[ CAS No. 89-05-4 ] {[proInfo.proName]}

Name: 89-05-4|1,2,4,5-Benzenetetracarboxylic acid|98%
Brand: Ambeed
SKU: A887143
Price: 5.0 USD
Availability: InStock
Rating: 95 (22 reviews)

,{[proInfo.pro_purity]}

Cat. No.: {[proInfo.prAm]}

DV 2D 3D

3d Animation Molecule Structure of 89-05-4

Structure of 89-05-4 * Storage: {[proInfo.prStorage]}

Cart0 Add to My Favorites Add to My Favorites Bulk Inquiry Inquiry Add To Cart

Search after Editing

* Storage: {[proInfo.prStorage]}

For Research Only 110K+ Compounds Competitive Price 1-2 Day Shipping

Quality Control of [ 89-05-4 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 89-05-4 ]

SDS Specification

Alternatived Products of [ 89-05-4 ]

Product Details of [ 89-05-4 ]

CAS No. :	89-05-4	MDL No. :	MFCD00002471
Formula :	C₁₀H₆O₈	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	CYIDZMCFTVVTJO-UHFFFAOYSA-N
M.W :	254.15	Pubchem ID :	6961
Synonyms :

Calculated chemistry of [ 89-05-4 ]

Physicochemical Properties

Num. heavy atoms :	18
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	4
Num. H-bond acceptors :	8.0
Num. H-bond donors :	4.0
Molar Refractivity :	54.28
TPSA :	149.2 Å²

Pharmacokinetics

GI absorption :	Low
BBB permeant :	No
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-7.83 cm/s

Lipophilicity

Log Po/w (iLOGP) :	-0.52
Log Po/w (XLOGP3) :	0.03
Log Po/w (WLOGP) :	0.48
Log Po/w (MLOGP) :	0.58
Log Po/w (SILICOS-IT) :	-0.43
Consensus Log Po/w :	0.03

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	1.0
Egan :	1.0
Muegge :	0.0
Bioavailability Score :	0.56

Water Solubility

Log S (ESOL) :	-1.42
Solubility :	9.72 mg/ml ; 0.0383 mol/l
Class :	Very soluble
Log S (Ali) :	-2.72
Solubility :	0.489 mg/ml ; 0.00193 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	0.1
Solubility :	321.0 mg/ml ; 1.26 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	0.0
Synthetic accessibility :	1.62

Safety of [ 89-05-4 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P280-P302+P352-P305+P351+P338	UN#:	N/A
Hazard Statements:	H315-H319-H335	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 89-05-4 ]

* 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.

Upstream synthesis route of [ 89-05-4 ]
Downstream synthetic route of [ 89-05-4 ]

[ 89-05-4 ] Synthesis Path-Upstream 1~5

1
[ 89-05-4 ]
[ 15383-49-0 ]
[ 2754-41-8 ]

Reference： [1] Patent: US2016/137789, 2016, A1,

2
[ 89-05-4 ]
[ 2754-41-8 ]

Reference： [1] Patent: CN108069978, 2018, A,
[2] Patent: CN108069978, 2018, A,
[3] Patent: CN108069978, 2018, A,
[4] Patent: CN108069978, 2018, A,
[5] Patent: CN108069978, 2018, A,
[6] Patent: CN108069978, 2018, A,
[7] Patent: CN108069978, 2018, A,

3
[ 89-05-4 ]
[ 712-74-3 ]

Reference： [1] Journal of Organic Chemistry, 1992, vol. 57, # 11, p. 3051 - 3057
[2] Patent: CN105016939, 2017, B,
[3] Patent: CN105001032, 2018, B,

4
[ 89-05-4 ]
[ 34240-10-3 ]
[ 528-44-9 ]
[ 88-99-3 ]
[ 89-32-7 ]
[ 2479-49-4 ]
[ 7487-10-7 ]

Reference： [1] Patent: EP1746081, 2007, A1, . Location in patent: Page/Page column 8-10

5
[ 89-05-4 ]
[ 15383-49-0 ]

Yield	Reaction Conditions	Operation in experiment
99.1%	at 33℃; for 2 h; Autoclave	34.3 g of commercially available pyromellitic dianhydride (GC analysis purity: 98.2percent) was charged into 500 mL high pressure kettle, meanwhile 250 mL of deionized water and 2.5 g of a 5 wtpercent Pd-C catalyst as a precious metal catalyst were added, then the hydrogen gas was introduced into the high pressure kettle (autoclave) and the hydrogen pressure was controlled at 2MPa, the temperature was controlled at 33 ° C ± 1 ° C, and carried the reaction for 2h. [0024] And then cooled to room temperature (15 ° C ~ 25 ° C, the same below) to discharge the filter, the filter cake separated Pd-C catalyst, this catalyst was placed in air overnight after that it can be recycled for the next batch of catalytic hydrogenation reaction. After the filtrate was distilled off, hydrogenated pyromellitic acid wass precipitated; Filtered again, and the filter cake was subjected to decolourization and purification using deionized water and activated carbon and then obtained 38.8g of white solid hydrogenated pyromellitic acid, the yield was 99.1percent, GC analysis was 99.46percent.
85%	With rhodium contaminated with carbon; hydrogen In water at 60℃; for 2 h; Autoclave	Made from Hastelloy with an internal volume of 5 liters (HC 22)An autoclave was charged with 552 g of pyromellitic acid,200 g of a catalyst in which rhodium was supported on activated carbon (manufactured by N. E. Chemcat Corporation)1656 g of water was charged,The inside of the reactor was replaced with nitrogen gas while stirring.Subsequently, the interior of the reactor was replaced with hydrogen gas,The temperature was raised to 60 ° C. with the hydrogen pressure in the reactor set at 5.0 MPa.The reaction was carried out for 2 hours while keeping the hydrogen pressure at 5.0 MPa. Hydrogen gas in the reactor was replaced with nitrogen gas,The reaction solution was withdrawn from the autoclave,The reaction solution was filtered while hot to separate the catalyst.The filtrate was concentrated by evaporating water under reduced pressure with a rotary evaporator,Crystals were precipitated.The precipitated crystal was subjected to solid-liquid separation at room temperature,And dried to obtain 481 g (yield: 85.0percent) of 1,2,4,5-cyclohexanetetracarboxylic acid.

Reference： [1] Patent: CN103992330, 2016, B, . Location in patent: Page/Page column 5-7
[2] Patent: JP2017/202981, 2017, A, . Location in patent: Paragraph 0105
[3] Patent: EP2316811, 2011, A1, . Location in patent: Page/Page column 7-8
[4] Patent: JP6083270, 2017, B2, . Location in patent: Paragraph 0048; 0056
[5] Patent: CN108069978, 2018, A,
[6] Patent: CN108069978, 2018, A,
[7] Patent: CN108069978, 2018, A,

[ 89-05-4 ] Synthesis Path-Downstream 1~88

1
[ 16440-97-4 ]
[ 89-05-4 ]

Reference： [1]Journal of the American Chemical Society,1948,vol. 70,p. 2791

2
[ 89-05-4 ]
[ 89-32-7 ]

Yield	Reaction Conditions	Operation in experiment
90%	2,6-bis[(2,2,6,6-tetramethylpiperidin-1-yl)methyl]phenylboronic acid; In butryonitrile; for 12h;Reflux;	Examples 28 to 32Synthesis of a tetracarboxylic dianhydride used as a raw material for polyimide resin synthesis was investigated. In particular, in accordance with Examples 21 to 27, the dehydrative condensation reaction of a tetracarboxylic acid (2.5 mmol) shown in Table 5 was performed in butyronitrile (10 mL) in the presence of the boronic acid compound E (0.025 mmol, 1 percent by mole). After the reaction mixture was cooled to room temperature, 50 mL of pentane was added, and a precipitated solid was collected by filtration, so that a target tetracarboxylic dianhydride was obtained. In addition, in Example 32, instead of the isolated yield, the conversion yield was obtained by analysis using 1H NMR. The results are shown in Table 5. Each tetracarboxylic acid showed excellent reactivity, and a carboxylic dianhydride corresponding thereto was obtained in high yield (85% to 99%). Although the results obtained by reaction performed under no catalyst conditions were also shown in Table 5, the reaction hardly progressed under no catalyst conditions.
88%	With bathophenanthroline; In N,N-dimethyl acetamide; toluene; for 12h;Reflux;	General procedure: In a 25ml three-necked flask, add 4,7-diphenyl-1,10-phenanthroline (17mg, 2mol%), 4-methylphthalic acid (450mg, 2.5mmol), and finally add solvent toluene (9mL) ) and N,N-dimethylacetamide (1 ml) to help dissolve, the mixture was heated under azeotropic reflux conditions for 12 hours, and the reflux liquid was passed through molecular sieves to remove water. After the reaction was completed, the mixture was cooled and filtered to remove the solvent to obtain 4-methylphthalic anhydride in a yield of 97%.
	at 190 - 270℃; under 150.015 - 15001.5 Torr; for 0.1 - 24h;	The purified crystals of <strong>[89-05-4]pyromellitic acid</strong> is converted to pyromellitic anhydride in the dehydration step by a heat dehydration method or an acetic anhydride method. The heat dehydration is conducted by known method, for example, by heating the purified crystals of <strong>[89-05-4]pyromellitic acid</strong> at 190 to 270C under 0.02 to 2 MPa for 0.1 to 24 h.

	With acetic anhydride; under 760.051 Torr; for 0.5 - 24h;Heating / reflux;	The acetic anhydride method is conducted, for example, by heating a mixture of one part by weight of the purified crystals of <strong>[89-05-4]pyromellitic acid</strong> and 1 to 20 parts by weight of acetic anhydride at reflux temperature under atmospheric pressure for 0.5 to 24 h.
	With acetic anhydride; for 6h;Reflux;	Synthesis of compound 2. (Jiao, G., Castro, J. C, Thoresen, L. H. & Burgess, K. Microwave-assisted syntheses of regioisomerically pure bromorhodamine derivatives. Org. Lett. 5, 3675-3677 (2003)). Pyromellitic acid was dissolved in acetic oxide, and the resulting solution was brought to and maintained under reflux for 6 h. The reaction mixture was then cooled to room temperature and filtered. The yellow solid collected, raw pyromellitic dianhydride, was washed with diethyl ether and dried in vacuo. A sample of this solid (5.45 g, 0.025 mol) was then added to a melt of resorcinol (5.5 g, 0.050 mol) at 150 C with vigorous stirring. Fused ZnCI2 (6.80 g, 0.050 mol) was then added slowly, and the temperature of the resulting mixture was slowly raised to 180 C over 20 min until the reaction mixture solidified. The brick red solid was pulverized and extracted in 100 mL of 0.5 M HCI for 1 h. The red solid was collected, washed with water and dried in vacuo. Crude product was subjected to column chromatography on silica gel with 1 :2 (volume ratio) concentrated ammonia/isopropanol as the eluting solution. Isolated yield: 31 .4%. 1H NMR (DMSO-d6, 300 MHz) δ 10.17 (s, 2H), 8.29 (d, J = 15.0 Hz, 1 H), 7.52 (s, 1 H), 6.67 (dd, J = 7.9, 5.5 Hz, 4H), 6.56 (dd, J = 8.7, 2.3 Hz, 2H). 13C NMR (DMSO-d6, 600 MHz) δ 167.35, 159.73, 154.60, 151.75, 140.51 , 133.94, 129.32, 127.49, 125.55, 123.94, 112.70, 108.49, 102.28, 83.47. HRMS [M-H]" calcd for [C22H11O9]" 419.0401 ; found 419.0392.
42 g	In N,N-dimethyl acetamide; chlorobenzene; toluene; at 111℃; for 20h;Inert atmosphere;	Into a 3 L three-neck flask were added 100 g of <strong>[89-05-4]pyromellitic acid</strong> and the solvent made up of 200 mL of N,N-dimethylacetamide, 1000 mL of chlorobenzene, and 400 mL of toluene at room temperature in a nitrogen flow. After being heated up to 111 C., the materials in the flask were subjected to a reaction with stirring at that temperature for 20 hours. After the solvent was removed, the reaction product was washed by being dispersed in toluene and then filtered to yield 42 g of <strong>[89-05-4]pyromellitic acid</strong> dianhydride.

Reference： [1]ARKIVOC,2010,vol. 2010,p. 63 - 74
[2]Organic Letters,2011,vol. 13,p. 892 - 895
[3]Patent: US2011/319620,2011,A1 .Location in patent: Page/Page column 10-11
[4]Patent: CN114213372,2022,A .Location in patent: Paragraph 0045-0050
[5]Chemische Berichte,1911,vol. 44,p. 137
[6]Chemische Berichte,1924,vol. 57,p. 2014
Chemisches Zentralblatt,1928,vol. 99,p. 1386
[7]Chemische Berichte,1942,vol. 75,p. 1330,1336
[8]Monatshefte fur Chemie,1922,vol. 43,p. 629
[9]Journal of Organic Chemistry,1981,vol. 46,p. 4569 - 4570
[10]Patent: EP1439161,2004,A2 .Location in patent: Page column 4
[11]Patent: EP1439161,2004,A2 .Location in patent: Page column 4
[12]Patent: WO2016/196359,2016,A1 .Location in patent: Paragraph 0047
[13]Patent: US2016/376285,2016,A1 .Location in patent: Paragraph 0115

3
[ 89-05-4 ]
[ 7710-20-5 ]

Yield	Reaction Conditions	Operation in experiment
	With thionyl chloride; In N-methyl-acetamide; tetrachloromethane; benzene;	A mixture of 50.0 g of 1,2,4,5-benzene tetracarboxylic acid, 250 ml of thionyl chloride and 1.0 ml of dimethylformamide is refluxed for 18 hours. The resulting solution is evaporated to an oil which is dissolved in carbon tetrachloride and filtered through diatomaceous earth. The filtrate is evaporated to an oil which solidifies on cooling to give a colorless solid. The solid is dissolved in 250 ml of benzene, the solution filtered, and the filtrate is concentrated to 110 ml and cooled to provide a precipitate. The precipitate is removed by filtration and the filtrate is again concentrated and filtered as above. The filtrate is concentrated and diluted with hexane to precipitate a product (26.4 g) which is collected by filtration. The filtrate is evaporated and the residue is washed with hexane to provide 5.7 g of additional product. The combined product (32.1 g) is recrystallized twice from carbon tetrachloride, collected and washed with carbon tetrachloride and hexane and dried to yield 9.6 g of 1,2,4,5-benzenetetracarbonyl chloride.

Reference： [1]Zeitschrift fur Naturforschung, B: Chemical Sciences,2000,vol. 55,p. 567 - 575
[2]Justus Liebigs Annalen der Chemie,1870,vol. Suppl.7,p. 20
    Justus Liebigs Annalen der Chemie,1873,vol. 166,p. 325
[3]Bulletin of the Academy of Sciences of the USSR Division of Chemical Science,1972,vol. 21,p. 558 - 560
    Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,1972,vol. 21,p. 599 - 601
[4]Chemistry Letters,1987,p. 1025 - 1028
[5]Patent: US4118585,1978,A
[6]Dalton Transactions,2012,vol. 41,p. 7092 - 7097
[7]Angewandte Chemie - International Edition,2012,vol. 51,p. 12534 - 12537
    Angew. Chem.,2012,vol. 124,p. 12702 - 12705,4
[8]Chemistry - A European Journal,2014,vol. 20,p. 10266 - 10270
[9]European Journal of Organic Chemistry,2017,vol. 2017,p. 609 - 617

4
[ 95-93-2 ]
[ 89-05-4 ]

Yield	Reaction Conditions	Operation in experiment
97%	With 3H3N3H(1+)[MnMo6O18(OH)6](3-)*7H2O; sodium acetate; In acetonitrile; at 100℃; under 7500.75 Torr; for 15h;	1.3422 g (0.01 mol) of tetramethylbenzene,0.1200 g (0.0001 mol) of [NH4]3[MnMo6O18 (OH)6]·7H2O polyoxometallate catalyst,0.0136g (0.0001mol) of sodium acetate additive,And 8mL of solvent acetonitrile inputIn the dry reaction tube,After heating to 100 C,React in the air,The pressure (gauge pressure) is 1.0MPaAfter the heat preservation reaction for 15 hours,Stop the reaction,The reaction system was extracted 3 times with ethyl acetate.The obtained product is removed under reduced pressure,Separation by column chromatography yields pyromellitic acid,Get the product 2.4652g,The yield was 97%.
50.6%	With oxygen;hydrogen bromide; manganese(II) acetate; zirconium(IV) acetate; In water; acetic acid; at 220℃; under 24752.5 Torr; for 1.5h;Conversion of starting material;	A catalyst liquid (zirconium concentration 0.01% by weight, manganese concentration 0.37% by weight, bromine concentration 0.4% by weight and water concentration 5% by weight) mixed zirconium acetate, manganese acetate tetrahydrate, 47 wt % hydrogen bromide aqueous solution, glacial acetic acid and water at the rate of 300 g/h and durene at the rate of 73 g/h were fed to a zirconium autoclave of 2L, equipped with a gas exhaust pipe with a reflux cooling tube, a gas injection nozzle and a stirrer. Air was introduced at 220 C. under 3.3 MPaG and oxidation was performed in batch one stage in a residence time of 90 minutes. The result is shown in Table 2.
91%Chromat.	With oxygen;zirconium(IV) sulfate; cobalt(II) acetate; manganese(II) acetate; 2,6-dihydroxypyrrolo[3,4-f]isoindolo-1,3,5,7(2H,6H)tetrone; In acetic acid; at 80 - 130℃; under 15001.5 Torr; for 6h;Product distribution / selectivity;	Example 2; Reaction Temperature 80 C.→120 C.→130 C., Pressure 2 MPa; Into an air-flow reactor, 40 g (0.30 mol) of durene, 320 g of acetic acid, 0.19 g (0.7 mmol) of cobalt acetate (bivalent), 0.55 g (2.2 mmol) of manganese acetate (bivalent), and 1.06 g (3.0 mmol) of zirconium sulfate were charged. The reactor pressure was raised to 2 MPa by nitrogen, and the mixture was heated to 80 C.A slurry having 14.8 g (60 mmol) of N,N'-dihydroxypyromellitimide added in 300 g of acetic acid and a mixed gas of air and nitrogen were fed to the reactor, and at this time the reaction was initiated. The slurry was fed to the reactor over 5 hours by a slurry pump, and the gas was fed to the reactor to adjust the oxygen concentration contained in off-gas to 2 to 8%. After the reaction was initiated, the reaction temperature was raised to 120 C. over 0.5 hours and then continued being maintained for 1.5 hours. At this point in time, a sample for HPLC analysis was taken. Thereafter, the reaction was continued for 3 hours at 130 C. During the reaction, the feed rate of the gas and that of the catalyst were adjusted, if necessary, to control the reaction.After the catalyst addition was completed (5 hours after the reaction was initiated), the reaction mixture was aged at 130 C. for one hour with maintaining the oxygen concentration contained in off-gas at 8%. Thereafter, the supply of the gas was stopped, and the reactor was cooled and the pressure was released.The results of the HPLC analysis at 2 hours after the reaction was initiated revealed that pyromellitic acid. (yield 8% (6.1 g)), methyltrimellitic acid (yield 50% (33.4 g)), and dimethylterephthalic acid (yield 23% (13.3 g)) were produced. The oxidation degree at this point in time was as follows: 8%+37.5%+11.5%=57%. Moreover, the HPLC analysis of the reaction mixture after the pressure was released revealed that pyromellitic acid (yield 91% (68.9 g)) and methyltrimellitic acid (yield 2% (1.3 g)) were produced.

In this example, a 1 gallon (3.785 liters) titanium autoclave equipped with a reflux condenser, stirrer and air blowing nozzle was used as the reactor. The reactor was charged with 90.1 g of duren, 720 g of acetic acid, 2.85 g of cobalt acetate and 1.23 g of sodium bromide as a reactant, purged with an inert gas of helium gas, and then heated to a temperature of 150 C. The pressure was maintained at 400 psig and the liquid phase oxidation reaction was initiated while the compressed air was slowly injected into the autoclave. 100 minutes after the reaction was completed, the injection of compressed air was stopped briefly, and 1.53 g of manganese acetate was dissolved in 140 g of water, and the temperature was raised to 220 C., and then the oxidation reaction was continued while injecting the compressed air into the reactor. The concentration of oxygen in the off-gas was analyzed by gas chromatography. When the oxygen concentration in the off-gas began to exceed 8 vol%, the injection of compressed air was stopped and the reaction was terminated. Upon completion of the reaction, the reaction product was extracted, the reaction product was methylesterified, and the yield of pyromellitic acid was calculated by gas chromatography (product name: 5890, HP). As a result, a yield of pyromellitic acid of 88.1 mol% was obtained.

Reference： [1]Patent: CN108218686,2018,A .Location in patent: Paragraph 0011; 0037; 0038; 0039 0040; 0041; 0041-0046
[2]Journal of Organic Chemistry USSR (English Translation),1980,vol. 16,p. 612 - 615
Zhurnal Organicheskoi Khimii,1980,vol. 16,p. 698 - 702
[3]Science China Chemistry,2021,vol. 64,p. 1487 - 1492
[4]Patent: US2005/85663,2005,A1 .Location in patent: Page/Page column 5-6
[5]Patent: US2509855,1948,A
[6]Chemische Berichte,1884,vol. 17,p. 2517
[7]Journal of the Chemical Society,1957,p. 1196,1198
[8]Patent: US2011/71314,2011,A1 .Location in patent: Page/Page column 13
[9]Patent: KR101735110,2017,B1 .Location in patent: Paragraph 0048-0051

5
[ 528-90-5 ]
[ 89-05-4 ]

Reference： [1]Journal of the Chemical Society,1912,vol. 101,p. 2192

6
[ 89-32-7 ]
[ 89-05-4 ]

Yield	Reaction Conditions	Operation in experiment
96.6%	With water; for 4h;Reflux;	(1) 34.3 g of commercially available pyromellitic dianhydride (GC analysis purity: 98.2%) and 250 mL of deionized water was charged into 500 mL and the reaction was heated to reflux for 4h.after cooling the reaction to room temperature, filtrated , then the filter cake was subjected to decolourization and purification using deionized water and activated carbon and then obtained 38.5g of white solid hydrogenated pyromellitic acid, the yield was 96.6%, GC analysis was 98.50%.

Reference： [1]Patent: CN103992330,2016,B .Location in patent: Page/Page column 5-7
[2]Journal fur praktische Chemie (Leipzig 1954),1851,vol. <1> 52,p. 432
 Justus Liebigs Annalen der Chemie,1851,vol. 80,p. 281
[3]Journal fur praktische Chemie (Leipzig 1954),1851,vol. <1> 52,p. 432
 Justus Liebigs Annalen der Chemie,1851,vol. 80,p. 281
[4]Angewandte Chemie - International Edition,2020,vol. 59,p. 15050 - 15060
 Angew. Chem.,2020,vol. 132,p. 15160 - 15171,12

7
[ 64-17-5 ]
[ 89-05-4 ]
[ 6634-01-1 ]

Yield	Reaction Conditions	Operation in experiment
80%	With sulfuric acid; for 12h;Reflux;	In a 1L three-necked flask equipped with a thermometer, mechanical stirring, and reflux condenser, 100g of <strong>[89-05-4]pyromellitic acid</strong> was added,500mL of anhydrous ethanol, 10g of concentrated sulfuric acid, heated to reflux for 12h, evaporated half of the solvent, and then added 250mL of anhydrous ethanol. After refluxing for 12h, remove half of the solvent, stop heating, cool to 0-5C, and stir for 1h. , suction filtration, filter cake washed with 20mL absolute ethanol.After drying under reduced pressure at room temperature, 97.6 g of ethylbenzene tetracarboxylate was obtained. The yield was 80%. HPLC purity was 99.2%.

Reference： [1]Patent: CN108069978,2018,A .Location in patent: Paragraph 0076; 0077; 0078
[2]Journal of Organic Chemistry,1962,vol. 27,p. 3479 - 3482

8
[ 528-90-5 ]
alkaline permanganate [ No CAS ]
[ 89-05-4 ]

Reference： [1]Journal of the Chemical Society,1912,vol. 101,p. 2192

9
[ 1003-68-5 ]
[ 89-05-4 ]
benzene-1,2,4,5-tetracarboxylic acid; compound with 5-methyl-1H-pyridin-2-one [ No CAS ]

Reference： [1]Mendeleev Communications,2004,vol. 14,p. 247 - 249

10
[ 89-05-4 ]
[ 2550-73-4 ]

Reference： [1]Journal of Organic Chemistry,1993,vol. 58,p. 1740 - 1745

11
[ 5779-72-6 ]
[ 528-90-5 ]
[ 89-05-4 ]

Yield	Reaction Conditions	Operation in experiment
		Trimethyl benzoic acid at the rate of 25 g/h, trimethyl benzaldehyde at the rate of 5 g/h separated in step B as raw materials and water as a solvent at the rate of 230 g/h was fed to a zirconium autoclave of 2 L (reactor 3), equipped with a gas exhaust tube with a reflux cooling tube, a gas injection nozzle and a stirrer. Manganese bromide tetrahydrate, iron bromide and hydrogen bromide as a catalyst were added thereto so as to maintain manganese concentration 0.43% by weight, iron concentration 0.0008% by weight and bromine concentration 2.4% by weight to the solvent. The reactor interior temperature was raised in a nitrogen atmosphere. Air was introduced therein at 215 C. under 3.0 MPaG and the continuous reaction was performed in a residence of 90 minutes. The reaction products thus obtained were analyzed. The yield of pyromellitic acid to reacted durene in all steps was 73.2 mol %. The result is shown in Table 1.; EXAMPLE 2 The experiment was performed in the same manner as in Example 1 except that the feeding rate of trimethyl benzoic acid in step A was changed to 165 g/h. The result is shown in Table 1. EXAMPLE 3 The experiment was performed in the same manner as in Example 1 except that cobalt naphthenate in step D was used instead of manganese naphthenate. The result is shown in Table 1. EXAMPEL 4 The experiment was performed in the same manner as in Example 1 except that the feeding rate of trimethyl benzoic acid in step A was changed to 0 g/h. The result is shown in Table 1. EXAMPLE 5 The experiment was performed in the same manner as in Example 1 except that the feeding rate of water as a solvent in step A was changed to 0 g/h. The result is shown in Table 1. EXAMPLE 6 The experiment was performed in the same manner as in Example 1 except that the feeding rate of durene as a solvent in step D was changed to 0 g/h. The result is shown in Table 1.; (Step C) Trimethyl benzoic acid at the rate of 25 g/h, trimethyl benzaldehyde at the rate of 5 g/h separated in step B as raw materials and water as a solvent at the rate of 230 g/h were fed to a zirconium autoclave of 2 L (reactor 3), equipped with a gas exhaust tube with a reflux cooling tube, a gas injection nozzle and a stirrer. Manganese bromide tetrahydrate, iron bromide and hydrogen bromide as a catalyst were added thereto so as to maintain manganese concentration 0.43% by weight, iron concentration 0.0008% by weight and bromine concentration 2.4% by weight to the solvent. The reactor interior temperature was raised in a nitrogen atmosphere. Air was introduced therein at 215 C. under 3.0 MPaG and the continuous reaction was performed in a residence time of 90 minutes. The reaction products thus obtained was analyzed. The yield of pyromellitic acid to reacted durene in all steps was 72.0 mol %. The result is shown in Table 2. EXAMPLE 8 The experiment was performed in the same manner as in Example 7 except that the feeding rate of trimethyl benzoic acid in step A was changed to 165 g/h. The result is shown in Table 2. EXAMPLE 9 The experiment was performed in the same manner as in Example 7 except that the feeding rate of trimethyl benzoic acid in step A was changed to 0 g/h. The result is shown in Table 2. EXAMPLE 10 The experiment was performed in the same manner as in Example 7 except that the feeding rate of water as a solvent in step A was changed to 0 g/h. The result is shown in Table 2.

Reference： [1]Patent: US2005/85663,2005,A1 .Location in patent: Page/Page column 3-6

12
[ 89-05-4 ]
[ 3102-70-3 ]
[ 143907-75-9 ]

Yield	Reaction Conditions	Operation in experiment
	In nitrogen; water;	EXAMPLE 6 Synthesis of 2,6-Bis(3-amino-2,4,6-trimethylphenyl)-benzo[1,2-c:4;5-c']-dipyrrole-1,3,5,7(2H,6H)-tetrone A mixture of pyromellitic acid (5.08 g; 0.02 mole) and 2,4,6-trimethyl-1,3-phenylenediamine (6.00 g; 0.04 mole) in water was degassed under vacuum and the air in the sealed vessel replaced with nitrogen. The mixture was heated with stirring at 250C. and 3585 KPa for 4 h. When cool the fine powder was filtered off, washed with water, and dried to give the diaminobisimide 7.27 g (70% yield calculated as monomer). The reaction product gave a 1H nmr spectrum in dimethylsulphoxide typical of a bisimide and confirmed the absence of starting materials, oligomers and side reaction products.

Reference： [1]Patent: US5693822,1997,A

13
[ 5779-72-6 ]
[ 89-05-4 ]
[ 34240-10-3 ]
[ 528-44-9 ]
[ 88-99-3 ]

Yield	Reaction Conditions	Operation in experiment
		Into the first reactor of a continuous two-stage reactor composed of two Zr oxidation reactors each equipped with a reflux condenser, a stirring device, a heating device, an inlet for raw materials, a gas inlet and an outlet for discharging the reaction product, was charged 1000 parts by weight of an aqueous catalyst solution containing 2.3% by weight of bromide ion, 0.44% by weight of manganese ion and 13 ppm of iron ion. Into the second reactor, 500 parts by weight of the aqueous catalyst solution of the same type was charged. The inner pressure was increased to 1 MPa by introducing nitrogen under pressure from the gas inlet. The inner temperature was raised to 210C by the heating device. Into the first reactor, 2,4,5-trimethylbenzaldehyde was supplied at a rate of 90 parts by weight/h, and separately, the aqueous catalyst solution of the same type was supplied at a rate of 780 parts by weight/h. Simultaneously with the beginning of supply of 2,4,5-trimethylbenzaldehyde, the supply of air from the gas inlet was started at a controlled flow rate so as to maintain the oxygen concentration of the exhaust gas from the reactor at 2.5% by weight. Then, the solution was started to be transferred from the first reactor to the second reactor while maintaining the liquid level of the first reactor at its initial level. At the same time, the supply of an aqueous catalyst solution containing 3.3% by weight of bromide ion, which had been prepared by mixing 58 parts by weight of water and 2 parts by weight of pure hydrogen bromide, into the second reactor was started at a rate of 60 parts by weight/h, and the supply of air from the gas inlet was started at a controlled flow rate so as to maintain the oxygen concentration of the exhaust gas from the second reactor at 4.5% by weight. Thereafter, the reaction product was discharged from the second reactor at a rate of 150 parts by weight/h, while maintaining the liquid level of the second reactor at its initial level. During the above operations, the inner pressure was kept at 3.2 MPa for the first reactor and at 2.9 MPa for the second reactor. The reaction product was then hydrogenated at 150C under 1 MPa in the presence of a 0.5%-Pd/C catalyst. After cooling, the crystals were separated by filtration and dried. The dried crystals were dissolved in 2.5 times by weight water at 130C. The solution was cooled to 30C, and the precipitated crystals were separated, rinsed with the same amount of water and dried at 130C for 5 h, to obtain a crude pyromellitic acid (pyromellitic acid: 98.8% by weight; trimellitic acid: 0.6% by weight; methyltrimellitic acid: 0.1% by weight; phthalic acid: 0.2% by weight).

Reference： [1]Patent: EP1746081,2007,A1 .Location in patent: Page/Page column 7

14
europium(III) chloride hexahydrate [ No CAS ]
[ 126-71-6 ]
[ 89-05-4 ]
Eu₄(PM)3*3H₂O*TIBP₃ [ No CAS ]

Reference： [1]Koordinatsionnaya Khimiya,1988,vol. 14,p. 780 - 787
Koordinatsionnaya Khimiya,1988,vol. 14,p. 1377 - 1384

15
[ 4199-89-7 ]
nickel(II) perchlorate hexahydrate [ No CAS ]
[ 89-05-4 ]
[ 207453-66-5 ]

Reference： [1]Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry,1998,vol. 28,p. 367 - 381

16
cobalt(II) chloride tetrahydrate [ No CAS ]
[ 89-05-4 ]
[ 1137-67-3 ]
Co(2-(3-pyridyl)benzimidazole)(1,2,4,5-benzenetetracarboxylate)0.5(H₂O) [ No CAS ]

Reference： [1]Journal of Molecular Structure,2007,vol. 831,p. 195 - 202

17
[ 89-05-4 ]
[ 710351-11-4 ]

Reference： [1]Bulletin of the Chemical Society of Japan,2008,vol. 81,p. 278 - 286

18
[ 95-93-2 ]
[ 89-05-4 ]
[ 34240-10-3 ]

Yield	Reaction Conditions	Operation in experiment
66%Chromat.; 24%Chromat.	With oxygen;zirconium(IV) sulfate; cobalt(II) acetate; manganese(II) acetate; 2,6-dihydroxypyrrolo[3,4-f]isoindolo-1,3,5,7(2H,6H)tetrone; In acetic acid; at 120℃; under 6000.6 Torr; for 6h;Product distribution / selectivity;	Comparative Example 2; Reaction Temperature 120 C. Constant; Into an air-flow reactor, 40 g (0.30 mol) of durene, 320 g of acetic acid, 0.19 g (0.7 mmol) of cobalt acetate (bivalent), 0.55 g (2.2 mmol) of manganese acetate (bivalent), and 1.06 g (3.0 mmol) of zirconium sulfate were charged. The reactor pressure was raised to 0.8 MPa by nitrogen, and the mixture was heated to 120 C.A slurry having 14.8 g (60 mmol) of N,N' -dihydroxypyromellitimide added in 300 g of acetic acid and a mixed gas of air and nitrogen were fed to the reactor, and at this time the reaction was initiated. The slurry was fed to the reactor over 5 hours by a slurry pump, and the gas was fed to the reactor to adjust the oxygen concentration contained in off-gas to 2 to 8%. During the reaction, the feed rate of the gas and that of the catalyst were adjusted, if necessary, to control the reaction.After the catalyst addition was completed (5 hours after the reaction was initiated), the reaction mixture was aged at 120 C. for one hour with maintaining the oxygen concentration contained in off-gas at 8%. Thereafter, the supply of the gas was stopped, and the reactor was cooled and the pressure was released.The HPLC analysis of the reaction mixture after the pressure was released revealed that pyromellitic acid (yield 66% (50.3 g)) and methyltrimellitic acid (yield 24% (16.1 g)) were produced.
12%Chromat.; 48%Chromat.	With oxygen;zirconium(IV) sulfate; cobalt(II) acetate; manganese(II) acetate; 2,6-dihydroxypyrrolo[3,4-f]isoindolo-1,3,5,7(2H,6H)tetrone; In acetic acid; at 80 - 130℃; for 6h;Product distribution / selectivity;	Comparative Example 4; Catalyst Bulk Feeding; Into an air-flow reactor, 40 g (0.30 mol) of durene, 14.8 g (60 mmol) of N,N'-dihydroxypyromellitimide, 320 g of acetic acid, 0.19 g (0.7 mmol) of cobalt acetate (bivalent), 0.55 g (2.2 mmol) of manganese acetate (bivalent), and 1.06 g (3.0 mmol) of zirconium sulfate were charged. The reactor pressure was raised to 0.8 MPa by nitrogen, and the mixture was heated to 80 C. Acetic acid (300 g) and a mixed gas of air and nitrogen were fed. to the reactor, and at this time the reaction was initiated. The acetic acid was fed to the reactor over 5 hours, and the gas was fed to the reactor to adjust the oxygen concentration contained in off-gas to 2 to 8%. After the reaction was initiated, the reaction temperature was raised to 120 C. over 0.5 hours and then continued being maintained for 1.5 hours. At this point in time, a sample for HPLC analysis was taken. Thereafter, the reaction was continued for 3 hours at 130 C. During the reaction, the feed rate of the gas and that of the catalyst were adjusted, if necessary, to control the reaction.After the acetic acid addition was completed (5 hours after the reaction was initiated), the reaction mixture was aged at 130 C. for one hour with maintaining the oxygen concentration contained in off-gas at 8%. Thereafter, the supply of the gas was stopped, and the reactor was cooled and the pressure was released.The results of the HPLC analysis at 2 hours after the reaction was initiated revealed that pyromellitic acid (yield 10%) and methyltrimellitic acid (yield 48%) were produced. The oxidation degree at this point in time was as follows: 10%+48%×¾+23%×½=57.5%. Moreover, the HPLC analysis of the reaction mixture after the pressure was released revealed that pyromellitic acid (yield 12%) and methyltrimellitic acid (yield 48%) were produced.

Reference： [1]Patent: US2011/71314,2011,A1 .Location in patent: Page/Page column 15
[2]Patent: US2011/71314,2011,A1 .Location in patent: Page/Page column 15

19
[ 89-05-4 ]
[ 15383-49-0 ]

Yield	Reaction Conditions	Operation in experiment
99.1%	With ruthenium-carbon composite; water; hydrogen; at 33℃; under 15001.5 Torr; for 2.0h;Autoclave;	34.3 g of commercially available pyromellitic dianhydride (GC analysis purity: 98.2%) was charged into 500 mL high pressure kettle, meanwhile 250 mL of deionized water and 2.5 g of a 5 wt% Pd-C catalyst as a precious metal catalyst were added, then the hydrogen gas was introduced into the high pressure kettle (autoclave) and the hydrogen pressure was controlled at 2MPa, the temperature was controlled at 33 C ± 1 C, and carried the reaction for 2h. [0024] And then cooled to room temperature (15 C ~ 25 C, the same below) to discharge the filter, the filter cake separated Pd-C catalyst, this catalyst was placed in air overnight after that it can be recycled for the next batch of catalytic hydrogenation reaction. After the filtrate was distilled off, hydrogenated pyromellitic acid wass precipitated; Filtered again, and the filter cake was subjected to decolourization and purification using deionized water and activated carbon and then obtained 38.8g of white solid hydrogenated pyromellitic acid, the yield was 99.1%, GC analysis was 99.46%.
85%	With rhodium contaminated with carbon; hydrogen; In water; at 60℃; under 37503.8 Torr; for 2.0h;Autoclave;	Made from Hastelloy with an internal volume of 5 liters (HC 22)An autoclave was charged with 552 g of pyromellitic acid,200 g of a catalyst in which rhodium was supported on activated carbon (manufactured by N. E. Chemcat Corporation)1656 g of water was charged,The inside of the reactor was replaced with nitrogen gas while stirring.Subsequently, the interior of the reactor was replaced with hydrogen gas,The temperature was raised to 60 C. with the hydrogen pressure in the reactor set at 5.0 MPa.The reaction was carried out for 2 hours while keeping the hydrogen pressure at 5.0 MPa. Hydrogen gas in the reactor was replaced with nitrogen gas,The reaction solution was withdrawn from the autoclave,The reaction solution was filtered while hot to separate the catalyst.The filtrate was concentrated by evaporating water under reduced pressure with a rotary evaporator,Crystals were precipitated.The precipitated crystal was subjected to solid-liquid separation at room temperature,And dried to obtain 481 g (yield: 85.0%) of 1,2,4,5-cyclohexanetetracarboxylic acid.
	With hydrogen;5% Rh/C; 5% Pd(II)/C(eggshell); In water; at 55 - 65℃; under 60006.0 Torr; for 2.0h;Inert atmosphere;Product distribution / selectivity;	EXAMPLE 4 (97 repeated activations by air) The cycle composed of the separation of the mixture of carbon supported catalysts, the activation by air and the nuclear hydrogenation was repeated 97 times in the same manner as in Example 2 to conduct the recycling test of catalyst, except for conducting each run of the nuclear hydrogenations in the same manner as in Example 3. The results are shown in Table 1.

	With hydrogen; In water; at 50℃; under 67506.8 Torr; for 1.5h;Autoclave;	In a 200 ml SUS 316 autoclave, 0.5 g of catalyst A and 30 g of water were charged. After replacing the gas phase part three times with 1 MPa of nitrogen, the gas phase part was substituted three times with 1 MPa of hydrogen to make a hydrogen atmosphere. The pressure was increased up to 5 MPa with hydrogen and stirred with an electromagnetic stirring blade for 60 minutes at room temperature. Thereafter, the pressure was dropped, the flange was opened, and 5 g of trimesic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 g of water were charged in the autoclave. The pressure was increased to 9 MPa with hydrogen, the temperature was raised to 50 C. while stirring with an electromagnetic type stirring blade, and the reaction was stopped in 75 minutes from the start of the heating. When the reaction product is derivatized to a methyl ester form and analyzed by gas chromatography, the conversion of trimesic acid is 100%, the selectivity of hydrogenated trimesic acid (1,3,5-cyclohexanetricarboxylic acid) is 94.6 mol% . When the catalyst was repeatedly used under the same conditions as this method, the conversion rate of trimesic acid in the third use of the catalyst was 98.6%, and the selectivity of hydrogenated trimesic acid was 94.6 mol%.
	With 5% rhodium-on-charcoal; 5%-palladium/activated carbon; hydrogen; In water; at 50℃; under 60006.0 Torr;Large scale;	First, 390.1 kg of pyromellitic acid, 2340.9 kg of water, 131.0 kg of a 5% by mass Pd-carbon powder catalyst (manufactured by N.E. Chemcat Corporation, a product wetted with water, PE-type, a water content of 55% by mass), and 56.2 kg of a 5% by mass Rh-carbon powder catalyst (manufactured by N.E. Chemcat Corporation, a product wetted with water, a water content of 50% by mass) were charged into a 3.86 m3 SUS316L reaction vessel equipped with a thermocouple, a stirrer, a temperature controller, and the like. While stirring the mixture, hydrogen was fed to 8 MPa, and the temperature was raised to 50 C. While retaining the pressure and the temperature, the hydrogenation reaction was continued until the molar amount of absorbed hydrogen was 3 times the molar amount of pyromellitic acid charged. The resulting reaction solution was discharged, the catalyst was separated by filtration, and thus a colorless, transparent filtrate was obtained. Thereafter, the resulting filtrate was concentrated until the concentration of nuclear-hydrogenated pyromellitic acid was 33% by mass, and then cooled to 20 C. to precipitate crystals of 1,2,4,5-cyclohexanetetracarboxylic acid. The precipitated crystals were separated by filtration. The resulting crystals of 1,2,4,5-cyclohexanetetracarboxylic acid were charged into a 2.5 m3 SUS316 conical dryer, and the crystals were dried at 40 C. for 16 hours and then further dried at 90 C. for 29 hours (total 45 hours) to obtain white crystals. The particle size of the resulting 1,2,4,5-cyclohexanetetracarboxylic acid measured by SEM observation revealed an average particle size of 33.4 mum. The proportion of particles having a particle size of 10 mum or less was 5% by number, the proportion of particles having a particle size of 20 mum or more was 82% by number, and the proportion of particles having a particle size of 40 mum or more was 28% by number. The lengths of the major axes of particles on a 100× or 1000× image taken by FE-SEM (manufactured by Hitachi High-Technologies Corporation, S-3000N, voltage of 10 kV) were measured using image processing software Image J. Measurement was made on 100 particles, and the average value of the obtained results was regarded as the average particle size of cyclohexanetetracarboxylic acid. Also, the proportion of particles having a particle size (major axis length) of 10 mum or less, the proportion of particles having a particle size of 20 mum or more, and the proportion of particles having a particle size (major axis length) of 40 mum or more were calculated.

Reference： [1]Patent: CN103992330,2016,B .Location in patent: Page/Page column 5-7
[2]Patent: JP2017/202981,2017,A .Location in patent: Paragraph 0105
[3]Patent: EP2316811,2011,A1 .Location in patent: Page/Page column 7-8
[4]Patent: JP6083270,2017,B2 .Location in patent: Paragraph 0048; 0056
[5]Patent: CN108069978,2018,A
[6]Patent: CN108069978,2018,A
[7]Patent: CN108069978,2018,A
[8]Patent: US2020/31841,2020,A1 .Location in patent: Paragraph 0103-0107; 0111-0114; 0118-0120; 0149-0151

20
[ 89-05-4 ]
[ 16834-13-2 ]
C₁₀H₆O₈*C₄₀H₂₆N₈ [ No CAS ]

Reference： [1]Journal of Inclusion Phenomena and Macrocyclic Chemistry,2010,vol. 66,p. 403 - 408

21
gallium(III) nitrate hexahydrate [ No CAS ]
[ 89-05-4 ]
Gd₄(1,2,4,5-benzenetetracarboxylate)₃(H₂O)₁₆*12H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%		An aqueous solution (9.5 mL) of <strong>[89-05-4]1,2,4,5-benzenetetracarboxylic acid</strong> (0.2 M), and whose pH was adjusted to 4.5 with sodium hydroxide (0.2 M), was added to a 0.9 ml of tetramethoxysilane. The resulting mixture was introduced into a test tube, covered with parafilm, and stored for one day at room temperature to allow the gel formation. Finally, an aqueous solution (5 mL) of gadolinium(III) nitrate hexahydrate (0.2 M) was carefully layered on the gel in order to prevent any damage of its surface, and the test tubes were stored at 30 C. X-ray quality colourless prisms of 1 appeared after two days. Yield: 60%. Anal. Calc. for C15H31Gd2O26 (1): C, 19.12; H, 3.32%. Found: C, 19.23; H, 3.28%.

Reference： [1]Polyhedron,2013,vol. 52,p. 321 - 332

22
gallium(III) nitrate hexahydrate [ No CAS ]
[ 89-05-4 ]
Gd₄(1,2,4,5-benzenetetracarboxylate)₃(H₂O)₁₂*15H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
23%	With sodium carbonate; In water; at 20℃;	An aqueous solution of <strong>[89-05-4]1,2,4,5-benzenetetracarboxylic acid</strong> 0.2 M (15 mL) was allowed to react with solid sodium carbonate (2 mmol, 212 mg). To the resulting clear mixture a water solution (16 mL) of gadolinium(III) nitrate hexahydrate (0.02 M) was added. The mixture was stored at room temperature, and colourless prisms suitable for X-ray analysis were obtained after a few days. Yield: 23%. Anal. Calc. for C30H60Gd4O51 (2): C, 19.30; H, 3.24%. Found: C, 19.38; H, 3.19%.

Reference： [1]Polyhedron,2013,vol. 52,p. 321 - 332

23
gallium(III) nitrate hexahydrate [ No CAS ]
[ 89-05-4 ]
Gd₂(1,2,4,5-benzenetetracarboxylic acid)(1,2,4,5-benzenetetracarboxylate)(H₂O)₂*4H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
77%	In water; at 150℃; for 48h;	An aqueous solution (10 mL) of <strong>[89-05-4]1,2,4,5-benzenetetracarboxylic acid</strong> (1.5 M) was poured into an aqueous solution (20 mL) of gadolinium(III) nitrate hexahydrate (1 M). The resulting mixture was sealed in a 45 mL stainless-steel reactor with a teflon liner, and heated at 150 C for 48 hours. After cooling, colourless prismatic crystals were collected from the teflon-liner and air dried. This crystalline material was suitable for X-ray analyses and therefore it was used in all the measurements. Yield: 77%. Anal. Calc. for C10H9GdO11 (3): C, 25.96; H, 1.96%. Found: C, 25.91; H, 2.01%.

Reference： [1]Polyhedron,2013,vol. 52,p. 321 - 332

24
[ 23974-93-8 ]
[ 89-05-4 ]
[ 1428149-32-9 ]
C₁₈H₁₃N₅*C₁₀H₆O₈*HI₃ [ No CAS ]

Reference： [1]Dalton Transactions,2013,vol. 42,p. 5619 - 5622

25
[ 7343-34-2 ]
zinc(II) nitrate hexahydrate [ No CAS ]
[ 89-05-4 ]
[Zn₂(3,5-dimethyl-1-H-1,2,4-triazole)₂(1,2,4,5-benzenetetracarboxylate)(H₂O)₂]_n [ No CAS ]

Reference： [1]Zeitschrift fur Anorganische und Allgemeine Chemie,2013,vol. 639,p. 1884 - 1887

26
zinc(II) nitrate hexahydrate [ No CAS ]
[ 89-05-4 ]
[ 33513-42-7 ]
[H₂N(CH₃)₂]₂[Zn(1,2,4,5-benzenetetracarboxylate acid)]·DMF [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With 1,3-dimethyl-2-imidazolidinone; 5,5'-(1,4-phenylene)bis(1H-tetrazole); at 100℃; for 96h;	Zn(NO3)2.6H2O (0.071 g, 0.24 mmol), 1,2,4,5-benzenetetracarboxylateacid (H4btec, 0.06 g, 0.24mmol), 5,5′-(1,4-phenylene)bis(1H-tetrazole) [6] (H2pbtz,0.05 g, 0.2 mmol), 2 mL N, N′-dimethylformamide (DMF), 1 mL 1,3-Dimethyl-2-imidazolidinone (DMI) in a 20 mL vial was heated at 100 C for 4 days, and then cooled to room temperature, colorless block crystals of 1 were obtained (0.104 g;yield: 90% based on H4btec).

Reference： [1]Inorganic Chemistry Communications,2013,vol. 36,p. 195 - 198

27
zinc(II) nitrate hexahydrate [ No CAS ]
[ 89-05-4 ]
[ 554-13-2 ]
[ 33513-42-7 ]
[H₂N(CH₃)₂]₂[ZnLi(1,2,4,5-benzenetetracarboxylate acid)]·DMF [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With 1,3-dimethyl-2-imidazolidinone; 5,5'-(1,4-phenylene)bis(1H-tetrazole); at 100℃; for 96h;	General procedure: Zn(NO3)2.6H2O (0.071 g, 0.24 mmol), 1,2,4,5-benzenetetracarboxylateacid (H4btec, 0.06 g, 0.24mmol), 5,5′-(1,4-phenylene)bis(1H-tetrazole) [6] (H2pbtz,0.05 g, 0.2 mmol), 2 mL N, N′-dimethylformamide (DMF), 1 mL 1,3-Dimethyl-2-imidazolidinone (DMI) in a 20 mL vial was heated at 100 C for 4 days, and then cooled to room temperature, colorless block crystals of 1 were obtained (0.104 g;yield: 90% based on H4btec).

Reference： [1]Inorganic Chemistry Communications,2013,vol. 36,p. 195 - 198

28
manganese(II) perchlorate hexahydrate [ No CAS ]
[ 64-17-5 ]
[ 89-05-4 ]
[ 1206883-86-4 ]
Cu(2,3-dioxo-5,6:13,14-dibenzo-7,12-trimethyl-1,4,8,11-tetraazacyclo-tetradeca-7,12-diene)Mn(1,2,4,5-benzenetetracarboxylic acid)0.5EtOH [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
56%	With sodium hydroxide; In water; at 100℃; for 72h;pH 7 - 8;	A mixture of Mn(ClO4)3·6H2O (0.01 mmol), H4btec (0.01 mmol), CuL (0.01 mmol, 11.8 mg), H2O (10 mL) and EtOH (2 mL) was stirred at room temperature, then NaOH was added until the pH value of the solution was adjusted to about 7-8. After stirring for 0.5 h, the mixture was transferred to the Teflon-lined reactor and heated to 110 C for 3 days. Deep red crystals was obtained with a yield of 56% based on Mn(ClO4)3·6H2O. Anal. calcd (wt.%) for C27H25CuMnN4O7: C 50.99, H 3.96,N 8.81; found C 50.51, H 3.94, N 8.57. Crystal data For 3: C27H25CuMnN4O7,Mr = 635.99, Orthorhombic, Pbca, a = 11.681(2) Å, b = 16.994(3) Å,c = 24.444(5), α = 90, β = 90, γ = 90, V = 4852.3(17) Å3, Z = 8, Dc =1.741 gcm-3, F(000) = 2600, T = 293 K, R1 = 0.0900, wR2 = 0.1356 with I N 2σ(I) and S = 1.179.

Reference： [1]Inorganic Chemistry Communications,2014,vol. 40,p. 87 - 91

29
[ 127-19-5 ]
[ 89-05-4 ]
uranyl(VI) acetate dihydrate [ No CAS ]
(UO2)2(1,2,4,5-benzenetetracarboxylate)(N,N-dimethylacetamide)2 [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
69%	With nitric acid; In water; at 20 - 120℃; for 26h;pH 1;	General procedure: A mixture of 21.0 mg (0.1 mmol) H4bta ligand, 42.0 mg(0.10 mmol) UO2(CH3COO)22H2O, 10 mL of demineralized waterand 5 mL of DMA was put in a glass vessel and stirred for 2 h atroom temperature. Adjust the pH value with 5 mol/L HNO3 tillthe solution in the glass vessel become clear liquid (pH = 1). Thenthe solution was transferred to a Pyrex flask and kept at 120 Cfor one day. After filtration and wash with demineralized water,light yellow crystals were obtained with a yield of 69% based onUO2(CH3COO)22H2O. By replacing DMA with DMF, complex 2was obtained with a yield of 76%. Anal. Calc. for complex 1, C18H20-N2O14U2 (964.42): C, 22.42; H, 2.09; N, 2.90. Found: C, 22.25; H,2.58; N, 2.67%. IR data (KBr, cm1): 3442(vs), 3050(vw), 2925(w),1285(w), 1570(vs), 1501(s), 1385(vs), 1250(w), 1188(w),1139(w), 930(vs), 869(s), 814(s), 758(s), 642(s), 580(s), 525(s).Anal. Calc. for complex 2, C14H20N2O14U2 (964.42): C, 18.35; H,2.20; N, 3.06. Found: C, 18.53; H, 2.59; N, 2.95%. IR data (KBr,cm1): 3446(vs), 3336(s), 3129(vs), 3011(w), 2776(vw), 1655(vs),1610(vs), 1453(vs), 1402(vs), 1133(s), 1072(w), 915(s), 876(s),803(w), 578(s), 528(s), 472(s).

Reference： [1]Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2014,vol. 123,p. 267 - 272

30
[ 89-05-4 ]
[ 7732-18-5 ]
uranyl(VI) acetate dihydrate [ No CAS ]
[ 33513-42-7 ]
[(UO₂)₂(1,2,4,5-benzenetetracarboxylate)(μ₃-OH₂)]*2[HN(CH₃)₂]*H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With nitric acid; at 20 - 120℃; for 26h;pH 1;	General procedure: A mixture of 21.0 mg (0.1 mmol) H4bta ligand, 42.0 mg(0.10 mmol) UO2(CH3COO)22H2O, 10 mL of demineralized waterand 5 mL of DMA was put in a glass vessel and stirred for 2 h atroom temperature. Adjust the pH value with 5 mol/L HNO3 tillthe solution in the glass vessel become clear liquid (pH = 1). Thenthe solution was transferred to a Pyrex flask and kept at 120 Cfor one day. After filtration and wash with demineralized water,light yellow crystals were obtained with a yield of 69% based onUO2(CH3COO)22H2O. By replacing DMA with DMF, complex 2was obtained with a yield of 76%.

Reference： [1]Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy,2014,vol. 123,p. 267 - 272

31
[ 143131-66-2 ]
[ 89-05-4 ]
[ 6147-53-1 ]
2C₁₀H₂O₈^(4-)*5Co⁽²⁺⁾*C₁₂H₁₂N₆*2HO^(1-)*4H₂O [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
38%		A mixture of Co(OAc)2·4H2O (0.10 mmol, 24.9 mg),1,2,4,5-benzenetetracarboxylatic acid (0.10 mmol, 25.4 mg), 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (0.10 mmol, 24.0 mg) in 10 mL of distilled H2O was stirred for20 min in air, and the pH value of the mixture was adjusted to approximately 6 by NaOH (0.10 mol/dm3), then transferred to a 25 mL Teflon-lined stainless vessel and heated to 140 C for 3 days under autogenous pressure. Purple block crystalsof the complex were obtained after the autoclave was cooled to room temperature at a rate of 5 C/h. With Co(OAc)2·4H2O. Yields: ca. 38% based on Co. Anal. Calcd.for C32H26Co5N6O22 (Fw = 1141.24): C, 33.68; H, 2.30; N, 7.36. Found: C, 33.26; H,2.59; N, 7.62. IR (KBr, cm-1) for the compelx: 3449vs, 2365 s, 1668 m, 1613 m,1544 m, 1412 m, 1086 m, 879w, 796w, 671w, 546w.

Reference： [1]Inorganic Chemistry Communications,2014,vol. 41,p. 43 - 46

32
[ 13160-06-0 ]
copper nitrate hemi(pentahydrate) [ No CAS ]
[ 89-05-4 ]
[Cu₂(1,2,4,5-benzenetetracarboxylate)(1,2,4,5-benzenetetracarboxylate(H₂))(3-pyridylnicotinamide(H))₂(H₂O)₂]_n [ No CAS ]