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麝香酮中间体2,15-十六烷二酮的制备
文佺佺
Subtype硕士
Thesis Advisor高 林
2007-06-20
Degree Grantor中国科学院研究生院
Place of Conferral北京
Degree Discipline有机化学
Keyword麝香酮 制备 十四碳二酸 有机锌试剂 2 15-十六烷二酮
Abstract

作为一种名贵的香料和药材,麝香已经使用了数千年,具有很高的应用价值,然而天然麝香的产量长期以来受制于野生麝鹿的数量。麝香酮是麝香中最有价值的成分之一,现在我们可以通过合成麝香酮来得到人工麝香,用它来替代部分的天然麝香。闭环法是合成麝香酮最早采用的方法,而2,15-十六烷二酮就是该法中最重要的中间体,本文以价廉易得的直链十四碳二酸为原料通过不同的方法获得了较高产率的2,15-十六烷二酮。 以乙醚为溶剂,将正十四碳二酸用5倍的氯化亚砜酰化3 h后得到十四碳二酰氯,然后与丙二酸二乙酯在乙醇镁的作用下反应,产物用一定浓度的硫酸水解10~12 h后用甲醇重结晶即得较高产率的产品2,15-十六烷二酮(71%)。实验发现温度对酰化反应和水解反应影响较大,硫酸的浓度也直接影响了水解脱羧反应的效果,实验证明7 mol/L的硫酸的脱羧效果最好,但反应时间较长。 酰氯与烷基镁、烷基锌等有机金属试剂反应也能方便地制备酮,本文首次利用正十四碳二酰氯与甲基镁、甲基锌直接反应制取2,15-十六烷二酮,产率分别为13%和73%。有机镁试剂由于活性过高不易获得高产率的酮产物,但有机锌试剂与酮产物的反应很慢,因而可以获得较高产率的2,15-十六烷二酮(73%),制备时间也较短,但这类反应对体系内的水份很敏感,且一般都是在低温下快速反应。实验证明使用甲基锌等较低活性的有机金属试剂与正十四碳二酰氯反应可获得较高产率的2,15-十六烷二酮。 通过对比认为,以上两种方法可以获得产率相当的2,15-十六烷二酮产品,前者操作简单,但制备时间较长,后者虽能快速制备2,15-十六烷二酮,但反应过程中对体系的无水要求较高。两者各有特点与不足,均可有效制备2,15-十六烷二酮。

Other Abstract

As a precious perfume and medicinal material, musk is used for thousands of years, but the amount of nature musk is always limited by the amount of wild musk deer. Muscone is one of the most valuable parts of musk, now we can use manual musk instead of nature musk by preparation of muscone. Cyclization is the oldest way to prepare muscone, and 2,15-hexadecanedione is the most important intermediate for cyclization. In the paper, the titled compound is obtained in high yield from different ways, from an easily available starting material : tetradecanedioic acid . Tetradecanedioic acid is chlorinated by thionyl chloride for 3 hours, using ethyl ether as a solvent, the product reacts with diethyl malonate under magnesium ethoxide, then hydrolyzed with sulfuric acid for 10 to 12 hours, high yield of product will be obtained by recrystallization with methanol. Temperature plays an important role during the whole reaction, and 7 mol/L sulfuric acid gives the best effect in hydrolization. The titled compound can also be obtained by reacting tetradecanyl dichloride with organic metallic reagents, such as grignard reagent, organozinc reagent and so on. Grignard reagent is too active to prepare ketone, but high yield of ketone can be obtained with organozinc reagent, because of the very slow reaction between them. These reactions are usually sensitive with water in system, and react quickly under a low temperature. Similar yield can be given by the two different ways, though the first takes much more time. Both of them can prepare the titled compound efficiently.

Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/3495
Collection资源化学研究室
Affiliation中国科学院新疆理化技术研究所
Recommended Citation
GB/T 7714
文佺佺. 麝香酮中间体2,15-十六烷二酮的制备[D]. 北京. 中国科学院研究生院,2007.
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