Method for preparing compound having dicarboxylic acid derivative structure

Abstract

Provided is a method for producing a compound having a dicarboxylic acid derivative structure, the method comprising a reaction step in which an olefin, an alcohol, carbon monoxide, and oxygen are reacted in the presence of an ammonium salt and a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier. Preferably, the ammonium salt is ammonium chloride. Preferably, the olefin is an alicyclic olefin.

Description

Technical Field

[0001] The present invention relates to a method for producing a compound having a dicarboxylic acid derivative structure.

[0002] This application claims priority based on Japanese Patent Application No. 2022-182584 filed in Japan on November 15, 2022, and incorporates its content herein. Background Art

[0003] Conventionally, compounds having a dicarboxylic acid derivative structure formed by introducing a total of two carboxyl groups and / or carboxylic acid ester groups onto the carbon-carbon double bond of an olefin (unsaturated hydrocarbon) have been used as raw materials for various compounds, additives in resins, and the like.

[0004] As a method for producing such a compound having a dicarboxylic acid derivative structure, there are the methods described in Patent Document 1 or Patent Document 2.

[0005] Patent Document 1 discloses a method for producing dicyclopentadiene, carbon monoxide, an alcohol and / or an acetal, ketal, or orthoformic acid alkyl ester as a derivative thereof in the presence of a palladium catalyst, a copper or iron compound, and / or oxygen to produce tricyclo[5.2.1.0 2,6 dec-3-ene-8,9-dicarboxylic acid diester.

[0006] Patent Document 2 describes a method for producing norbornenes in which norbornenes are reacted with an alcohol, carbon monoxide, and oxygen in the presence of a catalyst containing a palladium metal or its compound, a copper compound, a chlorine compound, and a manganese or zinc compound to introduce two carboxylic acid ester groups onto the carbon-carbon double bond of the norbornenes.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Laid-Open No. 60-104039 (A)

[0010] Patent Document 2: Japanese Patent Laid-Open No. 7-138205 (A) Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] However, in the conventional methods for producing a compound having a dicarboxylic acid derivative structure by reacting an olefin, an alcohol, carbon monoxide, and oxygen to introduce a total of two carboxyl groups and / or carboxylic acid ester groups onto the carbon-carbon double bond of the olefin, it is necessary to improve the yield of the compound having a dicarboxylic acid derivative structure.

[0013] The present invention has been completed in view of the above circumstances, and an object thereof is to provide a production method capable of introducing a total of two carboxyl groups and / or carboxylic acid ester groups into a carbon-carbon double bond of an olefin and producing a compound having a dicarboxylic acid derivative structure in a high yield.

[0014] It should be noted that the "dicarboxylic acid derivative structure" in the present invention refers to a structure having at least one of two or more carboxyl groups and carboxylic acid ester groups in total.

[0015] Means for Solving the Problem

[0016] In order to solve the above problems, the present inventors focused on a catalyst used for producing a compound having a dicarboxylic acid derivative structure by reacting an olefin, an alcohol, carbon monoxide, and oxygen to introduce a total of two carboxyl groups and / or carboxylic acid ester groups into the carbon-carbon double bond of the olefin, and conducted in-depth research.

[0017] As a result, it was found that as the catalyst, a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier and an ammonium salt can be used.

[0018] Furthermore, the present inventors confirmed that by reacting an olefin, an alcohol, carbon monoxide, and oxygen in the presence of the above catalyst, a compound having a dicarboxylic acid derivative structure in which a total of two carboxyl groups and / or carboxylic acid ester groups are introduced into the carbon-carbon double bond of the olefin can be produced in a high yield, and thus the present invention was conceived.

[0019] That is, the present invention relates to the following matters.

[0020] [1] A production method of a compound having a dicarboxylic acid derivative structure, which includes a reaction step of reacting an olefin, an alcohol, carbon monoxide, and oxygen in the presence of a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier and an ammonium salt.

[0021] [2] The production method of a compound having a dicarboxylic acid derivative structure according to [1], wherein the ammonium salt is ammonium chloride.

[0022] [3] The production method of a compound having a dicarboxylic acid derivative structure according to [1] or [2], wherein the olefin is an alicyclic olefin.

[0023] [4] The production method of a compound having a dicarboxylic acid derivative structure according to [1] or [2], wherein the olefin is a compound represented by the following formula (1),

[0024]

[0025] In formula (1), R 1 and R 2 each independently represent an alkyl group having 1 or more and 5 or less carbon atoms.

[0026] [5]The method for producing a compound having a dicarboxylic acid derivative structure according to any one of [1] to [4], wherein the compound having a dicarboxylic acid derivative structure is a compound represented by the following formula (2).

[0027]

[0028] In formula (2), R 11 , R 12 , R 3 and R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0029] Advantages of the Invention

[0030] In the method for producing a compound having a dicarboxylic acid derivative structure of the present invention, an olefin, an alcohol, carbon monoxide, and oxygen are reacted in the presence of a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier and an ammonium salt. Therefore, a compound having a dicarboxylic acid derivative structure in which a total of two carboxyl groups and / or carboxylic acid ester groups are introduced into the carbon-carbon double bond of the olefin can be produced in a high yield. Detailed Embodiments

[0031] Hereinafter, the method for producing a compound having a dicarboxylic acid derivative structure of the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments shown below.

[0032] The method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment includes a reaction step of reacting an olefin, an alcohol, carbon monoxide, and oxygen in the presence of a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier and an ammonium salt.

[0033] In the reaction step of the production method according to this embodiment, a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier and an ammonium salt are used as the catalyst, so the reaction rate of the dicarboxylation reaction of the olefin is fast enough. Thus, a compound having a dicarboxylic acid derivative structure, which is the target product and in which a total of two carboxyl groups (-COOH) and / or carboxylic acid ester groups (-COOR (R is an alkyl group derived from the alcohol (R-OH) used as a raw material)) are introduced into the carbon-carbon double bond of the olefin (unsaturated hydrocarbon), can be produced in a high yield.

[0034] In addition, in the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, since an ammonium salt is used, there is no possibility of forming a metal-derived precipitate due to the reaction as in the case of using a metal salt that is often used in conventional production methods. Moreover, the production method according to this embodiment is also advantageous in terms of cost and is therefore suitable for industrial applications.

[0035] "Olefin"

[0036] In the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, the olefin used as a raw material can be appropriately determined according to the structure of the compound having a dicarboxylic acid derivative structure as the target product. The olefin used as a raw material can be a chain olefin, an alicyclic olefin, or can have substituents.

[0037] Examples of the chain olefin include ethylene, propylene, butadiene, pentene, hexene, octene, dodecene, and the like.

[0038] Examples of the alicyclic olefin include cyclopentene, norbornene, dicyclopentadiene, cyclooctene, norbornadiene, tricyclopentadiene, ethylidene norbornene, 3a,4,7,7a-tetrahydroindene, 4-vinyl-1-cyclohexene, and the like. When an alicyclic olefin is used as a raw material, the effect of improving the yield brought about by using the production method of this embodiment can be significantly obtained, and thus it is preferred.

[0039] The substituents that the olefin used as a raw material can have are not particularly limited as long as they are stable under weakly acidic conditions, and examples include a carboxylic acid ester group having an alkyl group, a carboxyl group, a formyl group, a hydroxyl group, a tertiary amine, an acetal, and the like. As the carboxylic acid ester group having an alkyl group, a carboxylic acid ester group having an alkyl group with 1 to 5 carbon atoms is preferred, and a carboxylic acid ester group having an alkyl group with 1 to 3 carbon atoms is more preferred. This is because by using the production method of this embodiment, an industrially useful compound having a dicarboxylic acid derivative structure having a carboxylic acid ester group can be produced in a high yield.

[0040] The number of substituents that the olefin can have can be one or more, and can be appropriately determined according to the structure of the compound having a dicarboxylic acid derivative structure as the target product.

[0041] As the olefin used as a raw material, specifically, norbornene compounds selected from the following substances are preferred. For example, bicyclo[2.2.1]hept-2-ene (common name norbornene), 5-methyl-bicyclo[2.2.1]hept-2-ene, bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, methyl, ethyl or propyl ester of bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, 2-methyl-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, methyl, ethyl or propyl ester of 2-methyl-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid, or dimethyl, diethyl or dipropyl ester of bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid.

[0042] The olefin used as a raw material is preferably a compound represented by the following formula (1). This is because when the compound represented by formula (1) is used as a raw material, by using the production method of the present embodiment, an industrially useful tetracarboxylic acid derivative can be produced in a high yield.

[0043]

[0044] In formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 5 carbon atoms.

[0045] In the compound represented by formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. R 1 and R 2 may be the same or different. R 1 and / or R 2 is particularly preferably a methyl group because a compound having a dicarboxylic acid derivative structure that is industrially useful can be produced in a high yield by using the production method of the present embodiment.

[0046] The compound represented by formula (1) can be easily produced by a known method such as a method using a Diels - Alder reaction.

[0047] "Alcohol"

[0048] In the production method of the compound having a dicarboxylic acid derivative structure of the present embodiment, the alcohol used as a raw material can be appropriately determined according to the structure of the compound having a dicarboxylic acid derivative structure as the target product. As the alcohol used as a raw material, an alkyl alcohol (R-OH, where R is an alkyl group) is preferred. Specifically, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, octanol, dodecanol, etc. can be cited. Among them, as the alcohol, an alcohol in which the above R is an alkyl group having 1 to 5 carbon atoms is preferred. This is because a compound having a dicarboxylic acid derivative structure can be produced in a higher yield. Since by using the production method of the present embodiment, a compound having a dicarboxylic acid derivative structure that is industrially useful can be produced in a high yield, methanol is particularly preferably used as the alcohol.

[0049] "Carbon monoxide"

[0050] In the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, the amount of carbon monoxide used as a raw material is preferably an amount such that the partial pressure in the atmosphere for the dicarboxylation reaction of an olefin is in the range of 0.01 MPa (absolute pressure, the same hereinafter) to 10 MPa, more preferably in the range of 0.1 MPa to 5.0 MPa. When the partial pressure of carbon monoxide in the atmosphere for the dicarboxylation reaction of an olefin is 0.01 MPa or more, the dicarboxylation reaction of the olefin becomes easy to proceed, and a compound having a dicarboxylic acid derivative structure can be produced in a higher yield. When the partial pressure of carbon monoxide in the atmosphere for the dicarboxylation reaction of an olefin is 10 MPa or less, the reaction vessel becomes easy to supply in terms of the ease of pressure-resistant design of the reaction vessel, and thus is preferred.

[0051] "Oxygen"

[0052] In the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, the amount of oxygen used as a raw material is preferably an amount such that the partial pressure in the atmosphere for the dicarboxylation reaction of an olefin is in the range of 0.01 MPa (absolute pressure, the same hereinafter) to 2.0 MPa, more preferably in the range of 0.1 MPa to 1.0 MPa. When the partial pressure of oxygen in the atmosphere for the dicarboxylation reaction of an olefin is 0.01 MPa or more, the dicarboxylation reaction of the olefin becomes easy to proceed, and a compound having a dicarboxylic acid derivative structure can be produced in a higher yield. If the partial pressure of oxygen in the atmosphere for the dicarboxylation reaction of an olefin is 2.0 MPa or less, it is possible to prevent the atmosphere in the dicarboxylation reaction of the olefin from reaching the explosive range, and thus is preferred.

[0053] In the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, carbon monoxide and / or oxygen used as raw materials can be mixed with a dilution gas such as nitrogen, argon, helium, carbon dioxide, etc. that does not hinder the dicarboxylation reaction of an olefin as needed. In this case, it is possible to prevent the atmosphere in the dicarboxylation reaction of the olefin from reaching the explosive range, and thus is preferred.

[0054] When carbon monoxide and / or oxygen are mixed with a dilution gas, carbon monoxide and / or oxygen can be mixed with the dilution gas to form a mixed gas and then supplied to the reaction apparatus, or can be supplied to the reaction apparatus separately from the dilution gas and mixed with the dilution gas in the reaction apparatus. In the production method of this embodiment, air can also be used as the mixed gas of oxygen and the dilution gas.

[0055] In the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, hydrogen can be supplied to the atmosphere in the dicarboxylation reaction of an olefin as needed. When the atmosphere in the dicarboxylation reaction of an olefin contains hydrogen, the hydrogen can be mixed with carbon monoxide and / or oxygen and then supplied to the reaction apparatus, or can be supplied to the reaction apparatus separately from carbon monoxide and / or oxygen. Further, OXOGAS (a mixed gas of carbon monoxide and hydrogen), which is one of the basic raw materials in C1 chemistry known as synthesis gas, can be used as a raw material. In this case, compared with the case of using pure carbon monoxide gas, it can be used as an economically inexpensive carbon monoxide source.

[0056] After the dicarboxylation reaction of an olefin, the residual gas containing any one or more of carbon monoxide, oxygen, and a dilution gas used as needed in the reaction apparatus can be recovered from the reaction apparatus, the concentration can be adjusted, and then it can be used again in the dicarboxylation reaction of an olefin.

[0057] "Heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier"

[0058] The heterogeneous catalyst used in this embodiment is a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier. One type of heterogeneous catalyst can be used alone, or two or more types can be used.

[0059] In the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, since a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier is used as a catalyst, for example, compared with the case of using a homogeneous catalyst containing palladium, a compound having a dicarboxylic acid derivative structure as a target can be produced in a high yield.

[0060] The reason why good results can be obtained by using a heterogeneous catalyst is not yet clear. In the dicarboxylation reaction of an olefin, the palladium-containing compound functions as a catalyst to promote the conversion of the olefin into a compound having a dicarboxylic acid derivative structure. It is considered that thereafter, due to the action of the ammonium salt and oxygen present in the reaction system, the palladium-containing compound changed by the reaction returns to a state where it can be used as a catalyst again (being catalyzed). Regarding the phenomenon of returning to a state where it can be used as a catalyst here, it is presumed that there is a certain reason why it becomes more advantageous in the case of using a heterogeneous catalyst compared with the case of using a homogeneous catalyst.

[0061] The heterogeneous catalyst used in this embodiment can be easily separated from the reaction solution by using methods such as centrifugation and / or filtration after the dicarboxylation reaction of an olefin. Moreover, the heterogeneous catalyst separated from the reaction solution can be used again in the dicarboxylation reaction of an olefin, etc. Thus, compared with a homogeneous catalyst, the heterogeneous catalyst is preferably used as a catalyst in an industrial production method.

[0062] As a carrier for a heterogeneous catalyst, for example, activated carbon, titanium dioxide, zirconium oxide, silica, alumina, silica-alumina, diatomaceous earth, magnesia, pumice, or molecular sieve can be used. Among them, as the carrier, activated carbon and / or alumina are preferably used. This is because these carriers are easily available and have a high specific surface area. Therefore, by finely dispersing the fine particles formed from the palladium-containing compound inside the carrier, high activity can be obtained and the poisoning resistance is also high.

[0063] The carrier of the heterogeneous catalyst can be only one kind or two or more kinds.

[0064] The shape and size of the carrier of the heterogeneous catalyst are not particularly limited, and a shape having sufficient strength and capable of sufficiently ensuring the contact area with the raw material is preferred.

[0065] Specifically, as the carrier of the heterogeneous catalyst, for example, a spherical carrier with an average particle diameter of 0.020 mm to 0.36 mm can be used.

[0066] In addition, as the carrier of the heterogeneous catalyst, for example, a carrier with a specific surface area of 5 m 2 / g to 1500 m 2 / g can be used. In addition, as the carrier of the heterogeneous catalyst, for example, a carrier with an average micropore diameter of 1 nm to 50 nm can be used. The above values are the values obtained by measurement by the BET method (nitrogen adsorption method).

[0067] The palladium-containing compound supported on the carrier of the heterogeneous catalyst can be metallic palladium or a palladium compound. As the palladium compounds that can be used as the palladium-containing compound, for example, inorganic acid salts of palladium such as palladium oxide, palladium nitrate, palladium sulfate, palladium chloride, palladium phosphate, etc., halides of palladium such as palladium chloride, palladium bromide, etc., and organic acid salts of palladium such as palladium acetate, palladium propionate, palladium benzoate, etc. can be cited. Among them, as the palladium-containing compound, metallic palladium is preferably used. This is because the dicarboxylation reaction of olefins can be effectively promoted, and a compound having a dicarboxylic acid derivative structure in which a total of 2 carboxyl groups and / or carboxylic acid ester groups are introduced into the carbon-carbon double bond of the olefin can be produced in a higher yield.

[0068] The palladium-containing compound supported on the carrier of the heterogeneous catalyst can be only one kind or two or more kinds.

[0069] The loading amount (content of palladium atoms) of the palladium-containing compound in the heterogeneous catalyst is not particularly limited. For example, it can be set to 0.1% by mass to 20% by mass, preferably set to 0.5% by mass to 10% by mass, and can be appropriately determined according to the usage amount of the heterogeneous catalyst relative to the usage amount of the olefin used as the raw material, etc.

[0070] The heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier is not particularly limited. For example, when alumina is exemplified as the carrier, it can be produced by the method shown below or the like.

[0071] Prepare 250 μL of an aqueous solution of palladium(II) nitrate with a concentration of 200 g / L. Add 0.95 g of an alumina carrier to the aqueous solution of palladium(II) nitrate and stir at room temperature for 30 minutes. Then, remove the water by vacuum drying. The resulting residue is calcined in air at a temperature of 550 °C for 4 hours to obtain an alumina-supported palladium catalyst in which palladium(II) oxide is supported on alumina as a heterogeneous catalyst. At this time, the palladium loading amount (content of palladium atoms) in the obtained heterogeneous catalyst is 5% by mass.

[0072] As the heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier, a commercially available heterogeneous catalyst can be used. Examples of the commercially available heterogeneous catalyst include a heterogeneous catalyst in which metallic palladium is supported on activated carbon (Scitem, manufactured by YMC), Pd supported on barium sulfate (manufactured by TCI), Pd supported on calcium carbonate (manufactured by TCI), Pd supported on activated carbon (manufactured by SIGMA-ALDRICH), and the like.

[0073] Relative to 1 mole of the olefin used in the reaction, the palladium-containing compound contained in the heterogeneous catalyst is preferably 1.0 μmol% to 10 mol%, more preferably 5.0 μmol% to 1.0 mol%. If the amount of the palladium-containing compound contained in the heterogeneous catalyst is 1.0 μmol% or more relative to 1 mole of the olefin, the dicarboxylation reaction of the olefin is effectively promoted, and a compound having a dicarboxylic acid derivative structure in which a total of 2 carboxyl groups and / or carboxylic acid ester groups are introduced into the carbon-carbon double bond of the olefin can be produced in a higher yield. If the amount of the above palladium-containing compound is 10 mol% or less, side reactions in the dicarboxylation reaction of the olefin can be effectively suppressed, and a compound having a dicarboxylic acid derivative structure as the target can be produced in a higher yield.

[0074] The heterogeneous catalyst used in this embodiment can be separated from the reaction solution by a method such as centrifuging the reaction solution after the dicarboxylation reaction of the olefin is diluted as needed and / or a method of filtration. The heterogeneous catalyst separated from the reaction solution can be reused for the dicarboxylation reaction of the olefin.

[0075] "ammonium salt"

[0076] Examples of the ammonium salt used in the present embodiment include ammonium chloride, ammonium bromide, ammonium iodide, methylammonium chloride, benzyltrimethylammonium chloride, tetraalkylammonium salts, etc. Examples of the tetraalkylammonium salt include tetrabutylammonium chloride. Among them, as the ammonium salt, a halogen-containing ammonium salt is preferably used, and ammonium chloride is particularly preferably used. The halogen-containing ammonium salt can effectively promote the regeneration and catalyst formation due to the reoxidation of the palladium-containing compound changed by the reaction, and stabilize the palladium-containing compound possessed by the heterogeneous catalyst through the halide ion of the counter anion. This is because the dicarboxylation reaction of olefins can be effectively promoted, and a compound having a dicarboxylic acid derivative structure in which a total of two carboxyl groups and / or carboxylic acid ester groups are introduced into the carbon-carbon double bond of the olefin can be produced in a higher yield.

[0077] The ammonium salt used in the present embodiment may be only one kind, or two or more kinds.

[0078] With respect to 1 mol of the olefin used as a raw material, the amount of the ammonium salt used is preferably 1.0 to 10 molar amounts, more preferably 2.0 to 5.0 molar amounts. If the amount of the ammonium salt contained in the heterogeneous catalyst is 1.0 molar amount or more with respect to 1 mol of the olefin, the dicarboxylation reaction of the olefin is effectively promoted, and a compound having a dicarboxylic acid derivative structure in which a total of two carboxyl groups and / or carboxylic acid ester groups are introduced into the carbon-carbon double bond of the olefin can be produced in a higher yield. If the amount of the above ammonium salt used is 10 molar amounts or less, precipitation of the ammonium salt in the dicarboxylation reaction of the olefin can be effectively suppressed, and a compound having a dicarboxylic acid derivative structure as a target can be produced in a higher yield.

[0079] "Solvent"

[0080] In the method for producing a compound having a dicarboxylic acid derivative structure of the present embodiment, one or more solvents that do not hinder the dicarboxylation reaction of the olefin may be contained in the reaction solution for carrying out the dicarboxylation reaction of the olefin as needed. In the method for producing a compound having a dicarboxylic acid derivative structure of the present embodiment, the alcohol used as a raw material can be substantially used as a solvent.

[0081] Examples of the solvent that can be used in the production method of the present embodiment include ethers such as diethyl ether, dipropyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol diethyl ether, or triethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, or acetophenone; esters such as methyl acetate, ethyl acetate, or methyl propionate; aromatic hydrocarbons or their substituted compounds such as benzene, toluene, p-xylene, ethylbenzene, chlorobenzene, or dichlorobenzene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-pentane, isooctane, or cyclohexane; carbonates such as propylene carbonate or dimethyl carbonate; nitriles such as acetonitrile or benzonitrile; amide compounds such as dimethylformamide; or sulfone compounds such as sulfolane.

[0082] In addition, when the solvent does not dissolve the ammonium salt used, a small amount of distilled water can be added to assist the dissolution of the ammonium salt.

[0083] "Reaction conditions"

[0084] The reaction process in the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment is preferably the process shown below. First, a specified amount of an olefin, an alcohol, the above-mentioned heterogeneous catalyst, an ammonium salt, and a solvent used as needed are added into the reaction vessel of the reaction apparatus. Then, carbon monoxide, oxygen, and a dilution gas used as needed are supplied into the reaction vessel serving as the reaction apparatus, and while stirring the inside of the reaction vessel by a known method, the dicarboxylation reaction of the olefin is carried out.

[0085] For carbon monoxide, all of the amount required for the dicarboxylation reaction of the olefin can be supplied to the reaction apparatus at once, or it can be supplied continuously or intermittently. In this embodiment, it is particularly preferable to carry out the reaction while replenishing the carbon monoxide consumed by the dicarboxylation reaction of the olefin in such a manner that the partial pressure of carbon monoxide in the atmosphere for carrying out the dicarboxylation reaction of the olefin is maintained within the range of 0.01 MPa to 10 MPa.

[0086] For oxygen, all of the amount required for the dicarboxylation reaction of the olefin can be supplied to the reaction apparatus at once, or it can be supplied continuously or intermittently. In this embodiment, it is particularly preferable to carry out the reaction while replenishing the oxygen consumed by the dicarboxylation reaction of the olefin in such a manner that the partial pressure of oxygen in the atmosphere for carrying out the dicarboxylation reaction of the olefin is maintained within the range of 0.01 MPa to 2.0 MPa.

[0087] The reaction conditions of the reaction process in the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment can be appropriately determined according to the types of the olefin and alcohol as raw materials, the types of the above-mentioned heterogeneous catalyst and ammonium salt as the catalyst, etc., within the range where the dicarboxylation reaction of the olefin proceeds.

[0088] The reaction conditions preferably satisfy any one or more of the following conditions: (a) reaction apparatus, (b) reaction pressure, (c) reaction temperature, and (d) reaction time shown below.

[0089] (a) Reaction apparatus

[0090] In this embodiment, the reaction apparatus used in the dicarboxylation reaction of an olefin preferably includes a pressure-resistant reaction vessel capable of enclosing the olefin, alcohol, carbon monoxide, and oxygen together with the above-mentioned heterogeneous catalyst and ammonium salt and being hermetically sealed under pressure. Specifically, as the reaction apparatus, for example, an autoclave having a pressure-resistant reaction vessel made of stainless steel such as SUS304, SUS316, SUS316L, titanium, tantalum, nickel, Hastelloy, Inconel, etc. is preferably used.

[0091] (b) Reaction pressure

[0092] Regarding the pressure of the atmosphere (pressure inside the pressure-resistant reaction vessel) for carrying out the dicarboxylation reaction of an olefin, the partial pressures of carbon monoxide and oxygen are preferably within the above ranges. Moreover, the pressure (total pressure) inside the pressure-resistant reaction vessel is preferably in the range of 0.1 MPa (absolute pressure, the same hereinafter) to 10 MPa, more preferably in the range of 0.1 MPa to 5 MPa. If the pressure inside the pressure-resistant reaction vessel is 0.1 MPa or more, the dicarboxylation reaction of the olefin can be effectively promoted, and the dicarboxylic acid derivative can be produced in a higher yield. In addition, if the pressure inside the pressure-resistant reaction vessel is 10 MPa or less, the specifications of the reaction vessel can be containers that can be used in general industrial applications in process design, so no special structure is required, which is preferable.

[0093] (c) Reaction temperature

[0094] The temperature of the atmosphere (temperature inside the pressure-resistant reaction vessel) for carrying out the dicarboxylation reaction of an olefin is preferably in the range of 0 °C to 150 °C, more preferably in the range of 20 °C to 100 °C. If the temperature inside the pressure-resistant reaction vessel is 0 °C or more, the dicarboxylation reaction of the olefin is effectively promoted, and a compound having a dicarboxylic acid derivative structure can be produced in a higher yield. If the temperature inside the pressure-resistant reaction vessel is 150 °C or less, side reactions in the dicarboxylation reaction of the olefin can be effectively suppressed, and a compound having a dicarboxylic acid derivative structure can be produced in a higher yield.

[0095] (d) Reaction time

[0096] The reaction time in the reaction process is preferably in the range of 0.5 hours to 100 hours, more preferably 3 to 48 hours. If the reaction time is 0.5 hours or more, the dicarboxylation reaction of the olefin proceeds sufficiently, so a compound having a dicarboxylic acid derivative structure can be produced in a higher yield. If the reaction time is 100 hours or less, a compound having a dicarboxylic acid derivative structure can be efficiently produced, and side reactions in the dicarboxylation reaction of the olefin can be effectively suppressed.

[0097] "Compound having a dicarboxylic acid derivative structure"

[0098] In the method for producing a compound having a dicarboxylic acid derivative structure according to this embodiment, a compound having a dicarboxylic acid derivative structure in which a total of two carboxyl groups (-COOH) and / or carboxylic acid ester groups (-COOR (R is an alkyl group derived from the alcohol used as a raw material)) are introduced into the carbon-carbon double bond of an olefin (unsaturated hydrocarbon) is obtained. The obtained compound having a dicarboxylic acid derivative structure is a compound in which a carboxyl group or a carboxylic acid ester group is bonded to adjacent carbon atoms, and is a useful compound that can be used as a raw material for various compounds, an additive in resins, etc. Specifically, for example, by reacting a compound having a dicarboxylic acid derivative structure produced by using the production method of this embodiment with an amino compound, an industrially useful compound having an imide bond can be produced. Therefore, the compound having a dicarboxylic acid derivative structure produced by using the production method of this embodiment can be used as a raw material for a compound having an imide bond.

[0099] In the production method of this embodiment, when an alicyclic olefin is used as a raw material, as the compound having a dicarboxylic acid derivative structure, a compound having a cyclic skeleton and in which a carboxyl group or a carboxylic acid ester group is bonded to adjacent carbon atoms can be obtained. The obtained compound having a dicarboxylic acid derivative structure can be used as a raw material for an industrially more useful compound having an imide bond. Therefore, the effect of increasing the yield by using the production method of this embodiment becomes remarkable.

[0100] For example, in the production method of this embodiment, when a compound represented by the formula (1) which is an alicyclic olefin is used as a raw material, as the compound having a dicarboxylic acid derivative structure, a compound represented by the following formula (2) can be obtained. At this time, R 11 and R 12 in the formula (2) are respectively groups derived from R 1 and R 2 in the formula (1).

[0101]

[0102] In the formula (2), R 11 、R 12 、R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms.

[0103] In the compound represented by the formula (2), R 11 、R 12 、R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, preferably a hydrogen atom or an alkyl group having 1 or more and 3 or less carbon atoms. R 11 、R 12 、R3 and R 4 may be different from each other, or may be partially or entirely the same.

[0104] In the compound represented by formula (2), R 11 and R 12 are groups derived from R 1 and R 2 in the compound represented by formula (1) used as a raw material.

[0105] R in formula (2) 11 , may be the same as R 1 in formula (1), or may be -COOR 1 in formula (1) as an ester moiety hydrolyzes to form a carboxyl group (-COOH), thereby becoming a hydrogen atom. Additionally, R 12 in formula (2), may be the same as R 2 in formula (1), or may be -COOR 2 in formula (1) hydrolyzes to form a carboxyl group (-COOH), thereby becoming a hydrogen atom.

[0106] R 3 and R 4 are groups derived from the alcohol used as a raw material. For example, when an alkyl alcohol is used as the alcohol, R 3 and R 4 are groups of the alkyl from the alkyl alcohol. When only one type of alcohol is used as a raw material, R 3 and R 4 tend to be the same group. Considering the ease of separating and purifying the target product from the reaction solution after the reaction, it is preferred that R 3 and R 4 are the same. R 3 and / or R 4 are particularly preferably methyl, because in this case, it is an industrially useful compound having a dicarboxylic acid derivative structure.

[0107] R 11 , R 12 , R 3 and R 4 in part or in whole may be hydrogen atoms. That is, the compound represented by formula (2) may be a carboxylic acid. R 11 , R 12 , R 3 and R 4 in part or in whole being hydrogen atoms, are formed by any one or more of the reactions <1> to <3> shown below in the reaction for generating a dicarboxylic acid derivative structure.

[0108] <1> When the carbon-carbon double bond in the compound represented by the formula (1) reacts, the water molecules present in the reaction system react instead of the alcohol used as a raw material.

[0109] <2> As -COOR which is an ester moiety introduced onto the carbon-carbon double bond in the compound represented by the formula (2) 3 and -COOR 4 One or both of them react with the water molecules present in the reaction system and undergo hydrolysis.

[0110] <3> As -COOR which is an ester moiety in the compound represented by the formula (1) 1 and -COOR 2 One or both of them react with the water molecules present in the reaction system and undergo hydrolysis.

[0111] In the production method of the present embodiment, when evaluating the reaction yield, R 11 , R 12 , R 3 and R 4 respectively being alkyl groups having 1 or more and 5 or less carbon atoms, the yield of the compound, R 11 , R 12 , R 3 and R 4 part or all of which being hydrogen atoms, the yield of the compound, and their total yield can be considered for evaluation.

[0112] The compound represented by the formula (2) can be used as a raw material for a diimide compound, for example. Specifically, the ester group of the compound represented by the formula (2) is hydrolyzed to form a carboxylic acid structure. Thereby, a tetracarboxylic acid compound in which R 11 , R 12 , R 3 and R 4 are all replaced by hydrogen atoms is formed. Then, the obtained tetracarboxylic acid compound is used to produce an imide compound by a known method.

[0113] When the compound represented by the formula (2) is used as a raw material for a diimide compound in this way, it is used after hydrolyzing the ester group to form a carboxylic acid structure. Therefore, by the production method of the present embodiment, as the compound represented by the formula (2), when obtaining a compound in which R 11 , R 12 , R 3 and R 4 are respectively alkyl groups having 1 or more and 5 or less carbon atoms, when obtaining R 11 , R 12 , R 3 and R 4In the case of a compound in which part or all of the hydrogen atoms are hydrogen atoms, and in the case of producing a mixture of these compounds, they can all be used as raw materials in the synthesis of the diimide compound in the same manner.

[0114] The compound represented by formula (2) has -COOR 11 , -COOR 12 , -COOR 3 , -COOR 4 A structure in which these 4 groups are bonded to the norbornene skeleton. Therefore, the compound represented by formula (2) can be used as a raw material for a polyimide having a norbornene skeleton and an imide bond, which is industrially useful, by reacting with an amino compound. Therefore, the effect of increasing the yield by using the production method of the present embodiment becomes remarkable.

[0115] Examples

[0116] Hereinafter, the present invention will be described more specifically by way of examples and comparative examples. It should be noted that the present invention is not limited to the following examples.

[0117] (Reference Example)

[0118] [Synthesis of the compound represented by formula (1)]

[0119] Dissolve 10.3 g (57 mmol) of bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (sometimes also referred to as "bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid") in 200 mL of N,N-dimethylformamide (manufactured by Fujifilm Wako). To this solution, add 31.3 g of potassium carbonate (manufactured by Fujifilm Wako, 226 mmol) and 14 mL of methyl iodide (manufactured by Tokyo Chemical Industry, 226 mmol), and stir at room temperature for 48 hours to react.

[0120] Add water and ethyl acetate to the reaction solution after the reaction for liquid separation. Wash the organic layer with water, dry it over anhydrous sodium sulfate, and then distill off the solvent under reduced pressure. Purify the residue by column chromatography to obtain dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate as a white solid (yield 10.0 g, yield 84%).

[0121] Using the gas chromatograph shown below, analyze the obtained white solid under the analysis conditions shown below. As a result, it was confirmed to be dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate as the compound represented by formula (1) (R 1 and R 2 ) in formula (1).

[0122] (Analysis conditions for gas chromatography)

[0123] As the gas chromatography method, GC6850 Series II manufactured by Agilent was used. As the detector, FID (flame ionization detector) was used. As the column, J&W HP-1 column (0.25 μm thick, 0.32 mm I.D., 30 m) was used. Then, the measurement was carried out at a column temperature of 40 °C and a measurement temperature of 40 to 240 °C. Specifically, the procedure was as follows: After maintaining at 40 °C for 5 minutes, the temperature was raised to 240 °C at a rate of 10 °C per minute and maintained at 240 °C for 5 minutes.

[0124] (Example 1)

[0125] [Manufacture of Compounds with Dicarboxylic Acid Derivative Structure]

[0126] 200 mg (0.95 mmol) of dimethyl bicyclo[2.2.1]hept-5-ene-2endo,3endo-dicarboxylate, which is the compound represented by formula (1) synthesized by the above method (R 1 and R 2 in formula (1) are methyl), 10.2 mg (4.8 μmol) of palladium on activated carbon (manufactured by YMC), and 127 mg (2.4 mmol) of ammonium chloride (manufactured by Sigma-Aldrich) were weighed and placed in a glass cylindrical container.

[0127] For the palladium on activated carbon (manufactured by YMC), palladium on activated carbon was used in which metallic palladium was supported on a carrier composed of spherical activated carbon with an average particle diameter of 0.36 mm, a specific surface area of 1371 m 2 / g, and an average micropore diameter of 1.7 nm, and the palladium loading amount (content of palladium atoms) was 5 mass%. The specific surface area of the activated carbon is a value obtained by measurement by the BET method (surface area measurement method).

[0128] 3.0 mL of methanol (manufactured by FUJIFILM Wako) and 1.0 mL of distilled water (added to dissolve ammonium chloride) were further added into the above cylindrical container. Then, the cylindrical container containing the above materials was placed in a pressure-resistant reaction vessel of an autoclave and sealed.

[0129] After supplying oxygen into the pressure-resistant reaction vessel so that the partial pressure of oxygen was 1.0 MPa, carbon monoxide was supplied so that the partial pressure of carbon monoxide was 3.5 MPa, and the total pressure in the pressure-resistant reaction vessel was 4.5 MPa. Then, while vigorously stirring the inside of the pressure-resistant reaction vessel, the reaction was carried out at 60 °C for 24 hours.

[0130] After the reaction was completed, the mixture was cooled until the temperature inside the pressure-resistant reaction vessel reached room temperature, and the pressure was released. The reaction solution in the above-mentioned cylindrical container was recovered. A part of the reaction solution was sampled as a test sample by the method shown below, and analyzed using the above gas chromatography under the above analysis conditions to identify the reaction products. As a result, it was confirmed that the reaction product was bicyclo[2.2.1]heptane-2-endo,3-endo,5-exo,6-exo-tetracarboxylic acid tetramethyl ester (the compound represented by formula (2) (R 11 and R 12 and R 3 and R 4 in formula (2) are methyl groups)), which is the target substance of Example 1).

[0131] (Sampling method of test sample)

[0132] 50 μL of diethylene glycol dimethyl ether as an internal standard substance was added to the reaction solution in the cylindrical container after the reaction, and the mixture was transferred to a screw-cap test tube together with the reaction solution, and then diluted with 7 mL of methanol. The diluted reaction solution was centrifuged at 3000 rpm for 5 minutes at room temperature to precipitate the heterogeneous catalyst contained in the diluted reaction solution, and the supernatant was collected (sampled) as a test sample for analysis.

[0133] In addition, using the identification results of the reaction products, the conversion rate of the compound represented by formula (1), the yield of the target substance (the compound in which R 11 and R 12 and R 3 and R 4 in formula (2) are methyl groups), the yield of the hydrolysis product of the target substance of Example 1 (the total of the compounds in which a part or all of R 11 and R 12 and R 3 and R 4 in formula (2) are hydrogen atoms), and their total yield (yield of the target substance + yield of the hydrolysis product) were calculated. The results are shown in Table 1.

[0134] As shown in Table 1, in Example 1, the conversion rate of the reaction was 100%. In addition, the yield of bicyclo[2.2.1]heptane-2-endo,3-endo,5-exo,6-exo-tetracarboxylic acid tetramethyl ester (the compound represented by formula (2) (R 11 and R 12 and R 3 and R 4 in formula (2) are methyl groups)), which is the target substance, was 100%.

[0135] Table 1

[0136]

[0137] (Example 2)

[0138] As a heterogeneous catalyst, palladium - supported alumina in which a palladium - containing compound is supported on a carrier made of alumina and which is produced by the method shown below was used. Otherwise, the same operations as in Example 1 were carried out to produce a compound having a dicarboxylic acid derivative structure.

[0139] The resulting reaction product was identified in the same manner as in Example 1. As a result, it was confirmed that the reaction product was a compound in which R 11 , R 12 , R 3 , R 4 in formula (2) as the target product of Example 2 was methyl, and a mixture of a compound in which R 11 , R 12 , R 3 and R 4 in formula (2) as the hydrolyzate of the target product of Example 2 were partly or wholly hydrogen atoms.

[0140] In addition, using the identification result of the reaction product, the conversion rate of the compound represented by formula (1), the yield of the target product, the yield of the hydrolyzate, and their total yield (yield of the target product + yield of the hydrolyzate) were calculated in the same manner as in Example 1. The results are shown in Table 1.

[0141] As shown in Table 1, in Example 2, the conversion rate of the reaction was 98%, which is a very high result. In addition, the total yield was 97%, which is high enough.

[0142] (Method for producing a heterogeneous catalyst (palladium - supported alumina))

[0143] A palladium - supported alumina catalyst was prepared through the following steps.

[0144] First, 250 μL of an aqueous palladium(II) nitrate solution with a concentration of 200 g / L was prepared. The palladium concentration in the aqueous palladium(II) nitrate solution was adjusted so that the palladium loading amount (content of palladium atoms) in the heterogeneous catalyst produced using it became 5% by mass.

[0145] 0.95 g of an alumina carrier was added to the resulting aqueous palladium(II) nitrate solution, and the mixture was stirred at room temperature for 30 minutes to impregnate the aqueous palladium(II) nitrate solution into the alumina carrier. As the alumina carrier, one with an average particle size of 0.0201 mm and a specific surface area of 104 m 2 / g, spherical alumina support (JRC-ALO-10, manufactured by Nippon Light Metal Co., Ltd.) with an average micropore diameter of 20.1 nm. Then, through vacuum drying, water was removed from the alumina support impregnated with an aqueous solution of palladium(II) nitrate. The resulting residue was calcined in air at a temperature of 550 °C for 4 hours, thereby obtaining an alumina-supported palladium catalyst with palladium(II) oxide supported on alumina.

[0146] (Comparative Example 1)

[0147] Oxygen was not supplied into the pressure-resistant reaction vessel, and otherwise, the same operations as in Example 1 were carried out to produce a compound having a dicarboxylic acid derivative structure. However, as shown in Table 1, the conversion rate of the compound represented by the formula (1) was 0%, and the compound represented by the formula (2) as the target product was not formed.

[0148] (Comparative Example 2)

[0149] As an alternative to the heterogeneous catalyst, 8.5 mg (5 mol%) of palladium chloride (manufactured by Fujifilm Wako Pure Chemical Corporation) as a homogeneous catalyst was used, and otherwise, the same operations as in Example 1 were carried out to produce a compound having a dicarboxylic acid derivative structure.

[0150] Then, the reaction solution after the reaction was sampled directly without centrifugation, and analyzed by gas chromatography in the same manner as in Example 1 to identify the reaction products. As a result, it was confirmed that the reaction product was a compound in which R 11 , R 12 , R 3 , R 4 in the formula (2) as the target product of Comparative Example 2 was methyl, and a mixture of compounds in which part or all of R 11 , R 12 , R 3 and R 4 in the formula (2) as the hydrolyzate of the target product of Comparative Example 2 were hydrogen atoms.

[0151] In addition, using the identification results of the reaction products, the conversion rate of the compound represented by the formula (1), the yield of the target product, the yield of the hydrolyzate, and their total yield (yield of the target product + yield of the hydrolyzate) were calculated in the same manner as in Example 1. The results are shown in Table 1.

[0152] As shown in Table 1, in Comparative Example 2, the conversion rate of the reaction was 100%. However, the total yield of the target product and the hydrolyzate was 22%, which was lower than that of Example 1 and Example 2.

[0153] (Examples 3 to 5, Comparative Example 3, Comparative Example 4)

[0154] Use 2.4 mmol of the ammonium salt shown in Table 2 or a nitrogen-containing compound that is not an ammonium salt instead of ammonium chloride, and perform the same operations as in Example 1 to produce a compound having a dicarboxylic acid derivative structure.

[0155] (Comparative Example 5)

[0156] Except for not adding ammonium chloride, perform the same operations as in Example 1 to produce a compound having a dicarboxylic acid derivative structure.

[0157] Identify the reaction products obtained in Examples 3 to 5 and Comparative Examples 3 to 5 in the same manner as in Example 1. As a result, it was confirmed that the reaction products contained bicyclo[2.2.1]heptane-2endo,3endo,5exo,6exo-tetracarboxylic acid tetramethyl ester (the compound represented by Formula (2) (R 11 、R 12 、R 3 、R 4 in Formula (2) being methyl)) as the target substance.

[0158] In addition, using the identification results of the reaction products obtained in Examples 3 to 5 and Comparative Examples 3 to 5, calculate the conversion rate of the compound represented by Formula (1), the yield of the target substance, the yield of the hydrolyzate of the target substance, and the total yield (yield of the target substance + yield of the hydrolyzate) in the same manner as in Example 1. The results are shown in Table 2. Moreover, Table 2 also shows the usage amount (mass) and purchase source of the ammonium salt, and the results of Example 1.

[0159] Table 2

[0160]

[0161] As shown in Table 2, in Examples 3 to 5 where other ammonium salts were used instead of ammonium chloride, the total yields of the target substance and the hydrolyzate were all 60% or more, which is sufficiently high.

[0162] In contrast, Comparative Examples 3 and 4, which used a nitrogen-containing compound that is not an ammonium salt instead of ammonium chloride, and Comparative Example 5, which did not add an ammonium salt, gave low yields of the target substance and total yields.

[0163] Industrial Applicability

[0164] React an olefin, an alcohol, carbon monoxide, and oxygen in the presence of a heterogeneous catalyst formed by supporting a palladium-containing compound on a carrier and an ammonium salt. A compound having a dicarboxylic acid derivative structure in which a total of two carboxyl groups and / or carboxylic acid ester groups are introduced into the carbon-carbon double bond of the olefin can be produced in a high yield.

Claims

1. A method for producing a compound having a dicarboxylic acid derivative structure, which comprises a reaction step of reacting an olefin, an alcohol, carbon monoxide, and oxygen in the presence of a heterogeneous catalyst formed by supporting a palladium compound on a carrier and an ammonium salt.

2. The method for producing a compound having a dicarboxylic acid derivative structure according to claim 1, wherein the ammonium salt is ammonium chloride.

3. The method for producing a compound having a dicarboxylic acid derivative structure according to claim 1 or 2, wherein the olefin is an alicyclic olefin.

4. The method for producing a compound having a dicarboxylic acid derivative structure according to claim 1 or 2, wherein the olefin is a compound represented by the following formula (1), In formula (1), R 1 and R 2 each independently represent an alkyl group having 1 to 5 carbon atoms.

5. The method for producing a compound having a dicarboxylic acid derivative structure according to claim 1 or 2, wherein the compound having a dicarboxylic acid derivative structure is a compound represented by the following formula (2), In formula (2), R 11 , R 12 , R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

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