CN106939026B - Preparation and application of ruthenium metal olefin metathesis catalyst - Google Patents
Preparation and application of ruthenium metal olefin metathesis catalyst Download PDFInfo
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Abstract
The invention discloses a ruthenium metal olefin metathesis catalyst formed by a novel alkene ligand and ruthenium carbene and application thereof. The invention selects salicylaldehyde which has simple structure and is easy to obtain and contains substituent groups as an initial raw material, obtains the needed alkene ligand by simple synthesis, and then carries out ligand exchange with the catalyst precursor to obtain the corresponding novel ruthenium metal catalyst. The catalyst can efficiently catalyze olefin metathesis reaction, is used for catalyzing ring closing metathesis reaction of multiple kinds of diolefins to obtain a cyclic compound and catalyzing dicyclopentadiene to carry out ring opening metathesis polymerization reaction. The method has the advantages of easily available raw materials, simple operation, stable process, environmental protection and suitability for large-scale production, and provides a good idea and method for preparing various macrocyclic drug molecules and super-performance polymer materials by using the olefin metathesis catalyst.
Description
Technical Field
The invention relates to a preparation method and application of an olefin metathesis catalyst, in particular to a preparation method of a ruthenium metal catalyst and application of the ruthenium metal catalyst in catalyzing diolefin substrates to carry out ring closing metathesis reaction and catalyzing dicyclopentadiene to carry out ring opening metathesis polymerization reaction.
Technical Field
In recent decades, the research on olefin metathesis has been rapidly developed due to the great value of the synthesized products in the fields of medicines, pesticides, materials and the like. Ring-closing metathesis (RCM) is an important type of olefin metathesis reaction, and has gained increasing attention due to its remarkable characteristics in synthesizing various macrocyclic molecules. It provides an important means for synthesizing cyclic organic compounds by constructing a carbon-carbon double bond to cyclize the compound. Currently, some macrocycles have been used clinically as drugs, and more macrocycles are in the corresponding drug development stage (Nature,2008,7, 608-. Ring-opening metathesis polymerization (ROMP) is another important type of olefin metathesis reaction. Research in this field mainly focuses on synthesizing efficient ROMP reaction catalysts and preparing multifunctional new materials based on ROMP reaction (Macromolecules,2012,45,4447 and 4453), and researchers have studied a large number of new polymer materials with excellent properties, such as polydicyclopentadiene, polynorbornene, polycyclooctene, etc., by using ROMP reaction.
Catalysts for olefin metathesis have evolved over the years to produce a variety of different types, with carbene-type catalysts being the most important RCM catalysts currently under study and development. Of these catalysts, the most important and most used are the Schrock catalyst (J.am. chem. Soc.1990,112,3875-3886) and the Grubbs catalyst (Bioorganic & Medicinal Chemistry 2001,9(1),199-209) as well as the Hoveyda-Grubbs catalyst, the Grela catalyst and the Zhan catalyst, which are modified with the Grubbs catalyst. The invention synthesizes a novel ruthenium metal olefin polymerization catalyst and applies the catalyst to catalyzing diolefin substrates to carry out ring closing metathesis reaction.
Disclosure of Invention
The invention aims to select substituted salicylaldehyde which is simple enough to be combined as a starting material, so that the required alkene ligand can be conveniently obtained, and the obtained alkene ligand and a catalyst precursor are subjected to ligand exchange to obtain the corresponding novel ruthenium metal catalyst. The catalyst can efficiently catalyze olefin metathesis reaction, is used for catalyzing various diene substrates to carry out ring closing metathesis reaction to synthesize macrocyclic organic molecules, and can also be used for catalyzing dicyclopentadiene polymerization reaction to obtain high-performance polymer materials. The method has the advantages of easily available raw materials, simple operation, stable process, environmental protection and suitability for large-scale production, and provides a good idea and method for the preparation of the alkene ligand and the ruthenium carbene catalyst and the preparation of large cyclic drug molecules and super-performance polymer materials by using the alkene double decomposition catalyst.
The invention provides a ruthenium metal olefin metathesis catalyst, which is characterized in that: the specific structural formula is as follows:
wherein R is1Hydrogen, alkyl, aryl;
R2hydrogen, alkyl, aryl;
R3hydrogen, alkyl, aryl;
R4hydrogen, alkyl, aryl;
R5hydrogen, alkyl, aryl;
R1' is hydrogen, alkyl, aryl;
R2' is hydrogen, alkyl, aryl;
R3' is hydrogen, alkyl, aryl;
R4' is hydrogen, alkyl, aryl;
R5' is hydrogen, alkyl, aryl;
R7hydrogen, alkyl, aryl;
l is halogen;
y is oxygen or sulfur;
Z1is halogen (preferably: chlorine, bromine, iodine), nitro, amino, aryl, alkyl, alkoxy, which is substituted on any or several of benzene rings;
Z2hydrogen, alkyl and aryl.
The above alkyl group is preferably selected from linear or branched alkyl groups having not more than 6 carbon atoms, such as: methyl, ethyl, propyl, gem-dimethyl (-CH (CH)3)2)、-C(CH3)3Pentane, -n-hexane, etc.;
the above alkoxy group is preferably selected from alkoxy groups having not more than 6 carbon atoms, such as: -OCH3，-OC2H5，-OC3H8，-OC4H9；
The above aryl group is preferably a phenyl group, a benzyl group, a p-methylphenyl group, a p-methoxyphenyl group, a m-methylphenyl group, a m-methoxyphenyl group, a p-hydroxyphenyl group, a p-methylbenzyl group, a p-methoxybenzyl group, a m-methylbenzyl group, a m-methoxybenzyl group or the like;
r is as defined above1、R2、R3、R4、R5、R1‘、R2‘、R3‘、R4‘、R5' are identical or different substituents.
Z above1Preferred are meta-or ortho-disubstituted groups.
Further, the present invention provides a method for preparing the ruthenium metal olefin metathesis catalyst, which is characterized by comprising the following steps:
protecting exposed hydroxyl in substituted salicylaldehyde or exposed sulfhydryl in 2-thiosalicylaldehyde by a nitrile compound;
wherein, the structure of the nitrile compound is shown as follows:
y is an oxygen or sulfur atom;
secondly, alkenylating carbonyl in the substituted salicylaldehyde;
the olefination reaction is preferably a Wittig reaction.
Step three, carrying out reduction and acylation reaction on the cyano group introduced in the step one to obtain an amide compound;
the amidation reagent used in the amidation process is a compound represented by the following structure:
the X is3Are electron withdrawing groups such as: halogen (preferably: chlorine, bromine, iodine), hydroxyl, etc.;
and step four, reacting the product obtained in the step three with a catalyst precursor to obtain a target product.
The catalyst precursor is typically Grubbs 2ndA catalyst precursor.
Further, the preparation method of the ruthenium metal olefin metathesis catalyst provided by the invention comprises the following specific process steps:
step 1-1, adding substituted salicylaldehyde, a solvent, strong base and a nitrile compound into a reactor, uniformly stirring at room temperature, and reacting for 0.5-20 hours at the temperature of 20-80 ℃;
the strong base is selected from sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, diisopropylethylamine, potassium tert-butoxide, sodium hydride, potassium hydride; preferably, the base is selected from inorganic bases such as potassium carbonate and cesium carbonate, and organic bases such as triethylamine and diisopropylethylamine.
The solvent is selected from nitrile solvent, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ether solvent, alkane solvent, toluene, chlorobenzene and alkyl halide; preferred solvents include acetonitrile, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide. The mass ratio of the solvent to the substituted salicylaldehyde is preferably 5-10: 1.
The reaction temperature is preferably 50-60 ℃;
the reaction time can be properly adjusted according to different reaction raw materials, and the end point of the reaction is judged to be the end of the reaction of the substituted salicylaldehyde raw material by TLC or other central control methods.
Step 1-2, extracting the reaction solution, and removing the solvent of an organic phase to obtain an intermediate I;
the extraction reagent is selected from esters, ethers, halogenated hydrocarbon, toluene, etc., preferably from ethyl acetate, methyl acetate, etc., and its usage amount is 3-4 times of total volume amount of reaction solution, and for improving extraction effect, water with 1-2 times volume amount can be selected for washing organic layer for at least 2 times.
The structural formula of the intermediate I is shown as follows:
step 2-1, dissolving the intermediate I in a solvent, adding triphenylphosphine bromomethane, cooling, adding strong base into the reaction liquid in batches, and reacting at the temperature of-10-120 ℃ for 0.5-20 hours to complete the Wittig reaction;
the strong base is selected from sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, diisopropylethylamine, potassium tert-butoxide, sodium hydride, potassium hydride, tert-butyllithium; preferably from potassium tert-butoxide, sodium hydride.
The solvent is selected from nitrile solvent, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ether solvent, alkane solvent, toluene, chlorobenzene and alkyl halide; preferably selected from methyl tert-butyl ether, diethyl ether or tetrahydrofuran. The mass ratio of the solvent to the intermediate I is preferably 10-15: 1.
The temperature of the reaction is preferably-10-0 ℃;
the reaction time can be properly adjusted according to different reaction raw materials, and the end point of the reaction is judged to be the end of the reaction of the intermediate I raw material by TLC or other central control methods.
Step 2-2, after the intermediate I finishes the reaction, removing the solvent, adding water, extracting the reaction solution, and removing the solvent of an organic phase to obtain an intermediate II;
the extraction reagent is selected from esters, ethers, halogenated hydrocarbons, toluene and other reagents, and is preferably selected from dichloromethane, trichloromethane and other halogenated hydrocarbons. The dosage of the organic solvent is 3-4 times of the total volume of the reaction solution, and 1-2 times of water can be selected for washing the organic layer for at least 2 times in order to improve the extraction effect.
Step 3-1, dissolving the intermediate II in a solvent, adding a reducing agent at a low temperature of below 0 ℃, reacting at a temperature of between 10 ℃ below zero and 120 ℃ for 0.5 to 20 hours, and reducing cyano groups into amino groups;
the solvent is selected from nitrile solvent, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ether solvent, alkane solvent, toluene, chlorobenzene and alkyl halide; preferably selected from ether solvents; most preferably selected from methyl tert-butyl ether, diethyl ether, tetrahydrofuran or 1, 4-dioxane). The mass ratio of the solvent to the intermediate II is preferably 5-15: 1.
The reaction temperature is preferably-10-0 ℃;
the reducing agent may be selected from any agent that reduces a cyano group to an amino group, preferably borane in tetrahydrofuran, lithium aluminum hydride, and the like.
Step 3-2, after the reaction is finished, quenching the reaction by using acid, and carrying out column chromatography to obtain an intermediate III;
the acid is preferably an inorganic acid, such as: hydrochloric acid or sulfuric acid, etc.; the concentration is preferably 7-85% acid.
The eluent used in the column chromatography process is preferably selected from esters, ethers, ketones, alkanes; preferably selected from ethyl acetate, methyl acetate, and the like, and alkanes having not more than 8 carbon atoms.
The eluent is most preferably ethyl acetate and n-hexane/n-pentane/cyclohexane/cyclopentane ═ 1: 0.5-5.
3-3, dissolving the intermediate III in a solvent, adding an acetylation reagent and strong base, and reacting at the temperature of 0-10 ℃ for 0.5-20 hours to perform amidation reaction;
the solvent is selected from nitrile solvent, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ether solvent, alkane solvent, toluene, chlorobenzene and alkyl halide; preferably selected from halogenated hydrocarbon solvents such as dichloromethane and trichloromethane. The mass ratio of the solvent to the intermediate III is preferably 5-15: 1.
The acetylating agent is preferably acetyl chloride or acetic anhydride;
the organic base is preferably triethylamine, diisopropylethylamine, potassium tert-butoxide, sodium tert-butoxide and the like, most preferably triethylamine or diisopropylethylamine;
step 3-4, after the reaction is finished, quenching the reaction by using acid, and drying to remove the solvent to obtain an alkene ligand;
the acid is preferably an inorganic acid, such as: hydrochloric acid or sulfuric acid, etc.; the concentration is preferably 7-85% acid.
Step 4-1, dissolving a catalyst precursor and an alkene ligand in a solvent, adding a catalyst, and reacting for 2-4 hours at the temperature of 30-50 ℃;
the solvent is selected from nitrile solvent, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ether solvent, alkane solvent, toluene, chlorobenzene and alkyl halide; the solvent is preferably n-hexane, n-heptane, petroleum ether, toluene, chlorobenzene, tetrahydrofuran, dichloromethane and the like, and the optimized solvent is toluene and dichloromethane; the ratio of solvent to catalyst precursor added is between 3mL:1g and 10mL:1g, with an optimal ratio of 5mL:1 g.
The catalyst is selected from metal catalysts, preferably from the group consisting of the iodinated ketones and the like.
And 4-2, filtering out solids, removing the solvent, and recrystallizing to obtain the target catalyst.
The solid is mostly inorganic salt solid after the reaction is finished;
before the final catalyst is separated out, the system is cooled to 0-20 ℃ and placed for 1-2 hours, and then impurities precipitated in the system are filtered and removed. Then, the solvent is removed by reduced pressure distillation, and a benign solvent and a poor solvent are added for crystallization to obtain a final product, namely a dark green solid.
The benign solvent can be selected from halogenated hydrocarbon such as dichloromethane and chloroform, ester solvent such as ethyl acetate and methyl acetate, and the poor solvent can be selected from alcohol solvent such as methanol, ethanol and isopropanol, ether solvent and ketone solvent.
The volume ratio of the benign solvent to the poor solvent is between 1:5 and 1:20, the most preferred volume ratio is 1:10, and the ratio of the total volume of solvent used for crystallization to the catalyst precursor used is between 5mL:1g and 20mL:1 g. The crystallization temperature required for precipitating the crystals of the final product is between 0 and 30 ℃, and the crystallization time is between 1 hour and 5 hours.
Further, the preparation method of the ruthenium metal olefin metathesis catalyst provided by the invention also has the following characteristics: namely, the molar ratio of the salicylaldehyde to the strong base to the nitrile compound is 1:1.0-2.5: 1.0-2.5; the preferred ratio is 1:1.2-1.5: 1.0-1.5;
the molar ratio of the intermediate I, the strong base and the triphenylphosphine bromomethane is 1:1.0-2.5: 1.0-2.5; the preferred ratio is 1:1.2-1.5: 1.0-1.5;
the molar ratio of the intermediate II to the reducing agent is 1: 2-3;
the molar ratio of the intermediate III, the acetylation reagent and the strong base is 1:1.0-2.5: 1.0-2.5; the preferred ratio is 1:1.0-1.2: 1.3-1.5;
the molar ratio of the catalyst precursor to the alkene ligand is 1: 1-2.5; the preferred ratio is 1: 1.0-1.2.
Further, the ruthenium metal olefin metathesis catalyst provided by the invention also has the following characteristics: that is, the ruthenium metal olefin metathesis catalyst is a compound represented by one of the following structures:
wherein, X is1Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；
X is above2Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt。
When the ruthenium metal olefin metathesis catalyst is of the above structure, its preferred method of preparation is as follows: namely, the method for preparing the novel ruthenium metal olefin metathesis catalyst is characterized by comprising the following five steps:
A. optionally substituted salicylaldehyde
The intermediate I is obtained by protecting the exposed hydroxyl in salicylaldehyde molecules through the reaction with bromoacetonitrile, and the structural formula of the intermediate I is as follows:
intermediate I
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
B. And C, reacting the intermediate I prepared in the step A with a Wittig reagent to obtain an olefin intermediate II, wherein the structural formula of the olefin intermediate II is as follows:
intermediate II
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
C. Reducing the cyano group in the intermediate II prepared in the step B into amino group by using a reducing agent to obtain an intermediate III with the structure of
Intermediate III
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
D. Protecting amino group in the intermediate III prepared in the step C by acetyl to obtain the required alkene ligand, wherein the structural formula is shown in the specification
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
E. D, preparing the alkene ligand obtained in the step D and a catalyst precursor Grubbs2ndBy carrying out a reaction to obtain the novel catalyst of claim 1
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S。
The specific preparation steps of the step A are as follows:
adding substituted salicylaldehyde, a solvent, strong base and bromoacetonitrile into a reactor, stirring uniformly at room temperature, slowly heating until the internal temperature of the reactor reaches 50-60 ℃, and continuously keeping the temperature for reaction until the reaction of the raw material substituted salicylaldehyde is finished. Then, a large amount of ethyl acetate was added to the reactor, and the organic phase was washed with water several times. Finally, spin-drying the organic layer drying solvent to obtain an intermediate I
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
The strong base used in the reaction system may be an inorganic base such as potassium carbonate or cesium carbonate, or an organic base such as triethylamine or diisopropylethylamine.
The solvent used in the step A can be acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and the like, the mass ratio of the solvent to the raw material substituted salicylaldehyde is 5:1-10:1, the volume of the added ethyl acetate after the reaction is 3-4 times of the total volume of the reaction liquid, and the organic layer is stirred and washed for 3-4 times by using clear water with the volume being about 1 time of the volume of the reaction liquid.
The preparation steps of the step B are as follows:
adding the intermediate I and a solvent into a reaction bottle together, stirring and dissolving at room temperature, and then adding triphenylphosphine bromomethane. Cooling, adding strong base into the reaction liquid in batches to enable the Wittig reaction to occur. After the intermediate I is reacted, evaporating the solvent to dryness, adding water, extracting the product by using dichloromethane, and evaporating the dichloromethane to dryness to obtain an intermediate II.
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
The strong base used in the reaction system can be potassium tert-butoxide, sodium hydride and the like, and the ratio of the amount of the strong base to the substance of the substrate intermediate I is 1.2:1 to 1.5:1.
The preparation method of the ruthenium metal olefin metathesis catalyst is characterized in that the solvent used in the reaction in the step B can be methyl tert-butyl ether, diethyl ether or tetrahydrofuran, and the mass ratio of the solvent to the substrate intermediate I is 10:1-15: 1. The ratio of the amounts of triphenylphosphine bromomethane and intermediate I material was 1.0:1-1.5:1, the reaction temperature was maintained at-10-0 ℃.
The specific preparation steps of the step C are as follows:
dissolving the intermediate II in an ether solvent (methyl tert-butyl ether, diethyl ether, tetrahydrofuran or 1, 4-dioxane, etc.), and adding a reducing agent at low temperature (-10-0 ℃) to reduce a cyano group in the molecular structure of the intermediate II into an amino group. Wherein the reducing agent used can be borane tetrahydrofuran solution or lithium aluminum hydride, and the amount of the reducing agent used is 2-3 equivalent of the substrate intermediate II. After completion of the reaction, the reaction was quenched with dilute hydrochloric acid. The reduced product intermediate III was purified over a silica gel column using ethyl acetate as eluent: n-hexane 1:1.
The specific preparation steps of the step D are as follows:
adding the intermediate III prepared after reduction into a reactor, adding a solvent of dichloromethane, stirring and dissolving, then adding an acetylation reagent (acetyl chloride or acetic anhydride) and an organic base (triethylamine or diisopropylethylamine), and stirring and reacting. Wherein the reaction temperature is 0-10 ℃, the added acetylation reagent is 1.0-1.2 equivalents of intermediate III, and the added organic base is 1.3-1.5 equivalents of substrate intermediate III. Inverse direction
Washing the reaction solution with dilute hydrochloric acid after reaction, and drying to remove the solvent to obtain the required alkene ligand
Wherein, X1,X2＝F,Cl,Br,I,NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
The specific preparation steps of the step E are as follows:
catalyst precursor and alkene ligand required for preparing certain catalyst
Adding the mixture into a reactor, adding a solvent, stirring and dissolving, then adding the iodinated ketone, and stirring and reacting. After the catalyst precursor is reacted, filtering to remove inorganic salt solids, evaporating the solvent to dryness, and then recrystallizing and purifying the product to obtain the required novel ruthenium metal olefin polymerization catalyst;
wherein, X, Y ═ F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；Y＝O,S；
The mass ratio of the above-mentioned catalyst precursor and olefinic ligand is between 1:1 and 1:2.5, wherein the optimized ratio is 1: 1.2.
In the preparation method of the ruthenium metal olefin metathesis catalyst, the used solvent can be n-hexane, n-heptane, petroleum ether, toluene, chlorobenzene, tetrahydrofuran, dichloromethane and the like, and the optimized solvent is toluene and dichloromethane; solvent and procatalyst Grubbs added2ndIn a ratio of between 3ml:1g and 10ml:1g, the optimum ratio being 5ml:1 g.
The reaction temperature of the preparation method of the ruthenium metal olefin metathesis catalyst is between 30 and 50 ℃, and the reaction time is between 2 and 4 hours.
In the preparation method of the ruthenium metal olefin metathesis catalyst, before the final catalyst is separated out, the system needs to be cooled to 0-20 ℃, and after the system is placed for 1-2 hours, impurities precipitated in the system are filtered and removed. Then, the solvent is removed by reduced pressure distillation, and a benign solvent and a poor solvent are added for crystallization to obtain a final product, namely a dark green solid.
In the above method for producing a ruthenium metal olefin metathesis catalyst, the benign solvent to be added when the final product crystals are precipitated may be methylene chloride, chloroform or ethyl acetate, and the poor solvent may be methanol, ethanol or isopropanol.
The volume ratio of the benign solvent to the poor solvent in the crystallization of the final product is 1:5 to 1:20, wherein the optimized volume ratio is 1:10, and the ratio of the total volume of the solvent used for crystallization to the catalyst precursor used is 5ml:1g to 20ml:1 g.
According to the preparation method of the ruthenium metal olefin metathesis catalyst, the crystallization temperature required when crystals of a final product are precipitated is between 0 and 30 ℃, and the crystallization time is between 1 hour and 5 hours.
In addition, the invention also provides an application method of the ruthenium metal olefin metathesis catalyst, which is characterized in that: the ruthenium metal olefin metathesis catalyst is applied to olefin ring-closing metathesis reaction, and the substrate of the olefin ring-closing metathesis reaction is a diene compound.
Further, the application method of the ruthenium metal olefin metathesis catalyst provided by the invention also has the following characteristics: step A, dissolving a diene compound in a solvent, adding a ruthenium metal olefin metathesis catalyst into a reactor in batches under the condition of protecting gas, and carrying out olefin metathesis reaction at the temperature of 30-80 ℃;
and step B, after the reaction is finished, removing the solvent or obtaining a product by reduced pressure distillation.
The solvent can be n-hexane, n-heptane, petroleum ether, toluene, chlorobenzene, tetrahydrofuran, dichloromethane and the like, and the optimized solvent is an aromatic solvent or halogenated hydrocarbon, and toluene and dichloromethane are most preferable;
the specific method comprises the following steps: the metathesis catalyst is added in portions to the reactor under the condition of protecting bubbles such as nitrogen gas, and the ring closing metathesis reaction is promoted by heating the reactor and controlling the temperature. The completion of the reaction was monitored by TLC, and after completion of the reaction, the solvent was distilled off under reduced pressure. The product obtained by the reaction can also be purified under the condition of high vacuum and reduced pressure distillation.
Further, the application method of the ruthenium metal olefin metathesis catalyst provided by the invention also has the following characteristics: that is, the mass ratio of the above diene compound to the ruthenium metal olefin metathesis catalyst is 1000:0.1 to 0.3. The concentration of the above catalyst solution is 0.1 to 1 g/L.
Further, the application method of the ruthenium metal olefin metathesis catalyst provided by the invention also has the following characteristics: that is, the above diene compound is a compound represented by the following structure:
further, the application method of the ruthenium metal olefin metathesis catalyst provided by the invention is applied to catalyzing dicyclopentadiene to perform ring-opening metathesis polymerization reaction, and the specific application method is as follows: adding dicyclopentadiene into a polymerization container, dissolving a catalyst in a solvent, dropwise adding the catalyst into dicyclopentadiene, and stirring the catalyst solution uniformly while dropwise adding. Then the stirring is stopped and the catalyst is initiated by heating to catalyze the polymerization of dicyclopentadiene.
The solvent can be n-heptane, toluene, chlorobenzene, acetone, isopropanol, dioxane, tetrahydrofuran, dichloromethane, dichloroethane, etc., and the optimized solvent is aromatic solvent or halogenated hydrocarbon, and most preferably toluene and dichloromethane;
further, the application method of the ruthenium metal olefin metathesis catalyst provided by the invention also has the following characteristics: namely, the mass ratio of the dicyclopentadiene to the ruthenium metal olefin metathesis catalyst is 1000:0.1-0.55, the heating temperature for initiating the catalyst to catalyze the polymerization of the dicyclopentadiene is 50-70 ℃, and the polymerization initiation time is 5-10 minutes.
The invention has the following functions and effects:
the invention selects simple and easily obtained substituted salicylaldehyde as a raw material, designs and prepares a series of alkene ligand ruthenium catalysts with different substituents, and the activity of the catalyst is determined by different substituents, thereby providing a plurality of choices for the application of the catalyst in catalyzing a diene substrate to carry out ring closing metathesis reaction.
In addition, a series of ruthenium metal catalysts are used for catalyzing a diene substrate to perform ring closing metathesis reaction and catalyzing dicyclopentadiene to perform ring opening metathesis polymerization reaction, so that the catalyst is high in activity, small in catalyst dosage, good in tolerance to various functional groups, simple and clean in reaction and simple in post-treatment, and can be used for large-scale production of various macrocyclic drug molecules and super-performance high polymer materials.
Detailed Description
Example 1
Comprises the following five steps:
A. optionally substituted salicylaldehyde
The intermediate I is obtained by protecting the exposed hydroxyl in salicylaldehyde molecules through the reaction with bromoacetonitrile, and the structural formula of the intermediate I is as follows:
intermediate I
To a 2L reaction flask were added 200g of 3-methylsalicylaldehyde and 1L N, N-dimethylformamide, and the mixture was dissolved with stirring. Then, 200g of bromoacetonitrile and 100g of potassium carbonate were slowly added to the reaction flask, and the reaction was continued with stirring after heating to 60 ℃. After completion of the reaction of the starting material as monitored by TLC, the reaction solution was poured into 4L of ethyl acetate and washed three times with water under stirring, 4L of water being added each time. After drying with anhydrous sodium sulfate, filtration and complete removal of the solvent under reduced pressure, 240g of crude product were obtained in 75% yield.
B. And C, reacting the intermediate I prepared in the step A with a Wittig reagent to obtain an olefin intermediate II, wherein the structural formula of the olefin intermediate II is as follows:
intermediate II
Protecting salicylaldehyde intermediate I
250g and triphenylphosphine bromide 400g were added together in a 10L reaction flask, and then solvent tetrahydrofuran 5L was added. After cooling to 0 ℃, 100g of potassium tert-butoxide is slowly added in portions. After the reaction, the solvent was removed under reduced pressure, and 5L of water was added for dissolution. Extracting with 10L dichloromethane, drying with anhydrous sodium sulfate, filtering, evaporating to remove solvent to obtain alkene ligand crude product, and purifying by reduced pressure distillation to obtain intermediate II
210g of yellow oily liquid, 88% yield.
C. Reducing the cyano group in the intermediate II prepared in the step B into amino group by using a reducing agent to obtain an intermediate III with the structure of
Intermediate III
Subjecting intermediate II
500g is added into 5L of dried tetrahydrofuran, and then 100g of lithium aluminum hydride powder is added into the system slowly in batches at 0 ℃ under the protection of nitrogen. After the addition, the temperature is raised to room temperature, the mixture is stirred and reacts for 5 hours, and then the TLC detects that the reaction of the raw materials is finished. The reaction was quenched with water and ethyl acetate at 0 ℃ and filtered to remove solids. After tetrahydrofuran is removed by distillation under reduced pressure, the product is extracted by ethyl acetate. After the solvent is evaporated by separating, the product is separated and purified by silica gel column chromatography to obtain 410 g of pure product with 90% yield.
D. Protecting amino group in the intermediate III prepared in the step C by acetyl to obtain the required alkene ligand, wherein the structural formula is shown in the specification
Reacting the intermediate III
200g was dissolved in 1L of methylene chloride, 90 g of triethylamine and 80g of acetyl chloride were added at 0 ℃ and the reaction was stirred for 2 hours, and then the organic layer was washed 3 times with a saturated aqueous ammonium chloride solution. The separated liquid is dried and dried to obtain 230g of the required alkene ligand with the yield of 90 percent.
The specific preparation steps of step E are as follows:
catalyst precursor 620g and olefinic ligand
340g of the mixture is added into a 10L reactor, 5L of solvent dichloromethane is added, 150g of cuprous chloride is added, the mixture is heated and reacted at 30 ℃ under the protection of nitrogen until the raw materials disappear, the mixture is cooled to room temperature, and impurities are filtered out. After toluene is removed from the filtrate by reduced pressure distillation, 100mL of dichloromethane and 5L of methanol are added to precipitate the product catalyst solid, and the final catalyst is obtained after filtration and drying
330g, yield 65%.
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ＝11.17(s,1H),8.04(s,1H),7.70(s,1H),7.44(s,1H),6.76(s,4H),5.34(m,1H),3.83(s,1H),3.51(m,2H),3.33(m,2H),3.22(s,4H),2.34(s,3H),2.66(s,3H),2.22(s,12H),1.35(d,J＝7.8Hz,6H)ppm.
The specific implementation steps of the ruthenium catalyst for catalyzing diene to carry out ring closing metathesis reaction are as follows: a500 mL reactor was charged with 10g of diene substrate. Preparing a dichloromethane solution of the catalyst, dissolving 100mg of catalyst solid in 10mL of dichloromethane, uniformly stirring, and adding a certain amount of the catalyst solid into the reaction solution. Heating the reactor to 40 ℃, blowing nitrogen bubbles into the solution of the reactor and discharging, evaporating the solvent after TLC detection reaction is finished, and distilling under reduced pressure in high vacuum to obtain a pure product.
The following table shows the case where the catalyst catalyzes the ring closing metathesis reaction of various diene substrates:
example 2
Comprises the following five steps:
A. optionally substituted salicylaldehyde
The intermediate I is obtained by protecting the exposed hydroxyl in salicylaldehyde molecules through the reaction with bromoacetonitrile, and the structural formula of the intermediate I is as follows:
intermediate I
To a 2L reaction flask, 200g of substituted salicylaldehyde and 1L of DMSO were added and dissolved with stirring. To the reaction flask were then slowly added 250g of bromoacetonitrile and 100g of potassium carbonate, and the reaction was continued with stirring after heating to 80 ℃. After completion of the reaction of the starting material as monitored by TLC, the reaction solution was poured into 4L of ethyl acetate and washed three times with water under stirring, 4L of water being added each time. After drying with anhydrous sodium sulfate, filtration and removal of the solvent under reduced pressure, 265g of crude product was obtained.
B. And C, reacting the intermediate I prepared in the step A with a Wittig reagent to obtain an olefin intermediate II, wherein the structural formula of the olefin intermediate II is as follows:
intermediate II
Protecting salicylaldehyde intermediate I
265g and 450g of triphenylphosphine bromomethane were added together in a 10L reaction flask, and 5L of dioxane solvent was added. After cooling to 0 ℃, 120g of potassium tert-butoxide is slowly added in portions. After the reaction, the solvent was removed under reduced pressure, and 5L of water was added for dissolution. Extracting with 10L chloroform, drying with anhydrous sodium sulfate, filtering, evaporating to remove solvent to obtain alkene ligand crude product, and purifying by vacuum distillation to obtain intermediate II
C. Reducing the cyano group in the intermediate II prepared in the step B into amino group by using a reducing agent to obtain an intermediate III with the structure of
Intermediate III
Subjecting intermediate II
500g is added to 4L of dried tetrahydrofuran, then 100g of sodium borohydride (dissolved in 1L of tetrahydrofuran) is slowly added to the system in portions at 0 ℃ under the protection of nitrogen. After the addition, the temperature is raised to room temperature, the mixture is stirred and reacts for 5 hours, and then the TLC detects that the reaction of the raw materials is finished. The reaction was quenched with water and ethyl acetate at 0 ℃ and filtered to remove solids. After tetrahydrofuran is removed by distillation under reduced pressure, the product is extracted by ethyl acetate. After the solvent is evaporated by separating liquid, the product is separated and purified by silica gel column chromatography to obtain 460 g of pure product.
D. Protecting amino group in the intermediate III prepared in the step C by acetyl to obtain the required alkene ligand, wherein the structural formula is shown in the specification
Reacting the intermediate III
200g was dissolved in 1L of methylene chloride, 120g of diisopropylethylamine and 100g of acetyl chloride were added at 0 ℃ and the reaction was stirred for 3 hours, and then the organic layer was washed 3 times with a saturated aqueous ammonium chloride solution. The mixture is separated, dried and dried to obtain 245 g of the required alkene ligand.
The specific preparation steps of step E are as follows:
680g of catalyst precursor and an olefinic ligand
340g of the mixture is added into a 10L reactor, 5L of solvent dichloromethane is added, 150g of cuprous chloride is added, the mixture is heated and reacted at 60 ℃ under the protection of nitrogen until the raw materials disappear, the mixture is cooled to room temperature, and impurities are filtered out. After toluene is removed from the filtrate by reduced pressure distillation, 100mL of dichloromethane and 5L of methanol are added to precipitate the product catalyst solid, and the final catalyst is obtained after filtration and drying
361g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ＝11.37(s,1H),8.10(s,1H),7.70(s,2H),6.84(s,2H),6.76(s,4H),5.42(s,2H),4.10(t,2H),3.51(t,2H),2.87(m,4H),2.15(s,3H),1.84(s,3H),1.20(d,24H)ppm.
The specific implementation steps of the ruthenium catalyst for catalyzing diene to carry out ring closing metathesis reaction are as follows: a500 mL reactor was charged with 10g of diene substrate. Preparing a dichloromethane solution of the catalyst, dissolving 100mg of catalyst solid in 10mL of dichloromethane, uniformly stirring, and adding a certain amount of the catalyst solid into the reaction solution. Heating the reactor to 60 ℃, blowing nitrogen bubbles into the solution of the reactor and discharging, evaporating the solvent after TLC detection reaction is finished, and distilling under reduced pressure in high vacuum to obtain a pure product.
The following table shows the case where the catalyst catalyzes the ring closing metathesis reaction of various diene substrates:
examples 3,
To a 2L reaction flask were added 200g of 3-methyl-4-methoxy-salicylaldehyde and 1L of DMF, and the mixture was dissolved with stirring. Then, 200g of 2-methylbromoacetonitrile and 100g of sodium carbonate were slowly added to the reaction flask, and the reaction was continued with stirring after heating to 40 ℃. After completion of the reaction of the starting materials as monitored by TLC, the reaction solution was poured into 4L of methyl acetate and washed three times with water under stirring, 4L of water being added each time. After drying with anhydrous sodium sulfate, filtration and complete removal of the solvent under reduced pressure, 260g of crude intermediate I product was obtained.
The protected salicylaldehyde intermediate I, 260g and triphenylphosphine bromomethane 500g were added together in a 10L reaction flask, followed by toluene solvent 5L. After cooling to 0 ℃ and slowly adding 150g of sodium tert-butoxide in portions. After the reaction, the solvent was removed under reduced pressure, and 5L of water was added for dissolution. Extracting with 10L chloroform, drying with anhydrous sodium sulfate, filtering, evaporating to remove solvent to obtain alkene ligand crude product, and purifying by vacuum distillation to obtain intermediate II
240g。
Subjecting intermediate II
500g is added into 5L of dried tetrahydrofuran, and then 100g of lithium aluminum hydride powder is added into the system slowly in batches at 0 ℃ under the protection of nitrogen. After the addition, the temperature is raised to room temperature, the mixture is stirred and reacts for 6 hours, and then the TLC detects that the reaction of the raw materials is finished. The reaction was quenched with water and ethyl acetate at 0 ℃ and filtered to remove solids. After tetrahydrofuran is removed by distillation under reduced pressure, the product is extracted by ethyl acetate. Separating and evaporating the solvent, and separating and purifying the product by silica gel column chromatography to obtain a pure product
435 g.
Reacting the intermediate III
200g was dissolved in 1L of methylene chloride, 90 g of triethylamine and 80g of acetyl chloride were added at 0 ℃ and the reaction was stirred for 4 hours, and then the organic layer was washed 3 times with a saturated aqueous ammonium chloride solution. The mixture is separated, dried and dried to obtain 245 g of the required alkene ligand.
700g of catalyst precursor and olefinic ligand
Adding 350g of the mixture into a 10L reactor, adding 5L of chloroform serving as a solvent, adding 150g of cuprous chloride, heating to react at 50 ℃ under the protection of nitrogen until the raw materials disappear, cooling to room temperature, and filtering out impurities. Evaporating the filtrate under reduced pressure to remove toluene, adding 100mL of chloroform and 1L of ethanol to precipitate a product catalyst solid, filtering and drying to obtain a final catalyst
369g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ＝12.07(s,1H),8.03(s,1H),6.90(s,1H),6.71(s,4H),6.66(s,1H),6.76(s,4H),4.49(m,1H),3.83(s,3H),3.61(m,2H),3.24(s,4H),2.34(s,6H),2.15(s,3H),2.12(s,3H),1.84(s,3H),1.40(d,24H)ppm.
Ruthenium metal olefin complexes Application of decomposition catalyst No. 3
The specific implementation steps of the ruthenium catalyst for catalyzing diene to carry out ring closing metathesis reaction are as follows: a1000 mL reactor was charged with 10g of diene substrate. Preparing a toluene solution of the catalyst, dissolving 300mg of catalyst solid in 60mL of toluene, uniformly stirring, and adding a certain amount of the catalyst solid into a reaction solution. Heating the reactor to 80 ℃, blowing nitrogen bubbles into the solution of the reactor and discharging, evaporating the solvent after TLC detection reaction is finished, and distilling under reduced pressure in high vacuum to obtain a pure product.
The following table shows the case where the catalyst catalyzes the ring closing metathesis reaction of various diene substrates:
examples 4,
To a 2L reaction flask were added 200g of p-phenylsalicylaldehyde and 1L N, N-dimethylformamide, and the mixture was dissolved with stirring. To the reaction flask were added slowly 300g of bromoacetonitrile and 150g of potassium carbonate, and after completion of the reaction at room temperature until TLC monitoring of the starting materials, the reaction solution was poured into 4L of ethyl acetate/chloroform (80/20), and washed with water with stirring three times, 4L of water was added each time. Adding anhydrous sodium sulfate, drying, filtering, and removing solvent under reduced pressure to obtain the final product
265g of crude product.
Protecting salicylaldehyde intermediate I
250g of this solution and 300g of triphenylphosphine bromomethane were put together in a 10L reaction flask, and 5L of tetrahydrofuran was added as a solvent. After cooling to 0 ℃, 130g of potassium tert-butoxide is slowly added in portions. After the reaction, the solvent was removed under reduced pressure, and 5L of water was added for dissolution.Extracting with 10L dichloromethane, drying with anhydrous sodium sulfate, filtering, evaporating to remove solvent to obtain alkene ligand crude product, and purifying by reduced pressure distillation to obtain intermediate II
225g of oily liquid.
Subjecting intermediate II
500g is added into 5L of dried tetrahydrofuran, and then 120g of lithium aluminum hydride powder is added into the system slowly in batches at 0 ℃ under the protection of nitrogen. After the addition, the temperature is raised to room temperature, the mixture is stirred and reacts for 5 hours, and then the TLC detects that the reaction of the raw materials is finished. The reaction was quenched with water and ethyl acetate at 0 ℃ and filtered to remove solids. After tetrahydrofuran is removed by distillation under reduced pressure, the product is extracted by ethyl acetate. After the solvent is evaporated by separating, the product is separated and purified by silica gel column chromatography to obtain 435 g of pure product.
Reacting the intermediate III
200g was dissolved in 1L of methylene chloride, 130g of triethylamine and 250g of acetic anhydride were added thereto at 0 ℃ and the mixture was stirred to react for 5 hours, and then the organic layer was washed 3 times with a saturated aqueous ammonium chloride solution. The solution is separated, dried and dried to obtain 230g of the required alkene ligand.
Mixing 600g of catalyst precursor and alkene ligand
Adding 400g of the mixture into a 10L reactor, adding 5L of solvent dichloromethane, adding 180g of cuprous chloride, heating to react at 30 ℃ under the protection of nitrogen until the raw materials disappear, cooling to room temperature, and filtering out impurities. After toluene is removed from the filtrate by reduced pressure distillation, 100mL of dichloromethane and 5L of methanol are added to precipitate the product catalyst solid, and the final catalyst is obtained after filtration and drying
360g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ＝12.01(s,1H),8.13(s,1H),7.80(s,1H),7.68(d,1H),7.51(m,4H),7.41(d,1H),7.05(d,1H),6.66(s,4H),5.43(s,2H),4.10(t,2H),3.53(t,2H),2.34(s,6H),2.12(s,12H),1.84(s,3H)ppm.
The specific implementation steps of the ruthenium catalyst for catalyzing diene to carry out ring closing metathesis reaction are as follows: a500 mL reactor was charged with 10g of diene substrate. Preparing a dichloromethane solution of the catalyst, dissolving 150mg of catalyst solid in 10mL of dichloromethane, uniformly stirring, and adding a certain amount of the catalyst solid into the reaction solution. Heating the reactor to 40 ℃, blowing nitrogen bubbles into the solution of the reactor and discharging, evaporating the solvent after TLC detection reaction is finished, and distilling under reduced pressure in high vacuum to obtain a pure product.
Examples 5,
To a 2L reaction flask were added 100g of p-2-thiosalicylaldehyde and 1L N, N-dimethylformamide, and the mixture was dissolved with stirring. To the reaction flask were added 120g of bromoacetonitrile and 80g of potassium carbonate slowly, and after completion of the reaction of the starting materials monitored by TLC at room temperature, the reaction mixture was poured into 4L of ethyl acetate and washed three times with saturated saline solution, 4L of saturated saline solution was added each time. Adding anhydrous sodium sulfate, drying, filtering, and removing solvent under reduced pressure to obtain the final product
155g of crude product.
Protecting salicylaldehyde intermediate I
155g of this solution and 180g of triphenylphosphine bromomethane were put together in a 5L reaction flask, and 2L of tetrahydrofuran was added as a solvent. After cooling to 0 ℃, 130g of potassium tert-butoxide is slowly added in portions. After the reaction, the solvent was removed under reduced pressure, and 1L of water was added for dissolution. Extracting with 10L dichloromethane, drying with anhydrous sodium sulfate, filtering, evaporating to remove solvent to obtain alkene ligand crude product, and purifying by reduced pressure distillation to obtain intermediate II
120g of oily liquid.
Subjecting intermediate II
100g of the lithium aluminum hydride powder is added into 1L of dried tetrahydrofuran, and 50g of lithium aluminum hydride powder is slowly added into the system in batches at 0 ℃ under the protection of nitrogen. After the addition, the temperature is raised to room temperature, the mixture is stirred and reacts for 5 hours, and then the TLC detects that the reaction of the raw materials is finished. The reaction was quenched with water and ethyl acetate at 0 ℃ and filtered to remove solids. After tetrahydrofuran is removed by distillation under reduced pressure, the product is extracted by ethyl acetate. After the solvent was evaporated, the product was purified by silica gel column chromatography to obtain 105 g of pure product.
Reacting the intermediate III
100g was dissolved in 1L of methylene chloride, 60g of triethylamine and 90 g of acetic anhydride were added thereto at 0 ℃ and the mixture was stirred to react for 5 hours, and then the organic layer was washed 3 times with a saturated aqueous ammonium chloride solution. 120g of the required alkene ligand is obtained after liquid separation, drying and spin drying.
300g of catalyst precursor and olefinic ligand
Adding 100g of the mixture into a 10L reactor, adding 5L of solvent dichloromethane, adding 60g of cuprous chloride, heating to react at 30 ℃ under the protection of nitrogen until the raw materials disappear, cooling to room temperature, and filtering out impurities. The toluene was distilled off from the filtrate under reduced pressure, 100mL of methylene chloride and 1.5L of methanol were added to precipitate a solid product as a catalyst, which was then filteredDrying to obtain the final catalyst
160g。
1H NMR(300.18MHz,22℃,CDCl3,Me4Si):δ＝11.01(s,1H),8.03(s,1H),6.69(m,4H),3.54(t,2H),3.41(t,2H),3.29(s,4H),2.37(s,6H),2.10(s,12H),1.80(s,3H)ppm.
The specific implementation steps of the ruthenium catalyst for catalyzing diene to carry out ring closing metathesis reaction are as follows: a500 mL reactor was charged with 10g of diene substrate. Preparing a dichloromethane solution of a catalyst (the mass ratio of the diene compound to the catalyst is selected within the range of 1000: 0.1-0.3), dissolving 120mg of catalyst solid in 10mL of dichloromethane, uniformly stirring, and adding a certain amount of the catalyst solid into a reaction solution. Heating the reactor to 40 ℃, blowing nitrogen bubbles into the solution of the reactor and discharging, evaporating the solvent after TLC detection reaction is finished, and distilling under reduced pressure in high vacuum to obtain a pure product.
The reaction data for different catalyst amounts and different diene substrates are as follows:
Adding 10g of dicyclopentadiene into a polymerization container, dissolving a catalyst (the mass ratio of the dicyclopentadiene to the catalyst is selected within the range of 1000: 1-5) in 10ml of dichloromethane, dropwise adding the catalyst into the dicyclopentadiene, stirring the catalyst solution uniformly while dropwise adding the catalyst, stopping stirring, and heating to initiate the catalyst to catalyze the polymerization of the dicyclopentadiene.
The data for the catalyzed dicyclopentadiene polymerization are shown in the following table:
Claims (3)
1. a preparation method of a ruthenium metal olefin metathesis catalyst is characterized in that the preparation process is realized by the following steps:
step 1-1, adding substituted salicylaldehyde or substituted 2-thiosalicylaldehyde, a solvent, alkali and a nitrile compound into a reactor, uniformly stirring at room temperature, and reacting at the temperature of 20-80 ℃ for 0.5-20 hours;
step 1-2, extracting the reaction solution, and removing the solvent of an organic phase to obtain an intermediate I;
step 2-1, dissolving the intermediate I in a solvent, adding triphenylphosphine bromomethane, cooling, adding alkali into the reaction solution in batches, and reacting at the temperature of-10-120 ℃ for 0.5-20 hours to complete the Wittig reaction;
step 2-2, after the intermediate I finishes the reaction, removing the solvent, adding water, extracting the reaction solution, and removing the solvent of an organic phase to obtain an intermediate II;
step 3-1, dissolving the intermediate II in a solvent, adding a reducing agent at a low temperature of below 0 ℃, reacting at a temperature of between 10 ℃ below zero and 120 ℃ for 0.5 to 20 hours, and reducing cyano groups into amino groups;
step 3-2, after the reaction is finished, quenching the reaction by using acid, and carrying out column chromatography to obtain an intermediate III;
3-3, dissolving the intermediate III in a solvent, adding an acetylation reagent and alkali, and reacting at the temperature of 0-10 ℃ for 0.5-20 hours to perform amidation reaction;
step 3-4, after the reaction is finished, quenching the reaction by using acid, and drying to remove the solvent to obtain an alkene ligand;
step 4-1, dissolving a catalyst precursor and an alkene ligand in a solvent, adding a catalyst, and reacting for 2-4 hours at the temperature of 30-50 ℃;
4-2, filtering out solids, removing the solvent, and recrystallizing to obtain the target catalyst;
wherein the base is selected from sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, diisopropylethylamine, potassium tert-butoxide, sodium hydride, potassium hydride;
wherein, the specific structural formula of the target catalyst is shown as follows:
wherein R is1Hydrogen, alkyl, aryl;
R2hydrogen, alkyl, aryl;
R3hydrogen, alkyl, aryl;
R4hydrogen, alkyl, aryl;
R5hydrogen, alkyl, aryl;
R1' is hydrogen, alkyl, aryl;
R2' is hydrogen, alkyl, aryl;
R3' is hydrogen, alkyl, aryl;
R4' is hydrogen, alkyl, aryl;
R5' is hydrogen, alkyl, aryl;
R7is methyl;
l is halogen;
y is oxygen or sulfur;
Z1is halogen, nitryl, amino, aryl, alkyl or alkoxy substituted on any or several of benzene rings;
Z2hydrogen, alkyl, aryl;
the structure of the nitrile compound is shown as follows:
the structural formula of the intermediate I is shown as follows:
the structural formula of the intermediate II is shown as follows:
the structural formula of the intermediate III is shown as follows:
2. a method of preparing a ruthenium metal olefin metathesis catalyst as claimed in claim 1 wherein:
the solvent is selected from nitrile solvents, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, ether solvents, alkane solvents, toluene, chlorobenzene and alkyl halides;
the acid is an inorganic acid;
the reagent for extraction is selected from esters, ethers, halogenated hydrocarbons and toluene;
the molar ratio of the substituted salicylaldehyde to the alkali to the nitrile compound is 1:1.0-2.5: 1.0-2.5;
the molar ratio of the intermediate I, the alkali and the triphenylphosphine bromomethane is 1:1.0-2.5: 1.0-2.5;
the molar ratio of the intermediate II to the reducing agent is 1: 2-3;
the molar ratio of the intermediate III to the acetylation reagent to the alkali is 1:1.0-2.5: 1.0-2.5;
the molar ratio of the catalyst precursor to the alkene ligand is 1: 1-2.5.
3. A method of preparing a ruthenium metal olefin metathesis catalyst as claimed in claim 1 wherein:
the ruthenium metal olefin metathesis catalyst is a compound represented by one of the following structures:
wherein, X is1Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt；
Said X2Selected from F, Cl, Br, I, NO2,Ph,Me,Et,OMe,OEt。
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| CN107641165B (en) * | 2017-08-08 | 2020-05-08 | 上海克琴科技有限公司 | Ruthenium metal catalyst DREAM-2nd and application thereof in olefin ring-closing metathesis and dicyclopentadiene polymerization reaction |
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| CN111732681B (en) * | 2020-07-02 | 2022-03-18 | 张玉清 | Bi-component latent metal carbene catalytic system, dicyclopentadiene polymeric bi-material system and polydicyclopentadiene composite material |
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Denomination of invention: Preparation and application of a ruthenium metal olefin metathesis catalyst Effective date of registration: 20231218 Granted publication date: 20200320 Pledgee: Industrial Bank Co.,Ltd. Shanghai Jinshan Branch Pledgor: SHANGHAI COACHCHEM TECHNOLOGY CO.,LTD. Registration number: Y2023980071859 |