JP2022086694A - Method for Producing Fluorosilane Compound - Google Patents

Abstract

To provide a novel method for producing a fluorosilane compound.SOLUTION: A method for producing, e.g., a fluorosilane compound represented by the following formula (IV) includes a step of obtaining the fluorosilane compound by reacting a compound represented by the following formula (III) with at least one fluorinating agent selected from the group consisting of antimony fluoride and ammonium hydrogen fluoride in a reaction solution containing the compound III, the fluorinating agent, and a solvent.SELECTED DRAWING: None

Description

The present disclosure relates to a method for producing a fluorosilane compound.

Functionalized silanes such as fluorosilane compounds having a Si—F bond have been studied for use as electrolyte compositions and the like used in electrochemical devices (Patent Document 1).

Special Table 2017-538667

One aspect of the present invention is to provide a novel method for producing a fluorosilane compound.

［式（１）中、Ｒ^１は置換基を有していてもよいアルキレン基を示し、Ｒ^２は置換基を有していてもよいアルキル基を示し、Ｙ^１及びＹ^２はそれぞれ独立にアルキル基を示す。］
下記式（Ａ）で表される化合物Ａと、フッ化アンチモン及びフッ化水素アンモニウムからなる群より選択される少なくとも１種のフッ素化剤と、溶媒とを含む反応液中で、化合物Ａとフッ素化剤とを反応させて、フルオロシラン化合物を得る工程を含む、方法に関する。

［式（Ａ）中、Ｒ^１、Ｒ^２、Ｙ^１及びＹ^２は前記と同意義を示し、Ｌは脱離基を示す。］ One aspect of the present invention is a method for producing a fluorosilane compound represented by the following formula (1).

[In the formula (1), R ¹ indicates an alkylene group which may have a substituent, R ² indicates an alkyl group which may have a substituent, and Y ¹ and Y ² are independent of each other. Indicates an alkyl group. ]
Compound A and fluorine in a reaction solution containing compound A represented by the following formula (A), at least one fluorinating agent selected from the group consisting of antimony pentafluoride and ammonium hydrogen fluoride, and a solvent. The present invention relates to a method comprising reacting with an agent to obtain a fluorosilane compound.

[In the formula (A), R ¹ , R ² , Y ¹ and Y ² have the same meanings as described above, and L indicates a leaving group. ]

［式（Ａ－１）中、Ｒ^１、Ｒ^２、Ｙ^１及びＹ^２は前記と同意義を示し、複数存在するＲ^１、Ｒ^２、Ｙ^１及びＹ^２はそれぞれ同一であっても異なっていてもよい。］ The compound A may be a compound represented by the following formula (A-1).

[In the formula (A-1), R ¹ , R ² , Y ¹ and Y ² have the same meaning as described above, and a plurality of R ¹ , R ² , Y ¹ and Y ² are different even if they are the same. May be. ]

Compound A may be 1,3-bis (3-methylsulfonylpropyl) -1,1,3,3-tetramethyldisiloxane.

When reacting the reaction solution, the fluorinating agent may be added to compound A and the solvent in a plurality of times.

［式（Ｂ）中、Ｒ^１、Ｒ^２、Ｙ^１、Ｙ^２及びＬは前記と同意義を示す。］ Prior to the step of obtaining the fluorosilane compound, the step of obtaining the compound A by oxidizing the compound B represented by the following formula (B) to form a sulfonyl group may be further included.

[In the formula (B), R ¹ , R ² , Y ¹ , Y ² and L have the same meanings as described above. ]

In the step of obtaining compound A, compound B may be oxidized by reacting with permanganate in the presence of an acid.

［式（Ｃ）及び式（Ｄ）中、Ｒ^１、Ｒ^２、Ｙ^１、Ｙ^２及びＬは前記と同意義を示し、Ｘはハロゲン原子又はカルボキシル基を示す。］ Prior to the step of obtaining compound A, in a reaction solution containing compound C represented by the following formula (C), a salt of compound D represented by the following formula (D), and an alcohol having 3 or more carbon atoms. , The step of reacting compound C with compound D to obtain compound B may be further included.

[In the formula (C) and the formula (D), R ¹ , R ² , Y ¹ , Y ² and L have the same meanings as described above, and X represents a halogen atom or a carboxyl group. ]

According to one aspect of the present invention, it is possible to provide a novel method for producing a fluorosilane compound.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments.

［式（１）中、Ｒ^１は置換基を有していてもよいアルキレン基を示し、Ｒ^２は置換基を有していてもよいアルキル基を示し、Ｙ^１及びＹ^２はそれぞれ独立にアルキル基を示す。］
下記式（Ａ）で表される化合物Ａと、フッ化アンチモン及びフッ化水素アンモニウムからなる群より選択される少なくとも１種のフッ素化剤と、溶媒とを含む反応液中で化合物Ａとフッ素化剤とを反応させて、フルオロシラン化合物を得る工程を含む。

［式（Ａ）中、Ｒ^１、Ｒ^２、Ｙ^１及びＹ^２は前記と同意義を示し、Ｌは脱離基を示す。］ The method according to this embodiment is a method for producing a fluorosilane compound represented by the following formula (1).

[In the formula (1), R ¹ indicates an alkylene group which may have a substituent, R ² indicates an alkyl group which may have a substituent, and Y ¹ and Y ² are independent of each other. Indicates an alkyl group. ]
Compound A and fluorination in a reaction solution containing compound A represented by the following formula (A), at least one fluorinating agent selected from the group consisting of antimony pentafluoride and ammonium hydrogen fluoride, and a solvent. The step of reacting with an agent to obtain a fluorosilane compound is included.

[In the formula (A), R ¹ , R ² , Y ¹ and Y ² have the same meanings as described above, and L indicates a leaving group. ]

The carbon number of the alkylene group in R ¹ may be, for example, 1 or more, or 2 or more, and may be 10 or less, or 5 or less. It is preferable that R ¹ is an alkylene group having 2 or more carbon atoms or 3 or more carbon atoms independently. The alkylene group in R ¹ may or may not have a substituent. Examples of the substituent of the alkylene group in R ¹ include an ether group, an amide group, a phenyl group, and an oxo group (= O). Examples of the alkylene group in R ¹ include methylene, ethylene group, propylene group, isopropylene group, n-butylene group and pentyl group.

The number of carbon atoms of the alkyl group represented by ^R2 may be, for example, 1 or more, and may be 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group (for example, an n-pentyl group), and a hexyl group (for example, n-hexyl). Group).

The alkyl group represented by ^R2 may have a substituent or may not have a substituent. Examples of the substituent of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group and a hexyl group.

The number of carbon atoms of the alkyl group represented by Y ¹ and Y ² may be 1 or more, and may be 3 or less. Y ¹ and Y ² may be a methyl group, an ethyl group, or a propyl group, and may be linear or branched.

The leaving group represented by L is a group that can be removed by reaction with a fluorinating agent. Examples of the leaving group include a chlorine atom, a substituted silyloxy group (—O—SiR ₃ ), a bromine atom, an iodine atom, a hydroxy group and the like.

Examples of the fluorosilane compound include 3-methylsulfonylpropyl-dimethylfluorosilane.

The compound A may be a compound represented by the following formula (A-1). When compound A has the following formula (A-1), two molecules of the above fluorosilane compound can be obtained from one molecule of compound A.

In formula (A-1), R ¹ , R ² , Y ¹ and Y ² may be the groups described by R ¹ , R ² , Y ¹ and Y ² in formula (A). A plurality of R ¹ , R ² , Y ¹ and Y ² may be the same or different from each other.

Examples of the compound A include 1,3-bis (3-methylsulfonylpropyl) -1,1,3,3-tetramethyldisiloxane and (3-methylsulfonylpropyl) pentamethyldisiloxane.

The solvent may be, for example, a solvent capable of dissolving (compatible) the compound A and / or the fluorinating agent. As the solvent, for example, a hydrophobic solvent can be used. The solvent may be, for example, a solvent having a boiling point of 110 ° C. or higher under atmospheric pressure from the viewpoint of enabling the reaction under high temperature conditions.

Examples of the solvent (hydrophobic solvent) include aromatic hydrocarbon solvents, ester solvents, and aliphatic hydrocarbon solvents. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the ester solvent include ethyl acetate, butyl acetate, propyl acetate and pentyl acetate. Examples of the aliphatic hydrocarbon solvent include cyclohexane, hexane, and heptane. As the solvent, one type may be used alone, or two or more types may be used in combination.

The solvent may be toluene, xylene, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, cyclohexane, hexane, heptane and a mixed solvent containing at least two of these solvents.

The compound represented by the above formula (1) can be obtained by reacting the compound A with the fluorinating agent in a reaction solution containing the compound A, the fluorinating agent and the solvent. The reaction conditions (reaction temperature, reaction time, etc.) can be appropriately set according to, for example, the type of the compound A as a raw material, the fluorinating agent, the solvent, and the like. The temperature of the reaction solution may be, for example, 70 ° C to 130 ° C, or 90 to 120 ° C. The reaction temperature may be raised to near the boiling point of the solvent and refluxed. The temperature of the reaction solution may be raised stepwise or continuously. The time (reaction time) for maintaining the temperature of the reaction solution at the above temperature may be, for example, 10 minutes or more, or 1 hour or more, and may be, for example, 12 hours or less, 10 hours or less, or 8 hours or less. good.

The reaction may be carried out in an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and argon gas.

When reacting the reaction solution, the fluorinating agent may be added to compound A and the solvent in a plurality of times. In this case, the desired fluorosilane compound can be obtained in a shorter time. When adding in multiple batches, it is desirable to add the fluorinating agent in equal mols. It is better to add the fluorinating agent at intervals when the fluorinating agent begins to solidify. Specifically, it is preferable to put it every hour in the early stage of the reaction and every 2 to 5 hours at intervals in the late stage of the reaction.

After completion of the reaction, post-treatment may be performed if necessary. For example, the desired fluorosilane compound can be obtained by removing the unreacted fluorinating agent, starting material, solvent and the like. The unreacted fluorinating agent can be removed, for example, by filtration. Oily components including a solvent and the like can be removed by a method using a decompression device such as an evaporator.

The reaction rate of the reaction for obtaining the fluorosilane compound represented by the formula (1) may be, for example, 95% to 100%. The reaction rate is measured by the method described in Examples described later.

The method according to the present embodiment further comprises a step of obtaining compound A by oxidizing compound B represented by the following formula (B) to form a sulfonyl group before the step of obtaining a fluorosilane compound. You can stay.

In formula (B), R ¹ , R ² , Y ¹ , Y ² and L have the same meanings as described above.

The compound B may be, for example, a compound represented by the following formula (B-1). In this case, the compound A represented by the above formula (A-1) can be obtained by the oxidation reaction of the compound B.

R ¹ , R ² , Y ¹ and Y ² in the formula (B-1) may be the groups described in the formula (A-1).

Examples of compound B include 1,3-bis (3-methylthiopropyl) -1,1,3,3-tetramethyldisiloxane and (3-methylsulfonylpropyl) pentamethyldisiloxane.

The oxidation reaction of compound B can be carried out using an oxidizing agent. Examples of the oxidizing agent include permanganate, hydrogen peroxide and hypochlorite.

In the step of obtaining the compound A, it is preferable to oxidize the compound B by reacting the permanganate in the presence of an acid. In this case, the reaction can proceed more efficiently.

Examples of the permanganate include potassium permanganate, sodium permanganate, ammonium permanganate, silver permanganate, zinc permanganate, magnesium permanganate, calcium permanganate, and barium permanganate. Will be. The permanganate salt is preferably potassium permanganate.

Examples of the acid include sulfuric acid, nitric acid, phosphoric acid, acetic acid, formic acid and oxalic acid.

In the step of obtaining the compound A, the compound B and the permanganate may be reacted in a reaction solution containing, for example, the compound B, the permanganate, the acid and the solvent. The solvent may be water or an organic solvent. Examples of the organic solvent include toluene, xylene, ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, cyclohexane, hexane and heptane.

The concentration of compound B in the total amount of the reaction solution may be, for example, 0.001 to 10 mol / L or 0.01 to 1.0 mol / L.

The acid concentration in the total amount of the reaction solution may be, for example, 0.001 to 10 mol / L. The pH of the reaction solution may be in the range of 1-6.

The temperature of the reaction solution can be appropriately set according to the type of the component such as the solvent in the reaction solution. The temperature of the reaction solution may be, for example, 5 to 40 ° C. or 10 to 30 ° C. The time (reaction time) for maintaining the temperature of the reaction solution at the above temperature may be, for example, 10 minutes or more, or 1 hour or more, and may be, for example, 12 hours or less, 10 hours or less, or 8 hours or less. good.

The reaction may be carried out in an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and argon gas.

After completion of the reaction, post-treatment may be performed if necessary. For example, when the reaction solution contains water, the sulfone compound can be obtained by removing the water by separating the reaction solution and volatilizing the solvent in the oil layer. According to the method according to the present embodiment, the sulfone compound can be obtained without performing a purification operation other than the liquid separation operation, so that the sulfone compound can be obtained in a high yield.

After completion of the reaction, post-treatment may be performed if necessary. For example, when the reaction solution contains water, the compound A can be obtained by removing the water by separating the reaction solution and volatilizing the solvent in the oil layer.

The reaction rate of the reaction forming a sulfonyl group may be, for example, 95% to 100%. The reaction rate is measured by the method described in Examples described later.

［式（Ｃ）及び式（Ｄ）中、Ｒ^１、Ｒ^２、Ｙ^１、Ｙ^２及びＬは前記と同意義を示し、Ｘはハロゲン原子又はカルボキシル基を示す。］ The method according to the present embodiment may further include a step of obtaining compound B before the step of obtaining compound A. The step of obtaining compound B is carried out in a reaction solution containing compound C represented by the following formula (C), a salt of compound D represented by the following formula (D), and an alcohol having 3 or more carbon atoms. It may be a step of reacting C with compound D to obtain compound B.

[In the formula (C) and the formula (D), R ¹ , R ² , Y ¹ , Y ² and L have the same meanings as described above, and X represents a halogen atom or a carboxyl group. ]

The reaction mechanism between the compound C and the salt of the thiol compound is, for example, as follows, but is not limited thereto. When X is a halogen atom, it is presumed that compound C reacts with a salt of a thiol compound to form a sulfide bond. When X is a carboxyl group, it is presumed that the thiol group S attacks the C = O bond of the carboxyl group to form a bond. At that time, it is presumed that a part of the carboxyl group -OH is eliminated to form a thioester bond.

Examples of the halogen atom represented by X include a chlorine atom, a bromine atom and an iodine atom. X may be, for example, a chlorine atom.

［式（Ｃ－１）中、Ｒ^１、Ｙ^１及びＹ^２は、それぞれ式（Ａ－１）中のＲ^１、Ｙ^１及びＹ^２と同意義を示し、Ｘは、式（Ｃ）中のＸと同意義を示す。］ Compound C may be a compound represented by the following formula (C-1).

[In the formula (C-1), R ¹ , Y ¹ and Y ² have the same meaning as R ¹ , Y ¹ and Y ² in the formula (A-1), respectively, and X is in the formula (C). Shows the same meaning as X in. ]

Examples of the compound C include 1,3-bis (3-chloropropyl) -1,1,3,3-tetramethyldisiloxane and (3-chloropropyl) pentamethyldisiloxane.

Compound D may be, for example, an alkyl mercaptan. Examples of the compound D include methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, tert-butyl, tert butyl mercaptan, pentyl mercaptan and hexyl mercaptan.

The salt of compound D may be, for example, an alkali metal salt. Examples of the salt include sodium salt, potassium salt, magnesium salt, calcium salt, ammonium salt and phosphonium salt.

The molar ratio (d / c) of the number of moles (d) of compound D to the number of moles (c) of compound C in the reaction solution is 0.5 or more, 1.0 or more, 1.5 or more, 2.0 or more. , Or 2.5 or more, and may be, for example, 10 or less, 5 or less, or 3 or less.

In the step of obtaining compound B, the reaction solution contains a solvent. Some components in the reaction solution may not be dissolved in the solvent. The reaction solution contains an alcohol having 3 or more carbon atoms as a solvent. The alcohol having 3 or more carbon atoms may be a monohydric alcohol or a polyhydric alcohol. The carbon number of the alcohol having 3 or more carbon atoms may be, for example, 3 or more and 8 or less, or 3 or more and 6 or less, or 3 or 4. Examples of the alcohol having 3 or more carbon atoms include isopropanol (2-propanol), isobutyl alcohol, butanol, and pentanol. As for the alcohol having 3 or more carbon atoms, one type may be used alone, or two or more types may be used in combination.

The reaction solution may or may not contain a solvent (other solvent) other than alcohol having 3 or more carbon atoms. The amount of alcohol having 3 or more carbon atoms may be 10 parts by volume or more, or 20 parts by volume or more, and may be 80 parts by volume or less, or 60 parts by volume or less with respect to 100 parts by volume of the total amount of the solvent.

Examples of other solvents include water, methanol, ethanol, and ethylene glycol-based solvents (for example, polyethylene glycol, 1,2-dimethoxyethane, ethylene glycol monoethyl ether).

The reaction solution may contain methanol as a solvent. When the reaction solution contains methanol, the ratio of the volume of alcohol having 3 or more carbon atoms to the volume of methanol (alcohol / methanol having 3 or more carbon atoms) is, for example, 1/10 to 1 / 0.1. It may be 1/5 to 1 / 0.5, and may be 1 / 1.2 to 1 / 0.8.

The reaction solution may contain water as a solvent. When the reaction solution contains water, the ratio of the volume of water to the volume of a solvent other than water (water / solvent other than water) may be, for example, 1/10 to 1 / 0.1, and 1/5. It may be ~ 1 / 0.5, and may be 1 / 1.2 to 1 / 0.8.

The reaction solution may contain alcohol and water having 3 or more carbon atoms as a solvent, and may contain alcohol, water and methanol having 3 or more carbon atoms. When the reaction solution contains alcohol with 3 or more carbon atoms, water and methanol, the ratio of the volume of water, the volume of alcohol with 3 or more carbon atoms to the volume of methanol (water / alcohol with 3 or more carbon atoms / methanol). May be, for example, 1/1/1 to 7/1/1.

Compound C is reacted with a salt of compound D in a reaction solution to obtain compound B. The reaction solution can be prepared by mixing compound C, a salt of compound D, an alcohol having 3 or more carbon atoms, and other components, if necessary. The reaction solution may be prepared by using compound D instead of the salt of compound D to form a salt of compound D in the reaction solution.

The concentration of compound C in the total amount of the reaction solution may be, for example, 0.001 to 10 mol / L or 0.01 to 1.0 mol / L. The concentration of compound D in the total amount of the reaction solution may be, for example, 0.001 to 10 mol / L or 0.2 to 2.0 mol / L.

The temperature of the reaction solution can be appropriately set according to the type of the solvent or the like in the reaction solution. The temperature of the reaction solution may be, for example, 50 ° C. or higher, 60 ° C. or higher, or 70 ° C. or higher, and may be lower than 100 ° C., 90 ° C. or lower, or 80 ° C. or lower. The time (reaction time) for maintaining the temperature of the reaction solution at the above temperature may be, for example, 10 minutes or more, 1 hour or more, 5 hours or more, and for example, 12 hours or less, 10 hours or less, or 8 hours or less. There may be.

The reaction may be carried out in an atmosphere of an inert gas. Examples of the inert gas include nitrogen gas and argon gas.

After completion of the reaction, post-treatment may be performed if necessary. For example, when the reaction solution contains water, the compound B can be obtained by removing the water by separating the reaction solution and volatilizing the solvent component in the oil layer. According to the method according to the present embodiment, post-treatment tends to be easy. For example, when compound B is 1,3-bis (3-methylthiopropyl) -1,1,3,3-tetramethyldisiloxane, since the compound and water are separated, a liquid separation operation is performed. Can be easily separated by.

The reaction rate of the reaction between the compound C and the salt of the compound D may be, for example, 85% or more or 95% or more. The yield of the target compound may be, for example, 90% or more or 95% or more. The reaction rate and yield are measured by the methods described in Examples described later.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Test Example 1: Synthesis of 1,3-bis (3-methylthiopropyl) -1,1,3,3-tetramethyldisiloxane (BTDS) Reaction with a three-necked flask connected to a cooling tube, thermometer and dropping funnel It was made into a container. The inside of the reaction vessel was made into an N ₂ atmosphere. Then, in the reaction vessel, the stirrer chip, the solvent shown in Table 1, 1,3-bis (3-chloropropyl) -1,1,3,3-tetramethyldisiloxane (BCDS, represented by the following formula (I)) is represented. The compound) was added, and the mixture was heated to 70-80 ° C. and stirred. An aqueous solution of sodium methyl mercaptan (described later) was added to the dropping funnel, and the solution was added dropwise to the reaction vessel at a pace of 1 drop every 3 seconds. After the dropping, the temperature of the reaction solution in the reaction vessel was maintained at 70-80 ° C., and the reaction was carried out for a predetermined time. After completion of the reaction, the aqueous layer is removed from the reaction solution with a separating funnel, the oil layer is evaporated, and 1,3-bis (3-methylthiopropyl) -1,1,3,3-tetramethyl is used as the reaction product. Disiloxane (BTDS, a compound represented by the following formula (II)) was obtained.

The measurement results of ¹ H NMR of the obtained BTDS are shown below.
^{1 1} H NMR (300 MHz, CDCI ₃ ) δ2.52 (t, J = 3.75 Hz, 4H), 2.10 (s, 6H), 1.67-1.57 (m-4H), 0.66- 0.63 (t, J = 4.32Hz, 4H), 0.07 (s, 12H)

Table 1 shows the results of the reaction rate. The reaction rate is a value calculated from the integral ratio of the chloroterminal methylene group of the raw material and the terminal methylene group of methylthiol after the reaction calculated from ¹ H NMR. Table 1 also shows the yield by the method of synthesis condition 2. The yield is a value obtained by defining the yield of BTDS obtained from the charged amount (mol) of the raw material (BCDS) and the reaction rate as the theoretical yield and dividing the actual yield of BTDS by the theoretical yield.

In Table 1, "IPA" means isopropanol, "MeOH" means methanol, "EtOH" means ethanol, and "EG" means ethylene glycol.

Test Example 2: Synthesis of 1,3-bis (3-methylsulfonylpropyl) -1,1,3,3-tetramethyldisiloxane (BSDS) A three-necked flask connected with a cooling tube, a thermometer and a dropping funnel. It was used as a reaction vessel. The inside of the reaction vessel was made into an N ₂ atmosphere. Then, the stirrup chip, solvent, catalyst, and 1,3-bis (3-methylthiopropyl) -1,1,3,3-tetramethyldisiloxane (BTDS) are placed in the reaction vessel in the flask and stirred at room temperature. did. An aqueous solution containing an oxidant was dropped into the reaction vessel at a pace of 1 drop every 3 seconds from the dropping funnel to which the aqueous solution containing the oxidant was added. After the dropping, the reaction solution was reacted at room temperature for a predetermined time. After completion of the reaction, the aqueous layer is removed with a separating funnel, the oil layer is evaporated, and 1,3-bis (3-methylsulfonylpropyl) -1,1,3,3-tetramethyldisiloxane is used as a reaction product. (BSDS, a compound represented by the following formula (III)) was obtained.

得られたＢＳＤＳの^１Ｈ ＮＭＲの測定結果を以下に示す。
１Ｈ ＮＭＲ（３００ＭＨｚ，ＣＤＣＩ_３）δ３．１０（ｔ，Ｊ＝４．０９，４Ｈ），２．９４（ｓ，６Ｈ），２．０１－１．９０（ｍ―４Ｈ），０．７６－０．７０（ｔ，J=４．２７Ｈｚ－４Ｈ），０．１８（ｓ，１２Ｈ）

The measurement results of ¹ H NMR of the obtained BSDS are shown below.
1H NMR (300MHz, CDCI ₃ ) δ3.10 (t, J = 4.09, 4H), 2.94 (s, 6H), 2.01-1.90 (m-4H), 0.76-0 .70 (t, J = 4.27Hz-4H), 0.18 (s, 12H)

Table 2 shows the results of the reaction rate. The reaction rate is a value calculated from the integral ratio of the terminal methyl group of the raw material methyl thiol and the terminal methyl group of the post-reaction methyl sulfonyl calculated from ¹ H NMR. The yield is a value calculated by defining the yield of BSDS obtained from the charged amount (mol) of the raw material (BTDS) and the reaction rate as the theoretical yield and dividing the actual yield of BSDS by the theoretical yield.

According to the methods of synthesis conditions 2-1 and 2-2, it was shown that the sulfone compound can be produced with the same reaction efficiency as the method of synthesis conditions 2-6 using hydrogen peroxide.

Test Example 3: Synthesis of 3-methylsulfonylpropyl-dimethylfluorosilane A cooling tube is connected to a PFA flask, a three-way cock is attached on the cooling tube, a tube is attached to one of the three-way cocks, and the tube is filled with water. I put it in a container. N ₂ gas was blown from the other side of the 3-way cock to create an N ₂ atmosphere. Then, toluene and 1,3-bis (3-methylsulfonylpropyl) -1,1,3,3-tetramethyldisiloxane (BSDS) were put into a flask and stirred at 70 ° C. After putting a part or all of the fluorinating agent into the flask, the temperature was raised to 110 ° C. and the reaction was carried out for a predetermined time. After completion of the reaction, the fluorinating agent is removed from the post-reaction liquid with a Kiriyama funnel, the oil layer is evaporated, and the desired reaction product is represented by 3-methylsulfonylpropyl-dimethylfluorosilane (formula (IV) below). Compound) was obtained.

Under the synthesis condition 1, the fluorinating agent was added in two portions (first input amount: 50 g, second input amount: 50 g). Under the synthesis condition 1, the addition of the fluorinating agent was carried out in two steps, one at the start of the reaction (the first addition of the fluorinating agent) and the other at the time when one hour had passed from the start of the reaction.

Under the synthesis condition 2, the fluorinating agent was added in four portions (first input amount: 3.5 g, second input amount: 3.5 g, third input amount: 3.5 g, fourth time). Input amount: 3.5 g). Under the synthesis condition 2, the addition of the fluorinating agent is divided into four times, that is, at the time of starting the reaction (first addition of the fluorinating agent) and at the time when 1.5 hours, 5 hours and 10 hours have passed from the start time of the reaction. did.

Under the synthesis condition 3, the entire amount of the fluorinating agent was added at the time of starting the reaction (the first addition of the fluorinating agent).

The measurement results of ¹ H NMR of the obtained 3-methylsulfonylpropyl-dimethylfluorosilane are shown below.
^{1 1} H NMR (300 MHz, CDCI ₃ ) δ3.07 (t, J = 4.04, 2H), 2.92 (s, 3H), 2.05-1.95 (m-2H), 0.95- 0.82 (q, J = 4.04Hz, 2H), 0.29 (s, 6H)

The reaction rate in Table 3 is the integral of the methyl group of the siloxane portion of 1,3-bis (3-methylsulfonylpropyl) -1,1,3,3-tetramethyldisiloxane, which is the raw material calculated from ¹ H NMR. It is a value calculated by comparing the value obtained by halving the value with the integrated value of the methyl group of the silane moiety of 3-methylsulfonylpropyl-dimethylfluorosilane after the reaction. The yield was calculated by defining the yield of the formula (IV) obtained from the charged amount (mol) of the raw material (BSDS) and the reaction rate as the theoretical yield, and dividing the actual yield of the formula (IV) by the theoretical yield. The value.

The target fluorosilane compound could be obtained under the conditions shown in the synthesis conditions 1 to 3. It was shown that the reaction time was significantly shortened by adding the fluorinating agent stepwise (comparison between synthesis conditions 1 and 2 and synthesis condition 3).

Claims (7)

A method for producing a fluorosilane compound represented by the following formula (1).

[In the formula (1), R ¹ indicates an alkylene group which may have a substituent, R ² indicates an alkyl group which may have a substituent, and Y ¹ and Y ² are independent of each other. Indicates an alkyl group. ]
In a reaction solution containing the compound A represented by the following formula (A), at least one fluorinating agent selected from the group consisting of antimony pentafluoride and ammonium hydrogen fluoride, and a solvent, the compound A and the compound A A method comprising a step of reacting with the fluorinating agent to obtain the fluorosilane compound.

[In the formula (A), R ¹ , R ² , Y ¹ and Y ² have the same meanings as described above, and L indicates a leaving group. ] The method according to claim 1, wherein when the reaction solution is reacted, the fluorinating agent is added to the compound A and the solvent in a plurality of times. The step 1 or 2 further comprises a step of obtaining the compound A by oxidizing the compound B represented by the following formula (B) to form a sulfonyl group before the step of obtaining the fluorosilane compound. The method described.

[In the formula (B), R ¹ , R ² , Y ¹ , Y ² and L have the same meanings as described above. ] The method according to claim 3, wherein the compound B is oxidized by reacting with permanganate in the presence of an acid. Prior to the step of obtaining the compound A, the reaction solution contains the compound C represented by the following formula (C), the salt of the compound D represented by the following formula (D), and an alcohol having 3 or more carbon atoms. The method according to claim 2 or 3, further comprising a step of reacting the compound C with the compound D to obtain the compound B.

[In the formula (C) and the formula (D), R ¹ , R ² , Y ¹ , Y ² and L have the same meanings as described above, and X represents a halogen atom or a carboxyl group. ] The method according to any one of claims 1 to 5, wherein the compound A is a compound represented by the following formula (A-1).

[In the formula (A-1), R ¹ , R ² , Y ¹ and Y ² have the same meaning as described above, and a plurality of R ¹ , R ² , Y ¹ and Y ² are different even if they are the same. May be. ] The production method according to any one of claims 1 to 6, wherein the compound A is 1,3-bis (3-methylsulfonylpropyl) -1,1,3,3-tetramethyldisiloxane.