A non-cyclic aminooxy carbene complex ruthenium catalyst, a preparation method and application thereof

Abstract

This invention belongs to the field of composite ruthenium compound synthesis technology, specifically relating to an acyclic aminooxycarbene composite ruthenium catalyst with the following structure: M is a ruthenium atom, Z1 and Z2 each independently represent an anionic ligand, X1 is an oxygen atom, and L1 represents an inert ligand selected from one of the acyclic aminocarbene ligands shown in [examples omitted]. This catalyst simultaneously achieves high catalytic efficiency and excellent selectivity in olefin metathesis reactions, and the inert ligand can be conveniently synthesized in a one-pot, multi-gram scale reaction, thereby reducing catalyst production costs.

Description

Technical Field

[0001] This invention belongs to the field of composite ruthenium compound synthesis technology, specifically relating to an acyclic aminooxycarbene composite ruthenium catalyst, its preparation method, and its application. Background Technology

[0002] Olefin metathesis is one of the most common synthetic strategies for constructing carbon-carbon double bonds, widely used in the synthesis of various target products in pharmaceuticals, petrochemicals, fine chemicals, and polymer materials. Producing straight-chain α-olefins via ethylene alcoholysis (cross-metathesis with ethylene) has become an effective route utilizing renewable feedstocks (such as fatty acid methyl esters). Ethylene alcoholysis can selectively prepare 1-decene and methyl 9-decenoate from biomass. 1-Decanene is an important industrial chemical used in the production of polyα-olefins, while the latter is commonly used as a high-performance lubricant. Currently, homogeneous metal carbene complexes, represented by ruthenium, tungsten, and molybdenum alkylene complexes, have been shown to achieve highly selective ethylene alcoholysis reactions.

[0003] Nitrogen heterocyclic carbenes (NHCs) have been widely used in ruthenium-based metathesis catalysts, and their structural tuning is often crucial for optimizing challenging metathesis reactions. In 2015, Grubbs and his collaborators reported achieving up to 95% α-olefin selectivity in the ethylene alcoholysis using asymmetric NHCs. Since then, numerous studies have focused on improving the selectivity of target terminal olefins to reduce the formation of self-metathesis and secondary metathesis byproducts. In 2019, Grela's team demonstrated that the asymmetric structural features of NHCs play a key role in achieving high selectivity (up to 98%) in the ethylene alcoholysis of methyl oleate.

[0004] The cyclic (alkyl) (amino)carbene (CAACs) ruthenium complexes developed by Bertrand, Grubbs, and their collaborators are currently the best-performing catalysts for ethylene alcoholysis. Their superior performance can be attributed to the strong electron-donating ability of the CAAC ligands, which enhances the carbene-metal bond and helps stabilize the ruthenium intermediate. Therefore, in recent years, researchers have developed various strategies to enhance α-electron-donating ability without weakening π-electron-withdrawing ability. Among these, acyclic diaminocarbenes (ADCs), as auxiliary ligands, have shown potential application value due to their stronger α-electron-donating properties than CAACs. For example, Bielawski and his collaborators reported that ruthenium catalysts containing acyclic diaminocarbenes (ADCs) exhibited a higher Z / E selectivity ratio in stereoselective metathesis reactions. In 1998, Alder's group first reported the free carbene structure of acyclic aminooxycarbenes with steric hindrance requirements. In 2011, Hong's team reported the highly efficient catalytic performance of sterically hindered acyclic aminooxycarbene (AAOC) composite gold catalysts in intramolecular hydroammoniation reactions. Acyclic aminooxycarbene (AAOC) ligands possess both strong electron-donating properties and structural asymmetry, which may help stabilize ruthenium intermediates and improve reaction selectivity. They hold promise as a novel class of auxiliary ligands, exhibiting excellent catalytic performance in ethylene hydrolysis. Furthermore, from an industrial application perspective, catalyst availability is crucial, particularly the ability to synthesize its precursors (ligands) on a large scale and without hindrance. While CAAC-type ruthenium catalysts exhibit excellent catalytic efficiency, more convenient catalyst preparation routes could further reduce production costs. Summary of the Invention

[0005] The purpose of this invention is to provide an acyclic aminooxycarbene composite ruthenium catalyst, in order to reduce the preparation cost of catalysts in olefin metathesis reactions.

[0006] To achieve the above objectives, the present invention provides an acyclic aminooxycarbene composite ruthenium catalyst, the structure of which is shown in formula (I): ; In formula (Ⅰ), M is a ruthenium atom; Z1 and Z2 each independently represent an anionic ligand; X1 represents one oxygen atom; L1 represents an inert ligand, and L1 is selected from one of the acyclic aminocarbene ligands shown in formula (II), formula (III), or formula (IV); ; In formulas (II), (III), and (IV), R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1-C atoms, and C4 atoms. 12 Alkyl, C3-C12 cycloalkyl, C2-C 12 alkenyl and C5-C 20 One of the aryl groups, wherein R1, R2, R3, and R4 may optionally be separated by at least one C1-C. 12 Alkyl, C1-C 12 All-haloalkyl, C1-C 12 Alkoxy or one halogen atom can be substituted; R1, R2, R3 and R4 can bond to each other.

[0007] The present invention also provides an acyclic aminooxycarbene ligand, the structure of which is shown in formula (V): ; In formula (V), X2 represents an anionic ligand, and X2 is selected from chloride ions and hexafluorophosphate ions; R5, R6, R7 and R8 each independently represent a hydrogen atom or a C1-C atom. 12 Alkyl groups; R5, R6, R7, and R8 can bond to each other.

[0008] The present invention also provides a method for preparing the above-mentioned acyclic aminooxycarbene ligand, the method comprising: reacting a substituted formamide compound having the structure shown in formula (VI) with an aryl silyl ether or phenol as an intermediate via a variant of the Vilsmeier-Haack reagent; the synthetic route is shown in formula (1); ; .

[0009] This invention also provides a method for preparing the above-mentioned acyclic aminooxycarbene composite ruthenium catalyst. When the structure of the acyclic aminooxycarbene composite ruthenium catalyst is as shown in formula (a), its synthesis route is as shown in formula (2). The preparation method includes the following steps: ; ; 1) Take an organic base and the acyclic aminooxycarbene ligand as described in claim 4, add them to a solvent, react at -78°C for 0.5 to 3 h, then add Hoveyda-Grubbs first-generation catalyst, continue stirring for 2 h, and concentrate to obtain crude product I; 2) Dissolve the crude product I obtained in step 1) in dichloromethane, add cuprous chloride or ion exchange resin, and heat the reaction at 40℃~60℃ for 1~2 h to obtain the reaction mixture. Wash with dichloromethane, combine the filtrates and concentrate to obtain crude product II. Crude product II is purified to obtain the product shown in formula (a).

[0010] Optionally, in step 1), the organic base is one or more of bis(trimethylsilyl)aminopotassium, potassium tert-butoxide, and potassium tert-pentoxide.

[0011] Optionally, in step 1), the solvent is an ether solvent.

[0012] Optionally, in step 1), the Hoveyda-Grubbs first-generation catalyst is dissolved in an aromatic hydrocarbon solvent and then added to the reaction.

[0013] This invention also provides the application of the above-mentioned acyclic aminooxycarbene composite ruthenium catalyst in olefin metathesis reactions.

[0014] Optionally, the above-mentioned acyclic aminooxycarbene composite ruthenium catalyst is supported in a solid material to obtain a supported acyclic aminooxycarbene composite ruthenium catalyst, and then the supported acyclic aminooxycarbene composite ruthenium catalyst is applied to the metathesis reaction of olefins.

[0015] Optionally, the solid material is silicon dioxide.

[0016] Compared with the prior art, the present invention has the following beneficial effects: 1. The acyclic aminooxycarbene composite ruthenium catalyst of this invention can catalyze the cross-metathesis reaction of methyl oleate and ethylene with excellent stability and reactivity, achieving a product selectivity of over 90% and a catalyst TON exceeding 50,000. Compared to existing homogeneous catalysts, the supported acyclic aminooxycarbene composite ruthenium catalyst of this invention is easier to separate from the reaction products, avoiding metal residues in the pure product and solving the problem of high cost due to difficult catalyst recovery.

[0017] 2. The strong electron-donating properties and asymmetric structure of the acyclic aminooxycarbene (AAOC) ligand in this invention jointly enhance the activity and selectivity of the ruthenium catalyst. This represents a rare example of supported acyclic aminooxycarbene composite ruthenium catalysts simultaneously achieving high catalytic efficiency and excellent selectivity in olefin metathesis reactions, providing a unique research paradigm for the field of transition metal catalysis and demonstrating broad potential in the development of novel acyclic aminooxycarbene ligands and their applications in metal catalysis. Furthermore, the acyclic aminooxycarbene ligand in this invention can be conveniently synthesized via a one-pot, multi-gram-guar-scale reaction. From an industrial application perspective, the ligand can be synthesized on a large scale without obstacles. The convenient preparation route increases the availability of the catalyst, further reducing production costs and enabling large-scale industrial production.

[0018] 3. In the cross metathesis reaction of methyl oleate and ethylene carried out in this invention, ethylene under normal pressure is used as raw material, eliminating the need for pressure-resistant reactors, high-pressure pipelines and other pressure equipment, resulting in lower production costs, significant economic benefits, and good versatility. Detailed Implementation

[0019] The present invention will be further described in detail below through specific examples to enable those skilled in the art to implement it based on the description. The following description is intended to disclose the present invention so that those skilled in the art can implement it. The preferred embodiments described below are merely examples, and those skilled in the art can conceive of other obvious modifications. The basic principles of the present invention defined in the following description can be applied to other embodiments, modifications, improvements, equivalents, and other technical solutions that do not depart from the spirit and scope of the present invention. In this invention, unless otherwise specified, the raw materials and equipment used are commercially available or commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0020] Example 1: Synthesis of AAOC ligand L1-1 At -78°C, (COCl)₂ (6.75 mmol, 0.84 mL, 1.5 equivalents) was added to a dichloromethane solution of N,N-diisopropylformamide (4.5 mmol, 0.65 mL, 0.95 equivalents). The mixture was stirred at room temperature for 1 h, and after removing all volatiles by vacuum evaporation, dichloromethane was added. A dichloromethane solution (10 mL) of (2,6-diisopropylphenoxy)trimethylsilane (5 mmol) was added dropwise to the above reaction solution at -78°C. After stirring at room temperature for 3 h, the reaction solution was concentrated to 2 mL, and the precipitated solid was washed with n-hexane. The resulting chloride salt (1 equivalent) was added to a small amount of aqueous solution of KPF₆ (1.1 equivalents), and the resulting precipitate was extracted with dichloromethane. The organic layers were combined, dried with anhydrous Na2SO4, filtered and concentrated, and the resulting solid was recrystallized from n-hexane to give the product AAOC ligand L1-1 (1.6 g), with a yield of 82%.

[0021] The 1H NMR spectrum of the product AAOC ligand L1-1 is as follows: 1 H NMR (CDCl3, 400 MHz), δ (ppm):8.29 (1H, s, NC H O), 7.33 (1H, t, J = 7.6 Hz, Ar H ), 7.23 (2H, t, J = 8.0 Hz, Ar H ), 4.43-4.31 (2H, m, NC H ), 2.85-2.75 (2H, m, ArC H ), 1.62 (6H, d, J = 5.7Hz, CHCH3 ), 1.47 (6H, d, J = 5.7 Hz, CHC H3 ), 1.24 (12H, d, J = 6.9 Hz, CHC H3 ). The carbon NMR spectrum of the product AAOC ligand L1-1 is as follows: 13 C NMR (CDCl3, 101 MHz), δ (ppm): 165.3, 149.7, 139.1, 129.3, 125.3, 58.5, 52.6, 27.7, 23.2, 20.8, 19.7. Therefore, the structure of the product AAOC ligand L1-1 is as follows: .

[0022] Example 2 Synthesis of AAOC ligand L1-2 At -78°C, (COCl)₂ (4 mmol, 0.34 mL, 1.5 equivalents) was added to a dichloromethane solution of piperidine-1-carboxaldehyde (2.85 mmol, 322 mg, 0.95 equivalents), and the mixture was stirred at room temperature for 1 h. After removing all volatiles by vacuum evaporation, dichloromethane was added. A dichloromethane solution (10 mL) of (3 mmol) trimethylsilane was added dropwise to the above reaction solution at -78°C, and the mixture was stirred at room temperature for 3 h. The reaction solution was then concentrated to 2 mL, and the precipitated solid was washed with n-hexane, with a yield of 85% (748 mg). The resulting chloride salt (748 mg, 1 equivalent) was added to a small amount of aqueous solution of KPF₆ (444 mg, 1.1 equivalents), and the resulting precipitate was extracted with dichloromethane. The organic layers were combined, dried with anhydrous Na2SO4, filtered and concentrated, and the resulting solid was recrystallized from n-hexane to give the product AAOC ligand L1-2 (327 mg), with a yield of 32%.

[0023] The 1H NMR spectrum of the product AAOC ligand L1-2 is as follows: 1H NMR (CDCl3, 400 MHz), δ (ppm): 8.32 (1H, s, NC). H O), 7.33 (1H, dd, J = 8.2, 7.3 Hz, Ar H ), 7.21 (2H, d, J = 7.7Hz, Ar H ), 4.12 – 3.95 (4H, m, NC H2 ), 2.89 (2H, hept,J = 6.8 Hz, C H ), 1.99 –1.78 (6H, m, C H2 ), 1.23 (12H, d, J = 6.8 Hz, C H3 ). The carbon NMR spectrum of the product AAOC ligand L1-2 is as follows: 13 C NMR (CDCl3, 101 MHz), δ (ppm): 162.8, 149.0, 139.3, 129.2, 125.2, 53.2, 47.3, 27.5, 26.4, 25.9, 22.9, 22.8. Therefore, the structure of the product AAOC ligand L1-2 is as follows: .

[0024] Example 3 Synthesis of AAOC ligand L1-3 At -78°C, (COCl)₂ (8.6 mmol, 0.73 mL, 1.5 equivalents) was added to a dichloromethane solution of pyrrole-1-carboxaldehyde (5.7 mmol, 565 mg, 0.95 equivalents), and the mixture was stirred at room temperature for 1 h. After removing all volatiles by vacuum evaporation, dichloromethane was added. A dichloromethane solution (2 mL) of (6 mmol) of (2,6-diisopropylphenoxy)trimethylsilane was added dropwise to the above reaction solution at -78°C, and the mixture was stirred at room temperature for 3 h. The reaction solution was then concentrated to 2 mL, and the precipitated solid was washed with n-hexane (yield 91%, 1.54 g). The resulting chloride salt (100 mg, 1 equivalent) was added to a small amount of aqueous solution of KPF₆ (62 mg, 1.1 equivalents), and the resulting precipitate was extracted with dichloromethane. The organic layers were combined, dried with anhydrous Na2SO4, filtered and concentrated, and the resulting solid was recrystallized from n-hexane to give the product AAOC ligand L1-3 (70 mg), with a yield of 51%.

[0025] The 1H NMR spectrum of the product AAOC ligand L1-3 is as follows: 1H NMR (CDCl3, 400 MHz), δ (ppm): 8.41 (1H, s, NC). H O), 7.36 – 7.28 (1H, m, Ar H ), 7.21 (2H, d, J = 7.7 Hz, Ar H ),4.20 (2H, t, J = 6.7 Hz, NC H 2), 3.99 (2H, t, J = 6.9 Hz, NC H 2 ), 2.91 (2H,hept, J = 6.8 Hz, CC H ), 2.34 – 2.14 (4H, m, CH2), 1.21 (12H, d, J = 6.8 Hz,C H 3 ). The carbon NMR spectrum of the product AAOC ligand L1-3 is as follows: 13 C NMR (CDCl3, 101 MHz), δ (ppm): 163.0, 149.3, 139.5, 129.1, 125.1, 77.4, 77.1, 76.8, 52.6, 49.6, 27.4, 24.6,23.9, 23.0. Therefore, the structure of the product AAOC ligand L1-3 is as follows: .

[0026] Example 4 Synthesis of AAOC ligand L1-4 Pyrrole-1-carboxaldehyde (5 mmol, 496 mg) was dissolved in dichloromethane (0.02 M), and Tf₂O (5 mmol, 0.84 mL) was slowly added dropwise at -78 °C. The mixture was heated to room temperature and stirred for 1 h. Then, a solution of 2-tert-butyl-6-propylphenol (5 mmol, 961 mg) and triethylamine (5.5 mmol, 0.77 mL) in dichloromethane (10 mL) was added at -78 °C, and the mixture was stirred at room temperature for 4 h to obtain the crude product. The crude product was purified by short silica gel column chromatography, and the residue was ground with additional ethane to precipitate a solid, yielding the product AAOC ligand L1-4 (1.11 g), with a yield of 52%.

[0027] The 1H NMR spectrum of the product AAOC ligand L1-4 is as follows: 1H NMR (CDCl3, 400 MHz), δ (ppm): δ9.19 (1H, s, NC). H O), 7.30-7.17 (2H, m, Ar H ), 4.35 (2H, t, J = 6.5 Hz, C H 2 ),3.99 (2H, t, J = 6.7 Hz, C H 2), 3.18-3.11 (3H, m, C H 2 ), 2.50 (2H, t, J = 7.4Hz, C H 2 ), 2.25 (4H, dq, J = 28.6, 6.7 Hz, C H 2 ), 1.61 (2H, td, J = 14.9, 7.4Hz, C H 2 ), 1.36-1.33 (12H, m, C H 3 ), 0.90 (3H, t, J = 7.2 Hz, C H 3 ). The carbon NMR spectrum of the product AAOC ligand L1-3 is as follows: 13 C NMR (CD2Cl2, 101 MHz), δ (ppm):164.9, 151.7, 140.8, 133.8, 129.4, 128.4, 126.2, 49.8, 46.0, 34.8, 32.0,30.7, 24.9, 24.1, 22.9, 13.5. Therefore, the structure of the product AAOC ligand L1-4 is as follows: .

[0028] Example 5 Synthesis of Ruthenium Catalyst AAOC-Ru1 The AAOC ligand L1-1 (0.2 mmol, 87 mg) prepared in Example 1 and potassium bis(trimethylsilyl)amino (KHMDS, 0.22 mmol, 44 mg) were added to tetrahydrofuran (2 mL), and the mixture was stirred at -78 °C for 0.5 h. Hoveyda-Grubbs first-generation catalyst (purchased from Adamas, HGI, 0.1 mmol, 60 mg) dissolved in benzene (2 mL) was added, and the mixture was stirred for another 2 h. After the reaction was complete, the reaction solution was concentrated to obtain crude product I. Crude product I was dissolved in dichloromethane, and Amberlyst 15 resin (purchased from Alfa Aesar, 4 equivalents) was added. The mixture was heated at 50 °C for 1 h to obtain a reaction mixture. The reaction mixture was filtered through a diatomaceous earth filter, washed with dichloromethane, and the filtrates were combined and concentrated to obtain crude product II. Crude product II was purified by silica gel column chromatography to obtain product AAOC-Ru1 (43 mg), with a yield of 70%.

[0029] The proton NMR spectrum of product AAOC-Ru1 is as follows: 1 H NMR (CD2Cl2, 400 MHz), δ (ppm): 15.64(1H, s, Ru=C H ), 7.56-7.52 (1H, m, Ar H ), 7.48 (1H, t, J = 7.6 Hz, Ar H ), 7.33(2H, d, J = 8.0 Hz, Ar H ), 6.94 (1H, d, J = 8.4 Hz, Ar H ), 6.89 (2H, t, J = 2.9Hz, Ar H ), 5.25 (1H, m, J = 6.3 Hz, C H ), 5.13-5.04 (1H, m, C H ), 3.79-3.69 (1H,m, C H ), 3.19-3.09 (2H, m, C H ), 1.67 (12H, d, J = 6.1 Hz, C H 3 ), 1.55 (6H, d, J = 6.9 Hz, C H 3), 1.12 (6H, d, J = 6.7 Hz, C H 3 ), 0.86 (6H, d, J = 6.9 Hz, C H 3 ). The carbon NMR spectrum of product AAOC-Ru1 is as follows: 13 C NMR (CD2Cl2, 101 MHz), δ (ppm):223.6, 152.1, 151.4, 144.0, 142.5, 130.4, 127.2, 124.6, 122.9, 122.5, 112.9,74.9, 56.8, 50.3, 26.4, 25.4, 22.4, 22.0, 21.8, 20.1. Therefore, the structure of the product AAOC-Ru1 is as follows: .

[0030] Example 6 Synthesis of Ruthenium Catalyst AAOC-Ru2 The AAOC ligand L1-2 (0.4 mmol, 124 mg) prepared in Example 2 and potassium bis(trimethylsilyl)amino (KHMDS, 0.44 mmol, 88 mg) were added to tetrahydrofuran (2 mL), and the mixture was stirred at -78 °C for 0.5 h. Hoveyda-Grubbs first-generation catalyst (purchased from Adamas, HGI, 0.1 mmol, 60 mg) dissolved in benzene (2 mL) was added, and the mixture was stirred for another 2 h. After the reaction was complete, the reaction solution was concentrated to obtain crude product I. Crude product I was dissolved in dichloromethane, and Amberlyst 15 resin (purchased from Alfa Aesar, 4 equivalents) was added. The mixture was heated at 50 °C for 1 h to obtain a reaction mixture. The reaction mixture was filtered through a diatomaceous earth filter, washed with dichloromethane, and the filtrates were combined and concentrated to obtain crude product II. Crude product II was purified by silica gel column chromatography to obtain product AAOC-Ru2 (22 mg), with a yield of 38%.

[0031] The 1H NMR spectrum of the product AAOC-Ru2 is as follows: 1 H NMR (CD2Cl2, 400 MHz), δ (ppm): 15.67(1H, s, Ru=CH), 7.56-7.52 (1H, m, ArH), 7.45 (1H, t, J = 7.6 Hz, ArH), 7.30 (2H, d, J= 7.6 Hz, ArH), 6.96-6.87 (3H, m, ArH), 5.16-5.07 (1H, m, OCH), 4.51 (2H, t, J = 5.5 Hz, CH2), 4.01 (2H, t, J = 5.5 Hz, CH2), 3.24-3.13 (2H,m, CH2), 2.13-2.07 (2H, m, CH2), 1.88-1.82 (2H, m, CH2), 1.74-1.68 (8H, m,CH2, and CH3), 1.11 (6H, d, J = 6.9 Hz, CH3), 0.95 (6H, d, J = 6.9 Hz, CH3). The carbon NMR spectrum of the product AAOC-Ru2 is as follows: 13 C NMR (CD2Cl2, 101 MHz), δ (ppm):220.0, 152.1, 152.0, 143.6, 141.8, 130.4, 127.0, 124.1, 122.7, 122.5, 112.9,75.2, 47.7, 26.8, 26.3, 24.3, 24.1, 21.9, 21.1. Therefore, the structure of the product AAOC-Ru2 is as follows: .

[0032] Example 7 Synthesis of Ruthenium Catalyst AAOC-Ru3 The AAOC ligand L1-3 (0.4 mmol, 118 mg) prepared in Example 3 and potassium bis(trimethylsilyl)amino (KHMDS, 0.44 mmol, 88 mg) were added to tetrahydrofuran (2 mL), and the mixture was stirred at -78 °C for 0.5 h. Hoveyda-Grubbs first-generation catalyst (purchased from Adamas, HGI, 0.1 mmol, 60 mg) dissolved in benzene (2 mL) was added, and the mixture was stirred for another 2 h. After the reaction was complete, the reaction solution was concentrated to obtain crude product I. Crude product I was dissolved in dichloromethane, and Amberlyst 15 resin (purchased from Alfa Aesar, 4 equivalents) was added. The mixture was heated at 50 °C for 1 h to obtain a reaction mixture. The reaction mixture was filtered through a diatomaceous earth filter, washed with dichloromethane, and the filtrates were combined and concentrated to obtain crude product II. Crude product II was purified by silica gel column chromatography to obtain product AAOC-Ru3 (30 mg), with a yield of 51%.

[0033] The 1H NMR spectrum of the product AAOC-Ru3 is as follows: 1 H NMR (CD2Cl2, 400 MHz), δ (ppm): 15.70(1H, s, Ru=CH), 7.56-7.51 (1H, m, Ar H ), 7.46 (1H, t, J = 7.8 Hz, Ar H ), 7.30(2H, d, J = 7.6 Hz, Ar H ), 6.98-6.87 (3H, m, Ar H ), 5.20-5.10 (1H, m, OC H ),4.81 (2H, t, J = 6.7 Hz, C H 2 ), 4.04 (2H, t, J = 7.2 Hz, C H 2 ), 3.24-3.13 (2H,m, C H 2 ), 2.24-2.18 (2H, m, C H 2 ), 2.09-2.02 (2H, m, C H 2 ), 1.72 (6H, d, J = 6.1Hz, C H 3 ), 1.12 (6H, d, J = 7.2 Hz, C H 3 ), 0.93 (6H, d, J = 6.5 Hz, C H 3 ). The carbon NMR spectrum of the product AAOC-Ru3 is as follows: 13 C NMR (CD2Cl2, 101 MHz), δ (ppm): 221.1, 152.3, 152.2, 143.5, 141.8, 130.2, 127.0, 124.1, 122.4, 112.8, 75.4,50.5, 50.3, 26.8, 26.1, 24.5, 23.8, 21.9, 21.2. Therefore, the structure of the product AAOC-Ru3 is as follows: .

[0034] Example 8 Synthesis of Ruthenium Catalyst AAOC-Ru4 The AAOC ligand L1-4 (0.6 mmol, 254 mg) prepared in Example 4 and potassium bis(trimethylsilyl)amino (KHMDS, 0.66 mmol, 180 mg) were added to tetrahydrofuran (2 mL), and the mixture was stirred at -78 °C for 0.5 h. Hoveyda-Grubbs first-generation catalyst (purchased from Adamas, HGI, 0.3 mmol, 180 mg) dissolved in benzene (2 mL) was added, and the mixture was stirred for another 2 h. After the reaction was complete, the reaction solution was concentrated to obtain crude product I. Crude product I was dissolved in dichloromethane, and Amberlyst 15 resin (purchased from Alfa Aesar, 4 equivalents) was added. The mixture was heated at 50 °C for 1 h to obtain a reaction mixture. The reaction mixture was filtered through a diatomaceous earth filter, washed with dichloromethane, and the filtrates were combined and concentrated to obtain crude product II. Crude product II was purified by silica gel column chromatography to obtain product AAOC-Ru4 (195 mg), with a yield of 37%.

[0035] The proton NMR spectrum of the product AAOC-Ru4 is as follows: 1 H NMR (CD2Cl2, 400 MHz), δ (ppm): 15.90(1H, s, Ru=C H ), 7.55-7.47 (2H, m, Ar H ), 7.33 (1H, t, J = 7.6 Hz, Ar H ), 7.09(1H, dd, J = 7.4, 1.3 Hz, Ar H ), 6.99-6.92 (3H, m, Ar H ), 5.21-5.12 (1H, m, OC) H ), 4.92-4.80 (2H, m, C H 2 ), 3.99 (2H, ddd, J = 27.9, 12.7, 7.2 Hz, C H 2 ), 2.66-2.58 (1H, m, C) H 2 ), 2.32-1.99 (5H, m, C H2 C H 2 C H 2 ), 1.65-1.81 (6H, m, C H 3 ), 1.51-1.39 (2H, m, C H 2 ), 1.30 (9H, s, (C H 3 ) 3 ), 0.82 (3H, t, J = 7.2 Hz, C H 3 ). The carbon NMR spectrum of the product AAOC-Ru4 is as follows: 13 C NMR (CD2Cl2, 101 MHz), δ (ppm): 221.8, 154.1, 152.6, 143.1, 142.1, 137.3, 130.2, 128.5, 126.3, 125.9, 122.5,122.4, 112.9, 75.4, 51.0, 50.7, 35.6, 33.3, 31.6, 25.9, 24.1, 23.6, 21.9,21.8, 13.6. Therefore, the structure of the product AAOC-Ru4 is as follows: .

[0036] Example 9 Synthesis of supported ruthenium catalyst Cat1 0.2 g of commercial silica (Sigma-Aldrich G62, 230 m) was added. 2 The silica solid material (200 mesh) was calcined at 773 K for 2 h beforehand. The silica solid material was then impregnated in an anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru1 (prepared in Example 5) at 298 K, stirred for 1 h, filtered, and the solid was dried under vacuum to obtain silica-supported ruthenium catalyst Cat1, namely AAOC-Ru1 / SiO2.

[0037] The loading of AAOC-Ru1 / SiO2 was determined by measuring the absorbance of the anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru1 before and after impregnation using UV-Vis spectroscopy (Perkin-Elmer Lambda 20 spectrophotometer). Specifically, at 298 K, a small amount of 0.68 × 10⁻⁶ SiO2 was continuously added to a stirred beaker containing 100 mg SiO2 and 3 mL cyclohexane.-3 In the case of AAOC-Ru1 cyclohexane solution M, the supernatant was analyzed by UV-Vis spectroscopy after each addition of AAOC-Ru1 cyclohexane solution, tracking the absorbance signal at 570 nm (the maximum absorption peak of the AAOC-Ru1 complex) until the presence of the AAOC-Ru1 complex was detected. The AAOC-Ru1 monolayer loading obtained by this experiment was approximately 0.81 wt%.

[0038] Example 10 Synthesis of supported ruthenium catalyst Cat2 0.2 g of commercial silica (Sigma-Aldrich G62, 230 m) was added. 2 The silica solid material (200 mesh) was calcined at 773 K for 2 h, and then impregnated in an anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru2 (prepared in Example 6) at 298 K. The mixture was stirred for 1 h, then filtered, and the solid was dried under vacuum to obtain silica-supported ruthenium catalyst Cat2, namely AAOC-Ru2 / SiO2.

[0039] The loading of AAOC-Ru2 / SiO2 was determined by measuring the absorbance of the anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru2 before and after impregnation using UV-Vis spectroscopy (Perkin-Elmer Lambda 20 spectrophotometer). Specifically, at 298 K, a small amount of 0.68 × 10⁻⁶ SiO2 was continuously added to a stirred beaker containing 100 mg SiO2 and 3 mL cyclohexane. -3 In the case of AAOC-Ru2 cyclohexane solution M, the supernatant was analyzed by UV-Vis spectroscopy after each addition of AAOC-Ru2 cyclohexane solution, tracking the absorbance signal at 570 nm (the maximum absorption peak of the AAOC-Ru2 complex) until the presence of the AAOC-Ru2 complex was detected. The AAOC-Ru2 monolayer loading obtained by this experiment was approximately 0.75 wt%.

[0040] Example 11 Synthesis of supported ruthenium catalyst Cat3 0.2 g of commercial silica (Sigma-Aldrich G62, 230 m) was added. 2 The silica solid material (200 mesh) was calcined at 773 K for 2 h beforehand. The silica solid material was then impregnated in an anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru3 (prepared in Example 7) at 298 K, stirred for 1 h, filtered, and the solid was dried under vacuum to obtain silica-supported ruthenium catalyst Cat3, namely AAOC-Ru3 / SiO2.

[0041] The loading of AAOC-Ru3 / SiO2 was determined by measuring the absorbance of the anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru3 before and after impregnation using UV-Vis spectroscopy (Perkin-Elmer Lambda 20 spectrophotometer). Specifically, at 298 K, a small amount of 0.68 × 10⁻⁶ SiO2 was continuously added to a stirred beaker containing 100 mg SiO2 and 3 mL cyclohexane. -3 In the case of AAOC-Ru3 cyclohexane solution M, the supernatant was analyzed by UV-Vis spectroscopy after each addition of AAOC-Ru3 cyclohexane solution, tracking the absorbance signal at 570 nm (the maximum absorption peak of the AAOC-Ru3 complex) until the presence of the AAOC-Ru3 complex was detected. The AAOC-Ru3 monolayer loading obtained by this experiment was approximately 0.84 wt%.

[0042] Example 12 Synthesis of supported ruthenium catalyst Cat4 0.2 g of commercial silica (Sigma-Aldrich G62, 230 m) was added. 2 The silica solid material (200 mesh) was calcined at 773 K for 2 h beforehand. The silica solid material was then impregnated in an anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru4 (prepared in Example 8) at 298 K, stirred for 1 h, filtered, and the solid was dried under vacuum to obtain silica-supported ruthenium catalyst Cat4, namely AAOC-Ru4 / SiO2.

[0043] The loading of AAOC-Ru4 / SiO2 was determined by measuring the absorbance of the anhydrous cyclohexane solution of ruthenium catalyst AAOC-Ru4 before and after impregnation using UV-Vis spectroscopy (Perkin-Elmer Lambda 20 spectrophotometer). Specifically, at 298 K, a small amount of 0.68 × 10⁻⁶ SiO2 was continuously added to a stirred beaker containing 100 mg SiO2 and 3 mL cyclohexane. -3 In the case of AAOC-Ru4 cyclohexane solution M, the supernatant was analyzed by UV-Vis spectroscopy after each addition of AAOC-Ru4 cyclohexane solution, tracking the absorbance signal at 570 nm (the maximum absorption peak of the AAOC-Ru4 complex) until the presence of the AAOC-Ru4 complex was detected. The AAOC-Ru4 monolayer loading obtained by this experiment was approximately 0.82 wt%.

[0044] Application Example 1: Cross-metathesis reaction between methyl oleate and ethylene In a nitrogen-filled glove box, methyl oleate (0.2 mmol, 0.5 mL) and n-dodecane (0.2 mmol, 1.0 equivalent) were added to an oven-dried Shrek tube, along with toluene (2 mL) as a solvent. Ethylene was bubbled through the reaction tube for 5 minutes at 1 atm. A CH2Cl2 solution of AAOC-Ru1 / SiO2 was measured using a syringe and added to the Shrek tube outside the glove box. The resulting solution was bubbled with ethylene for another 20 minutes, then stirred at 40°C for 2 hours, followed by quenching the reaction and analysis by GC.

[0045] The above quenching reaction solution was subjected to GC analysis, and the conversion rate of methyl oleate was calculated to be 90%, the yield of 1-decene was 72%, the yield of methyl 9-decenoate was 75%, and the TON of the reaction catalyst was 15000, based on the standard curve of raw material, product and internal standard determined in advance by GC.

[0046] Application Example 2: Cross-metathesis reaction between methyl oleate and ethylene In a nitrogen-filled glove box, methyl oleate (0.2 mmol, 0.5 mL) and n-dodecane (0.2 mmol, 1.0 equivalent) were added to an oven-dried Shrek tube, along with toluene (2 mL) as a solvent. Ethylene was bubbled through the reaction tube for 5 minutes at 1 atm. A CH2Cl2 solution of AAOC-Ru2 / SiO2 was measured using a syringe and added to the Shrek tube outside the glove box. The resulting solution was bubbled with ethylene for another 20 minutes, then stirred at 40°C for 2 hours, followed by quenching the reaction and analysis by GC.

[0047] The above quenching reaction solution was subjected to GC analysis, and the conversion rate of methyl oleate was calculated to be 81% by using the standard curve of raw material, product and internal standard determined in advance by GC, the yield of 1-decene was 71%, the yield of methyl 9-decenoate was 73%, and the TON of the reaction catalyst was 14800.

[0048] Application Example 3: Cross-metathesis reaction between methyl oleate and ethylene In a nitrogen-filled glove box, methyl oleate (0.2 mmol, 0.5 mL) and n-dodecane (0.2 mmol, 1.0 equivalent) were added to an oven-dried Shrek tube, along with toluene (2 mL) as a solvent. Ethylene was bubbled through the reaction tube for 5 minutes at 1 atm. A CH2Cl2 solution of AAOC-Ru3 / SiO2 was measured using a syringe and added to the Shrek tube outside the glove box. The resulting solution was bubbled with ethylene for another 20 minutes, then stirred at 40°C for 2 hours, followed by quenching the reaction and analysis by GC.

[0049] The above quenching reaction solution was subjected to GC analysis, and the conversion rate of methyl oleate was calculated to be 81%, the yield of 1-decene was 99%, the yield of methyl 9-decenoate was 73%, and the TON of the reaction catalyst was 15100, based on the standard curve of raw material, product and internal standard determined in advance by GC.

[0050] Application Example 4: Cross-metathesis reaction between methyl oleate and ethylene In a nitrogen-filled glove box, methyl oleate (0.2 mmol, 0.5 mL) and n-dodecane (0.2 mmol, 1.0 equivalent) were added to an oven-dried Shrek tube, along with toluene (2 mL) as a solvent. Ethylene was bubbled through the reaction tube for 5 minutes at 1 atm. A CH2Cl2 solution of AAOC-Ru4 / SiO2 was measured using a syringe and added to the Shrek tube outside the glove box. The resulting solution was bubbled with ethylene for another 20 minutes, then stirred at 40°C for 2 hours, followed by quenching the reaction and analysis by GC.

[0051] The above quenching reaction solution was subjected to GC analysis, and the conversion rate of methyl oleate was calculated to be 98%, the yield of 1-decene was 97%, the yield of methyl 9-decenoate was 96%, and the TON of the reaction catalyst was 110000, based on the standard curve of raw material, product and internal standard determined in advance by GC.

[0052] The above are merely embodiments of the present invention. The invention is not limited to the fields covered by these embodiments. Commonly known structures and characteristics are not described in detail here. Those skilled in the art are aware of all common technical knowledge in the field prior to the application date or priority date, are aware of all existing technologies in that field, and have the ability to apply conventional experimental methods prior to that date. Those skilled in the art can improve and implement this solution based on the guidance provided in this application and their own capabilities. Some typical known structures or methods should not be obstacles for those skilled in the art to implement this application. It should be noted that those skilled in the art can make several modifications and improvements without departing from the structure of the present invention. These should also be considered within the scope of protection of the present invention, and will not affect the effectiveness or practicality of the invention. The scope of protection claimed in this application should be determined by the content of its claims. The specific embodiments described in the specification can be used to interpret the content of the claims.

Claims

1. A non-cyclic aminooxycarbene composite ruthenium catalyst, characterized in that: The structure of the acyclic aminooxycarbene composite ruthenium catalyst is shown in formula (Ⅰ): ； In formula (Ⅰ), M is a ruthenium atom; Z1 and Z2 each independently represent an anionic ligand; X1 represents one oxygen atom; L1 represents an inert ligand, and L1 is selected from one of the acyclic aminocarbene ligands shown in formula (II), formula (III), or formula (IV); ； In formulas (II), (III), and (IV), R1, R2, R3, and R4 are each independently selected from hydrogen atoms, C1-C atoms, and C4 atoms. 12 Alkyl, C3-C 12 cycloalkyl, C2-C 12 alkenyl and C5-C 20 One of the aryl groups, wherein R1, R2, R3, and R4 may optionally be separated by at least one C1-C. 12 Alkyl, C1-C 12 All-haloalkyl, C1-C 12 Alkoxy or one halogen atom can be substituted; R1, R2, R3 and R4 can bond to each other.

2. An acyclic aminooxycarbene ligand, characterized in that: The structure of the acyclic aminooxycarbene ligand is shown in formula (V): ； In formula (V), X2 represents an anionic ligand, and X2 is selected from chloride ion and hexafluorophosphate ion; R5, R6, R7 and R8 each independently represent a hydrogen atom or a C1-C atom. 12 Alkyl groups; R5, R6, R7, and R8 can bond to each other.

3. A method for preparing the acyclic aminooxycarbene ligand as described in claim 2, characterized in that: The preparation method includes: reacting a substituted formamide compound having the structure shown in formula (VI) with an aryl silyl ether or phenol as an intermediate via a variant of the Vilsmeier-Haack reagent; 。 4. A method for preparing the acyclic aminooxycarbene composite ruthenium catalyst as described in claim 1, characterized in that: When the structure of the acyclic aminooxycarbene composite ruthenium catalyst is as shown in formula (a), its preparation method includes the following steps: ； 1) Take an organic base and the acyclic aminooxycarbene ligand as described in claim 4, add them to a solvent, react at -78°C for 0.5 to 3 h, then add Hoveyda-Grubbs first-generation catalyst, continue stirring for 2 h, and concentrate to obtain crude product I; 2) Dissolve the crude product I obtained in step 1) in dichloromethane, add cuprous chloride or ion exchange resin, and heat the reaction at 40℃~60℃ for 1~2 h to obtain the reaction mixture. Wash with dichloromethane, combine the filtrates and concentrate to obtain crude product II. Crude product II is purified to obtain the product shown in formula (a).

5. The preparation method according to claim 4, characterized in that: In step 1), the organic base is one or more of bis(trimethylsilyl)aminopotassium, potassium tert-butoxide, and potassium tert-amyloxide; And / or, in step 1), the solvent is an ether solvent.

6. The preparation method according to claim 4, characterized in that: In step 1), the Hoveyda-Grubbs first-generation catalyst is dissolved in an aromatic hydrocarbon solvent and then added to the reaction.

7. The application of the acyclic aminooxycarbene composite ruthenium catalyst as described in claim 1 in the metathesis reaction of olefins.

8. The application according to claim 7, characterized in that: The acyclic aminooxycarbene composite ruthenium catalyst as described in claim 1 is supported in a solid material to obtain a supported acyclic aminooxycarbene composite ruthenium catalyst, which is then applied to the metathesis reaction of olefins.

9. The application according to claim 8, characterized in that: The solid material is silicon dioxide.

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