A compound containing adamantyl and its applications

Abstract

This invention provides a compound containing adamantyl alkyl group and its applications, belonging to the field of dye compound technology. By designing the structure of the adamantyl alkyl-containing compound and further introducing the adamantyl alkyl group, this invention obtains a compound with good thermal stability. This adamantyl alkyl-containing compound can be used as a colorant, thereby preparing a high-performance filter.

Description

Technical Field

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

[0002] Among many types of displays, liquid crystal displays (LCDs) offer advantages such as lightness, thinness, low cost, low power consumption, and increased reliance on integrated circuits, and are increasingly used in laptops, monitors, and TV screens. LCD screens are closely related to our daily work and life, displaying rich color images through internal color filters. An LCD device comprises a lower substrate on which a black matrix, color filters, and ITO pixel electrodes are formed; and an upper substrate on which active circuitry, including a liquid crystal layer, thin-film transistors, and capacitor layers, and ITO pixel electrodes are formed. Each pixel is formed by sequentially stacking multiple color filters (typically the three primary colors of red, green, and blue) in a predetermined order, forming color filters within the pixel area, and a black matrix layer is arranged in a predetermined pattern on a transparent substrate to form boundaries between pixels.

[0003] With technological advancements, the demands on optical filters are constantly increasing, with a growing need for high brightness and high contrast. The colored layer of an optical filter primarily consists of a resin composition containing colorants, typically dyes or pigments. Generally, pigments offer good heat resistance and solvent resistance, but their brightness is not ideal. Therefore, providing a novel dye compound with high thermal stability has become a pressing technical challenge. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a compound containing adamantyl alkyl group and its applications. By designing the structure of the adamantyl alkyl-containing compound and further introducing the adamantyl alkyl group, the present invention obtains a compound with good thermal stability. This adamantyl alkyl-containing compound can be used as a colorant, thereby preparing a high-performance optical filter.

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

[0006] In a first aspect, the present invention provides a compound containing an adamantyl group, said adamantyl group having the structure shown in Formula I:

[0007] ;

[0008] Where R represents a hydrogen atom; R1-R6, R a -R dEach of Ar1 and Ar2 independently represents any one of the following: hydrogen atom, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, and C1-C10 alkoxy group; each of Ar1 and Ar2 independently represents a substituted or unsubstituted C6-C20 arylene group; the substituents in Ar1 and Ar2 include any one of the following: deuterium atom, halogen atom, cyano group, hydroxyl group, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, and C1-C10 alkoxy group; 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 the following; s represents 0 or 1; m represents an integer between 1 and 20, n represents an integer between 1 and 10, and (s+1)×m=n×y, where y represents 2, 3, 4, 6 or 8.

[0009] This invention designs the structure of adamantyl-containing compounds and further introduces adamantyl groups to obtain compounds with good thermal stability. These adamantyl-containing compounds can be used as colorants to prepare filters with good performance.

[0010] In this invention, C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0011] C3-C10 can be C3, C4, C5, C6, C7, C8, C9, or C10.

[0012] In this invention, m represents 1, 2, 3, 4, 6, 8, 10, 12, 14, 16, 18 or 20, etc.

[0013] n represents 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0014] 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.

[0015] 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.

[0016] Preferably, the C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0017] Preferably, the C1-C10 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentooxy, hexoxy, heptoxy, octoxy, nonoxy, or decoxy.

[0018] Preferably, R1 and R2 each independently represent any one of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.

[0019] Preferably, R3-R6 each independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0020] Preferably, the R a -R d Each can independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

[0021] Preferably, m represents an integer between 1 and 8, such as 1, 2, 3, 4, 5, 6, 7 or 8.

[0022] Preferably, s represents 1.

[0023] Preferably, n represents 1 or 2.

[0024] Preferably, the adamantyl-containing compound has the structure shown in Formula I-1 or Formula I-2:

[0025] ;

[0026] Among them, R, R3-R6, R a -R d Ar1, Ar2, Y, m, and n have the same definitions as above.

[0027] Preferably, the adamantyl-containing compound has the structure shown in Formula I-1-1 or Formula I-2-1:

[0028] ;

[0029] Among them, R, R3-R6, R a -R d Y, m, and n have the same definitions as above.

[0030] Preferably, the adamantyl-containing compound is selected from any one of the following compounds:

[0031] .

[0032] It should be noted that the present invention does not impose any special limitations on the synthesis method of the above-mentioned adamantyl-containing compounds, and commonly used synthesis methods in the art are applicable.

[0033] In a second aspect, the present invention provides a filter comprising a coloring layer, wherein the coloring agent in the coloring layer comprises an adamantyl-containing compound as described in the first aspect.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] This invention designs the structure of adamantyl-containing compounds and further introduces adamantyl groups to obtain compounds with good thermal stability. These adamantyl-containing compounds can be used as colorants to prepare filters with good performance. Detailed Implementation

[0036] 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.

[0037] Example 1

[0038] This embodiment provides a compound containing adamantyl alkyl group, the preparation method of which is as follows:

[0039] (1) Synthesis of intermediate A1

[0040]

[0041] Weigh 100 g (0.294 mol) of 4,4'-dibromobenzophenone, 99.42 g (0.735 mol) of N-ethyl-2-methylaniline, 84.79 g (0.88 mol) of sodium tert-butoxide, 29.75 g (0.15 mol) of tritert-tert-butylphosphine, and 2.69 g (2.94 mmol) of tridibenzylacetone dipalladium (2.69 g, 2.94 mmol) and disperse them in 1300 mL of toluene solvent. The nitrogen gas was purged three times and the reaction was carried out 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 slurried with n-heptane and ethanol (volume ratio of n-heptane to ethanol 3:1, total 5200 mL). After cooling to room temperature, the mixture was filtered to obtain intermediate A1 (92.3 g, yield 70%).

[0042] The intermediate A1 obtained was characterized and measured by LC-MS (C 31 H 32 N2O): 448.5.

[0043] (2) Synthesis of intermediate B1

[0044]

[0045] Weigh out 1,3-adamantanediamine (1 g, 6.01 mmol), 1-iodonaphthalene (3.2 g, 12.59 mmol), sodium tert-butoxide (1.8 g), and methanesulfonic acid (2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl)(2'-amino-1,1'-biphenyl-3-yl)palladium(II) (0.46 g) and disperse them in 10 mL of THF. Replace with nitrogen three times, heat to reflux, and react at 67 °C for 12 h. After the reaction is complete, cool slightly, add water, and cool to room temperature. Filter and separate by column chromatography to obtain intermediate B1 (1.13 g, yield 45%).

[0046] The prepared intermediate B1 was characterized and measured by LC-MS (C 30 H 30 N2): 419.5.

[0047] (3) Synthesis of intermediate C1

[0048]

[0049] Intermediate B1 (1.93 g, 1.43 mmol), intermediate A1 (1.35 g, 3 mmol), and phosphorus oxychloride (0.66 g) were weighed and dispersed in 6 mL of chlorobenzene. The mixture was heated to reflux and reacted for 24 h. After the reaction was completed, 6 mL of dichloromethane was added after cooling to room temperature, and then pure water was added for extraction until neutral. The mixture was then rotary evaporated to obtain intermediate C1 (1.56 g, yield 80%).

[0050] The intermediate C1 obtained was characterized and measured by LC-MS (C 92 H 92 N6 2+ ): 641.0.

[0051] (4) Synthesis of compounds containing adamantyl groups

[0052]

[0053] 10 g of intermediate C1 was weighed and dissolved in 100 mL of methanol to obtain a methanol solution of intermediate C1. 17.7 g of tungstate 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 the above-mentioned compound containing adamantyl (15 g, yield 63%).

[0054] The prepared adamantyl-containing compound was characterized, and the results were obtained by LC-MS (C 92 H 92 N6 2+ ): 641.5.

[0055] Example 2

[0056] This embodiment provides a compound containing adamantyl alkyl group, the preparation method of which is as follows:

[0057] (1) Synthesis of intermediate A1

[0058] Intermediate A1 was synthesized using the synthesis method for intermediate A1 provided in Example 1;

[0059] (2) Synthesis of intermediate B2

[0060]

[0061] Following the method for synthesizing intermediate B1 provided in Example 1, 1,3-adamantanediamine (6.01 mmol) was replaced with adamantaneamine (3 mmol) to obtain intermediate B2 (0.46 g, yield 55%).

[0062] The intermediate B2 obtained was characterized by LC-MS (C 20 H 23 N ): 277.6.

[0063] (3) Synthesis of intermediate C2

[0064]

[0065] Following the synthesis method of intermediate C1 provided in Example 1, intermediate B1 (1.43 mmol) was replaced with intermediate B2 (0.72 mmol) to obtain intermediate C2 (0.41 g, yield 76%).

[0066] The intermediate C2 obtained was characterized by LC-MS (C 51 H 54 N3 + ): 709.0.

[0067] (4) Synthesis of compounds containing adamantyl groups

[0068]

[0069] Referring to the method for synthesizing the adamantyl-containing compound provided in Example 1, intermediate C1 was replaced with intermediate C2 to obtain the above-mentioned adamantyl-containing compound (yield 65%).

[0070] The prepared adamantyl-containing compounds were characterized by LC-MS (C 51 H 54 N3 + ): 709.6.

[0071] The properties of the adamantyl-containing compounds provided in the above embodiments were characterized using the following specific test methods:

[0072] Thermal stability (TGA): The temperature of the adamantyl-containing compound provided in the above examples or the compound provided in the comparative examples at 5% weight loss was determined using a “STAR SYSTEM TGA2” manufactured by METTLER TOLEDO, and the results are used as TGA data.

[0073] UV characteristic peak wavelength: The UV spectrum of the dye was determined using a "UV-1900" manufactured by SHIMADZU. 1 mg of the adamantyl compound provided in the above examples was dissolved in dichloromethane for testing.

[0074] The performance test results are shown in Table 1 below:

[0075] Table 1 Performance test results of compounds containing adamantyl groups

[0076]

[0077] This invention designs the structure of adamantyl-containing compounds and further introduces adamantyl groups to obtain compounds with good thermal stability. These adamantyl-containing compounds can be used as colorants to prepare filters with good performance.

[0078] 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 compound containing adamantyl alkyl group, characterized in that, The adamantyl-containing compound has the structure shown in Formula I: ； Where R represents a hydrogen atom; R1-R6, R a -R d Each of the following can be independently represented: hydrogen atom, C1-C10 straight-chain or branched alkyl group, C3-C10 cycloalkyl group, and C1-C10 alkoxy group; Ar1 and Ar2 each independently represent any one of phenylene, naphthylene, or biphenylene; 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; s represents 0 or 1; m represents an integer between 1 and 20, n represents an integer between 1 and 10, and (s+1)×m=n×y, where y represents 2, 3, 4, 6 or 8.

2. The compound containing adamantyl alkyl group according to claim 1, characterized in that, 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. The C3-C10 cycloalkyl group is selected from any one of cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl; The C1-C10 alkoxy groups are selected from any one of methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentooxy, hexoxy, heptoxy, octoxy, nonoxy, or decoxy.

3. The compound containing adamantyl alkyl group according to claim 1, characterized in that, R1 and R2 each independently represent any one of hydrogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; R3-R6 each independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl. The R a -R d Each can independently represent any one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.

4. The compound containing adamantyl alkyl group according to claim 1, characterized in that, The s represents 1.

5. The compound containing adamantyl alkyl group according to claim 1, characterized in that, The m represents an integer between 1 and 8; The n represents 1 or 2.

6. The compound containing adamantyl alkyl group according to claim 1, characterized in that, The adamantyl-containing compound has the structure shown in Formula I-1 or Formula I-2: ； Among them, R, R3-R6, R a -R d Ar1, Ar2, Y, m, and n have the same definitions as in claim 1.

7. The compound containing adamantyl alkyl group according to claim 1, characterized in that, The adamantyl-containing compound has the structure shown in formula I-1-1 or formula I-2-1: ； Among them, R, R3-R6, R a -R d Y, m, and n have the same definitions as in claim 1.

8. The compound containing adamantyl alkyl group according to claim 1, characterized in that, The adamantyl-containing compound is selected from any one of the following compounds: 。 9. A filter, characterized in that, The filter includes a coloring layer, wherein the colorant in the coloring layer includes an adamantyl compound as described in any one of claims 1-8.

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