* 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.
Example 12 130 g (1200 mmol) of 2-methylglutaronitrile and 20 g (120 mmol) of isophthalic acid are introduced into a 250 ml glass reactor. The white suspension is stirred and 0.32 g (2.4 mmol) of anhydrous aluminum chloride is added. The mixture is gradually heated to 270° C. and is maintained under these conditions for 4 h. During the rise in temperature, the isophthalic acid dissolves in the MGN. The reaction medium is subsequently analyzed by GC. An RY percent for MGI of 76percent and a yield of 1,3-dicyanobenzene of 69percent are obtained.
Reference：
[1] Journal fuer Praktische Chemie (Leipzig), 1896, vol. <2>54, p. 85
[2] Organic and Biomolecular Chemistry, 2014, vol. 12, # 25, p. 4445 - 4453
[3] Patent: CN103864711, 2016, B,
[4] RSC Advances, 2018, vol. 8, # 10, p. 5473 - 5483
[5] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2018, vol. 204, p. 225 - 231
[6] Bioorganic Chemistry, 2018, vol. 81, p. 389 - 395
5
[ 201230-82-2 ]
[ 626-00-6 ]
[ 121-91-5 ]
[ 618-51-9 ]
Reference：
[1] Journal of Organic Chemistry, 1999, vol. 64, # 18, p. 6921 - 6923
6
[ 124-38-9 ]
[ 626-00-6 ]
[ 121-91-5 ]
[ 618-51-9 ]
Reference：
[1] European Journal of Organic Chemistry, 2014, vol. 2014, # 21, p. 4562 - 4570
7
[ 121-91-5 ]
[ 95-54-5 ]
[ 29914-81-6 ]
Yield
Reaction Conditions
Operation in experiment
57%
at 190℃; for 24 h;
Isophthalic acid (1.130 g, 6.8 mmol) and 1,2-diaminobenzene (1.417 g, 13.1 mmol) were dissolved in 20 mL of polyphosphoric acid. The stirred mixture was maintained at 190 °C for 24 h. The solution was allowed to cool at room temperature (20 – 25 °C) and slowly stirred in 50 mL of ice. The reaction mixture was neutralized with NaOH and the precipitate was filtered out and washed with cold water. The solid was recrystallized from methanol to yield a white-off solid (1.06 g, yield 57percent, mp 183-186 °C). 1H NMR (DMSO-d6, 400 MHz): 13.16 (s, 2H, Hc), 9.06 (t, 4Jf-d = 1.6 Hz, 1H, Hf), 8.26 (dd, 4Jd-f = 1.6 Hz, 3Jd-e = 7.8 Hz, 2H, Hd), 7.74 (t, 3Je-d = 7.8 Hz, 1H, He), 7.69 (bs, 2H, Hb’), 7.58 (bs, 2H, Hb), 7.24 (d, 3Ja-b = 4.3 Hz, 4H, HaHa’). 13C NMR (DMSO-d6, 100 MHz): 125.3 (Cf), 128.0 (Cd), 130.2 (Ce), 119.5-112.1 (Cb), 123.3-122.4 (Ca). HRMS-ESI (m/z): calcd for [BBB+H]+ C20H15N4, 311.1291; found, 311.1294 (error: 1 ppm).
Reference：
[1] Organometallics, 2013, vol. 32, # 6, p. 1807 - 1814
[2] Asian Journal of Chemistry, 2013, vol. 25, # 7, p. 4013 - 4016
[3] Indian Journal of Chemistry, Section A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical Chemistry, 1993, vol. 32, # 1-3, p. 33 - 38
[4] Journal of Materials Chemistry, 2012, vol. 22, # 42, p. 22496 - 22500,5
[5] Journal of the American Chemical Society, 1992, vol. 114, # 11, p. 4230 - 4237
[6] Tetrahedron Letters, 2015, vol. 56, # 45, p. 6177 - 6182
[7] Organic and Biomolecular Chemistry, 2016, vol. 14, # 35, p. 8232 - 8236
[8] Chemistry - A European Journal, 2012, vol. 18, # 7, p. 1961 - 1968
[9] RSC Advances, 2015, vol. 5, # 109, p. 90001 - 90009
[10] Journal of Materials Chemistry C, 2018, vol. 6, # 31, p. 8495 - 8501
8
[ 121-91-5 ]
[ 626-18-6 ]
Yield
Reaction Conditions
Operation in experiment
69%
With sodium tetrahydroborate In tetrahydrofuran; ethanol at 20℃; for 3 h;
To a stirred THF (40 mL) solution of isophthalaldehyde (0.27 g, 2.0 mmol) was slowlyadded NaBH4 (0.30 g, 7.9 mmol). To the mixture was slowly added EtOH (10 mL) andthe resulting mixture was stirred at room temperature for 3 h. To the solution was slowlyadded ice water (10 mL) at 0 °C followed by 10percent HCl aq until reaching a pH<7. Themixture was extracted with Et2O (50 mL x 5). The combined organic layers werewashed with brine (50 mL x 5), dried over Na2SO4, filtered and concentrated in vacuo togive benzene-1,3-dimethanol (7a, 0.25 g, 69percent yield). The resultingsolution was stirred at reflux for 2 h. To the solution was added THF (100 mL) solutionof 1,3-bis(bromomethyl)benzene (8a, 1.53 g, 5.7 mmol), and the mixture was stirred atreflux for 2 days. To the solution was added ice water (20 mL) at<10 °C. The mixturewas extracted with Et2O (50 mL x 3). The combined organic layers were washed withbrine (50 mL x 3), dried over Na2SO4, filtered, and concentrated in vacuo, giving aresidue that was subjected to silica gel column chromatography (three times, eacheluent; hexane:AcOEt = 1:1, hexane:CHCl3 = 10:1, CHCl3:AcOEt = 20:1) followed byrecrystallization from CH2Cl2/hexane gave 2,11-dioxa[3.3]metacyclophane (6a, 0.01 g,7percent yield). Colorless solid; mp 115-117 °C.
Reference：
[1] Organic Preparations and Procedures International, 2002, vol. 34, # 6, p. 665 - 670
[2] Chemistry - A European Journal, 2017, vol. 23, # 30, p. 7207 - 7211
[3] Tetrahedron Letters, 2006, vol. 47, # 5, p. 771 - 774
[4] Chemistry Letters, 2017, vol. 46, # 9, p. 1357 - 1360
[5] Chemische Berichte, 1906, vol. 39, p. 2938
9
[ 121-91-5 ]
[ 626-18-6 ]
[ 28286-79-5 ]
Reference：
[1] Organic Preparations and Procedures International, 2002, vol. 34, # 6, p. 665 - 670
10
[ 201230-82-2 ]
[ 150177-91-6 ]
[ 591-18-4 ]
[ 121-91-5 ]
[ 585-76-2 ]
Reference：
[1] Journal of Organic Chemistry, 1993, vol. 58, # 18, p. 4794 - 4795
11
[ 121-91-5 ]
[ 3971-31-1 ]
Yield
Reaction Conditions
Operation in experiment
96.3%
With hydrogen; acetic acid In methanol
1,3-cyclohexanedicarboxylic acid To a suspension of isophthalic acid (500 g, 3 mol) in methanol (2.81) was added 5percent Rhodium-on-alumina catalyst (50 g) and acetic acid (150 ml). The reaction mixture was shaken under hydrogen (50 psi) at room temperature overnight. The mixture was filtered through celite. To this solution was added fresh 5percent Rhodium-on-alumina catalyst (25 g), and the mixture was shaken under 50 psi of hydrogen for another 24 hours. The final reaction mixture was filtered through celite. The solution was concentrated under vacuum to give 493 g of the title compound as a white powder (96.3 percent yield). m.p. 163-165° C.
96.3%
With hydrogen; acetic acid In methanol
PREPARATION a 1,3-cyclohexanedicarboxylic acid To a suspension of isophthalic acid (500 g, 3 mol) in methanol (2.8 1) was added 5percent Rhodium-on-alumina catalyst (50 g) and acetic acid (150 ml). The reaction mixture was shaken under hydrogen (50 psi) at room temperature overnight. The mixture was filtered through celite. To this solution was added fresh 5percent Rhodium-on-alumina catalyst (25 g), and the mixture was shaken under 50 psi of hydrogen for another 24 hours. The final reaction mixture was filtered through celite. The solution was concentrated under vacuum to give 493 g of the title compound as a white powder (96.3percent yield). m.p. 163-165° C.
96.3%
With hydrogen; acetic acid In methanol at 20℃; for 24 h;
To a suspension of isophthalic acid (500 g, 3 mol) in methanol (2.8 l) was added 5percent Rhodium-on-alumina catalyst (50 g) and acetic acid (150 ml).The reaction mixture was shaken under hydrogen (50 psi) at room temperature overnight.The mixture was filtered through celite.To this solution was added fresh 5percent Rhodium-on-alumina catalyst (25 g), and the mixture was shaken under 50 psi of hydrogen for another 24 hours.The final reaction mixture was filtered through celite.The solution was concentrated under vacuum to give 493 g of the title compound as a white powder (96.3percent yield).m.p. 163-165° C. 1H NMR of 2: (300 MHz, CDCl3) δ 9.00-10.00 (sb, 2H), 2.95 (m, 0.5H), 2.20-2.40 (m, 2.5H), 1.90-2.10 (m, 3H), 1.78 (m, 1H), 1.58 (t, 1H), 1.39 (d, 2H).
95%
With hydrogen In acetic acid at 25℃; for 16 h;
To a suspension of isophthalic acid (5.0 g, 30.1 mmol) in 45 ml of acetic acid was added a slurry of 0.1 g of platinum oxide in 5 ml of acetic acid.The resulting mixture was stirred under 50 psi of hydrogen at 25° C. for 16 hours. NMR analysis (DMSO-d6) at this time showed complete reduction of starting material.The reaction mixture was filtered through Celite and the filter cake was rinsed with methanol.The combined filtrate and washes were concentrated under reduced pressure, using heptane to azeotropically remove residual acetic acid.Trituration of the resultant semi-solid with heptane and filtration of the precipitate provided 4.92 g (95percent) of the title compound as a white powder. mp: 163-165° C. 1H NMR (300 MHz, CDCl3) δ 9.00-10.00 (br s, 2H), 2.95 (m, 0.5H), 2.20-2.40 (m, 2.5H), 1.90-2.10 (m, 3H), 1.78 (m, 1H), 1.58 (t, 1H), 1.39 (d, 2H).
95%
With hydrogen In n-heptane; acetic acid
PREPARATION u 1,3-cyclohexanedicarboxylic acid To a suspension of isophthalic acid (5.0 g, 30.1 mmol) in 45 ml of acetic acid was added a slurry of 0.1 g of platinum oxide in 5 ml of acetic acid. The resulting mixture was stirred under 50 psi of hydrogen at 25° C. for 16 hours. NMR analysis (DMSO-d6) at this time showed complete reduction of starting material. The reaction mixture was filtered through Celite and the filter cake was rinsed with methanol. The combined filtrate and washes were concentrated under reduced pressure, using heptane to azeotropically remove residual acetic acid. Trituration of the resultant semi-solid with heptane and filtration of the precipitate provided 4.92 g (95percent) of the title compound as a white powder. mp: 163-165° C.
99 %Chromat.
With palladium 10% on activated carbon; hydrogen In water at 150℃; Autoclave; Inert atmosphere
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 25.1 g of isophthalic acid, 2.8 g of a catalyst (10percent Pd/C, manufactured by NE Chemcat Corporation), and 100 mL of water. The autoclave was purged with nitrogen introduced from the autoclave nozzle inlet three times at 5 MPa, and the mixture was heated to 150° C. while stirring at 400 rpm under normal pressure. [0163] When the temperature reached 150° C., hydrogen supply was started intermittently to achieve a pressure of 3.5 MPa, and the reaction was performed until there is no hydrogen absorption. [0164] After the completion of reaction, the product was cooled to room temperature. The reaction mixture was taken out, and after a 5N aqueous NaOH solution containing sodium hydroxide of 2.5 times mol the charged isophthalic acid amount was added thereto, the mixture was filtered to remove the catalyst. [0165] The filtrate was neutralized with a 5N aqueous HCl solution, and then analyzed by high-performance liquid chromatography. It was found that the conversion of isophthalic acid was 100percent, and the yield of 1,3-cyclohexanedicarboxylic acid was 99percent.
10 kg
With 5% active carbon-supported ruthenium; hydrogen In water at 100 - 120℃; Autoclave; Large scale
In a 50 L autoclave, 10 kg of isophthalic acid, 30 kg of water and 0.3 kg of a 5percent ruthenium-carbon catalyst were added, and the mixture was purged once with nitrogen and then with hydrogen three times. Turn on stirring, hydrogen pressure to 2MPa, heating to 100 degrees, began to hydrogen absorption, and gradually warming to 120 degrees, maintaining the temperature until no hydrogen absorption so far. Sampling monitoring, high performance liquid chromatography (HPLC) analysis, the raw material isophthalic acid reaction completely. Drop to room temperature, drain hydrogen, nitrogen once. The catalyst was filtered off, and the water in the reaction mixture was distilled off to obtain a viscous product. 10 L of methanol was added and the mixture was stirred for beating to obtain a white powder with good dispersibility. Filtration and drying afforded 10 kg of 1,3-cyclohexanedicarboxylic acid with a cis content of 80percent.
Reference：
[1] Patent: US2003/100576, 2003, A1,
[2] Patent: US2003/100576, 2003, A1,
[3] Patent: US2004/10005, 2004, A1, . Location in patent: Page 18
[4] Patent: JP2004/509897, 2004, A, . Location in patent: Page 45
[5] Patent: US2004/10005, 2004, A1, . Location in patent: Page 22
[6] Patent: JP2004/509897, 2004, A, . Location in patent: Page 54-55
[7] RSC Advances, 2017, vol. 7, # 30, p. 18178 - 18188
[8] Journal of Organic Chemistry, 1990, vol. 55, # 10, p. 3006 - 3007
[9] Patent: US2003/100576, 2003, A1,
[10] Patent: US2013/197269, 2013, A1, . Location in patent: Paragraph 0162-0165
[11] Patent: CN106316831, 2017, A, . Location in patent: Paragraph 0006; 0007
12
[ 201230-82-2 ]
[ 150177-91-6 ]
[ 625-99-0 ]
[ 121-91-5 ]
[ 585-76-2 ]
Reference：
[1] Journal of Organic Chemistry, 1993, vol. 58, # 18, p. 4794 - 4795
13
[ 121-91-5 ]
[ 618-88-2 ]
Yield
Reaction Conditions
Operation in experiment
88.3%
Stage #1: at 75℃; for 0.5 h; Stage #2: at 75 - 90℃;
Concentrated sulfuric acid (120 mL, 2.21 mol) was added to a three-necked flask and isophthalic acid (80 g, 0.48 mol) was added. The mixture was heated to 75° C. with stirring and incubated for 0.5 h. 60percent nitric acid (73.5 g, 0.70 mol) was added dropwise. , control the dropping rate and finish dropping in 2 to 2.5 hours. After the addition, the reaction was incubated at 75°C for 2 hours. Then, the temperature was raised to 90C and the reaction was carried out for 1 hour. The reaction was monitored completely, cooled to below 50C, and then 120 mL of water was added dropwise. The material was cooled to room temperature, filtered, and the waste acid was removed by suction filtration. The filter cake was washed three times with water, and the washing water was drained. The filter cake was added with pure water (120 mL), stirred and heated to dissolve, and the mixture was stirred well and stirred well. After hot filtration, cooling and crystallization, the filter cake was dried to obtain a white crystalline solid (89.6 g), yield 88.3percent,
Reference：
[1] Patent: CN107721859, 2018, A, . Location in patent: Paragraph 0025; 0027; 0029; 0031; 0033; 0034; 0035; 0036
[2] RSC Advances, 2016, vol. 6, # 10, p. 8495 - 8502
[3] Journal fuer Praktische Chemie (Leipzig), 1986, vol. 328, # 4, p. 497 - 514
[4] Langmuir, 2016, vol. 32, # 36, p. 9301 - 9312
[5] Acta Crystallographica Section C: Crystal Structure Communications, 1999, vol. 55, # 11, p. 1845 - 1847
[6] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1991, # 5, p. 645 - 650
[7] Journal fuer Praktische Chemie (Leipzig), 1880, vol. <2> 22, p. 352[8] Journal fuer Praktische Chemie (Leipzig), 1882, vol. <2> 25, p. 470
[9] Justus Liebigs Annalen der Chemie, 1870, vol. 153, p. 285
[10] Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 277
[11] Chemische Berichte, 1917, vol. 50, p. 434
[12] Yakugaku Zasshi, 1958, vol. 78, p. 1401[13] Chem.Abstr., 1959, p. 8056
14
[ 121-91-5 ]
[ 618-88-2 ]
[ 4315-09-7 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 277
[2] Journal fuer Praktische Chemie (Leipzig), 1888, vol. <2> 38, p. 313
15
[ 121-91-5 ]
[ 7697-37-2 ]
[ 618-88-2 ]
[ 4315-09-7 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 277
[2] Journal fuer Praktische Chemie (Leipzig), 1888, vol. <2> 38, p. 313
[3] Journal fuer Praktische Chemie (Leipzig), 1880, vol. <2> 22, p. 352[4] Journal fuer Praktische Chemie (Leipzig), 1882, vol. <2> 25, p. 470
[5] Justus Liebigs Annalen der Chemie, 1870, vol. 153, p. 285
[6] Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 277
16
[ 121-91-5 ]
[ 109-63-7 ]
[ 636-53-3 ]
Yield
Reaction Conditions
Operation in experiment
69%
at 120℃; for 4 h;
General procedure: In a 50 mL two-necked round-bottomed flask equipped with a magnetic stirring bar, a reflux condenser and a calcium chloride drying tube was placed nicotinic acid (1 g, 8.1 mmol) suspended in boron trifluoride etherate (10 mL). The reaction mixture was stirred and heated to 120 °C overnight during which the creamy reaction mixture changed into a brownish solution. Thin layer chromatography (hexane/ethyl acetate 3:1) revealed complete reaction. The cooled reaction mixture was diluted with water (25 mL) and extracted with ethyl acetate (3 x 10 mL). The combined organic extract was washed to the end of effervescence with a saturated solution of NaHCO3. The organic phase was dried over anhydrous Na2SO4 and concentrated in vacuo giving a crude yield of 1.11 g (92percent).
Reference：
[1] Bulletin of the Chemical Society of Ethiopia, 2018, vol. 32, # 2, p. 387 - 392
17
[ 64-67-5 ]
[ 121-91-5 ]
[ 636-53-3 ]
Reference：
[1] Synthesis, 1985, # 1, p. 40 - 45
18
[ 64-17-5 ]
[ 121-91-5 ]
[ 636-53-3 ]
Reference：
[1] Journal of the Chemical Society, 1896, vol. 69, p. 1241[2] Journal of the Chemical Society, 1900, vol. 77, p. 278
[3] Justus Liebigs Annalen der Chemie, 1870, vol. 153, p. 285
19
[ 121-91-5 ]
[ 618-88-2 ]
[ 4315-09-7 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 277
[2] Journal fuer Praktische Chemie (Leipzig), 1888, vol. <2> 38, p. 313
20
[ 121-91-5 ]
[ 7697-37-2 ]
[ 618-88-2 ]
[ 4315-09-7 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 277
[2] Journal fuer Praktische Chemie (Leipzig), 1888, vol. <2> 38, p. 313
[3] Journal fuer Praktische Chemie (Leipzig), 1880, vol. <2> 22, p. 352[4] Journal fuer Praktische Chemie (Leipzig), 1882, vol. <2> 25, p. 470
[5] Justus Liebigs Annalen der Chemie, 1870, vol. 153, p. 285
[6] Recueil des Travaux Chimiques des Pays-Bas, 1908, vol. 27, p. 277
21
[ 121-91-5 ]
[ 328-72-3 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1991, vol. 27, # 1.2, p. 108 - 112[2] Zhurnal Organicheskoi Khimii, 1991, vol. 27, # 1, p. 125 - 129
22
[ 121-91-5 ]
[ 328-70-1 ]
Reference：
[1] Journal of Organic Chemistry USSR (English Translation), 1991, vol. 27, # 1.2, p. 108 - 112[2] Zhurnal Organicheskoi Khimii, 1991, vol. 27, # 1, p. 125 - 129
23
[ 121-91-5 ]
[ 62638-06-6 ]
Reference：
[1] Journal of the American Chemical Society, 1980, vol. 102, p. 6862
[2] Journal of Organic Chemistry, 1990, vol. 55, # 10, p. 3006 - 3007
24
[ 67-56-1 ]
[ 121-91-5 ]
[ 62638-06-6 ]
Reference：
[1] Journal of Organic Chemistry, 1971, vol. 36, p. 924 - 928
Into a 50 ml pressure and sealable glass tube, 1.66 g (10 mmol) of isopthalic acid, 6.00 g of 10 wt percent fuming sulfuric acid and 1.6 g (10 mmol) of bromine were charged, and the content was stirred at 150° C. for 7 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. The resulting solid was filtered off, washed with cooling, and further dried under reduced pressure to give a crude crystal of the aimed product. Then, dimethyl esters were derived from the crystal by heating and stirring it at 120° C. with 13.1 g (408 mmol) of methanol and 0.35 g (30 mol percent) of sulfuric acid in an autoclave. In succession, the esters were subjected to rectification to give 1.78 g (yeild: 65.1percent, vacuum boiling point: 159° C./4.8 mmHg) of aimed dimethyl 5-bromoisophthalate and 0.52 g (yield: 26.8percent, vacuum boiling point: 133° C./4.8mmHg) of dimethyl isophthalate corresponding to a raw material. The resulting crystals were identified as dimethyl 5-bromoisophthalate and 5-bromoisophthalic acid by MASS, 1H-NMR and melting point.
Into a 100 ml pressure and sealable glass tube, 9.70 g (50 mmol) of dimethyl isophthalate, 30.00 g of 10 wt percent fuming sulfuric acid and 10.40 g (100 mmol) of bromine were charged, and the content was stirred at 120° C. for 7 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. The resulting solid was filtered off, washed with cooling, and further dried under reduced pressure to give 11.95 g of a crude crystal of the aimed product (reaction yield: 50.4percent 5-bromoisophthalic acid, 19.6percent isophthalic acid, 4.9percent 2,5-dibromoisophthalic acid, 7.2percent 4,5-dibromoisophthalic acid, 7.0percent dimethyl 5-bromoisophthalate, 1.5percent dimethyl isophthalate, 0.9percent dimethyl 2,5-dibromoisophthalate and 0.2percent dimethyl 4,5-dibromoisophthalate). Then, dimethyl esters were derived from the crystal by heating and stirring it with 65.50 g (2.04 mol) of methanol and 1.75 g (30 mol percent) of sulfuric acid in an autoclave at 120° C. [0038] In succession, the esters were subjected to rectification to give 6.73 g (yield: 49.3percent, vacuum boiling point: 159° C./4.8mmHg) of aimed dimethyl 5-bromoisophthalate and 1.67 g (yield: 17.2percent, vacuum boiling point: 133° C./4.8mmHg) of dimethyl isophthalate corresponding to a raw material. The resulting crystals were identified as dimethyl 5-bromoisophthalate and 5-bromoisophthalic acid by MASS, 1H-NMR and melting point.
33.23 g (0.2 mol) of isophthalic acid and 37.42 g (0.12 mol) of silver sulphate are dissolved in 330 ml of sulphuric acid. 13.3 ml (0.26 mol) of bromine are then added over 1 h. The solution is heated at 55° C. for 24 h. The medium is then poured into ice, the insoluble material is filtered and taken up in ethyl acetate. The remaining solid is taken up in water and basified with a saturated aqueous sodium hydrogen carbonate solution. The insoluble material is filtered and the filtrate is acidified and then extracted with ethyl acetate. The organic phase is washed with water and then dried over magnesium sulphate and concentrated. [00640] White powder. m=42.1 g. Y=86percent. m.p.=285-7° C. 1H NMR (DMSO): 8.40 (2H, s), 8.57 (1H, t), 13.76 (2H, COOH, s).
86.7%
at 60℃; for 32 h;
A mixture ofA (12.2 g, 73.5 mmol), Ag2SO4 (13.3g, 43 mmol) and Br2 (5 ml, 97 mmol) in conc. sulphuric acid was stirred at 60° C. for 32 h. The excess of Br2 was removed by addition of saturated Na2S2O3 solution very slowly. The residue was poured into ice-watet The solids were isolated by filtration and given into a NaHCO3 solution. The AgBr was then removed by filtration. The solution was acidified with concentrated hydrochloric acid to give white precipitates. The solid was filtered and washed with water several times to give the product as white solid 20.5 g (Yield. 86.7percent). 1H-NMR (DMSO-d5): ö=8.23 (d, 2H), 8.40 (t, 1H).
86.7%
With silver(II) sulfate; sulfuric acid; bromine In water at 60℃; for 32 h;
A mixture of A (12.2 g, 73.5 mmol), Ag2SO4 (13.3 g, 43 mmol) and Br2 (5ml, 97 mmol) in conc. sulphuric acidwas stirred at 60°C for 32 h. The excess of Br2 was removed by addition of saturated Na2S2O3 solution very slowly. Theresidue was poured into ice-water. The solids were isolated by filtration and given into a NaHCO3 solution. The AgBrwas then removed by filtration. The solution was acidified with concentrated hydrochloric acid to give white precipitates.The solid was filtered and washed with water several times to give the product as white solid 20.5g (Yield. 86.7percent). 1HNMR(DMSO-d6): δ = 8.23 (d, 2H), 8.40 (t, 1H).
20%
at 60℃;
Into a 100-mL round-bottom flask, was placed a solution of isophthalic acid (10 g, 60 24 mmol, 1 00 equiv) in 980ZoH2SO4 (60 mL) This was followed by the addition of N-bromosuccimmide (12 80 g, 72 32 mmol, 1 20 equiv), in portions at 6O0C in 10 mm The resulting solution was stirred overnight at 6O0C in an oil bath The reaction was cooled to room temperature and then quenched by the addition of water/ice The solids were collected by filtration, and washed with 2x60 mL of hexane The solid was dried in an oven under reduced pressure The crude product was purified by re-crystallization from ethyl acetate to give 3 g (20percent) of 5-bromoisophthalic acid as a white solid.
13.2 g
at 60℃; for 6 h;
Isophthalic acid (II) (5 g, 60 mmol) was dissolved in concentrated sulfuric acid (30 mL) at room temperature and raised to 60 ° C. NBS (10.6 g, 60 mmol) was then added to the solution in three batches and 3 g was added every half hour. TLC followed the reaction. After the reaction was completed, the reaction solution was poured into ice (200 g) and precipitated as a white solid. Filtered, filtered with water (100 mL) and petroleum ether (50 mL). The solvent was evaporated to dryness using a rotary evaporator to give 13.2 g of 5-bromoisophthalic acid as a white solid in a yield of 90percent and used directly in the next step.
Reference：
[1] Tetrahedron, 2001, vol. 57, # 24, p. 5027 - 5038
[2] Tetrahedron Letters, 2000, vol. 41, # 7, p. 1015 - 1018
[3] Journal of Organic Chemistry, 2007, vol. 72, # 15, p. 5867 - 5869
[4] Patent: US6689922, 2004, B1, . Location in patent: Page column 40-41
[5] Patent: US2015/152123, 2015, A1, . Location in patent: Paragraph 0156; 0157; 0158
[6] Patent: EP2876112, 2015, A1, . Location in patent: Paragraph 0163; 0164
[7] Chemical Communications, 2015, vol. 51, # 40, p. 8508 - 8511
[8] Patent: WO2010/78449, 2010, A2, . Location in patent: Page/Page column 310
[9] Asian Journal of Chemistry, 2015, vol. 27, # 8, p. 3127 - 3128
[10] Patent: CN106831397, 2017, A, . Location in patent: Paragraph 0006; 0010
30
[ 121-91-5 ]
[ 379711-35-0 ]
[ 379711-34-9 ]
[ 23351-91-9 ]
Yield
Reaction Conditions
Operation in experiment
11.9%
at 110 - 150℃; for 7 - 22 h;
Into a 50 ml pressure and sealable glass tube, 1.66 g (10 mmol) of isophthalic acid, 6.00 g of 10 wt percent fuming sulfuric acid and 1.6 g (10 mmol) of bromine were charged, and the content was stirred at 130° C. for 22 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. The resulting solid was filtered off, washed with cooling, and further dried under reduced pressure to give 2.41 g (purity: 83.5percent) of a crude crystal of the aimed product (yield: 81.9percent). Then, the crystals were solved in 10 g of methanol at 60° C., cooled to room temperature, and thereafter filtered off to give 1.61 g (purity: 100percent) of a white crystal (yield of recrystallization: 80.1percent). This crystal was identified as 5-bromopisophthalic acid by MASS, 1H-NMR and melting point. EXAMPLES 2 TO 7 [0033] Procedures were carried out similarly to that of Example 1 except that the reaction temperature, the concentration of fuming sulfuric acid and the amount of bromine were changed. The results on the resulting monobromo products were shown in Table 1. [TABLE-US-00001] TABLE 1 Concentration of Fuming Quantitative Yield (percent) Ex. Sulfuric Acid Bromine Tempera- Time 4,5- 2,5- No. (wt percent)-(g) g(mmol) ture(° C.) (h.) 5BIP IP DBIP DBIP 2 10-6 1.6(10) 110 22 34.5 58.0 trace - 3 20-6 1.6(10) 110 22 48.6 43.2 trace - 4 30-6 1.6(10) 110 22 62.8 24.6 2.3 - 5 10-6 1.6(10) 150 22 77.0 4.1 8.0 - 6 20-6 1.6(10) 150 7 53.8 46.5 0.7 - 7 10-6 3.2(20) 150 7 79.1 6.4 5.8 trace IP: Isophthalic Acid, 5BIP:5-Bromoisophthalic Acid, 4,5-DBIP: 4,5-Dibromoisophthalic Acid 2,5-DBIP: 2,5-Dibromoisophthalic Acid EXAMPLE 8 [0034] Into a 50 ml pressure and sealable glass tube, 1.66 g (10 mmol) of isopthalic acid, 6.00 g of 30 wt percent fuming sulfuric acid and 1.6 g (10 mmol) of bromine were charged, and the content was stirred at 150° C. for 22 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. Then, the resulting solid was filtered off, washed with cooling, and further purified by column chromatography on silica gel (chloroform/methanol=6/1, v/v) to give 0.51 g (yield: 20.7percent) of 5-bromoisophthalic acid, 0.76 g (yield: 23.5percent) of 4,5-dibromoisophthalic acid and 0.07 g (yield: 2.1percent) of 2,5-dibromoisophthalic acid. These crystals were identified by MASS, 1H-NMR and melting point. EXAMPLES 9 TO 16 [0035] Procedures were carried out similarly to that of Example 8 except that the reaction temperature, the concentration of fuming sulfuric acid and the amount of bromine were changed. The results on the resulting monobromo and dibromo products were shown in Table 2. [TABLE-US-00002] TABLE 2 Concentration of Fuming Quantitative Yield (percent) Ex. Sulfuric Acid Bromine Tempera- Time 4,5- 2,5- No. (wt percent)-(g) g(mmol) ture(° C.) (h.) 5BIP IP DBIP DBIP 9 60-6 1.6(10) 110 22 45.0 1.4 18.7 1.0 10 20-6 1.6(10) 130 22 49.2 0.0 15.3 trace 11 30-6 1.6(10) 130 22 53.1 0.8 13.6 1.0 12 20-6 1.6(10) 150 22 43.1 0.0 20.0 0.8 13 20-6 3.2(20) 150 7 37.5 0.0 23.3 1.5 14 10-12 1.6(10) 150 7 47.0 0.6 18.1 1.2 15 20-12 1.6(10) 150 7 49.8 0.7 20.3 1.4 16 20-12 3.2(10) 150 7 11.9 0.0 26.2 4.9 IP: Isophthalic Acid, 5BIP:5-Bromoisophthalic Acid, 4,5-DBIP: 4,5-Dibromoisophthalic Acid 2,5-DBIP: 2,5-Dibromoisophthalic Acid
Reference：
[1] Patent: US2004/15010, 2004, A1, . Location in patent: Page 3-4
[2] Organic Process Research and Development, 2002, vol. 6, # 5, p. 591 - 596
31
[ 1459-93-4 ]
[ 379711-35-0 ]
[ 379711-34-9 ]
[ 244768-63-6 ]
[ 121-91-5 ]
[ 51760-21-5 ]
[ 23351-91-9 ]
Yield
Reaction Conditions
Operation in experiment
50.4%
at 120℃; for 7 h;
Into a 100 ml pressure and sealable glass tube, 9.70 g (50 mmol) of dimethyl isophthalate, 30.00 g of 10 wt percent fuming sulfuric acid and 10.40 g (100 mmol) of bromine were charged, and the content was stirred at 120° C. for 7 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. The resulting solid was filtered off, washed with cooling, and further dried under reduced pressure to give 11.95 g of a crude crystal of the aimed product (reaction yield: 50.4percent 5-bromoisophthalic acid, 19.6percent isophthalic acid, 4.9percent 2,5-dibromoisophthalic acid, 7.2percent 4,5-dibromoisophthalic acid, 7.0percent dimethyl 5-bromoisophthalate, 1.5percent dimethyl isophthalate, 0.9percent dimethyl 2,5-dibromoisophthalate and 0.2percent dimethyl 4,5-dibromoisophthalate). Then, dimethyl esters were derived from the crystal by heating and stirring it with 65.50 g (2.04 mol) of methanol and 1.75 g (30 mol percent) of sulfuric acid in an autoclave at 120° C. [0038] In succession, the esters were subjected to rectification to give 6.73 g (yield: 49.3percent, vacuum boiling point: 159° C./4.8mmHg) of aimed dimethyl 5-bromoisophthalate and 1.67 g (yield: 17.2percent, vacuum boiling point: 133° C./4.8mmHg) of dimethyl isophthalate corresponding to a raw material. The resulting crystals were identified as dimethyl 5-bromoisophthalate and 5-bromoisophthalic acid by MASS, 1H-NMR and melting point.
Stage #1: With cesiumhydroxide monohydrate; C24H19F3N7O3RuS(1+)*CF3O3S(1-) In water at 150℃; for 24 h; Inert atmosphere; Schlenk technique Stage #2: With hydrogenchloride In waterInert atmosphere; Schlenk technique
Complex 2 (8.3 mg, 10 mmol), CsOHH2O (0.84 g, 5 mmol),alcohol (5 mmol) was added to a 25 mL schlenk tube and the solutionwas heated at 150 C (oil bath) for 24 h in an open systemunder argon. After cooling to room temperature, the degassedwater (5 mL)was added and the mixturewas extracted with diethylether (3 10 mL). A sample of ether phasewas subjected to the GCMSanalysis and the residual solution was evaporated, then subjected to the NMR analysis. The aqueous phase was acidifiedwith 6 M HCl and extracted with ethyl acetate (5 20 mL). Thecombined organic phasewaswashed with brine (25 mL), dried overanhydrous Na2SO4, and evaporated under reduced pressure, thepure carboxylic acid was collected and weighed for calculating theyield, which was further characterized by its 1H NMR which isconsist with the standard sample.
52%
Stage #1: With cesiumhydroxide monohydrate; C24H19F3N7O3RuS(1+)*CF3O3S(1-) In water at 150℃; for 24 h; Inert atmosphere; Schlenk technique Stage #2: With hydrogenchloride In waterInert atmosphere; Schlenk technique
Complex 2 (8.3 mg, 10 mmol), CsOHH2O (0.84 g, 5 mmol),alcohol (5 mmol) was added to a 25 mL schlenk tube and the solutionwas heated at 150 C (oil bath) for 24 h in an open systemunder argon. After cooling to room temperature, the degassedwater (5 mL)was added and the mixturewas extracted with diethylether (3 10 mL). A sample of ether phasewas subjected to the GCMSanalysis and the residual solution was evaporated, then subjected to the NMR analysis. The aqueous phase was acidifiedwith 6 M HCl and extracted with ethyl acetate (5 20 mL). Thecombined organic phasewaswashed with brine (25 mL), dried overanhydrous Na2SO4, and evaporated under reduced pressure, thepure carboxylic acid was collected and weighed for calculating theyield, which was further characterized by its 1H NMR which isconsist with the standard sample.
Reference：
[1] Journal of Organometallic Chemistry, 2017, vol. 830, p. 11 - 18
[2] Journal of Organometallic Chemistry, 2017, vol. 830, p. 11 - 18
35
[ 121-91-5 ]
[ 626-18-6 ]
[ 28286-79-5 ]
Reference：
[1] Organic Preparations and Procedures International, 2002, vol. 34, # 6, p. 665 - 670
With sodium tetrahydroborate; In tetrahydrofuran; ethanol; at 20℃; for 3h;
To a stirred THF (40 mL) solution of isophthalaldehyde (0.27 g, 2.0 mmol) was slowlyadded NaBH4 (0.30 g, 7.9 mmol). To the mixture was slowly added EtOH (10 mL) andthe resulting mixture was stirred at room temperature for 3 h. To the solution was slowlyadded ice water (10 mL) at 0 C followed by 10% HCl aq until reaching a pH<7. Themixture was extracted with Et2O (50 mL x 5). The combined organic layers werewashed with brine (50 mL x 5), dried over Na2SO4, filtered and concentrated in vacuo togive benzene-1,3-dimethanol (7a, 0.25 g, 69% yield). The resultingsolution was stirred at reflux for 2 h. To the solution was added THF (100 mL) solutionof 1,3-bis(bromomethyl)benzene (8a, 1.53 g, 5.7 mmol), and the mixture was stirred atreflux for 2 days. To the solution was added ice water (20 mL) at<10 C. The mixturewas extracted with Et2O (50 mL x 3). The combined organic layers were washed withbrine (50 mL x 3), dried over Na2SO4, filtered, and concentrated in vacuo, giving aresidue that was subjected to silica gel column chromatography (three times, eacheluent; hexane:AcOEt = 1:1, hexane:CHCl3 = 10:1, CHCl3:AcOEt = 20:1) followed byrecrystallization from CH2Cl2/hexane gave 2,11-dioxa[3.3]metacyclophane (6a, 0.01 g,7% yield). Colorless solid; mp 115-117 C.
1,3-cyclohexanedicarboxylic acid To a suspension of isophthalic acid (500 g, 3 mol) in methanol (2.81) was added 5% Rhodium-on-alumina catalyst (50 g) and acetic acid (150 ml). The reaction mixture was shaken under hydrogen (50 psi) at room temperature overnight. The mixture was filtered through celite. To this solution was added fresh 5% Rhodium-on-alumina catalyst (25 g), and the mixture was shaken under 50 psi of hydrogen for another 24 hours. The final reaction mixture was filtered through celite. The solution was concentrated under vacuum to give 493 g of the title compound as a white powder (96.3 % yield). m.p. 163-165 C.
96.3%
With hydrogen; acetic acid; In methanol;
PREPARATION a 1,3-cyclohexanedicarboxylic acid To a suspension of isophthalic acid (500 g, 3 mol) in methanol (2.8 1) was added 5% Rhodium-on-alumina catalyst (50 g) and acetic acid (150 ml). The reaction mixture was shaken under hydrogen (50 psi) at room temperature overnight. The mixture was filtered through celite. To this solution was added fresh 5% Rhodium-on-alumina catalyst (25 g), and the mixture was shaken under 50 psi of hydrogen for another 24 hours. The final reaction mixture was filtered through celite. The solution was concentrated under vacuum to give 493 g of the title compound as a white powder (96.3% yield). m.p. 163-165 C.
96.3%
With hydrogen; acetic acid;5% rhodium on alumina; In methanol; at 20℃; under 2585.81 Torr; for 24h;
To a suspension of isophthalic acid (500 g, 3 mol) in methanol (2.8 l) was added 5% Rhodium-on-alumina catalyst (50 g) and acetic acid (150 ml).The reaction mixture was shaken under hydrogen (50 psi) at room temperature overnight.The mixture was filtered through celite.To this solution was added fresh 5% Rhodium-on-alumina catalyst (25 g), and the mixture was shaken under 50 psi of hydrogen for another 24 hours.The final reaction mixture was filtered through celite.The solution was concentrated under vacuum to give 493 g of the title compound as a white powder (96.3% yield).m.p. 163-165 C. 1H NMR of 2: (300 MHz, CDCl3) delta 9.00-10.00 (sb, 2H), 2.95 (m, 0.5H), 2.20-2.40 (m, 2.5H), 1.90-2.10 (m, 3H), 1.78 (m, 1H), 1.58 (t, 1H), 1.39 (d, 2H).
95%
With hydrogen;platinum(IV) oxide; In acetic acid; at 25℃; under 2585.81 Torr; for 16h;
To a suspension of isophthalic acid (5.0 g, 30.1 mmol) in 45 ml of acetic acid was added a slurry of 0.1 g of platinum oxide in 5 ml of acetic acid.The resulting mixture was stirred under 50 psi of hydrogen at 25 C. for 16 hours. NMR analysis (DMSO-d6) at this time showed complete reduction of starting material.The reaction mixture was filtered through Celite and the filter cake was rinsed with methanol.The combined filtrate and washes were concentrated under reduced pressure, using heptane to azeotropically remove residual acetic acid.Trituration of the resultant semi-solid with heptane and filtration of the precipitate provided 4.92 g (95%) of the title compound as a white powder. mp: 163-165 C. 1H NMR (300 MHz, CDCl3) delta 9.00-10.00 (br s, 2H), 2.95 (m, 0.5H), 2.20-2.40 (m, 2.5H), 1.90-2.10 (m, 3H), 1.78 (m, 1H), 1.58 (t, 1H), 1.39 (d, 2H).
4.92 g (95%)
With hydrogen; In n-heptane; acetic acid;
PREPARATION u 1,3-cyclohexanedicarboxylic acid To a suspension of isophthalic acid (5.0 g, 30.1 mmol) in 45 ml of acetic acid was added a slurry of 0.1 g of platinum oxide in 5 ml of acetic acid. The resulting mixture was stirred under 50 psi of hydrogen at 25 C. for 16 hours. NMR analysis (DMSO-d6) at this time showed complete reduction of starting material. The reaction mixture was filtered through Celite and the filter cake was rinsed with methanol. The combined filtrate and washes were concentrated under reduced pressure, using heptane to azeotropically remove residual acetic acid. Trituration of the resultant semi-solid with heptane and filtration of the precipitate provided 4.92 g (95%) of the title compound as a white powder. mp: 163-165 C.
99%Chromat.
With palladium 10% on activated carbon; hydrogen; In water; at 150℃; under 26252.6 Torr;Autoclave; Inert atmosphere;
A 100 mL stainless steel-made autoclave equipped with a stirrer was charged with 25.1 g of isophthalic acid, 2.8 g of a catalyst (10% Pd/C, manufactured by NE Chemcat Corporation), and 100 mL of water. The autoclave was purged with nitrogen introduced from the autoclave nozzle inlet three times at 5 MPa, and the mixture was heated to 150 C. while stirring at 400 rpm under normal pressure. [0163] When the temperature reached 150 C., hydrogen supply was started intermittently to achieve a pressure of 3.5 MPa, and the reaction was performed until there is no hydrogen absorption. [0164] After the completion of reaction, the product was cooled to room temperature. The reaction mixture was taken out, and after a 5N aqueous NaOH solution containing sodium hydroxide of 2.5 times mol the charged isophthalic acid amount was added thereto, the mixture was filtered to remove the catalyst. [0165] The filtrate was neutralized with a 5N aqueous HCl solution, and then analyzed by high-performance liquid chromatography. It was found that the conversion of isophthalic acid was 100%, and the yield of 1,3-cyclohexanedicarboxylic acid was 99%.
10 kg
With 5% active carbon-supported ruthenium; hydrogen; In water; at 100 - 120℃; under 15001.5 Torr;Autoclave; Large scale;
In a 50 L autoclave, 10 kg of isophthalic acid, 30 kg of water and 0.3 kg of a 5% ruthenium-carbon catalyst were added, and the mixture was purged once with nitrogen and then with hydrogen three times. Turn on stirring, hydrogen pressure to 2MPa, heating to 100 degrees, began to hydrogen absorption, and gradually warming to 120 degrees, maintaining the temperature until no hydrogen absorption so far. Sampling monitoring, high performance liquid chromatography (HPLC) analysis, the raw material isophthalic acid reaction completely. Drop to room temperature, drain hydrogen, nitrogen once. The catalyst was filtered off, and the water in the reaction mixture was distilled off to obtain a viscous product. 10 L of methanol was added and the mixture was stirred for beating to obtain a white powder with good dispersibility. Filtration and drying afforded 10 kg of 1,3-cyclohexanedicarboxylic acid with a cis content of 80%.
With sulfuric acid; bromine; silver sulfate; at 55℃; for 25h;
33.23 g (0.2 mol) of isophthalic acid and 37.42 g (0.12 mol) of silver sulphate are dissolved in 330 ml of sulphuric acid. 13.3 ml (0.26 mol) of bromine are then added over 1 h. The solution is heated at 55 C. for 24 h. The medium is then poured into ice, the insoluble material is filtered and taken up in ethyl acetate. The remaining solid is taken up in water and basified with a saturated aqueous sodium hydrogen carbonate solution. The insoluble material is filtered and the filtrate is acidified and then extracted with ethyl acetate. The organic phase is washed with water and then dried over magnesium sulphate and concentrated. [00640] White powder. m=42.1 g. Y=86%. m.p.=285-7 C. 1H NMR (DMSO): 8.40 (2H, s), 8.57 (1H, t), 13.76 (2H, COOH, s).
86.7%
With silver(II) sulfate; sulfuric acid; bromine; In water; at 60℃; for 32h;
A mixture of A (12.2 g, 73.5 mmol), Ag2SO4 (13.3 g, 43 mmol) and Br2 (5ml, 97 mmol) in conc. sulphuric acidwas stirred at 60C for 32 h. The excess of Br2 was removed by addition of saturated Na2S2O3 solution very slowly. Theresidue was poured into ice-water. The solids were isolated by filtration and given into a NaHCO3 solution. The AgBrwas then removed by filtration. The solution was acidified with concentrated hydrochloric acid to give white precipitates.The solid was filtered and washed with water several times to give the product as white solid 20.5g (Yield. 86.7%). 1HNMR(DMSO-d6): delta = 8.23 (d, 2H), 8.40 (t, 1H).
86.7%
With silver(II) sulfate; sulfuric acid; bromine; at 60℃; for 32h;
A mixture ofA (12.2 g, 73.5 mmol), Ag2SO4 (13.3g, 43 mmol) and Br2 (5 ml, 97 mmol) in conc. sulphuric acid was stirred at 60 C. for 32 h. The excess of Br2 was removed by addition of saturated Na2S2O3 solution very slowly. The residue was poured into ice-watet The solids were isolated by filtration and given into a NaHCO3 solution. The AgBr was then removed by filtration. The solution was acidified with concentrated hydrochloric acid to give white precipitates. The solid was filtered and washed with water several times to give the product as white solid 20.5 g (Yield. 86.7%). 1H-NMR (DMSO-d5): oe=8.23 (d, 2H), 8.40 (t, 1H).
20%
With N-Bromosuccinimide; sulfuric acid; at 60℃;
Into a 100-mL round-bottom flask, was placed a solution of isophthalic acid (10 g, 60 24 mmol, 1 00 equiv) in 980ZoH2SO4 (60 mL) This was followed by the addition of N-bromosuccimmide (12 80 g, 72 32 mmol, 1 20 equiv), in portions at 6O0C in 10 mm The resulting solution was stirred overnight at 6O0C in an oil bath The reaction was cooled to room temperature and then quenched by the addition of water/ice The solids were collected by filtration, and washed with 2x60 mL of hexane The solid was dried in an oven under reduced pressure The crude product was purified by re-crystallization from ethyl acetate to give 3 g (20%) of 5-bromoisophthalic acid as a white solid.
With N-Bromosuccinimide; sulfuric acid; water; at 59.84℃; for 20h;Sealed tube;
5-Bromoisophthalic acid was prepared under the hydrothermal conditions. A mixture of isophthalic acid (16.6 mg, 0.1 mmol), H2SO4 (9.8 mg, 0.2mmol) and N-bromosuccinimide (NBS) (14.13 mg, 0.1 mmol), H2O (12 mL) was sealed into a 25 mL stainless steel reactor with a Teflon liner and heated at 333 K for 20 h. The reactor was then cooled slowly to room temperature and the solution filtered. Yellow block-shaped crystals were obtained from the filtrate after several days at room temperature.
13.2 g
With N-Bromosuccinimide; sulfuric acid; at 60℃; for 6h;
Isophthalic acid (II) (5 g, 60 mmol) was dissolved in concentrated sulfuric acid (30 mL) at room temperature and raised to 60 C. NBS (10.6 g, 60 mmol) was then added to the solution in three batches and 3 g was added every half hour. TLC followed the reaction. After the reaction was completed, the reaction solution was poured into ice (200 g) and precipitated as a white solid. Filtered, filtered with water (100 mL) and petroleum ether (50 mL). The solvent was evaporated to dryness using a rotary evaporator to give 13.2 g of 5-bromoisophthalic acid as a white solid in a yield of 90% and used directly in the next step.
12 g
With N-Bromosuccinimide; sulfuric acid; at 60℃; for 2h;
A (14.0 g, 0.084 mol) was dissolved in 40 mL cone. H2SO4 at 60 C under stirring. N-Bromosuccinimide (NBS, 16 g, 0.090 mol) was added to the reaction in portions over 1 hour and the mixture was stirred at 60 C for an additional hour. After the reaction was completed, the mixture was poured into 200 g crushed ice and stirred at room temperature for 1 hour. Light yellow solid was obtained by filtration and washed with DI water (100 mL). The crude product was recrystallized from ethyl acetate to give pure B (12 g, 59 % yield).
Isophthalic acid in an amount of 18 mmol (3.0 g) and N-methyl-1,2-phenylenediamine in an amount of 36 mmol (4.4 g) were placed into an eggplant type flask with a capacity of 500 milliliter and added polyphosphoric acid in an amount of 75 milliliter. The resultant solution reacted at the temperature of 100 C for 15 hours and further, it was heated at the temperature of 200 C for 4 hours. After the resultant solution was cooled by leaving it standing, it was added to 600 milliliter of pure water and then, the resultant solution was neutralized with NaOH aqueous solution of 5M until it became pH7, subsequently gathering a precipitated purple solid by filtration, the purple solid was washed with pure water thoroughly. The resultant solid was re-crystallized with the use of methanol and as a result, 3.3 g of aimed mbib was obtained (yield: 54 %).
With sulfuric acid; sulfur trioxide; bromine; at 110 - 150℃; for 7 - 22h;
Into a 50 ml pressure and sealable glass tube, 1.66 g (10 mmol) of isophthalic acid, 6.00 g of 10 wt percent fuming sulfuric acid and 1.6 g (10 mmol) of bromine were charged, and the content was stirred at 130° C. for 22 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. The resulting solid was filtered off, washed with cooling, and further dried under reduced pressure to give 2.41 g (purity: 83.5percent) of a crude crystal of the aimed product (yield: 81.9percent). Then, the crystals were solved in 10 g of methanol at 60° C., cooled to room temperature, and thereafter filtered off to give 1.61 g (purity: 100percent) of a white crystal (yield of recrystallization: 80.1percent). This crystal was identified as 5-bromopisophthalic acid by MASS, 1H-NMR and melting point. EXAMPLES 2 TO 7 [0033] Procedures were carried out similarly to that of Example 1 except that the reaction temperature, the concentration of fuming sulfuric acid and the amount of bromine were changed. The results on the resulting monobromo products were shown in Table 1. [TABLE-US-00001] TABLE 1 Concentration of Fuming Quantitative Yield (percent) Ex. Sulfuric Acid Bromine Tempera- Time 4,5- 2,5- No. (wt percent)-(g) g(mmol) ture(° C.) (h.) 5BIP IP DBIP DBIP 2 10-6 1.6(10) 110 22 34.5 58.0 trace - 3 20-6 1.6(10) 110 22 48.6 43.2 trace - 4 30-6 1.6(10) 110 22 62.8 24.6 2.3 - 5 10-6 1.6(10) 150 22 77.0 4.1 8.0 - 6 20-6 1.6(10) 150 7 53.8 46.5 0.7 - 7 10-6 3.2(20) 150 7 79.1 6.4 5.8 trace IP: Isophthalic Acid, 5BIP:5-Bromoisophthalic Acid, 4,5-DBIP: 4,5-Dibromoisophthalic Acid 2,5-DBIP: 2,5-Dibromoisophthalic Acid EXAMPLE 8 [0034] Into a 50 ml pressure and sealable glass tube, 1.66 g (10 mmol) of isopthalic acid, 6.00 g of 30 wt percent fuming sulfuric acid and 1.6 g (10 mmol) of bromine were charged, and the content was stirred at 150° C. for 22 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. Then, the resulting solid was filtered off, washed with cooling, and further purified by column chromatography on silica gel (chloroform/methanol=6/1, v/v) to give 0.51 g (yield: 20.7percent) of 5-bromoisophthalic acid, 0.76 g (yield: 23.5percent) of 4,5-dibromoisophthalic acid and 0.07 g (yield: 2.1percent) of 2,5-dibromoisophthalic acid. These crystals were identified by MASS, 1H-NMR and melting point. EXAMPLES 9 TO 16 [0035] Procedures were carried out similarly to that of Example 8 except that the reaction temperature, the concentration of fuming sulfuric acid and the amount of bromine were changed. The results on the resulting monobromo and dibromo products were shown in Table 2. [TABLE-US-00002] TABLE 2 Concentration of Fuming Quantitative Yield (percent) Ex. Sulfuric Acid Bromine Tempera- Time 4,5- 2,5- No. (wt percent)-(g) g(mmol) ture(° C.) (h.) 5BIP IP DBIP DBIP 9 60-6 1.6(10) 110 22 45.0 1.4 18.7 1.0 10 20-6 1.6(10) 130 22 49.2 0.0 15.3 trace 11 30-6 1.6(10) 130 22 53.1 0.8 13.6 1.0 12 20-6 1.6(10) 150 22 43.1 0.0 20.0 0.8 13 20-6 3.2(20) 150 7 37.5 0.0 23.3 1.5 14 10-12 1.6(10) 150 7 47.0 0.6 18.1 1.2 15 20-12 1.6(10) 150 7 49.8 0.7 20.3 1.4 16 20-12 3.2(10) 150 7 11.9 0.0 26.2 4.9 IP: Isophthalic Acid, 5BIP:5-Bromoisophthalic Acid, 4,5-DBIP: 4,5-Dibromoisophthalic Acid 2,5-DBIP: 2,5-Dibromoisophthalic Acid
With sulfuric acid; sulfur trioxide; bromine; at 120℃; for 7h;
Into a 100 ml pressure and sealable glass tube, 9.70 g (50 mmol) of dimethyl isophthalate, 30.00 g of 10 wt percent fuming sulfuric acid and 10.40 g (100 mmol) of bromine were charged, and the content was stirred at 120° C. for 7 hours. After the conclusion of the reaction, the content was cooled to room temperature, and placed in a beaker containing ice water to give a solid. The resulting solid was filtered off, washed with cooling, and further dried under reduced pressure to give 11.95 g of a crude crystal of the aimed product (reaction yield: 50.4percent 5-bromoisophthalic acid, 19.6percent isophthalic acid, 4.9percent 2,5-dibromoisophthalic acid, 7.2percent 4,5-dibromoisophthalic acid, 7.0percent dimethyl 5-bromoisophthalate, 1.5percent dimethyl isophthalate, 0.9percent dimethyl 2,5-dibromoisophthalate and 0.2percent dimethyl 4,5-dibromoisophthalate). Then, dimethyl esters were derived from the crystal by heating and stirring it with 65.50 g (2.04 mol) of methanol and 1.75 g (30 mol percent) of sulfuric acid in an autoclave at 120° C. [0038] In succession, the esters were subjected to rectification to give 6.73 g (yield: 49.3percent, vacuum boiling point: 159° C./4.8mmHg) of aimed dimethyl 5-bromoisophthalate and 1.67 g (yield: 17.2percent, vacuum boiling point: 133° C./4.8mmHg) of dimethyl isophthalate corresponding to a raw material. The resulting crystals were identified as dimethyl 5-bromoisophthalate and 5-bromoisophthalic acid by MASS, 1H-NMR and melting point.
EXAMPLE 5 83 g isophthalic acid (0.5 mol) are added to 200 ml tetramethylene sulphone and heated to 210-220 C. At this temperature 61.5 g cyanogen chloride (1 mol) are added dropwise within 2 hours, the mixture is stirred for a further 15 minutes, filtered, allowed to cool, poured into water and the reaction product precipitated is filtered. Yield: 58 g isophthalic acid dinitrile (91% of theory), m.p.: 162 C. (from ethyl acetate).
[Cd2(levofloxacin)(1,3-benzenedicarboxylate)2(H2O)2][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
46%
With Adipic acid; triethylamine; In water; at 150 - 160℃; for 128h;Autoclave;
A mixture of Cd(OAc)22H2O (0.5 mmol), LevofH (0.25 mmol),1,3-bdc (0.25 mmol), adipic acid (0.25 mmol), Et3N (0.5 mL), anddistilled water (8 mL) was stirred for 30 min in air, then sealed inan 18 mL Teflon-lined autoclave, which was heated at 150C for48 h and then heated at 160 C for 80 h under autogenous pressure.After slow cooling to room temperature, yellow block crystals of 3were filtered off, washed with distilled water and dried at ambienttemperature (55 mg, yield: 46% based on 1,3-bdc). Anal. Calc. forC34H32Cd2F2N3O14 (3): C, 42.97; H, 3.39; N, 4.42; Cd, 23.65. Found:C, 42.77; H, 3.54; N, 4.62; Cd, 23.49%. FT/IR data (cm1): 3386 (br),2860(w), 2658(w), 2523(w), 2483(w), 1902(w), 1630(s), 1606(s),1582(w), 1561(w), 1474(m), 1456(w), 1442(w), 1425(w), 1384(s),1347(w), 1268(m), 1185(w), 1151(w), 1126(s), 1092(w),1051(m), 1023(m), 977(m), 951(s), 914(w), 875(w), 838(w),819(s), 755(m), 737(w), 724(s), 690(w), 657(w), 631(w), 594(w),497(w), 464(m), 434(w), 413(w).
With sodium hydroxide; In ethanol; at 150℃; for 72h;pH 6.0;
A mixture of <strong>[86386-73-4]fluconazole</strong> (153 mg, 0:5 mmol), isophthalic acid (83 mg, 0:5 mmol), CdSO4 (208 mg, 1:0 mmol), 15 mL H2O, and 4 mL ethanol was sealed in a 30 mL Teflon-lined stainless-steel container. An aqueous solution of sodium hydroxide was added dropwise with stirring to adjust the pH value of the solution to 6.0. The mixture was kept under autogenous pressure at 150 C for 3 days before cooling to room temperature at a rate of 5 C h-1. Transparent crystals of 1 were obtained, washed with alcohol three times, and dried in a vacuum desiccator using silica gel (yield 71.8%). Elemental analysis (%) for C21H20F2N6O7Cd: calcd. C 40.76, H 3.26,N 13.58; found C 40.68, H 3.17, N 13.70. - IR (KBr, cm-1): v =3165w, 3116m, 1606s, 1553s, 1504m, 1476w, 1435m,1385s, 1282m, 1215w, 1134s, 1097w, 962w, 725m, 674m.
With sodium hydroxide; In ethanol; water; at 150℃; for 72h;pH 6.0;Sealed tube; Inert atmosphere;
For preparation of complex 1, a mixture of <strong>[86386-73-4]fluconazole</strong>(153 mg, 0.5 mmol), isophthalic acid (83 mg, 0.5 mmol),ZnCl2 (136 mg, 1.0 mmol), 15 mL H2O, and 4 mL ethanolwas sealed in a 30 mL Teflon-lined stainless steel container.An aqueous solution of sodium hydroxide was addeddropwise with stirring to adjust the pH value of the solutionbeing 6.0. Kept under autogenous pressure at 150 C for 3days before cooling to room temperature at a rate of 5 C h-1;Then the transparent crystals of 1 were obtained. Thecrystals were isolated, washed with alcohol three times,and dried in a vacuum desiccator using silicagel (yield72.6%, based on Zn). Elemental analysis Calcd (%) forC21H16F2N6O5Zn: C 47.08, H 3.01, N 15.69. Found (%): C47.11, H 3.04, N 15.73. IR (KBr, cm-1): 3430w, 3159w,3124w, 1611s, 1565s, 1500m, 1477w, 1359s, 1276m, 1130m,1102w, 994w, 965w, 740m, 674w, 658w.
[Mn(2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol)2(IPA)(H2O)]·H2O}n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67.2%
With sodium hydroxide; In ethanol; at 150℃; for 72h;pH 5;
General procedure: A mixture of <strong>[86386-73-4]fluconazole</strong> (153 mg, 0.5 mM), diphenic acid (120 mg, 0.5 mM), CoSO4·7H2O (281 mg, 1.0 mM), 15 mL H2O, and 3 mL ethanol was adjusted to pH 5 by dropwise addition of an aqueous solution of sodium hydroxide, then sealed in a 30 mL Teflon-lined stainless steel container. The mixture was kept under autogenous pressure at 150 C for 3 days before cooling to room temperature at a rate of 5 C h-1. Light red crystals (0.157 g, 65.6% yield) were isolated, washed with alcohol three times, and dried in a vacuum desiccator over silica gel.
[Zn(2-(2,4-difluorophenyl)-1,3-bis(1,2,4-triazol-1-yl)propan-2-ol)(IPA)]·H2O}n[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70.1%
With sodium hydroxide; In ethanol; at 150℃; for 72h;pH 5;
General procedure: A mixture of <strong>[86386-73-4]fluconazole</strong> (153 mg, 0.5 mM), diphenic acid (120 mg, 0.5 mM), CoSO4·7H2O (281 mg, 1.0 mM), 15 mL H2O, and 3 mL ethanol was adjusted to pH 5 by dropwise addition of an aqueous solution of sodium hydroxide, then sealed in a 30 mL Teflon-lined stainless steel container. The mixture was kept under autogenous pressure at 150 C for 3 days before cooling to room temperature at a rate of 5 C h-1. Light red crystals (0.157 g, 65.6% yield) were isolated, washed with alcohol three times, and dried in a vacuum desiccator over silica gel.
Example 12 130 g (1200 mmol) of 2-methylglutaronitrile and 20 g (120 mmol) of isophthalic acid are introduced into a 250 ml glass reactor. The white suspension is stirred and 0.32 g (2.4 mmol) of anhydrous aluminum chloride is added. The mixture is gradually heated to 270 C. and is maintained under these conditions for 4 h. During the rise in temperature, the isophthalic acid dissolves in the MGN. The reaction medium is subsequently analyzed by GC. An RY % for MGI of 76% and a yield of 1,3-dicyanobenzene of 69% are obtained.
[Mn(2-(5-methyl-1H-pyrazol-3-yl)pyridine)2(m-phthalic acid)2][ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
In methanol; for 0.25h;
A 5mL methanol solution of L (0.2mmol, 31.8mg) and m-phthalic acid (0.2mmol, 33.2mg) was mixed with a 5mL methanol solution of Mn(HCOO)2·2H2O (0.1mmol, 14.5mg), and the resulting mixture was then stirred 15min to obtain a colorless solution. This colorless solution was filtered and left to evaporate for one week, giving rise to colorless stick-like crystals. The resulting crystals were washed with n-hexane 2?3 times, then dried in vacuum. Yield: 47.1mg (67%), M. p. > 300C. Anal. Calc. for C34H28MnN6O8 (FW, 703.56): C, 58.04; H, 4.01; N, 11.95. Found: C, 58.98; H, 4.73; N, 11.49%. Selected IR data (cm-1, KBr): 3256 (b, s), 3128 (m), 3073 (m), 2925 (m), 2883 (m), 1694 (s) (nu(C=O)), 1606 (m) (nu(C=N)), 1561 (s) (nu(C=C)), 1428 (m) (delta(CH3)), 1392 (s), 1296 (m) (nu(C-N)), 1161 (w), 777 (m), 733 (m), 689 (m).
In ethanol; water; at 150℃; for 72h;pH 6;Autoclave;
A mixture of <strong>[86386-73-4]fluconazole</strong> (153 mg, 0.5 mmol), isophthalic acid (83 mg, 0.5 mmol), ZnCl2(136 mg, 1.0 mmol), 17 mL H2O, and 2 mL ethanol was sealed in a 30 mL Teflon-linedstainless-steel container. An aqueous solution of sodium hydroxide was added dropwisewith stirring to adjust the pH value of the solution to 6.0. The mixture was kept underautogenous pressure at 150C for 3 days before cooling to room temperature at a rate of5C hr-1. Transparent crystals of 1 were obtained, washed with alcohol three times, anddried in a vacuum desiccator using silicagel (yield: 62.8% based on Zn). Elemental analysis(%) for C34H46F4N12O15Zn: calcd. C 40.67, H 4.62, N 16.74; found: C 40.56, H 4.65, N16.69. IR (KBr, cm-1): 3480 s, 3117 m, 1616 s, 1540 s, 1419 m, 1374 m, 1320 m, 1385 s,1277 s, 1260 w, 1129 s, 1111 w, 993 w, 862 m, 655 m.
A solution of CoCl2¢6H2O (0.25 g, 1.05 mmol), 3-PBIM(0.2 g, 1.03 mmol), 1,3-H2BDC (0.2 g, 1.2 mmol), and H2O(15 mL) was stirred under ambient condition. The mixturewas then sealed in a Teflon-lined steel vessel and heated at170C for three days. After slow cooling to room temperature, the resulting product was obtained (yield: 55%). Anal.Calcd. for C64H56Co2N12O14: C, 57.58; N, 12.59; H, 4.23%.Found: C, 58.13; N, 12.87; H, 4.54%. IR (KBr pellet, cm1):3450 s, 3050 s, 1870 m, 1615 s, 1565 w, 1535 m, 1500 m, 1478m, 1448 m, 1371 m, 1270 s, 1145 m, 1130 m, 1060 s, 1018 s,970 s, 880 m, 840 s, 770 m, 745 s, 705 m, 695 m, 593 m, 565 m.
(tetraethylammonium)[Cd3(adenine)2(isophtalate)2bromide]*3methanol*3.5(N,N-dimethylacetamide)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
at 20 - 100℃; for 72h;
Isophthalic acid (H2ipa, 166 mg,1 mmol), <strong>[73-24-5]adenine</strong> (Had, 135 mg, 1 mmol), Cd(NO3)2 4H2O (462 mg, 1 mmol) and tetraethylammonium bromide (220 mg, 1 mmol)were added to 4 mL DMA (N,N-dimethylacetamide) and 1.5 mL MeOH (methanol)mixed solvents, and then the solution was placed in a 20 mL vial and stired at room temperature for 1h. The mixture was heated at 100 C for 3 days, and then cooled slowly to room temperature over 4h. Colourless rod-like crystals of the product were formed and collected by filtration and washed with DMA several times. (Yield: 65%based on H2ipa).
In a typical example, 18.3 mg (0.97 mmol) of 1 and 16.6 mg (0.99 mmol) of pyridine-2,6-dicarboxylic acid, a, were dissolved by heating up to 80 C in 2 mL DMSO and allowed for slow evaporation at ambient conditions. Good quality single crystals suitable for X-ray diffraction study were obtained in 48 h.
, weighing 0.25g cobalt chloride hexahydrate,0.2 g of 2- (3-pyridyl) benzimidazole,0.2 g of 1,3-benzenedicarboxylic acid and 15 mL of water in a 50 mL flask,The flask was placed on a magnetic stirrer and stirred for 30 minutes.(2)The mixed homogeneous solution was transferred to a 25 mL autoclave.,The autoclave was placed in an oven,Heated from room temperature to 170 C at a rate of 1 C / min,At this temperature for 72h,And then to 5 / h rate down to room temperature,Solid-liquid separation is shown in Figure 1-3,The dinuclear cobalt complex shown in Figures 4-6,The yield was about 65%.
Complex 2 (8.3 mg, 10 mmol), CsOHH2O (0.84 g, 5 mmol),alcohol (5 mmol) was added to a 25 mL schlenk tube and the solutionwas heated at 150 C (oil bath) for 24 h in an open systemunder argon. After cooling to room temperature, the degassedwater (5 mL)was added and the mixturewas extracted with diethylether (3 10 mL). A sample of ether phasewas subjected to the GCMSanalysis and the residual solution was evaporated, then subjected to the NMR analysis. The aqueous phase was acidifiedwith 6 M HCl and extracted with ethyl acetate (5 20 mL). Thecombined organic phasewaswashed with brine (25 mL), dried overanhydrous Na2SO4, and evaporated under reduced pressure, thepure carboxylic acid was collected and weighed for calculating theyield, which was further characterized by its 1H NMR which isconsist with the standard sample.
23%; 52%
Complex 2 (8.3 mg, 10 mmol), CsOHH2O (0.84 g, 5 mmol),alcohol (5 mmol) was added to a 25 mL schlenk tube and the solutionwas heated at 150 C (oil bath) for 24 h in an open systemunder argon. After cooling to room temperature, the degassedwater (5 mL)was added and the mixturewas extracted with diethylether (3 10 mL). A sample of ether phasewas subjected to the GCMSanalysis and the residual solution was evaporated, then subjected to the NMR analysis. The aqueous phase was acidifiedwith 6 M HCl and extracted with ethyl acetate (5 20 mL). Thecombined organic phasewaswashed with brine (25 mL), dried overanhydrous Na2SO4, and evaporated under reduced pressure, thepure carboxylic acid was collected and weighed for calculating theyield, which was further characterized by its 1H NMR which isconsist with the standard sample.
[0022] 2) Isophthalic acid (4.9839 g, 0.03 mol) was dissolved in DMSO (40 ml) Poured into a single mouth flask, Dropwise 10percent NaOH aqueous solution to rhoH = 8 ~ 9, Heated to 50 ° C, Magnetic stirring 0.5h, A solution of the product <strong>[39149-80-9]ter<strong>[39149-80-9]t-butyl 2-bromopropionate</strong></strong> (6.2724 g, 0.03 mol) The reaction was continued for 6 h. The reaction solution was washed with caustic, Gradual acidification, Drying treatment.
C22H15N3O2*Nd(3+)*Cu(2+)*C8H4O4(2-)*2NO3(1-)*2H2O*C22H14N3O2(1-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
21%
In water; at 180℃; for 192h;Autoclave;
General procedure: 0.1M Ln(NO3)3 solution (3mL, 0.3mmol), Htyba (0.071g, 0.2mmol), m-H2bdc (0.017g, 0.1mmol) and CuSO4·5H2O (0.025g, 0.1mmol) was dissolved in 8mL distilled water, and then the solution was stirred for half an hour at room temperature, sealed in a 28mL Teflon-lined stainless steel autoclave, and heated at 180C for 8days. Then, the steel vessel was taken out from the oven and cooled to room temperature. Green blue block crystals of [LnCu(Htyba)(tyba)(m-bdc)(NO3)]NO3}n (9, 10) (yield: 21, 15% respectively, based on CuSO4·5H2O). IR (KBr, cm-1) for 9: 3058.28(b), 1698.16(s), 1598.08(s), 1549.34(s), 1398.87(vs), 775.13(s)
C22H15N3O2*Sm(3+)*Cu(2+)*C8H4O4(2-)*2NO3(1-)*2H2O*C22H14N3O2(1-)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
15%
In water; at 180℃; for 192h;Autoclave;
General procedure: 0.1M Ln(NO3)3 solution (3mL, 0.3mmol), Htyba (0.071g, 0.2mmol), m-H2bdc (0.017g, 0.1mmol) and CuSO4·5H2O (0.025g, 0.1mmol) was dissolved in 8mL distilled water, and then the solution was stirred for half an hour at room temperature, sealed in a 28mL Teflon-lined stainless steel autoclave, and heated at 180C for 8days. Then, the steel vessel was taken out from the oven and cooled to room temperature. Green blue block crystals of [LnCu(Htyba)(tyba)(m-bdc)(NO3)]NO3}n (9, 10) (yield: 21, 15% respectively, based on CuSO4·5H2O
General procedure: In a 50 mL two-necked round-bottomed flask equipped with a magnetic stirring bar, a reflux condenser and a calcium chloride drying tube was placed nicotinic acid (1 g, 8.1 mmol) suspended in boron trifluoride etherate (10 mL). The reaction mixture was stirred and heated to 120 C overnight during which the creamy reaction mixture changed into a brownish solution. Thin layer chromatography (hexane/ethyl acetate 3:1) revealed complete reaction. The cooled reaction mixture was diluted with water (25 mL) and extracted with ethyl acetate (3 x 10 mL). The combined organic extract was washed to the end of effervescence with a saturated solution of NaHCO3. The organic phase was dried over anhydrous Na2SO4 and concentrated in vacuo giving a crude yield of 1.11 g (92%).
Ni4(tris(4-pyridyl)triazine)4(m-benzenedicarboxylate)4·H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65.3%
In acetonitrile; at 160℃; for 72h;High pressure;
NiCl2·6H2O (0.045mmol, 0.011g), tpt (0.03mmol, 0.0094g) and m-H2bdc (0.03mmol, 0.0051g) were dissolved in a mixed solvent containing H2O and MeCN (6mL, 4:5). Then, the reaction mixture was added into Teflon lined reactor (20mL) and heated at 160C for 72h. After cooling to room temperature, green block crystals were obtained by filtration. The yield of obtained crystals was 65.3% based on tpt. Analysis calcd (%) for C104H66N24Ni4O17: C 57.87%; H 3.06%; N 15.57%. Found: C 56.66%; H 4.02%; N 14.13%. IR (KBr pellet, cm-1): 3071 (w), 2318 (w), 1642 (m), 1573 (w), 1521 (s), 1374 (s), 1061 (m), 1026 (m), 810 (m), 776 (m), 663 (m), 516 (m).
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