阅读说明：本技术 基于钯催化的分子内关环反应构造荧蒽及其衍生物的新方法 (Novel method for constructing fluoranthene and derivatives thereof based on palladium-catalyzed intramolecular cyclization reaction ) 是由 危岩 胡仁健 于 2021-10-11 设计创作，主要内容包括：本发明公开了基于钯催化的分子内关环反应构造荧蒽及其衍生物的新方法。该方法包括：(1)使式I所示化合物与式II所示化合物发生偶联反应,得到式III所示化合物；(2)使式III所示化合物发生分子内关环反应,得到式IV所示化合物；其中,X为卤素原子,Ar为取代或未取代的芳基。该方法以萘的1号、8号位卤素取代物为底物,与芳基硼酸经两步反应合成荧蒽及其衍生物,底物获取简单、适用范围宽,且容易调控荧蒽衍生物的7号、8号、9号、10号取代位,为最终的目标分子结构提供了广泛的可能性。(The invention discloses a novel method for constructing fluoranthene and derivatives thereof based on palladium-catalyzed intramolecular cyclization reaction. The methodThe method comprises the following steps: (1) carrying out coupling reaction on a compound shown as a formula I and a compound shown as a formula II to obtain a compound shown as a formula III; (2) carrying out intramolecular ring closure reaction on the compound shown in the formula III to obtain a compound shown in a formula IV;)

1. A method for producing fluoranthene and derivatives thereof, characterized by comprising:

(1) carrying out coupling reaction on a compound shown as a formula I and a compound shown as a formula II to obtain a compound shown as a formula III;

(2) carrying out intramolecular ring closure reaction on the compound shown in the formula III to obtain a compound shown in a formula IV;

wherein X is a halogen atom, and Ar is a substituted or unsubstituted aryl group.

2. A method of preparing fluoranthene and its derivatives according to claim 1, characterized in that X is Cl or Br and Ar is a substituted or unsubstituted C4-C16 aryl group.

3. Method according to claim 2, wherein the C4-C16 aryl is phenyl, naphthyl, anthracenyl, phenanthrenyl, furanyl, pyranyl, pyrrolyl, pyridinyl or thienyl.

4. Method for preparing fluoranthene and its derivatives according to claim 2, characterized in that the C4-C16 aryl groups are optionally substituted by at least one of C1-C4 alkyl groups, C1-C4 alkoxy groups, halogen atoms.

5. The method according to any one of claims 1 to 4, wherein the coupling reaction is carried out in a first solvent selected from at least one of toluene, water, tetrahydrofuran, ethanol, benzene, acetonitrile, 1, 4-dioxane.

6. The method according to any one of claims 1 to 4, wherein the molar ratio of the compound represented by the formula I to the compound represented by the formula II in the coupling reaction is 1 (1.05 to 1.2);

optionally, the coupling reaction is carried out in the presence of a first palladium catalyst selected from the group consisting of Pd (PPh)₃)₄、Pd(dppf)Cl₂、Pd(OAc)₂、Pd(PPh₃)₂Cl₂At least one of;

optionally, the coupling reaction is carried out in the presence of a first additive selected from at least one of tetrabutylammonium bromide, potassium carbonate, sodium carbonate, potassium phosphate, cesium fluoride, sodium tert-butoxide;

optionally, the addition amount of the tetrabutylammonium bromide is 8 mol% to 12 mol%;

optionally, the addition amount of the potassium carbonate is 225 mol% to 275 mol%.

7. The method according to any one of claims 1 to 4, wherein the coupling reaction is carried out at 80 ℃ to 100 ℃ for 45h to 50 h.

8. The method according to any one of claims 1 to 4, wherein the intramolecular ring closure reaction is carried out in a second solvent selected from at least one of dimethyl sulfoxide, 1, 4-dioxane, acetonitrile, tetrahydrofuran, and isopropanol.

9. The process according to any one of claims 1 to 4, wherein the intramolecular ring closure reaction is carried out in the presence of a second palladium catalyst selected from Pd (dppf) Cl₂、Pd(PPh₃)₄、Pd(OAc)₂、Pd(PPh₃)₂Cl₂At least one of;

optionally, the intramolecular ring closure reaction is carried out in the presence of a second additive selected from at least one of bis (pinacolato) diboron, potassium acetate, potassium carbonate, sodium carbonate, potassium phosphate, cesium fluoride, sodium tert-butoxide;

optionally, the addition amount of the bis (pinacolato) diboron is 100 mol% to 120 mol%;

optionally, the addition amount of the potassium acetate is 280-320 mol%.

10. The method according to any one of claims 1 to 4, wherein the intramolecular ring closure reaction is carried out at 80 ℃ to 100 ℃ for 10h to 14 h.

Technical Field

The invention relates to the field of synthetic chemistry, in particular to a novel method for constructing fluoranthene and derivatives thereof based on palladium-catalyzed intramolecular cyclization reaction.

Background

Fluoranthene and derivatives thereof (substituted fluoranthene) are organic small molecules with simple molecular systems and definite structures, and are widely applied to the emerging research fields of OLED light-emitting layers, dye-sensitized solar cell construction, fluorescent chemical sensors, living cell imaging, electrochemiluminescence and the like. The discovery of fluoranthene can be traced back to the 19 th century, chemists determine the molecular structure of fluoranthene in the 20 th century, and the current main means for industrially producing the unsubstituted fluoranthene is to extract and purify the coal tar from high-boiling-point components. Research on the synthesis methodology of fluoranthene derivatives can be traced back to the fifth and sixty years of the twentieth century, c.f.h.allen and j.a.vanallan adopt Knoevenagel reaction to firstly condense acenaphthenequinone and beta-substituted carbonyl compounds to obtain structural units of (substituted) acenaphthocyclopentadienone, and then obtain fluoranthene derivatives through Diels-Alder reaction and subsequent retro-Diels-Alder or oxidative dehydrogenation reaction. In 1992, Joseph E.Rice and Zhen-Wei Cai developed an intramolecular coupling reaction of 1-phenylnaphthalene-based trifluoromethanesulfonate derivatives, which was capable of yielding a series of fluoranthene derivatives at 140 ℃ under the catalysis of bis-triphenylphosphine palladium dichloride. In 2003, Armin de Meijere et al reported a novel method for constructing a fluoranthene derivative based on a series Suzuki-Heck reaction, and the basic idea is to introduce bromine atoms into 1-position or 3-position of a benzene ring of 1-phenylnaphthalene, and then realize intramolecular cyclization through Heck type reaction so as to realize the construction of a fluoranthene molecular skeleton. Peter Langer et al developed a new method for synthesizing 8, 9-disubstituted fluoranthene structures in 2011, which achieved satisfactory yields and substrate applicability based on a Heck/electrocyclization/dehydrogenation tandem reaction strategy. In 2014, a new strategy for constructing fluoranthene derivatives by ruthenium-catalyzed [4+2] cycloaddition of acenaphthylene glycol and diene and then further dehydration is reported by a Michael J.Krische task group, so that a tool library for synthesizing fluoranthene structures is further enriched.

Overall, the above methodologies can be largely divided into the following categories:

(1) the method has the advantages that raw materials are cheap and easy to obtain, the yield is relatively high, functionalization of fluoranthene No. 7 and No. 10 can be realized through condensation reaction, functionalization of No. 8 and No. 9 can be realized through selection of Diels-Alder reaction substrates, and substitution of No. 3 and No. 4 can be realized through pre-modification of the substrate acenaphthenequinone. The defect is mainly embodied in that the synthesis of 8-position, 9-position short alkyl chain substituted or halogen substituted fluoranthene structure is incapable; for the 7-position, the 10-position halogen substituted fluoranthene derivative synthesis can not be realized; there are difficulties in synthesizing aryl [ k ] fluoranthene structures based on this strategy. In addition, the synthesis of carbonyl compounds with different beta substituents is not easy, and dimethyl benzene solvents commonly used in the subsequent Diels-Alder cycloaddition reaction have high toxicity and certain risks.

(2) The substituted 1-phenylnaphthalene ring-closing coupling type method is effective for synthesis of an aryl fluoranthene structure, however, synthesis of the substituted or brominated 1-phenylnaphthalene through triflate is subjected to more complicated steps, so that the applicability of the substrate of the method is quite limited. In the final catalytic ring closing reaction, it is also a great limitation to adopt severer reaction conditions (high temperature above 100 ℃) and use noble metal catalysts.

(3) Methodologies based on other acenaphthene derivatives have the advantage of wider substrate applicability and are extremely important and abundant for fluoranthene derivative synthesis methodologies, but these reaction systems all use very expensive catalysts, and their application is temporarily limited to laboratory-scale preparation, and further condition optimization and catalyst development are needed to achieve large-scale production.

In summary, the existing methods for preparing fluoranthene and its derivatives still need to be improved.

Disclosure of Invention

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the present invention to propose a novel method for the construction of fluoranthene and its derivatives based on a palladium-catalyzed intramolecular cyclization reaction. According to the method, the No. 1 and No. 8 halogen substitutes of naphthalene are used as substrates, and the fluoranthene derivatives are synthesized through two-step reaction with aryl boric acid, the substrates are easy to obtain, the application range is wide, the No. 7, No. 8, No. 9 and No. 10 substitution positions of the fluoranthene derivatives are easy to regulate and control, and wide possibility is provided for the final target molecular structure.

In one aspect of the present invention, the present invention provides a method for producing fluoranthene and a derivative thereof, characterized by comprising:

(1) carrying out coupling reaction on a compound shown as a formula I and a compound shown as a formula II to obtain a compound shown as a formula III;

(2) carrying out intramolecular ring closure reaction on the compound shown in the formula III to obtain a compound shown in a formula IV;

wherein X is a halogen atom, and Ar is a substituted or unsubstituted aryl group.

According to the method for preparing fluoranthene and the derivatives thereof in the above embodiment of the invention, firstly, halogen substitutes at the 1 st and 8 th positions of naphthalene (compound shown in formula I) are coupled with aryl boric acid (compound shown in formula II) to obtain aryl substitutes of naphthalene (compound shown in formula III). Wherein, Ar of the compound species shown in the formula II is substituted or unsubstituted aryl, and substituents at positions 7, 8,9 and 10 in the prepared fluoranthene and the derivatives thereof can be regulated and controlled by regulating and controlling the substituents in the aryl (it can be understood that when Ar is unsubstituted phenyl, the prepared product is fluoranthene, and when Ar is substituted phenyl and substituted or unsubstituted other aryl, the prepared product is fluoranthene derivatives), so that wide possibility is provided for the final target molecular structure. In the method provided by the invention, the reaction substrates are cheap and easy to obtain, the application range is wide, the related reaction conditions are mild, and the large-scale preparation is easy.

In addition, the method for preparing fluoranthene and derivatives thereof according to the above embodiment of the present invention may also have the following additional technical features:

in some embodiments of the invention, X is Cl or Br and Ar is a substituted or unsubstituted C4-C16 aryl group.

In some embodiments of the invention, the C4-C16 aryl is phenyl, naphthyl, anthracenyl, phenanthrenyl, furyl, pyranyl, pyrrolyl, pyridyl, or thienyl.

In some embodiments of the present invention, the C4-C16 aryl group is optionally substituted with at least one of a C1-C4 alkyl group, a C1-C4 alkoxy group, and a halogen atom.

In some embodiments of the invention, the coupling reaction is carried out in a first solvent selected from at least one of toluene, water, tetrahydrofuran, ethanol, benzene, acetonitrile, 1, 4-dioxane.

In some embodiments of the present invention, in the coupling reaction, the molar ratio of the compound represented by formula I to the compound represented by formula II is 1 (1.05-1.2).

In some embodiments of the invention, the coupling reaction is carried out in the presence of a first palladium catalyst selected from Pd (PPh)₃)₄、Pd(dppf)Cl₂、Pd(OAc)₂、Pd(PPh₃)₂Cl₂At least one of (a).

In some embodiments of the invention, the coupling reaction is carried out in the presence of a first additive selected from at least one of tetrabutylammonium bromide, potassium carbonate, sodium carbonate, potassium phosphate, cesium fluoride, sodium tert-butoxide.

In some embodiments of the present invention, the tetrabutylammonium bromide is added in an amount of 8 mol% to 12 mol%;

in some embodiments of the invention, the potassium carbonate is added in an amount of 225 mol% to 275 mol%.

In some embodiments of the invention, the coupling reaction is carried out at 80 ℃ to 100 ℃ for 45h to 50 h.

In some embodiments of the invention, the intramolecular ring closure reaction is carried out in a second solvent selected from at least one of dimethyl sulfoxide, 1, 4-dioxane, acetonitrile, tetrahydrofuran, isopropanol.

In some embodiments of the invention, the intramolecular ring closure reaction is carried out in the presence of a second palladium catalyst selected from the group consisting of pd (dppf) Cl₂、Pd(PPh₃)₄、Pd(OAc)₂、Pd(PPh₃)₂Cl₂At least one of (a).

In some embodiments of the invention, the intramolecular ring closure reaction is carried out in the presence of a second additive selected from at least one of bis (pinacolato) diboron, potassium acetate, potassium carbonate, sodium carbonate, potassium phosphate, cesium fluoride, sodium tert-butoxide.

In some embodiments of the invention, the bis (pinacolato) diboron is added in an amount of from 100 mol% to 120 mol%;

in some embodiments of the invention, the potassium acetate is added in an amount of 280 mol% to 320 mol%.

In some embodiments of the invention, the intramolecular ring closure reaction is carried out at 80 ℃ to 100 ℃ for 10h to 14 h.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Detailed Description

The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.

In addition, the description of the mole percent (mol%) of a substance added in the present invention refers to the mole percent of the substance relative to the compound represented by formula I.

In one aspect of the present invention, the present invention provides a method for producing fluoranthene and a derivative thereof, characterized by comprising:

(1) carrying out coupling reaction on a compound shown as a formula I and a compound shown as a formula II to obtain a compound shown as a formula III;

(2) carrying out intramolecular ring closure reaction on the compound shown in the formula III to obtain a compound shown in a formula IV;

wherein X is a halogen atom, and Ar is a substituted or unsubstituted aryl group.

According to some embodiments of the invention, X may be Cl or Br, preferably X is Br, i.e. the compound of formula I is 1, 8-dibromonaphthalene.

According to some embodiments of the invention, Ar may be a substituted or unsubstituted C4-C16 aryl group. By regulating and controlling the selection of the substituent in Ar, the substituents at the positions of No. 7, No. 8, No. 9 and No. 10 in the prepared fluoranthene and the derivatives thereof can be regulated and controlled, thereby providing wide possibility for the final target molecular structure.

According to some embodiments of the invention, the C4-C16 aryl group may be phenyl, naphthyl, anthracenyl, phenanthrenyl, furyl, pyranyl, pyrrolyl, pyridyl or thienyl.

According to some embodiments of the present invention, the above-mentioned C4 to C16 aryl group may be optionally substituted with at least one of a C1 to C4 alkyl group, a C1 to C4 alkoxy group, and a halogen atom. Specific examples of the C1-C4 alkyl group include methyl, ethyl, propyl, butyl, specific examples of the C1-C4 alkoxy group include methoxy, ethoxy, propoxy, butoxy, and specific examples of the halogen atom include F, Cl, Br, I.

According to some embodiments of the present invention, the coupling reaction is performed in a first solvent, and the first solvent may be at least one selected from the group consisting of toluene, water, tetrahydrofuran, ethanol, benzene, acetonitrile, and 1, 4-dioxane, and is preferably a mixed solvent of toluene and water.

According to some embodiments of the present invention, in the coupling reaction, the molar ratio of the compound represented by formula I to the compound represented by formula II is 1 (1.05-1.2), and may be, for example, 1:1.05, 1:1.06, 1:1.08, 1:1.1, 1:1.15, 1:1.2, and the like, and is preferably 1: 1.1.

According to some embodiments of the invention, the coupling reaction is carried out in the presence of a first palladium catalyst, which may be selected from Pd (PPh)₃)₄、Pd(dppf)Cl₂、Pd(OAc)₂、Pd(PPh₃)₂Cl₂At least one of them, preferably Pd (PPh)₃)₄。

According to some embodiments of the present invention, the coupling reaction is performed in the presence of a first additive, which may be selected from at least one of tetrabutylammonium bromide, potassium carbonate, sodium carbonate, potassium phosphate, cesium fluoride, sodium tert-butoxide, preferably tetrabutylammonium bromide and potassium carbonate.

According to some embodiments of the present invention, tetrabutylammonium bromide may be added in an amount of 8 mol% to 12 mol%, such as 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, etc., preferably 10 mol%; if the addition amount of tetrabutylammonium bromide is too low, the reaction yield may be greatly reduced; if the amount of tetrabutylammonium bromide added is too high, a large amount of insoluble matter may be generated in the system, increasing the difficulty of post-treatment and, accordingly, increasing the reaction cost.

According to some embodiments of the invention, the potassium carbonate may be added in an amount of 225 mol% to 275 mol%, such as 225 mol%, 235 mol%, 245 mol%, 250 mol%, 255 mol%, 265 mol%, 275 mol%, and the like, preferably 250 mol%. If the addition amount of potassium carbonate is too low, the reaction yield may be greatly reduced; if the amount of potassium carbonate added is too high, a large amount of insoluble matter may be generated in the system, increasing the difficulty of post-treatment and correspondingly increasing the reaction cost.

According to some embodiments of the invention, the coupling reaction is carried out at 80 ℃ to 100 ℃ for 45h to 50 h. Specifically, the reaction temperature may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or the like, and the reaction time may be 45 hours, 46 hours, 47 hours, 48 hours, 49 hours, 50 hours or the like, preferably 48 hours at 90 ℃. If the reaction temperature is too high, thermal decomposition of the reactants may be initiated, resulting in uncontrollable safety accidents.

According to some embodiments of the invention, the coupling reaction is carried out in an inert gas atmosphere, for example, may be carried out in a nitrogen atmosphere.

According to some embodiments of the present invention, the intramolecular ring closure reaction is performed in a second solvent, which may be selected from at least one of dimethyl sulfoxide, 1, 4-dioxane, acetonitrile, tetrahydrofuran, isopropanol, preferably dimethyl sulfoxide.

According to some embodiments of the invention, the intramolecular ring closure reaction is carried out in the presence of a second palladium catalyst, which may be selected from pd (dppf) Cl₂、Pd(PPh₃)₄、Pd(OAc)₂、Pd(PPh₃)₂Cl₂At least one of (b), preferably Pd (dppf) Cl₂。

According to some embodiments of the present invention, the intramolecular ring closure reaction is carried out in the presence of a second additive, which may be at least one selected from the group consisting of bis (pinacolato) diboron, potassium acetate, potassium carbonate, sodium carbonate, potassium phosphate, cesium fluoride, sodium tert-butoxide, preferably bis (pinacolato) diboron and potassium acetate.

According to some embodiments of the present invention, the bis (pinacolato) diboron may be added in an amount of 100 mol% to 120 mol%, such as 100 mol%, 105 mol%, 110 mol%, 115 mol%, 120 mol%, etc., preferably 110 mol%. If the amount of bis (pinacolato) diboron added is too low, the reaction yield may be greatly reduced; if the amount of bis (pinacolato) diboron added is too high, the post-treatment difficulty and reaction cost may increase.

According to some embodiments of the present invention, the amount of potassium acetate added may be 280 mol% to 320 mol%, such as 280 mol%, 290 mol%, 300 mol%, 310 mol%, 320 mol%, etc., preferably 300 mol%. If the addition amount of potassium acetate is too low, the reaction yield may be greatly reduced; if the amount of potassium acetate added is too high, a large amount of insoluble matter may be generated in the system, increasing the difficulty of post-treatment and correspondingly increasing the reaction cost.

According to some embodiments of the invention, the intramolecular ring closure reaction is carried out at 80 ℃ to 100 ℃ for 10h to 14 h. Specifically, the reaction temperature may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or the like, and the reaction time may be 10 hours, 11 hours, 12 hours, 13 hours, 14 hours or the like, preferably at 90 ℃ for 12 hours. If the reaction temperature is too high, thermal decomposition of the reactants may be initiated, resulting in uncontrollable safety accidents.

According to some embodiments of the invention, the intramolecular cyclization reaction is performed in an inert gas atmosphere, for example, may be performed in a nitrogen atmosphere.

In summary, the method for preparing fluoranthene and the derivatives thereof according to the embodiment of the present invention has at least the following advantages:

(1) the substrate is convenient to obtain: the main substrates adopted by the new method developed by the people are 1, 8-dibromo naphthalene and (substituted) aryl boric acid, wherein the 1, 8-dibromo naphthalene is commercialized, cheap and easy to obtain; (substituted) arylboronic acids have a number of commercial options and the synthetic route is well established. Compared with the prior art, if the 1-phenylnaphthalene substituted by the triflate is adopted for ring closing coupling to obtain the fluoranthene derivative, firstly the 1-phenylnaphthalene substituted by the triflate can be obtained only by multi-step synthesis (commercialization is not realized), secondly, the applicable substrate range is narrow, and the fluoranthene derivative capable of being constructed is only limited to single substitution. If the bromine-substituted 1-phenylnaphthalene is adopted to carry out ring-closing coupling to obtain the fluoranthene derivative, the key substrates of the fluoranthene derivative, namely the o-dibromoarene or the o-bromoaryl boric acid, are molecules which are difficult to synthesize, so that the substrate range of the method is naturally limited.

(2) The applicable range of the substrate is wide: as described above, since various (substituted) arylboronic acids can be purchased directly or obtained rapidly by a lithium reagent, and it is verified that most substrates can be finally coupled to give a structure of substituted fluoranthene. However, in the similar prior art, it is difficult to have wide substrate applicability due to the problems mentioned above.

(3) The reaction conditions are mild: the method of the invention relates to a two-step chemical reaction process, the reaction temperature is below 100 ℃, and the used additives (tetrabutyl ammonium bromide, potassium carbonate, potassium acetate and the like) and solvents (toluene, water, dimethyl sulfoxide and the like) are low in toxicity. The prior art methods of triflate-substituted 1-phenylnaphthalene ring-closure coupling require the use of hazardous chemicals such as triflic anhydride and high temperatures of 140 ℃. In the prior art, the bromine-substituted 1-phenylnaphthalene ring-closing coupling method also needs to use high temperature of about 150 ℃.

(4) Is suitable for large-scale preparation: due to the advantages, gram-scale preparation of a series of fluoranthene derivatives can be realized based on the method, and higher yield is kept. The prior art has milligram-level yield, and has certain obstacles to practical application.

The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.

Example 1

X＝Br

Step 1: a magneton was placed in a round-bottom flask, and 1, 8-dibromonaphthalene (5.72g,20mmol), phenylboronic acid (2.68g,22mmol), anhydrous potassium carbonate (6.91g,50mmol), tetrabutylammonium bromide (665mg,2.0mmol), and tetratriphenylphosphine palladium (116mg,0.10mmol) were added in that order. The round-bottom flask was purged with nitrogen, and 80mL of toluene and 25mL of deionized water were added and the mixture was allowed to react in an oil bath at 90 ℃ for 48 hours. Then cooling to room temperature, adding a certain amount of deionized water, extracting with ethyl acetate for three times, washing the combined organic phases with brine, adding anhydrous sodium sulfate after liquid separation, drying, and distilling under reduced pressure to obtain a crude product S1. Further purification using column chromatography gave intermediate S1.

Step 2: in thatTo a round-bottomed flask equipped with magnetons, the intermediate S1(5.66g,20mmol), bis (pinacolato) diboron (5.59g,22mmol), Pd (dppf) Cl were added in this order₂(439mg,0.6mmol), potassium acetate (5.89g,60 mmol). After nitrogen substitution, 120mL of dimethyl sulfoxide was added, and the mixture was reacted in an oil bath at 90 ℃ for 12 hours. Then cooling to room temperature, adding a certain amount of deionized water, extracting with dichloromethane for three times, washing the combined organic phases with brine, adding anhydrous sodium sulfate after liquid separation, drying, and distilling under reduced pressure to obtain a crude product P1. Further purifying by column chromatography to obtain the target product P1.

And (3) characterization:

S1：

1H-NMR(400MHz,chloroform-d)δ＝7.86–7.83(m,1H),7.82(t,J＝1.6Hz,1H),7.75(dd,J＝7.4,1.1Hz,1H),7.48–7.43(m,1H),7.40(dd,J＝7.1,1.5Hz,1H),7.36(dd,J＝4.2,2.4Hz,3H),7.31(dd,J＝6.6,3.0Hz,2H),7.27–7.20(m,1H).

13C-NMR(101MHz,chloroform-d)δ＝142.99,140.53,136.22,133.90,131.36,130.37,129.76,129.05,129.01,127.57,127.08,126.19,125.46,120.30.

P1：

1H-NMR(400MHz,DMSO-d6)δ＝8.07(d,J＝6.9Hz,2H),8.00(dd,J＝5.5,3.1Hz,2H),7.91(d,J＝8.2Hz,2H),7.66(dd,J＝8.0,7.1Hz,2H),7.38(dd,J＝5.5,3.1Hz,2H).

13C-NMR(101MHz,DMSO-d6)δ＝139.24,136.68,131.95,130.11,128.79,128.31,127.37,122.42,121.30.

example 2

X＝Br

Step 1: a round-bottomed flask was charged with a magneton, followed by 1, 8-dibromonaphthalene (5.72g,20mmol), 3, 4-dimethoxyphenylboronic acid (4.00g,22mmol), anhydrous potassium carbonate (6.91g,50mmol), tetrabutylammonium bromide (665mg,2.0mmol), and tetratriphenylphosphine palladium (116mg,0.10 mmol). The round-bottom flask was purged with nitrogen, and 80mL of toluene and 25mL of deionized water were added and the mixture was allowed to react in an oil bath at 90 ℃ for 48 hours. Then cooling to room temperature, adding a certain amount of deionized water, extracting with ethyl acetate for three times, washing the combined organic phases with brine, adding anhydrous sodium sulfate after liquid separation, drying, and distilling under reduced pressure to obtain a crude product S2. Further purification using column chromatography gave intermediate S2.

Step 2: to a round-bottomed flask equipped with magnetons, the intermediate S2(6.86g,20mmol), bis (pinacolato) diboron (5.59g,22mmol), Pd (dppf) Cl were added in this order₂(439mg,0.6mmol), potassium acetate (5.89g,60 mmol). After nitrogen substitution, 120mL of dimethyl sulfoxide was added, and the mixture was reacted in an oil bath at 90 ℃ for 12 hours. Then cooling to room temperature, adding a certain amount of deionized water, extracting with dichloromethane for three times, washing the combined organic phases with brine, adding anhydrous sodium sulfate after liquid separation, drying, and distilling under reduced pressure to obtain a crude product P2. Further purifying by column chromatography to obtain the target product P2.

And (3) characterization:

S2：

1H-NMR(400MHz,DMSO-d6)δ＝8.00(dd,J＝11.5,8.2Hz,2H),7.79(d,J＝7.4Hz,1H),7.54(t,J＝7.6Hz,1H),7.45–7.40(m,1H),7.36(t,J＝7.8Hz,1H),6.94(d,J＝8.2Hz,1H),6.81(d,J＝1.8Hz,1H),6.75(dd,J＝8.1,1.9Hz,1H),3.77(s,3H),3.68(s,3H).

13C-NMR(101MHz,DMSO-D6)δ＝148.65,148.33,140.00,136.38,135.07,134.28,131.78,129.73,129.41,129.32,126.97,126.13,122.73,119.72,114.68,111.45,56.01,55.99.

P2：

1H-NMR(400MHz,DMSO-d6)δ＝7.97(d,J＝6.9Hz,2H),7.80(d,J＝8.2Hz,2H),7.68(s,2H),7.63–7.57(m,2H),3.87(s,6H).

13C-NMR(101MHz,DMSO-D6)δ＝149.67,137.29,132.29,131.96,129.75,128.65,126.36,120.42,106.71,56.40.

example 3

X＝Br

Step 1: a magneton was placed in a round-bottom flask, and 1, 8-dibromonaphthalene (5.72g,20mmol), 2-naphthylboronic acid (3.78g,22mmol), anhydrous potassium carbonate (6.91g,50mmol), tetrabutylammonium bromide (665mg,2.0mmol) and tetratriphenylphosphine palladium (116mg,0.10mmol) were added in this order. The round-bottom flask was purged with nitrogen, and 80mL of toluene and 25mL of deionized water were added and the mixture was allowed to react in an oil bath at 90 ℃ for 48 hours. Then cooling to room temperature, adding a certain amount of deionized water, extracting with ethyl acetate for three times, washing the combined organic phases with brine, adding anhydrous sodium sulfate after liquid separation, drying, and distilling under reduced pressure to obtain a crude product S3. Further purification using column chromatography gave intermediate S3.

Step 2: to a round-bottomed flask equipped with magnetons, the intermediate S3(6.66g,20mmol), bis (pinacolato) diboron (5.59g,22mmol), Pd (dppf) Cl were added in this order₂(439mg,0.6mmol), potassium acetate (5.89g,60 mmol). After nitrogen substitution, 120mL of dimethyl sulfoxide was added, and the mixture was reacted in an oil bath at 90 ℃ for 12 hours. Then cooling to room temperature, adding a certain amount of deionized water, extracting with dichloromethane for three times, washing the combined organic phases with brine, adding anhydrous sodium sulfate after liquid separation, drying, and distilling under reduced pressure to obtain a crude product P3. Further purifying by column chromatography to obtain the target product P3.

And (3) characterization:

S3：

1H-NMR(400MHz,DMSO-d6)δ＝8.10–8.03(m,2H),7.91(dt,J＝11.8,7.2Hz,3H),7.82–7.77(m,2H),7.63–7.57(m,1H),7.53–7.47(m,3H),7.44–7.37(m,2H).

13C-NMR(101MHz,DMSO-D6)δ＝140.53,139.98,136.45,134.34,133.12,132.59,132.20,129.85,129.70,129.41,129.35,128.52,128.45,128.11,127.19,127.12,126.78,126.48,126.24,119.68.

P3：

1H-NMR(400MHz,DMSO-d6)δ＝8.52(s,2H),8.17(d,J＝6.9Hz,2H),8.00(dq,J＝6.4,3.0Hz,2H),7.94(d,J＝8.2Hz,2H),7.72(dd,J＝8.0,7.1Hz,2H),7.52(dt,J＝6.2,3.3Hz,2H).

13C-NMR(101MHz,DMSO-D6)δ＝137.53,136.55,134.81,133.56,130.61,129.21,129.10,126.96,126.86,121.07,120.44.

in the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.