A process for the preparation of sodium 5-dodecyloxycarbonylfuran-2-carboxylate
By using a method of unilateral esterification and salt formation of 2,5-furandicarboxylic acid and dodecyl alcohol under acidic conditions, the problems of low production efficiency and high cost of sodium 5-dodecyloxycarbonylfuran-2-carboxylate have been solved, realizing a high-efficiency and low-cost preparation process suitable for industrial production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- ZHONGKE GUOSHENG (HANGZHOU) TECH CO LTD
- Filing Date
- 2023-12-06
- Publication Date
- 2026-07-31
AI Technical Summary
The existing technology for producing sodium 5-dodecyloxycarbonylfuran-2-carboxylate has low production efficiency, high cost, and is not suitable for industrial production. It also suffers from problems such as high equipment corrosion and difficult operation.
Sodium 5-dodecanooxycarbonylfuran-2-carboxylate is prepared by unilateral esterification of 2,5-furandicarboxylic acid and dodecyl alcohol under acidic conditions, followed by salt formation under weak base conditions. The reaction is mild, simple to operate, and produces few byproducts, making it suitable for large-scale chemical production.
The preparation of sodium 5-dodecyloxycarbonylfuran-2-carboxylate was achieved with high efficiency and low cost. The reaction conditions were mild and the equipment was not corrosive, making it suitable for industrial production.
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Figure CN117624093B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of surfactant preparation, specifically to a method for preparing sodium 5-dodecyloxycarbonylfuran-2-carboxylate. Background Technology
[0002] Currently, sodium 5-dodecanooxycarbonylfuran-2-carboxylate is widely studied and applied as a surfactant, possessing numerous advantages such as being a bio-based and renewable raw material. According to literature reports, sodium 5-dodecanooxycarbonylfuran-2-carboxylate is generally prepared by using 2,5-furandicarboxylic acid to prepare an acyl chloride with thionyl chloride to enhance its activity, followed by unilateral esterification with dodecyl alcohol, and then hydrolysis to form a salt. This method has a long synthetic route, high production costs, and the thionyl chloride used is highly corrosive to equipment, making experimental operations difficult and dangerous. Therefore, it is not an ideal route for industrialization. In view of this, finding a simple experimental route, mild reaction conditions, convenient post-processing, safe and reliable, and low-cost method to synthesize sodium 5-dodecanooxycarbonylfuran-2-carboxylate is an urgent problem to be solved.
[0003] CN106699613A (application number 201611015919.3) discloses a method for preparing sodium dodecyl diphenyl ether disulfonate, a highly efficient bifunctional anionic surfactant using tributene as a raw material. The method for preparing sodium dodecyl diphenyl ether disulfonate involves: using tributene and excess diphenyl ether as alkylation raw materials, using an acidic catalyst as the alkylation catalyst, and controlling the alkylation reaction at a temperature of 30°C. After the reaction, the catalyst is removed, and unreacted tributene is recovered. Butene reacts with diphenyl ether to obtain the intermediate product alkyl diphenyl ether. Using alkyl diphenyl ether as the sulfonation raw material and chlorosulfonic acid as the sulfonating agent, the sulfonation reaction is carried out at 0-10°C. The generated hydrogen chloride is absorbed using a hydrogen chloride absorption device. The sulfonated product is neutralized, treated with softened water, and then the final product is obtained. This method, which involves alkylation followed by neutralization via sulfonation to obtain sodium dodecyl diphenyl ether disulfonate, is not suitable for the preparation of the surfactant sodium 5-dodecyloxycarbonylfuran-2-carboxylate. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing sodium 5-dodecyloxycarbonylfuran-2-carboxylate, in order to solve the problems of low efficiency, high production cost, and inability to be industrialized in the production of sodium 5-dodecyloxycarbonylfuran-2-carboxylate in the prior art.
[0005] This invention proposes a method for preparing sodium 5-dodecanoic acid by unilateral esterification with dodecyl alcohol under acidic conditions, followed by salt formation under weak base conditions. The preparation method of this invention has advantages such as high production efficiency, low cost, mild reaction, and convenient operation.
[0006] To address the above problems, the present invention provides: 1. A method for preparing sodium 5-dodecyloxycarbonylfuran-2-carboxylate, comprising the following steps:
[0007] I. Unilateral esterification:
[0008] S1.1 First, add 2,5-furandicarboxylic acid and dodecyl alcohol to the container, and then add the acid;
[0009] S1.2 After adding acid, stir the reaction at 25-160℃ for 0.5-24 hours;
[0010] S1.3 The oily substance obtained from the reaction was post-treated to obtain pure 5-dodecanooxycarbonylfuran-2-carboxylic acid;
[0011] II. Preparation of sodium salts:
[0012] S2.1 Dissolve the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid in an organic solvent to obtain a solution;
[0013] S2.2. Start stirring and add sodium carbonate, sodium bicarbonate, or sodium tert-butoxide dropwise to the solution obtained in step S2.1. After the addition is complete, stir the reaction for 0.5-24 hours to obtain the reaction solution.
[0014] S2.3 Filter the reaction solution from step S2.2, and transfer the filter cake to an oven to dry to obtain pure sodium 5-dodecanooxycarbonylfuran-2-carboxylate.
[0015] In step S1.1, the acid is one of hydrochloric acid, concentrated sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid.
[0016] In step S1.2, after adding the acid, the mixture is stirred and reacted at a temperature of 100-140℃ for 12-24 hours; most preferably, after adding the acid, the mixture is stirred and reacted at a temperature of 120℃ for 16 hours.
[0017] In step S1.3, the post-processing specifically includes:
[0018] S1.3.1 Add ethyl acetate and water to the oily substance obtained from the reaction, and separate and collect the organic phase;
[0019] S1.3.2. Organic phase distillation removes the solvent to obtain crude 5-dodecanooxycarbonylfuran-2-carboxylic acid;
[0020] S1.3.3 Add solvent to crude 5-dodecyloxycarbonylfuran-2-carboxylic acid and beat at 0-100℃ for 0.5-24 hours;
[0021] S1.3.4 Filter the pulped solution and dry the filter cake to obtain pure 5-dodecanooxycarbonylfuran-2-carboxylic acid.
[0022] In step S1.3.3, the solvent is one or a mixture of dichloromethane, ethyl acetate, n-heptane, methyl tert-butyl ether, and deionized water.
[0023] In step S1.3.3, pulping is performed at 15-35℃ for 1-4 hours, with the most preferred method being pulping at 25℃ for 2 hours.
[0024] In step S1.3.3, the filter cake is dried at 50-70°C, and most preferably, the filter cake is dried at 60°C.
[0025] In step S2.1, the organic solvent is tetrahydrofuran, methanol, or ethanol.
[0026] In step S2.2, the reaction is stirred for 0.5-2 hours.
[0027] In step S2.3, the filter cake is transferred to an oven and dried at 50-70°C for 8-20 hours. The most preferred step is to transfer the filter cake to an oven and dry it at 60°C for 12 hours.
[0028] Compared with the prior art, the present invention has the following advantages:
[0029] This invention uses 2,5-furandicarboxylic acid as a raw material, and obtains the product through unilateral esterification followed by salt formation. It produces fewer byproducts, which are easily removed, and exhibits less corrosiveness to equipment, making it suitable for large-scale chemical production.
[0030] The entire process of this invention requires a short reaction time and is extremely efficient. The reaction is mild, the cost is low, the purification method is simple and easy to operate, and the reaction route is straightforward. Attached Figure Description
[0031] Figure 1 A traditional process roadmap;
[0032] Figure 2 The reaction route diagram for synthesizing the compounds of this invention;
[0033] Figure 3 The mass spectrum of sodium 5-dodecyloxycarbonylfuran-2-carboxylate prepared in Example 1 ([M+Na] = 347);
[0034] Figure 4 The chromatogram of sodium 5-dodecyloxycarbonylfuran-2-carboxylate prepared in Example 1;
[0035] Figure 5 The hydrogen spectrum of sodium 5-dodecyloxycarbonylfuran-2-carboxylate prepared in Example 1. Detailed Implementation
[0036] like Figure 1The diagram shows the traditional process route. Sodium 5-dodecyloxycarbonylfuran-2-carboxylate is generally prepared by using 2,5-furandicarboxylic acid to prepare acyl chloride with thionyl chloride to improve its activity, then unilaterally esterifying it with dodecyl alcohol, and finally hydrolyzing it to form a salt to obtain sodium 5-dodecyloxycarbonylfuran-2-carboxylate.
[0037] like Figure 2 As shown, a method for preparing sodium 5-dodecyloxycarbonylfuran-2-carboxylate includes the following steps:
[0038] Unilateral esterification:
[0039] S1. Dissolve 2,5-furandicarboxylic acid and dodecyl alcohol in one or more of dichloromethane, tetrahydrofuran, or toluene in a container, and add hydrochloric acid, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid.
[0040] S2, temperature 25-160℃, start stirring and react for 0.5-24 hours;
[0041] S3. Quench the oily substance obtained from the reaction with water, and separate and collect the organic phase;
[0042] S4. Organic phase distillation removes the solvent to obtain crude 5-dodecanooxycarbonylfuran-2-carboxylic acid;
[0043] S5. Control the temperature inside the container to 0-100℃, add crude 5-dodecyloxycarbonylfuran-2-carboxylic acid, and add one or a mixture of dichloromethane, ethyl acetate, n-heptane, methyl tert-butyl ether, or deionized water. Stir for 0.5-24 hours.
[0044] S6. Filter by suction, transfer the filter cake to an oven to dry and obtain pure 5-dodecanooxycarbonylfuran-2-carboxylic acid.
[0045] Preparation of sodium salts:
[0046] S1. Dissolve the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid in tetrahydrofuran, methanol, or ethanol solvent;
[0047] S2. Start stirring and slowly add sodium carbonate, sodium bicarbonate, or sodium tert-butoxide. After adding, stir for 0.5-24 hours.
[0048] S3. Filter by suction, and transfer the filter cake to an oven to dry to obtain pure sodium 5-dodecyloxycarbonylfuran-2-carboxylate.
[0049] Example 1
[0050] Step (1)
[0051] 100.0 g of 2,5-furandicarboxylic acid, 119.5 g of 5-dodecyl alcohol, and 110.3 g of p-methanesulfonic acid were added to a 500 mL reaction flask. The mixture was stirred at 120 °C for 16 h. The resulting oily substance was added to 300.0 mL of ethyl acetate and 300.0 mL of water. The organic phase was separated and collected. The ethyl acetate was removed by vacuum distillation of the organic phase. 300.0 mL of n-heptane was added and the mixture was stirred at 25 °C for 2 h. The mixture was filtered, and the filter cake was transferred to an oven and dried at 60 °C to obtain pure 5-dodecyloxycarbonylfuran-2-carboxylic acid.
[0052] Step (2)
[0053] Add 500 mL of tetrahydrofuran to the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid in step (1), slowly add 61.6 g of sodium tert-butoxide, stir and react for 1 h, filter, wash the filter cake three times with 50 mL of tetrahydrofuran, and then transfer it to an oven at 60 °C to dry for 12 h to obtain a white solid with a purity of 97.1% and a yield of 85%.
[0054] Step (3)
[0055] The sodium 5-dodecyloxycarbonylfuran-2-carboxylate obtained in step (2) was placed at room temperature to balance the moisture content to 9% to obtain sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant. The surface tension of the obtained sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant was 40 mN / m (mass concentration 0.25%) and the viscosity was 170 mPa·s (mass concentration 10%, room temperature).
[0056] The mass spectrum of sodium 5-dodecyloxycarbonylfuran-2-carboxylate prepared in Example 1 ([M+Na] = 347) is as follows: Figure 3 As shown, this indicates that the relative molecular weight is consistent with that of the target product.
[0057] The chromatogram of sodium 5-dodecyloxycarbonylfuran-2-carboxylate prepared in Example 1 is shown below. Figure 4 As shown, the purity is 97.1%.
[0058] The 1H NMR spectrum of sodium 5-dodecyloxycarbonylfuran-2-carboxylate prepared in Example 1 is as follows: Figure 5 As shown, this indicates that the chemical shift is consistent with that of the target product.
[0059] Example 2
[0060] Step (1)
[0061] 100.0 g of 2,5-furandicarboxylic acid and 119.5 g of 5-dodecyl alcohol were added to a 500 mL reaction flask, along with 12.0 g of concentrated sulfuric acid. The mixture was stirred at 120 °C for 16 h. The resulting oily substance was added to 300.0 mL of ethyl acetate and 300.0 mL of water. The organic phase was separated and collected. The ethyl acetate was removed by vacuum distillation of the organic phase. 300.0 mL of n-heptane was added, and the mixture was stirred at 25 °C for 2 h. The mixture was filtered, and the filter cake was transferred to an oven and dried at 60 °C to obtain pure 5-dodecyloxycarbonylfuran-2-carboxylic acid.
[0062] Step (2)
[0063] Add 500 mL of tetrahydrofuran to the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid from step (1), then slowly add 61.6 g of sodium tert-butoxide, stir the reaction for 1 h, filter, wash the filter cake three times with 50 mL of tetrahydrofuran, and then transfer it to an oven at 60 °C to dry for 12 h to obtain a white solid with a purity of 96.2% and a yield of 71%.
[0064] Step (3)
[0065] The sodium 5-dodecyloxycarbonylfuran-2-carboxylate obtained in step (2) was placed at room temperature to balance the moisture content to 9% to obtain sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant. The surface tension of the obtained sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant was 39 mN / m (mass concentration 0.25%), and the viscosity was 173 mPa·s (mass concentration 10%, room temperature).
[0066] Example 3
[0067] Step (1)
[0068] 100.0 g of 2,5-furandicarboxylic acid, 119.5 g of 5-dodecyl alcohol, and 61.6 g of methanesulfonic acid were added to a 500 mL reaction flask. The mixture was stirred at 120 °C for 16 h. The resulting oily substance was added to 300.0 mL of ethyl acetate and 300.0 mL of water. The organic phase was separated and collected. The ethyl acetate was removed by vacuum distillation of the organic phase. 300.0 mL of n-heptane was added, and the mixture was stirred at 25 °C for 2 h. The mixture was filtered, and the filter cake was transferred to an oven and dried at 60 °C to obtain pure 5-dodecyloxycarbonylfuran-2-carboxylic acid.
[0069] Step (2)
[0070] Add 500 mL of tetrahydrofuran to the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid from step (1), slowly add 61.6 g of sodium tert-butoxide, stir and react for 1 h, filter, wash the filter cake three times with 50 mL of tetrahydrofuran, and then transfer it to an oven at 60 °C to dry for 12 h to obtain a white solid with a purity of 96.5% and a yield of 79%.
[0071] Step (3)
[0072] The sodium 5-dodecyloxycarbonylfuran-2-carboxylate obtained in step (2) was placed at room temperature to balance the moisture content to 9% to obtain sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant. The surface tension of the obtained sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant was 42 mN / m (mass concentration 0.25%) and the viscosity was 171 mPa·s (mass concentration 10%, room temperature).
[0073] Example 4
[0074] Step (1)
[0075] 100.0 g of 2,5-furandicarboxylic acid, 119.5 g of 5-dodecyl alcohol, and 110.3 g of p-methanesulfonic acid were added to a 500 mL reaction flask. The mixture was stirred at 120 °C for 16 h. The resulting oily substance was added to 300.0 mL of ethyl acetate and 300.0 mL of water. The organic phase was separated and collected. The ethyl acetate was removed by vacuum distillation of the organic phase. 300.0 mL of n-heptane was added and the mixture was stirred at 25 °C for 2 h. The mixture was filtered, and the filter cake was transferred to an oven and dried at 60 °C to obtain pure 5-dodecyloxycarbonylfuran-2-carboxylic acid.
[0076] Step (2)
[0077] Add 500 mL of tetrahydrofuran to the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid in step (1), slowly add 34 g of solid sodium carbonate, stir and react for 1 h, filter, wash the filter cake three times with 50 mL of tetrahydrofuran, and then transfer it to an oven at 60 °C to dry for 12 h to obtain a white solid with a purity of 96.6% and a yield of 82%.
[0078] Step (3)
[0079] The sodium 5-dodecyloxycarbonylfuran-2-carboxylate obtained in step (2) was placed at room temperature to balance the moisture content to 9% to obtain sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant. The surface tension of the obtained sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant was 41 mN / m (mass concentration 0.25%), and the viscosity was 175 mPa·s (mass concentration 10%, room temperature).
[0080] Example 5
[0081] Step (1)
[0082] 100.0 g of 2,5-furandicarboxylic acid, 119.5 g of 5-dodecyl alcohol, and 110.3 g of p-methanesulfonic acid were added to a 500 mL reaction flask. The mixture was stirred at 120 °C for 16 h. The resulting oily substance was added to 300.0 mL of ethyl acetate and 300.0 mL of water. The organic phase was separated and collected. The ethyl acetate was removed by vacuum distillation of the organic phase. 300.0 mL of n-heptane was added and the mixture was stirred at 25 °C for 2 h. The mixture was filtered, and the filter cake was transferred to an oven and dried at 60 °C to obtain pure 5-dodecyloxycarbonylfuran-2-carboxylic acid.
[0083] Step (2)
[0084] Add 500 mL of tetrahydrofuran to the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid from step (1), slowly add 53.8 g of solid sodium bicarbonate, stir and react for 1 h, filter, wash the filter cake three times with 50 mL of tetrahydrofuran, and then transfer it to an oven at 60 °C to dry for 12 h to obtain a white solid with a purity of 97.2% and a yield of 81%.
[0085] Step (3)
[0086] The sodium 5-dodecyloxycarbonylfuran-2-carboxylate obtained in step (2) was placed at room temperature to balance the moisture content to 9% to obtain sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant. The surface tension of the obtained sodium 5-dodecyloxycarbonylfuran-2-carboxylate surfactant was 41 mN / m (mass concentration 0.25%), and the viscosity was 172 mPa·s (mass concentration 10%, room temperature).
Claims
1. A process for the preparation of sodium 5-dodecyloxycarbonylfuran-2-carboxylate, characterized in that, Includes the following steps: I. Unilateral esterification: S1.1 First, add 2,5-furandicarboxylic acid and dodecyl alcohol to the container, and then add the acid; The acid mentioned is one of hydrochloric acid, sulfuric acid, methanesulfonic acid, or p-toluenesulfonic acid; S1.2 After adding acid, stir and react at 100-140℃ for 12-24 hours; S1.3 The oily substance obtained from the reaction was post-treated to obtain pure 5-dodecanooxycarbonylfuran-2-carboxylic acid; Post-processing specifically includes: S1.3.1 Add ethyl acetate and water to the oily substance obtained from the reaction, and separate and collect the organic phase; S1.3.
2. Organic phase distillation removes the solvent to obtain crude 5-dodecanooxycarbonylfuran-2-carboxylic acid; S1.3.3 Add solvent to crude 5-dodecyloxycarbonylfuran-2-carboxylic acid and beat at 0-100℃ for 0.5-24 hours; S1.3.4 Filter the pulped solution and dry the filter cake to obtain pure 5-dodecanooxycarbonylfuran-2-carboxylic acid; II. Preparation of sodium salts: S2.1 Dissolve the pure 5-dodecyloxycarbonylfuran-2-carboxylic acid in an organic solvent to obtain a solution; The organic solvent is tetrahydrofuran, methanol, or ethanol; S2.
2. Start stirring and add sodium carbonate, sodium bicarbonate, or sodium tert-butoxide dropwise to the solution obtained in step S2.
1. After the addition is complete, stir the reaction for 0.5-2 hours to obtain the reaction solution. S2.3 Filter the reaction solution from step S2.2, transfer the filter cake to an oven and dry it at 50~70℃ for 8~20h to obtain pure sodium 5-dodecyloxycarbonylfuran-2-carboxylate.
2. The method for preparing sodium 5-dodecyloxycarbonylfuran-2-carboxylate according to claim 1, characterized in that, In step S1.3.3, the solvent is one or a mixture of dichloromethane, ethyl acetate, n-heptane, methyl tert-butyl ether, and deionized water.
3. The process for the preparation of sodium 5-dodecyloxycarbonylfuran-2-carboxylate according to claim 1, characterized in that, In step S1.3.3, pulping is carried out at 15-35℃ for 1-4 hours.
4. The method for preparing sodium 5-dodecanooxycarbonylfuran-2-carboxylate according to claim 1, characterized in that, In step S1.3.4, the filter cake is dried at 50~70℃.