: With sodium hydroxide In water
The procedure is similar to the preparation of 2. Mixture of 2,2'-bipyridine (0.5 g, 3.2 mmol), KBr (0.46 g, 3.87 mmol), and a mixed acid (3.9 ml of concentrated HNO3 and 7.7 ml of concentrated H2SO4) was allowed to react for 24 h under reflux after the temperature ascending to 100 °C rapidly. The reaction mixture was poured into 50 ml water and neutralized with solid sodium hydroxide until pH=7. The precipitate was filtered and washed with CHCl3, then extracted with CHCl3. The filtrate was dried over anhydrous MgSO4, the solvent was removed by rotary evaporation, and the residue was purified by column chromatography (EtOAc/petroleum ether, 1:5) to give desired product 5 (0.34 g, 45percent) as a white solid; mp 74-75 °C; Rf 0.40 (silica gel, EtOAc/petroleum ether, 1:3); [found: C, 51.11; H, 2.94. C10H7BrN2 requires C, 51.09; H, 3.00percent]; 1H NMR (400 MHz, CDCl3, ppm) δ 8.74-8.743 (d, J=2 Hz, 1H), 8.70-8.69 (d, J=4 Hz, 1H), 8.40-8.38 (d, J=8 Hz, 1H), 8.35-8.33 (d, J=8 Hz, 1H), 7.97-7.95 (d, J=8 Hz 1H), 7.86-7.82 (t, J=8 Hz, 1H), 7.36-7.33 (t, J=8 Hz, 1H); 13C NMR (100 MHz, CDCl3, ppm) δ 155.13, 154.59, 150.17, 149.23, 139.47, 137.00, 123.99, 122.33, 121.14. GC-MS (m/z) calcd for C10H7BrN2+ [M]+, found 233.95. The compound is known and that the data obtained matches that of the literature values.24b
Reference:
[1] Phosphorus, Sulfur and Silicon and the Related Elements, 1994, vol. 94, # 1-4, p. 405 - 410
11
[ 67-56-1 ]
[ 26437-48-9 ]
[ 366-18-7 ]
[ 15862-19-8 ]
[ 61864-97-9 ]
Reference:
[1] Phosphorus, Sulfur and Silicon and Related Elements, 1996, vol. 109, # 1-4, p. 605 - 608
[2] Phosphorus, Sulfur and Silicon and Related Elements, 1996, vol. 109, # 1-4, p. 605 - 608
12
[ 366-18-7 ]
[ 178039-84-4 ]
Reference:
[1] Journal of the Chemical Society, 1938, p. 1662,1669
[2] Organic Letters, 2015, vol. 17, # 6, p. 1497 - 1500
[3] Organometallics, 2016, vol. 35, # 15, p. 2429 - 2432
13
[ 366-18-7 ]
[ 10495-73-5 ]
Reference:
[1] Tetrahedron Letters, 2006, vol. 47, # 39, p. 6941 - 6943
[2] Acta Chemica Scandinavica, 1998, vol. 52, # 1, p. 77 - 85
[3] Beilstein Journal of Organic Chemistry, 2012, vol. 8, p. 1037 - 1047
14
[ 366-18-7 ]
[ 10495-73-5 ]
[ 49669-22-9 ]
Reference:
[1] Journal of the Chemical Society, 1938, p. 1662,1669
15
[ 366-18-7 ]
[ 15862-18-7 ]
Yield
Reaction Conditions
Operation in experiment
86%
at 150℃; for 15 h;
2,2′-bipyridine (1, 4.99 g, 0.032 mol) and bromine (10.24 g,0.064 mol) were first added in a hydrothermal reaction container andheated to 150 °C and annealed for 15 h. Then, the mixture was cooledand the hard solidwas powdered and following treatedwith Na2SO3 solutionto remove the unreacted bromine. Finally itwas basifiedwith sodiumhydroxide and filtered. The white solid product 5,5′-dibromo-2,2′-bipyridine was obtained by the chromatography on silica(CH2Cl2). 5,5′-dibromo-2,2′-bipyrimidine, 8.64 g (86percent). m.p. 221.6–222.1 °C. 1H-NMR (400 MHz, CDCl3, δ): 7.95 (d, 2H), 8.28 (s, 2H),8.71(d, 2H); 13C-NMR (100 MHz, CDCl3, δ): 121.47 (C5), 122.25 (C3),139.64 (C4); 150.28 (C6),153.64 (C2); IR (KBr): 3049 (C\\H,stretching), 1562, 1453, 1356 (Ar, stretching), 636 (C\\Br, stretching).Anal. calcd for C10H6N2Br2: C 38.22, H 1.91, N 8.92, Br 50.95; found: C38.26, H 1.94, N 8.90, Br 50.97.
86%
at 150℃; for 15 h;
2,2'-bipyridyl (4.99 g, 0.032 mol) and liquid bromine (10.24 g, 0.064 mol)Put into a reaction kettle at a pressure of 2.0 atm at 150 ° C for 15 hours, then cool to room temperature after the reaction, pulverize the solid, add to the Na2SO3 solution and stir to remove unreacted bromine, filter, and alkalizate the acid with a 5percent NaOH solution. , filtration, to obtain a crude product, column separation with ethyl acetate / petroleum ether,8.64 g of white 5,5'-dibromo-2,2'-bipyridine was obtained in a yield of 91percent.
Reference:
[1] Reactive and Functional Polymers, 2016, vol. 106, p. 93 - 98
[2] Patent: CN105130885, 2018, B, . Location in patent: Paragraph 0024; 0026; 0027; 0030; 0033; 0036
[3] New Journal of Chemistry, 2018, vol. 42, # 17, p. 14067 - 14070
[4] Chemistry - A European Journal, 2015, vol. 21, # 51, p. 18576 - 18579
[5] Patent: WO2009/118742, 2009, A1,
16
[ 366-18-7 ]
[ 18511-69-8 ]
Reference:
[1] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2009, vol. 72, # 5, p. 1117 - 1121
[2] Synlett, 2011, # 2, p. 223 - 226
[3] Journal of Organometallic Chemistry, 2015, vol. 791, p. 175 - 182
[4] European Journal of Inorganic Chemistry, 2016, vol. 2016, # 10, p. 1470 - 1479
[5] Patent: CN104478922, 2017, B,
17
[ 626-05-1 ]
[ 110-86-1 ]
[ 366-18-7 ]
[ 49669-22-9 ]
Yield
Reaction Conditions
Operation in experiment
23 %Chromat.
With bis(bipyridine)nickel(II) bromide; sodium iodide In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; Inert atmosphere
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm.x.3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7percent or 20percent of NiBr2*xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
7 %Chromat.
With bis(bipyridine)nickel(II) bromide; sodium iodide In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; Inert atmosphere
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm.x.3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7percent or 20percent of NiBr2*xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
Reference:
[1] Journal of Organic Chemistry, 2006, vol. 71, # 1, p. 315 - 319
[2] Advanced Synthesis and Catalysis, 2003, vol. 345, # 4, p. 497 - 505
24
[ 366-18-7 ]
[ 18511-72-3 ]
Reference:
[1] Yakugaku Zasshi, 1955, vol. 75, p. 733,735[2] Chem.Abstr., 1956, p. 3436
[3] Advanced Synthesis and Catalysis, 2003, vol. 345, # 4, p. 497 - 505
[4] Nippon Kagaku Zasshi, 1956, vol. 77, p. 682,685[5] Chem.Abstr., 1958, p. 9100
25
[ 366-18-7 ]
[ 18511-72-3 ]
[ 51595-55-2 ]
Reference:
[1] Journal of Chemical Sciences, 2018, vol. 130, # 6,
26
[ 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
27
[ 109-04-6 ]
[ 4926-28-7 ]
[ 108-89-4 ]
[ 366-18-7 ]
[ 1134-35-6 ]
[ 56100-19-7 ]
Yield
Reaction Conditions
Operation in experiment
45 %Chromat.
With nickel(II) bromide hydrate; sodium iodide In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; Inert atmosphere
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm.x.3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7percent or 20percent of NiBr2*xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
With nickel(II) bromide hydrate; sodium iodide In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; Inert atmosphere
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm.x.3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7percent or 20percent of NiBr2*xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
Reference:
[1] Journal of the Chinese Chemical Society, 2003, vol. 50, # 2, p. 189 - 192
[2] Journal of Heterocyclic Chemistry, 1986, vol. 23, # 4, p. 1071 - 1077
[3] Journal of Heterocyclic Chemistry, 1986, vol. 23, # 4, p. 1071 - 1077
30
[ 366-18-7 ]
[ 14162-94-8 ]
Reference:
[1] Journal of Heterocyclic Chemistry, 1986, vol. 23, # 4, p. 1071 - 1077
31
[ 366-18-7 ]
[ 14162-95-9 ]
Reference:
[1] Journal of Organic Chemistry, 2007, vol. 72, # 18, p. 6653 - 6661
[2] Synthesis, 1998, # 3, p. 321 - 324
[3] Molecules, 2011, vol. 16, # 6, p. 4615 - 4631
[4] Molecules, 2011, vol. 16, # 10, p. 8353 - 8367
[5] Patent: US2012/247546, 2012, A1,
[6] Chemical Papers, 2012, vol. 66, # 8, p. 733 - 740
[7] Tetrahedron Letters, 2013, vol. 54, # 40, p. 5514 - 5517
[8] Tetrahedron Letters, 2013, vol. 54, # 40, p. 5514 - 5517
[9] Polyhedron, 2014, vol. 67, p. 381 - 387
[10] Journal of Inorganic Biochemistry, 2014, vol. 134, p. 83 - 91
[11] Inorganic Chemistry, 2015, vol. 54, # 6, p. 2742 - 2751
[12] Monatshefte fur Chemie, 2017, vol. 148, # 6, p. 991 - 998
32
[ 366-18-7 ]
[ 99970-84-0 ]
Reference:
[1] Journal of Chemical Sciences, 2018, vol. 130, # 6,
33
[ 366-18-7 ]
[ 917-54-4 ]
[ 56100-22-2 ]
Yield
Reaction Conditions
Operation in experiment
63.8%
at 0℃; for 5 h; Inert atmosphere; Reflux
Methyllithium (1.3 M, 33.80 mmol) in THF (26 mL) was added dropwise to a solution of 2,2'-bipyridine (5.30 g, 34.00 mmol) in diethyl ether (100 mL) at 0 °C under N2 atmosphere. The reaction mixture was stirred for 2 h, and then refluxed for 3 h. Water (10 mL) was added when the mixture cooled to room temperature. The organic layer was separated and the aqueous layer was extracted three times with ether. The combined organic layer was dried by anhydrous Na2SO4. The solvent was removed by evaporation. The resulting orange oil was oxidized with saturated KMnO4/acetone (300 mL) and stirred for 1 h. The filtrate was placed in a flask and acetone was removed by evaporation. The resulting dark oil was distilled under vacuum and finally gave pure 6-methyl-2,2'-bipyridine as colourless oil (3.73 g, 63.8percent). 1H NMR (400 MHz, CDCl3) δ ppm: 8.65 (s, 1H), 8.38 (d, J = 8.0 Hz, 1H), 8.15 (d, J = 7.9 Hz, 1H), 7.72-7.82 (m, 1H), 7.66 (d, J = 7.7 Hz, 1H), 7.21-7.30 (m, 1H), 7.13 (d, J = 7.7 Hz, 1H), 2.61 (s, 3H). 13C NMR (100 MHz, CDCl3) δ ppm: 157.7, 156.3, 155.4, 149.0, 136.9, 136.7, 123.6, 123.2, 121.02, 117.9, 24.5. ESI-MS (m/z): calcd for C11H10N2 [M + H]+ 171.22, found 171.61.
63.8%
at 0℃; for 5 h; Inert atmosphere; Reflux
5.30 g of 2,2'-bipyridine was placed in a three-necked flask,Nitrogen and reduced to below 0 & lt; 0 & gt; C with an ice bath,Then take 100 ml of dry ether to the flask to 2,2 '- bipyridine all dissolved;Another 26 ml of methyl lithium (1.3 moles per liter) was added dropwise to the flask,The reaction was carried out under ice-cooling for 2 hours and then refluxed for 3 hours.After cooling to room temperature,The reaction was quenched by the addition of 10 ml of water,After separation,The aqueous phase was extracted with ether,The solvent was evaporated,300 ml of a saturated potassium permanganate solution in acetone was added,Stirring for one hour,The produced manganese dioxide was removed by filtration,The solvent was distilled off,The pure product II, 3.278 g, was isolated by distillation under reduced pressure at a yield of 63.8percent.
36%
at 0℃; for 0.5 h; Inert atmosphere; Schlenk technique
2,2’-Bipyridyl(180 mg, 1.0 mmol) was added into a 100-mL 2-neck round-bottom flask with amagnetic stirring bar. The flask was evacuated and refilled with N2 gas following theusual Schlenk technique. Dry toluene (30 mL, 0.30 M) was added while stirring andthe reaction mixture was cooled to 0 °C. Methyl lithium in ether solution (3.1 M, 0.32mL, 1.0 mmol, 1.0 equiv) was added dropwise in the course of 30 min, and stirred foran additional 30 min at 0 C. The reaction mixture was quenched with dropwiseaddition of H2O (10 mL). The resulting mixture was extracted with CH2Cl2 (3 10mL) and the combined organic layer was treated with excess MnO2, followed bystirring for 30 min. The crude product was filtered through a pad of Celite® andconcentrated in vacuo. Purification through silica gel column chromatography(hexane/EtOAc = 3:2) and removal of solvent in vacuo gave 6-Mebpy in 36percent (61 mg,0.31 mmol) yield as an oil.
Reference:
[1] Angewandte Chemie - International Edition, 2014, vol. 53, # 23, p. 5872 - 5876
[2] Dyes and Pigments, 2016, vol. 128, p. 33 - 40
[3] Patent: CN105669689, 2016, A, . Location in patent: Paragraph 0032
[4] Angewandte Chemie - International Edition, 2016, vol. 55, # 37, p. 11207 - 11211[5] Angew. Chem., 2016, vol. 128, # 37, p. 11373 - 11377,5
[6] Organic Letters, 2012, vol. 14, # 1, p. 86 - 89
[7] Chemistry Letters, 2018, vol. 47, # 3, p. 329 - 331
[8] Journal of Organic Chemistry, 2012, vol. 77, # 20, p. 8968 - 8979,12
[9] Synthesis, 1992, # 6, p. 519 - 521
[10] Russian Chemical Bulletin, 1997, vol. 46, # 1, p. 202 - 203
[11] Inorganic Chemistry, 2010, vol. 49, # 3, p. 823 - 832
34
[ 5315-25-3 ]
[ 2402-78-0 ]
[ 366-18-7 ]
[ 4411-80-7 ]
[ 57154-73-1 ]
[ 33777-92-3 ]
[ 56100-22-2 ]
Yield
Reaction Conditions
Operation in experiment
47%
With [Ni(2,2'-bipyridine)2Br2]; sodium iodide In N,N-dimethyl-formamide at 20℃; for 8 h; Electrochemical reaction; Inert atmosphere
General procedure: To an undivided electrochemical cell, fitted by a zinc rod as the anode and surrounded by a nickel foam as the cathode, were added DMF (50 mL), 0.1 M NaI, and 1,2-dibromoethane (2.5 mmol, 215 μL). The mixture was electrolyzed under argon at a constant current intensity of 0.2 A at room temperature for 20 min. Then the current was stopped, and [Ni(bpy)]Br2 complex21 (2.6 mmol, 562 mg), 2,6-dichloropyridine (5 mmol, 0.74 g), and 2-bromo-6-methylpyridine (10 mmol, 1.72 g) were sequentially added. The solution was electrolyzed at 0.1 A and room temperature until the starting material was totally consumed (8 h).
With nickel(II) bromide hydrate; sodium iodide In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; Inert atmosphere
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm.x.3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7percent or 20percent of NiBr2*xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
With [Ni(2,2'-bipyridine)2Br2]; sodium iodide In N,N-dimethyl-formamide at 20℃; for 8 h; Electrochemical reaction; Inert atmosphere
General procedure: To an undivided electrochemical cell, fitted by a zinc rod as the anode and surrounded by a nickel foam as the cathode, were added DMF (50 mL), 0.1 M NaI, and 1,2-dibromoethane (2.5 mmol, 215 μL). The mixture was electrolyzed under argon at a constant current intensity of 0.2 A at room temperature for 20 min. Then the current was stopped, and [Ni(bpy)]Br2 complex21 (2.6 mmol, 562 mg), 2,6-dichloropyridine (5 mmol, 0.74 g), and 2-bromo-6-methylpyridine (10 mmol, 1.72 g) were sequentially added. The solution was electrolyzed at 0.1 A and room temperature until the starting material was totally consumed (8 h).
Reference:
[1] European Journal of Medicinal Chemistry, 1984, vol. 19, # 5, p. 399 - 404
38
[ 2402-78-0 ]
[ 110-86-1 ]
[ 366-18-7 ]
[ 53344-72-2 ]
Yield
Reaction Conditions
Operation in experiment
25 %Chromat.
With bis(bipyridine)nickel(II) bromide; sodium iodide In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; Inert atmosphere
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm.x.3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7percent or 20percent of NiBr2*xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
40 %Chromat.
With bis(bipyridine)nickel(II) bromide; sodium iodide In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; Inert atmosphere
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm.x.3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7percent or 20percent of NiBr2*xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
Reference:
[1] Journal of the Chemical Society, Perkin Transactions 1, 1980, p. 2527 - 2530
[2] Dalton Transactions, 2017, vol. 46, # 7, p. 2238 - 2248
[3] Research on Chemical Intermediates, 2017, vol. 43, # 6, p. 3539 - 3552
40
[ 366-18-7 ]
[ 79-37-8 ]
[ 1201-31-6 ]
[ 94695-48-4 ]
[ 94695-50-8 ]
Reference:
[1] Patent: US4617308, 1986, A,
41
[ 366-18-7 ]
[ 103505-54-0 ]
Reference:
[1] Journal of Organic Chemistry, 1998, vol. 63, # 10, p. 3379 - 3385
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Reference:
[1] Journal of Organometallic Chemistry, 1990, vol. 393, # 1, p. 137 - 142
[2] Russian Journal of General Chemistry, 2002, vol. 72, # 2, p. 168 - 172
[3] New Journal of Chemistry, 2002, vol. 26, # 2, p. 207 - 212
[4] Russian Chemical Bulletin, 2002, vol. 51, # 5, p. 796 - 804[5] Izvestiya Akademi Nauk, Seriya Khimicheskaya, 2002, vol. 51, # 5, p. 734 - 741
[6] Russian Chemical Bulletin, 2003, vol. 52, # 3, p. 567 - 569
[7] Organometallics, 2010, vol. 29, # 22, p. 6002 - 6011
[8] Russian Chemical Bulletin, 2005, vol. 54, # 4, p. 942 - 947
[9] Patent: KR101581821, 2015, B1, . Location in patent: Paragraph 0041; 0043
43
[ 366-18-7 ]
[ 1295-35-8 ]
[ 12145-47-0 ]
[ 5259-72-3 ]
[ 46389-47-3 ]
[ 917346-05-5 ]
Reference:
[1] Journal of Organometallic Chemistry, 2006, vol. 691, # 23, p. 4868 - 4873
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[2] New Journal of Chemistry, [3] New Journal of Chemistry, 1989, vol. 13, p. 53 - 60
In tetrahydrofuran; diethyl ether; at 0℃; for 5h;Inert atmosphere; Reflux;
Methyllithium (1.3 M, 33.80 mmol) in THF (26 mL) was added dropwise to a solution of 2,2'-bipyridine (5.30 g, 34.00 mmol) in diethyl ether (100 mL) at 0 C under N2 atmosphere. The reaction mixture was stirred for 2 h, and then refluxed for 3 h. Water (10 mL) was added when the mixture cooled to room temperature. The organic layer was separated and the aqueous layer was extracted three times with ether. The combined organic layer was dried by anhydrous Na2SO4. The solvent was removed by evaporation. The resulting orange oil was oxidized with saturated KMnO4/acetone (300 mL) and stirred for 1 h. The filtrate was placed in a flask and acetone was removed by evaporation. The resulting dark oil was distilled under vacuum and finally gave pure 6-methyl-2,2'-bipyridine as colourless oil (3.73 g, 63.8%). 1H NMR (400 MHz, CDCl3) delta ppm: 8.65 (s, 1H), 8.38 (d, J = 8.0 Hz, 1H), 8.15 (d, J = 7.9 Hz, 1H), 7.72-7.82 (m, 1H), 7.66 (d, J = 7.7 Hz, 1H), 7.21-7.30 (m, 1H), 7.13 (d, J = 7.7 Hz, 1H), 2.61 (s, 3H). 13C NMR (100 MHz, CDCl3) delta ppm: 157.7, 156.3, 155.4, 149.0, 136.9, 136.7, 123.6, 123.2, 121.02, 117.9, 24.5. ESI-MS (m/z): calcd for C11H10N2 [M + H]+ 171.22, found 171.61.
63.8%
In diethyl ether; at 0℃; for 5h;Inert atmosphere; Reflux;
5.30 g of 2,2'-bipyridine was placed in a three-necked flask,Nitrogen and reduced to below 0 & lt; 0 & gt; C with an ice bath,Then take 100 ml of dry ether to the flask to 2,2 '- bipyridine all dissolved;Another 26 ml of methyl lithium (1.3 moles per liter) was added dropwise to the flask,The reaction was carried out under ice-cooling for 2 hours and then refluxed for 3 hours.After cooling to room temperature,The reaction was quenched by the addition of 10 ml of water,After separation,The aqueous phase was extracted with ether,The solvent was evaporated,300 ml of a saturated potassium permanganate solution in acetone was added,Stirring for one hour,The produced manganese dioxide was removed by filtration,The solvent was distilled off,The pure product II, 3.278 g, was isolated by distillation under reduced pressure at a yield of 63.8%.
36%
In diethyl ether; toluene; at 0℃; for 0.5h;Inert atmosphere; Schlenk technique;
2,2?-Bipyridyl(180 mg, 1.0 mmol) was added into a 100-mL 2-neck round-bottom flask with amagnetic stirring bar. The flask was evacuated and refilled with N2 gas following theusual Schlenk technique. Dry toluene (30 mL, 0.30 M) was added while stirring andthe reaction mixture was cooled to 0 C. Methyl lithium in ether solution (3.1 M, 0.32mL, 1.0 mmol, 1.0 equiv) was added dropwise in the course of 30 min, and stirred foran additional 30 min at 0 C. The reaction mixture was quenched with dropwiseaddition of H2O (10 mL). The resulting mixture was extracted with CH2Cl2 (3 10mL) and the combined organic layer was treated with excess MnO2, followed bystirring for 30 min. The crude product was filtered through a pad of Celite andconcentrated in vacuo. Purification through silica gel column chromatography(hexane/EtOAc = 3:2) and removal of solvent in vacuo gave 6-Mebpy in 36% (61 mg,0.31 mmol) yield as an oil.
The palladium complex PdCl2Bipy was prepared as follows: 0.0030 mole 2,2'-bipyridine was taken in 10 ml methanol and to it 0.0029 mole PdCl2 was added. The mixture as stirred for 6 hrs at room temperature. The resulting yellowish red coloured precipitate as filtered washed with methanol and dried under vacuum. The yield of the complex is 85%.
General procedure: The complexes [Pd(bipy)Cl2] and [Pd(phen)Cl2], were obtained by adding 1 mmol of the respective ligand to 0.326 g (1 mmol) of K2[PdCl4] suspended/dissolved in 40 mL of wet methanol under reflux for about 1 h. The precipitated crystalline powders were recovered by filtration and dried under vacuum for 2 h.
Chloro[l,3-bis(2,6-di-i-propylphenyl)imidazol-2-ylidene]copper(I) (195.1 mg, 0.4 mmol) and silver triflate (102.7 mg, 0.4 mmol) were mixed under nitrogen in 25 mL flask and 10 mL of dry THF were added. Reaction mixture was stirred at RT for 30 minutes.Solution of 2,2'-bipyridine (62.4 mg, 0.4 mmol) in dry THF (5 mL) was added. Reaction mixture turned orange and was stirred at RT overnight. Resulting mixture was filtered through Celite and solvent was evaporated on rotovap. Recrystallization from CH2CI2 by vapor diffusion of EtaO gave 215 mg (70.9%) of orange crystals. Anal, calcd. forC38H44CUF3N4O3S: C, 60.26; H, 5.86; N, 7.40; Found: C, 60.18; H, 5.82; N, 7.38. Structure was confirmed by iH-NMR spectrum of [(IPR)Cu(bipy)]OTf (CDCb, 400MHz).
With nickel(II) bromide hydrate; sodium iodide; In N,N-dimethyl-formamide; at 20℃;Electrochemical reaction; Inert atmosphere;
General procedure: The controlled current preparative electrolysis were carried out with a potentiostat/galvanostat equipment. Undivided cells with 20 mL compartment were used. Zn or Fe metallic rod with 8 mm diameter was used as the sacrificial anode. Ni foam (6 cm×3.5 cm) was used as the cathode. It could be re-used after washing with a 6 M HCl solution following by water and acetone, and dried. The same solution was used to clean the anode. A 5 mL DMF solution containing 7% or 20% of NiBr2·xH2O or [Ni(bpy)]Br221 and x mmol of the corresponding mixture of 2-bromomethylpyridines or 2,6-dihalopyridines (heterocouplings in Table 1, Table 2, Table 4 and Table 5), or (2.5 mmol) of 2,6-dihalopyridines (homocoupling in Table 3) was stirred or sonicated before the electrolysis, to ensure the solubilization of reagents. A pre-electrolysis was carried out with 15 mL of the electrolytic solution (DMF, 0.1 M NaI and 0.75 mmol of 1,2-dibromoethane), passing a charge of 146 C (I=150 mA). Then, the previous prepared solution of bromopicoline or bromopyridine and the catalyst in 5 mL DMF, was added to the electrolytic cell and the constant current electrolysis (I=100 mA) applied. It is important to ensure that the cell potential must not exceed 1.8 V in order to avoid the reduction of the substrate on the cathode surface. After the total consumption of the reagent (number of coulombs described in the tables), the reaction was stopped and the solvent removed under reduced pressure. The residue was dissolved in CH2Cl2 and washed with several portions of a 6 M NH4OH solution. After drying over Na2SO4, the organic layer was evaporated under reduced pressure.
With bis(bipyridine)nickel(II) bromide; sodium iodide; In N,N-dimethyl-formamide; at 20℃; for 8h;Electrochemical reaction; Inert atmosphere;
General procedure: To an undivided electrochemical cell, fitted by a zinc rod as the anode and surrounded by a nickel foam as the cathode, were added DMF (50 mL), 0.1 M NaI, and 1,2-dibromoethane (2.5 mmol, 215 muL). The mixture was electrolyzed under argon at a constant current intensity of 0.2 A at room temperature for 20 min. Then the current was stopped, and [Ni(bpy)]Br2 complex21 (2.6 mmol, 562 mg), 2,6-dichloropyridine (5 mmol, 0.74 g), and 2-bromo-6-methylpyridine (10 mmol, 1.72 g) were sequentially added. The solution was electrolyzed at 0.1 A and room temperature until the starting material was totally consumed (8 h).
[Mn6(2,2'-bipyridine)4(5-methylisophthalic acid(-2H))6]*3.5H2O}n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
61%
With sodium hydroxide; at 150℃; for 72h;Autoclave;
General procedure: Under vigorous magnetic stirring, <strong>[499-49-0]5-methylisophthalic acid</strong> (H2mip, 0.090 g, 0.50 mmol) was suspended in 10 ml water, an accurate amount of 1.0 mmol (if not mentioned specially) NaOH was slowly added, and then the (hydrated) chloride salt of manganese, iron, cobalt, nickel, copper or zinc was added. Finally, 2,2?-bipyridine (bpy, 0.078 g, 0.50 mmol) or 1,10-phenanthroline (phen, 0.100 g, 0.50 mmol) was added. The mixture was transferred into a 20 ml Teflon-lined vessel, heated to 120?200 °C at the rate of 5 °C/h, and kept at that temperature for 3 days, then slowly cooled down to room temperature at the rate of 5 °C/h. Crystals were obtained by filtration, washed with water and dried in air. The purity of products was verified by powder X-ray diffraction measurement.
[Co3(2,2'-bipyridine)2(5-methylisophthalic acid(-2H))3]*2H2O}n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
39%
With sodium hydroxide; at 200℃; for 72h;Autoclave;
General procedure: Under vigorous magnetic stirring, <strong>[499-49-0]5-methylisophthalic acid</strong> (H2mip, 0.090 g, 0.50 mmol) was suspended in 10 ml water, an accurate amount of 1.0 mmol (if not mentioned specially) NaOH was slowly added, and then the (hydrated) chloride salt of manganese, iron, cobalt, nickel, copper or zinc was added. Finally, 2,2?-bipyridine (bpy, 0.078 g, 0.50 mmol) or 1,10-phenanthroline (phen, 0.100 g, 0.50 mmol) was added. The mixture was transferred into a 20 ml Teflon-lined vessel, heated to 120?200 °C at the rate of 5 °C/h, and kept at that temperature for 3 days, then slowly cooled down to room temperature at the rate of 5 °C/h. Crystals were obtained by filtration, washed with water and dried in air. The purity of products was verified by powder X-ray diffraction measurement.
[Ni(2,2'-bipyridine)(H2O)(5-methylisophthalic acid(-2H))]*H2O}n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
With sodium hydroxide; at 150℃; for 72h;Autoclave;
General procedure: Under vigorous magnetic stirring, <strong>[499-49-0]5-methylisophthalic acid</strong> (H2mip, 0.090 g, 0.50 mmol) was suspended in 10 ml water, an accurate amount of 1.0 mmol (if not mentioned specially) NaOH was slowly added, and then the (hydrated) chloride salt of manganese, iron, cobalt, nickel, copper or zinc was added. Finally, 2,2?-bipyridine (bpy, 0.078 g, 0.50 mmol) or 1,10-phenanthroline (phen, 0.100 g, 0.50 mmol) was added. The mixture was transferred into a 20 ml Teflon-lined vessel, heated to 120?200 °C at the rate of 5 °C/h, and kept at that temperature for 3 days, then slowly cooled down to room temperature at the rate of 5 °C/h. Crystals were obtained by filtration, washed with water and dried in air. The purity of products was verified by powder X-ray diffraction measurement.
[Cu3(2,2'-bipyridine)2(5-methylisophthalic acid(-1H))2(5-methylisophthalic acid(-2H))2]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
50%
With sodium hydroxide; at 150℃; for 72h;Autoclave;
General procedure: Under vigorous magnetic stirring, <strong>[499-49-0]5-methylisophthalic acid</strong> (H2mip, 0.090 g, 0.50 mmol) was suspended in 10 ml water, an accurate amount of 1.0 mmol (if not mentioned specially) NaOH was slowly added, and then the (hydrated) chloride salt of manganese, iron, cobalt, nickel, copper or zinc was added. Finally, 2,2?-bipyridine (bpy, 0.078 g, 0.50 mmol) or 1,10-phenanthroline (phen, 0.100 g, 0.50 mmol) was added. The mixture was transferred into a 20 ml Teflon-lined vessel, heated to 120?200 °C at the rate of 5 °C/h, and kept at that temperature for 3 days, then slowly cooled down to room temperature at the rate of 5 °C/h. Crystals were obtained by filtration, washed with water and dried in air. The purity of products was verified by powder X-ray diffraction measurement.
[Zn2(2,2'-bipyridine)2(H2O)(5-methylisophthalic acid(-2H))2]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydroxide; at 200℃; for 72h;Autoclave;
General procedure: Under vigorous magnetic stirring, <strong>[499-49-0]5-methylisophthalic acid</strong> (H2mip, 0.090 g, 0.50 mmol) was suspended in 10 ml water, an accurate amount of 1.0 mmol (if not mentioned specially) NaOH was slowly added, and then the (hydrated) chloride salt of manganese, iron, cobalt, nickel, copper or zinc was added. Finally, 2,2?-bipyridine (bpy, 0.078 g, 0.50 mmol) or 1,10-phenanthroline (phen, 0.100 g, 0.50 mmol) was added. The mixture was transferred into a 20 ml Teflon-lined vessel, heated to 120?200 °C at the rate of 5 °C/h, and kept at that temperature for 3 days, then slowly cooled down to room temperature at the rate of 5 °C/h. Crystals were obtained by filtration, washed with water and dried in air. The purity of products was verified by powder X-ray diffraction measurement.
Ni<SUB>2</SUB>Cl<SUB>2</SUB>(2,2'-bipyridine)<SUB>2</SUB>(1,3-adamanranedicarboxylate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
In N,N-dimethyl-formamide; acetonitrile; at 120℃; for 72h;Autoclave; High pressure;
A mixture of NiCl2*6H2O (0.04 g,0.17 mmol), 1,3-H2adc (0.04 g, 0.18 mmol) and 2,2'-bipyridine (0.03 g, 0.19 mmol) was added to 3 ml N,N'-dimethylformamide (DMF) and 3 ml acetonitrile (CH3CN) with stirring. Then this mixture was sealed in a 23 ml Teflon-lined stainless steel autoclave and heated at 120 °C for 3 days. The green block crystals were obtained by filtration and washed by DMF several times. The yield of product was 70percent in weight based on Ni. The elemental analysis results are listed as follows: Anal. Calc. For 1: C, 52.97; H, 4.41; N,1.93. Found: C, 52.5; H, 4.32; N, 1.87percent. IR (KBr pellet, cm1): 3448(br, m), 2929 (m), 2864 (w), 1637 (w), 1596 (m), 1521(s), 1444 (s),1134 (w), 1070 (m), 943 (w), 858 (w), 771 (m), 527 (s), 414 (w).
General procedure: In the preparation of the Ln(CA)3·Phn and Ln(CA)3·Bpy adducts the 3-N NaOH water solution and an ethanol solution of Phn or Bpy were added to an ethanol solution of CA. Then, a water?ethanol (1:1) solution of LnCl3·6H2O was drop by drop added to the previous mixture at heating in a water bath (at 60?70°C) or sometimes without heating. A molar ratio of the reagents CA: Phn (Bpy): lanthanide chloride: NaOH was equal to 3:1:1:3. The compound Eu(AcCHex)3·Phen was also synthesized by other method involving the preparation of an ethanol solution of a mixture of CA, Phen and EuCl3·6H2O in a molar ratio of 3:1:1 and adjusting the pH value of reaction mixture to 6 with a liquid ammonia. It should be pointed out that the heating of the reaction mixture results in a decrease in the keto/enol ratio of cycloalkanone [37] that promotes a binding of CA with the Ln3+ ion. At the same time, the probability of decomposition of cycloalkanonate anion increases.
An aqueous solution of zinc chloride (0.137 g, 1.0 mmol; 10 mL) was added to ethanolic solution of H2mesc (0.192 g, 1.0 mmol; 15 mL). The reaction mixture was stirred for 24 h and 2,2'-bipyridyl (0.156 g, 1.0 mmol) in DMF (10 mL) was added. The orange solution was slowly evaporated and orange microcrystals suitable for X-ray were separated. They were filtered off, washed with ethanol and air-dried. Anal. Calc. For C20H14N2O4Zn: C, 58.3; H, 3.4; N, 6.8; Zn, 15.9percent, Found: C, 58.2, H, 3.5; N, 6.8; Zn, 15.8percent. Conductivity data (10-3 M in DMSO): LambdaM = 3.0 Ohm-1 cm2 mol-1. IR (cm-1); nu(C=O) 1663; nu(C-C) 1480; nu(C-O) 1265; nu(Zn-O) 509; nu(Zn-N) 410. 1H NMR (d6-DMSO/TMS, ppm), delta: CH3, 3.41; H(3), 6.69; H(8), 5.94; H(5), 6.55. ESI-MS: m/z: 412.0 (Calcd 411.5) [Zn(bpy)(mesc)]+; 222 (Calcd 221.5) [Zn(bpy)]+.
[Ag(2,2'-bipyridyl)2]*(2,2'-bipyridyl)(4-methyl-6,7-dihydroxycoumarin)(NO3)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
An aqueous solution of silver nitrate (0.17 g, 1.0 mmol; 1 mL) was added to 2,2'-bipyridyl (0.156 g, 1.0 mmol) in acetonitrile (10 mL). The reaction mixture was stirred for 2 h in the dark and to the yellow solution produced, H2mesc (0.192 g, 1.0 mmol) in methanol (15 mL) was added. The resulting mixture was stirred for 24 h and a pale yellow precipitate was isolated, washed with methanol and air-dried. Anal. Calc. For AgC40H32N7O7: Ag 13.0; C, 57.8; H, 3.9; N, 11.8percent, Found: Ag 12.8; C, 57.9, H, 3.8; N, 11.8percent. Conductivity data (10-3 M in DMSO): LambdaM = 67.0 Ohm-1 cm2 mol-1. IR (cm-1); nu(OH) 3298; nu(C=O) 1627; nu(C-C) 1466; nu(C-O) 1282; nu(Ag-N) 412. 1H NMR (d6-DMSO/TMS, ppm), delta: CH3, 4.19; H(3), 6.08; H(8), 6.74; H(5), 6.69; OH(6), 9.35; OH(7), 10.25; H(bpy), 7.08-7.75. ESI-MS: m/z: 829.92 (Calcd 830) [Ag(bpy)2][(bpy)(H2mesc)(NO3)]+; 567.4 (Calcd 568.0) [Ag(bpy)2](H2mesC-CO2)}+; 420.0 (Calcd 420.0) [Ag(bpy)2]+; 264 (Calcd 264) [Ag(bpy)]+.
With phosphotungstic acid; sodium tungstate; titanium(IV) oxide; zirconium(IV) oxide; triethylamine; In methanol; at 90℃; under 22502.3 Torr; for 5h;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.
A solution of CuI (0.019 g, 0.1 mmol) in CH3CN(5 mL) wasadded to a stirred solution of 2,2?-Bipy (0.016 g, 0.1 mmol)and 2-(Dpp)bp (0.034 g, 0.1 mmol) in CH3CN(5 mL). Themixture was stirred for 10 min, with no visible precipitation.After filtration, the clear filtrate was set aside for evaporationin air. Orange block crystals of complex 4 were obtainedafter several hours. Yield: 43.4 mg (63.4percent, based on Cu).Anal. Calc. for 4 C34H27N2P1Cu1I1:C, 59.63; H, 3.94; N,4.09. Found (percent): C, 59.64; H, 3.92; N, 3.98. IR (KBr pellet,cm?1): 3430sh, 3054vw, 1610m, 1431s, 1146w, 1103w,770, 699.
(4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione) 2,2′-bipyridinedysprosium(III)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
A mixture of triethylamine (0.014 mL, 0.1 mmol) and 4,4,4-trifluoro-1-(2-naphthyl)1,3-butanedione(TFNB) (0.080 g, 0.3 mmol) in absolute methanol (20 mL) was kept stirring for anhour, to which DyCl3·6H2O (0.113 g, 0.3 mmol) and 2,2?-bipyridine (bpy) (0.0781 g, 0.5 mmol)were added. The mixed system was stirred in a semiclosed beaker for 4 h at room temperature.After filtration, the resultant solution was shelved at ambient temperature. Colorlesscrystals appeared within two weeks (yield 75%, based on Dy3+). Elemental Anal.: (%) Calcdfor C52H32DyF9N2O6 (1114.30): C, 56.05; N, 2.51; H, 2.89%. Found: C, 56.01; N, 2.47; H, 2.86%.Main IR (KBr): 3027 (w), 2113 (s), 1638 (s), 1521 (s), 1338 (m), 1281 (s), 1238 (m), 1130 (s), 1029(m), 834 (m), 781 cm-1 (s), 709 cm-1 (w).