Segal A, Maté U, Solomon J J
Chem Biol Interact. 1979 Dec;28(2-3):333-44. doi: 10.1016/0009-2797(79)90173-x.
The new adduct N6-(2-carboxyethyl)adenine (N6-CEA) was prepared from 1-(2-carboxyethyl)adenine (1-CEA) by base catalyzed (Dimroth) rearrangement of 1-CEA. The structure of N6-CEA was assigned on the basis of UV spectra and electron impact and isobutane chemical ionization mass spectra. When the carcinogen beta-propiolactone was reacted in vitro with calf thymus DNA, 1-CEA but not N6-CEA was detected on paper chromatograms following acid hydrolysis of the DNA. When BPL-reacted single-stranded DNA was incubated at pH 11.7 (37 degrees C, 18 h) prior to acid hydrolysis, it was found that 1-CEA was completely converted to N6-CEA in DNA by Dimroth rearrangement, whereas no conversion occurred at pH 7.5. The extent of Dimroth rearrangement at various pHs and temperatures was determined for 1-CEA, 1-methyladenine (1-MeA), 1-(2-carboxyethyl)-deoxyadenosine-5'-monophosphoric acid (1-CEdAdo5'P) and the phosphodiester 5'-O-(2-carboxyethyl)phosphono-1-(2-carboxyethyl)deoxyadenosine (1-CE-Ado-5'-P-CE).
新加合物N6-(2-羧乙基)腺嘌呤（N6-CEA）是由1-(2-羧乙基)腺嘌呤（1-CEA）通过1-CEA的碱催化（迪姆罗特）重排反应制备而成。N6-CEA的结构是根据紫外光谱、电子轰击质谱和异丁烷化学电离质谱确定的。当致癌物β-丙内酯在体外与小牛胸腺DNA反应时，DNA经酸水解后，在纸色谱上检测到的是1-CEA而非N6-CEA。当BPL反应后的单链DNA在酸水解前于pH 11.7（37℃，18小时）孵育时，发现DNA中的1-CEA通过迪姆罗特重排完全转化为N6-CEA，而在pH 7.5时未发生转化。测定了1-CEA、1-甲基腺嘌呤（1-MeA）、1-(2-羧乙基)-脱氧腺苷-5'-单磷酸（1-CEdAdo5'P）和磷酸二酯5'-O-(2-羧乙基)膦酰基-1-(2-羧乙基)脱氧腺苷（1-CE-Ado-5'-P-CE）在不同pH值和温度下的迪姆罗特重排程度。
