KR101335184B1 - Grubbs supported catalyst and process for producing of it - Google Patents

Abstract

The present invention relates to a Grubbs supported catalyst and a method for manufacturing the Grubbs supported catalyst according to an embodiment of the present invention, in which the carrier of Formula 1 is bound to the vinylidene ligand of the Grubbs catalyst. It features.

≪ Formula 1 >

R1 is a compound group having a structure capable of resonance with a vinyl group,

R2 is C1-C12 alkyl group, phenyl group or benzophenyl group,

Cv is ester group, ether group, amide group and disulfide group, diphenylphosphine amide group, acetal group, ketal group, oxime group, imine group, oxazolidine group, thioester group, thioether group, carbomate group, A compound group comprising one selected from the group consisting of sulfonamide groups, or aromatic amine oxide groups, arylformaldehyde groups, carbomite groups, benzylsulfonamide groups, ester groups, acetal groups or ketal groups, hydrazone groups, A compound group including one selected from the group consisting of a sulfonyl ester group, a dithiolane group, a nitroamide group, a nitrile ester group, a nitroanilide group, an amine group, an ether group, a dioxane group, an amide group, or , Imidazolidine group, thiazolidine group, ester group, sulfonamide group, amide group, thioester group, thioether group Is a compound group containing one selected from

R3 is a resin group based on polystyrene obtained by polymerizing 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB).

Grubbs catalyst, supported catalyst.

Description

Grubbs supported catalyst and process for producing of it

The present invention relates to a Grubbs supported catalyst and a preparation method thereof.

For cyclic olefin polymers (COPs, hereinafter referred to as 'COP'), it is important to secure core raw materials and high-purity monomers, and to secure metal catalysts that can be used in mass production for ring-opening polymerization.

The production method of COP is a catalyst polymerization (ROMP) and a hydrogenation reaction, and then a catalyst removal process to obtain a final COP, a lot of research has been conducted around the world about the metal catalyst mainly used here, Examples include Grubbs catalysts and Schrock catalysts.

However, the removal of the metal catalyst used in the catalytic polymerization (ROMP) and hydrogenation reaction is not easy, it is difficult to obtain a high purity COP.

In addition, in order to overcome the problem that the removal of the catalyst is not easy in the general catalytic polymerization reaction, it is environmentally friendly during the polymerization using the supported catalyst, and research on the supported catalyst for the purpose of recycling (Steven P. Nolan et al., Sustainable Concepts in Olefin Metathesis, Angew. Chem. Int. Ed. 2007, 46, 6786-6801); A study to synthesize high density carriers (Anthony GM Barrett et al., ROMP-Spheres: A Novel High-Loading Polymer Support Using Cross Metathesis between Vinyl Polystyrene and Norbornene Derivatives, Org. Lett. 1999. Vol. 1.No. 7. 1083-1086); Terminal functionalization using click reaction; (Chi-Huey Wong et al., A Potent and Highly Selective Inhibitor of Human α-1,3-Fucosyltransferase via Click Chemistry, J. Am. Chem. Soc. 125: 9588-9589, 2003); Supported catalysts for easy metal removal (MR Buchmeiser et al., Monolithic Materials: New High-Performance Supports for Permanently Immobilized Metathesis Catalysts, Agnew. Chem. Int. Ed. 2001, 40, 3839) In order to achieve high efficiency and high yield of COP polymers, the research on obtaining high purity COP polymer is insufficient.

The present invention aims to provide a Grubbs supported catalyst and a method for preparing the catalyst which facilitate the removal of the catalyst, particularly during the synthesis of COP.

The Grubbs supported catalyst according to the embodiment of the present invention is characterized in that the support of Formula 1 is bound to the vinylidene ligand of the Grubbs catalyst.

≪ Formula 1 >

R1 is a compound group having a structure capable of resonance with a vinyl group,

R2 is C1-C12 alkyl group, phenyl group or benzophenyl group,

Cv is ester group, ether group, amide group and disulfide group, diphenylphosphine amide group, acetal group, ketal group, oxime group, imine group, oxazolidine group, thioester group, thioether group, carbomate group, A compound group comprising one selected from the group consisting of sulfonamide groups, or aromatic amine oxide groups, arylformaldehyde groups, carbomite groups, benzylsulfonamide groups, ester groups, acetal groups or ketal groups, hydrazone groups, A compound group including one selected from the group consisting of a sulfonyl ester group, a dithiolane group, a nitroamide group, a nitrile ester group, a nitroanilide group, an amine group, an ether group, a dioxane group, an amide group, or , Imidazolidine group, thiazolidine group, ester group, sulfonamide group, amide group, thioester group, thioether group Emitter and the compound groups containing one selected,

R3 is a resin group based on polystyrene obtained by polymerizing 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB).

Here, it is preferable that the support bonded to the vinylidene ligand of the Grubbs catalyst is a compound of the formula (2) or (3).

(2)

Crp is an insoluble carrier of carboxyl acid-based polystyrene (Carboxypolystyrene) base and has a weight average molecular weight (Mw) of 10,000 to 1,000,000.

<Formula 3>

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000.

The method for preparing a Grubbs supported catalyst according to the second embodiment of the present invention includes a one-stage reaction for alkyne reaction of the carboxyl end of a polystyrene-based resin having a carboxyl group (Carboxypolystyrene resin); A two-step reaction of reacting the polystyrene-based resin having the carboxyl group at the alkyne end with vinylbenzylazide; By including a three-step reaction for reacting the compound synthesized by the second step and the Grubbs catalyst, the carrier of the formula (2) to prepare a Grubbs supported catalyst bonded to the vinylidene ligand of the Grubbs catalyst It is characterized by.

A method for preparing a Grubps supported catalyst according to a third embodiment of the present invention includes a step A reaction of reacting polystyrene-based Wang resin having a alcohol group with terephthaloyl dichloride; A step B reaction for alkynating the ends of the compound synthesized by the step A reaction; A step C reaction of reacting the compound synthesized by the step B reaction with vinylbenzylazide; Including the D-step reaction for reacting the compound synthesized by the C-step reaction with the Grubbs catalyst, to prepare a Grubps supported catalyst in which the carrier of the formula (3) is bonded to the vinylidene ligand of the Grubbs catalyst It features.

Here, in the one-step reaction or the B-step reaction, it is preferable to react Propargyl alcohol (2-propyn-1-ol) with a compound synthesized by the polystyrene-based resin having the carboxyl group or alcohol or the A-step reaction. Do.

In addition, the vinylbenzyl azide (Vinylbenzylazide) is preferably synthesized by reacting 4-vinylbenzylchloride and sodium azide (sodiun azide) in the two-step or C-step reaction.

Thus, the present invention provides a Grubbs supported catalyst which is easy to remove the catalyst during the catalytic polymerization reaction, in particular for the synthesis of COP and a method for producing the catalyst.

The Grubbs supported catalyst according to an embodiment of the present invention is characterized in that the support of Formula 1 is bound to the vinylidene ligand of the Grubbs catalyst, that is, the support of Formula 1 is a support. and the alkynyl membered ring bond, N-a, and Cv is a direct bond and R ₃ around the R ₃ forming the central structure, and R ₂ is bonded to the other side, azide applying the click chemistry (click chemistry) to R ₂ R ₁ is bonded to the zide-alkyne ring compound, and a vinyl group is bonded to R1.

Here, R1 is a compound having a structure capable of resonance with the vinyl group, and in order to cause an exchange reaction with the benzylidene portion of the Grubbs catalyst, R1 has a resonance structure capable of transferring electrons to the vinyl group more than the benzylidene of the Grubbs catalyst. Must have If R1 is an alkyl vinyl group which does not have a resonance structure with the vinyl group, it may cause side reaction with the Grubbs catalyst. The compound group having a structure capable of resonance with the vinyl group of R1 may be a phenyl group, a benzene derivative group, a thiophene group, an alkylidene group, a pyrrole group, or the like.

Cv represents R ₃ constituting the central skeleton of the carrier by the Cv group separation reaction, if necessary, after completion of the catalytic polymerization reaction using the Grubbs supported catalyst according to the present invention. It can be separated. In this case, Cv is an ester group, an ether group, an amide group and a disulfide group, a diphenylphosphine amide group, an acetal group, a ketal group, an oxime group, an imine group, an oxazolidine group, a thioester which can be easily separated by an acid. A compound group comprising one selected from the group consisting of a group, a thioether group, a carbomate group, and a sulfonamide group, or an aromatic amine oxide group (300 nm) and an arylformaldehyde group which can be easily separated through light. (254 nm), carbomite group, benzyl sulfonamide group, ester group, acetal group or ketal group, hydrazone group, sulfonyl ester group, dithiolane group, nitroamide group, nitrile ester group, nitroaniyl Compound can be easily separated by a base including one selected from the group consisting of a lide group, an amine group, an ether group, a dioxane group, an amide group, or a base. Imidazolidin dingi, thiazolidine dingi, may be a compound date, including one member selected from an ester group, a sulfonamide group, an amide group, a thioester group, a thioether group group of.

In addition, R ₃ forms a central skeleton of the carrier, insoluble polystyrene obtained through suspension polymerization and crosslinking of 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB). As the resin group of (Polystyrene) base, it is possible to swell by solvent, and the higher the content of styrene, the easier the swelling of the resin obtained, thereby making it easier to access the monomer in the catalytic polymerization reaction. It can be. That is, since it is not dissolved by a solvent, it can be easily removed after completion of the ring-opening polymerization reaction, and swelling can be performed by a solvent during the ring-opening polymerization reaction, so that the monomer can be easily accessed during the ring-opening polymerization reaction. It can be done actively.

In addition, the other side of the Cv in combination with R ₃ has access to an alkyl group, a phenyl group or a benzoyl phenyl group R ₂ is a combination of C1 ~ C12, whereby by spaced away from the center of Ru metal of Grubbs catalyst from R3 monomer is a Ru metal It is easy to further activate the catalytic polymerization reaction.

In addition, since the azide-alkyne ring compound applied by Click Chemistry (R) between R1 and R2 is disclosed and bound, it is possible to easily bind R1 and R2 having a vinyl group bonded thereto. That is, in order to support a high yield of the metal catalyst on the support, a large amount of vinyl groups (vinyl groups bonded with R1) that can be combined with the vinylidene ligand of the Grubbs catalyst should be included. It is. Click chemistry is an azide-alkyne ring addition reaction, which has a very high thermodynamic propulsion force (typically 20 kcal / mol or more), which can efficiently form a carbon-heteroatomic bond between an azide compound and an alkyne compound in high yield. Therefore, the click chemistry is capable of forming intermolecular bonds with high yields not only with low molecules but also with polymers such as oligomers and polymers by high reactivity.

That is, by binding the vinyl group R1 and R2 to the azide-alkyne cyclic compound by applying the click chemistry, the compound from R3 to R2 and R1 bonded to the vinyl group can form a chemical bond, thereby A vinyl group can be provided to a support body. That is, the vinyl group bonded to R1 can bind to the vinylidene ligand of the Grubbs catalyst.

As an example of a Grubbs supported catalyst in which the carrier of Formula 1 is bound to the vinylidene ligand of the Grubbs catalyst, the form of the Grubbs catalyst combined with an example of the first generation Grubbs catalyst is the same as that of Formula 4, and the second generation Grubbs The form combined with one example of the catalyst is the same as the formula (5), and the form combined with one example of the third generation Grubbs catalyst is the same as the formula (6).

&Lt; Formula 4 >

R1 is a compound group having a structure capable of resonance with a vinyl group,

R2 is C1-C12 alkyl group, phenyl group or benzophenyl group,

Cv is ester group, ether group, amide group and disulfide group, diphenylphosphine amide group, acetal group, ketal group, oxime group, imine group, oxazolidine group, thioester group, thioether group, carbomate group, A compound group comprising one selected from the group consisting of sulfonamide groups, or aromatic amine oxide groups, arylformaldehyde groups, carbomite groups, benzylsulfonamide groups, ester groups, acetal groups or ketal groups, hydrazone groups, A compound group including one selected from the group consisting of a sulfonyl ester group, a dithiolane group, a nitroamide group, a nitrile ester group, a nitroanilide group, an amine group, an ether group, a dioxane group, an amide group, or , Imidazolidine group, thiazolidine group, ester group, sulfonamide group, amide group, thioester group, thioether group Emitter and the compound groups containing one selected,

R3 is a resin group based on polystyrene obtained by polymerizing 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB).

&Lt; Formula 5 >

R1 is a compound group having a structure capable of resonance with a vinyl group,

R2 is C1-C12 alkyl group, phenyl group or benzophenyl group,

Cv is ester group, ether group, amide group and disulfide group, diphenylphosphine amide group, acetal group, ketal group, oxime group, imine group, oxazolidine group, thioester group, thioether group, carbomate group, A compound group comprising one selected from the group consisting of sulfonamide groups, or aromatic amine oxide groups, arylformaldehyde groups, carbomite groups, benzylsulfonamide groups, ester groups, acetal groups or ketal groups, hydrazone groups, A compound group including one selected from the group consisting of a sulfonyl ester group, a dithiolane group, a nitroamide group, a nitrile ester group, a nitroanilide group, an amine group, an ether group, a dioxane group, an amide group, or , Imidazolidine group, thiazolidine group, ester group, sulfonamide group, amide group, thioester group, thioether group Emitter and the compound groups containing one selected,

R3 is a resin group based on polystyrene obtained by polymerizing 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB).

(6)

R1 is a compound group having a structure capable of resonance with a vinyl group,

R2 is C1-C12 alkyl group, phenyl group or benzophenyl group,

Cv is ester group, ether group, amide group and disulfide group, diphenylphosphine amide group, acetal group, ketal group, oxime group, imine group, oxazolidine group, thioester group, thioether group, carbomate group, A compound group comprising one selected from the group consisting of sulfonamide groups, or aromatic amine oxide groups, arylformaldehyde groups, carbomite groups, benzylsulfonamide groups, ester groups, acetal groups or ketal groups, hydrazone groups, A compound group including one selected from the group consisting of a sulfonyl ester group, a dithiolane group, a nitroamide group, a nitrile ester group, a nitroanilide group, an amine group, an ether group, a dioxane group, an amide group, or , Imidazolidine group, thiazolidine group, ester group, sulfonamide group, amide group, thioester group, thioether group Emitter and the compound groups containing one selected,

R3 is a resin group based on polystyrene obtained by polymerizing 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB).

As such, the support of Formula 1 may be combined with various forms of Grubbs catalyst to form a Grubbs supported catalyst.

When the carrier of the formula (1) is used in the catalytic polymerization reaction of the Grubbs supported catalyst bound to the vinylidene ligand of the Grubbs catalyst, in particular, when used in the ROMP and hydrogenation reaction for synthesizing COP, and By the mechanism of extraction, the Grubbs catalyst can be easily removed from the finally obtained high molecular compound, that is, COP.

Scheme 1 uses the Grubbs supported catalyst of Formula 4 in which the carrier of Formula 1 is combined with the vinylidene ligand of the first generation Grubbs catalyst.

<Reaction Scheme 1>

R1 is a compound group having a structure capable of resonance with a vinyl group,

R2 is C1-C12 alkyl group, phenyl group or benzophenyl group,

Cv is ester group, ether group, amide group and disulfide group, diphenylphosphine amide group, acetal group, ketal group, oxime group, imine group, oxazolidine group, thioester group, thioether group, carbomate group, A compound group comprising one selected from the group consisting of sulfonamide groups, or aromatic amine oxide groups, arylformaldehyde groups, carbomite groups, benzylsulfonamide groups, ester groups, acetal groups or ketal groups, hydrazone groups, A compound group including one selected from the group consisting of a sulfonyl ester group, a dithiolane group, a nitroamide group, a nitrile ester group, a nitroanilide group, an amine group, an ether group, a dioxane group, an amide group, or , Imidazolidine group, thiazolidine group, ester group, sulfonamide group, amide group, thioester group, thioether group Emitter and the compound groups containing one selected,

R3 is a resin group based on polystyrene obtained by polymerizing 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB).

That is, as shown in Scheme 1, when the catalyst polymerization reaction (ROMP) of the norbornene derivative, which is a basic monomer of COP, is carried out using the Grubbs supported catalyst of Chemical Formula 4, the carrier of Chemical Formula 1 and Grubbs catalyst are separated and The vinylidene ligand of the catalyst is bound to one side of the COP, and the carrier of Formula 1 forms a vinyl bond to the other side of the COP. Thereafter, when the hydrogenation reaction proceeds, the Grubbs catalyst is separated from the COP and is dissolved in the solvent, and the carrier of the formula (1) maintains the bond with the COP in the state where the vinyl group is alkylated. It will be in an undissolved state. Thereafter, the COP to which the carrier of Formula 1 is bound is precipitated in the form of an insoluble matter through the filter process, and the Grubbs catalyst can be almost completely removed together with the solvent. In addition, by performing a cleavage reaction on the precipitated insoluble matter, the chemical bond with R3 forming the central skeleton of the carrier can be separated by the Cv group separation reaction, and then the insoluble material is filtered out. By doing so, pure COP can be obtained. By this reaction mechanism, the Grubbs catalyst can be almost completely removed from the final reaction product COP after catalytic polymerization, hydrogenation, and cleavage.

More preferably, the carrier of the Grubbs supported catalyst according to the present invention is a compound of the formula (2) or (3).

The carrier of formula (2) can have a stable resonance structure with a vinyl group by using R1 as a phenyl group in the carrier of formula (1), and can improve the reaction yield of the catalyst because it is a derivative of the benzylidene moiety of the Grubbs catalyst. In addition, R3 is an insoluble carrier of a carboxylic acid terminal polystyrene (Carboxypolystyrene) base, Crp having a weight average molecular weight (Mw) of 10,000 to 1,000,000, thereby swelling in a solvent such as dimethylformamide (DMF) about 8.4 It can be done as good as ml / g. Here, Crp is the initial reactant of styrene, vinyl benzyl chloride and divinyl benzene, and the degree of functionalization of the terminal is determined from the content of vinyl benzyl chloride, and the content of vinyl benzyl chloride and divinyl benzene is 10 to 40 mole% and 1 to styrene, respectively. It is preferable that it is-25 mole%. The carboxylic acid at the Crp end can be produced by carboxylation of the chloride end determined from vinyl benzyl chloride. In addition, by using Cv as an ester, it is possible to prevent the polymer (COP) polymerized by the catalytic polymerization reaction from the carrier with a stable functional group that does not occur under the Ru catalyst during the hydrogenation in the catalytic polymerization reaction. In addition, after hydrogenation and filtration, the polymer (COP), which is easily decomposed into carboxylic acid and alcohol under mild acid conditions and polymerized by catalytic polymerization, can be easily separated from R3 forming the central skeleton of the carrier.

The carrier of formula (3) is an insoluble carrier of alcohol-terminated polystyrene (Carboxypolystyrene) base in the carrier of formula (1), dichloromethane by making a Wang resin (Wa) having a weight average molecular weight (Mw) of 10,000 ~ 1,000,000 In solvents such as (Dichloro methane), the swelling can be as good as about 7.2ml / g. Here, Wang resin (Wa) is Styrene, vinyl benzyl chloride and divinyl benzene as initial reactants, the degree of functionalization of the terminal is determined from the content of vinyl benzyl chloride, vinyl benzyl chloride and divinyl benzene content of 10 ~ It is preferable that they are 40 mole% and 1-25 mole%. In addition, the alcohol group at the end of Wang resin (Wa) can be produced by subjecting the chloride end determined from vinyl benzyl chloride to alcoholation. In addition, by using Cv as an ester, it is possible to prevent the polymer (COP) polymerized by the catalytic polymerization reaction from the carrier with a stable functional group that does not occur under the Ru catalyst during the hydrogenation in the catalytic polymerization reaction. In addition, after hydrogenation and filtration, the polymer (COP), which is easily decomposed into carboxylic acid and alcohol under mild acid conditions and polymerized by catalytic polymerization, can be easily separated from R3 forming the central skeleton of the carrier.

Further, as an example of a Grubbs supported catalyst in which the carrier of Formula 2 is bound to the vinylidene ligand of the Grubbs catalyst, the form of the Grubbs catalyst combined with an example of the first generation Grubbs catalyst is the same as that of Formula 7, and the second generation Grubbs ( The combined form with one example of the Grubbs) catalyst is shown in Formula 8, and the combined form with one example of the third generation Grubbs catalyst is shown in Formula 9.

&Lt; Formula 7 >

Crp is an insoluble carrier of carboxyl acid-based polystyrene (Carboxypolystyrene) base and has a weight average molecular weight (Mw) of 10,000 to 1,000,000.

(8)

Crp is an insoluble carrier of carboxyl acid-based polystyrene (Carboxypolystyrene) base and has a weight average molecular weight (Mw) of 10,000 to 1,000,000.

&Lt; Formula 9 >

Crp is an insoluble carrier of carboxyl acid-based polystyrene (Carboxypolystyrene) base and has a weight average molecular weight (Mw) of 10,000 to 1,000,000.

In addition, as an example of a Grubbs supported catalyst in which the carrier of Formula 3 is bound to the vinylidene ligand of the Grubbs catalyst, the form of the Grubbs catalyst combined with an example of the first generation Grubbs catalyst is the same as that of Formula 10, and the second generation Grubbs ( The combined form with one example of the Grubbs) catalyst is shown in Formula 11, and the combined form with one example of the third generation Grubbs catalyst is shown in Formula 12.

&Lt; Formula 10 >

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000.

&Lt; Formula 11 >

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000.

&Lt; Formula 12 >

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000.

The method for preparing a Grubbs supported catalyst according to the second embodiment of the present invention includes a one-stage reaction for alkyne reaction of the carboxyl end of a polystyrene-based resin having a carboxyl group (Carboxypolystyrene resin); A two-step reaction of reacting the polystyrene-based resin having the carboxyl group at the alkyne end with vinylbenzylazide; By including a three-step reaction for reacting the compound synthesized by the second step and the Grubbs catalyst, to prepare a Grubbs-supported catalyst in which the carrier of the formula (2) is bonded to the vinylidene ligand of the Grubbs catalyst Characterized in that.

That is, by alkynating the carboxyl terminal of the polystyrene resin having a carboxyl group (Carboxypolystyrene resin), the azide group of vinylbenzyl azide and the click chemistry reaction can be caused in the two-step reaction. will be.

At this time, the one-step reaction of alkynating the carboxyl terminal of the polystyrene resin having a carboxyl group (Carboxypolystyrene resin) is a polystyrene-based resin having a carboxyl group and propargyl alcohol (2-propyn- 1-ol) is preferred.

<Reaction Scheme 2>

Crp is an insoluble carrier of carboxyl acid-based polystyrene (Carboxypolystyrene) base and has a weight average molecular weight (Mw) of 10,000 to 1,000,000.

A method for preparing a Grubps supported catalyst according to a third embodiment of the present invention includes a step A reaction of reacting polystyrene-based Wang resin having a alcohol group with terephthaloyl dichloride; A step B reaction for alkynating the ends of the compound synthesized by the step A reaction; A step C reaction of reacting the compound synthesized by the step B reaction with vinylbenzylazide; Including the D-step reaction for reacting the compound synthesized by the C-step reaction with the Grubbs catalyst, to prepare a Grubps supported catalyst in which the carrier of the formula (3) is bonded to the vinylidene ligand of the Grubbs catalyst It features.

That is, the step A reaction of reacting polystyrene-based Wang resin having an alcohol group with terephthaloyl dichloride may be performed as in Scheme 3 below.

<Reaction Scheme 3>

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000.

In addition, by alkynating the terminal of the compound synthesized by the step A reaction, it is possible to cause a click chemistry reaction of the azide group of vinylbenzyl azide in the step C reaction. At this time, the step B reaction for alkynating the terminal of the compound synthesized by the step A reaction is carried out with the compound synthesized by the step A reaction and Propargyl alcohol (2-propyn-1-ol) as shown in Scheme 3 below. It is preferable to react).

<Reaction Scheme 4>

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000.

In addition, the vinylbenzyl azide (Vinylbenzylazide) in the two-step reaction or the C-step reaction, synthesized by reacting 4-vinylbenzylchloride and sodium azide (sodiun azide), as shown in Scheme 5 It is preferable.

<Reaction Scheme 5>

Hereinafter, the production method and the Grubbs supported catalyst of the present invention will be described in detail with reference to Examples.

<Examples>

In each example, a synthesis example of vinylbenzyl azide to be used for the click chemistry reaction will be described first, and then each specific example of preparing the Grubbs supported catalyst to which the carriers of Formulas 2 and 3 are combined will be described. do.

<Synthesis of vinyl benzyl azide (VBA)>

In an argon (Ar) atmosphere, 5.55 ml (0.04 mol) of 4-vinyl benzyl chloride (VBC) and 60 ml of purified dimethylformamide (DMF) were added to a 100 ml round flask, and 3.84 g of sodium azide. (0.06 mol) in 15 ml of DMF was added. Thereafter, the mixture was reacted at room temperature for 24 hours, and then methylene chloride (MC) was added to the reaction solution, followed by extraction with water five times to remove impurities. The obtained organic solution was treated with MgSO 4, and then distilled vinylbenzyl. Obtained azide.

4-vinyl benzyl chloride (VBC) and the reaction product vinyl benzyl azide before reaction were confirmed by NMR measurement. As shown in FIG. 1, the position of CH2 of d in VDC was changed from VBA to D after reaction. It can be seen that the movement, through which it can be confirmed that the VBA synthesized from the VBC.

<Example 1>-Preparation of Grubbs supported catalyst to which the carrier of formula 2 is bonded

1) 1st step reaction

3 g (13.5 mmol) of carboxypolystyrene resin and 4.72 ml (81 mmol) of Progagyl acohol and 35.41, which are polystyrene-based insoluble carriers having 4.5 mmol / g carboxyl groups at the ends in a 1 L round flask in an argon (Ar) atmosphere. g (135 mmol) triphenylphosphine (triphenylphosphine) and 545 ml of tetrahydrofuran (THF) were added and then cooled to 5 ° C. Thereafter, 26.58 ml (135 mmol) of diisopropyl azodicarboxylate (DIAD) was diluted in 75 ml THF and added dropwise to the reactor, stirred at room temperature for 24 hours, and the reaction was terminated and filtered to insoluble reactants. After removing the unreacted reagent by repeatedly washing the insoluble reactant with THF and methanol, and drying the insoluble reactant in a vacuum oven, the carboxyl end of the polystyrene resin having a carboxyl group (Carboxypolystyrene resin) Alkyne.

The carboxypolystyrene resin and the reaction product of the pre-reaction compound were analyzed by FT-IR. As shown in FIG. 2, the -OH group (3400 cm ^-1 ) of the carboxylic acid of the pre-reaction compound of the carboxypolystyrene resin disappeared, and the newly produced ester The alkyne group was introduced at the end of the reactant by moving the carbonyl group of the group to the left side (near 1700 cm ⁻¹ ) compared with the carbonyl group of the carboxylic acid and the carbonyl group of the carboxylic acid.

2) two-step reaction

In an argon (Ar) atmosphere, 1g (4.5mmol), CuBr 1.4346g (10mmol), VBA 1.4516g (10mmol), and 50ml THF were placed in a 250ml round flask in n, n, n, n, n, -pentamethyldiethltriamine (PMDETA) 1.752ml (10mmol) was added to the reaction at room temperature for 24 hours to synthesize a carrier of formula (2). The synthesized support was insoluble in THF and methanol to be washed repeatedly to remove unreacted reagents, and then dried in a vacuum oven to obtain a carrier of Formula 2 having an alkene group at the end.

The reaction before compound, carrier of the general formula (2) first-step reaction and the resulting two-phase reaction product of the second-step reaction was analyzed by the FT-IR result, as shown in Figure 3, 2100cm a triazole asleep generated Cleveland reaction ^-1 It was confirmed in the vicinity, it can be seen that the two-step reaction was completed through this.

3) 3-step reaction

a. Synthesis of 1st Generation Grubbs Supported Catalyst

In an argon atmosphere, 0.51355 g (2.0542 mmol) of a carrier of Formula 2 having an alkene group and 70 ml of THF were added to a round flask in a round flask and stirred for 12 hours. Thereafter, a solution of 1.646 g (2 mmol) of the first generation Grubbs catalyst was added to the reaction vessel in 44 ml THF, and then reacted for 1 hour and 30 minutes, and then the insoluble reactant was filtered and washed several times with THF, thereby removing the unreacted catalyst. After removing and drying in a vacuum oven, a supported Grubbs supported catalyst was bonded to the carrier of the formula (2). The progress of the reaction was found to be due to the change of the color of the supported catalyst to dark brown.

b. Synthesis of Second Generation Grubbs Supported Catalyst

In an argon atmosphere, 0.51355 g (2.0542 mmol) of a carrier of Formula 2 having an alkene group and 70 ml of THF were added to a round flask in a round flask and stirred for 12 hours. Thereafter, a solution of 1.698 g (2 mmol) of the second generation Grubbs catalyst was added to the reaction vessel in 44 ml THF, and then reacted for 1 hour and 30 minutes. Then, the insoluble reactant was filtered and washed several times with THF to remove the unreacted catalyst. After removing and drying in a vacuum oven, a supported Grubbs supported catalyst was bonded. The progress of the reaction was found to be due to the change of the color of the supported catalyst to dark brown.

<Example 2>-Preparation of a Grubps supported catalyst to which the carrier of formula 3 is bonded

1) Stage A reaction

After arranging 6.0906g (30mmol) of terephthaloyl dichloride and 300ml of THF in a 1L round flask in argon (Ar) atmosphere, polystyrene series having 1mmol / g of alcohol (alcohol) at the end 3g (3mmol) of Wang resin was added dropwise. Thereafter, after stirring for 24 hours at room temperature, the reaction was terminated, the insoluble reactant was obtained through filtration, and washed repeatedly with THF, methanol to remove the unreacted reagent and dried.

2) stage B reaction

In an argon (Ar) atmosphere, 2 g (2 mmol) of the reaction product of the A stage reaction was placed in a 500 ml round flask, 200 ml of THF and dicyclohexylcarbodiimide (DCC) 0.4539 g (2.2 mmol), propargyl alcohol 1.164 After addition of ml (20 mmol) was stirred for 24 hours at room temperature. Thereafter, the reaction was terminated, an insoluble reactant was obtained through filtration, and then washed repeatedly with THF and methanol to remove unreacted reagents and dried to obtain a reaction product having an Alkyne group at the end. .

As a result of analyzing the Wang resin, the resultant reaction of Step A and the resultant reaction of B through FT-IR, as shown in FIG. 4, the alcohol group (3400cm ^-1 ) of the king resin disappeared from the graph of the resultant reaction of A step, and newly generated. Formation of carbonyl group of ester group and acid chloride group was confirmed around 1700cm ^-1 . In addition, the carbonyl group of the ester group is shifted to a lower frequency band (1700cm ^-1 ), it can be confirmed that the Alkyne group was introduced at the end of the carrier.

2) Step C reaction

In a 250 ml round flask in an argon (Ar) atmosphere, 1 g (1 mmol) of the result of the B stage reaction, 0.287 g (2 mmol) of CuBr, 0.29 g (2 mmol) of VBA, and 10 ml of THF were added, n, n, and n. The carrier of Formula 3 was synthesized by adding 0.3504 ml (2 mmol) of, n, n, -pentamethyldiethltriamine (PMDETA) at room temperature for 24 hours. The synthesized carrier was insoluble in THF and methanol to be washed repeatedly to remove unreacted reagents, and then dried in a vacuum oven to finally provide a carrier of Formula 3 having an alkene group at the end.

To the carrying member of the formula 3 in the reaction of compound C before reaction step B reaction product and C stage reaction product was analyzed through an FT-IR, as shown in Figure 5, 2100cm a triazole asleep generated Cleveland reaction ^-1 It was confirmed in the vicinity, it can be seen that the C-step reaction was completed through this.

3) step D reaction

a. Synthesis of 1st Generation Grubbs Supported Catalyst

In an argon atmosphere, 0.1 g (0.1 mmol) of a carrier of Chemical Formula 3 having an alkene group and 13.5 ml of THF were added to a round flask in a round flask and stirred for 12 hours. Thereafter, a solution of 0.27855 g (0.34 mmol) of the first generation Grubbs catalyst was added to the reaction vessel and reacted for 1 hour and 30 minutes, and then the insoluble reactants were filtered and washed several times with THF. The reaction catalyst was removed and dried in a vacuum oven to obtain a Grubbs supported catalyst to which the carrier of Formula 3 was bound. The progress of the reaction was found to be due to the change of the color of the supported catalyst to dark brown.

b. Synthesis of Second Generation Grubbs Supported Catalyst

In an argon atmosphere, 0.1 g (0.1 mmol) of a carrier of Chemical Formula 3 having an alkene group and 13.5 ml of THF were added to a round flask in a round flask and stirred for 12 hours. Thereafter, a solution of 0.28865 g (0.34 mmol) of the second generation Grubbs catalyst was added to the reaction vessel and reacted for 1 hour and 30 minutes, and then the insoluble reactants were filtered and washed several times with THF. The reaction catalyst was removed and dried in a vacuum oven to obtain a Grubbs supported catalyst to which the carrier of Formula 3 was bound. The progress of the reaction was found to be due to the change of the color of the supported catalyst to dark brown.

1 is a graph showing the results of NMR measurement of the compound before and after the reaction of the vinylbenzyl azide synthesis of the embodiment of the present invention.

Figure 2 is a graph of the results of measuring the FT-IR of the compound before the first step reaction and the reaction product after the reaction of Example 1 of the present invention.

Figure 3 is a graph of the results of measuring the FT-IR of the first stage reaction product and the second stage reaction product of Example 1 of the present invention.

Figure 4 is a graph of the result of measuring the FT-IR of the compound, the step A reaction product and the step B reaction product before the step A reaction of Example 2 of the present invention.

Figure 5 is a graph of the results of measuring the FT-IR of the B step reaction product and the C step reaction product of Example 2 of the present invention.

Claims (8)

A carrier supported by Grubbs, characterized in that the carrier of Formula 1 is bound to the vinylidene ligand of the Grubbs catalyst. &Lt; Formula 1 >

R 1 is one selected from the group consisting of a phenyl group, a benzene derivative group, a thiophene group, an alkylidene group and a pyrrole group, R2 is a phenyl group, a benzophenyl group or a C1-C12 alkyl group, Cv is ester group, ether group, amide group and disulfide group, diphenylphosphine amide group, acetal group, ketal group, oxime group, imine group, oxazolidine group, thioester group, thioether group, carbomate group, A compound group comprising one selected from the group consisting of sulfonamide groups, or aromatic amine oxide groups, arylformaldehyde groups, carbomite groups, benzylsulfonamide groups, ester groups, acetal groups or ketal groups, hydrazone groups, A compound group including one selected from the group consisting of a sulfonyl ester group, a dithiolane group, a nitroamide group, a nitrile ester group, a nitroanilide group, an amine group, an ether group, a dioxane group, an amide group, or , Imidazolidine group, thiazolidine group, ester group, sulfonamide group, amide group, thioester group, thioether group Emitter and the compound groups containing one selected, R3 is a resin group based on polystyrene obtained by polymerizing 95 to 99 mol% of styrene and 1 to 5 mol% of divinylbenzene (DVB). delete The method of claim 1, The carrier is a grub supported catalyst, characterized in that the following formula (2). (2)

Crp is an insoluble carrier of carboxyl acid-based polystyrene (Carboxypolystyrene) base and has a weight average molecular weight (Mw) of 10,000 to 1,000,000. The method of claim 1, The carrier is a grub supported catalyst, characterized in that the following formula (3). <Formula 3>

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000. A one-step reaction for alkynating the carboxyl end of a polystyrene-based resin having a carboxyl group (Carboxypolystyrene resin); A two-step reaction of reacting the polystyrene-based resin having the carboxyl group at the alkyne end with vinylbenzylazide; Including the three-step reaction for reacting the compound synthesized by the second step with the Grubbs catalyst, to prepare a Grubps supported catalyst in which the carrier of the formula (2) is bonded to the vinylidene ligand of the Grubbs catalyst A method for producing a grub supported catalyst. (2)

Crp is an insoluble carrier of carboxyl acid-based polystyrene (Carboxypolystyrene) base and has a weight average molecular weight (Mw) of 10,000 to 1,000,000. A step A reaction of reacting polystyrene-based Wang resin having an alcohol group with terephthaloyl dichloride; A step B reaction for alkynating the ends of the compound synthesized by the step A reaction; A step C reaction of reacting the compound synthesized by the step B reaction with vinylbenzylazide; By including the step D reaction of reacting the compound synthesized by the step C with the Grubbs catalyst, the carrier of the formula (3) is characterized in that to prepare a Grubbs supported catalyst bonded to the vinylidene ligand of the Grubbs catalyst Method for producing a supported grub catalyst. <Formula 3>

Wa is a Wang resin, an insoluble support of alcohol-based polystyrene (Carboxypolystyrene) base, the weight average molecular weight (Mw) of 10,000 ~ 1,000,000. The method according to claim 5 or 6, The one-stage reaction or the B-stage reaction is a Grubbs supporting, characterized in that the polystyrene-based resin having the carboxyl group or the compound synthesized by the A-stage reaction reacts with Propargyl alcohol (2-propyn-1-ol) Method for preparing a catalyst. The method according to claim 5 or 6, The vinylbenzyl azide (Vinylbenzylazide) in the two-step reaction or step C reaction of the Grubbs supported catalyst, characterized in that synthesized by reacting 4-vinylbenzylchloride and sodium azide (sodiun azide) Manufacturing method.

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