Spiropyrane derivative, synthetic method thereof and application of spiropyrane derivative to silk fabric

Abstract

The invention discloses a spiropyrane derivative, a synthesis method thereof and application of the spiropyrane derivative to silk fabrics, 2, 5-dihydroxy terephthalaldehyde and 2, 3, 3-trimethyl-3H-indole are used as raw materials to react to synthesize the spiropyrane derivative, and the spiropyrane derivative is used for finishing the silk fabrics to realize dyeing of the silk fabrics. The spiropyran derivative prepared by the invention is used as a photochromic dye to be combined with silk fabric in a chemical bond combination manner, a spectrum and chromatic aberration can be measured by simulating an illumination condition through a xenon lamp, and the spiropyran derivative is sensitive in color change and has a washing-resistant function. The synthetic method disclosed by the invention has the advantages of simple process, low cost and high efficiency, and meanwhile, the fabric has a remarkable photochromic effect and still has a good photochromic effect after being washed for multiple times.

Description

Technical Field

[0001] The invention belongs to the field of photochromism of spiropyran derivatives, and specifically relates to the synthesis of a novel spiropyran derivative and the application of the derivative to silk fabrics. Background Art

[0002] Spiropyran derivatives are organic photochromic compounds that can undergo reversible structural isomerization between colorless closed-ring spiropyran and colored open-ring body cyanine, and have good color change and thermal stability. In addition, the properties and thermal properties of spiropyran derivatives can be adjusted by modifying the structure of the molecule, making spiropyran derivatives a hot topic in photochromic research. So far, there is no technical solution for using spiropyran derivatives to exhibit photochromism in fabrics. As a fabric finishing agent, it is not only necessary to effectively exert the performance of the agent itself, but also to have good water wash resistance. Summary of the invention

[0003] The object of the present invention is to provide a spiropyran derivative which can be used as a photochromic agent, namely 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole], which is applied to silk fabrics and has the advantages of sensitive color change, water-washing resistance, simple preparation and low cost.

[0004] To achieve the above object, the technical solution of the present invention is as follows: A spiropyran derivative is (1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole], and its chemical structure is shown in Formula I: .

[0005] The present invention also provides a method for synthesizing the spiropyran derivatives, comprising the following steps: using 2,5-dihydroxyterephthalaldehyde and 2,3,3-trimethyl-3H-indole as raw materials to react and synthesize the spiropyran derivatives.

[0006] In the present invention, the reaction temperature is 60-100° C., and the reaction time is 3-10 h; preferably, the reaction temperature is 70-90° C., and the reaction time is 4-8 h.

[0007] In the present invention, the reaction is carried out in a solvent, preferably, the solvent is a small molecule alcohol, such as ethanol.

[0008] In the present invention, the ratio of 2,5-dihydroxyterephthalaldehyde to 2,3,3-trimethyl-3H-indole is 1:(0.8-1.2), preferably 1:1.

[0009] The present invention discloses the use of the above-mentioned spiropyran derivatives on silk fabrics. Preferably, the present invention discloses the use of the above-mentioned spiropyran derivatives on silk fabric dyeing. Further preferably, the present invention discloses the use of the above-mentioned spiropyran derivatives as dyes, especially photochromic dyes, on silk fabric dyeing.

[0010] The invention discloses application of the spiropyran derivatives in preparing photochromic silk fabrics.

[0011] In an embodiment of the present invention, the prepared spiropyran derivative is combined with silk fabric as a photochromic dye through chemical bonding, and the spectrum and color difference thereof can be measured by simulating lighting conditions with a xenon lamp, wherein the chemical bonding method is a Schiff base reaction.

[0012] The invention discloses a method for dyeing silk fabrics, comprising the following steps: using the spiropyran derivatives to finish the silk fabrics to achieve dyeing of the silk fabrics.

[0013] In the present invention, when the spiropyran derivatives are used to finish silk fabrics, the concentration of the dye is 3-8% owf, and the bath ratio is 1:30-60.

[0014] The invention discloses photochromic silk fabric prepared according to the silk fabric dyeing method.

[0015] The synthesis method of the spiropyran derivatives of the present invention is schematically shown as follows:

[0016] The spiropyran derivatives provided by the present invention can be applied to silk fabrics, have a short response time, and have a significant photochromic effect.

[0017] The beneficial effect of the present invention is that: the present invention uses 1,4-dimethoxybenzene as a raw material to prepare 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole]. The synthesis method of the present invention has the advantages of simple process, low cost and high efficiency. At the same time, the fabric has a significant photochromic effect and still has a good photochromic effect after multiple washings. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The H NMR spectrum of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] prepared in Example 1 of the present invention.

[0019] Figure 2The NMR carbon spectrum of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] prepared in Example 1 of the present invention.

[0020] Figure 3 is the response time of dyed silk fabric.

[0021] Figure 4 is the number of cycles for dyeing silk fabric.

[0022] Figure 5 It is the number of cycles after dyed silk fabric is washed ten times.

[0023] Figure 6 H NMR spectrum of the contrast dye.

[0024] Figure 7 The NMR spectrum of the contrast dye.

[0025] Figure 8 The number of cycles before washing the fabric dyed with the comparison dye.

[0026] Fig. 9 It is the number of cycles after 10 washings after dyeing with comparative dye. DETAILED DESCRIPTION

[0027] To further illustrate the present invention, the preparation method and application of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] provided by the present invention are described in detail below in conjunction with the examples.

[0028] Specifically, the synthesis method of the spiropyran derivative of the present invention comprises the following steps: (1) Dissolve 1,4-dimethoxybenzene and formaldehyde solution in a solvent, raise the temperature, control the temperature, dropwise add concentrated hydrochloric acid, react after the dropwise addition is complete, then dropwise add hydrochloric acid, react after the dropwise addition is complete; after the reaction is complete, cool to room temperature, filter, wash the filter cake with distilled water, and recrystallize the obtained crude product with acetone to obtain 1,4-bis(chloromethyl)-2,5-dimethoxybenzene; (2) dissolving the obtained 1,4-bis(chloromethyl)-2,5-dimethoxybenzene in a solvent, adding N-methylmorpholine-N-oxide and molecular sieves, and reacting at 10-35° C., removing excess solvent after the reaction, and further purifying the crude product to obtain 2,5-dimethoxyterephthalaldehyde; (3) Add the obtained 2,5-dimethoxyterephthalaldehyde to dichloromethane, cool it down, then add a dichloromethane solution of boron tribromide, slowly raise the temperature to room temperature, and react. After the reaction is completed, cool the reaction solution to 0°C, add deionized water, solid precipitates, filter, extract the filtrate with dichloromethane, dry it with anhydrous sodium sulfate, spin dry to obtain a crude product, and purify it through a column to obtain 2,5-dihydroxyterephthalaldehyde; (4) The obtained 2,5-dihydroxyterephthalaldehyde is dissolved in ethanol, 2,3,3-trimethyl-3H-indole is added, and the temperature is controlled at 70-90°C for reaction. After the reaction is completed, the reaction solution is cooled to room temperature, filtered, and the filter cake is recrystallized to obtain 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole].

[0029] Preferably, the amount of the molecular sieve used in step (1) is 3 to 5 times the mass of 1,4-bis(chloromethyl)-2,5-dimethoxybenzene, the solvent is dichloromethane, and the reaction time is 6 hours.

[0030] Preferably, the temperature for preparing 2,5-dimethoxyterephthalaldehyde in step (2) is 15 to 30° C., and the reaction time is 2 to 2.5 hours.

[0031] Preferably, in step (3), the molar ratio of 1,4-bis(chloromethyl)-2,5-dimethoxybenzene to N-methylmorpholine-N-oxide is 1:3, and the reaction time is 12 hours.

[0032] Preferably, the reaction temperature in step (4) is 60-80° C., and the reaction time is 6 hours; preferably, the reaction is carried out in nitrogen.

[0033] The instruments and reagents are conventional techniques, and the specific preparation operations and performance tests are conventional techniques. All the following KS tests were performed on a HunterLab spectrophotometer; the nuclear magnetic resonance spectra were obtained on a Bruker DRX-400 spectrometer (using deuterated chloroform and deuterated dimethyl sulfoxide as solvents).

[0034] 1,4-Dimethoxybenzene was purchased from Shanghai Mairui Chemical Technology Co., Ltd., formaldehyde solution was purchased from Shanghai Mairui Chemical Technology Co., Ltd., concentrated hydrochloric acid was purchased from Shanghai Yonghua Chemical Technology Co., Ltd., and 2,3,3-trimethyl-3H-indole was purchased from Shanghai Sinopharm Group Co., Ltd. All water used in the experiment was deionized water. Unless otherwise specified, other chemical reagents were of analytical grade and could be used directly without further purification and treatment. The silk fabric was double wrinkled silk (52 g / m 2 Suzhou Jiali Silk Garment Co., Ltd., China).

[0035] The color fastness to washing with soap is determined according to GB / T 3921-2008 “Textiles—Tests for Color Fastness—Colour Fastness to Washing with Soap”, with 5g / L soap flakes, bath ratio 50:1, test temperature 40°C and test time 30min.

[0036] The following specific embodiments are described in detail. These specific embodiments are only for description and are not used to limit the scope or implementation principles of the present invention. The scope of protection of the present invention is subject to the claims, including obvious changes or modifications made on this basis. Example 1

[0037] (1) Synthesis of 2,5-dihydroxyterephthalaldehyde Refer to Example 1 of a method for synthesizing 2,5-dihydroxyterephthalaldehyde in CN117384019A.

[0038] (2) Synthesis of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole]: In a 100 mL brown reaction bottle, take 3.3424 g of 2,5-dihydroxyterephthalaldehyde, add 3.1846 g of 2,3,3-trimethyl-3H-indole, add 60 mL of anhydrous ethanol under a nitrogen atmosphere, react at 80°C for 6 h, and analyze the reaction of the raw materials by thin layer chromatography. After cooling to room temperature, solids precipitated, filtered, and recrystallized from anhydrous ethanol to obtain 4.94 g of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] with a yield of 76.8%.

[0039] Figure 1 The H NMR spectrum of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] prepared in Example 1 of the present invention. Figure 2 The NMR carbon spectrum of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] prepared in Example 1 of the present invention. Example 2

[0040] In a 100 mL brown reaction bottle, 3.3424 g of 2,5-dihydroxyterephthalaldehyde was added, 3.1846 g of 2,3,3-trimethyl-3H-indole was added, 60 mL of anhydrous ethanol was added under a nitrogen atmosphere, and the reaction was carried out at 60°C for 6 h. The reaction of the raw materials was complete by thin layer chromatography analysis, and solids were precipitated after cooling to room temperature. The solids were filtered and recrystallized from anhydrous ethanol to obtain 4.76 g of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole], with a yield of 75%. Example 3

[0041] In a 100 mL brown reaction bottle, 3.3424 g of 2,5-dihydroxyterephthalaldehyde was added, 3.1846 g of 2,3,3-trimethyl-3H-indole was added, 60 mL of anhydrous ethanol was added under a nitrogen atmosphere, and the reaction was carried out at 70°C for 6 h. The reaction of the raw materials was complete by thin layer chromatography analysis, and solids were precipitated after cooling to room temperature. The solids were filtered and recrystallized from anhydrous ethanol to obtain 4.66 g of 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole], with a yield of 74.3%. Example 4 Photochromic silk fabric

[0042] 1,3-Dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] was used as dye, the dye was 5% owf, the bath ratio was 1:50, put into a shaking water bath, constant temperature finishing at 80°C for 90min, and then dyed silk fabric to prepare the desired silk fabric.

[0043] Photochromic response time Figure 3 As shown in the figure, the prepared silk fabric was 2 Under light, there is an obvious color change within 5 seconds, and the color change reaches a maximum value within 30 seconds. This experiment shows that the prepared silk fabric has a good photochromic effect and a short response time.

[0044] The number of photochromic cycles is as follows Figure 4 As shown in the figure, the prepared silk fabric was 2 Under light, the illumination time is 2 minutes, and the current △E is recorded. After 2 minutes at 80℃ and normal pressure, the current △E is recorded. This process is a cycle. After multiple cycles, it still has obvious photochromic effect and good stability.

[0045] like Figure 5 As shown in the figure, after 10 times of soap washing, the prepared silk fabric has a 2Under light, it still has obvious photochromic effect. Comparative Example 1

[0046]

[0047] Under nitrogen atmosphere, 1,3,3-trimethyl-2-methyleneindoline (1 eq) and 2,5-dihydroxybenzaldehyde (1 eq) were dissolved in anhydrous ethanol and then refluxed for 3 hours. After the reaction, the mixture was cooled to room temperature, and the excess solvent was removed by rotary evaporation. The crude product was purified by column to obtain a contrast dye. Its NMR is shown in Figure 6 , Figure 7 .

[0048] Photochromic silk fabric was prepared according to the experimental method of Example 4. The number of photochromic cycles was as follows: Figure 8 As shown, the number of photochromic cycles after soap washing 10 times is as follows Fig. 9 shown.

[0049] The 1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole] of the present invention is used as a photochromic dye, and is further combined with silk fabrics. The photochromic dye has sensitive color change and is resistant to water washing, and has important practical significance.

[0050] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic features of the present invention. Therefore, no matter from which point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the attached claims rather than the above description, and it is intended to include all changes within the meaning and scope of the equivalent elements of the claims. Although the embodiments of the present invention have been shown and described, it is understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the attached claims and their equivalents.

Claims

1. A spiropyran derivative, which is (1,3-dihydro-1,3,3-trimethyl-6-nitro-7-hydroxyspiro[2H-1-benzopyran-2,2`-(2H)-indole].

2. The method for synthesizing the spiropyran derivatives according to claim 1, comprising the following steps: using 2,5-dihydroxyterephthalaldehyde and 2,3,3-trimethyl-3H-indole as raw materials to react and synthesize the spiropyran derivatives.

3. The method for synthesizing the spiropyran derivative according to claim 2, characterized in that: The reaction temperature is 60-100°C and the reaction time is 3-10 hours.

4. The method for synthesizing the spiropyran derivative according to claim 2, characterized in that: The reaction is carried out in a solvent; the ratio of 2,5-dihydroxyterephthalaldehyde to 2,3,3-trimethyl-3H-indole is 1:(0.8-1.2).

5. Use of the spiropyran derivative according to claim 1 on silk fabrics.

6. Use of the spiropyran derivatives according to claim 1 in dyeing silk fabrics.

7. Use of the spiropyran derivative according to claim 1 in the preparation of photochromic silk fabrics.

8. A method for dyeing silk fabrics, comprising the following steps: finishing the silk fabrics with the spiropyran derivatives according to claim 1 to achieve dyeing of the silk fabrics.

9. The method for dyeing silk fabric according to claim 8, characterized in that: When the spiropyran derivatives described in claim 1 are used as dyes for finishing silk fabrics, the concentration of the dye is 3 to 8% owf and the bath ratio is 1:30 to 60.

10. The photochromic silk fabric prepared according to the method for dyeing silk fabric according to claim 8.

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