【作者】 孙凯；

【导师】 周新锐；

【作者基本信息】 大连理工大学 ， 应用化学， 2016， 硕士

【摘要】 α,β-不饱和醇化合物包含有化学性质活泼的不饱和双键和羟基基团,该类化合物能够参与加成、酯化、醚化和卤代等很多不同类型的反应,是合成香料、农药、表面活性剂及医药等的重要中间体。不饱和醇有很多不同路径的制备方法,以烯烃为原料合成α,p-不饱和醇一直是有机合成化学领域中的研究热点之一。本文主要对两个方面进行了介绍：1.以烯烃为原料,探索了两种不同的反应路径合成对应的α,β-不饱和醇。2.制备多官能团的磷叶立德试剂,探索用Wittig反应制备多冠能团的Z式烯烃,为育亨宾的D,E砌块的合成进行部分重要的探索。两种制备α,β-不饱和醇的路径：路径一主要是先生成对应的酯,然后通过水解反应将酯转化成对应的不饱和醇。实验以环己烯为底物进行探索,利用不同的过氧化物作为氧化剂进行氧化,得到的产物利用高效液相色谱(HPLC)进行产率检测。实验的检测结果显示利用过氧化苯甲酸叔丁酯做氧化剂时生成对应的苯甲酸环己烯酯的产率最高,产率为49%。当用苯甲酸和过氧化环己酮(CYHPO)做氧化剂时并没有产物生成。路径二主要是先生成对应的过氧化氢化合物,然后将过氧化物进行还原。其中卟啉类催化剂R-TPP进行催化反应,得到的过氧化氢化合物在分子筛催化剂Cu-OMS-1的作用下分解还原成对应的α,β-不饱和醇产物。实验中以2,3-二甲基-2-丁烯(DMB)为代表进行实验探索,分离得到对应的氢过氧化物,然后对生成的过氧化氢化合物的催化还原反应进行了探索。制备纯度较高的2,3-二甲基-3-丁烯-2醇,用其作为标准物绘制标准曲线,对反应产率进行定量探索。换用环己烯,2-甲基-2-丁烯,香茅醇等底物进行反应时,也能得到对应的α,β-不饱和醇。在育亨宾的全合成路径中,其中有一条以D,E砌块为中间体的合成路径,该路径的难点在于如何获得多官能团Z式结构的三烯烃,以便进一步生成对应的D,E砌块。实验过程中以巴豆酸甲酯和氯磷酸二苯酯为原料,合成并分离出了可用于制备Z式烯烃的磷叶立德试剂,为进一步探索D,E砌块的合成提供了前提条件。更多还原

【Abstract】 α, β-unsaturated alcohol contains two function groups with high chemical activity,i. e. double bond and hydroxyl group.They provide the competition during the reactions like addition, esterification, etherification, etc., and halogenated reaction which is an important intermediate in synthetic perfumes, pesticides, surfactants and pharmaceuticals, etc. Many different ways have been researched to synthesize the unsaturated alcohol,but it is a research focus in the field of organic synthetic chemistry research using the olefin as the starting material to synthesize α,β-unsaturated alcohol.The paper will focus on two aspects:1.Two different paths to synthesize the α,β-unsaturated alcohol have been explored using the olefin as the starting material.2.In order to obtain the D, E blocks of the Yohimbine, polyfunctional phosphorus Ylide reagent has been prepared out which will be used to synthesize the Z-type olefin by the Wittig Reaction.This article describes two paths to prepare α,β-unsaturated alcohols.Route 1 prepare ester as a reaction intermediate, which will be hydrolysis to give the corresponding unsaturated alcohol.Cyclohexene is used as a substrate in the experiments. The product yields are detected by HPLC in the oxidation reaction which use different peroxide as the oxidant.The results show that the yield of cyclohex-2-en-1-yl benzoate is 49% which is the highest when tert-butyl benzoperoxoate is used as the oxidant.There is no product detected when benzoic acid and CYHPO are used as the oxidant.In Route 2 peroxide will be reduced after olefins have been converted to organic hydroperoxide.R-TPP type porphyrin is used as a catalyst to obtain the organic hydroperoxide, which will be decomposed reduction by the Zeolite Catalysts Cu-OMS-1 to α, β-unsaturated alcohol.2,3-dimethylbut-2-ene is a representative in the experiment exploration process.The reduction decomposition reaction of the hydrogen peroxide isolated is explored later.A standard curve line of 2,3-dimethylbut-3-en-2-ol which has been purified will be applied to the quantitative reaction. The corresponding α, β-unsaturated alcohol will be prepared when cyclohexene,2-methyl-2-butene, citronellol and other substrates participate in the reaction.There are many different paths to prepare the Yohimbine. Our team has designed a new route in which the D,E blocks are important intermediate.Given multi-functional structure of Z-type olifin which contain three double bonds is the key of the route. By using methyl crotonate and diphenyl chlorophosphate as the starting material, a novel poly functional phosphorus Ylide reagent has been prepared and isolated which can be used for the selective synthesis of Z-type olefin in the experiment. Our work provide a prerequisite for the synthesis of the D,E blocks.更多还原