CN114773280A - Method for continuously synthesizing prothioconazole by utilizing tubular reactor - Google Patents

Method for continuously synthesizing prothioconazole by utilizing tubular reactor Download PDF

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CN114773280A
CN114773280A CN202210455839.9A CN202210455839A CN114773280A CN 114773280 A CN114773280 A CN 114773280A CN 202210455839 A CN202210455839 A CN 202210455839A CN 114773280 A CN114773280 A CN 114773280A
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tubular reactor
reaction
continuously synthesizing
prothioconazole
chloro
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沈运河
熊国银
祝玉超
余正莲
于扩
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Anhui Jiuyi Agriculture Co ltd
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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 continuously synthesizing prothioconazole by utilizing a tubular reactor, belonging to the technical field of synthesis of broad-spectrum triazolethione bactericides. In the reaction, materials enter the pipe reactor through a metering pump, so that the length of the residence time of a system in a pipeline can be controlled through controlling the flow rate, and the reaction time is adjusted; the temperature can be more accurately controlled through heat transfer, and the influence on the reaction effect caused by the fact that the temperature of materials cannot be timely adjusted in the reaction process is avoided; after passing through the pipeline, the materials are directly subjected to crystallization treatment, the whole process greatly shortens the reaction time, improves the atom utilization efficiency, reduces the raw material cost, has less three wastes and is beneficial to continuous production.

Description

Method for continuously synthesizing prothioconazole by using tubular reactor
Technical Field
The invention belongs to the technical field of synthesis of broad-spectrum triazolethione bactericides, and particularly relates to a method for continuously synthesizing prothioconazole by utilizing a tubular reactor.
Background
Prothioconazole is a broad spectrum triazolethione fungicide, which is chemically known as (RS) -2- [2- (1-chlorocyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl ] -2, 4-dihydro-1, 2, 4-triazole-3-thione, a broad spectrum fungicide manufactured and developed by the bayer company and which possesses a unique triazolethione structure and acts by inhibiting the demethylation at the 14-position of the sterol precursor, lanosterol or 2, 4-methylenedihydrolanosterol, in fungi, i.e. a demethylation inhibitor (DMIS). The prothioconazole not only has the intrinsic absorption activity, but also has excellent activity of protection, treatment and eradication, and the yield increase effect is obvious. Compared with triazole bactericides, prothioconazole has broader bactericidal activity. The prothioconazole has low toxicity, no teratogenicity, mutagenicity and no toxicity to embryos and is safe to human and environment. The bactericidal composition is mainly used for preventing and treating a plurality of diseases of crops such as cereals, wheat and beans, and has a good prevention effect on almost all diseases of wheat, such as powdery mildew, banded sclerotial blight, leaf spot, rust disease, sclerotinia, net spot, leaf streak and the like.
At present, few patent documents are available for domestic synthetic research on prothioconazole technical products. The existing industrial production process basically uses alpha-acetyl-gamma-butyrolactone as a starting material, and 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane is generated through a series of reactions and then is oxidized to generate the required prothioconazole. In the oxidation reaction, the reaction time is long and the solid waste is large. Patents CN108689952A and CN109232452A use ferric trichloride to directly oxidize 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3-1, 2, 4-triazolidine-5-thione-1-yl) -propane or perform catalysis by a phase transfer catalyst, so that the yield of prothioconazole can reach more than 95%. However, the greatest disadvantage of ferric chloride oxidation is the production of a large amount of solid waste, typically more than 2 times the product quality. Patents CN109912522A, CN111303059A and CN111527071A use oxidizing agents such as nitric acid, hydrogen peroxide and sodium nitrite, respectively, to oxidize, which can also achieve good yield, but do not substantially improve the problem of three wastes.
Based on the above, a method for continuously synthesizing prothioconazole by using a tubular reactor is provided.
Disclosure of Invention
The present invention has been made to solve the above problems and an object of the present invention is to provide a method for continuously synthesizing prothioconazole using a tubular reactor.
The invention achieves the above purpose through the following technical scheme:
the invention provides a method for continuously synthesizing prothioconazole by utilizing a tubular reactor, which comprises the following steps of:
(1) taking a tubular reactor as a reaction vessel, dissolving 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane in a solvent, and simultaneously adding an oxidant into the solvent to be uniformly mixed;
(2) and (2) introducing the uniformly mixed material and oxygen in the step (1) into the tubular reactor at the same time, reacting, and after the reaction process is finished, purifying and crystallizing the reaction liquid discharged from the discharge port of the tubular reactor to obtain the high-purity prothioconazole.
As a further optimization scheme of the invention, the oxidant in the step (1) is one of ferric chloride, cuprous chloride, cupric chloride, cuprous bromide, cuprous iodide and lead acetate.
As a further optimization scheme of the invention, the solvent in the step (1) is one of methanol, toluene, dichloroethane and water.
As a further optimized scheme of the invention, the molar ratio of the 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane, the oxidant and the oxygen is 1: 0.01: 1.
as a further optimization scheme of the invention, the temperature of the step (1) is 30-80 ℃.
As a further optimization scheme of the invention, the pressure of the oxygen in the step (2) is 0.4MPa-1.06 MPa.
As a further optimization scheme of the invention, the flow rate of the blending material introduced into the tubular reactor is 0.2-1.0L/min, and the flow rate of the oxygen introduced into the tubular reactor is 0.1-1.0L/min.
As a further optimization scheme of the invention, the reaction temperature of the mixture obtained in the step (1) and oxygen after being introduced into the tubular reactor is 10-100 ℃.
As a further optimization scheme of the invention, the reaction time of the mixture obtained in the step (1) and oxygen after being introduced into the tubular reactor is 1-20 min.
The invention has the beneficial effects that:
the invention achieves the purpose of preparing the propylsulfide by leading 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thion-1-yl) -propane to pass through a tubular reactor in a corresponding solvent in the presence of oxygen and other oxidants. In the reaction, materials enter the pipe reactor through a metering pump, so that the length of the residence time of a system in a pipeline can be controlled through controlling the flow rate, and the reaction time is adjusted; the temperature can be more accurately controlled through heat transfer, and the influence on the reaction effect caused by the fact that the temperature of materials cannot be timely adjusted in the reaction process is avoided; after passing through the pipeline, the materials are directly subjected to crystallization treatment, the whole process greatly shortens the reaction time, improves the atom utilization efficiency, reduces the raw material cost, has less three wastes and is beneficial to continuous production.
Drawings
FIG. 1 is a formula for the continuous synthesis of prothioconazole using a tubular reactor in accordance with the present invention.
Detailed Description
The present application is described in further detail below, and it should be noted that the following detailed description is provided for illustrative purposes only, and should not be construed as limiting the scope of the present application, and that those skilled in the art can make insubstantial modifications and adaptations to the present application based on the above disclosure.
Example 1
500g of raw material 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane (1.45mol) is dissolved in 800g of methanol, 19.6g of ferric trichloride hexahydrate (0.072mol) is added, the mixture is stirred and dissolved clearly, the mixture is injected into a tubular reactor by a metering pump at 0.5L/min, air is simultaneously introduced into an air vent at a flow rate of 0.5L/min, the temperature in the pipeline is regulated and controlled to be 50 ℃, the timing is started when the raw material enters a pipeline port, after 68s, the material liquid is all pumped out, after the detection reaction is finished, the material liquid is directly cooled, crystallized and filtered, and 493.2g (content: 98.35%) of a product is obtained, and the yield is 97%.
Example 2
Dissolving 500g of raw material 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane (1.45mol) in 800g of methanol, adding 196g of ferric chloride hexahydrate (0.72mol), stirring and clearing, pumping into a tubular reactor at 0.5L/min by using a metering pump, simultaneously introducing air into an air vent at a flow rate of 0.5L/min, regulating and controlling the temperature in the pipeline to be 45 ℃, starting timing when the raw material liquid enters a pipeline port, completely pumping out the material liquid in the pipeline after 65s, after the detection reaction is finished, directly cooling, crystallizing and filtering to obtain 497.2g (content: 98.1%) of a product, wherein the yield is 97.5%.
Example 3
500g of raw material 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane (1.45mol) is dissolved in 800g of toluene, 19.6g of ferric chloride hexahydrate (0.072mol) is added, the mixture is stirred and dissolved clearly, the mixture is pumped into a tubular reactor by a metering pump at 0.2L/min, air is simultaneously introduced into an air vent at a flow rate of 0.2L/min, the temperature in the pipeline is regulated and controlled at 50 ℃, the timing is started when the raw material enters a pipeline port, all the material in the pipeline is pumped out after 165s, and after the detection reaction is finished, the material liquid is directly cooled, crystallized and filtered, so that 476.7.2g (content: 97.2%) of a product is obtained, and the yield is 93%.
Example 4
500g of raw material 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane (1.45mol) is dissolved in 800g of methanol, 7.18g of cuprous chloride (0.072mol) is added to be stirred and dissolved, the solution is pumped into a tubular reactor by a metering pump at 0.2L/min, air is simultaneously introduced into an air vent at a flow rate of 0.2L/min, the temperature in the pipeline is regulated and controlled to be 50 ℃, timing is started when the raw material enters a pipeline port, all feed liquid in the pipeline is pumped out after 165s, after the detection reaction is finished, the feed liquid is directly cooled, crystallized and filtered, and 470.2g (content: 97.0%) of a product is obtained, and the yield is 91.2%.
Example 5
500g of raw material 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane (1.45mol) is dissolved in 800g of methanol, 19.6g of ferric trichloride hexahydrate (0.072mol) is added, the mixture is stirred and dissolved clearly, the mixture is injected into a tubular reactor by a metering pump at 0.5L/min, oxygen is simultaneously introduced into an air vent at a flow rate of 0.5L/min, the temperature in the pipeline is regulated and controlled to be 50 ℃, timing is started when the raw material enters a pipeline port, the material liquid is completely pumped out after 66s, after the detection reaction is finished, the material liquid is directly cooled, crystallized and filtered, and 490g (content: 99%) of a product is obtained, and the yield is 98%.
Example 6
500g of raw material 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane (1.45mol) is dissolved in 800g of methanol, 19.6g of ferric trichloride hexahydrate (0.072mol) is added, the mixture is stirred and dissolved clearly, the mixture is injected into a tubular reactor by a metering pump at 0.2L/min, oxygen is simultaneously introduced into an air vent at a flow rate of 0.2L/min, the temperature in the pipeline is regulated and controlled to be 50 ℃, timing is started when the raw material enters a pipeline port, the material liquid is completely pumped out after 30s, after the detection reaction is finished, the material liquid is directly cooled, crystallized and filtered, 485g of the product (content: 99%) is obtained, and the yield is 97%.
The filtrate was subjected to distillation under reduced pressure at 60 ℃ and 0.03MPa to give 790g of methanol (containing 0.1% water) and 25g of a residue. The main component of the residual liquid is ferric chloride hexahydrate, the residual liquid is continuously used for catalytic oxidation reaction, and the TON value of the catalyst can reach more than 500. The whole reaction almost has no three wastes.
Example 7
500g of raw material 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane (1.45mol) is dissolved in 800g of methanol, 588g of ferric trichloride hexahydrate (2.16mol) is added, then the temperature is raised to 40 ℃ and the stirring is carried out for 1h, the high performance liquid chromatography detects that the raw material is completely reacted, the feed liquid is directly cooled, crystallized and filtered, 479g of product (content: 98%) is obtained, and the yield is 95%.
The filtrate was subjected to distillation under reduced pressure at 60 ℃ and 0.03MPa to give 760g of methanol (containing 0.2% water) and 610g of a residue. The main components of the raffinate are ferrous chloride, basic ferric chloride and other mixtures. The iron in the residual liquid can be treated as three wastes under the condition of no treatment, and can not be recycled.
The types and amounts of the oxidizing agents and the reaction conditions of examples 1 to 7 are summarized in the following table:
Figure BDA0003620422660000061
Figure BDA0003620422660000071
as can be seen from examples 1 and 2, in example 1, 0.072mol of ferric chloride hexahydrate is used as an oxidizing agent, and in example 2, 0.72mol of ferric chloride hexahydrate is used as an oxidizing agent, the changes of reaction time, reaction temperature and yield are not obvious;
as can be seen from examples 1 and 3, in example 1, the mixture of the raw material and the oxidant and air are introduced at a flow rate of 0.5L/min, and in example 3, the mixture of the raw material and the oxidant and air are introduced at a flow rate of 0.2L/min, the reaction time is increased from 68s to 165s, and the yield is reduced;
as can be seen from examples 3 and 4, in example 4, 0.072mol of cuprous chloride is used as the oxidant, and the mixture of the raw material and the oxidant and air are introduced at a flow rate of 0.2L/min, so that the reaction time is unchanged, and the yield is further reduced;
as can be seen from examples 1 and 5, examples 1 and 5 both used 0.072mol of ferric chloride hexahydrate as the oxidant, but except that example 5 used a flow rate of 0.5L/min to introduce oxygen, rather than air, to beneficially but not significantly affect reaction time and yield;
as can be seen from examples 6 and 5, the difference between example 6 and example 5 is that in example 6, the mixed mixture of the raw material and the oxidant and oxygen are introduced at a flow rate of 0.2L/min, so that the reaction time is greatly shortened, the reaction time is reduced from 66s to 30s, the yield is deficient compared with example 5, but the reaction time is shortened compared with example 1;
as can be seen from example 7, increasing the amount of the oxidizing agent, no oxygen was introduced during the reaction, and the reaction was not carried out in the tubular reactor, the reaction time being much longer than in examples 1 to 6.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention.

Claims (9)

1. A method for continuously synthesizing prothioconazole by using a tubular reactor, which is characterized by comprising the following steps of:
(1) taking a tubular reactor as a reaction vessel, dissolving 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane in a solvent, and simultaneously adding an oxidant into the solvent to be uniformly mixed;
(2) and (2) introducing the uniformly mixed material and oxygen in the step (1) into the tubular reactor at the same time, reacting, and after the reaction process is finished, purifying and crystallizing the reaction liquid discharged from the discharge port of the tubular reactor to obtain the high-purity prothioconazole.
2. The method for continuously synthesizing prothioconazole according to claim 1, wherein the oxidant in step (1) is one of ferric chloride, cuprous chloride, cupric chloride, cuprous bromide, cuprous iodide and lead acetate.
3. The method for continuously synthesizing prothioconazole according to claim 1, wherein the solvent in step (1) is one of methanol, toluene, dichloroethane and water.
4. The method for continuously synthesizing prothioconazole according to claim 1, wherein the molar ratio of 2- (1-chloro-cyclopropyl-1-yl) -1- (2-chloro-phenyl) -2-hydroxy-3- (1,2, 4-triazolidine-5-thione-1-yl) -propane, oxidant and oxygen is 1: 0.01: 1.
5. the method for continuously synthesizing prothioconazole using tubular reactor according to claim 1, wherein the temperature of step (1) is 30-80 ℃.
6. The method for continuously synthesizing prothioconazole using a tubular reactor according to claim 1, wherein the pressure of the medium oxygen in step (2) is 0.4MPa to 1.06 MPa.
7. The method for continuously synthesizing prothioconazole according to claim 1, wherein the flow rate of the blending substance into the tubular reactor is 0.2 to 1.0L/min, and the flow rate of the oxygen into the tubular reactor is 0.1 to 1.0L/min.
8. The method for continuously synthesizing prothioconazole according to claim 1, wherein the reaction temperature of the mixture obtained in the step (1) and oxygen after being introduced into the tubular reactor is between 10 and 100 ℃.
9. The method for continuously synthesizing prothioconazole according to claim 1, wherein the reaction time of the mixture obtained in the step (1) and oxygen after the mixture are introduced into the tubular reactor is 1-20 min.
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