Production method for halogenated alkane sulfonyl chloride

Abstract

The present invention provides a production method for a halogenated alkane sulfonyl chloride that makes it possible to produce a halogenated alkane sulfonyl chloride at high yield with little waste. The present invention relates to a production method for a halogenated alkane sulfonyl chloride that includes a step for reacting a halogenated alkane sulfonyl compound represented by general formula (1) with hydrogen chloride gas to obtain a halogenated alkane sulfonyl chloride and a hydrochloride compound represented by general formula (2). (In formula (1) and formula (2), R1 represents a hydrogen atom or a C1–6 aliphatic hydrocarbon group, R2 represents a hydrogen atom, a halogen atom, a C1–6 aliphatic hydrocarbon group, a nitro group, a C6–14 aromatic hydrocarbon group, or a C3–14 aromatic heterocyclic group, it being possible for each R2 to be the same or different when there are more than one, R3 represents a hydrogen atom, a halogen atom, a C1–6 aliphatic hydrocarbon group, or a group in which there is an oxygen atom, a nitrogen atom, or an NH group at the end or between the carbon atoms of a C1–6 aliphatic hydrocarbon group, it being possible for all or a portion of the hydrogen atoms of an aliphatic hydrocarbon group to be substituted with a halogen atom, and it being possible for each R3 to be the same or different when there are more than one, X represents a nitrogen atom or C(R4), it being possible for each X to be the same or different when there are more than one, Y represents a nitrogen atom or C(R5), R4 represents a hydrogen atom, a C1–6 aliphatic hydrocarbon group, a C6–14 aromatic hydrocarbon group, or a C3–14 aromatic heterocyclic group, it being possible for R2 and R4 to bond to form a ring, R5 represents a hydrogen atom, a C1–6 aliphatic hydrocarbon group, a C6–14 aromatic hydrocarbon group, or a C3–14 aromatic heterocyclic group, it being possible for R2 and R5 to bond to form a ring, m is an integer from 1 to 5, inclusive, and n is an integer that is 1 or 2.)

Description

Method for producing halogenated alkanesulfonyl chlorides

[0001] The present disclosure relates to a method for producing halogenated alkanesulfonyl chlorides.

[0002] Halogenated alkanesulfonyl chlorides such as trifluoromethanesulfonyl chloride are useful compounds as intermediates for pharmaceuticals and agricultural chemicals. A method for synthesizing trifluoromethanesulfonyl chloride by reacting trifluoromethanesulfonic acid with phosphorus pentachloride has been disclosed (Patent Document 1). Another method for synthesizing fluoroalkanesulfonyl chloride by reacting fluoroalkanesulfonyl fluoride with imidazole and then with concentrated hydrochloric acid has been disclosed (Non-Patent Document 1).

[0003] Patent No. 3963607

[0004] Journal of Fluorine Chemistry 2006, Vol. 127, pp. 1595-1600

[0005] Among the above methods, the method of Patent Document 1 is known to generate waste phosphorus compounds, and there is room for improvement in terms of waste reduction. The method of Non-Patent Document 1 has problems such as a low yield, a large amount of wastewater due to treatment with an aqueous solution, and the recovery of the by-product imidazole hydrochloride is time-consuming and costly.

[0006] The present disclosure aims to solve the above problems and provide a method for producing halogenated alkanesulfonyl chloride, which can produce halogenated alkanesulfonyl chloride in high yield with a small amount of waste.

[0007] As a result of extensive research, the present inventors have found that when a halogenated alkane sulfonyl chloride is produced by reacting a halogenated alkane sulfonyl compound having a specific structure as a raw material with hydrogen chloride gas, the halogenated alkane sulfonyl chloride can be obtained in a higher yield than conventional methods. This method is useful because it is easy to reuse the compounds by-produced in the reaction, and therefore produces little waste and can efficiently produce a halogenated alkane sulfonyl chloride. Specifically, the present disclosure (1) relates to a method for producing a halogenated alkane sulfonyl chloride, which includes a step of reacting a halogenated alkane sulfonyl compound represented by the following general formula (1) with hydrogen chloride gas to obtain a halogenated alkane sulfonyl chloride and a hydrochloride compound represented by the following general formula (2):

[0008]

[0009]

[0010] [In formula (1) and formula (2), R １ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. ２ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a nitro group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ When there are a plurality of R, they may be the same or different. ３ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a group having an oxygen atom, a nitrogen atom, or an NH group at the terminal or between carbon atoms of an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms constituting the aliphatic hydrocarbon group may be substituted with halogen atoms, and multiple R ３ may be the same or different. X is a nitrogen atom or C(R ４ ) and when there are a plurality of X's, they may be the same or different. Y represents a nitrogen atom or C(R ５ ) represents. ４represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ４ may be bonded to form a ring. ５ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ５ may be bonded to form a ring, m is an integer of 1 to 5, and n is an integer of 1 or 2.

[0011] The present disclosure (2) relates to a method for producing the halogenated alkane sulfonyl chloride of the present disclosure (1), further comprising a step of reacting the hydrochloride compound represented by the general formula (2) produced in the above step with a base and a halogenated alkane sulfonyl halide to obtain the halogenated alkane sulfonyl compound represented by the general formula (1).

[0012] The present disclosure (3) relates to a method for producing a halogenated alkanesulfonyl chloride according to the present disclosure (1) or (2), wherein in the step, the reaction is carried out by introducing hydrogen chloride gas in an amount of 0.8 to 50 moles per mole of the halogenated alkanesulfonyl compound represented by the general formula (1).

[0013] The present disclosure (4) relates to a method for producing a halogenated alkane sulfonyl chloride according to any one of the present disclosures (1) to (3), wherein the halogenated alkane sulfonyl compound represented by the general formula (1) is an N-halogenated alkane sulfonylimidazole.

[0014] According to the method for producing halogenated alkanesulfonyl chloride of the present disclosure, by including a step of reacting a halogenated alkanesulfonyl compound having a specific structure with hydrogen chloride gas to obtain halogenated alkanesulfonyl chloride, not only can halogenated alkanesulfonyl chloride be obtained in a higher yield than conventional methods, but also the amount of waste can be reduced because the compounds by-produced by the reaction can be easily reused. Furthermore, when the halogenated alkanesulfonyl compound serving as the raw material is produced by reacting a metal salt compound having a specific structure with a halogenated alkanesulfonyl halide, the entire process for producing halogenated alkanesulfonyl chloride, including the production of the raw material, can be an excellent production method that can produce halogenated alkanesulfonyl chloride without requiring a large amount of solvent.

[0015] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the present disclosure.

[0016] 1. Method for Producing Halogenated Alkanesulfonyl Chloride The method for producing halogenated alkanesulfonyl chloride disclosed herein includes a step of reacting a halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas to obtain halogenated alkanesulfonyl chloride. When hydrochloric acid is used as in Non-Patent Document 1, hydrolysis of the resulting halogenated alkanesulfonyl chloride occurs. However, by using hydrogen chloride gas, such hydrolysis can be prevented, and the desired halogenated alkanesulfonyl chloride can be obtained in high yield. Furthermore, since imidazole hydrochloride, a by-product in obtaining halogenated alkanesulfonyl chloride, dissolves in water, using hydrochloric acid requires dehydration for reuse of the by-product, which is time-consuming and costly. On the other hand, when hydrogen chloride gas is used, dehydration is not required, allowing imidazole hydrochloride to be easily reused and reducing waste.

[0017] The method for reacting the halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas is not particularly limited as long as they are brought into contact with each other, but it is preferable to introduce hydrogen chloride gas into a solution containing the halogenated alkanesulfonyl compound represented by the general formula (1). In this way, the halogenated alkanesulfonyl compound represented by the general formula (1) can be brought into sufficient contact with the hydrogen chloride gas, and the yield of halogenated alkanesulfonyl chloride can be further increased.

[0018] When a solution containing the halogenated alkanesulfonyl compound represented by the general formula (1) is used, the solvent used to prepare the solution is not particularly limited as long as it can dissolve the halogenated alkanesulfonyl compound represented by the general formula (1), and examples of solvents that can be used include dimethoxyethane, toluene, xylene, hexane, heptane, methyl t-butyl ether, tetrahydrofuran, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, etc. These solvents may be used alone or in combination of two or more.

[0019] When a solution containing the halogenated alkanesulfonyl compound represented by the general formula (1) is used, the concentration of the halogenated alkanesulfonyl compound represented by the general formula (1) in the solution is not particularly limited, but is preferably 0.01 to 20 mol / L. More preferably, it is 0.1 to 10 mol / L. By using a solution with such a concentration, halogenated alkanesulfonyl chloride can be produced with a smaller amount of waste.

[0020] The amount of hydrogen chloride gas used in the reaction of the halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas is not particularly limited, but is preferably 0.8 to 50 mol per 1 mol of the halogenated alkanesulfonyl compound represented by the general formula (1). More preferably, it is 1 to 20 mol per 1 mol of the halogenated alkanesulfonyl compound represented by the general formula (1), and even more preferably, it is 1 to 10 mol per 1 mol of the halogenated alkanesulfonyl compound represented by the general formula (1). By using hydrogen chloride gas in such a ratio, it is possible to produce halogenated alkanesulfonyl chloride in a higher yield while reducing production costs.

[0021] When hydrogen chloride gas is introduced into a solution containing a halogenated alkanesulfonyl compound represented by general formula (1) to carry out a reaction, the rate at which hydrogen chloride gas is introduced is preferably 0.1 to 500 mmol / min per mol of the halogenated alkanesulfonyl compound represented by general formula (1) contained in the solution. More preferably, it is 1 to 100 mmol / min. Introducing hydrogen chloride gas at such a rate allows the production of halogenated alkanesulfonyl chloride in a higher yield.

[0022] The temperature at which the reaction between the halogenated alkanesulfonyl compound represented by the general formula (1) and hydrogen chloride gas is carried out is not particularly limited as long as the reaction proceeds, but is preferably 0 to 100°C. More preferably, it is 10 to 90°C. By carrying out the reaction at such a temperature, halogenated alkanesulfonyl chloride can be produced in a higher yield. The temperature at which the reaction is carried out may be changed during the reaction, and it is preferable to set the temperature of the solution of the halogenated alkanesulfonyl compound represented by the general formula (1) to 20 to 140°C after the supply of hydrogen chloride gas is completed. More preferably, it is set to 50 to 140°C. By raising the temperature of the solution of the halogenated alkanesulfonyl compound represented by the general formula (1) after the supply of hydrogen chloride gas is completed in this way, the reaction between the hydrogen chloride gas remaining in the solution and the halogenated alkanesulfonyl compound represented by the general formula (1) can be sufficiently promoted, or the dissolved halogenated alkanesulfonyl chloride can be distilled off, thereby producing halogenated alkanesulfonyl chloride in a high yield.

[0023] The time for reacting the halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas is not particularly limited as long as the reaction proceeds, but in consideration of obtaining halogenated alkanesulfonyl chloride in a high yield and production efficiency, it is preferably 0.2 to 10 hours, and more preferably 0.5 to 5 hours. The pressure for reacting the halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas is preferably 0.0 to 1.0 MPa, and more preferably 0.0 to 0.5 MPa.

[0024] The method for obtaining the halogenated alkanesulfonyl compound used in the step of obtaining a halogenated alkanesulfonyl chloride by reacting a halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas is not particularly limited, but a method of reacting a metal salt compound represented by the following general formula (3) with a halogenated alkanesulfonyl halide is preferably used:

[0025]

[0026] [In formula (3), R １ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. ２ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a nitro group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ When a plurality of X's are present, they may be the same or different. X's are nitrogen atoms or C(R ４ ) and when there are a plurality of X's, they may be the same or different. Y represents a nitrogen atom or C(R ５ ) represents. ４ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ４ may be bonded to form a ring. ５ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ５ may be bonded to form a ring; M represents a metal atom; and n is an integer of 1 or 2.

[0027] In the process of obtaining a halogenated alkane sulfonyl chloride by reacting a halogenated alkane sulfonyl compound represented by the general formula (1) with hydrogen chloride gas, a hydrochloride compound represented by the general formula (2) is by-produced along with the halogenated alkane sulfonyl chloride. Reacting this hydrochloride compound represented by the general formula (2) with a base can obtain a neutralized salt represented by the general formula (3), and reacting this neutralized salt with a halogenated alkane sulfonyl halide can obtain the halogenated alkane sulfonyl compound represented by the general formula (1). By reusing the halogenated alkane sulfonyl compound represented by the general formula (1) thus obtained as a raw material in the process of obtaining a halogenated alkane sulfonyl chloride, halogenated alkane sulfonyl chloride can be produced with reduced waste. As described above, the hydrochloride compound represented by the general formula (2), which is by-produced in the reaction of a halogenated alkane sulfonyl compound represented by the general formula (1) with hydrogen chloride gas, is soluble in water. Therefore, when hydrochloric acid is used as in Non-Patent Document 1, the by-produced hydrochloride compound dissolves in hydrochloric acid and requires dehydration for reuse. In contrast, the production method of the present disclosure uses hydrogen chloride gas instead of hydrochloric acid, eliminating the need for such a dehydration step when reusing the hydrochloride compound, and facilitating the reuse of by-products. While the use of neat hydrogen chloride would have been expected to result in harsh reaction conditions, the reaction can actually proceed without harsh conditions. Furthermore, reactions using neat hydrogen chloride suppress side reactions, enabling the target product to be obtained with high selectivity. The high selectivity is presumably due in part to the suppression of hydrolysis of the product. In these respects, the production method of the present disclosure is advantageous over conventional methods for producing halogenated alkanesulfonyl chlorides. Furthermore, the reaction of reacting the neutralized salt represented by the general formula (3) with a halogenated alkanesulfonyl halide to produce the halogenated alkanesulfonyl compound represented by the general formula (1) does not require a large amount of solvent.Therefore, when the halogenated alkanesulfonyl compound represented by the general formula (1) is produced in this manner, the halogenated alkanesulfonyl chloride can be produced without using a large amount of solvent in the entire process for producing the halogenated alkanesulfonyl chloride, including the production of the raw materials, and in this respect, the production method is also advantageous.

[0028] Hereinafter, the step of reacting a metal salt compound represented by the general formula (3) with a halogenated alkane sulfonyl halide as raw materials to obtain a halogenated alkane sulfonyl compound represented by the general formula (1) will be referred to as the first step of the production method of the present disclosure, and the step of reacting a halogenated alkane sulfonyl compound represented by the general formula (1) with hydrogen chloride gas to obtain a halogenated alkane sulfonyl chloride will be referred to as the second step. Furthermore, the step of reusing the hydrochloride compound represented by the general formula (2) produced as a by-product in the second step to obtain a halogenated alkane sulfonyl compound represented by the general formula (1) will be referred to as the third step of the production method of the present disclosure. The reactions in the first to third steps are represented by the following formulas (I) to (III), respectively. In formulas (I) and (III), Z represents a halogen atom other than a chlorine atom (such as a fluorine atom, a bromine atom, or an iodine atom), preferably a fluorine atom.

[0029]

[0030] The temperature at which the reaction of the metal salt compound represented by the general formula (3) with the halogenated alkanesulfonyl halide in the first step is carried out is not particularly limited as long as the reaction proceeds, but is preferably −50 to 120°C. More preferably, it is −20 to 100°C. In the case of a pressure vessel, the reaction time for the first step is preferably 0.1 to 40 hours. More preferably, it is 0.5 to 10 hours. The pressure at which the reaction in the first step is carried out is preferably 0.0 to 1.0 MPa. More preferably, it is 0.0 to 0.5 MPa.

[0031] The reaction of the first step may be carried out by blowing the halogenated alkane sulfonyl halide into the reactor. In this case, the halogenated alkane sulfonyl halide gas itself may be blown in, or a gas mixture with nitrogen, hydrogen, etc. may be blown in. When a mixed gas is used, the ratio is 1 / m of halogenated alkane sulfonyl halide. ３ For mixed gas, 0.01 to 100 m ３ It is preferable that the ratio is 0.1 to 10 m. ３ The introduction rate of the halogenated alkanesulfonyl halide is preferably 0.1 to 500 mmol / min relative to 1 mol of the metal salt compound represented by general formula (3). More preferably, it is 1 to 100 mmol / min. When the halogenated alkanesulfonyl halide is a liquid at room temperature, the halogenated alkanesulfonyl halide may be directly introduced into the reactor using a metering pump or the like. In this case, the introduction rate is preferably the same as the introduction rate described above.

[0032] The amount of the metal salt compound represented by the general formula (3) used in the first step is preferably 0.5 to 2.0 mol, more preferably 1 to 1.5 mol, per 1 mol of the halogenated alkanesulfonyl halide.

[0033] The reaction in the first step may be carried out using a solvent. The solvent to be used is not particularly limited as long as the reaction proceeds, and examples thereof include dimethoxyethane, toluene, xylene, hexane, heptane, methyl t-butyl ether, tetrahydrofuran, diisopropyl ether, dibutyl ether, and cyclopentyl methyl ether. These solvents may be used alone or in combination of two or more.

[0034] The method for obtaining the metal salt compound represented by general formula (3) used in the first step is not particularly limited, and for example, a method of reacting a compound represented by general formula (4) below with a basic metal compound such as sodium hydride, lithium hydride, potassium hydride, rubidium hydride, cesium hydride, sodium, lithium, potassium, rubidium, or cesium can be used. This reaction can be carried out as part of the first step. In this case, the amount of the basic metal compound used is preferably 0.5 to 2.0 mol per 1 mol of the compound represented by general formula (4) below. More preferably, it is 1 to 1.5 mol.

[0035]

[0036] [In formula (4), R １ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. ２ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a nitro group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ When a plurality of X's are present, they may be the same or different. X's are nitrogen atoms or C(R ４ ) and when there are a plurality of X's, they may be the same or different. Y represents a nitrogen atom or C(R ５ ) represents. ４ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ４ may be bonded to form a ring. ５ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ５ may be bonded to form a ring, and n is an integer of 1 or 2.

[0037] The reaction of the compound represented by general formula (4) with a basic metal compound such as sodium hydride, lithium hydride, potassium hydride, rubidium hydride, cesium hydride, sodium, lithium, potassium, rubidium, or cesium is preferably carried out at −50 to 100° C., more preferably at −20 to 80° C. The reaction time for the reaction of the compound represented by general formula (4) with a basic metal compound is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours.

[0038] The third step is a step of reacting a base with the hydrochloride compound represented by the general formula (2), and then reacting the resulting neutralized salt of the hydrochloride compound represented by the general formula (2) with a halogenated alkanesulfonyl halide to obtain a halogenated alkanesulfonyl compound represented by the general formula (1).

[0039] The base used in the third step is not particularly limited, and a basic metal compound such as sodium hydride, lithium hydride, potassium hydride, rubidium hydride, cesium hydride, sodium, lithium, potassium, rubidium, or cesium can be used. The amount of the base used in the third step is preferably 1.0 to 8.0 mol, more preferably 1.8 to 5.0 mol, per mol of the hydrochloride compound represented by general formula (2).

[0040] In the third step, the reaction temperature when reacting the hydrochloride compound represented by general formula (2) with a base is preferably −50 to 100°C, and more preferably −20 to 80°C. The reaction time for reacting the hydrochloride compound represented by general formula (2) with a base is preferably 0.1 to 20 hours, and more preferably 0.5 to 10 hours. The pressure for reacting the hydrochloride compound represented by general formula (2) with a base is preferably 0.0 to 0.2 MPa, and more preferably 0.0 to 0.15 MPa.

[0041] In the third step, the amount of halogenated alkanesulfonyl halide used is preferably 0.5 to 2.0 mol, more preferably 0.8 to 1.5 mol, per 1 mol of the hydrochloride compound represented by the general formula (2).

[0042] The halogenated alkanesulfonyl halide used in the third step may be selected according to the structure of the desired halogenated alkanesulfonyl chloride.

[0043] In the third step, the reaction of the product obtained by the reaction of the hydrochloride compound represented by general formula (2) with a base with a halogenated alkane sulfonyl halide is preferably carried out at −50 to 120° C., more preferably −20 to 100° C. The reaction time for the reaction of the product obtained by the reaction of the hydrochloride compound represented by general formula (2) with a base with a halogenated alkane sulfonyl halide is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours. The pressure for the reaction of the product obtained by the reaction of the hydrochloride compound represented by general formula (2) with a base with a halogenated alkane sulfonyl halide is preferably 0.0 to 1.0 MPa, more preferably 0.0 to 0.5 MPa.

[0044] The method for producing a halogenated alkanesulfonyl chloride according to the present disclosure may include steps other than the above-described steps 1 to 3. Examples of such steps include a step of purifying the halogenated alkanesulfonyl chloride obtained in step 2, and a step of removing the alkali metal halide salt obtained in step 1 or step 3.

[0045] 2. Reaction Raw Materials, etc. In the method for producing a halogenated alkanesulfonyl chloride according to the present disclosure, a halogenated alkanesulfonyl compound represented by the general formula (1) is used.

[0046] In general formula (1), R １represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be linear, branched, or cyclic. When the hydrocarbon group is branched or cyclic, the aliphatic hydrocarbon group has 3 to 6 carbon atoms. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups, and any of these may be used, but alkyl groups are preferred. Examples of linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms include methyl groups, ethyl groups, n-propyl groups, n-butyl groups, n-pentyl groups, and n-hexyl groups; branched alkyl groups having 3 to 6 carbon atoms such as isopropyl groups, isobutyl groups, sec-butyl groups, and tert-butyl groups; and cyclic alkyl groups having 3 to 6 carbon atoms such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, and cyclohexyl groups.

[0047] Among these, R １ is preferably any one of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

[0048] In general formula (1), R ２ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a nitro group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms. The aliphatic hydrocarbon group having 1 to 6 carbon atoms may be linear, branched, or cyclic. When the hydrocarbon group is branched or cyclic, the aliphatic hydrocarbon group has 3 to 6 carbon atoms. Examples of linear aliphatic hydrocarbon groups having 1 to 6 carbon atoms include linear alkyl groups having 1 to 6 carbon atoms, linear alkenyl groups having 2 to 6 carbon atoms, and linear alkynyl groups having 2 to 6 carbon atoms. Examples of linear alkyl groups having 1 to 6 carbon atoms include R １Examples of the linear alkyl group having 1 to 6 carbon atoms include the linear alkenyl group having 2 to 6 carbon atoms and the linear alkynyl group having 2 to 6 carbon atoms. Examples of the linear alkenyl group having 2 to 6 carbon atoms and the linear alkynyl group having 2 to 6 carbon atoms include groups obtained by removing two and four hydrogen atoms, respectively, from a linear alkyl group having 1 to 6 carbon atoms. Examples of the branched aliphatic hydrocarbon group having 3 to 6 carbon atoms include branched alkyl groups having 3 to 6 carbon atoms, branched alkenyl groups having 3 to 6 carbon atoms, and branched alkynyl groups having 3 to 6 carbon atoms. Examples of the branched alkyl group having 3 to 6 carbon atoms include R １ Examples of the branched alkyl group having 3 to 6 carbon atoms include the same as the branched alkyl group having 3 to 6 carbon atoms as defined above. Examples of the branched alkenyl group having 3 to 6 carbon atoms and the branched alkynyl group having 3 to 6 carbon atoms include groups obtained by removing two and four hydrogen atoms, respectively, from a branched alkyl group having 3 to 6 carbon atoms. Examples of the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms include cyclic alkyl groups having 3 to 6 carbon atoms, cyclic alkenyl groups having 3 to 6 carbon atoms, and cyclic alkynyl groups having 3 to 6 carbon atoms. Examples of the cyclic alkyl group having 3 to 6 carbon atoms include R １ Examples of the cyclic alkenyl group having 3 to 6 carbon atoms and the cyclic alkynyl group having 3 to 6 carbon atoms include groups obtained by removing two and four hydrogen atoms, respectively, from a cyclic alkyl group having 3 to 6 carbon atoms.

[0049] Examples of aromatic hydrocarbon groups having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, an anthryl group, etc. Examples of aromatic heterocyclic groups having 3 to 14 carbon atoms include a pyrrole group, a pyrazine group, a pyrimidine group, a pyridazine group, etc.

[0050] Among these, R ２ is preferably a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a nitro group, and is preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. More preferably, it is a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a nitro group, and even more preferably, it is a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0051] In general formula (1), R ３ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or a group having an oxygen atom, a nitrogen atom, or an NH group at the terminal or between carbon atoms of an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and some or all of the hydrogen atoms constituting the aliphatic hydrocarbon group may be substituted with halogen atoms. Examples of halogen atoms include a bromine atom, a chlorine atom, a fluorine atom, and an iodine atom, with a chlorine atom or a fluorine atom being preferred, and a fluorine atom being more preferred. Examples of aliphatic hydrocarbon groups having 1 to 6 carbon atoms include R １ Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms which has an oxygen atom, a nitrogen atom, or an NH group at the terminal or between carbon atoms include -(R ６ ) ｐ -NHR ７ , -(R ６ ) ｐ -N(R ７ ) ２ , -(R ６ ) ｐ -OR ７ (R ６ , R ７ represents an aliphatic hydrocarbon group, and R ６ and R ７ The total number of carbon atoms in R is 1 to 6. ７ If there are two R ７ The aliphatic hydrocarbon groups represented by the formula (I) may be the same or different, and p represents the number 0 or 1.

[0052] In the general formula (1), X is a nitrogen atom or C(R ４ ) represents. ４ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms. ４ R when there are multiple ４ may be the same or different. ２ and R ４may be bonded to form a ring. Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms include a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms. Examples of the linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and an aromatic heterocyclic group having 3 to 14 carbon atoms include R ２ Examples of the alkyl group include the linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, the aromatic hydrocarbon group having 6 to 14 carbon atoms, and the aromatic heterocyclic group having 3 to 14 carbon atoms.

[0053] Among these, R ４ is preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0054] In the general formula (1), Y is a nitrogen atom or C(R ５ ) represents. ５ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms. ２ and R ５ may be bonded to form a ring. Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms include a linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, and a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms. Examples of the linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, a cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and an aromatic heterocyclic group having 3 to 14 carbon atoms include R ２ Examples of the alkyl group include the linear aliphatic hydrocarbon group having 1 to 6 carbon atoms, the branched aliphatic hydrocarbon group having 3 to 6 carbon atoms, the cyclic aliphatic hydrocarbon group having 3 to 6 carbon atoms, the aromatic hydrocarbon group having 6 to 14 carbon atoms, and the aromatic heterocyclic group having 3 to 14 carbon atoms.

[0055] Among these, R ５ is preferably a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.

[0056] In general formula (1), m is an integer of 1 to 5, preferably 1 to 4, and more preferably 1. In general formula (1), n ​​is an integer of 1 or 2, and more preferably 1.

[0057] R ２ and R ４ may be bonded to form a ring. ２ and R ４ The ring formed by the bonding of R is not particularly limited, but examples thereof include aromatic hydrocarbon rings having 6 to 14 carbon atoms (e.g., naphthalene ring, anthracene ring) and aromatic heterocyclic rings having 3 to 14 carbon atoms. ２ and R ５ may be bonded to form a ring. ２ and R ５ The ring formed by bonding is not particularly limited, and examples thereof include an aromatic hydrocarbon ring having 6 to 14 carbon atoms (e.g., a naphthalene ring, an anthracene ring) or an aromatic heterocyclic ring having 3 to 14 carbon atoms.

[0058] The halogenated alkanesulfonyl compound represented by the general formula (1) includes R １ , R ２ , R ４ are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and R ３ is a fluorine atom and n is 1. Particularly preferably, R １ , R ２ , R ４ are all hydrogen atoms, and n is 1. In this case, the halogenated alkanesulfonyl compound represented by general formula (1) is an N-halogenated alkanesulfonylimidazole. Most preferably, R ３is a fluorine atom and m is 1. In this case, trifluoromethanesulfonyl chloride is obtained by the production method of the present disclosure.

[0059] R in general formula (1) １ , R ２ , R ４ , R ５ Specific examples and preferred structures of X and Y are R １ , R ２ , R ４ , R ５ The same applies to X and Y. The preferred range of n in general formula (1) also applies to n in general formulas (2) to (4). Examples of the metal atom M in general formula (3) include monovalent metals such as lithium, sodium, and potassium, and among these, sodium is preferred.

[0060] The halogenated alkane sulfonyl halide other than the halogenated alkane sulfonyl chloride used in the third step of the method for producing a halogenated alkane sulfonyl chloride of the present disclosure is preferably a halogenated alkane sulfonyl fluoride.

[0061] Examples that more specifically disclose embodiments of the present disclosure are given below, but the present disclosure is not limited to these examples.

[0062] Example (First Step) Dimethoxyethane (62 ml), sodium hydride (5.2 g, 129 mmol), and imidazole (8.0 g, 117 mmol) were placed in a 300 ml pressure-resistant glass stainless steel reactor, and the mixture was cooled with ice water, the lid was closed, and the mixture was stirred for 30 minutes. If the pressure increased during this process, the valve was opened appropriately to purge the gas. Next, the reactor was depressurized using a vacuum pump, and trifluoromethanesulfonyl fluoride (17.8 g, 117 mmol) was placed in the reactor, and the reaction was carried out for 20 hours at a jacket temperature of 0 to 25°C and an internal pressure of 0 to 0.22 MPa. After that, the lid was opened, and the reaction solution was analyzed. As a result, it was confirmed that the reaction had progressed almost quantitatively, with 120 mmol of the target N-trifluoromethanesulfonylimidazole being obtained. The reaction solution was filtered using a centrifuge and used in the next reaction. (Step 2) The reaction liquid obtained in Step 1 (N-trifluoromethanesulfonylimidazole content: 96 mmol) was placed in a 300 ml three-neck flask equipped with a gas inlet dip tube, a thermometer protection tube, and a Liebig condenser, and heated to 70°C in an oil bath. Next, hydrogen chloride gas (17.4 g, 476 mmol) was introduced over 1.6 hours. The distillate was collected in an eggplant-shaped flask cooled with ice water. After the introduction of hydrogen chloride gas was completed, the temperature of the oil bath was raised to 107°C, and further distillate was collected. As a result, 46.8 g of distillate was collected, which contained 79.8 mmol of trifluoromethanesulfonyl chloride (yield: 83%). (Step 3) The distillation residue from Step 2 (imidazole hydrochloride content: 48.1 mmol) was placed in a 300 ml pressure-resistant glass stainless steel reactor, cooled with ice water, and sodium hydride (4.2 g, 106 mmol) was added. The reactor was then capped and reacted for 5 hours. During this time, the valve was opened as appropriate to purge the gas. Next, trifluoromethanesulfonyl fluoride (8.1 g, 53 mmol) was added and the reaction was carried out for 15 hours at a jacket temperature of 25°C and a pressure of 0.09 to 0.1 MPa. After that, the cap was opened, and the reaction solution was analyzed, confirming that it contained 28.8 mmol (yield: 60%) of the target N-trifluoromethanesulfonylimidazole.

[0063] The production method shown in the examples was able to produce the target trifluoromethanesulfonyl chloride in a high yield. Furthermore, in the third step, N-trifluoromethanesulfonylimidazole, which serves as the starting material for the reaction in the second step, can be obtained from the imidazole hydrochloride by-produced in the second step. Since the by-product of the second step can be reused in the reaction in the second step, the amount of waste can also be reduced. Furthermore, the production method shown in the examples does not require a large amount of solvent in the first step, in which N-trifluoromethanesulfonylimidazole, which serves as the starting material for the second step, is produced. Therefore, the entire series of trifluoromethanesulfonyl chloride production processes, including the first step, are useful in that they can produce trifluoromethanesulfonyl chloride without using a large amount of solvent.

Claims

1. A method for producing a halogenated alkanesulfonyl chloride, comprising the step of reacting a halogenated alkanesulfonyl compound represented by the following general formula (1) with hydrogen chloride gas to obtain a halogenated alkanesulfonyl chloride and a hydrochloride compound represented by the following general formula (2): [In formula (1) and formula (2), R １ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. ２ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a nitro group, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ When there are a plurality of R, they may be the same or different. ３ represents any one of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 6 carbon atoms having any one of an oxygen atom, a nitrogen atom, and an NH group at the terminal or between carbon atoms, and some or all of the hydrogen atoms constituting the aliphatic hydrocarbon group may be substituted with halogen atoms, and a plurality of R ３ may be the same or different. X is a nitrogen atom or C(R ４ When there are a plurality of X's, they may be the same or different. Y represents a nitrogen atom or C(R ５ ) represents R ４ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ４ may be bonded to form a ring. ５ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or an aromatic heterocyclic group having 3 to 14 carbon atoms; R ２ and R ５ may be bonded to form a ring. m is an integer of 1 to 5. n is an integer of 1 or 2.] 2. A method for producing a halogenated alkane sulfonyl chloride according to claim 1, further comprising a step of reacting the hydrochloride compound represented by the general formula (2) produced in the above step with a base and a halogenated alkane sulfonyl halide to obtain a halogenated alkane sulfonyl compound represented by the general formula (1).

3. The method for producing a halogenated alkanesulfonyl chloride according to claim 1, wherein in the step, 0.8 to 50 moles of hydrogen chloride gas are introduced per mole of the halogenated alkanesulfonyl compound represented by the general formula (1) to carry out the reaction.

4. The method for producing a halogenated alkanesulfonyl chloride according to claim 1, wherein the halogenated alkanesulfonyl compound represented by the general formula (1) is an N-halogenated alkanesulfonylimidazole.

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