CN112295608A - Recycling method for regenerating ferric trichloride for aromatizing triazole compounds - Google Patents
Recycling method for regenerating ferric trichloride for aromatizing 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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- 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
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Abstract
The invention relates to a method for regenerating and recycling ferric trichloride for aromatizing triazole compounds, which belongs to the technical field of industrial production of pesticides. The invention uses chlorine gas to regenerate after the ferric trichloride is used, can be repeatedly applied for a plurality of times without influencing the reaction effect, avoids the environmental pollution, saves the production raw materials and reduces the production cost.
Description
Technical Field
The invention relates to a method for recycling ferric trichloride for aromatizing triazole compounds, belonging to the technical field of industrial production of pesticides.
Background
Triazole compounds are important functional groups of human antibiotics and agricultural bactericides which are most widely applied globally at present. In agricultural production, the triazole compound is used as an agricultural bactericide, can improve the yield of crops and control plant diseases of the crops caused by fungi. In recent years, in landscaping, vegetable crops, field crops, grain crops and the like, the yield is reduced and the selling price is increased due to the fact that the disease control is not timely performed to different degrees every year. Therefore, the intensive research on the triazole compounds, the improvement on the synthesis process of the bactericide, the improvement on the yield of the triazole bactericide and the research and development of a more environment-friendly and safer production process become more significant.
Ferric trichloride is used as a mild and suitable oxidant in the preparation process of triazole compound bactericides, and the direct discharge of a byproduct, namely ferrous chloride, can cause serious environmental pollution. In patent WO0146158A1, ferric chloride acidified by hydrochloric acid is reported as an oxidation reagent for aromatizing triazole compounds, and after treatment, reaction liquid is poured into ice water and is extracted by ethyl acetate, so that a large amount of acidic ferrous chloride aqueous solution is generated, and the treatment is difficult. Patent CN108752283A reports that ferric chloride is used as an oxidant to react for 6 hours in an oxygen atmosphere to aromatize triazole group, but does not report the problem of recycling generated ferrous chloride.
Patent CN111303059A reports that a catalytic amount of ferric chloride is added into a reaction solution, ferric chloride oxidizes triazole groups to generate ferrous chloride, hydrogen peroxide is added dropwise into the reaction solution, and ferrous chloride is oxidized by hydrogen peroxide and then continuously reacts with triazole compounds. Patent CN106986838A reports that hydrogen peroxide is used as an oxidant instead of ferric trichloride for reaction. In the method, the generation of a large amount of ferric trichloride wastewater is avoided by reducing the consumption of ferric trichloride or selecting a substitute oxidant, but hydrogen peroxide has strong oxidizability, and the generation of desulfurization impurities is avoided by strictly controlling the reaction temperature and the addition of hydrogen peroxide.
In addition, the obtained ferrous chloride aqueous solution is oxidized by adopting chlorine or oxygen and then is continuously applied, and the oxidation efficiency is sharply reduced after repeated application. In order to solve the problems, the invention provides a method for regenerating and recycling ferric trichloride, which is economical and environment-friendly and can maintain the effect of repeatedly recycling and oxidizing.
Disclosure of Invention
The invention aims to provide a method for regenerating and recycling ferric trichloride for aromatizing triazole compounds, which is used for recycling ferrous chloride serving as a byproduct generated after the aromatization of the triazole compounds.
In order to achieve the purpose, the invention adopts the technical scheme that:
a ferric trichloride regeneration recycling method for triazole compound aromatizing comprises the steps of firstly oxidizing a compound I containing triazolyl into a compound II containing unsaturated triazolyl by using a ferric trichloride aqueous solution, simultaneously separating to obtain a ferrous chloride aqueous solution, adding ferric oxide into the obtained ferrous chloride aqueous solution, then introducing chlorine gas to oxidize to obtain ferric trichloride, reusing the obtained ferric trichloride for reaction, recycling and oxidizing the ferric trichloride for multiple times, wherein the specific reaction formula is as follows:
wherein, R is one or a combination of 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 a compound I into a solvent under the stirring state, heating to 30-80 ℃, slowly dripping 10-40% of ferric trichloride aqueous solution, and preserving heat until the content of the compound I is less than 0.1% after dripping is finished, so as to obtain a qualified reaction product; cooling, filtering to obtain a compound II, and separating to obtain a ferrous chloride aqueous solution;
B. and D, 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 which is used in the step A again.
The technical scheme of the invention is further improved as follows: and B, judging whether the ferrous iron ions in the ferrous chloride are completely converted into ferric iron ions or not, and detecting by a spectrophotometry.
The technical scheme of the invention is further improved as follows: and B, determining the amount of chlorine gas in the step B to be 0.5-0.6 of the mole number of the ferrous chloride by weighing the added weight of the reaction liquid, blowing nitrogen gas into the excess chlorine gas to take out the excess chlorine gas, and absorbing the tail gas by using sufficient 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 the ferric oxide in the step B is 0.05 to 0.15 of the mole number of the ferrous chloride.
The technical scheme of the invention is further improved as follows: the solvent in the step A is toluene or xylene.
Due to the adoption of the technical scheme, the invention has the following technical effects:
according to the invention, ferric trichloride which is a milder oxidant is selected to aromatize triazole compounds, so that the generation of desulfurization impurities due to strong oxidizability is avoided, the separated ferrous chloride solution is oxidized and regenerated by chlorine, other heteroatoms are not introduced, the regenerated ferric trichloride solution can be repeatedly applied repeatedly, ferrous chloride wastewater is not generated, the ferrous chloride wastewater is not discharged into the environment, and the environmental pollution is avoided.
The application times of the ferric trichloride do not influence the oxidation effect of the ferric trichloride, and the yield and the content of the product obtained by oxidation are not influenced by the application times, so that the ferric trichloride can be regenerated by chlorine after being used, can be repeatedly applied, avoids the environmental pollution and also reduces the production cost.
The regeneration reagent chlorine used in the invention is a common industrial raw material, is cheap and easy to obtain, has low cost, and is suitable for large-scale industrial production; chlorine and ferric oxide are used, other heteroatoms are not introduced, and production is not influenced.
Detailed Description
The present invention will be further described in detail with reference to specific examples below:
a method for recycling ferric trichloride for aromatizing triazole compounds comprises the following steps:
A. adding a compound I into a solvent toluene or xylene under a stirring state, heating to 30-80 ℃, slowly dripping 10-40% of ferric trichloride aqueous solution, and preserving heat until the content of the compound I is less than 0.1% after dripping is finished, so as to obtain a qualified reaction product; cooling, filtering to obtain a compound II, and separating to obtain a ferrous chloride aqueous solution;
B. and B, adding ferric oxide with the mole number of 0.05-0.15 of ferrous chloride 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 0.5-0.6 of ferrous chloride, determining the introduction amount of the chlorine by weighing the added weight of the reaction solution, blowing nitrogen into the excess chlorine to take out the excess chlorine, and absorbing the tail gas by using sufficient alkali liquor. And C, obtaining an aqueous solution of ferric trichloride through reaction, detecting and judging whether ferrous ions in the ferrous chloride are completely converted into ferric ions through a spectrophotometry, and reusing the obtained aqueous solution of ferric trichloride 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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, 195g of 30% ferric trichloride aqueous solution is added dropwise when the temperature is increased to 30 ℃, the temperature is kept for 6h after the dripping, the raw material is monitored by liquid chromatography tracking to be less than 0.5%, the temperature is reduced to 0-5 ℃, the pressure is reduced and the filtration is carried out, the product is washed twice by 15g of water and dried to obtain 47.88g of white solid, 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 solution2+Content 10.60% Fe3+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 chlorine gas is introduced to increase the weight by about 11.2g, analyzing and detecting to be qualified (no ferrous ion), keeping the temperature and stirring for 1h, blowing nitrogen gas to bring out redundant chlorine gas, introducing the gas into sufficient sodium hydroxide solution to absorb, and performing a mechanical experiment on the obtained ferric trichloride.
EXAMPLE 2 Recycling of iron trichloride
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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, the temperature is increased to 50 ℃, the ferric trichloride aqueous solution oxidized in the example 1 is dripped into the bottle, the temperature is kept for 3h after dripping, the liquid chromatography tracking monitoring raw materials are less than 0.1%, the temperature is reduced to 0-5 ℃, the vacuum filtration is carried out, the product is washed twice by 15g of water and is dried to obtain 48.1g of white solid with the content of 98.1%, and the yield of 95.2%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution2+Content 10.01%, Fe3+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 introducing chlorine when the weight of chlorine is increased by about 11.8g, analyzing and detecting to be qualified (no ferrous ion), keeping the temperature and stirring for 1h, blowing nitrogen to bring out redundant chlorine, introducing the gas into sufficient sodium hydroxide solution to absorb, and performing a mechanical experiment on the obtained ferric trichloride.
EXAMPLE 3 Recycling of iron trichloride for two 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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, the temperature is increased to 80 ℃, the ferric trichloride aqueous solution oxidized in the example 2 is dripped, the temperature is kept for 1h after dripping, the liquid chromatography tracking monitoring raw material is less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced and suction filtration is carried out, the product is washed twice by 15g of water, and the white solid is obtained by drying 48.3g, the content is 98.0%, and the yield is 95.3%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution2+9.98% of Fe3+The content is 0.98 percent. Transferring the recovered ferric trichloride solution into a 500ml four-mouth bottle, heating to 10-60 ℃, adding 8.5g of ferric oxide, then stopping ventilation when chlorine gas is introduced to increase weight by about 11.5g, analyzing and detecting to be qualified (no ferrous ion), stirring for 1h at the constant temperature, blowing nitrogen gas to bring out redundant chlorine gas, introducing the gas into sufficient sodium hydroxide solution to absorb, and carrying out a mechanical application experiment on the obtained ferric trichloride.
EXAMPLE 4 Recycling of iron 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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, the temperature is increased to 40 ℃, the ferric trichloride aqueous solution oxidized in the embodiment 3 is dripped, the temperature is kept for 4h after dripping, the liquid chromatography tracking monitoring raw material is less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced and the filtration is carried out, the product is washed twice by 15g of water and is dried to obtain 48.2g of white solid with the content of 98.1%, and the yield of 95.2%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution2+9.95% of Fe3+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, then stopping ventilation when chlorine gas is introduced to increase weight by about 11.2g, analyzing and detecting to be qualified (no ferrous ion), stirring for 1h at the constant temperature, blowing nitrogen gas to bring out redundant chlorine gas, introducing the gas into sufficient sodium hydroxide solution to absorb, and carrying out a mechanical application experiment on the obtained ferric trichloride.
Example 5 ferric trichloride four uses of ferric trichloride after removal of excess hydrogen chloride and regeneration
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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, the temperature is increased to 65 ℃, the ferric trichloride aqueous solution obtained in the example 4 is dripped, the temperature is kept for 2h after the dripping, the liquid chromatography tracking monitoring raw material is less than 0.1%, the temperature is reduced to 0-5 ℃, the pressure is reduced and the filtration is carried out, the product is washed twice by 15g of water and is dried to obtain 48.3g of white solid with the content of 98.2%, and the yield of 95.4%.
The examples show that the application times do 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 times, so that the ferric trichloride can be regenerated by chlorine after being oxidized, and can be repeatedly applied, thereby avoiding the 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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, 195g of 30% ferric trichloride aqueous solution is dripped when the temperature is increased to 35 ℃, the temperature is kept for 5.5 hours after dripping, the raw material is monitored by liquid chromatography tracking and is reduced to 0 to 5 ℃, the temperature is reduced to 0 to 5 ℃, the pressure is reduced and suction filtration is carried out, the product is washed twice by 15g of water, and the white solid is obtained by drying, the content is 47.65g, and the yield is 95.3%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution2+Content 10.51% Fe3+The content is 0.37%. Transferring the recovered solution into 500ml four-mouth bottle, controlling temperature to 10-60 deg.C, adding 2.9g ferric oxide, introducing chlorine gas to increase weight by 11.2g, stopping introducing gas, analyzing and detecting to be qualified (no ferrous ion), stirring for 1h, blowing nitrogen gas to carry out excessive chlorine gas, introducing gas into sufficient sodium hydroxide solution to performAbsorbing to obtain ferric trichloride which can be used in indiscriminate application experiment.
Comparative example 2 ferric trichloride regeneration was used once without ferric oxide addition
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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, the temperature is raised to 60 ℃, the ferric trichloride aqueous solution oxidized in the example 1 is dripped, the temperature is kept for 2h after dripping, the liquid chromatography tracking monitoring raw material is less than 0.1%, the temperature is lowered to 0-5 ℃, the pressure is reduced and suction filtration is carried out, the product is washed twice by 15g of water and dried to obtain 46.1g of white solid with the content of 96.2%, and the yield of 92.2%.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution2+Content 10.01%, Fe3+The content is 1.26%. Transferring the recovered solution into a 500ml four-mouth bottle, heating to 10-60 ℃, introducing chlorine gas to increase weight by about 11.8g, stopping introducing the chlorine gas, analyzing and detecting to be qualified (no ferrous ions), keeping the temperature and stirring for 1h, blowing nitrogen gas to bring out redundant chlorine gas, introducing the gas into sufficient sodium hydroxide solution to absorb, and carrying out a mechanical application experiment on the obtained ferric trichloride.
Comparative example 3 ferric trichloride regeneration for secondary use without adding 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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, the temperature is raised to 45 ℃, the ferric trichloride aqueous solution oxidized in the example 2 is dripped in, the temperature is kept for 3.5h after the dripping, the liquid chromatogram tracks and monitors that the raw material is less than 0.1 percent, the temperature is lowered to 0-5 ℃, the pressure is reduced and the filtration is carried out, the product is washed twice by 15g of water and is dried to obtain 43.3g of white solid, the content is 94.3 percent, and the yield is 86.6 percent.
Separating to obtain ferrous chloride aqueous solution, and detecting Fe in the ferrous chloride aqueous solution2+Content 9.98％，Fe3+The content is 0.98 percent. Transferring the recovered ferric trichloride solution into a 500ml four-mouth bottle, heating to 10-60 ℃, then stopping ventilation when chlorine gas is introduced to increase weight by about 11.5g, analyzing and detecting to be qualified (no ferrous ion), stirring for 1h while keeping the temperature, blowing nitrogen gas to bring out redundant chlorine gas, introducing the gas into sufficient sodium hydroxide solution to absorb, and carrying out a mechanical application experiment on the obtained ferric trichloride.
Comparative example 4 ferric trichloride regeneration was used for three times without adding 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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) phenyl-2-hydroxy-3- [1,2,4- (2, 4-dihydro) triazolyl-5-thione-1-yl ] -propane is added under the stirring state, the temperature is raised to 50 ℃, the ferric trichloride aqueous solution oxidized in the comparative example 3 is dripped, the temperature is kept for 3h after dripping, the liquid chromatogram tracks and monitors that the content of the raw material is less than 0.1%, the temperature is lowered to 0-5 ℃, the pressure is reduced and the filtration is carried out, the product is washed twice by 15g of water and is dried to obtain 40.6g of white solid with the content of 91.1%, and the yield of 81.2%.
Comparative example 5
Synthesis of 2- (1-chlorocyclopropyl) -1- (2-chlorophenyl) -2-hydroxy-3- (1,2, 4-triazolyl-5-thione-1-yl) -propane
In 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 and 0.7g of ferric chloride were added under stirring, followed by slowly dropping 7.36g of hydrogen peroxide. The reaction was stirred at 20 ℃ for 2 h. After the reaction is finished, 9.39g of sodium sulfite is added into the reaction solution to reduce excessive hydrogen peroxide, the reaction solution is stirred for 1 hour at room temperature, and starch potassium iodide test paper is used for detecting, and the test paper does not turn blue, so that the hydrogen peroxide is completely reduced. The reaction was washed with 60ml of water, the organic phases were combined and dried over sodium sulfate and concentrated. 50.8g of crude product with a content of 89% are obtained. The crude product obtained was recrystallized from toluene to give 43.3g of a white solid, content 95.2% and yield 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-mouth bottle, 50g of 2- (1-chlorocyclopropyl) -1- (2-chlorphenyl) -2-hydroxy-3- (1,2, 4-triazolyl-5-thione-1-yl) -propane is added under the stirring state, 6.58g of hydrogen peroxide is slowly dripped, the mixture is stirred for 3 hours at the temperature of 20 ℃, 3.6g of sodium sulfite is added into the reaction solution after the reaction is finished, the excessive hydrogen peroxide is reduced, the mixture is stirred for 1 hour at the room temperature, and the potassium iodide starch test paper is used for detecting, and the test paper does not turn blue, which indicates that the hydrogen peroxide is completely reduced. The reaction system was washed with 40ml of water, separated and the organic phase concentrated to give 49.1g of crude product, 86% content. The crude product obtained was recrystallized from toluene to give 40.1g of a white solid, content 93.0% and yield 75.0%.
Product quality comparison table:
as shown in the table, (1) the application times of the method do not influence the oxidation of ferric trichloride, and the yield and the content of the product obtained by oxidation are not influenced by the application times; (2) when ferric oxide is not added in the oxidation process of the ferrous chloride aqueous solution, the indiscriminate ferric chloride oxidation effect is obviously reduced; (3) the content and yield of the product obtained by the reaction of the hydrogen peroxide serving as an oxidant or the ferric trichloride oxidized by the hydrogen peroxide are reduced to different degrees.
Claims (7)
1. A method for regenerating and recycling ferric trichloride for aromatizing triazole compounds is characterized by comprising the following steps: firstly, oxidizing a compound I containing triazolyl into a compound II containing unsaturated triazolyl by using an iron trichloride aqueous solution, simultaneously separating to obtain an iron dichloride aqueous solution, adding ferric oxide into the obtained iron dichloride aqueous solution, then introducing chlorine gas to oxidize to obtain ferric trichloride, reusing the obtained ferric trichloride for reaction, recycling and oxidizing the ferric trichloride for multiple times, wherein the specific reaction formula is as follows:
wherein, R is one or a combination of more of hydrogen, alkyl, alkoxy, heterocyclic group, aryl, heteroaryl, halogenated C6-C10 aryl or C1-C9 heteroaryl;
x is oxygen or sulfur.
2. The method for recycling and reusing ferric trichloride for aromatizing triazole compounds according to claim 1, which comprises the following steps:
A. adding a compound I into a solvent under the stirring state, heating to 30-80 ℃, slowly dripping 10-40% of ferric trichloride aqueous solution, and preserving heat until the content of the compound I is less than 0.1% after dripping is finished, so as to obtain a qualified reaction product; cooling, filtering to obtain a compound II, and separating to obtain a ferrous chloride aqueous solution;
B. and D, 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 which is used in the step A again.
3. The method for recycling and reusing ferric trichloride used for aromatizing triazole compounds according to claim 2, wherein: and B, judging whether the ferrous iron ions in the ferrous chloride are completely converted into ferric iron ions or not, and detecting by a spectrophotometry.
4. The method for recycling and reusing ferric trichloride used for aromatizing triazole compounds according to claim 2, wherein: and B, determining the amount of chlorine gas in the step B to be 0.5-0.6 of the mole number of the ferrous chloride by weighing the added weight of the reaction liquid, blowing nitrogen gas into the excess chlorine gas to take out the excess chlorine gas, and absorbing the tail gas by using sufficient alkali liquor.
5. The method for recycling and reusing ferric trichloride used for aromatizing triazole compounds according to claim 2, wherein: the temperature of the ferrous chloride aqueous solution in the step B is 10-60 ℃.
6. The method for recycling and reusing ferric trichloride used for aromatizing triazole compounds according to claim 1, wherein: the dosage of the ferric oxide in the step B is 0.05 to 0.15 of the mole number of the ferrous chloride.
7. The method for recycling and reusing ferric trichloride used for aromatizing triazole compounds according to claim 2, wherein: the solvent in the step A is toluene or xylene.
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| CN111170842A (en) * | 2020-01-14 | 2020-05-19 | 中化健康产业发展有限公司 | Preparation method of aloe-emodin |
| CN113788778A (en) * | 2021-10-09 | 2021-12-14 | 河北威远生物化工有限公司 | Aromatizing method of nitrogen-containing heterocyclic compound |
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| FI906351A0 (en) * | 1990-12-21 | 1990-12-21 | Neste Oy | FOER FARING FOR FRAMSTAELLNING AV ETT MATERIAL. |
| 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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| FI906351A0 (en) * | 1990-12-21 | 1990-12-21 | Neste Oy | FOER FARING FOR FRAMSTAELLNING AV ETT MATERIAL. |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111170842A (en) * | 2020-01-14 | 2020-05-19 | 中化健康产业发展有限公司 | Preparation method of aloe-emodin |
| CN113788778A (en) * | 2021-10-09 | 2021-12-14 | 河北威远生物化工有限公司 | Aromatizing method of nitrogen-containing heterocyclic compound |
| CN113788778B (en) * | 2021-10-09 | 2023-11-17 | 河北威远生物化工有限公司 | Aromatization method of nitrogen-containing heterocyclic compound |
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