CN114436932A - Synthetic process of chlorfenapyr homolog - Google Patents
Synthetic process of chlorfenapyr homolog Download PDFInfo
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- CN114436932A CN114436932A CN202210030434.0A CN202210030434A CN114436932A CN 114436932 A CN114436932 A CN 114436932A CN 202210030434 A CN202210030434 A CN 202210030434A CN 114436932 A CN114436932 A CN 114436932A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
Abstract
The invention discloses a synthesis process of a chlorfenapyr homolog, which relates to the technical field of pesticides and is characterized in that parachlorobenzene glycine is used as a starting material, and the chlorfenapyr homolog is synthesized through cyclization, addition decarboxylation, condensation and chlorination.
Description
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a synthetic process of a chlorfenapyr homolog.
Background
The chlorfenapyr is a typical representative of pyrrole compounds, the pyrrole compounds, particularly the 2-aryl pyrrole compounds, the chlorfenapyr are novel insecticides developed by taking natural product dioxapyrrolnitrin as a lead, and the action mechanism of the chlorfenapyr is to block the oxidation phosphorylation of mitochondria. Through continuous and intensive research on the synthetic process of the pyrrole compounds, a plurality of new high-activity compounds, in particular to a representative high-activity pyrrole compound chlorfenapyr homologue, the main structural modification or group transformation of which is still the change of groups such as 1-position N-substituent, 2-position aromatic ring and 5-position trifluoromethyl, and the like, and new substituents are introduced, so that a new medicament different from chlorfenapyr can be obtained.
Bromine is needed to be added for bromination reaction in the synthesis process of the chlorfenapyr, the price of the bromine is high, bromine-containing wastewater is easy to generate, and the environmental protection property is poor.
Disclosure of Invention
Aiming at the problems, the invention provides a synthesis process of a chlorfenapyr homolog, which takes p-chlorophenyl glycine as a starting material to synthesize the chlorfenapyr homolog, and the homolog has similar drug effect to chlorfenapyr, low cost, high yield and economic value.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a synthetic process of a chlorfenapyr homolog takes p-chlorophenyl glycine as a starting material, and synthesizes the chlorfenapyr homolog through cyclization, addition decarboxylation, condensation and chlorination, which comprises the following steps:
and (3) cyclization reaction: adding p-chlorophenylglycine, acetonitrile and trifluoroacetic acid into a reaction container, dropwise adding triethylamine under a stirring state, controlling the temperature to be 5-15 ℃, dropwise adding phosphorus trichloride after the dropwise adding is finished, keeping the temperature to be less than 20 ℃ in the dropwise adding process, and keeping the system temperature at 15-25 ℃ for 1.5 hours after the dropwise adding is finished to obtain an intermediate;
addition and decarboxylation reactions: adding 2-chloroacrylonitrile into a reaction container containing the intermediate, cooling the material to a temperature of less than 20 ℃, dropwise adding triethylamine, keeping the temperature at 10-20 ℃ in the dropwise adding process, detecting the pH value of the material after dropwise adding is finished, heating to 55-65 ℃, and keeping the temperature for 2 hours; distilling, removing solvent, washing with water, stirring for 0.5h, vacuum filtering, and oven drying to obtain dried pyrrole compound;
condensation reaction: putting a dried pyrrole compound into a condensation reaction bottle, adding potassium carbonate and ethyl acetate, heating to 45-55 ℃ under stirring, dropwise adding chloromethyl ethyl ether, heating to 50-55 ℃ after dropwise adding, keeping the temperature for 2 hours, sampling, adding water when the content of the pyrrole compound in the material is detected to be less than or equal to 0.5%, stirring for 0.5 hour, standing for layering, taking an ethyl acetate layer, continuously heating, and distilling under normal pressure and reduced pressure to obtain a condensation compound; adding dichloromethane into the condensation compound, stirring and dissolving to obtain a condensation compound dichloromethane solution;
chlorination reaction: cooling the dichloromethane solution of the condensation compound to 10-20 ℃, introducing chlorine into the solution, keeping the temperature at 10-15 ℃ in the aeration process, stopping introducing the chlorine when the content of the condensation compound in the materials is detected to be less than or equal to 0.3% by sampling, and finishing chlorination reaction; and (3) after distillation and desolventizing, adding methanol, heating to 45-55 ℃, keeping the temperature for 0.5h, cooling to 15-25 ℃ after all the materials are dissolved, keeping the temperature for 3h, adjusting the temperature to 15-20 ℃, keeping the temperature, crystallizing, filtering, and drying to obtain the chlorfenapyr homolog chlorine-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethyl pyrrole-3-nitrile.
Preferably, in the cyclization reaction, the molar ratio of p-chlorophenyl glycine to acetonitrile is 1 (2-4), the molar ratio of p-chlorophenyl glycine to trifluoroacetic acid is 1 (1.05-1.5), the molar ratio of p-chlorophenyl glycine to triethylamine is 1 (1-1.2), the molar ratio of p-chlorophenyl glycine to phosphorus trichloride is 1 (1.02-2), and the residual content of p-chlorophenyl glycine in the intermediate is less than or equal to 0.5%.
Preferably, in the addition decarboxylation reaction, the molar ratio of 2-chloroacrylonitrile to p-chlorophenyl glycine in the cyclization reaction is (1-2): 1, the molar ratio of triethylamine to p-chlorophenyl glycine in the cyclization reaction is (1-1.5): 1, the molar ratio of water to p-chlorophenyl glycine in the cyclization reaction is 3:1, and the content of an intermediate in the material is less than or equal to 1%.
Preferably, in the addition decarboxylation reaction, the distillation is reduced pressure distillation, the negative pressure is-0.09 Mpa, and the temperature is 70 ℃; the pH of the material is = 7.5-8.5.
Preferably, in the condensation reaction, the molar ratio of chloromethyl ethyl ether to p-chlorophenyl glycine in the cyclization reaction is (1-2): 1, the molar ratio of potassium carbonate to p-chlorophenyl glycine in the cyclization reaction is (1-2): 1, the molar ratio of ethyl acetate to p-chlorophenyl glycine in the cyclization reaction is (2-4): 1, and the molar ratio of water to p-chlorophenyl glycine in the cyclization reaction is 2: 1.
Preferably, in the condensation reaction, the atmospheric distillation temperature is 90 ℃, the reduced pressure distillation negative pressure is-0.09 Mpa, and the temperature is 90 ℃.
Preferably, in the chlorination reaction, the molar ratio of chlorine to p-chlorophenyl glycine in the cyclization reaction is (1-1.5): 1, the molar ratio of dichloromethane to p-chlorophenyl glycine in the cyclization reaction is (2-4): 1, and the molar ratio of methanol to p-chlorophenyl glycine in the cyclization reaction is (2-4): 1.
Preferably, in the chlorination reaction, the distillation desolventizing is reduced pressure distillation desolventizing, the negative pressure is-0.06 Mpa, and the temperature is 50 ℃.
After the technical scheme is adopted, the invention has the beneficial effects that:
1) the chlorfenapyr homologue prepared by introducing Cl has similar drug effect to chlorfenapyr, is low in cost, does not generate bromine-containing wastewater, has economic value and is suitable for industrial production.
2) The synthesis process provided by the invention has high yield of intermediate products, the content of the final product chlorfenapyr homolog is more than 99%, and the yield reaches 97.5%.
Detailed Description
The following examples are provided to illustrate the synthesis of a chlorfenapyr homologue according to the present invention, but they should not be construed as limiting the scope of the present invention. In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art, unless otherwise specified.
Example 1
And (3) cyclization reaction: adding 0.35mol of p-chlorophenyl glycine, 0.7mol of acetonitrile and 0.37mol of trifluoroacetic acid into a reaction container, dropwise adding 0.385mol of triethylamine under a stirring state, controlling the temperature to be 5 ℃, dropwise adding 0.36mol of phosphorus trichloride after the dropwise adding is finished, keeping the temperature to be less than 20 ℃ in the dropwise adding process, and keeping the system temperature to be 15 ℃ for 1.5 hours after the dropwise adding is finished to obtain an intermediate;
addition and decarboxylation reactions: adding 0.385mol of 2-chloroacrylonitrile into a reaction container containing the intermediate, cooling the material to the temperature of less than 20 ℃, dropwise adding 0.385mol of triethylamine, keeping the temperature at 10 ℃ in the dropwise adding process, detecting the pH value of the material after dropwise adding is finished, heating to 55 ℃, and keeping the temperature for 2 hours; distilling, removing solvent, washing with water, stirring for 0.5h, vacuum filtering, and oven drying to obtain dried pyrrole compound;
condensation reaction: putting a dried pyrrole compound into a condensation reaction bottle, adding 0.35mol of potassium carbonate and 0.7mol of ethyl acetate, heating to 45 ℃ under stirring, dropwise adding 0.35mol of chloromethyl ethyl ether, heating to 50 ℃ after dropwise adding, keeping the temperature for 2 hours, sampling, adding water when the content of the pyrrole compound in the material is detected to be less than or equal to 0.5%, stirring for 0.5 hour, standing for layering, continuously heating an ethyl acetate layer, distilling under normal pressure and reduced pressure to obtain a condensation compound, adding 1.05mol of dichloromethane into the condensation compound, and stirring and dissolving to obtain a dichloromethane solution of the condensation compound;
chlorination reaction: cooling the dichloromethane solution of the condensation compound to 10 ℃, introducing 0.46mol of chlorine into the solution, keeping the temperature at 10 ℃ in the aeration process, stopping introducing the chlorine when the content of the condensation compound in the materials is detected to be less than or equal to 0.3% by sampling, and finishing chlorination reaction; and (3) after distillation and desolventizing, adding 0.7mol of methanol, heating to 45 ℃, preserving heat for 0.5h, cooling to 15 ℃ after complete dissolution, preserving heat for 3h, adjusting the temperature to 15 ℃, performing heat preservation crystallization, suction filtration and drying to obtain the chlorfenapyr homolog chlorine-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethyl pyrrole-3-nitrile.
In the cyclization reaction product, the intermediate content is 97.3 percent, and the yield is 96.8 percent; in the addition decarboxylation reaction product, the content of the pyrrole compound is 96.4 percent, and the yield is 96.4 percent; in the condensation reaction product, the content of the condensation compound is 96.2 percent, and the yield is 97.1 percent; in the final product, the chlorfenapyr homolog chloro-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile content was 99%, and the yield was 97.4%.
Example 2
And (3) cyclization reaction: adding 0.35mol of p-chlorophenyl glycine, 0.875mol of acetonitrile and 0.53mol of trifluoroacetic acid into a reaction container, dropwise adding 0.37mol of triethylamine under a stirring state, controlling the temperature to be 10 ℃, dropwise adding 0.42mol of phosphorus trichloride after the dropwise adding is finished, keeping the temperature to be less than 20 ℃ in the dropwise adding process, and keeping the system temperature at 20 ℃ for 1.5 hours after the dropwise adding is finished to obtain an intermediate;
addition and decarboxylation reactions: adding 0.36mol of 2-chloroacrylonitrile into a reaction container containing the intermediate, cooling the material to a temperature of less than 20 ℃, dropwise adding 0.36mol of triethylamine, keeping the temperature at 15 ℃ in the dropwise adding process, detecting the pH value of the material after dropwise adding is finished, heating to 60 ℃, and keeping the temperature for 2 hours; distilling, removing the solvent, adding 1.05mol of water for washing, stirring for 0.5h, performing suction filtration, and drying to obtain a dried pyrrole compound;
condensation reaction: putting a dried pyrrole compound into a condensation reaction bottle, adding 0.39mol of potassium carbonate and 1.05mol of ethyl acetate, heating to 450 ℃ under stirring, dropwise adding 0.36mol of chloromethyl ethyl ether, heating to 53 ℃ after dropwise adding, keeping the temperature for 2 hours, sampling, adding water when the content of the pyrrole compound in the material is detected to be less than or equal to 0.5%, stirring for 0.5 hour, standing for layering, continuously heating an ethyl acetate layer, and distilling under normal pressure and reduced pressure to obtain a condensation compound; adding 0.875mol of dichloromethane into the condensation compound, stirring and dissolving to obtain a condensation compound dichloromethane solution;
chlorination reaction: cooling the dichloromethane solution of the condensation compound to 15 ℃, introducing 0.32mol of chlorine into the solution, keeping the temperature at 13 ℃ in the aeration process, stopping introducing the chlorine when the content of the condensation compound in the materials is detected to be less than or equal to 0.3% by sampling, and finishing chlorination reaction; and (2) after distillation and desolventizing, adding 0.875mol of methanol, heating to 50 ℃, preserving heat for 0.5h, cooling to 15-25 ℃ after all dissolution, preserving heat for 3h, adjusting the temperature to 18 ℃, carrying out heat preservation crystallization, carrying out suction filtration and drying to obtain the chlorfenapyr homolog chlorine-2- (4-chlorphenyl) -1-ethoxymethyl-5-trifluoromethyl pyrrole-3-nitrile.
According to the synthesis process provided by the invention, in the cyclization reaction product, the content of the intermediate is 97.5%, and the yield is 97%; in the addition decarboxylation reaction product, the content of the pyrrole compound is 96.5 percent, and the yield is 96.5 percent; in the condensation reaction product, the content of the condensation compound is 96 percent, and the yield is 97 percent; in the final product, the chlorfenapyr homolog chloro-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile content was 99%, and the yield was 97.5%.
Example 3
And (3) cyclization reaction: adding 0.35mol of p-chlorophenyl glycine, 0.7mol of acetonitrile and 0.46mol of trifluoroacetic acid into a reaction container, dropwise adding 0.42mol of triethylamine under a stirring state, controlling the temperature at 15 ℃, dropwise adding 0.7mol of phosphorus trichloride after the dropwise adding is finished, keeping the temperature less than 20 ℃ in the dropwise adding process, and keeping the system temperature at 25 ℃ for 1.5 hours after the dropwise adding is finished to obtain an intermediate;
addition and decarboxylation reactions: adding 2-chloroacrylonitrile 0.7mol into a reaction container containing the intermediate, cooling the material to a temperature of less than 20 ℃, dropwise adding triethylamine 0.53mol, keeping the temperature at 20 ℃ in the dropwise adding process, detecting the pH value of the material after dropwise adding is finished, heating to 65 ℃, and keeping the temperature for 2 hours; distilling, removing solvent, washing with water, stirring for 0.5h, vacuum filtering, and oven drying to obtain dried pyrrole compound;
condensation reaction: putting a dried pyrrole compound into a condensation reaction bottle, adding 0.7mol of potassium carbonate and 1.4mol of ethyl acetate, heating to 55 ℃ under stirring, dropwise adding 0.7mol of chloromethyl ethyl ether, heating to 55 ℃ after dropwise adding, keeping the temperature for 2 hours, sampling, adding water when the content of the pyrrole compound in the material is detected to be less than or equal to 0.5%, stirring for 0.5 hour, standing for layering, continuously heating an ethyl acetate layer, and distilling under normal pressure and reduced pressure to obtain a condensation compound; adding 1.4mol of dichloromethane into the condensation compound, stirring and dissolving to obtain a dichloromethane solution of the condensation compound;
chlorination reaction: cooling the dichloromethane solution of the condensation compound to 20 ℃, introducing 0.5mol of chlorine into the solution, keeping the temperature at 15 ℃ in the aeration process, stopping introducing the chlorine when the content of the condensation compound in the materials is detected to be less than or equal to 0.3% by sampling, and finishing chlorination reaction; and after distillation and desolventization, adding 1.4mol of methanol, heating to 55 ℃, preserving heat for 0.5h, cooling to 25 ℃ after complete dissolution, preserving heat for 3h, adjusting the temperature to 20 ℃, carrying out heat preservation crystallization, carrying out suction filtration and drying to obtain the chlorfenapyr homolog chlorine-2- (4-chlorphenyl) -1-ethoxymethyl-5-trifluoromethyl pyrrole-3-nitrile.
According to the synthesis process provided by the invention, in the cyclization reaction product, the content of the intermediate is 97.3%, and the yield is 96.8%; in the addition decarboxylation reaction product, the content of the pyrrole compound is 96.2 percent, and the yield is 96.3 percent; in the condensation reaction product, the content of the condensation compound is 96.1 percent, and the yield is 97 percent; in the final product, the chlorfenapyr homolog chloro-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrole-3-carbonitrile content was 99%, and the yield was 97.4%.
Claims (8)
1. A synthetic process of a chlorfenapyr homolog is characterized in that p-chlorophenyl glycine is used as a starting material, and the chlorfenapyr homolog is synthesized through cyclization, addition decarboxylation, condensation and chlorination, and has a chemical structural formula as follows:
the process of claim 1, wherein the reaction equation is:
the method comprises the following steps:
and (3) cyclization reaction: adding p-chlorophenylglycine, acetonitrile and trifluoroacetic acid into a reaction container, dropwise adding triethylamine under a stirring state, controlling the temperature to be 5-15 ℃, dropwise adding phosphorus trichloride after the dropwise adding is finished, keeping the temperature to be less than 20 ℃ in the dropwise adding process, and keeping the system temperature at 15-25 ℃ for 1.5 hours after the dropwise adding is finished to obtain an intermediate;
addition and decarboxylation reactions: adding 2-chloroacrylonitrile into a reaction container containing the intermediate, cooling the material to a temperature of less than 20 ℃, dropwise adding triethylamine, keeping the temperature at 10-20 ℃ in the dropwise adding process, detecting the pH value of the material after dropwise adding is finished, heating to 55-65 ℃, and keeping the temperature for 2 hours; distilling, removing solvent, washing with water, stirring for 0.5h, vacuum filtering, and oven drying to obtain dried pyrrole compound;
condensation reaction: putting a dried pyrrole compound into a condensation reaction bottle, adding potassium carbonate and ethyl acetate, heating to 45-55 ℃ under stirring, dropwise adding chloromethyl ethyl ether, heating to 50-55 ℃ after dropwise adding, keeping the temperature for 2 hours, sampling, adding water when the content of the pyrrole compound in the material is detected to be less than or equal to 0.5%, stirring for 0.5 hour, standing for layering, taking an ethyl acetate layer, continuously heating, and distilling under normal pressure and reduced pressure to obtain a condensation compound; adding dichloromethane into the condensation compound, stirring and dissolving to obtain a condensation compound dichloromethane solution;
chlorination reaction: cooling the dichloromethane solution of the condensation compound to 10-20 ℃, introducing chlorine into the solution, keeping the temperature at 10-15 ℃ in the aeration process, stopping introducing the chlorine when the content of the condensation compound in the materials is detected to be less than or equal to 0.3% by sampling, and finishing chlorination reaction; and (3) after distillation and desolventizing, adding methanol, heating to 45-55 ℃, preserving heat for 0.5h, cooling to 15-25 ℃ after all the materials are dissolved, preserving heat for 3h, adjusting the temperature to 15-20 ℃, carrying out heat preservation crystallization, carrying out suction filtration and drying to obtain the chlorfenapyr homolog.
2. The process for synthesizing a chlorfenapyr homolog according to claim 2, wherein in the cyclization reaction, the molar ratio of p-chlorophenyl glycine to acetonitrile is 1 (2-4), the molar ratio of p-chlorophenyl glycine to trifluoroacetic acid is 1 (1.05-1.5), the molar ratio of p-chlorophenyl glycine to triethylamine is 1 (1-1.2), the molar ratio of p-chlorophenyl glycine to phosphorus trichloride is 1 (1.02-2), and the residual content of p-chlorophenyl glycine in the intermediate is less than or equal to 0.5%.
3. The process for synthesizing a chlorfenapyr homolog according to claim 2, wherein in the addition decarboxylation reaction, the molar ratio of 2-chloropropene nitrile to p-chlorophenyl glycine in the cyclization reaction is (1-2): 1, the molar ratio of triethylamine to p-chlorophenyl glycine in the cyclization reaction is (1-1.5): 1, the molar ratio of water to p-chlorophenyl glycine in the cyclization reaction is 3:1, and the content of the intermediate in the material is less than or equal to 1%.
4. The process of claim 2, wherein the distillation in the addition decarboxylation reaction is a reduced pressure distillation, the negative pressure is-0.09 Mpa, and the temperature is 70 ℃; the pH of the material is = 7.5-8.5.
5. The process for synthesizing a chlorfenapyr homolog according to claim 2, wherein in the condensation reaction, the molar ratio of chloromethyl ethyl ether to p-chlorophenyl glycine in the cyclization reaction is (1-2): 1, the molar ratio of potassium carbonate to p-chlorophenyl glycine in the cyclization reaction is (1-2): 1, the molar ratio of ethyl acetate to p-chlorophenyl glycine in the cyclization reaction is (2-4): 1, and the molar ratio of water to p-chlorophenyl glycine in the cyclization reaction is 2: 1.
6. The process of claim 2, wherein the condensation reaction is carried out at a distillation temperature of 90 ℃ under atmospheric pressure, at a distillation pressure of-0.09 MPa under reduced pressure, and at a temperature of 90 ℃.
7. The process for synthesizing the chlorfenapyr homolog according to claim 2, wherein in the chlorination reaction, the molar ratio of chlorine to p-chlorophenyl glycine in the cyclization reaction is (1-1.5): 1, the molar ratio of dichloromethane to p-chlorophenyl glycine in the cyclization reaction is (2-4): 1, and the molar ratio of methanol to p-chlorophenyl glycine in the cyclization reaction is (2-4): 1.
8. The process of claim 2, wherein the step of the chlorination reaction comprises the step of distillation and desolventizing under reduced pressure at a pressure of-0.06 MPa and at a temperature of 50 ℃.
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| CN109169668A (en) * | 2018-09-11 | 2019-01-11 | 江苏省血吸虫病防治研究所 | 2- aryl substituted pyrroles class compound is killing the application in vesicle spiral shell drug |
| CN110382462A (en) * | 2017-03-13 | 2019-10-25 | 巴斯夫农业公司 | Aryl-pyrrole compound is produced in the presence of DIPEA alkali |
| CN113754561A (en) * | 2021-08-20 | 2021-12-07 | 李通 | Production method of 2-chloropropene nitrile and application thereof in synthesis of chlorfenapyr |
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2022
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| CN1091127A (en) * | 1992-11-30 | 1994-08-24 | 美国氰胺公司 | Pyrroles's Debrominative chlorination |
| WO1995018122A2 (en) * | 1993-12-30 | 1995-07-06 | Ciba-Geigy Ag | Heteroarylpyrroles |
| CN1224577A (en) * | 1997-08-08 | 1999-08-04 | 美国氰胺公司 | Arylpyrroles for protection of wood, wood products and wooden structures from insect attack |
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| CN110382462A (en) * | 2017-03-13 | 2019-10-25 | 巴斯夫农业公司 | Aryl-pyrrole compound is produced in the presence of DIPEA alkali |
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| CN113754561A (en) * | 2021-08-20 | 2021-12-07 | 李通 | Production method of 2-chloropropene nitrile and application thereof in synthesis of chlorfenapyr |
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