Nitration phase continuous flow nitration method

Abstract

The invention relates to a nitration phase continuous flow nitration method. The method comprises the following steps: mixing a nitrating agent with a solvent 1 to obtain a nitration phase; dissolving and dispersing the raw materials through a solvent 2 to obtain a raw material phase; the nitration phase and the raw material phase are conveyed into a continuous flow reactor according to a certain flow velocity ratio, a nitration product is obtained after reaction, and continuous nitration synthesis is achieved. The nitrating agent comprises one or more of nitrate or a solid nitrating agent obtained by mixing nitrate and sulfate, grinding and sieving; nitrate, or a mixture of nitrate and sulfate, and a nitration auxiliary agent are mixed to obtain a solid nitrating agent; the fluid nitrating agent is prepared from nitrate, or a mixture of nitrate and sulfate, and water and / or a nitrating auxiliary agent; nitric acid is used as a nitrating agent; nitric acid and a nitration auxiliary agent are mixed to obtain a fluid nitrating agent; and nitrogen pentoxide. Compared with the prior art, the method provided by the invention has the advantages of no use of mixed acid, mild and controllable reaction conditions, less by-products, less amount of acid wastewater generated by the process and obvious industrialization prospect.

Description

Technical Field

[0001] This invention relates to the field of fine chemical technology, and in particular to a continuous flow nitration method for nitration phase. Background Technology

[0002] Nitration refers to the reaction that introduces a nitro group into an organic molecule. Conventional nitration processes are generally batch processes. CN116478094A discloses a method for preparing 3,4-dinitropyrazole using a batch nitration process, employing fuming nitric acid as the nitrating agent. However, nitration is a highly hazardous process, and the stability and safety of the nitration reaction have always been key concerns in chemical safety production. Batch nitration processes have high production risks, while continuous flow nitration processes offer better safety and are currently the main direction for technological research and industrialization. CN114957107A discloses a method for the continuous synthesis of 2,6-diamino-3,5-dinitropyridine using a mixed acid composed of sulfuric acid and nitric acid as the nitrating phase and a microchannel reactor. This method achieves the development of a continuous nitration process, but on the one hand, the mixed acid is highly corrosive to metal equipment, shortening its service life; on the other hand, the cost of treating and recovering the remaining nitric acid after the reaction is high. Therefore, the overall process still faces many challenges in industrialization. CN117945821A discloses the development of an intermittent nitration process for aromatic compounds using metal nitrates such as ferric nitrate and cerium nitrate as nitrating agents. While this method avoids the use of mixed acids, the intermittent operation cannot prevent batch-to-batch product quality variations. Furthermore, this process is a solid-liquid reaction system, and the low solid-liquid heterogeneous mass transfer efficiency of the intermittent process leads to a longer reaction time, increasing the risk of thermal decomposition of the reaction product and limiting the process's efficiency improvement. CN114773201A discloses a method for the rapid preparation of 1-methoxy-4-nitronaphthalene based on microchannel continuous flow technology. This method includes the following steps: 1. Pumping a nitrating agent and a corresponding solvent into a microchannel mixer at a certain ratio and mixing them at a certain temperature to form a nitrating agent solution; 2. Pumping the 1-methoxynaphthalene solution and the online-mixed nitrating agent solution into a microchannel reactor at a certain molar ratio and reacting at a certain temperature for a certain time to nitrate the product 1-methoxy-4-nitronaphthalene. The nitrating agent is at least one selected from nitric acid, nitrate, nitrogen oxides, and acetyl nitrate; preferably, the nitrate is potassium nitrate or sodium nitrate; preferably, the nitrogen oxide is dinitrogen trioxide or dinitrogen tetroxide. Although this method employs a sulfuric acid-free continuous flow process, its reaction system is specifically designed for the particular substrate 1-methoxynaphthalene, thus significantly limiting its substrate versatility. The potential compatibility and effectiveness of this method for other types of substrates (such as aromatic compounds with electron-withdrawing groups) remain to be verified. Therefore, there is an urgent need to develop a sulfuric acid-free, mild, and green nitration phase and establish a universal continuous flow nitration method. Summary of the Invention

[0003] The purpose of this invention is to overcome the defects of the prior art and provide a continuous flow nitration method with a nitrification phase. The method of this invention can overcome the defects of the existing intermittent nitration process with mixed acid or mixed nitrate system nitrification phase, such as large amount of sulfuric acid industrial wastewater, long reaction time, violent reaction and easy explosion of product decomposition, and low solid-liquid heterogeneous mass transfer efficiency. It provides a new, mild and green continuous flow nitration method with a sulfuric acid-free nitrification phase.

[0004] This invention can be achieved through the following technical solutions:

[0005] The purpose of this invention is to provide a continuous flow nitration method for a nitration phase, the continuous flow nitration method for a nitration phase comprising the following steps:

[0006] A certain amount of nitrifying agent is mixed with an appropriate amount of solvent 1 to obtain a homogeneous or heterogeneous fluid (suspension, emulsion, etc.) as the nitrifying phase;

[0007] After the raw materials are dissolved and dispersed in solvent 2, a mixed solution is obtained as the raw material phase;

[0008] The nitration phase and the feed phase are fed into a continuous flow reactor at a certain flow rate ratio, and the nitration product is obtained after the reaction, thus realizing continuous nitration synthesis.

[0009] Further, the nitrifying agent includes one or more of the following: a solid nitrifying agent obtained by grinding and sieving nitrates; a solid nitrifying agent obtained by grinding and sieving a mixture of nitrates and sulfates in a certain proportion; a solid nitrifying agent obtained by mixing nitrates and nitrification aids in a certain proportion; a solid nitrifying agent obtained by mixing nitrates and sulfates with nitrification aids in a certain proportion; a fluid nitrifying agent formed by mixing nitrates with water and / or nitrification aids in an appropriate proportion; a homogeneous or heterogeneous fluid nitrifying agent formed by mixing nitrates and sulfates with water and / or nitrification aids; nitric acid of a certain concentration used alone as a nitrifying agent; a homogeneous or heterogeneous fluid nitrifying agent obtained by mixing nitric acid with nitrification aids in an appropriate proportion; and nitrogen pentoxide.

[0010] Furthermore, the mass ratio of the mixture of nitrate and sulfate is 1:(0.1 to 100).

[0011] Furthermore, nitrates include one or more of the following: ferric nitrate nonahydrate, cerium nitrate, bismuth nitrate, potassium nitrate, gallium nitrate, magnesium nitrate hexahydrate, sodium nitrate, ammonium nitrate, and aluminum nitrate.

[0012] Furthermore, the sulfate includes one or more of magnesium sulfate, ferric sulfate, anhydrous aluminum sulfate, and ammonium sulfate.

[0013] Furthermore, the grinding process uses 500-3000 mesh particles for screening.

[0014] Preferably, the grinding process uses 1500-2000 mesh particles for screening.

[0015] Furthermore, the water has a molar concentration of 0.1–100 mol / L, calculated based on nitrate content.

[0016] Furthermore, the nitrification aid is 0.1% to 200% of the mass of nitric acid or nitrate.

[0017] Furthermore, the nitration aid is one or more of the following: phosphorus pentoxide, molecular sieve, calcium chloride, silica gel, activated alumina, glycerol, magnesium oxide, magnesium perchlorate, magnesium sulfate, sodium sulfate, activated carbon, montmorillonite, sodium polyacrylate, and acetic anhydride. The nitration aid is primarily a dehydrating agent and / or an aid for providing an acidic environment.

[0018] Furthermore, when the nitric acid is used alone as a nitrating agent, the concentration of the nitric acid is 10-98% by mass.

[0019] Further, the solvent 1 is selected from one or a mixture of more of the following: ethyl acetate, n-hexane, methanol, ethanol, isopropanol, difluoroethanol, trifluoroethanol, tetrafluoropropanol, hexafluoroisopropanol, hexafluorobutanol, dichloromethane, chloroform, dichloroethane, tetrahydrofuran, dioxane, acetic acid, diethyl ether, and acetonitrile.

[0020] Furthermore, the mixing ratio of the nitrifying agent to solvent 1 is a mass (g) to volume (mL) ratio of 1:(0.1~1000).

[0021] Furthermore, the raw material is one or more of a carbon-containing compound, a nitrogen-containing compound, or an oxygen-containing compound.

[0022] Furthermore, the solvent 2 is selected from one or more of methanol, ethanol, n-hexane, ethyl acetate, diethyl ether, dichloromethane, chloroform, difluoroethanol, trifluoroethanol, hexafluoroisopropanol, dichloroethane, tetrahydrofuran, 1,4-dioxane, and acetic acid.

[0023] Furthermore, the raw material phase is prepared by mixing the raw material and solvent 2 at a mass (g) to volume (mL) ratio of (1-100):10.

[0024] Further, the carbon-containing compound satisfies the following general structural formula: RC(R1R2)-H, the oxygen-containing compound satisfies the following general structural formula: ROH, and the nitrogen-containing compound satisfies the following general structural formula: RN(R1)-H, wherein R is a chain or cyclic saturated or unsaturated alkane group containing or not containing heteroatomic groups, or an aromatic group, and R1 and R2 are independently selected from H or C1-C6 alkane groups.

[0025] More preferably, R is a chain-like or cyclic saturated or unsaturated C1-C4 alkane group or a C6-C9 aromatic group, which may or may not contain heteroatom groups.

[0026] More preferably, the nitration products obtained from carbon-containing compound raw materials, oxygen-containing compound raw materials, or nitrogen-containing compound raw materials respectively satisfy the following general structural formulas: RC(R1R2)-NO2, RO-NO2, RN(R1)-NO2.

[0027] Furthermore, the ratio of the nitrification phase to the feed phase is: the ratio of the total amount of nitrate in the nitrifying agent in the nitrification phase to the amount of feed in the feed phase is 1 to 20:1.

[0028] Furthermore, the volumetric flow rate ratio of the nitrification phase to the feed phase is 0.3–2.5:1.

[0029] Furthermore, the nitrated phase and the feed phase are transported to the continuous flow reactor at a certain flow rate ratio using fluid transport equipment.

[0030] More preferably, the fluid transport device is a pump.

[0031] Furthermore, the continuous flow reactor is selected from one or more of microchannel reactors and tubular reactors.

[0032] Furthermore, the tubular reactor is selected from one or more of static tubular reactors and dynamic tubular reactors.

[0033] Furthermore, the reaction conditions for the continuous nitration synthesis are 0–160°C, the material residence time is 2–60 minutes, and the reaction pressure is 0–5 MPa. The preferred reaction pressure is 0.1–5 MPa.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] 1) The present invention provides a continuous flow nitration method for the nitration phase, in which the nitration phase does not contain concentrated sulfuric acid. Compared with the traditional continuous nitration process that uses a mixed acid of concentrated nitric acid and concentrated sulfuric acid as the nitration phase nitration system, this method does not use a mixed acid, therefore the reaction conditions are mild and controllable, there are few by-products, and the amount of acidic wastewater generated by the process is small, showing significant industrialization prospects.

[0036] 2) The continuous flow nitration method provided by this invention uses solid nitrifying agent obtained by grinding and sieving nitrate, or solid nitrifying agent obtained by mixing nitrate and sulfate in a certain proportion and then grinding and sieving, or solid nitrifying agent obtained by mixing nitrate and nitration aid in a certain proportion, or solid nitrifying agent obtained by mixing nitrate and sulfate in a certain proportion and then mixing with nitration aid in a certain proportion, or fluid nitrifying agent formed by nitrate and appropriate proportion of water and / or nitration aid, or homogeneous or heterogeneous fluid nitrifying agent formed by mixing nitrate and sulfate and then water and / or nitration aid, or nitric acid of a certain concentration used alone as nitrifying agent, or homogeneous or heterogeneous fluid nitrifying agent obtained by mixing nitric acid and appropriate proportion of nitration aid, or nitrogen pentoxide as nitrifying agent, combined with microchannel reactors and tubular reactors, to achieve continuous nitration synthesis. Compared to batch synthesis processes that use mixed acids or mixtures of nitrates, sulfates, and cerium nitrates as nitrating agents, its advantage lies in utilizing the high mass transfer coefficient of a continuous flow reactor, which improves reaction efficiency and shortens reaction time.

[0037] 3) The continuous flow nitration method provided by the present invention has the advantage of introducing nitration aids and utilizing the enhanced mass transfer characteristics of the continuous flow reactor, combined with continuous flow technology, to easily achieve heating and pressurization by introducing nitration aids and utilizing the enhanced mass transfer characteristics of the continuous flow reactor. Detailed Implementation

[0038] The present invention will now be described in detail with reference to specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments. In the specification and claims, "comprising" and "including" should be understood as "including, but not limited to," and the specific details disclosed are to make the present invention easier to understand. Those skilled in the art who implement this solution using one or more technical details also fall under the technical solution of the present invention. Component models, material names, connection structures, control methods, and other features not explicitly stated in the present invention are considered common technical features disclosed in the prior art.

[0039] In the following examples, the molecular sieves were all 3A molecular sieves purchased from Merck Chemical Technology (Shanghai) Co., Ltd.

[0040] The following examples all provide a rapid nitration phase continuous flow nitration method, and the specific steps are described in each example.

[0041] Example 1

[0042] Styrene (200g) and solvent 2 (dichloromethane) were mixed at a mass (g) to volume (mL) ratio of 33:100 as the raw material phase. Ferric nitrate nonahydrate and anhydrous aluminum sulfate were mixed at a mass ratio of 7:3, ground, and sieved to obtain 1000g of 2000-mesh particles. These particles were then mixed with anhydrous sodium sulfate as a nitrating agent, with the amount of anhydrous sodium sulfate added being 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (dichloroethane) to form the nitrated phase, with a volume of 2000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.8:1. The residence time of the materials in the tubular reactor was 25 minutes, the reaction temperature was 110℃, and the pressure was 2MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 196 g of the nitrated product 3-nitrostyrene, with a yield of 68%. 1 H NMR (300MHz, CDCl3): δ8.31(t,J=1.5Hz,1H); δ8.14(q,J=7.5,1.5Hz,1H); δ7.80(q,J=7.5,1.5Hz,1H); δ7.69( t,J=7.5Hz,1H); δ6.83(dd,J=16.8,10.0Hz,1H); δ6.01(dd,J=16.8,2.1Hz,1H); δ5.49(dd,J=10.0,2.1Hz,1H).

[0043] Example 2

[0044] Styrene (200g) and solvent 2 (ethanol) were mixed at a mass (g) to volume (mL) ratio of 4:10 as the raw material phase. Ferric nitrate nonahydrate (400g) and phosphorus pentoxide were used as nitrating agents, with phosphorus pentoxide accounting for 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1, which was isopropanol, at a volume of 1000mL, to form the nitrated phase. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 100℃, and the pressure was 1MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 190g of the nitrated product 3-nitrostyrene, with a yield of 66%.

[0045] Example 3

[0046] Styrene (200g) and solvent 2 (methanol) were mixed at a mass (g) to volume (mL) ratio of 3:10 as the raw material phase. Ferric nitrate nonahydrate (350g) was prepared as an aqueous solution with a concentration of 1 mol / L based on nitrate content, serving as the nitrating agent. The nitrating agent was mixed with solvent 1 to form the nitrated phase, where solvent 1 was ethanol, and the volume was 1000 mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.3:1. The residence time of the materials in the tubular reactor was 25 minutes, the reaction temperature was 90℃, and the pressure was 1 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 185g of the nitrated product 3-nitrostyrene, with a yield of 65%.

[0047] Example 4

[0048] Styrene (200g) and solvent 2 (ethanol) were mixed at a mass (g) to volume (mL) ratio of 4:10 as the raw material phase; 68% (w / w) concentrated nitric acid (400g) was used as the nitrating agent; the nitrating agent was mixed with solvent 1 to form the nitrated phase, wherein solvent 1 was isopropanol, and the volume was 300mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.2:1, the residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 100℃, and the pressure was 1MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the crude product was purified by vacuum distillation to obtain 195g of the nitrated product 3-nitrostyrene, with a yield of 68%.

[0049] Example 5

[0050] Ethyl 2-methylacetoacetate (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 3:10 as the raw material phase. Ferric nitrate nonahydrate and anhydrous aluminum sulfate were mixed at a mass ratio of 9:1, ground, and sieved to obtain 400g of 2000-mesh particles. These particles were then mixed with activated alumina as a nitrating agent, with the activated alumina addition being 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of isopropanol:dichloroethane = 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor, respectively. The cross-sectional area of ​​the pipes for the raw material phase and the nitrated phase was the same (the same in the following examples). The flow rate ratio was nitrated phase:raw material phase = 1.2:1. The residence time of the materials in the tubular reactor was 5 minutes, the reaction temperature was 60°C, and the pressure was 1MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was purified by vacuum distillation to give 192 g of the nitrated product, ethyl 2-methyl-2-nitroacetoacetate, in 73% yield. 1H NMR (300MHz, CDCl3): δ4.21 (d, J = 8.0 Hz, 2H), 2.10 (S, 3H), 1.99 (S, 3H), 1.28 (d, J = 8.0 Hz, 3H).

[0051] Example 6

[0052] Resorcinol (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 27:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2000-mesh particles. These particles were then mixed with silica gel as the nitrating agent, with the silica gel addition amount being 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of hexafluoroisopropanol:dichloromethane = 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.5:1. The residence time of the materials in the tubular reactor was 34 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 193 g of the nitrated product 4,6-dinitroresorcinol, with a yield of 65%. 1 H NMR (300MHz, DMSO): 14.43 (s, 1H); δ 14.43 (s, 1H); δ 8.47 (d, J = 8.0 Hz, 1H); δ 6.79 (d, J = 8.0 Hz, 1H).

[0053] Example 7

[0054] Benzoic acid (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with montmorillonite, a nitrating agent, as the nitrating agent. The amount of montmorillonite added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 188g of the nitrated product m-nitrobenzoic acid, with a yield of 70%. 1H NMR (300MHz, CDCl3): δ12.0(S1H),8.70(t,J=1.5,1.5Hz,1H),8.59(q,J=7.5 ,1.5,1.5Hz,1H),8.54(q,J=7.5,1.5,1.5Hz,1H),7.79(t,J=1.5,1.5Hz,1H).

[0055] Example 8

[0056] N-methylphthalimide (200g) and solvent 2 (acetic acid) were mixed at a mass (g) to volume (mL) ratio of 50:100 as the raw material phase. Ferric nitrate nonahydrate was ground and sieved, and 1000g of 2500-mesh particles were collected and mixed with acetic anhydride as a nitrating agent, wherein the amount of acetic anhydride added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was acetic acid, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 198 g of the nitrated product 4-nitro-N-methylphthalimide, with a yield of 70%. 1 H NMR (300MHz, CDCl3): δ3.95(3H,s),8.52(1H,dd,J=8.5,0.5Hz), 8.67-8.86(2H,8.73(dd,J=8.5,1.8Hz), 8.81(dd,J=1.8,0.5Hz).

[0057] Example 9

[0058] 2-(4-phenyl)butyric acid (200g) and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 50:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1, which was isopropanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 10 minutes, the reaction temperature was 89℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 189 g of the nitrated product 2-(4-nitrophenyl)butyric acid, with a yield of 68%. 1 H NMR (300MHz, DMSO): δ12.72(s,1H),8.17(dd,J=7.5,1.5Hz,2H),7.70(dd,J=7.5,1.5Hz,2H) ,3.55(d,J=7.0Hz,1H),1.90(d,J=7.0Hz,1H),1.90(d,J=7.0Hz,1H),0.86(d,J=8.0Hz,3H).

[0059] Example 10

[0060] 200g of benzonitrile and solvent 2 (hexafluoroisopropanol) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the raw material phase. Ferric nitrate nonahydrate was ground and sieved, and 1000g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, wherein the amount of molecular sieve added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was ethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.3:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 95℃, and the pressure was 1.0MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the crude product was purified by vacuum distillation to obtain 165g of the nitrated product p-nitrobenzonitrile, with a yield of 62%. 1 H NMR (300MHz, DMSO): δ7.85 (2H,ddd,J=8.7,2.1,0.5Hz), 8.18 (2H,ddd,J=8.7,2.2,0.5Hz).

[0061] Example 11

[0062] 200 g of o-nitrotoluene and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the feed phase; 1000 g of 68% nitric acid was added; and a nitrifying agent, trifluoroethanol, was dispersed in solvent 1 to form the nitrated phase, with a solvent volume of 1000 mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.5:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 120 °C, and the pressure was 1.5 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 190 g of the nitrated product 2,6-dinitrotoluene, with a yield of 73%. 1 H NMR: δ2.39(3H,s),7.66(1H,dd,J=8.1,0.4Hz), 8.43(1H,dd,J=8.1,1.9Hz), 8.59(1H,dd,J=1.9,0.4Hz).

[0063] Example 12

[0064] Ethyl 2-cyclohexanone carboxylate (200g) and solvent 2 (ethanol) were mixed at a mass (g) to volume (mL) ratio of 1:1 as the raw material phase. Ferric nitrate nonahydrate was ground and sieved, and 500g of 2000-mesh particles were mixed with molecular sieve as a nitrating agent, wherein the amount of molecular sieve powder added was 15% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 50℃, and the pressure was 1.0MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. Then, the crude product was purified by vacuum distillation to obtain 180g of 6-nitro-6-(ethoxycarbonyl)hexanoic acid, with a yield of 66%. 1 H NMR (300MHz, DMSO): δ11.87(s,1H),4.54(d,J=7.0Hz,1H),4.21(t,J=8.0Hz,1H),2.24(d,J=7.0Hz,1H) ,2.21(d,J=7.1Hz,1H),1.54(dd,J=7.1,7.1Hz,1H),1.25(dd,J=7.1,7.1Hz,1H),1.21(d,J=7.1Hz,3H).

[0065] Example 13

[0066] N,N-Diethylacetylacetamide (200g) and solvent 2 (ethanol) were mixed at a mass (g) to volume (mL) ratio of 1:1 as the raw material phase. Ferric nitrate nonahydrate was ground and sieved, and 450g of 2000-mesh particles were taken and mixed with molecular sieve as a nitrating agent, with the molecular sieve powder added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 80℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 152g of N,N-diethyl-2-nitroacetamide, with a yield of 75%. 1 H NMR (300MHz, DMSO): δ5.30 (t, J = 8.0 Hz, 2H), 3.34 (t, J = 8.0 Hz, 4H), 1.08 (d, J = 8.0 Hz, 6H).

[0067] Example 14

[0068] 1,4-Dimethylbenzene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with montmorillonite, a nitrating agent, as the nitrating agent. The amount of montmorillonite added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 221 g of the nitrated product 1,4-dimethyl-3-nitrobenzene, with a yield of 76%. 1 H NMR (300MHz, CDCl3): δ2.41-2.53(6H,2.46(s),2.48(s)),7.38-7.51(2H,7.44(dd,J=8.0,0.5Hz),7.45(dd,J=8.0,1.8Hz)),7.87(1H,dd,J=1.8,0.5Hz).

[0069] Example 15

[0070] 1,3,5-Trimethylbenzene (200g) and solvent 2 (tetrahydrofuran) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ammonium sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with montmorillonite, a nitrating agent, at a concentration of 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 95℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 221 g of the nitrated product 2-nitro-1,3,5-trimethylbenzene, with a yield of 74%. 1 H NMR (300MHz, CDCl3): δ2.30-2.42 (9H, 2.35 (s), 2.37 (s)), 7.17 (2H, d, J = 1.3Hz).

[0071] Example 16

[0072] 1,2,4,5-Tetramethylbenzene (200g) and solvent 2 (acetic acid) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Magnesium nitrate hexahydrate and ferric sulfate were mixed at a mass ratio of 100:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with phosphorus pentoxide as a nitrating agent, with the phosphorus pentoxide addition amounting to 10% of the mass of magnesium nitrate hexahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of trifluoroethanol:ethanol = 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.8:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 187 g of the nitrated product 1,2,4,5-tetramethyl-3-nitrobenzene, with a yield of 71%. 1 H NMR (300MHz, CDCl3): δ2.34-2.44(12H,2.39(s),2.39(s)),7.09(1H,s).

[0073] Example 17

[0074] Chlorobenzene (200g) and solvent 2 (dichloromethane) were mixed at a mass (g) to volume (mL) ratio of 30:100 as the raw material phase. Potassium nitrate and magnesium sulfate were mixed at a mass ratio of 50:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with calcium chloride, a nitrifying aid, as the nitrifying agent. The amount of calcium chloride added was 20% of the mass of potassium nitrate. The nitrifying agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of tetrafluoropropanol to dichloroethane of 100:30, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 125g of the nitrated product p-nitrochlorobenzene, with a yield of 56%. 1 H NMR (300MHz, CDCl3): δ7.62 (2H,ddd,J=8.5,1.5,0.4Hz), 8.09 (2H,ddd,J=8.5,2.1,0.4Hz).

[0075] Example 18

[0076] 200g of bromobenzene and solvent 2 (1,4-dioxane) were mixed at a mass-to-volume ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass-to-volume ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with silica gel as the nitrating agent. The silica gel was added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 133g of the nitrated product p-nitrobromobenzene, with a yield of 50%. 1 H NMR (300MHz, CDCl3): δ7.57 (2H,ddd,J=8.5,1.3,0.4Hz), 8.09 (2H,ddd,J=8.5,2.1,0.4Hz).

[0077] Example 19

[0078] Fluorobenzene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 80:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 20% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to dichloromethane of 100:30, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 1.3:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 100℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 123g of the nitrated product p-nitrofluorobenzene, with a yield of 50%. 1 H NMR (300MHz, CDCl3): δ7.42 (2H,ddd,J=8.6,1.2,0.4Hz), 8.11 (2H,ddd,J=8.6,2.1,0.4Hz).

[0079] Example 20

[0080] 200g of p-nitrobromobenzene and solvent 2 (hexafluorobutanol) were mixed at a mass (g) to volume (mL) ratio of 25:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with montmorillonite, a nitrating aid, as the nitrating agent. The amount of montmorillonite added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of diethyl ether to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 1.5:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 196 g of the nitrated product 2,4-dinitrobromobenzene, with a yield of 69%. 1 H NMR (300MHz, CDCl3): δ7.77(1H,dd,J=7.7,0.5Hz), 8.40(1H,dd,J=7.7,1.9Hz), 8.63(1H,dd,J=1.9,0.5Hz).

[0081] Example 21

[0082] 200g of p-nitrochlorobenzene and solvent 2 (hexafluoroisopropanol) were mixed at a mass (g) to volume (mL) ratio of 50:100 as the raw material phase. Magnesium nitrate hexahydrate and magnesium sulfate were mixed at a mass ratio of 60:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with magnesium perchlorate, a nitrating aid, as the nitrating agent. The amount of magnesium perchlorate added was 15% of the mass of magnesium nitrate hexahydrate. The nitrating agent was dispersed in solvent 1 (dichloroethane) to form the nitrated phase, with 1000mL of solvent 1. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 190 g of the nitrated product 2,4-dinitrochlorobenzene, with a yield of 71%. 1 H NMR (300MHz, CDCl3): δ7.88(1H,dd,J=8.6,0.5Hz), 8.32(1H,dd,J=8.6,1.9Hz), 8.62(1H,dd,J=1.9,0.5Hz).

[0083] Example 22

[0084] 200g of p-nitrofluorobenzene and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with montmorillonite, a nitrating aid, as the nitrating agent. The amount of montmorillonite added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 75℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 195 g of the nitrated product 2,4-dinitrofluorobenzene, with a yield of 70%. 1 H NMR (300MHz, CDCl3): δ7.79 (1H,dd,J=8.3,0.5Hz), 8.42 (1H,dd,J=8.3,1.9Hz), 8.70 (1H,dd,J=1.9,0.5Hz).

[0085] Example 23

[0086] Benzene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Sodium nitrate was ground and sieved, and 1000g of 2500-mesh particles were taken and mixed with activated alumina, a nitrating aid, as the nitrating agent. The amount of activated alumina added was 10% of the mass of sodium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was prepared at a volume ratio of methanol:difluoroethanol = 90:15, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor separately using a pump at a flow rate ratio of nitrated phase:raw material phase = 0.9:1. The residence time of the materials in the tubular reactor was 10 minutes, the reaction temperature was 60℃, and the pressure was 0.1MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 163g of the nitrated product nitrobenzene, with a yield of 58%. 1 HNMR (300MHz, CDCl3): δ7.41-7.63(3H,7.48(dddd,J=8.3,7.9,1.5,0.4Hz),7.57(tt,J=7.9,1.9Hz)),8.20(2H,dtd,J=8.3,1.9,0.4Hz).

[0087] Example 24

[0088] 200g of refined naphthalene and solvent 2 (ethyl acetate) were mixed at a mass (g) to volume (mL) ratio of 45:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 100:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:20, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 1.2:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 110℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 170 g of the nitrated product 1-nitronaphthalene, with a yield of 59%. 1HNMR (300MHz, CDCl3): δ7.59-7.75(2H,7.67(dddd,J=7.7,7.3,1.5,0.4Hz) ,7.68(ddd,J=8.6,8.1,0.4Hz)),7.81-8.04(3H,7.87(dtt,J=7.7,1.4,0.5H z),7.91(ddd,J=7.9,7.3,1.4Hz),7.98(ddq,J=7.9,1.5,0.5Hz)),8.05-8. 30(2H,8.12(dddt,J=8.1,2.5,1.4,0.5Hz),8.23(ddd,J=8.6,2.5,0.5Hz)).

[0089] Example 25

[0090] Methyl benzoate (200g) and solvent 2 (chloroform) were mixed at a mass (g) to volume (mL) ratio of 12:100 as the raw material phase. Ammonium nitrate was mixed, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with acetic anhydride, a nitrating agent, as the nitrating agent. The amount of acetic anhydride added was 10% of the mass of ammonium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of n-hexane:acetic acid = 100:30, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.2:1. The residence time of the materials in the tubular reactor was 35 minutes, the reaction temperature was 100℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 187g of the nitrated product, methyl m-nitrobenzoate, with a yield of 69%. 1 H NMR (300MHz, CDCl3): δ3.82(3H,s),7.72(1H,ddd,J=8.1,8.0,0.4Hz),8.07(1H,ddd ,J=8.0,1.9,1.7Hz),8.37(1H,ddd,J=8.1,1.9,1.6Hz),8.78(1H,td,J=1.7,0.4Hz).

[0091] Example 26

[0092] Trifluorotoluene (200g) and solvent 2 (hexafluoroisopropanol) were mixed at a mass (g) to volume (mL) ratio of 10:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 100:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with activated alumina, a nitrating agent, as the nitrating agent. The activated alumina was added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase. Solvent 1 was prepared from dichloroethane, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 120℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 188 g of the nitrated product m-nitrotrifluorotoluene, with a yield of 67%. 1 H NMR (300MHz, CDCl3): δ7.62(1H,ddd,J=8.2,7.7,0.5Hz), 7.83(1H,dt,J=7.7,1.6Hz), 8.22(1H,ddd,J=8.2,1.9,1.6Hz), 8.56(1H,ddd,J=1.9,1.6,0.5Hz).

[0093] Example 27

[0094] 200g of bromotrifluorotoluene and solvent 2 (tetrahydrofuran) were mixed at a mass (g) to volume (mL) ratio of 15:100 to form the raw material phase. Ferric nitrate nonahydrate was ground and sieved, and 1000g of 2500-mesh particles were collected and mixed with phosphorus pentoxide as a nitrating agent, wherein the amount of phosphorus pentoxide added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was prepared at a volume ratio of ethyl acetate:tetrafluoropropanol = 100:35, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.4:1. The residence time of the materials in the tubular reactor was 50 minutes, the reaction temperature was 120℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 179 g of the nitrated product 4-bromo-3-nitrotrifluorotoluene, with a yield of 65%. 1 H NMR (300MHz, CDCl3): δ7.72-7.86(2H,7.78(dd,J=8.7,1.6Hz),7.80(dd,J=8.7,0.5Hz)),8.72(1H,dd,J=1.6,0.5Hz).

[0095] Example 28

[0096] p-Toluenesulfonic acid (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with molecular sieves as a nitrating agent. The molecular sieves were added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 176 g of the nitrated product 3-nitro-4-methylbenzenesulfonic acid, with a yield of 64%. 1 H NMR (300MHz, CDCl3): δ2.39(3H,s),8.12-8.32(2H,8.18(dd,J=7.9,1.4Hz),8.26(dd,J=7.9,0.5Hz)), 8.83(1H,dd,J=1.4,0.5Hz).

[0097] Example 29

[0098] 200g of m-nitrobenzoic acid and solvent 2 (n-hexane) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the raw material phase. Cerium nitrate and ammonium sulfate were mixed at a mass ratio of 120:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with a molecular sieve nitrating aid as the nitrating agent. The molecular sieve nitrating aid was added at 20% of the mass of cerium nitrate. The nitrating agent was dispersed in solvent 1 (acetonitrile) to form the nitrated phase, with 1000mL of solvent 1. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 140℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 201g of the nitrated product 3,5-dinitrobenzoic acid, with a yield of 72%. 1 H NMR (300MHz, DMSO): δ12.74 (1H, s), 9.21 (1H, t, J = 1.5Hz), 9.09 (2H, t, J = 1.5Hz).

[0099] Example 30

[0100] Anthraquinone (200g) and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 5:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 100:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 30% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of tetrafluoropropanol:ethanol = 100:50, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.3:1. The residence time of the materials in the tubular reactor was 45 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 187 g of the nitrated product 1-nitroanthraquinone, with a yield of 67%. 1 HNMR (300MHz, CDCl3): δ7.59(1H,ddd,J=8.5,8.2,1.7Hz),7.81(1H,dd,J=8.8,7.6Hz),8.14(1H,ddd,J=8.2,8.0,1.8Hz),8.36 -8.61(3H,8.43(dd,J=8.8,1.4Hz),8.51(ddd,J=8.5,1.8,0.5Hz),8.55(ddd,J=8.0,1.7,0.5Hz)),8.77(1H,dd,J=7.6,1.4Hz).

[0101] Example 31

[0102] Isopropanol (200g) and solvent 2 (dichloromethane) were mixed at a mass (g) to volume (mL) ratio of 30:100 as the feed phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 179g of the nitrated product, isopropyl nitrate, with a yield of 69%. 1 HNMR (300MHz, CDCl3): δ1.20 (6H, d, J = 6.8Hz), 5.21 (1H, q, J = 6.8Hz).

[0103] Example 32

[0104] Ethanol (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 25:100 as the raw material phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (dichloroethane) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.2:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 110℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 195g of the nitrated product, ethyl nitrate, with a yield of 50%. 1 H NMR (300MHz, CDCl3): δ1.19 (3H, t, J = 7.0Hz), 4.61 (2H, q, J = 7.0Hz).

[0105] Example 33

[0106] Ethylene glycol (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. 500g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (dichloroethane) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.2:1. The residence time of the materials in the tubular reactor was 9 minutes, the reaction temperature was 85℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 197g of the nitrated product, ethylene glycol dinitrate, with a yield of 49%. 1 H NMR (300MHz, CDCl3): δ4.86 (4H,t,J=4.9Hz).

[0107] Example 34

[0108] Phenol (200g) and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, wherein the amount of montmorillonite added as the nitrating agent was 15% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 15 minutes, the reaction temperature was 88℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 183g of the nitrated product o-nitrophenol, with a yield of 62%. 1 H NMR (300MHz, CDCl3): δ6.95(1H,ddd,J=8.3,1.2,0.5Hz),7.42(1H,ddd,J=8.1,7 .3,1.2Hz),7.63(1H,ddd,J=8.3,7.3,1.8Hz),8.13(1H,ddd,J=8.1,1.8,0.5Hz).

[0109] Example 35

[0110] 200 g of o-nitrophenol and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. 200 g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000 mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.9:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 110 °C, and the pressure was 1.5 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 201 g of the nitrated product 2,4-dinitrophenol, with a yield of 76%. 1 H NMR (300MHz, CDCl3): δ7.29 (1H,dd,J=7.9,0.5Hz), 8.37 (1H,dd,J=7.9,1.9Hz), 8.67 (1H,dd,J=1.9,0.5Hz).

[0111] Example 36

[0112] 200g of p-cresol and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 110℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 201g of the nitrated product 2-nitro-4-methylphenol, with a yield of 74%. 1 H NMR (300MHz, DMSO): δ14.43(s,1H),7.93(d,J=1.5Hz,1H),7.43(dd,J=7.5,1.5Hz,1H),7.14(d,J=7.5Hz,1H), δ2.30(s,3H).

[0113] Example 37

[0114] 2-Nitro-4-methylphenol (200g) and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 165g of the nitrated product 2,6-dinitro-4-methylphenol, with a yield of 54%. 1 H NMR (300MHz, DMSO): δ10.69 (s, 1H), 8.32 (d, J = 1.5Hz, 2H), 2.36 (s, 3H).

[0115] Example 38

[0116] 200 g of p-hydroxybenzaldehyde and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. 200 g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000 mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 15 minutes, the reaction temperature was 110 °C, and the pressure was 1.5 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 176 g of the nitrated product 3-nitro-4-hydroxybenzaldehyde, with a yield of 57%. 1 H NMR (300MHz, DMSO): δ14.43(s,1H), 9.80(s,1H), 8.25(d,J=1.5Hz,1H,), 8.10(dd,J=7.5,1.5Hz,1H), 7.26(d,J=7.5Hz,1H).

[0117] Example 39

[0118] Trifluoromethylphenol (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 25:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with phosphorus pentoxide as a nitrating agent, with the phosphorus pentoxide addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 196 g of the nitrated product 2-nitro-4-trifluoromethylphenol, with a yield of 75%. 1 H NMR (300MHz, DMSO): δ14.43 (s, 1H), 8.24 (d, J = 1.5Hz, 1H), 7.69 (dd, J = 7.5, 1.5Hz, 1H), 7.12 (d, J = 7.5Hz, 1H).

[0119] Example 40

[0120] 200g of 4-hydroxybenzonitrile and solvent 2 (methanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with molecular sieve as a nitrating agent. The amount of montmorillonite added as the nitrating agent was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of hexafluorobutanol to methanol of 100:20, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 1.2:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 166 g of the nitrated product 4-hydroxy-3-nitrobenzene, with a yield of 52%. 1 H NMR (300MHz, CDCl3): δ14.43 (s, 1H), 8.27 (d, J = 1.5Hz, 1H), 8.10 (dd, J = 7.5, 1.5Hz, 1H), 7.25 (d, J = 7.5Hz, 1H).

[0121] Example 41

[0122] 200 g of 4-hydroxybenzoic acid and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. 200 g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000 mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 85 °C, and the pressure was 1.5 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 192 g of the nitrated product, 4-hydroxy-3-nitrobenzoic acid, with a yield of 69%. 1 H NMR (300MHz, DMSO): δ14.43(s,1H),12.74(s,1H),8.41(d,J=1.5Hz,1H), δ8.32(dd,J=7.5,1.5Hz,1H), δ7.28(d,J=7.5Hz,1H).

[0123] Example 42

[0124] 200g of methyl 2-nitrobenzene and solvent 2 (difluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Bismuth nitrate and magnesium sulfate were mixed at a mass ratio of 100:20, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with magnesium sulfate, a nitrating aid, as the nitrating agent. The amount of magnesium sulfate added was 10% of the mass of bismuth nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 196 g of the nitrated product methyl 2,4-dinitrobenzoate, with a yield of 70%. 1 H NMR (300MHz, CDCl3): δ3.73(3H,s),7.84(1H,dd,J=8.5,0.5Hz), 8.32(1H,dd,J=8.5,1.8Hz), 8.79(1H,dd,J=1.8,0.5Hz).

[0125] Example 43

[0126] Dimethyl terephthalate (200g) and solvent 2 (diethyl ether) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with molecular sieves as a nitrating agent. The amount of molecular sieves added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to chloroform of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 35 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 201g of the nitrated product, dimethyl 2-nitroterephthalate, with a yield of 73%. 1 H NMR (300MHz, CDCl3): δ3.70(3H,s), 3.81(3H,s), 7.93(1H,dd,J=7.8,0.5Hz), 8.19(1H,dd,J=7.8,1.8Hz), 8.88(1H,dd,J=1.8,0.5Hz).

[0127] Example 44

[0128] Toluene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the feed phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.2:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 80℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 185g of the nitrated product, o-nitrotoluene, with a yield of 65%. 1 H NMR (300MHz, CDCl3): δ2.50(3H,s),7.41-7.71(3H,7.47(ddd,J=8.0,1.3,0.5Hz),7.53(d dd,J=8.2,7.7,1.3Hz),7.63(ddd,J=8.0,7.7,1.8Hz)),8.01(1H,ddd,J=8.2,1.8,0.5Hz).

[0129] Example 45

[0130] 200g of p-chlorotoluene and solvent 2 (ethyl acetate) were mixed at a mass (g) to volume (mL) ratio of 30:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, with the molecular sieve addition amounting to 25% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (hexafluoroisopropanol) to form the nitrated phase, with 1000mL of solvent 1. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.9:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 95℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 168 g of the nitrated product 2-nitro-4-chlorotoluene, with a yield of 51%. 1 H NMR (300MHz, CDCl3): δ2.50(3H,s),7.54(1H,dd,J=8.0,0.4Hz), 7.78(1H,dd,J=8.0,1.7Hz), 8.31(1H,dd,J=1.7,0.4Hz).

[0131] Example 46

[0132] 200g of 4-methylphenyl-p-toluenesulfonamide and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, with the molecular sieve added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.2:1. The residence time of the materials in the tubular reactor was 45 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 175 g of the nitrated product 4-methyl-3-nitrophenyl-p-toluenesulfonamide, with a yield of 53%. 1 HNMR (300MHz, CDCl3): δ10.20(s,1H),7.76(dd,J=7.5,1.5Hz,1H),7.69(d,J=1.5Hz,1H),7.68(dd ,J=7.5,1.5Hz,2H),7.53(d,J=7.5Hz,1H),7.34(dd,J=7.5,1.5Hz,2H),2.50(s,3H),2.43(s,3H).

[0133] Example 47

[0134] Iodobenzene (200g) and solvent 2 (acetic acid) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with molecular sieves as a nitrating agent. The amount of molecular sieves added was 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 120℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 167g of p-nitroboiodobenzene, with a yield of 56%. 1 HNMR (300MHz, CDCl3): δ7.56 (2H,ddd,J=8.5,1.4,0.4Hz), 8.08 (2H,ddd,J=8.5,1.9,0.4Hz).

[0135] Example 48

[0136] 1,3-Dichlorobenzene (200g) and solvent 2 (dichloromethane) were mixed at a mass (g) to volume (mL) ratio of 30:100 as the feed phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (tetrafluoropropanol) to form the nitrated phase, with a volume of 1000mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.5:1. The residence time of the materials in the tubular reactor was 50 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 165g of the nitrated product 2,4-dichloronitrobenzene, with a yield of 55%. 1 H NMR (300MHz, CDCl3): δ7.44(1H,dd,J=2.3,0.5Hz), 7.58(1H,dd,J=8.5,2.3Hz), 8.08(1H,dd,J=8.5,0.5Hz).

[0137] Example 49

[0138] 1,3-Dibromobenzene (200g) and solvent 2 (ethanol) were mixed at a mass (g) to volume (mL) ratio of 35:100 as the raw material phase. Sodium nitrate and sodium sulfate were mixed at a mass ratio of 100:20, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid added at 10% of the mass of sodium nitrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 155 g of the nitrated product 2,4-dibromonitrobenzene, with a yield of 50%. 1 H NMR (300MHz, CDCl3): δ7.31-7.50(2H,7.37(dd,J=1.9,0.5Hz),7.43(dd,J=8.6,1.9Hz)),8.09(1H,dd,J=8.6,0.5Hz).

[0139] Example 50

[0140] 1,3-Difluorobenzene (200g) and solvent 2 (chloroform) were mixed at a mass (g) to volume (mL) ratio of 10:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1, which was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.3:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 168 g of the nitrated product 2,4-difluoronitrobenzene, with a yield of 52%. 1 H NMR (300MHz, CDCl3): δ7.24(1H,dd,J=1.9,0.5Hz), 7.49(1H,dd,J=8.3,1.9Hz), 8.10(1H,dd,J=8.3,0.5Hz).

[0141] Example 51

[0142] 1,3-Diiodobenzene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 40:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 100:20, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with silica gel as the nitrating agent. The silica gel was added at 15% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (hexafluorobutanol) to form the nitrated phase, with 1000mL of solvent 1. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.9:1. The residence time of the materials in the tubular reactor was 60 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 166 g of the nitrated product 2,4-diiodonitrobenzene, with a yield of 52%. 1 H NMR (300MHz, CDCl3): δ7.07 (1H,dd,J=1.7,0.5Hz), 7.43 (1H,dd,J=8.6,1.7Hz), 8.09 (1H,dd,J=8.6,0.5Hz).

[0143] Example 52

[0144] 2-Bromotrifluoromethoxybenzene (200g) and solvent 2 (dichloromethane) were mixed at a mass (g) to volume (mL) ratio of 40:100 as the raw material phase. Gallium nitrate was ground and sieved, and 1000g of 2500-mesh particles were taken and mixed with acetic anhydride as a nitrating agent, wherein the amount of acetic anhydride added was 20% of the mass of gallium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was hexafluorobutanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor separately using a pump at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 175 g of the nitrated product 2-bromo-5-(trifluoromethoxy)nitrobenzene, with a yield of 54%. 1 HNMR (300MHz, CDCl3): δ7.59 (1H, dd, J = 8.5, 0.5 Hz), 8.10-8.24 (2H, 8.16 (dd, J = 8.5, 1.9 Hz), 8.19 (dd, J = 1.9, 0.5 Hz)).

[0145] Example 53

[0146] 2-Chlorotrifluoromethoxybenzene (200g) and solvent 2 (methanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Bismuth nitrate was ground and sieved, and 1000g of 2500-mesh particles were mixed with a nitrating agent molecular sieve as the nitrating agent, wherein the amount of the nitrating agent molecular sieve added was 15% of the mass of bismuth nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was trifluoroethanol:tetrafluoropropanol = 4:1 (volume ratio), and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.8:1. The residence time of the materials in the tubular reactor was 35 minutes, the reaction temperature was 140℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 125 g of the nitrated product 2-chloro-5-(trifluoromethoxy)nitrobenzene, with a yield of 43%. 1 H NMR (300MHz, CDCl3): δ7.69 (1H, dd, J = 7.8, 0.5 Hz), 8.08-8.22 (2H, 8.14 (dd, J = 1.9, 0.5 Hz), 8.16 (dd, J = 7.8, 1.9 Hz)).

[0147] Example 54

[0148] 2-Fluorotrifluoromethoxybenzene (200g) and solvent 2 (hexafluoroisopropanol) were mixed at a mass (g) to volume (mL) ratio of 40:100 as the raw material phase. Aluminum nitrate was ground and sieved, and 1000g of 2500-mesh particles were taken and mixed with activated alumina, a nitrating agent, as the nitrating agent. The amount of activated alumina added was 10% of the mass of aluminum nitrate. The nitrating agent was dispersed in solvent 1, which was trifluoroethanol, and the volume of solvent 1 was 1000mL to form the nitrated phase. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 177 g of the nitrated product 2-fluoro-5-(trifluoromethoxy)nitrobenzene, with a yield of 62%. 1 H NMR (300MHz, CDCl3): δ7.67 (1H, dd, J = 8.4, 0.5 Hz), 8.09-8.30 (2H, 8.15 (dd, J = 8.4, 1.9 Hz), 8.25 (dd, J = 1.9, 0.5 Hz)).

[0149] Example 55

[0150] 2-Iodotrifluoromethoxybenzene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:20, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1, which was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 165 g of the nitrated product 2-iodo-5-(trifluoromethoxy)nitrobenzene, with a yield of 52%. 1 H NMR (300MHz, CDCl3): δ7.27 (1H, dd, J = 8.5, 0.5 Hz), 8.09-8.22 (2H, 8.15 (dd, J = 8.5, 1.9 Hz), 8.17 (dd, J = 1.9, 0.5 Hz)).

[0151] Example 56

[0152] 2-Bromoanisole (200g) and solvent 2 (ethyl acetate) were mixed at a mass (g) to volume (mL) ratio of 25:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:15, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 consisted of acetic acid and difluoroethanol at a volume ratio of 3:1, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.9:1. The residence time of the materials in the tubular reactor was 35 minutes, the reaction temperature was 145℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 163 g of the nitrated product 2-bromo-5-nitroanisole, with a yield of 54%. 1 HNMR (300MHz, CDCl3): δ3.76(3H,s),7.47-7.61(2H,7.52(dd,J=1.9,0.5Hz),7.54(dd,J=8.6,0.5Hz)),7.72(1H,dd,J=8.6,1.9Hz).

[0153] Example 57

[0154] 2-Chloroanisole (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the feed phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (tetrafluoropropanol) to form the nitrated phase, with a volume of 1000mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 0.8:1. The residence time of the materials in the tubular reactor was 25 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 179g of the nitrated product, 2-chloro-5-nitrobenzene ether, with a yield of 56%. 1 H NMR (300MHz, CDCl3): δ3.75(3H,s),7.47-7.79(3H,7.53(dd,J=1.9,0.5Hz),7.61(dd,J=8.5,0.5Hz),7.72(dd,J=8.5,1.9Hz)).

[0155] Example 58

[0156] 2-Fluoroanisole (200g) and solvent 2 (hexafluoroisopropanol) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 100:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was ethanol:hexafluoroisopropanol at a volume ratio of 3:2, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 120℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 195 g of the nitrated product 2-fluoro-5-nitroanisole, with a yield of 63%. 1 HNMR (300MHz, CDCl3): δ3.78(3H,s),7.49-7.68(2H,7.54(dd,J=2.1,0.5Hz),7.62(dd,J=8.6,0.5Hz)), 8.04(1H,dd,J=8.6,2.1Hz).

[0157] Example 59

[0158] 2-Iodoanisole (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 12:100 as the feed phase. 200g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 110℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 198g of the nitrated product, 2-iodo-5-nitroanisole, with a yield of 70%. 1 H NMR (300MHz, CDCl3): δ3.69(3H,s),7.42-7.66(3H,7.48(dd,J=8.4,1.5Hz),7.53(dd,J=8.4,0.5Hz),7.61(dd,J=1.5,0.5Hz)).

[0159] Example 60

[0160] Anisole (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 28:100 as the raw material phase. Ammonium nitrate and ammonium sulfate were mixed at a mass ratio of 90:15, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid being 10% of the mass of ammonium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was dichloromethane:trifluoroethanol = 1:2 (volume ratio), and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 155g of the nitrated product p-nitrobenzyl ether, with a yield of 49%. 1 H NMR (300MHz, CDCl3): δ8.16 (2H, dd, J = 7.5, 1.5 Hz), 7.22 (2H, dd, J = 7.5, 1.5 Hz), 3.81 (3H, s).

[0161] Example 61

[0162] Nitroanisole (200g) and solvent 2 (ethanol) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, with the molecular sieve added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 165 g of the nitrated product 2,4-dinitroanisole, with a yield of 51%. 1 H NMR (300MHz, CDCl3): δ3.90(3H,s),7.35(1H,dd,J=7.9,0.5Hz), 8.36(1H,dd,J=7.9,1.9Hz), 8.65(1H,dd,J=1.9,0.5Hz).

[0163] Example 62

[0164] 200g of p-nitrobenzene and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 37:100 as the raw material phase. Ferric nitrate nonahydrate was ground and sieved, and 1000g of 2500-mesh particles were collected and mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1, which was trifluoroethanol, and the volume of solvent 1 was 1000mL to form the nitrated phase. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 10 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 157g of the nitrated product 2,4-dinitroiodobenzene, with a yield of 50%. 1 H NMR (300MHz, CDCl3): δ7.76 (1H,dd,J=8.6,0.5Hz), 8.39 (1H,dd,J=8.6,1.9Hz), 8.63 (1H,dd,J=1.9,0.5Hz).

[0165] Example 63

[0166] 200g of p-dimethoxybenzene and solvent 2 (ethyl acetate) were mixed at a mass (g) to volume (mL) ratio of 26:100 as the raw material phase. Sodium nitrate and sodium sulfate were mixed at a mass ratio of 80:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid being 10% of the mass of sodium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was a trifluoroethanol:ethyl acetate ratio of 2:1 (volume ratio), and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 1.5:1. The residence time of the materials in the tubular reactor was 25 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 178 g of the nitrated product 1,4-dimethoxy-2-nitrobenzene, with a yield of 58%. 1 H NMR (300MHz, CDCl3): δ3.82(3H,s),3.96(3H,s),6.97-7.13(2H,7.03(dd,J=8.5,0.5Hz),7.06(dd,J=8.5,2.8Hz)),7.48(1H,dd,J=2.8,0.5Hz).

[0167] Example 64

[0168] 3,5-Di-tert-butylbromobenzene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Aluminum nitrate was ground and sieved, and 1000g of 3000-mesh particles were taken and mixed with acetic anhydride as a nitrating agent, wherein the amount of acetic anhydride added was 10% of the mass of aluminum nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 190 g of the nitrated product 1-bromo-3,5-di-tert-butyl-2-nitrobenzene, with a yield of 72%. 1 HNMR (300MHz, CDCl3): δ2.25(3H,s), 2.35(3H,s), 6.58(1H,d,J=1.3Hz), 7.16(1H,d,J=1.3Hz).

[0169] Example 65

[0170] 200g of 4-bromo-2-chlorotoluene and solvent 2 (n-hexane) were mixed at a mass (g) to volume (mL) ratio of 26:100 as the raw material phase. Potassium nitrate was ground and sieved, and 1000g of 2000-mesh particles were taken and mixed with montmorillonite, a nitrifying aid, as the nitrating agent. The amount of montmorillonite added was 10% of the mass of potassium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was trifluoroethanol:n-hexane = 2:1 (volume ratio), and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 15 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 188 g of the nitrated product 3-chloro-5-bromo-2-methylnitrobenzene, with a yield of 64%. 1 H NMR (300MHz, CDCl3): δ2.46 (3H,s), 7.66 (1H,d,J=1.8Hz), 7.92 (1H,d,J=1.8Hz).

[0171] Example 66

[0172] 2-Bromo-4-fluoroanisole (200g) and solvent 2 (1,4-dioxane) were mixed at a mass (g) to volume (mL) ratio of 34:100 as the raw material phase. Cerium nitrate was ground and sieved, and 1000g of 3000-mesh particles were taken and mixed with activated carbon as a nitrating agent, wherein the amount of activated carbon added was 10% of the mass of cerium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was isopropanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.4:1. The residence time of the materials in the tubular reactor was 10 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 175 g of the nitrated product 2-bromo-4-fluoro-6-nitroanisole, with a yield of 63%. 1 H NMR (300MHz, CDCl3): δ3.93(3H,s),7.67-7.86(2H,7.72(d,J=1.8Hz),7.81(d,J=1.8Hz)).

[0173] Example 67

[0174] 200g of 3,4-methylenedioxyacetophenone (MDA) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 1000-mesh particles were collected and mixed with molecular sieve as a nitrating agent, with the molecular sieve added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 120℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 161 g of the nitrated product 4',5'-methylenedioxy-2'-nitroacetophenone, with a yield of 53%. 1 HNMR (300MHz, CDCl3): δ2.47(3H,s),6.34(2H,d,J=12.2Hz),7.62-7.78(2H,7.67(d,J=0.5Hz),7.73(d,J=0.5Hz)).

[0175] Example 68

[0176] 2-(6-methoxy-2-naphthyl)propionic acid (200 g) and solvent 2 (tetrahydrofuran) were mixed at a mass (g) to volume (mL) ratio of 18:100 as the raw material phase. 200 g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000 mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 35 minutes, the reaction temperature was 130 °C, and the pressure was 1.5 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 167 g of the nitrated product 2-(6-methoxy-5-nitro-2-naphthyl)propionic acid, with a yield of 54%. 1 H NMR (300MHz, DMSO): δ12.72(d,J=1.5Hz,1H),8.61(d,J=7.5Hz,1H),8.11(d,J=7.5Hz,1H),7.91(d,J=1.5Hz,1H),7. 15(dd,J=7.5,1.5Hz,1H),6.97(d,J=7.5Hz,1H),4.02(d,J=1.5Hz,1H),3.75(d,J=6.8Hz,1H),1.52(d,J=6.8Hz,3H).

[0177] Example 69

[0178] 200g of 4-(6-methoxy-2-naphthyl)but-2-one and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 22:100 as the raw material phase. Magnesium nitrate hexahydrate and magnesium sulfate were mixed at a mass ratio of 90:20, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with magnesium sulfate as a nitrating agent, with the magnesium sulfate addition amount being 10% of the mass of magnesium nitrate hexahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was trifluoroethanol:dichloroethane at a volume ratio of 5:2, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor separately, with a flow rate ratio of nitrated phase:raw material phase of 1.3:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to give 165 g of the nitrated product 4-(6-methoxy-5-nitro-2-naphthyl)but-2-one, in 51% yield. 1H NMR (300MHz, CDCl3): δ2.15(3H,s),2.53(2H,t,J=7.4Hz), 3.08(2H,t,J=7.4Hz), 3.87(3H,s),7.04(1H,dd,J=8.8,0.5Hz),7.70-7.93 (2H,7.76(dd,J=8.6,1.8Hz),7.88(ddt,J=1.8,1.5,0.5Hz)),7.96-8.13(2H,8.02(dt,J=8.6,0.5Hz),8.07(ddd,J=8.8,1.5,0.5Hz)).

[0179] Example 70

[0180] L-tyrosine (200g) and solvent 2 (difluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 38:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, with the molecular sieve added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with 1000mL of solvent 1. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.9:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 188 g of the nitrated product 3-nitro-L-tyrosine, with a yield of 62%. 1 H NMR (300MHz, DMSO): δ14.43(s,1H),12.89(s,1H),8.71(s,2H),7.97(d,J=1.5Hz,1H), 7.35(dd,J=7.5,1.5Hz,1H),7.19(s,1H),4.18(d,J=7.0Hz,1H),3.30(d,J=7.0Hz,2H).

[0181] Example 71

[0182] N-acetyl-L-tyrosine (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 25:100 as the raw material phase. Sodium nitrate and sodium sulfate were mixed at a mass ratio of 90:20, ground, and sieved. 1000g of 2000-mesh particles were collected and mixed with activated alumina, a nitrating agent, as the nitrating agent. The amount of activated alumina added was 20% of the mass of sodium nitrate. The nitrating agent was dispersed in solvent 1, which was tetrafluoropropanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrating phase were pumped into a tubular reactor separately. The flow rate ratio of nitrating phase to raw material phase was 1.5:1. The residence time of the materials in the tubular reactor was 10 minutes. The reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 145 g of the nitrated product N-acetyl-3-nitro-L-tyrosine, with a yield of 48%. 1 H NMR (300MHz, DMSO): δ14.43(s,1H),12.89(s,1H),9.37(s,1H); δ8.32(s,1H),7.97(d,J=1.5Hz,1H),7.35(dd,J=7.5,1.5Hz, 1H), 7.19 (d, J = 7.5Hz, 1H), 4.72 (d, J = 7.0Hz, 1H), 3.12 (dd, J = 12.4, 7.0Hz, 1H), 2.865 (dd, J = 12.4, 7.0Hz, 1H), 1.84 (s, 3H).

[0183] Example 72

[0184] Anthracene (200g) and solvent 2 (acetic acid) were mixed at a mass (g) to volume (mL) ratio of 35:100 as the raw material phase. Magnesium nitrate hexahydrate and magnesium sulfate were mixed at a mass ratio of 90:20, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with magnesium perchlorate as a nitrating agent, with the amount of magnesium perchlorate added being 25% of the mass of magnesium nitrate hexahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.6:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 185 g of the nitrated product 9-nitroanthracene, with a yield of 64%. 1H NMR (300MHz, CDCl3): δ7.76(2H,dddd,J=7.6,7.1,2.4,0.4Hz),7.87-8.20(7H,7.94(dddd,J=7.6,1.8,1.4, 0.5Hz), 8.02 (ddd, J=8.5, 7.1, 1.4Hz), 8.10 (tquint, J=1.8, 0.4Hz), 8.13 (dddd, J=8.5, 2.4, 0.5, 0.4Hz)).

[0185] Example 73

[0186] 1,8-Dibromonaphthalene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Aluminum nitrate was ground and sieved, and 1000g of 2000-mesh particles were mixed with a molecular sieve nitrating aid as the nitrating agent, wherein the amount of molecular sieve nitrating aid added was 25% of the mass of aluminum nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was hexafluoroisopropanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.4:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 120℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 195g of the nitrated product 4,5-dibromo-1-nitronaphthalene, with a yield of 72%. 1 H NMR (300MHz, CDCl3): δ7.46 (1H, dd, J = 7.8, 1.9Hz), 7.58-7.71 (2H, 7.64 (t, J = 7.8Hz) ,7.65(d,J=9.5Hz)),7.80(1H,ddd,J=7.9,1.9,0.5Hz),8.05(1H,dd,J=9.5,0.5Hz).

[0187] Example 74

[0188] 1-Bromonaphthalene (200g) and solvent 2 (ethyl acetate) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the raw material phase. Bismuth nitrate was ground and sieved, and 1000g of 2500-mesh particles were collected and mixed with acetic anhydride as a nitrating agent, with the amount of acetic anhydride added being 20% ​​of the mass of bismuth nitrate. The nitrating agent was dispersed in solvent 1, which was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 120℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 162g of the nitrated product 1-bromo-5-nitronaphthalene, with a yield of 55%. 1 H NMR (300MHz, CDCl3): δ7.49-7.74(3H,7.55(ddd,J=7.6,1.5,0.4Hz),7.57(dd,J=8.6,8.0Hz),7.67(dd,J=8.1,7.6Hz )),7.94(1H,ddt,J=8.1,1.5,0.5Hz),8.06-8.26(2H,8.12(ddt,J=8.0,1.8,0.5Hz),8.20(ddd,J=8.6,1.8,0.5Hz)).

[0189] Example 75

[0190] 9-Bromoanthracene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 35:100 as the raw material phase. Ammonium nitrate and ammonium sulfate were mixed at a mass ratio of 100:10, ground, and sieved. 1000g of 3000-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid being 10% of the mass of ammonium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was ethyl acetate:dichloroethane at a volume ratio of 3:1, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 177 g of the nitrated product 9-bromo-10-nitroanthracene, with a yield of 57%. 1H NMR (300MHz, CDCl3): δ7.42(2H,ddd,J=9.8,8.6,1.4Hz),8.00(2H,ddd,J=9.8,9 .0,1.4Hz),8.25(2H,ddd,J=9.0,1.4,0.5Hz),8.39(2H,ddd,J=8.6,1.4,0.5Hz).

[0191] Example 76

[0192] 1-Bromoanthraquinone (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 42:100 as the raw material phase. Aluminum nitrate and anhydrous aluminum sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with activated alumina as a nitrating agent, with the activated alumina addition being 10% of the mass of aluminum nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was trifluoroethanol:isopropanol at a volume ratio of 1:2, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase of 1.1:1. The residence time of the materials in the tubular reactor was 15 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 183 g of the nitrated product 1-bromo-5-nitroanthraquinone, with a yield of 66%. 1 H NMR (300MHz, CDCl3): δ7.73-8.07(3H,7.80(dd,J=8.8,7.6Hz),7.90(dd,J=8.5,2.0Hz),8.00(dd,J= 8.5,8.3Hz)),8.25(1H,dd,J=8.3,2.0Hz),8.39(1H,dd,J=8.8,1.4Hz),8.73(1H,dd,J=7.6,1.4Hz).

[0193] Example 77

[0194] 1-Nitroanthraquinone (200g) and solvent 2 (trifluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 36:100 as the feed phase. 500g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 150℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 159g of the nitrated product 1,5-dinitroanthraquinone, with a yield of 51%. 1 H NMR (300MHz, CDCl3): δ7.80 (2H, dd, J = 8.4, 7.4Hz), 8.62-8.80 (4H, 8.68 (dd, J = 7.4, 1.3Hz), 8.74 (dd, J = 8.4, 1.3Hz)).

[0195] Example 78

[0196] 1,8-Dichloronaphthalene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, with the molecular sieve added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 194 g of the nitrated product 4,5-dichloro-1-nitronaphthalene, with a yield of 75%. 1 H NMR (300MHz, CDCl3): δ7.60-7.95(4H,7.67(dd,J=7.9,7.5Hz),7.72(dd,J=7.9,1.8 Hz),7.80(ddd,J=7.5,1.8,0.5Hz),7.89(d,J=8.8Hz)),8.16(1H,dd,J=8.8,0.5Hz).

[0197] Example 79

[0198] 1-Chloronaphthalene (200g) and solvent 2 (dichloromethane) were mixed at a mass (g) to volume (mL) ratio of 40:100 as the raw material phase. Potassium nitrate was ground and sieved, and 1000g of 2500-mesh particles were taken and mixed with acetic anhydride as a nitrating agent, wherein the amount of acetic anhydride added was 20% of the mass of potassium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was trifluoroethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor separately using a pump at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 35 minutes, the reaction temperature was 140℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 163g of the nitrated product 1-chloro-5-nitronaphthalene, with a yield of 51%. 1 H NMR (300MHz, CDCl3): δ7.37(1H,ddd,J=7.6,1.6,0.4Hz),7.55-7.76(2H,7.62(dd,J=8.6,8.0Hz),7.69(dd,J=8.1 ,7.6Hz)),7.86(1H,ddt,J=8.1,1.6,0.5Hz),7.99(1H,ddt,J=8.0,1.6,0.5Hz),8.22(1H,ddd,J=8.6,1.6,0.4Hz).

[0199] Example 80

[0200] 200g of 9-chloroanthracene and solvent 2 (tetrafluoropropanol) were mixed at a mass (g) to volume (mL) ratio of 25:100 as the raw material phase. Gallium nitrate and sodium sulfate were mixed at a mass ratio of 90:30, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid added at 15% of the mass of gallium nitrate. The nitrating agent was dispersed in solvent 1 (isopropanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 171 g of the nitrated product 9-chloro-10-nitroanthracene, with a yield of 57%. 1H NMR (300MHz, CDCl3): δ7.57(2H,ddd,J=9.9,8.6,1.4Hz),8.00(2H,ddd,J=9.9,9.1,1 .4Hz),8.23-8.45(4H,8.29(ddd,J=9.1,1.4,0.5Hz),8.39(ddd,J=8.6,1.4,0.5Hz)).

[0201] Example 81

[0202] 1-Chloroanthraquinone (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 30:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles. The nitrifying agent was dispersed in solvent 1 (hexafluorobutanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 135℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 182g of the nitrated product 1-chloro-5-nitroanthraquinone, with a yield of 61%. 1 H NMR (300MHz, CDCl3): δ7.80 (1H, dd, J = 8.8, 7.6 Hz), 7.89-8.07 (2H, 7.95 (dd, J = 8.6, 2.0 Hz)), 8.00 (dd, J = 8. 6,8.4Hz)),8.24-8.45(2H,8.30(dd,J=8.4,2.0Hz),8.39(dd,J=8.8,1.4Hz)),8.73(1H,dd,J=7.6,1.4Hz).

[0203] Example 82

[0204] 1,8-Difluoronaphthalene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the feed phase. 500g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with a volume of 1000mL. The feed phase and nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.5:1. The residence time of the materials in the tubular reactor was 15 minutes, the reaction temperature was 140℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 194g of the nitrated product 4,5-difluoro-1-nitronaphthalene, with a yield of 73%.1 H NMR (300MHz, CDCl3): δ7.42-7.71(3H,7.48(dd,J=7.9,1.9Hz),7.54(dd,J=7.9,7.5Hz) ),7.65(d,J=8.5Hz)),7.93(1H,ddd,J=7.5,1.9,0.5Hz),8.24(1H,dd,J=8.5,0.5Hz).

[0205] Example 83

[0206] 1-Fluoronaphthalene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 10:100 as the raw material phase; 500g of dinitrogen pentoxide was used as the nitrating agent; the nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was hexafluoroisopropanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1, the residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 161g of the nitrated product 1-fluoro-5-nitronaphthalene, with a yield of 54%. 1 H NMR (300MHz, CDCl3): δ7.38 (1H, ddd, J = 7.5, 1.5, 0.5Hz), 7.61-7.91 (3H, 7.68 (dd, J = 8.1, 7.5Hz), 7.82 (dd, J = 8.6, 8. 1Hz),7.84(ddt,J=8.1,1.5,0.5Hz)),8.13-8.27(2H,8.20(ddd,J=8.6,1.8,0.4Hz),8.21(ddt,J=8.1,1.8,0.5Hz)).

[0207] Example 84

[0208] 200g of 9-fluoroanthracene and solvent 2 (ethyl acetate: dichloromethane = 4:1) were mixed at a mass (g) to volume (mL) ratio of 35:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles. 500g of water was mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid added at 5% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (dichloroethane) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 10 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 175 g of the nitrated product 9-fluoro-10-nitroanthracene, with a yield of 61%. 1 H NMR (300MHz, CDCl3): δ7.52(2H,ddd,J=8.0,7.4,1.9Hz),7.91(2H,ddd,J=8.2,7 .4,1.5Hz),8.27(2H,ddd,J=8.2,1.9,0.4Hz),8.47(2H,ddd,J=8.0,1.5,0.4Hz).

[0209] Example 85

[0210] 1-Fluoroanthraquinone (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 30:100 as the raw material phase. Magnesium nitrate hexahydrate and magnesium sulfate were mixed at a mass ratio of 100:20, ground, and sieved to obtain 1000g of 2500-mesh particles. The nitrating agent was dispersed in solvent 1 (ethyl acetate) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 181g of the nitrated product 1-fluoro-5-nitroanthraquinone, with a yield of 66%. 1H NMR (300MHz, DMSO): δ8.54(dd,J=7.5,1.5Hz,1H); 8.24(dd,J=7.5,1.5Hz,1H); 8.00(dd,J=7.5,7.5H z, 1H); 7.62 (dd, J=7.5, 1.5Hz, 1H); 7.60 (q, J=7.5, 7.5, 5.0Hz, 1H); 7.49 (q, J=8.0, 7.5, 1.5Hz, 1H).

[0211] Example 86

[0212] 1,8-Diiodonaphthalene (200g) and solvent 2 (diethyl ether: tetrahydrofuran) were mixed at a mass (g) to volume (mL) ratio of 35:100 to form the raw material phase. Potassium nitrate was ground and sieved, and 1000g of 2500-mesh particles were collected as the nitrating agent. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was tetrahydrofuran, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.5:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 192g of the nitrated product 4,5-diiodo-1-nitronaphthalene, with a yield of 75%. 1 H NMR (300MHz, CDCl3): δ7.42(1H,dd,J=8.7,1.7Hz),7.61(1H,dd,J=8.7,8.4Hz),7.72-7 .96(2H,7.79(d,J=9.6Hz),7.90(ddd,J=8.4,1.7,0.5Hz)),8.06(1H,dd,J=9.6,0.5Hz).

[0213] Example 87

[0214] 1-Iodonaphthalene (200g) and solvent 2 (ethanol) were mixed at a mass (g) to volume (mL) ratio of 40:100 as the raw material phase. Ammonium nitrate and ammonium sulfate were mixed at a mass ratio of 100:30, ground, and sieved. 1000g of 2500-mesh particles were taken and mixed with 300g of water and acetic anhydride as the nitrating agent, with the acetic anhydride addition being 10% of the mass of ammonium nitrate. The nitrating agent was dispersed in solvent 1 (ethanol) to form the nitrated phase, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.3:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 163 g of the nitrated product 1-iodo-5-nitronaphthalene, with a yield of 54%. 1 H NMR (300MHz, CDCl3): δ7.52-7.75(3H,7.59(dd,J=8.6,8.0Hz),7.59(ddd,J=7.7,1.4,0.4Hz),7.68(dd,J=8.5,7.7Hz )),7.89-8.13(2H,7.95(ddt,J=8.5,1.4,0.5Hz),8.07(ddt,J=8.0,1.8,0.5Hz)),8.22(1H,ddd,J=8.6,1.8,0.5Hz).

[0215] Example 88

[0216] 200 g of 9-iodoanthracene was mixed with solvent 2 (dichloroethane) at a mass (g) to volume (mL) ratio of 35:100 as the feed phase. 500 g of nitrogen pentoxide was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 consisted of ethyl acetate and dichloroethane in a volume ratio of 3:1, and the volume of solvent 1 was 1000 mL. The feed phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 1.5:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 130 °C, and the pressure was 1.5 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 174 g of the nitrated product 9-iodo-10-nitroanthracene, with a yield of 58%. 1H NMR (300MHz, CDCl3): δ7.68(2H,ddd,J=9.6,8.5,1.5Hz),7.93-8.12(4H,8.01(ddd,J =9.6,8.6,1.1Hz),8.06(ddd,J=8.5,1.1,0.5Hz)),8.25(2H,ddd,J=8.6,1.5,0.5Hz).

[0217] Example 89

[0218] 1-Iodoanthraquinone (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 24:100 as the raw material phase. Ferric nitrate nonahydrate was ground and sieved, and 1000g of 2500-mesh particles were collected. 200g of water was mixed with a molecular sieve nitrating aid as the nitrating agent, wherein the molecular sieve nitrating aid was added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 was ethanol, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.2:1. The residence time of the materials in the tubular reactor was 35 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 184 g of the nitrated product 1-iodo-5-nitroanthraquinone, with a yield of 60%. 1 HNMR (300MHz, CDCl3): δ7.73-8.06(3H,7.80(dd,J=8.8,7.6Hz),7.91(dd,J=7.4,7.1Hz),8.00(dd,J =7.4,2.0Hz)),8.26(1H,dd,J=7.1,2.0Hz),8.40(1H,dd,J=8.8,1.4Hz),8.73(1H,dd,J=7.6,1.4Hz).

[0219] Example 90

[0220] N-methylpyrrole (2g) and solvent 2 (ethyl acetate: dichloroethane = 5:1) were mixed at a mass (g) to volume (mL) ratio of 18:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:20, ground, and sieved. 10g of 2500-mesh particles were collected and mixed with a molecular sieve nitrating aid as the nitrating agent, with the molecular sieve nitrating aid added at 20% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with 10mL of solvent 1. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.4:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 1.78 g of the nitrated product N-methyl-2,3,4,5-tetranitro-1-hydropyrrole, with a yield of 65%. 1 HNMR (300MHz, CDCl3): δ3.94 (3H,s).

[0221] Example 91

[0222] Cyclohexamethylenetetramine (2g) and solvent 2 (n-hexane: dichloroethane = 1:1) were mixed at a mass (g) to volume (mL) ratio of 15:100 as the raw material phase. Bismuth nitrate was ground and sieved, and 1000g of 2500-mesh particles were mixed with a nitrating aid molecular sieve as the nitrating agent, wherein the amount of the nitrating aid molecular sieve added was 20% of the mass of bismuth nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was n-hexane: trifluoroethanol = 1:5 (volume ratio), and the volume of solvent 1 was 10mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.05:1. The residence time of the materials in the tubular reactor was 10 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 1.53 g of the nitrated product cyclotrimethylenetrinitramine, with a yield of 52%. 1 H NMR (300MHz, CDCl3): δ5.24 (6H,d,J=15.7Hz).

[0223] Example 92

[0224] Cyclohexamethylenetetramine (2g) and solvent 2 (acetic acid) were mixed at a mass (g) to volume (mL) ratio of 35:100 as the raw material phase. Aluminum nitrate and anhydrous aluminum sulfate were mixed at a mass ratio of 90:20, ground, and sieved to obtain 10g of 2500-mesh particles. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, where solvent 1 consisted of ethyl acetate and difluoroethanol at a volume ratio of 4:1, and the volume of solvent 1 was 10mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.5:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 2.4g of the nitrated product, cyclotetramethylenetetranitramine, with a yield of 76%. 1 H NMR (300MHz, CDCl3): δ5.21 (8H,d,J=14.9Hz).

[0225] Example 93

[0226] Diethylamine hydrochloride (2g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 10g of 2500-mesh particles were collected and mixed with molecular sieve as a nitrating agent, with the molecular sieve added at 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (trifluoroethanol) to form the nitrated phase, with 10mL of solvent 1. The raw material phase and the nitrated phase were pumped into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 20 minutes, the reaction temperature was 130℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by recrystallization from ethanol to obtain 1.87 g of the nitrated product N-nitrodiethylamine, with a yield of 68%. 1 H NMR (300MHz, CDCl3): δ1.28 (6H, t, J = 7.1Hz), 3.62 (4H, q, J = 7.1Hz).

[0227] Example 94

[0228] 200 g of p-bromotoluene and solvent 2 (ethyl acetate: trifluoroethanol = 1:4) were mixed at a mass (g) to volume (mL) ratio of 25:100 as the feed phase. 200 g of 98% nitric acid was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was prepared at a volume ratio of ethyl acetate: n-hexane = 100:15, and the volume of solvent 1 was 1000 mL. The feed phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:feed phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 90 °C, and the pressure was 1.5 MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 191 g of the nitrated product 4-bromo-2-nitrotoluene, with a yield of 71%. 1 H NMR (300MHz, CDCl3): δ2.50(3H,s),7.54(1H,dd,J=8.0,0.4Hz), 7.75(1H,dd,J=8.0,1.7Hz), 8.30(1H,dd,J=1.7,0.4Hz).

[0229] Example 95

[0230] 200g of p-fluorotoluene and solvent 2 (methanol) were mixed at a mass (g) to volume (mL) ratio of 30:100 as the raw material phase. Gallium nitrate was ground and sieved, and 1000g of 2500-mesh particles were taken and mixed with phosphorus pentoxide as a nitrating agent, wherein the amount of phosphorus pentoxide added was 20% of the mass of gallium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was prepared at a volume ratio of ethyl acetate:n-hexane = 100:15, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor separately using a pump at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 193 g of the nitrated product 4-fluoro-2-nitrotoluene, with a yield of 70%. 1 H NMR (300MHz, CDCl3): δ2.46 (3H, s), 7.18 (1H, dd, J = 8.2, 1.8 Hz), 7.53 (1H, dd, J = 8.2, 0.4 Hz), 7.98 (1H, dd, J = 1.8, 0.4 Hz).

[0231] Example 96

[0232] 200g of p-iodotoluene and solvent 2 (chloroform) were mixed at a mass (g) to volume (mL) ratio of 45:100 as the raw material phase. 1000g of magnesium nitrate hexahydrate was ground and sieved, and 2500-mesh particles were mixed with magnesium sulfate as a nitrating agent, with the magnesium sulfate addition amount being 20% ​​of the mass of magnesium nitrate hexahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate:dichloromethane = 100:35, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.7:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 198 g of the nitrated product 4-iodo-2-nitrotoluene, with a yield of 72%. 1 H NMR (300MHz, CDCl3): δ2.54(3H,s),7.54(1H,dd,J=8.0,0.5Hz),7.65-7.83(2H,7.71(dd,J=8.0,1.8Hz),7.78(dd,J=1.8,0.5Hz)).

[0233] Example 97

[0234] 2-Bromo-4-methylbenzene (200g) and solvent 2 (difluoroethanol) were mixed at a mass (g) to volume (mL) ratio of 45:100 as the raw material phase. Sodium nitrate was ground and sieved, and 1000g of 2500-mesh particles were taken and mixed with sodium sulfate as a nitrating agent, wherein the amount of molecular sieve added as nitrating agent was 10% of the mass of sodium nitrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was prepared at a volume ratio of acetic acid:n-hexane = 100:25, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped into a tubular reactor separately using a pump at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 95℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 188 g of the nitrated product 2-bromo-4-methyl-1-nitrobenzene, with a yield of 67%. 1 H NMR (300MHz, CDCl3): δ2.35(3H,s),7.31-7.45(2H,7.36(dd,J=1.0,0.4Hz),7.39(dd,J=8.1,1.0Hz)), 8.02(1H,dd,J=8.1,0.4Hz).

[0235] Example 98

[0236] 2-Chloro-4-methylbenzene (200g) and solvent 2 (1,4-dioxane) were mixed at a mass (g) to volume (mL) ratio of 20:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected and mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 (hexafluorobutanol) to form the nitrated phase, with solvent 1 being 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.4:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 182 g of the nitrated product 2-chloro-4-methyl-1-nitrobenzene, with a yield of 64%. 1 H NMR (300MHz, CDCl3): δ2.26 (3H, s), 7.45 (1H, dd, J = 8.1, 1.0 Hz), 7.65 (1H, dd, J = 1.0, 0.5 Hz), 8.02 (1H, dd, J = 8.1, 0.5 Hz).

[0237] Example 99

[0238] 2-Fluoro-4-methylbenzene (200g) and solvent 2 (methanol) were mixed at a mass (g) to volume (mL) ratio of 35:100 as the raw material phase. 500g of dinitrogen pentoxide was used as the nitrating agent. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, wherein solvent 1 was prepared at a volume ratio of ethyl acetate:n-hexane = 100:30, and the volume of solvent 1 was 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 1.1:1. The residence time of the materials in the tubular reactor was 30 minutes, the reaction temperature was 80℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 183g of the nitrated product 2-fluoro-4-methyl-1-nitrobenzene, with a yield of 63%. 1 H NMR (300MHz, CDCl3): δ2.26(3H,s),7.29-7.49(2H,7.34(dd,J=1.0,0.5Hz),7.43(dd,J=8.1,1.0Hz)), 8.02(1H,dd,J=8.1,0.5Hz).

[0239] Example 100

[0240] 2-Iodo-4-methylbenzene (200g) and solvent 2 (dichloroethane) were mixed at a mass (g) to volume (mL) ratio of 35:100 as the raw material phase. Ferric nitrate nonahydrate and ferric sulfate were mixed at a mass ratio of 90:10, ground, and sieved to obtain 1000g of 2500-mesh particles, which were then mixed with acetic anhydride as a nitrating agent, with the acetic anhydride addition amounting to 10% of the mass of ferric nitrate nonahydrate. The nitrating agent was dispersed in solvent 1 to form the nitrated phase, which was prepared at a volume ratio of ethyl acetate to n-hexane of 100:15, with a volume of 1000mL. The raw material phase and the nitrated phase were pumped separately into a tubular reactor at a flow rate ratio of nitrated phase:raw material phase = 0.6:1. The residence time of the materials in the tubular reactor was 40 minutes, the reaction temperature was 90℃, and the pressure was 1.5MPa. The reaction mixture was cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was then purified by vacuum distillation to obtain 181 g of the nitrated product 2-iodo-4-methyl-1-nitrobenzene, with a yield of 64%. 1 H NMR (300MHz, CDCl3): δ2.39(3H,s), 6.63(1H,dd,J=1.1,0.4Hz), 7.40(1H,dd,J=8.1,1.1Hz), 8.02(1H,dd,J=8.1,0.4Hz).

[0241] To examine the superiority of the technology of this invention, the experiment also attempted the benzoic acid nitration reaction in Example 7 using both the batch reaction of this green nitration process and the continuous process of traditional mixed acid nitration. The reaction steps and results are shown below:

[0242] Comparative Example 1

[0243] Benzoic acid, dichloroethane, ferric nitrate nonahydrate, ferric sulfate, montmorillonite, ethyl acetate, and n-hexane were placed in a batch reactor. The mass ratio (g) of benzoic acid (200g) to solvent 2 (dichloroethane) was 15:100 (mL). Ferric nitrate nonahydrate and ferric sulfate were mixed in a mass ratio of 90:10, ground, and sieved. 1000g of 2500-mesh particles were collected. The amount of montmorillonite added was 10% of the mass of ferric nitrate nonahydrate. 1000mL of a mixed solution of ethyl acetate and n-hexane was added, with an ethyl acetate:n-hexane ratio of 100:15 (volume ratio). The reaction was carried out at 150℃ and 1.5MPa for 40 minutes. The reaction mixture was then cooled to room temperature, and the solvent was removed under reduced pressure. The crude product was purified by recrystallization from ethanol to obtain 100g of the nitrated product, m-nitrobenzoic acid, with a yield of 37%. Using a batch reactor, the yield for the same reaction time is much lower than that of a continuous flow reactor. This shows that using a continuous flow reactor can significantly improve reaction efficiency and shorten reaction time.

[0244] Comparative Example 2

[0245] Take 200g of benzoic acid and prepare a mixed acid solution, wherein the molar ratio of 68% nitric acid to benzoic acid is 1.1:1, and the molar ratio of concentrated nitric acid to concentrated sulfuric acid is 1:2. The reaction temperature is 70℃, and the residence time of the material in the tubular reactor is 30 minutes. Cool the reaction solution to 15-20℃ and let it stand for 1-2 hours. Separate the lower waste acid layer and retain the upper organic phase. Slowly add 5% sodium carbonate solution to the organic phase and stir to neutralize to pH 6.5-7.0. During this process, the temperature should be controlled ≤40℃ to avoid local overheating. After standing and separating the layers, discard the aqueous phase and wash it several times with an equal volume of deionized water to remove residual salts. After washing, the organic phase is centrifuged to obtain the crude product. Due to the strong oxidizing property of concentrated sulfuric acid, the crude product contains, in addition to m-nitrobenzoic acid, o-nitrobenzoic acid, p-nitrobenzoic acid, and a small amount of dinitrobenzoic acid as byproducts. The crude product was then purified by recrystallization from ethanol to obtain 188g of the nitrated product, m-nitrobenzoic acid, with a yield of 69%. In the waste acid treatment stage, the separated waste acid was first cooled to 10–15°C and allowed to stand for 1 hour. Residual organic impurities in the waste acid crystallized out and were separated by plate and frame filtration. The waste acid was then sent to a graphite concentration reactor, where a vacuum of 0.085–0.095 MPa and a heating temperature of 180–200°C were controlled. Water was evaporated until the sulfuric acid concentration reached 95%–98%. The dilute nitric acid (10%–15%) volatilized during concentration could be recovered by condensation. Using mixed acids generates numerous byproducts and a large amount of acidic wastewater, and the treatment process for this acidic wastewater is complex and costly.

[0246] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A continuous flow nitration process for the nitration of a phase, characterized in that, The continuous flow nitration method of the nitration phase comprises the following steps: The nitration agent is mixed with solvent 1 to obtain a fluid as the nitration phase; After the raw material is dissolved and dispersed by solvent 2, a mixed solution is obtained as the raw material phase; The nitration phase and the raw material phase are transported into a continuous flow reactor at a certain flow rate ratio, and the nitration product is obtained after reaction, realizing continuous nitration synthesis.

2. A continuous flow nitration process according to claim 1 wherein, The nitration agent comprises one or more of the following: Solid nitration agent after grinding and sieving of nitrate salt; Solid nitration agent after grinding and sieving of mixture of nitrate salt and sulfate salt; Solid nitration agent obtained by mixing nitrate salt and nitration aid; Solid nitration agent obtained by mixing nitrate salt and sulfate salt and mixing with nitration aid; Fluid nitration agent formed by mixing nitrate salt with water and / or nitration aid; Fluid nitration agent formed by mixing nitrate salt and sulfate salt with water and / or nitration aid; Nitric acid alone as the nitration agent; Fluid nitration agent obtained by mixing nitric acid and nitration aid; Dinitrogen pentoxide.

3. A continuous flow nitration process according to claim 2 wherein, The mass ratio of the mixture of nitrate salt and sulfate salt is 1:0.1-100; The nitrate salt comprises one or more of ferric nitrate nonahydrate, cerium nitrate, bismuth nitrate, potassium nitrate, gallium nitrate, magnesium nitrate hexahydrate, sodium nitrate, ammonium nitrate, and aluminum nitrate; The sulfate salt comprises one or more of magnesium sulfate, ferric sulfate, anhydrous aluminum sulfate, and ammonium sulfate; The grinding and sieving is performed with particles of 500-3000 mesh; The mass concentration of water is 0.1-100 mol / L in terms of nitrate content; The mass of the nitration aid is 0.1-200% of the mass of the nitric acid or nitrate salt; The nitration aid is a mixture of one or more of phosphorus pentoxide, molecular sieve, calcium chloride, silica gel, activated alumina, glycerol, magnesium oxide, magnesium perchlorate, magnesium sulfate, sodium sulfate, activated carbon, montmorillonite, sodium polyacrylate, and acetic anhydride; When the nitric acid is used alone as the nitration agent, the concentration of the nitric acid is 10-98% by mass.

4. A continuous flow nitration process according to claim 1 wherein, The solvent 1 is selected from one or more of the following: ethyl acetate, n-hexane, methanol, ethanol, isopropanol, difluoroethanol, trifluoroethanol, tetrafluoropropyl alcohol, hexafluoroisopropyl alcohol, hexafluorobutyl alcohol, dichloromethane, trichloromethane, dichloroethane, tetrahydrofuran, dioxane, acetic acid, diethyl ether, and acetonitrile; The mixing ratio of the nitration agent and solvent 1 is 1 g: (0.1-1000) mL by mass and volume.

5. The continuous flow nitration process of claim 1, wherein, The raw material is one or more of a carbon-containing compound, a nitrogen-containing compound, or an oxygen-containing compound; The solvent 2 is selected from one or more of the following: methanol, ethanol, n-hexane, ethyl acetate, diethyl ether, dichloromethane, chloroform, difluoroethanol, trifluoroethanol, hexafluoroisopropyl alcohol, dichloroethane, tetrahydrofuran, 1,4-dioxane, and acetic acid; The raw material phase is prepared by mixing the raw material and solvent 2 at a mass ratio of (1-100) g: 10 mL.

6. A continuous flow nitration process according to claim 5 wherein, The carbon-containing compound satisfies the following general structure: R-C(R1R2)-H, The oxygen-containing compound satisfies the following general structure: R-O-H, The nitrogen-containing compound satisfies the following general structure: R-N(R1)-H, wherein R is a chain or cyclic saturated or unsaturated alkyl group with or without heteroatoms, or an aromatic group, and R1 and R2 are independently selected from H or a C1-C6 alkyl group.

7. The continuous flow nitration process of claim 1, wherein, The ratio of the nitration phase and the raw material phase is that the ratio of the amount of substance of the total nitrate contained in the nitration agent in the nitration phase to the amount of substance of the raw material in the raw material phase is 1-20:

1.

8. The continuous flow nitration process of claim 1, wherein, The ratio of the volume flow rate of the nitration phase and the raw material phase is 0.3-2.5:

1. The nitration phase and the raw material phase are delivered into the continuous flow reactor by a fluid delivery device at a certain ratio of flow rate; The continuous flow reactor is selected from one or more of a micro-channel reactor, a pipe reactor.

9. A continuous flow nitration process according to claim 8 wherein, The fluid delivery device is a pump.

10. The continuous flow nitration process of claim 1, wherein, The reaction conditions of the continuous nitration synthesis are 0-160℃, the residence time of the material is 2-60 minutes, and the reaction pressure is 0-5 MPa.