CN110981680A - Preparation method for constructing hexabenzocoronene by polycyclic aromatic hydrocarbon phenanthrene in coal tar - Google Patents

Preparation method for constructing hexabenzocoronene by polycyclic aromatic hydrocarbon phenanthrene in coal tar Download PDF

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CN110981680A
CN110981680A CN201911333831.XA CN201911333831A CN110981680A CN 110981680 A CN110981680 A CN 110981680A CN 201911333831 A CN201911333831 A CN 201911333831A CN 110981680 A CN110981680 A CN 110981680A
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hexabenzocoronene
phenanthrene
coal tar
polycyclic aromatic
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张建兰
张亚婷
张博超
邱介山
党永强
李可可
张睿哲
刘国阳
贺新福
王鹏
李思祎
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Xian University of Science and Technology
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Abstract

The invention discloses a preparation method for constructing hexabenzocoronene by polycyclic aromatic hydrocarbon phenanthrene in coal tar, which comprises the steps of taking polycyclic aromatic hydrocarbon phenanthrene in coal tar as a raw material, firstly carrying out an oxidative addition reaction with chromium trioxide to generate phenanthrenequinone, then carrying out a nucleophilic addition elimination reaction with dibenzyl ketone in a potassium hydroxide methanol solution to generate 9, 10-phenanthro 1, 12-diphenylcyclopentadienone, then carrying out a Diels-Alder cycloaddition reaction with tolane in a diphenyl ether solution to obtain 1,2,3, 4-tetraphenyltriphenylene, and finally carrying out an oxidative cyclization dehydrogenation reaction with anhydrous ferric chloride to generate hexabenzocoronene. According to the method, the hexabenzocoronene is prepared by taking the polycyclic aromatic hydrocarbon substance phenanthrene in the coal tar as a raw material, and the yield of each step is improved through reasonable planning of a synthesis route, so that the yield of the hexabenzocoronene is improved, the method can be popularized and applied to the process of synthesizing graphene from other polycyclic aromatic hydrocarbons in the coal tar, and the high value-added utilization of the coal tar resource is improved.

Description

Preparation method for constructing hexabenzocoronene by polycyclic aromatic hydrocarbon phenanthrene in coal tar
Technical Field
The invention belongs to the technical field of preparation of hexabenzocoronene, and particularly relates to a preparation method for constructing hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar.
Background
Coal tar is a liquid coking byproduct, and can generate toxic gas by direct combustion, thereby causing great pollution to the environment. China is the country with the largest coal tar yield in the world, and the annual coal tar yield of China is about 1773 million tons, which accounts for more than 60% of the world yield. How to utilize coal tar with high quality is a considerable problem in the chemical industry. China is in a relatively laggard state in the aspect of coal tar deep processing technology, and the concentration degree of an industrial chain is also insufficient. The coal tar is one of the products in the crude gas generated by pyrolyzing coal in the coking industry, the yield of the coal tar is large and accounts for about 3% -4% of the coal charged in the furnace, the composition is very complex, and the coal tar is specially separated and purified by the coal tar industry for utilization in most cases. The main products extracted are: naphthalene, phenanthrene, pyrene, anthracene, and the like. The industries related to the coal tar at present comprise dye manufacturing and medicine manufacturing. And the high added value of the coal tar product is less in application and poor in effective utilization.
The graphene molecule has a non-zero forbidden band width, so that the limitation of graphene in field effect transistor application can be compensated, and the graphene molecule has a wide application prospect in the fields of semiconductor materials, sensors, electronic devices and the like. The synthesis of graphene molecules can be prepared by two synthetic strategies: "top-down" or "bottom-up". In comparison, the morphology and the size of the graphene molecule can be more easily and accurately regulated from bottom to top, and the influence of the structure of the graphene molecule on the performance can be favorably researched. Hexabenzocoronene (HBC) is known as the most elegant graphene motif. Is a disk-shaped molecule with a regular hexagonal structure formed by connecting 7 benzene rings, has the diameter of about 1.5nm, and is a macrocyclic aromatic compound with a rigid condensed biphenyl unit.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method for constructing hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar aiming at the defects of the prior art. According to the method, the hexabenzocoronene is prepared by taking the polycyclic aromatic hydrocarbon substance phenanthrene in the coal tar as a raw material, the yield of each step is improved by reasonably planning a synthesis route and respectively controlling the yield of each step, so that the yield of the hexabenzocoronene is improved, the method can be popularized and applied to the process of synthesizing graphene from other polycyclic aromatic hydrocarbons in the coal tar, and the high value-added utilization of the coal tar resource is further improved.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method for constructing hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar is characterized by comprising the following steps:
dissolving polycyclic aromatic hydrocarbon phenanthrene in acetic acid, dropwise adding an acetic acid water solution of chromium trioxide to react to obtain a reacted solution, adding the reacted solution into a potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by adopting anhydrous magnesium sulfate, and removing the solvent by evaporation to obtain a dicarboxyl compound phenanthrenequinone;
step two, adding the dicarboxyl compound phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, then dropwise adding an alcoholic solution of potassium hydroxide under the condition of stirring, heating and refluxing to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to obtain a solid, washing the solid with an alcohol solution, and drying to obtain a monocarbonyl compound 9, 10-phenanthro 1, 12-diphenyl cyclopentadienone;
dissolving alkyne compound diphenylacetylene and monocarbonyl compound 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in diphenyl ether, then reacting under the condition of stirring and heating, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, and carrying out rotary evaporation on collected eluent to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
step four, dissolving the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the step three in a polar solvent to obtain a phenyl compound solution, dissolving anhydrous ferric chloride in nitromethane to obtain a ferric chloride solution, then dropwise adding the ferric chloride solution into the phenyl compound solution under the protection of inert gas for reaction to obtain a solution after reaction, mixing the solution after reaction with 0.1mol/L HCl solution, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain the hexabenzocoronene.
The preparation mechanism of the invention is as follows:
Figure BDA0002330409670000031
the method takes polycyclic aromatic hydrocarbon substance phenanthrene in coal tar as a raw material, firstly generates an oxidative addition reaction with chromium trioxide to generate a dicarboxyl compound phenanthrenequinone with a yield of up to 83%, then generates a nucleophilic addition elimination reaction with dibenzyl ketone in a potassium hydroxide methanol solution to generate a monocarboxyl compound 9, 10-phenanthro 1, 12-diphenylcyclopentadienone with a yield of up to 78.3%, and then generates a Diels-Alder cycloaddition reaction with tolane in a diphenyl ether solution to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene with a yield of up to 85%, and finally generates an oxidative cyclization dehydrogenation reaction with anhydrous ferric chloride to generate the hexabenzocoronene with a yield of up to 98.8%. The invention firstly proposes to synthesize the hexabenzocoronene by taking the polycyclic aromatic hydrocarbon substance-phenanthrene in the coal tar as the raw material, and improves the yield of each step by reasonably planning the synthesis route and respectively controlling the yield of each step, thereby improving the preparation efficiency and the yield of the hexabenzocoronene.
The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that the amount ratio of the polycyclic aromatic hydrocarbon phenanthrene to the chromium trioxide in the acetic acid aqueous solution of the chromium trioxide in the first step is 1: 4. The amount ratio of the substances is beneficial to full oxidation reaction of phenanthrene and chromium trioxide, the yield of phenanthrenequinone is improved, and meanwhile, waste of raw materials is avoided.
The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that in the step one, the volume ratio of acetic acid to water in an acetic acid aqueous solution used as a solvent for the acetic acid aqueous solution of the chromium trioxide is 5:2, and the reaction time is 2-3 hours. The composition of the acetic acid aqueous solution is favorable for fully dissolving the chromium trioxide; the optimized reaction time is beneficial to the full progress of the oxidation reaction, and the yield of the phenanthrenequinone is further improved.
The preparation method for constructing the hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar is characterized in that in the step one, the ratio of the amount of the substance of the dibenzyl ketone in the alcoholic solution of the dicarboxyl compound phenanthrenequinone to the amount of the substance of the dibenzyl ketone in the alcoholic solution of the dibenzyl ketone is 1:1, and the solvent adopted in the alcoholic solution of the dibenzyl ketone is methanol or ethanol.
The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that the heating reflux temperature in the second step is 60-100 ℃, and the time is 2-5 hours. The preferred heating reflux temperature promotes the rapid progress of the reflux reaction, reduces the generation of side reactions and improves the yield of the 9, 10-phenanthro 1, 12-diphenyl cyclopentadienone.
The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that the mass ratio of the alkyne compound tolane to the monocarbonyl compound 9, 10-phenanthro 1, 12-diphenylcyclopentadienone is 1:1 in the third step. The preferred amount ratio of substances facilitates the Diels-Alder cycloaddition reaction to proceed sufficiently, and improves the yield of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene.
The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that the heating reaction in the third step is carried out at the temperature of 200-300 ℃ for 3-8 h. The preferred heating reaction temperature promotes the rapid progress of the reaction and increases the yield of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene.
The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that a polar solvent in the step four is dichloromethane or methanol, and the mass ratio of the phenyl compound to anhydrous ferric chloride is 1: 1.
The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that the inert gas is nitrogen or argon in the fourth step, and the reaction time is 60-120 min.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the hexabenzocoronene is prepared by taking the polycyclic aromatic hydrocarbon substance-phenanthrene in the coal tar as a raw material, and the yield of each step is improved by reasonably planning a synthesis route and respectively controlling the yield of each step, so that the preparation efficiency and the yield of the hexabenzocoronene are improved.
2. The method effectively improves the yield of the product hexabenzocoronene to 98.8% by controlling the yield of the compound obtained by each step of reaction, has high yield and controllable process, and improves the practical value of the method.
3. The invention firstly provides a new idea of constructing graphene molecules by polycyclic aromatic hydrocarbons in coal tar, integrates and develops a new process route for synthesizing the hexabenzocoronene based on phenanthrene in the coal tar, and also synthesizes the hexabenzocoronene by taking 1,2,3, 4-tetraphenyltriphenylene as a raw material, and the process flow can be popularized and applied to the process of synthesizing graphene by other polycyclic aromatic hydrocarbons (such as naphthalene, pyrene, anthracene and the like) in the coal tar, thereby further improving the high-added-value utilization of coal tar resources.
The invention is explained in more detail below with reference to the figures and examples.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of phenanthrenequinone prepared in example 1 of the present invention.
FIG. 2 is a nuclear magnetic carbon spectrum of phenanthrenequinone prepared in example 1 of the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of 9, 10-phenanthro 1, 12-diphenylcyclopentone prepared in example 1 of the present invention.
FIG. 4 is a nuclear magnetic carbon spectrum of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone prepared in example 1 of the present invention.
FIG. 5 is a nuclear magnetic hydrogen spectrum of 1,2,3, 4-tetraphenyltriphenylene prepared in example 1 of the present invention.
FIG. 6 shows the nuclear magnetic carbon spectrum of 1,2,3, 4-tetraphenyltriphenylene prepared in example 1 of the present invention.
FIG. 7 is a mass spectrum of hexabenzocoronene prepared in example 1 of the invention.
Detailed Description
Example 1
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into 5mL of acetic acid and 2mL of water (prepared acetic acid aqueous solution to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing for 5 hours at 80 ℃ to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 99.8% as detected and calculated.
FIG. 1 is the nuclear magnetic hydrogen spectrum of the phenanthrenequinone prepared in this example, and as can be seen from FIG. 1, 4 groups of peaks appear in the nuclear magnetic hydrogen spectrum of the phenanthrenequinone, which indicates that the phenanthrenequinone contains 4 types of hydrogen, and a total of 8 aromatic hydrogens can be found by integration (1)1H NMR d(400M,CDCl3) 8.14-8.10(m,2H),7.97-7.93(m,2H),7.72-7.66(m,2H),7.47-7.41(m,2H)), consistent with the number of hydrogens in phenanthrenequinone, and chemical shifts consistent with literature descriptions.
FIG. 2 is the nuclear magnetic carbon spectrum of phenanthrenequinone prepared in this exampleAs can be seen from FIG. 2, 7 groups of peaks (A) appear in the nuclear magnetic carbon spectrum of phenanthrenequinone13C NMR d(100M,CDCl3) 180.1,135.9,135.6,130.8,130.3,129.5,123.9), indicating that there are 7 types of carbon in total, consistent with the number of carbons in phenanthrenequinone, and chemical shifts consistent with literature.
FIG. 3 is a nuclear magnetic hydrogen spectrum of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone prepared in this example, and it can be seen from FIG. 3 that 4 sets of peaks appear in the nuclear magnetic hydrogen spectrum of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone, which shows 5 types of total hydrogen according to molecular symmetry, and a total of 18 aromatic hydrogens (H NMR d (400M, CDCl) are found by integration3) 7.82-7.77(m,2H),7.57-7.53(m,2H),7.44-7.36(m,10H),7.30-7.24(m,2H),6.97-6.91(m,2H), consistent with the number of hydrogens in 9, 10-phenanthro 1, 12-diphenylcyclopentadienone; FIG. 4 is the nuclear magnetic carbon spectrum of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone prepared in this example, and it can be found by integration that there are 29 carbon atoms (total13C NMR d(100M,CDCl3) 200.1,148.2,135.6,132.2,131.4,130.0,129.0,128.6,128.5,128.2,128.1,124.4,123.1), indicating that the compound prepared in step two of this example has the structure of cyclopentadienone.
FIG. 5 is a nuclear magnetic hydrogen spectrum of 1,2,3, 4-tetraphenyltriphenylene prepared in this example, which shows a total of 28 hydrogen atoms by integration (1H NMR d(400M,CDCl3) 8.40(d, J ═ 8.4Hz,2H),7.59(d, J ═ 8.4Hz,2H),7.38(t, J ═ 7.6Hz,2H),7.06-6.98(m,12H),6.89-6.87(m,6H),6.71-6.69(m, 4H)); FIG. 6 is the NMR spectrum of 1,2,3, 4-tetraphenyltriphenylene prepared in this example, which shows a total of 42 carbon atoms by integration (C: (A))13CNMR d(100M,CDCl3) 142.9,140.4,137.2,132.1,131.6,131.5,131.2,130.8,130.0,127.9,126.6,126.3,126.2,125.4,125.2,123.2) indicating that the compound prepared in step three of this example has the structure of 1,2,3, 4-tetraphenyltriphenylene.
Fig. 7 is a mass spectrum of the hexabenzocoronene prepared in this example, and as can be seen from fig. 7, the measured value of the molecular weight of the hexabenzocoronene prepared in this example is 522.27, which is very close to theory 522.14, and within an allowable error range, the hexabenzocoronene is illustrated as the compound prepared in this example.
Example 2
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 1h to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing at 80 ℃ for 3 hours to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 94.9% as detected and calculated.
Example 3
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution for reaction for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene, oscillating, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and removing the solvent by evaporation to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing at 80 ℃ for 3 hours to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 95.1% as detected and calculated.
Example 4
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 3 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing at 80 ℃ for 3 hours to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 97.7% as detected and calculated.
Example 5
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing at 80 ℃ for 2 hours to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 97.3% as detected and calculated.
Example 6
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing for 5 hours at 80 ℃ to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 200 ℃, heating and reacting for 3h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 97.1% as detected and calculated.
Example 7
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing for 5 hours at 80 ℃ to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 300 ℃, carrying out heating reaction for 8h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 96.9% as detected and calculated.
Example 8
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing for 5 hours at 80 ℃ to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg into 6mL of methanol;
step three, dissolving 0.986g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenyl cyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
step four, dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the step three in 8mL of dichloromethane to obtain a phenyl compound solution, introducing argon gas for 30min, dropwise adding the ferric chloride solution into the phenyl compound solution under the protection of argon gas for reacting for 60min to obtain a reacted solution, adding 50mL of methanol into the reacted solution, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid, namely the hexabenzocoronene.
The hexabenzocoronene yield of the invention was 96.6% as detected and calculated.
Example 9
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing for 5 hours at 80 ℃ to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of methanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reaction for 120min to obtain a solution after the reaction, adding 50mL of methanol into the solution after the reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 96.3% as detected and calculated.
Example 10
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing at 100 ℃ for 5 hours to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of ethanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of dichloromethane, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 96.1% as detected and calculated.
Example 11
The preparation method of this example includes the following steps:
step one, dissolving 1.0g of phenanthrene in 8mL of acetic acid solution at the temperature of 60 ℃ to obtain phenanthrene acetic acid solution, then adding 2.2g of chromium trioxide into acetic acid aqueous solution prepared from 5mL of acetic acid and 2mL of water to obtain chromium trioxide acetic acid aqueous solution, dropwise adding the chromium trioxide acetic acid aqueous solution into the phenanthrene acetic acid solution to react for 2 hours to obtain reacted solution, adding the reacted solution into 350mL of 1M potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by using anhydrous magnesium sulfate, and evaporating to remove the solvent to obtain orange solid phenanthrenequinone;
step two, adding 0.75g of phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, heating to 80 ℃, then dropwise adding the alcoholic solution of potassium hydroxide under the condition of stirring, continuously refluxing at 100 ℃ for 5 hours to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to separate out a solid, washing the solid with methanol, and drying to obtain a dark brown solid, namely, monocarbonyl compound 9, 10-phenanthrene 1, 12-diphenyl cyclopentadienone;
the methanol solution of the dibenzyl ketone is prepared by adding 0.75g of dibenzyl ketone into 45mL of ethanol; the alcoholic solution of potassium hydroxide is prepared by adding 400mg of potassium hydroxide into 6mL of methanol;
step three, dissolving 0.9786g of tolane and 2.1g of 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in 5mL of diphenyl ether, then placing the diphenyl ether in silicone oil at 240 ℃, carrying out heating reaction for 5h under the condition of stirring, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, collecting the obtained eluent, and carrying out rotary evaporation to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
dissolving 120mg of anhydrous ferric chloride in 0.4mL of nitromethane, introducing argon gas for 1min to obtain a ferric chloride solution, dissolving 9.8mg of the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the third step in 8mL of methanol, introducing argon gas for 30min to obtain a phenyl compound solution, dropwise adding the ferric chloride solution into the phenyl compound solution by using a liquid transfer gun under the protection of argon gas for reacting for 90min to obtain a solution after reaction, adding 50mL of methanol into the solution after reaction, mixing with 0.1mol/L of HCl solution to remove incompletely reacted ferric chloride, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain a light red solid of hexabenzocoronene.
The hexabenzocoronene yield of the invention was 94.3% as detected and calculated.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (9)

1. A preparation method for constructing hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar is characterized by comprising the following steps:
dissolving polycyclic aromatic hydrocarbon phenanthrene in acetic acid, dropwise adding an acetic acid water solution of chromium trioxide to react to obtain a reacted solution, adding the reacted solution into a potassium carbonate solution, adding toluene to oscillate, separating to obtain an organic layer, drying the organic layer by adopting anhydrous magnesium sulfate, and removing the solvent by evaporation to obtain a dicarboxyl compound phenanthrenequinone;
step two, adding the dicarboxyl compound phenanthrenequinone obtained in the step one into an alcoholic solution of dibenzyl ketone, then dropwise adding an alcoholic solution of potassium hydroxide under the condition of stirring, heating and refluxing to obtain a solution after reflux reaction, cooling the solution after reflux reaction to room temperature, filtering to obtain a solid, washing the solid with an alcohol solution, and drying to obtain a monocarbonyl compound 9, 10-phenanthro 1, 12-diphenyl cyclopentadienone;
dissolving alkyne compound diphenylacetylene and monocarbonyl compound 9, 10-phenanthro 1, 12-diphenylcyclopentadienone obtained in the step two in diphenyl ether, then reacting under the condition of stirring and heating, cooling to room temperature to obtain a reacted solution, separating the reacted solution by adopting a silica gel column chromatography, and carrying out rotary evaporation on collected eluent to obtain a phenyl compound 1,2,3, 4-tetraphenyltriphenylene; the eluent adopted by the silica gel column chromatography is prepared from petroleum ether and dichloromethane according to the volume ratio of 15: 1;
step four, dissolving the phenyl compound 1,2,3, 4-tetraphenyltriphenylene obtained in the step three in a polar solvent to obtain a phenyl compound solution, dissolving anhydrous ferric chloride in nitromethane to obtain a ferric chloride solution, then dropwise adding the ferric chloride solution into the phenyl compound solution under the protection of inert gas for reaction to obtain a solution after reaction, mixing the solution after reaction with 0.1mol/L HCl solution, separating by using a separating funnel to obtain an organic layer solution, and filtering to remove the organic solvent to obtain the hexabenzocoronene.
2. The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar is characterized in that the amount ratio of the polycyclic aromatic hydrocarbon phenanthrene to the chromium trioxide in the acetic acid aqueous solution of the chromium trioxide in the step one is 1: 4.
3. The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar according to claim 1, characterized in that in the step one, the volume ratio of acetic acid to water in the acetic acid aqueous solution of the solvent adopted by the acetic acid aqueous solution of the chromium trioxide is 5:2, and the reaction time is 2 h-3 h.
4. The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar according to claim 1, characterized in that the ratio of the amount of the phenanthrene quinone serving as the dicarboxyl compound to the amount of the dibenzyl ketone substance in the alcoholic solution of the dibenzyl ketone in the first step is 1:1, and the solvent adopted in the alcoholic solution of the dibenzyl ketone is methanol or ethanol.
5. The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar according to claim 1, characterized in that the heating reflux temperature in the second step is 60-100 ℃ and the time is 2-5 h.
6. The method for preparing hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar according to claim 1, characterized in that the mass ratio of the alkyne compound tolane to the monocarbonyl compound 9, 10-phenanthro 1, 12-diphenylcyclopentadienone in step three is 1: 1.
7. The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar according to claim 1, characterized in that the heating reaction in the third step is carried out at the temperature of 200-300 ℃ for 3-8 h.
8. The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar according to claim 1, characterized in that a polar solvent in the fourth step is dichloromethane or methanol, and the mass ratio of the phenyl compound to anhydrous ferric chloride is 1: 1.
9. The preparation method for constructing the hexabenzocoronene by utilizing the polycyclic aromatic hydrocarbon phenanthrene in the coal tar according to claim 1, characterized in that the inert gas in the fourth step is nitrogen or argon, and the reaction time is 60-120 min.
CN201911333831.XA 2019-12-23 2019-12-23 Preparation method for constructing hexabenzocoronene by polycyclic aromatic hydrocarbon phenanthrene in coal tar Pending CN110981680A (en)

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Application publication date: 20200410