Imidazole coordinated ruthenium carbene olefin metathesis catalyst and preparation and application thereof

Abstract

The invention discloses an imidazole coordinated ruthenium carbene olefin metathesis catalyst, which is shown as a formula (I): # imgabs0 #, in which R is selected from benzyl, 2, 4, 6-trimethylphenyl or methyl. The invention also discloses a preparation method and application thereof. The method provided by the invention is simple in steps and mild in required conditions.

Description

Technical Field

[0001] The invention relates to an imidazole coordinated ruthenium carbene olefin metathesis catalyst and the preparation and application thereof. Background Art

[0002] Unsaturated octadecane dicarboxylic acid dimethyl ester is an important chemical raw material, which has important applications in the synthesis of high-grade lubricating oil, high-grade nylon and high-grade fragrance. The most efficient way to synthesize unsaturated octadecane dicarboxylic acid dimethyl ester is to obtain 9-decenoic acid methyl ester through the ethylene decomposition of methyl oleate or directly obtain unsaturated octadecane dicarboxylic acid dimethyl ester. This reaction is a special case of olefin metathesis reaction.

[0003] Since the 1990s, ruthenium metal olefin metathesis catalysts have developed very rapidly. The most representative and epoch-making one is the catalyst developed by the Grubbs research group with alkyl phosphine and halogen atoms as ligands. This type of catalyst is called the Grubbs first-generation catalyst. It is stable in air, has high catalytic activity, and has good functional group compatibility. It is a very classic catalyst structure. In 1999, Grubbs et al. modified the first-generation catalyst. A tricyclohexylphosphine ligand in its structure was replaced by a larger sterically hindered and electron-donating N-heterocyclic carbene (NHC) ligand to obtain a new catalyst structure, which was later called the Grubbs II catalyst. The catalytic activity of Grubbs II is two orders of magnitude higher than that of Grubbs I, which greatly reduces the amount of catalyst used in the catalytic reaction. In addition, this type of catalyst has high thermal stability and better compatibility with functional groups. After that, the Grubbs research group used pyridine to exchange the tricyclohexylphosphine ligand in the Grubbs II catalyst, and obtained the Grubbs III catalyst with a high initiation rate containing two pyridines. In 2009, Hoveyda et al. prepared a phenolic oxygen chelated ruthenium carbene complex based on the Grubbs I catalyst, which has obvious activity and good stability and can be used for large-scale preparation of various olefin compounds. Moreover, this catalyst is recyclable and can be recovered by simple chromatography after the reaction. This is the first recyclable olefin metathesis catalyst. It can efficiently catalyze homogeneous olefin metathesis reactions and has no loss of activity when reused. This catalyst was later called the Hoveyda-Grubbs I catalyst. In 2010, based on the Grubbs II catalyst, the Hoveyda research group successfully developed the Hoveyda-Grubbs II catalyst. Compared with other ruthenium catalysts before, this type of catalyst has a higher initiation rate and stability (air stability), and the reaction conditions are relatively mild. It can obtain a high yield at room temperature and has high catalytic activity for electron-deficient olefins such as acrylonitrile and fluoroolefins. Most importantly, this type of catalyst can be immobilized by chemical and physical methods and then recovered, and the recovery efficiency is very high.

[0004] However, in the ethylene decomposition reaction of methyl oleate, these types of catalysts did not perform well and could not meet the requirements of industrialization. In 2014, Grubbs' research group discovered a new type of mononitrogen ring carbene (CAAC) ruthenium catalyst, which changed the nitrogen heterocyclic carbene ligand of the traditional catalyst and replaced one of the nitrogen atoms with a carbon atom, which has great advantages for such reactions. Its products are mainly 9-decenoic acid methyl ester and 9-decenoic acid, and the selectivity of the products for these two compounds is as high as more than 95%, and the selectivity for 9-octadecenedioic acid dimethyl ester is very low. However, this type of catalyst has weak activity for metathesis reactions such as cross- and ring-closing reactions. Therefore, if 9-octadecenedioic acid dimethyl ester is needed, it is necessary to use a traditional olefin metathesis catalyst to catalyze the cross-metathesis of 9-decenoic acid methyl ester. Therefore, this type of catalyst is also limited to basic research and has not been applied to industrial production. The Grubbs III type catalyst mainly produces 9-octadecenedioic acid dimethyl ester and 9-octadecene products in the ethylene reaction of methyl oleate, with a product selectivity of ≥97%, but a low catalytic activity. Therefore, it is of great significance to change the structure of the Grubbs III catalyst to increase the yield of the 9-octadecenedioic acid dimethyl ester product. Summary of the invention

[0005] In order to further improve the catalytic activity of Grubbs III catalyst, a series of studies were conducted and it was found that the reason for the low catalytic activity of Grubbs III catalyst is that the pyridine ligand of Grubbs III catalyst is easy to dissociate, and after dissociation, the methyl group on the trimethylphenyl of nitrogen heterocyclic carbene is easy to react with the Ru active center to obtain structure b. Structure b destroys the benzylic methylene carbene structure through proton transfer to obtain structure c. At this point, the catalyst has lost its catalytic activity. Structure c continues to remove the benzylic methylene structure and can form a stable inactive dimer with structure a. For details, please refer to the following diagram:

[0006]

[0007] Based on this discovery, it is proposed to use a ligand substituted pyridine with stronger coordination ability and more difficult to dissociate, to suppress the decomposition process of the catalyst, thereby significantly improving the stability and catalytic activity of the catalysis. The new catalyst provided by the invention has important application prospects in the catalytic conversion of unsaturated octadecane dicarboxylic acid dimethyl ester, 1-decene and 9-decenoic acid methyl ester. The new catalyst provided by the invention can also be controlled by adding a co-catalyst to its catalytic product structure, which is of great significance in practical applications.

[0008] Research has found that using imidazole to replace pyridine can achieve relatively good results. As a five-membered aromatic heterocyclic compound, imidazole has two double bonds and is rich in π electrons. In its molecular structure, the two nitrogen atoms are in the meta position. The nitrogen atom in the 1st position participates in the ring conjugation, which makes the hydrogen on it easily replaced by H+ The imidazole ring is weakly acidic because it leaves in the form of protons. The nitrogen atom at position 3 does not participate in the ring conjugation and can accept proton attack, so the imidazole ring also has a certain degree of alkalinity. The amphoteric nature of the imidazole ring can be explained by resonance. There are 6 electrons on the imidazole ring, which are delocalized between 5 atoms. Therefore, the electron cloud density of the imidazole ring is higher, and the alkalinity and coordination ability are stronger than pyridine. In addition, since the imidazole ring has both acidic and basic properties, when imidazole is used as a ligand, the two N atoms on the imidazole ring can serve as coordinating atoms to form a complex with other metals. First, when the imidazole ring acts as a neutral ligand, it can be coordinated through the nitrogen atom at position 1 to form a monodentate chelating ligand; second, when imidazole loses protons to become a negative monovalent imidazole salt, it can self-assemble with the transition metal through the two nitrogen atoms in the molecule to form a bidentate chelating ligand; third, the imidazole ring receives protons to form a positive monovalent imidazole salt, and the carbon atom at position 2 participates in the coordination. Therefore, the characteristics of imidazole under different conditions make the coordination mode of imidazole more diverse. The protonation and deprotonation of imidazole can be understood by referring to the following formula. For details, please refer to the following diagram:

[0009]

[0010] In the ring-closing metathesis process of olefins, the chemical selectivity of the catalyst can be controlled by adding 3-bromo-1-propyne to obtain a single catalytic product. First, when 3-bromo-1-propyne is not added, the substrate has a competitive reaction during the catalytic process, and the process is as follows:

[0011]

[0012] By adding 3-bromo-1-propyne, the structure and chemical selectivity of the product can be controlled. The mechanism is shown in the figure below:

[0013]

[0014] As one aspect of the present invention, it relates to an imidazole-coordinated ruthenium carbene olefin metathesis catalyst, as shown in formula (I):

[0015]

[0016] Wherein, R is selected from benzyl (Bn), 2,4,6-trimethylphenyl (Mes) or methyl (Me).

[0017] As another aspect of the present invention, it relates to a method for preparing the above-mentioned imidazole-coordinated ruthenium carbene olefin metathesis catalyst, comprising: in an organic solvent system, reacting a Grubbs II catalyst with a benzyl-substituted imidazole salt, a trimethylphenyl-substituted imidazole salt or a methyl-substituted imidazole salt.

[0018] In a specific embodiment, the method comprises: dissolving the Grubbs II catalyst in an organic solvent (such as dichloromethane, chloroform, tetrahydrofuran or toluene), adding a benzyl-substituted imidazole salt, a trimethylphenyl-substituted imidazole salt or a methyl-substituted imidazole salt to the reaction system at 10-60°C, preferably 30°C to 60°C.

[0019] In a specific embodiment, the molar ratio of the added benzyl-substituted imidazole salt, trimethylphenyl-substituted imidazole salt or methyl-substituted imidazole salt to the Grubbs II catalyst is 1:1-4:1, preferably 2:1-3:1.

[0020] In a specific embodiment, the benzyl-substituted imidazole salt is specifically N-benzylimidazole, the trimethylphenyl-substituted imidazole salt is specifically N-2,4,6-trimethylphenylimidazole, and the methyl-substituted imidazole salt is specifically N-methylimidazole.

[0021] In a specific embodiment, the method further comprises: after the reaction is completed, removing part of the solvent under reduced pressure, adding n-hexane, centrifuging, filtering and drying the precipitated product. In a specific embodiment, after adding the benzyl substituted imidazole salt, the trimethylphenyl substituted imidazole salt or the methyl substituted imidazole salt, the temperature is maintained for reaction for more than 2 hours.

[0022] The reaction process of the preparation method provided by the present invention is schematically shown as follows:

[0023]

[0024] Among them, Bn is benzyl; Mes is 2,4,6-trimethylphenyl; and Me is methyl.

[0025] As another aspect of the present invention, it relates to the use of the above-mentioned imidazole-coordinated ruthenium carbene olefin metathesis catalyst in the catalytic conversion of saturated octadecenedioic acid dimethyl ester, 1-decene, and 9-decenoic acid methyl ester.

[0026] As another aspect of the present invention, it relates to a catalytic conversion process of unsaturated octadecane dicarboxylic acid dimethyl ester, 1-decene, and 9-decenoic acid methyl ester, using the above-mentioned imidazole-coordinated ruthenium carbene olefin metathesis catalyst. In a specific embodiment, 3-bromo-1-propyne can also be added.

[0027] The method provided by the invention has simple steps and requires mild conditions.

[0028] In the ring-closing metathesis of olefins, the present invention can improve the catalytic efficiency and control the configuration of the product by adding 3-bromo-1-propyne.

[0029] The imidazole-coordinated ruthenium carbene olefin metathesis catalyst provided by the present invention has higher stability than the Grubbs III catalyst, and has a higher turnover number (TON) value for oleic acid methyl ethenolysis, and the catalytic activity is greatly improved. Figure 1 . BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 :The stability test results of the imidazole-coordinated ruthenium carbene olefin metathesis catalyst and Grubbs III catalyst provided by the present invention. The figure uses benzophenone as the internal standard at 40°C. 1 H NMR monitored the decomposition of Grubbs III, I, II, and III in THF-d8. The results showed that the stability of the catalyst was: II>I>III>Grubbs III. DETAILED DESCRIPTION

[0031] Synthesis of Ruthenium Complexes I-III

[0032] Example 1

[0033] Synthesis of ruthenium complex [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(pheny-lmethylene)bis(N-benzylimidazole)ruthenium(I):

[0034] Synthesis method 1: Add 0.42g (0.50mmol, 1.0equiv.) of Grubbs II catalyst to a round-bottom flask, add 20mL of organic solvent (such as toluene, tetrahydrofuran, acetonitrile, dichloromethane and ether, etc., which can be used to synthesize the target catalyst I) to dissolve it, heat the reaction system to 30°C, slowly add N-benzylimidazole salt (0.08g, 0.5mmol, 1.0equiv.), continue to react for 2h, the color of the mixture changes from reddish brown to brownish green, and the reaction progress is judged by TLC, and the reaction liquid is spotted on a silica gel plate to monitor the reaction progress (developing agent ratio PE:DCM=1:1). When the reaction is completed until the reaction of Grubbs II catalyst is completed, stop stirring. Put the flask on a rotary evaporator, under the water pump pressure (-0.1MPa), when the rotary evaporation water bath temperature is 24°C, evaporate 18mL of solvent, add an appropriate amount of n-hexane for ultrasonic oscillation, and solid precipitates. Add filter paper to the Buchner funnel and place it on a suction flask, which is connected to a water pump. Pour the reaction solution with solids into the Buchner funnel and filter out the solids. After the solids are rinsed with n-hexane (3×20 mL) in the Buchner funnel, collect the solids in a dry flask and use a vacuum pump to drain the solvent to obtain a green solid I (ruthenium complex I). The yield of the target compound is 33% when toluene is used as the solvent; the yield of the target compound is 41% when tetrahydrofuran is used as the solvent; the yield of the target compound is 26% when acetonitrile is used as the solvent; the yield of the target compound is 53% when dichloromethane is used as the solvent; and the yield of the target compound is 15% when ether is used as the solvent.

[0035] Synthesis method 2: 0.42 g (0.50 mmol, 1.0 equiv.) of Grubbs II catalyst was added to a round-bottom flask, and 20 mL of dichloromethane was added to dissolve it. After the reaction system was heated to 40°C, N-benzylimidazole salt (0.08 g, 0.5 mmol, 1.0 equiv., 0.16 g, 1.0 mmol, 2.0 equiv., 0.24 g, 1.5 mmol, 3.0 equiv., 0.32 g, 2.0 mmol, 4.0 equiv.) was slowly added, and the reaction was continued for 2 h. The color of the mixture changed from reddish brown to brownish green. The reaction progress was judged by TLC. The reaction liquid was spotted on a silica gel plate to monitor the reaction progress (developer ratio PE:DCM = 1:1). When the reaction was completed with the Grubbs II catalyst, stirring was stopped. The flask was placed on a rotary evaporator. Under water pump pressure (-0.1MPa), when the rotary evaporation water bath temperature was 24°C, 18mL of solvent was evaporated, and an appropriate amount of n-hexane was added for ultrasonic oscillation, and solids were precipitated. Filter paper was added to the Buchner funnel, and it was placed on a suction flask, and the suction flask was connected to a water pump. The reaction solution with solids was poured into the Buchner funnel to filter out the solids. After the solids were rinsed with n-hexane (3×20mL) in the Buchner funnel, the solids were collected in a dry flask, and the solvent was drained with a vacuum pump to obtain a green solid I (ruthenium complex I). When the amount of catalyst to N-benzyl imidazole salt is 1:1 (molar ratio), the yield of the catalyst is 53%; when the amount of catalyst to N-benzyl imidazole salt is 1:2 (molar ratio), the yield of the catalyst is 76%; when the amount of catalyst to N-benzyl imidazole salt is 1:3 (molar ratio), the yield of the catalyst is 74%; when the amount of catalyst to N-benzyl imidazole salt is 1:4 (molar ratio), the yield of the catalyst is 75%.

[0036] Synthesis method 3: Add 0.42g (0.50mmol, 1.0equiv.) of Grubbs II catalyst to a round-bottom flask, add 20mL of dichloromethane and dissolve it, heat the reaction system to a certain temperature (such as 10℃, 20℃, 30℃, 40℃, 50℃, 60℃), slowly add a certain proportion of N-benzylimidazole salt (.), continue the reaction for 2h, the color of the mixture changes from reddish brown to brownish green, and the reaction progress is judged by TLC, and the reaction liquid is spotted on a silica gel plate to monitor the reaction progress (developer ratio PE:DCM=1:1). When the reaction is completed with the Grubbs II catalyst, stop stirring. Put the flask on a rotary evaporator, under the pressure of a water pump (-0.1MPa), when the rotary evaporation water bath temperature is 24℃, evaporate 18mL of solvent, add an appropriate amount of n-hexane for ultrasonic oscillation, and solid precipitates. Add filter paper to the Buchner funnel, place it on a suction flask, and connect the suction flask to a water pump. Pour the reaction solution with solid into a Buchner funnel and filter out the solid. After the solid is rinsed with n-hexane (3×20 mL) in the Buchner funnel, collect the solid into a dry flask and use a vacuum pump to drain the solvent to obtain a green solid I (ruthenium complex I). The yield of the target product at 10°C is 34%; the yield of the target product at 20°C is 48%; the yield of the target product at 30°C is 64%, the yield of the target product at 40°C is 76%; the yield of the target product at 50°C is 72%, and the yield of the target product at 60°C is 55%.

[0037] After testing, the ruthenium complex I 1 H NMR (400 MHz, CDCl 3 ): δ19.15(s,1H),7.67(d,J=31.0Hz,3H),7.44(t,J=7.4Hz,1H),7.30(s,4H),7.16(s,4H),7.06(d,J=7.2Hz,4H ),6.99-6.59(m,8H),6.38(s,1H),5.02(s,2H),4.75(s,2H),4.00(s,4H),2.56(d,J=35.0Hz,6H),2.24(s,12H). 13 C NMR (101 MHz, CDCl 3 )δ219.47,152.51,138.69,137.42,136.40,135.56,130.35,128.80,128.73,128.58, 128.10,127.93,127.49,127.25,126.66,117.60,51.50,50.84,21.10,19.35,19.06.

[0038] The structural formula of the obtained product, ruthenium complex I, is shown in formula (I), wherein R is benzyl (Bn).

[0039] Example 2

[0040] Ruthenium complex [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolyl]dichloro(benzylidene)bis(N-(2,4,6-trimethylphenyl)imidazole)ruthenium

[0041] Synthesis of [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylmethylene)bis(N-(2,4,6-trimethylphenyl)imidazole)ruthenium(II):

[0042] Synthesis method 1: Add 0.42g (0.50mmol, 1.0equiv.) of Grubbs II catalyst to a round-bottom flask, add 20mL of organic solvent (such as toluene, tetrahydrofuran, acetonitrile, dichloromethane and ether, etc., which can be used to synthesize the target catalyst I) to dissolve it, heat the reaction system to 50°C, slowly add N-2,4,6-trimethylphenyl imidazole salt (0.095g, 0.5mmol, 1.0equiv.), continue to react for 2h, the color of the mixture changes from reddish brown to brownish green, and the reaction progress is judged by TLC, and the reaction liquid is spotted on a silica gel plate to monitor the reaction progress (developing agent ratio PE:DCM=1:1). When the reaction is completed until the Grubbs II catalyst reacts, stop stirring. Put the flask on a rotary evaporator, under the water pump pressure (-0.1MPa), when the rotary evaporation water bath temperature is 24°C, evaporate 18mL of solvent, add an appropriate amount of n-hexane for ultrasonic oscillation, and solid precipitates. Add filter paper to the Buchner funnel and place it on a suction flask, which is connected to a water pump. Pour the reaction solution with solids into the Buchner funnel and filter out the solids. After the solids are rinsed with n-hexane (3×20 mL) in the Buchner funnel, collect the solids in a dry flask and use a vacuum pump to drain the solvent to obtain a green solid II (ruthenium complex II). The yield of the target compound is 35% when toluene is used as the solvent; the yield of the target compound is 48% when tetrahydrofuran is used as the solvent; the yield of the target compound is 18% when acetonitrile is used as the solvent; the yield of the target compound is 57% when dichloromethane is used as the solvent; and the yield of the target compound is 12% when ether is used as the solvent.

[0043] Synthesis method 2: 0.42 g (0.50 mmol, 1.0 equiv.) of Grubbs II catalyst was added to a round-bottom flask, and 20 mL of dichloromethane was added to dissolve it. After the reaction system was heated to 40°C, N-2,4,6-trimethylphenylimidazole salt (0.095 g, 0.5 mmol, 1.0 equiv., 0.19 g, 1.0 mmol, 2.0 equiv., 0.285 g, 1.5 mmol, 3.0 equiv., 0.38 g, 2.0 mmol, 4.0 equiv.) was slowly added, and the reaction was continued for 2 h. The color of the mixture changed from reddish brown to brownish green. The reaction progress was judged by TLC. The reaction liquid was spotted on a silica gel plate to monitor the reaction progress (developer ratio PE:DCM = 1:1). When the reaction was completed with the Grubbs II catalyst, stirring was stopped. The flask was placed on a rotary evaporator. Under water pump pressure (-0.1MPa), when the temperature of the rotary evaporation water bath was 24°C, 18mL of solvent was evaporated, and an appropriate amount of n-hexane was added for ultrasonic oscillation, and solids were precipitated. Filter paper was added to the Buchner funnel, and it was placed on a suction flask, and the suction flask was connected to a water pump. The reaction solution with solids was poured into the Buchner funnel to filter out the solids. After the solids were rinsed with n-hexane (3×20mL) in the Buchner funnel, the solids were collected in a dry flask, and the solvent was drained with a vacuum pump to obtain a green solid II (ruthenium complex II). The yield of the catalyst when the amount of the catalyst followed by the N-2,4,6-trimethylphenylimidazolium salt is 1:1 (molar ratio) is 57%; the yield of the catalyst when the amount of the catalyst followed by the N-2,4,6-trimethylphenylimidazolium salt is 1:2 (molar ratio) is 77%; the yield of the catalyst when the amount of the catalyst followed by the N-2,4,6-trimethylphenylimidazolium salt is 1:3 (molar ratio) is 78%; the yield of the catalyst when the amount of the catalyst followed by the N-2,4,6-trimethylphenylimidazolium salt is 1:4 (molar ratio) is 74%.

[0044] Synthesis method 3: Add 0.42g (0.50mmol, 1.0equiv.) of Grubbs II catalyst to a round-bottom flask, add 20mL of dichloromethane to dissolve it, heat the reaction system to a certain temperature (such as 10℃, 20℃, 30℃, 40℃, 50℃, 60℃), slowly add a certain proportion of N-2,4,6-trimethylphenyl imidazole salt (such as 0.19g, 1mmol, 2.0equiv.), continue to react for 2h, the color of the mixture changes from reddish brown to brownish green, and the reaction progress is judged by TLC, and the reaction liquid is spotted on a silica gel plate to monitor the reaction progress (developer ratio PE:DCM=1:1). When the reaction is completed until the Grubbs II catalyst reacts, stop stirring. Put the flask on a rotary evaporator, under water pump pressure (-0.1MPa), when the rotary evaporation water bath temperature is 24℃, evaporate 18mL of solvent, add an appropriate amount of n-hexane for ultrasonic oscillation, and solid precipitates. Add filter paper to the Buchner funnel and place it on a suction flask, which is connected to a water pump. Pour the reaction solution with solids into the Buchner funnel and filter out the solids. After the solids are rinsed with n-hexane (3×20 mL) in the Buchner funnel, collect the solids in a dry flask and use a vacuum pump to drain the solvent to obtain a green solid II (ruthenium complex II). The yield of the target product is 38% at 10°C; the yield of the target product is 42% at 20°C; the yield of the target product is 59% at 30°C, and the yield of the target product is 77% at 40°C; the yield of the target product is 71% at 50°C, and the yield of the target product is 66% at 60°C.

[0045] After testing, the nuclear magnetic resonance of ruthenium complex II is: 1 H NMR (400 MHz, CDCl 3 )δ19.08(s,1H),7.67(d,J=7.7Hz,2H),7.61(s,1H),7.47(s,1H),7.41(t,J=7.3Hz,1H),7.23(s,1H),7.03(t,J=7.6Hz,2H),6.96(s ,3H),6.83(d,J=5.8Hz,7H),6.46(s,1H),4.06(s,4H),2.44(d,J=31.3Hz,8H),2.33(s,5H),2.26(s,11H),1.98(s,6H),1.70(s,6H). 13 C NMR (101 MHz, CDCl 3)δ219.44,152.27,139.00,138.75,138.60,138.28,137.90,137.59,135.04,134.89,130 .06,129.27,128.97,128.76,127.48,119.22,118.84,51.49,21.02,19.36,17.66,16.99.

[0046] The structural formula of the obtained product (ruthenium complex II) is shown in formula (I), wherein R is 2,4,6-trimethylphenyl (Mes).

[0047] Example 3

[0048] Synthesis of ruthenium complex [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phen-ylmethylene)bis(N-methylimidazole)ruthenium(III):

[0049] Synthesis method 1: Add 0.42g (0.50mmol, 1.0equiv.) of Grubbs II catalyst to a round-bottom flask, add 20mL of organic solvent (such as toluene, tetrahydrofuran, acetonitrile, dichloromethane and ether, etc., which can be used to synthesize the target catalyst I) to dissolve it, heat the reaction system to 40°C, slowly add methyl imidazole salt (0.075g, 0.5mmol, 1.0equiv.), continue to react for 2h, the color of the mixture changes from reddish brown to brownish green, and the reaction progress is judged by TLC, and the reaction liquid is spotted on a silica gel plate to monitor the reaction progress (developing agent ratio PE:DCM=1:1). When the reaction is completed until the reaction of Grubbs II catalyst is completed, stop stirring. Put the flask on a rotary evaporator, under the water pump pressure (-0.1MPa), when the rotary evaporation water bath temperature is 24°C, evaporate 18mL of solvent, add an appropriate amount of n-hexane for ultrasonic oscillation, and solid precipitates. Add filter paper to the Buchner funnel and place it on a suction flask, which is connected to a water pump. Pour the reaction solution with solids into the Buchner funnel and filter out the solids. After the solids are rinsed with n-hexane (3×20 mL) in the Buchner funnel, collect the solids in a dry flask and use a vacuum pump to drain the solvent to obtain a green solid III (ruthenium complex III). The yield of the target compound is 18% when toluene is used as the solvent; the yield of the target compound is 42% when tetrahydrofuran is used as the solvent; the yield of the target compound is 11% when acetonitrile is used as the solvent; the yield of the target compound is 48% when dichloromethane is used as the solvent; and the yield of the target compound is 10% when ether is used as the solvent.

[0050] Synthesis method 2: 0.42 g (0.50 mmol, 1.0 equiv.) of Grubbs II catalyst was added to a round-bottom flask, and 20 mL of dichloromethane was added to dissolve it. After the reaction system was heated to 40°C, methylimidazole salt (0.075 g, 0.5 mmol, 1.0 equiv., 0.15 g, 1.0 mmol, 2.0 equiv., 0.225 g, 1.5 mmol, 3.0 equiv., 0.30 g, 2.0 mmol, 4.0 equiv.) was slowly added, and the reaction was continued for 2 h. The color of the mixture changed from reddish brown to brownish green. The reaction progress was judged by TLC. The reaction liquid was spotted on a silica gel plate to monitor the reaction progress (developer ratio PE:DCM = 1:1). When the reaction was completed with the Grubbs II catalyst, the stirring was stopped. The flask was placed on a rotary evaporator. Under the pressure of a water pump (-0.1MPa), when the temperature of the rotary evaporation water bath was 24°C, 18mL of solvent was evaporated, and an appropriate amount of n-hexane was added for ultrasonic oscillation, and solids were precipitated. Filter paper was added to the Buchner funnel, and it was placed on a suction flask, and the suction flask was connected to a water pump. The reaction solution with solids was poured into the Buchner funnel to filter out the solids. After the solids were rinsed with n-hexane (3×20mL) in the Buchner funnel, the solids were collected in a dry flask, and the solvent was drained with a vacuum pump to obtain a green solid III (ruthenium complex III). The catalyst yield was 48% when the catalyst was followed by methylimidazolium salt in an amount of 1:1 (molar ratio); the catalyst yield was 71% when the catalyst was followed by methylimidazolium salt in an amount of 1:2 (molar ratio); the catalyst yield was 73% when the catalyst was followed by methylimidazolium salt in an amount of 1:3 (molar ratio); the catalyst yield was 59% when the catalyst was followed by methylimidazolium salt in an amount of 1:4 (molar ratio).

[0051] Synthesis method 3: Add 0.42g (0.50mmol, 1.0equiv.) of Grubbs II catalyst to a round-bottom flask, add 20mL of dichloromethane to dissolve it, heat the reaction system to a certain temperature (such as 10℃, 20℃, 30℃, 40℃, 50℃, 60℃), slowly add a certain proportion of methyl imidazole salt (such as 0.15g, 1mmol, 2.0equiv.), continue to react for 2h, the color of the mixture changes from reddish brown to brownish green, and the reaction progress is judged by TLC, and the reaction liquid is spotted on a silica gel plate to monitor the reaction progress (developer ratio PE:DCM=1:1). When the reaction is completed until the Grubbs II catalyst reacts, stop stirring. Put the flask on a rotary evaporator, under water pump pressure (-0.1MPa), when the rotary evaporation water bath temperature is 24℃, evaporate 18mL of solvent, add an appropriate amount of n-hexane for ultrasonic oscillation, and solid precipitates. Add filter paper to the Buchner funnel and place it on a suction flask, which is connected to a water pump. Pour the reaction solution with solids into the Buchner funnel and filter out the solids. After the solids are rinsed with n-hexane (3×20mL) in the Buchner funnel, collect the solids in a dry flask and use a vacuum pump to drain the solvent to obtain a green solid III (ruthenium complex III). The yield of the target product is 27% at 10°C; the yield of the target product is 38% at 20°C; the yield of the target product is 54% at 30°C, and the yield of the target product is 71% at 40°C; the yield of the target product is 70% at 50°C, and the yield of the target product is 59% at 60°C.

[0052] After testing, the nuclear magnetic resonance of ruthenium complex III is: 1 H NMR (400 MHz, CDCl 3 )δ19.13(s,1H),7.67(d,J=7.7Hz,2H),7.44(d,J=7.1Hz,2H),7.17-6.87(m,7H),6.82(s,1H),6.69 (s,2H),6.49(s,1H),4.05(d,J=44.6Hz,4H),3.66(s,3H),3.41(s,3H),2.64(s,6H),2.25(s,12H). 13 C NMR (101 MHz, CDCl 3 )δ219.37,152.23,138.58,138.18,137.32,130.01,128.91,128.45,127.29,118.70,51.40,33.65,31.46,21.04,19.05.

[0053] The structural formula of the obtained product (ruthenium complex III) is shown in formula (I), wherein R is methyl.

[0054] Example 4

[0055] The ethylene decomposition reaction of methyl oleate by the catalyst I-III (ruthenium complex I-III) of the present invention:

[0056] This reaction has high requirements on the purity of methyl oleate, and commercially available methyl oleate needs to be purified:

[0057] First, there may be residual impurities such as acid or alkali in the commercially available methyl oleate. This has a great impact on the catalytic efficiency of the catalyst, so it is necessary to remove the influence of acid and alkali factors. The specific method is: the bottom layer of the column is filled with 7-12 cm thick neutral alumina, and the upper layer is filled with 7-12 cm thick alkaline alumina. 10mL of methyl oleate is dissolved in 50-100mL of petroleum ether, added to the column, and the column is directly flushed with petroleum ether until the methyl oleate is completely flushed out. After removing the petroleum ether, the vacuum pump is pumped down for 3-8 hours to remove the residual petroleum ether.

[0058] Secondly, oxygen and other gases in methyl oleate will also affect the catalyst, so methyl oleate needs to be degassed. The specific method is: put the methyl oleate with acid and alkali impurities removed into liquid nitrogen until the liquid is converted into a solid state, then put it into a vacuum pump and pump it to room temperature. At this time, methyl oleate is converted from a solid state to a liquid state. This process is repeated 3-5 times to remove oxygen and other gases dissolved in methyl oleate. After degassing, fill it with nitrogen and store it in a glove box for later use.

[0059]

[0060] Method 1 for the ethylene decomposition of methyl oleate: add a stirring bar, 50 mL of n-dodecane (chromatographically pure, internal standard) and methyl oleate (1 mL) treated according to the above method to a 10 mL high-pressure reactor, and then add 10 uL of a toluene solution of catalyst I-III or Grubbs III (1 mg of catalyst is dissolved in 1 mL of toluene, and the catalyst concentration is 100 ppm at this time). Evacuate the reactor with a vacuum pump for 1 minute, introduce ethylene gas to make the reactor slightly positive, and cycle this process 3 times. Then evacuate the reactor with a vacuum pump for another minute, and increase the pressure of ethylene in the reactor to a certain level (such as 150 psi). Put the reactor into a reaction module that is thermostated at a certain temperature (20°C, 30°C, 40°C, 50°C), stir the reaction, and take samples every half an hour to detect the gas chromatography. The yield will not continue to increase after 6 hours of reaction, and the selectivity of the products 9-octadec-9-ene and dimethyl 9-octadec-9-enedioate is greater than 99%.

[0061] At a temperature of 20°C, the methyl oleate conversion rate catalyzed by catalyst I reached 31.0%, and the TON value was 2973; at a temperature of 30°C, the methyl oleate conversion rate catalyzed by catalyst I reached 35.0%, and the TON value was 3359; at a temperature of 40°C, the methyl oleate conversion rate catalyzed by catalyst I reached 49.3%, and the TON value was 3742; at a temperature of 50°C, the methyl oleate conversion rate catalyzed by catalyst I reached 46.3%, and the TON value was 3515. At a temperature of 20°C, the methyl oleate conversion rate catalyzed by catalyst II reached 32.8%, and the TON value was 3147; at a temperature of 30°C, the methyl oleate conversion rate catalyzed by catalyst II reached 39.6%, and the TON value was 3793; at a temperature of 40°C, the methyl oleate conversion rate catalyzed by catalyst II reached 58.4%, and the TON value was 4431; at a temperature of 50°C, the methyl oleate conversion rate catalyzed by catalyst II reached 49.9%, and the TON value was 3793. At 20°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 23.9%, and the TON value was 2291; at 30°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 26.6%, and the TON value was 2546; at 40°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 43.9%, and the TON value was 3328; at 50°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 38.4%, and the TON value was 2916. At 20°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 20.8%, and the TON value was 1994; at 30°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 24.7%, and the TON value was 2368; at 40°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 34.7%, and the TON value was 2631; at 50°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 32.2%, and the TON value was 2446. At different reaction temperatures, the conversion rates and TON values ​​of catalysts I-III are higher than those of Grubbs III.

[0062] Method 2 for the ethylene decomposition of methyl oleate: Add a stirrer, 50 mL of n-dodecane (chromatographically pure, internal standard) and methyl oleate (1 mL) treated as described above to a 10 mL autoclave, followed by the addition of 10 uL of a toluene solution of catalyst I-III or Grubbs III (1 mg of catalyst dissolved in 1 mL of toluene, with a catalyst concentration of 100 ppm). Evacuate the reactor with a vacuum pump for 1 minute, introduce ethylene gas to make the reactor slightly positively pressurized, and cycle this process 3 times. Evacuate the reactor with a vacuum pump for another minute, and increase the pressure of ethylene in the reactor to a certain level (50 psi, 100 psi, 150 psi, 200 psi). The reactor is placed in a reaction module which is kept at a constant temperature (such as 40° C.), stirred for reaction, and samples are taken every half an hour to detect the gas chromatography. After 6 hours of reaction, the yield does not continue to increase, and the selectivity for the products 9-octadec-9-ene and dimethyl octadec-9-enedioate is greater than 99%.

[0063] When the ethylene pressure is 50psi, the methyl oleate conversion rate of catalyst I reaches 32.1%, and the TON value is 2431; when the ethylene pressure is 100psi, the methyl oleate conversion rate of catalyst I reaches 36.9%, and the TON value is 2795; when the ethylene pressure is 150psi, the methyl oleate conversion rate of catalyst I reaches 49.3%, and the TON value is 3742; when the ethylene pressure is 200psi, the methyl oleate conversion rate of catalyst I reaches 40.9%, and the TON value is 3103. When the ethylene pressure is 50psi, the methyl oleate conversion rate of catalyst II reaches 39.7%, and the TON value is 3011; when the ethylene pressure is 100psi, the methyl oleate conversion rate of catalyst II reaches 50.7%, and the TON value is 3844; when the ethylene pressure is 150psi, the methyl oleate conversion rate of catalyst II reaches 58.4%, and the TON value is 4431; when the ethylene pressure is 200psi, the methyl oleate conversion rate of catalyst II reaches 50.6%, and the TON value is 3804. When the ethylene pressure is 50psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 34.2%, and the TON value is 2591; when the ethylene pressure is 100psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 47.6%, and the TON value is 3608; when the ethylene pressure is 150psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 43.9%, and the TON value is 3328; when the ethylene pressure is 200psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 35.5%, and the TON value is 2694. When the ethylene pressure is 50psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 23.8%, and the TON value is 1804; when the ethylene pressure is 100psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 25.1%, and the TON value is 1902; when the ethylene pressure is 150psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 34.7%, and the TON value is 2631; when the ethylene pressure is 200psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 26.7%, and the TON value is 2026. Under different ethylene pressures, the conversion rate and TON value of catalysts I-III are higher than those of Grubbs III.

[0064] Example 5

[0065] Ring-closing metathesis reaction: 0.5mmol of N,N-diallyl-p-toluenesulfonamide was dissolved in 0.5mL of toluene, and 1% of catalyst (I-III, GIII) was added thereto. The reaction was carried out at 80°C for 4h. After the reaction, it was added to a 10cm high silica gel column (300 mesh), and the target product was purified using a solvent of petroleum ether: ethyl acetate = 10:1 as a developing solvent. When the catalyst I-III was added, the catalytic products were 1-tosyl-2,5-dihydro-1H-pyrrole (yield: 43%) and 3-methyl-4-methylene-1-tosylpyrrolidine (yield: 52%). When the catalyst GIII was added, the catalytic product was 1-tosyl-2,5-dihydro-1H-pyrrole (yield: 97%).

[0066] When 0.5mmol of N,N-diallyl p-toluenesulfonamide is dissolved in 0.5mL of toluene, 1% (I-III) catalyst is added thereto, and then 3-bromo-1-propyne (3%) is added to the reaction system. The reaction is carried out at 80°C for 4h. After the reaction is completed, column chromatography is used for purification. The addition of 3-bromo-1-propyne produces selective control of the reaction, and at this time, the product is only 1-toluenesulfonyl-2,5-dihydro-1H-pyrrole.

[0067] 1-Tosyl-2,5-dihydro-1H-pyrrole: Yield: 95% (I), 97% (II), 93% (III), 92% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.72(d,J=8.2Hz,2H),7.32(d,J=7.9Hz,2H),5.65(s,2H),4.12(s,4H),2.43(s,3H). 13 C NMR (101 MHz, CDCl 3 )δ143.45,134.20,129.78,127.43,125.46,54.86,21.56.

[0068] Catalyst I-III directly catalyzes N, N-diallyl p-toluenesulfonamide to obtain 1-toluenesulfonyl-2,5-dihydro-1H-pyrrole and 3-methyl-4-methylene-1-tolylpyrrolidine at the same time, while GIII catalyst only obtains 1-toluenesulfonyl-2,5-dihydro-1H-pyrrole. When 3-bromo-1-propyne is added to the catalytic system of catalysts I-III, 1-toluenesulfonyl-2,5-dihydro-1H-pyrrole can be obtained with a catalytic yield higher than that of GIII catalyst.

[0069] Example 6

[0070] Ring-closing metathesis reaction: 0.5mmol of N,N-di(3-ene-1-butyl)-4-p-toluenesulfonamide was dissolved in 0.5mL toluene, and 1% (I-III, GIII) catalyst was added thereto, and then 3-bromo-1-propyne (3%) was added to the reaction system. The reaction was carried out at 80°C for 4h. After the reaction was completed, the reaction solution was added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0071] 1-tosyl-2,3,6,7-tetrahydro-1H-azepine: Yield: 93% (I), 90% (II), 89% (III), 87% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.67(d,J=8.2Hz,2H),7.30(d,J=8.0Hz,2H),5.75(t,J=3.4Hz,2H),3.30-3.25(m,4H),2.42(s,3H),2.31(q,J=4.2Hz,4H). 13 C NMR (101 MHz, CDCl 3 )δ143.11,136.22,130.26,129.68,127.07,48.28,29.91,21.53.

[0072] When 3-bromo-1-propyne is added to the catalyst I-III catalytic system, 1-toluenesulfonyl-2,3,6,7-tetrahydro-1-H-azepine can be obtained with a catalytic yield higher than that of the GIII catalyst.

[0073] Example 7

[0074] Ring-closing metathesis reaction: 0.5mmol of N-allyl, N-3-ene-1-butyl-4-p-toluenesulfonamide was dissolved in 0.5mL toluene, and 1% (I-III, GIII) catalyst was added thereto, and then 3-bromo-1-propyne (3%) was added to the reaction system. The reaction was carried out at 80°C for 4h. After the reaction was completed, the reaction solution was added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0075] 1-Tosyl-1,2,3,6-tetrahydropyridine: Yield: 88% (I), 84% (II), 89% (III), 81% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.58(d,J=8.2Hz,2H),7.23(d,J=8.0Hz,2H),5.66(d,J=13.9Hz,1H),5.52(d ,J=13.3Hz,1H),3.48(s,2H),3.08(t,J=5.7Hz,2H),2.33(s,3H),2.11(s,2H). 13 C NMR (101 MHz, CDCl 3 )δ143.54,133.26,129.63,127.64,125.04,122.72,44.79,42.65,25.25,21.50.

[0076] When 3-bromo-1-propyne is added to the catalyst I-III catalytic system, 1-tosyl-1,2,3,6-tetrahydropyridine can be obtained at a catalytic yield higher than that of the GIII catalyst.

[0077] Example 8

[0078] Ring-closing metathesis reaction: 0.5mmol of N-allyl, N-4-ene-1-pentyl-4-toluenesulfonamide was dissolved in 0.5mL toluene, and 1% (I-III, GIII) catalyst was added thereto, and then 3-bromo-1-propyne (3%) was added to the reaction system. The reaction was carried out at 80°C for 4h. After the reaction was completed, the reaction solution was added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0079] 1-tosyl-2,3,4,7-tetrahydro-1H-azepine: Yield: 89% (I), 90% (II), 89% (III), 86% (Grubbs III). 1 H NMR (400 MHz, CDCl 3)δ7.67(d,J=7.9Hz,2H),7.29(d,J=8.0Hz,2H),5.82–5.71(m,1H),5.71–5.58(m,1H),3.82(d, J=5.0Hz,2H),3.38(t,J=6.1Hz,2H),2.41(s,3H),2.17(d,J=6.0Hz,2H),1.79(p,J=5.7Hz,2H). 13 C NMR (101 MHz, CDCl 3 )δ143.07,136.20,132.94,129.55,127.16,126.59,49.63,46.37,26.81,26.75,21.50.

[0080] When 3-bromo-1-propyne is added to the catalyst I-III catalytic system, 1-toluenesulfonyl-2,3,4,7-tetrahydro-1H-azepine can be obtained with a catalytic yield higher than that of the GIII catalyst.

[0081] Example 9

[0082] Ring-closing metathesis reaction: 0.5 mmol of N, N-diallyl-4-fluorobenzamide was dissolved in 0.5 mL of toluene, and 1% (I-III, GIII) catalyst was added thereto, and then 3-bromo-1-propyne (3%) was added to the reaction system. The reaction was carried out at 80°C for 4 hours. After the reaction was completed, the reaction solution was added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0083] (2,5-dihydro-1H-pyrrol-1-yl)(4-fluorophenyl)methanone: Yield: 87% (I), 85% (II), 84% (III), 80% (Grubbs III). 1 HNMR (400MHz, CDCl 3 )δ7.59–7.38(m,2H),7.02(t,J=8.6Hz,2H),5.83(s,1H),5.68(s,1H),4.37(s,2H),4.14(s,2H). 13 C NMR (101 MHz, CDCl 3)δ168.86,163.48(d,J CF=249.7Hz), 132.86(d,J CF=3.5Hz), 129.18(d,J CF=8.7Hz), 126.00,125.11,115.53,115.31,55.85,53.53. 19 F NMR (376MHz, CDCl 3)δ-110.12.

[0084] When 3-bromo-1-propyne is added to the catalyst I-III catalytic system, (2,5-dihydro-1H-pyrrol-1-yl)(4-fluorophenyl)methanone can be obtained with a catalytic yield higher than that of the GIII catalyst.

[0085] Example 10

[0086] Ring-closing metathesis reaction: 0.5mmol of N, N-diallyl-2,4,6-trimethylbenzamide was dissolved in 0.5mL toluene, and 1% (I-III, GIII) catalyst was added thereto, and then 3-bromo-1-propyne (3%) was added to the reaction system. The reaction was carried out at 80°C for 4h. After the reaction was completed, the reaction solution was added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0087] (2,5-dihydro-1H-pyrrol-1-yl)(mesityl)methanone: Yield: 86% (I), 84% (II), 88% (III), 84% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ6.85(s,2H),5.96–5.84(m,1H),5.78–5.67(m,1H),4.43(s,2H),3.80(s,2H),2.26(s,3H),2.22(s,6H). 13 C NMR (101 MHz, CDCl 3 )δ169.96,137.98,134.55,132.83,128.27,125.89,125.35,54.11,52.16,21.07,18.83.

[0088] By adding 3-bromo-1-propyne to the catalyst I-III catalytic system, (2,5-dihydro-1H-pyrrol-1-yl)(trimethyl)ketone can be obtained with a catalytic yield no less than that of the GIII catalyst.

[0089] Embodiment 11

[0090] Cross metathesis reaction: 0.5mmol of 4-phenoxy-1-propylene and 0.5mmol of styrene were dissolved in 1mL of dichloromethane, and then 2.5mol% (I-III, GIII) catalyst was added thereto. The reaction was stirred at 40°C for 12h. After the reaction, the reaction solution was added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0091] (Cinnamyloxy)benzene: Yield: 86% (I), 89% (II), 81% (III), 86% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.52–7.19(m,7H),6.96(d,J=7.9Hz,3H),6.73(d,J=15.9Hz,1H),6.42(d,J=15.1Hz,1H),4.69(d,J=5.8Hz,2H). 13 CNMR (101MHz, CDCl 3 )δ158.64,136.48,133.00,129.54,128.63,127.93,126.62,124.54,120.93,114.80,68.58.

[0092] The catalyst I-II catalytic system can obtain (cinnamoyloxy)benzene at a catalytic yield no lower than that of the GIII catalyst.

[0093] Example 12

[0094] Cross metathesis reaction: 0.5 mmol of 4-phenoxy-1-propylene and 0.5 mmol of 4-fluorostyrene were dissolved in 1 mL of dichloromethane, and then 2.5 mol% (I-III, GIII) catalyst was added thereto. The reaction was stirred at 40°C for 12 h. After the reaction, the reaction solution was added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0095] (E)-1-fluoro-4-(3-phenoxyprop-1-en-1-yl)benzene: Yield: 85% (I), 86% (II), 84% (III), 82% (Grubbs III). 1 H NMR (400 MHz, CDCl 3)δ7.39–7.33(m,2H),7.33–7.26(m,2H),7.04–6.92(m,5H),6.68(d,J=15.9Hz,1H),6.33(dt,J=16.0,5.8Hz,1H),4.67(d,J=4.7Hz,2H). 13 C NMR (101 MHz, CDCl 3 )δ162.51(d,J CF=247.2Hz),158.59,132.65(d,J CF=3.3Hz),131.85,129.56,128.16(d,J CF=8.0Hz),124.25(d,J CF=2.2Hz),120.99,115.56(d,J CF=21.6Hz),114.76,68.44. 19 F NMR (376 MHz, CDCl 3 )δ-113.92.

[0096] Catalysts I-III catalytic systems can all produce (E)-1-fluoro-4-(3-phenoxyprop-1-en-1-yl)benzene with a catalytic yield higher than that of catalyst GIII.

[0097] Embodiment 13

[0098] Cross metathesis reaction: 0.5 mmol of 4-phenoxy-1-propylene and 0.5 mmol of 4-methylstyrene were dissolved in 1 mL of dichloromethane, and then 2.5 mol% (I-III, GIII) catalyst was added. The reaction was stirred at 40°C for 12 hours. After the reaction, the reaction solution was added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0099] (E)-1-methyl-4-(3-phenoxyprop-1-en-1-yl)benzene: Yield: 79% (I), 82% (II), 77% (III), 75% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.30(d,J=7.8Hz,4H),7.12(d,J=7.7Hz,2H),6.99–6.90(m,3H),6.69(d,J= 15.9Hz, 1H), 6.36 (dt, J=16.0, 5.9Hz, 1H), 4.67 (d, J=5.9Hz, 2H), 2.33 (s, 3H). 13CNMR (101MHz, CDCl 3 )δ158.68,137.81,133.69,133.07,129.53,129.34,126.55,123.42,120.88,114.80,68.72,21.29.

[0100] Catalysts I-III catalytic systems can all produce (E)-1-methyl-4-(3-phenoxyprop-1-en-1-yl)benzene with a catalytic yield higher than that of catalyst GIII.

[0101] Embodiment 14

[0102] Cross metathesis reaction: 0.5mmol of 4-(4'-methoxy)phenoxy-1-propylene and 0.5mmol of styrene were dissolved in 1mL of dichloromethane, and then 2.5mol% (I-III, GIII) catalyst was added thereto. The reaction was stirred at 40°C for 12h. After the reaction, the reaction solution was added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0103] 1-(Cinnamyloxy)-4-methoxybenzene: Yield: 86% (I), 87% (II), 81% (III), 84% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.41(d,J=7.2Hz,2H),7.32(t,J=7.5Hz,2H),7.26(d,J=7.4Hz,1H),6.90(d,J=9.0Hz,2H),6.84(d,J=9 .1Hz,2H),6.71(d,J=16.0Hz,1H),6.41(dt,J=15.9,5.8Hz,1H),4.65(dd,J=5.8,1.6Hz,2H),3.77(s,3H). 13 C NMR (101 MHz, CDCl 3 )δ153.96,152.78,136.51,132.85,128.60,127.87,126.58,124.79,115.82,114.67,69.39,55.74.

[0104] The catalyst I-II catalytic system can obtain 1-(cinnamoyloxy)-4-methoxybenzene with a catalytic yield higher than that of the GIII catalyst.

[0105] Embodiment 15

[0106] Cross metathesis reaction: 0.5 mmol of 4-(4'-methoxy)phenoxy-1-propylene and 0.5 mmol of 4-fluorostyrene were dissolved in 1 mL of dichloromethane, and then 2.5 mol% of (I-III, GIII) catalyst was added. The reaction was stirred at 40°C for 12 hours. After the reaction, the reaction solution was added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0107] (E)-1-fluoro-4-(3-(4-methoxyphenoxy)prop-1-en-1-yl)benzene: Yield: 78% (I), 83% (II), 70% (III), 75% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.36(s,2H),7.09–6.80(m,6H),6.76–6.62(m,1H),6.45–6.19(m,1H),4.61(t,J=5.7Hz,2H),3.88–3.69(m,3H). 13 C NMR (101 MHz, CDCl 3 )δ154.00,152.74,132.68,131.70,128.12(d,J CF=7.9Hz),124.53,115.79,115.64,115.43,114.69,69.26,55.73. 19 F NMR (376MHz, CDCl 3) δ-114.01.

[0108] The catalyst I-II catalytic system can obtain (E)-1-fluoro-4-(3-(4-methoxyphenoxy)prop-1-en-1-yl)benzene with a catalytic yield higher than that of the GIII catalyst.

[0109] Example 16

[0110] Cross metathesis reaction: 0.5 mmol of 4-(4'-methoxy)phenoxy-1-propylene and 0.5 mmol of 4-methylstyrene were dissolved in 1 mL of dichloromethane, and then 2.5 mol% of (I-III, GIII) catalyst was added thereto. The reaction was stirred at 40°C for 12 hours. After the reaction was completed, the reaction solution was added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0111] (E)-1-methoxy-4-((3-(p-tolyl)allyl)oxy)benzene: Yield: 77% (I), 74% (II), 66% (III), 71% (Grubbs III). 1 HNMR (400MHz, CDCl 3 )δ7.30(d,J=7.7Hz,2H),7.13(d,J=7.7Hz,2H),6.90(d,J=9.0Hz,2H),6.84(d,J=9.3Hz,2H),6.68(d ,J=16.0Hz,1H),6.36(dt,J=16.1,5.8Hz,1H),4.67–4.60(m,2H),3.77(d,J=1.8Hz,3H),2.34(s,3H). 13 CNMR (101MHz, CDCl 3 )δ153.92,152.81,137.74,133.70,132.90,129.28,126.49,123.67,115.82,114.64,69.53,55.74,21.25.

[0112] The catalyst I-II catalytic system can obtain (E)-1-methoxy-4-((3-(p-tolyl)allyl)oxy)benzene with a catalytic yield higher than that of the GIII catalyst.

[0113] Embodiment 17

[0114] Cross metathesis reaction: 0.5mmol of 4-(4'-phenyl)phenoxy-1-propylene and 0.5mmol of styrene were dissolved in 1mL of dichloromethane, and then 2.5mol% (I-III, GIII) catalyst was added thereto. The reaction was stirred at 40°C for 12h. After the reaction, the reaction solution was added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0115] 4-(cinnamyloxy)-1,1'-biphenyl: Yield: 60% (I), 64% (II), 61% (III), 56% (Grubbs III). 1 H NMR (400 MHz, CDCl 3)δ7.55(t,J=8.1Hz,4H),7.43(d,J=7.7Hz,4H),7.33(q,J=6.5,5.7Hz,3H),7.28(s,1H),7.07- 7.02(m,2H),6.76(d,J=16.0Hz,1H),6.45(dt,J=15.9,5.7Hz,1H),4.75(dd,J=5.9,1.6Hz,2H). 13 C NMR (101 MHz, CDCl 3 )δ158.22,140.80,136.44,134.01,133.12,128.73,128.62,128.20,127.95,126.76,126.70,126.61,124.43,115.09,68.77.

[0116] Catalyst I-III catalytic systems can all produce 4-(cinnamoyloxy)-1,1'-biphenyl with a catalytic yield higher than that of GIII catalyst.

[0117] Embodiment 18

[0118] Cross metathesis reaction: 0.5 mmol of 4-(4'-phenyl)phenoxy-1-propylene and 0.5 mmol of 4-fluorostyrene were dissolved in 1 mL of dichloromethane, and then 2.5 mol% of (I-III, GIII) catalyst was added. The reaction was stirred at 40°C for 12 hours. After the reaction, the reaction solution was added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0119] (E)-4-((3-(4-fluorophenyl)allyl)oxy)-1,1'-biphenyl: Yield: 58% (I), 56% (II), 38% (III), 52% (Grubbs III). 1 HNMR (400MHz, CDCl 3 )δ7.47(t,J=7.9Hz,4H),7.37–7.28(m,4H),7.22(t,J=7.3Hz,1H),6.95(d,J=8.3H z, 4H), 6.64 (d, J = 15.9Hz, 1H), 6.27 (dt, J = 16.0, 5.8Hz, 1H), 4.64 (d, J = 5.8Hz, 2H). 13 C NMR (101 MHz, CDCl 3)δ158.16,140.76,134.05,131.97,128.76,128.22,128.13,126.76,124.14(d,J CF=2.1Hz),115.68,115.46,115.05,68.64. 19 F NMR (376 MHz, CDCl 3 )δ-113.93.

[0120] The catalyst I-II catalytic system can obtain (E)-4-((3-(4-fluorophenyl)allyl)oxy)-1,1'-biphenyl with a catalytic yield higher than that of the GIII catalyst.

[0121] Embodiment 19

[0122] Cross metathesis reaction: 0.5 mmol of 4-(4'-phenyl)phenoxy-1-propylene and 0.5 mmol of 4-methylstyrene were dissolved in 1 mL of dichloromethane, and then 2.5 mol% of (I-III, GIII) catalyst was added thereto. The reaction was stirred at 40°C for 12 hours. After the reaction was completed, the reaction solution was added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 was used as a developing solvent to purify the target product.

[0123] (E)-4-((3-(p-tolyl)allyl)oxy)-1,1'-biphenyl: Yield: 53% (I), 55% (II), 33% (III), 49% (Grubbs III). 1 H NMR (400 MHz, CDCl 3 )δ7.54(t,J=8.7Hz,4H),7.41(t,J=7.7Hz,3H),7.34–7.30(m,2H),7.14(d,J=7.6Hz,2H),7.06–7.01( m,2H),6.72(d,J=16.0Hz,1H),6.39(dt,J=16.0,5.9Hz,1H),4.73(dd,J=5.9,1.5Hz,2H),2.35(s,3H). 13 C NMR (101 MHz, CDCl 3 )δ158.24,140.81,137.84,133.94,133.17,129.32,128.73,128.18,126.75,126.68,126.53,123.29,115.08,68.90,21.26.

[0124] The catalyst I-II catalytic system can obtain (E)-4-((3-(p-tolyl)allyl)oxy)-1,1'-biphenyl with a catalytic yield higher than that of the GIII catalyst.

Claims

1. An imidazole-coordinated ruthenium carbene olefin metathesis catalyst, characterized in that: The imidazole-coordinated ruthenium carbene olefin metathesis catalyst is shown in formula (I): Wherein, R is selected from benzyl, 2,4,6-trimethylphenyl or methyl.

2. A method for preparing the imidazole-coordinated ruthenium carbene olefin metathesis catalyst according to claim 1, characterized in that: include: In an organic solvent system, the Grubbs II catalyst reacts with a benzyl-substituted imidazolium salt, a trimethylphenyl-substituted imidazolium salt or a methyl-substituted imidazolium salt.

3. The method according to claim 2, characterized in that The method comprises: dissolving the Grubbs II catalyst in an organic solvent, adding a benzyl-substituted imidazole salt, a trimethylphenyl-substituted imidazole salt or a methyl-substituted imidazole salt to the reaction system at 10-60° C., and the reaction temperature is preferably 30-60° C.

4. The method according to claim 2, characterized in that The organic solvent is dichloromethane, acetonitrile, tetrahydrofuran, ether or toluene.

5. The method according to claim 2, characterized in that The molar ratio of the benzyl-substituted imidazole salt, the trimethylphenyl-substituted imidazole salt or the methyl-substituted imidazole salt to the Grubbs II catalyst is (1:1) to (4:1).

6. The method according to claim 5, characterized in that The molar ratio of the benzyl-substituted imidazole salt, the trimethylphenyl-substituted imidazole salt or the methyl-substituted imidazole salt to the Grubbs II catalyst is (2:1) to (3:1).

7. The method of claim 2, characterized in that After adding the benzyl-substituted imidazole salt, the trimethylphenyl-substituted imidazole salt or the methyl-substituted imidazole salt, the temperature is maintained to react for more than 2 hours.

8. The method according to any one of claims 2, 3, 5 and 6, characterized in that: The benzyl-substituted imidazole salt is N-benzylimidazole; preferably, the trimethylphenyl-substituted imidazole salt is N-2,4,6-trimethylphenylimidazole; and preferably, the methyl-substituted imidazole salt is N-methylimidazole.

9. The method according to any one of claims 2 to 8, characterized in that: The method further comprises: after the reaction is completed, removing part of the solvent under reduced pressure, adding n-hexane, cyclohexane, petroleum ether or acetonitrile, and centrifuging, filtering and drying the precipitated product.

10. The imidazole-coordinated ruthenium carbene olefin metathesis catalyst as claimed in claim 1 is used in the catalytic conversion of unsaturated octadecane dicarboxylic acid dimethyl ester, 1-decene or 9-decenoic acid methyl ester.

11. The imidazole-coordinated ruthenium carbene olefin metathesis catalyst as claimed in claim 1 is used in the ring-closing metathesis of olefins.

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