Halka-zincir-halka dinamik kombinatoryal kütüphane sentezlerinde lineer serbest enerji ilişkilerinin araştırılması









































































ii
ABSTRACT
An Investigation of Lineer Free Energy Relationships in the Synthesis of RingChain-Ring Tautomeric Dynamic Combinatorial Library
The treatment of the ring-chain-ring tautomeric mixture of imidazolidine-1-ole, nitrone and oxadiazinane (INO) with hydroxylamine hydrochloride gives hydroxylaminoamine hydrochloride and the corresponding oxime. The addition of 5 different substituted aldehydes (each equivalent with the amine in the library) provides Dynamic Combinatorial Library (DCL). The concentration of the aldehydes in the equilibrated at 25oC for 20 hours were measured chromatographycally using GC/MS. The mean equilibria in DCL were defined as the interconversions of INOAr-X and INOAr-Y (X and Y represent the substituents on the aromatic ring). Thus KXY = [INOAr-Y][X-ArCHO]/[INOAr-X][INO-ArCHO] equilibrium constants were calculated and correlated with Hammett constants and their combinations. The reactivity order of the aldeydes in the DCL was determined as follows: p-NO2 > m-NO2 > p-Cl > p-H > p-MeO. Analogously, a second library was created based on the benzilydene exchange reaction of INO and aldehyde mixture in the presence of F3CSO3H. Addition of Zinc(II) as a template to the library caused a substituent effect change over and the Hammett correlations produced better results with the corresponding I constants. Thus the benzylidene exchange reactions of ring-chain-ring tautomeric mixtures (INOAr-X(Y)) in the presence of acids allow to construct a more rich and sensitive to amplification DCLs since the recognition fragment undergo reaction with the modifier group to give l component tautomeric mixture then an mxn DCL matrix produce mxnxl ligands.
Keywords: INO, Nitrones, Imidazolidine-1-ole, Imidazoline-3-oxides, Oxadiazinanes, RingChain-Ring Tautomers, Dynamic Combinatorial Library, Lineer Free Energy Relationships, Hammett Correlations.



7. SAYFAYA BENZER SAYFALAR

Biyolojik aktif bazı maddelerin teorik olarak incelenmesi - Sayfa 32
19 Benzilidenin yer değiştirme reaksiyonları DCL' ye göre (Dynamic Combinatorial Library) imidazolidin-1-ol, azot ve okzadiazin (INO) arasında, zincir-halka-zincir tautomeri oda sıcaklığında oluşturmuşlardır. Reaksiyonun olası mekanizması Hammet türü koralasyon analizine göre tartışılmıştır. DCL içindeki denge, INOAr-X' in INOArY' ye karşılıklı değişmesini açıklamışlardır. Benzer aldehitlerle Y...
Biyolojik aktif bazı maddelerin teorik olarak incelenmesi - Sayfa 144
131 KAYNAKLAR DİZİNİ Aslan, S., 1985, Modem Teşhis İlaç ve Tedavi. Beta Basım Yayın Dağıtım, İstanbul, I. Cilt; 258-273s. Atkins, PW., and Friedman, RS.,1997, Molecular Quantum Mechanics, Third Edition, Oxford University Press, Malta Buckner, J.S., and Newman, S. M., 1990, Uric acid stroge in the epidermal cells of Manduca sexta:Localization and movement during the pupa! transformation, Joumal...

7. SAYFADAKI ANAHTAR KELIMELER

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7. SAYFA ICERIGI

ii
ABSTRACT
An Investigation of Lineer Free Energy Relationships in the Synthesis of RingChain-Ring Tautomeric Dynamic Combinatorial Library
The treatment of the ring-chain-ring tautomeric mixture of imidazolidine-1-ole, nitrone and oxadiazinane (INO) with hydroxylamine hydrochloride gives hydroxylaminoamine hydrochloride and the corresponding oxime. The addition of 5 different substituted aldehydes (each equivalent with the amine in the library) provides Dynamic Combinatorial Library (DCL). The concentration of the aldehydes in the equilibrated at 25oC for 20 hours were measured chromatographycally using GC/MS. The mean equilibria in DCL were defined as the interconversions of INOAr-X and INOAr-Y (X and Y represent the substituents on the aromatic ring). Thus KXY = [INOAr-Y][X-ArCHO]/[INOAr-X][INO-ArCHO] equilibrium constants were calculated and correlated with Hammett constants and their combinations. The reactivity order of the aldeydes in the DCL was determined as follows: p-NO2 > m-NO2 > p-Cl > p-H > p-MeO. Analogously, a second library was created based on the benzilydene exchange reaction of INO and aldehyde mixture in the presence of F3CSO3H. Addition of Zinc(II) as a template to the library caused a substituent effect change over and the Hammett correlations produced better results with the corresponding I constants. Thus the benzylidene exchange reactions of ring-chain-ring tautomeric mixtures (INOAr-X(Y)) in the presence of acids allow to construct a more rich and sensitive to amplification DCLs since the recognition fragment undergo reaction with the modifier group to give l component tautomeric mixture then an mxn DCL matrix produce mxnxl ligands.
Keywords: INO, Nitrones, Imidazolidine-1-ole, Imidazoline-3-oxides, Oxadiazinanes, RingChain-Ring Tautomers, Dynamic Combinatorial Library, Lineer Free Energy Relationships, Hammett Correlations.

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