Four nucleic acid bases and their nucleosides were chlorinated by acyl chloride in dimethylformamide and m-chloroperbenzoic acid(MCPBA). The reaction of bases or nucleosides with MCPBA and acyl chlorides in dimethylformamide shows that under such conditions N-oxidation and chlorination of the primary hydroxyl group was not observed and the major product obtained was from the chlorination of heterocyclic bases. In the absence of MCPBA, the reaction took place the chlorination of 5'-hydroxy group of nucleosides. In the pyrimidine series, the product was the 5-chlorinated derivative and in the purine series, the 8-chlorinated analog was formed. In addition, other halide ion sources that could make complexes with dimethylformamide were investigated. 5-Bromouridine was also synthesized by using phosphorous tribromide in analogous manner.
The halogenated compounds thus obtained were all separated by using silica gel column except for the 5-chlorouracil, and their structures or purities were characterized by the physical (mp, TLC) and spectroscopic (UV, NMR, HPLC) methods.
Application and limitation of the chlorination reaction is discussed as well as mechanistic implications.
피리미딘 및 푸린 계열의 염기와 그들의 뉴클레오시드 또는 2'-데옥시 뉴클레오시드들의 염소화 반응이 염화 벤조일과 N,N-디메틸포름아미드, 그리고 3-클로로-퍼옥시벤조산에 의하여 이루어졌다.
피리미딘 염기와 이의 뉴클레오시드들은 5 위치에 염소화 반응이 일어나며 수율이 좋다. 푸린 염기와 이의 뉴클로오시드들은 8 위치에 염소화 반응이 일어나며 피리미딘 계열에 비하여 수율이 좋지 않다.
염화 벤조일 외에도 N,N-디메틸포름아미드와 작용하여 착물을 만들 수 있는 여러가지 다른 할로겐을 포함한 화합물들에 대한 연구도 이루어졌다.
