WO2019208355A1

WO2019208355A1 - Method for producing trifluoromethyl thioalkyl compound, and composition of trifluoromethyl thioalkyl halide compound

Info

Publication number: WO2019208355A1
Application number: PCT/JP2019/016449
Authority: WO
Inventors: 信吾安村
Original assignee: クミアイ化学工業株式会社
Priority date: 2018-04-25
Filing date: 2019-04-17
Publication date: 2019-10-31
Also published as: CN111699172B; IL278051B1; TWI719457B; CN111699172A; IL278051B2; IL278051A; JPWO2019208355A1; TW201945335A; JP6660518B1

Abstract

A method for producing a trifluoromethyl thioalkyl halide compound represented by formula (1) (wherein X¹ represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; and n represents an integer of 1 to 10), the method being characterized by comprising adding thiophosgene while heating at 45°C or higher in the presence of a dihalogenated alkyl compound represented by formula (2) (wherein X² represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; and X¹ and n are as defined above) and a fluorine compound.

Description

Method for producing trifluoromethylthioalkyl compound and composition of trifluoromethylthioalkyl halide compound

The present invention relates to a method for producing a trifluoromethylthioalkyl compound having a trifluoromethylthio group at one end of an alkyl chain and a halogen atom at the other end. The present invention also relates to a composition comprising such a trifluoromethylthioalkyl halide compound.

The fluoroalkylthio group is a useful substituent in pharmaceutical and agrochemical compounds. For example, the pest control agent disclosed in Patent Document 1 has a trifluoroethylsulfinyl group and a trifluoromethylthioalkoxy group on the benzene ring, and the fluoroalkylthio group is important in the expression of the pest control activity. Have a role.

In order to produce pharmaceutical and agrochemical compounds having a trifluoromethylthioalkyl group, it is indispensable to produce a synthetic equivalent that functions as a trifluoromethylthioalkylating reagent, and various trifluoromethylthioalkyl synthons have been produced so far. Synthetic methods have been investigated.

For example, in Patent Document 2, the hydroxy group of bromohexanol, which is a raw material, is acetyl protected, and after reacting a metal thiocyanate to synthesize a thiocyanate compound, the resulting thiocyanate compound is reacted with a trifluoromethylation reagent, The target trifluoromethylthiohexyl bromide is produced through deprotection and bromination of the group ("Reference Example 1" in this document).

For example, in Patent Document 3, the hydroxy group of bromopentanol as a raw material is acetyl protected, and after reacting a metal thiocyanate to synthesize a thiocyanate compound, the resulting thiocyanate compound is reacted with a trifluoromethylation reagent, The target trifluoromethylthiopentyl bromide is produced through deprotection and bromination of the hydroxy group (“Examples 122 to 123, Reference Examples 2 to 3” in this document).

For example, in Non-Patent Document 1, a target trifluoromethylthiohexyl bromide is produced in one step by performing a coupling reaction between a raw material bromohexaneboronic acid and a trifluoromethylthiolation reagent in the presence of a copper catalyst. Yes.

For example, in Non-Patent Document 2, bromoundecanoic acid as a raw material is reacted with a trifluoromethyl thiolating reagent in the presence of an iridium catalyst to produce the target trifluoromethyl thiodecyl bromide in one step.

Patent Document 4 describes a trifluoromethylthiolation reaction in which a raw material alkyl halide compound is reacted with thiophosgene in the presence of a fluorine compound. The method described in Patent Document 4 is a method for producing a trifluoromethylthioalkyl compound from a low-reactivity alkyl halide compound using a single step and a less expensive raw material. It is superior to the conventional technology. However, Patent Document 4 neither describes nor suggests a method for producing an alkyl compound having a trifluoromethylthio group at one end of an alkyl chain and a halogen atom at the other end.

WO2013 / 157229A1 WO2015 / 122396A1 WO2015 / 199109A1 WO2016 / 076183A1

The method for producing a trifluoromethylthioalkyl halide compound disclosed in Patent Documents 2 and 3 is a very long process that requires 5 steps to produce the target compound, and is costly and labor-intensive, and is improved in terms of industrial production. It was desired.

On the other hand, the method for producing a trifluoromethylthioalkyl halide compound disclosed in Non-Patent Documents 1 and 2 can obtain the target compound in one step. However, in this method, since it is necessary to use a special catalyst, a special ligand, a special reaction apparatus, etc., it costs. For this reason, although the manufacturing method of these literatures is an excellent method as a laboratory manufacturing method, it cannot be said that it is preferable in terms of industrial manufacturing. Further, in the trifluoromethyl thioating agent used in Non-Patent Documents 1 and 2, a portion not introduced into the product remains as an extra organic compound, which may adversely affect the subsequent reaction. Furthermore, in this method, the yield of the target compound is low, and improvement has been desired from this aspect.

The object of the present invention is to produce a trifluoromethylthioalkyl halide compound having a trifluoromethylthio group at one end of an alkyl chain and a halogen atom at the other end in a single step using relatively inexpensive raw materials and reagents. Is to provide a simple method. Another object of the present invention is to provide a composition containing such a trifluoromethylthioalkyl halide compound.

In view of the above situation, the present inventor has conducted extensive research on a method for producing a trifluoromethylthioalkyl halide compound. As a result, surprisingly, by using a dihalogenated alkyl compound having halogen atoms at both ends as a raw material and adding thiophosgene while heating in the presence of a fluorine compound, the target trifluoromethylthioalkyl halide compound is obtained as follows: It has been found that it can be obtained in one step without using a special catalyst or the like. And based on this knowledge, it came to complete this invention.

That is, this invention solves the said subject by providing the invention as described in the following [1] to [11].

[1] Formula (1):

(In the formula, X ¹ represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and n represents an integer in the range of 1 to 10.)
A process for producing a trifluoromethylthioalkyl halide compound represented by:
Formula (2):

(Wherein, X ² represents a fluorine atom, a chlorine atom, a bromine atom, a halogen atom selected from the group consisting of an iodine atom, X ¹ and n are as defined above.)
A method for producing a trifluoromethylthioalkyl halide compound, comprising adding thiophosgene while heating at 45 ° C. or higher in the presence of a dihalogenated alkyl compound represented by formula (I) and a fluorine compound.

[2] The method for producing a trifluoromethylthioalkyl halide compound according to [1], wherein X ¹ and X ² are different halogen atoms, and the atomic number of X ¹ is smaller than the atomic number of X ² .

[3] X ¹ represents a chlorine atom or a bromine atom,
X ² represents a bromine atom or an iodine atom,
n shows 5 or 6, The manufacturing method of the trifluoromethylthioalkyl halide compound as described in [1] characterized by the above-mentioned.

[3 ′] X ¹ represents a chlorine atom or a bromine atom,
X ² represents a bromine atom or an iodine atom,
n shows the integer of the range of 3 to 8, The manufacturing method of the trifluoromethylthioalkyl halide compound as described in [1] characterized by the above-mentioned.

[3 ″] X ¹ represents a chlorine atom,
X ² represents a bromine atom or an iodine atom,
n shows 5 or 6, The manufacturing method of the trifluoromethylthioalkyl halide compound as described in [3] characterized by the above-mentioned.

[4] X ¹ represents a chlorine atom,
X ² represents a bromine atom,
n shows 5 or 6, The manufacturing method of the trifluoromethylthioalkyl halide compound as described in [1] characterized by the above-mentioned.

[5] The method for producing a trifluoromethylthioalkyl halide compound according to [1], wherein the addition of thiophosgene is performed at a temperature in the range of 60 ° C to 100 ° C.

[5 '] The method for producing a trifluoromethylthioalkyl halide compound according to [5], wherein the addition of thiophosgene is performed at a temperature in the range of 70 ° C to 90 ° C.

[6] The method for producing a trifluoromethylthioalkyl halide compound according to [1], wherein the fluorine compound used in the reaction is a tetraalkylammonium fluoride salt, an alkali metal fluoride salt or a mixture thereof.

[6 '] The fluorine compound used in the reaction is tetramethylammonium fluoride, tetrabutylammonium fluoride, sodium fluoride, potassium fluoride, cesium fluoride or a mixture thereof. The manufacturing method of the trifluoromethylthioalkyl halide compound of description.

[6 ″] The method for producing a trifluoromethylthioalkyl halide compound according to [6], wherein the fluorine compound used in the reaction is an alkali metal fluoride salt.

[6 ′ ″] The method for producing a trifluoromethylthioalkyl halide compound according to [6], wherein the fluorine compound used in the reaction is potassium fluoride.

[7] The trifluoromethylthioalkyl according to [1], wherein the fluorine compound is used in an amount of 3.0 to 12.0 mol per 1.0 mol of the compound of the formula (2). A method for producing a halide compound.

[7 '] The trifluoromethylthio according to [7], wherein a fluorine compound in a range of 4.0 mol to 9.0 mol is used with respect to 1.0 mol of the compound of the formula (2). A method for producing an alkyl halide compound.

[8] The trifluoromethylthioalkyl halide according to [1], wherein thiophosgene is used in an amount of 1.0 mol or more and 3.0 mol or less with respect to 1.0 mol of the compound of the formula (2). Compound production method.

[8 ′] The trifluoromethylthioalkyl according to [8], wherein thiophosgene is used in an amount of 1.0 mol or more and 2.0 mol or less with respect to 1.0 mol of the compound of the formula (2). A method for producing a halide compound.

[9] The method for producing a trifluoromethylthioalkyl halide compound according to [1], wherein the reaction is performed at a temperature in the range of 60 ° C. or higher and 100 ° C. or lower.

[9 '] The process for producing a trifluoromethylthioalkyl halide compound according to [9], wherein the reaction is performed at a temperature in the range of 70 ° C to 90 ° C.

[10] The production method according to [1], wherein the solvent used in the reaction is a nitrile, an ether, an amide, an aromatic hydrocarbon, or a mixture thereof.

[10 '] The method for producing a trifluoromethylthioalkyl halide compound according to [10], wherein the solvent used in the reaction is a nitrile.

[10 ′ ′] The method for producing a trifluoromethylthioalkyl halide compound according to [10], wherein the solvent used in the reaction is acetonitrile.

[11] Formula (1):

(In the formula, X ¹ represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and n represents an integer in the range of 1 to 10.)
A trifluoromethylthioalkyl halide compound represented by:
Formula (3):

And a bis (trifluoromethylthio) alkyl compound represented by the formula: a composition of a trifluoromethylthioalkyl halide compound.

According to the present invention, a trifluoromethylthioalkyl halide compound having a trifluoromethylthio group at one end of an alkyl chain and a halogen atom at the other end can be produced in a single step using relatively inexpensive raw materials and reagents. It is possible to provide a simple method. Moreover, according to this invention, it becomes possible to provide the composition containing such a trifluoromethylthioalkyl halide compound.

1. The symbols and terms described in this specification will be described.

The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

2. The manufacturing method of the trifluoromethylthioalkyl halide compound of this invention is demonstrated.

The present invention relates to formula (1):

(In the formula, X ¹ represents a halogen atom, and n represents an integer in the range of 1 to 10.)
A process for producing a trifluoromethylthioalkyl halide compound represented by:
Formula (2):

(Wherein X ² represents a halogen atom, and X ¹ and n are as defined above.)
In the presence of a dihalogenated alkyl compound represented by the formula (I) and a fluorine compound, thiophosgene is added while heating, a method for producing a trifluoromethylthioalkyl halide compound.

That is, the present invention can produce the target trifluoromethylthioalkyl halide compound of the formula (1) in one step according to the following reaction formula.

For this reason, as in the prior art, a multi-step process is not necessary for producing a trifluoromethylthioalkyl halide compound, and no special catalyst is required, so that it is an industrially preferred production method in terms of production cost. It is. Hereinafter, the compounds and reaction conditions used in the present invention will be described in detail.

(Raw compound)
The raw material used in the present invention is a dihalogenated alkyl compound represented by the formula (2), which is a known compound or can be produced from a known compound by a known method. Examples of the dihalogenated alkyl compound of the formula (2) include bromochloromethane, dibromomethane, chloroiodomethane, bromoiodomethane, 1-bromo-2-chloroethane, 1,2-dibromoethane, 1-chloro-2-iodoethane. 1-bromo-2-iodoethane, 1-bromo-3-chloropropane, 1,3-dibromopropane, 1-chloro-3-iodopropane, 1-bromo-3-iodopropane, 1-bromo-4-chlorobutane, 1,4-dibromobutane, 1-chloro-4-iodobutane, 1-bromo-4-iodobutane, 1-bromo-5-chloropentane, 1,5-dibromopentane, 1-chloro-5-iodopentane, 1- Bromo-5-iodopentane, 1-bromo-6-chlorohexane, 1,6-dibromohexane, 1-chloro -6-iodohexane, 1-bromo-6-iodohexane, 1-bromo-7-chloroheptane, 1,7-dibromoheptane, 1-chloro-7-iodoheptane, 1-bromo-7-iodoheptane, 1 -Bromo-8-chlorooctane, 1,8-dibromooctane, 1-chloro-8-iodooctane, 1-bromo-8-iodooctane, 1-bromo-9-chlorononane, 1,9-dibromononane, 1- Chloro-9-iodononane, 1-bromo-9-iodononane, 1-bromo-10-chlorodecane, 1,10-dibromodecane, 1-chloro-10-iododecane, 1-bromo-10-iododecane, etc. It is not limited to these.

As the dihalogenated alkyl compound of formula (2), preferably 1-bromo-3-chloropropane, 1,3-dibromopropane, 1-chloro-3-iodopropane, 1-bromo-4-chlorobutane, 1,4-dibromo Butane, 1-chloro-4-iodobutane, 1-bromo-5-chloropentane, 1,5-dibromopentane, 1-chloro-5-iodopentane, 1-bromo-6-chlorohexane, 1,6-dibromohexane 1-chloro-6-iodohexane, 1-bromo-7-chloroheptane, 1,7-dibromoheptane, 1-chloro-7-iodoheptane, 1-bromo-8-chlorooctane, 1,8-dibromooctane 1-chloro-8-iodooctane and the like, more preferably 1-bromo-5-chloropentane, 1,5-dibromope And 1-chloro-5-iodopentane, 1-bromo-6-chlorohexane, 1,6-dibromohexane, 1-chloro-6-iodohexane and the like, more preferably 1-bromo-5-chloro. Examples include pentane and 1-bromo-6-chlorohexane.

In the formula (2), X ¹ and X ² may be the same halogen atom or different halogen atoms. From the viewpoint of the yield of the target compound of the formula (1), X ¹ and X ² Are preferably different halogen atoms. Further, also in terms of yield, it is preferred that X ¹ atomic number is smaller than the atomic number of the X ^2. The reason is as follows.

Since X ¹ and X ² are both halogen atoms, both may be substituted with a trifluoromethylthio group by the reaction of a fluorine compound and thiophosgene. For this reason, by making X ¹ and X ² different halogen atoms, the trifluoromethylthio group is preferentially introduced into only ^one of the X ¹ and X ² with a difference in reactivity. This is because the desired formula (1) can be obtained in a high yield. Here, since the reactivity of the halogen atoms is in the order of F <Cl <Br <I, in order to preferentially substitute the trifluoromethylthio group with X ² , the atom with the atomic number of X ¹ being X ² It is preferably smaller than the number.

Further, in the formula (2), X ¹ and X ² are different halogen atoms from the viewpoint of reducing the by-product bis (trifluoromethylthio) alkyl compound (described later) of the formula (3). preferable. When many by-products are generated, the yield of the target compound of the formula (1) is lowered accordingly. Also from this point, it is preferable that X ¹ and X ² are different halogen atoms, and that the atomic number of X ¹ is smaller than the atomic number of X ² .

Furthermore, in the formula (2), it is preferable that X ¹ and X ² are different halogen atoms from the viewpoint of reducing the unreacted formula (2). When the dihalogenated alkyl of formula (2) remains unreacted, the reaction is carried out in the step of producing an alkylphenyl sulfide derivative by reacting the compound of formula (1) (hereinafter sometimes referred to as “post-step”). It becomes a factor to inhibit. For this reason, reducing unreacted Formula (2) is preferable not only from the viewpoint of the yield of the compound of Formula (1) but also from the viewpoint of reactivity in the subsequent steps. If X ¹ and X ² are different halogen atoms, thiophosgene preferentially nucleophilic attacks on one halogen atom, so that the yield increases and the amount of unreacted compound of formula (2) is reduced. Can do. From the same viewpoint, it is preferable X ¹ atomic number is smaller than the atomic number of the X ^2.

As a combination of X ¹ and X ² , X ¹ is preferably a chlorine atom or a bromine atom, and X ² is preferably a bromine atom or an iodine atom. In particular, from the viewpoint of the yield of the target trifluoromethylthioalkyl halide compound of the formula (1), it is preferable that X ¹ is a chlorine atom and X ² is a bromine atom.

The value of n in formula (2) is not particularly limited, but n is preferably in the range of 3 to 8, more preferably in the range of 4 to 7, and preferably 5 or 6. Particularly preferred.

(Fluorine compound)
The fluorine compound used in the present invention may be any fluorine compound as long as the reaction proceeds. Examples of the fluorine compound used in the present invention include a tetraalkylammonium fluoride salt (eg, tetramethylammonium fluoride, tetrabutylammonium fluoride), an alkali metal fluoride salt (eg, sodium fluoride, fluoride). Potassium, cesium fluoride, etc.), alkaline earth metal fluoride salts (eg, magnesium fluoride, calcium fluoride, etc.), and mixtures thereof, but are not limited thereto.

From the viewpoint of reactivity, yield, economic efficiency, etc., the fluorine compound used in the present invention preferably includes a tetraalkylammonium fluoride salt and an alkali metal fluoride salt, more preferably an alkali metal fluoride salt. It is done.

Specific examples of the fluorine compound used in the present invention preferably include tetramethylammonium fluoride, tetrabutylammonium fluoride, sodium fluoride, potassium fluoride, cesium fluoride and the like, more preferably fluoride. Sodium, potassium fluoride, cesium fluoride, etc. are mentioned, More preferably, potassium fluoride is mentioned.

(Form of potassium fluoride)
The form of potassium fluoride used in the present invention may be any form as long as the reaction proceeds, and those skilled in the art can appropriately select it. As potassium fluoride, commercially available potassium fluoride can be used directly, and it can be used evenly dissolved in a solvent or partially dissolved. The potassium fluoride includes potassium fluoride produced by a spray-drying method with a fine powder and a large specific surface area in terms of dissolution and dispersibility in a reaction organic solvent.

(Amount of fluorine compound used)
The amount of the fluorine compound used in the present invention may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., it is usually 3.0 mol or more, preferably 3.0 mol or more and 15.0 mol or less, relative to 1.0 mol of the dihalogenated alkyl compound of formula (2) More preferably, the range is 3.0 mol or more and 12.0 mol or less, more preferably 4.0 mol or more and 9.0 mol or less, and further preferably 4.0 mol or more and 7.0 mol or less.

(Thiophosgene form)
The form of thiophosgene used in the present invention may be any form as long as the reaction proceeds, and those skilled in the art can appropriately select it. When thiophosgene is added dropwise, thiophosgene may be used directly without a solvent, or may be used in a state dissolved in a solvent. When using thiophosgene in the state melt | dissolved in the solvent, those skilled in the art can select from the solvent mentioned later suitably. However, this is not the case when thiophosgene is obtained as a solution other than the solvent described below.

(Amount of thiophosgene used)
The amount of thiophosgene used in the present invention may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., it is usually 0.9 mol or more and 5.0 mol or less, preferably 1.0 mol or more with respect to 1.0 mol of the dihalogenated alkyl compound of formula (2). Examples include a range of 3.0 mol or less, more preferably 1.0 mol or more and 2.0 mol or less, and still more preferably 1.0 mol or more and 1.5 mol or less.

(solvent)
The present invention is preferably carried out using a solvent. The solvent used in the present invention may be any solvent as long as the reaction proceeds. Examples of the solvent used in the present invention include nitriles (for example, acetonitrile), ethers (for example, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), dioxane, monoglyme, diglyme and the like. ), Carboxylic acid esters (eg, ethyl acetate, butyl acetate, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethane, etc.), aromatic hydrocarbons (eg, benzene, chlorobenzene, Dichlorobenzene, nitrobenzene, toluene, xylene, etc.), amides (eg, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc.), Zorinon compound (such as 1,3-dimethyl-2-imidazolinone (DMI), etc.), sulfoxides (e.g., dimethyl sulfoxide (DMSO) etc.) and the like, but is not limited thereto. These solvents can be used alone or as a mixed solvent having an arbitrary mixing ratio.

From the viewpoint of reactivity, yield, economic efficiency, etc., the solvent used in the present invention is preferably nitriles, ethers, aromatic hydrocarbons and amides, more preferably nitriles.

Specific examples of the solvent used in the present invention are preferably acetonitrile, propionitrile, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 1,4-dioxane, monoglyme, diglyme, Benzene, chlorobenzene, dichlorobenzene, nitrobenzene, toluene, xylene, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and the like, more preferably acetonitrile, A propionitrile etc. are mentioned, More preferably, acetonitrile is mentioned.
The acetonitrile used in the present invention is preferably dehydrated, but a person skilled in the art can appropriately adjust the dehydration method.

(Amount of solvent used)
The amount of the solvent used in the present invention may be any amount as long as the reaction proceeds. From the viewpoints of yield, by-product suppression, economic efficiency, etc., usually 0.01 to 50 L (liter), preferably 0.1 to 15 L, relative to 1.0 mol of the dihalogenated alkyl compound of formula (2), A range of 0.1 to 10 L is more preferable, and a range of 0.1 to 5 L is more preferable.

(Reaction temperature)
The reaction temperature in the present invention may be any temperature as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products and economic efficiency, the reaction temperature is usually 50 ° C. or higher and below the boiling point of the solvent used, preferably 50 ° C. or higher and 110 ° C. or lower, more preferably 60 ° C. or higher and 100 ° C. or lower. More preferably, a range of 70 ° C. or higher and 90 ° C. or lower can be exemplified.

(Reaction time)
The reaction time in the present invention is not particularly limited. The reaction time in this invention can adjust the reaction time of this invention suitably for those skilled in the art. From the viewpoint of yield, by-product suppression, economic efficiency, etc., a range of usually 0.5 hours to 48 hours, preferably 1 hour to 36 hours, more preferably 1 hour to 24 hours can be exemplified. Here, “reaction time” means the time from immediately after the addition of the entire amount of thiophosgene to the end of the reaction. The reaction time in the present invention is an aging period for consuming unreacted raw materials, and is distinguished from the addition time of thiophosgene.

(Main product)
The product produced by the present invention is a trifluoromethylthioalkyl halide compound represented by the formula (1). Examples of the trifluoromethylthioalkyl halide compound of the formula (1) include chloromethyl (trifluoromethyl) sulfide, bromomethyl (trifluoromethyl) sulfide, chloroethyl (trifluoromethyl) sulfide, bromoethyl (trifluoromethyl) sulfide, and chloropropyl. (Trifluoromethyl) sulfide, bromopropyl (trifluoromethyl) sulfide, chlorobutyl (trifluoromethyl) sulfide, bromobutyl (trifluoromethyl) sulfide, chloropentyl (trifluoromethyl) sulfide, bromopentyl (trifluoromethyl) sulfide, Chlorohexyl (trifluoromethyl) sulfide, bromohexyl (trifluoromethyl) sulfide, chloroheptyl (trifluoromethyl) ) Sulfide, bromoheptyl (trifluoromethyl) sulfide, chlorooctyl (trifluoromethyl) sulfide, bromooctyl (trifluoromethyl) sulfide, chlorononyl (trifluoromethyl) sulfide, bromononyl (trifluoromethyl) sulfide, chlorodecyl (trifluoro) Methyl) sulfide, bromodecyl (trifluoromethyl) sulfide, and the like, but are not limited thereto.

The trifluoromethylthioalkyl halide compound of formula (1) is preferably chloropropyl (trifluoromethyl) sulfide, bromopropyl (trifluoromethyl) sulfide, chlorobutyl (trifluoromethyl) sulfide, bromobutyl (trifluoromethyl) sulfide, chloro Pentyl (trifluoromethyl) sulfide, bromopentyl (trifluoromethyl) sulfide, chlorohexyl (trifluoromethyl) sulfide, bromohexyl (trifluoromethyl) sulfide, chloroheptyl (trifluoromethyl) sulfide, bromoheptyl (trifluoromethyl) ) Sulfide, chlorooctyl (trifluoromethyl) sulfide, bromooctyl (trifluoromethyl) sulfide, etc. Examples thereof include chloropentyl (trifluoromethyl) sulfide, bromopentyl (trifluoromethyl) sulfide, chlorohexyl (trifluoromethyl) sulfide, bromohexyl (trifluoromethyl) sulfide, and more preferably chloropentyl (trifluoromethyl). Methyl) sulfide, chlorohexyl (trifluoromethyl) sulfide and the like.

(By-product)
In the production method of the present invention, a by-product may be generated depending on conditions. As a by-product, a bis (trifluoromethylthio) alkyl compound represented by the following formula (3) can be exemplified.

The bis (trifluoromethylthio) alkyl compound of the formula (3) does not inhibit the reaction in the production of the alkylphenyl sulfide derivative, which is a subsequent step of the formula (1). The compound of the formula (1) is a raw material for producing the alkylphenyl sulfide derivative and reacts with a trifluoroalkylthiophenol derivative in a later step (described later). In this step, the compound of the formula (3) inhibits the reaction. There is nothing to do. Therefore, even if the by-product of formula (3) remains, the production method of the present invention does not lower the reactivity in the subsequent step. Therefore, the removal of the compound of formula (3) and formula (1) It is not always necessary to purify the compound, and the reaction can be carried out more easily. Furthermore, in the present invention, since only thiophosgene and potassium fluoride are used as raw materials, the remaining portion not introduced into the product becomes an inorganic salt and can be easily removed by a washing operation with water. For this reason, as in Non-Patent Documents 1 and 2, there is an advantage that there is little possibility of adverse effects in the post-process without the excess organic compound remaining.

3. Addition conditions of thiophosgene The present invention is characterized in that thiophosgene is added to a raw material mixture containing the raw material compound of general formula (2) and a fluorine compound at an addition temperature of 45 ° C. or more and an addition time of 0.25 hours or more. . Hereinafter, conditions for adding thiophosgene will be described in detail.

(Addition method)
Addition of thiophosgene to the raw material mixture can be performed by a known method. For example, the method etc. which are dripped at a reaction system using a separating funnel, a dropping funnel, a burette, a syringe, etc. can be mentioned. When a small amount of thiophosgene is added over time, it is preferable to use a combination of a syringe and a syringe pump. In the case where a large amount of thiophosgene is added to a reaction can or the like over time, a method of dropping it into the reaction system using a metering pump, a dropping tank or the like can be mentioned. Moreover, when adding thiophosgene, in order to advance reaction, it is preferable to stir a raw material mixture with a stirrer.

(Addition temperature)
The addition temperature of thiophosgene in the present invention can be appropriately adjusted by those skilled in the art if it is 45 ° C. or higher. From the viewpoints of yield, by-product suppression, economic efficiency, etc., the addition temperature is usually in the range of 45 ° C. or higher and the boiling point of the solvent used, preferably 50 ° C. or higher and 110 ° C. or lower. More preferably, the range of 60 degreeC or more and 100 degrees C or less can be illustrated, More preferably, the range of 70 degreeC or more and 90 degrees C or less can be illustrated. Here, “addition temperature” means the temperature of the reaction system immediately after the addition of thiophosgene. Note that if the amount of thiophosgene added to the raw material mixture at a time is relatively small, the temperature of the thiophosgene is considered to have little effect on the reaction system, so the temperature of the raw material mixture at the time of addition should be the addition temperature. You can also.

(Addition time)
The addition time of thiophosgene in the present invention can be appropriately adjusted by those skilled in the art as long as it is 0.25 hours (that is, 15 minutes) or longer. In particular, from the viewpoint of yield improvement, the lower limit of the addition time in the present invention is preferably 0.5 hours or more, more preferably 1.0 hours or more, still more preferably 2.0 hours or more, and particularly preferably 3.5 hours. The above can be illustrated. In addition, particularly from the viewpoints of suppressing by-products and economic efficiency, the upper limit of the addition time in the present invention is preferably 48 hours or less, more preferably 36 hours or less, still more preferably 24 hours or less, and particularly preferably 12 hours. The following can be illustrated. The range of addition time in the present invention can be appropriately adjusted by those skilled in the art by combining the above lower limit and upper limit. The combination of the upper limit and the lower limit of the addition time is, for example, preferably 0.5 hours to 48 hours, more preferably 1.0 hours to 36 hours, still more preferably 2.0 hours to 24 hours, and particularly preferably 3. Examples are 5 hours to 12 hours. However, the present invention is not limited by these combinations. Here, the “addition time” means the time from the start of adding thiophosgene to the reaction system until the completion of the addition of the entire amount to the reaction system.

As the addition time of thiophosgene, the following conditions are particularly preferable.
Addition time (h) × (addition temperature (° C.) − 45) ≧ 10
Moreover, it is preferable that the addition rate of thiophosgene with respect to 1 mol of dihalogenated alkyl compounds of Formula (2) is 10 mol / hour or less.
Furthermore, it is preferable to add thiophosgene under the following conditions.
1 ≦ addition rate (mol / hour) × (addition temperature (° C.) − 45) ≦ 400

4). The composition of the trifluoromethylthioalkyl halide compound of the present invention will be described.
The composition of the trifluoromethylthioalkyl halide compound of the present invention comprises a trifluoromethylthioalkyl halide compound represented by the above formula (1), a bis (trifluoromethylthio) alkyl compound represented by the above formula (3), and Containing.

The bis (trifluoromethylthio) alkyl compound of the formula (3) is a by-product in the production method of the present invention, but does not inhibit the reaction in the production of the alkylphenyl sulfide derivative, which is a subsequent step of the formula (1). Therefore, there is no problem even if the expression (3) is included. The composition of the present invention can be used as a raw material in an alkylphenyl sulfide derivative.
In the composition of the present invention, the content of the compound of the formula (3) is usually not more than 1 time, preferably not more than 0.1 times, based on the weight with respect to the content of the compound of the formula (1). More preferably, it is 0.01 times or less. When the ratio of the compound of the formula (3) to the compound of the formula (1) exceeds 1 time, the ratio of the by-product becomes too high, and the ratio of the compound of the formula (1) becomes low in the post-process. It is easy to deteriorate.

5. A method for producing an alkylphenyl sulfide derivative (post-process) will be described.
The trifluoromethylthioalkyl halide compound of formula 1 can be used for the production of alkylphenyl sulfide derivatives. Alkylphenyl sulfide derivatives are useful as pest control agents or intermediates thereof. The alkylphenyl sulfide derivative can be produced by the following formula.

(In the formula, m represents an integer of 0, 1, 2;
R ¹ is a C1-C6 haloalkyl group (excluding 2-bromoethyl group), C2-C8 alkenyl group (excluding allyl group), C2-C8 haloalkenyl group, C2-C6 alkynyl group, C2-C6 halo An alkynyl group, a branched C4-C6 alkyl group (excluding an isobutyl group), a C3-C6 cycloalkyl C1-C6 alkyl group or a C3-C6 halocycloalkyl C1-C6 alkyl group,
R ² represents a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a cyano group, or a nitro group. Group,
R ³ represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group or a C1-C6 haloalkyl group. )

The above reaction is performed in the presence of a base. The base used in the above reaction may be any base as long as the reaction proceeds. From the viewpoint of reactivity, yield, economic efficiency, etc., examples of the base include alkali metal hydroxides, alkali metal carbonates, and alkali metal hydrogen carbonates. Preferable specific examples of the base for the above reaction include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, more preferably sodium carbonate. You may use the base in the said reaction individually or in combination of 2 or more types of arbitrary ratios. The amount of the base used in the above reaction may be any amount as long as the reaction proceeds.

In order to accelerate the reaction, the above reaction may be performed in the presence of a catalytic amount of iodides. Examples of iodides include sodium iodide and potassium iodide, and preferably sodium iodide. The amount of iodide used may be any amount as long as the reaction proceeds.

The above reaction is preferably performed using a solvent. Any solvent may be used as long as the reaction proceeds. From the viewpoints of reactivity, yield, and economic efficiency, the solvent preferably includes nitriles, ethers, aromatic hydrocarbons, and amides, and more preferably aromatic hydrocarbons and amides. As specific examples of the solvent used in the above reaction, preferably acetonitrile, propionitrile, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 1,4-dioxane, chlorobenzene, dichlorobenzene , Toluene, xylene, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), etc., more preferably chlorobenzene, dichlorobenzene, toluene, xylene, N , N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and the like. These solvents can be used alone or as a mixed solvent having an arbitrary mixing ratio.

The amount of solvent used may be any amount as long as the reaction proceeds. Further, the ratio of the mixed solvent may be any ratio as long as the reaction proceeds.

The reaction temperature in the above reaction is not particularly limited as long as the reaction proceeds. From the viewpoint of yield, suppression of by-products and economic efficiency, the reaction temperature is usually 50 ° C. or higher and below the boiling point of the solvent used, preferably 50 ° C. or higher and 110 ° C. or lower, more preferably 60 ° C. or higher and 100 ° C. or lower. More preferably, a range from 70 ° C. to 90 ° C. can be exemplified. The reaction time in the above reaction is not particularly limited as long as the reaction proceeds. From the viewpoint of yield, by-product suppression, economic efficiency, etc., a range of usually 0.5 hours to 48 hours, preferably 1 hour to 36 hours, more preferably 1 hour to 24 hours can be exemplified.

In the above method for producing an alkylphenyl sulfide derivative, as described above, even if a bis (trifluoromethylthio) alkyl compound of the formula (3) is mixed, there is no influence such as inhibiting the reaction. For this reason, even if the by-product bis (trifluoromethylthio) alkyl compound produced by the method for producing a trifluoromethylthioalkyl halide compound of the present invention is mixed, it can be used as it is for producing an alkylphenyl sulfide derivative. . In addition, after the production method of the trifluoromethylthioalkyl halide compound of the present invention, after producing the trifluoromethylthioalkyl halide compound and removing the by-product bis (trifluoromethylthio) alkyl compound, the alkylphenyl sulfide derivative Needless to say, it may be used for manufacturing.

Next, the production method of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

In this specification, the following apparatus was used for the measurement of each physical property of Examples and Reference Production Examples.
( ¹ H nuclear magnetic resonance spectrum ( ¹ H-NMR))
Varian Mercury-300, internal reference material: tetramethylsilane (TMS)
(Gas chromatography (GC) analysis method)
GC-2010 (manufactured by Shimadzu Corporation), detection method: FID
Regarding the GC analysis method, the following documents can be referred to as necessary.
(A): (Corporation) The Chemical Society of Japan, “New Experimental Chemistry Course 9 Analytical Chemistry II”, pp. 60-86 (1977), publisher Shingo Iizumi, Maruzen Co., Ltd. (See page 66 for phase liquid)
(B): 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, hollow capillary (See pages 124-125 for specific use of the separation column.)

Example 1
Production of (5-chloropentyl) trifluoromethyl sulfide

To a reaction flask equipped with a magnetic stirrer, 1.85 g (10 mmol) of 1-bromo-5-chloropentane, 2.32 g (40 mmol) of potassium fluoride (spray dried product) and 20 mL of acetonitrile were added. While stirring the mixture under heating under reflux (temperature in the reaction system was 82 ° C.), 1.38 g (12 mmol) of thiophosgene was added dropwise over 1 hour, and then the reaction mixture was stirred under heating under reflux for 1 hour. The obtained reaction solution was analyzed by a GC internal standard method using biphenyl as an internal standard substance. As a result, the yield of (5-chloropentyl) trifluoromethyl sulfide was 90.0% and 1,5-bis ((tri The yield of fluoromethyl) thio) pentane was 6.0%, and the recovery rate of 1-bromo-5-chloropentane which was an unreacted raw material was 0.5%. A part of the obtained reaction solution was isolated and purified by a method well known to those skilled in the art, and subjected to NMR measurement to confirm the following spectrum.

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.55 (t, J = 6.6 Hz, 2H), 2.90 (t, J = 7.2 Hz, 2H), 1.86-1 .69 (m, 4H), 1.62-1.54 (m, 2H)

(Example 2)
Production of (5-chloropentyl) trifluoromethyl sulfide

To a reaction flask equipped with a magnetic stirrer, 3.71 g (20 mmol) of 1-bromo-5-chloropentane, 4.65 g (80 mmol) of potassium fluoride (spray dried product) and 30 mL of acetonitrile were added. While stirring the mixture with heating under reflux (the temperature in the reaction system was 82 ° C.), 9.20 g (24 mmol) of a 30% o-xylene solution of thiophosgene was added dropwise over 3 hours, and then the reaction mixture was heated under reflux. Stir for 1 hour. The obtained reaction solution was analyzed by a GC internal standard method using biphenyl as an internal standard substance. As a result, the yield of (5-chloropentyl) trifluoromethyl sulfide was 89.5% and 1,5-bis ((tri The yield of fluoromethyl) thio) pentane was 4.7%, and the recovery rate of unreacted starting material 1-bromo-5-chloropentane was 0.6%.

(Example 3)
Production of (5-chloropentyl) trifluoromethyl sulfide

In a four-necked flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 5.57 g (30 mmol) of 1-bromo-5-chloropentane, 6.97 g (120 mmol) of potassium fluoride (spray-dried product), 12 mL o-xylene and 30 mL acetonitrile were added. While stirring the mixture under heating under reflux (temperature in the reaction system was 90 ° C.), 4.14 g (36 mmol) of thiophosgene was added dropwise over 3 hours, and then the reaction mixture was stirred under heating under reflux for 1 hour. When the obtained reaction solution was analyzed by the GC area percentage method, the components other than the solvent and the like in the reaction solution were 9-2.0% (5-chloropentyl) trifluoromethyl sulfide and 1,5-bis ((trimethyl Fluoromethyl) thio) pentane was 1.0%, and unreacted starting material 1-bromo-5-chloropentane was 3.0%.

(Comparative Example 1)
Production of (5-chloropentyl) trifluoromethyl sulfide

In a four-necked reaction flask equipped with a stirrer, reflux condenser, thermometer and dropping funnel, 3.99 g (20 mmol) of 1-bromo-5-chloropentane, 4.65 g (80 mmol) of potassium fluoride (spray-dried product) And 40 mL of acetonitrile was added. While stirring the mixture at an internal temperature of 35 ° C., 2.76 g (24 mmol) of thiophosgene was added dropwise over 3 hours, and then the reaction mixture was stirred at an internal temperature of 35 ° C. for 1 hour. When the obtained reaction solution was analyzed by the GC area percentage method, the components other than the solvent and the like in the reaction solution were 9.9% for (5-chloropentyl) trifluoromethyl sulfide and 1,5-bis ((trimethyl Fluoromethyl) thio) pentane was 0%, and unreacted starting material 1-bromo-5-chloropentane was 88.6%.

Example 4
Production of (6-chlorohexyl) trifluoromethyl sulfide

To a reaction flask equipped with a magnetic stirrer, 2.00 g (10 mmol) of 1-bromo-6-chlorohexane, 2.32 g (40 mmol) of potassium fluoride (spray dried product) and 20 mL of acetonitrile were added. While stirring the mixture under heating under reflux (temperature in the reaction system was 82 ° C.), 1.38 g (12 mmol) of thiophosgene was added dropwise over 1 hour, and then the reaction mixture was stirred under heating under reflux for 1 hour. When the obtained reaction solution was analyzed by the GC area percentage method, the components other than the solvent and the like in the reaction solution were 9-0.1% (6-chlorohexyl) trifluoromethyl sulfide, 1,6-bis ((tri Fluoromethyl) thio) hexane was 3.0%, and unreacted starting material 1-bromo-6-chlorohexane was 4.3%. A part of the obtained reaction solution was isolated and purified by a method well known to those skilled in the art, and subjected to NMR measurement to confirm the following spectrum.

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.54 (t, J = 6.6 Hz, 2H), 2.89 (t, J = 7.2 Hz, 2H), 1.75 (m , 4H), 1.47 (m, 4H)

(Example 5)
Production of (5-bromopentyl) trifluoromethyl sulfide

To a reaction flask equipped with a magnetic stirrer, 2.30 g (10 mmol) of 1,5-dibromopentane, 2.32 g (40 mmol) of potassium fluoride (spray dried product) and 20 mL of acetonitrile were added. While stirring the mixture under heating under reflux (temperature in the reaction system was 82 ° C.), 1.38 g (12 mmol) of thiophosgene was added dropwise over 1 hour, and then the reaction mixture was stirred under heating under reflux for 1 hour. When the obtained reaction mixture was analyzed by GC internal standard method using biphenyl as an internal standard substance, the yield of (5-bromopentyl) trifluoromethyl sulfide was 45.2% and 1,5-bis ((tri The yield of fluoromethyl) thio) pentane was 26.5%, and the recovery rate of 1,5-dibromopentane which was an unreacted raw material was 22.4%. A part of the obtained reaction solution was isolated and purified by a method well known to those skilled in the art, and subjected to NMR measurement to confirm the following spectrum.

( ¹ H-NMR shift of (5-bromopentyl) trifluoromethyl sulfide)
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.39 (t, J = 6.6 Hz, 2H), 2.90 (t, J = 7.2 Hz, 2H), 1.90 (m , 2H), 1.74 (m, 2H), 1.57 (m, 2H)
( ¹ H-NMR shift of 1,5-bis ((trifluoromethyl) thio) pentane)
¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 2.89 (t, J = 7.2 Hz, 4H), 1.74 (quin, J = 7.2 Hz, 4H), 1.55 (m , 2H)

(Example 6, Example 7)
Except having changed the usage-amount of potassium fluoride and thiophosgene, operation similar to Example 5 was performed and Example 6 and Example 7 were implemented. The results are summarized in Table 1.

The result of Example 5 shows that when the reaction was carried out using 1,5-dibromopentane having bromine atoms at both ends of the alkyl chain as a raw material, the target compound (5-bromopentyl) trifluoromethyl sulfide, This shows that a mixture of 1,5-bis ((trifluoromethyl) thio) pentane having both ends trifluoromethylthiolated and 1,5-dibromopentane, which is an unreacted raw material, is obtained.
In Example 6, when the reaction was carried out using twice the amount of thiophosgene and potassium fluoride used in Example 5, the reaction proceeded rapidly and 1,5-bis ((trifluoromethyl) thio) Pentane was obtained quantitatively.
In Example 7, the reaction was carried out using half the amount of thiophosgene and potassium fluoride used in Example 5 to obtain (5-bromopentyl) trifluoromethyl sulfide in a yield of 73%. It was. The result of Example 7 is better than that of Example 5, but 51% of unreacted raw material remains.

The starting material 1,5-dibromopentane is a known substance, and 1,5-dibromopentane can be found in literature (for example, the Journal of Organic Chemistry, 51 (12), 2206-2210, (1986)) and reagent catalogs. It is described that the boiling point of pentane is 111-112 ° C / 15 mmHg and 221 ° C / 760 mmHg. On the other hand, when the boiling point of (5-bromopentyl) trifluoromethyl sulfide was measured, they were 90 ° C./15 mmHg (actual measured value) and 210 ° C./760 mmHg (calculated value).
As described above, the boiling points of 1,5-dibromopentane and (5-bromopentyl) trifluoromethyl sulfide are very close, and isolation and purification by distillation is difficult. Therefore, it is preferable from the viewpoint of industrial production to reduce unreacted raw materials as in Examples 1 to 4.

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

Into a reaction vessel equipped with a magnetic stirrer, 10.1 g (30 mmol) of 4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenol having a purity of 77.1%, a purity of 88.2. % (5-chloropentyl) trifluoromethyl sulfide 7.7 g (33 mmol), sodium carbonate 3.5 g (33 mmol), sodium iodide 0.45 g (3 mmol) and N, N-dimethylformamide 15 mL were added and the mixture was Stir at 90 ° C. for 8 hours. After confirming the completion of the reaction, the reaction mixture was cooled, 4.8 g of 25% aqueous sodium hydroxide solution and 30 mL of water were added, and the mixture was extracted with 15 mL of dichloromethane. Partitioning between the organic layer and water gave 5-trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2,2-trifluoroethylthio) phenyl] ether as 31.9 g of dichloromethane solution. When the obtained dichloromethane solution was analyzed by LC absolute calibration curve method, it was found that the purity was 36.6% and the yield was 90.3%. A part of the obtained dichloromethane solution was isolated and purified by a method well known to those skilled in the art, and subjected to NMR measurement to confirm the following spectrum.

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.23 (d, J = 3.9 Hz, 1H), 7.20 (d, J = 6.0 Hz, 1H), 4.03 (t , J = 6.3 Hz, 2H), 3.41 (q, J = 9.9 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 1.90-1.74 (m, 4H), 1.66-1.58 (m, 2H)

The same operations as in Reference Production Example 1 were carried out except that the type and amount of the solvent were changed, and Reference Production Examples 2, 3, 4 and 5 were carried out. The results are summarized in Table 2.

According to the present invention, an industrially preferable method for producing an alkyl compound having a trifluoromethylthio group at one end of an alkyl chain and a halogen atom at the other end is provided.
According to the present invention, there is provided an industrially preferable production method of an alkyl compound having a trifluoromethylthio group at one end of an alkyl chain and a halogen atom at the other end, which does not require many steps until the production of the target compound. Is done.
According to the present invention, industrial use of an alkyl compound having a trifluoromethylthio group at one end of an alkyl chain and a halogen atom at the other end, which does not require a special catalyst, a special ligand, a special reaction apparatus or the like. A preferred manufacturing method is provided.
According to the present invention, there is provided an industrially preferred method for producing an alkyl compound having trifluoromethylthio at one end of an alkyl chain and a halogen atom at the other end, in which the target compound is obtained in high yield.
Furthermore, according to the present invention, trifluoromethylthioalkyl halide compounds useful as medical pesticides and intermediates thereof can be produced on an industrial scale.
For example, (5-chloropentyl) trifluoromethyl sulfide produced in Example 1 was prepared according to the method described in Reference Production Example 1, and 5-trifluoromethylthiopentyl [4-chloro-2-fluoro-5- (2,2 , 2-trifluoroethylthio) phenyl] ether and then an oxidation reaction disclosed in International Publication No. 2013/157229 can be derived into a compound having excellent pest control activity.
Therefore, the present invention has a high industrial utility value.

Claims

Formula (1):

(In the formula, X 1 represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and n represents an integer in the range of 1 to 10.)
A process for producing a trifluoromethylthioalkyl halide compound represented by:
Formula (2):

(Wherein, X 2 represents a fluorine atom, a chlorine atom, a bromine atom, a halogen atom selected from the group consisting of an iodine atom, X 1 and n are as defined above.)
A method for producing a trifluoromethylthioalkyl halide compound, comprising adding thiophosgene while heating at 45 ° C. or higher in the presence of a dihalogenated alkyl compound represented by formula (I) and a fluorine compound.
A X 1 and X 2 are different halogen atoms, the production method of the trifluoromethylthio alkyl halide compound of claim 1 in which X 1 atomic number is equal to or smaller than the atomic number of the X 2.
X 1 represents a chlorine atom or a bromine atom,
X 2 represents a bromine atom or an iodine atom,
The method for producing a trifluoromethylthioalkyl halide compound according to claim 1, wherein n represents 5 or 6.
X 1 represents a chlorine atom,
X 2 represents a bromine atom,
4. The method for producing a trifluoromethylthioalkyl halide compound according to claim 3, wherein n represents 5 or 6.
The method for producing a trifluoromethylthioalkyl halide compound according to claim 1, wherein the addition of thiophosgene is performed at a temperature in the range of 60 ° C to 100 ° C.
The method for producing a trifluoromethylthioalkyl halide compound according to claim 1, wherein the fluorine compound used in the reaction is a tetraalkylammonium fluoride salt, an alkali metal fluoride salt or a mixture thereof.
2. The trifluoromethylthioalkyl halide compound according to claim 1, wherein a fluorine compound in a range of 3.0 mol to 12.0 mol is used with respect to 1.0 mol of the compound of the formula (2). Production method.
2. The production of a trifluoromethylthioalkyl halide compound according to claim 1, wherein thiophosgene in the range of 1.0 mol to 3.0 mol is used with respect to 1.0 mol of the compound of the formula (2). Method.
The method for producing a trifluoromethylthioalkyl halide compound according to claim 1, wherein the reaction is carried out at a temperature in the range of 60 ° C to 100 ° C.
The method for producing a trifluoromethylthioalkyl halide compound according to claim 1, wherein the solvent used in the reaction is a nitrile, an ether, an amide, an aromatic hydrocarbon, or a mixture thereof.
Formula (1):

(In the formula, X 1 represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and n represents an integer in the range of 1 to 10.)
A trifluoromethylthioalkyl halide compound represented by:
Formula (3):

And a bis (trifluoromethylthio) alkyl compound represented by the formula: a composition of a trifluoromethylthioalkyl halide compound.