【作者】 徐叔军；

【导师】 李桂玲；

【作者基本信息】 华中科技大学 ， 有机化学， 2006， 硕士

【摘要】 本文概述了环氧-二十碳三烯酸(EETs)及其结构类似物14, 15-环氧-5(Z)-二十碳二烯酸(14,15-EE-5-ZE)的研究近况,对14,15-EE-5-ZE的全合成进行了探讨,设计了14,15-EE-5-ZE的前体化合物5(Z), 14(Z)-二十碳二烯-1-醇的一条新合成路线,并对其合成进行了详细的研究。以1,8-辛二醇为原料,与40%氢溴酸进行单溴代反应,得到8-溴-1-辛醇,在对甲苯磺酸吡啶盐(PPTs)的催化下与2,3-二氢吡喃反应,保护分子中的羟基,再与1-庚炔进行偶联,以P-2镍为催化剂立体选择性催化加氢,酸性条件下脱末端的2,3-二氢吡喃对羟基的保护,使用氯铬酸吡啶盐(PCC)将醇氧化成醛(a)。再以1,5-戊二醇为原料,三溴化磷使之单溴代,得到5-溴-1-戊醇,在对甲苯磺酸吡啶盐(PPTs)的催化下与2,3-二氢吡喃反应保护其另一端的羟基,与三苯基膦反应生成季磷盐(b)。(a)与(b)在强碱正丁基锂的作用下进行Wittig反应,然后脱去末端的2,3-二氢吡喃保护基,得到5(Z), 14(Z)-二十碳二烯醇。反应总收率为3.4%。本文在合成方面所做的工作:系统研究了对称二醇的单溴代反应反应时间、反应温度、溶剂用量、反应物摩尔比等因素对产率的影响。末端炔与溴代物的偶联反应条件的优化,初步探讨了反应机理。顺式加氢催化剂P-2镍制备方法的改进。其他反应条件的探索及讨论。实验过程中应用薄层层析的方法摸索产品的分离条件,利用硅胶柱层析提纯产品,并通过红外光谱、核磁共振碳谱及质谱验证了产品结构。实验表明,这一合成路线具有反应条件温和,立体选择性较高的特点,合成路线是可行的。更多还原

【Abstract】 In this paper, we overviewed the epoxyeicosatrienoic acid(EETs) and its analogue-14, 15-epoxyeicosa-5(Z)-enoic acid(14,15-EE-5-ZE) recent status. The total synthesis of 14, 15-EE-5-ZE was primarily explored. A new stereoselective synthesis route of the key intermediate -(5Z,14Z)-gadoleyl-1-ol was designed and researched.In this work , 1,8-octodiol, the starting material, reacted with 40% hydrobromic acid to produce 8-bromooctan-1-ol, with the catalytic action of PPTs, its hydroxyl group was protected by 2,3-dihydropyran. Then it coupled with 1-heptaalkyne, by means of P-2 nickel as catalyst, stereoselectivity catalysis hydrogenated, with the catalytic action of acid to take off extremital 2, 3-dihydropyran which protected hydroxy group, then used PCC to oxidize alcohol into corresponding aldehyde(a). 1,5-Pentanediol reacted with phosphorus tribromide to make it mono-bromination, under the catalytic action of PPTs it reacted with 2,3-dihydropyran to protect another hydroxy group, then to react with triphosphine, produced quarterphossal(b). (a) with (b) under strong base butyl Lithium, Wittig reaction was carried out, after cast off extremital 2,3-dihydropyran which protected hydroxy group, then 5(Z),14(Z)-gadoleyl-1-ol was obtained. Total yield was 3.4%.The main work we did on synthesis: We studied bromination reaction influence factor in detail, such as reaction time、reaction temperature、solvent dosage、reagent mole ratio, and optimized the reaction condition, discussed reaction mechanism rudimentally. We optimized reaction condition and discussed the mechanism of 1-heptaalkyne coupled with mono-bromide. We improved on the technique of preparation P-2 nickel catalyst. We explored and discussed the reaction condition of other reactions. During experiment we applied thin-layer chromatography to grope the separating condition of product, utilized silica gel column chromatography to separate and purify product, and applied infrared spectrum, 13C NMR, mass spectrum to testify product structure. Result indicated this route of synthesis possess mild reaction conditions, a higher stereoselectivity. Synthetic route was feasible.更多还原