Compound, and photochromic material and use thereof

Abstract

The present disclosure belongs to the technical field of photochromism. Provided are a compound, and a photochromic material and the use thereof. The compound is a compound as represented by formula (1) or a stereoisomer or tautomer of the compound as represented by formula (1), wherein R1 is -CH2-, -CH[(CH2)n1CH3]- or -C[(CH2)n1CH3][(CH2)n2CH3]-；R2 is H, -(CH2)n3CH3, phenyl or a fused-ring aromatic hydrocarbonyl; n1, n2 and n3 are each independently selected from an integer between 0 and 6; the phenyl or fused-ring aromatic hydrocarbonyl is optionally substituted with one or more Rn; and Rn is C1-C6 alkyl.

Description

Compounds, photochromic materials and uses TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of photochromic technology, in particular to a compound, photochromic material and use. BACKGROUND

[0002] Breakthroughs in computer and optical technologies have provided various display products for reconstructing the visual world, which is changing our daily life. Currently commercialized display products mainly rely on panel display technology, which only provides two-dimensional (2D) images. Due to the significant advantages of stereoscopic imaging in understanding and explaining visual information, such as being able to provide more information, a wider viewing angle, more stereoscopic image information, etc., the demand for developing 3D display technology is also increasing, especially in the fields of military command and control, industrial design, flight simulators, medical imaging, advertising, movies and exhibitions, etc. Three-dimensional display technology can currently be divided into four categories: automatic light-splitting stereoscopic display, light-splitting stereoscopic glasses, holographic display, and volumetric three-dimensional display. The first two categories, i.e. automatic light-splitting stereoscopic display and light-splitting stereoscopic glasses, both use parallax to give people the feeling of 3D display. The 3D scene constructed by this artificial parallax method is not natural and will increase the brain burden of the observer. Holography uses the interference and diffraction phenomena of light waves. Based on this mechanism, holography can only generate static three-dimensional optical scenes and can only be viewed at a specific angle. Volumetric three-dimensional display technology displays three-dimensional objects through three-dimensional space voxels. This technology presents a real stereoscopic image that can provide all depth information and meet the demand for all-around observation.

[0003] In volumetric three-dimensional display technology, the display medium material properties under existing computer technology are the key to the imaging effect. Taking a static volumetric display system as an example, commonly used materials include dual-frequency up-conversion materials (TSTF-UC), rare earth doped single crystals, dye-based composite materials, and gas materials. Up-conversion materials have fast response speed, but low luminous efficiency, and require high-energy lasers as light sources. Gas display technology is affected by the differences in medium types and refractive indices, making it difficult to be practically applied. Single crystal medium materials are difficult to make large due to high preparation costs. Dye-based medium materials have various types, but some dyes and solvent types are hazardous and difficult to control. In addition, the emission shift of general organic dyes is small, and the excitation light and emission light wavelengths are similar, resulting in poor imaging clarity.

[0004] In organic materials, photochromic compounds can be reversibly switched between colorless and colored states under the influence of light stimuli. Their photoinduced and reversible transformation can be used to modulate fluorescence in molecular and supramolecular structures. Specifically, fluorescent and photochromic components can be paired covalently or non-covalently, and the mutual transformation of the latter can adjust the emission intensity of the formed body according to the electron or energy transfer between the components, thus also known as photoswitching materials. Organic photochromic materials have the advantages of low cost, flexible performance, large formation area, sensitive absorption, controllable physical parameters such as refractive index and dielectric constant, etc. Their own switching light source characteristics have great potential in the field of spatial point addressing. Reports of organic photochromic materials used for three-dimensional display are increasing year by year, but most of the reports show static two-dimensional image effects. Since the switching speed of the materials involved in the reports is slow, the image cannot be updated at the refresh frequency of the human eye, so it is difficult to realize dynamic changes of the graphics.

[0005] Schiff base materials are a kind of materials with fast photochromic speed, mainly referring to a kind of organic compounds containing imine or azomethine characteristic groups (-RC=N-). Schiff base is usually condensed from amine and active carbonyl. The Schiff base derived from salicylaldehyde derivatives with 2-hydroxy mainly exists O-H···N and O···H-N type hydrogen bonds, which occur excited-state interconversion through the excited-state intramolecular proton transfer (ESIPT) process between enolimine and ketoenamine. At present, most of the researches on Schiff base are focused on photochromism and catalysis, and there are few reports on three-dimensional display using Schiff base photochromic materials. The main reason is that the material itself is not transparent in the powder state, which cannot realize spatial display; in solution, the environment of Schiff base changes, and it is difficult to observe obvious photochromism of the material, and the current Schiff base still has the disadvantages of poor luminosity, slow color changing and recovery time, etc., which leads to the difficulty in three-dimensional display light path design. SUMMARY

[0006] The present disclosure aims to at least partially solve one of the technical problems in the related art.

[0007] In one aspect of the present disclosure, a compound is provided, which is a compound represented by formula (1) or a stereoisomer or tautomer of the compound represented by formula (1):

[0008] wherein R1 is -CH2-, -CH[(CH2) n1 CH3]- or -C[(CH2) n1 CH3][(CH2) n2 CH3]-; R2 is H, -(CH2) n3CH3, phenyl or fused ring aromatic hydrocarbon group; n1, n2, n3 are independently selected from an integer between 0 and 6, the phenyl or fused ring aromatic hydrocarbon group is optionally substituted by one or more R n substituted, R n is C1-C6 alkyl.

[0009] The compound of the present disclosure has photochromic properties, is highly colorless and transparent in the closed ring state, can be directly penetrated by visible light without fluorescence change when not irradiated by short wave ultraviolet light, forms open ring isomers after ultraviolet light irradiation, produces photochromism, produces fluorescent points at the intersection of visible light and ultraviolet light irradiation, immediately forms spatial fluorescent points (intersection luminescence characteristics), and the color difference between the fluorescent points and ultraviolet light is large, so that the contrast of the fluorescent points is good. The photochromic and recovery speed of the compound is fast, and the recovery process is a thermal recovery reaction, which can be quickly recovered at room temperature. The chemical properties of the compound are stable, and it can be repeatedly used.

[0010] According to an embodiment of the present disclosure, the R1 is -CH2-, -CH(CH2CH3)-, -CH[(CH2) 14 CH3]-, -C(CH2CH3)(CH2CH3)-, -CH(CH3)- or -C(CH3)2-.

[0011] According to an embodiment of the present disclosure, the R2 is H, -(CH2) n3 CH3, phenyl or naphthyl, the phenyl or naphthyl is optionally substituted by one or more R n substituted, R n is C1-C6 alkyl.

[0012] According to an embodiment of the present disclosure, the R n is methyl.

[0013] According to an embodiment of the present disclosure, the compound has one of the following structures:

[0014] According to an embodiment of the present disclosure, the compound has one of the following structures:

[0015] In another aspect of the present disclosure, a photochromic material is provided, comprising the compound described above. The photochromic material has good luminosity, and the photochromic and recovery speed of the photochromic material is fast, which can be used in the field of three-dimensional imaging. Further, the raw material of the photochromic material is cheap and easy to obtain.

[0016] In still another aspect of the present disclosure, a use of the photochromic material in three-dimensional imaging is provided. In the present disclosure, the photochromic material of the present disclosure can be used in the field of three-dimensional imaging by utilizing the photochromic characteristics of the photochromic material of the present disclosure, and the process of three-dimensional imaging using the photochromic material of the present disclosure is simple.

[0017] According to embodiments of the present disclosure, the three-dimensional imaging comprises the following steps: performing a first irradiation treatment on the photochromic material by using ultraviolet light; and performing a second irradiation treatment on the photochromic material by using visible light, to form a three-dimensional image at the intersection of the light sources of the ultraviolet light and the visible light.

[0018] According to embodiments of the present disclosure, the direction of the visible light source irradiating the photochromic material is perpendicular to the direction of the ultraviolet light source irradiating the photochromic material. BRIEF DESCRIPTION OF DRAWINGS

[0019] The above and / or additional aspects and advantages of the present disclosure will become apparent and more readily appreciated from the following description of embodiments, taken in conjunction with the accompanying drawings in which:

[0020] FIG. 1 is a flowchart of synthesis of compounds according to some embodiments;

[0021] FIG. 2 is a schematic diagram of a photochromic process of a compound according to some embodiments;

[0022] FIG. 3 is a schematic diagram of a light path design for achieving three-dimensional imaging by a photochromic material according to some embodiments;

[0023] FIG. 4 is a spatial point light emitting effect of a photochromic material according to Example 1;

[0024] FIG. 5 is a spatial three-dimensional image display of a photochromic material according to Example 1;

[0025] FIG. 6 is a nuclear magnetic hydrogen spectrum of a compound S-1 according to Example 1;

[0026] FIG. 7 is a nuclear magnetic hydrogen spectrum of a compound S-2 according to Example 2;

[0027] FIG. 8 is a nuclear magnetic hydrogen spectrum of a compound S-3 according to Example 3;

[0028] FIG. 9 is a nuclear magnetic hydrogen spectrum of a compound S-4 according to Example 4;

[0029] FIG. 10 is a nuclear magnetic hydrogen spectrum of a compound S-5 according to Example 5.

[0030] Reference numerals: 1: curtain; 2: ultraviolet light; 3: spatial three-dimensional voxel. DETAILED DESCRIPTION

[0031] Embodiments of the present disclosure are described in detail below with reference to the attached drawing figures, wherein the same or like reference numerals and characters throughout the figures denote the same or like components or elements having the same or similar functions. The embodiments described below are exemplary and intended to be illustrative of the disclosure and are not to be understood as limited in scope.

[0032] In one aspect of the present disclosure, a compound is provided, which is a compound of formula (1) or a stereoisomer, a tautomer of the compound of formula (1):

[0033] wherein R1 is -CH2-, -CH[(CH2) n1 CH3]- or -C[(CH2) n1 CH3][(CH2) n2 CH3]-; R2 is H, -(CH2) n3 CH3, phenyl or fused ring aromatic hydrocarbon group; n1, n2, n3 are independently selected from an integer between 0 and 6, the phenyl or fused ring aromatic hydrocarbon group is optionally substituted by one or more R n , R n is C1-C6 alkyl.

[0034] The compound of the present disclosure has photochromic properties, in the closed ring state, it is highly colorless and transparent by itself, under visible light, the material can be directly penetrated without fluorescence change; after ultraviolet light irradiation, open ring isomers are formed, photochromism is generated, fluorescence points are generated at the intersection of visible light and ultraviolet light irradiation, spatial fluorescence points (intersection luminescence characteristics) are immediately formed, and the color difference between the fluorescence points and the ultraviolet light is large, so that the contrast of the fluorescence points is good. The photochromic and recovery speed of the compound is fast, and the recovery process is a thermal recovery reaction, which can be quickly recovered at room temperature. The chemical properties of the compound are stable, and it can be repeatedly used. In addition, in the compound of the present disclosure, R1 is -CH2-, -CH[(CH2) n1 CH3]- or -C[(CH2) n1 CH3][(CH2) n2 CH3]-; R2 is H, -(CH2) n3 CH3, phenyl or fused ring aromatic hydrocarbon group; n1, n2, n3 are independently selected from an integer between 0 and 6, the phenyl or fused ring aromatic hydrocarbon group is optionally substituted by one or more R n , R n is C1-C6 alkyl.

[0035] Specifically, the color change mechanism of the compounds of the present disclosure is as follows: the compound in the closed ring state, under the external stimulus (such as ultraviolet light), the proton transfer process of O-H···N to O···H-N type hydrogen bond occurs inside the adsorption cavity, the H atom in the hydroxyl group connected to the N atom in the amine group part by a virtual bond is transferred to the N atom in the initial state, the virtual bond of the O···H-N type hydrogen bond of the hydroxyl group is opened, and the structure of the amine group part of the Schiff base is deflected to form an open ring isomer. The process is shown as follows:

[0036] It is understood that the compounds of the present disclosure, as described herein, can be optionally substituted with one or more substituents, such as the compounds of the general formula above, or as in the specific examples, sub-classes, and classes of compounds encompassed by the present disclosure. It is understood that the term "optionally substituted" is used interchangeably with the term "substituted or unsubstituted". The term "optionally", "optional", or "may" means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where the event or circumstance occurs, and instances where it does not. In general, the term "optionally", whether preceded by the term "substituted" or not, indicates that one or more hydrogen atoms of the given structure are replaced with a particular substituent. Unless otherwise indicated, an optional substituent group can be substituted at any available position of the group. When more than one position of the given structure can be substituted with one or more substituents selected from a particular group, the substituents can be the same or different at each position. The substituents can be C1-C6 alkyl.

[0037] The term fused ring aromatic hydrocarbon group refers to a group in which several benzene rings are fused together, wherein the fused ring aromatic hydrocarbon group is optionally substituted with one or more R n .

[0038] The term alkyl represents a saturated straight chain or branched chain monovalent hydrocarbon radical containing from 1 to 6 carbon atoms.

[0039] In some embodiments, R1 is -CH2-, -CH(CH2CH3)-, -CH[(CH2) 14 CH3]-, -C(CH2CH3)(CH2CH3)-, -CH(CH3)-, or -C(CH3)2-.

[0040] In some embodiments, R2 is H, -CH3, phenyl, or naphthyl, which is optionally substituted with one or more R n , R n is C1-C6 alkyl.

[0041] In some embodiments, examples of alkyl groups include, but are not limited to, methyl (-CH3), ethyl (-CH2CH3), n-propyl (-CH2CH2CH3), isopropyl (-CH(CH3)2), n-butyl (-CH2CH2CH2CH3), isobutyl (-CH2CH(CH3)2), sec-butyl (-CH(CH3)CH2CH3), t-butyl (-C(CH3)3), n-pentyl (-CH2CH2CH2CH2CH3), and the like.

[0042] As some examples, the compound Schiff base derivative has a structure as follows:

[0043] As some examples, the compound Schiff base derivative has a structure as follows:

[0044] Among these compounds, R1 contains a chiral C atom, so these compounds have better electrochromic properties and can recover faster after color change.

[0045] In another aspect of the present disclosure, the present disclosure provides a method for preparing the above-mentioned compound, comprising the following steps: (1) performing a protonation reaction on a compound having a structure shown in formula (II) and a first amine compound to obtain compound 1 (as shown in formula (III)); (2) performing a substitution reaction on the compound 1 and sodium methoxide to obtain compound 2 (as shown in formula (IV)); (3) performing an alcoholization reaction on the compound 2 to obtain compound 3 (as shown in formula (V)); (4) performing a bonding reaction on the compound 3 and urotropine to obtain compound 4 (as shown in formula (VI)); and (5) performing a condensation reaction on the compound 4 and a second amine compound to obtain the compound,

[0046] X is selected from bromine or chlorine,

[0047] The method of the present disclosure has a simple process, and through sequentially performing a protonation reaction, a substitution reaction, an alcoholization reaction, a bonding reaction and a condensation reaction, a compound having a photochromic property can be obtained.

[0048] Specifically, the protonation reaction is a dehydration condensation reaction of the first amine compound and 4-X-1,8-naphthalic anhydride in formula (2), so that the first amine compound replaces the oxygen in the anhydride to form the desired compound 1. The first amine compound has electron-withdrawing ability, which can reduce the energy required for the ESIPT process of the Schiff base derivative, and the molecular group of the first amine compound is small, which is conducive to the conversion between the isomers formed by bond site rotation. The substitution reaction is that X in compound 1 is replaced by methoxy in sodium methoxide, and sodium bromide (or sodium chloride) and compound 2 are generated. Sodium methoxide has strong alkalinity, and the substitution reaction has good effect. The alcoholization reaction is to generate compound 3 and iodoalkane through the substitution reaction between hydriodic acid and methoxy in compound 2. The bonding reaction is to add an aldehyde group to the ortho position of the hydroxyl group of compound 3. Urotropine generates formaldehyde under acidic conditions, and then formaldehyde bonds with compound 3 to generate compound 4. The condensation reaction is the condensation of aldehyde compound 4 and the second amine compound, and then the compound is obtained. The second amine compound is selected for reaction, and the second amine compound contains an electron-donating group, which can promote the ESIPT process, and the second amine compound is a small molecular group, the reaction is simple and controllable, and the final product containing the small molecular group has a small conjugated energy system, which is easy to isomerize by bond site rotation.

[0049] According to the present disclosure, in step (1), a compound having a structure shown in formula (2) and a first amine compound are subjected to a protonation reaction to obtain compound 1.

[0050] Generally, the first amine compound can undergo protonation reaction because it is an organic compound having an amino group.

[0051] In some embodiments, the first amine compound includes n-butylamine, tert-butylamine, 3-pentylamine, etc.

[0052] In some embodiments, the conditions of the protonation reaction include refluxing at 110-125°C in a protective atmosphere for 4-8h.

[0053] In some embodiments, step (1) further includes washing treatment, filtering treatment and recrystallization treatment to obtain compound 1.

[0054] According to the present disclosure, in step (2), compound 1 and sodium methoxide are subjected to a substitution reaction to obtain compound 2.

[0055] Generally, sodium methoxide has strong alkalinity and good substitution effect between halogen molecules, and sodium methoxide is used to substitute halogen molecules in the compound to generate alkyl bromide and compound 2 with methoxy.

[0056] In some embodiments, step (2) is performed in the presence of a first catalyst.

[0057] Optionally, the first catalyst comprises copper sulfate, ferric chloride, zinc sulfate, etc.

[0058] It can be understood that the form of adding sodium methoxide is not particularly limited, for example, the sodium methoxide can be directly added to the reaction system.

[0059] In some embodiments, the conditions of the substitution reaction comprise: refluxing at 70-80℃ under a protective atmosphere for 6-10h.

[0060] In some embodiments, the step (2) further comprises a filtration treatment and a washing treatment, so as to obtain the compound 2.

[0061] According to the present disclosure, in the step (3), the compound 2 is subjected to an alcoholization reaction, so as to obtain a compound 3.

[0062] Generally, the alcoholization reaction is performed in the presence of an acid.

[0063] In some embodiments, the acid comprises hydroiodic acid, hydrobromic acid.

[0064] Optionally, the mass fraction of the hydroiodic acid or the hydrobromic acid is 40-60%.

[0065] In some embodiments, the conditions of the alcoholization reaction comprise: refluxing at 100-120℃ under a protective atmosphere for 8-12h.

[0066] In some embodiments, the step (3) further comprises a filtration treatment, a washing treatment and a purification treatment, so as to obtain the compound 3.

[0067] Optionally, the purification treatment is a silica gel column chromatography.

[0068] According to the present disclosure, in the step (4), the compound 3 and urotropine are subjected to a bonding reaction, so as to obtain a compound 4.

[0069] Generally, the bonding reaction of urotropine and the compound 3 can bond the formaldehyde generated under an acidic condition of the urotropine to the compound 3, and the second catalyst can promote the bonding reaction.

[0070] In some embodiments, the step (4) is performed in the presence of the second catalyst.

[0071] Optionally, the second catalyst comprises trifluoroacetic acid, acetic acid.

[0072] In some embodiments, the conditions of the bonding reaction comprise: refluxing at 65-70℃ under a protective atmosphere for 8-12h.

[0073] In some embodiments, the step (4) further comprises a filtration treatment, a washing treatment and a purification treatment to obtain the compound 4.

[0074] Optionally, the crude product after the washing treatment in step (4) can be purified by a short plug of silica.

[0075] In some embodiments, the molar ratio of the compound 3, urotropine and the second catalyst is (1) : (1-3) : (5-20).

[0076] According to the present disclosure, in step (5), the compound 4 and the second amine compound are subjected to a condensation reaction to obtain the compound.

[0077] Generally, the second amine compound and the compound 4 are subjected to a condensation reaction in the presence of a solvent to obtain the compound.

[0078] In some embodiments, the second amine compound has a structural formula as shown in formula (VII), wherein R1 is -CH2-, -CH[(CH2) n1 CH3]- or -C[(CH2) n1 CH3][(CH2) n2 CH3]-; R2 is H, -(CH2) n3 CH3, phenyl or fused ring aromatic hydrocarbon group; n1, n2, n3 are independently selected from integers between 0 and 6, and the phenyl or fused ring aromatic hydrocarbon group is optionally substituted by one or more R n s, R n is C1-C6 alkyl.

[0079] Further, the second amine compound includes at least one of chiral methylbenzylamine, achiral methylbenzylamine, chiral 1-(p-tolyl)ethylamine, achiral 1-(p-tolyl)ethylamine, chiral (1-naphthyl)-2-ethylamine, achiral (1-naphthyl)-2-ethylamine, isobornylamine, alkylamine.

[0080] In some embodiments, the condensation reaction is performed under the following conditions: refluxing at 75-85°C under a protective atmosphere for 2-6h.

[0081] In some embodiments, the step (5) further comprises a filtration treatment, a washing treatment to obtain the compound.

[0082] In some embodiments, the molar ratio of the compound 4, the second amine compound and ethanol is (1) : (0.9-2) : (20-100).

[0083] In some embodiments, the molar ratio of the compound of formula (2), the amine compound, the sodium methoxide, the first catalyst, the urotropine, the second amine compound is 1: (2-4): (7-8): (0.1-0.3): (1-3): (0.8-1.5). Thus, the compound can be obtained.

[0084] As an example, the compound of formula (2) is 4-bromo-1,8-naphthalic anhydride, the amine compound is n-butylamine, the first catalyst is copper sulfate, the second amine compound is S-alpha-methylbenzylamine, the second catalyst is HFT (trifluoroacetic acid), and the urotropine is HMTA. The process of synthesizing the above compound by the method of the present disclosure is shown in FIG. 1.

[0085] In yet another aspect of the present disclosure, a photochromic material is provided, which comprises the compound described above. The photochromic material has good luminosity, and the photochromic material has a relatively fast photochromic and recovery speed, and can be used in the field of three-dimensional imaging. Further, the raw material of the photochromic material is cheap and easy to obtain.

[0086] In some embodiments, the photochromic material further comprises a non-polar solution. The non-polar solution is selected as the medium, and compared with solid materials, the non-polar solution is easier to be made large in urban and rural areas.

[0087] Optionally, the non-polar solution comprises a cyclohexane solution, and the concentration of the cyclohexane solution is 0.001-0.01 mg / ml.

[0088] In some embodiments, the molar ratio of the compound to the non-polar solution is 1: (3000-30000).

[0089] In still another aspect of the present disclosure, the use of the photochromic material in three-dimensional imaging is provided. In the present disclosure, the photochromic material is used in the field of three-dimensional imaging by using the photochromic characteristics of the photochromic material, and the process of three-dimensional imaging by using the photochromic material is simple.

[0090] In some embodiments, as shown in FIGS. 2-5, the compound can exhibit photochromic characteristics under the irradiation of ultraviolet light and visible light source at one time, so that the photochromic material can be used in the field of erasable organic photonic information storage devices, the field of light-controlled switches, and the field of three-dimensional display devices.

[0091] As an example, the working process of the light-controlled switch is as follows: the compound of the photochromic material after color change can absorb visible light, and linking the fluorescent molecules together can achieve switch control of the light emission of the fluorescent molecules. Specifically, if the material after linking the fluorescent molecules is irradiated with ultraviolet light, the color change of the compound will absorb the light of the fluorescent molecules, and the fluorescent molecules are in a non-light-emitting state. If irradiated with visible light, the compound will return to the initial state, the fluorescent molecules do not absorb visible light, and the fluorescent molecules are in a light-emitting state, that is, the function of the light-controlled switch can be realized.

[0092] In some embodiments, the three-dimensional imaging includes the following steps: S1, performing first irradiation treatment on the photochromic material with ultraviolet light; and S2, performing second irradiation treatment on the photochromic material with visible light, to form spatial three-dimensional imaging at the intersection of the light sources of the ultraviolet light and the visible light.

[0093] In step S1, the photochromic material is irradiated with ultraviolet light to cause the compound to change color. Specifically, ultraviolet light of a suitable wavelength is selected, and at the part of the photochromic material irradiated, the compound undergoes ring-opening isomerization, and the photochromic phenomenon occurs.

[0094] As a specific example, the photochromic material is irradiated with ultraviolet light, the spot size of the light source can be adjusted to a suitable size by using an optical lens or a light barrier, and after adjustment by a galvanometer and a mirror, the light source is perpendicular to the side of the transparent container containing the photochromic material and is irradiated into the interior of the photochromic material, thereby forming a spatial light switch opening and closing area in the closed photochromic material.

[0095] In step S2, the photochromic material is irradiated with visible light for second irradiation treatment, to form spatial three-dimensional imaging at the intersection of the light sources of the ultraviolet light and the visible light. In this step, the intersection of the ultraviolet light and the visible light produces fluorescent emission to form a spatial three-dimensional image, that is, spatial three-dimensional imaging is achieved. Specifically, the photochromic material is first irradiated with ultraviolet light to cause photochromism, and then the photochromic material is irradiated with sunlight, and combined with the optical path design, a fluorescent point is generated at the intersection of the two beams of light to form three-dimensional imaging, and no spatial fluorescent point is generated at the part not irradiated with visible light. The color difference between the fluorescent point and the ultraviolet light is large, so that the contrast of the three-dimensional imaging pattern is good, and compared with other photochromic materials, the occurrence area of the photochromic material of the present disclosure will not diffuse in an organic solvent, and the clarity of the imaging will not become blurred due to the movement of the light source (ultraviolet light or visible light). In addition, according to the optical path design, the intersection of the ultraviolet light and the visible light is controlled to move inside the photochromic material, so that the spatial three-dimensional imaging at the intersection also moves.

[0096] In some embodiments, the visible light is incident on the photochromic material in a direction perpendicular to the direction of the ultraviolet light source. In this way, the image quality is improved, and the image distortion or deformation caused by the angle between the photochromic plane and the direction of the ultraviolet light source is reduced.

[0097] Optionally, the wavelength of the ultraviolet light source is 365-450 nm.

[0098] Optionally, the wavelength of the visible light source is 470-500 nm.

[0099] The present disclosure will be described below with reference to specific embodiments, which are merely illustrative and not in any way limit the present disclosure.

[0100] Embodiment 1:

[0101] The synthetic compound S-1: 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1-phenylethyl] azanyl]methyl}-2,3-dihydro-1H-benzo[de]isoquinoline-1,3-dione, has the following structural formula:

[0102] The specific synthesis steps of compound S-1 are as follows:

[0103] (1) According to the flow chart shown in Figure 1, 4-bromo-1,8-naphthalic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) are mixed in acetic acid, and refluxed at 120°C under a protective atmosphere for 5h. After cooling, the mixture is poured into water to produce a precipitate, which is filtered and recrystallized to obtain compound 1.

[0104] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol), and copper sulfate (1.44 g, 9 mmol) are mixed in dry methanol, and refluxed at 75°C under a protective atmosphere for 10h. After cooling, filtration and washing are performed to obtain compound 2.

[0105] (3) A mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) is refluxed at 125°C under a protective atmosphere for 12h. The product is filtered and washed to obtain a crude product, which is purified by silica column chromatography to obtain compound 3.

[0106] (4) Compound 3 (6.73 g, 25 mmol), urotropine (7.01 g, 50 mmol), trifluoroacetic acid (22.8 g, 200 mmol), are refluxed at 70°C for 12h. The reaction mixture is diluted with distilled water, and the precipitate is filtered and washed. The crude product is purified with a short silica plug to obtain compound 4.

[0107] (5) Compound 4 (2.93 g, 10 mmol), S-a-methylbenzylamine (1.21 g, 10 mmol), ethanol (36 g, 500 mmol), reflux at 80 °C for 4 h, filtration, washing to obtain the target compound S-1.

[0108] As shown in Figure 4a, the compound is a light yellow powder; in combination with the nuclear magnetic resonance data in Figure 6, the compound, i.e., 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1- phenylethyl]hydrazono]methyl}-2,3-dihydro-1H-benzo[de]isoquinoline-1,3-dione, can be synthesized by the method of the present disclosure, and as can be seen in the figure 1 H NMR (400 MHz, DMSO-d6) δ 13.32 (s, 1H), 8.88 (d, J = 13.5 Hz, 1H), 8.55 - 8.49 (m, 1H), 8.45 - 8.37 (m, 2H), 7.63 (t, J = 7.7 Hz, 1H), 7.38 (d, J = 7.9 Hz, 2H), 7.25 (d, J = 7.9 Hz, 2H), 5.09 (p, J = 6.6 Hz, 1H), 4.00 (t, J = 7.4 Hz, 2H), 2.31 (s, 3H), 1.73 (d, J = 6.8 Hz, 3H), 1.57 (tt, J = 8.0, 6.4 Hz, 2H), 1.33 (h, J = 7.4 Hz, 2H), 0.92 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, DMSO-d6) δ 13.72, 19.80, 20.65, 21.18, 29.77, 58.64, 106.29, 109.49, 121.85, 125.14, 126.40, 128.48, 129.49, 130.99, 132.15, 132.33, 137.53, 137.85, 162.66, 163.65.

[0109] Example 2

[0110] Synthesis of compound S-1: 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1-(4-methylphenyl)ethyl]hydrazono]methyl}-2,3-dihydro-1H-benzo[de]isoquinoline-1,3-dione, with the following structural formula

[0111] (1) According to the flow chart shown in Figure 1, 4-bromo-1,8-naphthalic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) are mixed in acetic acid, refluxed at 120 °C in a protective atmosphere for 5 h, after cooling, the mixture is poured into water to produce a precipitate, which is filtered and recrystallized to obtain compound 1.

[0112] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, filtration and washing gave compound 2.

[0113] (3) A mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to give a crude product, which was purified by column chromatography on silica to give compound 3.

[0114] (4) Compound 3 (6.73 g, 25 mmol), urotropine (7.01 g, 50 mmol), trifluoroacetic acid (22.8 g, 200 mmol) were refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water and the precipitate was filtered and washed. The crude product was purified using a short silica plug to give compound 4.

[0115] (5) Compound 4 (2.93 g, 10 mmol), (1S)-1-(4-methylphenyl)ethan-1-amine (1.35 g, 10 mmol), ethanol (36 g, 500 mmol) were refluxed at 80 °C for 4 h. Filtration and washing gave the target compound S-2.

[0116] In combination with the nuclear magnetic resonance data of Figure 7, it can be seen that the method of the present disclosure can be used to synthesize the compound, 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1-(4-methylphenyl)ethyl]hydrazono]methyl}-2,3-dihydro-1H- benzo[de]isoquinoline-1,3-dione, from Figure 7 it can be seen that 1 H NMR (400 MHz, DMSO-d6) δ 13.32 (s, 1H), 8.88 (d, J = 13.5 Hz, 1H), 8.55 - 8.49 (m, 1H), 8.45 - 8.37 (m, 2H), 7.63 (t, J = 7.7 Hz, 1H), 7.38 (d, J = 7.9 Hz, 2H), 7.25 (d, J = 7.9 Hz, 2H), 5.09 (p, J = 6.6 Hz, 1H), 4.00 (t, J = 7.4 Hz, 2H), 2.31 (s, 3H), 1.73 (d, J = 6.8 Hz, 3H), 1.57 (tt, J = 8.0, 6.4 Hz, 2H), 1.33 (h, J = 7.4 Hz, 2H), 0.92 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, DMSO-d6) δ 13.72, 19.80, 20.65, 21.18, 29.77, 58.64, 106.29, 109.49, 121.85, 125.14, 126.40, 128.48, 129.49, 130.99, 132.15, 132.33, 137.53, 137.85, 162.66, 163.65.

[0117] Example 3

[0118] Synthesis of compound S-3: 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1-(naphthalen-2- yl)ethyl]hydrazono]methyl}-2,3-dihydro-1H-benzo[de]isoquinoline-1,3-dione, having the following structure

[0119] (1) According to the flow chart shown in Figure 1, 4-bromo-1,8-naphthalic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water, which resulted in the precipitation of compound 1, which was filtered and recrystallized.

[0120] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0121] (3) A mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain the crude product, which was purified by column chromatography on silica to obtain compound 3.

[0122] (4) A mixture of compound 3 (6.73 g, 25 mmol), urotropine (7.01 g, 50 mmol), trifluoroacetic acid (22.8 g, 200 mmol) was refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water and the precipitate was filtered and washed. The crude product was purified using a short silica plug to obtain compound 4.

[0123] (5) A mixture of compound 4 (2.93 g, 10 mmol), (1S)-1-(4-methylphenyl)ethan-1- amine (1.35 g, 10 mmol) in ethanol (36 g, 500 mmol) was refluxed at 80 °C for 4 h. The target compound S-2 was obtained by filtration and washing.

[0124] In view of the NMR data of FIG. 8, a compound, 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1- (naphthalen-2-yl)ethyl]hydrazono]methyl}-2,3-dihydro-1H-benzo[de]isoquinoline-1,3- dione, can be synthesized using the method of the present disclosure. As can be seen from FIG. 8, 1 H NMR (400 MHz, DMSO-d6) δ 8.95 (s, 1H), 8.56 - 8.38 (m, 3H), 8.02 - 7.92 (m, 4H), 7.69 - 7.59 (m, 2H), 7.57 - 7.52 (m, 2H), 5.29 (s, 1H), 4.00 (t, J = 7.4 Hz, 2H), 1.85 (d, J = 6.8 Hz, 3H), 1.57 (p, J = 7.3 Hz, 2H), 1.33 (q, J = 7.4 Hz, 2H), 0.91 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDC13) δ 13.87, 20.41, 22.69, 30.29, 40.02, 60.27, 109.10, 109.68, 122.67, 123.67, 125.57, 125.80, 126.92, 127.01, 127.85, 128.05, 128.72, 129.70, 131.33, 132.72, 133.28, 133.34, 136.84, 138.94, 162.25, 163.74, 164.55.

[0125] Example 4

[0126] Synthesis of compound S-4: 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1-(naphthalen-2- yl)ethyl]hydrazono]methyl}-2,3-dihydro-1H-benzoisoquinoline-1,3-dione, having the following structural formula

[0127] (1) According to the flow chart shown in FIG. 1, 4-bromo-1,8-naphthalic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water to produce a precipitate which was filtered and recrystallized to obtain compound 1.

[0128] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol), and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0129] (3) The mixture of compound 2 (14.15 g, 50 mmol) and 57% hydriodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain a crude product, which was purified by column chromatography on silica gel to obtain compound 3.

[0130] (4) The mixture of compound 3 (6.73 g, 25 mmol), urotropine (7.01 g, 50 mmol), trifluoroacetic acid (22.8 g, 200 mmol) was refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water, and the precipitate was filtered and washed. The crude product was purified with a short silica plug to obtain compound 4.

[0131] (5) The mixture of compound 4 (2.93 g, 10 mmol), (1S)-1-(naphthalen-2- yl)ethan-1-amine (1.71 g, 10 mmol), and ethanol (36 g, 500 mmol) was refluxed at 80 °C for 4 h. The target compound S-2 was obtained by filtration and washing.

[0132] In combination with the nuclear magnetic resonance data in FIG. 9, it can be seen that the compound, 2-butyl-6-hydroxy-5-{[(E)-[(1S)-1-(naphthalen-2- yl)ethyl]hydrazono]methyl}-2,3-dihydro-1H-benzoisoquinoline-1,3-dione, can be synthesized using the method of the present disclosure. As can be seen in the figure, 1 H NMR (400 MHz, CDC13) δ 8.66 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 7.5 Hz, 1H), 8.28 (s, 1H), 8.08 (d, J = 13.1 Hz, 1H), 7.61 (t, J = 7.7 Hz, 1H), 4.15 (dd, J = 8.6, 6.5 Hz, 2H), 1.70 (dd, J = 10.2, 4.9 Hz, 2H), 1.55 (s, 9H), 1.44 (q, J = 7.6 Hz, 2H), 0.97 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDC13) δ 13.89, 20.44, 29.49, 30.32, 40.02, 55.80, 108.54, 109.32, 122.64, 125.41, 128.88, 131.26, 132.72, 133.24, 139.19, 159.55, 163.86, 164.64.

[0133] Example 5

[0134] Synthesis of compound S-5: 2-butyl-6-hydroxy-5-{[(E)-hexadecylhydrazono]methyl}- 2,3-dihydro-1H-benzoisoquinoline-1,3-dione, having the following structural formula

[0135] (1) According to the flow chart shown in Figure 1, 4-bromo-1,8-naphthalic anhydride (27.71 g, 100 mmol) and n-butylamine (21.94 g, 300 mmol) were mixed in acetic acid and refluxed at 120 °C under a protective atmosphere for 5 h. After cooling, the mixture was poured into water, which resulted in the precipitation of compound 1, which was filtered and recrystallized.

[0136] (2) Compound 1 (26.58 g, 80 mmol), sodium methoxide (34.03 g, 630 mmol) and copper sulfate (1.44 g, 9 mmol) were mixed in dry methanol and refluxed at 75 °C under a protective atmosphere for 10 h. After cooling, the mixture was filtered and washed to obtain compound 2.

[0137] (3) A mixture of compound 2 (14.15 g, 50 mmol) and 57% hydroiodic acid (700 mL) was refluxed at 125 °C under a protective atmosphere for 12 h. The product was filtered and washed to obtain the crude product, which was purified by column chromatography on silica to obtain compound 3.

[0138] (4) A mixture of compound 3 (6.73 g, 25 mmol), urotropine (7.01 g, 50 mmol), trifluoroacetic acid (22.8 g, 200 mmol) was refluxed at 70 °C for 12 h. The reaction mixture was diluted with distilled water and the precipitate was filtered and washed. The crude product was purified using a short silica plug to obtain compound 4.

[0139] (5) A mixture of compound 4 (2.93 g, 10 mmol), pentadecan-1-amine (2.28 g, 10 mmol) and ethanol (36 g, 500 mmol) was refluxed at 80 °C for 4 h. The mixture was filtered and washed to obtain the target compound S-2.

[0140] In view of the nuclear magnetic resonance data shown in Figure 10, it can be seen that the method of the present disclosure can be used to synthesize the compound 2-butyl-6-hydroxy-5-{[(E)-hexadecylazomethyl]- methyl}-2,3-dihydro-1H-benzoisoquinoline-1,3-dione. As can be seen in the figure, 1HNMR (400 MHz, CDC13) δ 8.67 (d, J = 8.1 Hz, 1H), 8.58 (d, J = 7.4 Hz, 1H), 8.27 (s, 1H), 7.98 (d, J = 10.7 Hz, 1H), 7.61 (t, J = 7.5 Hz, 1H), 4.17 - 4.12 (m, 2H), 3.65 (s, 2H), 1.80 (q, J = 7.3 Hz, 2H), 1.70 (t, J = 7.6 Hz, 2H), 1.45 (p, J = 7.4 Hz, 8H), 1.25 (s, 20H), 0.97 (t, J = 7.3 Hz, 3H), 0.88 (t, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDC13) δ 13.88, 14.11, 20.44, 22.69, 26.53, 29.07, 29.37, 29.52, 29.59, 29.65, 29.68, 30.07, 30.32, 31.93, 40.04, 51.33, 108.72, 109.49, 122.64, 125.45, 128.84, 131.37, 132.76, 133.29, 138.94, 163.71, 163.87, 164.60.

[0141] Test Example

[0142] The three-dimensional image display test method of compound S-1 is as follows:

[0143] (1) Compound S-1 and cyclohexane are used as photochromic materials, the cyclohexane solution concentration is 0.005 mg / ml, and cyclohexane is used as an imaging medium, and the photochromic materials are loaded in a transparent container with a size of 6*6*6 cm. According to the optical path schematic diagram shown in Figure 3, a 200 mW 405 nm ultraviolet light 2 is used to irradiate the photochromic material to form a photochromic region 3 (spatial three-dimensional voxel), which can be projected on a screen 1, and the color change reaction principle is shown in Figure 2;

[0144] (2) A 100 mW 488 nm blue light source is projected by a scanning galvanometer along the vertical direction perpendicular to the ultraviolet light irradiation direction;

[0145] (3) The exit pattern of the 405 nm ultraviolet light is controlled by a scanning galvanometer, which can produce a specific intersection with the 488 nm blue light path, and a clear spatial light point is generated.

[0146] Figure 4 is a spatial point light emitting effect based on a photochromic material composed of a compound (compound S-1) and a non-polar reagent solution. a is a picture of compound S-1; b is a photochromic material solution containing compound S-1 and cyclohexane, the solution is in a light yellow transparent state, the concentration is 0.005 mg / ml; c is a yellow-green point light generated at the intersection of the two beams when irradiated by 405 nm violet light and 488 nm sky blue light.

[0147] Figure 5 is a spatial static three-dimensional image display based on a photochromic material composed of a compound (compound S-1) and a non-polar reagent solution. a is a spatial three-dimensional cubic fluorescent image generated by the material when irradiated by 405 nm ultraviolet light and 488 nm sky blue light; b is a three-dimensional image filtered by a 510 nm long pass filter for 405 nm ultraviolet light; c is a spatial three-dimensional five-point star-shaped fluorescent image generated when irradiated by 405 nm ultraviolet light and 488 nm sky blue light. As shown in Figures 5a and 5b, a three-dimensional cubic pattern with yellow-green light can be generated at the intersection of the two light paths; changing the scanning trajectory of the light path can form other spatial patterns, such as the spatial three-dimensional five-point star pattern shown in Figure 5c.

[0148] In summary, since the photochromic reaction of the compound is a reversible reaction that is thermally recovered, in this design, when the intersection position of the two beams of light is changed, the spatial light emitting point also moves; by adjusting the intersection position of the violet laser light source and the blue light source in the solution at a certain speed, a moving spatial three-dimensional image can be generated, thereby realizing dynamic refreshing of the spatial three-dimensional image.

[0149] 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 disclosure. 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. In addition, different embodiments or examples described in the present specification and the features of different embodiments or examples can be combined and combined by those skilled in the art without contradiction.

[0150] Although the embodiments of the present disclosure have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present disclosure, and those skilled in the art can make changes, modifications, replacements and variations to the above embodiments within the scope of the present disclosure.

Claims

1. A compound, wherein, The compound is a compound represented by formula (1) or a stereoisomer, a tautomer of the compound represented by formula (1): wherein R1is -CH2-, -CH[(CH2) n1 CH3]- or -C[(CH2) n1 CH3][(CH2) n2 CH3]-; R2is H, -(CH2) n3 CH3, phenyl or fused ring aromatic hydrocarbon group; n1, n2, n3 are independently selected from an integer between 0 and 6, the phenyl or fused aromatic hydrocarbon group being optionally substituted by one or more R n R is a C1-C6alkyl group. n R is a C1-C6alkyl group.

2. The compound of claim 1, wherein, said R1is -CH2-, -CH(CH2CH3)-, -C(CH2CH3)(CH2CH3)-, -CH[(CH2) 14 CH3]-, -CH(CH3)- or -C(CH3)2-.

3. The compound of claim 1 or 2, wherein, R2is H, -(CH2) n3 CH3, phenyl or naphthyl, said phenyl or naphthyl being optionally substituted by one or more R n substituted, R n is C1-C6 alkyl.

4. The compound according to any one of claims 1 to 3, wherein, The R n is methyl.

5. The compound according to any one of claims 1-4, wherein, having a structure as follows:

6. The compound according to any one of claims 1-5, wherein, having a structure as follows:

7. A photochromic material wherein, The compound according to any one of claims 1 to 6.

8. Use of the photochromic material according to claim 7 in three-dimensional imaging.

9. Use according to claim 8, wherein, The three-dimensional imaging comprises the following steps: The photochromic material is subjected to a first irradiation treatment with ultraviolet light; The photochromic material is subjected to a second irradiation treatment with visible light, forming a three-dimensional image at the intersection of the light sources of the ultraviolet light and the visible light.

10. Use according to claim 9, wherein, The direction of the visible light source irradiating the photochromic material is perpendicular to the direction of the ultraviolet light source irradiating the photochromic material.

Images