CN113968775A - Intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, preparation method and application thereof - Google Patents

Intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, preparation method and application thereof Download PDF

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CN113968775A
CN113968775A CN202010708786.8A CN202010708786A CN113968775A CN 113968775 A CN113968775 A CN 113968775A CN 202010708786 A CN202010708786 A CN 202010708786A CN 113968775 A CN113968775 A CN 113968775A
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殷平
殷凤山
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Jiangsu Fengshan Group Co ltd
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    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
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Abstract

An intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone is prepared from 2- (4-chloro-2- (trifluoromethyl) benzoyl) malonate, 3, 4-dimethyl chlorobenzene as initial raw material through chlorination, exchange reaction between fluorine and chlorine, hydrolysis, continuous chlorination and coupling with malonate, and the intermediate compound 2- (4-chloro-2- (trifluoromethyl) benzoyl) malonate can be hydrolyzed and decarboxylated to obtain 4-chloro-2-trifluoromethyl-acetophenone.

Description

Intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, preparation method and application thereof
Technical Field
The invention belongs to the field of synthesis of pesticide intermediates, and particularly relates to an intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, and a preparation method and application thereof.
Background
The compound 4-chloro-2-trifluoromethyl-acetophenone is a key intermediate for synthesizing triazole bactericide of chlorofluoroether oxazole (Revysol), and is also an important raw material applied to the fields of medicines, dyes and liquid crystal materials.
The world patent WO2015/091045A1 discloses a compound 4-chloro-2-trifluoromethyl-acetophenone, which is used as a key intermediate for synthesizing triazole fungicide clobetazole, and 4-chloro-2-trifluoromethyl-acetophenone and 4-chlorophenol react to obtain 4- (4-chlorophenol) -2-trifluoromethyl acetophenone, wherein the reaction formula is as follows:
Figure BDA0002595727670000011
the preparation method comprises the following steps of taking 2-bromo-5-chlorotrifluoromethylbenzene as a raw material, carrying out Grignard exchange by isopropyl magnesium chloride, and coupling with acetyl chloride to obtain 2-trifluoromethyl-4-chloroacetophenone, wherein the reaction formula is as follows:
Figure BDA0002595727670000012
the synthesis method has two problems: firstly, dangerous reaction Grignard reaction is involved, secondly, the raw material 2-bromo-5-chloro-trifluoromethyl-benzene is not easy to obtain, and the commonly used synthetic method of the 2-bromo-5-chloro-trifluoromethyl-benzene also relates to nitration, reduction reaction and Sandmeyer reaction, and the reaction formula is as follows:
Figure BDA0002595727670000013
disclosure of Invention
The invention aims to provide an intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, a preparation method and application thereof, wherein the method has the advantages that the initial raw materials are easy to obtain, the dangerous reactions such as nitration, Grignard reaction and the like are avoided, and the integral synthesis route is suitable for industrial production so as to overcome the problems that the raw materials are not easy to obtain and the dangerous reactions are involved in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
an intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, which has the following chemical structural formula:
Figure BDA0002595727670000021
wherein R is1、R2The groups are the same or different and are any combination selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl and benzyl.
The invention provides a preparation method of the compound, which comprises the following steps:
1) chlorination of
Using 3, 4-dimethyl chlorobenzene as a starting material, turning on a light source under the conditions of normal pressure and no solvent, introducing chlorine gas, reacting at the temperature of 50-150 ℃, and treating to obtain a compound V;
2) fluorine exchange reaction
Adding a compound V and a fluorination catalyst, taking hydrogen fluoride as a fluorine source, and carrying out a fluorine-chlorine exchange reaction on the compound V to obtain a compound IV under the solvent-free condition at the reaction temperature of 50-200 ℃ and the pressure of 0.1-0.5 MPa;
3) hydrolysis reaction
Under the condition of the existence of Lewis acid catalyst, dropwise adding 1-5 equivalent of water, and hydrolyzing the compound IV to obtain a compound III; the reaction temperature is 90-200 ℃;
4) chlorination of
Further chlorinating compound III in the presence of catalyst BPO and/or AIBN to obtain compound II;
5) coupling reaction
Aromatic hydrocarbon, alkane or halogenated aromatic hydrocarbon are taken as solvents, NaH, magnesium ethoxide, sodium tert-butoxide, triethylamine or pyridine and malonate COOR1CH2COOR2After the reaction, coupling with a compound II to obtain a compound I; wherein malonate COOR1CH2COOR2R in (1)1、R2The groups are the same or different and are any combination selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl and benzyl;
the reaction formula is as follows:
Figure BDA0002595727670000031
further, in step 1), the light source is a low-pressure mercury lamp, a high-pressure mercury lamp or an ultraviolet lamp.
Preferably, in the step 2), the fluorination catalyst is antimony trichloride or antimony pentachloride, the reaction temperature is 100-120 ℃, and the pressure is 0.1MPa-0.5 MPa.
In the step 3), the Lewis acid catalyst is zinc chloride or ferric chloride, and the reaction temperature is 50-200 ℃, preferably 100-120 ℃.
Preferably, in step 4), the reaction temperature is 50-200 ℃, preferably 100-120 ℃.
In the step 5), the aromatic hydrocarbon is toluene or xylene; the alkane is n-heptane or cyclohexane; the halogenated aromatic hydrocarbon is chlorobenzene or dichlorobenzene; the amount of the solvent is 1 to 20 times of the mass of the compound II.
The invention provides an application of the intermediate compound in preparation of triazole fungicide chlorofluoromethane, wherein the application is preparation of 4-chloro-2-trifluoromethyl-acetophenone.
A preparation method of a compound 4-chloro-2-trifluoromethyl-acetophenone is characterized in that a compound I is subjected to saponification hydrolysis and decarboxylation under an acidic condition to obtain the 4-chloro-2-trifluoromethyl-acetophenone, a catalyst is hydrochloric acid and/or sulfuric acid, and the reaction formula is as follows:
Figure BDA0002595727670000032
wherein R is1、R2The groups are the same or different and are any combination selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl and benzyl.
The invention has the following beneficial effects:
the method takes 3, 4-dimethyl chlorobenzene as an initial raw material, and obtains the intermediate compound 2- (4-chloro-2- (trifluoromethyl) benzoyl) malonate by chlorination, fluorine-chlorine exchange reaction, hydrolysis, continuous chlorination and coupling with malonate, the raw material is cheap and easy to obtain, dangerous processes such as nitration, Grignard and the like are avoided, and the method is suitable for industrial production.
The preparation method disclosed by the invention is mild in reaction condition, simple to operate, environment-friendly, low in cost, high in reaction conversion rate, high in total yield of the route and suitable for industrial production.
Drawings
FIG. 1-2 shows the LC-MS detection spectrum of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate as the compound in example 1 of the present invention.
FIG. 3 is a drawing showing a reaction scheme of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate as the compound in example 1 of the present invention19FNMR spectrogram.
FIG. 4 shows a scheme for preparing diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate as the compound in example 1 of the present invention1HNMR spectrogram.
FIG. 5 shows the preparation of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate as the compound in example 1 of the present invention13CNMR spectrogram.
Detailed Description
The present invention will be further described with reference to the following embodiments.
Both low-pressure mercury lamps and high-pressure mercury lamps commonly used in the art are suitable for the light source of the present invention.
EXAMPLE 12 Synthesis of dimethyl (4-chloro-2-trifluoromethylbenzoyl) malonate
1. Synthesis of compound 3-trichloromethyl-4-dichloromethyl chlorobenzene by different methods
1-1, adding 500g of 3, 4-dimethyl chlorobenzene into a tower reactor with a reflux device, raising the temperature to 120-.
Sampling and detecting that the content of 3, 4-bis (dichloromethyl) chlorobenzene is less than 1.0 percent, ensuring that the reaction is qualified, and introducing nitrogen for 1 hour to purge residual chlorine and hydrogen chloride gas. Cooling, cooling to 70-80 ℃, transferring to a crystallization kettle, adding 1000g of ethanol, heating to be completely dissolved, gradient cooling to 0 ℃, filtering and drying the precipitated product to obtain the 3-trichloromethyl-4-dichloromethyl chlorobenzene with the purity of 98% and the yield of 65%.
1-2, adding 500g of 3, 4-dimethyl chlorobenzene into a tower reactor with a reflux device, raising the temperature to 120-.
Sampling and detecting that the content of 3, 4-bis (dichloromethyl) chlorobenzene is less than 1.0 percent, ensuring that the reaction is qualified, and introducing nitrogen for 1 hour to purge residual chlorine and hydrogen chloride gas. Cooling to 70-80 deg.c and transferring to crystallizing kettle. Adding 1000g of ethanol, heating until the ethanol is completely dissolved, reducing the temperature to 0 ℃ in a gradient manner, filtering and drying the precipitated product to obtain the 3-trichloromethyl-4-dichloromethyl chlorobenzene with the purity of 98 percent and the yield of 63 percent.
2. Synthesis of 3-trifluoromethyl-4-dichloromethyl chlorobenzene by different methods
2-1, adding 300g of 3-trichloromethyl-4-dichloromethyl chlorobenzene and 1g of antimony trichloride into a high-pressure reaction kettle, closing the high-pressure reaction kettle, replacing with nitrogen, adding 56g of HF at one time, heating to 110 ℃, reacting for 3 hours, sampling, checking, and releasing pressure to normal pressure.
The tail gas is condensed to recover hydrogen fluoride, and the residual gas is absorbed by alkali liquor. The product 3-trifluoromethyl-4-dichloromethyl chlorobenzene is obtained by rectification, the purity is 99 percent, and the yield is 90 percent.
2-2, adding 300g of 3-trichloromethyl-4-dichloromethyl chlorobenzene and 1g of antimony pentachloride into the high-pressure reaction kettle, closing the high-pressure reaction kettle, replacing the high-pressure reaction kettle with nitrogen, and adding 56g of HF at one time. Heating to 110 ℃, reacting for 3 hours under the pressure of 0.1-0.5 MPa, sampling and checking to be qualified, and then releasing pressure to normal pressure.
The tail gas is condensed to recover hydrogen fluoride, and the residual gas is absorbed by alkali liquor. The product 3-trifluoromethyl-4-dichloromethyl chlorobenzene is obtained by rectification, the purity is 99 percent, and the yield is 83 percent.
3. Synthesis of 4-chloro-2-trifluoromethylbenzaldehyde by different methods
3-1, adding 500g of 3-trifluoromethyl-4-dichloromethyl chlorobenzene and 3g of zinc chloride into a reaction kettle, heating to 120 ℃, and dropwise adding 50g of water. After the addition was complete, stirring was continued for 1 hour. The product is distilled to obtain 4-chloro-2-trifluoromethyl benzaldehyde with the content of 95 percent and the yield of 93 percent.
3-2 adding 500g of 3-trifluoromethyl-4-dichloromethyl chlorobenzene and 3g of ferric trichloride into a reaction kettle, heating to 120 ℃, and dropwise adding 50g of water. After the dropwise addition, stirring is continued for 1 hour, and the product is distilled to obtain 4-chloro-2-trifluoromethylbenzaldehyde with the content of 95% and the yield of 88%.
4. Synthesis of 4-chloro-2-trifluoromethylbenzoyl chloride by different methods
4-1. adding 200g of 4-chloro-2-trifluoromethylbenzaldehyde into a reaction kettle, adding 1g of azobisisobutyronitrile AIBN, and heating to 90 ℃ to 95 ℃. And slowly introducing quantitative chlorine, detecting that the residual of the raw materials is less than 0.5%, stopping introducing chlorine, purging with nitrogen for half an hour to obtain a crude product for later use, wherein the yield is 92%, and the by-product 4-chloro-2-trifluoromethylbenzoic anhydride is 2%.
4-2. adding 200g of 4-chloro-2-trifluoromethylbenzaldehyde into a reaction kettle, adding 1g of benzoyl peroxide BPO, and heating to 90-95 ℃. And slowly introducing quantitative chlorine, detecting that the residual of the raw materials is less than 0.5%, stopping introducing chlorine, purging with nitrogen for half an hour to obtain a crude product for later use, wherein the yield is 90%, and the by-product 4-chloro-2-trifluoromethylbenzoic anhydride is 2%.
5. Synthesis of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate by different methods
And 5-1, dissolving 180g of diethyl malonate in 1L of tetrahydrofuran, cooling to 0 ℃, slowly adding 54.5g of sodium hydride in batches, and directly discharging generated gas into the atmosphere after washing and absorption. After the addition, stirring was continued for 1 hour and the temperature was raised to room temperature.
Slowly dripping 4-chloro-2-trifluoromethyl benzoyl chloride into the solution, and heating for reacting for 3 hours until the raw materials completely react. Adding water and methylbenzene for layering, adding and extracting the methylbenzene once, and enabling the water phase to enter a wastewater treatment system; and combining organic phases, distilling to recover toluene and tetrahydrofuran, and directly carrying out next hydrolysis decarboxylation on the concentrated solution without purification, wherein the yield of the liquid phase content is 75%.
The obtained 2- (4-chloro-2-trifluoromethyl benzoyl) diethyl malonate toluene/tetrahydrofuran solution is concentrated to remove toluene,detection is carried out, LC-MS detection spectrogram is shown in figure 1-2,19FNMR spectra referring to figure 3,1HNMR spectra referring to figure 4,13the CNMR spectra are shown in FIG. 5.
Spectrogram analysis data:
19F NMR(377MHz，CDCl3)δ-59.78(s)。
1H NMR(400MHz，CDCl3)δ8.03(d，J＝8.4Hz，1H)，7.80-7.55(m，2H)，4.27(q，J＝7.1Hz，2H)，4.07(q，J＝7.1Hz，2H)，1.25(t，J＝7.1Hz，5H)，1.06(t，J＝7.1Hz，3H)。
13C NMR(100MHz，CDCl3)δ175.87，162.52，161.76，160.71，155.54，139.29，136.92，133.43，133.03，132.05，131.92，131.44，131.32，130.59，130.29，129.97，128.96，127.67，126.96，126.44，122.65，62.00，60.80，13.92，13.50。
LC-MS[M-1]：365。
and 5-2, dissolving 180g of dimethyl malonate in 1L of tetrahydrofuran, cooling to 0 ℃, slowly adding 130.9g of sodium tert-butoxide in batches, stirring for 1 hour continuously after the addition is finished, and heating to room temperature.
Slowly dripping 4-chloro-2-trifluoromethyl benzoyl chloride into the solution, and heating for reacting for 3 hours until the raw materials completely react. Adding water and methylbenzene for layering, adding and extracting the methylbenzene once, and enabling the water phase to enter a wastewater treatment system; and combining organic phases, distilling to recover toluene and tetrahydrofuran, and directly feeding the concentrated solution into the next step for hydrolysis and decarboxylation without purification. The yield of the liquid phase content is 85%.
5-3, dissolving 180g of dimethyl malonate in 1L of chlorobenzene, cooling to 0 ℃, slowly adding 69.2g of magnesium ethoxide in batches, continuing to stir for 1 hour after the addition is finished, and heating to 60 ℃.
Slowly dripping 4-chloro-2-trifluoromethyl benzoyl chloride into the solution at the temperature of 75 ℃, and stirring for 3 hours under the condition of heat preservation until the raw materials completely react. Adding water to quench the reaction, standing for layering overnight, extracting the water phase once with chlorobenzene, and allowing the water phase to enter a wastewater treatment system; the organic phases are combined and directly enter the next step of hydrolysis and decarboxylation, and the yield of the liquid phase content is 90 percent.
6. Synthesis of dimethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate by different methods
6-1, dissolving 170g of dimethyl malonate in 1L of tetrahydrofuran, cooling to 0 ℃, slowly adding 54.5g of sodium hydride with the content of 60% in batches, and directly discharging generated gas into the atmosphere after washing and absorption. After the addition, stirring was continued for 1 hour and the temperature was raised to room temperature.
Slowly dripping 4-chloro-2-trifluoromethyl benzoyl chloride into the solution, and heating for reacting for 3 hours until the raw materials completely react. Adding water and methylbenzene for layering, adding and extracting the methylbenzene once, and enabling the water phase to enter a wastewater treatment system; and combining organic phases, distilling to recover toluene and tetrahydrofuran, and directly carrying out next hydrolysis decarboxylation on a concentrated solution without purification, wherein the liquid phase area content is 75%.
6-2, dissolving 170g of dimethyl malonate in 1L of tetrahydrofuran, cooling to 0 ℃, slowly adding 130.9g of sodium tert-butoxide in batches, and directly discharging generated gas into the atmosphere after washing and absorption. After the addition, stirring was continued for 1 hour and the temperature was raised to room temperature.
Slowly dripping 4-chloro-2-trifluoromethyl benzoyl chloride into the solution, and heating for reacting for 3 hours until the raw materials completely react. Adding water and methylbenzene for layering, adding and extracting the methylbenzene once, and enabling the water phase to enter a wastewater treatment system; and combining organic phases, distilling to recover toluene and tetrahydrofuran, and directly carrying out next hydrolysis decarboxylation on the concentrated solution without purification, wherein the yield of the liquid phase content is 85%.
6-3, dissolving 180g of dimethyl malonate in 1L of chlorobenzene, cooling to 0 ℃, slowly adding 69.2g of magnesium ethoxide in batches, continuing to stir for 1 hour after the addition is finished, and heating to 60 ℃.
Slowly dripping 4-chloro-2-trifluoromethyl benzoyl chloride into the solution at the temperature of 75 ℃, and stirring for 3 hours under the condition of heat preservation until the raw materials completely react. Adding water to quench the reaction, standing for layering overnight, extracting the water phase once with chlorobenzene, and allowing the water phase to enter a wastewater treatment system; the organic phases are combined and directly enter the next step of hydrolysis and decarboxylation, and the yield of the liquid phase content is 91%.
Example 2 Synthesis of 4-chloro-2-trifluoromethyl-acetophenone by different methods
Synthesis of 1, 4-chloro-2-trifluoromethyl-acetophenone
150g of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate in example 1 was transferred to a reaction kettle, 500g of chlorobenzene solvent was added, the temperature was raised to 110 ℃ to 130 ℃, 50g of 50% sulfuric acid was slowly added, and after 6 hours of reaction, completion of the reaction was detected.
Separating the liquid by layers, recovering xylene which is dissolved out of the organic phase, recycling the xylene, adding 500g of ethanol into the concentrated solution, heating and refluxing the mixture until the mixture is clear, performing gradient cooling crystallization, filtering and drying to obtain the product 4-chloro-2-trifluoromethyl-acetophenone, wherein the purity is 99 percent, and the yield is 90 percent.
Synthesis of 2, 4-chloro-2-trifluoromethyl-acetophenone
150g of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate of example 1 is transferred to a reaction kettle, 500g of chlorobenzene solvent is added, the temperature is raised to 110 ℃ to 130 ℃, 50g of mixed acid is slowly added, and the mixed acid is mixed with 36% hydrochloric acid: 50% sulfuric acid ═ 1: 1, mass ratio, and detecting the reaction is complete after 6 hours of reaction.
And (3) separating the layers, recovering xylene dissolved out of the organic phase, recycling, adding 500g of ethanol into the concentrated solution, heating and refluxing to be clear, performing gradient cooling crystallization, filtering and drying to obtain the product 4-chloro-2-trifluoromethyl-acetophenone, wherein the purity is 99%, and the yield is 75%.
Synthesis of 3.4-chloro-2-trifluoromethyl-acetophenone
150g of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate of example 1 is transferred to a reaction kettle, 500g of xylene as a solvent is added, the temperature is raised to 110 ℃ to 130 ℃, and 50g of mixed acid, 36% hydrochloric acid: 50% sulfuric acid ═ 1: 1, mass ratio, and detecting the reaction is complete after 6 hours of reaction.
Separating the layers, recovering xylene dissolved out of the organic phase, recycling, adding 500g of ethanol into the concentrated solution, heating and refluxing to be clear, performing gradient cooling crystallization, filtering and drying to obtain the product 4-chloro-2-trifluoromethyl-acetophenone, wherein the purity is 99 percent, and the yield is 79 percent.
4.4 Synthesis of chloro-2-trifluoromethyl-acetophenone
150g of diethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate in example 1 was transferred to a reaction kettle, 500g of toluene as a solvent was added, the temperature was raised to 110 ℃ to 130 ℃, 100g of 50% sulfuric acid was slowly added, and after 6 hours of reaction, completion of the reaction was checked.
Separating the layers, recovering xylene dissolved out of the organic phase, recycling, adding 500g of ethanol into the concentrated solution, heating and refluxing to be clear, performing gradient cooling crystallization, filtering and drying to obtain the product 4-chloro-2-trifluoromethyl-acetophenone, wherein the purity is 99 percent, and the yield is 79 percent.
Synthesis of 5.4-chloro-2-trifluoromethyl-acetophenone
150g of dimethyl 2- (4-chloro-2-trifluoromethylbenzoyl) malonate in example 1 is transferred to a reaction kettle, 500g of chlorobenzene solvent is added, the temperature is raised to 110 ℃ to 130 ℃, 50g of 50% sulfuric acid is slowly added, and after 6 hours of reaction, the reaction is detected to be complete.
Separating the liquid by layers, recovering xylene which is dissolved out of the organic phase, recycling the xylene, adding 500g of ethanol into the concentrated solution, heating and refluxing the mixture until the mixture is clear, performing gradient cooling crystallization, filtering and drying to obtain the product 4-chloro-2-trifluoromethyl-acetophenone, wherein the purity is 99 percent, and the yield is 92 percent.

Claims (10)

1. An intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, which has the following chemical structural formula:
Figure FDA0002595727660000011
wherein R is1、R2The groups are the same or different and are any combination selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl and benzyl.
2. A process for the preparation of an intermediate compound as claimed in claim 1, comprising the steps of:
1) chlorination of
Using 3, 4-dimethyl chlorobenzene as a starting material, turning on a light source under the conditions of normal pressure and no solvent, introducing chlorine gas, reacting at the temperature of 50-150 ℃, and treating to obtain a compound V;
2) fluorine exchange reaction
Adding a compound V and a fluorination catalyst, taking hydrogen fluoride as a fluorine source, and carrying out a fluorine-chlorine exchange reaction on the compound V to obtain a compound IV under the solvent-free condition at the reaction temperature of 50-200 ℃ and the pressure of 0.1-1 MPa;
3) hydrolysis reaction
Under the condition of the existence of Lewis acid catalyst, dropwise adding 1-5 equivalent of water, and hydrolyzing the compound IV to obtain a compound III; the reaction temperature is 90-200 ℃;
4) chlorination of
Further chlorinating compound III in the presence of catalyst BPO and/or AIBN to obtain compound II;
5) coupling reaction
Aromatic hydrocarbon, alkane or halogenated aromatic hydrocarbon are taken as solvents, NaH, magnesium ethoxide, sodium tert-butoxide, triethylamine or pyridine and malonate COOR1CH2COOR2After the reaction, coupling with a compound II to obtain a compound I; wherein malonate COOR1CH2COOR2R in (1)1、R2The groups are the same or different and are any two combinations selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl and benzyl;
the reaction formula is as follows:
Figure FDA0002595727660000021
3. the method for producing an intermediate compound according to claim 2, wherein in the step 1), the light source is a low-pressure mercury lamp, a high-pressure mercury lamp, or an ultraviolet lamp.
4. The method for preparing an intermediate compound as claimed in claim 2, wherein in the step 2), the fluorination catalyst is antimony trichloride or antimony pentachloride, the reaction temperature is 100-.
5. The process for preparing an intermediate compound according to claim 2, wherein the Lewis acid catalyst in step 3) is zinc chloride or ferric chloride, and the reaction temperature is 50-200 ℃, preferably 100-120 ℃.
6. The process for producing an intermediate compound according to claim 2, wherein the reaction temperature in the step 4) is 50 to 200 ℃.
7. The process for preparing an intermediate compound as claimed in claim 2, wherein the reaction temperature in the step 4) is 100-120 ℃.
8. The process for preparing an intermediate compound according to claim 2, wherein in step 5), the aromatic hydrocarbon is toluene or xylene; the halogenated aromatic hydrocarbon is chlorobenzene or dichlorobenzene; the amount of the solvent is 1 to 20 times of the mass of the compound II.
9. The use of the intermediate compound as claimed in claim 1 for the preparation of the triazole fungicide triflumizole.
10. A preparation method of a compound 4-chloro-2-trifluoromethyl-acetophenone is characterized in that a compound I is subjected to saponification hydrolysis and decarboxylation under an acidic condition to obtain the 4-chloro-2-trifluoromethyl-acetophenone, a catalyst is hydrochloric acid and/or sulfuric acid, and the reaction formula is as follows:
Figure FDA0002595727660000031
wherein R is1、R2The groups are the same or different and are any combination selected from methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, aryl and benzyl.
CN202010708786.8A 2020-07-22 2020-07-22 Intermediate compound for preparing 4-chloro-2-trifluoromethyl-acetophenone, preparation method and application thereof Pending CN113968775A (en)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2005139166A (en) * 2003-10-15 2005-06-02 Central Glass Co Ltd Method for producing 4-trifluoromethyl-3-methylfluorobenzene
JP2006213630A (en) * 2005-02-03 2006-08-17 Central Glass Co Ltd Method for producing 2-trifluoromethyl-6-fluorobenzaldehyde and its derivative
JP2006282511A (en) * 2005-03-31 2006-10-19 Central Glass Co Ltd 2-trifluoromethyl-6-fluorobenzal chloride and production method of it and its derivative
CN102516047A (en) * 2011-12-13 2012-06-27 联化科技股份有限公司 Preparation methods of 2-(trifluoromethyl)benzaldehyde and intermediate thereof
CN104016840A (en) * 2014-06-16 2014-09-03 辽宁天予化工有限公司 Method for preparing o-trifluoromethyl benzaldehyde
CN111348996A (en) * 2018-12-24 2020-06-30 江苏联化科技有限公司 2-benzoyl malonate compound, preparation method and application thereof

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* Cited by examiner, † Cited by third party
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JP2005139166A (en) * 2003-10-15 2005-06-02 Central Glass Co Ltd Method for producing 4-trifluoromethyl-3-methylfluorobenzene
JP2006213630A (en) * 2005-02-03 2006-08-17 Central Glass Co Ltd Method for producing 2-trifluoromethyl-6-fluorobenzaldehyde and its derivative
JP2006282511A (en) * 2005-03-31 2006-10-19 Central Glass Co Ltd 2-trifluoromethyl-6-fluorobenzal chloride and production method of it and its derivative
CN102516047A (en) * 2011-12-13 2012-06-27 联化科技股份有限公司 Preparation methods of 2-(trifluoromethyl)benzaldehyde and intermediate thereof
CN104016840A (en) * 2014-06-16 2014-09-03 辽宁天予化工有限公司 Method for preparing o-trifluoromethyl benzaldehyde
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