Triarylmethane dyes and their use

Abstract

The application relates to a triarylmethane dye and application thereof, and belongs to the technical field of dye compounds. The triarylmethane dye is prepared by designing the structure of the triarylmethane dye, and a dye compound with good thermal stability and high transmittance is obtained. The optical filter prepared from the triarylmethane dye has excellent comprehensive performance.

Description

Technical Field

[0001] This invention belongs to the field of dye compound technology, specifically relating to a triarylmethane dye and its applications. Background Technology

[0002] Liquid crystal displays (LCDs) have become the mainstream flat-panel displays due to their advantages such as thinness, high image quality, low power consumption, and no radiation. Generally, an LCD consists of a backlight module and a liquid crystal display panel, which typically includes a pixel array substrate, a liquid crystal layer, and a color filter. LCDs can display rich color images thanks to their internal color filters. Therefore, the requirements for color filters are constantly increasing, with demands for high brightness and high contrast ratios rising daily.

[0003] The colored layer of a filter is mainly composed of a resin composition containing colorants, which are generally dyes or pigments. Generally speaking, pigments offer better heat resistance and solvent resistance, but their brightness is not ideal; dyes, on the other hand, guarantee brightness, and triarylmethane dyes are widely used in this field. Triarylmethane dyes are characterized by their very bright colors and high color rendering, and are used as colorants for purple, blue, or green in a wide range of applications, including coatings, water-based inks, oil-based inks, inkjet inks, and color filter inks. Generally, the required properties of colorants vary depending on their intended use, but regardless of the application, most require bright hues, high color rendering, and fastness to light and heat. Known triarylmethane dyes include cationic dyes with cationic groups such as quaternary nitrogen atoms in their structure, and anionic dyes that incorporate anionic groups such as sulfonyl groups into the structure of cationic dyes, forming anionic dyes. Although the dyes mentioned above all have excellent color development, they also have drawbacks such as poor fastness in terms of light, heat, damp heat, and water.

[0004] Therefore, providing a novel triarylmethane dye with excellent overall performance has become an urgent technical problem to be solved. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a triarylmethane dye and its applications. By designing the structure of the triarylmethane dye, the present invention obtains dye compounds with good thermal stability and high transmittance. Filters prepared from this triarylmethane dye exhibit excellent overall performance.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a triarylmethane dye, said triarylmethane dye comprising compounds having the structure shown in Formula I:

[0008] ;

[0009] R1-R8 each independently represent any one of the following: substituted or unsubstituted C1-C10 straight-chain or branched alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, or halogen atom.

[0010] ah can each independently represent an integer from 1 to 4;

[0011] M1-M4 each independently represent any one of the following: single bond, O, S, substituted or unsubstituted C1-C10 straight-chain or branched alkylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C6-C20 arylene, or substituted or unsubstituted C3-C20 heteroarylene.

[0012] L indicates or , Indicates the connection site;

[0013] R A It refers to any one of substituted or unsubstituted C1-C10 straight-chain or branched alkylene groups, or substituted or unsubstituted C3-C10 cycloalkylene groups;

[0014] R B It represents any one of O, S, substituted or unsubstituted C1-C10 straight-chain or branched alkylene, substituted or unsubstituted C3-C10 cycloalkylene, substituted or unsubstituted C6-C20 arylene, and substituted or unsubstituted C3-C20 heteroarylene.

[0015] R9-R 12 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.

[0016] i or j each independently represents an integer between 0 and 2;

[0017] The R1-R8, M1-M4, R A R B R9-R 12 The substituents described herein are selected from at least one of halogen atoms, hydroxyl groups, cyano groups, C1-C6 straight-chain or branched alkyl groups, C1-C6 alkoxy groups, and C6-C15 aryl groups;

[0018] m represents an integer from 1 to 4;

[0019] Y represents PW12 O 40 3- P2W 18 O 62 6- SiW 12 O 40 4- SiW 10 O 36 8- SiW 11 O 39 8- W6O 19 2- W 10 O 32 4- WO4 2- , , , , , , Any one of the following; n represents an integer from 1 to 4.

[0020] In this invention, by designing the structure of triarylmethane dyes, and further by designing the connection between the two phenyl groups attached to the N atom via M1-M4, and further by designing specific substituents R1-R8 on the two phenyl groups attached to the N atom, a dye compound with good thermal stability and high transmittance was obtained. The filter prepared by this triarylmethane dye has excellent comprehensive performance.

[0021] In this invention, C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0022] C3-C10 can be C3, C4, C5, C6, C7, C8, C9, or C10.

[0023] C6-C20 can be C6, C8, C10, C12, C15, C18, or C20, etc.

[0024] C3-C20 can be C3, C4, C5, C7, C8, C9, C10, C12, C15, or C20, etc.

[0025] C1-C6 can be C1, C2, C3, C4, C5, or C6.

[0026] ah can each independently represent an integer from 1 to 4, for example, it can be 1, 2, 3 or 4.

[0027] i or j can each independently represent an integer between 0 and 2, for example, 0, 1 or 2.

[0028] m represents an integer from 1 to 4, such as 1, 2, 3 or 4.

[0029] n represents an integer from 1 to 4, such as 1, 2, 3, or 4.

[0030] It should be noted that when M1-M4 in the compound shown in Formula I represent single bonds, it means that the two phenyl groups are connected by single bonds.

[0031] 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.

[0032] Preferably, the triarylmethane dye has the structure shown in Formula I-1:

[0033] ;

[0034] Among them, R1-R8, M1-M4, L, m, Y, and n have the same definitions as above.

[0035] Preferably, the triarylmethane dye has the structure shown in Formula I-1-1:

[0036] ;

[0037] Among them, R1-R8, L, m, Y, and n have the same definitions as above.

[0038] This invention improves the heat resistance and transmittance of triarylmethane dyes by designing M1-M4 to represent single bonds, i.e., two phenyl groups connected by single bonds, and by designing R1-R8 to be located at the para position of the nitrogen atom.

[0039] Preferably, the C1-C10 straight-chain or branched alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, or n-decyl.

[0040] Preferably, the C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or adamantyl.

[0041] Preferably, the C6-C20 aryl group is selected from any one of phenyl, naphthyl, biphenyl, 9,9-dimethylfluorenyl, anthracene, phenanthrene, or triphenylene.

[0042] Preferably, the C3-C20 heteroaryl group is selected from any one of triazinyl, pyridyl, furanyl, carbazoleyl, dibenzofuranyl, or dibenzothiopheneyl.

[0043] Preferably, the halogen atom is selected from any one of -F, -Cl, -Br or -I.

[0044] Preferably, the C1-C10 straight-chain or branched alkylene groups are selected from any one of methylene, ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, or n-decylene.

[0045] Preferably, the C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0046] Preferably, the C6-C20 arylene group is selected from any one of phenylene, naphthylene, biphenylene, 9,9-dimethylfluorene, anthracene, phenanthrene, or triphenylene.

[0047] Preferably, the C3-C20 heteroaryl group is selected from any one of triazinyl, pyridyl, furanyl, carbazoyl, dibenzofuranyl, or dibenzothiopheneyl.

[0048] Preferably, the C1-C6 straight-chain or branched alkyl group is selected from any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 3-methylbutyl, and n-hexyl.

[0049] Preferably, the C1-C6 alkoxy group is selected from any one of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy-pentoxy, and n-hexoxy.

[0050] Preferably, the C6-C15 aryl group is selected from any one of phenyl, naphthyl, biphenyl, and 9,9-dimethylfluorenyl.

[0051] Preferably, each of R1-R8 independently represents any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0052] Preferably, L represents , , Any one of them, Indicates the connection site.

[0053] Preferably, the R A It represents any one of methylene, ethylene, or n-propylene.

[0054] Preferably, the R BIt represents any one of O, S, methylene, ethylene, n-propylene, difluoromethylene, tetrafluoroethylene, hexafluoron-propylene, or hexafluoroisopropylene.

[0055] Preferably, R9-R 12 Each can independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0056] Preferably, L represents , , , , , Any one of them, Indicates the connection site.

[0057] Preferably, the triarylmethane dye comprises the following compounds:

[0058] , , , , , , , .

[0059] It should be noted that the present invention does not impose any special limitations on the synthesis method of the triarylmethane dyes shown in Formula I, and commonly used synthesis methods in the art are applicable.

[0060] In a second aspect, the present invention provides a coloring composition comprising a triarylmethane dye as described in the first aspect.

[0061] Thirdly, the present invention provides a filter comprising a coloring layer prepared from a coloring composition as described in the second aspect.

[0062] Compared with the prior art, the present invention has the following beneficial effects:

[0063] This invention designs the structure of triarylmethane dyes, further designs the connection between two phenyl groups bonded to the N atom via M1-M4, and further designs the two phenyl groups bonded to the N atom to have specific substituents R1-R8, thus obtaining dye compounds with good thermal stability and high transmittance. The filters prepared from these triarylmethane dyes have excellent comprehensive performance. Detailed Implementation

[0064] 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.

[0065] Example 1

[0066] This embodiment provides a triarylmethane dye compound 1 and its synthesis method, which is as follows:

[0067] (1) Synthesis of intermediate A1

[0068]

[0069] Weigh 100 g (0.294 mol) of 4,4'-dibromobenzophenone, 99.42 g (0.735 mol) of 3,6-diisopropylcarbazole, and 0.19 g (0.25 mmol) of methanesulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) in 1300 mL of toluene solvent. The mixture was purged with nitrogen three times and reacted at 110 °C for 5 h. After the reaction was completed, water was added after slight cooling, and the mixture was cooled to room temperature. The mixture was filtered, and the solution was slurried and refluxed with n-heptane and ethanol (volume ratio of n-heptane to ethanol was 1:3). After cooling to room temperature, the mixture was filtered to obtain intermediate A1 (yield 75%).

[0070] Characterization of intermediate A1: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.15–7.95 (m, 8.2H), 7.75–7.40 (m, 11.9H), 2.98 (sept, 4.0H), 1.32 (d, 24.1H). LC-MS (C 49 H 48 N2O): 680.38.

[0071] (2) Synthesis of intermediate B1

[0072]

[0073] Weigh 5 g (24.97 mmol) of 3,3'-dimethyl-4,4-diaminodicyclohexylmethane, 13.32 g (52.44 mmol) of 1-iodonaphthalene, 12 g (124.85 mmol) of sodium tert-butoxide, and 0.19 g (0.25 mmol) of methanesulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) in 50 mL of toluene. The mixture was purged with nitrogen three times, heated to reflux, and reacted at 110 °C for 12 h. After the reaction was complete, water was added after cooling, and the mixture was allowed to cool to room temperature. The mixture was then filtered and separated by column chromatography to obtain intermediate B1 (75% yield).

[0074] Intermediate B1 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.88–7.76 (m, 4H), 7.50–7.30 (m, 10H), 4.52 (br s, 2H), 3.15–3.00 (m, 2H), 1.85–1.15 (m, 18H), 0.92 (d, J = 6.5 Hz, 6H). LC-MS (C 35 H 42 N2): 490.33.

[0075] (3) Synthesis of intermediate C1

[0076]

[0077] Intermediate B1 (10 g, 22.07 mmol), intermediate A1 (20.73 g, 46.25 mmol), and phosphorus oxychloride (8.46 g, 55.18 mmol) were weighed and dispersed in 100 mL of chlorobenzene. The mixture was heated to reflux and reacted for 24 h. After the reaction was completed, water and dichloromethane were added and stirred. The mixture was extracted and rotary evaporated to obtain intermediate C1 (yield 95%).

[0078] Intermediate C1 was characterized as follows: 1¹H NMR (400 MHz, deuterated chloroform) δ 8.2 (2H), 7.84–7.11 (42H), 7.11–6.9 (3H), 6.7 (3H), 6.5 (2H), 6.4 (2H), 5.3 (1H), 5.1 (1H), 4.4 (1H), 3.9 (1H), 3.36 (2H), 3.22–3.1 (4H), 2.88 (1H), 2.63–2.61 (3H), 2.15–2.05 (2H), 1.9 (1H), 1.80–1.52 (23H), 1.38–1.18 (26H), 1.05–0.9 (18H). LC-MS (C 133 H 138 N6 2+ ): 1818.16.

[0079] (4) Synthesis of triarylmethane dye compound 1

[0080]

[0081] Intermediate C1 (40 g, 21.52 mmol) was weighed and dissolved in 1000 g of methanol to obtain a methanol solution of intermediate C1. 70 g of tungstic phosphate·12 hydrate was weighed and dissolved in 1000 g of deionized water to obtain an aqueous solution of phosphotungstic acid. The methanol solution of intermediate C1 was added dropwise to the aqueous solution of phosphotungstic acid, and the mixture was heated to reflux and reacted for 6 h. After the reaction was completed, the mixture was filtered to obtain triarylmethane dye compound 1 (yield 80%).

[0082] Example 2

[0083] This embodiment provides a triarylmethane dye compound 2 and its synthesis method, which is as follows:

[0084] (1) Synthesis of intermediate A1

[0085] Intermediate A1 was synthesized according to the synthesis method of intermediate A1 provided in Example 1.

[0086] (2) Synthesis of intermediate B2

[0087]

[0088] Weigh 1.5 g (4.49 mmol) of 2,2-bis(4-aminophenyl)hexafluoropropane, 2.3 g (9.05 mmol) of 1-iodonaphthalene, 1.3 g (13.53 mmol) of sodium tert-butoxide, and 35 mg (0.45 mmol) of methanesulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) in 15 mL of toluene. The mixture was purged with nitrogen three times, heated to reflux, and reacted at 110 °C for 12 h. After the reaction was completed, water was added after cooling, and the mixture was cooled to room temperature. The mixture was filtered and separated by column chromatography to obtain intermediate B2 (yield 80%).

[0089] Characterization of intermediate B2: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.95–7.82 (m, 4H), 7.55–7.28 (m, 14H), 7.15–7.05 (m, 4H), 5.72 (br s, 2H). LC-MS (C 35 H 24 F6N2):586.18.

[0090] (3) Synthesis of intermediate C2

[0091]

[0092] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate B1 was replaced with an equimolar amount of intermediate B2 to obtain intermediate C2 (yield 80%).

[0093] Intermediate C2 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.2 (2H), 7.84–7.11 (54H), 6.9 (6H), 5.1 (2H), 3.22–3.1 (8H), 1.80–0.9 (48H). LC-MS (C 133 H 120 F6N6 2+ ):1913.61.

[0094] (4) Synthesis of triarylmethane dye compound 2

[0095]

[0096] Following the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate C2 to obtain triarylmethane dye compound 2 (yield 80%).

[0097] Example 3

[0098] This embodiment provides a triarylmethane dye compound 3 and its synthesis method, which is as follows:

[0099] (1) Synthesis of intermediate A1

[0100] Intermediate A1 was synthesized according to the synthesis method of intermediate A1 provided in Example 1.

[0101] (2) Synthesis of intermediate B3

[0102]

[0103] Weigh 4,4-diaminodiphenyl sulfide (2 g, 9.25 mmol), 1-iodonaphthalene (4.9 g, 19.43 mmol), sodium tert-butoxide (2.67 g, 27.78 mmol), and methanesulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) (72.17 mg, 0.0925 mmol) and disperse them in 20 mL of toluene. The mixture was purged with nitrogen three times, heated to reflux, and reacted at 110 °C for 12 h. After the reaction was completed, water was added after cooling, and the mixture was cooled to room temperature. The mixture was filtered and separated by column chromatography to obtain intermediate B3 (yield 80%).

[0104] Intermediate B3 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.90–7.78 (m, 4H), 7.52–7.30 (m, 10H), 7.20–7.08 (m, 8H), 5.68 (br s, 2H). LC-MS (C 32 H 24 N2S):468.16.

[0105] (3) Synthesis of intermediate C3

[0106]

[0107] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate B1 was replaced with an equimolar amount of intermediate B3 to obtain intermediate C3 (yield 80%).

[0108] Intermediate C3 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.2 (2H), 7.84–7.11 (58H), 6.96–6.62 (2H), 5.1 (2H), 3.22–3.1 (8H), 1.80–0.9 (48H). LC-MS (C130 H 120 N6S 2+ ): 1795.51.

[0109] (4) Synthesis of triarylmethane dye compound 3

[0110]

[0111] Referring to the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate C3 to obtain triarylmethane dye compound 3 (yield 80%).

[0112] Example 4

[0113] This embodiment provides a triarylmethane dye compound 5 and its synthesis method, which is as follows:

[0114] (1) Synthesis of intermediate A1

[0115] Intermediate A1 was synthesized according to the synthesis method of intermediate A1 provided in Example 1.

[0116] (2) Synthesis of intermediate B4

[0117]

[0118] 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylaniline (3 g, 11.8 mmol), 1-iodonaphthalene (6 g, 23.6 mmol), sodium tert-butoxide (3.4 g, 35.38 mmol), tris(dibenzylacetone)palladium (108 mg, 0.118 mmol), and tri-tert-butylphosphine (120 mg, 0.59 mmol) were weighed and dispersed in 30 mL of toluene. The mixture was purged with nitrogen three times, and the mixture was refluxed at 110 °C for 12 h. After the reaction was complete, water was added after cooling to room temperature. The mixture was filtered, and column chromatography was used to separate the intermediate B4 (yield 80%).

[0119] Intermediate B4 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.88–7.78 (m, 4H), 7.52–7.32 (m, 10H), 6.95 (s, 4H), 5.58 (br s, 2H), 3.82 (s, 2H), 2.26 (s, 12H). LC-MS (C 37 H 34 N2): 506.27.

[0120] (3) Synthesis of intermediate C4

[0121]

[0122] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate B1 was replaced with an equimolar amount of intermediate B4 to obtain intermediate C4 (yield 80%).

[0123] Characterization of intermediate C4: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.2 (2H), 7.84–7.11 (48H), 7.11 (2H), 6.9 (2H), 6.7 (2H), 6.5 (2H), 5.1 (2H), 3.55 (2H), 3.22–3.1 (8H), 2.31–2.05 (12H), 1.80–0.9 (48H). LC-MS (C 135 H 130 N6 2+ ): 1844.91.

[0124] (4) Synthesis of triarylmethane dye compound 5

[0125]

[0126] Following the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate C4 to obtain triarylmethane dye compound 5 (yield 80%).

[0127] Example 5

[0128] This embodiment provides a triarylmethane dye compound 6 and its synthesis method, which is as follows:

[0129] (1) Synthesis of intermediate A1

[0130] Intermediate A1 was synthesized according to the synthesis method of intermediate A1 provided in Example 1.

[0131] (2) Synthesis of intermediate B5

[0132]

[0133] Weigh 4,4'-diaminobibenzyl (1 g, 4.71 mmol), 1-iodonaphthalene (2.51 g, 9.89 mmol), sodium tert-butoxide (1.36 g, 14.13 mmol), and sulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) (74 mg, 0.094 mmol) and disperse them in 10 mL of toluene. The mixture was purged with nitrogen three times, heated to reflux, and reacted at 110 °C for 12 h. After the reaction was completed, water was added after cooling, and the mixture was cooled to room temperature. The mixture was filtered and separated by column chromatography to obtain intermediate B5 (yield 80%).

[0134] Intermediate B5 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.90–6.95 (m, 22H), 5.65 (br s, 2H), 2.88 (s, 4H). LC-MS (C 34 H 28 N2): 464.22.

[0135] (3) Synthesis of intermediate C5

[0136]

[0137] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate B1 was replaced with an equimolar amount of intermediate B5 to obtain intermediate C5 (yield 80%).

[0138] Intermediate C5 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.16–8.11 (4H), 7.94–7.38 (48H), 7.27–7.08 (6H), 6.97 (1H), 6.63–6.52 (3H), 5.3 (1H), 5.1 (1H), 4.4–3.9 (8H), 3.36 (2H), 2.88 (2H), 2.15–0.9 (48H). LC-MS (C 132 H 124 N6 2+ ):1791.62.

[0139] (4) Synthesis of triarylmethane dye compound 6

[0140]

[0141] Referring to the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate C5 to obtain triarylmethane dye compound 6 (yield 80%).

[0142] Example 6

[0143] This embodiment provides a triarylmethane dye compound 7 and its synthesis method, which is as follows:

[0144] (1) Synthesis of intermediate A2

[0145]

[0146] Weigh 1.00 g (2.94 mmol) of 4,4'-dibromobenzophenone, 1.66 g (6.20 mmol, 2.1 eq) of 2,7-diisopropyl-10H-phenoxazine, 847 mg (8.82 mmol, 3.0 eq) of sodium tert-butoxide, 54 mg (0.059 mmol, 0.02 eq) of bis(benzylacetone)palladium (54 mg, 0.059 mmol, 0.02 eq) or 93 mg (0.12 mmol, 0.04 eq) of sulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) (2'-amino-1,1'-biphenyl-3-yl)palladium(II), disperse them in 10 mL of dry toluene, purge with nitrogen three times, heat to reflux, and react at 110 °C for 16 minutes. After h, the reaction was completed, cooled, quenched with water, cooled to room temperature, filtered, and separated by column chromatography (eluent: petroleum ether / dichloromethane = 3:1) to obtain intermediate A2 (yield 80%).

[0147] Characterization of intermediate A2: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.85–7.10 (m, 12H), 6.65–6.45 (m, 8H), 2.95 (sept, J = 6.8 Hz, 4H), 1.28 (d, J = 6.8 Hz, 24H). LC-MS (C 49 H 48 N2O3): 696.37.

[0148] (2) Synthesis of intermediate B1

[0149] Intermediate B1 was synthesized according to the synthesis method of intermediate B1 provided in Example 1.

[0150] (3) Synthesis of intermediate C6

[0151]

[0152] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate A1 was replaced with an equimolar amount of intermediate A2 to obtain intermediate C6 (yield 80%).

[0153] Intermediate C6 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.25 (4H), 7.81 (4H), 7.65–6.92 (45H), 6.75 (3H), 5.3 (1H), 5.1 (1H), 3.9 (2H), 3.10–2.95 (8H), 2.57 (2H), 2.14 (2H), 1.85–1.36 (14H), 1.01–0.95 (54H). LC-MS (C 133 H 138 N6O4 2+ ):1882.34.

[0154] (4) Synthesis of triarylmethane dye compound 7

[0155]

[0156] Referring to the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate C6 to obtain triarylmethane dye compound 7 (yield 80%).

[0157] Example 7

[0158] This embodiment provides a triarylmethane dye compound 8 and its synthesis method, which is as follows:

[0159] (1) Synthesis of intermediate A3

[0160]

[0161] Weigh out bis(2,7-diisopropylphenoxazine)benzophenone (A3) (1.00 g, 1.18 mmol), photocatalyst [Ir(ppy)2(dtbbpy)]PF6 (22 mg, 0.024 mmol, 0.02 eq) or palladium acetate (26 mg, 0.12 mmol, 0.1 eq) / ligand (e.g., Xantphos, 69 mg, 0.12 mmol), cesium carbonate (768 mg, 2.36 mmol, 2.0 eq), disperse in 10 mL of dry, degassed 1,2-dichloroethane (or acetonitrile), purge with nitrogen three times, and react for 24 hours under blue LED irradiation (or at 80°C). h, the reaction was completed, cooled and quenched with saturated sodium thiosulfate solution, cooled to room temperature, extracted with ethyl acetate, dried with anhydrous sodium sulfate, filtered, and separated by column chromatography (eluent: petroleum ether / dichloromethane = 2:1, volume ratio), to obtain intermediate A3 in 80% yield.

[0162] Intermediate A3 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.15–7.90 (m, 12H), 7.75–7.40 (m, 8H), 2.95 (sept, J = 6.8 Hz, 4H), 1.28 (d, J = 6.8 Hz, 24H). LC-MS (C 49 H 48 N2O): 680.38.

[0163] (2) Synthesis of intermediate B1

[0164] Intermediate B1 was synthesized according to the synthesis method of intermediate B1 provided in Example 1.

[0165] (3) Synthesis of intermediate C7

[0166]

[0167] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate A1 was replaced with an equimolar amount of intermediate A3 to obtain intermediate C7 (yield 80%).

[0168] Intermediate C7 was characterized as follows: 1¹H NMR (400 MHz, deuterated chloroform) δ 8.2 (2H), 7.84–7.11 (42H), 7.11–6.9 (3H), 6.7 (3H), 6.5 (2H), 6.4 (2H), 5.3 (1H), 5.1 (1H), 4.4 (1H), 3.9 (1H), 3.36 (2H), 3.22–3.1 (4H), 2.88 (1H), 2.63–2.61 (3H), 2.15–2.05 (2H), 1.81–0.9 (68H). LC-MS (C 133 H 138 N6 2+ ): 1818.24.

[0169] (4) Synthesis of triarylmethane dye compound 8

[0170]

[0171] Following the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate C7 to obtain triarylmethane dye compound 8 (yield 80%).

[0172] Comparative Example 1

[0173] This embodiment provides a triarylmethane dye compound A and its synthesis method, which is as follows:

[0174] (1) Synthesis of intermediate 1

[0175]

[0176] Weigh out 4,4'-dibromobenzophenone (1.00 g, 2.94 mmol), N,N-di(4-isopropylphenyl)amine (1.48 g, 6.20 mmol, 2.1 eq), sodium tert-butoxide (847 mg, 8.82 mmol, 3.0 eq), sulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) (93 mg, 0.12 mmol, 0.04 eq) or bis(dibenzylideneacetone)palladium (54 mg, 0.059 mmol, 0.02 eq) and a ligand (such as Xantphos), disperse them in 10 mL of dry toluene, purge with nitrogen three times, heat to reflux, and react at 110 °C for 16 minutes. After h, the reaction was completed, cooled, quenched with water, cooled to room temperature, filtered, and separated by column chromatography (eluent: petroleum ether / ethyl acetate = 10:1) to obtain intermediate 1 (yield 80%).

[0177] Intermediate 1 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 7.80–7.10 (m, 24H), 2.90 (sept, J = 6.8 Hz, 4H), 1.25 (d, J = 6.8 Hz, 24H). LC-MS (C 49 H 52 N2O): 684.40.

[0178] (2) Synthesis of intermediate B1

[0179] Intermediate B1 was synthesized according to the synthesis method of intermediate B1 provided in Example 1.

[0180] (3) Synthesis of intermediate 2

[0181]

[0182] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate A1 was replaced with an equimolar amount of intermediate 1 to obtain intermediate 2 (yield 80%).

[0183] Intermediate 2 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.2 (2H), 7.81 (2H), 7.64–7.2 (24H), 7.17–6.98 (8H), 6.85–6.42 (26H), 5.3 (1H), 5.1 (1H), 4.4 (1H), 3.9 (1H), 2.97–2.89 (8H), 2.63–2.61 (2H), 2.15–2.05 (2H), 1.80–1.52 (10H), 1.38–1.28 (4H), 1.05–0.9 (54H). LC-MS (C 133 H 146 N6 2+ ): 1826.14.

[0184] (4) Synthesis of triarylmethane dye compound A

[0185]

[0186] Following the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate 2 to obtain triarylmethane dye compound A (yield 80%).

[0187] Comparative Example 2

[0188] This embodiment provides a triarylmethane dye compound B and its synthesis method, which is as follows:

[0189] (1) Synthesis of intermediate 3

[0190]

[0191] Weigh 1.00 g (1.98 mmol) of bis(9H-carbazole-9-yl)benzophenone, 1.29 g (7.92 mmol, 4.0 eq) of anhydrous ferric chloride, or DDQ (1.35 g, 5.94 mmol, 3.0 eq), disperse them in 10 mL of dry nitromethane (or 1,2-dichloroethane), purge with nitrogen three times, reflux at 80 °C for 4 h, and after the reaction is complete, cool and quench with methanol, filter, and separate by column chromatography (eluent: petroleum ether / dichloromethane = 3:1) to obtain intermediate 3 (yield 80%).

[0192] Intermediate 3 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.15–7.95 (m, 8H), 7.75–7.45 (m, 12H), 7.38–7.15 (m, 4H). LC-MS (C 37 H 24 N2O): 512.19.

[0193] (2) Synthesis of intermediate B1

[0194] Intermediate B1 was synthesized according to the synthesis method of intermediate B1 provided in Example 1.

[0195] (3) Synthesis of intermediate 4

[0196]

[0197] Referring to the synthesis method of intermediate C1 provided in Example 1, intermediate A1 was replaced with an equimolar amount of intermediate 3 to obtain intermediate 4 (yield of 80%).

[0198] Intermediate 4 was characterized as follows: 1 ¹H NMR (400 MHz, deuterated chloroform) δ 8.35–8.01 (4H), 7.99–7.41 (54H), 7.2 (2H), 6.74 (2H), 5.3 (1H), 5.1 (1H), 3.95 (2H), 2.59 (2H), 2.14 (2H). 1.85–1.36 (14H), 0.95 (6H). LC-MS (C 109 H 90N6 2+ ): 1481.41.

[0199] (4) Synthesis of triarylmethane dye compound B

[0200]

[0201] Referring to the synthesis method of triarylmethane dye compound 1 provided in Example 1, intermediate C1 was replaced with an equimolar amount of intermediate 4 to obtain triarylmethane dye compound B (yield 80%).

[0202] Comparative Example 3

[0203] This comparative example provides a triarylmethane dye compound C, which is a DNP, with the following structural formula: .

[0204] The performance of the triarylmethane dye compounds provided in the above embodiments and comparative examples was tested, and the specific test methods are as follows:

[0205] Thermal stability: TGA data for the dyes were determined using a STAR SYSTEM TGA2 instrument manufactured by METTLER TOLEDO.

[0206] UV absorption (nm): 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.

[0207] The performance test results are detailed in Table 1 below.

[0208] Table 1 Performance test data of triarylmethane dye compounds

[0209]

[0210] As can be seen from the above, this invention designs the structure of triarylmethane dyes, further designs the connection between the two phenyl groups attached to the N atom via M1-M4, and further designs the two phenyl groups attached to the N atom to have specific substituents R1-R8, thus obtaining dye compounds with good thermal stability and high transmittance. The filters prepared from these triarylmethane dyes have excellent comprehensive performance.

[0211] A comparison of Examples 1-5 and Comparative Example 3 shows that, under the premise of similar UV absorption wavelengths, the triarylmethane dyes provided by the present invention have higher thermal stability and higher transmittance at a wavelength of 450 nm.

[0212] By comparing Examples 1-7 and Comparative Examples 1-2, it can be seen that the present invention obtains triarylmethane dyes with superior performance by designing the structure of triarylmethane dyes.

[0213] 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 dye, characterized in that, The triarylmethane dyes are selected from compounds having the structure shown in Formula I: ； R1-R8 each independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. ah each independently represents 1; M1-M4 each independently represent any one of the following: single bond, O, and S; L indicates , , , , , Any one of them, Indicates the connection site; m represents an integer from 1 to 4; Y represents PW 12 O 40 3- P2W 18 O 62 6- SiW 12 O 40 4- SiW 10 O 36 8- SiW 11 O 39 8- W6O 19 2- W 10 O 32 4- WO4 2- Any one of them; n represents an integer from 1 to 4.

2. The triarylmethane dye according to claim 1, characterized in that, The triarylmethane dye has the structure shown in Formula I-1: ； Among them, R1-R8, M1-M4, L, m, Y, and n have the same definitions as in claim 1.

3. The triarylmethane dye according to claim 1, characterized in that, The triarylmethane dye has the structure shown in Formula I-1-1: ； Wherein, R1-R8, L, m, Y, and n have the same definition as in claim 1.

4. The triarylmethane dye according to claim 1, characterized in that, The triarylmethane dyes include the following compounds: , , , , , , , .

5. A coloring composition, characterized in that, The coloring composition comprises a triarylmethane dye as described in any one of claims 1-4.

6. A filter, characterized in that, The filter includes a coloring layer, which is prepared from a coloring composition as described in claim 5.

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