A method for preparing triphenylchloromethane

Abstract

The application provides a preparation method of triphenyl chloromethane and belongs to the technical field of pharmaceutical intermediates. The preparation method comprises the following steps: obtaining a suspension by using pure benzene, a composite catalyst and an adsorbent, then adding carbon tetrachloride drop by drop to obtain a reaction liquid, stirring and treating the reaction liquid with 808 nm laser when the reaction liquid is heated to 60-80 DEG C, and then performing post-treatment to obtain the triphenyl chloromethane. The composite catalyst catalyzes the reaction of pure benzene and carbon tetrachloride to generate triphenyl chloromethane and release hydrogen chloride, and the adsorbent can adsorb hydrogen chloride in situ, thereby preventing acid corrosion and catalyst poisoning while maintaining the forward progress of the reaction. The composite catalyst and the adsorbent realize catalysis-adsorption synergistic promotion of the forward progress of the reaction, thereby reducing the catalyst consumption, shortening the reaction time, reducing the wastewater generation amount, improving the reaction yield and the purity of the triphenyl chloromethane.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of pharmaceutical intermediates, and particularly relates to a preparation method of triphenyl chloromethane. BACKGROUND

[0002] Triphenyl chloromethane is a white crystal, insoluble in water, easily soluble in benzene, carbon disulfide, petroleum ether and n-hexane, slightly soluble in alcohol and ether, and becomes triphenyl carbinol after water absorption. Triphenyl chloromethane is one of the basic organic raw materials commonly used in the field of pharmaceutical and chemical industry. In the process of organic chemical industry and drug synthesis, triphenylmethyl and its similar protective groups have developed into one of the most commonly used amino or hydroxyl protective groups due to the characteristics of easy on and off, mild conditions, high stability and large steric hindrance, and are particularly advantageous in the selective protection of polyhydroxyl compounds.

[0003] In the current industrial production, the main synthesis method of triphenyl chloromethane is that benzene and carbon tetrachloride occur Friedel-Crafts alkylation in the presence of Lewis acid to produce a complex of triphenyl chloromethane and aluminum trichloride, and triphenyl chloromethane is obtained through post-processing such as hydrolysis, filtration and decolorization, petroleum ether and toluene recrystallization. However, the above process still has some problems, such as the use of aluminum trichloride which is easy to hydrolyze with the generated hydrogen chloride or water, resulting in the loss of acidity and difficulty in recovery; the accumulation of hydrogen chloride will corrode the equipment, and additional neutralization treatment is required, which increases the cost and environmental pressure; the traditional homogeneous aluminum trichloride catalyst is easy to cause the mixing of the product and the catalyst, and the purification step is complex.

[0004] Patent CN 102718624A discloses a synthesis method of triphenyl chloromethane, which first prepares a suspension of aluminum trichloride of benzene by using aluminum powder, pure benzene and hydrogen chloride gas, then adds carbon tetrachloride to react to generate a complex reaction liquid containing triphenyl chloromethane, and uses thionyl chloride for reaction and purification, and recrystallization at 10℃. This process increases the reaction step of aluminum powder and hydrogen chloride gas, and thionyl chloride has high pollution.

[0005] Therefore, it is an important problem to be solved in the field to provide a preparation method of triphenyl chloromethane which can improve the yield and purity of triphenyl chloromethane and reduce wastewater discharge. SUMMARY

[0006] In order to solve the problems in the prior art, the present application provides a preparation method of triphenyl chloromethane, and specifically, the technical scheme of the present application includes the following contents.

[0007] A preparation method of triphenyl chloromethane, the preparation method includes the following steps:

[0008] 210-240 parts by weight of pure benzene, 2.5-5.5 parts by weight of the composite catalyst and 3-6 parts by weight of the adsorbent to obtain a suspension, then 75-115 parts by weight of carbon tetrachloride is added dropwise to obtain a reaction liquid, the reaction liquid is heated to 60-80℃ and treated with 808nm laser under stirring, and then post-treatment is performed to obtain the triphenylmethyl chloride.

[0009] Further, the preparation method of the composite catalyst comprises the following steps:

[0010] Silica, tetrabutyl titanate and a hydrochloric acid solution with a mass fraction of 35% are sequentially subjected to stirring reaction and high-temperature calcination to obtain porous titanium dioxide;

[0011] Anhydrous aluminum chloride and porous titanium dioxide are sequentially subjected to stirring reaction and high-temperature calcination to obtain an intermediate;

[0012] The intermediate and 3-aminopropyl triethoxysilane are reacted to obtain an aminated intermediate;

[0013] The aminated intermediate, N-isopropyl acrylamide, N,N'-methylene bisacrylamide and azobisisobutyronitrile are reacted to obtain the composite catalyst.

[0014] Further, the weight ratio of the silica, tetrabutyl titanate and the hydrochloric acid solution with a mass fraction of 35% is 1.5-2.5:12-15:35-45.

[0015] Further, the stirring reaction conditions of the silica, tetrabutyl titanate and the hydrochloric acid solution with a mass fraction of 35% include a reaction temperature of 30-40℃ and a reaction time of 12-16h.

[0016] Further, the high-temperature calcination conditions of the silica, tetrabutyl titanate and the hydrochloric acid solution with a mass fraction of 35% include a calcination temperature of 530-550℃ and a calcination time of 3-4h.

[0017] Further, the weight ratio of the anhydrous aluminum chloride and the porous titanium dioxide is 0.2-0.4:0.8-1.2.

[0018] Further, the stirring reaction conditions of the anhydrous aluminum chloride and the porous titanium dioxide include a reaction temperature of 50-60℃ and a reaction time of 6-8h.

[0019] Further, the high-temperature calcination conditions of the anhydrous aluminum chloride and the porous titanium dioxide include a calcination temperature of 300-320℃ and a calcination time of 2-4h.

[0020] Further, the weight ratio of the aminated intermediate, N-isopropyl acrylamide, N,N'-methylene bisacrylamide and azobisisobutyronitrile is 1.5-2.5:4-6:0.08-0.12:0.006-0.017.

[0021] Further, the reaction conditions of the aminated intermediate, N-isopropyl acrylamide, N,N'-methylene bisacrylamide and azobisisobutyronitrile include a reaction temperature of 55-65 DEG C and a reaction time of 8-10 h.

[0022] Further, the preparation method of the adsorbent comprises the following steps:

[0023] The hexadecyl trimethyl ammonium bromide, the ferric tetroxide, the tetraethyl orthosilicate and the (3-mercaptopropyl) trimethoxysilane are sequentially subjected to stirring reaction, vacuum drying and high-temperature calcination to obtain the mercapto compound;

[0024] The 1-vinylimidazole and the chlorine-containing compound are reacted to obtain the imidazole-based compound;

[0025] The mercapto compound, the imidazole-based compound and the azobisisobutyronitrile are reacted to obtain the adsorbent.

[0026] Further, the weight ratio of the hexadecyl trimethyl ammonium bromide, the ferric tetroxide, the tetraethyl orthosilicate and the (3-mercaptopropyl) trimethoxysilane is 4-6:0.4-0.6:14-16:2-4.

[0027] Further, the conditions of the vacuum drying include a drying temperature of 50-60 DEG C and a drying time of 12 h.

[0028] Further, the conditions of the high-temperature calcination include a calcination temperature of 330-360 DEG C and a calcination time of 3-4 h.

[0029] Further, the chlorine-containing compound includes one of 2-(2-chloroethoxy)ethanol, chloroacetaldehyde diethyl acetal or 3-chloro-1-propanol.

[0030] Further, the weight ratio of the 1-vinylimidazole and the chlorine-containing compound is 4-6:9-11.

[0031] Further, the reaction conditions of the 1-vinylimidazole and the chlorine-containing compound include a reaction temperature of 60-75 DEG C and a reaction time of 20-24 h.

[0032] Further, the weight ratio of the mercapto compound, the imidazole-based compound and the azobisisobutyronitrile is 1-3:9-12:0.01-0.03.

[0033] Further, the reaction conditions of the mercapto compound, the imidazole-based compound and the azobisisobutyronitrile include a reaction temperature of 50-60 DEG C and a reaction time of 12-16 h.

[0034] Further, the mixing time is 20-30 min.

[0035] Further, the temperature during the dropwise addition of carbon tetrachloride is 35-40 DEG C.

[0036] Further, the conditions of the 808nm laser treatment include that the laser power is 1W / cm 2 and the irradiation mode is irradiation for 5min and stop for 15min.

[0037] Further, the post-treatment step includes cooling to 15-20 DEG C after the reaction ends, standing for 10min, decanting the upper reaction liquid to a separation funnel, collecting the precipitate, separating and treating the composite catalyst and the hydrogen chloride adsorbent, then combining the decanted upper reaction liquid and the methanol used for washing the composite catalyst, adjusting the pH to 7 with saturated sodium bicarbonate solution, removing the water phase after phase separation, drying the organic phase with anhydrous sodium sulfate for 1-2h, filtering, distilling the filtrate under reduced pressure to obtain the crude product, dispersing the crude product in hot ethanol at 60 DEG C, slowly cooling to 5 DEG C, and completing the post-treatment through suction filtration and vacuum drying after 3-5h of incubation.

[0038] Further, the step of separating and treating the composite catalyst and the hydrogen chloride adsorbent includes separating the hydrogen chloride adsorbent and the composite catalyst by using a magnet, washing the composite catalyst with 4 DEG C methanol for 3 times, and recycling the composite catalyst after vacuum drying at 40 DEG C, and dispersing the hydrogen chloride adsorbent in deionized water, heating to 120-130 DEG C, stirring for 1-2h, washing to neutral, and recycling the hydrogen chloride adsorbent after vacuum drying at 40 DEG C.

[0039] Compared with the prior art, the application has the following beneficial effects:

[0040] (1) The application obtains porous titanium dioxide by using silica as a template and tetrabutyl titanate as a titanium source through a template method, loads anhydrous aluminum chloride into the pores of the mesoporous titanium dioxide to obtain an intermediate through an impregnation method, modifies the intermediate to obtain an aminated intermediate after 3-aminopropyltriethoxysilane, and reacts N-isopropyl acrylamide and N,N'-methylene bisacrylamide to form polyisopropyl acrylamide to load the aminated intermediate to obtain a composite catalyst with a temperature-sensitive effect; the composite catalyst provided by the application has good catalytic activity and recycling performance; the porous titanium dioxide in the composite catalyst can enhance the catalytic performance of the anhydrous aluminum chloride when irradiated by 808nm laser; the local heating of the composite catalyst by 808nm laser irradiation can reduce the reaction activation energy and accelerate the reaction process; the presence of the polyisopropyl acrylamide endows the composite catalyst with temperature-sensitive performance, which is hydrophobic and dispersed in the reaction system at high temperature (>32 DEG C) and is hydrophilic and precipitated from the reaction system at low temperature (<25 DEG C), thereby physically protecting the anhydrous aluminum chloride, reducing the loss of the active component, and realizing recycling after simple treatment.

[0041] (2)The application coats a layer of thiol-containing silicon dioxide on the surface of ferroferric oxide to obtain a thiolated compound, reacts 1-vinylimidazole and a chlorine-containing compound to obtain an imidazole-based compound, and prepares the adsorbent through thiol-alkene reaction of the thiolated compound and the imidazole-based compound; the adsorbent provided by the application has good adsorption effect on hydrogen chloride generated in the reaction, can be reused after separation by a magnet and high-temperature treatment after use, and has good cycle performance.

[0042] (3)In the application, the composite catalyst can catalyze pure benzene and carbon tetrachloride to generate triphenylmethyl chloride, and release hydrogen chloride at the same time; the adsorbent can adsorb hydrogen chloride in situ, can prevent acid corrosion and catalyst poisoning while maintaining the forward progress of the reaction; the adsorbent and the composite catalyst are recovered through magnetic-temperature double modes respectively, to avoid cross contamination; the hydrogen chloride adsorbed by the adsorbent can be released after high-temperature treatment to prepare hydrochloric acid solution, to realize resource recycling; the application realizes catalysis-adsorption synergistic promotion of the reaction forward progress through the composite catalyst and the adsorbent, reduces the catalyst dosage, shortens the reaction time, reduces the amount of waste water generated, and improves the reaction yield and the purity of triphenylmethyl chloride. DETAILED DESCRIPTION

[0043] The technical solutions of the application will be described clearly and completely through the embodiments of the application. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor are within the protection scope of the application.

[0044] Unless otherwise specified, the raw materials and reagents used in the application below are commercially available or can be prepared by known methods.

[0045] Preparation Example 1:

[0046] The preparation method of the composite catalyst comprises the following steps:

[0047] 1.5 parts by weight of silica was dispersed in 12 parts by weight of tetrabutyl titanate and 100 parts by weight of anhydrous ethanol, ultrasonic dispersion was carried out for 30 min, then 35 parts by weight of a 35% mass fraction hydrochloric acid solution was added, after stirring and reaction at 30°C for 12 h, the precipitate was collected by centrifugation, and the precipitate was calcined at 530°C for 3 h to obtain porous titanium dioxide; 0.2 parts by weight of anhydrous aluminum chloride was dispersed in 50 parts by weight of anhydrous ethanol, ultrasonic dispersion was carried out for 10 min, then 0.8 parts by weight of the porous titanium dioxide was added, stirring and reaction were carried out at 50°C for 6 h, after the reaction was completed, the solid was collected by centrifugation, vacuum drying was carried out at 80°C for 12 h, then calcination was carried out at 300°C for 2 h in a nitrogen protection environment to obtain an intermediate; 0.8 parts by weight of the intermediate and 1.3 parts by weight of 3-aminopropyl triethoxysilane were dispersed in 100 parts by weight of toluene, stirring and reaction were carried out at 110°C for 12 h, after the reaction was completed, centrifugation, washing and drying were carried out in sequence to obtain an aminated intermediate; 1.5 parts by weight of the aminated intermediate, 4 parts by weight of N-isopropyl acrylamide, 0.08 parts by weight of N,N'-methylene bisacrylamide and 0.006 parts by weight of azobisisobutyronitrile were dispersed in 50 parts by weight of methanol, stirring and reaction were carried out at 55°C for 8 h in a nitrogen protection environment, after the reaction was completed, centrifugation, washing and drying were carried out in sequence to obtain the composite catalyst.

[0048] Preparation Example 2:

[0049] A method for preparing a composite catalyst comprises the following steps:

[0050] 1.5 parts by weight of silica was dispersed in 12 parts by weight of tetrabutyl titanate and 100 parts by weight of anhydrous ethanol, ultrasonic dispersion was carried out for 30 min, then 35 parts by weight of a 35% mass fraction hydrochloric acid solution was added, after stirring and reaction at 30°C for 12 h, the precipitate was collected by centrifugation, and the precipitate was calcined at 530°C for 3 h to obtain porous titanium dioxide; 0.2 parts by weight of anhydrous aluminum chloride was dispersed in 50 parts by weight of anhydrous ethanol, ultrasonic dispersion was carried out for 10 min, then 0.8 parts by weight of the porous titanium dioxide was added, stirring and reaction were carried out at 50°C for 6 h, after the reaction was completed, the solid was collected by centrifugation, vacuum drying was carried out at 80°C for 12 h, then calcination was carried out at 300°C for 2 h in a nitrogen protection environment to obtain an intermediate; 0.8 parts by weight of the intermediate and 1.3 parts by weight of 3-aminopropyl triethoxysilane were dispersed in 100 parts by weight of toluene, stirring and reaction were carried out at 110°C for 12 h, after the reaction was completed, centrifugation, washing and drying were carried out in sequence to obtain an aminated intermediate; 1.5 parts by weight of the aminated intermediate, 4 parts by weight of N-isopropyl acrylamide, 0.08 parts by weight of N,N'-methylene bisacrylamide and 0.006 parts by weight of azobisisobutyronitrile were dispersed in 50 parts by weight of methanol, stirring and reaction were carried out at 55°C for 8 h in a nitrogen protection environment, after the reaction was completed, centrifugation, washing and drying were carried out in sequence to obtain the composite catalyst.

[0051] Preparation Example 3:

[0052] A method for preparing a composite catalyst, comprising the steps of:

[0053] 2 parts by weight of silica were dispersed in 14 parts by weight of tetrabutyl titanate and 100 parts by weight of anhydrous ethanol, ultrasonic dispersion was performed for 30 min, 40 parts by weight of a hydrochloric acid solution with a mass fraction of 35% was then added, stirring reaction was performed at 36°C for 15 h, the precipitate was collected by centrifugation, the precipitate was calcined at 540°C for 3.7 h to obtain porous titanium dioxide; 0.3 parts by weight of anhydrous aluminum chloride was dispersed in 50 parts by weight of anhydrous ethanol, ultrasonic dispersion was performed for 10 min, 1.0 part by weight of the porous titanium dioxide was then added, stirring reaction was performed at 56°C for 7.5 h, the solid was collected by centrifugation after the reaction was completed, vacuum drying was performed at 80°C for 12 h, and calcination was performed at 315°C for 3 h in a nitrogen protection environment to obtain an intermediate; 1.1 parts by weight of the intermediate and 1.6 parts by weight of 3-aminopropyl triethoxysilane were dispersed in 100 parts by weight of toluene, stirring reaction was performed at 115°C for 12 h, and the aminated intermediate was obtained by sequentially performing centrifugation, washing and drying after the reaction was completed; 2.1 parts by weight of the aminated intermediate, 5 parts by weight of N-isopropyl acrylamide, 0.1 part by weight of N,N'-methylene bisacrylamide and 0.013 part by weight of azobisisobutyronitrile were dispersed in 50 parts by weight of methanol, stirring reaction was performed at 60°C for 9 h in a nitrogen protection environment, and the composite catalyst was obtained by sequentially performing centrifugation, washing and drying after the reaction was completed.

[0054] Preparation Example 4:

[0055] A method for preparing a composite catalyst, comprising the steps of:

[0056] 2.5 parts by weight of silica were dispersed in 15 parts by weight of tetrabutyl titanate and 100 parts by weight of anhydrous ethanol, ultrasonic dispersion was performed for 30 min, 45 parts by weight of a hydrochloric acid solution with a mass fraction of 35% was then added, stirring reaction was performed at 40°C for 16 h, the precipitate was collected by centrifugation, the precipitate was calcined at 550°C for 4 h to obtain porous titanium dioxide; 0.4 parts by weight of anhydrous aluminum chloride was dispersed in 50 parts by weight of anhydrous ethanol, ultrasonic dispersion was performed for 10 min, 1.2 parts by weight of the porous titanium dioxide was then added, stirring reaction was performed at 60°C for 8 h, the solid was collected by centrifugation after the reaction was completed, vacuum drying was performed at 80°C for 12 h, and calcination was performed at 320°C for 4 h in a nitrogen protection environment to obtain an intermediate; 1.2 parts by weight of the intermediate and 1.7 parts by weight of 3-aminopropyl triethoxysilane were dispersed in 100 parts by weight of toluene, stirring reaction was performed at 120°C for 12 h, and the aminated intermediate was obtained by sequentially performing centrifugation, washing and drying after the reaction was completed; 2.5 parts by weight of the aminated intermediate, 6 parts by weight of N-isopropyl acrylamide, 0.12 part by weight of N,N'-methylene bisacrylamide and 0.017 part by weight of azobisisobutyronitrile were dispersed in 50 parts by weight of methanol, stirring reaction was performed at 65°C for 10 h in a nitrogen protection environment, and the composite catalyst was obtained by sequentially performing centrifugation, washing and drying after the reaction was completed.

[0057] Preparation Example 5:

[0058] The method for preparing the composite catalyst comprises the following steps:

[0059] 2.5 parts by weight of silica was dispersed in 15 parts by weight of tetrabutyl titanate and 100 parts by weight of anhydrous ethanol, ultrasonic dispersion for 30 min, then 45 parts by weight of 35% hydrochloric acid solution was added, stirring and reacting at 40℃ for 16 h, then the precipitate was collected by centrifugation, and the precipitate was calcined at 550℃ for 4 h to obtain porous titanium dioxide; 0.4 parts by weight of anhydrous aluminum chloride was dispersed in 50 parts by weight of anhydrous ethanol, ultrasonic dispersion for 10 min, then 0.4 parts by weight of 35% hydrochloric acid solution was added, stirring and reacting at 40℃ for 16 h, then the precipitate was collected by centrifugation, and the precipitate was calcined at 550℃ for 4 h to obtain porous aluminum oxide.

[0060] 1.2 parts by weight of porous titanium dioxide was stirred and reacted at 60℃ for 8 h, then the solid was collected by centrifugation, vacuum dried at 80℃ for 12 h, and then calcined at 320℃ for 4 h in a nitrogen protection environment to obtain the composite catalyst.

[0061] Preparation Example 6:

[0062] 2.5 parts by weight of anhydrous aluminum chloride, 6 parts by weight of N-isopropyl acrylamide, 0.12 parts by weight of N,N'-methylene bisacrylamide and 0.017 parts by weight of azobisisobutyronitrile were dispersed in 50 parts by weight of methanol, stirring and reacting at 65℃ for 10 h in a nitrogen protection environment, then the composite catalyst was obtained by centrifugation, washing and drying in sequence.

[0063] Preparation Example 7:

[0064] The method for preparing the adsorbent comprises the following steps:

[0065] 4 parts by weight of cetyltrimethylammonium bromide and 0.4 parts by weight of ferroferric oxide were dispersed in 100 parts by weight of deionized water, ultrasonic dispersion for 20 min, then 50 parts by weight of 10 mM sodium hydroxide solution and 400 parts by weight of deionized water were added, stirring at 60℃ for 30 min, then 14 parts by weight of tetraethyl orthosilicate, 2 parts by weight of (3-mercaptopropyl)trimethoxysilane and 20 parts by weight of methanol were added, stirring and reacting at 50℃ for 12 h, then the mixture was separated by a magnet, washed with deionized water and ethanol alternately for 3 times, vacuum dried at 50℃ for 12 h, and then calcined at 330℃ for 3 h to obtain a mercapto compound; 4 parts by weight of 1-vinylimidazole and 9 parts by weight of 3-chloro-1-propanol were stirred and reacted at 60℃ for 20 h in a nitrogen protection environment, then the mixture was washed with ethyl acetate and anhydrous ether alternately for 3 times, vacuum dried at 50℃ for 12 h to obtain an imidazole compound; 1 part by weight of the mercapto compound, 9 parts by weight of the imidazole compound and 0.01 part by weight of azobisisobutyronitrile were dispersed in 100 parts by weight of N,N-dimethylformamide, stirring and reacting at 50℃ for 12 h in a nitrogen protection environment, then the adsorbent was obtained by centrifugation, washing and vacuum drying in sequence.

[0066] Preparation Example 8:

[0067] The method for preparing the adsorbent comprises the following steps:

[0068] 4.5 parts by weight of cetyltrimethylammonium bromide and 0.45 parts by weight of ferric oxide are dispersed in 100 parts by weight of deionized water, after ultrasonic dispersion for 22 min, 50 parts by weight of a 10 mM sodium hydroxide solution and 400 parts by weight of deionized water are added, stirring is carried out at 60°C for 30 min, then 14.5 parts by weight of tetraethyl orthosilicate, 2.5 parts by weight of (3-mercaptopropyl)trimethoxysilane and 20 parts by weight of methanol are added, after stirring and reaction at 52°C for 12 h, the product is separated by a magnet, washed with deionized water and ethanol alternately for 3 times, then vacuum dried at 52°C for 12 h, and finally calcined at 335°C for 3.2 h to obtain a mercapto compound; 4.5 parts by weight of 1-vinylimidazole and 9.5 parts by weight of chloroacetaldehyde diethyl acetal are stirred and reacted at 65°C for 21 h in a nitrogen protection environment, after the reaction is completed, the product is washed with ethyl acetate and anhydrous diethyl ether alternately for 3 times, then vacuum dried at 50-60°C for 12 h to obtain an imidazole compound; 1.5 parts by weight of the mercapto compound, 10 parts by weight of the imidazole compound and 0.02 parts by weight of azobisisobutyronitrile are dispersed in 100 parts by weight of N,N-dimethylformamide, stirring and reaction are carried out at 52°C for 13 h in a nitrogen protection environment, after the reaction is completed, the product is subjected to centrifugation, washing and vacuum drying in sequence to obtain the adsorbent.

[0069] Preparation Example 9:

[0070] The method for preparing the adsorbent comprises the following steps:

[0071] 5 parts by weight of hexadecyltrimethylammonium bromide and 0.5 parts by weight of ferric tetroxide are dispersed in 100 parts by weight of deionized water, after ultrasonic dispersion for 26 min, 50 parts by weight of a 10 mM sodium hydroxide solution and 400 parts by weight of deionized water are added, stirring at 60°C for 30 min, then 15 parts by weight of tetraethyl orthosilicate, 3 parts by weight of (3-mercaptopropyl)trimethoxysilane and 20 parts by weight of methanol are added, after stirring and reaction at 57°C for 12 h, the product is separated by a magnet and washed with deionized water and ethanol alternately for 3 times, then vacuum dried at 56°C for 12 h, and calcined at 345°C for 3.6 h to obtain a mercapto compound; 5 parts by weight of 1-vinylimidazole and 10 parts by weight of (2-(2-chloroethoxy)ethanol are stirred at 70°C for 23 h in a nitrogen protection environment, after the reaction is completed, the product is washed with ethyl acetate and anhydrous diethyl ether alternately for 3 times, then vacuum dried at 56°C for 12 h to obtain an imidazole compound; 2 parts by weight of the mercapto compound, 11 parts by weight of the imidazole compound and 0.02 parts by weight of azobisisobutyronitrile are dispersed in 100 parts by weight of N,N-dimethylformamide, stirring and reaction at 57°C for 15 h in a nitrogen protection environment, after the reaction is completed, the product is prepared by centrifugation, washing and vacuum drying in sequence to obtain an adsorbent.

[0072] Preparation Example 10:

[0073] The preparation method of the adsorbent comprises the following steps:

[0074] 6 parts by weight of hexadecyltrimethylammonium bromide and 0.6 parts by weight of ferric tetroxide are dispersed in 100 parts by weight of deionized water, after ultrasonic dispersion for 30 min, 50 parts by weight of a 10 mM sodium hydroxide solution and 400 parts by weight of deionized water are added, stirring at 60°C for 30 min, then 16 parts by weight of tetraethyl orthosilicate, 4 parts by weight of (3-mercaptopropyl)trimethoxysilane and 20 parts by weight of methanol are added, after stirring and reaction at 60°C for 12 h, the product is separated by a magnet and washed with deionized water and ethanol alternately for 3 times, then vacuum dried at 60°C for 12 h, and calcined at 350°C for 4 h to obtain a mercapto compound; 6 parts by weight of 1-vinylimidazole and 11 parts by weight of chloroacetaldehyde diethyl acetal are stirred at 75°C for 24 h in a nitrogen protection environment, after the reaction is completed, the product is washed with ethyl acetate and anhydrous diethyl ether alternately for 3 times, then vacuum dried at 60°C for 12 h to obtain an imidazole compound; 3 parts by weight of the mercapto compound, 12 parts by weight of the imidazole compound and 0.03 parts by weight of azobisisobutyronitrile are dispersed in 100 parts by weight of N,N-dimethylformamide, stirring and reaction at 60°C for 16 h in a nitrogen protection environment, after the reaction is completed, the product is prepared by centrifugation, washing and vacuum drying in sequence to obtain an adsorbent.

[0075] Preparation Example 11:

[0076] The preparation method of the adsorbent comprises the following steps:

[0077] The chloroacetaldehyde diethyl acetal in Preparation Example 10 is replaced by chloromethyloctyl ether, and other operations are the same as those in Preparation Example 10.

[0078] Example 1:

[0079] A preparation method of triphenyl chloromethane, comprising the following steps:

[0080] 210 parts by weight of pure benzene, 2.5 parts by weight of the composite catalyst prepared in Preparation Example 1 and 3 parts by weight of the adsorbent prepared in Preparation Example 7 are placed in a flask, stirred and mixed for 20 min to obtain a suspension, 65 parts by weight of carbon tetrachloride is added dropwise to the suspension under stirring at 35 ℃ in a nitrogen protection environment to obtain a reaction liquid, the reaction liquid is heated to 60 ℃, and the reaction is treated by intermittent irradiation (irradiation for 5 min and stop for 15 min) of an 808 nm laser with a power of 1 W / cm 2 at a distance of 10 cm from the surface of the reaction liquid under stirring for 6 h, after the reaction is completed, the temperature is lowered to 15 ℃, and after standing for 10 min, the precipitate and the reaction liquid are separated, and the upper reaction liquid is decanted into a separation funnel; the precipitate is collected and separated by a magnet to separate the hydrogen chloride adsorbent and the composite catalyst, the composite catalyst is washed with 4 ℃ methanol for 3 times, and after vacuum drying at 40 ℃, the composite catalyst can be recycled, the hydrogen chloride adsorbent is dispersed in deionized water, heated to 120 ℃ and stirred for 1 h, then washed to neutral and vacuum dried at 40 ℃, and the hydrogen chloride adsorbent can be recycled; the decanted upper reaction liquid and the methanol used for washing the composite catalyst are combined, the pH is adjusted to 7 with a saturated sodium bicarbonate solution, after the aqueous phase is removed by liquid separation, the organic phase is dried with anhydrous sodium sulfate for 1 h, filtered, and the filtrate is distilled under reduced pressure to obtain a crude product, the crude product is dispersed in hot ethanol at 60 ℃, then slowly cooled to 5 ℃, and after standing for 3 h, the triphenyl chloromethane is prepared by sequential suction filtration and vacuum drying.

[0081] Example 2:

[0082] A preparation method of triphenyl chloromethane, comprising the following steps:

[0083] 220 parts by weight of pure benzene, 3.5 parts by weight of the composite catalyst prepared in Preparation Example 2 and 4 parts by weight of the adsorbent prepared in Preparation Example 8 are placed in a flask, stirred and mixed for 24 min to obtain a suspension, 70 parts by weight of carbon tetrachloride is added dropwise to the suspension under stirring at 37 ℃ in a nitrogen protection environment to obtain a reaction liquid, the reaction liquid is heated to 65 ℃, and the reaction is treated by intermittent irradiation (irradiation for 5 min and stop for 15 min) of an 808 nm laser with a power of 1 W / cm 2The 808 nm laser irradiates the reaction liquid intermittently (irradiation for 5 min and stop for 15 min) at a distance of 10 cm from the surface of the reaction liquid for 6.5 h of stirring reaction. After the reaction is completed, the temperature is lowered to 16°C, and the precipitate and the reaction liquid are separated after standing for 10 min. The upper layer of the reaction liquid is decanted into a separation funnel. The precipitate is collected and separated by a magnet to separate the hydrogen chloride adsorbent and the composite catalyst. The composite catalyst and the hydrogen chloride adsorbent are collected. The composite catalyst is washed with 4°C methanol for 3 times, and is dried at 40°C under vacuum for recycling. The hydrogen chloride adsorbent is dispersed in deionized water, heated to 122°C, and stirred for 1.2 h. After being washed with water to neutral, the hydrogen chloride adsorbent is dried at 40°C under vacuum for recycling. The upper layer of the reaction liquid and the methanol used for washing the composite catalyst are combined, and the pH is adjusted to 7 with a saturated sodium bicarbonate solution. After the water phase is removed by liquid separation, the organic phase is dried with anhydrous sodium sulfate for 1.2 h. After filtration, the filtrate is distilled under reduced pressure to obtain a crude product. The crude product is dispersed in hot ethanol at 60°C, and is slowly cooled to 5°C. After standing for 3.5 h, triphenylmethyl chloride is obtained by suction filtration and vacuum drying in sequence.

[0084] Example 3

[0085] A method for preparing triphenylmethyl chloride includes the following steps:

[0086] 230 parts by weight of pure benzene, 4.5 parts by weight of the composite catalyst prepared in Preparation Example 3, and 5 parts by weight of the adsorbent prepared in Preparation Example 9 are placed in a flask, and are mixed by stirring for 28 min to obtain a suspension. In a nitrogen protection environment, 75 parts by weight of carbon tetrachloride is added dropwise to the suspension at 38°C while stirring. The reaction liquid is heated to 75°C, and is irradiated with an 808 nm laser having a power of 1 W / cm 2 The 808 nm laser irradiates the reaction liquid intermittently (irradiation for 5 min and stop for 15 min) at a distance of 10 cm from the surface of the reaction liquid for 6.5 h of stirring reaction. After the reaction is completed, the temperature is lowered to 16°C, and the precipitate and the reaction liquid are separated after standing for 10 min. The upper layer of the reaction liquid is decanted into a separation funnel. The precipitate is collected and separated by a magnet to separate the hydrogen chloride adsorbent and the composite catalyst. The composite catalyst and the hydrogen chloride adsorbent are collected. The composite catalyst is washed with 4°C methanol for 3 times, and is dried at 40°C under vacuum for recycling. The hydrogen chloride adsorbent is dispersed in deionized water, heated to 122°C, and stirred for 1.2 h. After being washed with water to neutral, the hydrogen chloride adsorbent is dried at 40°C under vacuum for recycling. The upper layer of the reaction liquid and the methanol used for washing the composite catalyst are combined, and the pH is adjusted to 7 with a saturated sodium bicarbonate solution. After the water phase is removed by liquid separation, the organic phase is dried with anhydrous sodium sulfate for 1.2 h. After filtration, the filtrate is distilled under reduced pressure to obtain a crude product. The crude product is dispersed in hot ethanol at 60°C, and is slowly cooled to 5°C. After standing for 3.5 h, triphenylmethyl chloride is obtained by suction filtration and vacuum drying in sequence.

[0087] Example 4

[0088] A method for preparing triphenyl chloromethane, comprising the following steps:

[0089] 240 parts by weight of pure benzene, 5.5 parts by weight of the composite catalyst prepared in Preparation Example 4, and 6 parts by weight of the adsorbent prepared in Preparation Example 10 are placed in a flask, stirred and mixed for 30 min to obtain a suspension, and 85 parts by weight of carbon tetrachloride is added dropwise under stirring at 40℃ in a nitrogen-protected environment to obtain a reaction solution. The reaction solution is heated to 80℃, and the stirring reaction is treated intermittently (irradiation for 5 min and stop for 15 min) for 8 h by using an 808 nm laser with a power of 1 W / cm 2 at a distance of 10 cm from the surface of the reaction solution. After the reaction is completed, the temperature is lowered to 20℃, and the precipitate and the reaction solution are separated after standing for 10 min. The upper layer of the reaction solution is decanted into a separation funnel. The precipitate is collected and separated by using a magnet to separate the hydrogen chloride adsorbent and the composite catalyst. The composite catalyst and the hydrogen chloride adsorbent are collected, the composite catalyst is washed with 4℃ methanol for 3 times, and then dried at 40℃ under vacuum to be recycled. The hydrogen chloride adsorbent is dispersed in deionized water, heated to 130℃, and stirred for 2 h. After being washed to neutral, the hydrogen chloride adsorbent is dried at 40℃ under vacuum to be recycled. The decanted upper layer of the reaction solution and the methanol used for washing the composite catalyst are combined, and the pH is adjusted to 7 by using a saturated sodium bicarbonate solution. After the aqueous phase is removed by liquid separation, the organic phase is dried by using anhydrous sodium sulfate for 2 h, filtered, and then the filtrate is distilled under reduced pressure to obtain a crude product. The crude product is dispersed in hot ethanol at 60℃, slowly cooled to 5℃, and then treated by vacuum filtration and vacuum drying for 5 h to obtain triphenyl chloromethane.

[0090] Comparative Example 1

[0091] A method for preparing triphenyl chloromethane, comprising the following steps:

[0092] In Example 4, the composite catalyst prepared in Preparation Example 4 is replaced by the composite catalyst prepared in Preparation Example 5, and the other operations remain the same as those in Example 4.

[0093] Comparative Example 2

[0094] A method for preparing triphenyl chloromethane, comprising the following steps:

[0095] In Example 4, the composite catalyst prepared in Preparation Example 4 is replaced by the composite catalyst prepared in Preparation Example 6, and the other operations remain the same as those in Example 4.

[0096] Comparative Example 3

[0097] A method for preparing triphenyl chloromethane, comprising the following steps:

[0098] In Example 4, the adsorbent prepared in Preparation Example 10 is replaced by the adsorbent prepared in Preparation Example 11, and the other operations remain the same as those in Example 4.

[0099] Comparative Example 4:

[0100] A method for preparing triphenylchloromethane, comprising the following steps:

[0101] Without using the adsorbent prepared in Preparation Example 10 in Example 4, other operations are consistent with Example 4.

[0102] Comparative Example 5:

[0103] A method for preparing triphenylchloromethane, comprising the following steps:

[0104] Replacing 5.5 parts by weight of the composite catalyst prepared in Preparation Example 4 in Example 4 with 10 parts by weight of the composite catalyst prepared in Preparation Example 4, other operations are consistent with Example 4.

[0105] Comparative Example 6:

[0106] A method for preparing triphenylchloromethane, comprising the following steps:

[0107] Replacing 5.5 parts by weight of the composite catalyst prepared in Preparation Example 4 in Example 4 with 1.5 parts by weight of the composite catalyst prepared in Preparation Example 4, other operations are consistent with Example 4.

[0108] Performance test:

[0109] The yield and purity of triphenylchloromethane prepared in Examples 1-4 and Comparative Examples 1-6 are detected, and the detection results are shown in Table 1.

[0110] Table 1. Yield and purity of triphenylchloromethane

[0111] Yield Purity Example 1 81.9％ 99.1％ Example 2 82.4％ 99.2％ Example 3 83.1％ 99.3％ Example 4 83.6％ 99.3％ Comparative Example 1 75.9％ 97.3％ Comparative Example 2 72.4％ 96.8％ Comparative Example 3 73.8％ 97.1％ Comparative Example 4 71.9％ 96.5％ Comparative Example 5 83.3％ 95.9％ Comparative Example 6 69.3％ 97.6％

[0112] It can be observed from the detection results in Table 1 that the triphenyl chloromethane prepared by Examples 1-4 of the present application has good yield and purity. The reasons for the decrease in yield and purity of Comparative Example 1 can be that part of the polyisopropyl acrylamide is missing in the composite catalyst, and the dispersion degree of the composite catalyst in the reaction system is reduced, thereby affecting the catalytic performance; the reasons for the decrease in yield and purity of Comparative Example 2 can be that the porous titanium dioxide is missing in the composite catalyst, and the catalytic performance of anhydrous aluminum chloride cannot be promoted under 808 nm laser irradiation; the reasons for the decrease in yield and purity of Comparative Example 3 can be that chloroacetaldehyde diethyl acetal is replaced by chloromethyloctyl ether, and the increase in carbon chain length affects the adsorption effect of the adsorbent on hydrogen chloride, thereby affecting the progress of the forward reaction; the reasons for the decrease in yield and purity of Comparative Example 4 can be that no adsorbent is added, and the speed of the forward reaction cannot be improved; Comparative Example 5 has good yield, but the purity of triphenyl chloromethane decreases, and the reasons can be that the excessive amount of the composite catalyst leads to an increase in side reactions, and a large amount of by-products are produced, thereby affecting the purity of triphenyl chloromethane; the reasons for the decrease in yield and purity of Comparative Example 6 can be that the amount of the composite catalyst is insufficient, and the reaction cannot be fully catalyzed.

[0113] The above-described examples have described the technical solutions and beneficial effects of the present application in detail. It should be understood that the above-described examples are only specific embodiments of the present application, and are not used to limit the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the present application.

Claims

1. A method for preparing triphenylchloromethane, characterized in that, The preparation method includes the following steps: 210-240 parts by weight of pure benzene, 2.5-5.5 parts by weight of composite catalyst and 3-6 parts by weight of adsorbent are stirred and mixed to obtain a suspension. Then, 75-115 parts by weight of carbon tetrachloride are added dropwise to obtain a reaction solution. The reaction solution is heated to 60-80°C and treated with an 808nm laser while stirring. After post-treatment, the triphenylchloromethane is obtained. The preparation method of the composite catalyst includes the following steps: Porous titanium dioxide was obtained by sequentially reacting silicon dioxide, tetrabutyl titanate, and a 35% hydrochloric acid solution with stirring and high-temperature calcination. Anhydrous aluminum trichloride and porous titanium dioxide were reacted sequentially by stirring and calcination at high temperature to obtain an intermediate. The intermediate reacts with 3-aminopropyltriethoxysilane to give an aminated intermediate; The composite catalyst was prepared by reacting an aminated intermediate, N-isopropylacrylamide, N,N'-methylenebisacrylamide and azobisisobutyronitrile. The method for preparing the adsorbent includes the following steps: A mercaptolated complex was obtained by sequentially reacting hexadecyltrimethylammonium bromide, iron(II,III) oxide, sodium hydroxide, tetraethyl orthosilicate, and (3-mercaptopropyl)trimethoxysilane with stirring, vacuum drying, and high-temperature calcination. 1-Vinylimidazole reacts with chlorine-containing compounds to yield imidazole-based compounds; The adsorbent was prepared by reacting a thiolized complex, an imidazole compound, and azobisisobutyronitrile. The post-processing steps include cooling to 15-20°C after the reaction, allowing it to stand for 10 minutes, and then decanting the upper reaction layer into a separation funnel; collecting the precipitate, separating and treating the composite catalyst and hydrogen chloride adsorbent, combining the decanted upper reaction layer and the methanol used to wash the composite catalyst, adjusting the pH to 7 with saturated sodium bicarbonate solution, removing the aqueous phase by separation, drying the organic phase with anhydrous sodium sulfate for 1-2 hours, filtering, and then distilling the filtrate under reduced pressure to obtain the crude product. The crude product is dispersed in hot ethanol at 60°C, then slowly cooled to 5°C, kept warm for 3-5 hours, and then sequentially filtered and dried under vacuum to complete the post-processing. The chlorine-containing compound includes one of 2-(2-chloroethoxy)ethanol, chloroacetaldehyde diethanol, or 3-chloro-1-propanol.

2. The method for preparing triphenylchloromethane as described in claim 1, characterized in that, The weight ratio of anhydrous aluminum trichloride to porous titanium dioxide is 0.2~0.4:0.8~1.

2.

3. The method for preparing triphenylchloromethane as described in claim 1, characterized in that, The weight ratio of the aminated intermediate, N-isopropylacrylamide, N,N'-methylenebisacrylamide and azobisisobutyronitrile is 1.5~2.5:4~6:0.08~0.12:0.006~0.

017.

4. The method for preparing triphenylchloromethane as described in claim 1, characterized in that, The weight ratio of hexadecyltrimethylammonium bromide, iron tetroxide, tetraethyl orthosilicate and (3-mercaptopropyl)trimethoxysilane is 4~6:0.4~0.6:14~16:2~4.

5. The method for preparing triphenylchloromethane as described in claim 1, characterized in that, The weight ratio of the thiolized complex, the imidazole compound, and the azobisisobutyronitrile is 1~3:9~12:0.01~0.

03.

6. The method for preparing triphenylchloromethane as described in claim 1, characterized in that, The temperature during the addition of carbon tetrachloride is 35~40℃.

7. The method for preparing triphenylchloromethane as described in claim 1, characterized in that, The conditions for the 808nm laser treatment include a laser power of 1W / cm². 2 The irradiation method is to irradiate for 5 minutes and then stop for 15 minutes.