合成化学2024,Vol.32Issue(8) :731-736.DOI:10.15952/j.cnki.cjsc.1005-1511.23115

F2O2S促进吡嗪N-氧化物的合成

F2 O2 S Promoted The Synthesis of Pyrazine N-Oxides

陈阳 温乐乐 陈文博
合成化学2024,Vol.32Issue(8) :731-736.DOI:10.15952/j.cnki.cjsc.1005-1511.23115

F2O2S促进吡嗪N-氧化物的合成

F2 O2 S Promoted The Synthesis of Pyrazine N-Oxides

陈阳 1温乐乐 2陈文博3
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作者信息

  • 1. 上海电力大学 环境与化学工程学院 上海市电力材料防护与新材料重点实验室,上海 200090;中国科学院 上海有机化学研究所中科院能量调控材料重点实验室,上海 200032
  • 2. 中国科学院 上海有机化学研究所中科院能量调控材料重点实验室,上海 200032
  • 3. 上海电力大学 环境与化学工程学院 上海市电力材料防护与新材料重点实验室,上海 200090
  • 折叠

摘要

吡嗪N-氧化物广泛运用在有机合成、生物医药和含能材料领域.传统合成方法主要是双氧水/乙酸氧化体系,会造成环境污染,同时也限制了对酸敏感底物的使用.因此,发展吡嗪N-氧化物的绿色合成方法变得尤为迫切.以2,5-二甲基吡嗪为模板底物,通过筛选反应的投料比,碱和溶剂,得到了最优的反应条件:以甲醇为反应溶剂,底物、H2O2和NaHCO3的物质的量之比为1.0∶1.2∶3.6,在F2O2S的促进下,于室温反应50 min.合成的11个吡嗪N-氧化物(2a~2k)的产率为10%-84%,其结构通过1H NMR,13C NMR和MS(ESI)确证.2,6-二甲氧基吡嘻的2个氮原子处于不同的化学环境,通过确认氮氧化反应的选择性,对化合物2f进行单晶X-射线衍射实验,确定该氧化反应优先发生在位阻较小的4-位N原子.该反应可以在弱碱性条件下进行,避免了酸的使用,符合绿色化学理念.

Abstract

Pyrazine N-oxides are widely used in the fields of organic synthesis,biomedicine,and ener-getic materials.The traditional synthesis method mainly involves the hydrogen peroxide/acetic acid oxi-dation system,which can cause the environmental pollution and also limit the use of acid sensitive sub-strates.Therefore,it is urgent to develop a green method for the synthesis of pyrazine N-oxides.In this study,using 2,5-dimethylpyrazine as a template substrate,the optimal reaction conditions were ob-tained by screening the ratio of raw materials,bases,and solvents.Methanol was used as the reaction solvent,and the ratio of substrate,H2O2 and NaHCO3 to each other was 1.0∶1.2∶3.6.Under the promotion of F2O2S,the reaction occurred at room temperature for 50 minutes.Eleven corresponding pyrazine N-oxides 2a~2k were obtained with yields ranging from 10%~84%.Their structures were confirmed by 1H NMR,13C NMR and MS(ESI).The two nitrogen atoms of 2,6-dimethoxy-pyrazine are in different chemical environments.By confirming the selectivity of the nitrogen oxidation reaction,compound 2f was characterized by single crystal X-ray diffraction,and it was determined that the oxi-dation reaction preferentially occurred at the 4-position N atom with low site-resistance.This reaction can be carried out under weakly alkaline conditions,avoiding the use of acids and conforming to the concept of green chemistry.

关键词

吡嗪/F2O2S/H2O2/氧化/绿色合成/N-氧化物/弱碱

Key words

pyrazine/F2O2S/H2O2/oxidation/green synthesis/N-oxides/weakly alkaline

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基金项目

上海市自然科学基金资助项目(20ZR1471600)

上海市科学技术委员会资助项目(19DZ2271100)

中国科学院能量调控材料重点实验室开放基金资助项目(ORFP2020-06)

出版年

2024
合成化学
四川省化学化工学会 中国科学院成都有机化学研究所

合成化学

CSTPCD
影响因子:0.42
ISSN:1005-1511
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