Search

In this work, new heterocyclic compounds containing1,2,4-triazole ring were synthesizedstarting from iminoester hydrochlorides and benzhydrazide. The fluorescenceproperties of the novel triazole compounds synthesized were determined inorganic solvents such as methanol and DMSO. The diimine derivatives among thenew triazoles show high fluorescence intensities in methanol. Reduced diimines(8) have lower fluorescenceproperties in methanol than diimine compounds (6). The compounds were also tested for their antioxidant andcarbonic anhydrase inhibitory (CAI) activities. Low CAI activity was observed.Bis Schiff bases (6) showed betteractivity with lower IC50 values of 200 and 330 μM. The compoundsshowed moderate to high antioxidant activity in both DPPH and FRAP antioxidanttests. The SC50 values in DPPH test were as low as 0.01 mg/mL, closeto that of standard antioxidants. Similarly, a high TEAC value as 8197 mM wasobserved showing considerably high FRAP activity. Structural differences wereeffective on the antioxidant activities of the new compounds. Benzoylhydrazones(2), oxadiazoles (3) and amino-triazoles (4) showed higher activity in bothantioxidant tests as compared to compounds 5-8., Buçalışmada, iminoester hidroklorürler ve benzhidrazidden başlanarak1,2,4-triazol halkası içeren yeni heterosiklik bileşikler sentezlendi. Triazolbileşiklerinin floresans özellikleri metanol ve DMSO gibi organik çözücülerdebelirlendi. Triazol bileşikleri arasında diimin bileşikleri metanolde yüksekfloresans şiddeti gösterdi. İndirgenmiş bileşikler (8) dimin bileşiklerine (6)göre metanolde düşük floresans özelliğine sahiptir. Yeni sentezlenenbileşiklerin antioksidan ve karbonik anhidraz inhibitör (CAI) aktiviteleriincelendi. Bileşiklerde düşük CAI aktivitesi gözlendi. Bis Schiff bazları (6), 200 ve 330 μM'ın altındaki IC50değerleriyle daha iyi aktiviteye sahipti. Bileşikler DPPH ve FRAP testlerininher ikisinde de orta ve yüksek seviyede antioksidan aktivite gösterdi. DPPHradikal temizleme testinde bileşiklerin bazılarının SC50 değerleristandart antioksidanlarınkine yakın 0,01 mg/mL seviyesinde olduğu görüldü.Benzer şekilde 8197 mM TEAC değeriyle yüksek FRAP aktivitesi tespit edildi.Yeni bileşiklerin yapısal farklılıkları antioksidan aktivitelerinde etkilioldu. Benzoilhidrazonlar (2), oksadiazoller(3) ve amino-triazoller (4), 5-8 billeşiklerinekıyasla yüksek aktivite gösterdiler.

Stoichiometric protonation constants of some 3-alkyl(aryl)-4-(p-t-butyl(benzyl/benzyliden)amino)-4,5-dihydro-1H-1,2,4-triazole-5-one derivatives were determined potentiometrically in 50% (v/v) ethanol-water mixtures at 25 oC with an ionic strength of 0.10 M. The calculation of the stoichiometric protonation constants was carried out using a PKAS computer program. The effect of solvents composition on the stoichiometric protonation constants are discussed. KEY WORDS: Ethanol-water mixtures, Stoichiometric protonation constants, Potentiometry Bull. Chem. Soc. Ethiop. 2010, 24(2), 185-192.

WOS: 000237294700004 A series of 4-arylidenamino-4H-1,2,4-triazole derivatives (3-11) were synthesized from the treatment of 4-amino-4H-1,2,4-triazoles (2) with certain aldehydes. Compounds 3-11 were reduced with NaBH4 to afford the corresponding 4-arylmethylenamino-4H-1,2,4-triazoles (12-20). Compounds 1-10 and 12-19 were characterized by elemental analyses and H-1 NMR, C-13 NMR, IR, and UV spectral data. Compounds 11 and 20 were characterized by H-1 NMR, C-13 NMR, IR and mass spectral data. Compounds 14, 16, 17, and 18 were tested for anticancer activities. Compound 17, chosen for its higher anticancer activity in the preliminary tests with the cancer cell lines of MCF7, NCI-H460, and SF-268, exhibited remarkable anticancer potential in screening tests with 60 human cancer cell lines.

ÖZET Bu çalışmada, önce N-benzoil etil imidobenzoat ve N-benzoil etil imido-p-metil- benzoat sentez edilmiş ve bunların etil karbazat, tert-butil karbazat, asetilhidrazin, formilhidrazin, benzoilhidrazin, metilhidrazin, 3-amino- 1,2,4-triazol ve üre ile olan reaksiyonları incelenerek bazı açık zincirli hidrazin türevleri ile bazı 1,2,4-triazol türevleri elde edilmiştir. Çalışmada elde edilen bazı hidrazin türevlerinin başka yöntemlerle de sentezlenebilmesi için amid etoksikarbonilhidrazonlar bazı acil klorürler ile muamele edilmiş, ancak bu reaksiyonun N^-disubstitue hidrazin türevlerinin oluşumuna yol açtığı kanıtlanmıştır. Çalışmanın bundan sonraki bölümünde etil benzoat benzoilhidrazon ve etil p- metilbenzoat benzoilhidrazon bileşikleri ile çalışılmıştır. Bu bileşiklerin etil karbazat ve metil hidrazin ile reaksiyonundan 2,5-disubstitue-l,3,4-oksadiazol bileşiklerine varıldığı beUrlenmiştir. Aym bileşiklerin hidrazin hidrat ile reaksiyonundan ise 4-amino-4H-l,2,4- triazol türevlerinin oluştuğu saptanmıştır. Çalışmada, bunlara ilaveten, 4-amino-3,5-difenil-4H- 1,2,4-triazol ile 4-amino-3- fenil-5-p-tolil-4H-l,2,4-triazol bileşiklerinin değişik aldehidler ile reaksiyonlan incelenerek 4-arilidenamino-3,5-difenil-4H-l,2,4-triazoller ile 4-arihdenamino-3-fenil-5-p-toUl-4H- 1,2,4-triazollerin sentezleri gerçekleştirilmiş, bu bileşikler üzerinde yapılan yanempirik kuantum kimyasal çalışmalarla E ve Z izomerlerinin kararlılıkları belirlenmiş ve diğer bazı kuantum-kimyasal parametreler hesaplanmıştır. Çalışmada, ayrıca, elde edilen arilidenamino bileşiklerinin NN=CH grubunda indirgenmeleri için genel bir yöntem olıuşturulmuş ve 3,5-&substime-4-arüberızüamino-4H- 1,2,4-triazorier elde edilmiştir. Çalışmada 44' ü yeni 17` si literatürde kayıtlı olmak üzere toplam 61 madde sentez edilmiş olup, yapı aydınlatılmaları için mikroanaliz, İR, İH-NMR, 13C-NMR ve UV spektroskopik yöntemleri kullanılmıştır. Ayrıca çalışmada uygulanan reaksiyonlar için reaksiyon mekanizmaları önerilmiştir. Anahtar Kelimeler : Alkil imidatlar, İmidik asid türevleri, hidrazonik asid türevleri, hidrazin türevleri, 1,3,4-oksadiazorier, 1,2,4-triazorier, arilidenamino bileşikleri, arilbenzilamino bileşikleri, indirgenme, kuantum kimyası, yarı empirik metodlar. VI SUMMARY The Preparation of Some Imidic and Hydrazonic Acid Derivatives, The Synthesis of Some Heterocyclic Compounds and The Investigation of Their Reactions In this study first, N-benzoyl ethyl imidobenzoate and N-benzoyl ethyl imido-p- methylbenzoate were synthesized and the reactions of these compounds with ethyl carbazate, tert-butyl carbazate, acetylhydrazine, formylhydrazine, benzoylhydrazine, methylhydrazine, 3-amino-l,2,4-triazole and urea to give some open-chain hydrazine derivatives or 1,2,4- triazoles were investigated. In order to obtain the open- chain hydrazine derivatives via a different method, amide etoxy carbonylhydrazones were treated with several acyl chlorides. But, these treatments led to the formation of some TSL.N'- (^substituted hydrazines. In another part of the study, ethyl benzoate benzoylhydrazone and ethyl p-methyl benzoate benzoylhydrazone were respectively reacted with ethyl carbazate and methylhydrazine to give 2,5-di-substituted-l,3,4-oxadiazoles. However, the reactions of the same compounds with hydrazine hydrate resulted in the formation of 4-amino-4H- 1,2,4- triazoles. Moreover, the reactions of 4-amino-3,5-diphenyl-4H-l,2,4-triazole and 4-amino-3- phenyl-5-p-tolyl-4H-l,2,4-triazole with various aldehydes were also investigated in the study, and so, 4-arylidenamino-3,5-diphenyl-4H-l,2,4-triazoles and 4-arylidenamino-3- phenyl-5-p-tolyl-4H-l,2,4-triazoles were synthesized. The stabilities of the E and Z isomers of the arylidenamino compounds were determined using quantum-chemical semi empiric methods. Some other quantum-chemical parameters related to these compounds were also calculated. In addition, a general method for the selective reduction of NN=CH group of the arylidenamino compounds synthesized in the study was established and the corresponding 3,5-disubstituted-4-arylbenzylamino-4H-l,2,4-triazoles were obtained. 44 new and 17 known compounds were synthesized using different routes in the study, Combustion analyses and spectracopic methods such as IR^H-NMR^C-NMR and UV were used for the identification of these compounds. Furthermore, some reaction mechanisms were proposed for the reactions applied in the study. Keywords : Alkyl imidates, imidic acid derivatives, hydrazonic acid derivatives, hydrazine derivatives, l,3,4-oxadiazoles,l,2,4- triazoles, arylidenamino compounds, arylbenzylamino compounds, reduction, quantum chemistry, semi empirical methods. VTT 302