CN115490608A - Production method of propachlor - Google Patents
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Abstract
The invention provides a production method of propyzamide, belonging to the technical field of pesticide production and comprising the following steps: sequentially adding N-isopropyl aniline and an organic solvent into a reaction kettle, then stirring and dropwise adding chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100-105 ℃ after dropwise adding is finished, preserving heat and refluxing for 4.5-6 hours, washing with water, separating, and performing suction filtration to obtain a propachlor product; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 65-80 ℃. The production method solves the problems of multiple types of byproducts, large generation amount, low product purity and yield, low utilization rate of reaction raw materials, high difficulty in wastewater treatment and high production cost in the existing toxapham production. The method has the advantages of simple operation, short preparation period, few byproducts, easy purification, high yield, high utilization rate of raw materials and easy treatment of waste, and the prepared toxapham has high purity and low impurity content.
Description
Technical Field
The invention relates to the technical field of pesticide production, in particular to a production method of propyzamide.
Background
Propachlor, also known as: 2-chloro-N- (1-methylethyl) -N-phenylacetamide, N-isopropyl-2-chloroacetanilide, N-isopropyl-chloroacetanilide; CAS number 1918-16-7, molecular formula C 11 H 14 ClNO, molecular weight 211.68796, melting point 67-76 deg.C, boiling point 110 deg.C (0.004 kPa), is slightly soluble in water, is usually a pale tan crystalline powder solid, and is stable at normal temperature and pressure.
The thamnine is a high-efficiency, low-toxicity, drought-resistant and harmless herbicide,A dual-purpose herbicide for paddy field is an amide-type selective preemergence herbicide with wide herbicidal spectrum, and is used for crops such as rice, cotton, corn, peanut, cane, rape and beans. The toxaphamine has the dosage form of 10 percent or 20 percent wettable powder and 30 percent emulsifiable concentrate, is suitable for soil application, can inhibit the growth of weed roots or seedlings, effectively controls annual monocotyledonous and partial dicotyledonous weeds such as barnyard grass, green bristlegrass and amaranth, has poor effect on purslane, crab grass, polygonum and the like, has no effect on perennial weeds, is safe to use, and is not easy to generate phytotoxicity. The application dosage of the toxaphamine is 35-50g/100m 2 At this dose, it has a residual life in soil of about 30 days. The molecular mechanism of action of propachlor is unknown, and researches report that propachlor inhibits cell division mainly by inhibiting protein synthesis.
However, the production process of the product on the market at present usually adopts hydrochloric acid gas and propylene to synthesize 2-chloropropane, then uses aniline and 2-chloropropane to prepare N-isopropyl aniline, and finally uses N-isopropyl aniline and chloroacetyl chloride to prepare the clomazone. However, in the above-mentioned production scheme, a large amount of by-products such as N-isopropyl aniline hydrochloride, 2,2-dichloro-N-isopropyl acetanilide (C) are easily produced 12 H 15 Cl 2 NO, CAS No. 39105-95-8), and the like, and the purity of the product thamnazin can only reach more than 80%, the yield also only reaches more than 80%, the raw materials in the reaction system react insufficiently and have a large amount of residue, the utilization rate of the raw materials is low, the treatment difficulty of the reaction wastewater is high, and the environmental protection cost and the production cost of enterprises are increased.
Disclosure of Invention
The invention provides a production method of propachlor, which is used for solving the problems of multiple types of byproducts, large generation amount, low product purity and yield, low utilization rate of reaction raw materials, high difficulty in wastewater treatment and high production cost in the existing propachlor production.
The invention provides a production method of propachlor, which comprises the following steps: sequentially adding N-isopropyl aniline and an organic solvent into a reaction kettle, then stirring and dropwise adding chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100-105 ℃ after dropwise adding is finished, preserving heat and refluxing for 4.5-6 hours, washing with water, separating, and performing suction filtration to obtain a propachlor product; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 65-80 ℃.
The method has the advantages of simple operation, short preparation period, few byproducts, easy purification, high yield, high raw material utilization rate and easy treatment of waste, the prepared toxaphamine has high purity and low impurity content, can be used as a toxaphamine standard substance, is applied to qualitative and quantitative research and detection of the toxaphamine, has certain significance for quality control of the toxaphamine and related preparations thereof, and can also be directly popularized in the market.
Further, the weight ratio of the N-isopropyl aniline to the chloroacetyl chloride is 1.1-1.3.
Further, the weight ratio of the N-isopropyl aniline to the organic solvent is 1.7-1.9.
Preferably, the organic solvent is at least one of toluene, benzene and carbon tetrachloride. More preferably, the organic solvent is toluene, and the purity of toluene is not less than 99.5%.
Further, the stirring speed of the chloracetyl chloride is 200-500rpm, and the dropping speed is 0.5-2kg/min in the stirring and dropping operation of the chloracetyl chloride. In the stirring and dripping operation, the dripping speed is controlled within a reasonable range, and the slow dripping is more favorable for generating the target product of the clodinafop-propargyl.
Compared with the prior art, the method is characterized in that the organic solvent is added into the reaction kettle before the chloroacetyl chloride is dripped, instead of adding the organic solvent to extract the target product during water washing separation as in the prior art, the improvement of the method enables the reaction substrate N-isopropyl aniline in the reaction kettle to be diluted and dispersed by the organic solvent, the dispersion degree of the N-isopropyl aniline is higher, multiple acylation of the same aromatic ring caused by overlarge local concentration after the chloroacetyl chloride is dripped can be effectively avoided, the generation amount of reaction byproducts is reduced, the purity and yield of the target product are improved, and potential safety hazards caused by obvious temperature rise caused by severe local reaction can be prevented.
The specific operation of the water washing is further set as follows: cooling the reaction material after the heat preservation and reflux is finished to be below 80 ℃, adding water into the reaction kettle, and then stirring and washing for 1-1.5h.
Further, the weight ratio of the N-isopropyl aniline to the water is 2.2-2.4.
It is further set that the specific operations of separation are: cooling the reaction material after water washing to below 70 ℃, adding sodium carbonate into the reaction kettle, adjusting the pH of the reaction material to 6.5-7, standing for layering for 0.5-1h, then discharging the upper water phase to a wastewater pool, and reserving the lower oil phase for later use.
Further, the specific operations of the suction filtration are as follows: cooling the lower oil phase to 0-2 deg.C, maintaining the temperature for 0.5-2h, vacuum filtering to remove organic solvent, and crystallizing to obtain the final product.
Further setting the cooling speed of cooling to be 10-20 ℃/h; the vacuum degree of vacuum filtration is 0.04-0.06MPa, and the time is 10-30min. The cooling is favorable for cooling and crystallizing the toxaphamine, the crystal form can be controlled by controlling the cooling speed, and the toxaphamine product with more stable crystal form can be obtained.
Further set up is that the yield of the propyzamide product is at least 85.0%.
Further, the purity of the N-isopropyl aniline is not less than 99.5%, and the purity of the chloroacetyl chloride is not less than 99.0%.
The invention also aims to provide the thamnine, which is prepared by the production method and has the purity of at least 98.0%. The production method simplifies the process steps while obtaining the high-purity and high-yield thamnine product, is easy to recycle and separate reagents, has mild reaction conditions and low system energy consumption, and achieves the purposes of emission reduction and energy conservation.
Further setting that the purity of the propachlor product is more than or equal to 98.5 percent.
Furthermore, the water content of the thaumatin product is less than or equal to 0.1 percent, the pH value is 6.5-7, the content of acetone insoluble substances is less than or equal to 0.1 percent, and the thaumatin product is white crystal powder in appearance.
The production method of the thamnine provided by the invention realizes the following effects by controlling the conditions such as the adding sequence, the temperature, the time and the like of the reaction materials:
1) The method has the advantages of simple operation, short preparation period, few byproducts, high product purity, high yield, high raw material utilization rate and easy treatment of waste and sewage, improves the conversion rate of raw materials, has good product selectivity, ensures that the prepared toxoramine has high purity and low impurity content, can be used as a toxoramine standard substance, is applied to qualitative and quantitative research and detection of the toxoramine, has certain significance on the quality control of the toxoramine and related preparations thereof, can be directly popularized in the market, and has the advantages of wide herbicidal spectrum, convenient use, safe growth of rice seedlings and the like.
2) The production method has the advantages of simplified process steps, mild reaction conditions, stable process, good reproducibility, reduced and reduced raw material consumption, easy recovery and separation of reagents, low system energy consumption, reduced byproduct generation amount, corresponding reduction of pollutants in wastewater, great reduction of wastewater treatment difficulty, achievement of the environmental protection aims of emission reduction and energy conservation, reduction of production cost, and good stability performance, high purity and high yield of the obtained toxamine product.
The invention adopts the technical scheme to provide the production method of the toxaphamine, which makes up the defects of the prior art, and has reasonable design and convenient operation.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without any inventive step, also belong to the scope of protection of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Those skilled in the art who do not specify any particular technique or condition in the examples can follow the techniques or conditions described in the literature in this field or follow the product specification.
The invention provides a production method of propyzamide, which comprises the following steps: sequentially adding N-isopropyl aniline and an organic solvent into a reaction kettle, then stirring and dropwise adding chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100-105 ℃ after dropwise adding is finished, preserving heat and refluxing for 4.5-6 hours, washing with water, separating, and performing suction filtration to obtain a propachlor product; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 65-80 ℃.
In a specific embodiment, the synthetic route for propyzamide is as follows:
in one embodiment, the weight ratio of N-isopropylaniline to chloroacetyl chloride is 1.1 to 1.3.
In one embodiment, the weight ratio of N-isopropylaniline to organic solvent is from 1.7 to 1.9.
Preferably, the organic solvent is at least one of toluene, benzene, carbon tetrachloride. More preferably, the organic solvent is toluene, and the purity of toluene is not less than 99.5%.
In one embodiment, the chloroacetyl chloride is added dropwise with stirring at a rate of 200 to 500rpm, and at a rate of 0.5 to 2kg/min. In the stirring and dripping operation, the dripping speed is controlled within a reasonable range, and the slow dripping is more favorable for generating the target product of the clodinafop-propargyl.
The method has the advantages of simple operation, short preparation period, few byproducts, easy purification, high yield, high raw material utilization rate and easy treatment of waste, the prepared toxaphamine has high purity and low impurity content, can be used as a toxaphamine standard substance, is applied to qualitative and quantitative research and detection of the toxaphamine, has certain significance for quality control of the toxaphamine and related preparations thereof, and can also be directly popularized in the market.
Compared with the prior art, the method is characterized in that the organic solvent is added into the reaction kettle before the chloroacetyl chloride is dripped, instead of adding the organic solvent to extract the target product during water washing separation as in the prior art, the improvement of the method enables the reaction substrate N-isopropyl aniline in the reaction kettle to be diluted and dispersed by the organic solvent, the dispersion degree of the N-isopropyl aniline is higher, multiple acylation of the same aromatic ring caused by overlarge local concentration after the chloroacetyl chloride is dripped can be effectively avoided, the generation amount of reaction byproducts is reduced, the purity and yield of the target product are improved, and potential safety hazards caused by obvious temperature rise caused by severe local reaction can be prevented.
In one embodiment, a method for producing propachlor includes the steps of:
1) Adding N-isopropyl aniline and an organic solvent into a reaction kettle, then stirring and dropwise adding chloroacetyl chloride into the reaction kettle, after dropwise adding is completed, heating the reaction materials in the reaction kettle to 100-105 ℃, and carrying out heat preservation and reflux for 4.5-6 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 65-80 ℃, the stirring speed is 200-500rpm, and the dropping speed is 0.5-2kg/min.
Wherein the weight ratio of the N-isopropyl aniline to the chloroacetyl chloride is 1.1-1.3. The weight ratio of the N-isopropyl aniline to the organic solvent is 1.7-1.9. The organic solvent is at least one of toluene, benzene and carbon tetrachloride.
2) Cooling the reaction material after the heat preservation and reflux is finished to be below 80 ℃, adding water into the reaction kettle, and then stirring and washing for 1-1.5h. Wherein the weight ratio of the N-isopropyl aniline to the water is 2.2-2.4.
3) Cooling the reaction material after water washing to below 70 ℃, adding sodium carbonate into the reaction kettle, adjusting the pH of the reaction material to 6.5-7, standing for layering for 0.5-1h, then discharging the upper water phase to a wastewater pool, and reserving the lower oil phase for later use.
4) Cooling the lower oil phase to 0-2 deg.C, maintaining the temperature for 0.5-2h, vacuum filtering to remove organic solvent, and crystallizing to obtain the final product. Wherein the cooling speed of cooling is 10-20 ℃/h; the vacuum degree of vacuum filtration is 0.04-0.06MPa, and the time is 10-30min.
As another embodiment, the production of propyzamide comprises the following steps: sequentially adding N-isopropyl aniline and toluene into a reaction kettle, adding triethylamine and L-cysteine hydrochloride into the reaction kettle, uniformly stirring, dropwise adding chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100-105 ℃ after dropwise adding, preserving heat, refluxing for 4.5-6h, washing with water, separating, and performing suction filtration to obtain a propachlor product; in the stirring and dripping process, controlling the temperature of reaction materials in the reaction kettle to be 65-80 ℃; the addition amounts of triethylamine and L-cysteine hydrochloride are 0.5-3.0% and 0.1-1.0% of the weight of N-isopropyl aniline, respectively. The triethylamine and the L-cysteine hydrochloride are added into the reaction system, so that the selectivity of the N-isopropyl aniline and the chloroacetyl chloride is improved possibly in a synergistic manner, the occurrence of side reactions is effectively inhibited, the acylation degree of amino groups on the N-isopropyl aniline is improved, the multiple acylation of the N-isopropyl aniline is avoided, the utilization rate of raw materials is improved, the yield and the purity of the target product coumarone are improved, and the triethylamine and the L-cysteine hydrochloride have the advantages of low price and simple post-treatment.
It should be noted that one of the reaction products of N-isopropyl aniline and chloroacetyl chloride is hydrogen chloride, and during the reaction, the hydrogen chloride gas is timely discharged and recovered by the reaction kettle through a hydrochloric acid gas tail gas pipeline, and meanwhile, part of the hydrogen chloride dissolved in the reaction material can be removed through washing, separation and other operations.
The present invention will be described in further detail with reference to examples.
Example 1:
a production method of propachlor comprises the following steps:
1) Adding 675kg of N-isopropylaniline and 1200kg of toluene into a 5000L reaction kettle, then stirring and dropwise adding 600kg of chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100 ℃ after the dropwise adding is finished, and carrying out heat preservation and reflux for 5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 80 ℃, the stirring speed is 400rpm, and the dropping speed is 0.5kg/min.
2) And cooling the reaction material after the heat preservation and reflux are finished to be below 80 ℃, adding 300kg of water into the reaction kettle, and then stirring and washing for 1h.
3) Cooling the reaction material after water washing to below 70 ℃, adding sodium carbonate into the reaction kettle, adjusting the pH of the reaction material to 6.5-7, standing for layering for 1h, then discharging the upper water phase to a wastewater tank, and reserving the lower oil phase for later use.
4) And cooling the lower oil phase, keeping the temperature for 1h after cooling to 0-2 ℃, and then removing the organic solvent by vacuum filtration to obtain crystals, namely the propachlor product. Wherein the cooling speed of cooling is 10 ℃/h; the vacuum degree of vacuum filtration is 0.04MPa, and the time is 30min.
The yield of the thamnine product obtained in this example was 812.80kg, the yield was 85.4%, and the purity was 98.7%.
Example 2:
a production method of propachlor comprises the following steps:
1) 725kg of N-isopropyl aniline and 1350kg of toluene are added into a 5000L reaction kettle, 655kg of chloroacetyl chloride is dropwise added into the reaction kettle while stirring, after dropwise addition is completed, the temperature of reaction materials in the reaction kettle is raised to 105 ℃, and heat preservation and reflux are carried out for 4.5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 70 ℃, the stirring speed is 450rpm, and the dropping speed is 1kg/min.
2) And cooling the reaction material after the heat preservation and the reflux are finished to be below 80 ℃, adding 320kg of water into the reaction kettle, and then stirring and washing for 1.5 hours.
3) Cooling the reaction material after water washing to below 70 ℃, adding sodium carbonate into the reaction kettle, adjusting the pH of the reaction material to 6.5-7, standing for layering for 0.5h, then discharging the upper water phase to a wastewater tank, and reserving the lower oil phase for later use.
4) And cooling the lower oil phase, keeping the temperature for 1.5h after cooling to 0-2 ℃, and then removing the organic solvent by vacuum filtration to obtain crystals, namely the propachlor product. Wherein the cooling speed of cooling is 15 ℃/h; the vacuum degree of vacuum filtration is 0.05MPa, and the time is 20min.
The yield of the fenchloramine product obtained in the embodiment is 920.96kg, the yield is 86.1%, and the purity is 98.8%.
Example 3:
in this example, during the production of propyzamide, the influence of different organic solvents on the yield, yield and purity of propyzamide products was tested, and the specific test conditions are as follows:
in step 1) on the basis of example 1, replacing the weight of toluene and the like with benzene (test example 1) and carbon tetrachloride (test example 2), and then dropwise adding chloroacetyl chloride into the reaction kettle while stirring for reaction to produce the toxapham product. Comparing the results, analyzing the effect of different organic solvents on the reaction, the results are shown in table 1. Each test group was provided with 3 replicates and the average was taken.
TABLE 1 results of the effect of organic solvents on the production of propyzamide products
| Yield kg | Yield% | Purity% | |
| Example 1 | 812.80 | 85.4 | 98.7 |
| Test example 1 | 807.40 | 83.2 | 96.8 |
| Test example 2 | 778.15 | 80.6 | 97.3 |
The results show that the yield, the yield and the product purity are optimal when the organic solvent is toluene, and the method is more favorable for obtaining high-yield and high-purity picrasm products.
Example 4:
in this embodiment, during the production of clomazone, experiments were performed on the influence of different temperatures of reaction materials in a reaction kettle on the yield, yield and purity of clomazone products in the process of dropwise adding chloroacetyl chloride under stirring, and specific test conditions were as follows:
on the basis of example 1, in the step 1), in the stirring and dropping process of chloroacetyl chloride, the temperature of the reaction materials in the reaction kettle is controlled to be 90 ℃ (experimental example 1), 65 ℃ (experimental example 2) and 60 ℃ (experimental example 3), the stirring speed is 400rpm, the dropping speed is 0.5kg/min, and the reaction materials in the reaction kettle are heated to 100 ℃ and are kept at the temperature for refluxing for 5 hours after the stirring and dropping are finished. Comparing the results, analyzing the effect of different temperatures on the reaction, the results are shown in Table 2. Each test group was provided with 3 replicates and the average was taken.
TABLE 2 influence results of different stirring dropping temperatures on the production of propyzamide
| Yield kg | Yield% | Purity% | |
| Example 1 | 812.80 | 85.4 | 98.7 |
| Test example 1 | 812.55 | 85.2 | 98.5 |
| Test example 2 | 835.14 | 85.1 | 98.5 |
| Test example 3 | 811.59 | 71.3 | 80.2 |
From the results, it can be seen that the results of example 1 and test examples 1 and 2 are not significantly different, and are only significantly different from the results of test example 3, which shows that it is feasible to control the temperature at 65-80 ℃ during the stirring and dropping process of chloroacetyl chloride, and it is possible to save the energy consumption of the system without controlling the temperature at 90 ℃ for a long time, and when the temperature is lower than 65 ℃, the yield and purity of the clomazone product are not good.
Example 5:
in this embodiment, when performing the production of propyzamide, on the basis of embodiment 1, the step 1) is adjusted to: adding 675kg of N-isopropylaniline and 1200kg of toluene into a 5000L reaction kettle, adding 10.13kg of triethylamine and 3.38kg of L-cysteine hydrochloride into the reaction kettle, stirring uniformly, dropwise adding 600kg of chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100 ℃ after dropwise adding, and carrying out heat preservation and reflux for 5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 80 ℃, the stirring speed is 400rpm, and the dropping speed is 0.5kg/min.
Example 6:
in this embodiment, when performing the production of propyzamide, on the basis of embodiment 1, the step 1) is adjusted to: adding 675kg of N-isopropylaniline and 1200kg of toluene into a 5000L reaction kettle, adding 10.13kg of triethylamine into the reaction kettle, stirring uniformly, dropwise adding 600kg of chloroacetyl chloride into the reaction kettle, heating the reaction material in the reaction kettle to 100 ℃ after dropwise adding, and carrying out heat preservation and reflux for 5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 80 ℃, the stirring speed is 400rpm, and the dropping speed is 0.5kg/min.
Example 7:
in this embodiment, when performing the production of propyzamide, on the basis of embodiment 1, the step 1) is adjusted to: adding 675kg of N-isopropylaniline and 1200kg of toluene into a 5000L reaction kettle, adding 3.38kg of L-cysteine hydrochloride into the reaction kettle, uniformly stirring, dropwise adding 600kg of chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100 ℃ after dropwise adding, and carrying out heat preservation and reflux for 5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 80 ℃, the stirring speed is 400rpm, and the dropping speed is 0.5kg/min.
Example 8:
in this embodiment, when performing the production of propyzamide, on the basis of embodiment 1, the step 1) is adjusted to: adding 675kg of N-isopropylaniline and 1200kg of toluene into a 5000L reaction kettle, adding 2.7kg of triethylamine and 0.61kg of L-cysteine hydrochloride into the reaction kettle, stirring uniformly, dropwise adding 600kg of chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100 ℃ after dropwise adding, and carrying out heat preservation and reflux for 5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 80 ℃, the stirring speed is 400rpm, and the dropping speed is 0.5kg/min.
Example 9:
in this embodiment, when performing the production of propyzamide, on the basis of embodiment 1, the step 1) is adjusted to: adding 675kg of N-isopropylaniline and 1200kg of toluene into a 5000L reaction kettle, adding 20.93kg of triethylamine and 7.43kg of L-cysteine hydrochloride into the reaction kettle, stirring uniformly, dropwise adding 600kg of chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100 ℃ after dropwise adding, and carrying out heat preservation and reflux for 5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 80 ℃, the stirring speed is 400rpm, and the dropping speed is 0.5kg/min.
The production of clomazone was carried out according to the methods of examples 5 to 9, and the produced clomazone products were analyzed to compare the effect of the different methods on clomazone production, the results of which are shown in Table 3. Each test group was provided with 3 replicates and the average was taken.
TABLE 3 results of the effect of different production methods on the production of propyzamide
| Yield kg | Yield% | Purity% | |
| Example 1 | 812.80 | 85.4 | 98.7 |
| Example 5 | 845.63 | 89.3 | 99.2 |
| Example 6 | 820.29 | 86.1 | 98.6 |
| Example 7 | 813.50 | 85.3 | 98.5 |
| Example 8 | 798.62 | 83.4 | 98.1 |
| Example 9 | 793.60 | 82.2 | 97.3 |
From the results, it can be seen that the method of example 5 produces thaumatin in higher yield, yield and purity than the method of example 1. Compared with the example 5 and the example 7, the results show that the triethylamine and the L-cysteine hydrochloride have a certain synergistic effect, so that the selectivity of the N-isopropyl aniline and the chloroacetyl chloride is improved, the acylation degree of amino groups on the N-isopropyl aniline is improved, the multiple acylation of the N-isopropyl aniline is avoided, the utilization rate of raw materials is improved, and the yield and the purity of the target product, namely the fenugreek amine, are improved. Comparing example 5 with example 8 and example 9, it is demonstrated that the addition of triethylamine and L-cysteine hydrochloride in the range defined in the present invention has a positive effect on the production of oxamine, and that the addition of triethylamine and L-cysteine hydrochloride in the range not defined in the present invention has a negative effect on the production of oxamine, so that the addition of triethylamine and L-cysteine hydrochloride is controlled to 0.5-3.0% and 0.1-1.0% by weight of N-isopropylaniline, respectively.
Example 10:
a production method of propachlor comprises the following steps:
1) Adding 675kg of N-isopropyl aniline into a 5000L reaction kettle, then stirring and dropwise adding 600kg of chloroacetyl chloride into the reaction kettle, heating the reaction materials in the reaction kettle to 100 ℃ after dropwise adding, and carrying out heat preservation and reflux for 5 hours; in the stirring and dropping process, the temperature of the reaction materials in the reaction kettle is controlled to be 80 ℃, the stirring speed is 400rpm, and the dropping speed is 0.5kg/min.
2) After cooling the reaction material after the heat preservation and reflux is finished to be below 80 ℃, adding 300kg of water and 1200kg of toluene into the reaction kettle, and then stirring and washing for 1h.
3) Cooling the reaction material after water washing to below 70 ℃, adding sodium carbonate into the reaction kettle, adjusting the pH of the reaction material to 6.5-7, standing for layering for 1h, then discharging the upper water phase to a wastewater tank, and reserving the lower oil phase for later use.
4) And cooling the lower oil phase, keeping the temperature for 1h after cooling to 0-2 ℃, and then removing the organic solvent by vacuum filtration to obtain crystals, namely the propachlor product. Wherein the cooling speed of cooling is 10 ℃/h; the vacuum degree of vacuum filtration is 0.04MPa, and the time is 30min.
The yield of the thamnine product obtained in this example was 698.93kg, the yield was 74.3% and the purity was 95.7%. Compared with the example 1, the organic solvent is added to extract the target product during water washing separation in the embodiment, and the yield and the purity of the obtained propyzamide product are obviously different from those of the example 1, so that the organic solvent is added into the reaction kettle before chloroacetyl chloride, the reaction substrate N-isopropyl aniline in the reaction kettle is diluted and dispersed by the organic solvent, the dispersion degree of the N-isopropyl aniline is higher, multiple acylation of the same aromatic ring caused by overlarge local concentration after the chloroacetyl chloride is dripped can be effectively avoided, the generation amount of reaction byproducts is reduced, and the purity and the yield of the target product are improved.
It should be noted that, in the present invention, concentrations, ratios, and the like which are not specifically described are weight concentrations, weight ratios, and the like, which belong to the common writing habits of those skilled in the art, and therefore, are not described in detail herein.
It should be noted that, in the present invention, the detailed steps of some operations are not detailed, but belong to the prior art known to those skilled in the art, and therefore, are not described herein again.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; while the invention has been described in detail and with reference to the foregoing embodiments, those skilled in the art will appreciate that; the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The production method of the toxaphamine is characterized by comprising the following steps: the method comprises the following steps: sequentially adding N-isopropyl aniline and an organic solvent into a reaction kettle, then stirring and dropwise adding chloroacetyl chloride into the reaction kettle, after dropwise adding is completed, heating the reaction materials in the reaction kettle to 100-105 ℃, carrying out heat preservation and reflux for 4.5-6h, washing with water, separating, and carrying out suction filtration to obtain a propachlor product;
and in the stirring and dripping process, controlling the temperature of reaction materials in the reaction kettle to be 65-80 ℃.
2. The method for producing propyzamide according to claim 1, wherein the production process comprises the following steps: the weight ratio of the N-isopropyl aniline to the chloroacetyl chloride is 1.1-1.3.
3. The method for producing propyzamide according to claim 1, wherein the production process comprises the following steps: the weight ratio of the N-isopropyl aniline to the organic solvent is 1.7-1.9.
4. The method for producing propyzamide according to claim 1, wherein the method comprises the following steps: the organic solvent is at least one of toluene, benzene and carbon tetrachloride.
5. The method for producing propyzamide according to claim 1, wherein the production process comprises the following steps: in the stirring and dripping operation of the chloracetyl chloride, the stirring speed is 200-500rpm, and the dripping speed is 0.5-2kg/min.
6. The method for producing propyzamide according to claim 1, wherein the production process comprises the following steps: the concrete operation of washing is as follows: cooling the reaction material after the heat preservation and reflux is finished to be below 80 ℃, adding water into the reaction kettle, and then stirring and washing for 1-1.5h.
7. The method for producing propyzamide according to claim 6, wherein the production method comprises the following steps: the weight ratio of the N-isopropyl aniline to the water is 2.2-2.4.
8. The method for producing propyzamide according to claim 1, wherein the production process comprises the following steps: the specific operation of the separation is as follows: cooling the reaction material after water washing to below 70 ℃, adding sodium carbonate into the reaction kettle, adjusting the pH of the reaction material to 6.5-7, standing for layering for 0.5-1h, then discharging the upper water phase to a wastewater pool, and reserving the lower oil phase for later use.
9. The method for producing propyzamide according to claim 8, wherein the production process comprises the following steps: the concrete operation of suction filtration is as follows: cooling the lower oil phase to 0-2 deg.C, maintaining the temperature for 0.5-2h, vacuum filtering to remove organic solvent, and crystallizing to obtain the final product.
10. The method for producing propyzamide according to claim 9, wherein: the cooling speed of the cooling is 10-20 ℃/h; the vacuum degree of the vacuum filtration is 0.04-0.06MPa, and the time is 10-30min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2304615A1 (en) * | 1972-08-28 | 1974-03-21 | Nitrokemia Ipartelepek | N-isopropyl chloroacetanilide prodn - by chloroacetylation of N-isopropylaniline |
| CN110117233A (en) * | 2018-02-05 | 2019-08-13 | 潍坊中农联合化工有限公司 | A kind of synthetic method of chloroacetamide-based compounds |
-
2022
- 2022-10-19 CN CN202211282180.8A patent/CN115490608A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2304615A1 (en) * | 1972-08-28 | 1974-03-21 | Nitrokemia Ipartelepek | N-isopropyl chloroacetanilide prodn - by chloroacetylation of N-isopropylaniline |
| CN110117233A (en) * | 2018-02-05 | 2019-08-13 | 潍坊中农联合化工有限公司 | A kind of synthetic method of chloroacetamide-based compounds |
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| PENG DU等: ""Design, Synthesis, and Evaluation of Indolebutylamines as a Novel Class of Selective Dopamine D3 Receptor Ligands"", 《CHEM BIOL DRUG DES》, vol. 82, pages 326 - 335, XP072380199, DOI: 10.1111/cbdd.12158 * |
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