Publication: Yeni 2, 4-dinitrofenilhidrazon türevi taç eterlerin sentezi ve katyon bağlama özelliklerinin incelenmesi
Abstract
Literatürde 1,2-dihidroksibenzen türevlerinin CH3COONa/ H2O/ aseton ortamında KIO3 veya K3[Fe(CN)6] gibi inorganik bileşiklerle oda sıcaklığında orto-kinonlara yükseltgenmesinden yararlanarak biyokimyasal aktiviteye sahip bileşikler elde edilmektedir. Reaksiyonun siklohekzan-1,3-dion, 4-hidroksikumarin ve bunların türevleri varlığında gerçekleşmesiyle sırasıyla orto-dihidroksi-3,4-dihidro-2H-dibenzofuran-1-on ve orto-dihidroksikumestan türevleri sentezlenmektedir. Elde edilen bileşiklerin östrojen aktiviteye sahip östradiol yapısına benzemesi, bu tür bileşiklere ilgiyi artırmaktadır. Bu maksatla laboratuvarlarımızda 8,9-dihidroksi- kumestan türevi makrohalkalı eter ligandları sentezlenerek alkali ve toprak alkali metal katyonlara karşı davranışları incelenmiştir. Bu çalışmada, kumestan (6H-benzofuro[3,2-c][1]benzopyran-6-on) türevleriyle yapısal benzerlik gösteren 6,7-dihidroksi-3,4-dihidro-2H-dibenzofuran-1-on ve 6,7-dihidroksi-3,3-dimetil-3,4-dihidro-2H-dibenzo furan-1-on bileşikleri sentezlendi. Bu kondenzasyon reaksiyonunda baz olarak CH3COONa/ su, yükseltgen olarak KIO3 veya K3[Fe(CN)6], nüklofil olarak da dimedon ve siklohekzan-1,3-dion kullanılmıştır. Çalışmanın ikinci aşamasında kristallendirilerek elde edilen benzofuran bileşiklerinin metileter, [9]taç-3, [12]taç-4, [15]taç-5 ve [18]taç-6 türevleri, metileter türevleri için dimetilsülfat/ K2CO3/ aseton, makrohalkalı eter türevleri için polietilenglikolditosilat/ Me2CO3, su, asetonitril kullanılarak elde edilmiştir (Şekil 1.1). Ayrıca elde edilen taç eterlerin polar aprotik çözücülerde daha kolay çözülebilmelerini sağlamak için 2,4-dinitrofenilhidrazin ile reaksiyona sokarak kristallendirilme ile saflaştırılabilen orjinal hidrazon türevi taç eterleri sentezlenmiştir (Şekil 1.2). Elde edilen yeni taç eter ve hidrazon türevi taç eterlerin yapıları elementel analiz, IR, 1H-NMR, 13C-NMR, UV/ Vis verileriyle aydınlatılmıştır. Çalışmanın son aşamasında elde edilen taç eterler ile Li+, Na+, K+, Mg2+, Ca2+, Sr2+ ve Ba2+ katyonlarının perklorat tuzlarının kompleks- leşme denemeleri yapıldı. 6,7-([15]taç-5)-3,3-dimetil-3,4-dihidro-2H-dibenzofuran-1-(2¢,4¢-dinitrofenil)hidrazon ligandının NaSCN, 6,7-([18]taç-6)-3,3-dimetil-3,4-dihidro-2H-dibenzofuran-1-(2¢,4¢-dinitrofenil) hidrazon ligandının KSCN ile asetonitril içinde kaynatılarak katı kompleksleri elde edildi. Diğer taç eterlerin bazı katyonlarla verebilecekleri kayma değerleri UV/ Vis çalışmalarıyla tayin edildi.
The synthetic method found in the literature to afford compounds possesing biological activity includes the connection of two bonds by oxidative condensation of 1,3-cyclicdiketones with 1,2-benzendiols, quinones and related compounds at room temperatures. Oxidation was performed with inorganic oxidation agents with both potassium iodate (KIO3) and potassium ferricyanide (K3[Fe(CN)6]). According to this procedure; ortho-dihydroxybenzofuran, 6,7-dihydroxy-3,4-dihydro-2H-dibenzofuran-1-one and ortho-dihydroxycoumestan have been prepared by the reaction carried out with cyclohexane-1,3-dione and 4-hydroxycoumarins respectively. A significant feature common to these benzofuran derivatives is the resembling coumestrol 3,9-dihydroxycoumestan structure which is known to be a potent estrogen. That increases the interest in these kind of benzofuran derivatives. For this purpose 8,9-dihydroxycoumestan derivatives of macrocyclic crown ether ligands were synthesized and examined on their alkali and earth alkali metal cation binding property in our laboratory. In this study, 6,7-dihydroxy-3,4-dihydro-2H-dibenzofuran-1-one and 6,7-dihydroxy-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-one which show the structural similarity with coumestan (6H-benzofuro-[3,2,c][1]benzopyran-6-one) derivatives were synthesized. In these condensation reactions cyclohexan-1,3-dion derivatives act as a nucleophile and react with ortho-benzoquinone (formed in situ by oxidation of catechol) in aqua acetone in the presence of sodium acetate (CH3COONa) and potassium iodate or potassium ferricyanide. At the second stage of this study, methylether, [9]crown-3, [12]crown-4, [15]crown-5 and [18]crown-6 derivatives of obtained benzofuran compounds which were purified by crystallization were sysnthesized using dimethylsulphate/ K2CO3/ acetone for methylether derivatives, polyethyleneglycolditosilate/ Me2CO3/ H2O/ acetonitrile for macrocyclic polyethers derivatives (Figure 1.1). In addition, novel hydrazon derivatives of obtained crown ethers were prepared by the reaction of the macrocyclic polyethers with 2,4-dinitrophenylhydrazine (Figure 1.2) . These original hydrazon derivatives of crown ethers are easily soluble in aprotic solvents. Structures of all synthesized crown ethers were determined by IR, 1H-NMR, 13C-NMR and UV/ Vis. The complexion studies of these novel crown ethers with perchlorate salts of Li+, Na+, K+, Mg2+, Ca2+, Sr2+ and Ba2+ cations were examined. Then, solid complexes of 6,7-([15]crown-5)-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-(2¢,4¢-dinitrophenyl)hydrazon with NaSCN and 6,7-([18]crown-6)-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-(2¢,4¢-dinitrophenyl) hydrazon with KSCN were prepared by boiling in acetonitrile. Shift values of other crown ethers with some cations were determinated by UV/ Vis studies.
The synthetic method found in the literature to afford compounds possesing biological activity includes the connection of two bonds by oxidative condensation of 1,3-cyclicdiketones with 1,2-benzendiols, quinones and related compounds at room temperatures. Oxidation was performed with inorganic oxidation agents with both potassium iodate (KIO3) and potassium ferricyanide (K3[Fe(CN)6]). According to this procedure; ortho-dihydroxybenzofuran, 6,7-dihydroxy-3,4-dihydro-2H-dibenzofuran-1-one and ortho-dihydroxycoumestan have been prepared by the reaction carried out with cyclohexane-1,3-dione and 4-hydroxycoumarins respectively. A significant feature common to these benzofuran derivatives is the resembling coumestrol 3,9-dihydroxycoumestan structure which is known to be a potent estrogen. That increases the interest in these kind of benzofuran derivatives. For this purpose 8,9-dihydroxycoumestan derivatives of macrocyclic crown ether ligands were synthesized and examined on their alkali and earth alkali metal cation binding property in our laboratory. In this study, 6,7-dihydroxy-3,4-dihydro-2H-dibenzofuran-1-one and 6,7-dihydroxy-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-one which show the structural similarity with coumestan (6H-benzofuro-[3,2,c][1]benzopyran-6-one) derivatives were synthesized. In these condensation reactions cyclohexan-1,3-dion derivatives act as a nucleophile and react with ortho-benzoquinone (formed in situ by oxidation of catechol) in aqua acetone in the presence of sodium acetate (CH3COONa) and potassium iodate or potassium ferricyanide. At the second stage of this study, methylether, [9]crown-3, [12]crown-4, [15]crown-5 and [18]crown-6 derivatives of obtained benzofuran compounds which were purified by crystallization were sysnthesized using dimethylsulphate/ K2CO3/ acetone for methylether derivatives, polyethyleneglycolditosilate/ Me2CO3/ H2O/ acetonitrile for macrocyclic polyethers derivatives (Figure 1.1). In addition, novel hydrazon derivatives of obtained crown ethers were prepared by the reaction of the macrocyclic polyethers with 2,4-dinitrophenylhydrazine (Figure 1.2) . These original hydrazon derivatives of crown ethers are easily soluble in aprotic solvents. Structures of all synthesized crown ethers were determined by IR, 1H-NMR, 13C-NMR and UV/ Vis. The complexion studies of these novel crown ethers with perchlorate salts of Li+, Na+, K+, Mg2+, Ca2+, Sr2+ and Ba2+ cations were examined. Then, solid complexes of 6,7-([15]crown-5)-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-(2¢,4¢-dinitrophenyl)hydrazon with NaSCN and 6,7-([18]crown-6)-3,3-dimethyl-3,4-dihydro-2H-dibenzofuran-1-(2¢,4¢-dinitrophenyl) hydrazon with KSCN were prepared by boiling in acetonitrile. Shift values of other crown ethers with some cations were determinated by UV/ Vis studies.