CN102020622A - Method for preparing 2,3,3',4'-biphenyltetracarboxylic di-anhydride - Google Patents
Method for preparing 2,3,3',4'-biphenyltetracarboxylic di-anhydride Download PDFInfo
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- 0 *c1ccc(CI)c(*)c1 Chemical compound *c1ccc(CI)c(*)c1 0.000 description 3
- XDWABIXSGFIDAC-UHFFFAOYSA-N CCc(cc1)c(C)cc1-c(cccc1I)c1[IH]CC Chemical compound CCc(cc1)c(C)cc1-c(cccc1I)c1[IH]CC XDWABIXSGFIDAC-UHFFFAOYSA-N 0.000 description 1
- NBWYBNAJKZMTHK-UHFFFAOYSA-N N=C(c1c2cccc1-c(cc1C(N3)=[Cl-])ccc1C3=[ClH])[Cl-]C2=[ClH] Chemical compound N=C(c1c2cccc1-c(cc1C(N3)=[Cl-])ccc1C3=[ClH])[Cl-]C2=[ClH] NBWYBNAJKZMTHK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a method for preparing 2,3,3',4'-biphenyltetracarboxylic di-anhydride shown in a formula I. The method comprises the following steps: a) mixing a compound shown in a formula II and a compound shown in a formula III based on the molar ratio of (1-3):(1-3) to obtain a first mixture; mixing the first mixture, catalyst, ligand and reductive agent based on the molar ratio of 1:(0.01-0.5):(0.01-5):(0.5-6) in a first solvent; carrying out coupling reaction to obtain a compound shown in a formula IV; b) mixing the compound shown in the formula IV and the oxidant based on the molar ratio of 1:(4-20) in the second solvent, and carrying out oxidizing reaction to obtain a compound shown in a formula V; and c) carrying out dehydration reaction on the compound shown in the formula V to obtain the compound shown in the formula I, wherein, the X in the formula II and the X in the formula III are respectively dehydration, bromine or iodine. The preparation method provided by the invention has the advantages of simple process and moderate condition, and is suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to the compound field, be specifically related to a kind of 2,3,3 ', 4 '-the bibenzene tetracarboxylic dianhydride preparation method.
Background technology
Bibenzene tetracarboxylic dianhydride (BPDA) is the important monomer of synthetic heat-proof macromolecule material polyimide (PI).There are three kinds of isomer in bibenzene tetracarboxylic dianhydride.Promptly 3,4,3 ', 4 '-bibenzene tetracarboxylic dianhydride (s-BPDA), 2,3,2 ', 3 '-bibenzene tetracarboxylic dianhydride (i-BPDA) and 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride (a-BPDA).Wherein, have 2,3,3 of unsymmetric structure ', 4 '-bibenzene tetracarboxylic dianhydride (a-BPDA) is suc as formula shown in the I, is the important source material of synthesising different structure polyimide, has been subjected to extensive concern in recent years.But,, often need cross-coupling to obtain, and cross-coupling to use organometallic reagent, makes raw material generation linked reaction under precious metal palladium catalysis, much is the operation of anhydrous and oxygen-free because the biphenyl dianhydride of this isomery has asymmetrical structure.Therefore synthesizing of the bibenzene tetracarboxylic dianhydride of isomery become one of the difficult point problem in synthesising different structure polyimide field.The patent of report and document are seldom at present.
Formula I.
Phthalic ester in the presence of the catalyst acetic acid palladium, can coupling synthetic 3,4,3 ', 4 '-bibenzene tetracarboxylic dianhydride, in this reaction process, can produce by product 2,3 simultaneously, 3 ', 4 '-bibenzene tetracarboxylic dianhydride.But, utilize this method preparation 2,3,3 ', 4 '-the bibenzene tetracarboxylic dianhydride overall yield is very low, poor selectivity, simultaneously, the isomer separation complexity.At this problem, in some patents, invented the part of multiple special construction, wish to improve 2,3,3 ', 4 '-selectivity of bibenzene tetracarboxylic dianhydride, for example, US 7271281, US 6914152 etc., still, in these patents, 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride overall yield is still very low, general less than 10%.
U.S. Pat 7271281 reported the oxidative coupling reaction of the phthalic ester under the rhodium catalysis can optionally obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, carry out but be to use metal rhodium to react as catalyst, cost an arm and a leg, and yield is very low, less than 6%.
That Chinese patent CN200810051688 discloses is a kind of 2,3,3 ', 4 '-preparation method of bibenzene tetracarboxylic dianhydride and derivative thereof, with two kinds of phthalic ester or phthalic imidines that the chloro position is different, cross-coupling reaction obtains 2 under nickel catalysis, 3,3 ', 4 '-biphenyl dianhydride.With respect to other coupling method of palladium, rhodium noble metal catalyst etc., yield is brought up to more than 80% from less than 10%; Raw materials cost reduces more than 30%.The operational path of Chinese patent 200810051688 is:
Wherein X is F, Cl, Br, I.
Though this operational path has been avoided precious metal catalyst, and operation is simple, the yield height; But, increase the protection of halobenzoyl anhydride in the reaction scheme and removed the reaction process of protection, thereby increased the complicacy of technology, reduced overall yield, improved cost.
Summary of the invention
That the technical problem to be solved in the present invention is to provide is a kind of 2,3,3 ', 4 '-the bibenzene tetracarboxylic dianhydride preparation method, technology is simple, mild condition, preparation is easily.
In order to overcome the above problems, the invention provides 2,3,3 shown in a kind of formula I ', 4 '-preparation method of bibenzene tetracarboxylic dianhydride, comprising:
A is to mix obtain first mixture at 1～3: 1～3 with compound shown in the formula II and the compound shown in the formula III in molar ratio, with described first mixture and catalyzer, part, reductive agent is 1: 0.01～0.5: 0.01～5: 0.5～6 to be blended in first solvent in molar ratio, carries out linked reaction and obtains the described compound of formula IV;
B) be 1: 4～20 to be blended in second solvent in molar ratio with the compound shown in the formula IV and oxygenant, oxidizing reaction takes place, obtain the described compound of formula V;
C) compound shown in the formula V is carried out dehydration reaction, obtain the compound shown in the formula I.
X in formula II and the formula III is respectively chlorine, bromine or iodine.
Preferably, the catalyzer in the step a) is the hydrate of nickel halogenide or nickel halogenide.
Preferably, described catalyzer is anhydrous chlorides of rase nickel or anhydrous nickelous bromide.
Preferably, the part in the step a) be trialkyl phosphine, triaryl phosphine or 2,2 '-in dipyridyl and the derivative thereof one or more.
Preferably, described first solvent is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, tetramethylene sulfone, tetrahydrofuran (THF), dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, one or more in methyl tertiary butyl ether and the acetonitrile.
Preferably, described reductive agent is a zinc.
Preferably, step a) comprises also that in described first solvent adding with first mixture is 0～1: 1 catalyst aid in molar ratio, described catalyst aid is alkali-metal bromide, tetraalkyl brometo de amonio, tetraalkyl ammonium iodide, and described alkyl is the alkyl of 1～12 carbon.
Preferably, described oxygenant is potassium permanganate, potassium bichromate, sodium dichromate 99 or nitric acid.
Preferably, b) be specially:
B11) be 1: 4～20 to be dissolved in second solvent in molar ratio with the compound shown in the formula IV and potassium permanganate, potassium bichromate or sodium dichromate 99, obtain mixing solutions; Described second solvent is that pyridine and water are the solution that 1～3: 1～3 mixing obtains by mass ratio;
B12) with b11) mixing solutions that obtains is heated to and carries out oxidizing reaction under 80 ℃～120 ℃ and obtain the compound shown in the formula V.
Preferably, b) be specially:
B21) with the compound shown in the formula IV and nitric acid be in molar ratio 1: 4～20 mixed dissolutions in second solvent, obtain mixing solutions; Described second solvent is a water, and the concentration of nitric acid in the described mixing solutions is 10wt%～30wt%;
B22) mixing solutions that b21 is obtained is heated to and carries out oxidizing reaction under 80 ℃～120 ℃ and obtain the compound shown in the formula V.
The invention provides 2,3,3 ', 4 '-the bibenzene tetracarboxylic dianhydride preparation method, 3-halo o-Xylol and 4-halo o-Xylol are carried out linked reaction under nickel catalyzator catalysis, obtain 2,3,3 ', 4 '-tetramethyl biphenyl, then with described 2,3,3 ', 4 '-tetramethyl biphenyl is oxidized to 2,3,3 ', 4 '-bibenzene tetracarboxylic, at last with described 2,3,3 ', 4 '-bibenzene tetracarboxylic dehydration obtains bibenzene tetracarboxylic dianhydride.The present invention is earlier with 3-halo o-Xylol and the coupling of 4-halo neck dimethylbenzene, and then the methyl on the biphenylene oxide makes it become carboxyl, and then dehydration obtains acid anhydrides.This method need not be earlier with 3-halo o-Xylol and 4-halo neck xylene oxygen change into carboxylic acid then esterification again coupling take off ester group, reduced reaction process, saved time and raw material, make synthesis technique become simple.
Description of drawings
2,3,3 of Fig. 1 embodiment of the invention 1 preparation ', 4 '-the nucleus magnetic hydrogen spectrum spectrogram of bibenzene tetracarboxylic dianhydride.
Embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that just restriction of these descriptions for further specifying the features and advantages of the present invention rather than patent of the present invention being required.
The invention provides a kind of 2,3,3 ', 4 '-preparation method of bibenzene tetracarboxylic dianhydride, comprising:
A is to mix obtain first mixture at 1～3: 1～3 with compound shown in the formula II and the compound shown in the formula III in molar ratio, with described first mixture and catalyzer, part, reductive agent is 1: 0.01～0.5: 0.01～5: 0.5～6 to be blended in first solvent in molar ratio, carries out linked reaction and obtains the described compound of formula IV;
B) be 1: 4～20 to be blended in second solvent in molar ratio with the compound shown in the formula IV and oxygenant, oxidizing reaction takes place, obtain the described compound of formula V;
C) compound shown in the formula V is carried out dehydration reaction, obtain the compound shown in the formula I.
Wherein X is chlorine, bromine or iodine.
According to the present invention; 4-halo o-Xylol shown in 3-halo o-Xylol shown in the formula II and the formula III obtains by the halo of o-Xylol; but the o-Xylol behind the halo is difficult to separate; therefore just can earlier the halo o xylene oxidation be become halobenzoyl anhydride in the prior art; just can separate two kinds by industrial rectifying like this; but directly coupling of halobenzoyl anhydride; need carry out coupling again after esterification or the amidated protection earlier; take off ester group or amide group then as blocking group; dewater again after the acidifying and obtain acid anhydrides; can under the prerequisite of not separating 3-halo o-Xylol and 4-halo o-Xylol, react and this law is bright; by halo, obtain containing is 1～3: 1～3 3-halo o-Xylol and mixture coupling under the catalysis of nickel catalyzator and part of 4-halo o-Xylol to the ratio of control raw material in molar ratio with o-Xylol.
According to the present invention, with compound shown in the formula II and the compound shown in the formula III is to mix obtain first mixture at 1～3: 1～3 in molar ratio, with described first mixture and catalyzer, part, reductive agent is 1: 0.01～0.5: 0.01～5: 0.5～6 to be blended in first solvent in molar ratio, carries out linked reaction and obtains the described compound of formula IV; Wherein X is chlorine, bromine or iodine, the preferred chlorine of the present invention, so the compound shown in the formula II is preferably the 3-chloro-o-xylene, the compound shown in the formula III is preferably the 4-chloro-o-xylene, the hydrate of preferred nickel halogenide of described catalyzer or nickel halogenide is more elected anhydrous chlorides of rase nickel or anhydrous nickelous bromide as.Described part is preferably trialkyl phosphine, triaryl phosphine or 2,2 '-in dipyridyl and the derivative thereof one or more, alkyl in the described trialkyl phosphine is preferably the alkyl of 1～12 carbon atom, aryl in the described triaryl phosphine is preferably the phenyl that phenyl, alkyl or alkoxyl group replace, described in addition part also preferred alkyl or alkoxyl group replace 2,2 '-dipyridyl, most preferably be triphenylphosphine.Also preferably add catalyst aid in described first mixture according to the present invention, cocatalyst improves reaction efficiency, and described catalyst aid is preferably alkali-metal bromide, tetraalkyl brometo de amonio, tetraalkyl ammonium iodide, and described alkyl is the alkyl of 1～12 carbon.
Synthetic according to 3-chloro-o-xylene of the present invention and 4-chloro-o-xylene according to Chinese patent CN92104637.5, concrete grammar is: be raw material with the o-Xylol, with Lewis acids such as iron trichloride, aluminum chloride or iodine, iron etc. is catalyzer, with the chlorine direct chloro-substituted, obtain the monochloro-o-dimethyl benzene of high yield.
According to the present invention, described reductive agent is preferably zinc, zinc powder more preferably, and the particle diameter of described zinc powder is preferably the 40-160 order.
According to the present invention, described first solvent is preferably N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, tetramethylene sulfone, tetrahydrofuran (THF), dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, one or more in methyl tertiary butyl ether and the acetonitrile.Described solvent is preferably 1: 2 with the ratio of the weight summation of first mixture, catalyzer, catalyst aid, reductive agent, part～and 10.
According to the present invention, the compound shown in the formula IV is 2,3,3 ', 4 '-tetramethyl biphenyl, 4 substituent methyls are oxidized to 2 shown in the carboxylic acid preparation formula V, 3,3 ', 4 '-bibenzene tetracarboxylic, be specially, with described 2,3,3 ', 4 '-tetramethyl biphenyl and oxide compound are 1: 4～20 to mix in second solvent in molar ratio, and oxidizing reaction takes place.Described oxide compound is preferably potassium permanganate, potassium bichromate, sodium dichromate 99 or nitric acid; Wherein use potassium permanganate, when potassium bichromate or sodium dichromate 99 are made oxygenant, described second solvent is the aqueous solution of pyridine, described pyridine and water are 1～3: 1～3 by mass ratio, with described 2,3,3 ', 4 '-tetramethyl biphenyl, second solution that the oxide compound and second solvent obtain is heated to 80～120 ℃, reaction 4～12h, then described second solution is cooled to room temperature, get the mixed in hydrochloric acid acidifying of filtrate and 20wt% after the filtration, leave standstill 24～30h, the adularescent solid is separated out from second solution, described solid of separating out is 2,3,3 ', 4 '-bibenzene tetracarboxylic.
According to the present invention, if described oxygenant uses nitric acid, corresponding second solvent is a water, the weight ratio of described nitric acid and water is 0.1～0.3: 1, with described 2,3,3 ', 4 '-tetramethyl biphenyl, the oxide compound and second solvent obtain the 3rd solution and are heated to 90～110 ℃, and reaction 4～12h is cooled to room temperature with described second solvent then, then described second solution is cooled to room temperature, get the mixed in hydrochloric acid acidifying of filtrate and 20wt% after the filtration, leave standstill 24～30h, the adularescent solid is separated out from second solution, described solid of separating out is 2,3,3 ', 4 '-bibenzene tetracarboxylic.
According to the present invention, with prepare 2,3,3 ', 4 '-bibenzene tetracarboxylic dehydration obtains the compound 2,3 shown in the formula I, 3 ', 4 '-bibenzene tetracarboxylic dianhydride, dehydration method is optional to be used in the diacetyl oxide azeotropic dehydration in reflux dehydration, fusion dehydration, toluene, ethylbenzene or the dimethylbenzene.The reflux dehydration is specially in diacetyl oxide: with 2,3,3 ', 4 '-bibenzene tetracarboxylic and diacetyl oxide are 1: 2～10 to mix in molar ratio, and under 120～140 ℃, reacting 10～15h, per two carboxyls are sloughed an one's share of expenses for a joint undertaking water and are obtained the compound 2,3 shown in the formula I, 3 ', 4 '-bibenzene tetracarboxylic dianhydride.
According to the present invention, described fusion dehydration is specially, with 2,3,3 ', 4 '-bibenzene tetracarboxylic is heated to 210～380 ℃, till not having water to generate, is preferably 4～10h heat-up time, more preferably 6～8h.Obtain the compound 2,3,3 shown in the formula I ', 4 '-bibenzene tetracarboxylic dianhydride.
According to the present invention, described toluene, ethylbenzene or dimethylbenzene azeotropic dehydration are specially, with 2,3,3 ', 4 '-bibenzene tetracarboxylic and toluene, ethylbenzene or dimethylbenzene are 1: 10～50 to mix reflux by weight, Heating temperature is preferably 100～200 ℃, not generating, obtain the compound 2,3 shown in the formula I up to water, 3 ', 4 '-bibenzene tetracarboxylic dianhydride.
In order to further specify technical scheme of the present invention, the preferred embodiment of the invention is described below in conjunction with embodiment.Need to prove that the source of main raw material used in the present invention and reagent is as follows:
Table 1, the embodiment of the invention are used raw material and reagent source table
Embodiment 1
At room temperature, add 3-chloro-o-xylene 140.6g in the reaction vessel, 1.0mol and 4-chloro-o-xylene 140.6g, 1.0mol, nickelous bromide 21.8g, 0.1mol, triphenylphosphine 131g, 0.5mol, zinc powder 130.8g, 2mol and dimethyl formamide 300ml were 70 ℃ of reactions 8 hours.Reaction finishes, and adds toluene in the system, the filtering solid residue.After twice of the toluene layer washing, concentrate and remove solvent, mainly contain 2,3,3 in the residuum ', 4 '-tetramethyl biphenyl.
In residuum, add KMnO
41264g, 8.0mol, pyridine 2800g and water 5600g are heated to 100 ℃, react 8 hours.After reaction system drops to room temperature, filter, filtrate was left standstill 24 hours with 20% hcl acidifying, and white solids are separated out in a large number.The solid product that filtration obtains, behind the distilled water recrystallization, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic.
With 2,3,3 ', 4 '-bibenzene tetracarboxylic is heated to 250 ℃ of fusion dehydrations 12 hours, acquisition 138.08g target product 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, yield 66%.
As shown in Figure 1, for 2,3,3 of present embodiment preparation ', 4 '-the nucleus magnetic hydrogen spectrum spectrogram of bibenzene tetracarboxylic dianhydride, the spectrogram parameter is Rruker AV600
1H NMR 600M DMSO-d
6
Embodiment 2
At room temperature, add 3-chloro-o-xylene 140.6g in the reaction vessel, 1.0mol and 4-chloro-o-xylene 281.2g, 2.0mol, nickelous bromide 21.8g, 0.1mol, triphenylphosphine 131g, 0.5mol, zinc powder 196.6g, 3mol and tetrahydrofuran (THF) 800ml were 70 ℃ of reactions 8 hours.Reaction finishes, and adds toluene in the system, the filtering solid residue.After twice of the toluene layer washing, concentrate and remove solvent, mainly contain 2,3,3 in the residuum ', 4 '-tetramethyl biphenyl.
In residuum, add KMnO
41264g, 8.0mol, pyridine 2800g and water 5600g are heated to 100 ℃, react 8 hours.After reaction system drops to room temperature, cross and filter to remove insolubles.Filtrate with 20% hcl acidifying after, be heated to 80 ℃.The white precipitate that filtering forms.After filtrate was left standstill 24 hours, new white solid was separated out.The solid product that filtration obtains, behind the distilled water recrystallization, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic.
With 2,3,3 ', 4 '-bibenzene tetracarboxylic is heated to 250 ℃ of fusions dehydration 12 hours, obtain 117.8g target product 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, yield 56%.
Embodiment 3
At room temperature, add 3-chloro-o-xylene 281.2g in the reaction vessel, 2.0mol and 4-chloro-o-xylene 140.6g, 1.0mol, nickelous bromide 21.8g, 0.1mol, 2,2 '-dipyridyl 78.1g, 0.5mol, zinc powder 196.6g, 3mol and N,N-DIMETHYLACETAMIDE 400ml were 70 ℃ of reactions 8 hours.Reaction finishes, and adds toluene in the system, the filtering solid residue.After twice of the toluene layer washing, concentrate and remove solvent, mainly contain 2,3,3 in the residuum ', 4 '-tetramethyl biphenyl, residuum is directly used in next step without being further purified.
In residuum, add KMnO
41264g, 8.0mol, pyridine 2800g and water 5600g are heated to 100 ℃, react 8 hours.After reaction system drops to room temperature, cross and filter to remove insolubles.Filtrate with 20% hcl acidifying after, leave standstill 24 hours after, a large amount of white solids are separated out.The solid product that filtration obtains, behind the distilled water recrystallization, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic.
With 2,3,3 ', 4 '-bibenzene tetracarboxylic joins in the 1000ml diacetyl oxide, reflux dehydration 12 hours, obtain 134.6g target product 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, yield 64%.
Embodiment 4
At room temperature, add 3-chloro-o-xylene 421.8g in the reaction vessel, 3.0mol and 4-chloro-o-xylene 140.6g, 1.0mol, nickelous bromide 65.4g, 0.3mol, Sodium Bromide 102.9g, 1.0mol, triphenylphosphine 393g, 1.5mol, zinc powder 392.4g, 3mol and tetramethylene sulfone 800ml were 70 ℃ of reactions 8 hours.Reaction finishes, and adds toluene in the system, the filtering solid residue.After twice of the toluene layer washing, concentrate and remove solvent, mainly contain 2,3,3 in the residuum ', 4 '-tetramethyl biphenyl, residuum is directly used in next step without being further purified.
In residuum, add KMnO
41264g, 8.0mol, pyridine 2800g and water 5600g are heated to 100 ℃, react 8 hours.After reaction system drops to room temperature, filter, filtrate with 20% hcl acidifying after, be heated to 80 ℃.The white precipitate that filtering forms.Left standstill 24 hours, new white solid is separated out.The solid product that filtration obtains, behind the distilled water recrystallization, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic.
With 2,3,3 ', 4 '-bibenzene tetracarboxylic is heated to 250 ℃ of fusions dehydration 12 hours, obtain 103g target product 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, yield 49%.
Embodiment 5
At room temperature, add 3-chloro-o-xylene 140.6g in the reaction vessel, 1.0mol and 4-chloro-o-xylene 421.8g, 3.0mol, nickelous bromide 65.4g, 0.3mol, triphenylphosphine 393g, 1.5mol, zinc powder 392.4g, 3mol and dimethyl formamide 800ml were 70 ℃ of reactions 8 hours.Reaction finishes, and adds toluene in the system, the filtering solid residue.After twice of the toluene layer washing, concentrate and remove solvent, mainly contain 2,3,3 in the residuum ', 4 '-tetramethyl biphenyl, residuum is directly used in next step without being further purified.
In residuum, add KMnO
41264g, 8.0mol, pyridine 2800g and water 5600g are heated to 100 ℃, react 8 hours.After reaction system drops to room temperature, filter, filtrate was left standstill 24 hours with 20% hcl acidifying, and white solids are separated out in a large number.The solid product that filtration obtains, behind the distilled water recrystallization, obtain 2,3,3 ', 4 '-bibenzene tetracarboxylic.
With 2,3,3 ', 4 '-bibenzene tetracarboxylic is heated to 250 ℃ of fusions dehydration 12 hours, obtain 90.4g target product 2,3,3 ', 4 '-bibenzene tetracarboxylic dianhydride, yield 43%.
The invention provides 2,3,3 ', 4 '-the bibenzene tetracarboxylic dianhydride preparation method, 3-halo o-Xylol and 4-halo neck dimethylbenzene is carried out linked reaction under nickel catalyzator catalysis, obtain 2,3,3 ', 4 '-tetramethyl biphenyl, then with described 2,3,3 ', 4 '-tetramethyl biphenyl is oxidized to 2,3,3 ', 4 '-bibenzene tetracarboxylic, at last with described 2,3,3 ', 4 '-bibenzene tetracarboxylic dehydration obtains bibenzene tetracarboxylic dianhydride.The present invention is earlier with 3-halo o-Xylol and the coupling of 4-halo neck dimethylbenzene, and then the methyl on the biphenylene oxide makes it become carboxyl, and then dehydration obtains acid anhydrides.This method need not be earlier with 3-halo o-Xylol and 4-halo neck xylene oxygen change into carboxylic acid then esterification again coupling take off ester group, reduced reaction process, saved time and raw material, make synthesis technique become simple.
More than to provided by the invention a kind of 2; 3; 3 '; 4 '-preparation method of bibenzene tetracarboxylic dianhydride is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. 2,3,3 shown in the formula I ', 4 '-preparation method of bibenzene tetracarboxylic dianhydride, it is characterized in that, comprising:
A is to mix obtain first mixture at 1～3: 1～3 with compound shown in the formula II and the compound shown in the formula III in molar ratio, with described first mixture and catalyzer, part, reductive agent is 1: 0.01～0.5: 0.01～5: 0.5～6 to be blended in first solvent in molar ratio, carries out linked reaction and obtains the described compound of formula IV;
B) be 1: 4～20 to be blended in second solvent in molar ratio with the compound shown in the formula IV and oxygenant, oxidizing reaction takes place, obtain the described compound of formula V;
C) compound shown in the formula V is carried out dehydration reaction, obtain the compound shown in the formula I.
X in formula II and the formula III is respectively chlorine, bromine or iodine.
2. preparation method according to claim 1 is characterized in that, the catalyzer among the step a is the hydrate of nickel halogenide or nickel halogenide.
3. preparation method according to claim 2 is characterized in that, described catalyzer is anhydrous chlorides of rase nickel or anhydrous nickelous bromide.
4. preparation method according to claim 1 is characterized in that, the part among the step a be trialkyl phosphine, triaryl phosphine or 2,2 '-in dipyridyl and the derivative thereof one or more.
5. preparation method according to claim 1, it is characterized in that, described first solvent is N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, tetramethylene sulfone, tetrahydrofuran (THF), dioxane, glycol dimethyl ether, ethylene glycol diethyl ether, one or more in methyl tertiary butyl ether and the acetonitrile.
6. preparation method according to claim 1 is characterized in that, described reductive agent is a zinc.
7. preparation method according to claim 1, it is characterized in that, step a) comprises also that in described first solvent adding with first mixture is 0～1: 1 catalyst aid in molar ratio, described catalyst aid is alkali-metal bromide, tetraalkyl brometo de amonio, tetraalkyl ammonium iodide, and described alkyl is the alkyl of 1～12 carbon.
8. preparation method according to claim 1 is characterized in that, described oxygenant is potassium permanganate, potassium bichromate, sodium dichromate 99 or nitric acid.
9. according to any described preparation method in the claim 1～2,4～8, it is characterized in that, b) be specially:
B11) be 1: 4～20 to be dissolved in second solvent in molar ratio with the compound shown in the formula IV and potassium permanganate, potassium bichromate or sodium dichromate 99, obtain mixing solutions; Described second solvent is that pyridine and water are the solution that 1～3: 1～3 mixing obtains by mass ratio;
B12) with b11) mixing solutions that obtains is heated to and carries out oxidizing reaction under 80 ℃～120 ℃ and obtain the compound shown in the formula V.
10. according to any described preparation method in the claim 1～2,4～8, it is characterized in that, b) be specially:
B21) with the compound shown in the formula IV and nitric acid be in molar ratio 1: 4～20 mixed dissolutions in second solvent, obtain mixing solutions; Described second solvent is a water, and the concentration of nitric acid in the described mixing solutions is 10wt%～30wt%;
B22) mixing solutions that b21 is obtained is heated to and carries out oxidizing reaction under 80 ℃～120 ℃ and obtain the compound shown in the formula V.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010611991A CN102020622B (en) | 2010-12-29 | 2010-12-29 | Method for preparing 2,3,3',4'-biphenyltetracarboxylic di-anhydride |
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| CN103086838A (en) * | 2013-02-08 | 2013-05-08 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
| CN104341256A (en) * | 2014-10-20 | 2015-02-11 | 哈尔滨工业大学（威海） | Low-cost and environment-friendly synthesis method of biphenyl derivatives |
| CN104703949A (en) * | 2012-10-10 | 2015-06-10 | 国立大学法人九州大学 | Method for producing multisubstituted biphenyl compound and solid catalyst to be used therein |
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN109529937A (en) * | 2018-12-14 | 2019-03-29 | 四川理工学院 | A kind of preparation method of the Ni-based procatalyst of trifluoroethyl coordination |
| CN112390769A (en) * | 2020-11-19 | 2021-02-23 | 山东科思姆特种材料技术开发有限公司 | Preparation method of 2,2',3,3' -biphenyl tetracid dianhydride |
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| CN101659647A (en) * | 2008-08-26 | 2010-03-03 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
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| CN104703949A (en) * | 2012-10-10 | 2015-06-10 | 国立大学法人九州大学 | Method for producing multisubstituted biphenyl compound and solid catalyst to be used therein |
| US9469621B2 (en) | 2012-10-10 | 2016-10-18 | Kyushu University, National University Corporation | Method for producing multisubstituted biphenyl compound and solid catalyst to be used therein |
| CN103086838A (en) * | 2013-02-08 | 2013-05-08 | 中国科学院长春应用化学研究所 | Preparation method of tetramethyl biphenyl |
| CN103086838B (en) * | 2013-02-08 | 2016-02-03 | 中国科学院长春应用化学研究所 | A kind of preparation method of tetramethyl biphenyl |
| CN104341256A (en) * | 2014-10-20 | 2015-02-11 | 哈尔滨工业大学（威海） | Low-cost and environment-friendly synthesis method of biphenyl derivatives |
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN106279085B (en) * | 2016-08-17 | 2018-07-10 | 万华化学集团股份有限公司 | A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN109529937A (en) * | 2018-12-14 | 2019-03-29 | 四川理工学院 | A kind of preparation method of the Ni-based procatalyst of trifluoroethyl coordination |
| CN112390769A (en) * | 2020-11-19 | 2021-02-23 | 山东科思姆特种材料技术开发有限公司 | Preparation method of 2,2',3,3' -biphenyl tetracid dianhydride |
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