【作者】 彭桂丽；

【导师】 林原斌；

【作者基本信息】 湘潭大学 ， 有机化学， 2011， 硕士

【摘要】 环丙基化合物是一类比较重要的有机化合物,是具有很好生物活性和高选择性的构效基团,因此广泛应用于医药,农药等行业。目前,虽然其合成方法很多,但是考虑到产率和原料获得的难易程度,本文主要采取亲核取代和卡宾反应来获得。同时环丙基化合物不稳定,容易开环;醇还容易发生β-消除得到烯烃类化合物,因此环丙基烷基醇容易发生开环消除反应得到高烯丙基卤化物,其具有着烯烃和卤化物的双重性质,也是有机合成中的重要中间体。本文就是通过环丙基烷基醇开环消除来制备高烯丙基卤化物。本文的主要研究工作可分为以下两大方面:一:环丙基化合物的合成研究1.利用亲核取代反应合成环丙基酮类化合物,并通过格式反应制备环丙基烷基醇类化合物,对其影响因素进行了探讨,获得了一条反应条件温和、产率较高的合成路线。2.利用卡宾反应合成了环丙基羧酸酯即第一菊酸乙酯化合物。3.分别以丙酮和二氯甲烷为溶剂,第一菊酸乙酯为原料,高锰酸钾为氧化剂的反应条件制得环丙基二羧酸,并对以二氯甲烷为溶剂的方法进行了条件探讨。该方法使用了相转移催化剂,提高了产率,同时减少了硫酸的用量,有利于环保。4.根据邻位的二羧酸易脱水可以形成较稳定的五元环的特性,我们使用醋酸酐为脱水剂,以环丙基二羧酸为原料进行反应制得具有生物活性的环丙基羧酸酐即6,6-二甲基-3-氧杂双环[3.1.0]己烷-2,4-二酮。二:环丙基烷基醇的开环产物即高烯丙基卤化合物的合成研究我们使用氢卤酸在不同的反应条件下将环丙基烷基醇开环制得了一系列的高烯丙基卤化物。此方法具有操作简单、原料易得、反应时间短、产率较高和制得的烯烃具有顺反异构的特点。本文通过1~H核磁共振(1~H NMR)、(13)~C核磁共振((13)~C NMR)等测试手段对所合成的目标产物进行了结构表征。其中1-环丙基-1-甲基丁醇、1-环丙基-1-甲基戊醇、1-环丙基-1-苄基乙醇、1-氯-4-甲基-3-庚烯、1-氯-4-甲基-3-辛烯、5-氯-2-苄基-2-戊烯、1-溴-4-甲基-3-庚烯、1-溴-4-甲基-3-辛烯、5-溴-2-苄基-2-戊烯、1-碘-4-甲基-3-庚烯、1-碘-4-甲基-3-辛烯、5-碘-2-苄基-2-戊烯为未报道的化合物。更多还原

【Abstract】 As an important kind of organic compounds, cyclopropyl compounds have a wide range of applications in medicine, pesticide and other industries for its good biological activity and selectivity of the strucure-activity groups. At present, there have been many methods to synthesize cyclopropyl compounds, but we adopted nucleophilic substitution reactions and carbene reactions considering the yields and the ease of access to raw materials.At the same time, cyclopropyl compounds are unstable and easy to be open-loop and alcohols are prone to proceedingβ-elimination to produce alkenes, therefore cyclopropyl alkanols are prone to proceeding ring-opening elimination to get high homoallylic halides which have the dual natures of alkenes and halides and are important intermediates in organic synthesis. High homoallylic halides were synthesized by the ring-opening elimination reaction of cyclopropyl alkanols in this paper.The main research work of this paper was divided into two aspects:Ⅰ: The research of the synthesis of cyclopropyl compounds(1) We took the nucleophilic substitution reaction to synthsize cyclopropyl ketones compounds, then used the format reaction to prepare cyclopropyl alcohol compounds.We discussed the influencing factors and accessed a mild reaction conditions and high yield synthetic route.(2) The cyclopropyl carboxylate that was the first Ju-ethyl compounds was synthesized through the carbene reaction.(3) The cyclopropyl dicarboxylic acid was obtained by using the acetone and dichloromethane as solvents, the first Ju-ethyl as raw material and the potassium permanganate as oxidant. The reaction conditions of the method of dichloromethane as solvent were aslo discussed, in this method the phase transfer catalyst was used, the yield was improved and the amount of sulfuric acid was reduced, it is friendly to the environment.(4) According to the character that o-dicarboxylic acid is easily dehydrated to form a more stable five-membered ring, we used acetic anhydride as dehydrating agent and cyclopropyl dicarboxylic acid as raw materials to prepare the biological activity cyclopropyl anhydride: 6,6-dimethyl-3-oxa-bicyclo[3.1.0]hexane- 2,4-dione.Ⅱ: The research of cyclopropyl alkanol’s ring-opening product (high homoallylic halides )A series of high homoallylic halides were synthesized by the open-loop system of cyclopropyl alkanols and halogen acid under different reaction conditions. This method is simple, the raw materials are readily available, the reaction time is short and the yield is high and alkenes have the character of cis-trans isomerization.The structures of the synthesized compounds are confirmed by 1~H-NMR, (13)~C-NMR and several other means. In this paper, 1-cyclopropyl-1-methyl butanol, 1-cyclopropyl-1-methyl pentanol, 1-cyclopropyl-1-benzyl alcohol, 1-chloro- 4-methylhept-3-ene, 1-chloro-4-methyloct-3-ene, 5-chloro-2-benzylpent-2-ene, 1-bromo-4-methylhept-3-ene, 1-bromo-4-methyloct-3-ene, 5-bromo-2-benzylpent- 2-ene, 1-iodo-4-methylhept-3-ene, 1-iodo-4-methyloct-3-ene and 5-iodo-2-benzylpent- 2-ene were synthesized, which were not reported before.更多还原