Highly Active Pandanus Nanocellulose-Supported Poly(amidoxime) Copper (II) Complex for Ullmann Cross-Coupling Reaction

C. Fui, Md. Hafizur Rahman, T. Ting, M. Sarjadi
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Abstract

: The transition metal-catalyzed chemical transformation of organic electrophiles, and organometallic reagents have turned up as an exceedingly robust synthetic tool. The evolution of transition metal catalysts has attained a stage of civilization that authorizes for an extensive scope of chemical bonds formation partners to be combined efficiently. The applications of Cu-based nanoparticles have received great attention owing to the earth-abundant, low toxicity and inexpensive. Due to these characteristics, copper nanoparticles have generated a great deal of interest especially in the field of catalysis. In this study, poly(acrylonitrile) was synthesized by undergoes free-radical initiation process and followed by Beckmann rearrangement with hydroxylamine solution converted into the poly(amidoxime) ligand and anchored the copper onto poly(amidoxime). Cu(II)@PAM was characterized using different techniques such as FTIR, FESEM, EDX, TEM, TGA, DSC, ICP-OES, and XPS analyses. The Cu(II)@PAM showed high stability and high catalytic activity in a wide variety of electrophilic substituted phenols with substituted aryl/benzyl halides. 0.15 mol%, ±3 mg of Cu(II)@PAM could efficiently promote Ullmann reaction to give the corresponding coupling product up to 99 % yields. The complex was easy separated and recovered from the reaction mixture by simple filtration.
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用于乌尔曼交叉偶联反应的高活性Pandanus纳米纤维素负载聚偕胺肟铜(II)配合物
过渡金属催化的有机亲电试剂和有机金属试剂的化学转化已经成为一种非常强大的合成工具。过渡金属催化剂的发展已经达到了一个文明的阶段,这使得广泛的化学键形成伙伴能够有效地结合。铜基纳米颗粒因其资源丰富、毒性低、价格低廉等优点而受到广泛关注。由于这些特性,铜纳米颗粒引起了人们极大的兴趣,特别是在催化领域。本研究采用自由基引发法合成聚丙烯腈,羟胺溶液经贝克曼重排转化为聚偕胺肟配体,并将铜固定在聚偕胺肟上。采用FTIR、FESEM、EDX、TEM、TGA、DSC、ICP-OES和XPS等技术对Cu(II)@PAM进行了表征。Cu(II)@PAM对多种取代芳基/苄基卤化物取代的亲电性取代酚具有较高的稳定性和催化活性。0.15 mol%,±3 mg Cu(II)@PAM能有效促进Ullmann反应,偶联产物产率可达99%。该配合物易于从反应混合物中分离和回收。
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