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With anhydrous sodium carbonate at 20℃; for 5h; Green chemistry; |
General procedure for the hydroalkoxylation reactions
General procedure: To a solution of activated alkene(0.5 mmol) in alcohol (2.0 mmol) was added Na2CO3 (0.2 mL, 0.05 M aq.), and the solution wasstirred until alkene was completely consumed (monitored by TLC) or an appropriate time andextracted with ethyl acetate (3 ×5 mL). The combined organic layers washed with brine (10 mL),dried over Na2SO4, filtered, and concentrated in vacuo. The crude product was purified by silicagel column chromatography to give the β-alkoxycarbonyl compound. |
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in Gegenwart eines basischen Anionenaustauschers; |
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With 1,8-diazabicyclo[5.4.0]undec-7-ene at 20℃; for 96h; |
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at 120℃; for 0.166667h; Microwave irradiation; |
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With Mg3.0Al(OH)8.95(C(00)O3)25*2.04H2O for 4h; Reflux; |
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With CsAlSi2O6 at 170℃; for 12h; Autoclave; |
Reaction Procedure
General procedure: Alcohols (38 mmol, excess amount), olefin (9.5 mmol), and the catalyst (0.03 g) were reacted in a suitable vessel. No additional solvent was used except for the reaction of phenol. For reactions performed under reflux conditions, a 10-mL two-neck round-bottom flask equipped with a reflux condenser and argon inlet and for reaction under autogenously pressure a 5 mL, a high pressure stainless steel reactor was used. Reactions with microwave irradiation were performed in a 15mL polytetrafluoroethylene (PTFE) container at 900W for 30 min. After the reaction, the solid catalyst was separated by centrifugation (5040 g for 5 min) and the products were analyzed by gas chromatography mass spectrometry (GC-MS). Conversions were determined by using o-xylene as an internal standard. In some cases, the used catalysts were washed with ethanol, dried at 100°C overnight, and calcined at 300°C for 4 h. |
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With sodium hydroxide |
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With potassium etoxide at 60 - 70℃; Flow reactor; |
Figure 1 is a process chart showing a method for preparing ethyl 3-ethoxypropionate of the present invention. The method for preparing ethyl 3-ethoxypropionate of the present invention can be broadly divided into a synthesis step, a salt removal step, and a purification step, and can be performed in a continuous process. In the synthesis step, an ethanol (11), an ethyl acrylate monomer (13) and a catalyst (12) are added and reacted to the synthesis reactor (10). In one embodiment the reaction is carried out at a temperature of 60 ° C. to 70 ° C. for 120 to 180 minutes. When the reaction time is 120 minutes or less, the yield of the product, ethyl 3-ethoxypropionate, may be lowered. When the reaction time is longer than 180 minutes, all the amounts that can be synthesized may be completed to reduce the synthesis efficiency or to generate side reactions. Can be. The ethanol and ethyl acrylate is added in a molar ratio of 1.0 to 2: 1, the catalyst is sodium ethoxide (Sodium ethoxide) in one embodiment, 0.2 to 0.6% by weight relative to the ethyl acrylate monomer is preferred. The reaction product after the reaction in the synthesis reactor 10 is introduced into the neutralization reactor 20, the neutralization reactor may neutralize the reaction product showing the basicity by sodium ethoxide using the acid (21), the Neutralization can inhibit side reactions by lowering the activity of the catalyst. The acid may be sulfuric acid, for example, and may be used by diluting 30% in ethanol or undiluted sulfuric acid. The reaction product which has been neutralized in the neutralization reactor 20 is transferred to the first product storage tank 22, which is then transferred to the desalination filter 23 to remove the salt and to the second product storage tank 24. Can be stored. The material of the desalted second product storage tank 24 is a mixture containing ethyl 3-ethoxypropionate, unreacted material ethyl acrylate, a large amount of ethanol and a small amount of water, as the object of the present invention. . The first product storage tank 22 and the second product storage tank 24 may further include a chiller having a heat exchanger. |
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With sodium methoxide In lithium hydroxide monohydrate at 60℃; for 1h; Large scale; |
1-4 Examples 1 to 4
In Examples 1 to 4 was an experiment for synthesizing the alkyl 3-alkoxypropionate product from the alkyl acrylate and alkyl alcohol as a reactant. EAM (ethyl acrylate monomer) was used as alkyl acrylate and ethanol was used as alkyl alcohol. In addition, the molar ratio of alkyl acrylate: alkyl alcohol is 1: 1 to 1: 3 so that the content of EtOH was used. The product of the reactionEEP ethyl 3-ethoxypropionate was produced.The moisture content was based on 100 wt% of the total weight of the mixture of alkylalcohol, catalyst and added water.First, a 20-wt% sodium ethoxide (CH3CH2O-Na+) solution in EtOH as a strong alkali catalyst was added to an EtOH of 18 kiloliter sized large reactor as the weight shown in Table 1 below, and stirred. Mix uniformly. Thereafter, water was added to the mixture such that the water content was set forth in Table 1 below.The mixture was heated to 60°C with stirring and reacted by dropwise addition of EAM of the weight shown in Table 1 below over 60 minutes.When the exothermic reaction was stopped, a sample of the reaction product was completed and analyzed by Gas Chromatography (GC).When the conversion rate is less than 97wt% analysis result was added to the content described in Table 1 below and stirred for an additional 30 minutes. |
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at 108℃; |
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With potassium etoxide at 60℃; for 1h; Large scale; |
1 Reaction process 1. Pre-batch reaction process
In the reaction system, a pre-batch reaction process was performed according to the following procedure. Put EtOH 1.50kg in 5L reactor Add 35g of strong alkali catalyst 20wt% sodium ethoxide EtOH solution (a solution in which the catalyst is dissolved in EtOH) to the above EtOH and stir to achieve a uniform concentration and mix Analyze the moisture content of the mixture, add an appropriate amount of moisture to the mixture, stir and mix, and adjust the moisture content of the mixture to 600~1,000 wtppm. Heat to 60 °C while stirring the above mixture Add 1.97kg of EAM to the mixture gradually dropwise for 60 minutes (inject to reduce droplets) After the EAM dropping was completed, a small amount of the reaction mixture was collected and analyzed by GC to calculate the conversion rate. At this time, the conversion rate was 90~95 wt%, and the moisture content was analyzed. At this time, the moisture content was less than 50 wtppm. Add moisture to the above mixture, stir and mix, and adjust the moisture content of the mixture to 50~200 wtppm Stir for 60 minutes so that the mixture result is further reacted As a result of collecting a small amount of the mixture and analyzing it by GC, the conversion rate was more than 97 wt%. |
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With potassium etoxide at 50℃; |
1-5 [Experimental Examples and Comparative Examples]
In the experimental example of the present invention, an experiment for synthesizing the product ethyl 3-ethoxy propionate from ethyl acrylate and ethyl alcohol was conducted.First, the water content of the reactants, ethyl alcohol and ethyl acrylate monomer (EAM; Ethyl acrylate monomer), was measured using a Karl-Fisher moisture analyzer.Sodium ethoxide (CH3CH2O-Na+) was used as a reaction catalyst, and sodium ethoxide was prepared as a 20 wt% solution using ethyl alcohol as a solvent.The molar ratio of ethyl acrylate monomer (EAM): ethyl alcohol was set to be 1:1 to 1:1.5.After completion of the reaction, 1,000 ppm of a phenolic antioxidant, Dibutyl Hydroxyl Toluene (BHT) was added to the reaction product, and then a sample was collected and analyzed by GC (Gas Chromatography). |
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