A phenoxazine dye intermediate, dye precursor, dye and method for the preparation thereof

Abstract

The present application relates to a kind of phenoxazine type dye intermediates, dye precursor, dye and its preparation method, belong to dye technical field.The phenoxazine type dye of the present application is the dye matrix with the phenoxazine intermediate, grafting cyanuric chloride with genipin double active groups, phenoxazine type dye intermediate has excellent color light stability, and high color strength, color light bright, can be dyed in supercritical fluid to fiber.Through the reaction of the iridoid structure of genipin and the amino group on protein fiber, the trinity of fiber-dye-color is generated in the dyeing process.The phenoxazine type dye does not need to apply to water and other dyeing auxiliaries in the dyeing process, the novel special dyeing method, the green environmental protection of dyeing process, the equipment friendly, has better application prospect in supercritical CO2 dyeing.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of dyes, and particularly relates to a phenoxazine type dye intermediate, a dye precursor, a dye and a preparation method thereof. BACKGROUND

[0002] Supercritical CO2 fluid technology changes CO2 gas into a supercritical state under high temperature and high pressure conditions, replaces water medium, and performs dyeing and functional finishing on textiles under the action of various dyes or auxiliaries. After dyeing, there is no need for drying, which solves the problem of consumption of a large amount of water resources and heat energy in the printing and dyeing process (see document: Banchero M. Recent advances in supercritical fluid dyeing [J]. Coloration Technology, 2020, 136(4): 317-335.).

[0003] In supercritical CO2 fluid, a single dye molecule exhibits excellent diffusion efficiency, and its diffusion rate significantly exceeds that in a conventional aqueous solution environment, effectively improving the dyeing efficiency. The sample after SCF-CO2 dyeing is colored uniformly, and the effect is comparable to that of traditional water bath dyeing. Among them, good results have been achieved in dyeing processing of polyester fibers using disperse dyes in supercritical CO2 fluid, and several reactive disperse dyes have been developed to successfully dye cellulose fibers, but there are very few reactive disperse dyes for protein fibers. Protein fibers have very wide performance in life, and it is necessary to develop a supercritical CO2 special protein fiber reactive disperse dye (see document: Zhu W W, Long J J, Shi MW. Resveratrol-Loaded Diacetate Fiber by Supercritical CO2 Fluid Assisted Impregnation [J]. Materials, 2022, 15(16): 797-804.).

[0004] Currently, there are few types of reactive disperse dyes suitable for use in supercritical CO2. Generally, azo or anthraquinone structures are used as dye precursors, and triazine, ethylene sulfone and bromoacrylamide are used as reactive groups to synthesize reactive disperse dyes. Azo reactive disperse dyes are generally suitable for preparing light color dyes, such as orange, yellow and other similar bright colors. Anthraquinone reactive disperse dyes tend to produce dark colors, especially blue-green tones, and often have higher production costs. In addition, the colorfastness of these two types of reactive disperse dyes after dyeing protein fibers is poor, which also greatly limits their application.

[0005] Therefore, it is still of market value to prepare non-azolium reactive disperse dyes for protein fibers to obtain bright and high-intensity color performance. SUMMARY

[0006] To solve the above technical problems, the present application provides a phenoxazine type dye intermediate, a dye precursor, a dye and a preparation method thereof. The oxazine structure contains N, O and other heteroatoms, has high color strength and excellent heat resistance, and can be used as a dye intermediate. In order to improve the dyeing performance on protein fibers, a cyanuric chloride group is grafted on the molecular structure to form a dye precursor, and then a genipin group is grafted to form a reactive disperse dye. The phenoxazine type dye can be used for dyeing fibers such as wool, cashmere and silk in supercritical CO2 fluid due to its low polarity and the effect of active groups.

[0007] The first object of the present application is to provide a phenoxazine type dye intermediate, the structure of which is shown in formula III:

[0008]

[0009] X = Br, Cl, F or NO2;

[0010] Y = OH, NH2 or NHR, R = CH3 or CH2CH3.

[0011] The second object of the present application is to provide a preparation method of the phenoxazine type dye intermediate, comprising the following steps: under the action of an oxidizing agent, a compound of formula I and a compound of formula II are reacted in water to obtain a phenoxazine type dye intermediate of formula III.

[0012] The structural formulas of formula I-III are as follows:

[0013]

[0014] X = Br, Cl, F or NO2;

[0015] Y = OH, NH2 or NHR, R = CH3 or CH2CH3.

[0016] In an embodiment of the present application, the molar ratio of the compound of formula I to the compound of formula II is 1:(1-3).

[0017] In an embodiment of the present application, the oxidizing agent is selected from one or more of sodium periodate, potassium permanganate, potassium persulfate, sodium persulfate and ferric chloride.

[0018] In one embodiment of the present application, the reaction is carried out at a pH of 9-11, a temperature of 20-40℃, and for a time period of 30-90 minutes.

[0019] In one embodiment of the present application, the pH adjusting agent is sodium carbonate.

[0020] A third object of the present application is to provide a phenoxazine dye precursor having the structure of Formula V:

[0021]

[0022] wherein X = Br, Cl, F or NO2;

[0023] Y = OH, NH2 or NHR, wherein R = CH3 or CH2CH3;

[0024] Z = Cl or F.

[0025] A fourth object of the present application is to provide a method for preparing the phenoxazine dye precursor, comprising the steps of: reacting the phenoxazine dye intermediate of Formula III and the compound of Formula IV in a solvent to obtain the phenoxazine dye precursor of Formula V.

[0026] wherein the structural formulae of Formula IV-Formula V are as follows:

[0027]

[0028] wherein X = Br, Cl, F or NO2;

[0029] Y = OH, NH2 or NHR, wherein R = CH3 or CH2CH3;

[0030] Z = Cl or F.

[0031] In one embodiment of the present application, the molar ratio of the phenoxazine dye intermediate of Formula III and the compound of Formula IV is 1: (1-3).

[0032] In one embodiment of the present application, the reaction is carried out at a pH of 9-11, a temperature of 0-16℃, and for a time period of 18-26 hours.

[0033] In one embodiment of the present application, the pH adjusting agent is sodium carbonate.

[0034] A fifth object of the present application is to provide a phenoxazine dye having the structure of Formula VI:

[0035]

[0036] wherein X = Br, Cl, F or NO2;

[0037] Y = OH, NH2 or NHR, where R = CH3 or CH2CH3;

[0038] Z = Cl or F.

[0039] A sixth object of the present application is to provide a method for preparing the phenoxazine dye, comprising the following steps: reacting the phenoxazine dye precursor of the structure of formula V and genipin in a solvent to obtain the phenoxazine dye of the structure of formula VI.

[0040] In an embodiment of the present application, the reaction is carried out at a pH of 9-11, a temperature of 32-48℃, and for a time of 10-18h.

[0041] In an embodiment of the present application, the pH regulator is sodium carbonate.

[0042] The technical solution of the present application has the following advantages compared with the prior art:

[0043] (1) The phenoxazine dye of the present application is prepared from a phenoxazine dye precursor and genipin. The phenoxazine dye intermediate has a conjugated cyclic structure containing N, O and other heteroatoms, has high color strength, and has excellent heat resistance. The phenoxazine dye precursor is a cyanuric chloride group grafted on a phenoxazine ring. It not only has the excellent performance of the phenoxazine dye intermediate, but also introduces a cyanuric chloride group, which is an excellent active group that can undergo a nucleophilic substitution reaction with a fiber, allowing the dye to adhere firmly to the fiber. The phenoxazine dye precursor thus obtained can be used as a dye precursor and as a separate active disperse dye.

[0044] (2) The active group of the phenoxazine dye of the present application is fixed to the protein fiber through a nucleophilic substitution reaction, and the iridoid structure of genipin reacts with the amino group on the protein fiber. The dyeing process produces a trinity of fiber-dye-color. The phenoxazine dye does not need to be applied to water and other dyeing auxiliaries during the dyeing process. The dyeing method is novel and special, the dyeing process is green and environmentally friendly, friendly to equipment, and has good application prospects in supercritical CO2 dyeing.

[0045] (3) The phenoxazine type dye has phenoxazine as a parent body, contains two active groups of trichloro cyanogen and genipin. Due to the low polarity of the dye itself and the activity of the active groups, when the protein fiber is dyed in the supercritical CO2 fluid system, not only can it be smoothly dissolved in the supercritical fluid, but also can react with the amino group in the protein to form a new conjugated system to produce color, which can be used as a special dye for protein in the supercritical CO2 system, adds the variety of active disperse dyes, and solves the problem of limited protein fiber dyeing in the supercritical dyeing system.

[0046] (4) The phenoxazine type dye contains elements such as nitrogen and sulfur in the molecular structure, and such a conjugated system enhances the color performance of the dye, so that it exhibits higher color saturation and brightness.

[0047] (5) The preparation method is simple to operate, easy to control, has high reaction conversion rate, and the obtained phenoxazine type active disperse dye has bright color, good directness to fiber, stable color light, and the two active groups are more firmly combined with the fiber, which has broad application prospect in supercritical CO2 dyeing. BRIEF DESCRIPTION OF DRAWINGS

[0048] In order to make the content of the present application more easily understood, the present application will be further described in detail below according to specific embodiments of the present application and in conjunction with the drawings, in which:

[0049] Figure 1 It is a Fourier infrared spectrum of the phenoxazine type dye intermediate of example 1 in test example 1 of the present application;

[0050] Figure 2 It is a Fourier infrared spectrum of the phenoxazine type dye precursor of example 2 in test example 1 of the present application;

[0051] Figure 3 It is a Fourier infrared spectrum of the phenoxazine type dye of example 3 in test example 1 of the present application;

[0052] Figure 4 It is a UV-Vis absorption spectrum of the phenoxazine type dye intermediate, the phenoxazine type dye precursor and the phenoxazine type dye in test example 2 of the present application;

[0053] Figure 5 It is a practical effect diagram of the phenoxazine type dye in different dyeing samples in supercritical CO2 in test example 3 of the present application;

[0054] Figure 6 It is a K / S curve of the phenoxazine type dye in different dyeing samples in supercritical CO2 in test example 3 of the present application. DETAILED DESCRIPTION

[0055] The present application will be further described below in connection with the drawings and specific embodiments so that those skilled in the art can better understand and implement the present application. Obviously, the described embodiments are only a part of the embodiments of the present application and are not all the embodiments. It should be understood that the specific embodiments are only used to explain the present application, but the embodiments are not limited to the present application.

[0056] In the present application, unless otherwise specified, the technical and scientific terms used in the present application have the same meanings as those commonly understood by the skilled in the art to which the present application belongs.

[0057] In the present application, unless otherwise specified, the term "and / or" used in the embodiments of the present application includes any and all combinations of one or more related listed items.

[0058] In the present application, unless otherwise specified, the experimental methods used in the embodiments of the present application are conventional methods, and the materials, reagents, etc. used are commercially available, unless otherwise specified.

[0059] Example 1

[0060] The phenoxazine dye intermediate and the preparation method thereof of the present application specifically include the following steps:

[0061] Accurately weigh 0.25 g (2.5 mmol) of catechol, dissolve it in 50 mL of deionized water, and use 2.5 mmol of sodium periodate to oxidize it. When the solution changes from transparent to red, it indicates that the catechol has been oxidized to an o-benzoquinone intermediate. Then, 0.188 g (1 mmol) of 2-amino-4-bromophenol is added to the solution, and the mixed solution is stirred uniformly and then placed in an ultrasonic device until it is completely dissolved. Use 1 mol / L sodium carbonate aqueous solution to adjust the pH value of the system to 9, and react at 25°C for 45 min. Track the reaction degree by spotting.

[0062] After the reaction is completed, the reaction solution is acidified with hydrochloric acid to adjust the pH value of the system to 1. The reaction solution is placed in a 5°C ice bath and allowed to stand for 3 h to allow the product to be separated from the aqueous phase. When the reaction solution shows obvious layering phenomenon (the aqueous phase is yellow and transparent on top, and the product layer is brown on the bottom), equal volume of ethyl acetate is used for extraction, which is repeated three times and then the organic phase is concentrated. After the ethyl acetate is dried by rotary evaporation, the product is washed to neutral with deionized water, and the water solution is removed by a high-speed centrifuge.

[0063] The obtained product is concentrated and then purified by column chromatography using silica gel powder with a specification of 200-300 mesh. The eluent is acetone:methanol = 1:1 (v / v). The separated components are dried by low-pressure rotary evaporation and vacuum drying to obtain the phenoxazine dye intermediate, and the final separation yield is 69%.

[0064] The structure of the phenoxazine dye intermediate is as follows:

[0065]

[0066] Example 2

[0067] The phenoxazine dye precursor of the present application and the preparation method thereof specifically include the following steps:

[0068] 1 mmol (0.293 g) of the phenoxazine dye intermediate of Example 1 is weighed, dissolved in 10 mL of acetone and 10 mL of methanol, and poured into a three-necked flask; 2.5 mmol (0.46 g) of cyanuric chloride is weighed, dissolved in 20 mL of acetone; 2 mmol (0.212 g) of sodium carbonate is weighed, dissolved in 5 mL of deionized water and 15 mL of acetone; the cyanuric chloride solution and the sodium carbonate solution are poured into constant-pressure dropping funnels and connected to the interface of the three-necked flask; a rotor is placed in the three-necked flask, which is placed in a low-temperature constant-temperature stirring reaction bath, the pH value of the system is adjusted to 9, and the reaction is carried out at 4°C for 26 h, and the reaction progress is tracked by spotting.

[0069] After the reaction is completed, the organic solvent is first spin-dried with a rotary evaporator, then washed with deionized water until neutral, centrifuged to separate the deionized water and the product, dissolved in acetone to collect the product, and spin-dried with a rotary evaporator to remove acetone to obtain a solid product; then purified by column chromatography, eluent ethyl acetate: acetone = 1:2 (v / v), the separated components are spin-evaporated to remove the solvent, and then fully dried in a vacuum oven to obtain the dye precursor, and the final separation yield is 67%;

[0070] The structure of the phenoxazine dye precursor is as follows:

[0071]

[0072] Example 3

[0073] The phenoxazine dye of the present application and the preparation method thereof specifically include the following steps:

[0074] Weigh 1 mmol (0.292 g) of the phenoxazine dye intermediate of Example 1, dissolve in 10 mL of acetone and 10 mL of methanol and pour into a three-neck flask; weigh 2.5 mmol (0.46 g) of cyanuric chloride and 1 mmol (0.106 g) of sodium carbonate, dissolve and pour into a constant pressure dropping funnel, which is connected to the interface of the three-neck flask, and slowly drop into the flask; put a rotor into the three-neck flask and place it in a low-temperature constant-temperature stirring bath, adjust the pH of the system to 9, and react at 4°C for 26 h; weigh 1 mmol of genipin (0.226 g) and 1 mmol of sodium carbonate (0.106 g), respectively, dissolve in acetone and deionized water, and pour into the constant pressure dropping funnel, which is connected to the interface of the three-neck flask, and slowly drop into the flask; adjust the pH of the system to 9, and react at 44°C for 10 h, and track the reaction degree by spotting.

[0075] After the reaction is completed, first remove the acetone, methanol and other solvents from the reaction solution using a rotary evaporator; then wash with deionized water until neutral, separate the unpurified product after reaction from deionized water using a centrifuge, spin dry a small amount of water using a rotary evaporator, and purify using column chromatography, with acetone:methanol = 1:1 (v / v) as the eluent; collect the separated components, remove the solvent by rotary evaporation, and fully dry in a vacuum oven to obtain the phenoxazine dye, with a final separation yield of 52%;

[0076] The structure of the phenoxazine dye is as follows:

[0077]

[0078] Test Example 1

[0079] The Fourier infrared spectra of the phenoxazine dye intermediate of Example 1, the phenoxazine dye precursor of Example 2, and the phenoxazine dye of Example 3 are shown in Figures 1-3 .

[0080] As can be seen from Figure 1 , the peak at a wave number of 3420 cm -1 is the stretching vibration peak of -OH. The absorption peak at 3172 cm -1 is from the stretching vibration of the -N= bond in the phenoxazine heterocycle. The characteristic peak at a wave number of 1620 cm -1 is from C=O. The wave number in the figure is around 1620 cm -1 , which is generally greater than 1700 cm -1 , but because the carbonyl group is connected to a benzene ring, the absorption peak wave number is less than 1700 cm -1 due to conjugation. The peak at 1063 cm -1 is the stretching vibration of the C-O-C group, and the vibration peak of the C-Br bond appears at a wave number of 580 cm-1 This indicates that phenoxazine-type dye intermediates possess reactive groups and stable conjugated structures, making them suitable as raw materials for the synthesis of other compounds.

[0081] from Figure 2 It can be seen that 3412cm -1 The peak at 3118 cm⁻¹ is produced by the stretching vibration of the free -OH group. -1 The peak at 3027 cm⁻¹ represents the vibrational peak of the C=N bond in cyanuric chloride. This is due to the hydrogen bonding effect of the nitrogen atom in the cyanuric chloride molecule. -1 The absorption peak of hydrogen bonding of nitrogen atoms in cyanuric chloride molecules is located at 1605 cm⁻¹. -1 The peak at 1055 cm⁻¹ corresponds to the C=O stretching vibration on the phenoxazine ring. -1 The peak at 774 cm⁻¹ is a vibrational peak resulting from the superposition of vibrational signals of the cyclic ether within the phenoxazine heterocycle and the ether bond between the phenoxazine and cyanuric chloride molecules. -1 The peak at 537 cm⁻¹ represents the stretching vibration of the C-Cl bond on the cyanuric chloride ring. -1 The peak at this point represents the stretching vibration of the C-Br bond on the phenoxazine ring. This indicates that phenoxazine dye precursors can be grafted with reactive groups and used as reactive disperse dyes, and due to the presence of cyanuric chloride, they can also be used as a standalone dye.

[0082] from Figure 3 It can be seen that 3445cm -1 The vibrational peak at 2954 cm⁻¹ originates from the hydroxyl group on the side chain of genipin. -1 and 2868cm -1 The peak at 1604 cm⁻¹ originates from the antisymmetric and symmetric stretching vibrations of -CH₃ and -CH₂. -1 The peak at 1192 cm⁻¹ originates from the stretching vibration of the C=O ring on the phenoxazine ring. -1 The peak at 1081 cm⁻¹ originates from the vibration of the acetate ester. -1 and 1104cm -1 The absorption peak at 1044 cm⁻¹ originates from the ether bond on the acetate ester. -1 and 1277cm -1 The vibrational peaks at 897 cm⁻¹ originate from phenoxazine and cyanuric chloride molecules, respectively, and from the ether bond between the cyanuric chloride molecule and the genipin group. -1 A vibrational peak of the genie ring was discovered at 770 cm⁻¹. -1 The peak at 551 cm⁻¹ originates from the vibration of the C-Cl bond. -1 The peak at this point originates from the C-Br vibration. This indicates that the phenoxazine dye possesses both cyanuric chloride and genipin dual reactive groups, and due to the low polarity of the parent structure, it can ensure that the dye can dissolve smoothly in supercritical CO2 fluid and bind firmly to the fiber.

[0083] Test Example 2

[0084] The phenoxazine dye intermediate of Example 1, the phenoxazine dye precursor of Example 2 and the phenoxazine dye of Example 3 were detected using acetone as a solvent at a concentration range of 5.29 x 10 -5 mol / L to 6.92 x 10 -5 mol / L. The measured UV-Vis absorption spectra are shown in Figure 4 From Figure 4 it can be seen that the maximum absorption wavelength of the phenoxazine dye intermediate is 444 nm, and the corresponding molar absorption coefficient is 6.576 x 10 3 L / (mol·cm)- 1 . The maximum absorption wavelength of the phenoxazine dye precursor is 400 nm, and the corresponding molar absorption coefficient is 5.276 x 10 3 L / (mol·cm)- 1 . The maximum absorption wavelength of the dye is 448 nm, and the corresponding molar absorption coefficient is 6.252 x 10 3 L / (mol·cm)- 1 . The maximum absorption wavelength of the phenoxazine dye precursor is blue-shifted by the action of the cyanuric chloride group, and the maximum absorption wavelength of the phenoxazine dye is red-shifted by the action of the genipin group. The maximum absorption wavelengths of the three substances in acetone are different, but the solutions are all yellow and absorb blue light. This indicates that the dye chromophore structure of the phenoxazine dye is less affected by the induction of active groups, which is conducive to obtaining active disperse dyes with different structures but the same color light, and further adjusting the dyeing performance of the phenoxazine dye.

[0085] Test Example 3

[0086] The phenoxazine dye of Example 3 was applied to the dyeing of several dyeing substrates, such as silk, wool, cashmere, polyester and nylon, in a supercritical CO2 dyeing device (T = 110°C, P = 20 MPa, t = 90 min).

[0087] The actual effects and color intensity (K / S value) of different dyeing samples are shown in Figures 5-6 From Figures 5-6It can be seen that the maximum K / S value of several dyeing samples is obtained at 435 nm, and the dyed fabric has yellow tone. And the color is uniform, and the dyeing property is good. Phenoxazine type dyeing silk, wool, cashmere fiber relies on the reaction of nitrogen atom on genipin with amino group, and the nitrogen atom enters the genipin ring to form a new conjugated system, and the fiber-dye-color trinity occurs depending on the nucleophilic substitution reaction, and a second chromophore system is generated. Due to the dual action of the dye matrix and the second chromophore system, intramolecular color mixing effect occurs in the interior of wool, cashmere and other fibers, so there is a small characteristic peak at 455 nm. Whether it is synthetic fiber or natural fiber, phenoxazine type dye has good dyeing effect on fabric in SCF-CO2 fluid.

[0088] By soaping experiment, the color fastness of different dyeing samples was tested according to GB / T 3921-2008, and the specific test results are shown in Table 1:

[0089] Table 1

[0090]

[0091] As can be seen from Table 1, phenoxazine type dyeing on several dyeing samples can obtain ideal dyeing fastness. The color transfer fastness of several samples reaches 4-5 or 5. The color change fastness of wool and cashmere fiber is 4-5, and the color change fastness of silk fabric is 4-5, which shows that the combination effect of amino group in fiber and genipin is good. The dry rubbing fastness and wet rubbing fastness of five samples are good, and reach 4-5 or 5. Comprehensive analysis shows that phenoxazine type dye can realize the dyeing application of protein fiber in SCF-CO2, and has good color characteristics and fastness index.

[0092] Obviously, the above examples are only examples for the sake of clarity, and are not limited to the embodiments. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and impossible to exhaust all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A phenoxazine dye precursor, characterized in that, The structure of the phenoxazine dye precursor is shown in formula V: X = Br, Cl, F or NO2; Y = OH, NH2 or NHR, R = CH3 or CH2CH3; Z = Cl or F.

2. A process for the preparation of a phenoxazine dye precursor according to claim 1, characterized in that The method comprises the following steps: The phenoxazine dye intermediate of formula III and the compound of formula IV are reacted in a solvent to obtain the phenoxazine dye precursor of formula V; The structure of formula III to formula V is as follows: X = Br, Cl, F or NO2; Y = OH, NH2 or NHR, R = CH3 or CH2CH3; Y = OH, NH2 or NHR, R = CH3 or CH2CH3; Z = Cl or F.

3. The method of claim 2, wherein the method is carried out in the presence of a base. The molar ratio of the phenoxazine dye intermediate of formula III and the compound of formula IV is 1: (1-3).

4. A phenoxazine dye characterized in that, The structure of the phenoxazine dye is shown in formula VI: X = Br, Cl, F or NO2; Y = OH, NH2 or NHR, R = CH3 or CH2CH3; Z = Cl or F.

5. A process for the preparation of a phenoxazine dye according to claim 4, characterized in that The method comprises the following steps: the phenoxazine dye precursor of formula V and genipin are reacted in a solvent to obtain the phenoxazine dye of formula VI.

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