Thiazole Orange Organosilicon Quaternary Ammonium Salt Compound, Its Preparation Method and Application

Abstract

The present invention discloses a thiazole orange organosilicon quaternary ammonium salt compound, a preparation method thereof and an application. The structure of the compound is shown in Formula I, wherein, X 1 and X 2 are independently selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R 1 , R 2 , R 3 , R 4 are independently selected from methyl, ethyl, C3-C8 alkyl, phenyl, nitro, nitroso, sulfonyl, methanesulfonyl, fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethyl, m = 0-30, n = 0-30. The present invention simultaneously has four structures of thiazole ring, quinoline ring, quaternary ammonium group and organosiloxane, has a broad antibacterial spectrum, and simultaneously has antibacterial activity against Staphylococcus aureus, Escherichia coli, Candida albicans and Aspergillus niger, has good wash resistance, compared with the existing preparation methods, the operation of the present invention is simple, the raw materials are convenient to obtain, is environmentally friendly, suitable for industrial production, and has good application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial dyes for textiles, and relates to a thiazole orange organosilicon quaternary ammonium salt compound, a preparation method thereof, and an application thereof. Background Art

[0002] Antibacterial dyes are a class of multifunctional compounds with both dyeing and antibacterial functions, and have great application prospects in industries such as medicine, clothing, and food. For example, the dyeing and antibacterial finishing of fabrics are usually two independent processes traditionally. However, such a treatment method has the following problems: on the one hand, certain antibacterial finishing may affect the dyeing performance or other functional finishing; on the other hand, antibacterial finishing often requires a separate post-treatment process. Performing dyeing and finishing step by step will lead to an increase in cost and waste of resources, and will also cause greater environmental damage, which does not meet the requirements of sustainable development. Using antibacterial dyes can perform the dyeing and antibacterial finishing of fabrics simultaneously in the same step, and endow the fabrics with antibacterial properties while dyeing the fabrics. Compared with the traditional process, using antibacterial dyes reduces one wet treatment process, well reduces energy consumption, and reduces the amount of water used and wastewater discharged, which is undoubtedly more environmentally friendly.

[0003] Thiazole orange is a class of cationic dyes containing both thiazole ring and quinoline ring in the molecular structure. It has many characteristics such as bright color, high fluorescence quantum yield, and large molar extinction coefficient. Thiazole orange is often used as a fluorescent probe for nucleic acids and is widely used in fields such as electrophoresis separation and quantitative determination of DNA. The cationic structural characteristics of thiazole orange make it have the potential to be used in combination with other cationic antibacterial agents. Designing a series of antibacterial dye compounds with thiazole orange as the parent nucleus will be a very meaningful work. Summary of the Invention

[0004] In view of the problems existing in the above-mentioned prior art, the present invention has developed a thiazole orange organosilicon quaternary ammonium salt compound, a preparation method thereof, and an application of this thiazole orange organosilicon quaternary ammonium salt compound in the antibacterial field.

[0005] One technical solution of the present invention is to provide a thiazole orange organosilicon quaternary ammonium salt compound, and the structure of the above compound is shown in Formula I, , wherein, X 1 and X 2 are selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R 1 , R 2 , R 3 , R 4Independently selected from methyl, ethyl, C3-C8 alkyl, phenyl, nitro, nitroso, sulfonyl, mesyl, fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethyl, m = 0-30, n = 0-30.

[0006] In a preferred embodiment of the present invention, m is greater than or equal to 8 and less than or equal to 12; n is greater than or equal to 10 and less than or equal to 15.

[0007] The second technical solution of the present invention is to provide a preparation method of the above thiazole orange organosilicon quaternary ammonium salt compound, including the following steps: , (a) Under the condition of air isolation, a first reaction solvent, a compound of formula 1, and a compound of formula 2 are added to the reaction kettle, the reaction temperature is 60-200 °C, and the reaction time is 6-72 hours to obtain a compound of formula 3, wherein the molar ratio of the above-mentioned compound of formula 1 to the compound of formula 2 is 1:1-10;

[0008] (b) Under the condition of air isolation, a second reaction solvent is added to the reaction kettle, and then a compound of formula 4 and a compound of formula 5 are added, the reaction temperature is 60-200 °C, and the reaction time is 3-72 hours to obtain a compound of formula 6, wherein the molar ratio of the above-mentioned compound of formula 4 to the compound of formula 5 is 1:1-10;

[0009] (c) Under the condition of air isolation, a third reaction solvent, a compound of formula 3 and a compound of formula 6 are added to the reaction kettle, and the reaction is carried out at a reaction temperature of 25-60 °C and kept warm for 1-5 hours to obtain a compound of formula 7, wherein the molar ratio of the above-mentioned compound of formula 3 to the compound of formula 6 is 1:1-10;

[0010] (d) Under the condition of air isolation, a fourth reaction solvent, a compound of formula 7 and a compound of formula 8 are added to the reaction kettle, and the reaction is carried out at a reaction temperature of 80-200 °C and kept warm for 12-102 hours to obtain a compound of formula I, wherein the molar ratio of the above-mentioned compound of formula 7 to the compound of formula 8 is 1:1-10;

[0011] Wherein, X 1 and X 2 are selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R 1 , R 2 , R 3 , R 4 Independently selected from methyl, ethyl, C3-C8 alkyl, phenyl, nitro, nitroso, sulfonyl, mesyl, fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethyl, m = 0-30, n = 0-30.

[0012] In a preferred embodiment of the present invention, m is greater than or equal to 8 and less than or equal to 12; n is greater than or equal to 10 and less than or equal to 15.

[0013] In a preferred embodiment of the present invention, in step (a), the first reaction solvent is at least one of acetonitrile, p-xylene, o-xylene, m-xylene, toluene, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, acetonitrile, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane.

[0014] In a preferred embodiment of the present invention, in step (b), the second reaction solvent is at least one of acetonitrile, p-xylene, o-xylene, m-xylene, toluene, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, ethyl acetate, tetrahydrofuran, 2-methyltetrahydrofuran or dioxane.

[0015] In a preferred embodiment of the present invention, in step (c), the third reaction solvent is at least one of ethanol, methanol, isopropanol, n-butanol, p-xylene, o-xylene, m-xylene, toluene, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane.

[0016] In a preferred embodiment of the present invention, the fourth reaction solvent is at least one of o-xylene, p-xylene, m-xylene, toluene, ethylene glycol diethyl ether, DMF, DMSO, acetonitrile or acetone.

[0017] In a preferred embodiment of the present invention, in step (d), it is also necessary to continue to add a basic reagent, and the basic reagent is at least one of triethylamine and N,N-diisopropylethylamine.

[0018] The third technical solution of the present invention is to provide the application of the above-mentioned thiazole orange organosilicon quaternary ammonium salt compound and the thiazole orange organosilicon quaternary ammonium salt compound prepared by the preparation method using the above-mentioned thiazole orange organosilicon quaternary ammonium salt compound in antibacterial materials. Beneficial effects

[0019] The thiazole orange organosilicon quaternary ammonium salt compound of the present invention has four structures: thiazole ring, quinoline ring, quaternary ammonium group and organosiloxane, and has a broad antibacterial spectrum. The present invention has antibacterial activity against Staphylococcus aureus, Escherichia coli, Candida albicans and Aspergillus niger.

[0020] The wash resistance of the present invention is particularly good. The antibacterial rate remains at 99.9% after 100 washes, above 80% after 200 washes, and above 70% after 300 washes.

[0021] Compared with the existing preparation methods, the operation of the present invention is simple, the raw materials are easily accessible, it is environmentally friendly, suitable for industrial production, and has good application prospects. Detailed implementation manners

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present invention. Example 1

[0023]

[0024] Step (a): Preparation of the compound of formula 3-1

[0025] While maintaining a slightly positive pressure of nitrogen, 2 L of acetonitrile, 149.21 g (1.0 mol) of the compound of formula 1-1, 2-methylbenzothiazole, and 201.89 g (1.0 mol) of the compound of formula 2-1, 1,3-dibromopropane, were successively added to a 5 L reaction flask. After addition, the mixture was stirred evenly, and the reaction solution was heated to 82 °C for reaction. The reaction was maintained for 24 hours until completion.

[0026] The reaction solution was cooled to room temperature, 1.5 L of petroleum ether was added thereto, cooled to 0 °C, and kept overnight. A large amount of solid was precipitated, filtered, and the filter cake was collected to obtain 258.41 g (0.736 mol) of the yellow solid product of formula 3-1.

[0027] The yield was 73.6%.

[0028] Product purity: 98.89% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.49 (d, 1H), 8.36 (d, 1H), 7.90 (t, 1H), 7.82 (t, 1H), 4.77 - 4.89 (m, 2H), 3.73 (t, 2H), 3.24 (s, 3H), 2.39 - 2.49 (m, 2H).

[0029] Step (b): Preparation of the compound of formula 6-1

[0030] While maintaining a slightly positive pressure of nitrogen, 2 L of acetonitrile, 327.2 g (2.0 mol) of the compound of formula 4-1, 4-chloroquinoline, and 403.78 g (2.0 mol) of the compound of formula 5-1, 1,3-dibromopropane, were successively added to a 5 L reaction flask. After addition, the mixture was stirred evenly, and the reaction solution was heated to 82 °C for reaction. The reaction was maintained for 16 hours until completion.

[0031] The reaction solution was cooled to room temperature, 1 L of petroleum ether was added thereto, cooled to 0 °C, kept warm overnight, a large amount of solid was precipitated, filtered, and the filter cake was collected to obtain 508.03 (1.39 mol) of yellow solid product.

[0032] The yield was 69.5%.

[0033] Product purity: 98.74% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.49 - 8.74 (m, 2H), 8.31 - 8.41 (m, 2H), 8.06 - 8.21 (m, 2H), 5.29 - 5.36 (m, 2H), 3.78 (t, 2H), 2.49–2.57 (m, 2H).

[0034] Step (c): Preparation of the compound of formula 7-1

[0035] While maintaining a slightly positive pressure of nitrogen, 1.2 L of ethanol, 258.41 g (0.736 mol) of the compound of formula 3-1 and 269.00 g (0.436 mol) of the compound of formula 6-1 were successively added to a 5 L reaction flask and stirred evenly. Then 7.45 g (0.074 mol) of triethylamine was added thereto. After addition, it was stirred evenly, and the reaction solution was heated to 40 °C for reaction. The reaction was kept warm for 3 hours and the reaction was completed.

[0036] The reaction solution was cooled to room temperature, 1 L of ethyl acetate and 1 L of petroleum ether were added thereto, cooled to 0 °C, kept warm overnight, a large amount of solid was precipitated, filtered, and the filter cake was collected to obtain 391.19 g (0.653 mol) of red solid product.

[0037] The yield was 88.70%.

[0038] Product purity: 99.25% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.50 (d, 1H), 8.37 (d, 1H), 8.25 - 8.30 (m, 3H), 7.74 - 7.93 (m, 5H), 6.87 (s, 1H), 4.77 - 4.89 (m, 2H), 3.73 (t, 2H), 3.21 (t, 2H), 3.05 - 3.21 (m, 2H), 2.39 - 2.49 (m, 2H), 2.01 - 2.05 (m, 2H).

[0039] Step (d): Preparation of the compound of formula I-1

[0040] Maintain a slightly positive pressure of nitrogen. Add 1.8 L of o-xylene, g (0.632 mol) of the compound of Formula 7-1, and g (1.355 mol) (2-10 eq) of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to a 5 L reaction flask in sequence. After adding, stir well; heat the reaction solution to 140 °C for reaction. Keep the reaction at this temperature for 8 hours until the reaction is completed.

[0041] Let the reaction solution cool naturally to room temperature, then continue to cool to 0 °C, keep the temperature for 3 hours for crystallization. A large amount of solid precipitates. Filter and collect the filter cake to obtain 594.39 g (0.586 mol) of a red solid product.

[0042] The yield is 89.8%, and the total yield of the four-step reaction is 40.74%. The product purity is 99.21% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.53 (d, 1H), 8.36 (d, 1H), 8.25 - 8.30 (m, 3H), 7.74 - 7.93 (m, 5H), 6.93 (s, 1H), 4.79 - 4.92 (m, 2H), 3.52 (bs, 18H), 3.05 - 3.25 (m, 22H), 2.23 - 2.32 (m, 2H), 1.96 - 2.01 (m, 2H), 1.72 - 1.77 (m, 4H), 0.65 (t, 4H). Example 2

[0043]

[0044] Step (a): Preparation of the compound of Formula 3-2

[0045] Maintain a slightly positive pressure of nitrogen. Add 2 L of 2-methyltetrahydrofuran, 149.21 g (1.0 mol) of the compound of Formula 1-2, 2-methylbenzothiazole, and 282.08 g (2.0 mol) of the compound of Formula 2-2, 1,5-dichloropentane to a 5 L reaction flask in sequence. After adding, stir well; heat the reaction solution to 80 °C for reaction. Keep the reaction at this temperature for 25 hours until the reaction is completed.

[0046] Cool the reaction solution to room temperature, add 3000 mL of petroleum ether to it, cool to 0 °C, keep the temperature overnight. A large amount of solid precipitates. Filter and collect the filter cake to obtain 208.4 g (0.718 mol) of a yellow solid product.

[0047] The yield is 71.8%.

[0048] Product purity: 99.13% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.51 (d, 1H), 8.37 (d, 1H), 7.91 (t, 1H), 7.82 (t, 1H), 4.75 - 4.85 (m, 2H), 3.58 (t, 2H), 3.25 (s, 3H), 2.01 - 2.03 (m, 2H), 1.75 - 1.79 (m, 2H), 1.27 - 1.30 (m, 2H).

[0049] Step (b): Preparation of the compound of Formula 6-2

[0050] Maintain a slightly positive pressure of nitrogen. Sequentially add 6 L of ethylene glycol diethyl ether, 532.89 g (3.0 mol) of the compound of Formula 4-2, 2-methyl-4-chloroquinoline, and 1856.52 g (6.0 mol) of the compound of Formula 5-2, 1,4-diiodobutane into a 20 L reaction flask. After adding, stir well, and heat the reaction solution to 120 °C for reaction. Keep the temperature for reaction for 10 hours until the reaction is complete.

[0051] Cool the reaction solution to room temperature, add 3000 mL of petroleum ether to it, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 1004.84 (2.061 mol) of yellow solid product.

[0052] Yield: 68.7%.

[0053] Product purity: 98.95% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.56 (d, 1H), 8.46 (d, 1H), 8.22 (t, 1H), 8.01 (t, 1H), 7.55 (s, 1H), 5.18 - 5.25 (m, 2H), 2.93 (t, 2H), 2.67 (s, 3H), 2.00 - 2.03 (m, 2H), 1.82 - 1.85 (m, 2H)

[0054] Step (c): Preparation of the compound of Formula 7-2

[0055] Maintain a slightly positive pressure of nitrogen. Sequentially add 1.2 L of ethanol, 208.4 g (0.718 mol) of the compound of Formula 3-2, and 700.12 g (1.436 mol) of the compound of Formula 6-2 into a 5 L reaction flask, and stir well. Then add 14.53 g (0.144 mol) of triethylamine to it. After adding, stir well, and heat the reaction solution to 40 °C for reaction. Keep the temperature for reaction for 4 hours until the reaction is complete.

[0056] The reaction solution was cooled to room temperature, 1 L of ethyl acetate and 1 L of petroleum ether were added thereto, cooled to 0 °C, kept warm overnight, a large amount of solid was precipitated, filtered, and the filter cake was collected to obtain 395.04 g (0.644 mol) of a red solid product.

[0057] The yield was 89.7%.

[0058] Product purity: 99.46% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.50 (d, 1H), 8.37 (d, 1H), 8.25 - 8.30 (m, 3H), 7.74 - 7.93 (m, 5H), 6.87 (s, 1H), 4.77 - 4.89 (m, 2H), 3.73 (t, 2H), 3.21 (t, 2H), 3.05 - 3.21 (m, 2H), 2.39 - 2.49 (m, 2H), 2.01 - 2.05 (m, 2H).

[0059] Step (d): Preparation of the compound of formula I-2

[0060] While maintaining a slightly positive pressure of nitrogen, 1.8 L of o-xylene, 395.04 g (0.644 mol) of the compound of formula 7-2 and 481.93 g (1.932 mol) (3 eq) of 3-N,N-dimethylaminopropyl(triethoxy)silane (CAS: 43108-00-5) were successively added to a 5 L reaction flask. After addition, it was stirred evenly; the reaction solution was heated to 140 °C for reaction. The reaction was kept warm for 8 hours and the reaction was completed.

[0061] The reaction solution was naturally cooled to room temperature, then further cooled to 0 °C, kept warm for crystallization for 3 hours, a large amount of solid was precipitated, filtered, and the filter cake was collected to obtain 650.45 g (0.585 mol) of a red solid product.

[0062] The yield was 90.8%, and the total yield of the 4-step reaction was 40.18%. Product purity: 98.64% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.53 (d, 1H), 8.36 (d, 1H), 8.25 - 8.30 (m, 3H), 7.74 - 7.93 (m, 5H), 6.93 (s, 1H), 4.79 - 4.92 (m, 2H), 3.85 (q, 12H), 3.05 - 3.25 (m, 22H), 2.23 - 2.32 (m, 2H), 1.96 - 2.01 (m, 2H), 1.73 - 1.78 (m, 4H), 1.22 (t, 18H), 0.64 (t, 4H). Example 3

[0063]

[0064] Step (a): Preparation of Compound of Formula 3-3

[0065] Maintain a slightly positive pressure of nitrogen. Sequentially add 2 L of ethylene glycol diethyl ether, 149.21 g (1.0 mol) of the compound of Formula 1-1, 2-methyl-6-nitrobenzothiazole, and 1279.62 g (3.0 mol) (1 - 10 eq) of the compound of Formula 2-3, 1,6-di(p-toluenesulfonyloxy)hexane into a 5 L reaction flask. After adding, stir well, and heat the reaction solution to 120 °C (60 - 200) for reaction. Keep the temperature for reaction for 18 hours until the reaction is complete.

[0066] Cool the reaction solution to room temperature, add 2000 mL of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 430.80 g (0.694 mol) of a green solid product.

[0067] Yield: 70.9%. Product purity: 98.87% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 9.45 (s, 1H), 8.67 (d, 1H), 8.52 (d, 1H), 7.79 (d, 2H), 7.47 (d, 2H), 7.34 (d, 2H), 7.10 (d, 2H), 4.80 - 4.93 (m, 2H), 4.02 (t, 2H), 3.28 (s, 3H), 2.45 (s, 3H), 2.28 (s, 3H), 2.02 - 2.04 (m, 2H), 1.62 - 1.66 (m, 2H), 1.42 - 1.45 (m, 2H), 1.22 - 1.27 (m, 2H).

[0068] Step (b): Preparation of Compound of Formula 6-3

[0069] Maintain a slightly positive pressure of nitrogen. Sequentially add 6 L of DMF, 507.16 g (3.1 mol) of the compound of Formula 4-3, 4-chloroquinoline, and 1442.06 g (9.3 mol) of the compound of Formula 5-3, 1,6-dichlorohexane into a 20 L reaction flask. After adding, stir well, and heat the reaction solution to 150 °C for reaction. Keep the temperature for reaction for 8 hours until the reaction is complete.

[0070] Cool the reaction solution to room temperature, add 6000 mL of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 681.73 g (2.140 mol) of a yellow solid product.

[0071] Yield: 69.01%. Product purity: 98.89% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.49 - 8.74 (m, 2H), 8.31 - 8.41 (m, 2H), δ 8.06 - 8.21 (m, 2H), 5.29 - 5.36 (m, 2H), 3.56 (t, 2H), 2.49–2.57 (m, 2H), 2.01 - 2.03 (m, 2H), 1.75 - 1.79 (m, 2H), 1.45 - 1.48 (m, 2H), 1.27 - 1.30 (m, 2H).

[0072] Step (c): Preparation of the compound of Formula 7-3

[0073] Maintaining a slightly positive nitrogen pressure, successively add 1.2 L of ethanol, 430.80 g (0.694 mol) of the compound of Formula 3-3 and 663.47 g (2.082 mol) of the compound of Formula 6-3 to a 5 L reaction flask, and stir well. Then add 21.07 g (0.208 mol) of triethylamine thereto. After adding, stir well, and raise the temperature of the reaction solution to 40 °C for reaction. Keep the temperature for reaction for 5 hours until the reaction is completed.

[0074] Cool the reaction solution to room temperature, add 1 L of ethyl acetate and 1 L of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 542.42 g (0.626 mol) of an orange solid product.

[0075] Yield: 90.2%.

[0076] Product purity: 98.36% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 9.45 (s, 1H), 8.67 (d, 1H), 8.52 (d, 1H), 8.25 - 8.30 (m, 3H), 7.79 (d, 2H), 7.65 - 7.70 (m, 2H), 7.47 (d, 2H), 7.34 (d, 2H), 7.31 (d, 1H), 7.15 (s, 1H), 7.10 (d, 2H), 4.80 - 4.93 (m, 2H), 4.02 (t, 2H), 3.57 (d, 2H), 3.52 (bs, 18H), 3.25 - 3.38 (m, 2H), 2.45 (s, 3H), 2.28 (s, 3H), 2.01 - 2.04 (m, 4H), 1.75 - 1.79 (m, 2H), 1.62 - 1.66 (m, 2H), 1.42 - 1.45 (m, 2H), 1.22 - 1.27 (m, 6H).

[0077] Step (d): Preparation of the compound of Formula I-3

[0078] Maintain a slightly positive nitrogen pressure. Sequentially add 1.8 L of o-xylene, 542.42 g (0.626 mol) of the compound of Formula 7-3, and 389.40 g (1.878 mol) (2 - 10 eq) of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to a 5 L reaction flask. After adding, stir well; heat the reaction solution to 140 °C for reaction. Keep the temperature for 10 hours for the reaction to complete.

[0079] Let the reaction solution cool naturally to room temperature, then continue to cool to 0 °C, keep the temperature for crystal precipitation for 3 hours, a large amount of solid precipitates, filter, and collect the filter cake to obtain 729.03 g (0.569 mol) of an orange solid product.

[0080] The yield is 90.9%, the total yield of the 4-step reaction is 39.27%, and the product purity is 98.74% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 9.49 (s, 1H), 8.71 (d, 1H), 8.54 (d, 1H), 8.25 - 8.30 (m, 3H), 7.65 - 7.70 (m, 2H), 7.47 (d, 4H), 7.32 (d, 1H), 7.17 (s, 1H), 7.10 (d, 4H), 4.80 - 4.93 (m, 2H), 3.25 - 3.38 (m, 2H), 3.12 (bs, 20H), 2.28 (s, 6H), 2.01 - 2.04 (m, 4H), 1.72 - 1.77 (m, 4H), 1.55 - 1.59 (m, 4H), 1.22 - 1.30 (m, 8H), 0.64 (t, 4H). Example 4

[0081]

[0082] Step (a): Preparation of the compound of Formula 3-4

[0083] Maintain a slightly positive nitrogen pressure. Sequentially add 2 L of DMF, 149.21 g (1.0 mol) of the compound of Formula 1-4, 2-methylbenzothiazole, and 451.92 g (4.0 mol) of the compound of Formula 2-4, 1,3-dichloropropane to a 5 L reaction flask. After adding, stir well, and heat the reaction solution to 150 °C for reaction. Keep the temperature for 6 hours for the reaction to complete.

[0084] Cool the reaction solution to room temperature, add 2000 mL of petroleum ether to it, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 190.87 (0.728 mol) of a yellow solid product.

[0085] The yield is 72.8%.

[0086] Product purity: 98.68% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.51 (d, 1H), 8.38 (d, 1H), 7.90 (t, 1H), 7.82 (t, 1H), 4.81 - 4.89 (m, 2H), 3.85 (t, 2H), 3.26 (s, 3H), 2.45 - 2.56 (m, 2H).

[0087] Step (b): Preparation of the compound of Formula 6-4

[0088] Maintain a slightly positive pressure of nitrogen. Add 8 L of tetrahydrofuran, 703.48 g (4.3 mol) of the compound of Formula 4-4, 4-chloroquinoline, and 3472.51 g (17.2 mol) of the compound of Formula 5-4, 1,3-dichloropropane, successively into a 50 L reaction flask. After adding, stir well, and heat the reaction solution to 66 °C for reaction. Keep the temperature for 68 hours until the reaction is completed.

[0089] Cool the reaction solution to room temperature, add 8000 mL of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 811.10 g (2.933 mol) of a yellow solid product.

[0090] Yield: 68.2%.

[0091] Product purity: 98.86% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.49 - 8.74 (m, 2H), 8.31 - 8.41 (m, 2H), δ 8.51 - 8.72 (m, 2H), 8.31 - 8.41 (m, 2H), 8.06 - 8.21 (m, 2H), 5.29 - 5.38 (m, 2H), 3.84 (t, 2H), 2.50–2.58 (m, 2H).

[0092] Step (c): Preparation of the compound of Formula 7-4

[0093] Maintain a slightly positive pressure of nitrogen. Add 2.0 L of ethanol, 190.87 (0.728 mol) of the compound of Formula 3-4, and 805.40 g (2.912 mol) of the compound of Formula 6-4, successively into a 5 L reaction flask, and stir well. Then add 29.47 g (0.291 mol) of triethylamine thereto. After adding, stir well, and heat the reaction solution to 40 °C for reaction. Keep the temperature for 3 hours until the reaction is completed.

[0094] Cool the reaction solution to room temperature, add 1 L of ethyl acetate and 1 L of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 301.50 g (0.647 mol) of a red solid product.

[0095] The yield is 88.9%.

[0096] Product purity: 99.31% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.48 (d, 1H), 8.36 (d, 1H), 8.25 - 8.31 (m, 3H), 7.74 - 7.92 (m, 5H), 6.87 (s, 1H), 4.77 - 4.89 (m, 2H), 3.73 (t, 2H), 3.21 (t, 2H), 3.05 - 3.21 (m, 2H), 2.39 - 2.49 (m, 2H), 2.01 - 2.04 (m, 2H).

[0097] Step (d): Preparation of the compound of formula I-4

[0098] Maintain a slightly positive nitrogen pressure. Add 1.8 L of o-xylene, 301.50 g (0.647 mol) of the compound of formula 7-4, and 645.72 g (2.589 mol) of 3-N,N-dimethylaminotriethoxysilane (CAS: 43108-00-5) to a 5 L reaction flask in sequence. After addition, stir well; heat the reaction solution to 140 °C for reaction. Keep the reaction at this temperature for 8 hours until the reaction is complete.

[0099] Let the reaction solution cool naturally to room temperature, then continue to cool to 0 °C and keep it for 3 hours for crystallization. A large amount of solid is precipitated. Filter and collect the filter cake to obtain 553.18 g (0.573 mol) of a red solid product.

[0100] The yield is 88.60%, and the total yield of the 4-step reaction is 39.11%. Product purity: 98.89% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.52 (d, 1H), 8.37 (d, 1H), 8.24 - 8.29 (m, 3H), 7.74 - 7.93 (m, 5H), 6.93 (s, 1H), 4.79 - 4.93 (m, 2H), 3.86 (q, 12H), 3.03 - 3.24 (m, 18H), 2.23 - 2.31 (m, 2H), 1.96 - 2.00 (m, 2H), 1.73 - 1.78 (m, 4H), 1.22 (t, 18H), 0.64 (t, 4H). Example 5

[0101]

[0102] Step (a): Preparation of the compound of formula 3-5

[0103] Maintain a slightly positive pressure of nitrogen. Add 4 L of DMF, 149.21 g (1.0 mol) of the compound of Formula 1-5, 2-methylbenzothiazole, and 2392.2 g (10 mol) of the compound of Formula 2-5, 1,12-dichlorododecane, successively into a 20 L reaction flask. After adding, stir well, and heat the reaction solution to 150 °C for reaction. Keep the temperature for 6 hours for the reaction to complete.

[0104] Cool the reaction solution to room temperature, add 3000 mL of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 273.46 g (0.704 mol) of a yellow solid product.

[0105] The yield is 70.4%.

[0106] Product purity: 99.43% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.51 (d, 1H), 8.38 (d, 1H), 7.90 (t, 1H), 7.82 (t, 1H), 4.81 - 4.89 (m, 2H), 3.85 (t, 2H), 3.26 (s, 3H), 2.01 - 2.04 (m, 2H), 1.73 - 1.79 (m, 2H), 1.46 - 1.51 (m, 2H), 1.23 - 1.29 (m, 14H).

[0107] Step (b): Preparation of the compound of Formula 6-5

[0108] Maintain a slightly positive pressure of nitrogen. Add 13 L of tetrahydrofuran, 850.75 g (5.0 mol) of the compound of Formula 4-5, 4-chloroquinoline, and 11407.9 g (26 mol) of the compound of Formula 5-5, 1,14-diiodotetradecane, successively into a 50 L reaction flask. After adding, stir well, and heat the reaction solution to 66 °C for reaction. Keep the temperature for 75 hours for the reaction to complete.

[0109] Cool the reaction solution to room temperature, add 10000 mL of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 2179.97 g (3.552 mol) of a yellow solid product.

[0110] The yield is 68.3%.

[0111] Product purity: 98.67% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.49 - 8.74 (m, 2H), 8.31 - 8.41 (m, 2H), δ 8.06 - 8.21 (m, 2H), 5.29 - 5.36 (m, 2H), 2.95 (t, 2H), 2.01 - 2.04 (m, 2H), 1.82 - 1.87 (m, 2H), 1.23 - 1.29 (m, 20H).

[0112] Step (c): Preparation of the compound of Formula 7-5

[0113] Maintain a slightly positive pressure of nitrogen. Add 2.0 L of ethanol, 273.46 g (0.704 mol) of the compound of Formula 3-5, and 2160.58 g (3.52 mol) of the compound of Formula 6-5 to a 5 L reaction flask in sequence, and stir well. Then add 35.62 g (0.352 mol) of triethylamine thereto. After adding, stir well, and heat the reaction solution to 40 °C for reaction. Keep the temperature for reaction for 4 hours until the reaction is completed.

[0114] Cool the reaction solution to room temperature, add 2 L of ethyl acetate and 2 L of petroleum ether thereto, cool to 0 °C, keep the temperature overnight, a large amount of solid precipitates, filter, and collect the filter cake to obtain 514.94 g (0.615 mol) of a red solid product.

[0115] Yield: 87.3%.

[0116] Product purity: 98.94% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.48 (d, 1H), 8.36 (d, 1H), 8.25 - 8.30 (m, 3H), 7.74 - 7.93 (m, 5H), 6.87 (s, 1H), 4.81 - 4.89 (m, 2H), 3.85 (t, 2H), 3.05 - 3.21 (m, 2H), 2.95 (t, 2H), 2.01 - 2.04 (m, 4H), 1.82 - 1.87 (m, 2H), 1.73 - 1.79 (m, 2H), 1.46 - 1.51 (m, 2H), 1.23 - 1.29 (m, 34H).

[0117] Step (d): Preparation of the compound of Formula I-5

[0118] Maintain a slightly positive pressure of nitrogen, and sequentially add 5 L of o-xylene, 514.94 g (0.615 mol) of the compound of Formula 7-5, and 637.18 g (3.073 mol) (2 - 10 eq) of (N,N-dimethyl-3-aminopropyl)trimethoxysilane to a 20 L reaction flask. After adding, stir well; heat the reaction solution to 140 °C for reaction. Keep the temperature for 7 hours until the reaction is completed.

[0119] Let the reaction solution cool naturally to room temperature, then continue to cool to 0 °C, keep the temperature for crystal precipitation for 3 hours. A large amount of solid is precipitated, filtered, and the filter cake is collected to obtain 678.20 g (0.541 mol) of a red solid product.

[0120] The yield is 88.10%, the total yield of the 4-step reaction is 36.98%, and the product purity is 99.28% (HPLC); NMR data: 1H NMR (400 MHz, DMSO-d6): δ 8.49 (d, 1H), 8.37 (d, 1H), 8.25 - 8.30 (m, 3H), 7.74 - 7.93 (m, 5H), 6.94 (s, 1H), 4.81 - 4.89 (m, 2H), 3.85 (t, 2H), 3.51 (bs, 18H), 3.05 - 3.21 (m, 22H), 2.01 - 2.04 (m, 4H), 1.92 - 1.97 (m, 4H), 1.72 - 1.77 (m, 4H), 1.22 - 1.31 (m, 36H), 0.65 (t, 4H).

[0121] Antibacterial performance test of the compound:

[0122] Determination of MIC (Minimum Inhibitory Concentration): The compounds (I-1, I-2, I-3, I-4, I-5) prepared in Examples 1 - 5 are mixed in LB nutrient broth and serially diluted two-fold by the microbroth dilution method. After adding a quantitative test bacterium and culturing for a certain time, the lowest compound concentration at which no bacterial growth is observed is the MIC (Minimum Inhibitory Concentration) of the compound against this bacterium.

[0123] The specific determination steps are as follows:

[0124] (1) Preparation of the bacterial suspension: On a sterile operating table, use a sterilized inoculation loop to pick an appropriate amount of bacterial culture and transfer it to 10 mL of LB broth culture medium. Culture it in a shaker at 37 °C for 6 - 8 h until the bacterial suspension reaches a slight or moderate turbidity. To ensure the accuracy and precision of the drug sensitivity test, the concentration of the inoculated bacterial suspension must be controlled accordingly. Therefore, transfer a small amount of the bacterial suspension to a colorimetric tube, dilute it to 0.5 McFarland standard concentration and then dilute it 1000 times, and the bacterial suspension content is about 1×10 5 cfu / mL.

[0125] (2) Preparation of the stock solution of the antibacterial compound: Dissolve the compound in sterile water to prepare a stock solution of the antibacterial compound at a specific concentration, and use a sterile filter head to remove any bacteria that may be present in the solution.

[0126] (3) Preparation of the MIC plate: Add 100 μL of LB broth to each well in rows 2 to 7 of columns 2 to 10 of a 96-well plate. Add 100 μL of the stock solution of the antibacterial compound to column 2. After pipetting and mixing well, aspirate 100 μL and transfer it to column 3, and so on, for a total of 8 concentration gradients. Discard 100 μL of the mixed solution from column 9. Do not add any drug solution to column 10 as a positive control. Then add 100 μL of the bacterial suspension to each well, and pipette and mix the mixed solution evenly. Add 200 μL of LB broth to column 11 without adding any bacterial solution as a negative control. After pipetting and mixing the compound and the bacterial solution, cover the 96-well plate and incubate it in a 37 °C biochemical incubator for 20 - 24 h (for Escherichia coli ATCC 25922 and Staphylococcus aureus ATCC 6538) or in a 28 °C biochemical incubator for 40 - 48 h (for Candida albicans ATCC 10231 and Aspergillus niger ATCC 16404). Measure the OD570 value (optical density) of the bacterial solution using a microplate reader.

[0127] (4) Result determination: The MIC (minimum inhibitory concentration) is the concentration at which bacterial growth is completely inhibited in the 96-well plate. The specific results are shown in Table 1.

[0128]

[0129] From the above experimental results, it can be seen that thiazole orange organosilicon quaternary ammonium salt compounds (Compound I-1, Compound I-2, Compound I-3, Compound I-4, Compound I-5) have excellent antibacterial effects against common bacterial strains (Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, Candida albicans ATCC 10231, Aspergillus niger ATCC 16404), and the minimum inhibitory concentrations are all below 35 mg / L.

[0130] Among them, Compound I-5 has particularly excellent antibacterial effects. The minimum inhibitory concentrations against common bacterial strains are all below 3 mg / L, and the minimum inhibitory concentrations against the three bacterial strains of Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, and Candida albicans ATCC 10231 are even as low as below 0.4 mg / L.

[0131] Performance test of the compound in fabric antibacterial finishing:

[0132] According to the mass percentage, 2 parts of the compounds (I-1, I-2, I-3, I-4, I-5) prepared in Examples 1-5 and 98 parts of water were mixed evenly to prepare antibacterial compositions 6-10.

[0133] For the antibacterial compositions 6-10, with a bath ratio of 1:15, pure cotton fabrics were immersed in the antibacterial finishing agent solution for 10 minutes, then passed through a squeezing roller with a liquor pick-up rate of 80%, and then the fabrics were placed in a drying oven at 150 °C for baking for 5 minutes. The fabrics were taken out of the drying oven to obtain the corresponding antibacterial fabrics respectively.

[0134] Antibacterial property test of antibacterial fabrics: Referring to GB / 120944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Oscillation method", the selected strains were Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 25922), Candida albicans (ATCC 10231), and Aspergillus niger (ATCC 16404). The specific results are shown in Table 2.

[0135]

[0136] It can be seen from the above experimental results that the antibacterial fabrics prepared by antibacterial finishing of cotton fabrics with the thiazole orange organosilicon quaternary ammonium salt compound of the present invention have very excellent antibacterial properties, and have good antibacterial effects on common strains (Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, Candida albicans ATCC 10231, Aspergillus niger ATCC 16404), and the antibacterial rates are all 99.9%. Moreover, these antibacterial fabrics all have good wash resistance, can withstand washing, and the antibacterial rates after 100 washes are all above 90%.

[0137] More excellently, when m in the compound molecular formula is greater than or equal to 8 and less than or equal to 12, and n is greater than or equal to 10 and less than or equal to 15, the wash resistance is particularly good. The antibacterial rates after 100 washes are all maintained at 99.9%, the antibacterial rates after 200 washes are all above 80%, and the antibacterial rates after 300 washes are also all above 70%.

[0138] The above examples are only for explaining the technical concept and characteristics of the present invention, and the purpose is to enable those who are familiar with this technology to understand the content of the present invention and implement it accordingly, and cannot be used to limit the protection scope of the present invention; all equivalent transformations or modifications made according to the spirit and essence of the present invention should be covered within the protection scope of the present invention.

Claims

1. A thiazole orange organosilicon quaternary ammonium salt compound, characterized in that, the structure of the said compound is shown in Formula I, ， Among them, X 1 and X 2 are selected from chlorine, bromine, iodine, tosylate, benzenesulfonyloxy, mesyloxy, R 1 , R 2 , R 3 , R 4 are each independently selected from methyl, ethyl, C3-C8 alkyl, phenyl, nitro, nitroso, sulfonyl, mesyl, fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethyl, m = 0 - 30, n = 0 - 30.

2. The thiazole orange organosilicon quaternary ammonium salt compound according to Claim 1, characterized in that, the m is greater than or equal to 8 and less than or equal to 12; the n is greater than or equal to 10 and less than or equal to 15.

3. A preparation method of the thiazole orange organosilicon quaternary ammonium salt compound according to Claim 1, characterized in that, it comprises the following steps: ， (a) Under the condition of air isolation, add a first reaction solvent, a compound of Formula 1, and a compound of Formula 2 into a reaction kettle, the reaction temperature is 60 - 200 °C, and the reaction time is 6 - 72 hours to obtain a compound of Formula 3, wherein the molar ratio of the compound of Formula 1 to the compound of Formula 2 is 1:1 - 10; (b) Under the condition of air isolation, add a second reaction solvent into the reaction kettle, and then add a compound of Formula 4 and a compound of Formula 5, the reaction temperature is 60 - 200 °C, and the reaction time is 3 - 72 hours to obtain a compound of Formula 6, wherein the molar ratio of the compound of Formula 4 to the compound of Formula 5 is 1:1 - 10; (c) Under the condition of air isolation, add a third reaction solvent, the compound of Formula 3 and the compound of Formula 6 into the reaction kettle, react at a reaction temperature of 25 - 60 °C, and keep the temperature for reaction for 1 - 5 hours to obtain a compound of Formula 7, wherein the molar ratio of the compound of Formula 3 to the compound of Formula 6 is 1:1 - 10; (d) Under the condition of air isolation, add a fourth reaction solvent, the compound of Formula 7 and the compound of Formula 8 into the reaction kettle, react at a reaction temperature of 80 - 200 °C, and keep the temperature for reaction for 12 - 102 hours to obtain a compound of Formula I, wherein the molar ratio of the compound of Formula 7 to the compound of Formula 8 is 1:1 - 10; Among them, X 1 and X 2 are selected from chlorine, bromine, iodine, tosylate, benzenesulfonyloxy, mesyloxy, R 1 , R 2 , R 3 , R 4 are each independently selected from methyl, ethyl, C3-C8 alkyl, phenyl, nitro, nitroso, sulfonyl, mesyl, fluorine, chlorine, bromine, iodine, trifluoromethyl, difluoromethyl, m = 0 - 30, n = 0 - 30.

4. The preparation method of the thiazole orange organosilicon quaternary ammonium salt compound according to Claim 3, characterized in that, the m is greater than or equal to 8 and less than or equal to 12; the n is greater than or equal to 10 and less than or equal to 15.

5. The preparation method of the thiazole orange organosilicon quaternary ammonium salt compound according to Claim 3, characterized in that, in step (a), the said first reaction solvent is at least one of acetonitrile, p - xylene, o - xylene, m - xylene, toluene, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, acetonitrile, ethyl acetate, tetrahydrofuran, 2 - methyltetrahydrofuran or dioxane.

6. The preparation method of the thiazole orange organosilicon quaternary ammonium salt compound according to Claim 3, characterized in that, in step (b), the said second reaction solvent is at least one of acetonitrile, p - xylene, o - xylene, m - xylene, toluene, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, ethyl acetate, tetrahydrofuran, 2 - methyltetrahydrofuran or dioxane.

7. The preparation method of the thiazole orange organosilicon quaternary ammonium salt compound according to Claim 3, characterized in that, In step (c), the third reaction solvent is at least one of ethanol, methanol, isopropanol, n-butanol, p-xylene, o-xylene, m-xylene, toluene, ethylene glycol diethyl ether, ethylene glycol dimethyl ether, DMF, DMSO, acetonitrile, tetrahydrofuran, 2-methyltetrahydrofuran, and dioxane.

8. The method for preparing the thiazole orange organosilicon quaternary ammonium salt compound according to claim 3, characterized in that, in step (d), the fourth reaction solvent is at least one of o-xylene, p-xylene, m-xylene, toluene, ethylene glycol diethyl ether, DMF, DMSO, acetonitrile or acetone.

9. The method for preparing the thiazole orange organosilicon quaternary ammonium salt compound according to claim 3, characterized in that, in step (d), it is also necessary to continue to add a basic reagent, and the basic reagent is at least one of triethylamine and N,N-diisopropylethylamine.

10. The application of the thiazole orange organosilicon quaternary ammonium salt compound according to claims 1-2 or the thiazole orange organosilicon quaternary ammonium salt compound prepared by the method for preparing the thiazole orange organosilicon quaternary ammonium salt compound according to any one of claims 3-9 in the preparation of materials against Staphylococcus aureus, materials against Escherichia coli, materials against Candida albicans, and materials against Aspergillus niger.

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