钴催化烯丙基C（sp~3）-H键氧化酯化机理研究及β-大马烯酮合成工艺优化

发布时间：2018-04-07 18:31

  本文选题：β-大马烯酮　切入点：Co(Ⅱ)催化　出处：《中国科学院大学(中国科学院过程工程研究所)》2017年硕士论文

【摘要】：β-大马烯酮是一种由大马士革玫瑰中提取的、具有浓郁花香和果香的名贵香料,主要用于配制高档日化产品香精和食品香精,亦可用作烟草调香。目前,全球仅有瑞士Firmenich公司掌握工业化制备β-大马烯酮的工艺技术。近年来,随着香料工业的迅速发展,β-大马烯酮的应用范围更加广泛,需求量也有所增长。为满足国内市场的迫切需求,β-大马烯酮合成工艺的研究值得关注。本论文在实验室前期研究基础上,针对以β-紫罗兰酮为起始原料的合成工艺路线中最关键的最后一步β-二氢大马酮一锅法氧化脱氢制得β-大马烯酮进行放大实验研究,实现单次合成300g产品,溶剂用量减少50%,β-大马烯酮产率高于80%。并且通过改良提纯装置优化产品纯化工艺,实现快速分离百克量级产物,得到纯度为94%的β-大马烯酮产品。与此同时,针对β-大马烯酮现有合成工艺路线中最后一步氧化脱氢产率低、条件苛刻等问题,本论文以β-二氢大马酮的环内烯丙基位氧化官能化为目标,对Co(Ⅱ)催化烯丙基位C(sp3)-H键的氧化酯化方法学进行研究,以探索新的β-大马烯酮合成路线,实现在过氧化物DTBP氧化条件下,CoCl2催化烯丙基C(sp3)-H键与羧酸的氧化酯化。通过机理研究,揭示碳氢化合物C(sp3)-H键的活化是该反应过程的决速步。反应过程中原位生成的[Co(Ⅲ)]Ot-Bu不参与C(sp3)-H键中氢原子夺取(HAA)过程。同时,还发现Co(Ⅱ)可以催化苄位C(sp3)-H键的氧化酯化。该催化体系应用于β-二氢大马酮的环内烯丙基位C(sp3)-H键的氧化酯化,产率达到61%;酯化产物经催化脱羧后生成β-大马烯酮。开发新的β-大马烯酮合成工艺路线,避免传统路线中N-溴代丁二酰亚胺(NBS)的使用。
[Abstract]:尾 -malaenone is a rare perfume extracted from Damascus rose with rich flower and fruit flavours. It is mainly used to prepare high-grade daily chemical product flavor and food flavor, and can also be used for tobacco flavoring.At present, only Swiss company Firmenich has mastered the technology of industrialized preparation of 尾-malaenone in the world.In recent years, with the rapid development of spice industry, the application range of 尾-malaenone is more extensive, and the demand is also increasing.In order to meet the urgent needs of the domestic market, the synthesis process of 尾-malaenone deserves attention.In this paper, on the basis of the previous research in laboratory, the last key step in the synthesis process of 尾 -ionone was studied, which is the most important step in the one-pot oxidative dehydrogenation of 尾 -dihydrotamanone to 尾 -malonone.The single synthesis of 300g product was achieved, the amount of solvent was reduced by 50%, and the yield of 尾 -malaenone was higher than that of 80 g.The purification process was optimized by the improved purification device to achieve the rapid separation of 100 grams of the product, and the purity of the product was 94%.At the same time, in order to solve the problems of low yield and harsh conditions of the last step oxidation dehydrogenation of 尾 -Dimaenone, the aim of this thesis is to take the function of allyl in the ring of 尾 -dihydrotamanone as the target.The oxidative esterification method of allyl C(sp3)-H bond catalyzed by Co (鈪，

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