Cyclization And Ring Opening Reactions Of Nitrogen Oxides Using Tert-butyl Nitrite As Precursor

Nitric oxide is an important physiological regulator,which plays a crucial role in signal transduction of biology.As a stable inorganic small molecule free radical,it also owns many unique reactivity properties in organic reactions.In this thesis,various organic reactions involving nitric oxide directly or indirectly are summarized.The reactions of tert-butyl nitrite,the representative of nitric oxide source,are described in detail.Finally,the feasibility of nitric oxide reactions via visible light photocatalysis is described.It is listed specially as following aspects:1.Nitric oxide radical reactions are described in first.Various nitric oxide sources are summarized and their characters are generalized furthermore for the path releasing nitric oxide.For the representative nitric oxide sources tert-butyl nitrite,relative nitric oxide reactions in organic chemistry are reviewed.2.The synthesis approaches of isoxazoline N-oxides are summarized.And we report the synthesis of 4-oxoisoxazoline N-oxides from propargylic alcohols and tert-butyl nitrite.The reaction proceeds through a palladium-catalyzed NO₂ cyclization.Other organic reactions about tert-butyl nitrite are briefly discussed.3.Based on the limitations of tert-butyl nitrite in thermochemical process,a mild visible light reaction conception is proposed to realize the possible nitric oxide reaction.The ring opening reaction of tert-butyl nitrite under visible light irradiation and the visible light photocatalytic reaction of N-hydroxy-4-methylbenzenesulfonamides are designed,and their feasibility was analyzed.Finally,it is pointed out that the ideal photocatalytic reactions could be designed through the energy transfer process between photocatalysts and nitrosamines.