Thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound and preparation method and application thereof

Abstract

The present invention discloses a thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound, the structure of the compound is shown in Formula I, wherein X 1 is selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R 1 , R 2 , R 3 and R 4 They are respectively selected from methyl, ethyl, C3-C8 alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-fluorophenyl, 4-iodophenyl, 4-trifluoromethoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, m=0-100, n=0-100. The thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound of the present invention has five structures of thiazole ring, quinoline ring, organosiloxane, quaternary phosphonium salt and quaternary ammonium salt, has a broad antibacterial spectrum, and has antibacterial activity against Staphylococcus aureus, Escherichia coli, Candida albicans and Aspergillus niger.

Description

Technical Field

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

[0002] Antibacterial dyes are a class of multifunctional compounds that have both dyeing and antibacterial functions, and have great application prospects in the medical, clothing, food and other industries. For example, dyeing and antibacterial finishing of fabrics are usually two independent links in traditional Chinese medicine. However, such a treatment method will have the following problems: on the one hand, some antibacterial finishing may affect the dyeing performance or other functional finishing; on the other hand, antibacterial finishing often requires a separate post-processing process. Separate dyeing and finishing will lead to increased costs and waste of resources, and will also cause greater environmental damage, which does not meet the requirements of sustainable development. The use of antibacterial dyes can carry out the dyeing and antibacterial finishing of fabrics in the same step, giving the fabric antibacterial properties while dyeing it. Compared with traditional processes, the use of antibacterial dyes reduces one step of wet processing, greatly reduces energy consumption, and reduces water consumption and wastewater discharge, which is undoubtedly more green and environmentally friendly.

[0003] Thiazole orange is a cationic dye that contains both thiazole and quinoline rings in its 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 electrophoretic separation, quantitative determination of DNA and other fields. The cationic structural characteristics of thiazole orange make it potential for combination with other cationic antimicrobial agents. It will be a very meaningful work to design a series of antimicrobial dye compounds using thiazole orange as the parent core.

[0004] Conventional quaternary ammonium salt antimicrobial agents have become the leading antimicrobial products due to their low cost. Four generations of typical quaternary ammonium salt antimicrobial agents have been developed internationally. Among them, the DC-5700 organosilicon quaternary ammonium salt antimicrobial agent developed by Dow Corning and the BV6000E organosilicon quaternary ammonium salt antimicrobial agent developed by J&K are the most representative. They are widely used at home and abroad, with fast sterilization speed, high antimicrobial efficacy and good stability.

[0005] Quaternary phosphonium salts and quaternary ammonium salts have similar structures. Since the P element is located below the N element in the periodic table, the phosphorus atom has a larger ionic radius than the nitrogen atom, has a stronger polarization effect, and has a weaker electronegativity. Therefore, the molecular structure of quaternary phosphonium salts is relatively stable, and it is difficult to react with general oxidants and reductants, as well as acids and alkalis. It can be used in water within the pH range of 2-12. It has the advantages of high efficiency, rapidity, broad spectrum, easy degradation, low toxicity, and easy use. It can kill algae and has a good bactericidal effect on iron-oxygen bacteria, heterotrophic bacteria, and sulfate-reducing bacteria. It has been widely used as a bactericide and algaecide in industrial circulating water systems, oilfield water injection fungicides, and agricultural pesticides. Due to its low foaming, strong slime stripping ability and wide pH application range, it is used as an upgraded product of traditional quaternary ammonium salt fungicides in industrial circulating water and oilfield water injection systems. However, there is no research on combining quaternary phosphonium salts with quaternary ammonium salts for antibacterial purposes, nor is there any research on using quaternary phosphonium salts alone or in combination with quaternary ammonium salts for antibacterial finishing of textiles.

[0006] So far, there have been many studies on organic small molecule antibacterial agents. People have found that long-chain alkyl quaternary ammonium salts and quaternary phosphonium salts have strong antibacterial properties, but these organic small molecule antibacterial agents have disadvantages such as easy volatility, easy residue, difficult processing, and poor stability. Therefore, the development of new antibacterial materials with these antibacterial groups is a recent research direction and hotspot. These new antibacterial materials can overcome these disadvantages, will not penetrate into human skin, are safer, and have better antibacterial properties. Summary of the invention

[0007] In view of the above problems in the prior art, the present invention develops a thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound and a preparation method thereof, as well as the application of the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound in antibacterial materials.

[0008] One of the technical solutions of the present invention is to provide a thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound, characterized in that the compound structure is as shown in Formula I, wherein X1 and X2 are selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R1, R2, R3 and R4 are selected from methyl, ethyl, C3-C8 alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-fluorophenyl, 4-iodophenyl, 4-trifluoromethoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, m=0-100, n=0-100.

[0009] In a preferred embodiment of the present invention, the m is greater than or equal to 8 and less than or equal to 12; and the n is greater than or equal to 10 and less than or equal to 15.

[0010] The second technical solution of the present invention is to provide a method for preparing a thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound, comprising the following steps:

[0011]

[0012] (a) adding a first reaction solvent, a compound of formula 1, and a compound of formula 2 to a reaction kettle under air-tight conditions, reacting at a temperature of 60-200° C. for 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;

[0013] (b) adding a second reaction solvent to the reaction kettle in an airtight state, reacting the compound of formula 4 with triphenylphosphine at a reaction temperature of 80-200° C. for a reaction time of 12-102 hours to obtain a compound of formula 5;

[0014] (c) adding a third reaction solvent to the reaction kettle under air-tight conditions, and then adding the compound of formula 5 and the compound of formula 6, the reaction temperature is 60-200° C., the reaction time is 3-72 hours, to obtain a compound of formula 7, wherein the molar ratio of the compound of formula 3 to the compound of formula 4 is 1:1-10;

[0015] (d) adding a fourth reaction solvent, a compound of formula 3 and a compound of formula 7 to a reaction kettle under air conditions, reacting at a reaction temperature of 25-60° C., and keeping the temperature for 1-5 hours to obtain a compound of formula 8, wherein the molar ratio of the compound of formula 3 to the compound of formula 7 is 1:1-10;

[0016] (e) adding a fifth reaction solvent, a compound of formula 8 and a compound of formula 9 to a reaction kettle under air-tight conditions, reacting at a reaction temperature of 80-200° C., and keeping the temperature for 12-102 hours to obtain a compound of formula I, wherein the molar ratio of the compound of formula 8 to the compound of formula 9 is 1:1-10, and the fifth reaction solvent is at least one of o-xylene, p-xylene, m-xylene, toluene, ethylene glycol diethyl ether, DMF, DMSO, acetonitrile or acetone;

[0017] wherein X1 and X2 are selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R1, R2, R3 and R4 are selected from methyl, ethyl, C3-C8 alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-fluorophenyl, 4-iodophenyl, 4-trifluoromethoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, m=0-100, n=0-100.

[0018] In a preferred embodiment of the present invention, the m is greater than or equal to 8 and less than or equal to 12; and the n is greater than or equal to 10 and less than or equal to 15.

[0019] 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.

[0020] In a preferred embodiment of the present invention, in step (b), the second reaction solvent is at least one of o-xylene, p-xylene, o-xylene, m-xylene, toluene, ethylene glycol diethyl ether, DMF, DMSO, acetonitrile and acetone.

[0021] In a preferred embodiment of the present invention, in step (c), the third 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.

[0022] In a preferred embodiment of the present invention, in step (d), the fourth 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.

[0023] In a preferred embodiment of the present invention, step (d) further comprises the step of continuing to add an alkaline reagent, wherein the alkaline reagent is at least one of triethylamine and N,N-diisopropylethylamine.

[0024] The third technical solution of the present invention is to provide the above-mentioned thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound and the use of the thiazole orange quaternary ammonium quaternary phosphonium salt prepared by the preparation method of the above-mentioned thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound in antibacterial materials. Beneficial Effects

[0025] The thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound of the present invention has five structures of thiazole ring, quinoline ring, organosiloxane, quaternary phosphonium salt and quaternary ammonium salt, has a broad antibacterial spectrum, and has antibacterial activity against Staphylococcus aureus, Escherichia coli, Candida albicans and Aspergillus niger.

[0026] The washability of the invention is particularly good, and the antibacterial rate after 100 washings is above 80%, and the antibacterial rate after 200 washings is still above 70%. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention. Example 1

[0028]

[0029] Step (a): Preparation of the compound of formula 3-1

[0030] Maintaining a slight positive pressure of nitrogen, add 2L of acetonitrile, 149.21 g (1.0 mol) of the compound 2-methylbenzothiazole of formula 1-1, and 201.89 g (1.0 mol) of the compound 1,3-dibromopropane of formula 2-1 to the 5L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 82°C for reaction. Keep the temperature for 22 hours, and the reaction is complete.

[0031] The reaction solution was cooled to room temperature, 1.5 L of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, and the mixture was filtered and the filter cake was collected to obtain 254.55 g (0.725 mol) of a yellow solid product of formula 3-1.

[0032] Yield: 73.8%.

[0033] Product purity: 98.21% (HPLC); NMR data: 1H NMR (400MHz, 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).

[0034] Step (b): Preparation of the compound of formula 5-1

[0035] Keeping nitrogen slightly positive pressure, add 1.8L p-xylene, 201.89g (1.0mol) 1,3-dibromopropane of Formula 4-1 and 262.29g (1.0mol) triphenylphosphine to the 5L reaction bottle in sequence, stir evenly after adding, heat the reaction solution to 138℃ and react. Keep the temperature for 15 hours, and the reaction is complete.

[0036] The reaction solution was naturally cooled to room temperature, and then continued to cool to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid was precipitated, and the filter cake was collected to obtain 421.48 g (0.908 mol) of white solid product of formula 5-1.

[0037] Yield: 90.8%, product purity: 99.48% (HPLC); 1H NMR (400MHz, DMSO-d6): δ 7.73-7.83 (m, 15H), 3.78 (t, 2H), 3.66 (t, 2H), 2.12-2.26 (m, 2H).

[0038] Step (c): Preparation of the compound of formula 7-1

[0039] Keeping nitrogen slightly positive pressure, add 2L acetonitrile, 421.48g (0.908mol) of compound 5-1, and 148.55g (0.908mol) of compound 6-1, 4-chloroquinoline, to the 5L reaction bottle in sequence. After adding, stir evenly and heat the reaction solution to 82℃ for reaction. Keep the temperature for 16 hours and the reaction is complete.

[0040] The reaction solution was cooled to room temperature, 1000 ml of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 394.74 g (0.629 mol) of a yellow solid product.

[0041] Yield: 69.25%.

[0042] Product purity: 99.25% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.49-8.74 (m, 2H), 8.31-8.41 (m, 2H), 8.06-8.21 (m, 2H), 7.74-7.85 (m, 15H), 5.29-5.38 (m, 2H), 3.81 (t, 2H), 2.50–2.58 (m, 2H).

[0043] Step (d): Preparation of the compound of formula 8-1

[0044] Keeping nitrogen slightly positive pressure, add 1.2 L ethanol, 220.84 g (0.629 mol) of compound 3-1 and 394.74 g (0.629 mol) of compound 7-1 to the 5 L reaction bottle in turn and stir evenly. Then add 6.37 g (0.063 mol) of triethylamine. After adding, stir evenly and heat the reaction solution to 40 °C for reaction. Keep the temperature for 4 hours and the reaction is complete.

[0045] The reaction solution was cooled to room temperature, 2000 mL of ethyl acetate and petroleum ether were added thereto, and the solution was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 492.04 g (0.571 mol) of a red solid product.

[0046] Yield: 90.8%.

[0047] Product purity: 98.68% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.50 (d, 1H), 8.37 (d, 1H), 8.25-8.30 (m, 3H), 7.74-7.93 (m, 20H), 6.88 (s, 1H), 4.77-4.89 (m, 2H), 3.79 (t, 2H), 3.73 (t, 2H), 3.05-3.21 (m, 2H), 2.39-2.49 (m, 2H), 2.01-2.05 (m, 2H).

[0048] Step (e): Preparation of the compound of formula I-1

[0049] Keeping nitrogen slightly positive pressure, add 1.8L o-xylene, 492.04g (0.571mol) of compound 8-1 and 87.36g (0.421mol) of compound 9-1 to the 5L reaction bottle in sequence, stir evenly after adding, heat the reaction solution to 140℃ and react. Keep the temperature for 22 hours, and the reaction is complete.

[0050] The reaction solution was naturally cooled to room temperature, and then continued to be cooled to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid was precipitated, which was filtered and the filter cake was collected to obtain 546.97 g (0.512 mol) of a red solid product.

[0051] Yield 89.6%, total yield of 5 steps reaction 37.75%, product purity: 98.86% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.53 (d, 1H), 8.39 (d, 1H), 8.26-8.30 (m, 3H), 7.72-7.93 (m, 20H), 6.89 (s, 1H), 4.77-4.89 (m, 2H), 3.79 (t, 2H), 3.52 (bs, 9H), 3.05-3.21 (m, 12H), 2.23-2.32 (m, 2H), 2.01-2.05 (m, 2H), 1.70-1.75 (m, 2H), 0.62 (t, 2H). Example 2

[0052]

[0053] Step (a): Preparation of the compound of formula 3-2

[0054] Maintaining a slight positive pressure of nitrogen, add 2L of 2-methyltetrahydrofuran, 149.21 g (1.0 mol) of the compound 2-methylbenzothiazole of formula 1-2, and 282.08 g (2.0 mol) of the compound 1,3-dichloropentane of formula 2-2 to the 5L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 80°C for reaction. Keep the temperature for 30 hours, and the reaction is complete.

[0055] The reaction solution was cooled to room temperature, 3000 mL of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 208.4 g (0.718 mol) of a yellow solid product.

[0056] Yield: 71.8%.

[0057] Product purity: 98.55% (HPLC); NMR data: 1H NMR (400MHz, 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).

[0058] Step (b): Preparation of the compound of formula 5-2

[0059] Maintaining a slight positive pressure of nitrogen, add 4.5 L of p-xylene, 774.8 g (2.5 mol) of compound 4-1 1,4-diiodobutane and 983.59 g (3.75 mol) of triphenylphosphine to the 10 L reaction bottle in sequence, stir evenly after adding, and heat the reaction solution to 138 °C for reaction. Keep the temperature for 12 hours, and the reaction is complete.

[0060] The reaction solution was naturally cooled to room temperature, and then continued to cool to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 1280.32 (2.24 mol) of the white solid product of formula 5-1.

[0061] Yield: 89.5%, product purity: 99.05% (HPLC); 1H NMR (400MHz, DMSO-d6): δ 7.73-7.83 (m, 15H), 3.72 (t, 2H), 2.95 (t, 2H), 2.05-2.13 (m, 2H), 1.86-1.92 (m, 2H).

[0062] Step (c): Preparation of the compound of formula 7-2

[0063] Keeping nitrogen slightly positive pressure, add 5L ethylene glycol diethyl ether, 1280.32 (2.24 mol) of compound 5-2, and 794.89 g (4.48 mol) of compound 6-2, 2-methyl-4-chloroquinoline, to the 20L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 120℃ for reaction. Keep the temperature for 12 hours, and the reaction is complete.

[0064] The reaction solution was cooled to room temperature, 1000 mL of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 1145.93 (1.528 mol) of a yellow solid product.

[0065] Yield: 68.3%.

[0066] Product purity: 99.45% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.56 (d, 1H), 8.46 (d, 1H), 8.22 (t, 1H), 8.01 (t, 1H), 7.74-7.85 (m, 15H), 7.55 (s, 1H), 5.18-5.25 (m, 2H), 3.80 (t, 2H), 2.67 (s, 3H), 2.00-2.03 (m, 2H), 1.82-1.85 (m, 2H).

[0067] Step (d): Preparation of the compound of formula 8-2

[0068] Keeping nitrogen slightly positive pressure, add 2 L of p-xylene, 208.4 g (0.718 mol) of compound 3-2 and 1076.79 (1.436 mol) of compound 7-2 to the 5 L reaction bottle in turn and stir well. Then add 18.56 g (0.2 mol) of N,N-diisopropylethylamine. After adding, stir well and heat the reaction solution to 50 °C for reaction. Keep the temperature for 2 hours and the reaction is complete.

[0069] The reaction solution was cooled to room temperature, 2000 mL of ethyl acetate and 2000 mL of petroleum ether were added thereto, and the solution was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 568.41 g (0.649 mol) of a red solid product.

[0070] Yield: 90.4%.

[0071] Product purity: 99.35% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.52 (d, 1H), 8.39 (d, 1H), 8.25-8.30 (m, 3H), 7.90-7.93 (m, 2H), 7.73-7.83 (m, 16H), 7.27 (s, 1H), 6.91 (s, 1H), 4.75-4.83 (m, 2H), 3.76 (t, 2H), 3.58 (t, 2H), 3.03-3.14 (m, 2H), 2.54 (s, 3H), 2.01-2.03 (m, 2H), 1.89-1.95 (m, 2H), 1.42-1.47(m, 4H), 1.27-1.30(m, 2H).

[0072] Step (e): Preparation of the compound of formula I-2

[0073] Keeping nitrogen slightly positive pressure, add 1.8L o-xylene, 568.41g (0.649mol) of compound 8-2 and 269.17g (1.298mol) of compound 9-2 to the 5L reaction bottle in sequence, stir evenly after adding, heat the reaction liquid to 140℃ and react. Keep the temperature for 22 hours, and the reaction is complete.

[0074] The reaction solution was naturally cooled to room temperature, and then continued to be cooled to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid was precipitated, which was filtered and the filter cake was collected to obtain 642.53 g (0.593 mol) of a red solid product.

[0075] Yield 91.4%, total yield of 5 steps 36.26%, product purity: 98.25% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.53 (d, 1H), 8.41 (d, 1H), 8.25-8.30 (m, 3H), 7.90-7.93 (m, 2H), 7.73-7.83 (m, 16H), 7.27 (s, 1H), 6.91 (s, 1H), 4.75-4.83 (m, 2H), 3.76 (t, 2H), 3.52 (bs, 9H), 3.03-3.19 (m, 12H), 2.54 (s, 3H), 2.01-2.03 (m, 2H), 1.88-1.95 (m, 2H), 1.72-1.77(m, 2H), 1.42-1.47(m, 4H), 1.27-1.31(m, 2H), 0.66(t, 2H). Example 3

[0076]

[0077] Step (a): Preparation of the compound of formula 3-3

[0078] Keeping nitrogen slightly positive pressure, add 2L ethylene glycol diethyl ether, 135.95 g (0.7 mol) of the compound of formula 1-3 2-methyl-6-nitrobenzothiazole, and 895.73 g (2.1 mol) of the compound of formula 2-3 1,6-di-p-toluenesulfonyloxyhexane to the 5L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 120℃ (60-200℃) for reaction. Keep the temperature for 16 hours, and the reaction is complete.

[0079] The reaction solution was cooled to room temperature, 2000 mL of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 300.69 g (0.484 mol) of a green solid product.

[0080] Yield: 69.2%. Product purity: 98.24% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ9.45 (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)

[0081] Step (b): Preparation of the compound of formula 5-3

[0082] Keeping nitrogen slightly positive pressure, add 6L o-xylene, 465.18g (3.0 mol) of compound 4-3 and 1573.74g (6.0 mol) of triphenylphosphine to the 20L reaction bottle in sequence, stir evenly after adding, heat the reaction solution to 140℃ and react. Keep the temperature for 15 hours, and the reaction is complete.

[0083] The reaction solution was naturally cooled to room temperature, and then continued to cool to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid was precipitated, and the filter cake was collected by filtration to obtain 1110.57 g (2.661 mol) of a green solid product.

[0084] Yield: 88.7%, product purity: 99.36% (HPLC); NMR data:

[0085] 1H NMR (400MHz, DMSO-d6): δ 7.73-7.83(m, 15H), 3.75(t, 2H), 3.70(t, 2H), 2.24-2.27(m, 2H), 2.01-2.05(m, 2H), 1.75-1.79(m, 2H), 1.27-1.30(m, 2H).

[0086] Step (c): Preparation of the compound of formula 7-3

[0087] Keeping nitrogen slightly positive pressure, add 5L DMF, 1110.57 g (2.661 mol) of compound 5-3, and 490.8 g (3.0 mol) of compound 6-3, 4-chloroquinoline, to the 20L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 150℃ for reaction. Keep the temperature for 5 hours, and the reaction is complete.

[0088] The reaction solution was cooled to room temperature, 5000 mL of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 1074.42 g (1.849 mol) of a yellow solid product.

[0089] Yield: 69.5%. Product purity: 99.27% ​​(HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ8.49-8.74 (m, 2H), 8.31-8.41 (m, 2H), δ 8.06-8.21 (m, 2H), 7.74-7.85 (m, 15H), 5.29-5.36 (m, 2H), 3.80 (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).

[0090] Step (d): Preparation of the compound of formula 8-3

[0091] Keeping nitrogen slightly positive pressure, add 1.2 L of ethylene glycol diethyl ether, 300.69 g (0.484 mol) of compound 3-3 and 462.71 g (1.452 mol) of compound 7-3 to the 5 L reaction bottle in turn and stir well. Then add 14.69 g (0.145 mol) of N,N-diisopropylethylamine. After adding, stir well and heat the reaction solution to 60 °C for reaction. Keep the temperature for 1 hour and the reaction is complete.

[0092] The reaction solution was cooled to room temperature, 2000 mL of ethyl acetate and 2000 mL of petroleum ether were added thereto, and the solution was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 495.53 g (0.439 mol) of an orange solid product.

[0093] Yield: 90.7%. Product purity: 99.36% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ9.45 (s, 1H), 8.68 (d, 1H), 8.51 (d, 1H), 7.68-7.83 (m, 21H), 7.47 (d, 4H), 7.34 (d, 4H), 7.31 (d, 1H), 7.15 (s, 1H), 7.10 (d, 4H), 4.80-4.93 (m, 2H), 4.02(t, 2H), 3.78(t, 2H), 3.25-3.38(m, 2H), 2.45(s, 3H), 2.28(s, 3H), 2.01-2.04( m, 4H), 1.87-1.92 (m, 2H), 1.62-1.66 (m, 2H), 1.40-1.42 (m, 2H), 1.22-1.30 (m, 6H).

[0094] Step (e): Preparation of the compound of formula I-3

[0095] Maintaining a slight positive pressure of nitrogen, add 1.8 L of ethylene glycol diethyl ether, 495.53 g (0.439 mol) of the compound of formula 8-3 and 273.07 g (1.317 mol) of the compound of formula 9-3 to the 5 L reaction bottle in sequence, stir evenly, and heat the reaction solution to 120 °C for reaction. Keep the temperature for 20 hours, and the reaction is complete.

[0096] The reaction solution was naturally cooled to room temperature, and then continued to be cooled to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid was precipitated, which was filtered and the filter cake was collected to obtain 529.07 g (0.396 mol) of an orange solid product.

[0097] Yield: 90.2%, total yield of 5-step reaction: 34.90%, product purity: 99.36% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 9.46(s, 1H), 8.69(d, 1H), 8.50(d, 1H), 7.66-7.82(m, 17H), 7.48(d, 8H), 7.31(d, 1H), 7.15(s, 1H), 7.10(d, 8H), 4. 80-4.93(m, 2H), 3.78(t, 2H), 3.11(bs, 10H), 3.25-3.38(m, 2H), 2.28(s, 6H), 2.01-2.04(m, 4H), 1.87-1.92(m, 2H), 1.72-1.77 (m, 2H), 1.62-1.66 (m, 2H), 1.40-1.42 (m, 2H), 1.22-1.30 (m, 6H), 0.65 (t, 2H). Example 4

[0098]

[0099] Step (a): Preparation of the compound of formula 3-4

[0100] Maintaining a slight positive pressure of nitrogen, add 2LDMF, 104.45 g (0.7 mol) of the compound 2-methylbenzothiazole of formula 1-4, and 316.34 g (4.0 mol) of the compound 1,3-dichloropropane of formula 2-4 to the 5 L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 150 °C for reaction. Keep the temperature for 5 hours, and the reaction is complete.

[0101] The reaction solution was cooled to room temperature, 2000 mL of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 126.27 (0.482 mol) of a yellow solid product.

[0102] Yield: 68.8%.

[0103] Product purity: 99.68% (HPLC); NMR data: 1H NMR (400MHz, 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)

[0104] Step (b): Preparation of the compound of formula 5-4

[0105] Keeping nitrogen slightly positive pressure, add 6L ethylene glycol diethyl ether, 361.54g (3.2 mol) 4-4 compound 1,3-dichloropropane and 2098.32g (8.0 mol) triphenylphosphine to the 20L reaction bottle in sequence, stir evenly after adding, heat the reaction solution to 120℃ and react. Keep the temperature for 15 hours, and the reaction is complete.

[0106] The reaction solution was naturally cooled to room temperature, and then continued to be cooled to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid was precipitated, which was filtered and the filter cake was collected to obtain 1061.56 g (2.829 mol) of a white solid product.

[0107] Yield: 88.4%, product purity: 98.35% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ7.73-7.83 (m, 15H), 3.75 (t, 2H), 3.71 (t, 2H), 2.24-2.36 (m, 2H).

[0108] Step (c): Preparation of the compound of formula 7-4

[0109] Keeping nitrogen slightly positive pressure, add 6L tetrahydrofuran, 1061.56g (2.829mol) of compound 5-4, and 1851.17g (11.32mol) of compound 6-4 4-chloroquinoline to the 20L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 66℃ for reaction. Keep the temperature for 72 hours, and the reaction is complete.

[0110] The reaction solution was cooled to room temperature, 5000 mL of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 1068.67 g (1.983 mol) of a yellow solid product.

[0111] Yield: 70.1%.

[0112] Product purity: 98.17% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.48-8.73 (m, 2H), 8.31-8.41 (m, 2H), 8.06-8.21 (m, 2H), 7.74-7.85 (m, 15H), 5.29-5.38 (m, 2H), 3.80 (t, 2H), 2.50–2.57 (m, 2H).

[0113] Step (d): Preparation of the compound of formula 8-4

[0114] Keeping nitrogen slightly positive pressure, add 2.5L DMF, 126.27 (0.482mol) of compound 3-4 and 1038.10g (1.926mol) of compound 7-4 to the 20L reaction bottle in turn and stir well. Then add 19.49g (0.193mol) of triethylamine. After adding, stir well and heat the reaction solution to 60℃ for reaction. Keep the temperature for 1 hour and the reaction is complete.

[0115] The reaction solution was cooled to room temperature, 5000 mL of ethyl acetate and 5000 mL of petroleum ether were added thereto, cooled to 0°C, and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 316.66 (0.435 mol) of a red solid product.

[0116] Yield: 90.3%.

[0117] Product purity: 98.76% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.49 (d, 1H), 8.36 (d, 1H), 8.25-8.30 (m, 3H), 7.75-7.95 (m, 20H), 6.89 (s, 1H), 4.77-4.89 (m, 2H), 3.85 (t, 2H), 3.79 (t, 2H), 3.06-3.22 (m, 2H), 2.42-2.50 (m, 2H), 2.01-2.04 (m, 2H).

[0118] Step (e): Preparation of the compound of formula I-4

[0119] Keeping nitrogen slightly positive pressure, add 2.0L ethylene glycol diethyl ether, 316.66 (0.435mol) of compound 8-4 and +360.69g (1.740mol) of compound 9-4 to the 5L reaction bottle in sequence, stir evenly after adding, heat the reaction liquid to 120℃ and react. Keep the temperature for 20 hours, and the reaction is complete.

[0120] The reaction solution was naturally cooled to room temperature, and then continued to be cooled to 0°C, and kept warm for 3 hours for crystallization, during which a large amount of solid was precipitated. The solid was filtered and the filter cake was collected to obtain 364.52 g (0.390 mol) of an orange solid product.

[0121] Yield 89.6%, total yield of 5 steps reaction 34.49%, product purity: 99.36% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.52 (d, 1H), 8.37 (d, 1H), 8.25-8.31 (m, 3H), 7.74-7.93 (m, 20H), 6.88 (s, 1H), 4.79-4.89 (m, 2H), 3.79 (t, 2H), 3.52 (bs, 9H), 3.05-3.21 (m, 12H), 2.23-2.32 (m, 2H), 2.01-2.05 (m, 2H), 1.72-1.77 (m, 2H), 0.65 (t, 2H). Example 5

[0122]

[0123] Step (a): Preparation of the compound of formula 3-5

[0124] Maintaining a slight positive pressure of nitrogen, add 2L DMF, 104.45 g (0.7 mol) of the compound 2-methylbenzothiazole of formula 1-5, and 837.27 g (3.5 mol) of the compound 1,12-dichlorododecane of formula 2-5 to the 5L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 150°C for reaction. Keep the temperature for 5 hours, and the reaction is complete.

[0125] The reaction solution was cooled to room temperature, 2000 mL of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 192.51 g (0.496 mol) of a yellow solid product.

[0126] Yield: 70.8%.

[0127] Product purity: 99.28% (HPLC); NMR data: 1H NMR (400MHz, 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).

[0128] Step (b): Preparation of the compound of formula 5-5

[0129] Keeping nitrogen slightly positive pressure, add 8L p-xylene, 1800.76g (4.0mol) of compound 1,14-diiodotetradecane of formula 4-5 and 3147.48g (12.0mol) of triphenylphosphine to the 20L reaction bottle in sequence, stir evenly after adding, heat the reaction liquid to 138℃ and react. Keep the temperature for 12 hours, and the reaction is complete.

[0130] The reaction solution was naturally cooled to room temperature, and then continued to cool to 0°C, and kept warm for 3 hours for crystallization. A large amount of solid was precipitated, and the filter cake was collected to obtain 2504.02 g (3.516 mol) of white solid product of formula 5-1.

[0131] Yield: 87.9%, product purity: 99.05% (HPLC); 1H NMR (400MHz, DMSO-d6): δ 7.73-7.83 (m, 15H), 3.72 (t, 2H), 2.95 (t, 2H), 2.05-2.13 (m, 2H), 1.82-1.87 (m, 2H), 1.23-1.31 (m, 20H).

[0132] Step (c): Preparation of the compound of formula 7-5

[0133] Keeping nitrogen slightly positive pressure, add 8L acetonitrile, 2504.02g (3.516mol) of compound 5-5, and 2871.18g (17.55mol) of compound 6-5, 2-methyl 4-chloroquinoline, to the 20L reaction bottle in sequence. After adding, stir evenly, and heat the reaction solution to 82℃ for reaction. Keep the temperature for 19 hours, and the reaction is complete.

[0134] The reaction solution was cooled to room temperature, 5000 ml of petroleum ether was added thereto, and the mixture was cooled to 0°C and kept warm overnight. A large amount of solid precipitated, which was filtered and the filter cake was collected to obtain 2205.77 g (2.478 mol) of a yellow solid product.

[0135] Yield: 70.6%.

[0136] Product purity: 98.55% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.57 (d, 1H), 8.47 (d, 1H), 8.22 (t, 1H), 8.01 (t, 1H), 7.74-7.85 (m, 15H), 7.55 (s, 1H), 5.18-5.25 (m, 2H), 3.80 (t, 2H), 2.67 (s, 3H), 2.00-2.03 (m, 2H), 1.82-1.88 (m, 2H), 1.23-1.31 (m, 20H).

[0137] Step (d): Preparation of the compound of formula 8-5

[0138] Keeping nitrogen slightly positive pressure, add 2.0L ethanol, 192.51g (0.496 mol) of compound 3-5 and 2205.77g (2.478 mol) of compound 7-5 to the 5L reaction bottle in turn and stir evenly. Then add 25.07g (0.247 mol) of triethylamine. After adding, stir evenly and heat the reaction solution to 40℃ for reaction. Keep the temperature for 3 hours and the reaction is complete.

[0139] The reaction solution was cooled to room temperature, 2000 mL of ethyl acetate and 2000 mL of petroleum ether were added thereto, cooled to 0°C, and kept warm overnight to precipitate a large amount of solid. The solid was filtered and the filter cake was collected to obtain 489.79 g (0.439 mol) of a red solid product.

[0140] Yield: 88.7%.

[0141] Product purity: 99.38% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.51 (d, 1H), 8.39 (d, 1H), 8.25-8.30 (m, 3H), 7.90-7.93 (m, 2H), 7.73-7.83 (m, 16H), 7.27 (s, 1H), 6.91 (s, 1H), 4.81-4.89 (m, 2H), 3.85 (t, 2H), 3.76 (t, 2H), 3.05-3.21 (m, 2H), 2.54 (s, 3H), 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).

[0142] Step (e): Preparation of the compound of formula I-5

[0143] Keeping nitrogen slightly positive pressure, add 2.0L o-xylene, 489.79g (0.439mol) of compound 8-5 and 889.39 (0.421mol) of compound 9-5 to the 5L reaction bottle in sequence, stir evenly after adding, heat the reaction solution to 140℃ and react. Keep the temperature for 22 hours, and the reaction is complete.

[0144] The reaction solution was naturally cooled to room temperature, and then continued to be cooled to 0°C. The solution was kept warm for 3 hours for crystallization, and a large amount of solid was precipitated. The solid was filtered and the filter cake was collected to obtain 521.68 g (0.395 mol) of a red solid product.

[0145] Yield: 89.8%, total yield of 5-step reaction: 35.00%, product purity: 99.16% (HPLC); NMR data: 1H NMR (400MHz, DMSO-d6): δ 8.52 (d, 1H), 8.38 (d, 1H), 8.25-8.30 (m, 3H), 7.91-7.95 (m, 2H), 7.74-7.83 (m, 16H), 7.28 (s, 1H), 6.92 (s, 1H), 4.82-4.89 (m, 2H), 3.77 (t, 2H), 3.54 (bs, 9H), 3.03-3.21 (m, 12H), 2.55 (s, 3H), 2.02-2.05 (m, 4H), 1.82-1.87 (m, 2H), 1.72-1.77 (m, 2H), 1.46-1.51 (m, 2H), 1.23-1.29 (m, 36H), 0.64 (t, 2H).

[0146] Compound antibacterial performance test:

[0147] Determination of MIC (minimum inhibitory concentration): The compounds prepared in Examples 1-5 (8-1, 8-2, 8-3, 8-4, 8-5, I-1, I-2, I-3, I-4, I-5) were mixed in LB nutrient broth by the microbroth dilution method and serially diluted by two times. A certain amount of test bacteria was added and cultured for a certain period of time. The lowest compound concentration at which no bacterial growth was observed was the MIC (minimum inhibitory concentration) of the compound against this bacterium.

[0148] The specific measurement steps are as follows:

[0149] (1) Preparation of bacterial suspension: On a sterile operating table, use a sterile inoculation loop to pick up an appropriate amount of bacterial culture, transfer it to 10 mL of LB broth culture medium, and culture it in a shaker at 37 °C for 6-8 h until the bacterial solution reaches slight or moderate turbidity. In order to ensure the accuracy and precision of the drug sensitivity test, the concentration of the inoculated bacterial solution must be controlled accordingly. Therefore, a small amount of bacterial solution is transferred to a colorimetric tube, diluted to 0.5 McFarland standard concentration, and then diluted 1000 times. The bacterial solution content is about 1×10 5 cfu / mL.

[0150] (2) Preparation of antimicrobial compound stock solution: The compound is dissolved in sterile water to prepare an antimicrobial compound stock solution of a specific concentration, and a sterile filter is used to remove bacteria that may be contained in the solution.

[0151] (3) Preparation of MIC plate: Add 100 μL LB broth to each well of the 2nd to 10th columns of the 96-well plate, and add 100 μL of the stock solution of the antimicrobial compound to the 2nd column. Mix it by pipetting and then transfer 100 μL to the 3rd column. Repeat this process for a total of 8 concentration gradients. Discard 100 μL of the mixture in the 9th column. Add no drug solution to the 10th column as a positive control. Then add 100 μL of bacterial suspension to each well and pipette the mixture evenly. Add 200 μL LB broth to the 11th column without bacterial solution as a negative control. After the compound and bacterial solution are mixed by pipetting, cover the 96-well plate with a lid and culture in a 37°C biochemical incubator for 20-24 h (Escherichia coli ATCC 25922, Staphylococcus aureus ATCC 6538) or in a 28°C biochemical incubator for 40-48 h (Candida albicans ATCC 10231, Aspergillus niger ATCC 16404), and measure the OD570 value (optical density) of the bacterial solution with an enzyme-labeled instrument.

[0152] (4) Determination results: MIC (minimum inhibitory concentration) is the concentration that completely inhibits bacterial growth in a 96-well plate. The specific results are shown in Table 1.

[0153] Table 1 Minimum inhibitory concentration (MIC) of the intermediate compounds and final product compounds of Examples 1-5 against some microorganisms

[0154]

[0155] It can be seen from the above experimental results that the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compounds (Compound I-1, Compound I-2, Compound I-3, Compound I-4, Compound I-5) have excellent antibacterial effects on common bacteria (Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, Candida albicans ATCC 10231, Aspergillus niger ATCC 16404), and the minimum inhibitory concentration is all below 60 mg / L; especially when m in the molecular formula of the compound 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 antibacterial effect is particularly excellent, and the minimum inhibitory concentration is all below 3 mg / L, and the best effect is even as low as 0.3 mg / L.

[0156] At the same time, the intermediate compounds (compound 8-1, compound 8-2, compound 8-3, compound 8-4, compound 8-5) for preparing thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compounds also showed good antibacterial effects, and the minimum inhibitory concentrations for common bacteria were all below 900 mg / L, but in general, they were much worse than the corresponding thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compounds. The combination of organosiloxane, quaternary ammonium salt group, thiazole ring, quinoline ring, and quaternary phosphonium salt group has achieved unexpected technical effects, which has increased the antibacterial effect by more than 3 times. According to the general understanding in the industry, the antibacterial activity of a single quaternary phosphonium salt group is higher than that of a quaternary ammonium salt group. If a quaternary ammonium salt group with weaker antibacterial activity and an organosilicon group with obviously no antibacterial activity are added to a quaternary phosphonium salt group, its overall antibacterial activity should only be less than 1 times higher than the antibacterial activity of a quaternary phosphonium salt group, but the present invention found that its overall antibacterial activity was increased by more than 3 times, which is very unexpected. The reason for this unexpected technical effect is not yet clear, and the synergistic antibacterial principle of organosiloxane, quaternary ammonium salt group, thiazole ring, quinoline ring, and quaternary phosphonium salt group is still under further study.

[0157] Performance test of compounds on antibacterial finishing of fabrics:

[0158] According to the mass ratio, 1 part of the compounds (8-1, 8-2, 8-3, 8-4, 8-5, I-1, I-2, I-3, I-4, I-5) prepared in Examples 1-5 were respectively mixed with 99 parts of water to prepare antibacterial composition Examples 6-15. At the same time, 1 part of DC5700 was mixed with 99 parts of water to prepare comparative antibacterial composition Example 16.

[0159] Antibacterial composition examples 6-11, bath ratio 1:15, the pure cotton fabric is placed in the antibacterial finishing agent solution and soaked for 10 minutes, then passed through a pressing roller with a rolling rate of 80%, and then the fabric is placed in a drying room at 150°C for 5 minutes, and the fabric is taken out of the drying room to obtain the corresponding antibacterial fabrics.

[0160] Antibacterial fabric antibacterial test: Refer to GB / 120944.3-2008 "Evaluation of antibacterial properties of textiles Part 3: Oscillation method", the bacterial species selected are Staphylococcus aureus (ATCC 6538), Escherichia coli (ATCC 25922), Candida albicans (ATCC 10231), Aspergillus niger (ATCC 16404), and the specific results are shown in Table 2.

[0161] Table 2 Antibacterial rate of antibacterial fabrics prepared from antibacterial composition examples 8-22

[0162]

[0163]

[0164] It can be seen from the above experimental results that the antibacterial fabric obtained by antibacterial finishing of cotton fabric with the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound of the present invention has very excellent antibacterial properties, and has a very good antibacterial effect on common bacteria (Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, Candida albicans ATCC 10231, Aspergillus niger ATCC 16404), and the antibacterial rate is 99.9%. In addition, these antibacterial fabrics have good washability and can withstand washing. The antibacterial rate after 50 washings is still maintained at more than 90%. More excellent is that 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 washability is particularly good, and the antibacterial rate after 100 washings is more than 80%, and the antibacterial rate after 200 washings is still more than 70%.

[0165] At the same time, the antibacterial fabrics prepared by antibacterial finishing of cotton fabrics using the intermediate compounds (8-1, 8-2, 8-3, 8-4, 8-5) of the present invention also have very excellent antibacterial properties, and have very good antibacterial effects on common bacteria (Staphylococcus aureus ATCC 6538, Escherichia coli ATCC 25922, Candida albicans ATCC 10231, Aspergillus niger ATCC 16404), with an antibacterial rate of 99.9%. However, the washability of these antibacterial fabrics is relatively poor, and the antibacterial rates have dropped to less than 50% after 100 washes, and to 0% after 200 washes.

[0166] As a control, the antibacterial fabric prepared by antibacterial finishing of cotton fabric with antibacterial agent DC5700 containing both organosilicon group and quaternary ammonium salt group in comparative antibacterial composition 16 also has good antibacterial performance. However, the washing resistance of the antibacterial fabric is slightly worse than that of the antibacterial fabric prepared by the intermediate compound of the present invention, and the antibacterial rate after 50 washings has dropped below 75%.

[0167] It can be seen that the synergistic combination of organosiloxane, quaternary ammonium salt group, thiazole ring, quinoline ring, and quaternary phosphonium salt group significantly improves the overall washability of the antibacterial material.

[0168] Under the guidance of this specification and without departing from the scope of protection of the claims of the present invention, ordinary technicians in this field can also make many forms, which are all protected by the present invention.

Claims

1. A thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound, characterized in that: The compound structure is shown in Formula I, In the formula, X1 and X2 are selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R1, R2, R3 and R4 are respectively selected from methyl, ethyl, C3-C8 alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-fluorophenyl, 4-iodophenyl, 4-trifluoromethoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, m 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.

2. A method for preparing the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound according to claim 1, characterized in that: The steps include: (a) adding a first reaction solvent, a compound of formula 1, and a compound of formula 2 to a reaction kettle under air-tight conditions, reacting at a temperature of 60-200° C. for 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) adding a second reaction solvent to the reaction kettle in an airtight state, reacting the compound of formula 4 with triphenylphosphine at a reaction temperature of 80-200° C. for a reaction time of 12-102 hours to obtain a compound of formula 5; (c) adding a third reaction solvent to the reaction kettle under air-tight conditions, and then adding the compound of formula 5 and the compound of formula 6, the reaction temperature is 60-200° C., the reaction time is 3-72 hours, to obtain a compound of formula 7, wherein the molar ratio of the compound of formula 3 to the compound of formula 4 is 1:1-10; (d) adding a fourth reaction solvent, a compound of formula 3 and a compound of formula 7 to a reaction kettle under air conditions, reacting at a reaction temperature of 25-60° C., and keeping the temperature for 1-5 hours to obtain a compound of formula 8, wherein the molar ratio of the compound of formula 3 to the compound of formula 7 is 1:1-10; (e) adding a fifth reaction solvent, a compound of formula 8 and a compound of formula 9 to a reaction kettle under air-tight conditions, reacting at a reaction temperature of 80-200° C., and keeping the temperature for reaction for 12-102 hours to obtain a compound of formula I, wherein the molar ratio of the compound of formula 8 to the compound of formula 9 is 1:1-10, and the fifth reaction solvent is at least one of o-xylene, p-xylene, m-xylene, toluene, ethylene glycol diethyl ether, DMF, DMSO, acetonitrile or acetone; In the formula, X1 and X2 are selected from chlorine, bromine, iodine, p-toluenesulfonyloxy, benzenesulfonyloxy, methanesulfonyloxy, R1, R2, R3 and R4 are respectively selected from methyl, ethyl, C3-C8 alkyl, phenyl, 4-chlorophenyl, 4-bromophenyl, 4-fluorophenyl, 4-iodophenyl, 4-trifluoromethoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-methylphenyl, 4-trifluoromethylphenyl, 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.

3. The method for preparing the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound according to claim 2, characterized in that: 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.

4. The method for preparing the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound according to claim 2, characterized in that: In step (b), the second reaction solvent is at least one of o-xylene, p-xylene, o-xylene, m-xylene, toluene, ethylene glycol diethyl ether, DMF, DMSO, acetonitrile and acetone.

5. The method for preparing the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound according to claim 2, characterized in that: In step (c), the third 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.

6. The method for preparing the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound according to claim 2, characterized in that: In step (d), the fourth 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.

7. The method for preparing the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound according to claim 2, characterized in that: In step (d), it is also necessary to continue adding an alkaline reagent, wherein the alkaline reagent is at least one of triethylamine and N,N-diisopropylethylamine.

8. Use of the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound prepared according to claim 1 and the preparation method of the thiazole orange organosilicon quaternary ammonium quaternary phosphonium salt compound prepared by any one of claims 2 to 7 in antibacterial materials.

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