Amino-bridged triaryloxy rare earth metal complex and its preparation method and application

Abstract

The invention discloses an amino-bridged triaryloxy rare earth metal complex and a preparation method and application thereof. The amino-bridged triaryloxy rare earth metal complex is prepared by reacting a tricyclopentadienyl rare earth compound and an amino-bridged triphenol. The preparation method is simple to operate, convenient for separation and purification, low in raw material cost, and mild in reaction conditions. The amino-bridged triaryloxy rare earth metal complex provided by the invention can be used for catalytic oxidation of chalcone compounds and carbon dioxide cycloaddition reaction, the reaction conditions are relatively mild, the reaction substrate has wide universality, the reaction time is short, the yield of the target product is high, and the reaction operation process is simple.

Description

Technical Field

[0001] The invention relates to the technical field of amino-bridged triaryloxy rare earth metal complexes, and in particular to an amino-bridged triaryloxy rare earth metal complex and a preparation method and application thereof. Background Art

[0002] As a multifunctional compound, cyclic carbonate plays an important role in many industries such as textile, dyeing, lubricating oil, cosmetics, etc. In addition, it is also used as a green solvent for chemical synthesis and a raw material for plastics. Especially in the field of lithium-ion batteries, high-energy-density electrolytes are mainly composed of carbonates. In view of the wide application and importance of cyclic carbonates, the development of efficient methods for the synthesis of cyclic carbonates has always been a hot topic in chemical research. One of the main methods for synthesizing cyclic carbonate compounds is the cycloaddition reaction of alkylene oxide and carbon dioxide. To achieve the efficient conduct of this reaction, the key lies in the selection and design of catalysts. At present, there are only the following four effective catalyst systems for the cycloaddition reaction of oxidized chalcone compounds and carbon dioxide, which mainly include two categories: transition metal compound catalytic system and organic reagent catalytic system.

[0003] In terms of transition metal compound catalytic systems, complexes of metals such as ruthenium and cobalt are widely used in catalytic oxidation of chalcone compounds and carbon dioxide cycloaddition reactions. For example, Qiu, WY's research group reported in 2007 the use of a binary catalyst system consisting of a ruthenium-Salen complex and phenyltrimethylammonium tribromide, but the yield of this system was relatively low, only 30-35%. Subsequently, Belokon, Y.'s research group reported in 2016 the use of a chiral cobalt (III) complex as a single-component bifunctional (Bronsted acid-Lewis base) catalyst. Although the yield was improved, it still required a higher catalyst dosage and CO. 2 Pressure. Recently, Larionov, VA group also reported the use of ( R,R )-1,2-diphenylethylenediamine and salicylaldehyde as raw materials to synthesize the cationic octahedral cobalt (III) complex as a catalyst, but the yield was only 33%.

[0004] In terms of organic reagent catalytic systems, some naturally occurring compounds and simple organic reagents are also used as catalysts. For example, in 2022, the research group of Rostami, A. reported the use of 2-carboxylic acid pyridine as a hydrogen bond donor (HBD) and the addition of tetrabutylammonium iodide (TBAI) as a co-catalyst to successfully catalyze the cycloaddition reaction of oxidized chalcone compounds and carbon dioxide, obtaining a high yield (88%), but the reaction requires pressure (10 bar) and high temperature conditions (100 ° C) to proceed.

[0005] These catalyst systems all have some problems, such as large catalyst dosage, harsh reaction conditions, poor substrate universality, etc. Therefore, there is an urgent need to develop a preparation method with simple raw material sources, mild reaction conditions, and good universality to achieve efficient synthesis of cyclic carbonates. Summary of the invention

[0006] In order to solve the above technical problems, the purpose of the present invention is to provide an amino-bridged triaryloxy rare earth metal complex.

[0007] Another object of the present invention is to provide a method for preparing the amino-bridged triaryloxy rare earth metal complex.

[0008] The third object of the present invention is to provide an application of the above amino-bridged triaryloxy rare earth metal complex in the catalytic oxidation cycloaddition reaction of chalcone compounds and carbon dioxide.

[0009] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0010] An amino-bridged triaryloxy rare earth metal complex, the structural formula of the amino-bridged triaryloxy rare earth metal complex is as follows:

[0011] ,

[0012] Among them, RE is a rare earth metal, R 1 is selected from one of alkyl, cumyl and halogen, R 2 One selected from the group consisting of alkyl, cumyl and halogen.

[0013] Furthermore, the rare earth metal is lanthanum, neodymium, samarium, europium, ytterbium, yttrium or scandium.

[0014] The present invention provides a method for preparing the above-mentioned amino-bridged triaryloxy rare earth metal complex, comprising the following steps:

[0015] (1) under an inert atmosphere, a rare earth metal halide is dispersed in an ether solvent, and an ether solution of cyclopentadienyl sodium (NaCp) is added to the obtained suspension to react and obtain a tricyclopentadienyl rare earth compound;

[0016] (2) The tricyclopentadienyl rare earth compound obtained in step (1) and the amino-bridged triphenol are dissolved in tetrahydrofuran, and reacted at 45-65° C. to obtain the amino-bridged triaryloxy rare earth metal complex.

[0017] The preparation method provided by the present invention is simple to operate, convenient for separation and purification, has low raw material cost, mild reaction conditions, and the prepared compound has a clear structure and can be characterized by single crystal X-ray diffraction (X-ray).

[0018] The amino-bridged triphenol provided by the present invention is abbreviated as LH3 , the structural formula is , where R 1 is selected from one of alkyl, cumyl and halogen, R 2 One selected from the group consisting of alkyl, cumyl and halogen.

[0019] The structural formula of the amino-bridged triaryloxy rare earth metal complex provided by the present invention can be abbreviated as LRE (THF) or L'RE (THF), wherein RE is a rare earth metal.

[0020] Furthermore, in step (1), the rare earth metal in the rare earth metal halide is lanthanum, neodymium, samarium, europium, ytterbium, yttrium or scandium.

[0021] Furthermore, in step (1), the halogen in the rare earth metal halide is chlorine, bromine or iodine, preferably chlorine.

[0022] Furthermore, in step (1), the inert atmosphere is argon.

[0023] Furthermore, in step (1), the ether solvent is tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether, preferably tetrahydrofuran.

[0024] Furthermore, in step (1), the concentration of cyclopentadienyl sodium in the ether solution of cyclopentadienyl sodium is 2-3 mol / L.

[0025] Furthermore, in step (1), the ether solution of cyclopentadienyl sodium is a tetrahydrofuran solution of cyclopentadienyl sodium, an ether solution of cyclopentadienyl sodium or an ethylene glycol dimethyl ether solution of cyclopentadienyl sodium, preferably a tetrahydrofuran solution of cyclopentadienyl sodium.

[0026] Furthermore, in step (1), the molar ratio of the rare earth metal halide to cyclopentadienyl sodium is 1:(2-4).

[0027] In a specific embodiment, in step (1), under an inert atmosphere, a rare earth metal halide is dispersed in an ether solvent, and stirred and activated at room temperature overnight until no lumps are present, and then an ether solution of cyclopentadienyl sodium is added to the obtained suspension, and the reaction is carried out at room temperature overnight. After the reaction is completed, the mother liquor is transferred to a centrifuge bottle, centrifuged, and the supernatant is transferred to a crystallization bottle. The precipitate at the bottom of the centrifuge bottle is extracted several times with hot tetrahydrofuran, and the mother liquor and the extract are combined. The obtained solution is concentrated to precipitate a large amount of powdery crystals, which is the tricyclopentadienyl rare earth compound (RECp 3 ).

[0028] Furthermore, in step (2), the molar ratio of the tricyclopentadienyl rare earth compound to the amino-bridged triphenol is (0.5-2):1.

[0029] Furthermore, in step (2), the amino-bridged triphenol may be N,N',N'-tri-(2,4-disubstituted-6-methylenephenyl)-N-(pyridin-2-ylmethyl)-1,2-ethylenediamine.

[0030] Furthermore, in step (2), the amino-bridged triphenol may be first dissolved in a tetrahydrofuran solution and then mixed with the tricyclopentadienyl rare earth compound.

[0031] Furthermore, in step (2), the reaction time is 8-12 h.

[0032] In a specific embodiment, in step (2), the tricyclopentadienyl rare earth compound obtained in step (1) and the amino-bridged triphenol (LH 3 ) is dissolved in tetrahydrofuran and reacted at 45-65 ℃ for 8-12 hours. After the reaction is completed, the mother liquor is centrifuged, and the supernatant is transferred to a crystallization bottle, concentrated until a large number of crystals appear, hot-dissolved, and then cooled to room temperature. The bottle is sealed and allowed to stand, and crystals are precipitated, which is the amino-bridged triaryloxy rare earth metal complex (LRE(THF) or L'RE(THF)).

[0033] Furthermore, in step (2), the preparation method of the amino-bridged triphenol comprises the following steps: N -(Pyridin-2-yl-methyl)-1,2-ethylenediamine and 2,4-disubstituted phenol are mixed at 85-95° C., and then formaldehyde or paraformaldehyde is added to react to obtain the amino-bridged triphenol.

[0034] Furthermore, the N The molar ratio of -(pyridin-2-yl-methyl)-1,2-ethylenediamine to 2,4-disubstituted phenol is (1.5-2.5):(5-7).

[0035] Furthermore, the N The molar ratio of -(pyridin-2-yl-methyl)-1,2-ethylenediamine to formaldehyde is (1.5-2.5):(5-7).

[0036] Furthermore, the N The molar ratio of -(pyridin-2-yl-methyl)-1,2-ethylenediamine to paraformaldehyde is (1.5-2.5):(5-7).

[0037] In a specific embodiment, in step (2), the preparation method of the amino-bridged triphenol comprises the following steps: N-(pyridin-2-yl-methyl)-1,2-ethylenediamine and 2,4-disubstituted phenol are mixed at 85-95°C, and after the solid reactant is melted, formaldehyde or polyformaldehyde is added, and the mixture is heated under reflux at 90-110°C for 70-72 hours without solvent. A small amount of water in the reaction mixture is removed under reduced pressure, and the crude product is purified by column chromatography, eluted with petroleum ether and ethyl acetate, and the volatile solvent is removed under vacuum to obtain the amino-bridged triphenol.

[0038] The present invention also protects the use of the amino-bridged triaryloxy rare earth metal complex in the catalytic oxidation cycloaddition reaction of chalcone compounds and carbon dioxide, wherein the amino-bridged triaryloxy rare earth metal complex is used as a catalyst.

[0039] The conditions for the cycloaddition reaction of the oxidized chalcone compounds and carbon dioxide provided by the present invention are relatively mild, the amino-bridged triaryloxy rare earth metal complex as a catalyst has high catalytic activity, the amount of catalyst used is small, and it is beneficial to the purification of the product, and the regioselectivity of the cycloaddition reaction is good (carbon dioxide only acts on the alkylene oxide reaction site), and the substrate adaptability range is wide.

[0040] Furthermore, the method for the cycloaddition reaction of an oxidized chalcone compound and carbon dioxide catalyzed by an amino-bridged triaryloxy rare earth metal complex comprises the following steps: in an anhydrous and oxygen-free environment and under the protection of an inert gas, the amino-bridged triaryloxy rare earth metal complex, a co-catalyst and an oxidized chalcone compound are mixed, carbon dioxide is introduced and a cycloaddition reaction is carried out at 40-70°C to obtain a cyclocarbonate compound.

[0041] Furthermore, the co-catalyst is selected from one or more of tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetraethylammonium bromide, tetra-n-octylammonium bromide and (2-bromoethyl)trimethylammonium bromide.

[0042] Furthermore, the inert gas is argon or nitrogen.

[0043] Furthermore, the molar ratio of the amino-bridged triaryloxy rare earth metal complex, the co-catalyst and the oxidized chalcone compound is (0.5-4):(2-6):(50-100).

[0044] Furthermore, the temperature of the cycloaddition reaction is preferably 50-70°C, more preferably 50-60°C.

[0045] Furthermore, the cycloaddition reaction time is 12-30 h.

[0046] Furthermore, the pressure of the cycloaddition reaction is 10-40 bar, preferably 20-40 bar, more preferably 30-40 bar.

[0047] Furthermore, the amino-bridged triaryloxy rare earth metal complex, the co-catalyst, the oxidized chalcone compound and the solvent are mixed, and the solvent is selected from one or more of toluene, p-xylene, 1,4-dioxane, dimethyl sulfoxide, 1,1,2,2-tetrachloroethane, benzonitrile and halobenzene.

[0048] In a specific embodiment, in an anhydrous and oxygen-free, inert gas environment, an amino-bridged triaryloxy rare earth metal complex, a co-catalyst and an oxidized chalcone compound are mixed, and carbon dioxide is introduced to react. After the reaction, the carbon dioxide is vented, silica gel powder is added and spin-dried, and the product is separated by rapid column chromatography.

[0049] In a specific embodiment, the amino-bridged triaryloxy rare earth metal complex can be added to the reaction vessel in solid form.

[0050] Beneficial effects of the present invention:

[0051] 1. The amino-bridged triaryloxy rare earth metal complex provided by the present invention has a clear structure, a simple synthesis method, a high yield, and is simple to separate and purify.

[0052] 2. The amino-bridged triaryloxy rare earth metal complex provided by the present invention can be used to catalyze the oxidative cycloaddition reaction of chalcone compounds and carbon dioxide. The reaction conditions are relatively mild, the reaction substrates are widely applicable, the reaction time is short, the yield of the target product is high, and the reaction operation process is simple. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is a schematic diagram of the crystal structure of the amino-bridged triaryloxylanthanum complex (LLa(THF)) prepared in Example 1.

[0054] Figure 2 This is a schematic diagram of the crystal structure of the amino-bridged triaryloxy neodymium complex (LNd(THF)) prepared in Example 2.

[0055] Figure 3 This is a schematic diagram of the crystal structure of the amino-bridged triaryloxy samarium complex (LSm(THF)) prepared in Example 3.

[0056] Figure 4 This is a schematic diagram of the crystal structure of the amino-bridged triaryloxy lanthanum complex (L'La(THF)) prepared in Example 4. DETAILED DESCRIPTION

[0057] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0058] The present invention provides a method for preparing an amino-bridged triaryloxy rare earth metal complex, comprising the following steps:

[0059] (1) under an inert atmosphere, a rare earth metal halide is dispersed in an ether solvent, and an ether solution of cyclopentadienyl sodium is added to the obtained suspension to react and obtain a tricyclopentadienyl rare earth compound;

[0060] (2) The tricyclopentadienyl rare earth compound obtained in step (1) and the amino-bridged triphenol are dissolved in tetrahydrofuran, and reacted at 45-65° C. to obtain the amino-bridged triaryloxy rare earth metal complex.

[0061] In a specific embodiment, in step (2), the amino-bridged triphenol (LH 3 ) comprises the following steps: N -(pyridin-2-yl-methyl)-1,2-ethylenediamine and 2,4-disubstituted phenol are mixed at 85-95°C, and then formaldehyde or paraformaldehyde is added to react to obtain the amino-bridged triphenol. The reaction equation is as follows:

[0062] .

[0063] In a specific embodiment, the method for the cycloaddition reaction of an amino-bridged triaryloxy rare earth metal complex catalyzed by an oxidized chalcone compound and carbon dioxide comprises the following steps: in an anhydrous and oxygen-free, inert gas protection, an amino-bridged triaryloxy rare earth metal complex (cat.), a co-catalyst (co-cat.) and an oxidized chalcone compound are mixed, and carbon dioxide is charged to carry out a cycloaddition reaction to obtain a product. The reaction equation is as follows:

[0064] , where R 3 It is a hydrocarbon group or an aromatic group.

[0065] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0066] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used are all available from commercial sources unless otherwise specified. Example 1

[0067] A method for preparing an amino-bridged triaryloxylanthanum complex (LLa(THF)) comprises the following steps:

[0068] (1) In a dry, argon-filled reaction flask, weigh 10 mmol of anhydrous LaCl 3 , add 20 mL of tetrahydrofuran solution, seal the bottle, and stir and activate at room temperature overnight until no lumps exist. Under an argon atmosphere, use a syringe to add 2.1 mol / L NaCp tetrahydrofuran solution to the above solution, so that the amount of NaCp added is 30 mmol, seal the bottle, and continue to react at room temperature overnight. After the reaction is completed, transfer the mother liquor to a centrifuge bottle, centrifuge, transfer the supernatant to a crystallization bottle, and extract the precipitate at the bottom of the centrifuge bottle with hot tetrahydrofuran several times. Concentrate the obtained solution to precipitate a large amount of powdery crystals, which is LaCp 3 .

[0069] (2) In a 100 mL round-bottom flask with a stirrer, add N -(Pyridin-2-yl-methyl)-1,2-ethylenediamine (3.02 g, 20 mmol) and 2,4-di-tert-butylphenol (12.8 g, 62 mmol) were stirred at 90 °C. After the solid reactant was melted, paraformaldehyde (1.8 g, 60 mmol) was added and the mixture was heated under reflux at 100 °C for 72 h without solvent. After the reaction was completed, a small amount of water generated was removed under reduced pressure. The crude product was purified by column chromatography, eluted with petroleum ether and ethyl acetate (93:7), and all volatiles were removed under vacuum to obtain the product. N,N',N' -Tris-(2,4-di-tert-butyl-6-methylenephenyl)- N -(Pyridin-2-yl-methyl)-1,2-ethylenediamine (LH 3 ), the yield was 56%. Product LH 3 The NMR data are: 1 H NMR (400 MHz, CDCl 3 ): δ 8.52 (d, J = 4.8 Hz, 1H, ArH), 7.63 (td, J = 7.7, 1.7 Hz, 1H, ArH),7.25-7.15 (m, 5H, ArH), 6.88 (d, J = 2.3 Hz, 2H, ArH), 6.76 (d, J = 2.3 Hz, 1H,ArH), 3.81 (s, 2H, CH 2 ), 3.67 (s, 2H, CH2 ), 3.61 (s, 4H, CH 2 ), 2.80 (dd, J =10.4, 4.7 Hz, 4H, NCH 2 CH 2 N), 1.38 (s, 27H, (CH 3 ) 3 ), 1.26 (s, 18H, (CH 3 ) 3 ), 1.24(s, 9H, (CH 3 ) 3 ).

[0070] (3) LaCp was weighed into the reaction flask at a molar ratio of 1:1. 3 and LH 3 , add 20 mL of tetrahydrofuran to dissolve, and react at 55 °C for 12 h. After the reaction, the mother liquor was centrifuged, and the supernatant was transferred to a crystallization bottle and concentrated until a large number of crystals appeared. The hot solution was cooled to room temperature, and the bottle was sealed and allowed to stand. Crystals precipitated, which was the amino-bridged triaryloxylanthanum complex LLa(THF), with a yield of 84%. The precipitated crystals were placed in single crystal oil, and the crystal structure was measured by X-ray single crystal diffraction. The schematic diagram of the crystal structure is shown in the figure. Figure 1 As shown, it was proved that LLa(THF) was successfully prepared. Example 2

[0071] A method for preparing an amino-bridged triaryloxy neodymium complex (LNd(THF)) is basically the same as that in Example 1, except that: in step (1), LaCl 3 Replaced by NdCl 3 .

[0072] After the reaction, purple crystals were precipitated by post-treatment at room temperature, which was the amino-bridged triaryloxy neodymium complex LNd(THF) with a yield of 80%. The crystal structure was measured by X-ray single crystal diffraction. The schematic diagram of the crystal structure is shown in the figure. Figure 2 As shown, it is proved that LNd(THF) was successfully prepared. Example 3

[0073] A method for preparing an amino-bridged triaryloxy samarium complex (LSm(THF)) is basically the same as that in Example 1, except that: in step (1), LaCl 3 Replaced by SmCl 3 .

[0074] After the reaction, after post-treatment, light yellow block crystals were precipitated at room temperature, which was the amino-bridged triaryloxy samarium complex LSm(THF) with a yield of 76%. The crystal structure was measured by X-ray single crystal diffraction. The schematic diagram of the crystal structure is shown in the figure. Figure 3 As shown, it is proved that LSm(THF) was successfully prepared. Example 4

[0075] A method for preparing an amino-bridged triaryloxy lanthanum complex (L'La(THF)) is substantially the same as that of Example 1, except that in step (2), 2,4-di-tert-butylphenol is replaced by 2,4-dicumylphenol.

[0076] After the reaction, after post-treatment, colorless block crystals were precipitated at room temperature, namely, amino-bridged triaryloxy lanthanum complex L'La(THF), with a yield of 65%. The crystal structure was measured by X-ray single crystal diffraction. The schematic diagram of the crystal structure is shown in the figure. Figure 4 As shown, it is proved that L'La(THF) was successfully prepared.

[0077] Application Example 1

[0078] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0079] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, the molar percentage of catalyst in substrate is 2 mol%) LLa(THF) and 4.4 mg (1.2×10 -5 mole, the mole percentage of the co-catalyst in the substrate is 4 mol%), tetrabutylammonium iodide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved in 0.1 ml toluene, transferred into a reactor, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 barCO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-benzoyl-5-phenyl-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 60%. The NMR data of the product were: 1 H NMR (400 MHz, CDCl 3 ): δ 7.96 (d, J = 8.2 Hz, 2H, ArH), 7.67 (t, J =7.5 Hz, 1H, ArH), 7.51 (t,J = 7.8 Hz, 2H, ArH), 7.45 (d, J = 7.4 Hz, 5H, ArH),5.99 (d, J = 6.2 Hz, 1H, CH), 5.59 (d, J = 6.2 Hz, 1H, CH). Comparative Example 1

[0080] Tetrabutylammonium iodide was used to catalyze the oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0081] In anhydrous and oxygen-free environment, 4.4 mg (1.2 × 10 -5 molar, 4 mol%) tetrabutylammonium iodide was added to the reaction flask, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved in 0.1 ml toluene, transferred into a reactor, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 6%. Comparative Example 2

[0082] Amino-bridged triaryloxylanthanum complexes (LLa(THF)) were used to catalyze the oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0083] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 molar, 2 mol%) LLa(THF) was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved in 0.1 ml toluene, transferred into a reactor, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 3%.

[0084] By comparing Application Example 1, Comparative Example 1 and Comparative Example 2, it can be seen that when LLa(THF) is used as a catalyst in combination with the co-catalyst tetrabutylammonium iodide, the final yield is greatly improved compared with the yield of using the catalyst alone or the co-catalyst alone.

[0085] Application Example 2

[0086] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that in Application Example 1, the difference being that toluene is not added, and the final calculated yield is 40%.

[0087] Application Example 3

[0088] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.3 ml of toluene is used for dissolution, and the final calculated yield is 42%.

[0089] Application Example 4

[0090] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.1 ml of p-xylene is used for dissolution, and the final calculated yield is 19%.

[0091] Application Example 5

[0092] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.1 ml of chlorobenzene is used for dissolution, and the final calculated yield is 36%.

[0093] Application Example 6

[0094] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.1 ml of bromobenzene is used for dissolution, and the final calculated yield is 40%.

[0095] Application Example 7

[0096] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.1 ml of benzonitrile is used for dissolution, and the final calculated yield is 20%.

[0097] Application Example 8

[0098] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.1 ml of dimethyl sulfoxide is used for dissolution, and the final calculated yield is 9%.

[0099] Application Example 9

[0100] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.1 ml of 1,1,2,2-tetrachloroethane is used for dissolution, and the final calculated yield is 20%.

[0101] Application Example 10

[0102] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 1, the difference being that 0.1 ml of 1,4-dioxane is used for dissolution, and the final calculated yield is 70%.

[0103] Application Example 11

[0104] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium bromide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0105] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 3.9 mg (1.2×10 -5 molar, 4 mol%) tetrabutylammonium bromide was added to the reaction flask, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 45%.

[0106] Application Example 12

[0107] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium chloride for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0108] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 3.4 mg (1.2×10 -5 molar, 4 mol%) tetrabutylammonium chloride was added to the reaction flask, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 37%.

[0109] Application Example 13

[0110] Amino-bridged triaryloxylanthanum complexes (LLa(THF)) and tetrabutylammonium fluoride for the catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0111] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 molar, 2 mol%) LLa(THF) and 12 μl (1.2×10 -5 molar, 4 mol%) tetrabutylammonium fluoride was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 8%.

[0112] Application Example 14

[0113] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetraethylammonium bromide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0114] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 2.5 mg (1.2×10 -5molar, 4 mol%) tetraethylammonium bromide was added to the reaction flask, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 11%.

[0115] Application Example 15

[0116] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetra-n-octylammonium bromide for the catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0117] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.2×10 -5 molar, 4 mol%) tetra-n-octylammonium bromide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 30%.

[0118] Application Example 16

[0119] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and (2-bromoethyl)trimethylammonium bromide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0120] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 3.0 mg (1.2×10 -5 molar, 4 mol%) (2-bromoethyl)trimethylammonium bromide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 23%.

[0121] Application Example 17

[0122] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0123] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 81%.

[0124] Application Example 18

[0125] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0126] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 8.8 mg (2.4×10 -5 molar, 8 mol%) tetrabutylammonium iodide was added to the reaction flask, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 45%.

[0127] Application Example 19

[0128] Amino-bridged triaryloxy neodymium complex (LNd(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0129] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LNd(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 52%.

[0130] Application Example 20

[0131] Amino-bridged triaryloxy samarium complex (LSm(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0132] In anhydrous and oxygen-free environment, 6.3 mg (6.0 × 10 -6 mol, 2 mol%) LSm(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 38%.

[0133] Application Example 21

[0134] Amino-bridged triaryloxylanthanum complex (L'La(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0135] In anhydrous and oxygen-free inert gas environment, 8.4 mg (6.0 × 10 -6mole, 2 mol%) L'La(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 ° C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried, and the product was separated by rapid column chromatography, with a calculated yield of 39%.

[0136] Application Example 22

[0137] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0138] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reactor, filled with carbon dioxide gas, placed at 40 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, with a calculated yield of 4%.

[0139] Application Example 23

[0140] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 22, the difference being that: the mixture is placed at 60°C and stirred at a constant temperature, and the final calculated yield is 68%.

[0141] Application Example 24

[0142] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 22, the difference being that: the mixture is placed at 70°C and stirred at a constant temperature, and the final calculated yield is 54%. Comparative Example 3

[0143] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 22, the difference being that: it is placed at 30°C and stirred at a constant temperature, and no product is generated in the end.

[0144] Application Example 25

[0145] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method comprises the following steps:

[0146] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction bottle, and 67.3 mg (3×10 -4 mol) oxidized chalcone, dissolved with 0.1 ml 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 30 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product was separated by rapid column chromatography, and the final calculated yield was 70%.

[0147] Application Example 26

[0148] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 25, the difference is that: at 20 bar CO 2 The reaction was carried out under pressure and the final calculated yield was 53%.

[0149] Application Example 27

[0150] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide for catalytic oxidation of chalcone ( ) and carbon dioxide cycloaddition reaction, the specific method is basically the same as that of Application Example 25, the difference is that: at 10 bar CO 2 The reaction was carried out under pressure and the final calculated yield was 38%.

[0151] Application Example 28

[0152] Amino-bridged triaryloxy lanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-(4-methylphenyl)oxirane-2-yl)(phenyl)methanone and carbon dioxide. The specific method includes the following steps:

[0153] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 71.4 mg (3×10 -4 mol) (3-(4-methylphenyl)oxirane-2-yl)(phenyl)methanone was dissolved in 0.1 ml of 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-benzoyl-5-(4-methylphenyl)-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 75%. The NMR data of the product were: 1 H NMR (400 MHz, CDCl 3 ): δ 8.12 (d, J = 7.2 Hz, 2H, ArH), 7.84 (t, J = 7.4 Hz, 1H, ArH),7.68 (t, J = 7.8 Hz, 2H, ArH), 7.49 (d, J = 8.2 Hz, 2H, ArH), 7.45 (d, J = 6.1 Hz,2H, ArH), 6.09 (d, J = 6.2 Hz, 1H, CH), 5.77 (d, J = 6.2 Hz, 1H,CH), 2.57 (s, 3H,CH 3 ).

[0154] Application Example 29

[0155] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-(4-methoxyphenyl)oxirane-2-yl)(phenyl)methanone and carbon dioxide. The specific method includes the following steps:

[0156] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 76.2 mg (3×10 -4 mol) (3-(4-methoxyphenyl)oxirane-2-yl)(phenyl)methanone was dissolved in 0.1 ml of 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-benzoyl-5-(4-methoxyphenyl)-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 71%. The NMR data of the product were: 1 H NMR (400 MHz, CDCl 3 ): δ 7.94 (s, 2H, ArH), 7.66 (t, J = 7.5 Hz, 1H, ArH), 7.50 (t, J =7.8 Hz, 2H, ArH), 7.36 (d, J = 8.7 Hz, 2H, ArH), 6.97 (d, J = 8.8 Hz, 2H, ArH),5.87 (d, J = 6.3 Hz, 1H, CH), 5.61 (d, J = 6.3 Hz, 1H, CH), 3.84 (s, 3H, CH 3 ).

[0157] Application Example 30

[0158] Amino-bridged triaryloxy lanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-(4-fluorophenyl)oxirane-2-yl)(phenyl)methanone and carbon dioxide. The specific method includes the following steps:

[0159] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 72.6 mg (3×10 -4mol) (3-(4-fluorophenyl)oxirane-2-yl)(phenyl)methanone was dissolved in 0.1 ml of 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-benzoyl-5-(4-fluorophenyl)-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 91%. The NMR data of the product were: 1 H NMR (400MHz, CDCl 3 ): δ 7.97 (d, J = 7.2 Hz, 2H, ArH), 7.67 (t, J = 7.4 Hz, 1H, ArH), 7.54-7.49 (m, 3H, ArH), 7.16 (t, J = 8.6 Hz, 3H, ArH), 6.00 (d, J = 6.5 Hz, 1H, CH),5.54 (d, J = 6.5 Hz, 1H, CH).

[0160] Application Example 31

[0161] Amino-bridged triaryloxy lanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of phenyl(3-(4-(trifluoromethyl)phenyl)oxirane-2-yl)methanone and carbon dioxide. The specific method includes the following steps:

[0162] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 87.6 mg (3×10 -4 1,4-dioxane, and transferred into a reaction kettle. Carbon dioxide gas was introduced and stirred at 50 °C. The mixture was heated to 40 bar CO. 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-benzoyl-5-(4-(trifluoromethyl)phenyl)-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 89%. The NMR data of the product were: 1 HNMR (400 MHz, CDCl3 ): δ 7.99 (d, J = 7.3 Hz, 2H, ArH), 7.73 (d, J = 8.2 Hz, 2H,ArH), 7.68 (d, J = 7.4 Hz, 1H, ArH), 7.58 (d, J = 8.3 Hz, 2H, ArH), 7.53 (t, J =7.8 Hz, 2H, ArH), 6.14 (d, J = 6.5 Hz, 1H, CH), 5.50 (d, J = 6.5 Hz, 1H, CH).

[0163] Application Example 32

[0164] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-phenyloxirane-2-yl)(p-tolyl)ketone and carbon dioxide. The specific method includes the following steps:

[0165] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 71.4 mg (3×10 -4 mol) (3-phenyloxirane-2-yl)(p-tolyl) ketone was dissolved in 0.1 ml of 1,4-dioxane, transferred to a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-((4-methylphenyl)formyl)-5-phenyl-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 80%. The NMR data of the product were: 1 H NMR (400MHz, CDCl 3 ): δ 7.85 (d, J = 8.3 Hz, 2H, ArH), 7.48-7.41 (m, 5H, ArH), 7.30 (d, J =8.0 Hz, 2H, ArH), 5.97 (d, J = 6.2 Hz, 1H, CH), 5.56 (d, J= 6.2 Hz, 1H, CH),2.44 (s, 3H, CH 3 ).

[0166] Application Example 33

[0167] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (4-methoxyphenyl)(3-phenyloxirane-2-yl)ketone and carbon dioxide. The specific method includes the following steps:

[0168] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 76.2 mg (3×10 -4 mol) (4-methoxyphenyl)(3-phenyloxirane-2-yl) ketone was dissolved in 0.1 ml of 1,4-dioxane, transferred to a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and the reaction mixture was dried by rotation, and the product 4-((4-methoxyphenyl)formyl)-5-phenyl-1,3-dioxolane-2-one was obtained by rapid column chromatography separation. The calculated yield was 76%, and the NMR data of the product was: 1 HNMR (400 MHz, CDCl 3 ): δ 7.94 (d, J = 9.0 Hz, 2H, ArH), 7.44 (d, J = 5.1 Hz, 5H,ArH), 6.96 (d, J = 9.0 Hz, 2H, ArH), 6.00 (d, J = 6.3 Hz, 1H, CH), 5.53 (d, J = 6.3Hz, 1H, CH), 3.89 (s, 3H, CH 3 ).

[0169] Application Example 34

[0170] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-phenyloxirane-2-yl)(4-(trifluoromethyl)phenyl)methanone and carbon dioxide. The specific method includes the following steps:

[0171] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 87.6 mg (3×10 -4 mol) (3-phenyloxirane-2-yl)(4-(trifluoromethyl)phenyl)methanone was dissolved in 0.1 ml of 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-((4-(trifluoromethyl)phenyl)formyl)-5-phenyl-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 77%. The NMR data of the product were: 1 H NMR (400 MHz, CDCl 3 ): δ 8.10 (d, J = 8.1 Hz, 2H, ArH), 7.78 (d, J = 8.2Hz, 2H, ArH), 7.48-7.43 (m, 5H, ArH), 6.04 (d, J = 6.3 Hz, 1H, CH), 5.55 (d, J =6.3 Hz, 1H, CH).

[0172] Application Example 35

[0173] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-(4-fluorophenyl)oxirane-2-yl)(4-fluorophenyl)methanone and carbon dioxide. The specific method includes the following steps:

[0174] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction bottle, and 78 mg (3×10 -4 mol) (3-(4-fluorophenyl)oxirane-2-yl)(4-fluorophenyl)methanone was dissolved in 0.1 ml of 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-((4-fluorophenyl)formyl)-5-(4-fluorophenyl)-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 77%. The NMR data of the product were: 1 HNMR (400 MHz, CDCl 3 ):δ 8.02 (dd, J = 8.9, 5.3 Hz, 2H, ArH), 7.43 (dd, J = 8.7, 5.1Hz, 2H, ArH), 7.16 (dd, J = 8.4, 6.1 Hz, 4H, ArH), 6.02 (d, J = 6.6 Hz, 1H, CH),5.48 (d, J = 6.6 Hz, 1H, CH).

[0175] Application Example 36

[0176] Amino-bridged triaryloxylanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-(4-chlorophenyl)oxirane-2-yl)(4-chlorophenyl)methanone and carbon dioxide. The specific method includes the following steps:

[0177] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 87.6 mg (3×10 -4 mol) (3-(4-chlorophenyl)oxirane-2-yl)(4-chlorophenyl)methanone was dissolved in 0.1 ml of 1,4-dioxane, transferred into a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried by rotation, and the product 4-((4-chlorophenyl)formyl)-5-(4-chlorophenyl)-1,3-dioxolane-2-one was obtained by rapid column chromatography separation, with a calculated yield of 74%. The NMR data of the product were: 1 HNMR (400 MHz, CDCl 3 ): δ 7.93 (d, J= 8.7 Hz, 2H, ArH), 7.50 (s, 1H, ArH), 7.48(s, 1H, ArH), 7.45 (s, 1H, ArH), 7.43 (s, 1H, ArH), 7.38 (s, 2H, ArH), 6.02(d, J = 6.6 Hz, 1H, CH), 5.44 (d, J = 6.6 Hz, 1H, CH).

[0178] Application Example 37

[0179] Amino-bridged triaryloxy lanthanum complex (LLa(THF)) and tetrabutylammonium iodide are used to catalyze the cycloaddition reaction of (3-methyloxirane-2-yl)phenyl-ketone and carbon dioxide. The specific method includes the following steps:

[0180] In anhydrous and oxygen-free inert gas environment, 6.2 mg (6.0 × 10 -6 mole, 2 mol%) LLa(THF) and 6.6 mg (1.8×10 -5 molar, 6 mol%) tetrabutylammonium iodide was added to the reaction flask, and 48.6 mg (3×10 -4 mol) (3-methyl-2-oxiranyl) phenyl-methanone was dissolved in 0.1 ml of 1,4-dioxane, transferred to a reaction kettle, filled with carbon dioxide gas, placed at 50 °C with constant temperature stirring, and heated at 40 bar CO 2 The reaction was carried out under pressure; after the reaction was completed, the carbon dioxide in the reactor was evacuated, the reactor was vented, silica gel powder was added and dried, and the product 4-benzoyl-5-methyl-1,3-dioxolane-2-one was obtained by rapid column chromatography separation. The calculated yield was 91%, and the NMR data of the product was: 1 H NMR (400 MHz, CDCl 3 ): δ8.03-7.96 (m, 2H, ArH), 7.68 (t, J = 7.4 Hz, 1H, ArH), 7.54 (t, J = 7.8 Hz, 2H,ArH), 5.28 (d, J = 6.0 Hz, 1H, CH), 5.09 (m, 1H, CH), 1.64 (d, J = 6.3 Hz, 3H,CH 3 ).

[0181] In summary, the amino-bridged triaryloxy rare earth metal complex LRE (THF) provided by the present invention can be prepared by ligand precursor LH3 With RECp 3 Reaction preparation. The catalyst has a clear structure, simple synthesis, and high yield. The two-component catalytic system composed of an amino-bridged triaryloxy rare earth metal complex and a quaternary ammonium salt can catalyze the cycloaddition reaction of oxidative chalcone compounds with carbon dioxide. It has high catalytic activity, low catalyst dosage, relatively mild reaction conditions, wide substrate universality, high yield of the target product, and simple reaction operation and post-processing.

[0182] Obviously, the above embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art should understand that other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. An amino-bridged triaryloxy rare earth metal complex, characterized in that: The structural formula of the amino-bridged triaryloxy rare earth metal complex is as follows: ， Wherein, RE is lanthanum, neodymium or samarium, R 1 , R 2 At the same time, it is tert-butyl or cumyl.

2. A method for preparing the amino-bridged triaryloxy rare earth metal complex according to claim 1, characterized in that: The following steps are involved: (1) under an inert atmosphere, a rare earth metal halide is dispersed in an ether solvent, and an ether solution of cyclopentadienyl sodium is added to the obtained suspension to react and obtain a tricyclopentadienyl rare earth compound; (2) dissolving the tricyclopentadienyl rare earth compound and amino-bridged triphenol obtained in step (1) in tetrahydrofuran, and reacting at 45-65° C. to obtain the amino-bridged triaryloxy rare earth metal complex; The structural formula of the amino-bridged triphenol is , where R 1 , R 2 At the same time, it is tert-butyl or cumyl.

3. The preparation method according to claim 2, characterized in that: In step (1), the molar ratio of the rare earth metal halide to cyclopentadienyl sodium is 1:(2-4).

4. The preparation method according to claim 2, characterized in that In step (2), the preparation method of the amino-bridged triphenol comprises the following steps: N -(Pyridin-2-yl-methyl)-1,2-ethylenediamine and 2,4-disubstituted phenol are mixed at 85-95° C., and then formaldehyde or paraformaldehyde is added to react to obtain the amino-bridged triphenol.

5. Use of the amino-bridged triaryloxy rare earth metal complex according to claim 1 in the catalytic oxidation cycloaddition reaction of chalcone compounds and carbon dioxide.

6. The use according to claim 5, characterized in that The method for the cycloaddition reaction of an oxidized chalcone compound and carbon dioxide catalyzed by an amino-bridged triaryloxy rare earth metal complex comprises the following steps: in anhydrous and oxygen-free environment and under the protection of an inert gas, an amino-bridged triaryloxy rare earth metal complex, a co-catalyst and an oxidized chalcone compound are mixed, carbon dioxide is introduced and a cycloaddition reaction is carried out at 40-70°C to obtain a cyclocarbonate compound; the co-catalyst is selected from one or more of tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetraethylammonium bromide, tetra-n-octylammonium bromide and (2-bromoethyl)trimethylammonium bromide.

7. The use according to claim 6, characterized in that: The molar ratio of the amino-bridged triaryloxy rare earth metal complex, the co-catalyst and the oxidized chalcone compound is (0.5-4):(2-6):(50-100).

8. The use according to claim 6, characterized in that The pressure of the cycloaddition reaction is 10-40 bar.

9. The use according to claim 6, characterized in that: An amino-bridged triaryloxy rare earth metal complex, a co-catalyst, an oxidized chalcone compound and a solvent are mixed, wherein the solvent is selected from one or more of toluene, p-xylene, 1,4-dioxane, dimethyl sulfoxide, 1,1,2,2-tetrachloroethane, benzonitrile and halobenzene.

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