Halogenated ornamental blue as well as preparation method and application thereof
By introducing halogens into the blue pigment molecule, haloblue blue is generated, solving the problem of blue pigment molecule modification, achieving better staining effect and molecular properties, providing a new modification path, and laying the foundation for the synthesis of blue pigment derivatives.
Patent Information
- Application Number
- CN202512057519.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-31
- Publication Date
- 2026-04-21
AI Technical Summary
In existing technologies, the modification of the molecular structure of styrax mainly focuses on the derivation of the active amino group, making it difficult to find new modification pathways. This results in poor solubility and reactivity, limiting its application potential.
Introducing halogens into the blue molecule and reacting it with a halogenating agent to generate halogenated blue breaks the traditional modification path and provides a new modification method.
Halogenated blue has outstanding staining effect and improved molecular properties, and can be used as an important intermediate for the synthesis of other derivatives, with simple synthesis methods and post-processing procedures.
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Figure CN121895223A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of pigment synthesis technology, and in particular to a halogenated blue pigment, its preparation method, and its application. Background Technology
[0002] Indigoidine, derived from microbial metabolites, is a natural blue pigment belonging to the indigo pigment class. Structurally, it belongs to the natural compound class of alkaloids. Indigoidine is characterized by poor solubility and low reactivity. Based on the molecular structure of natural products with indigoidine, the synthesis of novel derivatives and the improvement of the physicochemical properties of the molecules are important directions for the innovative development of natural blue pigments.
[0003] Currently, most modifications to the molecular structure of *Gynostemma pentaphyllum* are based on further derivation of its active amino groups, such as amidation, esterification, and diazotization. Other types of reactions are more difficult to carry out. Finding new breakthroughs and new derivation pathways is an important direction for the innovative development of *Gynostemma pentaphyllum* structure. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides a halogenated viscose cyanide, its preparation method, and its applications. This invention introduces halogens into the viscose cyanide molecule, yielding a series of halogenated derivative compounds. The halogenated viscose cyanide not only exhibits outstanding staining effects but also breaks with the conventional approach of modifying based on the active amino group, and can serve as an important intermediate for the synthesis of other derivatives.
[0005] To achieve this objective, the present invention adopts the following technical solution:
[0006] In a first aspect, the present invention provides a halogenated viscose, the halogenated viscose having the following structure:
[0007] ;
[0008] R is selected from F, Cl, Br or I.
[0009] Preferably, the halogenated blue has the following structure:
[0010] , , , .
[0011] In a second aspect, the present invention provides a method for preparing halocyanine blue according to the first aspect, the method comprising: mixing and reacting 5,5-dihydroxycyanine blue and a halogenating agent to obtain the halocyanine blue, wherein the reaction formula is as follows:
[0012] ;
[0013] R is selected from F, Cl, Br or I.
[0014] Preferably, the halogenating agent includes any one of pyridine hydrofluoric acid (PPHF), phosphorus trichloride (PCl3), phosphorus pentachloride (PCl5), phosphorus pentabromide (PBr5), phosphorus tribromide (PBr3), or phosphorus triiodide (PI3).
[0015] Preferably, the molar ratio of 5,5-dihydroxyviscosine to the halogenating agent is 1:1 to 1:3 (e.g., 1:1, 1:2, 1:3, etc.).
[0016] Preferably, when the product is a fluorinated compound, the halogenating agent is pyridine hydrofluoric acid salt.
[0017] Preferably, when the product is a chlorinated derivative, the halogenating agent is phosphorus pentachloride.
[0018] Preferably, when the product is a chlorinated derivative, the halogenating agent is phosphorus pentabromide.
[0019] Preferably, when the product is an iodinated derivative, the halogenating agent is phosphorus triiodide.
[0020] Preferably, the reaction is carried out in the presence of a solvent.
[0021] Preferably, the solvent includes any one or a combination of at least two of dioxane, acetonitrile, or tetrahydrofuran.
[0022] Preferably, the reaction temperature is 20-30℃ (e.g., 20℃, 25℃, 30℃, etc.), and the reaction time is 1-2 h (e.g., 1 h, 1.5 h, 2 h, etc.).
[0023] Preferably, the reaction further includes a post-processing step: pouring the reaction solution into water to generate a precipitate, washing and drying the precipitate to obtain the halocyanine blue.
[0024] Preferably, the temperature of the water is 0~5℃ (e.g., 0℃, 2℃, 5℃, etc.).
[0025] Thirdly, the present invention provides an application of haloblue as described in the first aspect in dyeing.
[0026] Compared with the prior art, the present invention has at least the following beneficial effects:
[0027] This invention introduces halogens into the molecule of *Indigofera tinctoria*, resulting in a series of halogenated derivative compounds. Halogenated *Indigofera tinctoria* not only has outstanding staining effects, but also breaks the conventional approach of modifying based on the active amino group. It can be used as an important intermediate to introduce other structural fragments, further enriching the structure of the *Indigofera tinctoria* family, and can be applied in various fields in the future.
[0028] The method for synthesizing halogenated woad provided by this invention is simple and has a straightforward post-processing procedure, providing important reference for the synthesis of woad-derived structures. Attached Figure Description
[0029] Figure 1 This is the 1H NMR spectrum of 5,5-dichloroviscosine.
[0030] Figure 2 This is the mass spectrum of 5,5-dichloroviscosine.
[0031] Figure 3 This is a picture showing the staining effect of 5,5-dichlorospectroblue.
[0032] Figure 4 This is a picture showing the staining effect of 5,5-difluoroblue.
[0033] Figure 5 This is a diagram showing the staining effect of 5,5-dibromoviscose blue.
[0034] Figure 6 This is a diagram showing the staining effect of 5,5-diiodoblue. Detailed Implementation
[0035] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.
[0036] The 5,5-dihydroxyviscosine used in the following examples was provided by Nanjing Hegu Life Biotechnology Co., Ltd., while other reagents and consumables were obtained through market procurement.
[0037] The proton nuclear magnetic resonance (NMR) spectrometry was performed using an Avance II (400 MHz) NMR spectrometer; the mass spectrometry was performed using a matrix-assisted laser desorption / ionization time-of-flight mass spectrometer (MALDI-TOF).
[0038] Example 1
[0039] This embodiment provides a method for preparing 5,5-difluoroblue, comprising the following steps:
[0040] 1) Add 0.02 mol of 5,5-dihydroxyviscose blue to the reaction vessel, add 100 mL of acetonitrile and stir, add 0.02 mol of PPHF, and react at 20℃ for 2 h to obtain the reaction solution;
[0041] 2) The reaction solution was slowly added to ice water to quench the reaction, and the product precipitated out;
[0042] 3) Solid-liquid separation was performed by vacuum filtration. The retained solid was then washed with water and finally dried to obtain 3.04 g of 5,5-difluoroblue, with a yield of 49% and a purity of 81%. ESI-MS: 253.02. [MH] - .
[0043] Example 2
[0044] This embodiment provides a method for preparing 5,5-difluoroblue, comprising the following steps:
[0045] 1) Add 0.02 mol of 5,5-dihydroxyviscose blue to the reaction vessel, add 100 mL of acetonitrile and stir, add 0.06 mol of PPHF, and react at 30℃ for 1 h to obtain the reaction solution;
[0046] 2) The reaction solution was slowly added to 0°C ice water to quench the reaction, and the solid precipitated out;
[0047] 3) Solid-liquid separation was performed by vacuum filtration. The retained solid was then washed with water and finally dried to obtain 2.83 g of 5,5-difluoroblue, with a yield of 46% and a purity of 82%.
[0048] Example 3
[0049] This embodiment provides a method for preparing 5,5-dichloroviscose blue, comprising the following steps:
[0050] 1) Add 0.01 mol of 5,5-dihydroxyviscose blue to the reaction vessel, add 100 mL of tetrahydrofuran and stir, then add 0.02 mol of PCl5 and reflux for 2 h to obtain the reaction solution.
[0051] 2) Concentrate the reaction solution and slowly add it to 5°C ice water to quench it, causing the product to precipitate.
[0052] 3) Solid-liquid separation was performed by vacuum filtration. The retained solid was then washed with water and finally dried to obtain 1.43 g of 5,5-dichloroviscose blue, with a yield of 41% and a purity of 81%. The proton NMR spectrum is shown below. Figure 1 ESI-MS: 285.9. [M] Figure 2 ).
[0053] Example 4
[0054] This embodiment provides a method for preparing 5,5-dichloroviscose blue, comprising the following steps:
[0055] 1) Add 0.01 mol of 5,5-dihydroxyviscose blue to the reaction vessel, add 100 mL of tetrahydrofuran and stir, then add 0.03 mol of PCl5 and react at 25℃ for 2 h to obtain the reaction solution;
[0056] 2) The reaction solution was slowly added to ice water at 2°C to quench it, and products were also precipitated.
[0057] 3) Solid-liquid separation was performed by vacuum filtration. The retained solid was then washed with water and finally dried to obtain 1.67 g of 5,5-dichloroviscose blue, with a yield of 46% and a purity of 79%.
[0058] Example 5
[0059] This embodiment provides a method for preparing 5,5-dibromoviscose blue, comprising the following steps:
[0060] 1) Add 0.01 mol of 5,5-dihydroxyviscose blue to the reaction vessel, add 100 mL of dioxane and stir, then add 0.02 mol of PBr5 and react at 20℃ for 2 h to obtain the reaction solution;
[0061] 2) The reaction solution was slowly added to ice water to quench the reaction, and the product precipitated out;
[0062] 3) Solid-liquid separation was performed by vacuum filtration. The solid was then washed with water and finally dried to obtain 1.26 g of 5,5-dibromoviscosine, with a yield of 24% and a purity of 72%. ESI-MS m / z: 373.8 [M].
[0063] Example 6
[0064] This embodiment provides a method for preparing 5,5-dibromoviscose blue, comprising the following steps:
[0065] 1) Add 0.01 mol of 5,5-dihydroxyviscose blue to the reaction vessel, add 100 mL of tetrahydrofuran and stir, then add 0.03 mol of PBr5 and react at 30℃ for 2 h to obtain the reaction solution;
[0066] 2) The reaction solution was slowly added to ice water to quench the reaction, causing a solid to precipitate.
[0067] 3) Solid-liquid separation was performed by vacuum filtration. The solid was then washed with water and finally dried to obtain 1.36 g of 5,5-dibromoviscose blue, with a yield of 26% and a purity of 70%.
[0068] Example 7
[0069] This embodiment provides a method for preparing 5,5-diiodoblue, comprising the following steps:
[0070] 1) Add 0.01 mol of 5,5-dihydroxyviscose blue to a reaction vessel, add 100 mL of acetonitrile and stir, add 0.02 mol of PI3, and react at 25℃ for 1.5 h to obtain the reaction solution;
[0071] 2) The reaction solution was slowly added to ice water to quench the reaction, and the product precipitated out;
[0072] 3) Solid-liquid separation was performed by vacuum filtration. The solid was then washed with water and finally dried to obtain 2.05 g of 5,5-diiodoblue, with a yield of 31% and a purity of 70%. ESI-MS m / z: 468.83 [MH] - .
[0073] Comparative Example 1
[0074] This comparative example provides a method for preparing 5,5-diiodoblue, comprising the following steps:
[0075] 1) Add 0.02 mol of 5,5-dihydroxyviscose blue to a reaction vessel, add 100 mL of acetonitrile and stir, add 0.01 mol of PI3, and react at 30℃ for 1 h to obtain the reaction solution;
[0076] 2) The reaction solution was slowly added to ice water to quench it, and almost no solid was precipitated.
[0077] As can be seen from the comparison of the above embodiments, reducing the molar ratio of halogenated agents will significantly reduce the yield of the product.
[0078] Comparative Example 2
[0079] This comparative example provides a method for preparing 5,5-dichloroviscose blue, comprising the following steps:
[0080] 1) Add 0.02 mol of 5,5-dihydroxyviscose blue to a reaction vessel, add 100 mL of acetonitrile and stir, then add 0.04 mol of PCl5 and react at 35℃ for 1 h to obtain the reaction solution;
[0081] 2) The reaction solution was slowly added to ice water to quench it, and almost no solid was precipitated, and the solution turned yellow.
[0082] As can be seen from the comparison of the above embodiments, heating will cause the product to decompose, making it impossible to obtain the product.
[0083] Comparative Example 3
[0084] This comparative example provides a method for preparing 5,5-dichloroviscose blue, comprising the following steps:
[0085] 1) Add 0.02 mol of 5,5-dihydroxyviscose blue to a reaction vessel, add 100 mL of acetonitrile and stir, then add 0.04 mol of PCl5 and react at 15℃ for 1 h to obtain the reaction solution;
[0086] 2) The reaction solution was slowly added to ice water for quenching, and a blue solid precipitated out, which was identified as the raw material.
[0087] As can be seen from the comparison of the above embodiments, the reaction cannot occur at low temperatures.
[0088] Application Example 1
[0089] This application example demonstrates the use of halogenated viscose in cotton fabric dyeing: 5,5-difluoroviscose provided in Example 1 is dyed using a direct method. The steps are as follows:
[0090] 1. Dissolve the dye: Weigh 0.5g of dye and disperse it in 100mL of water.
[0091] 2. Dyeing: Heat the prepared dye solution to 30°C, then immerse the fabric in the dye solution and dye for 30 minutes.
[0092] 3. Washing: After dyeing, rinse the fabric with warm water and cold water respectively to remove any unadsorbed dye.
[0093] 4. Drying: Air dry or bake the treated fabric to ensure even dyeing and stable color.
[0094] Application Examples 2-4
[0095] Application Examples 2-4 provide an application of halogenated blue in cotton fabric dyeing. The only difference between these examples and Application Example 1 is that the 5,5-difluoroblue provided in Example 1 is replaced in equal amounts with the 5,5-dichloroblue provided in Example 3, the 5,5-dibromoblue provided in Example 6, and the 5,5-diiodoblue provided in Example 7. Other aspects are the same as in Application Example 1.
[0096] Comparative Application Example 1
[0097] The only difference between this comparative application example and application example 1 is that the 5,5-difluoroblue provided in example 1 is replaced with lemon yellow in equal amounts; otherwise, the same applies as application example 1.
[0098] Comparative Application Example 2
[0099] The only difference between this comparative application example and application example 1 is that the 5,5-difluoroviscose blue provided in example 1 is replaced with an equal amount of 5,5-dihydroxyviscose blue; otherwise, the same applies as application example 1.
[0100] The obtained cotton textiles were tested as follows: the color depth K / S value was determined using a colorimeter; the dyeing rate (%) was determined according to GB / T2391-2014 "Determination of Fixation Rate"; the lightfastness was tested according to GB / T 8427-2019 "Textiles - Tests for Color Fastness to Artificial Light: Xenon Arc"; the waterfastness was tested according to GB / T 5713-2013 "Textiles - Tests for Color Fastness to Water"; and the wet rubbing fastness was tested according to GB / T 3920-2008 "Textiles - Tests for Color Fastness to Rubbing".
[0101] The test results are shown in Table 1. The staining effects of 5,5-dichlorospectroblue, 5,5-difluorospectroblue, 5,5-dibromospectroblue, and 5,5-diiodospectroblue are respectively as follows: Figure 3 , Figure 4 , Figure 5 , Figure 6 As shown.
[0102] Table 1
[0103]
[0104] Through Table 1 and Figure 3 , Figure 4 , Figure 5 , Figure 6 As can be seen, compared to lemon yellow, the halogenated viscose of this invention exhibits more prominent application advantages: its K / S value (>10) and dyeing rate (>91%) are higher, meaning superior coloring strength and dyeing effect; at the same time, all fastness properties are comprehensively superior—lightfastness reaches grade 5 (lemon yellow is grade 4), and both washfastness (color change) and wet rubbing fastness reach grade 5, making it more competitive in terms of overall coloring ability and stability. Compared to 5,5-dihydroxy viscose, not only has the color changed significantly, but lightfastness, washfastness, and wet rubbing fastness have all been improved.
[0105] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.
Claims
1. A halogenated blue pigment, characterized in that, The halogenated blue has the following structure: ； R is selected from F, Cl, Br or I.
2. The halogenated blue according to claim 1, wherein the halogenated blue has the following structure: 、 、 、 。 3. A method for preparing halogenated viscosine according to claim 1 or 2, characterized in that, The preparation method includes: mixing and reacting 5,5-dihydroxyviscose blue and a halogenating agent to obtain the haloviscose blue, with the following general reaction formula: ； R is selected from F, Cl, Br or I.
4. The preparation method according to claim 3, characterized in that, The halogenating agent includes any one of pyridine hydrofluoric acid, phosphorus trichloride, phosphorus pentachloride, phosphorus pentabromide, phosphorus tribromide, or phosphorus triiodide.
5. The preparation method according to claim 3, characterized in that, The molar ratio of 5,5-dihydroxyviscosine to the halogenating agent is 1:1 to 1:
3.
6. The preparation method according to claim 3, characterized in that, The reaction is carried out in the presence of a solvent, which includes any one or a combination of at least two of dioxane, acetonitrile, or tetrahydrofuran.
7. The preparation method according to claim 3, characterized in that, The reaction temperature is 20-30℃, and the reaction time is 1-2 h.
8. The preparation method according to claim 3, characterized in that, The reaction also includes a post-processing procedure: the reaction solution is poured into water to generate a precipitate, and the precipitate is washed and dried to obtain the halocyanine blue.
9. The application of halocyanine blue according to claim 1 or 2 in staining.