CN109824560B - Preparation method of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione - Google Patents
Preparation method of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione Download PDFInfo
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Abstract
The invention provides a preparation method of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, belonging to the technical field of organic synthesis, and the method comprises the following steps: (1) mixing 2-nitro-4-trifluoromethylbenzoic acid with n-butanol and concentrated sulfuric acid, and reacting to obtain 2-nitro-4-trifluoromethylbenzoic acid butyl ester; (2) reacting 2-nitro-4-trifluoromethyl butyl benzoate with sodium methanethiol to obtain 2-methylthio-4-trifluoromethyl butyl benzoate; (3) reacting 2-methylthio-4-trifluoromethylbenzoic acid butyl ester with cyclopropane ketone to obtain 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-diketone. The preparation method can obtain high-purity 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione in a short time and high yield when the using amount of concentrated sulfuric acid and n-butyl alcohol is small, has low cost and less three wastes, and provides favorable conditions for industrial production of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione.
Background
1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione is an important organic synthesis intermediate and can be used for producing pesticides such as insecticides, herbicides and the like.
The prior art generally adopts the following route to prepare 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, and because the boiling point of methanol in the esterification reaction is low, the reaction activity is difficult to improve by further heating. Even with a large excess of methanol, 3.5 equivalents of concentrated sulfuric acid are required for a long time to react enough to achieve an in situ yield of 87% of product. For example, CN1972932A discloses a preparation method of 2-nitro-4-trifluoromethyl-benzoic acid methyl ester, which uses a large amount of methanol and concentrated sulfuric acid, and the reaction time is as long as 48 hours; US20080269265a1 discloses a process for the preparation of 2-nitro-4-trifluoromethyl-benzoic acid methyl ester, which likewise uses large amounts of methanol and concentrated sulfuric acid, with reaction times of up to 24 hours. Namely, in the prior art, a large amount of methanol and concentrated sulfuric acid are used in the esterification reaction, so that the whole post-treatment process is complicated to operate, more in three wastes, high in cost, not environment-friendly and long in reaction time.
Therefore, a new method for preparing 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione with low cost, less three wastes and high product yield is still needed.
Disclosure of Invention
The invention solves the technical problems that the existing preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-diketone has high cost, generates more waste acid and is not beneficial to environmental protection.
The technical scheme adopted by the invention for solving the technical problems is to provide a preparation method of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-diketone, which comprises the following steps:
(1) mixing 2-nitro-4-trifluoromethylbenzoic acid with n-butanol and concentrated sulfuric acid, and reacting to obtain 2-nitro-4-trifluoromethylbenzoic acid butyl ester;
(2) reacting 2-nitro-4-trifluoromethyl butyl benzoate with sodium methanethiol to obtain 2-methylthio-4-trifluoromethyl butyl benzoate;
(3) reacting 2-methylthio-4-trifluoromethylbenzoic acid butyl ester with cyclopropane ketone to obtain 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-diketone.
In the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the n-butanol is 1: 1-16.
Preferably, in the preparation method of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to n-butanol is 1: 1.05-9.5.
More preferably, in the above process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione, the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to n-butanol in step (1) is 1: 1.05.
in the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to concentrated sulfuric acid is 1: 0.1-2.
Preferably, in the above method for preparing 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the concentrated sulfuric acid is 1:0.1 to 0.2.
More preferably, in the above process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione, the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the concentrated sulfuric acid in the step (1) is 1: 0.1.
In the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, an organic solvent is added in the step (1).
Wherein, the organic solvent is a nonpolar organic solvent.
Preferably, the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione comprises the step of preparing the nonpolar organic solvent from one or more of alkanes, cycloalkanes, aromatic hydrocarbons, halogenated alkanes and halogenated aromatic hydrocarbons.
More preferably, the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione comprises the step of preparing the nonpolar organic solvent from one or more of n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, dichloromethane, dichloroethane, benzotrifluoride, p-chlorotrifluoromethyl, m-chlorotrifluoromethyl, o-chlorotrifluoromethyl, p-chlorotoluene, m-chlorotoluene, o-chlorotoluene and p-chloroxylene.
Most preferably, the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione comprises the step of preparing the nonpolar organic solvent from toluene or cyclohexane.
The preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione comprises the step of preparing the 2-nitro-4-trifluoromethylbenzoic acid and the organic solvent in a mass-volume ratio of 1g to 1-10 mL.
Preferably, in the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, the mass volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1-3 mL.
More preferably, in the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, the mass volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1.5-2 mL.
In the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, in the step (1), the reaction temperature is 80-120 ℃.
Wherein, in the above process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione, the reaction is carried out in a reflux state in the step (1).
In the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione, in the step (1), the refluxing time is 4-14 h.
The invention has the beneficial effects that: (1) the method adopts the n-butyl alcohol as the esterification raw material, so that the consumption of concentrated sulfuric acid can be greatly reduced, and the reaction time can be shortened; (2) according to the invention, on the basis of taking n-butyl alcohol as an esterification raw material, after adding an organic solvent for water separation, the raw material is reacted more completely, a butyl ester product can be directly subjected to the next reaction without treatment, the butyl ester product does not cause adverse effect on the subsequent reaction, and the yield of the final product can reach more than 95%.
Detailed Description
Specifically, the preparation method of the 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione comprises the following steps:
(1) mixing 2-nitro-4-trifluoromethylbenzoic acid with n-butanol and concentrated sulfuric acid, and reacting to obtain 2-nitro-4-trifluoromethylbenzoic acid butyl ester;
(2) reacting 2-nitro-4-trifluoromethyl butyl benzoate with sodium methanethiol to obtain 2-methylthio-4-trifluoromethyl butyl benzoate;
(3) reacting 2-methylthio-4-trifluoromethylbenzoic acid butyl ester with cyclopropane ketone to obtain 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-diketone.
The reaction formula of the method is as follows:
the invention selects the n-butyl alcohol as the esterification raw material, and can reduce the dosage of concentrated sulfuric acid. Wherein the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the n-butyl alcohol is 1: 1-16; further, in order to ensure that the raw materials are reacted completely and post-treatment is convenient, the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the n-butyl alcohol is 1: 1.05-9.5; in order to further complete the reaction of the raw materials, the molar ratio of 2-nitro-4-trifluoromethylbenzoic acid to n-butanol was 1: 1.05.
in the invention, in order to reduce the generation of waste acid in the later period, the molar ratio of 2-nitro-4-trifluoromethylbenzoic acid to concentrated sulfuric acid is 1: 0.1-2; preferably, the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the concentrated sulfuric acid is 1: 0.1-0.2; more preferably, the molar ratio of 2-nitro-4-trifluoromethylbenzoic acid to concentrated sulfuric acid is 1: 0.1.
On the basis of using n-butyl alcohol as an esterification raw material, in order to reduce the influence of water generated in the esterification reaction process on the reaction and omit the step of removing excessive butanol at the later stage, the invention adds an organic solvent and water for azeotropy so as to achieve the purposes of water diversion and reaction promotion. The organic solvent may be added during and/or after the esterification reaction.
The organic solvent used in the present invention should be a non-polar organic solvent which can be azeotroped with water but is immiscible with water, and which is inert in the reaction and does not react with the raw materials and the product, preferably, the non-polar organic solvent is selected from one or more of alkanes, cycloalkanes, aromatic hydrocarbons, halogenated alkanes or halogenated aromatic hydrocarbons; more preferably, the non-polar organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, dichloromethane, dichloroethane, benzotrifluoride, p-chlorotrifluoroethylene, m-chlorotrifluoroethylene, o-chlorotrifluoroethylene, p-chlorotoluene, m-chlorotrifluoroethylene, o-chlorotrifluoroethylene, or p-chloroxylene; higher boiling nonpolar organic solvents, such as toluene or cyclohexane, are generally used for higher safety in production when the boiling point of the nonpolar organic solvent is higher, the faster the reaction, and the higher the flash point, especially for large batches.
In the invention, if the solvent is too little, the dissolving effect is poor, and if the solvent is too much, the dissolving effect is not economical, and the mass-volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent can be 1g: 1-10 mL; preferably, the mass volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1-3 mL; more preferably, the mass volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1.5-2 mL.
In the invention, the reaction temperature is 80-120 ℃, and the water-dividing effect is better when the reaction is carried out in a reflux state.
In the invention, the reaction end point can be monitored by HPLC, when the raw materials are basically not left, the next reaction can be carried out, generally, the reflux reaction time is 4-14 h, and longer reaction time is feasible, but no economic significance is realized.
When the organic solvent is added for water separation, the reaction product can be directly used for the next reaction without treatment. However, if n-butanol itself is used as a solvent, the excess butanol needs to be removed, otherwise, more by-products are generated in the next reaction.
In the present invention, after the reaction is completed, the post-treatment is carried out by the conventional operations in the art, such as distillation under reduced pressure to remove the solvent, washing, vacuum drying, etc.
From the above contents, the invention can obtain high-purity 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione in high yield in a short time with less use of concentrated sulfuric acid and n-butyl alcohol through a large number of optimization experiments, has low reaction cost and less three wastes, and provides favorable conditions for industrial production of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-dione.
The present invention is further illustrated in detail by the following test examples and examples, but the scope of the present invention is not limited thereto.
Test example 1: process screening of butyl ester route
100g of 2-nitro-4-trifluoromethylbenzoic acid (0.425mol, 1eq), n-butanol and concentrated sulfuric acid are added into a 500mL four-neck flask, then the temperature is raised for reaction, HPLC detects the residual amount (raw material%) of the 2-nitro-4-trifluoromethylbenzoic acid in the reaction solution, and the reaction solution is a crude product of butyl 2-nitro-4-trifluoromethylbenzoate, and the result is shown in Table 1.
TABLE 1 Process Screen for butyl ester route
Product%: HPLC purity of butyl 2-nitro-4-trifluoromethylbenzoate.
As can be seen from Table 1, the use of n-butanol as the esterification raw material can greatly reduce the use amount of concentrated sulfuric acid; when n-butanol is used as a solvent, the residual amount of 2-nitro-4-trifluoromethylbenzoic acid is large, and when toluene or cyclohexane is added into a reaction system for water separation, the 2-nitro-4-trifluoromethylbenzoic acid can be reacted more completely.
Example 1
(1) Preparation of 2-nitro-4-trifluoromethylbenzoic acid butyl ester
200mL of toluene is added into a 500mL four-mouth bottle, 100g of 2-nitro-4-trifluoromethylbenzoic acid (0.425mol, 1eq), 33.1g of n-butyl alcohol (0.447mol, 1.05eq) and 4.25g of concentrated sulfuric acid (0.0425mol, 0.1eq) are added, then the temperature is raised to the internal temperature of 117 ℃ for reflux, a water separator is used for water separation, after 5 hours of heat preservation reaction, HPLC (high performance liquid chromatography) detection shows that no 2-nitro-4-trifluoromethylbenzoic acid is left in the reaction liquid (less than 1 percent), the reaction liquid is a crude product of butyl 2-nitro-4-trifluoromethylbenzoate, and the HPLC purity is 99 percent.
(2) Preparation of 2-methylthio-4-trifluoromethylbenzoic acid butyl ester
Adding 2.74g of tetrabutylammonium bromide (0.00851mol, 0.02eq) and 164g of 20% sodium methyl mercaptide (0.468mol, 1.1eq) into another 1L four-mouth bottle, heating to 60 ℃, stirring until the tetrabutylammonium bromide is dissolved, dripping the crude product of the butyl 2-nitro-4-trifluoromethylbenzoate obtained in the step, carrying out heat preservation reaction for 2 hours after dripping, monitoring by HPLC (high performance liquid chromatography) that no butyl 2-nitro-4-trifluoromethylbenzoate remains at the upper layer, layering, standing, and taking the upper layer. And recovering toluene and n-butanol from the upper layer under reduced pressure, wherein the concentrated solution is a crude product of butyl 2-methylthio-4-trifluoromethylbenzoate, and the weight of the crude product is 126.2g, and the HPLC purity is 98%.
(3) Preparation of 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane 1, 3-dione
A dry 1L four-necked bottle was taken, 100g of butyl 2-methylthio-4-trifluoromethylbenzoate (0.342mol, 1eq) prepared in the above step, 318.4g N, N-dimethylacetamide (340mL, 3.4V) and 276.3g of dried cyclopropane ketone (0.376mol, 1.1eq) were added, and after stirring, 25.9g of sodium methoxide (0.479mol, 1.4eq) was added at a time. Keeping the temperature at 50 ℃ for reaction for 0.5h, monitoring no residual 2-methylthio-4-trifluoromethylbenzoic acid butyl ester by HPLC, cooling to room temperature, slowly dropwise adding 48.6g of concentrated hydrochloric acid (0.479mol, 1.4eq) to adjust the pH to 5-6, obviously releasing heat, controlling the temperature to be below 50 ℃, and then decompressing and recovering the N, N-dimethylacetamide within 80 ℃. And adding 250g of water, stirring uniformly, adding 10.2g of sodium carbonate (0.0958mol, 0.28eq) at room temperature to adjust the pH value to 7-8, stirring for 0.5h, filtering, leaching a filter cake with a small amount of water, and drying in vacuum at 45 ℃ to obtain a brown yellow solid product with the purity of 98% and the yield of 95%.
Comparative example 1
100g of 2-nitro-4-trifluoromethylbenzoic acid (0.425mol, 1eq), 300g of methanol and concentrated sulfuric acid are added into a 500mL four-neck flask, then the temperature is raised to reflux reaction, HPLC detects the residual amount (raw material%) of the 2-nitro-4-trifluoromethylbenzoic acid in the reaction solution, and the reaction solution is the crude product of the 2-nitro-4-trifluoromethylbenzoic acid methyl ester, and the result is shown in Table 2.
TABLE 2 methyl ester route
Product%: HPLC purity of methyl 2-nitro-4-trifluoromethylbenzoate.
As can be seen from Table 2, when methanol is used as the esterification raw material, the yield of the product is improved only by increasing the dosage of concentrated sulfuric acid, and when the dosage of the concentrated sulfuric acid reaches 3.5 equivalents of 2-nitro-4-trifluoromethylbenzoic acid, the yield of the product reaches only 87%, and the larger the dosage of the concentrated sulfuric acid is, the higher the cost is, the more waste acid at the later stage is, which is not beneficial to the post-treatment and is not environment-friendly.
Comparative example 2
200mL of toluene is added into a 500mL four-neck flask, 100g of 2-nitro-4-trifluoromethylbenzoic acid (0.425mol, 1eq), n-butanol (or methanol) (0.6375mol, 1.5eq) and concentrated sulfuric acid (0.085mol, 0.2eq) are added, then the temperature is raised for reaction, HPLC (high performance liquid chromatography) is used for detecting the residual amount (raw material%) of the 2-nitro-4-trifluoromethylbenzoic acid in the reaction liquid, and the reaction liquid is a crude product of butyl 2-nitro-4-trifluoromethylbenzoate (or methyl 2-nitro-4-trifluoromethylbenzoate), and the result is shown in Table 3.
TABLE 3 comparison of methyl and butyl ester routes
Product%: HPLC purity of methyl 2-nitro-4-trifluoromethylbenzoate (or butyl 2-nitro-4-trifluoromethylbenzoate).
As can be seen from Table 3, n-butanol has no advantage in reactivity with respect to methanol as the starting material of 2-nitro-4-trifluoromethylbenzoic acid of the present invention, and the effects are comparable.
Claims (22)
- A process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione, which comprises the steps of:(1) mixing 2-nitro-4-trifluoromethylbenzoic acid with n-butanol and concentrated sulfuric acid, and reacting to obtain 2-nitro-4-trifluoromethylbenzoic acid butyl ester;(2) reacting 2-nitro-4-trifluoromethyl butyl benzoate with sodium methanethiol to obtain 2-methylthio-4-trifluoromethyl butyl benzoate;(3) reacting 2-methylthio-4-trifluoromethylbenzoic acid butyl ester with cyclopropane ketone to obtain 1-cyclopropyl-3- (2-methylthio-4-trifluoromethylphenyl) propane-1, 3-diketone;in the step (1), the reaction temperature is 80-120 ℃;in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the concentrated sulfuric acid is 1: 0.1-2;the reaction time of the step (1) is 4-14 h.
- 2. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 1, wherein: in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the n-butyl alcohol is 1: 1-16.
- 3. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 2, wherein: in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the n-butyl alcohol is 1: 1.05-9.5.
- 4. A process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 3, characterized in that: in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the n-butanol is 1: 1.05.
- 5. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 1, wherein: in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the concentrated sulfuric acid is 1: 0.1-0.2.
- 6. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 5, wherein: in the step (1), the molar ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the concentrated sulfuric acid is 1: 0.1.
- 7. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to any one of claims 1 to 6, wherein: in the step (1), an organic solvent is also added.
- 8. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 7, wherein: the organic solvent is a non-polar organic solvent.
- 9. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 8, wherein: the non-polar organic solvent is selected from one or more of alkane, cyclane, aromatic hydrocarbon, halogenated alkane or halogenated aromatic hydrocarbon.
- 10. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 9, wherein: the non-polar organic solvent is selected from one or more of n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, dichloromethane, dichloroethane, benzotrifluoride, p-chlorotrifluoromethylene, m-chlorotrifluoromethylene, o-chlorotrifluoromethylene, p-chlorotoluene, m-chlorotoluene, o-chlorotoluene or p-chloroxylene.
- 11. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 10, wherein: the non-polar organic solvent is selected from toluene or cyclohexane.
- 12. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 7, wherein: the mass-volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1-10 mL.
- 13. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 12, wherein: the mass-volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1-3 mL.
- 14. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 13, wherein: the mass-volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1.5-2 mL.
- 15. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to any one of claims 8 to 11, wherein: the mass-volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1-10 mL.
- 16. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 15, wherein: the mass-volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1-3 mL.
- 17. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione as claimed in claim 16, wherein: the mass-volume ratio of the 2-nitro-4-trifluoromethylbenzoic acid to the organic solvent is 1g: 1.5-2 mL.
- 18. The method for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to any one of claims 1 to 6, 8 to 14, or 16 to 17, wherein: in the step (1), the reaction is carried out in a reflux state.
- 19. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 7, wherein: in the step (1), the reaction is carried out in a reflux state.
- 20. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 15, wherein: in the step (1), the reaction is carried out in a reflux state.
- 21. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione as claimed in claim 18, wherein: in the step (1), the refluxing time is 4-14 h.
- 22. The process for producing 1-cyclopropyl-3- (2-methylsulfanyl-4-trifluoromethylphenyl) propane-1, 3-dione according to claim 19 or 20, wherein: in the step (1), the refluxing time is 4-14 h.
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