Method for producing sulfone derivative using haloacetic acid

Abstract

The present invention provides an industrially advantageous method for producing sulfone derivatives useful as herbicides and intermediates thereof.

Description

Technical Field

[0001] The present invention relates to a method for producing a sulfone derivative useful as a herbicide, namely, a compound of the following formula (2):

[0002] [Chemistry 1]

[0003]

[0004] In the formula, R 1 , R 2 , R 3 , R 4 and R 5 As described in this manual. Background Art

[0005] The sulfone derivatives of the formula (2) are known to have herbicidal activity as disclosed in WO2002 / 062770A1 (Patent Document 1). Among them, the compound of the formula (2-a) (pyroxasulfone) is well known to be an excellent herbicide.

[0006]

[0007] As a method for producing the compound of formula (2), a method by oxidation of a sulfide derivative, that is, a compound of formula (1) is known as shown below.

[0008] [Chemistry 2]

[0009]

[0010] As shown in the scheme below, Reference Example 3 of WO2004 / 013106A1 (Patent Document 2) describes a method for producing 3-(5-difluoromethoxy-1-methyl-3-trifluoromethyl-1H-pyrazol-4-ylmethylsulfonyl)-5,5-dimethyl-2-isoxazoline (2-a) (pyrazolone) by oxidizing 3-(5-difluoromethoxy-1-methyl-3-trifluoromethyl-1H-pyrazol-4-ylmethylthio)-5,5-dimethyl-2-isoxazoline (1-a) (ISFP) using m-chloroperbenzoic acid (mCPBA).

[0011] [Chemistry 3]

[0012] WO2004 / 013106A1, ReferenceExample3

[0013]

[0014] In the method for producing the compound of formula (2) from the compound of formula (1), the meta-chloroperbenzoic acid (mCPBA) described in WO2004 / 013106A1 (Patent Document 2) is expensive for industrial application and has problems with handling and waste. Therefore, the production method described in WO2004 / 013106A1 (Patent Document 2) is not suitable for industrial-scale production.

[0015] In addition, in the method for producing a compound of formula (2) (sulfone derivative: SO2 derivative) from a compound of formula (1) (sulfide derivative: S derivative), the reaction may be stopped due to the intermediate sulfoxide derivative (SO derivative), i.e., the compound of formula (3) below:

[0016] [Chemistry 4]

[0017]

[0018] In the formula, R 1 , R 2 , R 3 , R 4 and R 5 As described in this specification. Therefore, the compound of formula (3) sometimes remains in the product as a by-product. The compound of formula (3) mixed in products such as herbicides may cause quality degradation and damage to crops. However, since the physical and chemical properties of the compound of formula (3) are very similar to those of the compound of formula (2), it is difficult to separate the compound of formula (3) to purify the compound of formula (2). Therefore, for the method of manufacturing the compound of formula (2) from the compound of formula (1), a manufacturing method is required in which the oxidation reaction is fully carried out and the amount of the compound of formula (3) in the product is sufficiently small.

[0019] WO2021 / 002484A9 (Patent Document 5) describes a method for producing pyroxasulfone. This method is an excellent method for solving the above-mentioned problems. On the other hand, due to the use of transition metals, this method still has room for improvement.

[0020] Example 9C of Japanese Patent Publication No. 2013-512201 (JP2013-512201A) (Patent Document 6) describes a method for producing sulfonepyraclostrobin using acetic acid. However, the above-mentioned problems have not been solved, and since a transition metal is also used, there is a need to improve the method.

[0021] Japanese Patent Publication No. 2013-512201 (JP 2013-512201 A) (Patent Document 6) corresponds to US 2012 / 264947 A1 (Patent Document 7).

[0022] Example 4 of CN111574511 A (Patent Document 8) describes a production method without using a transition metal. However, the yield described is low and has no reproducibility.

[0023] Prior art patent literature

[0024] Patent Document 1: International Patent Publication No. 2002 / 062770

[0025] Patent Document 2: International Patent Publication No. 2004 / 013106

[0026] Patent Document 3: International Patent Publication No. 2005 / 095352

[0027] Patent Document 4: International Patent Publication No. 2005 / 105755

[0028] Patent Document 5: International Patent Publication No. 2021 / 002484

[0029] Patent Document 6: Japanese Patent Publication No. 2013-512201

[0030] Patent Document 7: U.S. Patent Publication No. 2012 / 264947 Specification

[0031] Patent Document 8: Chinese Patent Publication No. 111574511 Summary of the invention

[0032] Technical Problems to be Solved by the Invention

[0033] The object of the present invention is to provide a method for producing a compound of formula (2) from a compound of formula (1), that is, to provide an industrially advantageous production method in which the proportion of the compound of formula (3) in the product is sufficiently low, the yield is high, and the method is conducive to industrial-scale production.

[0034] Another object of the present invention is to provide an environmentally friendly method for preparing the compound of formula (2).

[0035] Means used to solve problems

[0036] After careful study, the present inventors found that, as described below, by reacting the compound of formula (1) with an oxidant in the presence of a haloacetic acid, the compound of formula (2) can be effectively produced without using a transition metal as a catalyst. Based on this discovery, the present inventors have completed the present invention.

[0037] [Chemistry 5]

[0038]

[0039] In the formula, R 1 , R 2 , R3 , R 4 and R 5 As described in this manual.

[0040] Effects of the Invention

[0041] The present invention provides a method for producing the compound of formula (2), which is a novel method for producing the compound of formula (2) with high yield and being environmentally friendly because no transition metal is used. Therefore, the present invention contributes to sustainable development.

[0042] The present invention also provides a method for producing a compound of formula (2) (sulfone derivative: SO2 derivative) from a compound of formula (1) (sulfide derivative: S derivative), that is, a method for producing a compound of formula (3) (sulfoxide derivative: SO derivative) in which the proportion of the compound in the product is sufficiently low, the yield is high, and the method is conducive to industrial-scale production. In the compound of formula (2) produced by the method of the present invention, the amount of the compound of formula (3) that may cause a decrease in quality as a herbicide and damage to crops is sufficiently small, so that it can be used as a herbicide.

[0043] The method of the present invention can be implemented on a large scale using low-cost materials, has excellent economic benefits, and is suitable for industrial-scale production. DETAILED DESCRIPTION

[0044] The present invention will now be described in detail.

[0045] In one aspect, the present invention is as follows:

[0046] [I-1] A method for producing a compound of formula (2), comprising: reacting a compound of formula (1) with an oxidizing agent in the presence of a halogenated acetic acid and in the absence of a transition metal:

[0047] [Chemistry 6]

[0048]

[0049] In the formula,

[0050] R 1 , R 2 and R 3 each independently represents (C1-C6)alkyl optionally substituted by one or more substituents, (C3-C6)cycloalkyl optionally substituted by one or more substituents, (C2-C6)alkenyl optionally substituted by one or more substituents, (C2-C6)alkynyl optionally substituted by one or more substituents, or (C6-C10)aryl optionally substituted by one or more substituents;

[0051] R 4 and R 5each independently represents (C1-C6)alkyl optionally substituted by one or more substituents, (C3-C6)cycloalkyl optionally substituted by one or more substituents, (C2-C6)alkenyl optionally substituted by one or more substituents, (C2-C6)alkynyl optionally substituted by one or more substituents, (C1-C6)alkoxy optionally substituted by one or more substituents, or (C6-C10)aryl optionally substituted by one or more substituents, or

[0052] R 4 and R 5 Together with the carbon atoms to which they are attached, they form a 4- to 12-membered carbocyclic ring, which is optionally substituted by one or more substituents.

[0053] [I-2] The method according to [I-1], wherein in the method, the halogenated acetic acid is selected from monochloroacetic acid, dichloroacetic acid and trichloroacetic acid.

[0054] [I-3] The method according to [I-1], wherein in the method, the halogenated acetic acid is one or more (preferably one or two, more preferably one) halogenated acetic acids selected from monochloroacetic acid, dichloroacetic acid and trichloroacetic acid.

[0055] [I-4] The method according to [I-1], wherein in the method, the halogenated acetic acid is dichloroacetic acid.

[0056] [I-5] The method according to [I-1], wherein in the method, the halogenated acetic acid is trichloroacetic acid.

[0057] [I-6] The method according to any one of [I-1] to [I-5], wherein in the method, the amount of the halogenated acetic acid used is 1 mol or more based on 1 mol of the compound of formula (1).

[0058] [I-7] The method according to any one of [I-1] to [I-5], wherein in the method, the amount of the halogenated acetic acid used is 3 mol or more based on 1 mol of the compound of formula (1).

[0059] [I-8] The method according to any one of [I-1] to [I-5], wherein in the method, the amount of the halogenated acetic acid used is 5 mol or more based on 1 mol of the compound of formula (1).

[0060] [I-9] The method according to any one of [I-1] to [I-5], wherein in the method, the amount of the halogenoacetic acid used is 8 mol or more based on 1 mol of the compound of formula (1).

[0061] [I-10] The method according to any one of [I-1] to [I-5], wherein in the method, the amount of the halogenated acetic acid used is 10 mol or more based on 1 mol of the compound of formula (1).

[0062] [I-11] The method according to any one of [I-1] to [I-5], wherein in the method, the amount of the halogenated acetic acid used is 15 mol or more based on 1 mol of the compound of formula (1).

[0063] [I-12] The method according to any one of [I-1] to [I-11], wherein in the method, the amount of the halogenated acetic acid used is 100 mol or less based on 1 mol of the compound of formula (1).

[0064] [I-13] The method according to any one of [I-1] to [I-11], wherein in the method, the amount of the halogenated acetic acid used is 60 mol or less based on 1 mol of the compound of formula (1).

[0065] [I-14] The method according to any one of [I-1] to [I-11], wherein in the method, the amount of the halogenated acetic acid used is 35 mol or less based on 1 mol of the compound of formula (1).

[0066] [I-15] The method according to any one of [I-1] to [I-11], wherein in the method, the amount of the halogenated acetic acid used is 25 mol or less based on 1 mol of the compound of formula (1).

[0067] [I-16] The method according to any one of [I-1] to [I-11], wherein in the method, the amount of the halogenated acetic acid used is 20 mol or less based on 1 mol of the compound of formula (1).

[0068] [I-17] The method according to any one of [I-1] to [I-16], wherein in the method, the amount of the halogenoacetic acid used is 0.1 liter or more based on 1 mol of the compound of formula (1).

[0069] [I-18] The method according to any one of [I-1] to [I-16], wherein in the method, the amount of the haloacetic acid used is 0.3 liter or more based on 1 mol of the compound of formula (1).

[0070] [I-19] The method according to any one of [I-1] to [I-16], wherein in the method, the amount of the halogenoacetic acid used is 0.4 liter or more based on 1 mol of the compound of formula (1).

[0071] [I-20] The method according to any one of [I-1] to [I-16], wherein in the method, the amount of the halogenoacetic acid used is 0.8 liters or more based on 1 mol of the compound of formula (1).

[0072] [I-21] The method according to any one of [I-1] to [I-16], wherein in the method, the amount of the haloacetic acid used is 1.2 liters or more based on 1 mol of the compound of formula (1).

[0073] [I-22] The method according to any one of [I-1] to [I-16], wherein in the method, the amount of the haloacetic acid used is 1.3 liters or more based on 1 mol of the compound of formula (1).

[0074] [I-23] The method according to any one of [I-1] to [I-22], wherein in the method, the amount of the haloacetic acid used is 10 liters or less based on 1 mol of the compound of formula (1).

[0075] [I-24] The method according to any one of [I-1] to [I-22], wherein in the method, the amount of the halogenoacetic acid used is 5.0 liters or less based on 1 mol of the compound of formula (1).

[0076] [I-25] The method according to any one of [I-1] to [I-22], wherein in the method, the amount of the halogenated acetic acid used is 3.0 liters or less based on 1 mol of the compound of formula (1).

[0077] [I-26] The method according to any one of [I-1] to [I-22], wherein in the method, the amount of the haloacetic acid used is 2.0 liters or less based on 1 mol of the compound of formula (1).

[0078] [I-27] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is performed in the presence of an organic solvent other than a halogenated acetic acid.

[0079] [I-28] A method according to any one of [I-1] to [I-26], wherein in the method, the reaction is carried out in the presence of an organic solvent other than halogenated acetic acid, and the organic solvent is selected from aromatic hydrocarbon derivatives, halogenated aliphatic hydrocarbons, carboxylic acids, nitriles, carboxylates, ethers, ketones, amides, ureas and sulfones.

[0080] [I-29] A method according to any one of [I-1] to [I-26], wherein in the method, the reaction is carried out in the presence of an organic solvent other than halogenated acetic acid, and the organic solvent is one or more (preferably one or two, more preferably one) organic solvents selected from aromatic hydrocarbon derivatives, halogenated aliphatic hydrocarbons, carboxylic acids, nitriles, carboxylates, ethers, ketones, amides, ureas and sulfones.

[0081] [I-30] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is carried out in the presence of an organic solvent other than halogenated acetic acid, and the organic solvent is selected from nitriles, carboxylic acids and amides.

[0082] [I-31] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is carried out in the presence of an organic solvent other than halogenated acetic acid, and the organic solvent is one or two (preferably one) organic solvents selected from nitriles, carboxylic acids and amides.

[0083] [I-32] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is performed in the presence of an organic solvent other than a halogenated acetic acid, and the organic solvent is acetonitrile.

[0084] [I-33] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is performed in the presence of an organic solvent, and the organic solvent is an organic solvent that does not include alcohols.

[0085] [I-34] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is carried out in the presence of an organic solvent, and the organic solvent is an organic solvent that does not include (C1-C6) alcohols.

[0086] [I-35] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is carried out in the presence of an organic solvent, and the organic solvent is an organic solvent that does not include (C1-C4) alcohols.

[0087] [I-36] The method according to any one of [I-1] to [I-35], wherein in the method, the amount of the organic solvent other than the halogenated acetic acid used in the reaction is 0.3 liters or more based on 1 mol of the compound of formula (1).

[0088] [I-37] The method according to any one of [I-1] to [I-35], wherein in the method, the amount of the organic solvent other than the halogenated acetic acid used in the reaction is 0.5 liter or more based on 1 mol of the compound of formula (1).

[0089] [I-38] The method according to any one of [I-1] to [I-35], wherein in the method, the amount of the organic solvent other than the halogenated acetic acid used in the reaction is 3.0 liters or less based on 1 mol of the compound of formula (1).

[0090] [I-39] The method according to any one of [I-1] to [I-35], wherein in the method, the amount of the organic solvent other than the halogenated acetic acid used in the reaction is 2.0 liters or less based on 1 mol of the compound of formula (1).

[0091] [I-40] The method according to any one of [I-1] to [I-26], wherein in the method, the reaction is performed in the absence of an organic solvent other than halogenated acetic acid.

[0092] [I-41] The method according to any one of [I-1] to [I-40], wherein in the method, the reaction is performed at 10°C to 100°C.

[0093] [I-42] The method according to any one of [I-1] to [I-40], wherein in the method, the reaction is performed at 30°C to 80°C.

[0094] [I-43] The method according to any one of [I-1] to [I-40], wherein in the method, the reaction is performed at 40°C to 80°C.

[0095] [I-44] The method according to any one of [I-1] to [I-40], wherein in the method, the reaction is performed at 40°C to 65°C.

[0096] [I-45] The method according to any one of [I-1] to [I-44], wherein in the method, the reaction is performed for 30 minutes or longer.

[0097] [I-46] The method according to any one of [I-1] to [I-44], wherein in the method, the reaction is performed for 1 hour or longer.

[0098] [I-47] The method according to any one of [I-1] to [I-46], wherein in the method, the reaction is performed for 48 hours or less.

[0099] [I-48] The method according to any one of [I-1] to [I-46], wherein in the method, the reaction is performed for 12 hours or less.

[0100] [I-49] The method according to any one of [I-1] to [I-46], wherein in the method, the reaction is performed for 6 hours or less.

[0101] [I-50] The method according to any one of [I-1] to [I-46], wherein in the method, the reaction is performed for 4 hours or less.

[0102] [I-51] The method according to any one of [I-1] to [I-46], wherein in the method, the reaction is performed for 2 hours or less.

[0103] [I-52] The method according to [I-1] to [I-51], wherein in the method, the reaction is performed in the presence of an aqueous solvent.

[0104] [I-53] The method according to any one of [I-1] to [I-52], wherein in the method, the amount of the aqueous solvent used in the reaction is 0.05 liter or more based on 1 mol of the compound of formula (1).

[0105] [I-54] The method according to any one of [I-1] to [I-52], wherein in the method, the amount of the aqueous solvent used in the reaction is 0.1 liter or more based on 1 mol of the compound of formula (1).

[0106] [I-55] The method according to any one of [I-1] to [I-54], wherein in the method, the amount of the aqueous solvent used in the reaction is 0.5 liter or less based on 1 mol of the compound of formula (1).

[0107] [I-56] The method according to any one of [I-1] to [I-54], wherein in the method, the amount of the aqueous solvent used in the reaction is 0.3 liters or less based on 1 mol of the compound of formula (1).

[0108] [I-57] The method according to any one of [I-1] to [I-56], wherein in the method, the oxidizing agent is hydrogen peroxide, a persulfate, or a hydrogen persulfate.

[0109] [I-58] The method according to any one of [I-1] to [I-56], wherein in the method, the oxidizing agent is hydrogen peroxide.

[0110] [I-59] The method according to any one of [I-1] to [I-56], wherein in the method, the oxidizing agent is a 10 wt % to 70 wt % aqueous hydrogen peroxide solution.

[0111] [I-60] The method according to any one of [I-1] to [I-56], wherein in the method, the oxidizing agent is a 25% by weight to 65% by weight aqueous hydrogen peroxide solution.

[0112] [I-61] The method according to any one of [I-1] to [I-60], wherein in the method, the oxidant is used in an amount of 2 mol to 8 mol based on 1 mol of the compound of formula (1).

[0113] [I-62] The method according to any one of [I-1] to [I-60], wherein in the method, the oxidant is used in an amount of 2 mol to 5 mol based on 1 mol of the compound of formula (1).

[0114] [I-63] The method according to any one of [I-1] to [I-60], wherein in the method, the amount of the oxidant used is 2.5 mol to 4 mol based on 1 mol of the compound of formula (1).

[0115] [I-64] The method according to any one of [I-1] to [I-63], wherein in the method,

[0116] In formula (1) and formula (2),

[0117] R 1 is (C1-C4)alkyl,

[0118] R 2 is a (C1-C4)perfluoroalkyl group,

[0119] R 3 is (C1-C4)alkyl optionally substituted by 1 to 9 fluorine atoms,

[0120] R 4 and R 5 Each is independently (C1-C4) alkyl.

[0121] [I-65] The method according to any one of [I-1] to [I-63], wherein in the method,

[0122] In formula (1) and formula (2),

[0123] R 1 It is methyl.

[0124] R 2 is trifluoromethyl,

[0125] R 3 is difluoromethyl,

[0126] R 4 and R 5 It's methyl.

[0127] In another aspect, the present invention is as follows.

[0128] [II-1] A method for producing a compound of formula (2), comprising reacting a compound of formula (1) with an oxidizing agent in the presence of a halogenated acetic acid and in the absence of a transition metal:

[0129] [Chemistry 7]

[0130]

[0131] In formula (1) and formula (2),

[0132] R 1 , R 2 and R 3 each independently represents (C1-C6)alkyl optionally substituted by one or more substituents, (C3-C6)cycloalkyl optionally substituted by one or more substituents, (C2-C6)alkenyl optionally substituted by one or more substituents, (C2-C6)alkynyl optionally substituted by one or more substituents, or (C6-C10)aryl optionally substituted by one or more substituents;

[0133] R 4 and R 5 each independently represents (C1-C6)alkyl optionally substituted by one or more substituents, (C3-C6)cycloalkyl optionally substituted by one or more substituents, (C2-C6)alkenyl optionally substituted by one or more substituents, (C2-C6)alkynyl optionally substituted by one or more substituents, (C1-C6)alkoxy optionally substituted by one or more substituents, or (C6-C10)aryl optionally substituted by one or more substituents, or

[0134] R 4 and R 5 Together with the carbon atoms to which they are attached, they form a 4- to 12-membered carbocyclic ring, which is optionally substituted by one or more substituents.

[0135] [II-2] The method according to [II-1], wherein in the method, the halogenated acetic acid is selected from monochloroacetic acid, dichloroacetic acid and trichloroacetic acid.

[0136] [II-3] The method according to [II-1], wherein in the method, the halogenated acetic acid is dichloroacetic acid.

[0137] [II-4] The method according to [II-1], wherein in the method, the halogenated acetic acid is trichloroacetic acid.

[0138] [II-5] The method according to any one of [II-1] to [II-4], wherein in the method, the oxidizing agent is hydrogen peroxide.

[0139] [II-6] The method according to any one of [II-1] to [II-5], wherein in the method,

[0140] In formula (1) and formula (2),

[0141] R 1 is (C1-C4)alkyl,

[0142] R 2 is a (C1-C4)perfluoroalkyl group,

[0143] R 3 is (C1-C4)alkyl optionally substituted by 1 to 9 fluorine atoms,

[0144] R 4 and R 5 Each is independently (C1-C4) alkyl.

[0145] [II-7] The method according to any one of [II-1] to [II-5], wherein in the method,

[0146] In formula (1) and formula (2),

[0147] R 1 It is methyl.

[0148] R 2 is trifluoromethyl,

[0149] R 3 is difluoromethyl,

[0150] R 4 and R 5 It's methyl.

[0151] The symbols and terms used in this manual are explained below.

[0152] In this manual, the following abbreviations and prefixes are used and their meanings are as follows:

[0153] Me:Methyl

[0154] Et: Ethyl

[0155] Pr, n-Pr and Pr-n: Propyl (i.e. n-propyl)

[0156] i-Pr and Pr-i: isopropyl

[0157] Bu, n-Bu and Bu-n: butyl (i.e. n-butyl)

[0158] s-Bu and Bu-s: sec-butyl (i.e., sec-butyl)

[0159] i-Bu and Bu-i: isobutyl

[0160] t-Bu and Bu-t: tert-butyl (i.e. tert-butyl)

[0161] Ph: phenyl

[0162] n-: positive

[0163] s- and sec-:

[0164] i- and iso-: different

[0165] t- and tert-: uncle

[0166] c- and cyc-: ring

[0167] o-: adjacent

[0168] m-: room

[0169] p-: yes

[0170] The term "nitro" refers to the substituent "-NO2".

[0171] The term "cyano" or "nitrile" refers to the substituent "-CN".

[0172] The term "hydroxy" refers to the substituent "-OH".

[0173] The term "amino" refers to the substituent "-NH2".

[0174] (Ca-Cb) means the number of carbon atoms is a to b. For example, "(C1-C4)" in "(C1-C4)alkyl" means the number of carbon atoms in the alkyl group is 1 to 4, and "(C2-C5)" means the number of carbon atoms in the alkyl group is 2 to 5. "(Ca-Cb)" indicating the number of carbon atoms can be written as "Ca-Cb" without parentheses. So, for example, "C1-C4" in "C1-C4alkyl" means the number of carbon atoms in the alkyl group is 1 to 4.

[0175] In the specification, the general concept such as "alkyl" should be interpreted as including straight chain and branched chain, such as butyl and tert-butyl. On the other hand, for example, the subordinate concept "butyl" refers to the straight chain "n-butyl" but not the branched chain "tert-butyl". Branched chain isomers such as "tert-butyl" will be specifically mentioned when necessary.

[0176] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0177] (C1-C6) alkyl refers to a straight chain alkyl or branched chain alkyl having 1 to 6 carbon atoms. Examples of (C1-C6) alkyl include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, and hexyl.

[0178] The (C1-C4)alkyl group refers to a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the (C1-C4)alkyl group include suitable examples of the above-mentioned (C1-C6)alkyl group.

[0179] The (C3-C6)cycloalkyl group refers to a cycloalkyl group having 3 to 6 carbon atoms. Examples of the (C3-C6)cycloalkyl group are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0180] (C2-C6)alkenyl refers to a straight or branched alkenyl group having 2 to 6 carbon atoms. Examples of (C2-C6)alkenyl include, but are not limited to, ethenyl, 1-propenyl, isopropenyl, 2-propenyl, 1-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-pentenyl, and 1-hexenyl.

[0181] (C2-C6) alkynyl refers to a straight chain alkynyl or branched chain alkynyl having 2 to 6 carbon atoms. Examples of (C2-C6) alkynyl include, but are not limited to, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and 1-hexynyl.

[0182] Examples of (C6-C10)aryl are phenyl, 1-naphthyl and 2-naphthyl.

[0183] The (C1-C6)haloalkyl group refers to a straight or branched alkyl group having 1 to 6 carbon atoms substituted by 1 to 13 identical or different halogen atoms, wherein the halogen atom has the same meaning as defined above. Examples of (C1-C6)haloalkyl include, but are not limited to, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, bromodifluoromethyl, 2-fluoroethyl, 1-chloroethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3-fluoropropyl, 3-chloropropyl, 2-chloro-1-methylethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, heptafluoropropyl, 1,2,2,2-tetrafluoro-1-trifluoromethylethyl, 4-fluorobutyl, 4-chlorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, nonafluorobutyl, 1,1,2,3,3,3-hexafluoro-2-trifluoromethylpropyl, 2,2,2-trifluoro-1,1-bis(trifluoromethyl)ethyl, undecafluoropentyl, and tridecafluorohexyl.

[0184] (C1-C4) perfluoroalkyl refers to a linear or branched alkyl group having 1 to 4 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms. Examples of (C1-C4) perfluoroalkyl groups are trifluoromethyl (i.e., -CF3), pentafluoroethyl (i.e., -CF2CF3), heptafluoropropyl (i.e., -CF2CF2CF3), 1,2,2,2-tetrafluoro-1-trifluoromethylethyl (i.e., -CF(CF3)2), nonafluorobutyl (i.e., -CF2CF2CF2CF3), 1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl (i.e., -CF(CF3)CF2CF3), 1,1,2,3,3,3-hexafluoro-2-trifluoromethylpropyl (i.e., -CF2CF(CF3)2) and 2,2,2-trifluoro-1,1-bis(trifluoromethyl)ethyl (i.e., -C(CF3)3).

[0185] (C1-C6) alkoxy refers to (C1-C6) alkyl-O-, wherein the (C1-C6) alkyl portion has the same meaning as defined above. Examples of (C1-C6) alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentoxy, isopentyloxy, neopentyloxy, and hexyloxy.

[0186] (C1-C6) alcohol refers to (C1-C6) alkyl-OH, wherein the (C1-C6) alkyl moiety has the same meaning as defined above. Examples of (C1-C6) alcohols include, but are not limited to, methanol, ethanol, propanol (i.e., 1-propanol), 2-propanol, butanol (i.e., 1-butanol), sec-butanol, isobutanol, tert-butanol, amyl alcohol (i.e., 1-pentanol), sec-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentanol, tert-pentanol, hexanol (i.e., 1-hexanol), and cyclohexanol. Polyols (e.g., diols and triols) having 1 to 6 carbon atoms, such as ethylene glycol, propylene glycol, and glycerol, are counterparts of (C1-C6) alcohols.

[0187] Examples of 4- to 12-membered carbocyclic rings include, but are not limited to, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, and cyclododecane.

[0188] In the present specification, the "substituents" in the phrase "optionally substituted with one or more substituents" are not particularly limited as long as they are chemically acceptable and exhibit the effects of the present invention.

[0189] In the present specification, examples of the "substituent" in the phrase "optionally substituted with one or more substituents" include, but are not limited to, one or more substituents (preferably 1 to 3 substituents) independently selected from substituent group (a).

[0190] Substituent group (a) is a group consisting of halogen atoms, nitro, cyano, hydroxyl, amino, (C1-C6) alkyl, (C1-C6) haloalkyl, (C3-C6) cycloalkyl, (C2-C6) alkenyl, (C2-C6) alkynyl, (C1-C6) alkoxy, phenyl and phenoxy.

[0191] In addition, one or more substituents (preferably 1 to 3 substituents) independently selected from substituent group (a) may be substituted by one or more substituents (preferably 1 to 3 substituents) independently selected from substituent group (b). In this article, substituent group (b) is the same as substituent group (a).

[0192] Examples of “(C1-C6)alkyl optionally substituted by one or more substituents” include, but are not limited to, (C1-C6)haloalkyl, (C1-C4)perfluoroalkyl, (C1-C4)alkyl optionally substituted by 1 to 9 fluorine atoms.

[0193] Examples of (C1-C4)alkyl groups optionally substituted with 1 to 9 fluorine atoms include, but are not limited to, fluoromethyl (i.e., -CH2F), difluoromethyl (i.e., -CHF2), trifluoromethyl (i.e., -CF3), 2-fluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3-fluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, heptafluoropropyl, 1,2,2,2-tetrafluoro-1-trifluoromethylethyl, 4-fluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, nonafluorobutyl, 1,1,2,3,3,3-hexafluoro-2-trifluoromethylpropyl, and 2,2,2-trifluoro-1,1-bis(trifluoromethyl)ethyl.

[0194] In this specification, when referring to a substituent (e.g., R 1 , R 2 , R 3 , R 4 and R 5 The phrase "as described in the present specification" and similar phrases used when referring to the present invention are incorporated by reference into all definitions of substituents in the present specification and all examples, preferred examples, more preferred examples, further preferred examples and particularly preferred examples, if any.

[0195] In the present specification, the non-limiting terms "comprise(s) / comprising" may be arbitrarily replaced by the limiting phrases "consist(s) of / consisting of", respectively.

[0196] Unless otherwise defined, all technical and scientific terms used in the specification have the same meaning as commonly understood by one of ordinary skill in the art to which the present disclosure belongs.

[0197] Unless otherwise indicated, the numbers used in this specification to represent features such as quantity, size, concentration, and reaction conditions are understood to be modified by the term "about". In some embodiments, the disclosed values ​​are interpreted using the number of reported significant figures and conventional rounding. In some embodiments, the disclosed values ​​are interpreted as including errors necessarily caused by the standard deviation present in their respective test measurements.

[0198] (Raw material: compound of formula (1))

[0199] As a raw material, a compound of formula (1) is used. The compound of formula (1) is a known compound, or can be manufactured from a known compound according to a known method. For example, the preparation of the compound of formula (1) is described in reference examples 1-1, 1-2 and 1-3 of WO 2004 / 013106 A1 (patent document 2), examples 3-5 of WO 2005 / 095352 A1 (patent document 3), and examples 1-5 of WO 2005 / 105755 A1 (patent document 4).

[0200] (Product: Compound of formula (2))

[0201] The product is a compound of formula (2) corresponding to the compound of formula (1) used as the starting material.

[0202] In formula (1) and formula (2), R 1 , R 2 , R 3 , R 4 and R 5 As defined above.

[0203] Particularly preferred specific examples of the compound of formula (2) are as follows:

[0204] [Chemistry 8]

[0205]

[0206] The intermediate of the oxidation reaction is a compound of formula (3) corresponding to the compound of formula (1) used as a starting material.

[0207] [Chemistry 9]

[0208]

[0209] Specific examples of the compound of formula (3) are shown below:

[0210] [Chemistry 10]

[0211]

[0212] As described above, in the method for producing the compound of formula (2) (SO2 derivative) from the compound of formula (1) (S derivative), it is desirable that the oxidation reaction proceeds sufficiently and the proportion of the compound of formula (3) (SO derivative) in the product is sufficiently low. For example, in the reaction mixture after the reaction, the proportion of the compound of formula (3) (SO derivative) is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less, further preferably 2% or less, and further preferably 1% or less.

[0213] (Oxidant)

[0214] As the oxidant, peroxide, alkali metal persulfate, ammonium persulfate, alkali metal hydrogen persulfate, hypochlorite, etc. can be used. Preferably, hydrogen peroxide, alkali metal persulfate, ammonium persulfate and alkali metal hydrogen persulfate can be used, more preferably, hydrogen peroxide and alkali metal hydrogen persulfate can be used, further preferably, hydrogen peroxide, sodium hydrogen persulfate, sodium persulfate, potassium persulfate, ammonium persulfate and potassium hydrogen persulfate can be used, and particularly preferably, hydrogen peroxide can be used.

[0215] As long as the reaction proceeds, the form of hydrogen peroxide can be in any form. The form of hydrogen peroxide can be appropriately selected by those skilled in the art. However, in view of safety, danger, economic benefits, etc., preferred examples of the form of hydrogen peroxide include 10% to 70% by weight of aqueous hydrogen peroxide solution, more preferably 20% to 70% by weight of aqueous hydrogen peroxide solution, still more preferably 25% to 65% by weight of aqueous hydrogen peroxide solution, further preferably 30% to 65% by weight of aqueous hydrogen peroxide solution, and particularly preferably 30% to 60% by weight of aqueous hydrogen peroxide solution. Specific examples of the form of hydrogen peroxide include, but are not limited to, 25% by weight of aqueous hydrogen peroxide solution, 30% by weight of aqueous hydrogen peroxide solution, 35% by weight of aqueous hydrogen peroxide solution, 50% by weight of aqueous hydrogen peroxide solution, and 60% by weight of aqueous hydrogen peroxide solution. For the concentration range of hydrogen peroxide, it can be any combination of the lower limit and the upper limit of the above range, and any combination of the lower limit and the upper limit of the above range is also within the scope of the present invention.

[0216] As long as the reaction proceeds, the amount of hydrogen peroxide can be any amount. The amount of hydrogen peroxide used can be appropriately adjusted by those skilled in the art. However, considering aspects such as yield, by-product inhibition, economic benefit, and safety, based on 1 mole of the compound of formula (1) (raw material), the lower limit of the amount of hydrogen peroxide used is, for example, 2 moles or more, 2.3 moles or more, 2.5 moles or more, or 2.8 moles or more. Based on 1 mole of the compound of formula (1) (raw material), the upper limit of the amount of hydrogen peroxide used is, for example, 10 moles or less, 8 moles or less, 7 moles or less, 6 moles or less, 5 moles or less, 4 moles or less, or 3 moles or less. The amount of hydrogen peroxide used is in the range of any combination of the lower limit and the upper limit of the above range. Based on 1 mole of the compound of formula (1) (raw material), the amount of hydrogen peroxide used is, for example, 2 to 10 moles, preferably 2 to 8 moles, more preferably 2 to 5 moles, further preferably 2 to 4 moles, further preferably 2.5 to 4 moles, and further preferably 2.5 to 3 moles.

[0217] (In the absence of transition metals)

[0218] The oxidation reaction using hydrogen peroxide as an oxidant in the presence of a transition metal catalyst has been reported. However, in the method of the present invention, a transition metal catalyst is not required. Therefore, the term "in the absence of a transition metal" refers to not using a catalyst containing a transition metal catalyst. Therefore, "in the absence of a transition metal" in this specification can be arbitrarily replaced by "in the absence of a transition metal catalyst". Examples of transition metals that are not used include, but are not limited to, tungsten, molybdenum, iron, manganese, vanadium, niobium, tantalum, titanium, zirconium and copper. Examples of transition metal catalysts that are not used include, but are not limited to, tungsten catalysts (e.g., sodium tungstate dihydrate), molybdenum catalysts (e.g., ammonium molybdate tetrahydrate), iron catalysts (e.g., iron (III) acetylacetonate and iron (III) chloride), manganese catalysts (e.g., manganese (III) acetylacetonate), vanadium catalysts (e.g., vanadium acetylacetonate), niobium catalysts (e.g., sodium niobate), tantalum catalysts (e.g., lithium tantalate), titanium catalysts (e.g., titanium acetylacetonate and titanium tetrachloride), zirconium catalysts (e.g., zirconium oxide chloride octahydrate) and copper catalysts (e.g., copper acetate (II) and copper bromide (I)).

[0219] (Haloacetic acid)

[0220] Taking into account the yield, by-product suppression, economic benefits, etc., examples of halogenated acetic acids include, but are not limited to, the following: monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, bromochloroacetic acid, dibromoacetic acid, bromodichloroacetic acid, dibromochloroacetic acid, tribromoacetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, and mixtures thereof, preferably monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and mixtures thereof, and more preferably dichloroacetic acid, trichloroacetic acid, and mixtures thereof.

[0221] Haloacetic acid can be used alone or in any combination of two or more. As long as the reaction is carried out, the haloacetic acid can be in any form. The form of the haloacetic acid can be appropriately selected by those skilled in the art.

[0222] (Lower limit of the amount of halogenated acetic acid used)

[0223] As long as the effect of the present invention is shown, the amount of carboxylic acid used is not particularly limited. However, considering the yield, by-product suppression, economic benefit, etc., in one embodiment, based on 1 mole of the compound of formula (1) (raw material), the lower limit of the amount of haloacetic acid used is, for example, more than 0 (zero) mole, preferably 1 mole or more, 2 moles or more, or 3 moles or more, more preferably 5 moles or more, or 6 moles or more, further preferably 8 moles or more, 9 moles or more, or 10 moles or more, and further preferably 12 moles or more, 15 moles or more, or 18 moles or more.

[0224] As considered above, in another embodiment, based on 1 mol of the compound of formula (1) (raw material), the lower limit of the amount of haloacetic acid used is, for example, more than 0 (zero) liter, preferably 0.1 liter or more, 0.2 liter or more, or 0.3 liter or more, more preferably 0.4 liter or more, 0.5 liter or more, or 0.6 liter or more, further preferably 0.8 liter or more, 0.9 liter or more, or 1.0 liter or more, and even more preferably 1.2 liter or more, 1.3 liter or more, or 1.5 liter or more.

[0225] (Upper limit of the amount of haloacetic acid used)

[0226] As considered above, in one embodiment, based on 1 mole of the compound of formula (1) (raw material), the upper limit of the amount of the haloacetic acid used is, for example, 100 moles or less, preferably 60 moles or less, more preferably 35 moles or less, further preferably 25 moles or less, and further preferably 20 moles or less.

[0227] As considered above, in another embodiment, the upper limit of the amount of haloacetic acid used is, for example, 10.0 liters or less, preferably 5.0 liters or less, more preferably 3.0 liters or less, and further preferably 2.0 liters or less, based on 1 mol of the compound of formula (1) (raw material).

[0228] (Range of the amount of halogenated acetic acid used)

[0229] Consider the same as described above, in one embodiment, the scope of the use amount of haloacetic acid is any suitable and arbitrary combination of the above lower limit and upper limit. The example of the combination of upper limit and lower limit includes but is not limited to the following: based on 1 mole of formula (1) compound (raw material), the use amount of haloacetic acid is, for example, 3 moles to 60 moles, preferably 5 moles to 35 moles, 8 moles to 35 moles, or 10 moles to 35 moles.

[0230] As mentioned above, in another embodiment, the scope of the amount of haloacetic acid is any suitable and arbitrary combination of the above lower limit and upper limit. Examples of the combination of upper and lower limits include, but are not limited to, the following: Based on 1 mole of compound of formula (1) (raw material), the amount of haloacetic acid is, for example, 0.3 to 5.0 liters, preferably 0.5 to 3.0 liters, 0.8 to 3.0 liters, or 1.0 to 3.0 liters.

[0231] Haloacetic acid can also be used as a solvent. In this case, the haloacetic acid promotes the reaction itself and also acts as a solvent.

[0232] As long as the reaction is carried out, the solvent can be a monolayer, or it can be divided into two layers. As long as the reaction is carried out, the reaction system can be homogeneous or inhomogeneous. However, after the present invention is completed, the following discovery has been made by studying the present invention. In the present invention, when using haloacetic acid, particularly when using haloacetic acid such as dichloroacetic acid or trichloroacetic acid etc. as solvent, from the perspective of the affinity of the components in the reaction system such as raw material, product, reactant and solvent etc. and / or the homogeneity of the reaction system, favorable conditions (reaction system) are obtained in the present invention. As a result, for example, high response rate is obtained. Faster reaction is preferred industrially. In addition, it has been found that, in the present invention, stirring is also easy to carry out.

[0233] (Acid Catalyst)

[0234] Oxidation reaction of the present invention can be carried out in the presence of an acid catalyst, or in the absence of an acid catalyst. Those skilled in the art can appropriately determine whether to use an acid catalyst. In this article, an acid catalyst refers to an acid other than halogenated acetic acid. Examples of acid catalysts include, but are not limited to, the following: mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and phosphoric acids such as phosphoric acid, methyl phosphate, ethyl phosphate and phenyl phosphate, preferably sulfuric acid, phosphoric acid or phenyl phosphate, more preferably sulfuric acid or phenyl phosphate, further preferably sulfuric acid. The acid catalyst can be its salt.

[0235] The acid catalyst can be used alone or in combination of two or more in any proportion. As long as the reaction is carried out, the acid catalyst can be in any form. For example, examples of sulfuric acid include but are not limited to 50% to 98% sulfuric acid and 50% to 100% sulfuric acid, preferably 90% to 98% sulfuric acid and 90% to 100% sulfuric acid (concentrated sulfuric acid). The form of the acid catalyst can be appropriately selected by those skilled in the art. As long as the reaction is carried out, the amount of the acid catalyst can be any amount. The amount of the acid catalyst can be appropriately adjusted by those skilled in the art. However, considering yield, by-product suppression, economic benefit, etc., when the reaction of the present invention is carried out in the presence of an acid catalyst, based on 1 mole of formula (1) compound (raw material), the amount of the acid catalyst is, for example, greater than 0 (zero) to 0.5 mole, 0.01 mole to 0.3 mole or 0.05 mole to 0.2 mole.

[0236] (Phase transfer catalyst)

[0237] The oxidation reaction of the present invention can be carried out in the presence of a phase transfer catalyst, or in the absence of a phase transfer catalyst. Those skilled in the art can appropriately determine whether to use a phase transfer catalyst. The example of a phase transfer catalyst includes, but is not limited to, the following: quaternary ammonium salts (e.g., tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, octyltrimethylammonium chloride, octyltrimethylammonium bromide, trioctylmethylammonium chloride, trioctylmethylammonium bromide, benzyllauryldimethylammonium chloride (benzyldodecyldimethylammonium chloride), benzyllauryldimethylammonium bromide (benzyldodecyldimethyl bromide) The phase transfer catalyst preferably includes tetrabutylammonium chloride, tetrabutylammonium bromide and tetrabutylammonium hydrogen sulfate, and more preferably tetrabutylammonium hydrogen sulfate. Tetrabutylammonium hydrogen sulfate can be abbreviated as TBAHS.

[0238] Phase transfer catalyst can be used alone, and can also be used in combination of two or more in any proportion. As long as the reaction is carried out, the phase transfer catalyst can be in any form. Those skilled in the art can appropriately select the form of the phase transfer catalyst. As long as the reaction is carried out, the usage amount of the phase transfer catalyst can be any amount. The usage amount of the phase transfer catalyst can be appropriately adjusted by those skilled in the art. However, considering the yield, by-product inhibition, economic benefit, etc., when the reaction of the present invention is carried out in the presence of a phase transfer catalyst, based on 1 mole of formula (1) compound (raw material), the usage amount of the phase transfer catalyst is, for example, greater than 0 (zero) to 0.5 mole, 0.01 mole to 0.3 mole or 0.05 mole to 0.2 mole.

[0239] (Reaction solvent)

[0240] From the viewpoint of making the reaction proceed smoothly, the reaction is preferably carried out in the presence of a solvent. As long as the reaction proceeds, the reaction solvent can be any solvent. The reaction solvent can be a haloacetic acid or an organic solvent other than the haloacetic acid. In either case, the reaction can be carried out in the presence of an aqueous solvent.

[0241] Examples of organic solvents other than halogenated acetic acids include, but are not limited to, the following: aromatic hydrocarbon derivatives (e.g., benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, and nitrobenzene, etc.), halogenated aliphatic hydrocarbons (e.g., dichloromethane, 1,2-dichloroethane (EDC), etc.), alcohols (e.g., methanol, ethanol, propanol, 2-propanol (2-propanol is also known as isopropyl alcohol or isopropanol), butanol, sec-butanol, isobutanol, and tert-butanol (tert-butanol is also known as tert-butyl alcohol), pentanol, sec-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentanol, tert-pentanol, hexanol, and cyclohexanol, etc.), nitriles (e.g., acetonitrile, propionitrile, etc.), carboxylic acids (e.g., acetic acid, propionic acid, etc.), carboxylic acid esters (e.g., methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate and isomers thereof, amyl acetate and isomers thereof, etc. (in the present invention, “acetonitrile” is referred to as “acetonitrile”). The isomers of butyl acetate are equivalent to "butyl acetate", and the isomers of amyl acetate are equivalent to "amyl acetate"), ethers (for example, tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, dibutyl ether, di-tert-butyl ether, cyclopentyl methyl ether (CPME), methyl tert-butyl ether, 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether, etc.), ketones (for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone (MIPK), methyl isobutyl ketone (MIBK)), amides (for example, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP)), ureas (for example, N,N'-dimethylimidazolidinone (DMI), tetramethylurea, etc.), sulfones (for example, cyclopentane, etc.), and any combination thereof in any proportion.

[0242] Examples of the organic solvent other than the halogenated acetic acid preferably include one or more (preferably one or two, more preferably one) organic solvents selected from nitriles, carboxylic acids and amides, and the organic solvent other than the halogenated acetic acid is more preferably nitriles.

[0243] As considered above, preferred specific examples of the organic solvent other than the halogenated acetic acid include one or more (preferably one or two, more preferably one) organic solvents selected from acetonitrile, propionitrile, acetic acid, propionic acid, N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAC), and the organic solvent other than the halogenated acetic acid is more preferably acetonitrile.

[0244] As long as the reaction system can be fully stirred, the amount of the organic solvent other than the haloacetic acid used in the reaction is not particularly limited. However, in consideration of yield, by-product suppression, economic benefit, etc., when an organic solvent other than the haloacetic acid is used, the lower limit of the amount of the organic solvent other than the haloacetic acid is, for example, more than 0 (zero) liter, preferably 0.3 liter or more, or 0.4 liter or more, more preferably 0.5 liter or more, and further preferably 0.8 liter or more, or 1.0 liter or more, based on 1 mol of the compound of formula (1) (raw material).

[0245] As considered above, when an organic solvent other than halogenated acetic acid is used, the upper limit of the amount of the organic solvent other than halogenated acetic acid based on 1 mol of the compound of formula (1) (raw material) is, for example,

[0246] As considered above, in another embodiment, the upper limit of the amount of halogenated acetic acid is, for example, 10.0 liters or less, preferably 5.0 liters or less, more preferably 3.0 liters or less, and further preferably 2.0 liters or less, based on 1 mol of the compound of formula (1) (raw material).

[0247] As mentioned above, when an organic solvent other than haloacetic acid is used, the range of the amount of haloacetic acid used is any suitable and arbitrary combination of the above lower limit and upper limit. Examples of the combination of upper and lower limits include, but are not limited to, the following: Based on 1 mole of compound of formula (1) (raw material), the amount of haloacetic acid used is, for example, 0.3 liters to 5.0 liters, preferably 0.5 liters to 3.0 liters, or 0.8 liters to 2.0 liters.

[0248] When a combination of two or more reaction solvents is used, the ratio of the two or more reaction solvents may be any ratio as long as the reaction proceeds.

[0249] (Reaction temperature)

[0250] The reaction temperature is not particularly limited. However, considering the yield, by-product suppression, economic benefits, etc., the reaction temperature is, for example, the range of any combination of the lower limit and the upper limit of the following range: In one embodiment, the reaction temperature is, for example, 0 (zero) ° C to 100 ° C, or 10 ° C to 100 ° C, preferably 30 ° C to 100 ° C, more preferably 30 ° C to 80 ° C, further preferably 40 ° C to 80 ° C, further preferably 40 ° C to 70 ° C, further preferably 40 ° C to 65 ° C, and further preferably 40 ° C to 60 ° C. In another embodiment, the reaction temperature is, for example, 40 ° C to 100 ° C, preferably 45 ° C to 100 ° C, more preferably 45 ° C to 80 ° C, further preferably 45 ° C to 70 ° C, and further preferably 45 ° C to 60 ° C.

[0251] (Reaction time)

[0252] The reaction time is not particularly limited. The reaction time can be appropriately adjusted by those skilled in the art. However, considering the inhibition of yield, by-product, economic benefit, etc., in one embodiment, the reaction time is, for example, 5 minutes to 48 hours, preferably 10 minutes to 24 hours, more preferably 30 minutes to 24 hours, more preferably 30 minutes to 12 hours, more preferably 30 minutes to 6 hours, more preferably 30 minutes to 4 hours, more preferably 30 minutes to 2 hours. In another embodiment, the reaction time is, for example, 30 minutes to 48 hours, preferably 1 hour to 48 hours, more preferably 1 hour to 24 hours, more preferably 1 hour to 12 hours, more preferably 1 hour to 6 hours, more preferably 1 hour to 4 hours, more preferably 1 hour to 2 hours. For the scope of the reaction time, the lower limit and the upper limit of the above range can be arbitrarily combined, and any combination of the lower limit and the upper limit of the above range is within the scope of the present invention.

[0253] (addition time, aging time and reaction time)

[0254] In this specification, "ripening time" refers to the stirring time after the addition of raw materials and / or reactants (e.g., hydrogen peroxide, acidic compounds) is completed. When "batch addition" is adopted as a method for adding raw materials and reactants, etc., "reaction time" corresponds to "ripening time". When raw materials and / or reactants, etc. are added within a specified time, "addition time" refers to the time from the beginning of adding raw materials and / or reactants such as hydrogen peroxide to the completion of the addition of their entire amount. In this case as well, "ripening time" corresponds to the stirring time after the addition of raw materials and / or reactants is completed. In this case, it is presumed that the reaction begins after the addition is started, and "reaction time" is the sum of "addition time" and "ripening time".

[0255] (Embodiment of the reaction)

[0256] The reaction of the present invention can be carried out in a batch manner using a reactor, or by a flow reaction using a continuous reactor. A continuous reactor refers to a reactor for making the supply of raw materials and the reaction continuous and simultaneous. Examples of continuous reactors include flow reactors (flow reactors). A flow reactor is a reactor that can continuously supply raw materials and continuously react. Flow reactors are roughly divided into tubular flow reactors (including tubular flow reactors) and trough flow reactors, both of which can react in a continuous manner. The flow reactor of the present invention can be provided with a temperature control device for controlling the temperature of the flow reactor, and a temperature control unit for heating and cooling, for example, can be provided. The temperature control unit can be any suitable unit, and examples of the temperature control unit include a bath and a jacket. The form of the bath and the jacket can be any suitable form. In addition, as the material of the flow reactor, as long as it is not corroded by the raw materials and the solvent, there is no particular limitation, and examples thereof include metals (e.g., titanium, nickel, stainless steel and Hastelloy C), resins (e.g., fluororesins), glass and porcelain (e.g., ceramics).

[0257] The continuous reaction of the present invention does not exclude the implementation in a tank-type flow reactor. However, as a preferred flow reactor, for example, a tubular flow reactor can be cited. The tubular flow reactor of the present invention can be any one of a circular, rectangular, polygonal and elliptical tubular shape, or a combination of these shapes as long as it can make a liquid mixture or a gas-liquid mixture flow continuously through, and the cross-sectional shape of the tube can be any one of a circular, rectangular, polygonal and elliptical tubular shape, or a combination of these shapes. In addition, as the material of the tube, as long as it is not corroded by the raw material and the solvent, there is no particular restriction, and for example, metals (for example, titanium, nickel, stainless steel and Hastelloy C), resins (for example, fluororesins), glass and porcelain (for example, ceramics) can be cited, and preferably, fluororesins (for example, Teflon (registered trademark)) are preferred. In addition, the tubular flow reactor of the present invention can be provided with a temperature control device for controlling the temperature, and a temperature control unit for heating and cooling can be provided, for example. The temperature control unit can be any suitable unit, and examples of the temperature control unit include a bath and a jacket. The form of the bath and the jacket can be any suitable form. As such a flow reactor, for example, a spiral, shell and tube and plate heat exchange reactors can be used.

[0258] There is no particular restriction on the configuration method of the tube in the tubular flow reactor of the present invention, for example, it can be a straight line, a curve or a coil. As a preferred configuration method, for example, a tubular reactor in which the tube is configured as a coil can be cited. In addition, the tube can be one, or two or more tubes can be bundled regularly or irregularly at appropriate intervals. In this specification, for convenience, a tubular flow reactor with one tube is described, but if it is desired to improve production efficiency, a tubular flow reactor in which two or more tubes are bundled regularly or irregularly at appropriate intervals according to the description of this specification can be used.

[0259] In addition, the tubular flow reactor of the present invention may include a mixer as required. The mixer is not particularly limited as long as it has the function of continuously mixing two or more fluids such as gas and liquid or liquid and liquid, and a Y-type mixer, a T-type mixer and a pipeline mixer (including a pipeline mixer such as a static mixer) can be listed. A pipeline mixer including a static mixer can be a tubular flow reactor.

[0260] (Flow-through reaction)

[0261] When a flow-through type is adopted, a mixture of a specified amount of compound (1), an acidic compound, hydrogen peroxide and a solvent (if necessary, further addition may be made) is made to flow through a tubular reactor and react. In this case, it is preferred that the tubular reactor used has a heating device, and the mixture is made to flow through a reaction tube heated to a specified temperature. The reaction temperature is not particularly limited. However, in consideration of the yield, by-product suppression, economic benefits, etc., 0° C. (zero) to 120° C., preferably 30° C. to 100° C., can be exemplified.

[0262] The equivalent diameter of the tube in the tubular reactor of the present invention is not particularly limited as long as the liquid mixture or the gas-liquid mixture can flow continuously through it, but from the perspective of production efficiency, it is preferably 0.5 mm or larger. As a preferred equivalent diameter, about 0.5 mm to 50 mm can be cited, preferably about 0.5 mm to 30 mm.

[0263] The "equivalent diameter (De)" in the present invention is a value defined according to the following formula:

[0264] De=4·Af / Wp

[0265] Where Af represents the flow path cross-sectional area and Wp represents the wetted edge length.

[0266] For example, the equivalent diameter of a circular tube with radius r is:

[0267] De=4·πr 2 / 2πr

[0268] =2r

[0269] There is no particular limitation on the length of the tube of the tubular flow reactor of the present invention, as long as the raw material compound can be heated and reacted sufficiently. For example, 1 m or longer, preferably in the range of 5 m to 80 m. In order to effectively carry out the method of the present invention, the reaction must be carried out at a specified temperature, and / or in order to ensure sufficient reaction time, a length of 5 m or longer is generally preferred, but not limited thereto.

[0270] The flow rate in the flow-through reactor, preferably the tubular flow reactor, of the present invention depends on the equivalent diameter of the tube, but is usually 0.01 mL / min or more, preferably 0.05 mL / min or more.

[0271] The pressure in the tubular flow reactor is, for example, 0.1 MPa to 10 MPa, preferably 0.3 MPa to 5 MPa, but is not limited thereto.

[0272] (Post-treatment; Separation and Purification)

[0273] The compound of formula (2), especially the target product sulfonepyraclostrobin (2-a), can be separated and purified from the reaction mixture by methods known to those skilled in the art (e.g., extraction, washing, crystallization including recrystallization, crystal washing and / or other operations) and improved methods thereof, and any combination thereof.

[0274] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples in any way.

[0275] In this specification, each physical property and yield of Examples, Comparative Examples and Reference Examples were measured using the following instruments and conditions. In addition, the products obtained in the present invention are known compounds and were identified by conventional methods known to those skilled in the art.

[0276] (pH measurement)

[0277] Instrument: Glass electrode type hydrogen ion concentration meter, HM-20P manufactured by DKK-TOA Co., Ltd. or a concentration meter based thereon

[0278] (HPLC analysis: High Performance Liquid Chromatography analysis)

[0279] (HPLC analysis conditions)

[0280] Instrument: LC 2010 series products manufactured by Shimadzu Corporation or products based thereon

[0281] Chromatographic column: YMC-Pack, ODS-A, A-312 (150mm x 6.0mm ID, S-5μm, 120A)

[0282] Eluent:

[0283] [Table 1]

[0284] Time (minutes) Acetonitrile (%) 0.1% phosphoric acid aqueous solution (%) 0 45 55 10 45 55 15 80 20 20 80 20

[0285] Flow rate: 1.0ml / min

[0286] Detection: UV 230nm

[0287] Column temperature: 40°C

[0288] Injection volume: 5 μL

[0289] For HPLC analysis methods, please refer to the following documents as needed.

[0290] Document (a): (Company) The Chemical Society of Japan, "New Experimental Chemistry Lectures 9 Analytical Chemistry II", pp. 86-112 (1977), Published by Iizumi Shingo and Maruzen Co., Ltd.

[0291] Reference (b): (Company) The Chemical Society of Japan, "Experimental Chemistry Lectures 20-1 Analytical Chemistry", 5th edition, pages 130 to 151 (2007), published by Seishiro Murata and Maruzen Co., Ltd.

[0292] (yield and purity)

[0293] Unless otherwise specified, the yield in the present invention can be calculated based on the number of moles of the obtained target compound relative to the number of moles of the raw material compound (starting compound).

[0294] That is, the term "yield" refers to "molar yield".

[0295] Therefore, the yield is expressed by the following equation:

[0296] Yield (%) = (the number of moles of the target compound obtained) / (the number of moles of the starting compound)×100.

[0297] However, for example, when evaluating the reaction yield of the target product, the yield of impurities, and the purity of the product, HPLC area percentage analysis or GC area percentage analysis may be used.

[0298] In the present specification, room temperature and normal temperature are 10° C. to 30° C. In the present specification, “RT”, “rt”, “rt” and “rt” all refer to room temperature.

[0299] In the present specification, the term "overnight" means 8 hours to 16 hours.

[0300] In this specification, the operation of "aging" includes stirring the mixture by common methods known to those skilled in the art.

[0301] Example 1

[0302] Production of 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methanesulfonyl]-4,5-dihydro-5,5-dimethylisoxazole

[0303] [Chemistry 11]

[0304]

[0305] Under nitrogen flow, compound (1-a) (0.90 g, purity: 100%, 2.5 mmol, 100 mol%), dichloroacetic acid (5.85 g, 45.4 mmol, 1815 mol%, 1.5 L / mol), 35% aqueous hydrogen peroxide solution (0.69 g, 7.13 mmol, 285 mol%, containing 0.45 g (0.18 L / mol) of water) were added to the reaction flask, followed by stirring and aging for 1 hour at an internal temperature of 50° C. to 55° C. The resulting mixture was homogeneous from the beginning to the end of the reaction.

[0306] At this time, the reaction intermediate 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methylsulfinyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 3-a; SO derivative) was 0% (HPLC area percentage; 230 nm).

[0307] Acetonitrile was added to the reaction mixture, and analysis by HPLC external standard method revealed that the target product (2-a) was obtained with a yield of 88%.

[0308] Example 2

[0309] Production of 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methanesulfonyl]-4,5-dihydro-5,5-dimethylisoxazole

[0310] The reaction process is the same as that in Example 1.

[0311] Under nitrogen flow, compound (1-a) (0.90 g, purity: 100%, 2.5 mmol, 100 mol%), dichloroacetic acid (5.85 g, 45.4 mmol, 1815 mol%, 1.5 L / mol), 98% sulfuric acid (0.025 g, 0.25 mmol, 10 mol%) and 35% aqueous hydrogen peroxide solution (0.69 g, 7.13 mmol, 285 mol%, containing 0.45 g (0.18 L / mol) of water) were added to a reaction flask, followed by stirring and aging for 1 hour at an internal temperature of 50° C. to 55° C. The resulting mixture was homogeneous from the beginning to the end of the reaction.

[0312] At this time, the reaction intermediate 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methylsulfinyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 3-a; SO derivative) was 0% (HPLC area percentage; 230 nm).

[0313] Acetonitrile was added to the reaction mixture, and analysis by HPLC external standard method revealed that the target product (2-a) was obtained with a yield of 87%.

[0314] Example 3

[0315] Production of 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methanesulfonyl]-4,5-dihydro-5,5-dimethylisoxazole

[0316] The reaction process is the same as that in Example 1.

[0317] Under nitrogen flow, compound (1-a) (0.90 g, purity: 100%, 2.5 mmol, 100 mol%), dichloroacetic acid (1.95 g, 15.1 mmol, 605 mol%, 0.5 L / mol), acetonitrile (1.97 g, 1.0 L / mol) and 35% aqueous hydrogen peroxide solution (0.69 g, 7.13 mmol, 285 mol%, containing 0.45 g (0.18 L / mol) of water) were added to a reaction flask, followed by stirring and aging for 1 hour at an internal temperature of 50° C. to 55° C. The resulting mixture was homogeneous from the beginning to the end of the reaction.

[0318] At this time, the reaction intermediate 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methylsulfinyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 3-a; SO derivative) was 0% (HPLC area percentage; 230 nm).

[0319] Acetonitrile was added to the reaction mixture, and analysis by HPLC external standard method revealed that the target product (2-a) was obtained with a yield of 89%.

[0320] Example 4

[0321] Production of 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methanesulfonyl]-4,5-dihydro-5,5-dimethylisoxazole

[0322] The reaction process is the same as that in Example 1.

[0323] Under nitrogen flow, compound (1-a) (0.90 g, purity: 100%, 2.5 mmol, 100 mol%), dichloroacetic acid (1.95 g, 15.1 mmol, 605 mol%, 0.5 L / mol), trichloroacetic acid (3.79 g, 23.2 mmol, 929 mol%, 0.93 L / mol) and 35% aqueous hydrogen peroxide solution (0.69 g, 7.13 mmol, 285 mol%, containing 0.45 g (0.18 L / mol) of water) were added to a reaction flask, followed by stirring and aging for 1 hour at an internal temperature of 50° C. to 55° C. The resulting mixture was homogeneous from the beginning to the end of the reaction.

[0324] At this time, the reaction intermediate 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methylsulfinyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 3-a; SO derivative) was 0% (HPLC area percentage; 230 nm).

[0325] Acetonitrile was added to the reaction mixture, and analysis by HPLC external standard method revealed that the target product (2-a) was obtained with a yield of 88%.

[0326] Example 5

[0327] Production of 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methanesulfonyl]-4,5-dihydro-5,5-dimethylisoxazole

[0328] The reaction process is the same as that in Example 1.

[0329] Under nitrogen flow, compound (1-a) (0.90 g, purity: 100%, 2.5 mmol, 100 mol%), trichloroacetic acid (3.79 g, 23.2 mmol, 929 mol%, 0.93 L / mol) and 35% aqueous hydrogen peroxide solution (0.69 g, 7.13 mmol, 285 mol%, containing 0.45 g (0.18 L / mol) of water) were added to a reaction flask, followed by stirring and aging for 1 hour at an internal temperature of 50° C. to 55° C. The resulting mixture was homogeneous from the beginning to the end of the reaction.

[0330] At this time, the reaction intermediate 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methylsulfinyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 3-a; SO derivative) was 0% (HPLC area percentage; 230 nm).

[0331] Acetonitrile was added to the reaction mixture, and analysis by HPLC external standard method revealed that the target product (2-a) was obtained with a yield of 91%.

[0332] Example 6

[0333] Production of 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methanesulfonyl]-4,5-dihydro-5,5-dimethylisoxazole

[0334] The reaction process is the same as that in Example 1.

[0335] Under nitrogen flow, compound (1-a) (0.90 g, purity: 100%, 2.5 mmol, 100 mol%), chloroacetic acid (3.34 g, 35.3 mmol, 1412 mol%, 0.84 L / mol) and 35% aqueous hydrogen peroxide solution (0.69 g, 7.13 mmol, 285 mol%, containing 0.45 g (0.18 L / mol) of water) were added to a reaction flask, followed by stirring and aging at an internal temperature of 50° C. to 55° C. for 2.5 hours. At this time, crystals were precipitated and the mixture became a suspension. The resultant was further aged at the same temperature for 0.5 hours.

[0336] At this time, the reaction intermediate 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methylsulfinyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 3-a; SO derivative) was 0% (HPLC area percentage; 230 nm).

[0337] Acetonitrile was added to the reaction mixture to dissolve the reaction mixture into a homogeneous solution. As a result of analysis by HPLC external standard method, the target product (2-a) was obtained with a yield of 91%.

[0338] Reference Example 1

[0339] Reproduction experiment of Example 4 of CN 111574511 A (Patent Document 8)

[0340] Production of 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methanesulfonyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 2-a)

[0341] The reaction process is the same as that in Example 1.

[0342] Under a nitrogen flow, compound (1-a) (0.90 g, purity: 100%, 2.5 mmol, 100 mol%), methanol (2.97 g, 1.5 L / mol), 98% sulfuric acid (0.023 g, 0.225 mmol, 9 mol%) and 30% aqueous hydrogen peroxide solution (0.81 g, 7.12 mmol, 285 mol%, containing 0.57 g (0.2 L / mol) of water) were added to a reaction flask, followed by stirring and ripening at room temperature for 6 hours.

[0343] At this time, the reaction intermediate 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl)methylsulfinyl]-4,5-dihydro-5,5-dimethylisoxazole (Compound 3-a; SO derivative) was 13.97% (HPLC area percentage; 230 nm).

[0344] Acetonitrile was added to the reaction mixture to dissolve the reaction mixture into a homogeneous solution. Analysis by HPLC external standard method showed that the target product (2-a) was not obtained and the yield was 0%. This method was not reproducible.

[0345] For the purpose of describing and disclosing methods described in publications, patents, and patent applications that may be relevant to the description of this specification, all publications, patents, and patent applications described in this specification are fully incorporated into this specification by reference. To the extent necessary to understand or complete the disclosure of the present invention, all publications, patents, and patent applications described in this specification are expressly incorporated into this specification by reference to the same extent as each document is individually incorporated. All publications, patents, and patent applications discussed above and throughout this specification are provided only for disclosure as of the filing date of this application.

[0346] Any method and reagent similar or equivalent to that described in this specification can be used in the method and implementation of the present invention. Therefore, the present invention is not limited by the above description, but is defined by the claims and their equivalents. These equivalents all fall within the scope of the present invention defined by the appended claims.

[0347] Industrial Applicability

[0348] As disclosed in Patent Document 1, the compound of the general formula (2) (sulfone derivative: SO2 derivative) has excellent herbicidal activity. According to the present invention, there is provided an industrially advantageous new method for producing the compound of the general formula (2) useful as a herbicide.

[0349] As described above, the method of the present invention is economically efficient, environmentally friendly, and has a high industrial practical value. In particular, in the method of the present invention, the proportion of the compound of formula (3) (sulfoxide derivative: SO derivative) in the product is sufficiently low. In this article, the compound of formula (3) (sulfoxide derivative: SO derivative) is an intermediate of the oxidation reaction and may cause the herbicide to be reduced in quality and the crop to be damaged. In addition, the present invention also provides a method that can be implemented with reproducibility. Therefore, the present invention has a high industrial practical value.

Claims

1. A method for producing a compound of formula (2), comprising: The compound of formula (1) is reacted with an oxidizing agent in the presence of a haloacetic acid but without a transition metal: In formula (1) and formula (2), R 1 , R 2 and R 3 each independently represents (C1-C6)alkyl optionally substituted by one or more substituents, (C3-C6)cycloalkyl optionally substituted by one or more substituents, (C2-C6)alkenyl optionally substituted by one or more substituents, (C2-C6)alkynyl optionally substituted by one or more substituents, or (C6-C10)aryl optionally substituted by one or more substituents; R 4 and R 5 each independently represents (C1-C6)alkyl optionally substituted by one or more substituents, (C3-C6)cycloalkyl optionally substituted by one or more substituents, (C2-C6)alkenyl optionally substituted by one or more substituents, (C2-C6)alkynyl optionally substituted by one or more substituents, (C1-C6)alkoxy optionally substituted by one or more substituents, or (C6-C10)aryl optionally substituted by one or more substituents, or R 4 and R 5 Together with the carbon atoms to which they are attached, they form a 4- to 12-membered carbocyclic ring, which is optionally substituted by one or more substituents.

2. The process according to claim 1, wherein in the process, the halogenated acetic acid is selected from the group consisting of monochloroacetic acid, dichloroacetic acid and trichloroacetic acid.

3. The process according to claim 1, wherein in the process, the haloacetic acid is dichloroacetic acid.

4. The process according to claim 1, wherein in said process, the haloacetic acid is trichloroacetic acid.

5. The method according to any one of claims 1 to 4, wherein in the method the oxidizing agent is hydrogen peroxide.

6. The method according to any one of claims 1 to 5, wherein in the method, In formula (1) and formula (2), R 1 is (C1-C4)alkyl, R 2 is a (C1-C4)perfluoroalkyl group, R 3 is (C1-C4)alkyl optionally substituted by 1 to 9 fluorine atoms, R 4 and R 5 Each is independently (C1-C4) alkyl.

7. The method according to any one of claims 1 to 5, wherein in the method, in formula (1) and formula (2), R 1 It is methyl, R 2 is trifluoromethyl, R 3 is difluoromethyl, R 4 and R 5 It's methyl.

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