Acid red functional fiber as well as preparation method, use method and application thereof

Abstract

The invention belongs to the technical field of catalysts, and particularly relates to an acid red functional fiber as well as a preparation method, a use method and application thereof. The acid red functional fiber is prepared from a quaternary amine fiber and an acid red 94 dye, and acid red 94 nanoparticles in the acid red functional fiber are uniform in particle size and good in dispersion degree on the surface of the fiber. The acid red functional fiber can be used as a catalyst to efficiently catalyze an Aza-Henry reaction, has the advantages of high catalytic efficiency, good catalytic effect and high yield, can be repeatedly used after being simply filtered and cleaned, the catalytic activity is not obviously reduced after the acid red functional fiber is repeatedly used, and the catalyst is suitable for industrial fluidization production.

Description

Technical Field

[0001] The present invention belongs to the technical field of catalysts, and in particular relates to an acid red functionalized fiber and a preparation method, a use method and an application thereof. Background Art

[0002] The Aza-Henry reaction (also known as the Aza-Henry reaction or the Nitro-Mannich reaction) has important applications in the synthesis of drugs and drug intermediates, particularly in the construction of nitrogen-containing chiral centers. It has provided new insights into the synthesis of numerous drugs, including omaglitin (for type 2 diabetes), riluzole (for the treatment of amyotrophic lateral sclerosis), ubenimex (for adjuvant cancer therapy), and aminopeptidase inhibitors (antiviral and antibacterial drugs).

[0003] According to literature, organometallic catalysts and recently discovered dye catalysts are commonly used to catalyze the Aza-Henry reaction, such as copper, cobalt, gold, eosin Y, and Acid Red 94. Metal catalysts are complex to synthesize, require harsh reaction conditions, and suffer from poor catalyst recovery. Therefore, dye-supported catalysts that can be synthesized under mild conditions, achieve higher yields, and achieve efficient utilization have attracted widespread research interest.

[0004] Acid red dye is difficult to recycle due to its high dispersion in the system. Its large molecular structure also makes it difficult to degrade. If used in large quantities and discharged without restraint, it will inevitably lead to a series of environmental problems. Based on the twelve principles of green chemistry and the concept of green chemistry, the preparation of a new heterogeneous acid red catalyst is of great significance from an environmentally friendly perspective.

[0005] In recent years, various carrier-supported dye catalysts have been developed, but most suffer from poor yields and recycling effects, and require stringent conditions. Therefore, existing acid red catalysts suffer from shortcomings such as poor recycling performance and catalytic effect, low yields, and high catalytic temperatures.

[0006] The tetrahydroisoquinoline (THIQ) skeleton is an important nitrogen-containing heterocyclic structure in medicinal chemistry, present in a wide range of biologically active natural products and synthetic drugs. 1-(Nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline and its derivatives, as structural modifiers of THIQ, show broad application prospects in drug design and development due to their unique electronic properties and spatial configuration.

[0007] The tetrahydroisoquinoline skeleton is widely distributed in nature and forms the core structure of numerous alkaloids. According to statistics, over 300 natural isoquinoline alkaloids have been identified, many of which have significant pharmacological activity. In the field of synthetic pharmaceuticals, THIQ derivatives form the core skeleton of numerous clinically important drugs, including the antihypertensive drug Quinapril, the antitussive drug Noscapine, the anti-Parkinson's disease drug Apomorphine, the skeletal muscle relaxant Atracurium, and the anti-tumor drug Trabectedin.

[0008] There are two main technologies for preparing 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline (oxidized furazan compounds): (1) 2-phenyl-1,2,3,4-tetrahydroisoquinoline and nitromethane are reacted at 60°C for 16 h in the presence of cuprous bromide and methanol as solvent to obtain 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline. The catalytic reaction process is shown in the following formula:

[0009] (2) 2-phenyl-1,2,3,4-tetrahydroisoquinoline and nitromethane react under the catalysis of TFB-COF and CFL light as the light source at 25°C for 36 h to obtain 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline. The catalytic reaction process is shown in the following formula:

[0010] However, the existing methods for synthesizing furazan oxide have the following disadvantages: (1) using organic reagents as reaction solvents; (2) high reaction temperatures; (3) high catalyst loading requirements; and (4) long reaction times and low yields.

[0011] Therefore, providing a catalyst with mild reaction conditions, small usage amount, high catalytic efficiency and high yield becomes a problem that needs to be solved. Summary of the Invention

[0012] Based on the above technical background, the main purpose of the present invention is to provide an acid red functionalized fiber and its preparation method, use method and application, so as to overcome the shortcomings of the existing technology.

[0013] To achieve the aforementioned object of the invention, the technical solutions adopted by the present invention include: The first aspect of the present invention is to provide an acid red functionalized fiber, wherein the acid red functionalized fiber is prepared from quaternary ammonium fiber and acid red 94 dye, and the mass ratio of the quaternary ammonium fiber to acid red 94 dye is (0.8-1.3):1.

[0014] Preferably, the mass ratio of the quaternary ammonium fiber to the acid red 94 dye is 1:1.

[0015] The quaternary amine fiber is prepared from tertiary amine functionalized fiber and halogenated hydrocarbon in a mass ratio of 0.5:(2-5).

[0016] Preferably, the quaternary ammonium fiber is made from tertiary amine functionalized fiber and halogenated hydrocarbon in a mass ratio of 0.5:(2.5-4.4).

[0017] The halogenated hydrocarbon is one or more selected from methyl iodide, ethyl bromide, n-propyl bromide, n-butyl bromide, n-pentane bromide, n-hexane bromide, n-heptane bromide, n-octane bromide, dodecane bromide and benzyl bromide.

[0018] Preferably, the halogenated hydrocarbon is methyl iodide, n-butyl bromide, n-hexane bromide, n-octane bromide, dodecane bromide or benzyl bromide.

[0019] The tertiary amine functionalized fiber is prepared from acrylic fiber and organic amine in a mass ratio of 1: (30-40).

[0020] Preferably, the tertiary amine functionalized fiber is made from acrylic fiber and organic amine in a mass ratio of 1:36.

[0021] The organic amine is selected from one or more of N,N'-dimethyl-1,3-propylene diamine, N,N'-dimethylethylenediamine, ethylenediamine, propylene diamine, N,N-dimethyl-1,3-butylene diamine, butylene diamine, N,N-dimethyl-1,3-pentane diamine, pentane diamine and 3-dimethylaminopropylamine.

[0022] Preferably, the organic amine is 3-dimethylaminopropylamine.

[0023] The experiments showed that the acid red catalyst loaded with quaternary ammonium salt had better catalytic effect and efficiency.

[0024] The second aspect of the present invention is to provide a method for preparing the acid red functionalized fiber according to the first aspect of the present invention, the preparation method comprising the following steps: Figure 1 As shown: The quaternary amine functionalized fiber and acid red 94 dye are added into water, reacted under stirring, and then washed and dried to obtain the acid red functionalized fiber.

[0025] Preferably, the reaction conditions are: stirring the reaction at room temperature for 10 to 15 hours.

[0026] More preferably, the reaction conditions are: stirring the reaction at room temperature for 12 hours.

[0027] Preferably, the amount of water added is 900 to 1100 times the mass of the quaternary amine functionalized fiber.

[0028] More preferably, the amount of water added is 1000 times the mass of the quaternary amine functionalized fiber.

[0029] According to a preferred embodiment of the present invention, the method for preparing the quaternary amine functionalized fiber comprises the following steps: The tertiary amine functionalized fiber and halogenated hydrocarbon are added into ethanol for reflux reaction. After the reaction is completed, the fiber is washed and dried to obtain the quaternary amine functionalized fiber.

[0030] Preferably, the reflux reaction is carried out at 100-120° C. for 5 to 7 hours.

[0031] More preferably, the reflux reaction is carried out at 120° C. for 6 h.

[0032] Preferably, washing is performed with ethanol at 50-65° C., and then drying is performed at 50-65° C. for 10-15 hours.

[0033] More preferably, washing is performed with ethanol at 60° C., and then drying is performed at 60° C. for 12 h.

[0034] According to a preferred embodiment of the present invention, the method for preparing the tertiary amine functionalized fiber comprises the following steps: Acrylic fiber and organic amine are added into water for reflux reaction, and then washed and dried to obtain tertiary amine functionalized fiber.

[0035] Preferably, the reflux reaction is carried out at 100-120° C. for 4 to 7 h.

[0036] More preferably, the reflux reaction is carried out at 120° C. for 5 h.

[0037] Preferably, washing is performed with water at 50-70° C. until the filtrate is neutral, and then drying is performed at 50-70° C. for 10-15 hours.

[0038] More preferably, washing is performed with water at 60° C. until the filtrate is neutral, and then drying is performed at 60° C. for 12 h.

[0039] The amount of water added is 25 to 35 times the mass of the acrylic fiber. Preferably, the amount of water added is 30 times the mass of the acrylic fiber.

[0040] The third aspect of the present invention is to provide an application of the acid red functionalized fiber described in the first aspect of the present invention, wherein the acid red functionalized fiber can be used as a catalyst.

[0041] Preferably, the acid red functionalized fiber can be used as a catalyst to synthesize oxidized furazan compounds.

[0042] The fourth aspect of the present invention is to provide a method for using the acid red functionalized fiber described in the first aspect of the present invention as a catalyst, the method comprising the following steps: Tetrahydroisoquinoline, reaction auxiliary materials and acid red functionalized fiber are added into ethanol, and reacted at room temperature under light irradiation to obtain oxidized furazan compounds.

[0043] Preferably, the molar ratio of tetrahydroisoquinoline to reaction auxiliary materials is 1:9-11.

[0044] More preferably, the molar ratio of tetrahydroisoquinoline to the reaction auxiliary material is 1:10.

[0045] Preferably, the added amount of the acid red functionalized fiber is 1.5 to 2.5 mol%.

[0046] More preferably, the added amount of the acid red functionalized fiber is 2 mol%.

[0047] The acid red functionalized fiber of the present invention can achieve higher catalytic efficiency and excellent catalytic effect with a smaller addition amount.

[0048] Preferably, the tetrahydroisoquinoline is one of 2-phenyl-1,2,3,4-tetrahydroisoquinoline, 2-(4-methylphenyl)-1,2,3,4-tetrahydroisoquinoline, 2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinoline, 2-(4-bromophenyl)-1,2,3,4-tetrahydroisoquinoline, and 6,7-dimethoxy-2-phenyl-1,2,3,4-tetrahydroisoquinoline.

[0049] More preferably, the tetrahydroisoquinoline is 2-phenyl-1,2,3,4-tetrahydroisoquinoline.

[0050] Preferably, the reaction auxiliary material is nitromethane or ethyl cyanoacetate.

[0051] More preferably, the reaction auxiliary material is nitromethane.

[0052] Experiments have shown that the acid red functionalized fiber exhibits a better catalytic effect on the synthesis of oxidized furazan compounds using 2-phenyl-1,2,3,4-tetrahydroisoquinoline and nitromethane as reaction products.

[0053] Preferably, the light source is green light (λ=520±20 nm) or blue light.

[0054] More preferably, the light source is green light (λ=520±20 nm).

[0055] Experiments have shown that using green light as a light source has higher catalytic efficiency and better catalytic effect.

[0056] The reaction principle of 2-phenyl-1,2,3,4-tetrahydroisoquinoline and nitromethane catalyzed by acid red functionalized fiber is as follows: During the reaction, in the presence of oxygen, 2-phenyl-1,2,3,4-tetrahydroisoquinoline (Ⅰ) is excited by green light and catalyzed by acid red 94 (acid red functionalized fiber). Oxygen molecules are converted into activated state O2 under the catalysis of acid red 94. - At the same time, 2-phenyl-1,2,3,4-tetrahydroisoquinoline becomes activated state (Ⅱ), activated state O2 - Attack the benzyl position and take away a H to become HO2 - At the same time, the free radical activation electron on N forms a double bond with the benzyl activation electron (III). Nitromethane in HO2 - Under the attack, it takes away a molecule of H to become a nitro carbon anion, which attacks (III) to generate the product 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compound. Its synthetic route is as follows Figure 2 shown.

[0057] Preferably, the reaction time at room temperature is 10 to 15 hours, more preferably, the reaction time at room temperature is 12 hours.

[0058] The acid red-functionalized fiber can synthesize furazan oxide compounds in a relatively short period of time at room temperature, demonstrating its high efficiency under mild conditions. Experiments have also shown that the acid red-functionalized fiber can be reused 5 to 10 times after simple filtration, washing, and recycling. The results show that even after five reuses, the catalytic yield can still reach 87% or higher, demonstrating excellent reusability.

[0059] The present invention uses ethanol as a solvent for the reaction. Compared with traditional organic solvents, ethanol is a green solvent and more environmentally friendly. Organic reagents are not only limited in source, but also relatively expensive and toxic, which can have certain health effects on experimenters. In addition, the addition of organic solvents makes product post-processing more difficult. Relatively speaking, ethanol as a solvent is more in line with the requirements of green chemistry.

[0060] The method for using the acid red functionalized fiber is mainly to catalyze the reaction of 2-phenyl-1,2,3,4-tetrahydroisoquinoline with nitromethane in ethanol. The acid red functionalized fiber as a catalyst can generate 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline derivatives under reaction conditions of 25°C, and the pure product can be obtained through column chromatography. The reaction yield can reach 98%, greatly improving the conversion rate of the raw materials. At the same time, the acid red functionalized fiber can be recycled 5-10 times as a heterogeneous catalyst and is also suitable for flow catalysis. The flow catalysis yield is still as high as 98%. The acid red functionalized fiber catalyst improves experimental efficiency and is more suitable for industrial flow production.

[0061] The beneficial effects of the present invention are: (1) The Acid Red 94 nanoparticles in the Acid Red functionalized fiber of the present invention have a uniform particle size and are well dispersed on the fiber surface. The Acid Red functionalized fiber can be used as a catalyst, which can efficiently catalyze the Aza-Henry reaction and has the advantages of high catalytic efficiency, good catalytic effect, and high yield. Moreover, the catalyst can be reused as a catalyst multiple times after simple filtration, washing, and drying, and the catalytic activity after repeated use does not show a significant decrease. The Acid Red functionalized fiber of the present invention solves the problems of the existing Acid Red catalyst, such as poor recycling performance, poor catalytic effect, low yield, high catalytic temperature, and harsh catalytic conditions.

[0062] (2) The acid red functionalized fiber can be used as a catalyst to synthesize oxidized furazan compounds. The catalyst can enable the reaction to proceed at room temperature of 25°C. The reaction temperature is low and the reaction conditions are mild, which reduces the energy consumption during the reaction process. It meets the requirements of green chemistry and is also suitable for industrial production.

[0063] (3) The acid red functionalized fiber can be recycled 5-10 times as a heterogeneous catalyst. After 5 cycles, the HPLC (high performance liquid chromatography) yield only decreased from 98% to 87%. At the same time, the acid red functionalized fiber is also suitable for flow catalysis, and the flow catalysis yield is still as high as 98%. The acid red functionalized fiber catalyst improves experimental efficiency and is more suitable for industrial flow production. Column chromatography purification of the product is also relatively simple and convenient. If the system volume is large, it is possible to directly use the solvent crystallization method for purification, making the purification of the product more convenient and quick.

[0064] (4) The method for preparing the acid red functionalized fiber of the present invention comprises loading an organic amine onto the surface of acrylic fiber to prepare a tertiary amine fiber, then reacting a halogenated hydrocarbon with the tertiary amine fiber to prepare a quaternary amine fiber having different chain lengths and different functional groups. Finally, the acid functionalized fiber is prepared by stirring Acid Red 94 with the quaternary amine fiber in room temperature deionized water as a solvent through an ion exchange method.

[0065] The acid red 94 nanoparticles in the acid red functionalized fiber prepared by the present invention are well dispersed on the fiber surface and have uniform particle size. They can efficiently catalyze the Aza-Henry reaction under the conditions of ethanol as a solvent and room temperature. They can be used to catalyze the reaction of 2-phenyl-1,2,3,4-tetrahydroisoquinoline and nitromethane. They have the advantages of high catalytic efficiency and are recyclable. After being recycled five times, the catalytic activity does not show a significant decrease, and the HPLC yield only decreases from 98% to 87%. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1 The preparation method and general structural formula of acid red functionalized fiber are shown; Figure 2 A roadmap showing the synthesis of furazan compounds using the acid red functionalized fiber of the present invention as a catalyst; Figure 3 Shown is a scanning electron microscope image of the acid red functionalized fiber provided in an embodiment of the present invention; Figure 4 Shows a scanning electron microscope mapping image of the acid red functionalized fiber provided in an embodiment of the present invention; Figure 5 A graph showing the test results of the cyclic performance of the Aza-Henry reaction of 2-phenyl-1,2,3,4-tetrahydroisoquinoline and nitromethane catalyzed by the acid red functionalized fiber provided in an embodiment of the present invention; Figure 6 The hydrogen spectrum of the product obtained in Example 13 is shown; Figure 7 The carbon spectrum of the product obtained in Example 13 is shown. DETAILED DESCRIPTION

[0067] The present invention will be described in detail below, and the characteristics and advantages of the present invention will become clearer and more distinct with the following description.

[0068] Example The present invention is further described below by way of specific examples, which are intended to illustrate the present invention but not to limit the scope of the present invention. The raw materials used in the examples of the present invention were all purchased.

[0069] Example 1 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by 30 g of deionized water. After reflux at 120°C for 5 h, the filtrate was washed with warm water at 60°C until the filtrate was neutral, and then dried in an oven at 60°C for 12 h to obtain a light yellow tertiary amine-functionalized fiber.

[0070] 0.5 g of dried tertiary amine functionalized fiber and 2.5 g of iodomethane were added to a reaction flask, followed by 30 g of ethanol. After reflux reaction at 100°C for 6 h, the fiber was washed with 60°C ethanol and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fiber.

[0071] The above 0.5 g quaternary amine functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the fiber was washed and dried to obtain red acid red functionalized fiber.

[0072] Example 2 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by 30 g of deionized water. After reflux at 100°C for 5 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then dried in an oven at 60°C for 12 h to obtain a light yellow tertiary amine-functionalized fiber.

[0073] 0.5 g of dry tertiary amine functionalized fiber and 2.5 g of n-butane bromide were added to a reaction flask, followed by 30 g of ethanol. After reflux at 110°C for 6 h, the fiber was washed with 60°C ethanol and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fiber.

[0074] The above 0.5 g quaternary amine functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber. Example 3 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by 30 g of deionized water. After reflux at 120°C for 5 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then dried in an oven at 60°C for 12 h to obtain a light yellow tertiary amine-functionalized fiber.

[0075] 0.5 g of dry tertiary amine functionalized fiber and 2.9 g of bromohexane were added to a reaction flask, followed by 30 g of ethanol. After reflux at 110°C for 6 h, the fiber was washed with 60°C ethanol and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fiber.

[0076] The above 0.5 g quaternary amine functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber. Example 4 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by 30 g of deionized water. After reflux at 100°C for 5 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then dried in an oven at 60°C for 12 h to obtain a light yellow tertiary amine-functionalized fiber.

[0077] 0.5 g of dry tertiary amine functionalized fiber and 3.4 g of octane bromide were added to a reaction flask, followed by 30 g of ethanol. After reflux reaction at 100°C for 6 h, the fiber was washed with 60°C ethanol and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fiber.

[0078] The above 0.5 g quaternary amine functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber.

[0079] Example 5 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by 30 g of deionized water. After reflux at 120°C for 5 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then dried in an oven at 60°C for 12 h to obtain a light yellow tertiary amine-functionalized fiber.

[0080] 0.5 g of dry tertiary amine functionalized fiber and 4.4 g of bromododecane were added to a reaction flask, followed by 30 g of ethanol. After reflux at 120°C for 6 h, the fiber was washed with 60°C ethanol and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fiber.

[0081] The above 0.5 g quaternary amine functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber.

[0082] Example 6 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by 30 g of deionized water. After reflux at 110°C for 5 h, the mixture was washed with warm water at 60°C until the filtrate became neutral. The filtrate was then dried in an oven at 60°C for 12 h to obtain a light yellow tertiary amine-functionalized fiber.

[0083] 0.5 g of dried tertiary amine functionalized fiber and 3 g of benzyl bromide were added to a reaction flask, followed by 30 g of ethanol. After reflux reaction at 110°C for 6 h, the fiber was washed with 60°C ethanol and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fiber.

[0084] The above 0.5 g quaternary amine functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber.

[0085] Example 7 Acid red functionalized fiber was prepared in a manner similar to Example 1, except that 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by the addition of 30 g of deionized water. After reflux at 120°C for 4 h, the mixture was washed with warm water at 60°C until the filtrate was neutral, and then dried in an oven at 60°C for 12 h to obtain light yellow tertiary amine functionalized fiber.

[0086] Example 8 Acid red functionalized fiber was prepared in a manner similar to Example 1, except that 1 g of dry acrylic fiber and 36 g of 3-dimethylaminopropylamine were added to a reaction flask, followed by the addition of 30 g of deionized water. After reflux at 120°C for 7 h, the filtrate was washed with warm water at 60°C until the filtrate was neutral, and then dried in an oven at 60°C for 12 h to obtain a light yellow tertiary amine functionalized fiber.

[0087] Example 9 Acid red functionalized fibers were prepared in a manner similar to Example 1, except that 0.5 g of dried tertiary amine functionalized fibers and 2.5 g of iodomethane were added to a reaction flask, followed by the addition of 30 g of ethanol. The fibers were refluxed at 100°C for 5 h, washed with 60°C ethanol, and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fibers.

[0088] Example 10 Acid red functionalized fibers were prepared in a manner similar to Example 1, except that 0.5 g of dried tertiary amine functionalized fibers and 2.5 g of iodomethane were added to a reaction flask, followed by the addition of 30 g of ethanol. The fibers were refluxed at 100°C for 7 h, washed with 60°C ethanol, and then dried in an oven at 60°C for 12 h to obtain orange quaternary amine functionalized fibers.

[0089] Example 11 Acid red functionalized fiber was prepared in a manner similar to Example 1, except that 0.5 g of the above-mentioned quaternary amine functionalized fiber was placed in a 500 mL reaction flask, 500 g of deionized water and 0.5 g of acid red 94 dye were added, and the mixture was stirred at room temperature for 10 h, washed and dried to obtain red acid red functionalized fiber.

[0090] Example 12 Acid red functionalized fiber was prepared in a manner similar to Example 1, except that 0.5 g of the above-mentioned quaternary amine functionalized fiber was placed in a 500 mL reaction flask, 500 g of deionized water and 0.5 g of acid red 94 dye were added, and the mixture was stirred at room temperature for 15 h, washed and dried to obtain red acid red functionalized fiber.

[0091] Example 13 Catalytic reaction: 0.1 mmol of 2-phenyl-1,2,3,4-tetrahydroisoquinoline and 1 mmol of nitromethane were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added, with a catalyst loading of 2 mol%. The reaction was carried out at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0092] Example 14 Catalytic reaction: 0.1 mmol of 2-phenyl-1,2,3,4-tetrahydroisoquinoline and 1 mmol of ethyl cyanoacetate were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added. The catalyst loading was 2 mol%. The reaction was carried out at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0093] Example 15 Catalytic reaction: 0.1 mmol of 2-(4-methylphenyl)-1,2,3,4-tetrahydroisoquinoline and 1 mmol of nitromethane were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added, with a catalyst loading of 2 mol%. The reaction was carried out at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0094] Example 16 Catalytic reaction: 0.1 mmol of 2-(4-methoxyphenyl)-1,2,3,4-tetrahydroisoquinoline and 1 mmol of nitromethane were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added, with a catalyst loading of 2 mol%. The reaction was carried out at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0095] Example 17 Catalytic reaction: 0.1 mmol of 2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinoline and 1 mmol of nitromethane were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added, with a catalyst loading of 2 mol%. The reaction was carried out at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0096] Example 18 Catalytic reaction: 0.1 mmol of 2-(4-bromophenyl)-1,2,3,4-tetrahydroisoquinoline and 1 mmol of nitromethane were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added, with a catalyst loading of 2 mol%. The reaction was carried out at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0097] Example 19 Catalytic reaction: 0.1 mmol of 6,7-dimethoxy-2-phenyl-1,2,3,4-tetrahydroisoquinoline and 1 mmol of nitromethane were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added, with a catalyst loading of 2 mol%. The reaction was carried out at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0098] Example 20 Catalytic reaction: 0.1 mmol of 2-(4-chlorophenyl)-1,2,3,4-tetrahydroisoquinoline and 1 mmol of ethyl cyanoacetate were added to ethanol, and then the acid red functionalized fiber catalyst prepared in Example 1 was added, with a catalyst loading of 2 mol%. The mixture was reacted at room temperature (25°C) for 21 h under green light (λ = 520 ± 20 nm).

[0099] Comparative Example Comparative Example 1 1 g of dry acrylic fiber and 10 g of 1-(3-aminopropyl)imidazole were added to a reaction flask, and then 15 g of deionized water was added. After reflux reaction for 18 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then placed in an oven at 60°C for 12 h to obtain light yellow tertiary amine imidazole functionalized fiber.

[0100] 0.5 g of dry tertiary amine imidazole functionalized fiber and 2.5 g of iodomethane were added to a reaction flask, and then 30 g of ethanol was added. After reflux reaction for 6 h, it was washed with 60°C ethanol and then dried in a 60°C oven for 12 h to obtain orange quaternary amine imidazole functionalized fiber.

[0101] The above 0.5 g of quaternary amine imidazole functionalized fiber was placed in a 500 mL reaction flask, and 500 g of deionized water and 0.5 g of acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber. Comparative Example 2 1 g of dry acrylic fiber and 10 g of 1-(3-aminopropyl)imidazole were added to a reaction flask, and then 15 g of deionized water was added. After reflux reaction for 18 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then placed in a 60°C oven to dry for 12 h to obtain light yellow tertiary amine imidazole functionalized fiber.

[0102] 0.5 g of dry tertiary amine imidazole functionalized fiber and 2.5 g of n-butane bromide were added to a reaction flask, and then 30 g of ethanol was added. After reflux reaction for 6 h, it was washed with 60°C ethanol and then dried in a 60°C oven for 12 h to obtain orange quaternary amine imidazole functionalized fiber.

[0103] The above 0.5 g quaternary aminoimidazole functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber. Comparative Example 3 1 g of dry acrylic fiber and 10 g of 1-(3-aminopropyl)imidazole were added to a reaction flask, and then 15 g of deionized water was added. After reflux reaction for 18 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then placed in a 60°C oven to dry for 12 h to obtain light yellow tertiary amine imidazole functionalized fiber.

[0104] 0.5 g of dry tertiary amine imidazole functionalized fiber and 2.9 g of brominated n-hexane were added to a reaction flask, and then 30 g of ethanol was added. After reflux reaction for 6 h, it was washed with 60°C ethanol and then dried in a 60°C oven for 12 h to obtain orange quaternary amine imidazole functionalized fiber.

[0105] The above 0.5 g quaternary aminoimidazole functionalized fiber was placed in a 500 mL reaction flask, and 500 g deionized water and 0.5 g acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber.

[0106] Comparative Example 4 1 g of dry acrylic fiber and 10 g of 1-(3-aminopropyl)imidazole were added to a reaction flask, and then 15 g of deionized water was added. After reflux reaction for 18 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then placed in a 60°C oven to dry for 12 h to obtain light yellow tertiary amine imidazole functionalized fiber.

[0107] 0.5 g of dry tertiary amine imidazole functionalized fiber and 3.4 g of octane bromide were added to a reaction flask, and then 30 g of ethanol was added. After reflux reaction for 6 h, it was washed with 60°C ethanol and then dried in a 60°C oven for 12 h to obtain orange quaternary amine imidazole functionalized fiber.

[0108] The above 0.5 g of quaternary amine imidazole functionalized fiber was placed in a 500 mL reaction flask, and 500 g of deionized water and 0.5 g of acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber.

[0109] Comparative Example 5 1 g of dry acrylic fiber and 10 g of 1-(3-aminopropyl)imidazole were added to a reaction flask, and then 15 g of deionized water was added. After reflux reaction for 18 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then placed in an oven at 60°C for 12 h to obtain light yellow tertiary amine imidazole functionalized fiber.

[0110] 0.5 g of dry tertiary amine imidazole functionalized fiber and 4.4 g of bromododecane were added to a reaction flask, and then 30 g of ethanol was added. After reflux reaction for 6 h, it was washed with 60°C ethanol and then dried in a 60°C oven for 12 h to obtain orange quaternary amine imidazole functionalized fiber.

[0111] The above 0.5 g of quaternary amine imidazole functionalized fiber was placed in a 500 mL reaction flask, and 500 g of deionized water and 0.5 g of acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber.

[0112] Comparative Example 6 1 g of dry acrylic fiber and 10 g of 1-(3-aminopropyl)imidazole were added to a reaction flask, and then 15 g of deionized water was added. After reflux reaction for 18 h, the filtrate was washed with warm water at 60°C until the filtrate became neutral, and then placed in an oven at 60°C for 12 h to obtain light yellow tertiary amine imidazole functionalized fiber.

[0113] 0.5 g of dry tertiary amine imidazole functionalized fiber and 3 g of benzyl bromide were added to a reaction flask, and then 30 g of ethanol was added. After reflux reaction for 6 h, it was washed with 60°C ethanol and then dried in a 60°C oven for 12 h to obtain orange quaternary amine imidazole functionalized fiber.

[0114] The above 0.5 g of quaternary amine imidazole functionalized fiber was placed in a 500 mL reaction flask, and 500 g of deionized water and 0.5 g of acid red 94 dye were added. After stirring at room temperature for 12 h, the mixture was washed and dried to obtain red acid red functionalized fiber.

[0115] Experimental example Experimental Example 1 SEM test The acid red functionalized fiber prepared in Example 1 was tested by scanning electron microscopy. The test results are as follows: Figure 3 and Figure 4 shown.

[0116] from Figure 3 and Figure 4 It can be seen that the particle size of the Acid Red 94 nanoparticles in the Acid Red functionalized fibers is uniform, and the Acid Red 94 nanoparticles are evenly dispersed on the fiber surface.

[0117] Experimental Example 2 Yield Test An appropriate amount of the acid red functionalized fiber prepared in Examples 1-6 of the present invention and Comparative Examples 1-6 was added to a quartz Schreck tube pre-filled with 0.1 mmol 2-phenyl-1,2,3,4-tetrahydroisoquinoline, 1 mmol nitromethane, 2 mL ethanol and 1-2 mol% of the above acid red functionalized fiber to carry out reaction activity tests under different conditions. After the reaction was completed, samples were taken for HPLC detection. The test results are shown in Table 1.

[0118] Table 1

[0119] As can be seen from Table 1, under different light sources, the acid red catalyst of 12 kinds of imidazole salts and quaternary ammonium salt loads of embodiment 1-12 and comparative example 1-6, the catalytic activity for Aza-Henry reaction is different through HPLC detection.The above results show that, under green light and blue light irradiation, reaction is all efficiently carried out, but the catalytic effect driven by green light is significantly better than blue light.In addition, the acid red catalyst of quaternary ammonium salt load shows the catalytic performance of the similar catalyst that is obviously better than imidazole salt load in these conversion reactions, and this performance difference may be attributed to the conjugated imidazole salt group in the corresponding functionalized fiber absorbing green light, thus interfering with the efficiency of photocatalytic reaction.Wherein, the acid red functionalized fiber prepared by embodiment 3 shows high catalytic efficiency in the Aza-Henry reaction driven by green light, and productive rate reaches 98%. As the nitromethane content decreases, it will be detrimental to the efficient conversion of 2-phenyl-1,2,3,4-tetrahydroisoquinoline; the shortening of reaction time will also lead to a decrease in reaction yield; the reduction of catalyst content is also not conducive to the conversion of the product; that is, the reaction activity is affected by the amount of catalyst, reaction time, substrate amount, and light source. The optimal reaction conditions determined after screening are 0.1 mmol 2-phenyl-1,2,3,4-tetrahydroisoquinoline, 1 mmol nitromethane, 2 mL ethanol and 1-2 mol% acid red functionalized fiber reacted at room temperature for 21 h, and the yield value under these optimal conditions is 98%.

[0120] Experimental Example 3 Cyclic Use Test The acid red functionalized fiber prepared in Example 3 was reused, and it was found that the fiber catalyst had good recycling performance. After a single catalytic process, the acid red functionalized fiber catalyst could be separated by filtration and simply cleaned before being used in the next reaction. The recycling effect was as follows: Figure 5 shown.

[0121] from Figure 5 It can be seen that the acid red functionalized fiber catalyst prepared in Example 3 can be reused 5 times, and the catalyst activity does not decrease significantly after recycling. The HPLC yield only decreases from 98% to 87%, indicating that the acid red functionalized fiber described in the present invention has good reusability.

[0122] Experimental Example 4 The product obtained in Example 13 was subjected to hydrogen spectrum test and carbon spectrum test respectively. The hydrogen spectrum test is as follows: Figure 6 As shown, the carbon spectrum test spectrum is as follows Figure 7 shown.

[0123] Figure 6 middle, 1 H NMR (400 MHz, CDCl3) δ 7.24 - 7.08 (m, 5H), 7.08 - 7.02 (m,1H), 6.90 (d, J = 8.0 Hz, 2H), 6.77 (t, J = 7.3 Hz, 1H), 5.47 (t, J = 7.2 Hz,1H), 4.79 (dd, J = 11.8, 7.8 Hz, 1H), 4.48 (dd, J = 11.8, 6.6 Hz, 1H), 3.64 -3.48 (m, 2H), 3.01 (m, 1H), 2.71 (dt, J = 16.4, 5.0 Hz, 1H). 13C NMR (101MHz, CDCl3) δ : 148.45, 135.31, 132.94, 129.55, 129.23, 128.16, 127.04, 126.74,121.23, 119.46, 115.13, 114.63, 78.81, 65.85, 62.91, 58.24, 42.10, 26.48,20.95.

[0124] from Figure 6 and Figure 7It can be determined that the product obtained in Example 13 is a 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compound, indicating that the acid red functionalized fiber of the present invention can be used as a catalyst to synthesize a 1-(nitromethyl)-2-phenyl-1,2,3,4-tetrahydroisoquinoline compound.

[0125] The present invention has been described in detail above with reference to specific embodiments and exemplary examples. However, these descriptions should not be construed as limiting the present invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications, or improvements may be made to the technical solutions and implementations of the present invention without departing from the spirit and scope of the present invention, all of which fall within the scope of the present invention. The scope of protection of the present invention shall be determined by the appended claims.

Claims

1. An acid red functionalized fiber, characterized in that: The acid red functionalized fiber is prepared from quaternary ammonium fiber and acid red 94 dye, and the mass ratio of the quaternary ammonium fiber to the acid red 94 dye is (0.8-1.3):

1.

2. The acid red functionalized fiber according to claim 1, characterized in that The quaternary amine fiber is prepared from tertiary amine functionalized fiber and halogenated hydrocarbon in a mass ratio of 0.5:(2-5).

3. The acid red functionalized fiber according to claim 2, characterized in that The halogenated hydrocarbon is one or more selected from methyl iodide, ethyl bromide, n-propyl bromide, n-butyl bromide, n-pentane bromide, n-hexane bromide, n-heptane bromide, n-octane bromide, dodecane bromide and benzyl bromide.

4. The acid red functionalized fiber according to claim 2, characterized in that The tertiary amine functionalized fiber is prepared from acrylic fiber and organic amine in a mass ratio of 1: (30-40).

5. The acid red functionalized fiber according to claim 4, characterized in that: The organic amine is selected from one or more of N,N'-dimethyl-1,3-propylene diamine, N,N'-dimethylethylenediamine, ethylenediamine, propylene diamine, N,N-dimethyl-1,3-butylene diamine, butylene diamine, N,N-dimethyl-1,3-pentane diamine, pentane diamine and 3-dimethylaminopropylamine.

6. A method for preparing the acid red functionalized fiber according to any one of claims 1 to 5, characterized in that: The preparation method comprises: The quaternary amine functionalized fiber and acid red 94 dye are added into water, reacted under stirring, and then washed and dried to obtain acid red functionalized fiber; The reaction conditions are: stirring the reaction at room temperature for 10 to 15 hours.

7. The preparation method according to claim 6, characterized in that The preparation method of the quaternary amine functionalized fiber comprises the following steps: The tertiary amine functionalized fiber and halogenated hydrocarbon are added into ethanol for reflux reaction. After the reaction is completed, the fiber is washed and dried to obtain the quaternary amine functionalized fiber.

8. The preparation method according to claim 7, characterized in that The preparation method of the tertiary amine functionalized fiber comprises the following steps: Acrylic fiber and organic amine are added into water for reflux reaction, and then washed and dried to obtain tertiary amine functionalized fiber.

9. Use of the acid red functionalized fiber according to any one of claims 1 to 5, characterized in that: The acid red functionalized fiber can be used as a catalyst.

10. A method for using the acid red functionalized fiber according to any one of claims 1 to 5, characterized in that: The method of use comprises the following steps: Tetrahydroisoquinoline, reaction auxiliary materials and acid red functionalized fiber are added to ethanol, and the reaction is carried out at room temperature under light irradiation to obtain oxidized furazan compounds; The light source is green light or blue light; The reaction time at room temperature is 10 to 15 hours.

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