Preparation method and three-dimensional application of 4-{[(e)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol schiff base

Abstract

The present invention discloses a preparation method and three-dimensional application of a 4-{[(E)-(2-phenylpropane-2-yl)nitrogen-ylidene]methyl}benzene-1,3-diphenol Schiff base. Specifically, the molecular structure of the Schiff base compound is shown in the following formula (I): wherein R 1 C 1‑6 Alkyl, R 2 is an aryl group, R 3 C 1‑12 The Schiff base compound has high transparency and good light transmittance in solutions, solids and other media, and can be stored and used stably for a long time.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of optical materials, in particular to a preparation method and three-dimensional application of 4-{[(E)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol Schiff base. BACKGROUND

[0002] The current three-dimensional display technology can be divided into four categories: split light stereoscopic glasses, automatic split light stereoscopic display, holography (Hologram) and volumetric three-dimensional display. The first two of them should be familiar technologies, they both use parallax to give people the feeling of 3D display: showing slightly different images to the left and right eyes, thus deceiving the brain and making the observer feel 3D. The 3D scene constructed by the artificial parallax method is not natural, which increases the brain burden of the observer, so that people will have headaches after a long time. The holography does not use digital means, but uses interference and diffraction of light waves. It can only generate static three-dimensional optical scenes, and has requirements for observation angles. Therefore, at present, it is not suitable for human-computer interaction applications. Volumetric three-dimensional display is different from the previous three, it is a real 3D technology that can achieve dynamic effects, it can make you see the three-dimensional perspective image "suspended" in the air in science fiction movies. Volumetric three-dimensional display technology can be divided into two types: scanning volumetric display and solid-state volumetric display. Most of the solid-state volumetric display technology uses two light sources to form "space voxel" in the medium material, and draws three-dimensional stereoscopic images through the movement of space voxel, so as to achieve the purpose of three-dimensional display, which has the advantages of good anti-vibration, high brightness, large screen display, etc.

[0003] In the application of volumetric three-dimensional display, organic photonic color-changing materials show great potential. Among them, Schiff base photochromic materials have attracted widespread attention due to their convenient synthesis, simple structure, fast color change speed, cheap raw materials and other characteristics. However, in the application of volumetric three-dimensional display, there are still many limiting factors for Schiff base medium materials, such as weak photochromic fluorescence, single frequency fluorescence, low material transparency, difficulty in selecting excitation and emission wavelength, complex color change mechanism, slow recovery speed, etc. SUMMARY

[0004] In order to solve the technical problem of application of Schiff base with optical switching performance in in-vivo three-dimensional display in the prior art, the application provides a preparation method of 4-{[(E)-(2-phenylpropan-2-yl)azene]methyl}benzene-1,3-diol Schiff base and application of the Schiff base in in-vivo three-dimensional display. The solution reagent of the material has high transparency, no body color and stable property, and has the optical fluorescence color change and optical switching characteristics; under excitation of two light sources with specific wavelengths, the material can realize the photochromism and spatial fluorescence emission, that is, the "spatial voxel point" can be formed. The photochromic process of the material is a reversible process of thermal recovery, and the material can quickly return to the initial state without fluorescence emission under excitation of the excitation light at room temperature, so that the three-dimensional voxel point can be quickly and automatically erased, and the dynamic display effect of real-time refreshing can be achieved.

[0005] In a first aspect, the application provides a Schiff base compound. According to an embodiment of the application, the molecular structure of the Schiff base compound is shown in the following formula (I):

[0006]

[0007] wherein R 1 is C 1-6 alkyl,

[0008] R 2 is aryl,

[0009] R 3 is C 1-12 alkyl.

[0010] According to an embodiment of the application, the compound can further include at least one of the following additional technical features:

[0011] According to an embodiment of the application, R 1 is methyl or ethyl.

[0012] According to an embodiment of the application, R 2 is phenyl.

[0013] According to an embodiment of the application, R 3 is methyl or ethyl.

[0014] According to an embodiment of the application, the compound shown in the formula (I) is The -OCH3 of the compound is conjugated with the benzene ring, and the -C=N- is also conjugated with the benzene ring, so that the conjugated system is increased, and the -OCH3 and the -C=N- both have electron-donating ability, so that the electron cloud density of the benzene ring is greatly increased, which provides favorable conditions for the enol form and the keto form of the Schiff base to be interchanged, and plays a key role in the rapid response thereof.

[0015] In another aspect of the present application, the present application further provides a method for preparing the Schiff base compound as described above. According to an embodiment of the present application, the method comprises: refluxing a compound shown in formula (A) with a compound shown in formula (B) to obtain a compound shown in formula (I).

[0016]

[0017] wherein, R 1 is C 1-6 alkyl,

[0018] R 2 is aryl,

[0019] R 3 is C 1-12 alkyl. The method has the advantages of easy availability of raw materials, low cost, simple synthesis and purification process, high yield, low requirement for production equipment and large-scale production.

[0020] According to an embodiment of the present application, the method described above can further comprise at least one of the following additional technical features:

[0021] According to an embodiment of the present application, R 1 is methyl or ethyl.

[0022] According to an embodiment of the present application, R 2 is phenyl.

[0023] According to an embodiment of the present application, R 3 is methyl or ethyl.

[0024] According to an embodiment of the present application, the compound shown in formula (A) is 4-methoxysalicylaldehyde.

[0025] According to an embodiment of the present application, the compound shown in formula (B) is 2-phenylpropan-2-amine.

[0026] According to an embodiment of the present application, the compound shown in formula (I) is

[0027] According to an embodiment of the present application, the reflux reaction is performed at a temperature of 85-95℃.

[0028] According to an embodiment of the present application, the reflux reaction is performed for 3-6h.

[0029] According to an embodiment of the present application, the reflux reaction is further followed by a post-treatment operation.

[0030] According to an embodiment of the present application, the post-treatment operation comprises cooling treatment, filtration treatment, washing treatment and recrystallization treatment of the reflux reaction solution.

[0031] According to an embodiment of the present application, the molar ratio of the compound shown in formula (A) to the compound shown in formula (B) is 1:1.2-3.

[0032] According to an embodiment of the present application, the molar ratio of the 4-methoxy salicylaldehyde to the 2-phenylpropan-2-amine is 1:1.2-3.

[0033] According to an embodiment of the present application, the reflux reaction is performed in ethanol.

[0034] According to an embodiment of the present application, the ethanol is anhydrous ethanol.

[0035] According to an embodiment of the present application, the molar ratio of the ethanol to the 4-methoxy salicylaldehyde is 30-100:1.

[0036] According to an embodiment of the present application, the application further provides a use of the Schiff base compound or the Schiff base compound prepared by the above method in a three-dimensional display.

[0037] According to an embodiment of the present application, the above use can further include at least one of the following additional technical features:

[0038] According to an embodiment of the present application, the display medium is one or a mixture of several of acetonitrile, methyl tert-butyl ether, dimethyl sulfoxide, ethyl acetate of 4-{[(E)-(2-phenylpropan-2-yl)azomethine]methyl}benzene-1,3-diol Schiff base, or a solid material doped in epoxy resin or polymethyl methacrylate.

[0039] According to an embodiment of the present application, the preferred mass ratio of the 4-{[(E)-(2-phenylpropan-2-yl)azomethine]methyl}benzene-1,3-diol Schiff base to the solvent is 1:5000-10000.

[0040] According to an embodiment of the present application, the method for the three-dimensional display application is as follows:

[0041] (1) selecting a photochromic light source and an excitation light source of a photochromic isomer, respectively;

[0042] (2) making the two light sources in step (1) intersect perpendicularly in the material to generate luminescent voxel points;

[0043] (3) controlling the scanning path and scanning speed of the light source to realize the three-dimensional application.

[0044] According to an embodiment of the present application, the excitation light source of the photochromic light source is blue light with a wavelength of 365-410 nm.

[0045] According to an embodiment of the present application, the ultraviolet light of the photochromic isomer and the blue light with a wavelength of 440-470 nm.

[0046] According to the embodiments of the present application, the present application has at least one of the following technical effects:

[0047] 1) The 4-{[(E)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol Schiff base provided in the present application has raw materials that are easy to obtain, low cost, simple synthesis and purification method, high yield, low requirement for production equipment, and can be produced on a large scale.

[0048] 2) The 4-{[(E)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol Schiff base provided in the present application has -OCH3 conjugated with the benzene ring, and -C=N- also conjugated with the benzene ring, which increases the conjugated system, and -OCH3 and -C=N- both have electron-donating ability, greatly increasing the electron cloud density of the benzene ring, providing favorable conditions for the enol and keto tautomerism of the Schiff base, and playing a key role in the rapid response thereof.

[0049] 3) The intersection has strong light emission and fast response speed, and under the action of a beam of light, ESIPT occurs to produce isomers, another beam of light excites the isomers to emit light, and the intersection can be controlled to emit light by intersecting two light sources, and the excellent response speed thereof can be used as an active light source of a three-dimensional display system.

[0050] 4) The 4-{[(E)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol Schiff base provided in the present application has high transparency and good light transmittance in solution, solid and other media, and can be stored and used stably for a long time.

[0051] According to the embodiments of the present application, the compound represented by formula (I) has the following advantages compared with The compound represented by formula (I) has the following advantages compared with 1 The compound represented by formula (I) has the following advantages compared with

[0052] Terms and Definitions

[0053] Unless otherwise specified, the terms and definitions used in the present application, including the specification and claims of the present application, are as follows.

[0054] The term "C 1-12"Alkyl" is understood to mean preferably a straight-chain or branched saturated monovalent hydrocarbon group having from 1 to 12 carbon atoms; the term "Ci-C6-alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5 or 6 carbon atoms. Said alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1 -methylbutyl, 1 -ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1 -dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1 -methylpentyl, 2-ethylbutyl, 1 -ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1 -dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl and the like or their isomers. In particular, the groups have 1, 2, 3, 4, 5, 6 carbon atoms ("Ci-C6-alkyl"), for example methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly the groups have 1, 2 or 3 carbon atoms ("Ci-C3-alkyl"), for example methyl, ethyl, n-propyl or isopropyl.

[0055] The term "aryl" is understood to mean any stable 6- to 10-membered monocyclic or bicyclic aromatic radical, for example: phenyl, naphthyl, tetrahydronaphthyl, indanyl or biphenyl and the like. BRIEF DESCRIPTION OF DRAWINGS

[0056] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, in which:

[0057] Figure 1 is a process flow chart of 4-{[(E)-(2-phenylpropan-2-yl)hydrazono]methyl}benzene-1,3-diol Schiff base provided by the present application;

[0058] Figure 2 is a nuclear magnetic hydrogen spectrum of 4-{[(E)-(2-phenylpropan-2-yl)hydrazono]methyl}benzene-1,3-diol Schiff base provided by the present application;

[0059] Figure 3 is an absorption spectrum of 4-{[(E)-(2-phenylpropan-2-yl)hydrazono]methyl}benzene-1,3-diol Schiff base provided by the present application;

[0060] Figure 4 is a photoluminescence picture of 4-{[(E)-(2-phenylpropan-2-yl)hydrazono]methyl}benzene-1,3-diol Schiff base provided by the present application. a) solution picture of the Schiff base material, b) intersection luminescence picture of the Schiff base solution under excitation of two different wavelength light sources. DETAILED DESCRIPTION

[0061] The embodiments described below are exemplary and are intended to be illustrative of the present application, and are not to be construed as limiting the present application.

[0062] The present application is described below with reference to specific embodiments, it should be noted that these embodiments are merely descriptive and do not limit the present application in any way.

[0063] Example 1

[0064] The specific synthesis steps of 4-{[(E)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol provided by the present application are as follows:

[0065] 4-methoxysalicylaldehyde: 1.52 g; 2-phenylpropan-2-amine: 1.62 g are mixed in 40 mL of anhydrous ethanol, and refluxed for 4 h. Precipitate is generated after standing at room temperature or low temperature. The precipitate is obtained by filtration, washed with cold ethanol, and recrystallized (the recrystallization process is to place the precipitate in a small amount of solvent, including but not limited to ethanol, ethyl acetate, dichloromethane, tetrahydrofuran, etc., to prepare a supersaturated solution. After heating and stirring until completely dissolved, the solution is naturally cooled to room temperature. The dissolved precipitate slowly precipitates, and the precipitate is filtered and washed), to obtain the target product. Figure 2 and Figure 3 are the nuclear magnetic hydrogen spectrum and absorption spectrum of the target product, respectively.

[0066] Example 2

[0067] The specific synthesis steps of 4-{[(E)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol provided by the present application are as follows:

[0068] 4-methoxysalicylaldehyde: 1.52 g; 2-phenylpropan-2-amine: 2.03 g are mixed in 40 mL of anhydrous ethanol, and refluxed for 4 h. Precipitate is generated after standing at room temperature or low temperature. The precipitate is obtained by filtration, washed with cold ethanol, and recrystallized, to obtain the target product.

[0069] Example 3

[0070] The specific synthesis steps of 4-{[(E)-(2-phenylpropan-2-yl)azomethyl]methyl}benzene-1,3-diol provided by the present application are as follows:

[0071] 4-methoxysalicylaldehyde: 1.52 g; 2-phenylpropan-2-amine: 4.05 g are mixed in 40 mL of anhydrous ethanol, and refluxed for 4 h. Precipitate is generated after standing at room temperature or low temperature. The precipitate is obtained by filtration, washed with cold ethanol, and recrystallized, to obtain the target product.

[0072] Example 4

[0073] The application provides a method for applying 4-{[(E)-(2-phenylpropan-2-yl) azo] methyl} benzene-1,3-diol Schiff base in three-dimensional display in vivo, as follows:

[0074] (1) A 0.15 mg / mL 4-{[(E)-(2-phenylpropan-2-yl) azo] methyl} benzene-1,3-diol dimethyl sulfoxide solution is prepared, as shown in a of Figure 4 , which is a transparent solution.

[0075] (2) According to absorption spectrum and continuous adjustable laser test, 365 nm ultraviolet light is the optimal wavelength for producing photochromism, and 450 nm blue light is the fluorescence excitation light source of isomers.

[0076] (3) As shown in Figure 4 , two light sources intersect perpendicularly with the inside of the material, as shown in Figure 4 , to produce voxel point light emission. The three-dimensional display in vivo can be completed by using a computer to control the scanning path and scanning speed of the two light sources.

[0077] In the description of the present specification, the description of the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in the present specification and the features of the different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

Claims

1. A Schiff base compound, characterized in that The molecular structure of the Schiff base compound is shown in the following formula (I):

2. A method for preparing the Schiff base compound according to claim 1, characterized in that: include: 4-methoxysalicylaldehyde and 2-phenylpropan-2-amine are subjected to reflux reaction to obtain a compound represented by formula (I); 3. The method according to claim 2, characterized in that The temperature of the reflux reaction is 85-95°C.

4. The method according to claim 2, characterized in that The reflux reaction time is 3 to 6 hours.

5. The method according to claim 2, characterized in that The reflux reaction further includes post-processing operations.

6. The method according to claim 5, characterized in that The post-processing operation includes cooling, filtering, washing and recrystallizing the reflux reaction liquid.

7. The method according to claim 2, characterized in that The molar ratio of the 4-methoxysalicylaldehyde to the 2-phenylpropan-2-amine is 1:1.2-3.

8. The method according to claim 2, characterized in that The reflux reaction is carried out in ethanol.

9. The method according to claim 8, characterized in that The ethanol is anhydrous ethanol.

10. The method according to claim 8, characterized in that The molar ratio of the ethanol to the 4-methoxysalicylaldehyde is 30-100:

1.

11. Use of the Schiff base compound according to claim 1 or the Schiff base compound prepared according to the method according to any one of claims 2 to 10 in volumetric three-dimensional display, wherein the use is for non-diagnostic or therapeutic purposes.

12. The use according to claim 11, characterized in that The display medium is a mixed solvent of one or more of acetonitrile, methyl tert-butyl ether, dimethyl sulfoxide, and ethyl acetate for the compound represented by formula (I), or a solid material in which the compound represented by formula (I) is doped in epoxy resin or polymethyl methacrylate.

13. The use according to claim 12, characterized in that The mass ratio of the compound represented by formula (I) to the solvent is 1:5000-10000.

14. The use according to claim 11, characterized in that The method for applying the volumetric three-dimensional display is as follows: (1) Select the photochromic light source and the excitation light source of the photochromic isomer respectively; (2) making the two light sources in step (1) intersect vertically inside the compound material represented by formula (I) to generate light-emitting voxel points; (3) Control the light source scanning path and scanning speed to achieve volumetric three-dimensional applications.

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