TWI583688B - Method for preparing bicyclooctane tetracarboxylic dianhydride - Google Patents

Description

Method for preparing bicyclooctane tetracarboxylic dianhydride

The invention relates to a method for preparing a bicyclooctane tetracarboxylic dianhydride, in particular to a bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid II with high yield and simple steps. A method of preparing an anhydride.

In the Japanese Patent Publication No. JP-A-1994-119611 and the document Macromolecules 1997, 30, 993-1000, the step of synthesizing bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride comprises: The phthalic acid is placed in the assembled electrochemical reaction tank, and after 3 hours of reaction, it is concentrated to obtain (±)-trans-1,2-dihydrophthalic acid ((±)- Trans-1,2-dihydrophthalic acid); put 50 g of (±)-trans-1,2-dihydrophthalic acid, 400 ml of methanol (Methanol) and 8 ml of concentrated sulfuric acid into a 1-liter three-necked flask was heated at reflux for 18 hours, the reaction solution with saturated sodium bicarbonate (NaHCO ₃₎ and an aqueous solution, and extracted three times with 300 ml of ether (Dimethyl ether), magnesium sulphate (MgSO ₄₎ removal of water, and then the solvent was concentrated under reduced pressure to Purification by distillation to obtain dimethyl(±)-trans-1,2-dihydrophthalate (Dimethyl(±)-trans-1,2-dihydrophthalate); 113.6 g of dimethyl (±)- Reverse-1,2-dihydrophthalate and 79.4 g of dimethyl maleate were placed in a 200 ml three-necked flask equipped with a spherical condenser, slowly passed through a nitrogen gas and heated to Reaction at 190 ° C for 9 hours, the resulting reaction solution Purification by fractional distillation gives colorless and viscous tetramethylbicyclo[2.2.2]oct-7-ene-2-endo,3-exo,5-exo,6-exo-tetracarboxylate (Tetramethyl Bicyclo[ 2.2.2] oct-7-ene-2-endo, 3-exo, 5-exo, 6-exo-tetracarboxylate); 24.4 g of the aforementioned tetracarboxylic acid ester with 50 ml of absolute alcohol (containing 5% Pd/C) Placed in a 200 ml hydrogenation reactor and hydrogenated at room temperature for 12 hours at a pressure of 50 kg/cm 2 , filtered Pd/C with diatomaceous earth and easily collected under reduced pressure to give an oil. Purification by fractional distillation gave colorless tetramethylbicyclo[2.2.2]octane-2- endo ,3- exo ,5- exo ,6- exo -tetracarboxylate (Tetramethyl Bicyclo[2.2.2] Octane-2- endo , 3- exo , 5- exo , 6- exo- tetracarboxylate); 43.7 g of tetramethylbicyclo[2.2.2]octane-2- endo , 3- exo , 5- exo , 6 - exo - tetracarboxylic acid ester, 30.6 g of sodium hydroxide, 220 ml of distilled water and 440 ml of alcohol were placed in a 1 liter three-necked flask and heated under reflux for 6 hours, concentrated under reduced pressure and the unreacted portion was treated with acetic acid The ester was extracted and removed, and the aqueous layer was taken and acidified with aqueous hydrochloric acid, and extracted with ethyl acetate three times. The organic layer was concentrated under magnesium sulfate and concentrated to give a white solid. The white solid was placed in a 1 liter three-necked flask, and 300 ml of acetic anhydride and 200 ml of decahydronaphalene were added, and the mixture was slowly introduced with nitrogen and heated to reflux for 16 hours, and then concentrated under reduced pressure. Another white solid is obtained, and the obtained white solid is recrystallized from acetic anhydride to obtain (BODAdx) white crystals, yield 53%; (BODAxx) solid, then 24.5 g of tetramethylbicyclo[2.2.2]octane-2- endo , 3- exo , 5- exo , 6- exo -tetracarboxylic acid ester were placed in the reactor and 20 ml was added. Concentrated hydrochloric acid (HCl) and 100 ml of water were heated to reflux, and another 10 ml of concentrated hydrochloric acid was added, and the mixture was heated under reflux for 9 hours in 1 hour, and the reaction liquid was concentrated to give a white crude product. In the form of the above-mentioned BODAdx ring closure and purification method, BODAxx white crystals can be obtained in a yield of 19%.

Further, in Japanese Patent Laid-Open Publication No. JP2003-140427, 7.5 g of bicyclooctene tetracarboxylic dianhydride, 142.5 g of γ-butyrolactone and 0.375 g of 5% Pd/C are placed in an electromagnetic stirring function. In the hydrogenation reactor, 1 MPa of hydrogen was poured into the reactor, and the temperature was raised to 100 ° C to carry out a reduction reaction until the starting reaction was completed. After completion of the reaction, the metal catalyst was removed by filtration under reduced pressure, and the reaction liquid was concentrated under reduced pressure and cooled to obtain precipitated crystals. After the crystals were separated, they were dried under reduced pressure to give a mixture (yield: 94.5%).

In the above process for producing bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride, the reaction step is complicated and the yield obtained is low (up to about 50% up and down). Further, even if a high yield can be obtained, the stereoisomer contained in the product is very difficult to purify or separate. On the other hand, by-products in the manufacturing process also cause the processing of reactive waste to increase the overall process cost invisibly.

Therefore, it is necessary to provide a preparation method of bicyclooctane tetracarboxylic dianhydride, which can simplify the process steps, improve the reaction efficiency and yield, separate stereoisomers and reduce the overall process cost, so as to solve the problems in the conventional technology. .

The main object of the present invention is to provide a bicyclooctane tetracarboxylic dianhydride system. Preparation method, the whole process is carried out in a simple and mild reaction condition, and the stereoisomer of the intermediate product can be separated first, and then the ring-closing reaction is separately carried out, so that a high yield of the bicyclooctane tetracarboxylic dianhydride can be obtained. The product of two stereoisomers, which has the advantages of high reaction efficiency and reduced overall process cost.

In order to achieve the above object, an embodiment of the present invention provides a method for preparing a bicyclooctane tetracarboxylic dianhydride, which comprises the steps of: (1) dissolving a bicyclooctene tetracarboxylic dianhydride in an acidic aqueous solution for hydrogenation; Reacting to obtain a mixed product comprising a first product and a second product; (2) separating the first product and the second product; and (3) selecting the first or second product with acetic acid The anhydride is subjected to a cyclization reaction to form a bicyclooctane tetracarboxylic dianhydride.

In one embodiment of the invention, the bicyclooctene tetracarboxylic dianhydride has the structure of formula (I):

In one embodiment of the invention, the acidic aqueous solution comprises a group consisting of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, and trifluoroacetic acid, and the concentration of the acidic aqueous solution is from 3 to 15% by weight.

In one embodiment of the invention, the hydrogenation reaction is carried out using a metal catalyst at a temperature of 80 to 120 ° C and a hydrogen pressure of 100 to 260 psi, wherein the metal catalyst comprises a metal selected from the group consisting of nickel, A group of palladium, platinum, and rhodium.

In an embodiment of the invention, the metal catalyst further comprises a carrier, and the carrier is carbon.

In an embodiment of the invention, the first product has the structure of formula (II) and the second product has the structure of formula (III):

In an embodiment of the invention, the step (2) comprises the steps of: (2A) washing the mixed product with a second acidic aqueous solution; and (2B) collecting the insoluble solid portion to obtain the first product.

In an embodiment of the present invention, the step (2) comprises the steps of: (2A') washing the mixed product with a second acidic aqueous solution; and (2B') filtering out the insoluble solid portion to obtain the first Two products.

In one embodiment of the present invention, the second acidic aqueous solution is selected from the group consisting of acetic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid, and phosphoric acid, and the concentration of the second acidic aqueous solution is 8 to 25% by weight.

In one embodiment of the invention, the bicyclooctane tetracarboxylic dianhydride obtained after the cyclization reaction of the first product has the structure of formula (IV):

In one embodiment of the invention, the bicyclooctane tetracarboxylic dianhydride obtained after the cyclization reaction of the second product has the structure of formula (V):

In one embodiment of the invention, the temperature of the cyclization reaction is from 80 to 120 °C.

The above and other objects, features, and advantages of the present invention will become more apparent from The singular forms "a", "the", and "the" For example, the term "a compound" or "at least one compound" may include a plurality of compounds, including mixtures thereof; "%" as referred to in the present specification means "percent by weight (wt%)" unless otherwise specified; For example, 10%~11% of A) include upper and lower limits (ie 10% ≦A≦11%) unless otherwise specified; if the value range does not define a lower limit (such as B below 0.2%, or 0.2) B) below B) means that the lower limit may be 0 (ie 0% ≦ B ≦ 0.2%); the proportional relationship of the "weight percentage" of each component may also be replaced by the proportional relationship of "parts by weight". The above terms are used to illustrate and understand the present invention and are not intended to limit the invention.

An embodiment of the invention provides a preparation method of bicyclooctane tetracarboxylic dianhydride The method comprises the steps of: (S1) dissolving the bicyclooctene tetracarboxylic dianhydride in an acidic aqueous solution for a hydrogenation reaction to obtain a mixed product comprising a first product and a second product; (S2) Separating the first product and the second product; and (S3) subjecting the first or second product to a cyclization reaction with acetic anhydride to form a bicyclooctane tetracarboxylic dianhydride. The details of the implementation of the above steps and the principles thereof will be described in detail below.

The preparation method of the bicyclooctane tetracarboxylic dianhydride according to an embodiment of the present invention is firstly: (S1) dissolving the bicyclooctene tetracarboxylic dianhydride in an acidic aqueous solution to carry out a hydrogenation reaction to obtain a mixture comprising a first product and a second product. In this step, the bicyclooctene tetracarboxylic dianhydride has the structure of the formula (I) and can be synthesized synthetically or commercially. The acidic aqueous solution comprises a group consisting of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid and trifluoroacetic acid, preferably acetic acid. The concentration of the acidic aqueous solution is from 3 to 15% by weight, and may be, for example, 4.5, 5.5, 6.5 or 7.5%, but is not limited thereto. Preferably, the acidic aqueous solution is 4.8% acetic acid. In actual practice, when the bicyclooctene tetracarboxylic dianhydride is mixed with the acidic aqueous solution, the dissolution state thereof can be slightly adjusted by heating. In general, it is permissible to rapidly dissolve the bicyclooctene tetracarboxylic dianhydride in the acidic aqueous solution by slightly heating (not exceeding 100 ° C).

Further, after the bicyclooctene tetracarboxylic dianhydride is dissolved, the hydrogenation reaction belongs to a high pressure hydrogenation process, mainly using a metal catalyst, at a temperature of 80 to 120 ° C, preferably 100, for example. The temperature is °C and is carried out at a hydrogen pressure of 100 to 260 psi. The metal catalyst may comprise a metal selected from the group consisting of nickel, palladium, platinum and rhodium. The metal catalyst may further comprise a carrier, for example, platinum/carbon (Pt/C) supported on carbon. However, it is not limited thereto, and the metal and the carrier may be used according to actual conditions, or only the metal may be used. . Preferably, the hydrogenation reaction can be carried out using a 5 wt% palladium on carbon (Pd/C) under a hydrogen pressure of 200 psi. After the hydrogenation reaction, the first product and the second product contained in the mixture have the structures of the formula (II) and the formula (III) shown below:

The first product and the second product are stereoisomers with each other, the yield of the first product is about 60 to 65%, and the yield of the second product is about 25 to 30%.

The preparation method of the bicyclooctane tetracarboxylic dianhydride according to an embodiment of the present invention is followed by: (S2) separating the first product and the second product. In this step, the difference in solubility between the first product and the second product for a second acidic aqueous solution may be utilized, and the mixed product is first washed with the second acidic aqueous solution, and a solid which is insoluble in the second acidic aqueous solution may be found. Partially, the first product can be separated from the second product. Next, the undissolved solid portion is collected to obtain the first product. Alternatively, the insoluble solid portion can be filtered to obtain the second product. The second acidic aqueous solution may, for example, be a group selected from the group consisting of acetic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid and phosphoric acid, preferably hydrochloric acid. The concentration of the second acidic aqueous solution is 8 to 25% by weight, and may be, for example, 8, 10, 12 or 15%, but is not limited thereto. Preferably, the second acidic aqueous solution is 8% hydrochloric acid. Thus, by this step, the first product or the second product can each be taken.

The preparation method of the bicyclooctane tetracarboxylic dianhydride according to an embodiment of the present invention is followed by: (S3) subjecting the first or second product to a cyclization reaction with acetic anhydride to form a bicyclooctane tetracarboxylic acid anhydride. In this step, the conditions of the cyclization reaction are not critical, and it is only necessary to control the temperature at about 80 to 120 ° C, preferably at 100 ° C. The bicyclooctane tetracarboxylic dianhydride obtained after the cyclization reaction of the first product has the structure of the formula (IV): The yield can reach 90%.

The bicyclooctane tetracarboxylic dianhydride obtained after the cyclization reaction of the second product has the structure of the formula (V): The yield can reach 90%.

In order to make the preparation method of the bicyclooctane tetracarboxylic dianhydride of the present invention clearer and easier to understand, please refer to the following practical procedure, but it is not intended to limit the preparation method of the bicyclooctane tetracarboxylic dianhydride of the present invention. The steps included in .

Example 1

Please refer to the general reaction agency below.

Step 1: Hydrogenation

As shown in the above reaction mechanism, 200 g of bicyclooctene tetracarboxylic dianhydride (COeDA), 140.41 g of acetic acid, and 3000 g of water were placed in a reactor, respectively, and the reactor was heated until COeDA was completely dissolved. Next, 10 g of Pd/C was added to the reactor, followed by hydrogenation to 200 psi, and reaction at 100 ° C for 4 hours. After the temperature was lowered to room temperature, Pd/C was filtered off, and then the solution was concentrated under reduced pressure to a viscous mixture to obtain a mixed product (BODAcxx and BODAcdx).

Step 2: Separate the product BODAcxx from the product BODAcdx

The mixed product was washed with an aqueous solution of 8% hydrochloric acid (HCl), and the insoluble solid portion was collected, and dried to give 145.72 g of BODAcxx solid. The yield was about 63.2%. Further, the collected aqueous solution portion was allowed to stand at room temperature for three days to be recrystallized, and after collecting the solid by filtration, about 62.45 g of BODAcdx solid was collected, and the yield was about 27.1%.

Step 3: Cyclization of the product BODAcxx or the product BODAcdx

145.72 g of BODAcxx solid (or BODAcdx solid) obtained in step 2 and 1457.2 g of acetic anhydride (Acetic anhydride) were placed in a reaction tank and heated to 100 ° C. Reaction for 18 hours. After completion of the cyclization reaction, the precipitated solid was filtered, washed with hexane (Hexane), and dried to give bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride. BODAxx has a total of 114.64 grams, the yield is calculated to be about 90.0%, and the melting point is greater than 380 °C. On the other hand, the yield of bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride BODAdx was calculated to be about 90.0%.

Compared with the prior art, the manufacturing method provided by the present invention can utilize a relatively simple step, and the stereoisomer of the intermediate product can be separated first without the complicated separation or synthesis step, and then the ring closure reaction is separately carried out. Therefore, two stereoisomers of bicyclooctane tetracarboxylic dianhydride in high yield can be obtained, and the method has high reaction efficiency and can effectively reduce manufacturing cost and synthesis complexity.

The present invention has been disclosed in its preferred embodiments, and is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Claims (12)

A method for preparing a bicyclooctane tetracarboxylic dianhydride, comprising the steps of: (1) dissolving a bicyclooctene tetracarboxylic dianhydride in an acidic aqueous solution to carry out a hydrogenation reaction to obtain a mixed product comprising a first a product and a second product; (2) separating the first product and the second product; and (3) subjecting the first or second product to a cyclization reaction with acetic anhydride to form a bicyclooctane IV Carboxylic dianhydride. The method for producing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the bicyclooctene tetracarboxylic dianhydride has a structure of the formula (I): The method for preparing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the acidic aqueous solution comprises a group selected from the group consisting of hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid and trifluoroacetic acid, and the acidic aqueous solution The concentration is from 3 to 15% by weight. The method for preparing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the hydrogenation reaction is carried out using a metal catalyst at a temperature of 80 to 120 ° C and a pressure of 100 to 260 psi, wherein The metal catalyst comprises a metal selected from the group consisting of nickel, palladium, platinum, and rhodium. The method for preparing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the metal catalyst further comprises a carrier, and the carrier is carbon. The method for producing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the first product has the structure of the formula (II): And the second product has the structure of formula (III): The method for preparing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the step (2) comprises the steps of: (2A) washing the mixed product with a second acidic aqueous solution; and (2B) The insoluble solid portion is collected to obtain the first product. The method for preparing a bicyclooctanetetracarboxylic dianhydride according to claim 1, wherein the step (2) comprises the steps of: (2A') washing the mixed product with a second acidic aqueous solution; and (2B) ') Filter out the insoluble solid portion to obtain the second product. The method for preparing a bicyclooctane tetracarboxylic dianhydride according to claim 7 or 8, wherein the second acidic aqueous solution is selected from the group consisting of acetic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid and phosphoric acid, and The concentration of the second acidic aqueous solution is 8 to 25% by weight. The method for producing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the bicyclooctane tetracarboxylic dianhydride obtained after the cyclization reaction of the first product has the structure of the formula (IV) : The method for producing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the bicyclooctane tetracarboxylic dianhydride obtained after the cyclization reaction of the second product has the structure of the formula (V) : The process for producing a bicyclooctane tetracarboxylic dianhydride according to claim 1, wherein the temperature of the cyclization reaction is from 80 to 120 °C.