* 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] Inorganic Chemistry, 2013, vol. 52, # 5, p. 2505 - 2518
[2] Bulletin des Societes Chimiques Belges, 1990, vol. 99, # 9, p. 741 - 768
2
[ 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
3
[ 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℃; 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).
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.
With potassium permanganate; water;Heating / reflux;
A suspension of 1.59 mmol of 5, 2.38 mmol of 2, and 1.9 mmol of BOP reagent in 100 mL of DMF was stirred overnight and the solvent was removed under reduced pressure. The residue was dissolved in 50 mL of acetic acid and stirred at reflux overnight before acetic acid was removed in vacuo. The residue was diluted with 50 mL of ethyl acetate and the organic solution was washed with saturated NaCl, dried over MgSO4, and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel to give 0.5 mmol of 6.
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); In tetrachloromethane; for 12h;Reflux;
Commercially available <strong>[56100-22-2]6-methyl-2,2'-bipyridine</strong> (200 mg, 1.17 mmol) was dissolved in carbon tetrachloride; N-bromosuccinimide (1.4 g, 5.85 mmol) and 2,2'-azobis isobutyronitrile (13.5 mg, 82.32 mumol) were added to the solution, and the mixture was heated under reflux for 12 hours. After cooling to room temperature, a saturated sodium chloride solution was added, the resulting mixture was extracted with dichloromethane, and the organic layer was dried over anhydrous sodium sulfate, filtered and concentrated. The concentrate was purified by silica gel column chromatography to produce 6-tribromomethyl-2,2'-bipyridine in a quantitative yield as colorless crystals. The subsequent reduction reaction was performed using the 6-tribromomethyl-2,2'-bipyridine.
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