Makrosiklik grup taşıyan yeni tetrapirrolik makrosikliklerin sentezi, karakterizasyonu ve kompleks oluşumlarının incelenmesi

Bu çalışmada, periferalinde N2S4 makrobisiklik gruplar taşıyan MgPz (8) olarak gösterilen yeni magnezyum porfirazin, H2Pc (11) olarak gösterilen metalsiz ftalosiyanin ile kobalt ftalosiyanin CoPc (12); ve periferalinde N2S2 makrosiklik gruplar taşıyan H2Pc (18) ve onların sentezinde kullanılan oniki yeni başlangıç maddesi ile literatürden faklı yöntemle sentezlenen iki bileşiğin sentezi ve karakterizasyonu yapıldı. N-Tosilbis(3-iyodopropil)amin (1), N-Tosil-bis(3-(tosiloksi)propil)amin ve sodyum iyodürden hazırlandı. N-Tosilbis(3-bromopropil) amin (2), N-Tosil-bis(3-(tosiloksi) propil) amin ve sodyum bromürden hazırlandı. N-Tosilbis(3-merkaptopropil)amin (4) ise N-Tosilbis(3-tiyoasetoksipropil)amin (3) ve %37'lik HCl'den hazırlandı. N,N'-Bistosil-1,9-ditiya-5,13-diazasiklohekzadekan (5) bileşiği, `high dilution' yöntemi ile N-Tosilbis(3-iyodopropil)amin (1) ve N-Tosilbis(3-merkaptopropil)amin (4) bileşiklerinin reaksiyonundan elde edildi. (5) bileşiğindeki tosil gruplarının LiAlH4 ile kesilmesiyle 1,9-Ditiya-5,13-Diazasiklohekzadekan (6) bileşiği sentezlendi. (6) bileşiğinin Cs2CO3'ın template etkisi varlığında 5,8-ditiya-6,7-dikarbonitril-1,12-diiyodododeka-6-en bileşiği ile ve 5,8-Ditiyadodek-6-en-6,7-dikarbonitril-1,2-di-p-toluensülfonat bileşiği ile verdiği reaksiyonla farklı iki metotla MgPz başlangıç maddesi 5,8,16,24-tetratiya-1,12-Diazabisiklo [10.7.7] oktakos-6-en-6,7-dikarbonitril (7) elde edildi. Mağnezyum bütoksit ve (7) bileşiğinin varlığında tipik bir metot olarak genellikle uygulanan siklotetramerizasyonla tetrapirrol bileşiği N2S4 karışık donörlü makrobisiklik sübstitüe MgPz (8) elde edildi. (9) bileşiği literatürde belirtilen metottan farklı bir metotla sentezlendi. 1,2-bis(2-tosiloksietilmerkapto)-4,5-disiyanobenzen ile NaI'ün kuru aseton içerisinde argon atmosferinde oda sıcaklığında karıştırılmasıyla pratik olarak (9) bileşiği sentezlendi. (6) bileşiği ile 1,2-bis(2-iyodoetilmerkapto) -4,5-disiyanobenzen ve 1,2-bis(2-tosiloksietilmerkapto)-4,5-disiyanobenzen reaksiyonlarından makrobisiklik ftalonitril (10) bileşiği elde edildi. Makrobisiklik ftalonitril (10) bileşiğinin, n-pentanol ve DBU varlığında siklotetramerizasyon reaksiyonundan H2Pc (11) ve elde edilen metalsiz ftalosiyaninin, kinolin içinde anhidro kobalt(II) klorür tuzu ile kaynatılmasıyla da CoPc (12) elde edildi. Pikolil amin ve 3-kloro-1-propanolün reaksiyonundan (13) bileşiği sentezlendi. (13) bileşiğinin de tiyoüre ve fuming HCl ile geri soğutucu altında ısıtılması sonucu (14) bileşiği elde edildi. (1) bileşiği ile (14) bileşiğinin aşırı seyreltik ortamda reaksiyona girmesiyle makrosiklik (15) bileşiği sentezlendi. (15) bileşiğindeki tosil grubunun LiAlH4 ile kesilmesiyle (17) bileşiği sentezlendi. Makrosiklik ftalonitril (17) bileşiğinin, n-pentanol ve DBU varlığında siklotetramerizasyon reaksiyonundan H2Pc (18) elde edildi. Yeni bileşiklerin yapıları IR, NMR, MS ve UV-vis spektral verileri ve elementel analiz ile karakterize edildi.In this work, we reported the synthesis and structural properties of novel MgPz (8) peripherally attached N2S4 (11) and N2S2 macrobicyclic moiety, metal free phytallocyanine, H2Pc, (11) and CoPc (12). Also, we have synthesized and characterized twelve novel reactants. N-Tosylbis(3-iodopropyl)amine (1) was prepared from N-Tosyl-bis(3-(tosyloxy)propyl)amine and NaI; N-Tosylbis(3-bromopropyl)amine (2) was from N-Tosyl-bis(3-(tosyloxy) propyl)amine and NaBr; N-Tosylbis(3-merkaptoproyl)amine (4) was also prepared from N-Tosylbis(3-thioasetoxypropyl)amine (3) and %37 solution of HCl. The preparation of compound N,N'-Bistosyl-1,9-dithia-5,13-diazasiclohexadecane (5) was carried out with the reaction of N-Tosylbis(3-iodopropyl)amine (1) and N-Tosylbis(3-merkaptopropyl)amine (4) by high dilution technique. Detosylation of compound (5) was performed a reductive detosylation by using LiAlH4 to yield 1,9-dithia-5,13-diazasiclohexadecane (6). Porphirazinato magnesium MgPz (8) was obtained from the reaction of 5,8-dithia-6,7-dicarbonitrile-1,12-diiodododeca-6-en and 5,8-Dithiadodec-6-en-6,7-dicarbonitrile-1,2-di-p-toluenesulphonat under the template effect of Cs2CO3 to yield 5,8,16,24-tetrathia-1,12-Diazabicyclo [10.7.7] oktacos-6-en-6,7-dicarbonitrile (7) by two new methods. Synthesis of MgPz (8) peripherally attached N2S4 macrobicyclic moiety was carried out by cyclomerisation of compound (7) using magnesium butoxide. Compound (9) was synthesized by the novel proposed strategy. Treatment of 1,2-bis(2-tosiloxyetilmercapto)-4,5-dicyanobenzene with NaI by stirring at room temperature in dry acetone under argon atmosphere resulted .n the formation of desired compound (9). The reaction of compound (6) with 1,2-bis(2-iodoetylmercapto)-4,5-dicyanobenzene and 1,2-bis(2-tosyloxyetylmercapto)-4,5-dicyanobenzene yielded to macrobicyclic phtalonitrile compound (10). Treatment of macrobicyclic phtalonitrile compound (10) with n-pentanol and DBU by cyclomerisation reaction yielded H2Pc (11) and metal free phtalocyanine. Boiling of this metal free phtalocyanine in quinoline with anhydro CoCl2 yielded CoPc (12). Compound (13) was synthesized from the reaction of picolyl amine and 3-chloro-1-propanol. The reflux of compound (13) with thiourea and fuming HCl yielded compound (14). Macrocyclic compound (15) obtained from the reaction of (1) and (14) by high dilution. Detosylation of compound (15) was performed a reductive detosylation by using LiAlH4 to yield (17). Treatment of macrobicyclic phtalonitrile compound (17) with n-pentanol and DBU by cyclotetramerisation reaction yielded H2Pc (18). All new compounds were characterized by a combination of elemental analysis and 1H, 13C NMR, IR, UV-vis and MS spectral data

Yeni o-o'-dihidroksi azo boyarmaddelerin metal komplekslerinin sentezi ve yapılarının aydınlatılması

Azo boyarmaddeler ve metal kompleksleri, kemoterapik ve antiseptik özellikleri yanında, bazı yiyecek maddelerinin boyanması, yiyecek tohumlarının saklanması için, redoks indikatörû olarak ve en yaygın şekilde de tekstil boyarmaddesi olarak kullanılmaktadır. Bu çalışmada, l-(2'-hidroksi-5'-ter^-bütil azo benzen)-2-naftol-4-sülfonik asit, l-(2'- hidroksi-5'~nitro azo benzen)-2-naftol-4-sülfonik asit azo boyarmaddeler ve Cu, Co, Ni, Zn, Cd ve Hg(ü) geçiş metal klorür tuzlan ile komplekslerinin sentezi gerçekleştirildi. Sentezlenen boyarmaddeler ve kompleMerinin yapılan; İR, UV-VIS, DTA-TG, Job Metodu, mağnetik sûsseptibilite teknikleri ile aydınlatıldı. Ligandlann ve komplekslerin boyama özellikleri araştırıldı ve yünlü kumaşların boyanmasında yüksek yıkama ve ışık haslığı değerleriyle kullanılabilirliği belirlendi.Azo dyes and theirmetal complexes are used as antineoplastic and antiseptic agents, dyes for food stuffs, preserving seeds and grains and redox indicator. They aremost commonly used for dying textiles. In this study, l-(2'-hydroxy-5'-tert-butylazo benzene)-2-naphthol-4-sulphonic acid, 1- (2'-hydroxy-5'-nitro azo benzene)-2-naphthol-4-sulphonic acid and their Cu, Co, Ni, Zn, Cd and Hg(II) transition metal complexes were synthesized. The structures of these complexes were identified by TR, UV-VIS spectra, DTA-TG analysis, Job Method, magnetic susceptibility techniques and by using their physical properties such as the colours of calcination product and solubility. Dying properties of washing and sun light bleeching test results were studied azo dyes and metal complexes

Synthesis, characterization and liquid-liquid extraction properties of new methoxyaminobiphenylglyoxime derivatives and their complexes with some transition metals

In this study, three new aminobiphenylglyoximes, [L1H 2] N-(2-methoxy)aminobiphenylglyoxime, [L2H2] N-(3-methoxy)aminobiphenylglyoxime and L[3H2] N-(4-methoxy)aminobiphenylglyoxime have been synthesized by the reaction of (E,E)-4'-biphenylchloroglyoxime with 2-Methoxyaniline, 3-Methoxyaniline and 4-Methoxyaniline in absolute ethanol. The preparation NiII, CoII and CuII complexes of these ligands are described. The ligands and their complexes were characterized by elemental analyses, IR, mass, H1 and 13C NMR spectra, thermogravimetric analyses (t.g.a) and magnetic susceptibility measurements. Ligands complexing properties were studied by the liquid-liquid extraction of selected alkali (Li+, Na+, K+, Cs+) and transition metals (Co 2+, Ni2+, Cu2+, Zn2+, Cd 2+, Pb2+). It has been observed that all ligands show a high affinity to Cu2+ ions, whereas almost no affinity to alkali metals. The extraction equilibrium constants (K ex) for complexes of ligands with Cu2+ metal picrates between dichloromethane and water have been determined at 25°C. © 2007 Springer

Synthesis and characterisation of new porphyrazinato magnesium containing macrobicyclic moieties

Novel porphyrazinato magnesium (MgPz) containing symmetrically four diaza-tetrathia-macrobicycles on peripheral positions was synthesized by the cyclotetramerisation reaction of 5,8,16,23-tetrathia-1,12-diazabicyclo[9.7. 7Şpentacosane-6-en-6,7-dicarbodinitril (9), which was prepared by sequence reaction of N-tosyl-bis[3-bis(tosyloxypropyl)Ş amine (1) and disodium cis-1,2-dicyano-1,2-ethylenedithiolate (8). Elemental analysis, IR, NMR, MS and UV-vis data confirmed the ability of bulky cryptand moieties to induce steric isolation of Pz core in the solid state. © 2011 Taylor ; Francis

Synthesis and characterization of new metal-free and metallophthalocyanines containing macrobicyclic moieties

The synthesis and characterization of novel metal-free and cobalt phthalocyanine, peripherally symmetrically derived from 2,3,6,7,10,11,13,14- octahydro-5H,9H-4,12-(propanothiopropano)-1,8,15,23,4,12- benzotetrathiodiazacycloheptadecane-17,18-dicarbonitrile (4) which was prepared by the reaction of 1,9-diaza-5,13-dithiocyclohexadecane (3) and 1,2-bis(2-iodoethylmercapto)-4,5-dicyanobenzene (2) was carried out. The novel compounds were characterized by using elemental analysis, 1H, 13C NMR, IR, UV-vis and MS techniques. © 2011 Elsevier B.V. All rights reserved

Synthesis and characterisation of new porphyrazinato magnesium containing macrobicyclic moieties

Novel porphyrazinato magnesium (MgPz) containing symmetrically four diaza-tetrathia-macrobicycles on peripheral positions was synthesized by the cyclotetramerisation reaction of 5,8,16,23-tetrathia-1,12-diazabicyclo[9.7. 7Şpentacosane-6-en-6,7-dicarbodinitril (9), which was prepared by sequence reaction of N-tosyl-bis[3-bis(tosyloxypropyl)Ş amine (1) and disodium cis-1,2-dicyano-1,2-ethylenedithiolate (8). Elemental analysis, IR, NMR, MS and UV-vis data confirmed the ability of bulky cryptand moieties to induce steric isolation of Pz core in the solid state. © 2011 Taylor & Francis

The synthesis and characterization of novel metalloporphyrazine containing crown ether linked calix[4]arene moieties

The synthesis and characterization of novel magnesium porphyrazine, peripherally symmetrically derived from 1,3-alternate 26,28-[35,36-dicyano-34,37-dithia-29,32,40,43-tetraoxa-35-en]calix[4]arene-crown-5, were carried out. This compound was prepared starting from cis-1,2-dicyano-1,2-ethylenedithiolate and 1,3-alternate 26,28-bis(5'-chloro-3'-oxapentyloxy)calix[4]arene-crown-5. The new macrocycle was characterized using the techniques of UV-vis, 1H, 13C NMR, IR, MS and elemental analysis. © 2009 Elsevier B.V. All rights reserved