Bifunctional compound comprising branched perfluoroalkyl group and method for producing derivative thereof

Abstract

Provided is a bifunctional compound comprising a branched perfluoroalkyl group represented by formula (1) (Rf1 is –F or –CF3. Rf2 is –CnF2n+1 (n = 1-3). X is selected from the group consisting of –F, –O–M+, –N–HM+, and –N–M+SO2Rf3. Y is selected from the group consisting of –SO2F, –SO3 −M+, –SO2N–HM+, –SO2N–M+SO2Rf3, and –I. Rf3 is –CnF2n+1 (n = 1-4). M is selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions).

Description

Methods for producing difunctional compounds containing branched perfluoroalkyl groups and their derivatives.

[0001] This invention relates to a method for producing bifunctional compounds containing branched perfluoroalkyl groups and their derivatives. This application claims priority under Japanese Patent Application No. 2024-186632, filed in Japan on October 23, 2024, the contents of which are incorporated herein by reference.

[0002] Conventionally, difunctional perfluoroalkyl compounds having two sulfonyl groups have been widely used in battery materials and other applications.

[0003] For example, Patent Document 1 describes a conductive polymer composite containing a dopant polymer, and states that the dopant polymer contains repeating units of a 1,1-difluoromethanedisulfonyl structure. Furthermore, Patent Document 1 describes a compound having a structure in which two sulfonyl groups are bonded to a carbon atom to which two fluorine atoms are bonded, as a monomer that provides the repeating units.

[0004] For example, Patent Document 2 describes a polyfunctional electrolyte having a 1,1,2,2,3,3-hexafluoropropanedisulfonylimide structure derived from a bifunctional perfluoroalkyl compound. Patent Document 2 also describes the molecular structure of a polyfunctional electrolyte in which a sulfonyl group is bonded to a carbon atom to which two fluorine atoms are bonded, located at one end of a perfluoroalkyl chain.

[0005] Furthermore, Non-Patent Document 1 states that (CH ３ ) ２ CHSO ２ By electrolytic fluorination of F, a perfluoro compound (CF ３ ) ２ CFSO ２ It is stated that F was synthesized.

[0006] Japanese Patent No. 6343593 (B) Japanese Patent No. 3630306 (B)

[0007] J. Fluorine Chem.2003,124,21-37

[0008] Conventionally, as a perfluoroalkyl compound having a sulfonyl group, a bifunctional compound containing a branched perfluoroalkyl group has not been reported. In this specification, the "bifunctional compound containing a branched perfluoroalkyl group" means a perfluoroalkyl group (—C ｎ F ２ｎ＋１ (n = integer)), a fluorine atom (—F) or a perfluoroalkyl group, and a carbon atom to which two functional groups other than the perfluoroalkyl group are bonded, and one or both of the two functional groups is a group having a sulfonyl group.

[0009] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a bifunctional compound containing a branched perfluoroalkyl group and derivatives thereof.

[0010] The inventors of the present invention have intensively studied to produce a bifunctional compound containing a branched perfluoroalkyl group, and have conceived the present invention. That is, the present invention relates to the following matters.

[0011] [1] A bifunctional compound containing a branched perfluoroalkyl group represented by the following general formula (1).

[0012] (In the general formula (1), Rf １ is —F or —CF ３ . Rf ２ is —C ｎ F ２ｎ＋１ (n = 1 to 3). X is any group selected from the group consisting of —F, —O － M ＋ , —N － HM ＋ , —N － M ＋ SO ２ Rf ３ . Y is —SO ２ F, —SO ３ － M ＋ , —SO ２ N － HM ＋ , —SO ２ N － M ＋ SO ２Rf ３ It is one of the groups selected from the group consisting of , -I. Rf in X and Y ３ These are -C respectively. ｎ F ２ｎ＋１ (n = 1 to 4, and M is one of the groups selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions.)

[0013] [2] Rf in general formula (1) １ However, it is -F and Rf ２ However, -CF ３ [1] A difunctional compound containing a branched perfluoroalkyl group as described in [1]. [3] A difunctional compound containing a branched perfluoroalkyl group as described in [1], wherein X in general formula (1) is -F. [4] Y in general formula (1) is -SO ２ F is a bifunctional compound containing the branched perfluoroalkyl group described in [3].

[0014] [5] X in general formula (1) is -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ A difunctional compound comprising a branched perfluoroalkyl group as described in [1], wherein M is an alkali metal ion, and the group is one of the groups selected from the group consisting of the above.

[0015] [6] X in general formula (1) is -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf３ Any group selected from the group consisting of, and / or Y is, -SO ３ － M ＋ ,-SO ２ N － HM ＋ ,-SO ２ N － M ＋ SO ２ Rf ３ Any group selected from the group consisting of, and M is an ammonium ion, the bifunctional compound containing a branched perfluoroalkyl group according to [1]. [7] The bifunctional compound containing a branched perfluoroalkyl group according to [1], wherein the general formula (1) is an iodide.

[0016] [8] A method for producing a bifunctional compound containing a branched perfluoroalkyl group, represented by the following general formula (1), comprising an electrolytic fluorination step of an alkyl group-containing bifunctional compound having a sulfonyl group represented by the following general formula (2) to obtain a bifunctional compound containing a branched perfluoroalkyl group represented by the following general formula (3).

[0017] (In the general formula (1), Rf １ is -F or -CF ３ . Rf ２ is -C ｎ F ２ｎ＋１ (n = 1 to 3). X is any group selected from the group consisting of -F, -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ . Y is -SO ２ F, -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO[[ID=7S]] ２ Rf３ It is one of the groups selected from the group consisting of , -I. Rf in X and Y ３ These are -C respectively. ｎ F ２ｎ＋１ (n = 1 to 4, and M is one of the groups selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions.) (R in general formula (2) １ is hydrogen or -CH ３ That is. R ２ is, -C ｎ H ２ｎ＋１ (n = 1 to 3.) (Rf in general formula (3) １ is -F or -CF ３ Rf ２ is, -C ｎ F ２ｎ＋１ (n = 1 to 3.)

[0018] [9] A difunctional compound containing a branched perfluoroalkyl group represented by the general formula (3) is reacted with water to form two -SO compounds in the general formula (3). ２ One of F is -SO ３ A method for producing a bifunctional compound containing a branched perfluoroalkyl group as described in [8], comprising a hydrolysis step of H.

[0019]

[10] A bifunctional compound containing the branched perfluoroalkyl group represented by the general formula (3) is dissolved in a solvent and reacted with water to form two -SO compounds in the general formula (3). ２ One of F is -SO ３ A method for producing a bifunctional compound containing a branched perfluoroalkyl group as described in [8], comprising a hydrolysis step of H.

[0020]

[11] A difunctional compound comprising a branched perfluoroalkyl group represented by the general formula (3) above, and NHMSO ２ Rf ３ (Rf ３ is, -C ｎ F ２ｎ＋１A method for producing a bifunctional compound containing a branched perfluoroalkyl group as described in [8], comprising an imidation step of reacting (n=1-4), where M is any group selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions, with a solvent and water in the presence of magnesium oxide.

[0021]

[12] A difunctional compound containing a branched perfluoroalkyl group represented by the general formula (3) is reacted with iodine, acid potassium fluoride, and a solvent in the presence of silver nitrate and / or silver sulfate to form two -SO compounds in the general formula (3). ２ A method for producing a bifunctional compound containing a branched perfluoroalkyl group as described in [8], comprising an iodization step in which one of F is -I.

[0022] According to the present invention, perfluoroalkyl group (-C ｎ F ２ｎ＋１ (n=1-3)) and a fluorine atom (-F) or a trifluoromethyl group (-CF ３ This provides a novel branched perfluoroalkyl group represented by general formula (1) having a carbon atom bonded to two specific functional groups that are not perfluoroalkyl groups, and having a structure in which one or both of the two functional groups are groups having a sulfonyl group.

[0023] Furthermore, the method for producing a difunctional compound containing a branched perfluoroalkyl group according to the present invention includes a fluorination step in which a difunctional compound containing an alkyl group having a sulfonyl group represented by general formula (2) is electrolytically fluorinated to obtain a difunctional compound containing a branched perfluoroalkyl group represented by general formula (3). Therefore, according to the production method of the present invention, a novel difunctional compound containing a branched perfluoroalkyl group represented by general formula (1) can be produced.

[0024] The inventors diligently conducted research to produce a bifunctional compound containing a branched perfluoroalkyl group. As a result, they found that alkyl (-C ｎ H ２ｎ＋１ (n=1-3)) and a hydrogen atom (-H) or a methyl group (-CH) ３ Two sulfonyl fluoride groups (-SO) are attached to the carbon atom bonded to it. ２We discovered that a manufacturing method using a bifunctional compound having a structure in which F) is bonded as a raw material, and then electrolytically fluorinating it, is sufficient.

[0025] Conventionally, when perfluoro compounds are produced by electrolytic fluorination of compounds having a branched structure, many side reactions occur, resulting in the formation of many by-products in addition to the target product. For example, (CH ３ ) ２ CHSO ２ By electrolytic fluorination of F, a perfluoro compound (CF ３ ) ２ CFSO ２ When F is synthesized, the yield of the target product is low at 23% (see, for example, Non-Patent Document 1). Thus, conventional techniques have not been able to produce perfluoro compounds in sufficiently high yields using electrolytic fluorination of branched compounds. Industrial production of perfluoro compounds using the above method has been difficult.

[0026] However, the inventors of the present invention have found an alkyl group (-C ｎ H ２ｎ＋１ (n=1-3)) and a hydrogen atom (-H) or a methyl group (-CH) ３ Two sulfonyl fluoride groups (-SO) are attached to the carbon atom bonded to it. ２ We found that when a perfluoro compound is produced by electrolytic fluorination of a bifunctional compound having a structure to which F) is bonded, the target perfluoro compound can be obtained in a sufficiently high yield.

[0027] Furthermore, the present inventors have found that by the above manufacturing method, the alkyl group (-C) of the difunctional compound containing the alkyl group used as a raw material is obtained. ｎ H ２ｎ＋１ (n=1-3)) and a hydrogen atom (-H) or a methyl group (-CH) ３ A perfluoroalkyl group (-C) corresponds to the structure of a carbon atom bonded to it. ｎ F ２ｎ＋１ (n=1-3)) and a fluorine atom (-F) or a trifluoromethyl group (-CF ３ Two sulfonyl fluoride groups (-SO) are attached to the carbon atom bonded to it.２ We confirmed that it is possible to produce a novel bifunctional compound containing a branched perfluoroalkyl group having a structure to which F) is bonded.

[0028] Furthermore, the inventors conducted extensive research to produce a novel compound that is a derivative of the novel branched perfluoroalkyl group, using the above-mentioned novel branched perfluoroalkyl group-containing bifunctional compound as an intermediate compound. As a result, the perfluoroalkyl group (-C ｎ F ２ｎ＋１ (n=1-3)) and a fluorine atom (-F) or a trifluoromethyl group (-CF ３ The present invention was conceived when we discovered that it is possible to produce a variety of novel branched perfluoroalkyl groups represented by formula (1), which have a carbon atom bonded to two specific functional groups that are not perfluoroalkyl groups, and one or both of the two functional groups are groups having a sulfonyl group.

[0029] More specifically, the inventors have found that in formula (1), X is -F and Y is -SO ２ Without breaking the S-C bond of the compound represented by formula (1) where X is -F and Y is -SO in formula (1), ２ We conducted extensive research to produce derivatives of the compound represented by formula (1) that is not F. As a result, we found that in formula (1), X is -F and Y is -SO ２ Let the compound represented by formula (1) be F, and let X in formula (1) be -F, -O. － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ It is one of the groups selected from the group consisting of, and Y is -SO ２ F, -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３A group selected from the group consisting of X and Y is -SO ２ We discovered that we could synthesize various compounds that are not F.

[0030] Furthermore, the inventors have conducted extensive research and found that the compound represented by formula (1), in which Y in formula (1) is -I, is one in which X in formula (1) is -F and Y is -SO ２ We discovered that the compound represented by formula (1), where F is the intermediate compound, can be easily produced. The reason for this is that in formula (1), X is -F and Y is -SO ２ A difunctional compound containing a branched perfluoroalkyl group represented by formula (1) is, for example, Rf in formula (1). １ and Rf ２ A straight perfluoroalkyl chain with the same number of carbon atoms as the total number of carbon atoms (-(CF ２ ) ｎ At the end of the -) there are two sulfonyl fluoride groups (-SO ２ Compared to a difunctional compound containing a linear perfluoroalkyl group with a structure to which F is bonded, it has a property of the S-C bond being easily broken. As a result, in formula (1), X is -F and Y is -SO ２ It is presumed that the compound represented by formula (1), which is F, has a property that makes it easily iodized.

[0031] The following describes in detail the method for producing bifunctional compounds containing branched perfluoroalkyl groups and their derivatives according to the present invention. The scope of the present invention is not limited to the embodiment described herein, and various modifications can be made without departing from the spirit of the invention. Furthermore, if multiple upper and lower limits are given for a particular parameter, any upper and lower limit can be combined from among these upper and lower limits to obtain a suitable numerical range.

[0032] <Difunctional compound containing a branched perfluoroalkyl group> The difunctional compound containing a branched perfluoroalkyl group in this embodiment is a difunctional compound containing a branched perfluoroalkyl group represented by the following general formula (1).

[0033] (Rf in general formula (1)) １ is -F or -CF３ Rf ２ is, -C ｎ F ２ｎ＋１ (n = 1 to 3). X is -F, -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ It is one of the groups selected from the group consisting of . Y is -SO ２ F, -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ It is one of the groups selected from the group consisting of , -I. Rf in X and Y ３ These are -C respectively. ｎ F ２ｎ＋１ (n = 1 to 4, and M is one of the groups selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions.)

[0034] The difunctional compound containing the branched perfluoroalkyl group shown in formula (1) has a different "solvent solubility" than the difunctional compound containing the linear perfluoroalkyl group. Furthermore, the compound shown in formula (1) has Rf in formula (1). １ , Rf ２ Depending on the types of X and Y, various physical properties such as "diffusibility," "crystallinity," "conductivity," and "viscosity" are expected to differ. Therefore, difunctional compounds containing branched perfluoroalkyl groups represented by formula (1) can be used in a variety of applications according to their properties, and the selection of compounds with desirable physical properties according to the application can be increased.

[0035] In a difunctional compound containing a branched perfluoroalkyl group represented by formula (1), Rf １ and Rf ２ Both are -CF ３ You may also, Rf １and Rf ２ It may be different from the above. In a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1), Rf is used because it requires less raw material cost and can be manufactured with good yield. １ is -F, Rf ２ ga-CF ３ It is most preferable that this be the case.

[0036] In a difunctional compound containing a branched perfluoroalkyl group represented by formula (1), X is -F, -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ２ F, -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ It is one of the groups selected from the group consisting of -I. X shown in formula (1) is -F, -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ２ F, -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３A bifunctional compound containing a branched perfluoroalkyl group selected from the group consisting of , and -I is a compound having properties corresponding to the types of X and Y, and can be used in a variety of applications according to those properties.

[0037] The X shown in equation (1) is -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ A bifunctional compound containing a branched perfluoroalkyl group selected from the group consisting of the above is a compound salt having properties corresponding to the types of X and Y, and in addition to having excellent chemical stability, it can be used in a variety of applications depending on its properties, such as good conductivity and / or strong acidity.

[0038] The value of X shown in equation (1) is -F or -N － HM ＋ is, and / or Y is, -SO ２ F, -SO ２ N － HM ＋ A bifunctional compound containing a branched perfluoroalkyl group, which is one of the groups selected from the group consisting of , and -I, is preferably used as an intermediate compound when synthesizing various compounds corresponding to different applications, because X and / or Y, as shown in formula (1), are reactive functional groups.

[0039] In a difunctional compound containing a branched perfluoroalkyl group represented by formula (1), Rf in X and Y ３ These are -C respectively. ｎ F ２ｎ＋１(n = 1 to 4), and M is one of the groups selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions. Rf in X ３ Rf in Y ３ They may be the same or different. Also, M in X may be the same or different from M in Y. The difunctional compound containing the branched perfluoroalkyl group shown in formula (1) is Rf in X and Y. ３ Since M is as described above, it can be easily manufactured by the method described later.

[0040] Rf in X and Y ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4). Specifically, Rf ３ -CF ３ , -CF ２ CF ３ , - (CF ２ ) ２ CF ３ , -CF (CF ３ ) ２ , - (CF ２ ) ３ CF ３ , -CF ２ CF (CF ３ ) ２ , -CF (CF ３ ) CF ２ CF ３ , -C(CF ３ ) ３ It is one of the perfluoroalkyl groups selected from X and Y. ３ From the viewpoint of making it easier to obtain the raw materials for the compound shown in formula (1), a linear perfluoroalkyl group (-CF) having 1 to 4 carbon atoms is used. ３ , -CF ２ CF ３ , - (CF ２ ) ２ CF ３ , - (CF ２ ) ３ CF ３It is preferable that ) is the case. M in X and Y is one of the groups selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions.

[0041] When M in X and Y is an alkali metal ion, examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium. It is preferable that the alkali metal be selected from lithium, sodium, or potassium, with potassium being the most preferred, due to the ease of obtaining and handling the raw materials used in the synthesis.

[0042] Furthermore, when M in X and Y is an alkaline earth metal ion, examples of alkaline earth metals include magnesium, calcium, strontium, barium, and radium. From the standpoint of the ease of obtaining the raw materials used in synthesis, it is preferable that M be selected from magnesium, calcium, and barium, with calcium being the most preferable.

[0043] Furthermore, when M in X and Y is an onium ion, examples of onium include ammonium, pyrrolidinium, imidazolium, pyridinium, sulfonium, and phosphonium. From the standpoint of ease of handling of the raw materials used in synthesis, it is preferable that the onium be selected from ammonium, pyrrolidinium, imidazolium, pyridinium, and sulfonium, with ammonium being the most preferable.

[0044] Examples of ammonium compounds include tetramethylammonium, tetraethylammonium, tetrabutylammonium, ethyltrimethylammonium, trimethylpropylammonium, trimethylisopropylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, dodecyltrimethylammonium, vinyltrimethylammonium, allyltrimethylammonium, triethylmethylammonium, triethylpropylammonium, triethylmethoxymethylammonium, tributylethylammonium, diethyldimethylammonium, dimethyldipropylammonium, hexamethonium, diisopropylethylammonium, and others.

[0045] Examples of pyrrolidinium include N,N-dimethylpyrrolidinium, N,N-diethylpyrrolidinium, N,N-dipropylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, N-methyl-N-propylpyrrolidinium, N-butyl-N-methylpyrrolidinium, and N-hexyl-N-methylpyrrolidinium.

[0046] Examples of imidazolium include 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1,3-dipropylimidazolium, 1-ethyl-3-methylimidazolium, 1-methyl-3-propylimidazolium, 1-butyl-3-methylimidazolium, 1-isopropyl-3-propylimidazolium, and 1-tert-butyl-3-isopropylimidazolium.

[0047] Examples of pyridinium include N-ethylpyridinium and N-butylpyridinium. Examples of sulfonium include trimethylsulfonium, triethylsulfonium, tributylsulfonium, diethylmethylsulfonium, dimethylpropylsulfonium, and hexyldimethylsulfonium.

[0048] Examples of phosphoniums include tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tetraoctylphosphonium, tetraphenylphosphonium, ethyltrimethylphosphonium, triethylmethylphosphonium, hexyltrimethylphosphonium, and trimethyloctylphosphonium.

[0049] In a difunctional compound containing a branched perfluoroalkyl group represented by formula (1), -SO ２ X and Y may be the same or they may be different. -SO ２ When X and Y are the same, it may be even easier to manufacture. In a difunctional compound containing a branched perfluoroalkyl group represented by formula (1), X is -F and Y is -SO ２ A bifunctional compound containing a branched perfluoroalkyl group represented by the following formula (3), which is F, can be easily produced by electrolytic fluorination of a bifunctional compound containing an alkyl group represented by the following formula (2), as described later, and is therefore preferred.

[0050] (R in general formula (2)) １ is hydrogen or -CH ３ That is. R ２ is, -C ｎ H ２ｎ＋１ (n = 1 to 3.) (Rf in general formula (3) １ is -F or -CF ３ Rf ２ is, -C ｎ F ２ｎ＋１ (n = 1 to 3.)

[0051] If X shown in equation (1) is -F and / or Y is -SO ２ A difunctional compound containing a branched perfluoroalkyl group represented by formula (3) is Rf １ and Rf ２ The carbon atom to which it is bonded has a highly reactive sulfonyl group called -SO ２It has a structure in which two F atoms are bonded. For this reason, the difunctional compound containing the branched perfluoroalkyl group shown in formula (3) is an alkali metal compound, ammonia, perfluoroalkyl group (-C ｎ F ２ｎ＋１ It can be readily reacted with compounds such as perfluoroalkylsulfonamides having (n = 1 to 4), and / or with iodine. Therefore, X represented by formula (1) is -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ A bifunctional compound containing a branched perfluoroalkyl group, which is one of the groups selected from the group consisting of , and -I, can be easily produced by reacting one or more of the above compounds and / or iodine with a bifunctional compound containing a branched perfluoroalkyl group represented by formula (3).

[0052] The value of X shown in equation (1) is -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３In a bifunctional compound containing a branched perfluoroalkyl group which is one of the groups selected from the group consisting of, M in formula (1) is one of the groups selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions. Among these compounds, it is preferable that M in formula (1) is one of the groups selected from the group consisting of hydrogen, alkali metal ions, and ammonium ions. This is because the compound represented by formula (1) can be produced at low cost, has excellent solubility in water, and is easily derivatized into onium salts, etc. Furthermore, it is preferable that M in formula (1) is an alkali metal ion, and in particular, compounds in which M is potassium are preferred from the viewpoint of being easy to purify when producing the compound represented by formula (1).

[0053] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1) is one in which X in formula (1) is -O － M ＋ It is also preferable that M is an alkali metal ion and Y is an iodide with -I. Based on general knowledge (J. Fluorine Chem. 1994, 66, 175-177, J. Fluorine Chem. 2012, 138, 3-23, Heterocycles 2021, 103(2), 839-861, etc.), such compounds are thought to be able to react with unsaturated hydrocarbons, aromatic hydrocarbons, aldehydes, ketones, etc. From this, it is preferable that X in formula (1) is -O － M ＋ Therefore, an iodide in which M is an alkali metal ion and Y is -I is presumed to be a useful intermediate compound when synthesizing compounds into which 1,2,2,2-tetrafluoro-1-sulfonate has been introduced.

[0054] Difunctional compounds containing branched perfluoroalkyl groups represented by formula (1) include, specifically, the difunctional compounds containing branched perfluoroalkyl groups represented by formulas (1-1) to (1-21) shown below. All of the difunctional compounds containing branched perfluoroalkyl groups represented by formulas (1-1) to (1-21) can be easily produced by the production methods described later.

[0055] The difunctional compounds containing branched perfluoroalkyl groups represented by formulas (1-1) to (1-19) all contain Rf １ is -F, Rf ２ ga-CF ３ The difunctional compounds containing branched perfluoroalkyl groups represented by formulas (1-2) to (1-19) can all be easily produced using the difunctional compound containing branched perfluoroalkyl groups represented by formula (1-1) as an intermediate compound, and are derivatives of the difunctional compound containing branched perfluoroalkyl groups represented by formula (1-1).

[0056] The difunctional compounds containing branched perfluoroalkyl groups represented by formulas (1-20) and (1-21) all have Rf １ is -F, Rf ２ ga-CF ２ CF ３ The difunctional compound containing the branched perfluoroalkyl group shown in formula (1-21) can be easily produced using the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-20) as an intermediate compound, and is a derivative of the compound shown in formula (1-20).

[0057] The compounds represented by formulas (1-1) to (1-5) and (1-8) to (1-21) all contain multiple (2 to 6) sulfonyl groups (-SO ２ It has (-). Also, the compounds represented by formulas (1-2), (1-3), (1-11), (1-15), (1-16), (1-19), and (1-21) are potassium salts. The compound represented by formula (1-4) is an imide salt. The compound represented by formula (1-5) is both an imide salt and a potassium salt. The compound represented by formula (1-6) is an iodide, and the compound represented by formula (1-7) is a potassium salt of iodide. The compound represented by formula (1-8) is a hydroxide. The compounds represented by formulas (1-9) and (1-12) are sodium salts. The compounds represented by formulas (1-10) and (1-13) are lithium salts. The compounds represented by formulas (1-14) and (1-18) are amine salts. The compound represented by formula (1-17) is a calcium salt.

[0058]

[0059]

[0060] The difunctional compounds containing branched perfluoroalkyl groups represented by formulas (1-1) and (1-20) are such that in formula (1), X is -F and Y is -SO ２ F. Therefore, the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-1) is R in formula (2). １ is hydrogen, R ２ A bifunctional compound containing an alkyl group represented by formula (2), in which R is a methyl group, can be easily produced by electrolytic fluorination, which is preferable. Furthermore, a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-20) is preferred, in which R in formula (2) １ is hydrogen, R ２ This method is preferable because it can be easily produced by electrolytic fluorination of a bifunctional compound containing an alkyl group represented by formula (2), in which the alkyl group is an ethyl group.

[0061] Furthermore, difunctional compounds containing branched perfluoroalkyl groups represented by formulas (1-1) and (1-20) are Rf １ and Rf ２ The carbon atom to which it is bonded has a highly reactive sulfonyl group called -SO ２ It has a structure in which two F groups are bonded. For this reason, difunctional compounds containing the branched perfluoroalkyl group shown in formula (1-1) are not the same as compounds shown in formulas (1-2) to (1-5), which have two sulfonyl groups (-SO ２ It can be preferably used as an intermediate compound when producing a bifunctional compound containing a branched perfluoroalkyl group to which various functional groups are bonded, and when producing a bifunctional compound containing a branched perfluoroalkyl group in which one sulfonyl group is substituted with iodine, such as the compounds shown in formulas (1-6) and (1-7). Furthermore, the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-20) can be preferably used as an intermediate compound when producing a bifunctional compound containing a branched perfluoroalkyl group to which two sulfonyl groups (-SO) are bonded, such as the compound shown in formula (1-21). ２This intermediate compound can be preferably used when producing a bifunctional compound containing a branched perfluoroalkyl group to which various functional groups are bonded, and when producing a bifunctional compound containing a branched perfluoroalkyl group in which one sulfonyl group is substituted with iodine.

[0062] <Method for Producing a Difunctional Compound Containing a Branched Perfluoroalkyl Group> The difunctional compound containing the branched perfluoroalkyl group of this embodiment, represented by formula (1), can be produced, for example, by the method shown below. [First Production Method] (In formula (1), X is -F and Y is -SO ２ In the case of F (when producing a bifunctional compound containing a branched perfluoroalkyl group shown in formula (3)), first, R １ The target Rf １ This corresponds to R ２ The target Rf ２ A difunctional compound containing the alkyl group shown in formula (2), which corresponds to R, is prepared. More specifically, R １ The target Rf １ The -F that it possesses is hydrogen, and R ２ The target Rf ２ Prepare a compound in which the -F is a hydrogen alkyl group. The difunctional compound containing the alkyl group shown in formula (2) may be produced by conventionally known methods, or a commercially available one may be used.

[0063] Next, the difunctional compound containing the alkyl group having a sulfonyl group as shown in formula (2) is electrolytically fluorinated. This results in a difunctional compound containing the branched perfluoroalkyl group shown in formula (3) (fluorination step). As a method for electrolytic fluorination, for example, the Simmons method can be used, in which the difunctional compound containing the alkyl group shown in formula (2) is reacted with hydrofluoric anhydride using a Simmons electrolytic cell. Known conditions can be used for conditions such as current density, current flow rate, and temperature during electrolytic fluorination.

[0064] [Second Manufacturing Method] (In formula (1), X is -OH and Y is -SO ２ If F (X is -F, Y is -SO) ３(If H) In the same manner as the first manufacturing method described above, Rf corresponding to the target product １ and Rf ２ A bifunctional compound containing a branched perfluoroalkyl group represented by formula (3) is prepared as an intermediate compound.

[0065] Next, a bifunctional compound containing the branched perfluoroalkyl group shown in formula (3) is dissolved in alcohol and reacted with water (hydrolysis step). As a result, X in formula (1) becomes -OH and Y becomes -SO ２ A compound where F is (X is -F, Y is -SO) ３ It is possible to produce a compound (which is H).

[0066] In the above description, a preferred hydrolysis step was explained using the example of dissolving a bifunctional compound containing the branched perfluoroalkyl group shown in formula (3) in an alcohol and then adding water to react it. However, the hydrolysis step may also be a step in which the bifunctional compound containing the branched perfluoroalkyl group shown in formula (3) is reacted with water without dissolving it in an alcohol, or a step in which a solvent capable of dissolving the branched perfluoroalkyl group shown in formula (3) is used instead of alcohol.

[0067] Examples of solvents that can be used in the hydrolysis process include alcohols, acetonitrile, acetone, and tetrahydrofuran, and the Rf of the compound represented by formula (3) １ and Rf ２ The solvent can be appropriately determined depending on the type of product. The solvent used in the hydrolysis step is preferably an alcohol. This is because it increases the reaction rate of hydrolysis and allows for the acquisition of the target product, a bifunctional compound containing a branched perfluoroalkyl group, in high yield.

[0068] Examples of alcohols used in the hydrolysis process include methanol (MeOH), ethanol (EtOH), and 2-propanol (IPA). When using alcohol in the hydrolysis process, the fewer carbon atoms in the alcohol, the faster the hydrolysis reaction rate, and the higher the yield of the target product. For this reason, methanol is the most preferred alcohol to use in the hydrolysis process.

[0069] In the hydrolysis step, by adjusting the number of moles of water relative to the number of moles of the bifunctional compound containing the branched perfluoroalkyl group represented by formula (3), the two -SO groups in formula (3) are released. ２ Only one of F can be selectively hydrolyzed, and the two -SO in formula (3) ２ One of F is -SO ３ It can be represented as H.

[0070] In the hydrolysis process, the two -SO in formula (3) ２ Only one of F is -SO ３ The amount of water used in the reaction to form H is preferably in the range of 50 mol% to 400 mol%, more preferably in the range of 90 mol% to 400 mol%, and most preferably in the range of 250 mol% to 400 mol%, relative to the number of moles of the intermediate compound represented by formula (3). When the amount of water is 90 mol% or more relative to the number of moles of the intermediate compound represented by formula (3), X is -OH and Y is -SO ２ F is (X is -F, Y is -SO) ３ A difunctional compound containing a branched perfluoroalkyl group (H) can be sufficiently produced. Also, if the amount of water is 400 mol% or less, an excessive hydrolysis reaction occurs, resulting in X being -OH and Y being -SO ３ This prevents the formation of compounds containing H.

[0071] In the second manufacturing method, the two -SO in formula (3) ２ Hydrolyze only one of F, and remove the two -SO in formula (3). ２ Only one of F is -SO ３The method for producing a compound containing H was explained as an example, but in this embodiment, the two -SO in formula (3) ２ Both F are -SO ３ H is (where X is -OH and Y is -SO in equation (1)). ３ A bifunctional compound containing a branched perfluoroalkyl group (H) may be produced. Examples of methods for producing such a compound include the following:

[0072] For example, in the second manufacturing method described above, the two -SO in formula (3) ２ Hydrolyzing only one of F results in -SO ３ In the reaction involving H, the amount of water used can be set to an excess of, for example, 800 mol% or more relative to the number of moles of the intermediate compound represented by formula (3). In this case, the excess amount of water promotes hydrolysis, and in formula (1), X becomes -OH and Y becomes -SO ３ A difunctional compound containing a branched perfluoroalkyl group (H) is produced.

[0073] Also, in equation (1), X is -OH and Y is -SO ３ In the second production method described above, the two -SO groups in formula (3) are used to produce a bifunctional compound containing a branched perfluoroalkyl group that is H. ２ Only one of F is -SO ３ The reaction in which H is produced may also be carried out by heating, with the amount of water used being 200 mol% or more relative to the number of moles of the intermediate compound represented by formula (3). In this case, hydrolysis is accelerated by heating, and X in formula (1) becomes -OH and Y becomes -SO ３ A difunctional compound containing a branched perfluoroalkyl group (H) is produced.

[0074] [Third Manufacturing Method] (where X in formula (1) is -O) － M ＋ , Y is -SO ２ If F (X is -F, Y is -SO) ３ － M ＋ (If this is the case) or if X in equation (1) is -O － M ＋ , Y is -SO３ － M ＋ (When M is an alkali metal ion) In the same manner as the second manufacturing method described above, X in formula (1) is -OH and Y is -SO ２ If F (X is -F, Y is -SO) ３ (If H) or if X is -OH and Y is -SO in equation (1) ３ A compound containing H is produced as an intermediate compound.

[0075] The resulting intermediate compound is reacted with a solvent such as acetonitrile (MeCN) and an alkali metal compound containing the alkali metal corresponding to the alkali metal present in the target product. This reaction removes the -SO4 contained in the intermediate compound. ３ H is -SO ３ － M ＋ Therefore, X in equation (1) becomes -O － M ＋ , Y is -SO ２ F is (X is -F, Y is -SO) ３ － M ＋ (is) or X in equation (1) is -O － M ＋ , Y is -SO ３ － M ＋ An alkali metal salt of a difunctional compound containing a branched perfluoroalkyl group (where M is an alkali metal ion) is produced.

[0076] In the third manufacturing method, examples of alkali metal compounds to be reacted with the intermediate compound include alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates. Specifically, examples include lithium hydroxide, lithium carbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, cesium hydroxide, cesium carbonate, cesium bicarbonate, rubidium hydroxide, rubidium carbonate, and rubidium bicarbonate.

[0077] In the third manufacturing method, the -SO contained in the intermediate compound ３ H to -SO ３ － M ＋The reaction temperature in the reaction described above is preferably in the range of 0°C to 50°C, and more preferably in the range of 0°C to 40°C. If the reaction temperature is 0°C or higher, the reaction rate will be sufficiently fast. Also, if the reaction temperature is 50°C or lower, in the third manufacturing method, X in formula (1) is -O － M ＋ , Y is -SO ２ F is (X is -F, Y is -SO) ３ － M ＋ When producing a compound that is ( ), the intermediate compound contains -SO ２ F to -SO ３ － M ＋ This can suppress unwanted reactions from progressing.

[0078] In the third manufacturing method, X in formula (1) is -OH and Y is -SO ２ F is (X is -F, Y is -SO) ３ Using a compound (H), if X in formula (1) is -O － M ＋ , Y is -SO ２ F is (X is -F, Y is -SO) ３ － M ＋ When producing the compound (which is), the amount of alkali metal compound used is preferably in the range of 150 mol% to 400 mol%, more preferably in the range of 200 mol% to 350 mol%, and most preferably in the range of 200 mol% to 300 mol%, relative to the number of moles of the intermediate compound represented by formula (3). If the amount of alkali metal compound is 200 mol% or more, X is -O － M ＋ , Y is -SO ２ F is (X is -F, Y is -SO) ３ － M ＋ This allows for the sufficient generation of a bifunctional compound containing a branched perfluoroalkyl group. Furthermore, if the amount of alkali metal compound is 400 mol% or less, then X in formula (1) becomes -O － M ＋ , Y is -SO ３ － M ＋This can suppress the formation of unwanted compounds.

[0079] In the third manufacturing method, the compound shown in formula (3) is used as an intermediate compound, and X in formula (1) is -O － M ＋ , Y is -SO ３ － M ＋ When preparing a difunctional compound containing a branched perfluoroalkyl group (where M is an alkali metal), the two -SO groups in formula (3) ２ Hydrolyze one or both of F to obtain -SO ３ It is preferable to use a method in which H is reacted with an alkali metal compound, as this allows for efficient production. Therefore, the two -SO in formula (3) ２ Hydrolyzing only one of F results in -SO ３ It is preferable to use a method in which the hydrogen is first reacted with an alkali metal compound.

[0080] In other words, X in equation (1) is -O － M ＋ , Y is -SO ３ － M ＋ When producing a difunctional compound containing a branched perfluoroalkyl group (where M is an alkali metal ion), if X in formula (1) produced by the method described above is -O － M ＋ , Y is -SO ２ F is (X is -F, Y is -SO) ３ － M ＋ It is preferable to use a method in which an alkali metal salt of a difunctional compound containing a branched perfluoroalkyl group is further reacted with the alkali metal compound used as a raw material.

[0081] Using the compound shown in formula (3) as an intermediate compound, X in formula (1) becomes -O － M ＋ , Y is -SO ３ － M ＋When producing a bifunctional compound containing a branched perfluoroalkyl group (where M is an alkali metal ion), the amount of alkali metal compound used in the third production method is preferably 350 mol% or more and 450 mol% or less relative to the number of moles of the intermediate compound represented by formula (3), more preferably in the range of 380 mol% to 450 mol%, and most preferably in the range of 400 mol% to 450 mol%. When the amount of alkali metal compound is 400 mol% or more, X in formula (1) becomes -O － M ＋ , Y is -SO ３ － M ＋ This allows for the sufficient production of a bifunctional compound containing a branched perfluoroalkyl group. Furthermore, it is preferable that the amount of alkali metal compound is 450 mol% or less, as this reduces the amount of alkali metal compound that is not used in the reaction.

[0082] In the third manufacturing method, X in formula (1) is -O － M ＋ , Y is -SO ３ － M ＋ When preparing a difunctional compound containing a branched perfluoroalkyl group (where M is an alkali metal ion), X in formula (1) is -O － M ＋ , Y is -SO ２ F is (X is -F, Y is -SO) ３ － M ＋ The product may be manufactured without producing the product shown below. That is, a bifunctional compound containing a branched perfluoroalkyl group represented by formula (3) may be produced as an intermediate compound, and the product may be manufactured by reacting the compound represented by formula (3) with a solvent such as acetonitrile (MeCN) and an alkali metal compound containing an alkali metal corresponding to the alkali metal contained in the target product.

[0083] [Fourth Manufacturing Method] (where X in formula (1) is -O) － M ＋ And Y is -SO ２ NH ２ or -SO ２ NHM＋ (X is -NH ２ or -N － HM ＋ And Y is -SO ２ M ＋ (where M is an alkali metal ion) In the same manner as the third manufacturing method described above, if X in formula (1) is -O － M ＋ , Y is -SO ２ F is (X is -F, Y is -SO) ３ － M ＋ (is) or X in equation (1) is -O － M ＋ , Y is -SO ３ － M ＋ A compound (where M is an alkali metal ion) is prepared and used as the first intermediate compound.

[0084] The first intermediate compound is reacted in an aqueous ammonia solution to obtain -SO in the first intermediate compound. ３ － M ＋ SO ２ NH ２ or -SO ２ NHM ＋ This process generates a second intermediate compound. Subsequently, the second intermediate compound is reacted with an aqueous solution of an alkali metal compound containing the alkali metal corresponding to the alkali metal contained in the target product. As a result, X in formula (1) becomes -O － M ＋ And Y is -SO ２ NH ２ or -SO ２ NHM ＋ (X is -NH ２ or -N － HM ＋ And Y is -SO ２ M ＋ (where M is an alkali metal ion) This produces a difunctional compound containing a branched perfluoroalkyl group.

[0085] In the fourth manufacturing method, the alkali metal compound in the aqueous solution of the alkali metal compound reacted with the second intermediate compound is the same as the alkali metal compound reacted with the intermediate compound in the third manufacturing method.

[0086] [Fifth Manufacturing Method] (In formula (1), X is -F and Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ２ F is (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4). M is an alkali metal ion.) In the same manner as the first manufacturing method described above, Rf corresponding to the target product is prepared. １ and Rf ２ A bifunctional compound containing a branched perfluoroalkyl group represented by formula (3) is prepared and used as the first intermediate compound.

[0087] The first intermediate compound and the target product Rf ３ (Rf ３ is, -C ｎ F ２ｎ＋１ NH corresponding to (n=1 to 4) ２ SO ２ Rf ３ Then, a solvent such as acetonitrile (MeCN) is reacted with water in the presence of magnesium oxide, which acts as a catalyst, to produce a second intermediate compound (imidization step). Subsequently, the second intermediate compound is reacted with an alkali metal compound containing the alkali metal corresponding to the alkali metal contained in the target product, and the resulting product is dissolved in water.

[0088] The above indicates a preferred manufacturing method, NH ２ SO ２ Rf ３The explanation above used the example of a two-step reaction in which a solvent and water are reacted in the presence of magnesium oxide, and then reacted with an alkali metal compound. However, instead of the above two-step reaction, the NHMSO corresponding to the target product can be used. ２ Rf ３ Alternatively, a one-step reaction may be carried out in which the solvent and water are reacted in the presence of magnesium oxide.

[0089] Through the above steps, X in equation (1) becomes -F and Y becomes -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ２ F is (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4. M is an alkali metal ion.) A bifunctional compound containing a branched perfluoroalkyl group is obtained.

[0090] NH ratio to the number of moles of the first intermediate compound used in the imidation process ２ SO ２ Rf ３ By adjusting the number of moles, the two -SO compounds in the first intermediate compound can be changed. ２ Only one of F is -SO ２ N － M ＋ SO ２ Rf ３ It can be done this way.

[0091] In the imidation step to produce the second intermediate compound, the amount of magnesium oxide used as a catalyst is preferably in the range of 50 mol% to 200 mol%, more preferably in the range of 80 mol% to 160 mol%, and most preferably in the range of 100 mol% to 130 mol%, relative to the number of moles of the compound represented by formula (3), which is the first intermediate compound. If the amount of magnesium oxide used is 100 mol% or more, a sufficient effect of promoting the reaction to produce the second intermediate compound can be obtained. On the other hand, if the amount of magnesium oxide used is 200 mol% or less, it is possible to prevent a decrease in the yield of the second intermediate compound due to a decrease in the stirring efficiency of the reaction solution caused by using too much magnesium oxide.

[0092] The amount of water used in the imidation step to produce the second intermediate compound (the total amount of water used before reacting the second intermediate compound with the alkali metal compound) is preferably in the range of 50 mol% to 450 mol%, more preferably in the range of 200 mol% to 400 mol%, and most preferably in the range of 300 mol% to 400 mol%, relative to the number of moles of the compound represented by formula (3), which is the first intermediate compound. If the amount of water used in the imidation step to produce the second intermediate compound is 300 mol% or more, the second intermediate compound can be sufficiently produced. Furthermore, if the amount of water used in the imidation step to produce the second intermediate compound is 450 mol% or less, the hydrolysis reaction of the first intermediate compound can be suppressed, and the second intermediate compound can be produced in good yield.

[0093] The water used in the imidation step to generate the second intermediate compound is preferably added in multiple portions of 80 mol% to 150 mol% relative to the number of moles of the compound represented by formula (3), which is the first intermediate compound, and more preferably in portions of 100 mol% to 150 mol%. If the amount of water added at one time is 80 mol% or more, the reaction rate of the imidation reaction of the first intermediate compound in the imidation step becomes sufficiently fast. On the other hand, if the amount of water added at one time is 150 mol% or less, the hydrolysis reaction of the first intermediate compound in the imidation step proceeds preferentially over the imidation reaction, which prevents a decrease in the yield of the imide salt, which is the second intermediate compound.

[0094] In the fifth manufacturing method, the alkali metal compound to be reacted with the second intermediate compound is the same as the alkali metal compound reacted with the intermediate compound in the third manufacturing method.

[0095] [6th Manufacturing Method] (where X in formula (1) is -N) － HM ＋ And Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ２ N － HM ＋ (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4). M is an alkali metal ion.) In the same manner as the fifth manufacturing method described above, X in formula (1) is -F and Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ２ F is (Rf ３ is, -C ｎ F２ｎ＋１ (n = 1 to 4. M is an alkali metal ion.) The compound is produced as an intermediate compound.

[0096] The resulting intermediate compound is reacted in an aqueous ammonia solution. Then, the resulting reaction product is reacted with an alkali metal compound containing the alkali metal corresponding to the alkali metal in the target product. This process yields the -SO2 contained in the intermediate compound. ２ F is -SO ２ N － HM ＋ Therefore, X in equation (1) becomes -N － HM ＋ And Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ２ N － HM ＋ (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4. M is an alkali metal ion.) A bifunctional compound containing a branched perfluoroalkyl group is obtained.

[0097] In the sixth manufacturing method, the alkali metal compound to be reacted with the intermediate compound is the same as the alkali metal compound reacted with the intermediate compound in the third manufacturing method.

[0098] [Manufacturing Method 7] (where X in formula (1) is -O) － M ＋ And Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ３ － M ＋ (Rf ３is, -C ｎ F ２ｎ＋１ (n = 1 to 4). M is an alkali metal ion.) In the same manner as the fifth manufacturing method described above, X in formula (1) is -F and Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ２ F is (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4. M is an alkali metal ion.) The compound is produced as an intermediate compound.

[0099] The resulting intermediate compound is reacted with the alkali metal compound corresponding to the alkali metal contained in the target product, and the resulting product is dissolved in water. This allows the -SO contained in the intermediate compound to be released. ３ F is -SO ３ － M ＋ Therefore, X in equation (1) becomes -O － M ＋ And Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ３ － M ＋ (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4. M is an alkali metal ion.) A bifunctional compound containing a branched perfluoroalkyl group is obtained.

[0100] In the seventh manufacturing method, the alkali metal compound to be reacted with the intermediate compound is the same as the alkali metal compound reacted with the intermediate compound in the third manufacturing method.

[0101] [Manufacturing Method No. 8] (where X and Y in formula (1) are -SO ２ N － M ＋ SO ２ Rf ３ (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4). M is an alkali metal ion.) In the same manner as the fifth manufacturing method described above, X in formula (1) is -F and Y is -SO ２ N － M ＋ SO ２ Rf ３ (X is -N) － M ＋ SO ２ Rf ３ And Y is -SO ２ F is (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4. M is an alkali metal ion.) The compound is produced as an intermediate compound.

[0102] The obtained intermediate compound and the Rf of the target product ３ (Rf ３ is, -C ｎ F ２ｎ＋１ NH corresponding to (n=1 to 4) － M ＋ SO ２ Rf ３ Then, a solvent such as acetonitrile (MeCN) is reacted with the alkali metal fluoride corresponding to the alkali metal contained in the target product.

[0103] Through the above steps, X and Y in equation (1) become -SO ２ N － M ＋ SO ２ Rf ３ (Rf ３ is, -C ｎ F ２ｎ＋１ (n = 1 to 4). M is an alkali metal ion. A bifunctional compound containing a branched perfluoroalkyl group is obtained. Rf in X ３ and M and Rf in Y ３And M is Rf contained in the intermediate compound. ３ And the type of M, and the NH that reacts with the intermediate compound. － M ＋ SO ２ Rf ３ Ref ３ And it can be determined by the type of M. Rf in X ３ Rf in Y ３ They may be the same or different. Also, M in X may be the same or different from M in Y.

[0104] [9th Manufacturing Method] (where X in formula (1) is -F, -O) － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ (where M is hydrogen or an alkali metal ion, and Y is -I) In the same manner as the first manufacturing method described above, the Rf corresponding to the target product １ and Rf ２ A bifunctional compound containing a branched perfluoroalkyl group represented by formula (3) is prepared as an intermediate compound.

[0105] Next, a difunctional compound containing the branched perfluoroalkyl group shown in formula (3) is reacted with iodine, acid potassium fluoride (KF·HF), and a solvent such as acetonitrile (MeCN) in the presence of silver nitrate and / or silver sulfate as a catalyst (iodation step). This releases the two -SO groups of the difunctional compound containing the branched perfluoroalkyl group shown in formula (3). ２ One of the F atoms is iodine (where X is -F and Y is -I in equation (1)), which produces an iodide.

[0106] In the iodization step to produce an iodide of a bifunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I, the amount of potassium acid fluoride used is preferably in the range of 70 mol% to 150 mol%, more preferably in the range of 90 mol% to 140 mol%, and most preferably in the range of 110 mol% to 130 mol%, relative to the number of moles of the intermediate compound represented by formula (3). If the amount of potassium acid fluoride is 100 mol% or more, the reaction to produce the iodide can proceed sufficiently. Furthermore, if the amount of potassium acid fluoride is 150 mol% or less, it is preferable because a small amount of potassium acid fluoride is not used in the reaction.

[0107] In the iodization step to produce an iodide of a bifunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I, the amount of iodine used is preferably in the range of 70 mol% to 150 mol%, more preferably in the range of 90 mol% to 140 mol%, and most preferably in the range of 120 mol% to 140 mol%, relative to the number of moles of the intermediate compound represented by formula (3). If the amount of iodine is 100 mol% or more, the reaction to produce the iodide can proceed sufficiently. Furthermore, if the amount of iodine is 150 mol% or less, it is preferable because less iodine is not used in the reaction.

[0108] In the iodization step to produce an iodide of a bifunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I, one catalyst can be selected from silver nitrate, silver sulfate, or a mixture containing silver nitrate and silver sulfate in any proportion, with silver sulfate being preferred. This is because if silver nitrate is used as a catalyst, the resulting iodide may be reacted with ammonia in the next step without purification, potentially generating silver fulminate (silver nitride).

[0109] In the iodization step to produce an iodide of a bifunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I, the amount of catalyst used is, for example, when silver nitrate is used as the catalyst, preferably 80 mol% to 150 mol%, more preferably 100 mol% to 140 mol%, and most preferably 120 mol% to 140 mol%, relative to the number of moles of the intermediate compound represented by formula (3). When silver sulfate is used as the catalyst, preferably 40 mol% to 80 mol%, more preferably 50 mol% to 70 mol%, and most preferably 60 mol% to 70 mol%, relative to the number of moles of the intermediate compound represented by formula (3).

[0110] When the amount of silver nitrate or silver sulfate is equal to or greater than the lower limit mentioned above, side reactions can be suppressed in the iodide process, and the effect of promoting the reaction that produces iodide can be sufficiently obtained. However, even if the amount of silver nitrate or silver sulfate used exceeds the upper limit mentioned above, the effect of promoting the reaction does not improve. For this reason, it is preferable to keep the amount of silver nitrate or silver sulfate used within the range of the upper limit mentioned above.

[0111] In this embodiment, X in formula (1) is -O － M ＋ When producing a difunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I, the difunctional compound containing a branched perfluoroalkyl group obtained by the above method has the -SO ２ F, -SO ３ － M ＋ (Assume M is an alkali metal ion). Specifically, a bifunctional compound containing a branched perfluoroalkyl group in formula (1) obtained by the above method, where X is -F and Y is -I, is dissolved in a solvent and reacted in an aqueous solution of alkali metal hydroxide.

[0112] The -SO group of a difunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I ２ F, -SO ３ － M＋ When M is an alkali metal ion, the amount of alkali metal hydroxide used is preferably in the range of 150 mol% to 250 mol%, more preferably in the range of 180 mol% to 240 mol%, and most preferably in the range of 200 mol% to 230 mol%, relative to the number of moles of the bifunctional compound containing the branched perfluoroalkyl group in formula (1) where X is -F and Y is -I. If the amount of alkali metal hydroxide is 200 mol% or more, the -SO content of the bifunctional compound containing the branched perfluoroalkyl group where X is -F and Y is -I ２ F, -SO ３ － M ＋ The reaction (where M is an alkali metal ion) can proceed sufficiently. Furthermore, it is preferable that the amount of alkali metal hydroxide is 250 mol% or less, as this reduces the amount of alkali metal hydroxide that is not used in the reaction.

[0113] In this embodiment, X in formula (1) is -N － HM ＋ When producing a difunctional compound containing a branched perfluoroalkyl group (where M is an alkali metal ion) and Y is -I, the difunctional compound containing a branched perfluoroalkyl group in formula (1) obtained by the above method, where X is -F and Y is -I, has the -SO ２ F, -SO ２ N － HM ＋ Let M be an alkali metal.

[0114] Specifically, a difunctional compound containing a branched perfluoroalkyl group in formula (1) obtained by the above method, where X is -F and Y is -I, is reacted with ammonia to produce the -SO compound of the difunctional compound containing the branched perfluoroalkyl group. ２ F to -SO ２ NH ２ After that, it is reacted with an alkali metal hydroxide to produce -SO ２ NH ２ to -SO ２ N － HM ＋(M is an alkali metal ion.) The ammonia used in this reaction may be an aqueous ammonia solution or ammonia gas. When ammonia gas is used, a bifunctional compound containing a branched perfluoroalkyl group in formula (1), where X is -F and Y is -I, which has been dissolved in an organic solvent, is reacted with the ammonia gas. Examples of organic solvents that can be used include acetonitrile, diisopropyl ether, and tetrahydrofuran.

[0115] Furthermore, compounds in which X is -OH when Y is I can be produced, for example, by dissolving a bifunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I in an alcohol such as methanol (MeOH), adding water, aging, and hydrolysis.

[0116] Also, when Y is I, X is -N － M ＋ SO ２ Rf ３ For example, a difunctional compound containing a branched perfluoroalkyl group in formula (1) where X is -F and Y is -I is dissolved in a solvent such as acetonitrile, and the Rf corresponding to the target product is obtained. ３ SO ２ NH － M ＋ It can be produced by adding a compound having a - group to potassium fluoride and heating under reflux to allow the reaction to occur.

[0117] In the manufacturing method of this embodiment, the case in which M contained in X and / or Y is an alkali metal ion was described as an example. However, if M contained in X and / or Y is not an alkali metal ion, the same method can be used by replacing the alkali metal compound with a compound corresponding to M contained in X and / or Y.

[0118] For example, if M contained in X and / or Y is an alkaline earth metal ion, examples of alkaline earth metal compounds corresponding to M contained in X and / or Y include alkaline earth metal hydroxides and alkaline earth metal carbonates. Specifically, examples include magnesium hydroxide, calcium hydroxide, barium hydroxide, calcium carbonate, and barium carbonate.

[0119] (Solvent) In the method for producing a bifunctional compound containing a branched perfluoroalkyl group according to this embodiment, it is preferable to use a known solvent as appropriate for the reaction. The solvent can be any solvent that can dissolve the raw materials used in each reaction, and for example, one or more can be selected from alcohols such as methanol, linear esters such as ethyl acetate, carbonate esters such as diethyl carbonate, ethers such as t-butyl methyl ether, diisopropyl ether, and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane, linear nitriles such as acetonitrile and propionitrile, and ketones such as acetone. It is preferable to use acetone and / or acetonitrile as the solvent.

[0120] In the method for producing a bifunctional compound containing a branched perfluoroalkyl group according to this embodiment, a fluorination step is performed in which a bifunctional compound containing an alkyl group, represented by general formula (2), is electrolytically fluorinated to produce a bifunctional compound containing a branched perfluoroalkyl group, represented by general formula (3). Therefore, according to the production method of this embodiment, a bifunctional compound containing a branched perfluoroalkyl group, represented by general formula (3), which is an example of a novel compound represented by general formula (1), can be produced by an easy and industrially feasible method.

[0121] Furthermore, the novel difunctional compound containing a branched perfluoroalkyl group, represented by general formula (3), exhibits good reactivity and can be used as an intermediate compound when producing difunctional compounds containing branched perfluoroalkyl groups represented by general formula (1) other than general formula (3). By using the difunctional compound containing a branched perfluoroalkyl group represented by general formula (3) as an intermediate compound, it is possible to produce difunctional compounds containing branched perfluoroalkyl groups represented by general formula (1), other than general formula (3), which are derivatives of the compound represented by general formula (3).

[0122] The novel bifunctional compound containing a branched perfluoroalkyl group, represented by general formula (1), is useful because it can react with a variety of compounds. Examples of compounds that can readily react with the bifunctional compound containing a branched perfluoroalkyl group represented by general formula (1) include water, alcohols, ammonia, perfluoroalkylsulfonamides, aliphatic amines and aromatic amines, aliphatic amides and aromatic amides.

[0123] Examples of alcohols include methanol, ethanol, benzyl alcohol, and trifluoroethanol. Examples of perfluoroalkyl sulfonamides include trifluoromethanesulfonamide, pentafluoroethanesulfonamide, heptafluoropropanesulfonamide, and nonafluorobutanesulfonamide.

[0124] Examples of aliphatic amines and aromatic amines include ethylamine, propylamine, dimethylamine, diethylamine, 1-adamantanamine, aniline, and 2-naphthylamine. Examples of aliphatic amides and aromatic amides include acetamide, 1-adamantane carboxamide, trifluoroacetamide, and benzamide.

[0125] The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[0126] [Example 1] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-1) was prepared by the method shown below.

[0127]

[0128] Stainless steel double-tube reflux condenser with cooling jacket, stainless steel construction, standard capacity 500 ml, effective anode area 6.75 dm² ２ A Simmons-type electrolytic cell was prepared. In addition, as a raw material, R in formula (2) was used. １ is hydrogen, R ２ We prepared a 1,1-ethanedisulfonyl difluoride represented by formula (21), which is a bifunctional compound containing an alkyl group in which is a methyl group.

[0129] In the above-mentioned Simmons-type electrolytic cell, 25 g of 1,1-ethanedisulfonyl difluoride represented by formula (21) and 475 g of hydrofluoric anhydride were charged, and the current density was 0.6 A / dm². ２ Electrolytic fluorination was started with a current of 4.05 A. During electrolytic fluorination, 1,1-ethanedisulfonyl difluoride was continuously supplied to the electrolytic cell by syringe pump. The supply rate of 1,1-ethanedisulfonyl difluoride was increased or decreased depending on the current and voltage. The brine temperature to the reflux condenser was set to -35°C. The temperature inside the electrolytic cell was kept within the range of 9°C to 11°C. During electrolytic fluorination, the crude product that separated in the electrolytic cell and formed the lower layer was sequentially withdrawn from the bottom valve installed in the electrolytic cell.

[0130] Electrofluorination was terminated after a total energizing time of 148 hours. The total amount of 1,1-ethanedisulfonyl difluoride added during electrofluorination was 477 g, and the yield of crude product was 577 g. The total amount of current applied during electrofluorination was 599 Ahr, which was 114% of the theoretical current. The steady-state cell voltage during electrofluorination was 6.1 V to 6.4 V.

[0131] The crude composition obtained by electrolytic fluorination was subjected to GC-MS analysis using a gas chromatography-mass (GC-MS) analyzer (product name: GC-MS QP2020NX, manufactured by Shimadzu Corporation). Furthermore, nuclear magnetic resonance (NMR) spectroscopy (NMR) was performed using a nuclear magnetic resonance (NMR) spectrometer (product name: AVANCE NEO 400, manufactured by Bruker) with trifluorotoluene as the internal standard. １９ F-NMR measurements were performed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (CDCl ３ ): δ 56.8 to 57.0 (m, 2F), -70.08 to -70.47 (q, 3F), -147.2 to 147.5 (m, 1F)

[0132] GC-MS analysis of crude product and １９ Based on the results of F-NMR measurement, the crude product was identified. As a result, it was confirmed that 1,2,2,2-tetrafluoroethane-1,1-disulfonyl difluoride, a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1), was produced. Furthermore, the purity of the bifunctional compound containing the branched perfluoroalkyl group represented by formula (1-1) in the crude product, as confirmed by gas chromatography analysis, was 88%.

[0133] Subsequently, the crude product was quenched with crushed ice and washed twice with deionized water. After washing, the crude product was dried with anhydrous sodium sulfate, filtered, and purified by distillation to obtain 423 g of product. The purity of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-1) in the distilled product, as confirmed by gas chromatography analysis, was 99.8%. Furthermore, the starting material (R in formula (2)) of the distilled product was also analyzed. １ is hydrogen, R ２ The yield for a difunctional compound containing an alkyl group that is a methyl group was 65%.

[0134] [Example 2] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-2) was prepared by the method described below.

[0135]

[0136] 16.5 g of the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-1) prepared in Example 1 was dissolved in 25 mL of methanol, and 4.4 mL of water was added and the mixture was aged at 25°C for 24 hours (hydrolysis step). The amount of water used in this reaction was 394 mol% relative to the number of moles of the compound shown in formula (1-1).

[0137] Next, 125 mL of acetonitrile and 12.8 g of potassium bicarbonate were added to the matured solution and reacted at 25°C for at least 2 hours, adjusting the pH of the solution to 7-8. The amount of potassium bicarbonate (alkali metal compound) used in the reaction was 206 mol% relative to the number of moles of the compound shown in formula (1-1).

[0138] The reaction solution was filtered to separate the solid, and the solvent was removed from the filtrate to obtain 16.4 g of a white solid product. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 80%.

[0139] The product obtained in Example 2 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-2), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 51.3 (dq, 1F), -72.3 (dd, 3F), -150.48 to -150.55 (m, 1F)

[0140] [Example 3] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-3) was prepared by the method described below.

[0141]

[0142] 4.0 g of the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-2), prepared in Example 2, was slowly added to 8 mL of a 25% aqueous ammonia solution. As a result, the temperature of the aqueous ammonia solution, which was 24°C before adding the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-2), rose to 24°C to 39°C. After adding 4.0 g of the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-2) to the aqueous ammonia solution, it was allowed to mature for 30 minutes, and the solvent was removed from the reaction solution by distillation. 10 mL of water was added to the obtained product, and 20 mL of 2 mol / L hydrochloric acid was added while using an ice bath, and the product was extracted three times with 30 mL of ethyl acetate.

[0143] The solvent was removed from the ethyl acetate solution, and 10 mL of water and 2.1 mL of 48% potassium hydroxide aqueous solution were added. The mixture was then aged for 1 hour. By removing the solvent from the reaction solution, 4.4 g of a white solid product was obtained. The amount of potassium hydroxide (alkali metal compound) used in the reaction was 201 mol% relative to the number of moles of the compound shown in formula (1-1). The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group shown in formula (1-2)) was 92%.

[0144] The product obtained in Example 3 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-3), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (D2O): δ 69.7 (d, 3F), -150.7 (q, 1F)

[0145] [Example 4] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-4) was prepared by the method described below.

[0146]

[0147] 10.4 g of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-1) prepared in Example 1 and 5.9 g of the trifluoromethanesulfonylamide shown in formula (4) were dissolved in 50 mL of acetonitrile, and 1.7 g of magnesium oxide and 2.8 mL of water were added and the mixture was aged at 25°C for 96 hours (imidization step). 0.7 mL of water was added at the start of aging, 24 hours after the start of aging, 48 hours after the start of aging, and 72 hours after the start of aging. The amount of water used in this reaction was 397 mol% of the number of moles of the compound shown in formula (1-1). The amount of magnesium oxide (catalyst) used in the reaction was 108 mol% of the number of moles of the compound shown in formula (1-1).

[0148] Subsequently, 7.9 g of potassium bicarbonate was added to the matured solution and it was matured for 4 hours. The matured solution was filtered to separate the solid, and the solvent was removed from the filtrate. The obtained product was dissolved in 140 mL of water, washed with 50 mL of chloroform and 50 mL of diisopropyl ether, and then extracted with 60 mL of ethyl acetate and 20 mL of chloroform. The solvent was removed by distillation to obtain 12.5 g of a white solid product. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group shown in formula (1-1)) was 60%.

[0149] The product obtained in Example 4 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-4), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 54.0 (dq, 1F), -71.2 (dd, 3F), -80.4 (s, 3F), -147.21 to -147.25 (m, 1F)

[0150] [Example 5] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-4) was prepared by the method described below.

[0151] 5.0 g of the difunctional compound containing the branched perfluoroalkyl group represented by formula (1-1) prepared in Example 1 was dissolved in 25 mL of acetonitrile and heated in an ice bath, and trifluoromethanesulfonylamide potassium (CF ３ SO ２ N － HK ＋ 3.6 g of the substance and 1.6 g of potassium fluoride were added, and the mixture was aged at 5°C for 4 hours to obtain a solution containing the product.

[0152] The product obtained in Example 5 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-4), was formed. １９ Based on the results of F-NMR measurements, the yield of the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-4) relative to the starting material (the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-1)) was 27%.

[0153] [Example 6] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-5) was prepared by the method described below.

[0154]

[0155] 4.0 g of a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-4), prepared in Example 4, was slowly added dropwise to 8 mL of a 25% aqueous ammonia solution and aged at 5°C for 4 hours. After aging, the solvent was removed from the reaction mixture, and 20 mL of 2 mol / L hydrochloric acid was added. The mixture was then extracted twice with 20 mL of ethyl acetate. 4.8 g of the crude product was obtained by removing the solvent.

[0156] The obtained crude product was treated in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the crude product. As a result, X in equation (1) was -N － K ＋ SO ２ CF ３ And Y is -SO ２ NH ２ The imide salt (CF) of a difunctional compound containing a branched perfluoroalkyl group３ SO ２ N － K ＋ O ２ SCF (CF ３ ) SO ２ NH ２ We were able to confirm that it was generated.

[0157] Next, the crude product was dissolved in 10 mL of water, and 1.5 mL of 48% potassium hydroxide aqueous solution was added and the mixture was aged, confirming that the pH was within the range of 10 to 11. By distilling off the solvent from the aged solution, 5.4 g of the crude product was obtained. 22 mL of 2-propanol was added to the obtained crude product to recrystallize it, and the resulting crystals were vacuum-dried to obtain 3.5 g of a product consisting of a white to pale yellow solid. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group shown in formula (1-4)) was 80%.

[0158] The product obtained in Example 6 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-5), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (D ２ O): δ -68.9 (d, 3F), -78.4 (s, 3F), -147.6 (q, 1F)

[0159] [Example 7] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-7) was prepared by the method described below.

[0160]

[0161] 2.65 g of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-1), prepared in Example 1, was dissolved in 10 mL of acetonitrile and stirred in an ice bath. 3.56 g of iodine, 2.14 g of silver sulfate, and 0.94 g of acidic potassium fluoride (KFHF) were added, and the mixture was aged for 27 hours while gradually increasing the temperature to 23°C (iodation step). The aged solution was filtered to separate the solids, and a solution containing the product was obtained. The amount of iodine used in this reaction was 141 mol% relative to the number of moles of the compound shown in formula (1-1). The amount of acidic potassium fluoride (KFHF) used in the reaction was 121 mol% relative to the number of moles of the compound shown in formula (1-1).

[0162] The obtained product was treated in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-6), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 37.0 (dq, 1F), -74.5 (t, 3F), -139.9 (dq, 1F)

[0163] A solution containing 2.5 g of a bifunctional compound having a branched perfluoroalkyl group as shown in formula (1-6) was mixed with 5 mL of water and 1.8 mL of 48% potassium hydroxide aqueous solution, and the mixture was allowed to mature for 5 hours. After maturation, 15 mL of water was added to the reaction mixture, and it was washed five times with 30 mL of chloroform. The aqueous layer was then concentrated to dryness to obtain the crude product. The crude product was filtered to separate the solids by adding 20 mL of acetone, and the solvent was removed from the filtrate to obtain 2.69 g of a white solid product. The yield of the product relative to the starting material (a bifunctional compound having a branched perfluoroalkyl group as shown in formula (1-1)) was 78%.

[0164] The product obtained in Example 7 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-7), was formed. １９The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ -74.4 (d, 3F), -132.7 (q, 1F)

[0165] [Example 8] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-2) was prepared by the method described below.

[0166] 5.4 g of the bifunctional compound containing the branched perfluoroalkyl group represented by formula (1-1) prepared in Example 1 was dissolved in 25 mL of acetonitrile. 3.3 g of potassium fluoride was added to this solution, and the mixture was placed in an ice bath. 3.2 mL of 48% potassium hydroxide aqueous solution was added dropwise over 30 minutes to lower the solution temperature to 15°C or below, and the mixture was then aged for 4 hours. 50 mL of acetone was added to the aged solution, and the mixture was filtered to separate the solid. The solvent was then removed from the filtrate to obtain 4.1 g of a yellow solid product.

[0167] The product obtained in Example 8 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, a difunctional compound containing a branched perfluoroalkyl group represented by formula (1-2) and HCF (CF ３ ) SO ３ We were able to confirm that K was generated. １９ Based on the results of F-NMR measurements, the yield of the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-2) relative to the starting material of the product (the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-1)) was 36%, and HCF (CF ３ ) SO ３ The yield of K was 42%. HCF (CF ３ ) SO ３ K's １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ -75.6 (dd, 3F), -195.1 (dq, 1F)

[0168] [Example 9] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-8) was prepared by the method described below.

[0169]

[0170] Dissolve 10.06 g of the bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1) produced in Example 1 in 15 mL of methanol, add 2.7 mL of water, and age at 25°C for 24 hours (hydrolysis step). The amount of water used in this reaction was 395 mol% based on the number of moles of the compound represented by formula (1-1). Further, 2.0 g of basic alumina was added to the aged solution and aged for 1 hour. The solution after the reaction was filtered to separate the solid matter, and the solvent was distilled off from the filtrate to obtain 11.5 g of a strongly acidic liquid with a pungent odor.

[0171] For the product obtained in Example 9, in the same manner as in Example 1 １９ F-NMR measurement was performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-8) was formed. Also, １９ The mass of the compound represented by formula (1-8) in the product calculated from the results of the F-NMR measurement was 7.3 g, and the yield with respect to the raw material of the product (the bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 73%. The results of the F ２ OSCF(CF ３ )SO ３ H of １９ the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 53.1 (dq, 1F), -70.7 (dd, 3F), -148.93 to -148.99 (m, 1F)

[0172] [Example 10] A bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-9) was produced by the method shown below.

[0173]

[0174] The same procedure as in Example 2 was followed, except that sodium hydroxide carbonate was used instead of potassium bicarbonate, to obtain a product consisting of a white solid. The amount of water used in this reaction was 395 mol% relative to the number of moles of the compound shown in formula (1-1). The amount of sodium bicarbonate (alkali metal compound) used in the reaction was 254 mol% relative to the number of moles of the compound shown in formula (1-1).

[0175] The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 82%. The product obtained in Example 10 was prepared in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-9), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 51.5 (dq, 1F), -72.3 (dd, 3F), -150.45 to -150.51 (m, 1F)

[0176] [Example 11] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-10) was prepared by the method described below.

[0177]

[0178] The same procedure as in Example 2 was followed, except that lithium carbonate was used instead of potassium bicarbonate, to obtain a product consisting of a white solid. The amount of water used in this reaction was 395 mol% relative to the number of moles of the compound shown in formula (1-1). The amount of lithium carbonate (alkali metal compound) used in the reaction was 111 mol% relative to the number of moles of the compound shown in formula (1-1) (equivalent to 222 mol% in terms of the amount of lithium metal).

[0179] The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 80%. The product obtained in Example 11 was prepared in the same manner as in Example 1. １９F-NMR measurement was carried out to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-10) was produced. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 51.6 (dq, 1F), -72.3 (dd, 3F), -150.49 to -150.52 (m, 1F)

[0180] [Example 12] A bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-11) was produced by the method shown below.

[0181]

[0182] 2.57 g of the bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1) produced in Example 1 was dissolved in 3.8 mL of methanol, 0.68 mL of water was added, and the mixture was aged at 25 °C for 24 hours (hydrolysis step). The amount of water used in this reaction (the reaction in which one of the two -SO ２ F is converted to -SO ３ H) was 391 mol% based on the number of moles of the compound represented by formula (1-1).

[0183] Next, 15 mL of water and 3.3 mL of a 48% aqueous potassium hydroxide solution were added to the solution aged in the hydrolysis step, and the mixture was reacted at 25 °C for 2 hours or more to adjust the pH of the solution within the range of 10 to 12. The amount of potassium hydroxide (alkali metal compound) used in this reaction was 425 mol% based on the number of moles of the compound represented by formula (1-1).

[0184] After the reaction solution was filtered to remove the solid matter, the solvent was distilled off from the filtrate, and then 16 mL of water was added for recrystallization. The obtained crystals were dried by heating at 100 °C to obtain 2.2 g of a product composed of a white solid. The yield with respect to the raw material of the product (the bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 68%.

[0185] For the product obtained in Example 12, in the same manner as in Example 1 １９F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-11), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (D ２ O): δ -71.2 (d, 3F), -154.54 to -150.60 (m, 1F)

[0186] [Example 13] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-12) was prepared by the method described below.

[0187]

[0188] 3.07 g of the difunctional compound containing the branched perfluoroalkyl group represented by formula (1-1) prepared in Example 1 was dissolved in 4.5 mL of methanol, and 0.82 mL of water was added and the mixture was aged at 25°C for 24 hours (hydrolysis step). This reaction (the two -SO groups of the compound represented by formula (1-1)) ２ Of F, one is -SO ３ The amount of water used in the reaction (represented by H) was 396 mol% relative to the number of moles of the compound shown in formula (1-1).

[0189] Next, 15 mL of water and 1.97 g of sodium hydroxide were added to the matured solution in the hydrolysis step at 25°C, causing the solution temperature to rise to 50°C. The reaction was then allowed to proceed for more than 2 hours while allowing it to cool, and it was confirmed that the pH of the solution was within the range of 10 to 12. The amount of sodium hydroxide (alkali metal compound) used in this reaction was 430 mol% relative to the number of moles of the compound shown in formula (1-1).

[0190] The reaction solution was cooled in an ice bath, filtered to separate the solid, and the solvent was removed from the filtrate. The reaction mixture was then concentrated, and the resulting solid was heated and dried at 100°C to obtain 2.98 g of a white solid product.

[0191] The product obtained in Example 13 was processed in the same manner as in Example 1. １９F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, represented by formula (1-12), was formed. Furthermore, １９ Based on the results of F-NMR measurements, the yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 82%. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (D ２ O): δ -71.4 (d, 3F), -154.8 (q, 1F)

[0192] [Example 14] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-13) was prepared by the method described below.

[0193]

[0194] 3.10 g of the difunctional compound containing the branched perfluoroalkyl group represented by formula (1-1) prepared in Example 1 was dissolved in 4.5 mL of methanol, and 0.82 mL of water was added and the mixture was aged at 25°C for 24 hours (hydrolysis step). This reaction (the two -SO groups of the compound represented by formula (1-1)) ２ Of F, one is -SO ３ The amount of water used in the reaction (represented by H) was 393 mol% relative to the number of moles of the compound shown in equation (1-1).

[0195] Next, 15 mL of water and 1.97 g of lithium hydroxide monohydrate were added to the matured solution at 25°C during the hydrolysis process, causing the solution temperature to rise to 45°C. The reaction was then allowed to proceed for more than 2 hours while allowing it to cool, and it was confirmed that the pH of the solution was within the range of ~12. The amount of lithium hydroxide (alkali metal compound) used in this reaction was 405 mol% relative to the number of moles of the compound shown in formula (1-1).

[0196] The reaction solution was cooled in an ice bath, filtered to separate the solid, and the solvent was removed from the filtrate. The reaction mixture was then concentrated, and the resulting oily product was heated and dried at 120°C to obtain 2.79 g of a hygroscopic white solid product.

[0197] The product obtained in Example 14 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, represented by formula (1-13), was formed. Furthermore, １９ Based on the results of F-NMR measurements, the yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 80%. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (D ２ O): δ -71.4 (d, 3F), -154.7 (q, 1F)

[0198] [Example 15] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-14) was prepared by the method described below.

[0199]

[0200] In the same manner as in Example 4, 10.4 g of the bifunctional compound containing the branched perfluoroalkyl group represented by formula (1-1) prepared in Example 1 and 5.9 g of the trifluoromethanesulfonylamide represented by formula (4) were dissolved in 50 mL of acetonitrile, and 1.7 g of magnesium oxide and 2.8 mL of water were added and the mixture was aged at 25°C for 96 hours (imidization step). 0.7 mL of water was added at the start of aging, 24 hours after the start of aging, 48 hours after the start of aging, and 72 hours after the start of aging. The amount of water used in this reaction was 397 mol% of the number of moles of the compound represented by formula (1-1). The amount of magnesium oxide (catalyst) used in the reaction was 108 mol% of the number of moles of the compound represented by formula (1-1).

[0201] Subsequently, 14 mL of diisopropylethylamine (DIPEA) was added to the aged solution, replacing the potassium bicarbonate used in Example 4, and the mixture was aged for 1 hour. The aged solution was filtered to remove solids, and the solvent was removed from the filtrate. The obtained product was dissolved in chloroform, and the organic layer was washed with 1N hydrochloric acid and water. The solvent was then removed by distillation to obtain a pale yellow liquid product. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 60%.

[0202] The product obtained in Example 15 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-14), was formed.

[0203] １９ The results of the F-NMR measurement are shown below. １９ F-NMR (CDCl ３ ): δ 54.4 (dq, 3F), -71.2 (dd, 3F), -80.1 (d, 3F), -147.79 to -147.88 (m, 1F) １ H-NMR (CDCl ３ ): δ 6.37 (brs, 1H), 3.74-3.63 (m, 2H), 3.16 (dq, 2H), 1.43 (t, 3H), 1.42 (d, 6H), 1.40 (6H, d)

[0204] [Example 16] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-15) was prepared by the method shown below.

[0205]

[0206] ​1.45 g of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-4), prepared in Example 4, was dissolved in 2 mL of water. 0.55 mL of a 48% potassium hydroxide aqueous solution was added, and the mixture was aged at 25°C for 24 hours. The aged solution was then concentrated to dryness to obtain the crude product. The amount of potassium hydroxide (alkali metal compound) used in the reaction was 209 mol% relative to the number of moles of the compound shown in formula (1-4). 15 mL of acetone was added to the obtained crude product, and the solid was filtered off. Subsequently, the solvent was removed from the filtrate to obtain 1.42 g of a white solid product.

[0207] The product obtained in Example 16 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. The results confirmed the formation of a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-15). Furthermore, １９ Based on the results of F-NMR measurements, the yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-4)) was 92%.

[0208] １９ The results of the F-NMR measurement are shown below. １９ F-NMR (D ２ O): δ -70.3 (d, 3F), -79.2 (s, 3F), -151.4 (q, 1F) １９ F-NMR (MeOH-d4): δ -71.0 (d, 3F), -80.5 (s, 3F), -151.5 (q, 1F)

[0209] [Example 17] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-16) was prepared by the method described below.

[0210]

[0211] 2.23 g of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-4) prepared in Example 4 was dissolved in 20 mL of acetonitrile, and 2.20 g of potassium trifluoromethanesulfonylamide shown in formula (14) and 0.42 g of potassium fluoride were added, and the mixture was aged for 72 hours under heating reflux in an oil bath at 90°C.​

[0212] The matured solution is filtered to separate the solids, and CF ３ SO ２ N － K ＋ O ２ SCF (CF ３ ) SO ２ N － K ＋ O ２ SCF ３ And CF ３ SO ２ N － K ＋ O ２ SCF (CF ３ ) SO ３ A solution containing K was obtained. The obtained solution was concentrated and dissolved in 25 mL of ethyl acetate, then washed twice with 30 mL of water, and the ethyl acetate layer was concentrated to obtain 1.70 g of a white solid product.

[0213] The product obtained in Example 17 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. The results confirmed the formation of a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-16). Furthermore, １９ Based on the results of F-NMR measurements, the yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-4)) was 55%.

[0214] １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ -70.1 (d, 3F), -80.4 (s, 6F), -147.4 (q, 1F)

[0215] [Example 18] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-17) was prepared by the method described below.

[0216]

[0217] ​1.09 g of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-1) prepared in Example 1 and 0.62 g of the trifluoromethanesulfonylamide shown in formula (4) were dissolved in 5 mL of acetonitrile, and 0.18 g of magnesium oxide and 0.28 mL of water were added and the mixture was aged at 25°C for 96 hours (imidization step). 70 μL of water was added at the start of aging, 24 hours after the start of aging, 48 hours after the start of aging, and 72 hours after the start of aging. The amount of water used in this reaction was 380 mol% relative to the number of moles of the compound shown in formula (1-1). The amount of magnesium oxide (catalyst) used in the reaction was 109 mol% relative to the number of moles of the compound shown in formula (1-1).

[0218] Subsequently, the matured solution was filtered to separate the solids, and the solvent was removed from the filtrate. The obtained product was dissolved in 15 mL of water and washed with 5 mL of chloroform and 5 mL of diisopropyl ether. Then, it was extracted with 6 mL of ethyl acetate and 2 mL of chloroform, and the solvent was removed by distillation to obtain a pale yellow oily product.

[0219] The obtained oily product was dissolved in 10 mL of acetonitrile, a solvent, and 0.43 g (100 mol%) of calcium carbonate was added and the mixture was aged for 24 hours. After aging, the solvent was removed from the solution by distillation to obtain 1.58 g of a white solid product. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group shown in formula (1-1)) was 50%.

[0220] The product obtained in Example 18 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, represented by formula (1-17), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 54.0 (dq, 1F), -71.2 (dd, 3F), -80.4 (s, 3F), -147.21 to -147.25 (m, 1F)

[0221] [Example 19] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-18) was prepared by the method described below.

[0222]

[0223] 0.57 g of the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-3), prepared in Example 3, was dissolved in 10 mL of water, and 0.95 g of tetrabutylammonium chloride was added and the mixture was aged at 25°C for 4 hours. The reaction solution was extracted three times with 20 mL of chloroform and 10 mL of ethanol, and the solvent was removed from the filtrate to obtain 1.20 g of a pale yellow oily product. The yield of the product relative to the starting material (the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-3)) was 95%.

[0224] The product obtained in Example 19 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, represented by formula (1-18), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (CDCl ３ ): δ 70.4 (d, 3F), -150.3 (q, 1F) １ H-NMR (CDCl ３ ): δ 3.36-3.31 (m, 16H), 1.69-1.61 (m, 16H), 1.49-1.40 (m, 16H), 1.00 (t, 24H)

[0225] [Example 20] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-19) was prepared by the method described below.

[0226]

[0227] 7.41 g of the bifunctional compound containing a branched perfluoroalkyl group represented by the formula (1-1) produced in Example 1 and 5.78 g of pentafluoromethanesulfonylamide represented by the formula (24) were dissolved in 35 mL of acetonitrile, 1.23 g of magnesium oxide and 1.92 mL of water were added, and the mixture was aged at 25°C for 96 hours (imidation step). Water was added in amounts of 0.48 mL each at the start of aging, 24 hours after the start of aging, 48 hours after the start of aging, and 72 hours after the start of aging. The amount of water used in this reaction was 383 mol% based on the number of moles of the compound represented by the formula (1-1). Also, the amount of magnesium oxide (catalyst) used in the reaction was 110 mol% based on the number of moles of the compound represented by the formula (1-1).

[0228] Then, 7.8 g of potassium carbonate was added to the aged solution, and the mixture was further aged for 2 hours. The aged solution was filtered to separate the solid matter, and the solvent was distilled off from the filtrate. The obtained product was dissolved in 120 mL of water and washed with 60 mL of chloroform and 60 mL of diisopropyl ether. Then, extraction was performed using 60 mL of ethyl acetate and 20 mL of chloroform, and the solvent was distilled off to obtain 5.73 g of a product consisting of a white solid. The yield with respect to the raw material of the product (the bifunctional compound containing a branched perfluoroalkyl group represented by the formula (1-1)) was 43%.

[0229] For the product obtained in Example 20, １９ 19F-NMR measurement was performed in the same manner as in Example 1 to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group represented by the formula (1-19) was formed. １９ The results of the 19F-NMR measurement are shown below. １９ 19F-NMR (MeOH-d4): δ 54.1 (dq, F), -71.1 (dd, 3F), -80.3 (s, 3F), -118.0 (s, 2F), -147.1 (m, 1F)

[0230] [Example 21] A bifunctional compound containing a branched perfluoroalkyl group represented by the formula (1-20) was produced by the method shown below.

[0231]

[0232] In a Simmons electrolytic cell similar to the one used in Example 1, 89 g of 1,1-propanedisulfonyl difluoride represented by formula (5) and 410 g of hydrofluoric anhydride were charged, and the current density was 0.6 A / dm². ２ Electrolytic fluorination was started at a current of 4.05 A. During electrolytic fluorination, 64 g of 1,1-propanedisulfonyl difluoride was added every 24 hours. The temperature inside the electrolytic cell was kept within the range of 9°C to 11°C. During electrolytic fluorination, the crude product that separated in the electrolytic cell and formed the lower layer was sequentially withdrawn from the bottom valve installed in the electrolytic cell.

[0233] Electrofluorination was terminated after a total energizing time of 178.9 hours. The total amount of 1,1-propanedisulfonyl difluoride added during electrofluorination was 473 g, and the yield of crude product was 478 g. The total amount of current applied during electrofluorination was 864 Ahr, which was 118% of the theoretical current. The steady-state cell voltage during electrofluorination was 6.0 V to 6.9 V.

[0234] The crude composition obtained by electrolytic fluorination was subjected to GC-MS analysis using a gas chromatography-mass spectrometer, in the same manner as the crude composition obtained in Example 1. Furthermore, using a nuclear magnetic resonance spectrometer, the crude product was analyzed using trifluorotoluene as an internal standard, in the same manner as in Example 1. １９ F-NMR measurements were performed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (CDCl ３ ): δ 57.2 to 57.4 (m, 2F), -81.11 to -80.94 (m, 3F), -125.23 to -125.45 (m, 2F), -165.32 to -165.58 (m, 1F)

[0235] GC-MS analysis of crude product and １９Based on the results of F-NMR measurement, the crude product was identified. As a result, it was confirmed that 1,2,2,3,3,3-hexafluoropropane-1,1-disulfonyl difluoride, represented by formula (1-20), was formed. Furthermore, the purity of the bifunctional compound containing the branched perfluoroalkyl group represented by formula (1-20) in the crude product, as confirmed by gas chromatography analysis, was 85%.

[0236] Subsequently, the crude product was quenched with crushed ice and washed twice with deionized water. After washing, the crude product was dried with anhydrous sodium sulfate, filtered, and purified by distillation to obtain 338 g of product. The purity of the bifunctional compound containing the branched perfluoroalkyl group represented by formula (1-20) in the distilled product, as confirmed by gas chromatography analysis, was 97.2%. The yield of the distilled product relative to the starting material (compound represented by formula (5)) was 40%.

[0237] [Example 22] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-21) was prepared by the method described below.

[0238]

[0239] 2.5 g of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-20), prepared in Example 22, was dissolved in 5 mL of methanol, and 0.55 mL of water was added and the mixture was aged at 25°C for 24 hours. Next, 25 mL of acetonitrile and 1.66 g of potassium bicarbonate were added to the aged solution and the mixture was reacted at 25°C for at least 4 hours, adjusting the pH of the solution to 7-8. The amount of water used in this reaction was 386 mol% relative to the number of moles of the compound shown in formula (1-20). The amount of potassium bicarbonate (alkali metal compound) used in the reaction was 210 mol% relative to the number of moles of the compound shown in formula (1-20).

[0240] The reaction solution was filtered to separate the solid, and the solvent was removed from the filtrate to obtain 2.11 g of a white solid product. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-20)) was 76%. The product obtained in Example 22 was subjected to the same procedure as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, represented by formula (1-21), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 50.2 to 50.4 (m, 2F), -83.21 to -83.74 (m, 3F), -126.53 to -126.65 (m, 2F), -167.43 to -167.68 (m, 1F)

[0241] [Example 23] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-21) was prepared by the method shown below.

[0242]

[0243] 1.0 g of the difunctional compound containing the branched perfluoroalkyl group shown in formula (1-1) prepared in Example 1 was dissolved in 5 mL of acetonitrile, and 0.25 mL of water was added and the mixture was aged at 25°C for 2 weeks (hydrolysis step). The amount of water used in this reaction was 373 mol% relative to the number of moles of the compound shown in formula (1-1).

[0244] Next, 0.75 g of potassium bicarbonate was added to the matured solution and reacted at 25°C for at least 2 hours, adjusting the pH of the solution to 7-8. The amount of potassium bicarbonate (alkali metal compound) used in the reaction was 201 mol% relative to the number of moles of the compound shown in formula (1-1).

[0245] The reaction solution was filtered to separate the solid, and the solvent was removed from the filtrate to obtain 0.54 g of a white solid product. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group represented by formula (1-1)) was 48%.

[0246] The product obtained in Example 23 was processed in the same manner as in Example 1. １９ F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-2), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 51.3 (dq, 1F), -72.3 (dd, 3F), -150.48 to -150.55 (m, 1F)

[0247] [Example 24] A difunctional compound containing a branched perfluoroalkyl group represented by formula (1-4) was prepared by the method described below.

[0248]

[0249] 1.4 g of the bifunctional compound containing the branched perfluoroalkyl group shown in formula (1-1) prepared in Example 1 and 1.2 g of potassium trifluoromethanesulfonylamide shown in formula (14) were dissolved in 5 mL of acetonitrile, and 0.24 g of magnesium oxide and 0.36 mL of water were added and the mixture was aged at 25°C for 96 hours (imidization step). 0.09 mL of water was added at the start of aging, 24 hours after the start of aging, 48 hours after the start of aging, and 72 hours after the start of aging. The amount of water used in this reaction was 380 mol% relative to the number of moles of the compound shown in formula (1-1). The amount of magnesium oxide (catalyst) used in the reaction was 113 mol% relative to the number of moles of the compound shown in formula (1-1).

[0250] The aged solution was filtered to separate the solid, and the solvent was removed from the filtrate. The obtained product was dissolved in 14 mL of water, washed with 10 mL of chloroform and 10 mL of diisopropyl ether, extracted with 10 mL of ethyl acetate and 3.5 mL of chloroform, and the solvent was removed by distillation to obtain 0.87 g of a white solid product. The yield of the product relative to the starting material (a bifunctional compound containing a branched perfluoroalkyl group shown in formula (1-1)) was 38%.

[0251] The product obtained in Example 24 was processed in the same manner as in Example 1. １９F-NMR measurements were performed to identify the product. As a result, it was confirmed that a bifunctional compound containing a branched perfluoroalkyl group, as shown in formula (1-4), was formed. １９ The results of the F-NMR measurement are shown below. １９ F-NMR (MeOH-d4): δ 54.0 (dq, 1F), -71.2 (dd, 3F), -80.4 (s, 3F), -147.21 to -147.25 (m, 1F)

[0252] The bifunctional compound comprising a branched perfluoroalkyl group of the present invention is a novel compound represented by formula (1), wherein the perfluoroalkyl group (-C) ｎ F ２ｎ＋１ (n=1-3)) and a fluorine atom (-F) or a trifluoromethyl group (-CF ３ The present invention provides a structure in which a carbon atom is bonded to two specific functional groups that are not perfluoroalkyl groups, and one or both of the two functional groups are groups having a sulfonyl group. The bifunctional compounds containing branched perfluoroalkyl groups of the present invention may be used as semiconductor materials, battery electrolyte materials such as batteries and capacitors, ion conductive materials, polymer modifiers, battery separator materials, photoacid generators for resin polymerization, and intermediates thereof to improve various properties depending on the application.

Claims

A difunctional compound comprising a branched perfluoroalkyl group, represented by the following general formula (1). (Rf in general formula (1) ２ｎ＋１ , ｎ is -F or -CF ３ . Rf ２ is -C ｎ F ２ｎ＋１ (n = 1 to 3). X is -F, -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ and is any group selected from the group consisting of. Y is -SO ２ F, -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M​​​​​​​​​​​​ Rf in general formula (1) １ However, it is -F and Rf ２ However, -CF ３ A difunctional compound comprising a branched perfluoroalkyl group as described in claim 1. A difunctional compound comprising a branched perfluoroalkyl group according to claim 1, wherein X in general formula (1) is -F. In general formula (1), Y is -SO ２ A bifunctional compound comprising the branched perfluoroalkyl group described in claim 3, wherein F. In general formula (1), X is -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ A difunctional compound comprising a branched perfluoroalkyl group according to claim 1, wherein M is an alkali metal ion, and the group is selected from the group consisting of the following. In general formula (1), X is -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ Y is one of the groups selected from the group consisting of -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ A difunctional compound comprising a branched perfluoroalkyl group according to claim 1, wherein M is an ammonium ion, and the group is selected from the group consisting of the following. 　 A difunctional compound comprising a branched perfluoroalkyl group according to claim 1, wherein the general formula (1) is an iodide. 　 The method for producing a difunctional compound containing a branched perfluoroalkyl group, as shown in the general formula (1) below, A method for producing a bifunctional compound containing a branched perfluoroalkyl group, comprising a fluorination step of electrolytically fluorinating a bifunctional compound containing an alkyl group having a sulfonyl group represented by the following general formula (2) to obtain a bifunctional compound containing a branched perfluoroalkyl group represented by the following general formula (3). (In general formula (1), Rf １ is -F or -CF ３ . Rf ２ is -C ｎ F ２ｎ＋１ (n = 1 to 3). X is -F, -O － M ＋ , -N － HM ＋ , -N － M ＋ SO ２ Rf ３ selected from the group consisting of. Y is -SO ２ F, -SO ３ － M ＋ , -SO ２ N － HM ＋ , -SO ２ N － M ＋ SO ２ Rf ３ , -I selected from the group consisting of. Rf in X and Y ３ are each -C ｎ F ２ｎ＋１ (n = 1 to 4), and M is each selected from the group consisting of hydrogen, an alkali metal ion, an alkaline earth metal ion, and an onium ion. ) (R in general formula (2)) １ is hydrogen or -CH ３ That is. R ２ is, -C ｎ H ２ｎ＋１ (n = 1 to 3.) (Rf in general formula (3)) １ is -F or -CF ３ Rf ２ is, -C ｎ F ２ｎ＋１ (n = 1 to 3.) 　 A difunctional compound containing a branched perfluoroalkyl group represented by the general formula (3) is reacted with an alcohol and water to form two -SO compounds in the general formula (3). ２ One of F is -SO ３ A method for producing a bifunctional compound containing a branched perfluoroalkyl group according to claim 8, comprising a hydrolysis step of H. 　 A bifunctional compound containing a branched perfluoroalkyl group represented by the general formula (3) is dissolved in a solvent and reacted with water to form two -SO compounds in the general formula (3). ２ One of F is -SO ３ A method for producing a bifunctional compound containing a branched perfluoroalkyl group according to claim 8, comprising a hydrolysis step of H. 　 A difunctional compound containing a branched perfluoroalkyl group represented by the general formula (3) above, and NHMSO ２ Rf ３ (Rf ３ is, -C ｎ F ２ｎ＋１ A method for producing a bifunctional compound containing a branched perfluoroalkyl group according to claim 8, comprising an imidation step of reacting a solvent and water with (n = 1 to 4), where M is any group selected from the group consisting of hydrogen, alkali metal ions, alkaline earth metal ions, and onium ions, in the presence of magnesium oxide. 　 A difunctional compound containing a branched perfluoroalkyl group represented by the general formula (3) is reacted with iodine, acidic potassium fluoride, and a solvent in the presence of silver nitrate and / or silver sulfate to form two -SO compounds in the general formula (3). ２ A method for producing a bifunctional compound containing a branched perfluoroalkyl group according to claim 8, comprising an iodization step in which one of F is replaced with -I.

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