Diazo kenetli kaliks[4]arenlerin ester ve keton türevlerinin sentezi

Abstract

Bu çalışmada, p-terf4?ütilkaliks[43aren, kaliks[4]aren, (4-n-bütii-fenilazo) kaliks[4]aren, (4-asetanilidfenilazo)kaliks[4]aren ve (2-aminotiyoazol)kaliks[43aren literatüre göre sentezlendi. Azokaliks[4}arenler, diazo bağlama reaksiyonuna göre kaliks[4]arene, 4-etilanilin, 4-n-bütilanilin, 4-asetanilid ve 2-aminotiyoazol bağlanmasıyla yapıldı. Yeni azokaliks[4]aren [25326,27,28-Teö-ametil-5,ll517,23-teto-(4-etilfenilazo) kaliks[4]aren (1), 25,26,27,28-Tetrametil-5,l l,17,23-tetra-(4-etilfenilazo)kaliks[4]aren tetraketon<2), 25,26,27~Tribenzoil-28-bidroksi~5, 11,1 7,23-tetxa-(4-etilfenilazo) kaliks [4]aren (3), 25,26,27,28-Tetrametil-5,ll,17,23-tetra-(4-n-bütilfenilazo) kaliks[4]aren (4), 25,26,27,28-Teframetil-5,ll,17,23-tetra-(4-n-bütilfenilazo) kaliks[4]aren tetra keton (5), 25,26,27-Tribenzoil-28-hidroksi-5, 11,1 7,23 -tetra-(4-n-bütilfeniİazo) kaliks [4]aren <6), 25,26,27,28- Teframetil-5,ll,17,23^etra-<4-asetanilidazo) kaliks[4]aren (7), 25,26,27,28-Tetrametil-5, 11,1 7323-tetra-(4-asetanilidlazo)kaliks[4]aren tetraketon (8), 25,26,27-Triben2»il-28-Wdroksi-5,ll,17,23-tetra-<4-asetanilidazo) kaliks[4]aren (9), 25,26,27,28-Tetrametil-5,ll,17,23-tetra-(2-tiyoazolazo)kaliks[4]arett (10), 25,26, 27,28-Tetrametil-5,ll,17,23-tetra-(24iyoazolazo)kaliks[43aren tetraketon (11), 25,26, 27-Tribenzoü-28-hidroksi-5, 1 1, 17,23-tetra-(2-tiyoazolazo)kaliks[43aren(12)] azokaliks aren metil keton benzoil ve asetil gruplanmn bağlanmasıyla hazırlandı. Sentezlenen bileşiklerin karakterizasyonu UV-Vis, ER., ^-NMR ve elemental analizi ile yapıldı. Çalışma sonucunda; metal bağlama özelliğine sahip kaliks[4]arenin hem ester, hem eter hem de keton fonksiyonel grup içeren türevleri ve renk oluşturucu azofenil türevi bileşikler oluşturuldu. Ester, eter ve keton bağlı grupların varlığı sebebiyle bileşiklerde çözünme özellikleriyle potansiyel çift bağlı kompleks yapma özelliği gözlendi. Bu özelliğe dayalı olarak ester ve keton içeren bağlı grupların (1-12) yerdeğiştirmesi sonucu, 12 yeni diazo bağlı kaliksaren türevi hazırlanmış oldu. **25SS&,,,-B*

In this study, p~ter?-butylcalix[4Jarene, calix[4]arene, (4-n-butylphenylazo) calix[4]arene, (4-acetanüiclazo)calix[4]arene and (2-aminothiazol)calix[4]arene were synthesized according to the literature. Azocalix{4]arenes were prepared by linking 4- ethylaniline, 4-n-butylaniline, 4-acetamidanilin and 2-aminothiazol to calix[4]arene through a diazo-coupling reaction. A new family of azocalix[4]arene, [25,26,27,28-Tetrame%l-5,ll,17,23-tetra- (4-ethylphenyl azo)calixi;43arene (1), 25,26,27,28-Tetrarûethyl-5,ll,17,234etra-(4- ethylphenylazo)calix[4]arene tetraketone (2), 25,26,27-Tribenzoyloxy-28-hydroxy- 5,ll,17,23-tetra-(4-ethylphenyIazo)calix[4]arene (3), 25,26,27,28-Tetra acetoxy-5,11, 17,23-tetra-(4-n-butylphenlazo)calix[4]arene (4), 25,26,27,28-Tetramethyl-5,ll,17,23- tetra^4-nrbutylphenylazo)calix[4]arene tetraketone (5), 25,26,27-Tribenzoyloxy-28- hydroxy-5, 11,1 7,23-tetra-(4-n-butylphenylazo)calix[4]arene (6), 25,26,27,28-Tetra acetoxy-5,ll,17,234etra<4-acetanilidazo)cali44]arene (7), 25,26,27,28-Tetramethyl- 5,ll,17,23-tetra-(4-acetanilidazo)calix[4]arene tetraketone (8), 25,26,27-Tri benzoyloxy-28-hydroxy-5,ll,17,23-tetra-(4-acetanilid azo)calix{43arene (9), 25,26,27, 28-Tetraacetoxy-5sl l,17,23-tetra-(2-thiazolazo)calix[4]arene (10), 25,26,27,28-Tetra rnethyl-5,ll,17,23-tefra-(2-thiazolazo)calix[4]arene tetraketon (11), 25,26,27-Tri benzoyloxy-28-hydroxy-5,ll,17,234etra-(2-thiazolazo)calix[4]arene (12)] were prepared by the incorporation of acetyl, benzoyl and methyl ketone units to azocalix[4]arene. Characterization of the synthesized compound was carried out the help of elemental analyses, UV-Vis, IR and ^-NMR spectroscopic studies. Thus the aim of present work was to build molecular 4esing constituted of calix[4]arene which contain both ester, ether and ketone moiety as a metal binding site and azophenyl moiety as coloration site. The incorporation of ester, ether and ketone subunit has chosen here due to its potential double-site complexation abilities completed by its solubility properties. This led us to the preparation of twelve new diazo coupling calixarenes substitued by ester, ether and ketone subunits 1-12.