CN107698438A - A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons - Google Patents
A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons Download PDFInfo
- Publication number
- CN107698438A CN107698438A CN201610656820.5A CN201610656820A CN107698438A CN 107698438 A CN107698438 A CN 107698438A CN 201610656820 A CN201610656820 A CN 201610656820A CN 107698438 A CN107698438 A CN 107698438A
- Authority
- CN
- China
- Prior art keywords
- acid
- cobalt
- oxygen
- formula
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons.Specifically, the invention discloses a kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons, including step:In atent solvent, under the catalysis of metal salt and part, use or without using additive A as co-catalyst and use or without using additive B as co-catalyst in the case of, how methyl substituted aromatic hydrocarbons analog derivative shown in formula (I) is reacted with oxidant, so as to obtain the more formic acid analog derivatives of aromatic hydrocarbons shown in formula (II);Or 3,3 ', 4,4 ' tetramethyl biphenyl derivatives shown in formula (III) react with oxidant, 3,3 ', 4,4 ' the tetracarboxylic biphenyl derivatives obtained from shown in formula (IV).The invention provides one kind in low pressure, low temperature, energy consumption is low, pollution is small, technique is simple, equipment requirement is low, the inexpensive method for preparing the more formic acid analog derivatives of aromatic hydrocarbons.
Description
The application be the applying date on 08 09th, 2016, it is Application No. 201610648027.0, entitled " a kind of
The divisional application of the application for a patent for invention of the method for preparing the more formic acid analog derivatives of aromatic hydrocarbons ".
Technical field
The present invention relates to chemical field, specifically, being related to a kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons, more specifically
, it is related to a kind of method that metal catalytic oxidation prepares the more formic acid analog derivatives of aromatic hydrocarbons in two esters solvent.
Background technology
The more formic acid analog derivatives of aromatic hydrocarbons are important chemical industry and medical material, particularly aromatic hydrocarbons dioctyl phthalate such as terephthaldehyde
Acid, M-phthalic acid, phthalic acid, for example inclined phthalic acid of aromatic hydrocarbons tricarboxylic acid, trimesic acid, Pyromellitic Acid, 3,3 ', 4,
The polyacid compounds such as 4 '-tetracarboxylic biphenyl derivatives, in high polymer material, additive, film, laminate, coating, gluing
Agent, insulating materials etc., the method for the exploitation synthesis more formic acid analog derivatives of aromatic hydrocarbons have great importance.
The use of air or oxygen is at present the oxidant method for preparing the more formic acid analog derivatives of aromatic hydrocarbons, using trimellitic acid as
Example, nitric acid oxidation is because cost is high, serious three wastes, operational hazards and stop production.U.S.'s Middle Ages (Mid-Century) company exploitation into
Work(, abbreviation MC methods (US2245528), realizes industrialized production, the method with containing cobalt, manganese Metal component and bromide (such as
HBr, tetrabromoethane) solable matter make catalyst, using acetic acid as solvent, under HTHP power, pseudocumene is aoxidized
Trimellitic acid is generated, there are numerous patents to modify the system afterwards, but most of still using acetic acid as solvent, bromide
For initiator, reacted under very high temperature (being progressively warming up to more than 200 DEG C) and high pressure (2.0MPa oxygen).These systems are consolidated
So there is its advantage, but solvent effect on environment is bad, and bromide triggers it is also obvious that needing to use substantial amounts of acetic acid to act on for shortcoming
Hydrobromic acid caused by agent and substantial amounts of acetic acid easily cause corrosion to reaction vessel, it is necessary to be closed using expensive nickel system or titanium, zirconium system
Gold makes container, and pressure and temperature is too high, and the security requirement to equipment is high.Trimesic acid, Pyromellitic Acid, 3,3 ',
There is also Similar Problems in the preparation of 4,4 '-tetracarboxylic biphenyl derivatives etc..
Therefore, there is an urgent need to a kind of condition is relatively mild, equipment is cheap for this area, prepares easy, the low system of financial cost
The method of the more formic acid analog derivatives of standby aromatic hydrocarbons.
The content of the invention
It is an object of the present invention to provide one kind need not add bromide, condition are relatively mild, equipment is cheap, it is easy to prepare, easily
In expansion scale, the method for preparing the more formic acid analog derivatives of aromatic hydrocarbons that financial cost is low, selectivity is good.
More problems present in original production technology, mainly there is addition bromide and set using the corrosion of substantial amounts of acetic acid
For, it is necessary to make container using expensive nickel system or titanium, zirconium alloy, pressure and temperature is too high, the security requirement to equipment
It is high.The present inventor has found why need to use HTHP to solve the above problems by many experiments, be because
Acetic acid is poor to the dissolubility of intermediate product methyl phthalic acid so that reaction carries out very slow, it is necessary to increases centre using high pressure
Between dissolubility of the thing in acetic acid.It is in original production technology another problem is that product can with metallic catalyst formed dissolubility compared with
The complex of difference, so that catalyst changes work.In order to reduce the requirement to equipment and reduce energy consumption, inventor, which contemplates, uses normal pressure
The higher solvent of lower boiling point.Although dimethyl sulfoxide, dimethylformamide equal solvent boiling point are very high, otherwise coordinating force very much is urged
Agent inactivates, otherwise alkaline matter is easily decomposited under high temperature, it is unfavorable to reacting, found by substantial amounts of, inventor has found diester
Class solvent such as diethyl succinate etc., there is higher boiling point, while also relatively stable, alkaline matter, low toxicity, low will not be produced
It is taste, safe to use, do not belong to hazardous substances.Two esters solvents such as diethyl succinate etc. still yet another advantage is that it is coordinating compared with
It is weak, but have certain coordinating, the metal-complexing in inactivation complex that product is formed with metallic catalyst can be lived again
Change, so as to improve the service efficiency of metallic catalyst.The complex of inactivation, invention are formed to reduce product with metallic catalyst
People adds the weak ligand of catalytic amount into reaction system, forms a coordination balance.And in order to further improve middle production
Dissolubility of the thing in two ester solvents, some metal ions particularly surfactant etc. can be added and form ion pair, increase
Dissolubility.Some radical initiators can then improve reaction efficiency, avoid using corrosive substances such as bromides.Add in reaction
Enter a small amount of mixed solvent such as acetic acid, the higher azeotropic mixture of boiling point can be formed, reduce the concentration of acetic acid, so as to also reduce
Requirement to equipment.And two esters solvents can filter or distill after the completion of reaction, directly recycle, reduce cost.
, it was also found that two esters solvents cause reactivity to improve in actual experiment, so as to reduce reaction temperature.
The method provided by the present invention for preparing the more formic acid analog derivatives of aromatic hydrocarbons, including step:
Methods described is method (a), including step:
In atent solvent, under the catalysis of metal salt and part, using or without using additive A as co-catalyst
And use or without using additive B as co-catalyst in the case of, by shown in formula (I) how methyl substituted aromatic hydrocarbons derive
Thing reacts with oxidant, so as to obtain the more formic acid analog derivatives of aromatic hydrocarbons shown in formula (II);
It is above-mentioned it is various in,
Ar1Be substitution phenyl ring or naphthalene nucleus, substituent can be hydrogen, C1-C6 alkoxy, halogen, nitro, methylol,
Aldehyde radical or carboxyl;
Ar2It is the phenyl ring or naphthalene nucleus of substitution, substituent can be hydrogen, C1-C6 alkoxy, halogen, nitro or carboxyl;
N=2~6;
Or
Methods described is method (b), including step:
In atent solvent, under the catalysis of metal salt and part, using or without using additive A as co-catalyst
And use or without using additive B as co-catalyst in the case of, by 3 shown in formula (III), 3 ', 4,4 '-tetramethyl hexichol
Radical derivative reacts with oxidant, obtained from shown in formula (IV) 3,3 ', 4,4 '-tetracarboxylic biphenyl derivatives;
It is above-mentioned it is various in,
X is carbonyl, substituted methylene, and the substituent of substituted methylene can be hydroxyl, hydrogen or C1-C6 alkyl, now
Corresponding Y is carbonyl;
X=O, SO2,C(CF3)2, or CMe2When, Y=X;
P or q=1 or 2;
The metal salt is selected from the group:Mantoquita, molysite, cobalt salt, manganese salt, cerium salt, ruthenium salt, nickel salt, palladium salt, rhodium salt or its
Combination;It is preferred that the metal salt can be selected from the group:Copper acetate, copper chloride, stannous chloride, copper bromide, ferric acetate, chlorination
Iron, ferric acetyl acetonade, ferric sulfate, cobalt acetate, cobalt chloride, cobaltous fluoride, cobaltous bromide, lithium cobalt oxide, cobalt hydroxide, cobalt carbonate, grass
Sour cobalt, cobaltous sulfate, cobalt-chromate, cobalt aluminate, cobalt nitrate, cobaltous ammonium phosphate, molybdenum oxide cobalt, sulfamic acid cobalt, acetylacetone cobalt, six nitre
Base cobalt acid sodium, nitrification cobalt hexamine complex compound, manganese acetate, manganese chloride, manganous fluoride, manganese carbonate, 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, oxygen
Change zirconium 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, nickel chloride, nickel fluoride, nickel acetate, nickel sulfate, nitric acid
Nickel, nickel protoxide, hexafluorosilicic acid nickel, ammonium nickel sulfate, nickle cobalt lithium manganate, palladium, palladium trifluoroacetate, acetonitrile palladium chloride, acetic acid
Rhodium, radium chloride, rhodium hydroxide, rhodium oxide, rhodium sulfate, rhodium nitrate, chlorine rhodium acid potassium or its combination;
The part is selected from the group:Structure formula (V), (VI), substituted pyridines, quinoline, isoquinolin, bipyridyl, Phen,
Or its combination:
In formula (V), R1For hydrogen, methyl, isopropyl, isobutyl group, sec-butyl, tertiary fourth, cyclohexyl, benzyl, 2- carboxy ethyls,
2- carboxymethyl groups or phenyl, R2For methyl, ethyl, isopropyl, the tert-butyl group, methoxyl group, benzyloxy or phenyl;
In formula (VI), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dioxanes
Base amino, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dialkyl amidos, k 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, zirconium oxide,
Lanthana, samarium oxide, lanthanum nitrate, scandium nitrate, zirconium nitrate, samaric nitrate, lanthanum sulfate, scandium sulfate, zirconium sulfate, samarium sulphate, acetic acid oxygen
Zirconium, zirconium acetate, molybdenum oxide, acetic acid molybdenum, molybdenum trisulfate, acetic acid tungsten, tungsten oxide, acetic acid hafnium, hafnium oxide, acetic acid praseodymium, praseodymium oxide, hexafluoro
Potassium zirconium, zirconyl nitrate, zirconium oxycarbonate, zirconium carbonate, C2-C12 alkyl acid sodium, C2-C12 alkyl acid potassium, dodecyl
Sodium sulfonate, neopelex, TBAB, tetrabutylammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl
Ammonium chloride or its combination;Wherein, the cation of the metal salt I is lithium, sodium, potassium, calcium or ammonium, the anion of the metal salt I
For sulfate radical, inferior sulfate radical, nitrate anion, nitrite anions, phosphate radical, hydrogen phosphate, dihydrogen phosphate, orthophosphite, perchloric acid
Root or 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;Its
In, the N- hydroxyls dicarboximide can be:HP, perchloro--N- hydroxyls phthalyl are sub-
Amine, 4- carboxy-Ns-hydroxyphthalimide, the fluoro- HPs of 4-, 4- methyl-N-hydroxy neighbours benzene two
The fluoro- HP of carboximide, 2-, 4- methoxycarbonyl groups-HP, N, N '-dihydroxy
The equal pyromellitic dimide of base or n-hydroxysuccinimide, 1,2- hexamethylene dicarboximides.
The atent solvent is selected from the group:Two esters solvents or its combination, or more two esters solvents and chlorobenzene, dichloro
Benzene, water, C2~C6 aliphatic acid, R5CO2R6The mixing of esters solvent, dimethyl carbonate, diethyl carbonate, diisopropyl carbonate
Solvent, wherein R5For C1~C5 alkyl, R6For C1~C6 alkyl;Wherein, two esters solvent is C1~C12 fat
Two esters solvents that diacid is formed with methanol, ethanol, propyl alcohol, isopropanol;
The oxidant is selected from the group:30~70% concentration hydrogen peroxide, 0.1~10MPa oxygen, air or nitrogen dilution
Oxygen or air afterwards;
Reaction temperature is 40 DEG C~250 DEG C;
Reaction time is 1~120 hour.
In another preference, methods described (a) includes step:
In atent solvent, under the catalysis of metal salt and part, using or without using additive A as co-catalyst
And use or without using additive B as co-catalyst in the case of, by shown in formula (I) how methyl substituted aromatic hydrocarbons derive
Thing reacts with oxidant, so as to obtain the more formic acid analog derivatives of aromatic hydrocarbons shown in formula (II),
It is above-mentioned it is various in, wherein, Ar1It is phenyl ring;Ar2It is phenyl ring;N=3.
In another preference, methods described (a) includes step:
In atent solvent, under the catalysis of metal salt and part, using or without using additive A as co-catalyst
And use or without using additive B as co-catalyst in the case of, by shown in formula (I) how methyl substituted aromatic hydrocarbons derive
Thing reacts with oxidant, so as to obtain the more formic acid analog derivatives of aromatic hydrocarbons shown in formula (II);
It is above-mentioned it is various in, wherein, Ar1It is phenyl ring;Ar2It is phenyl ring;N=4.
In another preference, methods described (b) includes step:
In atent solvent, under the catalysis of metal salt and part, using or without using additive A as co-catalyst
And use or without using additive B as co-catalyst in the case of, by 3 shown in formula (III), 3 ', 4,4 '-tetramethyl hexichol
Radical derivative reacts with oxidant, obtained from shown in formula (IV) 3,3 ', 4,4 '-tetracarboxylic biphenyl derivatives;
It is above-mentioned it is various in,
X is carbonyl, substituted methylene, and the substituent of substituted methylene can be hydroxyl, hydrogen or C1-C6 alkyl, now
Corresponding Y is carbonyl;
X=O, SO2,C(CF3)2, or CMe2When, Y=X;
P or q=1 or 2.
In another preference, the part is selected from the group:Structure formula (V), (VI), substituted pyridines, quinoline, isoquinolin,
Bipyridyl, Phen or its combination:
In formula (V), R1For hydrogen, methyl, isopropyl, isobutyl group, sec-butyl, tertiary fourth, cyclohexyl, benzyl, 2- carboxy ethyls,
2- carboxymethyl groups or phenyl, R2For methyl, ethyl, isopropyl, the tert-butyl group, methoxyl group, benzyloxy or phenyl;
In formula (VI), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dioxanes
Base amino, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dialkyl amidos, k 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:Mantoquita, molysite, cobalt salt, manganese salt, cerium salt, ruthenium salt, nickel salt,
Palladium salt, rhodium salt or its combination;It is preferred that the metal salt is selected from the group:Copper acetate, copper chloride, copper bromide, copper sulphate, chlorination
Cuprous, cuprous bromide, cuprous iodide, 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, manganese phosphate, manganese oxalate, manganese sulfate, manganese oxide, cerous acetate, cerium chloride, cerium fluoride, cerium hydroxide, nitric acid
Cerium, 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), oxidation
Ruthenium, nickel chloride, nickel fluoride, nickel acetate, nickel sulfate, nickel nitrate, nickel protoxide, hexafluorosilicic acid nickel, ammonium nickel sulfate, nickel cobalt mangaic acid
Lithium, palladium, palladium trifluoroacetate, acetonitrile palladium chloride, rhodium acetate, radium chloride, rhodium hydroxide, rhodium oxide, rhodium sulfate, rhodium nitrate,
Chlorine rhodium acid potassium or its combination;Again goodly, the metal salt is selected from the group:Mantoquita, molysite, cobalt salt, cerium salt or its combination;More preferably
Ground, the metal salt can be selected from the group:Copper acetate, ferric acetate, ferric acetyl acetonade, ferric sulfate, cobalt acetate, lithium cobalt oxide, hydrogen
Cobalt oxide, 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, 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, carbonic acid
Cerium, cerium oxalate, perchloric acid cerium, isooctyl acid cerium, trifluoromethanesulfonic acid cerium or its combination.
In another preference, when using additive A, the additive A is selected from the group one or more:C2-C12's
Alkyl acid potassium, dodecyl sodium sulfate, neopelex, TBAB, the tetrabutyl of alkyl acid sodium, C2-C12
Ammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl ammonia chloride or its combination.
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, 2,2,6,6- tetramethyl piperidines nitrogen oxides, 2,2,6,6- tetramethyl -4- methoxy piperide nitrogen oxidations
Thing, 2,2,6,6- tetramethyl piperidine -4- ketone -1- oxygen radicals, 2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides,
Sodium peroxydisulfate, potassium peroxydisulfate, SODIUM PERCARBONATE, peroxosulphuric hydrogen potassium complex salt, sodium perborate, N- hydroxyls dicarboximide or its group
Close;Wherein, the N- hydroxyls dicarboximide can be:HP, perchloro--N- hydroxyl O-phthalics
Acid imide, 4- carboxy-Ns-hydroxyphthalimide, the fluoro- HPs of 4-, 4- methyl-N-hydroxies are adjacent
The fluoro- HP of BIDA, 2-, 4- methoxycarbonyl groups-HP, N, N '-
The equal pyromellitic dimide of dihydroxy or n-hydroxysuccinimide, 1,2- hexamethylene dicarboximides.
In another preference, the atent solvent is selected from the group:Two esters solvents being selected from the group:Succinic acid diformazan
Ester, diethyl succinate, dimethyl glutarate, ethyl glutarate, dimethyl adipate, diethylene adipate or its combination,
Or more two esters solvents and chlorobenzene, acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid, R5CO2R6Esters solvent, dimethyl carbonate,
The mixed solvent of diethyl carbonate, diisopropyl carbonate, wherein R5For C1~C5 alkyl, R6For C1~C6 alkyl.
In another preference, the oxidant is selected from the group:After 0.1~10MPa oxygen, air or nitrogen dilution
Oxygen or air.
In another preference, reaction temperature is 40 DEG C~250 DEG C.
In another preference, the reaction time is 1~120 hour.
In another preference, when being calculated with mol ratio, (I)/metal salt/part/additive A/additive B is 1.0/
0.001~0.2/0~0.3/0~0.3/0~0.3;(III)/metal salt/part/additive A/additive B is 1.0/0.001
~0.2/0~0.3/0~0.3/0~0.3;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;(III)/metal salt/part/adds
It is 1.0/0.005~0.1/0.005~0.01/0.005~0.01/0.005~0.01 to add agent A/ additive Bs.
In another preference, the oxidant is selected from the group:After 0.1~10MPa oxygen, air or nitrogen dilution
Oxygen or air;It is preferred that the oxidant is the oxygen or air after 0.1~2.5MPa oxygen, air or nitrogen dilution;
More preferably, the oxidant is 0.1~0.5MPa oxygen or air.
In another preference, reaction temperature is 40 DEG C~250 DEG C;It is preferred that reaction temperature is 80~200 DEG C;More preferably
Ground, reaction temperature are 100~160 DEG C.
In another preference, the reaction time is 1~120 hour;It is preferred that the reaction time is 5~72 hours;More preferably
Ground, reaction time are 4~12 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 vinegar
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 by long-term and in-depth study, find two esters solvents can realize low energy consumption, low-corrosiveness,
The more formic acid analog derivatives of aromatic hydrocarbons are prepared in high yield, and the more formic acid analog derivatives of gained aromatic hydrocarbons can be applied to high polymer material, addition
Agent, film, laminate, coating, adhesive, insulating materials etc., there is preferable application prospect.On this basis, inventor is complete
Into 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 first
Base, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group or similar group.
As used herein, term " C2-C12 alkyl acid " refers to the straight or branched alkyl with 2-12 carbon atom, example
Such as acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, caproic acid, dodecylic acid or similar aliphatic acid.
As used herein, term " C1-C6 alkoxy " refers to the straight or branched alkoxyl with 1-6 carbon atom, example
Such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy or similar group.
As used herein, term " C2~C6 aliphatic acid " refers to the straight or branched aliphatic acid with 2-6 carbon atom, example
Such as acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, caproic acid or similar aliphatic acid.
As used herein, term " C1~C12 fat diacid " refers to the straight chain fatty diacid with 1-12 carbon atom, example
Such as carbonic acid, ethanedioic acid (oxalic acid), malonic acid, succinic acid, glutaric acid, adipic acid, dodecanedioic acid or similar aliphatic acid.
As used herein, 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
Selecting property is high, financial cost is low prepares the more formic acid derivates of aromatic hydrocarbons, particularly benzenetricarboxylic acid analog derivative and benzene tetracarboxylic acid class is spread out
The method of biology;
(b) the more formic acid derivates of aromatic hydrocarbons obtained by the inventive method, it is the original commonly used in fine chemistry industry particularly material resin
Material, 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, an example goes out corresponding conditionses, and form is as follows:
From S compounds prepare T compounds [formula (I) to (II), 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 operation of embodiment 1 is as follows.
Embodiment 1 from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt chloride PA 12
Alkyl fatty acid sodium tempo, 0.5MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 24 hours (1.0/0.005/
0.005/0.005/0.005)]。
Cobalt chloride (0.020mmol), PA (0.020mmol), dodecyl aliphatic acid are added in a kettle
Sodium (0.020mmol), 2,2,6,6- tetramethyl piperidine nitrogen oxides (also known as Tempo, 0.020mmol), toluene (4.0mmol) and
Dimethyl succinate 2.0mL, acetic acid 0.2mL, 140 DEG C under 0.5MPa oxygen, stirring reaction 24 hours, stop reaction, cooling
Filter to obtain benzoic acid, yield 95%.
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, two esters 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.
(1) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt chloride PA dodecyl
Sodium soap Tempo, 1.0MPa oxygen (dimethyl succinate+acetic acid (50%)) 140 DEG C 12 hours (1.0/0.002/
0.002/0.002/0.002)], same embodiment 1, yield 91% are operated.
(2) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt chloride 2- aminomethyl-pyridines dodecane
Base sodium soap HP, 2.0MPa oxygen (dimethyl succinate+acetic acid) 40 DEG C 120 hours
(1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 4%.
(3) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), (cobalt acetate+manganese acetate)---,
2.0MPa oxygen (dimethyl succinate+acetic acid) 120 DEG C 120 hours (1.0/0.05/0/0/0)], operate same embodiment 1,
Yield 6%.
(4) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate quinoline--, 5.0MPa oxygen
(dimethyl succinate+acetic acid) 120 DEG C 120 hours (1.0/0.05/0.05/0/0)], operate same embodiment 1, yield 5%.
(5) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate quinoline -2,2,6,6- tetramethyls
Piperidine nitroxide, 10.0MPa oxygen (diethyl succinate+acetic acid (90%)) 120 DEG C 120 hours (1.0/0.05/
0.05/0/0.05)], same embodiment 1, yield 17% are operated.
(6) from Isosorbide-5-Nitrae-dimethylbenzene prepare Isosorbide-5-Nitrae-dibenzoic acid [formula (I) to (II), cobalt acetate isoquinolin potassium hyperchlorate 2,
2,6,6- tetramethyls-piperidines nitrogen oxides, 0.8MPa oxygen (dimethyl succinate+valeric acid+acetic acid) 160 DEG C 8 hours
(1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 53%.
(7) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate Phen sodium hypochlorite
(1,2- hexamethylene dicarboximide+n-hydroxysuccinimide), 1.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C
8 hours (1.0/0.01/0.02/0.01/0.02)], operate same embodiment 1, yield 37%.
(8) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate quinoline zirconium nitrate tempo,
0.8MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.02/0.02)], operation is same
Embodiment 1, yield 26%.
(9) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate Phen lithium nitrite 4-
Carboxy-N-hydroxyphthalimide, 1.5MPa oxygen (dimethyl succinate+caproic acid) 160 DEG C 8 hours (1.0/
0.01/0.02/0.02/0.01)], same embodiment 1, yield 32% are operated.
(10) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate (Phen+N- methoxy carbonyls
Base-aspartic acid) neopelex 2-aza-adamantane-N- oxygen radicals, 2.0MPa oxygen (succinic acid diformazan
Ester+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.02/0.01/0.01)], operate same embodiment 1, yield 36%.
(11) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate (Phen+4- amino pyrroles
Pyridine) dodecyl sodium sulfate 9- azabicyclos [3.3.1] nonane N- oxygen radicals, 1.0MPa oxygen (dimethyl succinate+
Butyric acid) 160 DEG C 8 hours (1.0/0.02/0.02/0.02/0.02)], operate same embodiment 1, yield 48%.
(12) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate (Phen+2- hydroxyl pyrroles
Pyridine) dodecyl sodium sulfate 4- carboxy-Ns-hydroxyphthalimide, 1.0MPa oxygen (dimethyl succinate+second
Acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 68%.
(13) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate Phen+2- amino pyrroles
Pyridine dodecyl sodium sulfate n-hydroxysuccinimide, 0.4MPa oxygen (diethyl succinate+butyric acid+acetic acid) 160 DEG C
8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 63%.
(14) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate (quinoline+Phen) ten
Dialkyl sulfonates peroxosulphuric hydrogen potassium complex salt, 0.5MPa oxygen (diethyl succinate+butyric acid+acetic acid) 250 DEG C it is 8 small
When (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 71%.
(15) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate (quinoline+pyridine) dodecane
Base sodium sulfonate sodium peroxydisulfate, 0.5MPa oxygen (diethyl succinate+valeric acid-acetic acid) 160 DEG C 8 hours (1.0/0.01/
0.01/0.01/0.01)], same embodiment 1, yield 73% are operated.
(16) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate (quinoline+2 hydroxy pyrimidine)
Liu Suanmu (perchloro--HP+2,2,6,6- tetramethyl piperidine nitrogen oxides), 0.3MPa Yang Qis
(dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield
82%.
(17) from Isosorbide-5-Nitrae-dimethylbenzene prepare Isosorbide-5-Nitrae-dibenzoic acid [formula (I) to (II), cobalt acetate (Phen+isoquinoline
Quinoline) acetic acid Wus (perchloro--HP+2,2,6,6- tetramethyl piperidine nitrogen oxides+potassium peroxydisulfate),
0.3MPa oxygen (dimethyl carbonate+acetic acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate with real
Apply example 1, yield 68%.
(18) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate succinic acid tungsten oxide perchloro-
Generation-HP, 0.4MPa oxygen (diethyl succinate+butyric acid) 160 DEG C 12 hours (1.0/
0.01/0.01/0.01/0.01)], same embodiment 1, yield 51% are operated.
(19) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate 4- tert-butoxies pyridine (ten
Dialkyl benzene sulfonic acids sodium+potassium dihydrogen phosphate) perchloro--HP, 0.5MPa oxygen (succinic acid methyl esters
+ acetic acid) 160 DEG C 8 hours 1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 56%.
(20) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate DAP 12
Sodium alkyl sulfonate perchloro--HP, 0.4MPa oxygen (dimethyl glutarate+acetic acid) 160 DEG C
12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 63%.
(21) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate 3,5- lutidines nitric acid
Samarium perchloro--HP, 0.4MPa oxygen (ethyl glutarate+acetic acid (20%)) 160 DEG C 12
Hour (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 64%.
(22) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate N- benzyloxycarbonyl groups-phenylpropyl alcohol ammonia
It is sour dodecyl sodium sulfate perchloro--HP, 0.4MPa oxygen (dimethyl adipate+acetic acid)
160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 67%.
(23) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), (cobalt acetate+ferric acetate) bipyridyl (ten
Dialkyl sulfonates+zirconium oxide] HP, 0.5MPa oxygen (dimethyl adipate+acetic acid) 160
DEG C 12 hours 1.0/0.01/0.01/0.01/0.01), operate same embodiment 1, yield 31%.
(24) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), (cobalt acetate+cerous nitrate) (3- isopropyl oxygen
Yl pyridines+N, N '-diisopropyl succinamide) (dodecyl sodium sulfate+zirconium nitrate) HP,
0.5MPa oxygen (diethylene 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%.
(25) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), (cobalt acetate+ruthenic chloride) (bipyridyl+N,
N, N ', N '-tetra isopropyl succinamide) scandium sulfate-, 50% hydrogen peroxide (dipropyl adipate+acetic acid) 160 DEG C 12
Hour (1.0/0.01/0.01/0.01/0)] operation with embodiment 1, yield 28%.
(26) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), (cobalt acetate+radium chloride) (penta chloropyridine+
N, N, N ', N '-tetrapropyl succinamide) lanthanum nitrate Tempo, 0.5MPa air (dimethyl adipate+acetic acid) 160 DEG C
12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 33%.
(27) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobalt acetate-chlorine rhodium acid potassium (bipyridyl+N,
N '-dipropyl succinamide) (dodecyl sodium sulfate+lanthana) potassium perborate, 0.5MPa air (dimethyl succinate+
Ethyl acetate+acetic acid) 100 DEG C 120 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield
46%.
(28) terephthalic acid (TPA) [formula (I) to (II), (the ruthenium hydrochloride ammonium) N- benzyloxies of cobalt acetate+five are prepared from Isosorbide-5-Nitrae-dimethylbenzene
Carbonyl-phenylalanine (dodecyl sodium sulfate+samarium oxide) HP, 0.5MPa oxygen (dodecane
Carbomethoxyphenyl+methyl propionate+acetic acid) 100 DEG C 120 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment
1, yield 19%.
(29) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), (cobalt acetate+palladium trifluoroacetate) N- acetyl
Base-phenylalanine (dodecyl sodium sulfate+zirconium sulfate) HP, 0.5MPa oxygen (water+second
Acid) 120 DEG C 48 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 26%.
(30) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cerous acetate N- acetyl group-leucine nitre
Sour oxygen zirconium TEMPO, 3.0MPa air (dimethyl adipate+water+acetic acid) 120 DEG C 12 hours (1.0/0.01/0.01/
0.01/0.01)], same embodiment 1, yield 23% are operated.
(31) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cerium hydroxide N- acetyl group-leucine
(dodecyl sodium sulfate+lanthanum sulfate) TEMPO, 70% hydrogen peroxide (dimethyl adipate+methyl caproate+acetic acid) 120 DEG C
12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 51%.
(32) from Isosorbide-5-Nitrae-dimethylbenzene prepare terephthalic acid (TPA) [formula (I) to (II), cobaltous ammonium phosphate 2- bromopyridines (scandium nitrate+
Potassium hydrogen phosphate) tempo, 1.2MPa oxygen (dimethyl succinate+acetic acid) 200 DEG C 8 hours (1.0/0.01/0.01/
0.01/0.01)], same embodiment 1, yield 78% are operated.
(33) from 1,3- dimethylbenzene prepare terephthalic acid (TPA) [formula (I) arrives (II), cobaltous bromide 2- methoxypyridines dodecane
Base sodium soap 2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides, 1.0MPa oxygen (dimethyl succinate+second
Sour (5%)) 120 DEG C 24 hours (1.0/0.001/0.001/0.001/0.001)], operate same embodiment 1, yield 36%.
(34) from 1,3- dimethylbenzene prepare terephthalic acid (TPA) [formula (I) arrives (II), cobalt acetate 2- benzyl pyridines dodecyl
Sodium soap tempo, 0.5MPa oxygen (diisopropyl ester amber acid+acetic acid) 80 DEG C 96 hours (1.0/0.005/0.005/
0.005/0.005)], same embodiment 1, yield 49% are operated.
(35) from 1,3- dimethylbenzene prepare terephthalic acid (TPA) [formula (I) arrives (II), cobalt acetate 3- pyridones dodecyl
Sodium soap perchloro--HP, 0.6MPa oxygen (ethyl glutarate+acetic acid) 100 DEG C 48
Hour (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 86%.
(36) from 1,3- dimethylbenzene prepare terephthalic acid (TPA) [formula (I) arrives (II), (cobalt acetate+manganese chloride) 4- acetyl pyrroles
Pyridine lithium nitrite tempo, 0.6MP oxygen (dimethyl succinate+acetic acid) 120 DEG C 12 hours (1.0/0.01/0.01/
0.02/0.02)], same embodiment 1, yield 91% are operated.
(37) from 1,2- dimethylbenzene prepare terephthalic acid (TPA) [formula (I) arrives (II), (cobalt acetate+manganous fluoride) 2,6- pyridines two
Formic acid (sodium hypochlorite+zirconium sulfate) HP, 1.0MPa oxygen (dimethyl succinate+acetic acid)
120 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 93%.
(38) from 1,2- dimethylbenzene prepare terephthalic acid (TPA) [formula (I) arrives (II), (cobalt acetate+manganese carbonate)-dodecyl
Sodium soap tempo, 0.5MPa oxygen (glutaric acid dipropyl+acetic acid) 120 DEG C 12 hours (1.0/0.01/0/0.01/
0.01) same embodiment 1, yield 81%], are operated.
(39) from fluoro- 1, the 2- dimethylbenzene of 4- prepare the fluoro- phthalic acids of 4- [formula (I) arrives (II), (cobalt acetate+manganese phosphate)
Pyridine dodecyl sodium soap tempo, 1.0MPa oxygen (dimethyl succinate+acetic acid) 120 DEG C 8 hours (1.0/
0.01/0.01/0.01/0.01)], same embodiment 1, yield 81% are operated.
(40) from 4- bromo-1,2-xylenes prepare 4- bromo- phthalic acids [formula (I) to (II), cobalt acetate manganese oxalate 3,
4- pyridinedicarboxylic acids (dodecyl aliphatic acid potassium+calcium hypochlorite) sodium perborate, 1.0MPa oxygen (glutaric acid diisopropyl ester+
Acetic acid) 120 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 83%.
(41) from chloro- 1, the 2- dimethylbenzene of 4- prepare the chloro- phthalic acids of 4- [formula (I) arrives (II), (cobalt acetate+manganese sulfate)
4- chloropyridines sodium sulfite 2,2,6,6- tetramethyl piperidine -4- ketone -1- oxygen radicals, 1.0MPa oxygen (diethylene adipate
+ acetic acid) 120 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 87%.
(42) 4- isopropoxies-[formula (I) arrives (II) to phthalic acid, (vinegar are prepared from 4- isopropoxies -1,2- dimethylbenzene
Sour cobalt+manganese sulfate) 3,5- pyridinedicarboxylic acids TBAB 4- carboxy-Ns-hydroxyphthalimide, 0.5MPa oxygen
Gas (glutaric acid diisopropyl ester+glutaric acid) 120 DEG C 6 hours 1.0/0.01/0.01/0.01/0.01], operate same embodiment
1, yield 91%.
(43) from 4- hexyloxies -1,2- dimethylbenzene prepare 4- hexyloxies-phthalic acid [formula (I) arrives (II), (cobalt acetate+
Manganese oxide) 4- bromopyridines (lithium hypochlorite+zirconium sulfate) 9- azabicyclos [3.3.1] nonane N- oxygen radicals, 0.5MPa oxygen
Gas (dimethyl adipate-acetic acid) 180 DEG C 6 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1,
Yield 83%.
(44) from 4- nitros -1,2- dimethylbenzene prepare 4- nitros-phthalic acid [formula (I) arrives (II), cobalt acetate 2,3-
Pyridinedicarboxylic acid acid anhydride (TBAB+zirconium acetate) 2-aza-adamantane-N- oxygen radicals, 30% hydrogen peroxide (oneself two
Dimethyl phthalate+acetic acid) 120 DEG C 4 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 63%.
(45) from the chloro- ortho-xylenes of 3- prepare the chloro- phthalic acids of 3- [formula (I) to (II), cobalt acetate 2- fluorine pyridine
(sodium hypochlorite+acetic acid molybdenum) sodium peroxide, 0.5MPa oxygen (diethylene adipate+acetic acid) 180 DEG C 8 hours (1.0/
0.01/0.01/0.01/0.01)], same embodiment 1, yield 74% are operated.
(46) from the bromo- ortho-xylenes of 3- prepare the bromo- phthalic acids of 3- [formula (I) to (II), cobalt acetate 2- methoxycarbonyl groups
Pyridine (sodium acetate+hafnium oxide) 2-aza-adamantane-N- oxygen radicals, 0.5MPa oxygen (dimethyl succinate+acetic acid
(95%)) 180 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 81%.
(47) from the fluoro- ortho-xylenes of 3- prepare the fluoro- phthalic acids of 3- [formula (I) to (II), cobalt acetate PA-
4- carboxylic acids (lanthana+acetic acid praseodymium) 2-aza-adamantane-N- oxygen radicals, 0.5MPa oxygen (dimethyl succinate+second
Acid) 180 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 72%.
(48) from 3,4- mesitylenic acids prepare 1,3,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate N- acetyl group-
Tyrosine (TBAB+acetic acid hafnium) 2-aza-adamantane-N- oxygen radicals, 0.6MPa oxygen (dimethyl succinate
+ acetic acid) 180 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 82%.
(49) from 3,4- dimethylphenylcarbinols prepare 1,3,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate N- acetyl group-
Tyrosine (TBAB+praseodymium oxide) 2-aza-adamantane-N- oxygen radicals, 0.5MPa oxygen (dimethyl succinate
+ acetic acid) 180 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 86%.
(50) from 3,4- dimethylbenzaldehydes prepare to 1,3,4- benzenetricarboxylic acid [formula (I) arrives (II), cobalt acetate 5- chlorine pyrroles
Pyridine zirconium nitrate 2-aza-adamantane-N- oxygen radicals, 0.5MPa oxygen (dipropyl adipate+acetic acid) 180 DEG C it is 12 small
When (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 84%.
(51) from 3,4- dimethylanisoles prepare to 4- methoxyl groups-phthalic acid [formula (I) arrives (II), cobaltous fluoride pyrrole
Pyridine dodecyl sodium soap the fluoro- HPs of 4-, 0.5MPa oxygen (dimethyl succinate+acetic acid)
140 DEG C 24 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 76%.
(52) from 1,3- dimethyl nitrobenzenes prepare 5- nitros -1,3 phthalic acids [formula (I) arrives (II), cobalt chloride pyridine
Dodecyl aliphatic acid potassium tempo, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 24 hours (1.0/
0.001/0.001/0.001/0.001)], same embodiment 1, yield 73% are operated.
(53) from 3,5- dimethylanisoles prepare to 5- methoxyl groups-M-phthalic acid [formula (I) arrives (II), lithium cobalt oxide
2,6- dioctyl phthalate pyridines six alkyl fatty acid sodium tempo, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C it is 12 small
When (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 81%.
(54) from 3,5- dimethylbenzaldehydes prepare to 1,3,5 benzenetricarboxylic acid [formula (I) arrives (II), acetylacetone cobalt 2- oneself
The tetramethyl piperidine nitrogen oxides of Ji Biding octyl aliphatic acid Jias 2,2,6,6-, 1.0MPa Yang Qis (diisopropyl adipate+
Acetic acid) 140 DEG C 8 hours (1.0/0.005/0.01/0.005/0.005)], operate same embodiment 1, yield 79%.
(55) from 3,5- dimethylphenylcarbinols prepare to 1,3,5 benzenetricarboxylic acid [formula (I) arrives (II), cobalt chloride 3- bromine pyrroles
Pyridine heptane base sodium soap tempo, 1.1MPa oxygen [dimethyl succinate+acetic acid] 140 DEG C 8 hours (1.0/0.01/
0.01/0.01/0.01)], same embodiment 1, yield 82% are operated.
(56) from 3,5- dimethylated chlorobenzenes prepare to the chloro- M-phthalic acids of 5- [formula (I) arrives (II), molybdenum oxide cobalt 2- chlorine pyrroles
Ding butyl Zhi Fangsuanna 2,2,6,6- tetramethyl piperidine nitrogen oxides, 1.2MPa Yang Qis (dimethyl succinates+acetic acid) 160
DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 83%.
(57) chloro- to 2- Isosorbide-5-Nitrae-phthalic acid [formula (I) to (II), (copper chloride+chlorination are prepared from the chloro- Isosorbide-5-Nitraes of 2--dimethylbenzene
Cobalt) 4- pyridones dodecyl sodium soap tempo, 0.5MPa oxygen (diisopropyl adipate+acetic acid) 300 DEG C
48 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 57%.
(58) from bromo- Isosorbide-5-Nitraes of 2--dimethylbenzene prepare Isosorbide-5-Nitrae-phthalic acid bromo- to 2- [formula (I) to (II), cobalt acetate pyridine
The tetramethyl piperidine nitrogen oxides of ten alkyl fatty acid Na 2,2,6,6-, 0.5MPa Yang Qis (dimethyl succinates+acetic acid) 160
DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 81%.
(59) from 2- nitros Isosorbide-5-Nitrae-dimethylbenzene prepare 2 nitros-Isosorbide-5-Nitrae phthalic acid [(formula (I) to (II), cobalt carbonate (N- second
Acyl glycine+pyridine) molybdenum oxide tempo, 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 68% are operated.
(60) from 2- methoxyl groups p-xylene prepare 2- methoxyl groups-terephthalic acid (TPA) [formula (I) to (II), cobalt carbonate 2-
Phenylpyridine potassium phosphate 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 63%.
(61) from 2,5- dimethyl-benzaldehydes prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt carbonate 2- methyl pyrroles
Pyridine dodecyl sodium soap 4- methyl-N-hydroxy phthalimides, 0.5MPa oxygen (dimethyl succinate+second
Acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 71%.
(62) from 2,5- dimethyl-benzoic acids prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt carbonate quinoline ten
Dialkyl group sodium soap the fluoro- HPs of 2-, 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 68%.
(63) from 2 chloro- meta-xylenes prepare to the chloro- M-phthalic acids of 2- [formula (I) to (II), cobalt carbonate N- propionyl-the third
Propylhomoserin dodecyl sodium soap 4- methoxycarbonyl groups-HP, 0.5MPa oxygen (succinic acid diformazan
Ester+acetic acid) 130 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 76%.
(64) from 2 bromo- meta-xylenes prepare to the bromo- M-phthalic acids of 2- [formula (I) to (II), cobalt carbonate isoquinolin ten
The tetramethyl piperidine nitrogen oxides of dialkyl group Zhi Fangsuanna 2,2,6,6-, 0.6MPa Yang Qis (dimethyl succinates+acetic acid) 160
DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 71%.
(65) from 2 fluoro- meta-xylenes prepare to the fluoro- M-phthalic acids of 2- [formula (I) to (II), cobalt carbonate (isoquinolin+neighbour
Phenanthroline) dodecyl sodium soap N, the equal pyromellitic dimide of N '-dihydroxy, 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 63%.
(66) from 2,6- dimethylphenylcarbinols prepare 1,2,3- benzenetricarboxylic acids [formula (I) arrives (II), stannous chloride 2- isopropyls
Yl 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 68%.
(67) from 2,6- dimethylbenzaldehydes prepare 1,2,3- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate (4- iodine pyridines
+ N- benzoyls-valine) dodecyl sodium soap n-hydroxysuccinimide, 0.5MPa oxygen (succinic acid diformazan
Ester+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 72%.
(68) from 2,6- mesitylenic acids prepare 1,2,3- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate (2- hydroxyl pyrroles
Pyridine+N- pivaloyls-isoleucine) tetrabutylammonium chloride potassium peroxydisulfate, 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 74%.
(69) from 2,6- dimethylanisoles prepare 2- methoxyl groups-M-phthalic acid [formula (I) arrives (II), cobalt acetate (4-
Pyridone+N- isobutyryls-alanine) undecyl aliphatic acid potassium 2,2,6,6- tetramethyl piperidine -4- ketone -1- oxygen it is free
Base, 2.0MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operation
With embodiment 1, yield 82%.
(70) from the chloro- meta-xylenes of 4- prepare the chloro- M-phthalic acids of 4- [formula (I) to (II), cobalt acetate (4- tert-butyl group pyrroles
Pyridine+acetylacetone,2,4-pentanedione) dodecyl sodium soap potassium percarbonate, 1.0Mpa nitrogen dilution oxygen (50%) (dimethyl succinate
+ acetic acid) 160 DEG C 8 hours 1.0/0.01/0.02/0.01/0.04], operate same embodiment 1, yield 91%.
(71) from the bromo- meta-xylenes of 4- prepare the bromo- M-phthalic acids of 4- [formula (I) to (II), (cobalt acetate+cerous acetate) 2-
Pyridone dodecyl sodium soap 4- carboxy-Ns-hydroxyphthalimide, 1.0MPa oxygen (succinic acid diformazan
Ester+acetic acid) 160 DEG C 6 hours (1.0/0.01/0.04/0.01/0.04)], operate same embodiment 1, yield 84%.
(72) 4- nitro-isophthalic acid [formula (I) to (II), (cobalt acetate+acetic acid are prepared from 4- nitros-meta-xylene
Palladium) 2- methoxypyridines TBAB HP, 1.5MPa nitrogen diluent air (succinic acid
Dimethyl ester+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.04/0.01)], operate same embodiment 1, yield 71%.
(73) from 2,4- dimethylanisoles prepare 4- methoxyl groups-M-phthalic acid [formula (I) arrives (II), cobalt acetate (2-
The tetramethyl piperidine nitrogen oxides of cyclohexyl epoxide pyridine+N- acetyl-phenylalanine) Liu Suanans 2,2,6,6-, 0.5MPa oxygen
Gas (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.04)], operate same embodiment 1,
Yield 62%.
(74) from 2,4- dimethylphenylcarbinols prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate N- acetyl group-
Phenylglycine sodium sulfite (2,2,6,6- tetramethyl -4- hydroxy 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%.
(75) from 2,4- mesitylenic acids prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate (Phen
+ 4-aminopyridine) potassium nitrate SODIUM PERCARBONATE, 0.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 8 hours (1.0/
0.01/0.04/0.04/0.04)], same embodiment 1, yield 43% are operated.
(76) from chloro- Isosorbide-5-Nitraes of 2--dimethylbenzene prepare the chloro- terephthalic acid (TPA)s of 2- [formula (I) to (II), cobalt acetate N- acetyl group-
Leucine dodecyl sodium sulfate perchloro--HP, 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 68%.
(77) from 2,5- dimethylanisoles prepare 2- methoxyl groups-terephthalic acid (TPA) [formula (I) arrives (II), cobalt acetate N- benzyls
Oxygen carbonyl-aspartic acid dodecyl sodium sulfate perchloro--HP, 0.5MPa oxygen (succinic acid
Dipropyl+acetic acid) 130 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 57%.
(78) from 2,5- dimethylphenylcarbinols prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate N- acetyl group-
Glutamic acid dodecyl sodium sulfate perchloro--HP, 0.5MPa oxygen (diisopropyl ester amber acid+
Acetic acid) 120 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 59%.
(79) 2- nitros-terephthalic acid (TPA) [formula (I) to (II), (cobalt acetate+acetic acid is prepared from Isosorbide-5-Nitrae-dimethyl nitrobenzene
Manganese) N- benzyloxycarbonyl groups-leucine dodecyl sodium sulfate perchloro--HP, 1.0MPa oxygen
(diethyl succinate+acetic acid) 140 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, produce
Rate 66%.
(80) from 2,6- dimethylnaphthalenes prepare 2,6- naphthalene dicarboxylic acids [formula (I) arrives (II), cobalt acetate N- acetyl-cyclohexyls
Glycine Potassium Zirconium Fluoride perchloro--HP, 1.0MPa oxygen (dimethyl succinate+acetic acid oneself
Ester+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 76%.
(81) from Isosorbide-5-Nitrae-dimethylnaphthalene prepare Isosorbide-5-Nitrae-naphthalene dicarboxylic acids [formula (I) to (II), cobalt acetate (PA+N-
Acetyl group-leucine) zirconium carbonate perchloro--HP, 1.0MPa oxygen (dimethyl succinate+second
Tert-butyl acrylate+acetic acid) 160 DEG C 8 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 83%.
(82) from 1,5- dimethylnaphthalenes prepare 1,5- naphthalene dicarboxylic acids [formula (I) arrives (II), cobalt acetate (PA+the third
Acid dimethyl) hexahydrobenzoid acid sodium perchloro--HP, 1.0MPa oxygen (dimethyl malenate
+ butyric acid) 160 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 91%.
(83) from 3,5- dimethylbenzaldehydes prepare 1,3,5-, benzenetricarboxylic acid [formula (I) arrives (II), cobalt acetate (2- amino
Pyridine-diethyl malonate) zirconium oxycarbonate perchloro--HP, 1.0MPa oxygen (succinic acid
Dimethyl ester+isopropyl acetate+acetic acid) 150 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment
1, yield 72%.
(84) from 2,4- dimethylbenzaldehydes prepare 1,2,4-, benzenetricarboxylic acid [formula (I) arrives (II), cobalt acetate (4- hydroxyls
Pyridine+ethylene dimethyl) sodium methacrylate perchloro--HP, 1.0MPa oxygen (ethanedioic acid two
Methyl esters+isobutyric acid) 140 DEG C 12 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 81%.
(85) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt chloride (Phen+
N, N, N ', N '-tetramethyl malonamide) pivalic acid sodium 4- carboxy-Ns-hydroxyphthalimide, 10.0MPa oxygen
(dimethyl succinate+ethyl isobutyrate+acetic acid) 140 DEG C 8 hours (1.0/0.005/0.005/0.005/0.005)], behaviour
Make with embodiment 1, yield 71%.1H NMR(400MHz,DMSO-d6):δ=13.0 (s, 3H), 8.24 (m, 1H), 8.15 (m,
1H),7.77(m,1H);13C NMR(100MHz,DMSO-d6):δ=168.4,167.5,166.0,137.3,132.5,132.1,
131.8,129.3,128.6.
(86) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt chloride 2- benzoyls
Pyridine pivalic acid potassium n-hydroxysuccinimide, 8.0MPa oxygen (dimethyl succinate+pivalic acid ethyl ester+acetic acid) 120
DEG C 8 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 72%.
(87) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobaltous bromide 2- carbethoxyl groups
Pyridine potassium isobutyrate n-hydroxysuccinimide, 5.0MPa oxygen (dimethyl succinate+acetic acid) 120 DEG C 8 hours
(1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 68%.
(88) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobaltous fluoride 3- pyridones
Potassium butyrate tempo, 2.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 12 hours (1.0/0.005/0.005/
0.005/0.005)], same embodiment 1, yield 63% are operated.
(89) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate 3- itrile groups pyridine
The tetramethyl piperidine nitrogen oxides of Ji Suanna 2,2,6,6-, (dimethyl succinate+DEG C 24 of acetic acid) 140 are small by 1.0MPa Yang Qis
When (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 65%.
(90) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt chloride 4- itrile groups pyridine
The tetramethyl piperidine nitrogen oxides of Yi Suanjia 2,2,6,6-, (dimethyl succinate+DEG C 24 of acetic acid) 140 are small by 0.5MPa Yang Qis
When (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 62%.
(91) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt chloride 4- acetylpyridines
(the undecyl sodium soap+tetramethyl piperidine nitrogen oxides of TBAB) 2,2,6,6-, 0.4MPa Yang Qi (succinic acid
Dimethyl ester+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield
64%.
(92) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate (PA
+ N- acetyl group-Terleu) samarium sulphate 2,2,6,6- tetramethyl -4- methoxy piperide nitrogen oxides, 0.4MPa oxygen (fourth
Acid dimethyl+ethyl glutarate+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], behaviour
Make with embodiment 1, yield 63%.
(93) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobaltous bromide N- benzyloxycarbonyl groups-
Glycine ten alkyl fatty acid sodium tempo, 70% hydrogen peroxide (dimethyl succinate+acetic acid) 100 DEG C 96 hours (1.0/
0.005/0.005/0.005/0.005)], same embodiment 1, yield 36% are operated.
(94) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt chloride N- acetyl group-benzene
Alanine dodecyl sodium soap 2-aza-adamantane-N- oxygen radicals, 50% hydrogen peroxide (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 43%.
(95) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobaltous fluoride N- benzyloxycarbonyl groups-
Phenylalanine TBAB 2-aza-adamantane-N- oxygen radicals, 0.3MPa 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 69%.
(96) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), lithium cobalt oxide N- benzyloxy carbonyls
Base-isoleucine tetrabutylammonium chloride 2-aza-adamantane-N- oxygen radicals, 0.3MPa air (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 32%.
(97) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt hydroxide quinoline four fourths
Base Xiu Huaan 2-aza-adamantanes-N- oxygen radicals-n-hydroxysuccinimide, 0.3MPa Kong Qis (dimethyl succinates+second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 43%.
(98) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt aluminate 2- picolines
TBAB 2-aza-adamantane-N- oxygen radicals, 0.2MPa oxygen (dimethyl succinate+propionic acid) 140 DEG C 32
Hour (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 37%.
(99) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobaltous ammonium phosphate 2- methyl pyrroles
Pyridine TBAB 2-aza-adamantane-N- oxygen radicals, 0.2MPa air (dimethyl succinate+butyric acid) 140 DEG C
32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 39%.(100) it is inclined from 1,2,4-
Trimethylbenzene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), cobalt acetate N, N '-diethyl oxalamide TBAB
2-aza-adamantane-N- oxygen radicals, 0.2MPa air dimethyl succinate+isobutyric acid 140 DEG C 32 hours (1.0/
0.005/0.005/0.005/0.005)], same embodiment 1, yield 38% are operated.
(101) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cobalt acetate+ruthenic chloride)
1,3- di-t-butyl propanedione TBAB 2-aza-adamantane-N- oxygen radicals, 0.2MPa air (succinic acid two
Methyl esters+acetic acid) 140 DEG C 32 hours 1.0/0.05/0.05/0.005/0.005)], operate same embodiment 1, yield 43%.
(102) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cobalt acetate+cerous acetate)
Succinic acid di tert butyl carbonate TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa 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 56%.
(103) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cobalt oxalate+cerous acetate)
4- picolines TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 59%.
(104) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cobalt hydroxide+acetic acid
Cerium) suberic acid dipropyl TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (succinic acid diformazan
Ester+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 63%.
(105) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+acetic acid
Cerium) 2- ethylpyridines TBAB 2-aza-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)], operate same embodiment 1, yield 68%.
(106) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+oxidation
Zirconium cerium) 3,5 lutidines TBAB 2-aza-adamantane-N- oxygen radical 0.1MPa oxygen (succinic acid two
Methyl esters+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.01)], operate same embodiment 1, yield 69%.
(107) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+oxidation
Cerium) 2- fluorine pyridine TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate the same yield 41% of embodiment 1.
(108) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cobalt acetate+cerium oxide)
2 hydroxy pyrimidine (TBAB) HP, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours 1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 43%.
(109) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cobalt hydroxide+carbonic acid
Cerium) PA TBAB 2-aza-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)], operate same embodiment 1, yield 53%.
(110) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (lithium cobalt oxide+trifluoro second
Sour palladium) 2,6- lutidines TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (succinic acid
Dimethyl ester+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield
61%.
(111) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+nitric acid
Cerium ammonium) PA (TBAB+zirconium acetate) 2-aza-adamantane-N- oxygen radicals, 0.1MPa pressure 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 64%.
(112) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cobaltous ammonium phosphate+sulfuric acid
Rhodium) 4- picolines TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa 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 80%.(100 grams of rule
Mould).
(113) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cobalt nitrate+chlorine rhodium acid
Potassium) 4-aminopyridine TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa 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 84%.(1.0Kg is advised
Mould).
(114) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (acetylacetone cobalt+chlorine rhodium
Sour potassium+cerium chloride) 2 hydroxy pyrimidine tri-methyl benzyl ammonium bromide 2-aza-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)], operate same embodiment
1, yield 81%.(10Kg scales).
(115) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cobaltous fluoride+chlorine rhodium acid potassium+
Perchloric acid cerium) 3- aminopyridines trimethyl benzyl ammonia chloride 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (fourth
Acid dimethyl+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, produce
Rate 82%.
(116) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+chlorine rhodium
Sour potassium+cerium oxalate) 2- picolines zirconium oxide 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (succinic acid diformazan
Ester+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 80%.
(117) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+chlorine rhodium
Sour potassium) 4-aminopyridine samarium oxide 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 74%.
(118) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cobalt-chromate+chlorine rhodium acid
Potassium) 4- benzyl pyridines zirconium nitrate 2-aza-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), operate same embodiment 1, yield 71%.
(119) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cobalt aluminate+chlorine rhodium acid
Potassium) 4- acetylpyridines lithium sulfate 2-aza-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)], operate same embodiment 1, yield 63%.
(120) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+chlorine rhodium
Sour potassium) 3,4- pyridinedicarboxylic acids ammonium sulfate 2-aza-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)], operate same embodiment 1, yield 73%.
(121) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), and (nitrification cobalt hexamine is complexed
Thing+chlorine rhodium acid potassium) 2- picolines natrium nitrosum 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (succinic acid two
Methyl esters+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.005/0.05/0.05)], operate same embodiment 1, yield 42%.
(122) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (hexanitro cobalt acid sodium+chlorine
Rhodium acid potassium) 2,6- lutidines sodium nitrate 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (succinic acid diformazan
Ester+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.005/0.05)], operate same embodiment 1, yield 47%.
(123) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+chlorine rhodium
Sour potassium) 2- pyridine carboxylic acids scandium nitrate 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 53%.
(124) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (molybdenum oxide cobalt+chlorine rhodium acid
Potassium) 4- picolines sodium phosphate 2-aza-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)], operate same embodiment 1, yield 59%.
(125) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+chlorine rhodium
Sour potassium) 2 hydroxy pyrimidine sodium phosphite 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 47%.
(126) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+chlorine rhodium
Sour potassium) PA sodium perchlorate 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.02/0.02/0.005/0.005)], operate same embodiment 1, yield 79%.
(127) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (sulfamic acid cobalt+chlorine rhodium
Sour potassium) 2- picolines calcium hypochlorite 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.03/0.03/0.005/0.005)], operate same embodiment 1, yield 83%.
(128) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cerous phosphate+nickel fluoride)
4- pyridones zirconyl acetate 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+acetic acid)
140 DEG C 32 hours (1.0/0.05/0.05/0.1/0.05)], operate same embodiment 1, yield 86%.
(129) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cerium oxalate+nickel nitrate)
4-aminopyridine dodecyl sodium sulfate 2-aza-adamantane-N- oxygen radicals, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.1)], operate same embodiment 1, yield 87%.
(130) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), and (perchloric acid cerium+oxidation is sub-
Nickel) 4- iodine pyridines dodecyl sodium sulfate HP, 0.1MPa oxygen (dimethyl succinate+second
Acid) 140 DEG C 32 hours 1.0/0.05/0.05/0.05/0.05)], operate same embodiment 1, yield 89%.
(131) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cerium hydroxide+Hexafluoro silicon Sour nickel)4- nitropyridines dodecyl sodium sulfate HP, 0.1MPa oxygen (dimethyl glutarate
+ acetic acid) 140 DEG C 32 hours (1.0/0.05/0.1/0.05/0.05)], operate same embodiment 1, yield 88%.
(132) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cerous sulfate+Nickel sulfate Ammonium)DAP dodecyl sodium sulfate HP, 0.1MPa oxygen propionic acid 140 DEG C
32 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, yield 81%.
(133) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cerium oxide+Nickel cobalt mangaic acid Lithium)2,6- dihydroxy-pyridines dodecyl sodium sulfate HP, 0.1MPa oxygen butyric acid 140 DEG C
32 hours (1.0/0.01/0.01/0.005/0.005)], operate same embodiment 1, yield 83%.
(134) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cerium chloride+chlorine rhodium acid
Potassium) DAP dodecyl sodium sulfate perchloro--HP, 0.1MPa oxygen (fourth
Acid dimethyl+dimethyl carbonate+acetic acid) 140 DEG C 32 hours 1.0/0.05/0.05/0.05/0.05)], operate with implement
Example 1, yield 90%.
(135) from 1,2,4- durene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (cerous acetate+chlorine rhodium acid potassium)
2,6- lutidines dodecyl sodium sulfate HP, 0.1MPa oxygen (dimethyl carbonate-second
Acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 49%.
(136) from 1,2,4- pseudocumene prepare 1,2,4- benzenetricarboxylic acids [formula (I) arrives (II), (bromination cerium+cobalt acetate)
2- pyridine carboxylic acids dodecyl sodium sulfate perchloro--HP, 0.1MPa oxygen (succinic acid diformazan
Ester+acetic acid) 140 DEG C 12 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 88%.
(137) from 1,2,4- pseudocumene preparation, 1,2,4- benzenetricarboxylic acids, [formula (I) arrives (II), (cerium fluoride+nitrification cobalt
Hexamine complex compound) 2- nitropyridines dodecyl sodium sulfate perchloro--HP, 0.3MPa oxygen
(dimethyl succinate+diethyl carbonate+acetic acid) 140 DEG C 32 hours 1.0/0.1/0.05/0.05/0.05)], operate with real
Apply example 1, yield 88%.
(138) from 2,4,6- trimethyl chlorobenzenes prepare 2- chloro- trimesic acids [formula (I) arrives (II), cobalt oxalate isoquinolin
TBAB 2-aza-adamantane-N- oxygen radicals, 0.1MPa air acetic acid 140 DEG C 32 hours (1.0/0.005/
0.005/0.005/0.005)], same embodiment 1, yield 35% are operated.
(139) from 3,4,5- trimethylbenzoic acids prepare 1,2,3,5- benzene tetracarboxylic acids [formula (I) arrives (II), (cuprous iodide+
Nitrification cobalt hexamine complex compound) 4- nitropyridines dodecyl sodium sulfate perchloro--HP,
0.3MPa oxygen (dimethyl succinate+diisopropyl carbonate+acetic acid) 140 DEG C 32 hours 1.0/0.05/0.05/0.05/
0.05) same embodiment 1, yield 71%], are operated.
(140) 1,2 is prepared from 2,4,6- trimethylbenzoic acids, 3,5- benzene tetracarboxylic acids [formula (I) arrives (II), (stannous chloride+
Nitrification cobalt hexamine complex compound) Isonicotinic acid dodecyl sodium sulfate perchloro--HP,
0.2MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.05/0.05/0.05/0.1)], operation is same
Embodiment 1, yield 76%.
(141) 1,2 is prepared from 2,4,6- trimethylbenzaldehydes, 3,5- benzene tetracarboxylic acids [formula (I) arrives (II), (cuprous bromide+
Sulfamic acid cobalt) 2- pyridine carboxylic acids methyl esters dodecyl sodium sulfate perchloro--HP, 0.2MPa
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 59%.
(142) from 2,4,6- trimethyls-fluorobenzene prepares 2- fluoro- 1, and [formula (I) arrives (II) to 3,5- benzenetricarboxylic acids, (stannous chloride
+ hexanitro cobalt acid sodium) acidum nicotinicum methyl esters dodecyl sodium sulfate perchloro--HP,
0.2MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], behaviour
Make with embodiment 1, yield 79%.
(143) from 2- bromo- 1,3,5- mesitylene prepare the benzenetricarboxylic acid of 2- bromines 1,3,5-, and [formula (I) arrives (II), (protochloride
Copper+hexanitro cobalt acid sodium) 4- iodine pyridines dodecyl sodium sulfate perchloro--HP, 0.2MPa oxygen
Gas (dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate with implement
Example 1, yield 27%.1H NMR(400MHz,DMSO-d6):δ=13.0 (s, 2H), 7.62 (m, 1H), 7.45 (m, 1H), 7.38
(m,1H);2.38(s,3H);13C NMR(100MHz,DMSO-d6):δ=169.0,168.3,141.1,133.7,130.8,
129.2,128.6,128.4,21.3.
(144) from 1,3,5- mesitylene preparation, 1,3,5- benzenetricarboxylic acids, [formula (I) arrives (II), (cuprous bromide+chromic acid
Cobalt) PA dodecyl sodium sulfate perchloro--HP, 0.5MPa oxygen (succinic acid
Dimethyl ester+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield
33%.
(145) from 1,3,5- mesitylene preparation, 1,3,5- benzenetricarboxylic acids, [formula (I) arrives (II), (cuprous iodide+hexanitro
Cobalt acid sodium) 2,6- dichloropyridines dodecyl sodium sulfate perchloro--HP, 1.0MPa 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 47%.
(146) from 1,3,5- mesitylene preparation, 1,3,5- benzenetricarboxylic acids, [formula (I) arrives (II), (ferric acetate+sixNickel sulfate Ammonium2- chloropyridines) dodecyl sodium sulfate perchloro--HP, 2.0MPa oxygen (succinic acid two
Methyl esters+acetic acid) 140 DEG C 32 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield
56%.
(147) from 1,3,5- mesitylene preparation, 1,3,5- benzenetricarboxylic acids, [formula (I) arrives (II), (iron chloride-hexanitro cobalt
Sour sodium) 2,4- dihydroxy-pyridines dodecyl sodium sulfate perchloro--HP, 5.0MPa 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 78%.
(148) from 1,3,5- mesitylene prepare 1,3,5- benzenetricarboxylic acids [formula (I) arrives (II), (cuprous iodide+Hexafluoro silicon Sour nickel)2,3- aminomethyl pyridines dodecyl sodium sulfate perchloro--HP, 5.0MPa 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 81%.
(149) from 1,3,5- mesitylene prepare 1,3,5- benzenetricarboxylic acids [formula (I) arrives (II), (ferric acetyl acetonade+Nickel cobalt LiMn2O4)2,4- lutidines dodecyl sodium sulfate perchloro--HP, 2.5MPa oxygen
(dimethyl succinate+acetic acid) 140 DEG C 32 hours (1.0/0.01/0.01/0.01/0.01)], operate same embodiment 1, produce
Rate 79%.
(150) from 1,3,5- mesitylene preparation, 1,3,5- benzenetricarboxylic acids, [formula (I) arrives (II), (ferric sulfate+hexanitro cobalt
Sour sodium) 2,5- dichloropyridines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 1.5MPa 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 81%.
(151) from 1,3,5- mesitylene preparation, 1,3,5- benzenetricarboxylic acids, [formula (I) arrives (II), (stannous chloride+hexanitro
Cobalt acid sodium) 2,5- dibromo pyridines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 1.0MPa oxygen (succinic acid diformazan
Ester+acetic acid) 140 DEG C 48 hours (1.0/0.01/0.02/0.02/0.02)], operate same embodiment 1, yield 83%.
(152) from 1,3,5- mesitylene preparation, 1,3,5- benzenetricarboxylic acids, [formula (I) arrives (II), (cuprous bromide+hexanitro
Cobalt acid sodium) 2,6- lutidines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 1.0MPa oxygen (succinic acid two
Methyl esters+acetic acid) 160 DEG C 48 hours (1.0/0.01/0.005/0.01/0.01)], operate same embodiment 1, yield 86%.
(153) from 1,2,3- trimethylbenzene prepare 1,2,3- benzenetricarboxylic acids [formula (I) arrives (II), (copper acetate+nickel fluoride) 2,
4- dichloropyridines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 2.0MPa oxygen (dimethyl succinate+acetic acid)
160 DEG C 48 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 66%.
1H NMR(400MHz,DMSO-d6):δ=13.0 (s, 3H), 8.06 (m, 2H), 7.63 (m, 1H);13C NMR
(100MHz,DMSO-d6):δ=168.5,166.7,136.6,132.8,129.9,128.8.
(154) from 1,2,3- trimethylbenzene prepare 1,2,3- benzenetricarboxylic acids [formula (I) arrive (II), (bromine is cuprous+hexanitro cobalt is sour
Sodium) 2,3- dichloropyridines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 4.0MPa oxygen (dimethyl succinate+
Acetic acid) 160 DEG C 48 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 89%.
(155) from 1,2,3 trimethylbenzene prepare 1,2,3- benzenetricarboxylic acids [formula (I) arrives (II), (cuprous iodide+nickel protoxide)
2,6- lutidines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 1.0MPa oxygen (dimethyl succinate+second
Acid) 160 DEG C 48 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 74%.
(156) from 1,2,3- trimethylbenzene prepare 1,2,3- benzenetricarboxylic acids [formula (I) arrives (II), (palladium+nickel sulfate) 2,
4 '-two pyridines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 1.0MPa oxygen (dimethyl succinate+acetic acid)
160 DEG C 48 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 72%.
(157) from 1,2,3,4- durene preparation, 1,2,3,4- benzene tetracarboxylic acids, [formula (I) arrives (II), (nitre of stannous chloride+six
Base cobalt acid sodium) 2,2 '-bipyridyl dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 0.5MPa oxygen (succinic acid two
Methyl esters+acetic acid) 160 DEG C 96 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield
43%.1H NMR(400MHz,DMSO-d6):δ=7.96 (s, 2H);13C NMR(100MHz,DMSO-d6):δ=167.3,
134.6,128.4.
(158) from 1,2,4,5- durene preparation, 1,2,4,5- benzene tetracarboxylic acids, [formula (I) arrives (II), (rhodium nitrate+cerous sulfate
Ammonia) 4- chloro-2-methyls pyridine dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 1.0MPa oxygen (succinic acid diformazan
Ester+acetic acid) 160 DEG C 96 hours 1.0/0.05/0.05/0.1/0.1)], operate same embodiment 1, yield 76%.1H NMR
(400MHz,DMSO-d6):δ=8.35~8.25 (m, 6H).
(159) from 1,2,3,5- durene preparation, 1,2,3,5- benzene tetracarboxylic acids, [formula (I) arrives (II), (bromination cerium+chlorine rhodium acid
Potassium) PA dodecyl sodium sulfate HP, 0.1MPa oxygen (dimethyl succinate+
Water+acetic acid) 140 DEG C 6 hours (1.0/0.005/0.005/0.005/0.005)], operate same embodiment 1, yield 42%.
(160) from mellitene prepare mellitic acid [formula (I) to (II), (manganese acetate+alum acid cerium) the chloro- 3- ethyls pyrroles of 4-
Pyridine dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 5.0MPa oxygen (dimethyl succinate+acetic acid) 240 DEG C 96
Hour (1.0/0.05/0.05/0.1/0.1)], operate same embodiment 1, LC-MS detection yield is 9%.
(161) 3,3 ' 4,4 '-tetracarboxylic benzophenone [formula (III) is prepared from double (3,4- 3,5-dimethylphenyls) ethane of 1,1-
To (IV), (rhodium hydroxide+hexanitro cobalt acid sodium) to dimethylamino naphthyridine dodecyl sodium sulfate peroxosulphuric hydrogen potassium it is compound
Salt, 0.2MPa oxygen (dimethyl succinate+acetic acid) 200 DEG C 96 hours (1.0/0.005/0.005/0.005/
0.005) same embodiment 1, yield 68%], are operated.
(162) from double (3,4- 3,5-dimethylphenyls) methanes of 1,1- for 3,3 ' 4,4 '-tetracarboxylic benzophenone [formula (III)
To (IV), (rhodium oxide+acetylacetone,2,4-pentanedione cerium) 4,4- bipyridyls dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt,
0.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 96 hours 1.0/0.05/0.05/0.05/0.05)], operation is same
Embodiment 1, yield 74%.
(163) from 3,3 ', 4,4 '-tetramethyl benzophenone, 3,3 ' 4,4 '-tetracarboxylic of preparation benzophenone, [formula (III) arrives
(IV), (cobalt acetate+stannous chloride) 2- methoxypyridines dodecyl sodium sulfate peroxosulphuric hydrogen potassium complex salt, 0.5MPa
Oxygen (dimethyl succinate+acetic acid) 160 DEG C 96 hours (1.0/0.005/0.005/0.005/0.005)], operate with real
Apply example 1, yield 76%.
(164) 3,3 ' 4,4 '-tetracarboxylic benzophenone [formula (III) is prepared from double (3,4- 3,5-dimethylphenyls) heptane of 1,1-
To (IV), (five ruthenium hydrochloride ammoniums+isooctyl acid cerium] 2- Yi Yangjibiding Shi Erwanjihuangsuanna peroxosulphuric hydrogen potassium complex salts,
0.5MPa oxygen (dimethyl succinate+acetic acid) 160 DEG C 96 hours (1.0/0.06/0.06/0.03/0.03)], operation is same
Embodiment 1, yield 64%.
(165) from double (3,4- 3,5-dimethylphenyls) butanes of 1,1- for 3,3 ' 4,4 '-tetracarboxylic benzophenone [formula (III)
To (IV), (hexachloro-potassium ruthenate+copper sulphate) 2- benzoylpyridines dodecyl sodium sulfate 2,2,6,6- tetramethyl piperidine nitrogen oxygen
Compound, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 96 hours (1.0/0.02/0.02/0.05/0.05)],
Operation is the same as embodiment 1, yield 63%.
(166) 3,3 ' 4,4 '-tetracarboxylic benzophenone is prepared from double (3,4- the 3,5-dimethylphenyls) -2- methyl-propans of 1,1-
[formula (III) arrives (IV), (ruthenium-oxide+copper bromide) 2,6- lutidines TBAB 2,2,6,6- tetramethyl piperidines
Nitrogen oxides, 1.0MPa oxygen (dimethyl succinate+dimethyl adipate+acetic acid) 140 DEG C 96 hours (1.0/0.05/
0.05/0.05/0.05)], same embodiment 1, yield 77% are operated.
(167) 3,3 ' 4,4 '-tetracarboxylic benzophenone [formula (III) is prepared from double (3,4- 3,5-dimethylphenyls) ethanol of 1,1-
To (IV), (cerium fluoride+rhodium acetate) 2, the tetramethyl piperidine nitrogen oxidations of 3- Bi Dingerjiasuan Si Dingjixiuhuaans 2,2,6,6-
Thing, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 96 hours (1.0/0.02/0.04/0.05/0.05)], behaviour
Make with embodiment 1, yield 56%.
(168) from 2,2 ', 4,4 '-tetramethyl benzophenone, 2,2 ', 4,4 "-tetracarboxylic of preparation benzophenone, [formula (III) arrives
(IV), (molybdenum oxide cobalt+acetonitrile palladium chloride) 2, dipicolimic acid 2 dimethyl ester TBAB 2,2,6,6- tetramethyl piperazines
Pyridine nitrogen oxides, 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 96 hours (1.0/0.005/0.005/
0.005/0.005)], same embodiment 1, yield 61% are operated.
(169) 3 are prepared from 3,3 '-dimethyl benzophenone, [formula (III) arrives (IV) to 3 '-benzophenonedicarboxylic acid, (phosphoric acid
Cobalt ammonium+tetramethyl piperidine the nitrogen oxides of cuprous iodide) 4- Xiao Jibiding Si Dingjixiuhuaans 2,2,6,6-, 1.0MPa Yang Qis
(dimethyl succinate+dichloro-benzenes+acetic acid) 140 DEG C 96 hours (1.0/0.005/0.005/0.005/0.005)], operation is same
Embodiment 1, yield 72%.
(170) 4 are prepared from 4,4 '-dimethyl benzophenone, [formula (III) arrives (IV) to 4 '-benzophenonedicarboxylic acid, (acetic acid
Cobalt+cerous nitrate+nickel nitrate) (PA+diisopropyl ester amber acid) TBAB 2,2,6,6- tetramethyl piperidines
Nitrogen oxides, 1.0MPa oxygen (dimethyl succinate+dichloro-benzenes+acetic acid) 140 DEG C 96 hours (1.0/0.005/0.005/
0.005/0.005)], same embodiment 1, yield 63% are operated.
(171) from double (3,4, -3,5-dimethylphenyl) ethers prepare double (3,4,-dicarboxyphenyi) ethers [formula (III) arrives (IV),
(cobalt acetate+nickel sulfate) (4- pyridones+dibutyl succinate) TBAB 2,2,6,6- tetramethyl piperidine nitrogen oxygen
Compound, 1.0MPa oxygen (Dimethyl 1,7-heptanedioate+acetic acid) 140 DEG C 96 hours (1.0/0.005/0.005/0.005/
0.005) same embodiment 1, yield 37%], are operated.
(172) from double (3,4, -3,5-dimethylphenyl) ethers prepare double (3,4,-dicarboxyphenyi) ethers [formula (III) arrives (IV),
(cobalt aluminate+nickel acetate) 1, the tetramethyl piperidine nitrogen oxides of 3- diphenylprop Er Tong Si Dingjixiuhuaans 2,2,6,6-,
1.0MPa oxygen (dimethyl succinate+dimethyl glutarate+acetic acid) 140 DEG C 96 hours (1.0/0.1/0.1/0.1/
0.1) same embodiment 1, yield 53%], are operated.
(173) from double (3,4- dimethyl benzene) sulfones prepare 3,3 ', 4,4 ' ,-diphenyl sulfone tetracid [formula (III) arrives (IV),
(cobalt-chromate+nickel chloride) 5, the tetramethyl piperidine nitrogen oxides of 6- last of the ten Heavenly stems Er Tong Si Dingjixiuhuaans 2,2,6,6-, 1.0MPa oxygen
Gas (dimethyl succinate+acetic acid) 140 DEG C 96 hours (1.0/0.02/0.02/0.02/0.02)], operate same embodiment 1,
Yield 32%.
(174) from double (3,4- dimethyl benzene) sulfones prepare 3,3 ', 4,4 ' ,-diphenyl sulfone tetracid [formula (III) arrives (IV),
(palladium trifluoroacetate+trifluoromethanesulfonic acid cerium) (4- pyridone+2,3- diacetyl) TBAB 2,2,6,6- tetramethyls
Piperidines nitrogen oxides, 1.0MPa oxygen (dimethyl succinate+dichloro-benzenes+acetic acid) 140 DEG C 96 hours (1.0/0.3/0.3/
0.3/0.3)], same embodiment 1, yield 68% are operated.
(175) double (3,4- dicarboxyphenyis) hexafluoros third of 2,2- are prepared from double (3,4- 3,5-dimethylphenyls) HFC-236fas of 2,2-
Alkane [formula (III) arrives (IV), (rhodium nitrate+cuprous iodide) dimethyl oxalate calcium hypochlorite 4- carboxy-Ns-hydroxyl O-phthalic
Acid imide, 1.0MPa oxygen (dimethyl succinate+chlorobenzene+acetic acid) 140 DEG C 96 hours (1.0/0.2/0.2/0.2/
0.2) same embodiment 1, yield 67%], are operated.
(176) double (3,4- dicarboxyphenyis) propane [formulas of 2,2- are prepared from double (3,4- 3,5-dimethylphenyls) propane of 2,2-
(III) arrive (IV), (palladium+acetylacetone cobalt) (4- pyridone+N, N '-dimethyl succinamide) calcium hypochlorite 4-
Carboxy-N-hydroxyphthalimide, 0.5MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C 96 hours 1.0/
0.1/0.1/0.1/0.1)], same embodiment 1, yield 72% are operated.
(177) double (3,4- dicarboxyphenyis) hexafluoros third of 2,2- are prepared from double (3,4- 3,5-dimethylphenyls) HFC-236fas of 2,2-
Alkane [formula (III) arrives (IV), (acetylacetone cobalt+chlorine rhodium acid potassium) (4- pyridones+N, N '-di-t-butyl adipamide) time
Calcium chlorate 4- carboxy-Ns-hydroxyphthalimide 1.0MPa oxygen (dimethyl succinate+acetic acid) 140 DEG C it is 96 small
When 1.0/0.1/0.1/0.1/0.1)], operate same embodiment 1, yield 71%.Reaction terminates, and solvent is recovered by filtration, then add
Acetic acid, available for next time with system reaction.
(178) double (3,4- dicarboxyphenyis) hexafluoros third of 2,2- are prepared from double (3,4- 3,5-dimethylphenyls) HFC-236fas of 2,2-
Alkane [formula (III) arrives (IV), (acetylacetone cobalt+chlorine rhodium acid potassium) (4- pyridones+dodecanedioic acid) calcium hypochlorite 4- carboxylics
Base-HP, 1.0MPa oxygen (dimethyl succinate+acetic acid) (recovery 1) 140 DEG C it is 96 small
When (1.0/0.1/0.1/0.1/0.1)], operate same embodiment 1, yield 67%.Reaction terminates, and solvent is recovered by filtration, then add
Acetic acid, available for next time with system reaction.
(179) double (3,4- dicarboxyphenyis) hexafluoros third of 2,2- are prepared from double (3,4- 3,5-dimethylphenyls) HFC-236fas of 2,2-
Alkane [formula (III) arrives (IV), (acetylacetone cobalt+chlorine rhodium acid potassium) (4- pyridones+Dimethyl 1,7-heptanedioate) calcium hypochlorite 4-
Carboxy-N-hydroxyphthalimide, 1.0MPa oxygen (dimethyl succinate+acetic acid) (recovery 2) 140 DEG C 96
Hour (1.0/0.1/0.1/0.1/0.1)], operate same embodiment 1, yield 63%.Reaction terminates, and solvent is recovered by filtration, then mend
Add acetic acid, available for next time with system reaction.
(180) double (3,4- dicarboxyphenyis) hexafluoros third of 2,2- are prepared from double (3,4- 3,5-dimethylphenyls) HFC-236fas of 2,2-
Alkane [formula (III) arrives (IV), (acetylacetone cobalt+chlorine rhodium acid potassium) (4- pyridones+Dimethyl 1,7-heptanedioate) calcium hypochlorite 4-
Carboxy-N-hydroxyphthalimide, 1.0MPa oxygen (dimethyl succinate+acetic acid) (recovery 3) 140 DEG C 96
Hour (1.0/0.1/0.1/0.1/0.1)], operate same embodiment 1, yield 62%.Reaction terminates, and solvent is recovered by filtration, then mend
Add acetic acid, available for next time with system reaction.
Above example is easy to operate, and yield is higher.That is realized prepares benzene polycarboxylic acid class by multi-methyl benzene analog derivative
Derivative, the compounds such as acid anhydrides can be further prepared into, applied to the synthesis of medicine intermediate and the synthesis of material, had 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 (7)
- A kind of 1. method for preparing the more formic acid analog derivatives of aromatic hydrocarbons, it is characterised in thatMethods described is method (a), including step:In atent solvent, under the catalysis of metal salt and part, using or as co-catalyst and making without using additive A By the use of or without using additive B as in the case of co-catalyst, by the how methyl substituted aromatic hydrocarbons analog derivative shown in formula (I) with Oxidant reacts, so as to obtain the more formic acid analog derivatives of aromatic hydrocarbons shown in formula (II);It is above-mentioned it is various in, Ar1It is phenyl ring;Ar2It is phenyl ring;N=4;Wherein, the metal salt is selected from the group:Mantoquita, molysite, cobalt salt, manganese salt, cerium salt, ruthenium salt, nickel salt, palladium salt, rhodium salt or its Combination;The part is selected from the group:Structure formula (V), (VI), substituted pyridines, quinoline, isoquinolin, bipyridyl, Phen or its Combination:In formula (V), R1For hydrogen, methyl, isopropyl, isobutyl group, sec-butyl, tertiary fourth, cyclohexyl, benzyl, 2- carboxy ethyls, 2- carboxylics Ylmethyl or phenyl, R2For methyl, ethyl, isopropyl, the tert-butyl group, methoxyl group, benzyloxy or phenyl;In formula (VI), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dialkyl aminos Base, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dialkyl amidos, k 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, zirconium oxide, oxidation Lanthanum, samarium oxide, lanthanum nitrate, scandium nitrate, zirconium nitrate, samaric nitrate, lanthanum sulfate, scandium sulfate, zirconium sulfate, samarium sulphate, zirconyl acetate, second Sour zirconium, molybdenum oxide, acetic acid molybdenum, molybdenum trisulfate, acetic acid tungsten, tungsten oxide, acetic acid hafnium, hafnium oxide, acetic acid praseodymium, praseodymium oxide, hexafluoro zirconate Potassium, zirconyl nitrate, zirconium oxycarbonate, zirconium carbonate, C2-C12 alkyl acid sodium, C2-C12 alkyl acid potassium, dodecyl sodium sulfonate Sodium, neopelex, TBAB, tetrabutylammonium chloride, tri-methyl benzyl ammonium bromide, trimethyl benzyl chlorination Ammonium or its combination;Wherein, the cation of the metal salt I is lithium, sodium, potassium, calcium or ammonium, and the anion of the metal salt I is sulphur Acid group, inferior sulfate radical, nitrate anion, nitrite anions, phosphate radical, hydrogen phosphate, dihydrogen phosphate, orthophosphite, perchlorate or 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 or its combination, or more two esters solvents and chlorobenzene, dichloro-benzenes, Water, C2~C6 aliphatic acid, R5CO2R6The mixed solvent of esters solvent, wherein R5For C1~C5 alkyl, R6For C1~C6 alkane Base;Wherein, two esters that the fat diacid that two esters solvent is C1~C12 is formed with methanol, ethanol, propyl alcohol, isopropanol Solvent;The oxidant is selected from the group:After 30~70% concentration hydrogen peroxide, 0.1~10MPa oxygen, air or nitrogen dilution Oxygen or air;Reaction temperature is 40 DEG C~250 DEG C;Reaction time is 1~120 hour.
- 2. the method as described in claim 1, it is characterised in thatThe part is selected from the group:Structure formula (V), (VI), substituted pyridines, quinoline, isoquinolin, bipyridyl, Phen or its Combination:In formula (V), R1For hydrogen, methyl, isopropyl, isobutyl group, sec-butyl, tertiary fourth, cyclohexyl, benzyl, 2- carboxy ethyls, 2- carboxylics Ylmethyl or phenyl, R2For methyl, ethyl, isopropyl, the tert-butyl group, methoxyl group, benzyloxy or phenyl;In formula (VI), R3For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dialkyl aminos Base, R4For C1-C4 alkyl, phenyl, hydroxyl, C1-C4 alkoxies, C1-C4 alkyl aminos, C1-C3 dialkyl amidos, k 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.
- 3. the method as described in claim 1, it is characterised in thatThe metal salt is selected from the group:Mantoquita, molysite, cobalt salt, manganese salt, cerium salt, ruthenium salt, nickel salt, palladium salt, rhodium salt or its combination; It is preferred that the metal salt is selected from the group:Copper acetate, copper chloride, copper bromide, copper sulphate, stannous chloride, cuprous bromide, iodate Cuprous, ferric acetate, iron chloride, ferric acetyl acetonade, ferric sulfate, cobalt acetate, cobalt chloride, cobaltous fluoride, cobaltous bromide, lithium cobalt oxide, hydrogen Cobalt oxide, 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, nickel chloride, nickel fluoride, Nickel acetate, nickel sulfate, nickel nitrate, nickel protoxide, hexafluorosilicic acid nickel, ammonium nickel sulfate, nickle cobalt lithium manganate, palladium, trifluoroacetic acid Palladium, acetonitrile palladium chloride, rhodium acetate, radium chloride, rhodium hydroxide, rhodium oxide, rhodium sulfate, rhodium nitrate, chlorine rhodium acid potassium or its combination; Again goodly, the metal salt can be selected from the group:Mantoquita, molysite, cobalt salt, cerium salt or its combination;More preferably, the metal salt It can be selected from the group:Copper acetate, ferric acetate, ferric acetyl acetonade, ferric sulfate, cobalt acetate, 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, cerous acetate, 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, three Fluorine methanesulfonic acid cerium or its combination;And/orWhen using additive A, the additive A is selected from the group one or more:C2-C12 alkyl acid sodium, C2-C12 alkane Base acid potassium, dodecyl sodium sulfate, neopelex, TBAB, tetrabutylammonium chloride, trimethyl benzyl bromine Change ammonium, trimethyl benzyl ammonia chloride or its combination;And/orWhen using additive B, the additive B is selected from the group one or more:2-aza-adamantane-N- oxygen radicals, 2, 2,6,6- tetramethyl piperidines nitrogen oxides, 2,2,6,6- tetramethyl -4- methoxy piperides nitrogen oxides, 2,2,6,6- tetramethyl piperazines Pyridine -4- ketone -1- oxygen radicals, 2,2,6,6- tetramethyl -4- acetylaminohydroxyphenylarsonic acid piperidines nitrogen oxides, sodium peroxydisulfate, potassium peroxydisulfate, SODIUM PERCARBONATE, peroxosulphuric hydrogen potassium complex salt, sodium perborate, N- hydroxyls dicarboximide or its combination;Wherein, the N- hydroxyls Dicarboximide can be:HP, perchloro--HP, 4- carboxy-Ns-hydroxyl The fluoro- HP of base phthalimide, 4-, 4- methyl-N-hydroxies phthalimide, 2- are fluoro- The equal formyl two of benzene four of HP, 4- methoxycarbonyl groups-HP, N, N '-dihydroxy Imines or n-hydroxysuccinimide, 1,2- hexamethylene dicarboximides.
- 4. the method as described in claim 1, it is characterised in thatThe atent solvent is selected from the group:Two esters solvents being selected from the group:Dimethyl succinate, diethyl succinate, penta 2 Dimethyl phthalate, ethyl glutarate, dimethyl adipate, diethylene adipate or its combination, or more two esters solvents and chlorine Benzene, acetic acid, propionic acid, butyric acid, isobutyric acid, caproic acid, R5CO2R6The mixed solvent of esters solvent, wherein R5For C1~C5 alkyl, R6 For C1~C6 alkyl;And/orThe oxidant is selected from the group:30~70% concentration hydrogen peroxide, after 0.1~10MPa oxygen, air or nitrogen dilution Oxygen or air;And/orReaction temperature is 40 DEG C~250 DEG C;And/orReaction time is 1~120 hour.
- 5. the method as described in claim 1, it is characterised in thatWhen being calculated with mol ratio, (I)/metal salt/part/additive A/additive B be 1.0/0.001~0.2/0~0.3/0~ 0.3/0~0.3;It is preferred that when being calculated with mol ratio, (I)/metal salt/part/additive A/additive B be 1.0/0.005~ 0.1/0.005~0.01/0.005~0.01/0.005~0.01.
- 6. the method as described in claim 1, it is characterised in that the oxidant is selected from the group:0.1~10MPa oxygen, sky Oxygen or air after gas or nitrogen dilution;It is preferred that the oxidant is that 0.1~2.5MPa oxygen, air or nitrogen are dilute Oxygen or air after releasing;More preferably, the oxidant is 0.1~0.5MPa oxygen or air.
- 7. the method as described in claim 1, it is characterised in thatReaction temperature is 40 DEG C~250 DEG C;It is preferred that reaction temperature is 80~200 DEG C;More preferably, reaction temperature be 100~ 160℃;And/orReaction time is 1~120 hour;It is preferred that the reaction time is 5~72 hours;More preferably, the reaction time is 4~12 small When.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610656820.5A CN107698438A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610656820.5A CN107698438A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
CN201610648027.0A CN107698436A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610648027.0A Division CN107698436A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107698438A true CN107698438A (en) | 2018-02-16 |
Family
ID=61168921
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610656255.2A Pending CN107698437A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
CN201610656866.7A Pending CN107698445A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
CN201610656820.5A Pending CN107698438A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
CN201610648027.0A Pending CN107698436A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610656255.2A Pending CN107698437A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
CN201610656866.7A Pending CN107698445A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610648027.0A Pending CN107698436A (en) | 2016-08-09 | 2016-08-09 | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons |
Country Status (1)
Country | Link |
---|---|
CN (4) | CN107698437A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114105755A (en) * | 2021-11-12 | 2022-03-01 | 浙江工业大学 | Preparation method of 2-methoxy-6-methylbenzoic acid |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108484381A (en) * | 2018-03-08 | 2018-09-04 | 上海应用技术大学 | A kind of method that Anderson types polyacid catalysis oxidation prepares 4,4`- oxydibenzoic acids |
CN108276275A (en) * | 2018-03-08 | 2018-07-13 | 上海应用技术大学 | A kind of method that metal oxide oxidation catalyst oxidation prepares 4,4`- oxydibenzoic acids |
CN108383710A (en) * | 2018-03-08 | 2018-08-10 | 上海应用技术大学 | A kind of method that Anderson types polyacid catalysis oxidation prepares benzoic acid |
CN108276273A (en) * | 2018-03-08 | 2018-07-13 | 上海应用技术大学 | A kind of method that metal oxide oxidation catalyst oxidation prepares benzoic acid |
CN108558804B (en) * | 2018-05-18 | 2020-05-12 | 宁夏大学 | Synthetic method of 3-fluorophthalic acid |
CN109942404A (en) * | 2019-01-10 | 2019-06-28 | 上海繁德生物科技有限公司 | A kind of method that polyacid catalysis oxidation prepares phthalic acid |
CN109928944B (en) * | 2019-04-01 | 2023-02-28 | 自贡中天胜新材料科技有限公司 | Preparation method of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride |
CN110143862B (en) * | 2019-06-11 | 2022-04-22 | 黄山华惠科技有限公司 | Method for preparing trimesic acid/trimellitic acid by liquid phase oxidation method |
CN110343257B (en) * | 2019-07-16 | 2021-11-09 | 三峡大学 | Polychlorinated cobalt-based composite material, preparation method and application thereof |
EP3838883B1 (en) * | 2019-12-16 | 2023-07-12 | Evonik Fibres GmbH | Method for oxidizing a 1,1-bis-(3,4-dimethylphenyl)-alkane to 3,3',4,4'-benzophenone tetracarboxylic acid |
CN111018695A (en) * | 2019-12-26 | 2020-04-17 | 菏泽职业学院 | Preparation method of tritenzoic acid |
CN111333601A (en) * | 2020-05-21 | 2020-06-26 | 山东冠森高分子材料科技股份有限公司 | Method for preparing 4, 4' - (hexafluoroisopropenyl) diphthalic anhydride |
CN113372553A (en) * | 2021-05-27 | 2021-09-10 | 江苏胜帆电子科技有限公司 | Low-melting-point circuit board substrate and preparation method thereof |
CN114605363A (en) * | 2022-03-11 | 2022-06-10 | 大连新阳光材料科技有限公司 | Preparation method of 3,3',4,4' -benzophenone tetracarboxylic dianhydride |
CN114656351B (en) * | 2022-05-24 | 2022-08-26 | 河北海力香料股份有限公司 | Method for treating 4-chlorophthalic acid or monosodium salt production wastewater thereof |
CN115010592B (en) * | 2022-07-07 | 2023-06-27 | 浙江大学 | Preparation method of 4-bromophthalic acid |
CN115160271A (en) * | 2022-07-28 | 2022-10-11 | 自贡中天胜新材料科技有限公司 | Preparation method of 3,3', 4' -benzophenonetetracarboxylic dianhydride |
CN115197060B (en) * | 2022-08-19 | 2024-03-29 | 山东京博石油化工有限公司 | Method for preparing phthalic acid |
CN117384028A (en) * | 2023-10-20 | 2024-01-12 | 济南久隆医药科技有限公司 | Synthesis method of 4-acetyl-1-naphthoic acid |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1865214A (en) * | 2006-06-20 | 2006-11-22 | 扬子石油化工股份有限公司 | Method for producing aromatic carboxylic acid using nitrogen oxide as catalytic additive |
CN102066306A (en) * | 2008-06-11 | 2011-05-18 | 大赛璐化学工业株式会社 | Aromatic polycarboxylic acid manufacturing method |
CN102059141A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic carboxylic acid and application thereof |
CN102060686A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Method for producing aromatic carboxylic acid by using nitrogen heterocyclic ring compound as oxidation accelerator |
CN102099324A (en) * | 2008-05-23 | 2011-06-15 | 大赛璐化学工业株式会社 | Process for production of aromatic carboxylic acids |
CN102516070A (en) * | 2011-12-06 | 2012-06-27 | 济南大学 | Method for preparing 2,2-bi(4-carboxylphenyl)hexafluoropropane under novel catalytic system |
-
2016
- 2016-08-09 CN CN201610656255.2A patent/CN107698437A/en active Pending
- 2016-08-09 CN CN201610656866.7A patent/CN107698445A/en active Pending
- 2016-08-09 CN CN201610656820.5A patent/CN107698438A/en active Pending
- 2016-08-09 CN CN201610648027.0A patent/CN107698436A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1865214A (en) * | 2006-06-20 | 2006-11-22 | 扬子石油化工股份有限公司 | Method for producing aromatic carboxylic acid using nitrogen oxide as catalytic additive |
CN102099324A (en) * | 2008-05-23 | 2011-06-15 | 大赛璐化学工业株式会社 | Process for production of aromatic carboxylic acids |
CN102066306A (en) * | 2008-06-11 | 2011-05-18 | 大赛璐化学工业株式会社 | Aromatic polycarboxylic acid manufacturing method |
CN102059141A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing aromatic carboxylic acid and application thereof |
CN102060686A (en) * | 2009-11-18 | 2011-05-18 | 中国科学院大连化学物理研究所 | Method for producing aromatic carboxylic acid by using nitrogen heterocyclic ring compound as oxidation accelerator |
CN102516070A (en) * | 2011-12-06 | 2012-06-27 | 济南大学 | Method for preparing 2,2-bi(4-carboxylphenyl)hexafluoropropane under novel catalytic system |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114105755A (en) * | 2021-11-12 | 2022-03-01 | 浙江工业大学 | Preparation method of 2-methoxy-6-methylbenzoic acid |
Also Published As
Publication number | Publication date |
---|---|
CN107698436A (en) | 2018-02-16 |
CN107698437A (en) | 2018-02-16 |
CN107698445A (en) | 2018-02-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107698438A (en) | A kind of method for preparing the more formic acid analog derivatives of aromatic hydrocarbons | |
Loukopoulos et al. | Recent advances of one-dimensional coordination polymers as catalysts | |
Karabach et al. | Self-assembled 3D heterometallic CuII/FeII coordination polymers with octahedral net skeletons: Structural features, molecular magnetism, thermal and oxidation catalytic properties | |
CN105121399B (en) | The synthetic method of 1-Phenylethanone. | |
Tabey et al. | Cross-dehydrogenative N–N couplings | |
CN104193600A (en) | Method for preparing aldehyde or ketone from air oxidized alcohol by using aluminum oxide as co-catalyst | |
CN106565600A (en) | Deuterated aza aromatic compound and synthesis method thereof | |
CN107759460A (en) | A kind of method for preparing the more acid monomers of polyphenyls | |
CN104492488A (en) | Double-ligand zinc complex catalyst and application thereof | |
Babjak et al. | Iron pentacarbonyl in alkoxy-and aminocarbonylation of aromatic halides | |
WO2018028505A1 (en) | Catalyst for synthesizing dimethyl carbonate by oxidative carbonylation of liquid phase methanol and method | |
Li et al. | Three new MOFs induced by organic linker coordination modes: gas sorption, luminescence, and magnetic properties | |
Li et al. | A novel helical chain zinc (II) coordination polymer derived from both ferrocenecarboxylato and bibenzimidazolyl ligands: synthesis, crystal structure and properties | |
Petit et al. | Lanthanide (III) squarates 1. Five families of compounds obtained from aqueous solutions in an open system. Crystal structure and thermal behaviour | |
CN100486951C (en) | Process of producing aromatic carboxylic acid with diamine compound as catalyst | |
Zou et al. | Two transition metal coordination polymers constructed from 1, 4-naphthalenedicarboxylate and N/O-donor auxiliary ligands: Syntheses, structures and magnetic property | |
CN104151133B (en) | A kind of method of methylbenzene selective preparing benzaldehyde by oxidizing | |
Hazari et al. | 1D lead (II) coordination chains with carboxylate containing ligands. A rare example of polyrotaxane 1D→ 1D interpenetrated coordination polymer | |
CN107413386B (en) | Catalyst for synthesizing methylal by methanol liquid-phase one-step oxidation, and preparation method and use method thereof | |
Li et al. | A two-dimensional zinc Phosphonate: Synthesis, structure and photoluminescence properties | |
CN102807469A (en) | Method for preparing tertiary butanol by oxidizing iso-butane | |
Zhang et al. | Seven new complexes based on various coordination modes of bifunctional ligand: Luminescent sensing and magnetic properties | |
Jiang et al. | Two new Nickel (II) complexes constructed by 2-carboxymethylsulfanyl nicotinic acid with different N-containing auxiliary ligands | |
Huan et al. | Syntheses, Structures, and Catalytic Properties of Two 2D Manganese (II) Coordination Polymers Containing Flexible Bis (benzimidazole) Ligands | |
CN104098595A (en) | Dual-core cupriferous three-dimensional polymer and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180216 |