Porphyrazines with peripheral phosphorous and naphthalene groups

Magnezyum butanolat varlığında 1,2-bis(1-naftilmetiltiyo)maleonitril’in (1) siklotetramerizasyonuyla periferal posizyonlardan bağlanmış sekiz adet naftilmetil grubu içeren sübstitüe mavi-yeşil renkli magnezyum porfirazin (2) sentez edilmiştir. Trifluoroasetik asitle muamele edilerek metalsiz türevine (3) geçilmiş ve bu ürünün çeşitli metal tuzlarıyla reaksiyona sokulmasıyla metal porfirazinler (4-6) elde edilmiştir  (M+2= Cu+2, Zn+2, Co+2). Bu çalışmanın ana hedefini oluşturan trifenilfosfin sübstitüe porfirazinler elde etmek için önce trifenilfosfinin metakrilik asit ve hidrobromik asit ile reaksiyonu sonucu oluşan (2-karboksi-1-metiletil)trifenilfosfonyum bromür’ün (9), oktakis(2-hidroksietiltiyo)porfirazinatomagnezyum’un (8) -OH grupları ile esterleştirme reaksiyonu yapılmıştır. Yeni bileşikler FT-IR, EPR, 1H ve 31P NMR, UV-görünür bölge spektrumlarıyla ve elementel analizle karakterize edilmiştir.  Anahtar Kelimeler: Porfirazin, naftalen, EPR, trifenilfosfin, fosfonyum.Peripherally functionalized porphyrazines have the potential to exhibit novel optical, magnetic and electronic properties; also maintain some additional features superior to the values met in related materials. The transition metal ion in the inner core offers new ways to induce, modify and control molecular properties. The starting point for a novel porphyrazine structure with eight naphthyl units bound to the periphery through flexible methylthio-chains is 1,2-bis(1-naphthylmethylthio)maleonitrile (1) which was obtained from disodium salt of dithiomaleonitrile and 1-(chloromethyl)naphthalene. By the template effect of magnesium, blue-green colored magnesium porphyrazinate (2) substituted with eight naphthylmethyl groups on the peripheral positions has been synthesized by cyclotetramerization of 1 in the presence of magnesium butanolate. The metal-free derivative (3) was obtained by its treatment with trifluoroacetic acid and further reaction of this product with copper(II) acetate, zinc(II) acetate and cobalt(II) acetate led to the metal porphyrazinates (4-6) (M+2= Cu+2, Zn+2, Co+2). In order to obtain triphenylphosphine substituted porphyrazines which is the main goal of this study, (2-carboxy-1-methylethyl) triphenylphosphonium bromide (9) is obtained by the reaction of triphenylphosphine and methacrylic acid with hydrobromic acid. Then, the -OH groups of octakis (2-hydroxyetyhylthio)porphyrazinatomagnesium (8) are reacted with 9 for esterification. The novel compounds were characterized by FT-IR, EPR, 1H NMR, 31P NMR, UV-Vis spectral techniques and elemental analysis. Keywords: Porphyrazine, naphthalene, EPR, triphenylphosphine, phosphonium

New polyfluorinated porphyrazine complexes: synthesis, characterization, aggregation, and solubility

<p>By cyclotetramerization of 2,3-bis(2,3,5,6-tetrafluoro-4-methylbenzylthio)maleonitrile in the presence of magnesium butoxide, magnesium porphyrazinate (MgPz) carrying eight (2,3,5,6-tetrafluoro-4-methylbenzylthio) functional units on the periphery positions has been synthesized. Conversion of MgPz into the metal-free derivative was achieved upon addition of a strong acid such as trifluoroacetic acid. Further reaction of this product with different metal(II) acetates led to metallo porphyrazines (MPz). The monomeric bisaxial complex FePz(py)₂ as well as the bridged complex [FePz(pyz)]_n were formed as stable complexes by reacting FePzCl with pyridine or pyrazine, respectively. These complexes were characterized by elemental analysis, together with FT-IR, ¹H NMR, ¹³C NMR, ¹⁹F NMR, UV–vis, and mass spectral data.</p

Metal-free and metallo-porphyrazines with eight [5-thiopentyl 2-methoxy-4,6-bis (trifluoromethyl) benzoate] substituent

<p>The reaction of (5-hydroxypentylthio magnesium porphyrazine) with 2-methoxy-4,6-bis(trifluoromethyl)benzoic acid in DCCI and PTSA, esterified MgPz having [5-thiopentyl 2-methoxy-4,6-bis(trifluoromethyl)benzoate] substituent was obtained. Further reactions of the metal-free porphyrazine with M²⁺(Mg, Co, Cu, Zn, Fe) acetates have produced the metallo-porphyrazines. Finally, by the reaction of FePzCl with pyridine or pyrazine compounds, [FePz(py)₂] and [FePz(pyz)]_n complexes were prepared as the novel stable complexes, respectively. The target compounds have been characterized by using different spectroscopic methods such as FT-IR, UV-Vis, mass, ¹H, ¹³C, and ¹⁹F NMR together with elemental analysis. The aggregation and the solubility features were indicated in various concentrations and solvents.</p

Metal-free, metallo-porphyrazines, monomeric bisaxial complex [FePz(py)₂] and the bridged complex [FePz(pyz)]_<i>n</i> with eight (4-thiobutyl 4-biphenylcarboxylate) groups

<div><p>Metal-free and metallo-porphyrazines (M = Mg, Co, Cu, Zn, and ClFe) carrying eight hydroxybutylthio groups at peripheral positions were prepared from 2,3-bis(4-hydroxybutylthio) maleonitrile. The hydroxybutyl groups were incorporated by esterification of porphyrazine derivatives with 4-biphenylcarboxylic acid in the presence of dicyclohexylcarbodiimide and <i>p</i>-toluenesulfonic acid. Unlike the parent porphyrazine, the symmetrically functionalized porphyrazines with eight ester units were soluble in common organic solvents such as chloroform, dichloromethane, tetrahydrofuran, acetone, and toluene and insoluble in water and <i>n</i>-hexane. Chloro-octakis(4-thiobutyl 4-biphenylcarboxylate) porphyrazinato iron(III) (FePzCl) was prepared by the reaction of metal-free porphyrazine with iron(II) acetate and further treatment with HCl solution. The monomeric bisaxial complex [FePz(py)₂] and the bridged complex [FePz(pyz)]_<i>n</i> were formed as stable complexes by reacting FePzCl with pyridine and pyrazine, respectively. The newly synthesized compounds were characterized by elemental analysis, FT-IR, UV‒vis, mass, ¹H and ¹³C NMR spectroscopy.</p></div

Binary Santrallerde Çalışma Akışkanı Olarak Kullanılan n-Pentan’ın Patlama Riskinin İncelenmesi

Günümüzde artan enerji ihtiyacını karşılamak için ülkemiz ve dünya genelinde birçok alternatif çalışma yapılmaktadır.  Ülkemizin jeotermal kaynaklar açısından oldukça zengin olduğu bilinmektedir. Modern teknoloji ile birlikte, jeotermal enerjiden elektrik üreten santral miktarı da her geçen gün artmaktadır. Yapılan bu çalışmada, binary santrallerde çalışma akışkanı olarak sıkça kullanılan Pentan’ın 1mm2’lik bir kesit alanından sızması durumunda ortaya çıkan patlama riski incelenmiştir. Çalışmanın sonucunda n-Pentane akışkanının 2 m yüksekte bir depo veya boru hattında bulunması durumundaki sızıntı debisi, sıvı fazındayken 0,00883 kg/sn, gaz fazında ise 0,000468 kg/sn olarak tespit edilmiştir. Bu değerlere göre, herhangi bir sızıntının tehlikeli patlamalara yol açabileceği görülmüştür

Binary Santrallerde Çalışma Akışkanı Olarak Kullanılan n-Pentan’ın Patlama Riskinin İncelenmesi

Günümüzde artan enerji ihtiyacını karşılamak için ülkemiz ve dünya genelinde birçok alternatif çalışma yapılmaktadır.  Ülkemizin jeotermal kaynaklar açısından oldukça zengin olduğu bilinmektedir. Modern teknoloji ile birlikte, jeotermal enerjiden elektrik üreten santral miktarı da her geçen gün artmaktadır. Yapılan bu çalışmada, binary santrallerde çalışma akışkanı olarak sıkça kullanılan Pentan’ın 1mm2’lik bir kesit alanından sızması durumunda ortaya çıkan patlama riski incelenmiştir. Çalışmanın sonucunda n-Pentane akışkanının 2 m yüksekte bir depo veya boru hattında bulunması durumundaki sızıntı debisi, sıvı fazındayken 0,00883 kg/sn, gaz fazında ise 0,000468 kg/sn olarak tespit edilmiştir. Bu değerlere göre, herhangi bir sızıntının tehlikeli patlamalara yol açabileceği görülmüştür