Preparation method of bifenthrin

Abstract

The invention relates to the field of organic synthesis, and discloses a preparation method of bifenthrin. The method comprises the following steps: in the presence of a catalyst composition, enabling kung-fu acid and 2-methyl-3-phenylbenzyl alcohol to be in contact for esterification reaction, the catalyst composition comprises a component A and a component B, wherein the component A is selected from an oxyacid ester of an IVB group element and / or a compound formed by the IVB group element and alcohol; wherein the component B is selected from at least one of inorganic salt of copper, oxide of copper, oxide of tin and inorganic salt of tin. The yield of the bifenthrin prepared by the method is high (more than 98%), the purity is high (up to 99.4%), the produced bifenthrin isomers are less (less than 0.5%), the market requirements can be met, and the whole process flow is efficient and environment-friendly.

Description

Technical Field

[0001] The invention relates to the field of organic synthesis, and in particular to a method for preparing bifenthrin. Background Art

[0002] Bifenthrin, commonly known as bifenthrin in English, is a pyrethroid insecticide developed by FMC. It can be used as a highly effective insecticide and acaricide, and has the advantages of broad-spectrum insecticide and high efficacy. The characteristic of bifenthrin is that it does not move in the soil and is relatively safe for the environment. More importantly, bifenthrin is metabolized quickly in mammals such as humans and does not have the risk of accumulation. In 1978, FMC disclosed the synthesis and biological activity of bifenthrin in patent US4341796A. Subsequently, the application research of bifenthrin was widely carried out worldwide. However, in fact, the synthesis process of bifenthrin compound raw materials still has problems such as large amount of three wastes, complex operation, and serious environmental pollution.

[0003] US4341796A discloses a method for producing bifenthrin by dehydrating gongfu acid (Z-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid, also known as trifluoroacetic acid) with potassium hydroxide aqueous solution to form a salt and then reacting with 2-methyl-3-chloromethylbiphenyl. In this method, since 1.26 equivalents of 12% potassium hydroxide aqueous solution are used, a large amount of wastewater is generated, and the yield of the reaction is only 40%.

[0004] US4473709A discloses a method for preparing bifenthrin from gongfu acid chloride and biphenyl alcohol (2-methylbiphenyl benzyl alcohol). In the process of preparing gongfu acid chloride from gongfu acid, thionyl chloride is used, which produces a large amount of hydrogen chloride and sulfuric acid dioxide gas. In the process of synthesizing bifenthrin by reacting gongfu acid chloride with biphenyl alcohol, pyridine is used as an acid-binding agent. The presence of pyridine increases the difficulty of three waste treatment.

[0005] CN103145558B and CN102827004A disclose a method of preparing cypermethrin by esterifying cypermethrin with cypermethrin and reacting cypermethrin with 3-biphenylmethanol. However, the method cannot be carried out thoroughly, has high cost and complicated steps, and is not suitable for industrial production.

[0006] CN109485564B discloses a method for preparing bifenthrin by condensing kungfu acid and biphenyl alcohol using trimethylsilyl magnesium chloride as a catalyst. The trimethylsilyl magnesium chloride used in the method is expensive and flammable, which limits its application in industrial production. In addition, a large amount of water is added during the post-treatment process for two water washings, resulting in a large amount of wastewater, which does not meet the requirements of green technology.

[0007] CN113788754A also reported that a single titanate was used as a catalyst for this reaction, with a preferred reaction temperature of 80-170°C and a reaction time of 2-8h. However, in actual research, only titanate catalysis requires a higher reaction temperature. When toluene is used as a solvent, the reflux reaction temperature is 112°C, and the remaining 32% of biphenylmethanol is no longer converted (Comparative Example 1). When xylene is used as a reflux reaction temperature of 140°C, it takes 58h to complete the reaction, and the generated bifenthrin isomer (Formula 2) (non-effective component, regarded as an impurity, and difficult to remove) is 2.8%; the effective content of bifenthrin crude oil is 93.3%, and the yield is 93.2% (Comparative Example 2), which cannot meet market requirements. There is no cost advantage.

[0008] Therefore, in order to make up for the above-mentioned defects, a preparation method of bifenthrin is needed. Summary of the invention

[0009] The purpose of the present invention is to overcome the problem that high yield, low by-products, low energy consumption and environmental friendliness cannot be achieved simultaneously in the prior art, and to provide a method for preparing bifenthrin.

[0010] In order to achieve the above object, the present invention provides a method for preparing bifenthrin, characterized in that the method comprises: contacting gongfu acid and 2-methyl-3-phenylbenzyl alcohol to carry out esterification reaction in the presence of a catalyst composition;

[0011] Wherein, the catalyst composition comprises component A and component B;

[0012] Wherein, the component A is selected from oxygen-containing acid esters of group IVB elements and / or compounds formed by group IVB elements and alcohols;

[0013] Wherein, the component B is at least one selected from the group consisting of an inorganic salt of copper, an oxide of copper, an oxide of tin and an inorganic salt of tin.

[0014] Through the above technical scheme, the present invention provides a method for preparing bifenthrin, and a low-cost catalyst composition is used to obtain a bifenthrin product with a high yield (>98%) and high purity (up to 99.4%), and the amount of bifenthrin isomers produced is less (<0.5%), which can meet market requirements, and the entire process is efficient and environmentally friendly. DETAILED DESCRIPTION

[0015] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0016] As mentioned above, the present invention provides a method for preparing bifenthrin, characterized in that the method comprises: contacting gongfu acid and 2-methyl-3-phenylbenzyl alcohol to carry out esterification reaction in the presence of a catalyst composition;

[0017] Wherein, the catalyst composition comprises component A and component B;

[0018] Wherein, the component A is selected from oxygen-containing acid esters of group IVB elements and / or compounds formed by group IVB elements and alcohols;

[0019] Wherein, the component B is at least one selected from the group consisting of an inorganic salt of copper, an oxide of copper, an oxide of tin and an inorganic salt of tin.

[0020] In some embodiments of the present invention, preferably, the component A is selected from at least one of titanate, zirconate and fatty alcohol zirconium.

[0021] In some embodiments of the present invention, preferably, the component B is selected from at least one of cuprous oxide, cupric hydroxide, cupric oxide, cuprous chloride, basic cupric chloride, cupric chloride, stannous oxide, tin hydroxide, tin oxide, stannous chloride and tin chloride.

[0022] In some embodiments of the present invention, preferably, the component A is selected from at least one of isopropyl titanate, propyl titanate, butyl titanate, isopropyl zirconate, butyl zirconate and zirconium isopropoxide.

[0023] In some embodiments of the present invention, preferably, the component B is selected from: copper hydroxide and / or tin hydroxide.

[0024] In some embodiments of the present invention, preferably, the component A is isopropyl titanate, and the component B is copper hydroxide.

[0025] In some embodiments of the present invention, preferably, the esterification reaction is carried out in the presence of a solvent.

[0026] In some embodiments of the present invention, preferably, the solvent is selected from at least one of aromatic hydrocarbons, halogenated aromatic hydrocarbons and alkanes, preferably at least one of toluene, xylene and trimethylbenzene.

[0027] In the present invention, the xylene and trimethylbenzene each include at least one of their respective isomers.

[0028] In some embodiments of the present invention, preferably, the mass ratio of component A to component B is 0.1-10:1, preferably 0.1-0.5:1, and more preferably 0.2-0.4:1.

[0029] In some embodiments of the present invention, preferably, the mass ratio of the catalyst composition, kung fu acid and 2-methyl-3-phenylbenzyl alcohol is 0.01-1:1-2:1, preferably 0.01-0.1:1-1.1:1.

[0030] In some embodiments of the present invention, preferably, the esterification reaction is carried out at a temperature of 80-175° C. and for a time of 10-30 h.

[0031] In some embodiments of the present invention, preferably, the esterification reaction is carried out at a temperature of 80-145° C. and for a time of 15-18 h.

[0032] In some embodiments of the present invention, preferably, the temperature of the esterification reaction is 80-115°C.

[0033] In some embodiments of the present invention, preferably, the esterification reaction is carried out under dehydration conditions.

[0034] In the present invention, the dehydration condition is achieved by refluxing with water.

[0035] In the present invention, the reflux with water refers to utilizing the principle of azeotropy of toluene and water to evaporate the components of refluxed vaporized toluene and water out of the system, and then the evaporated material is layered, the lower layer is the water layer, which is separated out of the system, and the toluene in the upper layer is returned to the reactor to continue to be used as a solvent, so as to remove the moisture in the reaction system generated by the mixing.

[0036] In the present invention, the temperature of the reflux water is 80-175°C, preferably 80-115°C; the time is 10-30h; preferably 15-18h.

[0037] The present invention will be described in detail below through examples. In the following examples, the gas phase internal standard content parameter is measured by the gas phase internal standard method; the HPLC normalization detection parameter is measured by the liquid phase normalization method; the kung fu acid raw material is a commercial product of Fuxin Dadeli Chemical Co., Ltd.; 2-methyl-3-phenylbenzyl alcohol is a commercial product of Fuxin Dadeli Chemical Co., Ltd.; isopropyl titanate is a commercial product of Maclean; and copper hydroxide is a commercial product of Maclean.

[0038] The equation for the esterification reaction is as follows:

[0039]

[0040] Example 1

[0041] 110 g of toluene was added to a 500 mL reaction bottle, and stirring was started before adding 40 g (0.162 mol) of kungfu acid, 31.7 g (0.158 mol) of 2-methyl-3-phenylbenzyl alcohol, and a catalyst composition (0.3 g of isopropyl titanate and 1 g of copper hydroxide) in sequence; the temperature was raised and refluxed with water for 16 hours; GC detected that 0.2% of 2-methyl-3-phenylbenzyl alcohol remained, and the temperature was lowered to 30° C.; 10 g of water and 2 g of NaOH were added under stirring, and the catalyst was removed by filtration after stirring for 30 min. The filtrate was separated to obtain an oil layer; the oil layer was concentrated and toluene was recovered to obtain 66.8 g of crude oil, with a gas phase internal standard content of 98.3% and a yield of 98.3%; HPLC normalization detected 99.4%, and 0.12% of bifenthrin isomers.

[0042] Example 2

[0043] 110 g of xylene was added to a 500 mL reaction bottle, and stirring was started before adding 40 g (0.162 mol) of kung fu acid, 31.7 g (0.158 mol) of 2-methyl-3-phenylbenzyl alcohol, and a catalyst composition (0.3 g of isopropyl titanate and 1 g of copper hydroxide) in sequence; the temperature was raised and refluxed with water for 16 hours; GC detected that 0.1% of 2-methyl-3-phenylbenzyl alcohol remained, and the temperature was lowered to 30° C.; 10 g of water and 2 g of NaOH were added under stirring, and the catalyst was removed by filtration after stirring for 30 min, and the filtrate was separated to obtain an oil layer; after the oil layer was concentrated and xylene was recovered, 66.8 g of crude oil was obtained, with a gas phase internal standard content of 98.3% and a yield of 98.3%; HPLC normalization detected 99.4%, and 0.25% of bifenthrin isomers.

[0044] Example 3

[0045] 110 g of toluene was added to a 500 mL reaction bottle, and stirring was started before adding 40 g (0.162 mol) of kungfu acid, 31.7 g (0.158 mol) of 2-methyl-3-phenylbenzyl alcohol, and a catalyst composition (0.5 g of 87% zirconium isopropoxide, 1 g of copper hydroxide) in sequence; the temperature was raised and refluxed with water for 16 hours; GC detected that 0.5% of 2-methyl-3-phenylbenzyl alcohol remained, and the temperature was lowered to 30° C.; 10 g of water and 2 g of NaOH were added under stirring, and the insoluble matter was removed by filtration after stirring for 30 min. The filtrate was separated to obtain an oil layer; the oil layer was concentrated and toluene was recovered to obtain 65.2 g of crude oil, with a gas phase internal standard content of 98.0% and a yield of 95.7%; HPLC normalization detected 99.0%, and 0.18% of bifenthrin isomers.

[0046] Example 4

[0047] 110 g of toluene was added to a 500 mL reaction bottle, and stirring was started and 40 g (0.162 mol) of kung fu acid, 31.7 g (0.158 mol) of 2-methyl-3-phenylbenzyl alcohol, and a catalyst composition (0.3 g of butyl titanate and 1 g of copper hydroxide) were added in sequence; the temperature was raised and refluxed with water for 16 hours; GC detected that the residual 2-methyl-3-phenylbenzyl alcohol was 0.5%, and the temperature was lowered to 30° C.; 10 g of water and 2 g of NaOH were added under stirring, and the insoluble matter was removed by filtration after stirring for 30 min. The filtrate was separated to obtain an oil layer; the oil layer was concentrated and toluene was recovered to obtain 66.5 g of crude oil, with a gas phase internal standard content of 98.5% and a yield of 98.1%; HPLC normalization detection was 99.2%, and the isomer of bifenthrin was 0.15%.

[0048] Example 5

[0049] 110 g of xylene was added to a 500 mL reaction bottle, and stirring was started and 40 g (0.162 mol) of kungfu acid, 31.7 g (0.158 mol) of 2-methyl-3-phenylbenzyl alcohol, and a catalyst composition (0.3 g of isopropyl titanate and 1 g of stannous chloride) were added in sequence; the temperature was raised and refluxed with water for 16 hours; GC detected that the residual 2-methyl-3-phenylbenzyl alcohol was 0.5%, and the temperature was lowered to 30° C.; 10 g of water and 2 g of NaOH were added under stirring, and the insoluble matter was removed by filtration after stirring for 30 min. The filtrate was separated to obtain an oil layer; the oil layer was concentrated and toluene was recovered to obtain 66.3 g of crude oil, with a gas phase internal standard content of 98.0% and a yield of 97.3%; HPLC normalization detected 98.8%, and the isomer of bifenthrin was 0.25%.

[0050] Example 6

[0051] The method of Example 1 was followed, except that the reflux was not performed with water, but directly refluxed for 16 hours to obtain 66.3 g of crude oil, with a gas phase internal standard content of 94.3% and a yield of 93.8%; HPLC normalization detection was 93.5%, and the bifenthrin isomers were 0.25%.

[0052] Example 7

[0053] The method of Example 1 was followed, except that the catalyst composition contained 1 g of isopropyl titanate and 1 g of copper hydroxide, and 66.6 g of crude oil was obtained, with a gas phase internal standard content of 95.9% and a yield of 95.9%; HPLC normalization detection was 96.9%, and the isomers of bifenthrin were 0.25%.

[0054] Comparative Example 1

[0055] 110 g of toluene was added to a 500 mL reaction bottle, and stirring was started before adding 40 g (0.162 mol) of kung fu acid, 31.7 g (0.158 mol) of 2-methyl-3-phenylbenzyl alcohol, and 1.5 g of isopropyl titanate in sequence; the temperature was raised and refluxed with water for 16 hours; GC detection showed that the residual 2-methyl-3-phenylbenzyl alcohol was 61%, and the reflux reaction with water was continued for 58 hours, and the residual biphenylmethanol was detected to be 32%; continued reaction detection showed that there was basically no more conversion.

[0056] Comparative Example 2

[0057] Add 110g of xylene to a 500mL reaction bottle, start stirring and add 40g (0.162mol) of gongfu acid, 31.7g (0.158mol) of 2-methyl-3-phenylbenzyl alcohol, and 1.5g of isopropyl titanate catalyst in sequence; heat and reflux with water for 16 hours; GC detection shows that 16.3% of 2-methyl-3-phenylbenzyl alcohol remains, continue to reflux with water for 58 hours, and detect that 1.6% of 2-methyl-3-phenylbenzyl alcohol remains. Cool to 30°C; add 10g of water and 2g of NaOH under stirring, stir for 30min, filter to remove the catalyst, and separate the filtrate to obtain an oil layer; concentrate the oil layer to recover xylene to obtain 65.3g of crude oil, with a gas phase internal standard content of 93.3% and a yield of 93.2%; HPLC normalization detection shows 93.4%, and 2.8% of bifenthrin isomers.

[0058] Comparative Example 3 (Trimethylsilyl Magnesium Chloride)

[0059] Add 242g of toluene to a 1L reaction bottle, add Kungfu acid (123.8g, 0.5mol), 2-methyl-3-phenylbenzyl alcohol (101.1g, 0.5mol), trimethylsilyl magnesium chloride (2.2g, 0.015mol) in sequence under stirring, heat to 60℃, and keep warm for 10 hours. Stop the reaction after HPLC central control detects no change in 2-methyl-3-phenylbenzyl alcohol. After the reaction is completed, filter while hot and collect the filtrate. The filtrate is decompressed to remove the solvent, and after removing 121g of toluene, it is slowly reduced to 0-5℃ and maintained at this temperature for 0.5 hours. Filter with suction, and wash the filter cake with 20g of toluene. Collect the solid, dry it, and get 199.1g of product, with a yield of 90.5%. The product normalized purity measured by HPLC is 96.1%, and the bifenthrin isomer is 2.5%.

[0060] Comparative Example 4

[0061] The method of Comparative Example 3 was followed, except that the catalyst composition contained 2.2 g of trimethylsilyl magnesium chloride and 1.5 g of isopropyl titanate, and 66.8 g of the product was obtained, with a gas phase internal standard content of 93.7% and a yield of 93.8%; HPLC normalization detection was 92.7%, and the content of bifenthrin isomers was 2.6%.

[0062] Comparative Example 5

[0063] The method of Comparative Example 3 was followed, except that the catalyst composition contained 2.2 g of copper hydroxide and 1.5 g of trimethylsilyl magnesium chloride, and 66.7 g of product was obtained, with a gas phase internal standard content of 91.7% and a yield of 91.7%; HPLC normalization detection was 90.3%, and the isomers of bifenthrin were 1.2%.

[0064] It can be seen from the experimental results of the above embodiments and comparative examples that the embodiments using the technical solution of the present invention have significantly better effects in terms of yield, purity and bifenthrin isomers.

[0065] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for preparing bifenthrin, characterized in that, The method comprises: contacting gongfu acid and 2-methyl-3-phenylbenzyl alcohol in the presence of a catalyst composition to carry out an esterification reaction; Wherein, the catalyst composition comprises component A and component B; Wherein, the component A is selected from oxygen-containing acid esters of group IVB elements and / or compounds formed by group IVB elements and alcohols; Wherein, the component B is at least one selected from the group consisting of an inorganic salt of copper, an oxide of copper, an oxide of tin and an inorganic salt of tin.

2. The method according to claim 1, wherein: The component A is selected from at least one of titanate, zirconate and fatty alcohol zirconium; And / or, the component B is selected from at least one of cuprous oxide, cupric hydroxide, cupric oxide, cuprous chloride, basic cupric chloride, cupric chloride, stannous oxide, tin hydroxide, tin oxide, stannous chloride and tin chloride.

3. The method according to claim 1 or 2, wherein: The component A is selected from at least one of isopropyl titanate, propyl titanate, butyl titanate, isopropyl zirconate, butyl zirconate and zirconium isopropoxide; And / or, the component B is selected from copper hydroxide and / or tin hydroxide.

4. The method according to any one of claims 1 to 3, wherein: The component A is isopropyl titanate, and the component B is copper hydroxide.

5. The method according to any one of claims 1 to 4, wherein: The esterification reaction is carried out in the presence of a solvent; Preferably, the solvent is selected from at least one of aromatic hydrocarbons, halogenated aromatic hydrocarbons and alkanes, preferably at least one of toluene, xylene and trimethylbenzene.

6. The method according to any one of claims 1 to 5, wherein: The mass ratio of component A to component B is 0.1-10:1, preferably 0.1-0.5:1, and more preferably 0.2-0.4:

1.

7. The method according to any one of claims 1 to 6, wherein: The mass ratio of the catalyst composition, kung fu acid and 2-methyl-3-phenylbenzyl alcohol is 0.01-1:1-2:1, preferably 0.01-0.1:1-1.1:

1.

8. The method according to any one of claims 1 to 7, wherein: The temperature of the esterification reaction is 80-175° C. and the time is 10-30 hours.

9. The method according to claim 8, wherein: The temperature of the esterification reaction is 80-145° C. and the time is 15-18 hours.

10. The method according to claim 9, wherein: The temperature of the esterification reaction is 80-135°C.

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