CN107759460A - A kind of method for preparing the more acid monomers of polyphenyls - Google Patents

A kind of method for preparing the more acid monomers of polyphenyls Download PDF

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CN107759460A
CN107759460A CN201610671354.8A CN201610671354A CN107759460A CN 107759460 A CN107759460 A CN 107759460A CN 201610671354 A CN201610671354 A CN 201610671354A CN 107759460 A CN107759460 A CN 107759460A
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds

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Abstract

The present invention relates to a kind of method for preparing the more acid monomers of polyphenyls.Methods described includes step：In atent solvent, under metal salt catalyst, in the case of use or without using part, use or without using additive A as co-catalyst and use or without using additive B as co-catalyst in the case of, more methyl polyphenyls are reacted with oxidant, so as to obtain multi-joint benzene polycarboxylic acid class monomer.The invention provides a kind of method for the preparation polyphenyls polyacid that condition is relatively mild, easy to operate, pollution is small, financial cost is low.Available for synthesis metal-organic framework material (MOF) or self-assembled material.

Description

A kind of method for preparing the more acid monomers of polyphenyls
Technical field
The present invention relates to technical field of material chemistry, specifically, being related to a kind of method for preparing the more acid monomers of polyphenyls, more specifically , a kind of method for preparing the more acid monomers of polyphenyls with being related to metal catalytic oxidation high efficiency low cost.
Background technology
Metal-organic framework materials (MOF) or organic self-assembled material are the popular domains of modern material chemistry, due to it Have the advantages that more safer than common steel cylinder, amount of storage is more to clean energy resource (hydrogen, methane) storage, be Future New Energy Source vapour Important foundation (" Heterogeneity within Order " in Metal-Organic of car (fuel cell car etc.) development Frameworks,H.Furukawa,U.Muller,O.M.Yaghi,《Angew.Chem.Int.Ed.》, 2015, volume 54, 3417-3430 pages).The most important monomer of metal-organic framework materials or organic self-assembled material is the more acid monomers of polyphenyls, The more acid monomers of polyphenyls of various structures are successfully developed, the method for the high efficiency low cost of the exploitation synthesis more acid monomers of polyphenyls Have great importance.
Prepare at present the more acid monomers of polyphenyls more efficiently method is the corresponding how methyl substituted polyphenyls of oxidation Compound, makes methyl be converted into corresponding formic acid, and other synthetic routes are required for harsh conditions or use using anhydrous and oxygen-free Precious metal palladium, it is worth without industrial applications.Current method for oxidation be mainly high temperature nitric acid oxidation (>170 DEG C), this method Because highly acid is not only very high to equipment requirement, and produce substantial amounts of nitric acid waste water, seriously polluted (Assembly of Metal-Organic Frameworks from Large Organic and Inorganic Secondary Building Units:New Examples and Simplifying Principles for Complex Structures,Omar M.Yaghi et al.,《J.Am.Chem.Soc.》, 2001, volume 123, page 8239-8247；Control over Catenation in Metal-Organic Frameworks via Rational Design of the Organic Building Block, Omar K.Farha et al.,《J.Am.Chem.Soc.》, 2010, volume 132, page 950-952).Another oxidation side Method is to be limited to the solubility problem of how methyl substituted multi-joint benzene compound using excessive potassium permanganate oxidation, this method, The how methyl substituted multi-joint benzene compound of oxidation is not particularly suited for, and this method can also produce substantial amounts of potassium permanganate contaminated wastewater (Facile Synthesis of 5,10,15-Hexaaryl Truxenes:Structure and Properties,Min- Tzu Kao et al.,《Org.Lett.》, 2011, volume 13,1714-1717 pages).
Therefore, this area is there is an urgent need to a kind of condition is relatively mild, and financial cost is low, waste water produces less, it is suitable extensively to have With property and it is suitable for the method for the more acid monomers of preparation polyphenyls of industrialized production.
The content of the invention
One of the object of the invention is to provide that a kind of condition is relatively mild, and financial cost is low, waste water produces less, it is suitable extensively to have With property and it is suitable for the method for the more acid monomers of preparation polyphenyls of industrialized production.
Original method for preparing the more acid monomers of polyphenyls, mainly has non-oxide methyl method and oxidation methyl method, all asks Inscribe more, non-oxide methyl method synthetic route is required for using the harsh conditions of anhydrous and oxygen-free or using precious metal palladium, industrialization Using more difficult.Current method for oxidation be mainly high temperature nitric acid oxidation (>170 DEG C), this method is because highly acid is not only to equipment It is required that it is very high, and substantial amounts of nitric acid waste water is produced, it is seriously polluted.Another method for oxidation is using excessive potassium permanganate oxygen Change, this method is limited to the solubility problem of how methyl substituted multi-joint benzene compound, is not particularly suited for aoxidizing more methyl substitutions Multi-joint benzene compound, and this method can also produce substantial amounts of potassium permanganate contaminated wastewater.The present invention is catalyzed using cheap metal, Air or oxygen or hydrogen peroxide carry out oxidation reaction as cheap oxidant in recyclable organic solvent, can be efficiently real Now the methyl of the multi-joint benzene compound of more methyl is oxidized, prepares the more acid monomers of polyphenyls in high yield.Whole course of reaction is without strong Sour highly basic, it is small to equipment corrosion, generated without a large amount of pollutants, it is green.Synthesis for the storage material of clean energy resource provides It is a kind of can large-scale industrial production preparation method.With preferable application prospect.
The method of the more acid monomers of preparation polyphenyls of the present invention：
Methods described is method (A), including step：In atent solvent, under metal salt catalyst, using or without using In the case of part, use or without using additive A as co-catalyst and use or without using additive B as altogether catalysis In the case of agent, the compound shown in formula (I) is reacted with oxidant, so as to obtain the Y type polyphenyls shown in formula (II) More formic acid monomers；
Or methods described is method (B), including step：In atent solvent, under metal salt catalyst, using or do not making In the case of with part, using or as co-catalyst and used or without using additive B as altogether urging without using additive A In the case of agent, the compound shown in formula (III) is reacted with oxidant, the Y types obtained from shown in formula (IV) Multi-joint benzene polycarboxylic acid monomer；
Or methods described is method (C), including step：In atent solvent, under metal salt catalyst, using or do not making In the case of with part, using or as co-catalyst and used or without using additive B as altogether urging without using additive A In the case of agent, the compound shown in formula (V) is reacted with oxidant, the X-type obtained from shown in formula (VI) is more Join benzene polycarboxylic acid monomer；
It is above-mentioned it is various in, a represent 1 or 2, b represent 1 or 2 or 34, c represent 1 or 2, R represent hydrogen or bromine；
Wherein,
The metal salt is selected from the group：Cobalt salt, manganese salt, ruthenium salt, palladium salt, rhodium salt, mantoquita, nickel salt, molysite, molybdenum salt, chromic salts, Tungsten salt, zirconates, hafnium salt, lanthanide metal salt or its combination；The anion of the metal salt can be oxygen, hydroxyl, halogen, nitre Acid group, sulfate radical, nitrite anions, acetylacetone,2,4-pentanedione acid group, oxalate, phosphate radical, hydrogen phosphate, vanadic acid root, aluminate, carbonic acid Root, C1~C8 fatty acid radicals, sulfonate radical anionoid；
When using part, the part is selected from the group：Formula (VII) compound, formula (VIII) compound, substituted pyridines, Quinoline, isoquinolin, bipyridyl, 2,6- bis- (2- pyridine radicals) pyridine, Phen, tetramethylethylenediamine or its combination：
In formula (VII), R1For hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, 2- carboxy ethyls, 2- carboxymethyl groups or Phenyl, R2For C1-C6 alkyl, adamantyl, C3-C6 cycloalkyl, C1-C6 alkoxies, benzyloxy or phenyl；
In formula (VIII), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 Alkyl amino, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 alkyl aminos, n For 0~10；
The substituent of substituted pyridines can be hydrogen, C1-C6 alkyl, benzyl, phenyl, C1-C6 alkoxies, fluorine, chlorine, bromine, iodine, Hydroxyl, amino, amino methyl, carboxyl, methoxycarbonyl group, carbethoxyl group, acetyl group, benzoyl, itrile group, nitro or diformazan ammonia Base；
When using additive A, the additive A is selected from the group one or more：Metal salt I, scandium oxide, scandium nitrate, Scandium sulfate, C2-C12 sodium soaps, C2-C12 aliphatic acid potassium, dodecyl sodium sulfate, neopelex, tetrabutyl bromine Change ammonium, tetrabutylammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl ammonia chloride or its combination；The sun of the metal salt I Ion is lithium, sodium, potassium, calcium, ammonium；The anion of the metal salt I is sulfate radical, inferior sulfate radical, nitrate anion, nitrite anions, phosphorus Acid group, hydrogen phosphate, dihydrogen phosphate, orthophosphite, perchlorate, hypochlorite；
When using additive B, the additive B is selected from the group one or more：2-aza-adamantane-N- oxygen is free Base, 9- azabicyclos [3.3.1] nonane N- oxygen radicals, 2,2,6,6- tetramethyl piperidines nitrogen oxides, 2,2,6,6- tetramethyls- 4- hydroxy piperidines nitrogen oxides, 2,2,6,6- tetramethyl -4- methoxy piperides nitrogen oxides, 2,2,6,6- tetramethyl piperidines -4- Ketone -1- oxygen radicals, 2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides, sodium peroxide, sodium peroxydisulfate, persulfuric acid Potassium, SODIUM PERCARBONATE, potassium percarbonate, peroxosulphuric hydrogen potassium complex salt, sodium perborate, N- hydroxyls dicarboximide or its combination；
The atent solvent is selected from the group：Two esters solvents, alkane solvents, cycloalkane solvent, chlorobenzene, dichloro-benzenes, C2-C6 aliphatic acid, R1CO2R2Esters solvent or its combination, wherein R1For C1~C5 alkyl, R2For C1~C6 alkyl；Two esters are molten Two esters solvents that the fat diacid that agent is C1-C12 is formed with methanol, ethanol, propyl alcohol, isopropanol；
The oxidant is selected from the group：0.1~10.0MPa oxygen, 0.1~10.0MPa air, 0.1~10.0MPa nitrogen Oxygen or air after dilution, or aqueous hydrogen peroxide solution；
Reaction temperature is 20 DEG C~300 DEG C；
Reaction time is 0.5~300 hour.
In another preference, methods described (A) includes step：In atent solvent, under metal salt catalyst, using Or without using part in the case of, using or as co-catalyst and using or make without using additive B without using additive A In the case of for co-catalyst, the compound shown in formula (I) is reacted with oxidant, so as to obtain the Y shown in formula (II) The multi-joint benzene polycarboxylic acid monomer of type；
It is above-mentioned it is various in, a represent 1 or 2.
In another preference, methods described (B) includes step：In atent solvent, under metal salt catalyst, using Or without using part in the case of, using or as co-catalyst and using or make without using additive B without using additive A In the case of for co-catalyst, the compound shown in formula (III) is reacted with oxidant, obtained from shown in formula (IV) The multi-joint benzene polycarboxylic acid monomer of Y types；
It is above-mentioned it is various in, b represent 1 or 2 or 3 or 4.
In another preference, methods described (C) includes step：In atent solvent, under metal salt catalyst, using Or without using part in the case of, using or as co-catalyst and using or make without using additive B without using additive A In the case of for co-catalyst, the compound shown in formula (V) is reacted with oxidant, obtained from shown in formula (VI) The multi-joint benzene polycarboxylic acid monomer of X-type；
It is above-mentioned it is various in, c represent 1 or 2, R represent hydrogen or bromine.
In another preference, the part is selected from the group：Formula (VII) compound, formula (VIII) compound, substitution pyrrole Pyridine, quinoline, isoquinolin, bipyridyl, 2,6- bis- (2- pyridine radicals) pyridine, Phen, tetramethylethylenediamine or its combination：
In formula (VII), R1For hydrogen, methyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, cyclohexyl, benzyl, 2- carboxyls Ethyl, 2- carboxymethyl groups or phenyl, R2For methyl, ethyl, propyl group, isopropyl, the tert-butyl group, adamantyl, cyclohexyl, methoxy Base, benzyloxy or phenyl；
In formula (VIII), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 Alkyl amino, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 alkyl aminos, n For 0~10；
The substituent of substituted pyridines can be hydrogen, C1-C6 alkyl, benzyl, phenyl, C1-C6 alkoxies, fluorine, chlorine, bromine, iodine, Hydroxyl, amino, amino methyl, carboxyl, methoxycarbonyl group, carbethoxyl group, acetyl group, benzoyl, itrile group, nitro or diformazan ammonia Base.
In another preference, the metal salt is selected from the group：Copper acetate, copper chloride, stannous chloride, copper bromide, chlorination Nickel, nickel acetate, ferric acetate, iron chloride, ferric acetyl acetonade, ferric sulfate, cobalt acetate, cobalt chloride, cobaltous fluoride, cobaltous bromide, lithia Cobalt, cobalt hydroxide, cobalt carbonate, cobalt oxalate, cobaltous sulfate, cobalt-chromate, cobalt aluminate, cobalt nitrate, cobaltous ammonium phosphate, molybdenum oxide cobalt, amino Sulfonic acid cobalt, acetylacetone cobalt, hexanitro cobalt acid sodium, nitrification cobalt hexamine complex compound, manganese acetate, manganese chloride, manganous fluoride, carbonic acid Manganese, manganese phosphate, manganese oxalate, manganese sulfate, manganese oxide, cerous acetate, cerium chloride, cerium fluoride, cerium hydroxide, cerous nitrate, ammonium ceric nitrate, Cerium oxide, cerous phosphate, cerium vanadate, zirconium oxide cerium, cerous sulfate, Cericammoniumsulfate, acetylacetone,2,4-pentanedione cerium, cerous carbonate, cerium oxalate, perchloric acid Cerium, isooctyl acid cerium, trifluoromethanesulfonic acid cerium, ruthenic chloride, five ruthenium hydrochloride ammoniums, the sour potassium of chlordene ruthenium (III), ruthenium-oxide, palladium bichloride, acetonitrile Palladium bichloride, acid chloride, palladium trifluoroacetate, radium chloride, rhodium acetate, chlorine rhodium acid potassium, rhodium nitrate, rhodium hydroxide, zirconium oxide, oxidation Lanthanum, samarium oxide, lanthanum nitrate, scandium nitrate, zirconium nitrate, samaric nitrate, lanthanum sulfate, zirconium sulfate, samarium sulphate, zirconyl acetate, zirconium acetate, oxygen Change molybdenum, acetic acid molybdenum, molybdenum trisulfate, acetic acid tungsten, tungsten oxide, acetic acid hafnium, hafnium oxide, acetic acid praseodymium, praseodymium oxide, Potassium Zirconium Fluoride, nitric acid Oxygen zirconium, zirconium oxycarbonate, zirconium carbonate or its combination；
It is preferred that when using additive part, the metal salt is selected from the group：Copper acetate, copper chloride, stannous chloride, Copper bromide, ferric acetate, iron chloride, ferric acetyl acetonade, ferric sulfate, cobalt acetate, cobalt chloride, cobaltous fluoride, cobaltous bromide, lithium cobalt oxide, Cobalt hydroxide, cobalt carbonate, cobalt oxalate, cobaltous sulfate, cobalt-chromate, cobalt aluminate, cobalt nitrate, cobaltous ammonium phosphate, molybdenum oxide cobalt, sulfamic acid Cobalt, acetylacetone cobalt, hexanitro cobalt acid sodium, nitrification cobalt hexamine complex compound, manganese acetate, manganese chloride, manganous fluoride, manganese carbonate, phosphorus Sour manganese, manganese oxalate, manganese sulfate, manganese oxide, cerous acetate, cerium chloride, cerium fluoride, cerium hydroxide, cerous nitrate, ammonium ceric nitrate, oxidation Cerium, cerous phosphate, cerium vanadate, zirconium oxide cerium, cerous sulfate, Cericammoniumsulfate, acetylacetone,2,4-pentanedione cerium, cerous carbonate, cerium oxalate, perchloric acid cerium, Isooctyl acid cerium, trifluoromethanesulfonic acid cerium, ruthenic chloride, five ruthenium hydrochloride ammoniums, the sour potassium of chlordene ruthenium (III), ruthenium-oxide, zirconium oxide, lanthana, Samarium oxide, lanthanum nitrate, scandium nitrate, zirconium nitrate, samaric nitrate, lanthanum sulfate, zirconium sulfate, samarium sulphate, zirconyl acetate, zirconium acetate, oxidation Molybdenum, acetic acid molybdenum, molybdenum trisulfate, acetic acid tungsten, tungsten oxide, acetic acid hafnium, hafnium oxide, acetic acid praseodymium, praseodymium oxide, Potassium Zirconium Fluoride, Nitric Acid Oxidation Zirconium, zirconium oxycarbonate, zirconium carbonate or its combination.
In another preference, when using additive A, the additive A is selected from the group one or more：Metal salt I, Scandium oxide, scandium nitrate, scandium sulfate, C2-C12 sodium soaps, C2-C12 aliphatic acid potassium, dodecyl sodium sulfate, detergent alkylate Sodium sulfonate, TBAB, tetrabutylammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl ammonia chloride or its combination； The cation of the metal salt I is lithium, sodium, potassium, calcium, ammonium；The anion of the metal salt I is sulfate radical, inferior sulfate radical, nitric acid Root, nitrite anions, phosphate radical, hydrogen phosphate, dihydrogen phosphate, orthophosphite, perchlorate, hypochlorite.
In another preference, when using additive B, the additive B is selected from the group one or more：2- azepines gold Firm alkane-N- oxygen radicals, 9- azabicyclos [3.3.1] nonane N- oxygen radicals, 2,2,6,6- tetramethyl piperidines nitrogen oxides, 2, 2,6,6- tetramethyl -4- hydroxy piperidines nitrogen oxides, 2,2,6,6- tetramethyl -4- methoxy piperides nitrogen oxides, 2,2,6,6- Tetramethyl piperidine -4- ketone -1- oxygen radicals, 2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides, sodium peroxide, mistake Sodium sulphate, potassium peroxydisulfate, SODIUM PERCARBONATE, potassium percarbonate, peroxosulphuric hydrogen potassium complex salt, sodium perborate, the formyl of N- hydroxyls two are sub- Amine or its combination；Wherein, the N- hydroxyls dicarboximide can be：HP, perchloro--N- hydroxyls Phthalimide, 4- carboxy-Ns-hydroxyphthalimide, the fluoro- HPs of 4-, 4- methyl- The fluoro- HP of HP, 2-, 4- methoxycarbonyl group-N- hydroxyls phthalyl are sub- Amine, 4- carbethoxyl groups-HP, 4- propylene carbonyl oxygens-HP, 4- isopropyl oxygen carbonyls Base-HP, 4- butoxy carbonyls-HP, 4- tertbutyloxycarbonyl-N- hydroxyls are adjacent BIDA, N, the equal pyromellitic dimide of N '-dihydroxy or n-hydroxysuccinimide, the formyl of 1,2- hexamethylenes two Imines, N- hydroxyl -2,3- naphthalimides, N- hydroxyl -1,8- naphthalimides.
In another preference, the atent solvent is selected from the group：Dimethyl succinate, diethyl succinate, succinic acid Dipropyl, diisopropyl ester amber acid, dimethyl glutarate, ethyl glutarate, glutaric acid dipropyl, glutaric acid diisopropyl ester, Dimethyl adipate, diethylene adipate, dipropyl adipate, diisopropyl adipate, n-hexane, normal heptane, dodecane, ring Hexane, chlorobenzene, dichloro-benzenes, acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid or its combination.
In another preference, when being calculated with mol ratio, (I)/metal salt/part/additive A/additive B is 1.0/ 0.001~0.3/0~0.3/0~0.3/0~0.3；Or (III)/metal salt/part/additive A/additive B is 1.0/ 0.001~0.3/0~0.3/0~0.3/0~0.3；Or (V)/metal salt/part/additive A/additive B is 1.0/0.001 ~0.3/0~0.3/0~0.3/0~0.3；It is preferred that when being calculated with mol ratio, (I)/metal salt/part/additive A/addition Agent B is 1.0/0.005~0.1/0.005~0.01/0.005~0.01/0.005~0.01；Or (III)/metal salt/part/ Additive A/additive B is 1.0/0.005~0.1/0.005~0.01/0.005~0.01/0.005~0.01；Or (V)/gold Category salt/part/additive A/additive B be 1.0/0.005~0.1/0.005~0.01/0.005~0.01/0.005~ 0.01。
In another preference, the oxidant is selected from the group：0.1~10.0MPa oxygen, 0.1~10.0MPa air, 0.1~10.0MPa diluted by nitrogen after oxygen or air or aqueous hydrogen peroxide solution；It is preferred that for 0.1~2.5MPa oxygen, 0.2~0.6MPa air or 0.1~2.5MPa diluted by nitrogen after oxygen or air；More preferably, it is 0.1~0.5MPa oxygen Gas or 0.2~0.5MPa air.
In another preference, reaction temperature is 20 DEG C~300 DEG C；It is preferred that for 100~240 DEG C；More preferably, it is 140 ~180 DEG C.
In another preference, the reaction time is 0.5~300 hour；It is preferred that for 5~72 hours；More preferably, for 8~ 24 hours.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment) It can be combined with each other between each technical characteristic of body description, so as to form new or preferable technical scheme.When above-mentioned metal When the hydrate of salt is more cheap and easily-available than metal salt, described metal salt is corresponding hydrates, if cobalt acetate is four hydration second Sour cobalt, the two catalytic effect are identical.As space is limited, no longer tire out one by one herein and state.
Embodiment
The present inventor and in-depth study, has found the cheap transition metal-catalyzed low-corrosiveness, low of can realizing by long-term Pollution, multi-joint benzene polycarboxylic acid monomer is prepared in high yield, the multi-joint benzene polycarboxylic acid monomer of gained can be applied to metal-organic framework material Expect the storage of the clean energy resource such as (MOF) or organic self-assembled material gas, there is preferable application prospect.On this basis, invent People completes the present invention.
Group definition
As used herein, term " C1-C6 alkyl " refers to the straight or branched alkyl with 1-6 carbon atom, such as methyl, Ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, hexyl or similar group.Similarly, term " C1-C4 Alkyl " refers to the straight or branched alkyl with 1-4 carbon atom.
As used herein, term " C3-C6 cycloalkyl " refers to the cycloalkyl with 3-6 carbon atom, such as cyclopenta, hexamethylene Base or similar group.
Term " C2-C12 aliphatic acid " refers to straight or branched or cyclic alkyl aliphatic acid with 2-12 carbon atom, such as Acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, caproic acid, dodecylic acid or similar aliphatic acid.It is similar Ground, term " C1-C8 aliphatic acid " refer to the straight or branched alkyl aliphatic acid with 1-8 carbon atom.
Term " C2-C6 aliphatic acid " refers to the straight or branched alkyl aliphatic acid with 2-6 carbon atom, such as acetic acid, third Acid, butyric acid, isobutyric acid, pivalic acid, cyclopentanecarboxylic acid, caproic acid or similar aliphatic acid.
Term " C1-C6 alkoxies " refers to the straight or branched alkoxyl with 1-6 carbon atom, such as methoxyl group, ethoxy Base, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, hexyloxy or similar group.It is similar Ground, term " C1-C4 alkoxies " refer to the straight or branched alkoxyl with 1-4 carbon atom.
Term " C3-C6 cycloalkyloxies " refers to the straight or branched alkoxyl with 3-6 carbon atom, such as cyclohexyloxy, Or similar group.
Term " C1-C12 fat diacid " refers to the straight chain fatty diacid with 1-12 carbon atom, such as carbonic acid, second two Sour (oxalic acid), malonic acid, succinic acid, glutaric acid, adipic acid, dodecanedioic acid or similar fat diacid.
Term " C1-C16 alkoxy carbonyl groups " refers to the alkoxy carbonyl group that the alkoxy with 1-16 carbon atom is formed with carbonyl, example Such as carbometoxyl, carbethoxyl group, propylene carbonyl oxygen, different oxygen carbonyl, tertbutyloxycarbonyl, hexamethylene oxygen carbonyl, dodecane oxygen carbonyl, 16 Alkoxy carbonyl group or similar alkoxy carbonyl group.
Term " alkane solvents " are preferably C2-C14 alkane solvents, such as the alkane such as n-hexane, normal heptane, dodecane Class solvent.
Term " cycloalkane solvent " is preferably C3-C14 cycloalkane solvents, such as the cycloalkane such as cycloheptane, hexamethylene Class solvent.
Term " halogen " refers to fluorine, chlorine, bromine or iodine.
Main advantages of the present invention are as follows：
(a) the invention provides a kind of simple, condition is relatively mild, energy consumption is low, high income low to equipment corrosion, choosing The method for the multi-joint benzene polycarboxylic acid monomer that selecting property is high, financial cost is low, pollution is small；
(b) multi-joint benzene polycarboxylic acid monomer obtained by the inventive method, it is fine chemistry industry particularly clean energy resource gas storage material The raw material of material, the exploitation to fuel cell power source class new-energy automobile is most important, has good application prospect.
Embodiments of the invention are elaborated below, the present embodiment is carried out lower premised on technical solution of the present invention Implement, give detailed embodiment and specific operation process, but protection scope of the present invention is not limited to following embodiments.
Because experimental implementation is similar, therefore in addition to embodiment 1, remaining embodiment only lists corresponding conditionses, and form is as follows： From S compounds prepare T compounds (formula (I) to (II)), [reactant metal part additive A additive B, oxidant pressure Power solvent temperature the reaction time (reactant metal part additive A additive B) mol ratio], operate same embodiment 1, yield.The concrete operations of embodiment 1 are as follows.
Embodiment (1) is into (180), and when embodiment uses various metals, ratio is 1 to 1 between each metal.Work as reality When applying example and using multiple ligands, ratio is 1 to 1 between each part.When embodiment uses multiple additives, each addition Ratio is 1 to 1 between agent.When embodiment uses mixed solvent, unless otherwise stated, the first described solvent with another or The volume ratio of multi-solvents is 9 to 1.Aforementioned proportion is only used for realizing following examples, not to the restricted effect of the application.
Embodiment 1
(1) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt chloride+acetylacetone,2,4-pentanedione cerium) PA dodecyl sodium soap (2,2,6,6- tetramethyl piperidines Nitrogen oxides (also known as Tempo)+potassium peroxydisulfate), 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 24 hours (1.0/0.005/0.005/0.005/0.005)]
Cobalt chloride-acetylacetone,2,4-pentanedione cerium (0.020mmol), PA (0.020mmol), 12 are added in a kettle Alkyl fatty acid sodium (0.020mmol), 2,2,6,6- tetramethyl piperidines nitrogen oxides-potassium peroxydisulfate (0.020mmol), toluene (4.0mmol) and diethyl succinate 1.8mL, acetic acid 0.2mL, 140 DEG C of stirring reactions 24 hours, stop under 1.0MPa oxygen Only react, cold filtration obtains product, yield 63%.
(2) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobaltous bromide+stannous chloride) PA dodecyl sodium soap tempo, 1.0MPa oxygen (penta Acid dimethyl+acetic acid) 140 DEG C 48 hours (1.0/0.002/0.002/0.002/0.002)], operate same embodiment 1, produce Rate 72%.
(3) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt chloride Isonicotinamide ten alkyl fatty acid sodium HP, 2.0MPa oxygen (dipropyl succinate+acetic acid) 20 DEG C 300 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 4% (HPLC detections).
(4) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate--, 2.0MPa oxygen (diisopropyl ester amber acid+acetic acid) 120 DEG C 300 hours (1.0/ 0.05/) same embodiment 1, yield], are operated<2% (HPLC detections).
(5) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate quinoline--, 10.0MPa oxygen (dimethyl succinate+acetic acid) 30 DEG C 300 hours (1.0/ 0.05/0.05/)], same embodiment 1, yield are operated<5%.
(6) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) Ben Cu Suangu Kui Lin-(2,2,6,6- tetramethyl piperidine nitrogen oxides+peroxosulphuric hydrogen potassium complex salt), 8.0MPa oxygen (dimethyl succinate+acetic acid) 60 DEG C 240 hours (1.0/0.05/0.05//0.05)], operate with implement Example 1, yield 17%.
(7) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobaltous bromide 2- methoxypyridines ten alkyl fatty acid sodium (2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines The fluoro- HPs of nitrogen oxides+2-), 1.5MPa oxygen (dimethyl succinate+acetic acid) 120 DEG C it is 48 small When (1.0/0.001/0.001/0.001/0.001)], operate same embodiment 1, yield 26%.
(8) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate-lanthanum nitrate) 2- benzyl pyridines TBAB (tempo- potassium peroxydisulfates), 1.0MPa oxygen Gas (dimethyl succinate+acetic acid) 80 DEG C 48 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, Yield 36%.
(9) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) (cobalt acetate+formyl of zirconium oxide) 3- Qiang Jibiding undecyl Zhi Fangsuanna N- hydroxyl -2,3- naphthalenes two is sub- by Ben Amine, 1.6MPa oxygen (dimethyl glutarate+acetic acid) 120 DEG C 48 hours (1.0/0.01/0.01/0.01/0.01)], behaviour Make with embodiment 1, yield 36%.
(10) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate 4- acetylpyridines (lithium nitrite+neopelex) tempo, 1.6MPa gas (penta 2 Diethyl phthalate+acetic acid) 120 DEG C 48 hours (1.0/0.01/0.01/0.02/0.02)], operate same embodiment 1, yield 52%.
(11) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+zirconium sulfate) 2,6- pyridines dimethanol sodium hypochlorite HP, 3.0MPa Oxygen (glutaric acid dipropyl+acetic acid) 120 DEG C 48 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 36%.
(12) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate 4- pyridones (dodecyl sodium soap+sodium hypochlorite) (tempo+4- methyl-N-hydroxies Phthalimide), 1.0MPa oxygen (glutaric acid diisopropyl ester+acetic acid) 120 DEG C 12 hours (1.0/0.01/0.01/ 0.01/0.01)], same embodiment 1, yield 61% are operated.
(13) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate 2 hydroxy pyrimidine (enanthic acid sodium+sodium sulfite) (potassium peroxydisulfate+4- alkoxy carbonyl group-N- hydroxyl neighbour's benzene Dicarboximide), 1.5MPa oxygen (diethylene adipate+acetic acid) 120 DEG C 8 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 68%], are operated.
(14) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+zirconium acetate) 3,4- pyridinedicarboxylic acids (pivalic acid potassium+potassium dihydrogen phosphate) (sodium perborate+N- hydroxyls Base phthalimide), 0.5MPa oxygen (dimethyl sebacate+acetic acid) 120 DEG C 24 hours (1.0/0.01/0.01/ 0.01/0.01)], same embodiment 1, yield 37% are operated.
(15) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (zirconium acetate+trifluoromethanesulfonic acid cerium) 4- chloropyridine -2- formamides (potassium sulfite+potassium nitrate) (2,2,6,6- Tetramethyl piperidine -4- ketone -1- oxygen radicals+HP), 0.8MPa oxygen (diethylene adipate+second Acid) 120 DEG C 16 hours (1.0/0.01/0.01/0.01/0.0)], operate same embodiment 1, yield 37%.
(16) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+manganese acetate+samaric nitrate) 3,5- pyridinedicarboxylic acids TBAB 4- carboxy-Ns-hydroxyl it is adjacent BIDA, 1.0MPa oxygen glutaric acid 120 DEG C 8 hours (1.0/0.01/0.01/0.01/0.0)], operate with real Apply example 1, yield 81%.
(17) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+ruthenic chloride) tetramethylethylenediamine (lithium hypochlorite+potassium phosphite) (9- azabicyclos [3.3.1] Nonane N- oxygen radicals+n-hydroxysuccinimide), 1.0MPa oxygen (dimethyl adipate+acetic acid) 180 DEG C 6 hours (1.0/0.01/0.01/0.01/0.0)], operate same embodiment 1, yield 83%.
(18) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+acetic acid molybdenum) 2,3- pyridinedicarboxylic acids acid anhydride TBAB 2-aza-adamantane-N- oxygen it is free Base, 30% hydrogen peroxide (dimethyl adipate+acetic acid) 120 DEG C 8 hours (1.0/0.01/0.01/0.01/0.0)], behaviour Make with embodiment 1, yield 43%.
(19) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+acetic acid hafnium) 2- fluorine pyridine sodium hypochlorite (sodium peroxide+1,2- hexamethylenes dicarboximide), 1.0MPa oxygen (propionic acid+acetic acid) 180 DEG C 8 hours (1.0/0.01/0.01/0.01/0.0)], operate same embodiment 1, produce Rate 74%.
(20) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate tetramethylethylenediamine (trimethyl benzyl ammonia chloride+potassium hydrogen phosphate) (2-aza-adamantane-N- oxygen Free radical+N, N '-equal pyromellitic dimide of dihydroxy), 1.0MPa oxygen (dimethyl succinate+chlorobenzene+acetic acid) 180 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 81%.
(21) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (4- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+acetic acid praseodymium+lanthana) PA -4- carboxylic acids potassium nitrate 2-aza-adamantane-N- oxygen from By base, 1.0MPa oxygen (dimethyl succinate+dichloro-benzenes+acetic acid) 180 DEG C 12 hours (1.00.1/0.1/0.1/0.)], Operation is the same as embodiment 1, yield 92%.
(22) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+acetylacetone,2,4-pentanedione cerium) N- acetyl group-cheese amino acid (TBAB+trimethyl benzyl bromine Change ammonium) 2-aza-adamantane-N- oxygen radicals, 1.0MPa oxygen (dimethyl succinate+acetic acid) 180 DEG C 12 hours (1.00.2/0.2/0.2/0.2)], operate same embodiment 1, yield 86%.
(23) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene stannous chloride 5- chloropyridines sodium hypochlorite 2-aza-adamantane-N- oxygen radicals, 1.0MPa oxygen (12 Docosandioic acid dimethyl ester+acetic acid) 180 DEG C 25 hours (1.0/0.01/0.01/0.01/0.0)], operate same embodiment 1, yield 72%.
(24) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene cobaltous fluoride 4- pyridones sodium methacrylate the fluoro- HPs of 4-, 0.5MPa oxygen (fourth Acid dimethyl+acetic acid (1:9)) 140 DEG C 24 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, Yield 76%.
(25) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt chloride+cerium hydroxide) tetramethylethylenediamine dodecyl aliphatic acid potassium tempo, 1.0MPa oxygen (diisopropyl ester amber acid+acetic acid) 140 DEG C 24 hours (1.0/0.001/0.001/0.001/0.001)], operate with implement Example 1, yield 37%.
(26) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene (lithium cobalt oxide+cerium hydroxide) 2,6- dioctyl phthalate pyridine six alkyl fatty acid sodium 4- tertbutyloxycarbonyl-N- hydroxyls Base phthalimide, 1.2MPa oxygen (butyric acid+acetic acid) 140 DEG C 12 hours (1.0/0.15/0.15/0.15/ 0.15) same embodiment 1, yield 81%], are operated.
(27) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) 2,2,6,6- tetramethyl piperidine nitrogen oxides of Ben Yi Xianbingtonggu 3- Bi Dingjiachun octyl aliphatic acid Jias, 1.2MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 24 hours (1.0/0.005/0.01/0.005/0.005)], behaviour Make with embodiment 1, yield 71%.
(28) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt chloride 3- bromopyridines heptane base sodium soap (tempo+N- HOSu NHSs), 1.2MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 72%.
(29) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) Ben molybdenum oxide Gu 2- Lv Biding butyl Zhi Fangsuanna 2,2,6,6- tetramethyl piperidine nitrogen oxides (0.040mmol), 1.2MPa oxygen (diethyl succinate+acetic acid) 160 DEG C 24 hours (1.0/0.01/0.02/0.01/ 0.01) same embodiment 1, yield 83%], are operated.
(30) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene cobaltous ammonium phosphate 2- bromopyridines hexahydrobenzoid acid sodium (2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxygen Compound+sodium peroxide), 1.2MPa oxygen (dipropyl succinate+acetic acid) 200 DEG C 24 hours (1.0/0.02/0.02/ 0.01/0.01)], same embodiment 1, yield 76% are operated.
(31) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene (copper bromide+cobalt chloride) 4- pyridones dodecyl sodium soap tempo, 0.5MPa oxygen (penta 2 Diethyl phthalate+acetic acid) 300 DEG C 24 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 57%.
(32) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) 2,2,6,6- tetramethyl piperidine nitrogen oxides of Ben Cu Suangu Bi Ding Yi Dingsuanjias, 0.5MPa Yang Qi (glutaric acids Dipropyl+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 41%.
(33) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt carbonate (N- acetyl group-glycine+pyridine) pivalic acid potassium tempo, 0.5MPa oxygen (glutaric acid two is different Propyl ester+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 58%.
(34) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt nitrate+manganese acetate) 2- phenylpyridines potassium phosphate the own oxygen carbonyl-HPs of 4-, 0.5MPa oxygen (diethylene adipate+chlorobenzene+acetic acid) 160 DEG C 8 hours (1.00.1/0.05/0.01/0.1)], operation With embodiment 1, yield 68%.
(35) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene cobaltous sulfate (N, N '-di-t-butyl malonamide+tetramethylethylenediamine) dodecyl sodium soap+phosphoric acid hydrogen Potassium 4- methyl-N-hydroxy phthalimides, 1.0MPa oxygen (glutaric acid diisopropyl ester+acetic acid (1:9))\160℃\8 Hour (1.0/0.01/0.01/0.05/0.05)], operate same embodiment 1, yield 57%.
(36) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt carbonate+manganese oxide) quinoline dodecyl sodium soap the fluoro- HPs of 2-, 1.0MPa oxygen (dimethyl succinate+cyclopentanecarboxylic acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], behaviour Make with embodiment 1, yield 68%.
(37) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt carbonate N- benzyloxycarbonyl groups-glutamic acid dodecyl sodium soap 4- methoxycarbonyl group-N- hydroxyl O-phthalics Acid imide, 1.0MPa oxygen (dimethyl succinate+acetic acid) 130 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], Operation is the same as embodiment 1, yield 52%.
(38) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) 2,2,6,6- tetramethyl piperidine nitrogen oxides of Ben Tan Suangu Yi Kuilin dodecyl Zhi Fangsuannas, 0.6MPa oxygen Gas (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.00.3/0.15/0.1/0.1)], operate same embodiment 1, yield 71%.
(39) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt carbonate+cuprous iodide) isoquinolin-Phen dodecyl sodium soap N, the equal benzene four of N- dihydroxy Formyl diimine, 0.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 63%], are operated.
(40) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3- first are prepared from more methyl polyphenyls Base phenyl) benzene stannous chloride 2- iodine pyridines dodecyl sodium soap tempo, 0.5MPa oxygen (dimethyl succinate+ Acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 4%.
(41) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate (4- iodine pyridine+N- methoxies acyl group-glycine) dodecyl sodium soap N- hydroxysuccinimidyls acyl it is sub- Amine, 1.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.05/0.05/0.05/0.05)], operation With embodiment 1, yield 76%.
(42) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate 4- propoxyl group pyridine tetrabutylammonium chloride (sodium peroxydisulfate+peroxosulphuric hydrogen potassium complex salt), 0.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 24 hours (1.0/0.01/0.01/0.01/0.01)], operation is same Embodiment 1, yield 81%.
(43) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate (4- pyridones+N- pivaloyl groups-alanine) undecyl aliphatic acid potassium 2,2,6,6- tetramethyls Phenylpiperidines -4- ketone -1- oxygen radicals, 5.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/ 0.01/0.01/0.01)], same embodiment 1, yield 82% are operated.
(44) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate 4- pyridones-pyridine dodecyl sodium soap potassium percarbonate, 8.0MPa oxygen (succinic acid Dimethyl ester+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.02/0.01/0.04)], operate same embodiment 1, yield 91%.
(45) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+cerous acetate) N, N, N ', N '-tetrapropyl-heptanedioyl amine dodecyl sodium soap tempo, 10.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 6 hours (1.0/0.01/0.04/0.01/0.04)], operation is same Embodiment 1, yield 78%.
(46) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt chloride+palladium) malonic acid TBAB HP, 0.5MPa oxygen Gas (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.04/0.01)], operate same embodiment 1, Yield 83%.
(47) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobaltous bromide+hexachloro-potassium ruthenate) (PA+N- benzyloxycarbonyl groups-aspartic acid) ammonium sulfate 2,2,6, 6- tetramethyl piperidine nitrogen oxides, the 0.5MPa Yang Qis (dimethyl succinates+ little Shi (1.0/0.01/ of 160 DEG C of acetic acid) 8 0.01/0.01/0.04)], same to 1,100 grams of scales of embodiment, yield 72% are operated.
(48) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobaltous bromide+hexachloro-potassium ruthenate) (PA+N- benzyloxycarbonyl groups-aspartic acid) ammonium sulfate 2,2,6, 6- tetramethyl piperidine nitrogen oxides, the 0.5MPa Yang Qis (dimethyl succinates+ little Shi (1.0/0.01/ of 160 DEG C of acetic acid) 8 0.01/0.01/0.04)], same to 1,500 grams of scales of embodiment, yield 73% are operated.
(49) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobaltous bromide+hexachloro-potassium ruthenate) ((2- pyridine radicals) pyridine+N- of 2,6- bis- benzyloxycarbonyl groups-aspartic acid) sulfuric acid The tetramethyl piperidine nitrogen oxides of An 2,2,6,6-, the 0.5MPa Yang Qis (dimethyl succinates+ little Shi of 160 DEG C of acetic acid) 8 (1.0/0.01/0.01/0.01/0.04)], operate the same kilogramme-scale of embodiment 1,5, yield 71%.
(50) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+manganese chloride) N- benzyloxycarbonyl groups-Terleu lithium sulfite (2,2,6,6- tetramethyl -4- hydroxyls Piperidines nitrogen oxides+n-hydroxysuccinimide), 0.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 47%.
(51) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobaltous fluoride+Cericammoniumsulfate) 4-aminopyridine lithium nitrite sodium peroxydisulfate, 0.5MPa oxygen (succinic acid two Methyl esters+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.04/0.04/0.04)], operate same embodiment 1, yield 43%.
(52) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (lithium cobalt oxide+cobalt oxalate) isoquinolin potassium hyperchlorate tempo, 0.8MPa oxygen (dimethyl succinate+second Acid) 160 DEG C 24 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 53%.
(53) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt hydroxide+stannous chloride) 4- pyridones sodium hypochlorite (1,2- hexamethylene dicarboximide+N- hydroxyls Base succinimide), 1.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.02/0.01/ 0.02) same embodiment 1, yield 37%], are operated.
(54) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+ferric acetate+nitric acid molybdenum) quinoline dodecyl sodium soap tempo, 0.8MPa oxygen (fourth two Dimethyl phthalate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.02/0.02)], operate same embodiment 1, yield 26%.
(55) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cobalt acetate 4- tert-butoxies pyridine lithium nitrite 4- carboxy-Ns-hydroxyphthalimide, 1.5MPa oxygen Gas (dimethyl succinate+acetic acid) 160 DEG C 16 hours (1.0/0.01/0.02/0.02/0.01)], operate same embodiment 1, Yield 32%.
(56) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene (cobalt acetate+iron chloride) N- methoxycarbonyl groups-aspartic acid dodecyl sodium sulfate 2-aza-adamantane-N- Oxygen radical, 2.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 24 hours (1.0/0.01/0.02/0.01/ 0.01) same embodiment 1, yield 36%], are operated.
(57) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene ammonium ceric nitrate 4-aminopyridine dodecyl sodium sulfate 9- azabicyclos [3.3.1] nonane N- oxygen radicals, 1.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 24 hours (1.0/0.02/0.02/0.02/0.02)], operation is same Embodiment 1, yield 48%.
(58) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene caproic acid cerium 2 hydroxy pyrimidine octyl sodium sulfonate 4- carboxy-Ns-hydroxyphthalimide, 1.0MPa oxygen Gas (dimethyl succinate+acetic acid) 160 DEG C 24 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, Yield 38%.
(59) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cerous phosphate PA (ten sodium alkyl sulfonates+potassium nitrite) n-hydroxysuccinimide, 0.4MPa oxygen Gas (dimethyl succinate+acetic acid) 160 DEG C 24 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, Yield 63%
(60) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cerium vanadate (quinoline+different Kui quinoline) dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 0.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 71%
(61) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cerium fluoride (quinoline+pyridine) dodecyl sodium sulfate (sodium peroxydisulfate+4- methyl-N-hydroxy phthalyls Imines), 1.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 24 hours (1.00.1/0.1/0.1/0.05)], operation With embodiment 1, yield 73%
(62) the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (2- first are prepared from more methyl polyphenyls Base phenyl) benzene cerium hydroxide (quinoline+3- cyclohexyloxies pyridine) dodecyl sodium sulfate 4- hexamethylene oxygen carbonyl-N- hydroxyls it is adjacent BIDA, 0.3MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 48 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 82%], are operated
(63) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene cobalt acetate (N, N, N ', N '-tetra isopropyl-malonamide+isoquinolin) dodecyl sodium sulfate perchloro- Generation-HP, 0.3MPa oxygen (diethyl carbonate+acetic acid) 160 DEG C 12 hours (1.00.1/ 0.1/0.05/0.05)], same embodiment 1, yield 58% are operated
(64) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=1), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene zirconium oxide (isoquinolin+pyridine) dodecyl sodium sulfate N- hydroxyls -1,8-naphthalimide, 0.5MPa oxygen butyric acid 160 DEG C 12 hours (1.0/0.05/0.025/0.01/0.01)], operate same embodiment 1, yield 51%
(65) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene nitrification cobalt hexamine complex compound pyridine-3-sulphonic acid neopelex 4- dodecanes oxygen carbonyl- HP, 1.0MPa oxygen (methyl butyrate+acetic acid) 160 DEG C 12 hours (1.0/0.05/0.1/ 0.01/0.1)], same embodiment 1, yield 56% are operated
(66) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene molybdenum oxide cobalt DAP dodecyl sodium sulfate HP, 1.0MPa oxygen (dimethyl glutarate+acetic acid) 160 DEG C 12 hours (1.0/0.03/0.03/0.03/0.03)], operation is same Embodiment 1, yield 63%
(67) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+perchloric acid cerium+samaric nitrate) 3,5- lutidines potassium acetate perchloro--N- hydroxyls it is adjacent BIDA, 1.0MPa oxygen (ethyl glutarate+acetic acid) 160 DEG C 12 hours (1.0/0.05/0.05/0.05/ 0.05) same embodiment 1, yield 64%], are operated
(68) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) Ben (the ruthenium hydrochloride ammonium) of cobalt acetate+five (N- benzyloxycarbonyl groups-phenylalanine+tetramethylethylenediamine) dodecyls Sodium sulfonate perchloro--HP, 0.4MPa oxygen (dimethyl adipate+acetic acid) 160 DEG C it is 12 small When (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 31%.
(69) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+zirconium acetate) bipyridyl dodecyl sodium sulfate tempo, 0.5MPa oxygen (adipic acid Dimethyl ester+acetic acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 31%.
(70) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+cerous nitrate) 3,5- lutidines-bipyridyl dodecyl sodium sulfate tempo, 0.5MPa oxygen (dimethyl adipate+acetic acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operation is same Embodiment 1, yield 46%.
(71) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+ruthenic chloride) (bipyridyl+pyridine) scandium sulfate tempo, 50% hydrogen peroxide (adipic acid Dimethyl ester+acetic acid) 160 DEG C 12 hours (1.0/0.001/0.001/0.001/0.001)], operate same embodiment 1, yield 28%.
(72) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+lanthanum nitrate) (penta chloropyridine+4- pyridones) dodecyl sodium sulfate rhodium acetate, 0.5MPa air (dimethyl adipate+acetic acid) 160 DEG C 12 hours (1.0/0.002/0.002/0.002/0.002)], behaviour Make with embodiment 1, yield 43%.
(73) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate-lanthana) (bipyridyl+4- pyridones) dodecyl sodium sulfate chlorine rhodium acid potassium, 0.5MPa air (ethyl acetate+acetic acid) 100 DEG C 120 hours (1.0/0.001/0.001/0.001/0.001)], operation With embodiment 1, yield 56%.
(74) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) Ben (cobalt acetate+samarium oxide) N- benzyloxycarbonyl groups-ruthenium hydrochloride ammoniums of Gan Ansuan Shi Erwanjihuangsuannas five, 0.5MPa air (ethyl propionate+acetic acid) 100 DEG C 120 hours (1.0/0.002/0.002/0.002/0.002)], operation With embodiment 1, yield 39%.
(75) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+zirconium sulfate) N- acetyl group-isoleucine dodecyl sodium sulfate acetonitrile palladium chloride, 0.5MPa oxygen (water+acetic acid) 120 DEG C 48 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, produce Rate 26%.
(76) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+hafnium oxide) N- acetyl group-leucine dodecyl sodium sulfate TEMPO, 1.0MPa is empty Gas (dimethyl adipate+acetic acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, Yield 43%.
(77) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+zirconium oxycarbonate) N- benzyloxycarbonyl-aminos glutaric acid dodecyl sodium sulfate TEMPO, 30% hydrogen peroxide (dimethyl adipate+acetic acid) 120 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operation is same Embodiment 1, yield 31%.
(78) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene Potassium Zirconium Fluoride N- acetyl group-aminoglutaric acid dodecyl sodium sulfate perchloro--N- hydroxyl neighbour's benzene Dicarboximide, 0.5MPa air (dimethyl succinate+acetic acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 38%], are operated.
(79) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene acetic acid tungsten N- acetyl group-phenylglycine dodecyl sodium sulfate perchloro--N- hydroxyl phthalyls Imines, 0.5MPa oxygen (diisopropyl ester amber acid+acetic acid) 130 DEG C 12 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 47%], are operated.
(80) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (acetic acid hafnium+manganese acetate) N- Ac-VaIs dodecyl sodium sulfate perchloro--N- hydroxyls it is adjacent BIDA, 0.6MPa oxygen (dimethyl malenate+acetic acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 29%], are operated.
(81) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+zirconyl acetate) N- propionos-glycine dodecyl sodium sulfate perchloro--N- hydroxyls Phthalimide, 1.0MPa air (dimethyl succinate+acetic acid) 140 DEG C 24 hours (1.0/0.01/0.01/ 0.01/0.01)], same embodiment 1, yield 46% are operated.
(82) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (I) to (II) a=2), [1,3,5- tri- (3,5- 3,5-dimethylphenyl) benzene (cobalt acetate+ruthenium-oxide) N- bytyries-glycine ten sodium alkyl sulfonates perchloro--N- hydroxyl neighbour's benzene Dicarboximide, 1.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 48 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 71%], are operated.
(83) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt acetate+manganese acetate) (dodecanedioic acid+N- isobutyryls-glycine) dodecyl sodium sulfate it is complete Chloro-HP, 1.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 24 hours (1.0/ 0.01/0.01/0.01/0.01)], same embodiment 1, yield 73% are operated.
(84) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt acetate+manganese chloride) (PA+dimethyl malenate) dodecyl sodium sulfate perchloro-- HP, 1.0MPa oxygen butyric acid 160 DEG C 24 hours (1.0/0.01/0.01/0.01/0.01)], Operation is the same as embodiment 1, yield 61%.
(85) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt acetate+manganese phosphate) (PA+diethyl malonate) dodecyl sodium sulfate perchloro-- HP, 1.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 12 hours (1.0/0.01/ 0.01/0.01/0.01)], same embodiment 1, yield 62% are operated.
(86) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt acetate+manganese oxalate) (4- pyridones+ethylene dimethyl) dodecyl sodium sulfate perchloro-- HP, 1.0MPa oxygen isobutyric acid 140 DEG C 36 hours (1.0/0.01/0.01/0.01/ 0.01) same embodiment 1, yield 71%], are operated.
(87) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt chloride+manganese carbonate+ferric sulfate) 4- pyridones ten alkyl fatty acid sodium 4- carboxy-Ns-hydroxyl it is adjacent BIDA, 10.0MPa oxygen (dimethyl succinate+acetic acid) 80 DEG C 24 hours (1.0/0.01/0.005/ 0.005/0.01)], same embodiment 1, yield 84% are operated.
(88) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt chloride+lanthana) 2- mercaptopyridines (dodecyl sodium soap+scandium oxide) N- hydroxysuccinimidyl acyls Imines, 5.0MPa oxygen (dimethyl succinate+acetic acid) 80 DEG C 24 hours (1.0/0.01/0.005/0.005/0.01)], Operation is the same as embodiment 1, yield 92%.
(89) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene cobaltous bromide 3- aminopyridines dodecyl sodium soap n-hydroxysuccinimide, 3.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 48 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 88%.
(90) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobaltous fluoride+acetylacetone,2,4-pentanedione cerium) 3- pyridones dodecyl sodium soap (tempo+ sodium hypochlorite), 2.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 24 hours (1.0/0.005/0.005/0.005/0.005)], behaviour Make with embodiment 1, yield 83%.
(91) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) 2,2,6,6- tetramethyl piperidine nitrogen oxides of Ben Cu Suangu 3- itrile group Bi Ding dodecyl Zhi Fangsuannas, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 48 hours (1.00.1/0.05/0.05/0.1)], operate with real Apply example 1, yield 65%.
(92) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) 2,2,6,6- tetramethyl piperidine nitrogen oxides of Ben Lv Huagu 4- itrile group Bi Ding dodecyl Zhi Fangsuannas, 0.5MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 96 hours (1.00.1/0.05/0.2/0.1)], operate with implement Example 1, yield 62%.
(93) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene cobalt chloride 4- acetylpyridines (undecyl sodium soap+TBAB) (tempo+2,2,6,6- Tetramethyl piperidine nitrogen oxides), the 0.1MPa Kong Qis (dimethyl succinates+ little Shi (1.00.1/0.2/ of 140 DEG C of acetic acid) 96 0.1/0.1)], same embodiment 1, yield 34% are operated.
(94) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene cobalt acetate (PA+N- benzoyls-leucine) dodecyl sodium soap tempo, 0.3MPa oxygen (dimethyl succinate+ethyl glutarate+acetic acid) 140 DEG C 64 hours (1.0/0.05/0.05/0.05/ 0.05) same embodiment 1, yield 46%], are operated.
(95) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene cobalt acetate N- benzoyls-glycine ten alkyl fatty acid sodium tempo, 70% hydrogen peroxide (succinic acid Dimethyl ester-acetic acid) 100 DEG C 96 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 36%.
(96) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt acetate+manganese acetate) N- acetyl group-alanine dodecyl sodium soap 2-aza-adamantane-N- Oxygen radical, 0.3MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 96 hours (1.0/0.05/0.1/0.05/ 0.05) same embodiment 1, yield 47%], are operated.
(97) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene (cobalt acetate+cerium oxide) (2,6- dimethoxy-pyridines+N- benzyloxycarbonyl groups-alanine) tetrabutyl phosphonium bromide Ammonium (2-aza-adamantane-N- oxygen radicals+peroxosulphuric hydrogen potassium complex salt), 0.5MPa oxygen (dimethyl succinate+second Acid) 140 DEG C 48 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 41%.
(98) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) Ben (cobalt acetate+stannous chloride) N- Buddha's warrior attendants alkanoyl-Liang Ansuan Si Dingjilvhuaans (2-aza-adamantane- The fluoro- HPs of N- oxygen radicals+2-), 0.5MPa air acetic acid 140 DEG C 32 hours (1.0/0.08/ 0.08/0.08/0.08)], same embodiment 1, yield 32% are operated.
(99) the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- are prepared from more methyl polyphenyls Aminomethyl phenyl) benzene cobalt acetate quinoline TBAB (2-aza-adamantane-N- oxygen radical+N- hydroxysuccinimidyls acyl is sub- Amine), 0.1MPa oxygen acetic acid 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 23%.
(100) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- aminomethyl phenyls) benzene cobalt acetate isoquinolin (TBAB+sodium perchlorate) 2-aza-adamantane-N- oxygen radicals, 0.3MPa air caproic acid 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, produce Rate 31%.
(101) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- aminomethyl phenyls) benzene (cobalt acetate+ruthenic chloride) 2,6- lutidines tri-methyl benzyl ammonium bromide N- hydroxysuccinimidyls acyl it is sub- Amine, 0.4MPa pressure oxygen (diethyl succinate+pivalic acid) 140 DEG C 24 hours (1.00.1/0.2/0.1/0.1)], operation With embodiment 1, yield 48%.
(102) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (4- aminomethyl phenyls) benzene cobalt acetate N- cyclohexyl acyl group-glycine (TBAB+potassium sulfate) potassium peroxydisulfate, 0.4MPa air acetic acid 140 DEG C 32 hours (1.0/0.05/0.1/0.1/0.055)], operate same embodiment 1, yield 33%.
(103) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene cobalt acetate 2- picolines (TBAB+neopelex) 2- azepine Buddha's warrior attendants Alkane-N- oxygen radicals, 0.2MPa air propionic acid 140 DEG C 32 hours (1.0/0.02/0.02/0.02/0.02)], operation is same Embodiment 1, yield 37%.
(104) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene cobalt acetate 2- propyIpyridines neopelex 4- propylene carbonyl oxygen-N- hydroxyl phthalyls Imines, 0.5MPa oxygen butyric acid 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 39%.
(105) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene acetic acid praseodymium N, N '-dimethyl-succinamide TBAB 4- butyloxycarbonyl-N- hydroxyls it is adjacent BIDA, 0.3MPa oxygen isobutyric acid 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], behaviour Make with embodiment 1, yield 8%.
(106) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (praseodymium oxide+ruthenic chloride) N, N '-isopropyl-oxalamide TBAB 4- tertiary butyloxycarbonyls Base-HP, 0.5MPa air (methyl caproate+acetic acid) 140 DEG C 32 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 43% are operated.
(107) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (cobalt acetate+cerous acetate) N, N '-dibutyl-adipamide TBAB (4- butoxy carbonyls- HP+2-aza-adamantane-N- oxygen radicals), 0.5MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 56%.
(108) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (cobalt oxalate+lanthana) 4- picolines (TBAB+dodecyl acid potassium) 2- azepines Adamantane-N- oxygen radicals, 0.5MPa oxygen (pivalic acid ethyl ester+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/ 0.005/0.005)], same embodiment 1, yield 59% are operated.
(109) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (cobalt hydroxide+manganese carbonate) 4- pyridones TBAB (potassium peroxydisulfate+2- azepine Buddha's warrior attendants Alkane-N- oxygen radicals), 0.1MPa pressure oxygen (methyl isobutyrate+isobutyric acid) 140 DEG C 32 hours (1.0/0.05/0.05/ 0.05/0.05)], same embodiment 1, yield 63% are operated.
(110) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (sulfamic acid cobalt+acetic acid tungsten) 2- isopropyl pyridines TBAB 2-aza-adamantane-N- Oxygen radical, 0.8MPa oxygen (dimethyl succinate+dimethyl glutarate+propionic acid) 140 DEG C 48 hours (1.0/0.05/ 0.1/0.05/0.05)], same embodiment 1, yield 58% are operated.
(111) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (manganous fluoride+cobalt acetate) 3,5 lutidines tetrabutylammonium chloride 2,2,6,6- tetramethyl -4- first Oxygen piperidine nitroxide, the 1.2MPa Yang Qis (tert-butyl isobutyrates+ little Shi (1.0/0.02/0.04/ of 140 DEG C of acetic acid) 32 0.02/0.02)], same embodiment 1, yield 61% are operated.
(112) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (manganese acetate+zirconium oxycarbonate) 2- fluorine pyridine trimethyl benzyl ammonia chloride 9- azabicyclos [3.3.1] nonane N- oxygen radicals, 1.0MPa oxygen (isopropyl acetate+acetic acid) 140 DEG C 32 hours (1.0/0.03/ 0.03/0.03/0.03)], the same yield 41% of embodiment 1 is operated.
(113) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (molybdenum oxide cobalt+Cericammoniumsulfate) 2- bromopyridines (TBAB+neopelex) 2-aza-adamantane-N- oxygen radicals, 1.5MPa oxygen (hexyl acetate+acetic acid) 140 DEG C 48 hours (1.0/0.05/ 0.05/0.05/0.05)], same embodiment 1, yield 71% are operated.
(114) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (ferric acetyl acetonade+Potassium Zirconium Fluoride) 2- hexyloxies pyridine TBAB (sodium perborate+4- Carboxy-N-hydroxyphthalimide), 1.2MPa oxygen (ethylene dimethyl+acetic acid) 140 DEG C 24 hours (1.0/ 0.005/0.005/0.005/0.005)], same embodiment 1, yield 53% are operated.
(115) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (sulfamic acid cobalt+palladium trifluoroacetate) 2,6- lutidines TBAB 2,2,6,6- tetra- Methyl piperidine nitrogen oxides, 0.8MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.01/0.02/ 0.02/0.02)], same embodiment 1, yield 61% are operated.
(116) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (acetic acid hafnium+rhodium acetate) PA TBAB 2-aza-adamantane-N- oxygen it is free Base, peroxosulphuric hydrogen potassium complex salt, 0.3MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 24 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 52% are operated.
(117) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (sulfamic acid cobalt+rhodium nitrate) 4- picolines TBAB perchloro--N- hydroxyl neighbour's benzene Dicarboximide, 0.5MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 36 hours (1.0/0.005/0.005/ 0.005/0.005)], same embodiment 1, yield 63% are operated.
(118) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (sulfamic acid cobalt+manganese acetate) 4-aminopyridine TBAB 9- azabicyclos [3.3.1] Nonane N- oxygen radicals, 0.5MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.02/0.02/ 0.05/0.05)], same embodiment 1, yield 69% are operated.
(119) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (cerous carbonate+chlorine rhodium acid potassium) N, N, N ', N '-tetramethyl-dodecane diamides trimethyl benzyl bromination Ammonium (2,2,6,6- tetramethyl piperidine -4- ketone -1- oxygen radical+4- methyl-N-hydroxies phthalimide), 0.5MPa oxygen Gas (dimethyl succinate+acetic acid) 140 DEG C 36 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, Yield 71%.
(120) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (cobaltous ammonium phosphate+chlorine rhodium acid potassium) 3- aminopyridines neopelex 2-aza-adamantane- N- oxygen radicals, 1.0MPa oxygen (dimethyl succinate+acetic acid) 120-160 DEG C 36 hours (1.0/0.05/0.05/ 0.05/0.05)], same embodiment 1, yield 82% are operated.
(121) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (sulfamic acid cobalt+acetic acid molybdenum+zirconium oxide) 4- tert .-butylpyridines sodium acetate 2-aza-adamantane-N- Oxygen radical, 0.1MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.01/0.02/0.01/ 0.01) same embodiment 1, yield 80%], are operated.
(122) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=1), [1,2,4,5- tetra- (3- aminomethyl phenyls) benzene (sulfamic acid cobalt+manganese acetate) 4-aminopyridine neopelex 2,2,6,6- tetramethyls Piperidin-4-one -1- oxygen radicals, 0.8MPa oxygen (dimethyl succinate+diethylene adipate+acetic acid) 140 DEG C it is 36 small When (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 74%.
(123) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (sulfamic acid cobalt+chlorine rhodium acid potassium+zirconium nitrate) 4- benzyl pyridines dodecyl sodium sulfate (2- Azaadamantane-N- oxygen radicals+potassium peroxydisulfate), 0.8MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 71%.
(124) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) Ben (the ruthenium hydrochloride ammonium) 4- Yi Xianbiding Liu Suanli 2,2,6,6- of lanthanum sulfate+five tetramethyl piperidines- 4- ketone -1- oxygen radicals, 0.5MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.02/0.02/ 0.02/0.02)], same embodiment 1, yield 23% are operated.
(125) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (lanthanum sulfate+chlorine rhodium acid potassium) 3,4- pyridinedicarboxylic acids ammonium sulfate the fluoro- N- hydroxyls neighbour benzene two of 4- Carboximide 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.003/0.003/0.003/ 0.003) same embodiment 1, yield 33%], are operated.
(126) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (acetic acid tungsten+zirconium carbonate) 4- cyclohexylmethylpyridines sodium sulfite 2-aza-adamantane-N- oxygen from By base, 0.2MPa oxygen (dimethyl succinate-acetic acid) 140 DEG C 32 hours (1.0/0.01/0.005/0.01/0.01)], Operation is the same as embodiment 1, yield 32%.
(127) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (sulfamic acid cobalt+chlorine rhodium acid potassium) 2,6- lutidines neopelex 2- nitrogen Miscellaneous adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 67% are operated.
(128) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (copper chloride+acetic acid hafnium) 2- pyridine carboxylic acids (neopelex+natrium nitrosum) 2- Azaadamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 32% are operated.
(129) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (cobalt acetate+chlorine rhodium acid potassium) 4- picolines sodium phosphate 2,2,6,6- tetramethyl piperidines -4- Ketone -1- oxygen radicals, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 36 hours (1.0/0.05/0.05/ 0.05/0.05)], same embodiment 1, yield 59% are operated.
(130) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (praseodymium oxide+manganous fluoride) N, N, N ', N '-tetramethyl malonamide sodium phosphite 2,2,6,6- Tetramethyl -4- hydroxy piperidine nitrogen oxides, 0.5MPa oxygen (dimethyl succinate-acetic acid) 140 DEG C 24 hours (1.0/ 0.05/0.05/0.05/0.05)], same embodiment 1, yield 37% are operated.
(131) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (sulfamic acid cobalt+chlorine rhodium acid potassium) N, N, N ', N '-tetraethyl succinamide sodium perchlorate (2-aza-adamantane-N- oxygen radicals+1,2- hexamethylenes dicarboximide), 0.5MPa oxygen (dimethyl succinate+second Acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 39%.
(132) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (manganese acetate+zirconyl nitrate) 2- hexyls pyridine calcium hypochlorite 4- carboxy-Ns-hydroxyl neighbour benzene two Carboximide, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/ 0.005) same embodiment 1, yield 53%], are operated.
(133) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (cerous phosphate+chlorine rhodium acid potassium) 4- pyridones tri-methyl benzyl ammonium bromide 2,2,6,6- tetramethyls Base -4- hydroxy piperidine nitrogen oxides, 0.1MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 48 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 46% are operated.
(134) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) Ben (cerium oxalates+chlorine rhodium acid potassium) 4-An Jibiding Wan Jihuangsuanna in heptan 9- azabicyclos [3.3.1] nonane N- oxygen radicals, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 12 hours (1.0/0.03/ 0.03/0.03/0.03)], same embodiment 1, yield 37% are operated.
(135) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (cerium chloride+stannous chloride) 4- iodine pyridines ten sodium alkyl sulfonates N- hydroxyls phthalyl it is sub- Amine, 0.1MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 48 hours (1.0/0.02/0.02/0.02/0.04)], behaviour Make with embodiment 1, yield 69%.
(136) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (cerium hydroxide+manganese phosphate) 4- nitropyridines (tetrabutylammonium chloride+undecyl sulfonic acid Sodium) HP, 1.0MPa air (dimethyl glutarate+acetic acid) 150 DEG C 48 hours (1.0/ 0.05/0.05/0.05/0.05)], same embodiment 1, yield 38% are operated.
(137) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (cerous sulfate+manganese oxalate) 2,6- diamino-pyridines (trimethyl benzyl ammonia chloride+dodecyl Sodium sulfonate) HP, 0.1MPa oxygen propionic acid 160 DEG C 32 hours (1.0/0.01/0.01/ 0.01/0.02)], same embodiment 1, yield 61% are operated.
(138) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (manganese sulfate+chlorine rhodium acid potassium) 2,6- dihydroxy-pyridines dodecyl sodium sulfate (potassium peroxydisulfate+ HP), 0.5MPa oxygen butyric acid 140 DEG C 24 hours (1.0/0.01/0.02/0.01/ 0.02) same embodiment 1, yield 63%], are operated.
(139) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (tungsten oxide+chlorine rhodium acid potassium) hexanedioic acid dodecyl sodium sulfate perchloro--N- hydroxyl neighbour's benzene Dicarboximide, 0.3MPa oxygen (water+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.1/0.1)], operation is same Embodiment 1, yield 52%.
(140) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (acetic acid hafnium+chlorine rhodium acid potassium) 2,6- lutidines dodecyl sodium sulfate 4- ethoxy carbonyls Base-HP, 0.3MPa oxygen (dimethyl carbonate+acetic acid) 140 DEG C 32 hours (1.0/0.005/ 0.005/0.02/0.02)], same embodiment 1, yield 49% are operated.
(141) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyl) benzene (hafnium oxide+chlorine rhodium acid potassium) DAP dodecyl sodium sulfate N, N '-dihydroxy The equal pyromellitic dimide of base, 0.3MPa air (dimethyl succinate+acetic acid) 150 DEG C 32 hours (1.0/0.05/ 0.05/0.01/0.01)], same embodiment 1, yield 42% are operated.
(142) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (V) to (VI) c=2), [1,2,4,5- tetra- (3,5- 3,5-dimethylphenyls) benzene (isooctyl acid cerium+manganese carbonate) 2- pyridine carboxylic acids dodecyl sodium sulfate perchloro--N- hydroxyls Phthalimide, 0.1MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/ 0.005) same embodiment 1, yield 28%], are operated.
(143) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (butyric acid cerium+nitrification cobalt hexamine complex compound) 2- nitropyridines dodecyl sodium sulfate 4- carbethoxyl groups-HP, 2.0MPa oxygen (dichloro-benzenes+acetic acid) 140 DEG C 32 hours (1.0/ 0.05/0.05/0.05/0.05)], same embodiment 1, yield 81% are operated.
(144) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cobalt chloride+acetic acid praseodymium) 4- nitropyridines undecyl sodium sulfonate 4- propylene carbonyl oxygens- HP, 2.0MPa oxygen (chlorobenzene+dichloro-benzenes+acetic acid) 140 DEG C 48 hours (1.0/0.05/ 0.05/0.05/0.05)], same embodiment 1, yield 75% are operated.
(145) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (stannous chloride+nitrification cobalt hexamine complex compound) Isonicotinamide ten alkyl sulfonic acids Sodium 4- butoxy carbonyls-HP, 1.0MPa oxygen (dimethyl succinate+chlorobenzene+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 46%.
(146) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cuprous iodide+manganese acetate+praseodymium oxide) 2- pyridine carboxylic acids methyl esters hexyl sodium sulfonate 2,2,6,6- tetramethyl piperidine -4- ketone -1- oxygen radicals, 1.0MPa air (chlorobenzene+propionic acid) 140 DEG C 32 hours (1.0/ 0.01/0.01/0.01/0.01)], same embodiment 1, yield 39% are operated.
(147) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (stannous chloride+samarium sulphate) acidum nicotinicum ethyl ester dodecyl sodium sulfate 2,2,6, 6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides, 0.5MPa oxygen (chlorobenzene+butyric acid) 140 DEG C 32 hours (1.0/ 0.05/0.05/0.05/0.05)], same embodiment 1, yield 36% are operated.
(148) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) Ben (ruthenium hydrochloride ammonium) 4- Dian Biding Shi Erwanjihuangsuanna N- hydroxyl ambers of cuprous iodide+five Amber acid imide, 0.2MPa oxygen (dichloro-benzenes+acetic acid+valeric acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/ 0.005) same embodiment 1, yield 27%], are operated.
(149) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (manganese acetate+tungsten oxide) 2- ethylpyridines dodecyl sodium sulfate (potassium peroxydisulfate+mistake Sodium carbonate), 0.5MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], behaviour Make with embodiment 1, yield 33%.
(150) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (stannous chloride+hafnium oxide) 2- chlorine-4-iodines pyridine dodecyl sodium sulfate N, N '-two The equal pyromellitic dimide of hydroxyl, 1.0MPa air (chlorobenzene+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/ 0.005/0.005)], same embodiment 1, yield 47% are operated.
(151) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cobalt acetate+lanthanum sulfate) the chloro- 3- iodine pyridines of 2- dodecyl sodium sulfate peroxosulphuric Hydrogen potassium complex salt, 2.0MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.05)], behaviour Make with embodiment 1, yield 56%.
(152) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cuprous bromide+ruthenium-oxide) 2,4- dihydroxy pyrrole dodecyl sodium sulfate (peroxide sulphur Potassium hydrogen phthalate complex salt+2-aza-adamantane-N- oxygen radicals, 5.0MPa air (chlorobenzene+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 48%.
(153) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cobalt acetate+lanthanum nitrate) 2- aminomethyl pyridines octyl sodium sulfonate perchloro--N- Hydroxyphthalimide, 5.0MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/ 0.05) same embodiment 1, yield 71%], are operated.
(154) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cuprous iodide+cerous phosphate) 2,4- lutidines dodecyl sodium sulfate 4- isopropyls Oxygen carbonyl-HP, 2.5MPa oxygen (chlorobenzene+butyric acid) 140 DEG C 48 hours (1.0/0.05/ 0.05/0.05/0.05)], same embodiment 1, yield 69% are operated.
(155) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cobalt acetate+samaric nitrate) 2,5- dichloropyridines dodecyl sodium sulfate peroxosulphuric hydrogen Potassium complex salt, 2.5MPa oxygen (chlorobenzene+propionic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.05)], operation With embodiment 1, yield 61%.
(156) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (stannous chloride+manganese sulfate) 2,6- bis- (2- pyridine radicals) pyridine dodecyl sodium sulfate Peroxosulphuric hydrogen potassium complex salt, 2.0MPa oxygen (dichloro-benzenes+propionic acid) 140 DEG C 48 hours (1.0/0.05/0.05/0.05/ 0.05) same embodiment 1, yield 73%], are operated.
(157) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cuprous bromide+samarium sulphate) 2,6- lutidines dodecyl sodium sulfate peroxide sulphur Potassium hydrogen phthalate complex salt, 2.0MPa air (dichloro-benzenes+acetic acid) 160 DEG C 48 hours (1.0/0.05/0.05/0.05/ 0.05) same embodiment 1, yield 26%], are operated.
(158) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (copper acetate+hexanitro cobalt acid sodium) 2,4- dichloropyridines dodecyl sodium sulfate peroxide Potassium acid sulfate complex salt, 2.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 48 hours (1.0/0.005/0.005/ 0.005/0.005)], same embodiment 1, yield 46% are operated.
(159) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (bromine cuprous+hexanitro cobalt acid sodium) 2,3- dichloropyridines dodecyl sodium sulfate peroxide Potassium acid sulfate complex salt, 4.0MPa oxygen (dichloro-benzenes+propionic acid) 160 DEG C 48 hours (1.0/0.005/0.005/0.005/ 0.005) same embodiment 1, yield 59%], are operated.
(160) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cuprous iodide+hexachloro-potassium ruthenate) 2,6- lutidines dodecyl sodium sulfate mistake Oxygen potassium acid sulfate complex salt, 5.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 48 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 64% are operated.
(161) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (palladium+hexachloro-potassium ruthenate) 2,4 '-bipyridyl dodecyl sodium sulfate peroxide sulphur Potassium hydrogen phthalate complex salt, 5.0MPa oxygen (dimethyl succinate+chlorobenzene+acetic acid) 160 DEG C 48 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 72% are operated.
(162) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=2), [1,3,5- tri- (4- (4- aminomethyl phenyls) phenyl) benzene (cuprous bromide+manganous fluoride) 2,2 '-bipyridyl dodecyl sodium sulfate peroxosulphuric Hydrogen potassium complex salt, 5.0MPa oxygen (dodecane+acetic acid) 160 DEG C 96 hours (1.0/0.005/0.005/0.005/ 0.005) same embodiment 1, yield 53%], are operated.
(163) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene cobalt nitrate 4- PMCs dodecyl sodium sulfate peroxosulphuric Hydrogen potassium complex salt, 5.0MPa oxygen (dimethyl succinate+dodecane+acetic acid) 160 DEG C 96 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 66% are operated.
(164) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium hydroxide+cobalt acetate) to dimethylamino naphthyridine dodecyl sulphur Sour sodium peroxosulphuric hydrogen potassium complex salt, 2.0MPa oxygen (chlorobenzene+acetic acid) 160 DEG C 96 hours (1.0/0.005/0.005/ 0.005/0.005)], same embodiment 1, yield 68% are operated.
(165) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (palladium bichloride+hafnium oxide) 4,4- bipyridyls dodecyl sodium sulfate Peroxosulphuric hydrogen potassium complex salt, 2.0MPa oxygen (dodecane+acetic acid) 160 DEG C 96 hours (1.0/0.005/0.005/ 0.005/0.005)], same embodiment 1, yield 64% are operated.
(166) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (palladium trifluoroacetate+lanthanum sulfate) 2- methoxypyridines dodecyl sulphur Sour sodium peroxosulphuric hydrogen potassium complex salt, 2.0MPa oxygen (dodecane+acetic acid) 160 DEG C 96 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 66% are operated.
(167) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) Ben (five ruthenium hydrochloride ammoniums+acetic acid tungsten) 2- Yi Yangjibiding dodecyl sulphurs Sour sodium peroxosulphuric hydrogen potassium complex salt, 2.0MPa oxygen (dichloro-benzenes+acetic acid) 160 DEG C 96 hours (1.0/0.005/ 0.005/0.005/0.005)], same embodiment 1, yield 64% are operated.
(168) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (hexachloro-potassium ruthenate+acetic acid praseodymium) 2- benzoylpyridines dodecyl sulphur The sour tetramethyl piperidine nitrogen oxides of Na 2,2,6,6-, the 2.0MPa Yang Qis (dodecanes+ little Shi (1.0/ of 140 DEG C of acetic acid) 96 0.005/0.005/0.005/0.005)], same embodiment 1, yield 63% are operated.
(169) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (ruthenium-oxide+praseodymium oxide) 2,6- lutidines tetrabutyl phosphonium bromide The tetramethyl piperidine nitrogen oxides of An 2,2,6,6-, the 2.0MPa Yang Qis (dichloro-benzenes+ little Shi (1.0/ of 140 DEG C of acetic acid) 96 0.005/0.005/0.005/0.005)], same embodiment 1, yield 27% are operated.
(170) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (molybdenum trisulfate+perchloric acid cerium) 2,3- pyridinedicarboxylic acids acid anhydride tetrabutyl bromine Change the tetramethyl piperidine nitrogen oxides of An 2,2,6,6-, the 2.0MPa Yang Qis (dichloro-benzenes+ little Shi (1.0/ of 140 DEG C of acetic acid) 96 0.02/0.005/0.005/0.005)], same embodiment 1, yield 56% are operated.
(171) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (molybdenum oxide cobalt+manganese acetate) 2,6- pyridinedicarboxylic acids dimethyl ester four fourths The tetramethyl piperidine nitrogen oxides of base Xiu Huaan 2,2,6,6-, the 2.0MPa Yang Qis (dichloro-benzenes+dodecane+DEG C 96 of acetic acid) 140 Hour (1.0/0.005/0.005/0.01/0.01)], operate same embodiment 1, yield 61%.
(172) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (cobaltous ammonium phosphate+manganous fluoride+molybdenum oxide) (4- nitropyridine+2,3- fourths The tetramethyl piperidine nitrogen oxides of diketone) Si Dingjixiuhuaans 2,2,6,6-, 2.0MPa Yang Qis (dichloro-benzenes+dodecane+second Acid) 140 DEG C 96 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 72%.
(173) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium nitrate+zirconium carbonate) (PA+2,6- dimethyl -3, - The tetramethyl piperidine nitrogen oxides of heptadione) Si Dingjixiuhuaans 2,2,6,6-, 2.0MPa Yang Qis (suberic acid dimethyl esters+second Acid) 140 DEG C 96 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 53%.
(174) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium nitrate+samarium sulphate) (4- pyridone+1,3- di-t-butyls third The tetramethyl piperidine nitrogen oxides of diketone) Si Dingjixiuhuaans 2,2,6,6-, the 2.0MPa Kong Qis (chlorobenzenes+DEG C 96 of acetic acid) 140 Hour (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 37%.
(175) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (cobalt aluminate+Potassium Zirconium Fluoride) (4- pyridones+acetylacetone,2,4-pentanedione) The tetramethyl piperidine nitrogen oxides of Si Dingjixiuhuaan 2,2,6,6-, the 2.0MPa Yang Qis (chlorobenzenes+ little Shi of 140 DEG C of acetic acid) 96 (1.00.1/0.1/0.1/0.1)], operate same embodiment 1, yield 53%.
(176) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (cobalt-chromate+Cericammoniumsulfate) (4- pyridones+5,6- last of the ten Heavenly stems diketone) The tetramethyl piperidine nitrogen oxides of Si Dingjixiuhuaan 2,2,6,6-, (dichloro-benzenes+DEG C 96 of acetic acid) 140 are small by 2.0MPa Yang Qis When (1.0/0.02/0.02/0.02/0.02)], operate same embodiment 1, yield 32%.
(177) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium nitrate+nickel chloride) (4- pyridone+1,3- diphenylprops two The tetramethyl piperidine nitrogen oxides of ketone) Si Dingjixiuhuaans 2,2,6,6-, (chlorobenzene+DEG C 96 of acetic acid) 140 are small by 2.0MPa Yang Qis When (1.00.3/0.3/0.3/0.3)], operate same embodiment 1, yield 58%.
(178) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium nitrate+nickel acetate) (4- pyridones+succinic acid) hypochlorous acid Calcium 4- carboxy-Ns-hydroxyphthalimide, 2.0MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 96 hours (1.00.2/ 0.2/0.2/0.2)], same embodiment 1, yield 47% are operated.
(179) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (hexachloro-potassium ruthenate+acetylacetone cobalt) (4- pyridones+succinic acid Di tert butyl carbonate) calcium hypochlorite 4- carboxy-Ns-hydroxyphthalimide, 2.0MPa oxygen (dichloro-benzenes+acetic acid) 140 DEG C 96 hours (1.00.1/0.1/0.1/0.1)], operate same embodiment 1, yield 56%.
(180) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium nitrate+manganese acetate) (4- pyridones+dodecanedioic acid diformazan Ester) calcium hypochlorite 4- carboxy-Ns-hydroxyphthalimide, 2.0MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 96 hours (1.00.1/0.1/0.1/0.1)], operate same embodiment 1, yield 51%.
(181) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium nitrate+manganese acetate) (4- pyridones+succinic acid diisopropyl Ester) calcium hypochlorite 4- carboxy-Ns-hydroxyphthalimide, 2.0MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 96 hours (1.00.1/0.1/0.1/0.1)], operate same embodiment 1, yield 48%.
(182) from more methyl polyphenyls prepare the multi-joint benzene polycarboxylic acid of Y types (formula (III) to (IV) b=4), [1,3,5- tri- (4- (4- (4- aminomethyl phenyls) phenyl) phenyl) benzene) benzene (rhodium nitrate+manganese acetate) (4- pyridones+Dimethyl 1,7-heptanedioate) Calcium hypochlorite 4- carboxy-Ns-hydroxyphthalimide, 2.0MPa oxygen (chlorobenzene+acetic acid) 140 DEG C 96 hours (1.00.1/0.1/0.1/0.1)], operate same embodiment 1, yield 46%.
Above example is easy to operate, and yield is higher.That is realized prepares polyphenyls by the multi-joint benzene-like compounds of more methyl More formic acid monomers, further self assembly functional material can be prepared into, applied to the storage of the clean energy resource gas such as hydrogen, methane, With preferable application prospect.
All it is incorporated as referring in this application in all documents that the present invention refers to, it is independent just as each document It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited Enclose.

Claims (10)

  1. A kind of 1. method for preparing the more acid monomers of polyphenyls, it is characterised in that
    Methods described is method (A), including step：In atent solvent, under metal salt catalyst, in use or without using part In the case of, using or as co-catalyst and used or without using additive B as co-catalyst without using additive A In the case of, the compound shown in formula (I) is reacted with oxidant, so as to obtain the more first of Y type polyphenyls shown in formula (II) Acid monomers；
    Methods described is method (B), including step：In atent solvent, under metal salt catalyst, in use or without using part In the case of, using or as co-catalyst and used or without using additive B as co-catalyst without using additive A In the case of, the compound shown in formula (III) is reacted with oxidant, the Y type polyphenyls obtained from shown in formula (IV) More formic acid monomers；
    Methods described is method (C), including step：In atent solvent, under metal salt catalyst, in use or without using part In the case of, using or as co-catalyst and used or without using additive B as co-catalyst without using additive A In the case of, the compound shown in formula (V) is reacted with oxidant, the X-type polyphenyls obtained from shown in formula (VI) is more Formic acid monomer；
    It is above-mentioned it is various in, a represent 1 or 2, b represent 1 or 2 or 34, c represent 1 or 2, R represent hydrogen or bromine；
    Wherein,
    The metal salt is selected from the group：Cobalt salt, manganese salt, ruthenium salt, palladium salt, rhodium salt, mantoquita, nickel salt, molysite, molybdenum salt, chromic salts, tungsten Salt, zirconates, hafnium salt, lanthanide metal salt or its combination；The anion of the metal salt can be oxygen, hydroxyl, halogen, nitric acid Root, sulfate radical, nitrite anions, acetylacetone,2,4-pentanedione acid group, oxalate, phosphate radical, hydrogen phosphate, dihydrogen phosphate, vanadic acid root, aluminic acid Root, carbonate, C1~C8 fatty acid radicals, sulfonate radical anionoid；
    When using part, the part is selected from the group：Formula (VII) compound, formula (VIII) compound, substituted pyridines, quinoline, Isoquinolin, bipyridyl, 2,6- bis- (2- pyridine radicals) pyridine, Phen, tetramethylethylenediamine or its combination：
    In formula (VII), R1For hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, 2- carboxy ethyls, 2- carboxymethyl groups or phenyl, R2For C1-C6 alkyl, adamantyl, C3-C6 cycloalkyl, C1-C6 alkoxies, benzyloxy or phenyl；
    In formula (VIII), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 alkyl ammonia Base, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 alkyl aminos, n is 0~ 10；
    The substituent of substituted pyridines can be hydrogen, C1-C6 alkyl, benzyl, phenyl, C1-C6 alkoxies, fluorine, chlorine, bromine, iodine, hydroxyl Base, amino, amino methyl, carboxyl, methoxycarbonyl group, carbethoxyl group, acetyl group, benzoyl, itrile group, nitro or dimethylamino；
    When using additive A, the additive A is selected from the group one or more：Metal salt I, scandium oxide, scandium nitrate, sulfuric acid Scandium, C2-C12 sodium soaps, C2-C12 aliphatic acid potassium, dodecyl sodium sulfate, neopelex, tetrabutyl phosphonium bromide Ammonium, tetrabutylammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl ammonia chloride or its combination；The metal salt I sun from Son is lithium, sodium, potassium, calcium, ammonium；The anion of the metal salt I is sulfate radical, inferior sulfate radical, nitrate anion, nitrite anions, phosphoric acid Root, hydrogen phosphate, dihydrogen phosphate, orthophosphite, perchlorate, hypochlorite；
    When using additive B, the additive B is selected from the group one or more：2-aza-adamantane-N- oxygen radicals, 9- Azabicyclo [3.3.1] nonane N- oxygen radicals, 2,2,6,6- tetramethyl piperidines nitrogen oxides, 2,2,6,6- tetramethyl -4- hydroxyls Piperidine nitroxide, 2,2,6,6- tetramethyl -4- methoxy piperides nitrogen oxides, 2,2,6,6- tetramethyl piperidine -4- ketone -1- Oxygen radical, 2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides, sodium peroxide, sodium peroxydisulfate, potassium peroxydisulfate, mistake Sodium carbonate, potassium percarbonate, peroxosulphuric hydrogen potassium complex salt, sodium perborate, N- hydroxyls dicarboximide or its combination；
    The atent solvent is selected from the group：Two esters solvents, alkane solvents, cycloalkane solvent, chlorobenzene, dichloro-benzenes, C2-C6 Aliphatic acid, R1CO2R2Esters solvent or its combination, wherein R1For C1~C5 alkyl, R2For C1~C6 alkyl；Two esters solvents are Two esters solvents that C1-C12 fat diacid is formed with methanol, ethanol, propyl alcohol, isopropanol；
    The oxidant is selected from the group：0.1~10.0MPa oxygen, 0.1~10.0MPa air, the dilution of 0.1~10.0MPa nitrogen Oxygen or air afterwards, or aqueous hydrogen peroxide solution；
    Reaction temperature is 20 DEG C~300 DEG C；
    Reaction time is 0.5~300 hour.
  2. 2. the method as described in claim 1, it is characterised in that methods described (A) includes step：In atent solvent, in gold Belong under salt catalysis, using or without using part in the case of, using or as co-catalyst and used without using additive A Or without using additive B as co-catalyst in the case of, the compound shown in formula (I) is reacted with oxidant, so as to Obtain the multi-joint benzene polycarboxylic acid monomer of Y types shown in formula (II)；
    It is above-mentioned it is various in, a represent 1 or 2.
  3. 3. the method as described in claim 1, it is characterised in that methods described (B) includes step：In atent solvent, in gold Belong under salt catalysis, using or without using part in the case of, using or as co-catalyst and used without using additive A Or without using additive B as co-catalyst in the case of, the compound shown in formula (III) is reacted with oxidant, from Obtained from the multi-joint benzene polycarboxylic acid monomer of Y types shown in formula (IV)；
    It is above-mentioned it is various in, b represent 1 or 2 or 3 or 4.
  4. 4. the method as described in claim 1, it is characterised in that methods described (C) includes step：In atent solvent, in gold Belong under salt catalysis, using or without using part in the case of, using or as co-catalyst and used without using additive A Or without using additive B as co-catalyst in the case of, the compound shown in formula (V) is reacted with oxidant, so as to The multi-joint benzene polycarboxylic acid monomer of X-type shown in obtained formula (VI)；
    It is above-mentioned it is various in, c represent 1 or 2, R represent hydrogen or bromine.
  5. 5. the method as described in claim any one of 1-4, it is characterised in that
    The part is selected from the group：Formula (VII) compound, formula (VIII) compound, substituted pyridines, quinoline, isoquinolin, connection pyrrole Pyridine, 2,6- bis- (2- pyridine radicals) pyridine, Phen, tetramethylethylenediamine or its combination：
    In formula (VII), R1For hydrogen, methyl, isopropyl, isobutyl group, sec-butyl, the tert-butyl group, cyclohexyl, benzyl, 2- carboxy ethyls, 2- carboxymethyl groups or phenyl, R2For methyl, ethyl, propyl group, isopropyl, the tert-butyl group, adamantyl, cyclohexyl, methoxyl group, benzyl Epoxide or phenyl；
    In formula (VIII), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 alkyl ammonia Base, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, two C1-C3 alkyl aminos, n is 0~ 10；
    The substituent of substituted pyridines can be hydrogen, C1-C6 alkyl, benzyl, phenyl, C1-C6 alkoxies, fluorine, chlorine, bromine, iodine, hydroxyl Base, amino, amino methyl, carboxyl, methoxycarbonyl group, carbethoxyl group, acetyl group, benzoyl, itrile group, nitro or dimethylamino.
  6. 6. the method as described in claim any one of 1-4, it is characterised in that
    The metal salt is selected from the group：Copper acetate, copper chloride, stannous chloride, copper bromide, nickel chloride, nickel acetate, ferric acetate, chlorine Change iron, ferric acetyl acetonade, ferric sulfate, cobalt acetate, cobalt chloride, cobaltous fluoride, cobaltous bromide, lithium cobalt oxide, cobalt hydroxide, cobalt carbonate, Cobalt oxalate, cobaltous sulfate, cobalt-chromate, cobalt aluminate, cobalt nitrate, cobaltous ammonium phosphate, molybdenum oxide cobalt, sulfamic acid cobalt, acetylacetone cobalt, six Nitro cobalt acid sodium, nitrification cobalt hexamine complex compound, manganese acetate, manganese chloride, manganous fluoride, manganese carbonate, manganese phosphate, manganese oxalate, sulfuric acid Manganese, manganese oxide, cerous acetate, cerium chloride, cerium fluoride, cerium hydroxide, cerous nitrate, ammonium ceric nitrate, cerium oxide, cerous phosphate, cerium vanadate, Zirconium oxide cerium, cerous sulfate, Cericammoniumsulfate, acetylacetone,2,4-pentanedione cerium, cerous carbonate, cerium oxalate, perchloric acid cerium, isooctyl acid cerium, fluoroform sulphur Sour cerium, ruthenic chloride, five ruthenium hydrochloride ammoniums, the sour potassium of chlordene ruthenium (III), ruthenium-oxide, palladium bichloride, acetonitrile palladium chloride, acid chloride, trifluoro second Sour palladium, radium chloride, rhodium acetate, chlorine rhodium acid potassium, rhodium nitrate, rhodium hydroxide, zirconium oxide, lanthana, samarium oxide, lanthanum nitrate, nitric acid Scandium, zirconium nitrate, samaric nitrate, lanthanum sulfate, zirconium sulfate, samarium sulphate, zirconyl acetate, zirconium acetate, molybdenum oxide, acetic acid molybdenum, molybdenum trisulfate, second Sour tungsten, tungsten oxide, acetic acid hafnium, hafnium oxide, acetic acid praseodymium, praseodymium oxide, Potassium Zirconium Fluoride, zirconyl nitrate, zirconium oxycarbonate, carbonic acid Zirconium or its combination；
    It is preferred that when using additive part, the metal salt is selected from the group：Copper acetate, copper chloride, stannous chloride, bromination Copper, ferric acetate, iron chloride, ferric acetyl acetonade, ferric sulfate, cobalt acetate, cobalt chloride, cobaltous fluoride, cobaltous bromide, lithium cobalt oxide, hydrogen-oxygen Change cobalt, cobalt carbonate, cobalt oxalate, cobaltous sulfate, cobalt-chromate, cobalt aluminate, cobalt nitrate, cobaltous ammonium phosphate, molybdenum oxide cobalt, sulfamic acid cobalt, Acetylacetone cobalt, hexanitro cobalt acid sodium, nitrification cobalt hexamine complex compound, manganese acetate, manganese chloride, manganous fluoride, manganese carbonate, phosphoric acid Manganese, manganese oxalate, manganese sulfate, manganese oxide, cerous acetate, cerium chloride, cerium fluoride, cerium hydroxide, cerous nitrate, ammonium ceric nitrate, cerium oxide, It is cerous phosphate, cerium vanadate, zirconium oxide cerium, cerous sulfate, Cericammoniumsulfate, acetylacetone,2,4-pentanedione cerium, cerous carbonate, cerium oxalate, perchloric acid cerium, different pungent Sour cerium, trifluoromethanesulfonic acid cerium, ruthenic chloride, five ruthenium hydrochloride ammoniums, the sour potassium of chlordene ruthenium (III), ruthenium-oxide, zirconium oxide, lanthana, oxidation Samarium, lanthanum nitrate, scandium nitrate, zirconium nitrate, samaric nitrate, lanthanum sulfate, zirconium sulfate, samarium sulphate, zirconyl acetate, zirconium acetate, molybdenum oxide, second Sour molybdenum, molybdenum trisulfate, acetic acid tungsten, tungsten oxide, acetic acid hafnium, hafnium oxide, acetic acid praseodymium, praseodymium oxide, Potassium Zirconium Fluoride, zirconyl nitrate, alkali Formula zirconium carbonate, zirconium carbonate or its combination.
  7. 7. the method as described in claim any one of 1-4, it is characterised in that
    When using additive A, the additive A is selected from the group one or more：Metal salt I, scandium oxide, scandium nitrate, sulfuric acid Scandium, C2-C12 sodium soaps, C2-C12 aliphatic acid potassium, dodecyl sodium sulfate, neopelex, tetrabutyl phosphonium bromide Ammonium, tetrabutylammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl ammonia chloride or its combination；The metal salt I sun from Son is lithium, sodium, potassium, calcium, ammonium；The anion of the metal salt I is sulfate radical, inferior sulfate radical, nitrate anion, nitrite anions, phosphoric acid Root, hydrogen phosphate, dihydrogen phosphate, orthophosphite, perchlorate, hypochlorite；And/or
    When using additive B, the additive B is selected from the group one or more：2-aza-adamantane-N- oxygen radicals, 9- Azabicyclo [3.3.1] nonane N- oxygen radicals, 2,2,6,6- tetramethyl piperidines nitrogen oxides, 2,2,6,6- tetramethyl -4- hydroxyls Piperidine nitroxide, 2,2,6,6- tetramethyl -4- methoxy piperides nitrogen oxides, 2,2,6,6- tetramethyl piperidine -4- ketone -1- Oxygen radical, 2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides, sodium peroxide, sodium peroxydisulfate, potassium peroxydisulfate, mistake Sodium carbonate, potassium percarbonate, peroxosulphuric hydrogen potassium complex salt, sodium perborate, N- hydroxyls dicarboximide or its combination；Wherein, institute Stating N- hydroxyls dicarboximide can be：HP, perchloro--HP, 4- The fluoro- HP of carboxy-N-hydroxyphthalimide, 4-, 4- methyl-N-hydroxies phthalyl are sub- The fluoro- HP of amine, 2-, 4- methoxycarbonyl groups-HP, 4- carbethoxyl group-N- hydroxyls Base phthalimide, 4- propylene carbonyl oxygens-HP, 4- butyloxycarbonyl-N- hydroxyl O-phthalics Acid imide, 4- butoxy carbonyls-HP, 4- tertbutyloxycarbonyls-HP, N, The equal pyromellitic dimide of N '-dihydroxy or n-hydroxysuccinimide, 1,2- hexamethylenes dicarboximide, N- hydroxyls -2,3- Naphthalimide, N- hydroxyl -1,8- naphthalimides.
  8. 8. the method as described in claim any one of 1-4, it is characterised in that the atent solvent is selected from the group：Succinic acid two Methyl esters, diethyl succinate, dipropyl succinate, diisopropyl ester amber acid, dimethyl glutarate, ethyl glutarate, penta 2 Sour dipropyl, glutaric acid diisopropyl ester, dimethyl adipate, diethylene adipate, dipropyl adipate, adipic acid diisopropyl Ester, n-hexane, normal heptane, dodecane, hexamethylene, chlorobenzene, dichloro-benzenes, acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid or its group Close.
  9. 9. the method as described in claim any one of 1-4, it is characterised in that
    When being calculated with mol ratio, (I)/metal salt/part/additive A/additive B be 1.0/0.001~0.3/0~0.3/0~ 0.3/0~0.3；Or (III)/metal salt/part/additive A/additive B is 1.0/0.001~0.3/0~0.3/0~0.3/ 0~0.3；Or (V)/metal salt/part/additive A/additive B be 1.0/0.001~0.3/0~0.3/0~0.3/0~ 0.3；
    It is preferred that when being calculated with mol ratio, (I)/metal salt/part/additive A/additive B is 1.0/0.005~0.1/ 0.005~0.01/0.005~0.01/0.005~0.01；Or (III)/metal salt/part/additive A/additive B is 1.0/ 0.005~0.1/0.005~0.01/0.005~0.01/0.005~0.01；Or (V)/metal salt/part/additive A/addition Agent B is 1.0/0.005~0.1/0.005~0.01/0.005~0.01/0.005~0.01.
  10. 10. the method as described in claim any one of 1-4, it is characterised in that
    The oxidant is selected from the group：0.1~10.0MPa oxygen, 0.1~10.0MPa air, 0.1~10.0MPa are dilute by nitrogen Oxygen or air or aqueous hydrogen peroxide solution after releasing；It is preferred that for 0.1~2.5MPa oxygen, 0.2~0.6MPa air or 0.1~2.5MPa diluted by nitrogen after oxygen or air；More preferably, it is empty for 0.1~0.5MPa oxygen or 0.2~0.5MPa Gas；And/or
    Reaction temperature is 20 DEG C~300 DEG C；It is preferred that for 100~240 DEG C；More preferably, it is 140~180 DEG C；And/or
    Reaction time is 0.5~300 hour；It is preferred that for 5~72 hours；More preferably, it is 8~24 hours.
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