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WO2025053142A1 - Procédé de production de chlorure d'alcane sulfonyle halogéné - Google Patents

Procédé de production de chlorure d'alcane sulfonyle halogéné Download PDF

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Publication number
WO2025053142A1
WO2025053142A1 PCT/JP2024/031611 JP2024031611W WO2025053142A1 WO 2025053142 A1 WO2025053142 A1 WO 2025053142A1 JP 2024031611 W JP2024031611 W JP 2024031611W WO 2025053142 A1 WO2025053142 A1 WO 2025053142A1
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carbon atoms
hydrocarbon group
group
halogenated
aliphatic hydrocarbon
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Japanese (ja)
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崇 柏葉
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Central Glass Co Ltd
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Central Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/80—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members

Definitions

  • This disclosure relates to a method for producing halogenated alkanesulfonyl chlorides.
  • Halogenated alkane sulfonyl 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).
  • a method for synthesizing fluoroalkanesulfonyl chloride by reacting fluoroalkanesulfonyl fluoride with imidazole and then reacting it with concentrated hydrochloric acid has been disclosed (Non-Patent Document 1).
  • Patent Document 1 is known to generate waste phosphorus compounds, and there is room for improvement in terms of reducing waste.
  • the method of Non-Patent Document 1 does not have a high yield, and since the treatment is performed using an aqueous solution, a large amount of wastewater is generated, and there are problems with the recovery of the by-product imidazole hydrochloride, which is time-consuming and costly.
  • the present disclosure aims to solve the above problems and provide a method for producing halogenated alkanesulfonyl chlorides that can produce halogenated alkanesulfonyl chlorides in high yields with a small amount of waste.
  • the present inventors have found that by using a halogenated alkanesulfonyl compound having a specific structure as a raw material and reacting it with hydrogen chloride gas to produce a halogenated alkanesulfonyl chloride, the halogenated alkanesulfonyl chloride can be obtained in a higher yield than in the past.
  • This method is a useful method that can efficiently produce a halogenated alkanesulfonyl chloride with a small amount of waste because the compounds by-produced in the reaction can be easily reused.
  • the present disclosure (1) relates to a method for producing a halogenated alkane sulfonyl chloride, comprising 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):
  • R 1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
  • R2 represents any one of 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, and when there are a plurality of R2s , they may be the same or different.
  • R3 represents any one of a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, or 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 multiple R3s may be the same or different.
  • X represents a nitrogen atom or C(R 4 ), and when a plurality of X's are present, they may be the same or different.
  • Y represents a nitrogen atom or C(R 5 ).
  • R4 represents any one of 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, and R2 and R4 may be bonded to form a ring.
  • R5 represents any one of 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, and R2 and R5 may be bonded to form a ring.
  • m is an integer from 1 to 5.
  • n is an integer of 1 or 2.
  • the present disclosure (2) relates to a method for producing the halogenated alkane sulfonyl chloride of the present disclosure (1), which further includes 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).
  • the present disclosure (3) relates to a method for producing the halogenated alkanesulfonyl chloride of the present disclosure (1) or (2), in which, in the above 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.
  • 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), in which the halogenated alkane sulfonyl compound represented by the general formula (1) is an N-halogenated alkane sulfonylimidazole.
  • the method includes a step of reacting a halogenated alkanesulfonyl compound having a specific structure with hydrogen chloride gas to obtain halogenated alkanesulfonyl chloride.
  • the entire process for producing a halogenated alkanesulfonyl chloride, including the production of the raw material can be an excellent production process that enables the production of a halogenated alkanesulfonyl chloride without requiring a large amount of a solvent.
  • the method for producing a halogenated alkane sulfonyl chloride according to the present disclosure is a method for producing a halogenated alkane sulfonyl chloride, comprising a 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.
  • Non-Patent Document 1 When hydrochloric acid is used as in Non-Patent Document 1, hydrolysis of the generated halogenated alkanesulfonyl chloride occurs, but by using hydrogen chloride gas, such hydrolysis can be prevented and the desired halogenated alkanesulfonyl chloride can be obtained in a high yield.
  • imidazole hydrochloride which is a by-product when obtaining halogenated alkanesulfonyl chloride, dissolves in water, when hydrochloric acid is used, dehydration is required to reuse the by-product imidazole hydrochloride, which is troublesome and costly.
  • hydrogen chloride gas when hydrogen chloride gas is used, dehydration is not required, so imidazole hydrochloride can be easily reused and the amount of waste can be reduced.
  • the method of reacting the halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas is not particularly limited as long as they come 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).
  • the halogenated alkanesulfonyl compound represented by the general formula (1) can be sufficiently contacted with hydrogen chloride gas, and the yield of halogenated alkanesulfonyl chloride can be further increased.
  • 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 dimethoxyethane, toluene, xylene, hexane, heptane, methyl t-butyl ether, tetrahydrofuran, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, etc. can be used. These solvents may be used alone or in combination of two or more.
  • 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, it is possible to produce halogenated alkanesulfonyl chloride with a smaller amount of waste.
  • the amount of hydrogen chloride gas used in the reaction between the halogenated alkanesulfonyl compound represented by the general formula (1) and 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).
  • hydrogen chloride gas in such a ratio, it is possible to produce halogenated alkanesulfonyl chloride in a higher yield while suppressing production costs.
  • 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 above 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.
  • R 1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
  • R2 represents any one of 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, and when there are a plurality of R2s , they may be the same or different.
  • X represents a nitrogen atom or C(R 4 ), and when a plurality of X's are present, they may be the same or different.
  • Y represents a nitrogen atom or C(R 5 ).
  • R4 represents any one of 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, and R2 and R4 may be bonded to form a ring.
  • R5 represents any one of 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, and R2 and R5 may be bonded to form a ring.
  • M represents a metal atom.
  • n is an integer of 1 or 2.
  • a hydrochloride compound represented by the general formula (2) is by-produced together with the halogenated alkanesulfonyl chloride.
  • a neutralized salt represented by the general formula (3) can be obtained, and by reacting the neutralized salt with a halogenated alkanesulfonyl halide, a halogenated alkanesulfonyl compound represented by the general formula (1) can be obtained.
  • the hydrochloride compound represented by general formula (2) produced as a by-product in the reaction of the halogenated alkanesulfonyl compound represented by general formula (1) with hydrogen chloride gas dissolves in water, and therefore when hydrochloric acid is used as in Non-Patent Document 1, the by-product hydrochloride compound dissolves in hydrochloric acid and requires dehydration for reuse.
  • the production method disclosed herein uses hydrogen chloride gas instead of hydrochloric acid, so that such a dehydration step is not required when reusing the hydrochloride compound, and the by-product can be easily reused.
  • the reaction conditions would be harsh when using neat hydrogen chloride, in reality, the reaction can proceed even under less harsh reaction conditions.
  • side reactions are suppressed, and the target product can be obtained with a high selectivity. It is presumed that the high selectivity is due in part to the suppression of hydrolysis of the product.
  • the production method disclosed herein is an advantageous production method compared to conventional production methods for halogenated alkanesulfonyl chlorides.
  • reaction of reacting the neutralized salt represented by the general formula (3) with a halogenated alkane sulfonyl halide to produce the halogenated alkane sulfonyl compound represented by the general formula (1) does not require a large amount of solvent, and therefore, when the halogenated alkane sulfonyl compound represented by the general formula (1) is produced in this manner, the halogenated alkane sulfonyl chloride can be produced without using a large amount of solvent in the entire process for producing the halogenated alkane sulfonyl chloride, including the production of the raw materials, making this a beneficial production method in this respect as well.
  • the step of reacting the metal salt compound represented by the general formula (3) with a halogenated alkanesulfonyl halide as a raw material to obtain a halogenated alkanesulfonyl compound represented by the general formula (1) will be referred to as the first step of the production method of the present disclosure
  • the step of reacting the halogenated alkanesulfonyl compound represented by the general formula (1) with hydrogen chloride gas to obtain a halogenated alkanesulfonyl chloride will be referred to as the second step
  • 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 alkanesulfonyl compound represented by the general formula (1) will be referred to as the third step of the production method of the present disclosure.
  • Z in formulas (I) and (III) represents a halogen atom other than a chlorine atom (such as a fluorine atom, a bromine atom, or an iodine atom), and is preferably a fluorine atom.
  • 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., and more preferably ⁇ 20 to 100° C.
  • the time for carrying out the reaction in the first step in a pressure vessel is preferably 0.1 to 40 hours, more preferably 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, and more preferably 0.0 to 0.5 MPa.
  • the reaction in the first step may be carried out by blowing the halogenated alkanesulfonyl halide into a reactor.
  • the halogenated alkanesulfonyl halide gas itself may be blown in, or a gas mixed with nitrogen, hydrogen, or the like may be blown in.
  • the ratio is preferably 0.01 to 100 m3 of the mixed gas per 1 m3 of the halogenated alkanesulfonyl halide, and more preferably 0.1 to 10 m3 .
  • the introduction rate of the halogenated alkanesulfonyl halide is preferably 0.1 to 500 mmol/min, more preferably 1 to 100 mmol/min, per 1 mol of the metal salt compound represented by the general formula (3).
  • the halogenated alkanesulfonyl halide may be directly introduced into the reactor by a metering pump, etc.
  • the introduction rate is preferably the same as the introduction rate described above.
  • 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 per 1 mol of the halogenated alkanesulfonyl halide. More preferably, it is 1 to 1.5 mol.
  • 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, cyclopentyl methyl ether, and the like. These solvents may be used alone or in combination of two or more.
  • the method for obtaining the metal salt compound represented by the general formula (3) used in the first step is not particularly limited, and for example, a method of reacting a compound represented by the following general formula (4) with a basic metal compound such as sodium hydride, lithium hydride, potassium hydride, rubidium hydride, cesium hydride, sodium, lithium, potassium, rubidium, cesium, etc.
  • a basic metal compound such as sodium hydride, lithium hydride, potassium hydride, rubidium hydride, cesium hydride, sodium, lithium, potassium, rubidium, cesium, etc.
  • the amount of the basic metal compound used is preferably 0.5 to 2.0 mol, more preferably 1 to 1.5 mol, per mol of the compound represented by the following general formula (4).
  • R 1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms.
  • R2 represents any one of 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, and when there are a plurality of R2s , they may be the same or different.
  • X represents a nitrogen atom or C(R 4 ), and when a plurality of X's are present, they may be the same or different.
  • Y represents a nitrogen atom or C(R 5 ).
  • R4 represents any one of 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, and R2 and R4 may be bonded to form a ring.
  • R5 represents any one of 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, and R2 and R5 may be bonded to form a ring.
  • n is an integer of 1 or 2.
  • the reaction of the compound represented by the 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., and more preferably at ⁇ 20 to 80° C.
  • the reaction time for the reaction between the compound represented by the general formula (4) and the basic metal compound is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours.
  • 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 alkane sulfonyl halide to obtain the halogenated alkane sulfonyl compound represented by the general formula (1).
  • 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 the general formula (2).
  • the reaction temperature when the hydrochloride compound represented by the general formula (2) is reacted 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 the general formula (2) with a base is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours.
  • the pressure at which the hydrochloride compound represented by the general formula (2) is reacted with a base is preferably 0.0 to 0.2 MPa, and more preferably 0.0 to 0.15 MPa.
  • the amount of halogenated alkanesulfonyl halide used is preferably 0.5 to 2.0 mol per 1 mol of the hydrochloride compound represented by the general formula (2). More preferably, it is 0.8 to 1.5 mol.
  • the halogenated alkanesulfonyl halide used in the third step may be selected according to the structure of the desired halogenated alkanesulfonyl chloride.
  • the reaction of the product obtained by the reaction of the hydrochloride compound represented by the general formula (2) with the base with the halogenated alkanesulfonyl halide is preferably carried out at ⁇ 50 to 120° C., and more preferably at ⁇ 20 to 100° C.
  • the reaction time for the reaction between the product obtained by the reaction of the hydrochloride compound represented by the general formula (2) with a base and a halogenated alkanesulfonyl halide is preferably 0.1 to 20 hours, more preferably 0.5 to 10 hours.
  • the pressure for reacting the product obtained by the reaction of the hydrochloride compound represented by the general formula (2) with a base with a halogenated alkanesulfonyl halide is preferably 0.0 to 1.0 MPa, more preferably 0.0 to 0.5 MPa.
  • the method for producing halogenated alkanesulfonyl chloride of the present disclosure may include other steps in addition to the above-mentioned first to third steps.
  • Examples of other steps include a step of purifying the halogenated alkanesulfonyl chloride obtained in the second step, and a step of removing the alkali metal halide salt obtained in the first or third step.
  • R 1 represents 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.
  • the aliphatic hydrocarbon group includes an alkyl group, an alkenyl group, and an alkynyl group, and any of these may be used, with an alkyl group being preferred.
  • linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms examples include linear alkyl groups having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group; branched alkyl groups having 3 to 6 carbon atoms, such as an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group; and cyclic alkyl groups having 3 to 6 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • R 1 is preferably any one of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • R2 represents any one of 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 the linear aliphatic hydrocarbon group 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 the linear alkyl group having 1 to 6 carbon atoms include the same as the linear alkyl group having 1 to 6 carbon atoms for R 1.
  • 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 a branched alkyl group having 3 to 6 carbon atoms, a branched alkenyl group having 3 to 6 carbon atoms, and a branched alkynyl group having 3 to 6 carbon atoms.
  • 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 of R 1.
  • 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 a cyclic alkyl group having 3 to 6 carbon atoms, a cyclic alkenyl group having 3 to 6 carbon atoms, and a cyclic alkynyl group having 3 to 6 carbon atoms.
  • Examples of the cyclic alkyl group having 3 to 6 carbon atoms include the same as the cyclic alkyl group having 3 to 6 carbon atoms of 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.
  • Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group, a naphthyl group, and an anthryl group.
  • Examples of the aromatic heterocyclic group having 3 to 14 carbon atoms include a pyrrole group, a pyrazine group, a pyrimidine group, and a pyridazine group.
  • R2 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 more 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.
  • 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 More preferred are a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group.
  • R3 represents any one of 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.
  • the halogen atom 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 the aliphatic hydrocarbon group having 1 to 6 carbon atoms include the same as the aliphatic hydrocarbon group having 1 to 6 carbon atoms for R1 .
  • Examples of groups 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 include -(R 6 ) p -NHR 7 , -(R 6 ) p -N(R 7 ) 2 and -(R 6 ) p -OR 7 (R 6 and R 7 represent aliphatic hydrocarbon groups, and the total number of carbon atoms in R 6 and R 7 is 1 to 6. When there are two R 7s , the aliphatic hydrocarbon groups represented by the two R 7s may be the same or different. p represents the number 0 or 1).
  • X represents a nitrogen atom or C(R 4 ).
  • R4 represents any one of a hydrogen atom, an aliphatic hydrocarbon group having 1 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. When there are a plurality of R4s , they may be the same or different. R2 and R4 may be bonded to form a ring.
  • the aliphatic hydrocarbon group having 1 to 6 carbon atoms include linear aliphatic hydrocarbon groups having 1 to 6 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 6 carbon atoms, and cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms.
  • Examples of 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 include the same as 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 for R2.
  • R4 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.
  • Y represents a nitrogen atom or C(R 5 ).
  • R5 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.
  • R2 and R5 may be bonded to form a ring.
  • Examples of the aliphatic hydrocarbon group having 1 to 6 carbon atoms include linear aliphatic hydrocarbon groups having 1 to 6 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 6 carbon atoms, and cyclic aliphatic hydrocarbon groups having 3 to 6 carbon atoms.
  • Examples of 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 include the same as 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 for R2.
  • R5 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.
  • n is an integer of 1 or 2, and is more preferably 1.
  • R2 and R4 may be bonded to form a ring.
  • the ring formed by bonding R2 and R4 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 heterocycle having 3 to 14 carbon atoms.
  • R2 and R5 may be bonded to form a ring.
  • the ring formed by bonding R2 and R5 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 heterocycle having 3 to 14 carbon atoms.
  • halogenated alkanesulfonyl compound represented by the general formula (1) those in which R 1 , R 2 and R 4 are each independently a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an isopropyl group, R 3 is a fluorine atom and n is 1 are more preferable. Particularly preferably, R 1 , R 2 and R 4 are all hydrogen atoms and n is 1. In this case, the halogenated alkanesulfonyl compound represented by the general formula (1) becomes an N-halogenated alkanesulfonylimidazole.
  • trifluoromethanesulfonylimidazole in which R 3 in general formula (1) is a fluorine atom and m is 1.
  • R 3 in general formula (1) is a fluorine atom and m is 1.
  • trifluoromethanesulfonyl chloride is obtained by the production method of the present disclosure.
  • R 1 , R 2 , R 4 , R 5 , X and Y in formula (1) are the same as those of R 1 , R 2 , R 4 , R 5 , X and Y in formulas (2) to (4).
  • the preferred range of n in formula (1) is the same as that in formulas (2) to (4).
  • Examples of the metal atom M in the general formula (3) include monovalent metals such as lithium, sodium, and potassium, and among these, sodium is preferred.
  • halogenated alkane sulfonyl halide other than the halogenated alkane sulfonyl chloride used in the third step of the method for producing halogenated alkane sulfonyl chloride of the present disclosure, halogenated alkane sulfonyl fluoride is preferred.
  • 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 stainless steel pressure-resistant glass reactor, and the reactor was cooled with ice water, the lid was closed, and the reactor was stirred for 30 minutes. If the pressure rose, the valve was opened appropriately to purge the gas. Next, the reactor was depressurized with 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.
  • reaction liquid (N-trifluoromethanesulfonylimidazole content: 96 mmol) obtained in the first step was placed in a 300 ml three-neck flask equipped with a gas introduction Dip tube, a thermometer protection tube, and a Liebig condenser, and heated to 70°C in an oil bath.
  • the target trifluoromethanesulfonyl chloride could be produced in high yield.
  • N-trifluoromethanesulfonylimidazole which is the raw material for the reaction in the second step, could be obtained from the imidazole hydrochloride by-produced in the second step, and the by-product of the second step could be reused in the reaction in the second step, so that the amount of waste could be reduced.
  • the production method shown in the examples does not require a large amount of solvent in the first step for producing N-trifluoromethanesulfonylimidazole, which is the raw material for the second step, and is a useful method in that it enables the production of trifluoromethanesulfonyl chloride without using a large amount of solvent in the entire series of production methods for trifluoromethanesulfonyl chloride including the first step.

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Abstract

La présente invention concerne un procédé de production d'un chlorure d'alcane sulfonyle halogéné qui permet de produire un chlorure d'alcane sulfonyle halogéné à un rendement élevé avec peu de déchets. La présente invention concerne un procédé de production d'un chlorure de sulfonyle alcane halogéné qui comprend une étape de réaction d'un composé alcane sulfonyle halogéné représenté par la formule générale (1) avec du chlorure d'hydrogène gazeux pour obtenir un chlorure de sulfonyle alcane halogéné et un composé chlorhydrate représenté par la formule générale (2). (dans la formule (1) et la formule (2), R1 représente un atome d'hydrogène ou un groupe hydrocarboné aliphatique en C1-6, R2 représente un atome d'hydrogène, un atome d'halogène, un groupe hydrocarboné aliphatique en C1-6, un groupe nitro, un groupe hydrocarboné aromatique en C6-14, ou un groupe hétérocyclique aromatique en C3-14, chaque R2 étant identique ou différent lorsqu'il y a plus d'un, R3 représente un atome d'hydrogène, un atome d'halogène, un groupe hydrocarboné aliphatique en C1-6, ou un groupe ayant un atome d'oxygène, un atome d'azote, ou un groupe NH à l'extrémité ou entre les atomes de carbone d'un groupe hydrocarboné aliphatique en C1-6, tout ou partie des atomes d'hydrogène d'un groupe hydrocarboné aliphatique devant être substitué par un atome d'halogène, et il est possible que chaque R3 soit identique ou différent lorsqu'il y a plus d'un, X représente un atome d'azote ou C(R4), chaque X pouvant être identique ou différent lorsqu'il y a plus d'un, Y représente un atome d'azote ou C(R5), R4 représente un atome d'hydrogène, un groupe hydrocarboné aliphatique en C1-6, un groupe hydrocarboné aromatique en C6-14, ou un groupe hétérocyclique aromatique en C3-14, R2 et R4 pour se lier pour former un cycle, R5 représente un atome d'hydrogène, un groupe hydrocarboné aliphatique en C1-6, un groupe hydrocarboné aromatique en C6-14, ou un groupe hétérocyclique aromatique en C3-14, R2 et R5 pour se lier pour former un cycle, m est un nombre entier de 1 à 5, inclus, et n est un nombre entier qui est 1 ou 2.)
PCT/JP2024/031611 2023-09-06 2024-09-03 Procédé de production de chlorure d'alcane sulfonyle halogéné Pending WO2025053142A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000264871A (ja) * 1999-03-16 2000-09-26 Central Glass Co Ltd トリフルオロメタンスルホニルクロリドの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000264871A (ja) * 1999-03-16 2000-09-26 Central Glass Co Ltd トリフルオロメタンスルホニルクロリドの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
UEMATSU, N. HOSHI, N. IKEDA, M.: "New preparation of 1,1,2,2-tetrafluoro-2-(trifluoroethenyloxy)-ethanesulfonyl fluoride", JOURNAL OF FLUORINE CHEMISTRY, ELSEVIER, NL, vol. 127, no. 12, 15 November 2006 (2006-11-15), NL , pages 1595 - 1600, XP005767824, ISSN: 0022-1139, DOI: 10.1016/j.jfluchem.2006.09.005 *
ZHANG FENG-XU, LIN JIN-HONG, XIAO JI-CHANG: "Difluoromethylsulfonyl Imidazolium Salt for Difluoromethylation of Alkenes", ORGANIC LETTERS, AMERICAN CHEMICAL SOCIETY, US, vol. 24, no. 41, 21 October 2022 (2022-10-21), US , pages 7611 - 7616, XP093288315, ISSN: 1523-7060, DOI: 10.1021/acs.orglett.2c03073 *

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