Method for producing siloxane compound as well as siloxane compound with hydroxysilyl group and alkoxysilyl group

Abstract

To provide a novel method for producing a siloxane compound in which a sequence of substituent groups is controlled.SOLUTION: A method for producing a siloxane compound, which includes an N times (where N represents an integer of 1 or more) siloxane chain elongation cycle comprises: a dehydrogenative condensation step of reacting a hydroxysilyl group of a compound having a hydrosilyl group and the hydroxysilyl group of a siloxane compound having a hydroxysilyl group and alkoxysilyl group, in the presence of a first boron compound having Lewis acidity, to synthesize a siloxane compound with an alkoxysilyl group; and a first dehydrocarbon condensation step of reacting the alkoxysilyl group of the siloxane compound with the alkoxysilyl group and the hydroxysilyl group of the first dihydrosilan compound, in the presence of a second boron compound with Lewis acidity, to synthesize a siloxane compound having a hydrosilyl group.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a method for producing a siloxane compound and a siloxane compound having a hydroxysilyl group and an alkoxysilyl group.

Background Art

[0002] The siloxane bond is a bond that constitutes the basic skeleton of siloxane compounds such as polysiloxane and oligosiloxane. In recent years, in the production of siloxane compounds, development of methods for controlling the arrangement of their substituents has been carried out.

[0003] For example, Patent Document 1 describes a method for producing an oligosiloxane including a dehydrogenative condensation step of reacting an alkoxysilane with a hydrosilane to produce a hydrosiloxane, and a hydrosilylation step of reacting the hydrosiloxane with a carbonyl compound to produce an alkoxysiloxane.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, methods for producing siloxane compounds with a controlled arrangement of substituents are limited, and development of new production methods is demanded.

[0006] An object of the present disclosure is to provide a novel method for producing a siloxane compound with a controlled arrangement of substituents.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that by using a siloxane compound having a hydroxysilyl group and an alkoxysilyl group as a building block, a siloxane compound with precisely controllable substituent sequences can be produced. That is, the present disclosure has the following gist.

[0008] 〔1〕 A dehydrogenative condensation step of reacting the hydrosilyl group of a compound having a hydrosilyl group with the hydroxysilyl group of a siloxane compound having a hydroxysilyl group and an alkoxysilyl group in the presence of a first boron compound having Lewis acidity to synthesize a siloxane compound having an alkoxysilyl group; A first decarbonization dehydrogenative condensation step of reacting the alkoxysilyl group of the siloxane compound having an alkoxysilyl group with the hydrosilyl group of a first dihydrosilane compound in the presence of a second boron compound having Lewis acidity to synthesize a siloxane compound having a hydrosilyl group; A method for producing a siloxane compound, comprising N times (N represents an integer of 1 or more) of a siloxane chain extension cycle consisting of: 〔2〕 The siloxane compound having a hydroxysilyl group and an alkoxysilyl group is represented by any of the formulas (A1) to (A6), and the compound having a hydrosilyl group is represented by the formula (B). The method for producing a siloxane compound according to 〔1〕.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chem.

Chem.

Chem.

[10] The dehydrogenation condensation step, the first dehydrogenation condensation step, the hydrosilylation step, and the second dehydrogenation condensation step are carried out in one pot, according to any one of [7] to [9] The method for producing a siloxane compound according to the description.

[11] A siloxane compound having a hydroxy silyl group and an alkoxy silyl group, represented by any one of formulas (A1) to (A6). [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] [Chemical formula] (In formulas (A1) to (A6), R 1 Each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; R 2 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; n1 to n3 and n7 each independently represent an integer of 1 to 20; n4 to n6 each independently represent an integer of 1 to 3.) [Advantages of the Invention]

[0009] According to the present disclosure, a novel method for producing a siloxane compound with a controlled substituent arrangement can be provided.

Brief Description of the Drawings

[0010]

Figure 1

Modes for Carrying Out the Invention

[0011] Hereinafter, the present disclosure will be described in detail. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present disclosure, and the present disclosure is not limited to these contents, and various modifications can be made and implemented within the scope of the gist.

[0012] In the present disclosure, "X to Y" indicating a range means "X or more and Y or less". Further, when numerical ranges represented by "X to Y" or "X or more and Y or less" are described stepwise (for example, in a preferred order), the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0013] In an embodiment of the present disclosure, in the presence of a first boron compound having Lewis acidity, the hydrosilyl group of a compound having a hydrosilyl group reacts with the hydroxysilyl group and the alkoxysilyl group of a siloxane compound having a hydroxysilyl group and an alkoxysilyl group, and a dehydrogenative condensation step of synthesizing a siloxane compound having an alkoxysilyl group, and in the presence of a second boron compound having Lewis acidity, the alkoxysilyl group of the siloxane compound having an alkoxysilyl group reacts with the hydrosilyl group of a first dihydrosilane compound, and a first decarburization hydrogen condensation step of synthesizing a siloxane compound having a hydrosilyl group, and a siloxane chain extension cycle including N times (N represents an integer of 1 or more) is included. It is a method for producing a siloxane compound.

[0014] 1. Siloxane chain extension cycle A scheme schematically showing an example of a siloxane chain extension cycle (hereinafter sometimes simply referred to as "cycle") consisting of a dehydrogenation condensation step and a first decarbonization hydrogenation condensation step is shown below. In the following scheme, an example of a siloxane chain extension cycle using a siloxane compound having a hydroxy silyl group and an alkoxy silyl group, where the siloxane compound has one hydroxy silyl group and one alkoxy silyl group each, is shown, but the siloxane compound having a hydroxy silyl group and an alkoxy silyl group is not limited thereto.

[0015]

Chemical formula

[0016] According to the production method according to the present embodiment, by repeating the siloxane chain extension cycle consisting of the dehydrogenation condensation step and the first decarbonization hydrogenation condensation step, the siloxane bond is extended. In such a mode, since the desired siloxane structure is sequentially introduced, the arrangement of the substituents of the siloxane compound can be precisely controlled. When producing a siloxane compound by a general method such as hydrolysis condensation polymerization, a mixture of a plurality of types of siloxane compounds having different substituent arrangements and molecular weights is generated. Since it is very difficult or impossible to separate only the siloxane compound having the desired substituent arrangement and the desired molecular weight from such a mixture, the production method according to the present embodiment selectively synthesizes a siloxane compound having the target substituent arrangement and the target molecular weight, which is highly useful.

[0017] In addition, in the method for producing an oligosiloxane described in International Publication No. 2018 / 159756 (Patent Document 1), in order to form one siloxane bond (Si-O), it was necessary to go through two steps, namely a dehydrogenative condensation step and a hydroxysilylation step. However, according to the present embodiment, it is possible to produce a siloxane compound in which the arrangement of substituents is controlled with a smaller number of steps than the conventional method. This is because, in the production method according to the present embodiment, a siloxane compound having a hydroxysilyl group and an alkoxysilyl group is used as a building block (hereinafter, this compound may be referred to as a "building block"). Since this building block is a siloxane (oligosiloxane or polysiloxane) containing one or more siloxane bonds, the siloxane bond can be extended by two or more in one dehydrogenative condensation step. For example, a nonadecasiloxane compound having 19 siloxane bonds requires 35 steps in the above-described method for producing an oligosiloxane, whereas in the examples described later, it can be obtained in only 10 steps. Therefore, the method for producing a siloxane compound according to the present embodiment has high production efficiency and is expected to be developed for industrialization.

[0018] The number of cycles of the siloxane chain extension is set according to the length of the siloxane chain of the target siloxane compound, the number of siloxane bonds contained in the building block, and the presence or absence of the hydrosilylation step and the second dehydrogenative condensation step described later, and is not particularly limited. For example, when the target siloxane compound for production is an oligosiloxane having 10 or fewer siloxane bonds, N may be 1 or more, or 2 or more, and may be 10 or less, 5 or less, or 3 or less. Further, for example, when the target siloxane compound for production is a polysiloxane having more than 10 siloxane bonds, from the viewpoint of ensuring a sufficient yield, N is preferably 100 or less, more preferably 50 or less, and still more preferably 20 or less.

[0019] In the manufacturing method according to this embodiment, in one or more cycles, it is preferable to perform the dehydrogenative condensation step and the first decarburization dehydrogenative condensation step in the same cycle in one pot, and in all cycles, it is more preferable to perform the dehydrogenative condensation step and the first decarburization dehydrogenative condensation step in one pot. In the present disclosure, "one pot" means continuously performing a synthesis reaction in the same reactor. By performing the dehydrogenative condensation step and the first decarburization dehydrogenative condensation step in one pot, the catalyst, solvent, etc. used in the dehydrogenative condensation step can be directly used as the catalyst, solvent, etc. in the first decarburization dehydrogenative condensation step, and the purification of the product in the dehydrogenative condensation step can also be omitted. Therefore, it is possible to improve the production efficiency of the siloxane compound and reduce the production cost.

[0020] Furthermore, when the manufacturing method according to this embodiment includes the hydrosilylation step and the second decarburization dehydrogenative condensation step described later, in addition to the dehydrogenative condensation step and the first decarburization dehydrogenative condensation step, it is also preferable to perform these steps in one pot.

[0021] 1-1. Dehydrogenative condensation step The dehydrogenative condensation step is a step of reacting the hydrosilyl group of a compound having a hydrosilyl group with the hydroxy silyl group of a siloxane compound having a hydroxy silyl group and an alkoxy silyl group in the presence of a first boron compound having Lewis acidity (hereinafter, may be simply referred to as "the first boron compound") to synthesize a siloxane compound having an alkoxy silyl group. The alkoxy silyl group of the produced siloxane compound is an alkoxy silyl group derived from the siloxane compound having a hydroxy silyl group and an alkoxy silyl group.

[0022] 1-1-1. Siloxane compound having a hydroxy silyl group and an alkoxy silyl group The siloxane compound having a hydroxy silyl group and an alkoxy silyl group is not particularly limited as long as it is a siloxane compound having one or more hydroxy silyl groups and one or more alkoxy silyl groups, and can be appropriately selected according to the substituent arrangement of the siloxane compound as the production target. Okay. The number of hydroxy silyl groups in the siloxane compound having a hydroxy silyl group and an alkoxy silyl group is preferably 1, and the number of alkoxy silyl groups is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. Further, the hydroxy silyl group and the alkoxy silyl group may be the same group (i.e., a hydroxyalkoxy silyl group) or different groups, but from the viewpoint of extending a plurality of siloxane bonds in a single dehydrogenation condensation step, it is preferable that they are different groups.

[0023] Examples of the siloxane compound having a hydroxy silyl group and an alkoxy silyl group preferably include compounds represented by any of formulas (A1) to (A6).

[0024] [Chemical formula]

[0025] [Chemical formula]

[0026] [Chemical formula]

[0027] [Chemical formula]

[0028] [Chemical formula]

[0029] [Chemical formula]

[0030] In formulas (A1) to (A6), R 1Each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

[0031] In the present disclosure, the "hydrocarbon group" may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic, and may have a carbon-carbon unsaturated bond. Further, the "halogenated hydrocarbon group" is a group in which some or all of the hydrogen atoms bonded to the carbon atoms of the hydrocarbon group are substituted with halogen atoms.

[0032] R 1 When the hydrocarbon group and the halogenated hydrocarbon group represented by are an aliphatic saturated hydrocarbon group and a halogenated aliphatic saturated hydrocarbon group, respectively, the number of carbon atoms is usually 1 to 20, preferably 1 to 16, more preferably 1 to 12, still more preferably 1 to 6. R 1 When the hydrocarbon group and the halogenated hydrocarbon group represented by are an aliphatic unsaturated hydrocarbon group and a halogenated aliphatic unsaturated hydrocarbon group, respectively, the number of carbon atoms is usually 2 to 20, preferably 2 to 16, more preferably 2 to 12, still more preferably 2 to 6. R 1 When the hydrocarbon group and the halogenated hydrocarbon group represented by are an aromatic hydrocarbon group and a halogenated aromatic hydrocarbon group, respectively, the number of carbon atoms is usually 6 to 20, preferably 6 to 16, more preferably 6 to 12.

[0033] R 1Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and dimethylcyclohexyl group; cycloalkylalkyl groups such as cyclopropylmethyl group and cyclohexylmethyl group; linear or branched aliphatic hydrocarbon groups having a carbon-carbon double bond such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, 2-methylallyl group, pentenyl group, isopentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, 1,3-butadienyl group, 3-methyl-1,3-butadienyl group, 2,4-hexadienyl group, and 2,6-octadienyl group; linear or branched aliphatic hydrocarbon groups having a carbon-carbon triple bond such as ethynyl group, propynyl group, propargyl group, 2-butynyl group, and 3-butynyl group; aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, phenanthrenyl group, anthracenyl group, and fluorenyl group; and aralkyl groups such as benzyl group, phenylethyl group, and naphthylmethyl group; etc. are preferably mentioned.

[0034] R 1 Examples of the halogen atom in the halogenated hydrocarbon group represented by include fluorine atom, chlorine atom, bromine atom, and iodine atom, etc., preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. The halogen atom contained in one hydrocarbon group may be one kind or two or more kinds.

[0035] R 1Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by include fluoromethyl group, chloromethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, trichloromethyl group, 2-fluoroethyl group, 2-chloroethyl group, pentafluoroethyl group, pentachloroethyl group, 3,3,3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 3,5-difluorophenyl group, 3,5-dichlorophenyl group, 2,4,6-trifluorophenyl group, 2,4,6-trichlorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,3,5,6-tetrachlorophenyl group, pentafluorophenyl group, pentachlorophenyl group, 4-trifluoromethylphenyl group, 3,5-bis(trifluoromethyl)phenyl group, and 3-(pentafluorophenyl)propyl group, etc. are preferably mentioned.

[0036] In formulas (A1) to (A6), R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.

[0037] R 2 When the hydrocarbon group represented by is an aliphatic saturated hydrocarbon group, its carbon number is usually 1 to 8, preferably 1 to 7, more preferably 1 to 6, still more preferably 1 to 3, and even more preferably 1. When the hydrocarbon group represented by R 7 is an aliphatic unsaturated hydrocarbon group, its carbon number is usually 2 to 8, preferably 2 to 6, and more preferably 2 to 3. When the hydrocarbon group represented by R 7 is an aromatic hydrocarbon group, its carbon number is usually 6 to 8.

[0038] R 2 Specific examples of the hydrocarbon group having 1 to 8 carbon atoms represented by include those among the specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 where the carbon number is 1 to 8.

[0039] In formulas (A1) to (A6), n1 to n3 and n7 each independently represent an integer of 1 to 20.

[0040] From the viewpoint of extending more siloxane bonds in one dehydrogenative condensation step, n1 to n3 and n7 are preferably 2 or more, more preferably 3 or more. Also, n1 to n3 and n7 are preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. That is, examples of the preferable range of n1 to n3 and n7 include ranges such as 1 to 16, 2 to 20, 2 to 12, and 3 to 8.

[0041] In formulas (A1) to (A6), n4 to n6 each independently represent an integer of 1 to 3.

[0042] n4 to n6 are preferably 1 or 2, more preferably 1.

[0043] Specific examples of the compound represented by any of formulas (A1) to (A6) include the following compounds.

[0044]

Chemical formula

[0045]

Chemical formula

[0046] The building blocks may use different compounds for each cycle, or the same compound may be used.

[0047] As shown in the examples described later, the building blocks can be produced by any method such as a method known in the field of organic synthesis or a method analogous thereto.

[0048] 1-1-2. Compounds having a hydrosilyl group A compound having a hydrosilyl group is a compound having a hydrosilyl group in which one hydrogen atom and two groups not participating in the reaction are bonded to a silicon atom (however, a compound in which a hydrogen atom is further bonded to the silicon atom of this hydrosilyl group is excluded). In the present disclosure, the "group not participating in the reaction" means a group that does not participate as a reactive group in the target reaction and does not inhibit the target reaction.

[0049] When N is 2 or more, the compound having a hydrosilyl group in the dehydrogenative condensation step of the M + 1th cycle is a siloxane compound having a hydrosilyl group obtained in the first dehydrogenative condensation step of the Mth cycle (M represents an integer of 1 or more and N - 1 or less). Alternatively, as described later, when a hydrosilylation step and a second dehydrogenative condensation step are performed between the Mth cycle and the M + 1th cycle, the compound having a hydrosilyl group in the dehydrogenative condensation step of the M + 1th cycle is a siloxane compound having a hydrosilyl group obtained in the second dehydrogenative condensation step.

[0050] Examples of the compound having a hydrosilyl group include a compound represented by formula (B).

[0051]

Chemical formula

[0052] In formula (B), R 3 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

[0053] R 3 When the hydrocarbon group and the halogenated hydrocarbon group represented by are each an aliphatic saturated hydrocarbon group and a halogenated aliphatic saturated hydrocarbon group, respectively, the number of carbon atoms is usually 1 to 20, preferably 1 to 16, more preferably 1 to 12, and still more preferably 1 to 6. R 3When the hydrocarbon group and the halogenated hydrocarbon group represented by are each an aliphatic unsaturated hydrocarbon group and a halogenated aliphatic unsaturated hydrocarbon group, respectively, the number of carbon atoms is usually 2 to 20, preferably 2 to 16, more preferably 2 to 12, and still more preferably 2 to 6. R 3 When the hydrocarbon group and the halogenated hydrocarbon group represented by are each an aromatic hydrocarbon group and a halogenated aromatic hydrocarbon group, respectively, the number of carbon atoms is usually 6 to 20, preferably 6 to 16, and more preferably 6 to 12.

[0054] R 3 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R 1 The groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by are included.

[0055] In formula (B), Y represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a siloxanyloxy group, or a silyloxy group.

[0056] The hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by Y are each synonymous with the hydrocarbon group having 1 to 20 carbon atoms or the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R 3 and the preferred embodiments thereof are also the same.

[0057] The siloxane structure in the siloxanyloxy group represented by Y is not particularly limited and may be a linear siloxane, a branched siloxane, a cyclic siloxane, or a combination thereof. Examples of the siloxanyloxy group include a group composed of one or more selected from the group consisting of the D unit represented by formula (b2), the T unit represented by formula (b3), and the Q unit represented by formula (b4), and the terminal of the group may be capped with the M unit represented by formula (b1) or a group that does not participate in the reaction.

[0058]

Chemical formula

[0059] In formulas (b1) to (b3), R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

[0060] R 4 The hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by are each synonymous with the hydrocarbon group having 1 to 20 carbon atoms or the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R 3 and their preferred embodiments are also the same.

[0061] The silyloxy group represented by Y is a group to which three groups that do not participate in the reaction are bonded to the silicon atom, and is, for example, a group represented by formula (b5).

[0062]

Chemical formula

[0063] In formula (b5), R 5 each independently represents a hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon group having 1 to 20 carbon atoms.

[0064] R 5 The hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by are each synonymous with the hydrocarbon group having 1 to 20 carbon atoms or the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R 3 and their preferred embodiments are also the same.

[0065] In the first cycle, specific examples of the compound represented by formula (B) include, for example, the following compounds.

[0066]

Chemical formula

[0067] In the cycles after the second cycle, as described above, the siloxane compound having a hydrosilyl group obtained in the first dehydrogenative condensation step or the siloxane compound having a hydrosilyl group obtained in the second dehydrogenative condensation step described later is used as the compound having a hydrosilyl group that is the reaction substrate in the dehydrogenative condensation step. Therefore, in the cycles after the second cycle, Y is a siloxanyloxy group containing a structure derived from a building block, a first dihydrosilane compound, and, if necessary, a second dihydrosilane compound.

[0068] The usage amount (charged amount) of the compound having a hydrosilyl group is preferably 0.80 equivalent or more, more preferably 0.90 equivalent or more, still more preferably 0.95 equivalent or more, and preferably 1.50 equivalent or less, more preferably 1.20 equivalent or less, still more preferably 1.10 equivalent or less, based on the amount of substance of the hydroxysilyl group of the siloxane compound having a hydroxysilyl group and an alkoxysilyl group. That is, the preferable range of the usage amount of the compound having a hydrosilyl group with respect to the amount of substance of the hydroxysilyl group of the siloxane compound having a hydroxysilyl group and an alkoxysilyl group includes ranges of 0.80 to 1.50 equivalents, 0.90 to 1.20 equivalents, and 0.95 to 1.10 equivalents.

[0069] 1-1-3. First Boron Compound Having Lewis Acidity The first boron compound having Lewis acidity is a compound that acts as a catalyst for the reaction between the compound having a hydrosilyl group and the building block. The specific type of the first boron compound is not particularly limited and can be appropriately selected according to the reactivity of the reaction substrate and the like.

[0070] Specific examples of the first boron compound include triarylboranes such as triphenylborane (BPh3); and tris(halogenated aryl)boranes such as tris(pentafluorophenyl)borane (B(C6F5)3) and tris(pentachlorophenyl)borane (B(C6Cl5)3); and the like. Among these, the first boron compound is preferably a tris(halogenated aryl)borane, more preferably tris(pentafluorophenyl)borane, in terms of high catalytic activity.

[0071] The first boron compound may be used alone or in combination of two or more in any combination and ratio.

[0072] The amount (charged amount) of the first boron compound used depends on the type of reaction substrate, reaction temperature, etc., but is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 1 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on the building block. That is, the amount of the first boron compound used relative to the building block is in the range of 0.01 to 20 mol%, 0.1 to 15 mol%, and 1 to 10 mol%.

[0073] 1-1-4. Reaction Conditions The reaction in the dehydrogenative condensation step is preferably carried out in a solvent in terms of easy reaction control. The solvent is not particularly limited and can be appropriately selected according to the solubility of the reaction substrate and the solubility of the first boron compound, etc.

[0074] As the solvent, an inert solvent that does not react with the reaction substrate and the catalyst is preferred. Examples of the inert solvent include hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, xylene, and dodecylbenzene; and halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichlorobenzene; and the like. Among these, the solvent is preferably a hydrocarbon solvent, particularly preferably toluene.

[0075] The solvent may be used alone or in combination of two or more in any combination and ratio.

[0076] In the dehydrogenation condensation step, the reaction temperature is preferably 0 °C or higher, more preferably 10 °C or higher, still more preferably 20 °C or higher, and is preferably 80 °C or lower, more preferably 60 °C or lower, still more preferably 40 °C or lower. That is, the preferable range of the reaction temperature includes ranges of 0 to 80 °C, 10 to 60 °C, and 20 to 40 °C.

[0077] In the dehydrogenation condensation step, the reaction time depends on the reaction temperature and the like, but is preferably 1 minute or longer, more preferably 5 minutes or longer, still more preferably 10 minutes or longer, and is preferably 12 hours or shorter, more preferably 6 hours or shorter, still more preferably 1 hour or shorter. That is, the preferable range of the reaction time includes ranges of 1 minute to 12 hours, 5 minutes to 6 hours, and 10 minutes to 1 hour.

[0078] The dehydrogenation condensation step may be carried out in an air atmosphere or in an inert atmosphere such as nitrogen and argon. Since strict water-free conditions are not required for the dehydrogenation condensation step, from the viewpoint of reaction efficiency it is preferably carried out in an inert atmosphere.

[0079] The dehydrogenation condensation step may be carried out under atmospheric pressure or under pressure, but is preferably carried out under atmospheric pressure.

[0080] 1-2. First dehydrogenation condensation step In the first dehydrogenation condensation step, in the presence of a second boron compound having Lewis acidity (hereinafter, may be simply referred to as "second boron compound"), the alkoxysilyl group of the siloxane compound having an alkoxysilyl group obtained in the dehydrogenation condensation step and the hydrosilyl group of the first dihydrosilane compound are reacted (Piers-Rubinsztajn reaction), and the silane having a hydrosilyl group This is a process for synthesizing a siloxane compound. The hydrosilyl group of the siloxane compound to be produced is a hydrosilyl group derived from a first dihydrosilane compound, that is, a group obtained by removing one hydrogen atom bonded to a silicon atom from the first dihydrosilane compound.

[0081] 1-2-1. First dihydrosilane compound The first dihydrosilane compound is a compound in which two hydrogen atoms and two groups not participating in the reaction are bonded to a silicon atom. The first dihydrosilane compound is not particularly limited and may be appropriately selected according to the substituent arrangement of the siloxane compound as the production target.

[0082] As the first dihydrosilane compound, a compound represented by formula (C) is preferably mentioned.

[0083]

Chemical formula

[0084] In formula (C), R 6 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

[0085] When the hydrocarbon group and the halogenated hydrocarbon group represented by R 6 are an aliphatic saturated hydrocarbon group and a halogenated aliphatic saturated hydrocarbon group, respectively, the number of carbon atoms thereof is usually 1 to 20, preferably 1 to 16, more preferably 1 to 12, and still more preferably 1 to 6. When the hydrocarbon group and the halogenated hydrocarbon group represented by R 6 are an aliphatic unsaturated hydrocarbon group and a halogenated aliphatic unsaturated hydrocarbon group, respectively, the number of carbon atoms thereof is usually 2 to 20, preferably 2 to 16, more preferably 2 to 12, and still more preferably 2 to 6. When the hydrocarbon group and the halogenated hydrocarbon group represented by R 6 are an aromatic hydrocarbon group and a halogenated aromatic hydrocarbon group, respectively, the number of carbon atoms thereof is usually 6 to 20, preferably 6 to 16, and more preferably 6 to 12.

[0086] R 6 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R 1 include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R

[0087] When the siloxane compound having a hydrosilyl group produced in the first dehydrogenative condensation step is used as it is as the siloxane compound having a hydrosilyl group in the dehydrogenative condensation step of the next cycle, R 6 is preferably a group with little steric hindrance in that the condensation reaction proceeds easily. More specifically, R 6 is preferably a linear saturated hydrocarbon group having 1 to 6 carbon atoms or a linear halogenated saturated hydrocarbon group having 1 to 6 carbon atoms, more preferably a linear saturated hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a methyl group or an ethyl group.

[0088] Specific examples of the first dihydrosilane compound include dialkylsilanes such as dimethylsilane, diethylsilane, ethylmethylsilane, di-n-propylsilane, di-n-butylsilane, and di-tert-butylsilane; bis(haloalkyl)silanes such as bis(trifluoromethyl)silane and bis(pentafluoroethyl)silane; diarylsilanes such as diphenylsilane, ditolylsilane, and dinaphthylsilane; bis(haloaryl)silanes such as bis(pentafluorophenyl)silane; and alkylarylsilanes such as methylphenylsilane; and the like.

[0089] Dimethylsilane is a gas at normal temperature and pressure and has high flammability, making it difficult to handle. Therefore, when using dimethylsilane as the first dihydrosilane compound, it is preferable to carry out a disproportionation reaction of 1,1,3,3,5,5,7,7 - octamethyltetrasiloxane in the presence of a boron compound having Lewis acidity to produce dimethylsilane and use it in the first dehydrogenative condensation step. As the boron compound having Lewis acidity, since a second boron compound having Lewis acidity can be used, it is preferable to carry out the disproportionation reaction in the reaction system of the first dehydrogenative condensation step. The disproportionation reaction can be carried out, for example, by the method described in JP - A - 2022 - 067243 or a method analogous thereto.

[0090] The usage amount (charged amount) of the first dihydrosilane compound is preferably 0.80 equivalent or more, more preferably 0.90 equivalent or more, still more preferably 0.95 equivalent or more, and preferably 1.50 equivalents or less, more preferably 1.20 equivalents or less, still more preferably 1.10 equivalents or less, based on the amount of substance of the alkoxysilyl group of the siloxane compound having an alkoxysilyl group. That is, the preferable range of the usage amount of the first dihydrosilane compound with respect to the amount of substance of the alkoxysilyl group of the siloxane compound having an alkoxysilyl group includes ranges of 0.80 - 1.50 equivalents, 0.90 - 1.20 equivalents, and 0.95 - 1.10 equivalents.

[0091] 1 - 2 - 2. Second Boron Compound Having Lewis Acidity The second boron compound having Lewis acidity (hereinafter, may be simply referred to as "second boron compound") is a compound that acts as a catalyst for the reaction between a siloxane compound having an alkoxysilyl group and a first dihydrosilane compound. The specific type of the second boron compound is not particularly limited and can be appropriately selected according to the reactivity of the reaction substrate and the like.

[0092] As the second boron compound, those described as the first boron compound can be used, and the preferred embodiments are the same as those of the first boron compound. The second boron compound may be the same compound as the first boron compound or a different compound, but it is preferably the same compound as the first boron compound, and more preferably the same compound as the first boron compound used in the previous dehydrogenation condensation step. When the dehydrogenation condensation step and the first decarbonization hydrogen condensation step are carried out in one pot, the first boron compound contained in the reaction system after the dehydrogenation condensation step is directly used as the catalyst in the first decarbonization hydrogen condensation step, that is, as the second boron compound. In the case of one-pot synthesis, a second boron compound identical or different from the catalyst in the previous dehydrogenation condensation step may be further added to the reaction system during the first decarbonization hydrogen condensation step.

[0093] The second boron compound may be used alone or in combination of two or more in any combination and ratio.

[0094] The amount of the second boron compound used (charged amount) depends on the type of the reaction substrate, the reaction temperature, etc., but is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 1 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on the siloxane compound having an alkoxysilyl group. That is, the amount of the first boron compound used relative to the building block ranges from 0.01 to 20 mol%, 0.1 to 15 mol%, and 1 to 10 mol%.

[0095] The siloxane compound having a hydrosilyl group produced in the first decarbonization hydrogen condensation step can be used directly as the compound having a hydrosilyl group which is the reaction substrate in the dehydrogenation condensation step of the next cycle, and can also be used as the compound having a hydrosilyl group which is the reaction substrate in the dehydrogenation condensation step of the next cycle through the hydrosilylation step and the second decarbonization hydrogen condensation step described below.

[0096] 1-2-3. Reaction conditions The reaction in the first dehydrogenative decarbonization condensation step is preferably carried out in a solvent in terms of easy reaction control. The solvent is not particularly limited and can be appropriately selected according to the solubility of the reaction substrate and the solubility of the second boron compound, etc.

[0097] As the solvent, an inert solvent that does not react with the reaction substrate and the catalyst is preferred. Examples of the inert solvent include hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, xylene, and dodecylbenzene; and halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichlorobenzene. Among these, the solvent is preferably a hydrocarbon solvent, and particularly preferably toluene.

[0098] The solvent may be used alone or in combination of two or more in any combination and ratio.

[0099] When the dehydrogenative condensation step and the first dehydrogenative decarbonization condensation step are carried out in one pot, the solvent contained in the reaction system after the dehydrogenative condensation step is directly used as the solvent in the first dehydrogenative decarbonization condensation step. In the case of one-pot synthesis, during the first dehydrogenative decarbonization condensation step, a solvent the same as or different from the solvent in the previous dehydrogenative condensation step may be further added to the reaction system.

[0100] In the first dehydrogenative decarbonization condensation step, the reaction temperature is preferably 0 °C or higher, more preferably 10 °C or higher, still more preferably 20 °C or higher, and is preferably 80 °C or lower, more preferably 60 °C or lower, still more preferably 40 °C or lower. That is, the preferable range of the reaction temperature includes the ranges of 0 to 80 °C, 10 to 60 °C, and 20 to 40 °C.

[0101] In the first hydrocarbon decarbonylation condensation step, the reaction time depends on the reaction temperature and the like, but is preferably 1 minute or more, more preferably 5 minutes or more, still more preferably 10 minutes or more, and is preferably 12 hours or less, more preferably 6 hours or less, still more preferably 1 hour or less. That is, the preferable range of the reaction time includes the ranges of 1 minute to 12 hours, 5 minutes to 6 hours, and 10 minutes to 1 hour.

[0102] The first hydrocarbon decarbonylation condensation step may be carried out in an air atmosphere or in an inert atmosphere such as nitrogen and argon. Since strict water-free conditions are not required for the first hydrocarbon decarbonylation condensation step, it is preferably carried out in an inert atmosphere from the viewpoint of reaction efficiency.

[0103] The first hydrocarbon decarbonylation condensation step may be carried out under atmospheric pressure or under pressure, but is preferably carried out under atmospheric pressure.

[0104] 2. Hydrosilylation step and second hydrocarbon decarbonylation condensation step In the production method according to the present embodiment, when N is an integer of 2 or more, between the M-th cycle and the (M + 1)-th cycle (M represents an integer of 1 or more and N - 1 or less), in the presence of a third boron compound having Lewis acidity, a hydrosilylation step of reacting the siloxane compound having a hydrosilyl group obtained in the first hydrocarbon decarbonylation condensation step with a carbonyl compound to synthesize a siloxane compound having an alkoxysilyl group, and in the presence of a fourth boron compound having Lewis acidity, reacting the siloxane compound having an alkoxysilyl group with the hydrosilyl group of a second dihydrosilane compound (Piers-Rubinsztajn reaction), and a second hydrocarbon decarbonylation condensation step of synthesizing a siloxane compound having a hydrosilyl group may be included. A scheme schematically showing an example of the hydrosilylation step and the second hydrocarbon decarbonylation condensation step is shown below.

[0105]

Chemical formula

[0106] ​ When the hydrosilyl group of the siloxane compound having a hydrosilyl group obtained in the first dehydrogenative condensation step in the M-th cycle has a bulky group such as a tert-butyl group and a phenyl group, the reaction with the siloxane compound having a hydroxy silyl group and an alkoxysilyl group in the dehydrogenative condensation step in the (M + 1)-th cycle may be difficult to proceed. Therefore, in such a case, before the (M + 1)-th cycle, a hydrosilylation step and a second dehydrogenative condensation step are sequentially performed, and the terminal of the siloxane compound obtained in the first dehydrogenative condensation step is modified with a hydrosilyl group having a small steric hindrance, so that the reaction in the dehydrogenative condensation step in the (M + 1)-th cycle can proceed easily, and the yield of the target product can be improved.

[0107] Alternatively, for the purpose of introducing another substituent into the siloxane compound in addition to the substituent sequence derived from the building block and the first dihydrosilane compound, a hydrosilylation step and a second hydrosilylation step may be performed.

[0108] The hydrosilylation step and the second dehydrogenative condensation step are preferably carried out in one pot. Further, it is more preferable to carry out these steps and the dehydrogenative condensation step and the first dehydrogenative condensation step in the M-th or (M + 1)-th cycle in one pot, and it is even more preferable to carry out these steps and the dehydrogenative condensation step and the first dehydrogenative condensation step in the M-th and (M + 1)-th cycles in one pot. Thereby, it becomes possible to improve the production efficiency of the siloxane compound and reduce the production cost.

[0109] 2-1. Hydrosilylation step The hydrosilylation step is a step of converting a hydrogen atom bonded to a silicon atom in the hydrosilyl group of the siloxane compound obtained in the first dehydrogenative condensation step in the M-th cycle into an alkoxy group derived from a carbonyl compound.

[0110] 2-1-1. Carbonyl compound The carbonyl compound used in the hydrosilylation step is not particularly limited and can be appropriately selected according to the target siloxane compound having an alkoxysilyl group. As the carbonyl compound, for example, a compound represented by formula (D) is preferably mentioned.

[0111]

Chemical formula

[0112] In formula (D), R 7 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.

[0113] When the hydrocarbon group represented by R 7 is an aliphatic saturated hydrocarbon group, its carbon number is usually 1 to 8, preferably 1 to 7, more preferably 1 to 6, and still more preferably 1 to 3. When the hydrocarbon group represented by R 7 is an aliphatic unsaturated hydrocarbon group, its carbon number is usually 2 to 8, preferably 2 to 6, and more preferably 2 to 3. When the hydrocarbon group represented by R 7 is an aromatic hydrocarbon group, its carbon number is usually 6 to 8.

[0114] Specific examples of the hydrocarbon group having 1 to 8 carbon atoms represented by R 7 include those among the specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R 1 that have 1 to 8 carbon atoms.

[0115] Specific examples of the carbonyl compound represented by formula (D) include formaldehyde, acetaldehyde, acetone, 3-pentanone, cyclohexanone, benzaldehyde, acetophenone, and benzophenone, and preferably acetone.

[0116] The amount of the carbonyl compound (charged amount) is preferably 0.80 equivalent or more, more preferably 0.90 equivalent or more, still more preferably 0.95 equivalent or more, and preferably 1.50 equivalent or less, more preferably 1.20 equivalent or less, still more preferably 1.10 equivalent or less, based on the amount of substance of the hydrosilyl group of the siloxane compound having a hydrosilyl group. That is, the preferable ranges of the amount of the carbonyl compound used with respect to the amount of substance of the hydrosilyl group of the siloxane compound having a hydrosilyl group include ranges of 0.80 to 1.50 equivalents, 0.90 to 1.20 equivalents, and 0.95 to 1.10 equivalents.

[0117] 2-1-2. Boron(III) compound having Lewis acidity The boron(III) compound having Lewis acidity (hereinafter sometimes simply referred to as "boron(III) compound") is a compound that acts as a catalyst for the reaction between a siloxane compound having a hydrosilyl group and a carbonyl compound. The specific types of the boron(III) compound are not particularly limited and can be appropriately selected according to the reactivity of the reaction substrate and the like.

[0118] As the boron(III) compound, those described as the boron(I) compound can be used, and the preferable embodiments thereof are also the same as those of the boron(I) compound. The boron(III) compound may be the same compound as the boron(I) compound or the boron(II) compound, or may be a different compound, but it is preferably the same compound as the boron(I) compound or the boron(II) compound, and more preferably the same compound as the boron(II) compound used in the previous first dehydrogenative condensation step. When the first dehydrogenative condensation step and the hydrosilylation step in the Mth cycle are carried out in one pot, the boron(II) compound contained in the reaction system after the first dehydrogenative condensation step is used as it is as the catalyst in the hydrosilylation step, that is, as the boron(III) compound. In the case of one-pot synthesis, during the hydrosilylation step, a boron(III) compound that is the same as or different from the catalyst in the previous first dehydrogenative condensation step may be further added to the reaction system.

[0119] The third boron compound may be used alone or in combination of two or more in any combination and ratio.

[0120] Although the amount used (charged amount) of the third boron compound depends on the type of reaction substrate, reaction temperature, etc., it is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 1 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on the siloxane compound having a hydrosilyl group. That is, the amount of the first boron compound used relative to the building block is in the range of 0.01 to 20 mol%, 0.1 to 15 mol%, and 1 to 10 mol%.

[0121] 2-1-3. Reaction conditions The reaction in the hydrosilylation step is preferably carried out in a solvent in terms of easy control of the reaction. The solvent is not particularly limited and can be appropriately selected according to the solubility of the reaction substrate and the solubility of the third boron compound, etc.

[0122] As the solvent, an inert solvent that does not react with the reaction substrate and the catalyst is preferable. Examples of the inert solvent include hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, xylene, and dodecylbenzene; and halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichlorobenzene. Among these, the solvent is preferably a hydrocarbon solvent, and particularly preferably toluene.

[0123] The solvent may be used alone or in combination of two or more in any combination and ratio.

[0124] When the first dehydrogenative condensation step and the hydrosilylation step are carried out in one pot, the solvent contained in the reaction system after the first dehydrogenative condensation step is used as the solvent in the hydrosilylation step as it is. In the case of one-pot synthesis, a solvent the same as or different from the solvent in the previous first dehydrogenative condensation step may be further added to the reaction system during the hydrosilylation step.

[0125] In the hydrosilylation step, the reaction temperature is preferably 0 °C or higher, more preferably 10 °C or higher, still more preferably 20 °C or higher, and is preferably 80 °C or lower, more preferably 60 °C or lower, still more preferably 40 °C or lower. That is, the preferable range of the reaction temperature includes the ranges of 0 to 80 °C, 10 to 60 °C, and 20 to 40 °C.

[0126] In the hydrosilylation step, the reaction time depends on the reaction temperature and the like, but is preferably 1 minute or longer, more preferably 5 minutes or longer, still more preferably 10 minutes or longer, and is preferably 12 hours or shorter, more preferably 6 hours or shorter, still more preferably 1 hour or shorter. That is, the preferable range of the reaction time includes the ranges of 1 minute to 12 hours, 5 minutes to 6 hours, and 10 minutes to 1 hour.

[0127] The hydrosilylation step may be carried out under an air atmosphere or under an inert atmosphere such as nitrogen and argon. Since strict water-free conditions are not required for the hydrosilylation step, it is preferably carried out under an inert atmosphere from the viewpoint of reaction efficiency.

[0128] The hydrosilylation step may be carried out under atmospheric pressure or under pressure, but it is preferably carried out under atmospheric pressure.

[0129] 2-2. Second dehydrogenative condensation step The second dehydrogenative condensation step is a step of converting an alkoxy group of a siloxane compound having an alkoxysilyl group into a hydrosilyl group derived from a second dihydrosilane compound.

[0130] 2-2-1. Second dihydrosilane compound The second dihydrosilane compound is, like the first dihydrosilane compound, a compound in which two hydrogen atoms and two groups not involved in the reaction are bonded to a silicon atom. The second dihydrosilane compound is not particularly limited and may be appropriately selected according to the target substituent sequence.

[0131] As the second dihydrosilane compound, a compound represented by formula (E) is preferably mentioned.

[0132] [Chemical formula]

[0133] In formula (E), R 8 each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.

[0134] R 8 When the hydrocarbon group and the halogenated hydrocarbon group represented by are each an aliphatic saturated hydrocarbon group and a halogenated aliphatic saturated hydrocarbon group, respectively, the number of carbon atoms thereof is usually 1 to 20, preferably 1 to 16, more preferably 1 to 12, and still more preferably 1 to 6. R 8 When the hydrocarbon group and the halogenated hydrocarbon group represented by are each an aliphatic unsaturated hydrocarbon group and a halogenated aliphatic unsaturated hydrocarbon group, respectively, the number of carbon atoms thereof is usually 2 to 20, preferably 2 to 16, more preferably 2 to 12, and still more preferably 2 to 6. R 8 When the hydrocarbon group and the halogenated hydrocarbon group represented by are each an aromatic hydrocarbon group and a halogenated aromatic hydrocarbon group, respectively, the number of carbon atoms thereof is usually 6 to 20, preferably 6 to 16, and more preferably 6 to 12.

[0135] R 8 Specific examples of the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by include the groups exemplified as the hydrocarbon group having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms represented by R 1 .

[0136] Specific examples of the second dihydrosilane compound include the same ones as those of the first dihydrosilane compound.

[0137] When performing the second hydrocarbon condensation step for the purpose of modifying the ends of the siloxane compound obtained in the first hydrocarbon condensation step with a hydrosilyl group having a small steric hindrance, the second dihydrosilane compound is preferably a compound having a hydrocarbon group with a small number of carbon atoms. Specifically, dimethylsilane, diethylsilane, ethylmethylsilane, or methylphenylsilane is preferred, and dimethylsilane is more preferred. As described in the item "1-2-1. First dihydrosilane compound", dimethylsilane is preferably generated in the reaction system by the disproportionation reaction of 1,1,3,3,5,5,7,7-octamethyltetrasiloxane and then used.

[0138] The amount of the second dihydrosilane compound used (charged amount) is preferably 0.80 equivalent or more, more preferably 0.90 equivalent or more, still more preferably 0.95 equivalent or more, and preferably 1.50 equivalent or less, more preferably 1.20 equivalent or less, still more preferably 1.10 equivalent or less, based on the amount of substance of the alkoxy group of the siloxane compound having an alkoxysilyl group. That is, the preferable ranges of the amount of the second dihydrosilane compound used with respect to the amount of substance of the alkoxy group of the siloxane compound having an alkoxysilyl group are in the ranges of 0.80 to 1.50 equivalents, 0.90 to 1.20 equivalents, and 0.95 to 1.10 equivalents. When performing the second hydrocarbon condensation step for the purpose of modifying the ends of the siloxane compound obtained in the first hydrocarbon condensation step with a hydrosilyl group having a small steric hindrance, the second dihydrosilane compound is preferably a compound having a hydrocarbon group with a small number of carbon atoms. Specifically, dimethylsilane, diethylsilane, ethylmethylsilane, or methylphenylsilane is preferred, and dimethylsilane is more preferred. As described in the item "1-2-1. First dihydrosilane compound", dimethylsilane is preferably generated in the reaction system by the disproportionation reaction of 1,1,3,3,5,5,7,7-octamethyltetrasiloxane and then used.

[0139] 2-2-2. Fourth boron compound having Lewis acidity The fourth boron compound having Lewis acidity (hereinafter, may be simply referred to as "fourth boron compound") is a compound that acts as a catalyst for the reaction between the siloxane compound having an alkoxysilyl group and the second dihydrosilane compound. The specific types of the fourth boron compound are not particularly limited and can be appropriately selected according to the reactivity of the reaction substrate and the like.

[0140] As the fourth boron compound, those described as the first boron compound can be used, and the preferred embodiments are the same as those of the first boron compound. The fourth boron compound may be the same compound as the first boron compound, the second boron compound, or the third boron compound, or may be a different compound, but it is preferably the same compound as the first boron compound, the second boron compound, or the third boron compound, and more preferably the same compound as the third boron compound used in the previous hydrosilylation step. When the hydrosilylation step and the second dehydrogenative condensation step are carried out in one pot, the third boron compound contained in the reaction system after the hydrosilylation step is directly used as the catalyst in the second dehydrogenative condensation step, that is, as the fourth boron compound. In the case of one-pot synthesis, a fourth boron compound identical or different from the catalyst in the previous hydrosilylation step may be further added to the reaction system during the second dehydrogenative condensation step.

[0141] The fourth boron compound may be used alone or in combination of two or more in any combination and ratio.

[0142] The amount (charged amount) of the fourth boron compound used depends on the type of the reaction substrate, the reaction temperature, etc., but is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 1 mol% or more, and preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, based on the siloxane compound having an alkoxysilyl group. That is, the amount of the first boron compound used relative to the building block is in the range of 0.01 to 20 mol%, 0.1 to 15 mol%, and 1 to 10 mol%.

[0143] 2-2-3. Reaction conditions The reaction in the second dehydrogenative condensation step is preferably carried out in a solvent in terms of easy control of the reaction. The solvent is not particularly limited and can be appropriately selected according to the solubility of the reaction substrate and the solubility of the fourth boron compound, etc.

[0144] As the solvent, an inert solvent that does not react with the reaction substrate and the catalyst is preferred. Examples of the inert solvent include hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, xylene, and dodecylbenzene; and halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichlorobenzene. Among these, the solvent is preferably a hydrocarbon solvent, and particularly preferably toluene.

[0145] The solvent may be used alone or in combination of two or more in any combination and ratio.

[0146] When the hydrosilylation step and the second dehydrogenative condensation step are carried out in one pot, the solvent contained in the reaction system after the hydrosilylation step is directly used as the solvent in the second dehydrogenative condensation step. In the case of one-pot synthesis, during the second dehydrogenative condensation step, a solvent the same as or different from the solvent in the previous hydrosilylation step may be further added to the reaction system.

[0147] In the second dehydrogenative condensation step, the reaction temperature is preferably 0 °C or higher, more preferably 10 °C or higher, still more preferably 20 °C or higher, and preferably 80 °C or lower, more preferably 60 °C or lower, still more preferably 40 °C or lower. That is, the preferable range of the reaction temperature includes the ranges of 0 to 80 °C, 10 to 60 °C, and 20 to 40 °C.

[0148] In the second dehydrogenative condensation step, the reaction time depends on the reaction temperature and the like, but is preferably 1 minute or longer, more preferably 5 minutes or longer, still more preferably 10 minutes or longer, and preferably 12 hours or shorter, more preferably 6 hours or shorter, still more preferably 1 hour or shorter. That is, the preferable range of the reaction time includes the ranges of 1 minute to 12 hours, 5 minutes to 6 hours, and 10 minutes to 1 hour.

[0149] The second hydrocarbon dehydrogenation condensation step may be carried out in an air atmosphere or in an inert atmosphere such as nitrogen and argon. Since the second hydrocarbon dehydrogenation condensation step does not require strict water-free conditions, it is preferably carried out in an inert atmosphere from the viewpoint of reaction efficiency.

[0150] The second hydrocarbon dehydrogenation condensation step may be carried out under atmospheric pressure or under pressure, but it is preferably carried out under atmospheric pressure.

[0151] 3. Other steps The production method according to the present embodiment may include any optional steps in addition to the above steps. Examples of the optional steps include a terminal capping step of capping the terminals of the siloxane compound obtained by the above steps with an inert group or a reactive group; and a purification step for increasing the purity of the product or the target siloxane compound in each step; and the like.

[0152] As the terminal capping step, a method usually carried out in the field of synthesis of siloxane compounds can be adopted. Examples of the usual terminal capping methods include methods using terminal capping agents such as trimethylchlorosilane, dimethylvinylchlorosilane, 3-methacryloxypropyldimethylchlorosilane, 3-acryloxypropyldimethylchlorosilane, trimethylsilanol, 1,1,3,3,5,5,5-heptamethyltrisiloxan-1-ol, and 1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxan-1-ol.

[0153] As the purification method in the purification step, a purification method usually carried out in the field of organic synthesis such as filtration, adsorption, distillation, and column chromatography can be adopted. For example, a method of purifying the reaction mixture by gel permeation chromatography can be mentioned.

[0154] In addition to these, after the siloxane chain extension cycle or the second hydrocarbon dehydrogenation condensation step, only the dehydrogenation condensation step of the above cycle may be carried out.

Examples

[0155] Hereinafter, the present disclosure will be described more specifically with reference to examples. However, the present disclosure is not limited to the following examples as long as it does not deviate from the gist thereof. In the following description, "room temperature" means a temperature condition without artificial heating or cooling, specifically, a temperature range of 20°C to 30°C.

[0156] <Example 1> To a eggplant flask under a nitrogen atmosphere, hexamethylcyclotrisiloxane (11.1 g, 50 mmol), chlorodimethylsilane (5.44 mL, 50.0 mmol), N,N-dimethylformamide (128 μL, 1.65 mmol), and acetonitrile (2.5 mL) were added and stirred for 72 hours, and further stirred at 0°C for 10 minutes. Subsequently, triethylamine (7.2 mL, 55.0 mmol) and 2-propanol (4.2 mL, 55.0 mmol) were gradually added to the reaction solution, and the temperature was gradually raised to room temperature and stirred for 12 hours. The reaction mixture was passed through a silica gel pad, and the filtrate was concentrated to obtain 1-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxane (colorless liquid, 15.9 g, 93%).

[0157] In an eggplant flask, 5% palladium carbon (73 mg, 0.037 mmol) was added to a solution obtained by mixing distilled water (2.65 g, 147 mmol) and tetrahydrofuran (20 mL), and stirred at 0°C for 10 minutes. A tetrahydrofuran solution (20 mL) of 1-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxane (12.5 g, 36.7 mmol) was added dropwise thereto over 10 minutes, and the temperature was gradually raised to room temperature and stirred for 1 hour. The reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane:acetone (10:1, v / v)) to obtain 7-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxan-1-ol (colorless liquid, 11.8 g, 90%).

[0158] Reaction scheme and product of Example 1 29 Si{1 The 1H NMR measurement results are shown below.

[0159]

Chemical formula

[0160] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -11.0, -13.8, -21.0, -21.3 ppm

[0161] <Example 2> In a nitrogen atmosphere in an eggplant flask, to a solution obtained by dissolving 7-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxan-1-ol (7.6 mL, 20.0 mmol) in n-hexane (100 mL), triethylamine (3.1 mL, 22.0 mmol) and 1-chloro-1,1,3,3,5,5,7,7-octamethyltetrasiloxane (6.34 g, 20.0 mmol) were added, and the mixture was stirred at room temperature for 9 hours. Then, the reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain 1-isopropoxy-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane (colorless liquid, 8.48 g, 67%).

[0162] In a round-bottom flask, 5% palladium on carbon (27 mg, 0.0133 mmol) was added to a solution obtained by mixing distilled water (1.0 g, 53.2 mmol) and tetrahydrofuran (10 mL), and the mixture was stirred at 0 °C for 10 minutes. A solution of 1-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxane (8.48 g, 13.3 mmol) in tetrahydrofuran (10 mL) was added dropwise thereto over 10 minutes, and the temperature was gradually raised to room temperature and stirred for 1 hour. The reaction mixture was passed through a Celite pad, and the filtrate was concentrated to obtain a crude product. The crude product was purified by silica gel column chromatography (n-hexane:acetone (2:1, v / v)) to obtain 15-isopropoxy-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxan-1-ol (colorless liquid, 5.13 g, 59%).

[0163] Reaction scheme and product of Example 2 29 Si{ 1 The 1H NMR measurement results are shown below.

[0164]

Chemical formula

[0165] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -10.6, -14.7, -20.8, -21.3, -21.4, -21.7, -21.9, -21.2 ppm

[0166] <Example 3> In a nitrogen atmosphere in an eggplant flask, to a solution obtained by dissolving 15-isopropoxy-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxan-1-ol (951 mg, 3.0 mmol) in n-hexane (15 mL), triethylamine (0.42 mL, 3.0 mmol) and 1-chloro-1,1,3,3,5,5,7,7-octamethyltetrasiloxane (1.96 g, 3.0 mmol) were added, and the mixture was stirred at room temperature for 20 hours. Then, the reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain 1-isopropoxy-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17,19,19,21,21,23,23-tetracosamethyl dodecasiloxane (colorless liquid, 2.25 g, 79%).

[0167] In an eggplant flask, to a solution obtained by mixing distilled water (0.17 g, 9.48 mmol) and tetrahydrofuran (3 mL), 5% palladium on carbon (4.7 mg, 0.024 mmol) was added, and the mixture was stirred at 0 °C for 10 minutes. To this, a tetrahydrofuran solution (10 mL) of 1-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxane (2.25 g, 2.37 mmol) was added dropwise over 10 minutes, and the temperature was gradually raised to room temperature and stirred for 1 hour. The reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain a crude product. This crude product was purified by silica gel column chromatography (n-hexane:acetone (5: 1, v / v)) to obtain 23-isopropoxy-1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15,17,17,19,19,21,21,23,23-tetracosamethyl dodecasiloxan-1-ol (colorless liquid, 1.62 g, 72%).

[0168] The reaction scheme of Example 3 and the 29 Si{ 1 H} NMR measurement results are shown below.

[0169]

Chemical formula

[0170] 29 Si{ 1 H} NMR (119 MHz, CDCl3): δ -10.4, -14.7, -20.8, -21.3, -21.3, -21.4, -21.7, -21.90, -21.93, -21.98, -22.00 ppm

[0171] Example 4 In a nitrogen atmosphere in an eggplant flask, 1,1,2,2-tetramethyldisiloxane (5.3 mL, 30 mmol) and tetrahydrofuran (90 mL) were mixed and stirred at -80 °C for 10 minutes. Trichloroisocyanuric acid (2.32 g, 10 mmol) was added little by little thereto, and the temperature was gradually raised to room temperature and stirred for 14 hours. Thereafter, triethylamine (8.4 mL, 60 mmol) and 2-propanol (4.6 mL, 60 mmol) were further added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (5 mL) and added dropwise to a slurry obtained by mixing 5% palladium carbon (64 mg, 0.030 mmol), distilled water (1.08 g) and tetrahydrofuran (25 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain a crude product. This crude product was purified by silica gel column chromatography (n-hexane:acetone (10:1, v / v)) to obtain 3-isopropoxy-1,1,3,3-tetramethyldisiloxan-1-ol (colorless liquid, 3.81 g, 61%).

[0172] Reaction scheme of Example 4 and the 29 Si{ 1 H} NMR measurement results are shown below.

[0173]

Chemical formula

[0174] 29 Si{ 1 H} NMR (119 MHz, CDCl3): δ -10.7, -13.4 ppm

[0175] <Example 5> In a glove box under a nitrogen atmosphere, B(C6F5)3 (102.4 mg, 0.20 mmol) was dissolved in toluene (80 mL). To the resulting solution, diphenylsilane (7.37 mL, 40 mmol) was added, and then acetone (1.47 mL, 20 mmol) was added dropwise over 5 minutes. After stirring at room temperature for 10 minutes, acetone (1.47 mL, 20 mmol) was added to the resulting reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (60 mL), mixed with 5% palladium on carbon (40 mg, 0.04 mmol) and distilled water (0.72 g, 40 mmol), and then heated to reflux for 16 hours. After the reaction mixture was passed through a celite pad, it was purified by silica gel column chromatography (n-hexane:dichloromethane (1:2, v / v)) to obtain 3-isopropoxy-1,1,3,3-tetraphenyldisiloxan-1-ol (colorless liquid, 4.28 g, 47%).

[0176] The reaction scheme of Example 5 and the 29 Si{ 1 H} NMR measurement results are shown below.

[0177]

Chemical formula

[0178] 29 Si{ 1 H} NMR (119 MHz, CDCl3): δ -36.9, -40.1 ppm

[0179] <Example 6> In a nitrogen atmosphere in a round-bottom flask, 1,1,3,3,5,5-hexamethyltrisiloxane (3.01 mL, 12 mmol) was dissolved in tetrahydrofuran (36 mL), and the mixture was stirred at -80 °C for 10 minutes. Trichloroisocyanuric acid (0.93 g, 4 mmol) was added thereto, and the temperature was gradually raised to room temperature and stirred for 12 hours. Triethylamine (3.36 mL, 24 mmol) and 2-propanol (1.85 mL, 24 mmol) were added to the resulting reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (4 mL) and added dropwise to a slurry obtained by mixing 5% palladium on carbon (24 mg, 0.03 mmol), distilled water (0.43 g), and tetrahydrofuran ( 20 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through a Celite pad, and the filtrate was concentrated to obtain a crude product. This crude product was produced by silica gel column chromatography (n-hexane:acetone (10:1, v / v)) to obtain 5-isopropoxy-1,1,3,3,5,5-hexamethyltrisiloxan-1-ol (colorless liquid, 1.46 g, 43%).

[0180] Reaction scheme and product of Example 6 29 Si{ 1 The 1H NMR measurement results are shown below.

[0181]

Chemical formula

[0182] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -8.8, -11.2, -47.1 ppm

[0183] <Example 7> In a nitrogen atmosphere in a round-bottom flask, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (3.99 g, 12 mmol) was dissolved in tetrahydrofuran (36 mL) and stirred at -80 °C for 10 minutes. Trichloroisocyanuric acid (0.93 g, 4 mmol) was added thereto, and the temperature was gradually raised to room temperature and stirred for 12 hours. Triethylamine (3.36 mL, 24 mmol) and 2-propanol (1.85 mL, 24 mmol) were added to the resulting reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (4 mL) and added dropwise to a slurry obtained by mixing 5% palladium on carbon (24 mg, 0.03 mmol), distilled water (0.43 g, 24 mmol), and tetrahydrofuran (20 mL), and stirred at room temperature for 1 hour. The reaction mixture was passed through a Celite pad, and the filtrate was concentrated to obtain a crude product. This crude product was purified by silica gel column chromatography (dichloromethane) to obtain 5-isopropoxy-1,1,5,5-tetramethyltrisiloxan-1-ol (colorless liquid, 2.05 g, 42%).

[0184] Reaction scheme and product of Example 7 29 Si{ 1 The 1H NMR measurement results are shown below.

[0185]

Chem.

[0186] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -10.4, -13.0, -20.2 ppm

[0187] <Example 8> In a nitrogen atmosphere in a round-bottom flask, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (3.99 g, 12 mmol) was dissolved in tetrahydrofuran (36 mL), and the mixture was stirred at -80 °C for 10 minutes. Trichloroisocyanuric acid (0.93 g, 4 mmol) was added thereto, and the temperature was gradually raised to room temperature and stirred for 12 hours. Triethylamine (3.36 mL, 24 mmol) and 2-propanol (1.85 mL, 24 mmol) were added to the resulting reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (4 mL) and added dropwise to a slurry obtained by mixing 5% palladium on carbon (24 mg, 0.03 mmol), distilled water (0.43 g) and tetrahydrofuran (20 mL), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain a crude product. This crude product was purified by silica gel column chromatography (n-hexane:acetone (10:1, v / v)) to obtain 5-isopropoxy-1,1,3,3,5,5-hexamethyltrisiloxan-1-ol (colorless liquid, 1.46 g, 43%).

[0188] Reaction scheme and product of Example 8 29 Si{ 1 The 1H NMR measurement results are shown below.

[0189]

Chemical formula

[0190] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -17.7, -37.9, -40.5 ppm

[0191] <Example 9> In a nitrogen atmosphere in an eggplant flask, B(C6F5)3 (51 mg, 0.10 mmol) and diphenylsilanediol (4.33 g, 20 mmol) were dissolved in toluene (80 mL), and the mixture was stirred at 0 °C. To the resulting solution, diphenylsilane (7.37 mL, 40 mmol) was added, and the temperature was gradually raised to room temperature and stirred for 30 minutes. Then, the reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain 1,1,3,3,5,5-hexaphenyltrisiloxane.

[0192] In a nitrogen atmosphere in an eggplant flask, 1,1,3,3,5,5-hexaphenyltrisiloxane (11.83 g, 20 mmol) was dissolved in tetrahydrofuran (60 mL), and the mixture was stirred at -80 °C. Trichloroisocyanuric acid (1.55 g, 6.67 mmol) was added little by little, and the temperature was gradually raised to room temperature and stirred for 3 hours. Triethylamine (5.6 mL, 40 mmol) and 2-propanol (3.1 mL, 40 mmol) were added to the resulting reaction solution, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran, mixed with 5% palladium on carbon (40 mg, 0.02 mmol) and distilled water (0.72 g, 40 mmol), and heated to reflux for 12 hours. After the reaction mixture was passed through a celite pad, it was purified by silica gel column chromatography (dichloromethane) to obtain 5-isopropoxy-1,1,3,3,5,5-hexaphenyltrisiloxan-1-ol (white solid, 3.77 g, 29%).

[0193] The reaction scheme and product of Example 9 29 Si{ 1 The 1H NMR measurement results are shown below.

[0194]

Chemical formula

[0195] 29 Si{ 11H NMR (119 MHz, CDCl3): δ -36.7, -39.4, -45.0 ppm

[0196] <Example 10> In a nitrogen atmosphere in an eggplant flask, 3-methyl-1,1,5,5-tetraphenyl-3-vinyltrisiloxane (2.05 g, 4.38 mmol) was dissolved in tetrahydrofuran and stirred at 0 °C for 10 minutes. Trichloroisocyanuric acid (339 mg, 1.46 mmol) was added thereto, and the temperature was gradually raised to room temperature and stirred for 3 hours. Triethylamine (1.22 mL, 8.76 mmol) and 2-propanol (0.68 mL, 8.76 mmol) were added thereto and stirred at room temperature for 3 hours. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (20 mL), mixed with 5% palladium on carbon (8.8 mg, 0.0044 mmol) and distilled water (0.16 g, 8.76 mmol), and heated under reflux for 12 hours. After the reaction mixture was passed through a celite pad, it was purified by silica gel column chromatography (dichloromethane) to obtain 5-isopropoxy-3-methyl-1,1,5,5-tetraphenyl-3-vinyltrisiloxan-1-ol (colorless liquid, 903 mg, 38%). l) were added and stirred at room temperature for 3 hours. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (20 mL), mixed with 5% palladium on carbon (8.8 mg, 0.0044 mmol) and distilled water (0.16 g, 8.76 mmol), and heated under reflux for 12 hours. After the reaction mixture was passed through a celite pad, it was purified by silica gel column chromatography (dichloromethane) to obtain 5-isopropoxy-3-methyl-1,1,5,5-tetraphenyl-3-vinyltrisiloxan-1-ol (colorless liquid, 903 mg, 38%).

[0197] Reaction scheme of Example 10 and 29 Si{ 1 1H NMR measurement results of the product are shown below.

[0198]

Chemical formula

[0199] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -32.2, -37.5, -40.2 ppm

[0200] <Example 11> In a nitrogen atmosphere in a eggplant flask, 1,1,7,7-tetramethyl-3,3,5,5-tetraphenyltetrasiloxane (3.74 g, 7.04 mmol) was dissolved in tetrahydrofuran and stirred at -80 °C for 10 minutes. Trichloroisocyanuric acid (0.55 g, 2.35 mmol) was added thereto, and the temperature was gradually raised to room temperature and stirred for 18 hours. Triethylamine (1.95 mL, 14 mmol) and 2-propanol (1.08 mL, 14 mmol) were added thereto, and the mixture was stirred at room temperature for 4 hours. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (6 mL), dropped into a slurry obtained by mixing 5% palladium carbon (14 mg, 0.007 mmol), distilled water (0.30 g) and tetrahydrofuran (15 mL), and then stirred at room temperature for 1 hour. After passing the reaction mixture through a Celite pad, purification by silica gel column chromatography gave 7-isopropoxy-1,1,7,7-tetramethyl-3,3,5,5-tetraphenyltetrasiloxan-1-ol (colorless liquid, 1.66 g, 39%).

[0201] Reaction scheme and product of Example 11 29 Si{ 1 The 1H NMR measurement results are shown below.

[0202]

Chemical formula

[0203] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -9.9, -12.2, -47.0, -47.2 ppm

[0204] <Example 12> In a nitrogen atmosphere glove box, B(C6F5)3 (102.4 mg, 0.20 mmol) was dissolved in toluene (80 mL). To the resulting solution, diphenylsilane (3.69 mL, 20 mmol) was added, followed by the addition of acetone (737 μL, 10 mmol) over 5 minutes, and then stirred at room temperature for 10 minutes. Acetone (1.47 mL, 20 mmol) was added to the resulting reaction solution and stirred at room temperature for 1 hour. Diphenylsilane (3.69 mL, 20 mmol) was added to the resulting reaction solution, stirred for 20 minutes, and then acetone (737 μL, 10 mmol) was further added and stirred for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (60 mL), mixed with 5% palladium on carbon (20 mg, 0.01 mmol) and distilled water (0.36 g, 20 mmol), and heated to reflux for 16 hours. After passing the reaction mixture through a celite pad, it was purified by silica gel column chromatography (n-hexane:dichloromethane (1:2, v / v)) to obtain 7-isopropoxy-1,1,3,3,5,5,7,7-octaphenyltetrasiloxan-1-ol (colorless liquid, 1.29 g, 15%).

[0205] Reaction scheme and product of Example 12 29 Si{ 1 The 1H NMR measurement results are shown below.

[0206]

Chem.

[0207] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -37.6, -40.4, -45.7, -46.2 ppm

[0208] <Example 13> In a nitrogen atmosphere in a eggplant flask, 2,2-bis((dimethylsilyl)oxy)-4,4,8,8-tetramethyl-6,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (1.62 g, 3.0 mmol) was dissolved in tetrahydrofuran (9 mL), and the mixture was stirred at -80 °C for 10 minutes. Trichloroisocyanuric acid (232 mg, 4 mmol) was added thereto, and the temperature was gradually raised to room temperature and stirred for 12 hours. Triethylamine (0.84 mL, 6.0 mmol) and 2-propanol (0.46 mL, 6.0 mmol) were added to the resulting reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (3 mL), and added dropwise to a slurry obtained by mixing 5% palladium on carbon (6 mg, 0.03 mmol), distilled water (0.11 g, 6.0 mmol) and tetrahydrofuran (6 mL), and stirred at room temperature for 1 hour. After the reaction mixture was passed through a celite pad, it was purified by gel permeation chromatography (n-hexane) to obtain ((2-((isopropoxydimethylsilyl)oxy-4,4,8,8-tetramethyl-6,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-yl)oxy)dimethylsilanol (colorless liquid, 1.46 g, 43%).

[0209] Reaction scheme and product of Example 13 29 Si{ 1 The 1H NMR measurement results are shown below.

[0210]

Chemical formula

[0211] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -8.9, -11.6, -16.3, -46.4, -106.9 ppm

[0212] <Example 14> In a nitrogen atmosphere glove box, acetone (147 μL, 2.0 mmol) was added to a solution obtained by dissolving B(C6F5)3 (10.2 mg, 0.02 mmol) and 2,2,6,6-tetramethyl-4,8-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (785 mg, 2.0 mmol) in toluene (8 mL), and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (8 mL), mixed with 5% palladium on carbon (4.0 mg, 0.002 mmol) and distilled water (72 mg, 4.0 mmol), and heated to reflux for 16 hours. After the reaction mixture was passed through a celite pad to concentrate and remove the solvent, it was purified by silica gel column chromatography (n-hexane:dichloromethane (1:2, v / v)) to obtain (2r,6r)-6-isopropoxy-4,4,8,8-tetramethyl-2,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-ol (trans form, 151.3 mg, 16%) and (2s,6s)-6-isopropoxy-4,4,8,8-tetramethyl-2,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-ol (cis form, 116.1 mg, 12%).

[0213] Reaction scheme of Example 14 and products 29 Si{ 1 The 1H NMR measurement results are shown below.

[0214]

Chemical formula

[0215] trans form: 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -16.5, -68.7, -72.5 ppm cis form: 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ -16.22, -68.3, -72.0 ppm

[0216] <Example 15> In a glove box under a nitrogen atmosphere, acetone (369 μL, 5.0 mmol) was added dropwise to a solution obtained by dissolving B(C6F5)3 (25.6 mg, 0.05 mmol) and 2,2,6,6,10,10,14,14-octamethyl-4,12-diphenyl-1,3,5,7,9,11,13,15-octaoxa-2,4,6,8,10,12,14-heptasilaspiro[7.7]pentadecane (3.01 g, 5.0 mmol) in toluene (20 mL), and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (20 mL), mixed with 5% palladium on carbon (10 mg, 0.005 mmol) and distilled water (0.18 g, 10 mmol), and heated under reflux for 1 hour. After the reaction mixture was passed through a celite pad, it was purified by silica gel column chromatography (n-hexane:dichloromethane (1:2, v / v)) to obtain 12-isopropoxy-2,2,6,6,10,10,14,14-octamethyl-4,12-diphenyl-1,3,5,7,9,11,13,15-octaoxa-2,4,6,8,10,12,14-heptasilaspiro[7.7]pentadecan-1-ol (colorless liquid, 1.24 g, 37%).

[0217] The reaction scheme of Example 15 and the 29 Si{ 1 1H} NMR measurement results are shown below.

[0218]

Chemical formula

[0219] 29 Si{ 1 1H} NMR (119 MHz, CDCl3): δ -16.02, -16.03, -16.6, -16.7, -68.8, -72.7, -105.7 ppm

[0220] <Example 16> In a nitrogen atmosphere glove box, B(C6F5)3 (51.2 mg, 0.1 mmol) was dissolved in toluene (80 mL) and mixed with acetone (2.95 mL, 40 mmol). To the resulting solution, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane (6.65 mL, 20 mmol) was added and stirred at room temperature for 30 minutes. Then, diphenylsilane (7.37 mL, 40 mmol) was added and stirred at room temperature for another 30 minutes. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain 3,3,7,7-tetramethyl-1,1,5,5,9,9-hexaphenylpentasiloxane.

[0221] In a nitrogen atmosphere eggplant flask, 3,3,7,7-tetramethyl-1,1,5,5,9,9-hexamethylpentasiloxane (14.66 g, 20 mmol) was dissolved in tetrahydrofuran (60 mL) and stirred at -80 °C. Trichloroisocyanuric acid (1.53 g, 6.67 mmol) was added little by little, and then the mixture was stirred for 12 hours while gradually warming up to room temperature. Triethylamine (5.6 mL, 40 mmol) and 2-propanol (3.1 mL, 40 mmol) were added to the resulting reaction solution and stirred at room temperature for 4 hours. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (60 mL), mixed with 5% palladium on carbon (40 mg, 0.02 mmol) and distilled water (0.72 g, 40 mmol), and heated under reflux for 12 hours. The reaction mixture was passed through a celite pad and then purified by silica gel column chromatography (n-hexane:dichloromethane (1:1, v / v)) to obtain 9-isopropoxy-3,3,7,7-tetramethyl-1,1,5,5,9,9-hexaphenylpentasiloxan-1-ol (colorless liquid, 7.21 g, 45%).

[0222] Reaction scheme and product of Example 16 29 Si{ 1 The 1H NMR measurement results are shown below.

[0223]

Chemical formula

[0224] 29 Si{ 1 H} NMR (119 MHz, CDCl3): δ -18.3, -19.1, -38.3, -41.7, -48.0 ppm

[0225] <Example 17> 3-Isopropoxy-1,1,3,3-tetraphenyldisiloxan-1-ol (5.86 g, 12.8 mmol) was dissolved in dichloromethane (40 mL). Triethylamine (2.7 mL, 19.3 mmol) and chlorodimethylsilane (2.1 mL, 19.3 mmol) were added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (10 mL) and added dropwise over 1 minute to a mixture of palladium on carbon (25 mg, 0.0125 mmol), water (0.50 g, 27.7 mmol), and tetrahydrofuran (30 mL), followed by stirring for 30 minutes. Then, the reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain 5-isopropoxy-1,1-dimethyl-3,3,5,5-tetraphenyltrisiloxan-1-ol (white solid, 6.72 g, 99%).

[0226] The reaction scheme of Example 17 and the 29 Si{ 1 H} NMR measurement results are shown below.

[0227]

Chemical formula

[0228] 29 Si{ 1 H} NMR (119 MHz, CDCl3): δ -9.0, -39.7, -46.6 ppm <Example 18> 5-Isopropoxy-1,1,3,3,5,5-hexaphenyltrisiloxan-1-ol (3.93 g, 6.0 mmol) was dissolved in dichloromethane (12 mL) and stirred at room temperature. Triethylamine (1.7 mL, 12 mmol) and chlorodimethylsilane (1.3 mL, 12 mmol) were added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (25 mL), added dropwise to a mixture of palladium carbon (10.8 mg, 0.0054 mmol), distilled water (0.20 g, 10.8 mmol), and tetrahydrofuran (5 mL) over 1 minute, and then stirred for 30 minutes. The reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in dichloromethane (20 mL) and stirred at room temperature. Triethylamine (1.5 mL, 10.8 mmol) and chlorodimethylsilane (1.2 mL, 10.8 mmol) were added thereto, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (15 mL), added dropwise to a mixture of palladium carbon (10.4 mg, 0.0052 mmol), distilled water (0.19 g, 10.4 mmol), and tetrahydrofuran (5 mL) over 1 minute, and then stirred for 30 minutes. Thereafter, the reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain 9-isopropoxy-1,1,3,3-tetramethyl-5,5,7,7,9,9-hexaphenylpentasiloxan-1-ol (colorless liquid, 4.04 g, 84%).

[0229] Reaction scheme and product of Example 18 29 Si{ 1 The 1H}NMR measurement results are shown below.

[0230]

Chemical formula

[0231] 29 Si{ 11H NMR (119 MHz, CDCl3): δ -10.8, -20.0, -41.0, -46.5, -47.5 ppm

[0232] <Example 19> 7-Isopropoxy-1,1,3,3,5,5,7,7-octaphenyltrisiloxan-1-ol (6.49 g, 7.61 mmol) was dissolved in dichloromethane (30 mL). Triethylamine (1.7 mL, 12 mmol) and chlorodimethylsilane (1.3 mL, 12 mmol) were added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (25 mL), added dropwise over 1 minute to a mixture of palladium carbon (15 mg, 0.0076 mmol), distilled water (0.27 g, 15.2 mmol), and tetrahydrofuran (5 mL), and then stirred for 30 minutes. The reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in dichloromethane (30 mL), mixed with triethylamine (1.7 mL, 12 mmol) and chlorodimethylsilane (1.3 mL, 12 mmol), and stirred at room temperature for 1 hour. The reaction mixture was passed through an alumina pad, and the filtrate was concentrated to obtain a residue. This residue was dissolved in tetrahydrofuran (25 mL), added dropwise over 1 minute to a mixture of palladium carbon (15 mg, 0.0076 mmol), distilled water (0.27 g, 15.2 mmol), and tetrahydrofuran (5 mL), and then stirred for 30 minutes. The reaction mixture was passed through a celite pad, and the filtrate was concentrated to obtain 13-isopropoxy-1,1,3,3,5,5-hexamethyl-7,7,9,9,11,11,13,13-octaphenylheptasiloxane (colorless liquid, 7.59 g, 93%).

[0233] Reaction scheme and product of Example 1929 Si{ 1 The 1H NMR measurement results are shown below.

[0234]

Chemical formula

[0235] 29 Si{ 1 H} NMR (119 MHz, CDCl3): δ -10.7, -20.5, -21.0, -41.2, -46.4, -46.5, -47.5 ppm

[0236] <Example 20> In a glove box under a nitrogen atmosphere, B(C6F5)3 (25.6 mg, 0.05 mmol) and 1-isopropoxy-3,3,3-trimethyl-1,1-diphenyldisiloxane (331 mg, 1.0 mmol) were dissolved in toluene (4 mL) and stirred at room temperature. To the resulting solution, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol) was added and stirred at room temperature for 15 minutes. To this reaction solution, 7-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasilox an-1-ol (380 μL, 1.0 mmol) was added and stirred at room temperature for 15 minutes. To this reaction solution, diphenylsilane (184 μL, 1.0 mmol) was added and stirred at room temperature for 15 minutes. To this reaction solution, acetone (73.4 μL, 1.0 mmol) was added and stirred at room temperature for 15 minutes. To this reaction solution, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H, 328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. To this reaction solution, 7-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxan-1-ol (380 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. To this reaction solution, diphenylsilane (184 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. To this reaction solution, acetone (73.4 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. To this reaction solution, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. To this reaction solution, 7-isopropoxy-1,1,3,3,5,5,7,7-octamethyltetrasiloxan-1-ol (380 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. After passing the reaction mixture through an alumina pad, it was purified by gel permeation chromatography (n-hexane) to obtain 1-isopropoxy-1,1,3,3,5,5,7,7,9,9,13,13,15,15,17,17,19,19,21,21,25,25,27,27,29,29,31,31,33,33,37,37,37-tritriacontamethyl-11,11,23,23,35,35-hexaphenylnonadecasiloxane (colorless liquid, 900 mg, 49%).

[0237] Reaction scheme of Example 20, product 29 Si{ 1 The 1H} NMR measurement results of the product and the MALDI-TOFMS measurement results of the product are shown below. The MALDI-TOFMS spectrum of the product is shown in Figure 1.

[0238]

Chemical formula

[0239] 29 Si{ 1 1H} NMR (119 MHz, CDCl3): δ 9.9, -14.7, -20.76, -20.766, -20.773, -20.78, -20.9, -21.66, -21.67, -21.7, -21.835, -21.843, -21.91, -21.95 -48.0, -48.50, -48.51 ppm MALDI-TOFMS [M+Na] + :1859.5

[0240] <Example 21> In a glove box under a nitrogen atmosphere, B(C6F5)3 (25.6 mg, 0.05 mmol) and 1-isopropoxy-3,3,7,7,11,11,11-heptamethyl-1,1,5,5,9,9-hexaphenylhexasiloxane (875 mg, 1.0 mmol) were dissolved in toluene (4 mL) and stirred at room temperature. To the resulting solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 9-isopropoxy-3,3,7,7-tetramethyl-1,1,5,5,9,9-hexaphenylpentasiloxan-1-ol (803 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 9-isopropoxy-3,3,7,7-tetramethyl-1,1,5,5,9,9-hexaphenylpentasiloxan-1-ol (803 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 9-isopropoxy-3,3,7,7-tetramethyl-1,1,5,5,9,9-hexaphenylpentasiloxan-1-ol (803 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( HMD2M H ((328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution, trimethylsilanol (104 μL, 1.1 mmol) was added and stirred at room temperature for 20 minutes. After concentrating the reaction mixture, it was purified by silica gel column chromatography (n - hexane:dichloromethane (2:1, v / v)), and further purified by gel permeation chromatography (n - hexane) to obtain 1,1,1,3,3,7,7,11,11,15,15,19,19,23,23,27,27,31,31,35,35,39,39,43,43,47,47,51,51 - triacontamethyl - 5,5,9,9,13,13,17,17,21,21,25,25,29,29,33,33,37,37,41,41,45,45,49,49 - tetracosaphenylhexacosasiloxane (colorless liquid, 1.83 g, 53%)).

[0241] Reaction scheme and product of Example 21 29 Si{ 1 The 1H NMR measurement results are shown below.

[0242]

Chemical formula

[0243] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ 9.9, 7.5, -19.0, -19.26, -19.27, -19.28, -19.2 9, -19.4, -19.5, -19.6, -20.4, -20.8, -21.7, -47.8, -48.0, -48.06, -48.08, -48.3 ppm

[0244] <Example 22> ​In a glove box under a nitrogen atmosphere, B(C6F5)3 (25.6 mg, 0.05 mmol) and 1-isopropoxy-5,5,5-trimethyl-1,1,3,3-tetraphenyltrisiloxane (529 mg, 1.0 mmol) were dissolved in toluene (4 mL) and stirred at room temperature. To the resulting solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 5-isopropoxy-1,1-dimethyl-3,3,5,5-tetraphenyltrisiloxane-1-ol (531 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 5-isopropoxy-1,1-dimethyl-3,3,5,5-tetraphenyltrisiloxane-1-ol (531 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 5-isopropoxy-1,1-dimethyl-3,3,5,5-tetraphenyltrisiloxane-1-ol (531 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 5-isopropoxy-1,1-dimethyl-3,3,5,5-tetraphenyltrisiloxane-1-ol (531 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H, 328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution, a toluene (2 mL) solution of 5-isopropoxy-1,1-dimethyl-3,3,5,5-tetraphenyltrisiloxan-1-ol (531 mg, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution, acetone (73.7 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature. To this reaction solution, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution, trimethylsilanol (104 μL, 1.1 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was concentrated and purified by silica gel column chromatography, and then further purified by gel permeation chromatography (n-hexane) to obtain 1,1,1,3,3,5,5,11,11,13,13,19,19,21,21,27,27,29,29,35,35,37,37,43,43,45,45,51,51,51-triacontamethyl-7,7,9,9,15,15,17,17,23,23,25,25,31,31,33,33,39,39,41,41,47,47,49,49-tetracosaphenylhexacosasiloxane (colorless liquid, 1.58 g, 46%).

[0245] Reaction scheme of Example 22 and 29 Si{ 1 The 1H NMR measurement results of the product are shown below.

[0246]

Chemical formula

[0247] 29 Si{ 11H NMR (119 MHz, CDCl3): δ 10.1, 7.3, -20.40, -20.41, -20.43, -20.8, -21. 2, -47.3, -47.68, -47.71, -47.73 ppm

[0248] <Example 23> In a glove box under a nitrogen atmosphere, B(C6F5)3 (25.6 mg, 0.05 mmol) and 1-isopropoxy-7,7,7-trimethyl-1,1,3,3,5,5-hexaphenyltetrasiloxane (727 mg, 1.0 mmol) were dissolved in toluene (4 mL) and stirred at room temperature. To the resulting solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. A toluene (2 mL) solution of 9-isopropoxy-1,1,3,3-tetramethyl-5,5,7,7,9,9-hexaphenylpentasiloxan-1-ol (803 mg, 1.0 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. A toluene (2 mL) solution of 9-isopropoxy-1,1,3,3-tetramethyl-5,5,7,7,9,9-hexaphenylpentasiloxan-1-ol (803 mg, 1.0 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. A toluene (2 mL) solution of 9-isopropoxy-1,1,3,3-tetramethyl-5,5,7,7,9,9-hexaphenylpentasiloxan-1-ol (803 mg, 1.0 mmol) was added to the reaction solution, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H, 328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution, 1,1,3,3,5,5,5-heptamethyltrisiloxan-1-ol (262 mg, 1.1 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was concentrated and purified by silica gel column chromatography (n-hexane:dichloromethane (2:1, v / v)), and further purified by gel permeation chromatography (n-hexane) to obtain 1,1,1,3,3,5,5,7,7,15,15,17,17,19,19,27,27,29,29,31,31,39,39,41,41,43,43,51,51,51-triacontamethyl-9,9,11,11,13,13,21,21,23,23,25,25,33,33,35,35,37,37,45,45,47,47,49,49-tetracosaphenylhexacosasiloxane (colorless liquid, 1.66 g, 48%).

[0249] Reaction scheme of Example 23 and the product 29 Si{ 1 The 1H NMR measurement results are shown below.

[0250]

Chemical formula

[0251] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ 10.0, 7.3, -20.6, -20.7, -21.4, -21.6, -21.8, -46.5, -46.6, -47.2, -47.57, -47.59 ppm

[0252] <Example 24> In a glove box under a nitrogen atmosphere, B(C6F5)3 (25.6 mg, 0.05 mmol) and 1-isopropoxy-9,9,9-trimethyl-1,1,3,3,5,5,7,7-octaphenylpentasiloxane (925 mg, 1.0 mmol) were dissolved in toluene (4 mL) and stirred at room temperature. To the resulting solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 13-isopropoxy-1,1,3,3,5,5-hexamethyl-7,7,9,9,11,11,13,13-octaphenylheptasiloxan-1-ol (1076 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 328 μL, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added a toluene (2 mL) solution of 13-isopropoxy-1,1,3,3,5,5-hexamethyl-7,7,9,9,11,11,13,13-octaphenylheptasiloxan-1-ol (1076 mg, 1.0 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H, 328 μL, 1.0 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. To this reaction solution, 1,1,3,3,5,5,7,7,7-nonamethyltetrasiloxan-1-ol (344 mg, 1.1 mmol) was added, and the mixture was stirred at room temperature for 20 minutes. The reaction mixture was concentrated and purified by silica gel column chromatography (n-hexane:dichloromethane (2:1, v / v)), and then further purified by gel permeation chromatography (n-hexane) to obtain 1,1,1,3,3,5,5,7,7,9,9,19,19,21,21,23,23,25,25,35,35,37,37,39,39,41,41,51,51,51-triacontamethyl-11,11,13,13,15,15,17,17,27,27,29,29,31,31,33,33,43,43,45,45,47,47,49,49-tetracosaphenylhexacosasiloxane (colorless liquid, 1.99 g, 58%).

[0253] Reaction scheme and product of Example 24 29 Si{ 1 The 1H NMR measurement results are shown below.

[0254]

Chemical formula

[0255] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ 9.9, 7.3, -20.67, -20.70, -21.36, -21.78, -21.83, -22.1, -46.39, -46.40, -46.43, -47.3, -47.6 ppm

[0256] <Example 25> In a nitrogen atmosphere glove box, B(C6F5)3 (5.1 mg, 0.01 mmol) and 1-isopropoxy-3,3,3-trimethyl-1,1-diphenyldisiloxane (66.1 mg, 0.20 mmol) were dissolved in toluene (0.8 mL) and stirred at room temperature. To the resulting solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 65.5 μL, 0.20 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added (2r,6r)-6-isopropoxy-4,4,8,8-tetramethyl-2 ,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane-2-ol (93.4 mg, 0.20 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added diphenylsilane (36.9 μL, 0.20 mmol), and the mixture was stirred at room temperature for 20 minutes. After passing the reaction mixture through an alumina pad, it was purified by gel permeation chromatography (n-hexane) to obtain (2r,6r)-2-((diphenylsilyl)oxy)-4,4,8,8-tetramethyl-6-((1,1,5,5,5-pentamethyl-3,3-diphenyltrisiloxaneyl)oxy)-2,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (colorless liquid, 94.6 mg, 50%).

[0257] The reaction scheme and product of Example 25 are 29 Si{ 1 H} NMR measurement results are shown below.

[0258]

Chemical formula

[0259] 29 Si{ 1 H} NMR (119 MHz, CDCl3): δ 10.0, -17.5, -19.7, -21.9, -47.8, -77.7, -79.3 ppm

[0260] <Example 26> In a nitrogen atmosphere glove box, B(C6F5)3 (2.6 mg, 0.005 mmol) and 1-isopropoxy-3,3,3-trimethyl-1,1-diphenyldisiloxane (33.1 mg, 0.10 mmol) were dissolved in toluene (0.4 mL) and stirred at room temperature. To the resulting solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 32.8 μL, 0.10 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added (2s,6s)-6-isopropoxy-4,4,8,8-tetramethyl-2,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocan-2-ol (46.7 mg, 0.10 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added diphenylsilane (18.4 μL, 0.10 mmol), and the mixture was stirred at room temperature for 20 minutes. After passing the reaction mixture through an alumina pad, it was purified by gel permeation chromatography (n-hexane) to obtain (2s,6s)-2-((diphenylsilyl)oxy)- 4,4,8,8-tetramethyl-6-((1,1,5,5,5-pentamethyl-3,3-diphenyltrisiloxanyl)oxy)-2,6-diphenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane (colorless liquid, 41.5 mg, 44%).

[0261] Reaction scheme and product of Example 26 29 Si{ 1 The 1H NMR measurement results are shown below.

[0262]

Chemical formula

[0263] 29 Si{ 1 1H NMR (119 MHz, CDCl3): δ 10.0, -17.4, -19.6, -21.9, -47.8, -77.6, -79.3 ppm

[0264] <Example 27> In a nitrogen atmosphere glove box, B(C6F5)3 (5.1 mg, 0.010 mmol) and 1-isopropoxy-3,3,3-trimethyl-1,1-diphenyldisiloxane (66.1 mg, 0.20 mmol) were dissolved in toluene (0.8 mL) and stirred at room temperature. To the resulting solution was added 1,1,3,3,5,5,7,7-octamethyltetrasiloxane ( H MD2M H , 65.5 μL, 0.20 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added 12-isopropoxy-2,2,6,6,10,10,14,14-octamethyl-4,12-diphenyl-1,3,5,7,9,11,13,15-octaoxa-2,4,6,8,10,12,14-heptasilaspiro[7.7]pentadecane-1-ol (135.0 mg, 0.20 mmol), and the mixture was stirred at room temperature for 20 minutes. To this reaction solution was added diphenylsilane (36.9 μL, 0.20 mmol), and the mixture was stirred at room temperature for 20 minutes. After passing the reaction mixture through an alumina pad, it was purified by gel permeation chromatography (n-hexane) to obtain 4-((diphenylsilyl)oxy)-2,2,6,6,10,10,14,14-octamethyl-12-((1,1,5,5,5-pentamethyl-3,3-diphenyltrisiloxanyl)oxy)-4,12-diphenyl-1,3,5,7,9,11,13,15-octaoxa-2,4,6,8,10,12,14-heptasilaspiro[7.7]pentadecane (colorless liquid, 131.6 mg, 57%).

[0265] The reaction scheme and product of Example 27 29 Si{ 1 H} NMR measurement results are shown below.

[0266]

Chemical formula

[0267] 29 Si{ 11H NMR (119 MHz, CDCl3): δ 10.0, -16.6, -16.7, -16.9, -17.0, -19.6, -21.9, -47.8, -77.7, -79.3 ppm

Industrial Applicability

[0268] According to the production method of the present disclosure, a novel method for producing a siloxane compound with a controlled substituent arrangement is provided.

Claims

1. In the presence of a first boron compound having Lewis acidity, reacting the hydrosilyl group of a compound having a hydrosilyl group with the hydroxysilyl group of a siloxane compound having a hydroxysilyl group and an alkoxysilyl group to synthesize a siloxane compound having an alkoxysilyl group by a dehydrogenative condensation step; In the presence of a second boron compound having Lewis acidity, reacting the alkoxysilyl group of the siloxane compound having an alkoxysilyl group with the hydrosilyl group of a first dihydrosilane compound to synthesize a siloxane compound having a hydrosilyl group by a first decarbonization hydrogen condensation step; A method for producing a siloxane compound, comprising N (N represents an integer of 1 or more) siloxane chain extension cycles consisting of:

2. The method for producing a siloxane compound according to claim 1, wherein the siloxane compound having a hydroxysilyl group and an alkoxysilyl group is represented by any one of formulas (A1) to (A6), and the compound having a hydrosilyl group is represented by formula (B). 【Chemical Formula 1】 【Chemical Formula 2】 【Chemical Formula 3】 【Chemical Formula 4】 【Chemical Formula 5】 【Chemical Formula 6】 (In formulas (A1) to (A6), R １ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; n1 to n3 and n7 each independently represent an integer of 1 to 20; n4 to n6 each independently represent an integer of 1 to 3.) 【Chemical Formula 7】 (In formula (B), R ３each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Y represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a siloxanyloxy group, or a silyloxy group. )

3. The method for producing a siloxane compound according to claim 1 or 2, wherein the first dihydrosilane compound is represented by formula (C). 【Chemical Formula 8】 (In formula (C), R ６ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. )

4. In one or more of the siloxane chain extension cycles, the first boron compound used in the dehydrogenative condensation step in the same cycle and the second boron compound used in the first decarburative dehydrogenative condensation step are the same compound. The method for producing a siloxane compound according to claim 1 or 2.

5. In one or more of the siloxane chain extension cycles, the dehydrogenative condensation step and the first decarburative dehydrogenative condensation step in the same cycle are carried out in one pot. The method for producing a siloxane compound according to claim 4.

6. The method for producing a siloxane compound according to claim 4, wherein the first boron compound and the second boron compound are tris(pentafluorophenyl)borane.

7. The above N is an integer of 2 or more, and between the Mth siloxane chain extension cycle and the (M + 1)th siloxane chain extension cycle (M represents an integer of 1 or more and N - 1 or less), in the presence of a third boron compound having Lewis acidity, reacting the siloxane compound having a hydrosilyl group obtained in the first decarburative dehydrogenative condensation step with a carbonyl compound to synthesize a siloxane compound having an alkoxysilyl group. A hydrosilylation step, In the presence of a boron tetra - compound having Lewis acidity, a second dehydrogenative condensation step of reacting a siloxane compound having an alkoxysilyl group with a hydrosilyl group of a second dihydrosilane compound to synthesize a siloxane compound having a hydrosilyl group, The method for producing a siloxane compound according to claim 1 or 2, comprising .

8. The method for producing a siloxane compound according to claim 7, wherein the carbonyl compound is represented by formula (D). 【Chemical formula 9】 (In formula (D), R ７ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.)

9. The method for producing a siloxane according to claim 7, wherein the second dihydrosilane compound is represented by formula (E). compound. 【Chemical formula 10】 (In formula (E), R ８ each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.)

10. The method for producing a siloxane compound according to claim 7, wherein the dehydrogenative condensation step, the first dehydrogenative condensation step, the hydrosilylation step, and the second dehydrogenative condensation step are performed in one - pot.

11. A siloxane compound having a hydroxy - silyl group and an alkoxysilyl group, represented by any one of formulas (A1) to (A6). 【Chemical formula 11】 【Chemical formula 12】 【Chemical formula 13】 【Chemical formula 14】 【Chemical formula 15】 【Chemical formula 16】 (In formulas (A1) to (A6), R １each independently represents a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; n1 to n3 and n7 each independently represent an integer of 1 to 20; n4 to n6 each independently represent an integer of 1 to 3.

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