A preparation method of phenylene compound

Abstract

The present invention relates to the technical field of organic synthesis, and in particular to a method for preparing a phenylene compound, the preparation method comprising the following steps: mixing compound 1, aluminum chloride, triphenylphosphine, a Lewis base and a solvent, reacting, and post-treating to obtain compound 2, wherein the Lewis base is selected from any one or more of sodium acetate, potassium acetate, sodium phosphate, potassium phosphate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, pyridine and triethylamine. The present invention adds an additional Lewis base in the reaction, so that the present application can reduce the generation of additional impurities and thus improve the yield of the target product.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for preparing a phenylene compound. Background Art

[0002] Monofunctional aromatic alkenyl compounds are widely used as polymerizable monomers in many polymer materials.

[0003] For example, Chinese patent CN 114729218A discloses an ink composition, which indicates that various phenylene compounds including 4-tert-butoxystyrene can be used as a monomer for preparing the ink composition.

[0004] In the prior art, A General Solution for Unstable Boronic Acids: Slow-Release Cross-Coupling from Air-Stable MIDA Boronates (Journal of the American Chemical Society, 2009, vol. 131, p. 6961-6963) reports a method for preparing 4-tert-butoxystyrene, but it requires the use of vinylboronic acid and palladium catalyst, and the cost of raw materials is relatively high.

[0005] At present, there is no method for preparing phenylene compounds with low cost and high yield in the prior art. Summary of the invention

[0006] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a low-cost and high-yield method for preparing phenylene compounds to solve the problems in the prior art.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] The present invention provides a method for preparing a phenylene compound, which has the following characteristics:

[0009]

[0010] In the formula, when R1 is a substituted aryl group substituted with at least one tert-butoxy group, R3 is H, and R2 is H or a C1-C6 alkyl group;

[0011] When R3 is a substituted aryl group substituted with at least one tert-butoxy group, R1 and R2 are independently selected from H, C1-C6 alkyl, aryl or substituted aryl;

[0012] The preparation method comprises the following steps:

[0013] Compound 1, aluminum chloride, triphenylphosphine, a Lewis base and a solvent are mixed and reacted, and then post-treated to obtain compound 2.

[0014] Compared with the prior art, the present invention has the following beneficial effects:

[0015] The preparation method of the phenylene compound of the present invention is to react compound 1, aluminum chloride, triphenylphosphine, a Lewis base and a solvent. Specifically, by adding an additional Lewis base in the reaction, the present invention can reduce the generation of additional impurities and thus improve the yield of the target product. More specifically, the yield of the present invention is greater than 80%, and the purity is as high as 99.8%. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is the HPLC spectrogram of the product in Example 5 of the present invention.

[0017] Figure 2 The product of Example 5 of the present invention 1 HNMR spectrum. DETAILED DESCRIPTION

[0018] Hereinafter, embodiments of the method for producing a phenylalkenyl compound disclosed specifically will be described in detail.

[0019] Definition of terms

[0020] Unless otherwise specified, the following words, phrases and symbols used in this specification generally have the meanings described below.

[0021] In general, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including for cell culture, organic chemistry, analytical chemistry, and pharmacology, etc.) are those well known and commonly used in the art. Unless otherwise defined, all scientific and technical terms used herein in conjunction with the present disclosure described herein have the same meanings as commonly understood by those skilled in the art. In addition, in the claims and / or the specification, when the term "one" or "an" is used in conjunction with the term "comprising" or a noun, its meaning may be "one", but it is also consistent with the meaning of "one or more", "at least one" and "one or more than one". Similarly, the term "another" or "other" can mean at least a second or more.

[0022] It should be understood that whenever various aspects are described herein with the terms "including" or "comprising," other similar aspects described by "consisting of" and / or "consisting essentially of" are also provided.

[0023] In this article, the term "substituted" used alone or in combination refers to substitution by one or more substituents selected from the following in the present application: deuterium, halogen, cyano, nitro, hydroxyl, sulfhydryl, carbonyl, ester, imido, amino, phosphine oxide group, oxo, alkoxy, trifluoromethoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, cycloalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamino, aralkylamino, heteroarylamino, arylamino, arylphosphino and heteroaryl, acenaphthenyl, or unsubstituted; or substituted by a substituent connecting two or more of the substituents in the above-exemplified substituents, or unsubstituted. For example, "a substituent connecting two or more substituents" may include biphenyl, that is, the biphenyl may be an aryl, or a substituent connecting two phenyls. Preferably, the substituent is selected from any one or more of halogen, alkyl, alkoxy, and nitro.

[0024] As used herein, the term "alkyl" used alone or in combination may be straight or branched, and the number of carbon atoms may be, for example, C1-C6, C1-C5, C1-C4, C1-C3, C1-C2, etc. As examples, alkyl includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc.

[0025] In this article, the term "aryl" used alone or in combination refers to a monovalent carbocyclic aromatic group containing one or more fused rings, such as C6-C12, C6-C10 aryl, etc. The aryl group may be a monocyclic arylene group or a polycyclic arylene group. In some embodiments, monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, etc. Polycyclic aryl groups include, but are not limited to, naphthyl, etc. In the present disclosure, "substituted aryl" refers to an aryl group substituted one or more times (e.g., 1-4, 1-3 times, or 1-2 times) by a substituent, such as an aryl group monosubstituted, disubstituted, or trisubstituted by a substituent, wherein the substituent is optionally selected from, for example, halogen (fluorine, chlorine, bromine, or iodine, etc.), trifluoromethyl, hydroxyl, cyano, alkoxy, alkyl, deuterium, amino, sulfhydryl, nitro, carbonyl, ester group, oxo group, imido group, phosphine oxide group, trifluoromethoxy, and any combination thereof. Preferably, the substituent is selected from any one or more of halogen, alkyl, alkoxy, and nitro. More preferably, the substituent is selected from any one or more of fluorine, chlorine, bromine or iodine, C1-C3 alkyl, C1-C3 alkoxy, nitro. In the present disclosure, "substituted phenyl" refers to a phenyl substituted one or more times (e.g., 1-4, 1-3 or 1-2 times) by a substituent, and the substituent is defined as above.

[0026] As used herein, the term "halogen", alone or in combination, refers to fluorine, chlorine, bromine or iodine.

[0027] As used herein, the term "alkoxy" used alone or in combination refers to -O(alkyl). Optionally, the alkyl portion of the alkoxy group may contain 1-6 (or 1-5, 1-4, or 1-3) carbon atoms. Alkoxy groups may include, for example, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexyloxy, 2-ethylbutoxy, and the like.

[0028] Preparation method

[0029] The present invention provides a method for preparing a phenylene compound, and the reaction formula is as follows:

[0030]

[0031] In the formula, when R1 is a substituted aryl group substituted with at least one tert-butoxy group, R3 is H, and R2 is H or a C1-C6 alkyl group;

[0032] When R3 is a substituted aryl group substituted with at least one tert-butoxy group, R1 and R2 are independently selected from H, a C1-C6 alkyl group, an aryl group or a substituted aryl group.

[0033] The preparation method comprises the following steps:

[0034] Compound 1, aluminum chloride, triphenylphosphine, a Lewis base and a solvent are mixed, and after the reaction is complete, post-treatment is performed to obtain compound 2.

[0035] In the preparation method of the phenylene compound provided by the present invention, the Lewis base is selected from any one or more of sodium acetate, potassium acetate, sodium phosphate, potassium phosphate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, pyridine, and triethylamine. Preferably, the Lewis base is selected from any one of sodium acetate, potassium acetate, sodium bicarbonate, or potassium bicarbonate.

[0036] In the preparation method of the phenylene compound provided by the present invention, generally, the compound 1 and triphenylphosphine need to meet a certain dosage ratio. In some embodiments, the molar ratio of the compound 1 to triphenylphosphine is 1: (0.05-0.10). In specific embodiments, the molar ratio of the compound 1 to triphenylphosphine can also be 1: (0.05-0.08), 1: (0.08-0.10), 1: (0.05-0.06), 1: (0.06-0.07), 1: (0.07-0.08), 1: (0.08-0.09), or 1: (0.09-0.10), etc.

[0037] In the preparation method of the phenylene compound provided by the present invention, the ratio of the sum of the molar amounts of triphenylphosphine and Lewis base to the molar amount of aluminum trichloride is (1.5-3.0): 1. In a specific embodiment, the ratio of the sum of the molar amounts of triphenylphosphine and Lewis base to the molar amount of aluminum trichloride can be, for example, (1.5-2.0): 1, (2.0-2.5): 1, or (2.5-3.0): 1, etc.

[0038] In the method for preparing the phenylene compound provided by the present invention, the molar ratio of triphenylphosphine to Lewis base is (1-2):(1-2). In a specific embodiment, the molar ratio of triphenylphosphine to Lewis base can also be (1-1.5):(1-2), (1.5-2):(1-2), 1:(1-2), or 2:(1-2), etc.

[0039] In the preparation method of the phenylene compound provided by the present invention, the mass volume ratio of the compound 1 to the solvent is 1g:(10-15)mL. In a specific embodiment, the mass volume ratio of the compound 1 to the solvent is 1g:(10-12)mL, 1g:(12-15)mL, 1g:(10-11)mL, 1g:(11-12)mL, 1g:(12-13)mL, 1g:(13-14)mL, or 1g:(14-15)mL, etc.

[0040] In the preparation method of the phenylene compound provided by the present invention, the solvent is an organic solvent, and the organic solvent is selected from any one or both of acetonitrile and nitromethane.

[0041] In the preparation method of the phenylene compound provided by the present invention, in the reaction formula, when R1 is a substituted aryl group substituted by at least one tert-butoxy group, R3 is H, and R2 is H or a C1-C4 alkyl group.

[0042] Optionally, when R1 is a substituted phenyl group substituted by at least one tert-butoxy group, R2 is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or sec-butyl, etc.

[0043] Preferably, when R1 is a substituted phenyl group substituted by at least one tert-butyloxy group, R3 is H, and R2 is H, methyl or tert-butyl, etc.

[0044] In the preparation method of the phenylene compound provided by the present invention, in the reaction formula, when R3 is a substituted aryl group substituted by at least one tert-butoxy group, R1 and R2 are independently selected from H, C1-C4 alkyl, C6-C15 aryl, C6-C20 substituted aryl; wherein the substituent of the C6-C20 substituted aryl group is selected from any one or more of halogen, alkyl, and alkoxy nitro.

[0045] Optionally, when R3 is a substituted phenyl group substituted by at least one tert-butoxy group, R1 and R2 are independently selected from H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, phenyl or substituted phenyl groups, and the substituents of the substituted phenyl groups in R1 and R2 are independently selected from any one or more of halogen, alkyl, alkoxy, and nitro groups, and preferably, the substituents of the substituted phenyl groups are selected from any one or more of fluorine, chlorine, bromine, iodine, C1-C4 alkyl, C1-C4 alkoxy, and nitro groups. More preferably, the substituents of the substituted phenyl groups in R1 and R2 are independently selected from any one or more of fluorine, chlorine, bromine, iodine, methyl, ethyl, tert-butyl, tert-butoxy, and nitro groups.

[0046] Preferably, when R3 is a substituted phenyl group substituted by at least one tert-butyloxy group, R1 and R2 are independently selected from H, methyl, ethyl or tert-butyl.

[0047] In the preparation method of the phenylene compound provided by the present invention, in a specific embodiment, compound 1 is any one of the following compounds:

[0048]

[0049] In the preparation method of the phenylene compound provided by the present invention, the reaction is usually carried out at a certain temperature. Specifically, the reaction temperature of the present invention is 70°C-90°C. In some embodiments, the reaction temperature of the present invention is 70°C-80°C, 80°C-85°C, or 85°C-90°C. Preferably, the reaction temperature is 80°C-85°C.

[0050] In the preparation method of the phenylene compound provided by the present invention, the reaction is carried out under the protection of an inert gas, wherein the inert gas is one or more of nitrogen, argon and helium. The inert gas is preferably nitrogen.

[0051] The preparation method of the phenylene compound provided by the present invention further comprises a post-treatment step, wherein the post-treatment step comprises cooling, concentrating to dryness, and column chromatography. In a specific embodiment, the post-treatment step comprises cooling to 35° C., concentrating to dryness under reduced pressure, and n-heptane column chromatography.

[0052] The technical solution of the present application is described clearly and completely below in conjunction with the embodiments of the present invention. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by professionals and technicians in this field based on the above-mentioned contents of the present invention still belong to the scope of protection of the present invention.

[0053] In the following examples, the reagents, materials and instruments used are all commercially available unless otherwise specified.

[0054] <Example 1>

[0055] Preparation of compound 2a

[0056] This embodiment provides a method for preparing compound 2a, and the reaction formula is as follows:

[0057]

[0058] The steps include:

[0059] 1 g of compound 1a (5.2 mmol, 1.0 eq), 35 mg of aluminum chloride (0.26 mmol, 0.05 eq), 34 mg of triphenylphosphine (0.13 mmol, 0.025 eq), 21.8 mg of sodium bicarbonate (0.26 mmol, 0.05 eq) and 15 mL of nitromethane were added to a reaction vessel. Under nitrogen protection, the temperature was raised to 80° C. for reaction for 2 h, then the temperature was lowered to 35° C., and the mixture was concentrated to dryness under reduced pressure. After chromatography on an n-heptane column, 0.758 g of compound 2a was obtained with a yield of 82.7%.

[0060] <Example 2>

[0061] Selection of the dosage of triphenylphosphine and sodium bicarbonate

[0062] In this example, on the basis of Example 1, the amounts of triphenylphosphine and sodium bicarbonate were screened. Except for the parameters listed in the following table, the remaining steps were the same as those described in Example 1.

[0063] Table 1 Screening of triphenylphosphine and sodium bicarbonate dosage

[0064] Serial number Triphenylphosphine dosage (eq) Sodium bicarbonate dosage (eq) Yield (%) 1 0.05 0.025 79.7 2 0.05 0.05 78.5 3 0.05 0.10 79.0

[0065] It can be seen from the above table and the contents recorded in Example 1 that when the amount of aluminum chloride is maintained at 0.05 eq, the ratio of the sum of the molar amounts of triphenylphosphine and sodium bicarbonate to the molar amount of aluminum chloride is (1.5-3.0):1 and the molar ratio of triphenylphosphine to sodium bicarbonate is (1-2):(1-2) when both can achieve good yields, and only trace amounts of de-tert-butylated impurities (4-vinylphenol) are observed.

[0066] <Comparative Example 1>

[0067] A kind of preparation method of tert-butoxystyrene

[0068] This comparative example provides a method for preparing p-tert-butoxystyrene, and the reaction formula is as follows:

[0069]

[0070] The steps include:

[0071] 1 g of compound 1a (5.2 mmol, 1.0 eq), aluminum chloride, triphenylphosphine and 15 mL of nitromethane were added to a reaction vessel. Under nitrogen protection, the temperature was raised to 80° C. for reaction for 2 h, then the temperature was lowered to 35° C., concentrated to dryness under reduced pressure, and subjected to n-heptane column chromatography to obtain compound 2a and compound 3a, respectively.

[0072] This comparative example screened the dosage of aluminum trichloride and triphenylphosphine, and the screening results are shown in Table 2.

[0073] Table 2 Screening of aluminum chloride and triphenylphosphine dosage

[0074]

[0075] a. This reaction also produced an unknown impurity in a yield of 22.9%.

[0076] As can be seen from the above table, without using an additional Lewis base, the reaction will generate at least two or more products, which will result in the inability to obtain the target product in high yield, and will also cause certain difficulties in the purification and separation of the product. In addition, the applicant also found that when the amount of aluminum chloride is less than 0.05eq, the reaction is difficult to proceed smoothly.

[0077] <Example 3>

[0078] Screening of Lewis bases

[0079] This example uses the following experimental steps to screen Lewis bases, and the reaction formula is as follows:

[0080]

[0081] The steps include:

[0082] 1 g of compound 1a (5.2 mmol, 1.0 eq), 35 mg of aluminum chloride (0.26 mmol, 0.05 eq), 34 mg of triphenylphosphine (0.13 mmol, 0.025 eq), a Lewis base (0.26 mmol, 0.05 eq) and 15 mL of acetonitrile were added to a reaction vessel. Under nitrogen protection, the temperature was raised to 80 ° C. for reaction for 2 h, then the temperature was lowered to 35 ° C., concentrated to dryness under reduced pressure, and chromatographed on an n-heptane column to obtain the target product compound 2a.

[0083] The screening results are shown in Table 3.

[0084] Table 3 Screening of Lewis bases

[0085] Serial number Lewis base Yield of compound 2a 1 Triethylamine 68.4％ 2 Pyridine 78.5％ 3 Sodium carbonate 77.3％ 4 Sodium acetate 82.6％ 5 Trimethylsilyl trifluoromethanesulfonate No response 6 Sodium phosphate 79.7％

[0086] When a Lewis base other than trimethylsilyl trifluoromethanesulfonate is used in the reaction system, the formation of 4-vinylphenol can be effectively suppressed, thereby obtaining the target product compound 2a with a higher yield.

[0087] <Example 4>

[0088] Screening of reaction solvents

[0089] This embodiment uses the following method to screen the reaction solvent, and the reaction formula is as follows:

[0090]

[0091] The steps include:

[0092] 1 g of compound 1a (5.2 mmol, 1.0 eq), 35 mg of aluminum chloride (0.26 mmol, 0.05 eq), 34 mg of triphenylphosphine (0.13 mmol, 0.025 eq), 21.3 mg of sodium acetate (0.26 mmol, 0.05 eq) and 15 mL of solvent were added to a reaction vessel. Under nitrogen protection, the temperature was raised to 80° C. for reaction for 2 h, then the temperature was lowered to 35° C., concentrated to dryness under reduced pressure, and chromatographed on a n-heptane column to obtain the target product, compound 2a.

[0093] The screening results are shown in Table 4.

[0094] Table 4 Screening of solvents

[0095] Serial number Solvents Yield of compound 2a 1 Acetonitrile 82.6％ 2 Toluene 1.5％ 3 Nitromethane 82.3％ 4 Isopropyl acetate 1.2％

[0096] It can be seen from the above table that acetonitrile and nitromethane are more suitable for the reaction system provided in this application.

[0097] <Example 5>

[0098] Amplification reaction

[0099] This embodiment carries out the following reaction, and the reaction formula is as follows:

[0100]

[0101] The steps include:

[0102] 151.87 g of compound 1a (0.782 mol, 1.0 eq), 5.21 g of aluminum chloride (39.1 mmol, 0.05 eq), 10.26 g of triphenylphosphine (39.1 mmol, 0.05 eq), 3.21 g of sodium acetate (39.1 mmol, 0.05 eq) and 2.28 L of acetonitrile were added to a 5 L reaction bottle, heated to 80 ° C under nitrogen protection, reacted for 2 h, cooled to 35 ° C and concentrated to dryness under reduced pressure, and chromatographed on an n-heptane column to obtain 111.4 g of compound 2a with a yield of 80.8% and a product purity of 99.8%.

[0103] The liquid phase spectrum of the product is as follows Figure 1 shown.

[0104] Product 1 HNMR spectrum Figure 2 shown.

[0105] <Example 6>

[0106] Preparation of compound 2a

[0107] This example provides a method for preparing compound 2a from compound 1g, and the reaction formula is as follows:

[0108]

[0109] 1 g of compound 1g (5.2 mmol, 1.0 eq), 35 mg of aluminum chloride (0.26 mmol, 0.05 eq), 34 mg of triphenylphosphine (0.13 mmol, 0.025 eq), 21.3 mg of sodium acetate (0.26 mmol, 0.05 eq) and 15 mL of acetonitrile were added to a reaction vessel. Under nitrogen protection, the temperature was raised to 80°C for reaction for 2 h, then the temperature was lowered to 35°C, and the mixture was concentrated to dryness under reduced pressure. After chromatography on an n-heptane column, 745 mg of compound 2a was obtained with a yield of 81.3%.

[0110] <Comparative Example 2>

[0111] This comparative example used the following method to screen the reaction solvent, and the reaction formula is as follows:

[0112]

[0113] The steps include:

[0114] 1 g of compound 1a (5.2 mmol, 1.0 eq), 0.05 eq of Lewis acid, 0.025 eq of triphenylphosphine, 21.3 mg of sodium acetate (0.26 mmol, 0.05 eq) and 15 mL of nitromethane were added to a reaction vessel. Under nitrogen protection, the temperature was raised to 80 ° C for reaction for 2 h, then the temperature was lowered to 35 ° C. The reaction solution was detected by HPLC, and the liquid phase yield was calculated.

[0115] The screening results are shown in Table 5.

[0116] Table 5 Screening of Lewis acids

[0117] Serial number Lewis acid Liquid phase yield 1 Titanium Tetrachloride NR 2 Tin tetrachloride 18％ 3 Boron trichloride 59.5％

[0118] As shown in the table above, the reaction yield is not high when other Lewis acids are used except aluminum chloride.

[0119] Functions and Effects of the Embodiments

[0120] According to the preparation method of the phenylene compound involved in the above embodiment, because an additional Lewis base, especially sodium bicarbonate or sodium acetate, is added in the reaction, the present application can reduce the generation of additional impurities and thus improve the yield of the target product.

[0121] According to the preparation method of the phenylene compound involved in the above embodiment, since acetonitrile or nitromethane is used as the reaction solvent, the present application can obtain a better product yield.

[0122] The applicant declares that the present invention illustrates the preparation method of the phenylene compound of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0123] The above embodiments are preferred cases of the present invention and are not intended to limit the protection scope of the present invention. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, and these simple modifications all belong to the protection scope of the present invention.

[0124] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A method for preparing a phenylene compound, characterized in that: The reaction formula is as follows: Compound 1 is any one of the following compounds: The preparation method comprises the following steps: Compound 1, aluminum chloride, triphenylphosphine, a Lewis base and a solvent are mixed and reacted, and then post-treated to obtain compound 2; Wherein, the Lewis base is selected from any one or more of sodium acetate, potassium acetate, sodium phosphate, potassium phosphate, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, pyridine, and triethylamine; The solvent is selected from any one or both of acetonitrile and nitromethane.

2. The method for preparing a phenylene compound according to claim 1, characterized in that: The Lewis base is selected from any one of sodium acetate, potassium acetate, sodium bicarbonate or potassium bicarbonate.

3. The method for preparing a phenylene compound according to claim 1, characterized in that: The molar ratio of the compound 1 to triphenylphosphine is 1:(0.05-0.10).

4. The method for preparing a phenylene compound according to claim 1, wherein: The ratio of the sum of the molar amounts of the triphenylphosphine and the Lewis base to the molar amount of aluminum chloride is (1.5-3.0):

1.

5. The method for preparing a phenylene compound according to claim 4, characterized in that: The molar ratio of the triphenylphosphine to the Lewis base is (1-2): (1-2).

6. The method for preparing a phenylene compound according to claim 1, characterized in that: The mass volume ratio of the compound 1 to the solvent is 1 g: (10-15) mL.

7. The method for preparing a phenylene compound according to claim 1, characterized in that: The reaction temperature is 70°C-90°C; and / or, the reaction is carried out under the protection of an inert gas; And / or, the post-treatment step includes cooling, concentrating to dryness, and column chromatography.

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