CN112079723A - Selective preparation method of copper-catalyzed alpha-nitronaphthalene - Google Patents
Selective preparation method of copper-catalyzed alpha-nitronaphthalene Download PDFInfo
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- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
A selective preparation method of copper-catalyzed alpha-nitronaphthalene comprises the steps of dissolving naphthalene and nitric acid in an organic solvent to form a homogeneous solution, adding a copper catalyst, reacting for 0.5-10 hours at 0-50 ℃, and carrying out aftertreatment to obtain the alpha-nitronaphthalene. The method uses copper as the catalyst, reduces the use amount of acid in the synthesis process, has simple operation, mild condition, short reaction time, very high selectivity on alpha-nitronaphthalene, can recycle the supported copper catalyst through centrifugal separation, has higher catalytic activity, and has cheap and easily obtained reaction raw materials, thereby being a novel high-efficiency preparation method.
Description
Technical Field
The invention relates to the field of organic synthesis and fine organic chemical industry, in particular to a selective preparation method of copper-catalyzed alpha-nitronaphthalene.
Background
Alpha-nitronaphthalene is a product after naphthalene nitration, is yellow crystalline powder at normal temperature, and is widely applied to manufacturing of important intermediates of rubber and organic synthesis and a stabilizer for explosives. Alpha-nitronaphthalene is also an important dye intermediate, and naphthoquinone imine, dinaphthylamine, nitronaphthylamine, naphthol and other compounds synthesized by the alpha-nitronaphthalene can be used as precursors of dyes or important components for synthesizing diazo compounds. Generally speaking, dyes derived from alpha-nitronaphthalene have the advantages of excellent performance, pure color light and the like, different varieties are frequently reported abroad, and some varieties are already put into the dye index (Penxinhua, Korean pine, Shichujie and the like. methods for synthesizing alpha-nitronaphthalene and beta-nitronaphthalene: China, CN102850225A [ P ] 2013, 01, 02.).
Some methods for synthesizing alpha-nitronaphthalene, such as classical synthesis, use naphthalene as raw material, and carry out nitration reaction in mixed acid composed of strong acid polar medium such as concentrated nitric acid and concentrated sulfuric acid to obtain mixture of alpha-nitronaphthalene and beta-nitronaphthalene (Johan, Chenxi Dong. Fine organic chemicals production handbook [ M Han Wen, Chenxi Dong. Fine organic chemicals production technology handbook ]]Beijing: the chemical industry of the publishing company has the following characteristics,2003: 489.); the Mohammad Ali Zolfigol topic group is NaNO3Water (H)2O)、SiO2As a nitration reagent, Silica gel supported Sulfuric Acid is used as a catalyst for reaction, and the reaction is carried out under the conditions of no solvent and 50 ℃ of reaction temperature to obtain a target product alpha-nitronaphthalene, (Mohammad A, BiBi F, Abdolamide B, et al]Bulletin of the Korea Chemical Society,2004,25(9): 1414-; bethany D.Powell group of subjects is naphthalene, nitric acid (HNO)3) And acetic anhydride (Ac)2O) as a reaction substrate, and trihexyl (tetradecyl) phosphine bis (trifluoromethylsulfonyl) amine as a solvent, and reacting at room temperature to obtain a mixture of alpha-nitronaphthalene and beta-nitronaphthalene (Bethany D, Gregory L, Perry C. phosphorus Ionic Liquids as solutions for Nitration Reactions of olefins [ J ]]Letters in Organic Chemistry,2005,2(6): 550-; Wan-Po Yin topic group is composed of naphthalene and 60% HNO3As a reaction substrate, in (OTf)3Reacting for 24 hours under the conditions of no solvent and 60 ℃ of reaction temperature by using a catalyst for reaction to obtain a target product alpha-nitronaphthalene (Wan-Po Yin, Min Shi. indium triflate as a reactive catalyst for the reaction of the nitro compound with the unsaturated carboxylic acid salt solution [ J-P Y ] (J-P-O-C)]Journal of Chemical Research,2006(9): 549-551), and the like. Although these methods are well established, there are some drawbacks, such as: the regioselectivity of the reaction is poor, and a large amount of beta-nitronaphthalene is generated in the nitration process; the mixed acid used in the reaction process generates a large amount of acidic waste, the treatment process is complicated, and the equipment is easy to corrode and the environment is easy to pollute; the reaction usually requires heating; longer reaction time, etc. Therefore, there is a need to develop new and efficient catalytic synthesis processes.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention aims to provide a selective preparation method of copper-catalyzed alpha-nitronaphthalene.
In order to achieve the purpose, the invention adopts the following technical scheme:
a selective preparation method of copper-catalyzed alpha-nitronaphthalene comprises the steps of dissolving naphthalene and nitric acid in an organic solvent to form a homogeneous solution, adding a copper catalyst, reacting for 0.5-10 hours at 0-50 ℃, and carrying out aftertreatment to obtain the alpha-nitronaphthalene.
The invention is further improved in that the organic solvent is one of dichloromethane, dichloroethane, toluene, dimethyl sulfoxide and 1, 4-dioxane.
A further improvement of the present invention is that the copper catalyst is a homogeneous catalyst or a supported heterogeneous catalyst.
The invention is further improved in that the homogeneous catalyst is copper powder, cuprous chloride, cuprous iodide, cupric oxide, copper trifluoromethanesulfonate, cupric nitrate, cupric acetate, cupric fluoride or cupric chloride.
In a further development of the invention, the supported heterogeneous catalyst is prepared by the following process: adding a carrier to Cu (NO)3)2·3(H2O) water solution, then roasting for 4 hours at 500 ℃, and finally reducing for 3 hours at 280 ℃ in a hydrogen atmosphere;
wherein the carrier is SiO2、Al2O3、ZnO、ZrO2、MgO、TiO2ZSM-5, SBA-15, USY or SAPO-11; the mass fraction of copper in the supported heterogeneous catalyst is 10%.
The further improvement of the invention is that when the copper catalyst is a supported heterogeneous catalyst, the catalyst is separated in a centrifugal mode after reacting for 0.5-10 hours, and can be recycled after drying.
A further development of the invention is that the ratio of the amounts of naphthalene and nitric acid substances is 1: (2-4), wherein the mass concentration of the nitric acid is 65%.
A further improvement of the invention is that the ratio of the amounts of the species of naphthalene and copper catalyst is 1: (0.05-0.20).
Compared with the prior art, the invention has the following beneficial effects: the invention changes the traditional mixed acid synthesis method, reduces the use of acid, and can ensure the smooth reaction by adding the copper catalyst in the reaction process. The reaction process is simple and efficient, the operation is convenient, the condition is mild, the reaction time is short, the high-selectivity synthesis of the nitronaphthalene compound is realized by a one-pot method, and the alpha-nitronaphthalene in the preparation process: mass ratio of β -nitronaphthalene > 98: 2; the synthetic route has strong selectivity and high synthetic efficiency; the reaction raw materials adopted by the invention are cheap and easy to obtain, and the method has wide application prospect.
Furthermore, the dosage of the copper catalyst is catalytic amount, and the dosage is less.
Furthermore, the supported copper catalyst can be recycled through centrifugal separation, and has high catalytic activity;
Detailed Description
In order to further understand the present invention, the following examples are further illustrated, which are only used for explaining the present invention and are not to be construed as limiting the scope of the present invention.
The invention takes naphthalene and nitric acid as raw materials and copper as a catalyst to prepare the alpha-nitronaphthalene at a certain temperature with high selectivity.
The invention provides a selective preparation method of copper-catalyzed alpha-nitronaphthalene, which comprises the following steps: dissolving naphthalene and nitric acid in an organic solvent to form a homogeneous solution, then adding a copper catalyst, and reacting for 0.5-10 hours at the temperature of 0-50 ℃, wherein in the preparation process, alpha-nitronaphthalene: mass ratio of β -nitronaphthalene > 98: 2, carrying out post-treatment to obtain the alpha-nitronaphthalene.
Wherein the organic solvent is one of dichloromethane, dichloroethane, toluene, dimethyl sulfoxide and 1, 4-dioxane.
The copper catalyst may be one of homogeneous catalysts such as copper powder, cuprous chloride, cuprous iodide, copper oxide, copper trifluoromethanesulfonate, copper nitrate, copper acetate, copper fluoride and copper chloride, or may be Cu (NO) by impregnation method3)2·3(H2O) is Cu/SiO prepared by taking precursor as2、Cu/Al2O3、Cu/ZnO、Cu/ZrO2、Cu/MgO、Cu/TiO2And one of supported heterogeneous catalysts such as Cu/ZSM-5, Cu/SBA-15, Cu/USY and Cu/SAPO-11, wherein the mass fraction of copper is 10% for all the supported heterogeneous catalysts.
In particular, the loadThe heterogeneous catalyst of type (II) is prepared by the following processes: adding a carrier to Cu (NO)3)2·3(H2O) water solution, then roasting for 4 hours at 500 ℃, and finally reducing for 3 hours at 280 ℃ in a hydrogen atmosphere;
wherein the carrier is SiO2、Al2O3、ZnO、ZrO2、MgO、TiO2ZSM-5, SBA-15, USY or SAPO-11; the mass fraction of copper in the supported heterogeneous catalyst is 10%.
When the copper catalyst is a heterogeneous catalyst, the catalyst can be separated in a centrifugal mode after the reaction is finished, and the catalyst can be directly recycled after being dried.
The reaction is carried out at normal pressure.
The mass ratio of naphthalene to copper catalyst was 1: (0.05-0.20); the mass ratio of naphthalene to nitric acid is 1: (2-4).
In the preparation process, alpha-nitronaphthalene: mass ratio of β -nitronaphthalene > 98: 2.
the following are specific examples.
Example 1
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 1mmol) and 2.5mg (0.025mmol) of cuprous chloride in a 25mL reaction tube, adding 2mL of toluene, wherein the mass ratio of naphthalene to cuprous chloride is 1: 0.05, the mass ratio of naphthalene to nitric acid is 1: 2; the reaction was carried out under magnetic stirring at 0 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 10 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, and taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product to obtain the alpha-nitronaphthalene.
Example 2
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 1.5mmol) and 9.6mg (0.05mmol) of cuprous iodide into a 25mL reaction tube, adding 2mL of 1, 2-dichloroethane, wherein the mass ratio of naphthalene to cuprous iodide is 1: 0.10, the mass ratio of naphthalene to nitric acid is 1: 3; the reaction was carried out under magnetic stirring at 10 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 10 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, and taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product to obtain the alpha-nitronaphthalene.
Example 3
64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and 6.4mg (0.1mmol) of copper powder are weighed respectively into a 25mL reaction tube, 2mL of dichloromethane is added, and the mass ratio of naphthalene to copper powder is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 1 hour, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 93 percent.
Example 4
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and 8mg (0.1mmol) of copper oxide in a 25mL reaction tube, adding 2mL of dimethyl sulfoxide, wherein the mass ratio of naphthalene to copper oxide is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 30 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 6 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 10%.
Example 5
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and 36.2mg (0.1mmol) of copper trifluoromethanesulfonate in a 25mL reaction tube, adding 2mL of 1, 4-dioxane, wherein the mass ratio of the naphthalene to the copper trifluoromethanesulfonate is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 40 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 10 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 5%.
Example 6
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and 24.2mg (0.1mmol) of copper nitrate into a 25mL reaction tube, adding 2mL of 1, 2-dichloroethane, wherein the mass ratio of the naphthalene to the copper nitrate is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 50 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 0.6 hour, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking 300-400 mesh silica gel as a stationary phase, and taking mixed solvents of ethyl acetate and petroleum ether in different proportions as eluents to separate and purify the product to obtain the alpha-nitronaphthalene, wherein the yield of the alpha-nitronaphthalene is 87%.
Example 7
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and 18.2mg (0.1mmol) of copper acetate in a 25mL reaction tube, adding 2mL of 1, 2-dichloroethane, wherein the mass ratio of the naphthalene to the copper acetate is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 10 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 57%.
Example 8
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and 10.2mg (0.1mmol) of copper fluoride into a 25mL reaction tube, adding 2mL of 1, 2-dichloroethane, wherein the mass ratio of the naphthalene to the copper fluoride is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 10 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 59%.
Example 9
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and 17.1mg (0.1mmol) of copper chloride into a 25mL reaction tube, adding 2mL of 1, 2-dichloroethane, wherein the mass ratio of the naphthalene to the copper chloride is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 10 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 84%.
Example 10
64mg (0.5mmol) of naphthalene, 2mmol of nitric acid (65 mass percent) and Cu/SiO are respectively weighed2Into a 25mL reaction tube, 2mL of methylene chloride, naphthalene and Cu/SiO were added2The mass ratio of (1): 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 2 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of the alpha-nitronaphthalene of 97%.
Example 11
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and Cu/SAPO-11 into a 25mL reaction tube, adding 2mL of dichloromethane, wherein the mass ratio of naphthalene to Cu/SAPO-11 is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 0.5 hour, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking 300-400 mesh silica gel as a stationary phase, and taking mixed solvents of ethyl acetate and petroleum ether in different proportions as eluents to separate and purify the product to obtain the alpha-nitronaphthalene, wherein the yield of the alpha-nitronaphthalene is 95%.
Example 12
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and Cu/ZnO in a 25mL reaction tube, adding 2mL of dichloromethane, wherein the mass ratio of naphthalene to Cu/ZnO is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 6 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 96%.
Example 13
64mg (0.5mmol) of naphthalene, 2mmol of nitric acid (65 mass percent) and Cu/ZrO were weighed out respectively2Into a 25mL reaction tube, 2mL of methylene chloride, naphthalene and Cu/ZrO were added2The mass ratio of (1): 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 2 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 92%.
Example 14
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and Cu/MgO in a 25mL reaction tube, adding 2mL of dichloromethane, wherein the mass ratio of naphthalene to Cu/MgO is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 6 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 80%.
Example 15
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and Cu/TiO2Into a 25mL reaction tube, 2mL of methylene chloride, naphthalene and Cu/TiO were added2The mass ratio of (1): 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. After 0.5 hourStopping the reaction, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking 300-400-mesh silica gel as a stationary phase, and taking mixed solvents of ethyl acetate and petroleum ether in different proportions as eluents to separate and purify the product to obtain the alpha-nitronaphthalene, wherein the yield of the alpha-nitronaphthalene is 93%.
Example 16
64mg (0.5mmol) of naphthalene, 2mmol of nitric acid (65 mass percent) and Cu/Al are respectively weighed2O3Into a 25mL reaction tube, 2mL of methylene chloride, naphthalene and Cu/Al were added2O3The mass ratio of (1): 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 1 hour, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 94 percent.
Example 17
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and Cu/SBA-15 into a 25mL reaction tube, adding 2mL of dichloromethane, wherein the mass ratio of naphthalene to Cu/SBA-15 is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 6 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 89%.
Example 18
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and Cu/USY into a 25mL reaction tube, adding 2mL of dichloromethane, wherein the mass ratio of naphthalene to Cu/USY is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 3 hours, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, washing the water phase with ethyl acetate for 3-5 times, combining, drying, filtering and concentrating the organic phase, separating by column chromatography, taking silica gel with 300-400 meshes as a stationary phase, taking mixed solvents of ethyl acetate and petroleum ether with different proportions as eluents to separate and purify the product, and obtaining the alpha-nitronaphthalene with the yield of 86%.
Example 19
Respectively weighing 64mg (0.5mmol) of naphthalene, 65% of nitric acid (mass concentration, 2mmol) and Cu/ZSM-5 into a 25mL reaction tube, adding 2mL of dichloromethane, wherein the mass ratio of naphthalene to Cu/ZSM-5 is 1: 0.20, the mass ratio of naphthalene to nitric acid is 1: 4; the reaction was carried out under magnetic stirring at 20 ℃ and the progress of the reaction was monitored by thin layer chromatography. Stopping the reaction after 1 hour, adding 5mL of saturated sodium carbonate solution to neutralize excessive nitric acid, centrifugally separating a catalyst Cu/ZSM-5, drying for later use, washing a water phase for 3-5 times by using ethyl acetate, combining, drying, filtering and concentrating an organic phase, separating by using column chromatography, separating and purifying a product by using 300-400 meshes of silica gel as a stationary phase and using mixed solvents of ethyl acetate and petroleum ether in different proportions as an eluent to obtain the alpha-nitronaphthalene, wherein the yield of the alpha-nitronaphthalene is 95%.
Example 20
The Cu/ZSM-5 catalyst recovered in example 19 was used for the second time, the catalytic reaction in example 19 was repeated, and the catalyst Cu/ZSM-5 was centrifugally separated and dried for use, and the objective compound α -nitronaphthalene was smoothly synthesized with a separation yield of 89%.
Example 21
The Cu/ZSM-5 catalyst recovered in the example 19 was used for the third time, the catalytic reaction in the example 19 was repeated, and the catalyst Cu/ZSM-5 was centrifugally separated and dried for later use to smoothly synthesize the objective compound, alpha-nitronaphthalene, with a separation yield of 80%.
Example 22
The Cu/ZSM-5 catalyst recovered in the example 19 is used for the fourth time, the catalytic reaction in the example 19 is repeated, the catalyst Cu/ZSM-5 is centrifugally separated, and the catalyst Cu/ZSM-5 is dried for standby use, so that the target compound alpha-nitronaphthalene is successfully synthesized, and the separation yield is 82%.
It can be seen from examples 19-22 that, taking naphthalene and nitric acid as raw materials to prepare the compound α -nitronaphthalene as an example, after the reaction is finished, the catalyst Cu/ZSM-5 is recovered by centrifugal separation and directly used in the next round of reaction, and is recycled for four times, the conversion rates of naphthalene are respectively 100%, 96%, 92% and 91%, and the separation yields of the target compound are respectively 95%, 89%, 80% and 82%, which proves that the catalyst has better cyclic usability, and still has good catalytic activity after four times.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and the modifications and decorations shall also fall within the scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (8)
1. A selective preparation method of copper-catalyzed alpha-nitronaphthalene is characterized by dissolving naphthalene and nitric acid in an organic solvent to form a homogeneous solution, then adding a copper catalyst, reacting for 0.5-10 hours at 0-50 ℃, and carrying out aftertreatment to obtain the alpha-nitronaphthalene.
2. The selective copper-catalyzed process of producing alpha-nitronaphthalene of claim 1, wherein the organic solvent is one of dichloromethane, dichloroethane, toluene, dimethyl sulfoxide, and 1, 4-dioxane.
3. The method of claim 1, wherein the copper catalyst is a homogeneous catalyst or a supported heterogeneous catalyst.
4. The selective copper-catalyzed preparation of α -nitronaphthalene of claim 3, wherein the homogeneous catalyst is copper powder, cuprous chloride, cuprous iodide, cupric oxide, cupric trifluoromethanesulfonate, cupric nitrate, cupric acetate, cupric fluoride or cupric chloride.
5. The selective copper-catalyzed preparation of α -nitronaphthalene of claim 3, wherein the supported heterogeneous catalyst is prepared by: adding a carrier to Cu (NO)3)2·3(H2O) water solution, then roasting for 4 hours at 500 ℃, and finally reducing for 3 hours at 280 ℃ in a hydrogen atmosphere;
wherein the carrier is SiO2、Al2O3、ZnO、ZrO2、MgO、TiO2ZSM-5, SBA-15, USY or SAPO-11; the mass fraction of copper in the supported heterogeneous catalyst is 10%.
6. The selective preparation method of copper-catalyzed alpha-nitronaphthalene according to claim 3, wherein when the copper catalyst is a supported heterogeneous catalyst, the catalyst is separated in a centrifugal manner after reacting for 0.5 to 10 hours, and can be recycled after drying.
7. The method of claim 1, wherein the amount of naphthalene to nitric acid is in a ratio of 1: (2-4), wherein the mass concentration of the nitric acid is 65%.
8. The method of claim 1, wherein the amount of naphthalene to copper catalyst is in a ratio of 1: (0.05-0.20).
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