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WO2004094365A1 - Procede de production d'un compose fluorure de sulfonyle contenant du fluor - Google Patents

Procede de production d'un compose fluorure de sulfonyle contenant du fluor Download PDF

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Publication number
WO2004094365A1
WO2004094365A1 PCT/JP2004/005874 JP2004005874W WO2004094365A1 WO 2004094365 A1 WO2004094365 A1 WO 2004094365A1 JP 2004005874 W JP2004005874 W JP 2004005874W WO 2004094365 A1 WO2004094365 A1 WO 2004094365A1
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Prior art keywords
compound
group
compound represented
formula
fluorine
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PCT/JP2004/005874
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English (en)
Japanese (ja)
Inventor
Koichi Murata
Takashi Okazoe
Eisuke Murotani
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Asahi Glass Company, Limited
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Publication of WO2004094365A1 publication Critical patent/WO2004094365A1/fr

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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
    • C07C303/22—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 from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • 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
    • C07C303/16—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 by oxidation of thiols, sulfides, hydropolysulfides, or polysulfides with formation of sulfo or halosulfonyl groups

Definitions

  • the present invention relates to a method for producing a fluorine-containing sulfonyl fluoride compound useful as an ion exchange resin raw material or the like.
  • Fluorine-containing sulfonyl fluoride compounds having a fluoroformyl group for example,
  • the following compound (i) is a compound useful as a raw material for an ion exchange resin.
  • a compound having a fluoroformyl group is tetrafluoroethylene and zirconium trioxide.
  • the following compound (i) can be obtained by reacting the above cyclic compound with hexafluoropropylene oxide (T. Hiyama (T. Hiyama)) , Organofluorin 'Compounds: Chemistry and Applications, Springer-Verlag (Springer-Verlag), Berlin (Ber 1 in), 2000, pp. 228-230).
  • mm ", F 2 C CF 2
  • conventional synthetic method was disadvantageous way to industrial implementation because it requires careful handling so 3.
  • price reduction could not be achieved.
  • the obtained compound (i) is limited to a compound having a side chain (one CF 3 )
  • the performance and membrane of an ion exchange membrane synthesized from a derivative of the compound (i) There were also characteristics problems.
  • a hydrocarbon-based sulfonic acid derivative having a hydroxyl group is used as a starting material to form an ester with a fluorinated carboxylic acid, which is directly fluorinated and thermally decomposed to obtain a fluorosulfonyl having a fluoroformyl group.
  • the following method for obtaining a fluoride compound has been proposed (see International Publication No. WO 02/41438, Pamphlet 1,).
  • the starting material is limited to a sulfonic acid compound such as isethionic acid, the skeleton of the obtained compound is limited.
  • the present invention has been made for the purpose of solving the problems of the prior art, and uses a readily available raw material, and has a structure which is difficult to obtain efficiently with the prior art.
  • the present invention provides a method capable of producing a compound.
  • the present inventors have invented a method of converting a disulfide compound into a sulfonyl halide compound, reacting the compound with fluorine in a liquid phase, and then decomposing the reactant to obtain a desired fluorine-containing sulfonylfluoride. And found that the compound can be produced, thereby completing the present invention.
  • the gist of the present invention is as follows: 1> to ⁇ 8>.
  • R A represents a divalent organic group.
  • R B represents a monovalent organic group.
  • E represents —COO CH 2 —, and the carbon atom forming the keto group of E is represented by R A.
  • X represents a halogen atom.
  • R AF is a bivalent organic radical divalent organic group or R a the same as R a is fluorinated.
  • R BF is . a monovalent organic group R B the same monovalent organic group or R B is fluorinated
  • E F is one CO_ ⁇ _CF 2 - represents a).
  • R AF is a perfluoro divalent saturated hydrocarbon group, a perfluoro (partially halogeno divalent saturated hydrocarbon) group, a perfluoro (divalent saturated hydrocarbon containing a hetero atom) group, and a perfluoro (partially halogeno (containing a hetero atom containing A divalent organic group selected from the group consisting of a divalent saturated hydrocarbon)) group, wherein R BF is a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partially halogeno monovalent saturated hydrocarbon) group, A monovalent organic group selected from the group consisting of a monovalent saturated hydrocarbon containing a hydrogen atom and a perfluoro (partially halogeno (monovalent saturated hydrocarbon containing a heteroatom)) group.
  • R BF is a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partially halogeno monovalent saturated hydrocarbon) group, A monovalent organic group
  • the compound represented by the formula (1) is a compound obtained by reacting a compound represented by the following formula (5) with a compound represented by the following formula (6): 1> to ⁇ 4 >
  • R BF has the same meaning as described above.
  • R BF has the same meaning as described above.
  • Hexafluoropropylene oxide is added to the compound represented by the formula (4) obtained by the production method described in any of ⁇ 1> to ⁇ 7>, and the compound is represented by the following formula (9).
  • a process for producing a fluorine-containing sulfonyl vinyl ether compound comprising obtaining a compound represented by the formula (9) and subjecting the compound (9) to a thermal decomposition reaction to obtain a compound represented by the following formula (10).
  • organic group refers to a group containing one or more carbon atoms.
  • a "halogeno group” is a group in which one or more of the hydrogen atoms bonded to a carbon atom has been replaced with a halogen atom.
  • Bellhalogeno group refers to a group in which substantially all of the hydrogen atoms bonded to carbon atoms have been replaced with halogen atoms
  • partial halogeno group refers to a group in which some of the hydrogen atoms bonded to carbon atoms have been substituted. Refers to a group substituted with a halogen atom.
  • octa-gen atom is a fluorine atom, it is described as “fluo port”, “perfluo port”, “partially fluoro”.
  • perfluoro group a group in which all of the hydrogen atoms bonded to carbon atoms are replaced by fluorine atoms is preferable, but even when an unsubstituted hydrogen atom remains, the property as a group is “ In the present invention, when it is substantially equivalent to a "perfluoro group", it is included in the concept of "perfluoro group” .
  • fluorination refers to introducing a fluorine atom into a compound. The fluorination is usually performed by replacing a hydrogen atom bonded to a carbon atom with a fluorine atom.
  • a group containing an etheric oxygen atom ((-) is particularly preferable.
  • compound 1 is oxidized to compound 2 (hereinafter also referred to as “oxidation step”), and then compound 2 is reacted with fluorine in a liquid phase.
  • compound 3 (hereinafter also referred to as “fluorination step”), and further decomposing compound 3 to obtain compound 4 below (hereinafter also referred to as “decomposition step”).
  • Compound 4 is a compound useful as an ion exchange resin raw material or the like.
  • a divalent hydrocarbon group, a halogeno divalent hydrocarbon group, a heteroatom-containing divalent hydrocarbon group, or a halogeno (hetero atom-containing divalent hydrocarbon) group is preferable.
  • the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group, and a divalent alicyclic hydrocarbon group, and a divalent aliphatic hydrocarbon group is preferable.
  • a single bond, a double bond, or a triple bond may exist (or coexist) as a carbon-carbon bond.
  • the divalent aliphatic hydrocarbon group has a linear structure, a branched structure, a cyclic structure, or a structure partially having a cyclic structure. Any of these may be used.
  • RA is more preferably a divalent saturated hydrocarbon group, a partially octalogeno divalent saturated hydrocarbon group, a heteroatom-containing divalent saturated hydrocarbon group or a partially octalogeno (heteroatom-containing divalent saturated hydrocarbon) group.
  • Those groups containing no atoms are particularly preferred, and divalent saturated hydrocarbon groups or heteroatom-containing divalent saturated hydrocarbon groups are particularly preferred.
  • R A is a divalent saturated hydrocarbon group
  • examples include an alkylene group, a cycloalkylene group, and a cycloalkylalkylene group.
  • the alkylene group an alkylene group having 1 to 10 carbon atoms is preferable.
  • the cycloalkylene group a 3- to 6-membered cycloalkylene group or a group in which at least one hydrogen atom of the cycloalkylene group is substituted with an alkyl group is preferable.
  • the cycloalkylalkylene group a group in which one hydrogen atom of an alkyl group having 1 to 3 carbon atoms is substituted with a 3- to 6-membered cycloalkyl group is preferable.
  • R A is a partially halogeno divalent saturated hydrocarbon group
  • a group in which the above divalent saturated hydrocarbon group is partially halogenated can be mentioned.
  • the partially halogeno divalent saturated hydrocarbon group may have a linear structure or a branched structure, or may have a partially cyclic structure, and may have a partially fluoroalkylene group or a partially fluoroalkyl group.
  • a chloroalkylene) group is preferred.
  • the partial halogeno divalent saturated hydrocarbon group preferably has 1 to 20 carbon atoms.
  • R A is a heteroatom-containing divalent saturated hydrocarbon group
  • a divalent heteroatom or a divalent heteroatom group is introduced between the carbon atoms of the divalent saturated hydrocarbon group.
  • a group in which a hetero atom is bonded to a carbon atom of the above divalent saturated hydrocarbon group, or a divalent hetero atom or a divalent heteroatom group is bonded to the carbon atom at the bonding terminal of the above divalent saturated hydrocarbon group. And a group bonded thereto.
  • heteroatom-containing divalent saturated hydrocarbon group a group having 1 to 20 carbon atoms is preferable, and from the viewpoint of usefulness of the compound, an etheric oxygen atom-containing divalent saturated hydrocarbon group is preferable, and an etheric oxygen atom-containing Alkylene groups are particularly preferred.
  • R A is a partial halogeno (hetero atom-containing divalent saturated hydrocarbon) group
  • a group in which the above-mentioned hetero atom-containing divalent saturated hydrocarbon group is partially halogenated can be mentioned, and a partial fluoro ( Etheric oxygen atom containing alkylene) groups are preferred.
  • Partial halo The geno (heteroatom-containing divalent saturated hydrocarbon) group may have a straight-chain structure or a branched structure, or may have a partial ring structure.
  • the partial halogeno (hetero atom-containing divalent saturated hydrocarbon) group preferably has 1 to 20 carbon atoms.
  • R B (monovalent organic group) in compound 1 is preferably a monovalent hydrocarbon group, a halogeno monovalent hydrocarbon group, a heteroatom-containing monovalent hydrocarbon group, or a halogeno (heteroatom-containing monovalent hydrocarbon) group. .
  • R B is preferably a group of the fluorine-containing, Furuoro monovalent saturated hydrocarbon group, or Furuoro particularly preferred (hetero atom-containing monovalent saturated hydrocarbon) group, Perufuruo port monovalent saturated hydrocarbon group or, Perfluoro (heteroatom containing monovalent saturated hydrocarbon) groups are particularly preferred.
  • RB When RB is a perfluoromonovalent saturated hydrocarbon group, it may have a linear structure, a branched structure, or may have a partial ring structure, and is preferably a perfluoroalkyl group. .
  • the carbon number of the perfluoro monovalent saturated hydrocarbon group is preferably 1 to 20, and particularly preferably 2 to 20.
  • R B is Perufuruoro (hetero atom-containing monovalent saturated hydrocarbon) group is preferably a group having a carbon number of 1 to 20, 2 to 10 carbon atoms are particularly preferred. Further, from the viewpoint of availability, ease of production, and usefulness of the product, a group containing an etheric oxygen atom is preferable, and a perfluoro (alkoxyalkyl) group or a perfluoroalkoxyl group is particularly preferable.
  • E one C_ ⁇ _ ⁇ _CH 2 - represents two E in formula (1) is, both of the two bind to R B by a carbon atom that form a keto group, or form two even keto group And is preferably bonded to R A at a carbon atom.
  • two molecules of compound 2 generated by oxidation of compound 1 become the same molecule.
  • Compound 1 can be obtained by subjecting compound 5 and compound 6 to an esterification reaction (hereinafter, referred to as “esterification step”).
  • E 1 and E 2 are one — COY and the other — CH 2 OH, especially as to which one of E 1 and E 2 is one CH 2 OH and which is one COY
  • Y represents an octylogen atom or a hydroxyl group
  • ⁇ is preferably a fluorine atom, a chlorine atom or a hydroxyl group.
  • the esterification reaction between compound 5 and compound 6 in the esterification step can be carried out under known esterification reaction conditions.
  • the reaction may be carried out in the presence of a solvent (hereinafter referred to as “solvent 1”), but is preferably carried out in the absence of solvent 1 from the viewpoint of volumetric efficiency (for example, edited by The Chemical Society of Japan). , "Experimental Chemistry Course", 4th edition, Vol. 22 (Organic synthesis IV-acid ⁇ amino acid-peptide), Maruzen, Tokyo, 1992, pp. 50-51).
  • solvent 1 a solvent
  • dichloromethane and chloroform are preferred.
  • the use amount of the solvent 1 is preferably 50 to 500% by mass based on the total amount of the compound 5 and the compound 6.
  • a dehydrating agent to be present in the reaction system to allow the reaction to proceed (for example, “The Chemical Society of Japan,” Experimental Chemistry ", 4th edition, Vol. 22 (organic synthesis IV-acid 'amino acid' peptide), Maruzen, Tokyo, 1992, pp. 45-46).
  • the dehydrating agent trifluoroacetic anhydride and thionyl chloride are preferably used.
  • the amount of the dehydrating agent is preferably 2 to 20 moles per mole of Compound 5.
  • the reaction temperature of the esterification reaction is preferably not less than 150 ° C., more preferably not more than + 100 ° C. or not more than the boiling point of the solvent.
  • the reaction time of the reaction can be appropriately changed depending on the supply rate of the raw materials and the amount of the compound used in the reaction.
  • the reaction pressure gauge pressure, hereinafter the same is preferably normal pressure to 2 MPa.
  • the crude product containing compound 1 produced by the esterification reaction may be purified according to the purpose or used as it is in the next reaction, etc., since the reaction in the next step can proceed smoothly. It is desirable to carry out purification.
  • Compound 5 is readily available or can be easily synthesized by known methods. It is a compound that can be used. Further, since the RA portion in Compound 5 can be easily designed, the molecular structure of Compound 1 obtained can be variously set.
  • Specific examples of the compound 5 include the following compounds.
  • compound 1 examples include, but are not limited to, the following compounds.
  • an oxidation step of oxidizing Compound 1 to Compound 2 is performed.
  • R A , R B , and E are the same as those in formula (1).
  • X represents a halogen atom.
  • X is preferably a fluorine atom, a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.
  • a method for producing compound 2 in which X is a halogen atom includes a method of reacting halogen (X 2 ) in a solvent containing water.
  • X in halogen (X 2 ) corresponds to X in compound 2.
  • compound 2 having a desired X can be produced regardless of the type of Y of compound 1.
  • the compound represented by the formula HO X is produced by the reaction of halogen (X 2 ) with water, and the compound represented by the HO X oxidizes a sulfur atom, and at the same time, a YS bond Is oxidatively cleaved. It is thought to do.
  • solvent 2 water, a mixed solvent of water and acetic acid, or a mixed solvent of water and acetate nitrile is preferable.
  • the amount of the solvent 2 is preferably at least 2 times, more preferably 5 to 50 times the mass of the compound 1.
  • the amount of water is preferably 4 to 2000 times, more preferably 20 to 1000 times, the mole of Compound 1.
  • chlorine gas may be used as it is, or chlorine gas diluted with an inert gas may be used.
  • inert gas nitrogen gas or helium gas is preferable, and nitrogen gas is particularly preferable for economic reasons.
  • the amount of chlorine in the nitrogen gas is not particularly limited, and is preferably 10 V o 1% or more in view of efficiency, and particularly preferably 20 vol% or more.
  • the reaction temperature in the oxidation reaction is preferably not lower than 120 ° C. and not higher than the boiling point of the solvent 2, and is preferably 0 ° C. to +60 in view of the reaction yield, selectivity, and ease of industrial implementation.
  • the reaction pressure in the oxidation reaction is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.
  • the method for forming a compound 2 X is a fluorine atom, it may be employed a method of oxidizing a compound 1 in full Tsu acid N0 2.
  • compound 2 when X is a chlorine atom include the following compounds.
  • Specific examples of the case where X is a bromine atom or a fluorine atom include the following compounds in which C 1 is replaced by Br or F.
  • X of the compound 2 generated in the oxidation step is a fluorine atom
  • the compound 2 is used as it is in the fluorination reaction.
  • X of compound 2 is a halogen atom other than a fluorine atom (hereinafter, referred to as another halogen atom)
  • the fluorination reaction is performed after replacing the other halogen atom with a fluorine atom.
  • Compound 2 in which X is a fluorine atom has an advantage that the yield of the fluorination reaction is remarkably improved as compared with the case where X is another halogen atom. Therefore, in the present invention, compound 2 in which X is a fluorine atom is used for the fluorination reaction.
  • fluorinated lithium Scott, R.B .; Gord Xon, M.J.J.Org.Chem. 1 9 5 6, 21, 38 5) or potassium hydrogen fluoride (Gramsta 5874
  • solvent 3 As a solvent (hereinafter, referred to as “solvent 3”) used for the substitution reaction, a mixed solvent of water and dioxane or a mixed solvent of water and acetate nitrile is preferable.
  • the amount of the solvent 3 is preferably at least 2 times, more preferably 5 to 50 times, the mass of the compound 6.
  • the reaction temperature of the substitution reaction is usually from 120 to the boiling point of the solvent 3, and is preferably from 0 ° C to 160 ° C from the viewpoint of the reaction yield, selectivity, and the ease of industrial implementation.
  • the reaction pressure of the substitution reaction is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoint of reaction yield, selectivity, and ease of industrial implementation.
  • Specific examples of the compound 2 in which X obtained by the substitution reaction is a fluorine atom include the compounds in which the chlorine atom in the specific examples of the compound 2 is replaced with a fluorine atom.
  • the fluorine content of compound 2 is preferably 30% by mass or more. By setting the fluorine content to 30% by mass or more, the solubility in the liquid phase during the fluorination reaction becomes good.
  • the fluorine content of compound 2 can be appropriately adjusted according to the type of the liquid phase of the fluorination reaction, and the fluorine content is more preferably 30 to 86% by mass, and still more preferably 30 to 76% by mass.
  • the use of compound 2 having a fluorine content of 86% by mass or less is advantageous in that it is excellent in economics and that the available compounds are not limited.
  • the molecular weight of compound 2 is preferably from 200 to 130.
  • the molecular weight of compound 2 is preferably from 200 to 130.
  • a decrease in the boiling point of compound 2 is suppressed, and in the course of fluorination, compound 2 is volatilized, thereby reducing the yield of fluorinated products and causing a decomposition reaction. Can be prevented.
  • the molecular weight is set to 1300 or less, it is possible to prevent a decrease in solubility in a liquid phase.
  • Compound 2 is a divalent organic radical
  • R AF is the R A the same divalent organic group or R A in formula (3) to give compound 3 performs fluorination step of reacting with fluorine in a liquid phase is fluorinated It is.
  • R A is a non-fluorinated group or R A can be fluorinated R AF , if not a group, but not fluorinated, is the same group as R A.
  • R A is a berhalogeno divalent hydrocarbon group or a berhalogeno (heteroatom-containing divalent hydrocarbon) group
  • the halogen atom in these groups does not change even when reacted with fluorine in the liquid phase. Therefore, R AF is the same group as R A.
  • R BF is a group the same group or R B and R B fluorinated.
  • R BF is or a group R B is not fluorinated, when R B is not fluorinated even if a group which can be fluorinated is the same group as R B.
  • R B is, Beruharogeno monovalent hydrocarbon group, Beruharogeno case of (hetero atom-containing monovalent hydrocarbon) group, a halogen atom in these groups may be reacted with fluorine in a liquid phase to a change Therefore , R BF is the same group as R B.
  • R AF is a perfluorinated divalent saturated hydrocarbon group, a perfluorinated (partially halogenated divalent saturated hydrocarbon) group, a perfluorinated (heteroatom-containing divalent saturated hydrocarbon) group, or a perfluoro (partially halogenated (heteroatom-containing divalent saturated hydrocarbon) group) preferably that it is a hydrocarbon)) group, these groups are each a group having a carbon skeleton structure corresponding to R a same number of carbon atoms and R a.
  • R BF is a perfluoro monovalent saturated hydrocarbon group, a perfluoro (partially halogeno monovalent saturated hydrocarbon) group, a perfluoro (monovalent saturated hydrocarbon containing a hetero atom) group, or a perfluoro (partially halogeno (heteroatom containing (Saturated hydrocarbon)).
  • R B and R BF and easily implement fluorine Kahan response to be described later of the same group are particularly preferred in that it can implement the continuous process. That is, R B in the formula (2) is also a perfluoro monovalent saturated hydrocarbon group or a perfluoro group.
  • E F represents one C ⁇ OCF 2 —.
  • the orientation of the base of E F also corresponds to E.
  • E For example, if a carbon atom forming a keto group E is bonded to R A, said carbon atom of E F is bound to R AF, carbon atom to form a keto group E is bonded to R B If there are, the carbon atom of E F is bound to R BF.
  • the fluorination reaction is carried out by a liquid-phase fluorination reaction carried out in the liquid phase from the viewpoint of operability and yield of the reaction (Ok azoe T. eta 1., Adv. Synth. Cata 1., 2001 , 343, 219 ⁇ ).
  • the fluorination reaction is performed by the ECF method, Four
  • the fluorination reaction is preferably carried out by a method of reacting compound 2 with fluorine (F 2 ) in the presence of a solvent (hereinafter referred to as “solvent 4”) to give compound 3.
  • fluorine fluorine gas may be used as it is, or fluorine gas diluted with an inert gas may be used.
  • the inert gas nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economic reasons.
  • the amount of fluorine in the nitrogen gas is not particularly limited, but is preferably 10 vo 1% or more from the viewpoint of efficiency, and particularly preferably 20 vol% or more.
  • the solvent 4 is preferably a solvent that does not contain a C—H bond and essentially has a C—F bond, and is further selected from perfluoroalkanes or a group consisting of a chlorine atom, a nitrogen atom, and an oxygen atom.
  • An organic solvent obtained by perfluorinating a known organic solvent having at least one atom in its structure is preferable.
  • a solvent having high solubility for the compound 2 is preferably used, and a solvent capable of dissolving the compound 2 in an amount of 1% by mass or more, particularly preferably a solvent capable of dissolving the compound 2 in an amount of 5% by mass or more is preferable.
  • the same solvent as the solvent used in the fluorination step described in WO 02/41438 can be used.
  • the amount of the solvent 4 is preferably at least 5 times the mass of the compound 2, and particularly preferably 10 to 100 times the mass of the compound 2.
  • the reaction system of the fluorination reaction may be a batch system or a continuous system, and for each method, the method described in WO 02/41438 can be applied. It is preferable to use a fluorine gas diluted with an inert gas such as nitrogen gas, regardless of whether the fluorine gas is used in the patch system or in the continuous system.
  • the amount of fluorine used in the fluorination reaction should be such that the amount of fluorine is always an excess equivalent to the hydrogen atoms that can be fluorinated, whether the reaction is carried out in a batch mode or in a continuous mode.
  • fluorine gas it is particularly preferable to use fluorine gas in an amount of 1.5 times equivalent or more (that is, 1.5 times mole or more) from the viewpoint of selectivity. It is preferable that the amount of fluorine gas is always maintained in an excessive amount from the start to the end of the reaction.
  • the reaction temperature of the fluorination reaction is usually preferably from 160 to the boiling point of compound 2, and from the viewpoint of the reaction yield, selectivity, and the ease of industrial implementation, it is -50 to +10. 0 ° C is particularly preferable, and 120 to 150 is particularly preferable.
  • the reaction pressure of the fluorination reaction is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoints of reaction yield, selectivity, and the ease of industrial implementation.
  • the fluorination reaction in the present invention is preferably a reaction for perfluorinating Compound 2. That is, the compound 3 is preferably a compound in which the compound 2 is perfluorinated.
  • compound 3 obtained in the fluorination step include the following compounds.
  • the decomposition step is preferably carried out by a thermal decomposition reaction or a decomposition reaction carried out in the presence of a nucleophile or an electrophile (Okazoe T. eta 1., A dv. Synth. Cata 1., 201, 334, 219.).
  • the thermal decomposition reaction can be performed by heating compound 3.
  • the reaction type of the thermal decomposition reaction is preferably selected depending on the boiling point of Compound 3 and its stability.
  • thermally decomposing compound 3 which is easily vaporized, adopt a gas phase pyrolysis method in which the exit gas containing the obtained compound 4 is condensed and recovered by continuously decomposing it in the gas phase. You.
  • the reaction temperature of the gas phase pyrolysis method is preferably from 50 to 350 ° C, particularly preferably from 50 to 300 ° C, and particularly preferably from 150 to 250 ° C.
  • the reaction may be carried out in the presence of an inert gas not directly involved in the reaction in the reaction system.
  • the inert gas include nitrogen gas and carbon dioxide gas. It is preferable to add about 0.01 to 50 vol% of the inert gas to the compound 3. Large amounts of inert gas may reduce the amount of product recovered.
  • reaction pressure in this case is not limited. Normally, the reaction is carried out in a reactor equipped with a distillation column, and the product containing compound 4 has a lower boiling point than compound 3, so the reaction distillation method is used to vaporize the product and continuously withdraw it. It is preferably obtained by a method. Alternatively, a method may be employed in which the products are collectively extracted from the reactor after the completion of the heating.
  • the reaction temperature of this liquid phase pyrolysis method is preferably from 50 to 300 ° C, particularly preferably from 100 to 250 ° C.
  • the thermal decomposition may be performed without a solvent or in the presence of a solvent (hereinafter, referred to as “solvent 5 J.”)
  • solvent 5 is not particularly limited as long as it does not react with the compound 3 and does not react with the compound 4.
  • the solvent 5 is easily separated during the purification of the compound 4. It is preferable to select one.
  • an inert solvent such as perfluorotrialkylamine and perfluoronaphthylene, and a trifluoromethyl ethylene oligomer having a high boiling point among chlorofluorocarbons are preferred.
  • the amount of the solvent 5 is preferably from 10 to 100% by mass based on the compound 3.
  • reaction can be carried out without solvent even in the presence of a solvent (hereinafter referred to as “solvent 6”).
  • solvent 6 is preferably the same as the solvent 5.
  • F— is preferable, and F— derived from alkali metal fluoride is particularly preferable.
  • the nucleophile used at the beginning of the reaction may be a catalytic amount or an excess amount.
  • the amount of the nucleophile such as F— is preferably from 1 to 500 mol%, more preferably from 1 to 100 mol%, particularly preferably from 5 to 50 mol%, based on compound 3.
  • the reaction temperature is preferably from ⁇ 30 ° C. to (a temperature between the boiling point of the solvent 6 and the compound 3), and particularly preferably from 120 ° C. to 120 ° C.
  • This method is also preferably carried out by a reactive distillation method in a reactor equipped with a distillation column.
  • the decomposition process occurs decomposition of E F, 2 two - COF group is formed.
  • Specific examples of the compound 4 obtained in the decomposition step include the following compounds.
  • Compound 4 obtained by the production method of the present invention is a compound useful as a monomer raw material for ion-exchange resins because it has an FS ⁇ 2 — group at a terminal.
  • various methods utilizing the reactivity of one C 0 F group present at the other end can be applied.
  • various compounds having an RA group can be obtained as the compound represented by the formula (1), it is possible to obtain a chemical prosthesis 4 having an RAF group corresponding to the RA .
  • the production process of the present invention can be improved to a more efficient process by producing the compounds in the process and recycling the products.
  • compound 5 Examples of the compound 6 to be reacted include a method using the following compound 7 or the following compound 8.
  • Compound 7 can be obtained together with compound 4 from the reaction product of the decomposition step of compound 3.
  • Compound 8 can be obtained by reduction reaction of compound 7.
  • compound 7 is obtained by reducing compound 7, a method in which compound 7 is replaced with a suitable ester and then reacted with a metal hydride in the liquid phase (for example, Niederpruem H., Voss, P Ger. 1, 300, 539, p. 3-4.) Or by contacting compound 7 with hydrogen gas in the presence of a suitable catalyst (Novo tny M "US 4, 273, 947, p. 7 ⁇ 10.)
  • the metal hydride is preferably sodium borohydride or lithium aluminum hydride.
  • solvent 7 tetrahydrofuran, dioxane, and tetrahydrogen are used as solvents (hereinafter, referred to as “solvent 7”). It is preferred to use mouth furan.
  • solvent 7 methanol, ethanol, or 2-propanol can be used as the solvent 7.
  • the amount of the solvent 7 is preferably at least 2 times, more preferably 5 to 50 times the mass of the compound 7.
  • the reaction temperature of the reduction reaction using a metal hydride is usually preferably 150 ° C. or higher and not higher than the boiling point of the solvent 7, in view of the reaction yield, selectivity, and low industrial practice. To 0 ° C. or higher and not higher than the boiling point of the solvent.
  • the reaction pressure is not particularly limited, and normal pressure to 2 MPa is particularly preferable from the viewpoints of reaction yield, selectivity, and ease of industrial implementation.
  • the catalyst is preferably a palladium-based, rhodium-based, or iridium-based catalyst.
  • the reaction may be carried out in the presence of a solvent, but is preferably carried out in the absence of a solvent from the viewpoint of volumetric efficiency.
  • the reaction temperature is usually preferably from 0 to 200.
  • the reaction pressure is not particularly limited, and normal pressure to 10 MPa (gauge pressure) is particularly preferable from the viewpoints of reaction yield, selectivity, and ease of industrial implementation.
  • Compound 4 produced by the above-mentioned process can be led to various useful compounds by utilizing the reactivity of one terminal C ⁇ ⁇ F group.
  • the terminal of compound 4 is a CF 2 CF 2 C ⁇ F group or a CF 2 CF (CF 3 ) COF group
  • a thermal decomposition reaction for example, Method sof Organic Chemistry ( H oub en—We y 1), the d., Ba as ne r B., Hagemann H., Ta t 1 ow J. C., Ed s., Ge org Thierne, S tutt ga rt, 1999, Vo l.
  • One S_ ⁇ 2 F groups derived from the monomers one is preferably converted to an ion-exchange group such as a subsequent step in one SO 3 H group.
  • HFPO Hexafluoropropylene oxide
  • Compound 10 is a compound useful as a monomer for synthesizing an ion exchange membrane.
  • Compound 1 As an example of a method for obtaining 0, the following compound (4-1) is reacted with HFPO to obtain the following compound (9-1), and the terminal group of the compound (9-1) is subjected to thermal decomposition reaction to obtain one. There is a method in which CF is converted into CF 2 groups to lead to the following compound (10-1).
  • thermal decomposition reaction of the compound 9 such as the compound 911 examples include a gas phase thermal decomposition reaction and a thermal decomposition reaction carried out after reacting alkali hydroxide with alkali hydroxide.
  • the reaction temperature in the gas phase thermal decomposition reaction is preferably from 250 to 400, more preferably from 250 to 35 O :.
  • the reaction temperature in the thermal decomposition reaction of the alkali carboxylate is preferably from 150 to 350, more preferably from 200 to 280 ° C.
  • the reaction temperature in the gas phase thermal decomposition reaction is 250 ° C. or higher, or when the reaction temperature in the thermal decomposition reaction of the alkali carboxylate is 150 or higher, there is an advantage that the conversion is excellent.
  • reaction temperature is less than 400 ° C or in the thermal decomposition
  • sulfonyl fluoride compounds having various structures can be produced at low cost from easily available raw materials. Furthermore, in the present invention, by-products in the product can be reused as raw materials and reaction solvents. Therefore, it is an economical way to reduce raw material usage and waste.
  • GC gas chromatography
  • GC-MS gas chromatography mass spectrometry
  • TMS tetramethylsilane CC 1 2 FCC 1 F 2
  • R-113 tetrahydrofuran
  • THF tetrahydrofuran
  • the NMR spectrum data is shown as an apparent chemical shift range. In the quantification by 19 FN MR, C 6 F 6 was used as an internal standard.
  • Example 1 one 2) C1S0 2 (CH 2) 3 COOC3 ⁇ 4CF (CF 3) preparation of OCF 2 CF (CF 3) OCF 2 CF 2 CF 3 ( oxidation step
  • the crude mixture was purified by silica gel column black Ma Bok photography (developing solvent: hexane (10): acetic acid Echiru (1) mixed solvent) to obtain FS0 2 (C) 3 COOC3 ⁇ 4CF ( CF 3) OCF 2 CF (CF 3) OCF 2 CF 2 CF 3 (4.9 g) was obtained. 80% yield, 98% purity.
  • R-113 (312 g) was added to a 50 OmL nickel autoclave and stirred at 25.
  • a cooler maintained at 20 ° C, a packed bed of NaF pellets, and a cooler maintained at 1 10 were installed in series.
  • a liquid return line was installed to return the condensed liquid from the cooler kept at -1 o ° c to the autoclave.
  • Example 3 was blown at room temperature at a flow rate of 12.86 L / h for 30 minutes, and then the pressure inside the autoclave was increased to 0.15 MPa and then further blown for 30 minutes. Next, while blowing the 20% diluted fluorine gas at the same flow rate while maintaining the pressure in the reactor at 0.1 MPa, the product (5 g) obtained in Example 3 was added to R-113 (100 g). The solution dissolved in was injected over 2.8 hours.
  • the R-113 solution with a benzene concentration of 0-01 g / mL was raised from 25 to 40 ° C. 9 mL was injected while the temperature was raised to, the benzene solution injection port of the autoclave was closed, and stirring was continued for 0.3 hour. The total amount of benzene injected was 0.09 g, and the total amount of R-113 injected was 9 mL.
  • Example 1 FS0 2 (CF 2 ) 3 C00CF 2 CF (CF 3 ) 0CF 2 CF (CF 3 ) 0CF 2 CF 2 CF 3 (4.2 g) obtained in 1-4 together with NaF powder (0.03 g)
  • the flask was charged and heated at .140 ° C. for 10 hours in an oil bath with vigorous stirring.
  • a reflux condenser whose temperature was adjusted to 20 was installed at the top of the flask. After cooling, a liquid sample (4.0 g) was recovered.
  • GC-MS analysis showed that CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COF
  • CF 3 CF 2 CF 2 OCF (CF 3 ) obtained in Example 1-5 CF 2 OCF (CF 3 ) COF and an equimolar amount of methanol, The reaction was carried out in the presence of sodium fluoride to obtain CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) C00CH 3 .
  • the obtained CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) C00C3 ⁇ 4 is reacted with sodium borohydride in 2-propanol to obtain CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF was obtained (CF 3) C3 ⁇ 4 OH.
  • FS0 2 (CH 2) 3 C00CH 2 CF (CF 3) 0CF 2 CF (CF 3) 0CF 2 CF 2 CF 3 are reacted under the same conditions as above fluorination step, FS0 2 (CF 2) 3 COOCF 2 CF (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 CF 3 was obtained.
  • the obtained FS0 2 (CF 2 ) 3 C00CF 2 CF (CF 3 ) 0CF 2 CF (CF 3 ) 0CF 2 CF 2 CF 3 is decomposed under the same conditions as in the above decomposition step to obtain FS0 2 (CF 2 ) 3 C0F and CF 3 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF (CF 3 ) COF were obtained.
  • Example 2 1 obtained in FS0 2 (CH 2) 3 C00CH 2 CF 2 CF 2 CF 2 CHF 2 (3 8 0 g) is the same as the method, the fluorination described in Example 1 one 4 Perform the process, FS0 2 (CF 2 ) C00CF 2 CF 2 CF 2 CF 2 CF 3 was obtained. Yield 55%.
  • Example 2-2 obtained in FS0 2 (CF 2) 3 g of C00CF 2 CF 2 CF 2 CF 2 CF 3 a 280 g containing crude liquid to the flask KF powder (3. 2 g), an oil while vigorously stirring Heated at 85-90 ° C for 2 hours in an oil bath at 85-90 ° C in a bath. At the top of the flask, a reflux condenser adjusted to 20 ° C was installed. After cooling, FS0 distilling the recovered liquid sample 2 (CF 2) 3 to obtain a COF (150 g). 95% yield.
  • Examples 2-3 obtained in FS0 2 (CF 2) 3 COF (1 50 g), C s F powder (6. 5 g), was charged to the O one Tokurebu (inner volume 250 mL) with di glyme (32 g) HFPO (93 g) was introduced over 3 hours while stirring under ice cooling. After stirring for 1 hour followed by the autoclave contents were vacuum distilled FS0 2 (CF 2) 4 0CF (CF 3) to give the COF (21 5 g). 90% yield.

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Abstract

La présente invention concerne un procédé de production d'un composé fluorure de sulfonyle contenant du fluor qui consiste à oxyder du RB-E-RA-S-S-RA-E-RB pour former du XSO2-RA-E-RB (2), à faire réagir le produit d'oxydation avec du fluor dans une phase liquide pour former du FSO2-RAF-EF-RBF puis à décomposer le produit de fluoration pour préparer du FSO2-RAF-COF, où RA représente un groupe organique bivalent, RAF représente un groupe organique bivalent ou similaire, RB représente un groupe organique monovalent, RBF représente un groupe organique monovalent ou similaire, E représente COOCH2-, EF représente COOCF2- et X représente un atome halogène. Le procédé selon l'invention est pratiquement exempt des problèmes classiques associés à la production du fluorure de sulfonyle et permet également de produire des composés fluorure de sulfonyle contenant du fluor ayant diverses structures moléculaires et pouvant servir de matière de départ pour une résine échangeuse d'ions ou similaire, avec une bonne efficacité et un faible coût.
PCT/JP2004/005874 2003-04-24 2004-04-23 Procede de production d'un compose fluorure de sulfonyle contenant du fluor WO2004094365A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7297815B2 (en) 2003-07-02 2007-11-20 Asahi Glass Company, Limited Process for producing fluorinated sulfonyl fluoride compound
US7781612B2 (en) 2003-07-04 2010-08-24 Asahi Glass Company, Limited Process for producing fluorinated sulfonyl fluoride
CN113583042A (zh) * 2021-09-02 2021-11-02 烟台大学 一种磷酰氟类化合物的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002044138A1 (fr) * 2000-11-28 2002-06-06 Asahi Glass Company, Limited Procede servant a preparer un compose de fluorure de fluorosulfonyle

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002044138A1 (fr) * 2000-11-28 2002-06-06 Asahi Glass Company, Limited Procede servant a preparer un compose de fluorure de fluorosulfonyle

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Title
BECK M L: "Synthesis of 3-sulfopropionimide", JOURNAL OF ORGANIC CHEMISTRY, vol. 33, no. 2, 1968, pages 897 - 899, XP002980598 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7297815B2 (en) 2003-07-02 2007-11-20 Asahi Glass Company, Limited Process for producing fluorinated sulfonyl fluoride compound
US7781612B2 (en) 2003-07-04 2010-08-24 Asahi Glass Company, Limited Process for producing fluorinated sulfonyl fluoride
CN113583042A (zh) * 2021-09-02 2021-11-02 烟台大学 一种磷酰氟类化合物的制备方法
CN113583042B (zh) * 2021-09-02 2023-08-29 烟台大学 一种磷酰氟类化合物的制备方法

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