Method for producing organosilicon compound

Abstract

Disclosed is a method for producing an organosilicon compound, the method including a step for reacting, in the presence of a catalyst, a hydrosilane compound A with a compound B that has a sulfonate group and a group having an unsaturated hydrocarbon bond and being capable of reacting with a hydrosilyl group. The catalyst contains at least one selected from the group consisting of an Ir catalyst and an Rh catalyst.

Description

Method for producing organosilicon compounds

[0001] The present disclosure relates to a method for producing organosilicon compounds.

[0002] Known conventional methods for producing organosilicon compounds include those described in Non-Patent Document 1 and Patent Document 1. Non-Patent Document 1 describes a method for producing an organosilicon compound having a sulfonate group by oxidizing a thioacetate compound having a silyl group. Patent Document 1 also describes a method for producing an organosilicon compound having a sulfonate group by hydrosilylation using a platinum (Pt) catalyst.

[0003] Non-patent document 1: Langmuir 2019, 35, 9785-9793

[0004] Patent Document 1: Japanese Patent Application Laid-Open No. 6-100695

[0005] The problem to be solved by the present disclosure is to provide a method for producing organosilicon compounds that is simple and has excellent yield.

[0006] Means for solving the above problems include the following aspects.<1> A method for producing an organosilicon compound, comprising: reacting a hydrosilane compound A with a compound B having a sulfonate group and a group having an unsaturated hydrocarbon bond reactive with a hydrosilyl group in the presence of a catalyst, wherein the catalyst comprises at least one catalyst selected from the group consisting of an Ir catalyst and a Rh catalyst.<2> The method for producing an organosilicon compound according to<1>, wherein the hydrosilane compound A is a hydrosilane compound represented by the following formula 1, the compound B is a compound having an unsaturated hydrocarbon bond represented by the following formula 2, and the resulting organosilicon compound is a compound represented by the following formula 3:

[0007]

[0008] In Formulas 1 to 3, w represents an integer of 1 or more, x represents an integer of 1 or more, and Sil １ represents a substituent containing three or more Si atoms, and a plurality of Si １may be the same or different, Ra represents a hydrogen atom or a monovalent substituent, and a plurality of Ra may be the same or different, R represents an (x+w)-valent organic group containing a carbon atom, M １ represents a monovalent to trivalent cation, and n is M １ represents an integer of 1 to 3 which is equal to the valence of the atom.

[0009] <3> The above Sil １ is a group represented by any one of the following formulae Si-1 to Si-4:

[0010]

[0011] In formula Si-1 to formula Si-4, R １ represents a hydrocarbon group, and a plurality of R １ may be the same or different, y represents an integer of 1 or more, R ２ represents a hydrocarbon group, and a plurality of R ２ may be the same or different, z represents 2 or 3, R ３ represents a hydrocarbon group, and a plurality of R ３ may be the same or different, p represents an integer of 1 to 3, q ​​represents an integer of 1 to 3, R ４ , R ４ａ and R ４ｂ represents a hydrocarbon group, and a plurality of R ４ , R ４ａ and R ４ｂ may be the same or different, and * indicates the bonding position to another structure.

[0012] <4> The method for producing an organosilicon compound according to <1> or <2>, wherein the catalyst contains at least one compound selected from the group consisting of chloro(1,5-cyclooctadiene)iridium(I) dimer, chlorobis(cyclooctene)iridium(I) dimer, chlorobis(ethylene)iridium(I) dimer, (1,5-cyclooctadiene)(methoxy)iridium(I) dimer, and chloro(1,5-cyclooctadiene)rhodium(I) dimer. <5> The method for producing an organosilicon compound according to <1> or <2>, wherein the amount of the catalyst used is 0.001 molar equivalent or more per molar equivalent of the hydrosilane compound A. <6> The method for producing an organosilicon compound according to <1> or <2>, wherein the catalyst contains an Ir catalyst. <7> The method for producing an organosilicon compound according to <2>, wherein w is 1 or 2. <8> The method for producing an organosilicon compound according to <1> or <2>, wherein the group having an unsaturated hydrocarbon bond is an allyl group or a (meth)acrylic group. <9> The method for producing an organosilicon compound according to <1> or <2>, wherein a solvent is used in the reacting step, and the solvent is at least one solvent selected from the group consisting of water and water-soluble solvents. <10> The method for producing an organosilicon compound according to <8>, wherein the solvent is at least one solvent selected from the group consisting of water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tetrahydrofuran.

[0013] According to the present disclosure, a method for producing an organosilicon compound can be provided that is simple and has excellent yield.

[0014] The contents of the present disclosure are described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present disclosure, but the present disclosure is not limited to such an embodiment. In this specification, the term "to" indicating a numerical range is used to mean that the numerical values ​​before and after it are included as the upper and lower limits. In the numerical ranges described in stages in this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with a value shown in the examples. Furthermore, in the description of groups (atomic groups) in this specification, a notation that does not specify whether they are substituted or unsubstituted encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "(meth)acrylic" is a term used as a concept encompassing both acrylic and methacrylic, and "(meth)acryloyl" is a term used as a concept encompassing both acryloyl and methacryloyl. Furthermore, the term "process" in this specification includes not only an independent process but also a process that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, in this disclosure, "mass %" and "weight %" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Furthermore, in this disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. Furthermore, the weight average molecular weight (Mw) and number average molecular weight (Mn) in this disclosure are values ​​measured by gel permeation chromatography (GPC) unless otherwise specified. The GPC measurement was performed using an HLC (registered trademark)-8020GPC (manufactured by Tosoh Corporation) as a measuring device, three TSKgel (registered trademark) Super Multipore HZ-H columns (4.6 mm ID x 15 cm, manufactured by Tosoh Corporation), and THF (tetrahydrofuran) as an eluent.The measurement conditions are a sample concentration of 0.45% by mass, a flow rate of 0.35 ml / min, a sample injection volume of 10 μL, and a measurement temperature of 40°C, and the measurement is performed using a refractive index (RI) detector. A calibration curve is prepared from eight samples of "Standard Sample TSK Standard, Polystyrene" from Tosoh Corporation: "F-40," "F-20," "F-4," "F-1," "A-5000," "A-2500," "A-1000," and "n-propylbenzene." In the present disclosure, "total solid content" refers to the total mass of the components excluding the solvent from the entire composition. Furthermore, as described above, "solid content" refers to the components excluding the solvent, and may be, for example, solid or liquid at 25°C. The present disclosure will be described in detail below.

[0015] (Method for Producing Organosilicon Compound) The method for producing an organosilicon compound according to the present disclosure comprises a step of reacting a hydrosilane compound A with a compound B having a sulfonate group and a group having an unsaturated hydrocarbon bond reactive with a hydrosilyl group in the presence of a catalyst, wherein the catalyst comprises at least one catalyst selected from the group consisting of an Ir catalyst and a Rh catalyst.

[0016] Conventionally, a platinum catalyst has often been used in the reaction between a hydrosilane compound and an unsaturated hydrocarbon compound reactive with a hydrosilyl group. However, the present inventors have found that when an unsaturated hydrocarbon compound having a sulfonate group is used, the platinum catalyst does not function, resulting in a low yield. The present inventors speculate that the sulfonate group is likely a catalyst poison that deactivates the platinum catalyst. The method for producing an organosilicon compound according to the present disclosure uses at least one catalyst selected from the group consisting of an Ir catalyst and a Rh catalyst, so that the catalyst is not poisoned by the sulfonate group and the reaction between a hydrosilane compound A and a compound B having a sulfonate group and a group having an unsaturated hydrocarbon bond reactive with a hydrosilyl group proceeds efficiently. Furthermore, the method can be produced simply with a small number of steps, resulting in an excellent yield.

[0017] The method for producing an organosilicon compound according to the present disclosure will be described in detail below.

[0018] <Reaction Step (Reaction Step)> The method for producing an organosilicon compound according to the present disclosure includes a step (also simply referred to as the "reaction step") of reacting hydrosilane compound A with compound B having a sulfonate group and a group having an unsaturated hydrocarbon bond reactive with a hydrosilyl group in the presence of a catalyst. In the reaction step, the Si-H group in hydrosilane compound A reacts with the unsaturated hydrocarbon bond in compound B, resulting in hydrosilylation.

[0019] [Hydrosilane Compound A] The hydrosilane compound A used in the reaction step is not particularly limited as long as it is a compound having a Si—H group, but from the viewpoint of further exerting the effects of the present disclosure, it preferably has 3 or more Si atoms, more preferably 3 to 20 Si atoms, even more preferably 3 to 12 Si atoms, particularly preferably 3 to 10 Si atoms, and most preferably 4 to 7 Si atoms. Furthermore, the hydrosilane compound A may be a compound having only one Si—H group or may be a compound having two or more Si—H groups, but from the viewpoint of surfactant activity, it is preferably a compound having only one Si—H group.

[0020] Furthermore, from the viewpoint of the surfactant ability of the resulting organosilicon compound (hereinafter also simply referred to as "surface activity"), it is preferable that all terminal structures other than Si-H groups of the hydrosilane compound A are hydrocarbon groups, and it is more preferable that all terminal structures other than Si-H groups are alkyl groups. From the viewpoint of surfactant ability, the hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms (also referred to as "number of carbon atoms"), more preferably a methyl group, an ethyl group, or a branched alkyl group having 3 to 6 carbon atoms, still more preferably a t-butyl group or a methyl group, and particularly preferably a methyl group.

[0021] Furthermore, from the viewpoint of further exhibiting the effects of the present disclosure, hydrosilane compound A is preferably a hydrosilane compound represented by the following formula 1:

[0022]

[0023] In formula 1, Sil１ represents a substituent containing three or more Si atoms.

[0024] Sil in Formula 1 １ From the viewpoint of surface activity, the number of Si atoms is preferably an integer of 3 to 20, more preferably an integer of 3 to 12, even more preferably an integer of 3 to 10, and particularly preferably an integer of 4 to 7. １ The substituent on the Si atom in is not particularly limited, but from the viewpoint of surfactant activity, it is preferably a hydrocarbon group or an alkoxy group other than a silyl group or a siloxy group, and more preferably a hydrocarbon group. From the viewpoint of surfactant activity, the hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or a branched alkyl group having 3 to 6 carbon atoms, even more preferably a t-butyl group or a methyl group, and particularly preferably a methyl group.

[0025] The above Sil １ From the viewpoint of surface activity, is preferably a group represented by any one of the following formulae Si-1 to Si-4, and more preferably a group represented by the following formulae Si-3 or Si-4.

[0026]

[0027] In formula Si-1 to formula Si-4, R １ represents a hydrocarbon group, and a plurality of R １ may be the same or different, y represents an integer of 1 or more, R ２ represents a hydrocarbon group, and a plurality of R ２ may be the same or different, z represents 2 or 3, R ３ represents a hydrocarbon group, and a plurality of R ３ may be the same or different, p represents an integer of 1 to 3, q ​​represents an integer of 1 to 3, R ４ , R ４ａ and R ４ｂ represents a hydrocarbon group, and a plurality of R ４ , R ４ａ and R ４ｂmay be the same or different, and * indicates the bonding position to another structure.

[0028] R １ ~R ４ , R ４ａ and R ４ｂ From the viewpoint of surface activity, the hydrocarbon group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or a branched alkyl group having 3 to 6 carbon atoms, further preferably a t-butyl group or a methyl group, and particularly preferably a methyl group. １ ~R ４ are preferably the same group. ４ａ or R ４ｂ When present, it is preferable that they are the same group. In formula Si-2, y is preferably an integer of 2 to 50, more preferably an integer of 2 to 20, even more preferably 2 to 10, and particularly preferably 2. In formula Si-3, z is preferably 2 from the viewpoint of surfactant ability. In formula Si-4, p is preferably 1 or 2 from the viewpoint of surfactant ability. In formula Si-4, q is preferably 1 or 2 from the viewpoint of surfactant ability. Furthermore, from the viewpoint of surfactant ability, it is preferable that the above p and q are integers that satisfy p+q=3 or p+q=4.

[0029] Preferred specific examples of the hydrosilane compound A include the following A1 to A20.

[0030]

[0031] Furthermore, as the hydrosilane compound A, for example, the compounds described in paragraph 0023 of JP-A-2021-11456 can be used.

[0032] [Compound B Having a Group Having an Unsaturated Hydrocarbon Bond Reactive with a Hydrosilyl Group and a Sulfonate Group] The compound B having a group having an unsaturated hydrocarbon bond reactive with a hydrosilyl group and a sulfonate group used in the above-mentioned reaction step is not particularly limited as long as it is a compound having one or more unsaturated hydrocarbon bonds and one or more sulfonate groups reactive with a hydrosilyl group. Examples of the unsaturated hydrocarbon bond reactive with a hydrosilyl group in compound B include an ethylenically unsaturated hydrocarbon bond and a carbon-carbon triple bond, with an ethylenically unsaturated hydrocarbon bond being preferred. The number of unsaturated hydrocarbon bonds reactive with a hydrosilyl group in compound B is not particularly limited, but from the viewpoint of surfactant activity, it is preferably 1 or 2, and more preferably 1.

[0033] The group having an unsaturated hydrocarbon bond in compound B is not particularly limited, but from the viewpoints of reactivity and yield, it is preferably an allyl group, a (meth)acrylic group, or a styryl group, more preferably an allyl group or a (meth)acrylic group, even more preferably an allyl group, a (meth)acrylate group, or a (meth)acrylamide group, and particularly preferably an allyl group or a (meth)acrylate group.

[0034] The number of sulfonate groups in Compound B is not particularly limited, but from the viewpoints of yield and surfactant ability, it is preferably 1 or 2, and more preferably 1. The counter cation of the sulfonate group in Compound B is not particularly limited, and may be any of a metal cation and an organic cation such as ammonium, but is preferably a monovalent to trivalent metal cation, more preferably a divalent or monovalent metal cation, and even more preferably a monovalent metal cation, and more preferably Na ＋ or K ＋ The counter cation is preferably an alkali metal ion, an alkaline earth metal ion, or an Al ３＋ , Fe ２＋ , Fe ３＋Alternatively, primary to quaternary ammonium cations are preferred, with alkali metal ions or alkaline earth metal ions being more preferred, and alkali metal ions being particularly preferred. Examples of alkali metals include lithium (Li), sodium (Na), potassium (K), and cesium (Cs). Examples of alkaline earth metals include calcium (Ca), strontium (Sr), and barium (Ba). The number of counter cations can be appropriately selected depending on the number of sulfonate groups and the valence of the counter cations. When multiple counter cations are present, the counter cations may be of the same type, or two or more types may be present.

[0035] Compound B may be a compound in which the group having an unsaturated hydrocarbon bond and a sulfonate group are directly bonded, or may be a compound in which the group having an unsaturated hydrocarbon bond and a sulfonate group are bonded via a linking group. The linking group is not particularly limited, but from the viewpoints of yield and surfactant activity, it is preferably a group having a carbon atom, more preferably a divalent or trivalent group having a carbon atom, and particularly preferably a trivalent group having a carbon atom. Furthermore, from the viewpoints of yield and surfactant activity, the linking group is preferably a group shown below. Here, n represents an integer of 1 to 10.

[0036]

[0037] In the above groups, # represents the bonding position to the group having an unsaturated hydrocarbon bond, and ## represents the bonding position to the sulfonate group.

[0038] Furthermore, from the viewpoint of further exerting the effects of the present disclosure, compound B is preferably a compound having an unsaturated hydrocarbon bond represented by the following formula 2.

[0039]

[0040] In formula 2, w represents an integer of 1 or more, x represents an integer of 1 or more, Ra represents a hydrogen atom or a monovalent substituent, and a plurality of Ra may be the same or different, R represents an (x+w)-valent organic group containing a carbon atom, and M １represents a monovalent to trivalent cation, and n is M １ represents an integer of 1 to 3 which is equal to the valence of the atom.

[0041] In formula 2, w is preferably an integer of 1 to 8, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1, from the viewpoint of surfactant ability. In formula 2, x is preferably an integer of 1 to 8, more preferably an integer of 1 to 4, even more preferably an integer of 1 to 3, particularly preferably 1 or 2, and most preferably 2, from the viewpoint of reactivity. In formula 2, Ra is preferably a hydrogen atom or a methyl group. When multiple Ra are present, it is preferable that Ra are the same group.

[0042] The number of carbon atoms in R in Formula 2 is preferably 2 to 60, more preferably 3 to 55, even more preferably 4 to 50, and particularly preferably 4 to 20, from the viewpoint of surfactant performance. Furthermore, R in Formula 2 is preferably a group having an oxygen atom, more preferably a group having at least one bond selected from the group consisting of ester bonds and ether bonds, even more preferably a group having two or more of at least one bond selected from the group consisting of ester bonds and ether bonds, and particularly preferably a group having two to 12 of at least one bond selected from the group consisting of ester bonds and ether bonds. Furthermore, from the viewpoint of surfactant performance, R in Formula 2 is preferably a group shown below.

[0043]

[0044] In the above groups, * represents the bonding position with the ethylenically unsaturated bond, and ** represents SO ３ － and n represents an integer of 1 to 10.

[0045] M in Equation 2 １is preferably a monovalent to trivalent metal cation or a primary to quaternary ammonium cation, more preferably a divalent or monovalent metal cation, and even more preferably a monovalent metal cation; Na ＋ or K ＋ In formula 2, n is preferably 1 or 2, and more preferably 1.

[0046] Specific examples of the compound B include the following B1 to B9.

[0047]

[0048] The amounts of hydrosilane compound A, hydrosilyl group, and compound B used in the reaction step are not particularly limited; however, the ratio of the molar equivalents of Si—H groups in hydrosilane compound A to the molar equivalents of unsaturated hydrocarbon bonds in compound B (Si—H groups:unsaturated hydrocarbon bonds) is preferably 3:1 to 1:3, more preferably 1.5:1 to 1:1.5, and even more preferably 1.2:1 to 1:1.2.

[0049] [Catalyst] The method for producing an organosilicon compound according to the present disclosure includes a step of reacting a hydrosilane compound A with a compound B in the presence of a catalyst, wherein the catalyst includes at least one selected from the group consisting of an Ir catalyst and a Rh catalyst.

[0050] Examples of the Ir (iridium) catalyst used in the present disclosure include chloro(1,5-cyclooctadiene)iridium(I) dimer, chloro(2,5-norbornadiene)iridium(I) dimer, 1,5-cyclooctadiene(acetylacetonato)iridium(I), chlorobis(cyclooctene)iridium(I) dimer, chlorocarbonylbis(triphenylphosphine)iridium(I), chlorobis(ethylene)iridium(I) (dimer), (1,5-cyclooctadiene)(methoxy)iridium(I) (dimer), and the like.

[0051] Rh (rhodium) catalysts used in the present disclosure include chlorobis(cyclooctene)rhodium(I) dimer, chlorobis(ethylene)rhodium(I) (dimer), chloro(1,5-cyclooctadiene)rhodium(I) dimer, and the like.

[0052] From the viewpoints of yield and reaction rate, the catalyst preferably includes an Ir catalyst, and from the viewpoints of yield and reaction rate, the catalyst preferably includes at least one catalyst selected from the group consisting of a monovalent Ir catalyst and a monovalent Rh catalyst.

[0053] Furthermore, the catalyst is preferably a catalyst having an olefin or diene as a ligand, and more preferably a catalyst having 1,5-cyclooctadiene as a ligand. Furthermore, in the reaction step, it is also preferable to add these ligands separately from the catalyst, from the viewpoints of yield, reaction rate, and catalyst stability. Specifically, the catalyst preferably contains at least one compound selected from the group consisting of chloro(1,5-cyclooctadiene)iridium(I) dimer, chlorobis(cyclooctene)iridium(I) dimer, chlorobis(ethylene)iridium(I) dimer, (1,5-cyclooctadiene)(methoxy)iridium(I) dimer, and chloro(1,5-cyclooctadiene)rhodium(I) dimer, and particularly preferably contains chloro(1,5-cyclooctadiene)iridium(I) dimer.

[0054] The catalyst may be prepared in the reaction system and used.

[0055] In terms of yield and reaction rate, the amount of the catalyst used in the reaction step is preferably 0.001 molar equivalent or more, more preferably 0.005 molar equivalent or more, and particularly preferably 0.01 molar equivalent or more, relative to 1 molar equivalent of the hydrosilane compound A. Furthermore, the amount of the catalyst used is preferably 0.2 molar equivalent or less, more preferably 0.1 molar equivalent or less, relative to 1 molar equivalent of the hydrosilane compound A.

[0056] [Solvent] It is preferable to use a solvent in the reaction step. Any solvent can be used as long as it does not inhibit the desired hydrosilylation reaction. The solvent is not particularly limited, and examples include water; alcohol-based solvents such as methanol, ethanol, isopropanol, and diacetone alcohol; alcohol ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, and 3-methoxy-3-methyl-1-butanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as tetrahydrofuran and dioxane; ester-based solvents such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate, t-butyl acetate, methyl lactate, and ethyl lactate; aromatic solvents such as benzene, toluene, and xylene; amide-based solvents such as formamide and dimethylformamide; and hydrocarbon-based solvents such as n-hexane, cyclohexane, n-heptane, n-octane, and n-decane.

[0057] Among these, from the viewpoints of yield and reaction rate, the solvent is preferably at least one solvent selected from the group consisting of water and water-soluble solvents, which are solvents that easily dissolve compound B, and more preferably at least one solvent selected from the group consisting of water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tetrahydrofuran. Furthermore, from the viewpoints of yield, reaction rate, and adjustment of the reaction temperature, a mixed solvent of water and a water-soluble solvent may be used. When a mixed solvent of water and a water-soluble solvent is used, the volume fraction of water in the mixed solvent is preferably 1% by volume or more and 30% by volume or less, more preferably 3% by volume or more and 25% by volume or less, and even more preferably 5% by volume or more and 20% by volume or less.

[0058] The water-soluble solvent may be any water-soluble solvent other than water, and examples thereof include alcohol compounds, ketone compounds, ester compounds, cyclic ether compounds, etc. Among these, the water-soluble solvent to be used in combination with water is preferably an alcohol compound or a cyclic ether compound, more preferably a monoalcohol compound. When the water-soluble solvent is used alone, it is preferably an alcohol compound or a cyclic ether compound, more preferably a cyclic ether compound. Examples of the alcohol compound include monoalcohol compounds and polyhydric alcohol compounds, such as monoalcohol compounds such as methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, isobutanol, s-butanol, t-butanol, 1-pentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-octanol, 2-ethylhexanol, 2-propyl-1-hexanol, 1-nonanol, and 1-decanol; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, glycerin, 1,2,6-hexanetriol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, and 2-ethyl-1,3- Examples of the cyclic ether compounds include polyhydric alcohol compounds such as hexanediol, 2-methyl-2,4-pentanediol, 1,2-octanediol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, dipropylene glycol, and polyoxyethylene polyoxypropylene glycol, and (poly)alkylene glycol monoether compounds such as ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, and polyoxypropylene glyceryl ether. Examples of the cyclic ether compounds include tetrahydrofuran, dioxane, and tetrahydropyran.

[0059] The solvent used in the reaction step may be one type alone or a combination of two or more types. The amount of the solvent used in the reaction step is not particularly limited and can be appropriately selected depending on the solubility of the compound used, etc. For example, the solvent is preferably used in an amount by mass that is 2 to 1,000 times, more preferably 3 to 200 times, and even more preferably 5 to 100 times the total mass of compound B.

[0060] [Reaction Conditions] The reaction temperature in the above reaction step may be any temperature at which the hydrosilylation reaction proceeds. From the viewpoints of yield and reaction rate, the reaction temperature is preferably 30°C or higher, more preferably 40°C or higher, even more preferably 40°C to 100°C, and particularly preferably 60°C to 90°C. The reaction time in the above reaction step is not particularly limited, and may be, for example, 10 minutes to 24 hours. The above reaction step is preferably carried out in an inert atmosphere such as nitrogen or argon. There are also no particular limitations on the reaction apparatus, reaction means, reaction tools, etc. used, and known reaction apparatuses can be used. There are also no particular limitations on the scale of the reaction in the above reaction step, and these may be selected appropriately as desired.

[0061] [Organosilicon Compound] The molecular weight of the organosilicon compound produced by the method for producing an organosilicon compound according to the present disclosure is not particularly limited, but is preferably 300 to 5,000, and more preferably 400 to 2,000.

[0062] In the method for producing an organosilicon compound according to the present disclosure, it is preferable that hydrosilane compound A is a hydrosilane compound represented by formula 1 below, compound B is a compound having an unsaturated hydrocarbon group represented by formula 2 below, and the resulting organosilicon compound is a compound represented by formula 3 below:

[0063]

[0064] In Formulas 1 to 3, w represents an integer of 1 or more, x represents an integer of 1 or more, and Sil １ represents a substituent containing three or more Si atoms, and a plurality of Si １may be the same or different, Ra represents a hydrogen atom or a monovalent substituent, and a plurality of Ra may be the same or different, R represents an (x+w)-valent organic group containing a carbon atom, M １ represents a monovalent to trivalent cation, and n is M １ represents an integer of 1 to 3 which is equal to the valence of the atom.

[0065] Formula 1 and Formula 2 have the same meanings as Formula 1 and Formula 2 described above, and preferred embodiments are also the same. １ ,Ra,R,M １ and n is w, x, Sil in Formula 1 or Formula 2. １ ,Ra,R,M １ and n have the same meanings as n, and preferred embodiments are also the same.

[0066] Specific examples of organosilicon compounds produced by the method for producing an organosilicon compound according to the present disclosure include compounds having any one of the following anion structures A1-1 to A1-14, A2-1 to A2-8, A3-1, A3-2, and A4-1, and Na ＋ , K. ＋ , Cs ＋ , Mg ２＋ , Fe ３＋ Alternatively, a compound having tetramethylammonium as a counter cation is preferred.

[0067]

[0068]

[0069] Specific preferred examples of organosilicon compounds produced by the method for producing an organosilicon compound according to the present disclosure include the following A1 to H1, D2 to D9, and G2 to G9.

[0070]

[0071]

[0072]

[0073] -Applications- The organosilicon compounds produced by the method for producing an organosilicon compound according to the present disclosure are not particularly limited in their applications, but can be suitably used as leveling agents or surfactants. Furthermore, the organosilicon compounds produced by the method for producing an organosilicon compound according to the present disclosure can be suitably used in known applications that use leveling agents or surfactants. Furthermore, the organosilicon compounds produced by the method for producing an organosilicon compound according to the present disclosure can be suitably used for film formation. Furthermore, the organosilicon compounds produced by the method for producing an organosilicon compound according to the present disclosure can be suitably used in photosensitive materials, surface modifiers, protective layer-forming compositions, conductive layer-forming compositions, undercoat layer-forming compositions, pressure-responsive materials, thermo-responsive materials, microcapsules, microgels, and the like. In particular, the organosilicon compounds produced by the method for producing an organosilicon compound according to the present disclosure can be suitably used in silver halide photographic photosensitive materials and diffusion transfer type silver halide photographic photosensitive materials.

[0074] [Other Steps] The method for producing an organosilicon compound according to the present disclosure may include other steps in addition to the reaction step. Examples of the other steps include a step of preparing a hydrosilane compound A, a step of preparing a compound B having an unsaturated hydrocarbon-bonded group and a sulfonate group that can react with a hydrosilyl group, a step of preparing a catalyst, a step of removing the solvent used in the reaction step, and a step of purifying the obtained organosilicon compound by column chromatography, thin-layer chromatography, reprecipitation, recrystallization, or the like. Furthermore, known steps may be performed as the other steps.

[0075] The present disclosure will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present disclosure. Therefore, the scope of the present disclosure is not limited to the specific examples shown below. In the examples, "%" and "parts" mean "% by mass" and "parts by mass," respectively, unless otherwise specified.

[0076] Example 1: Synthesis of Compound 1

[0077]

[0078] 2.38 g (16.5 mmol) of sodium allylsulfonate, 162 mg (1.50 mmol) of 1,5-cyclooctadiene (cod), and 18 mL of methanol (MeOH) were weighed into a three-necked flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer. After replacing the atmosphere with nitrogen, the mixture was stirred at 45°C for 10 minutes. chloro(1,5-cyclooctadiene)iridium(I) dimer ([IrCl(cod)] ２ After stirring for an additional 10 minutes, 3.34 g (15.0 mmol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added dropwise over 10 minutes. After the addition was complete, the reaction was carried out at 45°C for 2 hours. １ H-NMR spectrum measurement confirmed that 1,1,1,3,5,5,5-heptamethyltrisiloxane had completely disappeared and that the target product, Compound 1, had been produced. The methanol solvent was removed by distillation under reduced pressure, and the residue was then purified by silica gel column chromatography using ethyl acetate / methanol as a developing solvent, yielding 11.4 g (76% yield) of Compound 1. １ H-NMR (MeOD): δ (ppm) = 0.01 to 0.14 ppm (21H), 0.45 to 0.50 ppm (2H), 1.71 to 1.79 ppm (2H), 2.68 to 2.72 ppm (2H)

[0079] Comparative Example 1 A reaction was carried out in the same manner as in Example 1, except that chloro(1,5-cyclooctadiene)iridium(I) dimer was replaced with 200 mg of hexachloroplatinic(IV) acid hexahydrate. １ The reaction rate was determined by H-NMR spectroscopy. After 2 hours of reaction at 45°C, the production rate of Compound 1 was less than 1%.

[0080] Comparative Example 2 The reaction was carried out in the same manner as in Example 1, except that chloro(1,5-cyclooctadiene)iridium(I) dimer was replaced with 100 μL of a 2% xylene solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Karstedt catalyst). １The reaction rate was determined by H-NMR spectroscopy. After 2 hours of reaction at 45°C, the production rate of Compound 1 was less than 1%.

[0081] (Comparative Example 3)

[0082]

[0083] Compound 1 was synthesized via steps (C-1) to (C-3) with reference to the method described in Langmuir 2019, 35, 9785-9793 (Non-Patent Document 1). The yields of each step were 78% for step (C-1), 71% for step (C-2), and 45% for step (C-3), respectively, and the combined yield of all steps was 25%.

[0084] (Example 2: Synthesis of Compound 2) <Synthesis of Intermediate 1>

[0085]

[0086] In a 300 mL three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer, 19.62 g of diallyl fumarate and 71.3 g of 2-propanol (iPrOH) were added, and the flask was purged with nitrogen. Sodium hydrogen sulfite (NaHSO ) diluted with 24.7 g of ion-exchanged water was added to the flask. ３ 10.4 g of 2-propanol and water were distilled off under reduced pressure, and then 150 g of ethyl acetate was added and stirred, and the precipitated solid was collected by filtration. The obtained solid was dispersed and washed in 150 g of ethyl acetate for 1 hour, filtered, and dried to obtain 20.5 g of a white solid of intermediate 1. The white solid was determined to be intermediate 1. １ This was confirmed by H-NMR.

[0087] Example 2A: Synthesis of Compound 2

[0088]

[0089] 2.30 g (7.65 mmol) of intermediate 1, 162 mg (1.50 mmol) of 1,5-cyclooctadiene, and 18 mL of methanol were weighed into a three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer. After purging with nitrogen, the mixture was stirred at 45°C for 10 minutes. 201 mg (0.30 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer was added, and the mixture was stirred for an additional 10 minutes. 3.34 g (15.0 mmol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane was then added dropwise over 10 minutes. After the dropwise addition was complete, the mixture was allowed to react at 45°C for 2 hours. １ H-NMR spectrum measurement confirmed that 1,1,1,3,5,5,5-heptamethyltrisiloxane had completely disappeared and that the target product, Compound 2, had been produced. The methanol solvent was removed by distillation under reduced pressure, and the residue was then purified by silica gel column chromatography using ethyl acetate / methanol as a developing solvent, yielding 4.08 g (73% yield) of Compound 2. １ H-NMR (MeOD): δ (ppm) = -0.11 ~ 0.12 ppm (42H), 0.36 ~ 0.48 ppm (4H), 1.50 ~ 1.66 ppm (4H), 2.85 ~ 3.15 ppm (4H), 3.52 ~ 4.08 ppm (5H)

[0090] Example 2B Synthesis of Compound 2 Compound 2 was synthesized in the same manner as in Example 2A, except that 18 mL of methanol was changed to 18 mL of tetrahydrofuran, and 3.69 g of compound 2 was obtained (yield 66%).

[0091] (Examples 3 to 15: Synthesis of Compound 3) <Synthesis of Intermediate 2 and Intermediate 3>

[0092]

[0093] A 1000 mL three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer was charged with 499.0 g of ethyl acetate (AcOEt), 24.30 g of ion-exchanged water, and palladium / carbon (Pd / C, 5% palladium, approximately 55% wet with water), and the atmosphere was replaced with nitrogen. The three-neck flask was placed in an ice bath, and 100.0 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane was added dropwise over 30 minutes. After the dropwise addition, the mixture was returned to room temperature and allowed to react for 3 hours. After the reaction, the palladium / carbon was removed by filtration through Celite, and the mixture was concentrated under reduced pressure using a rotary evaporator, yielding 100.5 g of a colorless, transparent liquid. This liquid was determined to be Intermediate 2. １ The reaction mixture was confirmed by H-NMR. Subsequently, 99.0 g of the obtained intermediate 2 and 285 g of toluene were added to a 500 mL three-neck flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer, and the three-neck flask was immersed in an ice bath. After confirming that the temperature had reached 5°C or below, 32.5 g of pyridine was added dropwise, and stirring was continued until the temperature returned to 5°C or below. A separate solution was prepared by adding 18.4 g of toluene and 19.3 mL of dichloromethylsilane to a dropping funnel. The prepared solution was added dropwise to the three-neck flask over 30 minutes. After the addition was completed, the reaction solution was returned to room temperature and allowed to react for 3 hours. After the reaction, the precipitated solid was filtered off, and the resulting colorless, transparent liquid was subjected to a separation operation. The separation operation was performed twice using 350 mL of ion-exchanged water, and the organic layer was recovered. Magnesium sulfate was added to the organic layer, and the mixture was dehydrated for 30 minutes or more, and then concentrated under reduced pressure using a rotary evaporator. Crushed silica gel (Wakogel C-200, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the resulting liquid, and the mixture was stirred and then filtered under suction to obtain a colorless, transparent liquid. This liquid was determined to be Intermediate 3. １ This was confirmed by H-NMR.

[0094] <Synthesis of Compound 3>

[0095]

[0096] The reaction of intermediate 3 was investigated under the conditions shown in Table 1 below. 1.59 g (11.0 mmol) of sodium allylsulfonate, 20 mL of a solvent shown in Table 1, and optionally a ligand shown in Table 1 were added to a three-necked flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer, and after nitrogen substitution, the mixture was stirred for 10 minutes at the temperature shown in Table 1. A catalyst shown in Table 1 was added, and the mixture was stirred for a further 10 minutes. 5.19 g (10.0 mmol) of intermediate 3 was then added dropwise over 10 minutes. After the dropwise addition was complete, the reaction was continued for 2 hours at the temperature shown in Table 1. It was confirmed that the target compound 3 was produced. １ After confirmation by H-NMR, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using ethyl acetate / methanol as a developing solvent. The yields under each condition are shown in Table 1. １ H-NMR (MeOD): δ (ppm) = -0.12 ~ 0.12 ppm (45H), 0.52 ~ 0.58 ppm (2H), 1.74 ~ 1.82 ppm (2H), 2.68 ~ 2.76 ppm (2H)

[0097]

[0098] Details of the abbreviations listed in Table 1 are as follows: cod: 1,5-cyclooctadiene [IrCl(cod)] ２ : Chloro(1,5-cyclooctadiene)iridium(I) dimer [RhCl(cod)] ２ : Chloro(1,5-cyclooctadiene)rhodium(I) dimer [IrCl(coe) ２ ] ２ : chlorobis(cyclooctene)iridium(I) dimer [IrCl(C ２ H4) ２ ] ２ : chlorobis(ethylene)iridium(I) dimer Ir(acac)(cod): 1,5-cyclooctadiene(acetylacetonato)iridium(I) [Ir(OMe)(cod)] ２ : (1,5-cyclooctadiene)(methoxy)iridium(I) dimer H ２ PtCl ６ ・6H ２O: Hexachloroplatinic (IV) acid hexahydrate MeOH: Methanol IPA: 2-propanol 2-BuOH: 2-butanol

[0099] Example 16: Synthesis of Compound 4

[0100]

[0101] 3.83 g (16.5 mmol) of 3-sulfopropyl potassium acrylate, 162 mg (1.50 mmol) of 1,5-cyclooctadiene, and 30 mL of methanol were weighed into a three-necked flask equipped with a stirrer, a condenser, a nitrogen inlet tube, and a thermometer. After replacing the atmosphere with nitrogen, the mixture was stirred at 45°C for 10 minutes. 202 mg (30 mmol) of chloro(1,5-cyclooctadiene)iridium(I) dimer was added, and the mixture was stirred for an additional 10 minutes. Intermediate 3 (7.79 g, 15.0 mmol) was then added dropwise over 10 minutes. After the dropwise addition was complete, the mixture was allowed to react at 45°C for 2 hours. １ H-NMR spectrum measurement confirmed that intermediate 3 had completely disappeared and that the target compound 4 had been produced. After the methanol solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography using ethyl acetate / methanol as a developing solvent, yielding 6.99 g of compound 4 (yield 62%). １ H-NMR (MeOD): δ (ppm) = -0.10 to 0.10 ppm (42H), 0.72 to 0.82 ppm (2H), 1.96 to 2 .04ppm (2H), 2.26-2.36ppm (2H), 2.70-2.82ppm (2H), 4.04-4.14ppm (2H)

[0102] The disclosure of Japanese Patent Application No. 2024-043971, filed on March 19, 2024, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A method for producing an organosilicon compound, comprising the step of reacting a hydrosilane compound A with a compound B having a sulfonate group and a group having an unsaturated hydrocarbon bond reactive with a hydrosilyl group in the presence of a catalyst, wherein the catalyst comprises at least one catalyst selected from the group consisting of an Ir catalyst and a Rh catalyst.

2. The method for producing an organosilicon compound according to claim 1, wherein the hydrosilane compound A is a hydrosilane compound represented by the following formula 1, the compound B is a compound having an unsaturated hydrocarbon bond represented by the following formula 2, and the resulting organosilicon compound is a compound represented by the following formula 3: In Formulas 1 to 3, w represents an integer of 1 or more, x represents an integer of 1 or more, and Sil １ represents a substituent containing three or more Si atoms, and a plurality of Si １ may be the same or different, Ra represents a hydrogen atom or a monovalent substituent, and a plurality of Ra may be the same or different, R represents an (x+w)-valent organic group containing a carbon atom, M １ represents a monovalent to trivalent cation, and n is M １ represents an integer of 1 to 3 which is equal to the valence of the atom.

3. The Sil １ is a group represented by any one of the following formulae Si-1 to Si-4: In formula Si-1 to formula Si-4, R １ represents a hydrocarbon group, and a plurality of R １ may be the same or different, y represents an integer of 1 or more, R ２ represents a hydrocarbon group, and a plurality of R ２ may be the same or different, z represents 2 or 3, R ３ represents a hydrocarbon group, and a plurality of R ３ may be the same or different, p represents an integer of 1 to 3, q ​​represents an integer of 1 to 3, R ４ , R ４ａ and R ４ｂ represents a hydrocarbon group, and a plurality of R ４ , R ４ａ and R ４ｂ may be the same or different, and * indicates the bonding position to another structure.

4. The method for producing an organosilicon compound according to claim 1 or 2, wherein the catalyst comprises at least one compound selected from the group consisting of chloro(1,5-cyclooctadiene)iridium(I) dimer, chlorobis(cyclooctene)iridium(I) dimer, chlorobis(ethylene)iridium(I) (dimer), (1,5-cyclooctadiene)(methoxy)iridium(I) (dimer), and chloro(1,5-cyclooctadiene)rhodium(I) dimer.

5. The method for producing an organosilicon compound according to claim 1 or 2, wherein the amount of the catalyst used is 0.001 molar equivalent or more per molar equivalent of the hydrosilane compound A.

6. The method for producing an organosilicon compound according to claim 1 or 2, wherein the catalyst comprises an Ir catalyst.

7. The method for producing an organosilicon compound according to claim 2, wherein w is 1 or 2.

8. The method for producing an organosilicon compound according to claim 1 or 2, wherein the group having an unsaturated hydrocarbon bond is an allyl group or a (meth)acrylic group.

9. The method for producing an organosilicon compound according to claim 1 or 2, wherein a solvent is used in the reaction step, and the solvent is at least one solvent selected from the group consisting of water and water-soluble solvents.

10. The method for producing an organosilicon compound according to claim 8, wherein the solvent is at least one solvent selected from the group consisting of water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and tetrahydrofuran.

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