JP4542128B2 - Norbornane skeleton-containing organosilicon compound and method for producing the same - Google Patents

Description

  The present invention relates to a novel organosilicon compound containing a norbornane skeleton and a method for producing the same.

  In general, an organosilicon compound having a hydrolyzable silyl group generates a silanol group in the presence of water, and this silanol group reacts with a hydroxyl group on the surface of the inorganic material, so that it can be used for surface treatment of an inorganic material. These organosilicon compounds are widely used as silane coupling agents, organic / inorganic resin modifiers and adhesion aids, and various additives when they further have an organic functional group that reacts with organic resins. Many patent applications relating to its application have been made and are known techniques.

  In ordinary silane coupling agents, a hydrolyzable silyl group site that reacts with an inorganic material and an organic functional group site that reacts with an organic resin are connected by a linear hydrocarbon chain. An object to be treated obtained by the silane coupling agent treatment is often used at a high temperature, and at that time, the heat resistance of the linear hydrocarbon chain is often problematic.

  In such a background, the norbornane skeleton, which is a polycyclic hydrocarbon skeleton, has a three-dimensional rigid structure, and it is known that the heat resistance can be improved by incorporating the skeleton into the structure of an organic polymer. It has become.

  The present invention has been made in view of the above circumstances, and a novel organosilicon compound in which a norbornane skeleton that contributes to heat stability is incorporated in a linking site between a hydrolyzable silyl group and a haloalkyl group that is an organic functional group, and It aims at providing the manufacturing method.

  As a result of intensive studies to achieve the above object, the present inventor has developed a novel organosilicon compound in which a hydrolyzable silyl group and a haloalkyl group are linked by a norbornane skeleton, and a stable production method thereof. It came to make.

That is, the present invention firstly
(A) norbornane skeleton,
(B) Provided is an organosilicon compound having a hydrolyzable silyl group directly connected to the norbornane skeleton, and (C) a haloalkyl group which is directly connected to the norbornane skeleton and contains or does not contain a hetero atom.

The present invention secondly,
A hydrolyzable silane having a hydrogen atom directly bonded to a silicon atom, and a norbornene skeleton and a norbornene derivative having a haloalkyl group containing or not containing a heteroatom directly bonded to the norbornene skeleton are subjected to a hydrosilylation reaction in the presence of a catalyst. A method for producing the organosilicon compound.

  Since the organosilicon compound of the present invention has a norbornane skeleton which is a rigid polycyclic hydrocarbon skeleton as a unit for connecting a hydrolyzable silyl group and a haloalkyl group, it has a conventional structure having a linear hydrocarbon chain as the unit. Excellent heat stability compared to Therefore, the organosilicon compound of the present invention itself is useful as a silane coupling agent having excellent heat stability. Since various organic functional groups can be easily introduced into the haloalkyl group in the organosilicon compound of the present invention, the organosilicon compound is also useful as a precursor for various silane coupling agents having excellent heat stability. is there.

  Hereinafter, the present invention will be specifically described.

[Norbornane skeleton-containing organosilicon compound]
The organosilicon compound of the present invention is
(A) norbornane skeleton,
(B) An organosilicon compound having a hydrolyzable silyl group directly connected to the norbornane skeleton, and (C) a haloalkyl group which is directly connected to the norbornane skeleton and contains or does not contain a hetero atom.

<(A) Norbornane skeleton>
Structure (A) is a norbornane skeleton. In the present invention, the norbornane skeleton is a remaining atomic group obtained by removing 2 to 12 hydrogen atoms from norbornane, and as long as it is such an atomic group, the number and position of hydrogen atoms to be removed are not limited.

  Examples of the norbornane skeleton of the structure (A) include the following structural formula:

で示されるノルボルニレン基、即ち、ノルボルナンの2位又は3位と5位又は6位の水素原子を除いた残りの２価炭化水素基が挙げられる。

In other words, the norbornylene group represented by the above formula, that is, the remaining divalent hydrocarbon group excluding the hydrogen atom at the 2-position or 3-position and 5-position or 6-position of norbornane.

<(B) Hydrolyzable silyl group>
Structure (B) is a hydrolyzable silyl group directly linked to the norbornane skeleton of structure (A). In the present invention, the hydrolyzable silyl group includes a monovalent hydrolyzable atom directly bonded to a silicon atom (an atom that generates a silanol group by reacting with water) and a monovalent hydrolyzable group directly bonded to a silicon atom. It is not particularly limited as long as it is a silyl group having at least one of (a group that generates a silanol group by reacting with water). Such a hydrolyzable silyl group is hydrolyzed to produce a silanol group, and this silanol group is dehydrated and condensed with an inorganic material to form a chemical bond of the formula: Si-OM (M: inorganic material). One or two or more hydrolyzable silyl groups of structure (B) may be present in the organosilicon compound of the present invention, and when two or more are present, they may be the same or different. There may be.
Examples of the hydrolyzable silyl group having the structure (B) include a silyl group represented by the following general formula (1 ′); a chlorosilyl group, a bromosilyl group, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group. Group, phenoxysilyl group and the like.

<(C) haloalkyl group>
Structure (C) is a haloalkyl group that includes or does not include a heteroatom directly connected to the norbornane skeleton of structure (A). The haloalkyl group of structure (C) reacts or copolymerizes with an organic resin to form a bond. Only one or two or more haloalkyl groups of the structure (C) may be present in the organosilicon compound of the present invention, and when two or more haloalkyl groups are present, they may be the same or different. Good.

Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Only one hetero atom may be present in the haloalkyl group of the structure (C), or two or more hetero atoms may be present, and when two or more hetero atoms are present, they may be the same or different. A heteroatom is, for example, a carbonyl group (—C (═O) —), an oxy group (—O—), a thio group (—S—) between two carbon atoms constituting the haloalkyl group of the structure (C). ), An imino group (—NH—) or the like, or, among the three carbon atoms, for example, a nitrilo group (—N <).
Examples of the haloalkyl group of the structure (C) include a haloalkyl group represented by the general formula (1 ″) described later.

<Other structures>
The organosilicon compound of the present invention may have other structures other than the structures (A) to (C) as long as the object of the present invention is not impaired. Other structures, when present in the organosilicon compound of the present invention, may be present alone or in combination of two or more, and when present in two or more, they may be the same or different. Good. Other structures include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Examples thereof include alkyl groups having 1 to 10 carbon atoms.

<Examples of norbornane skeleton-containing organosilicon compounds>
The hydrolyzable silyl group of the structure (B) and the haloalkyl group of the structure (C) are directly connected to different carbon atoms on the norbornane skeleton of the structure (A) from the viewpoint of heat stability of the organosilicon compound of the present invention. It is preferable that one of the structures (B) and (C) is directly connected to the carbon atom at the 2nd or 3rd position, and the other is directly connected to the carbon atom at the 5th or 6th position.

  As a preferable example of the organosilicon compound of the present invention, the following general formula (1):

（式中、Xは独立にハロゲン原子、炭素原子数1〜10のアルコキシ基、フェニルオキシ基、またはアセトキシ基であり、
Yはハロゲン原子であり、
R¹は炭素原子数1〜10のアルキル基であり、
R²は酸素原子、硫黄原子、窒素原子もしくはこれらの組み合わせを含み又は含まない炭素原子数1〜10のアルキレン基であり、
mは0〜2の整数である。）
で表される有機ケイ素化合物が挙げられる。

(In the formula, X is independently a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a phenyloxy group, or an acetoxy group;
Y is a halogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms,
R ² is an alkylene group having 1 to 10 carbon atoms containing or not containing an oxygen atom, a sulfur atom, a nitrogen atom or a combination thereof;
m is an integer of 0-2. )
The organosilicon compound represented by these is mentioned.

  Of the general formula (1), the following general formula (1 ′):

（式中、X、R¹およびmは前記のとおりである。）
で表されるシリル基が構造（B）の加水分解性シリル基に該当し、下記一般式（１''）：

(Wherein, X, R ¹ and m are as described above.)
A silyl group represented by the formula corresponds to a hydrolyzable silyl group of the structure (B), and the following general formula (1 ″):

（式中、YおよびR²は前記のとおりである。）
で表される部分が構造（C）のハロアルキル基に該当する。

(Wherein Y and R ² are as described above.)
The part represented by these corresponds to the haloalkyl group of the structure (C).

  When X is a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  When X is an alkoxy group, the number of carbon atoms is 1-10, typically 1-8, more typically 1-6, and even more typically 1-4. It is. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and a nonyloxy group. And decyloxy group.

  X is preferably a chlorine atom, a methoxy group, or an ethoxy group.

  Examples of Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom and a bromine atom are preferable.

R ¹ has 1 to 10 carbon atoms, typically 1 to 8, more typically 1 to 6, and even more typically 1 to 4. Examples of R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Among them, a methyl group and an ethyl group are preferable.

The number of carbon atoms in R ² is 1-10, typically 1-8, more typically 1-6, and even more typically 1-3.

When R ² does not contain an oxygen atom, a sulfur atom, a nitrogen atom or a combination thereof, examples thereof include a methylene group, an ethylene group, a methylmethylene group, a propylene group (trimethylene group and a methylethylene group), a butylene group ( For example, tetramethylene group, 1,2-butylene group, 1,3-butylene group, 2,3-butylene group), pentene group (for example, pentamethylene group), hexene group (for example, hexamethylene group), heptene group (E.g., heptamethylene group), octene group (e.g., octamethylene group), nonene group (e.g., nonamethylene group), decene group (e.g., decamethylene group) and the like, and among them, methylene group, ethylene group, Trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, Tamechiren group, nonamethylene group, a linear alkylene group is preferable, such as decamethylene group, a methylene group is more preferable.

When R ² contains an oxygen atom, a sulfur atom, a nitrogen atom, or a combination thereof, examples thereof include the following general formula:
-(CH ₂ ) _a -C (= O)-(CH ₂ ) _b- ,
-(CH ₂ ) _c -O- (CH ₂ ) _d- ,
-(CH ₂ ) _c -S- (CH ₂ ) _d- , and
-(CH ₂ ) _e -N ((CH ₂ ) _f H)-(CH ₂ ) _g-
(Wherein, a and b are integers of 1 to 8, provided that a + b is an integer of 2 to 9,
c and d are integers from 1 to 9, where c + d is an integer from 2 to 10,
e and g are integers of 1 to 9, and f is an integer of 0 to 8, provided that e + f + g is an integer of 2 to 10. )
The bivalent group represented by these is mentioned.

  The m is an integer of 0 to 2, more typically 0.

  As a more preferable example of the organosilicon compound of the present invention, the following general formula (2):

（式中、X、Y、R¹およびmは前記のとおりであり、nは1〜10の整数である。）
で表される有機ケイ素化合物が挙げられる。

(In the formula, X, Y, R ¹ and m are as defined above, and n is an integer of 1 to 10.)
The organosilicon compound represented by these is mentioned.

  N is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and even more preferably 1 to 3.

  As an even more preferred example of the organosilicon compound of the present invention, the following general formula (3):

（式中、X、R¹およびmは前記のとおりであり、Y'は臭素原子又は塩素原子である。）
で表される有機ケイ素化合物が挙げられる。

(Wherein, X, R ¹ and m are as defined above, and Y ′ is a bromine atom or a chlorine atom.)
The organosilicon compound represented by these is mentioned.

  As a specific example of the organosilicon compound of the present invention,

などが挙げられる。

Etc.

  The organosilicon compound of the present invention may be a pure substance or a mixture of isomers. Examples of the isomer mixture include a mixture of endo isomer and exo isomer, a mixture of positional isomers, and the like. Examples of the mixture of positional isomers include, for example, the isomer having the position 2 on the norbornane skeleton to which the hydrolyzable silyl group of the structure (B) is directly linked and the isomer having the position 3 in the general formula (1). And a mixture of an isomer at the 5-position and an isomer at the 6-position on the norbornane skeleton to which the haloalkyl group of the structure (C) is directly linked in the general formula (1).

[Production method]
<Manufacturing method 1>
The organosilicon compound of the present invention having the structures (A) to (C) is, for example,
Norbornene having a hydrolyzable silane having a hydrogen atom directly connected to a silicon atom (hereinafter sometimes referred to as “SiH group”), a norbornene skeleton and a haloalkyl group containing or not containing a heteroatom directly connected to the norbornene skeleton The derivative can be produced by subjecting the derivative to a hydrosilylation reaction in the presence of a catalyst.

・ Hydrolyzable silane with SiH group
The hydrolyzable silane having a SiH group is not particularly limited as long as it generates a hydrolyzable silyl group having a structure (B) by a hydrosilylation reaction with the norbornene derivative.

  When the organosilicon compound to be obtained by the production method of the present invention is an organosilicon compound represented by any one of the above general formulas (1) to (3), the hydrolyzable silane having a SiH group includes General formula:

（式中、X、R¹およびmは前記のとおりである。）
で表されるものを使用することができる。

(Wherein, X, R ¹ and m are as described above.)
Can be used.

-Norbornene Derivative The norbornene derivative has a norbornene skeleton and a haloalkyl group that is directly connected to the norbornene skeleton and includes or does not include a hetero atom. In the present invention, the norbornene skeleton means a remaining atomic group in which a carbon-carbon double bond is formed between at least one pair of two adjacent carbon atoms and at least one hydrogen atom is removed in norbornane. It is. As long as the valence of the norbornene skeleton is 1 or more, the number and position of the carbon-carbon double bonds are not limited.

  One or two or more haloalkyl groups in the norbornene derivative may be present, or two or more haloalkyl groups may be the same or different in the case where two or more are present.

  Examples of the hetero atom, the form in the haloalkyl group, and the like are the same as those described in the section “<(C) haloalkyl group>”.

  When the organosilicon compound to be obtained by the production method of the present invention is an organosilicon compound represented by the above general formula (1), the norbornene derivative is represented by the following general formula (4):

（式中、R²およびYは前記のとおりである。）
で表されるものを使用することができる。なお、本発明の製造方法で得ようとする有機ケイ素化合物が上記一般式（２）で表される有機ケイ素化合物である場合、前記ノルボルネン誘導体としては、R²が-(CH₂)_n-である上記一般式（４）で表されるものを使用することができる。また、本発明の製造方法で得ようとする有機ケイ素化合物が上記一般式（３）で表される有機ケイ素化合物である場合、前記ノルボルネン誘導体としては、R²が-CH₂-である上記一般式（４）で表されるものを使用することができる。

(Wherein R ² and Y are as described above.)
Can be used. When the organosilicon compound to be obtained by the production method of the present invention is an organosilicon compound represented by the general formula (2), R ² is — (CH ₂ ) _n — as the norbornene derivative. What is represented by the above general formula (4) can be used. Further, when the organosilicon compound to be obtained by the production method of the present invention is an organosilicon compound represented by the above general formula (3), the norbornene derivative may be the above general formula in which R ² is —CH ₂ —. What is represented by Formula (4) can be used.

The norbornene derivative may be a compound sold by various reagent manufacturers, or a reaction product obtained by a Diels-Alder reaction of an olefin compound capable of forming the haloalkyl group and cyclopentadiene according to a known method. May be used. For example, the norbornene derivative represented by the general formula (4) is represented by the following general formula:
CH ₂ = CH-R ² -Y
It can obtain by Diels-Alder reaction of the olefin compound represented by and cyclopentadiene.

<Manufacturing method 2>
Among the organosilicon compounds of the present invention having the (A) to (C),
(A) norbornane skeleton,
(B ′) an organooxysilyl group directly connected to the norbornane skeleton, and (C) an organosilicon compound having a haloalkyl group containing or not containing a hetero atom directly connected to the norbornane skeleton
As a hydrolyzable silane having a SiH group, a halosilane having a SiH group is used.
(A) norbornane skeleton as a product of the hydrosilylation reaction,
(B '') an halosilyl group directly connected to the norbornane skeleton, and (C) an organosilicon compound having a haloalkyl group that is directly connected to the norbornane skeleton and includes or does not include a heteroatom.
After the hydrosilylation reaction, it can also be produced by reacting the organosilicon compound having the (A), (B ″) and (C) with a hydroxyl group-containing organic compound.

-Organosilicon compounds having structures (A), (B ') and (C) Organosilicon compounds having structures (A), (B') and (C) have the structure (B) in the structure (B ') Except for the limitation, it is the same as the organosilicon compound having the structures (A) to (C).

  The structure (B ′) is an organooxysilyl group directly connected to the norbornane skeleton of the structure (A). One or two or more organooxysilyl groups of the structure (B ′) may be present in the organosilicon compound having (A), (B ′) and (C). When present above, they may be the same or different.

  Examples of the organosilicon compound having (A), (B ′) and (C) include the following general formula (5):

（式中、X'は独立に炭素原子数1〜10のアルコキシ基、フェニルオキシ基、またはアセトキシ基であり、Y、R¹、R²およびmは前記のとおりである。）
で表されるものが挙げられる。上記X'がアルコキシ基である場合、その炭素原子数のより典型的な、および、更により典型的な範囲、ならびに、該アルコキシ基の例は、上記Xについて説明したものと同様である。

(In the formula, X ′ is independently an alkoxy group having 1 to 10 carbon atoms, a phenyloxy group, or an acetoxy group, and Y, R ¹ , R ² and m are as described above.)
The thing represented by is mentioned. When X ′ is an alkoxy group, more typical and even more typical ranges of the number of carbon atoms, and examples of the alkoxy group are the same as those described for X.

・ Halosilanes with SiH groups
The halosilane having a SiH group is not particularly limited as long as it generates a halosilyl group having a structure (B ″) by a hydrosilylation reaction with the norbornene derivative.

  When the organosilicon compound to be obtained by the production method of the present invention is an organosilicon compound represented by the above general formula (5), the halosilane has the following general formula:

（式中、X''はハロゲン原子であり、R¹およびmは前記のとおりである。）
で表されるものを使用することができる。

(Wherein X ″ is a halogen atom, and R ¹ and m are as described above.)
Can be used.

-Organosilicon compounds having structures (A), (B ") and (C) Organosilicon compounds having structures (A), (B") and (C) have a structure (B ' Except for being limited to '), it is the same as the organosilicon compound having the structures (A) to (C).

  The structure (B ″) is a halosilyl group directly connected to the norbornane skeleton of the structure (A). One or two or more halosilyl groups of the structure (B ″) may be present in the organosilicon compound having (A), (B ″) and (C). When present above, they may be the same or different.

  When the organosilicon compound to be obtained by the production method of the present invention is the organosilicon compound represented by the general formula (5), the organosilicon compound having the (A), (B ″) and (C) As the following general formula (6):

（式中、X''、Y、R¹、R²およびmは前記のとおりである。）
で表されるものが挙げられる。

(Wherein X ″, Y, R ¹ , R ² and m are as described above.)
The thing represented by is mentioned.

Hydroxyl group-containing organic compound The hydroxyl group-containing organic compound is not particularly limited as long as it reacts with the halosilyl group having the structure (B ″) to produce the organooxysilyl group having the structure (B ′). Examples of the hydroxyl group-containing organic compound include alcohols, phenols, and carboxylic acids.

When the organosilicon compound to be obtained by the production method of the present invention is the organosilicon compound represented by the general formula (5), the hydroxyl group-containing organic compound is represented by the following general formula:
X'-H
(In the formula, X ′ is as described above.)
In particular, methanol and ethanol are preferable.

<Reaction conditions>
・ Hydrosilylation reaction In the hydrosilylation reaction, it is generally known to use a catalyst such as a heavy metal complex. In the hydrosilylation reaction of this production method, a palladium complex, a platinum complex, a rhodium complex, etc. Use heavy metal complexes. Of these, palladium complexes and platinum complexes are preferable from the viewpoints of reactivity, use amount, and the like, and among them, palladium complexes are more preferable from the viewpoint of reactivity.

  Although the usage-amount of a catalyst is not specifically limited, The range of 0.000001-0.01 mol with respect to 1 mol of said norbornene derivatives with respect to 1 mol of said norbornene derivatives is preferable especially. When the amount used is within this range, it is easier to obtain a reaction promoting effect sufficient for the amount of the catalyst.

  The mixing ratio of the hydrolyzable silane having a SiH group and the norbornene derivative is not particularly limited, but in terms of reactivity and productivity, the hydrolyzable silane having a SiH group is 0.5 to 1 mol per 1 mol of the norbornene derivative. It is preferable to make it react in 2 mol, especially 0.8-1.2 mol.

  In performing the hydrosilylation reaction, an auxiliary agent may be added to control the catalytic reaction in addition to the catalyst shown above. As the auxiliary, known materials may be used, and examples thereof include organic phosphorus compounds, phosphite compounds, organic nitrogen compounds and the like.

  This hydrosilylation reaction is generally a solvent-free reaction, but from the viewpoint of reaction control, the reaction may be performed after diluting the solvent. The solvent at that time is not particularly limited as long as it has no reactivity with the raw materials used and is not affected by the catalyst poison or the like. Specific solvents include hydrocarbon solvents such as pentane, hexane, cyclohexane, benzene, toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran and dioxane; ester solvents such as ethyl acetate and butyl acetate; acetonitrile, Examples include aprotic polar solvents such as dimethylformamide; chlorinated hydrocarbon solvents such as dichloromethane and chloroform. These solvents may be used alone or in combination of two or more.

  The reaction temperature is not particularly limited as long as the hydrosilylation reaction proceeds, but 0 to 200 ° C, particularly 10 to 150 ° C is preferable.

-Organooxylation reaction In this specification, the organooxylation reaction is a hydroxyl group containing an organosilicon compound having structures (A), (B '') and (C) after the hydrosilylation reaction in Production Method 2. This is to react with an organic compound to convert a halosilyl group having the structure (B ″) into an organooxysilyl group having the structure (B ′). Specifically, for example, when the hydroxyl group-containing organic compound is an alcohol, it is called an alkoxylation reaction. More specifically, for example, when the hydroxyl group-containing organic compound is methanol, it is referred to as a methoxylation reaction.

  Although the organooxylation reaction proceeds spontaneously even without a catalyst, it is preferably carried out in the presence of urea, tertiary amine, metal alkoxide, etc. as a scavenger for the generated hydrogen halide from the viewpoint of reactivity and productivity. .

  The amount of the scavenger used is not particularly limited, but halogens in the structure (B ″) of the organosilicon compound having the structures (A), (B ″) and (C) from the viewpoint of reactivity and productivity. A range of 0.5 to 1.5 mol, particularly 0.8 to 1.2 mol is preferable with respect to 1 mol of an atom. When the amount used is within this range, it is easier to obtain a sufficient reaction promoting effect commensurate with the amount of the scavenger.

  The compounding ratio of the organosilicon compound having the structures (A), (B ″) and (C) and the hydroxyl group-containing organic compound is not particularly limited, but from the viewpoint of reactivity and productivity, the structure of the organosilicon compound It is preferable to adjust the compounding ratio so that the amount of hydroxyl group in the hydroxyl group-containing organic compound is 1 to 3 mol, particularly 1 to 2 mol, relative to 1 mol of the halogen atom in (B ″). .

  The reaction temperature is not particularly limited as long as the organooxylation reaction proceeds, but 50 to 80 ° C, particularly 60 to 70 ° C is preferable.

  EXAMPLES Hereinafter, although a synthesis example and an Example demonstrate this invention concretely, this invention is not restrict | limited to the following Example. In the examples, GC is an abbreviation for gas chromatography, NMR is an abbreviation for nuclear magnetic resonance spectroscopy, and bp is an abbreviation for boiling point.

[Synthesis Example 1]
A 2 L autoclave equipped with a stirrer, thermometer and heater was charged with 488.5 g (3.7 mol) of dicyclopentadiene, 1074.7 g (8.9 mol) of allyl bromide and 3.1 g of hydroquinone, and sealed and under normal pressure The mixture was heated and stirred at 150 ° C. After 20 hours, the reaction was completed by confirming that the raw material peak had disappeared and a new product-derived peak appeared by GC. The reaction product was distilled under reduced pressure to obtain a pale yellow transparent liquid (bp 54 to 56 ° C., 3 mmHg) with a yield of 70%. It was confirmed by GC that the purity of this reaction product was 98%. Further, it was confirmed by ¹ H NMR and ¹³ C NMR that this reaction product was 5-bromomethyl-2-norbornene, which was a mixture of an endo isomer and an exo isomer.
¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): Main isomer (endo isomer) 0.56 (m, 1H), 1.27 (d, J = 8.2 Hz, 1H), 1.45 (m, 1H), 1.91 (m, 1H), 2.48 (m, 1H), 2.84 (s, 1H), 2.96 (s, 1H), 3.00 (dd, J = 6.9Hz, 9.6Hz, 1H), 3.17 (dd, J = 6.9Hz , 9.6Hz, 1H), 5.96 (m, 1H), 6.17 (m, 1H).
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): main isomer (endo isomer) 32.6, 38.0, 42.0, 43.0, 45.3, 49.5, 131.4, 138.0.

[Synthesis Example 2]
In Synthesis Example 1, 679.5 g (8.9 mol) of allyl chloride was used instead of 1074.7 g (8.9 mol) of allyl bromide, and the amount of hydroquinone charged was changed from 3.1 g to 2.4 g. Were reacted and distilled under reduced pressure in the same manner as in Synthesis Example 1 to obtain a colorless and transparent liquid (bp 80 to 82 ° C., 50 mmHg) with a yield of 57%. It was confirmed by GC that the purity of this reaction product was 98%. Further, it was confirmed by ¹ H NMR and ¹³ C NMR that this reaction product was 5-chloromethyl-2-norbornene, which was a mixture of an endo isomer and an exo isomer.
¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): Main isomer (endo isomer) 0.56 (m, 1H), 1.27 (d, J = 8.2 Hz, 1H), 1.45 (m, 1H), 1.91 (m, 1H), 2.48 (m, 1H), 2.84 (s, 1H), 2.96 (s, 1H), 3.00 (dd, J = 6.9Hz, 9.6Hz, 1H), 3.17 (dd, J = 6.9Hz , 9.6Hz, 1H), 5.96 (m, 1H), 6.17 (m, 1H).
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): main isomer (endo isomer) 31.2, 41.8, 42.6, 44.5, 48.5, 49.3, 131.6, 137.9.

[Example 1]
In a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 150 g (0.802 mol) of 5-bromomethyl-2-norbornene and 45.6 mg of dichloro (1,5-cyclooctadiene) palladium. , 89.6 mg of tricyclohexylphosphine were charged and heated to 135 ° C. After the internal temperature was stabilized, 130.4 g (0.963 mol) of trichlorosilane was added dropwise over 4 hours. The reaction liquid was stirred at 135 degreeC after completion | finish of dripping. After 2 hours, it was confirmed by GC that the raw material peak had disappeared and a new product-derived peak appeared, and the hydrosilylation reaction was completed. The temperature of the reaction solution was lowered to 80 ° C., and 61.6 g (1.92 mol) of methanol was added dropwise. After completion of dropping, the reaction solution was stirred at 75 ° C. for 1 hour. Subsequently, 69.3 g (1.16 mol) of urea was added to the reaction solution, and 46.2 g (1.44 mol) of methanol was further added dropwise. After stirring this reaction liquid at 75 degreeC for 2 hours, heating stirring was stopped. When the reaction solution was allowed to stand, it was separated into a methanol solution layer of urea hydrochloride and a reaction product layer. Therefore, the reaction product layer was collected and subjected to GC. As a result, it was confirmed that the raw material peak disappeared and a new product-derived peak appeared, and the methoxylation reaction was terminated. The reaction product was distilled under reduced pressure to obtain a colorless and transparent liquid (bp 110 to 116 ° C., 3 to 5 mmHg) with a yield of 93%. GC confirmed that the purity of the reaction product was 95%. According to ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR, the reaction product is 5-bromomethyl-norbornyltrimethoxysilane, a mixture of endo isomer and exo isomer, and trimethoxysilyl group The mixture was confirmed to be a mixture of an isomer directly bonded to the 2nd position of the norbornane skeleton and an isomer directly bonded to the 3rd position. The NMR spectrum of this reaction product is shown in FIGS.
¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): Isomeric mixture 0.45 to 3.27 (m, 12H), 3.35 (s, 6H, Si-OCH ₃ ), 3.37 (s, 3H, Si-OCH ₃ ) .
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): Isomeric mixture (only main product is described) 14.2, 23.4, 24.4, 36.1, 38.2, 39.0, 39.8, 42.2, 50.2 (Si-OCH ₃ ).
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): Isomeric mixture -45.1, -45.5, -45.8, -46.4.

[Example 2]
In Example 1, 40 mg of a platinum complex in which vinyldimethyldisiloxane was coordinated to chloroplatinic acid was used in place of 45.6 mg of dichloro (1,5-cyclooctadiene) palladium as a catalyst for the hydrosilylation reaction, and tricyclohexylphosphine was used. The hydrosilylation reaction, the methoxylation reaction and the distillation under reduced pressure were carried out in the same manner as in Example 1 except that the temperature before dropping the trichlorosilane was changed from 135 ° C to 120 ° C. A liquid (bp 110-116 ° C., 3-5 mmHg) was obtained with a yield of 67%. GC confirmed that the purity of the reaction product was 95%. According to ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR, the reaction product is 5-bromomethyl-norbornyltrimethoxysilane, a mixture of endo isomer and exo isomer, and trimethoxysilyl group The mixture was confirmed to be a mixture of an isomer directly bonded to the 2nd position of the norbornane skeleton and an isomer directly bonded to the 3rd position. The NMR spectrum of this reaction product was the same as in FIGS.

[Example 3]
In a 1 L separable flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 290 g (2.03 mol) of 5-chloromethyl-2-norbornene, dichloro (1,5-cyclooctadiene) palladium 32 g and 0.62 g of tricyclohexylphosphine were charged and heated to 135 ° C. After the internal temperature was stabilized, 302 g (2.23 mol) of trichlorosilane was added dropwise over 4 hours. The reaction liquid was stirred at 135 degreeC after completion | finish of dripping. After 2 hours, it was confirmed by GC that the raw material peak had disappeared and a new product-derived peak appeared, and the hydrosilylation reaction was completed. The temperature of the reaction solution was lowered to 80 ° C., and 142.7 g (4.46 mol) of methanol was added dropwise. After completion of dropping, the reaction solution was stirred at 75 ° C. for 1 hour. Subsequently, 160.6 g (2.67 mol) of urea was added to the reaction solution, and 107.0 g (3.35 mol) of methanol was further added dropwise. After stirring this reaction liquid at 75 degreeC for 2 hours, heating stirring was stopped. When the reaction solution was allowed to stand, it was separated into a methanol solution layer of urea hydrochloride and a reaction product layer. Therefore, the reaction product layer was collected and subjected to GC. As a result, it was confirmed that the raw material peak disappeared and a new product-derived peak appeared, and the methoxylation reaction was terminated. The reaction product was distilled under reduced pressure to obtain a colorless and transparent liquid (bp 106 to 108 ° C., 3 to 5 mmHg) with a yield of 92%. GC confirmed that the purity of the reaction product was 95%. According to ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR, the reaction product is 5-chloromethyl-norbornyltrimethoxysilane, a mixture of endo isomer and exo isomer, and trimethoxysilyl group. Was a mixture of an isomer directly bonded to the 2nd position of the norbornane skeleton and an isomer directly bonded to the 3rd position. The NMR spectra of this reaction product are shown in FIGS.
¹ H NMR (300 MHz, CDCl ₃ , δ (ppm)): Isomeric mixture 0.45 to 3.26 (m, 12H), 3.38 (s, 6H, Si-OCH ₃ ), 3.39 (s, 3H, Si-OCH ₃ ) .
¹³ C NMR (75 MHz, CDCl ₃ , δ (ppm)): Isomeric mixture (only main product is described) 14.4, 23.7, 24.5, 37.0, 37.9, 38.9, 42.2, 46.9, 50.3 (Si-OCH ₃ ).
²⁹ Si NMR (60 MHz, CDCl ₃ , δ (ppm)): Isomeric mixture -45.1, -45.6, -45.9, -46.5.

[Example 4]
In Example 3, 40 mg of a platinum complex in which vinyldimethyldisiloxane was coordinated to chloroplatinic acid was used in place of 0.32 g of dichloro (1,5-cyclooctadiene) palladium as a catalyst for the hydrosilylation reaction, and tricyclohexylphosphine was used. The hydrosilylation reaction, the methoxylation reaction and the distillation under reduced pressure were carried out in the same manner as in Example 3 except that the temperature before dropping the trichlorosilane was changed from 135 ° C to 120 ° C. A liquid (bp 106-108 ° C., 3-5 mmHg) was obtained with a yield of 66%. GC confirmed that the purity of the reaction product was 95%. According to ¹ H NMR, ¹³ C NMR, ²⁹ Si NMR, the reaction product is 5-chloromethyl-norbornyltrimethoxysilane, a mixture of endo isomer and exo isomer, and trimethoxysilyl group. Was a mixture of an isomer directly bonded to the 2nd position of the norbornane skeleton and an isomer directly bonded to the 3rd position. The NMR spectrum of this reaction product was the same as in FIGS.

1 is a diagram showing a ¹ H NMR spectrum of a reaction product of Example 1. FIG. 1 is a diagram showing a ¹³ C NMR spectrum of a reaction product of Example 1. FIG. 2 is a diagram showing a ²⁹ Si NMR spectrum of the reaction product of Example 1. FIG. 3 is a diagram showing a ¹ H NMR spectrum of a reaction product of Example 3. FIG. 3 is a diagram showing a ¹³ C NMR spectrum of a reaction product of Example 3. FIG. 4 is a diagram showing a ²⁹ Si NMR spectrum of a reaction product of Example 3. FIG.

Claims (2)

The following general formula:

(Where X '' is a halogen atom,
R ¹ is an alkyl group having 1 to 10 carbon atoms,
m is an integer of 0-2. )
A halosilane having a hydrogen atom directly connected to a silicon atom represented by the following general formula (4):

(In the formula, R ² is an alkylene group having 1 to 10 carbon atoms that contains or does not contain an oxygen atom, a sulfur atom, a nitrogen atom, or a combination thereof;
Y is a halogen atom. )
And a norbornene derivative represented by the following general formula (6):

(Wherein X ″, Y, R ¹ , R ² and m are as described above.)
After obtaining the organosilicon compound represented by
The organosilicon compound is represented by the following general formula:
X'-H
(In the formula, X ′ is an alkoxy group having 1 to 10 carbon atoms, a phenyloxy group, or an acetoxy group.)
Reacting with a hydroxyl group-containing organic compound represented by
The following general formula (5):

(Wherein, X ′, Y, R ¹ , R ² and m are as described above.)
The manufacturing method of the organosilicon compound represented by these . The production method according to claim 1 , wherein the catalyst is a palladium complex, a platinum complex, or a combination thereof.

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