A method for one-step preparation of halogenated anthraquinone compounds

Abstract

The application relates to the field of organic synthesis, and discloses a method for one-step preparation of halogenated anthraquinone compounds. The method takes anthracene compounds as a substrate, uses oxygen-containing gas as an oxidant, and reacts with a halogenation reagent and a catalyst to realize one-step synthesis of halogenated anthraquinone compounds. The method has a short reaction flow, high atomic economy, high product yield, and is convenient for product separation and suitable for industrial production.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis, and more particularly to a method for one-step preparation of haloanthraquinone compounds. Background Technology

[0002] Halogenated anthraquinones are widely used chemical intermediates. For example, 1-chloroanthraquinone can be further converted into dye molecules such as olive green R, 1-aminoanthraquinone, and 1-hydroxyanthraquinone, and 1,4-dichloroanthraquinone can be further converted into dye molecules such as vat brown BR and vat yellow FFRK. They can also be used as precursors for anthraquinone antitumor drugs.

[0003] Traditional synthetic processes for haloanthraquinones generally consist of multiple steps. Taking the synthesis of 1-chloroanthraquinone as an example, these include the mercury directing method (sulfonation-chlorination), the sodium sulfite method (nitration-sulfonation-chlorination), the direct chlorination method (nitration-chlorination), and the phthalic anhydride method (nitration-chlorination-French acylation).

[0004] Among these methods, the mercury directive method is the most mature industrially available, offering a short reaction flow and high yield. However, mercury is a highly hazardous reagent to human health and the environment, placing stringent requirements on product quality and the emission of waste. The sodium sulfite method is an industrial alternative to the mercury directive method, avoiding the use of mercury. However, it involves a longer reaction flow, produces more substituted isomers, and results in a lower yield, making it less than ideal. Finally, the direct chlorination method and the phthalic anhydride method also suffer from similar problems. The formation of multi-substituted products and monosubstituted isomers leads to an overall lower yield, and product separation and purification present significant challenges. Therefore, industrial-scale production has not yet been achieved.

[0005] In summary, it is clear that developing a novel method for preparing halogenated anthraquinone compounds has significant industrial implications. This novel production process should possess advantages such as a short reaction flow, high product yield, simple product separation and purification, environmental friendliness, and low cost. Summary of the Invention

[0006] To address the aforementioned technical problems, this invention provides a one-step method for preparing haloanthraquinone compounds. The method uses anthracene compounds as substrates and oxygen-containing gas as an oxidant, reacting with a halogenating reagent and a catalyst to achieve one-step synthesis of haloanthraquinone compounds. This method features a short reaction flow, high atom economy, convenient product separation, high yield, and is suitable for industrial production.

[0007] The specific technical solution of this invention is as follows: a method for one-step preparation of haloanthraquinone compounds, comprising uniformly mixing anthracene compounds, halogenating reagents, catalysts, and solvents, continuously introducing oxygen-containing gas to carry out the reaction, and separating the haloanthraquinone compounds after the reaction is completed; the reaction formula is: Wherein, R is H, C1-C6 straight-chain alkyl, or C1-C6 branched alkyl.

[0008] The method of this invention uses anthracene compounds as substrates and oxygen-containing gas as oxidants. After mixing with halogenating reagents and catalysts, it can achieve one-step synthesis of haloanthraquinone compounds. Compared with the prior art, it has the advantages of short reaction process, high atom economy, convenient product separation, and high yield.

[0009] It is important to emphasize that when R is an alkyl group, it must be strictly limited to a C1-C6 straight-chain alkyl or a C1-C6 branched alkyl. This is because alkyl groups are weak electron-donating groups, which can increase the electron cloud density at the reaction site, making the substrate easier to activate. However, on the other hand, if the alkyl substituent is too large, it can lead to significant steric hindrance, making it difficult for the substrate to approach the catalytic center. Therefore, it is necessary to limit the substituent to achieve the best reaction results.

[0010] Preferably, the above method specifically includes: mixing the solvent and catalyst evenly, then adding anthracene compounds and halogenating reagents and sealing the reaction system, heating the reaction system to the reaction temperature and continuously introducing oxygen-containing gas, reacting under stirring, reaching the reaction endpoint, diluting the reaction mother liquor with water, and gradually precipitating the reaction product during the dilution process, filtering and washing to obtain haloanthraquinone compounds.

[0011] Preferably, the solvent is a mixture of acetic acid and water, with a mass ratio of acetic acid to water of 1:10 to 30, more preferably 1:15 to 20.

[0012] Preferably, the mass ratio of the anthracene compound to the solvent is 1:4 to 99, more preferably 1:10 to 20.

[0013] The amount of solvent used needs to be controlled within a certain range. From the perspective of reaction efficiency, if the amount of solvent is too small or the solvent-to-water ratio is inappropriate, it will lead to an increase in reaction byproducts, increased reactant consumption, and increased complexity in subsequent product purification. From the perspective of reaction economy, if the amount of solvent is too large and the substrate concentration is too low, it will lead to an increase in separation energy consumption. Therefore, the amount and ratio of solvent added need to be controlled within an appropriate range.

[0014] Preferably, the halogenating reagent is selected from HCl, HBr, LiCl, LiBr, NaCl, NaBr, KCl, and KBr.

[0015] Preferably, the molar ratio of the anthracene compound to the halogenating agent is 1:1 to 3, more preferably 1:1.2 to 1.5.

[0016] Increasing the proportion of halogenating reagents appropriately can improve the conversion rate of the reaction substrate. However, from an economic point of view, the amount of halogenating reagents should not be excessive.

[0017] Preferably, the catalyst is a mixture of cobalt acetate, manganese acetate and hydrogen bromide.

[0018] Preferably, the molar ratio of the anthracene compound to the catalyst is anthracene compound: cobalt acetate: manganese acetate: hydrogen bromide = 1:0.1-0.5:0.01-0.05:0.2-0.6, more preferably 1:0.2-0.3:0.02-0.03:0.3-0.4.

[0019] In the catalytic system of this invention, the addition of manganese and bromine can accelerate the oxidation reaction, reduce the production of over-oxidation products CO2 and CO, and also reduce the amount of cobalt added, shortening or eliminating the induction period of the reaction. For the preparation process of haloanthraquinones in this invention, the possible reaction mechanism consists of two parts, as shown below (taking anthracene as an example): Reaction 1 is the oxidation process from anthracene to anthraquinone, mainly consisting of the redox cycles of manganese and cobalt. Bromine acts as a co-catalyst, abstracting hydrogen atoms from the substrate to initiate a free radical reaction. Cobalt can not only oxidize manganese ions but also decompose the peroxide intermediates generated in the Haber-Weiss cycle, anthracene (R... 1 =H) is first converted to anthraquinone (R) under this catalytic cycle. 1 =OH), and then anthraquinone is converted to hydrogen anthraquinone under the same catalytic cycle. Finally, the oxidation process of hydrogen anthraquinone to anthraquinone can proceed smoothly without catalysis (not shown in the reaction formula); Reaction 2 is the conversion process of anthraquinone to chloroanthraquinone. The key intermediate of the reaction is the anthraquinone radical cation, which is generated by a single electron transfer (SET) process between anthraquinone and metal ions. After the radical cation reacts with the halogen in the reaction system, it undergoes radical addition and proton elimination reactions to generate the final haloanthraquinone product.

[0020] Preferably, the pressure of the oxygen-containing gas is 0.5–3 MPa and the ventilation rate is 0.5–3 L / min; more preferably, the pressure is 1–2 MPa and the ventilation rate is 1.5–2 L / min.

[0021] Preferably, the oxygen-containing gas is pure oxygen, air, or a mixture of oxygen and an inert gas, and more preferably pure oxygen or air.

[0022] Preferably, the reaction temperature is 120–200°C and the reaction time is 1–6 h; more preferably, the reaction temperature is 160–180°C and the reaction time is 2–4 h.

[0023] Different substrates require different activation energies to undergo oxidation reactions, thus necessitating different reaction temperatures. When the temperature is too low, the reaction substrate may not be completely converted or may remain largely in the intermediate stage, while excessively high temperatures can lead to the simultaneous appearance of numerous reactive free radical intermediates in the reaction system, resulting in the formation of large molecular weight byproducts, which is also detrimental to ensuring the reaction yield.

[0024] Preferably, the separation methods for halogenated anthraquinone compounds are dissolution crystallization and filtration separation.

[0025] Preferably, the mass ratio of water added to the initial solvent is 1 to 3, more preferably 1.5 to 2.

[0026] Compared with the prior art, the present invention has the following technical effects: (1) This invention starts from anthracene compounds and only requires one reaction to obtain haloanthraquinone products. The reaction process is short, the reaction yield is high, and the material and energy consumption are significantly reduced, which is more conducive to cost control in industrial production.

[0027] (2) The reaction raw materials and catalysts used in the method of the present invention are inexpensive and readily available. They do not use reagents that are harmful to human health or the environment, making the method more green and environmentally friendly, while greatly improving the safety of the reaction.

[0028] (3) The product obtained by the method of the present invention is easy to separate and purify, and only filtration and washing are required to obtain a product with high purity. Detailed Implementation

[0029] The present invention will be further described below with reference to embodiments.

[0030] General Implementation Examples A one-step method for preparing haloanthraquinone compounds involves uniformly mixing a solvent and a catalyst, then adding anthracene compounds and a halogenating reagent, sealing the reaction system, heating the reaction system to the reaction temperature, continuously introducing oxygen-containing gas, and reacting under stirring until the reaction endpoint is reached. Water is then added to the mother liquor to dilute the reaction product, which gradually precipitates during dilution. The product is then filtered and washed to obtain the haloanthraquinone compounds. The reaction formula is as follows: Wherein, R is H, C1-C6 straight-chain alkyl, or C1-C6 branched alkyl.

[0031] Preferably, the solvent is a mixture of acetic acid and water, with a mass ratio of acetic acid to water of 1:10 to 30, more preferably 1:15 to 20; the halogenating agent is selected from HCl, HBr, LiCl, LiBr, NaCl, NaBr, KCl, and KBr; the catalyst is a mixture of cobalt acetate, manganese acetate, and hydrogen bromide; the oxygen-containing gas is pure oxygen, air, or a mixture of oxygen and an inert gas, more preferably pure oxygen and air.

[0032] The mass ratio of anthracene compound to solvent is 1:4 to 99, more preferably 1:10 to 20; the molar ratio of anthracene compound to halogenating reagent is 1:1 to 3, more preferably 1:1.2 to 1.5; the molar ratio of anthracene compound to catalyst is anthracene compound:cobalt acetate:manganese acetate:hydrogen bromide = 1:0.1 to 0.5:0.01 to 0.05:0.2 to 0.6, more preferably 1:0.2 to 0.3:0.02 to 0.03: 0.3–0.4; the pressure of the oxygen-containing gas is 0.5–3 MPa, and the aeration rate is 0.5–3 L / min, more preferably 1–2 MPa and 1.5–2 L / min; the reaction temperature is 120–200 °C, and the reaction time is 1–6 h, more preferably 160–180 °C and 2–4 h; the mass ratio of the added dilution water to the initial solvent is 1–3, more preferably 1.5–2.

[0033] Example 1 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0034] Example 2 Add 10.68 g (60 mmol) of anthracene, 7.1 g (72 mmol) of hydrochloric acid (37 wt%), 2.64 g (15 mmol) of cobalt acetate, 0.26 g (1.5 mmol) of manganese acetate, 3.54 g (21 mmol) of hydrobromic acid (48 wt%), and 70 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0035] Example 3 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 150 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0036] Example 4 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 200 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0037] Example 5 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.5 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0038] Example 6 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 2 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0039] Example 7 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 1.5 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0040] Example 8 Add 5.34 g (30 mmol) of anthracene, 3.55 g (36 mmol) of hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 2 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0041] Example 9 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 0.66 g (3.75 mmol) cobalt acetate, 0.065 g (0.375 mmol) manganese acetate, 0.885 g (5.25 mmol) hydrobromic acid (48 wt%), 0.64 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0042] Example 10 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.065 g (0.375 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0043] Example 11 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.26 g (1.5 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0044] Example 12 Add 5.34 g (30 mmol) of anthracene, 3.94 g (40 mmol) of hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%) and 61 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0045] Example 13 Add 5.34 g (30 mmol) anthracene, 2.96 g (30 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.55 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0046] Example 14 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water, and 60 g acetic acid to a 100 mL reactor. Seal the reactor, turn on the mechanical stir, and heat to 180 °C. After the temperature stabilizes for 10 min, introduce nitrogen gas into the reactor at a purge rate of 2 L / min. A mixture of gas and oxygen (oxygen content 8 vol%) was used to stabilize the pressure inside the reactor at 1.8 MPa by adjusting the back pressure valve. The reaction began after 3 hours and reached the endpoint. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0047] Example 15 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water, and 60 g acetic acid to a 100 mL reactor. Seal the reactor, turn on the mechanical stir, and heat to 180 °C. After the temperature stabilizes for 10 min, introduce nitrogen gas into the reactor at a purge rate of 2 L / min. A mixture of gas and oxygen (oxygen content 35 vol%) was used to stabilize the pressure inside the reactor at 1.8 MPa by adjusting the back pressure valve. The reaction began after 3 hours and reached the endpoint. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0048] Example 16 Add 5.34 g (30 mmol) of anthracene, 3.55 g (36 mmol) of hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 1.84 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0049] Example 17 Add 5.34 g (30 mmol) anthracene, 3.55 g (36 mmol) hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) cobalt acetate, 0.13 g (0.75 mmol) manganese acetate, 1.77 g (10.5 mmol) hydrobromic acid (48 wt%), 0.18 g water and 60 g acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 150 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 1.

[0050] Table 1 Example 1 Standard conditions 91 Example 2 The substrate concentration was 11.3 wt%. 89 Example 3 Reaction temperature 150℃ 15 Example 4 Reaction temperature 200℃ 79 Example 5 Air pressure 1.5 MPa 80 Example 6 air pressure 2MPa 91 Example 7 Airflow rate 1.5 L / min 86 Example 8 Reaction time 2h 84 Example 9 <![CDATA[Co(OAc)212.5mol%,Mn(OAc)21.25mol%,HBr 17.5mol%]]> 37 Example 10 <![CDATA[Co(OAc)225mol%,Mn(OAc)21.25mol%,HBr 35mol%]]> 45 Example 11 <![CDATA[Co(OAc)225mol%,Mn(OAc)25mol%,HBr 35mol%]]> 76 Example 12 Halogenating reagent 1.33 eq. 92 Example 13 Halogenating reagent 1 eq. 86 Example 14 The oxygen content in the oxygen-containing gas is 8 vol%. 61 Example 15 The oxygen content in the oxygen-containing gas is 35 vol%. 89 Example 16 The solvent composition is water:acetic acid = 1:12 74 Example 17 Add 150 mL of water for dissolution and crystallization. 92 Example 18 Add 5.76 g (30 mmol) of 2-methylanthracene, 3.55 g (36 mmol) of hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0051] Example 19 Add 6.18 g (30 mmol) of 2-ethylanthracene, 3.55 g (36 mmol) of hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0052] Example 20 Add 7.44 g (30 mmol) of 2-tert-amyl anthracene, 3.55 g (36 mmol) of hydrochloric acid (37 wt%), 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0053] Example 21 Add 5.34 g (30 mmol) of anthracene, 1.53 g (36 mmol) of lithium chloride, 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0054] Example 22 Add 5.34 g (30 mmol) of anthracene, 2.1 g (36 mmol) of sodium chloride, 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0055] Example 23 Add 5.34 g (30 mmol) of anthracene, 2.68 g (36 mmol) of potassium chloride, 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0056] Example 24 Add 5.34 g (30 mmol) of anthracene, 3.68 g (36 mmol) of sodium bromide, 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0057] Example 25 Add 5.34 g (30 mmol) of anthracene, 4.28 g (36 mmol) of potassium bromide, 1.32 g (7.5 mmol) of cobalt acetate, 0.13 g (0.75 mmol) of manganese acetate, 1.77 g (10.5 mmol) of hydrobromic acid (48 wt%), 0.18 g of water and 60 g of acetic acid to a 100 mL reactor. After sealing the reactor, turn on the mechanical stirrer and heat to 180 °C. After the temperature stabilizes for 10 min, introduce standard air into the reactor at a ventilation rate of 2 L / min. Adjust the back pressure valve to stabilize the pressure inside the reactor at 1.8 MPa to start the reaction. The reaction reaches its endpoint after 3 h. After the reaction was completed, the reaction solution was transferred to a 250 mL crystallization vessel. The reaction solution was cooled to 10 °C and 120 mL of water was added dropwise while stirring continuously. The addition was completed in about 2 hours. The product was obtained by filtration using a Buchner funnel, washed with water, and dried in a 45 °C oven. The obtained product was analyzed by gas chromatography, with dimethyl phthalate as an internal standard. The results are shown in Table 2.

[0058] Table 2 Example 1 Standard conditions 91 Example 18 The substrate is 2-methylanthracene. 91 Example 19 The substrate is 2-ethylanthracene. 90 Example 20 The substrate is 2-tert-amyl anthracene. 93 Example 21 The halogenating agent is lithium chloride. 88 Example 22 The halogenating agent is sodium chloride. 92 Example 23 The halogenating agent is potassium chloride. 92 Example 24 The halogenating agent is sodium bromide. 78 Example 25 The halogenating agent is potassium bromide. 77 Unless otherwise specified, the raw materials and equipment used in this invention are all commonly used in the field; unless otherwise specified, the methods used in this invention are all conventional methods in the field.

[0059] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for one-step preparation of haloanthraquinone compounds, characterized in that: Anthracene compounds, halogenating reagents, catalysts, and solvents are mixed thoroughly, and oxygen-containing gas at a pressure of 0.5–3 MPa is continuously introduced. The reaction is carried out at 160–200 °C. After the reaction is completed, haloanthraquinone compounds are isolated. The reaction formula is as follows: ； Wherein, R is H, C1-C6 straight-chain alkyl, or C1-C6 branched alkyl; The solvent is a mixture of acetic acid and water; The halogenating reagents are selected from HCl, LiCl, LiBr, NaCl, NaBr, KCl, and KBr; The mass ratio of anthracene compounds to solvent is 1:4~99; The molar ratio of anthracene compounds to halogenating reagents is 1:1~3; The catalyst is a mixture of cobalt acetate, manganese acetate, and hydrogen bromide; The molar ratio of anthracene compounds to catalyst is anthracene compounds:cobalt acetate:manganese acetate:hydrogen bromide = 1:0.1~0.5:0.01~0.05:0.2~0.

6.

2. The method as described in claim 1, characterized in that: The solvent and catalyst were mixed evenly, and then anthracene compounds and halogenating reagents were added. The reaction system was sealed and heated to the reaction temperature. Oxygen-containing gas was continuously introduced and the reaction was carried out under stirring. When the reaction endpoint was reached, water was added to the mother liquor to dilute it. The reaction product gradually precipitated during the dilution process. After filtration and washing, haloanthraquinone compounds were obtained.

3. The method as described in claim 1 or 2, characterized in that: The mass ratio of the anthracene compound to the solvent is 1:10~20.

4. The method as described in claim 1 or 2, characterized in that: The molar ratio of the anthracene compound to the halogenating reagent is 1:1.2~1.

5.

5. The method as described in claim 1, characterized in that: The molar ratio of the anthracene compound to the catalyst is anthracene compound: cobalt acetate: manganese acetate: hydrogen bromide = 1:0.2~0.3:0.02~0.03:0.3~0.

4.

6. The method as described in claim 1 or 2, characterized in that: The ventilation rate of the oxygen-containing gas is 0.5~3 L / min.

7. The method as described in claim 1 or 2, characterized in that: The oxygen-containing gas is pure oxygen, air, or a mixture of oxygen and an inert gas.

8. The method as described in claim 1 or 2, characterized in that: The reaction time is 1 to 6 hours.

9. The method as described in claim 2, characterized in that: The separation methods for halogenated anthraquinone compounds are dissolution crystallization and filtration separation.

10. The method as described in claim 2 or 9, characterized in that: The mass ratio of water added to the initial solvent is 1 to 3.

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