JP6491493B2 - Method for producing linear trisiloxane compound - Google Patents

Description

  The present invention relates to a method for producing a terminal functional linear trisiloxane compound useful as a precursor of a silicone polymer material and a silica dispersant for a rubber compound.

  Polysiloxane polymers are generally called silicones, and are widely used industrially in the form of oils, rubbers, resins, and the like because of their advantages such as heat resistance and chemical stability. General-purpose polysiloxanes are generally produced by the polymerization reaction of monosilanes that are easily available, but their properties are strongly influenced by the molecular structure. Therefore, control of the molecular structure of silicone using a low molecular weight siloxane monomer, which is more structurally regulated, as a raw material is an important issue in terms of functional expression. Low molecular weight siloxanes having a reactive functional group such as a hydroxyl group in the molecule can be used for ligands such as silica dispersants for rubber compounds and transition metal complexes. For the linear siloxanes used for such purposes, it is particularly desirable to use a low molecular weight monodisperse with a fixed molecular weight from the viewpoint of controlling physical properties.

  Many prior studies have been made on the synthesis of linear siloxanes having a silicon number of 3 or more and having hydroxyl groups or alkoxy groups at both ends of the molecular chain. Low molecular weight linear siloxane having hydroxyl groups at both ends of the molecular chain is synthesized by hydrolysis of linear dichlorosiloxane having chlorine atoms at both ends or hydrolysis / dehydration condensation of dichloromonosilane (Patent Document 1). ). However, in this method, since the produced dihydroxy linear siloxanes are unstable under the synthesis conditions, a further condensation reaction occurs, and in addition to the intended low molecular weight linear siloxane, There was a problem that cyclic siloxane was by-produced and the yield of linear siloxane having a desired molecular weight was low.

  Patent Document 2 discloses a method for producing a low molecular weight linear siloxane having hydroxyl groups at both ends by hydrolysis of dialkoxysilane. Although this production method yields a low-molecular-weight linear siloxane having hydroxyl groups at both ends, there is still molecular weight dispersion, and linear siloxanes having alkoxy groups at both ends that are not completely hydrolyzed remain. There was a problem.

  Further, in Patent Document 3, 2,2,4,4,6,6-hexamethylcyclotrisiloxane, which is easily available, is reacted with water in the presence of an acid catalyst such as formic acid, and has a low molecular weight having hydroxyl groups at both ends. A method for producing a linear trisiloxane is reported. Also in this case, the yield of the generated linear trisiloxane having hydroxyl groups at both ends is not high, and it is necessary to remove the acid catalyst by distillation or neutralization treatment. In addition, a production method (Patent Document 4) using an ion exchange resin that is a solid acid as a catalyst has been reported as an acid catalyst that can be easily stopped and removed, but the selectivity of the reaction is still insufficient. In Patent Document 3, 2,2,4,4,6,6-hexamethylcyclotrisiloxane is reacted with an alcohol in the presence or absence of an acid catalyst such as formic acid to give 1-hydroxy-5-alkoxytrisiloxane. However, it is necessary to use an acid catalyst for the reaction with alcohols other than methanol under the conditions where no acid is used. . In Patent Document 5, 1,5-dimethoxyhexamethyltrisiloxane is hydrolyzed in the presence of zirconium oxide to produce 1,5-dihydroxyhexamethyltrisiloxane with a reaction yield of 85.2%. A method is described. However, there is a problem that it is not easy to obtain 1,5-dihydroxyhexamethyltrisiloxane which is a raw material in this production method, and the cost is high.

JP-A-7-233179 Japanese Patent Laid-Open No. 8-113649 US Pat. No. 4,113,690 JP 2012-140391 A JP-A-8-239476

  The present invention provides a method for producing a linear trisiloxane compound having a hydroxyl group at one of both ends of a molecular chain and a hydroxyl group or an alkoxy group at the other end in a high yield and in a single step from an easily available cyclic trisiloxane. The issue is to provide.

As a result of intensive studies to achieve the above object, the present inventors have found that various cyclic trisiloxanes are either water or water in the presence of hydrogen gas and / or a hydrogen generator and a rhenium catalyst or a platinum group transition metal catalyst. It has been found that a desired linear trisiloxane compound can be produced by reacting with alcohol, and the present invention has been completed.

That is, the present invention is a compound represented by the general formula (1) in the presence of hydrogen gas and / or a hydrogen generator and a rhenium catalyst or a platinum group transition metal catalyst :

（式中、Ｒは、ハロゲン原子で置換されていてもよい炭素数１〜８のアルキル基、又はハロゲン原子若しくは炭素数１〜２のアルキル基で置換されてもよいフェニル基を表す。複数のＲは、同一又は相異なっていてもよい。また、同一のケイ素原子に結合する二つのＲは、一体となって炭素数４〜６のアルカンジイル基を形成してもよい）で示される環状トリシロキサンと、一般式（２）：

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom or an alkyl group having 1 to 2 carbon atoms. R may be the same or different, and two R bonded to the same silicon atom may form an alkanediyl group having 4 to 6 carbon atoms together) Trisiloxane and general formula (2):

（式中、Ｒ^１は、水素原子；炭素数１〜８のアルキル基；又は炭素数７〜８のアラルキル基を表す。）で示される化合物を反応させることを特徴とする、一般式（３）：

(Wherein R ¹ represents a hydrogen atom; an alkyl group having 1 to 8 carbon atoms; or an aralkyl group having 7 to 8 carbon atoms), which is reacted with a compound represented by the general formula (3 ):

（式中、Ｒ及びＲ^１は前記と同じ意味を表す。）で示される直鎖状トリシロキサン化合物の製造方法（以下、本発明の製造方法と称する）に関する。

(Wherein R and R ¹ represent the same meaning as described above), and the production method of the linear trisiloxane compound (hereinafter referred to as the production method of the present invention).

  According to the production method of the present invention, a linear trisiloxane having 3 silicon atoms and having hydroxyl groups and / or alkoxy groups at both ends can be selectively produced under mild conditions.

  Hereinafter, the present invention will be described more specifically. First, the definition of R in the general formulas (1) and (3) will be described. The alkyl group having 1 to 8 carbon atoms represented by R may be linear, branched or cyclic, and specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group. , Sec-butyl group, tert-butyl group, cyclobutyl group, pentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, 1-methylpentyl group, 2,3-dimethyl Examples thereof include a butyl group, a cyclohexyl group, a cyclopentylmethyl group, a heptyl group, a 2-norbornyl group, and an octyl group. These alkyl groups may be substituted with a halogen atom. The halogen atom is preferably a fluorine atom or a chlorine atom. Specifically, fluoromethyl group, difluoromethyl group, chloromethyl group, dichloromethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloroethyl group , 3-fluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 3-chloropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3 4,4,5,5,5-heptafluoropentyl group, 3,3,4,4,5,5,7,7,7-nonafluorohexyl group and the like. Specific examples of the phenyl group that may be substituted with an alkyl group having 1 to 2 carbon atoms represented by R include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, and 4-methylphenyl. Group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,4-dimethylphenyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, 4-ethylphenyl group, etc. I can do it. In addition, two organic groups on the silicon atom represented by R can be bonded to each other to form a divalent alkanediyl group. Examples of the divalent organic group to be formed include 1,4-butanediyl group, 1,5-pentanediyl group, 1-methyl-1,4-pentanediyl group, 2-methyl-1,4-pentanediyl group and the like. I can do it.

In the production method of the present invention, R is preferably a linear alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a phenyl group, and is preferably a methyl group, 3 More preferably, it is a 3,3-trifluoropropyl group or a phenyl group.
Specific examples of the cyclic trisiloxane (1) that can be used as a raw material for the production method of the present invention include 2,2,4,4,6,6-hexamethylcyclotrisiloxane, 2,2,4,4. , 6,6-hexaethylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane, 2,2,4,4,6,6-hexapropylcyclotrisiloxane, 2, 4,6-trimethyl-2,4,6-tripropylcyclotrisiloxane, 2,2-diisopropyl-4,4,6,6-tetramethylcyclotrisiloxane, 2,4,6-trimethyl-2,4 6-tris (chloromethyl) cyclotrisiloxane, 2,4,6-trimethyl-2,4,6-tris (3,3-difluoropropyl) cyclotrisiloxane, 2,4,6-to Methyl-2,4,6-tris (3,3,3-trifluoropropyl) cyclotrisiloxane, 2,2,4,4,6,6-hexakis (3,3,3-trifluoropropyl) cyclotri Siloxane, 2-phenyl-2,4,4,6,6-pentamethylcyclotrisiloxane, 2,2-diphenyl-4,4,6,6-tetramethylcyclotrisiloxane, 2,4,6-tributyl- 2,4,6-trimethylcyclotrisiloxane, 2,4,6-trihexyl-2,4,6-trimethylcyclotrisiloxane, 2,4,6-trioctyl-2,4,6-trimethylcyclotrisiloxane, etc. It can be illustrated. These may have stereoisomers when they have two different substituents on the same silicon atom, but pure isomers or isomer mixtures may be used.

  In the manufacturing method of this invention, it can carry out using commercially available cyclic trisiloxane (1) as a raw material. Moreover, the cyclic trisiloxane (1) manufactured according to the manufacturing method reported in many nonpatent literatures can also be used. Examples of the method for producing the cyclic trisiloxane (1) include hydrolysis reaction of the corresponding dihalosilane or dialkoxysilane, reaction of dichlorosilane and zinc oxide, reaction of dichlorosilane and dimethyl sulfoxide, alkali of polysiloxane high molecular weight substance. Those skilled in the art can easily perform decomposition reactions with metal hydroxides, dehydrochlorination condensation reaction of 1,3-dihydroxydisiloxane and dihalosilane, dehydrochlorination condensation reaction of 1,3-dihalodisiloxane and silanediol, and the like. Manufacturing can be achieved.

Next, the definition of R ¹ will be described. R ¹ represents a hydrogen atom; an alkyl group having 1 to 8 carbon atoms; or an aralkyl group having 7 to 8 carbon atoms. In view of the high yield and purity of the manufactured product, R ¹ is preferably a hydrogen atom. In the production method using R ¹ as hydrogen, that is, water, forms such as ion-exchanged water, distilled water, and tap water can be used. Although not particularly limited, distilled water or ion-exchanged water is preferable because contamination with an ionic compound as an impurity may affect the reaction. The chemical equivalent of water with respect to the cyclic trisiloxane (1) is preferably 1 to 10,000 times, more preferably 2 to 10 equivalents in order to avoid the formation of a high molecular weight product and miscibility with an organic solvent. . Moreover, alcohol (2) which can be used for the manufacturing method of this invention is alcohol of a C1-C8 alkyl group. The alkyl alcohol of R ¹ -OH may be either a linear structure or a branched structure, and specifically includes methanol, ethanol, 2,2,2-trifluoroethanol, propyl alcohol, 2-propanol, butanol, Examples thereof include isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol and the like. The preferred alcohol is an alcohol having a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably methanol, ethanol or propanol. When an alcohol is used as the compound (2) in the production method of the present invention, it is preferable to use a dehydrated alcohol. As a chemical equivalent of alcohol with respect to cyclic trisiloxane (1), the range of 1-10000 equivalent is preferable, and 1-50 equivalent is still more preferable.

It is essential to carry out the production method of the present invention in the presence of a rhenium catalyst or a platinum group transition metal catalyst . The rhenium catalyst or platinum group transition metal catalyst that can be used in the production method of the present invention is any catalyst that promotes the ring-opening reaction of the cyclic trisiloxane (1) in the presence of hydrogen gas and / or a hydrogen generator. A specific example is a supported catalyst in which rhenium alone or platinum group transition metal alone is supported on a carrier, and a homogeneous platinum group transition metal complex catalyst. A supported catalyst is preferable in terms of easy handling. Examples of the platinum group transition metal in the supported catalyst include palladium, platinum, rhodium, iridium and ruthenium. In the supported catalyst, specific examples of the support include silica, alumina, diatomaceous earth, activated clay, activated carbon, barium sulfate, calcium carbonate and the like, and activated carbon is preferred. The supported catalyst is more preferably palladium activated carbon from the viewpoints of reaction rate, yield and purity, price, separation by filtration, and recovery and reuse of the catalyst. When using palladium activated carbon, what contains 1 to 10 weight% of palladium is suitable. As the homogeneous platinum group transition metal complex catalyst, a platinum group transition metal complex in which a neutral ligand such as olefin or phosphine is coordinated can be used. Specific examples include tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, bis (cyclooctadiene) platinum and the like. The amount of the rhenium catalyst or platinum group transition metal catalyst used in the production method of the present invention is usually 0.01 to 1000 mmol, preferably 1 to 1 mol of the rhenium or platinum group transition metal contained in the catalyst per 1 mol of the cyclic trisiloxane (1). Is preferably 0.5 to 50 mmol.

It is essential to carry out the production method of the present invention in the presence of hydrogen gas and / or a hydrogen generator. Examples of the hydrogen generator include a hydrogen generator that generates hydrogen gas by the action of a rhenium catalyst or a platinum group transition metal catalyst . Specific examples of the hydrogen generator include hydrides such as hydrosilanes and known hydrogen generators such as cyclic olefins such as cyclohexadiene, which can be appropriately selected from these. When a primary or secondary alcohol is used as the compound (2), the compound (2) can be used as a hydrogen generator by appropriately selecting a rhenium catalyst or a platinum group transition metal catalyst . Examples of alcohols that can be used include ethanol, isopropyl alcohol, sec-butyl alcohol, and the like. As the hydrogen generator, hydrosilanes and cyclohexadiene are preferable in terms of a good yield, such as 1,1,3,3,5,5-hexamethyl-1,5-dihydrotrisiloxane and 1,4-cyclohexadiene. Can be suitably used. It is preferable to carry out in the presence of hydrogen gas from the viewpoint of good yield and selectivity and easy removal. When carried out in the presence of hydrogen gas, hydrogen gas diluted with an inert gas such as nitrogen gas, helium, neon, argon, krypton, or xenon can be used as the reaction atmosphere as necessary. The pressure of the hydrogen gas is selected from the range of 10 kPa-100 MPa, preferably 10 kPa-10 MPa, more preferably atmospheric pressure. The fraction of hydrogen gas in the reaction atmosphere is selected from the range of 0.01 to 1.0, and 1.0 is preferable in terms of easy operation.

  The reaction temperature is not particularly limited, and those skilled in the art can use general temperature conditions for producing a siloxane having a hydroxyl group. As a specific example, the linear trisiloxane compound (3) can be obtained in good yield at a reaction temperature appropriately selected from a temperature range of −10 ° C. to 80 ° C. From the viewpoints of yield, safety and operability, an operating temperature selected from the range of 0 to 30 ° C. is preferred. The reaction time is appropriately selected by confirming the progress of the reaction by instrumental analysis, but it is preferable to carry out the reaction time appropriately selected from the range of 10 minutes to 300 hours.

  The production method of the present invention is preferably carried out in an organic solvent in terms of good yield. The organic solvent that can be used is not limited as long as it does not inhibit the reaction. Specifically, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, diethyl ether, diisopropyl ether, cyclopentyl methyl ether (CPME), Examples include ethers such as tetrahydrofuran (THF), 1,4-dioxane, 1,2-dimethoxyethane, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These organic solvents can be used singly or as a mixture of plural kinds at an arbitrary ratio. In terms of good yield and short reaction time, the organic solvent is preferably an ether, diethyl ether and THF are preferred, and THF is more preferred. In the case of carrying out the reaction between the cyclic trisiloxane (1) and an alcohol, if an alcohol compound is used in excess, the organic solvent may not be used.

In the production method of the present invention, when cyclic trisiloxane (1) and water are used, R ¹ is a hydrogen atom, that is, trisiloxane-1,5-diol having hydroxyl groups at both ends can be produced. When used, 1-alkoxy-5-hydroxytrisiloxane can be produced.

  Specific examples of the linear trisiloxane compound (3) that can be produced by the production method of the present invention include 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol, 1,1. , 3,3,5,5-hexaethyltrisiloxane-1,5-diol, 1,3,5-trimethyl-1,3,5-triethyltrisiloxane-1,5-diol, 1,1,3 3,5,5-hexapropyltrisiloxane-1,5-diol, 1,3,5-trimethyl-1,3,5-tripropyltrisiloxane-1,5-diol, 1,1,3,3- Tetramethyl-5,5-diisopropyltrisiloxane-1,5-diol, 1,1,5,5-tetramethyl-3,3-diisopropyltrisiloxane-1,5-diol, 1,3,5-trimethyl- 1,3,5-Tris Chloromethyl) trisiloxane-1,5-diol, 1,3,5-trimethyl-1,3,5-tris (3,3-difluoropropyl) trisiloxane-1,5-diol, 1,3,5- Trimethyl-1,3,5-tris (3,3,3-trifluoropropyl) trisiloxane-1,5-diol, 1,1,3,3,5,5-hexakis (3,3,3-tri Fluoropropyl) trisiloxane-1,5-diol, 1,1,3,3,5-pentamethyl-5-phenyltrisiloxane-1,5-diol, 1,3,5-trimethyl-1,3,5- Triphenyltrisiloxane-1,5-diol, 1,1,3,5,5-pentamethyl-3-phenyltrisiloxane-1,5-diol, 1,1,3,3-tetramethyl-5,5- Diphenyltri Loxane-1, 5-diol, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane-1, 5-diol, 1,3,5-tributyl-1,3,5-trimethyltrisiloxane -1,5-diol, 1,3,5-trihexyl-1,3,5-trimethyltrisiloxane-1,5-diol, 1,3,5-trimethyl-1,3,5-trioctyltrisiloxane- 1,5-diol, 1-hydroxy-5-methoxy-1,1,3,3,5,5-hexamethyltrisiloxane, 1-hydroxy-5-methoxy-1,1,3,3,5,5 -Hexaethyltrisiloxane, 1-hydroxy-5-methoxy-1,3,5-trimethyl-1,3,5-triethyltrisiloxane, 1-hydroxy-5-methoxy-1,1,3,3,5, 5-he Xapropyltrisiloxane, 1-hydroxy-5-methoxy-1,3,5-trimethyl-1,3,5-tripropyltrisiloxane, 1-hydroxy-5-methoxy-1,1,3,3-tetramethyl -5,5-diisopropyltrisiloxane, 1-hydroxy-5-methoxy-1,1,5,5-tetramethyl-3,3-diisopropyltrisiloxane, 1-hydroxy-5-methoxy-1,3,5- Trimethyl-1,3,5-tris (chloromethyl) trisiloxane, 1-hydroxy-5-methoxy-1,3,5-trimethyl-1,3,5-tris (3,3-difluoropropyl) trisiloxane, 1-hydroxy-5-methoxy-1,3,5-trimethyl-1,3,5-tris (3,3,3-trifluoropropyl) trisiloxane, 1 Hydroxy-5-methoxy-1,1,3,3,5,5-hexakis (3,3,3-trifluoropropyl) trisiloxane, 1-hydroxy-5-methoxy-1,1,3,3,5 Pentamethyl-5-phenyltrisiloxane, 1-hydroxy-5-methoxy-1,3,5-trimethyl-1,3,5-triphenyltrisiloxane, 1-hydroxy-5-methoxy-1,1,3 5,5-pentamethyl-3-phenyltrisiloxane, 1-hydroxy-5-methoxy-1,1,3,3-tetramethyl-5,5-diphenyltrisiloxane, 1-hydroxy-5-methoxy-1,1 , 5,5-tetramethyl-3,3-diphenyltrisiloxane, 1-hydroxy-5-methoxy-1,3,5-tributyl-1,3,5-trimethyltrisiloxane 1-hydroxy-5-methoxy-1,3,5-trihexyl-1,3,5-trimethyltrisiloxane, 1-hydroxy-5-methoxy-1,3,5-trimethyl-1,3,5- Trioctyltrisiloxane, 1-hydroxy-5-ethoxy-1,1,3,3,5,5-hexamethyltrisiloxane, 1-hydroxy-5-ethoxy-1,1,3,3,5,5- Hexaethyltrisiloxane, 1-hydroxy-5-ethoxy-1,3,5-trimethyl-1,3,5-triethyltrisiloxane, 1-hydroxy-5-ethoxy-1,1,3,3,5,5 -Hexapropyltrisiloxane, 1-hydroxy-5-ethoxy-1,3,5-trimethyl-1,3,5-tripropyltrisiloxane, 1-hydroxy-5-ethoxy-1,1,3 , 3-tetramethyl-5,5-diisopropyltrisiloxane, 1-hydroxy-5-ethoxy-1,1,5,5-tetramethyl-3,3-diisopropyltrisiloxane, 1-hydroxy-5-ethoxy-1 , 3,5-trimethyl-1,3,5-tris (chloromethyl) trisiloxane, 1-hydroxy-5-ethoxy-1,3,5-trimethyl-1,3,5-tris (3,3-difluoro Propyl) trisiloxane, 1-hydroxy-5-ethoxy-1,3,5-trimethyl-1,3,5-tris (3,3,3-trifluoropropyl) trisiloxane, 1-hydroxy-5-ethoxy- 1,1,3,3,5,5-hexakis (3,3,3-trifluoropropyl) trisiloxane, 1-hydroxy-5-ethoxy-1,1,3,3,5 Pentamethyl-5-phenyltrisiloxane, 1-hydroxy-5-ethoxy-1,3,5-trimethyl-1,3,5-triphenyltrisiloxane, 1-hydroxy-5-ethoxy-1,1,3,5 , 5-pentamethyl-3-phenyltrisiloxane, 1-hydroxy-5-ethoxy-1,1,3,3-tetramethyl-5,5-diphenyltrisiloxane, 1-hydroxy-5-ethoxy-1,1, 5,5-tetramethyl-3,3-diphenyltrisiloxane, 1-hydroxy-5-ethoxy-1,3,5-tributyl-1,3,5-trimethyltrisiloxane, 1-hydroxy-5-ethoxy-1 , 3,5-trihexyl-1,3,5-trimethyltrisiloxane, 1-hydroxy-5-ethoxy-1,3,5-trimethyl-1,3 -Trioctyltrisiloxane, 1-hydroxy-5-propyloxy-1,1,3,3,5,5-hexamethyltrisiloxane, 1-hydroxy-5-isopropyloxy-1,1,3,3,5 , 5-hexamethyltrisiloxane, 1-hydroxy-5-butoxy-1,1,3,3,5,5-hexamethyltrisiloxane and the like.

In the production method of the present invention, the neutralization step is unnecessary, and the target product with very few by-products can be obtained through the steps of filtration, concentration and drying under reduced pressure. When it is necessary to further increase the purity, it can be purified by a person skilled in the art appropriately selecting and using a general purification method for purifying a hydroxyl group-substituted siloxane or an alkoxy group-substituted siloxane. Specific examples of the purification method include filtration, extraction, distillation, sublimation, recrystallization, and fractionation by normal / reverse phase liquid chromatography.
In the production method of the present invention, when a plurality of R are different organic groups, the linear siloxane compound (3) may be produced as a mixture of two or more geometric isomers. These geometric isomers can be separated by technical means commonly used by those skilled in the art, such as liquid chromatography fractionation. If there is no particular problem, the isomer mixture may be used as it is.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not restrict | limited to these Examples at all.

撹拌子及び三方コックを備えた１Ｌ３口フラスコに、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン（ゲレスト社製）８０．０ｇ（３６０ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製、乾燥品、５ｗｔ％Ｐｄ）１６．８ｇ（３．６０ｍｍｏｌＰｄ）、ＴＨＦ８００ｍＬ（関東化学株式会社製、特級、安定剤不含）及び蒸留水６４．８ｇ（３．６０ｍｏｌ）を収めた。反応装置を穏やかに減圧にした後、風船から供給した水素ガスで置換し、１気圧の水素ガス雰囲気で２５℃で４時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いてろ別した。ろ液をロータリーエバポレーターを用いて濃縮し、得られた無色油状物を減圧下で２時間乾燥させることにより、１，１，３，３，５，５−ヘキサメチルトリシロキサン−１，５−ジオールを、無色の液体として７８．１ｇ（収率９０．３％）得た。^１Ｈ−ＮＭＲより求めた純度は９７％であった。
ＥＩ−ＭＳ（７０ｅＶ）ｍ/ｚ（％）２２５（２，［Ｍ−Ｍｅ］^＋），２０７（１００），１９３（１４）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ０．１１（ｓ，６Ｈ），０．１５（ｓ，１２Ｈ），４．０６（ｓ，２Ｈ）；^１３Ｃ−ＮＭＲ（１０１ＭＨｚ，ＣＤＣｌ_３）δ０．３５，０．８５；^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）δ−１９．４、−９．８；ＩＲ（ｎｅａｔ，ｃｍ^−１）３２６５，２９６４，１２５７，１０１６，８８５，８５６，７９４．

In a 1 L three-necked flask equipped with a stirrer and a three-way cock, 2,0.04 (360 mmol) of 2,2,4,4,6,6-hexamethylcyclotrisiloxane (manufactured by Gerest), palladium activated carbon (N.E. 16.8 g (3.60 mmol Pd) manufactured by Chemcat, 5 wt% Pd), 800 mL of THF (manufactured by Kanto Chemical Co., Ltd., special grade, without stabilizer) and 64.8 g (3.60 mol) of distilled water were stored. After the pressure in the reactor was reduced to a gentle pressure, the hydrogen gas supplied from the balloon was replaced, and the mixture was stirred at 25 ° C. for 4 hours in a hydrogen gas atmosphere at 1 atm. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a glass filter. The filtrate was concentrated using a rotary evaporator, and the resulting colorless oil was dried under reduced pressure for 2 hours to obtain 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol. Was obtained as a colorless liquid (yield: 90.3%). ^The purity determined from ¹ H-NMR was 97%.
EI-MS (70 eV) m / z (%) 225 (2, [M-Me] ⁺ ), 207 (100), 193 (14); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.11 (s, ^{6H), 0.15 (s, 12H} ), 4.06 (s, 2H); 13 C-NMR (101MHz, CDCl 3) δ0.35,0.85; 29 Si-NMR (79MHz, CDCl 3) δ −19.4, −9.8; IR (neat, cm ⁻¹ ) 3265, 2964, 1257, 1016, 885, 856, 794.

撹拌子及び三方コックを備えた１００ｍＬ３口フラスコをアルゴンで置換し、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン（ゲレスト社製）２．２２ｇ（１０．０ｍｍｏｌ）、白金／炭素（エヌ・イー・ケムキャット社製、乾燥品、５ｗｔ％Ｐｔ）３９０ｍｇ（０．１ｍｍｏｌＰｔ）、ＴＨＦ２０ｍＬ及び蒸留水１．８０ｇ（１００ｍｍｏｌ）を収めた。反応装置を穏やかに減圧にした後、風船から供給した水素ガスで置換し、１気圧の水素ガス雰囲気で２５℃で４時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いてろ別した。ろ液をロータリーエバポレーターを用いて濃縮し、得られた無色油状物を減圧下で２時間乾燥させることにより、目的とする１，１，３，３，５，５−ヘキサメチルトリシロキサン−１，５−ジオールを、無色の液体として２．１６ｇ（収率９０．０％）得た。

A 100 mL three-necked flask equipped with a stirrer and a three-way cock was replaced with argon, and 2,2,4,4,6,6-hexamethylcyclotrisiloxane (manufactured by Gerest) 2.22 g (10.0 mmol), platinum / 390 mg (0.1 mmol Pt) of carbon (made by N.E. Chemcat, dry product, 5 wt% Pt), 20 mL of THF, and 1.80 g (100 mmol) of distilled water were stored. After the pressure in the reactor was reduced to a gentle pressure, the hydrogen gas supplied from the balloon was replaced, and the mixture was stirred at 25 ° C. for 4 hours in a hydrogen gas atmosphere at 1 atm. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a glass filter. The filtrate was concentrated using a rotary evaporator, and the resulting colorless oil was dried under reduced pressure for 2 hours to obtain the desired 1,1,3,3,5,5-hexamethyltrisiloxane-1, 2.16 g (yield 90.0%) of 5-diol was obtained as a colorless liquid.

撹拌子及び三方コックを備えた３００ｍＬ３口フラスコをアルゴンで置換し、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン（ゲレスト社製）２．１８ｇ（９．７９ｍｍｏｌ）、レニウム活性炭素（アルドリッチ社製、含水、５ｗｔ％Ｒｅ）４１１ｍｇ（０．１００ｍｍｏｌＲｅ）、ＴＨＦ２０ｍＬ及び蒸留水１．８６ｇ（１０３ｍｍｏｌ）を収めた。反応装置を穏やかに減圧にした後、風船から供給した水素ガスで置換し、１気圧の水素ガス雰囲気で２５℃で７時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いてろ別した。ろ液をロータリーエバポレーターを用いて濃縮し、得られた無色油状物を減圧下で２時間乾燥させることにより、目的とする１，１，３，３，５，５−ヘキサメチルトリシロキサン−１，５−ジオールを、無色の液体として２．１５ｇ（収率９１．３％）得た。

A 300 mL three-necked flask equipped with a stirrer and a three-way cock was replaced with argon, and 2,2,4,4,6,6-hexamethylcyclotrisiloxane (Guerest) 2.18 g (9.79 mmol), rhenium activity 411 mg (0.100 mmol Re) of carbon (manufactured by Aldrich, water content, 5 wt% Re), 20 mL of THF, and 1.86 g (103 mmol) of distilled water were stored. The pressure in the reactor was reduced to a gentle pressure, and the gas was replaced with hydrogen gas supplied from a balloon, followed by stirring at 25 ° C. for 7 hours in a hydrogen gas atmosphere at 1 atm. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a glass filter. The filtrate was concentrated using a rotary evaporator, and the resulting colorless oil was dried under reduced pressure for 2 hours to obtain the desired 1,1,3,3,5,5-hexamethyltrisiloxane-1, 2.15 g (yield 91.3%) of 5-diol was obtained as a colorless liquid.

撹拌子及び三方コックを備えた１００ｍＬ２口フラスコをアルゴンで置換し、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン（ゲレスト社製）２．２３ｇ（１０．０ｍｍｏｌ）、ロジウム活性炭素（岩井化学薬品社製、乾燥品、５ｗｔ％Ｒｈ）２１４ｍｇ（０．１００ｍｍｏｌＲｈ）、ＴＨＦ２０ｍＬ及び蒸留水１．９０ｇ（１０５ｍｍｏｌ）を収めた。反応装置を穏やかに減圧にした後、風船から供給した水素ガスで置換し、１気圧の水素ガス雰囲気で２５℃で１８時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いて減圧ろ別した。ろ液をロータリーエバポレーターを用いて濃縮し、得られた無色油状物を減圧下で２時間乾燥させることにより、目的とする１，１，３，３，５，５−ヘキサメチルトリシロキサン−１，５−ジオールを、無色の液体として２．０８ｇ（収率８６．５％）得た。

A 100 mL two-necked flask equipped with a stir bar and a three-way cock was replaced with argon, and 2,2,4,4,6,6-hexamethylcyclotrisiloxane (manufactured by Gerest) 2.23 g (10.0 mmol), rhodium activity Carbon (made by Iwai Chemicals Co., Ltd., dried product, 5 wt% Rh) 214 mg (0.100 mmol Rh), THF 20 mL and distilled water 1.90 g (105 mmol) were stored. After the pressure in the reactor was reduced to a gentle pressure, the hydrogen gas supplied from the balloon was replaced, and the mixture was stirred at 25 ° C. for 18 hours in a hydrogen gas atmosphere at 1 atm. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off under reduced pressure using a glass filter. The filtrate was concentrated using a rotary evaporator, and the resulting colorless oil was dried under reduced pressure for 2 hours to obtain the desired 1,1,3,3,5,5-hexamethyltrisiloxane-1, 2.08 g (yield: 86.5%) of 5-diol was obtained as a colorless liquid.

撹拌子及び三方コックを備えた１００ｍＬ２口フラスコをアルゴンで置換し、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン（ゲレスト社製）２．２２ｇ（１０．０ｍｍｏｌ）、トリス（ジベンジリデンアセトン）ジパラジウム（東京化成株式会社製）２２９ｍｇ（０．５００μｍｏｌ）、ＴＨＦ２０ｍＬ及び蒸留水１．９０ｇ（１０５ｍｍｏｌ）を収めた。反応装置を穏やかに減圧にした後、風船から供給した水素ガスで置換し、１気圧の水素ガス雰囲気で２５℃で４８時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をセライトを敷いたガラスフィルターを用いて減圧ろ別した。ろ液をロータリーエバポレーターを用いて濃縮し、得られた無色油状物を減圧下で２時間乾燥させることにより、目的とする１，１，３，３，５，５−ヘキサメチルトリシロキサン−１，５−ジオールを、無色の液体として２．１９ｇ（収率９１．３％）得た。

A 100 mL two-necked flask equipped with a stir bar and a three-way cock was replaced with argon, and 2,2,4,4,6,6-hexamethylcyclotrisiloxane (manufactured by Gerest) 2.22 g (10.0 mmol), Tris ( Dibenzylideneacetone) dipalladium (manufactured by Tokyo Chemical Industry Co., Ltd.) 229 mg (0.500 μmol), THF 20 mL and distilled water 1.90 g (105 mmol) were stored. The pressure in the reaction apparatus was reduced to a gentle pressure, and then replaced with hydrogen gas supplied from a balloon, followed by stirring at 25 ° C. for 48 hours in a hydrogen gas atmosphere of 1 atm. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered under reduced pressure using a glass filter with celite. The filtrate was concentrated using a rotary evaporator, and the resulting colorless oil was dried under reduced pressure for 2 hours to obtain the desired 1,1,3,3,5,5-hexamethyltrisiloxane-1, 2.19 g (yield 91.3%) of 5-diol was obtained as a colorless liquid.

撹拌子及び三方コックを備えた３０ｍＬ２口フラスコに、２，２，４，４，６，６−ヘキサエチルシクロトリシロキサン１．０２ｇ（３．３３ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）３４７ｍｇ（５ｗｔ％Ｐｄ、３．６０ｍｍｏｌＰｄ）、ＴＨＦ２０ｍＬ及び蒸留水５８９ｍｇ（３２．７ｍｍｏｌ）を収めた。反応装置を減圧後、風船から供給した水素ガスで置換し、水素ガス雰囲気で２５℃で１２日間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をセライトを敷いたガラスフィルターを用いてろ別した。これを濃縮後減圧下で２時間乾燥させることにより、目的とする１，１，３，３，５，５−ヘキサエチルトリシロキサン−１，５−ジオールを、無色の液体として１．０８ｇ（収率９１．５％）得た。
ＭＳ（ＥＩ，７０ｅＶ）ｍ／ｚ（％）２９５（１９，［Ｍ−Ｅｔ］^＋），２７７（１００），２４９（９６），２２１（７２）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ａｃｅｔｏｎｅ−ｄ_６）δ０．５４４（ｑ，８Ｈ，Ｊ＝８．０Ｈｚ），０．５４８（ｑ，４Ｈ，Ｊ＝８．０Ｈｚ），０．９７５（ｔ，１８Ｈ，Ｊ＝８．０Ｈｚ），５．１３３（ｓ，２Ｈ）；ＩＲ（ｎｅａｔ，ｃｍ^−１）３３４０，２９５８，２８７９，１４５８、１２４０，１０６３，１００１，８５０，７４１，６９６．

In a 30 mL two-necked flask equipped with a stir bar and a three-way cock, 2,2,4,4,6,6-hexaethylcyclotrisiloxane 1.02 g (3.33 mmol), palladium activated carbon (manufactured by N.E. Chemcat) ) 347 mg (5 wt% Pd, 3.60 mmol Pd), THF 20 mL and distilled water 589 mg (32.7 mmol) were stored. The reactor was depressurized, replaced with hydrogen gas supplied from a balloon, and stirred at 25 ° C. for 12 days in a hydrogen gas atmosphere. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were separated by filtration using a glass filter with celite. This was concentrated and then dried under reduced pressure for 2 hours to obtain 1.08 g (contracted) of the desired 1,1,3,3,5,5-hexaethyltrisiloxane-1,5-diol as a colorless liquid. (Rate 91.5%).
MS (EI, 70 eV) m / z (%) 295 (19, [M-Et] ⁺ ), 277 (100), 249 (96), 221 (72); ¹ H-NMR (400 MHz, acetone-d ₆ ) Δ 0.544 (q, 8H, J = 8.0 Hz), 0.548 (q, 4H, J = 8.0 Hz), 0.975 (t, 18H, J = 8.0 Hz), 5.133 ( s, 2H); IR (neat, cm ⁻¹ ) 3340, 2958, 2879, 1458, 1240, 1063, 1001, 850, 741, 696.

撹拌子及び三方コックを備えた１００ｍＬ３口フラスコに、２，４，６−トリス（３，３，３−トリフルオロプロピル）−２，４，６−トリメチルシクロトリシロキサン０．９８２ｇ（アズマックス社製，２．１３ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）１．２５ｇ（５ｗｔ％Ｐｄ、０．５８５ｍｍｏｌＰｄ）、ＴＨＦ２０ｍＬ及び蒸留水４２０ｍｇ（２３．３ｍｍｏｌ）を収めた。反応装置を減圧後、風船から供給した水素ガスで置換し、水素ガス雰囲気で２５℃で６日間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をセライトを敷いたガラスフィルターを用いてろ別した。ろ液をロータリーエバポレーターを用いて濃縮し、得られた無色油状物を減圧下で２時間乾燥させることにより、目的とする１，３，５−トリス（３，３，３−トリフルオロプロピル）−１，３，５−トリメチルトリシロキサン−１，５−ジオールを、無色の液体として０．９２０ｇ（収率９０．２％）得た。これは、２種類のジアステレオマー混合物であった。
ＭＳ（ＥＩ，７０ｅＶ）ｍ／ｚ（％）２３７（１００），２１９（２７），２１５（９３），１５９（４５），１５７（３２），１３７（９０），１０９（３５）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ａｃｅｔｏｎｅ−ｄ_６）δ０．１７４（異性体１，Ｓｉ−Ｍｅ，ｓ，６Ｈ），０．１７７（異性体２，Ｓｉ−Ｍｅ，ｓ，６Ｈ），０．２１３（異性体１＋２，Ｓｉ−Ｍｅ，ｓ，６Ｈ），０．７５−０．８５（異性体１＋２，Ｓｉ−ＣＨ_２，ｍ，６Ｈ），２．１５−２．３２（異性体１＋２，ＣＨ_２，ｍ，６Ｈ），４．２９５（ｓ，２Ｈ）；ＩＲ（ｎｅａｔ，ｃｍ^−１）３２７８，２９７２，１３６９，１３１５，１２６３，１２０５，１１２２，１０６３，１０２２，８９７，７９８．

In a 100 mL three-necked flask equipped with a stir bar and a three-way cock, 0.982 g of 2,4,6-tris (3,3,3-trifluoropropyl) -2,4,6-trimethylcyclotrisiloxane (manufactured by Asmax Co., 2.13 mmol), 1.25 g (5 wt% Pd, 0.585 mmol Pd) of palladium activated carbon (manufactured by NE Chemcat), 20 mL of THF, and 420 mg (23.3 mmol) of distilled water. The reactor was depressurized, replaced with hydrogen gas supplied from a balloon, and stirred at 25 ° C. for 6 days in a hydrogen gas atmosphere. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were separated by filtration using a glass filter with celite. The filtrate was concentrated using a rotary evaporator, and the resulting colorless oil was dried under reduced pressure for 2 hours to obtain the desired 1,3,5-tris (3,3,3-trifluoropropyl)- 0.920 g (yield 90.2%) of 1,3,5-trimethyltrisiloxane-1,5-diol was obtained as a colorless liquid. This was a mixture of two diastereomers.
MS (EI, 70 eV) m / z (%) 237 (100), 219 (27), 215 (93), 159 (45), 157 (32), 137 (90), 109 (35); ¹ H- NMR (400 MHz, acetone-d ₆ ) δ 0.174 (isomer 1, Si-Me, s, 6H), 0.177 (isomer 2, Si-Me, s, 6H), 0.213 (isomer 1 + 2 , Si-Me, s, 6H ), 0.75-0.85 ( isomer _{1 + 2, Si-CH 2} , m, 6H), 2.15-2.32 ( isomer _{1 + 2, CH 2, m} , 6H ), 4.295 (s, 2H); IR (neat, cm ⁻¹ ) 3278, 2972, 1369, 1315, 1263, 1205, 1122, 1063, 1022, 897, 798.

撹拌子及び三方コックを備えた２００ｍＬ３口フラスコをアルゴンで置換し、これに、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン（ゲレスト社製）２．２４ｇ（１０．１ｍｍｏｌ）、パラジウム／炭素（エヌ・イー・ケムキャット社製）２１５ｍｇ（５ｗｔ％Ｐｄ、乾燥品、０．１０１ｍｍｏｌＰｄ）、ＴＨＦ５０ｍＬ及び蒸留水１．８０ｇ（１００ｍｏｌ）を収めた。溶液に、注射器より１，４−ヘキサジエン０．８０５ｇ（１０．１ｍｍｏｌ）をゆっくり加え、２５℃で２４時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いてろ別した。これを濃縮後、減圧下で２時間乾燥させることにより、目的とする１，１，３，３，５，５−ヘキサメチルトリシロキサン−１，５−ジオールを、無色の液体として１．６３ｇ（収率６７．１％）得た。

A 200 mL three-necked flask equipped with a stirrer and a three-way cock was replaced with argon, and 2.24 g (10.1 mmol) of 2,2,4,4,6,6-hexamethylcyclotrisiloxane (manufactured by Gerest) was added thereto. 215 mg (5 wt% Pd, dried product, 0.101 mmol Pd) of palladium / carbon (manufactured by N.E. Chemcat), 50 mL of THF, and 1.80 g (100 mol) of distilled water. To the solution, 0.805 g (10.1 mmol) of 1,4-hexadiene was slowly added from a syringe and stirred at 25 ° C. for 24 hours. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a glass filter. After concentration, this was dried under reduced pressure for 2 hours to obtain 1.63 g of the desired 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol as a colorless liquid ( Yield 67.1%).

撹拌子及び三方コックを備えた２００ｍＬ３口フラスコをアルゴンで置換し、これに、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン（ゲレスト社製）２．２３ｇ（１０．０ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）２２３ｍｇ（５ｗｔ％Ｐｄ、乾燥品、０．１０５ｍｍｏｌＰｄ）、ＴＨＦ５０ｍＬ及び蒸留水３．６０ｇ（２００ｍｍｏｌ）を収めた。溶液に、注射器より１，１，３，３，５，５−ヘキサメチルトリシロキサン２．２１ｇ（１０．６ｍｍｏｌ）をゆっくり加え、２５℃で６９時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いてろ別した。これを濃縮後、減圧下で２時間乾燥させることにより、目的とする１，１，３，３，５，５−ヘキサメチルトリシロキサン−１，５−ジオールを、無色の液体として４．１６ｇを得た。１，１，３，３，５，５−ヘキサメチル−１，５−ジヒドロトリシロキサン由来の１，１，３，３，５，５−トリシロキサンジオールの生成分を減じて計算した反応の収率は８３．９％であった。

A 200 mL three-necked flask equipped with a stirrer and a three-way cock was replaced with argon, and 2.23 g (10.0 mmol) of 2,2,4,4,6,6-hexamethylcyclotrisiloxane (manufactured by Gerest) was added thereto. 223 mg (5 wt% Pd, dried product, 0.105 mmol Pd) of palladium activated carbon (manufactured by N.E. Chemcat), 50 mL of THF, and 3.60 g (200 mmol) of distilled water. To the solution, 2.21 g (10.6 mmol) of 1,1,3,3,5,5-hexamethyltrisiloxane was slowly added from a syringe and stirred at 25 ° C. for 69 hours. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a glass filter. After concentration, this was dried under reduced pressure for 2 hours to give 4.16 g of the desired 1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diol as a colorless liquid. Obtained. Yield of reaction calculated by reducing the amount of 1,1,3,3,5,5-trisiloxanediol derived from 1,1,3,3,5,5-hexamethyl-1,5-dihydrotrisiloxane Was 83.9%.

Reference example 1

撹拌子及びジムロ−ト冷却管を備えた５００ｍＬ２口フラスコをアルゴンで置換し、１，１，３，３−テトラメチルジシロキサン２．７２ｇ（東京化成株式会社製、２０．２ｍｍｏｌ）、ジイソプロピルシランジオール３．００ｇ（２０．２ｍｍｏｌ）及び脱水ヘキサン３００ｍＬを収め、ここにゆっくりとトリス（ペンタフルオロフェニル）ボラン６．８ｍｇ（０．６８６ｍｍｏｌ）のトルエン２ｍＬ溶液を加えた。反応混合物を２５℃で１時間撹拌し、反応終了をガスクロマトグラフィーで確認した。ロ−タリーエバポレーターを用いて減圧下で溶媒を留去し、これをクーゲルロ−ル蒸留装置を用いて減圧蒸留（蒸留温度１００℃／３．３ｋＰａ）することにより、２，２−ジイソプロピル−４，４，６，６−テトラメチルシクロトリシロキサンを無色液体として４．０７ｇ（収率：７２％，ＧＣ純度：９５％）得た。
ＥＩ−ＭＳ（７０ｅＶ）ｍ／ｚ（％）２７８（Ｍ^＋，１），２６３（５），２３５（９６），２０７（８１），１９３（１００）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）０．１８（ｓ，１２Ｈ），０．８８〜１．００（ｍ，２Ｈ），１．０１（ｄ，１２Ｈ，Ｊ＝７．３Ｈｚ）；^１３Ｃ−ＮＭＲ（ＣＤＣｌ_３）−０．８９，１２．８，１６．６；^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）−１１．１、−８．８：ＩＲ（ｃｍ^−１）２９６０，２８６８，１４６６，１２５７，１００３，８００，６７７，６３１．

A 500 mL two-necked flask equipped with a stirrer and a Dimroth condenser was replaced with argon, and 2,72 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Tokyo Chemical Industry Co., Ltd., 20.2 mmol), diisopropylsilanediol 3.00 g (20.2 mmol) and 300 mL of dehydrated hexane were placed, and a solution of tris (pentafluorophenyl) borane (6.8 mg, 0.686 mmol) in toluene (2 mL) was slowly added thereto. The reaction mixture was stirred at 25 ° C. for 1 hour, and the completion of the reaction was confirmed by gas chromatography. The solvent was distilled off under reduced pressure using a rotary evaporator, and this was distilled under reduced pressure (distillation temperature 100 ° C./3.3 kPa) using a Kugelrohr distillation apparatus, whereby 2,2-diisopropyl-4, As a colorless liquid, 4.07 g (yield: 72%, GC purity: 95%) of 4,6,6-tetramethylcyclotrisiloxane was obtained.
EI-MS (70 eV) m / z (%) 278 (M ⁺ , 1), 263 (5), 235 (96), 207 (81), 193 (100); ¹ H-NMR (400 MHz, CDCl ₃ ) 0.18 (s, 12H), 0.88 to 1.00 (m, 2H), 1.01 (d, 12H, J = 7.3 Hz); ¹³ C-NMR (CDCl ₃ ) -0.89, 12.8, 16.6; ²⁹ Si-NMR (79 MHz, CDCl ₃ ) -11.1, -8.8: IR (cm ^-1 ) 2960, 2868, 1466, 1257, 1003, 800, 677, 631.

撹拌子及びジムロ−ト冷却管を備えた１００ｍＬの３口フラスコをアルゴンで置換し、２，２−ジイソプロピル−４，４，６，６−テトラメチルシクロトリシロキサン１．０２ｇ（３．５９ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）７５９ｍｇ（５ｗｔ％Ｐｄ、乾燥品、０．３５９ｍｍｏｌＰｄ）及び脱水テトラヒドロフラン１０ｍＬを収めた。反応容器を減圧後、１気圧の水素ガスで置換し、２５℃で２４時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いてろ別した。これを減圧下で濃縮後、クーゲルロール蒸留装置を用いて減圧下で蒸留（蒸留温度６０℃／５０Ｐａ）することにより、トリシロキサン留分を無色液体として０．６３５ｇ（収率：５８％）得た。これを核磁気共鳴分光装置により分析したところ、３，３−ジイソプロピル−１，１，５，５−テトラメチルトリシロキサン−１，５−ジオール及び１，１−ジイソプロピル−３，３，５，５−テトラメチルトリシロキサン−１，５−ジオールの１：２混合物であった。
ＥＩ−ＭＳ（７０ｅＶ）ｍ／ｚ（異性体混合物、相対強度）２８１（［Ｍ−Ｍｅ］^＋，１．８），２６３（１４），２３５（６４），２０７（６８），１９３（１００）；^１Ｈ−ＮＭＲ（３，３−ジイソプロピル−１，１，５，５−テトラメチルトリシロキサン−１，５−ジオール，４００ＭＨｚ，ＣＤＣｌ_３）δ０．１３０（ｓ，１２Ｈ），０．７８〜０．９２（ｍ，２Ｈ），０．９５２（ｄ，１２Ｈ，Ｊ＝６．９Ｈｚ），３．１７８（ｓ，２Ｈ）；^１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ_３）１．０４，１３．２３，１７．１３；^１Ｈ−ＮＭＲ（１，１−ジイソプロピル−３，３，５，５−テトラメチルトリシロキサン−１，５−ジオール，４００ＭＨｚ，ＣＤＣｌ_３）δ０．０９４（ｓ，６Ｈ），０．１１０（ｓ，６Ｈ），０．７８〜０．９２（ｍ，２Ｈ），０．９８２（ｄ，６Ｈ，Ｊ＝７．０Ｈｚ），０．９８７（ｄ，６Ｈ，Ｊ＝７．２Ｈｚ），３．１７８（ｓ，２Ｈ）；^１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ_３）０．５７，０．６４，１３．１４，１７．１６．

A 100 mL three-necked flask equipped with a stir bar and a Dimroth condenser was replaced with argon, and 1.02 g (3.59 mmol) of 2,2-diisopropyl-4,4,6,6-tetramethylcyclotrisiloxane, 759 mg (5 wt% Pd, dried product, 0.359 mmol Pd) of palladium activated carbon (manufactured by N.E. Chemcat) and 10 mL of dehydrated tetrahydrofuran were stored. The reaction vessel was replaced with 1 atm of hydrogen gas under reduced pressure, and stirred at 25 ° C. for 24 hours. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a glass filter. This was concentrated under reduced pressure and then distilled under reduced pressure using a Kugelrohr distillation apparatus (distillation temperature 60 ° C./50 Pa) to obtain 0.635 g (yield: 58%) of a trisiloxane fraction as a colorless liquid. It was. When this was analyzed by a nuclear magnetic resonance spectrometer, 3,3-diisopropyl-1,1,5,5-tetramethyltrisiloxane-1,5-diol and 1,1-diisopropyl-3,3,5,5 were detected. -A 1: 2 mixture of tetramethyltrisiloxane-1,5-diol.
EI-MS (70 eV) m / z (isomer mixture, relative intensity) 281 ([M-Me] ⁺ , 1.8), 263 (14), 235 (64), 207 (68), 193 (100) ¹ H-NMR (3,3-diisopropyl-1,1,5,5-tetramethyltrisiloxane-1,5-diol, 400 MHz, CDCl ₃ ) δ 0.130 (s, 12H), 0.78-0 .92 (m, 2H), 0.952 (d, 12H, J = 6.9 Hz), 3.178 (s, 2H); ¹³ C-NMR (100 MHz, CDCl ₃ ) 1.04, 13.23, 17.13; ¹ H-NMR (1,1-diisopropyl-3,3,5,5-tetramethyltrisiloxane-1,5-diol, 400 MHz, CDCl ₃ ) δ 0.094 (s, 6H), 0. 110 (s, 6H), .78 to 0.92 (m, 2H), 0.982 (d, 6H, J = 7.0 Hz), 0.987 (d, 6H, J = 7.2 Hz), 3.178 (s, 2H) ¹³ C-NMR (100 MHz, CDCl ₃ ) 0.57, 0.64, 13.14, 17.16.

撹拌子及びジムロ−ト冷却管を備えた１００ｍＬの３口フラスコをアルゴンで置換し、２，２−ジフェニル−４，４，６，６−テトラメチルシクロトリシロキサン１．００ｇ（２．８９ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）６１８ｍｇ（５ｗｔ％Ｐｄ、乾燥品、０．２９０ｍｍｏｌＰｄ）及び脱水テトラヒドロフラン１５ｍＬを収めた。反応容器を減圧後、１気圧の水素ガスで置換し、２５℃で２２時間撹拌した。反応装置内をアルゴンで置換して、反応混合物中の不溶物をガラスフィルターを用いてろ別した。これを減圧下で濃縮することにより、トリシロキサンを無色液体として１．０４ｇ（収率：９８％）得た。これを核磁気共鳴分光装置により分析したところ、３，３−ジフェニル−１，１，５，５−テトラメチルトリシロキサン−１，５−ジオール及び１，１−ジジフェニル−３，３，５，５−テトラメチルトリシロキサン−１，５−ジオールの１：２混合物であった。
ＥＩ−ＭＳ（７０ｅＶ）ｍ／ｚ（異性体混合物、相対強度）３４６（８），２８７（２２），２６９（３６），２５３（８９），１９３（１００）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ０．０７７（ｓ，１６Ｈ），０．１５（ｓ，１６Ｈ）０．１７（ｓ，１２Ｈ）７．４０（ｍ，２８Ｈ），７．６５（ｍ，１９Ｈ）；^１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ_３）０．１７，０．３３，０．９１，０．９８，１２７．８，１３０．１，１３４．３；；^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）−３７．８，−１８．２，−９．６，−８．４，−６．７；ＩＲ（ｎｅａｔ，ｃｍ^−１）３１７６，３０７０，２９６０，１４２９，１２５９，１００７，９９５，８０２，６９８．

A 100 mL three-necked flask equipped with a stir bar and a Dimroth condenser was replaced with argon, and 1.00 g (2.89 mmol) of 2,2-diphenyl-4,4,6,6-tetramethylcyclotrisiloxane, 618 mg (5 wt% Pd, dried product, 0.290 mmol Pd) of palladium activated carbon (manufactured by N.E. Chemcat) and 15 mL of dehydrated tetrahydrofuran were stored. The reaction vessel was replaced with 1 atm of hydrogen gas under reduced pressure, and stirred at 25 ° C. for 22 hours. The inside of the reaction apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a glass filter. This was concentrated under reduced pressure to obtain 1.04 g (yield: 98%) of trisiloxane as a colorless liquid. When this was analyzed by a nuclear magnetic resonance spectrometer, 3,3-diphenyl-1,1,5,5-tetramethyltrisiloxane-1,5-diol and 1,1-didiphenyl-3,3,5, It was a 1: 2 mixture of 5-tetramethyltrisiloxane-1,5-diol.
EI-MS (70 eV) m / z (isomer mixture, relative intensity) 346 (8), 287 (22), 269 (36), 253 (89), 193 (100); ¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.077 (s, 16H), 0.15 (s, 16H) 0.17 (s, 12H) 7.40 (m, 28H), 7.65 (m, 19H); ¹³ C-NMR ( 100 MHz, CDCl ₃ ) 0.17, 0.33, 0.91, 0.98, 127.8, 130.1, 134.3; ²⁹ Si-NMR (79 MHz, CDCl ₃ ) -37.8, − 18.2, −9.6, −8.4, −6.7; IR (neat, cm ⁻¹ ) 3176, 3070, 2960, 1429, 1259, 1007, 995, 802, 698.

撹拌子及び三方コックを備えた１Ｌ３口フラスコに、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン８０．０ｇ（０．３６０ｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）６．９０ｇ（５ｗｔ％Ｐｄ、乾燥品、３．２４ｍｍｏｌＰｄ）、脱水ＴＨＦ（関東化学株式会社製）６００ｍＬ及び脱水メタノ−ル（関東化学株式会社製）２５２ｍＬ（６．２２ｍｏｌ）を収めた。反応装置を減圧後、風船から供給した水素ガスで置換し、水素ガス雰囲気で２５℃で２４時間撹拌した。装置内をアルゴンで置換し、反応混合物中の不溶物を焼結ガラスフィルターを用いてろ別した。得られたろ液をモレキュラーシーブス３Ａを用いて乾燥させた。これを吸引ろ過後、ロータリーエバポレーターで濃縮し、得られた反応混合物をクーゲルロール蒸留装置を用いて減圧蒸留（蒸留温度５５℃／７０Ｐａ）を行うことにより、１−ヒドロキシ−５−メトキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサン及び１，５−ジメトキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサンの約１：１混合物を無色透明液体として４０．２ｇ（収率４２．６％）得た。
ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；２５３（［Ｍ−ＣＨ_３］^＋），２２３，２０７（［Ｃ_５Ｈ_１５Ｏ_３Ｓｉ_３］^＋），１９３；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）０．１１１（［Ｓｉ−ＣＨ_３］、モノメトキシモノヒドロキシトリシロキサン、ジメトキシトリシロキサンの重なり合ったシグナル），０．１１８（［Ｓｉ−ＣＨ_３］、ジメトキシトリシロキサン），０．１２８（［Ｓｉ−ＣＨ_３］、モノメトキシモノヒドロキシトリシロキサン），０．１４０７（［Ｓｉ−ＣＨ_３］、モノメトキシモノヒドロキシトリシロキサン），３．４８３（［ＣＨ_３−Ｏ］、ジメトキシトリシロキサン），３．４８８（［ＣＨ_３−Ｏ］、モノメトキシモノヒドロキシトリシロキサン）

In a 1 L three-neck flask equipped with a stir bar and a three-way cock, 80.0 g (0.360 mol) of 2,2,4,4,6,6-hexamethylcyclotrisiloxane, palladium activated carbon (manufactured by N.E. Chemcat) ) 6.90 g (5 wt% Pd, dried product, 3.24 mmol Pd), 600 mL of dehydrated THF (manufactured by Kanto Chemical Co., Ltd.) and 252 mL (6.22 mol) of dehydrated methanol (manufactured by Kanto Chemical Co., Ltd.) were stored. The reactor was depressurized, replaced with hydrogen gas supplied from a balloon, and stirred at 25 ° C. for 24 hours in a hydrogen gas atmosphere. The inside of the apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a sintered glass filter. The obtained filtrate was dried using Molecular Sieves 3A. This was subjected to suction filtration, concentrated with a rotary evaporator, and the resulting reaction mixture was subjected to distillation under reduced pressure (distillation temperature 55 ° C./70 Pa) using a Kugelrohr distillation apparatus, whereby 1-hydroxy-5-methoxy-1, 40. An approximately 1: 1 mixture of 1,3,3,5,5-hexamethyltrisiloxane and 1,5-dimethoxy-1,1,3,3,5,5-hexamethyltrisiloxane as a colorless transparent liquid. 2 g (yield 42.6%) was obtained.
EI-MS (70 eV), m / z (%); 253 ([M-CH ₃ ] ⁺ ), 223, 207 ([C ₅ H ₁₅ O ₃ Si ₃ ] ⁺ ), 193; ¹ H-NMR (400 MHz) , CDCl ₃ ) δ (ppm) 0.111 ([Si—CH ₃ ], monomethoxymonohydroxytrisiloxane, dimethoxytrisiloxane overlapped signal), 0.118 ([Si—CH ₃ ], dimethoxytrisiloxane) _{, 0.128 ([Si-CH 3} ], monomethoxy monohydroxy _{trisiloxane), 0.1407 ([Si-CH} 3], monomethoxy monohydroxy _{trisiloxane), 3.483 ([CH 3 -O} ], dimethoxy _{trisiloxane), 3.488 ([CH 3 -O} ], monomethoxy monohydroxy trisiloxane)

撹拌子及び三方コックを備えた１００ｍＬ３口フラスコに、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン１．１３ｇ（５．０６ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）０．１０７ｇ（５ｗｔ％Ｐｄ、乾燥品、０．０５０ｍｍｏｌＰｄ）及びヘキサノール（関東化学株式会社製）５．１３ｇ（５０．２ｍｍｏｌ）を収めた。反応装置を減圧後、風船から供給した水素ガスで置換し、水素ガス雰囲気で２５℃で１０１時間撹拌した。装置内をアルゴンで置換し、反応混合物中の不溶物を焼結ガラスフィルターを用いてろ別した。これを吸引ろ過後、ロータリーエバポレーターで濃縮し、得られた反応混合物をクーゲルロール蒸留装置を用いて減圧下で過剰のアルコールを留去することにより、１−ヒドロキシ−５−ヘキシルオキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサン及び１，５−ビス（ヘキシルオキシ）−１，１，３，３，５，５−ヘキサメチルトリシロキサンの約１：１混合物を無色透明液体として０．３８６ｇ（収率３８．９％）得た。
１−ヒドロキシ−５−ヘキシルオキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサン：ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；２２５（２９），２０７（１００），１９３（７）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）０．１２０（ｓ，６Ｈ），０．１３５（ｓ，６Ｈ），０．１５３（ｓ，６Ｈ），０．８６９-０．９０３（ｍ，３Ｈ），１．２６-１．３５（ｍ，６Ｈ），１．５１-１．５８（ｍ，２Ｈ），３．６３-３．６７（ｍ，２Ｈ）；^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）δ−１９．９，１１．２，１０．１；ＩＲ（ｎｅａｔ，ｃｍ^−１）３３３０，２９６０，２９３０，１２６０，１０４０，８９０．
１，５−ビス（ヘキシルオキシ）−１，１，３，３，５，５−ヘキサメチルトリシロキサン：ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；３０７（５），２２５（１００），２０７（９２）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）０．０９７（ｓ，１２Ｈ），０．１０２（ｓ，６Ｈ），０．８６９-０．９０３（ｍ，６Ｈ），１．２６-１．３５（ｍ，１２Ｈ），１．５１-１．５８（ｍ，４Ｈ），３．６３-３．６７（ｍ，４Ｈ）；^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）δ−２１．５，−１２．８．

In a 100 mL three-neck flask equipped with a stirrer and a three-way cock, 1.13 g (5.06 mmol) of 2,2,4,4,6,6-hexamethylcyclotrisiloxane, palladium activated carbon (manufactured by N.E. Chemcat) ) 0.107 g (5 wt% Pd, dried product, 0.050 mmol Pd) and 5.13 g (50.2 mmol) of hexanol (manufactured by Kanto Chemical Co., Inc.) were stored. After depressurizing, the reactor was replaced with hydrogen gas supplied from a balloon, and the mixture was stirred at 25 ° C. for 101 hours in a hydrogen gas atmosphere. The inside of the apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a sintered glass filter. This was subjected to suction filtration and then concentrated with a rotary evaporator, and the resulting reaction mixture was distilled off excess alcohol under reduced pressure using a Kugelrohr distillation apparatus, whereby 1-hydroxy-5-hexyloxy-1,1. , 3,3,5,5-hexamethyltrisiloxane and 1,5-bis (hexyloxy) -1,1,3,3,5,5-hexamethyltrisiloxane in a colorless transparent liquid As a result, 0.386 g (yield 38.9%) was obtained.
1-hydroxy-5-hexyloxy-1,1,3,3,5,5-hexamethyltrisiloxane: EI-MS (70 eV), m / z (%); 225 (29), 207 (100), 193 (7); ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) 0.120 (s, 6H), 0.135 (s, 6H), 0.153 (s, 6H), 0.869- 0.903 (m, 3H), 1.26-1.35 (m, 6H), 1.51-1.58 (m, 2H), 3.63-3.67 (m, 2H); ²⁹ Si _{-NMR (79MHz, CDCl 3) δ} -19.9,11.2,10.1; IR (neat, cm -1) 3330,2960,2930,1260,1040,890.
1,5-bis (hexyloxy) -1,1,3,3,5,5-hexamethyltrisiloxane: EI-MS (70 eV), m / z (%); 307 (5), 225 (100) , 207 (92); ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) 0.097 (s, 12H), 0.102 (s, 6H), 0.869-0.903 (m, 6H) , 1.26-1.35 (m, 12H), 1.51-1.58 (m, 4H), 3.63-3.67 (m, 4H); ²⁹ Si-NMR (79 MHz, CDCl ₃ ) δ-21.5, −12.8.

撹拌子及び三方コックを備えた１００ｍＬ３口フラスコに、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン１．１３ｇ（５．０６ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）０．１０６ｇ（５ｗｔ％Ｐｄ、乾燥品、０．０５０ｍｍｏｌＰｄ）及びオクタノール（関東化学株式会社製）６．５３ｇ（５０．１ｍｍｏｌ）を収めた。反応装置を減圧後、風船から供給した水素ガスで置換し、水素ガス雰囲気で２５℃で９７時間撹拌した。装置内をアルゴンで置換し、反応混合物中の不溶物を焼結ガラスフィルターを用いてろ別した。これを吸引ろ過後、ロータリーエバポレーターで濃縮し、得られた反応混合物をクーゲルロール蒸留装置を用いて減圧下で過剰のアルコールを留去することにより、１−ヒドロキシ−５−オクチルオキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサン及び１，５−ビス（オクチルオキシ）−１，１，３，３，５，５−ヘキサメチルトリシロキサンの約３２：６８混合物を無色透明液体として０．７９８ｇ（収率４９．９％）得た。
１−ヒドロキシ−５−オクチルオキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサン：ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；２２５（４１），２２３（３３），２０７（１００）．^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：０．１２０（ｓ，６Ｈ），０．１３５（ｓ，６Ｈ），０．１５３（ｓ，６Ｈ），０．８６９-０．９０３（ｍ，３Ｈ），１．２６-１．３５（ｍ，６Ｈ），１．５１-１．５８（ｍ，２Ｈ），３．６３-３．６７（ｍ，２Ｈ）．^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）δ−１９．９，１１．２，１０．１；ＩＲ（ｎｅａｔ，ｃｍ^−１）３３３０，２９６０，２９３０，１２６０，１０４０，８９０．
１，５−ビス（オクチルオキシ）−１，１，３，３，５，５−ヘキサメチルトリシロキサン：ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；４４９（１），３３５（８），２２５（１００），２０７（６６），１９３（１２）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）０．８５４-０．８８８（ｍ，３Ｈ），１．２７-１．２８（ｍ，１０Ｈ），１．５０-１．５７（ｍ，２Ｈ），３．６２-３．６６（ｍ，２Ｈ）；^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）δ−２１．５，−１２．８．

In a 100 mL three-neck flask equipped with a stirrer and a three-way cock, 1.13 g (5.06 mmol) of 2,2,4,4,6,6-hexamethylcyclotrisiloxane, palladium activated carbon (manufactured by N.E. Chemcat) ) 0.106 g (5 wt% Pd, dried product, 0.050 mmol Pd) and 6.53 g (50.1 mmol) of octanol (manufactured by Kanto Chemical Co., Inc.). The reactor was depressurized, replaced with hydrogen gas supplied from a balloon, and stirred in a hydrogen gas atmosphere at 25 ° C. for 97 hours. The inside of the apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a sintered glass filter. This was subjected to suction filtration and then concentrated with a rotary evaporator, and the resulting reaction mixture was distilled off excess alcohol under reduced pressure using a Kugelrohr distillation apparatus, whereby 1-hydroxy-5-octyloxy-1,1. 1,32,68 mixture of 1,3,5,5-hexamethyltrisiloxane and 1,5-bis (octyloxy) -1,1,3,3,5,5-hexamethyltrisiloxane As a result, 0.798 g (yield 49.9%) was obtained.
1-hydroxy-5-octyloxy-1,1,3,3,5,5-hexamethyltrisiloxane: EI-MS (70 eV), m / z (%); 225 (41), 223 (33), 207 (100). ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 0.120 (s, 6H), 0.135 (s, 6H), 0.153 (s, 6H), 0.869-0.903 ( m, 3H), 1.26-1.35 (m, 6H), 1.51-1.58 (m, 2H), 3.63-3.67 (m, 2H). ²⁹ Si-NMR (79 MHz, CDCl ₃ ) δ-19.9, 11.2, 10.1; IR (neat, cm ⁻¹ ) 3330, 2960, 2930, 1260, 1040, 890.
1,5-bis (octyloxy) -1,1,3,3,5,5-hexamethyltrisiloxane: EI-MS (70 eV), m / z (%); 449 (1), 335 (8) , 225 (100), 207 (66), 193 (12); ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) 0.854-0.888 (m, 3H), 1.27-1.28 (M, 10H), 1.50-1.57 (m, 2H), 3.62-3.66 (m, 2H); ²⁹ Si-NMR (79 MHz, CDCl ₃ ) δ-21.5, -12 .8.

撹拌子及び三方コックを備えた１００ｍＬ３口フラスコに、２，２，４，４，６，６−ヘキサメチルシクロトリシロキサン１．１２ｇ（５．０４ｍｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）０．１０５ｇ（５ｗｔ％Ｐｄ、乾燥品、０．０５０ｍｍｏｌＰｄ）及びデカノール（関東化学株式会社製）７．９２ｇ（５０．０ｍｍｏｌ）を収めた。反応装置を減圧後、風船から供給した水素ガスで置換し、水素ガス雰囲気で２５℃で１５０時間撹拌した。装置内をアルゴンで置換し、反応混合物中の不溶物を焼結ガラスフィルターを用いてろ別した。これを吸引ろ過後、ロータリーエバポレーターで濃縮し、得られた反応混合物をクーゲルロール蒸留装置を用いて減圧下で過剰のアルコールを留去することにより、１−ヒドロキシ−５−デシルオキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサン及び１，５−ビス（デシルオキシ）−１，１，３，３，５，５−ヘキサメチルトリシロキサンの約４４：５５混合物を無色透明液体として０．６４６ｇ（収率４４．８％）得た。
１−ヒドロキシ−５−デシルオキシ−１，１，３，３，５，５−ヘキサメチルトリシロキサン：ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；２２５（５２），２０７（１００），１９３（１９）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）：０．１０２（ｓ，６Ｈ），０．１１１（ｓ，６Ｈ），０．１３５（ｓ，６Ｈ），０．８６１-０．８９５（ｍ，３Ｈ），１．２６-１．３５（ｍ，１０Ｈ），１．５４-１．５６（ｍ，２Ｈ），３．６２-３．６５（ｍ，２Ｈ）．^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）δ−１９．９，１１．１，１０．０；ＩＲ（ｎｅａｔ，ｃｍ^−１）３３８０，２９６０，２９２０，１２６０，１０８０，１０４０，８００．
１，５−ビス（デシルオキシ）−１，１，３，３，５，５−ヘキサメチルトリシロキサン：ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；５０５（０．６），３６３（７），２２５（１００），２０７（５３），１９３（９）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）０．０９６０（ｓ，１８Ｈ），０．８５４-０．８８８（ｍ，６Ｈ），１．２７-１．２８（ｍ，１０Ｈ），１．５０-１．５７（ｍ，２Ｈ），３．６２-３．６６（ｍ，３Ｈ）；^２９Ｓｉ−ＮＭＲ（７９ＭＨｚ，ＣＤＣｌ_３）δ-２１．５，-１２．８．

In a 100 mL three-necked flask equipped with a stir bar and a three-way cock, 1.2, g (5.04 mmol) of 2,2,4,4,6,6-hexamethylcyclotrisiloxane, palladium activated carbon (manufactured by N.E. Chemcat) ) 0.105 g (5 wt% Pd, dried product, 0.050 mmol Pd) and 7.92 g (50.0 mmol) of decanol (manufactured by Kanto Chemical Co., Inc.) were stored. The reactor was depressurized, replaced with hydrogen gas supplied from a balloon, and stirred at 25 ° C. for 150 hours in a hydrogen gas atmosphere. The inside of the apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a sintered glass filter. This was subjected to suction filtration, and then concentrated with a rotary evaporator. The resulting reaction mixture was distilled off excess alcohol under reduced pressure using a Kugelrohr distillation apparatus, whereby 1-hydroxy-5-decyloxy-1,1, An approximately 44:55 mixture of 3,3,5,5-hexamethyltrisiloxane and 1,5-bis (decyloxy) -1,1,3,3,5,5-hexamethyltrisiloxane was obtained as a colorless transparent liquid. 646 g (yield 44.8%) was obtained.
1-hydroxy-5-decyloxy-1,1,3,3,5,5-hexamethyltrisiloxane: EI-MS (70 eV), m / z (%); 225 (52), 207 (100), 193 (19); ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 0.102 (s, 6H), 0.111 (s, 6H), 0.135 (s, 6H), 0.861- 0.895 (m, 3H), 1.26-1.35 (m, 10H), 1.54-1.56 (m, 2H), 3.62-3.65 (m, 2H). ²⁹ Si-NMR (79 MHz, CDCl ₃ ) δ-19.9, 11.1, 10.0; IR (neat, cm ⁻¹ ) 3380, 2960, 2920, 1260, 1080, 1040, 800.
1,5-bis (decyloxy) -1,1,3,3,5,5-hexamethyltrisiloxane: EI-MS (70 eV), m / z (%); 505 (0.6), 363 (7 ), 225 (100), 207 (53), 193 (9); ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) 0.0960 (s, 18H), 0.854-0.888 (m, 6H), 1.27-1.28 (m, 10H), 1.50-1.57 (m, 2H), 3.62-3.66 (m, 3H); ²⁹ Si-NMR (79 MHz, CDCl) ₃ ) δ-21.5, -12.8.

撹拌子及び三方コックを備えた５０ｍＬ２口フラスコに、２，２，４，４，６，６−ヘキサエチルシクロトリシロキサン０．９８８ｇ（３．２３ｍｏｌ）、パラジウム活性炭素（エヌ・イー・ケムキャット社製）６９．３ｍｇ（５ｗｔ％Ｐｄ、乾燥品、０．０３２ｍｍｏｌＰｄ）及び脱水メタノ−ル（関東化学株式会社製）５．０２ｇ（１５７ｍｍｏｌ）を収めた。反応装置を減圧後、風船から供給した水素ガスで置換し、水素ガス雰囲気で２５℃で２４０時間撹拌した。装置内をアルゴンで置換し、反応混合物中の不溶物を焼結ガラスフィルターを用いてろ別した。これをロータリーエバポレーターで濃縮し、得られた反応混合物を減圧下で乾燥させることにより、１−ヒドロキシ−５−メトキシ−１，１，３，３，５，５−ヘキサエチルトリシロキサンを無色透明液体として１．０５ｇ（収率９６．３％）得た。
ＥＩ−ＭＳ（７０ｅＶ），ｍ/ｚ（％）；３２３（［Ｍ−Ｅｔ］^＋，１００），２９３（２１）；^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３）δ（ｐｐｍ）０．５１−０．６４（ｍ，１２Ｈ），０．９４−１．０３（ｍ，１８Ｈ），２．８３（ｓ，１Ｈ），３．５０（ｓ，３Ｈ），

In a 50 mL two-necked flask equipped with a stir bar and a three-way cock, 0.988 g (3.23 mol) of 2,2,4,4,6,6-hexaethylcyclotrisiloxane, palladium activated carbon (manufactured by N.E. Chemcat) ) 69.3 mg (5 wt% Pd, dried product, 0.032 mmol Pd) and 5.02 g (157 mmol) of dehydrated methanol (manufactured by Kanto Chemical Co., Inc.). After depressurizing, the reactor was replaced with hydrogen gas supplied from a balloon, and the mixture was stirred at 25 ° C. for 240 hours in a hydrogen gas atmosphere. The inside of the apparatus was replaced with argon, and insoluble matters in the reaction mixture were filtered off using a sintered glass filter. This was concentrated with a rotary evaporator, and the resulting reaction mixture was dried under reduced pressure to give 1-hydroxy-5-methoxy-1,1,3,3,5,5-hexaethyltrisiloxane as a colorless transparent liquid. As a result, 1.05 g (yield 96.3%) was obtained.
EI-MS (70 eV), m / z (%); 323 ([M-Et] ⁺ , 100), 293 (21); ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm) 0.51-0 .64 (m, 12H), 0.94-1.03 (m, 18H), 2.83 (s, 1H), 3.50 (s, 3H),

The production method of the present invention is useful for simply producing a linear trisiloxane having silanol groups at both ends, which is a silica dispersant for producing a rubber compound. Moreover, the terminal functional linear trisiloxane obtained by this invention is useful as a precursor which manufactures another functional linear or cyclic siloxane simply.

Claims (4)

In the presence of hydrogen gas and / or hydrogen generator, rhenium catalyst or platinum group transition metal catalyst , the general formula (1)

(In the formula, R represents an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom or an alkyl group having 1 to 2 carbon atoms. R may be the same or different, and two R bonded to the same silicon atom may form an alkanediyl group having 4 to 6 carbon atoms together) Trisiloxane and general formula (2)

(Wherein R ¹ represents a hydrogen atom; an alkyl group having 1 to 8 carbon atoms; or an aralkyl group having 7 to 8 carbon atoms), and a compound represented by the general formula ( 3)

(Wherein R and R ¹ represent the same meaning as described above). The method for producing a linear trisiloxane according to claim 1, wherein R ¹ is a hydrogen atom. Rhenium catalyst or a platinum group transition metal catalyst, supported on carbon, the manufacturing method according to claim 1 or 2 rhenium alone or a platinum group transition metal alone The process according to any one of claims 1 3 R is a methyl group.