(4-Aryldiazenil)anilinlerin Karışık Skuarat Türevlerinin Sentezi, Karakterizasyonu ve Bazı Spektroskopik Özellikleri

Öz

Primer aromatik azo-aminlerin, dietoksiskuarat (DES) ile yer değiştirme tepkimesi sonucu;  olası ürünlerden tekli yer değiştirme ürünü olan (bileşik M ve G) karışık skuaramatlar (MSA’lar) sentezlendi. Bileşikler M ve G’nin kimyasal yapıları spektroskopik yöntemler (¹H-NMR, FTIR) ve mikro element analizi kullanılarak aydınlatıldı. Ayrıca bileşiklerin çeşitli çözücüler içinde UV-Görünür bölge absorpsiyon spektrumları da elde edildi.  Bileşik G’nin ¹H-NMR spektrumunda, etil grubu protonlarının sinyallerinde, syn/anti rotamer oluşumundan kaynaklanan bir bozulma gözlenmektedir. Bileşik M’in kloroform ve DMSO içindeki UV-Görünür bölge absorpsiyon spektrumlarından belirlenen λ_mak değerleri, p-Aminoazobenzen’in karşılık gelen değerleri ile karşılaştırıldığında, bileşik M’in 2-etoksi-3,4-dion-1-siklobütenil grubunun bu çözücüler içinde sırasıyla 14.5 ve 15 nm’lik hipsokromik kaymaya neden olduğu görülebilir. Spektroskopik veriler, bileşikler M ve G’nin kullanılan çözücüler içinde enamin-diketo formda bulunduğunu göstermektedir.  

Anahtar Kelimeler

• Azo,skuarat

Kaynakça

1. Bodur G. (2013).“Yeni skuar esteramid maddeleri”, Yayımlanmamış Yüksek Lisans tezi, Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Aydın, 33-50.
2. Charton J, Charruault L, Poulain RD and Deprez B. (2008).“Alkylsquarates as Key Intermediates for the Rapid Preparation of Original Drug-Inspired Compounds”, Combinatorial Chemistry & High Throughput Screening, 11, 294-303.
3. Cohen S and Cohen SG. (1966). “Preparation and Reactions of Derivatives of Squaric Acid. Alkoxy-, Hydroxy-, and Aminocyclobutenediones”, Journal of the American Chemical Society., 88(7), 1533-1536. Furniss BS, Hannoford AJ, Smith PWG and Tatchell AR. (1989).“Vogel's Textbook of practical Organic Chemistry”, Longman scientific&Techical, England, 952.
4. Gauger J and Manecke G. (1970).“Kondensationsprodukte der Quadratsaure mit primaren und sekundaren Aminen, I”, Chem. Ber. 103, 2696- 2706.
5. Hutchings MG, Ferguson I, Allen S, Zyssd J, Ledoux I. (1998).“Non-linear Optical Properties of Squarate Esters and Amides”, J. Chem. Research (S) , 244-245.
6. Ivanovsky SA, Dorogov MV, Kravchenko DV and Alexandre VI. (2007).“Synthesis of the Substituted 3-cyclobutene-1,2-diones”, Synthetic Communications, 37, 2527–2542.
7. Kumar SP, Glòria PMC, Gonçalves LM and Gut J, Rosenthal PJ, Moreira R, Santos MMM. (2012).“Squaric acid: a valuable scaffold for developing antimalarials?”, Med. Chem. Commun., 3, 489–493.
8. Lim NC, Morton MD, Jenkins HA and Bruckner C. (2003).“Squaric Acid N-Hydroxylamides: Synthesis, Structure, and Properties of Vinylogous Hydroxamic Acid Analogues”, J. Org. Chem., 68, 9233-9241.

9. Lòpez C, Vega M, Sanna E, Rotger C, Costa A. (2013).“Efficient microwave-assisted preparation of squaric acidmonoamides in water”, RSC Adv., 3, 7249–7253.Manecke G. and Gauger J. (1967).“Kondensationsprodukte der quadkatsaube mit primeren und sekunderen aromatischen aminen”, Tetrahedron Letters, 3509-3515.
10. Marin SDL, Xu Y, Meijler MM and Janda KD. (2007).“Antibody catalyzed hydrolysis of a quorum sensing signal found in Gram-negative bacteria”, Bioorganic & Medicinal Chemistry Letters, 17 1549–1552.
11. Mukkanti A and Periasamy M. (2005). “Methods of synthesis of cyclobutenediones”, Arkivoc (XI), 48-77.
12. Neuse E and Green B. (1973a).“Amidierung von quadratsaure”, Liebigs Ann. Chem., 633-635.
13. Neuse E and Green B. (1973b).“Amidierung von quadratsaure-estern”, Liebigs Ann. Chem., 619-632.
14. Neuse EW and Green BR. (1974).“Dianilino derivatives of squaric acid”, Polymer, 39(26), 3881-3887.
15. Park SY, Jun K and Oh SW. (2005).“The Novel Functional Chromophores Based on Squarylium Dyes”, Bull. Korean Chem. Soc.,26, 428-432.
16. Palekar VS, Pingale ND and Shukla SR. (2010). “Synthesis, spectral properties and application of novel disazo disperse dyes derived from polyester waste”, Color. Technol., 126, 86–91.Requena JVA, Lopez EM and Herrera RP. (2015).“One-pot synthesis of unsymmetrical squaramides”, RSC Adv., 5, 33450–33462.
17. Rostami A, Colin A, Li XY, Chudzinski MG, Lough AJ and Taylor MS. (2010).“N,N'-diarylsquaramides: General, high-yielding synthesis and applications in colorimetric anion sensing”, J. Org. Chem., 75, 3983–3992.
18. Rotger MC, Piňa MN, Frontera A, Martorell G, Ballester P, Deyà PM and Costa A. (2004). “Conformational Preferences and Self-Template Macrocyclization of Squaramide-Based Foldable Modules”, J. Org. Chem., 69, 2302-2308.
19. Sanna, E. Martinez, Rotger C, Blasco S, Gonżalez J, Espaňa EG, and Costa A. (2010). “Squaramide-Based Reagent for Selective Chromogenic Sensing of Cu(II) through a Zwitterion Radical”, Organic Letters, 12(17), 3840-3843.
20. Schmidt AH. (1980).“Reaktionen von Quadratsäure und Quadratsäure-Derivaten”, Sythesis, 12, 961-994.
21. Sprenger HE. (1971).“Verfahren zur Herstellung von Qadratsaurederivaten einer neunen Klasse”, DE Patent No: 000001618211A, Februar 25.
22. Storer RI, Aciroa C and Jonesb LH. (2011).“Squaramides: physical properties, synthesis and applications”, Chem. Soc. Rev.,40, 2330–2346.
23. Süleymanoğlu N, Ustabaş R, Alpaslan YB, Eyduran F and İskeleli NO. (2012). “Experimental and theoretical investigation of the molecular and electronic structure of 3-ethoxy-4-isopropylaminocyclobut-3-ene-1,2-dione”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 96, 35–41.
24. Ünsal M. (2013).“Yeni skuarmamid maddeleri”, Yayımlanmamış Yüksek Lisans tezi, Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Aydın, 33-46.
25. Xie J, Comeau AB and Seto CT. (2004).“Squaric Acids: A New Motif for Designing Inhibitors of protein tyrosine phosphatases”, Organic Letters, 6(1), 83-86.
26. Ximenis M, Bustelo E, Algarra AG, Vega M, Rotger C, Basallote MG and Costa A. (2017) “Kinetic Analysis and Mechanism of the Hydrolytic Degradation of Squaramides and Squaramic Acids”, J. Org. Chem., 82, 2160−2170.
27. Xu Y, Yamamoto N, Ruiz DI,. Kubitz DS and Janda KD. (2005).“Squaric monoamide monoester as a new class of reactive immunization hapten for catalytic antibodies”, Bioorganic & Medicinal Chemistry Letters, 15, 4304–4307.
28. Zadrozna I and Kaczorovska E. (2008). “Relationship between structure and nonlinear optical properties of new bisazo chromophores. Theoretical and experimental study”, Struct Chem., 19(1), 131–135.