CN107935970B - Preparation method of high-purity low-water-content 3-methylamine tetrahydrofuran - Google Patents
Preparation method of high-purity low-water-content 3-methylamine tetrahydrofuran Download PDFInfo
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Abstract
The invention discloses a preparation method of high-purity low-water content 3-methylamine tetrahydrofuran, which comprises the following steps: 1) reacting liquid ammonia and 3-formaldehyde tetrahydrofuran in the presence of anhydrous methanol to prepare an imine intermediate; 2) reacting the imine intermediate with hydrogen in the presence of a catalyst, cooling after the reaction is finished, filtering reaction liquid to remove the catalyst, transferring the reaction liquid to a distillation kettle, distilling to recover ammonia and methanol, heating for distillation, wherein the temperature in the kettle is 75-80 ℃, the temperature at the top of the kettle is 65-75 ℃, and collecting fractions, namely 3-methylamine tetrahydrofuran. Compared with the prior art, the prepared 3-methylamine tetrahydrofuran has higher purity and lower water content, provides an intermediate with excellent quality for further synthesizing other chemical products by utilizing the 3-methylamine tetrahydrofuran, and the raw materials of the invention are recycled, thereby not only reducing the production cost, but also saving energy and protecting environment, and conforming to the current concept of green chemistry.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of high-purity low-water-content 3-methylamine tetrahydrofuran.
Background
3-methylamine tetrahydrofuran is an important intermediate for synthesizing third-generation nicotine pesticide dinotefuran and other novel drugs, dinotefuran is developed by Mitsui corporation of Japan, is first registered and marketed in Japan in 2002, and is currently registered as pesticide in a plurality of countries. Due to the special structure, compared with the traditional nicotine pesticide, the dinotefuran has more excellent performance, excellent systemic osmosis effect and high insecticidal activity at a very low dosage. Therefore, the dinotefuran is safe to animals and plants, long in residual effect and wide in insecticidal spectrum, and is suitable for preventing and controlling pests such as orthoptera, hymenoptera, diptera, beetle, hemiptera, lepidoptera and the like of rice, vegetables, fruit trees and flowers.
Dinotefuran has a wide insecticidal spectrum, is safe to crops, people, livestock and environment, and is expected to become a large-scale worldwide pesticide by matching with application methods with various purposes, the market demand at home and abroad is increased rapidly at present, and 3-methylamine tetrahydrofuran is used as a key intermediate for synthesizing dinotefuran, and the demand of each ton of dinotefuran is 0.63 ton. At present, the demand of 3-methylamine tetrahydrofuran in the domestic medicine market is about 500 tons each year, the demand of the foreign market is more than 1700 tons, the total demand is estimated to be about 2200 tons in the domestic market, the demand of the foreign market is increased at a speed of 20-25% every year, and the demand of the foreign market is about 3800 tons, but the problems of low purity and high water content generally exist in the 3-methylamine tetrahydrofuran prepared by the prior art, which causes a barrier for the next synthesis, so that the research of a preparation method of the 3-methylamine tetrahydrofuran with high purity and low water content is urgently needed.
To solve this problem, research and study have been conducted on the production and life of people for a long time. For example, the chinese patent application discloses a method for preparing 3-methylamine tetrahydrofuran [ application No.: 201510447636.5], the invention comprising: (1) and (3) cyclization reaction: 1, 4-butylene glycol is taken as a raw material, and 2, 5-dihydrofuran is prepared by dehydration and cyclization under the catalytic action of solid acid; (2) hydroformylation reaction: reacting the 2, 5-dihydrofuran obtained in the step (1) with water gas under the catalytic action of cobalt acetate to generate 3-tetrahydrofuryl aldehyde; (3) hydrogenation reaction: and (3) reacting the 3-tetrahydrofuryl aldehyde obtained in the step (2) with ammonia and hydrogen under the catalytic action of 5% Pd/C to obtain the target product 3-methylamine tetrahydrofuran.
The invention provides a method for synthesizing 3-methylamine tetrahydrofuran, but the purity of the product prepared by the method still needs to be improved, and the conversion rate of the reaction is low, which results in higher production cost.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a method for preparing 3-methylamine tetrahydrofuran with high purity and low water content.
The preparation method of the high-purity low-water content 3-methylamine tetrahydrofuran is characterized by comprising the following steps of:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, sequentially adding liquid ammonia and 3-formaldehyde tetrahydrofuran while stirring and cooling, and stirring and reacting under the protection of nitrogen to obtain an imine intermediate;
step two: adding a catalyst and the imine intermediate prepared in the step one into a reaction kettle, stirring and heating under the protection of nitrogen, introducing hydrogen, and continuously heating for reaction until the reaction is finished;
step three: cooling, filtering the reaction liquid to remove the catalyst, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, decompressing to the degree of vacuum in the kettle of-0.095 MPa to-0.075 MPa, heating and distilling, wherein the temperature in the kettle is 70-75 ℃ and the temperature at the top of the kettle is 40-50 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes smoothly, decompressing to the degree of vacuum in the kettle of-0.1 MPa to-0.09 MPa, heating and distilling, wherein the temperature in the kettle is 75-80 ℃ and the temperature at the top of the kettle is 65-75 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
The preparation method of the high-purity low-water content 3-methylamine tetrahydrofuran is characterized in that the temperature of a reaction system is controlled not to exceed 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction in the step one.
The preparation method of the high-purity low-water content 3-methylamine tetrahydrofuran is characterized in that the temperature of a reaction system is controlled to be-10-0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction in the step one.
The preparation method of the high-purity low-water content 3-methylamine tetrahydrofuran is characterized in that the catalyst in the second step is palladium carbon or Raney nickel.
The preparation method of the high-purity low-water content 3-methylamine tetrahydrofuran is characterized in that the temperature of introducing hydrogen in the step two is 35-40 ℃, the pressure of hydrogen in a reaction kettle is 1.0-2.0MPa, the reaction temperature after introducing the hydrogen is 65-75 ℃, and the reaction time is 3-5 h.
The preparation method of the high-purity low-water content 3-methylamine tetrahydrofuran is characterized in that the mass ratio of the 3-formaldehyde tetrahydrofuran to the liquid ammonia to the catalyst is 1:1.2-1.5: 0.03-0.1.
The preparation method of the 3-methylamine tetrahydrofuran with high purity and low water content is characterized in that the GC purity of the 3-methylamine tetrahydrofuran is more than 99.0 percent, and the water content is less than 0.2 percent.
The reaction equation of the present invention is as follows:
by adopting the technology, compared with the prior art, the invention has the advantages that:
1) compared with the prior art, the 3-methylamine tetrahydrofuran prepared by the invention has higher purity and lower water content, and provides an intermediate with excellent quality for further synthesizing other chemical products by utilizing the 3-methylamine tetrahydrofuran;
2) the ammonia gas, the methanol, the catalyst and other reagents utilized by the invention can be recycled, so that the production cost is reduced, the energy is saved, the environment is protected, and the current green chemical concept is met;
3) the normal hexane is added after the reaction is finished for removing water, so that the water content in the product is greatly reduced, and the normal hexane is recovered after the reaction is finished, so that the cost is reduced;
4) compared with the prior art that the hydroxylamine compound or ammonia water is used as the amination reagent, the method has higher amination rate and reduces the generation of by-products, thereby improving the conversion rate of the reaction and the purity of the product.
Drawings
FIG. 1 is a gas chromatogram of the product produced in application example 1;
FIG. 2 is a gas chromatogram of the product produced in application example 2;
FIG. 3 is a gas chromatogram of the product produced in application example 3;
Detailed Description
The reagents used in the following examples, unless otherwise specified, were purchased from conventional biochemical reagent stores.
Example 1
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.2 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.1 part by mass of palladium-carbon and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 35 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 1.0MPa, and continuously heating to 65 ℃ for reaction for 3 hours;
step three: cooling, filtering the reaction liquid to remove palladium carbon, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, reducing the pressure to the vacuum degree of-0.095 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 75 ℃ and the temperature at the top of the kettle is 50 ℃, transferring the obtained fraction to another distillation kettle, adding n-hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the n-hexane after the moisture content changes gently, reducing the pressure to the vacuum degree of-0.1 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 80 ℃ and the temperature at the top of the kettle is 75 ℃, collecting the fraction, namely the 3-methylamine tetrahydrofuran, and the gas chromatogram of the fraction is shown in figure 1.
The reaction equation of the present invention is as follows:
the method comprises the steps of carrying out amination reaction on 3-formaldehyde tetrahydrofuran serving as a reaction starting material and ammonia gas in an anhydrous methanol solution to generate an imine intermediate, keeping the system temperature below 0 ℃ in the whole process to avoid over violent reaction, adding a catalyst such as palladium carbon or Raney nickel after the reaction is finished, introducing hydrogen gas for reduction to obtain a crude product of 3-methylamine tetrahydrofuran, filtering to remove the catalyst to realize cyclic utilization of the catalyst, distilling and recovering the ammonia gas and the methanol to realize cyclic utilization of the ammonia gas and the methanol, adding n-hexane, wherein the n-hexane can be subjected to azeotropic distillation with the water in the distillation process, so that water and byproducts which are difficult to separate can be taken away in the process of distilling the n-hexane, the effects of improving the product purity and reducing the water content of the product are achieved, samples are taken every 0.5-1 hour in the dehydration process, and the water content is detected, when the difference value of the detection data of two adjacent times is less than 0.01%, the change of the moisture content is judged to be smooth.
Example 2
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.5 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.03 part by mass of raney nickel and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 40 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 2.0MPa, and continuously heating to 75 ℃ for reaction for 5 hours;
step three: cooling, filtering the reaction liquid to remove Raney nickel, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, reducing the pressure to the vacuum degree of-0.095 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 75 ℃ and the temperature at the top of the kettle is 50 ℃, transferring the obtained fraction to another distillation kettle, adding n-hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the n-hexane after the moisture content changes gently, reducing the pressure to the vacuum degree of-0.1 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 80 ℃ and the temperature at the top of the kettle is 75 ℃, collecting the fraction, namely the 3-methylamine tetrahydrofuran, and the gas chromatogram of the fraction is shown in figure 1.
Example 3
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.35 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.05 part by mass of raney nickel and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 38 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 1.5MPa, and continuously heating to 70 ℃ for reaction for 4 hours;
step three: cooling, filtering the reaction liquid to remove Raney nickel, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, reducing the pressure to the vacuum degree of-0.095 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 75 ℃ and the temperature at the top of the kettle is 50 ℃, transferring the obtained fraction to another distillation kettle, adding n-hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the n-hexane after the moisture content changes gently, reducing the pressure to the vacuum degree of-0.1 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 80 ℃ and the temperature at the top of the kettle is 75 ℃, collecting the fraction, namely the 3-methylamine tetrahydrofuran, and the gas chromatogram of the fraction is shown in figure 1.
Example 4
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.2 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.1 part by mass of palladium-carbon and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 35 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 1.0MPa, and continuously heating to 65 ℃ for reaction for 3 hours;
step three: cooling, filtering the reaction liquid to remove palladium carbon, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, decompressing to the vacuum degree of-0.075 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 70 ℃ and the temperature at the top of the kettle is 40 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes gently, decompressing to the vacuum degree of-0.09 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 75 ℃ and the temperature at the top of the kettle is 65 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
Example 5
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.5 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.03 part by mass of raney nickel and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 40 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 2.0MPa, and continuously heating to 75 ℃ for reaction for 5 hours;
step three: cooling, filtering the reaction liquid to remove Raney nickel, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, decompressing to the vacuum degree of-0.075 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 70 ℃ and the temperature at the top of the kettle is 40 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes gently, decompressing to the vacuum degree of-0.09 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 75 ℃ and the temperature at the top of the kettle is 65 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
Example 6
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.35 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.05 part by mass of raney nickel and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 38 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 1.5MPa, and continuously heating to 70 ℃ for reaction for 4 hours;
step three: cooling, filtering the reaction liquid to remove Raney nickel, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, decompressing to the vacuum degree of-0.075 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 70 ℃ and the temperature at the top of the kettle is 40 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes gently, decompressing to the vacuum degree of-0.09 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 75 ℃ and the temperature at the top of the kettle is 65 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
Example 7
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.2 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.1 part by mass of palladium-carbon and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 35 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 1.0MPa, and continuously heating to 65 ℃ for reaction for 3 hours;
step three: cooling, filtering the reaction liquid to remove palladium carbon, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the recovery of ammonia and methanol is finished, reducing the pressure to the vacuum degree of-0.085 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 73 ℃ and the temperature at the top of the kettle is 45 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes gently, reducing the pressure to the vacuum degree of-0.095 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 77 ℃ and the temperature at the top of the kettle is 70 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
Example 8
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.5 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.03 part by mass of raney nickel and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 40 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 2.0MPa, and continuously heating to 75 ℃ for reaction for 5 hours;
step three: cooling, filtering the reaction liquid to remove Raney nickel, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the recovery of ammonia and methanol is finished, reducing the pressure to the vacuum degree of-0.085 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 73 ℃ and the temperature at the top of the kettle is 45 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes gently, reducing the pressure to the vacuum degree of-0.095 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 77 ℃ and the temperature at the top of the kettle is 70 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
Example 9
As shown in fig. 1, this example provides a method for preparing high-purity low-water content 3-methylamine tetrahydrofuran, which specifically includes the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, stirring and cooling, sequentially adding 1.35 parts by mass of liquid ammonia and 1 part by mass of 3-formaldehyde tetrahydrofuran, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding 0.05 part by mass of raney nickel and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating to 38 ℃ under the protection of nitrogen, introducing hydrogen to ensure that the pressure of the hydrogen in the kettle is 1.5MPa, and continuously heating to 70 ℃ for reaction for 4 hours;
step three: cooling, filtering the reaction liquid to remove Raney nickel, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the recovery of ammonia and methanol is finished, reducing the pressure to the vacuum degree of-0.085 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 73 ℃ and the temperature at the top of the kettle is 45 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes gently, reducing the pressure to the vacuum degree of-0.095 MPa in the kettle, heating and distilling, wherein the temperature in the kettle is 77 ℃ and the temperature at the top of the kettle is 70 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
Application example 1
170.0kg of 3-formaldehyde tetrahydrofuran was taken, a 1000L stainless steel kettle was used as a reaction vessel, the reaction was carried out according to the method described in example 1, and 151.3kg of the final product, 3-methylamine tetrahydrofuran, was collected according to the formula:
yield ═ 100% (amount of reaction product substance/amount of raw material substance) ×
The yield was calculated to be 88.1%.
The gas chromatography detection result of the obtained product is shown in fig. 2, the GC purity is 99.61%, and the detection result comes from a GC-2014C type gas chromatograph manufactured by Shimadzu corporation; the moisture content of the obtained product is 0.15%, and the detection result is obtained from a METTLER TOLEDO V20 moisture meter produced by Mettler-Toritodo group, wherein the moisture standard of the product is less than or equal to 0.5%.
Application example 2
170.0kg of 3-formaldehyde tetrahydrofuran was taken, a 1000L stainless steel kettle was used as a reaction vessel, the reaction was carried out according to the method described in example 5, and 147.6kg of the final product, 3-methylamine tetrahydrofuran, was collected according to the formula:
yield ═ 100% (amount of reaction product substance/amount of raw material substance) ×
The yield was calculated to be 85.9%.
The gas chromatography detection result of the obtained product is shown in fig. 2, the GC purity is 99.33%, and the detection result comes from a GC-2014C type gas chromatograph manufactured by Shimadzu corporation; the moisture content of the obtained product is 0.19%, and the detection result is obtained from a METTLER TOLEDO V20 moisture meter produced by Mettler-Toritodo group, wherein the moisture standard of the product is less than or equal to 0.5%.
Application example 3
170.0kg of 3-formaldehyde tetrahydrofuran was taken, a 1000L stainless steel kettle was used as a reaction vessel, the reaction was carried out according to the method described in example 9, and 151.9kg of the final product, 3-methylamine tetrahydrofuran, was collected according to the formula:
yield ═ 100% (amount of reaction product substance/amount of raw material substance) ×
The yield was calculated to be 88.4%.
The gas chromatography detection result of the obtained product is shown in fig. 2, the GC purity is 99.74%, and the detection result comes from a GC-2014C type gas chromatograph manufactured by Shimadzu corporation; the moisture content of the obtained product is 0.13%, and the detection result is obtained from a METTLER TOLEDO V20 moisture meter produced by Mettler-Toritodo group, wherein the moisture standard of the product is less than or equal to 0.5%.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (5)
1. A preparation method of high-purity low-water content 3-methylamine tetrahydrofuran is characterized by comprising the following steps:
the method comprises the following steps: adding anhydrous methanol into a reaction kettle, sequentially adding liquid ammonia and 3-formaldehyde tetrahydrofuran under stirring and cooling, stirring and reacting under the protection of nitrogen to obtain an imine intermediate, and controlling the temperature of a reaction system to be not more than 0 ℃ in the whole process from the addition of the anhydrous methanol to the completion of the reaction;
step two: adding a catalyst and the imine intermediate prepared in the first step into a reaction kettle, stirring and heating under the protection of nitrogen, introducing hydrogen, continuously heating for reaction until the reaction is finished, wherein the temperature when the hydrogen is introduced is 35-40 ℃, the pressure of the hydrogen in the reaction kettle is 1.0-2.0MPa, the reaction temperature after the hydrogen is introduced is 65-75 ℃, and the reaction time is 3-5 hours;
step three: cooling, filtering the reaction liquid to remove the catalyst, transferring the reaction liquid to a distillation kettle, and distilling to recover ammonia and methanol;
step four: and after the ammonia gas and the methanol are recovered, decompressing to the degree of vacuum in the kettle of-0.095 MPa to-0.075 MPa, heating and distilling, wherein the temperature in the kettle is 70-75 ℃ and the temperature at the top of the kettle is 40-50 ℃, transferring the obtained fraction to another distillation kettle, adding normal hexane, stirring and mixing uniformly, heating, refluxing and dehydrating, sampling and monitoring, recovering the normal hexane after the moisture content changes smoothly, decompressing to the degree of vacuum in the kettle of-0.1 MPa to-0.09 MPa, heating and distilling, wherein the temperature in the kettle is 75-80 ℃ and the temperature at the top of the kettle is 65-75 ℃, and collecting the fraction, namely the 3-methylamine tetrahydrofuran.
2. The method for preparing 3-methylamine tetrahydrofuran with high purity and low water content as claimed in claim 1, wherein the temperature of the reaction system is controlled to-10 ℃ to 0 ℃ throughout the process from the addition of anhydrous methanol to the completion of the reaction in the first step.
3. The process for preparing 3-methylamine tetrahydrofuran with high purity and low water content as claimed in claim 1, wherein the catalyst in the second step is palladium on carbon or Raney nickel.
4. The process for producing high-purity low-water content 3-methylamine tetrahydrofuran according to claim 1, wherein the mass ratio of 3-formaldehyde tetrahydrofuran, liquid ammonia and the catalyst is 1:1.2-1.5: 0.03-0.1.
5. The process for the preparation of high purity low water content 3-methylamine tetrahydrofuran according to claim 1 wherein the GC purity of 3-methylamine tetrahydrofuran is greater than 99.0% and the water content is less than 0.2%.
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| US4376208A (en) * | 1981-08-17 | 1983-03-08 | The Quaker Oats Company | Hydroformylation of dihydrofuran |
| US5840928A (en) * | 1996-03-12 | 1998-11-24 | Mitsui Chemicals, Inc. | Method for production of 3-formyl-tetrahydrofuran |
| CN101622237A (en) * | 2007-03-06 | 2010-01-06 | 可乐丽股份有限公司 | Method for continuously producing 2,5-dihydrofuran |
| CN106397372A (en) * | 2015-07-27 | 2017-02-15 | 浙江捷达科技有限公司 | 3-methylamine tetrahydrofuran preparation method |
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| US5840928A (en) * | 1996-03-12 | 1998-11-24 | Mitsui Chemicals, Inc. | Method for production of 3-formyl-tetrahydrofuran |
| CN101622237A (en) * | 2007-03-06 | 2010-01-06 | 可乐丽股份有限公司 | Method for continuously producing 2,5-dihydrofuran |
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