* 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.
With phosphorus pentachloride; ammonia In acetonitrile at -40 - 20℃; for 2 h;
The liquid ammonia (0.5 ml) and acetonitrile (50 ml) at -40 ° C in cold bath, adding pyridine -2,6-dicarboxylic acid (1.67g), to 0 °C, batch by adding phosphorus pentachloride (4g), is omitted, stirring the mixture at room temperature for 2 hours, the response finishes, concentrated under reduced pressure, the residue is dissolved with methylene chloride, washed with saturated sodium bicarbonate to neutral, anhydrous magnesium sulphate dried, concentrated, precipitated solid, the resulting solid is recrystallized with isopropyl alcohol, to obtain white crystal of 2,6-di-cyano pyridine (1.13g). The yield is 88percent.
Reference：
[1] Patent: CN105503716, 2016, A, . Location in patent: Paragraph 0016
[2] Journal of Organic Chemistry, 2015, vol. 80, # 5, p. 2676 - 2699
[3] Chemical Communications, 2017, vol. 53, # 42, p. 5718 - 5720
5
[ 499-83-2 ]
[ 1195-59-1 ]
Yield
Reaction Conditions
Operation in experiment
51.1%
Stage #1: With sodium tetrahydroborate In ethanol for 10 h; Inert atmosphere; Schlenk technique; Reflux Stage #2: Inert atmosphere; Schlenk technique; Reflux
Asolution of 2,6-pyridinedicarboxylic acid (3.30 g) in absolute ethyl alcohol (60 mL) was added NaBH4 (4.01 g) dropwise under stirred in ice-salt baths. After2 h, refluxed for 10 h following stirred at the room temperature for 3 h, the reaction mixture was evaporated under reduced pressure. Then, acetone was added (20 mL), and solution was refluxed and evaporated again. After cooling to room temperature, potassium carbonate solution (20 mL) and water were added, and the reaction mixture was extracted with CHCl3. The collected organic layers were dried over NaSO4, filtered and evaporated under reduced pressure to give a pale white acicular crystal (the yield was 1.20 g (51.1percent); m.p. = 115.6–116.7°C).
Reference：
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[15] Patent: WO2018/183965, 2018, A1,
6
[ 499-83-2 ]
[ 7703-74-4 ]
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[4] Organic and Biomolecular Chemistry, 2017, vol. 15, # 46, p. 9923 - 9931
7
[ 499-83-2 ]
[ 499214-11-8 ]
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8
[ 499-83-2 ]
[ 1197-10-0 ]
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[2] Journal of the American Chemical Society, 1982, vol. 104, # 8, p. 2251 - 2257
[3] Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 15, p. 5061 - 5074
9
[ 499-83-2 ]
[ 69950-65-8 ]
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[1] Bioorganic and Medicinal Chemistry Letters, 2003, vol. 13, # 4, p. 609 - 612
10
[ 499-83-2 ]
[ 39977-44-1 ]
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[12] Patent: US2015/344483, 2015, A1,
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[14] Patent: CN104926720, 2018, B,
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11
[ 67-56-1 ]
[ 499-83-2 ]
[ 7170-36-7 ]
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[2] Inorganic Chemistry, 2012, vol. 51, # 18, p. 10012 - 10024
[3] Journal of the American Chemical Society, 2011, vol. 133, # 40, p. 16219 - 16234
[4] Chemistry - A European Journal, 2016, vol. 22, # 24, p. 8113 - 8123
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[6] ChemMedChem, 2012, vol. 7, # 10, p. 1825 - 1839
[7] Patent: WO2006/117754, 2006, A1, . Location in patent: Page/Page column 50-51
12
[ 499-83-2 ]
[ 7170-36-7 ]
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[2] Journal of the American Chemical Society, 2003, vol. 125, # 1, p. 296 - 304
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[4] Journal of Medicinal Chemistry, 1987, vol. 30, # 10, p. 1918 - 1928
[5] Chemical Communications, 2011, vol. 47, # 22, p. 6416 - 6418
[6] Organic Letters, 2011, vol. 13, # 12, p. 3194 - 3197
[7] Tetrahedron, 2011, vol. 67, # 44, p. 8458 - 8464
[8] Organic and Biomolecular Chemistry, 2012, vol. 10, # 6, p. 1172 - 1180
[9] Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy, 2012, vol. 98, p. 170 - 177,8
[10] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2012, vol. 98, p. 170 - 177
[11] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2015, vol. 135, p. 953 - 958
[12] Inorganic Chemistry, 2015, vol. 54, # 10, p. 4611 - 4620
[13] Chemistry - A European Journal, 2015, vol. 21, # 26, p. 9493 - 9504
[14] Dalton Transactions, 2016, vol. 45, # 47, p. 19024 - 19033
[15] Journal of Medicinal Chemistry, 2017, vol. 60, # 17, p. 7267 - 7283
13
[ 67-56-1 ]
[ 499-83-2 ]
[ 5453-67-8 ]
[ 7170-36-7 ]
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[1] Journal of Organic Chemistry, 1981, vol. 46, # 24, p. 4914 - 4920
[2] Journal of Organometallic Chemistry, 1980, vol. 186, # 2, p. 147 - 153
14
[ 499-83-2 ]
[ 4722-94-5 ]
Reference：
[1] Journal of the Chemical Society, Dalton Transactions: Inorganic Chemistry (1972-1999), 1991, # 11, p. 3049 - 3054
15
[ 499-83-2 ]
[ 64-17-5 ]
[ 15658-60-3 ]
Yield
Reaction Conditions
Operation in experiment
92%
at -20 - 20℃; for 6 h;
Thionyl chloride (360 mg, 3 mmol) was added dropwise to a solution of pyridine-2,6-dicarboxylate (170 mg, 1 mmol) (2) in EtOH (5 mL) at -20 oC and then the mixture was stirred at room temperature for 6 h. The solvent was evaporated and the residue was taken up in methylene chloride, dried by MgSO4 and evaporated. The product was obtained following purification by silica gel column chromatography as a colorless solid powder 4 (205 mg, yield 92percent).
82.35%
Stage #1: for 8 h; Reflux Stage #2: at 20℃; for 8 h;
60 g (359.02 mmol) of pyridine-2,6-dicarboxylic acid and 250 mL (3446. 54 mmol) of S0C12 were added to a 1000 mL round bottom flask and mixed, After refluxing for 8 h, S0C12 was distilled off, and then 300 mL (5140.76 mmol) of absolute ethanol was added dropwise under ice-cooling. The mixture was stirred at room temperature for 8 hours and then concentrated to dryness. The residue was washed with 300 mL of water and then treated with potassium carbonate Adjusted to pH 7 and then extracted three times with 150 mL of methylene chloride. The organic phases were combined and the organic phase was washed with 200 mL of saturated brine, And dried over anhydrous sodium sulfate, filtered and dried to give 66 g (295. 66 mmol) of the yellowish crystalline solid, pyridine-2,6-dicarboxylic acid diethyl ester, in 82.35percent yield;
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 2009, vol. 19, # 9, p. 2599 - 2603
[2] Chemical Communications, 2008, # 21, p. 2444 - 2446
[3] Tetrahedron Letters, 2017, vol. 58, # 10, p. 991 - 994
[4] Molecular Crystals and Liquid Crystals, 2007, vol. 470, # 1, p. 369 - 381
[5] Organometallics, 2015, vol. 34, # 7, p. 1170 - 1176
[6] Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2014, vol. 78, # 1-4, p. 151 - 159
[7] Synthetic Communications, 2009, vol. 39, # 24, p. 4429 - 4440
[8] Synthetic Communications, 2005, vol. 35, # 17, p. 2317 - 2324
[9] Patent: CN104193673, 2016, B, . Location in patent: Paragraph 0070-0071
[10] Inorganic Chemistry, 2012, vol. 51, # 9, p. 5199 - 5207
[11] Dalton Transactions, 2012, vol. 41, # 48, p. 14480 - 14483
[12] Bulletin de l'Academie Polonaise des Sciences, Serie des Sciences Chimiques, 1955, vol. 3, p. 55,58[13] Chem.Abstr., 1956, # 7800,
[14] Chemistry - A European Journal, 2006, vol. 12, # 26, p. 6852 - 6864
[15] Patent: WO2006/66968, 2006, A1, . Location in patent: Page/Page column 36-37
[16] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2008, vol. 69, # 2, p. 513 - 516
[17] Australian Journal of Chemistry, 2009, vol. 62, # 9, p. 1130 - 1136
[18] Chemistry - A European Journal, 2013, vol. 19, # 50, p. 17141 - 17149
[19] RSC Advances, 2016, vol. 6, # 109, p. 107305 - 107309
[20] New Journal of Chemistry, 2018, vol. 42, # 11, p. 8567 - 8576
16
[ 499-83-2 ]
[ 15658-60-3 ]
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[1] Journal of the American Chemical Society, 1953, vol. 75, p. 3830
[2] Chemicke Listy, 1945, vol. 48, p. 869,871[3] Chem.Abstr., 1955, p. 9665
[4] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1995, # 7, p. 1365 - 1374
[5] Zeitschrift fuer Naturforschung, B: Chemical Sciences, 1994, vol. 49, # 8, p. 1127 - 1136
[6] Journal of the American Chemical Society, 1982, vol. 104, # 8, p. 2251 - 2257
[7] Australian Journal of Chemistry, 1991, vol. 44, # 8, p. 1041 - 1048
[8] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2011, vol. 79, # 2, p. 348 - 355
[9] Tetrahedron, 2011, vol. 67, # 44, p. 8458 - 8464
[10] RSC Advances, 2016, vol. 6, # 34, p. 28194 - 28199
17
[ 499-83-2 ]
[ 64-17-5 ]
[ 21855-16-3 ]
Reference：
[1] Bioorganic and Medicinal Chemistry, 2015, vol. 23, # 15, p. 5061 - 5074
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 8h;
100%
With thionyl chloride for 6h; Heating;
100%
With thionyl chloride In 1,4-dioxane for 4h; Heating;
100%
With thionyl chloride In N,N-dimethyl-formamide at 2℃; for 75h;
100%
With thionyl chloride for 7h; Reflux; Inert atmosphere;
100%
With thionyl chloride; N,N-dimethyl-formamide for 6h; Reflux; Inert atmosphere;
100%
With thionyl chloride In N,N-dimethyl-formamide for 2h; Reflux;
100%
With thionyl chloride for 24h; Inert atmosphere; Reflux;
100%
With thionyl chloride at 90℃; for 4h; Schlenk technique; Inert atmosphere;
pyridine-2,6-dicarbonyl dichloride (42)
Pyridine-2,6-dicarboxylic acid 7 (5.00 g, 29.9 mmol) was heated in 20 mL thionyl chloride (275 mmol) under reflux at 90 °C for 3-4 h until all of the starting material has dissolved which indicated the total conversion of the acid. The thionyl chloride was removed under vacuo and 20 mL dry toluene was added. Then the solvent was again evaporated to yield pyridine-2,6-dicarbonyl dichloride 42 (6.10 g, 29.9 mmol, quant.) as a pale brown solid
100%
With thionyl chloride for 3h; Reflux;
100%
With thionyl chloride Reflux; Inert atmosphere;
99%
With thionyl chloride for 18h; Heating;
99.8%
With thionyl chloride for 6h; Reflux; Inert atmosphere;
99%
With thionyl chloride Reflux;
99%
With thionyl chloride In N,N-dimethyl-formamide for 2h; Reflux;
Synthesis of pyridine-2,6-dicarbonyl dichloride
To a mixture of pyridine-2,6-dicarboxylic acid (1.34 g, 8 mmol) in DMF (0.05 mL) was added SOCl2 (15 mL, 20 mmol). The mixture was refluxed under stirring for 2 h, over which time the insoluble powder gradually dissolved. The excess amount of SOCl2 was then removed under reduced pressure by adding a small amount of toluene and a pale white solid (1.61 g, 99%) was obtained. 1H NMR (400 MHz,CDCl3), δ: 8.37 (d, 2H), 8.18 (t, 1 H). Anal. calcd.for C11H15N3O4: C, 41.21; H, 1.48; N, 6.87; found: C,41.37; H, 1.41; N, 6.74.
98.2%
With thionyl chloride for 24h; Reflux; Inert atmosphere;
98.8%
With thionyl chloride; N,N-dimethyl-formamide at 100℃; for 3h;
96%
With thionyl chloride for 13h; Inert atmosphere; Reflux;
96%
With thionyl chloride
95%
With thionyl chloride
93%
With thionyl chloride In N,N-dimethyl-formamide for 4h; Reflux;
92%
With thionyl chloride for 15h; Reflux; Schlenk technique; Inert atmosphere;
88%
With thionyl chloride; N,N-dimethyl-formamide at 65℃; for 16h;
87%
With thionyl chloride Heating;
86%
With thionyl chloride In dichloromethane
86%
With thionyl chloride In dichloromethane for 5h; Reflux; Inert atmosphere;
86%
With thionyl chloride In dichloromethane at 0℃; for 5h; Reflux; Inert atmosphere;
79%
With thionyl chloride for 4h; Heating;
70%
With thionyl chloride In N,N-dimethyl-formamide at 80℃; for 4h;
61%
With thionyl chloride In tetrahydrofuran at 0 - 70℃; Inert atmosphere;
With phosphorus(V) chloride
With thionyl chloride
With tetrahydrofuran for 24h; Heating;
With thionyl chloride for 2h; Heating;
With thionyl chloride Heating;
With thionyl chloride In benzene for 20h; Heating;
With 1-methyl-pyrrolidin-2-one; thionyl chloride
With thionyl chloride for 12h; Heating;
With thionyl chloride for 4h; Heating;
With thionyl chloride Heating;
With thionyl chloride; phosphorus(V) chloride for 12h; Heating;
With oxalyl dichloride In Carbon tetrachloride for 4h; Heating; Yield given;
With oxalyl dichloride; N,N-dimethyl-formamide for 0.333333h; Ambient temperature;
With thionyl chloride In N,N-dimethyl-formamide for 1h; Heating;
With thionyl chloride; N,N-dimethyl-formamide for 0.75h; Heating;
With thionyl chloride for 18h; Heating;
With thionyl chloride
With thionyl chloride for 72h; Heating;
With thionyl chloride; N,N-dimethyl-formamide for 10h; Heating;
With oxalyl dichloride In dichloromethane at 20℃;
With thionyl chloride for 6h; Heating;
With thionyl chloride for 2h; Heating;
With N-(chloromethylene)-N-methylmethanaminium chloride In dichloromethane at 30 - 40℃; for 5.5h;
With thionyl chloride In 1,4-dioxane at 80℃; for 24h;
With thionyl chloride In N,N-dimethyl-formamide for 1h; Heating;
With thionyl chloride In N,N-dimethyl-formamide
With thionyl chloride Heating;
With thionyl chloride In 1,4-dioxane at 105℃; for 4h;
In thionyl chloride
22 2,6-Pyridinedicarboxylic acid dichloride
Example 22 2,6-Pyridinedicarboxylic acid dichloride 2,6-pyridinedicarboxylic acid (111 g, 0.665 mol) was suspended in thionyl chloride (350 ml, 4.8 mol) and heated to be refluxed overnight until it became a clear solution. The excess of thionyl chloride was removed under reduced pressure. The resulting solid was ground to powder and dried under vacuum. The reaction was quantitative. 1 H-NMR (CDCl3): dH=8.36 (d, 3 J(HH)=7.8 Hz, 2 H, H3,5), 8.17 (t, 3 J(HH)=7.8 Hz, 1 H, H4). 13 C-NMR (CDCl3): dC=169.32 (C=O), 149.24 (C2,6), 139.41 (C4) and 128.97 (C3,5).
With thionyl chloride; N,N-dimethyl-formamide
With thionyl chloride; N,N-dimethyl-formamide for 0.75h; Heating;
With thionyl chloride
With oxalyl dichloride; N,N-dimethyl-formamide In tetrahydrofuran at 20℃; for 0.5h;
With thionyl chloride for 3h; Reflux;
With thionyl chloride for 4h; Reflux;
2.98 g
With pyridine; thionyl chloride at 20℃; for 10h;
With thionyl chloride
With thionyl chloride In N,N-dimethyl-formamide for 2h; Inert atmosphere; Reflux;
With thionyl chloride
With thionyl chloride In N,N-dimethyl-formamide
With thionyl chloride In N,N-dimethyl-formamide at 20℃; Inert atmosphere; Reflux;
With thionyl chloride for 6h; Reflux;
With thionyl chloride
With thionyl chloride for 5h; Reflux;
Synthesis of 2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine [BMSHCPH4]
A mixture of pyridine-2,6-dicarboxylic acid (1) (1.67 g, 10 mmol) and thionyl chloride (2) (10cm3) was refluxed for 5 h maintaining anhydrous conditions. Excess thionyl chloride was then removed under reduced pressure and further cooled in ice bath for 15 min to get (3). 15cm3 of super dry ethanol was added and refluxed for 3 h to obtain 2,6-diethylcarboxylatopyridine (4). This was further treated with hydrazine hydrate (5) (0.02 mol, 1cm3) in absolute ethanol (20cm3) and refluxed for 2-3 h to obtain 2,6-bis[hydrazinocarbonyl]pyridine (6), which was washed with distilled water and recrystallized from hot water to give colorless silky needles. Yield : 1.336 g, 80%; m.p.285-286 °C. 2,6-bis[(3-methoxysalicylidene)hydrazinocarbonyl]pyridine (BMSHCPH4) was synthesized by the literature method [2] with a slight modification. To a hot suspension of (6) (1.95 g, 10 mmol) in absolute ethanol (20cm3), a solution of 3-methoxy salicylaldehyde (7) (3.04 g, 20 mmol) in the same solvent (20cm3) was added, and refluxed for 4 h. The yellow microcrystalline product (BMSHCPH4) obtained was filtered, washed with hot water followed by hot ethanol, air dried and recrystallized from 2-ethoxyethanol to get crystals suitable for X-ray diffraction studies.
With thionyl chloride; N,N-dimethyl-formamide for 2h; Inert atmosphere; Reflux;
With thionyl chloride In 2-methoxy-N-(2-methoxyethyl)ethanamine Inert atmosphere;
With oxalyl dichloride at 40℃;
With thionyl chloride for 3h; Reflux;
4.2. Synthesis of 2-alkoycarbonyl-pyridine-6-carboxylic acid (3) and alkoyl pyridine-2,6-dicarbolic ester (4)
A general synthetic procedure is as follows. Pyridine-2,6-dicarboxylic acid (1, 1.5 g, 8.98 mmol) was mixed with 24 mL of SOCl2. The resulted mixture was refluxed for 3 h. The excess of SOCl2 was then removed under vacuum. To the white solid of 2, 50 mL of THF was added. After the solid dissolved, alkyl alcohol (10.5 mmol) and DIEA (10.5 mmol) were added using a syringe. The resulted solution was allowed to reflux for 4 h. After removal of the solvent the residue was applied to chromatography to afford the desired products 3 and 4.
With thionyl chloride; N,N-dimethyl-formamide at 70℃; for 4h;
With thionyl chloride In N,N-dimethyl-formamide for 1h; Reflux;
With thionyl chloride In N,N-dimethyl-formamide for 5h; Reflux;
With thionyl chloride for 3h; Reflux;
With thionyl chloride
With thionyl chloride
With thionyl chloride; triethylamine In dichloromethane for 2h;
With thionyl chloride for 0.75h; Cooling with ice; Reflux;
With thionyl chloride In N,N-dimethyl-formamide for 5h; Reflux;
With thionyl chloride Reflux;
N2,N6-bis(pyridin-2-yl)pyridine-2,6-dicarboxamide (A3)
General procedure: A mixture of dipicolinic acid (10mmol) and thionylchloride (20mL) were refluxed for 4-5h, till the evolution of HCl gas ceases, under anhydrous condition. Excess thionylchloride was removed under reduced pressure. The resulting solution was cooled in an ice bath for 15min. Dry toluene (25-30mL) followed by 2-aminopyridine (20mmol) was added to the above solution and further refluxed until no more HCl was evolved. The solvent was removed under reduced pressure and the resultant white solid was washed with petroleum ether and neutralized with 5% NaHCO3. It was filtered, washed with water and then alcohol. Recrystallization from chloroform and ethanol yield silky needles and air-dried. Yield: 88%,
With thionyl chloride for 4h; Reflux;
With thionyl chloride Reflux;
With thionyl chloride In dichloromethane; N,N-dimethyl-formamide at 20 - 40℃; for 4h;
With thionyl chloride at 20℃; Reflux;
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 0 - 20℃; for 5h; Inert atmosphere; Sealed tube;
With thionyl chloride at 80℃; for 48h; Inert atmosphere;
With thionyl chloride at 0 - 80℃; for 10h;
Synthesis of N2,N6-di(prop-2-ynyl)pyridine-2,6-dicarboxamide 7b:
Thionyl chloride (10.0mL) was added drop wise to pyridine-2,6-dicarboxylic acid 5b (200.0mg, 1.2mmol, 1.0equiv) at 0°C and allowed to stir at 80°C for 10h. The reaction mixture was concentrated and dried under vacuum to provide the crude pyridine-2,6-dicarboxylic acid chloride. The crude product was dissolved in DMF (10.0mL) and cooled to 0°C. NMM (1.1mL, 10.1mmol, 8.4equiv) and propargylamine 6 (0.3mL, 4.2mmol, 3.5equiv) were added under an argon atmosphere at 0°C and allowed to stir at room temperature for 12h. The solvent was removed in vacuum and the residue was purified by column chromatography using MeOH-CH2Cl2 (3:97) to give the compound 7b (228.0mg, 79%) as colorless solid
With thionyl chloride; N,N-dimethyl-formamide for 2h; Reflux;
2.6.1. 2,6-Dibenzoylpyridine (6)
Excess thionyl chloride (25 mL) and two drops of DMF were added to 2,6-pyridinedicarboxylic acid (14; 5.0 g, 0.03 mol) and the mixture was heated at reflux for 2 h. The excess thionyl chloride was reduced and the crude residue was dissolved in benzene (50 mL). Then AlCl3 (10 g, 0.07 mol) was added and the mixture was heated under reflux for 19 h. The resulting mixture was poured into a mixture of ice and concentrated HCl (32%, 50 mL), and extracted with diethyl ether (3 × 20 mL).The organic layer was washed with 1 M NaOH, dried over anhydrous Na2SO4 and evaporated under reduced pressure. The product was purified by flash chromatography using dichloromethane (DCM):n-hexane(7:3) to give dibenzoylpyridine (6) as a flaky-white powder (1.14 g,93%). M.p. 108-110 °C, lit. [64] 109-110 °C; 1H NMR (300 MHz,CDCl3): δ 7.44-7.47 (m, 3H, ArH), 7.60-7.63 (m, 3H, ArH), 8.13-8.19 (m, 6H, ArH), and 8.32 (d, J = 8.1 Hz, 1H, ArH); 13C NMR (75.6 MHz,CDCl3): δ 126.92 (ArCH), 128.04 (4 × ArCH), 131.17 (4 × ArCH),133.00 (2 × ArCH), 135.97 (ArCH), 138.32 (2 × ArC), 153.84 (2 × ArC), and 192.57 (2 × C_O).
2 Synthesis of ligand bbp
2,6-Pyridine dicarboxylic acid (0.50g)and o-phenylen ediamine (0.70 g)were dispersed in orthophosphoric acid (10 cm 3), and heated for 4h at 220°C. Whilst still hot,the resulting solution was poured into cold distilled water (1dm 3) with vigorous stirring. The resulting blue precipita te was collected by filtration,then dispersed in 500 cm 3 of hot 10% (w/v)Na 2CO3 (aq) and stirred for 30 min. The insoluble material was collected by filtration,dispersed in cold distilled water (800 cm 3), and adjusted to pH 4using 10% (v/v)HCl (aq)then recovered by filtrationand recrystal lized from the minimum amount of methanol.The final product obtained was a white powder (96%,0.90 g)with amelting point inexcess of 25 °C.
95%
With polyphosphoric acid at 200℃; for 6h;
92%
With phosphoric acid at 220℃; for 5h;
88%
With polyphosphoric acid at 180℃; for 15h;
3.1
Thoroughly crushed solid dipicolinic acid in an amount of 24 mmol (4.0 g) and o-phenylenediamine in an amount of 48 mmol (5. 2g) were thrown into 40 milliliter of polyphosphoric acid, and the resultant solution was stirred under heating at a temperature of 180 °C for 15 hours. After the resultant solution was cooled by leaving it standing, the resultant homogeneous reaction solution was poured into 500 milliliter of pure water and a precipitate generated. The solution was further stirred in the same condition for 30 minutes. Neutralizing pH of the solution with the use of sodium hydroxide aqueous solution, the precipitate was filtered and dried. After the drying, 6.6 g of white crystal was obtained through re-crystallization from methanol (yield: 88 %).
84.9%
With phosphoric acid at 230℃; for 10h;
1.1 (1) Synthesis of 2,6-bis(benzimidazolyl)pyridine:
mixture of 2,6-dicarboxypyridine (1.0g, 5.98mmol) and o-phenylenediamine (1.29g, 11.97mmol) Phosphoric acid, stirring at 230°C for 10 hours. After the reaction is over, the reaction system is cooled to room temperature, 200 mL of distilled water is added, and the pH is adjusted to 9 with 10% sodium carbonate. After the solid is precipitated out, it is suction filtered to obtain a crude product. The crude product was recrystallized in methanol to obtain a pure product of 1.58 g, and the yield was 84.9%.
82%
With silphox [POCl3-n(SiO2)n, silica phosphinoxide] In N,N-dimethyl-formamide for 0.283333h; Microwave irradiation;
80%
With polyphosphoric acid for 4h; Heating;
80%
With polyphosphoric acid at 220℃; Schlenk technique; Inert atmosphere;
4.1. General considerations
Reactions involving air-sensitive components were performed using a Schlenk-typeflask under an argon atmosphere with high vacuum-line techniques. The glass equipmentwas heated under vacuum in order to remove the oxygen and moisture, andthen filled with argon. The solvents were of analytical grade and distilled under anargon atmosphere from sodium (ethanol, methanol, diethyl ether, and pentane) andP2O5 (dichloromethane). Synthesis of bzimpy [44] and preparation of 2,4,6-bromideand 2,3,4,5,6-pentamethylbenzyl bromide were undertaken according to the literature[45]. PPA is generally freshly prepared. Approximately 25 mL PPA was obtained by mixing18 g P2O5 and 10 g 85% H3PO4. The reagents were stirred at 100 C under a dryatmosphere until a homogenous, clear viscous liquid was formed. Typically, this processtakes 24 h. The 1H and 13C NMR spectra were recorded on a Varian AS400Mercury at Ege University. As solvents, CDCl3 and d6-DMSO were employed, and the Jvalues were in Hz.Compound 1a: Yield: 80%. Elemental analysis: calcd (%) for C19H13N5 (311.12): C,73.30; H, 4.21; N, 22.49%. Found: C, 73.18; H, 4.27; N, 22.43%. 1H NMR (400 MHz, 303 KDMSO-d6) d: 7.41 (m, 4H, BI-H), 7.76 (m, 4H, BI-H), 8.21 (t, 1H, J7.7 Hz, Py-Hp), 8.41 (d,2H, J8.0 Hz, Py-Hm), 13.05 (2H, N-H). 13C NMR (100 MHz, 303 K, DMSO-d6) d: 115.8,121.6 (2 x BI-C), 124.3 (Py-Cm), 136.4 (Py-Cp), 140.4 (BI-C), 146.1 (Py-Co), 150.5(NC-NH).
79%
With polyphosphoric acid at 210℃; for 6h; Inert atmosphere;
74%
With phosphoric acid at 150℃; Inert atmosphere;
72%
With polyphosphoric acid at 220℃; for 5h; Inert atmosphere;
68%
With phosphoric acid for 4h; Inert atmosphere;
Bizimpy (1)
Bizimpy was synthesized according to published procedures [24]. Pyridine-2,6-dicarboxylic acid (dipicolinic acid) (20 mmol, 3.35 g) was added to 1,2-phenylenediamine (44 mmol, 4.7 g) in phosphoric acid (40 ml). The reaction mixture was stirred during 4 h under Ar atmosphere. The obtained green-blue melt waspoured into ice and after reaching room temperature, filtered off. Then sodium carbonate (10%, 100 ml) solution was added to the filtrate. After recrystallization from methanol, white-beige crystals were obtained. Yield: 68% melting point: 626 K.
68%
With phosphoric acid at 230℃;
65%
With polyphosphoric acid at 220℃; for 5h;
65%
With phosphoric acid at 190℃; for 10h;
Synthesis of DBIP
All solvents and chemicals (analytical grade) are commercially available, and used without further purification. 5.00g (0.046mol) of benzene-1,2-diamine and 3.35g (0.02mol) of pyridine-2,6-dicarboxylic acid were added to a 50mL of porcelain mortar, mixed and ground for 15min. The mixed material was transferred into a 25mL of three-neck round-bottom flask; 10mL of 85% (wt) phosphoric acid was added into the flask. The reaction was conducted under magnetic stirring and 190°C for 10h. Then, the content of the flask was allowed to cool to room temperature, and then poured into 300mL of purified water. The resulting mixture was filtered, washed with a 30% (w/w) aqueous sodium hydroxide and distilled water until the filtrate became neutral one. The crude product was dried at 80°C for 12h, and purified by using thermal sublimation. A light yellow powder was obtained, yield: 65% (w/w). 1H NMR (500MHz, DMSO-d6) ppm 13.01 (s, 2H), 8.36 (dd, J=7.8, 1.9Hz, 2H), 8.20 (td, J=8.1, 2.1Hz, 1H), 7.78 (s, 4H), 7.34 (s, 4H). m/z: 312.11 ([M+1]+), elemental analysis (EA) data for DBIP (C19H13N5) was found (calculated) % C=73.26 (73.30), H=4.30 (4.21), N=22..42 (22.49).
65%
With phosphoric acid at 240℃;
62%
With polyphosphoric acid at 120 - 140℃; for 4h;
Preparation of compound 3 i.e. 2,6-di(1H-benzo[d]imidazole-2-yl)pyridine, BBP
Pyridine-2,6-dicarboxylic acid 1 (3.34 gm, 20 mmol) and o-phenylenediamine 2 (4.32 gm, 40 mmol) were reacted together in polyphosphoric acid (PPA) by constant stirring and heating at 120-140 C for 4 h. After completion of reaction, the reaction mixture was cooled to about 50 Cand crushed ice was added with constant stirring. A white solid precipitated out, which was filtered, washed with water and air-dried to afford the desired 3 in 62 % yield(3.86 gm), mp[255 C [Lit. [16] m.p.[250 C].
55%
With phosphoric acid at 230℃; for 4h;
55%
In phosphoric acid at 230℃; for 4h;
Preparation of the Ligand L
The ligand 2,6-bis(benzimidazol-2-yl)pyridine was prepared by the reaction of pyridine-2,6-dicarboxylic acid and o-phenylenediamine in syrupy phosphoric acid (40 mL) at ca. 230° for 4 h as described previously,[11] yield 55%, m.p. >250°. IR (cm-1) in KBr pellet: ν(C = N) 1459s; ν(C = C): 1436s;ν(C-N):1274s; ν(N-H) 3083m, 3058m, and ν(O-H) 3180 m.
53%
With phosphoric acid at 230℃; for 4h;
50%
With polyphosphoric acid at 230℃; for 4h; Inert atmosphere;
48.5%
With polyphosphoric acid Microwave irradiation;
2.2.1 Synthesis of compound intermediate 2
General procedure: Based on our previous report in terms of the microwave-assisted method for the synthesis of benzimidazole compound [36], we conducted the synthesis of the intermediate 2 in a household microwave oven. Acid 1 (1.5mmol), 1,2-diaminobenzene (3.3mmol) and 25mL polyphosphoric acid (PPA) were added into a 50mL round bottom flask. The mixture was intermittently irradiated in a microwave cavity with an output at 40% (320W) for specified times (30s per irradiation). After that, the reaction was stopped by adding water, and the mixture was regulated to the pH range of 9-10 with sodium hydroxide, and a dark green solid was obtained by an immediate filtration. At last, the crude product was recrystallized by ethanol to give the intermediate 2.
46%
With phosphoric acid at 220℃;
2.2. Synthesis of 2,6-bis(2-benzimidazolyl)pyridine (L1)
Pyridine-2,6-dicarboxylic acid (6.68 g, 40 mmol) was stirred with o-phenylenediamine (9.52 g, 88 mmol) in syrupy 85% phosphoric acid (60-70 cm3) at 220°C for overnight [18,19]. The blue coloured melt was poured into 1000 cm3 of vigorously stirred cold water for 1 h. The blue precipitate was collected by filtration through a Büchner funnel, then slurried in 1000 cm3 of 10% aqueous sodium carbonate for 1 h to obtain ochroid-pink colour. The resulting solid was filtered off and recrystallized from hot methanol solution (250 cm3) and activated charcoal to give long, white needles. Yield: 5.70 g, 46%. Melting point 353-355°C. ESI-TOF MS(CH2Cl2): m/z = 334.11 M + Na+. 1H NMR (500 MHz, DMSO-d6,25°C) δ(ppm) 12.99 (s, 2H), 8.33 (d, J = 7.5, 2H), 8.17 (t,J = 7.5 Hz, 1H), 7.75 (t, J = 4.5, 4H), 7.31 (q, J = 2.5, 4H). 13C NMR (125 MHz, DMSO-d6, 25°C) δ(ppm) 150.47, 147.73, 139.19,123.04, 121.35, 79.14. FT-IR (KBr): νm/cm1 = 3178, 3061, 1775,1623, 1601(m), 1591, 1573(m), 1491, 1459(s), 1436(s), 1383,1320(s), 1277(s), 1230, 1146, 1115, 1102, 1023, 1013, 995, 963,929, 902, 880, 845, 822, 803, 767, 742(s), 693, 655, 622, 570,557. Elemental analysis calc. C19H13N5: C, 73.3; H, 4.21; N, 22.5.Found: C, 73.0; H, 4.45; N, 22.2%. X-ray structure analysis: C19H13-N53CH3OH, M = 407.47 g mol-1.
43%
With phosphoric acid at 200℃; for 6h;
2.2.1. Synthesis of 2,6-bis(2-benzimidazolyl)pyridine (L1)
Pyridine-2,6-dicarboxylic acid (0.0200mol, 3.35g) was stirredwith o-phenylenediamine (0.044mol, 4.7g) in 40 ml syrupy phosphoricacid at 200 C up to 6h [43,44]. The blue colloidal melt waspoured into 500ml cold water for 10 min with vigorous stirring.After blue precipitate was collected by filtration through a Büchnerfunnel and slurried in 500ml of 10% hot sodium carbonate for15 min to get ochroid-pink colour solid. The solid was filtered andrecrystallized using hot methanol solution to give long, whiteneedles. Yield 43%, 1H NMR (500 MHz, DMSO) d 8.33 (d, J 7.8 Hz,2H), 8.16 (t, J 7.8 Hz, 1H), 7.76 (dd, J 5.9, 3.2 Hz, 4H), 7.28 (dd,J 6.0, 3.1 Hz, 4H).13C NMR (126 MHz, DMSO) d 151.33, 148.48,139.54, 123.19, 121.67, 116.55. The mass spectrum (ESI) showed amolecular ion peak at m/z 311.90 (MH). The data is given in supp.data e Fig. S1aec.
43%
With phosphoric acid at 200℃; for 6h;
31%
With phosphoric acid at 250℃; for 4h;
2,6-Bis(benzimidazol-2′-yl)pyridine (A)11
To a 200 mL round-bottom flask equipped with a condenser wereadded 2,6-pyridinedicarboxylic acid (30 mmol, 5.01 g), o-phenylenediamine(65 mmol, 7.03 g), and phosphoric acid (90 mL), and the reactionmixture was stirred for 4 h at 250 °C. After cooling to roomtemperature, the mixture was poured into 500 mL of water, and thenneutralized with 1 M NaOH (aq). The resulting suspension was filteredand the obtained solid was purified by recrystallization fromMeOH to give ligand A as a white solid (31%, 3.0 g).Mp 192-194 °C.1H NMR (400 MHz, DMSO-d6): = 13.0 (brs, 2 H), 8.47-8.50 (m, 2 H),8.30-8.34 (m, 1 H), 7.80-7.85 (m, 4 H), 7.41-7.44 (m, 4 H).13C NMR (100 MHz, DMSO-d6): = 149.4, 146.2, 140.4, 137.0, 125.0,123.5, 115.8.
16%
at 230℃; for 4h; Autoclave;
With hydrogenchloride Heating;
With ethylene glycol at 190℃;
With polyphosphoric acid at 240℃;
With polyphosphoric acid at 220℃;
With polyphosphoric acid at 240℃; for 4h;
With polyphosphoric acid at 160℃; for 6h;
2.1 Compounds
General procedure: Most of the analogues were prepared by reaction of (substituted) pyridine-2,6-dicarboxylic acid with 2 equivalents of (a substituted) 1,2-phenylenediamine in PPA (polyphosphoric acid) at 160°C for 6h as depicted in Fig. 1. The synthesis of LZ37 [7-[3-(1,3-benzodioxol-5-yl)propyl]-2-(2-furyl)-7H-pyrazolo[4,3-e][1,2,4]triazolo[1,5-c]pyrimidin-5-amine] (Baraldi et al., 1996), BPIP (5-[(4-bromophenyl)methyl]-2-phenyl-5H-imidazo[4,5-c]pyridine (Puerstinger et al., 2006) and ethyl 2-methylimidazo[1,2-a]pyrrolo[2,3-c]pyridin-8-carboxylate (AG110) (Paeshuyse et al., 2007) were reported earlier. 3′-deoxyguanosine-5′-triphosphate (3′-dGTP) and 2′-C-methylguanosine-5′-triphosphate (2′-C-me-GTP) were purchased from Trilink (San Diego, CA).
With polyphosphoric acid at 190℃;
With phosphoric acid for 0.5h; Microwave irradiation;
With polyphosphoric acid at 230℃; for 4h; Inert atmosphere;
With phosphoric acid
With polyphosphoric acid at 230℃; Inert atmosphere;
With phosphoric acid for 4h; Inert atmosphere;
Synthesis of 2,6-bis(2-benzimidazolyl)pyridine
The tri-dentate NN’N’’ ligand, 2,6-bis(2-benzimidazolyl)pyridine,was synthesized according to the related literature.[41,42] Pyridine-2,6-dicarboxylic acid (20 mmol, 3.35 g)was added to 1,2-phenylenediamine (44 mmol, 4.7 g) inphosphoric acid (40 mL). The reaction mixture was stirredduring 4 hours under Ar atmosphere. The obtained bluecolored melt was poured into ice and after reaching roomtemperature, filtered off. Then sodium carbonate (10%,100 mL) solution was added to the filtrate. The obtainedpink-purple melt was washed with methanol numbers oftimes. And the solid was crystallized from MeOH. Theorange crystals were purified by adding activated carbon.After recrystallization from methanol white-beige crystalswere obtained.FT-IR (ATR/cm1): 3181, 3064, 1681, 1603, 1576, 1490,1457, 1434, 1409, 1386, 1317, 1277, 1230, 1144, 1112, 1012,958, 926, 845, 815, 738, 729, 693. 1H-NMR (400 MHz,DMSO-d6) d ppm 8.34 (d, J7.37 Hz, 2 H), 8.17 (t,J8.14 Hz, 1 H), 7.77 (d, J7.74 Hz, 2 H), 7.74 (d,J8.34 Hz, 2 H), 7.35 (t, J7.69 Hz, 2 H), 7.28 (t,J7.46 Hz, 2 H).
With polyphosphoric acid at 200℃; for 12h; Inert atmosphere; Schlenk technique;
[0118] 36 mg (0.1524 mmol) <strong>[298-46-4]carbamazepin</strong>e and 26 mg (0.1556 mmol) 2,6-pyridinedicarboxylic acid were dissolved in approximately 2 mL ethanol. Slow evaporation of the solvent yielded clear needles of a 1:1 <strong>[298-46-4]carbamazepin</strong>e/2,6-pyridinedicarboxylic acid cocrystal, as shown in FIG. 14B. [0119] Crystal data: (Bruker SMART-APEX CCD Diffractometer). C22H17N3O5, M=403.39, orthorhombic P2(1)2(1)2(1); a=7.2122, b=14.6491, c=17.5864 , alpha=90, beta=90, gamma=90, V=1858.0(2) 3, T=100 K, Z=4, mu(MO-Kalpha)=0.104 mm, Dc=1.442 Mg/m3, lambda=0.71073 3, F(000)840, 2thetamax=28.3.116641 reflections measured, 4466 unique (Rint=0.093). Final residuals for 271 parameters were R1=0.0425 and wR2=0.0944 for I>2?(I). [0120] Crystal packing: Each hydrogen on the CBZ 1 amine is hydrogen bonded to a carbonyl group of a different 2,6-pyridinedicarboxylic acid moiety. The carbonyl of the CBZ carboxamide is hydrogen bonded to two hydroxide groups of one 2,6-pyridinedicarboxylic acid moitey. [0121] Infrared Spectroscopy: (Nicolet Avatar 320 FTIR). 3439 cm-1, (N-H stretch, 1 amine, CBZ); 1734 cm-1, (CO); 1649 cm-1, (CC). [0122] Melting Point: 214-216 C. (MEL-TEMP). (<strong>[298-46-4]carbamazepin</strong>e m.p.=191-192 C., 2,6-pyridinedicarboxylic acid m.p.=248-250 C.). [0123] Thermogravimetric Analysis: (TA Instruments 2950 Hi-Resolution TGA). 69% weight loss starting at 215 C. and a 17% weight loss starting at 392 followed by complete decomposition.
Cu2(2,5-bis(4-pyridyl)-1,3,4-oxadiazole)(pyridine-2,6-dicarboxylate)2(H2O)3*2.75H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
51%
With triethylamine In methanol; water MeOH soln. of pyridine-2,6-dicarboxylic acid added to aq. soln. of Cu(CH3CO2)2*H2O, mixed for 3 min, MeOH soln. of 2,5-bis(4-pyridyl)-1,3,4-oxadiazole added, pH to 7 adjusted by (CH3CH2)3N; filtered, evapd. slowly under ambient temp. for 1 wk; elem. anal.;
With NaOH In water High Pressure; mixt. of Cu(CH3CO2)2*H2O, pyridine-2,6-dicarboxylic acid, NaOH, 2,5-bis(4-pyridyl)-1,3,4-oxadiazole heated at 140°C for 3 d in Teflon vessel, slowly cooled to room temp. at 5°C/h;
With NaOH In water High Pressure; mixt. of Pb(CH3CO2)2*3H2O, pyridine-2,6-dicarboxylic acid, NaOH, 2,5-bis(4-pyridyl)-1,3,4-oxadiazole heated at 140°C for 3 d in Teflon vessel, slowly cooled to room temp. at 5°C/h; elem. anal.;
Co(2,5-bis(4-pyridyl)-1,3,4-oxadiazole)(pyridine-2,6-dicarboxylate)(H2O)2*H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
With NaOH In water High Pressure; mixt. of Co(CH3CO2)2*4H2O, pyridine-2,6-dicarboxylic acid, NaOH, 2,5-bis(4-pyridyl)-1,3,4-oxadiazole heated at 140°C for 3 d in Teflon vessel, slowly cooled to room temp. at 5°C/h; elem. anal.;
Synthesis of [6mu]2[pydcH2] (1)
A well-ground mixture of 6mu (200 mg, 1.6 mmol), pydcH2(140 mg, 0.8 mmol) in distilled water (30 mL) was placed in aTeflon-lined stainless steel autoclave, heated to 180 °C for 72 h (seeScheme 1). The mixture was extracted with the mixed solvent ofDMF (20 mL) and CH3OH (15 mL), and then filtered. The filtrate wasremained in the atmosphere of laboratory. By slow evaporation ofsolution, the colorless solid obtained after 16 days, was filteredoff, washed with acetone and dried at 60 .C (yield: 30% based onpydcH2).
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; In dichloromethane;Reflux;
The synthesis of pyridine acyl sulfonamide derivatives was followed the general reaction pathway outlined in refPreviewPlaceHolderScheme 1. Compounds 1-24 were synthesized by coupling substituted benzenesulfonamide with nicotinic acid, isonicotinic acid, picolinic acid, pyridine-2,6-dicarboxylic acid or pyridine-3,5-dicarboxylic acid, using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI), 4-dimethylaminopyridine (DMAP) as condensing agent. The mixture was refluxed in anhydrous CH2Cl2 for 8-10 h. The products were extracted with ethyl acetate. The extract was washed successively with HCl, NaHCO3 and water, dried over Na2SO4, filtered and evaporated. The residue was purified by column chromatography using petroleum ether and ethyl acetate (1:1).
With polyphosphoric acid at 210℃; for 4h; Neat (no solvent);
90%
Stage #1: Pyridine-2,6-dicarboxylic acid; N-methyl-1,2-phenylenediamine With phosphoric acid In water at 250℃; for 24h; Inert atmosphere;
Stage #2: With potassium hydroxide In water for 2h; Cooling with ice;
90%
With phosphoric acid In water at 250℃; for 24h; Inert atmosphere;
85%
With phosphoric acid at 230℃; for 4h;
This ligand was prepared by a modification of the procedure reported for 2,6-bis(benzimidazol-2-yl)pyridine.4 A mixture of pyridine-2,6-dicarboxylic acid (3.35 g, 20 mmol) and N-methyl-1,2-phenylenediamine (5.38 g, 44 mmol) in 40 mL of 85% phosphoric acid was stirred at ca 230° C. for 4 h. The dark green melt was poured into 1 L of vigorously stirred cold water. After it was cooled to room temperature, the blue precipitate was collected by filtration, then slurried into 300 mL of hot aqueous sodium carbonate solution (10%). The resulting solid was filtered off and recrystallized from methanol to give a white solid. Yield: 5.77 g, 85%. NMR (CDCl3): δ 8.42 (d, 2H), 8.05 (t, 1H), 7.86-7.89 (m, 2H), 7.44-7.48 (m, 2H), 7.33-7.41 (m, 4H), 4.25 (s, 6H, 2CH3). This ligand was pure by 1H-NMR and was used without further purification
General procedure: 1 mmol of Cu(CH3COO)2·H2O in 10 mL of water was added dropwise to a mixed-ligand solution of 2,6-pyridinedicarboxylic acid (1 mmol) and the appropriate pyrimidine ligand (1 mmol) in 20 mL of water with stirring at room temperature. The solution was filtered and left standing at ambient temperature. After a few days blue crystals appeared. These were washed and dried at room temperature. Crystals for X-ray diffraction were used directly from the mother liquid. Yield ca. 75-85%. Elemental Anal. Calc. for C11H15CuN3O9 (1): C, 33.3; H, 3.8; N, 10.6. Found: C, 33.4; H, 3.9; N, 10.6%; for C11H9CuN5O7 (2): C, 34.2; H, 2.3; N, 18.1. Found: C, 34.1; H, 2.2; N, 18.1%; for C11H11ClCuN4O6 (3): C, 33.5; H, 2.8; N, 14.2. Found: C, 33.5; H, 2.7; N, 14.3%.
[H3O][Cr(2,6-pyridinedicarboxylate)2] [H3O+.Cl-][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With sodium hydroxide; In ethanol; water; for 12h;Reflux;
Dipicolinic acid (H2dipic, 0.167 g, 1.0 mmol) and NaOH (0.080 g, 2.0.mmol) were dissolved in the mixture of ethanol/water (20 mL) and dropwise added, under continuous stirring, to an aqueous solution (5 mL) of CrCl3·6H2O (0.988 g,0.50 mmol). Then <strong>[1115-70-4]metformin hydrochloride</strong> (0.057 g, 0.50 mmol) was added to the resulting mixture and was refluxed for 12 h, filtered off and then left to evaporate in a beaker in air at the ambient temperature. In an attempt to prepare the complex [MetH][Cr(dipic)2], after 5 day, dark purple crystals suitable for X-ray structural analysis from the title complex, (1) , were obtained. The yield was 65 %. Anal. Calc. for C14H12ClCrN2O10: C, 36.90; H, 2.65; N, 6.15. Found: C,36.7; H, 2.80; N, 5.9 %. IR (KBr) (nu, cm-1): 3599 (w), 3558(m), 3474 (m), 3423 (m), 3078 (m), 3049 (m), 2923 (w),1673 (s), 1598 (w ), 1479 (w), 1428 (m), 1332 (s), 1261 (w), 1169 (s), 1090 (s), 1036 (w), 1010 (w), 920 (s), 854 (w),779(s ), 750(s), 682 (s), 593 (w), 541 (w), 452 (s). UV-vis (aqueous solution) (nu, nm): 260, 267, 301, 352, 551.
7H2O*C5H5N*C21H9CeN3O12(3-)*3H(1+)*C5H12N2O2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
General procedure: For (H2His)(HPy)[Ce(dpc)3].4H2O (4) and (H2Orni)(HPy)[Ce(dpc)3].7H2O (5), to a solution of dipicolinic acid (0.50 g,3 mmol) in methanol (10 mL), a solution of Ce(NO3)3.6H2O(0.434 g, 1 mmol in 10 mL methanol) was added. The reactionmixture was stirred for half an hour to obtain a deep yellow precipitate.To the reaction mixture 10 mL solution of L-histidinehydrochloride (0.21 g, 1 mmol) or <strong>[3184-13-2]L-ornithine hydrochloride</strong> (0.17 g, 1 mmol) in water was added in small portions andstirred. Minimum amount of pyridine (py) was added to dissolvethe precipitate once the color of the precipitate changed tolight yellow. This led to dissolution of the precipitate to result a reddish yellow solution. The reaction mixture was filtered andleft for crystallization. After three days reddish yellow crystals were obtained.
General procedure: For (H2Arg)[Ce(dpc)3].7H2O (1), (H2His)[Ce(dpc)3].4H2O(2), and (H2Orni)[Ce(dpc)3].7H2O (3), to a solution of dipicolinicacid (0.501 g, 3 mmol) in methanol (10 mL), a solution of(NH4)2Ce(NO3)6 (0.548 g, 1 mmol) in methanol (10 mL) wasadded. The reaction mixture was stirred for 30 min and a yellowprecipitate was obtained. To the reaction mixture 10 mL solutionof L-arginine hydrochloride (0.21 g, 1 mmol) or L-histidinehydrochloride (0.21 g, 1 mmol) or <strong>[3184-13-2]L-ornithine hydrochloride</strong>(0.17 g, 1 mmol) in water was added in small portions andstirred. The respective precipitate obtained was dissolved inwater to obtain a yellow solution. The yellow solution was filteredand left for crystallization. After four days light yellowcrystals were obtained.
4H2O*C5H5N*C21H9CeN3O12(3-)*3H(1+)*C6H9N3O2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
General procedure: For (H2His)(HPy)[Ce(dpc)3].4H2O (4) and (H2Orni)(HPy)[Ce(dpc)3].7H2O (5), to a solution of dipicolinic acid (0.50 g,3 mmol) in methanol (10 mL), a solution of Ce(NO3)3.6H2O(0.434 g, 1 mmol in 10 mL methanol) was added. The reactionmixture was stirred for half an hour to obtain a deep yellow precipitate.To the reaction mixture 10 mL solution of L-histidinehydrochloride (0.21 g, 1 mmol) or L-ornithine hydrochloride (0.17 g, 1 mmol) in water was added in small portions andstirred. Minimum amount of pyridine (py) was added to dissolvethe precipitate once the color of the precipitate changed tolight yellow. This led to dissolution of the precipitate to result a reddish yellow solution. The reaction mixture was filtered andleft for crystallization. After three days reddish yellow crystals were obtained. For complex 4: Isolated yield (based on metal)70%. Elemental Anal. Calcd. for C32H37CeN7O18: C, 40.51; H,3.90; Found C, 40.57; H, 3.99. IR (KBr, cm-1): 3391 (bs), 1714(s), 1614 (s), 1428 (w), 1385 (s), 1366 (m), 1273 (w), 1188(w), 1076 (m), 765 (w). [alpha]D25 = + 7.2. Molar conductance:436.5 Scm2mol-1 in water. Magnetic moment mueff. at 298 K:1.98 BM.
General procedure: For (H2Arg)[Ce(dpc)3].7H2O (1), (H2His)[Ce(dpc)3].4H2O(2), and (H2Orni)[Ce(dpc)3].7H2O (3), to a solution of dipicolinicacid (0.501 g, 3 mmol) in methanol (10 mL), a solution of(NH4)2Ce(NO3)6 (0.548 g, 1 mmol) in methanol (10 mL) wasadded. The reaction mixture was stirred for 30 min and a yellowprecipitate was obtained. To the reaction mixture 10 mL solutionof <strong>[1119-34-2]L-arginine hydrochloride</strong> (0.21 g, 1 mmol) or L-histidinehydrochloride (0.21 g, 1 mmol) or L-ornithine hydrochloride(0.17 g, 1 mmol) in water was added in small portions andstirred. The respective precipitate obtained was dissolved inwater to obtain a yellow solution. The yellow solution was filteredand left for crystallization. After four days light yellowcrystals were obtained.For complex 1: Isolated yield (based on metal) 55%. ElementalAnal. Calcd. for C27H32CeN7O21: C, 34.81; H, 3.43; FoundC, 34.57; H, 3.36. IR (KBr, cm-1): 3365 (bs), 1639(s), 1465(m),1423 (m), 1360 (s), 1268 (w), 1176 (w), 1073(m), 1024 (m), 920(w). [alpha]D25 = + 7.5. Molar conductance: 430.3 Scm2mol-1 in water.
General procedure: For (H2Arg)[Ce(dpc)3].7H2O (1), (H2His)[Ce(dpc)3].4H2O(2), and (H2Orni)[Ce(dpc)3].7H2O (3), to a solution of dipicolinicacid (0.501 g, 3 mmol) in methanol (10 mL), a solution of(NH4)2Ce(NO3)6 (0.548 g, 1 mmol) in methanol (10 mL) wasadded. The reaction mixture was stirred for 30 min and a yellowprecipitate was obtained. To the reaction mixture 10 mL solutionof L-arginine hydrochloride (0.21 g, 1 mmol) or L-histidinehydrochloride (0.21 g, 1 mmol) or L-ornithine hydrochloride(0.17 g, 1 mmol) in water was added in small portions andstirred. The respective precipitate obtained was dissolved inwater to obtain a yellow solution. The yellow solution was filteredand left for crystallization. After four days light yellowcrystals were obtained.
With phosphorus pentachloride; ammonia; In acetonitrile; at -40 - 20℃; for 2h;
The liquid ammonia (0.5 ml) and acetonitrile (50 ml) at -40 C in cold bath, adding pyridine -2,6-dicarboxylic acid (1.67g), to 0 C, batch by adding phosphorus pentachloride (4g), is omitted, stirring the mixture at room temperature for 2 hours, the response finishes, concentrated under reduced pressure, the residue is dissolved with methylene chloride, washed with saturated sodium bicarbonate to neutral, anhydrous magnesium sulphate dried, concentrated, precipitated solid, the resulting solid is recrystallized with isopropyl alcohol, to obtain white crystal of 2,6-di-cyano pyridine (1.13g). The yield is 88%.
3 was produced by refluxing a mixture of adefovir (27.3 mg,0.1 mmol) and 2, 6-pyridine dicarboxylic acid (16.7 mg, 0.1 mmol) at 90C in 8 mL of ethanol-water (1:1, v/v) for about 3 h, the resulting mixtures were filtered, and the filtrate was placed at room temperature for 5 days. The colorless block crystals were obtained in 75% yield.
4,6-diaminoresorcinol-2,6-pyridinedicarboxylic acid[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With sodium hydroxide; In water; at 90℃; for 0.166667h;
Into a 1000 mL glass flask, equipped with a mechanical stirrer and a nitrogen inlet/outlet, were placed 400 mL water. 4,6-diaminoresorcinol dihydrochloride (4.26 g, 0.02 mol) was added. One equimolar amount of 2,6-pyridinedicarboxylic acid (PDA, 0.02 mol) dissolved in NaOH (0.04 mol) aqueous solution was slowly added. Afterwards, the mixture was heated to 90 C for 10 min and DAR-PDA salt solid precipitated, then the product was collected in nitrogen atmosphere. The product was dried under vacuum at 60 C for 48 h.
General procedure: All chemicals used in this study were obtained from commercial suppliers (Sigma-Aldrich) and were used without any further purification. The spectroscopic grade solvents employed for the crystallization purpose were of the highest available purity. All the molecular complexes were prepared by dissolving <strong>[230-07-9]4,7-phenanthroline</strong> (1) and the corresponding carboxylic acids in a solution of dimethylsulfoxide (DMSO), as listed in Chart 1, in a 1:1 ratio and then by slow evaporation of the solution at ambient conditions. Single crystals were obtained within 48h in all the cases. In a typical example, 18.3mg (0.97mmol) of 1 and 16.6mg (0.99mmol) of pyridine-2,6-dicarboxylic acid, a, were dissolved by heating up to 80C in 2mL DMSO and allowed for slow evaporation at ambient conditions. Good quality single crystals suitable for X-ray diffraction study were obtained in 48h.
With ammonium hydroxide; In N,N-dimethyl-formamide; at 20℃;Darkness;
The synthesis of 2 was similar to that of 1, but with H2pda(33.4 mg, 0.2 mmol) in place of H2pca. The resultant solution wasallowed to evaporate slowly in darkness at room temperature forseveral days to afford the product as block-shaped pink crystalsof 2. (Yield: 69%, based on silver). Anal. Calc. (found) for Ag2C12H10N4O6: C, 27.72 (27.69); H, 1.55 (1.61); N, 10.78 (10.96)%. IR (KBr): m(cm1) = 3395 (m), 3326 (m), 3211 (m), 3058 (m), 1664 (s), 1613(s), 1562 (s), 1428 (m), 1371 (s), 1268 (m), 1167 (w), 1046 (w),1021 (m), 900 (w), 816 (m), 753 (m), 715 (s), 651 (m), 619 (m),575 (w), 511 (w), 448 (w).
N<SUP>2</SUP>,N<SUP>6</SUP>-bis(2-(phenylamino)phenyl)pyridine-2,6-dicarboxamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
53%
Stage #1: Pyridine-2,6-dicarboxylic acid With thionyl chloride for 8h; Reflux;
Stage #2: N-phenyl-1,2-benzenediamine With triethylamine In dichloromethane at 20℃; for 2h;
2.4. Synthesis of N2, N6-bis(2-(phenylamino)phenyl)pyridine-2,6-dicarboxamide
Pyridine-2, 6-dicarboxylic acid (3.34 g,20mmol) was refluxed in thionyl chloride 20mL for8 h. Excess thionyl chloride was removed under vacuum.After cooling to room temperature, N1-phenylbenzene-1,2-diamine (7.36 g, 40mmol) and triethylamine (10 mL) in 60mL of CH2C12, were added to the solution of the residuein CH2C12 (30 mL). The mixture was further stirred for 2 hat ambient temperature. The yellow solid was collected byfiltration, washed with water, and dried in vacuo (yield: 5.31 g,53.00%). Analysis calculated for C31H25N5O2 (%), C, 74.53%,H, 5.04%, N, 14.02%. Found: C, 74.52%, H, 5.14%, N, 14.20%.IR (KBr)/cm-1, 3353, 3046, 1676, 1641, 1595, 1516, 1456, 1425,1310, 1260, 1176, 1150, 1076, 999, 882, 745, 676, 493. 1HNMR(400MHz, δ d6-DMSO, ): 6.74-6.77 (t, 2H), 6.89-6.91 (d,4H), 7.02-7.09 (t, 2H), 7.10-7.13 (t, 4H), 7.20-7.24 (t, 2H), 7.34-7.36 (d, 2H), 7.50-7.57 (t, 4H) 8.25-8.28 (q, 1H), 8.33-8.35 (d,2H).
With sodium hydroxide; In methanol; water; at 38℃; for 0.833333h;Reflux;
1) adding pyridinedicarboxylic acid, sodium hydroxide and <strong>[1115-70-4]metformin hydrochloride</strong> in an organic solvent at a molar ratio of 2: 5: 1,And the mixture was dissolved at a temperature of 38 C, and the organic solvent was a mixture of water and methanol in a molar ratio of 1: 1.5, and the mixture of water and methanol was 12 times the volume of the mixture of pyridinedicarboxylic acid, sodium hydroxide and <strong>[1115-70-4]metformin hydrochloride</strong>;2) Chromium chloride was dissolved in methanol at a molar ratio of chromium chloride to methanol of 1: 7, and the solution of chromium chloride was slowly added dropwise to the solution in Step 1) and heated to reflux for 50 min to stop the reaction , Standing for 12h, filtration, the red filtrate;3) Place the red filtrate at room temperature,Dark,Naturally volatile for half a month,To obtain purple crystal is dimethyl metformin pyridine dicarboxylic acid Cr (III) complex.
Vanadyl sulfate (434mg, 2.0mmol) was dissolved in 40mL of water. Solid 2,6- pyridinedicarboxylic acid (334mg, 2.0mmol) then was added. The mixture was stirred at 90C until the green solution was obtained. Afterward, solid <strong>[1115-70-4]metformin hydrochloride</strong> (165mg, 1.0mmol) was added to the resulting mixture and was heated at 90C for 30min until dissolution was complete. After 2 days, the white precipitated H2dipic ligand excess and blue crystalline 1 were filtered off. 10mL water was again added to the filtrate and was heated at 90C for 30min. After several weeks, dark crystals of the complex 2, suitable for X-ray structural analysis, were obtained. During this period the color of the solution changed to dark blue. Anal. Calc. for C18H19N7O12V2: C, 34.47; H, 3.05; N, 15.63. Found: C, 34.27; H, 2.69; N, 15.54%. 1H NMR (DMSO-d6): delta=2.95 (s, 6H, CH3, H2Met2+), 8.17 (s, 2H, dipic2-), 8.49 (s, 1H, dipic2-) ppm. 13C NMR (DMSO-d6): delta=36.2 (CH3, H2Met2+), 124.8 (dipic2-), 145.2 (dipic2-), 146.2 (dipic2-), 152.7 (H2Met2+), 153.8 (H2Met2+), 165.6 (dipic2-) ppm. FT-IR (KBr): 3410, 3330, 3182 nu(N-H), 3081 nu(aromatic C-H), 2922 nuas (aliphatic C-H), 2852 nus (aliphatic C-H), 1689 nuas (CO2-), 1658, 1341 nus (CO2-), 1172, 1076, 936, 862, 767, 674, 456cm-1. UV-Vis (aqueous solution) (lambda, nm): 207, 274.
Vanadyl sulfate (434mg, 2.0mmol) was dissolved in 40mL of water. Solid 2,6- pyridinedicarboxylic acid (334mg, 2.0mmol) then was added. The mixture was stirred at 90C until the green solution was obtained. Afterward, solid <strong>[1115-70-4]metformin hydrochloride</strong> (165mg, 1.0mmol) was added to the resulting mixture and was heated at 90C for 30min until dissolution was complete. After 2 days, the white precipitated H2dipic ligand excess and blue crystalline 1 were filtered off. 10mL water was again added to the filtrate and was heated at 90C for 30min. After several weeks, dark crystals of the complex 2, suitable for X-ray structural analysis, were obtained. During this period the color of the solution changed to dark blue. Anal. Calc. for C18H19N7O12V2: C, 34.47; H, 3.05; N, 15.63. Found: C, 34.27; H, 2.69; N, 15.54%. 1H NMR (DMSO-d6): delta=2.95 (s, 6H, CH3, H2Met2+), 8.17 (s, 2H, dipic2-), 8.49 (s, 1H, dipic2-) ppm. 13C NMR (DMSO-d6): delta=36.2 (CH3, H2Met2+), 124.8 (dipic2-), 145.2 (dipic2-), 146.2 (dipic2-), 152.7 (H2Met2+), 153.8 (H2Met2+), 165.6 (dipic2-) ppm. FT-IR (KBr): 3410, 3330, 3182 nu(N-H), 3081 nu(aromatic C-H), 2922 nuas (aliphatic C-H), 2852 nus (aliphatic C-H), 1689 nuas (CO2-), 1658, 1341 nus (CO2-), 1172, 1076, 936, 862, 767, 674, 456cm-1. UV-Vis (aqueous solution) (lambda, nm): 207, 274.
[mono-protonated 6-phenyl-1,3,5-triazine-2,4-diamine][Fe(2,6-pyridinedicarboxylate)2]3H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
To a solution of 2,6-pyridinedicarboxylicacid (0.167 g, 1.0 mmol) in methanol (10 ml), a solutionof anhydrous ferric chloride (0.053 g, 0.33 mmol) in methanol(10 ml) was added. A brown precipitate was obtained after stirring for half an hour. The precipitate was dissolved by adding 20 ml water and to this solution 6-phenyl-1,3,5-triazine-2,4-diamine (0.094 g, 0.5 mmol) was added. The reaction mixture was stirredfor 3 h at room temperature. Further standing for 4 days at room temperature resulted in crystals of 1. Isolated yield: (0.220 g) 70%. Elemental Anal. Calc. for C23H22N7O11Fe: C, 43.97; H, 3.53;N, 15.60; Found: C, 43.96; H, 3.50; N, 15.59%. IR (KBr, cm-1):3390 (m), 3140 (w), 3087 (s), 3048 (w), 1661 (s), 1609 (w), 1570(s), 1528 (m), 1427 (m), 1331 (s), 1169 (s), 1082 (s), 1027 (m),912 (s), 862 (w), 777 (m), 745 (s), 681 (s), 590 (w). Magnetic moment (28 C): 5.37 BM. UV-Vis (methanol, nm (epsilon, mol-1cm-1)): 212 (8210), 280 (3130), 720 (13).
[Cu(pyrazinecarboxamide)(dipicolinate)(H2O)].H2O}[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
85%
The synthesis of the compound [Cu(pca)(dipic)(H2O)]H2O}was proceeded in the following manner: to a water solution of copper(II) acetate monohydrate (0.15 g, 0.75 mmol) was added a stoichiometric amount of N-donor ligand pyrazinecarboxamide (0.09g, 0.75 mmol). The mixture was stirred for half an hour at laboratory temperature to obtain a homogeneous solution, then further reacted with stoichiometric ratio 1:1 of dipicolinic acid (0.125 g,0.75 mmol) and heated. The resulting blue solution was cooled down to the ambient temperature, filtered and left to slowly evaporate at laboratory temperature, what after a few days resulted in the single-crystals formation of targeted compound. Single-crystals for X-ray diffraction analysis were used directly from mother liquid.IR (ATR, cm-1): 3483(m), 3450(m), 3350(m), 3208(m), 3080(w),3043(w), 1688(s), 1673(s), 1634(s), 1606(s), 1593(s), 1527(w),1429(w), 1383(m), 1360(s), 1347(s), 1269(w), 1172(m), 1163(m),1088(m), 1080(m), 1022(m), 912(m), 883(w), 866(w), 781(s), 739(m), 705(w), 685(m), 633(m), 569(m), 515(w), 461(s), 440(s)UV-Vis (nm): 206, 274, 691.Elemental analysis for complex 1 (C12H12CuN4O7, Mw = 387.79g mol1) found % (expected %): C 36.99 (37.17); N 14.77 (14.45); H3.12 (3.12). Yield: 85%.
[Cu(N-methylnicotinamide)(dipicolinate)(H2O)].2H2O}[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
General procedure: The synthesis of the compound [Cu(pca)(dipic)(H2O)]H2O}was proceeded in the following manner: to a water solution of copper(II) acetate monohydrate (0.15 g, 0.75 mmol) was added a stoichiometric amount of N-donor ligand pyrazinecarboxamide (0.09g, 0.75 mmol). The mixture was stirred for half an hour at laboratory temperature to obtain a homogeneous solution, then further reacted with stoichiometric ratio 1:1 of dipicolinic acid (0.125 g,0.75 mmol) and heated. The resulting blue solution was cooled down to the ambient temperature, filtered and left to slowly evaporate at laboratory temperature, what after a few days resulted in the single-crystals formation of targeted compound. Single-crystals for X-ray diffraction analysis were used directly from mother liquid.
[Cu(N-(hydroxymethyl)nicotinamide)(dipicolinate)(H2O)]2.2[Cu(N-(hydroxymethyl)nicotinamide)(dipicolinate)(H2O)2].4H2O}[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
General procedure: The synthesis of the compound [Cu(pca)(dipic)(H2O)]H2O}was proceeded in the following manner: to a water solution of copper(II) acetate monohydrate (0.15 g, 0.75 mmol) was added a stoichiometric amount of N-donor ligand pyrazinecarboxamide (0.09g, 0.75 mmol). The mixture was stirred for half an hour at laboratory temperature to obtain a homogeneous solution, then further reacted with stoichiometric ratio 1:1 of dipicolinic acid (0.125 g,0.75 mmol) and heated. The resulting blue solution was cooled down to the ambient temperature, filtered and left to slowly evaporate at laboratory temperature, what after a few days resulted in the single-crystals formation of targeted compound. Single-crystals for X-ray diffraction analysis were used directly from mother liquid.
[Co<SUB>2</SUB>(4,4'-bis(1-imidazolyl)biphenyl)(2,6-pyridinedicarboxylate)<SUB>2</SUB>(water)<SUB>4</SUB>][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
General procedure: To a solution of the pyridinedicarboxylic acid (0.084g, 0.5 mmol) in distilled water (8 mL), NaOH (0.040 g, 1.0 mmol) was added and stirred for 5 min. Then the hexahydrated metal nitrate salt (0.5 mmol) and <strong>[855766-92-6]4,4′-bis(1-imidazolyl)biphenyl</strong> (0.143 g, 0.5 mmol) were added. The mixture was placed and sealed in a Teflon-lined stainless steel vessel (10 mL), heated at 160C for 3 days and cooled to room temperature with the rate of 0.06C/min. The obtained crystals were filtered, washed with water and ethanol then dried in air. [Co2(BIBP)(2,6-PDC)2(H2O)4] (1) The preparation of (1) was done according to the general procedure using 2,6-pyridinedicarboxylic acid and Co(NO3)2·6H2O (0.146 g, 0.5 mmol). Yield: 0.250 g, 62%. Anal. Calc. for C32H28N6O12Co2: C, 47.66; H, 3.50; N, 10.42. Found: C, 47.91; H, 3.76; N, 10.70%. FT-IR ( ν/cm-1): 3676 m, 3291 br, 3166 m, 3126 m, 2989 m, 2902 m, 1636 s, 1608vs, 1592 s,1576 s, 1520 s,1467 m, 1433 m, 1417 m, 1378 s, 1362 vs, 1343 m, 1311 m, 1281 m, 1268 m, 1255 m, 1195 m,1181 m, 1133 m, 1106 m, 1070 vs, 1036 m, 1003 m, 963 m, 944 m, 913 m, 862 w, 834 s, 822 m, 768 w, 747 s, 736 s, 722 m, 689 m, 673 m.
1D-[Zn(4,4'-bis(1-imidazolyl)biphenyl)(2,6-pyridinedicarboxylate)]*4.5(water)}<SUB>n</SUB>[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
General procedure: To a solution of the pyridinedicarboxylic acid (0.084g, 0.5 mmol) in distilled water (8 mL), NaOH (0.040 g, 1.0 mmol) was added and stirred for 5 min. Then the hexahydrated metal nitrate salt (0.5 mmol) and <strong>[855766-92-6]4,4′-bis(1-imidazolyl)biphenyl</strong> (0.143 g, 0.5 mmol) were added. The mixture was placed and sealed in a Teflon-lined stainless steel vessel (10 mL), heated at 160C for 3 days and cooled to room temperature with the rate of 0.06C/min. The obtained crystals were filtered, washed with water and ethanol then dried in air. 3.3.3 1D-[Zn(BIBP)(2,6-PDC)]∙4·.5H2O}n (3) The preparation of (3) was done according to the general procedure using 2,6-pyridinedicarboxylic acid and Zn(NO3)2·6H2O (0.148 g, 0.5 mmol). Yield: 0.220 g, 74%. Anal. Calc. for C25H26N5O8,5Zn: C, 50.22; H, 4.38; N, 11.71. Found: C, 50.16; H, 4.22; N, 11.92%. FT-IR (ν/cm-1): 3373 br, 3138 m, 2989 m, 2902 m, 1627 vs, 1593 s, 1575 m, 1521 vs, 1429 m, 1371 s, 1338 m, 1313 m, 1280 m, 1247 m, 1186 m, 1130 s, 1113 m, 1071 vs, 1036 m, 1008 m, 968 m, 953 m, 912 m, 857 w, 826 s, 774 m, 765 m, 731 m, 690 m, 674 w, 659 w.
[Ni<SUB>2</SUB>(4,4'-bis(1-imidazolyl)biphenyl)(2,6-pyridinedicarboxylate)<SUB>2</SUB>(water)<SUB>4</SUB>][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
General procedure: To a solution of the pyridinedicarboxylic acid (0.084g, 0.5 mmol) in distilled water (8 mL), NaOH (0.040 g, 1.0 mmol) was added and stirred for 5 min. Then the hexahydrated metal nitrate salt (0.5 mmol) and <strong>[855766-92-6]4,4′-bis(1-imidazolyl)biphenyl</strong> (0.143 g, 0.5 mmol) were added. The mixture was placed and sealed in a Teflon-lined stainless steel vessel (10 mL), heated at 160C for 3 days and cooled to room temperature with the rate of 0.06C/min. The obtained crystals were filtered, washed with water and ethanol then dried in air.
[Cu2(2-ethyl-1H-benzimidazole)2(dipicolinate)2]*0.5H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Stage #1: 2-ethylbenzimidazole; water; copper(II) acetate monohydrate In neat (no solvent) at 20℃; for 0.5h;
Stage #2: Pyridine-2,6-dicarboxylic acid In neat (no solvent) Reflux;
General procedure: The synthesis of the complexes [Cu(bzim)(dipic)(MeOH)] (1), [Cu2(2-Etbzim)2(dipic)2]n·0.5nH2O (2) and [Cu2(2-iPrbzim)2(dipic)2]n (3) was carried out in the following manner. To a water (40 cm3, complex 2) or a methanol (40 cm3, complexes 1 and 3) solution of copper(II) acetate monohydrate (0.15 g, 0.75 mmol) was added 1-H-benzimidazole (for 1, 0.09 g, 0.75 mmol), 2-ethyl-1-H-benzimidazole (for 2, 0.22 g, 1.5 mmol) or 2-isopropyl-1-H-benzimidazole (for 3, 0.24 g, 1.5 mmol). The mixture was stirredfor 30 min at ambient temperature to obtain a homogeneous solution, then further treated with dipicolinic acid (0.125 g, 0.75 mmol) and heated under reflux. The resulting blue or violet-blue solutions were cooled to ambient temperature, filtered, and left to crystallize.
General procedure: A mixture of Co(NO3)26H2O (0.20 mmol, 0.058 g), <strong>[855766-92-6]bibp</strong> (0.20 mmol,0.057 g), H2pdc (0.20 mmol, 0.033 g), DMF (5 mL) and H2O (5 mL) wasstirred for 0.5 h under ultrasonic conditions. And then the solution wastransformed into the Teflon-lined stainless steel vessel (25 mL), sealed,and heated to 130 C for 72 h by the temperature controller. Subsequently,the vessel was cooled to the room temperature at the degree of 5C h1. Red crystals were obtained (yield: 51% based on Co(NO3)26H2O). Anal. Calcd for C32H28N6O12Co2 (%): C, 47.64; H, 3.50; N,10.43. Found (%): C, 47.37; H, 3.22; N, 10.21. IR (KBr disk, cm1): 3224(m), 3144 (m), 3122 (m), 1639 (vs), 1610 (vs), 1591 (s), 1575 (s), 1517(s), 1428 (m), 1367 (s), 1322 (s), 1287 (s), 1191 (m), 1123 (m), 1075 (s),1034 (m), 1022 (w), 963 (m), 918 (w), 861 (w), 841 (w), 838 (m), 768(s), 739 (s), 694 (s), 656 (s), 524 (s).
A mixture of Co(NO3)26H2O (0.20 mmol, 0.058 g), <strong>[855766-92-6]bibp</strong> (0.20 mmol,0.057 g), H2pdc (0.20 mmol, 0.033 g), DMF (5 mL) and H2O (5 mL) wasstirred for 0.5 h under ultrasonic conditions. And then the solution wastransformed into the Teflon-lined stainless steel vessel (25 mL), sealed,and heated to 130 C for 72 h by the temperature controller. Subsequently,the vessel was cooled to the room temperature at the degree of 5C h1. Red crystals were obtained (yield: 51% based on Co(NO3)26H2O). Anal. Calcd for C32H28N6O12Co2 (%): C, 47.64; H, 3.50; N,10.43. Found (%): C, 47.37; H, 3.22; N, 10.21. IR (KBr disk, cm1): 3224(m), 3144 (m), 3122 (m), 1639 (vs), 1610 (vs), 1591 (s), 1575 (s), 1517(s), 1428 (m), 1367 (s), 1322 (s), 1287 (s), 1191 (m), 1123 (m), 1075 (s),1034 (m), 1022 (w), 963 (m), 918 (w), 861 (w), 841 (w), 838 (m), 768(s), 739 (s), 694 (s), 656 (s), 524 (s).
General procedure: A mixture of pyridine-2,6-dicarboxylic acid (2a, 83.5 mg, 0.5mmol, 1.0 equiv) and ethyl propiolate (3a, 157 mg, 1.6 mmol,3.2 equiv) was added a 10 mL tube along with a magnetic stirbar, and then 2 mL 1,4-dioxane was added. The tube was stirredand refluxed in oil bath at 80 C. Subsequently, N,N-dimethylbenzylamine(1a, 202 mg, 1.5 mmol, 3 equiv) solved in 1 mL1,4-dioxane was added to the tube slowly for 10 min. And thetube was stirred again and refluxed at 80 C for 12 h. After theremoval of the volatiles in vacuo, the crude residue was loadedon a silica gel (100-200 mesh) column and flashed with 20%ethyl acetate in petroleum ether to afford the desired product4aa in 81% yield.
2.2 Synthesis of[(2,6-CO2)2C5H3NSnBu2(H2O)]2·CHCl3 (1)
A methanolic solution containing 0.20 g (1.20 mmol) of2,6-pyridinedicarboxylic acid, was added to a chloroformsolution which contained 0.21 g (0.71 mmol) of di(n-butyl)dimethoxystannane. The mixture was stirred at room temperature for more than 4 h. After 72 h of slowevaporation of the solution, colorless crystals suitablefor single-crystal X-ray structure determination werecollected within the solvent and characterized as [(2,6-CO2)2C5H3NSnBu2(H2O)]2·CHCl3; yield: 70%; m.p.230 °C. - IR (ATR, cm-1): 1667 ν(O-C-O)asym, 1423 ν(O-C-O)sym, 1617, 1588 ν(C=C/C=N)asym, 689 ν(SnC2)asym, 439 w,518 m ν(Sn-O)/ν(Sn-N). - 1H NMR (CDCl3, ppm): δ = 8.43(t, p-C5H3, 1H), 8.26 (d, m-C5H3, 2H), 3.43 (s, H2O), 0.90(t, CH3), 1.84 (t, α-CH2), 1.54-1.84 (m, β-CH2), 1.36 (m,γ-CH2). - 13C NMR (CDCl3, ppm): δ = 25.8 (α-CH2), 25.6(β-CH2), 25.3 (γ-CH2), 13.6 (CH3), 176 (COO), 125.4-147.2 (m,Ar). - Anal. calcd. for C31H47Cl3N2O10Sn2 (951.4913 g mol-1):C 39.13, H 4.98, N 2.94; found C 39.46, H 4.86, N 3.10.
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