CN116143697A - Preparation method of tolfenpyrad - Google Patents
Preparation method of tolfenpyrad Download PDFInfo
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- CN116143697A CN116143697A CN202211607130.2A CN202211607130A CN116143697A CN 116143697 A CN116143697 A CN 116143697A CN 202211607130 A CN202211607130 A CN 202211607130A CN 116143697 A CN116143697 A CN 116143697A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention relates to the technical field of tolfenpyrad preparation, and discloses a tolfenpyrad preparation method, which comprises the following steps: s1, mixing and dissolving raw materials: sequentially adding 1-methyl-3-ethyl-4-chloro-5-carboxamide, 1H pyrazole and 4- (4-methylphenoxy) phenyl into a reaction kettle, stirring and dissolving; s2, acylation reaction: acylating to obtain 4-chloro-3-ethyl-1-methyl-5-pyrazole formyl chloride; s3, cooling and post-condensation reaction: adding the mixture into a refrigerator for rapid cooling, carrying out condensation reaction with 4- (4-methylphenoxy) benzylamine prepared by NaBH4 reduction, and then heating to room temperature; s4, drying and separating to obtain the product: the reaction solution is uniformly dried by a dryer and separated by column chromatography to obtain white solid, namely tolfenpyrad, which has the characteristics of high efficiency, broad spectrum, quick acting and the like, can well play a role in contact killing, is widely used for preventing and controlling pests on crops such as vegetables, fruit trees, flowers, tea leaves and the like, has better effect on fungal diseases, and has the effects of killing eggs, inhibiting food, inhibiting spawning and sterilizing.
Description
Technical Field
The invention relates to the technical field of tolfenpyrad preparation, in particular to a preparation method of tolfenpyrad.
Background
Tolfenpyrad is a compound, chemical name: 4-chloro-3-ethyl-1-methyl-N- { [4- (4-methylphenoxy) phenyl ] -methyl } -1H pyrazole-5-carboxamide, CAS:129558-76-5, code: OMI-88, chemical formula: C21H22ClN3O2, relative molecular mass: 383.9, traits: the pure product is white solid powder with the density (25 ℃): 1.18g/cm3, melting point: 87.8-88.2 ℃, the main mechanism of action is to prevent oxidative phosphorylation of insects.
The existing tolfenpyrad preparation method has the following defects: the prepared tolfenpyrad has a low effect, cannot well play a role in contact killing, has a limited application range, is difficult to detect the prepared solution efficiently, and has low quality. For this purpose, a corresponding technical solution needs to be designed to solve.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a preparation method of tolfenpyrad, which solves the technical problems that the prepared tolfenpyrad has lower effect, cannot well play a role in contact killing, has a limited application range, is difficult to detect the prepared solution efficiently, and causes lower quality of the prepared tolfenpyrad.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme: the preparation method of tolfenpyrad comprises the following steps: s1, mixing and dissolving raw materials: sequentially adding 1-methyl-3-ethyl-4-chloro-5-carboxamide, 1H pyrazole and 4- (4-methylphenoxy) phenyl into a reaction kettle, stirring and dissolving; s2, acylation reaction: acylating to obtain 4-chloro-3-ethyl-1-methyl-5-pyrazole formyl chloride; s3, cooling and post-condensation reaction: adding the mixture into a refrigerator for rapid cooling, carrying out condensation reaction with 4- (4-methylphenoxy) benzylamine prepared by NaBH4 reduction, and then heating to room temperature; s4, drying and separating to obtain the product: and (3) uniformly drying the reaction solution by a dryer, and separating by column chromatography to obtain white solid, namely tolfenpyrad.
Preferably, the top of reation kettle has sealed apron through bolted connection, and the manual sealed installation of being convenient for is safe explosion-proof, and driving motor is installed to sealed apron's middle extreme, and driving motor's bottom through connection has the (mixing) shaft, and the lateral part welding of (mixing) shaft distributes has the stirring leaf, but automated control (mixing) shaft and stirring leaf rapid mixing reaction raw materials, and heating device is wrapped up in reation kettle's the outside, and bubble generating device is installed to reation kettle's lower extreme, and solubility detection device is installed to reation kettle's upper end.
Preferably, the inside packing of heating device distributes has the heating wire, heating device's outside is pasted has rubber and plastic heat preservation cotton, heating device's outer end electric connection has heating controller, and heating controller installs in sealed apron's top side, and the manual operation of being convenient for, and the omnidirectional heating is in reation kettle, and it is effectual to keep warm, and rapid heating improves reation kettle's temperature for the dissolution rate is high.
Preferably, the inner side end of the bubble generating device is connected with a bubble connecting pipe in a penetrating manner, the bubble connecting pipe is of a 45-degree oblique structure, through holes are formed in the inner side upper end of the bubble connecting pipe in a direct mode, the air pump is installed in the bubble generating device, automatic control of uniform air outlet through the through holes in the upper end of the bubble connecting pipe is facilitated, and the dissolution effect of bubbles is improved.
Preferably, the inboard end of solubility detection device is connected with the sample connecting pipe, the inside of solubility detection device is equipped with detection mechanism, the outside front end electric connection of solubility detection device has the display screen, but the efficient control is sampled to detection mechanism detection solubility through the sample connecting pipe to improve the quality of preparation formation tolfenpyrad.
Preferably, in step S2, the acylating agent for the acylation reaction includes one or more of carboxylic acid, acid chloride, acid anhydride, carboxylic ester and amide, which are all active acylating agents, and the acylation reaction involving the acylating agent has strong acylating ability, and the acid anhydride is a strong acylating agent, and the acylating reaction is generally performed according to SN1, so that the acylating agent releases acyl positive ions or enhances the electrophilicity of the acyl positive ions.
Preferably, in step S3, the outer part of the refrigerator is circumferentially provided with a condenser pipe, the outer end of the condenser pipe is connected with a compressor, the cooling temperature is kept below 8 ℃, rapid and uniform cooling is facilitated, and the low-temperature environment is easy to keep.
Preferably, in step S4, the inside installation of drying-machine distributes and has the carousel, and the middle extreme of carousel is fixed to be equipped with the pivot pole, and the top of pivot pole is connected with driving motor, and the bottom rotation of pivot pole is connected with the bearing, and the steady support of being convenient for, automatic change slow control carousel is rotatory for the stoving effect is better.
(III) beneficial effects
The preparation method of the tolfenpyrad has the characteristics of high efficiency, broad spectrum, quick acting and the like, can well play a role in contact killing, is widely used for preventing and controlling pests on crops such as vegetables, fruit trees, flowers, tea leaves and the like, has a good effect on fungal diseases, and also has the effects of killing eggs, inhibiting food, inhibiting oviposition and sterilizing.
Drawings
FIG. 1 is a schematic diagram of the steps of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, the embodiment of the invention provides a technical scheme: the preparation method of tolfenpyrad comprises the following steps:
s1, mixing and dissolving raw materials: sequentially adding 1-methyl-3-ethyl-4-chloro-5-carboxamide, 1H pyrazole and 4- (4-methylphenoxy) phenyl into a reaction kettle, stirring and dissolving;
s2, acylation reaction: acylating to obtain 4-chloro-3-ethyl-1-methyl-5-pyrazole formyl chloride;
s3, cooling and post-condensation reaction: adding the mixture into a refrigerator for rapid cooling, carrying out condensation reaction with 4- (4-methylphenoxy) benzylamine prepared by NaBH4 reduction, and then heating to room temperature;
s4, drying and separating to obtain the product: and (3) uniformly drying the reaction solution by a dryer, and separating by column chromatography to obtain white solid, namely tolfenpyrad.
Further improved, the top of reation kettle has sealed apron through bolted connection, and the manual sealed installation of being convenient for is safe explosion-proof, and driving motor is installed to sealed apron's middle extreme, and driving motor's bottom through connection has the (mixing) shaft, and the lateral part welding of (mixing) shaft distributes has the stirring leaf, but automated control (mixing) shaft and stirring leaf rapid mixing reaction raw materials, and heating device is wrapped up in reation kettle's the outside, and bubble generating device is installed to reation kettle's lower extreme, and solubility detection device is installed to reation kettle's upper end.
Further improved, the inside of heating device fills and distributes there is the heating wire, heating device's outside is pasted there is rubber and plastic heat preservation cotton, heating device's outer end electric connection has heating controller, and heating controller installs in sealed apron's top side, and the manual control of being convenient for, the omnidirectional heating is in reation kettle, and it is effectual to keep warm, and rapid heating improves reation kettle's temperature for the dissolution rate is high.
The rubber-plastic heat-insulating cotton is a mixed foaming material formed by mixing, banburying, continuous extrusion, heating foaming, cooling and cutting, and has the advantages of low heat conductivity, fire resistance, moisture resistance, vibration reduction, noise reduction, environmental protection, health, long service life, elegant appearance, attractive appearance, convenient installation and the like, is widely applied, can achieve the effect of reducing cold loss and heat loss, is a cold insulation, heat insulation and condensation prevention gram, has low heat conductivity and keeps stable, and has isolation effect on any heat medium.
Further improved, the inner side end through connection of bubble generating device has the bubble connecting pipe, and the bubble connecting pipe is 45 italic structures, can directly set up the distribution to inside the forward reation kettle in the inboard upper end of bubble connecting pipe, bubble generating device's internally mounted has the air pump, and the through-hole of the automatic control of being convenient for through the bubble connecting pipe upper end evenly gives vent to anger, produces the bubble and improves the dissolution effect.
Further improved, the inboard end of solubility detection device is connected with the sample connecting pipe, the inside of solubility detection device is equipped with detection mechanism, the outside front end electric connection of solubility detection device has the display screen, but efficient control is sampled to detection mechanism detection solubility through the sample connecting pipe to improve the quality of preparation production tolfenpyrad.
The solubility value of the raw materials is mostly equilibrium solubility, and the specific method for measuring is as follows: the method comprises the steps of automatically taking filtrate for analysis through filter membrane filtration, determining the actual concentration of a drug in a solution, and plotting the concentration of the prepared solution to obtain the equilibrium solubility of the drug, wherein the determination of the characteristic solubility is determined according to a miscibility principle diagram, under the condition of determining a plurality of supersaturated solutions with different degrees, continuously oscillating the prepared solution at constant temperature to reach the dissolution equilibrium, centrifuging or filtering, taking out supernatant fluid, properly diluting, determining the concentration of the drug in a saturated solution, and plotting the concentration of the measured drug solution as an ordinate, and the ratio of the mass of the drug to the volume of the solvent as an abscissa, and linearly extrapolating to the position with the ratio of zero to obtain the characteristic solubility of the drug.
Further improved, in step S2, the acylating agent for the acylation reaction includes one or more of carboxylic acid, acyl chloride, anhydride, carboxylic ester and amide, which are all active acylating agents, and the acylating reaction is generally carried out according to a single molecular process, and the anhydride is a strong acylating agent, and the acylating reaction is generally carried out according to an SN1 process, so that acyl positive ions are released or the electrophilicity is enhanced.
The acylation reaction is a reaction in which hydrogen or other groups are substituted with an acyl group in organic chemistry, and a compound which provides an acyl group is called an acylating agent.
Further improved, in step S3, the outer part of the refrigerator is circumferentially provided with condensing pipes, the outer ends of the condensing pipes are connected with compressors, the cooling temperature is kept below 8 ℃, rapid and uniform cooling is facilitated, and the low-temperature environment is easy to keep.
Specifically improved, in step S4, the internally mounted of drying-machine distributes and has the carousel, and the fixed pivot pole that is equipped with in middle of carousel, the top of pivot pole are connected with driving motor, and the bottom rotation of pivot pole is connected with the bearing, and the steady support of being convenient for, automatic change slow control carousel is rotatory for the stoving effect is better.
The dryer is also called a dryer, the dryer is that hot air flow moves downwards from the top and fully contacts with materials, heat energy is directly transferred to the materials by heat conduction, convection and radiation heat transfer quantity fully utilized, so that moisture of the materials is continuously evaporated in a cylinder, a draught device of a feed inlet extracts a large amount of moisture and wet air flow, secondary pollution caused by dust discharge is prevented, and the whole drying process is completed.
Working principle: sequentially adding 1-methyl-3-ethyl-4-chloro-5-carboxamide, 1H pyrazole and 4- (4-methylphenoxy) phenyl into a reaction kettle, stirring for dissolution, acylating to obtain 4-chloro-3-ethyl-1-methyl-5-pyrazole formyl chloride, adding the 4-chloro-3-ethyl-1-methyl-5-pyrazole formyl chloride into a refrigerator for rapid cooling, condensing with 4- (4-methylphenoxy) benzylamine prepared by NaBH4 reduction, heating to room temperature, uniformly drying the reaction solution by a dryer, separating by column chromatography to obtain white solid, namely tolfenpyrad, which has the characteristics of high efficiency, broad spectrum, quick acting and the like, can play a role in contact killing, can be widely used for controlling pests on crops such as vegetables, fruit trees, flowers, tea leaves and the like, has better effects on fungi diseases, and also has the functions of killing eggs, inhibiting food, inhibiting and killing eggs.
The components of the invention are universal standard components or components known by the skilled person, the structure and principle of the components are known by the skilled person through technical manuals or known through routine experiment methods, the problem to be solved by the invention is that the prepared tolfenpyrad has lower effect, cannot well exert the contact killing effect, has a limited application range, is difficult to efficiently detect the prepared solution, and causes lower quality of the prepared tolfenpyrad.
While the fundamental and principal features of the invention and advantages of the invention have been shown and described, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The preparation method of tolfenpyrad is characterized by comprising the following steps:
s1, mixing and dissolving raw materials: sequentially adding 1-methyl-3-ethyl-4-chloro-5-carboxamide, 1H pyrazole and 4- (4-methylphenoxy) phenyl into a reaction kettle, stirring and dissolving;
s2, acylation reaction: acylating to obtain 4-chloro-3-ethyl-1-methyl-5-pyrazole formyl chloride;
s3, cooling and post-condensation reaction: adding the mixture into a refrigerator for rapid cooling, carrying out condensation reaction with 4- (4-methylphenoxy) benzylamine prepared by NaBH4 reduction, and then heating to room temperature;
s4, drying and separating to obtain the product: and (3) uniformly drying the reaction solution by a dryer, and separating by column chromatography to obtain white solid, namely tolfenpyrad.
2. The method for preparing tolfenpyrad according to claim 1, which is characterized in that: the top of reation kettle has sealed apron through bolted connection, and driving motor is installed to sealed apron's middle-end, and driving motor's bottom through connection has the (mixing) shaft, and the lateral part welding of (mixing) shaft distributes has the stirring leaf, and reation kettle's outside parcel has heating device, and air bubble generating device is installed to reation kettle's lower extreme, and solubility detection device is installed to reation kettle's upper end.
3. The method for preparing tolfenpyrad according to claim 2, which is characterized in that: the inside packing of heating device distributes has the heating wire, heating device's outside is pasted has rubber and plastic heat preservation cotton, heating device's outer end electric connection has heating controller, and heating controller installs in the top side of sealing cover plate.
4. The method for preparing tolfenpyrad according to claim 2, which is characterized in that: the inner side end of the bubble generating device is connected with a bubble connecting pipe in a penetrating mode, the bubble connecting pipe is of a 45-degree oblique structure, through holes are formed in the upper end of the inner side of the bubble connecting pipe, and an air pump is installed in the bubble generating device.
5. The method for preparing tolfenpyrad according to claim 2, which is characterized in that: the inside end of solubility detection device is connected with the sample connecting pipe, the inside of solubility detection device is equipped with detection mechanism, the outside front end electric connection of solubility detection device has the display screen.
6. The method for preparing tolfenpyrad according to claim 1, which is characterized in that: in step S2, the acylating agent for the acylation reaction includes one or more of carboxylic acid, acid chloride, acid anhydride, carboxylic acid ester and amide.
7. The method for preparing tolfenpyrad according to claim 1, which is characterized in that: in the step S3, a condensing pipe is distributed around the outside of the refrigerator, the outer end of the condensing pipe is connected with a compressor, and the cooling temperature is kept below 8 ℃.
8. The method for preparing tolfenpyrad according to claim 1, which is characterized in that: in step S4, the inside installation of drying-machine distributes and has the carousel, and the middle of carousel is fixed to be equipped with the pivot pole, and the top of pivot pole is connected with driving motor, and the bottom rotation of pivot pole is connected with the bearing.
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| CN202211607130.2A CN116143697A (en) | 2022-12-14 | 2022-12-14 | Preparation method of tolfenpyrad |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102307A (en) * | 2013-03-04 | 2013-05-15 | 黑龙江大学 | Method for synthesizing tolfenpyrad |
| CN103193708A (en) * | 2013-04-15 | 2013-07-10 | 盐城师范学院 | New method for synthetizing tolfenpyrad |
| CN103351340A (en) * | 2013-07-19 | 2013-10-16 | 浙江工业大学 | Novel preparation method of tolfenpyrad |
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- 2022-12-14 CN CN202211607130.2A patent/CN116143697A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103102307A (en) * | 2013-03-04 | 2013-05-15 | 黑龙江大学 | Method for synthesizing tolfenpyrad |
| CN103193708A (en) * | 2013-04-15 | 2013-07-10 | 盐城师范学院 | New method for synthetizing tolfenpyrad |
| CN103351340A (en) * | 2013-07-19 | 2013-10-16 | 浙江工业大学 | Novel preparation method of tolfenpyrad |
Non-Patent Citations (1)
| Title |
|---|
| 赵东江: "唑虫酰胺的合成工艺研究", 中国硕士学位论文库 * |
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