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

Year 2020, Volume: 10 Issue: 1, 386 - 398, 01.03.2020

Fatih Eyduran , Mine Aydoğan Yerlikaya

https://doi.org/10.21597/jist.542445

Abstract

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.

Keywords

Azo, Skuarik asit, Spektroskopi, Skuaramik asit

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

Abstract

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.

Keywords

Azo, Squaric acid, Spectroscopy, Squaramic acid

References

• Aydoğan M, 2107. Siklobürendion içeren yeni azo boyarmaddelerin sentezi ve sprktroskopik özelliklerinin belirlenmesi. Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Yüksek Lisans tezi (Basılmış).
• Bodur G, 2013. Yeni skuar esteramid maddeleri, Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Yüksek Lisans tezi (Basılmış).
• 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.
• 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.
• Dawson JF, 1983. The Structure and Properties of Disperse Dyes in Polyester Coloration. J Soc. Dyers Color., 99 (7-8): 183–191.
• Furniss BS, Hannoford AJ, Smith PWG and Tatchell AR. 1989. Vogel's Textbook of practical Organic Chemistry. Longman scientific &Techical, s.952. England.
• Gauger J and Manecke G, 1970. Kondensationsprodukte der Quadratsaure mit primaren und sekundaren Aminen, I. Chem. Ber., 103: 2696- 2706.
• Gordon PF and Gregory P. 1983. Organic Chemistry in Colour. Springer-Verlag, s.96-100. New York.
• 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.
• Ivanovsky SA, Dorogov MV, Kravchenko DV, Ivachtchenko AV, 2007. Synthesis of the Substituted 3-Cyclobutene-1,2-diones. Synthetic Communications, 37: 2527–2542.
• 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.
• 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.
• 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.
• 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.
• 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.
• Manecke G and Gauger J, 1967. Kondensationsprodukte der quadkatsaube mit primeren und sekunderen aromatischen aminen. Tetrahedron Letters, 36:3509-3515.
• 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.
• 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.
• Neuse E and Green B, 1973. Amidierung von quadratsaure. Justus Liebigs Ann. Chem., (4):633-635.
• Neuse E and Green BR, 1974. Dianilino Derivatives of Squaric Acid. J. Org. Chem., 39(26):3881-3887.
• Park SY, Jun K and Oh SW, 2005. The Novel Functional Chromophores Based on Squarylium Dyes. Bull. Korean Chem. Soc., 26:428-432.
• 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.
• Reichardt C, 1990. Solvents and Solvent Effects in Organic Chemistry, WILEY: s.408, New York.
• 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.
• Schwander H, 1981. Heterocyclıc azo coupling components. Dyes and pigments, 3: 133–160.
• 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.
• 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.
• Sprenger HE, 1971. Verfahren zur Herstellung von Qadratsaurederivaten einer neunen Klasse. DE Patent: 000001618211A.
• 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.
• Towns AD, 1999. Developments in azo disperse dyes derived from heterocyclic diazo components. Dyes Pigm.,42:3–28.
• Ünsal M, 2013. Yeni skuarmamid maddeleri, Adnan Menderes Üniversitesi Fen Bilimleri Enstitüsü, Yüksek Lisans tezi (Basılmış).
• 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.
• 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.
• 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.
• Yen MS and Kuo MC. 2012. Solegel synthesis of organiceinorganic hybrid materials comprising boehmite, silica, and thiazole dye. Dyes and Pigments, 94:349-354.
• 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.
• 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.
• Zollinger H, 1990. Color chemistry: Synthese, properties and applications of organic dyes and pigments. Colour Chemistry VCH, Weinheim, New York.