4-(Hetarilazoil)anilinlerin Skuaramik Asit Türevlerinin Sentezi ve Karakterizasyonu

Öz

Çalışmada, azo grubu taşıyan skuaramik asitlerin (bileşikler 4-6) sentezleri tek-kap içerisinde gerçekleştirildi. Bileşikler 4-6’nın sentezi için önce serbest amino grubu içeren azo boyarmaddeleri (bileşikler 1-3), diazo-kenetlenme yöntemiyle elde edildi. Bu yöntemde, çıkış bileşiği 3-hidroksi-4-metoksi-siklobut-3-en-1,2-dion, metanol ortamında, metanolün skuarik asit ile tekli yerdeğiştirmesi sonucunda elde edilmiş ve izole edilmeden bileşikler 4-6’nın sentezinde kullanılmıştır. Bileşikler 4-6, elde edilen bileşikler 1-3’ün 3-hidroksi-4-metoksi-siklobut-3-en-1,2-dion arasındaki tekli yerdeğiştirme tepkimesi sonucunda tek-kap içerisinde metanol ortamında düşük verimlerle sentezlenmiştir. Bileşikler 2, 4, 5 ve 6’nın kimyasal yapıları, spektroskopik yöntemler (FTIR, NMR) ile aydınlatılmıştır. Ayrıca, farklı çözelti ortamlarında bileşikler 4-6’nın UV-Görünür bölge absorpsiyon spektrumları alınmış ve değerlendirilmiştir. Bu sentez yönteminde, bileşikler 1-3, 3-hidroksi-4-metoksi-siklobut-3-en-1,2-dion’un -OCH3 grubu ile -OH grubuna göre bişelik 3 hariç seçimli yer değiştirdiği belirlenmiştir.

Anahtar Kelimeler

• Azo,Skuarik asit,Spektroskopi,Skuaramik asit

Synthesis and Characterization of Squaramic Acid Derivatives of 4-(Hetarilazoil)anilines

Öz

In the study, synthesis of squaramic acids having azo group (compounds 4-6) were carried out in a one-pot. For the synthesis of compounds 4-6, firstly azo dyes bearing the free amine group (compounds 1-3) were obtained by the diazo-coupling method. In this method, the starting compound 3-hydroxy-4-methoxy-cyclobut-3-en-1,2-dione was obtained in the methanol medium as a result of the single substitution of methanol with squaric acid and used in the synthesis of compounds 4-6 without isolation. Compounds 4-6 were synthesized in a one-pot in a low yield in methanol medium as a result of single displacement reaction between compounds 1-3 and 3-hydroxy-4-methoxy-cyclobut-3-en-1,2-dione. Chemical structures of compounds 2, 4, 5, 6 were confirmed by spectroscopic methods (FTIR, NMR). In addition, UV-Vis absorption spectra of compounds 4-6 in different solutions were taken and evaluated. In this synthesis method, it was determined that compound 1 and 2 were selectively substituted with the -OCH3 group of 3-hydroxy-4-methoxy-cyclobut-3-en-1,2-dione compared -OH group.

Anahtar Kelimeler

• Azo,Squaric acid,Spectroscopy,Squaramic acid

Kaynakça

1. Aydoğan M, 2107. Siklobürendion içeren yeni azo boyarmaddelerin sentezi ve sprktroskopik özelliklerinin belirlenmesi. Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Yüksek Lisans tezi (Basılmış).
2. Bodur G, 2013. Yeni skuar esteramid maddeleri, Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Yüksek Lisans tezi (Basılmış).
3. Charton J, Charruault L. Dѐprez-Poulain R, Dѐprez B, 2008. Alkylsquarates as key intermediates for the rapid preparation of original drug-inspired compounds. Combinatorial Chemistry & High Throughput Screening, 11(4):294-303.
4. 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.
5. Dawson JF, 1983. The Structure and Properties of Disperse Dyes in Polyester Coloration. J Soc. Dyers Color., 99 (7-8): 183–191.
6. Furniss BS, Hannoford AJ, Smith PWG and Tatchell AR. 1989. Vogel's Textbook of practical Organic Chemistry. Longman scientific &Techical, s.952. England.
7. Gauger J and Manecke G, 1970. Kondensationsprodukte der Quadratsaure mit primaren und sekundaren Aminen, I. Chem. Ber., 103: 2696- 2706.
8. Gordon PF and Gregory P. 1983. Organic Chemistry in Colour. Springer-Verlag, s.96-100. New York.

9. Hutchings MG, Ferguson I, Allen S, Zyssd J, Ledoux I, 1998. Non-linear Optical Properties of Squarate Esters and Amides. J. Chem. Research, Snopses, 5:244-245.
10. Ivanovsky SA, Dorogov MV, Kravchenko DV, Ivachtchenko AV, 2007. Synthesis of the Substituted 3-Cyclobutene-1,2-diones. Synthetic Communications, 37: 2527–2542.
11. Kitson SL. 2017. Squaryl Molecular Metaphors named publication of, AAs, Squaryl Molecular Metaphors – Application to Rational Drug Design and Imaging Agents. Journal of Diagnostic Imaging in Therapy, 4(1): 35-75.
12. 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.
13. 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.
14. Lòpez C, Sanna E, Carreras L, Vega M, Rotger C and Costa A, 2013a. Molecular Recognition of Zwitterions: Enhanced Binding and Selective Recognition of Miltefosine by a Squaramide-Based Host. Chem. Asian J. 8:84–87.
15. Lòpez C, Vega M, Sanna E, Rotger C and Costa A, 2013b. Efficient microwave-assisted preparation of squaric acidmonoamides in water. RSC Adv., 3:7249–7253.
16. Manecke G and Gauger J, 1967. Kondensationsprodukte der quadkatsaube mit primeren und sekunderen aromatischen aminen. Tetrahedron Letters, 36:3509-3515.
17. 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.
18. Mehrabi H, Anary-Abbasinejad M and Pour SA, 2013. The formation of squaramic acids and squaryl diamides by the reaction of squaric acid with alkyl isocyanides. Journal of Chemical Research, 37(6):342–344.
19. Neuse E and Green B, 1973. Amidierung von quadratsaure. Justus Liebigs Ann. Chem., (4):633-635.
20. Neuse E and Green BR, 1974. Dianilino Derivatives of Squaric Acid. J. Org. Chem., 39(26):3881-3887.
21. Park SY, Jun K and Oh SW, 2005. The Novel Functional Chromophores Based on Squarylium Dyes. Bull. Korean Chem. Soc., 26:428-432.
22. Peng Q, Li M, Gao K and Cheng L, 1992. Hydrazone-Azo Tautomerism of Pyridone Azo Dyes. Part III-Effect of Dye Structure and Solvents on the Dissociation of Pyridone Azo Dyes. Dyes and Pigments, 296:271-286.
23. Reichardt C, 1990. Solvents and Solvent Effects in Organic Chemistry, WILEY: s.408, New York.
24. Sanna E, Martinez L, Royger C, Blasco S, Gonżalez J, Garcίa-Espaňa E and Costa A, 2010. Squaramide-based reagent for selective chromogenic sensing of Cu(II) through a zwitterion radical. Organic Letters, 12(17): 3840-3843.
25. Schwander H, 1981. Heterocyclıc azo coupling components. Dyes and pigments, 3: 133–160.
26. Seio K, Miyashita T, Sato K and Sekine M, 2005. Synthesis and Properties of New Nucleotide Analogues Possessing Squaramide Moieties as New Phosphate Isosters. Eur. J. Org. Chem., 24: 5163–5170.
27. Sokolowska J, Podsiadly R, Sochocka E, 2007. Synthesis and properties of some disazo disperse dyes derivatives 2-amino-6-phenylazobenzothiazole and 2-amino-6-(4-nitro) phenylazobenzothiazole. Dyes and Pigments, 72: 223-227.
28. Sprenger HE, 1971. Verfahren zur Herstellung von Qadratsaurederivaten einer neunen Klasse. DE Patent: 000001618211A.
29. Süleymanoğlu N, Ustabaş R, Alpaslan YB, Eyduran F, 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.
30. Towns AD, 1999. Developments in azo disperse dyes derived from heterocyclic diazo components. Dyes Pigm.,42:3–28.
31. Ünsal M, 2013. Yeni skuarmamid maddeleri, Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Yüksek Lisans tezi (Basılmış).
32. Xie J, Comeau AB, Seto CT. 2004. Squaric Acids: A new motif for designing inhibitors of protein tyrosine phosphatases. Organic Letters, 6(1): 83-86.
33. 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.
34. Yen MS and Wang IJ, 2004. Synthesis and absorption spectra of hetarylazo dyes derivedfrom coupler 4-aryl-3-cyano-2-aminothiophenes. Dyes and Pigments, 61: 243–250.
35. Yen MS and Kuo MC. 2012. Solegel synthesis of organiceinorganic hybrid materials comprising boehmite, silica, and thiazole dye. Dyes and Pigments, 94:349-354.
36. Zadrożna I, Kaczorowska E, 2008. Relationship between structure and nonlinear optical properties of new bisazo chromophores. Theoretical and experimental study. Struct Chem, 19: 131–135.
37. Zakerhamidi MS, Ghanadzadeh A, Moghadam M, 2012. Solvent effects on the uv/ visible absorption spectra of some aminoazobenzene dyes. Chem Sci Trans., 1:1-8.
38. Zollinger H, 1990. Color chemistry: Synthese, properties and applications of organic dyes and pigments. Colour Chemistry VCH, Weinheim, New York.