JP5359185B2 - Organosilicon compound having amino group and protected hydroxyl group and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic silicon compound having an amino group and a protected hydroxy group, and capable of imparting rigidity and high mechanical strength to polymer materials. <P>SOLUTION: This invention relates to the organic silicon compound having the amino group and the protected hydroxy group and represented by general formula (1), wherein R<SP>1</SP>and R<SP>2</SP>are each identically or differently a 1 to 10C substituted or non-substituted aliphatic monovalent hydrocarbon group, provided that R<SP>1</SP>and R<SP>2</SP>may be bound to each other to form a ring together with the nitrogen atom bound to R<SP>1</SP>and R<SP>2</SP>; R<SP>1</SP>and R<SP>2</SP>may contain each one or more hetero atoms; R<SP>3</SP>, R<SP>4</SP>, R<SP>5</SP>, R<SP>6</SP>and R<SP>7</SP>are each identically or differently a 1 to 10C substituted or non-substituted monovalent hydrocarbon group; A is 1 to 10C substituted or non-substituted divalent hydrocarbon group; one or more carbon atoms may be replaced by N, O, or S; (n) is an integer of 0 to 2. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an organosilicon compound having an amino group and a protected hydroxyl group that are useful for silane coupling agents, surface treatment agents, fiber treatment agents, adhesives, paint additives, polymer modifiers, and the like, and a method for producing the same. It is.

  Conventionally, it is known that an organosilicon compound having an amino group is useful for a silane coupling agent, a surface treatment agent, a fiber treatment agent, an adhesive, a paint additive, and the like. In particular, when an inorganic material (for example, glass fiber, metal, oxide filler) is added for the purpose of improving the mechanical properties and heat resistance of the polymer material, the above organic silicon compound is used to make the polymer material and inorganic It is known that the adhesion with the material is improved and the dispersed state of the inorganic material is improved, and it is known that the expected addition effect becomes higher.

  Unlike the case of having an aromatic group such as an aromatic amino group or aniline, the silicon compound having an aliphatic amino group, in addition to the above coupling characteristics, retains transparency including the ultraviolet region, and has high water solubility. There are a wide variety of uses and methods of use.

  In recent years, in optical materials and electronic materials, these resins and cured products are required to have high properties such as rigidity, high mechanical strength, and transparency including an ultraviolet region. An organosilicon compound having both an aliphatic amino group and a hydroxyl group improves the adhesion and dispersion state between the polymer material and the inorganic material due to the synergistic effect of the amino group and the hydroxyl group. Various properties such as mechanical strength can be further improved, and having two functional groups greatly expands the range of polymer materials that can be expected to be effective. In addition, as a modifier, an amino group and a hydroxyl group can be simultaneously introduced into the polymer material. Therefore, in order to develop various polymer materials with higher added value, it has been desired to develop an organosilicon compound having both of them.

  However, an organosilicon compound having a hydroxyl group cannot be present in a stable state because it undergoes an intermolecular reaction between the hydroxyl group and a silicon atom and becomes a polymer (Non-patent Document 1). Therefore, until now, it has not been possible to isolate and purify an organosilicon compound having both an amino group and a hydroxyl group.

“ORGANOHALOSILANES Precursors to Silicone” (Netherlands), ELSEVIER PUBLISHING COMPANY, p. 350, 7th to 15th lines

  The present invention has been made in view of the above circumstances, and provides an organosilicon compound having a hydroxyl group protected with a triorganosilyl group capable of expressing the same effect as an amino group and a hydroxyl group, and a method for producing the same. Objective.

（式中、Ｒ¹及びＲ²は炭素数１〜１０の置換又は非置換の脂肪族１価炭化水素基であって、Ｒ¹とＲ²が結合してこれらが結合する窒素原子と共に環を形成しても良く、各々同一又は異なっていても良い。また、Ｒ¹及びＲ²はヘテロ原子を含んでも良い。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は炭素数１〜１０の置換又は非置換の１価炭化水素基で、各々同一又は異なっていても良い。Ａは炭素数１〜１０の置換又は非置換の２価炭化水素基であり、炭素原子の１個以上がＮ、Ｏ、Ｓで置き換えられていても良い。ｎは０〜２の整数である。）
で示されるアミノ基と保護された水酸基を有する有機ケイ素化合物を用いた場合に、シランカップリング剤、表面処理剤、高分子変性剤として用いた後で、脱保護することにより、任意で水酸基を発生することができ、アミノ基と水酸基を有する有機ケイ素化合物を用いたのと同等の効果が発現し、剛直性、高い機械的強度等の物性を高分子材料に付与することができることを知見した。更に、アニオン重合末端変性剤として用いた場合、アニオン重合末端は保護された水酸基とは反応せず、選択的にアルコキシケイ素部位と反応するため、定量的にアニオン重合末端に保護された水酸基を導入することができ、その後脱保護することにより容易にアミノ基及び水酸基変性高分子を製造できることを知見し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the following general formula (1)

(In the formula, R ¹ and R ² are substituted or unsubstituted aliphatic monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ¹ and R ² are bonded to form a ring together with the nitrogen atom to which they are bonded. R ¹ and R ² may contain a hetero atom, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may have 1 to 10 carbon atoms. Substituted or unsubstituted monovalent hydrocarbon groups, which may be the same or different, each A being a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, wherein one or more of the carbon atoms is (It may be replaced by N, O, or S. n is an integer of 0 to 2.)
In the case of using an organosilicon compound having an amino group and a protected hydroxyl group, the hydroxyl group is optionally protected by deprotection after use as a silane coupling agent, surface treatment agent, or polymer modifier. It has been found that the same effects as those obtained using an organosilicon compound having an amino group and a hydroxyl group can be produced, and physical properties such as rigidity and high mechanical strength can be imparted to the polymer material. . Furthermore, when used as an anionic polymerization terminal modifier, the anionic polymerization terminal does not react with the protected hydroxyl group, but selectively reacts with the alkoxysilicon moiety, so that the protected hydroxyl group is quantitatively introduced into the anionic polymerization terminal. It was found that the amino group and hydroxyl group-modified polymer can be easily produced by deprotection thereafter, and the present invention has been completed.

（式中、Ｒ¹及びＲ²は炭素数１〜１０の置換又は非置換の脂肪族１価炭化水素基であって、Ｒ¹とＲ²が結合してこれらが結合する窒素原子と共に環を形成しても良く、各々同一又は異なっていても良い。また、Ｒ¹及びＲ²はヘテロ原子を含んでも良い。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は炭素数１〜１０の置換又は非置換の１価炭化水素基で、各々同一又は異なっていても良い。Ａは炭素数１〜１０のアルキレン基又は−ＣＨ ₂ −Ｏ−（ＣＨ ₂ ） ₃ −基である。ｎは０〜２の整数である。）
で示されるアミノ基と保護された水酸基を有する有機ケイ素化合物。
請求項２：
下記一般式（５）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びｎは請求項１で定義した通りである。）
で示される請求項１記載のアミノ基と保護された水酸基を有する有機ケイ素化合物。
請求項３：
下記一般式（２）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は請求項１で定義した通りである。Ａ’は炭素数１〜８のアルキレン基又は−ＣＨ ₂ −Ｏ−ＣＨ ₂ −基である。）
で示される化合物と、下記一般式（３）
ＨＳｉＲ⁶ _n（ＯＲ⁷）_3-n （３）
（式中、Ｒ⁶、Ｒ⁷及びｎは請求項１で定義した通りである。）
で示されるハイドロジェンシラン化合物を反応させることを特徴とする請求項１記載のアミノ基と保護された水酸基を有する有機ケイ素化合物の製造方法。
請求項４：
式（２）の化合物１モルに対し、式（３）の化合物を０．５〜２モルの割合で反応させると共に、反応温度が０〜１２０℃である請求項３記載の製造方法。
請求項５：
反応を遷移金属触媒の存在下で行う請求項３又は４記載の製造方法。
請求項６：
下記一般式（４）

（式中、Ｒ¹、Ｒ²、Ｒ⁶、Ｒ⁷、Ａ及びｎは請求項１で定義した通りである。）
で示される化合物をＲ³Ｒ⁴Ｒ⁵Ｓｉ−基（Ｒ³、Ｒ⁴及びＲ⁵は請求項１で定義した通りである。）を有するシリル化剤によってシリル化することを特徴とする請求項１記載のアミノ基と保護された水酸基を有する有機ケイ素化合物の製造方法。
請求項７：
式（４）の化合物１モルに対し、シリル化剤をシリル基のモル数で１〜４モルの割合で反応させると共に、反応温度が０〜１５０℃である請求項６記載の製造方法。
That is, this invention provides the following organosilicon compound and its manufacturing method.
Claim 1:
The following general formula (1)

(In the formula, R ¹ and R ² are substituted or unsubstituted aliphatic monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ¹ and R ² are bonded to form a ring together with the nitrogen atom to which they are bonded. R ¹ and R ² may contain a hetero atom, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may have 1 to 10 carbon atoms. Substituted or unsubstituted monovalent hydrocarbon groups, which may be the same or different, and A is an alkylene group having 1 to 10 carbon atoms or a —CH ₂ —O— (CH ₂ ) ₃ — group. Is an integer from 0 to 2.)
An organosilicon compound having an amino group and a protected hydroxyl group.
Claim 2:
The following general formula (5)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n are as defined in claim 1).
The organosilicon compound which has the amino group and protected hydroxyl group of Claim 1 shown by these.
Claim 3:
The following general formula (2)

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined in claim 1. A ′ is an alkylene group having 1 to 8 carbon atoms or —CH ₂ —O—CH ₂ —. Group .)
And a compound represented by the following general formula (3)
HSiR ⁶ _n (OR ⁷ ) _3-n (3)
(Wherein R ⁶ , R ⁷ and n are as defined in claim 1).
The method for producing an organosilicon compound having an amino group and a protected hydroxyl group according to claim 1, wherein the hydrogensilane compound represented by formula (1) is reacted.
Claim 4:
The production method according to claim 3, wherein the compound of the formula (3) is reacted at a ratio of 0.5 to 2 mol with respect to 1 mol of the compound of the formula (2), and the reaction temperature is 0 to 120 ° C.
Claim 5:
The production method according to claim 3 or 4, wherein the reaction is carried out in the presence of a transition metal catalyst.
Claim 6:
The following general formula (4)

(Wherein R ¹ , R ² , R ⁶ , R ⁷ , A and n are as defined in claim 1).
The compound represented by the formula (1) is silylated with a silylating agent having an R ³ R ⁴ R ⁵ Si- group (R ³ , R ⁴ and R ⁵ are as defined in claim 1). Item 8. A process for producing an organosilicon compound having an amino group and a protected hydroxyl group according to Item 1.
Claim 7:
The process according to claim 6, wherein the silylating agent is reacted at a ratio of 1 to 4 moles of the silyl group with respect to 1 mole of the compound of the formula (4), and the reaction temperature is 0 to 150 ° C.

  According to the present invention, rigidity and high mechanical strength can be imparted to the polymer material by using the organosilicon compound having the amino group and the protected hydroxyl group.

（式中、Ｒ¹及びＲ²は炭素数１〜１０の置換又は非置換の脂肪族１価炭化水素基であって、Ｒ¹とＲ²が結合してこれらが結合する窒素原子と共に環を形成しても良く、各々同一又は異なっていても良い。また、Ｒ¹及びＲ²はヘテロ原子を含んでも良い。Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は炭素数１〜１０の置換又は非置換の１価炭化水素基で、各々同一又は異なっていても良い。Ａは炭素数１〜１０の置換又は非置換の２価炭化水素基であり、炭素原子の１個以上がＮ、Ｏ、Ｓで置き換えられていても良い。ｎは０〜２の整数である。）
で示されるアミノ基と保護された水酸基を有する有機ケイ素化合物である。 The compound of the present invention has the following general formula (1)

(In the formula, R ¹ and R ² are substituted or unsubstituted aliphatic monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ¹ and R ² are bonded to form a ring together with the nitrogen atom to which they are bonded. R ¹ and R ² may contain a hetero atom, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may have 1 to 10 carbon atoms. Substituted or unsubstituted monovalent hydrocarbon groups, which may be the same or different, each A being a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, wherein one or more of the carbon atoms is (It may be replaced by N, O, or S. n is an integer of 0 to 2.)
An organosilicon compound having an amino group and a protected hydroxyl group.

In the general formula (1), R ¹ and R ² are substituted or unsubstituted monovalent hydrocarbon groups, particularly aliphatic monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ¹ and R ² are bonded to each other. Thus, they may form a ring together with the nitrogen atom to which they are bonded, and may be the same or different. R ¹ and R ² may contain a hetero atom. Specific examples include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, Cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group And an acyclic or cyclic aliphatic monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group such as n-undecyl group, isoundecyl group, n-dodecyl group and isododecyl group. When R ¹ and R ² are combined to form a ring, R ¹ R ² N- is a nitrogen-containing heterocycle. The nitrogen-containing heterocycle may have a substituent, and specific examples of the substituent include alkyl groups such as a methyl group, an ethyl group, a (iso) propyl group, and a hexyl group; Alkoxy groups such as methoxy group, ethoxy group, (iso) propoxy group; groups consisting of halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, amino group, aromatic hydrocarbon group, ester group, An ether group, an acyl group, a thioether group, etc. are mentioned, These can also be used in combination. The substitution position of these substituents is not particularly limited, and the number of substituents is not limited. Specific examples of such nitrogen-containing heterocycles include piperidine, piperazine, morpholine, pyrrolidine, pyrrolidone, piperidone, and derivatives thereof.

R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, linear, branched or cyclic alkyl groups, alkenyl groups, An aryl group etc. are mentioned. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, vinyl Group, allyl group, methallyl group, butenyl group, phenyl group and the like are exemplified, and methyl group, ethyl group, (iso) propyl group and the like are particularly preferable.

A is a linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms, and one or more carbon atoms may be replaced by N, O, or S. For example, an alkylene group, an arylene group, an aralkylene group and the like can be mentioned. Specific examples include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an isobutylene group, and the like, and an ether group, a thioether group, A carbonyl group, an amino group, an ester group, an amide group, a urea group, a sulfide group, a disulfide group, and the like may be included. Specific examples include — (CH ₂ ) ₄ —, — (CH ₂ ) ₆ —, — (CH ₂ ) ₈ —, —CH ₂ —O— (CH ₂ ) ₃ —, etc. ₂ -O- (CH _{2) 3} - is preferable.

Specific examples of the organosilicon compound having an amino group and a protected hydroxyl group of the present invention include the following compound A and compound B, but the present invention is not limited by this illustration. Incidentally, Me is methyl, Et is ethyl, Pr is propyl, ⁱ Pr is an isopropyl group, Bu a butyl group, ^t Bu is tert- butyl, c-C ₆ H ₁₁ is a cyclohexyl group (hereinafter, The same).

但し、化合物Ａ及び化合物Ｂ中のＲａ、Ｒｂ並びにＲｃは、下記のＲａ、Ｒｂ並びにＲｃの組み合わせが例示される。

However, Ra, Rb and Rc in Compound A and Compound B are exemplified by the following combinations of Ra, Rb and Rc.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷及びｎは上記の通りである。） Among these, an organosilicon compound represented by the following general formula (5) is more preferable.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n are as described above.)

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴及びＲ⁵は上記の通りである。Ａ’は炭素数１〜８の置換又は非置換の２価炭化水素基であり、炭素原子の１個以上がＮ、Ｏ、Ｓで置き換えられていても良い。）
で示される化合物と、下記一般式（３）
ＨＳｉＲ⁶ _n（ＯＲ⁷）_3-n （３）
（式中、Ｒ⁶、Ｒ⁷及びｎは一般式（１）で定義した通りである。）
で示されるハイドロジェンシラン化合物を反応させる。反応は、遷移金属触媒の存在下で行うのが好ましく、遷移金属触媒としては白金触媒が好ましい。 A method for producing an organosilicon compound having an amino group represented by the general formula (1) and a protected hydroxyl group is represented by the following general formula (2).

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as described above. A ′ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 8 carbon atoms, One or more may be replaced with N, O, or S.)
And a compound represented by the following general formula (3)
HSiR ⁶ _n (OR ⁷ ) _3-n (3)
(In the formula, R ⁶ , R ⁷ and n are as defined in the general formula (1).)
The hydrogen silane compound shown by this is made to react. The reaction is preferably performed in the presence of a transition metal catalyst, and a platinum catalyst is preferred as the transition metal catalyst.

Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as described above.
A ′ is a linear or branched divalent hydrocarbon group having 1 to 8 carbon atoms, and one or more carbon atoms may be replaced by N, O, or S. For example, an alkylene group, an arylene group, an aralkylene group and the like can be mentioned. Specific examples include a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an isobutylene group, and the like, and an ether group, a thioether group, A carbonyl group, an amino group, an ester group, an amide group, a urea group, a sulfide group, a disulfide group, and the like may be included. Specific examples include — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₆ —, —CH ₂ —O—CH ₂ —, and the like, and in particular, —CH ₂ —O. -CH ₂ - is preferable.

但し、化合物Ｃ及び化合物Ｄ中のＲａ並びにＲｂは、上記のＲａ並びにＲｂの組み合わせが例示される。 Specific examples of the compound represented by the general formula (2) include the following compound C and compound D, but the present invention is not limited by this illustration.

However, Ra and Rb in Compound C and Compound D are exemplified by combinations of Ra and Rb described above.

  Specific examples of the hydrogensilane compound represented by the general formula (3) used in the above reaction include trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, and the like. Is exemplified.

  The compounding ratio of the compound represented by the general formula (2) and the hydrogensilane compound represented by the general formula (3) is not particularly limited, but from the viewpoint of reactivity and productivity, the compound represented by the general formula (2). The range of 0.5-2 mol, especially 0.7-1.2 mol of the hydrogen silane compound represented by the general formula (3) is preferred with respect to 1 mol.

  Examples of the platinum catalyst used in the above reaction include chloroplatinic acid, an alcohol solution of chloroplatinic acid, a toluene-1, xylene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, tetrakistri. Examples include phenylphosphine platinum, dichlorobistriphenylphosphine platinum, dichlorobisacetonitrile platinum, dichlorobisbenzonitrile platinum, dichlorocyclooctadiene platinum, and the like.

  Although the usage-amount of a platinum catalyst is not specifically limited, 0.000001-0.01 mol with respect to 1 mol of compounds shown by General formula (2) from the point of reactivity and productivity, especially 0.00001-0.001. A molar range is preferred.

  Although the reaction temperature of the above reaction is not particularly limited, it is preferably 0 to 120 ° C, particularly preferably 20 to 100 ° C, and the reaction time is preferably 1 to 20 hours, particularly preferably 1 to 10 hours.

  In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile and N, N-dimethylformamide, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

（式中、Ｒ¹、Ｒ²、Ｒ⁶、Ｒ⁷、Ａ及びｎは一般式（１）で定義した通りである。）
で示される化合物をＲ³Ｒ⁴Ｒ⁵Ｓｉ−基（Ｒ³、Ｒ⁴及びＲ⁵は一般式（１）で定義した通りである。）を有するシリル化剤によってシリル化する方法も例示される。 Moreover, as a manufacturing method of the organosilicon compound which has the amino group shown by the said General formula (1) and the protected hydroxyl group in this invention, following General formula (4)

(In the formula, R ¹ , R ² , R ⁶ , R ⁷ , A and n are as defined in the general formula (1).)
A method of silylating a compound represented by the following formula with a silylating agent having an R ³ R ⁴ R ⁵ Si— group (R ³ , R ⁴ and R ⁵ are as defined in the general formula (1)) is also exemplified. The

但し、化合物Ｅ及び化合物Ｆ中のＲａ並びにＲｃは、上記のＲａ並びにＲｃの組み合わせが例示される。 Specific examples of the compound represented by the general formula (4) include the following compound E and compound F, but the present invention is not limited by this illustration.

However, Ra and Rc in Compound E and Compound F are exemplified by combinations of Ra and Rc described above.

Examples of the silylating agent used in the above reaction include R ³ R ⁴ R ⁵ SiX (R ³ , R ⁴ , R ³ R ⁴ R ⁵ SiX such as trimethylchlorosilane, trimethylbromosilane, trimethyliodosilane, triethylchlorosilane, t-butyldimethylchlorosilane, and triisopropylchlorosilane. R ⁵ is as described above, and X is a (R ³ R ⁴ R ⁵ Si) ₂ NH such as a triorganohalosilane compound represented by a halogen atom such as a chlorine atom), hexamethyldisilazane, hexaethyldisilazane, etc. CR ₃ C such as disilazane represented by (R ³ , R ⁴ , R ⁵ are as described above), other silazane compounds, bis (trimethylsilyl) acetamide, bis (triethylsilyl) acetamide, bis (trimethylsilyl) trifluoroacetamide, etc. (-OSiR ³ R ⁴ R ⁵ ) = NSiR ³ R ⁴ R ⁵ (R is water Examples include silylamide compounds such as elemental or fluorine atoms, R ³ , R ⁴ and R ⁵ are as described above.

  The compounding ratio of the compound represented by the general formula (4) and the silylating agent is not particularly limited. However, from the viewpoint of reactivity and productivity, the silylating agent is used with respect to 1 mol of the compound represented by the general formula (4). Is preferably in the range of 1 to 4 mol, particularly 1 to 2 mol in terms of the number of moles of silyl group.

  Although the reaction temperature of the above reaction is not particularly limited, it is preferably 0 to 150 ° C., particularly preferably 20 to 130 ° C., and the reaction time is preferably 1 to 20 hours, particularly preferably 1 to 10 hours.

  The above reaction proceeds even without a catalyst, but a catalyst can also be used. Examples of the catalyst used include quaternary ammonium salts, acids such as sulfuric acid and sulfonic acid, derivatives thereof, and inorganic salts thereof.

  In addition, although the said reaction advances even without a solvent, a solvent can also be used. Solvents used include hydrocarbon solvents such as pentane, hexane, cyclohexane, heptane, isooctane, benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, and ester solvents such as ethyl acetate and butyl acetate. And aprotic polar solvents such as acetonitrile, N, N-dimethylformamide and N-methylpyrrolidone, and chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

  The organosilicon compound produced by the production method of the present invention can be further purified by various purification methods such as distillation, filtration, washing, column separation, solid adsorbent and the like depending on the target quality. In order to remove a small amount of impurities such as a catalyst and obtain a high purity, purification by distillation is preferable.

The obtained organosilicon compound is useful as a surface treatment agent such as a silane coupling agent, glass, silicon wafer, metal, or a polymer modifier. In this case, after use in such applications, the triorganosilyl group (R ³ R ⁴ R ⁵ Si— group) is eliminated by a conventional method such as hydrolysis or alcoholysis, and until then, the triorganosilyl group The protected hydroxyl group can be deprotected to reveal the hydroxyl group.

  EXAMPLES Hereinafter, although a synthesis example and an Example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

[Synthesis Example 1] Synthesis of 7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxa-1-heptene In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 33 g of methylpiperazine (0. 33 mol), 34 g (0.30 mol) of allyl glycidyl ether was added dropwise at 85 to 95 ° C. over 4 hours, and the mixture was stirred at that temperature for 1 hour. After cooling to 60 ° C., 36 g (0.23 mol) of hexamethyldisilazane was added dropwise at 60 to 70 ° C. over 1 hour and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 78.4 g of 7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxa-1-heptene as a fraction having a boiling point of 96 to 97 ° C./0.3 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 1 shows a chart of ¹ H-NMR spectrum, and FIG. 2 shows a chart of IR spectrum.
Mass spectrum m / z 286, 271, 245, 215, 113
From the above results, it was confirmed that the obtained compound was 7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxa-1-heptene.

[Example 1] Synthesis of 1-trimethoxysilyl-7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxaheptane Into a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 7- ( 4-methylpiperazino) -6-trimethylsiloxy-4-oxa-1-heptene (70 g, 0.25 mol), platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in toluene solution ( 0.16 g of platinum content (3% by mass) was charged and heated to 50 ° C. After the internal temperature was stabilized, 24 g (0.20 mol) of trimethoxysilane was added dropwise at 45 to 55 ° C. over 3 hours and stirred at that temperature for 2 hours. The reaction solution was distilled to obtain 73 g of a colorless transparent fraction having a boiling point of 154 to 155 ° C./0.3 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 3 shows a chart of ¹ H-NMR spectrum, and FIG. 4 shows a chart of IR spectrum.
Mass spectrum m / z 408, 393, 318, 229, 121, 113
From the above results, it was confirmed that the obtained compound was 1-trimethoxysilyl-7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxaheptane.

Example 2 Synthesis of 1-methyldiethoxysilyl-7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxaheptane Into a flask equipped with a stirrer, reflux, dropping funnel and thermometer, 7- Toluene solution of (4-methylpiperazino) -6-trimethylsiloxy-4-oxa-1-heptene (70 g, 0.25 mol), platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Platinum content 3% by mass) 0.16 g was charged and heated to 50 ° C. After the internal temperature was stabilized, 27 g (0.20 mol) of methyldiethoxysilane was added dropwise at 45 to 55 ° C. over 3 hours and stirred at that temperature for 2 hours. The reaction solution was distilled to obtain 76 g of a colorless transparent fraction having a boiling point of 162 to 163 ° C./0.3 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 5 shows a chart of ¹ H-NMR spectrum, and FIG. 6 shows a chart of IR spectrum.
Mass spectrum m / z 420, 405, 330, 229, 133, 113
From the above results, it was confirmed that the obtained compound was 1-methyldiethoxysilyl-7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxaheptane.

[Synthesis Example 2] Synthesis of 6-hydroxy-1-trimethoxysilyl-7- (4-methylpiperazino) -4-oxaheptane In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 33 g of methylpiperazine ( 0.33 mol) was charged, and 71 g (0.30 mol) of γ-glycidoxypropyltrimethoxysilane was added dropwise at 80 to 90 ° C. over 4 hours, followed by stirring at that temperature for 2 hours.

A mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent), and IR spectrum of the obtained reaction solution were measured. The results of the mass spectrum are shown below. FIG. 7 shows a chart of ¹ H-NMR spectrum, and FIG. 8 shows a chart of IR spectrum.
Mass spectrum m / z 336, 318, 273, 143, 121, 113
From the above results, it was confirmed that the obtained compound was a mixture containing 6-hydroxy-1-trimethoxysilyl-7- (4-methylpiperazino) -4-oxaheptane.

[Example 3] 1-trimethoxysilyl-7- (4-methylpiperazino) -6-trimethylsiloxy- using 6-hydroxy-1-trimethoxysilyl-7- (4-methylpiperazino) -4-oxaheptane as a raw material Synthesis of 4-oxaheptane A flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with 85 g (0.33 mol) of bis (trimethylsilyl) trifluoroacetamide and synthesized in Synthesis Example 2 while cooling with water. 123 g of the reaction solution was added dropwise over 1 hour and stirred at room temperature for 1 hour. The reaction solution was distilled to obtain 55 g of a colorless transparent fraction having a boiling point of 154 to 155 ° C./0.3 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured and found to be the same as the spectrum of the compound obtained in Example 1. It was confirmed that it was methoxysilyl-7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxaheptane.

[Synthesis Example 3] Synthesis of 6-hydroxy-1-methyldiethoxysilyl-7- (4-methylpiperazino) -4-oxaheptane In a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer, 20 g of methylpiperazine (0.20 mol) was charged, and 71 g (0.20 mol) of γ-glycidoxypropylmethyldiethoxysilane was added dropwise at 90 to 100 ° C. over 5 hours, followed by stirring at that temperature for 2 hours.

A mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent), and IR spectrum of the obtained reaction solution were measured. The results of the mass spectrum are shown below. Further, ¹ H-NMR spectrum chart of Figure 9, Figure 10 is the chart for the IR spectrum.
Mass spectrum m / z 348, 330, 287, 257, 143, 113
From the above results, it was confirmed that the obtained compound was a mixture containing 6-hydroxy-1-methyldiethoxysilyl-7- (4-methylpiperazino) -4-oxaheptane.

Example 4 1-methyldiethoxysilyl-7- (4-methylpiperazino) -6-trimethyl using 6-hydroxy-1-methyldiethoxysilyl-7- (4-methylpiperazino) -4-oxaheptane as a raw material Synthesis of Siloxy-4-oxaheptane In a flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer, 57 g (0.22 mol) of bis (trimethylsilyl) trifluoroacetamide was charged, and 91 g of the reaction solution synthesized in Synthesis Example 3 Was added dropwise at 65-75 ° C. over 4 hours and stirred at room temperature for 2 hours. The reaction solution was distilled to obtain 52 g of a colorless transparent fraction having a boiling point of 162 to 163 ° C./0.3 kPa.

When the mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured, it was the same as the spectrum of the compound obtained in Example 2, and the obtained compound was 1-methyl. It was confirmed to be diethoxysilyl-7- (4-methylpiperazino) -6-trimethylsiloxy-4-oxaheptane.

[Synthesis Example 4] Synthesis of 7-diethylamino-6-trimethylsiloxy-4-oxa-1-heptene 37 g (0.50 mol) of diethylamine was charged into a flask equipped with a stirrer, a refluxer, a dropping funnel and a thermometer. Then, 52 g (0.46 mol) of allyl glycidyl ether was added dropwise over 9 hours at -95 ° C under reflux, and the mixture was stirred at 95 ° C for 5 hours. After cooling to 70 ° C., 44 g (0.28 mol) of hexamethyldisilazane was added dropwise at 70 to 75 ° C. over 2 hours and stirred at that temperature for 1 hour. By distilling the reaction solution, 101 g of 7-diethylamino-6-trimethylsiloxy-4-oxa-1-heptene was obtained as a fraction having a boiling point of 93 to 94 ° C./0.8 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 11 shows a chart of ¹ H-NMR spectrum, and FIG. 12 shows a chart of IR spectrum.
Mass spectrum m / z 259,244,218,188,86
From the above results, it was confirmed that the obtained compound was 7-diethylamino-6-trimethylsiloxy-4-oxa-1-heptene.

Example 5 Synthesis of 1-methyldiethoxysilyl-7-diethylamino-6-trimethylsiloxy-4-oxaheptane Into a flask equipped with a stirrer, reflux, dropping funnel and thermometer, 7-diethylamino-6- 52 g (0.20 mol) of trimethylsiloxy-4-oxa-1-heptene, toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content 3 mass%) 0 .13 g was charged and heated to 60 ° C. After the internal temperature was stabilized, 22 g (0.16 mol) of methyldiethoxysilane was added dropwise at 55 to 65 ° C. over 3 hours and stirred at that temperature for 1 hour. The reaction solution was distilled to obtain 55 g of a colorless transparent fraction having a boiling point of 146 to 147 ° C./0.4 kPa.

The mass spectrum, ¹ H-NMR spectrum (deuterated chloroform solvent) and IR spectrum of the obtained fraction were measured. The results of the mass spectrum are shown below. FIG. 13 shows a chart of ¹ H-NMR spectrum, and FIG. 14 shows a chart of IR spectrum.
Mass spectrum m / z 378,303,202,133,86
From the above results, it was confirmed that the obtained compound was 1-methyldiethoxysilyl-7-diethylamino-6-trimethylsiloxy-4-oxaheptane.

2 is a ¹ H-NMR spectrum of a silane compound obtained in Synthesis Example 1. FIG. 3 is an IR spectrum of the silane compound obtained in Synthesis Example 1. 1 is a ¹ H-NMR spectrum of a silane compound obtained in Example 1. 2 is an IR spectrum of the silane compound obtained in Example 1. 2 is a ¹ H-NMR spectrum of a silane compound obtained in Example 2. 3 is an IR spectrum of the silane compound obtained in Example 2. 2 is a ¹ H-NMR spectrum of a silane compound obtained in Synthesis Example 2. 3 is an IR spectrum of the silane compound obtained in Synthesis Example 2. 2 is a ¹ H-NMR spectrum of a silane compound obtained in Synthesis Example 3. 4 is an IR spectrum of the silane compound obtained in Synthesis Example 3. 2 is a ¹ H-NMR spectrum of a silane compound obtained in Synthesis Example 4. 6 is an IR spectrum of the silane compound obtained in Synthesis Example 4. ¹ is a ¹ H-NMR spectrum of a silane compound obtained in Example 5. 4 is an IR spectrum of the silane compound obtained in Example 5.

Claims (7)

The following general formula (1)

(In the formula, R ¹ and R ² are substituted or unsubstituted aliphatic monovalent hydrocarbon groups having 1 to 10 carbon atoms, and R ¹ and R ² are bonded to form a ring together with the nitrogen atom to which they are bonded. R ¹ and R ² may contain a hetero atom, and R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ may have 1 to 10 carbon atoms. Substituted or unsubstituted monovalent hydrocarbon groups, which may be the same or different, and A is an alkylene group having 1 to 10 carbon atoms or a —CH ₂ —O— (CH ₂ ) ₃ — group. Is an integer from 0 to 2.)
An organosilicon compound having an amino group and a protected hydroxyl group. The following general formula (5)

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and n are as defined in claim 1).
The organosilicon compound which has the amino group and protected hydroxyl group of Claim 1 shown by these. The following general formula (2)

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are as defined in claim 1. A ′ is an alkylene group having 1 to 8 carbon atoms or —CH ₂ —O—CH ₂ —. Group .)
And a compound represented by the following general formula (3)
HSiR ⁶ _n (OR ⁷ ) _3-n (3)
(Wherein R ⁶ , R ⁷ and n are as defined in claim 1).
The method for producing an organosilicon compound having an amino group and a protected hydroxyl group according to claim 1, wherein the hydrogensilane compound represented by formula (1) is reacted.   The production method according to claim 3, wherein the compound of the formula (3) is reacted at a ratio of 0.5 to 2 mol with respect to 1 mol of the compound of the formula (2), and the reaction temperature is 0 to 120 ° C.   The production method according to claim 3 or 4, wherein the reaction is carried out in the presence of a transition metal catalyst. The following general formula (4)

(Wherein R ¹ , R ² , R ⁶ , R ⁷ , A and n are as defined in claim 1).
The compound represented by the formula (1) is silylated with a silylating agent having an R ³ R ⁴ R ⁵ Si- group (R ³ , R ⁴ and R ⁵ are as defined in claim 1). Item 8. A process for producing an organosilicon compound having an amino group and a protected hydroxyl group according to Item 1.   The process according to claim 6, wherein the silylating agent is reacted at a ratio of 1 to 4 moles of the silyl group with respect to 1 mole of the compound of the formula (4), and the reaction temperature is 0 to 150 ° C.

Images