CN111036158A - 2 chlorine-5 chloromethyl thiazole synthesis reaction system - Google Patents
2 chlorine-5 chloromethyl thiazole synthesis reaction system Download PDFInfo
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- CN111036158A CN111036158A CN201911383999.1A CN201911383999A CN111036158A CN 111036158 A CN111036158 A CN 111036158A CN 201911383999 A CN201911383999 A CN 201911383999A CN 111036158 A CN111036158 A CN 111036158A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
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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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
Abstract
The invention relates to the technical field of methylthiazole synthesis, in particular to a 2-chloro-5-chloromethyl thiazole synthesis reaction system. Because the chemical reaction can generate impurities to influence the reaction time and the subsequent treatment of a reaction substrate, when the adopted raw materials enter a reaction kettle, 2-amino-5-methylthiazole dissolved in an organic solvent is mixed with a sodium nitrite solution in a mixing device, so that organic matters form oily small drops which are easier to contact and react with hydrogen chloride gas when injected into the reaction kettle; the dispersing device used at the top of the reaction kettle is provided with a plurality of through round holes, the mixed liquid is sprayed out from the sprayer and then directly falls onto the dispersing device, and the mixed liquid is slowly sprayed into the reaction kettle through the round holes on the dispersing device, so that the contact time of the hydrogen chloride gas and the mixed liquid is prolonged, the gas is more easily dissolved, and the production efficiency is improved; the hydrogen chloride gas used by the chlorinating agent is used, the filtrate after the reaction is simply treated, the main component in the filtrate is hydrochloric acid, and the filtrate can be reused by a mixing device, so that the cost is saved.
Description
Technical Field
The invention relates to the technical field of methylthiazole synthesis, in particular to a 2-chloro-5-chloromethyl thiazole synthesis reaction system.
Background
The 2-chloro-5-chloromethyl thiazole is light yellow liquid or solid, and is used for synthesizing pesticides thiamethoxam, clothianidin and ritonavir. At present, thiamethoxam serving as a new generation of nicotine pesticide has strong killing power on pests, is concerned by the pesticide field, and has good market prospect; ritonavir is also indispensable as an inhibitor of Human Immunodeficiency Virus (HIV) without a specific drug. The synthesis route of the 2-chloro-5-chloromethylthiazole is more, but the production process is more complicated and the yield of the reaction product is lower.
Disclosure of Invention
Aiming at the technical defects, the invention provides a 2-chloro-5-chloromethylthiazole synthesis reaction system, which can generate other impurities in the chemical synthesis reaction to influence the reaction time and the subsequent treatment of a reaction substrate, and adopts the technical scheme that when raw materials enter a reaction kettle, 2-amino-5-methylthiazole dissolved in an organic solvent and a sodium nitrite solution are mixed in a mixing device, so that organic matters form oily small drops, and the organic matters are easier to contact and react with hydrogen chloride gas when being injected into the reaction kettle; the dispersing device used at the top of the reaction kettle is provided with a plurality of through round holes, the mixed liquid is sprayed out from the sprayer and then directly falls onto the dispersing device, and the mixed liquid is slowly sprayed into the reaction kettle through the round holes on the dispersing device, so that the contact time of the hydrogen chloride gas and the mixed liquid is prolonged, the gas is more easily dissolved, and the production efficiency is improved; as the chlorinating agent uses hydrogen chloride gas, the filtrate after reaction is simply treated, the main component in the filtrate is hydrochloric acid, and the filtrate can be reused by a mixing device, so that the cost is saved.
In order to solve the technical problems, the technical scheme adopted by the invention is that a 2 chloro-5 chloromethyl thiazole synthesis reaction system is characterized in that a reactor used in the reaction system is as follows: the device comprises a reaction kettle, a rectifying tower, a mixing device, a circulating pump and a hydraulic pump; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite, dilute hydrochloric acid and a chlorinating agent.
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by, includes the following step:
(1) dissolving sodium nitrite in distilled water to obtain solution with certain concentration, injecting into a mixing device, and mixing uniformly for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride gas into the reaction kettle, and after the introduction of the hydrogen chloride gas into the reaction kettle is finished, spraying the mixed solution from the top of the reaction kettle;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower under the action of a hydraulic pump, and rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and (4) refluxing the reacted filtrate to the mixing device, and recycling the filtrate.
The molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 0.6-0.8; the organic solvent is composed of one or a mixed solution of dichloromethane and chloroform; the chlorinating agent is chlorine gas or hydrogen chloride gas.
The temperature in the reaction kettle is 20-50 ℃; the stirring time in the reaction kettle is 2-5 h.
An air inlet is formed in the right side position of the top of the reaction kettle; a heat exchanger is arranged outside the mixing device; a feed inlet is formed in the right side of the top of the mixing device; the reaction devices are connected through pipelines.
A hydraulic pump is arranged between the reaction kettle and the rectifying tower; a hydraulic pump is arranged between the rectifying tower and the circulating pump; and a circulating pump is arranged between the reaction kettle and the mixing device.
A dispersion device is arranged at the middle position of the top of the reaction kettle; a plurality of round holes are formed in the dispersing device; an ejector is arranged at the top of the reaction kettle; the ejector is arranged at the lower end of the stop valve; the stop valve is arranged on a pipeline outside the top of the reaction kettle.
Compared with the prior art, the invention has the following advantages: 1. the top of the reaction kettle is provided with the dispersing device, so that the liquid is easier to mix with the hydrogen chloride gas when being sprayed, and the reaction time of the whole production process is reduced; 2. purifying the 2 chloro-5 chloromethyl thiazole solution generated in the reaction kettle in a rectifying tower to ensure that the purity of the product is higher; 3. filtrate in the rectifying tower and the reaction kettle flows back to the mixing device through pipelines, so that raw materials are saved, and the production cost is reduced; 4, the waste liquid after the reaction is easy to treat, and the influence of products in production on the environment is reduced; 5. the chlorinating agent is hydrogen chloride gas, the mutual solubility ratio of water and the hydrogen chloride gas is 1:500, and the residual gas after reaction is easy to absorb and treat; 6. the organic solvent for dissolving the 2-amino-5-methylthiazole adopts dichloromethane and chloroform, so that the absorption of the solvent to hydrogen chloride gas is reduced, the 2-amino-5-methylthiazole and sodium nitrite can absorb the hydrogen chloride more fully, and the reaction effect is better.
Drawings
FIG. 1 is a schematic structural diagram of a 2 chloro-5 chloromethylthiazole synthesis reaction system.
FIG. 2 is a schematic structural diagram of a dispersing apparatus of a 2 chloro-5 chloromethylthiazole synthesis reaction system.
FIG. 3 is a table showing the effect of the amount of hydrogen chloride introduced on the yield of reaction products in the reaction of a 2 chloro-5 chloromethylthiazole synthesis reaction system.
FIG. 4 is a table showing the measurement of the influence of the reaction time of raw materials in a reaction vessel on the yield of a product in a 2 chloro-5 chloromethylthiazole synthesis reaction system.
FIG. 5 is a table showing the detection results of the reaction system for synthesizing 2 chloro-5 chloromethylthiazole in the yield of the product by controlling the temperature in the reaction vessel.
FIG. 6 is a table showing the effect of different chlorinating agents introduced into the reaction kettle of a 2 chloro-5 chloromethylthiazole synthesis reaction system on the reaction products.
In the figure: 1. a reaction kettle; 101. a dispersing device; 102. an ejector; 103. a stop valve; 104. an air inlet; 105. a circular hole; 2. a rectifying tower; 3. a mixing device; 301. a feed inlet; 302. a heat exchanger; 4. a circulation pump; 5. a hydraulic pump.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings in conjunction with the following detailed description. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by that, the reactor that uses in the reaction system is: the device comprises a reaction kettle 1, a rectifying tower 2, a mixing device 3, a circulating pump 4 and a hydraulic pump 5; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite and a chlorinating agent.
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by, includes the following step:
(1) dissolving sodium nitrite in distilled water to prepare solution with certain concentration, injecting the solution into a mixing device 3, and uniformly mixing the solution for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device 3, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride gas into the reaction kettle 1, and after the hydrogen chloride gas in the reaction kettle 1 is completely introduced, spraying the mixed solution from the top of the reaction kettle 1;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower 2 under the action of a hydraulic pump, rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and (4) refluxing the reacted filtrate to the mixing device 3, and recycling the filtrate.
The molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 0.8; the organic solvent is composed of one or a mixed solution of dichloromethane and chloroform; the chlorinating agent is hydrogen chloride gas.
The temperature in the reaction kettle 1 is 20-35 ℃; the stirring time in the reaction kettle 1 is 2 hours.
An air inlet 104 is arranged at the right side position of the top of the reaction kettle 1; a heat exchanger 302 is arranged outside the mixing device 3; a feeding hole 301 is formed in the right side position of the top of the mixing device 3; the reaction devices are connected through pipelines.
A hydraulic pump 5 is arranged between the reaction kettle 1 and the rectifying tower 2; a hydraulic pump 5 is arranged between the rectifying tower 2 and the circulating pump 4; and a circulating pump 4 is arranged between the reaction kettle 1 and the mixing device 3.
A dispersing device 101 is arranged in the middle of the top of the reaction kettle 1; a plurality of round holes 105 are arranged on the dispersion device 101; the ejector 102 is arranged at the top of the reaction kettle 1; the ejector 102 is arranged at the lower end of the stop valve 103; the stop valve 103 is arranged on a pipeline outside the top of the reaction kettle 1.
Example 2
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by that, the reactor that uses in the reaction system is: the device comprises a reaction kettle 1, a rectifying tower 2, a mixing device 3, a circulating pump 4 and a hydraulic pump 5; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite, dilute hydrochloric acid and a chlorinating agent.
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by, includes the following step:
(1) dissolving sodium nitrite in distilled water to prepare solution with certain concentration, injecting the solution into a mixing device 3, and uniformly mixing the solution for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device 3, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride gas into the reaction kettle 1, and after the hydrogen chloride gas in the reaction kettle 1 is completely introduced, spraying the mixed solution from the top of the reaction kettle 1;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower 2 under the action of a hydraulic pump 5, rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and refluxing the reacted filtrate to the mixing device, and recycling the filtrate.
The molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 1.0-1.2; the organic solvent is composed of one or a mixed solution of dichloromethane and chloroform; the chlorinating agent is hydrogen chloride gas.
The temperature in the reaction kettle 1 is 20-35 ℃; the stirring time in the reaction kettle 1 is 2 hours.
An air inlet 104 is arranged at the right side position of the top of the reaction kettle 1; a heat exchanger 302 is arranged outside the mixing device 3; a feeding hole 301 is formed in the right side position of the top of the mixing device 3; the reaction devices are connected through pipelines.
A hydraulic pump 5 is arranged between the reaction kettle 1 and the rectifying tower 2; a hydraulic pump 5 is arranged between the rectifying tower 2 and the circulating pump 4; and a circulating pump 4 is arranged between the reaction kettle 1 and the mixing device 3.
A dispersing device 101 is arranged in the middle of the top of the reaction kettle 1; a plurality of round holes 105 are arranged on the dispersion device 101; the ejector 102 is arranged at the top of the reaction kettle 1; the ejector 102 is arranged at the lower end of the stop valve 103; the stop valve 103 is arranged on a pipeline outside the top of the reaction kettle 1.
Example 3
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by that, the reactor that uses in the reaction system is: the device comprises a reaction kettle 1, a rectifying tower 2, a mixing device 3, a circulating pump 4 and a hydraulic pump 5; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite, dilute hydrochloric acid and a chlorinating agent.
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by, includes the following step:
(1) dissolving sodium nitrite in distilled water to prepare solution with certain concentration, injecting the solution into a mixing device 3, and uniformly mixing the solution for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride gas into the reaction kettle 1, and after the hydrogen chloride gas in the reaction kettle 1 is completely introduced, spraying the mixed solution from the top of the reaction kettle 1;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower 2 under the action of a hydraulic pump 5, rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and (4) refluxing the reacted filtrate to the mixing device 3, and recycling the filtrate.
The molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 1; the organic solvent is composed of one or a mixed solution of dichloromethane and chloroform; the chlorinating agent is hydrogen chloride gas.
The temperature in the reaction kettle 1 is 20-35 ℃; the stirring time in the reaction kettle is 3-5 h.
An air inlet 104 is arranged at the right side position of the top of the reaction kettle 1; a heat exchanger 302 is arranged outside the mixing device 3; a feeding hole 301 is formed in the right side position of the top of the mixing device 3; the reaction devices are connected through pipelines.
A hydraulic pump 5 is arranged between the reaction kettle 1 and the rectifying tower 2; a hydraulic pump 5 is arranged between the rectifying tower 2 and the circulating pump 4; and a circulating pump 4 is arranged between the reaction kettle 1 and the mixing device 3.
A dispersing device 101 is arranged in the middle of the top of the reaction kettle 1; a plurality of round holes 105 are arranged on the dispersion device 101; the ejector 102 is arranged at the top of the reaction kettle 1; the ejector 102 is arranged at the lower end of the stop valve 103; the stop valve 103 is arranged on a pipeline outside the top of the reaction kettle 1.
Example 4
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by that, the reactor that uses in the reaction system is: the device comprises a reaction kettle 1, a rectifying tower 2, a mixing device 3, a circulating pump 4 and a hydraulic pump 5; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite, dilute hydrochloric acid and a chlorinating agent.
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by, includes the following step:
(1) dissolving sodium nitrite in distilled water to prepare solution with certain concentration, injecting the solution into a mixing device 3, and uniformly mixing the solution for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device 3, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride gas into the reaction kettle 1, and after the introduction of the hydrogen chloride gas into the reaction kettle is finished, spraying the mixed solution from the top of the reaction kettle 1;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower 2 under the action of a hydraulic pump, rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and (3) refluxing the reacted filtrate into the mixing device 3 through a pipeline, and recycling the filtrate.
The molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 1; the organic solvent is composed of one or a mixed solution of dichloromethane and chloroform; the chlorinating agent is hydrogen chloride gas.
The temperature in the reaction kettle 1 is 35-45 ℃; the stirring time in the reaction kettle 1 is 2 hours.
An air inlet 104 is arranged at the right side position of the top of the reaction kettle 1; a heat exchanger 302 is arranged outside the mixing device 3; a feeding hole 301 is formed in the right side position of the top of the mixing device 3; the reaction devices are connected through pipelines.
A hydraulic pump 5 is arranged between the reaction kettle 1 and the rectifying tower 2; a hydraulic pump 5 is arranged between the rectifying tower 2 and the circulating pump 4; and a circulating pump 4 is arranged between the reaction kettle 1 and the mixing device 3.
A dispersing device 101 is arranged in the middle of the top of the reaction kettle 1; a plurality of round holes 105 are arranged on the dispersion device 101; the ejector 102 is arranged at the top of the reaction kettle 1; the ejector 102 is arranged at the lower end of the stop valve 103; the stop valve 103 is arranged on a pipeline outside the top of the reaction kettle 1.
Example 5
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by that, the reactor that uses in the reaction system is: the device comprises a reaction kettle 1, a rectifying tower 2, a mixing device 3, a circulating pump 4 and a hydraulic pump 5; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite, dilute hydrochloric acid and a chlorinating agent.
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by, includes the following step:
(1) dissolving sodium nitrite in distilled water to prepare solution with certain concentration, injecting the solution into a mixing device 3, and uniformly mixing the solution for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device 3, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride gas into the reaction kettle 1, and after the hydrogen chloride gas in the reaction kettle 1 is completely introduced, spraying the mixed solution from the top of the reaction kettle 1;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower 2 under the action of a hydraulic pump 5, rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and (4) refluxing the reacted filtrate to the mixing device 3, and recycling the filtrate.
The molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 1; the organic solvent is composed of one or a mixed solution of dichloromethane and chloroform; the chlorinating agent is hydrogen chloride gas.
The temperature in the reaction kettle 1 is 45-60 ℃; the stirring time in the reaction kettle 1 is 2 hours.
An air inlet 104 is arranged at the right side position of the top of the reaction kettle 1; a heat exchanger 302 is arranged outside the mixing device 3; a feeding hole 301 is formed in the right side position of the top of the mixing device 3; the reaction devices are connected through pipelines.
A hydraulic pump 5 is arranged between the reaction kettle 1 and the rectifying tower 2; a hydraulic pump 5 is arranged between the rectifying tower 2 and the circulating pump 4; and a circulating pump 4 is arranged between the reaction kettle 1 and the mixing device 3.
A dispersing device 101 is arranged in the middle of the top of the reaction kettle 1; a plurality of round holes 105 are arranged on the dispersion device 101; the ejector 102 is arranged at the top of the reaction kettle 1; the ejector 102 is arranged at the lower end of the stop valve 103; the stop valve 103 is arranged on a pipeline outside the top of the reaction kettle 1.
Example 6
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by that, the reactor that uses in the reaction system is: the device comprises a reaction kettle 1, a rectifying tower 2, a mixing device 3, a circulating pump 4 and a hydraulic pump 5; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite, dilute hydrochloric acid and a chlorinating agent.
A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by, includes the following step:
(1) dissolving sodium nitrite in distilled water to prepare solution with certain concentration, injecting the solution into a mixing device, and uniformly mixing the solution 3 for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device 3, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride gas into the reaction kettle 1, and after the hydrogen chloride gas in the reaction kettle 1 is completely introduced, spraying the mixed solution from the top of the reaction kettle 1;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower 2 under the action of a hydraulic pump 5, rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and (4) refluxing the reacted filtrate to the mixing device 3, and recycling the filtrate.
The molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 1; the organic solvent is composed of one or a mixed solution of dichloromethane and chloroform; the chlorinating agent is chlorine gas.
The temperature in the reaction kettle 1 is 20-50 ℃; the stirring time in the reaction kettle 1 is 2-5 h.
An air inlet 101 is formed in the right side of the top of the reaction kettle 1; a heat exchanger 302 is arranged outside the mixing device 3; a feeding hole 301 is formed in the right side position of the top of the mixing device 3; the reaction devices are connected through pipelines.
A hydraulic pump 5 is arranged between the reaction kettle 1 and the rectifying tower 2; a hydraulic pump 5 is arranged between the rectifying tower 2 and the circulating pump 4; and a circulating pump 4 is arranged between the reaction kettle 1 and the mixing device 3.
A dispersing device 101 is arranged in the middle of the top of the reaction kettle 1; a plurality of round holes 105 are arranged on the dispersion device 101; the ejector 102 is arranged at the top of the reaction kettle 1; the ejector 102 is arranged at the lower end of the stop valve 103; the stop valve 103 is arranged on a pipeline outside the top of the reaction kettle 1.
Taking a product sample 2 chloro-5 chloromethyl thiazole in each embodiment, weighing 3g of the sample on a ten-thousand-position electronic balance, adding 3ml of acetonitrile or methanol reagent into a centrifuge tube, shaking to ensure that the 2 chloro-5 chloromethyl thiazole and the solvent are completely mutually dissolved, standing at room temperature for 10min, taking 1ml of the sample by using a sampling needle tube, and filtering the sample into a sample bottle through 0.25ul of organic membrane; a sample injection needle is taken newly, and the needle is washed for 25-30 times by using a sample solvent to be detected, so that the influence of magazines in the sample injection needle on the result is prevented; the prepared sample is tested for purity on a gas chromatograph, and data is recorded.
As can be seen from fig. 3, when the amount of hydrogen chloride gas introduced was increased under other conditions, the yield of the reaction product was high, and when the amount of hydrogen chloride gas introduced was continuously increased, the reaction product was not affected. As can be seen from FIG. 4, under other conditions, when the stirring time and the reaction time of the reactants in the reaction vessel 1 are increased, the yield of the product is slightly reduced, which indicates that the reaction time is too long, which is not favorable for improving the yield of the product; in addition, the reaction time of the 2-chloro-5-chloromethylthiazole is longer in the traditional production process by searching data. As can be seen from FIG. 5, when the temperature in the reaction kettle 1 is changed, the activity of sodium nitrite under acidic condition is affected, and the reaction effect of sodium nitrite and 2-amino-5-methylthiazole under acidic condition is better at 35-45 ℃, and the product yield is higher. As can be seen from fig. 6, since the solubility of chlorine in the solution is low, when chlorine with the same mole number is introduced into the reaction kettle 1 before the reaction to replace hydrogen chloride gas, the yield of the reaction product is low; and hypochlorous acid is generated when chlorine reacts with the solution, so that impurities in the filtrate are increased, and the filtrate cannot be directly used.
In summary, in the production, sodium nitrite is mixed with 2-amino-5-methylthiazole dissolved in an organic solvent, and then the mixture is mixed with a chlorinating agent in a proportion of 1: the molar ratio is 1, the temperature in the reaction kettle 1 is 35-45 ℃, the stirring and reaction time is 2 hours, and the yield of the product is highest when the chlorinating agent is hydrogen chloride gas. And because the hydrogen chloride is dissolved in water to generate dilute hydrochloric acid, the filtrate used in the mixing device provides a better environment for the oxidation catalysis of the sodium nitrite.
The control mode of the invention is automatically controlled by the controller, the control circuit of the controller can be realized by simple programming of a person skilled in the art, the invention belongs to the common knowledge in the field, and the invention is mainly used for protecting mechanical devices, so the control mode and the circuit connection are not explained in detail in the invention.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (7)
1. A2 chloro-5 chloromethyl thiazole synthesizes reaction system, characterized by that, the reactor that uses in the reaction system is: the device comprises a reaction kettle 1, a rectifying tower 2, a mixing device 3, a circulating pump 4 and a hydraulic pump 5; the reaction raw materials are as follows: 2-amino-5-methylthiazole, an organic solvent, sodium nitrite and a chlorinating agent.
2. The reaction system for the synthesis of 2 chloro-5 chloromethylthiazole according to claim 1, comprising the steps of:
(1) dissolving sodium nitrite in distilled water to prepare solution with certain concentration, injecting the solution into a mixing device 3, and uniformly mixing the solution for later use;
(2) injecting the 2-amino-5-methylthiazole dissolved by the organic solvent into a mixing device 3, and mixing the mixture and sodium nitrite according to a proportion to prepare a mixed solution for later use;
(3) introducing hydrogen chloride into the reaction kettle 1, and after the gas in the reaction kettle 1 is completely introduced, spraying the mixed solution from the top of the reaction kettle 1 through the dispersing device 101;
(4) after the mixed solution is completely poured, continuously stirring at the temperature to fully generate a 2-chloro-5-chloromethyl thiazole solution;
(5) after the reaction is finished, injecting the 2-chloro-5-chloromethyl thiazole solution into a rectifying tower 2 under the action of a hydraulic pump 5, rectifying and purifying;
(6) rectifying to obtain a pure 2 chloro-5 chloromethyl thiazole product;
(7) and (4) refluxing the reacted filtrate into the mixing device 3, and recycling the filtrate.
3. The reaction system for the synthesis of 2-chloro-5-chloromethylthiazole, according to claim 2, wherein: the molar ratio of the 2-amino-5-methylthiazole to the hydrogen chloride gas is 1: 0.8-1.2; the organic solvent is composed of dichloromethane, chloroform or a mixed solution of the dichloromethane and the chloroform; the chlorinating agent is chlorine gas or hydrogen chloride gas.
4. The reaction system for the synthesis of 2-chloro-5-chloromethylthiazole, according to claim 2, wherein: the temperature in the reaction kettle 1 is 20-60 ℃; the stirring time in the reaction kettle 1 is 2-5 h.
5. The reaction system for the synthesis of 2-chloro-5-chloromethylthiazole, according to claim 1, wherein: an air inlet 104 is arranged at the right side position of the top of the reaction kettle 1; a heat exchanger 302 is arranged outside the mixing device 3; a feeding hole 301 is formed in the right side position of the top of the mixing device 3; the reaction devices are connected through pipelines.
6. The reaction system for the synthesis of 2-chloro-5-chloromethylthiazole, according to claim 1, wherein: a hydraulic pump 5 is arranged between the reaction kettle 1 and the rectifying tower 2; a hydraulic pump 5 is arranged between the rectifying tower 2 and the circulating pump 4; and a circulating pump 4 is arranged between the reaction kettle 1 and the mixing device 3.
7. The reaction system for the synthesis of 2-chloro-5-chloromethylthiazole, according to claim 1, wherein: a dispersing device 101 is arranged in the middle of the top of the reaction kettle 1; a plurality of round holes 105 are arranged on the dispersion device 101; the ejector 102 is arranged at the top of the reaction kettle 1; the ejector 102 is arranged at the lower end of the stop valve 103; the stop valve 103 is arranged on a pipeline outside the top of the reaction kettle 1.
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