JP2019218279A - Method for producing organosilicon compound, method for producing amino aryl group-containing organosilicon compound and organosilicon compound - Google Patents

Abstract

To provide a production method that can efficiently produce an amino aryl group-containing organosilicon compound at low cost.SOLUTION: An organosilicon compound represented by general formula (1) is produced by the following reaction or the like, and a benzyl group is deprotected from an amino group thereof, so that an amino aryl group-containing silicon compound is produced. R-R, Reach represent a hydrogen atom, an alkyl group or an alkoxy group; Rand Reach represent an alkyl group; X is a halogen atom; M is a lithium atom or magnesium halide; n is an integer of 1-4; m is an integer of 1-n.SELECTED DRAWING: None

Description

  The present invention relates to an organosilicon useful as a precursor for producing an aminoaryl group-containing organosilicon compound and a method for producing the same.

  An organosilicon compound having an aryl group substituted with an unsubstituted amino group (aminoaryl group-containing organosilicon compound) is useful as a raw material for a polyimide resin, a polyimide silicone resin, or the like, or as a silane coupling agent, and has an industrial scale. Several production methods have been developed so far in order to achieve efficient production in the United States.

  For example, Patent Document 1 and Non-Patent Document 1 disclose that a Grignard reagent produced from N, N-bis (trimethylsilyl) -p-bromoaniline is reacted with a silicon compound such as dimethyldichlorosilane and protected with a trimethylsilyl group. A method of producing an aminoaryl group-containing organosilicon compound by producing an aminoaryl group-containing organosilicon compound and deprotecting the trimethylsilyl group from the amino group is described.

  Patent Document 2 and Non-Patent Document 2 disclose that a Grignard reagent is produced from a chloroaniline derivative in which a protecting group is introduced into an amino group with a bis (chlorosilyl) alkylene compound such as 1,2-bis (chlorodimethylsilyl) ethane. There has been proposed a method for producing an aminoaryl group-containing organosilicon compound by reacting the Grignard reagent with a silicon compound and then deprotecting the protecting group from the amino group.

  On the other hand, Non-Patent Document 3 discloses that an aminoaryl group-containing organosilicon compound is produced by performing a coupling reaction between p-iodoaniline having no introduced protective group and triethoxysilane in the presence of a catalyst and a ligand molecule. A method is described.

JP-A-08-09979 JP 2006-104104 A

Journal of Organic Chemistry 51 51 2434 (1986) Synthetic Communication, Vol. 16, p. 809 (1986) Journal of Organic Chemistry 66 No. 7449 (2001)

As described above, Patent Documents 1 and 2 and Non-Patent Documents 1 and 2 describe a method for producing an aminoaryl group-containing organosilicon compound from a haloaniline derivative in which an amino group is protected with a silyl-based protecting group. Patent Document 3 discloses that an aminoaryl group-containing organosilicon compound was produced by a coupling reaction between p-iodoaniline not protected by a protecting group and a silicon compound.
However, the haloaniline derivatives used in Patent Documents 1 and 2 and Non-patent Documents 1 and 2 in which the amino group is protected by a silyl-based protecting group are complicated in the production process and protected by the protective group used for introducing the protecting group. When the agent is expensive, when an aminoaryl group-containing organosilicon compound is produced using the haloaniline derivative, there is a problem that the cost is increased and the production efficiency is reduced.

  For example, Non-Patent Document 1 discloses that after introducing a trimethylsilyl group into p-bromoaniline to give N- (trimethylsilyl) -p-bromoaniline, another trimethylsilyl group is introduced using a Grignard reaction. A method for producing N, N-bis (trimethylsilyl) -p-bromoaniline is described. However, in this method, the introduction of a trimethylsilyl group in two steps, the Grignard reaction here, and the Grignard reaction performed to protect the amino group and then introduce the silyl group are performed twice. Therefore, there is a problem that the number of steps increases, and the loss of each step accumulates to lower the yield. On the other hand, Patent Document 1 describes an example in which a trimethylsilyl group is introduced into N- (trimethylsilyl) -p-bromoaniline by another method. However, even if this method is used, the introduction of the protecting group still requires a plurality of steps, and it cannot be said that the method is still satisfactory in terms of production efficiency.

  In Patent Document 2 and Non-Patent Document 2, a protecting group is introduced into chloroaniline by using a bis (chlorosilyl) alkylene compound such as 1,2-bis (chlorodimethylsilyl) ethane as a protecting agent. Here, since this silyl-based protective agent is expensive, it is not practical to use it on an industrial scale. In addition, when introducing the protecting group, it is necessary to heat the mixture to a high temperature to perform reflux, which increases the energy cost.

  On the other hand, in Non-Patent Document 3, an aminoaryl group-containing organosilicon compound is produced by using a coupling reaction without using a protecting group. However, at the time of the coupling reaction, expensive bis (dibenzylideneacetone) is used. It is necessary to use a large amount of palladium (0) catalyst. Also, 2- (di-tert-butylphosphino) biphenyl used for the ligand molecule is an expensive substance. Therefore, the method using the coupling reaction is also unsuitable as a production method performed on an industrial scale.

  In order to solve the problems of the related art, the inventors of the present invention have studied diligently for the purpose of providing a production method capable of efficiently producing an aminoaryl group-containing organosilicon compound at low cost. Advanced.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, by using a benzyl group as a protecting group for an amino group, without complicated operations and high-temperature heating, without using an expensive protecting agent, It has been found that a haloaniline derivative having an amino group protected can be obtained, and further, an aminoaryl group-containing organosilicon compound protected with a benzyl group can be efficiently produced by the reaction of the haloaniline derivative with a silicon compound. By deprotecting the aminosilyl group-containing organosilicon compound protected by the benzyl group, it has been found that an aminoaryl group-containing organosilicon compound can be obtained in a high yield. The present invention has been proposed based on these findings, and specifically has the following configuration.

［一般式（１）において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁷は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基を表し；
Ｒ⁵およびＲ⁶は、それぞれ独立して、炭素数１〜６のアルキル基を表し；
ｎは１〜４の整数を表し；
ｍは１〜ｎの整数を表す。］

［一般式（２）において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁷は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基を表し；
Ｘは、ハロゲン原子を表す。］

［一般式（３）において、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴およびＲ⁷は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基を表し；
Ｍは、リチウム原子またはハロゲン化マグネシウムを表す。］

［一般式（４）において、Ｒ⁵およびＲ⁶は、それぞれ独立して、炭素数１〜６のアルキル基を表し；
ｎは１〜４の整数を表す。］
［２］ 下記一般式（７）で表される化合物と下記一般式（８）で表される化合物とを塩基性の媒体中で反応させて、前記一般式（２）で表される化合物を製造する工程を有する、［１］に記載の有機シリコン化合物の製造方法。

［一般式（７）において、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基を表し；
Ｘは、ハロゲン原子を表す。］

［一般式（８）において、Ｒ⁷は水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基を表し；
Ｙはハロゲン原子を表す。］
［３］ 前記一般式（２）で表される化合物と有機リチウム化合物とを反応させて前記一般式（３）で表される化合物を製造する、［１］または［２］に記載の有機シリコン化合物の製造方法。
［４］ 一般式（１）のｍが１であり、一般式（１）および一般式（４）のｎが４である、［１］〜［３］１〜３のいずれか１項に記載の有機シリコン化合物の製造方法。
［５］ 一般式（７）のＸおよび一般式（８）のＹが、ともに臭素原子である、［２］〜［４］のいずれか１項に記載の有機シリコン化合物の製造方法。
［６］ 下記一般式（１）で表される有機シリコン化合物のベンジル基をアミノ基から脱保護する工程を有する、下記一般式（６）で表されるアミノアリール基含有有機シリコン化合物の製造方法。

［一般式（６）において、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、それぞれ独立して、水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基を表し；
Ｒ⁵およびＲ⁶は、それぞれ独立して、炭素数１〜６のアルキル基を表し；
ｎは１〜４の整数を表し；
ｍは１〜ｎの整数を表す。］
［７］ ［１］〜［５］のいずれか１項に記載の製造方法を用いて、前記一般式（１）で表される有機シリコン化合物を製造する工程を有する、［６］に記載のアミノアリール基含有有機シリコン化合物の製造方法。
［８］ アミノ基からのベンジル基の脱保護を、水素分子を用いた水素添加反応によって行う、［６］または［７］に記載のアミノアリール基含有有機シリコン化合物の製造方法。
［９］ 前記一般式（１）で表される有機シリコン化合物。 [1] A method for producing an organosilicon compound represented by the following general formula (1), which is selected from a compound represented by the following general formula (2), and metal magnesium, an organic lithium compound, and an organomagnesium compound. A step of producing a compound represented by the following general formula (3) by reacting at least one compound with the compound represented by the following general formula (3); Reacting the organic silicon compound.

[In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4;
m represents an integer of 1 to n. ]

[In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
X represents a halogen atom. ]

[In the general formula (3), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
M represents a lithium atom or a magnesium halide. ]

[In the general formula (4), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4. ]
[2] A compound represented by the following general formula (7) is reacted with a compound represented by the following general formula (8) in a basic medium to give a compound represented by the above general formula (2). The method for producing an organosilicon compound according to [1], comprising a step of producing.

[In the general formula (7), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
X represents a halogen atom. ]

[In the general formula (8), R ⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
Y represents a halogen atom. ]
[3] The organic silicon according to [1] or [2], wherein the compound represented by the general formula (2) is reacted with an organolithium compound to produce a compound represented by the general formula (3). A method for producing a compound.
[4] The method according to any one of [1] to [3], wherein m in the general formula (1) is 1 and n in the general formulas (1) and (4) is 4. Method for producing an organosilicon compound.
[5] The method for producing an organosilicon compound according to any one of [2] to [4], wherein X in the general formula (7) and Y in the general formula (8) are both bromine atoms.
[6] A method for producing an aminoaryl group-containing organosilicon compound represented by the following general formula (6), comprising a step of deprotecting a benzyl group of an organosilicon compound represented by the following general formula (1) from an amino group: .

[In the general formula (6), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4;
m represents an integer of 1 to n. ]
[7] The method according to [6], comprising a step of producing the organosilicon compound represented by the general formula (1) using the production method according to any one of [1] to [5]. A method for producing an aminoaryl group-containing organosilicon compound.
[8] The method for producing an aminoaryl group-containing organosilicon compound according to [6] or [7], wherein the deprotection of the benzyl group from the amino group is performed by a hydrogenation reaction using a hydrogen molecule.
[9] An organic silicon compound represented by the general formula (1).

  According to the present invention, an aminoaryl group-containing organosilicon compound protected with a benzyl group can be efficiently produced at low cost. By deprotecting the aminoaryl group-containing organosilicon compound protected by the benzyl group, an aminoaryl group-containing organosilicon compound can be obtained in a high yield.

  Hereinafter, the present invention will be described in detail. The description of the components described below may be made based on representative embodiments or specific examples, but the present invention is not limited to such embodiments. Note that in this specification and the like, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.

<Organic silicon compound>
The organosilicon compound of the present invention has a structure represented by the following general formula (1).
The organosilicon compound represented by the general formula (1) has a structure in which two benzyl groups are bonded to a nitrogen atom bonded to a central benzene ring, and this structure is protected by a benzyl group. Constructs an aminoaryl group. In this specification, the organosilicon compound represented by the general formula (1) may be referred to as an "aminoaryl group-containing organosilicon compound protected with a benzyl group".
The compound represented by the general formula (1) can be efficiently produced at a low cost as described in the section <Method for producing organosilicon compound> below, and deprotects its benzyl group. Thereby, an aminoaryl group-containing organosilicon compound can be obtained with a high yield. Therefore, the compound represented by the general formula (1) is highly useful as a precursor for producing an aminoaryl group-containing organosilicon compound.
Hereinafter, the chemical structure of the compound represented by the general formula (1) will be described.

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represent. R ¹ , R ² , R ³ , R ⁴ and R ⁷ may be the same or different from each other. R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each bonded to any of the substitutable positions of the benzene ring to which the bond is attached.
The alkyl group in R ¹ , R ² , R ³ , R ⁴ and R ⁷ may be linear, branched or cyclic. The alkyl group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, -Methylbutyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 1-methylpentyl group, 1-ethylbutyl group and the like.
The alkoxy group in R ¹ , R ² , R ³ , R ⁴ and R ⁷ has a structure in which an alkyl group is bonded to an oxy group. For the description, preferred range, and specific examples of the alkyl group constituting the alkoxy group, the description, preferred range, and specific examples of the alkyl group for R ^{1 and the} like can be referred to.
The alkyl group and the alkoxy group in R ¹ , R ² , R ³ , R ⁴ and R ⁷ may be substituted with a substituent. Examples of the substituent include a fluoro group and a vinyl group.
Particularly preferred groups as R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom or a methyl group because the raw materials for the organosilicon compound are easily available.
A group particularly preferable as R ⁷ is a hydrogen atom or a methoxy group because the raw material for the organosilicon compound is easily available and deprotection can be performed easily.

In the general formula (1), the group represented by _{^{-Si (OR 5) nm R 6}} 4-n is attached to any substitutable position of the benzene ring to which the bond is applied. -Si (OR ⁵⁾ _nm bonding position of the group represented by R ⁶ _4-n is not particularly limited, ortho relative to the amino group, meta, may be any of the para position.
R ⁵ and R ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms. R ⁵ and R ⁶ may be the same or different. For the description, preferred range, and specific examples of the alkyl group, the description, preferred range, and specific examples of the alkyl group for R ^{1 and the} like can be referred to. Among them, R ⁵ and R ⁶ are preferably a methyl group, an ethyl group, a propyl group, and a butyl group, and more preferably a methyl group and an ethyl group.

n represents an integer of 1 to 4, and m represents an integer of 1 to n. m is preferably 1 to 2, and nm is preferably 2 to 3. When m is 2 or more, the structures enclosed in parentheses may be the same or different from each other. That is, when m is 2 or more, a plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁷ may be the same or different from each other. Further, when m is 1, two R ⁷ present in the molecule may be the same or different from each other. When n-m is 2 or more, plural R ⁵ may be the being the same or different. When n is 2 or less, a plurality of R ⁶ may be the same or different.

  Hereinafter, specific examples of the organosilicon compound represented by the general formula (1) will be exemplified. However, the organic silicon compound represented by the general formula (1) of the present invention should not be construed as being limited by these specific examples. In the following formula, Me represents a methyl group.

<Production method of organic silicon compound>
Next, the method for producing an organosilicon compound of the present invention will be described in detail.
The method for producing an organosilicon compound of the present invention is a method for producing an organosilicon compound represented by the general formula (1), and comprises a compound represented by the following general formula (2), a metal magnesium, an organolithium compound and A step of reacting at least one selected from organomagnesium compounds to produce a compound represented by the following general formula (3) ([1-1] organometallic compound production step); And a step of reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (4) ([1-2] organosilicon compound production step).
For the description of the compound represented by the general formula (1) produced in the present invention, the description in the above section <organic silicon compound> can be referred to.
In the method for producing an organosilicon compound of the present invention, a compound used as a starting material is a compound represented by the following general formula (2).

In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represent. ^{R 1, R 2, R 3} , R 4 and R ⁷ in the general formula (2) are respectively synonymous with ^{R 1, R 2, R 3} , R 4 and R ⁷ in the general formula (1), the For the description, preferred ranges, and specific examples, the corresponding description of general formula (1) can be referred to.
X represents a halogen atom. Examples of the halogen atom include an iodine atom, a bromine atom and a chlorine atom, and an iodine atom and a bromine atom are preferable because the compound represented by the general formula (3) is easily produced. X is bonded to any substitutable position of the benzene ring to which the bond is attached. The bonding position is not particularly limited, and may be any of the ortho, meta, and para positions with respect to the amino group.

The compound represented by the general formula (2) has a structure in which the amino group of haloaniline or a derivative thereof is protected with a benzyl group. This avoids a chemical change of the amino group in each of the above steps, and after the completion of these steps, the target aminobenzyl group-containing organosilicon compound protected by a benzyl group (see the general formula (1)). Is obtained in good yield. Here, the compound represented by the general formula (2) may be a haloaniline or a derivative thereof, a benzyl halide or a benzyl halide or a benzyl halide or a derivative thereof, as described in the following section (Method for producing compound represented by general formula (2)). It can be produced by a simple method of reacting the derivative with a basic medium, and the production does not require complicated operations, high-temperature heating and expensive protective agents. Therefore, when the compound represented by the general formula (2) is used as a starting material, an aminoaryl group in which an amino group is protected is used as compared with a case where a haloaniline derivative in which an amino group is protected by a conventional silyl protecting agent is used. An organic silicon compound can be efficiently produced at low cost.
Hereinafter, a method for producing the compound represented by Formula (2) will be specifically described.

(Method for producing compound represented by general formula (2))
A compound represented by the general formula (2), in which each R ⁷ bonded to the benzene ring of two benzyl groups is the same (compound represented by the following general formula (2a)), It can be produced by reacting a compound represented by the general formula (7) with a compound represented by the following general formula (8) under basic conditions. In addition, a compound represented by the general formula (2) in which each R ⁷ bonded to the benzene ring of two benzyl groups is different is a compound represented by the following general formula (8): ⁷ can be produced by using two kinds of compounds different from each other.

In the general formula ^{(7), R 1, R} 2, R 3, R 4 and X are each synonymous with ^{R 1, R 2, R 3} , R 4 and X in the general formula (2), the description thereof For preferred ranges and specific examples, reference can be made to the corresponding descriptions of the general formula (2) and the general formula (1) referred to in the general formula (2).
In the general formula (8), R ⁷ has the same meaning as R ⁷ in the general formula (2), and describes the preferred range, for example, the corresponding of the referenced general formula the general formula (2) (1) Can be referred to. Y represents a halogen atom. Examples of the halogen atom include an iodine atom, a bromine atom and a chlorine atom, and a bromine atom is preferable.
The base for adjusting the liquid property of the reaction solvent may be an inorganic basic compound or an organic basic compound. Examples of the inorganic basic compound include potassium carbonate and sodium carbonate. Examples of the organic basic compound include aliphatic tertiary amines such as triethylamine, 1,4-diazabicyclo [2.2.2] octane, and diazabicycloundecene. One of these bases may be used alone, or two or more may be used in combination.

The molar ratio of the compound represented by the general formula (7) and the compound represented by the general formula (8) to be subjected to the reaction (the compound represented by the general formula (7): the compound represented by the general formula (8)) Is preferably 1: 2 to 1: 3, more preferably 1: 2 to 1: 2.5, and still more preferably 1: 2 to 1: 2.2.
As the reaction solvent, aprotic solvents such as dimethylformamide (DMF), tetrahydrofuran (THF), diethyl ether, 1,2-dimethoxyethane, hexane, heptane, and toluene, or a mixed solvent obtained by mixing two or more of these solvents Can be used.
The reaction temperature can be appropriately selected from 0 to 40 ° C, and is preferably selected from 0 to 30 ° C.
The reaction time is preferably from 0.1 to 24 hours, more preferably from 1 to 12 hours.
The obtained compound represented by the general formula (2) may be purified and then used for producing an organic silicon compound, or may be subjected to production of an organic silicon compound without purification. The purification method is not particularly limited, and for example, an appropriate combination of purification methods such as extraction, column chromatography, and recrystallization can be used.

(Manufacturing process of organic silicon compound)
Next, each step of the method for producing an organic silicon compound will be described.

[1-1] Organic Metal Compound Production Step In this step, as shown in the following reaction formula, a compound represented by the above general formula (2) and a metal magnesium, an organic lithium compound, and an organic magnesium compound are selected. The compound represented by the general formula (3) is produced by reacting at least one compound. The compounds represented by the general formula (2) to be subjected to the reaction may be all the same or may be used in combination as a mixture of two or more.

  In the reaction formula, Mg represents metallic magnesium, RLi (R represents a hydrocarbon group) represents an example of an organic lithium compound, and RMgX (R represents a hydrocarbon group and X represents a halogen) represents an organic magnesium compound. Represents an example. The type of the halogen X constituting RMgX may be the same as or different from the halogen atom X in the general formula (2). Examples of the organic lithium compound include alkyl lithium such as n-butyl lithium and sec-butyl lithium, and examples of the organic magnesium compound include alkyl magnesium halides such as isopropyl magnesium chloride.

In the general formula ^{(3), R 1, R} 2, R 3, R 4 and R ⁷ have the same meanings as ^{R 1, R 2, R 3} , R 4 and R ^7, respectively, in the general formula (2), the For the description, preferred ranges, and specific examples, the corresponding description of general formula (1) referred to in general formula (2) can be referred to.
M represents a lithium atom or a magnesium halide MgX (X represents a halogen). Examples of the halogen constituting the magnesium halide include I, Br, and Cl. I and Br are preferable because the compound represented by the general formula (3) can be easily produced. The kind of the halogen constituting the magnesium halide may be the same as or different from the halogen atom X in the general formula (2). M is introduced by replacing the halogen atom X of the general formula (2) by reacting the compound represented by the general formula (2) with at least one selected from metal magnesium, an organolithium compound and an organomagnesium compound. The bonding position corresponds to the bonding position of the halogen atom X in the general formula (2).
The compound represented by the general formula (3) produced here is an organometallic compound, and acts as a nucleophile for the compound represented by the general formula (4) in the next step [1-2].

The reaction in step [1-1] can be performed using general reaction conditions used in Grignard reaction and lithium-halogen exchange reaction.
The molar ratio of the compound represented by the general formula (2) and at least one selected from the group consisting of metal magnesium, an organolithium compound and an organic magnesium (compound represented by the general formula (2): magnesium metal, (At least one selected from organic lithium compounds and organic magnesium) is preferably 1: 1 to 1: 4, more preferably 1: 1 to 1: 2, and 1: 1 to 1: 1. .5 is more preferable.
As the reaction solvent, an aprotic solvent such as tetrahydrofuran (THF), diethyl ether, 1,2-dimethoxyethane, hexane, heptane, and toluene, or a mixed solvent obtained by mixing two or more of these can be used.
The reaction temperature can be appropriately selected from -78 to 150 ° C, and is preferably selected from -78 to 100 ° C.
The reaction time is preferably from 0.1 to 24 hours, more preferably from 1 to 4 hours.
The produced compound represented by the general formula (3) may be purified and then subjected to the next step [1-2], or may be subjected to the next step [1-2] without purification.

[1-2] Organic Silicon Compound Production Step In this step, the compound represented by the general formula (3) produced in the step [1-1] is reacted with a compound represented by the following general formula (4). . As a result, an organosilicon compound represented by the general formula (1) is generated. The compounds represented by the general formula (3) to be used for the reaction may be all the same or may be used for the reaction in combination of two or more.

In the general formula (4), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms. R ⁵ and R ⁶ in the general formula (4) are respectively synonymous with R ⁵ and R ⁶ in the general formula (1), and describes the preferred range, for example, the corresponding of the general formula (1) The description can be referred to. Above all, R ⁵ and R ⁶ are preferably a methyl group, an ethyl group, a propyl group, or a butyl group. In view of availability and reactivity with the compound represented by the general formula (3), R ⁵ and R ⁶ are preferably a methyl group. And more preferably an ethyl group. Preferred specific examples of the compound represented by the general formula (4) include tetramethyl orthosilicate, tetraethyl orthosilicate, dimethoxydimethylsilane, and diethoxydimethylsilane.
n represents an integer of 1 to 4. When n is 2 or more, a plurality of R ⁵ may be the same or different from each other. When n is 2 or less, a plurality of R ⁶ may be the same or different.
The compounds represented by the general formula (4) to be subjected to the reaction may be all the same, or may be used in combination of two or more.

In the general formula (1) compounds represented by the generated _{^{here, -Si (OR 5) nm R}} 6 group represented by _4-n is a compound represented by the general formula (3) and general formula (4 ) Is introduced in place of M by the reaction with the compound represented by the formula (1), and the bonding position thereof corresponds to the bonding position of M in the general formula (3). Further, the group represented by ^{_{-Si (OR 5) nm R 6}} 4-n has the general formula corresponds a compound represented by (4) in the portion excluding the m a (OR ^5).

The molar ratio of the compound represented by the general formula (3) and the compound represented by the general formula (4) (the compound represented by the general formula (3): the compound represented by the general formula (4)) ) Is preferably from 1: 1 to 1: 6, more preferably from 1: 1 to 1: 4, even more preferably from 1: 1 to 1: 2.
For the specific examples of the reaction solvent used here, the specific examples of the reaction solvent used in the above step [1-1] can be referred to.
The reaction temperature can be appropriately selected from -78 to 40 ° C, and is preferably selected from -78 to 20 ° C.
The reaction time is preferably from 0.1 to 24 hours, more preferably from 1 to 6 hours.

[1-3] Purification step In this step, if necessary, the compound represented by the general formula (2) produced, the compound represented by the general formula (3) obtained in the step [1-1], and This is a step of purifying at least one of the organosilicon compounds represented by the general formula (1) obtained in the step [1-2]. After the step of producing the compound represented by the general formula (2), the step [ 1-1] and after step [1-2]. According to the production method of the present invention, a highly pure organosilicon compound can be produced without performing the purification step, but by performing the purification step, trace metal impurities and the like can be removed, and the purity can be further improved. Can be obtained.
The purification method is not particularly limited, and the method can be appropriately combined with a method commonly used for purifying an organic compound, such as extraction, column chromatography, recrystallization, and distillation under reduced pressure.

<Method for producing aminoaryl group-containing organosilicon compound>
Next, a method for producing the aminoaryl group-containing organosilicon compound of the present invention will be described.
The method for producing an aminosilyl-containing organosilicon compound of the present invention is a method for producing an organosilicon compound represented by the following general formula (6). The method for producing an aminoaryl group-containing organosilicon compound of the present invention includes at least a step of deprotecting a benzyl group of an organosilicon compound represented by the general formula (1) from an amino group ([2-2] deprotection step). Including. Further, the method for producing an aminoaryl group-containing organosilicon compound of the present invention further includes a step of producing an organosilicon compound represented by the general formula (1) ([2-1] organosilicon compound production step). Is preferred.
Hereinafter, each step will be described.

[2-1] Organic Silicon Compound Production Step For the description of the method for producing the organic silicon compound represented by the general formula (1), the description in the above section <Method for producing organic silicon compound> can be referred to. .

[2-2] Deprotection Step In this step, as shown in the following reaction formula, the benzyl group of the organosilicon compound represented by the general formula (1) produced in step [2-1] is removed from the amino group. Protect. As a result, an aminoaryl group-containing organosilicon compound represented by the following general formula (6) is produced.

For the description of the general formula (1), the description in the columns <Method for producing organosilicon compound> and <Organic silicon compound> can be referred to.
In the general formula (6), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , m and n represent R ¹ , R ² , R ³ , R ⁴ , R in the general formula (1), respectively. It is synonymous with ⁵ , R ⁶ , m and n, and for its description, preferred range and specific examples, the corresponding description of general formula (1) can be referred to.

The deprotection of the benzyl group can be performed using a general deprotecting agent and deprotection conditions for deprotecting the benzyl group. Specific examples of the deprotecting agent include palladium carbon, hydrogen gas, formic acid, formic acid amide, sodium metal, ammonium hexanitratocerrate (IV), 2,3-dichloro-5,6-dicyano-p-benzoquinone and the like. One type may be used alone, or two or more types may be used in combination. Among them, deprotection is preferably carried out by a hydrogenation reaction using a combination of palladium carbon and hydrogen gas, since there are few by-products and the reaction operation and the purification procedure of the target product are simple.
The molar ratio of the compound represented by the general formula (1) and the deprotecting agent to be subjected to the reaction (the compound represented by the general formula (1): the deprotecting agent) varies depending on the type of the deprotecting agent. : Preferably 0.01 to 1:10, more preferably 1: 0.01 to 1: 5, and still more preferably 1: 0.1 to 1: 2.
As a reaction solvent, it is possible to use an organic solvent such as tetrahydrofuran (THF), diethyl ether, 1,2-dimethoxyethane, hexane, heptane, toluene, methanol, ethanol, or a mixed solvent obtained by mixing two or more of these. it can.
The reaction temperature can be appropriately selected from -78 to 40 ° C, and is preferably selected from 0 to 30 ° C.
The reaction time is preferably from 0.1 to 72 hours, more preferably from 1 to 48 hours.
The obtained aminoaryl group-containing organosilicon compound may be purified if necessary. For example, the aminoaryl group-containing organosilicon compound can be isolated and purified to a high degree of purity by appropriately combining methods such as filtration, extraction, column chromatography, and recrystallization.

  According to the present invention, an organosilicon compound produced by the method for producing an organosilicon compound of the present invention is used as a precursor, and an aminoaryl group-containing organosilicon compound is produced by deprotection of the precursor. An aryl group-containing organosilicon compound can be efficiently produced at low cost. Therefore, the production method of the present invention can be effectively used for industrial production of an aminoaryl group-containing organosilicon compound, and the thus produced aminoaryl group-containing organosilicon compound is a polyimide resin, a polyimide silicone. It can be preferably used as a raw material such as a resin or a silane coupling agent.

  Hereinafter, features of the present invention will be described more specifically with reference to Examples and Comparative Examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples described below.

(Example 1) Production of N, N-dibenzyl-4-trimethoxysilylaniline In this example, first, as an example of a compound represented by the general formula (2), N, N-dibenzyl-4-bromoaniline Was manufactured.
[Production process of N, N-dibenzyl-4-bromoaniline]

  4-Bromoaniline (32.2 g, 187 mmol) was dissolved in N, N-dimethylformamide (180 mL), potassium carbonate (62.1 g, 449 mmol) and potassium iodide (6.2 g, 37 mmol) were added, and the mixture was added. Manufactured. Benzyl bromide (70.4 g, 412 mmol) was slowly added dropwise to this mixture while cooling in an ice bath under a nitrogen gas atmosphere, and the mixture was allowed to react at room temperature, followed by stirring. The reaction solution was poured into water (400 mL) to stop the reaction, and the precipitated solid was collected by suction filtration. After the obtained solid was washed with running water, it was dried by heating under reduced pressure. The obtained crude product was recrystallized from ethanol to obtain 57.3 g of a target N, N-dibenzyl-4-bromoaniline white needle crystal in a yield of 87%.

[Production process of N, N-dibenzyl-4-trimethoxysilylaniline]
Next, using the produced N, N-dibenzyl-4-bromoaniline, N, N-dibenzyl-4-trimethoxysilylaniline was produced as an example of the organosilicon compound represented by the general formula (1). In the following reaction formula, Me represents a methyl group.

A solution of N, N-dibenzyl-4-bromoaniline (10.0 g, 28.4 mmol) and tetramethylorthosilicate (13.0 g, 85.2 mmol) dissolved in tetrahydrofuran (100 mL) was subjected to-under a nitrogen gas atmosphere. Cooled to 78 degrees. While stirring this solution, a solution of sec-butyllithium in cyclohexane / hexane (1.0 mol / L, 56.8 mL) was added dropwise, and the mixture was heated to room temperature and reacted. The reaction solution was poured into a saturated aqueous solution of sodium hydrogencarbonate (200 mL) to stop the reaction. Ethyl acetate (200 mL) was added, and the mixture was stirred well. After the solids were separated by filtration, the organic layer was separated from the filtrate. The organic layer was washed with a saturated saline solution (200 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude N, N-dibenzyl-4-trimethoxysilylaniline.
¹ H NMR (CDCl ₃ ): 7.44 (d, J = 8.8 Hz, 2H), 7.35-7.19 (br, 10H), 6.75 (d, J = 8.8 Hz, 2H) , 4.66 (s, 4H), 3.60 (s, 9H)

(Example 2) Production of 4-trimethoxysilylaniline In this example, N, N-dibenzyl-4-trimethoxysilylaniline produced in Example 1 was used, and aminoaryl represented by the general formula (6) was used. As an example of the group-containing organosilicon compound, 4-trimethoxysilylaniline was manufactured. In the following reaction formula, Me represents a methyl group.

  N, N-dibenzyl-4-trimethoxysilylaniline (11.1 g, 28.4 mmol) was dissolved in tetrahydrofuran (100 mL), and palladium carbon (0.56 g, 5% Pd, about 55% wet with water) was added. The reaction was carried out by stirring at room temperature under a hydrogen gas atmosphere. After replacing the hydrogen gas in the reaction vessel with nitrogen gas, palladium carbon was filtered off from the reaction solution, and the filtrate was concentrated under reduced pressure to obtain a crude product. The crude product was purified by distillation under reduced pressure to obtain 5.8 g of a target colorless and transparent product of 4-trimethoxysilylaniline at a yield of 96% and a yield of 96%.

(Comparative Example 1) Production of an organosilicon compound from a bromoaniline derivative having an amino group protected with a tert-butoxycarbonyl group For comparison, the following reaction was carried out using a bromoaniline derivative having an amino group protected with a tert-butoxycarbonyl group. An attempt was made to produce an organosilicon compound represented by the formula (N- (tert-butoxycarbonyl) -4-trimethoxysilylaniline). In the following reaction formula, Boc represents a tert-butoxycarbonyl group. The tert-butoxycarbonyl group is one generally used as a protecting group for an amino group.

  A solution of N- (tert-butoxycarbonyl) -4-bromoaniline (10.0 g, 36.8 mmol) and tetramethyl orthosilicate (11.2 g, 73.5 mmol) dissolved in tetrahydrofuran (100 mL) was subjected to a nitrogen gas atmosphere. Cool down to -78 degrees below. While stirring this solution, a solution of sec-butyllithium in cyclohexane / hexane (1.0 mol / L, 73.5 mL) was added dropwise, and the mixture was heated to room temperature and reacted. The reaction solution was poured into a saturated aqueous solution of sodium hydrogencarbonate (200 mL) to stop the reaction. Ethyl acetate (200 mL) was added, and the mixture was stirred well. After the solid content was filtered off, the organic layer was separated from the filtrate. The organic layer was washed with saturated saline (200 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was analyzed by NMR and GC-MS. As a result, it was confirmed that the mixture was a mixture containing plural types of products, and the desired N- (tert-butoxycarbonyl) -4-trimethoxysilylaniline was obtained. Was not observed.

(Comparative Example 2) Production of an organosilicon compound from a compound in which a nitro group was introduced instead of an amino group For comparison, an organosilicon compound (4) represented by the following reaction formula was used using a compound in which a nitro group was introduced instead of an amino group. -Trimethoxysilyl-nitrobenzene). In the following reaction formula, Me represents a methyl group.

  A solution of 4-bromonitrobenzene (2.00 g, 9.90 mmol) and tetramethyl orthosilicate (3.01 mg, 19.8 mmol) dissolved in tetrahydrofuran (10 mL) was cooled to −78 ° C. under a nitrogen gas atmosphere. While stirring this solution, a solution of sec-butyllithium in cyclohexane / hexane (1.0 mol / L, 9.9 mL) was added dropwise, and the mixture was heated to room temperature and reacted. The reaction solution was poured into a saturated aqueous solution of sodium hydrogencarbonate (20 mL) to stop the reaction. Ethyl acetate (20 mL) was added, the mixture was stirred well, and the solid content was filtered off. The organic layer of the filtrate was separated. The organic layer was washed with saturated saline (200 mL), dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a crude product. The crude product was analyzed by NMR and GC-MS. As a result, it was confirmed that the mixture was a mixture containing a plurality of types of products, and the presence of the objective 4-trimethoxysilyl-nitrobenzene was not recognized.

  According to the present invention, an aminoaryl group-containing organosilicon compound can be efficiently produced at low cost. Therefore, the present invention can be used for industrial production of an aminoaryl group-containing organosilicon compound useful as a raw material of a polyimide resin or a polyimide silicone resin, and has high industrial applicability.

Claims (9)

A method for producing an organosilicon compound represented by the following general formula (1),
A step of reacting a compound represented by the following general formula (2) with at least one selected from metallic magnesium, an organolithium compound and an organomagnesium compound to produce a compound represented by the following general formula (3) When,
A method for producing an organosilicon compound, comprising: reacting a compound represented by the general formula (3) with a compound represented by the following general formula (4).

[In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4;
m represents an integer of 1 to n. ]

[In the general formula (2), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
X represents a halogen atom. ]

[In the general formula (3), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
M represents a lithium atom or a magnesium halide. ]

[In the general formula (4), R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4. ] A step of reacting a compound represented by the following general formula (7) with a compound represented by the following general formula (8) in a basic medium to produce a compound represented by the above general formula (2) The method for producing an organosilicon compound according to claim 1, comprising:

[In the general formula (7), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
X represents a halogen atom. ]

[In the general formula (8), R ⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
Y represents a halogen atom. ]   The method for producing an organosilicon compound according to claim 1, wherein the compound represented by the general formula (3) is produced by reacting the compound represented by the general formula (2) with an organolithium compound.   The method for producing an organosilicon compound according to any one of claims 1 to 3, wherein m in the general formula (1) is 1, and n in the general formulas (1) and (4) is 4.   The method for producing an organosilicon compound according to any one of claims 2 to 4, wherein X in the general formula (7) and Y in the general formula (8) are both bromine atoms. A method for producing an aminoaryl group-containing organosilicon compound represented by the following general formula (6), comprising a step of deprotecting a benzyl group of an organosilicon compound represented by the following general formula (1) from an amino group.

[In the general formula (6), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms;
R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4;
m represents an integer of 1 to n. ]

[In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4;
m represents an integer of 1 to n. ]   The aminoaryl group-containing organic compound according to claim 6, further comprising a step of manufacturing the organosilicon compound represented by the general formula (1) using the method according to claim 1. A method for producing a silicon compound.   The method for producing an aminoaryl group-containing organosilicon compound according to claim 6 or 7, wherein the deprotection of the benzyl group is performed by a hydrogenation reaction using a hydrogen molecule. An organosilicon compound represented by the following general formula (1).

[In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁷ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Represents;
R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 6 carbon atoms;
n represents an integer of 1 to 4;
m represents an integer of 1 to n. ]