CN1271051C - Aza aromatic ring substitutional four branched functional molecule material and preparation method - Google Patents

Abstract

The present invention relates to a relates to an aza aromatic ring substitutional four-branch functional molecule material, a preparation method and an application method thereof, which belongs to the technical fields of organic functional molecule materials and organic synthesis intermediates. The aza aromatic ring substitutional four-branch functional molecule material structurally uses teera pentacite as a basic structure framework, and have four branchs, each branch has an aroylation heterocycle, and each aroylation heterocycle at least has on aza atom. Organic compounds prepared by the present invention can be used for organic synthesis of intermediates, molecule semiconductors, current carrier transmission materials, etc., and in addition, the organic compounds prepared by the present invention can also be used for preparing semiconductor polymer films, etc. The organic molecule material has wide application in the technical fields of organic electroluminescent devices, organic field effect transistors, non-linear optics, magnetic materials, etc.

Description

Four-branched functional molecular material substituted by azaaromatic ring and preparation method thereof

technical field

The invention belongs to the technical field of organic functional molecular materials, and specifically relates to a class of four-branch functional molecular materials and a preparation method thereof.

technical background

Organic molecules with specific structures have specific functional properties and can be used as functional molecular materials. Functional organic molecular materials can be used in a wide range of fields, such as molecular semiconductors, carrier transport materials, luminescent materials, nonlinear optical materials, etc. Certain groups or atoms in organic molecules have a strong ability to coordinate with metal ions, and can form metal-organic complexes and coordination polymer materials, which can further expand the properties of materials, including: electrical properties, magnetic properties, photosensitivity and photoelectric conversion performance.

Contents of the invention

The object of the present invention is to propose a class of functional molecular materials with a four-branched structure and a preparation method for the molecular materials.

The four-branched functional molecular material proposed by the present invention is prepared from pentaerythritol tetrabenzenesulfonate or tetrahalogenated pentapentane by reacting with organic molecules containing active hydrogen. Tetrahalogenated pentapentane adopts tetraiodopentapentane or tetrabromopentapentane, and the organic molecules with active hydrogen adopt various azaaromatic ring molecules and various derivatives, which have a pentaerythryl group as the skeleton. And connect with nitrogen-containing aromatic heterocyclic molecules to form a dendritic molecule with four identical branches, and its structural formula is as follows:

Wherein R ₁ and R ₂ are various substituents, X is an N atom or CH, and the compounds with this structure are collectively referred to as tetrakis((azaaryl ring)-1-ylmethyl)methane.

For the functional molecular material proposed by the present invention, different materials are used as the precursors of nitrogen-heteroaromatic ring molecules containing active hydrogen, so that organic molecular materials with different structures can be obtained. The present invention particularly proposes the following four-branched functional organic molecular materials:

(1) English name: Tetrakis(pyrrol-l-ylmethyl)methane

Chinese name: Tetra(pyrrol-1-ylmethyl)methane

The molecular formula is C ₂₁ H ₂₄ N ₄ , and the chemical structure is as follows:

(2) English name: Tetrakis(indol-l-ylmethyl)methane

Chinese name: Tetra(indol-1-ylmethyl)methane

The molecular formula is C ₃₇ H ₃₂ N ₄ , and the chemical structure is as follows:

(3) English name: Tetrakis (imidazol-l-ylmethyl) methane

Chinese name: Tetrakis(imidazol-1-ylmethyl)methane

The molecular formula is C ₁₇ H ₂₀ N ₈ , and the chemical structure is as follows:

A general method for preparing the above-mentioned four-branched functional molecular material is: using pentaerythritol tetrabenzenesulfonate or tetrahalogenated pentapentane as the starting material, and preparing it by reacting with various organic molecules containing active hydrogen. Among them, the tetrahalogenated pentapentane adopts tetraiodopentapentane or tetrabromopentapentane; organic molecules with active hydrogen can adopt azaaromatic ring molecules and various derivatives. Specific steps are as follows:

In a nitrogen atmosphere, add sodium hydride (NaH) and an organic solvent into the reaction flask, and then add a solution of nitrogen-containing heteroaromatic ring molecules dropwise under stirring. Continue to stir for 15-60 minutes, add pentaerythritol tetrabenzenesulfonate or tetrahalogenated pentapentane solution dropwise, and then react at 50-180° C. for 6-24 hours. The organic solvent can be one of N,N-dimethylformamide (DMF), tetrahydrofuran, dioxane, tetraethylene glycol dimethyl ether (TG) or a mixed solvent of several of them. In the above steps, the molar ratios of nitrogen-containing heteroaromatic ring molecules to sodium hydride, pentaerythritol tetrabenzenesulfonate or tetrahalogenated pentapentane are respectively 0.8-1, 4.2-6, and the nitrogen-containing heteroaryl ring molecules in the reaction solution The concentration is 0.2-5 mol/liter. After the reaction, cool down, and slowly add ice-cold ethanol-water mixture to neutralize excess NaH until no bubbles emerge. The reaction solution was poured into a large amount of ice water, a precipitate was precipitated, filtered, washed with ethanol and recrystallized.

In the above-mentioned steps, tetrahalogenated pentapentane can adopt tetraiodopentapentane or tetrabromopentapentane.

In the above steps, if pyrrole is used as a nitrogen-containing heteroaromatic ring molecule, compound (A) is obtained.

In the above steps, if indole is used as a nitrogen-containing heteroaryl ring molecule, compound (B) is obtained.

In the above steps, if imidazole (Imidole) is used as a nitrogen-containing heteroaromatic ring molecule, compound (C) is obtained.

The four-branch molecular material prepared by the invention has multiple uses, and they can also be formed into a film by vacuum thermal evaporation, which is a kind of functional organic thin film material. These organic molecules can also be used as intermediates in organic synthesis, and through further grafting and functionalization, more functional molecular materials can be constructed as needed.

The compound (A) contains four pyrrole units, and can be polymerized by electrochemical methods, or can be polymerized by ultraviolet light and oxidants to form conjugated polymers. Such polymers can be used as electrochromic polymers and as precursors for polymeric semiconductors. For example, the organic molecules are vapor-deposited on the metal substrate to form a film by vacuum thermal evaporation, and then irradiated with ultraviolet light to polymerize it to form a polymer film, and then vapor-deposit metal spots on the polymer film as the upper electrode, so that A metal-polymer-metal structure is formed. A voltage is applied between the upper electrode and the bottom electrode, and it is found that the resistance value of this structure changes significantly with the change of voltage, showing good nonlinear resistance characteristics, so it is expected to be used in the production of organic field effect transistors.

Other organic molecular materials reported in this invention also have their own applications. The compound (B) itself has semiconducting properties, and similar to the compound (A), the film of this molecular material can also form a polymer or a multimer, which can be used as a semiconducting polymer material. Compound (B) can also form a spiro molecule through intramolecular oxidation coupling, and has a very high melting point. This spiro molecule can be used as an organic semiconductor and a hole transport material, and has a wide range of applications in the field of field effect transistors and organic electroluminescent devices. the use of.

Compound (C) has similar uses as compound (A). In addition, the compound (C) can also form a coordination complex network structure with metal ions, and can constitute a magnetic polymer material.

Detailed ways

Further describe the present invention below by embodiment

Example 1

Under a nitrogen atmosphere, add 4.0 grams (0.1 mole) of 60% sodium hydride, 20 milliliters of DMF to the reaction flask, add dropwise a solution of 20 milliliters of DMF containing 6.2 grams (0.093 mole) of pyrrole under stirring, stir at room temperature for 1 hour, then drop A 30 ml DMF solution containing 6.0 g (0.0155 mol) of tetrabromopentapentane was added, and then the temperature was raised to 60° C. for 24 hours of reaction. After cooling, slowly add 20 milliliters of ice-cold 50% ethanol aqueous solution to the reaction flask until no bubbles emerge, then pour the reaction solution into 200 milliliters of ice water, a precipitate is precipitated, filtered, and recrystallized with ethanol to obtain 4.6 grams White crystals with a yield of 82%, namely compound (A).

Melting point (m.p.): 168-170°C.

Elemental analysis: C (75.85%), H (7.28%), N (16.92%).

IR (KBr, cm ^-1 ): 3099, 2926, 1493, 1450, 1281, 1088, 964, 733, 618. ¹ H NMR (500MHz, CDCl ₃ , δ): 7.58(t, 8H), 7.04(t, 8H), 3.94(s, 8H). ¹³ C NMR (500MHz, CDCl ₃ , δ): 45.1, 50.8, 109.3, 122.5 GC-MS m/z (%): 333(12.7), 332(52.9), 118 (100), 80(63.7).

Example 2

Under a nitrogen atmosphere, add 0.1 mole of 60% sodium hydride and 20 ml of DMF to the reaction flask, add dropwise a 20 ml DMF solution containing 0.093 mole of indole under stirring, stir at room temperature for 1 hour, then add dropwise a solution containing 0.0155 mole of tetrabromo 30 ml of DMF solution of pentapentane was then heated to 150° C. for 24 hours. After cooling, slowly add 20 ml of ice-cold 50% ethanol aqueous solution to the reaction bottle until no bubbles come out, then pour the reaction solution into 200 ml of ice water, precipitate precipitates, filter, and wash thoroughly with DMF, ethanol, and ether , to obtain a white solid with a yield of 80%, that is, compound (B).

Melting point (m.p.): >300°C.

IR (KBr, cm ^-1 ): 3026, 1687, 1510, 1453, 1308, 1263, 766, 741, 725, 425.

¹ H NMR (500MHz, DMSO, δ): 6.5-7.7(m, 24H), 4.3-4.6(m, 8H).

Example 3

Under a nitrogen atmosphere, add 0.1 mole of 60% sodium hydride and 20 ml of DMF to the reaction flask, dropwise add 20 ml of DMF solution containing 0.093 mole of imidazole under stirring, stir at room temperature for 1 hour, then dropwise add 20 ml of DMF solution containing 0.0155 mole of tetrabromoquaternary 30 ml of DMF solution of pentane, then heated to 60°C for 24 hours. After cooling, slowly add 20 milliliters of ice-cold 50% ethanol aqueous solution to the reaction flask until no bubbles emerge, then pour the reaction solution into 200 milliliters of ice water, a precipitate is precipitated, filtered, and recrystallized with ethanol-water to obtain White crystals with a yield of 70%, namely compound (C).

Melting point (m.p.): 176-178°C.

IR (KBr, cm ^-1 ): 3106, 1514, 1443, 1292, 1234, 1109, 1086, 1027, 918, 878, 742, 660.

¹ H NMR (500MHz, DMSO, δ): 7.49(s, 4H), 6.9-7.0(d, 8H), 4.15-4.19(d, 8H).

Claims (8)

1. A four-branched molecular material, which takes pentaerythritol as a skeleton and connects with nitrogen-containing heteroaryl ring molecules to form a branched molecule with four identical branches. It is characterized in that the molecular material is composed of pentaerythritol tetrabenzenesulfonate ester or tetrahalogenated pentapentane as the starting material, which is prepared by reacting with organic molecules containing active hydrogen, wherein tetrahalogenated pentapentane adopts tetraiodopentapentane or tetrabromopentapentane, containing The organic molecule of active hydrogen adopts nitrogen heteroaryl ring molecular compound, and the nitrogen heteroaryl ring molecular compound is selected from pyrrole, indole or imidazole. 2. The four-branched molecular material according to claim 1, characterized in that the azaaromatic ring molecule is pyrrole, the molecular formula of the molecular material is C ₂₁ H ₂₄ N ₄ , and the chemical structural formula is as follows:

The name of the compound is: tetrakis(pyrrol-1-ylmethyl)methane. 3. The tetra-branched molecular material according to claim 1, characterized in that the azaaromatic ring molecule is indole, the molecular formula of the molecular material is C ₃₇ H ₃₂ N ₄ , and the chemical structural formula is as follows:

The name of the compound is: tetrakis(indol-1-ylmethyl)methane. 4. The four-branched molecular material according to claim 1, characterized in that the azaaromatic ring molecule is imidazole, the molecular formula of the molecular material is C ₁₇ H ₂₀ N ₈ , and the chemical structural formula is as follows: The name of the compound is: tetrakis(imidazol-1-ylmethyl)methane. 5. A method for preparing the four-branch molecular material according to claim 1, characterized in that the specific steps are as follows: in a nitrogen atmosphere, add sodium hydride and an organic solvent to the reaction bottle, and then add nitrogen-containing impurities dropwise under stirring. For the solution of aromatic ring molecules, continue to stir for 15 to 60 minutes, add tetrahalogenated pentapentane solution dropwise, and then react at 50 to 180°C for 6 to 24 hours. The organic solvent is N, N-dimethylformamide, tetrahydrofuran, One of dioxane, tetraethylene glycol dimethyl ether or a mixed solvent; the molar ratios of nitrogen-containing heteroaromatic ring molecules to sodium hydride and tetrahalogenated pentapentane are 0.8-1 and 4.2-6 respectively, and the reaction The concentration of nitrogen-containing heteroaromatic ring molecules in the liquid is 0.2 to 5 moles/liter; after the reaction is completed, cool down and add ice-cold ethanol-water mixture to neutralize excess sodium hydride until no bubbles emerge; pour the reaction liquid Into a large amount of ice water, a precipitate precipitated out, filtered, washed with ethanol and recrystallized. 6. The preparation method according to claim 5, characterized in that pyrrole is used as a nitrogen-containing heteroaromatic ring molecule, and the reaction temperature is 50-80°C to obtain compound (A): tetrakis(pyrrol-1-ylmethyl)methane. 7. The preparation method according to claim 5, characterized in that indole is used as the nitrogen-containing heteroaromatic ring molecule, and the reaction temperature is 120-180°C to obtain compound (B): tetrakis(indol-1-ylmethyl) methane. 8. The preparation method according to claim 5, characterized in that imidazole is used as the nitrogen-containing heteroaromatic ring molecule, and the reaction temperature is 50-80°C to obtain compound (C): tetrakis(imidazol-1-ylmethyl)methane .