Piperidine and piperazine analogs in action : zinc(II)-mediated formation of amidines

Podjed, Nina (author), Košmrlj, Janez (author), Modec, Barbara (author)

The catalytic activity of zinc(II) compounds was exploited in the nucleophilic addition of amines to nitriles to form amidines. The reaction systems comprised a Zn(II) starting material [Zn(quin)$_2$(H$_2$O)] (quin− = quinaldinate, an anion of quinaldinic acid), secondary cyclic amine, acetonitrile, and in some cases, methanol. Amines with additional heteroatoms in the ring (thiomorpholine, piperazine) or ring substituents (piperidine derivatives, piperazine derivatives) with different steric and electronic effects were used. The aim of the study was to determine how the nature of the amine affects the formation of amidines. Different types of Zn(II) products were obtained: mono- or diamine complexes, amidine complexes, and also an ionic compound with a protonated amine. In one case, the amidine itself crystallized. A Zn(II) complex with acetamidine was also obtained. Acetamidine was formed from acetonitrile and ammonia, which most likely originated from the hydrolysis of acetonitrile under harsh reaction conditions. The hydrolysis could terminate at the acetamide step, which was confirmed by the isolation of a cocrystal containing acetamide. In the case of piperazine (pz), a polymeric compound with the composition [Zn(quin)$_2$(pz)]$_n$ was isolated regardless of the reaction conditions. The same coordination polymer was also observed to form in 1-methylpiperazine, 1-ethylpiperazine, and 1-acetylpiperazine reaction systems, containing piperazine as an inherent impurity. This was unambiguously confirmed by the crystal structure of a cocrystal, [Zn(quin)$_2$(1-Acpz)$_2$]·[Zn(quin)$_2$(pz)]$_n$·4CH$_3$CN, which formed in the 1-acetylpiperazine (1-Acpz) reaction system.

• Language: English
• Keywords: quinaldinate, piperazine, cyclic amines, amidines, zinc(II), crystal structure
• Work type: Article
• Typology: 1.01 - Original Scientific Article
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Publication status: Published
• Publication version: Version of Record
• Year: 2024
• Number of pages: Str. 8844-8859
• Numbering: Vol. 48, iss. 19
• PID: 20.500.12556/RUL-160080
• UDC: 547.85:546.47:544.1
• ISSN on article: 1369-9261
• DOI: 10.1039/D4NJ00235K
• COBISS.SI-ID: 195465475
• Publication date in RUL: 16.08.2024

Record is a part of a journal

• Title: New journal of chemistry
• Shortened title: New j. chem.
• Publisher: Royal Society of Chemistry
• ISSN: 1369-9261
• COBISS.SI-ID: 22573573

Licences

• License: CC BY 3.0, Creative Commons Attribution 3.0 Unported
• Link: https://creativecommons.org/licenses/by/3.0/deed.en
• Description: You are free to reproduce and redistribute the material in any medium or format. You are free to remix, transform, and build upon the material for any purpose, even commercially. You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not apply legal terms or technological measures that legally restrict others from doing anything the license permits.

Secondary language

• Language: Slovenian
• Keywords: kinaldinat, piperazin, ciklični amini, amidini, cink(II), kristalne strukture