Synthesis of imidazoles

Conclusions The synthesis of 4-alkylimidazoles was carried out by heating (2-oxoalkyl)triethylammonium bromides with formamide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No, 1, pp. 140–143, January, 1989.     

Synthesis of imidazoles

Silica gel was found to facilitate the conversion of 3-bromo-2-alkanones to imidazoles by the action of formamide. The selective 3-bromination of 2-alkanones was carried out in ethyl acetate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 511–513, February, 1991.     

Synthesis of tri- and tetrasubstituted imidazoles

A reliable sequence that allows for regiospecific incorporation of four alkyl substituents on an imidazole ring has been developed. This procedure involves the addition of a substituted amino alcohol to a thioamide and subsequent oxidation with PDC. Unlike many imidazole syntheses, acid-sensitive functionality is tolerated given the mild conditions.     

Synthesis of alkylated iridolactone analogs

Bicyclic δ-lactones, iridolactones analogs with an alkyl group at the bicyclic junction, are obtained from α-alkyl-α-hydroxymethylcyclopentanones via an intramolecular Horner-Wadsworth-Emmons reaction.     

Synthesis of highly alkylated functionalized cyclopentadienes

Tetra- and pentaalkylated cyclopentadienyl ketones and carboxylic acids are prepared by electrophilic allylation of enolizible 1,3-dicarbonyl compounds and successive acid catalyzed cyclisation.     

Synthesis of substituted imidazoles via organocatalysis

A one-pot synthesis of substituted imidazoles is described. The cornerstone of this methodology involves the thiazolium-catalyzed addition of an aldehyde to an acyl imine to generate the corresponding alpha-ketoamide in situ followed by ring closure to the imidazole in a one-pot sequence. The extension of this methodology to the one-pot synthesis of substituted oxazoles and thiazoles is also described. [reaction: see text]     

Synthesis of nitro derivatives of alkylated phenols

Summary 2-Mono- and 2,6-dinitro-4-alkylphenols with a tertiary alkyl group were synthesized and characterized.     

New alkylated and perfluoroalkylated phosphonic acids: Synthesis, adhesive and water-repellent properties on aluminum substrates

This paper describes the synthesis of phosphonic acids (R-S-(CH₂)₂-PO(OH)₂) containing a perfluoroalkylated chain (R = C₆F₁₃-(CH₂)₂, C₈F₁₇-(CH₂)₂) or an alkyl group (R = C₁₂H₂₅, C₁₈H₃₇). These compounds, obtained in excellent yield by telomerization of vinyl phosphonic acid in the presence of alkylated or perfluorinated mercaptans used as transfer agents, were characterized by ¹H, ¹⁹F and ³¹P nuclear magnetic resonance. Thermal characterization by differential scanning calorimetry (DSC) showed the presence of mesophases for compounds containing C₈F₁₇ and C₁₈H₃₇ end groups. A lamellar structure with a layered or bilayered organization was identified by small angle X-ray scattering (SAXS). Adhesion of these compounds on aluminum surfaces is improved by the presence of phosphonic groups. Hydrophobic properties of coated aluminum surfaces are enhanced by fluorinated groups.     

Synthesis and alkaline hydrolysis of (pentafluoroethyl)imidazoles

Photochemical ring substitution of the N-trifluoroacetyl derivatives of histamine and of L-histidine methyl ester by pentafluoroethyl radical provides the corresponding 2- and 4-pentafluoroethylated products in yields of 19% and 27%, respectively. Alkaline hydrolysis converts the 2-pentafluoroethyl group to trifluoroacetyl. The reaction mechanism, involving a diazafulvene intermediate, is analogous to that elucidated for (trifluoromethyl)imidazoles; however, the pentafluoroethyl group is markedly more reactive to hydrolysis than the trifluoromethyl group. For imidazole derivatives, the ratio of reactivities is 75 at C-2 and 40 at C-4. The hydrolysis of 4-(pentafluoroethyl)histamine affords the bicyclic product, 4-(trifluoromethyl)-6,7-dihydro-1H-imidazo[4,5-c]-pyridine in 65.4% yield.     

Synthesis and Antiproliferative Evaluation of 2-Deoxy-N-glycosylbenzotriazoles/imidazoles

A series of 2-deoxy-2-iodo-α-d-mannopyranosylbenzotriazoles was synthesized using the benzyl, 4,6-benzylidene and acetyl protected D-glucal in the presence of N-iodosuccinimide (NIS). Subsequent removal of the iodine at the C-2 position using tributyltin hydride under free radical conditions afforded the 2-deoxy-α-d-glucopyranosylbenzotriazoles in moderate to high yields. This method was extended to the preparation of substituted 2-deoxy-β-d-glucopyranosylimidazoles as well. The stereoselectivity of the addition reaction and the effect of the protecting group and temperature on anomer distribution of the benzotriazole series were also investigated. The anticancer properties of the newly synthesized compounds were evaluated in a series of viability studies using HeLa (human cervical adenocarcinoma), human breast and lung cancer cell lines. The N-[3,4,6-tri-O-benzyl-2-deoxy-α-d-glucopyranosyl]-1H-benzotriazole and the N-[3,4,6-tri-O-acetyl-2-deoxy-α-d-glucopyranosyl]-2H-benzotriazole were found to be the most potent cancer cell inhibitors at 20 µM concentrations across all four cell lines.     

Synthesis and fluorescent properties of a new class of heterocycles of isoindole fused imidazoles with phenolic subunits

A new class of heterocycles of isoindole fused imidazoles with phenolic subunits has been readily synthesized by a two-step one-pot reaction. In aprotic solvent they show high fluorescent properties (Phi(F) up to 0.93), but in protic polar solvent fluorescent intensity decreases. They show green fluorescence in weak acidic medium such as acetic acid but lack emission in basic medium. The compounds can also stain human squamous epithelium cells.     

Synthesis of alkylated methylene bisphosphonates via organothallium intermediates

Thallium(I) derivatives of esterified methylene bisphosphonates can be readily obtained by treating the latter with thallium(I) ethoxide under anhydrous conditions. Alkylation of the thallium(I) derivatives by a range of primary alkyl iodides takes place smoothly, and significantly higher yields are obtained than for the corresponding reactions with lithio or sodio derivatives.     

Preparation and properties of alkylated poly(styrene-graft-ethylene oxide)

Poly(styrene-graft-ethylene oxide), having alkyl chains (C₁₂ or C₁₈) on the polystyrene main chain or on the poly(ethylene oxide) (PEO) side chains, were synthesized. The main chain was alkylated by first ionizing amide groups in a styrene/acrylamide copolymer with tert-butoxide, and then using the amide anions as sites for reactions with 1-bromoalkanes. An excess of amide anions was used in the reaction, and the remaining anions were subsequently utilized as initiator sites for the anionic polymerization of ethylene oxide (EO). Synthesis of poly(styrene-graft-ethylene oxide) with alkylated side chains was accomplished by polymerization of EO onto the ionized styrene/acrylamide copolymer, followed by an alkylation of the terminal alkoxide anions with 1-bromoalkanes. The alkylated graft copolymers were structurally characterized by using elemental analysis, ¹H NMR, GPC, and IR spectroscopy. DSC analysis showed that only graft copolymers with PEO contents exceeding about 50 wt % and side chain crystallinities comparable to those of homo-PEO. Main chain alkylated graft copolymers generally had higher crystalinities, as compared to nonalkylated and side chain alkylated samples. The graft copolymers absorbed water corresponding to one water molecule per EO unit at low PEO contents. The water absorption increased progressively at PEO contents above 30 wt % for main chain alkylated samples and above 50 wt % for non-alkylated samples. © 1995 John Wiley & Sons, Inc.     

Synthesis of fused bicyclic imidazoles by ring-closing metathesis

The preparation of a number of dienylimidazole via chemoselective metal-halogen exchange and their utility in ring-closing metathesis is described. Essentially all regioisomeric permutations participate in metathesis with the notable exception of 4-vinyl-5-allylimidazoles, provided that the imidazole N3 atom is protonated.     

Synthesis on templates : Regiospecific synthesis of imidazoles

A new, biomimetic template operated strategy has been developed leading to regiospecific synthesis of imidazoles (CHARTS I & II).     

Synthesis of new polyaryl-substituted imidazoles bridged on enamine or urea moieties and evaluation of their optical and electrochemical properties

Research on Chemical Intermediates - The reaction of the free amine group in polyaryl-substituted imidazole structures with phenyl isocyanate or dimethyl acetylenedicarboxylate gave two new series...     

Synthesis of alkylated aminofluorenes by palladium-catalyzed substitution at halofluorenes

New N-substituted 2-amino-9,9-dialkylfluorenes optionally bearing electron-withdrawing substituents such as nitro or cyano in position 7 can be synthesized starting from 2-halo-9,9-dialkylfluorenes by Pd-catalyzed substitution with amines. Chiral amino groups can be introduced by this method too. 2-N,N-Dimethylamino-7-nitro-9H-fluorene was obtained in a convenient way by reductive amination. The N-substituted 2-amino-7-nitro-9H-fluorenes are promising candidates for fluorescence probes for femtosecond solvation dynamics.