Preparation method of aryl triepoxypropane compound

Abstract

The invention belongs to the technical field of fine chemicals, medicines and materials, and particularly relates to a preparation method of an aryl triepoxypropane compound. The preparation method comprises the following steps: 1) mixing 2, 6-diallylphenol with a first solvent, adding allyl bromide and alkali to obtain a mixture, heating and refluxing the mixture, reacting, and cooling to room temperature to obtain 1, 3-diallyl-2-allyloxybenzene as shown in a formula I; and 2) reacting the 1, 3-diallyl-2-allyloxybenzene as shown in the formula I, a metal complex catalyst and an oxidizing agent in a second solvent to obtain the aryl triepoxypropane compound as shown in a formula II. The preparation method has the advantages of cheap and easily available raw materials, simple and mild reaction, low catalyst price and high reaction yield, and can realize industrial production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of fine chemicals, medicine, material technology, more specifically, the present application relates to a preparation method of aryl triglycidyl ether compound. BACKGROUND

[0002] Aryl glycidylethers (also known as aryl glycidyl ethers) refers to compounds in which a benzene ring or other aromatic ring is connected to an epoxypropyl group through an ether bond, with the general formula Ar-O-CH2-CH(O)CH2. These compounds have both the high reactivity of epoxy groups and the rigidity, heat resistance, and electrical properties of aromatic groups. As active diluents for epoxy resins and flexible modification monomers, they are particularly useful in bisphenol A, phenolic, naphthalene-based, and other basic epoxy resin systems, and can simultaneously achieve the triple tasks of "viscosity reduction + toughening + improved wettability". They are widely used in the following areas:

[0003] Electronic and electrical device packaging and copper-clad boards. High-frequency high-speed PCBs: phenyl glycidyl ether dilutes low-polarity resins, reducing the dielectric constant (Dk) and loss factor (Df) to meet the needs of 5G / 6G. Power device packaging: blending with AlN and Si3N4 fillers improves the density of the thermal conduction path and prevents high-temperature cracking.

[0004] Aerospace and high-end composites. Carbon fiber prepreg: replacing part of the bisphenol A epoxy, the resin system viscosity is reduced to 2000-3000 mPa·s (25℃), which is beneficial to the preparation of ultra-thin prepreg tape by hot melt method. Flame-retardant toughening: introducing phosphorus-containing aryl glycidyl ether (such as DOPO-PGE) to achieve UL-94 V-0 while maintaining toughness (impact strength ↑ 35%).

[0005] Functional coatings and adhesives. Solvent-free high-solid coatings: PGE is used as an active diluent, and the system VOC is <100 g / L, meeting the low VOC requirements of GB / T 38597-2020. Metal structural adhesive: synergistic with silane coupling agents, significantly improving the lap shear strength on aluminum alloy.

[0006] Medicines, pesticides, and fine chemical intermediates. β-receptor blockers: through stereoselective ring opening of aryl glycidyl ether, the side chain of metoprolol and atenolol is prepared, with an optical purity of S-configuration ≥99%. Fungicides: fluorine-containing aryl glycidyl ether derivatives are used to synthesize methoxy acrylate fungicides, which can prevent and control powdery mildew and downy mildew. Chiral epoxy alcohol: after kinetic resolution, it is used as a key fragment for calcium antagonists and antidepressants.

[0007] Electronic cleaning and disinfectants: phenyl glycidyl ether has low foam and low surface tension, replacing glycol ethers for cleaning after semiconductor wafer cutting.

[0008] In the daily chemical industry: it is added in trace amounts to laundry detergent to improve the removal rate of stubborn stains by utilizing its surface activity, and it is also easily biodegradable.

[0009] Peroxide stabilizers: When combined with halogenated pesticides, they prevent thermal decomposition and extend shelf life.

[0010] The synthesis of aryl monoepoxides is very mature. Whether through substitution reactions of phenols and halogenated propylene oxides or oxidation and epoxidation reactions of aryl alkenes, industrialization has been achieved.

[0011] Reports on aryl dicyclooxyethylene oxides are relatively few. Among them, the synthesis of aryl dioxyethylene oxides is more common, mainly through the substitution reaction of diphenols and epichlorohydrin. The synthesis of aryl dimethylene oxide is only reported in 2003 (WO2003055861) of o-diallylbenzene synthesizing o-phenyl diglycidyl ether under the oxidation of m-chloroperoxybenzoic acid; the synthesis of aryl(oxy)(methylene) dicyclooxyethylene oxide is only reported in 2017 (CN109312052A) and 2018 (JP2018002691A) of o-allyl allylpropoxybenzene synthesizing o-glycidyl propoxybenzyl glycidyl ether under the action of hydrogen peroxide.

[0012] A literature search revealed that the only relevant report on aryltricyclopropane was published in 1972 on DE2239681C3, which described the preparation of aryltricyclopropane by oxidizing olefins with hydrogen peroxide using hexafluoroacetone or 1,1,3-trifluorotrichloroacetone and its hydrate as catalysts.

[0013] Therefore, given the limited reports on aryl tricyclooxypropylene in existing technologies and the difficulty in industrializing it, there is an urgent need to provide a high-efficiency and low-cost preparation method to achieve the industrialization of aryl tricyclooxypropylene. Summary of the Invention

[0014] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide a method for preparing aryl trioxypropane compounds, which mainly solves the problems of the scarcity of synthesis methods and the difficulty in industrialization in the prior art.

[0015] To address the above problems, the present invention provides a method for preparing aryl trioxypropane compounds, the method comprising the following steps:

[0016] 1) 2,6-diallylphenol was mixed with a first solvent and then allyl bromide and a base were added to obtain a mixture. The mixture was heated to reflux and then cooled to room temperature to obtain 1,3-diallyl-2-allyloxybenzene as shown in Formula I.

[0017] 2) The 1,3-diallyl-2-allyloxybenzene shown in Formula I, a metal complex catalyst, and an oxidant are reacted in a second solvent to obtain the aryl trioxypropane compound shown in Formula II.

[0018]

[0019] By adopting the aforementioned technical solution, the beneficial effects of the present invention are:

[0020] The present invention provides a method for preparing polyolefin-containing compounds by oxidizing them into corresponding aryl tricyclopropane compounds. This method uses inexpensive and readily available raw materials, has a simple and mild reaction process, uses inexpensive catalysts, and achieves high reaction yields, making it suitable for industrial production. Attached Figure Description

[0021] Figure 1 The hydrogen spectrum of the product prepared in Example 1. Detailed Implementation

[0022] The following describes in detail the embodiments of the preparation method of the aryl trioxypropylene compound provided by the present invention.

[0023] The technical features of the present invention will be further clearly and completely described below with reference to specific embodiments, which is not intended to limit the scope of protection thereof.

[0024] The terms "preferred," "more preferred," etc., used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0025] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included. For example, a specified range from “1 to 10” should be considered to include any and all subranges between the minimum value 1 and the maximum value 10. Exemplary subranges of the range 1 to 10 include, but are not limited to, 1 to 6.1, 3.5 to 7.8, 5.5 to 10, etc.

[0026] Through extensive research and exploration, the inventors of this invention have provided a method for preparing aryl tricyclooxypropylene compounds. This method uses 2,6-diallylphenol as a raw material, reacting it with allyl bromide under alkaline conditions to obtain a 1,3-diallyl-2-allyloxybenzene intermediate. This intermediate, under the catalysis of a metal complex, reacts with different oxidants to prepare the aryl tricyclooxypropylene compound shown in Formula II, namely 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]biscyclooxypropylene. This method has many advantages, including inexpensive and readily available raw materials, a simple and mild reaction process, inexpensive catalysts, and high reaction yield. Based on this, this application was completed.

[0027] Preparation methods of aryl trioxypropylene compounds

[0028] This invention provides a method for preparing aryl trioxypropylene compounds, the method comprising the following steps:

[0029] 1) 2,6-diallylphenol was mixed with a first solvent and then allyl bromide and a base were added to obtain a mixture. The mixture was heated to reflux and then cooled to room temperature to obtain 1,3-diallyl-2-allyloxybenzene as shown in Formula I.

[0030] 2) The 1,3-diallyl-2-allyloxybenzene shown in Formula I, a metal complex catalyst, and an oxidant are reacted in a second solvent to obtain the aryl trioxypropane compound shown in Formula II.

[0031]

[0032] The aryl tricyclopropane compound shown in Formula II is 2,2′-[[2-(cyclopropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]biscyclopropane.

[0033] In the preparation method of the aryl trioxypropane compound provided by this invention, step 1) involves mixing 2,6-diallylphenol with a first solvent, then adding allyl bromide and a base to obtain a mixture. The mixture is heated under reflux, and after the reaction, it is cooled to room temperature to obtain 1,3-diallyl-2-allyloxybenzene as shown in Formula I. Specifically:

[0034] In step 1) of the present invention, the first solvent is one or more of anhydrous acetone, methanol, ethanol, isopropanol, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, and N,N-dimethylformamide.

[0035] In step 1) of this invention, the potassium carbonate is one or more of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, and potassium tert-butoxide.

[0036] In step 1) of this invention, the molar ratio of 2,6-diallylphenol to allyl bromide is 1:1 to 2. Optionally, the molar ratio of 2,6-diallylphenol to allyl bromide can be, for example, 1:1 to 1.5 or 1:1.5 to 2.

[0037] In step 1) of this invention, the molar ratio of 2,6-diallylphenol to potassium carbonate is 1:1 to 2. Optionally, the molar ratio of 2,6-diallylphenol to potassium carbonate can be, for example, 1:1 to 1.5 or 1:1.5 to 2.

[0038] In step 1) of this invention, the mass ratio of 2,6-diallylphenol to the first solvent is 1:2 to 5. Optionally, the mass-volume ratio of 2,6-diallylphenol to the first solvent can be, for example, 1:2 to 3, 1:3 to 5, 1:2 to 4, or 1:4 to 5.

[0039] In step 1) of this invention, the reaction is carried out under a nitrogen atmosphere.

[0040] In step 1) of this invention, the reflux reaction temperature is 55-60°C. The reflux reaction time is 4-8 hours, which can be 4-6 hours or 6-8 hours.

[0041] Step 1) of the present invention also includes post-processing, which includes concentrating the reaction solution under reduced pressure to obtain 1,3-diallyl-2-allyloxybenzene as shown in Formula I.

[0042] In the preparation method of the aryltricyclopropane compound provided by this invention, step 2) involves reacting 1,3-diallyl-2-allyloxybenzene (Formula I), a metal complex catalyst, and an oxidant in a second solvent to obtain the aryltricyclopropane compound (Formula II). Specifically:

[0043] In step 2) of this invention, the metal complex catalyst used in the reaction is an iron complex catalyst. Optionally, the iron complex catalyst is selected from one or more of porphyrin iron, phthalocyanine iron, tetrachlorophenylporphyrin iron, tetraphenylporphyrin iron, hydroxyferric heme, and N,N'-bis(salicylyl)ethylenediamine iron.

[0044] In step 2) of this invention, the oxidant is selected from one or more of sodium hypochlorite, calcium hypochlorite, potassium persulfate, potassium persulfate, sodium persulfate, ammonium persulfate, sodium percarbonate, sodium perborate, hydrogen peroxide, and m-chloroperoxybenzoic acid. Preferably, the oxidant is selected from one or more of sodium hypochlorite, calcium hypochlorite, potassium persulfate, sodium percarbonate, sodium perborate, and hydrogen peroxide.

[0045] In step 2) of this invention, the molar ratio of 1,3-diallyl-2-allyloxybenzene, the metal complex catalyst, and the oxidant shown in Formula I in the reaction is 1:(0.0001-0.01):(3-6). Optionally, the molar ratio of 1,3-diallyl-2-allyloxybenzene, the metal complex catalyst, and the oxidant shown in Formula I can be, for example, 1:(0.0001-0.001):(3-6), 1:(0.001-0.005):(3-6), 1:(0.005-0.01):(3-6), 1:(0.0001-0.01):(3-4), 1:(0.0001-0.01):(4-5), or 1:(0.0001-0.01):(5-6).

[0046] In step 2) of this invention, the reaction is heated under nitrogen protection.

[0047] In step 2) of this invention, the mass ratio of 1,3-diallyl-2-allyloxybenzene (Formula I) to the second solvent is 1:2 to 5. Optionally, the mass ratio of 1,3-diallyl-2-allyloxybenzene (Formula I) to the second solvent can be, for example, 1:2 to 3 or 1:3 to 5.

[0048] In step 2) of this invention, the reaction temperature is 0–100°C. Optionally, the reaction temperature can be, for example, 0–10°C, 10–50°C, 0–50°C, 50–100°C, 0–30°C, 30–50°C, 50–70°C, 50–60°C, 60–70°C, 70–80°C, 80–100°C, 80–90°C, 90–100°C, etc. The reaction time is 3–8 hours, 3–6 hours, 6–8 hours, 3–7 hours, 7–8 hours, 3–4 hours, 4–6 hours, 6–7 hours, 7–8 hours, etc.

[0049] In step 2) of this invention, the second solvent used in the reaction is selected from one or more of acetonitrile, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dichloromethane, dichloroethane, and water. Preferably, the second solvent is selected from one or more of acetonitrile, dimethyl carbonate, diethyl carbonate, dichloromethane, and dichloroethane.

[0050] The beneficial effects of the present invention will be further illustrated below with reference to the embodiments.

[0051] To make the inventive objectives, technical solutions, and beneficial effects of this invention clearer, the invention is further described in detail below with reference to embodiments. However, it should be understood that the embodiments of this invention are merely for illustrative purposes and not for limiting the invention, and the embodiments are not limited to those given in the specification. Unless otherwise specified, specific experimental or operational conditions in the embodiments were prepared under conventional conditions or according to the conditions recommended by the material supplier.

[0052] Furthermore, it should be understood that the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, does not preclude the existence of other method steps before or after the combined steps, or the insertion of other method steps between these explicitly mentioned steps, unless otherwise stated. It should also be understood that the combined connection relationship between one or more devices / apparatus mentioned in this invention does not preclude the existence of other devices / apparatus before or after the combined devices / apparatus, or the insertion of other devices / apparatus between these explicitly mentioned devices / apparatus, unless otherwise stated. Moreover, unless otherwise stated, the numbering of each method step is merely a convenient tool for identifying each method step, and not for limiting the order of the method steps or limiting the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.

[0053] In the following embodiments, unless otherwise specified, all the raw materials of the present invention are commercially available or prepared according to conventional methods in the art.

[0054] Example

[0055] Example 1

[0056] Example 1 provides a method for preparing 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]bisepoxypropane using 2,6-diallylphenol and allyl bromide as raw materials, potassium carbonate as a base, 1,3-diallyl-2-allyloxybenzene, porphyrin iron as a catalyst, and hydrogen peroxide as an oxidant. The synthetic reaction formula is as follows:

[0057]

[0058] Under a nitrogen atmosphere, 242 g of allyl bromide and 276 g of potassium carbonate were added to a stirred solution of 348 g of 2,6-diallylphenol in 696 g of anhydrous acetone. The mixture was heated under reflux for 6 hours at a reaction temperature of 55-60 °C. After the reaction was complete, the mixture was cooled to room temperature. The reaction solution was concentrated under reduced pressure to give the product 1,3-diallyl-2-allyloxybenzene.

[0059] 214 g of 1,3-diallyl-2-allyloxybenzene was accurately weighed into a 2000 ml four-necked flask. 428 g of acetonitrile was added, followed by the addition of 65.1 mg of porphyrin iron. The mixture was heated to 50 °C under nitrogen protection, and 582 g of 35% hydrogen peroxide was slowly added dropwise, maintaining the temperature between 50-60 °C. After the addition was complete, the reaction was maintained at this temperature for 4 hours. 428 g of DCM was added to extract the organic phase, which was then dried, filtered, and solvent-removed to obtain 236.1 g of the product. The GC purity was 95.7%, and the yield was 90.1%.

[0060] Example 2

[0061] Example 2 provides a method for preparing 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]bisepoxypropane using 2,6-diallylphenol, allyl bromide as a raw material, sodium carbonate as a base, to obtain 1,3-diallyl-2-allyloxybenzene, followed by preparation of 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]bisepoxypropane using tetraphenylporphyrin iron as a catalyst and potassium persulfate as an oxidant. The synthetic reaction formula is as follows:

[0062]

[0063] Under a nitrogen atmosphere, 290 g of allyl bromide and 254 g of sodium carbonate were added to a stirred solution of 348 g of 2,6-diallylphenol in 696 g of methanol. The mixture was heated under reflux for 5 hours at a reaction temperature of 55-60 °C. After the reaction was complete, the mixture was cooled to room temperature. The reaction solution was concentrated under reduced pressure to give the product 1,3-diallyl-2-allyloxybenzene.

[0064] Accurately weigh 214 g of 1,3-diallyl-2-allyloxybenzene into a 2000 ml four-necked flask. Add 1070 g of dimethyl carbonate, then weigh 70.4 mg of tetraphenylporphyrin iron and add it to the reaction flask. Heat to 70 °C under nitrogen protection, then slowly add 1080 g of potassium persulfate, maintaining the temperature at 70-80 °C. After the addition is complete, maintain the reaction temperature for 6 hours. Filter and remove solvent to obtain 231.0 g of product with a GC purity of 94.6% and a yield of 88.17%.

[0065] Example 3

[0066] Example 3 provides a method for preparing 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]bisepoxypropane using 2,6-diallylphenol and allyl bromide as raw materials, potassium hydroxide as a base, and then using N,N'-bis(salicylyl)ethylenediamine iron as a catalyst and sodium hypochlorite as an oxidant. The synthetic reaction formula is as follows:

[0067]

[0068] Under a nitrogen atmosphere, 266 g of allyl bromide and 124 g of potassium hydroxide were added to a stirred solution of 348 g of 2,6-diallylphenol in 1392 g of ethyl acetate. The mixture was heated to 55-60 °C and reacted for 7 hours. After the reaction was complete, the mixture was cooled to room temperature. The reaction solution was concentrated under reduced pressure to give the product 1,3-diallyl-2-allyloxybenzene.

[0069] Accurately weigh 214 g of 1,3-diallyl-2-allyloxybenzene into a 5000 ml four-necked flask. After adding 1070 g of dichloromethane, weigh 70.4 mg of N,N'-bis(salicylic acid)ethylenediamine iron and add it to the reaction flask. Cool to 0 °C under nitrogen protection, and slowly add 2235 g of 10% sodium hypochlorite aqueous solution, controlling the temperature at 0-10 °C. After the addition is complete, maintain the reaction temperature for 3 hours. Separate the liquid, dry the organic phase, filter, and remove solvent to obtain 228.7 g of product with a GC purity of 95.0% and a yield of 87.3%.

[0070] Example 4

[0071] Example 4 provides a method for preparing 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]bisepoxypropane using 2,6-diallylphenol and allyl bromide as raw materials, sodium hydroxide as a base, 1,3-diallyl-2-allyloxybenzene, and then using iron phthalocyanine as a catalyst and sodium percarbonate as an oxidant. The synthetic reaction formula is as follows:

[0072]

[0073] Under a nitrogen atmosphere, 363 g of allyl bromide and 120 g of sodium hydroxide were added to a stirred solution of 348 g of 2,6-diallylphenol in 1044 g of acetonitrile. The mixture was heated to 55-60 °C and reacted for 4 hours. After the reaction was complete, the mixture was cooled to room temperature. The reaction solution was concentrated under reduced pressure to give the product 1,3-diallyl-2-allyloxybenzene.

[0074] 214 g of 1,3-diallyl-2-allyloxybenzene was accurately weighed into a 2000 ml four-necked flask. After adding 1070 g of diethyl carbonate, 568 mg of ferric phthalocyanine was weighed and added to the reaction flask. The mixture was heated to 90 °C under nitrogen protection, and 540 g of sodium percarbonate was slowly added, maintaining the temperature between 90 and 100 °C. After the addition was complete, the reaction was maintained at this temperature for 8 hours. After filtration and solvent removal, 220.9 g of product was obtained, with a GC purity of 93.9% and a yield of 84.3%.

[0075] Example 5

[0076] Example 5 provides a method for preparing 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]bisepoxypropane using 2,6-diallylphenol and allyl bromide as raw materials, sodium tert-butoxide as a base, and then using tetrachlorophenylporphyrin iron as a catalyst and calcium hypochlorite as an oxidant. The synthetic reaction formula is as follows:

[0077]

[0078] Under a nitrogen atmosphere, 484 g of allyl bromide and 384 g of sodium tert-butoxide were added to a stirred solution of 348 g of 2,6-diallylphenol in 1740 g of tetrahydrofuran. The mixture was heated to 55-60 °C and reacted for 8 hours. After the reaction was complete, the mixture was cooled to room temperature. The reaction solution was concentrated under reduced pressure to give the product 1,3-diallyl-2-allyloxybenzene.

[0079] Accurately weigh 214 g of 1,3-diallyl-2-allyloxybenzene into a 2000 ml four-necked flask. After adding 1070 g of dichloroethane, weigh 841 mg of tetrachlorophenylporphyrin iron and add it to the reaction flask. Heat to 70 °C under nitrogen protection, and slowly add 650 g of calcium hypochlorite, controlling the temperature at 70-80 °C. After the addition is complete, maintain the reaction temperature for 7 hours. After filtration and solvent removal, 214.8 g of product was obtained, with a GC purity of 93.3% and a yield of 82.0%.

[0080] Example 6

[0081] Example 6 provides a method for preparing 2,2′-[[2-(epoxypropane-2-ylmethoxy)-1,3-phenylene]bis(methylene)]bisepoxypropane using 2,6-diallylphenol and allyl bromide as raw materials, potassium tert-butoxide as a base, 1,3-diallyl-2-allyloxybenzene, and then using ferric heme as a catalyst and sodium perborate as an oxidant. The synthetic reaction formula is as follows:

[0082]

[0083] Under a nitrogen atmosphere, 242 g of allyl bromide and 224 g of potassium tert-butoxide were added to a stirred solution of 348 g of 2,6-diallylphenol and 696 g of N,N-dimethylformamide. The mixture was heated to 55-60 °C and reacted for 4 hours. After the reaction was complete, the mixture was cooled to room temperature. The reaction solution was concentrated under reduced pressure to give the product 1,3-diallyl-2-allyloxybenzene.

[0084] 214 g of 1,3-diallyl-2-allyloxybenzene was accurately weighed into a 2000 ml four-necked flask. After adding 1070 g of dichloroethane, 631 mg of ferric heme was weighed and added to the reaction flask. The mixture was heated to 70 °C under nitrogen protection, and 336 g of sodium perborate was slowly added, maintaining the temperature at 70-80 °C. After the addition was complete, the reaction was maintained at this temperature for 7 hours. After filtration and solvent removal, 227.2 g of product was obtained, with a GC purity of 95.3% and a yield of 86.7%.

[0085] In summary, this invention effectively overcomes the various shortcomings of the prior art and has high industrial application value.

[0086] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any form or substance. It should be noted that those skilled in the art can make various improvements and additions without departing from the method of the present invention, and these improvements and additions should also be considered within the scope of protection of the present invention. Any modifications, alterations, and equivalent changes made by those skilled in the art based on the above-disclosed technical content without departing from the spirit and scope of the present invention are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and evolutions made to the above embodiments based on the essential technology of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing an aryltricyclopropane compound, characterized in that, The preparation method includes the following steps: 1) 2,6-diallylphenol was mixed with a first solvent and then allyl bromide and a base were added to obtain a mixture. The mixture was heated to reflux and then cooled to room temperature to obtain 1,3-diallyl-2-allyloxybenzene as shown in Formula I. 2) The 1,3-diallyl-2-allyloxybenzene shown in Formula I, a metal complex catalyst, and an oxidant are reacted in a second solvent to obtain the aryl trioxypropane compound shown in Formula II.

2. The method for preparing the aryltricyclooxypropylene compound according to claim 1, characterized in that, It also includes one or more of the following conditions: In step 1), the first solvent is selected from one or more of anhydrous acetone, methanol, ethanol, isopropanol, acetonitrile, tetrahydrofuran, ethylene glycol dimethyl ether, ethyl acetate, and N,N-dimethylformamide. A2) In step 1), the alkali is selected from one or more of potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, and potassium tert-butoxide; In step 1) of A3), the molar ratio of 2,6-diallylphenol to allyl bromide is 1:1-2; In step 1) of A4), the molar ratio of 2,6-diallylphenol to base is 1:1-2; In step 1) of A5, the mass ratio of 2,6-diallylphenol to the first solvent is 1:2-5.

3. The method for preparing the aryltricyclooxypropylene compound according to claim 1, characterized in that, It also includes one or more of the following conditions: In step 1) of B1), the reaction is carried out under a nitrogen atmosphere; B2) In step 1), the reflux reaction temperature is 55-60℃; In step 1) of B3), the heating and reflux reaction time is 4 to 8 hours.

4. The method for preparing the aryltricyclooxypropylene compound according to claim 1, characterized in that, In step 2), the metal complex catalyst is an iron complex catalyst.

5. The method for preparing the aryltricyclooxypropylene compound according to claim 4, characterized in that, In step 2), the iron complex catalyst is selected from one or more of porphyrin iron, phthalocyanine iron, tetrachlorophenylporphyrin iron, tetraphenylporphyrin iron, hydroxyferric heme, and N,N'-bis(salicylyl)ethylenediamine iron.

6. The method for preparing the aryltricyclooxypropylene compound according to claim 1, characterized in that, In step 2), the oxidant is selected from one or more of sodium hypochlorite, calcium hypochlorite, potassium peroxymonosulfate, potassium persulfate, sodium persulfate, ammonium persulfate, sodium percarbonate, sodium perborate, hydrogen peroxide, and m-chloroperoxybenzoic acid.

7. The method for preparing the aryltricyclooxypropylene compound according to claim 6, characterized in that, In step 2), the oxidant is selected from one or more of sodium hypochlorite, calcium hypochlorite, potassium persulfate, sodium percarbonate, sodium perborate, and hydrogen peroxide.

8. The method for preparing the aryltricyclooxypropylene compound according to claim 1, characterized in that, Step 2) also includes one or more of the following conditions: In step 2) of C1), the molar ratio of 1,3-diallyl-2-allyloxybenzene, the metal complex catalyst and the oxidant shown in Formula I is 1:(0.0001-0.01):(3-6); C2) In step 2), the mass ratio of 1,3-diallyl-2-allyloxybenzene shown in Formula I to the second solvent is 1:2 to 5; C3) In step 2), the reaction is heated under nitrogen protection; In step 2) of C4), the reaction temperature is 0–100℃; In step 2 of C5, the reaction time is 3-8 hours.

9. The method for preparing the aryltricyclooxypropylene compound according to claim 1, characterized in that, In step 2), the second solvent is selected from one or more of acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dichloromethane, dichloroethane, and water.

10. The method for preparing the aryltricyclooxypropylene compound according to claim 9, characterized in that, In step 2), the second solvent is selected from one or more of acetonitrile, dimethyl carbonate, diethyl carbonate, dichloromethane, and dichloroethane.

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