TLC 상에서 1차 및 2차 아민 혼합물에 대한 FMOC-NHS 및 FMOC-Cl의 유도체화 반응성
Derivatization Reactivity of FMOC-NHS and FMOC-Cl in a Mixture with Primary- and Secondary Amines on TLC
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초록
Amine계 불법약물의 혼합물에 대하여 신속하고 용이한 동정과 반정량의 목적을 위한 예비실험으로, 이들 혼합물의 직접적인 유도체화 반응성을 평가하고자 구조적으로 유사한 2종의 amine(1, 2) 혼합물을 silica gel (SiO2) 및 alumina (Al2O3) TLC 상에서 유도체화 시약인 9-fluorenylmethyl chloroformate (FMOC-Cl, C) 및 N-(9-fluorenylmethoxycarbonyloxy)succinimide (FMOC-NHS, D) 와 각각 반응시켰다. 유도체화 반응 생성물을 대조 물질(A, B)과 비교한 후, TLC image 분석을 통하여 생성 spot(s)에 대한 반 정량화를 시도 하였다. C 및 D는 2종의 TLC상에서 1차 및 2차 amine과 반응하여 UV-active한 FMOC-group 을 함유한 유도체를 생성하였으며 각 시약에 따른 amine 화합물의 반응성 차이가 관찰되었다. TLC image 분석결과, silica gel TLC상 D를 사용한 유도체화 실험에서 1차 amine(1)이 2차 amine(2)에 비하여 높았으나(면적 비, 1 : 0.62 ~ 0.88), C를 사용하였을 경우에는 상대적으로 낮게 나타났다(면적 비, 1 : 1.06 ~ 1.67). 그러므로 반응성은 사용된 유도체화 시약 및 TLC의 종류에 따른 차이, 그리고 농도에 의존적이었다. 그러나 alumina TLC에서는 사용 시약의 종류에 무관하게 2차 amine(2)의 반응성이 높았다(면적 비, 1 : 1.01 ~ 1.62).
Abstract
As a preliminary test for a rapid and easy identification and semi-quantitative determination of the presence and amount of illegal amines in a mixture, two structurally similar amine compounds (1, 2) were reacted to evaluate their derivatization reactivity in a mixture on silica gel and alumina TLC with 9-fluorenylmethyl chloroformate (FMOC-Cl, C) or N-(9-fluorenylmethoxycarbonyloxy)succinimide (FMOC-NHS,D) as derivatizing reagents. The derivatized products were identified, compared with reference compounds (A,B) and TLC image analysis of corresponding spots was performed for semi-quantitative evaluation. The reagents C and D generated compounds containing strongly UV-absorbing FMOC-group on the TLC plate after reacting with primary- and secondary amines but different reactivity of amines with the reagents was observed. After TLC image analysis, in the experiment on silica gel plates with D the reactivity of primary amine (1) was higher than that of secondary amine (2) showing the area ratio of 1 (for A) : 0.62 ~ 0.88 (for B), but C reacted more with the secondary amine (2) demonstrating the area ratio of 1 (for A) : 1.06 ~ 1.67 (for B). The reactivity of the amines tested was dependent on the concentration and types of the derivatizing reagents, the concentration of each amines and types of TLCs. In the experiment on alumina plates the reactivity of secondary amine (2) was higher than that of primary amine (1) showing the area ratio of 1 (for A) : 1.01 ~ 1.62 (for B) irrespective of derivatizing reagents used.
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