* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Chemical Physics, 2016, vol. 472, p. 173 - 184
14
[ 91-63-4 ]
[ 100-26-5 ]
Reference：
[1] Journal of the American Pharmaceutical Association (1912-1977), 1944, vol. 33, p. 223
[2] Patent: US2513099, 1947, ,
15
[ 589-93-5 ]
[ 100-26-5 ]
Reference：
[1] Chemische Berichte, 1904, vol. 37, p. 2063[2] Chem. Zentralbl., 1903, vol. 74, # I, p. 1034
[3] Chemische Berichte, 1887, vol. 20, p. 136
[4] Journal of the Chemical Society, 1902, vol. 81, p. 449[5] Journal of the Chemical Society, 1903, vol. 83, p. 764
[6] Monatshefte fuer Chemie, 1880, vol. 1, p. 2,41, 46
[7] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1995, vol. 31, # 1, p. 80 - 85[8] Khimiya Geterotsiklicheskikh Soedinenii, 1995, # 1, p. 90 - 96
Reference：
[1] Memoirs of the Institute of Scientific and Industrial Research, Osaka University, 1950, vol. 7, p. 127,131[2] Chem.Abstr., 1951, p. 9054
19
[ 91-63-4 ]
[ 7664-93-9 ]
[ 7697-37-2 ]
[ 100-26-5 ]
Reference：
[1] Journal of the American Pharmaceutical Association (1912-1977), 1944, vol. 33, p. 223
Stage #1: With oxalyl dichloride In dichloromethane at 20℃; for 16.33 h; Stage #2: at 0℃; for 0.25 h; Stage #3: With sodium hydrogencarbonate In water; ethyl acetate
To a suspension of pyridine-2,5-dicarboxylic acid (20 g, 120 mmol) in dichloromethane (396 mL) and DMF (6.6 mL) was added oxalyl chloride (60.96 g, 480 mmol) dropwise over 20 minutes. After 16 hours at ambient temperature, the reaction mixture was concentrated in vacuo and the residue azeotroped with toluene. The residue was taken up in cold (00C) methanol (276 mL) and stirred for 15 minutes. The resultant solution was concentrated in vacuo and the residue taken up in ethyl acetate. The mixture was washed with a saturated aqueous solution of sodium bicarbonate, water and brine. A portion of the product was collected as a white precipitate. The organic phase was isolated, dried (Na2SO4), filtered and concentrated in vacuo to afford the title compound as a white solid (combined material obtained : 22.93 g, 98percent). LCMS (method B): Rx = 2.48 min, [M+H]+ = 196.
98%
at 0 - 80℃; for 4 h; Inert atmosphere
SOCl2 (28.5 mL, 0.24 mol) was added slowly to a stirred solution of compound 36 (10 g, 59.9 mmol)in methanol (100 mL) at 0 °C. After the addition, the solution was stirred at 80 °C for 4 h and thenconcentrated via rotary evaporator to get compound 37 (11.4 g, 98percent).
83%
Stage #1: for 16 h; Heating / reflux Stage #2: With sodium hydrogencarbonate In water
Dimethyl-2,5-pyridinedicarboxylate Dimethyl-2,5-pyridinedicarboxylate (inspired from Isagawa, K.; Kawai, M.; Fushizaki, Y. Nippon Kagaku Zasshi, 1967, 88, (5), 553-6; Dawson, M. I.; Cha, R.; Hobbs, P. D.; Chao, W-r; Schiff, L. J. J. Med. Chem., 1983, 26, 1282-1293; and Hull, K. G.; Visnick, M.; Sheffrom, A. Tetrahedron 1997, 53, 12405-12414) was prepared as described below. 2,5-pyridinedicarboxylic acid (30 g, 0.182 moles) and methanol (300 mL) were mixed together in a 1 L round bottom flask connected to a funnel containing sulfuric acid conc. (16 mL, 0.285 moles). The acid was added dropwise over a period of 30 min, and then the funnel was removed and replaced with a condenser. The mixture was heated at reflux for 16 h which becomes a brown and later a yellow solution. After the reaction cooled to r.t., the slurry was poured in 500 mL of ice water. Sodium bicarbonate solid (30 g) was added to neutralize the pH. The reaction mixture was concentrated with evaporation in a vacuum. The slurry was dissolved with water/chloroform and the compound processed by extraction. The organic layer was dried with brine and then MgSO4 before solvents were evaporated under reduced pressure to yield a pale yellow solid (29.05 g, 83percent). NMR 1H 300 MHz, CDCl3 (δ, ppm): 9.29 (dd, J=1.5 Hz and 0.6 Hz, 1H, CH), 8.42 (dd, J=6 Hz and 2.1 Hz, 1H, CH), 8.19 (dd, J=7.2 Hz and 0.9 Hz, 1H, CH), 4.02 (s, 3H, CH3), 3.97 (s, 3H, CH3).
83%
Stage #1: for 16.5 h; Heating / reflux
Dimethyl-2,5-pyridinedicarboxylate. The compound was synthesised from a procedures from Isagawa, K., et al., Nippon Kagaku Zasshi, 88(5), 553-6, 1967, Dawson, M. I., et al., J. Med. Chem. 26:1282-1293, 1983, and Hull, K. G., et al., Tetrahedron 53:12405-12414, 1997. 2,5-pyridinedicarboxylic acid (30 g, 0.182 moles) and methanol (300 mL) were mixed together in a 1 L round bottom flask connected to a funnel containing sulfuric acid conc. (16 mL, 0.285 moles). The acid was added dropwise over a period of 30 min, and then the funnel was removed and replaced with a condenser. The mixture was heated at reflux for 16 h which becomes a brown and later a yellow solution. After the reaction cooled to r.t., the slurry was poured in 500 mL of ice water. Sodium bicarbonate solid (30 g) was added to neutralize the pH. The reaction mixture was concentrated with evaporation in a vacuum. The slurry was dissolved with water/chloroform and the compound processed by extraction. The organic layer was dried with brine and then MgSO4 before solvents were evaporated under reduced pressure to yield a pale yellow solid (29.05 g, 83percent). NMR 1H 300 MHz, CDCl3 (δ, ppm): 9.29 (dd, J=1.5 Hz and 0.6 Hz, 1H, CH), 8.42 (dd, J=6 Hz and 2.1 Hz, 1H, CH), 8.19 (dd, J=7.2 Hz and 0.9 Hz, 1H, CH), 4.02 (s, 3H, CH3), 3.97 (s, 3H, CH3).
78%
at 0℃; for 3 h; Reflux
10311] Thionyl chloride (2.2 mE) was added dropwise to MeOH (14 mE) while stirring on ice. 2,5-Pyridinedicarbox- ylic acid (1.0 g, 6.0 mmoles) was added and the reaction heated at reflux for 3 hr. The reaction was cooled and the solvent removed under reduced pressure. The resulting residue was dissolved in DCM (15 mE), afier which saturated Na2CO3 (15 mE) was added while stirring on ice. Theaqueous layer was extracted with DCM (3x 15 mE), and the combined organics were washed with saturated Na2CO3 (2x40 mE), dried over Na2SO4(s), and concentrated under reduced pressure to afford the title compound (915 mg, 78percent) as a pale yellow solid. ‘H NMR (500 MHz, CDC13) ö 9.32 (dd, J=0.5, 2.0 Hz, 1H), 8.47 (dd, J=2.0, 8.0 Hz, 1H), 8.23 (dd, J=0.5, 8.0 Hz, 1H), 4.06 (s, 3H), 4.01 (s, 3H); ‘3C NMR (125 MHz, CDC13) ö 165.0, 164.9, 150.8, 150.8, 138.4, 128.6, 124.7, 53.3, 52.8; HRMS (ESI) mlz 196.0600 [calc’d for C9H,QNO4 (M+H) 196.0605].
Reference：
[1] Patent: WO2009/85983, 2009, A1, . Location in patent: Page/Page column 65
[2] Molecules, 2014, vol. 19, # 1, p. 102 - 121
[3] European Journal of Organic Chemistry, 2013, # 3, p. 541 - 549
[4] Tetrahedron Letters, 2005, vol. 46, # 6, p. 967 - 969
[5] Patent: US2007/231300, 2007, A1, . Location in patent: Page/Page column 13-14
[6] Patent: US2008/103192, 2008, A1, . Location in patent: Page/Page column 14
[7] European Journal of Organic Chemistry, 2010, # 1, p. 174 - 182
[8] Patent: US2016/280701, 2016, A1, . Location in patent: Paragraph 0309; 0310; 0311
[9] Journal of the Chemical Society, 1902, vol. 81, p. 449[10] Journal of the Chemical Society, 1903, vol. 83, p. 764
[11] Monatshefte fuer Chemie, 1913, vol. 34, p. 521
[12] Phytochemistry (Elsevier), 1984, vol. 23, # 6, p. 1225 - 1228
[13] Tetrahedron, 2005, vol. 61, # 45, p. 10748 - 10756
[14] Journal of the American Chemical Society, 2003, vol. 125, # 1, p. 296 - 304
[15] Bioorganic and Medicinal Chemistry, 2012, vol. 20, # 9, p. 2950 - 2956
[16] RSC Advances, 2014, vol. 4, # 35, p. 18100 - 18107
[17] Patent: WO2016/109215, 2016, A1, . Location in patent: Page/Page column 58
[18] Patent: WO2018/140809, 2018, A1, . Location in patent: Paragraph 00409
23
[ 100-26-5 ]
[ 881-86-7 ]
Yield
Reaction Conditions
Operation in experiment
98.3%
With thionyl chloride In methanol for 4 h; Reflux
A solution of compound 23 (10 g, 59.9 mmol)Dissolved in methanol (lOOmL)In the ice bath slowly addedTo a solution of dichlorosulfoxide (28.5 mL, 239.5 mmol)The reaction was refluxed for 4 h, Followed by spin-drying to give compound 24 (11.4 g, 98.3percent).
80%
With thionyl chloride In methanol; water
PREPARATION 1 dimethyl Pyridine-2,5-dicarboxylate To a stirred slurry of 2,5-pyridinedicarboxylic acid (2407 g; 14.4 mol) in methanol (8.0 liter) at -5° to -10°C, thionylchloride (3430 g; 2.10 liters; 28.8 mol) was added dropwise while maintaining the temperature in the -5° to -10°C range. After completing the addition, the reaction was allowed to warm to ambient temperature, and stirred for 18 hours. The resulting solution was concentrated in vacuo to a volume of 4 liters, and an equal volume of water was added. The PH of the well-stirred mixture was then adjusted to 10 with saturated aqueous sodium carbonate. Solids were removed by filtration. The organic layer of the filtrate was separated, washed with water (8 liters), and dried in vacuo to afford the title compound (2250 g; 80percent yield) as an amorphous solid.
80%
With thionyl chloride In methanol; water
PREPARATION 1 Dimethyl Pyridine-2,5-dicarboxylate To a stirred slurry of 2,5-pyridinedicarboxylic acid (2407 g; 14.4 mol) in methanol (8.0 liter) at -5° to -10° C. thionylchloride (3430 g; 2.10 liters; 28 8 mol) was added dropwise while maintaining the temperature in the -5° to -10° C. range. After completing the addition, the reaction was allowed to warm to ambient temperature, and stirred for 18 hours. The resulting solution was concentrated in vacuo to a volume of 4 liters, and an equal volume of water was added. The pH of the well-stirred mixture was then adjusted to 10 with saturated aqueous sodium carbonate. Solids were removed by filtration. The organic layer of the filtrate was separated, washed with water (8 liters), and dried in vacuo to afford the title compound (2250 g; 80percent yield) as an amorphous solid.
80%
With thionyl chloride In methanol; water
PREPARATION 1 Dimethyl Pyridine-2,5-dicarboxylate To a stirred slurry of 2,5-pyridinedicarboxylic acid (2407 g; 14.4 mol) in methanol (8.0 liter) at -5° to -10° C., thionylchloride (3430 g; 2.10 liters; 28.8 mol) was added dropwise while maintaining the temperature in the -5° to -10° C. range. After completing the addition, the reaction was allowed to warm to ambient temperature, and stirred for 18 hours. The resulting solution was concentrated in vacuo to a volume of 4 liters, and an equal volume of water was added. The pH of the well-stirred mixture was then adjusted to 10 with saturated aqueous sodium carbonate. Solids were removed by filtration. The organic layer of the filtrate was separated, washed with water (8 liters), and dried in vacuo to afford the title compound (2250 g; 80percent yield) as an amorphous solid.
Reference：
[1] Patent: CN104418811, 2017, B, . Location in patent: Paragraph 0234-0236
[2] Patent: EP536173, 1995, B1,
[3] Patent: US5616585, 1997, A,
[4] Patent: US5122525, 1992, A,
24
[ 67-56-1 ]
[ 100-26-5 ]
[ 881-86-7 ]
[ 17874-76-9 ]
Reference：
[1] Journal of the American Chemical Society, 2005, vol. 127, # 34, p. 11914 - 11915
25
[ 100-26-5 ]
[ 64-17-5 ]
[ 5552-44-3 ]
Yield
Reaction Conditions
Operation in experiment
75%
for 18 h; Reflux
Concentrated sulfuric acid (3.9 mL, 71.6 mmol) was added dropwise over 15 minutes to a stirred suspension of 2,5-pyridinedicarboxylic acid (3.0 g, 17.9 mol) in absolute ethanol (10 mL) and the resulting mixture heated to reflux for 18 hours. The solution was allowed to cool to room temperature and the solvents evaporated under reduced pressure. Saturated NaHCC>3 solution was added to the residue to adjust the pH to -8 then the aqueous phase was extracted with EtOAc (4 x 50 mL). The combined organic extracts were washed with brine (30 mL), dried (Na2S04) and evaporated under reduced pressure to leave the title compound (3.0 g, 75percent) which was used without further purification.
67%
for 4 h; Reflux
Diethyl pyridine-2,5-dicarboxylate (5.3)Pyridine-2,5-dicarboxylic acid (20.0 g, 120 mmol) was dissolved in ethanol (200 mL) and treated with concentrated solution of sulfuric acid (2.0 mL, 36 mmol) in ethanol (20 mL). The reaction was heated under reflux for 4hrs, concentrated and dissolved in EtOAc (10 mL). The mixture was washed with water (50mL), brine (50 mL), dried over sodium sulfate, filtered and evapourated to afford diethyl pyridine-2,5-dicarboxylate (18 g, 67 percent). 1 H NMR (400MHz CDCI3) δΗ ppm 1 .25 (t, 3H), 4.3 (q, 2H), 8.2 (d, 1 H), 8.4 (d, 1 H), 9.4 (s, 1 H).
26.61 g
With sulfuric acid In water at 78℃; for 58 h;
(0201) 2,5-pyridinedicarboxylic acid (25.08 g; 150 mmol) was added to ethanol (1,800 mL). Aqueous sulfuric acid (1.32 g) was added. The mixture was heated at reflux (about 78° C.) for 58 hours, during which time water was removed from the reaction. The reaction progress was monitored using NMR spectroscopy. After the 2,5-diethyl-2,5-pyridinedicarboxylate had been formed in >97percent purity by NMR, the reaction mixture was allowed to cool to ambient temperature and was extracted with 2-methyltetrahydrofuran. The combined organic layers were washed with a saturated aqueous brine solution and deionised water, and dried (MgSO4). The organics were filtered and the volatiles were removed in vacuo to afford the title compound (26.61 g; 120 mmol; >99percent conversion by GC).
Reference：
[1] Bioorganic and Medicinal Chemistry Letters, 1996, vol. 6, # 24, p. 3025 - 3028
[2] Journal of Porphyrins and Phthalocyanines, 2010, vol. 14, # 6, p. 469 - 480
[3] Dalton Transactions, 2015, vol. 44, # 35, p. 15391 - 15395
[4] European Journal of Organic Chemistry, 2010, # 1, p. 174 - 182
[5] CrystEngComm, 2011, vol. 13, # 8, p. 2915 - 2922
[6] Patent: WO2018/197714, 2018, A1, . Location in patent: Page/Page column 115; 116
[7] Liebigs Annalen der Chemie, 1981, # 12, p. 2164 - 2179
[8] Journal of Medicinal Chemistry, 1983, vol. 26, # 9, p. 1282 - 1293
[9] Patent: WO2013/72903, 2013, A1, . Location in patent: Page/Page column 67
[10] Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation), 1959, vol. 32, p. 2820; engl. Ausg. S. 2904
[11] European Journal of Medicinal Chemistry, 2004, vol. 39, # 10, p. 889 - 895
[12] Angewandte Chemie - International Edition, 2015, vol. 54, # 48, p. 14570 - 14574[13] Angew. Chem., 2015,
[14] Patent: US5350772, 1994, A,
[15] Patent: US2018/148752, 2018, A1, . Location in patent: Paragraph 0200-0201
26
[ 100-26-5 ]
[ 5552-44-3 ]
Reference：
[1] Arhiv za Kemiju, 1946, vol. 18, p. 3,6[2] Chem.Abstr., 1948, p. 3398
[3] Kobunshi Kagaku, 1958, vol. 15, p. 839,844[4] Chem.Abstr., 1960, p. 22636
[5] Synthesis, 1999, # 4, p. 597 - 602
27
[ 100-26-5 ]
[ 39977-41-8 ]
Reference：
[1] Journal of Medicinal Chemistry, 1983, vol. 26, # 9, p. 1282 - 1293
Progress toward analog 18 has been made as follows. 2,5- Pyridinedicarboxylic acid (58) was preferentially esterified according to literature protocols66 by reflux in methanol with catalytic sulfuric acid for 2 hours to the mono- methyl ester (59) in 42percent recovered yield after recrystallization from water. The monomethyl ester 59 was refluxed in excess thionyl chloride to effect its conversion to the acid chloride (60), and 60 was used to acylate 35 by reflux in DCM with excess aluminum trichloride (Scheme 10).
33%
for 2 h; Heating / reflux
EXAMPLE 83a Pyridine-2,5-dicarboxylic acid-2-methyl ester To a suspension of pyridine-2,5-dicarboxylic acid (4.2 g, 25.1 mmol) (Aldrich) in methanol (50 mL) was added concentrated sulfuric acid (1.5 g, 15.3 mmol) (Aldrich). The mixture was heated at refluxing for 2 hours. The crude was cooled down to room temperature and poured into water (250 mL). The precipitate formed was collected and washed with methanol to give pyridine-2,5-dicarboxylic acid-2-methyl ester as a grey solid. (Yield 1.5 g, 33percent).
Reference：
[1] Patent: WO2011/103321, 2011, A1, . Location in patent: Page/Page column 23
[2] Patent: US2006/293319, 2006, A1, . Location in patent: Page/Page column 47
[3] Patent: WO2007/70173, 2007, A2, . Location in patent: Page/Page column 145-146
[4] European Journal of Inorganic Chemistry, 2010, # 13, p. 1913 - 1928
[5] Patent: WO2012/121973, 2012, A1, . Location in patent: Page/Page column 89
[6] Patent: WO2008/156715, 2008, A1, . Location in patent: Page/Page column 66
[7] Angewandte Chemie - International Edition, 2018, vol. 57, # 22, p. 6572 - 6576[8] Angew. Chem., 2018, vol. 130, p. 6682 - 6686,5
31
[ 100-26-5 ]
[ 17874-76-9 ]
Reference：
[1] Patent: US4273779, 1981, A,
32
[ 100-26-5 ]
[ 7664-93-9 ]
[ 17874-76-9 ]
Reference：
[1] Patent: US6479519, 2002, B1,
33
[ 67-56-1 ]
[ 100-26-5 ]
[ 881-86-7 ]
[ 17874-76-9 ]
Reference：
[1] Journal of the American Chemical Society, 2005, vol. 127, # 34, p. 11914 - 11915
34
[ 100-26-5 ]
[ 17874-79-2 ]
Reference：
[1] Journal of the American Chemical Society, 2005, vol. 127, # 34, p. 11914 - 11915
[2] Tetrahedron, 2005, vol. 61, # 45, p. 10748 - 10756
[3] Tetrahedron Letters, 2005, vol. 46, # 6, p. 967 - 969
[4] Patent: US2016/280701, 2016, A1,
[5] Patent: US2008/103192, 2008, A1,
35
[ 100-26-5 ]
[ 50501-35-4 ]
Reference：
[1] Journal of Medicinal Chemistry, 1983, vol. 26, # 9, p. 1282 - 1293
[2] Patent: US2008/103192, 2008, A1,
Reference：
[1] European Journal of Inorganic Chemistry, 2010, # 13, p. 1913 - 1928
38
[ 100-26-5 ]
[ 337904-92-4 ]
Yield
Reaction Conditions
Operation in experiment
45.9%
With sodium hydroxide; triethylamine In <i>tert</i>-butyl alcohol
(A) 5-[(tert-Butoxycarbonyl)amino]nicotinic acid 5-Pyridinedicarboxylic acid (5.00 g, 29.9 mmol) was suspended in t-butanol (35 ml), and the solution was added dropwise with triethylamine (8.34 ml, 59.8 mmol) and diphenylphosphoric acid azide (7.10 ml, 32.9 mmol), and heated under reflux for 3 hours. The reaction mixture was adjusted to a pH lower than 10 by addition of 1 N aqueous sodium hydroxide under ice cooling, and then washed with ether. The reaction mixture was again cooled with ice, and adjusted to about pH 4 with 1 N aqueous sodium hydroxide. The deposited solids were collected by filtration, and washed with water and ether to obtain the title compound as white powder (3.27 g, 45.9percent). 1H-NMR (DMSO-d6) δ: 1.49 (9H, s), 8.45 (1H, s), 8.66 (1H, s), 8.75 (1H, s), 9.83 (1H, br)
To a suspension of pyridine-2,5-dicarboxylic acid (20 g, 120 mmol) in dichloromethane (396 mL) and DMF (6.6 mL) was added oxalyl chloride (60.96 g, 480 mmol) dropwise over 20 minutes. After 16 hours at ambient temperature, the reaction mixture was concentrated in vacuo and the residue azeotroped with toluene. The residue was taken up in cold (00C) methanol (276 mL) and stirred for 15 minutes. The resultant solution was concentrated in vacuo and the residue taken up in ethyl acetate. The mixture was washed with a saturated aqueous solution of sodium bicarbonate, water and brine. A portion of the product was collected as a white precipitate. The organic phase was isolated, dried (Na2SO4), filtered and concentrated in vacuo to afford the title compound as a white solid (combined material obtained : 22.93 g, 98%). LCMS (method B): Rx = 2.48 min, [M+H]+ = 196.
98%
With thionyl chloride; at 0 - 80℃; for 4h;Inert atmosphere;
SOCl2 (28.5 mL, 0.24 mol) was added slowly to a stirred solution of compound 36 (10 g, 59.9 mmol)in methanol (100 mL) at 0 C. After the addition, the solution was stirred at 80 C for 4 h and thenconcentrated via rotary evaporator to get compound 37 (11.4 g, 98%).
83%
Dimethyl-2,5-pyridinedicarboxylate Dimethyl-2,5-pyridinedicarboxylate (inspired from Isagawa, K.; Kawai, M.; Fushizaki, Y. Nippon Kagaku Zasshi, 1967, 88, (5), 553-6; Dawson, M. I.; Cha, R.; Hobbs, P. D.; Chao, W-r; Schiff, L. J. J. Med. Chem., 1983, 26, 1282-1293; and Hull, K. G.; Visnick, M.; Sheffrom, A. Tetrahedron 1997, 53, 12405-12414) was prepared as described below. 2,5-pyridinedicarboxylic acid (30 g, 0.182 moles) and methanol (300 mL) were mixed together in a 1 L round bottom flask connected to a funnel containing sulfuric acid conc. (16 mL, 0.285 moles). The acid was added dropwise over a period of 30 min, and then the funnel was removed and replaced with a condenser. The mixture was heated at reflux for 16 h which becomes a brown and later a yellow solution. After the reaction cooled to r.t., the slurry was poured in 500 mL of ice water. Sodium bicarbonate solid (30 g) was added to neutralize the pH. The reaction mixture was concentrated with evaporation in a vacuum. The slurry was dissolved with water/chloroform and the compound processed by extraction. The organic layer was dried with brine and then MgSO4 before solvents were evaporated under reduced pressure to yield a pale yellow solid (29.05 g, 83%). NMR 1H 300 MHz, CDCl3 (delta, ppm): 9.29 (dd, J=1.5 Hz and 0.6 Hz, 1H, CH), 8.42 (dd, J=6 Hz and 2.1 Hz, 1H, CH), 8.19 (dd, J=7.2 Hz and 0.9 Hz, 1H, CH), 4.02 (s, 3H, CH3), 3.97 (s, 3H, CH3).
83%
Dimethyl-2,5-pyridinedicarboxylate. The compound was synthesised from a procedures from Isagawa, K., et al., Nippon Kagaku Zasshi, 88(5), 553-6, 1967, Dawson, M. I., et al., J. Med. Chem. 26:1282-1293, 1983, and Hull, K. G., et al., Tetrahedron 53:12405-12414, 1997. 2,5-pyridinedicarboxylic acid (30 g, 0.182 moles) and methanol (300 mL) were mixed together in a 1 L round bottom flask connected to a funnel containing sulfuric acid conc. (16 mL, 0.285 moles). The acid was added dropwise over a period of 30 min, and then the funnel was removed and replaced with a condenser. The mixture was heated at reflux for 16 h which becomes a brown and later a yellow solution. After the reaction cooled to r.t., the slurry was poured in 500 mL of ice water. Sodium bicarbonate solid (30 g) was added to neutralize the pH. The reaction mixture was concentrated with evaporation in a vacuum. The slurry was dissolved with water/chloroform and the compound processed by extraction. The organic layer was dried with brine and then MgSO4 before solvents were evaporated under reduced pressure to yield a pale yellow solid (29.05 g, 83%). NMR 1H 300 MHz, CDCl3 (delta, ppm): 9.29 (dd, J=1.5 Hz and 0.6 Hz, 1H, CH), 8.42 (dd, J=6 Hz and 2.1 Hz, 1H, CH), 8.19 (dd, J=7.2 Hz and 0.9 Hz, 1H, CH), 4.02 (s, 3H, CH3), 3.97 (s, 3H, CH3).
78%
With thionyl chloride; at 0℃; for 3h;Reflux;
10311] Thionyl chloride (2.2 mE) was added dropwise to MeOH (14 mE) while stirring on ice. 2,5-Pyridinedicarbox- ylic acid (1.0 g, 6.0 mmoles) was added and the reaction heated at reflux for 3 hr. The reaction was cooled and the solvent removed under reduced pressure. The resulting residue was dissolved in DCM (15 mE), afier which saturated Na2CO3 (15 mE) was added while stirring on ice. Theaqueous layer was extracted with DCM (3x 15 mE), and the combined organics were washed with saturated Na2CO3 (2x40 mE), dried over Na2SO4(s), and concentrated under reduced pressure to afford the title compound (915 mg, 78%) as a pale yellow solid. ?H NMR (500 MHz, CDC13) oe 9.32 (dd, J=0.5, 2.0 Hz, 1H), 8.47 (dd, J=2.0, 8.0 Hz, 1H), 8.23 (dd, J=0.5, 8.0 Hz, 1H), 4.06 (s, 3H), 4.01 (s, 3H); ?3C NMR (125 MHz, CDC13) oe 165.0, 164.9, 150.8, 150.8, 138.4, 128.6, 124.7, 53.3, 52.8; HRMS (ESI) mlz 196.0600 [calc?d for C9H,QNO4 (M+H) 196.0605].
With sulfuric acid;Inert atmosphere; Reflux;
General procedure: Synthesis of methyl ester derivatives of M6, M7, and M17 was carried out under catalytic esterification conditions as depicted in Scheme 1. To a solution of the appropriate carboxylic acid in methanol few drops of conc. sulfuric acid were added. Subsequently, the reaction mixture was refluxed for 6-10 h. After completion, the volatile solvents were evaporated under reduced pressure and the residue was dissolved in water/ethyl acetate mixture. The aqueous phase was extracted with ethyl acetate and the combined organic phase was washed with 5% sodium bicarbonate, brine, and was dried over anhydrous sodium sulfate. After filtration the desired ester was obtained using flash column chromatography.
With thionyl chloride; at 70℃;
Step 1. Dimethyl pyridine-2.5-dicarboxylate SOCI2 (855 g, 7.2 mol) was added dropwise into the solution of pyridine-2,5-dicarboxylate (500 g, 3.0 mol) in MeOH (5 L) at room temperature. The mixture was stirred at 70 C overnight. After cooling, the mixture was evaporated, and the residue was added EA (5 L), followed by Na2C03 (sat.) until PH>7. The mixture was separated and the aqueous layer was extracted with EA (1 L*3). The combined organic layer was washed with brine, dried over Na2SC>4, filtered and concentrated to give dimethyl pyridine-2,5-dicarboxylate. The product was used for next step without further purification.
Concentrated sulfuric acid (3.9 mL, 71.6 mmol) was added dropwise over 15 minutes to a stirred suspension of 2,5-pyridinedicarboxylic acid (3.0 g, 17.9 mol) in absolute ethanol (10 mL) and the resulting mixture heated to reflux for 18 hours. The solution was allowed to cool to room temperature and the solvents evaporated under reduced pressure. Saturated NaHCC>3 solution was added to the residue to adjust the pH to -8 then the aqueous phase was extracted with EtOAc (4 x 50 mL). The combined organic extracts were washed with brine (30 mL), dried (Na2S04) and evaporated under reduced pressure to leave the title compound (3.0 g, 75%) which was used without further purification.
67%
With sulfuric acid; for 4h;Reflux;
Diethyl pyridine-2,5-dicarboxylate (5.3)<strong>[100-26-5]Pyridine-2,5-dicarboxylic acid</strong> (20.0 g, 120 mmol) was dissolved in ethanol (200 mL) and treated with concentrated solution of sulfuric acid (2.0 mL, 36 mmol) in ethanol (20 mL). The reaction was heated under reflux for 4hrs, concentrated and dissolved in EtOAc (10 mL). The mixture was washed with water (50mL), brine (50 mL), dried over sodium sulfate, filtered and evapourated to afford diethyl pyridine-2,5-dicarboxylate (18 g, 67 %). 1 H NMR (400MHz CDCI3) deltaEta ppm 1 .25 (t, 3H), 4.3 (q, 2H), 8.2 (d, 1 H), 8.4 (d, 1 H), 9.4 (s, 1 H).
With thionyl chloride; triethylamine;
a) Add 50 mL of thionyl chloride to 25 g of pyridene-2,5-dicarboxylic acid and heat the so-formed mixture at reflux for 6 hrs. Remove all volatiles by vacuum distillation to obtain crude di acid chloride. Immerse flask contain diacid chloride in an ice-batch and add 100 mL of absolute ethanol thereto. Slowly add 30 mL of triethlamine to the stirred reaction mixture and continue stirring for 1/2 hr. Add Ethyl acetate/water to stirred reaction mixture and separate the organic layer. Remove the solvent to produce crude product. Re-crystallize crude product from hexane/methylene chloride to give 25 g of the pyridine-2,5-bis(ethylcarboxylate).
26.61 g
With sulfuric acid; In water; at 78℃; for 58h;
(0201) 2,5-pyridinedicarboxylic acid (25.08 g; 150 mmol) was added to ethanol (1,800 mL). Aqueous sulfuric acid (1.32 g) was added. The mixture was heated at reflux (about 78 C.) for 58 hours, during which time water was removed from the reaction. The reaction progress was monitored using NMR spectroscopy. After the 2,5-diethyl-2,5-pyridinedicarboxylate had been formed in >97% purity by NMR, the reaction mixture was allowed to cool to ambient temperature and was extracted with 2-methyltetrahydrofuran. The combined organic layers were washed with a saturated aqueous brine solution and deionised water, and dried (MgSO4). The organics were filtered and the volatiles were removed in vacuo to afford the title compound (26.61 g; 120 mmol; >99% conversion by GC).
With thionyl chloride;N,N-dimethyl-formamide; In toluene; at 70℃;Product distribution / selectivity;
Example 5; (Preparation of Exemplary Compound (8)); 3.1 g of thionyl chloride was added dropwise to a mixture of 1.0 g of 2,5-pyridinedicarboxylic acid and 3 ml of toluene. A few drops of DMF were added, and the mixture was stirred at 70 C. for 2 hours. The reaction solution was added to a solution of 1.64 g of anthranilic acid in 4 ml of DMAc, and the solid obtained was filtered and washed with water, to give 2.3 g of a synthetic intermediate C (yield: 96%).5 ml of acetic anhydride and 5 ml of toluene were added to 1.0 g of the synthetic intermediate C. The mixture was allowed to react under reflux for 10 hours. The mixture was cooled to room temperature, and the solid obtained was filtered and washed with acetone, to give 0.6 g of an exemplary compound (8) (yield: 66%).MS:m/z 370(M+)1H NMR(CDCl3):delta7.61-7.66(2H),delta7.79-7.81(1H),delta7.91-7.93(3H),delta8.29-8.33(2H),delta8.52-8.54(1H),delta8.76-8.79(1H),delta9.73-9.74(1H)lambdamax=346nm(EtOAc)
With thionyl chloride;N,N-dimethyl-formamide; In dichloromethane; for 5h;Heating / reflux;
1) <strong>[100-26-5]Pyridine-2,5-dicarboxylic acid</strong> dibenzyl ester Thionyl chloride (250 mL) and N,N-dimethylformamide (10 mL) were added to 2,5-pyridinedicarboxylic acid (60 g) in methylene chloride (360 mL), and the mixture was refluxed for 5 hours and then cooled in air. The solvent of the reaction mixture was removed under reduced pressure, and toluene was added to the residue. The solvent was again removed through azeotropy under reduced pressure, and the residue was dissolved in methylene chloride (500 mL). At 0C, benzyl alcohol (81.7 mL) in methylene chloride (200 mL) was added dropwise to the solution, and the mixture was stirred for 4 hours at room temperature. Water was added thereto for partitioning the reaction mixture, and the organic layer was washed with saturated aqueous sodium hydrogencarbonate and then dried over sodium sulfate anhydrate. After a filtration step, the solvent was removed under reduced pressure, to thereby give pyridine-2,5-dicarboxylic acid dibenzyl ester as a solid product (65 g, 52%). 1H-NMR (400MHz, CDCl3) delta: 5.42 (2H, s), 5.47(2H,s), 7.38-7.46(10H,m), 8.19(1H,d,J=8.3Hz), 8.44(1H,dd,J=8.2,2.1Hz), 9.35-9.36(1H,m).
With thionyl chloride; In dichloromethane; N,N-dimethyl-formamide; for 5h;Heating / reflux;
1) <strong>[100-26-5]Pyridine-2,5-dicarboxylic acid</strong> dibenzyl ester Thionyl chloride (250 mL) and N, N-dimethylformamide (10 mL) were added to a solution of 2, 5-pyridinedicarboxylic acid (60 g) in dichloromethane (360 mL), and the resultant mixture was heated to reflux for 5 hours. After air cooling, the solvent of the reaction solution was evaporated under reduced pressure, and toluene was added to the residue thus obtained. The resultant mixture was further azeotropically evaporated under reduced pressure, and a residue thus obtained was dissolved in dichloromethane (500 mL). A solution of benzyl alcohol (81.7 mL) in dichloromethane (200 mL) was added dropwise to the solution at 0C, and the mixture was stirred at room temperature for 4 hours. Water was added to the reaction solution, and the mixture was partitioned. The organic layer was washed with a saturated aqueous solution of sodiumhydrogen carbonate, and then was dried over anhydrous sodium sulfate. After separating the organic layer by filtration, the solvent was evaporated under reduced pressure, to obtain pyridine-2,5-dicarboxylic acid dibenzyl ester (65 g, 52%) as a solid. 1H-NMR (400MHz, CDCl3) delta: 5.42 (2H, s), 5.47 (2H, s), 7.38-7.46 (10H, m), 8.19 (1H, d, J=8.3Hz), 8.44 (1H, dd, J=8.2, 2.1Hz), 9.35-9.36 (1H, m).
With thionyl chloride; at 85℃; for 3h;Inert atmosphere;
<strong>[100-26-5]Pyridine-2,5-dicarboxylic acid</strong> (100 mg, 0.59 mmol) was mixed with2 mL of SOCl2. The reaction mixture was refluxed at 85 C for 3 h underN2 to afford pyridine-2,5-dicarbonyl dichloride (PDC). Excess SOCl2 was removed by distillation under high vacuum. 9.54 mg(0.0456 mmol) of pyridine-2,5-dicarbonyl dichloride (PDC) and L-1 (80 mg, 0.114 mmol) were dissolved in 15 mL of CH2Cl2, followed by addition of 1 drop of Et3N. The reaction mixture was stirred at room temperature for 3 h to afford L-3. The obtained product was dried on a rotary evaporator, purified with a silica column (eluent: CH3OH/CH2Cl2, 3:97, v/v), followed by purification using GPC (eluent: CHCl3)and dried in vacuo affording a purple colour solid L-3 in 70.4% yield(50 mg).
With thionyl chloride; N,N-dimethyl-formamide; at 90℃; for 4h;
To a round bottom flask connected with condenser, pyridine-2, 5- dicarboxylic acid (20 mmol, 3.34 g), SOCI2 (60 mmol, 7.14 g) and 5 ml_ of DMF were added and the reaction was carried out at 90C under argon for 4 h. The reaction mixture was then cooled down to room temperature, Et3N (6 equiv. , 1 6.8 ml_) and glycerol carbonate (80 mmol, 9.45 g in 1 2 mL of THF) were added slowly and was further heated at 90C overnight. After the reaction, the excess amount of Et3N, SOCI2 and solvent were removed under vacuum. The product bis((2-oxo-1 ,3-dioxolan-4-yl)methyl)pyridine-2,5- dicarboxylate was isolated as a white solid, filtered and washed with water (30 mL, 2 times) and with Et20 (30 mL, 2 times) to give 4.61 g (1 2.6 mmol) of pure product (63%) which was characterized by 1 H, 13C-NMR and HRMS. 1 H- NMR (CDCb, 400 MHz) : 9.1 9 (dd, J = 2.1 , 0.8 Hz, 1 H), 8.49 (dd, J = 8.2, 2.2 Hz, 1 H), 8.21 (dd, J = 8.1 , 0.8 Hz, 1 H), 5.36 - 5.05 (m, 2H), 4.84 - 4.31 (m, 8H). 13C NMR (CDCb, 100 MHz): d= 168.8, 168.6, 159.9, 159.8, 1 55.5, 1 55.4, 143.8, 1 33.2, 1 30.3, 79.4, 79.3, 71 .4, 71 .3, 70.2, 70.1 . HR-MS (ESI) (M+H)+ m/z Calcd. for CisHuNOio: 368.061 2. Found: 368.061 0.
To a mixture of pyridine-2, 5-dicarboxylic acid (30.00 g, 179.51 mmol) in ethanol (380 ml, 179.51 mmol) was slowly added sulfuric acid (3.00 ml, 56.28 mmol) and the mixture was heated to reflux for 7 hours. The solution was cooled in an ice bath 5 and diluted with water (400 mL) . The resulting suspension was stirred overnight at room temperature. The solid was filtered and washed with water. The solid was triturated in 300 ml of refluxing EtOH for 2 hours and then cooled in an ice bath and the solid was filtered to give 6- (ethoxycarbonyl) nicotinic acid 0 (16.05 g, 46% yield): 1H NMR (400 MHz, DMSO-d6) δ 1.29 (t, J = 7.0 Hz, 3H), 4.29-4.35 (m, 2H), 8.10 (d, J = 8.0 Hz, IH), 8.39 (d, J - 8.2 Hz, IH), 9.11 (s, IH) .
46%
With sulfuric acid at 18 - 25℃; Heating / reflux;
To a mixture of pyridine-2, 5-dicarboxylic acid (30.00 g, 179.51 mmol) in ethanol (380 ml, 179.51 mmol) was slowly added sulfuric acid (3.00 ml, 56.28 mmol) and the mixture was heated to reflux for 7 hours. The solution was cooled in an ice bath 5 and diluted with water (400 mL) . The resulting suspension was stirred overnight at room temperature. The solid was filtered and washed with water. The solid was triturated in 300 ml of refluxing EtOH for 2 hours and then cooled in an ice bath and the solid was filtered to give 6- (ethoxycarbonyl) nicotinic acid 0 (16.05 g, 46% yield): 1H NMR (400 MHz, DMSO-d6) δ 1.29 (t, J = 7.0 Hz, 3H), 4.29-4.35 (m, 2H), 8.10 (d, J = 8.0 Hz, IH), 8.39 (d, J - 8.2 Hz, IH), 9.11 (s, IH) .
poly[(1,7-dihydrobenzo{1,2-d:4,5-d'}-bisimidazole-2,6-diyl)-2,5-pyridine]; monomer: 1,2,4,5-tetraminobenzene tetrahydrochloride; monomer: 2,5-pyridinedicarboxylic acid[ No CAS ]
With thionyl chloride; In methanol; for 4h;Reflux;
A solution of compound 23 (10 g, 59.9 mmol)Dissolved in methanol (lOOmL)In the ice bath slowly addedTo a solution of dichlorosulfoxide (28.5 mL, 239.5 mmol)The reaction was refluxed for 4 h, Followed by spin-drying to give compound 24 (11.4 g, 98.3percent).
80%
With thionyl chloride; In methanol; water;
PREPARATION 1 dimethyl Pyridine-2,5-dicarboxylate To a stirred slurry of 2,5-pyridinedicarboxylic acid (2407 g; 14.4 mol) in methanol (8.0 liter) at -5° to -10°C, thionylchloride (3430 g; 2.10 liters; 28.8 mol) was added dropwise while maintaining the temperature in the -5° to -10°C range. After completing the addition, the reaction was allowed to warm to ambient temperature, and stirred for 18 hours. The resulting solution was concentrated in vacuo to a volume of 4 liters, and an equal volume of water was added. The PH of the well-stirred mixture was then adjusted to 10 with saturated aqueous sodium carbonate. Solids were removed by filtration. The organic layer of the filtrate was separated, washed with water (8 liters), and dried in vacuo to afford the title compound (2250 g; 80percent yield) as an amorphous solid.
80%
With thionyl chloride; In methanol; water;
PREPARATION 1 Dimethyl Pyridine-2,5-dicarboxylate To a stirred slurry of 2,5-pyridinedicarboxylic acid (2407 g; 14.4 mol) in methanol (8.0 liter) at -5° to -10° C. thionylchloride (3430 g; 2.10 liters; 28 8 mol) was added dropwise while maintaining the temperature in the -5° to -10° C. range. After completing the addition, the reaction was allowed to warm to ambient temperature, and stirred for 18 hours. The resulting solution was concentrated in vacuo to a volume of 4 liters, and an equal volume of water was added. The pH of the well-stirred mixture was then adjusted to 10 with saturated aqueous sodium carbonate. Solids were removed by filtration. The organic layer of the filtrate was separated, washed with water (8 liters), and dried in vacuo to afford the title compound (2250 g; 80percent yield) as an amorphous solid.
80%
With thionyl chloride; In methanol; water;
PREPARATION 1 Dimethyl Pyridine-2,5-dicarboxylate To a stirred slurry of 2,5-pyridinedicarboxylic acid (2407 g; 14.4 mol) in methanol (8.0 liter) at -5° to -10° C., thionylchloride (3430 g; 2.10 liters; 28.8 mol) was added dropwise while maintaining the temperature in the -5° to -10° C. range. After completing the addition, the reaction was allowed to warm to ambient temperature, and stirred for 18 hours. The resulting solution was concentrated in vacuo to a volume of 4 liters, and an equal volume of water was added. The pH of the well-stirred mixture was then adjusted to 10 with saturated aqueous sodium carbonate. Solids were removed by filtration. The organic layer of the filtrate was separated, washed with water (8 liters), and dried in vacuo to afford the title compound (2250 g; 80percent yield) as an amorphous solid.
1-Boc-5-methyl-1,4,5,6-tetrahydro-2-(4-aminophenyl)pyrimidine[ No CAS ]
[ 100-26-5 ]
[ 681216-87-5 ]
Yield
Reaction Conditions
Operation in experiment
38%
With benzotriazol-1-ol; O-(1H-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate; N-ethyl-N,N-diisopropylamine; In DMF (N,N-dimethyl-formamide); at 20℃; for 15h;
Pyridine-2, 5-dicarboxylic acid (3.88 g, 23.2 mmol, 1.0 eq), o- benzotriazol-1-yl-N, N, N', [N'-TETRAMETHYLURONIUM] [HEXAFLUOROPHOSPHATE] (HBTU, 19.4 g, 51.1 mmol, 2.2 eq), [1-HYDROXYBENZOTRIAZOLE] hydrate (HOBT, 6.90 g, 51.1 mmol, 2.2 eq), intermediate 1 (14.8 g, 51.1 mmol, 2.2 eq) and anhydrous dimethylformamide (250 mL) were added to a 500 mL 3-necked round bottom flask under argon. With stirring, diisopropylethylamine (DIPEA, 13.2 g or 17.8 mL, 102 [MMOL,] 4.4 eq) was slowly added, resulting in a red solution. After stirring at room temperature for 15 h, a suspension was obtained. The solvent was removed by evaporation under vacuum. The residue was further purified by column chromatography (silica gel ; gradient eluants : 1.5%-5% methanol in methylene chloride) to give the Boc-protected coupling compound as a solid (3.15 g) in 38% yield. The Boc-protected coupling compound (3.14 g, 4.42 [MMOL)] was mixed with a cold saturated HCI solution in methanol (105 mL) at 0 [C.] The resulting reaction mixture was stirred at room temperature under argon for 1 h before concentrating to approximately 50 mL and cooling down to [0 C] for 30 min. An off-white solid precipitate was collected by filtration and washed with cold [MEOH] and diethyl ether, followed by drying at 65 C under high vacuum to give Formula [II] (1.89 g) in 74% yield.
Di(5-methyl-2-nitro-benzyl) pyridine-2,5-dicarboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With thionyl chloride; sodium hydrogencarbonate In dichloromethane; ethyl acetate
25 25.
25. Di(5-methyl-2-nitro-benzyl) pyridine-2,5-dicarboxylate Analogously to Example 1, 5 g of pyridine-2,5-dicarboxylic acid are converted into the acid chloride with 40 ml of thionyl chloride in 30 ml of methylene chloride and this is reacted with 10 g of 5-methyl-2-nitro-benzyl alcohol in 50 ml of methylene chloride. The reaction mixture is stirred overnight at room temperature, sodium bicarbonate solution is then added, the mixture is extracted with methylene chloride and the organic phase is dried. After the solvent has been stripped off, the residue is stirred with ethyl acetate, filtered off with suction and recrystallized twice from methylene chloride. Melting point 182° C. Yield 2.9 g
With sodium hydroxide; triethylamine; In tert-butyl alcohol;
(A) 5-[(tert-Butoxycarbonyl)amino]nicotinic acid 5-Pyridinedicarboxylic acid (5.00 g, 29.9 mmol) was suspended in t-butanol (35 ml), and the solution was added dropwise with triethylamine (8.34 ml, 59.8 mmol) and diphenylphosphoric acid azide (7.10 ml, 32.9 mmol), and heated under reflux for 3 hours. The reaction mixture was adjusted to a pH lower than 10 by addition of 1 N aqueous sodium hydroxide under ice cooling, and then washed with ether. The reaction mixture was again cooled with ice, and adjusted to about pH 4 with 1 N aqueous sodium hydroxide. The deposited solids were collected by filtration, and washed with water and ether to obtain the title compound as white powder (3.27 g, 45.9%). 1H-NMR (DMSO-d6) delta: 1.49 (9H, s), 8.45 (1H, s), 8.66 (1H, s), 8.75 (1H, s), 9.83 (1H, br)
Progress toward analog 18 has been made as follows. 2,5- Pyridinedicarboxylic acid (58) was preferentially esterified according to literature protocols66 by reflux in methanol with catalytic sulfuric acid for 2 hours to the mono- methyl ester (59) in 42% recovered yield after recrystallization from water. The monomethyl ester 59 was refluxed in excess thionyl chloride to effect its conversion to the acid chloride (60), and 60 was used to acylate 35 by reflux in DCM with excess aluminum trichloride (Scheme 10).
33%
With sulfuric acid; for 2h;Heating / reflux;
EXAMPLE 83a <strong>[100-26-5]Pyridine-2,5-dicarboxylic acid</strong>-2-methyl ester To a suspension of pyridine-2,5-dicarboxylic acid (4.2 g, 25.1 mmol) (Aldrich) in methanol (50 mL) was added concentrated sulfuric acid (1.5 g, 15.3 mmol) (Aldrich). The mixture was heated at refluxing for 2 hours. The crude was cooled down to room temperature and poured into water (250 mL). The precipitate formed was collected and washed with methanol to give pyridine-2,5-dicarboxylic acid-2-methyl ester as a grey solid. (Yield 1.5 g, 33%).
With sulfuric acid; for 2h;Heating / reflux;
To a suspension of 2,5-pyridine dicarboxylic acid (8.4 g, 0.055 mol) in MeOH (100 mL) was added concentrated H2SO4 (3 g), and the resulting mixture was heated under reflux for 2h. The reaction mixture was allowed to cool and then poured into H2O (500 mL). The resulting precipitate was collected by filtration and washed with H2O (2 x 40 mL) and dried overnight in a high vacuo oven to afford 6- (methoxycarbonyl)nicotinic acid. LCMS calc. = 181.15; found = 182.2 (M+l)+.
Preparation of picolyl 6-(methoxycarbonyl)nicotinic acid (2): 12.6 g of pyridine-2,5-dicarboxylic acid was suspended in 150 mL of methanol and 4.5 g of 95% sulfuric acid was slowly added. The reaction was heated to reflux for 2.5 h, cooled to 25C and the whole was poured into 750 mL of deionized (DI) water at room temperature. A white precipitate formed and the suspension was stirred for 20 minutes, filtered through a Buchner funnel with filter paper. The precipitate was rinsed with deionized and collected. This material was dissolved in 150 mL of dichioromethane heated to 35C, washed once with 150 mL of saturated sodium bicarbonate solution. The two layers were separated, and 2 N HC1 was added to the organic layer to until the pH was 1-2. A white precipitate formed and was filtered with a Buchner funnel fitted with filter paper. The product was rinsed with deionized water, collected, and dried under vacuum to provide 4.75 g of compound 2. TLC (80:20 ACN:H20, uv): Rf = .53 (bis-methyl ester Rf = 0.83). NMR (400 MHz, d6- DMSO): 9.12 (br s, 1 H), 8.42 (t, 1H), 8.15 (t, 1 H), 3.89 (s, 3H).
With sulfuric acid; for 2h;Reflux;
To a suspension of 2,5-pyridinecarboxylic acid (20.0 g, 0.131 mol) in methanol (238 ml) was added concentrated sulfuric acid (7.14 g). The reaction was heated to reflux and stirred at this temperature for 2 h. After cooling to room temperature, reaction was poured into water (1000 ml). The light yellow precipitate was filtered, washed with water (2 x 100 ml), and dried in vacuo to afford the title compound (14.2 g). Mass spectrum (ESI) 182 (M+l).
fac-bis(tetraethylammonium)tribromidotricarbonylrhenate[ No CAS ]
[ 7732-18-5 ]
fac-[Re(pyridine-2-carboxylato-5-carboxylic acid)(CO)3(H2O)][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
94%
fac-[NEt4]2[Re(CO)3(Br)3] (100.0 mg, 0.130 mmol) was dissolved in water at pH 2.2. Silver nitrate (66.0 mg, 0.389 mmol) was added to the solution and stirred for 24 h at room temperature. After the reaction mixture was filtered (AgBr), 2,5-pyridine dicarboxylic acid(22.0 mg, 0.133 mmol) was added to the solution and stirred under N2 at room temperature for 48 h. The mixture was filtered and the filtrate (pH 2.5) was dried in vacuo. Yield: 55.4 mg, 94 %. IR (KBr,cm-1): mCO = 1899, 2017, 2043. 1H NMR (CD3COCD3): delta = 7.93 (d,1H, J = 8.1 Hz), 8.58 (dd, 1H, J = 1.8 Hz, 8.1 Hz), 9.47 (s, 1H). 13CNMR (CD3COCD3): delta = 128.7, 132.9, 142.7, 151.6, 154.5, 164.5, 178.0, 195.0, 197.6, 198.1. HPLC: 17.84 min. Anal. Calc. C, 26.43;H, 1.33; N, 3.08. Found: C, 26.45; H, 1.30; N, 3.12%.
<strong>[100-26-5]Pyridine-2,5-dicarboxylic acid</strong> (1.00 g, 5.99 mmol) was suspended in allyl alcohol (10 ml) and cone. H2SO4 (0.4 ml) was added. The reaction was heated at 850C for 24 h. 4A Molecular sieves were then introduced into the reaction vessel and heating was continued for a further 24 h. The mixture was allowed to cool and sat. NaHCO3(aq) (50 ml) and DCM (80 ml) were added. The organic layer was separated, dried (hydrophobic frit) and evaporated. The product was isolated as a yellow oil after purification on an Isolute Si Il cartridge (10 g) eluting with DCM. Yield: 908 mg (61%) <n="53"/>LC-MS (Method 2): Rt = 3.28 min, m/z = 248 [M+H]+
Bi<SUB>2</SUB>O<SUB>2</SUB>(pyridine-2,5-dicarboxylate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
In water; at 180℃; for 72h;Autoclave; High pressure;
A mixture of Bi(NO3)3·5H2O (0.242 g, 0.5 mmol) or Bi2O3 (0.232 g, 0.5 mmol) and pyridine-2, 5-dicarboxylic acid (H2pydc) (0.250 g, 1.5 mmol) in H2O (25 ml) was sealed in a Teflon-lined autoclave and heated to a temperature of 180 C for 3 day, and then cooled slowly at 0.1 C/min to room temperature. Colorless, needle-like crystals were obtained in 90% yield (based on bismuth) admixed with an unidentified white powder phase, which was almost completely separated from the needle shaped crystals by sieving. The products were washed with DMF to dissolve and remove any unreacted ligand. The final product was isolated by vacuum filtration. The isolated needle crystals were used for structure and physical characterizations.
Bi<SUB>2</SUB>O<SUB>2</SUB>(pyridine-2,5-dicarboxylate)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
In water; at 180℃; for 72h;Autoclave; High pressure;
A mixture of Bi(NO3)3·5H2O (0.242 g, 0.5 mmol) or Bi2O3 (0.232 g, 0.5 mmol) and pyridine-2, 5-dicarboxylic acid (H2pydc) (0.250 g, 1.5 mmol) in H2O (25 ml) was sealed in a Teflon-lined autoclave and heated to a temperature of 180 C for 3 day, and then cooled slowly at 0.1 C/min to room temperature. Colorless, needle-like crystals were obtained in 90% yield (based on bismuth) admixed with an unidentified white powder phase, which was almost completely separated from the needle shaped crystals by sieving. The products were washed with DMF to dissolve and remove any unreacted ligand. The final product was isolated by vacuum filtration. The isolated needle crystals were used for structure and physical characterizations.
A solution of 2,5-pyridinedicarboxylic acid (0.070 g,0.410 mmol) in water (15 ml) at 70 C was added dropwise to a solution of K2[PtCl6] (0.100 g, 0.206 mmol) in water (8 ml) at 80 C. The reaction mixture was stirred for 4 days at 50 C. The yellow product was filtered off,washed with several drops ofwater,ethanol, diethyl ether and dried in vacuo (Yield: 0.07 g, 56.87%). Found: C, 28.61; H, 1.92; N, 4.84; Calc. for C14H8Cl2N2O8Pt (Mr 598.21): C, 28.11; H, 1.35; N, 4.68; nmax(ATR)/cm 1 3443 (w), 1717 (s,C]O), 1694 (s, C]O ), 1494 (m, C]N), 1397, 1318, 1273 (pyridine ring). 1H NMR (500.26 MHz, DMSO-d6, dH ppm): 9.20 (d, 1H, H6),8.99 (dd, 1H, H4), 8.41 (d, 1H, H3).
With sodium hydroxide; In water; at 140℃; for 72h;Sealed tube;
A mixture of EuCl3·6H2O (0.0366 g, 0.10 mmol), CuCl2·2H2O (0.0167 g, 0.10 mmol), H2pydc (0.0415 g, 0.25 mmol), NaOH (0.0020 g, 0.50 mmol), and H2O (6 mL) was sealed in a 10-mL Teflon-lined stainless steel container and heated at 140 C for 3 day. Upon being cooled to room temperature at a rate of 5 C/h, blue block crystals were obtained in 35% yield (based on Cu). Anal. for C42H50N6O40Cu3Eu2 (%): C, 28.45; H, 2.84; N, 4.74. Found: C, 28.37; H, 2.89; N, 4.70. IR (solid KBr pellet, cm-1): 3395(br, m), 1614(s), 1556(s), 1459(m), 1396(s), 1352(s), 1280(m), 1173(w), 1124(w), 1037(w), 891(w), 818(m), 770(m), 683(m), 649(m), 527(m), 459(w).
With sodium hydroxide; In water; at 130℃; for 72h;Sealed tube;
A mixture of DyCl3·6H2O (0.0377 g, 0.10 mmol), CuCl2·2H2O (0.0170 g, 0.10 mmol), H2pydc (0.0417 g, 0.25 mmol), NaOH (0.0020 g, 0.50 mmol), and H2O (6 mL) was sealed in a 10-mL Teflon-lined stainless steel container and heated at 130 C for 3 day. Upon being cooled to room temperature at a rate of 5 C/h, dark-blue block crystals were obtained in 38% yield (based on Cu). Anal. for C42H50N6O40Cu3Dy2 (%): C, 28.11; H, 2.81; N, 4.68. Found: C, 28.20; H, 2.90; N, 4.75. IR (solid KBr pellet, cm-1): 3412(br, m), 1615(s), 1560(s), 1456(m), 1393(s), 1344(s), 1274(m), 1170(m), 1128(m), 1038(m), 899(w), 822(m), 759(m), 690(m), 668(m), 515(m), 452(w).
With sodium hydroxide; In water; at 130℃; for 72h;Sealed tube;
A mixture of Ho(NO3)3·6H2O (0.0459 g, 0.10 mmol), CuSO4·5H2O (0.0251 g, 0.10 mmol), H2pydc (0.0420 g, 0.25 mmol), NaOH (0.0020 g, 0.50 mmol), and H2O (6 mL) was sealed in a 10-mL Teflon-lined stainless steel container and heated at 130 C for 3 day. Upon being cooled to room temperature at a rate of 5 C/h, pale-blue block crystals were obtained in 51% yield (based on Cu). Anal. for C42H50N6O40Cu3Ho2 (%): C, 28.04; H, 2.80; N, 4.67. Found: C, 28.10; H, 2.74; N, 4.74. IR (solid KBr pellet, cm-1): 3391(br, m), 1608(s), 1553(s), 1455(m), 1392(s), 1351(s), 1274(m), 1176(w), 1121(w), 1044(w), 898(w), 828(m), 766(m), 682(m), 648(m), 515(m), 460(w).
With sodium hydroxide; In water; at 130℃; for 72h;Sealed tube;
A mixture of LuCl3·6H2O (0.0389 g, 0.10 mmol), CuSO4·5H2O (0.0251 g, 0.10 mmol), H2pydc (0.0421 g, 0.25 mmol), NaOH (0.0020 g, 0.50 mmol), and H2O (6 mL) was sealed in a 10-mL Teflon-lined stainless steel container and heated at 130 C for 3 day. Upon being cooled to room temperature at a rate of 5 C/h, dark-blue block crystals were obtained in 42% yield (based on Cu). Anal. for C42H50N6O40Cu3Lu2 (%): C, 27.73; H, 2.77; N, 4.62. Found: C, 27.91; H, 2.84; N, 4.70. IR (solid KBr pellet, cm-1): 3419(m), 1644(s), 1615(s), 1560(s), 1455(m), 1399(s), 1365(s), 1274(m), 1176(w), 1121(w), 1037(w), 898(w), 828(m), 766(m), 682(m), 650(m), 522(m), 466(m).
With sodium hydroxide; In water; at 140℃; for 72h;Sealed tube;
A mixture of PrCl3·6H2O (0.0355 g, 0.10 mmol), CuSO4·5H2O (0.0247 g, 0.10 mmol), H2pydc (0.0420 g, 0.25 mmol), NaOH (0.0020 g, 0.50 mmol), and H2O (6 mL) was sealed in a 10-mL Teflon-lined stainless steel container and heated at 140 C for 3 day. Upon being cooled to room temperature at a rate of 5 C/h, dark-blue block crystals were obtained in 32% yield (based on Cu). Anal. for C42H52N6O41Cu3Pr2 (%): C, 28.51; H, 2.96; N, 4.75. Found: C, 28.82; H, 2.88; N, 4.80. IR (solid KBr pellet, cm-1): 3328(br, s), 1615(s), 1553(s), 1441(s), 1392(s), 1351(s), 1281(s), 1176(m), 1142(m), 1114(m), 1044(m), 953(m), 891(m), 856(m), 821(m), 766(s), 689(s), 571(m), 515(s), 460(m).
With sodium hydroxide; In water; at 130℃; for 72h;Sealed tube;
A mixture of NdCl3·6H2O (0.0359 g, 0.10 mmol), CuCl2·2H2O (0.0172 g, 0.10 mmol), H2pydc (0.0418 g, 0.25 mmol), NaOH (0.0020 g, 0.50 mmol), and H2O (6 mL) was sealed in a 10-mL Teflon-lined stainless steel container and heated at 130 C for 3day. Upon being cooled to room temperature at a rate of 5 C/h, blue block crystals were obtained in 53% yield (based on Cu). Anal. for C28H28N4O24CuNd2 (%): C, 29.08; H, 2.44; N, 4.84. Found: C, 29.75; H, 2.52; N, 4.91. IR (solid KBr pellet, cm-1): 3419(m), 1650(s), 1615(s), 1560(s), 1504(s), 1455(m), 1392(m), 1358(m), 1281(w), 1184(w), 1149(w), 1037(w), 884(w), 849(m), 766(m), 682(m), 669(s), 515(m), 453(m).
With sodium hydroxide; In water; at 170℃; for 72h;Sealed tube;
A mixture of TbCl3·6H2O (0.0373 g, 0.10 mmol), CuCl2·2H2O (0.0171 g, 0.10 mmol), H2pydc (0.0419 g, 0.25 mmol), NaOH (0.0020 g, 0.50 mmol), and H2O (6 mL) was sealed in a 10-mL Teflon-lined stainless steel container and heated at 170 C for 3 day. Upon being cooled to room temperature at a rate of 5 C/h, dark-blue block crystals were obtained in 43% yield (based on Cu). Anal. for C42H50N6O40Cu3Tb2 (%): C, 28.22; H, 2.82; N, 4.70. Found: C, 28.33; H, 2.74; N, 4.77. IR (solid KBr pellet, cm-1): 3399(m), 1638(s), 1610(s), 1554(s), 1456(m), 1394(s), 1352(s), 1276(m), 1171(w), 1150(w), 1039(w), 892(w), 823(m), 767(m), 691(m), 670(m), 510(m), 454(w).
With sodium hydroxide; In water; at 165℃; for 120h;
General procedure: A mixture of Cd(OAc)2·2H2O (0.133g, 0.5mmol), 2,5-H2pydc (0.083g, 0.5mmol), MEDPQ (0.124g, 0.5mmol), NaOH (0.004g, 0.1mmol) and H2O (18mL) was placed in a 25mL Teflon-lined stainless steel vessel under autogenous pressure at 165C for 5days. After cooling to room temperature, red block crystals of 1 were collected by filtration and washed with distilled water in 60% yield (based on Cd).
[Mn(2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)2(2,5-pydc)]·3H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
With sodium hydroxide; In water; at 165℃; for 120h;
General procedure: A mixture of Cd(OAc)2·2H2O (0.133g, 0.5mmol), 2,5-H2pydc (0.083g, 0.5mmol), MEDPQ (0.124g, 0.5mmol), NaOH (0.004g, 0.1mmol) and H2O (18mL) was placed in a 25mL Teflon-lined stainless steel vessel under autogenous pressure at 165C for 5days. After cooling to room temperature, red block crystals of 1 were collected by filtration and washed with distilled water in 60% yield (based on Cd).
[Cd2(2-(4-methoxyphenyl)-1H-imidazo[4,5-f][1,10]phenanthroline)2(2,5-pydc)2]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
With sodium hydroxide; In water; at 165℃; for 120h;
General procedure: A mixture of Cd(OAc)2·2H2O (0.133g, 0.5mmol), 2,5-H2pydc (0.083g, 0.5mmol), MEDPQ (0.124g, 0.5mmol), NaOH (0.004g, 0.1mmol) and H2O (18mL) was placed in a 25mL Teflon-lined stainless steel vessel under autogenous pressure at 165C for 5days. After cooling to room temperature, red block crystals of 1 were collected by filtration and washed with distilled water in 60% yield (based on Cd).
2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline[ No CAS ]
[ 5743-04-4 ]
[Cd(2-methyldipyrido[3,2-f:2′,3′-h]quinoxaline)(2,5-pydc)]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
With sodium hydroxide; In water; at 165℃; for 120h;
General procedure: A mixture of Cd(OAc)2·2H2O (0.133g, 0.5mmol), 2,5-H2pydc (0.083g, 0.5mmol), MEDPQ (0.124g, 0.5mmol), NaOH (0.004g, 0.1mmol) and H2O (18mL) was placed in a 25mL Teflon-lined stainless steel vessel under autogenous pressure at 165C for 5days. After cooling to room temperature, red block crystals of 1 were collected by filtration and washed with distilled water in 60% yield (based on Cd). Anal. Calc. for C22H13N5O4Cd (1): C, 50.45; H, 2.50; N, 13.37. Found: C, 50.47; H, 2.51; N, 13.35%. IR (KBr): nu=3439 (m), 3053 (m), 1628 (s), 1521 (m), 1474 (m), 1383 (s), 1334 (s), 1275 (m), 1167 (m), 1035 (w), 825 (m), 763 (m), 551 (w), 440 (w) cm-1.
[Zn3(5-benzoimidazoyltetrazolate)2(pyridine-2,5-dicarboxylate)2]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
40%
With sodium azide; In ethanol; water; at 159.84℃; for 72h;
The mixture of 1-cyanobenzoimidazole (29.8 mg, 0.21 mmol), ZnCl2 (23.8 mg,0.17 mmol), 2,5-pyridyldicarboxylic acid (29.9 mg, 0.18 mmol) and NaN3 (16.8 mg,0.26 mmol) in 15 ml EtOH and H2O (v/v = 1:2) were heated in a 25 ml bomb at 433 K for 3 d, then cooled to room temperature at a rate of 6 K h-1. Colorless block crystals suitable for X-ray analysis were obtained with a yield of 40% based on the ligand 1-cyanobenzoimidazole. The product was washed with EtOH and H2O, and then air-dried at ambient temperature. Elemental analysis for C30H16N14O8Zn3 found:C 40.20, H 1.87, N 21.74; calc: C 40.18, H 1.80, N 21.87. Selected IR (KBr, cm-1): 1642(w), 1613 (s), 1427 (w), 1395 (m), 1362 (m), 1283 (w), 1033 (w), 825 (s), 757 (s).
2.1. Synthesis of [Cu(2,5-pdc)(H2O)4]·H2O (1)A methanolic solution (10 mL) of pyridine-2,5 dicarboxylic acid (1 mM, 0.167 g) wasallowed to react with a methanolic solution (10 mL) of Cu(ClO4)2·6H2O (1 mM, 0.370 g)and stirred for 5 min. Then, a methanolic solution (5 mL) of triethylamine (2 mM) wasslowly poured with stirring. The whole green-colored reaction mixture was stirred for 2 hand filtered. The filtrate was kept in a CaCl2 desiccator and green single crystals suitablefor X-ray determination were obtained after a few days. Yield: 0.254 g (80%). Anal. Calcdfor C7H13CuNO9 (%): C, 26.35; H, 3.45; N, 4.39%. Found: C, 26.33; H, 3.41; N, 4.42.The infrared spectra exhibited the following absorptions: 3000-3500 (br), 2974 (w),1628 (s), 1560 (vs), 1470 (s), 1412 (s), 837 (w), and 538 (vw) cm-1.
[Sm(pic)2(pyridine-2,5-dicarboxylate)4(H2O)]n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With piperazine; at 160℃; for 72h;Autoclave;
All the starting materials were used directly without further purification. A mixture of Sm(NO3)3·6H2O (0.134 g, 0.3 mmol), pyridine 2,5-dicarboxylic acid (0.153 g, 0.9 mmol), piperazine (0.027 g, 0.3 mmol) and H2O (5 mL, 278 mmol) in the mole ratio 1.00:3.00:1.00:927 was sealed in a 23 mL Teflon reactor and kept under autogenous pressure at 160 C for 72 h. The mixture was cooled to room temperature at a rate of 20 C h-1, and bright yellow colored crystals were obtained. The heterogeneous solution was separated from the solid phase, the crystals washed with water and dried at room temperature. Yield: 81% based on Sm. Initial pH; 1.90, final pH; 3.40. The coordination polymer is insoluble in common solvents (ethanol, methanol, acetonitrile, etc.) and water. Anal. Calcd. for C13H9N2O7Sm: C, 34.24; H, 1.98; N, 6.15. Found: C, 33.95; H, 1.71; N, 5.62%. IR data (cm-1): 3478(w), 1660(m), 1566(s), 1392(s), 1361(s), 1033(m), 820(m), 769(s), 695(s), 505(s), 429(m).
Synthesis of [Cu(btb)(pydc)(H2O)]n (1).
A mixture of Cu(OAc)2 * H2O (29.9 mg, 0.15 mmol), btb (28.8 mg, 0.10mmol), NaOH (12.0 mg, 0.30 mmol), H2pydc (33.4 mg, 0.2mmol), and 10 mL water was heated at 140 C for 3 days in a Teflon-lined vessel (25 mL). Then, the mixture was cooled to room temperature at a rate of 5 C/h. Green block single crystals of 1, suitable for X-ray diffraction, were collected by filtration.
3Cu(2+)*2C18H18N4*2ClO4(1-)*2C7H3NO4(2-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
General procedure: To a mixture of tris(2-pyridylmethyl)amine, TPA (0.146g, 0.50mmol) and Cu(ClO4)2·6H2O (0.109g, 0.50mmol) dissolved in MeOH (20mL), pyridine-2,4-dicarboxylic acid disodium salt (Na2Py2,4-dc) (0.054g, 0.25mmol) dissolved in 5.0mL H2O was added drop by drop. The resulting solution was heated for 5min on a steam-bath, filtered through Celite and then was allowed to stand at room temperature. After two days, the resulting crude solid was collected by filtration and recrystallized from H2O to produe aqua blue single crystals of X-ray quality. These were collected by filtration, washed with propan-2-ol, Et2O and dried in air (overall yield: 0.105g, 61% based on Na2Py2,4-dc).
General procedure: [RuCl2(p-cymene)]2 (0.12 g, 0.20 mmol), glycine (0.03 g,0.40 mmol) and potassium tert-butoxide (0.05 g, 0.40 mmol) wereadded to dry methanol (40 mL), and the resulting mixture wasrefluxed for 30 min under argon atmosphere. AgNO3 (0.14 g,0.80 mmol) and dcmb (0.23 g, 0.85 mmol) were then added andthe reaction mixture was refluxed for additional 14 h in the dark.The reaction mixture was cooled to room temperature and filteredthrough a fine porosity frit to remove precipitated AgCl andexceeding dcmb. The filtrate was evaporated to dryness, and theresidue was recrystallized from a mixture of chloroform and hexane(v/v = 2:1), and dried in a vacuum to afford complex 3 as deepblue powder in a yield of 0.16 g (50percent).
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 sodium hydroxide; In water; at 179.84℃; for 72h;pH 8 - 9;Autoclave; High pressure;
General procedure: PrCl3·7H2O (0.1mmol), HNCP (0.1mmol) and 2,5-H2pydc (0.1mmol) were mixed in 10ml deionized water. And its pH value was controlled in the range of 8-9 with 1mol·L-1 NaOH solution. The resulting precursor was sealed in 25ml Teflon-lined stainless steel reactor and heated at 453K for 3d under autogenous pressure. The reaction system was then cooled slowly to room temperature. The obtained solid is a mixture of yellow block crystals and powder. The crystals of 1 suitable for X-ray single-crystal diffraction analysis are picked out from the solid mixture in 61% yield based on PrCl3·7H2O. Syntheses of [Ln(NCP)(2,5-pydc)]n (Ln=La(2), Nd(3), Sm(4)). The complexes 2, 3 and 4 were prepared as described as for 1 above, except that Ln(NO3)3·6H2O was used instead of PrCl3·7H2O. The crystals of complexes 2-4 are picked out from the solid mixture in 67%, 65% and 72% yield based on Ln(NO3)3·6H2O, respectively. Anal. Calcd for C54H34N10O15Pr2 (1): C 48.23, H 2.55, N 10.42%. Found: C 48.01, H 2.63, N 10.10%. Anal. Calcd for C27H14N5O6La (2): C 50.41, H 2.19, N 10.89%. Found: C 50.13, H 2.33, N 10.84%. Anal. Calcd for C27H14N5O6Nd (3): C 49.99, H 2.18, N 10.80%. Found: C 50.03, H 2.25, N 10.77%. C27H14N5O6Sm (4): C 49.53, H 2.16, N 10.70%. Found: C 49.47, H 2.20, N 10.67%.
With sodium hydroxide; In water; at 179.84℃; for 72h;pH 8 - 9;Autoclave; High pressure;
General procedure: PrCl3·7H2O (0.1mmol), HNCP (0.1mmol) and 2,5-H2pydc (0.1mmol) were mixed in 10ml deionized water. And its pH value was controlled in the range of 8-9 with 1mol·L-1 NaOH solution. The resulting precursor was sealed in 25ml Teflon-lined stainless steel reactor and heated at 453K for 3d under autogenous pressure. The reaction system was then cooled slowly to room temperature. The obtained solid is a mixture of yellow block crystals and powder. The crystals of 1 suitable for X-ray single-crystal diffraction analysis are picked out from the solid mixture in 61% yield based on PrCl3·7H2O. Syntheses of [Ln(NCP)(2,5-pydc)]n (Ln=La(2), Nd(3), Sm(4)). The complexes 2, 3 and 4 were prepared as described as for 1 above, except that Ln(NO3)3·6H2O was used instead of PrCl3·7H2O. The crystals of complexes 2-4 are picked out from the solid mixture in 67%, 65% and 72% yield based on Ln(NO3)3·6H2O, respectively. Anal. Calcd for C54H34N10O15Pr2 (1): C 48.23, H 2.55, N 10.42%. Found: C 48.01, H 2.63, N 10.10%. Anal. Calcd for C27H14N5O6La (2): C 50.41, H 2.19, N 10.89%. Found: C 50.13, H 2.33, N 10.84%. Anal. Calcd for C27H14N5O6Nd (3): C 49.99, H 2.18, N 10.80%. Found: C 50.03, H 2.25, N 10.77%. C27H14N5O6Sm (4): C 49.53, H 2.16, N 10.70%. Found: C 49.47, H 2.20, N 10.67%.
With sodium hydroxide; In water; at 179.84℃; for 72h;pH 8 - 9;Autoclave; High pressure;
General procedure: PrCl3·7H2O (0.1mmol), HNCP (0.1mmol) and 2,5-H2pydc (0.1mmol) were mixed in 10ml deionized water. And its pH value was controlled in the range of 8-9 with 1mol·L-1 NaOH solution. The resulting precursor was sealed in 25ml Teflon-lined stainless steel reactor and heated at 453K for 3d under autogenous pressure. The reaction system was then cooled slowly to room temperature. The obtained solid is a mixture of yellow block crystals and powder. The crystals of 1 suitable for X-ray single-crystal diffraction analysis are picked out from the solid mixture in 61% yield based on PrCl3·7H2O. Syntheses of [Ln(NCP)(2,5-pydc)]n (Ln=La(2), Nd(3), Sm(4)). The complexes 2, 3 and 4 were prepared as described as for 1 above, except that Ln(NO3)3·6H2O was used instead of PrCl3·7H2O. The crystals of complexes 2-4 are picked out from the solid mixture in 67%, 65% and 72% yield based on Ln(NO3)3·6H2O, respectively. Anal. Calcd for C54H34N10O15Pr2 (1): C 48.23, H 2.55, N 10.42%. Found: C 48.01, H 2.63, N 10.10%. Anal. Calcd for C27H14N5O6La (2): C 50.41, H 2.19, N 10.89%. Found: C 50.13, H 2.33, N 10.84%. Anal. Calcd for C27H14N5O6Nd (3): C 49.99, H 2.18, N 10.80%. Found: C 50.03, H 2.25, N 10.77%. C27H14N5O6Sm (4): C 49.53, H 2.16, N 10.70%. Found: C 49.47, H 2.20, N 10.67%.
praseodymium (III) chloride heptahydrate[ No CAS ]
[ 7732-18-5 ]
Pr(3+)*C20H11N4O2(1-)*C7H3NO4(2-)*1.5H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
61%
With sodium hydroxide; at 179.84℃; for 72h;pH 8 - 9;Autoclave; High pressure;
PrCl3·7H2O (0.1mmol), HNCP (0.1mmol) and 2,5-H2pydc (0.1mmol) were mixed in 10ml deionized water. And its pH value was controlled in the range of 8-9 with 1mol·L-1 NaOH solution. The resulting precursor was sealed in 25ml Teflon-lined stainless steel reactor and heated at 453K for 3d under autogenous pressure. The reaction system was then cooled slowly to room temperature. The obtained solid is a mixture of yellow block crystals and powder. The crystals of 1 suitable for X-ray single-crystal diffraction analysis are picked out from the solid mixture in 61% yield based on PrCl3·7H2O. Syntheses of [Ln(NCP)(2,5-pydc)]n (Ln=La(2), Nd(3), Sm(4)). The complexes 2, 3 and 4 were prepared as described as for 1 above, except that Ln(NO3)3·6H2O was used instead of PrCl3·7H2O. The crystals of complexes 2-4 are picked out from the solid mixture in 67%, 65% and 72% yield based on Ln(NO3)3·6H2O, respectively. Anal. Calcd for C54H34N10O15Pr2 (1): C 48.23, H 2.55, N 10.42%. Found: C 48.01, H 2.63, N 10.10%. Anal. Calcd for C27H14N5O6La (2): C 50.41, H 2.19, N 10.89%. Found: C 50.13, H 2.33, N 10.84%. Anal. Calcd for C27H14N5O6Nd (3): C 49.99, H 2.18, N 10.80%. Found: C 50.03, H 2.25, N 10.77%. C27H14N5O6Sm (4): C 49.53, H 2.16, N 10.70%. Found: C 49.47, H 2.20, N 10.67%.
In a 25 ml round-bottom flask, add 2 ml containing Co (NO 3) 2 · 6H 2 O (0.0436g, 0 . 15mmol) the ethanol solution, then adding 4 ml containing 3-amino-5-methyl-pyrazole (0.0582g, 0 . 6mmol) of ethanol solution, stirring the mixture at room temperature for 1h, solution is red, then slowly adding 4 ml NaOH to PH= 7 for the 2, 5-pyridine dicarboxylic acid (0.0251g, 0 . 15mmol) aqueous solution, after dripping, appear red solution, stirring 24h rear, left standstill obtain a red crystal. The crystal washing with water, vacuum drying. Yield: 55%,
[Ni<SUB>2</SUB>(4,4'-bis(1-imidazolyl)biphenyl)(2,5-pyridinedicarboxylate)<SUB>2</SUB>(water)<SUB>4</SUB>]<SUB>n</SUB>[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
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 4,4?-bis(1-imidazolyl)biphenyl (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.
With triethylamine; In water; at 80 - 120℃; for 24h;pH 5;High pressure;
Three series of [Ln2(pydc)2(SO4) (H2O)x]yH2O (x= 0, 2, 3; y= 0, 2,6), differing in numbers of the coordinated (x) and the crystallizing (y) water molecules, were hydrothermally synthesized through subtlealteration in reaction temperature and time (Scheme 1). [Ln2(pydc)2(SO4) (H2O)2]6H2O; LnLa (Ia), Pr (Ib), Nd (Ic). To synthesize Ia, a solution of La2(SO4)38H2O (0.1420 g, 0.2000 mmol) and H2pydc (0.0334 g, 0.200 mmol) was prepared using 10.00 ml of deionized water, into which 50.0 muL triethylamine was added to adjust pH of the solution to 5. The solution was then transferred into a 23mL Teflon lined hydrothermal reactor, which was then sealed and heated at two different temperatures, i.e. 80 and 120 C, for 1 day. After the reaction was cooled down to room temperature, colorless block crystals of Ia was obtained in ca. 35% yield based on LaIII. IR (KBr, cm-1): 3088 (br),1603(m), 1580(s), 1557(s), 1485(m), 1412(m), 1378(m), 1346(s),1282(s), 1172(m), 1151(m), 1100(m), 1035(s), 995(w), 933(w), 883(w),812(s), 758(s), 693(s), 654(m).
With triethylamine; In water; at 150 - 180℃; for 24h;pH 5;High pressure;
General procedure: Three series of [Ln2(pydc)2(SO4) (H2O)x]yH2O (x= 0, 2, 3; y= 0, 2,6), differing in numbers of the coordinated (x) and the crystallizing (y) water molecules, were hydrothermally synthesized through subtlealteration in reaction temperature and time (Scheme 1). [Ln2(pydc)2(SO4) (H2O)2]6H2O; LnLa (Ia), Pr (Ib), Nd (Ic). To synthesize Ia, a solution of La2(SO4)38H2O (0.1420 g, 0.2000 mmol) and H2pydc (0.0334 g, 0.200 mmol) was prepared using 10.00 ml of deionized water, into which 50.0 muL triethylamine was added to adjust pH of the solution to 5. The solution was then transferred into a 23mL Teflon lined hydrothermal reactor, which was then sealed and heated at two different temperatures, i.e. 80 and 120 C, for 1 day. After the reaction was cooled down to room temperature, colorless block crystals of Ia was obtained in ca. 35% yield based on LaIII.
With triethylamine; In water; at 120℃; for 24h;pH 5;High pressure;
General procedure: Three series of [Ln2(pydc)2(SO4) (H2O)x]yH2O (x= 0, 2, 3; y= 0, 2,6), differing in numbers of the coordinated (x) and the crystallizing (y) water molecules, were hydrothermally synthesized through subtlealteration in reaction temperature and time (Scheme 1). [Ln2(pydc)2(SO4) (H2O)2]6H2O; LnLa (Ia), Pr (Ib), Nd (Ic). To synthesize Ia, a solution of La2(SO4)38H2O (0.1420 g, 0.2000 mmol) and H2pydc (0.0334 g, 0.200 mmol) was prepared using 10.00 ml of deionized water, into which 50.0 muL triethylamine was added to adjust pH of the solution to 5. The solution was then transferred into a 23mL Teflon lined hydrothermal reactor, which was then sealed and heated at two different temperatures, i.e. 80 and 120 C, for 1 day. After the reaction was cooled down to room temperature, colorless block crystals of Ia was obtained in ca. 35% yield based on LaIII.
With triethylamine; In water; at 135 - 140℃; for 24h;pH 5;High pressure;
General procedure: Three series of [Ln2(pydc)2(SO4) (H2O)x]yH2O (x= 0, 2, 3; y= 0, 2,6), differing in numbers of the coordinated (x) and the crystallizing (y) water molecules, were hydrothermally synthesized through subtlealteration in reaction temperature and time (Scheme 1). [Ln2(pydc)2(SO4) (H2O)2]6H2O; LnLa (Ia), Pr (Ib), Nd (Ic). To synthesize Ia, a solution of La2(SO4)38H2O (0.1420 g, 0.2000 mmol) and H2pydc (0.0334 g, 0.200 mmol) was prepared using 10.00 ml of deionized water, into which 50.0 muL triethylamine was added to adjust pH of the solution to 5. The solution was then transferred into a 23mL Teflon lined hydrothermal reactor, which was then sealed and heated at two different temperatures, i.e. 80 and 120 C, for 1 day. After the reaction was cooled down to room temperature, colorless block crystals of Ia was obtained in ca. 35% yield based on LaIII.
With triethylamine; In water; at 120℃;pH 5;High pressure;
General procedure: Three series of [Ln2(pydc)2(SO4) (H2O)x]yH2O (x= 0, 2, 3; y= 0, 2,6), differing in numbers of the coordinated (x) and the crystallizing (y) water molecules, were hydrothermally synthesized through subtlealteration in reaction temperature and time (Scheme 1). [Ln2(pydc)2(SO4) (H2O)2]6H2O; LnLa (Ia), Pr (Ib), Nd (Ic). To synthesize Ia, a solution of La2(SO4)38H2O (0.1420 g, 0.2000 mmol) and H2pydc (0.0334 g, 0.200 mmol) was prepared using 10.00 ml of deionized water, into which 50.0 muL triethylamine was added to adjust pH of the solution to 5. The solution was then transferred into a 23mL Teflon lined hydrothermal reactor, which was then sealed and heated at two different temperatures, i.e. 80 and 120 C, for 1 day. After the reaction was cooled down to room temperature, colorless block crystals of Ia was obtained in ca. 35% yield based on LaIII.
With triethylamine; In water; at 120℃; for 168h;pH 5;High pressure;
General procedure: Three series of [Ln2(pydc)2(SO4) (H2O)x]yH2O (x= 0, 2, 3; y= 0, 2,6), differing in numbers of the coordinated (x) and the crystallizing (y) water molecules, were hydrothermally synthesized through subtlealteration in reaction temperature and time (Scheme 1). [Ln2(pydc)2(SO4) (H2O)2]6H2O; LnLa (Ia), Pr (Ib), Nd (Ic). To synthesize Ia, a solution of La2(SO4)38H2O (0.1420 g, 0.2000 mmol) and H2pydc (0.0334 g, 0.200 mmol) was prepared using 10.00 ml of deionized water, into which 50.0 muL triethylamine was added to adjust pH of the solution to 5. The solution was then transferred into a 23mL Teflon lined hydrothermal reactor, which was then sealed and heated at two different temperatures, i.e. 80 and 120 C, for 1 day. After the reaction was cooled down to room temperature, colorless block crystals of Ia was obtained in ca. 35% yield based on LaIII.
With triethylamine; In water; at 120℃; for 24h;pH 5;High pressure;
General procedure: Three series of [Ln2(pydc)2(SO4) (H2O)x]yH2O (x= 0, 2, 3; y= 0, 2,6), differing in numbers of the coordinated (x) and the crystallizing (y) water molecules, were hydrothermally synthesized through subtlealteration in reaction temperature and time (Scheme 1). [Ln2(pydc)2(SO4) (H2O)2]6H2O; LnLa (Ia), Pr (Ib), Nd (Ic). To synthesize Ia, a solution of La2(SO4)38H2O (0.1420 g, 0.2000 mmol) and H2pydc (0.0334 g, 0.200 mmol) was prepared using 10.00 ml of deionized water, into which 50.0 muL triethylamine was added to adjust pH of the solution to 5. The solution was then transferred into a 23mL Teflon lined hydrothermal reactor, which was then sealed and heated at two different temperatures, i.e. 80 and 120 C, for 1 day. After the reaction was cooled down to room temperature, colorless block crystals of Ia was obtained in ca. 35% yield based on LaIII.
The 5.1 g (5.3 mmol) of HfCl4 and 2.4 g of 2,5-pyridinedicarboxylic(14 mmol) acid were loaded into 150 mL of H2O/Acetic acid (3/2) solution.The resulting suspension was stirred at rate 200 rpm during theheating to the reflux (105-110 C) to evenly suspend the two solids inthe suspension. After the reaction reached reflux temperature, thesuspension was kept under static conditions for 24 h. After that time thesuspension was allowed to cool to the room temperature and filteredthrough 0.45 mum filter paper. The remaining white solid was soaked inanhydrous MeOH for 3 days, during that period the solvent phase waschanged to fresh MeOH each day. After the solvent has been removed,the remaining white solid was activated by heating to 120 C undervacuum for 16 h, yielding MOF 1 as reddish powder. Yield 83%, basedon HfCl4.
The 5.1 g (5.3 mmol) of HfCl4 and 2.4 g of 2,5-pyridinedicarboxylic(14 mmol) acid were loaded into 150 mL of H2O/Acetic acid (3/2) solution.The resulting suspension was stirred at rate 200 rpm during theheating to the reflux (105-110 C) to evenly suspend the two solids inthe suspension. After the reaction reached reflux temperature, thesuspension was kept under static conditions for 24 h. After that time thesuspension was allowed to cool to the room temperature and filteredthrough 0.45 mum filter paper. The remaining white solid was soaked inanhydrous MeOH for 3 days, during that period the solvent phase waschanged to fresh MeOH each day. After the solvent has been removed,the remaining white solid was activated by heating to 120 C undervacuum for 16 h, yielding MOF 1 as reddish powder. Yield 83%, basedon HfCl4.
To a mixture containing Cu(ClO4)2·6H2O (0.190 g, 0.5 mmol) and tris(3-aminopropyl)amine, trpn (0.0.094 g, 0.5 mmol) dissolved in MeOH (20 mL), an aqueous solution (5 mL) of pyridine-2,5-dicarboxylic acid disodium salt (0.053 g, 0.25 mmol) was added. The solution was then heated on a steam-bath for 10 min, filtered through celite and the resulting blue solution was allowed to stand at room temperature. The crude solid, which separated was collected by filtration. Crystallization of the product from H2O afforded tiny blue crystals suitable for X-ray analysis. These were collected by filtration, washed by propan-2-ol, Et2O and dried in air (overall yield: 0.150 g, 82% based on Cu(ClO4)2·6H2O). Characterization: C32H54Cl2Cu3N10O16 (1096.37 g/mol): Calcd: C, 35.06; H, 4.96; N, 12.78. Found: C, 34.88; H, 5.01; N,12.63%. Selected IR bands (ATR, cm1): 3323 (m), 3285 (m) nu(NeH) stretching; 2934 (w), 2889 (w) nu(CeH) stretching; 1594 (s), 1436 (vs)[nu(C]O+C]C+C]N)]; 1070 (vs, b) nu(CleO). UV-Vis (H2O): lambdamax, nm (epsilonmax M-1 cm-1 per Cu atom)=562 (sh), 679 (85), 906 (sh).
Stage #1: Pyridine-2,5-dicarboxylic acid With sodium hydroxide In water
Stage #2: copper(II) perchlorate hexahydrate; N,N,N',N'',N'''-pentamethyldiethylenetriamine; water With sodium dicyanamide In methanol for 0.166667h; Heating;
2.2.2. Synthesis of [Cu3(pmdien)2(μ2-Py2,5-dc)2(ClO4)2(H2O)2] (2)
To a mixture containing Cu(ClO4)2·6H2O (0.190 g, 0.5 mmol), N,N,N′,N″,N″-pentamethyldiethylenetriamine, pmdien (0.087 g,0.5 mmol) and sodium dicyanamide (0.045 g, 0.5 mmol), Nadca dissolved in H2O (10 mL), an aqueous solution (5 mL) of 2,5-pyridine dicarboxylic acid, H2Py2,5-dc (0.053 g, 0.25 mmol). The resulting solution was heated on a steam-bath for 10 min, filtered through celite and then allowed to stand at room temperature. The dark blue well-shaped single crystals, which were separated after four days, were collected by filtration, washed with propan-2-ol, Et2O and dried in air (overall yield: 0.165 g, 60% based on Cu(ClO4)2·6H2O). Characterization: C32H56Cl2Cu3N8O18 (1102.37 g/mol): Calcd: C, 34.86; H, 5.12; N,10.16. Found: C. 34.51, H, 5.04; N, 10.36%. Selected IR bands (cm1): 3355 (w,b) ν(OeH) stretching; 3169, 2921 (vw) ν(CeH) stretching; 1632 (s), 1612 (vs), 1463 (m); 1390 (s), 1344 (vs), 1276 [ν(C]O+C]C+C]N)]; 1077 (vs), 1040 (s) ν(Cl-O). UV-Vis (H2O): λmax,nm (εmax M-1 cm-1 per Cu atom)=555 (sh), 656 (151).
Stage #1: Pyridine-2,5-dicarboxylic acid; lead(II) chloride With air In water for 0.5h;
Stage #2: In water at 120℃; for 72h; Autoclave;
2.2. Synthesis of [Pb(Hpydc)2]n (1)
A mixture of PbCl2 (0.1391 g, 0.50 mmol), H2pydc (0.1671 g,1.0 mmol) and water (5 mL) was stirred for 30 min in air, then sealed in a23 mL Teflon autoclave and heated at 120 C for 3 days and then theultimate mixture was cooled and filtered. Colorless block crystals wereobtained in ca. 64% yield based on Pb(II). Anal. calcd for C14H8N2O8Pb(Mr 539.41): C, 31.17%; H,1.49%; N, 5.19%. Found: C, 31.08%; H,1.38%; N, 5.48%.
Stage #1: Pyridine-2,5-dicarboxylic acid; copper(II) dichloride dihydrate; N,N-dimethyl-formamide With triethylamine for 0.166667h;
Stage #2: With hydrogenchloride In lithium hydroxide monohydrate at 140℃; for 42h; Autoclave;
2.2.1. Solvothermal synthesis
First, H 2 pdc ligand (150 mg, 0.9 mmol) was dissolved in 10 mL DMF (N, N-Dimethylformamide), and then three drops of trimethy- lamine (TEA) as a weak base and Cu(Cl) 2 2H 2 O (51 mg, 0.3 mmol) were added to the solvent respectively, and stirred for 10 mins. The pH of the final mixture was adjusted 3 using 1M hydrochloric acid solution as a regulator of pH. Then the mixture was transferred into a Teflon-lined autoclave and heated solvothermally for 72 h at 140 °C and a cooling ramp of 2 °C/h. The product was washed sev- eral times with DMF solvent and dried at 120 °C for 2 h in the vac- uum oven. Finally, blue crystals of BCP-1 were formed in as high as 73% yield based on H 2 pdc ligand, with over 320 °C melting points.
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