19090-02-9Relevant articles and documents
o-directed lithiation of acylated hydroxythiophenes
Vendina, Ineta,Parkova, Anete,Trapencieris, Peteris
, p. 1565 - 1572 (2016/11/01)
O-Carbamates derived from 2-hydroxy- and 3-hydroxy-thiophenes generated o-directed carbanions, which were transformed to the corresponding methyl sulfides and methyl and trimethylsilyl substituted thiophenes.
Tautomerism of the Monohydroxy Derivatives of Five-Membered O, N, and S Heterocycles
Capon, Brian,Kwok, Fu-Chiu
, p. 5346 - 5356 (2007/10/02)
The O-deuterated enolic tautomers 3-deuteroxybenzofuran, 3-deuteroxybenzothiophene, 3-deuteroxyindole, 3-deuteroxy-1-methylindole, 3-deuteroxyfuran, 3-deuteroxythiophene, 2-deuteroxybenzothiophene, and 2-deuteroxythiophene have been generated in solution in mixtures of CD3COCD3, CD3CN, or CD3SOCD3 with D2O by hydrolysis of their trimethylsilyl derivatives in the presence of DCl (1E-3 - 1E-4 M) and characterized by 1H NMR spectroscopy.Solutions of 3-hydroxypyrrole and of 3-hydroxy-1-methylpyrrole were obtained by methanolysis of their trimethylsilyl derivatives,evaporation of the methanol, and immediate dissolution in DMSO-d6.The carbocyclic analogues of the bicyclic heterocyclic enols 3-deuteroxyindene and 2-deuteroxyindene were also generated in solution.Attempts to prepare solutions of 2-deuteroxyfuran, 2-deuteroxypyrrole, and 2-deuteroxy-1-methylpyrrole were unsuccessful.The kinetics of ketonization of the OH forms of these enols have been investigated in water or aqueous acetonitrile solution.The equilibrium constants for the keto-enol tautomerism were also determined either by direct measurement when sufficient enol was present at equilibrium or as the ratio of the rate constant for enolization of the keto form to that for ketonization of the enol form, the former being determined by the iodine-trapping technique.The effect of solvent on the equilibrium constants was also studied.Sufficient data were available for the equilibrium between 3-hydroxyindole and 3-ketoindole for them to be analyzed by the four-parameter equation of Mills and Beak to yield an a value of 2.4 and a b value of -3.0.The pKas of the bicyclic enols were measured. 3-Hydroxybenzofuran and3-hydroxybenzothiophene are stronger acids than 3-hydroxyindole and 3-hydroxy-1-methylindole.The ketonization reactions are general acid and general base catalyzed and their mechanisms are discussed.
HETEROCYCLIC SILYL ENOL ETHER CHEMISTRY: SYNTHESIS AND REACTIVITY OF 3-TRIMETHYLSILOXYFURAN AND 3-TRIMETHYLSILOXYTHIOPHENE
Camici, Lucia,Ricci, Alfredo,Taddei, Maurizio
, p. 5155 - 5158 (2007/10/02)
The preparation of the title compounds is reported starting from the corresponding bromo derivatives. 3-Trimethylsiloxyfuran gives rise easily to cycloadditions affording bicyclic tetrahydrofuranoic systems.