【作者】 王庆辉；

【导师】 杨锦宗； 张淑芬；

【作者基本信息】 大连理工大学 ， 应用化学， 2008， 博士

【摘要】 蔗糖酯由于其卓越的应用性能和良好的生物降解性能和毒理学性质已被广泛应用于食品、医药、化妆品和洗涤剂中,而具有优良杀虫活性的蔗糖酯是一类极具商业前景的绿色环保型杀虫剂,它的研究和开发对作为农业大国的我国有着特殊而重要的意义。本论文以DMF为反应溶剂,用酰氯直接酯化法和酯交换法分别合成了具有生物活性的蔗糖酯化合物,研究了反应条件对酰化试剂的转化率及产品酯化度的影响,结果表明酰化试剂的用量是控制产品酯化度的最直接因素;反应中蔗糖分子中羟基的反应活性基本遵循OH-6＞OH-6’＞OH-1’＞secondary-OHs的顺序。通过蔗糖锡醛缩合物中间体在吡啶存在下与酰氯直接酯化,同时得到了高区域选择性的6-O-蔗糖酯和6,3’-Di-O-蔗糖二酯,并用此方法合成了一系列具有不同脂肪链长的6-O-蔗糖酯和6,3’-Di-O-蔗糖二酯产品。通过探讨反应过程中吡啶的作用,并基于蔗糖锡醛缩合物的结构,提出生成6,3’-Di-O-蔗糖二酯的两种可能机理。对蔗糖酯化合物的杀虫和杀菌活性的研究结果表明,蔗糖辛酸单酯杀虫活性最高,杀虫范围最广,值得被开发为新型环保型杀虫剂。用FT-IR、ESI-MS与NMR对蔗糖酯产品的结构进行了表征,重点对产品的一维和二维NMR的结构表征方法进行了深入讨论。通过对¹H NMR、¹³C NMR、HSQC、¹H-¹HCOSY与HMBC谱综合运用分析,对糖骨架中各个碳和氢信号进行了准确的归属,提出了用HMBC谱来确定蔗糖酯产品酯化位置的新方法,该方法直观且准确,非常适合蔗糖酯化反应的被酯化羟基位置的确定。采用HPLC-ELSD,通过优化流动相、洗脱梯度等色谱条件,对不同脂肪链长度的蔗糖酯产品中的主要成分如单酯、二酯及多酯进行了有效分离,并结合ESI-MS对蔗糖酯样品进行了定性分析。对外标校正的纯蔗糖酯化合物的HPLC-ELSD准确定量方法进行了探讨,建立了实验室和工业化生产蔗糖酯产品的反应监控及质量控制的分析方法,对该类化合物在某些应用中的准确定量方法进行了探讨,满足了不同的要求。测定了不同脂肪酸链长的纯蔗糖酯化合物以及组成不同的蔗糖酯混合物的水溶液的表面性质和界面性质,并利用两维溶解度参数模型,对该类化合物的溶解性和疏水性进行了量化,在此基础上对其界面现象进行了分析和解释。结果表明,该模型适用于对糖基表面活性剂界面行为的解释。研究了蔗糖酯化合物的其它物化性能如HLB值、乳化力、硬水稳定性和发泡力及泡沫稳定性与结构和产品组成的关系。更多还原

【Abstract】 Sucrose esters（SE） have attracted continual interest in the past decades owing to their superior performance and compatibility in the health and environmental arenas and are currently being employed in the food,cosmetic and detergent industries.In addition,several types of synthetic SE have shown potent insecticidal activities and could be a new kind of insecticide with a brilliant commercial prospect.Research and development of it will be particularly important for China which is a big agricultural country.SE compounds were prepared in this work by esterification and transesterification of sucrose using DMF as reaction solvent.The influences of reaction conditions on the conversion of acylating agent and degree of substitution were investigated.Molar ratio of acylating agent to sucrose was found to be the critical factor to the degree of substitution.The reaction activities of free hydroxyl groups in sucrose follows the order OH-6＞OH-6’＞OH-1’＞secondary-OHs.Regioselective formation of 6-O-acylsucroses and 6,3’-di-O-acylsucroses in one pot with good yields were achieved by a typical acylation method of sucrose via dibutylstannylene acetal.Explanations for the regioselectivities observed during this stannylene acetal mediated reaction were also proposed based on the structures of stannylene acetal in solution and the intramolecular migration of stannylenes.C₈SE provides high levels of mortality against broad range of arthropods and will have a bright commercial future.6-O-acylsucroses and 6,3’-di-O-acylsucroses were fully characterized using FT-IR, ESI-MS and NMR spectroscopy.Spectral assignments of ¹H and ¹³C NMR spectra were performed using ¹H-¹H COSY,¹H-¹³C COSY and HMBC techniques.It was found that HMBC experiment was a convenient method to determine the position of acylation.A high performance liquid chromatographic method has been developed for the separation and quantitation of sucrose ester analogs using an evaporative light scattering detector（ELSD） in combination with the electrospray ionization mass spectrum（ESI-MS） technology.By varying the mobile phases and gradient conditions,the complex mixtures of synthetic or commercial sucrose esters were completely separated into several fractions such as mono-,dior higher esters with different regioisomers in each one on a single run.A separation and quantitative method of ten pure monoesters and diesters was also described to evaluate the method’s potential application in the quantitiation of all sucrose ester analogs using external standards.The described method is found to be accurate,relatively inexpensive, straight-forward and reproducible and in principle can be readily applied to the analysis of any sucrose ester analogs of interest with little variation to meet all requirements of qualitative and quantitative analytical procedure.In order to get some precise structure-activity relationships in this series of compounds, surface properties and interfacial properties of pure SE compounds and sucrose esters mixtures with different hydrophobic chain lengths were investigated.A two-dimensional model of solubility parameters was developed to interpret the interfacial phenomena of these compounds.Some physiochemical properties of these compounds,such as HLB value, emulsifying power,stability in hard water,foamability and form stability were also investigated.更多还原