KR20180129333A - catalysts for silylation, their preparation and their use for preparing silylated compounds - Google Patents

Abstract

The present invention relates to a hydrosilylation catalyst used for silylation of compounds having various functional groups, a process for producing the same, and a process for producing a silylated compound using the same, and more particularly, to a process for producing a silylated compound using carbon nanotubes, Wherein the carbon structure is one or more selected from nanohair, fullerene, carbon nanocone, carbon nanohorn, carbon nanorod, activated carbon, graphite, artificial graphite, graphene, graphite, and graphene nanoplatelets. And an organoboron compound, wherein the carbon structure and the organoboron compound are connected in a π-π bond, a process for producing the silylation catalyst, and a process for producing a silylated compound using the same.

Description

TECHNICAL FIELD The present invention relates to a silylation catalyst, a method for preparing the same, and a method for preparing a silylated compound using the silylation catalyst,

The present invention relates to a silylation catalyst, a method for producing the same, and a method for preparing a silylated compound using the silylation catalyst. More specifically, the present invention relates to a silylation catalyst capable of silylating various functional groups with excellent selectivity and yield, To a process for preparing a silylated compound.

It is already known that hydrosilylation using transition metal catalysts is very convenient and efficient in reducing conversion of various unsaturated functionalities such as carbonyls, imines and olefins.

The hydrosilylation using a catalyst can be carried out under convenient and mild conditions and can be used with various hydrosilanes due to its high reactivity range and product selectivity, and the silicon matrix of the hydrosilylated product is very useful as a functional group And can be used in a variety of ways, and has distinctive advantages distinct from conventional hydrogenation methods.

Substantially, hydrosilylation is one of the largest application industries in the field of homogeneous catalysts in the chemical industry, and is used extensively in a wide range of chemical applications, from organic synthesis, pharmaceutical chemistry and materials science.

However, effective catalysts related to homogeneous hydrosilylation depend mainly on noble metal compounds with Pt, Pd, Ru and Rh. The main disadvantage of these catalysts is that they can not be reused after the hydrosilylation catalytic reduction process, while using expensive noble metal compounds.

Therefore, there is a continuing need for the development of a hydrosilylation catalyst which can be effectively used, recovered and reused without using expensive noble metal compounds.

Although a number of reports on supported hydrosilylation catalysts are known in particular, such heterogeneous catalysts have the disadvantage that the use of noble metal compounds for immobilization, multistage pre-functionalization of molecular pre-catalysts, and that the immobilized molecules are easily leached from the catalyst during the catalysis and / It is disadvantageous in that it is disadvantageous in that it is disassembled or can not be recycled.

On the other hand, tris (pentafluorophenyl) borane [B (C ₆ F ₅ ) ₃ ] and related Lewis acid analogs have effective catalytic performance in reducing silylation of alkenes, carbonyls, imines, ethers and alcohols.

However, B (C ₆ F ₅ ) ₃ -catalyzed hydrosilylation often exhibits low functional-group tolerance when small volume silanes are used, so that only the reduction products are all produced. For example, a ketone and an ester are reacted with an excess of hydrosilane, such as PhSiH ₃ , Et ₂ SiH ₂ , under B (C ₆ F ₅ ) ₃ catalyst to produce a mixture of the corresponding alkane and siloxane as the main product. This low functionality tolerance in the reduction reaction is due to the low selectivity of the compound containing the multifunctional group and such catalysts can only be used for very limited applications.

Therefore, it is necessary to study an efficient and highly efficient catalyst for reducing (hydro) silylation.

Chem. Commun., 2016, 52, 10478--10481

The present inventors have made efforts to solve the above-mentioned problems, and have focused on the π-stacking interaction between the carbon material and the organic molecule, and have found that a silylation catalyst produced by π-π bonding of a carbon material and a boron compound has high chemical selectivity The present invention has been completed.

Accordingly, the present invention provides a process for producing a carbon nanotube, a carbon nanofiber, a carbon nanofiber, a fullerene, a carbon nanocone, a carbon nanohorn, a carbon nanorod, an activated carbon, a graphite, an artificial graphite, graphene nanoplatelets), and / or < RTI ID = 0.0 >

An organic boron compound,

Wherein the carbon structure and the organoboron compound are connected in a π-π bond, and a method for producing the silylation catalyst.

The present invention also provides a process for preparing a silylated compound using the silylation catalyst of the present invention.

The present invention provides a silylation catalyst which is reusable and has excellent chemical selectivity. The silylation catalyst of the present invention can be used as a catalyst for carbonization of carbon nanotubes, carbon nanofibers, carbon nanohair, fullerene, carbon nanocone, carbon nanohorn, carbon Carbon structures selected from the group consisting of nano-rods, activated carbon, graphite, artificial graphite, graphene, graphite, and graphene nanoplatelets;

An organic boron compound,

The carbon structure and the organic boron compound are connected by? -N bonds.

The present invention also provides a process for preparing a silylation catalyst according to the present invention, wherein the silylation catalyst of the present invention comprises a carbon nanotube, a carbon nanofiber, a carbon nanofiber, a fullerene, a carbon nanocone, A mixture of a carbon structure and an organic boron compound selected from the group consisting of activated carbon, graphite, artificial graphite, graphene, graphite, and graphene nanoplatelets;

Filtering the mixed solution, and washing and drying the obtained crude product to prepare a silylation catalyst.

The present invention also provides a process for preparing a silylated compound using the silylation catalyst of the present invention, wherein the silylated compound of the present invention is prepared in the presence of the silylation catalyst of the present invention

Reacting a silyl compound with a compound having one or two or more functional groups selected from a carboxylic acid group, an aldehyde group and a ketone group, a hydroxyl group and an epoxide group to prepare a silylated compound.

The silylation catalyst of the present invention can be used as a silylation catalyst in the presence of carbon nanotubes, carbon nanofibers, carbon nanohair, fullerene, carbon nanocone, carbon nanohorn, carbon nanorod, activated carbon, graphite, artificial graphite, It is possible to obtain a silylated product in a high yield under mild condition by bonding an organic boron compound with a carbon structure having one or two selected from graphene nanoplatelets as a π-π bond, and recovered and reused many times It is a very efficient catalyst.

In addition, the silylation catalyst of the present invention is excellent in catalytic activity without using an expensive metal and is economical and efficient, and has a high functional group resistance in the reduction reaction. Therefore, the chemical selectivity of a compound containing a multifunctional group is very high, Or can be very useful for synthesis of raw materials.

Further, the silylated compound of the present invention is economical by using the silylation catalyst of the present invention, and is a highly effective method for obtaining a product of high purity at a high yield with excellent selectivity under mild conditions.

The silylated compound of the present invention can be produced by using the silylation catalyst of the present invention which is excellent in chemical selectivity to react only with a specific functional group of a compound having a multifunctional group and has high yield even under mild conditions and can be reused several times It is possible to mass-produce and is very commercially available.

The present invention provides a silylation catalyst which is superior in catalytic activity, reusable, and excellent in chemical selectivity without using an expensive metal. The silylation catalyst of the present invention includes carbon nanotubes, carbon nanofibers, carbon Wherein the carbon structure is one or more selected from nanohair, fullerene, carbon nanocone, carbon nanohorn, carbon nanorod, activated carbon, graphite, artificial graphite, graphene, graphite, and graphene nanoplatelets. And

An organic boron compound,

The carbon structure and the organic boron compound are connected by? -N bonds.

The silylation catalyst according to the present invention is a compound in which a carbon structure and an organic boron compound according to an embodiment of the present invention are specifically bonded by a π-π stacking interaction with a noncovalent bond, and the organoboron compound of the present invention is bonded to the surface With π-π stacking interactions to obtain silylated compounds with high catalytic activity and chemical selectivity and with high yields under mild conditions.

The silylation catalysts of the present invention can be recovered, unlike the boron catalysts for the hydrogenation of a large number of transition metal complexes and unsaturated functional groups fixed on the external CNT surface based on the conventionally developed van der Waals interactions. The activity is not lowered even after the reuse, and it is very economical, and since it has high selectivity, it can be applied to a compound having various functional groups to obtain a desired product in a high yield, which is very efficient.

Preferably, the carbon structure according to an exemplary embodiment of the present invention may include carbon nanotubes, carbon nanofibers, carbon nanofibers, carbon nanocones, carbon nanofibers, carbon nanorods, activated carbon, graphite, artificial graphite, And graphene nanoplatelets, and may be a carbon nanotube, a carbon nanofiber, or a graphene as a preferable combination with an organic boron compound as a catalyst having excellent characteristics.

Preferably, the organic boron compound according to one embodiment of the silylation catalyst of the present invention may be contained in an amount of 0.2 to 20% by weight, and more preferably 2.0 to 15% by weight based on the total weight of the silylation catalyst.

Preferably, the organoboron compound according to one embodiment of the present invention is B (C ₆ F ₅ ) ₃ , PhB (C ₆ F ₃ ) ₂ , HOB (C ₆ F ₅ ) ₂ And Ph ₂ B (C ₆ F ₅ ). In terms of the activity of the catalyst and the selectivity of the product, it is preferred to use one or more of B (C ₆ F ₅ ) ₃ and PhB (C ₆ F ₃ ) ₂ And may be one or more selected.

In terms of excellent catalytic activity, chemical selectivity and reusability, the silylation catalyst according to one embodiment of the present invention may be one in which carbon nanotubes and B (C ₆ F ₅ ) ₃ are bonded by π-π bonds.

 The silylation catalyst according to an embodiment of the present invention may be prepared by silylation, specifically silylation or hydrolysis of a compound having one or two or more functional groups selected from a carboxylic acid group, an aldehyde group, a ketone group, a hydroxyl group and an epoxide group Can be used for silylation.

The present invention also provides a method for producing the silylation catalyst of the present invention, wherein the method for producing the silylation catalyst of the present invention is a method for producing a silylation catalyst, Preparing a mixed solution of a carbon structure and an organic boron compound which is one or both selected from carbon nanorods, activated carbon, graphite, artificial graphite, graphene, graphite, and graphene nanoplatelets; and

Filtering the mixed solution, and washing and drying the obtained crude product to prepare a silylation catalyst.

In the method for preparing a silylation catalyst according to an embodiment of the present invention, the weight ratio of the organic boron compound and the carbon structure may be 1: 1 to 1: 5, and preferably 1: 1.5 to 1: 4.5.

In the method for producing a silylation catalyst according to an embodiment of the present invention, the mixed solution may be prepared by stirring at 10 to 35 ° C for 8 to 24 hours, preferably at 25 to 35 ° C for 12 to 24 hours.

In the method for preparing a silylation catalyst according to an embodiment of the present invention, drying may be performed at 40 to 110 ° C for 10 to 76 hours, preferably at 60 to 80 ° C for 12 to 36 hours.

The present invention also relates to a process for producing a silylated compound by reacting a silyl compound with a compound having at least one functional group selected from a carboxylic acid group, an aldehyde group, a ketone group, a hydroxyl group and an epoxide group in the presence of the silylation catalyst of the present invention ≪ / RTI > to produce a silylated compound.

The silylation catalyst according to an embodiment of the present invention may be used in an amount of 0.2 to 0.5 mol per mol of a compound having any one or two or more functional groups selected from a carboxylic acid group, an aldehyde group, a ketone group, a hydroxyl group and an epoxide group %, Preferably 0.3 mol% to 0.4 mol%.

Specifically, the silylation catalyst of the present invention is used in an amount of about 1 mg to 40 mg per mol of the compound having any one or two or more functional groups selected from the carboxylic acid group, aldehyde group, ketone group, hydroxyl group and epoxide group described in the present invention And may be used in a preferred amount of 5 mg to 10 mg.

The molar amount described in the present invention represents the molar amount used relative to 100 moles of the reference compound. For example, the description that the silylation catalyst is used in an amount of 0.2 mol% is based on a carboxylic acid group, an aldehyde group, a ketone group, Means that the silylation catalyst is used in an amount of 0.2 moles per 100 moles of the compound having any one or two or more functional groups selected from the group consisting of

The silyl compound according to an embodiment of the present invention may be used in an amount of 1 to 10 moles per mole of a compound having any one or two or more functional groups selected from a carboxylic acid group, an aldehyde group, a ketone group, a hydroxyl group and an epoxide group And preferably 2 to 4 moles.

The reaction according to one embodiment of the process for the preparation of the silylated compounds of the present invention can be carried out at 15 to 35 ° C for 20 minutes to 15 hours, preferably at 20 to 25 ° C for 10 minutes to 12 hours, , Or may be carried out in one or more solvents selected from methanol, toluene, chloroform, chlorobenzene and hexane, preferably in a mixed solvent of one or more selected from chloroform, toluene and hexane .

The silyl compound according to one embodiment of the method for producing the silylated compound of the present invention can be represented by the following formula (1).

[Chemical Formula 1]

(R ¹ ) (R ² ) (R ³ ) SiH

Wherein R ¹ to R ³ are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or -OSiH (R ⁴ ) (R ⁵ ) And R ⁴ or R ⁵ independently from each other are hydrogen, (C 1 -C 20) alkyl or (C 6 -C 20) aryl.

Preferably, in Formula 1, R ¹ to R ⁵ independently of each other may be hydrogen, methyl, ethyl, or phenyl.

Specifically, the silylated compound of the present invention can be prepared by reacting the silyl compound of formula (1) with a compound of formula (3) in the presence of a silylation catalyst of the present invention to prepare a compound of formula .

(2)

(3)

(In the above formulas 2 and 3,

A is (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl

D is hydrogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 20) alkyl; A is an alkyl, aryl, arylalkyl or cycloalkyl of A, The arylalkyl may be further substituted with any one or more selected from halogen, nitro, (C1-C20) alkyl, (C1-C20) alkoxy and halo (C1-

In the general formulas (2) to (3) according to an embodiment of the present invention, when D is an aldehyde having hydrogen, A is substituted with (C1-C20) alkyl or (C6-C20) aryl (C1-C20) alkyl.

In the above formulas 2 to 3 according to an embodiment of the present invention, when D is a non-hydrogen ketone, A may be (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 6 -C 20) Alkyl, cycloalkyl or aryl may be further substituted with at least one of halogen, nitro, (C1-C20) alkyl, (C1-C20) alkoxy and halo (C1- Wherein A is a ketone other than hydrogen when D is a non-hydrogen, the substituent is selected from the group consisting of halogen, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy and halo Phenyl, benzyl, cyclopentyl, cyclohexyl, propyl, butyl or phenethyl.

More specifically, the process for preparing a silylated compound of the present invention comprises reacting a silyl compound of the formula (1) with a compound of the following formula (5) in the presence of a silylation catalyst of the present invention to prepare a compound of the formula May be a method for preparing the compound.

[Chemical Formula 4]

[Chemical Formula 5]

(In the formulas (4) and (5)

R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,

R is halogen, nitro, (C1-C20) alkyl, (C1-C20) alkoxy or halo (C1-C20) alkyl, n is 0 or an integer from 1 to 5,

R ¹¹ to R ¹² independently from each other are hydrogen or (C 1 -C 20) alkyl,

R ¹³ is hydrogen, (C1-C20) alkyl, (C6-C20) aryl or (C6-C20) aryl (C1-C20) alkyl, the R ¹³ alkyl, aryl or aryl alkyl is halogen, nitro, (C1- (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy and halo (C 1 -C 20) alkyl,

p is 0 or an integer of 1 to 5,

q is an integer of 1 to 6, and p + q? 6.

Preferably, the silylation catalyst of the present invention may be one in which carbon nanotubes and B (C ₆ F ₅ ) ₃ are connected in a π-π bond. In the above formulas 4 to 5, when R ¹³ is hydrogen, R is (C 1 -C 20 ) Alkyl, and n may be 0 or an integer of 1 to 5.

Preferably, the silylated compound of the present invention is prepared by reacting the silyl compound of formula 1 with a compound of formula 7 in the presence of a silylation catalyst to produce a compound of formula 6 May be a manufacturing method.

[Chemical Formula 6]

(7)

(In the formulas (6) and (7)

R ¹ to R ³ are, independently of each other, a (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ are each Independently, hydrogen, (C1-C20) alkyl or (C6-C20)

R is halogen, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or halo (C 1 -C 20) alkyl, s is an integer from 0 to 5,

p is 0 or an integer from 1 to 9, depending on s.

P is 0 or an integer of 1 to 4, and when s is 1, p is 0 or an integer of 1 to 5 P may be 0 or an integer from 1 to 6 when s is 2, and p may vary depending on s.

The method for preparing a silylated compound according to an embodiment of the present invention includes the step of reacting the silyl compound of Formula 1 and the compound of Formula 9 in the presence of a silylation catalyst of the present invention to prepare a compound of Formula 8 To obtain a compound of formula (8).

 [Chemical Formula 8]

[Chemical Formula 9]

(In the above formulas 8 and 9,

R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,

R is selected from the group consisting of halogen, nitro, (C1-C20) alkyl, (C1-C20) alkoxy or halo

R ¹¹ to R ¹² independently from each other are hydrogen or (C 1 -C 20) alkyl,

p is 0 or an integer of 1 to 5).

The method for preparing a silylated compound according to an embodiment of the present invention includes the step of reacting a silyl compound of the formula (1) with a compound of the following formula (11) in the presence of a silylation catalyst of the present invention to prepare a compound of the formula To form a silylated compound represented by the following general formula (10).

[Chemical formula 10]

(11)

 (In the above formulas 10 to 11,

R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,

R ⁷ is (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) arylalkyl or (C 3 -C 20)

The alkyl, aryl, arylalkyl or cycloalkyl of R ⁷ may be further substituted with any one or more selected from halogen, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy and halo (C 1 -C 20) .)

The method for preparing a silylated compound according to an embodiment of the present invention includes the step of reacting the silyl compound of the formula (1) with a compound of the following formula (13) in the presence of the silylation catalyst of the present invention to prepare a compound of the formula May be a process for producing a silylated compound represented by the following formula (12).

[Chemical Formula 12]

[Chemical Formula 13]

(In the above formulas 12 to 13,

R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,

R < ⁸ > is (C1-C20) alkyl.

The method for preparing a silylated compound according to an embodiment of the present invention includes the steps of reacting the silyl compound of the formula (1) with a compound of the following formula (15) in the presence of a silylation catalyst of the present invention to prepare a compound of the formula May be a process for producing a silylated compound represented by the following general formula (14).

[Chemical Formula 14]

[Chemical Formula 15]

(In the above formulas 14 and 15,

R ¹ to R ³ are, independently of each other, a (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ are each Independently, hydrogen, (C1-C20) alkyl or (C6-C20)

R ¹¹ to R ¹² independently of one another are (C 1 -C 20) alkyl.

The method for preparing a silylated compound according to an embodiment of the present invention includes the step of reacting the silyl compound of the formula (1) with a compound of the following formula (17) in the presence of a silylation catalyst of the present invention to prepare a compound of the formula May be a process for producing a silylated compound represented by the following formula (16).

[Chemical Formula 16]

[Chemical Formula 17]

(In the above formulas 16 and 17,

R ¹ to R ³ are, independently of each other, a (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ are each Independently, hydrogen, (C1-C20) alkyl or (C6-C20)

R < ¹¹ > is (C1-C20) alkyl.

The silylation catalyst of the present invention can produce silylated compounds with high selectivity and high yields of compounds having various functional groups under mild reaction conditions.

Further, the silylation catalyst of the present invention has high selectivity and does not react with the ester group, so that a silylated product of an ester group is not produced, and only a silylated product of an aldehyde, a ketone, an alcohol and a carboxyl group can be obtained.

In addition, the silylation catalyst of the present invention can be produced as a main product by reacting with a silane compound to deoxidize it to produce a silylated compound having high selectivity, which is not a mixture of an alkane and a siloxane. Can be easily introduced.

The silylation described in the present invention means a reaction in which a silyl group is introduced into a functional group, which means a wide range including reducing hydroxyl silylation and hydrosilylation.

The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both straight-chain or branched forms and include 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 Lt; / RTI > to 7 carbon atoms.

The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

The halogen-substituted alkyl or haloalkyl described in this invention means that at least one of the hydrogens present on the alkyl is substituted with a halogen.

&Quot; Cycloalkyl ", as used herein, refers to a non-aromatic monocyclic or multicyclic ring system having from 3 to 20 carbon atoms, including, but not limited to cyclopropyl, cyclobutyl , Cyclopentyl, and cyclohexyl. Examples of polycyclic cycloalkyl groups include perhydronaphthyl, perhydroindenyl, and the like; Branched polycyclic cycloalkyl groups include adamantyl and norbornyl and the like.

Refers to a group or moiety having one or more substituents attached to the structural or structural skeleton of the moiety or moiety and includes, but is not limited to, a hydroxy group, a halogen group, a carboxyl group, a cyano group, (= O), thio (= S), trifluoromethyl group, alkyl group, haloalkoxy group, alkenyl group, alkynyl group, aryl group, arylalkyl group, cycloalkyl group, cycloalkylalkyl group, cycloalkenyl group, (C1-C4) alkylamino group, an alkylamino group, a dialkylamino group, a heteroaryl group, a heterocyclylalkyl group, a heteroarylalkyl group and a heterocycloalkyl group, (C1-C20) alkyl, (C1-C20) alkoxy and halo (C1-C20) alkyl.

Hereinafter, the structure of the present invention will be described in more detail with reference to examples. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

[Example 1] Production of silylation catalyst B_MWCNT

To the three 20 mL vials into a chloroform 5.0 mL of B (C ₆ F _{5) 3} dissolved in 30, 60, 120 mg each, respectively, where the multi-walled carbon nanotube (MWCNT, 200 mg, Nanocyl ^TM, NC7000) on And the mixture was stirred at 25 DEG C for 18 hours. Thereafter, the reaction mixture was filtered, washed with 20 mL of chloroform, and dried at 40 to 100 ^° C. under reduced pressure (<0.1 mmHg) to prepare a silylation catalyst (B_MWCNT) of the present invention. This was later used as a silylation catalyst.

[Example 2] Production of silylation catalyst B_SWCNT

B_SWCNT was prepared in the same manner as in Example 1 except that single-walled carbon nanotubes (SWeNT ^® , CG300, Aldrich) were used instead of MWCNT in Example 1.

[Example 3] Production of silylation catalyst B_CNF

B_CNF was prepared in the same manner as in Example 1, except that carbon nanofibers (CNF, PR-25-XT-HHT, diameter 130 nm, Aldrich) were used instead of MWCNT in Example 1.

[Example 4] Production of silylation catalyst B_AC

A silylation catalyst B_AC was prepared in the same manner as in Example 1, except that activated carbon (AC, DARCO ^® , 20-40 mesh, Aldrich) was used instead of MWCNT in Example 1.

[Examples 5 to 14 and Comparative Examples 1 to 4] Method for producing a silylated compound using a silylation catalyst

4-methylacetophenone (0.50 mmol) and the silyl compound (1-2 mmol) shown in the following Table 1 were added to a 5 mL vial, and a solvent in which the silylation catalyst (1 to 10 mg) described in the following Table 1 was dissolved was added to 25 from to 55 ^o and stirred for 0.5 to 12 hours. The reaction mixture was then filtered and the filtrate was analyzed by ¹ H and ¹³ C { ¹ H} NMR. The reaction conditions and results are shown in Table 1 below.

catalyst
(mg) menstruum
(mL) [Si] H
(equiv) Reaction temperature
( ^o C) Reaction time
(h) Conversion Rate
(%) ^b 2a
(%) ^b 2aa
(%) ^b Example 5 B_MWCNT
(10) CHCl ₃ (0.5) Me ₂ PhSiH (4) 25 0.5 98 100 0 Example 6 B_MWCNT
(10) CHCl ₃ (0.5) Me ₂ PhSiH (4) 25 12 100 96
(91) ^c 4 Example 7 B_MWCNT
(10) CHCl ₃ (0.5) Et ₃ SiH (4) 25 12 100 100 0 Example 8 B_MWCNT
(10) CHCl ₃ (0.5) Et ₂ SiH ₂ (4) 25 12 100 96 4 Example 9 B_MWCNT
(10) CHCl ₃ (0.5) TMDS (4) 25 12 100 97 3 Example 10 B_MWCNT
(10) toluene (0.5) Me ₂ PhSiH (4) 25 12 100 97 3 Example 11 B_MWCNT
(10) neat Me ₂ PhSiH (4) 25 12 100 100 0 Example 12 B_MWCNT
(2) CHCl ₃ (0.5) Me ₂ PhSiH (2) 25 12 100 97 3 Example 13 B_SWCNT
(10) CHCl ₃ (0.5) Me ₂ PhSiH (4) 25 12 100 95 5 Example 14 B_CNF
(10) CHCl ₃ (0.5) Me ₂ PhSiH (4) 25 12 98 99 One Comparative Example 1 B (C ₆ F _{5) 3}
(One) CHCl ₃ (0.5) Me ₂ PhSiH (4) 25 12 100 0 100 Comparative Example 2 ^d _{B (C 6 F 5) 3} (1) + MWCNT
(10) CHCl ₃ (0.5) Me ₂ PhSiH (4) 25 12 100 0 100 Comparative Example 3 MWCNT
(10) CHCl ₃ (0.5) Me ₂ PhSiH (4) 25 12 0

b is the yield calculated by ¹ H NMR, c is the yield obtained by separating (), d is the yield of B (C ₆ F ₅ ) ₃ (1 mg) and CNT (10 mg) in CHCl ₃ After mixing and stirring for 3 hours, Ph Me ₂ SiH and 1a were added.

As shown in Table 1, when the organoboron compound or CNT was used alone as the catalyst, or when the organoboron compound and CNT were simply mixed, the deacidified 2aa compound not the 2a compound was obtained or the reaction did not proceed.

Therefore, it can be seen that the silylated catalyst of the present invention can produce silylated compounds with excellent selectivity, conversion and yield.

[Examples 15 to 18] A method for producing a silylated compound using the silylation catalyst of the present invention

The above-described use of the catalyst described in Table 2 in Example 5, and _{B (C 6 F 5) 3} (10 mg), CHCl 3 (0.5 mL), 1a (0.5 mmol) and _{PhMe 2 SiH (2.0 mmol) 25} o C for 12 hours to prepare a silylated compound. The reaction conditions and results are shown in Table 2 below.

2a: ^{1 H NMR (600 MHz, CDCl} 3) δ 7.54 - 7.50 (m, 2H), 7.26 (m, 3H, overlapped with dimethylphenylsilane), 7.15 (d, J = 7.8 Hz, 2H), 7.02 (d, J = 7.8 Hz, 2H), 4.78 (q, J = 6.3 Hz, 1H), 2.24 (s, 3H), 1.37 (d, J = 6.5 Hz, 3H), 0.30 (s, 3H), 0.25 ^{13 C NMR (150 MHz, CDCl} 3) δ 143.3, [138.2 - 127.7] (6C of -SiMe 2 Ph), 136.2, 128.8 (2C), 125.3 (2C), 71.0, 26.9, 21.0, [-0.8 - - _{1.3] (2C of -Si Me 2} Ph).

catalyst Adsorbed borane (wt%) ^c Normalized Adsorption of Borane (wt% g / m ² ) Conv. (%) ^d 2a (%): 2aa (%) ^d
Example 15 B_SWCNT 15.5 0.020 100 90:10 Example 16 B_MWCNT 8 0.032 100 96: 4 Example 17 B_CNF 0.5 0.021 98 99: 1 Example 18 B_AC 14.4 0.010 100 95: 5

c is the value measured by ICP-OES, and d is the yield calculated by ¹ H NMR.

[Example 19] Preparation of {1- (4-Methoxyphenyl) ethoxy} dimethyl (phenyl) silane

12 hours in 5mL vials 4-methoxy acetophenone (0.50 mmol) and a silyl compound, was added to PhSiMe ₂ H (2mmol) was added to CDCl ₃ (0.50 mL) dissolved B_MWCNT (10 mg) here 55 ^o C &Lt; / RTI &gt; The reaction mixture was then filtered and the filtrate was analyzed by ¹ H and ¹³ C { ¹ H} NMR to give the title compound (Crude yield = 84%).

^{1 H NMR (600 MHz, CDCl} 3) δ 7.51 (m, 2H), δ 7.30 - 7.24 (m, 3H, overlapped with dimethylphenylsilane), 7.17 (d, J = 8.5 Hz, 2H), 6.76 (d, J = 8.6 Hz, 2H), 4.77 ( q, J = 6.3 Hz, 1H), 3.63 (s, 3H), 1.37 (d, J = 6.4 Hz, 3H), 0.31 (s, 3H), 0.25 (s, 3H) ; ^{13 C NMR (150 MHz, CDCl} 3) δ 158.6, [138.4 - 127.7] (6C of -SiMe 2 Ph), 132.9, 126.5 (2C), 113.5 (2C), 70.7, 54.9, 26.8, [-0.8 - - _{1.3] (2C of -Si Me 2} Ph).

[Example 20] Preparation of dimethyl (phenyl) (1-phenylethoxy) silane

 (Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.51 (m, 2H), 7.30 - 7.23 (m, 5H, overlapped with dimethylphenylsilane), 7.20 (t, J = 7.6 Hz, 2H), 7.12 (t, J = 7.3 Hz, 1H), 4.80 (q, J = 6.4 Hz, 1H), 1.38 (d, J = 6.4 Hz, 3H), 0.30 (s, 3H), 0.25 ^{13 C NMR (150 MHz, CDCl} 3) δ 146.3, [138.1 - 127.8] (6C of -SiMe 2 Ph), 128.1 (2C), 126.9, 125.4 (2C), 71.1, 26.9, [-0.8 - -1.3] _{(2C of -Si Me 2 Ph)} .

[Example 21] Preparation of {1- (4-Chlorophenyl) ethoxy} dimethyl (phenyl) silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.52 - 7.45 (m, 2H, overlapped with dimethylphenylsilane), 7.27 (m, 3H, overlapped with dimethylphenylsilane), 7.17 (d, J = 8.5 Hz, 2H), 7.14 (d , J = 8.6 Hz, 2H) , 4.75 (q, J = 6.4 Hz, 1H), 1.33 (d, J = 6.4 Hz, 3H), 0.31 (s, 3H), 0.25 (s, 3H); ^{13 C NMR (150 MHz, CDCl} 3) δ 144.8, [137.8 - 127.8] (6C of -SiMe 2 Ph), 132.5, 128.3 (2C), 126.8 (2C), 70.4, 26.8, [-1.0 - -1.4] _{(2C of -Si Me 2 Ph)} .

[Example 22] Preparation of dimethyl (phenyl) [1- {4- (trifluoromethyl) phenyl} ethoxy] silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.53 - 7.47 (m, 2H, overlapped with dimethylphenylsilane), 7.46 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.5 Hz, 2H), 7.26 ( m, 3H, overlapped with dimethylphenylsilane), 4.81 (q, J = 6.4 Hz, 1H), 1.34 (d, J = 6.4 Hz, 3H), 0.32 (s, 3H), 0.27 ^{13 C NMR (150 MHz, CDCl} 3) δ 150.3, [137.6 - 127.9] (6C of -SiMe 2 Ph), 129.21 (q, J = 32.2 Hz), 125.7 (2C), 125.1 (2C, q, J = 3.9 Hz), 124.4 (q, J = 271.8 Hz), 70.6, 26.7, [-1.1 - -1.4] (2C of -Si Me 2 Ph).

[Example 23] Dimethyl {1- (4-nitrophenyl) ethoxy} (phenyl) silane

(Crude yield = 52%)

(Crude yield = 52%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.90 (d, J = 8.9 Hz, 2H), 7.53 - 7.46 (m, 2H, overlapped with dimethylphenylsilane), 7.34 (d, J = 8.6 Hz, 2H), 7.32 - (D, J = 6.4 Hz, 3H), 0.36 (s, 3H), 0.31 (s, 3H); 7.25 (m, 3H, overlapped with dimethylphenylsilane), 4.85 (q, J = 6.4 Hz, 1H). ^{13 C NMR (150 MHz, CDCl} 3) δ 153.5, 146.8, [139.6 - 127.8] (6C of -SiMe 2 Ph), 125.9 (2C), 123.5 (2C), 70.1, 26.5, [-1.3 - -1.5] _{(2C of -Si Me 2 Ph)} .

[Example 24] Preparation of diethyl {(1-phenylpropan-2-yl) oxy} silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.31 (t, J = 7.5 Hz, 2H), 7.24 (d, J = 7.6 Hz, 3H), 4.48 - 4.34 (m, 1H), 4.08 (p, J = 6.0 Hz, 1H), 2.86 ( dd, J = 13.4, 7.2 Hz, 1H), 2.75 (dd, J = 13.5, 5.9 Hz, 1H), 1.26 (d, J = 6.2 Hz, 3H), 1.02 (t, J = 7.9 Hz, 3H), 0.94 (t, J = 8.1 Hz, 3H), 0.67 (q, J = 7.5 Hz, 2H), 0.57 (q, J = 7.6 Hz, 2H); ¹³ C NMR (150 MHz, _{CDCl 3) δ 139.2, 129.6 (} 2C), 128.1 (2C), 126.1, 71.8, 46.1, 23.1, [6.6 - 5.3] (4C of -Si Et 2 H).

[Example 25] Preparation of (Hexan-2-yloxy) dimethyl (phenyl) silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.58 (t, J = 4.5 Hz, 2H), 7.38 - 7.23 (m, 3H, overlapped with Me 2 PhSiH), 3.77 (m, 1H), 1.52 - 1.13 (m , 6H), 1.12-1.03 (m, 3H), 0.92-0.77 (m, 3H), 0.37 (s, 3H, overlapped with dimethylphenylsilane), 0.32 (s, 3H, overlapped with dimethylphenylsilane); ^{13 C NMR (150 MHz, CDCl} 3) δ [138.6 - 127.7] (6C of -SiMe 2 Ph), 69.0, 39.3, 28.0, 23.7, 22.7, 14.1, [-1.0 - -1.1] (2C of -Si Me ₂ Ph).

[Example 26] Production of 1- (Benzhydryloxy) -1,1,3,3-tetramethyldisiloxane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.48 (d, J = 7.3 Hz, 4H), 7.38 (t, J = 7.7 Hz, 4H), 7.30 (t, J = 7.4 Hz, 2H), 6.03 (s , 1H), 4.80 (hept, J = 2.8 Hz, 1H), 0.21-0.18 (m, 12H); ^{13 C NMR (150 MHz, CDCl} 3) δ 144.7 (2C), 128.2 (4C), 127.1 (2C), 126.6 (4C), 76.2, [0.5 - -0.6] (4C of -Si Me 2 OSi Me 2 H ).

[Example 27] Preparation of 1- (1,2-diphenylethoxy) -1,1,3,3-tetramethyldisiloxane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.41 - 7.35 (m, 4H), 7.34 - 7.29 (m, 3H), 7.28 - 7.24 (m, 1H), 7.24 - 7.21 (m, 2H), 5.03 (dd J = 8.1, 5.0 Hz, 1H), 4.69 (m, 1H), 3.10 (dd, J = 13.4, 8.0 Hz, 1H), 3.03 (dd, J = 13.4, 4.9 Hz, 1H) (m, 6H), -0.01 (s, 3H), -0.06 (s, 3H); ^{13 C NMR (150 MHz, CDCl} 3) δ 144.6, 138.8, 129.9 (2C), 128.0 (2C), 128.0 (2C), 127.1, 126.2, 126.0 (2C), 76.1, 47.5, [-0.8 - -1.2] _{(4C of -Si Me 2 OSi Me} 2 H).

[Example 28] Preparation of triethyl [{(1R, 2S) -2-methylcyclopentyl} oxy] silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 4.12 - 4.02 (m, 1H), 1.86 - 1.72 (m, 3H), 1.71 - 1.59 (m, 2H), 1.52 (m, 1H), 1.40 (m, 1H ), 1.01 (m, 12H, overlapped with triethylsilane), 0.62 (m, 6H, overlapped with triethylsilane); ¹³ C NMR (150 MHz, CDCl ₃ )? 76.2, 40.1, 35.2, 30.9, 22.0, 14.1, [6.9-5.1] (6C of -Si Et ₃ ).

[Example 29] Preparation of [{(1 r , 4 r ) -4- ( tert- Butyl) cyclohexyl} oxy] triethylsilane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 4.01 (s, 1H), 1.76 (d, J = 12.8 Hz, 2H), 1.49 (m, 4H), 1.39 (t, J = 13.3 Hz, 2H), 1.00 (m, 10H, overlapped with triethylsilane), 0.88 (s, 9H), 0.62 (q, J = 8.9 Hz, 6H; overlapped with triethylsilane); ^{13 C NMR (150 MHz, CDCl} 3) δ 66.2, 48.3, 34.5 (2C), 32.6, 27.5 (3C), 21.1 (2C), [6.9 - 5.1] (6C of -Si Et 3).

[Example 30] Preparation of triethyl [{(3S) -3-methylcyclohexyl} oxy] silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 4.15 - 4.01 (m, 1H), 2.03 - 1.87 (m, 1H), 1.86 - 1.57 (m, 4H), 1.54 - 1.35 (m, 2H), 1.22 - 1.11 (m, 2H), 1.03 (m, 9H, overlapped with triethylsilane), 0.90 (d, J = 6.8 Hz, 3H), 0.65 (m, 6H, overlapped with triethylsilane); ^{13 C NMR (150 MHz, CDCl} 3) δ 67.2, 42.8, 34.7, 34.0, 26.6, 22.2, 20.3, [6.9 - 5.1] (6C of -Si Et 3).

[Example 31] Preparation of diethyl [{(1S, 2S, 5R) -2-isopropyl-5-methylcyclohexyl} oxy]

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 4.49 (m, 1H), 4.13 (s, 1H), 1.88 - 1.75 (m, 2H), 1.72 (m, 1H), 1.64 - 1.54 (m, 2H), (M, 4H, overlapped with diethylsilane), 1.01 (m, 8H), 0.95-0.85 (m, 9H), 1.41 (qd, J = ; ¹³ C NMR (150 MHz, CDCl ₃ )? 70.4, 49.2, 42.8, 35.5, 28.9, 25.8, 24.2, 22.4, 21.0, 20.9, [7.0-5.6] (4C of -Si Et ₂ H).

[Example 32] Preparation of dimethyl {(4-methylbenzyl) oxy} (phenyl) silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.59 - 7.53 (m, 2H), 7.34 - 7.21 (m, 3H, overlapped with dimethylphenylsilane), 7.14 (d, J = 7.6 Hz, 2H), 7.03 (d, J = 8.3 Hz, 2H), 4.60 (s, 2H), 2.23 (s, 3H), 0.35 (s, 6H); ^{13 C NMR (150 MHz, CDCl} 3) δ 137.8, [137.7 - 127.8] (6C of -SiMe 2 Ph), 136.5, 128.9 (2C), 126.6 (2C), 64.9, 21.0, -1.6 (2C of -Si Me ₂ Ph).

[Example 33] Preparation of (Benzyloxy) diethylsilane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.39 (m, 4H), 7.31 (d, J = 7.1 Hz, 1H), 4.83 (s, 2H), 4.61 (s, 1H), 1.17 - 1.02 (m, 6H, overlapped with diethylsilane), 0.87-0.66 (m, 4H, overlapped with diethylsilane); ^{13 C NMR (150 MHz, CDCl} 3) δ 140.7, 128.2 (2C), 127.2, 126.5 (2C), 66.6, [7.0 - 5.3] (4C of -Si Et 2 H).

[Example 34] Preparation of dimethyl ( tert- pentyloxy) (phenyl) silane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.59 - 7.55 (m, 2H), 7.27 (m, 3H, overlapped with dimethylphenylsilane), 1.45 (q, J = 7.5 Hz, 2H), 1.15 (s, 6H), 0.87 (t, J = 7.5 Hz, 3H), 0.35 (s, 6H); ^{13 C NMR (150 MHz, CDCl} 3) δ [140.6 - 127.6] (6C of -SiMe 2 Ph), 74.8, 37.4, 29.4 (2C), 8.8, 1.5 (2C of -Si Me 2 Ph).

[Example 35] Preparation of 1,1,3,3-Tetramethyl-1-phenethoxydisiloxane

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.32 (t, J = 7.4 Hz, 2H), 7.26 (m, 3H), 4.86 - 4.74 (m, 1H, overlapped with tetramethyldisiloxane), 3.93 (t, J = 7.2 Hz, 2H), 2.92 (t, J = 7.2 Hz, 2H), 0.19-0.08 (m, 12H, overlapped with tetramethyldisiloxane); ^{13 C NMR (150 MHz, CDCl} 3) δ 139.0, 129.1 (2C), 128.3 (2C), 126.2, 63.5, 39.5, [0.8 - -1.3] (4C of -Si Me 2 OSi Me 2 H).

Example 36 Preparation of 6-Benzyl-8 - {(dimethylsilyl) oxy} -2,4,4,8-tetramethyl-3,5,7-trioxa-2,4,8-trisilanonane

(Crude yield = 88%)

(Crude yield = 88%)

¹ H NMR (600 MHz, CDCl ₃ )? 7.35-7.17 (m, 5H, overlapped with 1,1,3,3-tetramethyl-1-phenethoxydisiloxane), 5.66 (t, J = 4.9 Hz, 1H), 4.78 m, 2 H, overlapped with tetramethyldisiloxane), 2.98 (d, J = 4.9 Hz, 2H), 0.32-0.04 (m, 24H, overlapped with tetramethyldisiloxane); ^{13 C NMR (150 MHz, CDCl} 3) δ 136.9, 130.0 (2C), 128.0 (2C), 126.3, 94.4, 46.5, [0.4 - -0.7] (8C of -Si Me 2 OSi Me 2 H).

[Example 37] Preparation of 2,6-Dimethyl-4-phenethyl-2,6-diphenyl-3,5-dioxa-2,6-disilaheptane

(Crude yield = 98%)

(Crude yield = 98%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.57 - 7.44 (m, 4H, overlapped with dimethylphenylsilane), 7.31 - 7.22 (m, 6H, overlapped with dimethylphenylsilane), 7.13 (t, J = 7.5 Hz, 2H), 7.06 (t, J = 7.4 Hz, 1H), 6.98-6.93 (m, 2H), 5.14 (t, J = 4.8 Hz, 1H), 2.65-2.55 0.29 (m, 12H, overlapped with dimethylphenylsilane); ^{13 C NMR (150 MHz, CDCl} 3) δ 141.8, [137.7 - 127.7] (12C of -SiMe 2 Ph), 128.3 (2C), 128.2 (2C), 125.6, 92.9, 41.6, 30.3, [-0.6 - - _{1.1] (4C of -Si Me 2} Ph).

[Example 38] Preparation of phenylsilyl acetate

(Crude yield = 100%)

(Crude yield = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 7.95 - 7.91 (m, 2H), 7.66 - 7.62 (m, 1H), 7.61 - 7.55 (m, 2H, overlapped with phenylsilane), 5.35 (s, 2H), 2.25 (s, 3 H); ¹³ C NMR (150 MHz, CDCl ₃ )? 171.9, [135.2 - 128.0] (6C of - Si Ph H ₂ ), 21.9.

[Example 39] Hydrosilylation reduction of 2,2-dimethyloxirane

(Conversion = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 4.99 (s, 2H of 2-methylprop-1-ene), 4.78 - 4.74 (m, 1H of 2x and 1H of 2y), 3.42 (d, J = 6.6 Hz, 2H of 2x), 1.77 (m , 1H of 2x), 1.72 (s, 6H of 2-methylprop-1-ene), 1.15 (s, 9H of 2y), 0.90 (d, J = 6.7 Hz, 6H of 2x ), 0.26-0.05 (m, 12H of 2x and 12H of 2y, overlapped with tetramethyldisiloxane); ^{13 C NMR (150 MHz, CDCl} 3) δ 144.0 (1C of 2-methylprop-1-ene), 109.8 (1C of 2-methylprop-1-ene), 74.8 (1C of 2y), 69.0 (1C of 2x) , 31.9, 30.8 (1C of 2x ), 23.2 (2C of 2-methylprop-1-ene), 19.0 (2C of 2x), [0.7 - -1.3] (4C of -Si Me 2 OSi Me 2 H in 2x and 2y).

[Example 40] Hydrosilylation reduction of 2-butyloxirane

(Conversion = 100%)

^{1 H NMR (600 MHz, CDCl} 3) δ 4.75 (m, 1H of 2h and 1H of 2z), 3.90 (m, 1H of 2h), 3.66 (t, J = 6.6 Hz, 2H of 2z), 1.55 (p , J = 6.9 Hz, 2H of 2z), 1.52 - 1.23 (m, 6H of 2h and 6H of 2z), 1.16 (d, J = 6.2 Hz, 3H of 2h), 0.95 - 0.87 (m, 3H of 2h and 3H of 2z), 0.25-0.04 (m, 12H of 2h and 12H of 2z, overlapped with tetramethyldisiloxane) .; ^{13 C NMR (150 MHz, CDCl} 3) δ 68.5 (1C of 2h), 62.4 (1C of 2z), 39.4 (1C of 2h), 32.7 (1C of 2z), 31.8 (1C of 2z), 28.2 (1C of (1C of 2h), 14.8 (1C of 2h), 22.8 (1C of 2h), 22.8 _{] (4C of -Si Me 2 OSi} Me 2 H in 2h and 2z).

[Example 41] Selectivity of silylation catalyst

To the 5 mL vial was added 4-methylacetophenone (0.25 mmol), ethyl 4-methylbenzoate (0.25 mmol) and the silyl compound Me ₂ PhSiH ( ₂ mmol), followed by addition of CDCl ₃ ) ^Was added and stirred at 25 ^° C for 12 hours. The reaction mixture was then filtered and the filtrate was analyzed by ¹ H and ¹³ C { ¹ H} NMR to give the title compound.

[Comparative Example 5]

Compound 2a was prepared in the same manner as in Example 41, except that 0.4 mol% of B (C6F5) 3 and Me ₂ PhSiH (1 equiv) were used in place of B_MWCNT in Example 41.

[Example 42]

Compound 2ab was prepared in the same manner as in Example 41, except that 4-acetylphenylacetate and Me ₂ PhSiH (4 equiv) were used as starting materials in Example 41.

[Example 43]

Compound 2ac was prepared in the same manner as in Example 42, except that 3-formylphenylacetate was used as the starting material in Example 42.

[Example 44]

Compound 2ad was prepared in the same manner as in Example 42, except that 5- (methoxycarbonyl) pentanoic acid was used as the starting material in Example 42.

As can be seen from Examples 41 to 44 and Comparative Example 5, the silylation catalyst of the present invention shows silylation of an aldehyde or a ketone functional group in comparison with an ester group. From this, it can be seen that the chemical selectivity of the silylation catalyst of the present invention It is very high.

[Example 45] Reuse of the silylation catalyst of the present invention

To the 5 mL vial was added 4-methylacetophenone (1.5 mmol) and Me ₂ PhSiH (3.0 mmol, ₂ equiv) as a silyl compound, and CDCl ₃ (1.50 g) obtained by dissolving B_MWCNT and B_AC (30 mg) mL) was added and the mixture was stirred at 25 ^° C for 12 hours. The reaction mixture was then filtered and the filtrate was analyzed by ¹ H and ¹³ C { ¹ H} NMR and the catalyst used in the reaction was recovered. The recovered catalyst was washed with CHCl ₃ (3 mL) or pentane (20 mL) and dried at 25 ^° C under reduced pressure for 6 hours. The recovered catalyst was similarly reused in the hydrosilylation reaction of the compound 1a under the same conditions as above. The reaction was carried out for 12 hours by the hydrosilylation reaction until the conversion of each catalyst was reduced to 40% or less. The results are shown in Table 3 below.

As shown in Table 3, the silylation catalyst of the present invention is recovered after the reaction and reused, so that the catalyst activity is not reduced, so that it can be reused several times, which is very economical.

Claims (24)

One selected from carbon nanotubes, carbon nanofibers, carbon nanohair, fullerene, carbon nanocone, carbon nanohorn, carbon nanorod, activated carbon, graphite, artificial graphite, graphene, graphite, Or two-carbon carbon structure and
An organic boron compound,
Wherein the carbon structure and the organoboron compound are connected in a π-π bond. The method according to claim 1,
Wherein the organic boron compound is contained in an amount of 0.2 to 20% by weight based on the total weight of the silylation catalyst. The method according to claim 1,
The organic boron compound is _{B (C 6 F 5) 3} , HOB (C 6 F 3) 2, PhB (C 6 F 5) 2 and Ph ₂ B Chemistry silyl least one or two selected from (C ₆ F ₅₎ catalyst. The method according to claim 1,
Wherein the silylation catalyst is a silylation catalyst in which carbon nanotubes and B (C ₆ F ₅ ) ₃ are bonded by π-π bonds. The method according to claim 1,
Wherein the silylation catalyst is used for silylation of a compound having any one or two or more functional groups selected from a carboxylic acid group, an aldehyde group, a ketone group, a hydroxyl group and an epoxide group. Carbon nanotubes, carbon nanofibers, carbon nanofibers, fullerenes, carbon nanocones, carbon nanohorns, carbon nanorods, activated carbon, graphite, artificial graphite, graphene, graphite, and graphene nanoplatelets. Preparing a mixed solution of a carbon structure and an organic boron compound in which one or both of them are selected, and
Filtering the mixed solution, and washing and drying the obtained crude product to prepare a silylation catalyst. The method according to claim 6,
Wherein the organoboron compound and the carbon structure are in a weight ratio of 1: 1 to 1: 5. The method according to claim 6,
Wherein the mixed solution is prepared by stirring at 10 to 35 DEG C for 8 to 24 hours. The method according to claim 6,
Wherein the drying is carried out at 40 to 110 DEG C for 10 to 76 hours. A process for the preparation of a silylation catalyst according to any one of claims 1 to 5
Comprising reacting a silyl compound with a compound having at least one functional group selected from a carboxylic acid group, an aldehyde group and a ketone group, a hydroxyl group and an epoxide group to produce a silylated compound Gt; 11. The method of claim 10,
The silylation catalyst is used in an amount of from 0.2 mol% to 0.5 mol% based on 1 mol of the compound having any one or two or more functional groups selected from a carboxylic acid group, an aldehyde group, a ketone group, a hydroxyl group and an epoxide group. &Lt; / RTI &gt; 11. The method of claim 10,
The silyl compound is used in an amount of 1 to 10 moles per 1 mole of a compound having any one or two or more functional groups selected from a carboxylic acid group, an aldehyde group, a ketone group, a hydroxyl group and an epoxide group . 11. The method of claim 10,
Wherein the reaction is carried out at 15 to 35 DEG C for 10 minutes to 12 hours. 14. The method of claim 13,
Wherein the reaction is carried out in the absence of solvent or is carried out in one or more solvents selected from methanol, toluene, chloroform, chlorobenzene and hexane. 11. The method of claim 10,
Wherein the silyl compound is represented by the following formula (1).
[Chemical Formula 1]
(R ¹ ) (R ² ) (R ³ ) SiH
Wherein R ¹ to R ³ are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, (C 6 -C 20) aryl or -OSiH (R ⁴ ) (R ⁵ ) And R ⁴ or R ⁵ independently from each other are hydrogen, (C 1 -C 20) alkyl or (C 6 -C 20) aryl. 16. The method of claim 15,
Wherein R ¹ to R ⁵ are, independently of each other, hydrogen, methyl, ethyl, or phenyl. 11. The method of claim 10,
Wherein the silylated compound of formula (1) is reacted with a compound of formula (3) in the presence of a silylation catalyst to produce a compound of formula (2).
(2)

(3)

(In the above formulas 2 and 3,
A is (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) aryl
D is hydrogen, (C 1 -C 20) alkyl, (C 6 -C 20) aryl or (C 6 -C 20) aryl (C 1 -C 20) alkyl; A is an alkyl, aryl, arylalkyl or cycloalkyl of A, The arylalkyl may be further substituted with any one or more selected from halogen, nitro, (C1-C20) alkyl, (C1-C20) alkoxy and halo (C1- The method of claim 10, wherein
Wherein the silylated compound of formula (1) is reacted with a compound of formula (5) in the presence of a silylation catalyst to produce a compound of formula (4).
[Chemical Formula 4]

[Chemical Formula 5]

(In the formulas (4) and (5)
R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,
R is selected from the group consisting of halogen, nitro, (C1-C20) alkyl, (C1-C20) alkoxy or halo
R ¹¹ to R ¹² independently from each other are hydrogen or (C 1 -C 20) alkyl,
R ¹³ is hydrogen, (C1-C20) alkyl, (C6-C20) aryl or (C6-C20) aryl (C1-C20) alkyl, the R ¹³ alkyl, aryl or aryl alkyl is halogen, nitro, (C1- (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy and halo (C 1 -C 20) alkyl,
p is 0 or an integer of 1 to 5,
q is an integer of 1 to 6, and p + q? 6. The method of claim 10, wherein
Wherein the silylated compound of formula (1) is reacted with a compound of formula (7) in the presence of a silylation catalyst to produce a compound of formula (6).
[Chemical Formula 6]

(7)

(In the formulas (6) and (7)
R ¹ to R ³ are, independently of each other, a (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ are each Independently, hydrogen, (C1-C20) alkyl or (C6-C20)
R is halogen, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy or halo (C 1 -C 20) alkyl, s is an integer from 0 to 5,
p is 0 or an integer from 1 to 9, depending on s. The method of claim 10, wherein
Wherein the silyl compound of formula (1) is reacted with a compound of formula (9) in the presence of a silylation catalyst to produce a compound of formula (8).
[Chemical Formula 8]

[Chemical Formula 9]

(In the above formulas 8 and 9,
R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,
R is selected from the group consisting of halogen, nitro, (C1-C20) alkyl, (C1-C20) alkoxy or halo
R ¹¹ to R ¹² independently from each other are hydrogen or (C 1 -C 20) alkyl,
p is 0 or an integer of 1 to 5). 11. The method of claim 10,
Wherein the silylated compound of formula (1) is reacted with a compound of formula (11) in the presence of a silylation catalyst to produce a compound of formula (10).
[Chemical formula 10]

(11)

(In the above formulas 10 to 11,
R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,
R ⁷ is (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) arylalkyl or (C 3 -C 20)
The alkyl, aryl, arylalkyl or cycloalkyl of R ⁷ may be further substituted with any one or more selected from halogen, nitro, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy and halo (C 1 -C 20) .) The method of claim 10, wherein
Wherein the silyl compound of formula (1) is reacted with a compound of formula (13) in the presence of a silylation catalyst to produce a compound of formula (12).
[Chemical Formula 12]

[Chemical Formula 13]

(In the above formulas 12 to 13,
R ¹ to R ³ are independently from each other, are hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ Are independently of each other hydrogen, (C1-C20) alkyl or (C6-C20) aryl,
R &lt; ⁸ &gt; is (C1-C20) alkyl. The method of claim 10, wherein
Wherein the silyl compound of formula (1) is reacted with a compound of formula (15) in the presence of a silylation catalyst to produce a compound of formula (14).
[Chemical Formula 14]

[Chemical Formula 15]

(In the above formulas 14 and 15,
R ¹ to R ³ are, independently of each other, a (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ are each Independently, hydrogen, (C1-C20) alkyl or (C6-C20)
R ¹¹ to R ¹² independently of one another are (C 1 -C 20) alkyl. The method of claim 10, wherein
The method comprises reacting the silyl compound of formula (1) with a compound of formula (17) in the presence of a silylation catalyst to produce a compound of formula (16).
[Chemical Formula 16]

[Chemical Formula 17]

(In the above formulas 16 and 17,
R ¹ to R ³ are, independently of each other, a (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryl or ^{-OSiH (R 4) (R 5} ), R 4 or R ⁵ are each Independently, hydrogen, (C1-C20) alkyl or (C6-C20)
R &lt; ¹¹ &gt; is (C1-C20) alkyl.