CN113354632A - Preparation method and system of thiacloprid - Google Patents
Preparation method and system of thiacloprid Download PDFInfo
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Abstract
A preparation method of thiacloprid comprises the following steps: mixing 2-cyanoimine-1, 3-thiazolidine, a reaction solvent, an iridium complex and an organic base to obtain a first material, and taking 2-chloro-5-chloromethylpyridine as a second material; mixing the first material and the second material, and then carrying out condensation reaction to generate thiacloprid; and (3) carrying out acid adjustment, cooling, crystallization and suction filtration on thiacloprid to obtain a thiacloprid finished product. The invention also provides a thiacloprid preparation system, the reaction conditions for preparing thiacloprid are mild, the reaction time is short, the steps are simple, no waste salt is generated, the environment is protected, the method is suitable for industrial production, and the yield of the final product is over 90 percent and the content is over 95 percent.
Description
Technical Field
The invention relates to preparation of fine chemical products, in particular to a method and a system for preparing thiacloprid.
Background
Thiacloprid is a pesticide for preventing and controlling pests of sucking mouth parts and chewing mouth parts, has the characteristics of high activity, high safety, wide activity spectrum and the like, and belongs to neonicotinoid pesticides. It has high safety to human and livestock, and the medicament has no odor or irritation; the steam pressure of the effective components is low, the air cannot be polluted, the half-life period is short, the residue can be quickly decomposed after entering the soil and the river, and the influence on the environment is small; the pesticide has low toxicity to aquatic organisms, basically has no influence on the aquatic organisms under normal conditions, has extremely strong contact and toxic killing effects on thiacloprid, has no cross resistance with other conventional pesticides, and is one of the pesticides which are not forbidden in Europe and America. The field test shows that thiacloprid has excellent control effect on important pests on pear fruits, cotton, vegetables and potatoes. In addition to being effective against aphids and whiteflies, thiacloprid is also effective against various beetles (e.g., potato beetle, sterling weevil, rice weevil) and lepidopteran pests (e.g., leaf miner and codling moth on apple trees), and is applicable to all crops accordingly.
The chemical accession number (CAS number) of thiacloprid is: 111988-49-9, the molecular formula is: C10H9ClN4S, molecular weight: 252.72, melting point: at 128 ℃.
At present, a plurality of patents at home and abroad report the preparation route of thiacloprid, and Chinese patent document with publication number CN1161354C discloses a method for preparing heterocyclic compounds, wherein the method adopts reaction potassium carbonate or potassium hydroxide as alkali to prepare thiacloprid, the reaction temperature is high, the impurities are higher, the waste salt content is large, and the yield is only 70%. Chinese patent publication No. CN102399216 discloses a method for producing thiacloprid technical, which adopts formaldehyde as a catalyst system, has a yield of only 80%, and has great environmental pollution, difficult recovery and difficult scale-up production. Other existing methods all adopt inorganic salts such as potassium carbonate, sodium hydroxide, potassium hydroxide and the like, have the defects of large amount of solid waste salt after reaction, low reaction yield and the like, do not meet the requirements of environmental protection and are not beneficial to industrial production. Therefore, there is an urgent need for improvement of the existing preparation method.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a thiacloprid preparation method and a thiacloprid preparation system, wherein an iridium complex and organic base DBU or DABCO are subjected to double catalytic condensation, inorganic base is adopted, the reaction rate and the final yield are improved, the waste salt amount is greatly reduced, and the process is green and environment-friendly.
In order to achieve the purpose, the preparation method of thiacloprid provided by the invention comprises the following steps:
mixing 2-cyanoimine-1, 3-thiazolidine, a reaction solvent, an iridium complex and an organic base to obtain a first material, and taking 2-chloro-5-chloromethylpyridine as a second material;
mixing the first material and the second material, and then carrying out condensation reaction to generate thiacloprid;
and (3) carrying out acid adjustment, cooling, crystallization and suction filtration on thiacloprid to obtain a thiacloprid finished product.
Further, the molar ratio of the 2-cyanoimine-1, 3-thiazolidine to the organic base is 1: 1-1.05.
Further, the organic base is DBU or DABCO.
Further, the reaction solvent is methanol or ethanol.
Further, the molar ratio of the 2-cyanoimine-1, 3-thiazolidine to the iridium complex is 1: 0.01-0.03.
Further, the volume ratio of the 2-cyanoimine-1, 3-thiazolidine to the reaction solvent is 1: 4-5.
Further, the molar ratio of the 2-cyanoimine-1, 3-thiazolidine to the 2-chloro-5-chloromethylpyridine is 1: 1-1.2.
Further, the step of mixing the first material and the second material and then carrying out condensation reaction to generate thiacloprid also comprises the following steps of,
setting the feeding flow rate of the first material to be 30 or 35ml/min, and setting the feeding flow rate of the second material to be 8 ml/min;
simultaneously feeding the first material and the second material into a continuous flow reactor for condensation reaction, wherein the reaction temperature is 30-60 ℃;
the reaction chemical equation is:
further, the step of adjusting the acid of the thiacloprid also comprises the steps of feeding the thiacloprid into an acid adjusting kettle, and dropwise adding a sodium citrate aqueous solution into the acid adjusting kettle to adjust the acid.
In order to achieve the above object, the present invention further provides a thiacloprid preparation system, which comprises a continuous flow reactor, a first feeding pump, a second feeding pump, an acid adjusting kettle, and a temperature reducing kettle, wherein,
the first feeding pump is used for feeding a first material flow into the continuous flow reactor according to a set flow rate;
the second feeding pump is used for feeding a second material into the continuous flow reactor according to a set flow rate;
the continuous flow reactor is used for carrying out condensation reaction on the first material and the second material to generate thiacloprid;
the acid adjusting kettle is used for adjusting the acid of the generated thiacloprid;
the cooling kettle is used for cooling, crystallizing and filtering the acid-adjusted thiacloprid to obtain a thiacloprid finished product;
the first strand of material is: 2-cyanoimine-1, 3-thiazolidine, a reaction solvent, an iridium complex and an organic base; the second stream was 2-chloro-5-chloromethylpyridine.
Compared with the prior art, the preparation method and the system of thiacloprid have the following beneficial effects:
1) by adopting a self-made iridium complex and organic base DBU or DABCO double-catalysis condensation mode, the raw materials can not generate alkaline hydrolysis to generate impurities in the system, and the reaction rate and the final yield are improved. The average yield is up to more than 90%.
2) The method completely uses safe and cheap raw materials, reduces the production cost, has mild reaction and is easier for industrial production.
3) And the inorganic alkali is adopted, so that the waste salt content is greatly reduced. The waste salt treatment cost is reduced, the continuous production operation is convenient and simple, the human error is greatly reduced, and the process safety is improved.
Drawings
In order to more clearly illustrate the technical solution in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly described below. It is clear that the described figures are only some embodiments of the invention, not all embodiments, and that a person skilled in the art can also derive other designs and figures from them without inventive effort.
FIG. 1 is a flow chart of the preparation method of thiacloprid of the invention;
FIG. 2 is a schematic structural diagram of a thiacloprid preparation system.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It is to be understood that these examples are for the purpose of illustrating the general principles, essential features and advantages of the present invention, and that the present invention is not limited by the following examples, and that the conditions employed in the examples may be further modified according to specific requirements, and that the conditions not specified are generally conditions in routine experimentation.
Example 1
Fig. 1 is a flow chart of a method for preparing thiacloprid of the present invention, and the method for preparing thiacloprid of the present invention will be described in detail with reference to fig. 1.
First, in step 101, a first stream of material is formed.
In the embodiment of the invention, 2-cyanoimine-1, 3-thiazolidine, a reaction solvent, a catalyst and an organic base are mixed and stirred to be used as a first material (Feed 1).
In the embodiment of the invention, the reaction solvent can be alcohols, lipids, and alkane compounds, such as methanol, ethanol, and the like; the catalyst is an iridium complex; as the organic base, DBU (1, 8-diazabicycloundecen-7-ene) or DABCO (triethylenediamine) can be used.
In step 102, 2-chloro-5-chloromethylpyridine is used as the second stream.
In step 103, the feeding flow rate is set, and the first material and the second material are sent into the continuous flow reactor to be mixed and undergo condensation reaction to generate thiacloprid.
In the embodiment of the invention, after the continuous flow reactor and the feeding pump are built, the feeding flow rate is set; and after the setting is finished, starting the feeding pumps of the two materials simultaneously. Mixing the two materials in a continuous flow reactor, and condensing to generate thiacloprid, wherein the specific reaction equation is as follows:
in step 104, the generated thiacloprid is sent to an acid adjusting kettle for acid adjustment.
In the embodiment of the invention, after the continuous flow reactor outlet is sampled and the detection reaction is completed, the generated thiacloprid is sent to the acid regulating kettle, and the sodium citrate aqueous solution is dripped into the acid regulating kettle to regulate the acid after the materials completely enter the acid regulating kettle.
And 105, sending the acid-adjusted thiacloprid into a cooling kettle for cooling, crystallizing and suction filtering to obtain a thiacloprid finished product.
Example 2
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 180g of the product, wherein the content is 98.4%, the yield is 95.4%, and the melting point is 128-130 ℃.
Example 3
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of ethanol (reaction solvent), 0.2g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 174g with the content of 97.5 percent, the yield of 93.4 percent and the melting point of 128-130 ℃.
Example 4
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 88g (0.8mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 177g with the content of 98 percent, the yield of 94.1 percent and the melting point of 128-130 ℃.
Example 5
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.1g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 170g of the product, wherein the content is 97.6%, the yield is 93.8%, and the melting point is 128-130 ℃.
Example 6
Preparing a first strand of material (Feed1), 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex ((catalyst) and 90g (0.8mol) of DBU (organic base), mixing and stirring the materials for standby, then preparing a second strand of material (Feed2), 148g (0.88mol) of 2-chloro-5 chloromethylpyridine, setting the feeding flow rate after the microreactor and a feeding pump are assembled, setting the feeding flow rate of Feed1 at 30ml/min, setting the flow rate of Feed2 at 8ml/min, simultaneously starting the feeding pumps of two strands of material after setting, carrying out mixing reaction on the materials in the microreactor, controlling the temperature at 40 ℃, fully mixing, then condensing to generate thiacloprid, adjusting the internal pressure of the microreactor to 0.7MPa, staying for 3min, then sampling from an outlet of the microreactor, detecting and completely entering an acid adjusting kettle, and (3) after the materials completely enter the kettle, dropwise adding 20g of saturated sodium citrate aqueous solution. Cooling, crystallizing and filtering to obtain 180g of crystal with the content of 95.4 percent, the yield of 94.2 percent and the melting point of 128-130 ℃.
Example 7
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 35ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 169g of crystal with the content of 96.4 percent, the yield of 94 percent and the melting point of 128-130 ℃.
Example 8
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 30 ℃. Mixing them fully and condensing to obtain thiacloprid. And adjusting the internal pressure of the microreactor to 0.7Mpa, standing for 8min, sampling from the outlet of the microreactor, and detecting the completion of the reaction. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 177g with the content of 96.7 percent, the yield of 94.2 percent and the melting point of 128-130 ℃.
Example 9
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 60 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, staying for 2min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 184g with the content of 95.8 percent, the yield of 94.7 percent and the melting point of 128-130 ℃.
Example 10
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 74g (0.8mol) of DABCO (triethylenediamine, organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 176g with the content of 97.1 percent, the yield of 95 percent and the melting point of 128-130 ℃.
Example 11
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 95g (0.84mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 182g with the content of 98 percent, the yield of 95.7 percent and the melting point of 128-130 ℃.
Example 12
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.2g of iridium complex (catalyst) and 92g (0.82mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 180g of the product, wherein the content is 98.9%, the yield is 95.5%, and the melting point is 128-130 ℃.
Example 13
A first batch (Feed1) of 100g (0.8mol) of 2-cyanoimine-1, 3-thiazolidine, 500ml of methanol (reaction solvent), 0.3g of iridium complex (catalyst) and 90g (0.8mol) of DBU (organic base) was prepared. Mixing the above materials, and stirring. Then prepare a second stream (Feed 2): 140g (0.85mol) of 2-chloro-5-chloromethylpyridine. Setting the feeding flow rate after the microreactor and the feeding pump are built, and setting the flow rate of Feed 1: 30ml/min, Feed2 flow rate setting: 8 ml/min. And after the setting is finished, starting the feeding pumps of the two materials simultaneously. The two materials are mixed and reacted in a microreactor, and the temperature is controlled to be 40 ℃. Mixing them fully and condensing to obtain thiacloprid. Adjusting the internal pressure of the micro-reactor to 0.7Mpa, standing for 3min, sampling from the micro-reactor outlet, and detecting the reaction completion. And (4) putting the mixture into an acid adjusting kettle, and dropwise adding 20g of saturated sodium citrate aqueous solution into the kettle when the mixture completely enters the kettle. Cooling, crystallizing and filtering to obtain 185g of crystal, wherein the content is 97.8%, the yield is 95.3%, and the melting point is 128-130 ℃.
Example 14
The embodiment of the invention also provides a thiacloprid preparation system, as shown in fig. 2, the thiacloprid preparation system of the invention comprises a continuous flow reactor 201, a first feeding pump 202, a second feeding pump 203, an acid adjusting kettle 204 and a cooling kettle 205, wherein,
the first feeding pump 202 and the second feeding pump 203 are respectively connected with the continuous flow reactor 201, and respectively feed the first material and the second material into the continuous flow reactor 201 according to set flow rates.
In the embodiment of the invention, the first strand of materials is as follows: 2-cyanoimine-1, 3-thiazolidine, a reaction solvent, an iridium complex and an organic base; the second stream was 2-chloro-5-chloromethylpyridine.
The continuous flow reactor 201 is a tubular reactor or a microreactor, and is used for performing condensation reaction on a first material and a second material to generate thiacloprid.
And the acid adjusting kettle 204 is used for adjusting the acid of the thiacloprid generated by the continuous flow reactor 201.
And the cooling kettle 205 is used for cooling, crystallizing and filtering the acid-adjusted thiacloprid to obtain a thiacloprid finished product.
Those of ordinary skill in the art will understand that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of thiacloprid comprises the following steps:
mixing 2-cyanoimine-1, 3-thiazolidine, a reaction solvent, an iridium complex and an organic base to obtain a first material, and taking 2-chloro-5-chloromethylpyridine as a second material;
mixing the first material and the second material, and then carrying out condensation reaction to generate thiacloprid;
and (3) carrying out acid adjustment, cooling, crystallization and suction filtration on thiacloprid to obtain a thiacloprid finished product.
2. The method for preparing thiacloprid according to claim 1, characterized in that the molar ratio of the 2-cyanoimine-1, 3-thiazolidine and the organic base is 1:1 to 1.05.
3. The method of claim 1, wherein the organic base is DBU or DABCO.
4. The method according to claim 1, wherein the reaction solvent is methanol or ethanol.
5. The method for preparing thiacloprid according to claim 1, characterized in that the molar ratio of the 2-cyanoimine-1, 3-thiazolidine to the iridium complex is 1: 0.01-0.03.
6. The method for preparing thiacloprid according to claim 1, characterized in that the volume ratio of the 2-cyanoimine-1, 3-thiazolidine to the reaction solvent is 1: 4-5.
7. The method for preparing thiacloprid according to claim 1, characterized in that the molar ratio of the 2-cyanoimine-1, 3-thiazolidine to the 2-chloro-5 chloromethylpyridine is 1:1 to 1.2.
8. The method for preparing thiacloprid according to claim 1, wherein the step of mixing the first material and the second material and then carrying out condensation reaction to generate thiacloprid further comprises,
setting the feeding flow rate of the first material to be 30 or 35ml/min, and setting the feeding flow rate of the second material to be 8 ml/min;
simultaneously feeding the first material and the second material into a continuous flow reactor for condensation reaction, wherein the reaction temperature is 30-60 ℃;
the reaction chemical equation is:
9. the method for preparing thiacloprid according to claim 1, which is characterized by comprising the step of adjusting the acid of the thiacloprid, and further comprising the step of feeding the thiacloprid into an acid adjusting kettle, and dropwise adding a sodium citrate aqueous solution into the acid adjusting kettle to adjust the acid.
10. A thiacloprid preparation system comprises a continuous flow reactor, a first feeding pump, a second feeding pump, an acid adjusting kettle and a cooling kettle, and is characterized in that,
the first feeding pump is used for feeding a first material flow into the continuous flow reactor according to a set flow rate;
the second feeding pump is used for feeding a second material into the continuous flow reactor according to a set flow rate;
the continuous flow reactor is used for carrying out condensation reaction on the first material and the second material to generate thiacloprid;
the acid adjusting kettle is used for adjusting the acid of the generated thiacloprid;
the cooling kettle is used for cooling, crystallizing and filtering the acid-adjusted thiacloprid to obtain a thiacloprid finished product;
the first strand of material is: 2-cyanoimine-1, 3-thiazolidine, a reaction solvent, an iridium complex and an organic base; the second stream was 2-chloro-5-chloromethylpyridine.
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| CN102399216A (en) * | 2011-11-30 | 2012-04-04 | 利民化工股份有限公司 | Method for producing thiacloprid technical |
| CN103145701A (en) * | 2013-03-27 | 2013-06-12 | 杨文茂 | Method for synthesizing thiacloprid active compound and co-producing carbon powder |
| CN107629045A (en) * | 2017-11-10 | 2018-01-26 | 上海生农生化制品股份有限公司 | A kind of aqueous synthesis method of thiacloprid |
| CN109354590A (en) * | 2018-12-18 | 2019-02-19 | 山东省联合农药工业有限公司 | A kind of new synthetic method of thiacloprid |
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| CN102399216A (en) * | 2011-11-30 | 2012-04-04 | 利民化工股份有限公司 | Method for producing thiacloprid technical |
| CN103145701A (en) * | 2013-03-27 | 2013-06-12 | 杨文茂 | Method for synthesizing thiacloprid active compound and co-producing carbon powder |
| CN107629045A (en) * | 2017-11-10 | 2018-01-26 | 上海生农生化制品股份有限公司 | A kind of aqueous synthesis method of thiacloprid |
| CN109354590A (en) * | 2018-12-18 | 2019-02-19 | 山东省联合农药工业有限公司 | A kind of new synthetic method of thiacloprid |
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