Asetik Anhidrit Alternatifi Olarak Trietilamonyum Hidrojen Sülfat Kullanılarak Kromenilyum-Siyanin Boya Sentezine Yeşil ve Pratik Bir Yaklaşım

Year 2025, Volume: 10 Issue: 6, 978 - 985, 30.11.2025

Yusuf Alçay

https://doi.org/10.35229/jaes.1737673

Abstract

Kromenilyum-siyanin boyaları, yakın kızılötesi (NIR) bölgesinde güçlü absorpsiyon ve emisyon özellikleri nedeniyle son yıllarda önemli ilgi görmüştür. Bu sebeple kromenilyum-siyanin boyaları, gelişmiş optik sensörler, biyolojik görüntüleme ajanları ve moleküler probların geliştirilmesi için oldukça umut verici adaylar haline gelmiştir. Bu tür boyaların hazırlanmasında geleneksel olarak kullanılan sentetik metodolojiler geleneksel olarak asetik anhidrit gibi reaksiyon ortamlarında ısıtmaya dayanır. Asetik anhidrit, temel olarak kondenzasyon reaksiyonlarını kolaylaştırmada etkili olsa da önemli sınırlamalar getirmektedir. Özellikle, asetik anhidrit oldukça uçucu, yanıcı ve toksiktir ve kullanımı sıkı güvenlik önlemleri gerektirir. Ayrıca, belirli ülkelerde tedarik edilmesine ilişkin düzenleyici kısıtlamalar olması sebebiyle, yeşil kimya ilkelerine uygun olarak daha sürdürülebilir ve çevre dostu alternatiflerinin belirlenmesine yönelik artan bir ihtiyaç durumu söz konusudur. Bu zorluklar ışığında, bu çalışma, yeni bir kromenilyum-siyanin boyasının sentezinde daha yeşil ve daha güvenli bir reaksiyon ortamı olarak trietilamonyum hidrojen sülfatın (TEAHS) kullanımını araştırmaktadır. Optimize edilmiş koşullar altında, hedef bileşik (CS2), 9-(2-karboksifenil)-6-(dietilamino)-1,2,3,4-tetrahidroksantilyum perkloratın (2) 2-(1,3,3-trimetilindolin-2-iliden)asetaldehit (3) ile TEAHS varlığında kondenzasyon reaksiyonu yoluyla başarıyla sentezlenmiştir. Elde edilen boya, karakteristik kromenilyum-siyanin optik özellikleri sergiler ve yapısı, gelişmiş iki boyutlu nükleer manyetik rezonans (2D NMR) spektroskopisi kullanılarak açıklanmıştır. Bildiğimiz kadarıyla, bu bileşiğin 2D NMR teknikleri ile tam yapısal karakterizasyonunu ayrıntılı olarak açıklayan literatürdeki ilk raporu temsil etmektedir ve böylece sürdürülebilir sentetik yollar aracılığıyla NIR-aktif floroforların tasarımına değerli görüler katmaktadır.

Keywords

karakterizasyon , kromenilyum-siyanin , TEAHS , yeşil kimya

Project Number

46427

A Green and Practical Approach to Chromenylium–Cyanine Dye Synthesis Using Triethylammonium Hydrogen Sulfate as an Alternative to Acetic Anhydride

Abstract

Chromenylium-cyanine dyes have attracted considerable attention in recent years due to their strong absorption and emission characteristics in the near-infrared (NIR) region, which make them highly promising candidates for the development of advanced optical sensors, bioimaging agents, and molecular probes. The synthetic methodologies traditionally employed for the preparation of such dyes typically rely on reaction media such as acetic anhydride. Although acetic anhydride is effective in facilitating key condensation reactions, it poses significant limitations. Specifically, acetic anhydride is highly volatile, flammable, and toxic, and its use requires strict safety precautions. Furthermore, regulatory restrictions on its availability in certain countries highlight the growing need to identify more sustainable and environmentally benign alternatives in accordance with the principles of green chemistry. In light of these challenges, the present study explores the use of triethylammonium hydrogen sulfate (TEAHS) as a greener and safer reaction medium in the synthesis of a novel chromenylium-cyanine dye. Under optimized conditions, the target compound (CS2) was successfully synthesized through the condensation reaction of 2 with 3 in the presence of TEAHS. The resulting dye exhibits characteristic chromenylium-cyanine optical properties, and its structure was unequivocally elucidated using advanced two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy for the first time in the literature.

Keywords

characterization , chromenylium-cyanine , green chemistry , TEAHS

Supporting Institution

Istanbul Technical University - Scientific Research Projects Coordination Unit

Project Number

46427

Thanks

I would like to express my sincere gratitude to Prof. Dr. Ismail Yılmaz and his research group for giving me the opportunity to work in their laboratory and for their valuable support.

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