CN112574010B

CN112574010B - Preparation method of triphenylene derivative

Info

Publication number: CN112574010B
Application number: CN202011324725.8A
Authority: CN
Inventors: 李桂云; 曾原; 姚腾飞; 陈学宇; 何立; 袁云龙
Original assignee: Shanghai Wanshou Pharmaceutical Co ltd; Shanghai Kangpeng Science And Technology Co ltd
Current assignee: Shanghai Wanshou Pharmaceutical Co ltd; Shanghai Kangpeng Science And Technology Co ltd
Priority date: 2020-11-23
Filing date: 2020-11-23
Publication date: 2022-11-29
Anticipated expiration: 2040-11-23
Also published as: CN112574010A

Abstract

The invention relates to the field of organic chemistry, in particular to a preparation method of triphenylene derivatives. The invention provides a preparation method of a triphenylene derivative, which comprises the following steps: the compound of formula 4 is subjected to a ring closure reaction in the presence of an acid, an initiator and an oxidizing agent to provide the compound of formula 5. According to the preparation method of the triphenylene derivative, the acid and the oxidant are used for carrying out the arylation reaction, so that the side reaction generated in the reaction is less, the conversion rate of the whole reaction is high, the raw materials are economical and practical, in addition, the whole reaction route has high reaction yield, the industrial production and operation are convenient, and the industrial prospect is good.

Description

Preparation method of triphenylene derivative

Technical Field

The invention relates to the field of organic chemistry, in particular to a preparation method of triphenylene derivatives.

Background

Triphenylene derivatives are important raw materials of novel organic light-emitting semiconductor materials, and are important raw materials capable of self-luminescence in OLEDs. In the existing literature reports, the compound has the advantages of longer synthetic route, difficult preparation of raw materials, more reaction impurities, difficult quality control and low overall yield. Particularly in the aromatization step, the yield is generally low, the conversion rate is low, side reactions are complicated, and the purification is difficult, so that the overall synthesis cost is high.

The existing data mainly comprise the following routes for synthesizing the compounds:

route one (US 20100072887, PCT int.appl.,2013085243, PCT int.appl., 2012002221):

the method takes triphenylene as a raw material, uses bromine or NBS and the like for bromination, has more reaction sites, obvious dibromination and polybromination impurities, and is difficult to crystallize and purify due to the fact that the impurities are close to the physical properties of the product. The conversion rate of the reaction is not high, and the overall yield is poor. And thus are difficult to be applied to industrial applications.

Route two (CN 110041165):

the method has the advantages that the initial raw materials are not easy to obtain and are expensive, the yield of ring closure through diazotization is general, meanwhile, a large amount of waste acid water is generated through reaction, the method is not environment-friendly, and the method is not suitable for industrial production.

Route three (CN 105503518):

the method needs to prepare the 2-biphenyl pinacol boric acid ester, needs to use a noble metal catalyst and has higher cost; meanwhile, the cost of the raw material p-bromoiodobenzene is obviously higher than that of p-dibromobenzene, so that the cost of the raw material of the scheme is higher; meanwhile, the efficiency of the scholl reaction carried out by using an iron chloride system is low, and the yield in literature reports can only reach about 40-50% generally; therefore, it is not an ideal industrial production method.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a method for preparing triphenylene derivatives, which solves the problems of the prior art.

To achieve the above and other related objects, the present invention provides a method for preparing triphenylene derivatives, comprising: subjecting the compound of formula 4 to a ring closure reaction in the presence of an acid, an initiator and an oxidizing agent to provide a compound of formula 5, the reaction equation being as follows:

wherein R is selected from Cl, br and OR ', and R' is selected from H, C1-C5 alkyl and benzyl.

In some embodiments of the invention, the oxidizing agent is selected from the group consisting of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, 2,3,5, 6-tetrachloro-1, 4-benzoquinone, and o-tetrachlorobenzoquinone;

and/or, in the ring closing reaction, the molar ratio of the compound of formula 4 to the oxidant is 1:1 to 3, preferably 1 to 2, more preferably 1.1 to 1.5;

and/or, in the ring closing reaction, the acid is selected from one or more of methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid and sulfuric acid;

and/or, in the ring closing reaction, the molar ratio of the compound of formula 4 to the acid is 1:1 to 5, preferably 1;

and/or, in the ring closing reaction, the initiator is selected from one or more of BPO and AIBN;

and/or, in the ring closing reaction, the molar ratio of the compound of the formula 4 to the initiator is 1:0.01 to 0.1, preferably 1.02 to 0.05;

and/or in the ring closing reaction, the reaction temperature is 20-120 ℃, and preferably 40-80 ℃;

and/or in the ring closing reaction, the reaction is carried out in the presence of a solvent, the reaction solvent in the ring closing reaction is selected from an aprotic solvent, preferably one or more combinations selected from halogenated alkane solvents, aromatic solvents, ether solvents and alkane solvents, and more preferably one or more combinations selected from dichloromethane, dichloroethane, chloroform, toluene, tetrahydrofuran, methyl tetrahydrofuran, n-hexane and cyclohexane;

and/or the post-treatment of the ring closure reaction comprises: removing solvent, and washing.

In some embodiments of the present invention, the method for preparing the compound of formula 4 comprises: carrying out a coupling reaction of the compound of formula 2 and the compound of formula 3 in the presence of a catalyst and a base to provide the compound of formula 4, wherein the reaction equation is as follows:

wherein X is selected from Cl and Br;

when X is Cl, R is selected from Cl, OR';

when X is Br, R is selected from Cl, br, OR'.

In some embodiments of the invention, the molar ratio of the compound of formula 2 to the compound of formula 3 is 1:1.0 to 4.0, preferably 1:1.0 to 3.0;

and/or, in the coupling reaction, the catalyst comprises a palladium catalyst selected from one or more of the group consisting of palladium ditriphenylphosphine dichloride, palladium tetrariphenylphosphine, 1' -bis (diphenylphosphino) ferrocene palladium chloride, palladium ditricyclohexylphosphine palladium chloride, palladium ditertiary butylphosphine palladium chloride, palladium chloride-Sphos, palladium acetate-Sphos, palladium chloride-Xphos, palladium acetate-Xphos, palladium on carbon;

and/or, in the coupling reaction, the catalyst comprises a phase transfer catalyst selected from one or more of tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, and trimethylbenzylammonium chloride;

and/or, in the coupling reaction, the base is selected from inorganic bases, preferably from one or more of alkali metal carbonate, alkali metal phosphate and alkali metal hydroxide, and more preferably from one or more of potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, potassium hydroxide and sodium hydroxide;

and/or, in the coupling reaction, the molar ratio of the compound of formula 2 to the base is 1:1.2 to 3.0, preferably 1.2 to 2.0;

and/or in the coupling reaction, the reaction temperature is 40-140 ℃, and preferably 60-100 ℃;

and/or in the coupling reaction, the reaction is carried out in the presence of a solvent, the reaction solvent in the coupling reaction is one or a combination of more of water, ether solvents, aromatic solvents, alkane solvents and alcohol solvents, and preferably one or a combination of water, tetrahydrofuran, methyl tert-butyl ether, toluene, cyclohexane, hexane and ethanol;

and/or, the post-treatment of the coupling reaction comprises: cooling and solid-liquid separation.

In some embodiments of the present invention, the method of preparing the compound of formula 2 comprises: providing a grignard reagent of the compound of formula 1, reacting the grignard reagent of the compound of formula 1 with a boronic ester and hydrolyzing to provide a compound of formula 2, the reaction equation is as follows:

in some embodiments of the present invention, the method of providing a grignard reagent of the compound of formula 1 specifically comprises: reacting the compound of formula 1 with magnesium metal to provide a corresponding Grignard reagent, wherein the molar ratio of magnesium metal to the compound of formula 1 is 0.9-1.3: 1, preferably 1 to 1.2:1;

and/or the reaction temperature of the reaction for preparing the Grignard reagent is 20-90 ℃.

In some embodiments of the present invention, the borate ester is selected from the group consisting of trimethyl borate, triisopropyl borate, triethyl borate, tributyl borate;

and/or, in the reaction for preparing the compound of formula 2, the molar ratio of the borate to the compound of formula 1 is 1.0-1.6: 1;

and/or in the reaction for preparing the compound shown in the formula 2, the reaction temperature is-50-60 ℃;

and/or, in the reaction for preparing the compound of formula 2, the reaction is carried out in the presence of a solvent, and the reaction solvent is selected from one or more of an ether solvent, an aromatic solvent, an alkane solvent and an alcohol solvent, preferably from one or more of tetrahydrofuran, diethyl ether, methyltetrahydrofuran, methyl tert-butyl ether, toluene, cyclohexane, hexane and xylene;

and/or, the post-treatment of the reaction to prepare the compound of formula 2 comprises: acidifying and desolventizing.

In some embodiments of the present invention, the method for preparing the compound of formula 2 comprises: preparing a compound of formula 1 as an aryl lithium, reacting the aryl lithium with a borate ester and hydrolyzing to provide a compound of formula 2, the reaction equation being as follows:

in some embodiments of the present invention, the method of preparing the compound of formula 1 as an aryl lithium specifically comprises: reacting the compound shown in the formula 1 with butyl lithium to prepare aryl lithium, wherein the molar ratio of the butyl lithium to the compound shown in the formula 1 is 0.9-1.3: 1, preferably 1 to 1.2:1;

and/or the reaction temperature for the preparation of aryl lithium is-60 to 50 ℃.

In some embodiments of the present invention, in the reaction to prepare the compound of formula 2, the borate ester is selected from a combination of one or more of trimethyl borate, triisopropyl borate, triethyl borate, tributyl borate;

and/or, in the reaction for preparing the compound of formula 2, the molar ratio of the boric acid ester to the compound of formula 1 is 1.0-1.6: 1;

and/or, the work-up of the reaction to prepare the compound of formula 2 comprises: acidifying and desolventizing.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments, and other advantages and effects of the present invention will be apparent to those skilled in the art from the disclosure of the present specification.

The inventor of the present invention has made extensive practical studies and provides a novel method for preparing a triphenylene derivative, which improves the ring formation efficiency of the oxidative ring formation by introducing a radical initiator, realizes a ring formation reaction which is difficult to be realized originally only by an oxidant, has a high overall yield of a reaction route, is easy and convenient to operate, has a low cost, and is suitable for an industrial production route, and thus the present invention has been completed.

The invention provides a preparation method of a triphenylene derivative, which comprises the following steps: subjecting the compound of formula 4 to a ring closure reaction in the presence of an acid, an initiator and an oxidizing agent to provide a compound of formula 5, the reaction equation being as follows:

wherein R is selected from Cl, br and OR ', and R' is selected from H, C1-C5 alkyl and benzyl. Since the compound of formula 4 has a problem that the reactivity is not high when it is used as a reaction substrate, it is difficult to efficiently realize the oxidation and ring closure by an oxidizing agent, which is generally used, on such a substrate. In the present invention, the initiator is introduced to excite the intermediate state of the reaction, so that the reaction can smoothly cross the reaction energy barrier, thereby smoothly completing the cyclization reaction.

In the present invention, the "alkyl group" generally refers to saturated aliphatic groups, which may be straight-chain or branched. For example, C1-C5 alkyl generally refers to an alkyl group including 1, 2,3, 4, 5 carbon atoms, which specifically may include, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, and the like.

In the above ring closure reaction, an oxidizing agent may be generally used to effect activation of the C-H bond on the aromatic ring. For example, a particularly suitable oxidizing agent may be one or a combination of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ), 2,3,5, 6-tetrachloro-1, 4-benzoquinone, o-tetrachlorobenzoquinone, and the like. The amount of the oxidizing agent to be used is usually substantially the same amount or in excess with respect to the compound of formula 4, so that the conversion rate of the reaction can be secured and the reaction can be sufficiently carried out in the forward direction. For example, the molar ratio of the compound of formula 4 to the oxidizing agent can be 1:1 to 3, 1: 1-1.1, 1: 1.1-1.2, 1: 1.2-1.3, 1: 1.3-1.5, 1:1.5 to 1.7, 1: 1.7-2, 1: 2-2.5, or 1:2.5 to 3, preferably 1:1 to 2, more preferably 1:1.1 to 1.5.

In the above-mentioned ring-closing reaction, the acid used may be generally any acid suitable for the ring-closing reaction in the art. For example, the specifically applicable acid may be an organic acid, or may be an inorganic acid, and more specifically may be one or a combination of more of methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid, sulfuric acid, and the like. The amount of the acid used may be appropriately adjusted by those skilled in the art so that the conversion rate of the reaction can be ensured and the reaction can be sufficiently advanced. For example, the molar ratio of the compound of formula 4 to the acid may be 1:0.5 to 3, 1:0.5 to 0.6, 1:0.6 to 0.7, 1:0.7 to 0.8, 1:0.8 to 0.9, 1: 0.9-1, 1: 1-1.1, 1: 1.1-1.2, 1: 1.2-1.3, 1: 1.3-1.5, 1: 1.5-1.7, 1: 1.7-2, 1: 2-2.5, or 1:2.5 to 3, preferably 1:1 to 2, more preferably 1:1.1 to 1.5.

In the above-mentioned ring-closing reaction, the initiator used may be any of various initiators suitable for radical reactions in the art. For example, the initiator may be a combination of one or more of BPO, AIBN, and the like. The amount of initiator used can generally be adjusted as appropriate to the person skilled in the art, for example, the molar ratio of the compound of formula 4 to the initiator can be 1:0.01 to 0.25, 1:0.01 to 0.0.05, 1:0.05 to 0.1, 1: 0.1-0.2, 1:0.2 to 0.25, preferably 1:0.01 to 0.1, and more preferably 1.

In the above ring-closing reaction, the reaction may be carried out usually under a temperature condition of from room temperature to the boiling point of the solvent. For example, the reaction temperature in the ring-closing reaction may be 20 to 120 ℃,20 to 40 ℃, 40 to 60 ℃, 60 to 80 ℃, 80 to 100 ℃, or 100 to 120 ℃, and preferably may be 40 to 80 ℃. The reaction time can be adjusted by those skilled in the art according to the reaction progress, and for example, the reaction progress of the ring-closing reaction can be judged by TLC, chromatography, etc., and for example, the reaction time of the ring-closing reaction can be 2 to 20 hours, 2 to 4 hours, 4 to 8 hours, 8 to 12 hours, or 12 to 20 hours.

In the above-mentioned ring-closing reaction, the reaction may be carried out usually in the presence of a solvent. The reaction solvent used in the ring-closing reaction is generally selected from aprotic solvents, more specifically organic solvents, and is generally a good solvent for the reaction system, so that the reactants are sufficiently dispersed and a certain concentration is secured to allow the reaction to proceed smoothly. For example, in the ring-closing reaction, the reaction solvent may be one or a combination of more of a halogenated alkane solvent, an aromatic solvent, an ether solvent, an alkane solvent, and the like, and more specifically one or a combination of more of dichloromethane, dichloroethane, chloroform, toluene, tetrahydrofuran, methyltetrahydrofuran, n-hexane, cyclohexane, and the like. For example, in the ring-closing reaction, the mass of the reaction solvent may be 2 to 20 times, 2 to 5 times, 5 to 10 times, 10 to 15 times, or 15 to 20 times that of the reaction substrate.

In the above-mentioned ring-closing reaction, the reaction can be carried out under a gas blanket. Suitable methods of providing a gas shield will be known to those skilled in the art, for example, the conditions for providing a gas shield may be provided by inert gases such as, in particular, one or a combination of more of helium, neon, argon, krypton, xenon, and the like, and/or nitrogen.

In the above-mentioned ring-closing reaction, one skilled in the art can select a suitable post-treatment method to post-treat the product obtained by the ring-closing reaction. For example, the post-treatment of the ring-closing reaction may include: removing solvent, and washing. After the reaction is completed, an appropriate amount or all of the solvent may be distilled off, and the obtained solid generally needs to be sufficiently washed, for example, acid washing (for example, washing with a hydrochloric acid solution or the like), alkali washing (for example, washing with an aqueous NaOH solution or the like), water washing, or the like may be performed to provide the compound of formula 5. The product obtained after extensive washing may be further purified (e.g., column purification, etc.) to provide a compound of formula 5 having a higher purity.

The preparation method of the triphenylene derivative provided by the invention can also comprise the following steps: carrying out a coupling reaction of the compound of formula 2 and the compound of formula 3 in the presence of a catalyst and a base to provide the compound of formula 4, wherein the reaction equation is as follows:

wherein X is selected from Cl and Br;

when X is Cl, R is selected from Cl, OR';

when X is Br, R is selected from Cl, br, OR'.

In the above coupling reaction, the compound of formula 3 is usually used in an amount substantially equal to or in excess of the compound of formula 2, so that the conversion rate of the reaction can be ensured and the reaction can be sufficiently carried out in the forward direction. For example, the molar ratio of the compound of formula 2 to the compound of formula 3 may be 1: 1.0-4.0, 1: 1.0-1.1, 1: 1.1-1.2, 1: 1.2-1.3, 1: 1.3-1.5, 1: 1.5-2.0, 1: 2.0-2.5, 1: 2.5-3.0, 1:3.0 to 3.5, or 1:3.5 to 4.0, preferably 1:1.0 to 3.

In the above coupling reaction, the reaction is usually carried out in the presence of a catalyst, and the catalyst used may usually include a palladium catalyst. The coupling reaction to prepare the compound of formula 4 generally requires the inclusion of a suitable catalyst to enable the SUZUKI coupling reaction to react selectively with Cl. For example, the palladium catalyst may be selected from one or a combination of more of palladium bistriphenylphosphine dichloride, palladium tetrakistriphenylphosphine, 1' -bis (diphenylphosphino) ferrocene palladium chloride, palladium bistyclohexylphosphine chloride, palladium bistert-butylphosphine chloride, palladium chloride-Sphos, palladium acetate-Sphos, palladium chloride-Xphos, palladium acetate-Xphos, palladium on carbon, and the like. The amount of palladium catalyst used is typically a catalytic amount, for example, the molar ratio of the compound of formula 2 to the palladium catalyst may be 1:0.0001 to 0.05, 1: 0.0001-0.001, 1:0.001 to 0.005, 1:0.005 to 0.01, 1:0.01 to 0.03, or 1:0.03 to 0.05, preferably 1:0.001 to 0.005.

In the above coupling reaction, the reaction is usually carried out in the presence of a catalyst, and the catalyst used may usually include a phase transfer catalyst. The kind and the amount of the phase transfer catalyst suitable for the coupling reaction should be appropriately selected by those skilled in the art. For example, the phase transfer catalyst can be selected from one or a combination of more of tetrabutylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, trimethylbenzylammonium chloride, and the like. For another example, the molar ratio of the compound of formula 2 to the phase transfer catalyst can be 1:0.05 to 0.3, 1:0.05 to 0.1, 1: 0.1-0.15, 1: 0.15-0.2, 1:0.2 to 0.25, or 1:0.25 to 0.3.

In the above coupling reaction, the reaction is usually carried out in the presence of a base, which is mainly used to provide basic reaction conditions. The base in the coupling reaction may be generally selected from inorganic bases, and more specifically, may be, for example, a combination of one or more of alkali metal carbonate, alkali metal phosphate, alkali metal hydroxide, and the like, and further may be, for example, a combination of one or more of potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, potassium hydroxide, sodium hydroxide, and the like. The base is generally used in an amount that is substantially equivalent or in excess relative to the compound of formula 2. For example, the molar ratio of the compound of formula 2 to the base can be 1: 1.2-3.0, 1: 1.2-1.5, 1: 1.5-2.0, 1:2.0 to 2.5, or 1:2.5 to 3.0, and preferably 1.2 to 2.0.

In the above coupling reaction, the reaction may be carried out usually under a temperature condition of from room temperature to the boiling point of the solvent. For example, the coupling reaction may be carried out under heating, and the reaction temperature in the coupling reaction may be 40 to 140 ℃, 40 to 50 ℃, 50 to 60 ℃, 60 to 70 ℃, 70 to 80 ℃, 80 to 100 ℃, 100 to 120 ℃, or 120 to 140 ℃, preferably 60 to 100 ℃. The reaction time can be adjusted by those skilled in the art according to the progress of the reaction, and for example, the progress of the coupling reaction can be judged by TLC, chromatography, etc., and for example, the reaction time of the coupling reaction for preparing the compound of formula 4 may be 2 to 20 hours, 2 to 4 hours, 4 to 8 hours, 8 to 12 hours, or 12 to 20 hours.

In the above coupling reaction, the reaction may be carried out usually in the presence of a solvent. The reaction solvent used in the coupling reaction is usually a good solvent for the reaction system, so that the reactants are sufficiently dispersed and a certain concentration is ensured to allow the reaction to proceed smoothly. For example, in the coupling reaction, the reaction solvent may be one or a combination of water, an ether solvent, an aromatic solvent, an alkane solvent, an alcohol solvent, and the like, and more specifically, may be one or a combination of water, tetrahydrofuran, methyltetrahydrofuran, methyl t-butyl ether, toluene, cyclohexane, hexane, ethanol, and the like. For example, in the coupling reaction, the mass of the reaction solvent may be 2 to 20 times, 2 to 5 times, 5 to 10 times, 10 to 15 times, or 15 to 20 times that of the reaction substrate.

In the above coupling reaction, one skilled in the art can select a suitable post-treatment method to post-treat the product obtained from the coupling reaction. For example, post-treatment of the coupling reaction may include: cooling and solid-liquid separation. After the reaction is completed, the reaction system may be cooled to sufficiently precipitate the product, and the solid-liquid separation may be carried out to provide the compound of formula 4. The solid phase obtained by solid-liquid separation may be further purified (e.g., column purification, etc.) to provide the compound of formula 4 with higher purity.

The preparation method of the triphenylene derivative provided by the invention can also comprise the following steps: providing a grignard reagent of the compound of formula 1, reacting the grignard reagent of the compound of formula 1 with a boronic ester and hydrolyzing to provide a compound of formula 2, the reaction equation is as follows:

in the above reaction for preparing the compound of formula 2, suitable methods for providing the grignard reagent of the compound of formula 1 by the compound of formula 1 should be known to those skilled in the art. For example, a method of providing a grignard reagent of the compound of formula 1 may specifically comprise: the compound of formula 1 is reacted with metallic magnesium to provide its corresponding grignard reagent. For another example, the amount of magnesium metal used may be appropriately adjusted by those skilled in the art so as to ensure the conversion rate of the reaction and to allow the reaction to proceed in a sufficiently forward direction, and the molar ratio of magnesium metal to the compound of formula 1 may be specifically 0.9 to 1.3: 1. 0.9 to 1.0: 1. 1.0 to 1.1:1. 1.1-1.2: 1. or 1.2 to 1.3:1, preferably 1 to 1.2:1. for another example, the reaction for preparing the grignard reagent may be generally carried out under a temperature condition from room temperature to the boiling point of the solvent. For example, the reaction temperature of the reaction for preparing the Grignard reagent may be 20 to 90 ℃,20 to 30 ℃, 30 to 50 ℃, 50 to 70 ℃, or 70 to 90 ℃.

In the above reaction for preparing the compound of formula 2, one skilled in the art can select an appropriate boronic ester to react with the Grignard reagent and further hydrolyze to produce the corresponding boronic acid compound. For example, the boric acid ester used may be specifically one or a combination of more of trimethyl borate, triisopropyl borate, triethyl borate, tributyl borate, and the like. The amount of the boric acid ester to be used is usually substantially the same amount or an excess amount with respect to the compound of formula 1, so that the conversion rate of the reaction can be secured and the reaction can be sufficiently advanced in the forward direction. For example, in the reaction for preparing the compound of formula 1 via a grignard reagent, the molar ratio of the boronic ester to the compound of formula 1 may be 1.0 to 1.6:1. 1.0 to 1.1:1. 1.1-1.2: 1. 1.2-1.4: 1. or 1.4 to 1.6:1.

in the above reaction for preparing the compound of formula 2, the reaction may be generally first mixed and/or reacted at a relatively low temperature to avoid the system from being too violent. For example, the reaction temperature in the reaction for preparing the compound of formula 2 by using the Grignard reagent may be-50 to 60 ℃, -50 to-40 ℃, -40 to-30 ℃, -30 to-20 ℃, -20 to-10 ℃, -10 to 0 ℃, 0 to 10 ℃, 10 to 20 ℃,20 to 30 ℃, 30 to 40 ℃, 40 to 50 ℃, or 50 to 60 ℃. The reaction time can be adjusted by those skilled in the art according to the progress of the reaction, and for example, the progress of the reaction can be judged by TLC, chromatography, etc., and for example, the reaction time of the reaction for preparing the compound of formula 2 by the Grignard reagent can be 2 to 8 hours, 2 to 4 hours, 4 to 6 hours, or 6 to 8 hours.

In the above reaction for preparing the compound of formula 2, the reaction may be carried out in the presence of a solvent, and the reaction solvent used is usually an organic solvent, anhydrous and usually a good solvent for the reaction system, so that the reactants are sufficiently dispersed and a certain concentration is secured to allow the reaction to proceed smoothly. For example, the reaction solvent of the reaction for preparing the compound of formula 2 by the grignard reagent may be one or a combination of more of an ether solvent, an aromatic solvent, an alkane solvent, an alcohol solvent, and the like, and more specifically, may be one or a combination of more of tetrahydrofuran, diethyl ether, methyltetrahydrofuran, methyl tert-butyl ether, toluene, cyclohexane, hexane, xylene, and the like.

In the above reaction for preparing the compound of formula 2, the reaction may be carried out under a gas atmosphere. Suitable methods of providing a gas shield will be known to those skilled in the art, for example, the conditions under which a gas shield may be provided by an inert gas and/or nitrogen, the inert gas used being, in particular, a combination of one or more of helium, neon, argon, krypton, xenon, etc., for example.

In the above reaction for preparing the compound of formula 2, one skilled in the art can select a suitable post-treatment method to post-treat the product obtained from the reaction. For example, post-treatment of the reaction to prepare the compound of formula 2 may include: acidifying and desolventizing. After the reaction of the Grignard reagent and the boric acid is completed, an appropriate amount of acid (e.g., hydrochloric acid, etc.) may be added to acidify the system, for example, the pH of the reaction system may be adjusted to 1-2, 1-1.5, or 1.5-2, and the appropriate amount of solvent may be removed to provide the compound of formula 2.

The preparation method of the triphenylene derivative provided by the invention can also comprise the following steps: preparing a compound of formula 1 as an aryl lithium, reacting the aryl lithium with a borate ester and hydrolyzing to provide a compound of formula 2, the reaction equation is as follows:

in the above reaction for preparing the compound of formula 2, suitable methods for providing aryl lithium corresponding to the compound of formula 1 by the compound of formula 1 should be known to those skilled in the art. For example, the method for preparing the compound of formula 1 as aryl lithium may specifically include: aryl lithium is prepared by reacting the compound of formula 1 with butyl lithium. For another example, the amount of butyllithium used may be appropriately adjusted by those skilled in the art so as to ensure the conversion rate of the reaction and to allow the reaction to proceed in a sufficient forward direction, and the molar ratio of butyllithium to the compound of formula 1 is 0.9 to 1.3: 1. 0.9 to 1.0: 1. 1.0-1.1: 1. 1.1-1.2: 1. or 1.2 to 1.3:1, preferably 1 to 1.1:1. as another example, the reaction to prepare the aryl lithium can generally be carried out by first mixing and/or reacting at a lower temperature to avoid the system being too vigorous. For example, the reaction temperature of the reaction for producing aryl lithium may be-50 to 60 ℃, -50 to-40 ℃, -40 to-30 ℃, -30 to-20 ℃, -20 to-10 ℃, -10 to 0 ℃, 0 to 10 ℃, 10 to 20 ℃,20 to 30 ℃, 30 to 40 ℃, 40 to 50 ℃, or 50 to 60 ℃.

In the above reaction for preparing the compound of formula 2, one skilled in the art can select an appropriate borate ester to react with the aryl lithium and further hydrolyze to produce the corresponding boronic acid compound. For example, the boric acid ester used may be specifically one or a combination of more of trimethyl borate, triisopropyl borate, triethyl borate, tributyl borate, and the like. The amount of the borate ester to be used is usually substantially the same amount or in excess amount relative to the compound of formula 1, so that the conversion rate of the reaction can be ensured and the reaction can be sufficiently advanced in the forward direction. For example, in the reaction of aryl lithium to prepare the compound of formula 1, the molar ratio of borate ester to the compound of formula 1 may be 1.0 to 1.6:1. 1.0-1.1: 1. 1.1-1.2: 1. 1.2-1.4: 1. or 1.4 to 1.6:1.

in the above reaction for preparing the compound of formula 2, the reaction may be generally first mixed and/or reacted at a relatively low temperature to avoid the system from being too violent. For example, the reaction temperature in the reaction for producing the compound of formula 2 from aryl lithium may be-50 to 60 ℃, -50 to-40 ℃, -40 to-30 ℃, -30 to-20 ℃, -20 to-10 ℃, -10 to 0 ℃, 0 to 10 ℃, 10 to 20 ℃,20 to 30 ℃, 30 to 40 ℃, 40 to 50 ℃, or 50 to 60 ℃. The reaction time can be adjusted by those skilled in the art according to the progress of the reaction, and for example, the progress of the reaction can be judged by TLC, chromatography, etc., and for example, the reaction time for the preparation of the compound of formula 2 from aryl lithium can be 2 to 8 hours, 2 to 4 hours, 4 to 6 hours, or 6 to 8 hours.

In the above reaction for preparing the compound of formula 2, the reaction may be carried out in the presence of a solvent, and the reaction solvent used is usually an organic solvent, anhydrous and usually a good solvent for the reaction system, so that the reactants are sufficiently dispersed and a certain concentration is secured to allow the reaction to proceed smoothly. For example, the reaction solvent of the reaction for preparing the compound of formula 2 by aryl lithium may be one or a combination of more of ether-based solvents, aromatic-based solvents, alkane-based solvents, alcohol-based solvents, etc., and more specifically, may be one or a combination of more of tetrahydrofuran, diethyl ether, methyl tetrahydrofuran, methyl tert-butyl ether, toluene, cyclohexane, hexane, xylene, etc.

In the above reaction for preparing the compound of formula 2, one skilled in the art can select a suitable post-treatment method to post-treat the product obtained from the reaction. For example, post-treatment of the reaction to prepare the compound of formula 2 may include: acidifying and desolventizing. After the reaction of aryl lithium and boric acid is completed, an appropriate amount of acid (e.g., hydrochloric acid, etc.) may be added to acidify the system, for example, the pH of the reaction system may be adjusted to 1 to 2, 1 to 1.5, or 1.5 to 2, and the appropriate amount of solvent may be removed to provide the compound of formula 2.

According to the preparation method of the triphenylene derivative, the acid and the oxidant are used for carrying out the arylation reaction, so that the side reaction generated in the reaction is less, the conversion rate of the whole reaction is high, the raw materials are economical and practical, in addition, the whole reaction route has high reaction yield, the industrial production and operation are convenient, and the industrial prospect is good.

The invention of the present application is further illustrated by the following examples, which are not intended to limit the scope of the present application.

Example 1

Preparation of biphenyl-2-boronic acid:

28.8g (1.2 mol) of magnesium metal and one iodine are added into a 2000ml four-mouth bottle, 233g (1.0 mol) of 2-bromobiphenyl is dissolved in 1100ml THF, a constant pressure dropping funnel is added, 50ml of the mixed solution is dripped into a reaction bottle, heating is carried out to initiate the format, the temperature is controlled between 50 ℃ and 55 ℃ after initiation, the rest 2-bromobiphenyl solution is dripped, the reflux and the heat preservation are carried out for 1 hour after the dripping is finished, and the gas chromatography monitors that the raw materials are completely reacted. Reducing the temperature of the system to-40 ℃, dropwise adding 135.2g (1.3 mol) of trimethyl borate solution in 240ml of THF, controlling the temperature to be less than-25 ℃, keeping the temperature for 1 hour after dropwise adding, naturally heating to room temperature, dropwise adding hydrochloric acid to adjust the pH to be =1, layering, evaporating THF under reduced pressure, adding water for pulping, performing suction filtration, adding petroleum ether into a filter cake for pulping, drying to obtain 163g of biphenyl-2-boric acid, wherein the content of liquid chromatogram is 99.0%, and the yield is 82.5%.

Example 2

Preparation of biphenyl-2-boronic acid:

233g (1.0 mol) of 2-bromobiphenyl and 1400ml of THF are added into a 5000ml four-mouth bottle, butyl lithium solution (1.2 mol) is dripped between-50 ℃ and-65 ℃, the temperature is kept for 1 hour after the dripping is finished, and the reaction of the raw materials is monitored by gas chromatography. 244.5g (1.3 mol) triisopropyl borate is dripped at the temperature of minus 50 ℃, the temperature is controlled to be less than minus 5 ℃, the temperature is kept for 1 hour after dripping, then the temperature is naturally raised to the room temperature, hydrochloric acid is dripped to adjust the PH to be =1, layering is carried out, THF is evaporated under reduced pressure, water is added for pulping, suction filtration is carried out, toluene is added for pulping into a filter cake, 169g of biphenyl-2-boric acid is obtained after drying, the content of a liquid chromatogram is 99.3 percent, and the yield is 85.5 percent.

Example 3

Preparation of 4-bromo-1, 1':2',1 ″ -terphenyl:

a2000 ml reaction flask was charged with 283g (1.2 mol) of p-dibromobenzene, 276g (2.0 mol) of potassium carbonate, 25g of tetraethylammonium bromide, 100g of toluene, and 800g of water, heated to 100 ℃ and charged with 1g of palladium bis (triphenylphosphine) dichloride, and 198g (1.0 mol) of biphenyl-2-boronic acid was added in portions, and the completion of the reaction of the starting materials was monitored by liquid chromatography. Cooling to 5 ℃, filtering, drying a filter cake to obtain 310g of crude product, dissolving the crude product by using petroleum ether, passing silica gel through a column, and concentrating and drying under reduced pressure to obtain 4-bromo-1, 1':2', 1' -terphenyl: 290.6g, gas phase purity: 99.2% and yield 94.0%.

Example 4

Preparation of 4-methoxy-1, 1':2', 1' -terphenyl:

a2000 ml reaction flask was charged with 205.7g (1.1 mol) of 4-bromoanisole, 276g (2.0 mol) of potassium carbonate, 10g of tetramethylammonium chloride, 200g of THF, and 600g of water, heated to 100 ℃ and charged with 2g of palladium bistriphenylphosphine dichloride, 198g (1.0 mol) of biphenyl-2-boronic acid in portions, and completion of the reaction of the raw materials was monitored by liquid chromatography. Cooling to 0 ℃, performing suction filtration, drying a filter cake to obtain 270g of crude product, dissolving the crude product by using petroleum ether, passing the crude product through a silica gel column, and performing reduced pressure concentration to obtain 4-methoxyl-1, 1':2', 1' -terphenyl: 247.3g, gas phase purity: 99.0% and a yield of 95.0%.

Example 5

Preparation of 4-chloro-1, 1':2', 1' -terphenyl:

a2000 ml reaction flask was charged with 229.7g (1.2 mol) of 4-chlorobromobenzene, 138g (1.3 mol) of sodium carbonate, 20g of tetrabutylammonium bromide, 200g of ethanol, and 800g of water, heated to 80 ℃ and charged with 1.2g of palladium tetratriphenylphosphine, and further charged with 198g (1.0 mol) of biphenyl-2-boronic acid in portions, and the completion of the reaction of the starting materials was monitored by liquid chromatography. Cooling to 0 ℃, filtering, drying a filter cake to obtain 275g of crude product, dissolving the crude product by using petroleum ether, passing silica gel through a column, and concentrating and drying under reduced pressure to obtain 4-chloro-1, 1':2', 1' -terphenyl: 250.0g, gas phase purity: 99.3% and yield 94.5%.

Example 6

Preparation of 4-hydroxy-1, 1':2', 1' -terphenyl:

a2000 ml reaction flask was charged with 135g (1.05 mol) of 4-chlorophenol, 339g (1.6 mol) of potassium phosphate, 20g of tetrabutylammonium bromide, 200g of methanol, and 800g of water, heated to 60 ℃, added with 0.5g of palladium chloride and 0.5g of Xphos, and then added with 198g (1.0 mol) of biphenyl-2-boronic acid in portions, and the completion of the reaction of the starting materials was monitored by liquid chromatography. Cooling to 0 ℃, performing suction filtration, drying a filter cake to obtain 255g of crude product, dissolving the crude product by using toluene, passing through a silica gel column, and performing reduced pressure concentration to obtain 4-chloro-1, 1':2', 1' -terphenyl: 216.8g, purity: 99.5% and a yield of 88.0%.

Example 7

Preparation of 4-benzyloxy-1, 1':2',1 "-terphenyl:

a2000 ml reaction flask was charged with 229.6g (1.05 mol) of 4-benzyloxychlorobenzene, 66g (1.2 mol) of potassium hydroxide, 200g of xylene and 800g of water, heated to 100 ℃ and charged with 0.5g of palladium acetate and 1g of Sphos, and 198g (1.0 mol) of biphenyl-2-boronic acid was added in portions, and completion of the reaction of the starting materials was monitored by liquid chromatography. Cooling to 0 ℃, performing suction filtration, drying a filter cake to obtain 321g of crude product, dissolving the crude product by using toluene, passing the crude product through a silica gel column, and performing reduced pressure concentration to obtain 4-benzyloxy-1, 1', 2', 1' -terphenyl: 310.5g, purity: 99.1% and yield 92.3%.

Example 8

Preparation of 2-bromotriphenylene:

34.2g (0.3 mol) of trifluoroacetic acid, 68.1g (0.3 mol) of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ), 1.45g (0.006 mol) of BPO and 250ml of dichloroethane are added into a reaction bottle with nitrogen protection, a solution of 4-bromo-1, 1':2', 1' -terphenyl 61.8g (0.2 mol) dissolved in 100ml of dichloroethane is dropwise added at the temperature of less than 50 ℃, the temperature is kept for 2 hours around 50 ℃ after the addition is finished, and the reaction completion of the raw materials is monitored by liquid chromatography. The dichloroethane is evaporated under reduced pressure, the solid is sequentially pulped by 5 percent hydrochloric acid, water, 20 percent sodium hydroxide solution and water, and the crude product is obtained after the pumping drying. Then, the mixture is subjected to silica gel column chromatography to obtain 51.2g of 2-bromotriphenylene, the liquid chromatography purity is 99.2 percent, and the yield is as follows: 83.0 percent.

Example 9

Preparation of 2-Bromotriphenylene (control without initiator):

a reaction bottle with nitrogen protection is added with 34.2g (0.3 mol) of trifluoroacetic acid, 68.1g (0.3 mol) of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) and 250ml of dichloroethane, a solution of 4-bromo-1, 1':2', 1' -terphenyl 61.8g (0.2 mol) dissolved in 100ml of dichloroethane is added dropwise at the temperature of less than 50 ℃, and after the addition is finished, the temperature is kept for 12 hours at about 50 ℃, and the conversion of raw materials is only 6 percent and the raw materials cannot be pushed forward continuously by liquid chromatography monitoring.

Example 10

Preparation of 2-methoxytriphenylene:

a reaction flask protected by nitrogen is added with 20.0g (133.4 mmol) of trifluoromethanesulfonic acid, 24.6g (100 mmol) of 2,3,5, 6-tetrachloro-1, 4-benzoquinone, 1.61g (6.67 mmol) of BPO and 125ml of dichloromethane, a solution of 4-methoxy-1, 1':2', 1' -terphenyl 17.4g (66.7 mmol) dissolved in 50ml of dichloromethane is added dropwise at 40 ℃, the temperature is controlled to be not higher than 40 ℃, the temperature is kept at 40 ℃ for 2 hours after the addition is finished, and the completion of the reaction of the raw materials is monitored by liquid chromatography. And (3) evaporating dichloromethane under reduced pressure, pulping solid water, and draining to obtain a crude product. Then, the mixture is subjected to silica gel column chromatography to obtain 15.1g of 2-methoxytriphenylene, the liquid chromatography purity is 99.5 percent, and the yield is as follows: 87.8 percent.

Example 11

Preparation of 2-chlorotriphenylene:

a reaction bottle protected by nitrogen is added with concentrated sulfuric acid 6.2g (63.2 mmol), DDQ 14.4g (63.2 mmol), AIBN0.47g (2.87 mmol) and 134ml of dichloromethane, a solution of 4-chloro-1, 1':2', 1' -terphenyl 15.2g (57.4 mmol) dissolved in 53ml of dichloromethane is added dropwise at 30 ℃, the temperature is controlled to be not higher than 40 ℃, the reflux temperature is kept after the addition is finished, and the liquid chromatography monitors that the raw materials are reacted completely. And (3) evaporating dichloromethane under reduced pressure, pulping the solid water, and draining to obtain a crude product. Then the mixture is subjected to silica gel column chromatography to obtain 12.4g of 2-chlorotriene, the liquid chromatogram purity is 99.6 percent, and the yield is as follows: 82.3 percent.

Example 12

Preparation of 2-hydroxytriphenylene:

19.6g (172.2 mmol) of trifluoroacetic acid, 14.4g (63.2 mmol) of DDQ, 1.88g (11.5 mmol) of AIBN and 134ml of dichloromethane are added into a reaction bottle with nitrogen protection, a solution of 4-hydroxy-1, 1':2', 1' -terphenyl 14.1g (57.4 mmol) dissolved in 53ml of dichloromethane is added dropwise at 30 ℃, the temperature is controlled to be less than 40 ℃, the reflux temperature is kept after the addition is finished, and the liquid chromatography is used for monitoring until the raw materials are reacted completely. And (3) evaporating the dichloromethane under reduced pressure, pulping the solid by using 5% hydrochloric acid and water in sequence, and drying by pumping to obtain a crude product. Then, 11.2g of 2-hydroxytriphenylene was obtained by passing through a silica gel column, the purity of liquid chromatography was 98.6%, and the yield was: 80.3 percent.

Example 13

Preparation of 2-benzyloxytriphenylene:

a reaction flask with nitrogen protection is charged with methanesulfonic acid 16.5g (0.1718 mol), DDQ 39.0g (0.1718 mol), BPO0.277g (0.00115 mmol) and 250ml toluene, a solution of 4-benzyloxy-1, 1':2', 1' -terphenyl 38.5g (0.1145 mol) in 100ml toluene is added dropwise at 90 ℃ and the temperature is controlled to less than 100 ℃ and the mixture is kept at this temperature for 2 hours, and the end of reaction of the starting materials is monitored by liquid chromatography. And (3) evaporating toluene under reduced pressure, pulping solid water, and draining to obtain a crude product. Then, the mixture is subjected to silica gel column chromatography to obtain 32.9g of 2-benzyloxy triphenylene, the liquid chromatography purity is 99.8 percent, and the yield is as follows: 86.0 percent. H ¹ NMR(400MHz,CDCl ₃ ):δ8.90-8.94(d,1H),δ8.80-8.82(d,1H),δ8.14-8.18(m,2H),δ7.80-7.88(m,4H),δ7.34-7.52(m,5H)。

In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.

The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. A method for preparing a triphenylene derivative, comprising: subjecting the compound of formula 4 to a ring closure reaction in the presence of an acid, an initiator and an oxidant to provide a compound of formula 5, the reaction equation being as follows:

wherein R is selected from Cl, br and OR ', R' is selected from H, C1-C5 alkyl and benzyl;

in the ring closing reaction, the initiator is selected from one or more of BPO and AIBN;

in the ring closing reaction, the molar ratio of the compound of the formula 4 to the initiator is 1.02-0.05;

in the ring closing reaction, the oxidant is selected from one or more of 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, 2,3,5, 6-tetrachloro-1, 4-benzoquinone and o-tetrachlorobenzoquinone;

in the ring closing reaction, the acid is selected from one or more of methanesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid and sulfuric acid.

2. The method for preparing a triphenylene derivative according to claim 1, wherein the molar ratio of the compound of formula 4 to the oxidizing agent in the ring-closing reaction is 1:1 to 3;

and/or, in the ring closing reaction, the molar ratio of the compound of formula 4 to the acid is 1:1 to 5;

and/or in the ring closing reaction, the reaction temperature is 20-120 ℃;

and/or in the ring closing reaction, the reaction is carried out in the presence of a solvent, and the reaction solvent in the ring closing reaction is selected from aprotic solvents;

3. The method for producing a triphenylene derivative according to claim 2, wherein in the ring-closing reaction, the molar ratio of the compound of formula 4 to the oxidizing agent is 1 to 2;

and/or, in the ring closing reaction, the molar ratio of the compound of formula 4 to the acid is 1-3;

and/or in the ring closure reaction, the reaction temperature is 40-80 ℃;

and/or the reaction solvent in the ring closing reaction is selected from one or more of halogenated alkane solvents, aromatic solvents, ether solvents and alkane solvents.

4. The method for producing a triphenylene derivative according to claim 2, wherein the molar ratio of the compound of formula 4 to the oxidizing agent is 1.1 to 1.5;

and/or the molar ratio of the compound of formula 4 to the acid is 1.1 to 1.5;

and/or the reaction solvent in the ring closing reaction is selected from one or more of dichloromethane, dichloroethane, chloroform, toluene, tetrahydrofuran, methyltetrahydrofuran, n-hexane and cyclohexane.

5. The method of claim 1, wherein the compound of formula 4 is prepared by a process comprising: carrying out a coupling reaction of the compound of formula 2 and the compound of formula 3 in the presence of a catalyst and a base to provide the compound of formula 4, wherein the reaction equation is as follows:

wherein X is selected from Cl and Br;

when X is Cl, R is selected from Cl, OR';

when X is Br, R is selected from Cl, br, OR';

in the coupling reaction, the catalyst comprises a palladium catalyst.

6. The method of claim 5, wherein the molar ratio of the compound of formula 2 to the compound of formula 3 in the coupling reaction is 1:1.0 to 4.0;

and/or, the palladium catalyst is selected from one or more of palladium bistriphenylphosphine dichloride, palladium tetrakistriphenylphosphine, 1' -bis (diphenylphosphino) ferrocene palladium chloride, palladium bistrihexylphosphine chloride, palladium bistributylphosphine chloride, palladium chloride-Sphos, palladium acetate-Sphos, palladium chloride-Xphos, palladium acetate-Xphos and palladium carbon;

and/or, in the coupling reaction, the base is selected from inorganic bases;

and/or, in the coupling reaction, the molar ratio of the compound of formula 2 to the base is 1:1.2 to 3.0;

and/or in the coupling reaction, the reaction temperature is 40-140 ℃;

and/or in the coupling reaction, the reaction is carried out in the presence of a solvent, and the reaction solvent in the coupling reaction is one or more of water, an ether solvent, an aromatic solvent, an alkane solvent and an alcohol solvent;

7. The method of claim 6, wherein the molar ratio of the compound of formula 2 to the compound of formula 3 in the coupling reaction is 1:1.0 to 3.0;

and/or, in the coupling reaction, the base is selected from one or more of alkali metal carbonate, alkali metal phosphate and alkali metal hydroxide;

and/or, in the coupling reaction, the molar ratio of the compound of formula 2 to the base is 1.2-2.0;

and/or in the coupling reaction, the reaction temperature is 60-100 ℃;

and/or the reaction solvent in the coupling reaction is selected from one or the combination of water, tetrahydrofuran, methyl tert-butyl ether, toluene, cyclohexane, hexane and ethanol.

8. The method of claim 6, wherein the base is selected from the group consisting of potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate, potassium hydroxide, sodium hydroxide, and combinations thereof.

9. The method of claim 5, wherein the compound of formula 2 is prepared by a process comprising: providing a grignard reagent of the compound of formula 1, reacting the grignard reagent of the compound of formula 1 with a boronic ester and hydrolyzing to provide a compound of formula 2, the reaction equation is as follows:

10. the method of claim 9, wherein the step of providing the grignard reagent of the compound of formula 1 comprises: reacting the compound of formula 1 with magnesium metal to provide a corresponding grignard reagent, wherein the molar ratio of magnesium metal to the compound of formula 1 is 0.9-1.3: 1;

11. The method of claim 10, wherein the molar ratio of magnesium metal to the compound of formula 1 is 1 to 1.2:1.

12. the method of claim 9, wherein the reaction to prepare the compound of formula 2 comprises a reaction in which the borate is selected from the group consisting of trimethyl borate, triisopropyl borate, triethyl borate, and tributyl borate;

and/or in the reaction for preparing the compound shown in the formula 2, the reaction is carried out in the presence of a solvent, and the reaction solvent is one or more of an ether solvent, an aromatic solvent, an alkane solvent and an alcohol solvent;

13. The method of claim 12, wherein the compound of formula 2 is prepared in a reaction solvent selected from the group consisting of tetrahydrofuran, diethyl ether, methyltetrahydrofuran, methyl tert-butyl ether, toluene, cyclohexane, hexane, and xylene.

14. The method of claim 5, wherein the compound of formula 2 is prepared by a process comprising: preparing a compound of formula 1 as an aryl lithium, reacting the aryl lithium with a borate ester and hydrolyzing to provide a compound of formula 2, the reaction equation is as follows:

15. the method of claim 14, wherein the step of preparing the compound of formula 1 as aryl lithium comprises: reacting the compound shown in the formula 1 with butyl lithium to prepare aryl lithium, wherein the molar ratio of the butyl lithium to the compound shown in the formula 1 is 0.9-1.3: 1;

and/or the reaction temperature of the reaction for preparing the aryl lithium is-60-50 ℃.

16. The method of claim 15, wherein the molar ratio of butyllithium to the compound of formula 1 is 1 to 1.2:1.

17. the method of claim 14, wherein the reaction to prepare the compound of formula 2 comprises a reaction in which the borate is selected from the group consisting of trimethyl borate, triisopropyl borate, triethyl borate, and tributyl borate;

18. The method of claim 17, wherein the compound of formula 2 is prepared by a reaction in a solvent selected from the group consisting of tetrahydrofuran, diethyl ether, methyltetrahydrofuran, methyl tert-butyl ether, toluene, cyclohexane, hexane, and xylene.