Method for producing cyclic disulfonic acid ester compound

Abstract

Provided is a novel production method capable of easily producing a cyclic disulfonic acid ester compound. This method for producing a cyclic disulfonic acid ester compound comprises reacting a specific sulfonic acid compound and a specific sulfuric acid ester compound.

Description

[Technical field]

[0001] The present disclosure relates to a method for producing a cyclic disulfonate compound, etc. The contents of all documents described in this specification are incorporated herein by reference. [Background technology]

[0002] Cyclic disulfonate compounds are useful as intermediates for pharmaceuticals and agricultural chemicals, and as functional materials. For example, methylene disulfonate compounds are known to be useful as pharmaceuticals such as drugs for treating leukemia in animals, and as stabilizers for electrolytes for secondary batteries.

[0003] For example, Patent Document 1 discloses a method for producing a methylene disulfonate compound by reacting silver disulfonate obtained by reacting disulfonyl chloride with silver carbonate with diiodomethane.

[0004] [ka]

[0005] Furthermore, for example, Patent Document 2 discloses a method for producing a methylene disulfonate compound by reacting an alkane disulfonic acid or the like with methylene diacetate or the like.

[0006] [ka]

[0007] Furthermore, for example, Patent Document 3 discloses a method for producing a methylene disulfonate compound by converting methane disulfonic acid into methane disulfonyl chloride using a chlorinating agent such as thionyl chloride, and reacting this with formaldehyde.

[0008] Furthermore, for example, Patent Document 4 discloses a method for producing a cyclic disulfonate compound by reacting silver disulfonate obtained by reacting disulfonyl chloride with silver carbonate, with 1,2-dibromoethane or 1,4-dibromobutane.

[0009] [ka] [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Special Publication No. 61-501089 [Patent Document 2] JP 2005-336155 A [Patent Document 3] China Patent Application Publication No. 102344436 [Patent Document 4] Special Publication No. 5-44946 Summary of the Invention [Problem to be solved by the invention]

[0011] However, in the method of Patent Document 1, the silver carbonate and diiodomethane used are expensive, the reaction proceeds slowly, and the target product may not be obtained in a satisfactory yield. In addition, poorly soluble silver iodide is by-produced in a stoichiometric amount, which may cause handling problems in the transfer and filtration steps.

[0012] The method of Patent Document 2 has a problem in that the methylene diacetate used is difficult to obtain and expensive.

[0013] The method of Patent Document 3 involves a multi-step reaction process, which makes the production steps complicated. In addition, there is a problem in that a toxic by-product is generated due to a side reaction caused by the chlorinating agent.

[0014] In the method of Patent Document 4, in addition to the fact that silver carbonate is expensive, the reaction proceeds slowly, and it may not be possible to obtain the target product in a satisfactory yield. In addition, poorly soluble silver bromide is by-produced in a stoichiometric amount, which may cause problems in handling during the transfer and filtration steps.

[0015] As described above, none of the conventionally known methods is necessarily satisfactory for implementing mass production on an industrial scale.

[0016] The present inventors have conducted research with the aim of providing a novel method for easily producing a cyclic disulfonate compound. Specifically, the present inventors have found that a cyclic disulfonate compound can be easily produced by reacting a specific sulfonic acid compound with a specific sulfate ester compound, and have made further improvements.

[0017] The present disclosure includes, for example, the subject matter described in the following sections: Item 1 Formula (1):

[0018] [ka]

[0019] (In the formula, two X's are the same or different and each represents a hydrogen atom or an alkali metal. 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. n1 represents an integer of 1 to 4, and when n1 is an integer of 2 to 4, n1 R 1 may be the same or different, and n1 R 2 may be the same or different. Formula (2):

[0020] [ka]

[0021] (wherein Y represents an alkaline earth metal; R1, R2 and n1 are the same as above). At least one sulfonic acid compound selected from the group consisting of Formula (3):

[0022] [ka]

[0023] (In the formula, R 3 and R 4 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; Formula (4):

[0024] [ka]

[0025] (In the formula, n2 represents an integer of 1 to 4. R 3 and R 4 is the same as above. comprising reacting Formula (5):

[0026] [ka]

[0027] (In the formula, R 1 , R 2 , R 3 , R 4 wherein n1 and n2 are as defined above. Section 2 2. The method for producing a cyclic disulfonate according to claim 1, wherein the sulfate ester compound is at least one sulfate ester compound selected from the group consisting of a compound represented by formula (3) and a compound represented by formula (4) in which n2 is 1. Section 3 3. The method for producing a cyclic disulfonate compound according to claim 1, wherein the sulfonic acid compound is a compound represented by formula (1) in which both of two Xs represent hydrogen atoms. Effect of the Invention

[0028] The present invention provides a method for easily and inexpensively producing a cyclic disulfonate compound, in which the viscosity of the reaction mixture during the process is relatively low and the handling properties are good even in industrial-scale production, and therefore the method is industrially advantageous. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] Each embodiment included in the present disclosure will be described in more detail below. The present disclosure preferably includes a method for producing a cyclic disulfonate compound, but is not limited thereto, and the present disclosure includes all that is disclosed in the present specification and that can be recognized by a person skilled in the art.

[0030] A method for producing a cyclic disulfonate compound encompassed by the present disclosure comprises reacting a specific sulfonic acid compound with a specific sulfate ester compound.

[0031] The specific sulfonic acid compound is at least one selected from the group consisting of compounds represented by formula (1) and compounds represented by formula (2).

[0032] [ka]

[0033] [ka]

[0034] In each of formulas (1) and (2), R 1 and R 2are each independently (i.e., the same or different) a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (1, 2, 3, or 4) which may be substituted with a halogen atom, and n1 is an integer of 1 to 4 (1, 2, 3, or 4). In addition, X are the same or different (preferably the same) a hydrogen atom or an alkali metal, and Y is an alkaline earth metal.

[0035] Examples of the halogen atom in the alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. 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, a bromomethyl group, etc.

[0036] R 1 and R 2 is preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and more preferably a hydrogen atom.

[0037] In formula (1) and formula (2), when n is an integer of 2 to 4 (2, 3, or 4), n1 R 1 and n1 R 2 may be the same as or different from each other. In addition, n1 is preferably 1.

[0038] Examples of the alkali metal represented by X include lithium, sodium, and potassium.

[0039] Examples of the alkaline earth metal represented by Y include magnesium, calcium, and barium.

[0040] The sulfonic acid compound used in the present invention is preferably one in which two Xs in formula (1) are hydrogen atoms, sodium or potassium, and more preferably one in which two Xs in formula (1) are hydrogen atoms.

[0041] As specific examples of the sulfonic acid compound represented by formula (1), the following compounds can be preferably mentioned.

[0042] Methane disulfonic acid (X=H, R 1 =R 2 =H, n=1), 1,1-ethanedisulfonic acid (X=H, R 1 =CH3, R 2 =H, n=1), 1,2-ethanedisulfonic acid (X=H, R 1 =R 2 =H, n=2), 1,1-propanedisulfonic acid (X=H, R 1 =CH2CH3,R 2 =H, n=1), 1,2-propanedisulfonic acid (X=H, R 1 =CH3 and H, R 2 =H, n=2), 1,3-propanedisulfonic acid (X=H, R 1 =R 2 =H, n=3), 2,2-propanedisulfonic acid (X=H, R 1 =R 2 =CH3, n=1), 1,4-butanedisulfonic acid (X=H, R 1 =R 2 =H, n=4), Sodium methane disulfonate (X=Na, R 1 =R 2 = H, n = 1), sodium 1,1-ethanedisulfonate (X = Na, R 1 =CH3, R 2 = H, n = 1), sodium 1,2-ethanedisulfonate (X = Na, R 1 =R 2 = H, n = 2), sodium 1,1-propanedisulfonate (X = Na, R 1 =CH2CH3,R 2 = H, n = 1), sodium 1,2-propanedisulfonate (X = Na, R 1 =CH3 and H, R 2 = H, n = 2), sodium 1,3-propanedisulfonate (X = Na, R 1 =R 2= H, n = 3), sodium 2,2-propanedisulfonate (X = Na, R 1 =R 2 = CH3, n = 1), sodium 1,4-butanedisulfonate (X = Na, R 1 =R 2 =H, n=4), Potassium methanedisulfonate (X=K, R 1 =R 2 = H, n = 1), potassium 1,1-ethanedisulfonate (X = K, R 1 =CH3, R 2 = H, n = 1), potassium 1,2-ethanedisulfonate (X = K, R 1 =R 2 = H, n = 2), potassium 1,1-propanedisulfonate (X = K, R 1 =CH2CH3,R 2 = H, n = 1), potassium 1,2-propanedisulfonate (X = K, R 1 =CH3 and H, R 2 = H, n = 2), potassium 1,3-propanedisulfonate (X = K, R 1 =R 2 = H, n = 3), potassium 2,2-propanedisulfonate (X = K, R 1 =R 2 =CH3, n=1), potassium 1,4-butanedisulfonate (X=K, R 1 =R 2 =H, n=4).

[0043] Specific preferred examples of the sulfonic acid compound represented by formula (2) include the following compounds.

[0044] Calcium methane disulfonate (Y=Ca, R 1 =R 2 = H, n = 1), calcium 1,2-ethanedisulfonate (Y = Ca, R 1 =R 2 = H, n = 2), magnesium methane disulfonate (Y = Mg, R 1 =R 2 =H, n=1), barium methanedisulfonate (Y=Ba, R 1 =R 2= H, n = 1), barium 1,2-ethanedisulfonate (Y = Ba, R 1 =R 2 = H, n = 2), barium 1,2-propanedisulfonate (Y = Ba, R 1 =CH3 and H, R 2 = H, n = 2), barium 1,3-propanedisulfonate (Y = Ba, R 1 =R 2 = H, n = 3), barium 1,4-butanedisulfonate (Y = Ba, R 1 =R 2 =H, n=4).

[0045] The sulfonic acid compound may be a commercially available product, or may be prepared by a known method or a method easily derived from a known method. For example, it may be prepared by reacting a corresponding disulfonyl halide with water, with reference to JP-A-2005-336155. It may be synthesized by reacting dichloromethane with an alkali sulfite in a water solvent at 150 to 160°C, with reference to Recueil des Travaux Chimiques des Pays-Bas, 48, 949-952 (1929).

[0046] The sulfonic acid compounds may be used alone or in combination of two or more.

[0047] The specific sulfate ester compound is at least one selected from the group consisting of compounds represented by formula (3) and compounds represented by formula (4).

[0048] [ka]

[0049] [ka]

[0050] In each of formulas (3) and (4), R 3 and R 4each independently (that is, the same or different) represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, or a hydrogen atom.

[0051] As described above, examples of the halogen atom in the alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. 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, a bromomethyl group, etc.

[0052] R 3 and R 4 is preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and more preferably a hydrogen atom.

[0053] In formula (3), two R 3 may be the same or different, and two R 4 may be the same or different.

[0054] In formula (4), n2 represents an integer of 1 to 4 (1, 2, 3, or 4). When n2 is an integer of 2 to 4, n2 R 3 may be the same or different, and n2 R 4 may be the same or different. In addition, n2 is preferably 1.

[0055] The specific sulfate ester compound can be synthesized, for example, by a known method or a method that can be easily derived from a known method.

[0056] For example, with reference to JOURNAL OF CHEMICAL SOCIETY, 1765-1771 (1931) or JOURNAL OF CHEMICAL SOCIETY, 86-91 (1932), it can be synthesized by adding paraformaldehyde to 50% fuming sulfuric acid (concentrated sulfuric acid containing 50% by mass of sulfur trioxide) and reacting at 60 to 70° C., or by reacting a corresponding dibromoalkylene with silver sulfate. It can also be synthesized by, for example, with reference to JP-B-5-507936, reacting sulfur trioxide with a corresponding alkylene oxide in a dioxane solvent at 45° C.

[0057] The specific sulfate ester compounds can be used alone or in combination of two or more.

[0058] The specific sulfonic acid compound is reacted with the specific sulfate ester compound to obtain a cyclic disulfonic acid ester compound represented by formula (5) (wherein R 1 , R 2 , R 3 , R 4 , n1, and n2 are the same as above.) can be produced.

[0059] [ka]

[0060] The amount of the sulfate ester compound used can be, for example, 0.3 to 10 mol, and is preferably 0.6 to 5.0 mol, per 1.0 mol of the sulfonic acid compound.

[0061] When the sulfate compound is particularly a compound represented by formula (3), the amount used can be, for example, 0.30 to 5.0 mol, preferably 0.35 to 4.0 mol, and more preferably 0.40 to 3.0 mol, per 1.0 mol of the sulfonic acid compound.

[0062] Furthermore, when the sulfate compound is particularly a compound represented by formula (4), the amount used can be, for example, 0.6 to 10 mol, preferably 0.7 to 7.0 mol, and more preferably 0.8 to 5.0 mol, per 1.0 mol of the sulfonic acid compound.

[0063] In the above reaction, a solvent may be used as necessary. The amount of the solvent used may be, for example, 0 to 1500 parts by mass, and preferably 0 to 1000 parts by mass, relative to 100 parts by mass of the sulfonic acid compound. The lower limit of this range is not particularly limited, but may be, for example, about 1, 5, or 10 parts by mass.

[0064] Examples of the solvent include hydrocarbon solvents, ether solvents, ketone solvents, ester solvents, amide solvents, nitrile solvents, sulfoxide solvents, sulfone solvents, and sulfuric acid. Examples of the hydrocarbon solvent include toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, hexane, heptane, and decane. Examples of the ether solvent include diethyl ether, ethylene glycol dimethyl ether, diisopropyl ether, diphenyl ether, tetrahydrofuran, dioxane, methyl-tert-butyl ether, and cyclopentyl methyl ether. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include ethyl acetate and butyl acetate. Examples of the amide solvent include dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Examples of the nitrile solvent include acetonitrile. Examples of the sulfoxide solvent include dimethyl sulfoxide. Examples of the sulfone solvent include ethyl methyl sulfone, ethyl isopropyl sulfone, sulfolane, and 3-methyl sulfolane. Among these, ether-based solvents, ketone-based solvents, ester-based solvents, amide-based solvents, nitrile-based solvents, sulfoxide-based solvents, sulfone-based solvents, and sulfuric acid are preferred, sulfoxide-based solvents, sulfone-based solvents, and sulfuric acid are more preferred, and sulfoxide-based solvents and sulfone-based solvents are even more preferred.

[0065] In producing a cyclic disulfonate compound, it is sufficient to react a sulfonic acid compound with a sulfate ester compound, and the reaction method is not particularly limited. For example, a method of charging a sulfate ester compound that has been synthesized and isolated in advance with reference to the above-mentioned literature and a sulfonic acid compound into a reaction vessel and reacting them, or a method of synthesizing a sulfate ester compound in a reaction vessel with reference to the above-mentioned literature, and adding the sulfonic acid compound to the reaction solution without isolating the produced sulfate ester compound, and allowing it to react, can be mentioned.

[0066] The reaction temperature is usually 0 to 200°C, and preferably 10 to 150°C.

[0067] The reaction time varies depending on the reaction temperature, but is usually 0.1 to 20 hours, preferably 1 to 12 hours.

[0068] By the above method, a cyclic disulfonic acid ester compound represented by the general formula (5) (wherein R 1 , R 2 , R 3 , R 4 , n1, and n2 are the same as above.) can be obtained.

[0069] [ka]

[0070] Specific examples of the cyclic disulfonate compound represented by formula (5) include methylenemethane disulfonate (R 1 =R 2 =H, R 3 =R 4 =H, n1=1, n2=1), methylene-1,1-ethane disulfonate (R 1=CH3, R 2 =H, R 3 =R 4 = H, n1 = 1, n2 = 1), methylene-1,2-ethane disulfonate (R 1 =R 2 =H, R 3 =R 4 =H, n1=2, n2=1), methylene-1,1-propane disulfonate (R 1 =CH2CH3,R 2 =H, R 3 =R 4 =H, n1=1, n2=1), methylene-1,2-propane disulfonate (R 1 =CH3 and H, R 2 =H, R 3 =R 4 = H, n1 = 2, n2 = 1), methylene-1,3-propane disulfonate (R 1 =R 2 =H, R 3 =R 4 = H, n1 = 3, n2 = 1), methylene-2,2-propane disulfonate (R 1 =CH3, R 2 =CH3, R 3 =R 4 =H, n1=1, n2=1), methylene-1,4-butane disulfonate (R 1 =R 2 =H, R 3 =R 4 =H, n1=4, n2=1), 1,2-Ethylenemethanedisulfonate (R 1 =R 2 =H, R 3 =R 4 = H, n1 = 1, n2 = 2), 1,2-ethylene-1,1-ethane disulfonate (R 1 =CH3, R 2 =H, R 3 =R 4 = H, n1 = 1, n2 = 2), 1,2-ethylene-1,2-ethane disulfonate (R 1 =R 2 =H, R 3 =R 4 = H, n1 = 2, n2 = 2), 1,2-ethylene-1,1-propane disulfonate (R1 =CH2CH3,R 2 =H, R 3 =R 4 = H, n1 = 1, n2 = 2), 1,2-ethylene-1,2-propane disulfonate (R 1 =CH3 and H, R 2 =H, R 3 =R 4 = H, n1 = 2, n2 = 2), 1,2-ethylene-1,3-propane disulfonate (R 1 =R 2 =H, R 3 =R 4 = H, n1 = 3, n2 = 2), 1,2-ethylene-2,2-propane disulfonate (R 1 =CH3, R 2 =CH3, R 3 =R 4 = H, n1 = 1, n2 = 2), 1,2-ethylene-1,4-butane disulfonate (R 1 =R 2 =H, R 3 =R 4 =H, n1=4, n2=2), 1,1-Ethylenemethanedisulfonate (R 1 =R 2 =H, R 3 =CH3, R 4 = H, n1 = 1, n2 = 1), 1,1-ethylene-1,1-ethane disulfonate (R 1 =CH3, R 2 =H, R 3 =CH3, R 4 = H, n1 = 1, n2 = 1), 1,1-ethylene-1,2-ethane disulfonate (R 1 =R 2 =H, R 3 =CH3, R 4 =H, n1=2, n1), 1,1-ethylene-1,1-propane disulfonate (R 1 =CH2CH3,R 2 =H, R 3 =CH3, R 4 = H, n1 = 1, n2 = 1), 1,1-ethylene-1,2-propane disulfonate (R 1 =CH3 and H, R 2 =H, R 3=CH3, R 4 = H, n1 = 2, n2 = 1), 1,1-ethylene-1,3-propane disulfonate (R 1 =R 2 =H, R 3 =CH3, R 4 = H, n1 = 3, n2 = 1), 1,1-ethylene-2,2-propane disulfonate (R 1 =CH3, R 2 =CH3, R 3 =CH3, R 4 = H, n1 = 1, n2 = 1), 1,1-ethylene-1,4-butane disulfonate (R 1 =R 2 =H, R 3 =CH3, R 4 =H, n1=4, n2=1), 1,3-Propylenemethane disulfonate (R 1 =R 2 =H, R 3 =R 4 = H, n1 = 1, n2 = 3), 1,3-propylene-1,1-ethane disulfonate (R 1 =CH3, R 2 =H, R 3 =R 4 = H, n1 = 1, n2 = 3), 1,3-propylene-1,2-ethane disulfonate (R 1 =R 2 =H, R 3 =R 4 = H, n1 = 2, n2 = 3), 1,3-propylene-1,1-propane disulfonate (R 1 =CH2CH3,R 2 =H, R 3 =R 4 = H, n1 = 1, n2 = 3), 1,3-propylene-1,2-propane disulfonate (R 1 =CH3 and H, R 2 =H, R 3 =R 4 = H, n1 = 2, n2 = 3), 1,3-propylene-1,3-propane disulfonate (R 1 =R 2 =H, R 3 =R 4= H, n1 = 3, n2 = 3), 1,3-propylene-2,2-propane disulfonate (R 1 =CH3, R 2 =CH3, R 3 =R 4 = H, n1 = 1, n2 = 3), 1,3-propylene-1,4-butane disulfonate (R 1 =R 2 =H, R 3 =R 4 =H, n1=4, n2=3), 1,2-Propylenemethane disulfonate (R 1 =R 2 =H, R 3 =CH3 and H, R 4 = H, n1 = 1, n2 = 2), 1,2-propylene-1,1-ethane disulfonate (R 1 =CH3, R 2 =H, R 3 =CH3 and H, R 4 = H, n1 = 1, n2 = 2), 1,2-propylene-1,2-ethane disulfonate (R 1 =R 2 =H, R 3 =CH3 and H, R 4 = H, n1 = 2, n2 = 2), 1,2-propylene-1,1-propane disulfonate (R 1 =CH2CH3,R 2 =H, R 3 =CH3 and H, R 4 = H, n1 = 1, n2 = 2), 1,2-propylene-1,2-propane disulfonate (R 1 =CH3 and H, R 2 =H, R 3 =CH3 and H, R 4 = H, n1 = 2, n2 = 2), 1,2-propylene-1,3-propane disulfonate (R 1 =R 2 =H, R 3 =CH3 and H, R 4 = H, n1 = 3, n2 = 2), 1,2-propylene-2,2-propane disulfonate (R 1 =CH3, R 2 =CH3, R 3 =CH3 and H, R 4= H, n1 = 1, n2 = 2), 1,2-propylene-1,4-butane disulfonate (R 1 =R 2 =H, R 3 =CH3 and H, R 4 =H, n1=4, n2=2) etc.

[0071] The methylene disulfonate compound obtained by the above method can be isolated, for example, by a conventionally known purification and isolation procedure, and the method is not particularly limited, but examples thereof include a method in which the compound is extracted from the reaction mixture using a solvent or the like, and then crystallized through washing with water, etc. Alternatively, for example, water or the like may be added to the reaction mixture to decompose sulfur trioxide, and then crystallized through solvent extraction, washing with water, etc. as described above, or a poor solvent such as water may be added to the reaction mixture to precipitate a crude product, which is then filtered off and purified by recrystallization.

[0072] In addition, in this specification, the term "comprising" includes "consisting essentially of" and "consisting of." In addition, the present disclosure includes all arbitrary combinations of the constituent features described in this specification.

[0073] In addition, the various characteristics (properties, structures, functions, etc.) described in 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

[0074] Hereinafter, the embodiments of the present disclosure will be described more specifically with reference to examples, but the embodiments of the present disclosure are not limited to the following examples.

[0075] [Production Example 1] In a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 100.0 g (0.62 moles as sulfur trioxide) of 50% fuming sulfuric acid (concentrated sulfuric acid containing 50% by mass of sulfur trioxide) was charged and cooled in an ice bath. 20.6 g (0.62 moles as formaldehyde) of 91% paraformaldehyde was slowly added thereto, and the mixture was stirred while being heated to 70°C. After stirring at 70°C for 12 hours, the mixture was cooled to 20°C, and the reaction liquid was dropped into ice water. The precipitated solid was filtered, washed with cold water and cold diethyl ether, and then vacuum dried for 12 hours to obtain the product of all R in formula (3). 3 and R 4 As a result, 28.9 g (yield 42%) of a sulfate ester compound in which the carbon atom is a hydrogen atom was obtained. 1H-NMR (400MHz, CD3CN)δ(ppm):5.30(s,4H)

[0076] [Example 1] In a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 7.0 g (0.04 mol) of methanedisulfonic acid, 20 g of sulfolane, and 4.4 g (0.02 mol) of the sulfate ester compound obtained in Production Example 1 were charged, heated to 100° C., and stirred for 1 hour. 1 , R 2 , R 3 and R 4 Methylenemethane disulfonate, a compound in which is a hydrogen atom, was produced. The production yield of the methylenemethane disulfonate was 47 mol% based on methane disulfonic acid. The production yield was determined from the peak area value obtained by sampling the reaction solution and analyzing it with HPLC.

[0077] Next, the reaction mixture was cooled to 25°C. Even at 25°C, the reaction mixture had low viscosity and excellent fluidity.

[0078] Further, methylene chloride and water were added thereto to separate the layers, and the organic layer was washed with water. The obtained organic layer was concentrated, and the precipitated crystals were separated by filtration. The crystals were dried at 40° C. and 10 mmHg for 6 hours to obtain a compound represented by formula (5), in which n1 and n2 are 1 and R 1 , R 2 , R 3 and R 4 methylenemethane disulfonate, a compound in which β is a hydrogen atom, was obtained in an amount of 3.2 g (yield: 42 mol%). It was confirmed by 1H-NMR analysis that the crystals were methylenemethane disulfonate. 1H-NMR (400MHz, CD3CN) δ (ppm): 5.33 (s, 2H), 6.00 (s, 2H).

[0079] [Example 2] In a four-neck flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel, 7.0 g (0.04 mol) of methanedisulfonic acid, 20 g of sulfolane, and 17.6 g (0.08 mol) of the sulfate ester compound obtained in Production Example 1 were charged, heated to 100° C., and stirred for 1 hour. 1 , R 2 , R 3 and R 4 Methylenemethane disulfonate, a compound in which is a hydrogen atom, was produced. The production yield of the methylenemethane disulfonate was 89 mol% based on methane disulfonic acid. The production yield was determined from the peak area value obtained by sampling the reaction solution and analyzing it with HPLC.

[0080] Next, the reaction mixture was cooled to 25°C. Even at 25°C, the reaction mixture had low viscosity and excellent fluidity.

[0081] As can be seen from the above results, the above production method allows the reaction to proceed satisfactorily without the precipitation of by-products or an increase in the viscosity of the reaction mixture that accompanies the progress of the reaction, etc. In other words, it is possible to easily and inexpensively produce a cyclic disulfonate compound without poor handling properties such as poor stirrability during the reaction or an increase in transport load, and is suitable for industrial-scale production.

Claims

1. Formula (1): 【Chemistry 1】 (In the formula, two X's are the same or different and each represents a hydrogen atom or an alkali metal. R １ and R ２ are the same or different and represent an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, or a hydrogen atom. n1 represents an integer of 1 to 4, and when n1 is an integer of 2 to 4, n1 R １ may be the same or different, n1 R ２ may be the same or different. Formula (2): 【Chemistry 2】 (wherein Y represents an alkaline earth metal; R1, R2 and n1 are the same as above) At least one sulfonic acid compound selected from the group consisting of Formula (3): 【Chemistry 3】 (In the formula, R ３ and R ４ 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; comprising reacting Formula (5): 【Chemistry 4】 (In the formula, R １ , R ２ , R ３ , R ４ and n1 is as defined above; and n2 is 1.

2. The method for producing a cyclic disulfonate compound according to claim 1, wherein the sulfonic acid compound is a compound represented by formula (1) in which both of the two Xs represent hydrogen atoms.

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