CN108623491B - Preparation method of halogenated benzamide compound - Google Patents
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Abstract
The invention discloses a preparation method of a halogenated benzamide compound. The preparation method comprises the following steps: adding hydrogen peroxide into a mixed solution obtained by mixing a compound shown in the formula I, water and alkali, and carrying out the reaction shown in the specification; wherein X is halogen and n is 1, 2,3,4 or 5; the feeding amount of the compound shown in the formula I is at least 8g, and the molar ratio of the hydrogen peroxide to the compound shown in the formula I is 1: 1-1.6: 1; the adding time of the hydrogen peroxide is 2-10 h. The preparation method adopts water as a reaction solvent, avoids the use of an organic solvent, can still achieve higher yield and good product quality on the basis of reducing the consumption of raw materials, is simple to operate, has less three wastes and high economic effect, and is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of a halogenated benzamide compound.
Background
The halogenated benzamide compound is a key intermediate for synthesizing the benzoylurea insecticides, the benzoylurea insecticides belong to chitin synthesis inhibitors, and kill insects by inhibiting the biosynthesis of chitin in the bodies of the insects, have different action mechanisms from other insecticides, have the characteristics of high insecticidal activity, wide insecticidal spectrum, low residual quantity, strong selectivity, safety to people and livestock and the like, and are environment-friendly insecticide varieties. The benzoylurea insecticides are the main varieties of current insect growth regulator pesticides, and the demand at home and abroad is large, so the development of key intermediates is paid great attention in the pesticide industry.
The preparation method of the halogenated benzamide compound mainly comprises a sulfuric acid hydrolysis method, a metal catalysis method, an alkaline hydrolysis method and the like. The traditional method for hydrolyzing cyanophenyl into amide uses excessive concentrated sulfuric acid for hydrolysis, the yield of the method is high, but a large amount of waste water is generated, and the method is not environment-friendly. The metal catalysis method is to use metal such as ruthenium, gold, silver, copper and the like and metal ligand as a catalyst, and hydrolyze the metal and the metal ligand in air or oxygen to obtain amide. The alkaline hydrolysis method usually requires high temperature and high pressure conditions, and byproducts such as deacidification or carboxylic acid generation in the reaction process are also subjected to dehalogenation reaction, so that the yield is low, and the method is not suitable for industrial production.
Among them, basic hydrolysis of halophenylnitriles is an important preparation method for preparing halogenated benzamides, and the literature "discovery patent Small molecular Inhibitors of cyclophilins A Using de Novo Drug Design Approach", Journal of Medicinal Chemistry,200,952(17), 5295-; ni, Shuaishuai, describes a method for hydrolyzing o-chlorobenzonitrile into o-chlorobenzamide, which adopts DMSO as a solvent and adds hydrogen peroxide to react in the presence of potassium carbonate. The method uses DMSO as a solvent, has high production cost and is environment-friendly and not suitable for industrial production.
Patents CN101503372A, CN101462980A, CN1580042A, etc. describe methods for preparing halogenated benzamide from halogenated benzonitrile, which use alkali as a catalyst, and then add hydrogen peroxide dropwise to perform hydrolysis reaction, but the process has high consumption of hydrogen peroxide and alkali, and the resources are not saved; and the reaction yield is not high.
Disclosure of Invention
The invention aims to overcome the defects of non-resource saving, non-friendly environment, low reaction yield and the like in the existing preparation method for preparing the halogenated benzamide from the halogenated benzonitrile, and provides a preparation method of the halogenated benzamide compound. The preparation method adopts water as a reaction solvent, avoids the use of an organic solvent, can still achieve higher yield and good product quality on the basis of reducing the consumption of raw materials, is simple to operate, has less three wastes and high economic effect, and is suitable for industrial production.
The invention provides a preparation method of a halogenated benzamide compound, which comprises the following steps: adding hydrogen peroxide into a mixed solution obtained by mixing a compound shown in the formula I, water and alkali, and carrying out the reaction shown in the specification; wherein X is halogen and n is 1, 2,3,4 or 5; the feeding amount of the compound shown in the formula I is at least 8g, and the molar ratio of the hydrogen peroxide to the compound shown in the formula I is 1: 1-1.6: 1; the adding time of the hydrogen peroxide is 2-10 h;
the halogen is preferably fluorine, chlorine, bromine or iodine.
In the compound of the formula I, X can be positioned at one or more of the ortho position, the meta position and the para position of a cyano group.
In the compound of formula I, the compound of formula I is preferably any one of the following compounds: o-chlorobenzonitrile, p-chlorobenzonitrile, 2, 6-dichlorobenzonitrile, 2,3,4, 5-tetrachlorobenzonitrile, pentachlorobenzonitrile, o-fluorobenzonitrile, p-fluorobenzonitrile and 2, 6-difluorobenzonitrile.
The position of X in the compound of formula I relative to cyano is known to the skilled person in the art, i.e. correspondingly the position of X in the compound of formula II relative to carboxamide group.
In the 'the dosage of the compound of the formula I is at least 8 g', the dosage of the compound of the formula I can be laboratory grade or industrial production grade, such as the weight range of gram grade (8g is less than or equal to gram grade and less than 1000g), kilogram grade (1kg is less than or equal to kilogram grade and less than 1 ton) or ton grade (ton grade is more than or equal to 1 ton); wherein, the gram level is, for example, 8g to 100g, and is, for example, 41.6g or 51.6 g; for example, the kilogram grade is 1kg to 10kg, and for example, 4.16 kg; the ton is, for example, 1 ton to 10 tons, and further, for example, 1.3 tons to 2 tons.
The adding time of the hydrogen peroxide is preferably 4-8 h (for example, 5h, 5.5h or 6 h).
The adding time of the hydrogen peroxide is preferably 2-6 h when the dosage of the compound of the formula I is on the gram scale (for example, the adding time of the hydrogen peroxide is preferably 4h, 5h, 5.5h or 6h when the dosage of the compound of the formula I is 41.6 g; and the adding time of the hydrogen peroxide is preferably 5h when the dosage of the compound of the formula I is 51.6 g); when the dosage of the compound of the formula I is in the kilogram grade, the adding time of the hydrogen peroxide is preferably 4-8 h (when the dosage of the compound of the formula I is 4.16kg, the adding time of the hydrogen peroxide is preferably 6 h); when the dosage of the compound of the formula I is on the ton scale, the addition time of the hydrogen peroxide is preferably 6-10 h (for example, when the dosage of the compound of the formula I is 1.25 tons, the addition time of the hydrogen peroxide is preferably 10 h).
The base may be a base conventionally used in this type of reaction in the art, and is preferably one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and aqueous ammonia. The alkali may be reacted in the form of an aqueous alkali solution, preferably an aqueous alkali solution having a mass concentration of 20% to 30%, more preferably an aqueous sodium hydroxide solution having a mass concentration of 20% to 30%. The molar ratio of the base to the compound of formula I is preferably 0.005-0.05, more preferably 0.01: 1-0.02: 1, and even more preferably 0.015: 1.
The hydrogen peroxide can participate in the reaction in the form of an aqueous solution thereof, which can be selected according to the conventional method of the reaction in the field, and the aqueous solution of hydrogen peroxide with the mass concentration of 27.5-30% is preferred. The molar ratio of the hydrogen peroxide to the compound shown in the formula I is preferably 1.2: 1-1.5: 1.
In the preparation method of the halogenated benzamide compound, the water is used in an amount which can disperse a reaction substrate and does not influence the reaction; the mass of said water to said compound of formula I is preferably 0.9:1 to 1.1:1, more preferably 1:1 (it is understood that said water in said "mass ratio of said water to said compound of formula I" does not comprise water in said aqueous base solution and aqueous hydrogen peroxide solution).
The reaction temperature of the reaction can be selected according to the conventional methods of the reactions in the field, and is preferably 20-50 ℃, more preferably 30-40 ℃, and further preferably 35 ℃.
The progress of the reaction can be monitored by detection methods conventional in the art (e.g., HPLC, NMR, TLC, etc.), and is generally terminated when the amount of the compound of formula I is less than 0.5% (i.e., 0.5% of the initial amount of the compound of formula I added).
The preparation method of the halogenated benzamide compound can further comprise the following post-treatment steps after the reaction is finished: filtering the reaction liquid, and drying the filter cake. The filtration also comprises a process of washing the filter cake with water.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the method adopts water as a reaction solvent, avoids the use of an organic solvent, can still achieve higher yield and good product quality on the basis of reducing the consumption of raw materials, is simple to operate, has less three wastes and high economic effect, and is suitable for industrial production.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 5 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when being less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 45.7g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98 percent.
Example 2
51.6g (0.3mol) of 2, 6-dichlorobenzonitrile, 41.6g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is added dropwise, the dropwise addition is completed within 5 hours, the sampling is carried out for central control after the dropwise addition is completed, and the 2, 6-dichlorobenzonitrile is qualified when the concentration is less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 55g of finished product 2, 6-dichlorobenzamide, wherein the purity is more than 99.0 percent, and the yield is 97 percent.
Example 3
Adding 41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 0.6g of 30% sodium hydroxide solution into a 500ml reaction bottle, heating to 35 ℃, dropwise adding 37.1g (0.3mol) of 27.5% hydrogen peroxide, finishing dropwise adding within 4 hours, sampling and controlling the samples after the dropwise adding is finished, and ensuring that the o-chlorobenzonitrile is not more than 0.5% qualified. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 45.4g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 97.5 percent.
Example 4
41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 59.3g (0.48mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 5.5 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when being less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 45.75g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98.1 percent.
Example 5
41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 0.2g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 5 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when being less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 45.6g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 97.8 percent.
Example 6
41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 2g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is dripped in the bottle, the dripping is finished within 5 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when being less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 45.7g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98.0 percent.
Example 7
41.6g (0.3mol) of o-chlorobenzonitrile, 37.4g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 5 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when being less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 45.7g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98.0 percent.
Example 8
41.6g (0.3mol) of o-chlorobenzonitrile, 45.8g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 5 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when being less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 45.8g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98.2 percent.
Example 9
Adding 8.3g (0.06mol) of o-chlorobenzonitrile, 8.3g of water and 0.12g of 30% sodium hydroxide solution into a 100ml reaction bottle, heating to 35 ℃, dropwise adding 11.1g (0.09mol) of 27.5% hydrogen peroxide, finishing dropwise adding within 2 hours, sampling and controlling the samples after dropwise adding, and ensuring that the o-chlorobenzonitrile is not more than 0.5% qualified. Filtering, leaching the filter cake with 17g of water, and drying the wet product to obtain 9.1g of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98 percent.
Example 10
Adding 4.16kg (30mol) of o-chlorobenzonitrile, 4.16kg of water and 60g of 30% sodium hydroxide solution into a 50L reaction kettle, heating to 35 ℃, dropwise adding 5.6kg (45mol) of 27.5% hydrogen peroxide, dropwise adding after 6 hours, sampling and controlling during the dropwise adding, wherein the o-chlorobenzonitrile is less than or equal to 0.5%, and the product is qualified. Filtering, leaching the filter cake with 8.3kg of water, and drying the wet product to obtain 4.6kg of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98.5 percent.
Example 11
1.25 tons (9.1kmol) of o-chlorobenzonitrile, 1.25 tons of water and 18kg of 30 percent sodium hydroxide solution are added into a 8000L reaction kettle, the temperature is raised to 35 ℃, 1.69 tons (13.6kmol) of 27.5 percent hydrogen peroxide is dripped, the dripping is finished within 10 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when the o-chlorobenzonitrile is less than or equal to 0.5 percent. Filtering, leaching the filter cake with 2.5 tons of water, and drying the wet product to obtain 1.39 tons of finished o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 98.5 percent.
Comparative example 1
41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 92.7g (0.75mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 8 hours, sampling and central control are carried out after the dripping is finished, and the o-chlorobenzonitrile is qualified when being less than or equal to 0.5%. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain a finished product of 42.9g of o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 92 percent.
Comparative example 2
41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 1.0 hour, and sampling and central control are carried out after the dripping is finished, the o-chlorobenzonitrile is more than 0.5%, and the product is not qualified. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain 41.1g of finished product o-chlorobenzamide with the purity of less than 99.0 percent and the yield of 88 percent.
Comparative example 3
41.6g (0.3mol) of o-chlorobenzonitrile, 41.6g of water and 0.6g of 30% sodium hydroxide solution are added into a 500ml reaction bottle, the temperature is raised to 35 ℃, 55.65g (0.45mol) of 27.5% hydrogen peroxide is dripped, the dripping is finished within 15 hours, and sampling and central control are carried out after the dripping is finished, wherein the o-chlorobenzonitrile is less than 0.5%, and the product is qualified. Filtering, leaching a filter cake with 83.2g of water, and drying a wet product to obtain a finished product of 43.9g of o-chlorobenzamide with the purity of more than 99.0 percent and the yield of 94 percent.
As can be seen from comparative examples 1-3, when the amount and the adding time of the hydrogen peroxide are out of the range of the application, the reaction effect is poor, and especially the amount of the hydrogen peroxide in comparative example 1 is high, so that the waste of resources is caused. When the technical scheme of the application is adopted, a higher reaction effect can be achieved on the basis of reducing the consumption of hydrogen peroxide. In addition, the hydrogen peroxide is active in property and strong in oxidizability, and the reduction of the consumption of the hydrogen peroxide not only saves resources, but also reduces the storage cost and improves the safety. And the preparation method of the application realizes kilogram-level production (such as example 10 and example 11), and has high industrial value.
Claims (10)
1. A method for preparing a halogenated benzamide compound, which is characterized by comprising the following steps:
adding hydrogen peroxide into a mixed solution obtained by mixing a compound shown in the formula I, water and alkali, and carrying out the reaction shown in the specification; wherein the feeding amount of the compound shown in the formula I is at least 8g, and the molar ratio of the hydrogen peroxide to the compound shown in the formula I is 1: 1-1.6: 1; the adding time of the hydrogen peroxide is 2-10 h; the compound of the formula I is o-chlorobenzonitrile or 2, 6-dichlorobenzonitrile; the molar ratio of the alkali to the compound of the formula I is 0.005-0.05; the reaction temperature of the reaction is 30-40 ℃;
2. the method according to claim 1, wherein the reaction mixture,
the hydrogen peroxide participates in the reaction in the form of an aqueous solution, and the aqueous solution of the hydrogen peroxide is 27.5-30% of aqueous solution of the hydrogen peroxide in mass concentration;
and/or the adding time of the hydrogen peroxide is 4-8 h;
and/or the molar ratio of the hydrogen peroxide to the compound of the formula I is 1.2: 1-1.5: 1;
and/or the dosage of the compound of the formula I is in the weight range of gram, kilogram or ton; wherein, the gram level is not less than 8g and is less than 1000g, the kilogram level is not less than 1kg and is less than 1 ton, and the ton level is not less than 1 ton.
3. The method according to claim 2,
the adding time of the hydrogen peroxide is 5-6 h;
and/or the gram level is 8g to 100 g;
and/or the kilogram grade is 1 kg-10 kg;
and/or the ton grade is 1 ton to 10 tons.
4. The production method according to claim 2 or 3,
when the feeding amount of the compound of the formula I is gram level, the adding time of the hydrogen peroxide is 2-6 h;
and/or when the feeding amount of the compound shown in the formula I is kilogram grade, the adding time of the hydrogen peroxide is 4-8 h;
and/or when the dosage of the compound of the formula I is the ton grade, the adding time of the hydrogen peroxide is 6-10 h.
5. The method according to claim 4,
when the dosage of the compound of the formula I is on the gram level, the adding time of the hydrogen peroxide is 4h, 5h or 5.5 h;
and/or, when the dosage of the compound of the formula I is in the kilogram grade, the adding time of the hydrogen peroxide is 6 h.
6. The method according to claim 1, wherein the reaction mixture,
the alkali is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate and ammonia water and/or takes part in the reaction in the form of an alkali water solution, and the alkali water solution is an alkali water solution with the mass concentration of 20-30%;
and/or the mass ratio of the water to the compound of the formula I is 0.9: 1-1.1: 1.
7. The method according to claim 6,
the molar ratio of the base to the compound of formula I is 0.01: 1-0.02: 1;
and/or the mass ratio of the water to the compound of the formula I is 1: 1.
8. The method according to claim 7,
the molar ratio of the base to the compound of formula I is 0.015: 1;
and/or the reaction temperature of the reaction is 35 ℃.
9. The method according to claim 1, wherein the reaction mixture,
the reaction is terminated with an amount of the compound of formula I of less than 0.5%.
10. The method of claim 1, further comprising the following post-treatment steps after the reaction is completed: filtering the reaction liquid, and drying the filter cake.
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Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0008532B1 (en) * | 1978-08-22 | 1983-07-20 | Sumitomo Chemical Company, Limited | Synthesis of amines |
| DE3026959A1 (en) * | 1980-07-16 | 1982-02-04 | Bayer Ag, 5090 Leverkusen | METHOD FOR THE PRODUCTION OF 3-BROM-4-FLUOR-BENZALDEHYDE - (- ACETALEN) AND NEW INTERMEDIATE PRODUCTS FOR THIS |
| FR2534580A1 (en) * | 1982-10-13 | 1984-04-20 | Synthelabo | PHENYL-1 PIPERIDINO-2 PROPANOL DERIVATIVES, THEIR PREPARATION, AND MEDICINES THAT CONTAIN THEM |
| CS264402B1 (en) * | 1987-02-12 | 1989-08-14 | Kalab Jiri | Process for preparing o-chlorbenzamide |
| JP4228587B2 (en) * | 2002-05-22 | 2009-02-25 | 昭和電工株式会社 | Process for producing aminomethyl group-containing benzamide compound |
| CN1218935C (en) * | 2003-08-15 | 2005-09-14 | 中国科学院动物研究所 | Substituted benzoyl urea insect growth regulator synthesizing method |
| CN101462980B (en) * | 2009-01-05 | 2013-01-09 | 扬州天辰精细化工有限公司 | Industrial production method of 2,6-difluorobenzamide |
| AU2010203512C1 (en) * | 2009-01-08 | 2013-10-17 | Curis, Inc. | Phosphoinositide 3-kinase inhibitors with a zinc binding moiety |
| CN101503372A (en) * | 2009-03-18 | 2009-08-12 | 中国中化集团公司 | Preparation of fluoro benzamide compound |
| CN102050754B (en) * | 2009-10-29 | 2013-09-11 | 中国中化股份有限公司 | Method for preparing alpha-amino-dialkyl substituted acetamide |
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Effective date of registration: 20220701 Address after: 318020 No. 8, yongjiao Road, Jiangkou street, Huangyan District, Taizhou City, Zhejiang Province Patentee after: Lianhua angjian Pharmaceutical (Taizhou) Co.,Ltd. Address before: No.8, yongjiao Road, Huangyan Economic Development Zone, Taizhou City, Zhejiang Province Patentee before: LIANHE CHEMICAL TECHNOLOGY Co.,Ltd. Patentee before: JIANGSU LIANHUA TECHNOLOGY Co.,Ltd. Patentee before: LIANHE CHEMICAL TECHNOLOGY (YANCHENG) Co.,Ltd. |