Method for producing methylene disulfonate compounds

Abstract

Provided is a method for producing a methylene disulfonate compound that is industrially advantageous and makes it possible to produce a methylene disulfonate compound easily and inexpensively by fewer raw materials.　The method for producing a methylene disulfonate compound of the present invention includes a step A for obtaining a reactant A that includes an alkane disulfonic acid compound by reacting at least one alkane sulfonic acid compound and sulfur trioxide in the presence of at least one selected from the group consisting of sulfoxide compounds and sulfone compounds and a step B for obtaining a methylene disulfonate compound by reacting the reactant A obtained in the step A and a formaldehyde compound in the presence of sulfur trioxide.

Description

[Technical field]

[0001] The present invention relates to a method for producing a methylene disulfonate compound. [Background technology]

[0002] Conventionally, methylene disulfonate compounds have been known to be useful not only as pharmaceuticals such as leukemia treatment drugs for animals, but also as raw materials for functional materials such as stabilizers for electrolytes for secondary batteries, and thus can be said to be highly valuable compounds. It is known that such methylene disulfonate compounds can be produced by various methods.

[0003] As an example of a method for producing a methylene disulfonate compound, a method using methanesulfonic acid, which is an inexpensive raw material, is known. For example, Patent Document 1 discloses a technique for producing a methylene disulfonate compound by reacting methanesulfonic acid with sulfur trioxide to produce methane disulfonic acid (first step), and then reacting the obtained methane disulfonic acid with paraformaldehyde in the presence of a dehydrating agent (second step). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] China Patent Application Publication No. 108840852 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the method disclosed in Patent Document 1 has a problem in that the reaction raw materials used in the first step and the second step are different, and in addition, there may be cases where the intermediate needs to be isolated, and therefore the process tends to be complicated.

[0006] The present invention has been made in view of the above, and an object of the present invention is to provide a method for producing a methylene disulfonate compound, which can produce a methylene disulfonate compound easily and inexpensively using a smaller amount of raw materials, and is industrially advantageous. [Means for solving the problem]

[0007] As a result of intensive research into achieving the above-mentioned object, the inventors have found that the above-mentioned object can be achieved by utilizing a product obtained by reacting a specific alkanesulfonic acid compound with sulfur trioxide in the presence of a specific sulfoxide compound and / or sulfone compound, and have thus completed the present invention.

[0008] That is, the present invention includes, for example, the subject matter described in the following sections. Item 1 A method for producing a methylene disulfonate compound, comprising the steps of: At least one alkane sulfonic acid compound and sulfur trioxide, A step A of obtaining a reactant A containing an alkane disulfonic acid compound by reacting in the presence of at least one compound selected from the group consisting of a sulfoxide compound and a sulfone compound; A step B of reacting the reactant A obtained in the step A with a formaldehyde compound in the presence of sulfur trioxide to obtain a methylene disulfonate compound; Including, The alkanesulfonic acid compound is represented by the following general formula (1):

[0009] [ka]

[0010] (In formula (1), R 1 and R 2 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom or a hydrogen atom; n represents an integer of 1 to 4; when n is an integer of 2 to 4, n R 1 may be the same or different, and n R 2may be the same or different.) A compound represented by the formula: The sulfoxide compound is represented by the following general formula (2):

[0011] [ka]

[0012] (In formula (2), R 3 and R 4 are the same or different and each represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, R 3 and R 4 may be bonded to each other together with the sulfur atom to which they are bonded, with or without a heteroatom to form a cyclic structure. A compound represented by the formula: The sulfone compound is represented by the following general formula (3):

[0013] [ka]

[0014] (In formula (3), R 3 and R 4 are the same or different and each represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, R 3 and R 4 may be bonded to each other together with the sulfur atom to which they are bonded, with or without a heteroatom to form a cyclic structure. A compound represented by the formula: The alkane disulfonic acid compound is represented by the following general formula (4):

[0015] [ka]

[0016] (In formula (4), R 1 , R 2 and n are each R in formula (1). 1 , R 2and n.) A compound represented by the formula: The methylene disulfonate compound is represented by the following general formula (5):

[0017] [ka]

[0018] (In formula (5), R 1 , R 2 and n are each R in formula (1). 1 , R 2 and n.) A method for producing a methylene disulfonate compound represented by the formula: Section 2 Item 2. The method for producing a methylene disulfonate compound according to Item 1, wherein the alkane disulfonic acid compound is not isolated from the reactant A obtained in the step A, and the reactant A is used in the step B. Section 3 Item 3. The method for producing a methylene disulfonate compound according to Item 1 or 2, wherein the reaction in step A and the reaction in step B are carried out in the presence of a solvent. Section 4 Item 4. The method for producing a methylene disulfonate compound according to Item 3, wherein the solvent contains a compound represented by formula (3). Section 5 Item 5. The method for producing a methylene disulfonate compound according to item 4, wherein the compound represented by formula (3) is sulfolane. Section 6 6. The method for producing a methylene disulfonate compound according to any one of items 1 to 5, wherein the formaldehyde compound is at least one selected from the group consisting of paraformaldehyde, anhydrous formaldehyde, trioxane, and methylal. Effect of the Invention

[0019] According to the production method of the present invention, it is possible to produce a methylene disulfonate compound easily and inexpensively using fewer raw materials, and therefore the production method of the present invention is industrially advantageous. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the term "comprising" includes "consisting essentially of" and "consisting of."

[0021] In the numerical ranges described in stages in this specification, the upper or lower limit of a certain numerical range can be arbitrarily combined with the upper or lower limit of another numerical range. In the numerical ranges described in this specification, the upper or lower limit of the numerical range may be replaced with a value shown in an example or a value that can be unambiguously derived from an example. In addition, in this specification, a numerical value connected with "~" means a numerical range that includes the numerical values ​​before and after "~" as the lower and upper limits.

[0022] The method for producing a methylene disulfonate compound of the present invention includes at least the following steps A and B. Step A: A step of reacting at least one alkane sulfonic acid compound with sulfur trioxide in the presence of at least one compound selected from the group consisting of a sulfoxide compound and a sulfone compound to obtain a reactant A containing an alkane disulfonic acid compound. Step B: A step of reacting the reactant A obtained in the step A with a formaldehyde compound in the presence of sulfur trioxide to obtain a methylene disulfonate compound.

[0023] 1. Project A In step A, at least one alkane disulfonic acid compound is reacted with sulfur trioxide in the presence of at least one compound selected from the group consisting of sulfoxide compounds and sulfone compounds. This reaction produces a reactant A containing an alkane disulfonic acid compound. Specifically, step A is a step for producing an alkane disulfonic acid compound.

[0024] (Alkanesulfonic acid compounds) The alkanesulfonic acid compound used in step A is a compound represented by the following general formula (1).

[0025] [ka]

[0026] Here, in formula (1), R 1 and R 2 are the same or different and each represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom or a hydrogen atom, and n represents an integer of 1 to 4. In formula (1), when n is an integer of 2 to 4, n R 1 may be the same or different. When n is an integer of 2 to 4, n R 2 may be the same or different.

[0027] R in Equation (1) 1 and R 2 In the above, the type of the alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom is not particularly limited. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Specific examples of the alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a chloroethyl group, a chloropropyl group, and a bromomethyl group.

[0028] In formula (1), R 1 R is preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and more preferably a hydrogen atom. 2 is preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and more preferably a hydrogen atom. 1 and R 2 are preferably the same.

[0029] In formula (1), when n is an integer of 2 to 4, that is, when n is 2, 3, or 4, n R 1 may be the same or different, and similarly, n R 2 In formula (1), when n is an integer of 2 to 4, n R 1 are preferably all the same, and when n is an integer of 2 to 4, n R 2 are preferably all the same.

[0030] In the formula (1), n ​​is particularly preferably 1, in which case the yield of the target alkanedisulfonic acid compound tends to be particularly high.

[0031] The alkane sulfonic acid compound is not particularly limited as long as it is a compound represented by formula (1). Preferably, the alkane sulfonic acid compound is methanesulfonic acid (in formula (1), R 1 =R 2 =H, n=1), ethanesulfonic acid (in formula (1), R 1 =CH3, R 2 =H, n=1), 1-propanesulfonic acid (in formula (1), R 1 =CH2CH3,R 2 =H, n=1), 2-propanesulfonic acid (in formula (1), R 1 =R 2 =CH3, n=1), 1-butanesulfonic acid (in formula (1), R 1 =R 2 =H, n=4), etc.

[0032] The alkane sulfonic acid compound used in step A can be obtained from a commercial product, or can be obtained by a known method or a method easily derived from a known method. For example, the alkane sulfonic acid compound can be synthesized by a method of oxidizing a corresponding disulfide compound using methyltrioxorhenium(VII) / hydrogen peroxide as a catalyst, with reference to Tetrahedron Letters (2009), 50(46), 6231-6232. Alternatively, the alkane sulfonic acid compound can be synthesized by a method of oxidizing a corresponding thiol compound using hydrogen peroxide, with reference to International Publication No. WO 2004 / 058693.

[0033] The alkanesulfonic acid compound used in step A may be one type alone or two or more types in combination.

[0034] (Sulfoxide compounds and sulfone compounds) In step A, either or both of a sulfoxide compound and a sulfone compound can be used.

[0035] The sulfoxide compound is a compound represented by the following general formula (2).

[0036] [ka]

[0037] Here, in formula (2), R 3 and R 4 are the same or different and each represents an alkyl group having 1 to 12 carbon atoms which may have a substituent. In formula (2), R 3 and R 4 may be bonded to each other together with the sulfur atom to which they are attached to form a cyclic structure with or without a heteroatom.

[0038] The sulfone compound is a compound represented by the following general formula (3).

[0039] [ka]

[0040] Here, in formula (3), R 3 and R 4 are the same or different and each represents an alkyl group having 1 to 12 carbon atoms which may have a substituent, R 3 and R 4 may be bonded to each other together with the sulfur atom to which they are bonded, with or without a heteroatom to form a ring structure. 3 and R 4 is R in Eq. (2). 3 and R 4 is synonymous with.

[0041] R in formula (2) and formula (3) 3 and R 4 In the formula (I), when the alkyl group having 1 to 12 carbon atoms has a substituent, the type of the substituent is not particularly limited. Specific examples of the substituent include a halogen atom, an alkoxy group, a carboxyl group, a cyano group, a nitro group, and a sulfo group.

[0042] R in formula (2) and formula (3) 3 and R 4In the above, examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, an n-octyl group, an n-decyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group, an adamantyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, and a 2-cyclohexylethyl group. These alkyl groups may also have the above-mentioned substituent. The number of carbon atoms is preferably 1 to 6, in that the yield of the target alkanedisulfonic acid compound is likely to be high. Therefore, among the above-listed examples of the alkyl group having 1 to 12 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, an n-hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cyclopentylmethyl group is preferred.

[0043] In formula (2) and formula (3), R 3 and R 4 and may be bonded together with the sulfur atom to which they are bonded to form a cyclic structure with or without a heteroatom. That is, a cyclic structure containing the sulfur atom in the compounds represented by formulas (2) and (3) as a ring member may be formed. In this case, for example, R 3 and R 4 The carbon atoms of R can form chemical bonds to form a ring structure. For example, R 3 and R 4 A cyclic structure can be formed together with the sulfur atom by a covalent bond between the terminal carbon atoms of the ring. The cyclic structure is, for example, a saturated ring containing a sulfur atom. When the cyclic structure has a hetero atom in addition to the sulfur atom, the type of the hetero atom is not particularly limited.

[0044] In the step A, when both the compound represented by formula (2) and the compound represented by formula (3) are used, R 3 and R in Eq. (3) 3may be the same or different. Similarly, in the case where both the compound represented by formula (2) and the compound represented by formula (3) are used in step A, R 4 and R in Eq. (3) 4 may be the same or different from each other.

[0045] Specific examples of the sulfoxide compound represented by formula (2) include dimethyl sulfoxide, ethyl methyl sulfoxide, methyl n-propyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, di-n-octyl sulfoxide, didodecyl sulfoxide, and tetramethylene sulfoxide. Among these, the sulfoxide compound represented by formula (2) is preferably dimethyl sulfoxide.

[0046] Specific examples of the sulfone compound represented by formula (3) include trimethylene sulfone, hexamethylene sulfone, trimethylene disulfone, tetramethylene disulfone, hexamethylene disulfone, sulfolane, 3-methyl sulfolane, dimethyl sulfone, ethyl methyl sulfone, diethyl sulfone, methyl n-propyl sulfone, ethyl n-propyl sulfone, di-n-propyl sulfone, methyl isopropyl sulfone, ethyl isopropyl sulfone, diisopropyl sulfone, n-butyl methyl sulfone, n-butyl ethyl sulfone, t-butyl methyl sulfone, t-butyl ethyl sulfone, etc. Among these, the sulfone compound represented by formula (3) is preferably sulfolane, 3-methyl sulfolane, ethyl methyl sulfone, or ethyl isopropyl sulfone, more preferably sulfolane or 3-methyl sulfolane, and even more preferably sulfolane.

[0047] In the case where both the compound represented by formula (2) and the compound represented by formula (3) are used in step A, the sulfoxide compound and the sulfone compound are preferably at least one selected from the group consisting of dimethyl sulfoxide, sulfolane, 3-methyl sulfolane, ethyl methyl sulfone, and ethyl isopropyl sulfone, more preferably at least one selected from the group consisting of sulfolane, 3-methyl sulfolane, ethyl methyl sulfone, and ethyl isopropyl sulfone, and particularly preferably contain at least sulfolane.

[0048] In step A, the sulfoxide compound and the sulfone compound may be used alone or in combination of two or more kinds.

[0049] The sulfoxide compound and the sulfone compound used in step A are both commercially available, or can be obtained by adopting a known production method or the like.

[0050] (Reaction in Step A) In step A, at least one alkanesulfonic acid compound is reacted with sulfur trioxide (SO3) in the presence of at least one compound selected from the group consisting of sulfoxide compounds and sulfone compounds.

[0051] The total amount of the sulfoxide compound and the sulfone compound used in the reaction of step A is preferably 0.1 mol or more, more preferably 0.2 mol or more, and even more preferably 0.3 mol or more, relative to 1 mol of sulfur trioxide, in that the yield of the target alkanedisulfonic acid compound is likely to be high. Moreover, the total amount of the sulfoxide compound and the sulfone compound used in the reaction of step A is preferably 10 mol or less, more preferably 8 mol or less, and even more preferably 6 mol or less, relative to 1 mol of sulfur trioxide, in that it is more economical.

[0052] The sulfoxide compound and sulfone compound used in the reaction of step A may form a complex with sulfur trioxide depending on the type. For example, when the sulfone compound is sulfolane, it is likely to form a complex with sulfur trioxide.

[0053] The amount of sulfur trioxide used in the reaction of step A is preferably 0.1 mol or more, more preferably 0.2 mol or more, and even more preferably 0.3 mol or more, relative to 1 mol of the alkane sulfonic acid compound, in that the yield of the target alkane disulfonic acid compound is likely to be high. Moreover, the amount of sulfur trioxide used in the reaction of step A is preferably 10 mol or less, more preferably 8 mol or less, and even more preferably 6 mol or less, relative to 1 mol of the alkane sulfonic acid compound, in that it is more economical. Here, "1 mol of the alkane sulfonic acid compound" means that when two or more kinds of alkane sulfonic acid compounds are used, the total amount of them is 1 mol.

[0054] In the reaction of step A, for example, a raw material containing the alkane sulfonic acid compound, sulfur trioxide, and at least one selected from the group consisting of the sulfoxide compound and the sulfone compound is placed in a reaction vessel, and the reaction can be carried out in the reaction vessel while stirring the raw material. Alternatively, in the reaction of step A, for example, a raw material containing the alkane sulfonic acid compound, and at least one selected from the group consisting of the sulfoxide compound and the sulfone compound is placed in a reaction vessel, and the reaction can be carried out by further adding sulfur trioxide while stirring the raw material. In this case, sulfur trioxide can be added in multiple batches.

[0055] A solvent can be used as necessary in the reaction of step A. When a solvent is used, the amount of the solvent used is not particularly limited, and can be, for example, 1500 parts by mass or less, and preferably 1000 parts by mass or less, per 100 parts by mass of the total amount of the alkanesulfonic acid compounds.

[0056] When a solvent is used, the solvent that can be used can be appropriately selected within a range that does not impair the effects of the present invention. Examples of such solvents include hydrocarbon solvents, halogen solvents, ether solvents, ketone solvents, ester solvents, amide solvents, nitrile solvents, sulfoxide solvents, sulfone solvents, and sulfuric acid. Examples of hydrocarbon solvents include toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, hexane, heptane, and decane. Examples of halogen solvents include dichloromethane and 1,2-dichloroethane. Examples of ether solvents include diethyl ether, ethylene glycol dimethyl ether, diisopropyl ether, diphenyl ether, tetrahydrofuran, dioxane, methyl-tert-butyl ether, and cyclopentyl methyl ether. Examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of ester solvents include ethyl acetate and butyl acetate. Examples of amide solvents include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples of nitrile solvents include acetonitrile, etc. Examples of sulfoxide solvents include dimethyl sulfoxide, etc. Examples of sulfone solvents include ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, 3-methyl sulfolane, etc.

[0057] In addition, when the compound represented by the formula (2) or the compound represented by the formula (3) is used in an excess amount relative to sulfur trioxide (SO3) in the reaction of step A, these compounds can essentially function as a solvent. Specifically, when the sulfoxide compound represented by the formula (2) is used in an excess amount, the sulfoxide compound that is not consumed in the reaction functions as a reaction solvent in step A. In this case, the reaction solvent is, for example, the sulfoxide-based solvent described above. In addition, when the sulfoxide compound represented by the formula (3) is used in an excess amount, the sulfone compound that is not consumed in the reaction functions as a reaction solvent in step A. In this case, the reaction solvent is, for example, the sulfone-based solvent described above.

[0058] When a solvent is used in the reaction of step A, the solvent preferably contains at least one selected from the group consisting of a compound represented by formula (2) (sulfoxide compound) and a compound represented by formula (3) (sulfone compound), and more preferably contains a compound represented by formula (3) (sulfone compound). In other words, in the reaction of step A, it is preferable to use an excess amount of a compound represented by formula (2) (sulfoxide compound) and / or a compound represented by formula (3) (sulfone compound), and to use the compound represented by formula (2) (sulfoxide compound) and / or a compound represented by formula (3) (sulfone compound) that is not consumed in the reaction as a solvent. In this case, it is particularly preferable that the solvent is sulfolane, since the yield of the alkane disulfonic acid compound is likely to be higher.

[0059] When the solvent contains the compound represented by formula (2) (sulfoxide compound) and / or the compound represented by formula (3) (sulfone compound), the content is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the solvent. The solvent may be composed only of the compound represented by formula (2) (sulfoxide compound) and / or the compound represented by formula (3) (sulfone compound).

[0060] The type of reaction vessel used in the reaction of step A is not particularly limited, and for example, a wide variety of known reaction vessels can be used.

[0061] The reaction conditions in step A are not particularly limited. For example, the reaction temperature in step A is not particularly limited and can be appropriately set depending on the conditions such as the type of raw material and the amount of raw material. For example, the reaction temperature can be 0 to 200°C, and is preferably 50 to 180°C, more preferably 80 to 170°C, and even more preferably 100 to 160°C, in that the yield of the target product is likely to be high. The reaction time can be appropriately set depending on the reaction temperature, and can be, for example, about 1 to 48 hours.

[0062] In the reaction of step A, the method for adjusting the reaction temperature is not particularly limited. For example, the reaction temperature can be set appropriately by heating a reaction vessel containing the raw materials.

[0063] The reaction in step A can be carried out under any of increased pressure, reduced pressure, and atmospheric pressure. The reaction in step A can also be carried out in an inert gas atmosphere such as nitrogen or argon. The reaction can also be carried out while blowing in an inert gas.

[0064] The reaction in step A produces the target product A containing an alkanedisulfonic acid compound. This alkanedisulfonic acid compound is a compound represented by the following general formula (4).

[0065] [ka]

[0066] Here, in formula (4), R 1 , R 2 and n are each R in formula (1). 1 , R 2 and n.

[0067] Specific examples of the alkane disulfonic acid compound represented by formula (4) include methane disulfonic acid (R 1 =R 2 =H, n=1), 1,1-ethanedisulfonic acid (R 1 =CH3, R 2 =H, n=1), 1,2-ethanedisulfonic acid (R 1 =R 2 =H, n=2), 1,1-propanedisulfonic acid (R 1 =CH2CH3,R 2 =H, n=1), 1,2-propanedisulfonic acid (R 1 =CH3 and H, R 2 =H, n=2), 1,3-propanedisulfonic acid (R 1 =R 2=H, n=3), 2,2-propanedisulfonic acid (R 1 =R 2 =CH3, n=1), 1,4-butanedisulfonic acid (R 1 =R 2 =H, n=4), etc. Among these, the alkanedisulfonic acid compound represented by formula (4) is preferably methanedisulfonic acid, and in this case, the production yield of methylene disulfonate in the subsequent step B is likely to be improved.

[0068] Product A produced in step A may contain unreacted raw materials and by-products in the reaction in addition to the alkanedisulfonic acid compound. When a solvent is used in the reaction of step A, product A is obtained in a state in which the alkanedisulfonic acid compound is dissolved or precipitated in the solvent. As described above, when the compound represented by formula (2) or the compound represented by formula (3) is used as a solvent in an excess amount relative to sulfur trioxide (SO3), product A may also contain these compounds as solvents.

[0069] The product A obtained in the reaction of step A can be used in the reaction of the next step B after isolating the alkane disulfonic acid compound by purification or the like. Alternatively, the reactant A can be used in the reaction of the next step B without isolating the alkane disulfonic acid compound from the product A obtained in the reaction of step A. From the viewpoint of making the entire production process simple and not complicated and facilitating improvement in production efficiency, it is preferable to use the reactant A in step B without isolating the alkane disulfonic acid compound from the product A obtained in the reaction of step A. In other words, the product A containing the alkane disulfonic acid compound obtained in step A can be used as a raw material for producing a methylene disulfonate compound.

[0070] When isolating the alkanedisulfonic acid compound from the product A obtained in step A, for example, a conventionally known purification operation and isolation operation can be adopted, and the method is not particularly limited. For example, the alkanedisulfonic acid compound can be isolated from the product A obtained in step A by a method of extracting and washing the product A obtained after the reaction in step A using a solvent or the like, followed by crystallization.

[0071] Usually, in the production of an alkanedisulfonic acid compound using sulfur trioxide, the reaction between sulfur trioxide and the alkanedisulfonic acid compound is difficult to occur, and the yield of the alkanedisulfonic acid compound is low. In contrast, when the reaction is carried out in the presence of at least one compound selected from the group consisting of sulfoxide compounds and sulfone compounds, as in step A, these compounds have the effect of effectively reacting sulfur trioxide with the alkanesulfonic acid compound, making the reaction between sulfur trioxide and the alkanesulfonic acid compound more likely to occur, and improving the yield of the produced alkanedisulfonic acid compound.

[0072] 2. Project B In step B, the reactant A obtained in step A is reacted with a formaldehyde compound in the presence of sulfur trioxide. This reaction produces the target compound, methylene disulfonate. Specifically, step B is a step for producing a methylene disulfonate compound from an alkane disulfonic acid compound in the product A.

[0073] (Formaldehyde compounds) Examples of the formaldehyde compound used in step B include paraformaldehyde, anhydrous formaldehyde, trioxane, and acetalized formaldehyde (e.g., methylal). Anhydrous formaldehyde can be obtained, for example, by heat-treating paraformaldehyde. Trioxane can be obtained, for example, by acid-treating paraformaldehyde. Among these, the formaldehyde compound used in step B is preferably at least one selected from the group consisting of paraformaldehyde, anhydrous formaldehyde, trioxane, and methylal, more preferably at least one selected from the group consisting of paraformaldehyde, anhydrous formaldehyde, and trioxane, and particularly preferably paraformaldehyde. In step B, the formaldehyde compound can be used alone or in combination of two or more.

[0074] (Reaction in Step B) The amount of the formaldehyde compound used in the reaction of step B is preferably 0.6 mol or more, more preferably 0.7 mol or more, and even more preferably 0.8 mol or more relative to 1 mol of the alkane disulfonic acid compound, in terms of the tendency to increase the yield of the target methylene disulfonate compound. The amount of the formaldehyde compound used in the reaction of step B is preferably 10 mol or less, more preferably 7 mol or less, and even more preferably 5 mol or less relative to 1 mol of the alkane disulfonic acid compound, in terms of the economical aspect.

[0075] The amount of sulfur trioxide used in the reaction of step B is preferably 0.1 mol or more, more preferably 0.2 mol or more, and even more preferably 0.3 mol or more relative to 1 mol of the alkane disulfonic acid compound, in that the yield of the target methylene disulfonate compound is likely to be high. Moreover, the amount of sulfur trioxide used in the reaction of step B is preferably 10 mol or less, more preferably 8 mol or less, and even more preferably 6 mol or less relative to 1 mol of the alkane disulfonic acid compound, in that it is more economical.

[0076] In the reaction of step B, a dehydrating agent may be further used for the purpose of promoting the reaction. Examples of the dehydrating agent include phosphorus pentoxide, phosphorus pentachloride, phosphorus oxychloride, thionyl chloride, acetyl chloride, acetic anhydride, and aluminum chloride. Among these, phosphorus pentoxide is preferably used from the viewpoint of reactivity. The dehydrating agent may be used alone or in combination of two or more kinds.

[0077] In the reaction of step B, the amount of the dehydrating agent used can be, for example, 0 to 10 mol, preferably 0 to 5.0 mol, and more preferably 0 to 3.0 mol, relative to 1 mol of the alkanedisulfonic acid compound. The lower limit of this range is not particularly limited, but can be, for example, about 0.1, 0.5, or 1 mol.

[0078] In the reaction of step B, a solvent can be used as necessary. When a solvent is used, the amount of the solvent used is not particularly limited, and can be, for example, 1500 parts by mass or less, preferably 1000 parts by mass or less, relative to 100 parts by mass of the total amount of the alkane disulfonic acid compound. In addition, when a solvent is used in step B, the amount can be, for example, 10 parts by mass or more, relative to 100 parts by mass of the total amount of the alkane disulfonic acid compound.

[0079] When a solvent is used in the reaction of step B, the type of the solvent can be appropriately selected within a range that does not impair the effects of the present invention. Examples of such solvents include hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, amide solvents, nitrile solvents, sulfoxide solvents, sulfone solvents, and sulfuric acid. Examples of hydrocarbon solvents include toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, hexane, heptane, and decane. Examples of ether solvents include diethyl ether, ethylene glycol dimethyl ether, diisopropyl ether, diphenyl ether, tetrahydrofuran, dioxane, methyl-tert-butyl ether, and cyclopentyl methyl ether. Examples of ketone solvents include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of ester solvents include ethyl acetate and butyl acetate. Examples of amide solvents include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples of nitrile solvents include acetonitrile. Examples of sulfoxide solvents include dimethyl sulfoxide, etc. Examples of sulfone solvents include ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, 3-methyl sulfolane, etc.

[0080] Among these, the solvent used in the reaction of step B is preferably an ether solvent, a ketone solvent, an ester solvent, an amide solvent, a nitrile solvent, a sulfoxide solvent, a sulfone solvent, or sulfuric acid, more preferably a sulfoxide solvent, a sulfone solvent, or sulfuric acid, and further preferably a sulfoxide solvent or a sulfone solvent.

[0081] When a solvent is used in step B, the solvent may contain the compound represented by formula (2) and / or the compound represented by formula (3) that has been used in excess in step A to function as a solvent, as described above. Therefore, the compound represented by formula (2) and / or the compound represented by formula (3) that has been used in excess in step A can be used as a reaction solvent in step B without additionally using any new solvent in step B.

[0082] When a solvent is used in the reaction of step B, the solvent preferably contains a compound represented by formula (3) (sulfone compound), and among them, the solvent is particularly preferably sulfolane, in that the yield of the alkane disulfonic acid compound is likely to be higher. When the solvent contains a compound represented by formula (3) (sulfone compound), the content thereof is 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total mass of the solvent. The solvent may be composed only of the compound represented by formula (3).

[0083] In the production method of the present invention, it is preferable to carry out the reaction in step A and the reaction in step B in the presence of a solvent, and in this case, the target methylene disulfonate compound can be obtained in good yield. In particular, it is preferable to use a solvent containing the compound represented by formula (3) as the solvent in the reaction in step A and the reaction in step B, and it is particularly preferable to use sulfolane as the solvent in the reaction in step A and the reaction in step B. In this case, the yield of the methylene disulfonate compound is improved and a purification treatment after the reaction in step A is not required, making the production process simpler.

[0084] The type of reaction vessel used in the reaction of step B is not particularly limited, and for example, a wide variety of known reaction vessels can be used.

[0085] The reaction method of step B is not particularly limited. For example, a formaldehyde compound (e.g., paraformaldehyde) can be added to a reaction vessel while stirring raw materials including the product A containing the alkane disulfonic acid compound obtained in step A, sulfur trioxide, the dehydrating agent used as necessary, and the solvent used as necessary. Alternatively, a reaction can be performed by adding sulfur trioxide to a reaction vessel while stirring raw materials including the alkane disulfonic acid compound obtained in step A, a formaldehyde compound, the dehydrating agent used as necessary, and the solvent used as necessary. As another method, a reaction can be performed by adding the product A containing the alkane disulfonic acid compound obtained in step A to a reaction vessel while stirring raw materials including the formaldehyde compound, sulfur trioxide, the dehydrating agent used as necessary, and the solvent used as necessary.

[0086] The reaction conditions in step B are not particularly limited. For example, the reaction temperature in step B is not particularly limited, and can be appropriately set according to conditions such as the type of raw material and the amount of raw material. For example, the reaction temperature can be 0 to 200°C, and is preferably 10 to 170°C, more preferably 20 to 160°C, and even more preferably 40 to 160°C, in that the yield of the target product is likely to be high. The reaction temperature can be a so-called multi-stage type, and after a reaction is performed at a certain temperature for a predetermined time, the temperature can be further increased to perform the reaction. Even when the reaction temperature is a multi-stage type, the reaction temperature can be adjusted in the range of 0 to 200°C.

[0087] The reaction time can be appropriately set depending on the reaction temperature, and can be, for example, about 0.1 to 20 hours.

[0088] In the reaction of step B, the method for adjusting the reaction temperature is not particularly limited. For example, the reaction temperature can be set appropriately by heating a reaction vessel containing the raw materials used in step B.

[0089] The reaction in step B can be carried out under any of increased pressure, reduced pressure, and atmospheric pressure. The reaction in step B can also be carried out in an inert gas atmosphere such as nitrogen or argon. The reaction can also be carried out while blowing in an inert gas.

[0090] The reaction in step B produces the target product B containing a methylene disulfonate compound. This methylene disulfonate compound is a compound represented by the following general formula (5).

[0091] [ka]

[0092] In formula (5), R 1 , R 2 and n are each R in formula (1). 1 , R 2 and n is the same as n. In other words, the methylene disulfonate compound represented by formula (5) can be determined depending on the type of the alkane sulfonic acid compound used in step A.

[0093] Specific examples of the methylene disulfonate compound represented by formula (5) include methylenemethane disulfonate (R 1 =R 2 =H, n=1), methylene 1,1-ethane disulfonate (R 1 =CH3, R 2 =H, n=1), methylene 1,2-ethane disulfonate (R 1 =R 2 =H, n=2), methylene 1,1-propane disulfonate (R 1 =CH2CH3,R 2 =H, n=1), methylene 1,2-propane disulfonate (R 1 =CH3 and H, R 2 =H, n=2), methylene 1,3-propane disulfonate (R 1 =R 2 =H, n=3), methylene 2,2-propane disulfonate (R 1 =CH3, R 2=CH3, n=1) and methylene 1,4-butane disulfonate (R 1 =R 2 =H, n=4) and the like.

[0094] The product B obtained in step B can be purified to isolate the methylene disulfonate compound. In this case, for example, conventionally known purification and isolation procedures can be adopted, and the method is not particularly limited. For example, the methylene disulfonate compound can be obtained by extracting the product B obtained after the reaction in step B using an organic solvent, washing with water, and then crystallizing the product. Alternatively, the methylene disulfonate compound can be obtained by adding water or the like to the product B to decompose sulfur trioxide, and then extracting with an organic solvent, washing with water, and crystallizing the product in the same manner as above. Furthermore, the methylene disulfonate compound can be obtained by adding a poor solvent such as water to the product B to precipitate a crude product, filtering the product, and recrystallizing the crude product.

[0095] Examples of organic solvents used in the purification treatment include methylene chloride and acetonitrile.

[0096] The present disclosure includes all arbitrary combinations of the constituent features described in this specification. In addition, the various characteristics (properties, structures, functions, etc.) described for each embodiment of the present disclosure above may be combined in any way to specify the subject matter included in the present disclosure. In other words, the present disclosure includes all subject matter consisting of all combinations of each combinable characteristic described in this specification. EXAMPLES

[0097] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the embodiments of these examples.

[0098] Example 1 Into a four-neck flask equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel, 9.6 g (0.10 mol) of methanesulfonic acid, 10 g (0.085 mol) of sulfolane, and 16 g (0.20 mol) of sulfur trioxide were charged as raw materials. The raw materials in the flask were heated to 150°C while being stirred, and the reaction was continued at this temperature for 6 hours to obtain reaction product A (step A). ​​An appropriate amount of the obtained reaction product A was sampled and subjected to ion chromatography analysis, and based on the area value of the peak obtained in this analysis, the product methanedisulfonic acid (R 1 and R 2 The production yield of the compound (wherein n is a hydrogen atom and n is 1) was calculated. As a result, the production yield of the obtained methanedisulfonic acid was 74 mol %.

[0099] Next, 12 g (0.15 mol) of sulfur trioxide was added to the reaction product A, and 3.6 g (0.11 mol as formaldehyde) of 91% paraformaldehyde was added at room temperature (25°C) under stirring. After the addition was completed, the temperature was raised to 55°C, and the reaction was continued with stirring at this temperature for 3 hours to obtain reaction product B (step B). The production yield of methylenemethane disulfonate in reaction product B obtained by this reaction was 81 mol% based on the methane disulfonic acid obtained in step A. The production yield was determined from the peak area value obtained by sampling the reaction solution containing reaction product B obtained by the reaction and analyzing it by HPLC (the same applies to the following examples).

[0100] Next, reactant B was cooled to 25°C, and methylene chloride and water were added to separate the liquids, and the organic layer was taken out and washed with water. The organic layer obtained was concentrated, and the precipitated crystals were filtered off and dried at 40°C and 10 mmHg for 6 hours to obtain 5.7 g of methylenemethane disulfonate as a solid content. The yield of methylenemethane disulfonate relative to the methanesulfonic acid used in step A was 30 mol%. The fact that the crystals were methylenemethane disulfonate can be confirmed by the following method. 1 This was determined from the results of H-NMR analysis. 1H-NMR (400MHz, CD3CN) δ (ppm): 5.33 (s, 2H), 6.00 (s, 2H).

[0101] Example 2 A four-neck flask equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel was charged with 14.4 g (0.15 mol) of methanesulfonic acid and 15 g (0.13 mol) of sulfolane as raw materials. The raw materials in the flask were heated to 150°C while stirring, and 12 g (0.15 mol) of sulfur trioxide was added dropwise at this temperature. Then, the reaction was carried out by continuing stirring for 5 hours. Next, 12 g (0.15 mol) of sulfur trioxide was further added, and stirring was continued for 1 hour to obtain reactant A (step A). ​​An appropriate amount of the obtained reactant A was sampled and analyzed by ion chromatography, and based on the area value of the peak obtained in this analysis, the product methane disulfonic acid (R 1 and R 2 The production yield of the compound (wherein n is a hydrogen atom and n is 1) was calculated. As a result, the production yield of the obtained methanedisulfonic acid was 70 mol %.

[0102] Next, 57g (0.72 mol) of sulfur trioxide was added to the reaction product A, and 20g of 91% paraformaldehyde (0.60 mol as formaldehyde) was added at room temperature (25°C) under stirring. After the addition was completed, the temperature was raised to 60°C, and the reaction was continued with stirring at this temperature for 1 hour, and then the temperature was raised to 100°C and stirred for 2 hours, thereby obtaining reaction product B (step B). The production yield of methylenemethane disulfonate in reaction product B obtained by this reaction was 83 mol% based on the methane disulfonic acid produced in step A.

[0103] Example 3 Into a four-neck flask equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel, 14.4 g (0.15 mol) of methanesulfonic acid and 15 g (0.13 mol) of sulfolane were charged as raw materials. The raw materials in the flask were heated to 150°C while being stirred, and 17 g (0.22 mol) of sulfur trioxide was added dropwise at this temperature. Then, the reaction was carried out by continuing the stirring for 10 hours. As a result, reactant A was obtained (step A). ​​An appropriate amount of the obtained reactant A was sampled and analyzed by ion chromatography, and based on the area value of the peak obtained in this analysis, the product methane disulfonic acid (R 1 and R 2 The production yield of the compound (wherein n is a hydrogen atom and n is 1) was calculated. As a result, the production yield of the obtained methanedisulfonic acid was 79 mol %.

[0104] Next, 24 g (0.30 mol) of sulfur trioxide was added to the reaction product A, and 5 g of 91% paraformaldehyde (0.15 mol as formaldehyde) was added at room temperature (25°C) under stirring. After the addition was completed, the temperature was raised to 60°C, and the reaction was continued with stirring at this temperature for 1.5 hours, and then the temperature was raised to 100°C and stirred for 1 hour, thereby obtaining reaction product B (step B). The production yield of methylenemethane disulfonate in reaction product B obtained by this reaction was 82 mol% based on the methane disulfonic acid produced in step A.

[0105] Example 4 Into a four-neck flask equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel, 9.6 g (0.10 mol) of methanesulfonic acid, 10 g (0.085 mol) of sulfolane, and 16 g (0.20 mol) of sulfur trioxide were charged as raw materials. The raw materials in the flask were heated to 150°C while being stirred, and the reaction was carried out by continuing stirring for 10 hours. As a result, reactant A was obtained (step A). ​​An appropriate amount of the obtained reactant A was sampled and analyzed by ion chromatography, and based on the area value of the peak obtained in this analysis, the product methanedisulfonic acid (R 1 and R 2The production yield of the compound (wherein n is a hydrogen atom and n is 1) was calculated. As a result, the production yield of the obtained methanedisulfonic acid was 78 mol %.

[0106] Next, 12 g (0.15 mol) of sulfur trioxide was charged into the reactant A, and 4 g of 91% paraformaldehyde (0.12 mol as formaldehyde) was added at room temperature (25°C) under stirring. After the addition was completed, the temperature was raised to 55°C, and the reaction was continued with stirring at this temperature for 4 hours to obtain reactant B (step B). The production yield of methylenemethane disulfonate in reactant B obtained by this reaction was 78 mol% based on the methane disulfonic acid produced in step A.

[0107] Example 5 A four-neck flask equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel was charged with 4.8 g (0.05 mol) of methanesulfonic acid, 10 g (0.085 mol) of sulfolane, and 24 g (0.30 mol) of sulfur trioxide as raw materials. The raw materials in the flask were heated to 145°C while being stirred, and the reaction was carried out by continuing the stirring for 11 hours. This resulted in the production of reactant A (Step A). ​​An appropriate amount of the obtained reactant A was sampled and analyzed by ion chromatography, and based on the area value of the peak obtained in this analysis, the product methanedisulfonic acid (R 1 and R 2 The production yield of the compound (wherein n is a hydrogen atom and n is 1) was calculated. As a result, the production yield of the obtained methanedisulfonic acid was 58 mol %. Next, 14g (0.17 mol) of sulfur trioxide was charged to the reactant A, and 6g of 91% paraformaldehyde (0.18 mol as formaldehyde) was added at room temperature (25°C) under stirring. After the addition was completed, the temperature was raised to 55°C, and the reaction was continued with stirring at this temperature for 1 hour, and then the temperature was raised to 100°C and stirred for 2 hours, thereby obtaining a reactant B (Step B). The production yield of methylenemethane disulfonate in the reactant B obtained by this reaction was 84 mol% based on the methane disulfonic acid produced in Step A.

[0108] From the above results, it was found that the production method carried out in each Example can easily and inexpensively produce a methylene disulfonate compound by including step A and step B, and can also produce a methylene disulfonate compound with a smaller amount of raw material. Therefore, the production method according to the present invention is also advantageous from an industrial viewpoint.

Claims

1. A method for producing a methylene disulfonate compound, comprising the steps of: A step A of reacting at least one alkane sulfonic acid compound with sulfur trioxide in the presence of a sulfone compound to obtain a reactant A containing an alkane disulfonic acid compound; A step B of reacting the reactant A obtained in the step A with a formaldehyde compound in the presence of sulfur trioxide to obtain a methylene disulfonate compound; Including, The alkanesulfonic acid compound is represented by the following general formula (1): 【Chemistry 1】 (In formula (1), R １ and R ２ are the same or different and each represents an alkyl group having 1 to 4 carbon atoms which may be substituted by a halogen atom or a hydrogen atom; n represents an integer of 1 to 4; when n is an integer of 2 to 4, n R １ may be the same or different, and n R ２ may be the same or different.) A compound represented by the formula: The sulfone compound is represented by the following general formula (3): 【Chemistry 2】 (In formula (3), R ３ and R ４ are the same or different and each represents an alkyl group having 1 to 12 carbon atoms which may have a substituent; R ３ and R ４ may be bonded to each other together with the sulfur atom to which they are bonded, with or without a heteroatom to form a cyclic structure. A compound represented by the formula: The alkanedisulfonic acid compound is represented by the following general formula (4): 【Chemistry 3】 (In formula (4), R １ , R ２ and n are each R in formula (1). １ , R ２ and n.) A compound represented by the formula: The methylene disulfonate compound is represented by the following general formula (5): 【Chemistry 4】 (In formula (5), R １ , R ２ and n are each R in formula (1). １ , R ２ and n.) A method for producing a methylene disulfonate compound represented by the formula:

2. 2. The method for producing a methylene disulfonate compound according to claim 1, wherein the reactant A obtained in the step A is used in the step B without isolating the alkane disulfonic acid compound from the reactant A.

3. The method for producing a methylene disulfonate compound according to claim 1 or 2, wherein the reaction in step A and the reaction in step B are carried out in the presence of a solvent.

4. The method for producing a methylene disulfonate compound according to claim 3 , wherein the solvent contains a compound represented by formula (3).

5. The method for producing a methylene disulfonate compound according to claim 4, wherein the compound represented by formula (3) is sulfolane.

6. The method for producing a methylene disulfonate compound according to any one of claims 1 to 5, wherein the formaldehyde compound is at least one selected from the group consisting of paraformaldehyde, anhydrous formaldehyde, trioxane, and methylal.

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