【作者】 陶亮；

【导师】 银董红；

【作者基本信息】 湖南师范大学 ， 有机化学， 2006， 硕士

【摘要】 20世纪90年代后期兴起的绿色化学,是从源头清除污染的一项措施,它为人类解决化学工业对环境的污染、实现经济和社会可持续发展提供了有效的手段,成为化学科学发展的前沿,而且是21世纪化学发展的重要方向之一。离子液体与传统溶剂相比具有无毒、无挥发性、无可燃性、热稳定性高、在宽广的温度范围（-100～200℃）内处于液体状态、可以溶解大多数有机物等特点,是一种新型的取代挥发性有机溶剂的绿色溶剂。研究其在化学领域的各个分支的应用可减少乃至消除溶剂造成的环境污染问题,同时也有着重要的理论意义。 本文分别采用直接合成法和两步合成法成功合成了一系列高纯度,性质稳定,不同组成的离子液体,如[Bmim][BF₄]、[Bmim][PF₆]、[BPy][BF₄]、[EtPy][BF₄]、[Emim][PF₆]、[Bmim]Cl和[Emim]Br等,并用FT-IR、¹H-NMR、¹³C-NMR对它们进行了结构确证。 以合成的离子液体为反应介质,以过氧化氢（H₂O₂）为氧化剂,研究了Mn（Salen）络合物催化环己烯的环氧化反应。考察了不同反应介质、不同结构Mn（Salen）络合物催化剂和反应温度等反应条件对环己烯环氧化反应规律的影响。结果表明,以相对廉价的绿色氧化剂H₂O₂代替较昂贵的二乙酸碘苯（PhI（OAc）₂）或间氯过氧苯甲酸（m-CPBA）,在离子液体—CH₂Cl₂混合溶剂中,Mn（Salen）络合物催化剂具有高活性,且可高选择性获得环氧环己烷产物。如当以邻苯二胺和水杨醛制更多还原

【Abstract】 The Green Chemistry aimed at eliminating pollutions from the beginning has been developed in the late of 1990’s. The Green Chemistry provides some measures to solve the pollution of the chemical industries and to keep the development of the economy and society, which is becoming an active area of chemical research in the 21 century. Room temperature ionic liquids （RTILs）, which have the advantages of no-toxicity, no-volatility, no-flammability, high thermal stability, wide liquid range （-100²00℃）, miscible with most of organic compounds, and have been becoming the latest green solvents to replace the volatile organic solvents. RTILs can reduce or eliminate the environment pollution of the solvents, which have a wide application in all branches of chemistry and important practical values.In this paper, a series of RTILs were synthesized by one-step and two-step method, which were identified by FT-IR,¹H-NMR and ¹³C-NMR spectra. These RTILs are 1-butyl-3-methyl imidazolium tetrafluoborate （[Bmim][BF₄）, 1-butyl-3-methyl imidazolium hexflorophosphate （[Bmim][PF₆]）, 1-butylpyridinium tetrafluoroborate （[BPy][BF₄]）, 1-ethylpyridinium hexflorophosphate （[EPy][PF₆]）, 1-butyl-3-methyl imidazolium chloride （[Bmim]CI） and 1-ethyl-3-methylimidazolium bromide （[Emim]Br）, repectively.The epoxidation of cyclohexene in ionic liquids catalyzed by Mn（Salen） complex with hydrogen peroxide as oxidant was studied. The effects of the reaction media, various Mn（Salen） complexes, and reaction temperatures on the epoxidation were investigated. It was found that handy hydrogen peroxide could be an alternative to expensive oxidant, such as PhI（OAc）2 and m-CPBA, and that ionic liquid medium gave higher conversion and selectivity to cyclohexene epoxide in comparison with the reaction performed in conventional organic solvent. 100% of the conversion of cyclohexene with 94% of selectivity to cyclohexene epoxide were obtained when the reaction was performed in the solvent of neutral [Bmim][BF4]-CH2Cl2（3:2, v/v） at 273 K using Mn（Salen） complex prepared by salicylaldehyde and o-phenyldiamine as a catalyst. Moreover, the final products could be easily separated from reaction system by simple extraction over hexane. The ionic liquids was reused and found it’s the decomposition of Mn（Salen） under the oxidant （H2O2） that leading to the decrease of conversion and selectivity.2-cyclohexene-l-one is synthesized by the oxidation reaction of cyclohexene under V2O5 using H2O2 as oxidant in RTILs. Several factors, such as reaction time, temperature, amount of V2O5 and H2O2, which may have effect on reaction, have been’studied. Comparision reaction between in organic solvents and in RTILs, fine conversion of cyclohexene andhigh productivity of cyclohexene-1-one have obtained in [Bmim][BF4]-acetone. Indeed the conversion of cyclohexene reached 88.7% with 91.1% of selectivity to 2-cyclohexene-l-one when the reaction was performed in the mixed solvent of neutral [Bmim][BF4]-acetone （2:5, v/v） using V2O5 （2%, molar ratio） as a catalyst and H2O2 （cyclohexene/ H2O2=1:3, v/v） as oxidant at 313 K for 10 h, The ionic liquids was reused for six times, and found decrease in the conversion of cyclohexene and slectivity of 2-cyclohexene-l-one.更多还原