JP7560857B2 - Method for producing sulfonic acid silyl ester and novel silicon compound - Google Patents

Description

The present invention relates to an efficient method for producing sulfonic acid silyl esters and a novel silicon compound.

Sulfonic acid silyl esters are functional chemicals that are used as reagents for precision synthesis of medicines, agricultural chemicals, electronic materials, etc., and as synthetic intermediates thereof.
As methods for producing these, for example, a method of reacting chlorosilane with sulfonic acid or a silver salt of sulfonic acid (Method A, Non-Patent Document 1), a method of reacting methylsilane (tetramethylsilane), allylsilane (allyltrimethylsilane), or the like with sulfonic acid (Method B, Non-Patent Documents 2 and 3), a method of reacting silanol (trimethylsilanol) with sulfonic acid anhydride (Method C, Patent Document 1), and a method of reacting disiloxane (hexamethyldisiloxane) with sulfonic acid anhydride (Method D, Non-Patent Document 4) have been considered.

However, the method using chlorosilanes (Method A) requires careful handling of the raw materials and design of the equipment because chlorosilanes generate highly corrosive hydrogen chloride upon hydrolysis, while the method using methylsilane, allylsilane, or the like (Method B) has problems such as the high cost of methylsilane, allylsilane, and the fact that the types of sulfonic acids that react with methylsilane are limited to highly acidic sulfonic acids such as trifluoromethanesulfonic acid.
Furthermore, the method using silanol (Method C) has problems such as the fact that the types of silanol that are readily available are limited, and that silanol is not very stable and therefore requires careful handling.
Furthermore, in the methods using chlorosilane, methylsilane, allylsilane, or silanol (Methods A, B, and C), hydrogen chloride, methane, propene, or sulfonic acid is generated as a co-product of the reaction, which causes problems such as low atom utilization efficiency.
On the other hand, the method using disiloxane (Method D) has the advantage that there are no co-products in the reaction and therefore the atom utilization efficiency is very high. However, when using sulfonic anhydrides with low reactivity, the reaction is slow and the product yield is low, which is a problem.
For these reasons, there has been a demand for an industrially more advantageous method.

Chinese Patent Publication No. 103665017

Chem. Ber., 103, 868-879 (1970) Synthesis, 827 (1982) Synthesis, 745-746 (1981) Synthesis, 206-207 (1985)

The present invention has been made in consideration of the above circumstances, and aims to provide an efficient method for producing sulfonic acid silyl esters.

As a result of intensive research aimed at solving the above problems, the present inventors have found that (1) a siloxane compound such as disiloxane having a Si—O—Si bond reacts smoothly with a sulfonic anhydride in the presence of an acidic compound to efficiently give a sulfonate silyl ester, (2) the produced sulfonate silyl ester reacts with a modifying agent such as an alkyne or alkene to give a silicon compound in which the Si—O— _SO2 bond of the sulfonate silyl ester is converted to a Si—C bond, and (3) a novel silicon compound can be obtained by the reaction of (1) and (2), and have completed the present invention.

Ｘ^１Ｏ（ＳｉＲ^６Ｒ^７Ｏ）_ｎＸ^２ （ＩＣ）
（これら式中、Ｒ^１～Ｒ^７は、それぞれ独立に炭素数１～２４の炭化水素基または水素原子であり、前記炭化水素基の炭素原子に結合した水素原子の一部または全部が反応に関与しない基で置換されていてもよく；Ｘ^１およびＸ^２は、それぞれ独立にシリル基または水素原子であり；ｍおよびｎは、それぞれ独立に２以上１００００以下の整数であり；Ｒ^１～Ｒ^７の各々が同一分子内に複数個ある場合、それらは互いに同一でも異なっていてもよい。）
＜５＞
前記スルホン酸無水物が、下記一般式（ＩＩ）で表される化合物である、＜１＞～＜４＞の何れかに記載のスルホン酸シリルエステルの製造方法。
（Ｒ^８ＳＯ_２）_２Ｏ （ＩＩ）
（式中、Ｒ^８は、炭素数１～２４の炭化水素基であり、前記炭化水素基の炭素原子に結合した水素原子の一部または全部が反応に関与しない基で置換されていてもよい。）
＜６＞
前記反応工程が、マイクロ波の照射下で行われる、＜１＞～＜５＞の何れかに記載のス
ルホン酸シリルエステルの製造方法。
＜７＞
＜１＞～＜６＞の何れかに記載の製造方法によりスルホン酸シリルエステルを製造するスルホン酸シリルエステル製造工程、および
生成したスルホン酸シリルエステルに、アルキンまたはアルケンから選ばれる修飾剤を反応させる修飾工程
を含む、Ｓｉ－Ｃ結合を有するケイ素化合物の製造方法。
＜８＞
前記修飾剤が、下記一般式（ＩＶＡ）で表されるアルキン、および、下記一般式（ＩＶＢ１）または（ＩＶＢ２）で表されるアルケンから選ばれる化合物である、＜７＞に記載のケイ素化合物の製造方法。
Ｒ^９Ｃ≡ＣＨ （ＩＶＡ）
Ｚ^１Ｒ^１０ＣＨＣＨ＝ＣＨＲ^１１ （ＩＶＢ１）
Ｚ^１Ｒ^１０Ｃ＝ＣＨＣＨ_２Ｒ^１１ （ＩＶＢ２）
（これら式中、Ｒ^９～Ｒ^１１は、それぞれ独立に炭素数１～２０の炭化水素基または水素原子であり、前記炭化水素基の炭素原子に結合した水素原子の一部または全部が反応に関与しない基で置換されていてもよく；Ｚ^１は、シアノ基、ニトロ基、アシル基、アミド基、アリールスルホニル基、およびアルキルスルホニル基から選ばれる基である。）
＜９＞
前記修飾工程が、塩基性化合物の存在下で行われる、＜７＞または＜８＞に記載のケイ素化合物の製造方法。
＜１０＞
前記塩基性化合物が、アミン化合物、アミジン化合物、グアニジン化合物、およびホスファゼン化合物から選ばれる化合物である、＜９＞に記載のケイ素化合物の製造方法。
＜１１＞
前記修飾工程が、マイクロ波の照射下で行われる、＜７＞～＜１０＞の何れかに記載のケイ素化合物の製造方法。
＜１２＞
下記一般式（Ｖ）、（ＶＩ）、（ＶＩＩ）、または（ＶＩＩＩ）で表されるケイ素化合物。
Ｒ^１２Ｒ^１３Ｒ^１４Ｓｉ（ＯＳＯ_２Ｒ^１５） （Ｖ）
Ｒ^１６Ｒ^１７Ｒ^１８Ｓｉ（Ｃ≡ＣＲ^１９） （ＶＩ）
Ｒ^２０Ｒ^２１Ｒ^２２Ｓｉ［Ｃ（ＣＮ）＝ＣＨＲ^２３］ （ＶＩＩ）
Ｘ^３（ＳｉＲ^２４Ｒ^２５Ｏ）_ａＳｉＲ^２４Ｒ^２５Ｘ^４ （ＶＩＩＩ）
（これら式中、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、およびＲ^２５は、それぞれ独立にメチル基、クロロメチル基、３－シアノプロピル基、フェニル基、およびビニル基より選ばれる基であり；Ｒ^１５は、トリフルオロメチル基、メチル基、およびｐ－トリル基から選ばれる基であり；Ｒ^１２～Ｒ^１４のうち少なくとも一つおよびＲ^２０～Ｒ^２２のうち少なくとも一つは、それぞれ独立にクロロメチル基、３－シアノプロピル基、フェニル基、およびビニル基より選ばれる基であり；Ｒ^１６～Ｒ^１８のうち少なくとも一つは、それぞれ独立にクロロメチル基、３－シアノプロピル基、およびビニル基より選ばれる基であり；Ｘ^３およびＸ^４は、それぞれ独立にトリフルオロメタンスルホニルオキシ基、メタンスルホニルオキシ基、ｐ－トルエンスルホニルオキシ基、エトキシ基、メトキシ基、フェニルエチニル基、および１－シアノ－１－プロペニル基から選ばれる基であり；Ｘ^３およびＸ^４のうちの少なくとも一つは、それぞれ独立にトリフルオロメタンスルホニルオキシ基、メタンスルホニルオキシ基、ｐ－トルエンスルホニルオキシ基、フェニルエチニル基、および１－シアノ－１－プロペニル基から選ばれる基であり；ａは、１以上５以下の整数である。） That is, this application provides the following inventions.
＜1＞
A method for producing a sulfonic acid silyl ester having an Si—O—SO ₂ bond, comprising a reaction step of reacting a siloxane compound having an Si—O—Si bond with a sulfonic acid anhydride in the presence of an acidic compound.
＜2＞
The method for producing a sulfonic acid silyl ester according to <1>, wherein the acidic compound is a compound selected from a Lewis acid compound containing an element of Groups 3 to 15, a sulfonic acid compound, and a solid acid.
＜3＞
The method for producing a sulfonic acid silyl ester according to <2>, wherein the acidic compound is a compound selected from the group consisting of Lewis acid compounds containing iron or indium, perfluoroalkanesulfonic acid, bis(perfluoroalkanesulfonyl)imide, montmorillonite, and zeolite.
＜4＞
The method for producing a sulfonic acid silyl ester according to any one of <1> to <3>, wherein the siloxane compound having a Si—O—Si bond is a siloxane compound represented by the following general formula (IA), (IB), or (IC):
R ¹ R ² R ³ Si-O-SiR ¹ R ² R ³ (IA)

X ¹ O(SiR ⁶ R ⁷ O) _n X ² (IC)
(In these formulas, R ¹ to R ⁷ are each independently a hydrocarbon group having 1 to 24 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction; X ¹ and X ² are each independently a silyl group or a hydrogen atom; m and n are each independently an integer of 2 or more and 10,000 or less; and when there are multiple R ¹ to R ⁷ in the same molecule, they may be the same or different.)
＜5＞
The method for producing a sulfonic acid silyl ester according to any one of <1> to <4>, wherein the sulfonic acid anhydride is a compound represented by the following general formula (II):
(R ⁸ SO ₂ ) ₂ O (II)
(In the formula, R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction.)
＜6＞
<5> The method for producing a sulfonic acid silyl ester according to any one of <1> to <5>, wherein the reaction step is carried out under microwave irradiation.
＜７＞
A method for producing a silicon compound having a Si-C bond, comprising: a sulfonate silyl ester production step of producing a sulfonate silyl ester by the production method according to any one of <1> to <6>; and a modification step of reacting the produced sulfonate silyl ester with a modifying agent selected from an alkyne or an alkene.
＜8＞
The method for producing a silicon compound according to <7>, wherein the modifying agent is a compound selected from an alkyne represented by the following general formula (IVA) and an alkene represented by the following general formula (IVB1) or (IVB2).
R ⁹ C≡CH (IVA)
Z ¹ R ¹⁰ CHCH=CHR ¹¹ (IVB1)
Z ¹ R ¹⁰ C=CHCH ₂ R ¹¹ (IVB2)
(In these formulas, R ⁹ to R ¹¹ are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with a group that does not participate in the reaction; Z ¹ is a group selected from a cyano group, a nitro group, an acyl group, an amido group, an arylsulfonyl group, and an alkylsulfonyl group.)
＜9＞
The method for producing a silicon compound according to <7> or <8>, wherein the modification step is carried out in the presence of a basic compound.
＜10＞
The method for producing a silicon compound according to <9>, wherein the basic compound is a compound selected from the group consisting of an amine compound, an amidine compound, a guanidine compound, and a phosphazene compound.
<11>
The method for producing a silicon compound according to any one of <7> to <10>, wherein the modification step is carried out under microwave irradiation.
＜12＞
A silicon compound represented by the following general formula (V), (VI), (VII), or (VIII):
R ¹² R ¹³ R ¹⁴ Si(OSO ₂ R ¹⁵ ) (V)
R ¹⁶ R ¹⁷ R ¹⁸ Si (C≡CR ¹⁹ ) (VI)
^R20R21R22Si [C( ^CN )= ^{CHR23 ]} (VII)
X ³ (SiR ²⁴ R ²⁵ O) _a SiR ²⁴ R ²⁵ X ⁴ (VIII)
(In these formulas, R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , and R ²⁵ are each independently a group selected from a methyl group, a chloromethyl group, a 3-cyanopropyl group, a phenyl group, and a vinyl group; R ¹⁵ is a group selected from a trifluoromethyl group, a methyl group, and a p-tolyl group; at least one of R ¹² to R ¹⁴ and at least one of R ²⁰ to R ²² are each independently a group selected from a chloromethyl group, a 3-cyanopropyl group, a phenyl group, and a vinyl group; at least one of R ¹⁶ to R ¹⁸ are each independently a group selected from a chloromethyl group, a 3-cyanopropyl group, and a vinyl group; X ³ and X X ⁴ are each independently a group selected from a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, an ethoxy group, a methoxy group, a phenylethynyl group, and a 1-cyano-1-propenyl group; at least one of X ³ and X ⁴ is each independently a group selected from a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a phenylethynyl group, and a 1-cyano-1-propenyl group; and a is an integer of 1 or more and 5 or less.

The manufacturing method of the present invention has the effect of efficiently producing sulfonic acid silyl esters and their modified compounds.

In detail, a preferred embodiment of the production method of the present invention has the following features.
(1) The raw materials are relatively easy to obtain, the reaction conditions are mild, and the reaction efficiency is high.
(2) Since there are no co-products in the reaction, it is a clean reaction system with high atom utilization efficiency.
(3) Since the reaction is promoted in the presence of an acidic compound, even reactions with sulfonic acid anhydrides, which are not highly reactive, can be easily carried out.
(4) Since the reaction step and the modification step can be carried out continuously, a silicon compound having a Si-C bond, such as an alkynylsilane or alkenylsilane, can be produced using an alkoxysilane as a raw material in a simple one-pot process.
(5) Novel functional silicon compounds can be produced efficiently.
In a preferred embodiment of the production method of the present invention, it is possible to efficiently produce silicon compounds having a Si-C bond, such as sulfonate silyl esters and modified compounds thereof, such as alkynylsilanes and alkenylsilanes, and the method has great advantages over conventional techniques in terms of safety, economy, etc.

The present invention will be described in detail below. Unless otherwise specified, when a symbol in a formula in this specification is used in other formulas, the same symbol has the same meaning.
A method for producing a sulfonic acid silyl ester according to one embodiment of the present invention is characterized by including a reaction step of reacting a siloxane compound having a Si—O—Si bond with a sulfonic acid anhydride in the presence of an acidic compound.

In this embodiment, the siloxane compound having a Si—O—Si bond used as a raw material is represented by, for example, the following general formulas (IA) to (IC).
R ¹ R ² R ³ Si-O-SiR ¹ R ² R ³ (IA)

X ¹ O(SiR ⁶ R ⁷ O) _n X ² (IC)
In these formulas, R ¹ to R ⁷ each independently represent a hydrocarbon group having 1 to 24 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group do not participate in the reaction. In addition, when there are a plurality of each of R ¹ to R ⁷ in the same molecule, they may be the same or different. "Does not" means that it does not directly participate as a reactant in the target reaction, and does not inhibit or promote the reaction.
^X1 and ^X2 each independently represent a silyl group or a hydrogen atom.
Furthermore, m and n are each independently an integer of 2 or more and 10,000 or less.

When R ¹ to R ⁷ are each a hydrocarbon group having 1 to 24 carbon atoms, examples of the hydrocarbon group include an alkyl group, an aryl group, an aralkyl group, and an alkenyl group.

When the hydrocarbon group is an alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 10, and particularly preferably 1 to 4. Some or all of the hydrogen atoms bonded to the carbon atoms of the alkyl group may be substituted with groups that do not participate in the reaction.

Examples of the group that is not involved in the reaction include an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 1 to 6 carbon atoms, a dialkylamino group having 1 to 6 carbon atoms, a cyano group, a nitro group, a halogen atom, etc. More specific examples of the alkoxy group, the alkoxycarbonyl group, the dialkylamino group, and the halogen atom include alkoxy groups such as a methoxy group, an ethoxy group, and a hexoxy group; alkoxycarbonyl groups such as a methoxycarbonyl group and a propoxycarbonyl group; dialkylamino groups such as a dimethylamino group and a diethylamino group; and halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.
Specific examples of the alkyl group which may be substituted with a group which does not participate in the reaction include a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group, a decyl group, a chloromethyl group, a 2-methoxyethyl group, a 3-ethoxypropyl group, a 2-methoxycarbonylethyl group, a 2-dimethylaminoethyl group, a 3-cyanopropyl group, a trifluoromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 1H,1H,2H,2H-tridecafluorooctyl group, and a 1H,1H,2H,2H-heptadecafluorodecyl group.

In addition, when the hydrocarbon group is an aryl group, a monovalent aromatic organic group of a hydrocarbon ring system or a heterocyclic ring system can be used. When the aryl group is a monovalent aromatic organic group of a hydrocarbon ring system, the number of carbon atoms is preferably 6 to 22, more preferably 6 to 14. Specific examples of the monovalent aromatic organic group of a hydrocarbon ring system include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, and a pentacenyl group. In addition, when the aryl group is a monovalent aromatic organic group of a heterocyclic ring system, the heteroatom in the heterocyclic ring is a sulfur atom, an oxygen atom, or the like. In addition, the number of carbon atoms of the monovalent aromatic organic group of a heterocyclic ring system is preferably 4 to 12, more preferably 4 to 8. Specific examples of the monovalent aromatic organic group of a heterocyclic ring system include a thienyl group, a benzothienyl group, a dibenzothienyl group, a furyl group, a benzofuryl group, and a dibenzofuryl group.
A part or all of the hydrogen atoms bonded to the carbon atoms of the aryl group may be substituted with a group that does not participate in the reaction. Examples of the group that does not participate in the reaction include those shown in the case of the alkyl group above. Other groups that do not participate in the reaction include an oxyethylene group, an oxyethyleneoxy group, etc., which are divalent groups that bond two carbon atoms on a ring. Specific examples of aryl groups having such groups include a methylphenyl group, an ethylphenyl group, a hexylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, an octoxyphenyl group, a methyl(methoxy)phenyl group, a fluoro(methyl)phenyl group, a chloro(methoxy)phenyl group, a bromo(methoxy)phenyl group, a 2,3-dihydrobenzofuranyl group, and a 1,4-benzodioxanyl group.

Furthermore, when the hydrocarbon group is an aralkyl group, the number of carbon atoms in the aralkyl group is preferably 7 to 23, more preferably 7 to 16. In addition, some or all of the hydrogen atoms bonded to the carbon atoms of the aralkyl group may be substituted with groups that are not involved in the reaction.
Examples of the group that does not participate in the reaction include those mentioned above for the alkyl group.
Specific examples of the aralkyl group which may be substituted by a group which does not participate in the reaction include a benzyl group, a phenethyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group, a (4-chlorophenyl)methyl group, and a 1-(4-methoxyphenyl)ethyl group.

When the hydrocarbon group is an alkenyl group, the number of carbon atoms in the alkenyl group is preferably 2 to 23, more preferably 2 to 20, still more preferably 2 to 10, and particularly preferably 2 to 4. Some or all of the hydrogen atoms bonded to the carbon atoms of the alkenyl group may be substituted with groups that are not involved in the reaction.
Examples of the group that does not participate in the reaction include those exemplified above for the alkyl group, as well as the aryl group and the like.
Specific examples of the alkenyl group which may be substituted by a group which does not participate in the reaction include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 5-hexenyl group, a 9-decenyl group, a 2-phenylethenyl group, a 2-(methoxyphenyl)ethenyl group, a 2-naphthylethenyl group, and a 2-anthrylethenyl group.

When ^X1 and ^X2 are silyl groups, examples of the silyl group include a trialkylsilyl group, a dialkylsilyl group, an aryldialkylsilyl group, an alkenyldialkylsilyl group, a monoalkylsilyl group, a triarylsilyl group, a diarylsilyl group, a monoarylsilyl group, a triaralkylsilyl group, a diaralkylsilyl group, a monoaralkylsilyl group, a trialkenylsilyl group, a dialkenylsilyl group, and a monoalkenylsilyl group. Examples of the alkyl group, aryl group, aralkyl group, and alkenyl group in these silyl groups include those described in the explanation of ^R1 to ^R7 . A preferred specific example of the silyl group is a trimethylsilyl group.

m is preferably an integer of 3 or more and 1000 or less, more preferably an integer of 3 or more and 200 or less, further preferably an integer of 3 or more and 50 or less, and particularly preferably an integer of 3 or more and 10 or less.
Further, n is preferably an integer of 3 or more and 5,000 or less, more preferably an integer of 3 or more and 3,000 or less, further preferably an integer of 3 or more and 1,000 or less, and particularly preferably an integer of 3 or more and 500 or less.

Therefore, specific examples of the siloxane compound having an Si-O-Si bond, which is a raw material having such a hydrocarbon group, include the following:
First, examples of the siloxane compounds represented by the general formula (IA) include hexamethyldisiloxane (Me ₃ SiOSiMe ₃ ), hexaethyldisiloxane (Et ₃ SiOSiEt ₃ ), 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane (Me ₂ PhSiOSiMe ₂ Ph), 1,1,3,3-tetraphenyl-1,3-dimethyldisiloxane (MePh ₂ SiOSiMePh ₂ ), 1,1,3,3-tetramethyl-1,3-divinyldisiloxane (Me ₂ ViSiOSiMe ₂ Vi), 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane ((ClCH ₂ )Me ₂ SiOSiMe ₂ (CH ₂ Cl), 1,3-bis(3-cyanopropyl)-1,1,3,3-tetramethyldisiloxane ([NC(CH ₂ ) ₃ ]Me ₂ SiOSiMe ₂ [(CH ₂ ) ₃ CN]), and the like.

Examples of the siloxane compound represented by general formula (IB) include hexamethylcyclotrisiloxane ((SiMe ₂ O) ₃ ), octamethylcyclotetrasiloxane ((SiMe ₂ O) ₄ ), 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane ((SiMeViO) ₄ ), decamethylcyclopentasiloxane ((SiMe ₂ O) ₅ ), dodecamethylcyclohexasiloxane ((SiMe ₂ O) ₆ ), and the like.

Further, examples of the siloxane compound represented by the general formula (IC) include poly(dimethylsiloxane) (X ^1a O(SiMe ₂ O) _p X ^2a ; X ^1a , X ^2a = SiMe ₃ or H), poly(methylphenylsiloxane) (X ^1b O(SiMePhO) _p X ^2b ; X ^1b , X ^2b = SiMe ₃ or H), poly(dimethylsiloxane-co-diphenylsiloxane) (X ^1c O
⁽ _SiMe2O ) _q ( _SiPh2O ) _rX2c ; ^X1c , ^X2c = _SiMe3 or H).
As the poly(dimethylsiloxane) or poly(dimethylsiloxane-co-diphenylsiloxane) having a trimethylsilyl group at the end, for example, those commercially available as silicone oils under the names KF-968 or KF-54 (both manufactured by Shin-Etsu Chemical Co., Ltd.) can be used.

On the other hand, the sulfonic acid anhydride to be reacted with the siloxane compound is, for example, represented by the following general formula (II):

(R ⁸ SO ₂ ) ₂ O (II)
In the general formula (II), R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group are substituted with groups that do not participate in the reaction. Good too.

Examples of the hydrocarbon group ^R8 include an alkyl group, an aryl group, an aralkyl group, and an alkenyl group, and examples of the group not involved in the reaction include those described above for ^R1 , ^R2 , or ^R3 in general formula (IA).
Regarding the number of carbon atoms in the hydrocarbon group, when the hydrocarbon group is an alkyl group, it is preferably 1 to 20, more preferably 1 to 18; when the hydrocarbon group is an aryl group, it is preferably 4 to 20, more preferably 4 to 18; when the hydrocarbon group is an aralkyl group, it is preferably 5 to 21, more preferably 5 to 19; and when the hydrocarbon group is an alkenyl group, it is preferably 2 to 20, more preferably 2 to 18.
Specific examples of the hydrocarbon group having 1 to 24 carbon atoms include those given in the explanation of R ¹ to R ⁷ in the above general formulae (IA) to (IC).

Therefore, specific examples of the sulfonic acid anhydride represented by the general formula (II) include trifluoromethanesulfonic acid anhydride (Tf ₂ O, Tf=SO ₂ CF ₃ ), nonafluorobutanesulfonic acid anhydride ([CF ₃ (CF ₂ ) ₃ SO ₂ ]O), p-toluenesulfonic acid anhydride ((p-TolSO ₂ ) ₂ O), methanesulfonic acid anhydride ((MeSO ₂ ) ₂ O), etc.

The molar ratio of sulfonic anhydride to the raw siloxane compound can be selected arbitrarily, but taking into consideration the yield of sulfonic acid silyl ester relative to the siloxane compound, the molar ratio per Si-O-Si bond in the siloxane compound is usually 0.5 to 300, more preferably 0.5 to 200, even more preferably 0.5 to 150, and particularly preferably 0.5 to 10.

According to this embodiment, the sulfonic acid silyl esters represented by the following general formulas (IIIA), (IIIB), and (IIIC) can be produced by the reaction of the siloxane compound represented by the general formula (IA) with the sulfonic acid anhydride represented by the general formula (II), the reaction of the siloxane compound represented by the general formula (IB) with the sulfonic acid anhydride represented by the general formula (II), and the reaction of the siloxane compound represented by the general formula (IC) with the sulfonic acid anhydride represented by the general formula (II), respectively.
R ¹ R ² R ³ Si (OSO ₂ R ⁸ ) (IIIA)
R ⁸ SO ₃ (SiR ⁴ R ⁵ O) _p SO ₂ R ⁸ (IIIB)
R ⁸ SO ₃ (SiR ⁶ R ⁷ O) _q SO ₂ R ⁸ (IIIC)
In these formulas, R ¹ to R ⁸ are defined in the same manner as R ¹ to R ⁷ in general formulas (IA) to (IC) and R ⁸ in general formula (II). Examples of R 1 to R 8 include those described in the explanation of general formulas (IA) to (IC) and (II).
Additionally, p and q each represent an integer of 1 to 1,000, preferably 1 to 500, and more preferably 1 to 200.

Specific examples of the compound represented by general formula (IIIA) include trimethylsilyl p-toluenesulfonate (Me ₃ SiOSO ₂ -p-Tol), trimethylsilyl trifluoromethanesulfonate (Me ₃ SiOTf), (3-cyanopropyl)dimethylsilyl triflate (NC(CH ₂ ) ₃ ]Me ₂ SiOTf), dimethylvinylsilyl tosylate (Me ₂ (CH ₂ ═CH)SiOSO ₂ -p-Tol), (3-cyanopropyl)dimethylsilyl tosylate ([NC(CH ₂ ) ₃ ]Me ₂ SiOSO ₂ -p-Tol), dimethylphenylsilyl tosylate (Me ₂ PhSiOSO ₂ -p-Tol), (chloromethyl)dimethylsilyl tosylate ((ClCH ₂ )Me ₂ SiOSO ₂ -p-Tol), and the like.

Specific examples of the compounds represented by the general formulas (IIIB) and (IIIC) include dimethylsilane bistriflate (TfO(SiMe ₂ O)Tf), 1,1,3,3-tetramethyldisiloxane-1,3-bistriflate (TfO(SiMe ₂ O) ₂ Tf), 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-bistriflate (TfO(SiMe ₂ O) ₃ Tf), 1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1,7-bistriflate (TfO(SiMe ₂ O) ₄ Tf), and 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane-1,9-bistriflate (TfO(SiMe ₂ O) _{5 Tf} ). Examples of the siloxane-1,11-bis(triflate) (TfO(SiMe ₂ O) ₆ Tf), dimethylsilane bismesylate (MeSO ₃ (SiMe ₂ O) SO ₂ Me), 1,1,3,3-tetramethyldisiloxane-1,3-bismesylate (MeSO ₃ (SiMe ₂ O) ₂ SO ₂ Me), and 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-bismesylate (MeSO ₃ (SiMe ₂ O) ₃ SO ₂ Me).

In the reaction step in this embodiment, it is believed that the reaction proceeds by nucleophilic interaction between the sulfonic anhydride and the siloxane compound having a Si—O—Si bond.
Therefore, the reaction in this embodiment is a reaction in which a bond recombination occurs between the Si-O-Si bond of the siloxane compound and the SO ₂ -O-SO ₂ bond of the sulfonic acid anhydride. For example, when a siloxane compound represented by the general formula (IA) is reacted with 1 equivalent of the sulfonic acid anhydride represented by the general formula (II), 2 equivalents of the sulfonic acid silyl ester represented by the general formula (IIIA) are produced (Scheme 1).

スキーム１

Scheme 1

On the other hand, when a cyclic or linear siloxane compound represented by the general formula (IB) or (IC) is reacted with a sulfonic anhydride represented by the general formula (II), a sulfonic acid silyl ester having acyloxy groups at both ends and represented by the general formula (IIIB) or (IIIC) is produced (Schemes 2 and 3).

スキーム２

Scheme 2

スキーム３

Scheme 3

The molecular weight distribution of the sulfonic acid silyl ester in Scheme 2 and Scheme 3 varies depending on the reactivity of the raw material siloxane compound and sulfonic acid anhydride, and their feed ratio, but generally, the higher the feed ratio of the raw material siloxane compound to the sulfonic acid anhydride, the higher the proportion of low molecular weight on the distribution.

In the reaction step of this embodiment, various homogeneous or heterogeneous acidic compounds are used as catalysts to promote the reaction.
As a method for carrying out the reaction in the presence of an acidic compound, not only a method in which an acidic compound is added to the reaction system, but also a method in which a small amount of water is added to the reaction system to partially hydrolyze the raw material sulfonic acid anhydride, and the resulting sulfonic acid is used as the acidic compound, is also possible.

As the acidic compound, a compound selected from Lewis acid compounds containing elements of Groups 3 to 15 and sulfonic acid compounds is preferred.

Examples of Lewis acid compounds containing elements from groups 3 to 15 include halides, perchlorates, sulfonates, bis(perfluoroalkanesulfonyl)imide salts, hexafluoroantimonates, thiocyanates, and the like of these elements.

The elements of Groups 3 to 15 are preferably selected from Groups 3, 8, and 13 to 15, more preferably from Groups 3, 8, 13, or 15, and even more preferably from Groups 8 or 13.
More specifically, the elements are preferably selected from scandium, yttrium, samarium, yttrium, iron, ruthenium, copper, aluminum, gallium, indium, tin, and bismuth, more preferably selected from scandium, iron, ruthenium, aluminum, gallium, indium, tin, and bismuth, and even more preferably selected from iron, ruthenium, aluminum, gallium, and indium.

More specifically, Lewis acid compounds containing these elements include scandium(III) chloride, titanium(III) chloride, titanium(IV) chloride, iron(III) chloride, iron(III) bromide, ruthenium(III) chloride, aluminum(III) chloride, gallium(III) chloride, indium(III) chloride, tin(IV) chloride, iron(III) perchlorate, scandium(III) trifluoromethanesulfonate, yttrium(III) trifluoromethanesulfonate, iron(III) trifluoromethanesulfonate, copper(II) trifluoromethanesulfonate, aluminum(III) trifluoromethanesulfonate, gallium(III) trifluoromethanesulfonate, indium(III) trifluoromethanesulfonate, and tin(IV) chloride. Examples of suitable Lewis acid compounds include tin(IV) trifluoromethanesulfonate, bismuth(IV) trifluoromethanesulfonate, lanthanum(III) trifluoromethanesulfonate, praseodymium(IV) trifluoromethanesulfonate, neodymium(IV) trifluoromethanesulfonate, ytterbium(IV) trifluoromethanesulfonate, bis(trifluoromethanesulfonyl)imide scandium(III), bis(trifluoromethanesulfonyl)imide zinc(II), bis(trifluoromethanesulfonyl)imide indium(III), bis(trifluoromethanesulfonyl)imide tin(IV), iron(III) hexafluoroantimonate, indium(III) hexafluoroantimonate, iron(III) thiocyanate, indium(III) thiocyanate, etc. Among these, Lewis acid compounds containing iron, indium, etc. are preferred, and more specifically, iron(III) perchlorate, bis(trifluoromethanesulfonyl)imide indium(III), etc. are preferred. Among these compounds, those containing water of crystallization (hydrates) are also preferably used.

As the acidic compound serving as a catalyst, a sulfonic acid compound is also preferably used.
Specific examples of such compounds that are preferably used include perfluoroalkanesulfonic acids such as trifluoromethanesulfonic acid and pentafluoroethanesulfonic acid; bis(trifluoromethanesulfonyl)imide and bis(pentafluoroethanesulfonyl)imide; and more specifically, trifluoromethanesulfonic acid, bis(trifluoromethanesulfonyl)imide, and the like are preferably used.

As the catalyst, various known solid acid catalysts can be used which are easy to separate and recover, etc. As the solid acid catalyst, inorganic and organic catalysts can be used.
Examples of inorganic solid acid catalysts include solid inorganic substances such as metal salts and metal oxides. More specifically, examples of such catalysts include zeolites, mesoporous silica, and montmorillonite having protic hydrogen atoms or metal cations (aluminum, gallium, indium, iron, titanium, scandium, cerium, tin, and the like), as well as inorganic solid acids supported on silica gel, heteropolyacids, carbon-based materials, and the like.
The types of zeolite include USY, Y, beta, mordenite, ZSM-5, etc., and the silica/alumina ratio is 3 to 2000, etc.
Examples of organic solid acid catalysts include various polymers and oligomers, such as polystyrene gel and polytetrafluoroethylene, which have acidic functional groups such as sulfo groups and carboxyl groups.
Among these solid acids, montmorillonite and zeolite are preferably used, and more specifically, montmorillonite having cations such as tin (IV), indium (III), aluminum (III), etc., and USY-based zeolites such as Montmorillonite K10 (manufactured by Merck) and CBV780 (manufactured by Zeolyst) are preferably used.

The amount of the acidic compound relative to the raw material siloxane compound can be determined as desired, but in terms of molar ratio or weight ratio, it is usually about 0.0001 to 20, preferably about 0.0001 to 10, more preferably about 0.001 to 8, and even more preferably about 0.001 to 6.
When water is added to generate sulfonic acid as a catalyst, the amount of water added to the reaction system is usually about 0.0001 to 0.4, preferably about 0.001 to 0.3, more preferably about 0.001 to 0.2, and particularly preferably about 0.01 to 0.2, in terms of a molar ratio to the sulfonic acid anhydride.

In this embodiment, the reaction in the reaction step can be carried out in a liquid phase or gas phase state depending on the reaction temperature or reaction pressure. The reaction can be carried out in various conventionally known reactor configurations, such as a batch type or a flow type.
The reaction temperature is usually −20° C. or higher, preferably −10 to 300° C., more preferably −10 to 200° C., and even more preferably 0 to 150° C. When the reaction is carried out at room temperature, the temperature range of room temperature is usually 0 to 40° C., preferably 5 to 40° C., and more preferably 10 to 35° C.
Furthermore, the reaction pressure is usually 0.1 to 100 atm, preferably 0.1 to 50 atm, and more preferably 0.1 to 10 atm.
The reaction time depends on the amount of the raw material, the amount of the catalyst, the reaction temperature, the form of the reaction apparatus, etc., but in consideration of productivity and efficiency, it is usually 0.1 to 72 hours, preferably 0.1 to 24 hours, more preferably 0.1 to 14 hours, and even more preferably 0.1 to 5 hours.

When the reaction is carried out in a liquid phase system, a solvent may be used or the reaction may be carried out without a solvent. When a solvent is used, various solvents that do not react with the raw materials can be used, such as hydrocarbons such as decalin (decahydronaphthalene), decane, benzene, and toluene; halogenated hydrocarbons such as chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,3-trichlorobenzene, and 1,2,4-trichlorobenzene; nitriles such as acetonitrile and benzonitrile; ethers such as tert-butyl methyl ether and dibutyl ether; and the like. Two or more of these solvents can also be used in combination.
As the solvent, a deuterated solvent, which is advantageous in analyzing the reaction product by a nuclear magnetic resonance spectrometer, can be used. For example, deuterated benzene, deuterated toluene, deuterated chloroform, deuterated acetonitrile, etc. can be used.
Furthermore, when the reaction is carried out in a gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen.

The reaction step in this embodiment can also be carried out under microwave irradiation. In the reaction step, the dielectric loss coefficients of the raw material sulfonic acid anhydride and the product sulfonic acid silyl ester are relatively large and efficiently absorb microwaves. Therefore, under microwave irradiation, these compounds are activated and the reaction can be carried out more efficiently.

In microwave irradiation reactions, various commercially available devices equipped with contact or non-contact temperature sensors can be used. In addition, the microwave irradiation output, type of cavity (multi-mode, single mode), irradiation form (continuous, intermittent), etc. can be determined as desired depending on the scale and type of reaction. The microwave frequency is usually 0.3 to 30 GHz. Among these, the IMS frequency band allocated for use in the industrial, scientific, and medical fields is preferable, and even more preferable among these are the 2.45 GHz band, 5.8 GHz band, etc.

In addition, in microwave irradiation reactions, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system in order to heat the reaction system more efficiently. As the type of heating material, various types of materials known in the art, such as activated carbon, graphite, silicon carbide, and titanium carbide, can be used. In addition, a molded catalyst can be used that is made by mixing the catalyst and heating material powder described above and calcining the mixture using an appropriate binder such as sepiolite or hormite.

The sulfonate silyl ester provided by the production method of the present embodiment generally has high reactivity, and therefore reactions when used as a synthetic intermediate, a surface treatment agent, a sol-gel material, or the like can be efficiently carried out under mild conditions.

In addition, the Si-O- _SO2 bond of the resulting sulfonic acid silyl ester can be easily converted to other bonds by reacting with an appropriate modifying agent.
For example, when a carbon-based modifying agent is reacted, the Si-O- _SO2 bond of the sulfonic acid silyl ester can be converted to a Si-C bond.

As such a carbon-based modifying agent, for example, an alkyne represented by the following general formula (IVA) or an alkene represented by the following general formula (IVB1) or (IVB2) can be used.
R ⁹ C≡CH (IVA)
(Z ¹ CH ₂ )R ¹⁰ C=CHR ¹¹ (IVB1)
Z ¹ HC=CR ¹⁰ (CH ₂ R ¹¹ ) (IVB2)

In the formula, R ⁹ to R ¹¹ are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction. Z ¹ is a group selected from a cyano group, a nitro group, an acyl group, an amido group, an arylsulfonyl group, and an alkylsulfonyl group, and some or all of the hydrogen atoms bonded to carbon atoms of the acyl group, the amido group, the arylsulfonyl group, and the alkylsulfonyl group may be substituted with groups that do not participate in the reaction.

Examples of the hydrocarbon group and the group not participating in the reaction for R ⁹ to R ¹¹ include those given in the explanation of R ¹ to R ⁸ above.
Specific examples of the acyl group include an acetyl group and a trifluoroacetyl group; specific examples of the amido group include an acetamido group and a trifluoroacetamido group; a specific example of the arylsulfonyl group includes a phenylsulfonyl group; and a specific example of the alkylsulfonyl group includes a methylsulfonyl group.

Therefore, examples of the alkyne represented by the general formula (IVA) include acetylene, 1-propyne, 1-butyne, 1-octyne, ethynylbenzene, 1-ethynylnaphthalene, 2-ethynylnaphthalene, 4-ethynylbiphenyl, and 9-ethynylanthracene.
Examples of the alkene represented by the general formula (IVB1) include allyl cyanide, 3-methyl-3-butenenitrile, 3-pentenenitrile, 4-phenyl-3-butenenitrile, 3-nitro-1-propene, methyl(2-propenyl)ketone, N,N-dimethyl-3-butenamide, 3-phenylsulfonyl-1-propene, and 3-methylsulfonyl-1-propene.
Examples of the alkene represented by the general formula (IVB2) include 2-butenenitrile, 2-pentenenitrile, and 4-phenyl-2-butenenitrile.

When the sulfonate silyl ester obtained in the above reaction step is reacted with an alkyne represented by general formula (IVA), a silicon compound in which the alkyl or arylsulfonyl group of the sulfonate silyl ester is converted to an alkynyl group (R ⁹ C≡C--) is obtained.
Furthermore, when an alkene represented by the general formula (IVB1) or (IVB2) is reacted, a silicon compound in which the alkyl or arylsulfonyl group of the sulfonic acid silyl ester is converted to an alkenyl group ((R ¹¹ CH ₂ )R ¹⁰ C═CX ¹ —) is obtained.

Specific examples of such silicon compounds having a Si--C bond (sometimes referred to as "modified compounds") include trimethyl(phenylethynyl)silane (PhC≡CSiMe ₃ ), (3-cyanopropyl)dimethyl(phenylethynyl)silane (PhC≡CSiMe ₂ [(CH _{2 ) 3 CN]), dimethyl(phenylethynyl)(vinyl)silane (PhC≡CSiMe 2 [(CH 2} ) ₃ CN]), and the like.
Examples of such _{silanes include} dimethyl(phenyl)(phenylethynyl)silane (PhC≡CSiMe ₂ Ph), 2-trimethylsilyl-2-butenenitrile (MeCH═C(CN)(SiMe ₃ )), and 2,4-bis(trimethylsilyl)-2-butenenitrile (Me ₃ SiCH ₂ CH═C(CN)(SiMe ₃ )).

スキーム４ This modification reaction is believed to proceed as shown in the following Scheme 4 or Scheme 5.

Scheme 4

スキーム５

Scheme 5

In these reactions, when an alkyne or alkene reacts with a sulfonic acid silyl ester, the sulfonic acid is eliminated to produce an alkynylsilane or alkenylsilane, respectively.
In the reaction with an alkene, an isomerization reaction may occur due to migration of a double bond so that conjugation with ^Z1 , which is an electron-withdrawing group, becomes favorable. In the presence of a base, this isomerization reaction is considered to proceed particularly easily.

In addition, when reacting alkenes, the alkenes represented by general formula (IVB1) or general formula (IVB2) can be interconverted by an isomerization reaction due to the shift of the double bond, as shown in Scheme 6, so products of similar structure may be obtained regardless of the structure of the alkene reacted. In particular, when a base is present, the isomerization reaction is more likely to occur, making it easier to obtain products of similar structure.

スキーム６

Scheme 6

In the modification step, the reaction can be accelerated by adding a basic compound that has the property of capturing sulfonic acid.
As such a basic compound, for example, an amine compound, an amidine compound, a guanidine compound, a phosphazene compound, etc. can be used, and organic or inorganic solid compounds having groups derived from these compounds can also be used.

Specific examples of the amine compound include triethylamine, diisopropylmethylamine, dicyclohexylmethylamine, diisopropylethylamine, 1,2,2,6,6-pentamethylpiperidine, tributylamine, trihexylamine, trioctylamine, N-methylpyrrolidine, and N-methylpiperidine. Specific examples of the amidine compound include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), and the like. Specific examples of the guanidine compound include 1,5,7-triazabicyclo[4.4.0]-5-decene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]-5-decene (MTBD), and the like. Specific examples of the phosphazene compound include tert-butylimino-tris(pyrrolidino)phosphorane (BTPP), tert-butylimino tris(dimethylamino)phosphorane (P1-t-Bu), 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP), tert-octylimino tris(dimethylamino)phosphorane (P1-t-Oct), 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2λ ⁵ ,4λ ⁵ -catenadi(phosphazene) (P2-Et), 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ ⁵ ,4λ ⁵ -catenadi(phosphazene) (P2-t-Bu), 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ ⁵ ,4λ ⁵ -catenadi(phosphazene) (P4-t-Bu), and the like.

Regarding the type of basic compound, in the case of a modification reaction of a highly reactive sulfonic acid silyl ester (triflate, etc.), amine compounds such as triethylamine and diisopropylmethylamine are preferably used, while in the case of a less reactive sulfonic acid silyl ester (tosylate, mesylate, etc.), highly basic amidine compounds such as DBU, DBN, MTBD, BTPP, BEMP, P2-t-Bu, guanidine compounds, or phosphazene compounds are preferably used. In particular, phosphazene compounds are advantageous in terms of lowering the reaction temperature and shortening the reaction time compared to amidine compounds.

The molar ratios of the carbon-based modifier and basic compound to the sulfonyl ester can be selected arbitrarily, but taking into consideration the yield to the sulfonyl ester, the molar ratio is usually 0.4 molar equivalents or more and 100 molar equivalents or less, more preferably 0.5 molar equivalents or more and 50 molar equivalents or less, even more preferably 0.5 molar equivalents or more and 20 molar equivalents or less, and particularly preferably 0.5 molar equivalents or more and 10 molar equivalents or less, relative to the sulfonyloxy group in the sulfonyl ester.

The reaction in the modification step can be carried out in a liquid or gas phase depending on the reaction temperature or pressure, and the reaction can be carried out in any of the conventionally known reactor configurations, such as a batch type or a flow type.
The reaction temperature is usually −20° C. or higher, preferably −10 to 300° C., more preferably −10 to 250° C., and even more preferably 0 to 200° C. When the reaction is carried out at room temperature, the temperature range of room temperature is usually 0 to 40° C., preferably 5 to 40° C., and more preferably 10 to 35° C.
Furthermore, the reaction pressure is usually 0.1 to 100 atm, preferably 0.1 to 50 atm, and more preferably 0.1 to 10 atm.
The reaction time depends on the amount of the raw materials, the reaction temperature, the shape of the reaction apparatus, etc., but in consideration of productivity and efficiency, it is usually 0.1 to 100 hours, preferably 0.1 to 72 hours, more preferably 0.1 to 24 hours, further preferably 0.1 to 14 hours, and particularly preferably 0.1 to 5 hours.

When the reaction is carried out in a liquid phase system, a solvent may be used or the reaction may be carried out without a solvent. When a solvent is used, examples of the solvent include those that can be used in the reaction step. Two or more types of solvents may be mixed and used.
Furthermore, when the reaction is carried out in a gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen.

The modification step in this embodiment can also be carried out under microwave irradiation. In the modification step, the dielectric loss coefficient of the raw material, such as sulfonic acid silyl ester, is relatively large and efficiently absorbs microwaves, so that under microwave irradiation, these compounds are activated and the reaction can be carried out more efficiently.

In microwave irradiation reactions, various commercially available devices equipped with contact or non-contact temperature sensors can be used. In addition, the microwave irradiation output, type of cavity (multi-mode, single mode), irradiation form (continuous, intermittent), etc. can be determined as desired depending on the scale and type of reaction. The microwave frequency is usually 0.3 to 30 GHz. Among these, the IMS frequency band allocated for use in the industrial, scientific, and medical fields is preferable, and even more preferable among these are the 2.45 GHz band, 5.8 GHz band, etc.

In addition, in microwave irradiation reactions, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system in order to heat the reaction system more efficiently. As the type of heating material, various types of materials known in the art, such as activated carbon, graphite, silicon carbide, and titanium carbide, can be used. In addition, a molded catalyst can be used that is made by mixing the catalyst and heating material powder described above and calcining the mixture using an appropriate binder such as sepiolite or hormite.

The modification step in this embodiment can be carried out not only by purifying the sulfonate silyl ester produced in the reaction step, but also by using the unpurified sulfonate silyl ester obtained in the reaction step.
The method using an unpurified sulfonic acid silyl ester is a method by which a modified compound can be obtained from the starting siloxane compound in a simple one-pot operation, and is an advantageous embodiment that represents the features of the present invention.

In addition, the sulfonic acid silyl ester produced in the reaction step and the modified compound produced in the modification step can be easily purified by means commonly used in organic chemistry, such as distillation, recrystallization, and chromatography.

In addition, in the case where unreacted sulfonyloxy groups remain in the modification step, another type of alkyne, alkene, or other modifying agent can be further added to convert the remaining sulfonyloxy groups to other substituents to obtain another modified compound.
For example, when an alcohol such as ethanol or methanol is used as the other modifying agent, a modified compound in which the remaining sulfonyloxy groups are converted to alkoxy groups such as ethoxy groups or methoxy groups is obtained.
When unreacted sulfonyloxy groups remain, sulfonyloxysilanes may react with each other to produce a modified compound accompanied by the formation of an Si--O--Si bond.

Specific examples of such modified compounds include trimethyl(phenylethynyl)silane (PhC≡CSiMe ₃ ), (3-cyanopropyl)dimethyl(phenylethynyl)silane (PhC≡CSiMe ₂ [(CH ₂ ) ₃ CN]), dimethyl(phenylethynyl)(vinyl)silane (PhC≡CSiMe ₂ (CH═CH ₂ )), dimethyl(phenyl)(phenylethynyl)silane (PhC≡CSiMe ₂ Ph), 2-trimethylsilyl-2-butenenitrile (MeCH═C(CN)(SiMe ₃ )), 2,4-bis(trimethylsilyl)-2-butenenitrile (Me ₃ SiCH ₂ CH═C(CN)(SiMe ₃ )), 2-[(cyanopropyl)dimethylsilyl]-2-butenenitrile (MeCH═C(CN){SiMe ₂ [(CH ₂ ) ₃ CN]}), 2,4-bis[(cyanopropyl)dimethylsilyl]-2-butenenitrile ({[NC(CH ₂ ) ₃ ]Me ₂ Si}CH ₂ CH═C(CN){SiMe ₂ [(CH ₂ ) ₃ CN]}).

Furthermore, the above-mentioned reaction step, or the reaction step and the modification step, can provide a novel silicon compound represented by the following general formula (V), (VI), (VII), or (VIII).
R ¹² R ¹³ R ¹⁴ Si(OSO ₂ R ¹⁵ ) (V)
R ¹⁶ R ¹⁷ R ¹⁸ Si (C≡CR ¹⁹ ) (VI)
^R20R21R22Si [C( ^CN )= ^{CHR23 ]} (VII)
X ³ (SiR ²⁴ R ²⁵ O) _a SiR ²⁴ R ²⁵ X ⁴ (VIII)
In these formulas, R ¹² , R ¹³ , R ¹⁴ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , and R ²⁵ are each independently a group selected from a methyl group, a chloromethyl group, a 3-cyanopropyl group, a phenyl group, and a vinyl group; R ¹⁵ is a group selected from a trifluoromethyl group, a methyl group, and a p-tolyl group. At least one of R ¹² to R ¹⁴ and at least one of R ²⁰ to R ²² are each independently a group selected from a chloromethyl group, a 3-cyanopropyl group, a phenyl group, and a vinyl group. At least one of R ¹⁶ to R ¹⁸ are each independently a group selected from a chloromethyl group, a 3-cyanopropyl group, and a vinyl group.
Furthermore, ^X3 and ^X4 are each independently a group selected from a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, an ethoxy group, a methoxy group, a phenylethynyl group, and a 1-cyano-1-propenyl group, and at least one of ^X3 and ^X4 is each independently a group selected from a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a phenylethynyl group, and a 1-cyano-1-propenyl group.
Furthermore, a is an integer of 1 or more and 5 or less.

In the general formula (V), preferred examples of the combination of (R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ ) include (methyl group, methyl group, 3-cyanopropyl group, trifluoromethyl group), (methyl group, methyl group, 3-cyanopropyl group, p-tolyl group), (methyl group, methyl group, chloromethyl group, p-tolyl group), (methyl group, methyl group, phenyl group, p-tolyl group), (methyl group, methyl group, vinyl group, p-tolyl group). In the general formula (VI), preferred examples of the combination of (R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ ) include (methyl group, methyl group, 3-cyanopropyl group, phenyl group), and the like. In the general formula (VII), preferred examples of the combination of (R ²⁰ , R ²¹ , R ²² , R ²³ ) include (methyl group, methyl group, 3-cyanopropyl group, phenyl group), and the like. Preferred examples of the combination of (R ²⁴ , R ²⁵ , X ³ , X ⁴ ) include (methyl group, methyl group, 3-cyanopropyl group, methyl group), and the like. Preferred examples of the combinations of a) include (methyl group, methyl group, trifluoromethanesulfonyloxy group, trifluoromethanesulfonyloxy group, 2), (methyl group, methyl group, trifluoromethanesulfonyloxy group, trifluoromethanesulfonyloxy group, 3), (methyl group, methyl group, trifluoromethanesulfonyloxy group, trifluoromethanesulfonyloxy group, 4), (methyl group, methyl group, trifluoromethanesulfonyloxy group, trifluoromethanesulfonyloxy group, 5), (methyl group, methyl group, trifluoromethanesulfonyloxy group, trifluoromethanesulfonyloxy group, 6), (methyl group, methyl group, methanesulfonyloxy group, methanesulfonyloxy group, 2), (methyl group, methyl group, methanesulfonyloxy group, methanesulfonyloxy group, 3), and the like.
These silicon compounds have reactive groups such as trifluoromethanesulfonyloxy and ethoxy groups; and functional groups such as alkynyl and alkenyl groups; and therefore can be used as functional silicon compounds useful as synthesis intermediates, surface treatment agents, etc.

Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
The main analytical instruments used in the following examples are as follows:
Nuclear magnetic resonance spectroscopy (hereinafter sometimes referred to as NMR): Bruker AVANCE III HD 600MHz (with cryoprobe)
Gas chromatograph analysis (hereinafter sometimes referred to as GC): Shimadzu Corporation GC-2014
Gas chromatograph mass spectrometry (hereinafter sometimes referred to as GC-MS): Shimadzu Corporation GCMS-QP2010Plus

Example 1
0.45 mmol of hexamethyldisiloxane (Me ₃ SiOSiMe ₃ ), 0.47 mmol of p-toluenesulfonic anhydride ((p-TolSO ₂ ) ₂ O), 0.0045 mmol of Fe(ClO ₄ ) _{3.6H 2} O, and 0.12 mL of o-dichlorobenzene were placed in a reaction vessel and stirred at 100° C. for 0.5 hours. The product was analyzed by NMR, and the yield of the product was measured by NMR, indicating that trimethylsilyl p-toluenesulfonate (Me ₃ SiOTf) was produced in a yield of 90% (see Table 1-1).

(Examples 2 to 57)
The reaction and analysis were carried out in the same manner as in Example 1, except that the reaction conditions (raw materials, catalyst, temperature, time, etc.) were changed. The product yields were measured by NMR, and the results are shown in Tables 1-1 to 1-5 (sometimes simply referred to as "Table 1").

The notes in Table 1 are as follows:
1) (Me ₃ Si) ₂ O: Hexamethyldisiloxane
{[NC( _CH2 ) ₃ ] _Me2Si } _2O : 1,3-bis(3-cyanopropyl)-1,1,3,3-tetramethyldisiloxane
[ _Me2 ( _CH2 =CH)Si] _2O : 1,1,3,3-tetramethyl-1,3-divinyldisiloxane
( _Me2PhSi ) _2O : 1,1,3,3-tetramethyl-1,3-diphenyldisiloxane
[( _ClCH2 ) _Me2Si ] _2O : 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane
( _SiMe2O ) ₃ : Hexamethylcyclotrisiloxane
( _SiMe2O ) ₄ : Octamethylcyclotetrasiloxane
( _SiMe2O ) ₅ : Decamethylcyclopentasiloxane
KF-968: Poly(dimethylsiloxane) (Shin-Etsu Chemical Co., Ltd., _Me3SiO ( _SiMe2O ) _nSiMe3 , _polysiloxane with methyl groups as substituents and trimethylsilyl groups at both ends). When the siloxane compound is a polymer, the number of moles used indicates the number of moles per repeating structural unit. The molecular weight of the repeating structural unit for KF-968 is 74.2.
2) (p-TolSO ₂ ) ₂ O: p-Toluenesulfonic anhydride
_Tf2O : Trifluoromethanesulfonic anhydride
( _MeSO2 ) _2O : Methanesulfonic anhydride
3) Fe( _ClO4 ) _3.6H2O : Iron(III) perchlorate _hexahydrate
TfOH: Trifluoromethanesulfonic acid
In( _NTf2 ) ₃ : Tris[bis(trifluoromethanesulfonyl)imide]indium(III)
Sn4 ⁺ -mont: Sn4 ⁺ -containing montmorillonite
K10 mont: Montmorillonite K10 (Merck)
CBV780: H ⁺ type USY zeolite (manufactured by Zeolyst)
_H2O : Water. The unit of the values in parentheses is mmol, and the unit of the values in square brackets is mg. In the examples where _H2O is listed in the catalyst column, the sulfonic acid generated by partial hydrolysis of the raw material sulfonic anhydride in the reaction system actually acts as a catalyst.
4) DCB: 1,2-dichlorobenzene
PhMe: Toluene
MeCN: Acetonitrile
_CHCl3 : Chloroform
_C6D6 : Heavy _benzene

5) 25°C indicates the reaction temperature at room temperature. For reactions at temperatures higher than room temperature, an oil bath (Riko Kagaku MH-5D) was used. All reactions were carried out in a sealed state.
6) Me ₃ SiOSO ₂ -p-Tol: Trimethylsilyl p-toluenesulfonate
Me ₃ SiOTf: Trimethylsilyl trifluoromethanesulfonate
[NC( _CH2 ) ₃ ] _Me2SiOTf : (3-cyanopropyl)dimethylsilyl triflate
(ClCH ₂ )Me ₂ SiOTf: (chloromethyl)dimethylsilyl triflate
_Me2 ( _CH2 =CH)SiOSO2- _p -Tol: Dimethylvinylsilyl tosylate
[NC( _CH2 ) ₃ ] _Me2SiOSO2 - _p -Tol: (3-cyanopropyl)dimethylsilyl tosylate
_Me2PhSiOSO2 - _p -Tol: Dimethylphenylsilyl tosylate
(ClCH ₂ )Me ₂ SiOSO ₂ -p-Tol: (chloromethyl)dimethylsilyl tosylate
TfO( _SiMe2O )Tf: dimethylsilane bistriflate
TfO( _SiMe2O ) _2Tf : 1,1,3,3-tetramethyldisiloxane-1,3-bistriflate
TfO( _SiMe2O ) _3Tf : 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-bistriflate
TfO( _SiMe2O ) _4Tf : 1,1,3,3,5,5,7,7-octamethyltetrasiloxane-1,7-bistriflate
TfO( _SiMe2O ) _5Tf : 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane-1,9-bistriflate
TfO( _SiMe2O ) _6Tf : 1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane-1,11-
Bistriflates
MeSO ₃ (SiMe ₂ O)SO ₂ Me: Dimethylsilane bismesylate
MeSO ₃ (SiMe ₂ O) ₂ SO ₂ Me: 1,1,3,3-tetramethyldisiloxane-1,3-bismesylate
MeSO ₃ (SiMe ₂ O) ₃ SO ₂ Me: 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-bismesylate
7) Yield by NMR (yield of sulfonic acid silyl ester relative to siloxane).
8) A mixture of compounds TfO(SiMe ₂ O) _p Tf (p = 1, 2, 3, 4, ≧5) with two sulfonyloxy groups. The numbers in brackets indicate the ratio of the compounds. The yield indicates the total yield.
9) A mixture of compounds having two sulfonyloxy groups, MeSO ₃ (SiMe ₂ O) _p SO ₂ Me (p = 1, 2, 3, 4, ≧5). The numbers in brackets indicate the ratio of the compounds. The yield indicates the total yield.
10) A mixture of Me ₃ SiOTf and a compound having two sulfonyloxy groups, TfO(SiMe ₂ O) _q Tf (q = 1, 2, 3, 4, ≧5). The figures in brackets indicate the ratio of the compounds. The yield indicates the total yield.

In the production method of the present invention, the reaction proceeds efficiently by using a catalyst.
For example, in the reaction of hexamethyldisiloxane with p-toluenesulfonic anhydride, when no catalyst was used, the yield of sulfonate silyl ester was only 5% under reaction conditions of 100° C. for 0.5 hours, as shown in Comparative Example 1 in Table 1. On the other hand, when Fe(ClO ₄ ) 3.6H 2 O or trifluoromethanesulfonic acid was used as a catalyst, the sulfonate silyl ester was obtained in high yields of 90% or 94%, respectively, as shown in Examples ₁ and ₂ .
Furthermore, when trifluoromethanesulfonic anhydride was used as the sulfonic anhydride, as shown in Comparative Example 2 and Example 10, the yields when no catalyst was used and when trifluoromethanesulfonic acid was used as a catalyst were 41% and 80%, respectively, under reaction conditions of about 25° C. and 60 hours, meaning that the use of a catalyst gave a higher yield of sulfonate silyl ester.
These results show that in the reaction process of the present invention, by using an acidic compound as a catalyst, a sulfonic acid silyl ester can be produced efficiently in high yield.

In addition, the sulfonic acid silyl ester obtained in the reaction process can be easily converted into a silicon compound having a Si-C bond by using an appropriate carbon-based modifier, as shown in the following examples.

(Example 58)
0.43 mmol of phenylacetylene and 0.43 mmol of DBU were added to an acetonitrile reaction solution (about 0.3 mL) containing 0.24 mmol of trimethylsilyl trifluoromethanesulfonate obtained in Example 30 in Table 1, and the mixture was heated at 180° C. for 0.25 hours. The product was analyzed by GC, GC-MS, and NMR, and the product yield was measured by NMR, revealing that trimethyl(phenylethynyl)silane (PhC≡CSiMe ₃ ) was produced in a yield of 70% (see Table 2).

(Examples 59 to 68)
The reaction and analysis were carried out in the same manner as in Example 58, but the reaction conditions (raw materials, temperature, time, etc.) were changed. The product yields were measured by NMR, and the results are shown in Table 2.

The notes in Table 2 are as follows:
1) A reaction with a modifier was carried out using a reaction solution containing a sulfonate silyl ester obtained under the same reaction conditions as in the Examples in Table 1. The Example numbers in brackets indicate the Example numbers of the reaction conditions under which the sulfonate silyl ester was prepared.
2) PhC≡CH: Phenylacetylene
_CH2 = _CHCH2CN : Allyl cyanide
3) DBU: 1,8-diazabicyclo[5.4.0]-7-undecene
BTPP: tert-butyliminotri(pyrrolidino)phosphorane
_Et3N : Triethylamine
4) MeCN: Acetonitrile
DCB: 1,2-dichlorobenzene
_C6D6 : Heavy _benzene
5) 25°C indicates reactions at room temperature. For reactions at temperatures higher than room temperature, an oil bath (MH-5D, manufactured by Riko Kagaku Co., Ltd.) or a microwave heating device (Initiator, manufactured by Vitaage Co., Ltd.) was used. MW indicates heating by microwaves. All reactions were carried out in a sealed state.
6) _PhC≡CSiMe3 : Trimethyl(phenylethynyl)silane
_PhC≡CSiMe2 [( _CH2 ) _3CN ]: (3-cyanopropyl)dimethyl(phenylethynyl)silane
_PhC≡CSiMe2 (CH= _CH2 ): Dimethyl(phenylethynyl)(vinyl)silane
PhC≡CSiMe ₂ Ph: Dimethyl(phenyl)(phenylethynyl)silane
MeCH=C(CN)( _SiMe3 ): 2-trimethylsilyl-2-butenenitrile
_Me3SiCH2CH =C( _CN )( _SiMe3 ): 2,4-bis(trimethylsilyl)-2-butenenitrile
MeCH=C(CN){ _SiMe2 [( _CH2 ) _3CN ]}: 2-[(cyanopropyl)dimethylsilyl]-2-butenenitrile
{[NC( _CH2 ) ₃ ] _Me2Si } _CH2CH =C(CN){ _SiMe2 [( _CH2 ) _3CN ]}: 2,4-bis[(cyanopropyl)dimethylsilyl]-2-butenenitrile. The ratio of the modified compounds produced is shown in parentheses. The yield is the total yield.
7) Yield by NMR (yield based on sulfonic acid silyl ester)

The ²⁹ Si nuclear magnetic resonance spectrum ( ²⁹ Si NMR) and GC-MS data of the sulfonic acid silyl esters and their modified compounds obtained in the above examples are shown in Tables 3-1 and 3-2.

1) The names of each compound are listed in Table 1, Note 6 and Table 2, Note 6.
2) Chemical shift value of ^29Si NMR. _C6D6 was used as the _NMR solvent. Measured by adding the relaxation agent Cr(acac) ₃ (chromium(III) acetylacetonate). The value in parentheses indicates the ratio of the number of silicon atoms based on the integral ratio of the peak areas.
3) GC-MS: Gas chromatograph mass spectrometry, EI method: Electron impact ionization method (70 eV).
4) Chemical shift values of the reaction products of (SiMe ₂ O) _m (m=4, 5) with Tf ₂ O or (MeSO ₂ ) ₂ O (CD ₃ CN solvent).
5) The values in brackets are the chemical shifts of the reaction product of KF-968 and Tf ₂ O (C ₆ D ₆ solvent).

The manufacturing method of the present invention makes it possible to more efficiently and safely produce sulfonic acid silyl esters, which are useful as functional chemicals, and modified compounds having Si-C bonds obtained from them, making the present invention highly valuable and of great industrial significance.

Claims (11)

A method for producing a sulfonic acid silyl ester having an Si—O—SO ₂ bond, comprising a reaction step of reacting a siloxane compound having an Si—O—Si bond with a sulfonic acid anhydride in the presence of an acidic compound. The method for producing a sulfonic acid silyl ester according to claim 1, wherein the acidic compound is a compound selected from Lewis acid compounds containing elements of groups 3 to 15, sulfonic acid compounds, and solid acids. The method for producing a sulfonic acid silyl ester according to claim 2, wherein the acidic compound is a compound selected from Lewis acid compounds containing iron or indium, perfluoroalkanesulfonic acid, bis(perfluoroalkanesulfonyl)imide, montmorillonite, and zeolite. The method for producing a sulfonic acid silyl ester according to any one of claims 1 to 3, wherein the siloxane compound having a Si-O-Si bond is a siloxane compound represented by the following general formula (IA), (IB), or (IC):
R ¹ R ² R ³ Si-O-SiR ¹ R ² R ³ (IA)

X ¹ O(SiR ⁶ R ⁷ O) _n X ² (IC)
(In these formulas, R ¹ to R ⁷ are each independently a hydrocarbon group having 1 to 24 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction; X ¹ and X ² are each independently a silyl group or a hydrogen atom; m and n are each independently an integer of 2 or more and 10,000 or less; and when there are multiple R ¹ to R ⁷ in the same molecule, they may be the same or different.) The method for producing a sulfonic acid silyl ester according to any one of claims 1 to 4, wherein the sulfonic acid anhydride is a compound represented by the following general formula (II):
(R ⁸ SO ₂ ) ₂ O (II)
(In the formula, R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with groups that do not participate in the reaction.) The method for producing a sulfonic acid silyl ester according to any one of claims 1 to 5, wherein the reaction step is carried out under microwave irradiation. A method for producing a silicon compound having a Si-C bond, comprising: a sulfonate silyl ester production step of producing a sulfonate silyl ester by the production method according to any one of claims 1 to 6; and a modification step of reacting the produced sulfonate silyl ester with a modifying agent selected from an alkyne or an alkene. The method for producing a silicon compound according to claim 7, wherein the modifying agent is a compound selected from an alkyne represented by the following general formula (IVA) and an alkene represented by the following general formula (IVB1) or (IVB2).
R ⁹ C≡CH (IVA)
Z ¹ R ¹⁰ CHCH=CHR ¹¹ (IVB1)
Z ¹ R ¹⁰ C=CHCH ₂ R ¹¹ (IVB2)
(In these formulas, R ⁹ to R ¹¹ are each independently a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, and some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group may be substituted with a group that does not participate in the reaction; Z ¹ is a group selected from a cyano group, a nitro group, an acyl group, an amido group, an arylsulfonyl group, and an alkylsulfonyl group.) The method for producing a silicon compound according to claim 7 or 8, wherein the modification step is carried out in the presence of a basic compound. The method for producing a silicon compound according to claim 9, wherein the basic compound is a compound selected from an amine compound, an amidine compound, a guanidine compound, and a phosphazene compound. The method for producing a silicon compound according to any one of claims 7 to 10, wherein the modification step is carried out under microwave irradiation.