A simple synthesis of 1,3,5,7-tetraalkoxyanthracene derivatives

Abstract

The application discloses a simple synthesis method of 1,3,5,7-tetraalkoxy anthracene derivatives, and particularly relates to the field of anthracene derivatives, and comprises the following steps: dissolving 3,5-dialkoxybenzene methanol in 1,2-dichloroethane, adding a Lewis acid into the 3,5-dialkoxybenzene methanol under preset conditions to perform a Friedel-Crafts alkylation reaction, and obtaining 1,3,5,7-tetraalkoxy anthracene derivatives. The 3,5-dialkoxybenzene methanol is subjected to a Friedel-Crafts alkylation reaction with 1,2-dichloroethane under the catalysis of a Lewis acid to rapidly synthesize 1,3,5,7-tetraalkoxy anthracene derivatives in one pot, and no special catalyst, solvent and reaction temperature are needed in the reaction process, so that the synthesis difficulty is reduced.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of anthracene derivatives, in particular to a simple synthesis method of 1,3,5,7-tetraalkoxy anthracene derivatives. BACKGROUND

[0002] 1,3,5,7-tetraalkoxy anthracene derivatives are an organic skeleton with important value. Anthracene derivatives have high luminescent efficiency and can be used as luminescent materials or luminescent host materials, which are applied in organic electroluminescent devices. These devices have the advantages of low manufacturing cost and long service life, and thus have broad application prospects in the fields of display and lighting.

[0003] Polysubstituted alkoxyl anthracene derivatives are mainly synthesized by intermolecular chemical reactions. There are few reports on the synthesis method of polysubstituted alkoxyl anthracene derivatives, and the reaction substrates are expensive, the reaction conditions are harsh, and special catalysts, solvents and reaction temperatures are required, which increases the difficulty and cost of synthesis. SUMMARY

[0004] The main purpose of the present application is to provide a simple synthesis method of 1,3,5,7-tetraalkoxy anthracene derivatives, aiming to solve the problem of high synthesis difficulty of existing anthracene derivatives.

[0005] To achieve the above-mentioned purpose, the present application provides a 1,3,5,7-tetraalkoxy anthracene derivative, whose structural formula is as follows:

[0006]

[0007] Among them, R is a linear alkyl group.

[0008] Optionally, R is C 1-6 alkyl.

[0009] To achieve the above-mentioned purpose, the present application further provides a simple synthesis method of the above-mentioned 1,3,5,7-tetraalkoxy anthracene derivative, which comprises: dissolving 3,5-dialkoxybenzene methanol in a solvent, and adding Lewis acid to it under a predetermined condition to carry out Friedel-Crafts alkylation reaction, to obtain 1,3,5,7-tetraalkoxy anthracene derivative.

[0010] Optionally, the molar ratio of 3,5-dialkoxybenzene methanol to Lewis acid is 1:3-20.

[0011] Optionally, the Lewis acid is boron trifluoride etherate.

[0012] Optionally, the solvent is 1,2-dichloroethane, and the reaction concentration of 3,5-dialkoxybenzene methanol is 0.1-10 mmoL / L.

[0013] Optionally, the reaction temperature of the Friedel-Crafts alkylation reaction is 30-80 DEG C, and the reaction time is 28-32 h.

[0014] Optionally, the preset condition is: argon atmosphere, and the temperature is -2-2 DEG C.

[0015] Optionally, after the Friedel-Crafts alkylation reaction is completed, the reaction product is subjected to the following post-treatment: water is added to the reaction product for quenching and extraction; the organic phase obtained by extraction is subjected to vacuum evaporation; and the reaction product after evaporation is subjected to column chromatography purification.

[0016] To achieve the above object, the application further provides application of the above 1,3,5,7-tetraalkoxyl anthracene derivative in an organic electroluminescent device.

[0017] Compared with the prior art, the application has the following beneficial effects:

[0018] The simple synthesis method of the 1,3,5,7-tetraalkoxyl anthracene derivative of the application is that 3,5-dialkoxybenzyl alcohol is subjected to Friedel-Crafts alkylation reaction with 1,2-dichloroethane under the catalysis of a Lewis acid to rapidly synthesize 1,3,5,7-tetraalkoxyl anthracene derivative in one pot, and the reaction process does not need special catalysts, solvents and reaction temperature, thereby reducing the difficulty of synthesis; raw materials are simple and easy to obtain, and the operation is simple, thereby reducing the synthesis cost; and the substrate 1,3,5,7-tetraalkoxyl anthracene derivative has a wide application range. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 A high-resolution mass spectrum of the methoxyl anthracene derivative obtained in Example 1 of the simple synthesis method of the 1,3,5,7-tetraalkoxyl anthracene derivative of the application;

[0020] Figure 2 A high-resolution mass spectrum of the methoxyl anthracene derivative obtained in Example 1 of the simple synthesis method of the 1,3,5,7-tetraalkoxyl anthracene derivative of the application; 1 HNMR diagram;

[0021] Figure 3 A high-resolution mass spectrum of the methoxyl anthracene derivative obtained in Example 1 of the simple synthesis method of the 1,3,5,7-tetraalkoxyl anthracene derivative of the application; 13 CNMR;

[0022] Figure 4 A high-resolution mass spectrum of the methoxyl anthracene derivative obtained in Example 1 of the simple synthesis method of the 1,3,5,7-tetraalkoxyl anthracene derivative of the application;

[0023] Figure 5 A high-resolution mass spectrum of the methoxyl anthracene derivative obtained in Example 1 of the simple synthesis method of the 1,3,5,7-tetraalkoxyl anthracene derivative of the application;

[0024] Figure 6 The butoxy anthracene derivative obtained in Example 2 of the simple synthesis method of the 1,3,5,7-tetraalkoxy anthracene derivative of the present application 1 HNMR chart;

[0025] Figure 7 The fluorescence performance test result chart of the butoxy anthracene derivative obtained in Example 2 of the simple synthesis method of the 1,3,5,7-tetraalkoxy anthracene derivative of the present application

[0026] The implementation, functional features and advantages of the present application will be further described with reference to the accompanying drawings in conjunction with the embodiments. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solutions and advantages of the present application more clear, the technical solutions of the present application will be described clearly and completely in conjunction with the drawings in the present application. Obviously, the described embodiments are part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the present application.

[0028] The first embodiment of the present application provides a 1,3,5,7-tetraalkoxy anthracene derivative, and the structural formula is as follows:

[0029]

[0030] Wherein, R is a linear alkyl group, and further, R is C 1-6 alkyl group.

[0031] The second embodiment of the present application provides a simple synthesis method of a 1,3,5,7-tetraalkoxy anthracene derivative, comprising:

[0032] 1,2-dichloroethane is added to 3,5-dialkoxybenzene methanol, and a Lewis acid is added under a preset condition to perform a Friedel-Crafts alkylation reaction to obtain a 1,3,5,7-tetraalkoxy anthracene derivative. The specific steps are as follows:

[0033] The 3,5-dialkoxybenzyl alcohol is added to a reaction container, 1,2-dichloroethane is added to dissolve the 3,5-dialkoxybenzyl alcohol, the concentration of the 3,5-dialkoxybenzyl alcohol in the mixture of the 3,5-dialkoxybenzyl alcohol and the 1,2-dichloroethane is 0.1-10 mmoL / L; the argon is pumped for three times under the ice water bath (the temperature is -2-2 ℃), the boron trifluoride ether (Lewis acid) is injected into the reaction container by using a syringe, the molar ratio of the 3,5-dialkoxybenzyl alcohol to the boron trifluoride ether is 1:3-20, the Friedel-Crafts alkylation reaction is carried out by heating to 30-80 ℃, the reaction product is quenched by adding water after the reaction for 28-32 h, and the quenched reaction product is extracted; the extracted organic phase is evaporated under reduced pressure; the evaporated reaction product is purified by column chromatography, the eluent includes dichloromethane and petroleum ether in a volume ratio of 1:4-8, and the 1,3,5,7-tetraalkoxyanthracene derivative is obtained.

[0034] The reaction formula is as follows:

[0035]

[0036] In the formula, R is C 1-6 alkyl. The reaction mechanism is as follows:

[0037]

[0038] In example 1, R is CH3

[0039] The reaction concentration of 168 mg of 3,5-dialkoxybenzyl alcohol is 1 mmoL / L, which is added to a two-necked flask with a condenser and a magnetic stirrer, 150 ml of 1,2-dichloroethane is added, the argon is pumped for three times under the ice water bath (the temperature is 0 ℃), 630 μl of boron trifluoride ether is extracted by using a syringe and injected into the two-necked flask through a rubber stopper, the condensation reflux is carried out under the oil bath at 80 ℃, the reaction product is quenched by adding water after the reaction for 30 h, the organic phase and the aqueous phase are separated, the organic phase is collected, and the water is extracted with 20 ml of dichloromethane (DCM) three times; the extracted organic phase is evaporated under reduced pressure; the evaporated reaction product is purified by column chromatography, the eluent includes dichloromethane and petroleum ether in a volume ratio of 1:4, and the 1,3,5,7-tetraalkoxyanthracene derivative is obtained.

[0040] The reaction formula of the example is as follows:

[0041]

[0042] In the example, the reaction process is detected by TLC, and the product obtained in the example is characterized by ESI-MS, 1 HNMR, 13 CNMR, and the results are shown in the following table. Figures 1-3 The product is obtained.Figure 1 The molecular weight error is less than 1 ppm, indicating reliable data. Figure 2 , 3 It can be inferred that its structure is C. 18 H 10 O4, namely a 1,3,5,7-tetramethoxyanthracene derivative. The fluorescence properties of the 1,3,5,7-tetramethoxyanthracene derivative obtained in this example were also tested, and the results are as follows. Figure 4 As shown in the figure, its quantum yield QY is 37.6%, fluorescence lifetime τ is 8.41 ns, and maximum excitation wavelength λ is... EX =390nm, maximum emission wavelength λ Em =460nm.

[0043] Example 2R is C4H9

[0044] 252 mg of 3,5-dialkoxybenzyl alcohol (1 mmol / L) was added to a two-necked flask equipped with a condenser and a magnetic stir bar. 150 mL of 1,2-dichloroethane was added, and the flask was purged three times with argon gas in an ice-water bath (0°C). 630 μL of boron trifluoride diethyl ether was drawn using a syringe and injected into the flask through a rubber stopper. The mixture was refluxed in an oil bath at 80°C for 30 h. Water was added to quench the reaction product, separating the organic and aqueous phases. The organic phase was collected, and water was extracted three times with 20 mL of dichloromethane (DCM). The extracted organic phase was then evaporated under reduced pressure. The evaporated reaction product was purified by column chromatography using dichloromethane and petroleum ether in a 1:8 volume ratio to obtain a 1,3,5,7-tetraalkoxyanthracene derivative.

[0045] The reaction formula for this embodiment is:

[0046]

[0047] In this embodiment, the reaction progress was monitored by TLC. The product obtained in this embodiment was also analyzed by HRMS. 1 HNMR characterization, results as follows Figures 5-6 As shown. From Figure 5 Molecular weight errors of less than 10 ppm can be obtained, indicating reliable data. From... Figure 6 Its structural formula can be deduced to be C. 30 H 40 O4, namely a 1,3,5,7-tetrabutanoxyanthracene derivative. The fluorescence properties of the 1,3,5,7-tetrabutanoxyanthracene derivative obtained in this example were also tested, and the results are as follows. Figure 7 As shown in the figure, its quantum yield QY is 24.2%, and the maximum excitation wavelength λ is... EX =380nm, maximum emission wavelength λEX = 450 nm.

[0048] The third embodiment of the present application provides a use of 1,3,5,7-tetraalkoxyanthracene derivatives in an organic electroluminescent device.

[0049] The above merely provides the preferred embodiments of the present application and is not intended to limit the patent scope of the present application, and any equivalent structure or equivalent flow transformation made by the contents of the present application specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A simple synthesis method of 1, 3, 5, 7-tetraalkoxyanthracene derivatives, characterized by, The application relates to a method for preparing 1,3,5,7-tetraalkoxyanthracene derivatives. The 3,5-dialkoxybenzene methanol is dissolved in a solvent, and a Lewis acid is added thereto under preset conditions to perform a Friedel-Crafts alkylation reaction, so as to obtain the 1,3,5,7-tetraalkoxyanthracene derivative, which has the structural formula as shown in the following formula: The Lewis acid is boron trifluoride etherate; the Friedel-Crafts alkylation reaction is carried out at a reaction temperature of 30-80 DEG C and a reaction time of 28-32 h.

2. The process for the facile synthesis of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that, The molar ratio of the 3,5-dialkoxybenzene methanol to the Lewis acid is 1:3-20.

3. The process for the facile synthesis of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that, The solvent is 1,2-dichloroethane, and the reaction concentration of the 3,5-dialkoxybenzene methanol is 0.1-10 mmoL / L.

4. The process for the facile synthesis of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that, The preset condition is an argon atmosphere and a temperature of-2-2 DEG C.

5. The process for the facile synthesis of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that, After the Friedel-Crafts alkylation reaction is completed, the reaction product is subjected to the following post-treatment: Water is added to the reaction product to perform quenching and extraction; The organic phase obtained through extraction is subjected to reduced-pressure evaporation; The reaction product after evaporation is subjected to column chromatography purification.

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