Metal-free and metalloporphyrazines with eight (4-biphenylmethylthio), (p-tolylmethylthio) and (o-tolylmethylthio) units

Abstract

Bu çalışmada periferal konumdaki sekiz adet (p-tolilmetiltiyo) ,(o-tolilmetiltiyo) ve (4-bifenilmetiltiyo) sübstitüentleri içeren porfirazinleri sentezledik. Magnezyum butanolat içerisinde 1,2-bis(p-tolilmetiltiyo)maleonitril, 1,2-bis(o-tolilmetiltiyo) maleonitril, 1,2-bis(4-bifenilmetiltiyo)maleonitril'in siklotetramerizasyon yöntemiyle reaksiyonu sonucunda magnezyum porfirazinler sentezlendi. Trifloroasetik asit gibi kuvvetli bir asitle muamele edilerek metalsiz türevine geçildi ve bu ürünün bakır(II) asetat, çinko(II) asetat ve kobalt(II) asetat ile reaksiyona sokulmasıyla metalli porfirazinler elde edildi (M+2= Cu+2, Zn+2, Co+2).

In this study, we report novel porphyrazines with eight (p-tolylmethylthio), (o-tolylmethylthio) and (4-biphenylmethylthio) substituents appending to the peripheral positions. Magnesium porphyrazinates have been synthesized by cyclotetramerization of 1,2-bis(p-tolylmethylthio)maleonitrile, 1,2-bis(o-tolylmethylthio)maleonitrile and 1,2-bis(4-biphenylmethylthio)maleonitrile in the presence of magnesium butanolate. The conversions of magnesium porphyrazinates into the metal-free derivatives were achieved by the treatment with relatively strong acids (e.g. trifluoroacetic acid). Further reactions of these products with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate have led to the metal porphyrazinates (M= Cu, Zn, Co).