Application of biodiesel as solvent for high-temperature cyclization reaction of 1, 2-cyclopentanedicarboxamide
By using biodiesel as a reaction solvent for high-temperature cyclosynthesis reaction of 1,2-cyclopentamorphamide, the problem of lack of green reaction solvents in the field of organic synthesis is solved, efficient and economical reaction effects are achieved, and more environmentally friendly solvents are provided choose.
Patent Information
- Application Number
- CN202411760436.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-03
- Publication Date
- 2025-02-11
AI Technical Summary
In the field of organic synthesis, there is a lack of green reaction solvents with low toxicity and low cost, especially in high-temperature organic reactions, and there are fewer types of suitable reaction solvents.
Biodiesel is used as the reaction solvent for the high-temperature cyclosynthesis reaction of 1,2-cyclopentamorphamide, and uses its substrate dispersion and heat transfer.
Biodiesel as a reaction solvent significantly improves reaction efficiency, shortens reaction time, and reduces production costs, while reducing dependence on fossil fuels, providing a more environmentally friendly and economical solvent choice.
Smart Images
Figure CN119409620A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of application of biomass chemicals, in particular to an application of biodiesel as a reaction solvent, in particular to an innovative application in the process of producing 1,2-cyclopentanedicarboxylic acid imide by high-temperature cyclization of 1,2-cyclopentanedicarboxylic acid amide. Background Art
[0002] Biodiesel is a renewable, low-carbon and environmentally friendly energy source, which is mainly produced by esterification or transesterification of vegetable oil, animal oil, waste oil or microbial oil. Traditionally, biodiesel is mainly used as transportation fuel and power sources such as industrial boilers and kilns, and is used in the chemical industry as a green chemical. However, there is a lack of green reaction solvents with low toxicity and low cost in the field of organic synthesis. Currently, organic reactions mostly use organic solvents such as benzene and alcohols as reaction media to transfer heat and disperse. These organic solvents mainly come from mineral oils and have the disadvantages of being volatile, highly toxic, high cost and non-renewable. In particular, for high-temperature organic reactions, there are fewer types of suitable reaction solvents, mainly silicone oils.
[0003] At present, there is no report on the use of biodiesel as a solvent for high-temperature organic reactions, especially in the process of high-temperature cyclization to produce 1,2-cyclopentanedicarboximide. Therefore, exploring the application of biodiesel in such reactions can not only enrich the utilization of biodiesel, but also provide a more environmentally friendly and economical solvent option for organic synthesis. Summary of the invention
[0004] The core of the new use of biodiesel involved in the present invention is to use biodiesel as a reaction solvent for high-temperature cyclization reaction of 1,2-cyclopentanedicarboxamide to play the role of substrate dispersion and heat transfer.
[0005] The technical solution adopted by the present invention is as follows:
[0006] 1,2-cyclopentanedicarboxamide is added to biodiesel, nitrogen is passed through to fully replace the air in the reaction system, and the reaction system is stirred and heated. 1,2-cyclopentanedicarboxamide is cyclized at high temperature to generate 1,2-cyclopentanedicarboximide. After the reaction is completed, the temperature of the reaction system is lowered to room temperature, and then deionized water is added thereto to extract the product from the biodiesel. After stratification and liquid separation, the extract (aqueous phase) is concentrated to about 1 / 5-1 / 4 of the original volume, cooled to 2-5°C for crystallization, filtered, and the solid is dried to obtain the 1,2-cyclopentanedicarboximide product; the raffinate (biodiesel phase) is dehydrated and recycled as a reaction solvent for the next reaction.
[0007] Further, the high temperature cyclization reaction equation is as follows:
[0008]
[0009] Furthermore, the biodiesel is a long-chain fatty acid methyl ester, and its molecular structure is: RCOOCH3, wherein R is an alkyl group with 16-20 carbon atoms and 0-3 double bonds, preferably 0-1 double bonds. The biodiesel is a fatty acid methyl ester compound or a mixture of several fatty acid methyl esters.
[0010] Furthermore, the biodiesel is methyl stearate.
[0011] Furthermore, the cyclization reaction temperature is 200-300°C, preferably 240-270°C; the cyclization reaction time is 0.5-5h, preferably 1.5-3h; the mass ratio of 1,2-cyclopentanedicarboxamide to biodiesel is 1 / 60-1 / 5, preferably 1 / 60-1 / 7.5.
[0012] The main innovations and beneficial effects are:
[0013] 1. The present invention introduces biodiesel, an energy substance, into the field of organic synthesis for the first time and uses it as a reaction solvent. This innovation not only expands the application scope of biodiesel and provides a new idea for its sustainable development in the chemical industry, but also provides new possibilities for the selection of organic synthesis reaction solvents.
[0014] 2. Using biodiesel as the reaction solvent has the following advantages:
[0015] 1) Biodiesel has a high boiling point (close to 350°C) and can maintain good chemical stability at high temperatures. It is not easy to decompose or produce harmful by-products. Therefore, biodiesel can be used in high-temperature organic reactions.
[0016] 2) Compared with conventional organic solvents, such as benzene, alcohols, chloroform, acetonitrile, tetrahydrofuran, etc., biodiesel is less toxic and less expensive.
[0017] 3) Compared with silicone oil high temperature solvents, biodiesel has a lower viscosity, which is more conducive to the dispersion of reactants and heat transfer during the reaction process, thus achieving better reaction effects. In the synthesis of 1,2-cyclopentanedicarboximide, biodiesel as a solvent can significantly improve reaction efficiency and shorten reaction time. In addition, the price of biodiesel is half of that of silicone oil solvents, and the production cost is low.
[0018] 4) As a renewable resource, biodiesel reduces dependence on fossil fuels. Compared with other solvents, biodiesel is greener and more sustainable. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Figure 1 Shown is the liquid chromatogram of the finished product of Example 1;
[0020] Figure 2Shown is the liquid chromatogram of the finished product of Comparative Example 1. DETAILED DESCRIPTION
[0021] The present invention takes the high-temperature cyclization of 1,2-cyclopentanedicarboxamide to prepare 1,2-cyclopentanedicarboximide as an example to illustrate the application of biodiesel as a reaction solvent in organic synthesis. However, the present invention is not limited to the reaction described in the example.
[0022] Take biodiesel as a high-temperature organic synthesis reaction, and take the synthesis of 1,2-cyclopentanedicarboximide as an example. Reaction equation:
[0023]
[0024] Embodiment 1:
[0025] 30g of biodiesel (the fatty acid composition of biodiesel is: 0.58% of methyl palmitate, 4.73% of methyl stearate, 36.63% of methyl oleate, 55.42% of methyl linoleate, 2.05% of methyl linolenate) and 0.5g of 1,2-cyclopentanedicarboxamide are added to the reactor, and the air in the reaction system is fully replaced by nitrogen. Stirring and heating to 270°C, keep the reaction for 1.5h. After the reaction is completed, stop heating, wait for the reaction system to cool to room temperature, transfer the reaction solution to a separatory funnel, add 45ml of deionized water in five times to extract 1,2-cyclopentanedicarboximide in biodiesel, after stratification and separation, the extract (aqueous phase) is concentrated to 1 / 5 of the volume before concentration, cooled to 5°C for crystallization, filtered, and the crystals are dried to obtain 1,2-cyclopentanedicarboximide products, and the product is subjected to liquid chromatography analysis, the product yield is 81.9%, and the purity is 92.2%. The raffinate (biodiesel phase) is heated and dehydrated and then recycled as a reaction solvent for the next reaction.
[0026] The operation process of Example 2 to Example 7 is the same as that of Example 1, except that only the amount of 1,2-cyclopentanedicarboxamide raw material, reaction temperature, and reaction time are changed. The specific changed conditions and the obtained experimental results are summarized in Table 1. The reaction time in Table 1 is the time required after the cyclization reaction of "preparing 1,2-cyclopentanedicarboxylic acid imide by high-temperature cyclization of 1,2-cyclopentanedicarboxylic acid amide" is completed.
[0027] The operation process of Example 8 is the same as that of Example 7, except that the type of biodiesel is changed, and the other conditions remain unchanged. The specific changed conditions and the obtained experimental results are shown in Table 1.
[0028] In addition, Example 9 used the biodiesel recovered in Example 1 to repeat the experiment for the next reaction. The experimental conditions were the same as in Example 1. The experimental results are summarized in Table 1.
[0029] Example 10 The biodiesel recovered in Example 8 was used to repeat the experiment for the next reaction. The experimental conditions were the same as in Example 8. The experimental results are summarized in Table 1.
[0030] Comparative Example 1 (using dimethyl silicone oil as reaction solvent)
[0031] 30g of dimethyl silicone oil (Article No. 01692531, purchased from Shanghai Titan Technology Co., Ltd.) and 0.5g of 1,2-cyclopentanedicarboxamide were added to the reactor, and the air in the reaction system was fully replaced by nitrogen. The mixture was stirred and heated to 250°C, and the reaction was kept warm for 1.5h. After the reaction was completed, the heating was stopped, and after the reaction system was cooled to room temperature, the reaction solution was transferred to a separatory funnel, and 45ml of deionized water was added five times to extract 1,2-cyclopentanedicarboximide from the dimethyl silicone oil. The extract was concentrated to about 1 / 5 of the volume before concentration, cooled to 5°C for crystallization, filtered, and the crystals were dried to obtain 1,2-cyclopentanedicarboximide products. The product was subjected to liquid chromatography analysis, and the product yield was 51.2% and the purity was 65.8%.
[0032] Table 1
[0033]
[0034] The liquid chromatograms of the 1,2-cyclopentanedicarboximide product obtained in Example 1 of the present invention and Comparative Example 1 are shown in FIG. Figure 1 and Figure 2 .
Claims
1. A method for using biodiesel as a solvent for high temperature cyclization of 1,2-cyclopentanedicarboxamide, characterized in that Biodiesel is used as a solvent for the high-temperature cyclization reaction of 1,2-cyclopentanedicarboxamide to play a role in substrate dispersion and heat transfer. The specific application method is as follows: 1,2-cyclopentanedicarboxamide is added to biodiesel, nitrogen is introduced to fully replace the air in the reaction system, stirring and heating are performed, and 1,2-cyclopentanedicarboxamide is cyclized at high temperature to generate 1,2-cyclopentanedicarboximide; after the reaction is completed, the temperature of the reaction system is lowered to room temperature, and then deionized water is added thereto to extract the product from the biodiesel, and after stratification and liquid separation, the aqueous phase of the extract is concentrated to about 1 / 5-1 / 4 of the original volume, the temperature is lowered to 2-5°C for crystallization, filtration is performed, and the solid is dried to obtain the 1,2-cyclopentanedicarboximide product; after the raffinate biodiesel phase is dehydrated, it is recycled as a reaction solvent for the next reaction.
2. The use of a biodiesel as claimed in claim 1 as a solvent for the high temperature cyclization reaction of 1,2-cyclopentanedicarboxamide, characterized in that The biodiesel used is long-chain fatty acid methyl ester, and its molecular structure formula is: RCOOCH3, wherein R is an alkyl group with 16-20 carbon atoms and 0-3 double bonds, preferably 0-1 double bonds.
3. The use of a biodiesel as a solvent for the high temperature cyclization reaction of 1,2-cyclopentanedicarboxamide as claimed in claim 2, characterized in that The biodiesel is methyl stearate.
4. The use of a biodiesel as a solvent for the high temperature cyclization reaction of 1,2-cyclopentanedicarboxamide according to claim 1, characterized in that The reaction temperature of the cyclization reaction is 200-300° C., and the cyclization reaction time is 0.5-5 h.
5. The use of a biodiesel as a solvent for the high temperature cyclization reaction of 1,2-cyclopentanedicarboxamide as claimed in claim 4, characterized in that The reaction temperature of the cyclization reaction is 240-270° C., and the cyclization reaction time is 1.5-3 h.
6. The use of a biodiesel as a solvent for high temperature cyclization reaction of 1,2-cyclopentanedicarboxamide according to claim 1, characterized in that The mass ratio of 1,2-cyclopentanedicarboxamide to biodiesel is 1 / 60-1 / 5.
7. The use of biodiesel as a solvent for high temperature cyclization reaction of 1,2-cyclopentanedicarboxamide as claimed in claim 6, characterized in that The mass ratio of 1,2-cyclopentanedicarboxamide to biodiesel is 1 / 60-1 / 7.5.