摘要
本论文分两部分,第一部分为2-咪唑烷酮衍生物的合成及工艺研究,第二部分为三氟乙酸的合成工艺研究。
第一部分：从工业化的角度设计2-咪唑烷酮衍生物的合成路线,合成了1-甲磺酰基-2-咪唑烷酮、1-氯甲酰基-3-甲磺酰基-2-咪唑烷酮、1-氯甲酰基-2-咪唑烷酮等15种化合物,所合成的化合物经过熔点比对和HNMR表征正确。提出了1-甲磺酰基-2-咪唑烷酮的合成新工艺,以甲烷磺酸酐代替甲烷磺酰氯进行磺酰化,具有收率高、操作安全、原料来源广、廉价易得等优点,并对该工艺各影响因素进行了系统研究,得出最佳工艺为：投料比甲烷磺酸酐：三乙胺：2-咪唑烷酮(mol)=1.25：1.25：1,反应温度为80℃,反应时间为6 h,反应溶剂为苯或者甲苯。提出了1-(2-氨乙基)-2-咪唑烷酮的合成新工艺,在无溶剂条件下,高温环化合成目标产物,并从反应原料、反应温度、反应时间等方面进行了讨论,得出1-(2-氨乙基)-2-咪唑烷酮的最佳工艺为：二乙烯三胺：尿素(mol)=2：1,反应温度为200-210℃,反应时间是4 h。
第二部分：以2,2,2-三氟乙醇为原料氧化制备三氟乙酸,该工艺具有反应装置简单、产品纯度高、反应温度低等优点,并对各影响因素进行了系统研究,得出2,2,2-三氟乙醇氧化为三氟乙酸的最佳工艺条件为：以三氧化铬为氧化剂,原料：氧化剂=1:1.25,在80-100℃之间反应4 h,以质量分数为30%的氢氧化钠进行中和时,三氟乙酸的收率最高为77%,产品纯度>98%。对三氟乙酸蒸馏后的母液进行套用,得出在2,2,2-三氟乙醇：硫酸(mol)=1:5时,蒸馏母液可以套用3次,而产率稳定。
This paper consists of two parts:the first part is the synthesis and studying on 2-imidazolidine derivatives. The second part is the study on the technology of trifluoroacetic acid.
PartⅠ:In this part, the synthesis routine of 2-imidazolidone derivatives were designed from the angle of view of industrialization, and fifteen compounds such as 1-Methanesulfonyl-2-imidazolidinone,3-Chlorocarbonyl-1-methanesulfonyl-2-imidazolidinone,1-Chlorocarbonyl-2-Imidazolidone and so on were synthesized. The molecular structures of fifteen products were characterized by 1HNMR and measuring melting-point, and the compounds obtained was final objective products. A new technology to synthesis of 1-Methanesulfonyl-2-imidazolidinone using methanesulfonic anhydride to replace methanesulfonyl chloride was put forward. This method was of characteristic of high yield, safe operation, the widely sources of raw material, low cost and so on. The effect factors on the new technology were investigated systematically, from the results it was concluded that the optimum technique was: methanesulfonic anhydride:Triethylamine:2-imidazolidinone (mol)=1.25:1.25:1, the reaction temperature was 80℃, reaction time was 6 hours and solvent was benzene or toluene. Under solvent-free condition, 1-(2-Aminoethyl)-2-imidazolidinone was synthesized by cyclization reaction at high temperature. The materials, reaction temperature and reaction time were discussed, and the optimum reaction condition was Diethylenetriamine:Urea (mol)=2:1, at the temperature of 200-210℃and reaction time of 4 hours.
PartⅡ:Trifluoroacetic acid was prepared by oxidation reaction from 2,2,2-Trifluoroethanol. The preparation process has advantages of sample apparatus, high product purity and low reaction temperature. The optimum technological condition was determined by systematically studying the effect factors and was that:chromic oxide as oxidant,2,2,2-Trifluoroethanol oxidation=1:1.25, at 80-100℃for 4 hours. Using 30%(mass fraction) sodium hydroxide solution neutralized the reaction solution, trifluoroacetic acid could be obtained with purity higher than 98%, the highest yield was 77%. Study on recycling of trifluoroacetic acid distillation mother liquid,2,2,2-Trifluoroethanol:sulfuric acid (mol)=1:5, the trifluoroacetic acid distillation mother liquid can recycle 3 time without obvious fluctuation.
引文
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