CN110698353B - Preparation method of 4-chloro-2,5-dimethoxyaniline - Google Patents
Preparation method of 4-chloro-2,5-dimethoxyaniline Download PDFInfo
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- CN110698353B CN110698353B CN201911142992.0A CN201911142992A CN110698353B CN 110698353 B CN110698353 B CN 110698353B CN 201911142992 A CN201911142992 A CN 201911142992A CN 110698353 B CN110698353 B CN 110698353B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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Abstract
The invention relates to the technical field of organic synthesis, and particularly discloses a preparation method of 4-chloro-2,5-dimethoxyaniline. The preparation method comprises the following steps: in the presence of a supported nickel catalyst, 4-chloro-2,5-dimethoxynitrobenzene reacts with hydrazine hydrate by taking ethanol as a solvent, and 4-chloro-2,5-dimethoxyaniline is obtained by separating from a reaction liquid, wherein a carrier of the supported nickel catalyst is TiO 2 ‑Al 2 O 3 And (3) compounding a carrier. The preparation method of 4-chloro-2,5-dimethoxyaniline provided by the invention can effectively avoid the use of dehalogenation inhibitor and hydrogen, and has the advantages of simple process, convenient operation, environmental protection, safety, reliability, lower cost and product yield of more than or equal to 95%.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4-chloro-2,5-dimethoxyaniline.
Background
4-chloro-2,5-dimethoxyaniline (CDMA) is an important azo organic dye intermediate, and can prepare a plurality of yellow and red azo dyes through diazotization. At present, the production process of 4-chloro-2,5-dimethoxyaniline mainly adopts a chlorination-nitration method, and mainly comprises four steps of alkylation, chlorination, nitration and reduction, wherein the reduction step comprises a chemical reduction method (iron powder reduction, alkali sulfide reduction and the like), a hydrogen transfer hydrogenation method, a catalytic hydrogenation reduction method and the like. In the industrial production of aniline and its derivatives, the reduction method mainly used is chemical reduction method and catalytic hydrogenation method.
The iron powder reduction method has a mature process route, but has large waste water amount and high energy consumption in the production process, the product obtained by the reaction cannot be directly applied, the product needs to be decolorized, the process is complicated, an iron mud polluting the environment can be generated, and the post-treatment cost is high. The sodium sulfide reduction method easily generates a large amount of sulfur-containing wastewater and polysulfide-containing waste residues, and is difficult to treat. Meanwhile, pungent sulfur-containing gas generated by the reduction method is difficult to treat, the whole production environment is relatively severe, and the yield of target products is low. With the development of industrial technology, such processes will be gradually eliminated.
The catalytic hydrogenation reduction is a clean reduction synthesis method, and the catalyst is low in consumption and can be recycled. However, catalytic hydrogenation directly uses hydrogen as a hydrogen source, hydrogen is flammable and explosive, and many hydrogenation reactions are carried out under higher pressure, so that production is dangerous. The method has higher requirements on synthesis sites, equipment facilities, surrounding environment and the like. In addition, organic auxiliary agents are required to be added in the catalytic reaction to inhibit the generation of dechlorination products, so that the difficulty of separating the reaction products is increased, and the popularization and the application of the catalytic hydrogenation reduction method are limited.
Disclosure of Invention
Aiming at the technical problems in the existing 4-chloro-2,5-dimethoxyaniline preparation process, the invention provides a preparation method of 4-chloro-2,5-dimethoxyaniline.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a preparation method of 4-chloro-2,5-dimethoxyaniline comprises the following steps:
in the presence of a supported nickel catalyst, 4-chloro-2,5-dimethoxy nitrobenzene reacts with hydrazine hydrate by using ethanol as a solvent, and 4-chloro-2,5-dimethoxy aniline is obtained by separating from a reaction liquid, wherein the supported nickel catalyst is used for catalyzingThe carrier of the agent is TiO 2 -Al 2 O 3 And (3) compounding a carrier.
Compared with the prior art, the preparation method of the 4-chloro-2,5-dimethoxyaniline provided by the invention takes the 4-chloro-2,5-dimethoxynitrobenzene and hydrazine hydrate as main raw materials, takes ethanol as a solvent, can initiate an ethanol reforming reaction to generate hydrogen and CO while promoting the hydrazine hydrate to be decomposed into hydrogen and nitrogen under the action of a supported nickel catalyst, and can directly use the hydrogen obtained by the reaction in an in-situ catalytic hydrogenation reaction of the nitrobenzene to complete the hydrogen transfer hydrogenation reduction and form CO/H while completing the hydrogen transfer hydrogenation reduction 2 And the O reduction system further promotes the nitrobenzene reduction reaction and is beneficial to improving the reaction efficiency. In addition, tiO of supported nickel catalyst 2 -Al 2 O 3 The composite carrier integrates the advantages of the two and takes Al into consideration 2 O 3 And TiO 2 The catalytic performance of (2) contributes to the progress of the catalytic reduction reaction, and further improves the reaction efficiency. The method can effectively avoid the use of dehalogenation inhibitor and hydrogen, reduce the using amount of hydrazine hydrate, simplify the process, reduce the cost and improve the safety of the process at the same time.
Furthermore, the nickel loading in the supported nickel catalyst is 6-8 wt%, so that the activity of the catalyst is ensured.
Further, the TiO is 2 -Al 2 O 3 TiO in composite carrier 2 With Al 2 O 3 1.5-4.0 in a mass ratio of 1 2 O 3 Mainly ensures that the catalyst has good catalytic activity to hydrazine hydrate and ethanol.
Furthermore, the dosage of the supported nickel catalyst is 3-5% of the mass of the 4-chloro-2,5-dimethoxy nitrobenzene.
Further, the preparation method of the supported nickel catalyst comprises the following steps:
s1: dissolving titanium sulfate and aluminum nitrate in deionized water, adjusting the pH value to 7.5-8.5, precipitating and aging for 1.5-2.5 h, filtering and washing, drying at 80-100 ℃ for 8-12 h, and roasting to obtain TiO 2 -Al 2 O 3 A composite carrier;
s2: mixing the TiO with a solution of a binder 2 -Al 2 O 3 The composite carrier is soaked in nickel nitrate solution with the concentration of 0.2-0.4 mol/L for 3.5-4.5 h, dried at the temperature of 60-80 ℃ for 3-5 h, and roasted to obtain the supported nickel catalyst.
Further, in the step S1, the roasting temperature is 550-650 ℃, the roasting time is 4-6 h, and TiO with a mesoporous structure is formed 2 -Al 2 O 3 The composite carrier is convenient for subsequent nickel loading; in the step S2, the roasting temperature is 400-600 ℃, the roasting time is 4-6 h, a catalytic active component NiO is formed and loaded on TiO 2 -Al 2 O 3 And (3) a composite carrier.
Further, the mass ratio of the 4-chloro-2,5-dimethoxynitrobenzene to the hydrazine hydrate is 1:1.1 to 1.3, and the hydrazine hydrate and the ethanol act together to ensure that the nitrobenzene is reduced into the aniline.
Furthermore, the dosage of the ethanol is 4 to 8 times of the mass of the 4-chloro-2,5-dimethoxy nitrobenzene.
Further, the reaction temperature is 70-90 ℃ and the reaction time is 1.5-2.5 h.
Further, the method for separating the 4-chloro-2,5-dimethoxyaniline from the reaction solution comprises the following steps: filtering the reaction solution, recycling the catalyst, and crystallizing the obtained filtrate to obtain the 4-chloro-2,5-dimethoxyaniline.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of 4-chloro-2,5-dimethoxyaniline comprises the following steps:
s1: a1 is 2 (SO 4 ) 3 And Ti (SO) 4 ) 2 Dissolving in deionized water, stirring, adjusting pH to 8 with ammonia water, stirring for 0.5h, precipitating at 70 deg.C for 2h, and respectively using deionized waterWashing with water and anhydrous ethanol for 3 times, drying at 100 deg.C for 12 hr, and calcining at 650 deg.C for 5 hr to obtain TiO 2 -Al 2 O 3 Composite carrier, tiO in composite carrier 2 With Al 2 O 3 The mass ratio was 1:4. Mixing TiO with 2 -Al 2 O 3 Putting the composite carrier into a nickel nitrate solution with the concentration of 0.4mol/L, uniformly stirring, dipping for 4h at 90 ℃, filtering, drying for 3h at 80 ℃, and roasting for 5h at 500 ℃ to obtain the supported nickel catalyst Ni/TiO 2 -Al 2 O 3 Nickel loading was 8wt%;
s2: 1800mL of ethanol is added into a 5000mL four-mouth bottle provided with a reflux pipe, a thermometer and a stirring device, and 217.6g (1.0 mol) of 4-chloro-2,5-dimethoxy nitrobenzene and 8.5gNi/TiO are added in turn under stirring 2 -Al 2 O 3 Then the temperature is raised to 80 ℃ for reflux, 37mL (1.15 mol) of hydrazine hydrate is added dropwise, the reflux is kept, and the reaction is carried out for 2h until the 4-chloro-2,5-dimethoxynitrobenzene is completely reacted (HPLC tracking). After the reaction is finished, filtering while the reaction is hot, cooling the filtrate to-5 ℃, crystallizing for 12h, filtering to separate out white crystals, and drying in vacuum at 60 ℃ to obtain 178.2g (0.95 mol) of 4-chloro-2,5-dimethoxyaniline with the purity of 99.7 percent (HPLC) and the yield of 95 percent.
Example 2
A preparation method of 4-chloro-2,5-dimethoxyaniline comprises the following steps:
s1: a1 is prepared 2 (SO 4 ) 3 And Ti (SO) 4 ) 2 Dissolving in deionized water, stirring, adjusting pH to 7.5 with ammonia water, stirring for 0.5 hr, aging at 70 deg.C for 1.5 hr, washing with deionized water and anhydrous ethanol for 3 times, drying at 80 deg.C for 10 hr, and calcining at 650 deg.C for 5 hr to obtain TiO 2 -Al 2 O 3 Composite carrier, tiO in composite carrier 2 With Al 2 O 3 The mass ratio is 1. Adding TiO into the mixture 2 -Al 2 O 3 Putting the composite carrier into a nickel nitrate solution with the concentration of 0.3mol/L, uniformly stirring, dipping for 3.5h at 90 ℃, filtering, drying for 5h at 60 ℃, and roasting for 4h at 600 ℃ to obtain the supported nickel catalyst Ni/TiO 2 -Al 2 O 3 Nickel loading was 6wt%;
s2: 1650m of ethanol is added into a 5000mL four-mouth bottle provided with a reflux pipe, a thermometer and a stirring device, and 4-chlorine-2,5-dimethoxy nitrobenzene 326.4g (1.5 mol) and 16.4g of supported nickel catalyst Ni/TiO are added in turn under stirring 2 -Al 2 O 3 And heating to 70 ℃ for refluxing, dropwise adding 60mL (1.95 mol) of hydrazine hydrate, keeping refluxing, and reacting for 2.5 hours until the 4-chloro-2,5-dimethoxynitrobenzene is completely reacted (HPLC tracking). After the reaction is finished, filtering while the reaction is hot, cooling the filtrate to-5 ℃, crystallizing for 12h, filtering to separate out white crystals, and drying in vacuum at 60 ℃ to obtain 270.2g (1.43 mol) of 4-chloro-2,5-dimethoxyaniline with the purity of 99.5 percent (HPLC) and the yield of 96 percent.
Example 3
A preparation method of 4-chloro-2,5-dimethoxyaniline comprises the following steps:
s1: a1 is 2 (SO 4 ) 3 And Ti (SO) 4 ) 2 Dissolving in deionized water, stirring, adjusting pH to 8.5 with ammonia water, stirring for 0.5 hr, aging at 70 deg.C for 2.5 hr, washing with deionized water and anhydrous ethanol for 3 times, drying at 90 deg.C for 8 hr, and calcining at 650 deg.C for 5 hr to obtain TiO 2 -Al 2 O 3 Composite carrier, tiO in composite carrier 2 With Al 2 O 3 The mass ratio was 1:3. Adding TiO into the mixture 2 -Al 2 O 3 Putting the composite carrier into a nickel nitrate solution with the concentration of 0.2mol/L, stirring uniformly, dipping for 4.5h at 90 ℃, filtering, drying for 4h at 70 ℃, and roasting for 6h at 400 ℃ to obtain the supported nickel catalyst Ni/TiO 2 -Al 2 O 3 Nickel loading was 7wt%;
s2: 2640mL of ethanol is added into a 5000mL four-mouth bottle provided with a reflux pipe, a thermometer and a stirring device, and 4-chloro-2,5-dimethoxynitrobenzene 261.1g (1.2 mol) and 7.8g of supported nickel catalyst Ni/TiO are sequentially added under stirring 2 -Al 2 O 3 And raising the temperature to 90 ℃ for refluxing, dropwise adding 40.8mL (1.32 mol) of hydrazine hydrate, keeping refluxing, and reacting for 1.5h until the 4-chloro-2,5-dimethoxynitrobenzene completely reacts (HPLC tracking). After the reaction is finished, filtering while the reaction is hot, cooling the filtrate to-5 ℃, crystallizing for 12h, filtering to separate out white crystals, and drying to obtain the 4-chloro-2,5-dimethoxyaniline218.4g (1.16 mol), purity 99.7% (HPLC), yield 97%.
In order to better illustrate the technical solution of the present invention, further comparison is made below by means of a comparative example and an example of the present invention.
Comparative example 1
The reaction solvent in the step S2 in the example 1 is replaced by methanol with the same amount as ethanol, the amount and the preparation method of other components are the same as those in the example 1, after the reaction is finished, the hot reaction solution is filtered, the filtrate is cooled to-5 ℃, crystallized for 12h, white crystals are separated out by filtration, and after drying, 155.7g (0.83 mol) of 4-chloro-2,5-dimethoxyaniline with the purity of 99.3 percent (HPLC) and the yield of 83 percent are obtained.
Comparative example 2
The catalyst in step S2 of example 1 was replaced with the same amount of Ni/gamma-Al 2 O 3 The other components and the preparation method are the same as those in the example 1, after the reaction is finished, the hot reaction solution is filtered, the filtrate is cooled to-5 ℃, the crystallization is carried out for 12 hours, white crystals are separated out by filtration, and 165.1g (0.88 mol) of 4-chloro-2,5-dimethoxyaniline, the purity of which is 99.4 percent (HPLC) and the yield of which is 88 percent, are obtained after drying.
Comparative example 3
The catalyst in step S2 in example 1 was replaced with the same amount of Pt/C, the amount of other components and the preparation method were the same as in example 1, after the reaction was completed, the hot filtrate was filtered, the filtrate was cooled to-5 ℃ and crystallized for 12 hours, white crystals were precipitated by filtration, and after drying, 153.8g (0.82 mol) of 4-chloro-2,5-dimethoxyaniline, purity 99.2% (HPLC), yield 82% were obtained.
The data show that the preparation method of the 4-chloro-2,5-dimethoxyaniline provided by the invention can effectively avoid the use of dehalogenation inhibitor and hydrogen, does not produce waste residue and waste liquid, and has the advantages of simple process, convenience in operation, environmental friendliness, safety, reliability, low cost and product yield of more than or equal to 95%. The method is suitable for industrial production.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (5)
1. A preparation method of 4-chloro-2,5-dimethoxyaniline is characterized by comprising the following steps: the method comprises the following steps:
in the presence of a supported nickel catalyst, 4-chloro-2,5-dimethoxynitrobenzene reacts with hydrazine hydrate by taking ethanol as a solvent, and 4-chloro-2,5-dimethoxyaniline is obtained by separating from a reaction liquid, wherein a carrier of the supported nickel catalyst is TiO 2 -Al 2 O 3 A composite carrier;
the mass ratio of the 4-chloro-2,5-dimethoxy nitrobenzene to the hydrazine hydrate is 1:1.1 to 1.3;
the dosage of the supported nickel catalyst is 3-5% of the mass of 4-chloro-2,5-dimethoxy nitrobenzene;
the TiO is 2 -Al 2 O 3 TiO in composite carrier 2 With Al 2 O 3 The mass ratio is 1.5-4.0;
the preparation method of the supported nickel catalyst comprises the following steps:
s1: dissolving titanium sulfate and aluminum nitrate in deionized water, adjusting the pH value to 7.5-8.5, precipitating and aging for 1.5-2.5 h, filtering and washing, drying at 80-100 ℃ for 8-12 h, and roasting to obtain TiO 2 -Al 2 O 3 A composite carrier; the roasting temperature is 550-650 ℃, and the roasting time is 4-6 h;
s2: subjecting the TiO to a reaction 2 -Al 2 O 3 The composite carrier is soaked in nickel nitrate solution with the concentration of 0.2-0.4 mol/L for 3.5-4.5 h, dried for 3-5 h at the temperature of 60-80 ℃, and roasted to obtain a supported nickel catalyst; the roasting temperature is 400-600 ℃, and the roasting time is 4-6 h.
2. The process for the preparation of 4-chloro-2,5-dimethoxyaniline of claim 1 wherein: the nickel loading in the supported nickel catalyst is 6-8 wt%.
3. The process for the preparation of 4-chloro-2,5-dimethoxyaniline of claim 1 wherein: the dosage of the ethanol is 4 to 8 times of the mass of the 4-chloro-2,5-dimethoxy nitrobenzene.
4. The process for the preparation of 4-chloro-2,5-dimethoxyaniline of claim 1 wherein: the reaction temperature is 70-90 ℃ and the reaction time is 1.5-2.5 h.
5. The process for the preparation of 4-chloro-2,5-dimethoxyaniline of any of claims 1 to 4, wherein: the method for separating the 4-chloro-2,5-dimethoxyaniline from the reaction liquid comprises the following steps: filtering the reaction solution, recycling the catalyst, and crystallizing the obtained filtrate to obtain the 4-chloro-2,5-dimethoxyaniline.
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Address after: 061600 Chengnan Da Zhang Zhuang, Dongguang County, Cangzhou City, Hebei Province Applicant after: Hebei caike New Material Technology Co.,Ltd. Address before: 061600 Chengnan Da Zhang Zhuang, Dongguang County, Cangzhou City, Hebei Province Applicant before: TSAKER CHEMICAL (ZHANGZHOU) CO.,LTD. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |