阅读说明：本技术 一种六氮杂苯并菲衍生物及其合成方法 (Hexaazatriphenylene derivative and synthesis method thereof ) 是由 姚斌 孙洪飞 于 2019-10-25 设计创作，主要内容包括：本发明公开了一种六氮杂苯并菲衍生物及其合成方法,该六氮杂苯并菲衍生物的结构通式为：<Image he="525" wi="567" file="DDA0002248461210000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,通式中X为O或N；R为C<Sub>6</Sub>～C<Sub>40</Sub>烷基或C<Sub>6</Sub>～C<Sub>40</Sub>芳香族取代基。该六氮杂苯并菲衍生物是一种新型N型半导体材料。同时,该合成方法的合成路线简短、产率高,操作简便,反应条件温和易控制,且无需特殊设备。(The invention discloses a hexaazatriphenylene derivative and a synthesis method thereof, wherein the hexaazatriphenylene derivative has a structural general formula as follows: wherein, X in the general formula is O or N; r is C 6 ～C 40 Alkyl or C 6 ～C 40 An aromatic substituent. The hexaazatriphenylene derivative is a novel N-type semiconductor material. Meanwhile, the synthesis method has the advantages of short synthesis route, high yield, simple and convenient operation, mild and easily controlled reaction conditions and no need of special equipment.)

1. The hexaazatriphenylene derivative is characterized by having the following structural general formula:

wherein, X in the general formula is O or N; r is C₆～C₄₀Alkyl or C₆～C₄₀An aromatic substituent.

2. A synthetic method of hexaazatriphenylene derivatives is characterized by comprising the following steps:

(1) Synthesis of 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene

1.1) putting 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene into a mixed solution of acetonitrile and water, heating to 80-90 ℃, and stirring until the 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene is completely dissolved;

1.2) slowly dropwise adding a mixed solution of excess liquid bromine and acetonitrile into a 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene dissolved solution, and continuously reacting a reaction system for 24-72 hours at the temperature of 80-90 ℃ after dropwise adding;

1.3) cooling the reaction system to room temperature, dropwise adding a sodium bisulfite solution to quench the reaction to remove excessive liquid bromine, then filtering, washing with distilled water until the filtrate is neutral, and collecting a filter cake;

1.4) adding carbon tetrachloride to dissolve the filter cake obtained in the step 1.3), then filtering, collecting filtrate, and evaporating carbon tetrachloride to obtain a green solid; finally, washing the green solid with ethanol for multiple times until the filtrate is colorless and transparent liquid to obtain light yellow solid which is 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene;

(2) Synthesis of hexaazatriphenylene derivatives

2.1) adding the 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene obtained in the step 1.4) and the compound A into an organic solvent in an oxygen-free state and in an inert gas atmosphere, adding a catalyst, heating to 70-100 ℃, and reacting for 12-72 hours; the structural general formula of the compound A is as follows:

Wherein, X in the general formula is O or N; r is C₆～C₄₀Alkyl or C₆～C₄₀an aromatic substituent;

2.2) cooling the reaction mixed liquor obtained in the step 2.1) to room temperature, then adding acetone into the reaction mixed liquor, stirring, filtering, washing with deionized water and acetone until the filtrate is colorless, collecting a filter cake, drying, and carrying out column chromatography to obtain a brown yellow solid which is a hexaazatriphenylene derivative.

3. The synthesis method of hexaazatriphenylene derivative according to claim 2, wherein the volume ratio of acetonitrile to water in the mixed solution of acetonitrile and water in step 1.1) is 95-99: 1-5.

4. The synthesis method of a hexaazatriphenylene derivative according to claim 2, wherein the molar ratio of 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene to liquid bromine in step 1.2) is 1: 25-200.

5. A synthesis method of hexaazatriphenylene derivatives according to claim 2, wherein the molar concentration of the sodium bisulfite solution in step 1.3) is 0.5-2 mol/L.

6. The synthesis method of hexaazatriphenylene derivative according to claim 2, wherein the filter cake collected in step 1.3) is completely dissolved and dispersed by adding carbon tetrachloride in step 1.4) and then oscillating for 0.5-1 h under ultrasonic conditions.

7. The synthesis method of a hexaazatriphenylene derivative according to claim 2, wherein the molar ratio of 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene to compound A in step 2.1) is 1: 3-4.

8. the synthesis method of hexaazatriphenylene derivative according to claim 2, wherein the catalyst in step 2.1) is sodium iodide or potassium iodide, and the molar ratio of the added catalyst to 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene is 10-25: 1.

9. A synthesis method of hexaazatriphenylene derivative according to claim 2, wherein the organic solvent in step 2.1) is N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dimethyl methylphosphonate.

10. A synthesis method of hexaazatriphenylene derivative according to claim 2, wherein in the step 2.1), the inert gas is nitrogen or argon.

Technical Field

The invention belongs to the technical field of semiconductor materials, and particularly relates to a hexaazatriphenylene derivative and a synthesis method thereof.

Background

Discotic liquid crystals have wide applications in physical devices such as light emitting diodes, photoconductors, photovoltaic devices, field effect transistors, and optical storage.

In recent years, more and more triphenylene discotic liquid crystal materials are synthesized, but due to the limitation of synthesis methods, the flexible side chains of many triphenylene discotic liquid crystal materials are mostly electron-donating groups such as-OR OR-SR, the accumulation of charges makes most triphenylene derivatives become potential P-type semiconductor materials (hole transport materials), and discotic liquid crystal N-type semiconductor materials with electron transport functions are very rare. In recent years, N-type semiconductor materials have played a significant role in the development of new devices in the technical fields of organic solar cells, organic light emitting diodes, organic field effect transistors, integrated circuits, and the like. With the rapid development of the optoelectronic industry, the demand for N-type semiconductor materials is increasing, and more N-type semiconductor materials are urgently needed to be developed.

The hexaazatriphenylene derivative is a heterocyclic compound very similar to the triphenylene derivative, and the basic core structure of the hexaazatriphenylene derivative is that six nitrogen atoms are introduced on the basis of the triphenylene, so that the electron-withdrawing capability is enhanced, and the hexaazatriphenylene derivative can be widely applied to the field of N-type semiconductor materials, such as an electron transmission layer of a field effect transistor, an electron acceptor material in an organic solar cell and the like. In addition, the traditional synthesis of hexaazatriphenylene derivatives utilizes the condensation reaction of cyclohexexanone and complex diamine (or hexaaminobenzene and complex diketone), the synthesis steps of complex diamine (or diketone) are usually longer, the comprehensive yield of hexaazatriphenylene derivatives is below 10%, and the adjustment range of material properties is also limited.

Therefore, the development of a novel hexaazatriphenylene derivative and the improvement of the overall yield of the hexaazatriphenylene derivative are technical problems to be solved by those skilled in the art.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a hexaazatriphenylene derivative and a synthesis method thereof, wherein the hexaazatriphenylene derivative is a novel N-type semiconductor material, and the synthesis method has the advantages of short synthesis route, high yield, simple and convenient operation, mild and easily controlled reaction conditions and no need of special equipment.

the technical scheme of the invention is realized as follows:

a hexaazatriphenylene derivative has the following structural formula:

Wherein, X in the general formula is O or N; r is C₆～C₄₀Alkyl or C₆～C₄₀An aromatic substituent.

A synthetic method of hexaazatriphenylene derivatives specifically comprises the following steps:

(1) Synthesis of 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene

1.1) putting 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene into a mixed solution of acetonitrile and water, heating to 80-90 ℃, and stirring until the 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene is completely dissolved;

1.2) slowly dropwise adding a mixed solution of excess liquid bromine and acetonitrile into a 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene dissolved solution, and continuously reacting a reaction system for 24-72 hours at the temperature of 80-90 ℃ after dropwise adding;

1.3) cooling the reaction system to room temperature, dropwise adding a sodium bisulfite solution to quench the reaction to remove excessive liquid bromine, then filtering, washing with distilled water until the filtrate is neutral, and collecting a filter cake;

1.4) adding carbon tetrachloride to dissolve the filter cake obtained in the step 1.3), then filtering, collecting filtrate, and evaporating carbon tetrachloride to obtain a green solid; finally, the green solid was washed with ethanol several times until the filtrate was a colorless and transparent liquid to give a pale yellow solid which was 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene.

(2) Synthesis of hexaazatriphenylene derivatives

2.1) adding the 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene obtained in the step 1.4) and the compound A into an organic solvent in an oxygen-free state and in an inert gas atmosphere, adding a catalyst, heating to 70-100 ℃, and reacting for 12-72 hours; the structural general formula of the compound A is as follows:

wherein, X in the general formula is O or N; r is C₆～C₄₀alkyl or C₆～C₄₀an aromatic substituent;

2.2) cooling the reaction mixed liquor obtained in the step 2.1) to room temperature, then adding acetone into the reaction mixed liquor, stirring, filtering, washing with deionized water and acetone until the filtrate is colorless, collecting a filter cake, drying, and carrying out column chromatography to obtain a brown yellow solid which is a hexaazatriphenylene derivative.

Further, the volume ratio of acetonitrile to water in the mixed solution of acetonitrile and water in the step 1.1) is 95-99: 1-5.

Further, in the step 1.2), the molar ratio of 2,3,6,7,10, 11-hexamethyl-1, 4,5,8,9, 12-hexaazatriphenylene to liquid bromine is 1: 25-200.

Further, the molar concentration of the sodium bisulfate solution in the step 1.3) is 0.5-2 mol/L.

Further, adding carbon tetrachloride in the step 1.4), and oscillating for 0.5-1 h under the ultrasonic condition to completely dissolve and disperse the filter cake collected in the step 1.3).

further, in the step 2.1), the molar ratio of the 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene to the compound A is 1: 3-4.

further, the catalyst in the step 2.1) is sodium iodide or potassium iodide, and the molar ratio of the added catalyst to 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene is 10-25: 1.

further, the organic solvent in step 2.1) is N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or dimethyl methylphosphonate.

Further, in step 2.1), the inert gas is nitrogen or argon.

The reaction scheme for synthesizing the hexaazatriphenylene derivative from the 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene is as follows:

In the above formula, X is O or N; r is C₆～C₄₀Alkyl or C₆～C₄₀an aromatic substituent.

Compared with the prior art, the invention has the following beneficial effects:

1. The hexaazatriphenylene derivative is a novel N-type semiconductor material, and effectively promotes the research and development process of the N-type semiconductor material.

2. The method has the advantages of short synthetic route, high yield, high maximum yield up to 64%, simple and convenient operation, mild and easily controlled reaction conditions, and great saving of economic cost, thereby being beneficial to industrial application.

Detailed Description

The present invention will be described in further detail with reference to specific embodiments.

the main reaction formula of the synthetic method is as follows:

(1) Synthesis of 2,3,6,7,10, 11-hexa (dibromomethyl) -1,4,5,8,9, 12-hexaazatriphenylene

(2) Synthesis of the above-mentioned hexaazatriphenylene derivative

In the reaction formula, X is O or N; r is C₆～C₄₀alkyl or C₆～C₄₀aromatic substituent