Method for producing halogenated alkanesulfonyl compounds, and method for producing compounds containing multiple bonds

Abstract

Provided is a method for producing a halogenated alkanesulfonyl compound that can achieve both excellent handling properties of raw materials and a high yield of the reaction product. Also provided is a method for producing a multiple bond-containing compound using the halogenated alkanesulfonyl compound. 【Solution means】The following formula (1); X-SO2-CF n1 Cl 3-n1 (1) (In the formula, n1 represents a number of 1 or 2. X represents a chlorine atom, a fluorine atom or an O-SO2-CF n2 Cl 3-n2 group. n2 represents a number of 1 or 2.) A compound (A) represented by the following formula (2); R 1 -OH(2) (In the formula, R 1 represents an organic group having a multiple bond.) And a compound (B) represented by the following formula (2) are reacted in the presence of a base and a solvent, and the method for producing a halogenated alkanesulfonyl compound includes this step.

Description

[Technical Field]

[0001] This disclosure relates to a method for producing alkanesulfonyl halogenated compounds and a method for producing compounds containing multiple bonds. [Background technology]

[0002] The trifluoromethanesulfonyl group (CF3SO2 group, Tf group) is a common leaving group in cross-coupling reactions. A well-known and representative method for synthesizing substrates for cross-coupling reactions involves reacting compounds containing a Tf group with phenols. For example, Non-Patent Document 1 discloses a reaction to convert phenols to Tf using trifluoromethanesulfonic acid chloride, etc. Since the Tf group can react with various functional groups, a desired structure can be introduced into a Tf-modified compound by performing a cross-coupling reaction between a Tf-modified compound, such as phenols, and a compound having a functional group that is reactive with the Tf group and a desired structure. Regarding such cross-coupling reactions, for example, Non-Patent Document 2 discloses the Suzuki-Miyaura coupling reaction, and Non-Patent Document 3 discloses the Heck reaction, among others. [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] Advanced Synthesis&Catalysis,2017,359(3),419-425 [Non-Patent Document 2] J.Angew.Chem.Int.Ed.2001,40,4544-4568 [Non-Patent Document 3] Chem.Rev.2000,100(8),3009-3066 [Non-Patent Document 4] Synthesis,1979,1979(12),972-975 [Overview of the project] [Problems that the invention aims to solve]

[0004] Tf-forming agents such as trifluoromethanesulfonyl fluoride exhibit excellent reactivity with phenols, but their low boiling points necessitate special equipment modifications during handling. To address these challenges, the CCl3SO2 nitrate, in which three F atoms in the Tf nitrate are replaced with Cl atoms, has a significantly higher boiling point compared to the Tf nitrate, resulting in better handling at room temperature. However, the CCl3SO2 nitrate has poor reactivity with phenols, which poses a problem in terms of yield.

[0005] Non-patent document 4 discloses a reaction between CF2ClSO2-X, which has a CF2ClSO2 group in which three F atoms of the Tf group are replaced with Cl atoms, and phenols. Although CF2ClSO2-X also has a high boiling point and is easy to handle, the yield of the reaction product obtained in the above reaction was not sufficient.

[0006] As mentioned above, various coupling reactions have been disclosed in the past, and Tf-forming agents and CCl3SO2-forming agents have been disclosed as raw materials. However, conventional methods for producing halogenated alkanesulfonyl compounds using these agents have not been sufficient in terms of balancing ease of handling of raw materials with the yield of reaction products.

[0007] This disclosure has been made in view of these circumstances. The object of this disclosure is to provide a method for producing a halogenated alkanesulfonyl compound that can achieve both excellent handling of raw materials and a high yield of reaction products. The object of this disclosure is to provide a method for producing a multibond-containing compound using the above halogenated alkanesulfonyl compound. [Means for solving the problem]

[0008] Therefore, the inventors conducted thorough research in consideration of the above problems. As a result, they found that compounds having fluorine and chlorine atoms as halogens in trihaloalkanesulfonyl compounds have a high boiling point and excellent handling properties. They also found that by reacting these compounds with compounds having an organic group with multiple bonds and a hydroxyl group in the presence of a base and a solvent, multiple-bonded halogenated alkanesulfonyl compounds can be obtained in high yield. Furthermore, the inventors found that by reacting the above-mentioned halogenated alkanesulfonyl compounds with predetermined compounds that can react with them, multiple-bonded compounds in which these compounds are cross-coupled can be obtained.

[0009] In other words, this disclosure provides the inventions described in [1]-[8] below.

[0010] [1] The following equation (1); X-SO2-CF n1 Cl 3-n1 (1) (In the formula, n1 represents the number 1 or 2. X is a chlorine atom, a fluorine atom, or O-SO2-CF) n2 Cl 3-n2 The compound (A) is represented by the following formula (2); n2 represents the number 1 or 2. R 1 -OH (2) (In the formula, R 1 A method for producing an alkanesulfonyl halide compound, comprising the step of reacting a compound (B) represented by ) in the presence of a base and a solvent.

[0011] [2] The aforementioned R 1 The method for producing a halogenated alkanesulfonyl compound according to [1], wherein is an aromatic hydrocarbon group or an unsaturated hydrocarbon group which may have a heteroatom.

[0012] [3] The aforementioned R 1The aromatic hydrocarbon group or unsaturated hydrocarbon group in [2] may have a substituent, and the substituent is at least one selected from the group consisting of a hydroxyl group, a nitro group, an alkoxy group, a halogeno group, an amino group, and an alkyl ester group. A method for producing a halogenated alkanesulfonyl compound as described in [2].

[0013] [4] The base is an inorganic base. A method for producing a halogenated alkanesulfonyl compound as described in any one of [1] to [3].

[0014] [5] The solvent is an aprotic polar solvent. A method for producing a halogenated alkanesulfonyl compound as described in any one of [1] to [4].

[0015] [6] The following formula (3); R 1 -OSO2-CF n1 Cl 3-n1 (3) (In the formula, n1 represents a number of 1 or 2. R 1 represents an organic group having a multiple bond.) A method for producing a multiple bond-containing compound, which includes reacting a halogenated alkanesulfonyl compound represented by the formula (3) with a compound (C) having a functional group capable of reacting with the -OSO2-CF n1 Cl 3-n1 group in the formula (3).

[0016] [7] In the compound (C), the functional group capable of reacting with the -OSO2-CF n1 Cl 3-n1 group in the formula (3) is at least one selected from the group consisting of an unsaturated hydrocarbon group, an amino group, a boronic acid group, a boronic acid ester group, a diboronic acid ester group, and a -MX' group (M represents Mg or Zn. X' represents a halogen atom). A method for producing a multiple bond-containing compound as described in [6].

[0017] [8] The method for producing a multiple bond-containing compound according to [6] or [7], wherein the compound (C) has an aromatic hydrocarbon group. [Effects of the Invention]

[0018] According to this disclosure, it is possible to provide a method for producing halogenated alkanesulfonyl compounds in high yield using raw materials that are easy to handle. Furthermore, it is possible to provide a method for producing multiple bond-containing compounds using the above-mentioned halogenated alkanesulfonyl compounds. [Modes for carrying out the invention]

[0019] The present disclosure will be described in detail below. While embodiments of the present disclosure will be described below, the present disclosure is not limited to the embodiments described below and may be implemented as appropriate by those skilled in the art, without prejudice to the spirit of the present disclosure.

[0020] <Method for producing halogenated alkanesulfonyl compounds> A method for producing a halogenated alkanesulfonyl compound in this disclosure is given by the following formula (1); X-SO2-CF n1 Cl 3-n1 (1) (In the formula, n1 represents the number 1 or 2. X is a chlorine atom, a fluorine atom, or O-SO2-CF) n2 Cl 3-n2 The compound (A) is represented by the following formula (2); n2 represents the number 1 or 2. R 1 -OH (2) (In the formula, R 1 The compound (B), represented by , represents an organic group having multiple bonds, and the reaction includes a step of reacting it with a base and a solvent (hereinafter also referred to as reaction step (α)). The above compound (A) is CF n1 Cl 3-n1 The presence of a chlorine atom in the SO2 group results in a high boiling point and excellent handling properties. Furthermore, CF n1 Cl 3-n1Because the SO2 group contains a fluorine atom, it exhibits excellent reactivity with compound (B) in the presence of a base and a solvent, allowing for the production of the reaction product, an alkanesulfonyl halogenated compound, in high yield.

[0021] (Compound (A)) The above compound (A) is not particularly limited as long as it is a compound represented by the above formula (1). In equation (1), n1 is a number that is either 1 or 2, preferably 2.

[0022] In formula (1) above, X is a chlorine atom, a fluorine atom, or O-SO2-CF n2 Cl 3-n2 It is the base. The above n2 is a number of 1 or 2, preferably 2. The above X is preferably a fluorine atom.

[0023] Specifically, the above compound (A) includes chlorodifluoromethanesulfonyl fluoride, chlorodifluoromethanesulfonyl chloride, dichlorofluoromethanesulfonyl fluoride, dichlorofluoromethanesulfonyl chloride, chlorodifluoromethanesulfonic anhydride, dichlorofluoromethanesulfonic anhydride, and CF2Cl-SO2-OSO2CFCl2. Among these, chlorodifluoromethanesulfonyl fluoride and chlorodifluoromethanesulfonyl chloride are preferred, and chlorodifluoromethanesulfonyl fluoride is more preferred.

[0024] (Compound (B)) The above compound (B) is not particularly limited as long as it is a compound represented by the above formula (2). R in equation (2) 1 It is an organic group that has multiple bonds. The above organic group is not particularly limited as long as it has double and / or triple bonds as multiple bonds, and the number of multiple bonds is also not particularly limited. Examples of the above-mentioned organic groups include aromatic hydrocarbon groups and unsaturated hydrocarbon groups, which may contain heteroatoms. The above heteroatoms are not particularly limited, but examples include oxygen atoms, sulfur atoms, nitrogen atoms, phosphorus atoms, boron atoms, halogen atoms, etc. Preferably, the above heteroatoms are oxygen atoms, nitrogen atoms, and halogen atoms. R 1 A form in which is an aromatic hydrocarbon group or an unsaturated hydrocarbon group that may have a heteroatom is one of the preferred embodiments in this disclosure.

[0025] The above-mentioned aromatic hydrocarbon group is not particularly limited as long as it has a structure derived from an aromatic cyclic compound, and may be a group derived from an aromatic heterocyclic compound having a heteroatom, and may also have hydrocarbon groups such as aliphatic hydrocarbon groups in addition to the aromatic cyclic structure. In this specification, the hydrocarbon group that may be present in the aromatic ring structure of the above aromatic hydrocarbon group is not treated as a substituent of the above aromatic hydrocarbon group, but is considered to be part of the above aromatic hydrocarbon group. On the other hand, groups other than the hydrocarbon group present in the above aromatic hydrocarbon group are treated as substituents. The above aromatic hydrocarbon group may have substituents. The above aliphatic hydrocarbon group is the same as the aliphatic hydrocarbon group in formula (4) described later, including preferred embodiments.

[0026] The number of aromatic ring structures in the above aromatic hydrocarbon group is not particularly limited and may be monocyclic or polycyclic. The number of aromatic ring structures is usually 1 to 5, preferably 1 to 3. The number of substituents on the above aromatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0027] The substituents other than hydrocarbon groups that the above aromatic hydrocarbon group may have are not particularly limited, but examples include hydroxyl groups, nitro groups, alkoxy groups, halogen groups, amino groups, alkyl ester groups, and the like. A form in which the above aromatic hydrocarbon group has at least one substituent selected from the group consisting of a hydroxyl group, a nitro group, an alkoxy group, a halogeno group, an amino group, and an alkyl ester group is one of the preferred embodiments in this disclosure. If the aromatic hydrocarbon group has substituents, their number and position are not particularly limited, and they may be bonded to carbon atoms that form a ring structure in the aromatic hydrocarbon group, or to carbon atoms other than those in the ring structure.

[0028] The above alkoxy group is not particularly limited, but examples include a methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, etc.

[0029] The above halogen group is not particularly limited, but examples include a fluorine atom, a chlorine atom, and a bromine atom.

[0030] The above-mentioned amino group is not particularly limited and includes primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium groups, etc.

[0031] The alkyl ester group (-COOR: R=alkyl group) is not particularly limited, but examples include methyl ester group, ethyl ester group, n-propyl ester group, i-propyl ester group, n-butyl ester group, i-butyl ester group, s-butyl ester group, t-butyl ester group, etc.

[0032] Preferably, the substituents are nitro groups, alkoxy groups, halogeno groups, amino groups, and alkyl ester groups, and more preferably nitro groups and halogeno groups.

[0033] The number of carbon atoms in the above aromatic hydrocarbon group is not particularly limited, but 3 to 30 is preferred. More preferably 4 to 25, even more preferably 5 to 20, even more preferably 6 to 16, and even more preferably 6 to 12. If the above aromatic hydrocarbon group has substituents, the above carbon number shall include the carbon number of the substituents.

[0034] Specific examples of the above-mentioned aromatic hydrocarbon groups include aryl groups, aralkyl groups, and groups derived from aromatic heterocyclic compounds. Examples of the aryl groups mentioned above include phenyl, 2-,3- or 4-tolyl, 2,3- or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthryl, and biphenylyl groups. Examples of the above-mentioned aralkyl groups include benzyl groups, phenethyl groups, phenylpropyl groups, and benzhydryl groups. Examples of the above aromatic heterocyclic compounds include pentasol, triazole, imidazole, benzimidazole, oxazole, isoxazole, thiazole, isothiazole, pyrazole, pyrrole, indole, carbazole, furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyridine, pyrazine, piperidine, morpholine, and thiazine.

[0035] The form in which the above aromatic hydrocarbon group is derived from an aromatic heterocyclic compound is also one of the preferred embodiments in this disclosure. 1 However, if the group is derived from an aromatic heterocyclic compound, specific examples of the above compound (A) include 3-hydroxypyridine and the like. A form in which the above aromatic hydrocarbon group is polycyclic is also one of the preferred embodiments in this disclosure. 1 However, if the group is derived from a polycyclic aromatic hydrocarbon, specific examples of the above compound (A) include 1-naphthol, 2-naphthol, and the like.

[0036] The above aromatic hydrocarbon group is preferably of the following formula (4);

[0037] [ka] (In the formula, R 2 , R3 , R 4 , R 5 , R 6 It is preferable that the group is represented by ), which is the same or different hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or a substituent other than an aliphatic hydrocarbon group.

[0038] R in equation (4) above 2 , R 3 , R 4 , R 5 , R 6 These are the same or different substituents, which are a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or a group other than an aliphatic hydrocarbon group. Specific examples and preferred forms of the above substituents are as described above.

[0039] The above aliphatic hydrocarbon group is not particularly limited, but examples include alkyl groups, alkenyl groups, and alkynyl groups. The number of carbon atoms in the above aliphatic hydrocarbon group is not particularly limited, but 1 to 12 is preferred. More preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 4.

[0040] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, dodecyl group, etc.

[0041] Examples of the above alkenyl groups include vinyl group, propenyl group, 2-propenyl group, 1-methylpropenyl group, 1-methyl-2-propenyl group, 1-ethylpropenyl group, 1-ethyl-2-propenyl group, 1-propylpropenyl group, 1-propyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, butenyl group, 2-butenyl group, 1-methyl-2-butenyl group, 1-methylbutenyl group, and 2-methyl-2-butenyl group. Nyl group, 2-methylbutenyl group, 3-methyl-2-butenyl group, 3-methylbutenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethylbutenyl group, 1,1-dimethyl-2-butenyl group, 1-ethyl-2-methyl-2-butenyl group, 1-ethyl-2-methylbutenyl group, pentenyl group, 2-pentenyl group, 1-methyl-2-pentenyl group, 1-methylpentenyl group, 2-methyl-2-pentenyl group, 2-methyl Pentenyl group, 3-methyl-2-pentenyl group, 3-methylpentenyl group, 4-methyl-2-pentenyl group, 4-methylpentenyl group, 2,4-dimethyl-2-pentenyl group, 2,4-dimethylpentenyl group, 1,4-dimethyl-2-pentenyl group, 1,4-dimethylpentenyl group, 1-ethyl-2-methyl-2-pentenyl group, 1-ethyl-2-methylpentenyl group, 2-hexenyl group, hexenyl group, 1-methyl- Examples include 2-hexenyl group, 1-methylhexenyl group, 3-methyl-2-hexenyl group, 3-methylhexenyl group, 2-heptenyl group, heptenyl group, 2-methyl-2-heptenyl group, 2-methylheptenyl group, 3,4,4-trimethyl-2-heptenyl group, 3,4,4-trimethylheptenyl group, 2-octenyl group, octenyl group, 2-nonenyl group, nonenyl group, 2-decenyl group, dekenyl group, dodecenyl group, etc.

[0042] Examples of the alkynyl groups mentioned above include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, desinyl group, and dodecynyl group.

[0043] In equation (4) above, R 3 , R 4 , R 5Preferably, at least one of the substituents is an aliphatic hydrocarbon group which may have substituents, or a group other than an aliphatic hydrocarbon group. More preferably R 4 This is a form in which the substituent is an aliphatic hydrocarbon group which may have substituents, or a group other than an aliphatic hydrocarbon group.

[0044] In equation (4) above, R 2 , R 3 , R 5 , R 6 is a hydrogen atom, R 4 However, it is in a form in which at least one selected from the group consisting of a methyl group, a nitro group, a methoxy group, a halogeno group, an amino group, and a methyl ester group (-COOCH3), or R 2 , R 4 , R 5 , R 6 is a hydrogen atom, R 3 A form in which is selected from the group consisting of a methyl group, a nitro group, a methoxy group, a halogeno group, an amino group, and a methyl ester group (-COOCH3) is one of the preferred embodiments in this disclosure.

[0045] R in equation (2) above 1 However, if the group is represented by formula (4) above, specific examples of compound (A) include phenol, 2-,3- or 4-nitrophenol, 2-,3- or 4-cresol, 2-,3- or 4-methoxyphenol, 2-,3- or 4-chlorophenol, 2-,3- or 4-fluorophenol, 2-,3- or 4-bromophenol, 2-,3- or 4-iodophenol, 2-,3- or 4-aminophenol, methyl 2-,3- or 4-hydroxybenzoate, hydroquinone, and the like.

[0046] R in equation (2) above 1 The unsaturated hydrocarbon group in this expression is not particularly limited as long as it is a hydrocarbon group having an unsaturated bond, and may have substituents. Specific examples and preferred forms of the substituents are as described above. The substituent on the above-mentioned unsaturated hydrocarbon group is more preferably an alkyl ester group, and even more preferably a methyl ester group or an ethyl ester group. The number of carbon atoms in the above-mentioned unsaturated hydrocarbon group is not particularly limited, but 2 to 20 is preferred.

[0047] Examples of the above-mentioned unsaturated hydrocarbon groups include alkenyl groups and alkynyl groups. Specific examples of the above-mentioned alkenyl group and alkynyl group include the aforementioned alkenyl group and alkynyl group. The above unsaturated hydrocarbon group is preferably an alkenyl group, and more preferably 1-methylpropenyl group, 1-methyl-2-propenyl group, 1-ethylpropenyl group, 1-ethyl-2-propenyl group, 1-propylpropenyl group, 1-propyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 1-methyl-2-butenyl group, 1-methylbutenyl group, 2-methyl-2-butenyl group, 2-methylbutenyl group, 3-methyl-2-butenyl group, 3-methylbutenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethylbutenyl group, 1,1-dimethyl-2-butenyl group, 1- These are branched alkenyl groups such as ethyl-2-methyl-2-butenyl group, 1-ethyl-2-methylbutenyl group, 1-methyl-2-pentenyl group, 1-methylpentenyl group, 2-methyl-2-pentenyl group, 2-methylpentenyl group, 3-methyl-2-pentenyl group, 3-methylpentenyl group, 4-methyl-2-pentenyl group, 4-methylpentenyl group, 2,4-dimethyl-2-pentenyl group, 2,4-dimethylpentenyl group, 1,4-dimethyl-2-pentenyl group, 1,4-dimethylpentenyl group, 1-ethyl-2-methyl-2-pentenyl group, and 1-ethyl-2-methylpentenyl group.

[0048] R in equation (2) above 1However, if it is an alkenyl group which may have substituents, compound (A) specifically includes, for example, 1-methylpropen-1-ol, 1-methylpropen-2-ol, 1-methyl-2-propen-1-ol, 1-ethylpropen-1-ol, 1-ethylpropen-2-ol, 1-ethyl-2-propen-1-ol, 1-propylpropen-1-ol, 1-propylpropen-2-ol, 1-propyl-2-propen-1-ol, 1,1-dimethyl-2-propen-1-ol, 1-methyl-2-buten-1-ol, 1-methyl-2-buten-2-ol, 1-methyl-1-buten-1-ol, 1-methyl-1-buten-2-ol, 2-methyl-2-buten-1-ol Examples of compounds that can be used include 2-methyl-2-buten-3-ol, 2-methyl-1-buten-1-ol, 2-methyl-1-buten-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-2-buten-2-ol, 3-methyl-1-buten-1-ol, 3-methyl-1-buten-2-ol, 2,3-dimethyl-2-buten-1-ol, 2,3-dimethyl-1-buten-1-ol, 2,3-dimethyl-1-buten-2-ol, 1,1-dimethyl-2-buten-1-ol, 1-ethyl-2-methyl-2-buten-1-ol, 1-ethyl-2-methyl-1-buten-1-ol, 1-ethyl-2-methyl-1-buten-2-ol, and compounds having the above substituents.

[0049] In the above reaction step (α), it is preferable that 0.7 to 2.0 moles of compound (A) are used per 1.0 mole of compound (B). More preferably, it is 0.8 to 1.6 moles, and even more preferably 0.9 to 1.2 moles.

[0050] (base) The base used in the above reaction step (α) is not particularly limited as long as it is a basic compound, and may be an inorganic base or an organic base. An inorganic base is preferred as the base. Examples of the above organic bases include diazabicycloundecene derivatives such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU); diazabicyclononene derivatives such as 1,5-diazabicyclo[4.3.0]-5-nonene (DBN); and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, 4-dimethylaminopyridine, N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylhexanediamine, bis(dimethylaminoethyl) ether, N,N',N'-trimethylaminoethylpiperazine, and N,N,N',N'',N''-pentamethyldiethylenetriamine.

[0051] Examples of the inorganic bases mentioned above include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; alkali metal carboxylates such as sodium formate, potassium formate, sodium acetate, and potassium acetate; alkaline earth metal carboxylates such as calcium formate; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; alkaline earth metal carbonates such as calcium carbonate; alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; alkaline earth metal bicarbonates such as calcium bicarbonate and barium bicarbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; alkaline earth metal phosphates such as calcium phosphate and barium phosphate; and alkali metal alkoxides such as lithium methoxide, sodium methoxide, potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, lithium isopropoxide, sodium isopropoxide, potassium isopropoxide, lithium tert-butoxide, sodium tert-butoxide, and potassium tert-butoxide. Among these, alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate are preferred, and potassium carbonate is more preferred.

[0052] The amount of the above base used is not particularly limited, but 0.7 to 2.2 moles and more preferably 0.9 to 1.4 moles per mole of compound (B) is preferred.

[0053] (solvent) The above solvents are not particularly limited, but examples include nitrile solvents, ether solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ester solvents, amide solvents, sulfoxide solvents, ketone solvents, etc.

[0054] Examples of the nitrile-based solvents mentioned above include acetonitrile, propionitrile, and benzonitrile. Examples of ether-based solvents include diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,4-dioxane, and cyclopentyl methyl ether. Examples of aliphatic hydrocarbon solvents include n-hexane, n-heptane, n-pentane, n-nonane, and n-decane. Examples of aromatic hydrocarbon solvents include toluene, xylene, mesitylene, and ethylbenzene. Examples of halogenated hydrocarbon solvents include methylene chloride (dichloromethane), chloroform, and 1,2-dichloroethane. Examples of ester solvents include ethyl acetate, isopropyl acetate, n-butyl acetate, and γ-butyrolactone. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone. Examples of sulfoxide-based solvents include dimethyl sulfoxide. Examples of ketone solvents include acetone.

[0055] Among the above reaction solvents, aprotic polar solvents such as nitrile solvents, ether solvents, halogenated hydrocarbon solvents, ester solvents, amide solvents, sulfoxide solvents, and ketone solvents are preferred. Nitrile solvents are more preferred, and acetonitrile is even more preferred.

[0056] There are no particular restrictions on the amount of solvent used, but it is sufficient to use 0.05 L (liters) or more per mole of compound (B), usually 0.01 to 20 L, and more preferably 0.1 to 10 L.

[0057] (Reaction temperature) The reaction temperature in the above reaction step (α) is not particularly limited, but it is preferably carried out at a reaction temperature of 150°C or lower, more preferably in the range of -100 to 100°C, even more preferably in the range of -78 to 80°C, and particularly preferably in the range of -78 to 50°C.

[0058] (Reaction time) The reaction time in the above reaction step (α) is not particularly limited and can be adjusted according to the raw materials and reaction conditions, but for example, it can be carried out in the range of 0.1 to 72 hours. It is preferable to track the progress of the reaction using analytical means such as NMR and terminate the reaction when the raw materials have almost completely disappeared.

[0059] (Reaction atmosphere) The reaction atmosphere in the above reaction step (α) is not particularly limited and may be an atmospheric atmosphere or an inert gas atmosphere such as nitrogen, helium, neon, or argon.

[0060] (Post-processing operations) After the above reaction, the resulting halogenated alkanesulfonyl compound can be isolated using work-up procedures that are common in organic synthesis. Examples of work-up procedures include filtration, washing with a solvent, and concentration.

[0061] <Method for producing compounds containing multiple bonds> A method for producing a multibond-containing compound in this disclosure is given by the following formula (3); R 1 -OSO2-CF n1 Cl 3-n1 (3) (In the formula, n1 represents a number of 1 or 2. 1 represents an organic group having multiple bonds. ) Halide alkanesulfonyl compounds represented by formula (3) (hereinafter also referred to as compounds represented by formula (3)) and -OSO2-CF in formula (3) 1n Cl 3-n1 The process includes a step of reacting a compound (C) having a functional group that can react with the group (hereinafter also referred to as reaction step (β)). -OSO2-CF in the compound represented by formula (3) above n1 Cl 3-n1 The group can react with various functional groups, therefore, -OSO2-CF n1 Cl 3-n1 By reacting compound (C), which has a functional group that can react with the group (hereinafter also called a reactive functional group), the structure of compound (C) other than the reactive functional group can be introduced into the compound represented by formula (3).

[0062] In the reaction between the compound represented by formula (3) and the compound (C) in reaction step (β) described above, -OSO2-CF in formula (3) n1 Cl 3-n1 The group reacts with the reactive functional group in compound (C), resulting in -OSO2-CF of formula (3). n1 Cl 3-n1 The group is eliminated. When a halogenated alkanesulfonyl compound has a -CF3 group, the compound with the -CF3 group after elimination is difficult to decompose and has a large impact on the environment and living organisms. In contrast, the compound represented by formula (3) above has a -CF n1 Cl 3-n1 Because the group contains a chlorine atom, the resulting -CF group is formed by elimination. n1 Cl 3-n1 Compounds containing this group exhibit excellent degradability. Therefore, the method for producing the multiple bond-containing compound described herein is of high technical significance, particularly in that it has a low impact on the environment and living organisms.

[0063] (Alkanesulfonyl halogenated compounds) The above-mentioned halogenated alkanesulfonyl compound is a compound represented by formula (3), where n1 in formula (3) is 1 or 2, preferably 2. R in equation (3) above 1 Specific examples and preferred forms are as described above for formula (2). The method for producing the compound represented by formula (3) above is not particularly limited, but it is preferably produced by the method for producing the halogenated alkanesulfonyl compound of this disclosure.

[0064] (Compound (C)) The above compound (C) is -OSO2-CF in formula (3). n1 Cl 3-n1 There are no particular restrictions as long as it has a functional group that can react with the group. The above-OSO2-CF n1 Cl 3-n1 The functional group that can react with the group is -OSO2-CF n1 Cl 3-n1 It reacts with the group to form a CC bond, and R in formula (3) above 1 This functional group can cross-couple with the group and structures other than the reactive functional group in compound (C) mentioned above.

[0065] The above-OSO2-CF n1 Cl 3-n1 Examples of functional groups that can react with the group include unsaturated hydrocarbon groups, amino groups, boronic acid groups, boronic acid ester groups, diboronic acid ester groups, and -MX' groups (where M represents Mg or Zn, and X' represents a halogen atom). One preferred embodiment in this disclosure is in which the above compound (C) has at least one selected from the group consisting of unsaturated hydrocarbon groups, amino groups, boronic acid groups, boronic acid ester groups, diboronic acid ester groups, and -MX' groups.

[0066] The above-mentioned unsaturated hydrocarbon group is not particularly limited as long as it is a hydrocarbon group having an unsaturated bond, and examples include alkenyl groups and alkynyl groups. Specific examples of the above alkenyl and alkynyl groups are R 1As described above. The unsaturated hydrocarbon group is preferably a terminal alkenyl group or a terminal alkynyl group having a double bond or a triple bond at the terminal.

[0067] The amino group is not particularly limited, and examples thereof include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium group, and the like.

[0068] The boronic acid group is a group represented by -B(OH)2.

[0069] The boronic acid ester group is represented by the following formula (5): -B(OR 7 )2(5) (In the formula, R 7 represents a hydrocarbon group, which may be the same or different. Two R 7 may combine to form a ring structure). It is preferably a group represented by the above formula. The boronic acid ester group can be esterified, for example, by reacting the boronic acid group with an alcohol. By reacting the boronic acid group with a diol, in the above formula (5), two R 7 combine to form a ring structure. Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups; aromatic hydrocarbon groups such as aryl groups and aralkyl groups. Specific examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and aralkyl group are as described in compound (B). The boronic acid ester group is preferably a group obtained by reacting the boronic acid group with an alkyl alcohol such as isopropanol; a diol such as pinacol or trimethylene glycol. Specific examples of the boronic acid ester group include a boronic acid pinacol ester group, a boronic acid diisopropyl ester group, a boronic acid propylene glycol ester group, and the like.

[0070] The above diboronic acid ester group is a group represented by -(O)2B-B(O)2-, and as the compound (C) having a diboronic acid ester group, the following formula (6); (R 8 O)(R 9 O)B-B(OR 10 )(OR 11 ) (6) (In the formula, R 8 , R 9 , R 10 , R 11 represent, independently of each other, a hydrogen atom or a hydrocarbon group which may have a hetero atom. However, at least one of R 8 , R 9 , R 10 , R 11 is a hydrocarbon group which may have a hetero atom. R 8 and R 9 may be bonded to each other, and R 10 and R 11 may be bonded to each other.)

[0071] R 8 , R 9 , R 10 , R 11 in the above formula (6) represent, independently of each other, a hydrogen atom or a hydrocarbon group which may have a hetero atom. Examples of the hydrocarbon group include aliphatic hydrocarbon groups such as an alkyl group, an alkenyl group, and an alkynyl group; and aromatic hydrocarbon groups such as an aryl group and an aralkyl group. Specific examples of the above alkyl group, alkenyl group, alkynyl group, aryl group, and aralkyl group are as described in compound (B).

[0072] The number of carbon atoms of the above hydrocarbon group is not particularly limited, but is preferably 1 to 30. Further, the total number of carbon atoms of R 8 and R 9 , and the total number of carbon atoms of R 10 and R 11 are preferably 2 to 30, more preferably 3 to 20, still more preferably 4 to 16, and even more preferably 5 to 12.

[0073] In equation (6) above, R 8 and R 9 They combine with each other, R 10 and R 11 A configuration in which these are coupled to one another is one of the preferred embodiments in this disclosure. For example, R 8 -R 9 , R 10 -R 11 Preferably, the alkylene group has 2 to 10 carbon atoms, such as an ethylene group, a 1,1,2,2-tetramethylethylene group, a 2,2-dimethylpropylene group, a hexylene group (or a 1,1,3-trimethylpropylene group). More preferably, it is a 1,1,2,2-tetramethylethylene group.

[0074] The above compound (C) is preferably a diboronic acid ester compound and / or the following formula (7); YZ (7) (In the formula, Y is -OSO2-CF) n1 Cl 3-n1 This represents a functional group that can react with the group. Z represents an organic group. ) This is a compound represented by ).

[0075] The above diboronic acid ester compound may be any of diboronic acid tetraester, diboronic acid triester, diboronic acid diester, or diboronic acid monoester, but diboronic acid tetraester is preferred. Examples of the above-mentioned diboronic acid ester compounds include alkyl diboronic acid esters, alkylene glycol diboronic acid esters, aryl diboronic acid esters, and arylene glycol diboronic acid esters. More preferably are alkyl diboronic acid esters, alkylene glycol diboronic acid esters, and aryl diboronic acid esters, and even more preferably bis(pinacolate)diborone, bis(neopentyl glycolate)diborone, bis(hexylene glycolate)diborone, bis(catecorate)diborone, and particularly preferably bis(pinacolate)diborone.

[0076] In equation (7) above, Y is -OSO2-CF n1 Cl 3-n1 It is a functional group that can react with the group. -OSO2-CF n1 Cl 3-n1 Specific examples and preferred forms of functional groups that can react with the group are as described above.

[0077] In equation (7) above, Z is an organic group. The above organic group is not particularly limited, but examples include hydrocarbon groups that may have a heteroatom. Examples of the hydrocarbon groups mentioned above include aliphatic hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, which may have substituents; and aromatic hydrocarbon groups such as aryl groups and aralkyl groups, which may have substituents. The number of carbon atoms in the hydrocarbon group is not particularly limited, but 1 to 30 is preferred. More preferably 2 to 25, even more preferably 3 to 20, even more preferably 4 to 18, even more preferably 5 to 16, and especially preferably 6 to 12.

[0078] Specific examples of the above substituents, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and aralkyl groups are as described in compound (B). The above Z is preferably an aromatic hydrocarbon group. A form in which the above compound (C) has an aromatic hydrocarbon group is one of the preferred embodiments in this disclosure.

[0079] The compound represented by the above formula (7) is preferably the following formula (8);

[0080] [ka] (In the formula, Y is -OSO2-CF) n1 Cl 3-n1 Represents a functional group that can react with the group. 12 , R 13 , R 14 , R 15 , R 16The compound is represented by ), where is the same or different, and represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or a substituent that is a group other than an aliphatic hydrocarbon group.

[0081] In equation (8) above, Y is -OSO2-CF n1 Cl 3-n1 It is a functional group that can react with the group. -OSO2-CF n1 Cl 3-n1 Specific examples and preferred forms of functional groups that can react with the group are as described above. Among these, alkenyl groups, alkynyl groups, amino groups, and boronic acid groups are more preferred.

[0082] In equation (8) above, R 12 , R 13 , R 14 , R 15 , R 16 These are the same or different substituents, which are a hydrogen atom, an optionally substituted aliphatic hydrocarbon group, or a group other than an aliphatic hydrocarbon group. Specific examples of the substituents and aliphatic hydrocarbon groups are as described in formula (4).

[0083] The number of carbon atoms in the above aliphatic hydrocarbon group is not particularly limited, but 1 to 12 is preferred. More preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 4. The above aliphatic hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, propyl group, or butyl group, and even more preferably a methyl group. In equation (8) above, R 14 is a methyl group, R 12 , R 13 , R 15 , R 16 A form in which is a hydrogen atom is one of the preferred embodiments in this disclosure. In equation (8) above, R 12 , R 13 , R 14 , R 15 , R 16A form in which is a hydrogen atom is also one of the preferred embodiments in this disclosure.

[0084] Specific examples of compounds represented by formula (8) above include unsaturated group-containing aromatic hydrocarbons such as styrene, 2-,3- or 4-methylstyrene, allylbenzene, 2-,3- or 4-methylallylbenzene, phenylacetylene, and 2-,3- or 4-methylphenylacetylene (ethynyltoluene); aromatic amines such as aniline and 2-,3- or 4-toluidine; aromatic boronic acids such as phenylboronic acid and 2-,3- or 4-methylphenylboronic acid; aromatic boronic acid esters such as phenylboronic acid pinacol ester; and aromatic organometallic compounds such as phenyl zinc halide and phenylmagnesium halide. Among these, unsaturated group-containing aromatic hydrocarbons, aromatic amines, and aromatic boronic acids are preferred, and 4-methylstyrene, 4-ethynyltoluene, and aniline are preferred.

[0085] In the above reaction step (β), it is preferable that the above compound (C) is used in an amount of 0.7 to 5.0 moles per 1.0 mole of the halogenated alkanesulfonyl compound represented by formula (3). More preferably, it is 0.8 to 3.0 moles, and even more preferably 0.9 to 2.5 moles.

[0086] (Coupling reaction) The type of reaction in the above reaction step (β) is not particularly limited, and an appropriate reaction can be selected depending on the functional groups of the above compound (C). For example, if compound (C) is a compound containing boron, the Suzuki-Miyaura coupling reaction or the Ishiyama-Miyaura boration reaction can be used. If the above compound (C) is a compound having an alkynyl group, the Sonogashira coupling reaction can be used. If the above compound (C) is a compound having an alkenyl group, the Heck reaction can be used. If the above compound (C) is a compound having an amino group, the Buchwald-Hartwig amination reaction can be used. If the above compound (C) is a compound having the above MX' group, the Negishi coupling reaction or the Kumada coupling reaction can be used.

[0087] (catalyst) In the above reaction step (β), it is preferable to use a catalyst. The catalyst is not particularly limited as long as it promotes the reaction between the compound represented by formula (3) and compound (C), but a metal catalyst is preferred. The above metals are not particularly limited, and may be typical metals (elements) or transition metals (elements), but transition metals are preferred.

[0088] Examples of typical metals (elements) mentioned above include aluminum, magnesium, gallium, germanium, indium, tin, antimony, thallium, lead, and bismuth.

[0089] Examples of the above transition metals (elements) include scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, and gold. Palladium and copper are preferred among these, and palladium is more preferred.

[0090] The form of the metal catalyst described above is not particularly limited, but examples include powdered or porous elemental metals; elemental metals or metal compounds supported on a carrier such as alumina, carbon, silica, or zeolite; salts of metals such as chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, and oxides; and metal complexes such as olefin complexes, phosphine complexes, amine complexes, ammine complexes, or acetylacetonate complexes. Among these, metal complexes such as phosphine complexes and salts of metals such as chlorides are preferred.

[0091] The above metal catalyst is preferably a palladium catalyst, and examples of palladium catalysts include zero-valent palladium compounds such as tetrakis(triphenylphosphine)palladium, bis[tris(2-methylphenyl)phosphine]palladium, tris(dibenzylideneacetone)dipalladium, and tris(dibenzylideneacetone)dipalladium chloroform complex; [1,1′-bis(diphenylphosphineno)ferrocene]dichloropalladium(II), dichlorobis(triphenylphosphine)palladium(II), and dichlorobis(tricyclohexylpho Examples of divalent palladium compounds include sphingo(palladium(II)), palladium acetylacetonate(II), dichlorobis(benzonitrile)palladium(II), bis(dibenzylideneacetone)palladium, dichlorobis(acetonitrile)palladium(II), dichlorotetraamminepalladium(II), dichloro(cycloocta-1,5-diene)palladium(II), palladium trifluoroacetate(II), palladium chloride(II), palladium bromide(II), palladium iodide(II), and palladium acetate(II). Preferably, these are tetrakis(triphenylphosphine)palladium, bis[tris(2-methylphenyl)phosphine]palladium, [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II), palladium chloride(II), and more preferably tetrakis(triphenylphosphine)palladium.

[0092] The amount of catalyst used is not particularly limited, but preferably 0.001 to 0.5 moles, and more preferably 0.01 to 0.1 moles, per mole of the compound represented by formula (3). One or more types of catalyst may be used.

[0093] (coordination compound) In this disclosure, from the viewpoint of further promoting the reaction between the compound represented by formula (3) and compound (C), a coordinating compound such as a phosphine compound may be used in addition to the catalyst. The above-mentioned coordinating compound is not particularly limited, but examples include phosphine compounds such as 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diphenylphosphino)propane, 1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)butane, and 1,2-bis(diphenylphosphino)ferrocene. Preferably, it is 1,2-bis(diphenylphosphino)ferrocene.

[0094] The amount of the above-mentioned coordinating compound used is not particularly limited, but preferably 0.001 to 1.5 moles and more preferably 0.01 to 0.3 moles per mole of the catalyst.

[0095] (base) In reaction step (β) described above, it is preferable to use a base from the viewpoint of promoting the reaction. The base is not particularly limited as long as it is a basic compound, and may be an inorganic base or an organic base. Specific examples of the base are as described in reaction step (α) described above. In the above reaction step (β), it is preferable to select a base that is appropriate depending on the type of compound (C) and the solvent used. When the above compound (C) is a diboronic acid ester compound, aromatic boronic acid, aromatic amine, etc., an inorganic base such as an alkali metal carbonate such as potassium carbonate, sodium carbonate, cesium carbonate, etc., or an alkali metal acetate such as potassium acetate, etc., is preferred. When the above compound (C) is an unsaturated group-containing aromatic hydrocarbon, an organic base such as a tertiary amine base such as triethylamine or diisopropylethylamine is preferred.

[0096] The amount of the above base used is not particularly limited, but it is preferably 0.7 to 10.0 moles, and more preferably 1.0 to 5.0 moles, per mole of the compound represented by formula (3) above.

[0097] (solvent) In reaction step (β) described above, it is preferable to use a solvent. The solvent is not particularly limited, and those described in reaction step (α) described above can be used. In the reaction step (β) described above, it is preferable to select an appropriate solvent depending on the type of compound (C) described above. Preferably, the solvents mentioned above are aromatic hydrocarbon solvents such as toluene, amide solvents such as N,N-dimethylformamide, and sulfoxide solvents such as dimethyl sulfoxide.

[0098] There are no particular restrictions on the amount of solvent used, but it is sufficient to use 0.05 L (liters) or more per 1 mole of the compound represented by formula (3) and compound (C) combined, with 0.5 to 20 L being preferred, and 0.1 to 10 L being particularly preferred.

[0099] (Reaction temperature) The reaction temperature in the above reaction step (β) is not particularly limited, but it is preferably carried out in the range of -20 to 200°C, more preferably in the range of 0 to 150°C, even more preferably in the range of 25 to 100°C, and particularly preferably in the range of 50 to 80°C.

[0100] (Reaction time) The reaction time in the above reaction step (β) is not particularly limited and can be adjusted according to the raw materials and reaction conditions, but for example, it can be carried out in the range of 0.1 to 72 hours. It is preferable to track the progress of the reaction using analytical means such as NMR and terminate the reaction when the raw materials have almost completely disappeared.

[0101] (Reaction atmosphere) The reaction atmosphere in the above reaction step (β) is not particularly limited and may be an atmospheric atmosphere or an inert gas atmosphere such as nitrogen, helium, neon, or argon. Preferably, it is an inert gas atmosphere such as nitrogen.

[0102] (Post-processing operations) After the above reaction, the workup to isolate the resulting multibond-containing compound can be carried out using general organic synthesis procedures. Examples of workup procedures include filtration, washing with a solvent, and concentration. [Examples]

[0103] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. Here, in the examples and comparative examples, NMR yield (%) refers to the nuclear magnetic resonance spectrum. 1 H-NMR or 19 Analysis using F-NMR revealed the internal standard method ( 1 H-NMR analysis and 19 In 1F-NMR, the value was obtained by quantification using 1,4-bistrifluoromethylbenzene or 2,2-difluoroethanol as an internal standard. The yields of the target products described in Examples 1 to 12, described later, were calculated using the isolation yield after purification, while the quantitative yields of the target products described in Examples 13 to 25 were calculated using the NMR yield.

[0104] <Method for producing halogenated alkanesulfonyl compounds> [Example 1] 227 mg (1.63 mmol, 1.0 eq.) of 4-nitrophenol as the substrate (compound (B)), 330 mg (1.96 mmol, 1.2 eq.) of sodium carbonate, and 8.2 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 330 mg (1.96 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride (boiling point: 27°C) as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 386 mg of the target product in 82% yield.

[0105] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.91(2H,d,J=9.1Hz),7.50(2H,d,J=9.2Hz) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.5(2F,s)

[0106] The reaction in Example 1 is shown below.

[0107] [ka]

[0108] [Example 2] 201 mg (1.86 mmol, 1.0 eq.) of 4-cresol as the substrate (compound (B)), 308 mg (2.23 mmol, 1.2 eq.) of sodium carbonate, and 9.28 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 375 mg (2.23 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 352 mg of the target product in 74% yield.

[0109] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.21(2H,d,J=8.7Hz),7.16(2H,d,J=8.5Hz),2.36(3H,s) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.8(2F,s)

[0110] The reaction in Example 2 is shown below.

[0111] [ka]

[0112] [Example 3] 208 mg (1.67 mmol, 1.0 eq.) of 4-methoxyphenol as the substrate (compound (B)), 277 mg (2.01 mmol, 1.2 eq.) of sodium carbonate, and 8.36 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 338 mg (2.01 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 363 mg of the target product in 78% yield.

[0113] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.21(2H,d,J=9.2Hz),6.91(2H,d,J=9.2Hz),3.82(3H,s) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.7(2F,s)

[0114] The reaction in Example 3 is shown below.

[0115] [ka]

[0116] [Example 4] 164 mg (1.28 mmol, 1.0 eq.) of 4-chlorophenol as the substrate (compound (B)), 212 mg (1.53 mmol, 1.2 eq.) of sodium carbonate, and 6.4 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 258 mg (1.53 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 260 mg of the target product in 73% yield.

[0117] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.42(2H,d,J=9.2Hz),7.24(2H,d,J=9.2Hz) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.7(2F,s)

[0118] The reaction in Example 4 is shown below.

[0119] [ka]

[0120] [Example 5] 209 mg (1.92 mmol, 1.0 eq.) of 4-aminophenol as the substrate (compound (B)), 318 mg (2.30 mmol, 1.2 eq.) of sodium carbonate, and 9.6 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 388 mg (2.30 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 366 mg of the target product in 74% yield.

[0121] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.06(2H,d,J=8.9Hz),6.64(2H,d,J=8.9Hz),3.80(2H,s) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.8(2F,s)

[0122] The reaction in Example 5 is shown below.

[0123] [ka]

[0124] [Example 6] 517 mg (3.39 mmol, 1.0 eq.) of methyl 4-hydroxybenzoate as the substrate (compound (B)), 563 mg (4.07 mmol, 1.2 eq.) of sodium carbonate, and 17 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 686.5 mg (4.07 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 811 mg of the target product in 79% yield.

[0125] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):8.14(2H,d,J=8.9Hz),7.37(2H,d,J=8.9Hz),3.94(2H,s) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.7(2F,s)

[0126] The reaction in Example 6 is shown below.

[0127] [ka]

[0128] [Example 7] 109 mg (0.976 mmol, 1.0 eq.) of 4-fluorophenol as the substrate (compound (B)), 162 mg (1.17 mmol, 1.2 eq.) of sodium carbonate, and 4.9 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 197 mg (1.17 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 250 mg of the target product in 98% yield.

[0129] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.26~7.30(2H,m),7.10~7.15(2H,m) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-59.7(2F,s),-112.6(1F,s) The reaction in Example 7 is shown below.

[0130] [ka]

[0131] [Example 8] 165 mg (1.47 mmol, 1.0 eq.) of 3-fluorophenol as the substrate (compound (B)), 243 mg (1.76 mmol, 1.2 eq.) of sodium carbonate, and 7.3 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 297 mg (1.76 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 382 mg of the target product in 99% yield.

[0132] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.39~7.45(1H,m), 7.09~7.13(2H,m), 7.03~7.06(1H,m) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.6(2F,s),-108.3(1F,s) The reaction in Example 8 is shown below.

[0133] [ka]

[0134] [Example 9] 91.7 mg (0.659 mmol, 1.0 eq.) of 4-nitrophenol as the substrate (compound (B)), 120 mg (0.791 mmol, 1.2 eq.) of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 3.3 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 133 mg (0.791 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed and the mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water, and the organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 94 mg of the target product in 50% yield.

[0135] The reaction in Example 9 is shown below.

[0136] [ka]

[0137] [Example 10] 144 mg (1.00 mmol, 1.0 eq.) of 1-naphthol as the substrate (compound (B)), 167 mg (1.21 mmol, 1.2 eq.) of sodium carbonate, and 5.0 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 202 mg (1.20 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride (boiling point: 27°C) as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 252 mg of the target product in 86% yield.

[0138] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):8.12(1H,d,J=8.5Hz),7.91(1H,d,J=7.6Hz),7.85~7.87(1H,m),7.58~7.66(2H,m),7.46~7.51(2H,m) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-59.5(2F,s)

[0139] The reaction in Example 10 is shown below.

[0140] [ka]

[0141] [Example 11] 110 mg (1.00 mmol, 1.0 eq.) of hydroquinone as the substrate (compound (B)), 332 mg (2.40 mmol, 2.4 eq.) of sodium carbonate, and 5.0 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 404 mg (2.40 mmol, 2.4 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 373 mg of the target product in 92% yield.

[0142] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.40(4H,s) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.5(4F,s)

[0143] The reaction in Example 11 is shown below.

[0144] [ka]

[0145] [Example 12] 239 mg (2.49 mmol, 1.0 eq.) of 3-hydroxypyridine as the substrate (compound (B)), 415 mg (3.00 mmol, 1.2 eq.) of sodium carbonate, and 5.0 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 424 mg (3.00 mmol, 1.2 eq.) of chlorodifluoromethanesulfonyl fluoride as compound (A) was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain 584 mg of the target product in 95% yield.

[0146] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):8.63~8.66(2H,m),7.65~7.68(1H,m),7.41~7.45(1H,m) 19 F-NMR(400MHz,chloroform-d)δ(ppm):-58.4(2F,s)

[0147] The reaction in Example 12 is shown below.

[0148] [ka]

[0149] Table 1 below shows the compound (B) used in the reaction (type and amount added), the base, the solvent, and the yield of the reaction product for Examples 1-12.

[0150] [Table 1]

[0151] [Comparative Example 1] 1.02 g (6.70 mmol, 1.0 eq.) of methyl 4-hydroxybenzoate as the substrate (compound (B)), 1.11 g (8.04 mmol, 1.2 eq.) of potassium carbonate, and 16.7 mL of acetonitrile as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After cooling the round-bottom flask to 0°C in an ice bath, 1.75 g (8.04 mmol, 1.2 eq.) of trichloromethanesulfonyl chloride was added, and the ice bath was removed. The mixture was stirred at room temperature for 16 hours. After filtering the reaction mixture, liquid-liquid separation was performed with ethyl acetate and supernatant water. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure, but the target product was not obtained.

[0152] The reaction in Comparative Example 1 is shown below.

[0153] [ka]

[0154] [Comparative Example 2] 665 mg (4.37 mmol, 1.0 eq.) of methyl 4-hydroxybenzoate as the substrate (Compound (B)) and 8.7 mL of tetrahydrofuran as the reaction solvent were taken and charged into a eggplant flask equipped with a stir bar. After cooling the eggplant flask to 0 °C in an ice bath, 184 mg (4.59 mmol, 1.05 eq.) of 60% NaH was added and stirred for 10 minutes. Then, 1.0 g (4.59 mmol, 1.05 eq.) of trichloromethanesulfonyl chloride was added, and then the ice bath was removed and stirred at room temperature for 16 hours. Ethyl acetate and water were added to the reaction solution, and then liquid separation was carried out. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure, but the target product could not be obtained.

[0155] The reaction in Comparative Example 2 is shown below.

[0156] [Chemical formula]

[0157] [Comparative Example 3] 396 mg (2.60 mmol, 1.0 eq.) of methyl 4-hydroxybenzoate as the substrate (Compound (B)) and 10.4 mL of dichloromethane as the reaction solvent were taken and charged into a eggplant flask equipped with a stir bar. 342 mg (3.38 mmol, 1.3 eq.) of triethylamine was added and stirred for 10 minutes. Then, 623 mg (2.86 mmol, 1.1 eq.) of trichloromethanesulfonyl chloride was added, and then the ice bath was removed and stirred at room temperature for 16 hours. Ethyl acetate and water were added to the reaction solution, and then liquid separation was carried out. The organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure, but the target product could not be obtained.

[0158] The reaction in Comparative Example 3 is shown below.

[0159] [Chemical formula]

[0160] Table 2 below shows the compound (B) used in the reaction (type and amount added), the base, the solvent, and the yield of the reaction product for Comparative Examples 1-3. [Table 2]

[0161] <Method for producing compounds containing multiple bonds: Coupling reaction> [Example 13] 67.7 mg (0.24 mmol, 1.0 eq.) of 4-nitrophenyl chlorodifluoromethanesulfonate as the substrate (compound represented by formula (3)), 48.0 mg (0.35 mmol, 1.5 eq.) of 4-methylphenylboronic acid and 65.1 mg (0.47 mmol, 2.0 eq.) of sodium carbonate as compound (C), and 1.2 mL of toluene and 0.1 mL of water as reaction solvents were taken and placed in a round-bottom flask equipped with a stirring bar. After bubbling the solution with nitrogen for 5 minutes, 13.6 mg (0.01 mmol, 0.05 eq.) of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added as the catalyst, the reactor was tightly sealed, and stirred at 60°C for 16 hours. The reaction mixture was separated with ethyl acetate and supernatant water, and the organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude product. To the crude sample, 42 mg of 1,4-BIS-trifluoromethylbenzene was added as an internal standard. 1 By analyzing with 1H-NMR, the target product was quantified by NMR yield, and it was confirmed that 50.2 mg of the corresponding coupling compound was produced with a quantitative yield of 100%.

[0162] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):8.27(2H,d,J=9.2Hz),7.71(2H,d,J=9.2Hz),7.52(2H,d,J=8.2Hz),7.31(2H,d,J=8.2Hz),2.42(3H,s)

[0163] The reaction in Example 13 is shown below.

[0164] [Chemical formula]

[0165] [Examples 14 - 18] Next, a Suzuki - Miyaura cross - coupling was carried out in the same procedure as in Example 13, except that the compound represented by formula (3) was changed.

[0166] For Examples 13 - 18, the quantitative yields (NMR yields) of the compound represented by formula (3) used in the reaction and the reaction product (coupled product) were shown in Table 3 below.

[0167] [Table 3]

[0168] [Example 19] 60.1 mg (0.20 mmol, 1.0 eq.) of methyl 4 - chlorodifluoromethanesulfonate benzoate as the substrate (compound represented by formula (3)), 49.6 mg (0.42 mmol, 2.1 eq.) of 4 - methylstyrene, 101.2 mg (1.00 mmol, 5.0 eq.) of triethylamine, and 1.0 mL of DMF as the reaction solvent were taken and charged into an eggplant flask with a stir bar. After nitrogen bubbling was carried out for 5 minutes for the solution, 11.6 mg (0.01 mmol, 0.05 eq.) of Pd(PPh3)4 was added as a catalyst, then the reactor was sealed, and stirred at 60 °C for 16 hours. The reaction solution was separated with ethyl acetate and water, the organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. 42 mg of 1,4 - BIS - trifluoromethylbenzene was added to the crude product as an internal standard substance, 1 By analyzing with 1H - NMR, the target product was quantified by the NMR yield, and it was confirmed that 50.5 mg of the corresponding coupled product was generated with a quantitative yield of 57%.

[0169] [Physical properties] 1H-NMR(400MHz,chloroform-d)δ(ppm):8.01(2H,d,J=8.5Hz),7.54(2H,d,J=8.2Hz),7.42(2H,d,J=8.0Hz),7.18(2H,d,J=8.5Hz),3.91(3H,s),2.31(3H,s)

[0170] The reaction in Example 19 is shown below.

[0171] [ka]

[0172] [Examples 20-22, Comparative Example 4] Next, the Heck reaction was carried out using the same procedure as in Example 19, except that the leaving group of the substrate (trihalomethanesulfonate moiety), the catalyst, or the base was changed.

[0173] Table 4 below shows the quantitative yields of the leaving group, compound (C), catalyst, base, and reaction product in the compound represented by formula (3) used in the reaction for Examples 19-22 and Comparative Example 4.

[0174] [Table 4]

[0175] The catalysts and bases in Table 4 above are as follows: Pd(PPh3)4: Tetrakis(triphenylphosphine)palladium Pd[(o-tol)3P]2:bis[tris(2-methylphenyl)phosphine]palladium Pd(dppf)Cl2:[1,1′-bis(diphenylphosphin)ferrocene]dichloropalladium(II) Et3N: Triethylamine DIPEA: N,N-diisopropylethylamine

[0176] [Example 23] 60.1 mg (0.20 mmol, 1.0 eq.) of methyl 4-chlorodifluoromethanesulfonate as the substrate (compound represented by formula (3)), 34.8 mg (0.30 mmol, 1.5 eq.) of 4-ethynyltoluene, and 0.5 mL of DMF and 0.5 mL of triethylamine as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After bubbling the solution with nitrogen for 5 minutes, 3.0 mg (0.016 mol, 0.08 eq.) of copper(I) iodide and 11.6 mg (0.01 mmol, 0.05 eq.) of Pd(PPh3)4 were added as catalysts, the reactor was sealed tightly, and the mixture was stirred at 80°C for 16 hours. The reaction mixture was separated with ethyl acetate and supernatant water, and the organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude product. To the crude sample, 42 mg of 1,4-BIS-trifluoromethylbenzene was added as an internal standard. 1 By analyzing with 1H-NMR, the target product was quantified by NMR yield, and it was confirmed that 50.1 mg of the corresponding coupling compound was produced with a quantitative yield of 100%.

[0177] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):8.00(2H,d,J=8.7Hz),7.56(2H,d,J=8.7Hz),7.43(2H,d,J=8.2Hz),7.15(2H,d,J=8.0Hz),3.91(3H,s),2.33(3H,s)

[0178] The reaction in Example 23 is shown below.

[0179] [ka]

[0180] [Example 24] 60.1 mg (0.20 mmol, 1.0 eq.) of methyl 4-chlorodifluoromethanesulfonate as the substrate (compound represented by formula (3)), 22.4 mg (0.24 mmol, 1.2 eq.) of aniline, 65.2 mg (0.20 mmol, 1.0 eq.) of cesium carbonate, 4 Å of molecular sieves, and 0.4 mL of toluene as the reaction solvent were collected and placed in a round-bottom flask equipped with a stirring bar. After bubbling the solution with nitrogen for 5 minutes, 11.6 mg (0.01 mmol, 0.05 eq.) of Pd(PPh3)4 as the catalyst was added, the reactor was tightly sealed, and stirred at 110°C for 19 hours. The reaction mixture was separated with ethyl acetate and saturated sodium bicarbonate aqueous solution, the organic phase was dried with sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude product. 42 mg of 1,4-BIS-trifluoromethylbenzene was added to the crude product as an internal standard. 1 By analyzing with 1H-NMR, the target product was quantified by NMR yield, and it was confirmed that 39.2 mg of the corresponding coupling compound was produced with a quantitative yield of 100%.

[0181] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.91(2H,d,J=8.7Hz), 7.43~7.47(1H,m), 7.29~7.38(2H,m),6.99(2H,d,J=8.9Hz) ,6.23(1H,s)

[0182] The reaction in Example 24 is shown below.

[0183] [ka]

[0184] [Example 25] 60.1 mg (0.20 mmol, 1.0 eq.) of methyl 4-chlorodifluoromethanesulfonate as substrate (compound represented by formula (3)), 76.2 mg (0.30 mmol, 1.5 eq.) of bispinacolatodiborone, 58.8 mg (0.60 mmol, 3.0 eq.) of potassium acetate, and 1.0 mL of DMSO as the reaction solvent were taken and placed in a round-bottom flask equipped with a stirring bar. After bubbling the solution with nitrogen for 5 minutes, 1.8 mg (0.01 mmol, 0.05 eq.) of PdCl2 and 5.5 mg (0.01 mmol, 0.05 eq.) of dppf were added as catalysts, the reactor was tightly sealed, and the mixture was stirred at 80°C for 21 hours. The reaction mixture was separated with ethyl acetate and saturated sodium bicarbonate aqueous solution, and the organic phase was dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain the crude product. To the crude sample, 42 mg of 1,4-BIS-trifluoromethylbenzene was added as an internal standard. 1 By analyzing with 1H-NMR, the target product was quantified by NMR yield, and it was confirmed that 26.8 mg of the corresponding coupling compound was produced with a quantitative yield of 58%.

[0185] [Physical properties] 1 H-NMR(400MHz,chloroform-d)δ(ppm):7.97(2H,d,J=8.2Hz),7.82(2H,d,J=8.2Hz),3.87(3H,s),1.30(12H,s)

[0186] The reaction in Example 25 is shown below.

[0187] [ka]

[0188] For Examples 23-25, the quantitative yields of the compound represented by formula (3), compound (C), catalyst, base, and reaction product used in the reaction are shown in Table 5 below.

[0189] [Table 5]

Claims

1. The following formula (1); X-SO ２ -CF ｎ１ Cl ３－ｎ１ (1) (In the formula, n1 represents a number of 1 or 2. X is a chlorine atom, a fluorine atom, or O-SO) ２ -CF ｎ２ Cl ３－ｎ２ Compound (A) represented by the following formula (2): n² represents the number 1 or 2, and compound (A) represented by the following formula (2); R １ -OH (2) (In the formula, R １ A method for producing an alkanesulfonyl halide compound, comprising the step of reacting a compound (B) represented by ( ) with a base and a solvent in the presence of a base and a solvent.

2. Said R １ is an aromatic hydrocarbon group or an unsaturated hydrocarbon group which may have a heteroatom, and is a method for producing a halogenated alkanesulfonyl compound according to claim 1.

3. The aforementioned R １ The method for producing a halogenated alkanesulfonyl compound according to claim 2, wherein the aromatic hydrocarbon group or unsaturated hydrocarbon group in may have substituents, and the substituent is at least one selected from the group consisting of a hydroxyl group, a nitro group, an alkoxy group, a halogeno group, an amino group, and an alkyl ester group.

4. The method for producing a halogenated alkanesulfonyl compound according to claim 1 or 2, wherein the base is an inorganic base.

5. The method for producing a halogenated alkanesulfonyl compound according to claim 1 or 2, wherein the solvent is an aprotic polar solvent.

6. The following formula (3); R １ -OSO ２ -CF ｎ１ Cl ３－ｎ１ (3) (In the formula, n1 represents a number of 1 or 2. R １ represents an organic group having multiple bonds. ) and the -OSO in formula (3) ２ -CF ｎ１ Cl ３－ｎ１ A method for producing a multiple bond-containing compound, comprising the step of reacting a compound (C) having a functional group that can react with the group.

7. In the compound (C) mentioned above, -OSO in formula (3) ２ -CF ｎ１ Cl ３－ｎ１ The method for producing a multiple bond-containing compound according to claim 6, wherein the functional group that can react with the group is at least one selected from the group consisting of an unsaturated hydrocarbon group, an amino group, a boronic acid group, a boronic acid ester group, a diboronic acid ester group, and an -MX' group (where M represents Mg or Zn, and X' represents a halogen atom).

8. The method for producing a multiple bond-containing compound according to claim 6 or 7, wherein the compound (C) has an aromatic hydrocarbon group.

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