CN114561435B - Method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using magnetic carbon nanotube immobilized enzyme catalysis - Google Patents
Method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using magnetic carbon nanotube immobilized enzyme catalysis Download PDFInfo
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Abstract
The invention belongs to the field of pesticide intermediate synthesis, and provides a method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using magnetic carbon nanotube immobilized enzyme catalysis. The method comprises the following steps: (1) preparing magnetic carbon nanotube immobilized lipase by using ferrous salt, ferric salt, a carbon nanotube, a surfactant and lipase; (2) preparing 1-methyl-3-ethyl-4-chloro-5-pyrazole ethyl formate from sodium ethoxide, diethyl oxalate, butanone, dichloroethane, hydrazine hydrate, dimethyl sulfate and chlorine; (3) preparing 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester, an organic solvent and magnetic carbon nanotube immobilized lipase. The magnetic carbon nanotube immobilized lipase used in the invention has the advantages of good catalytic activity, high recycling rate, easy recovery and the like, and effectively improves the production efficiency of products.
Description
Technical Field
The invention belongs to the field of synthesis of pesticide intermediates, and particularly relates to a method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using magnetic carbon nanotube immobilized enzyme catalysis.
Background
In recent years, with the adjustment of agricultural structures and the demand of agricultural markets, the proportion of insecticides and acaricides in the total production of agricultural chemicals in China is increasing, and the insecticides and acaricides become important components in agricultural production. The novel pyrazole amide insecticidal acaricide has the characteristics of novel action mechanism, low toxicity, broad spectrum, high efficiency, no cross resistance, rapid degradation, no mutagenesis and the like, and is of great interest. The tolfenpyrad serving as the novel pyrazole amide insecticide and acaricide has the effects of killing ova, inhibiting food, inhibiting spawning and sterilizing, and is widely applied to pest control of crops such as vegetables, flowers, fruit trees, tea leaves and the like.
4-chloro-3-ethyl-1-methylpyrazole-5-formic acid is a key intermediate for synthesizing tolfenpyrad, and the literature reports that the process route for synthesizing the 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid is less, and diethyl oxalate and butanone are mainly used as raw materials, and the raw materials are subjected to cyclization and methylation by different methods, and then are hydrolyzed to obtain the target product.
In the document "4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxylic acid", the method of synthesizing 4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxylic acid (i.e. 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid) by means of methylation, chlorination and hydrolytic acidification is reported by Hanxiacellu et al. The method is simple and convenient to operate, few in byproducts, but a large amount of concentrated hydrochloric acid is used as a catalyst, so that the reaction condition is harsh, and the environment is polluted.
Disclosure of Invention
Based on the defects of the prior art, the method for preparing the 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using the magnetic carbon nanotube immobilized enzyme is characterized in that firstly, ferrous metal iron salt, trivalent metal iron salt, a carbon nanotube, a surfactant and lipase are used for preparing the magnetic carbon nanotube immobilized lipase under the alkaline condition, and the prepared magnetic carbon nanotube immobilized lipase has the advantages of small particle size, easiness in dispersion, easiness in recovery, good reusability and the like; then preparing propionyl ethyl pyruvate by using sodium ethoxide, diethyl oxalate and butanone in a reaction kettle, then adding dichloroethane and hydrazine hydrate to prepare 3-ethyl-5-pyrazole ethyl formate, then adding dimethyl sulfate to prepare 1-3 methyl-3-ethyl-5-pyrazole ethyl formate, and finally introducing chlorine to prepare 1-methyl-3-ethyl-4-chloro-5-pyrazole ethyl formate; and finally, adding 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester, an organic solvent, magnetic carbon nanotube immobilized lipase and a phosphate buffer solution into a reaction kettle to prepare 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid, and recovering the magnetic carbon nanotube immobilized lipase by using a magnetic material. The production process of the 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid has simple and convenient operation and low production cost, and greatly reduces the use of acid liquor.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
a method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using magnetic carbon nanotube immobilized enzyme catalysis. The method comprises the following steps:
step 1, sequentially adding ferrous metal iron salt, ferric metal iron salt, a carbon nano tube, a surfactant and lipase into an aqueous solution in a reaction kettle, uniformly stirring, adding sodium hydroxide to adjust the pH value to 9.0, and after the reaction is finished, performing centrifugal separation, washing and drying to obtain magnetic carbon nano tube immobilized lipase;
step 2, adding an organic solvent and sodium ethoxide into a reaction kettle, adding diethyl oxalate and butanone after the temperature of a reaction system is reduced to 0 ℃, obtaining ethyl propionyl pyruvate after the reaction is finished, then adding dichloroethane and hydrazine hydrate, obtaining ethyl 3-ethyl-5-pyrazolecarboxylate after the reaction is finished, then adding dimethyl sulfate, obtaining ethyl 1-3-methyl-3-ethyl-5-pyrazolecarboxylate after the reaction is finished, and finally introducing chlorine to prepare ethyl 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylate;
and 3, adding 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester, dichloroethane, magnetic carbon nanotube immobilized lipase and phosphate buffer solution into a reaction kettle, stirring and mixing, and after the reaction is finished, performing centrifugal separation, washing and drying to prepare 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid.
In a modification, the ferrous metal iron salt in the step 1 is selected from ferrous sulfate, ferrous nitrate and ferrous chloride; the ferric salt is selected from ferric sulfate, ferric nitrate and ferric chloride; the number of the wall thickness layers of the carbon nano tube is 1-30; the surfactant is at least one selected from Tween-20, Tween-40, Tween-60, Tween-80, span-20, span-40, span-60, span-80, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, Pluronic F-108 and Pluronic F-127; the lipase is selected from Candida antarctica lipase, Candida rugosa lipase, Candida lipase, Rhizopus oryzae lipase, Aspergillus oryzae lipase, and porcine pancreatic lipase;
the improvement is that in the step 1, the concentration of ferrous metal iron salt is 10-100g/L, the concentration of ferric metal iron salt is 10-100g/L, the concentration of carbon nano tube is 10-50g/L, the concentration of surfactant is 1-10g/L, and the concentration of lipase is 1-10 g/L;
the improvement is that the organic solvent in the step 2 is at least one of toluene, ethanol, diethyl ether, acetone and dimethyl sulfoxide;
the improvement is that the concentration of sodium ethoxide in the step 2 is 100-500g/L, the concentration of diethyl oxalate is 1-1000g/L, the concentration of butanone is 1-500g/L, the concentration of hydrazine hydrate is 1-500g/L, and the concentration of dimethyl sulfate is 1-1000 g/L;
the improvement is that the pH value of the phosphate buffer solution in the step 3 is 6-8, and the concentration is 50-200 mmol/L;
the improvement is that the concentration of the 1-methyl-3-ethyl-4-chloro-5-pyrazole ethyl formate in the step 3 is 1-500g/L, the addition amount of dichloroethane is 1-100L, the concentration of the magnetic carbon nanotube immobilized lipase is 0.1-50g/L, and the addition amount of phosphate buffer is 1-100L;
the improvement is that the reaction time of the step 1 is 1-6h, the reaction time of the step 2 is 1-12h, and the reaction time of the step 3 is 1-12 h;
the improvement is that the drying mode of the step 1 and the step 3 is at least one selected from natural air drying, freeze drying and spray drying.
Advantageous effects
Compared with the prior art, the method for preparing the 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using the magnetic carbon nanotube immobilized enzyme for catalysis has the following advantages:
(1) the magnetic carbon nanotube immobilized enzyme prepared by the invention has the advantages of small particle size, easy dispersion, easy recovery, good reusability and the like;
(2) the magnetic carbon nanotube immobilized enzyme prepared by the invention contains a surfactant, and is beneficial to the mixing of an organic phase and a water phase in the process of catalyzing a product;
(3) the method for preparing the magnetic carbon nano tube immobilized enzyme is also suitable for immobilizing other enzyme systems, and can also be applied to other hydrolysis reactions, esterification reactions, ester exchange reactions and the like;
(4) the process route for synthesizing the 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid is simple, the production cost is low, the byproducts are less, the production efficiency is high, and the use of acid liquor is effectively reduced;
drawings
FIG. 1 high performance liquid chromatogram of 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid synthesized in example 1.
FIG. 2 Transmission Electron microscopy of magnetic carbon nanotube-immobilized Lipase prepared in example 1
Detailed Description
The invention is further described below with reference to specific examples:
example 1 method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid by using magnetic carbon nanotube immobilized enzyme as catalyst
(1) Sequentially adding 10L of water, 0.5kg of ferrous sulfate, 0.5kg of ferric chloride, 0.2kg of carbon nano tube and 50g of tween-80 into a reactor, uniformly stirring, adding 50g of candida antarctica lipase, slowly adding 1mol/L of sodium hydroxide solution to adjust the pH of the mixed solution to 9.0, stirring for reacting for 2 hours, finishing the reaction, and performing centrifugal separation, washing and freeze drying to obtain the magnetic carbon nano tube immobilized lipase;
(2) adding 5L of toluene and 1kg of sodium ethoxide into a reaction kettle, stirring and mixing, dropwise adding a mixed solution of 2kg of diethyl oxalate and 1kg of butanone when the temperature of the system reaches 0 ℃, preparing propionyl ethyl pyruvate, standing and layering, taking an oil layer, adding 6L of dichloroethane and 0.6kg of hydrazine hydrate into the oil layer to prepare 3-ethyl-5-pyrazole ethyl formate, standing and layering, taking an oil layer, adding 1.2kg of dimethyl sulfate into the oil layer to prepare 1-3 methyl-3-ethyl-5-pyrazole ethyl formate, and finally introducing chlorine gas to prepare 1-methyl-3-ethyl-4-chloro-5-pyrazole ethyl formate, wherein the total reaction time is 6 hours;
(3) 2.5kg of 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester, 10L of dichloroethane, 0.25kg of magnetic carbon nanotube immobilized lipase and 10L of 100mmol/L phosphate buffer (pH 7.0) were added to a reaction kettle, and after stirring and reacting for 6 hours, 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid was prepared by centrifugal separation, washing and freeze-drying, and magnetic carbon nanotube immobilized lipase was recovered from a magnetic material. The yield of 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid was 95% and the purity was 99% as determined by high performance liquid chromatography (model: Agilent 1260, column: Wonda Cract ODS-2, detector: UV detector, mobile phase: acetonitrile, water, PIC-B7, detection wavelength: 254nm, column temperature: 40 ℃).
Example 2 method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid by using magnetic carbon nanotube immobilized enzyme catalysis
(1) Sequentially adding 10L of water, 0.5kg of ferrous chloride, 0.5kg of ferric sulfate, 0.2kg of carbon nano tube and 50g of polyvinylpyrrolidone into a reactor, uniformly stirring, adding 50g of candida rugosa lipase, slowly adding 1mol/L of sodium hydroxide solution to adjust the pH of the mixed solution to 9.0, stirring for reacting for 2 hours, finishing the reaction, and performing centrifugal separation, washing and natural air drying to obtain the magnetic carbon nano tube immobilized lipase;
(2) adding 5L of diethyl ether and 1kg of sodium ethoxide into a reaction kettle, stirring and mixing, dropwise adding a mixed solution of 2kg of diethyl oxalate and 1kg of butanone when the temperature of the system reaches 0 ℃, preparing propionyl ethyl pyruvate, standing and layering, taking an oil layer, adding 6L of dichloroethane and 0.6kg of hydrazine hydrate to prepare 3-ethyl-5-pyrazole ethyl formate, standing and layering, taking an oil layer, adding 1.2kg of dimethyl sulfate to prepare 1-3 methyl-3-ethyl-5-pyrazole ethyl formate, and finally introducing chlorine to prepare 1-methyl-3-ethyl-4-chloro-5-pyrazole ethyl formate, wherein the total reaction time is 6 hours;
(3) 2.5kg of 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester, 10L of dichloroethane, 0.25kg of magnetic carbon nanotube immobilized lipase and 10L of 100mmol/L phosphate buffer (pH 7.0) were added to a reaction kettle, and after stirring and reacting for 6 hours, 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid was prepared by centrifugal separation, washing and natural air drying, and magnetic carbon nanotube immobilized lipase was recovered from a magnetic material. The yield of 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid was 93% and the purity was 99% as determined by high performance liquid chromatography (model: Agilent 1260, column: Wonda Cract ODS-2, detector: UV detector, mobile phase: acetonitrile, water, PIC-B7, detection wavelength: 254nm, column temperature: 40 ℃).
Example 3 method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid using magnetic carbon nanotube immobilized enzyme catalysis:
(1) sequentially adding 10L of water, 1kg of ferrous sulfate, 1kg of ferric chloride, 0.5kg of carbon nano tube and 0.1kg of tween-80 into a reactor, uniformly stirring, adding 0.1kg of candida antarctica lipase, slowly adding 1mol/L of sodium hydroxide solution to adjust the pH of the mixed solution to 9.0, stirring for reacting for 2 hours, finishing the reaction, and performing centrifugal separation, washing and freeze drying to obtain the magnetic carbon nano tube immobilized lipase;
(2) adding 5L of toluene and 2.5kg of sodium ethoxide into a reaction kettle, stirring and mixing, when the temperature of a system reaches 0 ℃, dropwise adding a mixed solution of 5kg of diethyl oxalate and 2.5kg of butanone to prepare propionyl ethyl pyruvate, standing and layering, taking an oil layer, adding 6L of dichloroethane and 3kg of hydrazine hydrate to prepare 3-ethyl-5-pyrazole ethyl formate, standing and layering, taking an oil layer, adding 6kg of dimethyl sulfate to prepare 1-3 methyl-3-ethyl-5-pyrazole ethyl formate, and finally introducing chlorine to prepare 1-methyl-3-ethyl-4-chloro-5-pyrazole ethyl formate, wherein the total reaction time is 6 hours;
(3) 5kg of 1-methyl-3-ethyl-4-chloro-5-pyrazole ethyl formate, 10L of dichloroethane, 0.5kg of magnetic carbon nanotube immobilized lipase and 10L of 100mmol/L phosphate buffer (pH 7.0) are added into a reaction kettle, the mixture is stirred and reacted for 6 hours, and then the mixture is centrifugally separated, washed and freeze-dried to prepare 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid, and the magnetic carbon nanotube immobilized lipase is recovered by using a magnetic material. The yield of 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid was 95% and the purity was 98% as determined by high performance liquid chromatography (model: Agilent 1260, column: Wonda Cract ODS-2, detector: UV detector, mobile phase: acetonitrile, water, PIC-B7, detection wavelength: 254nm, column temperature: 40 ℃).
The above detailed description is specific to one possible embodiment of the present invention, and the embodiment is not intended to limit the scope of the present invention, and all equivalent implementations or modifications without departing from the scope of the present invention should be included in the technical scope of the present invention.
Claims (1)
1. The method for preparing 4-chloro-3-ethyl-1-methylpyrazole-5-formic acid by using magnetic carbon nanotube immobilized enzyme catalysis comprises the following steps:
(1) sequentially adding a ferrous metal iron salt, a trivalent metal iron salt, a carbon nano tube, a surfactant and lipase into an aqueous solution in a reaction kettle, uniformly stirring, adding sodium hydroxide to adjust the pH to 9.0, and after the reaction is finished, performing centrifugal separation, washing and drying to obtain magnetic carbon nano tube immobilized lipase, wherein the ferrous metal iron salt is selected from ferrous sulfate, ferrous nitrate and ferrous chloride; the ferric salt is selected from ferric sulfate, ferric nitrate and ferric chloride; the wall thickness number of the carbon nano tube is 1-30; the surfactant is at least one selected from Tween-20, Tween-40, Tween-60, Tween-80, span-20, span-40, span-60, span-80, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, Pluronic F-108 and Pluronic F-127; the lipase is selected from Candida antarctica lipase, Candida rugosa lipase, Candida lipase, Rhizopus oryzae lipase, Aspergillus oryzae lipase and porcine pancreatic lipase, the concentration of divalent metal iron salt is 10-100g/L, the concentration of trivalent metal iron salt is 10-100g/L, the concentration of carbon nano tube is 10-50g/L, the concentration of surfactant is 1-10g/L, the concentration of lipase is 1-10g/L, the reaction time of the step is 1-6h, and the drying mode is selected from at least one of natural air drying, freeze drying and spray drying;
(2) adding an organic solvent and sodium ethoxide into a reaction kettle, adding diethyl oxalate and butanone after the temperature of a reaction system is reduced to 0 ℃, obtaining ethyl propionyl pyruvate after the reaction is finished, then adding dichloroethane and hydrazine hydrate to obtain ethyl 3-ethyl-5-pyrazolecarboxylate after the reaction is finished, then adding dimethyl sulfate to obtain ethyl 1-3-methyl-3-ethyl-5-pyrazolecarboxylate after the reaction is finished, and finally introducing chlorine to prepare ethyl 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylate, wherein in the step, the organic solvent is at least one of toluene, ethanol, diethyl ether, acetone and dimethyl sulfoxide, the concentration of the sodium ethoxide is 100-500g/L, and the concentration of the diethyl oxalate is 1-1000g/L, the concentration of butanone is 1-500g/L, the concentration of hydrazine hydrate is 1-500g/L, the concentration of dimethyl sulfate is 1-1000g/L, and the reaction time in the step is 1-12 h;
(3) adding 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester, dichloroethane, magnetic carbon nanotube immobilized lipase and a phosphate buffer solution into a reaction kettle, stirring and mixing, after the reaction is finished, performing centrifugal separation, washing and drying to obtain 4-chloro-3-ethyl-1-methylpyrazole-5-carboxylic acid, wherein the pH value of the phosphate buffer solution is 7, the concentration is 50-200mmol/L, the concentration of 1-methyl-3-ethyl-4-chloro-5-pyrazolecarboxylic acid ethyl ester is 1-500g/L, the addition amount of dichloroethane is 1-100L, and the concentration of the magnetic carbon nanotube immobilized lipase is 0.1-50g/L, the addition amount of the phosphate buffer solution is 1-100L, the reaction time in the step is 1-12h, and the drying mode is at least one of natural air drying, freeze drying and spray drying.
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