JPWO2015122396A1 - Method for producing pesticide and intermediate thereof - Google Patents

Abstract

An object of the present invention is to provide a production intermediate suitable for the production of a compound of the general formula (4) having pest control activity on an industrial scale, and a production method thereof. A mercaptophenol derivative is oxidized and then, in the presence of a base, represented by the general formula (a): R3-X (wherein R3 is a C1-C4 haloalkylthio C2-C10 alkyl group; X is a halogen atom, etc.) It is represented by the general formula (3) obtained by reacting with a compound represented by the formula: (wherein R1 and R2 are each independently a halogen atom or a C1-C4 alkyl group). In the presence of a base, the compound is reacted with a compound represented by the general formula (b): R4-Y (wherein R4 is a C1-C4 haloalkyl group; Y is a halogen atom or the like). , General formula (4): (In formula, R1-R4 is synonymous with the above.) The compound represented by this is manufactured. [Selection figure] None

Description

The present invention relates to a general formula (4):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group;
R ⁴ is a C1-C4 haloalkyl group. )
The present invention relates to a method for producing the compound and an intermediate thereof.

In particular, the present invention is a production intermediate of the compound of the general formula (4).
General formula (2):
(Wherein R ¹ and R ² are as defined above.)
And a compound of the general formula (3):
(Wherein R ¹ , R ² and R ³ are as defined above.)
And a compound of the general formula (5):
(Wherein R ¹ , R ² and R ³ are as defined above.)
Of the compound.

  The compound of the general formula (4) is useful as a pest control agent as an agricultural chemical or the like and a production intermediate thereof (see Examples 12, 13, 17, 18, 26 and 27 of Patent Document 1).

In Patent Document 1, for example, 6-thiocyanatohexyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether and trifluoromethyltrimethylsilane are mixed with tetra-n-butyl. A method is disclosed for obtaining the product of Example 26 by reacting in the presence of ammonium fluoride.
This method has a problem in industrial production of 6-thiocyanatohexyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether as a raw material. For example, special equipment is required for mass use of the raw material boronic acid derivatives, and there are problems such as mass use of expensive reagents, use of special reagents, and use of excessive amounts of reagents. (See Examples 21, 24, and 25 of Patent Document 1).
Furthermore, in the prior art, haloalkylating agents such as 1-iodo-2,2,2-trifluoroethane and p-toluenesulfonic acid 2,2,2-trifluoroethyl are used for the production of the compound of the general formula (4). Although used, these haloalkylating agents are expensive, and their large-scale use in the industrial production of the compound of the general formula (4) is a major problem in terms of cost. For example, Patent Document 1 specifically discloses production methods 6 and 7 by way of examples. However, in these production methods, a haloalkylation reaction using these haloalkylating agents is performed at an early stage of the production route of the pest control agent which is the final target compound. As a result, large amounts of expensive haloalkylating agents are used. The problem is that the amount is needed.
In general, sulfur-containing organic compounds often have a characteristic malodor, and the control of this malodor must be taken into consideration in industrial production.
Thus, there are various problems in carrying out the reaction on the scale of industrial production.
Under such circumstances, establishment of a simple method that does not require special equipment or complicated operations and that industrially produces the compound of the general formula (4) has been eagerly desired.

International Publication No. 2013/157229

  An object of the present invention is to provide an industrially preferred production intermediate of the above general formula (4). In other words, an object of the present invention is to provide a production intermediate suitable for production on a large scale in industrial production.

  Another object of the present invention is to provide an industrially preferable method for producing the compound of the general formula (4).

  In view of the above situation, the present inventor has intensively studied a method for producing the compound of the general formula (4). As a result, surprisingly, by providing the compound of the above general formula (2), the compound of the general formula (3) and / or the general formula (5), and using the compound of the above general formula (4) It has been found that the above-mentioned problem can be solved by providing a method for producing the compound. The present inventor has completed the present invention based on this finding.

  That is, the present invention is as follows.

[1] General formula (2):
(Wherein, R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group).

[2] R ¹ and R ² are each independently a halogen atom, or R ¹ and R ² are each independently a C1-C4 alkyl group,
The compound according to [1] above.

[3] R ¹ is a fluorine atom;
R ² is a chlorine atom, or R ¹ and R ² are each methyl.
The compound according to [1] above.

[4] R ¹ and R ² are each independently a halogen atom.
The compound according to [1] above.

[5] R ¹ is a fluorine atom;
R ² is a chlorine atom,
The compound according to [1] above.

[6] R ¹ and R ² are each independently a C1-C4 alkyl group,
The compound according to [1] above.

[7] R ¹ and R ² are each methyl.
The compound according to [1] above.

[8] General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. ) A compound represented by

[9] R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group, or R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
The compound according to [8] above.

[10] R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl or R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
The compound according to [8] above.

[11] R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
The compound according to [8] above.

[12] R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl,
The compound according to [8] above.

[13] R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
The compound according to [8] above.

[14] R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
The compound according to [8] above.

[15] General formula (5):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. ) A compound represented by

[16] R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group, or R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
The compound according to [15] above.

[17] R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl or R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
The compound according to [15] above.

[18] R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
The compound according to [15] above.

[19] R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl,
The compound according to [15] above.

[20] R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
The compound according to [15] above.

[21] R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
The compound according to [15] above.

[22] General formula (4):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group;
R ⁴ is a C1-C4 haloalkyl group. In which the following steps are performed:
(I) General formula (1):
(Wherein R ¹ and R ² are as defined above.)
From the compound represented by general formula (2):
(Wherein R ¹ and R ² are as defined above.)
A process for producing a compound represented by:
(Ii) The compound of the general formula (2) in the presence of a base is represented by the general formula (a):
(Where
R ³ is as defined above;
X is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Is reacted with a compound represented by the general formula (3):
(Wherein R ¹ , R ² and R ³ are as defined above.)
And (iii) a step of converting the compound of the general formula (3) into the compound of the general formula (4),
Including methods.

[23] Step (iii) includes the following steps:
(Iii-a) General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
In the presence of a base, the compound represented by the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Is a step of converting the compound of the general formula (3) into the compound of the general formula (4) by reacting with the compound represented by the formula:
The method according to [22] above.

[24] Step (iii) includes the following steps:
(Iii-b) General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
A compound represented by general formula (5):
(Wherein R ¹ , R ² and R ³ are as defined above.)
And (iii-c) the compound of the general formula (5) in the presence of a base in the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
A step of converting the compound of the general formula (5) into the compound of the general formula (4) by reacting with the compound represented by the formula:
including,
The method according to [22] above.

[25] R ¹ and R ² are each independently a halogen atom, or R ¹ and R ² are each independently a C1-C4 alkyl group,
The method according to [23] or [24] above.

[26] R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy, or R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy.
The method according to [23] or [24] above.

[27] R ¹ and R ² are each independently a halogen atom.
The method according to [23] or [24] above.

[28] R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy.
The method according to [23] or [24] above.

[29] R ¹ and R ² are each independently a C1-C4 alkyl group;
The method according to [23] or [24] above.

[30] R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy.
The method according to [23] or [24] above.

[31] General formula (1):
(In the formula, R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group.)
A compound represented by the general formula (2):
(Wherein R ¹ and R ² are as defined above.)
The method to manufacture the compound represented by these.

[32] General formula (2):
(In the formula, R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group.)
In the presence of a base, the compound represented by the general formula (a):
(Where
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group;
X is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Which is reacted with a compound represented by the general formula (3):
(Wherein R ¹ , R ² and R ³ are as defined above.)
The method to manufacture the compound represented by these.

[33] General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
In the presence of a base, the compound represented by the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Which is reacted with a compound represented by the general formula (4):
(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.)
The method to manufacture the compound represented by these.

[34] General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
Reducing the compound represented by:
General formula (5):
(Wherein R ¹ , R ² and R ³ are as defined above.)
The method to manufacture the compound represented by these.

[35] General formula (5):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
In the presence of a base, the compound represented by the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Which is reacted with a compound represented by the general formula (4):
(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.)
The method to manufacture the compound represented by these.

  According to the present invention, there is provided a novel production intermediate of the compound of the general formula (4) which is useful as a pest control agent and a production intermediate thereof.

  Furthermore, according to this invention, the novel manufacturing method of the compound of General formula (4) useful as a pest control agent and its manufacturing intermediate is provided.

Furthermore, according to the present invention, by using the compound of the general formula (2), (3) and / or (5) of the present invention, the haloalkylation reaction is carried out at a later stage of the pesticide production route. The amount of expensive haloalkylating agents used can be greatly reduced, and the production costs can be significantly reduced. Therefore, the present invention is economical and has high industrial utility value.
Moreover, the bis (2,4-dimethyl-5-hydroxyphenyl) disulfide produced in Example 1 of the present invention has almost no bad odor. Furthermore, bis (2,4-dimethyl-5-hydroxyphenyl) disulfide is a solid having a sufficiently high melting point. A high melting point means that the compound is preferred for storage and provides the option of recrystallization as an isolation and / or purification method. In the present invention, it has been found that bis (2,4-dimethyl-5-hydroxyphenyl) disulfide has such a plurality of advantages simultaneously. The bis (2-chloro-4-fluoro-5-hydroxyphenyl) disulfide produced in Example 6 of the present invention also has similar properties and advantages. Therefore, the compound of the general formula (2) represented by bis (2,4-dimethyl-5-hydroxyphenyl) disulfide and bis (2-chloro-4-fluoro-5-hydroxyphenyl) disulfide is industrially useful. It is.

  According to the present invention, the compounds of the general formulas (2), (3) and (5) which are intermediates for the production of the compound of the general formula (4) can be used without using special reaction conditions or special expensive reagents. Since it can be produced with good yield, it is suitable for industrial production. Therefore, by using these intermediates, industrial production of the compound of the general formula (4) is also a great merit in terms of cost.

  When the present invention was provided, the compounds of the general formulas (2), (3) and (5) and the production methods using them were first realized. Furthermore, the industrial utility value of the compounds of the general formulas (2), (3) and (5) and the production method using them has been realized for the first time by the present invention.

  Hereinafter, the present invention will be described in detail.

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

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. From the viewpoint of the usefulness of the product and the like, preferred examples of the halogen atom include a fluorine atom and a chlorine atom.

  “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.

  The C1-C4 alkyl group means a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of the C1-C4 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, and tert-butyl. From the viewpoint of the usefulness of the product and the like, preferred examples of the C1-C4 alkyl group include methyl.

  A C2-C10 alkyl group means a linear or branched alkyl group having 2 to 10 carbon atoms. Examples of the C2-C10 alkyl group include, but are not limited to, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decanyl and the like. Is not to be done.

  The C1-C4 haloalkyl group means a linear or branched alkyl group having 1 to 4 carbon atoms substituted with the same or different 1 to 9 halogen atoms (wherein the halogen atom is the above) Have the same meaning.) Examples of the C1-C4 haloalkyl group include fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3-fluoropropyl, 2,2,3,3. , 3-pentafluoropropyl, heptafluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, 2,2,3,3,4,4,4-heptafluorobutyl and the like. However, it is not limited to these.

  A C1-C4 haloalkylthio group means a (C1-C4 haloalkyl) -S- group (wherein C1-C4 haloalkyl has the same meaning as described above). Examples of the C1-C4 haloalkylthio group include fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, 2,2,2-trifluoroethylthio, pentafluoroethylthio, 3-fluoropropylthio, 2,2 , 3,3,3-pentafluoropropylthio, heptafluoropropylthio, 2,2,2-trifluoro-1-trifluoromethylethylthio, 2,2,3,3,4,4,4-hepta Although fluorobutylthio etc. are mentioned, it is not limited to these.

  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 the C1-C4 haloalkylthio C2-C10 alkyl group include 2-trifluoromethylthioethyl, 3-trifluoromethylthiopropyl, 4-trifluoromethylthiobutyl, 5-difluoromethylthiopentyl, 5-trifluoromethylthiopentyl, 5 -(2,2,2-trifluoroethylthio) pentyl, 5-pentafluoroethylthiopentyl, 5- (2,2,3,3,3-pentafluoropropylthio) pentyl, 5- (2,2, 3,3,4,4,4-heptafluorobutylthio) pentyl, 6-difluoromethylthiohexyl, 6-trifluoromethylthiohexyl, 6- (2,2,2-trifluoroethylthio) hexyl, 6-penta Fluoroethylthiohexyl, 6- (2,2,3,3,3-pentafluoropropyl Pyrthio) hexyl, 6- (2,2,3,3,4,4,4-heptafluorobutylthio) hexyl, 7-trifluoromethylthioheptyl, 8-trifluoromethylthiooctyl, 9-trifluoromethylthiononyl Examples thereof include, but are not limited to, 10-trifluoromethylthiodecanyl and the like. From the viewpoint of the usefulness of the product and the like, preferred examples of the C1-C4 haloalkylthio C2-C10 alkyl group include 5-trifluoromethylthiopentyl and 6-trifluoromethylthiohexyl.

The C1 -C4 alkylsulfonyloxy group, (C1 -C4 alkyl) means a _-SO 2 -O- group (wherein, C1 -C4 alkyl has the same meaning as above.). Examples of the C1-C4 alkylsulfonyloxy group include, but are not limited to, methanesulfonyloxy, ethanesulfonyloxy, and the like.

The C1 -C4 haloalkylsulfonyl group, means (C1～C haloalkyl) _-SO 2 -O- group (where, C1 -C4 haloalkyl has the same meaning as above.). Examples of the C1-C4 alkylsulfonyloxy group include, but are not limited to, trifluoromethanesulfonyloxy and the like.

C1~C4 The alkyl group or a phenyl sulfonyloxy groups optionally substituted by a halogen atom, means a C1~C4 alkyl group or a halogen atom by an optionally substituted phenyl -SO 2 _-O- group (where And C1-C4 alkyl and halogen atoms have the same meaning as above.) Examples of the phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom include, but are not limited to, benzenesulfonyloxy, p-toluenesulfonyloxy, p-chlorobenzenesulfonyloxy, and the like. It is not a thing.

Examples of R ¹ in the present invention include a halogen atom and a C1-C4 alkyl group.
In view of the usefulness of the product and the like, in one embodiment, preferred R ¹ in the present invention includes, for example, a halogen atom, more preferably a fluorine atom.
From the same viewpoint as described above, in another embodiment, preferable R ¹ in the present invention includes, for example, a C1-C4 alkyl group, more preferably methyl.

Examples of R ² in the present invention include a halogen atom and a C1-C4 alkyl group.
In view of the usefulness of the product and the like, in one embodiment, preferred R ² in the present invention includes, for example, a halogen atom, more preferably a chlorine atom.
From the same viewpoint as described above, in another embodiment, preferable R ² in the present invention includes, for example, a C1-C4 alkyl group, more preferably methyl.

Examples of R ³ in the present invention include C1-C4 haloalkylthio C2-C10 alkyl groups.
In view of the usefulness of the product and the like, in one embodiment, preferable R ³ in the present invention includes, for example, 5-trifluoromethylthiopentyl.
From the same viewpoint as described above, in another embodiment, preferable R ³ in the present invention includes, for example, 6-trifluoromethylthiohexyl.

Examples of R ⁴ in the present invention include a C1-C4 haloalkyl group.
From the viewpoint of the usefulness of the product and the like, preferable R ⁴ in the present invention includes, for example, 2,2,2-trifluoroethyl.

Examples of X in the present invention include a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, and a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. It is done.
In view of reactivity, yield, economic efficiency, etc., preferred X in the present invention includes, for example, chlorine atom, bromine atom, iodine atom, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy. And p-chlorobenzenesulfonyloxy,
More preferably chlorine atom, bromine atom, iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy and p-chlorobenzenesulfonyloxy, more preferably chlorine atom, bromine atom, iodine atom,
More preferably bromine atom and iodine atom,
Particularly preferred is a bromine atom.

Examples of Y in the present invention include a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, and a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. It is done.
In view of reactivity, yield, economic efficiency, etc., preferred X in the present invention includes, for example, chlorine atom, bromine atom, iodine atom, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy. And p-chlorobenzenesulfonyloxy,
More preferably a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy and p-chlorobenzenesulfonyloxy, more preferably a chlorine atom, bromine atom, iodine atom, methanesulfonyloxy, p- Toluenesulfonyloxy,
More preferably bromine atom, iodine atom, methanesulfonyloxy, p-toluenesulfonyloxy,
More preferably, an iodine atom, p-toluenesulfonyloxy,
Particularly preferred is p-toluenesulfonyloxy.

(Process (i))
First, step (i) will be described.

Step (i) is represented by the general formula (1):
(Wherein, R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group). From the compound represented by the general formula (2):
(Wherein R ¹ and R ² are as defined above.)
It is a process of manufacturing the compound represented by these.

  Here, the step (i) is a step of producing the compound of the general formula (2) by oxidizing the compound of the general formula (1). In other words, step (i) is a step of producing the compound of general formula (2) by reacting the compound of general formula (1) with an oxidizing agent.

(Raw material; compound of general formula (1))
The compound of the general formula (1) is used as a raw material for the method of the present invention. The compound of the general formula (1) is a known compound or a compound that can be produced from a known compound by a known method. Specific examples of the compound of the general formula (1) include, for example,
2,4-difluoro-5-mercaptophenol,
2,4-dichloro-5-mercaptophenol,
4-chloro-2-fluoro-5-mercaptophenol,
2-chloro-5-mercapto-4-methylphenol,
2-fluoro-5-mercapto-4-methylphenol,
Examples include 5-mercapto-2,4-dimethylphenol, but are not limited thereto.

(Oxidizing agent in step (i))
The oxidizing agent used in step (i) may be any oxidizing agent as long as the reaction proceeds. Examples of the oxidizing agent that can be used in step (i) include hydrogen peroxide; organic peracids such as peracetic acid and m-chloroperbenzoic acid; oxygen and air; hypochlorites such as sodium hypochlorite; Chlorates such as sodium chlorate; halogens such as chlorine, bromine and iodine; metal oxides such as manganese dioxide; potassium permanganate; potassium ferricyanide (potassium hexacyanoferrate (III)); iron (III) chloride; Examples thereof include, but are not limited to, sulfoxide. From the viewpoint of reactivity, selectivity, economic efficiency, etc., preferred examples of the oxidizing agent in step (i) include hydrogen peroxide and oxygen.

  You may use the oxidizing agent of a process (i) individually or in combination of 2 or more types of arbitrary ratios. The form of the oxidizing agent in step (i) may be any form as long as the reaction proceeds. The form of the oxidizing agent in step (i) can be appropriately selected by those skilled in the art. The amount of the oxidizing agent used in step (i) may be any amount as long as the reaction proceeds. The range of 0.5 to 5 mol, preferably 0.5 to 2 mol, more preferably 0.5 to 1.5 mol can be exemplified with respect to 1 mol of the compound of the general formula (1). The amount of the oxidizing agent used can be adjusted appropriately by those skilled in the art.

  When hydrogen peroxide is used as the oxidizing agent in step (i), the form of hydrogen peroxide may be any form as long as the reaction proceeds. Considering the danger and economic efficiency, the form of hydrogen peroxide includes, for example, an aqueous solution having a concentration of 5% or more and less than 40%, preferably an aqueous solution having a concentration of 10% or more and 35% or less.

  When hydrogen peroxide is used as the oxidizing agent in step (i), the amount of hydrogen peroxide used may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., 0.5 to 1.5 mol, preferably 0.5 to 1.0 mol, more preferably, relative to 1 mol of the compound of the general formula (1) Can exemplify a range of 0.5 to 0.6 mol.

  When hydrogen peroxide is used as the oxidizing agent in step (i), the reaction may be performed in the presence of a catalytic amount of iodides. Iodides may not be used. Whether or not iodides are used can be appropriately determined by those skilled in the art. Examples of iodides include sodium iodide and potassium iodide, preferably sodium iodide. The form of iodides may be any form as long as the reaction proceeds. The amount of iodide used may be any amount as long as the reaction proceeds. From the viewpoints of yield, byproduct suppression, economic efficiency, etc., 0 (zero) to 0.1 mol, preferably 0 to 0.05 mol, more preferably, with respect to 1 mol of the compound of the general formula (1). The range of 0-0.03 mol can be illustrated. In the case of using iodides, 0.001 to 0.1 mol, preferably 0.001 to 0.05 mol, more preferably 0.005 to 0.005 mol per mol of the compound of the general formula (1). A range of 03 moles can also be exemplified.

  When oxygen is used as the oxidizing agent in step (i), air can be used. That is, air oxidation can be used.

(Solvent in step (i))
From the viewpoint of smooth progress of the reaction, the reaction in step (i) is preferably carried out in the presence of a solvent. The solvent of step (i) may be any solvent as long as the reaction of step (i) proceeds.
Examples of the solvent in step (i) include:
water,
Alcohols (eg, methanol, ethanol, 2-propanol, butanol, etc.),
Ethers (for example, tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, dibutyl ether, di-tert-butyl ether, cyclopentyl methyl ether (CPME), methyl-tert-butyl ether, 1,2-dimethoxyethane (DME) Diglyme, triglyme, etc.),
Nitriles (eg acetonitrile),
Amides (for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.),
Alkyl ureas (for example, N, N′-dimethylimidazolidinone (DMI), etc.),
Sulfoxides (for example, dimethyl sulfoxide (DMSO), etc.),
Sulfones (for example, sulfolane),
Ketones (for example, acetone, isobutyl methyl ketone (MIBK), cyclohexanone, etc.),
Carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.),
Carboxylic acids (for example, acetic acid, etc.),
Carbonates (for example, ethylene carbonate, propylene carbonate, etc.),
Aromatic hydrocarbon derivatives (eg benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, etc.),
Halogenated aliphatic hydrocarbons (eg dichloromethane),
And any combination thereof in any proportion, but is not limited thereto.

  From the viewpoint of reactivity and economic efficiency, preferred examples of the solvent in step (i) include water, alcohols, nitriles, amides, sulfoxides, ketones, carboxylic acid esters, carboxylic acids, and aromatic carbonization. Examples include hydrogen derivatives, halogenated aliphatic hydrocarbons, and any combination thereof in any proportion. Preferable specific examples of the solvent in step (i) include water, methanol, ethanol, 2-propanol, acetonitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethyl sulfoxide, Acetone, isobutyl methyl ketone (MIBK), cyclohexanone, ethyl acetate, butyl acetate, acetic acid, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, and any combination thereof in any proportion.

  The amount of the solvent used in step (i) may be any amount as long as the reaction system can be sufficiently stirred. From the viewpoints of yield, by-product suppression, and economic efficiency, the range of 0.01 to 10.0 L (liter), preferably 0.1 to 5.0 L, with respect to 1 mol of the compound of the general formula (1). Can be illustrated. 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.

  When hydrogen peroxide or oxygen is used as the oxidizing agent in the step (i), for example, the compound of the general formula (1) is converted into a sodium salt or potassium in an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The reaction can be carried out in this aqueous solution as an alkali metal salt such as a salt.

(Reaction temperature of step (i))
The reaction temperature in step (i) is not particularly limited. From the viewpoints of yield, by-product suppression, economic efficiency, etc., a range of −30 ° C. (minus 30 ° C.) to 160 ° C., preferably −10 ° C. to 80 ° C. can be exemplified.

(Reaction time of step (i))
The reaction time in step (i) is not particularly limited. From the viewpoint of yield, by-product suppression, economic efficiency, etc., a range of 0.5 hours to 48 hours, preferably 0.5 hours to 24 hours, more preferably 1 hour to 12 hours can be exemplified.

Regarding the step (i), the following documents can be referred to as necessary.
(Corporation) The Chemical Society of Japan, “New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds III”, pp. 1736-1738 (1978), publisher Shingo Iizumi, Maruzen Co., Ltd., Japan Chemical Society, Laboratory Chemistry Lecture 24 Organic Synthesis VI "4th edition, pages 330-331 (1992), publisher Seishiro Murata, Maruzen Co., Ltd.

(Product of step (i); compound of general formula (2))
As the compound of the general formula (2) obtained in the step (i), specifically, for example,
Bis (2,4-difluoro-5-hydroxyphenyl) disulfide,
Bis (2,4-dichloro-5-hydroxyphenyl) disulfide,
Bis (2-chloro-4-fluoro-5-hydroxyphenyl) disulfide,
Bis (4-fluoro-2-methyl-5-hydroxyphenyl) disulfide,
Bis (4-chloro-2-methyl-5-hydroxyphenyl) disulfide,
Examples thereof include, but are not limited to, bis (2,4-dimethyl-5-hydroxyphenyl) disulfide.
Bis (2,4-difluoro-5-hydroxyphenyl) disulfide is also called 5,5′-dithiobis (2,4-difluorophenol).
Bis (2,4-dichloro-5-hydroxyphenyl) disulfide is also called 5,5′-dithiobis (2,4-dichlorophenol).
Bis (2-chloro-4-fluoro-5-hydroxyphenyl) disulfide is also called 5,5′-dithiobis (4-chloro-2-fluorophenol).
Bis (4-fluoro-2-methyl-5-hydroxyphenyl) disulfide is also called 5,5′-dithiobis (2-fluoro-4-methylphenol).
Bis (4-chloro-2-methyl-5-hydroxyphenyl) disulfide is also referred to as 5,5′-dithiobis (2-chloro-4-methylphenol).
Bis (2,4-dimethyl-5-hydroxyphenyl) disulfide is also called 5,5′-dithiobis (2,4-dimethylphenol).

  The compound of the general formula (2) that is the product of the step (i) can be used as a raw material for the step (ii). The compound of the general formula (2) obtained in the step (i) may be isolated and used in the next step, further purified and used in the next step, or used in the next step without isolation. Also good.

(Step (ii))
Next, process (ii) is demonstrated.

Step (ii) is represented by the general formula (2):
(In the formula, R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group.)
In the presence of a base, the compound represented by the general formula (a):
Wherein R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group;
X is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Is reacted with a compound represented by the general formula (3):
(Wherein R ¹ , R ² and R ³ are as defined above.)
It is a process of manufacturing the compound represented by these.

(Compound of general formula (a))
The compound of the general formula (a) is a known compound, or a compound that can be produced from a known compound according to a known method. Specific examples of the compound of the general formula (a) include, for example,
1-chloro-5-trifluoromethylthiopentane,
1-bromo-5-trifluoromethylthiopentane,
1-iodo-5-trifluoromethylthiopentane,
1-methanesulfonyloxy-5-trifluoromethylthiopentane,
1-trifluoromethanesulfonyloxy-5-trifluoromethylthiopentane,
1- (p-toluenesulfonyloxy) -5-trifluoromethylthiopentane,
1-chloro-6-trifluoromethylthiohexane,
1-bromo-6-trifluoromethylthiohexane,
1-iodo-6-trifluoromethylthiohexane,
1-methanesulfonyloxy-6-trifluoromethylthiohexane,
1-trifluoromethanesulfonyloxy-6-trifluoromethylthiohexane,
Examples include 1- (p-toluenesulfonyloxy) -6-trifluoromethylthiohexane, but are not limited thereto.

  The amount of the compound of the general formula (a) used may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., the range of 2.0 to 3.0 mol, preferably 2.0 to 2.4 mol, relative to 1 mol of the compound of the general formula (2) It can be illustrated.

(Base of step (ii))
The base used in step (ii) may be any base as long as the reaction proceeds. Examples of the base that can be used in step (ii) include:
Alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.),
Alkaline earth metal hydroxides (eg, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.),
Alkali metal carbonates (eg, lithium carbonate, sodium carbonate, potassium carbonate, etc.),
Alkaline earth metal carbonates (eg, magnesium carbonate, calcium carbonate, barium carbonate, etc.),
Alkali metal hydrogen carbonates (for example, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.),
Alkaline earth metal bicarbonates (eg, magnesium bicarbonate, calcium bicarbonate, etc.),
Phosphates (eg, sodium phosphate, potassium phosphate, calcium phosphate, etc.),
Hydrogen phosphate (for example, sodium hydrogen phosphate, potassium hydrogen phosphate, calcium hydrogen phosphate, etc.),
Metal hydrides (eg, sodium hydride, calcium hydride, etc.),
Metal alkoxide (for example, sodium methoxide, sodium ethoxide, potassium tert-butoxide and the like) and amines (for example, triethylamine, tributylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undeca- 7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4- (dimethylamino) -pyridine, 2 , 6-lutidine and the like), but is not limited thereto.

  In view of reactivity, yield, economic efficiency, etc., preferred examples of the base in the step (ii) include alkali metal hydroxides, alkali metal carbonates and alkali metal hydrogen carbonates, more preferably alkali metal hydroxides. And alkali metal carbonates. Preferred specific examples of the base in step (ii) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, more preferably sodium hydroxide, potassium hydroxide and sodium carbonate. And potassium carbonate.

  You may use the base of a process (ii) individually or in combination of 2 or more types of arbitrary ratios. The form of the base in step (ii) may be any form as long as the reaction proceeds. The base form of step (ii) can be appropriately selected by those skilled in the art.

  The amount of the base used in step (ii) may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression and economic efficiency, etc., the range of 0.5 to 3.0 mol, preferably 0.5 to 2.4 mol is used per 1 mol of the compound of the general formula (2). It can be illustrated.

(Phase transfer catalyst in step (ii))
The reaction in step (ii) may be performed in the presence of a phase transfer catalyst. A phase transfer catalyst may not be used. Whether or not to use a phase transfer catalyst can be appropriately determined by those skilled in the art. Examples of the phase transfer catalyst include, but are not limited to, quaternary ammonium salts, quaternary phosphonium salts, crown ethers, and the like.

  Examples of quaternary ammonium salts include tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium hydrogen sulfate, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, octyltrimethylammonium chloride, octyltrimethylammonium bromide. , Trioctylmethylammonium chloride, trioctylmethylammonium bromide, benzyllauryldimethylammonium chloride (benzyldodecyldimethylammonium chloride), benzyllauryldimethylammonium bromide (benzyldodecyldimethylammonium bromide), myristyltrimethylammonium chloride (tetradecyltrimethylaluminum) Moniumukurorido), myristyl trimethyl ammonium bromide (tetradecyl trimethyl ammonium bromide), benzyl dimethyl stearyl ammonium chloride (benzyl octadecyl dimethyl ammonium chloride), and benzyl dimethyl stearyl ammonium bromide (benzyl octadecyl dimethyl ammonium bromide) and the like.

  Examples of the quaternary phosphonium salt include tetrabutylphosphonium bromide, tetraoctylphosphonium bromide, and tetraphenylphosphonium bromide.

  Examples of crown ethers include 12-crown-4, 15-crown-5, and 18-crown-6.

  From the viewpoint of reactivity, yield and economic efficiency, the phase transfer catalyst is preferably a quaternary ammonium salt, more preferably tetrabutylammonium bromide or tetrabutylammonium iodide.

  You may use a phase transfer catalyst individually or in combination of 2 or more types of arbitrary ratios. The form of the phase transfer catalyst may be any form as long as the reaction proceeds. The form of the phase transfer catalyst can be appropriately selected by those skilled in the art.

  The amount of the phase transfer catalyst used in step (ii) may be any amount as long as the reaction proceeds. From the viewpoint of yield, by-product suppression, economic efficiency, etc., the range of 0 (zero) to 0.3 mol can be exemplified with respect to 1 mol of the compound of the general formula (2). The amount of the transfer catalyst used can be appropriately adjusted by those skilled in the art.

(Solvent in step (ii))
From the viewpoint of smooth progress of the reaction, the reaction in step (ii) is preferably carried out in the presence of a solvent. The solvent of step (ii) may be any solvent as long as the reaction of step (ii) proceeds. Examples of the solvent in step (ii) include:
Amides (for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.),
Alkyl ureas (for example, N, N′-dimethylimidazolidinone (DMI), etc.),
Sulfoxides (for example, dimethyl sulfoxide (DMSO), etc.),
Sulfones (for example, sulfolane),
Ethers (for example, tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, dibutyl ether, di-tert-butyl ether, cyclopentyl methyl ether (CPME), methyl-tert-butyl ether, 1,2-dimethoxyethane (DME) Diglyme, triglyme, etc.),
Ketones (for example, acetone, isobutyl methyl ketone (MIBK), cyclohexanone, etc.),
Carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.),
Nitriles (eg acetonitrile),
Alcohols (eg, methanol, ethanol, 2-propanol, butanol, etc.),
Aromatic hydrocarbon derivatives (eg benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, etc.),
Halogenated aliphatic hydrocarbons (eg dichloromethane),
water,
And any combination thereof in any proportion, but is not limited thereto.

  In view of reactivity and economic efficiency, preferred examples of the solvent in the step (ii) include amides, sulfoxides, ethers, ketones, nitriles, alcohols, aromatic hydrocarbon derivatives, water, and Any combination of these in any proportion is mentioned. Preferable specific examples of the solvent in the step (ii) include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetone, isobutyl methyl ketone (MIBK), acetonitrile, methanol, ethanol, 2-propanol, toluene, xylene, chlorobenzene, dichlorobenzene, water, and any combination thereof in any proportion.

  The amount of the solvent used in step (ii) may be any amount as long as the reaction system can be sufficiently stirred. From the viewpoints of yield, by-product suppression, economic efficiency, etc., in the range of 0.01 to 10.0 L (liter), preferably 0.1 to 5.0 L, relative to 1 mol of the compound of the general formula (2) Can be illustrated. 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 of step (ii))
The reaction temperature in step (ii) is not particularly limited. From the viewpoints of yield, byproduct suppression, economic efficiency, etc., a range of −10 ° C. (minus 10 ° C.) to 160 ° C., preferably 10 ° C. to 120 ° C. can be exemplified.

(Reaction time of step (ii))
The reaction time in step (ii) is not particularly limited. From the viewpoint of yield, by-product suppression, economic efficiency, etc., a range of 0.5 hour to 48 hours, preferably 1 hour to 24 hours can be exemplified.

(Product of step (ii); compound of general formula (3))
Specific examples of the compound of the general formula (3) obtained in the step (ii) include
Bis [2,4-difluoro-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide,
Bis [2,4-difluoro-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide,
Bis [2,4-dichloro-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide,
Bis [2,4-dichloro-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide,
Bis [2-chloro-4-fluoro-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide,
Bis [2-chloro-4-fluoro-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide,
Bis [4-fluoro-2-methyl-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide,
Bis [4-fluoro-2-methyl-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide,
Bis [4-chloro-2-methyl-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide,
Bis [4-chloro-2-methyl-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide,
Bis [2,4-dimethyl-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide,
Examples thereof include, but are not limited to, bis [2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide.

  The compound of the general formula (3) that is the product of the step (ii) can be used as a raw material for the step (iii). That is, the compound of the general formula (3) which is a product of the step (ii) can be used as a raw material for the step (iii-a) and the step (iii-b). The compound of the general formula (3) obtained in the step (ii) may be isolated and used in the next step, may be further purified and used in the next step, or may be used in the next step without isolation. Also good.

(Process (iii))
Next, process (iii) is demonstrated.

Step (iii) is represented by the general formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
A compound represented by general formula (4):
(Where
R ¹ , R ² and R ³ are as defined above;
R ⁴ is a C1-C4 haloalkyl group. )
It is the process of converting into the compound represented by these.

  Here, step (iii) is step (iii-a) or encompasses step (iii-b) and step (iii-c).

In one embodiment, step (iii) comprises the following steps:
(Iii-a) General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
In the presence of a base, the compound represented by the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
The compound of the said General formula (3) is converted into the compound of the said General formula (4) by making it react with the compound represented by these.

In another embodiment, step (iii) comprises the following steps:
(Iii-b) General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
A compound represented by general formula (5):
(Wherein R ¹ , R ² and R ³ are as defined above.)
And (iii-c) the compound of the general formula (5) in the presence of a base in the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
A step of converting the compound of the general formula (5) into the compound of the general formula (4) by reacting with the compound represented by the formula:
including. Specifically, for example, in step (iii), after step (iii-b) is performed, step (iii-c) is performed.

(Process (iii-a))
Next, process (iii-a) is demonstrated.

Step (iii-a) has the general formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
In the presence of a base, the compound represented by the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
By reacting the compound represented by general formula (3) with general formula (4):
(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.)
It is the process of converting into the compound represented by these.

(Compound of general formula (b) in step (iii-a))
The compound of the general formula (b) in the step (iii-a) is a known compound or a compound that can be produced from a known compound according to a known method. Specific examples of the compound represented by the general formula (b) in the step (iii-a) include, for example,
1-chloro-2,2,2-trifluoroethane,
1-bromo-2,2,2-trifluoroethane,
1-iodo-2,2,2-trifluoroethane,
Methanesulfonic acid 2,2,2-trifluoroethyl,
2,2,2-trifluoroethyl trifluoromethanesulfonate,
Although p-toluenesulfonic acid 2,2,2-trifluoroethyl etc. are mentioned, it is not limited to these.

  The amount of the compound of the general formula (b) used in the step (iii-a) may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., the range of 2.0 to 3.0 moles, preferably 2.0 to 2.4 moles, relative to 1 mole of the compound of the general formula (3). It can be illustrated.

(Base of step (iii-a))
The base used in step (iii-a) may be any base as long as the reaction proceeds. Examples of the base that can be used in the step (iii-a) include:
Alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.),
Alkaline earth metal hydroxides (eg, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.),
Alkali metal carbonates (eg, lithium carbonate, sodium carbonate, potassium carbonate, etc.),
Alkaline earth metal carbonates (eg, magnesium carbonate, calcium carbonate, barium carbonate, etc.),
Alkali metal hydrogen carbonates (for example, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.),
Alkaline earth metal bicarbonates (eg, magnesium bicarbonate, calcium bicarbonate, etc.),
Phosphates (eg, sodium phosphate, potassium phosphate, calcium phosphate, etc.),
Hydrogen phosphate (for example, sodium hydrogen phosphate, potassium hydrogen phosphate, calcium hydrogen phosphate, etc.),
Metal hydrides (eg, sodium hydride, calcium hydride, etc.),
Metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.),
Amines (eg, triethylamine, tributylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4- (dimethylamino) -pyridine, 2,6-lutidine, etc.) and radicals suitable as a base among the radical initiators described later Examples of the initiator include, but are not limited to, sodium bisulfite, potassium bisulfite, Rongalite (trade name) (sodium formaldehyde sulfoxylate dihydrate), and the like.

  In view of reactivity, yield, economic efficiency, and the like, preferred examples of the base in the step (iii-a) include alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates. Preferable specific examples of the base in step (iii-a) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate.

  You may use the base of a process (iii-a) individually or in combination of 2 or more types of arbitrary ratios. The form of the base in step (iii-a) may be any form as long as the reaction proceeds. The base form of step (iii-a) can be appropriately selected by those skilled in the art.

  The amount of the base used in step (iii-a) may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., 0.5 to 3.0 mol, preferably 0.5 to 2.4 mol, more preferably, with respect to 1 mol of the compound of general formula (3). Exemplifies a range of 1.0 to 2.4 mol.

(Radical initiator of step (iii-a))
The reaction of step (iii-a) is performed in the presence or absence of a radical initiator, preferably in the presence of a radical initiator. However, whether or not to use a radical initiator in step (iii-a) can be appropriately determined by those skilled in the art. The radical initiator used in step (iii-a) may be any radical initiator as long as the reaction proceeds. Examples of the radical initiator that can be used in the step (iii-a) include sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium sulfite, potassium sulfite, Rongalite (trade name) (sodium formaldehyde sulfoxylate dihydrate) and the like. However, it is not limited to these. Here, the radical initiator may be understood as a reducing agent. Sodium formaldehyde sulfoxylate dihydrate has the same meaning as sodium hydroxymethylsulfinate dihydrate. From the viewpoints of yield, reactivity, availability, price, ease of handling, and the like, a preferred example of the radical initiator used in step (iii-a) is Rongalite.

  You may use the radical initiator of a process (iii-a) individually or in combination of 2 or more types of arbitrary ratios. The form of the radical initiator in step (iii-a) may be any form as long as the reaction proceeds. The form of the radical initiator in step (iii-a) can be appropriately selected by those skilled in the art. The amount of radical initiator used in step (iii-a) may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, and the like, 0 (zero) to 6.0 mol, preferably 0.01 to 6.0 mol, relative to 1 mol of the compound of the general formula (3), A range of 0.1 to 4.0 mol, more preferably 1.0 to 4.0 mol can be exemplified, but the amount of the radical initiator used in step (iii-a) is appropriately adjusted by those skilled in the art. Can be done. The appropriate radical initiator as described above in the step (iii-a) can also be used as the base in the above step (iii-a). The radical initiator in the step (iii-a) and the base in the above step (iii-a) may be used in combination.

(Solvent of step (iii-a))
From the viewpoint of smooth progress of the reaction, the reaction in the step (iii-a) is preferably carried out in the presence of a solvent. The solvent for the step (iii-a) may be any solvent as long as the reaction of the step (iii-a) proceeds. As the solvent in the step (iii-a), for example,
Amides (for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.),
Alkyl ureas (for example, N, N′-dimethylimidazolidinone (DMI), etc.),
Sulfoxides (for example, dimethyl sulfoxide (DMSO), etc.),
Sulfones (for example, sulfolane),
Ethers (for example, tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, dibutyl ether, di-tert-butyl ether, cyclopentyl methyl ether (CPME), methyl-tert-butyl ether, 1,2-dimethoxyethane (DME) Diglyme, triglyme, etc.),
Ketones (for example, acetone, isobutyl methyl ketone (MIBK), cyclohexanone, etc.),
Carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.),
Nitriles (eg acetonitrile),
Alcohols (eg, methanol, ethanol, 2-propanol, butanol, etc.),
Aromatic hydrocarbon derivatives (eg benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, etc.),
Halogenated aliphatic hydrocarbons (eg dichloromethane),
water,
And any combination thereof in any proportion, but is not limited thereto.

  From the viewpoints of reactivity and economic efficiency, preferred examples of the solvent in step (iii-a) include amides, sulfoxides, ethers, ketones, nitriles, alcohols, aromatic hydrocarbon derivatives, water , And any combination thereof in any proportion. Preferred specific examples of the solvent in step (iii-a) include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO). , Tetrahydrofuran (THF), acetone, isobutyl methyl ketone (MIBK), acetonitrile, methanol, ethanol, 2-propanol, toluene, xylene, chlorobenzene, dichlorobenzene, water, and any combination thereof in any proportion.

  The amount of the solvent used in step (iii-a) may be any amount as long as the reaction system can be sufficiently stirred. From the viewpoints of yield, by-product suppression, economic efficiency, etc., the range of 0.01 to 10.0 L (liter), preferably 0.1 to 5.0 L, relative to 1 mol of the compound of the general formula (3) Can be illustrated. 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 of step (iii-a))
The reaction temperature in step (iii-a) is not particularly limited. From the viewpoints of yield, byproduct suppression, economic efficiency, etc., a range of −10 ° C. (minus 10 ° C.) to 160 ° C., preferably 10 ° C. to 120 ° C. can be exemplified.

(Reaction time of step (iii-a))
The reaction time in step (iii-a) is not particularly limited. From the viewpoint of yield, by-product suppression, economic efficiency, etc., a range of 0.5 hour to 48 hours, preferably 1 hour to 24 hours can be exemplified.

(Product of step (iii-a); compound of general formula (4))
As the compound of the general formula (4) obtained in the step (iii-a), specifically, for example,
5-trifluoromethylthiopentyl- [2,4-difluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether,
6-trifluoromethylthiohexyl- [2,4-difluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether,
5-trifluoromethylthiopentyl- [2,4-dichloro-5- (2,2,2-trifluoroethylthio) phenyl] ether,
6-trifluoromethylthiohexyl- [2,4-dichloro-5- (2,2,2-trifluoroethylthio) phenyl] ether,
5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether,
6-trifluoromethylthiohexyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether,
5-trifluoromethylthiopentyl- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] ether,
6-trifluoromethylthiohexyl- [2-fluoro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] ether,
5-trifluoromethylthiopentyl- [2-chloro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] ether,
6-trifluoromethylthiohexyl- [2-chloro-4-methyl-5- (2,2,2-trifluoroethylthio) phenyl] ether,
5-trifluoromethylthiopentyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether,
Examples thereof include, but are not limited to, 6-trifluoromethylthiohexyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether.

(Process (iii-b))
Next, step (iii-b) will be described.

Step (iii-b) has the general formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
A compound represented by general formula (5):
(Wherein R ¹ , R ² and R ³ are as defined above.)
It is the process of converting into the compound represented by these.

  Here, the step (iii-b) is a step of producing the compound of the general formula (5) by reducing the compound of the general formula (3). In other words, the step (iii-b) is a step of producing the compound of the general formula (5) by reacting the compound of the general formula (3) with a reducing agent.

(Reducing agent in step (iii-b))
The reducing agent used in step (iii-b) may be any reducing agent as long as the reaction proceeds. Examples of the reducing agent that can be used in step (iii-b) include metals (for example, zinc, iron, tin, etc.); borohydride compounds (for example, sodium borohydride, potassium borohydride, sodium cyanoborohydride) , Borane / tetrahydrofuran complex, etc.); aluminum hydride compounds (eg, lithium aluminum hydride, diisobutylaluminum hydride, etc.); triphenylphosphine-hydrous alcohols; tertiary phosphites (eg, triphenylphosphite, trimethylphosphite, Triethyl phosphite and the like); hydrazine hydrate and the like, but are not limited thereto. From the viewpoint of yield, reactivity, availability, price, ease of handling, and the like, preferred examples of the reducing agent in step (iii-b) include metals and borohydride compounds, and more preferably metals. Preferable specific examples of the reducing agent in the step (iii-b) include zinc, iron, tin and sodium borohydride, more preferably zinc, iron and tin.

  You may use the reducing agent of a process (iii-b) individually or in combination of 2 or more types of arbitrary ratios. The form of the reducing agent in step (iii-b) may be any form as long as the reaction proceeds. The form of the reducing agent in step (iii-b) can be appropriately selected by those skilled in the art. The amount of the reducing agent used in step (iii-b) may be any amount as long as the reaction proceeds. The range of 0.25 to 10 mol, preferably 0.25 to 2 mol, preferably 0.5 to 1.5 mol can be exemplified for 1 mol of the compound of the general formula (3). The amount of the reducing agent used in b) can be appropriately adjusted by those skilled in the art.

  When a metal (for example, zinc, iron, tin, etc.) is used as the reducing agent in step (iii-b), the form of the metal may be any form as long as the reaction proceeds. However, powdered metals are preferable from the viewpoints of reactivity, availability, and ease of handling. Accordingly, preferred specific examples of the metal as the reducing agent in the step (iii-b) include zinc powder, iron powder, tin powder and the like. When a metal (for example, zinc, iron, tin, etc.) is used as the reducing agent in step (iii-b), the amount of metal used may be any amount as long as the reaction proceeds. From the viewpoints of yield, byproduct suppression, economic efficiency, etc., 1.0 to 10 mol, preferably 1.0 to 3.0 mol, more preferably 1 to 1 mol of the compound of general formula (3). The range of 0.0-2.0 mol can be illustrated.

  When a metal (for example, zinc, iron, tin, etc.) is used as the reducing agent in step (iii-b), the reaction is preferably performed in the presence of an acid. Examples of the acid include hydrochloric acid, sulfuric acid, acetic acid, and the like, but are not limited thereto. From the viewpoints of yield, reactivity, availability, price, ease of handling, etc., examples of preferred acids include hydrochloric acid and sulfuric acid, more preferably hydrochloric acid. The form of the acid may be any form as long as the reaction proceeds. Examples of the acid form include a liquid or solid containing only an acid, or a solution of a solvent in the step (iii-b) described later other than an aqueous solution or water. From the viewpoints of availability, price, ease of handling, etc., preferred examples of the acid form include acid-only liquids (eg, concentrated sulfuric acid) or 5-50% aqueous solutions (eg, concentrated hydrochloric acid (ie, 35%). Hydrochloric acid) and the like, but the acid form can be appropriately selected by those skilled in the art. The amount of acid used may be any amount as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products and economic efficiency, the range of 1 to 100 mol, preferably 1 to 30 mol, can be exemplified with respect to 1 mol of the compound of the general formula (3). Can be appropriately adjusted by those skilled in the art.

  When a metal (for example, zinc, iron, tin, etc.) is used as the reducing agent in the step (iii-b), it is preferable to use water and / or alcohol. Examples of the alcohol include, but are not limited to, methanol, ethanol, 2-propanol and the like. Water and / or alcohol may be used alone or in combination of two or more in any proportion. The amount of water and / or alcohol used may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products and economic efficiency, the range of 1 to 50 mol can be exemplified with respect to 1 mol of the compound of the general formula (3), but the amount of water and / or alcohol used is It can be adjusted appropriately by the vendor. In addition, when water and / or alcohol is used together with the solvent described later, a large excess of water and / or alcohol may be used regardless of the range exemplified here.

  When using sodium borohydride or the like as the reducing agent in the step (iii-b), it is preferable to use alcohol or the like. Examples of the alcohol include, but are not limited to, methanol, ethanol, 2-propanol and the like. You may use alcohol individually or in combination of 2 or more types of arbitrary ratios. The amount of alcohol used may be any amount as long as the reaction proceeds. From the viewpoints of yield, suppression of by-products, economic efficiency, etc., a range of 1 to 10 mol can be exemplified with respect to 1 mol of the compound of the general formula (3). Can be adjusted. In addition, when alcohol is used also as a solvent to be described later, a large excess of alcohol may be used regardless of the range exemplified here.

(Solvent in step (iii-b))
From the viewpoint of smooth progress of the reaction and the like, the reaction in the step (iii-b) is preferably carried out in the presence of a solvent. The solvent in step (iii-b) may be any solvent as long as the reaction in step (iii-b) proceeds. As the solvent in the step (iii-b), for example,
water,
Alcohols (eg, methanol, ethanol, 2-propanol, butanol, etc.),
Ethers (for example, tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, dibutyl ether, di-tert-butyl ether, cyclopentyl methyl ether (CPME), methyl-tert-butyl ether, 1,2-dimethoxyethane (DME) Diglyme, triglyme, etc.),
Nitriles (eg acetonitrile),
Amides (for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.),
Alkyl ureas (for example, N, N′-dimethylimidazolidinone (DMI), etc.),
Sulfoxides (for example, dimethyl sulfoxide (DMSO), etc.),
Sulfones (for example, sulfolane),
Ketones (for example, acetone, isobutyl methyl ketone (MIBK), cyclohexanone, etc.),
Carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.),
Carboxylic acids (for example, acetic acid, etc.),
Carbonates (for example, ethylene carbonate, propylene carbonate, etc.),
Aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.),
Halogenated aromatic hydrocarbons (eg, chlorobenzene, dichlorobenzene, trichlorobenzene, etc.),
Halogenated aliphatic hydrocarbons (eg dichloromethane),
And any combination thereof in any proportion, but is not limited thereto.

  From the viewpoint of reactivity and economic efficiency, preferred examples of the solvent in step (iii-b) include water, alcohols, ethers, nitriles, amides, carboxylic acid esters, carboxylic acids, and aromatic hydrocarbons. , Halogenated aromatic hydrocarbons, halogenated aliphatic hydrocarbons, and any combination thereof in any proportion. Preferred specific examples of the solvent in step (iii-b) include water, methanol, ethanol, 2-propanol, tetrahydrofuran, acetonitrile, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC). , Ethyl acetate, butyl acetate, acetic acid, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, and any combination thereof in any proportion.

  The amount of the solvent used in step (iii-b) may be any amount as long as the reaction system can be sufficiently stirred. From the viewpoints of yield, by-product suppression, economic efficiency, etc., the range of 0.01 to 10.0 L (liter), preferably 0.1 to 5.0 L, relative to 1 mol of the compound of the general formula (3) Can be illustrated. 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 of step (iii-b))
The reaction temperature in step (iii-b) is not particularly limited. From the viewpoints of yield, byproduct suppression, economic efficiency, etc., a range of −10 ° C. (minus 10 ° C.) to 160 ° C., preferably 10 ° C. to 120 ° C. can be exemplified.

(Reaction time of step (iii-b))
The reaction time in step (iii-b) is not particularly limited. From the viewpoint of yield, by-product suppression, economic efficiency, etc., a range of 0.5 hours to 48 hours, preferably 0.5 hours to 24 hours, more preferably 1 hour to 12 hours can be exemplified.

Regarding the step (iii-b), the following documents can be referred to as necessary.
(Chemical Society of Japan), “New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds III”, pp. 1699-1700 (1978), publisher Shingo Iizumi, Maruzen Co., Ltd., Japan Chemical Society, Laboratory Chemistry Lecture 24 Organic Synthesis VI "4th edition, page 325 (1992), publisher Seishiro Murata, Maruzen Co., Ltd.

(Product of step (iii-b); compound of general formula (5))
Specific examples of the compound of the general formula (5) obtained in the step (iii-b) include, for example,
2,4-difluoro-5- (5-trifluoromethylthiopentyloxy) benzenethiol,
2,4-difluoro-5- (6-trifluoromethylthiohexyloxy) benzenethiol,
2,4-dichloro-5- (5-trifluoromethylthiopentyloxy) benzenethiol,
2,4-dichloro-5- (6-trifluoromethylthiohexyloxy) benzenethiol,
2-chloro-4-fluoro-5- (5-trifluoromethylthiopentyloxy) benzenethiol,
2-chloro-4-fluoro-5- (6-trifluoromethylthiohexyloxy) benzenethiol,
4-fluoro-2-methyl-5- (5-trifluoromethylthiopentyloxy) benzenethiol,
4-fluoro-2-methyl-5- (6-trifluoromethylthiohexyloxy) benzenethiol,
4-chloro-2-methyl-5- (5-trifluoromethylthiopentyloxy) benzenethiol,
4-chloro-2-methyl-5- (6-trifluoromethylthiohexyloxy) benzenethiol,
2,4-dimethyl-5- (5-trifluoromethylthiopentyloxy) benzenethiol,
Examples include 2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) benzenethiol, but are not limited thereto.

  The compound of the general formula (5) which is a product of the step (iii-b) can be used as a raw material for the step (iii-c). The compound of the general formula (5) obtained in the step (iii-b) may be isolated and used in the next step, may be further purified and used in the next step, or may be used in the next step without isolation. It may be used.

(Process (iii-c))
Next, step (iii-c) will be described.

Step (iii-c) is represented by the general formula (5):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
In the presence of a base, the compound represented by the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
By reacting with the compound represented by the formula (5), the compound of the general formula (5) is converted to the general formula (4):
(Wherein R ¹ , R ² , R ³ and R ⁴ are as defined above.)
It is the process of converting into the compound represented by these.

(Compound of general formula (b) in step (iii-c))
The compound of the general formula (b) in the step (iii-c) is a known compound or a compound that can be produced from a known compound according to a known method. The compound of the general formula (b) in the step (iii-c) is specifically as described in the step (iii-a).

  The amount of the compound of the general formula (b) used in the step (iii-c) may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression and economic efficiency, etc., the range of 1.0 to 1.5 mol, preferably 1.0 to 1.2 mol, per 1 mol of the compound of the general formula (5) It can be illustrated.

(Base of step (iii-c))
The base used in step (iii-c) may be any base as long as the reaction proceeds. Examples of the base that can be used in step (iii-c) include:
Alkali metal hydroxides (eg, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.),
Alkaline earth metal hydroxides (eg, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.),
Alkali metal carbonates (eg, lithium carbonate, sodium carbonate, potassium carbonate, etc.),
Alkaline earth metal carbonates (eg, magnesium carbonate, calcium carbonate, barium carbonate, etc.),
Alkali metal hydrogen carbonates (for example, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc.),
Alkaline earth metal bicarbonates (eg, magnesium bicarbonate, calcium bicarbonate, etc.),
Phosphates (eg, sodium phosphate, potassium phosphate, calcium phosphate, etc.),
Hydrogen phosphate (for example, sodium hydrogen phosphate, potassium hydrogen phosphate, calcium hydrogen phosphate, etc.),
Metal hydrides (eg, sodium hydride, calcium hydride, etc.),
Metal alkoxides (eg, sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.),
Amines (eg, triethylamine, tributylamine, diisopropylethylamine, 1,8-diazabicyclo [5.4.0] -7-undec-7-ene (DBU), 1,4-diazabicyclo [2.2.2] octane (DABCO), N, N-dimethylaniline, N, N-diethylaniline, pyridine, 4- (dimethylamino) -pyridine, 2,6-lutidine, etc.) and radicals suitable as a base among the radical initiators described later Examples of the initiator include, but are not limited to, sodium bisulfite, potassium bisulfite, Rongalite (trade name) (sodium formaldehyde sulfoxylate dihydrate), and the like.

  In view of reactivity, yield, economic efficiency, and the like, preferred examples of the base in the step (iii-c) include alkali metal hydroxides, alkali metal carbonates, and alkali metal hydrogen carbonates. Preferable specific examples of the base in step (iii-c) include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.

  You may use the base of a process (iii-c) individually or in combination of 2 or more types of arbitrary ratios. The form of the base in step (iii-c) may be any form as long as the reaction proceeds. The base form of step (iii-c) can be appropriately selected by those skilled in the art.

  The amount of the base used in step (iii-c) may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., the range of 0.5 to 1.5 mol, preferably 0.5 to 1.2 mol, per 1 mol of the compound of the general formula (5) It can be illustrated.

(Radical initiator of step (iii-c))
The reaction of step (iii-c) is carried out in the presence or absence of a radical initiator, preferably in the presence of a radical initiator. However, whether or not to use a radical initiator in step (iii-c) can be appropriately determined by those skilled in the art. The radical initiator used in step (iii-c) may be any radical initiator as long as the reaction proceeds. Examples of the radical initiator that can be used in the step (iii-c) include sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium sulfite, potassium sulfite, Rongalite (trade name) (sodium formaldehyde sulfoxylate dihydrate) and the like. However, it is not limited to these. Here, the radical initiator may be understood as a reducing agent. Sodium formaldehyde sulfoxylate dihydrate has the same meaning as sodium hydroxymethylsulfinate dihydrate. From the viewpoint of yield, reactivity, availability, price, ease of handling, and the like, a preferred example of the radical initiator used in step (iii-c) is Rongalite.

  You may use the radical initiator of a process (iii-c) individually or in combination of 2 or more types of arbitrary ratios. The form of the radical initiator in step (iii-c) may be any form as long as the reaction proceeds. The form of the radical initiator in step (iii-c) can be appropriately selected by those skilled in the art. The amount of the radical initiator used in step (iii-c) may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, and the like, 0 (zero) to 2.0 mol, preferably 0.01 to 2.0 mol, relative to 1 mol of the compound of the general formula (5), Although the range of 0.1-1.5 mol can be illustrated preferably, the usage-amount of the radical initiator of a process (iii-c) can be adjusted suitably by those skilled in the art. The appropriate radical initiator as described above in the step (iii-c) can also be used as the base in the above step (iii-c). The radical initiator in the step (iii-c) and the base in the above step (iii-c) may be used in combination.

(Solvent in step (iii-c))
From the viewpoint of smooth progress of the reaction, the reaction in step (iii-c) is preferably carried out in the presence of a solvent. The solvent for the step (iii-c) may be any solvent as long as the reaction of the step (iii-c) proceeds. As the solvent in the step (iii-c), for example,
Amides (for example, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.),
Alkyl ureas (for example, N, N′-dimethylimidazolidinone (DMI), etc.),
Sulfoxides (for example, dimethyl sulfoxide (DMSO), etc.),
Sulfones (for example, sulfolane),
Ethers (for example, tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, dibutyl ether, di-tert-butyl ether, cyclopentyl methyl ether (CPME), methyl-tert-butyl ether, 1,2-dimethoxyethane (DME) Diglyme, triglyme, etc.),
Ketones (for example, acetone, isobutyl methyl ketone (MIBK), cyclohexanone, etc.),
Carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.),
Nitriles (eg acetonitrile),
Alcohols (eg, methanol, ethanol, 2-propanol, butanol, etc.),
Aromatic hydrocarbon derivatives (eg benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene, etc.),
Halogenated aliphatic hydrocarbons (eg dichloromethane),
water,
And any combination thereof in any proportion, but is not limited thereto.

  From the viewpoints of reactivity and economic efficiency, preferred examples of the solvent in step (iii-c) include amides, sulfoxides, ethers, ketones, nitriles, alcohols, aromatic hydrocarbon derivatives, water , And any combination thereof in any proportion. Preferred specific examples of the solvent in step (iii-c) include N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO). , Tetrahydrofuran (THF), acetone, isobutyl methyl ketone (MIBK), acetonitrile, methanol, ethanol, 2-propanol, toluene, xylene, chlorobenzene, dichlorobenzene, water, and any combination thereof in any proportion.

  The amount of the solvent used in step (iii-c) may be any amount as long as the reaction system can be sufficiently stirred. From the viewpoints of yield, by-product suppression and economic efficiency, etc., the range of 0.01 to 10.0 L (liter), preferably 0.1 to 5.0 L, relative to 1 mol of the compound of the general formula (5) Can be illustrated. 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 of step (iii-c))
The reaction temperature in step (iii-c) is not particularly limited. From the viewpoints of yield, byproduct suppression, economic efficiency, etc., a range of −10 ° C. (minus 10 ° C.) to 160 ° C., preferably 10 ° C. to 120 ° C. can be exemplified.

(Reaction time of step (iii-c))
The reaction time in step (iii-c) is not particularly limited. From the viewpoint of yield, by-product suppression, economic efficiency, etc., a range of 0.5 hour to 48 hours, preferably 1 hour to 24 hours can be exemplified.

(Product of step (iii-c); compound of general formula (4))
Specific examples of the compound of the general formula (4) obtained in the step (iii-c) include specific examples of the compound of the general formula (4) obtained in the above-described step (iii-a). However, the present invention is not limited to this.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, this invention is not limited at all by these Examples.

Example 1
Production of bis (2,4-dimethyl-5-hydroxyphenyl) disulfide
To the reaction flask, 4.32 g (28.0 mmol) of 5-mercapto-2,4-dimethylphenol, 42 mg (0.28 mmol) of sodium iodide and 80 mL of ethyl acetate were added. While stirring the mixture at room temperature, 1.59 g (14 mmol) of 30% aqueous hydrogen peroxide was slowly added dropwise thereto. The mixture was stirred at room temperature for 1 hour. 5 mL of a saturated aqueous sodium sulfite solution was added to the reaction mixture, the mixture was stirred at room temperature for 10 minutes, and concentrated hydrochloric acid was added thereto to adjust the pH of the aqueous layer to about pH 1-2. The obtained mixture was partitioned into an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 3.03 g of bis (2,4-dimethyl-5-hydroxyphenyl) disulfide in a yield of 71%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 6.94 (s, 2H), 6.90 (s, 2H), 4.87 (s, 2H), 2.30 (s, 6H) , 2.17 (s, 6H).
Melting point: 125-127 ° C

Example 2
Preparation of bis [2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide
In a reaction flask, bis (2,4-dimethyl-5-hydroxyphenyl) disulfide 2.60 g (8.5 mmol), 1-bromo-6-trifluoromethylthiohexane 4.73 g (17.9 mmol), potassium carbonate 2.58 g (18.7 mmol), tetrabutylammonium iodide 0.63 g (1.7 mmol) and N, N-dimethylformamide 17 mL were added. The mixture was stirred at 80 ° C. for 20 hours under a nitrogen atmosphere. Dilute hydrochloric acid, water and diethyl ether were added to the reaction mixture, the mixture was partitioned into an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 4.95 g of bis [2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide in a yield of 86%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 6.92 (s, 2H), 6.90 (s, 2H), 3.78 (t, 4H), 2.88 (t, 4H) , 2.30 (s, 6H), 2.14 (s, 6H), 1.72 (m, 8H), 1.45 (m, 8H).

Example 3
Preparation of 6-trifluoromethylthiohexyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether
In a reaction flask, bis [2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide 337.4 mg (0.50 mmol), p-toluenesulfonic acid 2,2,2-trifluoroethyl 266. 9 mg (1.05 mmol), potassium carbonate 152.0 mg (1.10 mmol), Rongalite (trade name) (sodium formaldehyde sulfoxylate dihydrate) 231.2 mg (1.50 mmol) and N, N-dimethylformamide 2 mL Was added. The mixture was stirred at 50 ° C. for 16 hours under a nitrogen atmosphere. Dilute hydrochloric acid, water and diethyl ether were added to the reaction mixture, the mixture was partitioned into an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to collect 242.0 mg of 6-trifluoromethylthiohexyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether. Obtained at a rate of 58%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 6.96 (s, 1H), 6.70 (s, 1H), 3.94 (t, 2H), 3.30 (q, 2H) , 2.90 (t, 2H), 2.38 (s, 3H), 2.17 (s, 3H), 1.71-1.82 (m, 4H), 1.49-1.53 (m , 4H).

Example 4
Preparation of 2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) benzenethiol
Bis [2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) phenyl] disulfide 337.4 mg (0.50 mmol), concentrated hydrochloric acid 1 mL and methanol 2 mL were added to the reaction flask. While the mixture was stirred at room temperature, 32.7 mg (0.50 mmol) of zinc powder was added thereto. The mixture was stirred at 80 ° C. for 2 hours. Water and diethyl ether were added to the reaction mixture, the mixture was partitioned between an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 176.0 mg of 2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) benzenethiol in a yield of 52%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 6.92 (s, 1H), 6.74 (s, 1H), 3.90 (t, 2H), 3.22 (s, 1H) , 2.89 (t, 2H), 2.24 (s, 3H), 2.13 (s, 3H), 1.76 (m, 4H), 1.49 (m, 4H).

Example 5
Preparation of 6-trifluoromethylthiohexyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether
In a reaction flask, 176.0 mg (0.52 mmol) of 2,4-dimethyl-5- (6-trifluoromethylthiohexyloxy) benzenethiol, 138.8 mg of p-toluenesulfonate 2,2,2-trifluoroethyl (0 .55 mmol), 79.1 mg (0.57 mmol) of potassium carbonate, Rongalite (trade name) (sodium formaldehyde sulfoxylate dihydrate) 40.1 mg (0.26 mmol) and 2 mL of N, N-dimethylformamide were added. . The mixture was stirred at 50 ° C. for 15 hours under a nitrogen atmosphere. Dilute hydrochloric acid, water and diethyl ether were added to the reaction mixture, the mixture was partitioned into an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography to collect 188.0 mg of 6-trifluoromethylthiohexyl- [2,4-dimethyl-5- (2,2,2-trifluoroethylthio) phenyl] ether. Obtained at a rate of 86%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 6.96 (s, 1H), 6.70 (s, 1H), 3.94 (t, 2H), 3.30 (q, 2H) , 2.90 (t, 2H), 2.38 (s, 3H), 2.17 (s, 3H), 1.71-1.82 (m, 4H), 1.49-1.53 (m , 4H).

Example 6
Preparation of bis (2-chloro-4-fluoro-5-hydroxyphenyl) disulfide
To the reaction flask, 44.7 mg (0.25 mmol) of 4-chloro-2-fluoro-5-mercaptophenol and 1 mL of water were added. While stirring the mixture at room temperature, 26.7 mg (0.28 mmol) of 35% aqueous hydrogen peroxide was slowly added dropwise thereto. The mixture was stirred at room temperature for 1 hour. After filtration of the reaction mixture, the filtrate was washed with water and dried to obtain 39.9 mg of bis (2-chloro-4-fluoro-5-hydroxyphenyl) disulfide in a yield of 90%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.22 (d, J = 8.7 Hz, 2H), 7.16 (d, J = 9.6 Hz, 2H).
Melting point: 160 ° C

Example 7
Preparation of bis [2-chloro-4-fluoro-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide
The reaction flask was charged with 177.6 mg (0.50 mmol) of bis (2-chloro-4-fluoro-5-hydroxyphenyl) disulfide, 263.7 mg (1.05 mmol) of 1-bromo-5-trifluoromethylthiopentane, 152 of potassium carbonate. 0.0 mg (1.10 mmol) and 1 mL of N, N-dimethylformamide were added. The mixture was stirred at 50 ° C. for 15 hours under a nitrogen atmosphere. Dilute hydrochloric acid, water and diethyl ether were added to the reaction mixture, the mixture was partitioned into an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 277.0 mg of bis [2-chloro-4-fluoro-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide in a yield of 80%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.21 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 10.2 Hz, 2H), 3.97 (t , J = 6.3 Hz, 4H), 2.90 (t, J = 7.2 Hz, 4H), 1.78 (m, 8H), 1.56 (m, 4H).

Example 8
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether
In a reaction flask, 277.0 mg (0.40 mmol) of bis [2-chloro-4-fluoro-5- (5-trifluoromethylthiopentyloxy) phenyl] disulfide, 2,2,2-trifluoroethyl p-toluenesulfonate 213.5 mg (0.84 mmol), potassium carbonate 121.6 mg (0.88 mmol), Rongalite (trade name) (sodium formaldehyde sulfoxylate dihydrate) 184.9 mg (1.20 mmol), water 72.0 mg ( 4.0 mmol) and 1 mL of N, N-dimethylformamide were added. The mixture was stirred at 50 ° C. for 12 hours under a nitrogen atmosphere. Dilute hydrochloric acid, water and diethyl ether were added to the reaction mixture, the mixture was partitioned into an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 306.0 mg of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether Was obtained in 89% yield.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.23 (d, J = 8.4 Hz, 1H), 7.21 (d, J = 10.8 Hz, 1H), 4.03 (t , J = 6.3 Hz, 2H), 3.41 (d, J = 9.6 Hz, 2H), 2.92 (t, J = 7.5 Hz, 2H), 1.82 (m, 4H), 1 .61 (m, 2H).

Reference example 1
Production of 1-bromo-6-trifluoromethylthiohexane (1) Production of 6-bromohexyl acetate
To the reaction flask, 6.27 g (89.9 mmol) of 6-bromo-1-hexanol, 9.63 g (94.3 mmol) of acetic anhydride and 180 mL of toluene were added. While stirring with ice cooling, 10.48 g (98.9 mmol) of anhydrous sodium carbonate and 0.55 g (4.5 mmol) of N, N-dimethyl-4-aminopyridine were added to the reaction mixture. Thereafter, the mixture was stirred for 3 hours under ice cooling. Dilute hydrochloric acid and water were added to the resulting reaction mixture, and the mixture was partitioned between toluene and water to obtain a toluene layer containing 6-bromohexyl acetate. The obtained toluene layer containing 6-bromohexyl acetate was used for the next reaction.
(2) Production of 6-thiocyanatohexyl acetate
The total amount of the toluene layer containing 6-bromohexyl acetate obtained in (1) in the reaction flask, 8.75 g (107.9 mmol) of sodium thiocyanate, 2.90 g (9.0 mmol) of tetrabutylammonium bromide and 100 mL of water Was added. The mixture was then stirred at 80 ° C. for 5 hours. The resulting reaction mixture was partitioned between toluene and water, and the toluene layer was separated. Subsequently, the toluene layer was dried over anhydrous magnesium sulfate and filtered, and then toluene was distilled off under reduced pressure to obtain 6-thiocyanatohexyl acetate. The obtained 6-thiocyanatohexyl acetate was used in the next reaction without purification.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.07 (t, J = 6.6 Hz, 2H), 2.96 (t, J = 6.9 Hz, 2H), 2.06 (s , 3H), 1.85 (quin, J = 6.6 Hz, 2H), 1.66 (quin, J = 6.9 Hz, 2H), 1.43 (m, 4H).
(3) Production of 6-trifluoromethylthiohexyl acetate
To the reaction flask, the total amount of 6-thiocyanatohexyl acetate obtained in (2), 25.60 g (180 mmol) of trifluoromethyltrimethylsilane and 90 mL of tetrahydrofuran were added. Subsequently, 9 mL of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was added dropwise while stirring the mixture under ice cooling. Thereafter, the mixture was stirred for 1 hour under ice cooling. Tetrahydrofuran was distilled off under reduced pressure from the resulting reaction mixture. Diethyl ether and water were added to the resulting residue, and the mixture was partitioned between diethyl ether and water, and the diethyl ether layer was separated. Subsequently, the diethyl ether layer was dried over anhydrous magnesium sulfate and filtered, and then diethyl ether was distilled off under reduced pressure to obtain 6-trifluoromethylthiohexyl acetate. The obtained 6-trifluoromethylthiohexyl acetate was used for the next reaction without purification.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.06 (t, J = 6.6 Hz, 2H), 2.88 (t, J = 7.2 Hz, 2H), 2.05 (s , 3H), 1.67 (m, 4H), 1.41 (m, 4H).
(4) Production of 6-trifluoromethylthiohexane-1-ol
To the reaction flask, the total amount of 6-trifluoromethylthiohexyl acetate obtained in (3), 13.68 g (99 mmol) of potassium carbonate, and 90 mL of methanol were added. The mixture was then stirred at room temperature for 14 hours. Methanol was distilled off under reduced pressure from the resulting reaction mixture. Diethyl ether and water were added to the resulting residue, and the mixture was partitioned between diethyl ether and water, and the diethyl ether layer was separated. Subsequently, the diethyl ether layer was dried over anhydrous magnesium sulfate and filtered, and then diethyl ether was distilled off under reduced pressure to obtain 6-trifluoromethylthiohexane-1-ol. The obtained 6-trifluoromethylthiohexane-1-ol was used in the next reaction without purification.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.66 (t, J = 6.6 Hz, 2H), 2.89 (t, J = 7.5 Hz, 2H), 1.72 (quin , J = 7.5 Hz, 2H), 1.59 (quin, J = 6.6 Hz, 2H), 1.43 (m, 4H).
(5) Production of 1-bromo-6-trifluoromethylthiohexane
To the reaction flask, the total amount of 6-trifluoromethylthiohexane-1-ol obtained in (4), 45.51 g (270 mmol) of 48% hydrobromic acid and 2.90 g (9.0 mmol) of tetrabutylammonium bromide were added. It was. The mixture was then stirred at 130 ° C. for 4 hours. Dichloromethane and water were added to the resulting reaction mixture, and the mixture was partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure. The obtained residue was purified by distillation under reduced pressure to obtain 20.51 g of 1-bromo-6-trifluoromethylthiohexane. The yield of 5 steps was 86%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.41 (t, J = 6.9 Hz, 2H), 2.89 (t, J = 7.2 Hz, 2H), 1.87 (quin , J = 7.2 Hz, 2H), 1.72 (quin, J = 6.9 Hz, 2H), 1.47 (m, 4H).

Reference example 2
Production of 5-mercapto-2,4-dimethylphenol (1) Production of 2,4-dimethylphenylmethanesulfonate
To the reaction flask, 12.22 g (100.0 mmol) of 2,4-dimethylphenol, 11.68 g (102.0 mmol) of methanesulfonyl chloride and 100 mL of dichloromethane were added. Subsequently, while the mixture was stirred under ice-cooling, a solution of triethylamine 11.13 g (110.0 mmol) in 50 mL of dichloromethane was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. Water was added to the resulting reaction mixture, which was partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure to obtain 19.78 g of 2,4-dimethylphenylmethanesulfonate in a yield of 99%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.16 (d, J = 8.1 Hz, 1H), 7.07 (d, J = 0.6 Hz, 1H), 7.01 (dd , J = 8.1, 0.6 Hz, 1H), 3.17 (s, 3H), 2.32 (s, 3H), 2.31 (s, 3H).
(2) Production of 5-chlorosulfonyl-2,4-dimethylphenylmethanesulfonate
To the reaction flask was added 5.91 g (22.2 mmol) of 30% fuming sulfuric acid and 10 mL of dichloromethane. Subsequently, a solution prepared by dissolving 4.35 g (21.7 mmol) of 2,4-dimethylphenylmethanesulfonate in 12 mL of dichloromethane was added dropwise while stirring the mixture under ice-cooling. After completion of the dropwise addition, the mixture was stirred for 1 hour under ice cooling. Thereafter, 6.45 g (54.3 mmol) of thionyl chloride was added to the mixture. Subsequently, the mixture was stirred at 50 ° C. for 3 hours. The obtained reaction mixture was added dropwise to ice water and then partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 5.65 g of 5-chlorosulfonyl-2,4-dimethylphenylmethanesulfonate in a yield of 87%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.93 (s, 1H), 7.35 (s, 1H), 3.30 (s, 3H), 2.75 (s, 3H) , 2.45 (s, 3H).
(3) Production of 5-mercapto-2,4-dimethylphenylmethanesulfonate
To the reaction flask, 610.0 mg (2.0 mmol) of 5-chlorosulfonyl-2,4-dimethylphenylmethanesulfonate, 2 mL of 18% hydrochloric acid and 2 mL of methanol were added. Subsequently, 484.8 mg (4.1 mmol) of tin powder was added while stirring the mixture at room temperature. The mixture was then stirred at 80 ° C. for 1 hour. Methanol was distilled off under reduced pressure from the resulting reaction mixture. Dichloromethane and water were added to the resulting residue, and the mixture was partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 400.0 mg of 5-mercapto-2,4-dimethylphenylmethanesulfonate in a yield of 84%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.22 (s, 1H), 7.06 (s, 1H), 3.18 (s, 3H), 2.28 (s, 3H) , 2.27 (s, 3H).
(4) Production of 5-mercapto-2,4-dimethylphenol
To the reaction flask, 2.32 g (10.0 mmol) of 5-mercapto-2,4-dimethylphenylmethanesulfonate, 4.00 g (100.0 mmol) of sodium hydroxide and 15 mL of water were added. The mixture was then stirred at 80 ° C. for 1 hour. Hydrochloric acid was added to the resulting reaction mixture to adjust the pH to about 1. Subsequently, dichloromethane was added thereto, and the mixture was partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.48 g of 5-mercapto-2,4-dimethylphenol in a yield of 96%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 6.90 (s, 1H), 6.74 (s, 1H), 3.19 (s, 1H), 2.22 (s, 1H) , 2.17 (s, 1H).

Reference example 3
Production of 1-bromo-5-trifluoromethylthiopentane (1) Production of 5-bromopentyl acetate
To the reaction flask, 20.30 g (121.5 mmol) of 5-bromo-1-pentanol, 13.03 g (127.6 mmol) of acetic anhydride and 120 mL of toluene were added. To the reaction mixture, 14.17 g (133.7 mmol) of anhydrous sodium carbonate and 0.74 g (6.1 mmol) of N, N-dimethyl-4-aminopyridine were added while stirring under ice cooling. Thereafter, the mixture was stirred for 2 hours under ice cooling. Dilute hydrochloric acid and water were added to the resulting reaction mixture, and the mixture was partitioned between toluene and water to obtain a toluene layer containing 5-bromopentyl acetate. The obtained toluene layer containing 5-bromopentyl acetate was used for the next reaction.
(2) Production of 5-thiocyanatopentyl acetate
Total amount of toluene layer containing 5-bromopentyl acetate obtained in (1) in reaction flask, 14.78 g (182.3 mmol) of sodium thiocyanate, 3.92 g (12.2 mmol) of tetrabutylammonium bromide and 120 mL of water Was added. The mixture was then stirred at 80 ° C. for 3 hours. The resulting reaction mixture was partitioned between toluene and water, and the toluene layer was separated. Subsequently, the toluene layer was dried over anhydrous magnesium sulfate and filtered, and then toluene was distilled off under reduced pressure to obtain 5-thiocyanatopentyl acetate. The obtained 5-thiocyanatopentyl acetate was used in the next reaction without purification.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.09 (t, J = 6.3 Hz, 2H), 2.96 (t, J = 7.2 Hz, 2H), 2.06 (s , 3H), 1.88 (m, 2H), 1.71 (m, 2H), 1.53 (m, 2H).
(3) Production of 5-trifluoromethylthiopentyl acetate
To the reaction flask, the total amount of 5-thiocyanatopentyl acetate obtained in (2), 25.81 g (181.5 mmol) of trifluoromethyltrimethylsilane and 100 mL of tetrahydrofuran were added. Subsequently, 12 mL of tetrabutylammonium fluoride (1 mol / L tetrahydrofuran solution) was added dropwise while stirring the mixture under ice-cooling. Thereafter, the mixture was stirred for 2 hours under ice cooling. Tetrahydrofuran was distilled off under reduced pressure from the resulting reaction mixture. Diethyl ether and water were added to the resulting residue, and the mixture was partitioned between diethyl ether and water, and the diethyl ether layer was separated. Subsequently, the diethyl ether layer was dried over anhydrous magnesium sulfate and filtered, and then diethyl ether was distilled off under reduced pressure to obtain 5-trifluoromethylthiopentyl acetate. The obtained 5-trifluoromethylthiopentyl acetate was used in the next reaction without purification.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.07 (t, J = 6.3 Hz, 2H), 2.89 (t, J = 7.5 Hz, 2H), 2.05 (s , 3H), 1.70 (m, 4H), 1.48 (m, 2H).
(4) Production of 5-trifluoromethylthiopentan-1-ol
To the reaction flask, the total amount of 5-trifluoromethylthiopentyl acetate obtained in (3), 15.93 g (115.3 mmol) of potassium carbonate, and 100 mL of methanol were added. The mixture was then stirred at room temperature for 5 hours. Methanol was distilled off under reduced pressure from the resulting reaction mixture. Diethyl ether and water were added to the resulting residue, and the mixture was partitioned between diethyl ether and water, and the diethyl ether layer was separated. Subsequently, the diethyl ether layer was dried over anhydrous magnesium sulfate and filtered, and then diethyl ether was distilled off under reduced pressure to obtain 5-trifluoromethylthiopentan-1-ol. The obtained 5-trifluoromethylthiopentan-1-ol was used in the next reaction without purification.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.67 (t, J = 6.0 Hz, 2H), 2.90 (t, J = 7.2 Hz, 2H), 1.74 (m , 2H), 1.54 (m, 4H).
(5) Production of 1-bromo-5-trifluoromethylthiopentane
To the reaction flask, the total amount of 5-trifluoromethylthiopentan-1-ol obtained in (4) and 53.12 g (315 mmol) of 48% hydrobromic acid were added. The mixture was then stirred at 140 ° C. for 6 hours. Dichloromethane and water were added to the resulting reaction mixture, and the mixture was partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure. The obtained residue was purified by distillation under reduced pressure to obtain 14.11 g of 1-bromo-5-trifluoromethylthiopentane. The yield of 5 steps was 46%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.42 (t, J = 6.9 Hz, 2H), 2.90 (t, J = 7.2 Hz, 2H), 1.90 (m , 2H), 1.74 (m, 2H), 1.57 (m, 2H).

Reference example 4
Production of 4-chloro-2-fluoro-5-mercaptophenol (1) Production of 4-chloro-5-chlorosulfonyl-2-fluorophenol
To the reaction flask was added 6.67 g (25.0 mmol) of 30% fuming sulfuric acid and 2.5 mL of dichloromethane. Subsequently, while the mixture was stirred at room temperature, a solution in which 732.8 mg (5.0 mmol) of 4-chloro-2-fluorophenol was dissolved in 2.5 mL of dichloromethane was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. Thereafter, 5.95 g (50.0 mmol) of thionyl chloride was added to the mixture. Subsequently, the mixture was stirred at 50 ° C. for 1 hour. The obtained reaction mixture was added dropwise to ice water and then partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 941.0 mg of 4-chloro-5-chlorosulfonyl-2-fluorophenol in a yield of 77%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.83 (d, J = 8.4 Hz, 1H), 7.38 (d, J = 9.9 Hz, 1H).
(2) Production of 4-chloro-2-fluoro-5-mercaptophenol
To the reaction flask, 245.1 mg (1.0 mmol) of 4-chloro-5-chlorosulfonyl-2-fluorophenol, 1 mL of 18% hydrochloric acid and 1 mL of methanol were added. Subsequently, 237.4 mg (2.0 mmol) of tin powder was added while stirring the mixture at room temperature. The mixture was then stirred at 80 ° C. for 1 hour. Methanol was distilled off under reduced pressure from the resulting reaction mixture. Dichloromethane and water were added to the resulting residue, and the mixture was partitioned between dichloromethane and water, and the dichloromethane layer was separated. Subsequently, the dichloromethane layer was dried over anhydrous magnesium sulfate and filtered, and then dichloromethane was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 152.0 mg of 4-chloro-2-fluoro-5-mercaptophenol in a yield of 85%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.14 (d, J = 10.2 Hz, 1H), 7.01 (d, J = 8.7 Hz, 1H), 3.82 (s , 1H).

Reference Example 5
Preparation of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether
To the reaction flask was added 86.2 mg (0.20 mmol) of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether and 2 mL of dichloromethane. . While the mixture was stirred at room temperature, 50.6 mg (0.22 mmol) of m-chloroperbenzoic acid was added thereto. The mixture was stirred at room temperature for 2 hours. An aqueous sodium sulfite solution, water and dichloromethane were added to the reaction mixture, the mixture was partitioned into an organic layer and an aqueous layer, and the organic layer was separated. The organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 68.0 mg of 5-trifluoromethylthiopentyl- [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylsulfinyl) phenyl] ether Was obtained in a yield of 76%.
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.54 (d, J = 8.1 Hz, 1H), 7.21 (d, J = 9.9 Hz, 1H), 4.13 (t , J = 6.3 Hz, 2H), 3.72 (m, 1H), 3.37 (m, 1H), 2.92 (t, J = 7.2 Hz, 2H), 1.84 (m, 4H) ), 1.62 (m, 2H).

In the present specification, the following equipment was used for measuring physical properties of Examples and Reference Examples.
¹ H nuclear magnetic resonance spectrum ( ¹ H-NMR); JEOL JMN-Lambda 300 or JEOL JMN-Lambda-400 (manufactured by JEOL Ltd.), internal reference material: tetramethylsilane melting point; MP-500V (Anatech Corporation) Yanaco).

(High-performance liquid chromatography (HPLC) analysis method)
Regarding the HPLC analysis method, the following documents can be referred to as necessary.
(Corporation) The Chemical Society of Japan, “New Experimental Chemistry Course 9 Analytical Chemistry II”, pp. 86-112 (1977), publisher Shingo Iizumi, Maruzen Co., Ltd. (for example, usable packing material for column—mobile phase) (Refer to pages 93 to 96 for the combination.)
(Corporation) The Chemical Society of Japan, "Experimental Chemistry Course 20-1 Analytical Chemistry" 5th edition, pages 130-151 (2007), publisher Seishiro Murata, Maruzen Co., Ltd. (for example, reverse phase chromatography analysis) (See pages 135-137 for specific usage and conditions.)

(Gas chromatography (GC) analysis method)
Regarding the GC analysis method, the following documents can be referred to as necessary.
(Corporation) The Chemical Society of Japan, “New Experimental Chemistry Course 9 Analytical Chemistry II”, pp. 60-86 (1977), publisher Izumi Izumi, Maruzen Co., Ltd. , Page 66).
(Corporation) The Chemical Society of Japan, “Experimental Chemistry Course 20-1 Analytical Chemistry”, 5th edition, pages 121-129 (2007), publisher Seishiro Murata, Maruzen Co., Ltd. (for example, details of hollow capillary separation columns (See pages 124-125 for typical usage)

(Measurement method of pH)
The pH was measured with a glass electrode type hydrogen ion concentration indicator. As the glass electrode type hydrogen ion concentration indicator, for example, model: HM-20P manufactured by Toa DKK Corporation can be used.

  ADVANTAGE OF THE INVENTION According to this invention, the pest control agent as an agricultural chemical etc. and the novel manufacturing method of General formula (4) useful as its manufacturing intermediate, and its manufacturing intermediate are provided.

Therefore, the present invention is economical, friendly to the environment, and has high industrial utility value.

Claims (30)

General formula (2):
(Wherein, R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group). R ¹ and R ² are each independently a halogen atom, or R ¹ and R ² are each independently a C1-C4 alkyl group,
The compound of claim 1. R ¹ is a fluorine atom;
R ² is a chlorine atom, or R ¹ and R ² are each methyl.
The compound of claim 1. R ¹ and R ² are each independently a halogen atom,
The compound of claim 1. R ¹ is a fluorine atom;
R ² is a chlorine atom,
The compound of claim 1. R ¹ and R ² are each independently a C1-C4 alkyl group,
The compound of claim 1. R ¹ and R ² are each methyl.
The compound of claim 1. General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. ) A compound represented by R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group, or R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
9. A compound according to claim 8. R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl or R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
9. A compound according to claim 8. R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
9. A compound according to claim 8. R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl,
9. A compound according to claim 8. R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
9. A compound according to claim 8. R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
9. A compound according to claim 8. General formula (5):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. ) A compound represented by R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group, or R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
16. A compound according to claim 15. R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl or R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
16. A compound according to claim 15. R ¹ and R ² are each independently a halogen atom;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
16. A compound according to claim 15. R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl,
16. A compound according to claim 15. R ¹ and R ² are each independently a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group,
16. A compound according to claim 15. R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl,
16. A compound according to claim 15. General formula (4):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group;
R ⁴ is a C1-C4 haloalkyl group. In which the following steps are performed:
(I) General formula (1):
(Wherein R ¹ and R ² are as defined above.)
From the compound represented by general formula (2):
(Wherein R ¹ and R ² are as defined above.)
A process for producing a compound represented by:
(Ii) The compound of the general formula (2) in the presence of a base is represented by the general formula (a):
(Where
R ³ is as defined above;
X is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Is reacted with a compound represented by the general formula (3):
(Wherein R ¹ , R ² and R ³ are as defined above.)
And (iii) a step of converting the compound of the general formula (3) into the compound of the general formula (4),
Including methods. Step (iii) includes the following steps:
(Iii-a) General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
In the presence of a base, the compound represented by the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
Is a step of converting the compound of the general formula (3) into the compound of the general formula (4) by reacting with the compound represented by the formula:
The method of claim 22. Step (iii) includes the following steps:
(Iii-b) General formula (3):
(Where
R ¹ and R ² are each independently a halogen atom or a C1-C4 alkyl group;
R ³ is a C1-C4 haloalkylthio C2-C10 alkyl group. )
A compound represented by general formula (5):
(Wherein R ¹ , R ² and R ³ are as defined above.)
And (iii-c) the compound of the general formula (5) in the presence of a base in the general formula (b):
(Where
R ⁴ is a C1-C4 haloalkyl group;
Y is a halogen atom, a C1-C4 alkylsulfonyloxy group, a C1-C4 haloalkylsulfonyloxy group, or a phenylsulfonyloxy group optionally substituted by a C1-C4 alkyl group or a halogen atom. )
A step of converting the compound of the general formula (5) into the compound of the general formula (4) by reacting with the compound represented by the formula:
including,
The method of claim 22. R ¹ and R ² are each independently a halogen atom, or R ¹ and R ² are each independently a C1-C4 alkyl group,
25. A method according to claim 23 or 24. R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy, or R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy.
25. A method according to claim 23 or 24. R ¹ and R ² are each independently a halogen atom,
25. A method according to claim 23 or 24. R ¹ is a fluorine atom;
R ² is a chlorine atom;
R ³ is 5-trifluoromethylthiopentyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy.
25. A method according to claim 23 or 24. R ¹ and R ² are each independently a C1-C4 alkyl group;
25. A method according to claim 23 or 24. R ¹ and R ² are each methyl;
R ³ is 6-trifluoromethylthiohexyl;
R ⁴ is 2,2,2-trifluoroethyl;
X is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy;
Y is a chlorine atom, a bromine atom, an iodine atom, methanesulfonyloxy, benzenesulfonyloxy, p-toluenesulfonyloxy or p-chlorobenzenesulfonyloxy.
25. A method according to claim 23 or 24.