RESUMEN
We explored the optoelectronic and vibrational properties of a new class of halogen-terminated carbon atomic wires in the form of polyynes using UV-vis, infrared absorption, Raman spectroscopy, X-ray single-crystal diffraction, and DFT calculations. These polyynes terminate on one side with a cyanophenyl group and on the other side, with a halogen atom X (X = Cl, Br, I). We focus on the effect of different halogen terminations and increasing lengths (i.e., 4, 6, and 8 sp-carbon atoms) on the π-electron conjugation and the electronic structure of these systems. The variation in the sp-carbon chain length is more effective in tuning these features than changing the halogen end group, which instead leads to a variety of solid-state architectures. Shifts between the vibrational frequencies of samples in crystalline powders and in solution reflect intermolecular interactions. In particular, the presence of head-to-tail dimers in the crystals is responsible for the modulation of the charge density associated with the π-electron system, and this phenomenon is particularly important when strong I··· N halogen bonds occur.
RESUMEN
A method of palladium-catalyzed C-H arylation assisted with a 3,4,4-trimethylpyrazol-5-on directing group, selectively providing mono- and di-ortho-arylated products is reported. Steric hindrance appearing between the directing group and the already introduced aryl substituent enables control of mono- vs. diarylation selectivity by the temperature of the reaction. Taking advantage of this, a series of monosubstituted and disubstituted derivatives were obtained in good yields. Moreover, unsymmetrical double-arylation in a one-pot procedure was developed to give corresponding products in reasonable yields. Additionally, synthesis and X-ray study of intermediate palladium metallacycles of both, the first and second arylation reactions, were conducted. X-ray structure comparison emphasizes the geometrical differences that were consistent with the observed reactivity. Finally, decarboxylative cleavage of the pyrazolone directing group under mild conditions gave synthetically useful hydrazones. The presented solution opens the alternative synthetic way to such ortho arylated derivatives of arylhydrazines.
Asunto(s)
Paladio , Paladio/química , Catálisis , TemperaturaRESUMEN
Despite a large number of synthesis procedures for pyrazoles known today, those directly employing primary amines as substrates are rare. Herein, we report an original method for the preparation of N-alkyl and N-aryl pyrazoles from primary aliphatic or aromatic amines as a limiting reagent of the reaction. The protocol utilizes no inorganic reagents and requires a short reaction time, mild conditions, and the use of structurally simple and commercially available starting reagents. During this study, pyrazoles containing a wide variety of N-substituents were obtained using the same procedure for both aliphatic and aromatic amines.
Asunto(s)
Aminas , Pirazoles , Catálisis , Indicadores y ReactivosRESUMEN
The electron density of p-CH3CH2COC6H4-C≡CC≡C-p-C6H4COCH3CH2 has been investigated on the basis of single-crystal X-ray diffraction data collected to high resolution at 100 K and from theoretical calculations. An analysis of the X-ray data of the diyne showed interesting "liquidity" of electron distribution along the carbon chain compared to 1,2-diphenylacetylene. These findings are compatible with the results of topological analysis of Electron Localization Function (ELF), which has also revealed a larger (than expected) concentration of the electron density at the single bonds. Both methods indicate a clear π-type or "banana" character of a single bond and a significant distortion from the typical conjugated structure of the bonding in the diyne with a small contribution of cumulenic structures.
Asunto(s)
Alquinos/química , Modelos Moleculares , Cristalografía por Rayos X , Enlace de Hidrógeno , Difracción de Rayos XRESUMEN
3,5-Dimethylpyrazole was employed as a monodentate directing group for palladium-catalyzed ortho-sp2 C-H arylation with aryl iodides. The reaction shows good functional group tolerance and outstanding selectivity for mono- ortho-arylation. Ozonolysis of ortho-arylated arylpyrazoles gave acylated biphenylamines that were further arylated to afford unsymmetrically substituted 2,6-diarylacetanilides.
Asunto(s)
Compuestos de Anilina/síntesis química , Compuestos Organometálicos/química , Paladio/química , Compuestos de Anilina/química , Catálisis , Estructura Molecular , Ozono/químicaRESUMEN
We have developed a method for palladium-catalyzed, pyrazole-directed sp3 C-H bond arylation by aryl iodides. The reaction employs a Pd(OAc)2 catalyst at 5-10â mol % loading and silver(I) oxide as a halide-removal agent, and it proceeds in acetic acid or acetic acid/hexafluoroisopropanol solvent. Ozonolysis of the pyrazole moiety affords pharmaceutically important ß-phenethylamines.
Asunto(s)
Paladio/química , Fenetilaminas/síntesis química , Pirazoles/química , Catálisis , Yoduros/síntesis química , Yoduros/química , Óxidos/química , Fenetilaminas/química , Pirazoles/síntesis química , Compuestos de Plata/químicaRESUMEN
The synthesis of a unique series of long, asymmetric 1-iodopolyynes (1-Cn I and 2-Cn I) with the sp-hybridized carbon chain up to a decapentayne is reported. These compounds were then used as substrates in reactions with Pd(PPh3 )4 leading to another series of palladium end-capped polyynes, which were unstable in solution. Organometallic octatetraynes 1-C8 [Pd]I, 2-C8 [Pd]I, and decapentayne 1-C10 [Pd]I are palladium end-capped polyyne compounds with the longest carbon chains reported so far. All the complexes as well as their organic precursors were fully characterized by NMR, HRMS(ESI), IR, TGA-DTA, and UV/Vis techniques, and the X-ray crystal structures of two silyl-protected precursors and one palladium complex are presented. The synthetic approach for palladium species is envisioned as a general route for the synthesis of labile organometallic polyynes.
RESUMEN
A highly efficient one-pot procedure for the preparation of 1-chloroalkynes and 1-chlorobutadiynes from terminal and trialkylsilyl-protected precursors is reported. This convenient reaction, proceeding under mild conditions, utilizes N-chlorosuccinimide as the chlorinating agent and tolerates a range of functional groups.
Asunto(s)
Alquinos/síntesis química , Cloro/química , Succinimidas/síntesis química , Compuestos de Trimetilsililo/síntesis química , Alquinos/química , Halogenación , Estructura Molecular , Succinimidas/química , Compuestos de Trimetilsililo/químicaRESUMEN
OBJECTIVES: To assess the cytotoxicity of an experimental hybrid-glass-based infiltrant and its effect on biofilm attachment, growth and metabolic activity, and to compare it to the resin-based infiltrant Icon. METHODS: Cytotoxicity of hybrid-glass-based material (EXP) and resin-based infiltrant Icon (Icon) was tested in direct contact tests on freshly cured (direct_mat) and on materials kept for 24 h in cell culture medium (direct_exmat), and extract test with materials 24-h extracts (extract). Cell viability of L929 mouse fibroblast cell line was measured with MTT assay, according to ISO10993-5:2009. Biofilm attachment (5 h), growth (24 h and 48 h) and lactic-acid production (24 h and 48 h) on glass-disk specimens coated with EXP or Icon, or uncoated (control), were assessed using a microcosm biofilm model and Amsterdam Active Attachment system. At indicated time points, biofilms were harvested, plated, and CFU counts were determined, while lactic-acid production was measured colorimetrically. RESULTS: Cell viability reduction by EXP was below 30%-threshold in direct contact tests, while in extract test an increased cell viability was observed. Icon reduced cell viability substantially in all three tests. Significantly less bacteria attached to the surface of EXP after 5 h compared to Icon and control. Biofilm growth was significantly lower on EXP than on Icon and control after 24 h, but this difference was smaller and statistically insignificant after 48 h. There was no difference in lactic-acid production among groups. SIGNIFICANCE: Novel hybrid-glass-based infiltrant seems to have a better biocompatibility and accumulates on its surface less bacteria than resin-based infiltrant, which makes it an attractive resin-free alternative.
Asunto(s)
Susceptibilidad a Caries Dentarias , Caries Dental , Animales , Ratones , Biopelículas , Vidrio , Ácido LácticoRESUMEN
OBJECTIVES: To assess the effectiveness of two experimental, hybrid-glass-based infiltrants in arresting artificial white spot lesions (WSLs) in vitro, and to compare it with resin-based infiltrant Icon. METHODS: Artificial WSLs were formed on bovine enamel specimens (n = 68). Specimens were divided into four groups according to WSLs treatment: 1) no-treatment control (NTC), 2) infiltration with Icon (Icon), 3) infiltration with experimental hybrid-glass material (EXP), and 4) infiltration with experimental hybrid-glass material containing hydroxyapatite (HAp) nanoparticles (1%) (EXP-HAp). Half of the specimens from each group were subjected to cariogenic challenge using pH-cycling, consisting of a 7-day alternate incubation (37°C) in demineralization (4 h/day, pH=4.6) and remineralization solutions (20 h/day, pH=7.2). Another half of the specimens was incubated in distilled water (control). Caries progression was assessed by measuring surface micro-hardness (SMH), roughness (Ra) and average surface level, and by analyzing WSLs morphology. Non-cycled and pH-cycled specimens were compared with Man-Whitney U test, while different treatment groups were compared with Kruskal-Wallis test with pairwise comparisons (p < 0.05). RESULTS: In all groups (NTC, Icon and EXP-HAp) except EXP, SMH decreased significantly after pH cycling. In addition, SMH increased in EXP upon pH cycling and was significantly higher than in other pH-cycled groups (<0.001). Ra increased considerably, while surface level decreased after pH cycling in all groups except in EXP. Signs of demineralization and roughness increase in NTC, Icon and EXP-HAp were also observed with the SEM. SIGNIFICANCE: Experimental hybrid-glass-based material without HAp-nanoparticles could completely arrest the progression of WSLs, unlike its version with HAp-nanoparticles and resin-based infiltrant Icon.
Asunto(s)
Susceptibilidad a Caries Dentarias , Caries Dental , Animales , Bovinos , Caries Dental/patología , Caries Dental/terapia , Esmalte Dental/patología , Durapatita , Dureza , Humanos , Resinas SintéticasRESUMEN
The reaction of MgBu2, ZnEt2 or Ca(O(i)Pr)2 with 2 eq. of three-coordinating N-[methyl(2-hydroxy-3,5-dimethylphenyl)]-N-methyl-N-methyl-1,3-oxolaneamine (mpoa-H) or N-[methyl(2-hydroxy-3,5-di-tert-butylphenyl)]-N-methyl-N-methyl-1,3-oxolaneamine (tbpoa-H) gave neutral, monomeric [Mg(mpoa)2], [Zn(mpoa)2], [Zn(tbpoa)2], and [Ca(tbpoa)2] as white powders in 58-90% yields. The resulting aminophenolates were characterized in solution by NMR showing, in the case of [Zn(tbpoa)2], interesting dynamics. [Zn(tbpoa)2] and [Ca(tbpoa)2] were characterized by X-ray crystallography to show the Zn atom to be pseudo-octahedrally coordinated and the Ca atom in six-coordination mode. The new homoleptic complexes were tested in the polymerization of lactide with an external alcohol to reveal stable behaviour (during the polymerization process) only in the case of [Zn(tbpoa)2]. The high activity of the catalyst was correlated with a ligand flexibility that was further supported by theoretical studies.