Benzylmethylene o-halogenated Ru olefin metathesis catalyst as well as preparation and application thereof

Abstract

The invention discloses a benzylidene o-halogenated Ru olefin metathesis catalyst which is shown as a formula I: # imgabs0 #, and X is selected from fluorine (F), chlorine (Cl) or bromine (Br). 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, and the stability of the GrubbsI catalyst is improved.

Description

Technical Field

[0001] The invention relates to a benzylidene ortho-halogenated Ru olefin metathesis catalyst and a preparation method and application thereof. Background Art

[0002] The selective synthesis of unsaturated octadecane dimethyl ester is a new technology based on the ethylene decomposition reaction of methyl oleate. The ethylene decomposition reaction of methyl oleate is a special case of olefin metathesis reaction. Olein metathesis reaction is an effective method to construct complex molecules by reorganizing carbon-carbon double bonds. This method has the advantages of being simple, fast, efficient, and having good atom economy, and has important application prospects in the fields of biology, medicine, and organic synthesis. The smooth progress of olefin metathesis reaction depends on the development of efficient olefin metathesis catalysts.

[0003] In 1992, the Grubbs research group first reported a class of ruthenium carbene compounds, also known as Grubbs first-generation catalysts, which broke the "monopoly" of molybdenum and tungsten metals in the field of olefin metathesis research, made up for the shortcomings of molybdenum and tungsten catalysts, and greatly expanded the application scope of olefin metathesis reactions. Grubbs I catalyst is a widely used catalyst. The synthesis process of this type of catalyst is simple and the structure is very stable. It will not decompose even if it is exposed to air for a long time. The functional group applicability of this type of catalyst is very good. It can be used for metathesis reactions of olefins with various functional groups. The reaction conditions are not demanding and can be catalyzed in the presence of impurities such as oxygen and water. However, this type of catalyst is not suitable for substrates with amine groups. The primary amine in the reaction system will poison and inactivate the catalyst, and the sulfur-containing substrate will also coordinate with the metal to reduce the activity of the catalyst. Hoveyda made improvements on the basis of Grubbs I catalyst and prepared a phenol-oxygen chelated ruthenium carbene complex. Catalyst 2 has higher activity and better stability, and can be used for large-scale preparation of various olefin compounds. This catalyst was later called Hoveyda-Grubbs I catalyst.

[0004] It was found that replacing one of the PCy3 with a nitrogen heterocyclic carbene ligand (NHC) resulted in a ruthenium carbene complex carbene olefin metathesis catalyst with higher catalytic activity and functional group compatibility, which was called the Grubbs II catalyst. On this basis, the Hoveyda team successfully developed the Hoveyda-Grubbs II catalyst. Compared with other ruthenium catalysts, this type of catalyst has higher catalytic efficiency and higher 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. These advantages make the Hoveyda-Grubbs II catalyst the most commonly used ruthenium olefin metathesis catalyst so far. Later, it was found that replacing the PCy3 ligand in complex 3 with a pyridine ligand resulted in complex 5 with a higher initiation rate, and it can even initiate olefin metathesis reactions at lower temperatures.

[0005]

[0006] Although ruthenium carbene catalysts 1-5 have high catalytic activity in conventional olefin metathesis reactions, they do not perform well in the ethylene decomposition reaction of methyl oleate. It was found that by replacing the NHC ligands in complexes 3 and 4 with mononitrogen ring carbene ligands (CAAC), the resulting complexes 6 and 7 have good catalytic activity for the ethylene decomposition reaction of methyl oleate (6, 7).

[0007] Although people have made a series of improvements to the Grubbs I catalyst and improved its catalytic activity, these catalysts are expensive and not commercialized. Therefore, in actual production and application, the Grubbs I catalyst is still the main choice. However, the unique decomposition mechanism of this catalyst also leads to its lower stability than other catalysts, which greatly increases the amount of catalyst used and reduces the application range of its reaction. Hong and Grudzien′ et al. studied the decomposition mechanism of the catalyst and found that when a phosphine ligand on the complex 1 dissociates, an intermediate 8 is generated, which further reacts to form a ruthenium-based complex 11 containing a three-membered ring, and then the chemical bond breaks to release the RHC=PCy3 molecule, and then the catalyst is decomposed.

[0008]

[0009] This unique decomposition mechanism leads to the unsatisfactory performance of the Grubbs I catalyst in the ethylene decomposition reaction of methyl oleate, and its TON value is only 5900. If this decomposition process can be inhibited by simple structural modification, the stability of such catalysts will be greatly improved, the utilization rate and application scope of the catalyst will be improved, and the cost will be saved. The present invention introduces a halogen substituent group at the ortho position of the benzylidene aromatic ring, stabilizes the intermediate through the halogen bond coordination between the halogen and the metal center, and improves the utilization rate of the catalyst. Summary of the invention

[0010] The inventors found that the metal ruthenium center in the existing Grubbs I is unstable, which reduces the stability of the catalyst and further reduces the utilization rate of the catalyst. Based on the existing technology, the inventors made the present invention after further research and development.

[0011] The present invention introduces a halogen atom into the ortho position of the Grubbs I benzylidene ruthenium, utilizes the steric hindrance and halogen bond coordination of the halogen atom, hinders the free PCy3 ligand in the system from performing a nucleophilic attack reaction on the metal ruthenium carbene bond, thereby slowing down the decomposition speed of the catalyst and improving the stability and catalytic efficiency of the catalyst.

[0012] The inventors speculate that the implementation principle of the present invention may be that when a halogen atom is introduced into the complex, it can coordinate with the ruthenium center to form a stable structure, thereby stabilizing the catalyst intermediate. If a halogen atom is introduced at the ortho position of the benzylidene ruthenium, when one of the PCy3 ligands dissociates, the halogen atom may interact with the metal ruthenium center, thereby extending the life of the intermediate 14 (intermediate 14). In addition, due to the steric hindrance of the halogen atom and the coordination of the halogen bond, the free PCy3 ligand in the system is hindered from performing a nucleophilic attack reaction on the metal ruthenium carbene bond, thereby slowing down the decomposition rate of the catalyst and improving the stability of the catalyst intermediate, thereby greatly improving the utilization rate and application range of the catalyst.

[0013]

[0014] As one aspect of the present invention, it relates to a Ru olefin metathesis catalyst of benzylidene ortho-halogenation, as shown in Formula I:

[0015]

[0016] Wherein, X is selected from fluorine (F), chlorine (Cl) or bromine (Br).

[0017] As another aspect of the present invention, it relates to a method for preparing the above-mentioned benzylidene ortho-halogenated Ru olefin metathesis catalyst, comprising: in an organic solvent system, tri(triphenylphosphine)ruthenium dichloride reacts with ortho-fluorobenzyl azide, ortho-chlorobenzyl azide or ortho-bromobenzyl azide.

[0018] In a specific embodiment, the method comprises: dissolving tri(triphenylphosphine)ruthenium dichloride in an organic solvent (such as dichloromethane, ether, tetrahydrofuran or toluene), preferably dichloromethane, cooling the reaction system to -10 to -78°C, preferably -78°C, and slowly adding o-fluorobenzyl azide, o-chlorobenzyl azide or o-bromobenzyl azide.

[0019] In a specific embodiment, the molar ratio of the added o-fluorobenzyl azide, o-chlorobenzyl azide or o-bromobenzyl azide to tris(triphenylphosphine)ruthenium dichloride is (1:1) to (3:1).

[0020] In a specific embodiment, the above method further comprises: after the reaction is completed, removing part of the solvent under reduced pressure, adding methanol, filtering and drying the precipitated product. In a specific embodiment, after adding o-fluorobenzyl azide, o-chlorobenzyl azide or o-bromobenzyl azide, the temperature is maintained for reaction for more than 30 minutes, and after adding excess tricyclohexylphosphine at room temperature, the reaction time is required to be more than 30 minutes.

[0021] The reaction process of the preparation method provided by the present invention is schematically shown as follows:

[0022]

[0023] Wherein, X is fluorine (F), chlorine (Cl) or bromine (Br).

[0024] As another aspect of the present invention, it relates to the use of the above-mentioned benzylidene ortho-halogenated Ru olefin metathesis catalyst in the catalytic conversion of saturated octadecenedioic acid dimethyl ester, 1-decene, and 9-decenoic acid methyl ester.

[0025] As another aspect of the present invention, it relates to a catalytic conversion process of saturated octadecane dicarboxylic acid dimethyl ester, 1-decene, and 9-decenoic acid methyl ester, using the above-mentioned benzylidene ortho-halogenated Ru olefin metathesis catalyst.

[0026] The method provided by the invention has simple steps, requires mild conditions and improves the stability of the Grubbs I catalyst.

[0027] The benzylidene ortho-halogenated Ru olefin metathesis catalyst provided by the present invention has higher stability than the Grubbs I catalyst, has a higher TON value for ethylene decomposition of methyl oleate, and has greatly improved catalytic activity. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 : The stability test results of the Ru olefin metathesis catalyst with ortho-halogenated benzylidene provided by the present invention and the Grubbs I catalyst. The figure uses benzophenone as the internal standard at 25°C. 1The decomposition of complexes GrubbsIII, Ia, Ib, and Ic in THF-d8 was monitored by H NMR. DETAILED DESCRIPTION

[0029] Example 1

[0030] The synthesis method of the complex (2-fluorobenzyl methylene) bis (tricyclohexylphosphine) ruthenium dichloride (Ia):

[0031] 1) Synthesis of 2-fluorobenzyldiazo

[0032] Add 3.72 g (20.0 mmol, 1.0 equiv) of p-toluenesulfonyl hydrazide to a round-bottom flask, add CH3OH (35 mL) to dissolve it, then slowly add 2.48 g (20.0 mmol, 1.0 equiv) of 2-fluorobenzaldehyde, and stir the reaction mixture at room temperature for 2 h, during which a white solid precipitates. After the reaction is completed, 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. Wash the solids with CH3OH (3×20 mL) in the Buchner funnel. Collect the solids in a dry flask, drain the solvent with a vacuum pump, and weigh them on an electronic balance to obtain 4.68 g (16.0 mmol) of 2-fluorobenzaldehyde-p-toluenesulfonylhydrazone, with a yield of 80%.

[0033] Add 2.64 g (9.0 mmol, 1.0 equiv) of 2-fluorobenzaldehyde-p-toluenesulfonylhydrazone to a round-bottom flask, add 30 mL of triethylene glycol and heat and stir at 60°C to dissolve the solid, then slowly add 1.82 g (16.2 mmol, 1.8 equiv) of potassium tert-butoxide, place the reaction mixture at 60°C and continue stirring for 1 hour, the color of the solution changes from white to orange and finally to red. After the mixture is cooled to room temperature, pour it into 70 mL of ice water and extract it with petroleum ether 3 times, 50 mL each time, and combine the organic phases for later use.

[0034] 2) Synthesis of Catalyst Ia

[0035] Synthesis method 1: In a nitrogen environment, add 2.50 g (2.6 mmol, 1.0 equiv) of tris(triphenylphosphine)ruthenium dichloride (RuCl2(PPh3)3) to a round-bottom flask, add 40 mL of solvent to dissolve it (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, ether, etc.), place the reaction system at a certain temperature (such as -78°C), slowly drop the above-prepared petroleum ether solution of 2-fluorobenzyldiazo (the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-fluorobenzyldiazo is 1:1, 1:2, 1:3), and continue to react at this temperature for 30 minutes after the addition is complete. Then the reaction system is warmed to room temperature, and a certain amount of PCy3 (such as 3.62 g, 12.8 mmol, 5.0 equiv) in DCM (20 mL) is slowly added to it under nitrogen environment. The color of the mixture gradually changes from yellow-green to purple, and stirring is continued at this temperature for 30 minutes. After the reaction is completed, 80% of DCM is spun out at a water temperature of 30°C under a pressure of -0.1Mpa, and 100mL of a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) is added to the remaining solution, and purple solid precipitation is observed. Add filter paper to the Buchner funnel and place it on a suction filtration bottle, 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 washed with a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) in the Buchner funnel (3×20mL), the solids are collected in a dry flask, the solvent is drained with a vacuum pump, and the electronic balance is placed for weighing. When the solvent is dichloromethane, the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-fluorobenzyldiazo is 1:1, Ia 1.71g, yield 78%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-fluorobenzyldiazo is 1:2, Ia 1.77g, yield 81%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-fluorobenzyldiazo is 1:3, Ia 1.46g, yield 67%. When the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-fluorobenzyldiazo is 1:1, the solvent is toluene, Ia 0.94g, yield 43%; when the solvent is tetrahydrofuran, Ia 0.68g, yield 31%; when the solvent is acetonitrile, Ia 0.57g, yield 26%; when the solvent is ether, Ia 0.20g, yield 9%.

[0036] Synthesis method 2: Under a nitrogen environment, add 2.50 g (2.6 mmol, 1.0 equiv) of tri(triphenylphosphine)ruthenium dichloride (RuCl2(PPh3)3) into a round-bottom flask, add 40 mL of solvent to dissolve it (such as dichloromethane), place the reaction system at a certain temperature (-10°C, -30°C, -40°C, -50°C, -60°C, -78°C), slowly drop the above-prepared petroleum ether solution of 2-fluorobenzyldiazo (the molar ratio of tri(triphenylphosphine)ruthenium dichloride to 2-fluorobenzyldiazo is 1:1), and continue to react at this temperature for 30 minutes after the addition is completed. Then the reaction system is warmed to room temperature, and a certain amount of PCy3 (such as 3.0 equiv, 4.0 equiv, 5.0 equiv, 6.0 equiv, 7.0 equiv) in DCM (20 mL) solution is slowly added thereto under nitrogen atmosphere, and the color of the mixture gradually changes from yellow-green to purple, and stirring is continued at this temperature for 30 min. After the reaction is completed, 80% of DCM is spun out at a water temperature of 30°C under a pressure of -0.1 MPa, and 100 mL of a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) is added to the remaining solution, and purple solid precipitation is observed. Filter paper is added to the Buchner funnel, which is placed on a suction flask, and the suction flask is connected to a water pump. The reaction solution with solids is poured into the Buchner funnel to filter out the solids. After the solid was washed with a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) in a Buchner funnel (3×20 mL), the solid was collected in a dry flask, the solvent was drained with a vacuum pump, and the solid was weighed on an electronic balance. When the molar amount of PCy3 was 5.0 equiv of tris(triphenylphosphine)ruthenium dichloride, at -10°C, Ia 0.52g, yield 24%; at -30°C, Ia 1.21g, yield 55%; at -40°C, Ia 1.27g, yield 58%; at -50°C, Ia 1.45g, yield 66%; at -60°C, Ia1.58g, yield 72%; at -78°C, Ia 1.71g, yield 78%. When the temperature was controlled at -78°C and the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:3, Ia was 0.81 g, and the yield was 37%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:4, Ia was 1.27 g, and the yield was 58%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:5, Ia was 1.71 g, and the yield was 78%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:6, Ia was 1.69 g, and the yield was 77%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:7, Ia was 1.71 g, and the yield was 78%.

[0037] After testing, the melting point (MP) of ruthenium complex is 143-145℃. 1HNMR (400MHz, CDCl3): δ20.56(s,Ru=CH),9.07(s,1H),7.65(d,J=6.5Hz,1H),7.06(t,J=7.8Hz,1H),6.96(t,J=9.6Hz,1H),2.61,1.75,1.44,and 1.21(all m,P(C6H 11 )3). 13 C NMR(101MHz,CDCl3)δ282.18,152.75(d,J CF =256.8Hz),141.20(d,J CF =7.1Hz),33.98,132.50(d,J CF =8.8Hz),124.79(d,J CF =3.7Hz),116.33(d,J CF =23.4Hz), 2.00 (t, J = 9.2Hz), 29.62, 27.83 (t, J = 5.2Hz), 26.51. 31 PNMR(162MHz,CDCl3)36.50(s,PCy3). 19 F NMR (376MHz,CDCl3)δ-108.06.

[0038] The structural formula of the obtained product is shown in Formula I, wherein X is fluorine (F).

[0039] Example 2

[0040] Complex (2-chlorobenzyl methylene) bis (tricyclohexylphosphine) ruthenium dichloride (Ib) synthesis method:

[0041] 1) Synthesis of 2-chlorobenzyldiazo

[0042] Add 3.72 g (20.0 mmol, 1.0 equiv) of p-toluenesulfonyl hydrazide to a round-bottom flask, add CH3OH (35 mL) to dissolve it, then slowly add 2.43 g (20.0 mmol, 1.0 equiv) of 2-chlorobenzaldehyde, and stir the reaction mixture at room temperature for 2 h, during which a white solid precipitates. After the reaction is completed, 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. Wash the solids with CH3OH (3×20 mL) in the Buchner funnel. Collect the solids in a dry flask, drain the solvent with a vacuum pump, and weigh them on an electronic balance to obtain 4.80 g (16.8 mmol) of 2-chlorobenzaldehyde-p-toluenesulfonylhydrazone, with a yield of 83%.

[0043] Add 2.61 g (9.0 mmol, 1.0 equiv) of 2-chlorobenzaldehyde-p-toluenesulfonylhydrazone to a round-bottom flask, add 30 mL of triethylene glycol and heat and stir at 60°C to dissolve the solid, then slowly add 1.82 g (16.2 mmol, 1.8 equiv) of potassium tert-butoxide, place the reaction mixture at 60°C and continue stirring for 1 hour, the color of the solution changes from white to orange and finally to red. After the mixture is cooled to room temperature, pour it into 70 mL of ice water and extract it with petroleum ether 3 times, 50 mL each time, and combine the organic phases for later use.

[0044] 2) Synthesis of Catalyst Ib

[0045] Synthesis method 1: In a nitrogen environment, add 2.50 g (2.6 mmol, 1.0 equiv) of tris(triphenylphosphine) ruthenium dichloride (RuCl2(PPh3)3) to a round-bottom flask, add 40 mL of solvent to dissolve it (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, ether, etc.), place the reaction system at a certain temperature (such as -78°C), slowly drop the above-prepared 2-chloro petroleum ether solution (tris(triphenylphosphine) ruthenium dichloride and benzyl diazonium molar ratio is 1:1, 1:2, 1:3), and continue to react at this temperature for 30 minutes after the addition is complete. Then the reaction system is warmed to room temperature, and a certain amount of PCy3 (such as 3.62 g, 12.8 mmol, 5.0 equiv) DCM (20 mL) solution is slowly added thereto under nitrogen environment, and the color of the mixture gradually changes from yellow-green to purple, and stirring is continued at this temperature for 30 minutes. After the reaction is completed, 80% of DCM is spun out at a water temperature of 30°C under a pressure of -0.1Mpa, and 100mL of a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) is added to the remaining solution, and purple solid precipitation is observed. Add filter paper to the Buchner funnel and place it on a suction filtration bottle, 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 washed with a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) in the Buchner funnel (3×20mL), the solids are collected in a dry flask, the solvent is drained with a vacuum pump, and the electronic balance is placed for weighing. When the solvent is dichloromethane, the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-chlorobenzyldiazo is 1:1, Ib is 1.67g, and the yield is 75%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-chlorobenzyldiazo is 1:2, Ib is 1.71g, and the yield is 77%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-chlorobenzyldiazo is 1:3, Ib is 1.63g, and the yield is 73%. When the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-chlorobenzyldiazo is 1:1, and the solvent is toluene, Ib is 1.14g, and the yield is 51%; when the solvent is tetrahydrofuran, Ib is 0.76g, and the yield is 34%; when the solvent is acetonitrile, Ib is 0.60g, and the yield is 27%; when the solvent is ether, Ia is 0.24g, and the yield is 11%.

[0046] Synthesis method 2: Under a nitrogen environment, add 2.50 g (2.6 mmol, 1.0 equiv) of tri(triphenylphosphine)ruthenium dichloride (RuCl2(PPh3)3) into a round-bottom flask, add 40 mL of solvent to dissolve it (such as dichloromethane), place the reaction system at a certain temperature (-10°C, -30°C, -40°C, -50°C, -60°C, -78°C), slowly drop the above-prepared petroleum ether solution of 2-chlorobenzyldiazo (the molar ratio of tri(triphenylphosphine)ruthenium dichloride to 2-chlorobenzyldiazo is 1:1), and continue to react at this temperature for 30 minutes after the addition is completed. Then the reaction system is warmed to room temperature, and a certain amount of PCy3 (such as 3.0 equiv, 4.0 equiv, 5.0 equiv, 6.0 equiv, 7.0 equiv) in DCM (20 mL) solution is slowly added thereto under nitrogen atmosphere, and the color of the mixture gradually changes from yellow-green to purple, and stirring is continued at this temperature for 30 min. After the reaction is completed, 80% of DCM is spun out at a water temperature of 30°C under a pressure of -0.1 MPa, and 100 mL of a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) is added to the remaining solution, and purple solid precipitation is observed. Filter paper is added to the Buchner funnel, which is placed on a suction flask, and the suction flask is connected to a water pump. The reaction solution with solids is poured into the Buchner funnel to filter out the solids. After the solid was washed with a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, hexane, etc.) in a Buchner funnel (3×20 mL), the solid was collected in a dry flask, the solvent was drained with a vacuum pump, and the solid was weighed on an electronic balance. When the molar amount of PCy3 was 5.0 equiv of tris(triphenylphosphine)ruthenium dichloride, at -10°C, Ib 0.42 g, yield 19%; at -30°C, Ib 1.00 g, yield 45%; at -40°C, Ib 1.20 g, yield 54%; at -50°C, Ib 1.43 g, yield 64%; at -60°C, Ib 1.56 g, yield 70%; at -78°C, Ib 1.67 g, yield 75%. When the temperature is controlled at -78°C and the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 is 1:3, Ib is 0.96g, and the yield is 43%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 is 1:4, Ib is 1.47g, and the yield is 66%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 is 1:5, Ib is 1.67g, and the yield is 75%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 is 1:6, Ib is 1.64g, and the yield is 74%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 is 1:7, Ib is 1.58g, and the yield is 71%.

[0047] After testing, the melting point (MP) of ruthenium complex is 141-143℃. 1HNMR (400MHz, CDCl3) δ20.83(s,Ru=CH),9.27(d,J=8.0Hz,1H),7.56(t,J=7.7Hz,1H),7.32(d,J=8.0Hz,1H),7.19(t,J=7.6Hz,1H),2.58,1.72,1.44,and 1.21(all m,P(C6H 11 )3). 13 C NMR (101MHz, CDCl3) δ288.54, 148.85, 134.79, 131.27, 130.81, 130.65, 127.68, 32.05 (t, J = 9.1Hz), 29.68, 27.84 (t, J = 5.3Hz), 26.51. 31 P NMR (162MHz, CDCl3) δ36.59 (s, PCy3).

[0048] The structural formula of the obtained product is shown in Formula I, wherein X is chlorine (Cl).

[0049] Example 3

[0050] Complex (2-bromobenzyl methylene) bis (tricyclohexylphosphine) ruthenium dichloride (Ic) synthesis method:

[0051] 1) Synthesis of 2-bromobenzyldiazo

[0052] Add 3.72 g (20.0 mmol, 1.0 equiv) of p-toluenesulfonyl hydrazide to a round-bottom flask, add CH3OH (35 mL) to dissolve it, then slowly add 3.70 g (20.0 mmol, 1.0 equiv) of 2-bromobenzaldehyde, and stir the reaction mixture at room temperature for 2 h, during which a white solid precipitates. After the reaction is completed, 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. Wash the solids with CH3OH (3×20 mL) in the Buchner funnel. Collect the solids in a dry flask, drain the solvent with a vacuum pump, and weigh them on an electronic balance to obtain 5.21 g (16.8 mmol) of 2-bromobenzaldehyde-p-toluenesulfonylhydrazone, with a yield of 74%.

[0053] Add 3.17 g (9.0 mmol, 1.0 equiv) of 2-bromobenzaldehyde-p-toluenesulfonylhydrazone to a round-bottom flask, add 30 mL of triethylene glycol and heat and stir at 60°C to dissolve the solid, then slowly add 1.82 g (16.2 mmol, 1.8 equiv) of potassium tert-butoxide, place the reaction mixture at 60°C and continue stirring for 1 hour, the color of the solution changes from white to orange and finally to red. After the mixture is cooled to room temperature, pour it into 70 mL of ice water and extract it with petroleum ether 3 times, 50 mL each time, and combine the organic phases for later use.

[0054] 2) Synthesis of Catalyst Ic

[0055] According to the optimized synthesis conditions of catalyst Ia, the dosage and steps of catalyst Ic synthesis are as follows:

[0056] Under nitrogen, add 32.50g (2.6mmol, 1.0equiv) of RuCl2(PPh3) to a round-bottom flask, add 40mL of DCM to dissolve it, place the reaction system at -78°C, slowly drop the above-prepared petroleum ether solution of benzyl diazonium, and continue to react at this temperature for 30min after the dropwise addition. Then warm the reaction system to room temperature, slowly add PCy3 (3.62g, 12.8mmol, 5.0equiv) DCM (20mL) solution under nitrogen, the color of the mixture gradually changes from yellow-green to purple, and continue to stir at this temperature for 30min. After the reaction is completed, under -0.1Mpa pressure, 80% of DCM is spun out at 30°C, and 100mL of CH3OH is added to the remaining solution, and purple solid precipitation is observed. 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 the Buchner funnel and filter out the solid. After the solid was rinsed with CH3OH (3×20 mL) in a Buchner funnel, the solid was collected in a dry flask, the solvent was evacuated with a vacuum pump, and the solid was weighed on an electronic balance to obtain 1.78 g of catalyst Ic with a yield of 76% and a melting point (MP): 153-155°C.

[0057] Synthesis method 1: In a nitrogen environment, add 2.50 g (2.6 mmol, 1.0 equiv) of tris(triphenylphosphine)ruthenium dichloride (RuCl2(PPh3)3) to a round-bottom flask, add 40 mL of solvent to dissolve it (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, ether, etc.), place the reaction system at a certain temperature (such as -78°C), slowly drop the above-prepared 2-bromo petroleum ether solution (the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-bromobenzyldiazo is 1:1, 1:2, 1:3), and continue to react at this temperature for 30 minutes after the addition is complete. Then the reaction system is warmed to room temperature, and a certain amount of PCy3 (such as 3.62 g, 12.8 mmol, 5.0 equiv) in DCM (20 mL) is slowly added to it under nitrogen environment. The color of the mixture gradually changes from yellow-green to purple, and stirring is continued at this temperature for 30 minutes. After the reaction is completed, 80% of DCM is spun out at a water temperature of 30°C under a pressure of -0.1Mpa, and 100mL of a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) is added to the remaining solution, and purple solid precipitation is observed. Add filter paper to the Buchner funnel and place it on a suction filtration bottle, 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 washed with a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) in the Buchner funnel (3×20mL), the solids are collected in a dry flask, the solvent is drained with a vacuum pump, and the electronic balance is placed for weighing. When the solvent is dichloromethane, the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-bromobenzyldiazo is 1:1, Ic 1.78g, yield 76%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-bromobenzyldiazo is 1:2, Ic 1.80g, yield 77%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-bromobenzyldiazo is 1:3, Ic 1.73g, yield 74%. When the molar ratio of tris(triphenylphosphine)ruthenium dichloride to 2-bromobenzyldiazo is 1:1, the solvent is toluene, Ic 1.12g, yield 48%; when the solvent is tetrahydrofuran, Ic 0.89g, yield 38%; when the solvent is acetonitrile, Ic 0.73g, yield 31%; when the solvent is ether, Ic 0.16g, yield 7%.

[0058] Synthesis method 2: Under a nitrogen environment, add 2.50 g (2.6 mmol, 1.0 equiv) of tri(triphenylphosphine)ruthenium dichloride (RuCl2(PPh3)3) into a round-bottom flask, add 40 mL of solvent to dissolve it (such as dichloromethane), place the reaction system at a certain temperature (-10°C, -30°C, -40°C, -50°C, -60°C, -78°C), slowly drop the above-prepared petroleum ether solution of 2-bromobenzyldiazo (the molar ratio of tri(triphenylphosphine)ruthenium dichloride to 2-bromobenzyldiazo is 1:1), and continue to react at this temperature for 30 minutes after the addition is completed. Then the reaction system is warmed to room temperature, and a certain amount of PCy3 (such as 3.0 equiv, 4.0 equiv, 5.0 equiv, 6.0 equiv, 7.0 equiv) in DCM (20 mL) solution is slowly added thereto under nitrogen atmosphere, and the color of the mixture gradually changes from yellow-green to purple, and stirring is continued at this temperature for 30 min. After the reaction is completed, 80% of DCM is spun out at a water temperature of 30°C under a pressure of -0.1 MPa, and 100 mL of a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, n-hexane, etc.) is added to the remaining solution, and purple solid precipitation is observed. Filter paper is added to the Buchner funnel, which is placed on a suction flask, and the suction flask is connected to a water pump. The reaction solution with solids is poured into the Buchner funnel to filter out the solids. After the solid was washed with a poor solvent (such as methanol, ethanol, petroleum ether, cyclohexane, hexane, etc.) in a Buchner funnel (3×20 mL), the solid was collected in a dry flask, the solvent was drained with a vacuum pump, and the solid was weighed on an electronic balance. When the molar amount of PCy3 was 5.0 equiv of tris(triphenylphosphine)ruthenium dichloride, at -10°C, Ic 0.52g, yield 22%; at -30°C, Ic 1.10g, yield 47%; at -40°C, Ic 1.36g, yield 58%; at -50°C, Ic 1.48g, yield 63%; at -60°C, Ic 1.62g, yield 69%; at -78°C, Ic 1.78g, yield 76%. When the temperature was controlled at -78°C and the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:3, Ic 1.15g, with a yield of 49%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:4, Ic 1.62g, with a yield of 69%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:5, Ic 1.78g, with a yield of 76%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:6, Ic 1.80g, with a yield of 77%; when the molar ratio of tris(triphenylphosphine)ruthenium dichloride to PCy3 was 1:7, Ic 1.73g, with a yield of 74%.

[0059] The structural formula of the obtained product is shown in Formula I, wherein X is bromine (Br).

[0060] Study on the ethenolysis of methyl oleate over Ru olefin metathesis catalysts substituted with ortho-benzylidene halides.

[0061] Example 4

[0062] Ia-Ic Ethylene Decomposition of Methyl Oleate

[0063] This reaction has high requirements on the purity of methyl oleate, and commercially available methyl oleate needs to be purified:

[0064] 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.

[0065] 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.

[0066]

[0067] 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 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, at which point the catalyst concentration is 100 ppm). Evacuate the autoclave for 1 minute with a vacuum pump, introduce ethylene gas to give the autoclave a slight positive pressure (0.01 MPa), and repeat this process 3 times. Evacuate the autoclave again for one minute with a vacuum pump, and increase the ethylene pressure in the autoclave to a certain level (e.g., 150 psi). The reactor was placed in a reaction module maintained at a constant temperature (20°C, 30°C, 40°C, 50°C), the reaction was stirred, and samples were taken every half an hour to detect the gas chromatography. After 6 hours of reaction, the yield did not continue to increase, and the selectivity for the products 9-octadec-9-ene and dimethyl 9-octadec-9-enedioate was greater than 99%.

[0068] At a temperature of 20°C, the methyl oleate conversion rate catalyzed by catalyst I reached 28.4%, and the TON value was 5355; at a temperature of 30°C, the methyl oleate conversion rate catalyzed by catalyst I reached 34.6%, and the TON value was 6525; at a temperature of 40°C, the methyl oleate conversion rate catalyzed by catalyst I reached 39.4%, and the TON value was 7430; at a temperature of 50°C, the methyl oleate conversion rate catalyzed by catalyst I reached 38.6%, and the TON value was 7279. At a temperature of 20°C, the methyl oleate conversion rate catalyzed by catalyst II reached 26.1%, and the TON value was 4322; at a temperature of 30°C, the methyl oleate conversion rate catalyzed by catalyst II reached 32.1%, and the TON value was 5315; at a temperature of 40°C, the methyl oleate conversion rate catalyzed by catalyst II reached 38.3%, and the TON value was 6341; at a temperature of 50°C, the methyl oleate conversion rate catalyzed by catalyst II reached 38.0%, and the TON value was 6291. At 20°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 22.7%, and the TON value was 3342; at 30°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 29.1%, and the TON value was 4284; at 40°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 37.0%, and the TON value was 5447; at 50°C, the conversion rate of methyl oleate catalyzed by catalyst III reached 37.6%, and the TON value was 5535. At 20°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 19.6%, and the TON value was 3105; at 30°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 31.8%, and the TON value was 5037; at 40°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 37.8%, and the TON value was 5900; at 50°C, the conversion rate of methyl oleate catalyzed by Grubbs III reached 38.2%, and the TON value was 6053. At different reaction temperatures, the conversion rate and TON value of catalysts I-II are higher than those of Grubbs III.

[0069] Method 2 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 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 autoclave for 1 minute with a vacuum pump, introduce ethylene gas to give the autoclave a slight positive pressure (0.01 MPa), and cycle this process 3 times. Evacuate the autoclave for another minute with a vacuum pump, and increase the pressure of ethylene in the autoclave 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%.

[0070] When the ethylene pressure is 50psi, the methyl oleate conversion rate of catalyst I reaches 27.5%, and the TON value is 5195; when the ethylene pressure is 100psi, the methyl oleate conversion rate of catalyst I reaches 31.7%, and the TON value is 5978; when the ethylene pressure is 150psi, the methyl oleate conversion rate of catalyst I reaches 39.4%, and the TON value is 7430; when the ethylene pressure is 200psi, the methyl oleate conversion rate of catalyst I reaches 38.9%, and the TON value is 7336. When the ethylene pressure is 50psi, the methyl oleate conversion rate of catalyst II reaches 25.0%, and the TON value is 4131; when the ethylene pressure is 100psi, the methyl oleate conversion rate of catalyst II reaches 33.7%, and the TON value is 5579; when the ethylene pressure is 150psi, the methyl oleate conversion rate of catalyst II reaches 38.3%, and the TON value is 6341; when the ethylene pressure is 200psi, the methyl oleate conversion rate of catalyst II reaches 38.5%, and the TON value is 6374. When the ethylene pressure is 50psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 19.8%, and the TON value is 2914; when the ethylene pressure is 100psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 32.4%, and the TON value is 4470; when the ethylene pressure is 150psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 37.0%, and the TON value is 5447; when the ethylene pressure is 200psi, the methyl oleate conversion rate catalyzed by catalyst III reaches 36.7%, and the TON value is 5418. When the ethylene pressure is 50psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 23.6%, and the TON value is 3744; when the ethylene pressure is 100psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 26.6%, and the TON value is 4215; when the ethylene pressure is 150psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 37.8%, and the TON value is 5990; when the ethylene pressure is 200psi, the conversion rate of methyl oleate catalyzed by Grubbs III reaches 38.1%, and the TON value is 6038. At different ethylene pressures, the conversion rate and TON value of catalyst I-II are higher than those of Grubbs III.

[0071] Example 5

[0072] 0.5mmol of N,N-diallylbenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(phenyl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 77.9 mg, 90%; when the solvent is toluene, the catalytic yield of catalyst Ia is 55.4 mg, 64%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 65.0 mg, 75%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 41.6 mg, 48%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 77.1 mg, 89%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 72.7 mg, 84%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 66.7 mg, 77%.

[0073] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(phenyl)methanone were 78.8 mg, 91% (Ib), 80.5 mg, 93% (Ic), and 77.1 mg, 89% (Grubbs I). The results showed that under the same conditions, Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(phenyl)methanone with a higher catalytic efficiency than Grubbs I.

[0074] (2,5-Dihydro-1H-pyrrol-1-yl)(phenyl)methanone: 1 H NMR (400MHz, CDCl3) δ7.51 (dd, J=7.2, 2.6Hz, 2H), 7.46–7.32 (m, 3H), 5.88 (d t,J=4.5,2.3Hz,1H),5.78–5.68(m,1H),4.43(s,2H),4.17(d,J=1.8Hz,2H). 13 C NMR (101MHz, CDCl3) δ169.77,136.74,129.82,128.33,126.72,125.78,125.27,55.74,53.35.

[0075] Example 6

[0076] 0.5mmol of N,N-diallyl-4-methylbenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(p-tolyl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 90.8mg, 97%; when the solvent is toluene, the catalytic yield of catalyst Ia is 73.0mg, 78%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 60.8mg, 65%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 33.7mg, 36%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 90.8mg, 97%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 89.9mg, 96%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 85.2mg, 91%.

[0077] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(p-tolyl)methanone were 88.9 mg, 95% (Ib), 90.8 mg, 97% (Ic), and 85.2 mg, 91% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(p-tolyl)methanone with a higher catalytic efficiency than Grubbs I under the same conditions.

[0078] (2,5-dihydro-1H-pyrrol-1-yl)(p-tolyl)methanone: 1 H NMR (400MHz, CDCl3) δ7.43(d,J=7.7Hz,2H),7.21(d,J=7.7Hz,2H),5.90(s,1H),5.75(s,1H),4.45(s,2H),4.22(s,2H),2.38(s,3H). 13C NMR (101MHz, CDCl3) δ170.04,140.02,133.94,128.98,126.95,126.00,125.26,55.85,53.45,21.43.

[0079] Example 7

[0080] 0.5mmol of N,N-diallyl-4-ethylbenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(4-ethylphenyl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 52.3 mg, 52%; when the solvent is toluene, the catalytic yield of catalyst Ia is 37.2 mg, 37%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 31.2 mg, 31%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 19.1 mg, 19%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 51.3 mg, 51%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 50.3 mg, 50%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 46.3 mg, 46%.

[0081] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction to obtain (2,5-dihydro-1H-pyrrol-1-yl)(4-ethylphenyl)methanone in yields of 54.3 mg, 54% (Ib), 58.3 mg, 58% (Ic), and 46.3 mg, 46% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(4-ethylphenyl)methanone at a higher catalytic efficiency than Grubbs I under the same conditions.

[0082] (2,5-Dihydro-1H-pyrrol-1-yl)(4-ethylphenyl)methanone: 1HNMR(400MHz, CDCl3)δ7.46(d,J=7.7Hz,2H),7.23(d,J=7.8Hz,2H),5.91(s,1H),5 .75(s,1H),4.46(s,2H),4.24(s,2H),2.68(q,J=7.6Hz,2H),1.24(t,J=7.6Hz,3H). 13 C NMR (101MHz, CDCl3) δ170.07,146.29,134.16,127.82,127.00,126.01,125.25,55.86,53.45,28.78,15.42.

[0083] Example 8

[0084] 0.5mmol of N,N-diallyl-4-ethoxybenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(4-ethoxyphenyl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 96.7mg, 89%; when the solvent is toluene, the catalytic yield of catalyst Ia is 81.5mg, 75%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 67.3mg, 62%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 42.4mg, 39%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 97.7mg, 90%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 94.5mg, 87%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 86.9mg, 80%.

[0085] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(4-ethoxyphenyl)methanone were 96.7 mg, 89% (Ib), 98.8 mg, 91% (Ic), and 91.2 mg, 84% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(4-ethoxyphenyl)methanone with a higher catalytic efficiency than Grubbs I under the same conditions.

[0086] (2,5-dihydro-1H-pyrrol-1-yl)(4-ethoxyphenyl)methanone: 1 HNMR (400MHz, CDCl3) δ7.43(s,2H),6.81(s,2H),5.80(s,1H),5.66(s,1H),4.35(s,2H),4.17(s,2H),3.97(s,2H),1.32(s,3H). 13 C NMR (101MHz, CDCl3) δ169.61,160.17,128.87,128.69,125.91,125.26,113.95,63.47,55.89,53.55,14.72.

[0087] Example 9

[0088] 0.5mmol of N,N-diallyl-4-fluorobenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(4-fluorophenyl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 87.0 mg, 91%; when the solvent is toluene, the catalytic yield of catalyst Ia is 76.5 mg, 80%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 52.6 mg, 55%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 41.1 mg, 43%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 86.0 mg, 90%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 80.3 mg, 84%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 77.4 mg, 81%.

[0089] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction to obtain (2,5-dihydro-1H-pyrrol-1-yl)(4-fluorophenyl)methanone in yields of 87.0 mg, 91% (Ib), 89.9 mg, 94% (Ic), and 83.2 mg, 87% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(4-fluorophenyl)methanone at a higher catalytic efficiency than Grubbs I under the same conditions.

[0090] (2,5-Dihydro-1H-pyrrol-1-yl)(4-fluorophenyl)methanone: 1 H NMR (400MHz, CDCl3) 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). 13C NMR (101MHz, CDCl3) 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, CDCl3) δ-110.12.

[0091] Example 10

[0092] 0.5mmol of N,N-diallyl-4-chlorobenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25℃, 30℃, 40℃ and 50℃), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (4-chlorophenyl)(2,5-dihydro-1H-pyrrol-1-yl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 94.5mg, 91%; when the solvent is toluene, the catalytic yield of catalyst Ia is 86.2mg, 83%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 54.0mg, 52%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 47.8mg, 46%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 94.5mg, 91%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 90.3mg, 87%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 86.2mg, 83%.

[0093] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction to obtain (4-chlorophenyl)(2,5-dihydro-1H-pyrrol-1-yl)methanone in yields of 94.5 mg, 91% (Ib), 95.5 mg, 92% (Ic), and 91.4 mg, 88% (Grubbs I). The results showed that Ia-Ic could obtain (4-chlorophenyl)(2,5-dihydro-1H-pyrrol-1-yl)methanone at a higher catalytic efficiency than Grubbs I under the same conditions.

[0094] (4-Chlorophenyl)(2,5-dihydro-1H-pyrrol-1-yl)methanone:1 H NMR (400MHz, CDCl3) δ7.49(d,J=8.2Hz,2H),7.39(d,J=8.1Hz,2H),5.91(s,1H),5.76(s,1H),4.44(s,2H),4.20(s,2H). 13 CNMR (101MHz, CDCl3) δ168.76,135.92,135.12,128.68,128.41,126.01,125.10,55.79,53.53.

[0095] Embodiment 11

[0096] 0.5mmol of N,N-diallyl-4-cyanobenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product 4-(2,5-dihydro-1H-pyrrole-1-carbonyl)benzonitrile. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 57.5mg, 58%; when the solvent is toluene, the catalytic yield of catalyst Ia is 38.6mg, 39%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 32.7mg, 33%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 24.8mg, 25%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 58.5mg, 59%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 49.6mg, 50%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 41.6mg, 42%.

[0097] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction to obtain 4-(2,5-dihydro-1H-pyrrole-1-carbonyl)benzonitrile in yields of 56.5 mg, 57% (Ib), 60.5 mg, 61% (Ic), and 53.5 mg, 54% (Grubbs I). The results showed that under the same conditions, Ia-Ic could obtain 4-(2,5-dihydro-1H-pyrrole-1-carbonyl)benzonitrile with a higher catalytic efficiency than Grubbs I.

[0098] 4-(2,5-Dihydro-1H-pyrrole-1-carbonyl)benzonitrile: 1 H NMR (400MHz, CDCl3) δ7.75(d,J=7.8Hz,2H),7.66(d,J=7.9Hz,2H),5.94(s,1H),5.79(s,1H),4.45(s,2H),4.19(s,2H). 13 C NMR (101MHz, CDCl3) δ167.73,140.93,132.39,127.55,125.88,125.01,118.14,113.51,55.59,53.52.

[0099] Example 12

[0100] 0.5mmol of N,N-diallyl-4-nitrobenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(4-nitrophenyl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 93.8mg, 86%; when the solvent is toluene, the catalytic yield of catalyst Ia is 69.8mg, 64%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 56.7mg, 52%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 41.5mg, 38%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 94.9mg, 87%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 89.5mg, 82%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 86.2mg, 79%.

[0101] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(4-nitrophenyl)methanone were 98.2 mg, 90% (Ib), 99.3 mg, 91% (Ic), and 91.6 mg, 84% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(4-nitrophenyl)methanone with a higher catalytic efficiency than Grubbs I under the same conditions.

[0102] (2,5-Dihydro-1H-pyrrol-1-yl)(4-nitrophenyl)methanone: 1 HNMR (400MHz, CDCl3) δ8.30(d,J=8.5Hz,2H),7.71(d,J=8.6Hz,2H),5.99–5.92(m,1H),5.83–5.71(m,1H),4.48(s,2H),4.18(s,2H). 13 C NMR (101MHz, CDCl3) δ167.59,148.50,142.75,127.95,126.09,124.92,123.89,55.65,53.60.

[0103] Embodiment 13

[0104] 0.5mmol of N,N-diallyl-2-methylbenzamide was dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) was added thereto. The reaction was carried out at a certain temperature (such as 25℃, 30℃, 40℃ and 50℃), and the reaction progress was detected by spot plate. After the reaction was completed, it 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 (2,5-dihydro-1H-pyrrol-1-yl)(o-tolyl)methanone. When the temperature was at room temperature (25℃) and the solvent was dichloromethane, the catalytic yield of catalyst Ia was 85.2mg, 91%; when the solvent was toluene, the catalyst Ia had a catalytic yield of 1.5mg, 1.0%; when the solvent was toluene, the catalyst Ia had a catalytic yield of 2.5mg, 1.0%; when the solvent was toluene, the catalyst Ia had a catalytic yield of 1.5mg, 1.0%; when the solvent was toluene, the catalyst Ia had a catalytic yield of 1.0 ... The catalytic yield of the catalyst Ia is 78.6 mg, 84%; when the solvent is tetrahydrofuran, the catalytic yield of the catalyst Ia is 58.0 mg, 62%; when the solvent is acetonitrile, the catalytic yield of the catalyst Ia is 42.1 mg, 45%. When the solvent is dichloromethane, the catalytic yield of the catalyst Ia is 85.2 mg, 91% at 30°C; when the temperature is 40°C, the catalytic yield of the catalyst Ia is 82.3 mg, 88%; when the temperature is 50°C, the catalytic yield of the catalyst Ia is 71.1 mg, 76%.

[0105] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(o-tolyl)methanone were 87.0 mg, 93% (Ib), 88.9 mg, 95% (Ic), and 83.3 mg, 89% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(o-tolyl)methanone with a higher catalytic efficiency than Grubbs I under the same conditions.

[0106] (2,5-dihydro-1H-pyrrol-1-yl)(o-tolyl)methanone: 1 H NMR (400MHz, CDCl3) δ7.30–7.25(m,1H),7.22(t,J=3.8Hz,3H),5.91(dt,J=6.6, 2.2Hz,1H),5.73(dt,J=6.5,2.0Hz,1H),4.45(s,2H),3.93(s,2H),2.33(s,3H). 13C NMR (101MHz, CDCl3) δ169.95,137.31,133.70,130.54,128.94,126.01,125.95,125.40,125.30,54.94,52.58,18.98.

[0107] Embodiment 14

[0108] 0.5mmol of N,N-diallyl-2,4,6-trimethylbenzamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(mesityl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 95.8mg, 89%; when the solvent is toluene, the catalytic yield of catalyst Ia is 84.0mg, 78%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 57.1mg, 53%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 42.0mg, 39%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 96.9mg, 90%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 89.3mg, 83%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 82.9mg, 77%.

[0109] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(trimethyl)methanone were 95.8 mg, 89% (Ib), 98.0 mg, 91% (Ic), and 93.7 mg, 87% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(trimethyl)methanone at a higher catalytic efficiency than Grubbs I under the same conditions.

[0110] (2,5-dihydro-1H-pyrrol-1-yl)(mesitylmethyl)ketone: 1H NMR (400MHz, CDCl3) 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 (101MHz, CDCl3) δ169.96,137.98,134.55,132.83,128.27,125.89,125.35,54.11,52.16,21.07,18.83.

[0111] Embodiment 15

[0112] 0.5mmol of N,N-diallyl-1-naphthamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(naphthalen-1-yl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 101.6 mg, 91%; when the solvent is toluene, the catalytic yield of catalyst Ia is 82.6 mg, 74%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 68.1 mg, 61%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 35.7 mg, 32%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 102.7 mg, 92%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 93.8 mg, 84%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 80.4 mg, 72%.

[0113] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(naphthalene-1-yl)methanone were 102.9 mg, 92% (Ib), 105.0 mg, 94% (Ic), and 98.3 mg, 88% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(naphthalene-1-yl)methanone with a higher catalytic efficiency than Grubbs I under the same conditions.

[0114] (2,5-Dihydro-1H-pyrrol-1-yl)(naphthalen-1-yl)methanone: 1 HNMR (400MHz, CDCl3) δ7.86 (d, J = 5.9 Hz, 3H), 7.49 (dd, J = 11.7, 4.5 Hz, 4H), 5.90 (s, 1H), 5.65 (s, 1H), 4.57 (s, 2H), 3.90 (s, 2H). 13 C NMR (101MHz, CDCl3) δ169.34,135.27,133.59,129.30,128.98,128.47,127.10,126.40,125.77,125.43,125.29,124.82,123.72,54.98,52.93.

[0115] Example 16

[0116] 0.5mmol of N,N-diallyl-2-naphthamide is dissolved in 0.5mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 1mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product (2,5-dihydro-1H-pyrrol-1-yl)(naphthalen-2-yl)methanone. When the temperature is at room temperature (25°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 100.5 mg, 90%; when the solvent is toluene, the catalytic yield of catalyst Ia is 77.0 mg, 69%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 61.4 mg, 55%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 41.3 mg, 37%. When dichloromethane is used as the solvent and the temperature is 30°C, the catalytic yield of catalyst Ia is 99.9 mg, 90%; when the temperature is 40°C, the catalytic yield of catalyst Ia is 92.7 mg, 83%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 83.7 mg, 75%.

[0117] Using the same catalytic conditions as Ia (temperature 25°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction, and the yields of (2,5-dihydro-1H-pyrrol-1-yl)(naphthalene-2-yl)methanone were 101.6 mg, 91% (Ib), 101.2 mg, 91% (Ic), and 99.4 mg, 89% (Grubbs I). The results showed that Ia-Ic could obtain (2,5-dihydro-1H-pyrrol-1-yl)(naphthalene-2-yl)methanone with a higher catalytic efficiency than Grubbs I under the same conditions.

[0118] (2,5-Dihydro-1H-pyrrol-1-yl)(naphthalen-2-yl)methanone: 1 HNMR (400MHz, CDCl3) δ8.00 (s, 1H), 7.84 (t, J = 9.1Hz, 3H), 7.60 (d, J = 9.2Hz, 1H),7.54–7.46(m,2H),5.88(s,1H),5.71(s,1H),4.49(s,2H),4.22(s,2H). 13 C NMR (101MHz, CDCl3) δ169.90,134.12,133.78,132.62,128.49,128.29,127.79,127.14,126.71,126.65,125.93,125.29,124.14,55.91,53.54.

[0119] Study on the cross-metathesis reaction of Ru olefin metathesis catalysts with ortho-halogenated benzylidene groups (CM), Examples 17-19.

[0120] Embodiment 17

[0121] 0.5 mmol of 3-phenoxy-1-propylene and 0.5 mmol of 4-fluorostyrene are dissolved in 1.0 mL of a solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 2.5 mol% of a catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by a plate. After the reaction is completed, the mixture is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether:ethyl acetate = 10:1 is used as a developing solvent to purify the target product (E)-1-fluoro-4-(3-phenoxyprop-1-en-1-yl)benzene. When the temperature is at room temperature (40°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 97.0 mg, 85%; when the solvent is toluene, the catalytic yield of catalyst Ia is 76.5 mg, 67%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 55.9 mg, 49%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 36.5 mg, 32%. When dichloromethane is used as the solvent and the temperature is 25°C, the catalytic yield of catalyst Ia is 70.8 mg, 62%; when the temperature is 30°C, the catalytic yield of catalyst Ia is 84.5 mg, 74%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 93.6 mg, 82%.

[0122] Using the same catalytic conditions as Ia (temperature 40°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction to obtain (E)-1-fluoro-4-(3-phenoxyprop-1-en-1-yl)benzene in yields of 97.4 mg, 85% (Ib), 99.3 mg, 87% (Ic), and 95.9 mg, 84% (Grubbs I). The results showed that under the same conditions, Ia-Ic could obtain (E)-1-fluoro-4-(3-phenoxyprop-1-en-1-yl)benzene with a catalytic efficiency higher than that of Grubbs I.

[0123] (E)-1-Fluoro-4-(3-phenoxyprop-1-en-1-yl)benzene: 1 HNMR(400MHz, CDCl3)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). 13C NMR (101MHz, CDCl3) 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, JCF=2.2Hz), 120.99, 115.56 (d, J CF=21.6Hz), 114.76, 68.44.19F NMR (376MHz, CDCl3) δ-113.92.

[0124] Embodiment 18

[0125] 0.5 mmol of 3-(4'-methoxy)phenoxy-1-propylene and 0.5 mmol of 4-fluorostyrene are dissolved in 1.0 mL of a solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 2.5 mol% of a catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25°C, 30°C, 40°C and 50°C), and the reaction progress is detected by a plate. After the reaction is completed, the mixture is added to a 10 cm high silica gel column (300 mesh), and a solvent of petroleum ether:ethyl acetate = 10:1 is used as a developing solvent to purify the target product (E)-1-fluoro-4-(3-(4-methoxyphenoxy)prop-1-en-1-yl)benzene. When the temperature is at room temperature (40°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 98.2mg, 76%; when the solvent is toluene, the catalytic yield of catalyst Ia is 80.1mg, 62%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 55.5mg, 43%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 36.2mg, 28%. When dichloromethane is used as the solvent and the temperature is 25°C, the catalytic yield of catalyst Ia is 64.6mg, 50%; when the temperature is 30°C, the catalytic yield of catalyst Ia is 81.4mg, 63%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 87.8mg, 68%.

[0126] Using the same catalytic conditions as Ia (temperature 40°C, solvent dichloromethane), Ib, Ic and Grubbs I were used to catalyze the reaction to obtain (E)-1-fluoro-4-(3-(4-methoxyphenoxy)prop-1-en-1-yl)benzene in yields of 93.0 mg, 72% (Ib), 94.3 mg, 73% (Ic), and 90.4 mg, 70% (Grubbs I). The results showed that Ia-Ic could obtain (E)-1-fluoro-4-(3-(4-methoxyphenoxy)prop-1-en-1-yl)benzene at a higher catalytic efficiency than Grubbs I under the same conditions.

[0127] (E)-1-Fluoro-4-(3-(4-methoxyphenoxy)prop-1-en-1-yl)benzene: 1 HNMR (400MHz, CDCl3) 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 (101MHz, CDCl3) δ154.00, 152.74, 132.68, 131.70, 128.12 (d, JCF = 7.9Hz), 124.53, 115.79, 115.64, 115.43, 114.69, 69.26, 55.73. 19 F NMR (376MHz, CDCl3) δ-114.01.

[0128] Embodiment 19

[0129] 0.5mmol of 3-(4'-phenyl)phenoxy-1-propylene and 0.5mmol of styrene are dissolved in 1.0mL of solvent (such as dichloromethane, toluene, tetrahydrofuran, acetonitrile, etc.), and then 2.5mol% of catalyst (Ia) is added thereto, and the reaction is carried out at a certain temperature (such as 25℃, 30℃, 40℃ and 50℃), and the reaction progress is detected by spot plate. After the reaction is completed, it is added to a 10cm high silica gel column (300 mesh), and a solvent of petroleum ether: ethyl acetate = 10:1 is used as a developing solvent to purify the target product 4-(cinnamyloxy)-1,1'-biphenyl. When the temperature is at room temperature (40°C) and the solvent is dichloromethane, the catalytic yield of catalyst Ia is 94.5mg, 66%; when the solvent is toluene, the catalytic yield of catalyst Ia is 80.2mg, 56%; when the solvent is tetrahydrofuran, the catalytic yield of catalyst Ia is 53.0mg, 37%; when the solvent is acetonitrile, the catalytic yield of catalyst Ia is 34.4mg, 24%. When dichloromethane is used as the solvent and the temperature is 25°C, the catalytic yield of catalyst Ia is 58.7mg, 41%; when the temperature is 30°C, the catalytic yield of catalyst Ia is 74.5mg, 52%; when the temperature is 50°C, the catalytic yield of catalyst Ia is 85.9mg, 60%.

[0130] Using the same catalytic conditions as Ia (temperature 40°C, solvent dichloromethane), Ib and Ic were used to catalyze the reaction with Grubbs I to obtain 4-(cinnamoyloxy)-1,1'-biphenyl in yields of 88.8 mg, 62% (Ib), 91.6 mg, 64% (Ic), and 83.1 mg, 58% (Grubbs I). The results showed that Ia-Ic could obtain 4-(cinnamoyloxy)-1,1'-biphenyl with a higher catalytic efficiency than Grubbs I under the same conditions.

[0131] 4-(Cinnamoyloxy)-1,1'-biphenyl: 1 H NMR (400MHz, CDCl3) 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,1 H),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). 13C NMR(101MHz,CDCl3)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。

Claims

1. A benzylidene ortho-halogenated Ru olefin metathesis catalyst, characterized in that: As shown in Formula I: Wherein, X is selected from fluorine, chlorine or bromine.

2. A method for preparing the benzylidene ortho-halogenated Ru olefin metathesis catalyst according to claim 1, characterized in that: include: In an organic solvent system, tris(triphenylphosphine)ruthenium dichloride reacts with o-fluorobenzyl azide, o-chlorobenzyl azide or o-bromobenzyl azide.

3. The method according to claim 2, characterized in that Dissolve tri(triphenylphosphine)ruthenium dichloride in an organic solvent, cool the reaction system to -10 to -78°C, and add o-fluorobenzyl azide, o-chlorobenzyl azide or o-bromobenzyl azide to react.

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

5. The method according to claim 3, characterized in that The organic solvent is dichloromethane.

6. The method according to claim 2 or 3, characterized in that The molar ratio of the o-fluorobenzyl azide, the o-chlorobenzyl azide or the o-bromobenzyl azide to tris(triphenylphosphine)ruthenium dichloride is (1:1) to (3:1).

7. The method according to any one of claims 2 to 6, characterized in that: The method further comprises: after the reaction is completed, removing part of the solvent under reduced pressure, adding methanol for washing, filtering and drying the precipitated product.

8. The method of claim 7, characterized in that After adding o-fluorobenzyl azide, o-chlorobenzyl azide or o-bromobenzyl azide, the temperature is maintained for reaction for more than 30 minutes. After adding tricyclohexylphosphine at room temperature, the reaction time is required to be more than 30 minutes.

9. Use of the benzylidene ortho-halogenated Ru olefin metathesis catalyst according to claim 1 in the catalytic conversion of unsaturated octadecane dicarboxylic acid dimethyl ester, 1-decene, and 9-decenoic acid methyl ester.

10. A catalytic conversion process of saturated octadecane dicarboxylic acid dimethyl ester, 1-decene, and 9-decenoic acid methyl ester, characterized in that: The benzylidene ortho-halogenated Ru olefin metathesis catalyst according to claim 1 is used.

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