【作者】 孟桂英；

【导师】 安德烈；

【作者基本信息】 湖南大学 ， 有机化学， 2006， 硕士

【摘要】 大量文献表明末端含有多个-SCH₃的多头功能基团的有机分子可将纳米金组装成尺度或形态可调节的金纳米粒子簇。设计并合成一些形态多样的π共轭系多-SCH₃功能基的芳炔硫醚类分子对获得一些具有良好组装效果,尤其是能够控制团簇形态或控制团簇尺度有用的功能分子有着重要的理论和实际意义。为了合成上述芳炔硫醚类化合物需要构筑一些重要的末端功能砌块。本论文在大量的文献调研和本实验室过去研究结果的基础上,利用亲核硫试剂甲硫基甲基苯基砜（methylthiomethyl phenyl sulfone, MP-S）与芳香醛的“一锅反应”,成功的合成了一系列甲硫芳炔化合物I_a-h,从而为实现形态各异的芳炔硫醚类分子提供了一个良好的构筑平台。甲硫基甲基苯基砜（MP-S）是一种用途十分广泛的有机硫试剂。已知文献报道制备MP-S的方法产率偏低得不到有效利用,通过查阅大量文献以及对反应机理的充分认识之后,我们对MP-S的制备方法进行了多方面的改进,改进后的方法不仅使反应时间大大缩短,而且使MP-S的产率由文献的38%提高到51.2%.在此基础上,探讨了甲硫芳炔类化合物的“一锅合成”法。通过分析MP-S的结构可知,这类化合物都含有一个活泼的亚甲基,当该亚甲基经碱处理发生亲核加成反应时,与其相连的苯亚磺酰基又可以作为很好的离去基团发生消除反应。所以我们以MP-S为亲核硫试剂,严格控制实验条件,先用强碱对其进行处理,然后向反应体系中加入相应的反应物。“一锅法”以较高产率成功的合成了一系列甲硫芳炔目标化合物I_a-h。最后我们对“一锅合成”法的反应机理进行了深入系统地研究,据反应得到的产物推测,“一锅反应”经历了双消除过程,首先MP-S经强碱处理后生成了相应的碳负离子,该碳负离子与芳香醛反应后和氯磷酸二乙酯作用给出了中间体V,在强碱的作用下V中的两个离去基团经过两次消除得到了最终的目标分子I_a-h,为了验证V的生成我们用水和乙酰氯代替氯磷酸二乙酯捕捉到了相应的产物VI和VII。另外中间体化合物II_a-h也是支持这个反应机理的重要证据,我们在反应过程中通过改变碱来控制消除的进程,以较高产率分离得到了双键化合物II_a-h,本文还进一步考察了中间体II_a-h的消除反应,也成功的完成了从双键II_a-h向叁键I_a-h的转换,从而证实了“一锅合成法”反应经历了双消除过程。所有的目标分子以及中间体产物的结构均经过¹H NMR、¹³C NMR、IR及MS得到了确认。更多还原

【Abstract】 It was reported that organic compounds containing thiomethyls at the terminal can assemble gold nanoparticle to gold nanoparticle cluster. The shape and size of the cluster can be adjusted.πconjugate aryl alkynyl thio ethers containing thiomethyl in the end are important compounds. We can use such compounds to get some functional molecules that have good assemblied effect, especially in controlling the shape and the size of the cluster. Therefore, designing and synthesizingπconjugate compounds have prime theoretical and practical value.In order to get the aryl alkynyl thio ether, we need to synthesize some important terminal functional compounds. Based on the preceding reaearch of our laboratory, we selected methyl thio methyl phenyl sulfone （MP-S） as nucleophilic reagent to eract with aromatic aldehyde and synthesized successfully a series of methylthio aryl ethynes I_a-h by“one-pot”reaction .The target compounds I_a-h provide possibility to construct different aryl alkynyl thio ethers.MP-S is widely used an an orgaic sulfur reagent, but the utilization is limited for its low yield. According to the literature, we made some improvements in the method. The new method shortened react time and raised the yield of MP-S from 38% to 51.2%.Next, we tried to synthesize methyl thio aryl akkynes by“one-pot”reaction. After analyzing the structure of MP-S, we knew it had an active methylene, when the methylene took part in neclophilic addition reaction, a new elimination reaction would begin, in which benzensulfonyl and methythio connected with the methylene would be good leaving groups. So, we used MP-S as nucleophilic reagent. First we treated MP-S with strong base, second added reaction nass and then got the target compounds I_a-h in good yield with“one-pot”.In the end, we had a systematic study on the“one-pot”reaction mechanism. According to the products, we inferred it was a double elimination reaction. MP-S firsrt turned to carbanion in the existion of strong base. Then the carbanion of MP-S reacter with aryl aldehyde, diethyl chlorophosphate and the intermediate compounds V was synthesized. The compound V underwent two eliminations to attain the target compounds I_a-h. On testing compound V, diethyl chlorophosphate was displaced with water or acetyl chloride, intermediate compounds VI and VII were isolated. Compounds II_a-h were also good evidence to support this double更多还原