3,4-Dimetoksifenilasetonitril’in Kuaterner Amonyum Tipi Dimerik Yüzey Aktif Maddeler İle Faz Transfer Katalizli Siklopentilasyonu

Year 2024, Volume: 24 Issue: 6, 1313 - 1322, 02.12.2024

Ayşen Şuekinci Yılmaz , Mesut Boz

https://doi.org/10.35414/akufemubid.1437228

Abstract

Bir organik sentezde genellikle uygun bir baz ile C, O, N gibi atomlara bağlı asidik karakterde bir protonun koparılması gerekir. Bu amaçla uygun baz ve çözücü sisteminin seçimi önemlidir ki sıklıkla güçlü bazlar ve kurutulmuş çözücüler kullanılması gerekir. Kimya Endüstrisinin gelişmesiyle birlikte artan çevre sorunları sebebiyle, kimyasalların ve kimyasal proseslerin çevreye olumsuz etkilerini azaltmayı veya ortadan kaldırmayı amaç edinen "Yeşil Kimya" kavramı gitgide önem kazanmaktadır. Daha ılımlı bazlar, daha zararsız çözücüler içeren çevre dostu organik sentez prosedürlerinin uygulanması hayati derecede önemlidir. Bu prosesler arasında farklı fazlarda çözünebilen reaktiflerin etkileşmesini sağlayarak, reaksiyonların daha kısa sürede ve yüksek verimlerle gerçekleşmesini sağlayan faz transfer katalizli reaksiyonlar öne çıkmaktadır. Faz transfer katalizi sistemleri enerji sarfiyatını azaltmanın yanı sıra, yan ürün oluşumunu da baskılayarak saflaştırma aşamasında daha az çözücü kullanılması gibi ekonomik avantajlarda sunmaktadır. Organik sentezlerde sıklıkla bir kuarterner amonyum tuzu olan tetrabütilamonyum bromür (TBAB) faz transfer katalizörü olarak kullanılır. Son yıllarda kuaterner amonyum bileşiklerinin dimerik yapıda olanları monomerik olanlara göre üstün yüzey aktif özellikleriyle dikkat çekmekte ve bu bileşikler “gemini sürfaktan” olarak adlandırılmaktadır. Bilim insanları bu bileşiklerin fizikokimyası ve yüzey aktif özellikleri ile ilgili çok sayıda araştırma ortaya koymuşlardır. Fakat bu bileşiklerin tetrabütilamonyum bromür gibi faz transfer katalizli organik sentezlere uygulanması ile ilgili çalışmalar sınırlıdır. Bu çalışmada sekiz farklı dimerik kuaterner amonyum bileşiği sentezlenerek, bu bileşiklerin 3,4-dimetoksifenilasetonitril’in siklopentilasyonunda faz transfer katalizörü olarak davranışı incelenmiştir. Dimerik sürfaktanların 3,4-dimetoksifenilasetonitril’in siklopentilasyon reaksiyonunu geleneksel faz transfer katalizörü TBAB kadar iyi verimlerle katalizlediği, hatta bazı dimerik surfaktanların TBAB’den daha yüksek verimler oluşturduğu tespit edilmiştir.

Keywords

Faz transfer katalizi, Dimerik yüzey aktif madde, Nükleofilik yerdeğiştirme, Yeşil kimya

Ethical Statement

Yazarlar tüm etik standartlara uyduklarını beyan ederler.

Phase Transfer Catalyzed Cyclopentylation of 3,4-dimethoxyphenylacetonitrile with Quaternary Ammonium Type Dimeric Surfactants

Abstract

Generally, in an organic synthesis, an acidic proton bonded to atoms such as C, O, N must be removed with a suitable base. For this purpose, the selection of the appropriate base and solvent system is important that strong bases and dried solvents often need to be used. Due to the increasing environmental problems depending on development of the Chemical Industry, the concept of "Green Chemistry", which aims to reduce or prevent the harmful effects of chemicals and chemical processes on the environment, has gradually gained importance. It is vitally important to implement environmentally friendly organic synthesis procedures that include mild bases and more harmless solvents. Among these processes, phase transfer catalyzed reactions which enable the reactions to occur in a shorter time and with higher yields by enabling the interaction of reagents that can be dissolved in different phases, come into prominence. In addition to reducing energy consumption, phase transfer catalysis systems also offer economic advantages such as using less solvent in the purification stage by suppressing by-product formation. Tetrabutylammonium bromide (TBAB), a quaternary ammonium salt, is frequently used as a phase transfer catalyst in organic syntheses. In recent years, dimeric quaternary ammonium compounds have attracted attention with their superior surface active properties compared to monomeric ones, and these compounds are called "gemini surfactants". Scientists have conducted numerous studies on the physicochemistry and surface active properties of these compounds. However, studies on the application of these compounds to phase transfer catalyzed organic syntheses such as tetrabutylammonium bromide are limited. In this study, eight different dimeric quaternary ammonium compounds (gemini surfactant) were synthesized and the behavior of these compounds as phase transfer catalysts in the cyclopentylation of 3,4-dimethoxyphenylacetonitrile was examined. It has been determined that dimeric surfactants catalyze the cyclopentylation reaction of 3,4-dimethoxyphenylacetonitrile with yields as good as the traditional phase transfer catalyst TBAB, and some dimeric surfactants even produce higher yields than TBAB.

Keywords

Phase transfer catalysis, Dimeric surfactant, Nucleophilic substitution, Green Chemistry

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