生物基呋喃类含氮化合物催化氨氧化合成研究
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- 英文论文题名：Catalytic ammoxidation for the synthesis of biomass-derived furan N-containing chemicals
- 论文作者：贾秀全 ; 马继平 ; 马红 ; 徐杰
- 英文论文作者：Xiuquan Jia ; Jiping Ma ; Hong Ma ; Jie Xu ; Dalian Institute of Chemical Physics ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中科院大连化学物理研究所;
- 论文关键词：催化氨氧化 ; 硝酸铜 ; 锰氧化物 ; 5-羟甲基糠醛 ; 生物质转化
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十三分会：绿色化学
- 语种：中文
- 分类号：O626.11
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十三分会 ; 绿色化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：212k
- 原文格式：D
- 会议级别：全国
摘要
用催化方法将生物质资源高效转化为含氮化合物等高附加值化学品,缓解或补充化石资源短缺,具有重要科学意义和应用价值。我们以呋喃类生物基平台化合物5-羟甲基糠醛、糠醛等为原料,建立了温和条件下呋喃类化合物催化氨氧化制备呋喃类含氮化合物的新方法。取得了如下主要成果:(1)开发的Cu(NO_3)_2/VOSO_4催化体系,实现了高效选择氧化5-羟甲基糠醛制备2,5-二甲酰基呋喃。单独Cu(NO_3)_2或VOSO_4的催化效果均不佳。研究结果表明,Cu(NO_3)_2通过原位分解产生的NO_x促进V~Ⅴ/V~Ⅳ氧化还原循环高效进行,实现了5-羟甲基糠醛氧化制备2,5-二甲酰基呋喃~([1,2])。(2)报道了催化氨氧化合成2,5-呋喃二甲亚胺酸甲酯的新方法;锰氧八面体分子筛OMS-2催化剂,在温和条件下,一步实现了催化5-羟甲基糠醛氨氧化-Pinner加成串联反应,高效催化合成2,5-呋喃二甲亚胺酸甲酯~([3])。(3)设计制备的双功能锰氧化物α-MnO_2/Na_xMnO_2具有低温氨氧化活性和碱性,在温和条件下,两相之间协同作用,实现了芳香醛一步反应高效制备亚胺酸酯,收率最高可达到96%。
Efficiently catalytic transformation of biomass resources into value-added chemicals is of great scientific and application significance to alleviate or replenish the depletion of fossil resources.In this work,we established a new strategy of catalytic ammoxidation-Pinner tandem reaction of biomass-based 5-hydroxymethylfurfural and furfural,and fabricated efficient catalysts with low temperature ammoxidation activity and basicity for the synthesis of furan-based nitrogen containing chemicals.(1) The promoted effect of Cu(NO_3)_2 on aerobic oxidation of HMF to 2,5-diformylfuran catalyzed by VOSO_4 in acetonitrile was intensively investigated.(2) We report a new methodology of synthesizing imidate.OMS-2realized ammoxidation-Pinner tandem reaction of 5-hydroxymethylfurfural under mild reaction conditions to efficiently afford dimethyl furan-2,5-dicarboximidate.(3) A bifunctional manganese oxides catalyst with low temperature redox-basic activity was fabricated for ammoxidation-Pinner tandem reaction of aldehydes to synthesize imidates.
Efficiently catalytic transformation of biomass resources into value-added chemicals is of great scientific and application significance to alleviate or replenish the depletion of fossil resources.In this work,we established a new strategy of catalytic ammoxidation-Pinner tandem reaction of biomass-based 5-hydroxymethylfurfural and furfural,and fabricated efficient catalysts with low temperature ammoxidation activity and basicity for the synthesis of furan-based nitrogen containing chemicals.(1) The promoted effect of Cu(NO_3)_2 on aerobic oxidation of HMF to 2,5-diformylfuran catalyzed by VOSO_4 in acetonitrile was intensively investigated.(2) We report a new methodology of synthesizing imidate.OMS-2realized ammoxidation-Pinner tandem reaction of 5-hydroxymethylfurfural under mild reaction conditions to efficiently afford dimethyl furan-2,5-dicarboximidate.(3) A bifunctional manganese oxides catalyst with low temperature redox-basic activity was fabricated for ammoxidation-Pinner tandem reaction of aldehydes to synthesize imidates.
引文
[1]Ma,J.;Du,Z.;Xu,J.*;Chu,Q.;Pang,Y.*Chem Sus Chem 2011,4:51.
[2]Jia,X.;Ma,J.;Wang,M.;Du,Z.;Lu,F.;Wang F.;Xu,J.*Appl.Catal.A-Gen.2014,482:231.
[3]Jia,X.;Ma,J.;Wang,M.;Ma,H.;Chen,C.;Xu,J.*Green Chem.2016,18:974.
[2]Jia,X.;Ma,J.;Wang,M.;Du,Z.;Lu,F.;Wang F.;Xu,J.*Appl.Catal.A-Gen.2014,482:231.
[3]Jia,X.;Ma,J.;Wang,M.;Ma,H.;Chen,C.;Xu,J.*Green Chem.2016,18:974.