Premium
Treatment of Polyfluoro‐1,1‐dihydroalkyl Sulfones with Sodium Cyanate and Triethylamine: A New Method for the Synthesis of 6‐(Polyfluoroalkyl)uracils
Author(s) -
Timoshenko Vadim M.,
Nikolin Yarema V.,
Chernega Alexander N.,
Shermolovich Yuriy G.
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200205)2002:10<1619::aid-ejoc1619>3.0.co;2-8
Subject(s) - chemistry , triethylamine , cyanate , alkylation , methanol , uracil , aqueous solution , organic chemistry , pyrimidine , chlorine , medicinal chemistry , amination , ammonia , sodium , stereochemistry , catalysis , dna , biochemistry
Polyfluoro‐1,1‐dihydroalkyl benzyl sulfones 1 reacted with sodium cyanate in the presence of Et 3 N to give triethylammonium salts of uracil derivatives 2 . The structure of 2b was established by X‐ray determination. Acidification of compounds 2 with aqueous HCl gave 5‐(benzylsulfonyl)‐6‐(polyfluoroalkyl)pyrimidine‐2,4(1 H ,3 H )‐diones 3 . Alkylation of compounds 3 with CH 3 I afforded products methylated at N‐2, confirmed by X‐ray diffraction. Treatment of 3 with PCl 5 gave dichloropyrimidines 7 . The chlorine atoms in compounds 7 with polyfluoroalkyl substituents of different lengths showed differing reactivities in reactions with ammonia and methanol. The sites of substitution of chlorine atoms in 7 were elucidated by X‐ray studies. Direct amination of 3 occurred together with desulfonylation on heating in HMPA, with formation of 6‐(polyfluoroalkyl)‐substituted 2,4‐bis(dimethylamino)pyrimidines 13 . (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)