MECHANISM AND STEREOCHEMISTRY OF THE FLUORINATION OF URACIL AND CYTOSINE USING FLUORINE AND ACETYL HYPOFLUORITE

被引：45

作者：

VISSER, GWM ^{[1
]}

BOELE, S ^{[1
]}

VONHALTEREN, BW ^{[1
]}

KNOPS, GHJN ^{[1
]}

HERSCHEID, JDM ^{[1
]}

BRINKMAN, GA ^{[1
]}

HOEKSTRA, A ^{[1
]}

机构：

[1] NIKHEF-K, 1009 AJ AMSTERDAM, NETHERLANDS

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1986年 / 51卷 / 09期

关键词：

D O I：

10.1021/jo00359a015

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The products of the reaction of CH3COOF and F2 with uracil and cytosine dissolved in acetic acid and water were studied by using 18F as a tracer. Apart from 5-fluorouracil (2) and the 5,5-difluoro adducts 5a and 5b, the 1H NMR spectra of the crude reaction mixture showed the presence of two geometric isomers of both 5-fluoro-6-acetoxy-5,6-dihydrouracil (3a,4a) and 5-fluoro-6-hydroxy-5,6-dihydrouracil (3b,4b). In the fluorination of cytosine, corresponding products were observed with the exception of the acetoxy adducts. For both reagents and for both substrates a radical-cation mechanism is proposed. The observed conversions of the acetoxy adducts of uracil are explained by an acylimine (iii) as an intermediary.

引用

页码：1466 / 1471

页数：6