阅读说明：本技术 一种2-甲氧基-4,4’-二硝基苯酰替苯胺的制备方法 (Preparation method of 2-methoxy-4, 4' -dinitro-benzoyl aniline ) 是由 吴岳林 朱亚召 何慧红 王传浩 汤文敏 董莲 吴晨 杨可莉 于 2020-11-06 设计创作，主要内容包括：本发明涉及一种2-甲氧基-4,4’-二硝基苯酰替苯胺的制备方法,该方法为：将4-硝基-2-甲氧基苯胺、对硝基苯甲酰氯置于反应釜中,然后加入溶剂,加热反应后,经冷却、过滤、水洗后得到白色目标产物,即为2-甲氧基-4,4’-二硝基苯酰替苯胺。与现有技术相比,本发明具有高效、绿色环保、安全、生产的产品质量好、操作稳定、收率高、三废少、生产成本低等优点。(The invention relates to a preparation method of 2-methoxy-4, 4' -dinitro-benzene acyl aniline, which comprises the following steps: putting 4-nitro-2-methoxyaniline and p-nitrobenzoyl chloride into a reaction kettle, then adding a solvent, heating for reaction, cooling, filtering and washing to obtain a white target product, namely 2-methoxy-4, 4' -dinitrobenzoyl aniline. Compared with the prior art, the method has the advantages of high efficiency, environmental protection, safety, good quality of produced products, stable operation, high yield, less three wastes, low production cost and the like.)

1. A method for preparing 2-methoxy-4, 4' -dinitro-benzoyl aniline is characterized by comprising the following steps: putting 4-nitro-2-methoxyaniline and p-nitrobenzoyl chloride into a reaction kettle, then adding a solvent, heating for reaction, cooling, filtering and washing to obtain a white target product, namely 2-methoxy-4, 4' -dinitrobenzoyl aniline.

2. The method for preparing 2-methoxy-4, 4' -dinitro-benzanilide according to claim 1, wherein the molar ratio of 4-nitro-2-methoxyaniline to p-nitrobenzoyl chloride is 1.0 (0.8-2.0).

3. The method for preparing 2-methoxy-4, 4' -dinitro-benzanilide according to claim 2, wherein the molar ratio of 4-nitro-2-methoxyaniline to p-nitrobenzoyl chloride is 1.0 (1.0-1.3).

4. The method of claim 3, wherein the molar ratio of 4-nitro-2-methoxyaniline to p-nitrobenzoyl chloride is 1.0: 1.0.

5. The method of claim 1, wherein the solvent comprises one or more of toluene, xylene, chlorobenzene, o-dichlorobenzene, or 1, 6-dichlorohexane.

6. The method according to claim 5, wherein the solvent is o-dichlorobenzene.

7. The method for producing 2-methoxy-4, 4' -dinitro-benzenecarboxanilide as claimed in claim 1, wherein the heating temperature is 100-150 ℃.

8. The method for producing 2-methoxy-4, 4' -dinitro-benzenecarboxanilide as claimed in claim 7, wherein the heating temperature is 130-150 ℃.

9. The method of claim 8 wherein the heating is carried out at a temperature of about 145 ℃.

10. The process for the preparation of 2-methoxy-4, 4' -dinitro-benzenecarboxanilide according to claim 1, wherein the reaction time is 4-8 h.

Technical Field

The invention relates to the field of chemical synthesis, and in particular relates to a preparation method of 2-methoxy-4, 4' -dinitro-benzeneanilide.

Background

The substituted amine compound is an important chemical intermediate, is widely applied to the industries of medicines and dyes, and is also widely applied to washing products and cosmetics. Meanwhile, it can also be used as raw material for synthesizing herbicide, and has multiple uses.

The preparation literature of 2-methoxy-4, 4 '-dinitro-benzoyl aniline is numerous, Japanese patent JP2017203061 describes a method for synthesizing 2-methoxy-4, 4' -dinitro-benzoyl aniline by using pyridine as an acid-binding agent and tetrahydrofuran as a solvent, the yield is 91%, and the method has the defects that the acid-binding agent pyridine is used, a large amount of waste water is brought in the post-treatment process, the waste water containing pyridine cannot be directly discharged and needs to be treated, and the cost of waste water treatment is increased; japanese patent JP03161465 describes a method of synthesizing 2-methoxy-4, 4' -dinitro-benzoyl aniline with pyridine as acid-binding agent and acetonitrile as solvent, the yield is 94%, and the patent also has the same disadvantages as the above patent; the literature, Indian Journal of Chemistry, Section B, Organic Chemistry incorporating Medicinal Chemistry,25B (12), 1277-. The patent uses potassium carbonate as alkali, the yield is obviously reduced, and the production cost is increased; and meanwhile, the wastewater contains salt, so that the wastewater treatment cost is increased.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a preparation method of 2-methoxy-4, 4' -dinitro-benzenesulfilide, which has the advantages of high efficiency, environmental protection, safety, good quality of produced products, stable operation, high yield, less three wastes and low production cost.

The purpose of the invention can be realized by the following technical scheme:

a method for preparing 2-methoxy-4, 4' -dinitro-benzoyl aniline comprises the following steps: putting 4-nitro-2-methoxyaniline and p-nitrobenzoyl chloride into a reaction kettle, then adding a solvent, heating for reaction, cooling, filtering and washing to obtain a white target product, namely 2-methoxy-4, 4' -dinitrobenzoyl aniline. The yield thereof is 85 to 99 percent.

The process route is as follows:

furthermore, the molar ratio of the 4-nitro-2-methoxyaniline to the p-nitrobenzoyl chloride is 1.0 (0.8-2.0).

Furthermore, the molar ratio of the 4-nitro-2-methoxyaniline to the p-nitrobenzoyl chloride is 1.0 (1.0-1.3).

Further, the solvent comprises one or more of toluene, xylene, chlorobenzene, o-dichlorobenzene or 1, 6-dichlorohexane. Ortho-dichlorobenzene is preferred.

Further, the heating temperature is 100-150 ℃.

Further, the heating temperature is 130-150 ℃.

Further, the reaction time is 4-8 h. Preferably 5-7 h.

Compared with the prior art, the invention designs the preparation process of the 2-methoxy-4, 4' -dinitro-benzoyl aniline. The process is a high-efficiency, green, environment-friendly and safe preparation process of 2-methoxy-4, 4' -dinitrobenzoyl aniline, 4-nitro-2-methoxy aniline and p-nitrobenzoyl chloride are placed in a reaction kettle, then slowly heated to 145 ℃, a system is changed into liquid, the liquid is cooled to room temperature after the liquid reacts for 4 to 8 hours at the temperature, a large amount of white solid is separated out, and the white solid is obtained through filtration and washing. The reaction yield is 85-99%. The product produced by the method has the advantages of good quality, stable operation, high yield, less three wastes and low production cost.

Detailed Description

The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.

Example 1

The preparation process of 2-methoxy-4, 4' -dinitro benzoyl aniline includes the following steps:

330 liters of o-dichlorobenzene is put into a reaction kettle, 4-nitro-2-methoxyaniline (67.2 kg) is added, p-nitrobenzoyl chloride (74.2 kg) is added under stirring, then the reaction kettle is slowly heated to 145 ℃, a large amount of hydrogen chloride is discharged in the process, the hydrogen chloride is absorbed by water, the reaction kettle reacts for 6 hours at the temperature, the reaction kettle is cooled to room temperature, a large amount of white solid is separated out after stirring for a period of time, the white solid is obtained by filtration and washing, 123.1 kg of target product is dried, and the yield is 97.0%.

¹H NMR(500MHz,DMSO-d6)δ10.14(s,1H),8.35(d,2H),8.15-8.21(m, 3H),7.88-7.93(m,2H),3.98(s,3H)。

Example 2

The preparation process of 2-methoxy-4, 4' -dinitro benzoyl aniline includes the following steps:

150 liters of o-dichlorobenzene is put into a reaction kettle, 4-nitro-2-methoxyaniline (67.2 kg) is added, p-nitrobenzoyl chloride (74.2 kg) is added under stirring, then the reaction is slowly heated to 145 ℃ and carried out for 5 hours at the temperature, in the process, a large amount of hydrogen chloride is discharged, water is used for absorbing, the reaction product is cooled to room temperature, after stirring for a period of time, a large amount of white solid is separated out, the white solid is obtained by filtration and washing, 125.6 kg of target product is dried, and the yield is 99.0%.

¹H NMR(500MHz,DMSO-d6)δ10.14(s,1H),8.35(d,2H),8.15-8.21(m, 3H),7.88-7.93(m,2H),3.98(s,3H)。

Example 3

The preparation process of 2-methoxy-4, 4' -dinitro benzoyl aniline includes the following steps:

330 liters of chlorobenzene is put into a reaction kettle, 4-nitro-2-methoxyaniline (67.2 kg) is added, p-nitrobenzoyl chloride (74.2 kg) is added under stirring, then the temperature is slowly heated to 130 ℃, in the process, a large amount of hydrogen chloride is discharged, the hydrogen chloride is absorbed by water, after the reaction is carried out for 6 hours at the temperature, the room temperature is cooled, after stirring for a period of time, a large amount of white solid is separated out, the white solid is obtained by filtration and washing, 117.5 kg of target product is dried, and the yield is 92.6%.

¹H NMR(500MHz,DMSO-d6)δ10.14(s,1H),8.35(d,2H),8.15-8.21(m, 3H),7.88-7.93(m,2H),3.98(s,3H)。

Example 4

The preparation process of 2-methoxy-4, 4' -dinitro benzoyl aniline includes the following steps:

330 liters of dimethylbenzene is put into a reaction kettle, 4-nitro-2-methoxyaniline (67.2 kg) is added, p-nitrobenzoyl chloride (74.2 kg) is added under stirring, then the mixture is slowly heated to 135 ℃, in the process, a large amount of hydrogen chloride is discharged, the hydrogen chloride is absorbed by water, after the mixture reacts for 6 hours at the temperature, the mixture is cooled to room temperature, after stirring for a period of time, a large amount of white solid is separated out, the white solid is obtained by filtration and washing, 116.0 kg of target product is dried, and the yield is 91.4%.

¹H NMR(500MHz,DMSO-d6)δ10.14(s,1H),8.35(d,2H),8.15-8.21(m, 3H),7.88-7.93(m,2H),3.98(s,3H)。

Example 5

The preparation process of 2-methoxy-4, 4' -dinitro benzoyl aniline includes the following steps:

330 liters of toluene is put into a reaction kettle, 4-nitro-2-methoxyaniline (67.2 kg) is added, p-nitrobenzoyl chloride (74.2 kg) is added under stirring, then the temperature is slowly heated to 110 ℃, in the process, a large amount of hydrogen chloride is discharged, water is used for absorption, after the reaction is carried out for 6 hours at the temperature, the room temperature is cooled, after stirring for a period of time, a large amount of white solid is separated out, the white solid is obtained by filtration and washing, 113.8 kg of target product is obtained after drying, and the yield is 89.7%.

¹H NMR(500MHz,DMSO-d6)δ10.14(s,1H),8.35(d,2H),8.15-8.21(m, 3H),7.88-7.93(m,2H),3.98(s,3H)。

Example 6

The preparation process of 2-methoxy-4, 4' -dinitro benzoyl aniline includes the following steps:

330 l of 1, 6-dichlorohexane is put into a reaction kettle, 4-nitro-2-methoxyaniline (67.2 kg) is added, p-nitrobenzoyl chloride (74.2 kg) is added under stirring, then the mixture is slowly heated to 130 ℃, in the process, a large amount of hydrogen chloride is discharged, the hydrogen chloride is absorbed by water, after the mixture reacts for 6 hours at the temperature, the mixture is cooled to room temperature, after stirring for a period of time, a large amount of white solid is separated out, the mixture is filtered and washed by water to obtain white solid, after drying, 107.9 kg of target product is obtained, and the yield is 85.0%.

¹H NMR(500MHz,DMSO-d6)δ10.14(s,1H),8.35(d,2H),8.15-8.21(m, 3H),7.88-7.93(m,2H),3.98(s,3H)。

The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims.