本文選題：β-大馬烯酮　切入點(diǎn)：Co(Ⅱ)催化　出處：《中國(guó)科學(xué)院大學(xué)(中國(guó)科學(xué)院過程工程研究所)》2017年碩士論文

【摘要】：β-大馬烯酮是一種由大馬士革玫瑰中提取的、具有濃郁花香和果香的名貴香料,主要用于配制高檔日化產(chǎn)品香精和食品香精,亦可用作煙草調(diào)香。目前,全球僅有瑞士Firmenich公司掌握工業(yè)化制備β-大馬烯酮的工藝技術(shù)。近年來,隨著香料工業(yè)的迅速發(fā)展,β-大馬烯酮的應(yīng)用范圍更加廣泛,需求量也有所增長(zhǎng)。為滿足國(guó)內(nèi)市場(chǎng)的迫切需求,β-大馬烯酮合成工藝的研究值得關(guān)注。本論文在實(shí)驗(yàn)室前期研究基礎(chǔ)上,針對(duì)以β-紫羅蘭酮為起始原料的合成工藝路線中最關(guān)鍵的最后一步β-二氫大馬酮一鍋法氧化脫氫制得β-大馬烯酮進(jìn)行放大實(shí)驗(yàn)研究,實(shí)現(xiàn)單次合成300g產(chǎn)品,溶劑用量減少50%,β-大馬烯酮產(chǎn)率高于80%。并且通過改良提純裝置優(yōu)化產(chǎn)品純化工藝,實(shí)現(xiàn)快速分離百克量級(jí)產(chǎn)物,得到純度為94%的β-大馬烯酮產(chǎn)品。與此同時(shí),針對(duì)β-大馬烯酮現(xiàn)有合成工藝路線中最后一步氧化脫氫產(chǎn)率低、條件苛刻等問題,本論文以β-二氫大馬酮的環(huán)內(nèi)烯丙基位氧化官能化為目標(biāo),對(duì)Co(Ⅱ)催化烯丙基位C(sp3)-H鍵的氧化酯化方法學(xué)進(jìn)行研究,以探索新的β-大馬烯酮合成路線,實(shí)現(xiàn)在過氧化物DTBP氧化條件下,CoCl2催化烯丙基C(sp3)-H鍵與羧酸的氧化酯化。通過機(jī)理研究,揭示碳?xì)浠衔顲(sp3)-H鍵的活化是該反應(yīng)過程的決速步。反應(yīng)過程中原位生成的[Co(Ⅲ)]Ot-Bu不參與C(sp3)-H鍵中氫原子奪取(HAA)過程。同時(shí),還發(fā)現(xiàn)Co(Ⅱ)可以催化芐位C(sp3)-H鍵的氧化酯化。該催化體系應(yīng)用于β-二氫大馬酮的環(huán)內(nèi)烯丙基位C(sp3)-H鍵的氧化酯化,產(chǎn)率達(dá)到61%;酯化產(chǎn)物經(jīng)催化脫羧后生成β-大馬烯酮。開發(fā)新的β-大馬烯酮合成工藝路線,避免傳統(tǒng)路線中N-溴代丁二酰亞胺(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，

本文編號(hào)：1720362