50694-57-0Relevant academic research and scientific papers
SYNTHESIS OF 2,5-DILITHIO-1-METHYLIMIDAZOLE
Shapiro, Gideon,Marzi, Martin
, p. 3401 - 3404 (2007/10/02)
C5 to C2 position migrations of 2-trialkylsilyl and thiophenyl groups have been observed upon lithiation at the C5-position of corresponding C2-substituted 1-methylimidazoles.Double bromine-lithium exchange of 1-methyl-2,5-dibromoimidazole (5) affords a facile, quantitative and unequivocal synthesis of 2,5-dilithio-1-methyl-imidazole (4).Reaction of 4 with one equivalent of DMF occurs selectively at the C5 position to give 1-methylimidazole-5-carboxaldehyde.
Carbodesilylation of (Trimethylsilyl)imidazoles and -pyrazoles
Effenberger, Franz,Roos, Michael,Ahmad, Roshan,Krebs, Andreas
, p. 1639 - 1650 (2007/10/02)
The preparation of the 1-methyl(trimethylsilyl) (TMS)-substituted imidazoles 3a, 4a, 8, 9, and 11a by silylation of the corresponding metallated imidazoles is described.Carbodesilylation of 3 with aldehydes or carboxylic halogenides occurs selectively in 2-position.In the presence of a strong base (CsF) the reactivity against carbon electrophiles correlates well with the stability of the imidazolyl anions; regioselective carbodesilylation in 2-, 5-, or 4-position of the twofold TMS-substituted imidazoles 3a and 9 therefore is possible, which allows the synthesis of a great variety of hydroxyalkyl-substituted imidazoles and of acylimidazoles.By using the dimethylsulfamoyl substituent as an N-protecting group, the N-unsubstituted 5-benzoylimidazole (26) as well as the comparable 5-benzoyl-pyrazole (30b) and 5-(hydroxyphenylmethyl)pyrazole (30a) are accessible. Key Words : Imidazoles, (trimethylsilyl)-, carbodesilylation of / Pyrazoles, (trimethylsilyl)-, carbodesilylation of / Carbodesilylation
A General Route to 4-Substituted Imidazoles
Katritzky, Alan R.,Slawinski, Jaroslaw J.,Brunner, Frederic,Gorun, Sergiu
, p. 1139 - 1145 (2007/10/02)
Literature routes to di(imidazol-4-yl)methanol (1a) dinitrate and tri(imidazol-4-yl)methanol (2a) trihydrochloride were improved to give 32 and 16percent overall yields, respectively; but we failed to synthesize bis- (1b) and tris-(1-methylimidazol-4-yl)methanol (2b) by the methylation of the corresponding N-methoxymethyl compounds (3; x=2 and x=3).Attempted 4-lithiation of the 1,2,5-protected imidazole (4a) with BuLi-TMEDA failed, giving after hydrolysis 1-methyl-5-trimethylsilylimidazole (4b); similar failures were observed for 2,5-dicarboxy-1-methylimidazole, which after metallation with BuLi-TMEDA and hydrolysis afforded 1-methylimidazole-5-carboxylic acid (5).Our attempts to obtain 4-bromo-1-methylimidazole (10a) and 4-bromo-1-ethylimidazole suitable for a halogen-lithium exchange or for Grignard reaction also failed.Attempted selective lithiation of 2-phenylthio-1-tritylimidazole (16) at the 4-position, then theatment with ethyl formate, led only to a mixture of 4- and 5-substituted products in very low yield, and 1-diethoxymethyl-2-phenylthioimidazole (18) was unstable and difficult to purify. 4-Bromoimidazole with two mol equiv. of t-butyl-lithium gives 1,4-dilithioimidazole, which is now shown to provide a general route to 4-substituted imidazoles.
STUDIES ON THE DILITHIATION OF 1-METHYLIMIDAZOLE. OPTIMISATION OF REACTION CONDITIONS FOR SYNTHESES OF 2,5-DISUBSTITUTED DERIVATIVES
Carpenter, Andrew J.,Chadwick, Derek J.,Ngochindo Raphael I.
, p. 1913 - 1941 (2007/10/02)
Reaction of 1-methylimidazole with an excess of n-butyllithium yields the 2,5-dilithio intermediate.The extent of dilithiation is dependent on the solvent, reaction time, temperature and molar ratio of the lithiating agent to the substrate.Use of a chelating agent for Li(+) decreases the reaction time, temperature and molar excess of the alkyllithium required for high-yielding dilithiation.Syntheses via the dilithio intermediate of 2,5-bis(hydroxydiphenylmethyl)- (3) and 2,5-bis(methylthio)-1-methylimidazole (5), of 1-methyl-5-trimethylsilylimidazole (8), and (in poor yields) of 1-methylimidazole-2,5-dicarboxylic acid (9) and methyl 1-methylimidazole-2,5-dicarboxylate (10) are reported.
