Compound and method for producing same

Abstract

A compound represented by formula (1). (In formula (1), each of the plurality of Z5 is independently a hydrogen atom or a group represented by-SiR1R2R3, but at least one of the plurality of Z5 is a group represented by-SiR1R2R3. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to compounds and methods for their preparation.

[0002] This application claims priority based on Japanese Patent Application No. 2023-008656 filed in Japan on January 24, 2023, and incorporates the contents thereof herein. Background Art

[0003] Siloxane compounds, which are considered to be condensates of orthosilicic acid or its derivatives and have a cage-like skeleton, show promise as functional silicon materials in various fields. Numerous studies are underway to discover new compounds and to develop methods for their production.

[0004] For example, as one of such cage-type siloxane compounds, the following is disclosed: according to the synthesis route shown below, a compound represented by the following formula (90) (sometimes referred to as "compound (90)" in this specification) is used as a raw material to obtain a compound represented by the following formula (91) (sometimes referred to as "compound (91)" in this specification) (see non-patent document 1).

[0005] [Chemical Formula 1]

[0006]

[0007] Prior art literature

[0008] Non-patent literature

[0009] Non-patent document 1: Main Group Metal Chemistry 20 (1997) 515-529 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] However, the method described in Non-Patent Document 1 has the following problem: in order to obtain Compound (91), it is necessary to use a large amount of excessive dimethylsilyl chloride ((CH3)2HSiCl) for Compound (90) as a raw material. This is because Compound (90), as a silicate compound, contains a large amount of hydrated water.

[0012] As described above, some conventional cage siloxane compounds cannot be produced by practical methods, and improvements in production methods are desired.

[0013] Furthermore, currently, it cannot be said that sufficient research has been conducted on cage siloxane compounds, and research on new cage siloxane compounds is expected.

[0014] An object of the present invention is to provide a novel cage siloxane compound and a method for producing the same.

[0015] Means for solving problems

[0016] The present invention includes the following aspects.

[0017] [1] A compound represented by the following formula (1).

[0018] [Chemical Formula 2]

[0019]

[0020] (In formula (1), multiple Z 5 Each independently is a hydrogen atom or -SiR 1 R 2 R 3 The groups shown, but multiple Z 5 At least one of them is -SiR 1 R 2 R 3 The groups shown;

[0021] R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are the above-mentioned groups, these groups may be combined with each other to form a ring.

[0022] [2] The compound according to [1], wherein R 1 、R 2 and R 3Preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms; more preferably, each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; further preferably, each independently represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an ethyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group , n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecane alkyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl, cyclopentylmethyl, 1-cyclopentylethyl, cyclohexylmethyl, 1-cyclohexylethyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, dimethylcyclohexyl, vinyl, 1-propenyl, 2-propenyl (allyl), 2-butenyl, 2-butenyl, 3- butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, heptenyl, octenyl, nonenyl, decenyl, isopropenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, isopentenyl, butadienyl, pentadienyl, hexadienyl, octadienyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, or benzyl (dimethylphenyl).

[0023] [3] The compound according to [1] or [2], wherein the general formula "-SiR 1 R 2 R 3" The group represented by " is a trialkylsilyl group, a dialkylsilyl group, a monoalkylsilyl group, a trialkenylsilyl group, a dialkenylsilyl group, a monoalkenylsilyl group, a triarylsilyl group, a diarylsilyl group, a monoarylsilyl group, a dialkylmonoarylsilyl group, a monoalkyldiarylsilyl group, a monoalkylmonoarylsilyl group, a dialkenylmonoarylsilyl group, a monoalkenyldiarylsilyl group, a monoalkenylmonoarylsilyl group, a dialkenylmonoalkylsilyl group, a monoalkenyldialkylsilyl group, a monoalkenylmonoalkylsilyl group, or a silicon group (-SiH3); preferably a trimethylsilyl group, a dimethylmonovinylsilyl group, or a dimethylsilyl group.

[0024] [4] A method for producing a compound, comprising reacting a compound (10) represented by the following formula (10) with at least one compound (3) represented by the following formula (3) to obtain a compound (1) represented by the following formula (1).

[0025] [Chemical Formula 3]

[0026]

[0027] X-SiR 1 R 2 R 3 ……(3)

[0028] (In formula (3), R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are mentioned above, these groups may be combined with each other to form a ring; X is a halogen atom.

[0029] [Chemical Formula 4]

[0030]

[0031] (In formula (1), multiple Z 5 Each independently is a hydrogen atom or -SiR 1 R 2 R 3 The groups shown, but multiple Z 5 At least one of them is -SiR 1 R 2 R 3 The groups shown;

[0032] R 1 、R 2 and R 3are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are the above-mentioned groups, these groups may be combined with each other to form a ring.

[0033] [5] The method for producing the compound according to [4], wherein R 1 、R 2 and R 3 Preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or an aryl group having 6 to 20 carbon atoms; more preferably, each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms; further preferably, each independently represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an ethyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group, an alkyl group , n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecane alkyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, tricyclodecyl, cyclopentylmethyl, 1-cyclopentylethyl, cyclohexylmethyl, 1-cyclohexylethyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, dimethylcyclohexyl, vinyl, 1-propenyl, 2-propenyl (allyl), 2-butenyl, 2-butenyl, 3- butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, heptenyl, octenyl, nonenyl, decenyl, isopropenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, isopentenyl, butadienyl, pentadienyl, hexadienyl, octadienyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, or benzyl (dimethylphenyl).

[0034] [6] The method for producing a compound according to [4] or [5], wherein the compound of the general formula "-SiR 1 R 2 R 3 " The group represented by " is a trialkylsilyl group, a dialkylsilyl group, a monoalkylsilyl group, a trialkenylsilyl group, a dialkenylsilyl group, a monoalkenylsilyl group, a triarylsilyl group, a diarylsilyl group, a monoarylsilyl group, a dialkylmonoarylsilyl group, a monoalkyldiarylsilyl group, a monoalkylmonoarylsilyl group, a dialkenylmonoarylsilyl group, a monoalkenyldiarylsilyl group, a monoalkenylmonoarylsilyl group, a dialkenylmonoalkylsilyl group, a monoalkenyldialkylsilyl group, a monoalkenylmonoalkylsilyl group, or a silicon group (-SiH3); preferably a trimethylsilyl group, a dimethylmonovinylsilyl group, or a dimethylsilyl group.

[0035] [7] The method for producing a compound according to any one of [4] to [6], wherein the halogen atom is a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.

[0036] [8] The method for producing a compound according to any one of [4] to [7], wherein the total amount of the compound (3) used is preferably 24 times or less by mole, more preferably 18 times or less by mole, relative to the amount of the compound (10) used.

[0037] [9] The method for producing a compound according to any one of [4] to [8], wherein, when the compound (10) reacts with the compound (3), a base is preferably used; an organic base is more preferably used as the base, and an aromatic amine or an aliphatic amine is more preferably used as the organic base; and aniline, pyridine, piperidine, triethylamine or diisopropylethylamine is particularly preferably used as the aromatic amine or the aliphatic amine.

[0038]

[10] The method for producing the compound according to [9], wherein the amount of the base used is preferably 1 to 2 times the molar amount, more preferably 1 to 1.5 times the molar amount, relative to the amount of the compound (3) used.

[0039]

[11] The method for producing a compound according to any one of [4] to

[10] , wherein a solvent is preferably used when the compound (10) reacts with the compound (3); as the solvent, a compound having an ether bond, an amide compound having an amide bond or an amide group, an ester compound having an ester bond, a halogenated hydrocarbon having a halogen atom, a nitrile compound having a nitrile group, or a hydrocarbon without a substituent is more preferably used; and tetrahydrofuran (THF), 1,4-dioxane, tetrahydropyran, dibutyl ether, 1,2-dimethoxyethane, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), ethyl acetate, butyl acetate, 1,2-dichloroethane, dichloromethane, chlorobenzene, propionitrile, acetonitrile, toluene, n-hexane, or methylcyclohexane is further preferably used.

[0040]

[12] The method for producing the compound according to

[11] , wherein the amount of the solvent used is preferably 0 to 100 mL, more preferably 10 to 50 mL, relative to 1 mmol of the compound (10) used.

[0041]

[13] The method for producing the compound according to any one of [4] to

[12] , wherein the compound (3) is reacted with at least two or more kinds of the compound (3).

[0042]

[14] The method for producing a compound according to any one of [4] to

[13] , further comprising a proton exchange step, wherein the proton exchange step is to obtain the compound (10) by reacting a silicate having a structure represented by the following formula (10)' with an acidic compound.

[0043] [Chemical Formula 5]

[0044]

[0045] (In formula (10)', Q + represents a cation.)

[0046]

[15] The method for producing a compound according to

[14] , wherein the acid dissociation constant pKa of the acidic compound in dimethyl sulfoxide (DMSO) is preferably -1 to 20, more preferably 0 or more and 16 or less, further preferably 1 or more and 14 or less, and particularly preferably 2 or more and 8 or less.

[0047]

[16] The method for producing the compound according to

[14] or

[15] , wherein the acidic compound is preferably nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, benzoic acid, Michaelis acid, dimedone, or acetylacetone.

[0048]

[17] The method for producing a compound according to any one of

[14] to

[16] , wherein the amount of the acidic compound used in the proton exchange step is 1 to 50 times, preferably 1.5 to 20 times, and more preferably 2.0 to 5 times, the amount of the silicate in terms of mass.

[0049]

[18] The method for producing a compound according to any one of

[14] to

[17] , wherein the proton exchange step is preferably carried out in a reaction medium; the reaction medium is more preferably an ether liquid having an ether bond, an alcohol liquid having a hydroxyl group, an amide liquid having an amide bond or an amide group, an ester liquid having an ester bond, a halogen liquid having a halogen atom, a nitrile liquid having a nitrile group, a ketone liquid having a carbonyl group, a sulfinyl liquid having a sulfinyl group, or water; further preferably tetrahydrofuran (THF), tetrahydropyran, dioxane, diethyl ether (Et2O), dimethyl ether, diisopropyl ether, diphenyl ether, methyl ethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, methanol, ethanol, n-propanol, isopropanol, formamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide (DMAc), urea, tetramethylurea, ethyl acetate, n-amyl acetate, ethyl lactate, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethane, hexachloroethane, acetonitrile, acetone, methyl ethyl ketone, phenyl methyl ketone, dimethyl sulfoxide (DMSO), or water.

[0050]

[19] The method for producing the compound according to

[18] , wherein the amount of the reaction medium used in the proton exchange step is preferably an amount such that the content of the silicate is 0.005 to 0.04 mol / L.

[0051]

[20] The method for producing a compound according to any one of

[14] to

[19] , wherein the compound Q + The cation is preferably an alkali metal ion, an alkaline earth metal ion, a transition metal ion, or an ammonium ion; more preferably a lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), magnesium ions (Mg 2+ ), calcium ions (Ca 2+ ), iron (III) ions (Fe 3+ ), copper (II) ions (Cu 2+ ), zinc ions (Zn 2+ ), ammonium ions (NH4 + ), tetramethylammonium ion (NMe4 + ), ethyltrimethylammonium ion (NEtMe 3+), diethyldimethylammonium ion (NEt2Me 2+ ), triethylmethylammonium ion (Net3Me + ), tetraethylammonium ion (NEt4 + ), tetrapropylammonium ion (NPr4 + ), tetrabutylammonium ion (NBu4 + ); more preferably sodium ion (Na + ), potassium ion (K + ), tetramethylammonium ion (NMe4 + ), tetraethylammonium ion (NEt4 + ), or ethyltrimethylammonium ion (NEtMe 3+ ).

[0052]

[21] The method for producing a compound according to any one of

[14] to

[20] , wherein the proton exchange step includes a separation step of separating the compound (10) as a powder from a solution containing the compound (10).

[0053]

[22] The method for producing the compound according to

[21] , wherein the separation step preferably includes adding a poor solvent to a solution containing the compound (10) to precipitate the compound (10), thereby isolating the compound (10) as a powder.

[0054]

[23] The method for producing the compound according to

[22] , wherein the poor solvent is hexane, benzene, toluene, dibutyl ether, diisopropyl ether, diethyl ether, dichloromethane, chloroform, or ethyl acetate; preferably hexane, benzene, diisopropyl ether, or ethyl acetate; more preferably diethyl ether or ethyl acetate.

[0055]

[24] Use of a silanol compound-containing composition for producing a functional silicon material, the silanol compound-containing composition containing the compound according to any one of [1] to [3].

[0056]

[25] Use of a composition containing a silanol compound as a functional silicon material, the composition containing a silanol compound containing the compound described in any one of [1] to [3], the functional silicon material being used to improve heat resistance, cold resistance, weather resistance, light resistance, high light transmittance, transparency, insulation, mold release properties, or water repellency.

[0057]

[26] Use of a silanol compound-containing composition for producing a polymer, the silanol compound-containing composition comprising the compound according to any one of [1] to [3].

[0058]

[27] Use of a silanol compound-containing composition for producing a porous body, the silanol compound-containing composition containing the compound according to any one of [1] to [3].

[0059]

[28] A method for producing a functional silicon material, comprising using a composition containing a silanol compound, wherein the composition containing a silanol compound contains the compound described in any one of [1] to [3].

[0060] Effects of the Invention

[0061] According to the present invention, a novel cage siloxane compound and a method for producing the same can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] Figure 1 The product obtained in Preparation Example 1 29 Si-NMR measurement results.

[0063] Figure 2 These are the measurement results of the product obtained in Production Example 1 by high-resolution mass spectrometry (TOF-MS).

[0064] Figure 3 This is an example of a proton exchange reaction formula in which a silicate having a structure represented by formula (10)' is allowed to act with an inorganic acid (such as hydrochloric acid) to generate a silanol compound.

[0065] Figure 4 Compound (1)-1 obtained in Example 1 1 H-NMR measurement results.

[0066] Figure 5 Compound (1)-1 obtained in Example 1 13 C-NMR measurement results.

[0067] Figure 6 Compound (1)-1 obtained in Example 1 29 Si-NMR measurement results.

[0068] Figure 7 These are the measurement results of compound (1)-1 obtained in Example 1 by high-resolution mass spectrometry (TOF-MS).

[0069] Figure 8 Compound (1)-2 obtained in Example 2 1 H-NMR measurement results.

[0070] Figure 9 Compound (1)-2 obtained in Example 2 13 C-NMR measurement results.

[0071] Figure 10 Compound (1)-2 obtained in Example 2 29 Si-NMR measurement results.

[0072] Figure 11 These are the measurement results of compound (1)-2 obtained in Example 2 by high-resolution mass spectrometry (TOF-MS).

[0073] Figure 12 Compound (1)-3 obtained in Example 3 1 H-NMR measurement results.

[0074] Figure 13 Compound (1)-3 obtained in Example 3 13 C-NMR measurement results.

[0075] Figure 14 Compound (1)-3 obtained in Example 3 29 Si-NMR measurement results.

[0076] Figure 15 These are the measurement results of compound (1)-3 obtained in Example 3 by high-resolution mass spectrometry (TOF-MS).

[0077] Figure 16 Compound (1)-4 obtained in Example 4 1 H-NMR measurement results.

[0078] Figure 17 Compound (1)-4 obtained in Example 4 13 C-NMR measurement results.

[0079] Figure 18 Compound (1)-4 obtained in Example 4 29 Si-NMR measurement results.

[0080] Figure 19 In the compound (1)-4 obtained in Example 4, one Z in formula (1) 5 is dimethylsilyl and 11 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0081] Figure 20 In the compound (1)-4 obtained in Example 4, the two Z in formula (1) 5 is dimethylsilyl and 10 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0082] Figure 21 In the compound (1)-4 obtained in Example 4, the three Zs in formula (1) 5 is dimethylsilyl and 9 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0083] Figure 22 In the compound (1)-4 obtained in Example 4, the four Zs in formula (1) 5 is dimethylsilyl and 8 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0084] Figure 23 In the compound (1)-4 obtained in Example 4, the five Zs in formula (1) 5 is dimethylsilyl and 7 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0085] Figure 24 In the compound (1)-4 obtained in Example 4, the six Zs in formula (1) 5 is dimethylsilyl and 6 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0086] Figure 25 In the compound (1)-4 obtained in Example 4, the 7 Z in formula (1) 5 is dimethylsilyl and 5 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0087] Figure 26 In the compound (1)-4 obtained in Example 4, the 8 Z in formula (1) 5 is dimethylsilyl and 4 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0088] Figure 27 In the compound (1)-4 obtained in Example 4, the nine Zs in formula (1) 5 is dimethylsilyl and 3 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0089] Figure 28In the compound (1)-4 obtained in Example 4, the 10 Z in formula (1) 5 is dimethylsilyl and 2 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0090] Figure 29 These are the measurement results of a series of compounds (1)-4 obtained in Example 4 by high-resolution mass spectrometry (TOF-MS).

[0091] Figure 30 Compound (1)-5 obtained in Example 5 1 H-NMR measurement results.

[0092] Figure 31 Compound (1)-5 obtained in Example 5 13 C-NMR measurement results.

[0093] Figure 32 Compound (1)-5 obtained in Example 5 29 Si-NMR measurement results.

[0094] Figure 33 In the compound (1)-5 obtained in Example 5, one Z in formula (1) 5 is dimethylvinyl and 11 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0095] Figure 34 In the compound (1)-5 obtained in Example 5, the two Z in formula (1) 5 is dimethylvinyl and 10 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0096] Figure 35 In the compound (1)-5 obtained in Example 5, the three Z in formula (1) 5 is dimethylvinyl and 9 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0097] Figure 36 In the compound (1)-5 obtained in Example 5, the four Z in formula (1) 5 is dimethylvinyl and 8 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0098] Figure 37 In the compound (1)-5 obtained in Example 5, the five Zs in formula (1) 5 is dimethylvinyl and 7 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0099] Figure 38 In the compound (1)-5 obtained in Example 5, the six Zs in formula (1) 5 is dimethylvinyl and 6 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0100] Figure 39 In the compound (1)-5 obtained in Example 5, the 7 Z in formula (1) 5 is dimethylvinyl and 5 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0101] Figure 40 In the compound (1)-5 obtained in Example 5, the 8 Z in formula (1) 5 is dimethylvinyl and 4 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0102] Figure 41 In the compound (1)-5 obtained in Example 5, the nine Zs in formula (1) 5 is dimethylvinyl and 3 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0103] Figure 42 In the compound (1)-5 obtained in Example 5, the 10 Z in formula (1) 5 is dimethylvinyl and 2 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0104] Figure 43 In the compound (1)-5 obtained in Example 5, the 11 Z in formula (1) 5 is dimethylvinyl and 1 Z 5 The results of high-resolution mass spectrometry (TOF-MS) analysis of trimethylsilyl compounds were obtained.

[0105] Figure 44These are the measurement results of a series of compounds (1)-5 obtained in Example 5 using high-resolution mass spectrometry (TOF-MS). DETAILED DESCRIPTION

[0106] <<Compound>>

[0107] The compound according to the embodiment of the present invention is a compound represented by the following general formula (1) (sometimes referred to as "compound (1)" in this specification).

[0108] [Chemical Formula 6]

[0109]

[0110] (In formula (1), multiple Z 5 Each independently is a hydrogen atom or -SiR 1 R 2 R 3 The groups shown, but multiple Z 5 At least one of them is -SiR 1 R 2 R 3 The groups shown;

[0111] R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are the above-mentioned groups, these groups may be combined with each other to form a ring.

[0112] In the general formula (1), Z 5 A hydrogen atom (-H) or a general formula "-SiR 1 R 2 R 3 "The group shown. Moreover, R 1 、R 2 and R 3 Each is independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group.

[0113] R 1 、R 2 and R 3 The alkyl group in the group may be linear, branched, or cyclic.

[0114] R 1 、R 2 and R 3The number of carbon atoms in the linear or branched alkyl group is not particularly limited, but is preferably 1 to 20.

[0115] Examples of such linear or branched alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,3-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl.

[0116] The number of carbon atoms in the linear or branched alkyl group is more preferably 1 to 10, and may be, for example, 1 to 6 or 1 to 3.

[0117] R 1 、R 2 and R 3 The cyclic alkyl group in may be monocyclic or polycyclic.

[0118] The number of carbon atoms in the cyclic alkyl group is not particularly limited as long as it is 3 or more, but is preferably 3 to 20.

[0119] Examples of the cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2-adamantyl, and tricyclodecyl.

[0120] The number of carbon atoms in the cyclic alkyl group is more preferably 3 to 15, and may be, for example, 3 to 10 or 3 to 6, or 5 to 15 or 5 to 10.

[0121] R 1 、R 2 and R 3 The alkyl group in may be a group in which a linear or branched chain structure and a cyclic structure are mixed.

[0122] Examples of the alkyl group having a mixed chain structure and a cyclic structure include: cyclopentylmethyl, 1-cyclopentylethyl, cyclohexylmethyl, 1-cyclohexylethyl, and the like, and groups having a structure in which one or two or more hydrogen atoms in the above-mentioned straight-chain or branched alkyl groups are replaced by the above-mentioned cyclic alkyl groups; methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, dimethylcyclohexyl, and the like, and groups having a structure in which one or two or more hydrogen atoms in the above-mentioned cyclic alkyl groups are replaced by the above-mentioned straight-chain or branched alkyl groups; and the like.

[0123] The number of carbon atoms in the alkyl group having a mixed chain structure and a cyclic structure is not particularly limited as long as it is 4 or more, but is preferably 4 to 25, and can be, for example, 6 to 15.

[0124] R 1 、R 2 and R 3 The alkenyl group in may be linear, branched, or cyclic.

[0125] R 1 、R 2 and R 3 The number of carbon atoms of the linear or branched alkenyl group in is not particularly limited, but is preferably 2 to 20.

[0126] Examples of such straight-chain or branched alkenyl groups include vinyl, 1-propenyl, 2-propenyl (allyl), 2-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, heptenyl, octenyl, nonenyl, and decenyl; isopropenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, and isopentenyl; butadienyl, pentadienyl, hexadienyl, and octadienyl.

[0127] The number of carbon atoms in the linear or branched alkenyl group is more preferably 2 to 10, and may be, for example, 2 to 6 or 2 to 3.

[0128] R 1 、R 2 and R 3 The cyclic alkenyl group in may be monocyclic or polycyclic.

[0129] The number of carbon atoms in the cyclic alkenyl group is not particularly limited as long as it is 3 or more, but is preferably 3 to 20.

[0130] Examples of the cyclic alkenyl group include 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl.

[0131] The number of carbon atoms in the cyclic alkenyl group is more preferably 3 to 15, and may be, for example, 3 to 10 or 3 to 6, or 5 to 15 or 5 to 10.

[0132] R 1 、R 2 and R 3 The alkenyl group in may be a group in which a linear or branched chain structure and a cyclic structure are mixed.

[0133] Examples of the alkenyl group in which such a chain structure and a cyclic structure exist in combination include: a group having a structure in which one or two or more hydrogen atoms in the above-mentioned straight-chain or branched alkenyl group are substituted by the above-mentioned cyclic alkenyl group; a group having a structure in which one or two or more hydrogen atoms in the above-mentioned cyclic alkenyl group are substituted by the above-mentioned straight-chain or branched alkenyl group; and the like.

[0134] The number of carbon atoms in the alkenyl group having a mixed chain structure and a cyclic structure is not particularly limited as long as it is 4 or more, but is preferably 4 to 25, and can be, for example, 6 to 15.

[0135] R 1 、R 2 and R 3 The aryl group in may be monocyclic or polycyclic.

[0136] The number of carbon atoms of the aryl group is preferably 6 to 20. Examples of the aryl group include phenyl, 1-naphthyl, 2-naphthyl, o-tolyl, m-tolyl, p-tolyl, and benzyl (dimethylphenyl). Examples ... 1 ~R 3 The aryl group having such a substituent preferably has 6 to 20 carbon atoms.

[0137] The aryl group more preferably has 6 to 12 carbon atoms.

[0138] R 1 、R 2 and R 3 The alkyl group, the alkenyl group, and the aryl group in each of the groups may have a substituent.

[0139] In this specification, it is not limited to R 1 、R 2 and R 3In the case of an alkyl group, an alkenyl group, or an aryl group, unless otherwise specified, the term "alkyl group, alkenyl group, or aryl group having a substituent" means that one or more hydrogen atoms constituting these groups are replaced by groups other than hydrogen atoms. Furthermore, in this specification, unless otherwise specified, "group" includes not only an atomic group consisting of a plurality of atoms bonded together but also a single atom.

[0140] As R 1 、R 2 and R 3 The substituents in the group include, for example, halogen atoms such as a chlorine atom, a bromine atom, and an iodine atom; a hydroxyl group; a carboxyl group; an alkyl group and an aryl group in which one methylene group (-CH2-) or two or more non-adjacent methylene groups are substituted with an oxygen atom (-O-), a carbonyloxy group (-C(=O)-O-) or an oxycarbonyl group (-OC(=O)-); and the like.

[0141] Examples of the alkyl group in the above-mentioned "alkyl group in which the methylene group is substituted with an oxygen atom, a carbonyloxy group or an oxycarbonyl group" include: 1 、R 2 and R 3 The alkyl group is the same as the alkyl group.

[0142] In the above-mentioned "alkyl group in which a methylene group is substituted with an oxygen atom, a carbonyloxy group, or an oxycarbonyl group," the position of the methylene group substituted with the substituent (oxygen atom, carbonyloxy group, or oxycarbonyl group) is not particularly limited, and the number of substituents may be 1 or 2 or more. When the number of substituents is 2 or more, these substituents may be the same as or different from each other.

[0143] R 1 、R 2 and R 3 Preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (a linear or branched alkyl group having 1 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms), an alkylene group having 2 to 20 carbon atoms (a linear or branched alkyl group having 2 to 20 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms), or an aryl group having 6 to 20 carbon atoms; more preferably, each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (a linear or branched alkyl group having 1 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms), an alkylene group having 2 to 6 carbon atoms (a linear or branched alkyl group having 2 to 6 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms), or an aryl group having 6 to 12 carbon atoms. In such an R 1 、R 2 and R 3 In any of the above, the alkyl group, the alkenyl group or the aryl group may have a substituent.

[0144] In the general formula "-SiR 1 R2 R 3 " In the group shown in 1 、R 2 and R 3 When two or more (2 or 3) of the groups are the alkyl groups, alkenyl groups or aryl groups, these groups (alkyl groups, alkenyl groups or aryl groups) may be bonded to each other and form a ring together with the silicon atom (Si) to which these groups are bonded.

[0145] R 1 、R 2 and R 3 The ring formed by bonding two or more of the rings is a silicon-containing aliphatic ring or a silicon-containing aromatic ring containing a silicon atom as an atom constituting a ring skeleton.

[0146] When the ring is formed, R 1 、R 2 or R 3 The binding position of is not particularly limited. For example, when R 1 、R 2 or R 3 When the alkyl, alkenyl or aryl group has a chain structure, the binding position may be a carbon atom at the terminal end of the chain structure or a non-terminal carbon atom. However, when the alkyl, alkenyl or aryl group has a substituent, the substituent is not located at the binding position when forming a ring.

[0147] When the ring is formed, R 1 、R 2 or R 3 The number of binding sites may be 1 or 2 or more. That is, the ring may be monocyclic or polycyclic.

[0148] In the general formula (1), multiple Z 5 They can be the same or different. 5 They may all be the same, all be different, or only partly be the same.

[0149] However, in general formula (1), not all Z 5 All are hydrogen atoms, and can have 1 or 2 or more Z 5 The general formula "-SiR 1 R 2 R 3 "The group shown can also be 12 Z 5 All of the general formula "-SiR 1 R 2 R 3 "The group shown.

[0150] In the general formula (1), one or more Z 5When Z is a hydrogen atom (ie, in compound (1), not all Z 5 All of the general formula "-SiR 1 R 2 R 3 " shown in the group), the general formula "-SiR 1 R 2 R 3 The binding position of the group represented by " is not particularly limited.

[0151] As the general formula "-SiR 1 R 2 R 3 " ", more specifically, for example, a group represented by: trialkylsilyl, dialkylsilyl, monoalkylsilyl, trialkenylsilyl, dialkenylsilyl, monoalkenylsilyl, triarylsilyl, diarylsilyl, monoarylsilyl, dialkylmonoarylsilyl, monoalkyldiarylsilyl, monoalkylmonoarylsilyl, dialkenylmonoarylsilyl, monoalkenyldiarylsilyl, monoalkenylmonoarylsilyl, dialkenylmonoalkylsilyl, monoalkenyldialkylsilyl, monoalkenylmonoalkylsilyl, silicon group (-SiH3) and the like. Among them, a trimethylsilyl group is preferred, a dimethylmonovinylsilyl group is more preferred, and a dimethylsilyl group is still more preferred.

[0152] <<Method for producing compound>>

[0153] The method for producing a compound according to an embodiment of the present invention is to react a compound represented by the following general formula (10) (sometimes referred to as "compound (10)" in this specification) with a compound represented by the following general formula (3) (sometimes referred to as "compound (3)" in this specification) to obtain a compound (1) represented by the following general formula (1).

[0154] [Chemical Formula 7]

[0155]

[0156] X-SiR 1 R 2 R 3 ……(3)

[0157] (In formula (3), R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are mentioned above, these groups may be combined with each other to form a ring; X is a halogen atom.

[0158] [Chemical Formula 8]

[0159]

[0160] (In formula (1), multiple Z 5 Each independently is a hydrogen atom or -SiR 1 R 2 R 3 The groups shown, but multiple Z 5 At least one of them is -SiR 1 R 2 R 3 The groups shown;

[0161] R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are the above-mentioned groups, these groups may be combined with each other to form a ring.

[0162] Compound (1) is the same as described above. Next, Compound (3) and Compound (10) will be described in detail.

[0163] <Compound (3)>

[0164] Compound (3) is represented by the general formula (3).

[0165] The monovalent group having the structure after removing X in compound (3) and Z in compound (1) 5 Zhongtong type "-SiR 1 R 2 R 3 ” are the same groups.

[0166] R in the general formula (3) 1 、R 2 and R 3 With R in general formula (1) 1 、R 2 and R 3 same.

[0167] In the general formula (3), X is a halogen atom.

[0168] Examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.

[0169] For example, as the compound (3) when X is a chlorine atom, more specific examples include trialkylsilyl chloride, dialkylsilyl chloride, monoalkylsilyl chloride, trialkenylsilyl chloride, dialkenylsilyl chloride, monoalkenylsilyl chloride, triarylsilyl chloride, diarylsilyl chloride, monoarylsilyl chloride, dialkylmonoarylsilyl chloride, monoalkyldiarylsilyl chloride, monoalkylmonoarylsilyl chloride, dialkenylmonoarylsilyl chloride, monoalkenyldiarylsilyl chloride, monoalkenylmonoarylsilyl chloride, dialkenylmonoalkylsilyl chloride, monoalkenyldialkylsilyl chloride, and monoalkenylmonoalkylsilyl chloride.

[0170] Next, the overall method for reacting compound (10) with compound (3) will be described.

[0171] <Reaction Conditions of Compound (10) and Compound (3)>

[0172] Compound (1) is obtained by reacting compound (10) with compound (3).

[0173] The compound (3) to be reacted may be only one or two or more, and may be appropriately selected according to the structure of the target compound (1).

[0174] When two or more compounds (3) are used, their combination and ratio can be appropriately adjusted according to the purpose.

[0175] In addition, in the present specification, when describing the number of species of compounds (1), (10), and (3), stereoisomers are not considered unless otherwise specified.

[0176] The amount of compound (3) used can be appropriately adjusted depending on the structure of the target compound (1) and the like.

[0177] For example, according to the general formula "-SiR 1 R 2 R 3 The amount of compound (3) used can be adjusted by the number of groups shown in FIG.

[0178] For example, regardless of the value of p1, when the amount of compound (3) used is 1 to 2 times the molar amount of compound (10), the general formula "-SiR 1 R 2 R 3 " is a compound (1) in which the number of groups represented by " is 1 to 2.

[0179] For example, regardless of the value of p1, when the amount of compound (3) used is 3 to 4 times the molar amount of compound (10), the general formula "-SiR 1 R 2 R 3 " is a compound (1) in which the number of groups represented by " is 3 to 4.

[0180] For example, regardless of the value of p1, when the amount of compound (3) used is 5 to 6 times the molar amount of compound (10), the general formula "-SiR 1 R 2 R 3 The compound (1) wherein the number of the groups represented by " is 5 to 6.

[0181] For example, when p1 is 0, when the amount of compound (3) used is 6 times the molar amount of compound (10) used, the compound of the general formula "-SiR 1 R 2 R 3 In this case, for example, when the amount of compound (3) used is 10 times the molar amount or less, excessive use of compound (3) can be suppressed.

[0182] For example, when the amount of compound (3) used is 7 to 8 times the molar amount of compound (10), the general formula "-SiR 1 R 2 R 3 " is a compound (1) in which the number of groups represented by " is 7 to 8.

[0183] For example, when the amount of compound (3) used is 8 times the molar amount of compound (10) used, the compound of the general formula "-SiR 1 R 2 R 3 " is a compound (1) in which the number of groups represented by " is 8. In this case, for example, when the amount of compound (3) used is preferably 17 times the molar amount or less, more preferably 12 times the molar amount or less, excessive use of compound (3) can be suppressed.

[0184] For example, when the amount of compound (3) used is 9 to 10 times the molar amount of compound (10), the general formula "-SiR 1 R 2 R 3 " is a compound (1) in which the number of groups represented by " is 9 to 10.

[0185] For example, when the amount of compound (3) used is 10 times the molar amount of compound (10) used, the compound of the general formula "-SiR 1 R 2 R 3 The number of groups represented by " is 10" in the compound (1).

[0186] For example, when the amount of compound (3) used is 12 times the molar amount of compound (10) used, the compound of the general formula "-SiR 1 R 2 R 3 The number of groups represented by " is 12" in the compound (1).

[0187] In this case, for example, when the amount of compound (3) used is 18-fold or less by mole, excessive use of compound (3) can be suppressed.

[0188] The amount of compound (3) used described above is an example for obtaining the target compound (1) efficiently and in good yield, and the amount of compound (3) used can be appropriately adjusted in consideration of the overall production conditions of compound (1).

[0189] In addition, the usage amount of the compound (3) described above refers to the total usage amount of all types of the compound (3) used when two or more types of the compound (3) are used.

[0190] [Alkali]

[0191] When compound (10) is reacted with compound (3), it is preferred to use a base. By using a base, the amount of compound (1) produced increases significantly.

[0192] The base is preferably an organic base.

[0193] Examples of the organic base include aromatic amines such as aniline, pyridine, and piperidine; and aliphatic amines such as triethylamine and diisopropylethylamine.

[0194] When the above-mentioned bases are used, one type may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio thereof may be appropriately adjusted according to the intended purpose.

[0195] When the base is used, the amount of the base used can be adjusted according to the amount of compound (3) used, for example.

[0196] In this case, the amount of the base used is preferably 1 to 2 times the molar amount of the compound (3), for example, 1 to 1.5 times the molar amount. By setting the amount of the base used to 1 time or more, the amount of compound (1) produced is further increased. By setting the amount of the base used to 2 times or less, excessive use of the base can be suppressed.

[0197] [Solvent]

[0198] The reaction between compound (10) and compound (3) can be carried out without using a solvent, but is preferably carried out using a solvent. By using a solvent, the fluidity of the reaction solution can be improved, the reaction between compound (10) and compound (3) can be carried out more smoothly, and the amount of by-products generated can be reduced.

[0199] The solvent is preferably a substance that is non-reactive with the components used for the reaction, such as compound (10) and compound (3).

[0200] Examples of the solvent include ethers (compounds having an ether bond) such as tetrahydrofuran (THF), 1,4-dioxane, tetrahydropyran, dibutyl ether, and 1,2-dimethoxyethane; amides such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMAc); esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons (hydrocarbons having a halogen atom as a substituent) such as 1,2-dichloroethane, dichloromethane, and chlorobenzene; nitriles (compounds having a cyano group) such as propionitrile and acetonitrile; and hydrocarbons such as toluene, n-hexane, and methylcyclohexane.

[0201] When a solvent is used, one type of the solvent may be used alone, or two or more types may be used in combination. When two or more types are used in combination, the combination and ratio thereof may be appropriately adjusted according to the intended purpose.

[0202] The amount of the solvent used is not particularly limited, and for example, is preferably 0 to 100 mL, more preferably 10 to 50 mL, relative to 1 mmol of compound (10). By setting the amount of the solvent used to 10 mL or more, the effect of using the solvent can be more significantly achieved. By setting the amount of the solvent used to 100 mL or less, excessive use of the solvent can be suppressed.

[0203] [Other ingredients]

[0204] When the compound (10) and the compound (3) are reacted, other components other than the compound (10), the compound (3), the base, and the solvent may be used within the range not impairing the effects of the present invention.

[0205] The types of the other components are not particularly limited and may be arbitrarily selected according to the intended purpose.

[0206] When the other components are used, they may be used alone or in combination of two or more. When two or more are used in combination, the combination and ratio thereof may be appropriately adjusted according to the intended purpose.

[0207] When the other components are used, the amount of the other components used is not particularly limited and can be arbitrarily selected according to the type of the other components.

[0208] [Other reaction conditions]

[0209] The reaction temperature during the reaction of compound (10) and compound (3) may be appropriately adjusted and is not particularly limited.

[0210] The reaction temperature is preferably 10°C to 40°C, and may be, for example, 18°C ​​to 30°C or room temperature.

[0211] The reaction time for the reaction of compound (10) with compound (3) is not particularly limited and may be appropriately adjusted according to other conditions such as reaction temperature so as to increase the amount of compound (1) produced.

[0212] The reaction time is, for example, preferably 1 to 72 hours, more preferably 1 to 60 hours.

[0213] In the method for producing the compound of this embodiment, after completion of the reaction, post-treatment may be performed by a known method as needed, and then compound (1) may be taken out by a known method.

[0214] For example, after the reaction is completed, any one of the post-treatment operations such as filtration, washing, extraction, pH adjustment, dehydration, and concentration can be performed individually or in combination of two or more of these post-treatment operations as appropriate, and then compound (1) can be removed by concentration, crystallization, reprecipitation, column chromatography, etc. Furthermore, the removed compound (1) can be purified by performing any one of the operations such as crystallization, reprecipitation, column chromatography, extraction, and stirring and washing the crystals with a solvent individually or in combination of two or more of these operations once or twice as appropriate.

[0215] When another step using compound (1) is continued after the reaction, after the reaction, post-treatment may be performed by a known method as needed, and then the other step may be continued without removing compound (1).

[0216] When multiple compounds (1) are produced by the reaction of compound (10) and compound (3), the target compound (1) can be obtained by appropriately selecting and performing either or both of the above-mentioned post-treatment operations and purification operations. Even if multiple compounds (1) are produced, their properties can be inferred from the structure of the compound (1). Therefore, by selecting a post-treatment operation or purification operation suitable for their properties, the yield of the target compound (1) can be increased.

[0217] Furthermore, the yield of compound (1) can be increased by adjusting the amount of compound (3) used, other reaction conditions, etc. to increase the yield of target compound (1).

[0218] The structure of compound (1) can be confirmed by known methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), infrared spectroscopy (IR), ultraviolet / visible spectroscopy (UV-VIS absorption spectroscopy), and elemental analysis.

[0219] <Compound (10)>

[0220] In the method for producing a compound according to the present embodiment, the compound (10) is a silanol compound represented by the following formula (10).

[0221] [Chemical Formula 9]

[0222]

[0223] Since the silanol compound of compound (10) has the above-mentioned structure, it does not undergo dehydration condensation even in the absence of a crystallization solvent and can be isolated as a single powder.

[0224] Conventional silanol compounds, such as the cage-type octamer (Q8H8) of orthosilicic acid (Si(OH)4), undergo dehydration condensation in the absence of a crystallization solvent (such as an amide solvent) for coordination stabilization, and therefore cannot be isolated as a single powder.

[0225] On the other hand, the silanol compound of compound (10) can be kept stable as a single powder (eg, with a purity of 100%) and is therefore easy to handle, which is extremely advantageous in material development.

[0226] Furthermore, in this embodiment, the silanol compound of compound (10) can be confirmed by various NMR, high-resolution mass spectrometry, and X-ray crystal structure analysis.

[0227] <Method for producing compound (10)>

[0228] The silanol compound of compound (10) can be obtained by a method for producing a silanol compound including a proton exchange step, wherein a silicate having a structure represented by the following formula (10)' (hereinafter sometimes referred to as "silicate") is reacted with an acidic compound to obtain a solution containing the silanol compound represented by the following formula (10) (hereinafter sometimes referred to as "proton exchange step").

[0229] [Chemical Formula 10]

[0230]

[0231] (In formula (10)', Q + represents a cation.)

[0232] [Chemical Formula 11]

[0233]

[0234] In addition, the method for producing a silanol compound of compound (10) preferably further includes a step of adding a poor solvent to the solution obtained in the proton exchange step to precipitate the silanol compound represented by formula (10), thereby isolating the silanol compound represented by formula (10) as a powder (hereinafter sometimes referred to as the "separation step").

[0235] The silicate, acidic compound, and other reaction conditions in the proton exchange step will be described in detail below.

[0236] (Proton exchange process)

[0237] The specific type of silicate used in the proton exchange step, the specific type of the acidic compound, the amount of the acidic compound used, the type of the reaction medium as a solvent or dispersion medium, the reaction conditions, etc. are not particularly limited and can be appropriately selected depending on the purpose.

[0238] The acidic compound used in the proton exchange step is preferably an acidic compound having an acid dissociation constant pKa in dimethyl sulfoxide (DMSO) (hereinafter sometimes simply referred to as "pKa (DMSO)") of -1 to 20.

[0239] By exchanging protons with acidic compounds having a pKa (DMSO) of -1 to 20, silanol compounds tend to be produced efficiently. When the pKa (DMSO) is -1 to 20, the cation (Q + ) and the protons (H +) is efficiently exchanged and side reactions can be suppressed. Therefore, the silanol compound itself can be synthesized with a good yield. In addition, the method for producing the silanol compound of compound (10) is to react rapidly under mild conditions, and is therefore an industrially very suitable production method. In addition, the smaller the pKa (DMSO), the faster the proton exchange process tends to proceed.

[0240] In addition, pKa (DMSO) is a known value calculated from the concentration of each component of the acid dissociation equilibrium of the acidic compound in DMSO at 25° C. Specifically, it is a value obtained by performing common logarithm conversion on the value Ka calculated by the following formula.

[0241] [Mathematical formula 1]

[0242]

[0243]

[0244] In the proton exchange step, a silicate having a structure represented by the following formula (10)' is reacted with an acidic compound.

[0245] [Chemical Formula 12]

[0246]

[0247] (In formula (10)', Q + represents a cation.)

[0248] In formula (10)', regarding Q + The cation is not particularly limited, and examples thereof include lithium ions (Li + ), sodium ion (Na + ), potassium ion (K + ) and other alkali metal ions; magnesium ions (Mg 2+ ), calcium ions (Ca 2+ ) and other alkaline earth metal ions; iron (III) ions (Fe 3+ ), copper (II) ions (Cu 2+ ), zinc ions (Zn 2+ ) and other transition metal ions; ammonium ions (NH4 + ), tetramethylammonium ion (NMe4 + ), ethyltrimethylammonium ion (NEtMe3 + ), diethyldimethylammonium ion (NEt2Me2 + ), triethylmethylammonium ion (Net3Me + ), tetraethylammonium ion (NEt4 + ), tetrapropylammonium ion (NPr4 +), tetrabutylammonium ion (NBu4 + Among them, sodium ions (Na + ), potassium ion (K + ), tetramethylammonium ion (NMe4 + ), tetraethylammonium ion (NEt4 + ), and ethyltrimethylammonium ion (NEtMe3 + ).

[0249] In the proton exchange step, the silicate to be reacted with the acidic compound is not particularly limited, and may be, for example, a cage-type potassium silicate 12mer (Q) in which two α-cyclodextrins (αCD) are coordinated vertically as shown in Angew. Chem. Int. Ed. Engl. 1997, 36, 743. 12 K 12 ) hydrate (potassium-2,4,6,8,10,12,14,16,18,20,22,24,25,26,27,28,29,30-octadeca-1,3,5,7,9,11,13,15,17,19,21,23-dodecasilylheptacyclo[13.9.1.13,13.15,11.17,21.19,19.117,23]triacontyl-1,3,5,7,9,11,13,15,17,19,21,23-dodeca (alkoxide) bis(α-dextrin) hydrate (dodecakali um-2,4,6,8 ,10,12,14,16,18,20,22,24,25,26,27,28,29,30-オクタデカオキサ- 1, 3, 5, 7, 9, 11, 13, 15, 17, 19, 21, 23-ドデカシラヘプタシクロ[13.9.1.13 , 13.15, 11.17, 21.19, 19.117, 23] トリアコンタン-1, 3, 5, 7, 9, 11, 13 , 15, 17, 19, 21, 23-ドデカキス (オラート)ビス (α-デキストリン) water and substance) (hereinafter sometimes referred to as "Q" 12 K 12 ·2αCD·nH2O”)).

[0250] [Chemical Formula 13]

[0251]

[0252] As this Q 12 K 12·2αCD·nH2O is not particularly limited and can be prepared, for example, with reference to the description in Angew. Chem. Int. Ed. Engl. 1997, 36, 743., Crystals 2018, 8, 457.

[0253] The acidic compound preferably has a pKa (DMSO) of -1 to 20. The pKa (DMSO) of the acidic compound is preferably 0 or greater, more preferably 1 or greater, and even more preferably 2 or greater, and is preferably 16 or less, more preferably 14 or less, and even more preferably 8 or less. When the pKa (DMSO) of the acidic compound is within the above range, the silanol compound can be efficiently produced.

[0254] Specific examples of acidic compounds are not particularly limited, but include inorganic acids such as nitric acid (pKa(DMSO) is 1.4), sulfuric acid (pKa1(DMSO) is 1.4, pKa2(DMSO) is 14.7), hydrochloric acid (pKa(DMSO) is 2.1), phosphoric acid (pKa1(DMSO) is 1.83, pKa2(DMSO) is 6.43, pKa3(DMSO) is 11.46), and acetic acid, or at least one organic acid selected from the group consisting of compounds having structures represented by the following formulas (b-1) to (b-5).

[0255] [Chemical Formula 14]

[0256]

[0257] (In formulas (b-1) to (b-5), L each independently represents an oxygen atom, a sulfur atom or an amino group (-NR c -), R a represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, R b Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms.

[0258] In N,N-dimethylacetamide (hereinafter also referred to as "DMAc"), methanol (hereinafter also referred to as "MeOH"), etc. as the reaction medium described below, if an organic acid is used to carry out a proton exchange reaction, the ammonium salt or alkali metal salt generated will dissolve in the reaction medium. Therefore, it is preferred to separate the ammonium salt or alkali metal salt as a by-product by column purification or the like. On the other hand, in tetrahydrofuran (hereinafter also referred to as "THF"), etc. as the reaction medium described below, if an inorganic acid is used to carry out a proton exchange reaction, the ammonium salt or alkali metal salt generated, as well as α-dextrin and chemical species derived from α-dextrin, are not easily dissolved in the reaction medium. Therefore, the ammonium salt or alkali metal salt can be separated by a simple separation means such as filtration with a filter to obtain a silanol compound solution as a filtrate. Therefore, the acidic compound is preferably an inorganic acid.

[0259] Among inorganic acids, nitric acid, sulfuric acid, hydrochloric acid, and phosphoric acid are preferred, nitric acid or hydrochloric acid is more preferred, and hydrochloric acid is particularly preferred. Hydrochloric acid is inexpensive, and the yield tends to be higher when hydrochloric acid is used.

[0260] In addition, the wavy line in the above formula (b-2) to (b-5) means that the front end thereof is an arbitrary structure. For example, the acidic compound may contain a functional group that does not participate in the reaction. Therefore, for example, as an acidic compound having a structure shown in the above formula (b-4), it may be a compound containing a hydrocarbon group such as a methyl group at the front end of the oxygen atom corresponding to L, such as dimethyl malonate shown in the following formula. In addition, for example, as an acidic compound having a structure shown in the above formula (b-4), it may be a compound in which the hydrocarbon group at the front end of the oxygen atom corresponding to L is bonded to form a cyclic structure, such as Meldrum's acid shown in the following formula.

[0261] [Chemical Formula 15]

[0262]

[0263] It is known that the structures shown in the above formulas (b-1) to (b-5) are so-called β-dicarbonyl structures, but the hydrogen of the methylene group sandwiched between the two carbonyl groups, i.e., α-hydrogen, acts as an acid site. By having the structures shown in the above formulas (b-1) to (b-5), the acidic compound exhibits a suitable acid dissociation constant, and the electrons of the anions generated by the dissociation of the protons are delocalized within the structure. For example, as an acidic compound having a structure shown in the above formula (b-2), proton dissociation is performed as shown in the following formula. Therefore, it can be considered that the alkalinity and nucleophilicity of the anions of the acidic compounds having the structures shown in the above formulas (b-1) to (b-5) are suppressed, thereby effectively suppressing side reactions.

[0264] [Chemical Formula 16]

[0265]

[0266] Regarding the amino group (-NR c -), for example, a secondary amino group (-NH-). L is particularly preferably an oxygen atom. R a When it is a hydrocarbon group, the number of carbon atoms is preferably 6 or less, more preferably 5 or less, and further preferably 4 or less. a , is not particularly limited, and examples thereof include: a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), a n-propyl group (-nPr), an isopropyl group (-iPr), a n-butyl group (-nBu), and a phenyl group (-Ph), but a hydrogen atom is preferred.

[0267] Rb When it is a hydrocarbon group, the number of carbon atoms is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less. b Examples thereof include a hydrogen atom, a methyl group (—Me), an ethyl group (—Et), an n-propyl group (—nPr), an isopropyl group (—iPr), and an n-butyl group (—nBu), and a hydrogen atom is preferred.

[0268] The acidic compound represented by the above formula (b-4) is not particularly limited, and examples thereof include the acidic compound represented by the following formula (b-4-1). The acidic compound represented by the above formula (b-5) includes the acidic compound represented by the following formula (b-5-1).

[0269] [Chemical Formula 17]

[0270]

[0271] (In formulas (b-4-1) and (b-5-1), R a represents a hydrogen atom or a hydrocarbon group having 1 to 14 carbon atoms, R d represents a divalent hydrocarbon group having 1 to 14 carbon atoms.

[0272] As R d , are not particularly limited, and examples thereof include: methylene (-CH2-), ethylene (-CH2CH2-), n-propylene (-CH2CH2CH2-), dimethylmethylene (-C(CH3)2-), and isopropylene (-CH(CH3)CH2-).

[0273] Specific examples of acidic compounds are not particularly limited, and include: acetic acid (pKa (DMSO) is 12.6), benzoic acid (pKa (DMSO) is 11.1), Michaelis acid (pKa (DMSO) is 7.3), Michaelis acid derivatives, dimedone (pKa (DMSO) is 11.2), dimedone derivatives, acetylacetone (pKa (DMSO) is 13.3), and acetylacetone derivatives (see the following formula).

[0274] [Chemical Formula 18]

[0275]

[0276] As acidic compounds, it is possible to utilize low molecular weight compounds such as Michaelis' acid, organic solid materials such as resins or inorganic solid materials such as silicon dioxide and carbon, and to import the materials obtained by the compounds shown in the above-mentioned formulas (b-2) to (b-5). If the acidic compound is such a solid, it can be filled in a column and utilized like an ion exchange resin. Therefore, silanol compounds can be manufactured very efficiently. As acidic compounds, general solid acids (such as AmberLyst, AmberLite, etc.) can be used.

[0277] In particular, the acidic compound is preferably a resin having at least one structure selected from the group consisting of the above formulas (b-2) to (b-5), and is preferably a substance that can be regenerated into an acidic compound by exposure to an acidic aqueous solution such as hydrochloric acid after a proton exchange step.

[0278] In the proton exchange step, the usage amount of the acidic compound is, relative to silicate, converted with amount of substance, usually more than 1 time, preferably more than 1.5 times, more preferably more than 2.0 times, and usually less than 50 times, preferably less than 20 times, more preferably less than 5 times. If the usage amount of the acidic compound is within the above range, silanol compounds can be manufactured efficiently.

[0279] The reaction in the proton exchange step is preferably carried out in a liquid (reaction medium). Such a reaction medium is not particularly limited, and examples thereof include: ether liquids such as tetrahydrofuran (THF), tetrahydropyran, dioxane, diethyl ether (Et2O), dimethyl ether, diisopropyl ether, diphenyl ether, methyl ethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; alcohol liquids such as methanol, ethanol, n-propanol, and isopropanol; amide liquids such as formamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide (DMAc), urea, and tetramethylurea; ester liquids such as ethyl acetate, n-amyl acetate, and ethyl lactate; halogen liquids such as dichloromethane, chloroform, carbon tetrachloride, tetrachloroethane, and hexachloroethane; acetonitrile, acetone, methyl ethyl ketone, phenyl methyl ketone, dimethyl sulfoxide (DMSO), and water.

[0280] Furthermore, the reaction medium is not limited to one type, and two or more types may be combined.

[0281] The amount of the reaction medium used in the proton exchange step is preferably an amount that makes the content of silicate 0.005 to 0.04 mol / L. This is because, if it is the content of the silicate, silanol compounds can be efficiently manufactured. The reaction temperature in the proton exchange step is usually above -80°C, preferably above 0°C, more preferably above 20°C, and usually below 200°C, preferably below 70°C, more preferably below 40°C. The reaction time in the proton exchange step is usually below 48 hours, preferably below 24 hours, more preferably below 8 hours, and particularly preferably below 1 hour. If within the above range, silanol compounds can be efficiently manufactured.

[0282] (Separation process)

[0283] The method for producing a silanol compound of compound (10) preferably includes the following step: adding a poor solvent to the solution of the silanol compound represented by formula (10) obtained in the proton exchange step to precipitate the silanol compound represented by formula (10), thereby isolating the silanol compound represented by formula (10) as a powder. By including such a step, the method for producing a silanol compound of compound (10) can easily and easily isolate the silanol compound represented by formula (10) as a single powder without causing dehydration condensation even in the absence of a crystallization solvent.

[0284] The poor solvent used to precipitate the silanol compound represented by the above formula (10) is not particularly limited, and examples thereof include hexane, benzene, toluene, dibutyl ether, diisopropyl ether, diethyl ether, dichloromethane, chloroform, and ethyl acetate. Among them, hexane, benzene, diisopropyl ether, and ethyl acetate are preferred, and diethyl ether and ethyl acetate are particularly preferred.

[0285] In addition, in the separation step, when using a precursor (such as Q 12 K 12 When the silicate reacts with the acidic compound (e.g., αCD and its decomposition product), it is preferable to use a solvent that dissolves the ligand and its decomposition product (e.g., αCD and its decomposition product) as a poor solvent for precipitating the silanol compound represented by the above formula (10).

[0286] The boiling point of the poor solvent used to precipitate the silanol compound represented by formula (10) is usually 0°C or higher, preferably 10°C or higher, more preferably 30°C or higher, and usually 300°C or lower, preferably 200°C or lower, more preferably 150°C or lower.

[0287] The solution obtained in the proton exchange step is preferably a concentrated solution obtained by filtering out the salts generated during the reaction and concentrating the filtrate. By using this concentrated solution, the silanol compound represented by the above formula (10) can be precipitated more efficiently.

[0288] In the separation process, the time for separating the silanol compound shown in the above formula (10) is not particularly limited, and can be appropriately selected, usually less than 24 hours, preferably less than 12 hours, more preferably less than 6 hours, and usually more than 0.25 hours, preferably more than 0.5 hours, more preferably more than 1 hour. When the silanol compound is separated, the particles separated out by stirring become uniform and are easily powdered in the drying process.

[0289] The method for isolating the silanol compound represented by the above formula (10) as a powder is not particularly limited, and an example thereof is filtration.

[0290] Furthermore, the powder of the silanol compound represented by the above formula (10) obtained by such a separation method is preferably dried. The drying temperature, drying pressure, drying time, etc. are not particularly limited and can be appropriately selected according to the purpose.

[0291] <Silanol compound-containing composition>

[0292] In the method for producing the compound of this embodiment, a composition containing the above-mentioned compound (10) (hereinafter sometimes referred to as "silanol compound-containing composition") can be used as a raw material.

[0293] There are no particular limitations on the types of compounds other than the silanol compound represented by the above formula (10) contained in the composition containing the silanol compound, and they can be appropriately selected according to the purpose. In addition, as described above, since the compound (10) can be isolated as a single powder (with a purity of 100%), the content of the compound (10) in the composition containing the silanol compound can be appropriately adjusted. The content of the compound (10) in the composition containing the silanol compound is not particularly limited. For example, it is preferably 0.1 to 99.9% by mass, more preferably 25 to 50% by mass, further preferably 50 to 70% by mass, and particularly preferably 70 to 99% by mass, relative to the total mass of the composition containing the silanol compound.

[0294] The compound contained in the silanol compound-containing composition other than the silanol compound represented by the above formula (10) is not particularly limited, and examples thereof include water, ether compounds, amine compounds, amide compounds, ammonium salts, and metal complexes.

[0295] As an amine compound, as long as it has an amino group (which can be any of a primary amine, a secondary amine, and a tertiary amine), the specific type is not particularly limited. In addition, compounds having both an amino group and an amide group are classified as "amide compounds". As amine compounds, for example, aniline (NH2Ph), diphenylamine (NHPh2), lutidine (Me2Pyr), di-tert-butylpyridine (tBu2Pyr), pyrazine (Pyraz), triphenylamine (NPh3), triethylamine (Et3N), and diisopropylethylamine (iPR2EtN) can be mentioned. Among the amine compounds, aniline (NH2Ph) is particularly preferred. In addition, the amine compound contained in the composition is not limited to one type, and may also contain two or more types.

[0296] The content of the amine compound in the silanol compound-containing composition (the total content when two or more types are included) is preferably greater than 0.1% by mass, more preferably 1% by mass or more, and even more preferably 10% by mass or more, relative to the total mass of the composition, and is usually less than 95% by mass, preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0297] The amide compound is not particularly limited as long as it has an amide bond. Examples of the amide compound include compounds represented by the following formula (i) or (ii).

[0298] [Chemical Formula 19]

[0299]

[0300] (In formulas (i) and (ii), R' and R" each independently represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

[0301] There are no particular limitations on R' and R", and examples thereof include a hydrogen atom, a methyl group (-Me), an ethyl group (-Et), an n-propyl group (-nPr), an isopropyl group (-iPr), and a phenyl group (-Ph). There are no particular limitations on the compound represented by the above formula (i), and examples thereof include formamide, DMF, acetamide, N-methylacetamide, and DMAc. There are no particular limitations on the compound represented by the above formula (ii), and examples thereof include urea and tetramethylurea (Me4Urea). The content of the amide compound in the composition containing the silanol compound (the total content when two or more are included) can be 0% by mass or more (not included) and 90% by mass or less relative to the total mass of the composition.

[0302] Regarding ammonium salts, any compound consisting of an ammonium ion and a counter anion is sufficient, and the specific type is not particularly limited. As ammonium ions, there are no particular limitations, for example, tetrahydroammonium ions (NH4 +), tetramethylammonium ion (NMe4 + ), tetraethylammonium ion (NEt4 + ), tetrapropylammonium ion (NPr4 + ), tetrabutylammonium ion (NBu4 + ), benzyltributylammonium ion (NBnBu3 + ), tributyl (methyl) ammonium (NBu3Me + ) ion, tetrapentylammonium ion (NPen4 + ), tetrahexylammonium ion (NHex4 + ), tetraheptyl ammonium ion (NHep4 + ), 1-butyl-1-methylpyrrolidinium ion (BuMePyr + ), methyl trioctyl ammonium ion (NMeOct3 + ), dimethyldioctadecyl ammonium ion, hydrogen pyridinium ion (C5H5N + H), hydroanilinium ion (PhNH2 + H), trimethyladamantyl ammonium ion and Michaelisate ion. In addition, as a counter anion, for example, there can be mentioned: fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ), iodide ion (I - ), acetoxy ion (AcO - ), nitrate ions (NO3 - ), azide ion (N3 - ), tetrafluoroborate ion (BF4 - ), perchlorate ion (ClO4 - ), and sulfate ions (HSO4 - ).

[0303] As ammonium salts, tetrabutylammonium chloride (NBu4Cl), tetrabutylammonium bromide (NBu4Br), tetrapentylammonium chloride (NPen4Cl), dimethyldioctadecylammonium chloride, trimethyladamantylammonium hydroxide, and Michaelis acid-tetramethylammonium salt are particularly preferred. Furthermore, the ammonium salt contained in the composition is not limited to one type, and two or more types may be contained.

[0304] The content of the ammonium salt in the silanol compound-containing composition (the total content when containing two or more kinds) is preferably greater than 0.1% by mass, more preferably 50% by mass or more, and usually less than 95% by mass, preferably 80% by mass or less, relative to the total mass of the composition. In addition, the ratio of the ammonium salt to the silanol compound in the silanol compound-containing composition (total mass of ammonium salts / total mass of silanol compounds) is preferably greater than 0, more preferably 1 or more, and usually 12 or less, preferably 8 or less, and more preferably 6 or less.

[0305] Example

[0306] The present invention will be described in more detail below through specific examples, but the present invention is not limited to the examples shown below.

[0307] The meanings of the abbreviations used in this example are as follows.

[0308] AcOEt: ethyl acetate

[0309] THF: Tetrahydrofuran

[0310] Me:methyl

[0311] Vi: Vinyl

[0312] The yield of compound (1) shown below is based on compound (10).

[0313] Hereinafter, "mmol" means "10 -3 Moore".

[0314] Hereinafter, the names of the individual compounds of compound (1) are identified by the symbols attached to the expressions using these compounds. For example, the "compound represented by formula (1)-1" described below is referred to as "compound (1)-1".

[0315] <Production of silanol compound (compound (10))>

[0316] [Production Example 1] Synthesis of Compound (10)

[0317] Potassium-2,4,6,8,10,12,14,16,18,20,22,24,25,26,27,28,29,30-octadeca-1,3,5,7,9,11,13,15,17,19,21,23-dodecasilheptacyclo[13.9.1.13,13.15,11.17,21.19,19.117,23]triacontyl-1,3,5,7,9,11,13,15,17,19,21,23-dodeca(oxide)bis(α-dextrin)hydrate (hereinafter sometimes referred to as “Q 12 K 12·2αCD·nH2O”), 0.823 g (0.200 mmol) of Q 12 K 12 ·2αCD·49.2H2O was suspended in 10 mL of THF (reaction solvent), and 0.501 mL (6.00 mmol) of hydrochloric acid was added to the resulting dispersion, and the mixture was stirred for 15 minutes to obtain a suspension. The suspension was filtered to obtain a filtrate.

[0318] 10 mL of ethyl acetate (poor solvent) was added to the obtained filtrate and stirred for 10 minutes to allow it to precipitate again (solid matter was precipitated). The suspension was filtered to separate the solid matter. After the solid matter was recovered, it was dried under reduced pressure to obtain the composition Si with a yield of 90% (0.170 g). 12 O 30 H 12 The compound represented by the following formula (10), namely, 2,4,6,8,10,12,14,16,18,20,22,24,25,26,27,28,29,30-octadecaoxa-1,3,5,7,9,11,13,15,17,19,21,23-dodecasilheptacyclo[13.9.1.13,13.15,11.17,21.19,19.117,23]triacontyl-1,3,5,7,9,11,13,15,17,19,21,23-dodecanol (CAS No. 126347-25-9 (compound (10)) was isolated as a colorless solid (powder). In addition, the colorless solid (powder) of compound (10) was dissolved in deuterated DMSO-d6 and subjected to NMR measurement. 1 H-NMR observed a peak at 7.07 ppm, 29 Si-NMR observed a peak at -101.2 ppm. 29 The results of Si-NMR measurements are as follows Figure 1 In addition, Q 12 H 12 The colorless solid (powder) was dissolved in a mixed solvent of dimethyl sulfoxide and acetonitrile and subjected to high-resolution mass spectrometry (TOF-MS). The results showed that the 12 O 30 Si 12 The theoretical value of Na[M+Na] is 850.6537, and the measured value is 850.6538. The results of high-resolution mass spectrometry (TOF-MS) are as follows Figure 2As shown. Various NMR and high-resolution mass spectrometry analyses above confirmed that the product obtained in Preparation Example 1 was compound (10) having the structure shown in the following formula (10). It was found that compound (10) could be kept stable as a single powder (purity 100%).

[0319] [Chemical Formula 20]

[0320]

[0321] [Production Example 2] Synthesis of Compound (10)

[0322] 6.845 g (1.602 mmol) of Q 12 K 12 ·2αCD·59.3H2O was suspended in 80 mL of THF (reaction solvent), and 3.924 mL (46.99 mmol) of hydrochloric acid was added to the resulting dispersion, followed by stirring for 15 minutes to obtain a suspension. The suspension was filtered to obtain a filtrate.

[0323] 80 mL of ethyl acetate (poor solvent) was added to the obtained filtrate and stirred for 60 minutes to cause it to precipitate again (solid matter was precipitated). The suspension was filtered to separate the solid matter. After the solid matter was recovered, it was dried under reduced pressure to isolate the compound (10) as a colorless solid (powder) with a yield of 74% (1.167 g).

[0324] [Production Example 3] Synthesis of Compound (10)

[0325] 6.886 g (1.602 mmol) of Q 12 K 12 ·2αCD·59.3H2O was suspended in 80 mL of THF (reaction solvent), and 3.007 mL (47.44 mmol) of nitric acid was added to the resulting dispersion, and the mixture was stirred for 15 minutes to obtain a suspension. The suspension was filtered to obtain a filtrate.

[0326] 80 mL of ethyl acetate (poor solvent) was added to the obtained filtrate and stirred for 60 minutes to cause it to precipitate again (solid matter was precipitated). The suspension was filtered to separate the solid matter. After the solid matter was recovered, it was dried under reduced pressure to isolate the compound (10) as a colorless solid (powder) with a yield of 14% (0.215 g).

[0327] <Production of Compound (1)>

[0328] [Example 1] Synthesis of Compound (1)-1

[0329] Compound (1)-1 was produced as compound (1) using compound (10) obtained in Production Example 2. More specifically, the process is as follows.

[0330] [Chemical Formula 21]

[0331]

[0332] Compound (10) (36.6 mg, 0.04 mmol) was dissolved in THF (3 mL), and pyridine (45.6 mg, 0.576 mmol) and trimethylsilyl chloride (62.6 mg, 0.576 mmol) were added to the obtained solution, and stirred at room temperature for 24 hours to obtain a suspension solution. The various NMR spectra of the suspension solution confirmed the formation of compound (1)-1 ("Si 12 O 18 [OSiMe3] 12 ”). After filtering, the solvent was distilled off under reduced pressure from the obtained filtrate. Hexane (20 mL) was then added, filtered, and the solvent was distilled off under reduced pressure from the obtained filtrate to obtain compound (1)-1 as a solid (amount 64 mg, yield 95%).

[0333] The NMR data and TOF-MS spectrum of the obtained compound (1)-1 are shown below. Figure 4 express 1 H-NMR measurement results. Figure 5 express 13 C-NMR measurement results. Figure 6 express 29 Si-NMR measurement results. Figure 7 The graph shows the measurement results of high-resolution mass spectrometry (TOF-MS).

[0334] 1 H-NMR (CDCl3): 0.14 ppm.

[0335] 13 C-NMR (CDCl3): 1.31 ppm.

[0336] 29 Si-NMR (CDCl3): 11.7ppm, -110.2ppm.

[0337] For C 36 H 108 NaO 30 Si 24 , HRMS (ESI) m / z calculated as 1715.1280 [M+Na] + , the actual value is 1715.1246.

[0338] [Chemical Formula 22]

[0339]

[0340] [Example 2]

[0341] Compound (1)-2 was produced as compound (1) using compound (10) obtained in Production Example 2. More specifically, the process is as follows.

[0342] [Chemical Formula 23]

[0343]

[0344] Compound (10) (36.6 mg, 0.04 mmol) was dissolved in THF (3 mL), and pyridine (45.6 mg, 0.576 mmol) and dimethylvinylsilyl chloride (69.5 mg, 0.576 mmol) were added to the obtained solution, and stirred at room temperature for 24 hours to obtain a suspension solution. The various NMR spectra of the suspension solution confirmed the formation of compound (1)-2 ("Si 12 O 18 [OSiMe2Vi] 12 ”) (Vi represents a vinyl group). After filtering, the solvent was distilled off under reduced pressure from the obtained filtrate. Then, hexane (20 mL) was added, filtered, and the solvent was distilled off under reduced pressure from the obtained filtrate to obtain compound (1)-2 as a solid substance (amount 70 mg, yield 95%).

[0345] The NMR data and TOF-MS spectrum of the obtained compound (1)-2 are shown below. Figure 8 express 1 H-NMR measurement results. Figure 9 express 13 C-NMR measurement results. Figure 10 express 29 Si-NMR measurement results. Figure 11 The graph shows the measurement results of high-resolution mass spectrometry (TOF-MS).

[0346] 1 H-NMR (CDCl3): 0.18ppm, 5.73-5.77ppm,, 5.91-5.94ppm, 6.08-6.14ppm.

[0347] 13 C-NMR (CDCl3): -0.11ppm, 132.3ppm, 138.2ppm.

[0348] 29Si-NMR (CDCl3): -0.07ppm, -110.4ppm.

[0349] For C 48 H 108 NaO 30 Si 24 , HRMS (ESI) m / z calculated as 1859.1280 [M+Na] + , the actual value is 1859.1272.

[0350] [Chemical Formula 24]

[0351]

[0352] [Example 3]

[0353] Compound (1)-3 was produced as compound (1) using compound (10) obtained in Production Example 2. More specifically, the process is as follows.

[0354] [Chemical Formula 25]

[0355]

[0356] Compound (10) (36.6 mg, 0.04 mmol) was dissolved in THF (3 mL), and pyridine (45.6 mg, 0.576 mmol) and dimethylsilyl chloride (54.5 mg, 0.576 mmol) were added to the obtained solution, and stirred at room temperature for 4 hours to obtain a suspension solution. The various NMR spectra of the suspension solution confirmed the formation of compound (1)-3 ("Si 12 O 18 [OSiMe2H] 12 "). After filtering, the solvent was distilled off under reduced pressure from the obtained filtrate. Hexane (20 mL) was then added, filtered, and the solvent was distilled off under reduced pressure from the obtained filtrate to obtain compound (1)-3 as a solid substance (amount 60 mg, yield 98%).

[0357] The NMR data and TOF-MS spectrum of the obtained compound (1)-3 are shown below. Figure 12 express 1 H-NMR measurement results. Figure 13 express 13 C-NMR measurement results. Figure 14 express 29 Si-NMR measurement results. Figure 15 The graph shows the measurement results of high-resolution mass spectrometry (TOF-MS).

[0358] 1H-NMR (CDCl3): 0.24ppm, 4.73ppm.

[0359] 13 C-NMR (CDCl3): 0.2 ppm.

[0360] 29 Si-NMR (CDCl3): -2.3ppm, -109.6ppm.

[0361] For C 24 H 84 NaO 30 Si 24 , HRMS (ESI) m / z calculated as 1546.9402 [M+Na] + , the actual measured value is 1546.9382.

[0362] [Chemical Formula 26]

[0363]

[0364] [Example 4]

[0365] Compound (1)-4 was produced as compound (1) using compound (10) obtained in Production Example 2. More specifically, the process is as follows.

[0366] [Chemical Formula 27]

[0367]

[0368] Compound (10) (36.6 mg, 0.04 mmol) was dissolved in THF (3 mL), and dimethylchlorosilane (13.2 mg, 0.14 mmol) was added to the obtained solution, followed by trimethylchlorosilane (56.5 mg, 0.52 mmol), and then pyridine (52.2 mg, 0.66 mmol), and the mixture was stirred at room temperature for 20 hours to obtain a suspended solution. After filtering, the solvent was removed by distillation under reduced pressure from the obtained filtrate. Hexane (20 mL) was then added, filtered, and the solvent was removed by distillation under reduced pressure from the obtained filtrate to obtain a series of compounds (1)-4 as solid substances. According to the time-of-flight mass spectrometry (TOF-MS) of the solid substance, it was confirmed that a series of compounds (1)-4 ("Si 12 O 18 [OSiMe2H] n [OSiMe3] 12-n ”)(n=0~12).

[0369] Figure 16 express 1 H-NMR measurement results. Figure 17 express 13 C-NMR measurement results. Figure 18 express 29 Si-NMR measurement results. Figures 19-28 The results of high-resolution mass spectrometry (TOF-MS) analysis of each compound are shown. Figure 29 The figures show the measurement results of a series of compounds (1)-4 by high-resolution mass spectrometry (TOF-MS). Figures 19-28 The left side of each figure shows one example of the substituent position in a series of compounds (1)-4. No difference in the substituent position was observed in high-resolution mass spectrometry analysis. This indicates that a series of compounds (1)-4 were obtained as a mixture.

[0370] [Chemical Formula 28]

[0371]

[0372] In formula (1), at least one Z 5 is dimethylsilyl, and at least one Z 5 It is trimethylsilyl.

[0373] [Example 5]

[0374] Compound (1)-5 was produced as compound (1) using compound (10) obtained in Production Example 2. More specifically, the process is as follows.

[0375] [Chemical Formula 29]

[0376]

[0377] Compound (10) (18.6 mg, 0.02 mmol) was dissolved in THF (1.5 mL), and dimethylvinylsilyl chloride (17.4 mg, 0.16 mmol) and trimethylsilyl chloride (19.3 mg, 0.16 mmol) were added to the obtained solution, and then pyridine (25.3 mg, 0.32 mmol) was added, and the mixture was stirred at room temperature for 24 hours to obtain a suspension solution. After filtering, the solvent was removed by distillation under reduced pressure from the obtained filtrate. Hexane (20 mL) was then added, and the mixture was filtered, and the solvent was removed by distillation under reduced pressure from the obtained filtrate to obtain a series of compounds (1)-5 as solid substances. According to the time-of-flight mass spectrometry (TOF-MS) of the solid substance, it was confirmed that a series of compounds (1)-5 ("Si 12 O 18 [OSiMe2Vi] n [OSiMe3] 12-n ”)(n=0~12).

[0378] Figure 30 express 1 H-NMR measurement results. Figure 31 express 13 C-NMR measurement results. Figure 32 express 29 Si-NMR measurement results. Figures 33-43 The results of high-resolution mass spectrometry (TOF-MS) analysis of each compound are shown. Figure 44 The figures show the measurement results of a series of compounds (1)-5 by high-resolution mass spectrometry (TOF-MS). Figures 33-43 The left side of each figure shows one example of the substituent position in a series of compounds (1)-5. No difference in the substituent position was observed in high-resolution mass spectrometry analysis. This indicates that a series of compounds (1)-5 were obtained as a mixture.

[0379] [Chemical formula 30]

[0380]

[0381] In formula (1), at least one Z 5 is dimethylvinylsilyl, and at least one Z 5 It is trimethylsilyl.

[0382] Industrial applicability

[0383] The present invention can be used as a functional silicon material or an intermediate thereof, and can also be used as a method for producing the same.

Claims

1. A compound represented by the following formula (1): [Chemical Formula 1] (In formula (1), multiple Z 5 Each independently is a hydrogen atom or -SiR 1 R 2 R 3 The groups shown, but multiple Z 5 At least one of them is -SiR 1 R 2 R 3 The groups shown; R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are the above-mentioned groups, these groups may be combined with each other to form a ring.

2. A method for producing a compound, comprising reacting a compound (10) represented by the following formula (10) with at least one compound (3) represented by the following formula (3) to obtain a compound (1) represented by the following formula (1); [Chemical Formula 2] X-SiR 1 R 2 R 3 ……(3) (In formula (3), R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the groups are the alkyl groups, alkenyl groups or aryl groups, these groups may be combined to form a ring; X is a halogen atom;) [Chemical Formula 3] (In formula (1), multiple Z 5 Each independently is a hydrogen atom or -SiR 1 R 2 R 3 The groups shown, but multiple Z 5 At least one of them is -SiR 1 R 2 R 3 The groups shown; R 1 、R 2 and R 3 are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, when R 1 、R 2 and R 3 When two or more of the alkyl groups, alkenyl groups or aryl groups are the above-mentioned groups, these groups may be combined with each other to form a ring.

3. The method for producing the compound according to claim 2, wherein It is reacted with at least two or more of the compounds (3).

4. The method for producing a compound according to claim 2 or 3, wherein The method further comprises a proton exchange step, wherein the proton exchange step is to react a silicate having a structure represented by the following formula (10)' with an acidic compound to obtain the compound (10); [Chemical Formula 4] (In formula (10)', Q + represents a cation.) 5. The method for producing the compound according to claim 4, wherein The proton exchange step includes a separation step of isolating the compound (10) as a powder from a solution containing the compound (10).

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