CN117486759B - Method for preparing methyl glutarimate by using furfuryl amine as raw material - Google Patents
Method for preparing methyl glutarimate by using furfuryl amine as raw materialInfo
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- CN117486759B CN117486759B CN202311453669.1A CN202311453669A CN117486759B CN 117486759 B CN117486759 B CN 117486759B CN 202311453669 A CN202311453669 A CN 202311453669A CN 117486759 B CN117486759 B CN 117486759B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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Abstract
本发明为一种以糠胺为原料制备戊二氨基甲酸甲酯的方法。该方法以生物质基平台分子糠醛的下游产品糠胺为原料，经2‑糠基甲基氨基甲酸甲酯氢解胺化制备N‑(5‑氨基戊基)氨基甲酸甲酯，最后合成戊二氨基甲酸甲酯。本发明为一条合成戊二氨基甲酸甲酯的新工艺路线，解决了生产PDI工艺中污染严重的问题，符合绿色化工的发展要求，具有广阔的工业前景。
The present invention is a method for preparing methyl pentanedicarbamate using furfurylamine as a raw material. The method uses furfurylamine, a downstream product of biomass-based platform molecule furfural, as a raw material, prepares N-(5-aminopentyl) methyl carbamate through hydrogenolysis and amination of 2-furfurylmethyl methyl carbamate, and finally synthesizes methyl pentanedicarbamate. The present invention is a new process route for synthesizing methyl pentanedicarbamate, solves the problem of serious pollution in the production process of PDI, meets the development requirements of green chemical industry, and has broad industrial prospects.
Description
Technical Field
The invention relates to a method for preparing methyl glutarimate by using furfuryl amine as a raw material, belonging to the field of organic synthesis.
Background
1, 5-Pentamethylene Diisocyanate (PDI) is aliphatic diisocyanate with wider application range, compared with aromatic isocyanate, the molecular structure of PDI does not contain benzene ring, has smaller steric hindrance, and has better yellowing resistance, heat resistance and light stability, and the prepared polyurethane foam material can be used in the high-precision tip fields of airplanes, ships and the like. Meanwhile, PDI has saturated straight-chain symmetrical molecular skeleton, and the prepared product has good excellent performance and is often used in the fields of leather, paint, adhesive, soft and hard foam, elastic fiber and other high polymer materials.
The phosgene method is a main method for producing PDI at present, chinese patent CN103347852A discloses a method for preparing PDI, firstly, 1, 5-pentanediamine is prepared by a biological method, then the 1, 5-pentanediamine is directly reacted with phosgene COCl 2, a great amount of acyl chloride, hydrogen chloride and other byproducts exist in the path product, equipment can be corroded, the environment can be polluted, the environment is not met, and in addition, the problems of low strength, poor tolerance, easy dissolution, low enzyme reuse efficiency, high cost and the like exist in the biological method for synthesizing the 1, 5-pentanediamine. Therefore, the clean production process of PDI by the non-phosgene method has become a research hot spot. Among them, the pyrolysis method of carbamate is highly paid attention to the advantages of mild reaction conditions, recycling of by-products, and the like. Glutarimide (PDC) as an intermediate is a key step in the PDI production process.
From the green development strategy, the efficient synthesis of the biscarbamate by taking biomass resources as raw materials has important significance for synthesizing the diisocyanate by a non-phosgene method.
Disclosure of Invention
Aiming at overcoming the defects of the existing method for producing methyl glutarate, the invention provides a method for preparing methyl glutarate by taking furfuryl amine, which is a downstream product of biomass-based platform molecule furfural, as a raw material. The method takes furfuryl amine which is a downstream product of biomass-based platform molecule furfural as a raw material, prepares N- (5-aminopentyl) methyl carbamate through hydrogenolysis amination of 2-furfuryl methyl carbamate, and finally synthesizes methyl glutarimate. The invention is a new process route for synthesizing methyl glutarimate, solves the problem of serious pollution in the PDI production process, meets the development requirements of green chemical industry, and has wide industrial prospect.
The technical scheme of the invention is as follows:
a method for preparing methyl glutarimate by using furfuryl amine as a raw material, which comprises the following steps:
(1) A step of preparing 2-furfuryl methyl carbamate by furfuryl amine and dimethyl carbonate:
adding furfuryl amine, dimethyl carbonate and a catalyst into a reactor under the nitrogen atmosphere, stirring, carrying out reflux reaction for 0.5-8 h at 40-90 ℃, and cooling to room temperature to obtain a product of 2-furfuryl methyl carbamate;
The catalyst is sodium methoxide;
the molar ratio of the furfuryl amine to the dimethyl carbonate is 1:8-1:100, and the mass ratio of the furfuryl amine to the catalyst sodium methoxide is 1:0.12-1:0.8;
Cooling to room temperature, adding deionized water into the reaction liquid, dissolving the solid, separating an organic phase through a separating funnel, and removing the solvent through reduced pressure distillation to obtain 2-furfuryl methyl carbamate;
(2) The synthesis of methyl (5-aminopentyl) carbamate is one of two methods:
the method comprises the following steps of:
in the first step, methyl 2-furfuryl methyl carbamate is synthesized into methyl (5-hydroxypentyl) carbamate:
adding the 2-furfuryl methyl carbamate obtained in the previous step, a first supported metal catalyst and an organic solvent into a high-pressure reaction kettle, and reacting for 0.5-10 hours at the temperature of 20-170 ℃ under the H 2 pressure of 0.1-8 MPa to obtain (5-hydroxypentyl) methyl carbamate;
Wherein, 5-20 mL of organic solvent and 0.1-1 g of first supported metal catalyst are added into each 1mmol of 2-furfuryl methyl carbamate;
The first supported metal catalyst comprises an active metal component and a carrier, wherein the active metal component comprises an active metal element which is Pd, pt, ru, rh, preferably Pt and Ru, and the carrier is selected from γ-Al2O3、ZrO2、TiO2、CeO2、SiO2、Nb2O5、HZSM-5 or active carbon;
The active metal component load is 1wt% -10 wt%;
Wherein the mass of the active metal component is calculated by the mass of the active metal element contained in the active metal component, and the mass of the carrier is calculated by the mass of the carrier itself;
The organic solvent is one or two of methanol, ethanol, tetrahydrofuran, 1, 4-dioxane, toluene or isopropanol, preferably methanol;
the preferable hydrogen pressure is 1-4 MPa, the preferable reaction temperature is 100-170 ℃, and the preferable reaction time is 1-4 h;
second, aminating (5-hydroxypentyl) methyl carbamate to synthesize N- (5-aminopentyl) methyl carbamate:
The method comprises the steps of (5-hydroxypentyl) methyl carbamate synthesis reaction of 2-furfuryl methyl carbamate in the first step, cooling to room temperature, filtering out a first supported metal catalyst, transferring filtrate into a high-pressure reaction kettle, adding a second supported metal catalyst and ammonia water, and reacting for 2-12 hours at the pressure of 0.1-8 MPaH 2 and the temperature of 120-200 ℃ to obtain N- (5-aminopentyl) methyl carbamate;
Wherein, 0.1-1 g of metal catalyst is added to 1mmol of (5-hydroxypentyl) methyl carbamate, and 0.5-10mL of ammonia water is added to 20mL of filtrate;
The active component of the second supported metal catalyst is one or two of Ru, co or Ni, preferably Ru and Co bimetallic, and the carrier is gamma-Al 2O3、MgO、HAP、TiO2、SiO2 or HZSM-5;
The active metal component load is 1wt% -20 wt%;
The concentration of the ammonia water is 20-40wt%;
the preferable hydrogen pressure is 1-4 MPa, and the preferable reaction temperature is 150-180 ℃;
The method comprises the following steps of one-step synthesis:
One-step hydrogenolysis amination of methyl 2-furfuryl methylcarbamate to methyl N- (5-aminopentyl) carbamate:
adding 2-furfuryl methyl carbamate, a third supported metal catalyst, ammonia water and an organic solvent into a high-pressure reaction kettle, and reacting for 0.5-12H at 20-180 ℃ under H 2 pressure of 0.1-8 MPa to obtain N- (5-aminopentyl) methyl carbamate.
Wherein, 5-20 mL of organic solvent and 0.1-1 g of supported metal catalyst are added into each 1mmol of 2-furfuryl methyl carbamate, and 0.5-10mL of ammonia water is added into each 20mL of organic solvent;
The organic solvent is one or two of methanol, ethanol, tetrahydrofuran, 1, 4-dioxane, toluene or isopropanol, preferably methanol;
The concentration of the ammonia water is 20-40wt%;
the third supported metal catalyst comprises an active metal component and a carrier, wherein the active metal element is one or two of Pd, pt, ru, rh, co or Ni, preferably Pt-Co bimetallic or Ru-Co bimetallic, and the carrier is selected from γ-Al2O3、ZrO2、TiO2、CeO2、SiO2、Nb2O5、HZSM-5 or active carbon;
The active metal component loading is 1-20wt%;
The preferable hydrogen pressure is 1-6 MPa, the preferable reaction temperature is 120-170 ℃, and the preferable reaction time is 1-8 h;
(3) Methyl N- (5-aminopentyl) carbamate and dimethyl carbonate to synthesize methyl glutarate:
And (3) filtering the reaction liquid obtained in the step (2) to remove the catalyst, removing the solvent by rotary evaporation of the filtrate, transferring the filtrate into a reactor, adding sodium methoxide and dimethyl carbonate, heating to a reflux temperature under the stirring condition, reacting for 0.5-8 h at 40-90 ℃, and stopping heating.
The molar ratio of the N- (5-aminopentyl) methyl carbamate to the dimethyl carbonate is 1:8-1:100;
the mass ratio of the N- (5-aminopentyl) methyl carbamate to the catalyst sodium methoxide is 1:0.12-1:0.8.
The invention has the substantial characteristics that:
The method comprises three parts, namely, firstly, preparing 2-furfuryl methyl carbamate by taking furfuryl amine as a raw material, secondly, preparing N- (5-aminopentyl) methyl carbamate by hydrogenolysis amination of the 2-furfuryl methyl carbamate, and finally synthesizing a target product methyl glutarimide by a carbonate method.
The preparation of the 2-furfuryl methyl carbamate in the first step adopts dimethyl carbonate as a carbonylation agent, methanol is the only byproduct, the reaction process is pollution-free, and the preparation of the N- (5-aminopentyl) carbamate by the hydrogenolysis amination of the 2-furfuryl methyl carbamate opens up a new process route and lays a foundation for the subsequent production of PDC and PDI.
The invention has the beneficial effects that:
(1) The method realizes the synthesis of methyl glutarate by using furfuryl methyl carbamate and N- (5-aminopentyl) methyl carbamate as raw materials for the first time.
(2) Methyl glutarate (PDC) can be used as a precursor for preparing 1, 5-Pentamethylene Diisocyanate (PDI), and has important application value in the high-end polyurethane manufacturing industry. As a downstream product furfuryl amine of biomass-based platform molecular furfural, the biomass-based platform molecular furfural has the characteristics of sustainability, low cost and the like, opens up a new way for synthesizing isocyanate, and has the characteristics of green and intrinsic safety.
(3) The two steps of synthesizing 2-furfuryl methyl carbamate and synthesizing methyl glutarimide by using N- (5-aminopentyl) methyl carbamate take dimethyl carbonate as a carbonylation agent, methanol is the only byproduct, the conversion rate of the two steps can reach 100%, and the product yield is 99%.
(4) The furfuryl amine and the methyl carbonate react to prepare the 2-furfuryl methyl carbamate can effectively avoid the difficult problem of cyclizing the intermediate product of the subsequent furan ring hydrogenolysis at high temperature, and the selectivity of hydrogenolysis products is improved.
(5) The reaction condition is mild, the process is easy to control, the supported metal catalyst is easy to separate, the safety is greatly improved, the requirements of green chemistry are met, and the method has wide research prospect.
Drawings
FIG. 1 is a GCMS spectrum of methyl 2-furfuryl methylcarbamate obtained in example 1;
FIG. 2 is a GCMS spectrum of methyl (5-hydroxypentyl) carbamate obtained in example 1;
FIG. 3 is a GCMS spectrum of methyl N- (5-aminopentyl) carbamate obtained in example 1;
FIG. 4 is a GCMS spectrum of methyl glutarate obtained in example 1;
Detailed Description
The essential features and significant effects of the invention can be seen from the examples which follow, without however limiting the invention in any way, and those skilled in the art can make numerous insubstantial improvements and adaptations in accordance with the teachings of the invention. The invention is further illustrated by the following detailed description.
The invention provides a novel method for preparing methyl glutarimate by taking furfuryl amine, which is a downstream product of a biomass platform compound furfural, as a raw material, and opens up a novel way for preparing isocyanate. The specific path is as follows:
The first supported metal catalyst, the second supported metal catalyst and the third supported metal catalyst related by the invention are all made of known materials;
For example, a 5wt% Pt/gamma-Al 2O3 catalyst was prepared by dissolving 0.1403g H 2PtCl6·6H2 O (37 wt% Pt) in 2.5mL deionized water, slowly dropping the resulting solution into 1g gamma-Al 2O3, stirring well, and standing overnight. Then, the mixture was dried at 100℃for 12 hours and calcined at 300℃for 3 hours using a muffle furnace. And finally, reducing for 3h at 300 ℃ (volume flow rate N 2:H2 =60:40).
Different supported metal catalysts were prepared in the same way. But is not limited thereto.
Example 1
Step 1, adding 0.97g (0.01 mol) of furfuryl amine, 26mL (0.3 mol) of dimethyl carbonate and 0.16g of sodium methoxide into a 100mL three-necked flask in sequence, stirring, refluxing and condensing, reacting for 2 hours at 60 ℃ under nitrogen atmosphere, stopping heating, cooling the reaction liquid to room temperature, (taking supernatant at the moment and directly analyzing by gas chromatography), and dripping deionized water into the three-necked flask, wherein the conversion rate of the furfuryl amine is 100%, the yield of the 2-furfuryl methyl carbamate is more than 99%, and the solid is completely dissolved, so that layering phenomenon occurs, namely the upper layer is an aqueous phase, and the lower layer is an organic phase. Transferring the mixture into a separating funnel, separating an organic phase from the lower surface, and finally removing solvent dimethyl carbonate through reduced pressure distillation to obtain high-purity methyl 2-furfuryl methyl carbamate.
Step 21 g (6.45 mmol) of methyl 2-furfuryl methylcarbamate, 1.25g of Pt/gamma-Al 2O3 with a loading of 5wt% and 50mL of methanol were added to a 100mL autoclave, the atmosphere in the autoclave was replaced with nitrogen 5 times and then with hydrogen 5 times, and hydrogen was charged to 2MPa. The reaction was carried out at 170℃for 2 hours, cooled to room temperature after completion of the reaction, and the supernatant was collected and filtered and analyzed directly on a gas chromatograph, wherein the conversion of methyl 2-furfuryl methylcarbamate was 100%, the yield of methyl (5-hydroxypentyl) carbamate was 69%, the yield of methyl (tetrahydrofuran-2-ylmethyl) carbamate was 17%, and the yield of methyl (2-hydroxypentyl) carbamate was 14%.
And 3, filtering and removing the Pt/gamma-Al 2O3 catalyst in the step 2, transferring the filtrate into an autoclave (at the moment, the solution contains 0.717g (4.45 mmol) of (5-hydroxypentyl) methyl carbamate, 50mg of 5wt% Ru-10wt% Co/gamma-Al 2O3 and 4mL of 28wt% ammonia water, sealing the autoclave, replacing the air in the autoclave with nitrogen for 5 times, then replacing the air with hydrogen for 5 times, filling the hydrogen to 1MPa, reacting for 8 hours at 180 ℃, cooling to room temperature after the reaction is finished, taking the supernatant, filtering and directly analyzing on gas chromatography, wherein the conversion rate of the (5-hydroxypentyl) methyl carbamate is 57%, and the yield of the N- (5-aminopentyl) methyl carbamate is 39%.
Step 4 Ru-Co/gamma-Al 2O3 in step 3 was filtered, distilled under reduced pressure to remove the solvent, then methyl (5-aminopentyl) carbamate was 0.278g (1.73 mmol), 7mL (0.083 mol) dimethyl carbonate, 0.139g sodium methoxide was added, the mixture was transferred into a three-necked flask, stirred, refluxed and condensed, the heating was stopped after reacting at 60℃for 2 hours under nitrogen atmosphere, the supernatant was taken after the reaction solution was cooled to room temperature and analyzed directly by gas chromatography, and the conversion of methyl N- (5-aminopentyl) carbamate was 100% and the yield of methyl glutarimide was 99%.
Example 2
Step 1 was identical to example 1, and the remainder of step 2 was identical to example 1, except that the reaction temperature was 100 ℃, the conversion of methyl 2-furfuryl methylcarbamate was 100%, the yield of methyl (5-hydroxypentyl) carbamate was 39%, the yield of methyl (tetrahydrofuran-2-ylmethyl) carbamate was 50%, and the yield of methyl (2-hydroxypentyl) carbamate was 11%. Since the yield of methyl (5-hydroxypentyl) carbamate is not high under this condition, step 3 and step 4 are not continued.
Example 3
Step1 was the same as in example 1, and the other portions of step 2 were the same as in example 1 except that the catalyst was 5% Pt/ZrO 2, the reaction result was that the conversion of methyl 2-furfuryl methylcarbamate was 100%, the yield of methyl (5-hydroxypentyl) carbamate was 33%, the yield of methyl (tetrahydrofuran-2-ylmethyl) carbamate was 52%, and the yield of methyl (2-hydroxypentyl) carbamate was 15%. Since the yield of methyl (5-hydroxypentyl) carbamate is not high under this condition, step 3 and step 4 are not continued.
Example 4
Step 1 was the same as in example 1, and the other portions of step 2 were the same as in example 1 except that the pressure of H 2 was 1MPa, the conversion of methyl 2-furfuryl methylcarbamate was 100%, the yield of methyl (5-hydroxypentyl) carbamate was 28%, the yield of methyl (tetrahydrofuran-2-ylmethyl) carbamate was 63%, and the yield of methyl (2-hydroxypentyl) carbamate was 9%. Since the yield of methyl (5-hydroxypentyl) carbamate is not high under this condition, step 3 and step 4 are not continued.
Example 5
Step 1 was the same as in example 1, and the other portions of step 2 were the same as in example 1 except that the solvent was tetrahydrofuran, and the reaction result was that the conversion of methyl 2-furfuryl methylcarbamate was 95%, the yield of methyl (5-hydroxypentyl) carbamate was 18%, the yield of methyl (tetrahydrofuran-2-ylmethyl) carbamate was 72%, and the yield of methyl (2-hydroxypentyl) carbamate was 10%. Since the yield of methyl (5-hydroxypentyl) carbamate is not high under this condition, step 3 and step 4 are not continued.
Example 6
Steps 1 and 2 are the same as in example 1, and the other portions of step 3 are the same as in example 1 except that the reaction temperature is 150 ℃, the conversion of methyl (5-hydroxypentyl) carbamate is 27%, and the yield of methyl (5-aminopentyl) carbamate is 16%. At this time, methyl N- (5-aminopentyl) carbamate was 0.114g (0.712 mmol), and since the yield of methyl N- (5-aminopentyl) carbamate was too low, step 4 was not performed.
Example 7
Steps 1 and 2 are the same as in example 1, and the other portions of step 3 are the same as in example 1 except that the catalyst is Co/γ -Al 2O3, and the reaction result is that the conversion of methyl (5-hydroxypentyl) carbamate is 52% and the yield of methyl N- (5-aminopentyl) carbamate is 24%. At this time, methyl N- (5-aminopentyl) carbamate was 0.17g (1.068 mmol), and the conversion of methyl N- (5-aminopentyl) carbamate in step 4 was 100% and the yield of methyl glutarimide was 99%.
Example 8
Steps 1 and 2 were the same as in example 1, and the other portions of step 3 were the same as in example 1 except that 8mL of aqueous ammonia was used, and the reaction result was that the conversion of methyl (5-hydroxypentyl) carbamate was 62% and the yield of methyl (5-aminopentyl) carbamate was 9%. At this time, methyl N- (5-aminopentyl) carbamate was 0.064g (0.4 mmol), and since the yield of methyl N- (5-aminopentyl) carbamate was too low, step 4 was not performed.
Example 9
Step 1, 0.97g (0.01 mol) of furfuryl amine, 26mL (0.3 mol) of dimethyl carbonate and 0.16g of sodium methoxide are sequentially added into a 50mL three-necked flask, stirring, reflux condensing, reacting for 2 hours at 60 ℃ under nitrogen atmosphere, stopping heating, cooling the reaction liquid to room temperature, taking supernatant, and directly analyzing by gas chromatography, wherein the conversion rate of the furfuryl amine is 100%, and the yield of the 2-furfuryl methyl carbamate is more than 99%. Adding deionized water into a three-neck flask, completely dissolving solids in a solvent, layering, transferring the upper layer into a water phase, transferring the lower layer into a separating funnel, discharging the organic phase from the lower part, and finally removing solvent dimethyl carbonate by reduced pressure distillation to obtain the high-purity 2-furfuryl methyl carbamate.
Step 21 g (6.45 mmol) of methyl 2-furfuryl methylcarbamate, 1.25g of 5wt% Pt-10wt% Co/gamma-Al 2O3 catalyst, 50mL of methanol, 4mL of 28wt% ammonia were added to a 100mL autoclave, the atmosphere in the autoclave was replaced with nitrogen 5 times and then with hydrogen 5 times, and hydrogen was charged to 2MPa. The reaction was carried out at 170℃for 4 hours, cooled to room temperature after completion of the reaction, and the supernatant was collected and filtered and analyzed directly on a gas chromatograph, wherein the conversion of methyl 2-furfuryl methylcarbamate was 100%, the yield of methyl (5-hydroxypentyl) carbamate was 24%, the yield of methyl (tetrahydrofuran-2-ylmethyl) carbamate was 31%, the yield of methyl (2-hydroxypentyl) carbamate was 11%, and the yield of methyl N- (5-aminopentyl) carbamate was 32%.
Step 35 wt% Pt-10wt% Co/gamma-Al 2O3 catalyst in step 2 was filtered, the solvent was distilled off under reduced pressure (at this time, methyl (5-aminopentyl) carbamate was 0.33g (2.064 mmol)), 9mL (0.104 mol) of dimethyl carbonate was added, 0.16g of sodium methoxide was transferred into a three-necked flask, stirring was performed, reflux condensation was performed, heating was stopped after reacting for 2 hours under a nitrogen atmosphere at 60 ℃, and after cooling the reaction solution to room temperature, the supernatant was taken and analyzed directly by gas chromatography, and the reaction result was that the conversion of methyl N- (5-aminopentyl) carbamate was 100% and the yield of methyl glutarate was 99%.
The invention is not a matter of the known technology.
Claims (3)
1. The method for preparing methyl glutarimate by using furfuryl amine as a raw material is characterized by comprising the following steps:
(1) A step of preparing 2-furfuryl methyl carbamate by furfuryl amine and dimethyl carbonate:
adding furfuryl amine, dimethyl carbonate and a catalyst into a reactor under the nitrogen atmosphere, stirring, carrying out reflux reaction for 0.5-8 h at 40-90 ℃, and cooling to room temperature to obtain a product of 2-furfuryl methyl carbamate;
The catalyst is sodium methoxide;
the molar ratio of the furfuryl amine to the dimethyl carbonate is 1:8-1:100, and the mass ratio of the furfuryl amine to the catalyst sodium methoxide is 1:0.12-1:0.8;
(2) The synthesis of methyl N- (5-aminopentyl) carbamate is one of two methods:
the method comprises the following steps of:
in the first step, methyl 2-furfuryl methyl carbamate is synthesized into methyl (5-hydroxypentyl) carbamate:
Adding the 2-furfuryl methyl carbamate obtained in the previous step, a first supported metal catalyst and an organic solvent into a high-pressure reaction kettle, and reacting for 1-4 hours at the temperature of 100-170 ℃ under the H 2 pressure of 1-4 MPa to obtain (5-hydroxypentyl) methyl carbamate;
Wherein, 5-20 mL of organic solvent and 0.1-1 g of first supported metal catalyst are added into each 1mmol of 2-furfuryl methyl carbamate;
The first supported metal catalyst comprises an active metal component and a carrier, wherein the active metal component comprises an active metal element which is Pt or Ru, and the carrier is gamma-Al 2O3;
The active metal component load is 1wt% -10 wt%;
The organic solvent is methanol;
second, aminating (5-hydroxypentyl) methyl carbamate to synthesize N- (5-aminopentyl) methyl carbamate:
The method comprises the steps of (5-hydroxypentyl) methyl carbamate synthesis reaction of 2-furfuryl methyl carbamate in the first step, cooling to room temperature, filtering out a first supported metal catalyst, transferring filtrate into a high-pressure reaction kettle, adding a second supported metal catalyst and ammonia water, and reacting for 2-12 hours under the H 2 pressure of 1-4 MPa and the temperature of 150-180 ℃ to obtain N- (5-aminopentyl) methyl carbamate;
wherein, 0.1-1 g of metal catalyst is added to 1mmol of (5-hydroxypentyl) methyl carbamate, and 0.5-4mL of ammonia water is added to 20mL of filtrate;
the active component of the second supported metal catalyst is Ru and Co bimetal or Co, and the carrier is gamma-Al 2O3;
The active metal component load is 1wt% -20 wt%;
The method comprises the following steps of one-step synthesis:
One-step hydrogenolysis amination of methyl 2-furfuryl methylcarbamate to methyl N- (5-aminopentyl) carbamate:
adding 2-furfuryl methyl carbamate, a third supported metal catalyst, ammonia water and an organic solvent into a high-pressure reaction kettle, and reacting for 1-8 hours at the temperature of 120-170 ℃ under the H 2 pressure of 1-6 MPa to obtain (5-aminopentyl) methyl carbamate;
wherein, 5-20 mL of organic solvent and 0.1-1 g of supported metal catalyst are added into each 1mmol of 2-furfuryl methyl carbamate, and 0.5-10mL of ammonia water is added into each 20mL of organic solvent;
The organic solvent is one or two of methanol, ethanol, tetrahydrofuran, 1, 4-dioxane, toluene or isopropanol;
The third supported metal catalyst comprises an active metal component and a carrier, wherein the active metal element is Pt-Co bimetal or Ru-Co bimetal, and the carrier is gamma-Al 2O3;
The active metal component loading is 1-20wt%;
(3) Methyl N- (5-aminopentyl) carbamate and dimethyl carbonate to synthesize methyl glutarate:
filtering the reaction liquid obtained in the step (2) to remove the catalyst, removing the solvent by rotary evaporation of the filtrate, transferring the filtrate into a reactor, adding sodium methoxide and dimethyl carbonate, heating to a reflux temperature under stirring, reacting for 0.5-8 h at 40-90 ℃, and stopping heating;
The molar ratio of the N- (5-aminopentyl) methyl carbamate to the dimethyl carbonate is 1:8-1:100;
the mass ratio of the N- (5-aminopentyl) methyl carbamate to the catalyst sodium methoxide is 1:0.12-1:0.8.
2. The method for preparing methyl glutarimate by using furfuryl amine as material according to claim 1, wherein in the step (1), deionized water is added into the reaction solution after cooling to room temperature, the solid is dissolved, an organic phase is separated out through a separating funnel, and the solvent is removed by reduced pressure distillation to obtain the methyl 2-furfuryl methyl carbamate.
3. The method for preparing methyl glutarimate from furfuryl amine according to claim 1, wherein the concentration of the ammonia water in the first or second method in the step (2) is 20-40 wt%.
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