형광식별제로서 7-Aminocoumarin 유도체의 합성 및 물성

Abstract

석유회사들은 시장에서 경쟁력 있는 석유제품을 가지기 위하여 고품질의 제품을 개발하는데 많은 돈을 투자하고 있다. 자사의 개발된 석유제품이 다른 석유제품 또는 불법적인 유사 석유제품과 혼합되는 것을 막기 위하여 고유의 석유식별제, 즉 마커(marker)를 사용한다. 마커의 한 종류인 형광식별제는 등록된 석유제품과 불법적으로 제조된 석유제품을 휴대용 UV/VIS 측정기를 사용하여 쉽게 판별하는데 이용되고 있다. 본 연구에서는 형광식별제로서 coumarin계 유도체를 형광증백제 (Fluorescent Whitening Agent)로부터 개발하고자 하였다. 유기용제에 높은 용해도를 가진 7-(dialkylamino)coumarin 유도체는 7-amino group에 alkyl기를 도입하여 합성되었다. Ethyl phenylformylacetate (1)는 Claisen condensation 반응으로 methyl phenylacetate와 ethyl formate 로부터 합성되었다. 3-Aminophenol (2a)은 2당량의 alkyl bromide 유도체와 S_(N)2 반응에 의해 3-(dialkylamino)phenol (2b~h)로 합성되었다. Methyl phenylformylacetate (1)와 3-aminophenol (2a) 및 3-(dialkylamino)phenol (2b~h)은 AlCl3 존재 하에서 Pechmann reaction으로 coumarin계 유도체인 7-amino-3-phenylcoumarin (3a) 및 7-(dialkylamino)-3-phenylcoumarin (3b~h) 유도체가 합성되었다. Ethyl acetoacetate 와 3-Aminophenol (2a) 및 3-(dialkylamino)phenol (2b~h)과의 반응으로 7-amino-4-methylcoumarin (4a) 및 7-(dialkylamino)-4-methylcoumarin (4b~h)가 합성되었다. 합성한 화합물의 구조는 ^(1)H NMR spectrum으로 분석하였고 UV-Vis, PL (Photoluminescence spectrometer)을 통하여 물리적 성질을 확인하였다.; Petroleum companies have invested a colossal sum to develop the high- quality petroleum products so that they hope to have competitive products in oil market. A maker is usually used to protect the company owned high-quality petroleum products from mixed products or illegal imitations. Fluorescent markers which are a sort of the markers are used to distinguish readily the authorized petroleum products from the unauthorized by using potable UV/VIS detector. In this study, coumarin derivatives as the fluorescent marker for the petroleum products were developed from fluorescent whitening agent. 7-(Dialkylamino)coumarin derivatives with the high solubility in the nonpolar solvents have been prepared by the alkylation for 7-amino group. Ethyl phenylformylacetate (1) has been prepared by the Claisen reaction of methyl phenylacetate with ethyl formate. 3-(Dialkylamino)phenol (2b~h) have been prepared by the S_(N)2 reaction of 3-aminophenol with alkyl bromide. 7-Amino-3-phenylcoumarin (3a) and 7-(dialkylamino)-3-phenylcoumarin (3b~h) were synthesized by Pechmann reaction, which involves the condensation of ethyl phenylacetate (1) with 3-aminophenol (2a) or 3-(dialkylamino)phenol (2b~h) in presence of aluminum chloride. 7-Amino-4-methylcoumarin (4a) and 7-(dialkylamino)-4-methylcoumarin (4b~h) were synthesized by Pechmann reaction, which involves the condensation of ethyl acetoacetate with 3-aminophenol (2a) or 3-(dialkylamino)phenol (2b~h) in presence of aluminum chloride. The structures of synthesized compounds were characterized by the analysis of ^(1)H NMR spectrum. The physical properties of compounds were performed by the measurements of UV/VIS and PL(photoluminescence spectrometer).