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CAS No. : | 4411-80-7 | MDL No. : | MFCD00059776 |
Formula : | C12H12N2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | OHJPGUSXUGHOGE-UHFFFAOYSA-N |
M.W : | 184.24 | Pubchem ID : | 20445 |
Synonyms : |
|
Num. heavy atoms : | 14 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.17 |
Num. rotatable bonds : | 1 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 57.4 |
TPSA : | 25.78 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.81 cm/s |
Log Po/w (iLOGP) : | 2.52 |
Log Po/w (XLOGP3) : | 2.28 |
Log Po/w (WLOGP) : | 2.76 |
Log Po/w (MLOGP) : | 1.49 |
Log Po/w (SILICOS-IT) : | 3.43 |
Consensus Log Po/w : | 2.5 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.99 |
Solubility : | 0.19 mg/ml ; 0.00103 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.46 |
Solubility : | 0.641 mg/ml ; 0.00348 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -4.94 |
Solubility : | 0.0021 mg/ml ; 0.0000114 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 2.04 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
GHS Pictogram: |
* 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.
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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10% | 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56 %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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16% | 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With Ni(acetylacetate)2; 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-diaza-2,5-cyclo-hexadiene In toluene at 80℃; for 18h; | |
98% | In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; constant current intensity 200 mA; | |
98% | Stage #1: 2-bromo-6-methylpyridine With lithium chloride; nickel dichloride; zinc In N,N-dimethyl-formamide at 50℃; for 0.0833333h; Stage #2: With iodine; acetic acid In N,N-dimethyl-formamide at 50℃; for 0.333333h; Stage #3: 2-bromo-6-methylpyridine In N,N-dimethyl-formamide at 80℃; for 24h; |
87.5% | With bis(triphenylphosphine)nickel(II) chloride; tetraethylammonium iodide; zinc In tetrahydrofuran Inert atmosphere; | |
84% | With tetrakis(triphenylphosphine)nickel(0) | |
80% | With N,N,N,N,N,N-hexamethylphosphoric triamide; samarium; nickel dichloride In tetrahydrofuran for 24h; Inert atmosphere; Reflux; chemoselective reaction; | |
78% | With nickel(II) chloride hexahydrate; iodine; acetic acid; lithium chloride; zinc In N,N-dimethyl-formamide at 50 - 60℃; for 6h; | |
75% | With bis(triphenylphosphine)nickel(II) chloride; tetraethylammonium iodide; zinc In tetrahydrofuran at 50℃; for 12h; | |
74% | With tetrabutylammomium bromide; potassium carbonate In water; N,N-dimethyl-formamide at 110℃; for 48h; | |
73% | With nickel diacetate; triphenylphosphine; sodium t-butanolate In 1,2-dimethoxyethane at 45℃; for 2h; | |
68% | With NiCl2(PPh3)2; tetraethylammonium iodide; zinc In tetrahydrofuran at 50℃; for 48h; Inert atmosphere; | |
67% | With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; sodium formate for 168h; Heating; | |
67% | With tetrabutylammonium tetrafluoroborate; ethylene dibromide In N,N-dimethyl-formamide Electrochemical reaction; | |
60% | With dibromobis(triphenylphosphine)nickel(II); tetra-(n-butyl)ammonium iodide; zinc In tetrahydrofuran at 20℃; Inert atmosphere; Reflux; | Synthesis of 6,6'-dimethyl-2,2'-bipyridine A mixture of Ni(PPh3)2-Br2 (12.95 g, 0.01743 mol), Bu4NI (21.46 g, 0.05811 mol) and Zn dust (3.81 g, 0.0583 mol) in this order was added to a flask which was then charged with THF (210 mL) and mixture was stirred under N2 atmosphere at room temperature, after which 2-bromo-6-methylpyridine (10.0 g, 0.0581 mol) was added, and the mixture was refluxed overnight. The solvents were removed by rotary evaporation, and the crude product checked by 1H NMR.Diethyl ether (200 mL) and 10% NH4OH (50 mL) were added tothe crude reaction and the mixture was stirred for 1 h, after which solids were removed by filtration and purified by column chromatography on silica gel using ethyl acetate and hexane yielding 6,6'-dimethyl-2,2'-bipyridine as a white solid (4.20 g, 60%). |
59% | With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; sodium formate In ethanol; water | 1 6,6'-Dimethyl-2,2'-bipyridine (1) 6,6'-Dimethyl-2,2'-bipyridine (1) Ref. G. R. Newkome et al., J. Inorg. Nucl. Chem., 43, 1529-1531 (1981) 6-Bromo-2-methylpyridine (49.0 g, 0.285 moles), benzyltriethylammonium chloride (11.6 g, 0.0509 moles), sodium formate (25.7 g, 0.408 moles), 10% palladium on carbon (1.7 g), 32% sodium hydroxide (29 ml) and water (86 ml) were refluxed for 24 hours. The mixture was filtered and the aqueous phase was extracted with methylene chloride. After evaporation of solvent the product was distilled. Yield: 59% m.p. 82°-83° C. (Lit. 88°-89° C.) UV (in ethanol): 290 nm, 237 nm 1 H-NMR (400 MHz, CDCl3): 2.61 (s, 6H); 7.11 (d, 2H, J=7.6 Hz); 7.64 (t, 2H, 7.6 Hz); 8.18 (d, 2H, J=7.6 Hz) |
50% | With sodium hydroxide; sodium formate In water for 48h; Heating; | |
50% | With sodium hydroxide; N-benzyl-N,N,N-triethylammonium chloride; sodium formate In water for 216h; Heating; | |
40% | With nickel(II) chloride hexahydrate; lithium chloride; zinc In N,N-dimethyl-formamide at 70℃; | |
With copper | ||
With water; nickel 1) toluene, 22 h, reflux 2) 2 h, 40 deg C; Yield given. Multistep reaction; | ||
With water; nickel 1.) toluene, reflux, 20 h; 2.) 40 deg C, 2 h; Yield given. Multistep reaction; | ||
With water; nickel 1) toluene, 20 h, reflux, 2) 40 deg C, 90 min; Yield given. Multistep reaction; | ||
99 % Chromat. | With sodium iodide; nickel dibromide; zinc In N,N-dimethyl-formamide at 20℃; Electrochemical reaction; | |
With nickel In toluene at 110℃; for 22h; | ||
Stage #1: 2-bromo-6-methylpyridine In toluene at 110℃; for 22h; Stage #2: With water | ||
With lithium chloride; nickel dichloride; zinc | ||
With bis(triphenylphosphine)nickel(II) chloride; tetraethylammonium iodide; zinc In tetrahydrofuran Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With N-Bromosuccinimide In Carbon tetrachloride at 80℃; for 0.5h; Stage #2: With dibenzoyl peroxide In Carbon tetrachloride at 80℃; for 24h; | |
63% | With N-Bromosuccinimide; dibenzoyl peroxide In Carbon tetrachloride at 80℃; for 12.5h; Inert atmosphere; | |
53% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In dichloromethane; water monomer for 3h; Irradiation; | Compound 2 General procedure: 6,6'-Dimethyl-2,2'-bipyridine 1 (1.33 g, 7.22 mmol) and a mixture of dichloromethane (120 mL) and H2O (120 mL) were added to a three-necked flask. Then, NBS (3.00 g, 16.8 mmol) and AIBN (15.0mg, 0.09 mmol) were added and stirred for 3 h with the irradiation under a 150-W halogen lamp.The resulting mixture was neutralized with saturated aqueous NaHCO3. Then, the organic and water layers were separated. The organic layer was washed by water (50 mL x 3) and brine (50 mL x 3),and dried over Na2SO4. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (chloroform) to afford compound 2 (1.30 g, 53%yield). |
25% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile); hydrogen bromide; bromine In Carbon tetrachloride for 4h; Heating; | |
24.1% | With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In Carbon tetrachloride Heating; Irradiation; | |
21% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With N-Bromosuccinimide In Carbon tetrachloride for 0.5h; Heating; Stage #2: With dibenzoyl peroxide In Carbon tetrachloride Heating; Further stages.; | |
21% | With N-Bromosuccinimide; dibenzoyl peroxide In chloroform at 62℃; for 16h; | |
With N-Bromosuccinimide In Carbon tetrachloride Heating; | ||
With N-Bromosuccinimide; dibenzoyl peroxide In chloroform | 1.a a) a) Preparation of compound (1) A mixture of 6,6'-dimethyl-2,2'-bipyridine (2.76 g, 15 mmol) and N-bromosuccinimide (5.10 g, 28.6 mmol) is refluxed in 150 ml of chloroform for 30 min. 30 mg of benzoyl peroxide are then added. The mixture is subsequently refluxed for 2 h and then filtered to separate off the succinimide. The solution is cooled to 0° C. and the solid which deposits is filtered off and washed with methanol. 1.65 g of 6,6'-bis(bromomethyl)-2,2'-bipyridine are recovered in the form of a white solid crystal. The filtrate obtained above from the chloroform solution is concentrated and chromatographed on a silica column (eluent: CH2 Cl2 /MeOH 98:2). | |
With N-Bromosuccinimide; dibenzoyl peroxide In Carbon tetrachloride | ||
With N-Bromosuccinimide; dibenzoyl peroxide In Carbon tetrachloride |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With selenium(IV) oxide In glacial acetic acid for 24h; Heating; | |
48% | With iodine; oxygen In dimethyl sulfoxide at 160℃; for 0.75h; Microwave irradiation; | 4. Experimental section General procedure: A 2-5 mL microwave compatible, disposable vial was charged with the requisite methyl heteroarene (0.308 mmol, 1.00 equiv) in reagent grade dimethylsulfoxide (2.0 mL, 0.15 M) at ambient temperature. Subsequently, I2 (82.0 mg,0.32 mmol, 1.05 equiv) was charged in one portion followed by purging of the vial head space with O2. The resulting dark-brown solution was capped with an appropriately sized microwave vialcap and placed in a microwave reactor (high power level) for 0.75 hat 160 °C. The resulting dark brown mixture was cooled to ambient temperature, diluted with minimal ethyl acetate, and transferred toa separatory funnel. The combined organics were treated with a 3 mL of a saturated, aqueous solution of sodium thiosulfate and then separated. The aqueous layer was back-extracted with ethyl acetate (3 10 mL). The combined organics were washed with water (10 mL) to remove residual dimethylsulfoxide and then a saturated aqueous sodium chloride solution (10 mL). The mixture was dried over anhydrous sodium sulfate, filtered through a cotton plug, and subsequently evaporated under reduced pressure at ambient temperature to afford the crude material which was purified using automated flash column chromatography as described below. |
45% | With selenium(IV) dioxide In 1,4-dioxane; lithium hydroxide monohydrate for 4h; Reflux; |
30% | With selenium(IV) dioxide; glacial acetic acid for 48h; Reflux; | |
With selenium(IV) oxide In glacial acetic acid | ||
Multi-step reaction with 2 steps 1: 25 percent / NBS, AIBN, 62percent HBr, Br2 / CCl4 / 4 h / Heating 2: 20 percent / DMSO / 8 h / 150 °C | ||
With selenium(IV) dioxide In 1,4-dioxane Heating; Inert atmosphere; | ||
Multi-step reaction with 4 steps 1: sulfuric acid; chromium(VI) oxide / 22 h / 0 - 75 °C / Inert atmosphere 2: sulfuric acid / 16 h / Reflux; Inert atmosphere 3: sodium tetrahydridoborate / ethanol / 4 h / Reflux; Inert atmosphere 4: SIBX / ethyl acetate / Reflux; Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 56% 2: 8% | With N-Bromosuccinimide In tetrachloromethane for 6h; Heating; | |
1: 48.8% 2: 30% | With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane Reflux; | |
1: 37% 2: 35% | With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane |
30% | With N-Bromosuccinimide; dibenzoyl peroxide In tetrachloromethane Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With 2,2'-azobis(isobutyronitrile); 1,3,4,6-Tetrabromo-3α,6α-diphenylglycoluril In tetrachloromethane at 80℃; Inert atmosphere; Reflux; | |
With N-Bromosuccinimide | ||
With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 1.5h; Reflux; |
With N-Bromosuccinimide; dibenzoyl peroxide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
58% | With sodium hydroxide In methanol; water | 6 Example 6 Example 6 2.55 g of 6-chloro-2-picoline and 1.00 g of sodium hydroxide are stirred into a mixture of 15 ml of water and 8 ml of methanol. Following the addition of 1.3 g of palladium (5% by weight on activated carbon) as catalyst, the mixture is stirred for 20 h at 80-85° C. at 0.1 MPa. The mixture is then diluted with 20 ml of methanol and the catalyst is filtered off. After the methanol has been stripped off, the product, 6,6'-dimethyl-2,2'-bipyridyl, crystallizes in the form of lamellar crystals. This gives 1.10 g (58% yield). According to 1H NMR, the crude product has a purity of >98%. CAS Registry Number: 4411-80-7. 1H NMR (300 MHz, DMSO): d=8.18 (d, J=8 Hz, 2H); 7.81 (t, J=8 Hz, 2H); 7.29 (d, J=8 Hz, 2H); 2.56 (s, 6H). |
With copper(l) iodide; triethylamine; triphenylphosphine In acetonitrile at 82℃; | ||
With zinc In 1-methyl-pyrrolidin-2-one at 20 - 70℃; Inert atmosphere; | 24 To a glass reaction container equipped with a cooling apparatus, 15.3 mg of nickel bromide, 25.2 mg of 5,5'-bis(trimethylsilyl)-2,2'-bipyridine and 91.6 mg of zinc powder were added under an atmosphere of nitrogen at room temperature. To the obtained mixture, 89.3 mg of 6-chloro-2-picoline and 5 mL of N-methyl-2-pyrrolidone were added at room temperature. The obtained mixture was reacted at 70°C for 2 hours to obtain a reaction mixture containing 6,6'-diemthyl-2,2'-bipyridine. The yield of 6,6'-dimethyl-2,2'-bipyridine was 60.8 mg. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
53% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: Dichlorophenylphosphine In tetrahydrofuran; hexane at -78 - 20℃; for 1h; Stage #3: With sodium periodate In dichloromethane; water at 20℃; | |
53% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: Dichlorophenylphosphine In tetrahydrofuran; hexane at -78 - 20℃; for 1h; Stage #3: With sodium periodate In dichloromethane; water at 20℃; Further stages.; | |
53% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at -78 - 20℃; Stage #2: Dichlorophenylphosphine In tetrahydrofuran; hexane at -78℃; for 0.25h; Stage #3: With sodium periodate In dichloromethane; water at 20℃; for 1h; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 4-methyl-morpholine In tetrahydrofuran at -25 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: HBr; bromine / 2 h / -20 °C 1.2: 77 percent / sodium nitrite / H2O / 1.75 h / -20 - 15 °C 2.1: 50 percent / sodium formate; benzyltriethylammonium chloride; NaOH / Pd/C / H2O / 216 h / Heating | ||
Multi-step reaction with 2 steps 1.1: 48percent HBr; Br2 / 1.5 h / -20 °C 1.2: aq. NaNO2 / -20 - 15 °C 1.3: 90 percent / aq. NaOH / -10 - 20 °C 2.1: 50 percent / Pd(PPh3)4 / toluene / 48 h / Heating | ||
Multi-step reaction with 2 steps 1: 1) 48percent HBr, Br2, NaNO2 / 1) water, -20 to -10 deg C, 30 min, 2) water, 90 min 2: 1) Raney Ni, 2) H2O / 1) toluene, 20 h, reflux, 2) 40 deg C, 90 min |
Multi-step reaction with 2 steps 1: 1) 48percent HBr, Br2 2) NaNO2 / 1) -15 to -10 deg C, 30 min 2) water, 90 min 2: 1) Raney Nickel 2) water / 1) toluene, 22 h, reflux 2) 2 h, 40 deg C | ||
Multi-step reaction with 2 steps 1: sodium nitrite; hydrogen bromide; bromine 2: nickel dichloride; zinc; lithium chloride | ||
Multi-step reaction with 2 steps 1: bromine; hydrogen bromide / water 2: bis(triphenylphosphine)nickel(II) chloride; zinc; tetraethylammonium iodide / tetrahydrofuran / Inert atmosphere | ||
Multi-step reaction with 2 steps 1: hydrogen bromide; bromine; sodium nitrite / water 2: bis(triphenylphosphine)nickel(II) chloride; zinc; tetraethylammonium iodide / tetrahydrofuran / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: aq. KMnO4 / 2 h / 100 °C 2: EDCI / HOAt / dimethylformamide / 16 h / 23 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: aq. KMnO4 / 2 h / 100 °C 2: EDCI / HOAt / dimethylformamide / 16 h / 23 °C 3: 1,2-dichloro-ethane / 16 h / 60 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: aq. KMnO4 / 2 h / 100 °C 2: EDCI / HOAt / dimethylformamide / 16 h / 23 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: aq. KMnO4 / 2 h / 100 °C 2: EDCI / HOAt / dimethylformamide / 16 h / 23 °C 3: 1,2-dichloro-ethane / 16 h / 60 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: 85 percent / Et3N / CH2Cl2 / 8 h / 60 °C 2.1: n-BuLi; Bu3SnCl / tetrahydrofuran; hexane / -78 - 20 °C 2.2: PPh3 / PdCl2(PPh3)2 / xylene / 24 h / Heating | ||
Multi-step reaction with 2 steps 1.1: 85 percent / pyridine / 3 h / 20 °C 2.1: n-BuLi; Bu3SnCl / tetrahydrofuran; hexane / -78 - 20 °C 2.2: PPh3 / PdCl2(PPh3)2 / xylene / 24 h / Heating |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 74 percent / m-chloroperbenzoic acid / CHCl3 / 1 h / 25 °C 2: 92 percent / 0.25 h / Heating 3: 99 percent / 6N HCl / 12 h / Heating 4: 95 percent / thionyl chloride / 2 h / Heating | ||
950 mg | With N-chloro-succinimide; dibenzoyl peroxide In tetrachloromethane Inert atmosphere; Reflux; | 5 Preparation of chloromethyl-6-methyl-[2,2']bipyridinyl Under an argon atmosphere, 6,6'-dimethyl-[2,2']bipyridinyl (1.88 g; 10 mmol) was dissolved in tetrachloromethane (50 mL). N-Chlorosuccinimide (1.36 g; 10 mmol) and benzoyl peroxide (50 mg; 0.67 mmol) were added. The reaction mixture was stirred at reflux for overnight. The mixture was cooled with an ice bath, filtered, and the filtrate was concentrated under vacuum. The crude material was purified by chromatography on silica gel to give white crystals (950 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With 3-chloro-benzenecarboperoxoic acid In ethanol; chloroform | 15.8 6,6'-Dimethyl-2,2'-bipyridine-N-oxide (15) Scheme 8 6,6'-Dimethyl-2,2'-bipyridine-N-oxide (15) 6,6'-Dimethyl-2,2'-bipyridine (1.97 g, 0.0107 moles, Example 1) was dissolved in chloroform (10 ml). m-Chloroperbenzoic acid (1.85 g, 0.0107 moles) was dissolved in chloroform (40 ml), and added slowly to the bipyridine solution at 0°-5° C. After stirring for two hours at room temperature the solution was extracted twice with saturated sodium hydrogen carbonate solution and three times with water. The chloroform phase was dried and evaporated. The product was purified by flash chromatography. Yield: 70% UV (in ethanol): 270 nm, 250 nm 1 H-NMR (400 MHz, CDCl3): 2.61 (s, 3H); 2.62 (s, 3H); 7.19 (d, 1H, J=8 Hz); 7.28 (d, 1H, J=5 Hz); 7.69 (t, 1H, J=8 Hz); 7.97 (t, 1H, J=5 Hz); 8.53 (d, 1H, J=8 Hz) |
70% | With 3-chloro-benzenecarboperoxoic acid In chloroform at 0 - 20℃; for 4h; | 1.A; 2; 3; 4 Synthesis of -N-oxide 6,6'-dimethyl-2,2'-bipyridyl(5) 6,6'-Dimethyl-2,2'-bipyridyl (4) (39.4 g, 0.21 mol) was dissolved in 1000 ml of chloroform, and m-chloroperoxybenzoic acid (49.0 g, was added in small portions at 0 ° C, 0.21 mol, 75% by weight).Plus,Stir at room temperature for 4 hours.The reaction was monitored by TLC.The mixture is successively saturated with sodium bicarbonate solution,Washed with salt water,Dry over anhydrous sodium sulfate,filter,Evaporate the solvent under reduced pressure.The crude product was obtained.The crude product was purified by silica gel column chromatography (DCM:MeOH = 30:1)6,6'-Dimethyl-2,2'-bipyridyl-N-oxide (30.0 g, 70%) was obtained as a colorless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93.9% | With dihydrogen peroxide; acetic acid In water at 70℃; for 7h; | |
90% | With 3-chloro-benzenecarboperoxoic acid | |
68% | With 3-chloro-benzenecarboperoxoic acid In ethanol; chloroform | 16.8 6,6'-Dimethyl-2,2'-bipyridine-N,N'-dioxide (16) Scheme 8 6,6'-Dimethyl-2,2'-bipyridine-N,N'-dioxide (16) 6,6'-Dimethyl-2,2'-bipyridine (10.0 g, 0.054 moles) was dissolved in chloroform (50 ml). m-Chloroperbenzoic acid (21.0 g, 0.122 moles) was dissolved in chloroform (200 ml) and the solutions were combined. After stirring at room temperature overnight the solvent was evaporated and the product was purified by means of flash chromatography (silica, 0-30% methanol/chloroform). Yield: 68% UV (in ethanol): 263 nm, 225 nm 1 H-NMR (400 MHz, CDCl3): 2.58 (s, 6H); 7.23 (t, 2H, J=8 Hz); 7.34 (dd, 2H, J=8 Hz & 2 Hz); 7.36 (dd, 2H, J=8 Hz & 2 Hz) |
62% | With 3-chloro-benzenecarboperoxoic acid In chloroform for 48h; | |
With dihydrogen peroxide; acetic acid at 70℃; for 7h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In acetonitrile (N2), to a CH3CN soln. of Cu-salt added organic compound in CH3CN at 25°C, maintained with stirring at 40°C for 2 h; filtered, washed with CH3CN, dried in vac.; elem. anal.; | |
15% | In dichloromethane | 6 2.8. Synthesis of [(6,6′-di-methylbipy)CuCl2] (7) This compound was synthesized in an analogous fashion to compound1 by reacting 250.0 mg (1.36 mmol) of 6,6′ di-methyl-2,2′-bipyridine and 231.1mg (1.36mmol) of anhydrous CuCl2. This complex was isolated as orange crystals after recrystallization fromacetonitrile at-10 °C over a two day period (72 mg, 15% yield). Elemental analysis(C12H12N2Cl2Cu): Calculated: C = 45.23%, H = 3.80%; Experimental:C = 44.73%, H = 3.74%. IR: νmax/cm-1 3618 (w), 3506 (w), 3090(CH), 3058 (CH), 2923 (CH), 1599, 1481, 1332, 1015, 794, 650. UV-vis: λmax (DMSO, 20 °C)/nm (ε, M-1 cm-1) 297 (21,442), 305 (Sh,16,601), 321 (Sh, 5316), 806 (100). Mass spectrometry: Molecular ion(m/z): [Cu(6,6′-di-methylbipy)(Cl)]+ = 305.9983 amu (theoretical =305.9980 amu); [Cu2(6,6′-di-methylbipy)2(Cl)3]+ = 646.9623 amu (theoretical= 646.9653 amu). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With [PdCl(dppb)(C3H5)]; caesium carbonate In N,N-dimethyl-formamide at 150℃; for 20h; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 93.1% 2: 6.9% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; cesium fluoride In 2-pentanol at 100℃; for 18h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
14%Chromat.; 25%Chromat.; 56%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×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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 49 %Chromat. 2: 22 %Chromat. 3: 23 %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×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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 54 %Chromat. 2: 21 %Chromat. 3: 20 %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×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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 45 %Chromat. 2: 7 %Chromat. 3: 30 %Chromat. 4: 12 %Chromat. 5: 6 %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×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. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
16%; 29%; 6%; 9%; 11%; 18% | 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47%; 14%; 7%; 10%; 13% | 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56%; 6%; 19%; 10% | With nickel(II) bromide hydrate; 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 78% 2: 11% | With bis(bipyridine)nickel(II) bromide; sodium iodide In N,N-dimethyl-formamide at 20℃; for 8h; Electrochemical reaction; Inert atmosphere; | 4.7. Procedure for 2,6-dichloropyridine+2-bromo-6-methylpyridine preparative coupling reaction 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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: gold(III) tetrachloride trihydrate With sodium hydrogencarbonate In water; acetonitrile Stage #2: 6,6'-dimethyl-2,2'-bipyridine In water; acetonitrile at 120℃; for 0.333333h; Microwave irradiation; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With rhodium(III) acetylacetonate; 1,3-bis(mesityl)imidazolium chloride; sodium t-butanolate In toluene at 130℃; for 6h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With rhodium(III) acetylacetonate; 1,3-bis(mesityl)imidazolium chloride; sodium t-butanolate In toluene at 130℃; for 4h; High pressure; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In methanol; ethanol for 6h; Reflux; Inert atmosphere; | [Ru2(μ-O2CCH3)4(H2O)2](PF6) (0.100 g, 0.162 mmol) was dissolved in a minimal amount of methanol (∼15-25 mL) producing a dark orange solution. 6,6′-dimethyl-2,2′-bipyridine (0.119 g, 0.646 mmol) was dissolved in a minimal amount of methanol (∼10-20 mL) . Upon mixing, the reaction mixture was refluxed for 6 h under argon. The resulting solution was placed in the refrigerator (∼4 °C). dried in vacuo overnight. Reactions using other molar ratios from 1:1 to 8:1 (ligand to dimer) gave the same product. Anal. Calc. for C26H27N4O2RuPF6: C, 46.36; H, 4.04; N, 8.32. Found: C, 46.26; H, 4.32; N, 7.91%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | at 20℃; for 8h; | 1 [Cu2(dppa)3(CH3CN)2](BF4)2 (0.015 mmol) and the diimine (0.038 mmol) were placed in an oven dried 100 ml Schlenk flask in a glove box, sealed with a rubber septum and taken out. Freshly distilled, dried dichloromethane (10 ml) was injected through the septum using a long needle. The mixture was stirred at room temperature for 8 h, resulting in a clear orange solution. The later was filtered and the filtrate concentrated to 5 ml and then carefully layered with 20 ml of diethyl ether to afford, after few days, crystals were obtained. Anal. Calc. for C76H64Cu2N4P4B2F8: C, 62.55; H, 4.38; N, 3.84; Found: C, 62.27; H, 4.30; N, 4.23% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
126 mg | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With lithium diisopropyl amide In tetrahydrofuran at -65℃; for 0.75h; Stage #2: diiodomethane In tetrahydrofuran at -65 - -30℃; | 2 Preparation of P9 To a solution of 6,6'-dimethyl-2,2'-bipyridinyl (250 mg) in dry THF (6 mL) was added a freshly prepared LDA solution (8 mL; 0.18M solution in THF) at -65°C. After stirring for 45min at -65°C, methylene iodide (55 pL) dissolved in dry THF (3 mL) was slowly added. The reaction mixture was stirred for lh at -65°C then was allowed to warm up slowly until -30°C for lh. The reaction was then quenched with ammonium chloride solution and further stirred until ambient temperature was reached. The reaction mixture was extracted with ethyl acetate. The organic phase was washed with ammonium chloride solution, dried over magnesium sulphate, purified over silica gel to give white-yellow crystals (126 mg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44 g | With lithium diisopropyl amide In tetrahydrofuran at -60℃; for 1.25h; Inert atmosphere; | 6 Preparation of I12 Lithium diisopropyl amide (310 mL; 2M solution in tetrahydrofuran) was added under an argon atmosphere within lh at -60°C to a mixture of 6,6'-dimethyl-2,2'-dipyridyl (53.00 g) and diethyl carbonate (102 mL) in tetrahydrofuran (27 mL). After stirring for further 15min at -60°C a solution of ammonium chloride (50 mL; 25% in water) was carefully added. The reaction mixture was then poured on water and extracted with ethyl acetate. The organic phases were washed with water, dried over magnesium sulfate, concentrated and purified over silica gel to give 44 g of yellow liquid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With triethyl borane; lithium triethylborohydride; cobalt(II) bromide In tetrahydrofuran; toluene at 70℃; for 20h; Glovebox; Inert atmosphere; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | With 2,3,4,5,6-pentafluorostyrene; hydrogen; bis(pentafluorophenyl)borohydride In toluene at 100℃; for 20h; Glovebox; Autoclave; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39.1% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine; sodium tetrachloroaurate(III) dihyrate In acetonitrile for 1h; Reflux; Inert atmosphere; Stage #2: With silver tetrafluoroborate In acetonitrile Reflux; Microwave irradiation; | 2 Synthesis of [(methylbipy)AuCl3] The synthesis of [(methylbipy)AuCl3] has recently been carried outusing a microwave technique, and was published while compound 2was being evaluated in our laboratory for its in vitro antitumor activity[23]. In thework reported here, compound 2was synthesized in an analogousfashion to compound 1 [18]. NaAuCl4·2H2O (0.685 g, 1.63 mmol)and methylbipy (0.3174 g, 1.63 mmol) were dissolved in approximately50 mL acetonitrile. This yellow reaction mixture was refluxed for 1 h,followed by the addition of AgBF4 (0.3003 g, 1.63 mmol; dissolved inabout 5 mL of acetonitrile). This solution was refluxed overnight, uponwhich an orange color formed and the presence of AgCl was observed.The AgCl precipitate was filtered off through a celite pad, the solventremoved by rotary evaporation, and the residual solid dissolved inwarm methylene chloride (approximately 15 mL). The resulting orangesolution was extracted three times with 20 mL of deionizedwater, dried with MgSO4, and filtered once more through celite.The solution was placed in a refrigerator for recrystallization, andorange needles formed overnight at 5 °C (0.311 g; 39.1% yield). Elementalanalysis found: C = 29.66%, H = 2.43%; calculated: C, 29.56%; H2.48%. λmax(CH3CN, 20 °C)/nm (ε, M-1·cm-1) 225 (39, 100), 305(17, 500), and 315-330 (1220). IR: νmax/cm-1 3096 (CH), 2959, 2918,2851 (CH), 1589, 1572 (conj. CC). 1H NMR (300 MHz, CDCl3, 20 °C) δ7.93-7.89 (m, 4H, H3-6), 7.51 (d, 2H, H2,7), and 3.14 (s, 6H, H1,8) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | In benzene for 13h; Cooling with ice; Reflux; | 3.4. Synthesis of bis(6,6'-dimethyl-2,2'-bipyridyl) dichloro titanium(II) TiCl2(dpMe)2 , (D1) To a colorless solution of titanium tetrachloride (0.2 g, 1.05 mmol) in benzene (15 mL), a colorless turbid solution of 6,6'-dimethyl-2,2'-bipyridine (0.388 g, 2.10 mmol) in benzene (20 mL) was added dropwise with continuous stirring. The color of solution changed from colorless to light yellow immediately. The reaction mixture was stirred for 3 h, and then reuxed for 10 h until the evolution of chlorine gas ceased. The solvent was removed through vacuum ltration and the complex was dried under vacuum. Recrystallization of the complex was done in methanol. Yield 85%, mp 170-175 C (decompose); UV (MeOH) max 235, 290 nm; FTIR (KBr) (cm1)3030 (C-H stretching), 1634 (C=C stretching), 1413 (C=N stretching), 1282 (C-H bending), 794 (C-H out ofplane deformation), 447 (Ti-N stretching); 1H NMR (DMSO-d6 , 400 MHz) , ppm = 8.45 (d, 3 J = 7.8 Hz,4H, H3) , 8.25 (t, 3 J = 7.9, 7.8 Hz, 4H, H4) , 7.7 (d, 3 J = 7.84 Hz, 4H, H5) , 2.87 (s, 12H, CH3) . |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | In methanol; acetonitrile at 45℃; for 0.25h; | Synthesis of [Au(6,6'-dmbipy)Cl3] (1) A solution of 6,6'-dimethyl-2,2'-bipyridine (0.25 g,1.32 mmol) in methanol (15 mL) was added to a solution ofAuCl3 (0.40 g, 1.32 mmol) in acetonitrile (15 mL) and the resulting yellow solution was stirred for 15 min at 45C.Then, it was left to evaporate slowly at room temperature.After one week, yellow prysmatic crystals of1were isolated(yield 0.47 g, 73.0%; m.p. 220-221C). IR (CsI, cm1):3097w, 2910w, 1579s, 1452s, 1378m, 1237s, 1181m, 1124m,1035m, 1001m, 910m, 788s, 718w, 639m, 554m, 429w, 357s,288w, 257m. UV-Vis:λmax(CH3CN, nm), 226, 303.1H NMR(CD3CN, ppm): 1.96 (s, 3H), 3.06 (s, 3H), 7.64 (m, 2H) and8.18 (m, 4H).13C NMR (CD3CN, ppm): 21.1 (s), 25.1 (s),117.0 (s), 117.2 (s), 117.4 (s), 123.6 (s), 125.2 (s), 126.3 (s),127.6 (s), 140.9 (s), 153.6 (s) and 159.4 (s). Anal. Calcd. C,29.56; H, 2.46; N, 5.74. Found: C, 29.32; H, 2.44; N, 5.69%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74.4% | In methanol; acetonitrile at 45℃; for 0.25h; | Synthesis of [Au(6,6'-dmbipy)Br3] (2) A solution of 6,6'-dimethyl-2,2'-bipyridine (0.25 g,1.32 mmol) in methanol (15 mL) was added to a solution ofAuBr3 (0.58 g, 1.32 mmol) in acetonitrile (15 mL) and theresulting red solution was stirred for 15 min at 45C. Then, itwas left to evaporate slowly at room temperature. After oneweek, orange block crystals of2were isolated (yield 0.61 g,74.4%; m.p. 131-132C). IR (CsI, cm1): 3088w, 2915w,1571s, 1445s, 1363s, 1226s, 1160w, 1087m, 1034m, 998m,906w, 786s, 722w, 635m, 529m, 469w, 387s, 327w, 280s,260m. UV-Vis:λmax(CH3CN, nm), 254, 312, 395.1H NMR(CD3CN, ppm): 1.96 (s, 3H), 3.04 (s, 3H), 7.72 (m, 2H) and8.15 (m, 4H).13C NMR (CD3CN, ppm): 21.4 (s), 25.7 (s), 116.1 (s), 116.8 (s), 117.3 (s), 118.0 (s), 120.3 (s), 123.5 (s),127.6 (s), 140.7 (s), 143.0 (s) and 157.4 (s). Anal. Calcd. C,23.21; H, 1.93; N, 4.51. Found: C, 23.01; H, 1.91; N, 4.48%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82.9% | In acetonitrile at 20℃; for 168h; | 2 4.2. Synthesis [6,60-dmbipy.H]2[PtCl6] (1) 6,6'-Dimethyl-2,20-bipyridine (0.41 g, 2.20 mmol) in CH3CN(50 mL) was added to a solution of H2PtCl6.6H2O (0.58 g,1.10 mmol)in CH3CN (50 mL) without stirring at room temperature. This yellowsolution was left to evaporate slowly at room temperature.After one week, yellow plate crystals of 1 were isolated (yield0.71 g, 82.9%, m. p. 237 C). IR (CsI, cm1): 3221 w, 3148 m, 3070 m,2920 w, 1616 s, 1520 m, 1448 m, 1363 m, 1285 m, 1264 m, 1175 m,1112 m, 1025 m, 871 m, 797 s, 689 w, 627 w, 552 w, 531 w, 325 s.UVeVis: lmax (CH3CN, nm), 275. 1H NMR (CD3CN, ppm): 2.84 (s,3H), 6.55 (br, 1H), 7.73 (d, 1H) and 8.29 (t, 2H). Anal. Calcd. forC24H26Cl6N4Pt(%): C, 37.04; H, 3.34; N, 7.19. Found: C, 36.76; H, 3.32;N, 7.13. |
Yield | Reaction Conditions | Operation in experiment |
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75.4% | In methanol; acetonitrile at 40℃; for 0.5h; | 2.2. Synthesis of [Cd(6,6'-dmbipy)2(η2-NO3)][Cd(6,6'-dmbipy)(η2-NO3)3] (3) A solution of 6,6'-dimethyl-2,2'-bipyridine (0.28 g, 1.50 mmol)in acetonitrile (10 ml) was added to a solution of Cd(NO3)24H2O(0.23 g, 0.75 mmol) in methanol (10 ml) and the resulting colorlesssolution was stirred for 30 min at 40 C. This solution was left toslowly evaporate at room temperature. After 1 week, colorlessblock crystals of the title compound were isolated (yield 0.29 g,75.4%, m.p. = 226 C). Anal. Calc. for C36H36Cd2N10O12: C, 42.16; H,3.51; N, 13.65; O, 18.72. Found: C, 41.93; H, 3.49; N, 13.58; O,18.87%. IR (CsI, cm1): 3128w, 3070w, 2970w, 2920w, 1597s,1575m, 1459s, 1445s, 1364m, 1309m, 1293m, 1255m, 1180w,1127w, 1034m, 1016m, 817w, 808m, 789s, 744w, 705w, 646w,561w, 526w, 475w, 433w, 385w, 336w, 289w, 261m. UV-Vis: kmax(CH3CN) for free 6,60-dmbipyligand at 239, 289 nm and for complexat 208, 244 and 304 nm. 1H NMR (DMSO-d6, ppm) for free6,60-dmbipy ligand: 2.51 (s, -CH3), 7.24 (d, J = 7.4, 1H), 7.75 (t,1H), 8.15 (d, J = 7.4, 1H) and for complex: 2.55 (s, -CH3), 7.29 (d,J = 7.1, 1H), 7.81 (t, 1H), 8.18 (d, J = 7.1, 1H). 13C{1H}NMR (DMSOd6,ppm) for free 6,60-dmbipy ligand: 24.3(s), 117.1(s), 125.2(s),137.6(s), 154.1(s), 157.2(s) and for complex: 25.1(s), 118.4(s),124.3(s), 138.3(s), 155.5(s), 158.3(s). |
Yield | Reaction Conditions | Operation in experiment |
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58% | In acetonitrile at -20℃; Inert atmosphere; Schlenk technique; | General procedure: To a solution of CF3SO2Na (312mg, 2.0 mmol) and CuCl (198 mg, 2.0 mmol) in acetonitrile(8 mL, pre-cooled to - 20 C) were added Ph3P (1048 mg, 4.0mmol). The reaction mixture was stirred under N2 atmosphere at room temperature for 3-5 h until completion. Then the reaction mixture was filtrated through PTFE filter to remove the insoluble salts and get a clear solution. This solution was frozen (~ - 20C) for 24 h until the formation of crystalline Ph3PO. The acetonitrile solution of CuSCF3 was collected by decanting to remove Ph3PO and cooled to - 20 C again. Then the solution of 6,6′-dimethyl-2,2′-bipyridine (369 mg, 2 mmol) in acetonitrile(6.0 mL) was added in dropwise. The reaction solution was kept at the fridge (- 20 C) for crystallization. The resulting crystals were collected by filtration and washed with cold acetonitrile (3 mL, - 20 C) and ether (5 mL), and dried under reduced pressure to afford the corresponding [{(6,6′-dimethyl-2,2′-bipyridine)Cu(SCF3)}2] complex (red colour powder, 405mg, yield: 58 %). |
202 mg | In acetonitrile at -25℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With hydrogen In dichloromethane at 20℃; for 4h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
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54% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine; cis-dichloro(2,2′-bipyridine)ruthenium(II)chloride In ethylene glycol for 0.116667h; Reflux; Microwave irradiation; Inert atmosphere; Stage #2: potassium hexafluorophosphate In water; ethylene glycol at 20℃; Inert atmosphere; | Synthesis of the Hexafluorophosphate Salt of the RutheniumComplexes 2-6: General procedure: The ruthenium complex 2·(PF6)2 was synthesized by the following procedure. [Ru(bpy)2Cl2] (0.242 g, 0.5 mmol) and dmbpy (0.092 g, 0.5 mmol) were mixed in ethylene glycol (15 ml).After the suspended mixture was refluxed for 7 min in the microwave oven under purging nitrogen atmosphere. The reaction mixture was cooled to room temperature and then the saturated aqueous solution of KPF6 (20 ml)was added. An orange-red product began to precipitate and was collected in 60% yield. Complexes 2, 3,4, 5 and 6 were synthesized in the similar way. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
87% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine; bis(2,2'-bipyridine)dichlororuthenium(II) dihydrate In ethylene glycol for 6h; Darkness; Heating; Stage #2: potassium hexafluorophosphate In water; ethylene glycol Darkness; | 2 Compound 4: Compound 4: Ru(bpy)2Cl2.2H2O (200 mg, 0.384 mmol) and 6,6'-dimethyl-2,2'-bipyridine (78 mg, 0.423 mmol) were added to 8 mL of degassed ethylene glycol in a pressure tube. The mixture was heated in the dark for 6 hours, allowed to cool and poured into 50 mL of distilled water. Addition of a saturated aq. KPF6 solution produced a dark orange precipitate that was collected by vacuum filtration. The purification of the solid was carried out by flash chromatography (silica gel, 0.1% saturated KNO3, 2% H2O in MeCN ramped to 9% H2O) to give the pure complex. A saturated aq. solution of KPF6 was added, and the metal complex was extracted into CH2Cl2. It was dried down to give a red solid. Yield: 297 mg (87%). |
73% | for 6h; Inert atmosphere; Reflux; | [Ru(bpy)2(dmbpy)](PF6)2 (C1) General procedure: Ru(bpy)2Cl2·2H2O (200 mg, 0.384 mmol) and dmbpy(78 mg, 0.423 mmol) were added to 8 mL of N2degassedethylene glycol in a 50 ml round bottom flask. The mixturewas refluxed in the dark under argon for 6 h. The solutionwas then cooled at room temperature and the hexafluorophosphate(PF6) salt was precipitated by adding a saturatedaqueous solution of KPF6dropwise. The resulting orange precipitate was collected by vacuum filtration and washedthoroughly with water and diethyl ether. The product (C1)was purified on a sephadex LH-20 column with acetonitrileas eluent and finally dried under rotovap. Yield: 267 mg;73%. 1H NMR (CD3CN, 500 MHz): δ = 8.49 (d, J = 8 Hz,2H), 8.40 (d, J = 8 Hz, 2H), 8.28 (d, J = 8 Hz, 2H), 8.36 (d,J = 10 Hz, 2H), 8.10 (td, J = 8 Hz, 1.65 2H), 7.96-7.91 (m,6H), 7.63 (d, J = 6.5 Hz, 2H), 7.47 (td, J = 5.86 Hz, 1.65 Hz,2H), 7.28 (d, J = 7.5 Hz, 2H), 7.31 (td, J = 7.5 Hz, 1.65 Hz,2H), 1.66 (s, 6H) (Fig. S1). 13C NMR (CD3CN, 500 MHz):δ = 166.5, 159.7, 158.5, 158.3, 153.9, 152.7, 139.1, 138.7,138.6, 129.0, 128.3, 128.1, 125.3, 125.2, 123.0, 25.5 (Fig.S2). E. Anal. Calcd for C32H28F12N6P2Ru:C 43.30; H 3.18;N 9.47; found C 43.07; H 3.18; N 9.27. HR-ESI MS m/zfor [M-2(PF6)]2+ calcd. 299.0714; found 299.0732. Dowex22 chloride in water was used for counter-ion exchangeof the compound prior to biological testing with HPLCpurity > 95%, see Fig. S3. |
Stage #1: 6,6'-dimethyl-2,2'-bipyridine; bis(2,2'-bipyridine)dichlororuthenium(II) dihydrate In ethylene glycol at 120℃; for 6h; Inert atmosphere; Stage #2: potassium hexafluorophosphate In water; ethylene glycol |
Stage #1: 6,6'-dimethyl-2,2'-bipyridine; bis(2,2'-bipyridine)dichlororuthenium(II) dihydrate In glycerol at 120℃; Inert atmosphere; Stage #2: potassium hexafluorophosphate In water at 20℃; Inert atmosphere; | [Ru(bpy)3]Cl2 (Ru1): General procedure: Complex [Ru(bpy)3](PF6)2 was synthesizedaccording to methods described in our previous work [26]. Briefly, Ru(bpy)2Cl22H2O (100 mg, 0.192 mmol) was dissolved in 4 mL ethyleneglycol and bpy (45 mg, 0.288 mmol). After filling with argon to removethe oxygen, the mixture was heated to 120 C at reflux and stirred for 6h. After cooling to room temperature, 23 mL distilled water was addedexcess saturated KPF6 solution. A dark red precipitate was produced andcollected by centrifugation. The solid was washed three times withwater, diethyl ether, and purified by chromatography (aluminum oxide,acetonitrile: ethanol = 1:1). The solvent was evaporated, and theresultant residue was washed by saturated KPF6 solution. The productwas washed several times with water, and was then collected bycentrifugation. Finally, the solid was dissolved in acetone and precipitatedby adding diethyl ether. The procedure was repeated three times.The as-obtained pure [Ru(bpy)3](PF6)2 was dried by lyophilization. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.6% | In methanol at 45℃; for 0.5h; | Synthesis of [Zn(6,6'-dm-2,2'-bipy)(η2-NO3)2] General procedure: 6-Methyl-2,2′-bipyridine (0.15 g, 0.85 mmol,0.14 mL) in methanol (5 mL) was added to a solution ofZn(NO3)2·4H2O (0.22 g, 0.85 mmol) in 5 mL of methanoland the resulting colorless solution was stirred for30 min at 45 °C. This solution was left to evaporate slowlyat room temperature. After 1 week, colorless crystals of 1were isolated (yield 0.23 g, 75.2 %, |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | In tetrahydrofuran for 24h; Reflux; | |
90% | In N,N-dimethyl-formamide at 120℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at 0 - 25℃; for 1h; Inert atmosphere; Stage #2: Chlorodiisopropylphosphane With borane-THF In tetrahydrofuran; hexane | A1.1 (1) Synthesis of Compound 5 A stirrer, 6 6,6′-bi-2-picoline (184.2 mg, 1.0 mmol), and 7 THF (10 mL) were placed in a 200-mL double neck flask that had been dried and substituted with 8 argon gas, and the mixture was sufficiently stirred. Thereafter, while stirring, the flask was sufficiently cooled by being immersed in a refrigerant (icy 9 water) at 0° C., thereby obtaining a 10 6,6′-bi-2-picoline-THF solution. (0199) 7 THF (10 mL) and 12 diisopropylamine (0.85 mL, 6.0 mmol) were placed in a 300-mL double neck flask that had been dried and substituted with 8 argon gas, and the mixture was sufficiently stirred. Thereafter, while stirring, the flask was sufficiently cooled by being immersed in a refrigerant (icy 9 water) at 0° C. A 13 n-butyllithium-hexane solution (4.0-mL, 1.5-M hexane solution, 6.0 mmol) was gradually added dropwise to the solution, thereby causing a reaction. Subsequently, stirring of the reaction solution continued for another 10 minutes while keeping the temperature of the reaction solution at 0° C., thereby obtaining a 14 lithium diisopropylamide-THF solution. (0200) Subsequently, the lithium diisopropylamide-THF solution was added dropwise to the double neck flask containing the 6,6′-bi-2-picoline-THF solution using a cannular, thereby causing a reaction; as a result, a colorless and transparent reaction solution was changed to a bluish-purple solution. While thus adding the lithium diisopropylamide-THF solution dropwise, the temperature inside the flask was kept at 0° C. After the dropwise addition was completed, the flask was taken out of the refrigerant. While stirring of the reaction solution continued, the solution was restored to room temperature (25° C.). After an hour, chlorodiisopropylphosphine (314.6 μL, 2.0 mmol) was added dropwise to the reaction solution, and stirring of the solution continued for another 4 hours. Subsequently, a borane-THF solution (10-mL, 1.0-M THF solution, 10 mmol) was added, and stirring continued overnight. Thereafter, the flask was sufficiently cooled by being immersed in a refrigerant (icy water) at 0° C. After cooling, water was added to the reaction solution, and the whole solution was concentrated by an evaporator. The obtained residue was transferred to a 500-mL separatory funnel, and 100 mL of distilled water, 50 mL of dichloromethane and a small amount of saturated saline were added. This mixture was subjected to separation and extraction five times in total, and the desired organic compound was extracted in the organic layer (dichloromethane layer). The resulting organic layer was dehydrated with sodium sulfate. A filtrate obtained by filtration was concentrated by an evaporator. The concentrated filtrate was then subjected to column chromatography (developing solvent: dichloromethane/hexane=8/1) in which silica gels were shortly accumulated. Subsequently, the resulting dichloromethane/hexane solution containing the resulting purified product was concentrated under reduced pressure (0.1 to 2 mmHg), thereby obtaining 244.3 mg (0.55 mmol) of 6,6′-bis diisopropyl phosphino methyl-2,2′-bipyridine borane complex (Compound 5) as a white powder at an isolation yield of 55%. (0201) The spectral data of Compound 5 is shown below. (0202) 1H NMR (600 MHz, CDCl3): δ 8.24 (d, 2H, J=7.6 Hz, C10H6N2), 7.76 (t, 2H, J=7.6 Hz, C10H6N2), 7.34 (d, 2H, J=7.6 Hz, C10H6N2), 3.33 (d, 4H, J=11.0 Hz, PCH2), 2.12-2.23 (m, 4H, CH(CH3)2), 1.17-1.27 (m, 24H, CH(CH3)2), 0.10-0.70 (br, 6H, BH3). 13C NMR (151 MHz, CDCl3): δ 155.3, 154.2 (d, 2JPC=7.2 Hz), 137.3, 124.9, 118.8, 30.6 (d, JPC=26.0 Hz), 21.8 (d, 1JPC=31.8 Hz), 17.0 (d, 2JPC=5.8 Hz). 31P{1H} NMR (243 MHz, CDCl3): δ36.0, 36.3, HRMS (ESI, (M+H)+) Calcd for C24H44B2N2P2+: 445.3247. Found m/z=445.3247 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at 0 - 25℃; for 1h; Inert atmosphere; Stage #2: chlorodicyclohexylphosphane With borane-THF In tetrahydrofuran; hexane | A2.1 (1) Synthesis of Compound 6 A stirrer, 6,6′-bi-2-picoline (1850.0 mg, 10 mmol) and THF (60 mL) were placed in a 1,000-mL double neck flask that had been dried and substituted with argon gas, and the mixture was sufficiently stirred. Thereafter, while stirring, the flask was sufficiently cooled by being immersed in a refrigerant (icy water) at 0° C., thereby obtaining a 6,6′-bi-2-picoline-THF solution. THF (30 mL) and diisopropylamine (8.4 mL, 60 mmol) were placed in a 300-mL double neck flask that had been dried and substituted with argon gas, and the mixture was sufficiently stirred. Thereafter, while stirring, the flask was sufficiently cooled by being immersed in a refrigerant (icy water) at 0° C. A n-butyllithium-hexane solution (40-mL, 1.5-M hexane solution, 60 mmol) was gradually added dropwise to the solution, thereby causing a reaction. Subsequently, the stirring of the reaction solution continued for another 10 minutes while keeping the temperature of the reaction solution at 0° C., thereby obtaining a lithium diisopropylamide-THF solution. Subsequently, the lithium diisopropylamide-THF solution was added dropwise to the double neck flask containing the 6,6′-bi-2-picoline-THF solution using a cannular, thereby causing a reaction; as a result, a colorless and transparent reaction solution was changed to a bluish-purple solution. While thus adding the lithium diisopropylamide-THF solution dropwise, the temperature inside the flask was kept at 0° C. After the dropwise addition was completed, the flask was taken out of the refrigerant. While the stirring of the reaction solution continued, the solution was restored to room temperature (25° C.). After an hour, chlorodicyclohexylphosphine (4.4 mL, 20 mmol) was added dropwise to the reaction solution, and the stirring of the solution continued for another 2 and a half hours. Subsequently, a borane-THF solution (100-mL, 1.0-M THF solution, 100 mmol) was added, and the stirring continued overnight. Thereafter, the flask was sufficiently cooled by being immersed in a refrigerant (icy water) at 0° C. After cooling, water was added to the reaction solution, and the whole solution was concentrated by an evaporator. The obtained residue was transferred to a 1,000-mL separatory funnel, and 100 mL of distilled water, 50 mL of dichloromethane and a small amount of saturated saline were added. This mixture was subjected to separation and extraction four times in total, and the desired organic compound was extracted in the organic layer (dichloromethane layer). The resulting organic layer was dehydrated with sodium sulfate. A filtrate obtained by filtration was concentrated by an evaporator. After the concentration, a small amount of THF was added to the resulting residue to suspend the residue. White powder was obtained by filtration. The white powder was washed with THF several times, thereby obtaining 2,417.6 mg (4.0 mmol) of a 6,6′-bis dicyclohexyl phosphino methyl-2,2′-bipyridine borane complex (Compound 6) as a white powder at an isolation yield of 40%. The spectral data of Compound 6 is shown below. 1H NMR (600 MHz, CDCl3): δ 8.29 (d, 2H, J=8.3 Hz, C10H6N2), 7.75 (t, 2H, J=7.6 Hz, C10H6N2), 7.31 (d, 2H, J=7.6 Hz, C10H6N2), 3.31 (d, 4H, J=11.0 Hz, PCH2), 1.60-2.00 (m, 24H, C6H11), 1.11-1.50 (m, 20H, C6H). 13C NMR (151 MHz, CDCl3): δ 155.2, 154.5 (d, 2JPC=7.2 Hz), 137.2, 125.0, 118.7, 31.5 (d, 1JPC=30.3 Hz), 30.5 (d, 1JPC=27.5 Hz), 27.01, 26.94, 26.86, 26.75, 26.63, 25.97. 31P{1H} NMR (243 MHz, CDCl3): δ 28.6, HRMS (ESI, (M+H)+) Calcd for C36H60B2N2P2+: 605.4502. Found m/z=605.4502 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
36% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With n-butyllithium; diisopropylamine In tetrahydrofuran; hexane at 0 - 25℃; for 1h; Inert atmosphere; Stage #2: di(tert-butyl)chlorophosphine With borane-THF In tetrahydrofuran; hexane | A3.1 (1) Synthesis of Compound 7 A stirrer, 6,6′-bi-2-picoline (557.6 mg, 3.0 mmol) and THF (30 mL) were placed in a 300-mL double neck flask that had been dried and substituted with argon gas, and the mixture was sufficiently stirred. Thereafter, while stirring, the flask was sufficiently cooled by being immersed in a refrigerant (icy water) at 0° C., thereby obtaining a 6,6′-bi-2-picoline-THF solution. THF (20 mL) and diisopropylamine (2.52 mL, 18.0 mmol) were placed in a 200-mL double neck flask that had been dried and substituted with argon gas, and the mixture was sufficiently stirred. Thereafter, while stirring, the flask was sufficiently cooled by being immersed in a refrigerant (icy water) at 0° C. A n-butyllithium-hexane solution (12.0-mL, 1.5-M hexane solution, 18.0 mmol) was gradually added dropwise to the solution, thereby causing a reaction. Subsequently, the stirring of the reaction solution continued for another 10 minutes while keeping the temperature of the reaction solution at 0° C., thereby obtaining a lithium diisopropylamide-THF solution. Subsequently, the lithium diisopropylamide-THF solution was added dropwise to the double neck flask containing the 6,6′-bi-2-picoline-THF solution using a cannular, thereby causing a reaction; as a result, a colorless and transparent reaction solution was changed to a bluish-purple solution. While thus adding the lithium diisopropylamide-THF solution dropwise, the temperature inside the flask was kept at 0° C. After the dropwise addition was completed, the flask was taken out of the refrigerant. While the stirring of the reaction solution continued, the solution was restored to room temperature (25° C.). After an hour, chloro di-t-butyl phosphine (1.20 mL, 6.3 mmol) was added dropwise to the reaction solution, and the stirring of the solution continued for another two hours. Subsequently, a borane-THF solution (35-mL, 1.0-M THF solution, 35 mmol) was added, and the stirring continued overnight. Thereafter, the flask was sufficiently cooled by being immersed in a refrigerant (icy water) at 0° C. After cooling, water was added to the reaction solution, and the whole solution was concentrated by an evaporator. The obtained residue was transferred to a 500-mL separatory funnel, and 100 mL of distilled water, 50 mL of dichloromethane and a small amount of saturated saline were added. This mixture was subjected to separation and extraction five times in total, and the desired organic compound was extracted in the organic layer (dichloromethane layer). The resulting organic layer was dehydrated with sodium sulfate. A filtrate obtained by filtration was concentrated by an evaporator. After the concentration, a small amount of ethyl acetate was added to the resulting residue to suspend the residue. A pale red solid was obtained by filtration. The solid was washed with ethyl acetate several times, thereby obtaining 540 mg (1.08 mmol) of a 6,6′-bis di-t-phosphino methyl-2,2′-bipyridine borane complex (Compound 7) as a pale red powder at an isolation yield of 36%. The spectral data of Compound 7 is shown below. 1H NMR (600 MHz, CDCl3): δ 8.22 (d, 2H, J=8.3 Hz, C10H6N2), 7.73 (t, 2H, J=7.8 Hz, C10H6N2), 7.56 (d, 2H, J=7.8 Hz, C10H6N2), 3.43 (d, 4H, J=12.0 Hz, PCH2), 1.321 (s, 18H, C(CH3)3), 1.30 (s, 18H, C(CH3)3), 0.20-0.80 (br, 6H, BH3). 13C NMR (149 MHz, CDCl3): δ 154.9 (d, 1JPC=11.3 Hz), 136.8, 125.9, 118.8, 32.8 (d, 1JPC=25.6 Hz), 29.4 (d, 1JPC=22.9 Hz), 28.2, 31P{1H} NMR (241 MHz, CDCl3): δ 48.1, 47.8, (ESI, (M+H)+) Calcd for C28H52B2N2P2+: 501.3874. Found m/z=501.3869 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In ethanol; water at 20℃; Inert atmosphere; | 2 Cu(II)dmbp2Cl2 (4): One equivalent of CuC12 was mixedwith 2.2 equivalents of 2,2’-dimethyl bipyridine in ethanoland water (1: 1), under nitrogen atmosphere, at room temperature for 2 hours. Complex (4) was collected by filtrationand washed with water and diethyl ethet The yield was 80%(mol). |
In ethanol at 20℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In methanol at 20℃; | 2.4 Synthesis of [Hg(6,6′-dmbipy)(SCN)2] (3) The complex of 3 was prepared according to the procedure of complexes 1 and 2 except using 6,6′-dimethyl-2,2′-bipyridine instead of 4,4′-dimethyl-2,2′-bipyridine and 5,5′-dimethyl-2,2′-bipyridine in methanol. Colorless prismatic single crystals of 3 suitable for X-ray analyses were obtained by methanol diffusion into the colorless solution of 3 in DMSO over one week (yield 0.47g, 75.0%, m. p. 221°C). Infrared frequencies (CsI, cm-1) are reported in Table1. UV-Vis: λmax (DMSO, nm) for free 6,6′-dmbipy ligand: 292 and for complex: 294. 1H NMR (DMSO-d6, ppm) for free 6,6′-dmbipy ligand: 2.51 (s, -CH3), 7.24 (d, J=7.4, 1H), 7.75 (t, 1H), 8.15 (d, J=7.4, 1H) [59] and for complex: 2.78 (s, -CH3), 7.70 (d, J=7.2, 1H), 8.16 (t, 1H) and 8.51 (d, J=7.2, 1H). 13C{1H}NMR (DMSO-d6, ppm): for free 6,6′-dmbipy ligand: 24.3(s), 117.1(s), 125.2(s), 137.6(s), 154.1(s), 157.2(s) [59] and for complex: 25.8(s), 117.5(s), 121.7(s), 127.5(s), 141.8(s), 150.5(s) and 158.5(s). Elemental analysis: C14H12HgN4S2 (%) (501.01); Anal. Calcd (%): C, 33.56; H, 2.40; N, 11.18; S, 12.77. Found: C, 33.34; H, 2.38; N, 11.13; S, 12.64. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
32.9% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine; [{Rh(μ-Cl)(2-(p-tolyl)pyridinato)2}2] In methanol; dichloromethane; water for 3h; Reflux; Schlenk technique; Inert atmosphere; Stage #2: potassium hexafluorophosphate In methanol; dichloromethane; water at 20℃; for 0.333333h; Schlenk technique; Inert atmosphere; Stage #3: dichloromethane In 2-Methylpentane Schlenk technique; Inert atmosphere; | General procedure: General procedure: To a solution of [{M(µ-Cl)(ptpy)2}2] (M=Rh, Ir) (0.15mmol) in 25mL of a mixture of CH2Cl2/MeOH/H2O (1:1:0.5) the bipyridine ligand (0.3mmol) was added and the mixture refluxed with stirring for 3h. After cooling to room temperature KPF6 (0.5mmol) was added and stirred for 20min. The solvent was removed to dryness in vacuo and the residue dissolved in dichloromethane and chromatographed on alumina with CH2Cl2/acetone (9:1) as the eluent. The resulting solution was evaporated to dryness and the residue was redissolved in 5ml of dichloromethane and the product was precipitated by slow diffusion of isohexane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine; [{Ir(μ-Cl)(2-(p-tolyl)pyridinato)2}2] In methanol; dichloromethane; water for 3h; Reflux; Schlenk technique; Inert atmosphere; Stage #2: potassium hexafluorophosphate In methanol; dichloromethane; water at 20℃; for 0.333333h; Schlenk technique; Inert atmosphere; | General procedure: General procedure: To a solution of [{M(µ-Cl)(ptpy)2}2] (M=Rh, Ir) (0.15mmol) in 25mL of a mixture of CH2Cl2/MeOH/H2O (1:1:0.5) the bipyridine ligand (0.3mmol) was added and the mixture refluxed with stirring for 3h. After cooling to room temperature KPF6 (0.5mmol) was added and stirred for 20min. The solvent was removed to dryness in vacuo and the residue dissolved in dichloromethane and chromatographed on alumina with CH2Cl2/acetone (9:1) as the eluent. The resulting solution was evaporated to dryness and the residue was redissolved in 5ml of dichloromethane and the product was precipitated by slow diffusion of isohexane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.1% | With potassium graphite In toluene at 25℃; for 16h; | 2.4 Preparation of Th(BcMes)2Me2bpy (5) 6′6-dimethyl-2,2′-dipyridyl (0.034g, 0.186mmol) was added as a solid to a 17 toluene (6mL) solution of 8 1 (0.233g, 0.186mmol) immediately followed by the addition of solid 18 potassium 19 graphite (0.076mg, 0.561mmol) at 25°C. The resulting dark purple/black suspension was stirred for 16hat this temperature. The reaction mixture was filtered through a Celite pad atop an M-porosity fritted filter and concentrated to a black oily residue. The residue was triturated with hexanes (3×1mL) to afford a dark purple solid. The dark solid was then extracted into hexanes (3×5mL) and filtered. The combined filtrates were concentrated and stored at room temperature for 48h during such time dark purple blocks deposited from solution. Additional crops of 20 crystals were obtained by concentrating the mother liquor (combined yield: 0.196g, 89.1%). 1H NMR (400MHz, C6D6) δ 6.94 (d, 3JH-H=1.5Hz, HCImid, 2H), 6.89(d, 3JH-H=1.4Hz, HCImid, 2H), 6.86-6.82 (overlapping singlets, HCMes, 4H), 6.74 (s, HCMes, 2H), 6.64 (s, HCMes, 2H), 6.20 (d, 3JH-H=9.3Hz, HCbpy, 2H), 6.18 (d, 3JH-H=1.3Hz, HCImid, 2H), 6.05 (d, 3JH-H=1.5Hz, HCImid, 2H), 5.41 (br s, H2B, 2H), 5.13 (dd, 3JH-H=9.3, 5.6Hz, HCbpy, 2H), 4.05 (br s, H2B, 2H), 3.43 (d, JH-H=5.6Hz, HCbpy, 2H), 2.21 (s, H3CMes, 6H), 2.13 (s, H3CMes, 6H), 2.01 (s, H3CMes, 6H), 1.92 (s, H3CMes, 6H), 1.87 (s, H3CMes, 6H), 1.82 (s, H3CMes, 6H), 1.56 (s, H3CMe2bpy, 6H). 13C resonances that could be definitively assigned have been further specified. 13C{1H} NMR (101MHz, C6D6) δ 215.7 (CCarbene), 214.0 (CCarbene), 143.5 (CAr), 137.9 (CAr), 137.5 (CAr), 137.2 (CAr), 136.8 (CAr), 136.1 (CAr), 135.7 (CAr), 134.6 (CAr), 134.6 (CAr), 130.0 (CAr), 129.5 (CAr), 129.2 (CAr), 128.8 (CAr), 126.2 (CAr), 125.2 (Cimid), 123.8 (Cimid), 121.2 (Cbpy), 120.7 (Cimid), 120.5 (Cimid), 114.6 (Cbpy), 100.8 (Cbpy), 21.3 (CCH3), 21.0 (CCH3), 18.9 (CCH3), 18.6 (CCH3), 18.4 (CCH3), 18.3 (CCH3), 18.0 (CCH3). 11B{1H} NMR (193MHz, C6D6) δ -11.20. Anal. Calcd. for C60H68B2N10Th (1182.6): C 60.92H 5.79N 11.84; found: C 60.66 H 5.64N 11.64. M.p. 220.1-225.1°C (decomp). UV-Vis (toluene) λmax in nm (ε in 103Lmol-1cm-1) 398 (6.0), 486 (5.0), 538 (4.2), 584, (3.4), 678 (2.0), and 741 (1.3). FTIR (Nujol): νB-H 2455 (w), 2401 (m), 2304 (w), 2280 (w), 2225 (w), 2186 (m), 2064 (w) cm-1. Crystals suitable for single crystal X-ray diffraction studies were grown from a concentrated hexanes solution stored at room temperature for 48h. Alternatively, crystals could be grown from a room temperature vapor diffusion of hexane into a concentrated benzene solution. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In N,N-dimethyl-formamide at 140℃; for 24h; High pressure; | 2.2.5. Synthesis of [Co2(6,60-dimethyl-2,20-bipy)2(L)2]H2O (5) A mixture of 1H-indazole-3-carboxylic acid (8.5 mg, 0.05 mmol), 6,60-dimethyl-2,20-bipy(9.5 mg, 0.05 mmol) and cobalt(II) nitrate (14.6 mg, 0.05 mmol) in 2mL of DMF/H2O(v:v2:3) was placed in a pyrex glass tube at 140 C for 24 h to yield light red blockshapedcrystals. The crystals were washed with diethyl ether and dried. Yield: 78%(based on Co). Anal. Calcd for C40H33N8O5Co2: C, 58.33; N, 13.61; H, 4.01%. Found: C,58.05; N, 13.80; H, 4.36%. IR (KBr disk): 3447(s), 3071(s), 1626(s), 1574(m), 1454(m),1315(m), 1248(s), 788(m), 745(m). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.09% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine; sodium tetrachloroaurate (III) hydrate In ethanol at 20℃; for 3h; Stage #2: sodium dimethyldithiocarbamate In ethanol; water at 20℃; for 1h; | 2 Compound 7 was synthesized by following thesame procedure as described for compound 1 with minormodifications. Na[AuC14]H20, 0.5 mM (200 mg) and 6,6’-dimethyl-2,2’-dipyridyl 0.5 mM (92 mg) were added simultaneously in 20 mE of ethanol and mixture was stirred for 3h at room temperature. The sodium dimethyldithiocarbamate dihydrate 0.5 mM (72 mg) in 10 mE distilled water wasadded slowly in the bright yellow solution of above reactionmixture. The reaction mixture was stirred for 1 h at roomtemperature. The final product appeared as light yellowprecipitates in solution. The precipitates were collected byfiltration, washed with fresh distilled water (3x10 mE) anddried at room temperature under vacuum. Yield: 90.09%(187.27 mg). FT-IR (KSr, Vmax cm’): 3378 (m), 3033 (w),2925 (w), 1575 (s), 1477 (s), 1238 (m), 1162 (m), 1046 (m),998 (m), 868 (w), 567 (s), 440 (m). ‘H NMR (500 MHz,DMSO-d5): ö=2.49 (6H, 2xCH3), 3.36 (6H, 2xCH3), 7.41,7.93 and 8.22 (2H, 2xCH, SPY), ‘3C NMR (125.1 MHz, DMSO-d5): ö=13.77 (CH3), 45.25 (CH3), 119.15, 125.21, 139.47 and 158.57 (2,2-SPY), 187.83 (NCrrrS). Anal. calc. for C,5H,8C12N3S2Au (572.33): C, 31.48; H, 3.17; N, 7.34; S, 11.21%. Found: C, 31.67; H, 3.29; N, 7.38; S, 11.09%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | In ethanol at 60℃; for 0.5h; Inert atmosphere; Schlenk technique; Glovebox; | 8 Example 8. Preparation of a pyrimide-based iron complex catalyst 8 (the structural formula is as follows). Under an argon atmosphere, add anhydrous Fe(acac)3 (211.8mg, 0.6mmol) to a 50mL Schlenk flask, and dissolve it in 6mL of anhydrous ethanol at 60 ° C; Then, a solution of 6,6'-dimethyl-2,2'-bipyridine (110.4 mg, 0.6 mmol) in ethanol (4 mL) was added dropwise to the system. The reaction was carried out at 60 ° C for half an hour, and then returned to room temperature and stirred overnight. The filtrate was collected by filtration, concentrated, washed twice with cold ethanol, and dried under vacuum for 12 h to obtain a red-brown solid product 8 with a yield of 80%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
59% | In ethanol at 60℃; for 0.5h; Inert atmosphere; Schlenk technique; Glovebox; | 7 Example 7. Preparation of a pyrimide-based iron complex catalyst 7 (the structural formula is as follows). Under an argon atmosphere, add anhydrous Fe(acac)2 (127mg, 0.5mmol) to a 50mL Schlenk flask and dissolve it in 6mL of anhydrous ethanol at 60 ° C; Then, a solution of 6,6'-dimethyl-2,2'-bipyridine (92.0 mg, 0.5 mmol) in ethanol (4 mL) was added dropwise to the system. The reaction was carried out at 60 ° C for half an hour, and then returned to room temperature and stirred overnight. The filtrate was collected by filtration, concentrated, washed twice with cold ethanol, and dried under vacuum for 12 h to obtain a brown solid product 7, yield 59%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | In hexane; toluene at -94℃; for 0.166667h; Glovebox; Inert atmosphere; Schlenk technique; | 5.2 Synthesis of Lp-MedpyZnEt2 General procedure: Diethyl zinc (0.679g, 5mmol) in hexane (10ML) was transferred to the toluene solution of Lp-Medpy (0.921g, 5mmol, in toluene (25mL)) at -94°C, and the mixture was stirred for 10min to become red precipitate. A red powder was obtained after being filtered and under vacuum for 4h. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | In acetonitrile at 40℃; for 1h; Glovebox; | 3 Example 3 Synthesis of trifluoromethoxylation reagent I-3 with nitrogen phosphine ligand In the glove box, add [(PPhtBu2)Ag(μ-OCF3)]2 (1mmol) and substituted bipyridine (2mmol), acetonitrile (10mL) to the dried pressure-resistant reaction tube, oil at 40 After 1 hour of reaction in the bath, a colorless solution was obtained, which was allowed to stand and cool. After being taken into the glove box, it was filtered through a diatomaceous earth into a 100mL egg-shaped bottle to obtain a colorless solution. After pumping it dry with an oil pump (one hour), 886 mg of off-white was obtained. Solid I-3, yield 74%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | In diethyl ether for 4h; Inert atmosphere; Darkness; Reflux; | 2.2.1. Synthesis of fac-[Mn(6,6′-Me2bpy)(CO)3Br] (6,6′-Me2bpy-Br) The synthetic procedure was adapted from a previously reportedprocedure for related Mn(I) compounds [56]. Mn(CO)5Br (270 mg,0.98 mmol) and 6,6′-dimethyl-2,2′-dipyridyl (200 mg, 1.0 mmol) wereadded to 30 mL of diethyl ether and heated at reflux for 4 h under Ar.After cooling to room temperature, the yellow precipitate was collectedby vacuum filtration and washed with diethyl ether. Yield: 320 mg(0.79 mmol, 81%). 1H NMR (500 MHz, CD3CN): δ 8.01 (2H, d), 7.93(2H, t), 7.48 (2H, m), 3.1 (6H, s). Elemental analysis calculated forC15H12O3N2MnBr: 44.69% C, 3.00% H, 6.94% N. Found: 44.6% C,2.98% H, 7.00% N. HR-ESI(+)-MS (CH3CN): [M - Br + CH3CN]+, m/z = 364.048 (calcd m/z = 364.049). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile at 20℃; for 0.2h; Irradiation; | 2.2.10. Photolysis experiments General procedure: The photolysis studies were carried out with CH3CN solutions of thecompounds at room temperature and 405 nm LEDs (Luxeon Star LED,Quadica Developments, Inc., Lethbridge, Alberta, Canada). Each samplewas irradiated for varied time intervals and analyzed by the appropriatespectroscopic method (FTIR, electronic absorption and 1H NMR analysis).Analogous dark control experiments were performed in the absenceof irradiation. Ferrioxalate chemical actinometry was performedto determine the photon flux of the 405 nm light source (2.7 × 10-8mol photons/s) [65]. The quantum yield of CO dissociation (ΦCO) wasmeasured using electronic absorption spectroscopy by monitoring thedecrease in the MLCT absorbance band at very early times (< 10%change in absorbance). All samples were absorbance matched at theirradiation wavelength (405 nm). The rate of moles of reactant lost wasobtained from the slope of the moles of reactant vs irradiation time plot.Values were corrected for the fraction of light absorbed by the sample atthe 405 nm. The ΦCO values were calculated by dividing the rate ofmoles of reactant lost (in moles reactant/s) by the photon flux (moles ofphotons/s). Representative data for 6,6′-Me2bpy-Br and 6,6′-Me2bpy-pyare provided in Figure S1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile at 20℃; for 0.111111h; Irradiation; | 2.2.10. Photolysis experiments General procedure: The photolysis studies were carried out with CH3CN solutions of thecompounds at room temperature and 405 nm LEDs (Luxeon Star LED,Quadica Developments, Inc., Lethbridge, Alberta, Canada). Each samplewas irradiated for varied time intervals and analyzed by the appropriatespectroscopic method (FTIR, electronic absorption and 1H NMR analysis).Analogous dark control experiments were performed in the absenceof irradiation. Ferrioxalate chemical actinometry was performedto determine the photon flux of the 405 nm light source (2.7 × 10-8mol photons/s) [65]. The quantum yield of CO dissociation (ΦCO) wasmeasured using electronic absorption spectroscopy by monitoring thedecrease in the MLCT absorbance band at very early times (< 10%change in absorbance). All samples were absorbance matched at theirradiation wavelength (405 nm). The rate of moles of reactant lost wasobtained from the slope of the moles of reactant vs irradiation time plot.Values were corrected for the fraction of light absorbed by the sample atthe 405 nm. The ΦCO values were calculated by dividing the rate ofmoles of reactant lost (in moles reactant/s) by the photon flux (moles ofphotons/s). Representative data for 6,6′-Me2bpy-Br and 6,6′-Me2bpy-pyare provided in Figure S1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | Stage #1: 6,6'-dimethyl-2,2'-bipyridine With chromium(VI) oxide; sulfuric acid at 70℃; Cooling with ice; Stage #2: methanol at 70℃; for 24h; | 2.3.2. Synthesis of 6,6′-dimethyl-2,2′-bipyridinedicarboxylate (1) 6,6′-Dimethyl-2,2′-bipyridine (1a, 50mg, 0.3 mmol) was placed into a25 mL round-bottom flask cooled with an ice bath. Concentrated sulfuricacid (3 mL) was added dropwise under stirring, followed by small portionsof the chromium (VI) oxide (170 mg, 1.7 mmol). The mixture wasstirred overnight at 70 °C. Afterwards, the solution was cooled to roomtemperature and was slowly poured to 100 mL ofmethanol. After stirringunder reflux for 24 h at 70 °C, the reaction mixture was basified to apH 7.8 using Na2CO3 and 100 mL of brinewas added. Methanol was evaporatedunder vacuum, and the obtained aqueous solution was extractedwith ethyl acetate (3×). The combined organic layerswere dried over anhydrousMgSO4,filtered and concentrated to afford 1 (61mg, 0.23 mmol,75%). No further purification was needed. 1H NMR (300 MHz, CDCl3):δ = 8.73 (dd, J1 = 7.9 Hz, J2 = 1.1 Hz, 2H), 8.15 (dd, J1 = 7.9 Hz, J2 =1.1 Hz, 2H), 7.99 (t, J = 7.9 Hz, 2H), 4.0 (s, 6H). 13C NMR (75 MHz, CDCl3): δ=165.8, 155.6, 147.7, 138.3, 125.6, 125, 53.1.HRMS (ESI+): Calculatedfor C14H13N2O4 (M + H)+: 273.0875; Found: 273.0873. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With palladium diacetate; sodium hexamethyldisilazane; nixantphos In 1,2-dimethoxyethane at 80℃; for 1h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With palladium diacetate; lithium hexamethyldisilazane; nixantphos In 1,4-dioxane at 80℃; for 12h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With palladium diacetate; lithium hexamethyldisilazane; nixantphos In 1,4-dioxane at 80℃; for 12h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With palladium diacetate; lithium hexamethyldisilazane; nixantphos In 1,4-dioxane at 80℃; for 12h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75.6% | In methanol; acetonitrile Heating; | 2.2. Synthesis of [Co(mbipy)(H2O)(η2-NO3)(η-NO3)] (1) General procedure: A solution of 6-methyl-2,2'-bipyridine (0.14 g, 0.13 mL, 0.79 mmol) in 15 mL methanol was gradually added to a solution of Co(NO3)2·6H2O (0.23 g, 0.79 mmol) in 5 mL acetonitrile at 45 °C and stirred for 15 min. Slow evaporation at room temperature led to orange prismatic crystals of 1 after five days (yield 0.22 g, 75.0%, m. p. 147-149 °C). |
Tags: 4411-80-7 synthesis path| 4411-80-7 SDS| 4411-80-7 COA| 4411-80-7 purity| 4411-80-7 application| 4411-80-7 NMR| 4411-80-7 COA| 4411-80-7 structure
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H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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