亞硝鎓離子 與亞硝苯氧 化苄基碳生 成 芳基酮 之 反應研究 研;Investigation of the Benzylic Carbon Oxidation to Aryl Ketones via Reactions of Nitrosonium Ion and Nitrosobenzene

Please use this identifier to cite or link to this item: https://ir.lib.ncu.edu.tw/handle/987654321/97603

Title:	亞硝鎓離子與亞硝苯氧化苄基碳生成芳基酮之反應研究研;Investigation of the Benzylic Carbon Oxidation to Aryl Ketones via Reactions of Nitrosonium Ion and Nitrosobenzene
Authors:	林芳滺;Lin, Fang-Yu
Contributors:	化學學系
Keywords:	氧化苄基碳;芳基酮;亞硝鎓離子;亞硝苯;Benzylic Carbon Oxidation;Aryl Ketones;Nitrosonium Ion;Nitrosobenzene
Date:	2025-08-28
Issue Date:	2025-10-17 11:40:37 (UTC+8)
Publisher:	國立中央大學
Abstract:	中文摘要本篇以亞硝苯 (nitrosobenzene) 與四氟硼酸亞硝鎓 (nitrosonium tetrafluoroborate) 在酸性條件下對苄基碳進行氧化反應生成芳基酮 (aryl ketones) 及芳基醛 (aryl aldehydes)，並研究其反應機制。四氟硼酸亞硝鎓在酸性條件下會釋出 NO+ (nitrosonium ion)，藉由 (NO+, nitrosonium ion) 與亞硝苯 (nitrosobenzene) 形成的錯合物，進行苄基氫擷取反應 (benzylic hydrogen abstraction) 後生成次硝酸 (HNO, nitroxyl / azanone) 與苄自由基 (benzylic radical)，再與亞硝苯陽離子結合並去質子後得到氧化亞胺 (imine oxide)，經水解後得到芳基酮。此方法條件溫和且反應試劑容易取得，我們利用此方法製備出 21 種芳基酮與 4 種芳基醛，最高產率可達 99 %，期望此方法未來可以被經常應用在此氧化領域中。;Abstract In this study, we report the oxidation of benzylic carbons using nitrosobenzene and nitrosonium tetrafluoroborate (NOBF4) under acidic conditions to afford aryl ketones and aryl aldehydes. The reaction mechanism was also investigated. Under acidic conditions, NOBF4 generates the nitrosonium ion (NO+), which forms a complex with nitrosobenzene. This complex facilitates benzylic hydrogen abstraction, leading to the formation of nitroxyl (HNO, also known as azanone or nitroxyl) and a benzylic radical. Subsequent coupling of the benzylic radical with the nitrosobenzene-derived cation, followed by deprotonation, affords an imine oxide intermediate, which undergoes hydrolysis to yield the corresponding aryl ketone. This method features mild reaction conditions and employs readily available reagents. Using this protocol, we successfully synthesized 21 aryl ketones and 4 aryl aldehydes with yields of up to 99 %. We anticipate that this method will find broad application in the field of benzylic oxidation chemistry
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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