Preparation method of blue dye

Abstract

The invention belongs to the technical field of dyes, and particularly relates to a preparation method of a blue dye. Aromatic hydrocarbon and amine are used as substrates to react at 60-160 DEG C under the catalytic condition of a copper-based catalyst to obtain the triarylmethane dye as shown in the formula (I), according to the method, a noble metal Pd catalyst is replaced by a cheap metal Cu catalyst, so that the reaction cost is lower, the operability is higher, and the yield is more excellent.

Description

Technical Field

[0001] The invention belongs to the technical field of dyes, and particularly relates to a preparation method of a blue dye. Background Art

[0002] Liquid crystal display screens are closely related to our daily work and life. They rely on the internal color filters to display rich color images. Therefore, the requirements for filters are constantly increasing, and the demand for high brightness, high contrast and other performance is increasing. The coloring layer of the filter is mainly composed of a resin composition containing a colorant, and the colorant is generally a dye or a pigment. Generally speaking, when pigments are used, the heat resistance, solvent resistance and other properties are good, but the brightness is not ideal; when dyes are used, the brightness can be guaranteed, but the various tolerances are worse than pigments. In this regard, a dispersant with a special structure (JP2011006602) can be added to ensure that various performance standards are met; or the dye can be laked (salted) to improve its tolerance (JP2008304766, WO2012144521).

[0003] Triarylmethane dyes are widely used in this field. When used, they can be made into salt compounds to ensure high brightness, high contrast and high solvent resistance. In patent WO2012144521, a palladium-based catalyst is required to prepare triarylmethane dyes, but the palladium-based catalyst is a precious metal catalyst and the cost is too high. Summary of the invention

[0004] The main purpose of the invention is to provide a method for preparing a blue dye.

[0005] To achieve the above object, the technical solution adopted by the present invention is:

[0006] A method for preparing a blue dye, wherein aromatic hydrocarbons and amines are used as substrates and reacted at 60-160° C. under the catalytic conditions of a copper-based catalyst to obtain a triarylmethane dye represented by formula (I);

[0007] Formula (I):

[0008]

[0009] In formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6The same or different groups are selected from H, C1-C12 alkyl which is unsubstituted or substituted by at least one of the following substituents, and aryl which is unsubstituted or substituted by at least one of the following substituents; wherein the following substituents are halogen, nitro, cyano, C1-C12 alkyl, ester, C1-C12 alkyl ether, hydroxyl, amino, sulfonic acid, carboxyl or C3-C12 heterocycle containing at least one heteroatom.

[0010] Ar is unsubstituted or substituted with at least one R 7 substituted aryl;

[0011] R 7 It is halogen, C1-C12 alkyl, C1-C12 alkoxy, hydroxyl or amino.

[0012] In the formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 The same or different groups are selected from H, C1-C8 alkyl which is unsubstituted or substituted by at least one of the following substituents, and aryl which is unsubstituted or substituted by at least one of the following substituents; wherein the following substituents are halogen, C1-C8 alkyl, ester, C1-C8 alkyl ether, hydroxyl, and amino.

[0013] Ar is unsubstituted or substituted with at least one R 7 substituted aryl;

[0014] R 7 It is halogen, C1-C8 alkyl, C1-C8 alkoxy, hydroxyl or amino.

[0015] The aromatic group is benzene, naphthalene, anthracene or phenanthrene.

[0016] Specifically:

[0017] Mix halogen-containing aromatic hydrocarbons (Ar) and amines (R) in a solvent. 5 R 6 NH), add a Cu-based catalyst and a base, raise the temperature to T, react for t hours, and after the reaction is completed, add water, cool and precipitate solids, filter, wash and dry to obtain an intermediate;

[0018] The intermediate and benzophenone compounds are added to a solvent and stirred to disperse, then phosphorus oxychloride is added, the temperature is raised and refluxed for 2-5 hours, after the reaction is completed, the mixture is filtered, washed and dried to obtain the triarylmethane dye represented by formula (I).

[0019] The Cu-based catalyst is a substance containing copper and a ligand, wherein the amount of the substance containing copper is 1 mol%-10 mol% of the aryl group (Ar) containing halogen; the amount of the ligand is 1 mol%-20 mol% of the aryl group (Ar) containing halogen.

[0020] The copper-containing substance is a monovalent copper oxide or copper salt, specifically, Cu2O, CuI, or CuCl.

[0021] The ligand can be L-proline, N,N-dimethylglycine, 2-isobutyrylcyclohexanone, 1,1'-dinaphthalene-2,2'-diol, 1,10-phenanthroline and a substance represented by formula (L1);

[0022] Formula (L1):

[0023]

[0024] Furthermore, a halogen-containing aromatic hydrocarbon (Ar) and an amine (R 5 R 6 NH), add a Cu-based catalyst and a base, raise the temperature to 60-160°C, react for 6-36 hours, add water after the reaction is completed, cool and precipitate solids, filter, wash and dry to obtain an intermediate; the halogen-containing aromatic hydrocarbon (Ar) and amine (R 5 R 6 The molar ratio of NH) is 1:1-2.5:1.

[0025] The above-mentioned halogen-containing aromatic hydrocarbons (Ar) are m-iodotoluene, 1-iodonaphthalene, 1-bromonaphthalene, 1-iodo-2-naphthol, etc.; amines (R 5 R 6 NH) is p-phenylenediamine, p-methoxyaniline, and tetrahydrofurfurylamine.

[0026] The solvent is one or more of DMF, DMSO, toluene, xylene, tetrahydrofuran, ethanol, n-propanol, acetonitrile, and 1,4-dioxane;

[0027] The base is an organic base and / or an inorganic base, and the amount used is 1-1.2 equivalents of the halogen-containing aromatic hydrocarbon (Ar).

[0028] The intermediate and benzophenone compound are added to a solvent and stirred to disperse, then phosphorus oxychloride is added, the temperature is raised and refluxed for 2-5 hours, and after the reaction is completed, the filter is filtered, and the filter cake is washed with methanol, 5% dilute hydrochloric acid and water in sequence. After washing, the filter cake is dried at 110° C. for 6 hours to obtain the triarylmethane dye represented by formula (I); the molar ratio of the intermediate to phosphorus oxychloride is 1:1-1:2.

[0029] The benzophenone compounds are 4,4'-bis(diethylamino)benzophenone, 4,4'-dibromobenzophenone, 4,4'-dichlorobenzophenone, 4-(dimethylamino)benzophenone and the like.

[0030] The solvent may be one or more of DMF, DMSO, toluene, xylene, tetrahydrofuran, ethanol, n-propanol, acetonitrile, and 1,4-dioxane.

[0031] The present invention has the following beneficial effects:

[0032] The present invention uses a cheap metal Cu catalyst to replace a noble metal Pd catalyst, so the reaction cost is lower, the operability is stronger, and the yield is better. DETAILED DESCRIPTION

[0033] The present invention is further described below in conjunction with examples. It should be noted that the specific implementation methods described herein are only for illustrating and explaining the present invention and are not intended to limit the present invention.

[0034] Example 1

[0035] In a 250mL three-necked flask, add 1-iodonaphthalene 12.7g (0.05mol), p-phenylenediamine 3.41g (0.025mol), potassium tert-butoxide 6.73g (0.06mol), Cu-based catalyst 0.438g (2mol% CuI / 2mol% L1) and 60mL 1,4-dioxane, heat and reflux, and react for 12 hours. After the reaction is completed, add 120mL of water after slightly cooling, cool to room temperature, filter, wash with methanol first, then wash with water, and dry the filter cake to obtain 8.25g (yield 85%) of intermediate 1.

[0036] Intermediate 1:

[0037]

[0038] Mass spectrometry (MS) test: The molecular weight Mr was determined to be 388.

[0039] Element analysis test: CHN test values: 86.17%, 6.65%, 7.18% (theoretical values: 86.56%, 6.23%, 7.21%).

[0040] In a 150mL three-necked flask, add 8.25g (0.021mol) of intermediate 1, 80mL of toluene, and 13.63g (0.042mol) of 4,4'-bis (diethylamino) benzophenone. After stirring and dispersing, add 6.44g (0.042mol) of phosphorus oxychloride and reflux for 5 hours. After the reaction is completed, filter and wash with methanol first, then stir and disperse the filter cake in 5% dilute hydrochloric acid for 20 minutes, filter and wash with water. Dry the filter cake at 110°C for 6 hours to obtain 15.48g of the product triarylmethane dye (B1) (yield 68%).

[0041] B1:

[0042]

[0043] Mass spectrometry (MS) test: The molecular weight Mr was determined to be 1002.6.

[0044] Element analysis test: CHN test value: 83.71%, 7.80%, 8.49% (theoretical value: 83.79%, 7.84%, 8.38%).

[0045] Comparative Example 1

[0046] The Cu-based catalyst in Example 1 was changed to the Pd-based catalyst in the synthesis example of patent WO2012144521, and the other conditions remained unchanged. The final product (B1) was about 2.73 g (yield 12%).

[0047] Example 2

[0048] In a 150 mL three-necked flask, 12.7 g (0.05 mol) of 1-iodonaphthalene, 6.16 g (0.05 mol) of p-methoxyaniline, 2.81 g (0.05 mol) of potassium hydroxide, 0.219 g (1 mol% CuI / 1 mol% L1) of Cu-based catalyst and 40 mL of ethanol were added, and the mixture was heated to reflux and reacted for 12 hours. After the reaction was completed, 80 mL of water was added, the mixture was cooled to room temperature, filtered, washed with methanol first, then washed with water, and the filter cake was dried to obtain 11.59 g (yield 93%) of intermediate 2.

[0049] Intermediate 2:

[0050]

[0051] Mass spectrometry (MS) test: The molecular weight Mr was determined to be 249.

[0052] Element analysis test: CHON test values: 81.61%, 6.33%, 6.59%, 5.47% (theoretical values: 81.9%, 6.06%, 6.42%, 5.62%).

[0053] In a 150mL three-necked flask, add 11.59g (0.0465mol) of intermediate 2, 80mL of toluene, and 15.09g (0.0465mol) of 4,4'-bis (diethylamino) benzophenone. After stirring and dispersing, add 6.44g (0.0465mol) of phosphorus oxychloride and reflux for 2 hours. After the reaction is completed, filter and wash with methanol first, then stir and disperse the filter cake in 5% dilute hydrochloric acid for 20 minutes, filter and wash with water. Dry the filter cake at 110°C for 6 hours to obtain 24.51g of the product triarylmethane dye (B2) (yield 89%).

[0054] B2:

[0055]

[0056] Mass spectrometry (MS) test: determined molecular weight Mr = 556.3.

[0057] Element analysis test: CHON test values: 81.75%, 7.65%, 2.98%, 7.62% (theoretical values: 81.98%, 7.6%, 2.87%, 7.55%).

[0058] Example 3

[0059] In a 150mL three-necked flask, 12.7g (0.05mol) of 1-iodonaphthalene, 5.06g (0.05mol) of tetrahydrofurfurylamine, 19.55g (0.06mol) of cesium carbonate, 2.10g of Cu-based catalyst (10mol% CuI / 20mol% L-proline) and 60mL of DMF were added, and the temperature was raised to reflux, and the reaction was carried out for 24 hours. After the reaction was completed, it was cooled, 60mL of water was added, and then most of the solvent was removed by vacuum distillation, and then 50mL of dichloromethane was poured in, and the mixture was filtered after stirring, and washed with methanol first, then washed with water, and the filter cake was dried to obtain 9.42g (yield 83%) of intermediate 3.

[0060] Intermediate 3:

[0061]

[0062] Mass spectrometry (MS) test: molecular weight Mr=227.

[0063] Element analysis test: CHON test values: 79.11%, 7.58%, 7.16%, 6.15% (theoretical values: 79.26%, 7.54%, 7.04%, 6.16%).

[0064] In a 150mL three-necked flask, add 9.42g (0.0415mol) of intermediate 2, 80mL of toluene, and 13.46g (0.0415mol) of 4,4'-bis (diethylamino) benzophenone. After stirring and dispersing, add 5.75g (0.0415mol) of phosphorus oxychloride and reflux for 3 hours. After the reaction is completed, filter and wash with methanol first, then stir and disperse the filter cake in 5% dilute hydrochloric acid for 20 minutes, filter and wash with water. Dry the filter cake at 110°C for 6 hours to obtain 15.14g (yield 81%) of the product triarylmethane dye (B3).

[0065] B3:

[0066]

[0067] Mass spectrometry (MS) test: molecular weight Mr=534.

[0068] Element analysis test: CHON test values: 80.81%, 8.33%, 3.11%, 7.75% (theoretical values: 80.86%, 8.29%, 2.99%, 7.86%).

Claims

1. A method for preparing a blue dye, characterized in that: Aromatic hydrocarbons and amines are used as substrates and reacted at 60-160° C. under the catalytic conditions of a copper-based catalyst to obtain a triarylmethane dye represented by formula (I); Formula (I): In formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 The same or different groups are selected from H, C1-C12 alkyl groups which are unsubstituted or substituted by at least one of the following substituents, and aryl groups which are unsubstituted or substituted by at least one of the following substituents; wherein the following substituents are halogen, nitro, cyano, C1-C12 alkyl, ester, C1-C12 alkyl ether, hydroxyl, amino, sulfonic acid, carboxyl or C3-C12 heterocycle containing at least one heteroatom; Ar is unsubstituted or substituted with at least one R 7 substituted aryl; R 7 It is halogen, C1-C12 alkyl, C1-C12 alkoxy, hydroxyl or amino.

2. The method for preparing a blue dye according to claim 1, wherein: In the formula (I), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 The same or different are selected from H, C1-C8 alkyl which is unsubstituted or substituted by at least one of the following substituents, and aryl which is unsubstituted or substituted by at least one of the following substituents; wherein the following substituents are halogen, C1-C8 alkyl, ester, C1-C8 alkyl ether, hydroxyl, and amino; Ar is unsubstituted or substituted with at least one R 7 substituted aryl; R 7 It is halogen, C1-C8 alkyl, C1-C8 alkoxy, hydroxyl or amino.

3. The method for preparing a blue dye according to claim 1 or 2, characterized in that: The aromatic group is benzene, naphthalene, anthracene or phenanthrene.

4. The method for preparing a blue dye according to claim 1 or 2, characterized in that: Mix halogen-containing aromatic hydrocarbons (Ar) and amines (R) in a solvent. 5 R 6 NH), add a Cu-based catalyst and a base, raise the temperature to T, react for t hours, and after the reaction is completed, add water, cool and precipitate a solid, filter, wash, and dry to obtain an intermediate; The intermediate and benzophenone compounds are added to a solvent and stirred to disperse, then phosphorus oxychloride is added, the temperature is raised and refluxed for 2-5 hours, after the reaction is completed, the mixture is filtered, washed and dried to obtain the triarylmethane dye represented by formula (I).

5. The method for preparing a blue dye according to claim 4, wherein: The Cu-based catalyst is a substance containing copper and a ligand, wherein the amount of the substance containing copper is 1 mol%-10 mol% of the aryl group (Ar) containing halogen; the amount of the ligand is 1 mol%-20 mol% of the aryl group (Ar) containing halogen. The copper-containing substance is a monovalent copper oxide or copper salt.

6. The method for preparing a blue dye according to claim 5, wherein: The ligand can be L-proline, N,N-dimethylglycine, 2-isobutyrylcyclohexanone, 1,1'-dinaphthalene-2,2'-diol, 1,10-phenanthroline and a substance represented by formula (L1); Formula (L1):

7. The method for preparing a blue dye according to claim 4, wherein: Mix halogen-containing aromatic hydrocarbons (Ar) and amines (R) in a solvent. 5 R 6 NH), add a Cu-based catalyst and a base, raise the temperature to 60-160°C, react for 6-36 hours, add water after the reaction is completed, cool and precipitate solids, filter, wash and dry to obtain an intermediate; the halogen-containing aromatic hydrocarbon (Ar) and amine (R 5 R 6 The molar ratio of NH) is 1:1-2.5:

1.

8. The method for preparing a blue dye according to claim 7, wherein: The solvent is one or more of DMF, DMSO, toluene, xylene, tetrahydrofuran, ethanol, n-propanol, acetonitrile, and 1,4-dioxane; The base is an organic base and / or an inorganic base, and the amount used is 1-1.2 equivalents of the halogen-containing aromatic hydrocarbon (Ar).

9. The method for preparing a blue dye according to claim 4, wherein: The intermediate and benzophenone compound are added to a solvent and stirred to disperse, and then phosphorus oxychloride is added, and the temperature is raised to reflux for 2-5 hours. After the reaction is completed, the reaction is filtered, and the precipitate is washed with methanol, 5% dilute hydrochloric acid, and water in sequence. After washing, the filter cake is dried at 110° C. for 6 hours to obtain the triarylmethane dye represented by formula (I); the molar ratio of the intermediate to phosphorus oxychloride is 1:1-1:

2.

10. The method for preparing a blue dye according to claim 9, characterized in that: The solvent may be one or more of DMF, DMSO, toluene, xylene, tetrahydrofuran, ethanol, n-propanol, acetonitrile, and 1,4-dioxane.

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