阅读说明：本技术 一种多取代氯乙炔基苯类化合物及其制备方法和应用 (Polysubstituted chlorine ethynylbenzene compound and preparation method and application thereof ) 是由 刘培念 李登远 陈佳燕 王安 徐力 王成鑫 于 2020-07-22 设计创作，主要内容包括：本发明提供了一种多取代氯乙炔基苯类化合物及其制备方法和应用,涉及有机合成技术领域。本发明提供的多取代氯乙炔基苯类化合物具有式I所示的结构,式I中,所述R<Sup>1</Sup>、R<Sup>2</Sup>、R<Sup>3</Sup>、R<Sup>4</Sup>和R<Sup>5</Sup>为氯乙炔基；或,R<Sup>1</Sup>、R<Sup>2</Sup>和R<Sup>3</Sup>为氯乙炔基,R<Sup>4</Sup>和R<Sup>5</Sup>独立地为氢、烷基、芳基、芳杂基或卤素基；或,R<Sup>1</Sup>、R<Sup>3</Sup>和R<Sup>4</Sup>为氯乙炔基,R<Sup>2</Sup>和R<Sup>5</Sup>独立地为氢、烷基、芳基、芳杂基或卤素基；或,R<Sup>2</Sup>和R<Sup>4</Sup>为氯乙炔基,R<Sup>1</Sup>、R<Sup>3</Sup>和R<Sup>5</Sup>独立地为氢、烷基、芳基、芳杂基或卤素基。本发明提供的多取代氯乙炔基苯类化合物稳定性好,能够用于在二维基底表面进行的脱氯反应构建得到高稳定性的二维金属有机框架材料,为进一步实现石墨炔类材料的构建奠定基础。(The invention provides a polysubstituted chlorine ethynyl benzene compound and a preparation method and application thereof, relating to the technical field of organic synthesis. The polysubstituted chlorine ethynylbenzene compound provided by the invention has a structure shown in formula I, wherein R in the formula I 1 、R 2 、R 3 、R 4 And R 5 Is a chloroethynyl group; or, R 1 、R 2 And R 3 Is chloroethynyl, R 4 And R 5 Independently hydrogen, alkyl, aryl, heteroaryl or halo; or, R 1 、R 3 And R 4 Is chloroethynyl, R 2 And R 5 Independently hydrogen, alkyl, aryl, heteroaryl or halo; or, R 2 And R 4 Is chloroethynyl, R 1 、R 3 And R 5 Independently of each otherIs hydrogen, alkyl, aryl, heteroaryl or halogen. The polysubstituted chloroethynyl benzene compound provided by the invention has good stability, can be used for dechlorination reaction on the surface of a two-dimensional substrate to construct a high-stability two-dimensional metal organic framework material, and lays a foundation for further realizing the construction of graphite alkyne materials.)

1. A polysubstituted chlorine ethynylbenzene compound has a structure shown in a formula I:

in the formula I, R is¹、R²、R³、R⁴And R⁵Is a chloroethynyl group;

or, R¹、R²And R³Is chloroethynyl, R⁴And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R¹、R³And R⁴Is chloroethynyl, R²And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R²And R⁴Is chloroethynyl, R¹、R³And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo.

2. The polysubstituted chloroethynylbenzene compound according to claim 1, characterized in that said alkyl group is methyl or ethyl; the halogen group is-F, -Cl, -Br or-I.

3. The polysubstituted chloroacetophenone compound of claim 1 or 2 having a structure represented by any one of formulae I-1 to I-5:

4. a process for producing a polysubstituted chloroethynylbenzene compound according to any one of claims 1 to 3, which comprises the steps of:

(1) mixing a polysubstituted trimethylacetylene silylbenzene compound, an alkaline reagent, 18-crown ether-6 and a first organic solvent, and performing a trimethyl silicon removal reaction to obtain a polysubstituted acetylene silylbenzene compound;

(2) mixing the polysubstituted acetylene based phenyl compound, N-chlorosuccinimide and a second organic solvent, and carrying out nucleophilic substitution reaction to obtain a polysubstituted chlorine ethynylbenzene compound;

the polysubstituted trimethylacetylene silylbenzene compound has a structure shown in a formula II:

in the formula II, R is^1’、R^2’、R^3’、R^4’And R^5’Is trimethylsilylethynyl;

or, R¹、R^2’And R^3’Is trimethylsilylethynyl, R^4’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R^1’、R^3’And R^4’Is trimethylsilylethynyl, R^2’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R^2’And R^4’Is trimethylsilylethynyl, R^1’、R^3’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo.

5. The method according to claim 4, wherein in the step (1), the molar ratio of the polysubstituted trimethylacetylene silylbenzene compound, the alkaline agent and the 18-crown-6 is 1: (3-50): (0.1-5);

the alkaline reagent comprises potassium fluoride, tetrabutylammonium chloride or potassium carbonate;

the first organic solvent includes ethylene glycol dimethyl ether, tetrahydrofuran, or dimethyl ether.

6. The preparation method according to claim 4 or 5, wherein in the step (1), the temperature of the trimethyl silicon removal reaction is-78-30 ℃ and the time is 2-5 h.

7. The method according to claim 4, wherein in the step (2), the molar ratio of the polysubstituted acetylenic silylbenzene compound to the N-chlorosuccinimide is 1: (3-20).

8. The production method according to claim 4, wherein the production raw material of the step (2) further comprises a catalyst and/or an alkali agent;

the catalyst comprises n-butyl lithium, lithium diisopropylamide, tert-butyl lithium or silver carbonate;

the alkaline reagent in the step (2) comprises tetrabutylammonium fluoride, tetrabutylammonium chloride or 1, 8-diazabicycloundecen-7-ene;

the second organic solvent comprises acetonitrile or tetrahydrofuran.

9. The preparation method according to claim 4, 7 or 8, wherein the temperature of the nucleophilic substitution reaction is 0-30 ℃ and the time is 2-15 h.

10. Use of the polysubstituted chloroethynylbenzene compound as claimed in any one of claims 1 to 2 or prepared by the preparation method as claimed in any one of claims 3 to 9 in the construction of two-dimensional metal organic framework materials.

Technical Field

The invention relates to the technical field of organic synthesis, in particular to a polysubstituted chlorine ethynylbenzene compound and a preparation method and application thereof.

Background

Halogenated alkynes are a very useful class of organic synthesis intermediates, and have structural features mainly including C (sp) -C (sp) type carbon-carbon triple bonds and halogens directly connected with the C (sp) -C (sp) type carbon-carbon triple bonds, and because the C (sp) -C (sp) bonds and the C (sp) -X (X is halogen) bonds are simultaneously connected, nucleophilic and electrophilic reagents are likely to be attacked, the alkyne halides can show controllable electrophilicity and nucleophilicity, and thus can be used for important purposes in the synthesis of functional molecules.

At present, a two-dimensional metal framework structure connected by C (sp) -M-C (sp) structural units is constructed, wherein the C (sp) -M-C (sp) structural units are generated through debromination reaction by taking alkyne bromine as a reaction functional group, and then a two-dimensional organic metal framework structure (ACS Nano No.2016,10,7023; Nanoscale 2018,10,3769) is obtained. However, since the alkyne bromide activity is too high, it is difficult to achieve reaction control, an irregular two-dimensional organometallic framework structure is often obtained, and a two-dimensional organometallic framework structure cannot be obtained in a large area. Therefore, it is necessary to develop a more stable reactive group to realize the construction of a two-dimensional organometallic framework structure based on C (sp) -M-C (sp) structural units.

Disclosure of Invention

In view of the above, the present invention provides a polysubstituted chloroethynyl benzene compound, and a preparation method and an application thereof, and the polysubstituted chloroethynyl benzene compound provided by the invention has good stability and can construct a large-area and high-stability two-dimensional organic metal framework structure.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a polysubstituted chlorine ethynylbenzene compound, which has a structure shown in a formula I:

in the formula I, R is¹、R²、R³、R⁴And R⁵Is a chloroethynyl group;

or, R¹、R²And R³Is chloroethynyl, R⁴And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R¹、R³And R⁴Is chloroethynyl, R²And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R²And R⁴Is chloroethynyl, R¹、R³And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo.

Preferably, the alkyl group is methyl or ethyl; the halogen group is-F, -Cl, -Br or-I.

Preferably, the polysubstituted chlorine ethynylbenzene compound has a structure shown in any one of formulas I-1 to I-5:

the invention provides a preparation method of a polysubstituted chloroethynyl benzene compound in the technical scheme, which comprises the following steps:

(1) mixing a polysubstituted trimethylacetylene silylbenzene compound, an alkaline reagent, 18-crown ether-6 and a first organic solvent, and performing a trimethyl silicon removal reaction to obtain a polysubstituted acetylene silylbenzene compound;

(2) mixing the polysubstituted acetylene based phenyl compound, N-chlorosuccinimide and a second organic solvent, and carrying out nucleophilic substitution reaction to obtain a polysubstituted chlorine ethynylbenzene compound;

the polysubstituted trimethylacetylene silylbenzene compound has a structure shown in a formula II:

in the formula II, R is^1’、R^2’、R^3’、R^4’And R^5’Is trimethylsilylethynyl;

or, R¹、R^2’And R^3’Is trimethylsilylethynyl, R^4’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R^1’、R^3’And R^4’Is trimethylsilylethynyl, R^2’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R^2’And R^4’Is trimethylsilylethynyl, R^1’、R^3’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo.

Preferably, in the step (1), the molar ratio of the polysubstituted trimethylacetylene silylbenzene compound, the alkaline reagent and the 18-crown-6 is 1: (3-50): (0.1-5);

the alkaline reagent comprises potassium fluoride, tetrabutylammonium chloride or potassium carbonate;

the first organic solvent includes ethylene glycol dimethyl ether, tetrahydrofuran, or dimethyl ether.

Preferably, in the step (1), the temperature of the trimethyl silicon removal reaction is-78-30 ℃ and the time is 2-5 hours.

Preferably, in the step (2), the molar ratio of the polysubstituted acetylene silicon benzene compound to the N-chlorosuccinimide is 1: (3-20).

Preferably, the preparation raw material of the step (2) further comprises a catalyst and/or an alkaline reagent;

the catalyst comprises n-butyl lithium, lithium diisopropylamide, tert-butyl lithium or silver carbonate;

the alkaline reagent in the step (2) comprises tetrabutylammonium fluoride, tetrabutylammonium chloride or 1, 8-diazabicycloundecen-7-ene;

the second organic solvent comprises acetonitrile or tetrahydrofuran.

Preferably, the temperature of the nucleophilic substitution reaction is-10-30 ℃ and the time is 2-15 h.

The invention also provides application of the polysubstituted chlorine ethynylbenzene compound in the technical scheme or the polysubstituted chlorine ethynylbenzene compound prepared by the preparation method in the technical scheme in construction of a two-dimensional metal organic framework material.

The invention provides a polysubstituted chlorine ethynylbenzene compound which has a structure shown in a formula I, wherein R in the formula I¹、R²、R³、R⁴And R⁵Is a chloroethynyl group; or, R¹、R²And R³Is chloroethynyl, R⁴And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo; or, R¹、R³And R⁴Is chloroethynyl, R²And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo; or, R²And R⁴Is chloroethynyl, R¹、R³And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo. The polysubstituted (not less than 3) chloroethynyl benzene compound provided by the invention has the advantages of good structural symmetry, good thermal stability and good reaction selectivity, is used for carrying out mild dechlorination reaction construction on the surface of a two-dimensional substrate to obtain a two-dimensional metal organic framework material with high stability and large area, and lays a foundation for further realizing the construction of graphite alkyne materials.

The preparation method provided by the invention has the advantages of high product yield, high purity and simple operation, and is suitable for industrial production.

Drawings

Fig. 1 is a Scanning Tunneling Microscope (STM) image of a two-dimensional metal organic framework material prepared in application example 1, wherein a is an STM image of a polysubstituted chloroacetophenone compound having a formula I-5 vacuum-evaporated onto a Au (111) surface of 150K, b is a high resolution STM image of fig. a, c is an STM image of a polysubstituted chloroacetophenone compound having a formula I-5 annealed onto a Au (111) surface to 463K, and d is a high resolution STM image of fig. c.

Detailed Description

The polysubstituted chlorine ethynylbenzene compound has a structure shown in a formula I:

in the formula I, R is¹、R²、R³、R⁴And R⁵Is a chloroethynyl group;

or, R¹、R²And R³Is chloroethynyl, R⁴And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R¹、R³And R⁴Is chloroethynyl, R²And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R²And R⁴Is chloroethynyl, R¹、R³And R⁵Independently hydrogen, alkyl, aryl, heteroaryl or halo.

In the present invention, the alkyl group is preferably a methyl group or an ethyl group. In the present invention, the aryl group is preferably a phenyl group. In the present invention, the heteroaryl group is preferably a thienyl group. In the present invention, the halogen group is preferably-F, -Cl, -Br or-I.

In the present invention, the polysubstituted chloroethynylbenzene compound preferably has a structure represented by any one of formulas I-1 to I-5:

the invention provides a preparation method of a polysubstituted chloroethynyl benzene compound in the technical scheme, which comprises the following steps:

(1) mixing a polysubstituted trimethylacetylene silylbenzene compound, an alkaline reagent, 18-crown ether-6 and a first organic solvent, and performing a trimethyl silicon removal reaction to obtain a polysubstituted acetylene silylbenzene compound;

(2) mixing the polysubstituted acetylene based phenyl compound, N-chlorosuccinimide and a second organic solvent, and carrying out nucleophilic substitution reaction to obtain a polysubstituted chlorine ethynylbenzene compound;

the polysubstituted trimethylacetylene silylbenzene compound has a structure shown in a formula II:

in the formula II, R is^1’、R^2’、R^3’、R^4’And R^5’Is trimethylsilylethynyl;

or, R¹、R^2’And R^3’Is trimethylsilylethynyl, R^4’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R^1’、R^3’And R^4’Is trimethylsilylethynyl, R^2’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo;

or, R^2’And R^4’Is trimethylsilylethynyl, R^1’、R^3’And R^5’Independently hydrogen, alkyl, aryl, heteroaryl or halo.

In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.

Mixing a polysubstituted trimethyl acetylene silicon benzene compound, an alkaline reagent, 18-crown ether-6 and a first organic solvent, and carrying out trimethyl silicon removal reaction to obtain a polysubstituted acetylene silicon benzene compound; the polysubstituted trimethylacetylene silylbenzene compound has a structure shown in a formula II:

in the present invention, the alkyl, aryl, heteroaryl or halogen group is preferably the same as the alkyl, aryl, heteroaryl or halogen group described in the above technical solutions, and is not described herein again.

In the invention, the polysubstituted trimethylacetylene silylbenzene compound is preferably obtained by self-made references (Eur.J.org.chem.2014, 6295; adv.Mater.2017,29,1604665).

In the present invention, the alkali agent preferably includes potassium fluoride, tetrabutylammonium chloride or potassium carbonate. In the present invention, the molar ratio of the polysubstituted trimethylacetylene silylbenzene compound, the alkaline agent and the 18-crown-6 is preferably 1: (3-50): (0.1 to 5), more preferably 1: (10-45): (0.15-2), most preferably 1: (20-40): (0.15-0.5).

In the present invention, the first organic solvent preferably includes ethylene glycol dimethyl ether, tetrahydrofuran or dimethyl ether. The dosage of the first organic solvent is not particularly limited, and the polysubstituted trimethylacetylene silylbenzene compound can be dissolved; in the present invention, the ratio of the amount of the substance of the polysubstituted trimethylacetylene silylbenzene compound to the volume of the first organic solvent is preferably 1 mmol: (70-150) mL, more preferably 1 mmol: (75-135) mL, most preferably 1 mmol: (90-120) mL.

In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed. In the present invention, the mixing order is preferably that the polysubstituted trimethylacetylene silylbenzene compound is dissolved in the first organic solvent, and then the alkaline reagent and the 18-crown-6 are added and mixed.

In the invention, the temperature of the trimethyl silicon removal reaction is preferably-78-30 ℃, more preferably-50-25 ℃, and most preferably 0-20 ℃; the time for the trimethyl silicon removal reaction is preferably 2-5 hours, and more preferably 3-4 hours. In the invention, in the trimethyl silicon removal reaction process, the polysubstituted trimethyl acetylene silicon benzene compound is subjected to trimethyl silicon removal reaction under the action of an alkaline reagent and 18-crown ether-6 to generate the polysubstituted acetylene silicon benzene compound.

After the trimethyl silicon removal reaction, the invention preferably further comprises the steps of washing the reaction liquid obtained by the trimethyl silicon removal reaction with saturated saline solution, extracting, drying a drying agent, removing the drying agent and concentrating to obtain the polysubstituted ethynylsilylbenzene compound. In the present invention, the number of times of washing with saturated brine is preferably 3 to 4 times; the amount of the saturated saline solution used in each washing with the saturated saline solution is not particularly limited, and the amount of the saturated saline solution known to those skilled in the art can be used; in the embodiment of the invention, the ratio of the mass of the polysubstituted trimethylacetylene silylbenzene compound to the volume of the saturated saline solution is (50-100) mg: 30 mL. In the present invention, the extractant used for the extraction preferably comprises dichloromethane; the extraction frequency is preferably 3-4 times; the amount of the extracting agent used in each extraction is not particularly limited in the invention, and the amount of the extracting agent known to those skilled in the art can be used; in the embodiment of the invention, the ratio of the mass of the polysubstituted trimethylacetylene silylbenzene compound to the volume of the extracting agent is (50-100) mg: 30 mL. In the present invention, the drying agent preferably includes anhydrous sodium sulfate or anhydrous magnesium sulfate. In the present invention, the drying agent is preferably removed by filtration. In the present invention, the method of concentration is preferably distillation under reduced pressure; in the present invention, the distillation conditions under reduced pressure are not particularly limited, and those known to those skilled in the art can be used.

After the polysubstituted acetylene silicon benzene compound is obtained, the polysubstituted acetylene silicon benzene compound, N-chlorosuccinimide and a second organic solvent are mixed for nucleophilic substitution reaction to obtain the polysubstituted chlorine ethynylbenzene compound.

In the present invention, the molar ratio of the polysubstituted acetylenic silylbenzene compound to the N-chlorosuccinimide is preferably 1: (3-20), more preferably 1: (3.5 to 15), most preferably 1: (3.5-11).

In the present invention, the raw material participating in the nucleophilic substitution reaction preferably further comprises a catalyst and/or an alkaline agent. In the present invention, the catalyst preferably includes n-butyllithium, lithium diisopropylamide, t-butyllithium, or silver carbonate; in the present invention, the silver carbonate is preferably used in the form of a silver carbonate solid. In the present invention, when the catalyst is n-butyllithium, lithium diisopropylamide or t-butyllithium, the catalyst is preferably used in the form of a catalyst solution, and the solvent in the catalyst solution is preferably hexane, cyclohexane or benzene, and the concentration of the catalyst solution in the present invention is not particularly limited, and commercially available products well known to those skilled in the art may be used; in the embodiment of the present invention, the concentration of the catalyst solution is preferably 2.5 mol/L; the solvent in the catalyst solution is preferably cyclohexane. In the invention, the catalyst is used for reacting with terminal alkyne of the polysubstituted acetylene silicon benzene compound to generate an intermediate, and then carrying out subsequent nucleophilic substitution reaction. In the invention, the molar ratio of the polysubstituted acetylene silicon benzene compound to the catalyst is preferably 1: (0.1 to 5), more preferably 1: (1.15-4.8), and most preferably 1: 1. In the present invention, the basic agent preferably includes tetrabutylammonium fluoride, tetrabutylammonium chloride or 1, 8-diazabicycloundecen-7-ene (DBU); the alkaline reagent is used for capturing alkyne hydrogen. In the present invention, the molar ratio of the polysubstituted ethynylsilylbenzene compound to the basic agent is preferably 1: (0.1 to 1), more preferably 1: (0.2 to 0.8), most preferably 1: (0.2-0.5).

In the present invention, the second organic solvent preferably includes acetonitrile or tetrahydrofuran, and the ratio of the amount of the substance of the polysubstituted ethynyl silylbenzene-based compound to the volume of the second organic solvent is preferably 1 mmol: (10-60) mL, more preferably 1 mmol: (20-50) mL, most preferably 1 mmol: (30-40) mL.

In the present invention, the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed. In the present invention, the mixing order is preferably that a polysubstituted trimethylethynylene silylbenzene compound is dissolved in a second organic solvent to obtain a polysubstituted trimethylethynylene silylbenzene solution, and the polysubstituted trimethylethynylene silylbenzene compound and N-chlorosuccinimide are mixed.

In the present invention, when the raw material for participating in the nucleophilic substitution reaction further comprises a catalyst and/or an alkaline agent, the timing of adding the alkaline agent is preferably the same as the timing of adding the N-chlorosuccinimide; the adding time of the catalyst is preferably determined according to the type of the catalyst; when the catalyst is silver carbonate, the adding time of the catalyst is preferably the same as that of the N-chlorosuccinimide; when the catalyst is N-butyllithium, lithium diisopropylamide or tert-butyllithium, the catalyst is preferably added dropwise into the polysubstituted trimethylethynyl silylbenzene solution at-78 ℃, and then N-chlorosuccinimide is added or N-chlorosuccinimide and an alkaline reagent are added. The dropping speed is not particularly limited, and the dropping can be carried out at the uniform speed.

In the invention, the temperature of the nucleophilic substitution reaction is preferably-10-30 ℃, and more preferably 0-25 ℃; the time of the nucleophilic substitution reaction is preferably 2-15 h, and more preferably 10-12 h. In the nucleophilic substitution reaction process, the alkyne end group hydrogen of the polysubstituted trimethylacetylene phenyl compound is substituted by chlorine in N-chlorosuccinimide to generate the polysubstituted chlorine ethynylbenzene compound.

After the nucleophilic substitution reaction, the method preferably further comprises the steps of washing the reaction liquid obtained by the nucleophilic substitution reaction with saturated saline solution, extracting, drying with a drying agent, removing the drying agent, concentrating, and separating and purifying by column chromatography to obtain the polysubstituted chlorine ethynylbenzene compound. In the present invention, the number of times of washing with saturated brine is preferably 3 to 4. In the present invention, the extractant used for the extraction preferably comprises dichloromethane; the number of times of extraction is preferably 3-4. In the present invention, the drying agent preferably includes anhydrous sodium sulfate or anhydrous magnesium sulfate. In the present invention, the drying agent is preferably removed by filtration. In the present invention, the method of concentration is preferably distillation under reduced pressure; in the present invention, the distillation conditions under reduced pressure are not particularly limited, and those known to those skilled in the art can be used. In the present invention, the eluent for the column chromatography separation and purification preferably comprises petroleum ether.

The invention also provides application of the polysubstituted chlorine ethynylbenzene compound in the technical scheme or the polysubstituted chlorine ethynylbenzene compound prepared by the preparation method in the technical scheme in construction of a two-dimensional metal organic framework material.

In the present invention, the method of application preferably comprises the steps of: and depositing the polysubstituted chlorine ethynylbenzene compound on the surface of a two-dimensional metal substrate for dechlorination reaction to obtain the two-dimensional metal organic framework material. In the present invention, the two-dimensional metal substrate preferably includes a two-dimensional gold substrate or a two-dimensional silver substrate, more preferably Au (111) or Ag (111). In the present invention, the polysubstituted chloroethynylbenzene compound is preferably of a monolayer structure. In the present invention, the deposition is preferably performed by vacuum evaporation through a micro-leak valve at room temperature. In the invention, the temperature of the dechlorination reaction is preferably 120-240 ℃, and more preferably 160-200 ℃; the time is preferably 0.15 to 1 hour, and more preferably 0.2 to 0.5 hour; the pressure of the dechlorination reaction is preferably 10^-5～10^-10mbar, more preferably 10^-9～10^-10mbar. In the dechlorination process, a C-Cl bond is activated by a metal substrate to form a C- (sp) -M-Cl intermediate, then the C- (sp) -Cl intermediate and a chloroethynylene functional group in another molecule are subjected to C- (sp) -Cl cleavage reaction to form a C- (sp) -M-C (sp) structure, and further, the polysubstituted chloroethynylbenzene compounds are subjected to self-assembly on the surface of a two-dimensional metal substrate to form the two-dimensional metal organic framework material. In the present invention, the two-dimensional metal-organic framework material preferably has an island-like structure, and the island-like structure is preferably a honeycomb structure.

In the present invention, the two-dimensional metal-organic framework material is preferably further used for preparing graphite acetylene materials.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.