JP2022055604A - Method for producing sulfonic acid silyl ester and novel silicon compound - Google Patents

Abstract

To provide a method that can efficiently produce a sulfonic acid silyl ester, and a novel silicon compound.SOLUTION: A method for producing a sulfonic acid silyl ester having a Si-O-SO2 bond includes a reaction step for reacting an alkoxysilane having a Si-O-C bond with a sulfonic acid anhydride or a mixed acid anhydride of a sulfonic acid and a carboxylic acid. There is also provided a novel silicon compound. An example of the production method is illustrated by the following reaction scheme.SELECTED DRAWING: None

Description

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

Sulfonic acid silyl ester is a functional chemical used as a reagent for precision synthesis of pharmaceuticals, pesticides, electronic materials and the like, or a synthetic intermediate thereof.
Examples of the method for producing them include a method of reacting chlorosilane with a sulfonic acid or a silver salt of a sulfonic acid (Method A, Non-Patent Document 1), methylsilane (tetramethylsilane), allylsilane (allyltrimethylsilane) and the like. A method for reacting an acid (Method B, Non-Patent Documents 2 and 3), a method for reacting a sulfonic acid anhydride with disiloxane (hexamethyldisiloxane) (Method C, Non-Patent Document 4), and a silanol (trimethylsilanol). A method for reacting a sulfonic acid anhydride (Method D, Patent Document 1) and the like have been studied.

However, in the method using chlorosilane (method A), since chlorosilane that generates highly corrosive hydrogen chloride by hydrolysis is used, care must be taken in handling raw materials and designing equipment, and methylsilane, allylsilane, etc. are used. The method (method B) has problems such as that methylsilane, allylsilane and the like are expensive, and the type of sulfonic acid that reacts with methylsilane is limited to a strongly acidic sulfonic acid such as trifluoromethanesulfonic acid. Further, even in the methods using disiloxane and silanol (methods C and D), the types of easily available disiloxane and silanol are limited, and the type of easily reacting sulfonic acid anhydride is trifluoromethanesulfonic anhydride. There are problems such as being limited to trifluoromethanesulfonic acid having high reactivity. Further, the method using silanol (method D) has a problem that the stability of silanol is not high, and therefore care must be taken in handling. For these reasons, an industrially more advantageous method has been sought.

Chinese Patent Application 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 view of the above circumstances, and an object of the present invention is to provide an efficient method for producing a sulfonic acid silyl ester.

As a result of diligent research to solve the above problems, the present inventors have (1) that the easily available alkoxysilane reacts smoothly with the sulfonic acid anhydride and the like to efficiently give the sulfonic acid silyl ester. , (2) The produced sulfonic acid silyl ester reacts with a modifier such as alkyne or alkene to give a modified compound in which the Si—O _— SO2 bond of the sulfonic acid silyl ester is converted into a Si—C bond. (3) We have found that a novel silicon compound can be obtained by the reactions of (1) and (2), and have completed the present invention.

（式中、Ｒ^１１は、炭素数２～２４の２価の炭化水素基であり、前記２価の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。）
＜５＞
前記反応工程が、酸性化合物の存在下で行われる、＜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。
＜６＞
前記酸性化合物が、第３族～第１５族の元素を含むルイス酸化合物、およびスルホン酸
化合物から選ばれる化合物である、＜５＞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
前記スルホン酸シリルエステルに、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。
Ｒ^１２Ｃ≡ＣＨ （ＩＶＡ）
Ｚ^１Ｒ^１３ＣＨＣＨ＝ＣＨＲ^１４ （ＩＶＢ１）
Ｚ^１Ｒ^１３Ｃ＝ＣＨＣＨ_２Ｒ^１４ （ＩＶＢ２）
（これら式中、Ｒ^１２～Ｒ^１４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。）
＜８＞
前記修飾工程が、塩基性化合物の存在下で行われる、＜７＞に記載のケイ素化合物の製造方法。
＜９＞
前記塩基性化合物が、アミン化合物、アミジン化合物、およびグアニジン化合物から選ばれる化合物である、＜８＞に記載のケイ素化合物の製造方法。
＜１０＞
下記一般式（ＶＡ）、（ＶＢ）、（ＶＩ）、（ＶＩＩ）、または（ＶＩＩＩ）で表されるＳｉ－Ｃ結合を有するケイ素化合物。
Ｒ^１５ _ｅＲ^１６ _ｆＳｉ（ＯＲ^１７）_{４－（ｅ＋ｆ＋ｇ）}（ＯＳＯ_２Ｒ^１８）_ｇ （ＶＡ）Ｒ^１９ _ｈＲ^２０ _ｉ（Ｒ^２１Ｏ）_{３－（ｈ＋ｉ）}Ｓｉ－ＯＳＯ_２－（ｏ－Ｃ_６Ｈ_４）－ＣＯ_２Ｒ^２１ （ＶＢ）
Ｒ^２２ _ｊＲ^２３ _ｋＳｉ（ＯＲ^２４）_{４－（ｊ＋ｋ＋ｌ）}（Ｃ≡ＣＲ^２５）_ｌ （ＶＩ）
Ｒ^２６ _ｍＲ^２７ _ｎＳｉ（ＯＲ^２８）_{４－（ｍ＋ｎ＋ｏ）}［Ｃ（ＣＮ）＝ＣＨＲ^２９］_ｏ （ＶＩＩ）
Ｘ^７（ＳｉＲ^３０Ｒ^３１Ｏ）_ｑ－１ＳｉＲ^３０Ｒ^３１Ｘ^８ （ＶＩＩＩ）
（これら式中、Ｒ^１５、Ｒ^１６、Ｒ^１９、Ｒ^２０、Ｒ^２２、Ｒ^２３、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２９、Ｒ^３０、およびＲ^３１は、それぞれ独立にメチル基、フェニル基、およびビニル基より選ばれる基であり；Ｒ^１７、Ｒ^２１、Ｒ^２４、およびＲ^２８は、それぞれ独立にメチル基およびエチル基から選ばれる基であり；Ｒ^１８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；Ｘ^７およびＸ^８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^７およびＸ^８のうちの少なくとも一方は、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；ｅ、ｆ、ｈ、ｉ、ｊ、ｋ、ｍ、およびｎは、それぞれ独立に０以上２以下の整数であり；ｇおよびｌは、それぞれ独立に１または２であり；ｏは、１以上４以下の整数であり；ｅ＋ｆ＋ｇおよびｊ＋ｋ＋ｌは、それぞれ独立に２または３であり；ｈ＋ｉは、０以上３以下の整数であり；ｍ＋ｎ＋ｏは、１以上４以下の整数であり；ｑは、２以上６以下の整数である。） That is, this application provides the following inventions.
<1>
A sulfonic acid silyl ester having a Si—O _— SO2 bond, which comprises a reaction step of reacting an alkoxysilane having a Si—O—C bond with a sulfonic acid anhydride or a mixed acid anhydride of a sulfonic acid and a carboxylic acid. Manufacturing method.
<2>
The method for producing a sulfonic acid silyl ester according to <1>, wherein the alkoxysilane having a Si—OC bond is a compound represented by the following general formula (IA) or (IB).
R ¹ _a R ² _b R ³ _c Si (OR ⁴ ) _{4- (a + b + c)} (IA)
(In the equation, a, b, and c are each independently an integer of 0 or more and 3 or less; a + b + c is an integer of 0 or more and 3 or less; R ¹ , R ² , and R ³ are independent of each other. A hydrocarbon group or hydrogen atom having ¹ to 24 carbon atoms, and a part or all of the hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a group that does not participate in the reaction; It is an alkyl group having 1 to 6 carbon atoms.)
R ⁵ O (SiR ⁶ R ⁷ O) _p R ⁵ (IB)
(In the formula, p is an integer of 2 or more and 10000 or less; R ⁵ is an alkyl group having 1 to 6 carbon atoms; R ⁶ and R ⁷ are independently hydrocarbon groups having 1 to 24 carbon atoms, respectively. Alternatively, it is a hydrogen atom, and a part or all of the hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a group that does not participate in the reaction.)
<3>
The method for producing a sulfonic acid silyl ester according to <1> or <2>, wherein the sulfonic acid anhydride is a compound represented by the following general formula (IIA).
(R ⁸ SO ₂ ) ₂ O (IIA)
(In the formula, R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms, and a part 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. .)
<4>
The method for producing a sulfonic acid silyl ester according to <1> or <2>, wherein the mixed acid anhydride of the sulfonic acid and the carboxylic acid is a compound represented by the following general formula (IIB) or (IIC).
(R ⁹ SO ₂ ) O (COR ¹⁰ ) (IIB)
(In the formula, R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group do not participate in the reaction. It may be replaced.)

(In the formula, R ¹¹ is a divalent hydrocarbon group having 2 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the divalent hydrocarbon group does not participate in the reaction. It may be replaced.)
<5>
The method for producing a sulfonic acid silyl ester according to any one of <1> to <4>, wherein the reaction step is carried out in the presence of an acidic compound.
<6>
The method for producing a sulfonic acid silyl ester according to <5>, wherein the acidic compound is a compound selected from a Lewis acid compound containing elements of Groups 3 to 15 and a sulfonic acid compound.
<7>
The sulfonic acid silyl ester production step for producing a sulfonic acid silyl ester by the production method according to any one of <1> to <6>, and the sulfonic acid silyl ester to which an alkyne represented by the following general formula (IVA) is used. A method for producing a silicon compound having a Si—C bond, which comprises a modification step of reacting a modifier selected from an alkene represented by the following general formula (IVB1) or (IVB2).
R ¹² C≡CH (IVA)
Z ¹ R ¹³ CHCH = CHR ¹⁴ (IVB1)
Z ¹ R ¹³ C = CHCH ₂ R ¹⁴ (IVB2)
(In these formulas, R ¹² to R ¹⁴ are each independently a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group undergoes a reaction. It may be substituted with an uninvolved group; Z ¹ is a group selected from a cyano group, a nitro group, an acyl group, an amide group, an arylsulfonyl group, and an alkylsulfonyl group.)
<8>
The method for producing a silicon compound according to <7>, wherein the modification step is performed in the presence of a basic compound.
<9>
The method for producing a silicon compound according to <8>, wherein the basic compound is a compound selected from an amine compound, an amidine compound, and a guanidine compound.
<10>
A silicon compound having a Si—C bond represented by the following general formula (VA), (VB), (VI), (VII), or (VIII).
R ¹⁵ _e R ¹⁶ _f Si (OR ¹⁷ ) _{4- (e + f + g)} (OSO ₂ R ¹⁸ ) _g (VA) R ¹⁹ _h R ²⁰ _i (R ²¹ O) _{3- (h + i)} Si-OSO _2- (o-) C ₆ H ₄ ) -CO ₂ R ²¹ (VB)
R ²² _j R ²³ _k Si (OR ²⁴ ) _{4- (j + k + l)} (C≡CR ²⁵ ) _l (VI)
R ²⁶ _m R ²⁷ _n Si (OR ²⁸ ) _{4- (m + n + o)} [C (CN) = CHR ²⁹ ] _o (VII)
X ⁷ (SiR ³⁰ R ³¹ O) _q-1 SiR ³⁰ R ³¹ X ⁸ (VIII)
(In these formulas, R ¹⁵ , R ¹⁶ , R ¹⁹ , R ²⁰ , R ²² , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ , and R ³¹ , respectively, are independently methyl group and phenyl. A group selected from a group and a vinyl group; R ¹⁷ , R ²¹ , R ²⁴ , and R ²⁸ are groups independently selected from a methyl group and an ethyl group, respectively; R ¹⁸ is a trifluoromethyl group, A group selected from a methyl group and a p-tolyl group; X ⁷ and X ⁸ are independently trifluoromethanesulfonyloxy groups, methanesulfonyloxy groups, p-toluenesulfonyloxy groups, ethoxy groups, methoxy groups, phenyls, respectively. A group selected from an ethynyl group and a 1-cyano- ¹ -propenyl group, at least one of ^X7 and X8 is a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, phenyl. A group selected from an ethynyl group and a 1-cyano-1-propenyl group; e, f, h, i, j, k, m, and n are independently integers of 0 or more and 2 or less; g. And l are independently 1 or 2; o is an integer greater than or equal to 1 and 4 or less; e + f + g and j + k + l are independently 2 or 3; h + i is an integer greater than or equal to 0 and 3 or less. M + n + o is an integer of 1 or more and 4 or less; q is an integer of 2 or more and 6 or less.)

By using the production method of the present invention, there is an effect that a sulfonic acid silyl ester and a modified compound thereof can be efficiently produced, and a novel silicon compound can be provided.

In particular, a preferred embodiment of the production method of the present invention has the following characteristics.
(1) Raw materials are relatively easy to obtain, the reaction conditions are mild, and the reaction efficiency is high.
(2) Since the reaction is promoted by adding an acidic compound or water to the reaction system, the reaction of sulfonic acid anhydride or the like, which is not highly reactive, can be efficiently performed.
(3) Since the reaction proceeds stepwise, in a compound having a plurality of alkoxy groups, only one or two alkoxy groups can be selectively converted.
(4) Since the reaction step and the modification step can be continuously performed, the modifying compounds such as alkynylsilane and alkenylsilane can be produced by a simple one-pot step using alkoxysilane as a raw material.
(5) When a compound having a plurality of alkoxy groups such as tetraethoxysilane is used as a raw material, mono- and two-substituted alkynylsilanes, alkenylsilanes and the like can be selectively produced in a one-pot process.
(6) A novel functional silicon compound can be efficiently produced.
In a preferred embodiment of the production method of the present invention, an efficient production method of a sulfonic acid silyl ester and its modified compounds such as alkynylsilane and alkenylsilane is possible, and safety is improved as compared with the prior art. It has a great advantage in terms of economy and the like.

Hereinafter, the present invention will be described in detail. Unless otherwise specified, when a symbol in a certain formula in the present specification is also used in another formula, the same symbol has the same meaning.
The method for producing a sulfonic acid silyl ester according to an embodiment of the present invention is a reaction in which an alkoxysilane having a Si—OC bond is reacted with a sulfonic acid anhydride or a mixed acid anhydride of a sulfonic acid and a carboxylic acid. It is characterized by including a process.

In the present embodiment, the alkoxysilane used as a raw material is represented by, for example, the following general formula (IA) or (IB).

R ¹ _a R ² _b R ³ _c Si (OR ⁴ ) _{4- (a + b + c)} (IA)
In the general formula (IA), a, b, and c are independently integers of 0 or more and 3 or less, and a + b + c is an integer of 0 or more and 3 or less. Further, R ¹ , R ² and R ³ are each independently a hydrocarbon group or a hydrogen atom having 1 to 24 carbon atoms, and a part or all of the hydrogen atom bonded to the carbon atom of the hydrocarbon group reacts. It may be substituted with a group that does not participate in. ^R4 is an alkyl group having 1 to 6 carbon atoms. In addition, in this specification, "not involved in a reaction" means that it does not directly participate in a target reaction as a reactant and does not inhibit or promote the reaction.

R ⁵ O (SiR ⁶ R ⁷ O) _p R ⁵ (IB)
In the general formula (IB), p is an integer of 2 or more and 10000 or less. R5 is an alkyl group having 1 to ⁶ carbon atoms. Further, R ⁶ and R ⁷ are each independently a hydrocarbon group or a hydrogen atom having 1 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group do not participate in the reaction. It may be replaced with.

When R ¹ , R ² , R ³ , R ⁶ and R ⁷ are hydrocarbon groups having 1 to 24 carbon atoms in the general formulas (IA) and (IB), specific examples thereof include an alkyl group. , Aryl group, aralkyl group, alkenyl group and the like.

When the hydrocarbon group is an alkyl group, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 10, and particularly preferably 1 to 4. A part or all of the hydrogen atom bonded to the carbon atom of the alkyl group may be substituted with a group that does not participate in the reaction.

Groups that do not participate 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 and the like. Can be mentioned. More specifically, alkoxy groups, alkoxycarbonyl groups, dialkylamino groups, and halogen atoms are alkoxy groups such as methoxy groups, ethoxy groups, and hexoxy groups; alkoxycarbonyl groups such as methoxycarbonyl groups and propoxycarbonyl groups; dimethylamino. Dialkylamino groups such as groups and diethylamino groups; halogen atoms such as fluorine atoms, chlorine atoms and bromine atoms; can be mentioned.
Specific examples of the alkyl group that may be substituted with a group that 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, and 2 -Octyl group, decyl group, 2-methoxyethyl group, 3-ethoxypropyl group, 2-methoxycarbonylethyl group, 2-dimethylaminoethyl group, 2-cyanoethyl group, trifluoromethyl group, 3-chloropropyl group, 3 , 3,3-Trifluoropropyl group, 1H, 1H, 2H, 2H-tridecafluorooctyl group, 1H, 1H, 2H, 2H-heptadecafluorodecyl group and the like.

When the hydrocarbon group is an aryl group, a hydrocarbon ring system or a heterocyclic monovalent aromatic organic group can be used. When the aryl group is a hydrocarbon ring system, the monovalent aromatic organic group of the hydrocarbon ring system preferably has 6 to 22 carbon atoms, more preferably 6 to 14 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a peryleneyl group, a pentasenyl group and the like. When the aryl group is a heterocyclic system, the hetero atom in the hetero ring is sulfur, an oxygen atom, or the like. The number of carbon atoms of the monovalent aromatic organic group of the heterocyclic system is preferably 4 to 12, more preferably 4 to 8. Specific examples of the aryl group include a thienyl group, a benzothienyl group, a dibenzothienyl group, a frill group, a benzofuryl group, a dibenzofuryl group and the like.
A part or all of the hydrogen atom bonded to the carbon atom 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 above-mentioned alkyl group. In addition, examples of the group not involved in the reaction include an oxyethylene group and an oxyethyleneoxy group, which are divalent groups that bond two carbon atoms on the ring. Specific examples of the aryl group having these groups include a methylphenyl group, an ethylphenyl group, a hexylphenyl group, a methoxyphenyl group, an ethoxyphenyl group, a butoxyphenyl group, an octoxyphenyl group, and a methyl (methoxy) phenyl group. Fluoro (methyl) phenyl group, chloro (methoxy) phenyl group, bromo (methoxy) phenyl group, 2,3-dihydrobenzofuranyl group, 1,4-benzodioxanyl group and the like can be mentioned.

When the hydrocarbon group is an aralkyl group, the carbon number of the aralkyl group is preferably 7 to 23, more preferably 7 to 16. Further, a part or all of the hydrogen atom bonded to the carbon atom of the aralkyl 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 above-mentioned alkyl group.
Specific examples of the aralkyl group which may be substituted with a group not involved 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-chlorophenyl) methyl group. 4-Methylphenyl) ethyl group and the like can be mentioned.

Further, when the hydrocarbon group is an alkenyl group, the carbon number of 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. Is. Further, a part or all of the hydrogen atom bonded to the carbon atom of the alkenyl 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 for the above-mentioned alkyl group and the like, as well as the above-mentioned aryl group and the like.
Specific examples of the alkenyl group which may be substituted with a group not involved in the reaction include a vinyl group, a 2-propenyl group, a 3-butenyl group, a 5-hexenyl group, a 9-decenyl group and a 2-phenylethenyl group. Examples thereof include 2- (methoxyphenyl) ethenyl group, 2-naphthylethenyl group, 2-anthrylethenyl group and the like.

p is preferably 2 to 1000, and more preferably 2 to 100.

Therefore, specific examples of the alkoxysilanes of the general formula (IA) having those hydrocarbon groups include ethoxytrimethylsilane (Me ₃ SiOEt), methoxytrimethylsilane (Me ₃ SiOMe), and diethoxydimethylsilane (Me ₂ Si). (OEt) ₂ ), Methyldimethoxyphenylsilane (MePhSi (OME) ₂ ), Triethoxymethylsilane (MeSi (OEt) ₃ ), Triethoxyphenylsilane (PhSi (OEt) ₃ ), Triethoxyvinylsilane ((CH ₂ =) CH) Si (OEt) ₃ ), trimethoxyvinylsilane ((CH ₂ = CH) Si (OME) ₃ ), triethoxysilane (HSi (OEt) ₃ ), trimethoxysilane (HSi (OMe) ₃ ), tetraethoxy Examples thereof include silane (Si (OEt) ₄ ), tetramethoxysilane (Si (OMe) ₄ ), tetrapropoxysilane (Si (OPr) ₄ ), tetrabutoxysilane (Si (OBu) ₄ ) and the like.

Specific examples of the alkoxysilane of the general formula (IB) include 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane (EtO (SiMe ₂ O) ₂ Et) and 1,3-dimethoxy. -1,1,3,3-tetramethyldisiloxane (MeO (SiMe ₂ O) ₂ Me), 1,3-diethoxy-1,1,3,3-tetraphenyldisiloxane (EtO (SiPh ₂ O) ₂ ) Et), 1,5-diethoxy-1,1,3,3,5,5-hexamethyltrisiloxane (EtO (SiMe ₂ O) ₃ Et), 1,5-dimethoxy-1,1,3,3 5,5-Hexamethyldisiloxane (MeO (SiMe ₂ O) ₃ Me) and the like can be mentioned.

On the other hand, the sulfonic acid anhydride to be reacted with the alkoxysilane or the mixed acid anhydride of the sulfonic acid and the carboxylic acid is, for example, the following general formula (IIA), the following general formula (IIB), (IIC) or the like. expressed.

(R ⁸ SO ₂ ) ₂ O (IIA)
In the general formula (IIA), R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group are substituted with a group that does not participate in the reaction. May be.

(R ⁹ SO ₂ ) O (COR ¹⁰ ) (IIB)
In the general formula (IIB), R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group participate in the reaction. It may be substituted with a non-group.

In the general formula (IIC), R ¹¹ is a divalent hydrocarbon group having 2 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the divalent hydrocarbon group participate in the reaction. It may be substituted with a non-group.

Specific examples of the monovalent hydrocarbon group R ⁸ to R ¹⁰ include an alkyl group, an aryl group, an aralkyl group, an alkenyl group and the like. Examples of the group that does not participate in the reaction include those shown in the description of ^{R1 , R2} , and R3 of the above general formula (IA).
Regarding the number of carbon atoms of the hydrocarbon group, when the hydrocarbon group is an alkyl group, it is preferably 1 to 20, more preferably 1 to 18, and when the hydrocarbon group is an aryl group, it is preferably 4 to 4. 20, more preferably 4-18; preferably 5-21, more preferably 5-19 when the hydrocarbon group is an aralkyl group; preferably 5-19 when the hydrocarbon group is an alkenyl group. It is 2 to 20, more preferably 2 to 18.
Specific examples of the hydrocarbon group having 1 to 24 carbon atoms include those shown in the above general formulas (IA) and (IB) of R ¹ , R ² , R ³ , R ⁶ and R ⁷ . Can be mentioned.

On the other hand, specific examples of R ¹¹ which is a divalent hydrocarbon group include an arylene group, an alkylene group and the like, and examples of the group which does not participate in the reaction include R ¹ of the above general formulas (IA) and (IB). , R ² , R ³ , R ⁶ and those shown in the description of R ⁷ and the like can be mentioned.
The number of carbon atoms in the hydrocarbon group is preferably 6 to 20, more preferably 6 to 18 when the hydrocarbon group is an arylene group; preferably 2 to 2 when the hydrocarbon group is an alkylene group. 20, more preferably 2 to 10.
Specific examples of the divalent hydrocarbon group having 2 to 24 carbon atoms include a 1,2-phenylene group, an ethylene group, and a trimethylene group.

Therefore, regarding sulfonic acid anhydrides having those hydrocarbon groups, specific examples of the compound of the general formula (IIA) include trifluoromethanesulfonic anhydride (Tf ₂ O) and nonafluorobutane sulfonic acid anhydride ([CF). ₃ (CF ₂ ) ₃ SO ₂ ] O), p-toluenesulfonic anhydride ((p-TollSO ₂ ) ₂ O), methanesulfonic anhydride ((MeSO ₂ ) ₂ O) and the like can be mentioned.

Regarding the mixed acid anhydride of sulfonic acid and carboxylic acid, specific examples of the compound of the general formula (IIB) include trifluoroacetyl trifluoromethanesulfonic acid (TfOCOCF ₃ ), acetyl trifluoromethanesulfonic acid (TfOAc), and methane. Examples thereof include trifluoroacetyl sulfonate (MeSO ₃ COCF ₃ ), trifluoroacetyl p-toluene sulfonate (p-TolSO ₃ COCF ₃ ), and specific examples of the compound of the general formula (IIC) are 2-sulfobenzo. Acid Anhydrous ((1,2-C ₆ H ₄ ) (CO ₂ SO ₂ )), Tetrafluoro-2-Sulfonic Acid Anhydrous ((1, 2-C ₆ F ₄ ) (CO ₂ SO ₂ )) , Tetrachloro-2-sulfobenzoic acid anhydride ((1,2-C ₆ Cl ₄ ) (CO ₂ SO ₂ )) Tetrabromo-2-sulfobenzoic acid anhydride ((1,2-C ₆ Br ₄ )) ( CO ₂ SO ₂ )), tetraiodo-2-sulfobenzoic acid anhydride ((1,2-C ₆ I ₄ ) (CO ₂ SO ₂ )) and the like can be mentioned.

The molar ratio of the sulfonic acid anhydride or the mixed acid anhydride of the sulfonic acid and the carboxylic acid to the alkoxysilanes as a raw material can be arbitrarily selected, but if the yield of the sulfonic acid silyl ester to the alkoxysilane is taken into consideration. , Usually 0.4 or more and 300 or less, more preferably 0.5 or more and 200 or less, still more preferably 0.5 or more and 150 or less, and particularly preferably 0.5 or more and 5 or less.

In the reaction of the alkoxysilane of the general formula (IA) with the sulfonic acid anhydride of the general formula (IIA) or the mixed acid anhydride of the sulfonic acid and the carboxylic acid of the general formula (IIB), the general formula (IA) is used. ), A sulfonic acid silyl ester represented by the following general formula (IIIA) or (IIIB), in which a part or all of the alkoxy group (OR ⁴ ) is converted into a sulfonyloxy group (OSO ₂ R ⁸ or OSO ₂ R ⁹ ). Can be manufactured.

R ¹ _a R ² _b R ³ _c Si (OR ⁴ ) _{4- (a + b + c) -d} (OSO ₂ R ⁸ ) _d (IIIA)
R ¹ _a R ² _b R ³ _c Si (OR ⁴ ) _{4- (a + b + c) -e} (OSO ₂ R ⁹ ) _e (IIIB)
In these equations, a, b, c, a + b + c, and R ¹ to R ⁴ are synonymous with the above; d and e are each independently an integer of 1 or more and 4 or less; 4- (a + b + c) -d. , And 4- (a + b + c) -e are independently integers of 0 or more and 3 or less.

Further, in the reaction of the alkoxysilane of the general formula (IA) with the mixed acid anhydride of the sulfonic acid and the carboxylic acid of the general formula (IIC), the alkoxycarbonyl group-containing sulfonic acid represented by the following general formula (IIIC) Cyril esters can be provided.

R ¹ _a R ² _b R ³ _c (R ⁴ O) _{3- (a + b + c)} Si-OSO ₂ -R ¹¹ -CO ₂ R ⁴ (IIIC)
In the formula, a, b, c, a + b + c, R ¹ to R ⁴ , and R ¹¹ have the same meanings as described above.

Further, in the reaction between the alkoxysilane of the general formula (IB) and the sulfonic acid anhydride of the general formula (IIA), or the mixed acid anhydride of the sulfonic acid and the carboxylic acid of the general formula (IIB), the general formula is used. A sulfonic acid represented by the following general formula (IIID) or (IIIE) in which a part or all of the alkoxy group (OR ⁵ ) of (IB) is converted into a sulfonyloxy group (OSO ₂ R ⁸ or OSO ₂ R ⁹ ). Cyril ester can be produced.
X ¹ O (SiR ⁶ R ⁷ O) _p X ² (IIID)
X ³ O (SiR ⁶ R ⁷ O) _p X ⁴ (IIIE)
In these formulas, X ¹ and X ² are independently sulfonyl groups (SO ₂ R ⁸ ) or alkyl groups (R ⁵ ), respectively, and at least one of X ¹ and X ² is a sulfonyl group. Further, X ³ and X ⁴ are a sulfonyl group (SO ₂ R ⁹ ) or an alkyl group (R ⁵ ), and at least one of X ³ and X ⁴ is a sulfonyl group. p, R ⁵ , R ⁶ , R ⁷ and R ⁹ are synonymous with the above.

Further, in the reaction of the alkoxysilane of the general formula (IB) with the mixed acid anhydride of the sulfonic acid and the carboxylic acid of the general formula (IIC), a sulfonic acid silyl ester represented by the following general formula (IIIF) is produced. can.

X ⁵ O (SiR ⁶ R ⁷ O) _p X ⁶ (IIIF)
In the formula, X ⁵ and X ⁶ are independently alkoxycarbonyl group-containing sulfonyl groups (SO ₂ -R ¹¹ -CO ₂ R ⁵ ) or alkyl groups (R ⁵ ), respectively, and at least one of X ⁵ and X ⁶ . Is an alkoxycarbonyl group-containing sulfonyl group. p, R ⁵ , R ⁶ , R ⁷ and R ¹¹ have the same meanings as described above.

The reaction step in the present embodiment is a reaction step involving a nucleophilic substitution reaction with a sulfonic acid anhydride or a mixed acid anhydride of a sulfonic acid and a carboxylic acid with the raw material alkoxysilane.
Therefore, when the sulfonic acid anhydride represented by the general formula (IIA) or the mixed acid anhydride of the sulfonic acid and the carboxylic acid represented by the general formula (IIB) is used, the reaction in the present embodiment is carried out. , A reaction involving the desorption of a sulfonic acid ester or a carboxylic acid ester, and the reaction step can be expressed in the reaction of monoalkoxymonosilane, for example, as Scheme 1 or Scheme 2 below.

スキーム１

Scheme 1

スキーム２

Scheme 2

On the other hand, when a mixed acid anhydride of a cyclic sulfonic acid and a carboxylic acid represented by the general formula (IIC) is used, the mixed acid of the general formula (IIC) is used with respect to the Si—O bond of the alkoxysilane. The reaction is in the form of an anhydride inserted, and the reaction step can be expressed in the reaction of monoalkoxymonosilane, for example, as in Scheme 3 below.

スキーム３

Scheme 3

In these reactions, the number of alkoxy groups in the raw material alkoxysilane may be multiple, and the silanes produced by these reactions are those in which some or all of the alkoxy groups are converted into sulfonyloxy groups. ..
That is, the sulfonic acid silyl ester obtained in the reaction step in the present embodiment is not limited to one kind of compound, and when an alkoxysilane having a plurality of alkoxy groups is used as a raw material, one alkoxy group is used. It is possible to produce a plurality of converted silanes, which means that the sulfonic acid silyl ester provided in the production method according to the present embodiment may be a mixture thereof.

Since the conversion reaction of alkoxy groups in the reaction step proceeds stepwise in the case of monosilane, when monosilane having a plurality of alkoxy groups is used as a raw material, sulfonic acid anhydride or a mixed acid of sulfonic acid and carboxylic acid is used. By controlling the amount of anhydride used, it is possible to control the number of alkoxy groups to be converted.
For example, a reaction is carried out with monosilane having three or more alkoxy groups on a silicon atom by using about 1 equivalent or about 2 equivalents of a sulfonic acid anhydride or a mixed acid anhydride of a sulfonic acid and a carboxylic acid. Thereby, one or two alkoxy groups in the raw material can be selectively converted, respectively.
In such a selective conversion reaction, a mixed acid anhydride of a sulfonic acid and a carboxylic acid is more preferably used.

In the reaction step, various conventionally known homogeneous or heterogeneous acidic compounds can be used as catalysts in order to promote the reaction.
As a method for carrying out the reaction in the presence of an acidic compound, not only a method of adding the acidic compound to the reaction system but also a method of adding a small amount of water to the reaction system with the raw material sulfonic acid anhydride or sulfonic acid can be used. It is also possible to use a sulfonic acid produced by hydrolyzing a part of a mixed acid anhydride of a carboxylic acid as an acidic compound.

As the acidic compound which is a catalyst for accelerating the reaction, a compound selected from a Lewis acid compound containing Group 3 to Group 15 elements and a sulfonic acid compound is preferable.

The elements of Group 3 to Group 15 are preferably selected from Group 3, Group 8, Group 13 to Group 15, and more preferably Group 3, Group 8, Group 13, or Group 3. It is an element selected from Group 15, more preferably Group 8 or Group 13.

More specifically, these elements are preferably selected from scandium, ittrium, samarium, itribium, iron, ruthenium, copper, aluminum, gallium, indium, tin, or bismuth, and more preferably scandium, iron, It is an element selected from ruthenium, aluminum, gallium, indium, tin, or bismuth, and more preferably an element selected from iron, ruthenium, aluminum, gallium, or indium.

Examples of the Lewis acid compound containing these elements include halides, perchlorates, sulfonates, bis (perfluoroalkanesulfonyl) imide salts, hexafluoroantimonates, thiocyanates and the like containing these elements. Can be used.

Therefore, more specifically, examples of Lewis acid compounds include scandium chloride (III), titanium chloride (III), titanium chloride (IV), iron chloride (III), iron bromide (III), and ruthenium chloride (III). ), Aluminum chloride (III), Gallium chloride (III), Indium chloride (III), Tin chloride (IV), Iron perchlorate (III), Scandium trifluoromethanesulfonate (III), Ittribium trifluoromethanesulfonate (III) ), Iron trifluoromethanesulfonate (III), Copper trifluoromethanesulfonate (II), Aluminum trifluoromethanesulfonate (III), Gallium trifluoromethanesulfonate (III), Indium trifluoromethanesulfonate (III), Trifluoromethanesulfon Tin acid (IV), bismuth trifluoromethanesulfonate (IV), lanthanum trifluoromethanesulfonate (III), placeodium trifluoromethanesulfonate (IV), neodymium trifluoromethanesulfonate (IV), ittribium trifluoromethanesulfonate (IV) , Bis (trifluoromethanesulfonyl) imidescandium (III), bis (trifluoromethanesulfonyl) imidezinc (II), bis (trifluoromethanesulfonyl) imidedium (III), bis (trifluoromethanesulfonyl) imidestin (IV), hexafluoro Iron antimonate (I
II), indium hexafluoroantimonate (III), iron thiocyanate (III), indium thiocyanate (III) and the like can be mentioned.

As the acidic compound as a catalyst, a sulfonic acid compound is also preferably used.
Specific examples thereof include perfluoroalkanesulfonic acid, bis (perfluoroalcansulfonyl) imide, and more specifically, the sulfonic acid compound in the Lewis acid compound.

Further, as the catalyst, various conventionally known solid acid catalysts, which are easy to separate and recover, can also be used. As the solid acid catalyst, inorganic and organic catalysts can be used.
Examples of the inorganic solid acid catalyst include solid inorganic substances such as metal salts and metal oxides, and more specifically, protonic hydrogen atoms or metal atoms (aluminum, gallium, indium, tin, iron, titanium). , Scandium, cerium, etc.), zeolite, mesoporous silica, montmorillonite, etc., silica gel, heteropolyacid, and inorganic solid acid using a carbon-based material as a carrier.
Examples of the organic solid acid catalyst include various polymers, oligomers and the like having acidic functional groups such as a sulfo group and a carboxyl group, such as styrene gel and polytetrafluoroethylene.

The amount of catalyst for alkoxysilane can be arbitrarily determined, but in terms of molar ratio or weight ratio, it is usually about 0.0001 to 10, preferably about 0.001 to 8, more preferably about 0.001 to 6. More preferably, it is about 0.005 to 0.05.

In the present embodiment, the reaction in the reaction step can be carried out in a liquid phase or a gas phase state depending on the reaction temperature or the reaction pressure. Further, as the form of the reaction device, various conventionally known forms such as a batch type and a flow type can be used.
The reaction temperature is usually −20 ° C. or higher, preferably −10 to 300 ° C., more preferably −10 to 200 ° C., still 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.
Further, 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 and 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, and more. It is preferably about 0.1 to 14 hours.

When the reaction is carried out in a liquid phase system, a solvent may be used or a solvent-free system may be used. When a solvent is used, the solvent includes hydrocarbons such as decalin (decahydronaphthalene), decane, benzene and toluene, chloroform, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,3-. Hydrocarbons such as trichlorobenzene and 1,2,4-trichlorobenzene; nitriles such as acetonitrile and benzonitrile; ethers such as 1,4-dioxane, tert-butylmethyl ether and dibutyl ether; do not react with raw materials. Various solvents; etc. can be used, and two or more kinds can be mixed and used.
As the solvent, a deuterated solvent which is advantageous for analyzing the reaction product with a nuclear magnetic resonance apparatus can also be used, and for example, deuterated benzene, deuterated toluene, deuterated chloroform, deuterated acetonitrile and the like can be used.
Further, when the reaction is carried out in the gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen.

The reaction step proceeds even in a closed reaction device, but in the case of a reaction system involving desorption of a sulfonic acid ester or a carboxylic acid ester, the reaction device is set to an open system and their co-products are removed from the reaction system. The reaction can also proceed more efficiently by removing the ester continuously.

The reaction step of this embodiment can also be carried out under microwave irradiation. In this reaction system, the dielectric loss coefficient of the raw material sulfonic acid anhydride or the like is relatively large, and microwaves are efficiently absorbed. Therefore, the sulfonic acid anhydride or the like is activated under microwave irradiation, and the reaction is more efficient. Can be done.

In the microwave irradiation reaction, various commercially available devices equipped with contact type or non-contact type temperature sensors can be used. Further, the output of microwave irradiation, the type of cavity (multi-mode, single mode), the form of irradiation (continuous, intermittent) and the like can be arbitrarily determined according to the scale of the reaction, the type of reaction and the like. The frequency of the microwave is usually 0.3 to 30 GHz. Among them, the IMS frequency band assigned for use in the industrial field, the scientific field, the medical field and the like is preferable, and the 2.45 GHz band, the 5.8 GHz band and the like are more preferable.

Further, in the microwave irradiation reaction, in order to heat the reaction system more efficiently, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system. As the type of the heating material, various conventionally known materials such as activated carbon, graphite, silicon carbide, and titanium carbide can be used. Further, it is also possible to use a molding catalyst in which the above-mentioned catalyst and the powder of the heating material are mixed and fired using an appropriate binder such as sepiolite or formite.

Since the sulfonic acid silyl ester provided by the production method of the present embodiment generally has higher reactivity than the raw material alkoxysilanes, it is a reaction when used as a synthetic intermediate, a surface treatment agent, and a sol-gel material. The reaction and the like when used as a raw material can be carried out more efficiently under mild conditions than when the raw material alkoxysilanes are used.

Further, since the sulfonic acid silyl ester has high reactivity, the Si—O—SO ₂ bond of the sulfonic acid silyl ester can be easily converted to another bond by reacting with an appropriate modifier.
For example, when a carbon-based modifier is reacted, the Si—O _— SO2 bond of the sulfonic acid silyl ester is converted into a Si—C bond, and a silicon compound having a Si—C bond can be produced.

As such a carbon-based modifier, 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 ¹² C≡CH (IVA)
(Z ¹ CH ₂ ) R ¹³ C = CHR ¹⁴ (IVB 1)
Z ¹ HC = CR ¹³ (CH ₂ R ¹⁴ ) (IVB2)

In the formula, R ¹² to R ¹⁴ are each independently a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group do not participate in the reaction. It may be substituted with a group. Z ¹ is a group selected from a cyano group, a nitro group, an acyl group, an amide group, an arylsulfonyl group, and an alkylsulfonyl group, and is bonded to a carbon atom of the acyl group, the amide group, the arylsulfonyl group, and the alkylsulfonyl group. Some or all of the hydrogen atoms formed may be substituted with groups that do not participate in the reaction.

The hydrocarbon groups of R ¹² to R ¹⁴ and the groups not involved in the reaction are exemplified in the description of R ¹ , R ² , R ³ , R ⁶ and R ⁷ of the general formulas (IA) and (IB). And so on.
Specific examples of the acyl group include an acetyl group, a trifluoroacetyl group and the like; specific examples of the amide group include an acetamide group, a trifluoroacetamide group and the like; specific examples of the arylsulfonyl group include an arylsulfonyl group. , Phenylsulfonyl group and the like; specific examples of the alkylsulfonyl group include a methylsulfonyl group and the like.

Therefore, the alkynes represented by the general formula (IVA) include acetylene, 1-propyne, 1-butyne, 1-octyne, ethynylbenzene, 1-ethynylnaphthalene, 2-ethynylnaphthalene, 4-ethynylbiphenyl and 9-ethynylanthracene. And so on.
The alkenes represented by the general formula (IVB1) include allylcyanide, 3-methyl-3-butenenitrile, 3-pentenenitrile, 4-phenyl-3-butenenitrile, 3-nitro-1-propene, and methyl (2). -Propenyl) ketone, N, N-dimethyl-3-buteneamide, 3-phenylsulfonyl-1-propene, 3-methylsulfonyl-1-propene and the like can be mentioned.
Examples of the alkene represented by the general formula (IVB2) include 2-butenenitrile, 2-pentenenitrile, 4-phenyl-2-butenenitrile and the like.

When an alkyne represented by the general formula (IVA) is reacted with the sulfonic acid silyl ester obtained in the above reaction step, the alkyl or arylsulfonyl group of the sulfonic acid silyl ester is converted into an alkynyl group (R ¹² C≡C-). A converted compound or the like can be obtained.
When an alkene represented by the general formula (IVB1) or (IVB2) is reacted, an alkylsulfonyl group or an arylsulfonyl group of a sulfonic acid silyl ester is used as an alkenyl group ((R ¹⁴ CH ₂ ) R ¹³ C = CZ. A compound or the like converted to ^1- ) can be obtained.

This modification reaction is considered to be proceeding as shown in the following schemes 4 and 5.

スキーム４

Scheme 4

スキーム５

Scheme 5

In these reactions, when alkyne or alkene reacts with the sulfonic acid silyl ester, the sulfonic acid is desorbed to produce alkynylsilane or alkenylsilane, respectively.
In the reaction with an alkene, an isomerization reaction may occur due to the movement of a double bond so that conjugation with Z ¹ which is an electron-withdrawing group becomes advantageous, but if a base is present, the isomerization reaction may occur. It is considered that the isomerization reaction is particularly easy to proceed.

Further, when the alkene is reacted, the alkene of the general formula (IVB1) and the general formula (IVB2) can be mutually converted by the isomerization reaction by the transfer of the double bond as shown in Scheme 6, so whichever Reactions with alkenes of the same structure may also yield products of similar structure. In particular, when a base is present, the isomerization reaction is likely to occur, so that a product having a similar structure can be easily obtained.

スキーム６

Scheme 6

In the modification step, the reaction can be promoted by adding a basic compound having a property of capturing sulfonic acid.
As such a basic compound, for example, an amine compound, an amidine compound, a guanidine compound or the like can be used, and an organic or inorganic solid compound having a group derived from those 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 and N-methylpyrrolidin. , N-methylpiperidine and the like. 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. Will be. Specific examples of the guanidine compound include 1,5,7-triazabicyclo [4.4.0] -5-decene (TBD) and 7-methyl-1,5,7-triazabicyclo [4.4. 0] -5-Desen (MTBD) and the like can be mentioned.

The molar ratios of the carbon-based modifier and the basic compound to the sulfonic acid silyl ester can be arbitrarily selected, but considering the yield with respect to the sulfonic acid silyl ester, the sulfonyloxy group in the sulfonic acid silyl ester On the other hand, it is usually 0.4 molar equivalent or more and 100 molar equivalent or less, more preferably 0.5 molar equivalent or more and 50 molar equivalent or less, and further preferably 0.5 molar equivalent or more and 20 molar equivalent or less.

Further, the reaction in the modification step can be carried out in a liquid phase or a gas phase state depending on the reaction temperature or the reaction pressure. Further, as the form of the reaction device, various conventionally known forms such as a batch type and a flow type can be used.
The reaction temperature is usually −20 ° C. or higher, preferably −10 to 300 ° C., more preferably −10 to 200 ° C., still 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.
Further, 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 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 24 hours. It takes about 0.1 to 14 hours.

When the reaction is carried out in a liquid phase system, a solvent may be used or a solvent-free system may be used. When a solvent is used, examples of the solvent include a solvent that can be used in the reaction step. Two or more kinds of solvents can be mixed and used.
Further, when the reaction is carried out in the gas phase, the reaction can be carried out by mixing an inert gas such as nitrogen.

The modification step of the present embodiment can be carried out not only by purifying the sulfonic acid silyl ester produced in the reaction step, but also by using the unpurified sulfonic acid silyl ester obtained in the reaction step.
The method using an unpurified sulfonic acid silyl ester is a method in which a silicon compound can be obtained by a simple one-pot operation using alkoxysilane as a raw material, which is an advantageous embodiment showing the features of the present invention.

Further, purification of the sulfonic acid silyl ester produced in the reaction step and the silicon compound produced in the modification step can be easily achieved by means commonly used in organic chemistry such as distillation, recrystallization and chromatography.

When the sulfonic acid silyl ester is a sulfonic acid ester obtained by converting a part of the alkoxy group of an alkoxysilane having a plurality of alkoxy groups such as tetraalkoxysilane, the sulfonic acid silyl ester is used in the modification step. In some cases, a silicon compound is produced through the disproportionation reaction of.
For example, in the reaction of the modification step of the sulfonic acid silyl ester in which one alkoxy group in the tetraalkoxysilane is converted, not only the silanes having one Si—C bond but also the silanes having two of them are produced in a small amount. May be done.
The amount of these small amount products produced can be controlled by the type of basic compound used in the modification step. For example, when diisopropylmethylamine, dicyclohexylmethylamine, or the like, which are tertiary amines having a sterically relatively bulky secondary alkyl group, are used, the disproportionation of the sulfonic acid silyl ester in the modification step is suppressed. , The amount of small amount of product produced can be reduced.
That is, in the reaction of the modification step of the sulfonic acid silyl ester obtained by converting one alkoxy group in the tetraalkoxysilane, Si is used by using a tertiary amine having a secondary alkyl group such as diisopropylmethylamine and dicyclohexylmethylamine. It is possible to improve the selectivity and yield for a silicon compound having only one -C bond.

If an unreacted sulfonyloxy group remains in the modification step, another type of alkyne, alkene, or other modifying agent is further added to remove the remaining sulfonyloxy group. Another silicon compound converted to a substituent can also be obtained.
For example, when an alcohol such as ethanol or methanol is used as another modifier, a silicon compound obtained by converting the remaining sulfonyloxy group into an alkoxy group such as an ethoxy group or a methoxy group can be obtained.
When unreacted sulfonyloxy groups remain, sulfonyloxysilanes may react with each other to form a silicon compound with the formation of Si—O—Si bonds.

Specific examples of these silicon compounds include trimethyl (phenylethynyl) silane (PhC≡CSiMe ₃ ), dimethylbis (phenylethynyl) silane ((PhC≡C) ₂ SiMe ₂ ), and methylmethoxyphenyl (phenylethynyl) silane. (PhC≡CSiMePh (OMe)), Methylphenylbis (phenylethynyl) silane ((PhC≡C) ₂
SiMePh), diethoxyphenyl (phenylethynyl) silane (PhC≡CSiPh (OEt) ₂ ), diethoxy (phenylethynyl) vinylsilane (PhC≡CSi (CH = CH ₂ ) (OEt) ₂ :), ethoxybis (phenylethynyl) vinylsilane ((PhC≡C) ₂ Si (CH = CH ₂ ) (OEt)), Triethoxy (phenylethynyl) silane (PhC≡CSi (OEt) ₃ ), Diethoxybis (phenylethynyl) silane ((PhC≡C) 2 Si ((PhC≡C) ₂ Si ( OEt) ₂ ), Trimethoxy (Phenylethynyl) Silane (PhC≡CSi (OMe) ₃ ), Dimethoxybis (Phenylethynyl) Silane ((PhC≡C) ₂ Si (OMe) ₂ ), 1,1,3,3- Tetramethyl-1-phenylethynyldisiloxane-3-trifurate (PhC≡C (SiMe ₂ O) ₂ Tf), 1,3-bis (phenylethynyl) -1,1,3,3-tetramethyldisiloxane ((() PhC≡CSiMe ₂ ) ₂ O), 1,7-bis (phenylethynyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane ((PhC≡CSMe2 _{OSiMe 2) 2 O )} ), 1-ethoxy-1,1,3,3-tetramethyl-3-phenylethynyldisiloxane (PhC≡C (SiMe ₂ O) ₂ Et), 2-trimethylsilyl-2-butenenitrile (MeCH = C (CN)) ) (SiMe ₃ )), 2,4-bis (trimethylsilyl) -2-butenenitrile (Me ₃ SiCH ₂ CH = C (CN) (SiMe ₃ )), (1-cyano-1-propenyl) ethoxydimethylsilane ( [MeCH = C (CN)] SiMe ₂ (OEt)), bis (1-cyano-1-propenyl) dimethylsilane ([MeCH = C (CN)] ₂ SiMe ₂ ), (1-cyano-1-propenyl) Methylmethoxyphenylsilane ([MeCH = C (CN)] SiMePh (OMe)), (1-cyano-1-propenyl) diethoxyphenylsilane ([MeCH = C (CN)] SiPh (OEt) ₂ ), bis ( 1-Cyano-1-propenyl) ethoxyphenylsilane ([MeCH = C (CN)] ₂ SiPh (OEt)), (1-cyano-1-propenyl) diethoxyvinylsilane ([MeCH = C (CN)] Si ( CH = CH ₂ ) (OEt) ₂ ), screw ( 1-cyano-1-propenyl) ethoxyvinylsilane ([MeCH = C (CN)] ₂ Si (CH = CH ₂ ) (OEt)), (1-cyano-1-propenyl) triethoxysilane ([MeCH = C (] CN)] Si (OEt) ₃ ), bis (1-cyano-1-propenyl) diethoxysilane ([MeCH = C (CN)] ₂ Si (OEt) ₂ ), (1-cyano-1-propenyl) tri Methoxysilane ([MeCH = C (CN)] Si (OMe) ₃ ), bis (1-cyano-1-propenyl) dimethoxysilane ([MeCH = C (CN)] ₂ Si (OMe) ₂ ), 1-( 1-cyano-1-propenyl) -1,1,3,3-tetramethyldisiloxane-3-triflate ([MeCH = C (CN)] ( _{SiMe2O) 2 Tf} ), 1,3-bis (1) -Cyano-1-propenyl) -1,1,3,3-tetramethyldisiloxane ({[MeCH = C (CN)] SiMe2 _{} 2O} ), 1- (1-cyano-1-propenyl) -3 -Ethoxy-1,1,3,3-tetramethyldisiloxane ([MeCH = C (CN)] (SiMe ₂ O) ₂ Et) and the like can be mentioned.

Further, the reaction of the reaction step and the modification step described above can provide a novel silicon compound represented by the following general formula (VA), (VB), (VI), (VII), or (VIII).
R ¹⁵ _e R ¹⁶ _f Si (OR ¹⁷ ) _{4- (e + f + g)} (OSO ₂ R ¹⁸ ) _g (VA) R ¹⁹ _h R ²⁰ _i (R ²¹ O) _{3- (h + i)} Si-OSO _2- (o-) C ₆ H ₄ ) -CO ₂ R ²¹ (VB)
R ²² _j R ²³ _k Si (OR ²⁴ ) _{4- (j + k + l)} (C≡CR ²⁵ ) _l (VI)
R ²⁶ _m R ²⁷ _n Si (OR ²⁸ ) _{4- (m + n + o)} [C (CN) = CHR ²⁹ ] _o (VII)
X ⁷ (SiR ³⁰ R ³¹ O) _q-1 SiR ³⁰ R ³¹ X ⁸ (VIII)

In these formulas, R ¹⁵ , R ¹⁶ , R ¹⁹ , R ²⁰ , R ²² , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ , and R ³¹ are independently methyl and phenyl groups, respectively. , And a group selected from vinyl groups; R ¹⁷ , R ²¹ , R ²⁴ , and R ²⁸ are groups independently selected from methyl and ethyl groups, respectively; R ¹⁸ is a trifluoromethyl group, methyl. A group selected from a group and a p-tolyl group.
Further, X ⁷ and X ⁸ are independently composed of 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, respectively. The group of choice, at least one of X ⁷ and X ⁸ , is from a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, a phenylethynyl group, and a 1-cyano-1-propenyl group. It is the base of choice.
Further, e, f, h, i, j, k, m, and n are independently integers of 0 or more and 2 or less; g and l are independently 1 or 2, respectively; o is 1. An integer of 4 or more; e + f + g and j + k + l are independently 2 or 3, respectively; h + i is an integer of 0 or more and 3 or less; m + n + o is an integer of 1 or more and 4 or less; q is 2 It is an integer of 6 or more.

In the general formula (VA), (methyl group,-, ethyl group, trifluoromethyl group, 2,0) are preferable examples of the combination of (R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , e, f, g). 1, (Methyl group, phenyl group, methyl group, trifluoromethyl group, 1, 1, 1), (methyl group,-, ethyl group, trifluoromethyl group, 1, 0, 1), (phenyl group) ,-, Ethyl group, trifluoromethyl group, 1,0,1), (phenyl group,-, ethyl group, trifluoromethyl group, 1,0,2), (vinyl group,-, ethyl group, trifluoro Methyl group, 1,0,1), (vinyl group,-, ethyl group, trifluoromethyl group, 1,0,2), (-,-, ethyl group, trifluoromethyl group, 0,0,2) , (-,-, Methyl group, trifluoromethyl group, 0, 0, 2) and the like.
In the general formula (VB), preferred examples of the combination of (R ¹⁹ , R ²⁰ , R ²¹ , h, i) include (methyl group, methyl group, methyl group 2, 1) and the like.

In the general formula (VI), as a preferable example of the combination of (R ²² , R ²³ , R ²⁴ , R ²⁵ , j, k, l), (methyl group, phenyl group, methyl group, phenyl group, 1, 1, 1, 1), (Phenyl group,-, Ethyl group, Phenyl group, 1,0,1), (Vinyl group,-, Ethyl group, Phenyl group, 1,0,1), (Vinyl group,-, Ethyl group, Phenyl group, 1, 0, 2) and the like can be mentioned.

In the general formula (VII), (methyl group,-, ethyl group, methyl group, 2, 0, 1) are preferred examples of the combination of (R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , m, n, o). ), (Methyl group,-,-, Methyl group, 2,0,2), (Methyl group, phenyl group, Methyl group, Methyl group, 1,1,1), (Phenyl group,-, Ethyl group, Methyl) Group 1,0,1), (phenyl group,-, ethyl group, methyl group, 1,0,2), (vinyl group,-, ethyl group, methyl group, 1,0,1), (vinyl group) ,-, Ethyl group, methyl group, 1,0,2), (phenyl group,-, ethyl group, methyl group, 1,0,1), (-,-, ethyl group, methyl group, 0,0, 1), (-,-, ethyl group, methyl group, 0, 0, 2), (-,-, methyl group, methyl group, 0, 0, 1), (-,-, methyl group, methyl group, 0, 0, 2) and the like can be mentioned.

In the general formula (VIII), (methyl group, methyl group, trifluoromethanesulfonyloxy group, trifluoromethanesulfonyloxy group, 2) are preferred examples of the combination of (R ³⁰ , R ³¹ , X ⁷ , X ⁸ , q). , (Methyl group, methyl group, phenylethynyl group, trifluoromethanesulfonyloxy group, 2), (methyl group, methyl group, phenylethynyl group, ethoxy group, 2), (methyl group, methyl group, phenylethynyl group, phenyl) Ethynyl group, 4), (methyl group, methyl group, 1-cyano-1-propenyl group, trifluoromethanesulfonyloxy group, 2), (methyl group, methyl group, 1-cyano-1-propenyl group, ethyl group, 2), (methyl group, methyl group, 1-cyano-1-propenyl group, 1-cyano-1-propenyl group, 2) and the like can be mentioned.

Since these silicon compounds have reactive groups such as trifluoromethanesulfonyloxy group, ethoxy group and functional groups such as alkynyl group and alkenyl group, they have useful functions as synthetic intermediates, surface treatment agents and the like. It can be used as a sex silicon compound.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to those Examples.
The main analyzers and the like used in the following examples are as follows.
-Nuclear magnetic resonance spectrum analysis (hereinafter sometimes referred to as NMR): Bruker's AVANCE III HD 600 MHz (with cryoprobe attached)
-Gas chromatograph analysis (hereinafter sometimes referred to as GC): GC-2014 manufactured by Shimadzu Corporation
-Gas chromatograph mass spectrometry (hereinafter, may be referred to as GC-MS): GCMS-QP2010Plus manufactured by Shimadzu Corporation.

(Example 1)
1.16 mmol of ethoxytrimethylsilane (Me ₃ SiOEt) and 1.22 mmol of trifluoromethanesulfonic anhydride (Tf ₂ O) were placed in a reaction vessel and stirred at about 25 ° C. (room temperature) for 0.25 hours. As a result of analyzing the product by NMR and measuring the yield of the product by NMR, it was found that trimethylsilyl trifluoromethanesulfonate (Me ₃ SiOTf) was produced in a yield of ≧ 95% (see Table 1-1). ).

(Examples 2 to 46)
The reaction and analysis were carried out in the same manner as in Example 1 by changing the reaction conditions (catalyst, raw material, temperature, time, etc.), and the yield of the product was measured by GC or nuclear magnetic resonance spectrum analysis. -Shown in Table 1-4 (sometimes referred to simply as "Table 1").

The notes in Table 1 are shown below.
1) Me _3SiOEt : ethoxytrimethylsilane
Me _3SiOMe : Methoxytrimethylsilane
Me ₂ Si (OEt) ₂ : Diethoxydimethylsilane
MePhSi (OMe) ₂ : Methyldimethoxyphenylsilane
MeSi (OEt) ₃ : Triethoxymethylsilane
PhSi (OEt) ₃ : Triethoxyphenylsilane
(CH ₂ = CH) Si (OEt) ₃ : Triethoxyvinylsilane
Si (OEt) ₄ : Tetraethoxysilane
Si (OMe) ₄ : Tetramethoxysilane
EtO (SiMe ₂ O) ₂ Et: 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane
2) Tf ₂ O: Trifluoromethanesulfonic anhydride
(p-TolSO ₂ ) ₂ O: p-toluenesulfonic acid anhydride
(MeSO ₂ ) ₂ O: Methanesulfonic acid anhydride
TfOCOCF ₃ : Trifluoromethanesulfonic acid trifluoroacetyl
(1,2-C ₆ H ₄ ) (CO ₂ SO ₂ ): 2-Sulfonzoic anhydride
3) FeCl ₃ : Iron (III) chloride
Fe (ClO ₄ ) _{3.6H 2} O: Iron perchlorate (III) hexahydrate
In (NTf ₂ ) ₃ : Bis (trifluoromethanesulfonyl) imide indium (III)
TfOH: Trifluoromethanesulfonic acid
H ₂ O: Water
4) DCB: 1,2-dichlorobenzene
MeCN: acetonitrile
PhMe: Toluene
C ₆ D ₆ : Heavy benzene

5) At 25 ° C, the reaction at room temperature is shown. For the reaction at a temperature higher than room temperature, an oil bath (MH-5D manufactured by Riko Kagaku Co., Ltd.) was used.
6) Me _3SiOTf : Trimethylsilyl trifluoromethanesulfonate
Me _{3SiOSO 2} -p-Tol: trimethylsilyl p-toluenesulfonic acid
Me _{3SiOSO 2} Me: Trimethylsilyl Methanesulfonic Acid
1-MeOCO-2- (Me _{3SiOSO 2} ) C ₆ H ₄ : 1-Methoxycarbonyl-2- (trimethylsiloxysulfonyl) benzene
Me ₂ Si (OEt) (OTf): ethoxydimethylsilyl triflate
Me ₂ Si (OTf) ₂ : Dimethylsilyl bistriflate
MePhSi (OMe) (OTf): Methylmethoxyphenylsilyltriflate
MePhSi (OTf) ₂ : Methylphenylsilylbistriflate
MeSi (OEt) ₂ (OTf): Diethoxymethylsilyltriflate
PhSi (OEt) ₂ (OTf): Diethoxyphenylsilyl triflate
PhSi (OEt) (OTf) ₂ : ethoxyphenylsilyl bistriflate
(CH ₂ = CH) Si (OEt) ₂ (OTf): Diethoxyvinylsilyl triflate
(CH ₂ = CH) Si (OEt) (OTf) ₂ : ethoxyvinylsilyl bistriflate
Si (OEt) ₃ (OTf): Triethoxysilyl triflate
Si (OEt) ₂ (OTf) ₂ : Diethoxysilyl bistriflate
Si (OMe) ₃ (OTf): Trimethoxysilyl triflate
Si (OMe) ₂ (OTf) ₂ : Dimethoxysilyl bistriflate
TfO (SiMe ₂ O) ₂ Tf: 1,1,3,3-tetramethyldisiloxane-1,3-bistriflate The numbers in parentheses indicate the ratio of the produced sulfonic acid silyl ester. Yields also indicate their total yield.
7) Yield by NMR (yield of sulfonic acid silyl ester with respect to alkoxysilane).

In the production method of the present invention, the reaction proceeds efficiently even at a low temperature by using a catalyst.
For example, in the reaction of ethoxytrimethylsilane with p-toluenesulfonic acid anhydride, in the absence of a catalyst, as shown in Example 2 of Table 1, at 90 ° C. for 0.25 hours, the sulfonic acid silyl ester The yield was 47%. On the other hand, in the method using a catalyst, as shown in Examples 4 to 8, the yields of the sulfonic acid silyl esters are all 90% or more under the conditions of 90 ° C. and 0.25 hours, and no catalyst is used. It was found that the yield was higher than that of.
These results indicate that the sulfonic acid silyl ester can be produced more efficiently by adding a catalyst in the reaction step.

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

(Example 47)
To the reaction solution containing 0.6 mmol of trimethylsilyl trifluoromethanesulfonate obtained in Example 15 of Table 1, 0.9 mmol of phenylacetylene and 3 mmol of triethylamine were added, and the mixture was heated at 120 ° C. for 0.5 hour. The product was analyzed by GC, GC-MS, and NMR, and the yield of the product was measured by NMR. As a result, trimethyl (phenylethynyl) silane (PhC≡CSiMe ₃ ) was produced in a yield of 80%. Was found (see Table 2-1).

(Examples 48 to 106)
The reaction and analysis were carried out in the same manner as in Example 47 by changing the reaction conditions (raw materials, temperature, time, etc.), and the results of measuring the yield of the product by NMR are shown in Tables 2-1 to 2-7 (simply "". It may be referred to as "Table 2").

1) A reaction with a modifier was carried out using a reaction solution containing a sulfonic acid silyl ester obtained under the same reaction conditions as in the examples in Table 1. The example numbers in square brackets indicate the example numbers of the reaction conditions for which the sulfonic acid silyl ester was prepared.
2) PhC≡CH: Phenylacetylene
CH ₂ = CHCH ₂ CN: Allyl cyanide
EtOH: Ethanol
3) Et ₃ N: Triethylamine
ⁱ Pr ₂ NMe: Diisopropylmethylamine
cyc-Hex ₂ NMe: Dicyclohexylmethylamine
ⁱ Pr ₂ NEt: diisopropylethylamine
Me ₅ NC ₅ H ₆ : 1,2,2,6,6-pentamethylpiperidine
Bu ₃ N: Tributylamine
Hex ₃ N: Trihexylamine
Oct ₃ N: Trioctylamine
MeN (CH ₂ ) ₄ : N-methylpyrrolidin
MeN (CH ₂ ) ₅ : N-methylpiperidine
4) PhMe: Toluene
CHCl ₃ : Chloroform
Dioxane: 1,4-dioxane
C ₆ D ₆ : Heavy benzene
DCB: 1,2-dichlorobenzene
5) At 25 ° C, the reaction at room temperature is shown.

6) PhC≡CSiMe ₃ : trimethyl (phenylethynyl) silane
(PhC≡C) ₂ SiMe ₂ : Dimethylbis (phenylethynyl) silane
PhC≡CSiMePh (OMe): Methylmethoxyphenyl (phenylethynyl) silane
(PhC≡C) ₂ SiMePh: Methylphenylbis (phenylethynyl) silane
PhC≡CSiPh (OEt) ₂ : Diethoxyphenyl (phenylethynyl) silane
PhC≡CSi (CH = CH ₂ ) (OEt) ₂ : Diethoxy (phenylethynyl) vinylsilane
(PhC≡C) ₂ Si (CH = CH ₂ ) (OEt): ethoxybis (phenylethynyl) vinylsilane
PhC≡CSi (OEt) ₃ : Triethoxy (phenylethynyl) silane
(PhC≡C) ₂ Si (OEt) ₂ : Diethoxybis (phenylethynyl) silane
PhC≡CSi (OMe) ₃ : Trimethoxy (phenylethynyl) silane
(PhC≡C) ₂ Si (OMe) ₂ : Dimethoxybis (phenylethynyl) silane
PhC≡C (SiMe ₂ O) ₂ Tf: 1,1,3,3-tetramethyl-1-phenylethynyldisiloxane-3-triflate
(PhC≡CSiMe ₂ ) ₂ O: 1,3-bis (phenylethynyl) -1,1,3,3-tetramethyldisiloxane
(PhC≡CSiMe ₂ OSiMe ₂ ) ₂ O: 1,7-bis (phenylethynyl) -1,1,3,3,5,5,7,7-octamethyltetrasiloxane
PhC≡C (SiMe ₂ O) ₂ Et: 1-ethoxy-1,1,3,3-tetramethyl-3-phenylethynyldisiloxane
MeCH = C (CN) (SiMe ₃ ): 2-trimethylsilyl-2-butenenitrile
Me ₃ SiCH ₂ CH = C (CN) (SiMe ₃ ): 2,4-bis (trimethylsilyl) -2-butenenitrile
[MeCH = C (CN)] SiMe ₂ (OEt): (1-cyano-1-propenyl) ethoxydimethylsilane
[MeCH = C (CN)] ₂ SiMe ₂ : Bis (1-cyano-1-propenyl) dimethylsilane
[MeCH = C (CN)] SiMePh (OMe): (1-cyano-1-propenyl) Methylmethoxyphenylsilane
[MeCH = C (CN)] SiPh (OEt) ₂ : (1-cyano-1-propenyl) diethoxyphenylsilane
[MeCH = C (CN)] ₂ SiPh (OEt): Bis (1-cyano-1-propenyl) ethoxyphenylsilane
[MeCH = C (CN)] Si (CH = CH ₂ ) (OEt) ₂ : (1-cyano-1-propenyl) diethoxyvinylsilane
[MeCH = C (CN)] ₂ Si (CH = CH ₂ ) (OEt): Bis (1-cyano-1-propenyl) ethoxyvinylsilane
[MeCH = C (CN)] Si (OEt) ₃ : (1-cyano-1-propenyl) triethoxysilane
[MeCH = C (CN)] ₂ Si (OEt) ₂ : Bis (1-cyano-1-propenyl) diethoxysilane
[MeCH = C (CN)] Si (OMe) ₃ : (1-cyano-1-propenyl) Trimethoxysilane
[MeCH = C (CN)] ₂ Si (OMe) ₂ : Bis (1-cyano-1-propenyl) dimethoxysilane
[MeCH = C (CN)] (SiMe ₂ O) ₂ Tf: 1- (1-cyano-1-propenyl) -1,1,3,3-tetramethyldisiloxane-3-triflate
{[MeCH = C (CN)] SiMe ₂ } ₂ O: 1,3-bis (1-cyano-1-propenyl) -1,1,3,3-tetramethyldisiloxane
[MeCH = C (CN)] (SiMe ₂ O) ₂ Et: 1- (1-cyano-1-propenyl) -3-ethoxy-1,1,3,3-tetramethyldisiloxane The ratio of the silicon compound produced is shown. Yields also indicate their total yield.

7) Yield by NMR (yield for sulfonic acid silyl ester).
8) It is considered that two types of isomers (A and B) are present in PhC≡C (SiMe ₂ O) ₂ Tf (see Table 3, footnote 4). In the long-term reaction, (PhC≡CSiMe ₂ OSiMe ₂ ) ₂ O was generated, which is considered to be due to the dimerization of (PhC≡CSiMe ₂ ) ₂ O and PhC≡C (SiMe ₂ O) ₂ Tf. The numbers in parentheses show the ratio of these two isomers to a total of four compounds including (PhC≡CSiMe ₂ ) ₂ O and (PhC≡CSiMe ₂ OSiMe ₂ ) O.
9) After adding the first modifier (alkyne or alkene), the second modifier (alcohol) was added to convert the remaining sulfonyloxy groups to alkoxy groups.

The ²⁹ Si nuclear magnetic resonance spectra ( ²⁹ Si NMR) and GC-MS data of the sulfonic acid silyl esters and their silicon compounds obtained in the above examples are shown in Tables 3-1 to 3-3 (simply "Table 3"). It may be called.).

The notes in Table 3 are shown below.
1) The names of each compound are shown in Table 1 Footnote 6 and Table 2 Footnote 6.
2) ²⁹ Si NMR chemical shift value. C ₆ D ₆ is used as the NMR solvent. Measured by adding the relaxation reagent Cr (acac) ₃ (chromium (III) acetylacetonate).
3) GC-MS: Gas chromatograph mass spectrometry, EI method: Electron impact ionization method (70eV).
4) The monoalkynylated product (PhC≡C (SiMe ₂ O) ₂ Tf) having a TfO group has five SO ₂ oxygen atoms with respect to the terminal Si in the Si-O-Si-O-SO ₂ skeleton. It is possible that two types of isomers (A, B) with different steric positions of the alkynyl group are generated due to the positional interaction to form a 6-membered cyclic structure. In the monoalkynylated compound (PhC≡C (SiMe ₂ O) ₂ Et) in which the TfO group is converted to the EtO group by adding ethanol, one type is eliminated because the steric isomer due to such a 6-membered cyclic structure disappears. It is presumed that it became a compound of.

The production method of the present invention makes it possible to more efficiently and safely provide a sulfonic acid silyl ester useful as a functional chemical and a silicon compound having a Si—C bond obtained from the sulfonic acid silyl ester, and thus the utility value of the present invention. Is high, and its industrial significance is great.

Claims (10)

A sulfonic acid silyl ester having a Si—O _— SO2 bond, which comprises a reaction step of reacting an alkoxysilane having a Si—O—C bond with a sulfonic acid anhydride or a mixed acid anhydride of a sulfonic acid and a carboxylic acid. Manufacturing method. The method for producing a sulfonic acid silyl ester according to claim 1, wherein the alkoxysilane having a Si—OC bond is a compound represented by the following general formula (IA) or (IB).
R ¹ _a R ² _b R ³ _c Si (OR ⁴ ) _{4- (a + b + c)} (IA)
(In the equation, a, b, and c are each independently an integer of 0 or more and 3 or less; a + b + c is an integer of 0 or more and 3 or less; R ¹ , R ² , and R ³ are independent of each other. A hydrocarbon group or hydrogen atom having ¹ to 24 carbon atoms, and a part or all of the hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a group that does not participate in the reaction; It is an alkyl group having 1 to 6 carbon atoms.)
R ⁵ O (SiR ⁶ R ⁷ O) _p R ⁵ (IB)
(In the formula, p is an integer of 2 or more and 10000 or less; R ⁵ is an alkyl group having 1 to 6 carbon atoms; R ⁶ and R ⁷ are independently hydrocarbon groups having 1 to 24 carbon atoms, respectively. Alternatively, it is a hydrogen atom, and a part or all of the hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a group that does not participate in the reaction.) The method for producing a sulfonic acid silyl ester according to claim 1 or 2, wherein the sulfonic acid anhydride is a compound represented by the following general formula (IIA).
(R ⁸ SO ₂ ) ₂ O (IIA)
(In the formula, R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms, and a part 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. .) The method for producing a sulfonic acid silyl ester according to claim 1 or 2, wherein the mixed acid anhydride of the sulfonic acid and the carboxylic acid is a compound represented by the following general formula (IIB) or (IIC).
(R ⁹ SO ₂ ) O (COR ¹⁰ ) (IIB)
(In the formula, R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 1 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group do not participate in the reaction. It may be replaced.)

(In the formula, R ¹¹ is a divalent hydrocarbon group having 2 to 24 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the divalent hydrocarbon group does not participate in the reaction. It may be replaced.) The method for producing a sulfonic acid silyl ester according to any one of claims 1 to 4, wherein the reaction step is carried out in the presence of an acidic compound. The method for producing a sulfonic acid silyl ester according to claim 5, wherein the acidic compound is a compound selected from a Lewis acid compound containing elements of Groups 3 to 15 and a sulfonic acid compound. A sulfonic acid silyl ester production step for producing a sulfonic acid silyl ester by the production method according to any one of claims 1 to 6, and an alkyne represented by the following general formula (IVA) in the sulfonic acid silyl ester. A method for producing a silicon compound having a Si—C bond, which comprises a modification step of reacting a modifier selected from an alkene represented by the following general formula (IVB1) or (IVB2).
R ¹² C≡CH (IVA)
Z ¹ R ¹³ CHCH = CHR ¹⁴ (IVB1)
Z ¹ R ¹³ C = CHCH ₂ R ¹⁴ (IVB2)
(In these formulas, R ¹² to R ¹⁴ are each independently a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, and a part or all of the hydrogen atoms bonded to the carbon atom of the hydrocarbon group undergoes a reaction. It may be substituted with an uninvolved group; Z ¹ is a group selected from a cyano group, a nitro group, an acyl group, an amide group, an arylsulfonyl group, and an alkylsulfonyl group.) The method for producing a silicon compound according to claim 7, wherein the modification step is performed in the presence of a basic compound. The method for producing a silicon compound according to claim 8, wherein the basic compound is a compound selected from an amine compound, an amidine compound, and a guanidine compound. A silicon compound having a Si—C bond represented by the following general formula (VA), (VB), (VI), (VII), or (VIII).
R ¹⁵ _e R ¹⁶ _f Si (OR ¹⁷ ) _{4- (e + f + g)} (OSO ₂ R ¹⁸ ) _g (VA) R ¹⁹ _h R ²⁰ _i (R ²¹ O) _{3- (h + i)} Si-OSO _2- (o-) C ₆ H ₄ ) -CO ₂ R ²¹ (VB)
R ²² _j R ²³ _k Si (OR ²⁴ ) _{4- (j + k + l)} (C≡CR ²⁵ ) _l (VI)
R ²⁶ _m R ²⁷ _n Si (OR ²⁸ ) _{4- (m + n + o)} [C (CN) = CHR ²⁹ ] _o (VII)
X ⁷ (SiR ³⁰ R ³¹ O) _q-1 SiR ³⁰ R ³¹ X ⁸ (VIII)
(In these formulas, R ¹⁵ , R ¹⁶ , R ¹⁹ , R ²⁰ , R ²² , R ²³ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ , and R ³¹ , respectively, are independently methyl group and phenyl. A group selected from a group and a vinyl group; R ¹⁷ , R ²¹ , R ²⁴ , and R ²⁸ are groups independently selected from a methyl group and an ethyl group, respectively; R ¹⁸ is a trifluoromethyl group, A group selected from a methyl group and a p-tolyl group; X ⁷ and X ⁸ are independently trifluoromethanesulfonyloxy groups, methanesulfonyloxy groups, p-toluenesulfonyloxy groups, ethoxy groups, methoxy groups, phenyls, respectively. A group selected from an ethynyl group and a 1-cyano- ¹ -propenyl group, at least one of ^X7 and X8 is a trifluoromethanesulfonyloxy group, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, phenyl. A group selected from an ethynyl group and a 1-cyano-1-propenyl group; e, f, h, i, j, k, m, and n are independently integers of 0 or more and 2 or less; g. And l are independently 1 or 2; o is an integer greater than or equal to 1 and 4 or less; e + f + g and j + k + l are independently 2 or 3; h + i is an integer greater than or equal to 0 and 3 or less. M + n + o is an integer of 1 or more and 4 or less; q is an integer of 2 or more and 6 or less.)