JP2023079049A - Method for producing thionoacyloxysilane - Google Patents

Abstract

To provide a method for efficiently producing a thionoacyloxysilane.SOLUTION: A method for producing a thionoacyloxysilane includes a reaction step of reacting an alkoxysilane with a diacylsulfide.SELECTED DRAWING: None

Description

The present invention relates to an efficient method for producing thionoacyloxysilanes.

The thionoacyloxysilanes are functional chemicals that are used as reagents for precision synthesis of pharmaceuticals, agricultural chemicals, electronic materials and the like, intermediates for their synthesis, and the like.
Methods for producing thionoacyloxysilanes include, for example, (A) a method of reacting bissilylsilazane and thiocarboxylic acid (Non-Patent Document 1), and (B) a method of reacting chlorosilane and thiocarboxylic acid in the presence of a base (Non-Patent Document 1). Patent Document 1), (C) a method of reacting chlorosilane and potassium thiocarboxylic acid (Non-Patent Document 2), and the like are known.

J. Org. Chem. 1966, 31, 10, 3439-3440 Bull.Chem.Soc.Jpn.,46,244-248 (1973)

However, in the method using bissilylsilazane (Method A), there are problems such as that the silazane compound used as the starting material is easily hydrolyzed, requiring careful handling, and that there are only a few types of readily available commercially available compounds. The methods using chlorosilane (Methods B and C) also have problems such as difficulty in handling raw materials because chlorosilane is used which generates corrosive hydrogen chloride by hydrolysis. Furthermore, in the methods using bissilylsilazane or chlorosilane (Methods A to C), a large amount of salt is generated in the reaction, and the process of removing the salt by a method such as filtration is time-consuming and costly. For these reasons, there is a demand for an industrially more advantageous production method.

The present invention has been made in view of the circumstances as described above, and an object of the present invention is to provide a method for producing thionoacyloxysilanes more efficiently.

As a result of intensive research to solve the above problems, the present inventors have found that by reacting alkoxysilanes and diacyl sulfides, thionoacyloxysilanes can be produced efficiently without producing a large amount of salts. The inventors have found that it produces well, and have completed the present invention.

The manufacturing method of the present invention has the following features.
(1) Raw materials are readily available, handling is relatively easy, and safety is high.
(2) This reaction system does not produce salts and does not require a large amount of salt separation step.
(3) When an acidic solid catalyst is used, the catalyst can be easily separated by filtration, centrifugation, or the like.
The manufacturing method of the present invention makes it possible to reduce the cost and increase the efficiency of the manufacturing process, and is considered to have great advantages in terms of economic efficiency, environmental burden, etc., compared to conventional techniques.

That is, this application provides the following inventions.
<1>
A method for producing thionoacyloxysilanes, comprising a reaction step of reacting alkoxysilanes and diacylsulfides.
<2>
The method for producing thionoacyloxysilanes according to <1>, wherein the reaction step is performed in the presence of a catalyst.
<3>
The alkoxysilanes are represented by the following general formula (I), the diacyl sulfides are represented by the following general formula (II), and the thionoacyloxysilanes are represented by the following general formula (III). , <1> or <2>, the method for producing thionoacyloxysilanes.
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r) (I)
(Wherein, p, q, and r are each independently an integer of 0 to 3; p+q+r is an integer of 0 to 3; R ¹ , R ² , and R ³ 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; Each independently represents an alkyl group having 1 to 6 carbon atoms.)
( ^R5CO ) _2S (II)
(In the formula, R ⁵ 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. .)
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _{4−(p+q+r+s)} [OC(=S)R ⁵ ] _s
(III)
(In the formula, p, q, r, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same definitions as above; s is an integer of 1 or more and 4-(p+q+r) or less. )
<4>
The method for producing thionoacyloxysilanes according to any one of <1> to <3>, wherein the catalyst is an acidic catalyst.
<5>
The method for producing thionoacyloxysilanes according to <4>, wherein the acidic catalyst is an acidic compound selected from bis(perfluoroalkanesulfonyl)imides and metal salts thereof.
<6>
The method for producing thionoacyloxysilanes according to <4>, wherein the acidic catalyst is a solid acid catalyst selected from montmorillonite and zeolite.

According to the present invention, thionoacyloxysilanes can be produced more efficiently than conventional methods.

The present invention will be described in detail below. Unless otherwise specified, the same symbols have the same meanings when symbols in formulas in this specification are also used in other formulas.
A method for producing thionoacyloxysilanes according to one embodiment of the present invention includes a reaction step of reacting alkoxysilanes and diacylsulfides.
The reaction step can be performed in the presence of a catalyst to promote the reaction.

In the present embodiment, the alkoxysilanes used as raw materials are, for example, represented by the following general formula (I) (hereinafter, the alkoxysilanes represented by the general formula (I) are referred to as "alkoxysilanes (I)" sometimes referred to as).
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r) (I)
In general formula (I), p, q, and r are each independently an integer of 0 or more and 3 or less; p+q+r is an integer of 0 or more and 3 or less. R ¹ , R ² , and R ³ 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 react may be substituted with groups that do not participate in Each R ⁴ is independently an alkyl group having 1 to 6 carbon atoms.
As used herein, the term "does not participate in the reaction" means that it does not directly participate in the target reaction as a reactant and does not inhibit the reaction.

Examples of hydrocarbon groups represented by R ¹ , R ² and R ³ include alkyl groups, aryl groups, aralkyl groups and alkenyl groups.
When the hydrocarbon group is an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms. 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.

Groups that do not participate in the reaction include alkoxy groups having 1 to 6 carbon atoms, alkoxycarbonyl groups having 1 to 6 carbon atoms, dialkylamino groups having 1 to 6 carbon atoms, cyano groups, nitro groups, and halogen atoms. More specifically, alkoxy groups, alkoxycarbonyl groups, dialkylamino groups, and halogen atoms, specific examples of alkoxy groups having 1 to 6 carbon atoms include methoxy, ethoxy, and hexoxy groups; Specific examples of alkoxycarbonyl groups having 1 to 6 include methoxycarbonyl group, propoxycarbonyl group and the like; dialkylamino groups having 1 to 6 carbon atoms include dimethylamino group, diethylamino group and the like; halogen atom Specific examples of include a fluorine atom, a chlorine atom, a bromine atom, and the like.

Specific examples of alkyl groups optionally substituted with groups that do not participate in the reaction include methyl, ethyl, propyl, butyl, sec-butyl, pentyl, hexyl, cyclohexyl, octyl and decyl. group, 2-methoxyethyl group, 3-ethoxypropyl group, 2-methoxycarbonylethyl group, 2-dimethylaminoethyl group, 2-cyanoethyl group, trifluoromethyl group, 3-chloropropyl group and the like.

When the hydrocarbon group is an aryl group, the aryl group can be a monovalent aromatic organic group of a hydrocarbon ring system or a heterocyclic ring system. When the aryl group is a monovalent aromatic organic group of a hydrocarbon ring system, it preferably has 6-22 carbon atoms, more preferably 6-14 carbon atoms, and still more preferably 6-10 carbon atoms. Specific examples of monovalent aromatic organic groups having a hydrocarbon ring system include phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, and pentacenyl groups. When the aryl group is a heterocyclic monovalent aromatic organic group, the heteroatom in the heterocyclic ring is sulfur, oxygen, or the like. The number of carbon atoms in the heterocyclic monovalent aromatic organic group is preferably 4-12, more preferably 4-8. Specific examples of heterocyclic monovalent aromatic organic groups include thienyl, benzothienyl, dibenzothienyl, furyl, benzofuryl and dibenzofuryl groups.
Some or all of the hydrogen atoms bonded to the carbon atoms of the aryl group may be substituted with groups that do not participate in the reaction. Examples of the non-reaction-involved group include those shown as the non-reaction-involved group which may be substituted on the alkyl group. Examples of 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 the aryl group optionally substituted with groups that do not participate in the reaction include methylphenyl, ethylphenyl, hexylphenyl, methoxyphenyl, ethoxyphenyl, butoxyphenyl, octoxyphenyl, 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. .

Furthermore, when the hydrocarbon group is an aralkyl group, the aralkyl group preferably has 7 to 23 carbon atoms, more preferably 7 to 16 carbon atoms. Also, some or all of the hydrogen atoms bonded to the carbon atoms of the aralkyl group may be substituted with groups that do not participate in the reaction.
Examples of the non-reaction-involved group include those shown as the non-reaction-involved group which may be substituted on the alkyl group.
Specific examples of the aralkyl group optionally substituted with groups that do 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, a 1-( 4-methoxyphenyl)ethyl group and the like.

When the hydrocarbon group is an alkenyl group, the alkenyl group preferably has 2 to 23 carbon atoms, more preferably 2 to 20 carbon atoms. All may be substituted with groups that do not participate in the reaction.
Examples of the non-reaction-involved group include the groups shown as the non-reaction-involved groups which may be substituted on the alkyl group, as well as the above-mentioned aryl groups.
Specific examples of the alkenyl group optionally substituted with groups that do not participate in the reaction include vinyl group, 2-propenyl group, 3-butenyl group, 5-hexenyl group, 9-decenyl group, 2-phenylethenyl group, 2-(methoxyphenyl)ethenyl group, 2-naphthylethenyl group, 2-anthrylethenyl group and the like.

The carbon number of the alkyl group having 1 to 6 carbon atoms represented by R ⁴ is preferably 1 to 4, more preferably 1 to 3.
Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group, sec-butyl group, pentyl group, hexyl group and cyclohexyl group.

Specific examples of the alkoxysilane (I) include (methoxy)trimethylsilane (Me ₃ SiOMe), (ethoxy)trimethylsilane (Me ₃ SiOEt), (ethoxy)triethylsilane (Et ₃ SiOEt), (ethoxy)dimethyl(phenyl ) silane ( _Me2PhSiOEt ), (ethoxy)methyldi(phenyl)silane ₍ MePh2SiOEt), (ethoxy)dimethyl(vinyl)silane ( _Me2ViSiOEt ), methylphenyldi(methoxy)silane (MePhSi(OMe) ₂ ) , dimethyldi(methoxy)silane (Me ₂ Si(OMe) ₂ ), di(ethoxy)dimethylsilane (Me ₂ Si(OEt) ₂ ), di(ethoxy)(phenyl)vinylsilane (PhViSi(OEt) ₂ ), methyltri( methoxy)silane (MeSi(OMe) ₃ ), tri(ethoxy)methylsilane (MeSi(OEt) ₃ ), phenyltri(methoxy)silane (PhSi(OMe) ₃ ), phenyltri(ethoxy)silane (PhSi(OEt) ₃ ), vinyltri(methoxy)silane (ViSi(OMe) ₃ ), vinyltri(ethoxy)silane (ViSi(OEt) ₃ ), tri(methoxy)silane (HSi(OMe) ₃ ), tri(ethoxy)silane (HSi(OEt ) ₃ ), tetra(methoxy)silane (Si(OMe) ₄ ), tetra(ethoxy)silane (Si(OEt) ₄ ), tetra(propoxy)silane (Si(OPr) ₄ ), tetra(butoxy)silane (Si (OBu) ₄ ) and the like.

On the other hand, diacyl sulfides to be reacted with the alkoxysilanes are represented by, for example, the following general formula (II) (hereinafter, diacyl sulfides represented by general formula (II) are referred to as "diacyl sulfides (II)" sometimes referred to as).
( ^R5CO ) _2S (II)

In general formula (II), R ⁵ 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. may
Examples of the hydrocarbon group represented by R ⁵ include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. These are the alkyl groups and aryl groups shown in the description of R ¹ , R ² and R ³ , aralkyl group, alkenyl group and the like. Examples of groups that do not participate in the reaction include groups that do not participate in the reaction shown in the description of R ¹ , R ² and R ³ in the general formula (I).
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, even more preferably 1 to 12, and particularly preferably 1 to 6; 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. Yes; preferably 2 to 20, more preferably 2 to 18 when the hydrocarbon group is an alkenyl group.
Specific examples of these hydrocarbon groups include the hydrocarbon groups shown in the description of R ¹ , R ² and R ³ in the general formula (I).

Specific examples of diacyl sulfide (II) include diacetyl sulfide ((MeCO) ₂ S), dipropionyl sulfide ((EtCO) ₂ S), dibutyryl sulfide ((PrCO) ₂ S), diisobutyryl sulfide (( ⁱ PrCO) ₂ S), dihexanoyl sulfide ((PentCO) ₂ S), dibenzoyl sulfide ((PhCO) ₂ S), bis(benzylcarbonyl) sulfide ((PhCH ₂ CO) ₂ S), dicrotonoyl sulfide ( (MeCH=CHCO) ₂ S) and the like.

The molar ratio of diacyl sulfides to alkoxysilanes can be arbitrarily selected, but considering the yield of thionoacyloxysilanes based on alkoxysilanes, it is usually 0.4 or more and 300 or less. It is preferably 0.5 to 200, more preferably 0.5 to 150, and 0.5 to 100, 0.5 to 50, 0.5 to 10, or 0.5 It may be more than or equal to 5 or less.

In the present embodiment, thionoacyloxysilanes represented by the following general formula (III) can be produced by reacting alkoxysilanes (I) with diacylsulfides (II) (hereinafter, general formula (III ) is sometimes referred to as "thionoacyloxysilane (III)").
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r+s) [OC(=S)R ⁵ ] _s (III)

p, q, r, s, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in general formula (III) have the same meanings as defined above, and specific examples thereof include Examples include those represented by general formulas (I) and (II). Further, s is an integer of 1 or more and 4−(p+q+r) or less, preferably 1 or more and 2 or less, more preferably 1.

Specific examples of thionoacyloxysilane (III) include trimethyl(thionoacetoxy)silane (Me ₃ SiOC(=S)Me), triethyl(thionoacetoxy)silane (Et ₃ SiOC(=S)Me), dimethyl(phenyl)(thionoacetoxy)silane ( _Me2PhSiOC (=S)Me), methyldi(phenyl)(thionoacetoxy)silane ( _MePh2SiOC (=S)Me), dimethyl(vinyl)(thionoacetoxy) ) silane ( _{Me2ViSiOC (} =S)Me), (ethoxy)dimethyl(thionoacetoxy)silane (Me2Si(OEt)[OC(=S)Me]), dimethylbis(thionoacetoxy)silane (Me ₂ Si[OC(=S)Me] ₂ ), di(ethoxy)methyl(thionoacetoxy)silane (MeSi(OEt) ₂ [OC(=S)Me]), tri(ethoxy)(thionoacetoxy)silane (Si(OEt) ₃ [OC(=S)Me]), di(ethoxy)bis(thionoacetoxy)silane (Si(OEt) ₂ [OC(=S)Me] ₂ ), tri(methoxy)(thio Noacetoxy)silane (Si(OMe) ₃ [OC(=S)Me]), di(methoxy)bis(thionoacetoxy)silane (Si(OMe) ₂ [OC(=S)Me] ₂ ), trimethyl ( thiobenzoyloxy)silane ( _Me3SiOC (=S)Ph), tri(ethoxy)(thiobenzoyloxy)silane (Si(OEt) ₃ [OC(=S)Ph]), tri(methoxy)(thiobenzoyloxy) ) silane (Si(OMe) ₃ [OC(=S)Ph]) and the like.

The reaction step in the present embodiment involves a nucleophilic substitution reaction of alkoxysilanes, which are raw materials having alkoxy groups, with diacylsulfides.
For example, when monoalkoxysilane and diacyl sulfides are reacted, the reaction step involves elimination of carboxylic acid ester. In the reaction process of the present embodiment, in the presence of a Lewis acid catalyst containing cations (M ^m+ ) of elements of Groups 3 to 15, the reaction proceeds as shown in the following reaction formula (Scheme 1). .

スキーム１に示されるように、ルイス酸触媒の陽イオンは、ジアシルスルフィド類の酸素原子に配位することによって、カルボニル基の炭素原子の求核性を高め、反応を促進していると考えられる。

As shown in Scheme 1, the cation of the Lewis acid catalyst is believed to promote the reaction by increasing the nucleophilicity of the carbon atom of the carbonyl group by coordinating with the oxygen atom of the diacyl sulfides. .

As alkoxysilanes, not only monoalkoxysilane but also dialkoxysilane, trialkoxysilane, and tetraalkoxysilane can be used.
That is, the number of thionoacyloxysilanes obtained by the production method according to the present embodiment is one when monoalkoxysilane is used as a raw material, but when dialkoxysilane, trialkoxysilane, and tetraalkoxysilane are used as raw materials, is not limited to one type of thionoacyloxysilanes. For example, when dialkoxysilanes are used as raw materials, the thionoacyloxysilanes to be produced are thionoacyloxysilanes substituted with one alkoxy group, thionoacyloxysilanes substituted with two alkoxy groups, or It means that it may be a mixture of these. Furthermore, when trialkoxysilane is used as a raw material, the thionoacyloxysilanes to be produced include thionoacyloxysilanes substituted with one alkoxy group, thionoacyloxysilanes substituted with two alkoxy groups, and thionoacyloxysilanes substituted with two alkoxy groups. It may be thionoacyloxysilanes substituted with three groups, or a mixture thereof. In addition, when tetraalkoxysilane is used as a raw material, the thionoacyloxysilanes to be produced include thionoacyloxysilanes substituted with one alkoxy group, thionoacyloxysilanes substituted with two alkoxy groups, This means that it may be thionoacyloxysilanes substituted with three alkoxy groups, thionoacyloxysilanes substituted with four alkoxy groups, or a mixture thereof.

In the reaction step in this embodiment for producing thionoacyloxysilanes, a catalyst can also be used to promote the reaction.
Suitable catalysts include acidic catalysts. Various conventionally known acidic compounds can be used as the acidic catalyst.
As the conventionally known acidic compound, compounds selected from sulfonic acid compounds, imide compounds thereof, and Lewis acid compounds containing elements of Groups 3 to 15 are preferred.

Sulfonic acid compounds or imide compounds thereof include perfluoroalkanesulfonic acids such as trifluoromethanesulfonic acid and pentafluoroethanesulfonic acid; bis(trifluoromethanesulfonyl)imide, bis(pentafluoroethanesulfonyl)imide, bis(nonafluorobutane) Bis(perfluoroalkanesulfonyl)imide such as sulfonyl)imide; and the like are preferably used. Among these, the sulfonic acid compound or its imide compound is more preferably bis(trifluoromethanesulfonyl)imide, bis(nonafluorobutanesulfonyl)imide, or the like.

Lewis acid compounds containing elements of Groups 3 to 15 include halides, perchlorates, sulfonates, bis(perfluoroalkanesulfonyl)imide salts, and hexafluoroantimonates of these elements. , thiocyanate, etc. can be used.

With respect to the elements of Groups 3-15, they are preferably selected from Groups 3, 8, 13-15, more preferably Groups 3, 8, 13 or It is an element selected from Group 15, more preferably from Group 8 or Group 13.
More specifically, those elements are preferably selected from scandium, yttrium, samarium, yttrium, iron, ruthenium, copper, aluminum, gallium, indium, tin, and bismuth, more preferably scandium, iron, ruthenium, It is an element selected from aluminum, gallium, indium, tin and bismuth, more preferably selected from iron, ruthenium, aluminum, gallium and indium.

Therefore, more specifically, Lewis acid compounds containing these elements are scandium chloride (III), titanium chloride (III), titanium chloride (IV), iron chloride (III), iron bromide (III), chloride Ruthenium (III), aluminum (III) chloride, gallium (III) chloride, indium (III) chloride, tin (IV) chloride, iron (III) perchlorate, scandium (III) trifluoromethanesulfonate, trifluoromethanesulfonic acid yttrium (III), iron (III) trifluoromethanesulfonate, copper (II) trifluoromethanesulfonate, aluminum (III) trifluoromethanesulfonate, gallium (III) trifluoromethanesulfonate, indium (III) trifluoromethanesulfonate, tin (IV) trifluoromethanesulfonate, bismuth (IV) trifluoromethanesulfonate, lanthanum (III) trifluoromethanesulfonate, praseodymium (IV) trifluoromethanesulfonate, neodymium (IV) trifluoromethanesulfonate, yttrium trifluoromethanesulfonate (IV), bis(trifluoromethanesulfonyl)imide scandium (III), bis(trifluoromethanesulfonyl)imide zinc (II), bis(trifluoromethanesulfonyl)imide indium (III), bis(trifluoromethanesulfonyl)imide tin (IV) , tris[bis(trifluoromethanesulfonyl)imide]indium (III), iron (III) hexafluoroantimonate, indium hexafluoroantimonate (III), iron (III) thiocyanate, indium thiocyanate (III), etc. be done. In these compounds, those containing water of crystallization (hydrates) can also be used.
Among these Lewis acid compounds, the catalyst is preferably a Lewis acid compound containing iron, indium, etc. More specifically, bis(trifluoromethanesulfonyl)imide indium (III), bis(trifluoromethanesulfonyl) Imidoscandium (III), iron perchlorate (III) and the like are preferred.

Further, as the acidic catalyst, various conventionally known solid acid catalysts, which are easy to separate and recover, can be used. Inorganic and organic solid acid catalysts can be used.
Examples of inorganic solid acid catalysts include solid inorganic substances such as metal salts and metal oxides. zeolite, mesoporous silica, and montmorillonite having cations of elements or protic hydrogen atoms; inorganic solid acids using silica gel, heteropolyacid, carbon-based materials, etc. as carriers; and the like.
Types of zeolites include, for example, USY series, Y series, beta series, mordenite series, ZSM-5 series, etc., and the silica/alumina ratio is generally in the range of 3 to 2,000.

Among these inorganic solid acids, one or more selected from montmorillonite and zeolite are preferably used. In addition, as the cation of an element of Groups 3 to 15, a cation selected from tin (IV), indium (III), aluminum (III), iron (III), and scandium (III) is preferably used. be done.
More specifically, preferred inorganic solid acids include montmorillonite having cations selected from tin (IV), indium (III), and scandium (III); montmorillonite K10 having protic hydrogen atoms (Merck available from the company); Zeolites include USY zeolites having protic hydrogen atoms and selected from CBV780, CBV760, CBV720, and CBV600 (all available from Zeolist).

Furthermore, as the solid acid catalyst, in addition to the above inorganic solid acids, organic solid acids having an acidic functional group can also be used. An organic solid acid is a polymer or the like having an acidic functional group. Types of acidic functional groups include sulfo group, carboxyl group, phosphoryl group, etc. Types of polymer include Teflon (registered trademark) backbone polymer having perfluoro side chain, styrene-divinylbenzene copolymer polymer, and the like. mentioned. Specific examples of organic solid acids include Nafion (NAFION (registered trademark), available from DuPont and Merck), Dowex (DOWEX (registered trademark), Dow Chemical and Merck), which have a sulfo group. available from), AMBERLITE (registered trademark), available from Rohm & Hass, Merck), Amberlyst (available from Dow Chemical Company, Merck), and the like. More specific examples include Nafion NR50, Dowex 50WX2, Dowex 50WX4, Dowex 50WX8, Amberlite IR120, Amberlite IRP-64, Amberlyst 15, and Amberlyst 36.
The catalyst used in the production method according to the present embodiment can be used not only singly, but also in any combination and ratio of multiple catalysts.

The amount of the catalyst to the starting material can be determined arbitrarily, but the molar ratio or weight ratio is usually about 0.0001 to 10, preferably about 0.001 to 8, more preferably about 0.001 to 6. .

The reaction in the reaction step can be carried out in a liquid phase or gas phase depending on the reaction temperature, reaction pressure and the like. Moreover, as a form of a reaction apparatus, 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° C.
to 200°C, 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, more preferably 10 to 35°C.
Furthermore, the reaction pressure is generally 0.1 to 100 atmospheres, preferably 0.1 to 50 atmospheres, more preferably 0.1 to 10 atmospheres, and still more preferably 0.5 to 5 atmospheres.
The reaction time depends on the amount of raw materials, the amount of catalyst, the reaction temperature, the form of the reactor, etc., but in consideration of productivity and efficiency, it is usually 0.1 to 1200 minutes, preferably 0.1 to 600 minutes, It is more preferably about 0.1 to 300 minutes, still more preferably about 30 to 240 minutes.

Also, when the reaction is carried out in a liquid phase system, it can be carried out with or without a solvent. When a solvent is used, hydrocarbons such as decalin (decahydronaphthalene) and decane; chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,2,3-trichlorobenzene, , 4-trichlorobenzene and other halogenated hydrocarbons; tert-butyl methyl ether, dibutyl ether and other ethers; and the like. Two or more solvents can be used in any combination and ratio. 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 can also be performed under microwave irradiation. In this reaction system, diacyl sulfides, acid catalysts, etc. have relatively large dielectric loss coefficients and absorb microwaves efficiently. can be done systematically.

Various commercially available devices equipped with a contact or non-contact temperature sensor can be used in the microwave irradiation reaction. In addition, the power of microwave irradiation, the type of cavity (multimode, single mode), the mode of irradiation (continuous, intermittent), etc., can be arbitrarily determined according to the scale of the reaction, the type of raw material, the type of catalyst, etc. be able to. The frequency of microwaves is usually 0.3 to 30 GHz. Preferred among these are the IMS frequency bands allocated for use in the industrial, scientific, medical, and other fields, and more preferred are the 2.45 GHz band, the 5.8 GHz band, and the like.

In the microwave irradiation reaction, a heating material (susceptor) that generates heat by absorbing microwaves can be added to the reaction system in order to heat the reaction system more efficiently. As the type of heating material, various conventionally known ones such as activated carbon, graphite, silicon carbide, and titanium carbide can be used. Also, a molded catalyst obtained by mixing the above-described catalyst and heating material powder and firing the mixture using an appropriate binder such as sepiolite or formite can also be used.

The reaction process in the present embodiment proceeds even in a closed system reactor, but the reaction proceeds more efficiently by making the reactor an open system and continuously removing the reaction product out of the reaction system. can also

When a solid acid catalyst is used in the production method according to the present embodiment, separation and recovery of the catalyst after the reaction step can be easily performed by a method such as filtration or centrifugation.
Purification of the produced thionoacyloxysilanes can also be easily accomplished by means commonly used in organic chemistry, such as distillation, recrystallization, and column chromatography.

EXAMPLES 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 these Examples.
The main analyzers and the like used in the following examples are as follows.
・ Nuclear magnetic resonance spectroscopy (hereinafter sometimes referred to as NMR): Bruker AVANCE III HD 600 MHz (with cryoprobe)
・ Gas chromatograph analysis (hereinafter sometimes referred to as GC): GC-2014 manufactured by Shimadzu Corporation
・ Gas chromatograph mass spectrometry (hereinafter sometimes referred to as GC-MS): GCMS-QP2010Plus manufactured by Shimadzu Corporation

(Example 1)
(Ethoxy)trimethylsilane (Me ₃ SiOEt) 1.0 mmol, diacetyl sulfide ((MeCO) ₂ S) 1.1 mmol, and bis(trifluoromethanesulfonyl)imide (Tf ₂ NH) 0.01 mmol were placed in a reaction tube, Stirred at about 25° C. (room temperature) for 0.5 hour. The product was analyzed by GC, GC-MS, and NMR, and the yield was calculated by NMR. As a result, trimethyl(thionoacetoxy)silane (Me _Si [OC(=S)Me]) yielded 83%. (see Tables 1 and 2).

(Examples 2 to 22)
The reaction conditions (catalyst, raw materials, etc.) were changed as shown in Table 1, and the reaction and analysis were performed in the same manner as in Example 1, and the yield of the product was calculated. Table 1 shows the results.
Table 2 shows spectral data of the obtained thionoacyloxysilanes.

Notes in Table 1 are shown below.
1) _Me3SiOEt : (ethoxy)trimethylsilane
Et ₃ SiOEt: (ethoxy)triethylsilane
_Me2PhSiOEt : (ethoxy)dimethyl(phenyl)silane
_MePh2SiOEt : (ethoxy)methyldi(phenyl)silane
_Me2ViSiOEt : (ethoxy)dimethyl(vinyl)silane
_Me2Si (OEt) ₂ : Di(ethoxy)dimethylsilane
MeSi(OEt) ₃ : Tri(ethoxy)methylsilane
_Me3SiOMe : (methoxy)trimethylsilane
2) (MeCO) ₂ S: diacetyl sulfide
3) Tf ₂ NH: bis(trifluoromethanesulfonyl)imide
( _C4F9SO2 ) _2NH : _bis ( _{nonafluorobutanesulfonyl} )imide
In(NTf ₂ ) ₃ : tris[bis(trifluoromethanesulfonyl)imide]indium (
III)
Sc(NTf ₂ ) ₃ : tris[bis(trifluoromethanesulfonyl)imide]scandium(III)
Fe( _ClO4 ) _3.6H2O : Iron (III) _perchlorate hexahydrate
Sc(OTf) ₃ : scandium trifluoromethanesulfonate (III)
Mont-Sn ⁴⁺ : Sn ⁴⁺ -containing montmorillonite (Na ⁺ -type montmorillonite (Kunipia F manufactured by Kunimine Kogyo Co., Ltd.) is treated with an aqueous solution containing Sn ⁴⁺ (SnCl ₄ 5H ₂ O dissolved in water) , Na ⁺
(prepared by a cation-exchange reaction to exchange for Sn ⁴⁺ ).
Mont-K10: Montmorillonite K10 (manufactured by Merck)
CBV780: H-SDUSY type zeolite CBV780 (manufactured by Zeolyst, used after firing at 500°C)
Amberlyst15: H ⁺ type cation exchange resin Amberlyst 15 (manufactured by Merck)
4) Me ₃ SiOC(=S)Me: trimethyl(thionoacetoxy)silane
Et ₃ SiOC(=S)Me: triethyl(thionoacetoxy)silane
Me ₂ PhSiOC(=S)Me: dimethyl(phenyl)(thionoacetoxy)silane
MePh ₂ SiOC(=S)Me: methyldi(phenyl)(thionoacetoxy)silane
Me ₂ ViSiOC(=S)Me: dimethyl(vinyl)(thionoacetoxy)silane
Me ₂ Si(OEt)[OC(=S)Me]: (ethoxy)dimethyl(thionoacetoxy)silane
Me ₂ Si[OC(=S)Me] ₂ : dimethylbis(thionoacetoxy)silane
MeSi(OEt) ₂ [OC(=S)Me]: di(ethoxy)methyl(thionoacetoxy)silane
5) Yield was calculated by NMR.
6) 1-substituted and 2-substituted forms were produced. The numbers in parentheses indicate the product ratio, and the yield indicates the total yield.

Notes in Table 2 are shown below.
1) See Note 4 in Table 1 for the name of thionoacyloxysilane (III)
2) Measured value in deuterated chloroform
3) GC-MS (EI, 70eV)

Since thionoacyloxysilanes useful as functional chemicals can be produced more efficiently and safely by the production method of the present invention, the utility value of the present invention is high and its industrial significance is great.
In addition, the thionoacyloxysilanes provided by the production method of the present invention have thionoacyloxy groups with higher reactivity than alkoxy groups, and have higher reactivity than the raw material alkoxysilanes. , is characterized by having a sulfur atom. Therefore, it is thought that conversion of thionoacyloxy groups to other functional groups, etc., and physical property control of functional materials using siloxane-based compounds can be performed more efficiently, and high utility value as functional chemicals. have

Claims (6)

A method for producing thionoacyloxysilanes, comprising a reaction step of reacting alkoxysilanes and diacylsulfides. 2. The method for producing thionoacyloxysilanes according to claim 1, wherein said reaction step is carried out in the presence of a catalyst. The alkoxysilanes are represented by the following general formula (I), the diacyl sulfides are represented by the following general formula (II), and the thionoacyloxysilanes are represented by the following general formula (III). The method for producing thionoacyloxysilanes according to claim 1 or 2.
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _4-(p+q+r) (I)
(Wherein, p, q, and r are each independently an integer of 0 to 3; p+q+r is an integer of 0 to 3; R ¹ , R ² , and R ³ 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; Each independently represents an alkyl group having 1 to 6 carbon atoms.)
( ^R5CO ) _2S (II)
(In the formula, R ⁵ 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. .)
R ¹ _p R ² _q R ³ _r Si(OR ⁴ ) _{4−(p+q+r+s)} [OC(=S)R ⁵ ] _s
(III)
(In the formula, p, q, r, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same definitions as above; s is an integer of 1 or more and 4-(p+q+r) or less. ) The method for producing thionoacyloxysilanes according to any one of claims 1 to 3, wherein the catalyst is an acidic catalyst. 5. The method for producing thionoacyloxysilanes according to claim 4, wherein said acidic catalyst is an acidic compound selected from bis(perfluoroalkanesulfonyl)imides and metal salts thereof. 5. The method for producing thionoacyloxysilanes according to claim 4, wherein said acidic catalyst is a solid acid catalyst selected from montmorillonite and zeolite.