CN112295608B - Ferric trichloride regeneration recycling method for aromatization of triazole compounds - Google Patents
Ferric trichloride regeneration recycling method for aromatization of triazole compounds Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/42—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using halogen-containing material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
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Abstract
The invention relates to a ferric trichloride regeneration recycling method for aromatization of triazole compounds, which belongs to the technical field of pesticide industrial production, and comprises the steps of firstly oxidizing a compound I containing triazole groups into a compound II containing unsaturated triazole groups by using a ferric trichloride aqueous solution, separating to obtain a ferrous chloride aqueous solution, adding ferric oxide into the obtained ferrous chloride aqueous solution, introducing chlorine to oxidize to obtain ferric trichloride, and recycling and oxidizing the obtained ferric trichloride for multiple times. The invention regenerates with chlorine after ferric trichloride is used, can repeatedly use for many times without affecting the reaction effect, avoids environmental pollution, saves production raw materials and reduces production cost.
Description
Technical Field
The invention relates to a ferric trichloride regeneration recycling method for aromatization of triazole compounds, belonging to the technical field of pesticide industrial production.
Background
Triazole compounds are currently the most widely used important functional groups of human antibiotics and agricultural bactericides worldwide. In agricultural production, the triazole compound is used as an agricultural bactericide, so that the crop yield can be improved, and the plant diseases of crops caused by fungi can be controlled. In recent years, landscaping, vegetable crops, field crops, cereal crops and the like have reduced yield and increased selling price each year due to untimely disease control of different degrees. Therefore, the intensive research on triazole compounds improves the synthesis process of the bactericide, improves the yield of the triazole bactericide, and develops a more environment-friendly and safer production process.
Ferric trichloride is used as a mild and applicable oxidant in the preparation process of triazole compound bactericides, the direct discharge of by-product ferrous chloride can cause serious environmental pollution, and the recycling problem of ferrous chloride is needed to be solved in the present day of the gradual enhancement of people's environmental awareness. Patent WO0146158A1 reports that the oxidation reagent for the aromatization of triazole compounds is ferric trichloride acidified by hydrochloric acid, and the reaction solution is poured into ice water for extraction by ethyl acetate after the post-treatment, so that a large amount of acidic ferrous chloride aqueous solution is generated, and the treatment is difficult. Patent CN108752283a reports that ferric trichloride is used as an oxidant, triazole groups are aromatized by reacting for 6 hours in an oxygen atmosphere, but the problem of regeneration and recycling of generated ferrous chloride is not reported.
Patent CN111303059a reports that a catalytic amount of ferric trichloride is added into a reaction solution, the ferric trichloride oxidizes a triazole group to generate ferrous chloride, then hydrogen peroxide is added into the reaction solution in a dropwise manner, and the ferrous chloride continuously reacts with triazole compounds after being oxidized with the hydrogen peroxide. The reaction using hydrogen peroxide instead of ferric trichloride as the oxidizing agent is reported in patent CN 106986838A. In the method, the production of a large amount of ferric trichloride wastewater is avoided by reducing the dosage of ferric trichloride or selecting a substitute oxidant, but the oxydol has strong oxidizing property, and the reaction temperature and the hydrogen peroxide addition amount are strictly controlled to avoid the production of desulfurization impurities.
In addition, the obtained ferrous chloride aqueous solution is oxidized by chlorine or oxygen and then is continuously applied, and the oxidation efficiency is drastically reduced after repeated application. In order to solve the problems, the invention provides an economic and environment-friendly method for recycling ferric trichloride, which can maintain the oxidation effect.
Disclosure of Invention
The invention aims to provide a method for recycling ferric trichloride for aromatization of triazole compounds, which is used for recycling ferrous chloride which is a byproduct generated after the aromatization of triazole compounds.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
firstly, oxidizing a compound I containing triazole groups into a compound II containing unsaturated triazole groups by using an iron trichloride aqueous solution, separating to obtain an iron chloride aqueous solution, adding ferric oxide into the obtained iron chloride aqueous solution, then introducing chlorine to oxidize to obtain iron trichloride, and recycling the obtained iron trichloride for reaction, wherein the specific reaction formula is as follows:
wherein R is one or more of hydrogen, alkyl, alkoxy, heterocyclic group, aryl, heteroaryl, halogenated C6-C10 aryl or C1-C9 heteroaryl;
x is oxygen or sulfur.
The technical scheme of the invention is further improved as follows: the method comprises the following steps:
A. adding the compound I into a solvent under stirring, heating to 30-80 ℃, slowly dropwise adding 10-40% of ferric trichloride aqueous solution, and keeping the temperature until the content of the compound I is less than 0.1% and the reaction is qualified; cooling and filtering to obtain a compound II, and separating to obtain an aqueous solution of ferrous chloride;
B. and C, adding a certain amount of ferric oxide into the ferrous chloride aqueous solution obtained by the separation in the step A, and then introducing a certain amount of chlorine to react to obtain the ferric chloride aqueous solution for the step A again.
The technical scheme of the invention is further improved as follows: and B, judging whether ferrous ions in the ferrous chloride are completely converted into ferric ions or not, and detecting by a spectrophotometry.
The technical scheme of the invention is further improved as follows: and B, determining the introducing amount of the chlorine by weighing the added weight of the reaction solution, wherein the using amount of the chlorine in the step B is 0.5-0.6 of the mole number of ferrous chloride, and taking the excessive chlorine out by bubbling nitrogen through excessive chlorine, and absorbing the tail gas by using enough alkali liquor.
The technical scheme of the invention is further improved as follows: the temperature of the ferrous chloride aqueous solution in the step B is 10-60 ℃.
The technical scheme of the invention is further improved as follows: the dosage of ferric oxide in the step B is that the dosage of ferrous chloride is 0.05-0.15 of the mole number of ferrous chloride.
The technical scheme of the invention is further improved as follows: the solvent in the step A is toluene or xylene.
By adopting the technical scheme, the invention has the following technical effects:
according to the invention, the triazole compound is aromatised by selecting the milder oxidant ferric trichloride, so that desulfurization impurities generated due to strong oxidizing property are avoided, the separated ferrous chloride solution is oxidized and regenerated by chlorine, other hetero atoms are not introduced, the regenerated ferric trichloride solution can be repeatedly used for many times, ferrous chloride wastewater is not generated, the ferrous chloride wastewater is not discharged into the environment, and environmental pollution is avoided.
The application frequency of the ferric trichloride does not influence the oxidation effect of the ferric trichloride, and the yield and the content of a product obtained by oxidation are not influenced by the application frequency, so that the ferric trichloride can be repeatedly used for multiple times after being used, the environmental pollution is avoided, and the production cost is reduced.
The regeneration reagent chlorine gas used in the invention is a common industrial raw material, is low in cost and low in cost, and is suitable for large-scale industrial production; chlorine and ferric oxide are used, other hetero atoms are not introduced, and the production is not influenced.
Detailed Description
The invention will be described in further detail with reference to the following examples:
a method for regenerating and recycling ferric trichloride for aromatizing triazole compounds comprises the following steps:
A. adding a compound I into toluene or xylene serving as a solvent under stirring, heating to 30-80 ℃, slowly dropwise adding 10-40% of ferric trichloride aqueous solution, and keeping the temperature until the content of the compound I is less than 0.1% and the reaction is qualified; cooling and filtering to obtain a compound II, and separating to obtain an aqueous solution of ferrous chloride;
B. adding ferric oxide with the mole number of ferrous chloride of 0.05-0.15 into the ferrous chloride aqueous solution with the temperature of 10-60 ℃ obtained by separation in the step A, then introducing chlorine with the mole number of ferrous chloride of 0.5-0.6, determining the introducing amount of the chlorine by weighing the added weight of the reaction solution, taking out the excessive chlorine by bubbling nitrogen, and absorbing the tail gas by using a sufficient amount of alkali liquor. And (3) reacting to obtain an aqueous solution of ferric chloride, detecting and judging whether ferrous ions in the ferrous chloride are completely converted into ferric ions by a spectrophotometry method, and reusing the obtained aqueous solution of ferric chloride in the step (A).
Example 1
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under stirring, 195g of 30% ferric trichloride aqueous solution is dropwise added after heating to 30 ℃, the mixture is heated to 6h, the liquid chromatography is tracked and monitored to be less than 0.5%, the temperature is reduced to 0-5 ℃, the mixture is subjected to vacuum suction filtration, the product is washed twice with 15g of water, and the white solid is obtained after drying, wherein the content is 98.5%, and the yield is 94.9%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution 2+ 10.60% of Fe 3+ The content is 0.31%. Transferring the recovered solution into a 500ml four-mouth bottle, controlling the temperature to 10-60 ℃, adding 2.9g of ferric oxide, stopping ventilation when the weight gain of the introduced chlorine gas is about 11.2g, analyzing and detecting to be qualified (no ferrous ions), preserving heat and stirring for 1h, blowing nitrogen gas to carry out redundant chlorine gas, introducing the gas into a sufficient amount of sodium hydroxide solution for absorption, and thus the obtained ferric trichloride can be subjected to a mechanically applied experiment.
EXAMPLE 2 regeneration of ferric trichloride for reuse
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thioxo-1-yl ] -propane is added under stirring, the temperature is raised to 50 ℃, the oxidized ferric trichloride aqueous solution in the example 1 is dripped, the dripping is completed, the temperature is kept for 3 hours, the liquid chromatography is tracked and monitored to be less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, and the white solid 48.1g with the content of 98.1% and the yield of 95.2% is obtained after drying.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution 2+ 10.01% of Fe 3+ The content is 1.26%. Transferring the recovered solution into a 500ml four-mouth bottle, heating to 10-60 ℃, adding 5.6g of ferric oxide, stopping ventilation when the weight gain of the introduced chlorine gas is about 11.8g, analyzing and detecting to be qualified (no ferrous ions), carrying out heat preservation and stirring for 1h, blowing nitrogen gas to carry out redundant chlorine gas, introducing the gas into a sufficient amount of sodium hydroxide solution for absorption, and performing a mechanically applied experiment on the obtained ferric trichloride.
Example 3 regeneration of ferric trichloride for secondary use
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thioxo-1-yl ] -propane is added under stirring, the temperature is raised to 80 ℃, the oxidized ferric trichloride aqueous solution in the example 2 is dripped, the dripping is completed, the temperature is kept for 1h, the liquid chromatography is tracked and monitored to be less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, and the white solid 48.3g with the content of 98.0% and the yield of 95.3% is obtained after drying.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution 2+ Content 9.98%, fe 3+ The content is 0.98%. Transferring the recovered ferric trichloride solution into a 500ml four-mouth bottle, heating to 10-60 ℃, adding 8.5g of ferric oxide, stopping ventilation when the weight gain of the introduced chlorine gas is about 11.5g, analyzing and detecting to be qualified (no ferrous ions), preserving heat and stirring for 1h, blowing nitrogen gas to carry out redundant chlorine gas, introducing the gas into a sufficient amount of sodium hydroxide solution for absorption, and performing a mechanically-applied experiment on the obtained ferric trichloride.
Example 4 regeneration of ferric trichloride three times
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thioxo-1-yl ] -propane is added under stirring, the temperature is raised to 40 ℃, the oxidized ferric trichloride aqueous solution in the example 3 is dripped, the dripping is completed, the temperature is kept for 4 hours, the liquid chromatography is tracked and monitored to be less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, and the white solid 48.2g with the content of 98.1% and the yield of 95.2% is obtained after drying.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution 2+ Content 9.95%, fe 3+ The content is 1.15%. Transferring the recovered ferric trichloride solution into a 500ml four-mouth bottle, heating to 10-60 ℃, adding 5.5g of ferric oxide, stopping ventilation when the weight gain of the introduced chlorine gas is about 11.2g, analyzing and detecting to be qualified (no ferrous ions), preserving heat and stirring for 1h, blowing nitrogen gas to carry out redundant chlorine gas, introducing the gas into a sufficient amount of sodium hydroxide solution for absorption, and performing a mechanically-applied experiment on the obtained ferric trichloride.
EXAMPLE 5 ferric chloride was regenerated four times after removal of excess Hydrogen chloride
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-necked flask, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under stirring, the temperature is raised to 65 ℃, the ferric trichloride aqueous solution obtained in the example 4 is dripped, the dripping is completed, the temperature is kept for 2 hours, the liquid chromatography is tracked and monitored to be less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, and the white solid 48.3g with the content of 98.2% and the yield of 95.4% is obtained after drying.
The above examples show that the application frequency does not affect the oxidation of ferric trichloride, and the yield and content of the product obtained by oxidation are not affected by the application frequency, so that the ferric trichloride can be regenerated by chlorine after being oxidized, and can be repeatedly applied for many times, thereby avoiding environmental pollution.
Comparative example 1
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under stirring, the temperature is raised to 35 ℃, 195g of 30% ferric trichloride aqueous solution is dropwise added, the temperature is kept for 5.5h, the liquid chromatography is tracked and monitored to be less than 0.5%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, and the white solid is obtained after drying, the content is 98.2%, and the yield is 95.3%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution 2+ 10.51% of Fe 3+ The content is 0.37%. Transferring the recovered solution into a 500ml four-mouth bottle, controlling the temperature to 10-60 ℃, adding 2.9g of ferric oxide, stopping ventilation when the weight gain of the introduced chlorine gas is about 11.2g, analyzing and detecting to be qualified (no ferrous ions), preserving heat and stirring for 1h, blowing nitrogen gas to carry out redundant chlorine gas, introducing the gas into a sufficient amount of sodium hydroxide solution for absorption, and thus the obtained ferric trichloride can be subjected to a mechanically applied experiment.
Comparative example 2 regeneration of ferric chloride was carried out once without ferric oxide
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thioxo-1-yl ] -propane is added under stirring, the temperature is raised to 60 ℃, the oxidized ferric trichloride aqueous solution in the example 1 is dripped, the dripping is completed, the temperature is kept for 2 hours, the liquid chromatography is tracked and monitored to be less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, and the white solid 46.1g with 96.2 percent of content and 92.2 percent of yield is obtained after drying.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution 2+ 10.01% of Fe 3+ The content is 1.26%. Transferring the recovered solution into 500ml four-mouth bottle, heating toStopping ventilation when the weight gain of the introduced chlorine gas is about 11.8g at the temperature of 10-60 ℃, analyzing and detecting to be qualified (no ferrous ions), preserving heat and stirring for 1h, blowing nitrogen gas to bring out redundant chlorine gas, introducing the gas into a sufficient amount of sodium hydroxide solution for absorption, and performing a mechanically-applied experiment on the obtained ferric trichloride.
Comparative example 3 regeneration and secondary reuse of ferric trichloride without ferric oxide
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under stirring, the temperature is raised to 45 ℃, the oxidized ferric trichloride aqueous solution in the example 2 is dripped, the dripping is completed, the temperature is kept for 3.5h, the liquid chromatography is tracked and monitored, the temperature is reduced to 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, the content is 94.3%, and the yield is 86.6%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution 2+ Content 9.98%, fe 3+ The content is 0.98%. Transferring the recovered ferric trichloride solution into a 500ml four-mouth bottle, heating to 10-60 ℃, then introducing chlorine gas, stopping ventilation when the weight gain is about 11.5g, analyzing and detecting to be qualified (no ferrous ions), insulating and stirring for 1h, blowing nitrogen gas to carry out redundant chlorine gas, introducing the gas into a sufficient amount of sodium hydroxide solution for absorption, and performing a mechanically applied experiment on the obtained ferric trichloride.
Comparative example 4 regeneration of ferric chloride three times for reuse without ferric oxide
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thioxo-1-yl ] -propane is added under stirring, the temperature is raised to 50 ℃, the oxidized ferric trichloride aqueous solution in comparative example 3 is dripped, the dripping is completed, the temperature is kept for 3 hours, the liquid chromatography is tracked and monitored to be less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced, the suction filtration is carried out, the product is washed twice with 15g of water, and the white solid with the content of 91.1% and the yield of 81.2% is obtained after drying.
Comparative example 5
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
Into a 500ml four-necked flask, 200g of toluene or xylene was added, and 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane, 0.7g of iron trichloride was added under stirring, followed by slowly dropping 7.36g of hydrogen peroxide. The reaction solution was stirred at 20℃for 2h. After the reaction is finished, 9.39g of sodium sulfite is added into the reaction liquid to reduce excessive hydrogen peroxide, and the mixture is stirred for 1h at room temperature, and is detected by using starch potassium iodide test paper, and the test paper does not change blue to indicate that the hydrogen peroxide is thoroughly reduced. The reaction system was washed with 60ml of water, and the organic phases were combined, dried over sodium sulfate and concentrated. 50.8g of crude product are obtained, the content of which is 89%. The crude product was recrystallized from toluene to give 43.3g of a white solid with a content of 95.2% and a yield of 83.0%.
Comparative example 6
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thione-1-yl) -propane
200g of toluene or xylene is added into a 500ml four-port bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1, 2, 4-triazolyl-5-thioketone-1-yl) -propane is added under stirring, 6.58g of hydrogen peroxide is slowly added dropwise, stirring is carried out for 3 hours at 20 ℃, after the reaction is finished, 3.6g of sodium sulfite is added into the reaction solution, excessive hydrogen peroxide is reduced, stirring is carried out for 1 hour at room temperature, the reaction solution is detected by using starch potassium iodide test paper, and the test paper does not change blue to indicate that the reduction is complete. The reaction system was washed with 40ml of water, separated, and the organic phase was concentrated to give 49.1g of crude product with 86%. The crude product was recrystallized from toluene to give 40.1g of a white solid with a content of 93.0% and a yield of 75.0%.
Product quality comparison table:
as shown in the table above, (1) the application frequency of the method does not influence the oxidation of the ferric trichloride, and the yield and the content of the product obtained by oxidation are not influenced by the application frequency; (2) When ferric oxide is not added in the oxidation process of the ferrous chloride aqueous solution, the oxidation effect of ferric chloride which is used mechanically is obviously reduced; (3) The content and the yield of the product obtained by the reaction after the hydrogen peroxide is used as an oxidant or the hydrogen peroxide oxidizes the ferric trichloride are reduced to different degrees.
Claims (3)
1. A method for regenerating and recycling ferric trichloride for aromatizing triazole compounds is characterized by comprising the following steps of: firstly, oxidizing a compound I containing triazole groups into a compound II containing unsaturated triazole groups by using an iron trichloride aqueous solution, separating to obtain an iron chloride aqueous solution, adding ferric oxide into the obtained iron chloride aqueous solution, introducing chlorine to oxidize to obtain iron trichloride, and reusing the obtained iron trichloride for reaction, wherein the iron trichloride is recycled and oxidized for a plurality of times, and the specific reaction formula is as follows:
wherein R is one or more of hydrogen, alkyl, alkoxy, heterocyclic group, aryl, heteroaryl, halogenated C6-C10 aryl or C1-C9 heteroaryl;
x is oxygen or sulfur;
the method comprises the following steps:
A. adding the compound I into a solvent under stirring, heating to 30-80 ℃, slowly dropwise adding 10-40% of ferric trichloride aqueous solution, and keeping the temperature until the content of the compound I is less than 0.1% and the reaction is qualified; cooling and filtering to obtain a compound II, and separating to obtain an aqueous solution of ferrous chloride;
B. adding a certain amount of ferric oxide into the ferrous chloride aqueous solution obtained by separation in the step A, then introducing a certain amount of chlorine, and reacting to obtain an aqueous solution of ferric trichloride for the step A again; the dosage of the chlorine is 0.5-0.6 of ferrous chloride mole number; the temperature of the ferrous chloride aqueous solution is 10-60 ℃; the dosage of ferric oxide is 0.05-0.15 of ferrous chloride mole number, the introducing amount of chlorine is determined by weighing the weight of the reaction liquid, excessive chlorine is carried out by bubbling nitrogen, and the tail gas is absorbed by a sufficient amount of alkali liquor.
2. The method for regenerating and recycling ferric trichloride for aromatizing triazole compounds according to claim 1, which is characterized in that: and B, judging whether ferrous ions in the ferrous chloride are completely converted into ferric ions or not, and detecting by a spectrophotometry.
3. The method for regenerating and recycling ferric trichloride for aromatizing triazole compounds according to claim 1, which is characterized in that: the solvent in the step A is toluene or xylene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202011306822.4A CN112295608B (en) | 2020-11-19 | 2020-11-19 | Ferric trichloride regeneration recycling method for aromatization of triazole compounds |
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| CN202011306822.4A CN112295608B (en) | 2020-11-19 | 2020-11-19 | Ferric trichloride regeneration recycling method for aromatization of triazole compounds |
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| CN112295608B true CN112295608B (en) | 2023-05-19 |
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| CN111303059A (en) * | 2020-04-29 | 2020-06-19 | 江苏苏利精细化工股份有限公司 | Synthesis method of prothioconazole |
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