CN108484538B - Synthesis method of nematicide containing lactone ring - Google Patents
Synthesis method of nematicide containing lactone ring Download PDFInfo
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- CN108484538B CN108484538B CN201810585415.8A CN201810585415A CN108484538B CN 108484538 B CN108484538 B CN 108484538B CN 201810585415 A CN201810585415 A CN 201810585415A CN 108484538 B CN108484538 B CN 108484538B
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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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Abstract
The invention discloses a method for synthesizing a nematicide containing a lactone ring, which comprises the following steps: dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in a solvent, stirring uniformly, adding organic strong base into the solvent to perform salt forming reaction, then adding 4-bromo-1, 1, 2-trifluoro-1-butene into the solvent to perform substitution reaction to obtain a reaction solution, then performing acid washing, alkali washing, liquid separation, and removing the solvent by vacuum distillation of the organic phase to obtain [4- (1,1, 2-trifluoro-1-butene) ester of [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid; the invention solves the defect of incomplete reaction of 4-bromo-1, 1, 2-trifluoro-1-butene and carboxylic acid, reduces the decomposition of 4-bromo-1, 1, 2-trifluoro-1-butene, and has the product yield of over 85 percent, especially over 90 percent when DBU or tetramethyl guanidine is adopted; and the method has simple post-treatment process, is suitable for large-scale industrial production, greatly reduces the production cost and accelerates the popularization and application of new products.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing a nematicide containing a lactone ring.
Background
[2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester is a novel nematicide, the existing preparation method is a conventional synthesis method, and 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid and 4-bromo-1, 1, 2-trifluoro-1-butene are used as raw materials and are reacted in a conventional solvent such as methanol, acetonitrile, acetone and the like under the action of an acid-binding agent such as potassium carbonate, sodium carbonate and the like to obtain a target compound. However, the yield calculated by using 4-bromo-1, 1, 2-trifluoro-1-butene in the conventional synthesis method is only 58.9%, but the 4-bromo-1, 1, 2-trifluoro-1-butene is very expensive, so that the cost of the nematicide is high, and the popularization and the application of the nematicide are limited.
In the study on direct synthesis of esters from carboxylic acids and carboxylates and halogenated hydrocarbons, in the presence of triethylamine or triethylamine and sodium iodide, the carboxylic acids and carboxylates were directly acetified with halogenated hydrocarbons, and the experiments according to this article were not carried out. Through theoretical analysis and repeated experiment comparison, the main reason of low product yield is that 4-bromo-1, 1, 2-trifluoro-1-butene is decomposed in the reaction process of the 4-bromo-1, 1, 2-trifluoro-1-butene and the problem of controlling the decomposition of the 4-bromo-1, 1, 2-trifluoro-1-butene without influencing the reaction is the biggest problem of the project.
Disclosure of Invention
In order to solve the above problems, it is an object of the present invention to provide a method for synthesizing a lactone ring-containing nematicide.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a method for synthesizing a lactone ring-containing nematicide which is [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester, comprising the following steps:
dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in solvent, stirring, adding organic strong base, salifying reaction is carried out for 0.5-2 hours at the temperature of 0-80 ℃, then 4-bromo-1, 1, 2-trifluoro-1-butene is added into the reaction solution, carrying out substitution reaction for 1-72 hours at 40-110 ℃ to obtain a reaction solution, adding hydrochloric acid into the reaction solution, adjusting the pH value to 3-6, then adding a sodium carbonate aqueous solution with the mass concentration of 10-15% into the mixture until the pH value is 8-11, separating the mixture, and carrying out vacuum distillation on the organic phase to remove the solvent so as to obtain [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid [4- (1,1, 2-trifluoro-1-butylene) yl ] ester;
the organic strong base is alkali metal salt of alcohol, alkyl metal lithium compound, pyridine, tetramethyl guanidine, triethylamine or DBU; the solvent is toluene, benzene, dichloromethane or chloroform;
wherein the molar volume ratio of the 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid to the organic strong base to the solvent to the 4-bromo-1, 1, 2-trifluoro-1-butene is 1.5-3 mol: 1-2 mol: 0.5-1L: 1 mol.
A preferred synthesis method is characterized by: the organic strong base is DBU or tetramethylguanidine.
A preferred synthesis method is characterized by: the temperature of the salt forming reaction is 30-50 ℃, and the time is 1-2 hours.
A preferred synthesis method is characterized by: the temperature of the substitution reaction is 70-90 ℃, and the time is 48-60 hours.
A preferred synthesis method is characterized by: the solvent is chloroform.
A preferred synthesis method is characterized by: the organic strong base is tetramethylguanidine.
A preferred synthesis method is characterized by: the method comprises the following steps:
dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in chloroform, stirring uniformly, cooling to 10-30 ℃, dropwise adding organic strong base at the dropping speed of 1-5 drops/5 seconds, after the dropwise adding is finished, heating to 30-60 ℃, reacting for 0.5-2 hours, adding 4-bromo-1, 1, 2-trifluoro-1-butene, reacting for 48-60 hours under reflux to obtain a reaction solution, adding hydrochloric acid into the reaction solution, adjusting the pH to 3-4, then adding a sodium carbonate aqueous solution with the mass concentration of 10% into the reaction solution until the pH is 8-10, separating, carrying out vacuum distillation on the organic phase to remove the solvent to obtain [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester;
wherein the molar volume ratio of the 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid to the organic strong base to the solvent to the 4-bromo-1, 1, 2-trifluoro-1-butene is 1.5-2 mol: 1-1.5 mol: 0.5-1L: 1 mol;
the organic strong base is DBU or tetramethylguanidine.
Preferably, the strong organic base is tetramethylguanidine.
The reaction mechanism of the compounds of the present invention (for example tetramethyl guanidine) is:
the general chemical reaction formula of the invention is:
compared with the prior art, the invention has the following advantages:
the reaction of 4-bromo-1, 1, 2-trifluoro-1-butene with carboxylic acid must be carried out under alkaline conditions, whereas 4-bromo-1, 1, 2-trifluoro-1-butene is decomposed under alkaline conditions, and in order to control the decomposition of 4-bromo-1, 1, 2-trifluoro-1-butene, the conventional method is to use weak base for the reaction, but the reaction is carried out by the method, the reaction of 4-bromo-1, 1, 2-trifluoro-1-butene with carboxylic acid is incomplete, and impurities are easily generated, resulting in a product yield of only 30-40%, and the expensive cost of 4-bromo-1, 1, 2-trifluoro-1-butene severely limits the [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] - Production of a 4- (1,1, 2-trifluoro-1-butene) -carboxylic acid ester; the invention adopts carboxylic acid and organic strong base to generate carboxylate, and then the carboxylate reacts with 4-bromo-1, 1, 2-trifluoro-1-butene to obtain a target product, thereby solving the defect of incomplete reaction of 4-bromo-1, 1, 2-trifluoro-1-butene and carboxylic acid, reducing the decomposition of 4-bromo-1, 1, 2-trifluoro-1-butene, and ensuring that the yield of the product can reach more than 85 percent, particularly the yield of the product can reach more than 90 percent when DBU or tetramethylguanidine is adopted; and the method has simple post-treatment process, is suitable for large-scale industrial production, greatly reduces the production cost and accelerates the popularization and application of new products.
Detailed Description
Alkali metal salts of alcohols in the present invention include sodium methoxide, potassium ethoxide, potassium tert-butoxide, sodium tert-butoxide, etc.; the lithium alkyl metal compounds include n-butyl lithium, ethyl lithium and the like.
The invention is further described with reference to specific examples.
Example 1
Dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid (35.4 kg) in toluene (50L), stirring, adding sodium methoxide (5.4 kg) to the solution, reacting at 0 deg.C for 0.5 hr, adding 4-bromo-1, 1, 2-trifluoro-1-butene (18.9 kg) to the solution, reacting at 40 deg.C for 1 hr to obtain a reaction solution, adding hydrochloric acid to the reaction solution to adjust pH to 3, adding 10% by mass aqueous sodium carbonate solution to pH 8, separating, distilling the organic phase under reduced pressure to remove the solvent to obtain 29.3kg of [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester, the yield was 85.2%.
Example 2
70.86kg of 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid is dissolved in 100L of benzene, the mixture is stirred uniformly, 12.8kg of n-butyllithium is added into the mixture, salifying reaction is carried out for 2 hours at 80 ℃, 18.9kg of 4-bromo-1, 1, 2-trifluoro-1-butene is then added into the mixture, substitution reaction is carried out for 72 hours under reflux to obtain a reaction solution, hydrochloric acid is added into the reaction solution, the pH is adjusted to 6, then sodium carbonate aqueous solution with the mass concentration of 15% is added into the reaction solution until the pH is 11, liquid separation is carried out, organic phase is decompressed and distilled to remove the solvent, and 30kg of [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid [4- (1,1, 2-trifluoro-1-butene) -yl ] ester is obtained, the yield was 87.4%.
Example 3
Dissolving 47.2kg of 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in 60L of dichloromethane, stirring uniformly, adding 9.5kg of pyridine thereto, carrying out a salt-forming reaction at 20 ℃ for 1 hour, then adding 18.9kg of 4-bromo-1, 1, 2-trifluoro-1-butene thereto, carrying out a substitution reaction under reflux for 10 hours to obtain a reaction solution, adding hydrochloric acid to the reaction solution, adjusting the pH to 4, then adding an aqueous solution of sodium carbonate having a mass concentration of 12% thereto to a pH of 10, carrying out liquid separation, carrying out vacuum distillation on the organic phase to remove the solvent, to obtain 29.8kg of [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid [4- (1,1, 2-trifluoro-1-butene) -yl ] ester, the yield was 86.6%.
Example 4
Dissolving 59kg of 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in 80L of chloroform, stirring uniformly, adding 15.2kg of triethylamine thereto, carrying out a salt-forming reaction at 70 ℃ for 1.5 hours, then adding 18.9kg of 4-bromo-1, 1, 2-trifluoro-1-butene thereto, carrying out a substitution reaction under reflux for 60 hours to obtain a reaction solution, adding hydrochloric acid to the reaction solution, adjusting the pH to 5, then adding an aqueous solution of sodium carbonate having a mass concentration of 14% thereto to a pH of 9, carrying out liquid separation, carrying out vacuum distillation on the organic phase to remove the solvent, to obtain 30.1kg of [4- (1,1, 2-trifluoro-1-butene) -4-carboxylic acid [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] ester, the yield was 87.5%.
Example 5
Dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid 42.5kg in 70L dichloromethane, stirring, adding DBU 27.4kg, reacting at 50 deg.C for 1.2 hr, adding 4-bromo-1, 1, 2-trifluoro-1-butene 18.9kg, substituting under reflux for 50 hr to obtain a reaction solution, adding hydrochloric acid to the reaction solution to adjust pH to 4, adding 13% by mass aqueous solution of sodium carbonate to pH 10, separating, distilling under reduced pressure the organic phase to remove the solvent to obtain [4- (1,1, 2-trifluoro-1-butene) -4- [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid [ 1- (1,1, 2-trifluoro-1-butene) -yl ] ester 31.1kg, the yield was 90.5%.
Example 6
Dissolving 52kg of 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in 80L of toluene, stirring uniformly, adding 18.4kg of tetramethylguanidine thereto, carrying out a salt-forming reaction at 60 ℃ for 1.8 hours, then adding 18.9kg of 4-bromo-1, 1, 2-trifluoro-1-butene thereto, carrying out a substitution reaction under reflux for 30 hours to obtain a reaction solution, adding hydrochloric acid to the reaction solution, adjusting the pH to 5, then adding an aqueous solution of sodium carbonate having a mass concentration of 12% thereto to a pH of 9, carrying out liquid separation, carrying out vacuum distillation on the organic phase to remove the solvent, to obtain 31.5kg of [4- (1,1, 2-trifluoro-1-butene) -4-carboxylic acid [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] ester, the yield was 91.8%.
Example 7
Dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid 54.3kg in 70L chloroform, stirring, adding tetramethylguanidine 16.1kg, reacting at 30 ℃ for 1 hour, adding 4-bromo-1, 1, 2-trifluoro-1-butene 18.9kg, reacting under reflux for 48 hours to obtain a reaction solution, adding hydrochloric acid to the reaction solution to adjust pH to 4, adding a 10% sodium carbonate aqueous solution to pH 11, separating, subjecting the organic phase to vacuum distillation to remove the solvent to obtain 31.8kg of [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester, the yield was 92.4%.
Example 8
Dissolving 35.4kg of 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in 50L of benzene, stirring uniformly, adding 15.2kg of DBU, carrying out a salt-forming reaction at 80 ℃ for 2 hours, then adding 18.9kg of 4-bromo-1, 1, 2-trifluoro-1-butene, carrying out a substitution reaction under reflux for 8 hours to obtain a reaction solution, adding hydrochloric acid to the reaction solution, adjusting the pH to 3, then adding a sodium carbonate aqueous solution with the mass concentration of 15% to the pH of 8, carrying out liquid separation, carrying out vacuum distillation on the organic phase to remove the solvent, thus obtaining 32kg of [4- (1,1, 2-trifluoro-1-butene) -4- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid ester, the yield was 93.0%.
Example 9
Dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid 47.2kg in chloroform 100L, stirring, cooling to 30 deg.C, adding tetramethylguanidine 11.5kg dropwise at a rate of 1 drop/5 s, refluxing for 0.5 hr, adding 4kg of 4-bromo-1, 1, 2-trifluoro-1-butene, reacting at reflux for 60 hr to obtain a reaction solution, adding hydrochloric acid to the reaction solution to adjust pH to 3, adding 10% sodium carbonate aqueous solution to pH 8, separating, removing the solvent by vacuum distillation of the organic phase to obtain 32.8kg of [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -carboxylic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester in 95.6% yield.
Example 10
Dissolving 35.4kg of 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in 50L of chloroform, stirring uniformly, cooling to 10 ℃, dropwise adding 17.2kg of tetramethylguanidine at a dropping speed of 1-5 drops/5 seconds, after the dropwise addition, heating to 60 ℃, reacting for 2 hours, adding 18.9kg of 4-bromo-1, 1, 2-trifluoro-1-butene, reacting for 48 hours under reflux to obtain a reaction solution, adding hydrochloric acid to the reaction solution, adjusting the pH to 4, then adding a sodium carbonate aqueous solution with the mass concentration of 10% to the pH of 10, separating, carrying out vacuum distillation on the organic phase to remove the solvent, obtaining 33.3kg of [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester in 96.8% yield.
Claims (7)
1. A method for synthesizing a nematicide containing a lactone ring is characterized in that:
the nematicide containing the lactone ring is [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid [4- (1,1, 2-trifluoro-1-butylene) group ] ester, and the synthesis method comprises the following steps:
dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in solvent, stirring, adding organic strong base, salifying reaction is carried out for 0.5-2 hours at the temperature of 0-80 ℃, then 4-bromo-1, 1, 2-trifluoro-1-butene is added into the reaction solution, carrying out substitution reaction for 1-72 hours at 40-110 ℃ to obtain a reaction solution, adding hydrochloric acid into the reaction solution, adjusting the pH value to 3-6, then adding a sodium carbonate aqueous solution with the mass concentration of 10-15% into the mixture until the pH value is 8-11, separating the mixture, and carrying out vacuum distillation on the organic phase to remove the solvent so as to obtain [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid [4- (1,1, 2-trifluoro-1-butylene) yl ] ester;
the organic strong base is DBU or tetramethylguanidine; the solvent is toluene, benzene, dichloromethane or chloroform;
wherein the molar volume ratio of the 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid to the organic strong base to the solvent to the 4-bromo-1, 1, 2-trifluoro-1-butene is 1.5-3 mol: 1-2 mol: 0.5-1L: 1 mol.
2. The method of claim 1 for the synthesis of a nematicide comprising a lactone ring, wherein: the temperature of the salt forming reaction is 30-50 ℃, and the time is 1-2 hours.
3. The method of claim 1 for the synthesis of a nematicide comprising a lactone ring, wherein: the temperature of the substitution reaction is 70-90 ℃, and the time is 48-60 hours.
4. The method of claim 1 for the synthesis of a nematicide comprising a lactone ring, wherein: the solvent is chloroform.
5. The method of claim 1 for the synthesis of a nematicide comprising a lactone ring, wherein: the organic strong base is tetramethylguanidine.
6. The method of claim 1 for the synthesis of a nematicide comprising a lactone ring, wherein: the method comprises the following steps:
dissolving 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid in chloroform, stirring uniformly, cooling to 10-30 ℃, dropwise adding organic strong base at the dropping speed of 1-5 drops/5 seconds, after the dropwise adding is finished, heating to 30-60 ℃, reacting for 0.5-2 hours, adding 4-bromo-1, 1, 2-trifluoro-1-butene, reacting for 48-60 hours under reflux to obtain a reaction solution, adding hydrochloric acid into the reaction solution, adjusting the pH to 3-4, then adding a sodium carbonate aqueous solution with the mass concentration of 10% into the reaction solution until the pH is 8-10, separating, carrying out vacuum distillation on the organic phase to remove the solvent to obtain [2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-yl ] -formic acid [4- (1,1, 2-trifluoro-1-butene) yl ] ester;
wherein the molar volume ratio of the 2- (2-methoxyphenyl) -5-oxotetrahydrofuran-3-carboxylic acid to the organic strong base to the solvent to the 4-bromo-1, 1, 2-trifluoro-1-butene is 1.5-2 mol: 1-1.5 mol: 0.5-1L: 1 mol;
the organic strong base is DBU or tetramethylguanidine.
7. The method of claim 6, wherein the lactone ring-containing nematicide comprises: the organic strong base is tetramethylguanidine.
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