104048-92-2Relevant articles and documents
Synthesis of trifluoromethylated analogues of 4,5-dihydroorotic acid
Sukach, Volodymyr A.,Resetnic, Anastasia A.,Tkachuk, Viktor M.,Lin, Zhengguo,Kortz, Ulrich,Vovk, Mykhailo V.,R?schenthaler, Gerd-Volker
, p. 1290 - 1301 (2015)
4-(Trifluoromethyl)pyrimidin-2(1H)-ones react with trimethylsilyl cyanide in the presence of a tertiary amine catalyst to give Michael-like 1,4-conjugate hydrocyanation adducts exclusively at the 3,6-positions. The resulting 2-oxo-6-(trifluoromethyl)- 1,2,3,4-tetrahydropyrimidine-4-carbonitriles have been used to synthesize new trifluoromethylated 4,5-dihydroorotic acid analogues and their esters in racemic as well as enantiopure forms by a chiral auxiliary approach. The orthogonal intramolecular C-F...C=O interaction between the fluorine atom of the CF3 group and the carbon atom of the ester group observed in the crystal state may stabilize the sterically unfavourable conformation of the methyl 2-oxo-6-(trifluoromethyl) hexahydropyrimidine-4-carboxylate molecule with axially oriented substituents.
Electron-deficient heteroarenium salts: An organocatalytic tool for activation of hydrogen peroxide in oxidations
?turala, Ji?í,Bohá?ová, Soňa,Chudoba, Josef,Metelková, Radka,Cibulka, Radek
, p. 2676 - 2699 (2015/03/18)
A series of monosubstituted pyrimidinium and pyrazinium triflates and 3,5-disubstituted pyridinium triflates were prepared and tested as simple catalysts of oxidations with hydrogen peroxide, using sulfoxidation as a model reaction. Their catalytic efficiency strongly depends on the type of substituent and is remarkable for derivatives with an electron-withdrawing group, showing reactivity comparable to that of flavinium salts which are the prominent organocatalysts for oxygenations. Because of their high stability and good accessibility, 4-(trifluoromethyl)pyrimidinium and 3,5-dinitropyridinium triflates are the catalysts of choice and were shown to catalyze oxidation of aliphatic and aromatic sulfides to sulfoxides, giving quantitative conversions, high preparative yields and excellent chemoselectivity. The high efficiency of electron-poor heteroarenium salts is rationalized by their ability to readily form adducts with nucleophiles, as documented by low pKR+ values (pKR+ red > -0.5 V). Hydrogen peroxide adducts formed in situ during catalytic oxidation act as substrate oxidizing agents. The Gibbs free energies of oxygen transfer from these heterocyclic hydroperoxides to thioanisole, obtained by calculations at the B3LYP/6-311++g(d,p) level, showed that they are much stronger oxidizing agents than alkyl hydroperoxides and in some cases are almost comparable to derivatives of flavin hydroperoxide acting as oxidizing agents in monooxygenases.
4-TRIFLUOROMETHYLPYRIMIDINES
Gerus, I. I.,Vdovenko, S. I.,Gorbunova, M. G.,Kukhar', V. P.
, p. 398 - 406 (2007/10/02)
It is shown that β-alkoxyvinyl trifluoromethyl ketones are convenient reagents for the synthesis of 4-trifluoromethylpyrimidines that contain a hydrogen atom or hydroxy, mercapto, and amino groups in the 2 position.The NMR, IR, and UV spectra of the synth
