Simple synthesis method of 1, 3, 5, 7-tetraalkoxy anthracene derivative

Abstract

The invention discloses a simple and convenient synthesis method of a 1, 3, 5, 7-tetraalkoxy anthracene derivative, and particularly relates to the field of anthracene derivatives, and the simple and convenient synthesis method comprises the following steps: dissolving 3, 5-dialkoxy benzyl alcohol in 1, 2-dichloroethane, adding Lewis acid under preset conditions, and carrying out Friedel-Crafts alkylation reaction to obtain the 1, 3, 5, 7-tetraalkoxy anthracene derivative. According to the method, the 1, 3, 5-dialkoxy benzyl alcohol and 1, 2-dichloroethane are subjected to Friedel-Crafts alkylation reaction under the catalysis of Lewis acid to quickly synthesize the 1, 3, 5, 7-tetraalkoxy anthracene derivative in one pot, special catalyst, solvent and reaction temperature are not needed in the reaction process, and the synthesis difficulty is reduced.

Description

Technical Field

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

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

[0003] Polysubstituted alkoxyanthracene derivatives are mainly synthesized through intermolecular chemical reactions. There are few reports on the synthesis methods of polysubstituted alkoxyanthracene derivatives. In addition, the reaction substrates are expensive, the reaction conditions are relatively harsh, and special catalysts, solvents and reaction temperatures are required, which increases the difficulty and cost of the synthesis. Summary of the invention

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

[0005] To achieve the above purpose, the present application provides a 1,3,5,7-tetraalkoxyanthracene derivative, the structural formula of which is:

[0006]

[0007] Wherein, R is a straight chain alkyl group.

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

[0009] To achieve the above objectives, the present application also provides a simple synthesis method of the above-mentioned 1,3,5,7-tetraalkoxyanthracene derivatives, comprising: dissolving 3,5-dialkoxybenzyl alcohol in a solvent, and adding Lewis acid thereto under preset conditions to carry out Friedel-Crafts alkylation reaction to obtain 1,3,5,7-tetraalkoxyanthracene derivatives.

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

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

[0012] Optionally, the solvent is 1,2-dichloroethane and the reaction concentration of 3,5-dialkoxybenzyl alcohol is 0.1-10 mmol / L.

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

[0014] Optionally, the preset conditions are: argon atmosphere, temperature of -2-2°C.

[0015] Optionally, after the Friedel-Crafts alkylation reaction is completed, the reaction product is post-treated as follows: water is added to the reaction product for quenching and extraction; the organic phase obtained by the extraction is evaporated under reduced pressure; and the evaporated reaction product is purified by column chromatography.

[0016] To achieve the above objectives, the present application also provides a use of the above 1,3,5,7-tetraalkoxyanthracene derivative in an organic electroluminescent device.

[0017] Compared with the prior art, the beneficial effects of this application are as follows:

[0018] The invention discloses a simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives. 3,5-dialkoxybenzyl alcohol is subjected to Friedel-Crafts alkylation reaction with 1,2-dichloroethane under the catalysis of Lewis acid to quickly synthesize 1,3,5,7-tetraalkoxyanthracene derivatives in one pot. No special catalyst, solvent and reaction temperature are required during the reaction process, which reduces the difficulty of synthesis. The raw materials are simple and easy to obtain, the operation is simple, and the synthesis cost is reduced. The substrate 1,3,5,7-tetraalkoxyanthracene derivative has a wide application range. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a high-resolution mass spectrum of the methoxyanthracene derivative obtained in Example 1 of a convenient method for synthesizing 1,3,5,7-tetraalkoxyanthracene derivatives of the present application;

[0020] Figure 2 The methoxyanthracene derivative obtained in Example 1 of the present invention is a simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives. 1 HNMR spectra;

[0021] Figure 3 The methoxyanthracene derivative obtained in Example 1 of the present invention is a simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives. 13 CNMR;

[0022] Figure 4 This is a graph showing the fluorescence performance test results of the methoxyanthracene derivative obtained in Example 1 of a simple synthesis method for 1,3,5,7-tetraalkoxyanthracene derivatives of the present application;

[0023] Figure 5 This is a high-resolution mass spectrum of a butoxyanthracene derivative obtained in Example 2 of a convenient method for synthesizing 1,3,5,7-tetraalkoxyanthracene derivatives of the present application;

[0024] Figure 6 The butoxy anthracene derivative obtained in Example 2 of the present invention is a convenient method for synthesizing 1,3,5,7-tetraalkoxy anthracene derivatives. 1 HNMR spectra;

[0025] Figure 7 This is a graph showing the fluorescence performance test results of the butoxyanthracene derivative obtained in Example 2 of a simple synthesis method for 1,3,5,7-tetraalkoxyanthracene derivatives of the present application.

[0026] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solutions and advantages of this application clearer, the technical solutions in this application will be clearly and completely described below in conjunction with the drawings in this application. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0028] The first embodiment of the present invention provides a 1,3,5,7-tetraalkoxyanthracene derivative, the structural formula of which is:

[0029]

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

[0031] The second embodiment of the present invention provides a simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives, comprising:

[0032] Add 1,2-dichloroethane to 3,5-dialkoxybenzyl alcohol, and add Lewis acid under preset conditions to carry out Friedel-Crafts alkylation reaction to obtain 1,3,5,7-tetraalkoxyanthracene derivatives. The specific steps are as follows:

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

[0034] The reaction formula is:

[0035]

[0036] Where R is C 1-6 Alkyl. The reaction mechanism is as follows:

[0037]

[0038] Example 1 R is CH3

[0039] 168 mg of 3,5-dialkoxybenzyl alcohol at a reaction concentration of 1 mmoL / L was added to a two-necked bottle with a condenser and a magnet, 150 ml of 1,2-dichloroethane was added thereto, argon was pumped out three times in an ice-water bath (temperature of 0°C), 630 μl of boron trifluoride ether was drawn out using a syringe and injected into the two-necked bottle through a rubber stopper, condensed and refluxed in an oil bath at 80°C, and after reacting for 30 hours, water was added to the reaction product for quenching, the organic phase and the aqueous phase were separated, the organic phase was collected, and the water was extracted three times with 20 ml of dichloromethane (DCM); the organic phase obtained by extraction was evaporated under reduced pressure; the reaction product after evaporation was purified by column chromatography, and the eluent included dichloromethane and petroleum ether in a volume ratio of 1:4 to obtain 1,3,5,7-tetraalkoxyanthracene derivatives.

[0040] The reaction formula of the present embodiment is:

[0041]

[0042] In this example, the reaction progress was detected by TLC. The product obtained in this example was subjected to ESI-MS, 1 HNMR, 13 CNMR characterization, the results are as follows Figure 1-3 As shown. Figure 1 The molecular weight error can be less than 1ppm, and the data is reliable. Figure 2 , 3 It can be inferred that its structure is C 18 H 10 O4, i.e., 1,3,5,7-tetramethyleneoxyanthracene derivative. At the same time, the fluorescence properties of the 1,3,5,7-tetramethyleneoxyanthracene derivative obtained in this example were tested, and the results were as follows. Figure 4 As shown in the figure, it can be concluded that its quantum yield QY is 37.6%, the fluorescence lifetime τ is 8.41ns, and the maximum excitation wavelength λ EX =390nm, maximum emission wavelength λ Em =460nm.

[0043] Example 2 R is C4H9

[0044] 252 mg of 3,5-dialkoxybenzyl alcohol at a reaction concentration of 1 mmoL / L was added to a two-necked bottle with a condenser and a magnet, 150 ml of 1,2-dichloroethane was added thereto, argon was pumped out three times in an ice-water bath (temperature of 0°C), 630 μl of boron trifluoride ether was drawn out using a syringe and injected into the two-necked bottle through a rubber stopper, condensed and refluxed in an oil bath at 80°C, and after reacting for 30 hours, water was added to the reaction product for quenching, the organic phase and the aqueous phase were separated, the organic phase was collected, and the water was extracted three times with 20 ml of dichloromethane (DCM); the organic phase obtained by extraction was evaporated under reduced pressure; the reaction product after evaporation was purified by column chromatography, and the eluent included dichloromethane and petroleum ether in a volume ratio of 1:8 to obtain 1,3,5,7-tetraalkoxyanthracene derivatives.

[0045] The reaction formula of the present embodiment is:

[0046]

[0047] In this example, the reaction progress was detected by TLC. The product obtained in this example was subjected to HRMS, 1 HNMR characterization, the results are as follows Figure 5-6 As shown. Figure 5 The molecular weight error can be less than 10ppm, and the data is reliable. Figure 6 It can be inferred that its structural formula is C 30 H 40 O4, i.e., 1,3,5,7-tetrabutaneoxyanthracene derivative. At the same time, the fluorescence properties of the 1,3,5,7-tetrabutaneoxyanthracene derivative obtained in this example were tested, and the results were as follows. Figure 7 As shown in the figure, it can be concluded that its quantum yield QY is 24.2% and the maximum excitation wavelength λ EX =380nm, maximum emission wavelength λEX =450nm.

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

[0049] The above are only preferred embodiments of the present application, and are not intended to limit the patent scope of the present application. Any equivalent structure or equivalent process transformation made using 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 1,3,5,7-tetraalkoxyanthracene derivative, characterized in that: Its structural formula is: Wherein, R is a straight chain alkyl group.

2. The 1,3,5,7-tetraalkoxyanthracene derivative according to claim 1, characterized in that R is C 1-6 alkyl.

3. A simple method for synthesizing a 1,3,5,7-tetraalkoxyanthracene derivative as claimed in any one of claims 1 to 2, characterized in that: include: 3,5-Dialkoxybenzyl alcohol is dissolved in a solvent, and a Lewis acid is added thereto under preset conditions to carry out a Friedel-Crafts alkylation reaction to obtain a 1,3,5,7-tetraalkoxyanthracene derivative.

4. The simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that: The molar ratio of the 3,5-dialkoxybenzyl alcohol to the Lewis acid is 1:3-20.

5. The simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that: The Lewis acid is boron trifluoride etherate.

6. The simple synthesis method 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-dialkoxybenzyl alcohol is 0.1-10 mmol / L.

7. The simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that: The reaction temperature of the Friedel-Crafts alkylation reaction is 30-80° C., and the reaction time is 28-32 h.

8. The simple synthesis method of 1,3,5,7-tetraalkoxyanthracene derivatives according to claim 1, characterized in that: The preset conditions are: argon atmosphere, temperature -2-2°C.

9. The simple synthesis method 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 post-treated as follows: adding water to the reaction product for quenching and extraction; The organic phase obtained by extraction is evaporated under reduced pressure; The evaporated reaction product was purified by column chromatography.

10. Use of the 1,3,5,7-tetraalkoxyanthracene derivative according to any one of claims 1 to 2 in an organic electroluminescent device.

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