類辣椒素的合成研究： ( 1 ) 二壺反應將醛類轉變成一級胺 ( 2 ) 大量製備香草莢蘭壬醯胺的簡易法 ( 3 ) 以薄荷酮為原料新法合成類辣椒素

Studies on the synthesis of capsaicinoids : ( 1 ) Two - pot reactions for the conversion of aldehydes into primary amines ( 2 ) A facile large - scale preparation of vanillylnonanamide. ( 3 ) A new synthesis of capsaicinoids derived from (-)- menthone

曾景郁(Jing-Yu Tzeng)

指導教授 ： 王英基

高雄醫學大學/藥學院/藥學研究所/碩士(2007年)

https://doi.org/10.6832/KMU.2007.00157

摘要

Ⅰ. 一級胺類化合物的製備：
本研究主要在描述一系列的芳香基醛類化合物，藉由使用碘、氨水和氫硼化鈉、氯化鎳等試劑來進行一步二壺反應，得以高產率合成出一級胺類化合物。

Ⅱ. 大量製備辣椒素類化合物：
再以上述的方法為基礎，來改良原先辣椒素類化合物的全合成方法，並大量製備。合成順序如下：1 ). 將香草素以卞基來進行保護的作用，2 ). 再用碘、氨水將保護基保護的香草素一步轉變成月青化合物，3 ). 再將月青化合物以氫硼化鈉、氯化鎳還原轉變成卞基香草胺，4 ). 卞基香草胺和壬醯氯反應得到O -卞基辣椒素類化合物，5 ). 最後用Pd(OH)2 / C和環己烯來去保護基以得到辣椒素類化合物。

Ⅲ. 由薄荷酮新法合成出類辣椒素化合物：
先將薄荷酮與m-CPBA進行Baeyer-Villiger oxidation，再利用上述兩壺方法，分別得到香草胺、卞基香草胺和卞基異香草胺，然後繼續進行開環反應，最後可以得到高產率且新穎的類辣椒素化合物。

關鍵字

辣椒素 ； 薄荷酮 ； 一級胺

並列摘要

Ⅰ. Preparation of primary amines：
In this thesis, a series of the aryl aldehydes were readily converted to the corresponding primary amines in good yields using iodine, ammonium hydroxide and sodium borohydride, nickel (Ⅱ) chloride as reagents in a two - pot reaction.

Ⅱ. Large scale preparation of vanillylnonanamide：
Based on the above mentioned method, a practical strategy for the synthesis of vanillylnonanamide was accomplished in large scale.
The synthetic sequences are as follows :
( 1 ). Protecting vanillin with benzyl group to afford O- benzylvanillin,
( 2 ).Converting the formyl group of the protected vanillin into nitrile with iodine and ammonium hydroxide in one step,
( 3 ). Transformation of the nitrile functionally into primary amine with
sodium borohydride and nickel (Ⅱ) chloride,
( 4 ). Coupling the amine with corresponding nonanoyl chloride to give
O-benzylvanillylnonanamide,
( 5 ). And finally debenzylation with Pd(OH)2/ C and cyclohexene to afford the corresponding vanillylnonanamide.

Ⅲ. A new synthesis of capsaicinoids and its analogues from ( - )-menthone
Firstly, (-)-menthone was treated with m-chloroperoxybenzoic acid to undergo the Baeyer-Villiger Oxidation to give lactone A.
Subsequently, the lactone A was respectively ring-opened by benzylamine, vanillylamine and isovanillylamine which prepared from the method described in the part I of this thesis to give the desired O-benzylcapsaicinoids.
After deprotection of O-benzylcapsaicinoids, a novel synthesis of capsaicinoids would be afforded.

並列關鍵字

capsaicin ； capsaicinoids ； methone ； primary amine

參考文獻

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