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CAS No. : | 4506-61-0 |
Formula : | C20H14N4 |
M.W : | 310.35 |
SMILES Code : | C1(C2=NC3=CC=CC=C3N2)C=CC=CC=1C1=NC2=CC=CC=C2N1 |
InChI Key : | NQVCKXMOMGRVES-UHFFFAOYSA-N |
Pubchem ID : | 828108 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P280-P301+P312-P302+P352-P305+P351+P338 |
* 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 |
---|---|---|
With polyphosphoric acid; at 100 - 175℃;Schlenk technique; Inert atmosphere; | General procedure: A diamine compound (0.05 mol) was mixed with a dicarboxylicacid or an acid anhydride (0.025 mol) and the mixture was poured in 50 ml of preheated (100 C) polyphosphoric acid. The mixturewas stirred and heated at 175 C for 3-5 h. The reaction mixturewas then poured in ice cold water and allowed to stand overnight.The precipitate was removed by filtration and washed severaltimes with diluted sodium hydrogen carbonate solution and finallywith water. The reaction product was then air dried and weighed.The products were characterized by NMR and mass spectrometry(Table 4) and representative examples were characterized by elemental analysis. | |
With polyphosphoric acid; at 100 - 175℃;Schlenk technique; Inert atmosphere; | General procedure: A diamine compound (0.05mol) was mixed with a dicarboxylic acid or an acid anhydride (0.025mol) and the mixture was poured in 50 ml of preheated (100C) polyphosphoric acid. The mixture was stirred and heated at 175C for 3-5 hours. The reaction mixture was then poured into ice cold water and allowed to stand overnight. The precipitate was removed by filtration and washed several times with diluted sodium hydrogen carbonate solution and finally with water. The reaction product was then air dried and weighed. The products were characterized by NMR and mass spectrometry (Table 3) and elemental analyses (Table 32). | |
With polyphosphoric acid; at 100 - 175℃;Inert atmosphere; Schlenk technique; | General procedure: A diamine compound (0.05 mol) was mixed with a dicarboxylic acid or an acid anhydride (0.025 mol) and the mixture was poured into 50 mL of preheated (100 C) polyphosphoric acid. The mixture was stirred and heated at 175 C for 3 - 5 h. The reaction mixture was then poured into ice cold water and left to stand overnight. The precipitate was removed by filtration and washed several times with diluted sodium hydrogen carbonate solution and finally with water. The reaction product was then air dried and weighed. The products were characterized by elemental analyses (Table 2), NMR, and mass spectrometry (Table 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: Benzimidazole compounds as described herein were synthesized according to the following general procedure: To a solution of benzene- 1,2-diamine (1.1 mmol) and benzoic acid (1.0 mmol) in DMT (5 niL) were added EDCI (230 mg, 1.2 mmol) and HOBT (162 mg, 1.2 mmol), and the mixture was stirred for 4 hours followed by addition of HO Ac (5 niL). The reaction was heated to 110 C overnight and then concentrated under reduced pressure. The residue ws extracted using ethyl acetate (3 x 10 mL), and the combined organic layers were washed with 1M NaOH and brine, respectively. The solvent was dried over NaS04 and removed under reduced pressure, and the residue was purified via column chromatography to give corresponding benzimidazole product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 20℃; for 24h;Schlenk technique; Inert atmosphere; | To 0.87 g, (2.6 mmol) TiCl4(THF)2 in dichloromethane wasadded 2.6 mmol of the free ligand. The reaction mixture was stirredover night at room temperature, filtered and washed severaltimes with the reaction solvent pentane and dried under vacuumand weighed. The products were characterized by NMR and massspectroscopy (Table 4) and representative examples were characterizedby elemental analysis | |
In dichloromethane; at 20℃; for 24h;Schlenk technique; | General procedure: To 0.87g, (2.6mmol) TiCl4(THF)2 in dichloromethane was added 2.6mmol of the solid heterocycle. The reaction mixture was stirred over night at room temperature and filtered. The residue was washed several times with dichloromethane and pentane and dried in vacuo and weighed. The products were characterized by NMR and mass spectroscopy (Table 4). Representative samples were characterized by elemental analysis (Table 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 20℃; for 24h;Schlenk technique; Inert atmosphere; | To 0.45 g (1.2 mmol) ZrCl4(THF)2 in dichloromethane anamount of 1.2 mmol of the free ligand was added. The reactionmixture was stirred over night at room temperature, filtered andwashed several times with dichloromethane, then with pentane,dried under vacuum and weighed. The products were characterizedby NMR and mass spectroscopy (Table 4) and representativeexamples were characterized by elemental analysis | |
In dichloromethane; at 20℃; for 24h;Schlenk technique; | General procedure: To 0.45g (1.2mmol) ZrCl4(THF)2 in dichloromethane was added 1.2mmol of the free ligand. The reaction mixture was stirred over night at room temperature, the reaction product was filtered and washed several times with dichloromethane and pentane, dried in vacuo and weighed. The products were characterized by NMR and mass spectroscopy (Table 4). Representative samples were characterized by elemental analysis (Table 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In diethyl ether; at 20℃; for 24h;Schlenk technique; Inert atmosphere; | General procedure: To 0.41 g (2.6 mmol) VCl3 in ether an amount of 2.6 mmol of thefree ligand was added. The reaction mixture was stirred over nightat room temperature, filtered and washed several times with etherand pentane, dried under vacuum and weighed. The products werecharacterized by mass spectroscopy and representative exampleswere characterized by elemental analysis ( | |
In diethyl ether; at 20℃; for 24h;Schlenk technique; | General procedure: To 0.41g (2.6mmol) VCl3 in ether was added 2.6mmol of the ligand. The reaction mixture was stirred over night at room temperature. The product was filtered and washed several times with ether and pentane, dried in vacuo and weighed. Representative samples were characterized by elemental analysis (Table 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 20℃;Schlenk technique; Inert atmosphere; | General procedure: To 0.87g, (2.6 mmol) TiCl4 (THF)2 in dichloromethane was added 2.6 mmol of the solid ligand. The reaction mixture was stirred over night at room temperature; the solid formed was collected by filtration under reduced pressure and washed several times with dichloromethane, then with pentane, dried in vacuo and weighed. The products were characterized by NMR and mass spectroscopy (Table 3), and by elemental analyses (Table 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
General procedure: The general procedure for the reaction of N-allylation was as follows: Benzimidazolyl pyridine (5g, 25.6mmol) was dissolved in 10ml anhydrous DMF. Then K2CO3 (1.4 equiv) was added to the solution at room temperature. Shortly afterwards (20min), allylbromide (25.6mmol) was added in portions to the reaction mixture. The reaction was stirred at room temperature for two days. The inorganic salt was removed by filtration and rinsed twice with dichloromethane. The solution was poured into water and extracted with dichloromethane (2×50ml). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo resulting in a viscous oil. Addition of water resulted in the formation of the product in 85% yield. Other N-allyl substituted compounds were prepared similarly. The products were characterized by NMR and mass spectroscopy (Table 4). Representative samples were characterized by elemental analysis (Table 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In dichloromethane; at 20℃;Inert atmosphere; Schlenk technique; | General procedure: To 0.45 g (1.2 mmol) of ZrCl4(THF)2 in dichloromethane was added 1.2 mmol of the organic compound. The reaction mixture was stirred overnight at room temperature, filtered, washed several times with dichloromethane and then with pentane, dried in vacuo, and weighed. The products were characterized by elemental analyses (Table 2), NMR, and mass spectroscopy (Table 3). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | In tetrahydrofuran; methanol; for 4h;Inert atmosphere; Schlenk technique; Reflux; | A suspension of PhBIm2 (0.50 g, 1.61 mmol) in MeOH(10 ml) was added dropwise to a solution of CoCl26H2O (0.38 g,1.61 mmol) in THF/MeOH (10 ml). Once completed the additionof PhBIm2, the solution was refluxed for 4 h. After cooled at roomtemperature, the product was filtered and dried under vacuum toobtain 2 as naive semi-crystalline powder. Yield 0.60 g (1.35 mmol,84%). The solid was redissolved in methanol/THF and recrystallizedby slow diffusion of a pentane layer over the complex solution togive crystals suitable for X-ray analysis. IR (KBr, t/cm1), 3200(NH, s), 3000 (Ar-H, s), 1618-1556 (ArC = C, CN, m), 1437, 1424(NH, s), 1275 (CN, s), 750 (Ar-H, m). UV-VIS (CH3CH2OH): kmax/nm (emax/dm3mol-1cm1) = 581 (102), 616 (127), 650 (125). ESI-MS (m/z), 309.09 (31%, M - CoCl2), 401.95 (27), 437.92 (M, 100),439.92 (63), 440.95 (15), 441.94 (10). Calculated (m/z) 437.985(100%), 438.988 (22), 439.982 (65), 440.985 (14), 441.979 (10).leff. = 3,93 BM. Anal. Calc. for C20H14N4Cl2Co (F.W. 440.2) C54.57, H 3.21, N 12.73%. Found C 54.69, H 3.31, N 12.57%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | In tetrahydrofuran; methanol; for 4h;Inert atmosphere; Schlenk technique; Reflux; | General procedure: A suspension of PhBIm2 (0.50 g, 1.61 mmol) in MeOH(10 ml) was added dropwise to a solution of CoCl26H2O (0.38 g,1.61 mmol) in THF/MeOH (10 ml). Once completed the additionof PhBIm2, the solution was refluxed for 4 h. After cooled at roomtemperature, the product was filtered and dried under vacuum toobtain 2 as naive semi-crystalline powder. Yield 0.60 g (1.35 mmol,84%). The solid was redissolved in methanol/THF and recrystallizedby slow diffusion of a pentane layer over the complex solution togive crystals suitable for X-ray analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | In tetrahydrofuran; methanol; for 4h;Inert atmosphere; Schlenk technique; Reflux; | General procedure: A suspension of PhBIm2 (0.50 g, 1.61 mmol) in MeOH(10 ml) was added dropwise to a solution of CoCl26H2O (0.38 g,1.61 mmol) in THF/MeOH (10 ml). Once completed the additionof PhBIm2, the solution was refluxed for 4 h. After cooled at roomtemperature, the product was filtered and dried under vacuum toobtain 2 as naive semi-crystalline powder. Yield 0.60 g (1.35 mmol,84%). The solid was redissolved in methanol/THF and recrystallizedby slow diffusion of a pentane layer over the complex solution togive crystals suitable for X-ray analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In 1,2-dimethoxyethane; at 190℃; for 4h; | o-Phenylenediamine (6.09 g, 56.38 mmol)and dimethyl phthalate (4.6 ml, 28.19 mmol) were stirred in ethyleneglycol (20 ml) at 190 C for 4 h. During reaction, the evolvedmethanol was distilled out. Then, the mixture was allowed tocool-down to ambient temperature and stirred overnight. The productwas treated with water (120 ml), filtered, washed with water(4 20 ml) and finally dried at 60 C under vacuum for two days togive a beige powder. Yield 7.80 g (25.16 mmol, 90%). 1H NMR(300 MHz, J = Hz, D2O/HCl, r.t.) d (ppm) = 7.46 (dd, AA¢XX¢ system,4H, JH-H = 3, HBz), 7.58 (dd, AA¢XX¢ system 4H, JH-H = 3; HBz), 7.91(dd, AA¢XX¢ system, 2H, JH-H = 3; HPh), 8.01 (dd, AA¢XX¢ system,2H, JH-H = 3 Hz; HPh). 13C {1H} NMR (75 MHz, D2O/HCl, r.t.) d(ppm) = 113.62 (CBz), 126.67 (CBz), 132.28 (CPh), 133.64 (CPh),145.79 (Cq, Bz), 130.98 (Cq, Ph PhCq), 122.24 (Cipso). IR (KBr, t/cm1), 3000 (NH, s), 3050 (Ar-H, s), 1625-1525 (ArC = C, CN,m), 1430, 1410 (NH, s), 1275 (CN, s), 750 (Ar-H, m). Anal. Calc.for C20H14N4 (F.W. 310.35) C 77.40, H 4.55, N 18.05%. Found C77.62, H 4.45, N 17.66%. |