A triarylmethane compound, and a preparation method and application thereof

Abstract

The application provides a triarylmethane compound and a preparation method and application thereof, and belongs to the technical field of organic compounds. The triarylmethane compound is prepared by connecting a benzopentacyclic ring structure to a key position of a triarylmethane compound skeleton through structure design, and has excellent performance. The preparation method of the triarylmethane compound is simple and convenient, and has a high yield. The blue dye obtained by taking the triarylmethane compound as a blue dye has high selective absorption and transmission capacity at a wavelength of 450 nm, and has high thermal stability.

Description

Technical Field

[0001] This invention belongs to the field of organic compound technology, specifically relating to a triarylmethane compound, its preparation method, and its application. Background Technology

[0002] Color filters used in display devices such as liquid crystal displays, electroluminescent displays, and plasma displays, as well as solid-state imaging elements such as CCDs and CMOS sensors, are manufactured from coloring resin compositions. Various dyes, including blue dyes, are used as the coloring resin compositions for forming these filters. Existing blue dyes have the following drawbacks: 1. Insufficient optical performance: Some blue dyes have low transmittance at 450 nm wavelength (e.g., uneven dyeing and insufficient color saturation in lens dyeing), failing to meet the stringent requirements for narrowband spectral transmittance in high-resolution optical devices (such as laser filters and display backlight modules). 2. Limited thermal stability: Most organic blue dyes have thermal decomposition temperatures below 300℃, while inorganic cobalt blue, although reaching above 1000℃, has high synthesis costs and low optical transmittance, making it difficult to balance performance and economy in high-temperature processing scenarios. 3. Complex synthesis process: Traditional methods rely on salting-out purification steps, resulting in harsh reaction conditions, numerous byproducts, and high wastewater treatment costs, failing to meet the low-cost and environmentally friendly requirements of large-scale industrial production.

[0003] Therefore, how to provide a dye compound with good optical properties and high thermal stability, and with a simple preparation method, has become an urgent technical problem to be solved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a triarylmethane compound, its preparation method, and its applications. This invention designs the structure of the triarylmethane compound by attaching a benzo[a] five-membered ring structure (Q-linked structure in Formula I) at a key position in the compound's skeleton, thus preparing a triarylmethane compound with excellent performance. Furthermore, the preparation method for this triarylmethane compound is simple, convenient, and yields a high amount of material. Using this triarylmethane compound as a blue dye, the resulting blue dye exhibits high selective absorption and transmission at a wavelength of 450 nm, while also possessing high thermal stability.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides a triarylmethane compound having the structure shown in Formula I:

[0007] Formula I;

[0008] Where Q represents R b1 - R b5 Each element independently represents any one of the following: hydrogen atom, deuterium atom, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, or C1-C10 alkoxy group; the dashed line indicates the connection site.

[0009] T 1 T 2 Each can independently represent any one of substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene;

[0010] R k1 R k2 R1-R 16 Each of the following can be independently represented: hydrogen atom, deuterium atom, substituted or unsubstituted C1-C10 straight-chain or branched alkyl group, substituted or unsubstituted C3-C10 cycloalkyl group, or substituted or unsubstituted C6-C20 aryl group;

[0011] R a1 -R a8 Each of the following can be independently represented: a substituted or unsubstituted C1-C10 straight-chain or branched alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C3-C20 heteroaryl group.

[0012] T 1 T 2 R k1 R k2 R1-R 16 R a1 -R a8 The substituents described herein each independently represent any one of the following: deuterium atom, halogen atom, cyano group, amino group, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, and C6-C10 aryl group;

[0013] p represents 0 or 1;

[0014] q represents an integer from 1 to 20;

[0015] Y n- The denot represents an anion, n represents an integer from 1 to 20, and m represents an integer from 1 to 10.

[0016] This invention designs the structure of a triarylmethane compound and attaches a benzo5-membered ring structure (Q-linked structure in Formula I) at a key position in the compound's skeleton, thus preparing a high-performance triarylmethane compound. The preparation method for this triarylmethane compound is simple, convenient, and yields a high level of efficiency. Using this triarylmethane compound as a blue dye, the resulting blue dye exhibits high selective absorption and transmission at a wavelength of 450 nm, along with high thermal stability.

[0017] In this invention, the design of the benzo[a] five-membered ring structure (Q-connected structure in Formula I) in the triarylmethane compound increases the van der Waals forces between molecules, which helps to improve the dispersibility and stability of the blue dye containing the triarylmethane compound in the matrix. Furthermore, the presence of the large conjugated groups in the triarylmethane compound alters the electron cloud distribution of the molecule, significantly affecting its absorption spectrum and resulting in stronger absorption of blue light at 450 nm. Simultaneously, the rigid structural unit—the benzo[a] five-membered ring structure (Q-connected structure in Formula I)—introduces a constraint on the thermal motion of the triarylmethane compound molecular chain, improving its thermal stability. Compared with traditional dye structures, the rigid structural unit in the blue dye molecule provided by this invention enhances the overall rigidity of the molecule, making it less prone to molecular chain twisting, bending, or breakage due to heat. At high temperatures, the structure of the blue dye provided by this invention remains relatively stable, while traditional dyes of the same type exhibit significant structural changes and performance degradation.

[0018] In this invention, unless otherwise specified, the heteroatom of the heteroaryl group is selected from atoms or groups of atoms in N, O, S, P, B, Si or Se, preferably N, O or S.

[0019] In this invention, the way of expressing a ring structure with "—" or "------" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0020] In this invention, the expression Ca-Cb represents that the group has ab carbon atoms. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituents.

[0021] In this invention, "each independently" means that when there are multiple subjects, they can be the same or different from each other.

[0022] In this invention, the C1-C10 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C2, C3, C4, C5, C6, C7, C8, C9, C10, etc., and exemplary include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-octyl, n-heptyl, n-nonyl or n-decyl, etc.

[0023] In this invention, the C3-C10 cycloalkyl groups can all be cycloalkyl groups of C4, C5, C6, C7, C8, C9, C10, etc., and exemplary include but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.

[0024] In this invention, specific examples of the C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.) alkoxy groups can be exemplified by the above-mentioned straight-chain or branched alkyl groups connected to O to obtain monovalent groups.

[0025] In this invention, the C6-C20 arylene groups can all be arylene groups of C6, C9, C10, C12, C14, C16, C18, C20, etc., including monocyclic arylene groups or fused-ring arylene groups. A monocyclic arylene group means that the group contains at least one phenylene group. When it contains at least two phenyl groups, the phenyl groups are linked by a single bond, including but not limited to: phenylene, biphenylene, terphenylene, etc.; a fused-ring arylene group means that the group contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms that are fused together, including but not limited to: naphthylene, naphthylphenylene, phenylnaphthylene, anthracene, phenanthrene, fluorene, etc.; the aforementioned listed groups include all possible connection methods.

[0026] In this invention, the C3-C20 heteroaryl groups can all be heteroaryl groups of C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, etc., including monocyclic heteroaryl groups or fused-ring heteroaryl groups. A monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: furanyl, thiopheneyl, pyrrolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazolyl, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one heteroaryl ring and one aromatic ring (aromatic heterocycle or aromatic ring), and the two rings share two adjacent atoms fused together in a group, including but not limited to: benzofuranyl, benzothiopheneyl, isobenzofuranyl, isobenzothiopheneyl, dibenzofuranyl, dibenzothiopheneyl, carbazoyl, etc.; the aforementioned groups include all possible connection methods.

[0027] In this invention, the C6-C20 aryl groups can be aryl groups of C6, C9, C10, C12, C14, C16, C18, C20, etc., preferably C6-C10 aryl groups, including monocyclic aryl groups or fused-ring aryl groups. A monocyclic aryl group means that the group contains at least one phenyl group. When it contains at least two phenyl groups, the phenyl groups are linked by a single bond, including but not limited to: phenyl, biphenyl, terphenyl, etc.; a fused-ring aryl group means that the group contains at least two aromatic rings, and the aromatic rings share two adjacent carbon atoms fused together, including but not limited to: naphthyl, naphthylphenyl, phenylnaphthyl, anthraceneyl, phenanthryl, fluoreneyl, etc.; the aforementioned listed groups include all feasible connection methods.

[0028] In this invention, the C3-C20 heteroaryl groups can be heteroaryl groups of C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, etc., including monocyclic heteroaryl groups or fused-ring heteroaryl groups. A monocyclic heteroaryl group means that the molecule contains at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are connected by a single bond, exemplarily including but not limited to: furanyl, thiophene, pyrrole, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, oxazolyl, thiazolyl, imidazole, etc. The term "fused-ring heteroaryl" refers to a molecule containing at least one aromatic heterocycle and one aromatic ring (aromatic heterocycle or aromatic ring), and the two share two adjacent atoms fused together in a group, including but not limited to: benzofuranyl, benzothiophenyl, isobenzofuranyl, isobenzothiophenyl, dibenzofuranyl, dibenzothiophenyl, carbazoleyl, etc.; the aforementioned groups include all possible connection methods.

[0029] The halogen atom includes fluorine, chlorine, bromine, or iodine; the same descriptions used below have the same meaning.

[0030] In this invention, the integers from 1 to 20 can be 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, or 20, etc.

[0031] The integers from 1 to 10 can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0032] It should also be noted that when p represents 0, T 2 denoted as any one of substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl; when p represents 1, T 2 It represents any one of substituted or unsubstituted C6-C20 arylene or substituted or unsubstituted C3-C20 heteroarylene.

[0033] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The purpose and beneficial effects of the present invention can be better achieved and realized through the following preferred technical solutions.

[0034] Preferably, Q represents or R b1 - R b5 With the same definition as above, dashed lines represent connection sites.

[0035] Preferably, the R b1 - R b3 Each can be independently represented as a C1-C5 alkyl group.

[0036] Preferably, the R b4 - R b5 Each can be used independently to represent a hydrogen atom or a deuterium atom.

[0037] Preferably, Q represents or The dashed line indicates the connection point.

[0038] Preferably, the T 1 T 2 Each of the following groups, whether substituted or unsubstituted, independently represents any one of the following: phenylene, naphthylene; wherein each of the substituted substituents independently represents at least one of the following: deuterium atom, halogen atom, cyano, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl.

[0039] Preferably, the R k1 R k2 R1-R 16 Each of the following can be independently represented: hydrogen atom, deuterium atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl or phenyl.

[0040] Preferably, the R a1 R a3 R a5 R a7 Each independently represents any one of substituted or unsubstituted C1-C10 straight-chain or branched alkyl groups, or substituted or unsubstituted C3-C10 cycloalkyl groups, wherein R a2 R a4 R a6 R a8 Each can independently represent any one of substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C3-C20 heteroaryl.

[0041] Preferably, the R a1 R a3 R a5 R a7 Each of the following groups, whether substituted or unsubstituted, independently represents any one of the substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl; wherein each of the substituted substituents independently represents at least one of deuterium, halogen, cyano, amino, methyl or ethyl.

[0042] Preferably, the R a2 R a4 R a6 R a8Each of the following groups, whether substituted or unsubstituted, independently represents any one of the following: phenyl, naphthyl, biphenyl; wherein each of the substituted substituents independently represents at least one of deuterium, halogen, cyano, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0043] Preferably, the Y n- [PW] 12 O 40 3- [P2W] 18 O 62 6- ]、[SiW 12 O 40 4- [P2W] 17 O 61 10- [P2W] 15 O 56 12- [H2P2W] 12 O 48 12- [NaP5W] 30 O 110 14- [SiW9O] 34 10- ]、[SiW 10 O 36 8- ]、[SiW 11 O 39 8- [W6O] 19 2- ]、[W 10 O 32 4- ]、[WO4 2- ]、 , , , , , Any one of them.

[0044] Preferably, q represents an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0045] Preferably, m represents an integer from 1 to 5, such as 1, 2, 3, 4 or 5.

[0046] Preferably, the triarylmethane compound includes the following compounds:

[0047] .

[0048] In a second aspect, the present invention provides a method for preparing a triarylmethane compound as described in the first aspect, the method comprising the following steps:

[0049] (1) Raw material 1 and raw material 2 react in the presence of a catalyst to obtain intermediate 1;

[0050] Among them, raw material 1 is Raw material 2 is T 1 -X 1 and T 2 -X 2 Q, R k1 R k2 T 1 T 2 With the same definition as above, X 1 X 2 Each halogen atom represents itself independently;

[0051] (2) Intermediate 1 reacts with raw material 3 to obtain intermediate 2;

[0052] Among them, raw material 3 is and / or R1-R 16 R a1 -R a8 It has the same definition as above;

[0053] (3) Intermediate 2 and containing Y n- Anion exchange was performed on the compound to obtain a triarylmethane compound as shown in Formula I.

[0054] The triarylmethane compound provided by this invention can be prepared using a highly efficient and cheaper catalyst. The preparation method is simple and convenient, and the yield is high.

[0055] Preferably, the catalyst in step (1) comprises palladium acetate.

[0056] Preferably, the molar ratio of raw material 1 to raw material 2 is 1:(2-2.2), for example, it can be 1:2, 1:2.05, 1:2.1, 1:2.15, or 1:2.2, etc.

[0057] Preferably, in the raw material 2, T 1 -X 1 and T 2 -X 2 The molar ratio is 1:1.

[0058] Preferably, the reaction temperature in step (1) is 125-140℃ (e.g., it can be 125℃, 126℃, 128℃, 130℃, 132℃, 134℃, 136℃, 138℃ or 140℃, etc.), and the time is 40-60 h (e.g., it can be 40 h, 42 h, 44 h, 46 h, 48 h, 50 h, 52 h, 54 h, 56 h, 58 h or 60 h, etc.).

[0059] Preferably, the reaction in step (1) is carried out in the presence of sodium tert-butoxide, tri-tert-butylphosphine and solvent A.

[0060] Preferably, solvent A comprises xylene.

[0061] Preferably, the reaction in step (1) further includes a post-processing step, wherein the post-processing method includes steps of cooling, extraction, drying and concentration.

[0062] Preferably, the reaction temperature in step (2) is 40-60℃ (e.g., 40℃, 42℃, 44℃, 46℃, 48℃, 50℃, 52℃, 54℃, 56℃, 58℃ or 60℃, etc.), and the time is 15-30 h (e.g., 15 h, 16 h, 18 h, 20 h, 22 h, 24 h, 26 h, 28 h or 30 h, etc.).

[0063] Preferably, the molar ratio of the intermediate 1 to the raw material 3 is 1:(1-2.2), for example, it can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.1 or 1:2.2, etc.

[0064] Preferably, the reaction in step (2) is carried out in the presence of phosphorus oxychloride and solvent B.

[0065] Preferably, solvent B comprises chlorobenzene.

[0066] Preferably, the reaction in step (2) further includes a post-processing step, wherein the post-processing method includes the steps of separation, washing, drying, concentration and purification.

[0067] Preferably, the temperature of the anion exchange in step (3) is 20-30℃ (e.g., 20℃, 22℃, 24℃, 26℃, 28℃ or 30℃, etc.), and the time is 0.5-3 h (e.g., 0.5 h, 1 h, 2 h or 3 h, etc.).

[0068] Preferably, step (3) is carried out in the presence of the anion exchange solvent C.

[0069] Preferably, the solvent C comprises methanol and water.

[0070] Preferably, the reaction in step (3) further includes a post-processing step, wherein the post-processing method includes the steps of filtration, washing and drying.

[0071] Thirdly, the present invention provides a blue dye comprising at least one triarylmethane compound as described in the first aspect.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] This invention designs the structure of a triarylmethane compound and attaches a benzo5-membered ring structure (Q-linked structure in Formula I) at a key position in the compound's skeleton, thus preparing a high-performance triarylmethane compound. The preparation method for this triarylmethane compound is simple, convenient, and yields a high level of efficiency. Using this triarylmethane compound as a blue dye, the resulting blue dye exhibits high selective absorption and transmission at a wavelength of 450 nm, along with high thermal stability. Detailed Implementation

[0074] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0075] It should be noted that in Examples 1 and 2 below, the raw material 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindene used is a mixture of isomers, containing two structures ( , Therefore, the products prepared using this raw material are also mixtures of isomers (such as intermediates A1 and B1, or intermediates A2 and B2, or compound A3 and compound B3 as described below).

[0076] Example 1

[0077] This embodiment provides a method for synthesizing compound A3 / compound B3, as detailed below:

[0078] (1) Synthesis of intermediate A1 / intermediate B1:

[0079]

[0080] 1-Iodonaphthalene (5.1 g, 20 mmol), 5(6)-amino-1-(4-aminophenyl)-1,3,3-trimethylindene (2.7 g, 10 mmol), sodium tert-butoxide (2.7 g, 28 mmol), tri-tert-butylphosphine (1 g, 5 mmol), and palladium acetate (0.05 g, 0.2 mmol) were dispersed in 50 mL of xylene and reacted at 130–135 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and extracted with water. Then, it was dried with magnesium sulfate and concentrated to obtain a mixture of intermediate A1 and intermediate B1 (3.6 g, yield 71%), denoted as intermediate A1 / intermediate B1.

[0081] The intermediates A1 and B1 were characterized, and the characteristics are as follows: 1 H NMR (500 MHz, Chloroform-d)δ 7.97 – 7.88 (m, 2H), 7.78 – 7.67 (m, 6H), 7.53 – 7.43 (m, 6H), 7.32 – 7.24(ddt, 3H), 7.19 – 7.06 (m, 5H), 6.93 (dd, 1H), 3.89 (dqt, 1H), 2.63 (dd, H), 1.27 – 1.13 (ddt, 6H); LC-MS (C 37 H 32 N2): 503.1.

[0082] (2) Synthesis of intermediate C1

[0083]

[0084] 4,4'-Dibromobenzophenone (20 g, 60 mmol), N-ethyl-2-methylaniline (16 g, 120 mmol), sodium tert-butoxide (16 g, 168 mmol), tri-tert-butylphosphine (6 g, 30 mmol), and palladium acetate (0.134 g, 0.6 mmol) were dispersed in 200 mL of toluene and reacted at 115 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and extracted with water. The extract was then dried with magnesium sulfate and concentrated to give intermediate C1 (23.6 g, yield 88%).

[0085] Intermediate C1 was characterized, and the characterization results are as follows: 1H NMR (400 MHz, CDCl3) δ 7.81 – 7.20(m, 4H), 7.15 – 6.85 (dd, 4H), 3.50 (q, J = 7.2 Hz, 4H), 2.15 (s, 6H), 1.6(t, 6H); LC-MS (C 31 H 32 N2O): 448.5.

[0086] (3) Synthesis of intermediate A2 / intermediate B2:

[0087]

[0088] A mixture of intermediates A1 and B1 (3.1 g, 6 mmol), intermediate C1 (5.8 g, 13 mmol), and 30 mL of chlorobenzene were stirred and mixed thoroughly at 45–50 °C. Phosphorus oxychloride (1.99 g, 13 mmol) was added dropwise, and the mixture was stirred at 45–50 °C for 20 h. After the reaction was completed, 100 mL of chloroform and 100 mL of water were added to dissolve the mixture, and the chloroform layer was separated. The chloroform layer was washed with water, dried with magnesium sulfate, and concentrated under reduced pressure. The residue was diluted with chloroform and purified by silica gel column chromatography to obtain a mixture of intermediates A2 and B2 (7.4 g, yield 90%), denoted as intermediate A2 / intermediate B2.

[0089] The intermediates A2 and B2 were characterized, and the results are as follows: 1 H NMR (500 MHz, Chloroform-d)δ 7.97 – 7.86 (m, 6H), 7.73 – 7.51 (m, 14H), 7.38 (dd, 8H), 7.21 – 7.16 (m,8H), 7.07 – 6.88 (m, 17H), 5.47 – 5.33 (m, 2H), 4.21 – 3.97 (m, 9H), 2.76 –2.63 (m, 2H), 2.57 – 2.49 (d, 12H), 1.24 – 1.09 (d, 18H); LC-MS (C 99 H 96 N6):1368.1.

[0090] (4) Synthesis of compound A3 / compound B3

[0091]

[0092] After dissolving 12-tungstic phosphate·n hydrate (3.68 g, 1.28 mmol) by heating in a mixture of 60 mL methanol and 60 mL water, a mixture of intermediates A2 and B2 (2.76 g, 2 mmol) was added. The mixture was stirred at room temperature for 1 h, the precipitate was filtered, washed with water, and dried under reduced pressure to obtain a mixture of compounds A3 and B3 (26.07 g, yield 92%), denoted as compound A3 / compound B3.

[0093] The compounds A3 and B3 were characterized, and the results are as follows: 1 H NMR (500 MHz, Chloroform-d)δ 8.12 – 8.06 (m, 2H), 7.89 (ddd, 2H), 7.82 (d, 2H), 7.49 – 7.30 (m, 18H),7.23 – 7.18 (m, 8H), 7.11 – 7.02 (m, 22H), 5.31 – 5.27 (m, 2H), 4.16 – 3.93 (m, 9H), 2.72 – 2.61 (m, 2H), 2.28 (d, 12H), 1.51 – 1.28 (m, 12H), 1.09 –1.04 (dd, 6H); MALDI-TOF MS (C 99 H 96 N6 + ): calcd. 1368.7614.

[0094] Example 2

[0095] This embodiment provides a method for synthesizing compounds A6 / A7 / B6 / B7, as detailed below:

[0096] (1) Prepare intermediate A1 / intermediate B1 according to the synthesis method provided in step (1) of Example 1;

[0097] (2) Prepare intermediate C1 according to the synthesis method provided in step (2) of Example 1;

[0098] (3) Synthesis of intermediate A4 / intermediate A5 / intermediate B4 / intermediate B5:

[0099]

[0100] A mixture of intermediates A1 and B1 (3.1 g, 6 mmol), intermediate C1 (2.9 g, 6 mmol), and 30 mL of chlorobenzene were mixed and stirred at 0 °C. Phosphorus oxychloride (1.99 g, 13 mmol) was added dropwise, and the mixture was stirred at 45–50 °C for 20 h. After the reaction was completed, 100 mL of chloroform and 100 mL of water were added to dissolve the mixture, and the chloroform layer was separated. The chloroform layer was washed with water, dried with magnesium sulfate, and concentrated under reduced pressure. The residue was diluted with chloroform and purified by silica gel column chromatography to obtain a mixture of intermediates A4, A5, B4, and B5 (5.3 g, yield 83%), denoted as intermediate A4 / intermediate A5 / intermediate B4 / intermediate B5.

[0101] Intermediate A4 / Intermediate A5 / Intermediate B4 / Intermediate B5 were characterized, and the characterization results are as follows: 1 H NMR (500MHz, Chloroform-d) δ 8.01 – 7.88 (m, 3H), 7.77 – 7.62 (m, 3H), 7.52 – 7.40(m, 5H), 7.35 (dd, 2H), 7.28 – 7.20 (m, 5H), 7.19 – 7.05 (m, 12H), 7.05 –6.98 (m, 5H), 6.98 – 6.93 (m, 2H), 5.29 (h, 1H), 4.10 (dq, 2H), 4.04 – 3.90(m, 3H), 2.28 (d, 6H), 1.24 – 1.04 (m, 12H); LC-MS (C 68 H 64 N4): 935.4.

[0102] (4) Synthesis of compound A6 / compound A7 / compound B6 / compound B7

[0103]

[0104] Referring to the synthesis method provided in step (3) of Example 1, the mixture of intermediates A1 and B1 was replaced with a mixture of intermediates A4, A5, B4 and B5 to finally obtain a mixture of compounds A6, A7, B6 and B7 (yield of 90%), denoted as compound A6 / compound A7 / compound B6 / compound B7.

[0105] The compounds A6, A7, B6, and B7 were characterized, and the results are as follows: 1 H NMR (500MHz, Chloroform-d) δ 8.12 – 8.08 (m, 1H), 7.97 – 7.86 (m, 2H), 7.77 – 7.62(m, 3H), 7.52 – 7.40 (m, 5H), 7.35 (dd, 2H), 7.28 – 7.20 (m, 5H), 7.19 – 7.10(m, 9H), 7.10 – 7.05 (m, 3H), 7.05 – 6.98 (m, 5H), 6.98 – 6.93 (m, 2H), 5.29(h, 1H), 4.10 (dq, 2H), 4.04 – 3.90 (m, 3H), 2.28 (d, 6H), 1.24 – 1.04 (m,12H); MALDI-TOF MS (C 68 H 64 N4 + ): calcd. 936.5168.

[0106] Example 3

[0107] This embodiment provides a method for synthesizing compounds D3 and E3, as detailed below:

[0108] (1) Prepare a mixture of intermediate A1 / intermediate B1 by referring to the synthesis method provided in step (1) of Example 1;

[0109] (2) Synthesis of intermediate C2

[0110]

[0111] 4,4'-Dibromobenzophenone (20 g, 60 mmol), N-methyl-2-methylaniline (120 mmol), sodium tert-butoxide (16 g, 168 mmol), tri-tert-butylphosphine (6 g, 30 mmol), and palladium acetate (0.134 g, 0.6 mmol) were dispersed in 200 mL of toluene and reacted at 115 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and water was added for extraction. The extract was then dried with magnesium sulfate and concentrated to give intermediate C1 (23.6 g, yield 88%).

[0112] Intermediate C2 was characterized, and the characterization results are as follows: 1LC-MS (C 29 H 28 N2O): 419.1.

[0113] (3) Referring to the synthesis method provided in step (3) of Example 1, intermediate C2 was used to replace intermediate C1 to prepare intermediate D2 / intermediate E2;

[0114]

[0115] The intermediates D2 and E2 were characterized, and the results are as follows: 1 H NMR (500 MHz, Chloroform-d)δ 8.08 – 7.93 (m, 4H), 7.82 (d, 2H), 7.71 – 7.58 (m, 12H), 7.43 – 7.23 (m,18H), 7.18 – 6.91 (m, 17H), 5.33 – 5.27 (m, 2H), 3.08 (d, 14H), 2.27 – 1.81 (m, 12H), 1.09 (d, 3H), 1.04 (dt, 3H); LC-MS (C 95 H 88 N6): 1311.5.

[0116] (4) Compound D3 / Compound E3 were prepared by referring to the synthesis method provided in step (4) of Example 1;

[0117]

[0118] The compounds D3 and E3 were characterized, and the results are as follows: 1H NMR (500 MHz, Chloroform-d)δ 8.12 – 8.06 (m, 2H), 7.89 (ddd, 2H), 7.82 (d, 2H), 7.49 – 7.40 (m, 4H),7.35 (dd, 3H), 7.27 – 7.20 (m, 8H), 7.20 – 7.09 (m, 15H), 7.07 – 7.03 (m,4H), 7.01 – 6.91 (m, 13H), 5.29 (q, 2H), 3.30 (d, 12H), 2.27 (d, 12H), 1.09 –1.04 (m, 6H); MALDI-TOF MS (C 95 H 88 N6 + ): calcd. 1312.7051.

[0119] Comparative Example 1

[0120] This comparative example provides a method for synthesizing compound A-1, as follows:

[0121] (1) Synthesis of intermediate 1:

[0122]

[0123] 1-Iodonaphthalene (5.1 g, 20 mmol), 4,4'-diaminodiphenylmethane (1.98 g, 10 mmol), sodium tert-butoxide (2.7 g, 28 mmol), tri-tert-butylphosphine (1 g, 5 mmol), and palladium acetate (0.05 g, 0.2 mmol) were dispersed in 50 mL of xylene and reacted at 130–135 °C for 48 h. After the reaction was completed, the mixture was cooled to room temperature and extracted with water. The extract was then dried with magnesium sulfate and concentrated to give intermediate 1 (3.5 g, yield 78%).

[0124] Intermediate 1 was characterized, and the characterization results are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.97 –7.89 (m, 2H), 7.75 (dd, 2H), 7.68 – 7.62 (m, 3H), 7.56 (s, 1H), 7.50 (d, 1H),7.49 – 7.42 (m, 5H), 7.29 – 7.17 (m, 5H), 7.08 – 7.01 (m, 3H), 6.95 – 6.87(m, 2H), 4.09 (p, 2H); LC-MS (C33 H 26 N2): 449.8.

[0125] (2) The intermediate C1 was prepared according to the synthesis method provided in step (2) of Example 1;

[0126] (3) Synthesis of intermediate 2:

[0127]

[0128] Intermediate 1 (6 mmol), intermediate C1 (2.9 g, 6 mmol), and 30 mL of chlorobenzene were stirred and mixed thoroughly at 45–50 °C. Phosphorus oxychloride (1.99 g, 13 mmol) was then added dropwise, and the mixture was stirred at 45–50 °C for 20 h. After the reaction was completed, 100 mL of chloroform and 100 mL of water were added to dissolve the mixture, and the chloroform layer was separated. The chloroform layer was washed with water, dried with magnesium sulfate, and concentrated under reduced pressure. The residue was diluted with chloroform and purified by silica gel column chromatography to obtain intermediate 2 (7.4 g, 90% yield).

[0129] Intermediate 2 was characterized, and the characterization results are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.01 –7.89 (m, 2H), 7.74 – 7.68 (m, 4H), 7.58 – 7.44 (m, 6H), 7.36 – 7.27 (m, 11H),7.21 – 7.10 (m, 14H), 7.05 – 6.89 (m, 15H), 5.33 (ddt, 2H), 3.88 – 3.51 (m,10H), 2.28 – 1.87 (m, 16H), 1.36 – 1.09 (m, 8H); LC-MS (C 95 H 90 N6): 1313.7.

[0130] (3) Synthesis of compound A-1

[0131]

[0132] The compound D3 (26.07 g, 92% yield) was obtained by heating and dissolving 12-tungstic phosphate·n hydrate (3.68 g, 1.28 mmol) in a mixture of 60 mL methanol and 60 mL water, adding intermediate 2 (2 mmol), stirring for 1 h, filtering the precipitate, washing with water, and drying under reduced pressure.

[0133] The compound A-1 was characterized, and the characterization results are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 8.10– 8.07 (m, 2H), 7.89 (ddd, 2H), 7.74 (d, 2H), 7.59 – 7.45 (m, 6H), 7.39 –7.30 (m, 9H), 7.57 – 7.13 (m, 18H), 7.08 – 6.91 (m, 15H), 5.32 – 5.27 (m,2H), 4.16 – 3.93 (m, 10H), 2.58 – 2.23 (m, 12H), 1.87 – 1.24 (m, 12H); MALDI-TOF MS (C 95 H 90 N6 + ): calcd. 1314.7239.

[0134] Comparative Example 2

[0135] This comparative example provides a commercially available blue dye, for .

[0136] The properties of the mixtures or compounds provided in the above embodiments and comparative examples were tested using the following specific test methods:

[0137] UV (450 nm) absorbance: The UV spectrum of the dye was determined using a "UV-1900" manufactured by SHIMADZU. 1 mg of the mixture or compound provided in the above examples or comparative examples was dissolved in dichloromethane for testing.

[0138] Thermal stability (TGA): The TGA data of the dyes were determined using the “STAR SYSTEM TGA2” manufactured by METTLER TOLEDO.

[0139] UV characteristic peak wavelength: The UV spectrum of the dye was determined using a "UV-1900" manufactured by SHIMADZU. 1 mg of the mixture or compound provided in the above examples or comparative examples was dissolved in dichloromethane for testing.

[0140] The performance test results are shown in Table 1 below:

[0141] Table 1

[0142]

[0143] As described above, this invention achieves precise control over the overall performance of the blue dye by designing the specific composition of the blue dye and attaching a benzo5-membered ring structure (the Q-linked structure in Formula I) at a key position in the triarylmethane compound skeleton. The design of the benzo5-membered ring structure (the Q-linked structure in Formula I) in the triarylmethane compound increases the van der Waals forces between molecules, which helps improve the dispersibility and stability of the dye in the matrix. Furthermore, the presence of the large conjugated groups in the triarylmethane compound alters the electron cloud distribution of the molecule, significantly affecting the absorption spectrum of the dye and giving it stronger absorption capability at 450 nm for blue light. Simultaneously, the introduction of the benzo5-membered ring structure (the Q-linked structure in Formula I) restricts the thermal motion of the triarylmethane compound molecular chain. Compared with traditional dye structures, the rigid structural units in the blue dye molecule provided by this invention enhance the overall rigidity of the molecule, making it less prone to twisting, bending, or breaking of the molecular chain due to heat. At high temperatures, the structure of the blue dye of this invention remains relatively stable, while traditional dyes of the same type exhibit significant structural changes and performance degradation, as can be seen from the TGA comparative examples.

[0144] The applicant declares that the detailed process flow of this invention is illustrated by the above embodiments, but this invention is not limited to the above detailed process flow, that is, it does not mean that this invention must rely on the above detailed process flow to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product of this invention, addition of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this invention.

Claims

1. A triarylmethane compound, characterized in that, The triarylmethane compound has the structure shown in Formula I: Formula I; The structure shown in Formula I is selected from the following compounds: 。 2. A method for preparing the triarylmethane compound as described in claim 1, characterized in that, The preparation method includes the following steps: (1) Raw material 1 and raw material 2 react in the presence of palladium acetate, sodium tert-butoxide, tri-tert-butylphosphine and solvent A to obtain intermediate 1; Among them, raw material 1 is Raw material 2 is T 1 -X 1 and T 2 -X 2 Q, R k1 R k2 T 1 T 2 Having the same definition as claim 1, X 1 X 2 Each halogen atom represents itself independently; (2) Intermediate 1 and raw material 3 react in the presence of phosphorus oxychloride and solvent B to obtain intermediate 2; Among them, raw material 3 is and / or R1-R 16 R a1 -R a8 It has the same definition as claim 1; (3) Intermediate 2 and containing Y n- Anion exchange was performed on the compound to obtain a triarylmethane compound as shown in Formula I.

3. The preparation method according to claim 2, characterized in that, The molar ratio of raw material 1 to raw material 2 is 1:(2-2.2); And / or, T in raw material 2 1 -X 1 and T 2 -X 2 The molar ratio is 1:1; And / or, the reaction in step (1) is carried out at a temperature of 125-140°C for a time of 40-60 h; And / or, solvent A includes xylene; And / or, the reaction described in step (1) may be followed by a post-processing step, wherein the post-processing method includes steps of cooling, extraction, drying and concentration.

4. The preparation method according to claim 2, characterized in that, The molar ratio of intermediate 1 to raw material 3 is 1:(1-2.2); And / or, the reaction in step (2) is carried out at a temperature of 40-60°C for a time of 15-30 h; And / or, solvent B includes chlorobenzene; And / or, the reaction described in step (2) further includes a post-processing step, wherein the post-processing method includes the steps of separation, washing, drying, concentration and purification; And / or, the temperature of the anion exchange in step (3) is 20-30℃ and the time is 0.5-3 h; And / or, step (3) is carried out in the presence of anion exchange solvent C, wherein solvent C includes methanol and water; And / or, the reaction described in step (3) may be followed by a post-processing step, wherein the post-processing method includes steps of filtration, washing and drying.

5. A blue dye, characterized in that, The blue dye includes at least one triarylmethane compound as described in claim 1.

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