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光解一氧化氮饱和的脂芳族酰胺类和醛类化合物溶液成氮氧自由基的EPR研究

Nitroxides generated from photolysis of aliphatic amides and aldehydes in the presence of nitric oxide.Investigation by EPR technique

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【作者】 王帆金璟吴隆民

【Author】 Wang Fan Jin Jing Wu Longmin* National Laboratory of Applied Organic Chemistry,Lanzhou University,Lanzhou 730000,China

【机构】 兰州大学应用有机化学国家重点实验室

【摘要】 <正>在一氧化氮(NO)存在下,UV 光解脂芳族酰胺类和醛类化合物产生的酰基自由基、氢原子、碳中心自由基以及氮中心自由基,可以与 NO 反应生成各种稳定的氮氧自由基。通过 EPR 谱的研究,对这些氮氧自由基的结构进行了指认。典型的 EPR 谱如图l所示。这些氮氧自由基的生成主要涉及光分解反应、偶联反应、加成反应以及还原反应等。用于该研

【Abstract】 The free radicals generated from photolysis of aliphatic amides and aldehydes were trapped by nitric oxide.Nitroxides thus formed were detected by EPR technique.The generation of free radicals by other transient radical attack on amide or aldehyde molecules and by photolysing amines was used to help identify the free radicals produced in photochemical &compositions. Amides used in the present investigation were formamide,N,N-dimethylformamide, N,N-dimethylformamide-d7,acetamide,N,N-dimethylactamide and N-phenylacetamide. Aldehydes used in this study were formaldehyde and acetaldehyde.Transient radicals were generated from initiators such as AIBN,AAPH,BPO and BTBP,according to their solubility in various solvents and their H-abstracting reactivity.Possible mechanisms are proposed.As an example,a possible photochemical mechanism involving formamide is suggested as follows:

【基金】 国家自然科学基金委资助项目(20072013)
  • 【会议录名称】 第十二届全国波谱学学术会议论文摘要集
  • 【会议名称】第十二届全国波谱学学术会议
  • 【会议时间】2002-10
  • 【会议地点】中国辽宁大连
  • 【分类号】O631.3
  • 【主办单位】中国物理学会波谱专业委员会
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