* 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] Organic and Biomolecular Chemistry, 2013, vol. 11, # 6, p. 881 - 885
[2] Molecules, 2017, vol. 22, # 1,
[3] Chemistry - A European Journal, 2018, vol. 24, # 10, p. 2360 - 2364
2
[ 99-94-5 ]
[ 6232-88-8 ]
[ 100-21-0 ]
[ 7697-26-9 ]
[ 619-66-9 ]
Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 4, p. 591 - 594[2] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 4, p. 681 - 685
3
[ 99-94-5 ]
[ 6232-88-8 ]
[ 100-21-0 ]
[ 7697-26-9 ]
[ 15561-46-3 ]
[ 619-66-9 ]
[ 100-51-6 ]
Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 4, p. 583 - 591[2] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 4, p. 673 - 681
4
[ 99-94-5 ]
[ 76-05-1 ]
[ 6232-88-8 ]
[ 100-21-0 ]
[ 7697-26-9 ]
[ 15561-46-3 ]
[ 619-66-9 ]
[ 78504-88-8 ]
Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 4, p. 591 - 594[2] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 4, p. 681 - 685
5
[ 50-84-0 ]
[ 201230-82-2 ]
[ 89-20-3 ]
[ 100-21-0 ]
[ 528-44-9 ]
[ 1967-31-3 ]
[ 74-11-3 ]
Reference:
[1] Chemistry Letters, 1986, p. 299 - 302
6
[ 104-82-5 ]
[ 1642-81-5 ]
[ 100-21-0 ]
Reference:
[1] Technol. Rep. Kyushu Univ., 1951, vol. 24, p. 16,18[2] Chem.Abstr., 1953, p. 4867
7
[ 99-94-5 ]
[ 76-05-1 ]
[ 1642-81-5 ]
[ 100-21-0 ]
[ 5162-82-3 ]
[ 3006-96-0 ]
[ 619-66-9 ]
[ 78504-88-8 ]
Reference:
[1] Journal of Organic Chemistry USSR (English Translation), 1981, vol. 17, # 4, p. 583 - 591[2] Zhurnal Organicheskoi Khimii, 1981, vol. 17, # 4, p. 673 - 681
8
[ 100-21-0 ]
[ 610-29-7 ]
Yield
Reaction Conditions
Operation in experiment
68.6%
at 5 - 60℃; for 1 h;
1 part by weight of PTA was mixed with 8 parts by weight of concentrated sulfuric acid having a concentration of 82percent at 5 ° C, Then slowly add 1percent by weight of 66percent concentrated nitric acid, heat for 1 hour to 60 ° C, and heat for 1 hourTo 80 ° C for 10 hours at 80 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature and vacuum filtered.Filter cake and deionized water mixed evenly after vacuum filtration, repeated filter cake by adding deionized water for vacuum filtration operation untilThe collected filtrate was recrystallized in ice water, filtered, and dried in vacuo at 60 ° C for 2 hours to give PTANitro compound of PTA, the purity of the nitro compound of PTA is 93percent and the yield is 68.6percent;
Reference:
[1] RSC Advances, 2016, vol. 6, # 10, p. 8495 - 8502
[2] Patent: CN103664684, 2016, B, . Location in patent: Paragraph 0038
[3] Monatshefte fuer Chemie, 1886, vol. 7, p. 140
[4] Chemische Berichte, 1877, vol. 10, p. 145
[5] Justus Liebigs Annalen der Chemie, 1862, vol. 121, p. 90
[6] Hoppe-Seyler's Zeitschrift fuer Physiologische Chemie, 1915, vol. 95, p. 273,276, 288, 307[7] Hoppe-Seyler's Zeitschrift fuer Physiologische Chemie, 1916, vol. 98, p. 114
[8] Monatshefte fuer Chemie, 1900, vol. 21, p. 627[9] Monatshefte fuer Chemie, 1902, vol. 23, p. 410
[10] RSC Advances, 2014, vol. 4, # 87, p. 46476 - 46480
9
[ 100-21-0 ]
[ 7697-37-2 ]
[ 7783-05-3 ]
[ 610-29-7 ]
Reference:
[1] Chemische Berichte, 1877, vol. 10, p. 145
[2] Monatshefte fuer Chemie, 1900, vol. 21, p. 627[3] Monatshefte fuer Chemie, 1902, vol. 23, p. 410
With dmap In tetrahydrofuran; <i>tert</i>-butyl alcohol for 24 h; Reflux
Terephthalic acid (25) (1.66 g), di-tert-butyl dicarbonate (2.18 g) and 4-dimethylaminopyridine (305 mg) were added to a mixed solution of t-butanol (15 mL) / tetrahydrofuran ,And heated under reflux for 24 hours.After returning to room temperature, the reaction solution was concentrated under reduced pressure and the obtained residue was purified by silica gel flash column chromatography (developing solvent: chloroform: methanol = 20: 1) to give the title compound (26) (371 mg, yield 16.7 percent) As a white solid.
Reference:
[1] Journal of Medicinal Chemistry, 2011, vol. 54, # 10, p. 3524 - 3548
[2] Patent: JP2017/71567, 2017, A, . Location in patent: Paragraph 0183-0184; 0188
With photocatalytic titania-coated hollow glass microspheres; In water;Irradiation;
General procedure: HGM-TiO2 suspension was prepared by suspending HGM-TiO2into 100 mL TA aqueous solution in a Pyrex cylindrical reactor(12×1 in.,?150 mL capacity, with a vented Teflon screw top).The suspension was magnetically stirred and purged with oxygengently for 15 min prior to radiation and during the reaction, in orderto maintain the adsorption/desorption equilibrium. The suspensionswere irradiated in a Rayonet photochemical reactor (SouthernNew England Ultra Violet Company, http://www.rayonet.org,model RPR-100), equipped with a cooling fan on the bottom andfour phosphor-coated low-pressure mercury lamps (RPR 350 nm,8.34×10-9 Einstein mL-1 s-1). Samples (3 mL) were taken fromthe suspension at given time intervals and immediately filteredthrough a 0.45 m PTFE filter to remove suspended particles priorto analysis.TA is used to selectively trap ?OH and to produce 2-HTA with apercent yield of 35% [25] (Scheme 1). The yield of ?OH is quantifiedby fluorescent measurement of the generated 2-HTA. 2-HTA wasexcited at 315 nm to emit fluorescence at 425 nm [26], which wasmeasured on a Horiba FluoroMax 3 spectrofluorometer.
With cerium(IV) orthogermanate; sodium hydroxide; In water; for 2h;Irradiation;
The measurements of the amount of ·OH generated were conducted according to the following steps. Firstly, 10 mg of photocatalyst was suspended in 40 mL aqueous solution containing 0.01 M NaOH and 3 mM terephthalic acid. Before exposure to UV-visible light irradiation, the suspension was stirred in dark for 30 min. Then, 5 mL of the solution was taken out after every 30 min for UV-visible light irradiation, and centrifuged for fluorescence spectrum measurements. During the photoreactions, no oxygen was bubbled into the suspension. A fluorescence spectrophotometer (Fluorolog-3-P) was used to measure the fluorescence signal of the 2-hydroxy terephthalic acid generated. The excitation light employed in recording fluorescence spectra was 320 nm. The light source was a 300 W Xe lamp (CEL-HXUV300) with the wavelength of 240-1600 nm.
With lead yttrium oxide; sodium hydroxide; In water; at 20℃; for 0.5h;UV-irradiation;
Photoluminescence (PL) technique with terephthalic acid as a probe molecule was used to detect the formation of free·OH radicals on the surface of the UV-illuminated photocatalyst. The experiment produced at ambient temperature, 0.1 g of the PbYO composite photocatalyst calcined at different temperatures or BiYO3 was dispersed in 20 mL of the 5 × 10- 4 mol L- 1 terephthalic acid aqueous solution with a concentration of 2 × 10- 3 mol L- 1 NaOH in a dish with a diameter of about 9.0 cm. A 15 W, 365 nm UV lamp (6 cm above the dishes) was used as a light source. After UV irradiated for 30 min, the reaction solution was centrifuged and filtrated to measure the increasing amount in the PL intensity on a fluorescence spectrophotometer (Shimadzu RF-5301PC) at 425 nm excited by 315 nm light of 2-hydroxyterephthalic acid.
With sodium hydroxide; In water;UV-irradiation;Catalytic behavior; Kinetics;
The photocatalytic activities of the samples are evaluated by the degradation of terephthalic acid (TA) in an aqueous solution under visible light irradiation. The analysis of ?OH radical?s formation on the sample surface under visible light irradiation is performed by fluorescence technique using terephthalic acid, which readily reacted with ?OH radicals to produce highly fluorescent product, 2-hydroxyterephthalic acid [32]. The intensity of the peak attributed to 2-hydroxyterephtalic acid is known to be proportional to the amount of ?OH radicals formed [32]. The selected concentration of terephthalic acid solution is 5 × 10-4 M in a diluted NaOH aqueous solution with a concentration of 2 × 10-3 M. It has been proved that at these experimental conditions (low concentration of terephthalic acid, less than 10-3 M, room temperature), the hydroxylation reaction of terephthalic acid proceeds mainly by ?OH radicals [32]. Five hundred milligrams of the prepared samples is added to 100 mL of the 5 × 10-4 M terephthalic acid solution in 2 × 10-3 M NaOH under ultrasonic vibration for 10 min. Prior to light irradiation, the reactor is left in the dark for at least 30 min until an adsorption-desorption equilibrium is finally established. A 100 W tungsten lamp fixed at a distance of 150 mm above the surface solution is used as visible light source, and a UV cut-off filter is used to completely remove any radiation below 420 nm to ensure illumination by visible light source only. The average irradiation intensity of 100 W tungsten lamp was about 0.7 mW cm-2. The radiant flux was measured with a power meter from Institute of Electric Light Source (Beijing). Sampling is performed in every 15 min. Solution after filtration through 0.45 mum membrane filter is analyzed on a Hitachi F-4500 fluorescence spectrophotometer. The product of terephthalic acid hydroxylation, 2-hydroxyterephthalic acid, gave a peak at the wavelength of about 425 nm by the excitation with the wavelength of 315 nm.
With silver(I) bromide; hydroxyl; sodium hydroxide; In water;Sonication;
5 mg AgBr was added to 80 mL of aqueous solution comprising0.01 mol/L NaOH and 3 mmol/L terephthalic acid under ultrasonic irradiation.At a defined time interval, the concentration of solution in thesystem was analyzed by PL
General procedure: The photocatalytic activities of SrBiO2Cl and BaBiO2Cl were tested by photodegradation of rhodamine B (RhB) under UV lightirradiation of a 300 W high-pressure mercury lamp. The detailed procedure is as follows: 50 mg of photocatalyst was dispersed into 50 mL of 5x10-6 M RhB solution. Before irradiation, the suspension of SrBiO2Cl or BaBiO2Cl photocatalyst and RhB was vigorously stirred in the dark for 1 h to reach an adsorption-desorption equilibrium. Then, the mixture was irradiated for 10 min, and 2 mL of the suspension was taken, followed by centrifugation to remove the solid. The concentration of centrifuged solution was determined by UV-vis spectra based on the absorbance at 554 nm.
With bismuth(III) oxide; sodium hydroxide; for 0.5h;Darkness; Sonication; Irradiation;
By using terephthalic acid (TPA) as a probe molecule, the photoluminescence (PL) technique was used to examine the OH radicals produced by the ultrasonic-irradiated beta-Bi2O catalyst. TPA can readily react with OH radicals to produce a highly fluorescent compound, 2-hydroxyterephthalic acid (TAOH). The PL intensity of TAOH at 429nm is proportional to the amount of produced OH radicals. Terephthalic acid was added to sodium hydroxide solution (1.0×10-3molL-1), to obtain a 2.5×10-4molL-1 TPA solution. The catalyst was added to the solution with a concentration of 1.0gL-1. After magnetically stirred for 30min in the dark, the mixed solution was placed in the ultrasonic bath for ultrasonic irradiation. The reacted solution was centrifuged to remove the catalyst and analyzed by recording the PL measurements at a luminescence spectrometer with the excitation wavelength of 315nm.
With lutetium orthoferrite; water; sodium hydroxide; for 0.5h;Sonication;Catalytic behavior; Mechanism;
Photoluminescence (PL) spectroscopy was used to examine the ?OH radicals formed over the ultrasonic-irradiated LuFeO3 catalyst using terephthalic acid (TPA) as a probe molecule. TPA tends to react with ?OH to produce 2-hydroxyterephthalic acid (TAOH), which is a highly fluorescent compound [23]. The PL intensity of TAOH at around 429 nm is in proportion to the amount of produced ?OH radicals. Hence, we can obtain information on the ?OH radicals by detecting the PL intensity of the reacted solution. TPA was dissolved in NaOH solution (1.0 mmol/L) to make a 0.25 mmol/L TPA solution. The catalyst (0.08 g) was added to 20 mL of the TPA solution. After being magnetically stirred for 30 min in the dark, the mixed solution was ultrasonically irradiated. The reacted solution (2 mL) was pipetted out at a given reaction time interval, and then centrifuged at 4000 r/min for 10 min to remove the catalyst. The upper clear solution in the centrifuge tube was used for the PL measurements with a fluorescence spectrophotometer with an excitation wavelength of 315 nm. Ethanol in different volume fractions was added to the reaction solution to investigate its effect on the ?OH yield.
With water; sodium hydroxide; at 20℃; for 0.25h;Irradiation;
The experiments were performed as follows: photocatalyst(50 mg) was suspended in an aqueous solution (50mL) containing of NaOH (0.15 g) and TA (3 mmol/L) at roomtemperature. After irradiation for 15 min, a 4.0 mL aliquot ofsolution was taken out and centrifuged. The fluorescence spectrumof the sample was measured using an excitation wavelengthof 320 nm. During the photoreactions, oxygen was notbubbled into the suspension.
With water; sodium hydroxide; for 1h;Inert atmosphere; Irradiation;Catalytic behavior;
Each 5.0-mg photocatalyst sample was added to 50 cm3 of terephthalic acid(3.0 9 10-3 mol dm-3) and sodium hydroxide (1.0 9 10-2 mol dm-3). The suspensions were agitated in a glass beaker during near-UV light irradiation(300-400 nm, peak at 352 nm) from a 4-W black light bulb (Toshiba FL4BLB) and visible light irradiation from a 150-W xenon lamp (Hamamatsu Photonics C2577)using 420-nm-short cutoff filter. The reaction between the terephthalic acid and hydroxyl radical resulting from the photocatalytic water oxidation produces 2-hydroxy terephthalic acid [15, 16]. The fluorescence spectra of the 2-hydroxyterephthalic acid in the centrifuged solutions upon 312-nm excitation were obtained as a function of the light irradiation time using a fluorescence spectrophotometer (Shimadzu RF5300).
With copper(I) oxide; dihydrogen peroxide; sodium hydroxide; In water; at 20℃;Irradiation;
50 mg Cu2O catalyst is added to the beaker containing 100 mL of terephthalic acid (TPA) solution (0.25 mmol L-1 in 1 mmol L-1 NaOH solution) and 10 mumol H2O2. The solution is stirred for 30 min in dark followed by irradiation by 400 W metal halide lamp for 30 min. The reacted solution was centrifuged and the clear solution is used for photoluminescence measurements in a fluorescence spectroflourometer (Flouromax 4) with the excitation wavelength of 315 nm.
With sodium hydroxide; In water; for 0.333333h;UV-irradiation;Kinetics;
From the alkaline stock solution of TPA [14], with the concentration of 130 mg/L that was prepared by using 2 × 10-3M NaOH, working solution of TPA (100 mL, 83 mg/L) was freshly made prior to photocatalytic experiments. 25 mL of TPA and 10 mg of photocatalyst were mixed in 25 mL of double deionized water and stirred under sunlight irradiation. Samples (1 mL) of the water solution were taken from the reactor at different UV irradiation times (0 min,3 min, 6 min, 10 min, and 20 min) and centrifuged (1300 min-1) for 3 min. A fixed volume (159 L) of the solution was then sampled with an automatic pipette, and transferred into microliter platewells (microliter plate with 96 wells, flat bottom, black) for fluorescence measurements. Photocatalytic tests were carried out in solar simulator (Suntest XLS+, Atlas, USA) chamber with a simulated solar irradiation source (Xenon lamp), using daylight filter(300-800 nm), at UV light flux of 750 W/m2. During irradiationin the presence of the photocatalyst the TPA is decomposed and highly fluorescent 2-hydroxyterephthalic acid (HTPA) is formed as an intermediate oxidation product. Fluorescence measurements were performed using a microplate reader in the fluorescence mode(Infinite F200 Microplate reader, Tecan, Switzerland). The wave-length of the excitation light was 320 nm (filter band width: 25 nm)and emission was measured at 430 nm (filter bandwidth: 35 nm).The instrument was operating in top mode with 25 reads per well, with 20 s integration time. The amplification factor for the photomultiplier tube was 56 or 78. For each irradiation time, at leastfour parallel photocatalytic tests were done.
With (BiFeO3)0.5(Bi2WO6)0.5; sodium hydroxide; for 2h;Irradiation;
The generation of hydroxyl radicals (OH) on the surface of BiFeO3-Bi2WO6 nanocomposite was investigated by photoluminescence (PL) technique. Briefly, the samples containing 0.1g was mixed with 100ml of 5×10-4M of terephthalic acid (TA) solution and 2×10-3M of a diluted sodium hydroxide (NaOH) aqueous solution. Under visible light irradiation, the fluorescence production of 2-hydroxyterephthalic acid increased from the reactions of terephthalic acid and hydroxyl radicals. The suspensions were collected every 30min to evaluate the generated TA-OH, and analyzed by fluorescence spectroscopy at 425nm.
With Al2.7B6Cr0.3H5O16; dihydrogen peroxide; cyclohexanol; In acetonitrile;
2.2.7 Photoluminescence (PL) spectroscopy was used to detect OH radicals formed over Cr-PKU-1 catalyst using terephthalic acid (TA) as a probe molecule. In a typical run, 40mg of 10%Cr-PKU-1 was dispersed in a mixed aqueous solution containing 3mmol TA, 20mmol CHOL, 20mL CH3CN, and 40mmol H2O2. After stirring for a specified interval of time, the suspension was withdrawn and then centrifuged to remove the powder. The upper and transparent solution was used for the PL measurement with an excitation irradiation at 328nm on a Hitachi F4600 fluorescence spectrometer. PMT voltage was fixed to be 700V, and the width of excitation and emission slit were both set to 2.5nm.
With titanium(IV) dioxide; sodium hydroxide; for 1h;Irradiation;
TA was dissolved in dilute NaOH solution (2 × 10-3 mol L-1),and then 50 mg of photocatalyst was dispersed in 50 mL of TA solution(5 × 10-4 mol L-1). The mixed solution was stirred in the dark for 24 h and subsequently irradiated for 60 min under visible light. At different irradiation times, an aliquot was removed, and the mixture was centrifuged for 10 min at 4000 rpm, respectively. The supernatant was collected and analyzed by fluorescence. Fluorescence spectra of 2-HTA at an emission wavelength of 425 nm were measured on a PerkinElmer LS45 fluorescence spectrophotometer. A calibration curve using the hydroxylated product as a standard was constructed to quantify the relationship between the fluorescence signal and the produced hydroxylradicals.
poly[p-phenylenebenzobisoxazole-co-2,5-thienylbenzobisoxazole], feed molar content of 2,5-thiophene-dicarboxylic acid 30% from total feed content of terephthalic acid and 2,5-thiophene-dicarboxylic acid[ No CAS ]
poly[p-phenylenebenzobisoxazole-co-2,5-thienylbenzobisoxazole], feed molar content of 2,5-thiophene-dicarboxylic acid 50% from total feed content of terephthalic acid and 2,5-thiophene-dicarboxylic acid[ No CAS ]
poly[p-phenylenebenzobisoxazole-co-2,5-thienylbenzobisoxazole], feed molar content of 2,5-thiophene-dicarboxylic acid 5% from total feed content of terephthalic acid and 2,5-thiophene-dicarboxylic acid[ No CAS ]
poly[p-phenylenebenzobisoxazole-co-2,5-thienylbenzobisoxazole], feed molar content of 2,5-thiophene-dicarboxylic acid 15% from total feed content of terephthalic acid and 2,5-thiophene-dicarboxylic acid[ No CAS ]
poly[p-phenylenebenzobisoxazole-co-2,5-thienylbenzobisoxazole], feed molar content of 2,5-thiophene-dicarboxylic acid 25% from total feed content of terephthalic acid and 2,5-thiophene-dicarboxylic acid[ No CAS ]
With dmap; 2-chloro-1-methyl-pyridinium iodide; In N,N-dimethyl acetamide; at 50℃; for 4h;
Example 9 The Preparation of Mono-Tocopherol Terephthalate A 100 mL flask was charged with 4.30 grams of dl-alpha-tocopherol, 3.32 grams of terephthalic acid, 2.55 grams of 2-chloro-1-methylpyridinium iodide, 0.244 grams of 4-(dimethylamino)pyridine, and 50 ml of dry N,N-dimethylacetamide. The mixture was stirred at 50 C. for 4 hours. Thin layer chromatography showed that the reaction was complete. After the mixture was cooled to room temperature, the mixture was poured into 150 ml of ethyl acetate. The mixture was washed three times with saturated aqueous NaCl (3*100 mL), and dried over anhydrous MgSO4 overnight. The crude product was purified by column chromatography on silica gel with 30% ethyl ether in hexane. (Yield: 1.60 grams, 27.6%) 1H NMR (300 MHz, CDCl3) delta ppm: 11.80 (bs, 1H), 8.374-8.259 (q, J1=8.4 Hz, J2=26.1 Hz, 4H), 2.650-2.607 (t, 2H), 2.130 (s, 3H), 2.066 (s, 3H), 2.024 (s, 3H), 1.895-1.783 (m, 2H), 1.532-1.083 (m, 24H), 0.878-0.839 (m, 12H). Anal. Calcd. for C37H54O5: C, 76.78; H, 9.40. Found: C, 76.64; H, 9.39. IRnumaxKBrcm-1: 3062, 2924, 2858, 1737, 1696, 1573, 1460, 1424, 1373, 1276, 1240, 1097, 928, 774, 723.
Example 5 Synthesis of terephthaloyl chloride To 18.6 g (0.11 mole) of <strong>[37091-73-9]2-chloro-1,3-dimethylimidazolinium chloride</strong>, 83 g of toluene was added, and successively 8.31 g (0.05 mole) of terephthalic acid was added. The mixture was reacted at 110 ° C. for 4 hours. The reaction mass was analyzed by gas chromatography. The yield of terephthaloyl chloride was 98percent.
In N-methyl-acetamide; di-isopropyl ether; acetonitrile;
EXAMPLE 7 Preparation of N,N'-bis(4-dimethylamino-2-methylquinolin-6-yl)-terephthalamide 4-(4,6-Dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride (177 mg) is added to a solution of 48 mg (0.29 mmol) of terephthalic acid and 128 mg (0.64 mmol) of 4-dimethylamino-6-aminoquinaldine in 6 mL of dimethylformamide, at a temperature in the region of 20 C. The mixture obtained is stirred at a temperature in the region of 20 C. for about 12 hours. The reaction mixture is successively taken up in 2 mL of acetonitrile and 2 mL of diisopropyl ether, and the precipitate thus obtained is slowly filtered on a 6 mL BOND-ELUT cartridge filled with sintered material. The insoluble matter obtained is washed with diisopropyl ether and then dried under argon. 154 mg of N,N'-bis(4-dimethylamino-2-methylquinolin-6-yl)-terephthalamide are thus obtained in the form of a beige powder of whose characteristics are the following: 1H NMR spectrum (400 MHz, (CD3)2SO d6, at a temperature of 373K, delta in ppm): 2.70 (s: 6H); 3.44 (s: 12H); 6.87 (s: 2H); 7.98 (d, J=9 Hz: 2H); 8.23 (s: 4H); 8.27 (dd, J=9 and 1.5 Hz: 2H); 8.94 (broad s: 2H); 10.64 (broad s: 2H).
EXAMPLE 22 Synthesis of Compound (PBOZ)2Ir(FM2BOZPBOZ)Ir(PBOZ)2 Synthesis of 5-(trifluoromethyl)-2-(4-(trifluoromethyl)benzo[d]oxazole-2-yl)phenyl)benzo[d]oxazole: polyphosphoric acid (125 cm3) was heated at 70 C. for 1 hour while agitating. 0.1 mol of terephthalic acid was added and the resulting mixture was stirred for 15 minutes. 0.2 mol of <strong>[454-81-9]2-amino-4-(trifluoromethyl)phenol</strong> was added in a dropwise fashion for 10 minutes. The temperature of the mixture was increased to 150 C. and then this temperature was maintained for 2 hours. The mixture was stirred to cool down to a room temperature. The resulting reaction mixture was stirred for 1 hour with ice water (1.5 dm3), and neutralized with a diluted sodium carbonate hydrate solution. Then it was filtrated and dried in an oven for 1 day. The solid was crystallized from dimethylformide (200 cm3). The final filtrated product was rinsed with methanol (100 cm3) and then dried in a 100 C. vacuum oven. As a result, colorless needle-shaped crystalline 5-(trifluoromethyl)-2-(4-(trifluoromethyl)benzo[d]oxazole-2-yl)phenyl)benzo[d]oxazole was produced at a yield of 78%.
With phosphoric acid; In acetic anhydride; at 240℃; under 22502.3 Torr; for 32h;
FDCA and DM-FDCA were contacted with ethylene at 240 C in a solvent/dehydration catalyst comprising acetic anhydride or phosphoric acid in amounts shown in the table below and one of acetic acid anhydride and benzoic acid anhydride. Ethylene pressure at room temperature was 30 bar. The benzene derivative that was formed was in all instances the acid, viz. terephthalic acid. That confirms the finding in US7385081 that also the diester of FDCA reacts to form terephthalic acid and that the dimethyl ester of terephthalic acid is not formed. The yield of terephthalic acid ("TPA") was measured after 32 hr. The results are shown in Table 7.
With potassium hydroxide; at 150℃; for 72h;Autoclave; High pressure;
A mixture of Zn(OAc)2?H2O (87mg, 0.4mmol), Hflmq (52mg, 0.2mmol), H2bdc (33mg, 0.2mmol) and distilled water (8ml) was adjusted to pH with KOH (22mg, 0.4mmol) solution and then sealed in an 18ml Teflon-lined autoclave which was heated in an oven at 150C for 72h. After slow cooling to room temperature, brown block crystals of 1 were separated by filtration, washed with distilled water and dried at ambient temperature (Yield 48% based on Zn). Elemental analysis: Calcd. for C36H30F2N2O12Zn2: C, 50 .74; H, 3.52; N, 3.29. Found: C, 51.20; H, 4.05; N,3.52%. IR (KBr,cm-1): 1385s, 1390vs, 1587vs, 1589s, 1625s, 1630vs.
With Fe3O4/C/ZnO core-shell composite; CR dye; In water; for 0.166667h;Irradiation;
OH radical reactions were performed as follows. 5mg of each 1D Fe3O4/CZnO core-shell composite microrods with different ZnO nanocrystal sizes were suspended in 10mL of aqueous solution containing 100 mgL-1 of CR, 10 mM of NaOH and 5 mM of terephthalic acid (TA), respectively. Before exposure to visible-light, the suspension was stirred in the dark for 10min. After irradiatedfor10 min,the products were collected by a magnet , and the rest of solution was collected for fluorescence spectroscopy measurements. A fluorescence spectrophotometer was then used to measure the fluorescence signal of the generated 2-hydroxy-terephthalic acid (TAOH). The excitation light wavelength used in recording fluorescence spectra was 320nm.
With zinc(II) oxide; In water;UV-irradiation;
The synthesis of 2-hydroxyterephthalic acid (HTPA) was performed to examine the formation of OH radicals over the photocatalyst in a solution during visible light irradiation. The photocatalyst was dispersed in 50 mL of a 0.002 M NaOH (with2.4 105 mol terephthalic acid) solution. After irradiating visible light for 6 h, the solution was centrifuged and the photoluminescence(PL) spectrum was measured. HTPA was formed by a reaction of terephthalic acid (TPA) with OH radicals. The amount of HTPA could be examined by PL because TPA is non-luminescent,where as HTPA is.
With ammonium acetate; water; hydrogen bromide; oxygen; manganese(II) acetate; cobalt(II) diacetate tetrahydrate; 1-n-butyl-3-methylimidazolim bromide; acetic acid; 3-butyl-1-methylimidazolium acetate; at 206 - 215℃; for 3h;Autoclave;
In separate examples, ionic liquid was subjected to an oxidative aging treatment for 21 hours at 215C, similar to the thermal treatment but under flowing air and including Co, Mn, HBr catalyst but no methyl aromatic reactant (or intermediate). This process resulted in generation of all of the products that result from thermal treatment (in examples 1 and 2), plus significant amounts of compound (5), and trace amounts of compounds (2), (8), (11), and (13) observed in mass spectrometry. Compound (1) was also only observed in trace amounts. However, when conducted in the presence of para-xylene, even the trace amounts of oxygenated BMIm, compounds (2) and (11), were not observed. Similar results were obtained when the oxidation was conducted for only 3 hours. High performance liquid chromatography (HPLC) with UV-vis detection shows that no overall loss of imidazolium compounds occurred. The amounts of BMIm, and compounds (6), (1), (5), (7) and (10) as a percentage of moles of ionic liquid cations are shown in Table 2. The quantification of compound (10) is an estimate assuming similar UV-vis molar absorptivity as other cations. Table 2 Subsequently, 70 g of the product of this reaction was used as a solvent for para-xylene oxidation, after addition of 0.4 g HBr, 33.8 g acetic acid (to make up for loss during the initial oxidation), and 20 g para-xylene. The reaction was run by heating to a target temperature 215C with 2500 seem air flow for three hours, although the temperature dropped to 206C after the initial exotherm. After isolating the products by filtration and washing, the solid portion of the products of this reaction (as analyzed by HPLC) contained 6669 ppm 4-CBA, 19.8% toluic acid and 5.0% toluamide, with the remainder consisting of terephthalic acid and terephthalic acid-monoamide in a ratio of 1.2: 1. The high amount of toluic acid and toluamide indicate reaction did not reach full conversion, which may also be the reason for high 4-CBA.
With ammonium acetate; hydrogen bromide; oxygen; manganese(II) acetate; cobalt(II) diacetate tetrahydrate; 1-n-butyl-3-methylimidazolim bromide; acetic acid; 3-butyl-1-methylimidazolium acetate; In water; at 215℃; for 3h;
Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215 C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180 C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80 C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18%. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.
With ammonium acetate; water; hydrogen bromide; oxygen; manganese(II) acetate; cobalt(II) diacetate tetrahydrate; 1-n-butyl-3-methylimidazolim bromide; acetic acid; 3-butyl-1-methylimidazolium acetate; at 210 - 215℃; for 3h;Autoclave;
A starting mixture of 75.7 g acetic acid, ionic liquid (containing both 29.87 g BMIm bromide and 14.98 g BMIm acetate), 15 g ammonium acetate, and 0.6 g water was heated in a pressurized titanium autoclave under flowing nitrogen at 400 psig. (Other non- reactive gases could be used, if desired, and the gas does not need to be flowing) The mixture was first heated to 180C for two hours, and a sample was collected from the vessel. This sample contained no significant ionic liquid components (MS signal > 10e4 counts) other than BMIm. The mixture was heated for an additional 68 hours and analyzed after cooling. This process produces BMIm reaction products that are accessible by thermal reaction. High performance liquid chromatography (HPLC) with UV-vis detection showed that no overall loss of imidazolium compounds occurred. The mixture had 43% BMIm, 32% compound (6), 2% compound (1), 18% compound (7) and 5% compound (10) as a percentage of moles of ionic liquid cations. The quantification of compound (10) is an estimate assuming a similar UV-vis molar absorptivity as other cations. Subsequently, the product of this reaction was used as a solvent for para- xylene oxidation. The solvent included 80 g of the product of the above reaction, and 20 g of a mixture of acetic acid, BMImBr, BMImOAc and ammonium acetate (in the same proportion as original starting material). A catalyst including 0.4 g HBr, 0.8 g Cobalt(II) acetate tetrahydrate and 0.8 g Manganese(II) acetate was also added, along with 20 g para- xylene. The reaction was run by heating to a target temperature of 215C with 2500 seem air flow for three hours, although the temperature dropped to 210C after the initial exotherm which lasted 1 hour. After isolating the products by filtration and washing, the solid portion of the products of this reaction (as analyzed by HPLC) contained 463 ppm 4-CBA, 4641 ppm toluic acid and 823 ppm toluamide, with the remainder being terephthalic acid and terephthalic acid-monoamide in a ratio of 2.4: 1.
With ammonium acetate; hydrogen bromide; oxygen; manganese(II) acetate; cobalt(II) diacetate tetrahydrate; 1-n-butyl-3-methylimidazolim bromide; acetic acid; 3-butyl-1-methylimidazolium acetate; In water; at 215℃; for 3h;
Example 1 In one example, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215 C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180 C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80 C. for 30 min and filtered hot. The solid reaction products produced in this way (seven repetitions) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid to terephthalic acid monoamide ratio of 4.37. The used ionic liquid, generated as described above, was then subjected to vacuum distillation with centrifugation to remove volatile components at 72 C. for 14-20 hours utilizing a staged vacuum method. The non-volatile residue, which contained ionic liquid, catalyst, and reaction intermediates, was combined with the non-volatile components from other identical runs. This recycled ionic liquid was combined with fresh acetic acid and ammonium acetate in a 5:2:3 weight ratio of acetic acid to ammonium acetate to recycled ionic liquid. To this mixture, 0.4 g water and 0.4 g HBr were added to obtain a mixture similar to the starting mixture but with recycled ionic liquid. This solvent and catalyst were used for an oxidation reaction starting with 20 g para-xylene, run under similar conditions to the initial oxidation reaction in fresh ionic liquid. The solid products from this procedure contained 0 ppm of 4-CBA, 0 ppm toluic acid or toluamide, and a terephthalic acid to terephthalic acid monoamide ratio of 3.1. The process was repeated, and the solid products contained 34 ppm of 4-CBA, 4039 ppm toluic acid or toluamide, and the terephthalic acid to terephthalic acid monoamide ratio was 3.9. As a comparison, when no ammonium acetate was added to the recycled ionic liquid (the only ammonium was what remained after the first reaction and the vacuum distillation step), the resulting level of 4-CBA was 6811 ppm, and there was 6173 ppm of toluic acid.
With ammonium acetate; hydrogen bromide; oxygen; manganese(II) acetate; cobalt(II) diacetate tetrahydrate; 1-n-butyl-3-methylimidazolim bromide; acetic acid; 3-butyl-1-methylimidazolium acetate; In water; at 215℃; for 3h;
Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215 C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180 C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80 C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18%. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.
With ammonium acetate; hydrogen bromide; oxygen; manganese(II) acetate; cobalt(II) diacetate tetrahydrate; 1-n-butyl-3-methylimidazolim bromide; acetic acid; 3-butyl-1-methylimidazolium acetate; In water; at 215℃; for 3h;
Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215 C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180 C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80 C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18%. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.
With ammonium acetate; hydrogen bromide; oxygen; manganese(II) acetate; cobalt(II) diacetate tetrahydrate; 1-n-butyl-3-methylimidazolim bromide; acetic acid; 3-butyl-1-methylimidazolium acetate; In water; at 215℃; for 3h;
Example 1 Oxidation in the Presence of Ammonium Acetate to Generate Amide Containing Products In one set of examples, 20 g para-xylene was oxidized in a mixture of 50 g acetic acid, 20 g BMImBr, 10 g BMImOAc, 20 g ammonium acetate, and 0.4 g water with catalyst composed of 0.8 g Cobalt(II) acetate tetrahydrate, 0.6 g manganese(II) acetate and 0.4 g HBr. The reaction took place at 215 C. for three hours in semi-batch mode with continuous flow of air at 2500 sccm, and the temperature was maintained for the duration. After replacing air with nitrogen and cooling to room temperature to achieve crystallization, the product was filtered to remove solid reaction products. Note that room temperature filtration does not separate toluic acid from terephthalic acid, although filtration above 180 C. would. The solids were washed 3 times with room temperature water and then stirred in water at 80 C. for 30 min and filtered hot. The solid terephthalic acid reaction products produced in this way (seven repetitions, examples 1A-1E) had an average 4-CBA content of 19.7 ppm, an average toluic acid content of 2475 ppm, and an average terephthalic acid monoamide content of 18%. On two occasions p-toluamide content was measured and was 1106 and 5797 ppm respectively. The detailed data is shown in Table 1. The 4-CBA content of the solid products for this example, the comparative example and example 2, as well as the total amide content of the solid products (toluamide+terephthalic acid monoamide) are also shown in FIGS. 5 and 6 respectively. There, the data are plotted as a function of the cumulative amount of ammonium acetate or ammonia in moles that were added to the reactor.
(1R,4S)-cyclohexane-1,4-dimethanol diacetate[ No CAS ]
[ 100-21-0 ]
[ 3236-48-4 ]
[ 3236-47-3 ]
Yield
Reaction Conditions
Operation in experiment
0.12%Chromat.; 0.48%Chromat.; 90.5%Chromat.
With methanol; potassium carbonate; at 20℃; for 17h;
Example 17Preparation of cis-1,4-cyclohexanedimethanol by hydrolysis of its diacetateThe diacetate product from Example 5 (1.08 g, 4.73 mmol) was dissolved in methanol (9.50 mL, 0.50 M). Potassium carbonate (1.44 g, 10.4 mmol) was added all at once. The mixture was stirred for 17 hours at ambient temperature. The volatiles were then removed under reduced pressure. Water (10 mL) was added to the crude mixture. The aqueous phase was extracted three times with 25 mL of ethyl acetate. The organic extracts were combined and dried with sodium sulfate. After filtration, the volatiles were removed under reduced pressure to yield a colorless oil (0.43 g recovered). GC analysis: 90.5percent cis-CHDM, 0.48percent trans-CHDM, 0.12percent terephthalic acid (TPA), and 8.9percent unknown. 1H NMR delta (CDCl3): 3.57 (d, J=6.0 Hz, 4H), 1.71 (m, 2H), 1.61-1.29 (m, 8H).
0.02 mmol of cobalt nitrate trihydrate was dissolved in 2 mL of dimethylformamide and placed in a glass test tube having a diameter of 5 mm, on which 0.01 mmol of terephthalic acid and 4 mmol of 4,4 '- (1,4-phenylene) A solution in which 0.02 mmol of dipyridine was dissolved in 2 mL of methanol was gently laminated and the glass test tube was placed in a container containing a cushioning material so as not to vibrate for 14 days, and it was left to stand. Synthesis was carried out in the same manner as in Example, but no single crystal was obtained.
0.02 mmol of copper nitrate trihydrate was dissolved in 2 mL of dimethylformamide,Placed in a glass test tube having a diameter of 5 mm,A solution of 0.01 mmol of terephthalic acid and 0.02 mmol of 4,4 '- (1,4-phenylene) dipyridine in 2 mL of methanol was gently laminated thereon,The glass test tube was placed in a container containing buffer material so as not to give vibration for 14 days and it was left to stand.Synthesis was carried out in the same manner as in Example,A single crystal was not obtained.
1,4-bis(5-((4,6-dimethoxy-1,3,5-triazin-2-yl)oxy)-4-methyloxazol-2-yl)benzene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
General procedure: To a solution of benzoic acid 1a (2.2 g, 18.0 mmol) and N-methylmorpholine (396 muL, 3.60 mmol) in 1,4-dioxane/H2O(100 mL:50 mL) was added DMT-MM (5.23 g, 18.9 mmol) at room temperature. After stirring for 15 min, a solution ofalanine 2a (1.76 g, 19.8 mmol) and aq 1 M NaOH (19.8 mL, 19.8 mmol) was added. After the reaction was completed(monitored by TLC), N-methylmorpholine (3.96 mL, 36.0 mmol) and DMT-MM (14.9 g, 54 mmol) were added in order.After stirring for 3 h, the reaction mixture was diluted in EtOAc (100 mL) and washed with aq 1 M HCl (40 mL), sat. aqNaHCO3 (40 mL), and brine (30 mL). The organic layer was dried over Na2SO4, filtered, and evaporated under reducedpressure. The residue was purified by column chromatography (EtOAc:hexane = 7:3) to give oxazole 3aa in 78% yield.
2C22H14N3O2(1-)*Eu(3+)*0.5C8H4O4(2-)*2NO3(1-)*2H2O*Zn(2+)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
61%
In water; at 180℃; for 168h;Autoclave;
General procedure: A mixture of 0.1molL-1 Ln(NO3)3 solution (3mL, 0.3mmol), Htyba (0.071g, 0.2mmol), p-H2bdc (0.017g, 0.1mmol) and CuSO4·5H2O (0.025g, 0.1mmol) was dissolved in 8mL distilled water. The resulting solution was stirred for half an hour at room temperature, sealed in a 28mL Teflon-lined stainless steel autoclave, and heated at 180C for 7days. Then, the steel vessel was taken out from the oven and cooled to room temperature. The dark blue crystals of [NdCu(tyba)2(p-bdc)0.5(NO3)2]·2H2O}n (4) were obtained (yield: 57%, based on CuSO4·5H2O
2C22H14N3O2(1-)*0.5C8H4O4(2-)*2NO3(1-)*2H2O*Zn(2+)*Gd(3+)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
55%
In water; at 180℃; for 168h;Autoclave;
General procedure: A mixture of 0.1molL-1 Ln(NO3)3 solution (3mL, 0.3mmol), Htyba (0.071g, 0.2mmol), p-H2bdc (0.017g, 0.1mmol) and CuSO4·5H2O (0.025g, 0.1mmol) was dissolved in 8mL distilled water. The resulting solution was stirred for half an hour at room temperature, sealed in a 28mL Teflon-lined stainless steel autoclave, and heated at 180C for 7days. Then, the steel vessel was taken out from the oven and cooled to room temperature. The dark blue crystals of [NdCu(tyba)2(p-bdc)0.5(NO3)2]·2H2O}n (4) were obtained (yield: 57%, based on CuSO4·5H2O).
2C22H14N3O2(1-)*Nd(3+)*Cu(2+)*0.5C8H4O4(2-)*2NO3(1-)*2H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
In water; at 180℃; for 168h;Autoclave;
General procedure: A mixture of 0.1molL-1 Ln(NO3)3 solution (3mL, 0.3mmol), Htyba (0.071g, 0.2mmol), p-H2bdc (0.017g, 0.1mmol) and CuSO4·5H2O (0.025g, 0.1mmol) was dissolved in 8mL distilled water. The resulting solution was stirred for half an hour at room temperature, sealed in a 28mL Teflon-lined stainless steel autoclave, and heated at 180C for 7days. Then, the steel vessel was taken out from the oven and cooled to room temperature. The dark blue crystals of [NdCu(tyba)2(p-bdc)0.5(NO3)2]·2H2O}n (4) were obtained (yield: 57%, based on CuSO4·5H2O). IR (KBr, cm-1) for 4: 3423.09(b), 1603.97(s), 1555.88(s), 1403.93(vs), 1300.23(m), 785.36(s)
2C22H14N3O2(1-)*Nd(3+)*0.5C8H4O4(2-)*2NO3(1-)*2H2O*Zn(2+)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
In water; at 180℃; for 168h;Autoclave;
General procedure: A mixture of 0.1molL-1 Ln(NO3)3 solution (3mL, 0.3mmol), Htyba (0.071g, 0.2mmol), p-H2bdc (0.017g, 0.1mmol) and CuSO4·5H2O (0.025g, 0.1mmol) was dissolved in 8mL distilled water. The resulting solution was stirred for half an hour at room temperature, sealed in a 28mL Teflon-lined stainless steel autoclave, and heated at 180C for 7days. Then, the steel vessel was taken out from the oven and cooled to room temperature. The dark blue crystals of [NdCu(tyba)2(p-bdc)0.5(NO3)2]·2H2O}n (4) were obtained (yield: 57%, based on CuSO4·5H2O).
2C22H14N3O2(1-)*0.5C8H4O4(2-)*2NO3(1-)*2H2O*Zn(2+)*Tb(3+)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
59%
In water; at 180℃; for 168h;Autoclave;
General procedure: A mixture of 0.1molL-1 Ln(NO3)3 solution (3mL, 0.3mmol), Htyba (0.071g, 0.2mmol), p-H2bdc (0.017g, 0.1mmol) and CuSO4·5H2O (0.025g, 0.1mmol) was dissolved in 8mL distilled water. The resulting solution was stirred for half an hour at room temperature, sealed in a 28mL Teflon-lined stainless steel autoclave, and heated at 180C for 7days. Then, the steel vessel was taken out from the oven and cooled to room temperature. The dark blue crystals of [NdCu(tyba)2(p-bdc)0.5(NO3)2]·2H2O}n (4) were obtained (yield: 57%, based on CuSO4·5H2O).
[Cu7(μ-adeninato)6(μ3-OH)6(μ-H2O)6](terephthalate)2*12H2O[ No CAS ]
[Cu7(μ-adeninato)6(μ3-OH)6(μ-H2O)6](terephthalate)2*24H2O[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
40%
Compound 2 was obtained by adding to a 10 mL water solution of0.0488 g of Cu(NO3)2·3H2O (0.2 mmol), 0.0390 g of <strong>[73-24-5]adenine</strong> (0.3 mmol)dissolved in 15 mL of warm water-methanol mixture (1:1). The resultingsolution (pH=4.0) is basified with NaOH solution to pH~8.8and later 0.0997 g of terephthalic acid (0.6 mmol) dissolved in 20 mL ofwater basified with NaOH at 60 C is added. In two days a pale bluepowder appears corresponding to the formulae [Cu7(mu-ade)6(mu3-OH)6(mu-H2O)6](tereph)·~12H2O. Yield 40%. Calcd. forC38H70Cu7N30O28 (MW: 1839.97): C 24.80, H 3.83, N 22.84, Cu 24.18;found C 24.72, H 3.78, N 22.76, Cu 24.17%. Main IR features (cm-1; KBrpellets): 3420 s, 3200 m, 2930 s, 1645vs, 1610s, 1504 m, 1462s,1400vs, 1308 m, 1192s, 1146s, 933 m, 888w, 742 m, 657 s, 506w.Blue single-crystals of this compound have been obtained after one month using test tube diffusion technique in which over the aquo-methanolicsolution containing the copper(II) nitrate and <strong>[73-24-5]adenine</strong> mixture,an aqueous solution of the terephthalic acid is layered carefully.Depending on the handling of the crystals: storing them under roomconditions (2a), or directly picking them from the mother liquid (2b)specimens at different hydration stages were achieved.