JP2017155002A - Method for producing sulfoxide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a sulfoxide derivative that is satisfactory industrially.SOLUTION: The present invention provides a method for producing a sulfoxide derivative represented by formula (1), characterized by making a sulfide derivative represented by formula (2) react with an oxidizing agent in the presence of a catalyst that is a metal-ligand complex comprising a metal compound and a specific ligand, and a specific benzoic acid compound (where R1 is a C1-C4 haloalkylthio, a C2-C10 alkyl group or the like; R2 and R3 independently represent H, a C1-C4 alkyl group or the like).SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a sulfoxide derivative.

  Sulfoxide derivatives are attracting attention in the field of agricultural chemicals (see Patent Document 1). Therefore, it is important that the sulfoxide derivative be produced selectively and in high yield. As a method for producing a sulfoxide derivative, oxidation of a sulfide derivative is known. However, in general, this method has a problem that a sulfon derivative, which is an over-oxidized product, is produced as a by-product. By-product sulfone derivatives that are not required reduce the yield of the desired sulfoxide derivative. Furthermore, because the physical properties of both derivatives are similar, in industrial production, by removing the by-product sulfone derivative from the crude product after the oxidation reaction, a purified target sulfoxide derivative can be obtained. Is difficult. That is, it is difficult to separate and purify the target product at a high yield on an industrial scale. Therefore, it has been desired that a sulfoxide derivative can be selectively produced while avoiding excessive oxidation to the sulfone derivative.

  Patent Document 1 discloses that a sulfoxide derivative can be produced by an oxidation reaction with metachloroperbenzoic acid (for example, see Examples 13 and 27 of Patent Document 1). However, considering environmental aspects, the use of metachloroperbenzoic acid is not preferred for industrial production. The reason is as follows. After the reaction, metachloroperbenzoic acid becomes metachlorobenzoic acid which becomes waste. As a result, the use of metachloroperbenzoic acid places a heavy burden on the environment. In addition, since metachloroperbenzoic acid is expensive, a method using metachloroperbenzoic acid is industrially unpreferable.

  On the other hand, oxidation using hydrogen peroxide is an industrially preferable and useful method. The reason is as follows. Hydrogen peroxide is environmentally friendly because it becomes harmless water after the reaction. Furthermore, hydrogen peroxide is industrially inexpensive.

  Non-Patent Document 1 discloses asymmetric oxidation from a sulfide derivative to an optically active sulfoxide derivative. Non-Patent Document 1 discloses a method using a conventionally known Schiff base as a ligand and a benzoic acid compound. This method has also been reported to give some yield. However, the method described in Non-Patent Document 1 requires further improvement in yield. In addition, Non-Patent Document 1 describes that the yield and enantiomeric excess change depending on the difference in the substituent of the aryl moiety of the arylalkyl sulfide derivative. However, Non-Patent Document 1 only discloses the yield and enantiomeric excess when the substituents are limited. In other words, Non-Patent Document 1 does not disclose a method for producing a target compound of the present invention that can provide a satisfactory and satisfactory yield.

  As benzoic acid compounds, it is reported that 4-methoxybenzoic acid alkali metal salts and 4- (N, N-dimethylamino) benzoic acid alkali metal salts are superior from the viewpoints of yield and enantiomeric excess. . Furthermore, the Schiff base of the ligand has been reported as follows. As the amine moiety of the Schiff base as a ligand, tert-leucinol was superior to valinol from the viewpoints of yield and enantiomeric excess. As the salicylaldehyde moiety of the Schiff base as a ligand, from the same viewpoint as described above, 3,5-diiodosalicylaldehyde and 3,5-dibromosalicylaldehyde were superior to unsubstituted salicylaldehyde (non- (See Patent Document 1 and Table 1). However, it has not been known whether or not these benzoic acid compounds and ligands have an industrially advantageous effect in the production of the target compound of the present invention. In addition, the use of 3,5-diiodosalicylaldehyde as the salicylaldehyde moiety of the Schiff base as a ligand is industrially unfavorable due to difficulty in availability, difficulty in industrial production, and / or cost. .

International Publication No. 2013/157229

Chem. Eur. J. et al. 2005, 11: 1086-1092

  There was an urgent need for a method for producing sulfoxide derivatives that can overcome one or more of the disadvantages or problems of the prior art described above.

  Accordingly, an object of the present invention is to provide a method for producing a sulfoxide derivative which is industrially preferable, economical and environmentally friendly.

  A more specific object of the present invention is to provide a method capable of producing a sulfoxide derivative selectively and in high yield. To achieve this goal, it is necessary to provide a controlled oxidation reaction from sulfide derivatives to sulfoxide derivatives that avoids over-oxidation to sulfone derivatives.

  Another more specific object of the present invention is to provide a method that is inexpensive and can reduce the environmental load.

  For example, one of the specific objects of the present invention is to produce a sulfoxide derivative using hydrogen peroxide, which is attracting attention as a clean and excellent oxidizing agent, without using metachloroperbenzoic acid as an oxidizing agent. It is to be.

  Furthermore, an inexpensive compound is preferable as the ligand of the catalyst used in the oxidation reaction. For example, as a substituent on the benzene ring in the ligand, a chlorine atom is acceptable, but an iodine atom is not preferable because it is expensive. In other words, an industrially preferred salicylaldehyde derivative is used as the salicylaldehyde moiety of the Schiff base as a ligand without using a salicylaldehyde derivative having the above-mentioned drawbacks such as 3,5-diiodosalicylaldehyde. It is desirable to do.

  In view of the above situation, the present inventor has intensively studied a method for producing a sulfoxide derivative. As a result, the inventor surprisingly has the general formula (1):

(In the formula, R ¹ , R ² and R ³ are as described later.)
A sulfoxide derivative represented by the general formula (2):

(In the formula, R ¹ , R ² and R ³ are as described later.)
A sulfide derivative represented by the general formula (3) as a metal compound and a ligand:

(In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷¹ and R ⁷² are as described later.)
And a catalyst that is a metal-ligand complex containing a compound represented by formula (4):

(In the formula, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , M and n are as described later.)
It discovered that it could manufacture by making it react with an oxidizing agent in presence of the benzoic acid compound represented by these. The present inventor has completed the present invention based on this finding.

  That is, the present invention solves the above problems by providing the inventions described in the following items [1] to [21].

  [1] General formula (1):

(Where
R ¹ is a C1-C10 alkyl group,
C3-C6 cycloalkyl C1-C6 alkyl group, wherein the C3-C6 cycloalkyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group or C1-C4 haloalkyl group. May be
A phenyl C1-C6 alkyl group, wherein the phenyl group moiety may be mono- or poly-substituted by halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C6 haloalkyl groups, cyano groups or nitro groups. Good,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
A C1-C4 haloalkylsulfonyl C2-C10 alkyl group,
A C1-C6 haloalkyl group,
C3-C6 cycloalkyl C1-C6 haloalkyl group, wherein the C3-C6 cycloalkyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group or C1-C6 haloalkyl group. May be
A phenyl C1-C6 haloalkyl group, wherein the phenyl group moiety may be mono- or poly-substituted by halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 haloalkyl groups, cyano groups or nitro groups. Or a C1-C4 haloalkylthio C1-C6 haloalkyl group;
R ² and R ³ are each independently a hydrogen atom, a halogen atom or a C1-C4 alkyl group. ) A sulfoxide derivative represented by the general formula (2):

(Wherein R ¹ , R ² and R ³ are as defined above.)
A sulfide derivative represented by the general formula (3) as a metal compound and a ligand:

(Where
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a phenyl C1-C6 alkyl group, a C6-C10 aryl group, a cyano group, a nitro group, or a C1-C6 alkoxy group. ;
R ⁶ is a C1-C4 alkyl group, a cyano group, a nitro group, a carboxy group, a C1-C4 alkoxycarbonyl group, a C1-C4 alkylcarbonyl group, a hydroxy C1-C4 alkyl group, a C1-C4 alkoxy C1-C4 alkyl group, An amino C1-C4 alkyl group, a cyano C1-C4 alkyl group, a nitro C1-C4 alkyl group, a carboxy C1-C4 alkyl group or a C1-C4 alkoxycarbonyl C1-C4 alkyl group;
R ⁷¹ and R ⁷² are each independently a hydrogen atom, a C1-C6 alkyl group, a phenyl C1-C6 alkyl group, or a C6-C10 aryl group. However, the case where R ⁷¹ and R ⁷² are hydrogen atoms is excluded. )
And a catalyst that is a metal-ligand complex containing a compound represented by formula (4):

(Where
A ¹ is a C1-C2 alkoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom or a C1-C2 alkoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a C1-C2 alkoxy group;
M is a hydrogen atom, an alkali metal atom or an alkaline earth metal atom; and n is 1 or 2. )
And reacting with an oxidizing agent in the presence of a benzoic acid compound represented by the formula:

[2] R ¹ is a C1-C10 alkyl group,
A C3-C6 cycloalkyl C1-C6 alkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono- or poly-substituted with a halogen atom or a C1-C4 alkyl group,
A phenyl C1-C6 alkyl group, wherein the phenyl group moiety may be mono- or poly-substituted with a halogen atom or a C1-C4 alkyl group,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
A C1-C4 haloalkylsulfonyl C2-C10 alkyl group,
A C1-C6 haloalkyl group,
A C3-C6 cycloalkyl C1-C6 haloalkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono- or polysubstituted by a halogen atom or a C1-C4 alkyl group, or a phenyl C1-C6 haloalkyl group, The method according to [1], wherein the phenyl group moiety may be mono-substituted or poly-substituted with a halogen atom or a C1-C4 alkyl group.

[3] R ¹ is a C1-C10 alkyl group,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
The method according to [1], which is a C1-C4 haloalkylsulfonyl C2-C10 alkyl group or a C1-C6 haloalkoxy group.

[4] The method according to [ ¹ ], wherein R ¹ is a C1-C4 haloalkylthio C2-C10 alkyl group; and R ² and R ³ are each independently a halogen atom or a C1-C4 alkyl group. .

[5] R ¹ is a 5-trifluoromethylthiopentyl group or 6-trifluoromethylthiohexyl group; and R ² is a fluorine atom and R ³ is a chlorine atom, or R ² and R ³ are methyl The method according to [1], which is a group.

[6] R ¹ is a 5-trifluoromethylthiopentyl group;
The method according to [1], wherein R ² is a fluorine atom; and R ³ is a chlorine atom.

[7] The method according to [1], wherein R ¹ is a 6-trifluoromethylthiohexyl group; and R ² and R ³ are methyl groups.

[8] The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom or a halogen atom;
R ⁶ is a hydroxymethyl group; and R ⁷¹ and R ⁷² are each independently a hydrogen atom or a C1-C6 alkyl group (except when R ⁷¹ and R ⁷² are a hydrogen atom), [1] The method according to any one of [7].

[9] The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom, a chlorine atom or a bromine atom;
[1] to [7] wherein R ⁶ is a hydroxymethyl group; and R ⁷¹ is a methyl group and R ⁷² is a methyl group, or R ⁷¹ is a hydrogen atom and R ⁷² is an isopropyl group. ] The method of any one of these.

[10] The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom or a chlorine atom;
[1] to [7] wherein R ⁶ is a hydroxymethyl group; and R ⁷¹ is a methyl group and R ⁷² is a methyl group, or R ⁷¹ is a hydrogen atom and R ⁷² is an isopropyl group. ] The method of any one of these.

[11] The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom;
R ⁶ is a hydroxymethyl group;
The method according to any one of [1] to [7], wherein ^R71 is a methyl group; and ^R72 is a methyl group.

[12] The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a chlorine atom;
R ⁶ is a hydroxymethyl group;
The method according to any one of [1] to [7], wherein ^R71 is a methyl group; and ^R72 is a methyl group.

[13] The method according to any one of [1] to [12], wherein M is an alkali metal atom; and n is 1.

[14] The method according to any one of [1] to [12], wherein M is a sodium atom; and n is 1.

[15] ^{A 1} is methoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom or a methoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
The method according to any one of [1] to [12], wherein M is a sodium atom; and n is 1.

[16] ^{A 1} is methoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
The method according to any one of [1] to [12], wherein M is a sodium atom; and n is 1.

[17] ^{A 1} is methoxy group;
A ² is a hydrogen atom;
A ³ is a methoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
The method according to any one of [1] to [12], wherein M is a sodium atom; and n is 1.

  [18] The method according to any one of [1] to [17], wherein the reaction is performed at −10 ° C. to 30 ° C.

  [19] The method according to any one of [1] to [17], wherein the reaction is performed at −5 ° C. to 10 ° C.

  [20] The method according to any one of [1] to [19], wherein the reaction yield is 90 to 100%.

  [21] The method according to any one of [1] to [19], wherein the reaction yield is 95 to 100%.

  The present invention provides a novel and industrially applicable production method for the sulfoxide derivative represented by the general formula (1) useful as an acaricide or the like. According to the present invention, there is provided a method for producing a sulfoxide derivative, which can solve one or more of the above-mentioned disadvantages or problems in the prior art.

  According to the present invention, the target sulfoxide derivative can be selectively produced while avoiding excessive oxidation to the sulfone derivative. At the same time, the desired sulfoxide derivative can be produced in high yield.

  Furthermore, since hydrogen peroxide is used without using metachloroperbenzoic acid as an oxidizing agent, the present invention can reduce the environmental burden.

  In addition, the method of the present invention does not require a salicylaldehyde derivative having the aforementioned disadvantages such as 3,5-diiodosalicylaldehyde as the salicylaldehyde moiety of the Schiff base as the ligand.

  Therefore, the method of the present invention is industrially favorable, economical and environmentally friendly.

  Hereinafter, the present invention will be described in detail.

  The method according to the invention comprises the following scheme:

(In the formula, R ¹ , R ² and R ³ are as described in [1] above.)
Indicated by.

  Terms and symbols used in this specification will be described below.

  The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. From the viewpoint of the usefulness and economics of the product, preferred examples of the halogen atom are a fluorine atom and a chlorine atom.

  Examples of the alkali metal atom include a lithium atom, a sodium atom, a potassium atom, a rubidium atom and a cesium atom, preferably a lithium atom, a sodium atom, a potassium atom and a cesium atom, more preferably a lithium atom, a sodium atom and a potassium atom.

  Examples of alkaline earth metal atoms include magnesium, calcium, strontium and barium atoms, preferably magnesium, calcium and barium atoms.

  “Ca to Cb” means that the number of carbon atoms is a to b. For example, “C1 to C4” of “C1 to C4 alkyl group” means that the alkyl group has 1 to 4 carbon atoms.

  In this specification, generic terms such as “alkyl” are understood to include both straight and branched chain groups such as butyl and tert-butyl. However, when specific terms such as “butyl group” are used, this is specific for “normal butyl group”, ie “n-butyl group”. In other words, the specific term “butyl group” means a linear “normal butyl group” and branched isomers such as “tert-butyl” are specifically referred to when intended. . As another example, “pentyloxy group” means a linear “normal pentyloxy group”. As yet another example, “hexyloxy group” means a linear “normal hexyloxy group”.

  The prefixes “n−”, “s−” and “sec−”, “i−”, “t−” and “tert−”, [neo−], “c−” and “cyc−”, “o−” "," M- ", and" p- "have their usual meanings: normal, secondary, iso, tertiary, neo, cyclo, ortho, meta, and para.

The following abbreviations may be used throughout the specification:
“Me” means methyl group;
“Et” means ethyl group;
“Pr” and “n-Pr” mean a propyl group (ie, a normal propyl group);
“I-Pr” means an isopropyl group;
“Bu” and “n-Bu” mean a butyl group (ie, a normal butyl group);
“S-Bu” means sec-butyl group;
“I-Bu” means an isobutyl group;
“T-Bu” means a tert-butyl group;
“Ph” means phenyl group;
“Bn” means a benzyl group.

  In the present specification, the term “optionally monosubstituted” or “monosubstituted” means that one hydrogen atom on a target functional group is substituted with a substituent selected from the specified substituents. Means that

  As used herein, the term “optionally polysubstituted” or “polysubstituted” refers to at least two hydrogen atoms (eg, 2 to 5 in one embodiment) on the functional group of interest. Means that the hydrogen atom, in another embodiment 2 to 3 hydrogen atoms) is substituted by the same or different substituents independently selected from the specified substituents.

  Definitions and examples of functional groups used in the present specification will be described below.

  A C1-C10 alkyl group means a linear or branched alkyl group having 1 to 10 carbon atoms.

Examples of C1-C10 alkyl groups are:
Methyl group, ethyl group, propyl group, isopropyl group,
Butyl group, sec-butyl group, isobutyl group, tert-butyl group,
Including, but not limited to, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.

  A C2-C10 alkyl group means a linear or branched alkyl group having 2 to 10 carbon atoms.

  Examples of C2 to C10 alkyl groups include, but are not limited to, suitable examples of the above examples of C1 to C10 alkyl groups.

  A C1-C6 alkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms.

  Examples of C1-C6 alkyl groups include, but are not limited to, suitable examples of the above examples of C1-C10 alkyl groups.

  The C1-C4 alkyl group means a linear or branched alkyl group having 1 to 4 carbon atoms.

  Examples of C1-C4 alkyl groups are suitable examples of the above examples of C1-C10 alkyl groups.

  A C1-C2 alkyl group means a linear alkyl group having 1-2 carbon atoms.

  Examples of C1-C2 alkyl groups are methyl and ethyl groups.

  The haloalkyl group means a linear or branched alkyl group substituted with one or more halogen atoms which are the same or different.

  The C1-C6 haloalkyl group means a linear or branched alkyl group having 1 to 6 carbon atoms, which is substituted with the same or different 1 to 13 halogen atoms (wherein the halogen atom is Has the same meaning as defined above).

Examples of C1-C6 haloalkyl groups are
Fluoromethyl group, difluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group,
2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group,
3-fluoropropyl group, 3-chloropropyl group, 3-bromopropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1-trifluoromethylethyl group, Heptafluoropropyl group, 1,2,2,2-tetrafluoro-1-trifluoromethylethyl group,
4-fluorobutyl group, 4-chlorobutyl group, 4-bromobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group,
5-fluoropentyl group, 5-chloropentyl group, 5-bromopentyl group, 5-iodopentyl group,
Examples include, but are not limited to, 6-fluorohexyl group, 6-chlorohexyl group, 6-bromohexyl group, 6-iodohexyl group and the like.

  The C1-C4 haloalkyl group means a linear or branched alkyl group having 1 to 4 carbon atoms, which is substituted with the same or different 1 to 9 halogen atoms (wherein the halogen atom is Has the same meaning as defined above).

  Examples of C1-C4 haloalkyl groups include, but are not limited to, suitable examples of the above examples of C1-C6 haloalkyl groups.

  A C1-C6 alkoxy group means a (C1-C6 alkyl) -O- group (wherein the C1-C6 alkyl group moiety has the same meaning as defined above).

Examples of C1-C6 alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy,
Butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group,
Including, but not limited to, a pentyloxy group, an isopentyloxy group, a hexyloxy group, an isohexyloxy group, and the like.

  A C1-C4 alkoxy group means a (C1-C4 alkyl) -O- group (wherein the C1-C4 alkyl group has the same meaning as defined above).

  Examples of C1-C4 alkoxy groups are suitable examples of the above examples of C1-C6 alkoxy groups.

  A C1-C2 alkoxy group means a (C1-C2 alkyl) -O- group (wherein the C1-C2 alkyl group has the same meaning as defined above).

  Examples of C1-C2 alkoxy groups are methoxy and ethoxy groups.

  A C1-C6 haloalkoxy group means a (C1-C6 haloalkyl) -O- group (wherein the C1-C6 haloalkyl group moiety has the same meaning as described above).

Examples of C1-C6 haloalkoxy groups are
Fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group,
2-fluoroethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group,
3-fluoropropoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 2,2,3,3,3-pentafluoropropoxy group, 2,2,2-trifluoro-1-trifluoromethylethoxy group, Heptafluoropropoxy group, 1,2,2,2-tetrafluoro-1-trifluoromethylethoxy group,
4-fluorobutoxy group, 4-chlorobutoxy group, 4-bromobutoxy group, 2,2,3,3,4,4,4-heptafluorobutoxy group,
5-fluoropentyloxy group, 5-chloropentyloxy group, 5-bromopentyloxy group, 5-iodopentyloxy group,
Including, but not limited to, 6-fluorohexyloxy group, 6-chlorohexyloxy group, 6-bromohexyloxy group, 6-iodohexyloxy group and the like.

  A C1-C4 haloalkoxy group means a (C1-C4 haloalkyl) -O- group (wherein the C1-C4 haloalkyl group moiety has the same meaning as described above).

Examples of C1-C4 haloalkoxy groups are
Fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, chlorodifluoromethoxy group,
2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group,
3-fluoropropoxy group, 3-chloropropoxy group, 2,2,3,3,3-pentafluoropropoxy group, heptafluoropropoxy group, 2,2,2-trifluoro-1-trifluoromethylethoxy group,
Including, but not limited to, 4-fluorobutoxy group, 2,2,3,3,4,4,4-heptafluorobutoxy group and the like.

  A C1-C4 alkylthio group means a (C1-C4 alkyl) -S- group (wherein the C1-C4 alkyl group moiety has the same meaning as described above).

  Examples of the C1-C4 alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a sec-butylthio group, an isobutylthio group, and a tert-butylthio group.

  A C1-C4 haloalkylthio group means a (C1-C4 haloalkyl) -S- group (wherein the C1-C4 haloalkyl group moiety has the same meaning as described above).

Examples of C1-C4 haloalkylthio groups are:
Fluoromethylthio group, difluoromethylthio group, trifluoromethylthio group, chlorodifluoromethylthio group,
2-fluoroethylthio group, 2-chloroethylthio group, 2,2,2-trifluoroethylthio group, pentafluoroethylthio group,
3-fluoropropylthio group, 3-chloropropylthio group, 2,2,3,3,3-pentafluoropropylthio group, heptafluoropropylthio group, 2,2,2-trifluoro-1-trifluoromethyl An ethylthio group,
Including, but not limited to, 4-fluorobutylthio group, 2,2,3,3,4,4,4-heptafluorobutylthio group and the like.

  The C1-C4 alkylsulfinyl group means a (C1-C4 alkyl) -SO- group (wherein the C1-C4 alkyl group portion has the same meaning as described above).

  Examples of the C1-C4 alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, a sec-butylsulfinyl group, an isobutylsulfinyl group, and a tert-butylsulfinyl group.

  A C1-C4 haloalkylsulfinyl group means a (C1-C4 haloalkyl) -SO- group (wherein the C1-C4 haloalkyl group portion has the same meaning as described above).

Examples of C1-C4 haloalkylsulfinyl groups are
Fluoromethylsulfinyl group, difluoromethylsulfinyl group, trifluoromethylsulfinyl group, chlorodifluoromethylsulfinyl group,
2-fluoroethylsulfinyl group, 2-chloroethylsulfinyl group, 2,2,2-trifluoroethylsulfinyl group, pentafluoroethylsulfinyl group,
3-fluoropropylsulfinyl group, 3-chloropropylsulfinyl group, 2,2,3,3,3-pentafluoropropylsulfinyl group, heptafluoropropylsulfinyl group, 2,2,2-trifluoro-1-trifluoromethyl An ethylsulfinyl group,
Including, but not limited to, 4-fluorobutylsulfinyl group, 2,2,3,3,4,4,4-heptafluorobutylsulfinyl group and the like.

The C1 -C4 alkylsulfonyl group, (C1 -C4 alkyl) -SO ₂ - means a group (here, C1 -C4 alkyl moiety has the same meaning as above.).

  Examples of the C1-C4 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a sec-butylsulfonyl group, an isobutylsulfonyl group, and a tert-butylsulfonyl group.

The C1 -C4 haloalkylsulfonyl group, (C1 -C4 haloalkyl) -SO ₂ - means a group (here, C1 -C4 haloalkyl moiety has the same meaning as above.).

Examples of C1-C4 haloalkylsulfonyl groups are
Fluoromethylsulfonyl group, difluoromethylsulfonyl group, trifluoromethylsulfonyl group, chlorodifluoromethylsulfonyl group,
2-fluoroethylsulfonyl group, 2-chloroethylsulfonyl group, 2,2,2-trifluoroethylsulfonyl group, pentafluoroethylsulfonyl group,
3-fluoropropylsulfonyl group, 3-chloropropylsulfonyl group, 2,2,3,3,3-pentafluoropropylsulfonyl group, heptafluoropropylsulfonyl group, 2,2,2-trifluoro-1-trifluoromethyl An ethylsulfonyl group,
Including, but not limited to, 4-fluorobutylsulfonyl group, 2,2,3,3,4,4,4-heptafluorobutylsulfonyl group and the like.

  A C3-C6 cycloalkyl group means a cycloalkyl group having 3-6 carbon atoms.

  Examples of C3-C6 cycloalkyl groups include, but are not limited to, cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, and the like.

  C3-C6 cycloalkyl C1-C6 alkyl group means a C1-C6 alkyl group substituted by a C3-C6 cycloalkyl group (wherein the C3-C6 cycloalkyl group moiety and the C1-C6 alkyl group moiety are Has the same meaning as defined above).

Examples of C3-C6 cycloalkyl C1-C6 alkyl groups are:
Cyclopropylmethyl group, 2-cyclopropylethyl group, 3-cyclopropylpropyl group, 4-cyclopropylbutyl group, 5-cyclopropylpentyl group, 6-cyclopropylhexyl group,
Including, but not limited to, cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, 2-cyclohexylethyl group and the like.

“C3-C6 cycloalkyl C1-C6 alkyl group, wherein the C3-C6 cycloalkyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group or C1-C4 haloalkyl group An example of `` may be ''
Examples of the above C3-C6 cycloalkyl C1-C6 alkyl group, and 2- (2,2-difluorocyclopropyl) ethyl group, 2- (4,4-difluorocyclohexyl) ethyl group, 2- (4- tert-butylcyclohexyl) ethyl group, 2- (4-methoxycyclohexyl) ethyl group, 2- (4-trifluoromethylcyclohexyl) ethyl group,
Including, but not limited to, 3- (2,2-difluorocyclopropyl) propyl group, 4- (2,2-difluorocyclopropyl) butyl group and the like.

  Examples of “C3-C6 cycloalkyl C1-C6 alkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono-substituted or poly-substituted by a halogen atom or a C1-C4 alkyl group” are the above examples. Suitable examples are included, but are not limited to these.

  The phenyl C1-C6 alkyl group means a C1-C6 alkyl group substituted by phenyl (wherein the C1-C6 alkyl group portion has the same meaning as defined above).

  Examples of phenyl C1-C6 alkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl and the like. Including, but not limited to.

“Phenyl C1-C6 alkyl group, wherein the phenyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group, C1-C6 haloalkyl group, cyano group, nitro group An example of
Examples of the above phenyl C1-C6 alkyl group, and 2- (4-fluorophenyl) ethyl group, 2- (3,4,5-trifluorophenyl) ethyl group, 2- (4-methylphenyl) ethyl group, 2- (4-methoxyphenyl) ethyl group, 2- (4-trifluoromethylphenyl) ethyl group, 2- (4-cyanophenyl) ethyl group, 2- (4-nitrophenyl) ethyl group,
Including, but not limited to, 3- (4-fluorophenyl) propyl group, 4- (4-fluorophenyl) butyl group, 5- (4-fluorophenyl) pentyl group and the like.

  Examples of “phenyl C1-C6 alkyl group, wherein the phenyl group moiety may be mono- or poly-substituted by a halogen atom or a C1-C4 alkyl group” include suitable examples of the above examples However, it is not limited to these.

  C3-C6 cycloalkyl C1-C6 haloalkyl group means a C1-C6 haloalkyl group substituted by a C3-C6 cycloalkyl group (wherein the C3-C6 cycloalkyl group moiety and the C1-C6 haloalkyl group moiety are Has the same meaning as defined above).

Examples of C3-C6 cycloalkyl C1-C6 haloalkyl groups are:
2-cyclopropyl-2,2-difluoroethyl group, 3-cyclopropyl-3,3-difluoropropyl group, 4-cyclopropyl-4,4-difluorobutyl group, 5-cyclopropyl-5,5-difluoropentyl Group, 6-cyclopropyl-6,6-difluorohexyl group,
Including, but not limited to, 2-cyclobutyl-2,2-difluoroethyl group, 2-cyclopentyl-2,2-difluoroethyl group, 2-cyclohexyl-2,2-difluoroethyl group and the like.

"C3-C6 cycloalkyl C1-C6 haloalkyl group, wherein the C3-C6 cycloalkyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group, C1-C4 haloalkyl group An example of `` may be ''
Examples of the above C3-C6 cycloalkyl C1-C6 haloalkyl groups, and 2- (2,2-difluorocyclopropyl) -2,2-difluoroethyl groups, 2- (4,4-difluorocyclohexyl) -2 , 2-difluoroethyl group, 2- (4-tert-butylcyclohexyl) -2,2-difluoroethyl group, 2- (4-methoxycyclohexyl) -2,2-difluoroethyl group, 2- (4 -Trifluoromethylcyclohexyl) -2,2-difluoroethyl group,
Including, but not limited to, 3- (2,2-difluorocyclopropyl) -3,3-difluoropropyl group, 4- (2,2-difluorocyclopropyl) -4,4-difluorobutyl group is not.

  Examples of “C3-C6 cycloalkyl C1-C6 haloalkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono- or poly-substituted by a halogen atom or a C1-C4 alkyl group” are the above examples. Suitable examples are included, but are not limited to these.

  The phenyl C1-C6 haloalkyl group means a C1-C6 haloalkyl group substituted by phenyl (wherein the C1-C6 haloalkyl group portion has the same meaning as defined above).

  Examples of phenyl C1-C6 haloalkyl groups are 2-phenyl-2,2-difluoroethyl group, 3-phenyl-3,3-difluoropropyl group, 4-phenyl-4,4-difluorobutyl group, 5-phenyl- Including, but not limited to, a 5,5-difluoropentyl group.

"Phenyl C1-C6 haloalkyl group, wherein the phenyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group, C1-C6 haloalkyl group, cyano group, nitro group An example of
Examples of the above phenyl C1-C6 haloalkyl group, and 2- (4-fluorophenyl) -2,2-difluoroethyl group, 2- (3,4,5-trifluorophenyl) -2,2-difluoroethyl group 2- (4-methylphenyl) -2,2-difluoroethyl group, 2- (4-methoxyphenyl) -2,2-difluoroethyl group, 2- (4-trifluoromethylphenyl) -2,2- Difluoroethyl group, 2- (4-cyanophenyl) -2,2-difluoroethyl group, 2- (4-nitrophenyl) -2,2-difluoroethyl group,
3- (4-fluorophenyl) -3,3-difluoropropyl group, 4- (4-fluorophenyl) -4,4-difluorobutyl group, 5- (4-fluorophenyl) -5,5-difluoropentyl group However, it is not limited to these.

  Examples of “phenyl C1-C6 haloalkyl groups, where the phenyl group moiety may be mono- or polysubstituted by halogen atoms or C1-C4 alkyl groups” include suitable examples of the above examples However, it is not limited to these.

  The C1-C4 alkoxy C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 alkoxy group (wherein the C1-C4 alkoxy group and the C2-C10 alkyl group have the same meaning as described above). Have).

  Examples of C1-C4 alkoxy C2-C10 alkyl groups include, but are not limited to, 5-methoxypentyl group, 6-methoxyhexyl group and the like.

  The C1-C4 haloalkoxy C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 haloalkoxy group (wherein the C1-C4 haloalkoxy group and the C2-C10 alkyl group are as described above). Have the same meaning).

Examples of C1-C4 haloalkoxy C2-C10 alkyl groups are:
5-difluoromethoxypentyl group, 5-trifluoromethoxypentyl group,
Including, but not limited to, 6-difluoromethoxyhexyl group, 6-trifluoromethoxyhexyl group and the like.

  The C1-C4 alkylthio C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 alkylthio group (wherein the C1-C4 alkylthio group and the C2-C10 alkyl group have the same meanings as described above). Have).

Examples of C1-C4 alkylthio C2-C10 alkyl groups are:
2-methylthioethyl group, 3-methylthiopropyl group, 4-methylthiobutyl group,
5-methylthiopentyl group, 5-ethylthiopentyl group, 5-propylthiopentyl group, 5-butylthiopentyl group,
6-methylthiohexyl group, 6-ethylthiohexyl group, 6-propylthiohexyl group, 6-butylthiohexyl group,
Examples include, but are not limited to, 7-methylthioheptyl group, 8-methylthiooctyl group, 9-methylthiononyl group, 10-methylthiodecyl group, and the like.

  From the viewpoint of the usefulness and economy of the product, preferred examples of the C1-C4 alkylthio C2-C10 alkyl group include a 5-methylthiopentyl group and a 6-methylthiohexyl group.

  The C1-C4 haloalkylthio C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 haloalkylthio group (wherein the C1-C4 haloalkylthio group and the C2-C10 alkyl group are as described above). Have the same meaning).

Examples of C1-C4 haloalkylthio C2-C10 alkyl groups are:
2-trifluoromethylthioethyl group, 3-trifluoromethylthiopropyl group, 4-trifluoromethylthiobutyl group,
5-difluoromethylthiopentyl group, 5-trifluoromethylthiopentyl group, 5- (2,2,2-trifluoroethylthio) pentyl group, 5-pentafluoroethylthiopentyl group, 5- (2,2,3, 3,3-pentafluoropropylthio) pentyl group, 5- (2,2,3,3,4,4,4-heptafluorobutylthio) pentyl group,
6-difluoromethylthiohexyl group, 6-trifluoromethylthiohexyl group, 6- (2,2,2-trifluoroethylthio) hexyl group, 6-pentafluoroethylthiohexyl group, 6- (2,2,3, 3,3-pentafluoropropylthio) hexyl group, 6- (2,2,3,3,4,4,4-heptafluorobutylthio) hexyl group,
Examples include, but are not limited to, 7-trifluoromethylthioheptyl group, 8-trifluoromethylthiooctyl group, 9-trifluoromethylthiononyl group, 10-trifluoromethylthiodecyl group, and the like.

  From the viewpoint of the usefulness and economy of the product, preferred examples of the C1-C4 haloalkylthio C2-C10 alkyl group include a 5-trifluoromethylthiopentyl group and a 6-trifluoromethylthiohexyl group.

  The C1-C4 alkylsulfinyl C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 alkylsulfinyl group (wherein the C1-C4 alkylsulfinyl group and the C2-C10 alkyl group are as described above). Have the same meaning).

  Examples of the C1-C4 alkylsulfinyl C2-C10 alkyl group include, but are not limited to, a 5-methylsulfinylpentyl group and a 6-methylsulfinylhexyl group.

  The C1-C4 alkylsulfonyl C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 alkylsulfonyl group (wherein the C1-C4 alkylsulfonyl group and the C2-C10 alkyl group are as described above). Have the same meaning).

  Examples of the C1-C4 alkylsulfonyl C2-C10 alkyl group include, but are not limited to, a 5-methylsulfonylpentyl group and a 6-methylsulfonylhexyl group.

  The C1-C4 haloalkylsulfinyl C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 haloalkylsulfinyl group (wherein the C1-C4 haloalkylsulfinyl group and the C2-C10 alkyl group are as described above). Have the same meaning).

Examples of C1-C4 haloalkylsulfinyl C2-C10 alkyl groups include 5-difluoromethylsulfinylpentyl group, 5-trifluoromethylsulfinylpentyl group, 6-difluoromethylsulfinylhexyl group, 6-trifluoromethylsulfinylhexyl group and the like. Including, but not limited to.

  The C1-C4 haloalkylsulfonyl C2-C10 alkyl group means a C2-C10 alkyl group substituted by a C1-C4 haloalkylsulfonyl group (wherein the C1-C4 haloalkylsulfonyl group and the C2-C10 alkyl group are as described above). Have the same meaning).

  Examples of the C1-C4 haloalkylsulfonyl C2-C10 alkyl group include a 5-difluoromethylsulfonylpentyl group, a 5-trifluoromethylsulfonylpentyl group, a 6-difluoromethylsulfonylhexyl group, and a 6-trifluoromethylsulfonylhexyl group. Including, but not limited to.

  The C6-C10 aryl group means an aromatic cyclic group in which all atoms constituting the ring are 6 to 10 carbon atoms.

  Examples of C6-C10 aryl groups are a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The 1-naphthyl group is also referred to as a naphthalen-1-yl group. The 2-naphthyl group is also referred to as a naphthalen-2-yl group.

  A C1-C4 alkoxycarbonyl group means a (C1-C4 alkyl) -O-C (= O)-group (wherein the C1-C4 alkyl group portion has the same meaning as defined above).

  Examples of the C1-C4 alkoxycarbonyl group include, but are not limited to, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, and the like.

  A C1-C4 alkylcarbonyl group means a (C1-C4 alkyl) -C (= O)-group (wherein the C1-C4 alkyl group moiety has the same meaning as defined above).

  Examples of the C1-C4 alkylcarbonyl group include, but are not limited to, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group and the like.

  The hydroxy C1-C4 alkyl group means a C1-C4 alkyl group substituted by a hydroxy group (wherein the C1-C4 alkyl group has the same meaning as described above).

  Examples of hydroxy C1-C4 alkyl groups are hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, Including, but not limited to, a 3-hydroxybutyl group.

  The C1-C4 alkoxy C1-C4 alkyl group means a C1-C4 alkyl group substituted by a C1-C4 alkoxy group (wherein the C1-C4 alkoxy group and the C1-C4 alkyl group have the same meaning as described above). Have).

Examples of C1-C4 alkoxy C1-C4 alkyl groups are:
Methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group,
1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, 1-propoxyethyl group, 2-propoxyethyl group, 1-isopropoxyethyl group, 2-isopropoxyethyl group,
1-methoxypropyl group, 2-methoxypropyl group, 3-methoxypropyl group,
Including, but not limited to, 1-methoxybutyl group, 2-methoxybutyl group, 3-methoxybutyl group, 4-methoxybutyl group and the like.

  An amino C1-C4 alkyl group means a C1-C4 alkyl group substituted by an amino group (wherein the C1-C4 alkyl group has the same meaning as described above).

  Examples of amino C1-C4 alkyl groups include aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 1-aminopropyl group, 2-aminopropyl group, 1-aminobutyl group, 2-aminobutyl group, Including, but not limited to, a 3-aminobutyl group.

  The cyano C1-C4 alkyl group means a C1-C4 alkyl group substituted by a cyano group (wherein the C1-C4 alkyl group has the same meaning as described above).

  Examples of the cyano C1-C4 alkyl group include a cyanomethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, a 1-cyanopropyl group, a 2-cyanopropyl group, a 1-cyanobutyl group, a 2-cyanobutyl group, a 3-cyanobutyl group, and the like. However, it is not limited to these.

  A nitro C1-C4 alkyl group means a C1-C4 alkyl group substituted by a nitro group (wherein the C1-C4 alkyl group has the same meaning as described above).

  Examples of nitro C1-C4 alkyl groups are nitromethyl, 1-nitroethyl, 2-nitroethyl, 1-nitropropyl, 2-nitropropyl, 1-nitrobutyl, 2-nitrobutyl, 3-nitrobutyl, etc. However, it is not limited to these.

  The carboxy C1-C4 alkyl group means a C1-C4 alkyl group substituted by a carboxy group (wherein the C1-C4 alkyl group has the same meaning as described above).

  Examples of the carboxy C1-C4 alkyl group include carboxymethyl group, 1-carboxyethyl group, 2-carboxyethyl group, 1-carboxypropyl group, 2-carboxypropyl group, 1-carboxybutyl group, 2-carboxybutyl group, Including, but not limited to, 3-carboxybutyl group.

  The C1-C4 alkoxycarbonyl C1-C4 alkyl group means a C1-C4 alkyl group substituted by a C1-C4 alkoxycarbonyl group (wherein the C1-C4 alkoxycarbonyl group and the C1-C4 alkyl group are as described above). Have the same meaning).

Examples of C1-C4 alkoxycarbonyl C1-C4 alkyl groups are:
Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, isopropoxycarbonylmethyl group,
1-methoxycarbonylethyl group, 2-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 1-propoxycarbonylethyl group, 2-propoxycarbonylethyl group, 1-isopropoxycarbonylethyl group, 2-isopropoxycarbonylethyl group,
1-methoxycarbonylpropyl group, 2-methoxycarbonylpropyl group, 3-methoxycarbonylpropyl group,
Including, but not limited to, 1-methoxycarbonylbutyl group, 2-methoxycarbonylbutyl group, 3-methoxycarbonylbutyl group, 4-methoxycarbonylbutyl group and the like.

  A mono (C1-C4 alkyl) amino group means a (C1-C4 alkyl) -NH- group (wherein the C1-C4 alkyl group moiety has the same meaning as defined above).

  Examples of mono (C1-C4 alkyl) amino groups include, but are not limited to, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, and the like.

The di (C1-C4 alkyl) amino group means a (C1-C4 alkyl) ₂ N-group (wherein the C1-C4 alkyl group moieties are the same or different and have the same meaning as defined above). .)

  Examples of di (C1-C4 alkyl) amino groups include, but are not limited to, dimethylamino groups, diethylamino groups, dipropylamino groups, dibutylamino groups, methylethylamino groups, and the like.

  The definitions and examples of functional groups other than those described above can be understood by those skilled in the art in the same manner as the functional groups described above.

(Raw material compound: sulfide derivative represented by the general formula (2))
The preparation of the sulfide derivative represented by the general formula (2) is described in, for example, International Publication No. 2013/157229 (Patent Document 1) or can be performed in a similar manner.

From the viewpoint of the usefulness and economics of the product, in the general formula (2), preferred combinations of R ¹ , R ² and R ³ are:
R ¹ is a C1-C10 alkyl group,
A C3-C6 cycloalkyl C1-C6 alkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono- or poly-substituted with a halogen atom or a C1-C4 alkyl group,
A phenyl C1-C6 alkyl group, wherein the phenyl group moiety may be mono- or poly-substituted with a halogen atom or a C1-C4 alkyl group,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
A C1-C4 haloalkylsulfonyl C2-C10 alkyl group,
A C1-C6 haloalkyl group,
A C3-C6 cycloalkyl C1-C6 haloalkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono- or polysubstituted by a halogen atom or a C1-C4 alkyl group, or a phenyl C1-C6 haloalkyl group, Wherein the phenyl group moiety may be mono- or polysubstituted by a halogen atom or a C1-C4 alkyl group; and R ² and R ³ are each independently a halogen atom or a C1-C4 alkyl group. It is a group.

From the same viewpoint as above, in the general formula (2), more preferred combinations of R ¹ , R ² and R ³ are:
R ¹ is a C1-C10 alkyl group,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
A C1-C4 haloalkylsulfonyl C2-C10 alkyl group, or a C1-C6 haloalkoxy group; and R ² and R ³ are each independently a halogen atom or a C1-C4 alkyl group.

From the same viewpoint as above, in the general formula (2), more preferable combinations of R ¹ , R ² and R ³ are:
R ¹ is a C1-C4 haloalkylthio C2-C10 alkyl group; and R ² and R ³ are each independently a halogen atom or a C1-C4 alkyl group.

From the same viewpoint as above, in the general formula (2), more preferable combinations of R ¹ , R ² and R ³ are:
R ¹ is a 5-trifluoromethylthiopentyl group or 6-trifluoromethylthiohexyl group; and R ² is a fluorine atom and R ³ is a chlorine atom, or R ² and R ³ are methyl groups .

In one embodiment, from the same viewpoint as described above, in Formula (2), more preferable specific combinations of R ¹ , R ² and R ³ are:
R ¹ is a 5-trifluoromethylthiopentyl group;
R ² is a fluorine atom; and R ³ is a chlorine atom.

In another embodiment, from the same viewpoint as described above, in Formula (2), more preferable specific combinations of R ¹ , R ² and R ³ are:
R ¹ is a 6-trifluoromethylthiohexyl group; and R ² and R ³ are methyl groups.

From the same viewpoint as above, in the general formula (2), particularly preferred specific combinations of R ¹ , R ² and R ³ are:
R ¹ is a 5-trifluoromethylthiopentyl group;
R ² is a fluorine atom; and R ³ is a chlorine atom.

(Target compound: sulfoxide derivative represented by the general formula (1))
From the same viewpoint as above, in general formula (1), preferred combinations, more preferred combinations, further preferred combinations, and particularly preferred combinations of R ¹ , R ² and R ³ are those in general formula (2) described above. It is the same.

(Oxidant)
The oxidizing agent used in the present invention may be any oxidizing agent as long as the reaction proceeds. An oxidizing agent capable of oxidizing the corresponding raw material compound (sulfide derivative) to the target compound (sulfoxide derivative) can be used. Examples of the oxidizing agent used in the present invention include, but are not limited to, inorganic peroxides (for example, hydrogen peroxide, urea-hydrogen peroxide adduct, etc.) and the like. From the viewpoint of safety, reactivity, selectivity, economic efficiency, etc., a preferred oxidizing agent is hydrogen peroxide. You may use an oxidizing agent individually or in combination of 2 or more types of arbitrary ratios.

  The form of the oxidizing agent may be any form as long as the reaction proceeds. The form of the oxidizing agent can be appropriately selected by those skilled in the art. When hydrogen peroxide is used as the oxidizing agent, the hydrogen peroxide may be in any form as long as the reaction proceeds. In view of danger and economic efficiency, examples of preferred forms of hydrogen peroxide are 5-60 wt% aqueous hydrogen peroxide, preferably 5-40 wt% aqueous hydrogen peroxide, more preferably 10-35 wt% hydrogen peroxide. An aqueous solution, more preferably a 25 to 35 wt% aqueous hydrogen peroxide solution. In the present specification, for example, “30% hydrogen peroxide aqueous solution” is also referred to as “30% hydrogen peroxide”.

(Amount of oxidizing agent used)
The amount of the oxidizing agent used in the method of the present invention may be any amount as long as the reaction proceeds.

  From the viewpoint of improvement in yield and economic efficiency, the lower limit of the oxidizing agent in the present invention is preferably 0.9 mol or more, based on 1 mol of the sulfide derivative (raw material compound) represented by the general formula (2). Can illustrate 1.0 mol or more.

  From the viewpoints of safety, suppression of by-products and economic efficiency, the upper limit of the oxidizing agent in the present invention is 4.0 with respect to 1 mol of the sulfide derivative (raw material compound) represented by the general formula (2). Examples include a mole or less, preferably 3.0 mole or less, and more preferably 2.5 mole or less.

  Furthermore, as usage-amount of the oxidizing agent in this invention, the appropriate and arbitrary combinations of said minimum and upper limit can be illustrated. Therefore, from the viewpoints of safety, yield improvement, suppression of by-products, economic efficiency, etc., the amount of the oxidizing agent used in the present invention is the sulfide derivative (raw material compound) represented by the general formula (2). An amount of 0.9 to 4.0 mol, preferably 1.0 to 3.0 mol, and more preferably 1.0 to 2.5 mol can be exemplified with respect to 1 mol. However, the amount of the oxidizing agent used in the present invention can be appropriately adjusted by those skilled in the art according to the purpose and situation.

(Catalyst: Metal-ligand complex)
The catalyst in the present invention is a metal-ligand complex. The metal-ligand complex can be prepared from a metal compound and a ligand. In addition, the metal-ligand complex may contain components other than the metal compound and the ligand. Accordingly, the metal-ligand complex includes a metal compound ligand.

(Metal compound)
The metal compound contained in the metal-ligand complex in the present invention will be described. The metal compound used in the present invention may be any metal compound as long as the reaction proceeds. The metal compound used in the present invention is a known compound or a compound that can be produced from a known compound according to a known method.

  Examples of the metal compound include, but are not limited to, metal acetylacetonate, metal halide, metal oxide, and metal alkoxide.

  The metal of the metal compound is preferably a transition metal.

  Examples of metal compounds include, but are not limited to, iron compounds, vanadium compounds, titanium compounds, manganese compounds, copper compounds, molybdenum compounds, zirconium compounds, and the like.

  From the viewpoint of yield and economic efficiency, the metal compound is preferably an iron compound, a vanadium compound, and more preferably an iron compound.

Examples of iron compounds are iron (III) acetylacetonate, iron (III) chloride, iron (III) bromide, iron (III) methoxide, iron (III) ethoxide, iron (III) propoxide, iron (III) Including, but not limited to, isopropoxide. “Iron (III) acetylacetonate” is also referred to as “Fe (acac) ₃ ” or “tris (2,4-pentanedionato) iron (III)”. From the same viewpoint as described above, preferable examples of the iron compound include iron (III) acetylacetonate and iron (III) chloride. A more preferred example of the iron compound includes iron (III) acetylacetonate.

Examples of vanadium compounds include, but are not limited to, vanadyl acetylacetonate, vanadium oxide (V), triisopropoxy vanadium (V) oxide, and the like. “Vanadylacetylacetonate” is also referred to as “VO (acac) ₂ ”, “bis (2,4-pentanedionato) vanadium (IV) oxide” or “vanadium (IV) oxyacetylacetonate”. “Triisopropoxyvanadium (V) oxide” is also referred to as “VO (OiPr) ₃ ” or “triisopropoxyoxovanadium (V)”. From the same viewpoint as described above, preferable examples of the vanadium compound include vanadyl acetylacetonate and vanadium oxide (V). More preferred examples of vanadium compounds include vanadyl acetylacetonate.

  Examples of titanium compounds include titanium tetrachloride, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide, titanium (IV) tert-butoxide, etc. It is not limited to.

Examples of manganese compounds include, but are not limited to, manganese (III) acetylacetonate, manganese (II) chloride, and the like. “Manganese (III) acetylacetonate” is also referred to as “Mn (acac) ₃ ”.

Examples of copper compounds include, but are not limited to, copper (II) acetylacetonate, copper (I) chloride, copper (II) chloride, and the like. “Copper (II) acetylacetonate” is also referred to as “Cu (acac) ₂ ”.

Examples of molybdenum compounds include, but are not limited to, molybdenyl acetylacetonate and the like. “Molybenyl acetylacetonate” is also referred to as “MoO ₂ (acac) ₂ ”, “bis (2,4-pentanedionato) molybdenum (VI) dioxide” or “molybdenum (IV) dioxyacetylacetonate”.

Examples of zirconium compounds include, but are not limited to, zirconium (IV) acetylacetonate, zirconium tetrachloride, and the like. “Zirconium (IV) acetylacetonate” is also referred to as “Zr (acac) ₄ ” or “tetrakis (2,4-pentanedionato) zirconium (IV)”.

  You may use the metal compound in this invention individually or in combination of 2 or more types of arbitrary ratios. The form of the metal compound in the present invention may be any form as long as the reaction proceeds. The form of the metal compound in the present invention can be appropriately selected by those skilled in the art.

(Amount of metal compound used)
The amount of the metal compound used in the method of the present invention may be any amount as long as the reaction proceeds. The usage-amount of a metal compound can be reduced by use of the benzoic acid compound represented by General formula (4). In one embodiment, from the viewpoint of improving yield, reducing environmental burden, and economic efficiency, the amount of the metal compound used in the present invention is a sulfide derivative (raw material compound) 1 represented by the general formula (2). 0.1 to 20.0 mol%, preferably 0.1 to 10.0 mol%, more preferably 0.3 to 10.0 mol%, still more preferably 0.4 to 10.0 mol% with respect to mol can do. Furthermore, in another embodiment, from the same viewpoint as described above, the amount of the metal compound used in the present invention is preferably 0.1 with respect to 1 mol of the sulfide derivative (raw material compound) represented by the general formula (2). 3 to 6.0 mol%, more preferably 0.3 to 5.0 mol%, more preferably 0.4 to 5.0 mol%, still more preferably 0.4 to 4.0 mol%, still more preferably 0.4 to Examples also include 3.0 mol%, particularly preferably 0.4 to 2.0 mol%. However, the amount of the metal compound used in the present invention can be appropriately adjusted by those skilled in the art according to the purpose and situation.

(Ligand)
The ligand contained in the metal-ligand complex in the present invention will be described. The ligand used in the present invention is a known compound or a compound that can be produced from a known compound according to a known method.

  From the viewpoint of yield and economic efficiency, a preferred ligand is represented by the general formula (3):

(In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷¹ and R ⁷² are as follows.)
It is a compound represented by these.

In general formula (3), R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a phenyl C1-C6 alkyl group, a C6-C10 aryl group, a cyano group, a nitro group, or C1-C6 alkoxy group.

From the viewpoints of yield and economic efficiency, preferred examples of R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom or a C1-C6 alkyl group, more preferably each independently a hydrogen atom or a halogen atom.

A more preferred example of R ⁴ is a hydrogen atom.

More preferred examples of R ⁵ are a hydrogen atom or a chlorine atom, particularly preferably a hydrogen atom.

In general formula (3), R ⁶ is a C1-C4 alkyl group, a cyano group, a nitro group, a carboxy group, a C1-C4 alkoxycarbonyl group, a C1-C4 alkylcarbonyl group, a hydroxy C1-C4 alkyl group, C1-C4. An alkoxy C1-C4 alkyl group, an amino C1-C4 alkyl group, a cyano C1-C4 alkyl group, a nitro C1-C4 alkyl group, a carboxy C1-C4 alkyl group, or a C1-C4 alkoxycarbonyl C1-C4 alkyl group.

From the viewpoints of yield and economic efficiency, a preferred example of R ⁶ is a hydroxy C1-C4 alkyl group, more preferably a hydroxymethyl group.

In the general formula (3), R ⁷¹ and R ⁷² are each independently a hydrogen atom, a C1-C6 alkyl group, a phenyl C1-C6 alkyl group or a C6-C10 aryl group (provided that R ⁷¹ and R ⁷² are hydrogen atoms) Except when it is an atom).

From the viewpoints of yield and economic efficiency, preferred examples of R ⁷¹ and R ⁷² are each independently a hydrogen atom or a C1-C6 alkyl group (provided that R ⁷¹ and R ⁷² are hydrogen atoms). ) And
More preferably, R ⁷¹ is a methyl group and R ⁷² is a methyl group, or R ⁷¹ is a hydrogen atom and R ⁷² is an isopropyl group,
Particularly preferably, R ⁷¹ is a methyl group and R ⁷² is a methyl group.

In the general formula (3), preferred specific combinations of R ⁴ , R ⁵ , R ⁶ , R ⁷¹ and R ⁷² are:
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom or a chlorine atom;
R ⁶ is a hydroxymethyl group;
R ⁷¹ is a methyl group;
R ⁷² is a methyl group.

In the general formula (3), particularly preferred specific combinations of R ⁴ , R ⁵ , R ⁶ , R ⁷¹ and R ⁷² are:
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom;
R ⁶ is a hydroxymethyl group;
R ⁷¹ is a methyl group;
R ⁷² is a methyl group.

  Specific examples of the ligand include compounds of the following formulas (3-1) to (3-13).

  From the viewpoints of yield and economic efficiency, preferred specific examples of the ligand include the formulas (3-1), (3-2), (3-3), (3-4), (3-8), (3-9), (3-10), and (3-12) are included.

  More preferred specific examples of the ligand include the formula (3-1), (3-2), (3-3), (3-4), (3-9), or (3-12).

  More preferable specific examples of the ligand are represented by formula (3-1), (3-4), (3-9), or (3-12).

  A more preferable specific example of the ligand is the formula (3-4) or (3-9).

  A particularly preferred specific example of the ligand is a compound of the formula (3-4).

  You may use the ligand in this invention individually or in combination of 2 or more types of arbitrary ratios. The form of the ligand in the present invention may be any form as long as the reaction proceeds. The form of the ligand compound in the present invention can be appropriately selected by those skilled in the art.

(Ligand usage)
The amount of the ligand used in the method of the present invention may be any amount as long as the reaction proceeds. The usage-amount of a ligand can be reduced by use of the benzoic acid compound represented by General formula (4). In one embodiment, the amount of the ligand used in the present invention is a sulfide derivative represented by the general formula (2) (raw material compound) from the viewpoints of yield improvement, reduction of environmental burden, economic efficiency, and the like. 0.1 to 20.0 mol%, preferably 0.1 to 10.0 mol%, more preferably 0.3 to 10.0 mol%, and still more preferably 0.4 to 10.0 mol% with respect to 1 mol. It can be illustrated. Furthermore, in another embodiment, from the same viewpoint as described above, the amount of the ligand used in the present invention is preferably 0 with respect to 1 mol of the sulfide derivative (raw material compound) represented by the general formula (2). 0.3-6.0 mol%, more preferably 0.3-5.0 mol%, still more preferably 0.4-5.0 mol%, still more preferably 0.4-4.0 mol%, still more preferably 0.4. ˜3.0 mol%, particularly preferably 0.4 to 2.0 mol% can also be exemplified. However, the usage-amount of the ligand in this invention can be suitably adjusted by those skilled in the art according to the objective and the condition.

(Benzoic acid compound)
The benzoic acid compound represented by the general formula (4) in the present invention will be described. The reaction of the present invention has the general formula (4):

(In the formula, A ¹ , A ² , A ³ , A ⁴ , A ⁵ , M and n are as follows.)
It is performed in the presence of a benzoic acid compound represented by: The benzoic acid compound of the general formula (4) used in the present invention is a known compound or a compound that can be produced from a known compound according to a known method.

In the general formula (4), A ¹ , A ² , A ³ , A ⁴ and A ⁵ are preferably a C ¹ -C 2 alkoxy group from the viewpoint of yield, economic efficiency, and the like;
A ² is a hydrogen atom;
A ³ is a hydrogen atom or a C1-C2 alkoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a C1~C2 alkoxy group.

A more preferred example of A ¹ is a methoxy group.

A more preferred example of A ³ is a hydrogen atom or a methoxy group, more preferably a hydrogen atom.

A more preferred example of A ⁵ is a methoxy group.

  In general formula (4), M is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.

  From the viewpoint of yield and economic efficiency, M is preferably an alkali metal atom or an alkaline earth metal atom, more preferably an alkali metal atom.

  Specific examples of M include, but are not limited to, a lithium atom, a sodium atom, a potassium atom, a cesium atom, a magnesium atom, a calcium atom, and a barium atom.

  From the viewpoints of yield and economic efficiency, preferred specific examples of M are a lithium atom, a sodium atom, a potassium atom, a cesium atom, a magnesium atom, and a calcium atom.

  More preferable specific examples of M are a lithium atom, a sodium atom, a potassium atom, and a cesium atom.

  A more preferred specific example of M is a sodium atom.

  In general formula (4), n is 1 or 2. More specifically, n may be 1 or 2 as long as it is chemically acceptable. For example, n is 1 when M is a hydrogen atom or an alkali metal atom. As another example, n is 2 when M is an alkaline earth metal atom.

From the viewpoints of yield and economic efficiency, in the general formula (4), preferred combinations of A ¹ , A ² , A ³ , A ⁴ , A ⁵ , M and n are:
A ¹ is a C1-C2 alkoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom or a C1-C2 alkoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a C1-C2 alkoxy group;
M is a sodium atom; and n is 1.

In the general formula (4), more preferable combinations of A ¹ , A ² , A ³ , A ⁴ , A ⁵ , M and n are:
A ¹ is a methoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom or a methoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
M is a sodium atom; and n is 1.

In one embodiment, in Formula (4), more preferable specific combinations of A ¹ , A ² , A ³ , A ⁴ , A ⁵ , M and n are:
A ¹ is a methoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
M is a sodium atom; and n is 1.

In another embodiment, in Formula (4), more preferred specific combinations of A ¹ , A ² , A ³ , A ⁴ , A ⁵ , M and n are:
A ¹ is a methoxy group;
A ² is a hydrogen atom;
A ³ is a methoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
M is a sodium atom; and n is 1.

In general formula (4), particularly preferred specific combinations of A ¹ , A ² , A ³ , A ⁴ , A ⁵ , M and n are:
A ¹ is a methoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
M is a sodium atom; and n is 1.

  Specific examples of benzoic acid compounds used in Examples and Comparative Examples of the present invention, and related benzoic acid compounds and other benzoic acid compounds are shown below;

  Preferred specific examples of the benzoic acid compound in the present invention include the compounds of the formulas (4-1) and (4-2) described above.

  A particularly preferred specific example of the benzoic acid compound in the present invention is the compound of the formula (4-1) described above.

  In general, in an oxidation reaction for producing a sulfoxide derivative of general formula (1) (target compound of the present invention) from a sulfide derivative of general formula (2) (raw compound of the present invention), benzoic acid of general formula (4) is used. The reaction can proceed even when no compound is used. Therefore, as long as the reaction proceeds, the benzoic acid compound of the general formula (4) may or may not be used. However, from the viewpoint of improving the yield, etc., the benzoic acid compound of the general formula (4) is preferably used in the reaction of the present invention. In addition, from the viewpoint of reducing the amount of the catalyst (that is, the amount of the metal compound and the amount of the ligand), the benzoic acid compound of the general formula (4) is preferably used in the reaction of the present invention. In other words, the reaction of the present invention is preferably carried out in the presence of a benzoic acid compound of the general formula (4).

The advantageous effect of the present invention was obtained by using the benzoic acid compound represented by the general formula (4). In this connection, the most preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷¹ , R ⁷² , A ¹ , A ² , A ³ , A ⁴ , A ⁵ , in the present invention. The combination of M and n is a combination of the above-mentioned “particularly preferable specific combinations”.

(Use amount of benzoic acid compound represented by formula (4))
The amount of the benzoic acid compound represented by the general formula (4) in the method of the present invention may be any amount as long as the reaction proceeds. In one embodiment, from the viewpoint of yield, economic efficiency, etc., the amount of the benzoic acid compound represented by the general formula (4) in the present invention is the sulfide derivative (raw material compound) represented by the general formula (2). ) 0.1 to 20 mol%, preferably 3 to 20 mol%, more preferably 3 to 15 mol%, still more preferably 3 to 10 mol%, and particularly preferably 3 to 5 mol% with respect to 1 mol. . Furthermore, in another aspect, from the same viewpoint as described above, the amount of the benzoic acid compound represented by the general formula (4) in the present invention is the sulfide derivative (raw material compound) represented by the general formula (2). Preferably 1-20 mol% with respect to 1 mol, More preferably, it is 1-15 mol%, More preferably, it is 1-10 mol%, Most preferably, 1-5 mol% can also be illustrated. However, the usage-amount of the benzoic acid compound represented by General formula (4) in this invention can be suitably adjusted by those skilled in the art according to the objective and the condition.

(Preparation of catalyst solution)
A catalyst solution can be prepared by stirring a metal compound and a compound represented by the general formula (3) as a ligand and a benzoic acid compound represented by the general formula (4) in a predetermined solvent. Examples of the solvent in the preparation of the catalyst solution of the present invention include the following “solvent in the reaction of the present invention”. The temperature in the preparation of the catalyst solution of the present invention is not particularly limited, but can be exemplified in the range of 0 ° C. to 50 ° C., preferably 15 to 30 ° C. (room temperature) from the viewpoint of catalyst stability and the like. The time in the preparation of the catalyst solution of the present invention is not particularly limited, but from the viewpoint of catalyst stability and the like, it is in the range of 10 minutes to 12 hours, more preferably 10 minutes to 2 hours, and even more preferably 10 minutes to 1 hour. Can be illustrated. Specific examples include 30 minutes, 1 hour and 2 hours, preferably 30 minutes and 1 hour, more preferably 30 minutes. However, as long as the reaction proceeds, the method for preparing the catalyst solution can be appropriately selected and adjusted by those skilled in the art.

(Method for producing sulfoxide derivative)
The sulfoxide derivative represented by the general formula (1) can be produced by reacting the sulfide derivative represented by the general formula (2), the catalyst solution prepared above and an oxidizing agent in a predetermined solvent. However, as long as the reaction proceeds, the method of the present invention is not limited to the method for preparing the catalyst solutions shown in Examples and above. The order of adding raw materials, reagents, solvents, etc. can be appropriately selected and adjusted by those skilled in the art.

(solvent)
From the viewpoint of smooth progress of the reaction, the reaction of the present invention is preferably carried out in the presence of a solvent. The solvent in the reaction of the present invention may be any solvent as long as the reaction proceeds.

As the solvent in the reaction of the present invention, for example,
water,
Halogenated aliphatic hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, trichloroethane, trichloroethylene, tetrachloroethane, tetrachloroethylene, pentachloroethane, etc. , Preferably dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, more preferably dichloromethane)
Aromatic hydrocarbon derivatives (for example, benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, chlorotoluene, benzotrifluoride, 4-chlorobenzotrifluoride, difluorobenzene, bromobenzene, nitrobenzene, etc. Is toluene, xylene, chlorobenzene, dichlorobenzene, chlorotoluene)
Nitriles (for example, acetonitrile, propionitrile, butyronitrile, etc., preferably acetonitrile),
Carboxylates (eg, ethyl acetate, isopropyl acetate, butyl acetate, etc.),
Amides (for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N, N-diethylacetamide, N-methylpyrrolidone (NMP), etc., preferably N, N-dimethylformamide ( DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), more preferably N, N-dimethylformamide (DMF)),
Alkyl ureas (for example, N, N′-dimethylimidazolidinone (DMI), etc.),
Sulfoxides (for example, dimethyl sulfoxide (DMSO), etc.),
Sulfones (for example, sulfolane),
Carbonates (eg, ethylene carbonate, propylene carbonate, etc.)
Alcohols (eg, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, etc.),
Ethers (for example, tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, di-tert-butyl ether, cyclopentyl methyl ether (CPME), methyl-tert-butyl ether (MTBE) ), Tert-amyl methyl ether (TAME), 1,2-dimethoxyethane (DME), diglyme, triglyme, 4-methoxybenzene, diphenyl ether, etc.), and any combinations thereof However, it is not limited to these.

  From the viewpoint of reactivity and economic efficiency, preferred examples of the solvent include water, halogenated aliphatic hydrocarbons, aromatic hydrocarbon derivatives, nitriles, carboxylic acid esters, amides, and any proportion thereof. Including any combination of

  More preferred examples of solvents include water, halogenated aliphatic hydrocarbons, aromatic hydrocarbon derivatives, nitriles, amides, and any combination thereof in any proportion.

  Further preferred examples of solvents include water, halogenated aliphatic hydrocarbons, aromatic hydrocarbon derivatives, and any combination thereof in any proportion.

  Particularly preferred examples of solvents include water, halogenated aliphatic hydrocarbons, and any combination thereof in any proportion.

  Preferred examples of the solvent include water, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, chlorotoluene, acetonitrile, ethyl acetate, isopropyl acetate, butyl acetate, N, N- Including dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), and any combination thereof in any proportion.

  More preferred specific examples of solvents are water, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, acetonitrile, N, N-dimethylformamide (DMF), and any proportions of Including any combination thereof.

  More preferred embodiments of the solvent include water, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, and any combination thereof in any proportion.

  Particularly preferred embodiments of the solvent include water, dichloromethane, and any combination thereof in any proportion. However, the solvent in the reaction of the present invention can be appropriately selected by those skilled in the art.

  The amount of solvent used may be any amount as long as the reaction proceeds. From the viewpoint of improvement in yield, suppression of by-products, economic efficiency, etc., 0.01 to 10.0 L (liter) with respect to 1 mol of the sulfide derivative (raw material compound) represented by the general formula (2) Preferably, 0.1-5.0L can be illustrated. However, the amount of the solvent used in the reaction of the present invention can be appropriately adjusted by those skilled in the art. When a combination of two or more solvents is used, the ratio of the two or more solvents may be any ratio as long as the reaction proceeds.

(Reaction temperature)
The reaction temperature of the present invention is not particularly limited. In one embodiment, from the viewpoint of improvement in yield, suppression of by-products, economic efficiency, etc.
−20 ° C. to 50 ° C. (ie, minus 20 ° C. to plus 50 ° C.),
Preferably, −10 ° C. to 30 ° C. (that is, minus 10 ° C. to plus 30 ° C.),
More preferably, −10 ° C. to 20 ° C. (that is, minus 10 ° C. to plus 20 ° C.),
More preferably, −5 ° C. to 15 ° C. (that is, minus 5 ° C. to plus 15 ° C.),
The range of 0 degreeC-10 degreeC (namely, zero degreeC-plus 10 degreeC) can be illustrated especially preferably. In another embodiment, from the same viewpoint as above,
−20 ° C. to 50 ° C. (ie, minus 20 ° C. to plus 50 ° C.),
Preferably, −10 ° C. to 40 ° C. (that is, minus 10 ° C. to plus 40 ° C.),
More preferably, −5 ° C. to 40 ° C. (that is, minus 5 ° C. to plus 40 ° C.),
More preferably, −5 ° C. to 30 ° C. (that is, minus 5 ° C. to plus 30 ° C.),
Particularly preferably, the range of 0 ° C. to 10 ° C. (that is, zero ° C. to plus 10 ° C.) can also be exemplified.

(Reaction time)
The reaction time of the present invention is not particularly limited. In one embodiment, from the viewpoints of yield improvement, suppression of by-products, economic efficiency, etc., 0.5 hours to 120 hours, preferably 1 hour to 72 hours, more preferably 1 hour to 48 hours, More preferably, the range of 1 hour-24 hours can be illustrated. In another embodiment, from the same viewpoint as described above, a range of 6 hours to 120 hours, preferably 8 hours to 72 hours, more preferably 8 hours to 48 hours, and further preferably 8 hours to 24 hours can also be exemplified. . However, the reaction time of the present invention can be appropriately adjusted by those skilled in the art.

(Reaction yield and yield)
In the present specification, the terms “reaction yield” and “yield” have the following meanings, respectively.

(Reaction yield)
In the present invention, the organic layer of the reaction mixture was analyzed under the following HPLC analysis conditions (A) to determine the reaction yield. In this specification, the reaction yield is shown as the HPLC area percentage of the target compound.

  The reaction yield in the present invention is preferably 90 to 100%, more preferably 95 to 100%.

(yield)
The yield in the present invention is calculated from the number of moles of the sulfoxide compound (target compound) represented by the general formula (1) obtained with respect to the number of moles of the sulfide derivative (raw material compound) represented by the general formula (2). can do. That is, the yield in the present invention is represented by the following formula:
Yield (%) = (number of moles of target compound obtained) / (number of moles of starting compound) × 100

  The yield in the present invention is preferably in the range of 90 to 100%.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples.

  In the present specification, the following equipment and conditions were used for measuring physical properties of Examples and Comparative Examples.

(HPLC: High performance liquid chromatography)
(HPLC analysis conditions (A))
Pump: LC-20AT (manufactured by Shimadzu Corporation)
Detector: SPD-20A (manufactured by Shimadzu Corporation)
Column: CERI L-column ODS (4.6 × 250 mm), L-C18, 5 μm, 12 nm
Eluent:
Flow rate: 1.0 ml / min
Detection: UV 254nm
Column temperature: 40 ° C

  As described above, the area percentage based on the above HPLC analysis condition (A) was used in the evaluation of the reaction yield.

Regarding the HPLC analysis method, the following documents can be referred to as necessary.
Literature (a): (Corporation) The Chemical Society of Japan, “New Experimental Chemistry Lecture 9 Analytical Chemistry II”, pp. 86-112 (1977), publisher Izumi Izumi, Maruzen Co., Ltd. Literature (b): (Company) The Chemical Society of Japan, "Experimental Chemistry Course 20-1 Analytical Chemistry" 5th edition, pages 130-151 (2007), publisher Seishiro Murata, Maruzen Co., Ltd.

( ¹ H-NMR: ¹ H nuclear magnetic resonance spectrum; analysis condition (A))
Equipment: JEOL JMN-ECS-300 or JEOL JMN-Lambda-400 (manufactured by JEOL RESONANCE)
Internal reference material: Tetramethylsilane (TMS)

(LC / MS: liquid chromatograph mass spectrometry)
(LC / MS analysis conditions)
Pump: Waters Acquity H Class
Detector: Waters Q-Tof Premier
Column: CERI L-column ODS (4.6 × 250 mm), L-C18, 5 μm, 12 nm
Eluent:
Flow rate: 1.0 ml / min
Column temperature: 40 ° C

  In the examples and comparative examples of the present invention, reaction vessels commonly used by those skilled in the art were used as reaction vessels in preparation of the catalyst solution and production of the title compound. For example, about 6 mL screw vial (vial with screw cap) having an inner diameter of 15 mm and a height of 40 mm equipped with a magnetic stirrer with a cross-shaped magnetic stirrer having an outer diameter (length) of 10 mm and a height (thickness) of 5 mm and a thermostatic bath ) Was used.

  In this specification, room temperature is 15 to 30 degreeC.

Example 1
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 14 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 98%
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 0%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Example 2
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 15 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 98%
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 0%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.
After adding aqueous sodium hydrogen sulfite solution to the reaction mixture, the mixture was stirred at room temperature for 5 minutes. The mixture was partitioned into organic and aqueous layers and the organic layer was separated. After adding sodium hydrogen carbonate to the obtained organic layer, the mixture was stirred at room temperature for 5 minutes. The mixture was partitioned into organic and aqueous layers and the organic layer was separated. The obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain 214.2 mg (HPLC purity 97.6%) of the target compound.
Purity conversion yield: 94%.

¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm, TMS standard): 1.57-1.66 (m, 2H), 1.74-1.93 (m, 4H), 2.92 (t, 2H), 3.30-3.43 (m, 1H), 3.66-3.78 (m, 1H), 4.13 (t, 2H), 7.21 (d, 1H), 7.54 (D, 1H)

Example 3
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (5.3 mg, 0.015 mmol), compound of formula (3-12) (3.6 mg, 0.015 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 15.3 mg, 0.075 mmol), and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 60 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 96%
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 0%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Example 4
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-9) (1.1 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 22 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 97%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 0%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Example 5
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution 2,6-dimethoxybenzoic acid (4.6 mg, 0.025 mmol), sodium hydroxide powder (1.0 mg, 0.025 mmol), and dichloromethane (1 mL) were added to a vial with a screw cap. It was. The mixture was stirred at room temperature for 30 minutes. To the solution was added Fe (acac) ₃ (1.8 mg, 0.005 mmol) and the compound of formula (3-9) (1.1 mg, 0.005 mmol). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 21 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 96%
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 0%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Example 6
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 10 ° C. for 14 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 98%
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 0%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Example 7
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 20 ° C. for 36 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 94%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 4%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.
(3) Preparation of title compound using additional hydrogen peroxide To the reaction mixture obtained above, 30% hydrogen peroxide (56.7 mg, 0.5 mmol) was added. The mixture was stirred at 20 ° C. for 15 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 94%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 4%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Comparative Example 1
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-13) (1.0 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 15 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 14%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 83%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.
(3) Preparation of additional catalyst solution Fe (acac) ₃ (5.4 mg, 0.015 mmol), compound of formula (3-13) (3.0 mg, 0.015 mmol), formula (4) in a vial with a screw cap -1) (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL) were added. The mixture was stirred at room temperature for 30 minutes.
(4) Production of title compound using additional catalyst and additional hydrogen peroxide The catalyst solution prepared in (3) above was added to the reaction mixture obtained in (2) above at 0 ° C. 30% hydrogen peroxide (56.7 mg, 0.5 mmol) was added thereto. The mixture was stirred at 0 ° C. for 8 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 23%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 74%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Comparative Example 2
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-19) in a vial with a screw cap ) (Sodium 2-methoxybenzoate; 4.4 mg, 0.025 mmol) and dichloromethane (1 mL) were added. The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 14 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 20%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 77%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Comparative Example 3
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-5) in a vial with a screw cap ) Compound (sodium 4-methoxybenzoate; 4.4 mg, 0.025 mmol), and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 16 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 19%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 80%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Comparative Example 4
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-12) in a vial with a screw cap ) (Sodium benzoate; 3.6 mg, 0.025 mmol) and dichloromethane (1 mL) were added. The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 16 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 16%
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 82%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Comparative Example 5
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), sodium acetate (2. 1 mg, 0.025 mmol), and dichloromethane (1 mL) were added. The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 16 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 19%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 79%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Comparative Example 6
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), and dichloromethane (1 mL) in a vial with a screw cap Was added. The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of the title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 16 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 2%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 96%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.

Comparative Example 7
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (ethylsulfinyl) phenyl] ether

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (ethylthio) phenyl] ether (188.4 mg, 0.500 mmol) was dissolved in dichloromethane (1.0 mL). . The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 24 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (ethylsulfinyl) phenyl] ether (target compound): 39%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (ethylthio) phenyl] ether (raw compound): 55%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (ethylsulfonyl) phenyl] ether (byproduct by overoxidation): 0%.
LC / MS (target compound) of the product; Exact Mass: 392.0295, Found (positive): 393.0370

Comparative Example 8
Production of methylphenyl sulfoxide

(1) Preparation of catalyst solution Fe (acac) ₃ (1.8 mg, 0.005 mmol), compound of formula (3-4) (1.0 mg, 0.005 mmol), formula (4-1) in a vial with a screw cap ) Compound (sodium 2,6-dimethoxybenzoate; 5.1 mg, 0.025 mmol) and dichloromethane (1 mL). The mixture was stirred at room temperature for 30 minutes.
(2) Preparation of title compound Thioanisole (62.1 mg, 0.500 mmol) was dissolved in dichloromethane (1.0 mL). The catalyst solution prepared in (1) above was added thereto. The mixture was cooled to 0 ° C. 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at 0 ° C. for 20 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
Methylphenyl sulfoxide (target compound): 16%,
Thioanisole (raw compound): 77%,
Methylphenylsulfone (by-product by overoxidation): 7%.

LC / MS of target compound; Exact Mass: 140.0, measured value (positive): 141.1
LC / MS of by-product; Exact Mass: 156.0, Found (positive): 157.1

Comparative Example 9
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether

(1) Preparation of title compound 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (215.4 mg, 0.500 mmol) Dissolved in acetonitrile (1.0 mL). Thereto was added sodium tungstate dihydrate (8.2 mg, 0.025 mmol). While the mixture was stirred at room temperature, 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added thereto. The mixture was stirred at room temperature for 15 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 61%,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 32%,
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (byproduct by overoxidation): 2%.
(2) Preparation of title compound using additional hydrogen peroxide To the reaction mixture obtained above, 30% hydrogen peroxide (113.4 mg, 1.0 mmol) was added. The mixture was stirred at room temperature for 23 hours. The organic layer of the reaction mixture was analyzed by HPLC (area percentage). As a result, components other than the solvent and the like in the reaction mixture were as follows:
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether (target compound): 79%
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether (raw compound): 0%
5-Trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfonyl) phenyl] ether (by-product by overoxidation): 12%.

  As disclosed in Patent Document 1, the sulfoxide derivative represented by the general formula (1) has excellent acaricidal activity.

ADVANTAGE OF THE INVENTION According to this invention, the industrially preferable novel manufacturing method of the sulfoxide derivative represented by General formula (1) useful as agricultural chemicals, such as an acaricide, is provided.
As described herein above, the method of the present invention is economical, environmentally friendly and has a high industrial utility value.
In particular, according to the method of the present invention, the target sulfoxide derivative can be selectively produced while avoiding excessive oxidation to the sulfone derivative.
Therefore, the present invention has the advantage that it is not necessary to remove the by-product sulfone derivative, which is difficult to remove.

In short, the present invention has high industrial applicability.

Claims (17)

General formula (1):
(Where
R ¹ is a C1-C10 alkyl group,
C3-C6 cycloalkyl C1-C6 alkyl group, wherein the C3-C6 cycloalkyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group or C1-C4 haloalkyl group. May be
A phenyl C1-C6 alkyl group, wherein the phenyl group moiety may be mono- or poly-substituted by halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C6 haloalkyl groups, cyano groups or nitro groups. Good,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
A C1-C4 haloalkylsulfonyl C2-C10 alkyl group,
A C1-C6 haloalkyl group,
C3-C6 cycloalkyl C1-C6 haloalkyl group, wherein the C3-C6 cycloalkyl group moiety is mono- or poly-substituted by halogen atom, C1-C4 alkyl group, C1-C4 alkoxy group or C1-C6 haloalkyl group. May be
A phenyl C1-C6 haloalkyl group, wherein the phenyl group moiety may be mono- or poly-substituted by halogen atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, C1-C4 haloalkyl groups, cyano groups or nitro groups. Or a C1-C4 haloalkylthio C1-C6 haloalkyl group;
R ² and R ³ are each independently a hydrogen atom, a halogen atom or a C1-C4 alkyl group. ) A sulfoxide derivative represented by the general formula (2):
(Wherein R ¹ , R ² and R ³ are as defined above.)
A sulfide derivative represented by the general formula (3) as a metal compound and a ligand:
(Where
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a phenyl C1-C6 alkyl group, a C6-C10 aryl group, a cyano group, a nitro group, or a C1-C6 alkoxy group. ;
R ⁶ is a C1-C4 alkyl group, a cyano group, a nitro group, a carboxy group, a C1-C4 alkoxycarbonyl group, a C1-C4 alkylcarbonyl group, a hydroxy C1-C4 alkyl group, a C1-C4 alkoxy C1-C4 alkyl group, An amino C1-C4 alkyl group, a cyano C1-C4 alkyl group, a nitro C1-C4 alkyl group, a carboxy C1-C4 alkyl group or a C1-C4 alkoxycarbonyl C1-C4 alkyl group;
R ⁷¹ and R ⁷² are each independently a hydrogen atom, a C1-C6 alkyl group, a phenyl C1-C6 alkyl group, or a C6-C10 aryl group. However, the case where R ⁷¹ and R ⁷² are hydrogen atoms is excluded. )
And a catalyst that is a metal-ligand complex containing a compound represented by formula (4):
(Where
A ¹ is a C1-C2 alkoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom or a C1-C2 alkoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a C1-C2 alkoxy group;
M is a hydrogen atom, an alkali metal atom or an alkaline earth metal atom; and n is 1 or 2. )
And reacting with an oxidizing agent in the presence of a benzoic acid compound represented by the formula: R ¹ is a C1-C10 alkyl group,
A C3-C6 cycloalkyl C1-C6 alkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono- or poly-substituted with a halogen atom or a C1-C4 alkyl group,
A phenyl C1-C6 alkyl group, wherein the phenyl group moiety may be mono- or poly-substituted with a halogen atom or a C1-C4 alkyl group,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
A C1-C4 haloalkylsulfonyl C2-C10 alkyl group,
A C1-C6 haloalkyl group,
A C3-C6 cycloalkyl C1-C6 haloalkyl group, wherein the C3-C6 cycloalkyl group moiety may be mono- or polysubstituted by a halogen atom or a C1-C4 alkyl group, or a phenyl C1-C6 haloalkyl group, The method according to claim 1, wherein the phenyl group moiety may be mono-substituted or poly-substituted with a halogen atom or a C1-C4 alkyl group. R ¹ is a C1-C10 alkyl group,
A C1-C4 alkoxy C2-C10 alkyl group,
A C1-C4 haloalkoxy C2-C10 alkyl group,
A C1-C4 alkylthio C2-C10 alkyl group,
A C1-C4 alkylsulfinyl C2-C10 alkyl group,
A C1-C4 alkylsulfonyl C2-C10 alkyl group,
A C1-C4 haloalkylthio C2-C10 alkyl group,
A C1-C4 haloalkylsulfinyl C2-C10 alkyl group,
The method according to claim 1, which is a C1-C4 haloalkylsulfonyl C2-C10 alkyl group or a C1-C6 haloalkoxy group. R ¹ is C1~C4 haloalkylthio C2~C10 alkyl group; and ^{R 2} and ^{R 3} are each independently a halogen atom or a C1~C4 alkyl group, the process according to claim 1. R ¹ is a 5-trifluoromethylthiopentyl group or 6-trifluoromethylthiohexyl group; and R ² is a fluorine atom and R ³ is a chlorine atom, or R ² and R ³ are methyl groups The method of claim 1. R ¹ is a 5-trifluoromethylthiopentyl group;
The method of claim 1, wherein R ² is a fluorine atom; and R ³ is a chlorine atom. The method of claim 1, wherein R ¹ is a 6-trifluoromethylthiohexyl group; and R ² and R ³ are methyl groups. The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom or a halogen atom;
R ⁶ is a hydroxymethyl group; and R ⁷¹ and R ⁷² are each independently a hydrogen atom or a C1-C6 alkyl group (except when R ⁷¹ and R ⁷² are a hydrogen atom). The method according to any one of claims 1 to 7. The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom, a chlorine atom or a bromine atom;
R ⁶ is a hydroxymethyl group; and R ⁷¹ is a methyl group and R ⁷² is a methyl group, or R ⁷¹ is a hydrogen atom and R ⁷² is an isopropyl group. The method according to any one of the above. The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom or a chlorine atom;
R ⁶ is a hydroxymethyl group; and R ⁷¹ is a methyl group and R ⁷² is a methyl group, or R ⁷¹ is a hydrogen atom and R ⁷² is an isopropyl group. The method according to any one of the above. The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a hydrogen atom;
R ⁶ is a hydroxymethyl group;
R ⁷¹ is a methyl group; and ^{R 72} is a methyl group, the process according to any one of claims 1 to 7. The metal compound is an iron compound;
R ⁴ is a hydrogen atom;
R ⁵ is a chlorine atom;
R ⁶ is a hydroxymethyl group;
R ⁷¹ is a methyl group; and ^{R 72} is a methyl group, the process according to any one of claims 1 to 7. 13. A process according to any one of claims 1 to 12, wherein M is an alkali metal atom; 13. A method according to any one of claims 1 to 12, wherein M is a sodium atom; and n is 1. A ¹ is a methoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom or a methoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
13. A method according to any one of claims 1 to 12, wherein M is a sodium atom; and n is 1. A ¹ is a methoxy group;
A ² is a hydrogen atom;
A ³ is a hydrogen atom;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
13. A method according to any one of claims 1 to 12, wherein M is a sodium atom; and n is 1. A ¹ is a methoxy group;
A ² is a hydrogen atom;
A ³ is a methoxy group;
A ⁴ is a hydrogen atom;
A ⁵ is a methoxy group;
13. A method according to any one of claims 1 to 12, wherein M is a sodium atom; and n is 1.