Search results for "Ethyl group"
showing 10 items of 66 documents
Alkoxo, chlorido, and methyl derivatives of oxidomolybdenum(VI) complexes with tetradentate [O3N]-type ligands
2007
Dioxomolybdenum(VI) complex [MoO 2 (Heg) 2 ] (H 2 eg = 1,2-ethanediol) reacts with phenolic ligand precursors tris(2-hydroxy-3,5-dimethylbenzyl)amine (H 3 L Me ) and tris(2-hydroxy-3,5-di- tert -butylbenzyl)amine (H 3 L t Bu ) to form oxomolybdenum(VI) complexes of type [MoO(L R ) (Heg)]. The Heg ligand can be replaced by other alcohols (i.e. 2-aminoethanol, 2-amino-2-methylpropan-1-ol, 2-(dimethylamino)ethanol or allyl alcohol) in the reaction at refluxing toluene or at neat alcohol. Treatment of [MoO(L R )(Heg)] with Me 3 SiCl yields corresponding chlorido complexes [MoO(L R )Cl]. These are also formed in the reaction of H 3 L R with [MoO 2 Cl 2 (dmf) 2 ]. The reaction of [MoO(L R )Cl] wi…
Proton Acid-Catalysed Transformations of Estrogen Derivatives: New Results and Some Mechanistic Aspects of theKober Colour Reaction
1994
The 3-O-methylated estrogen derivatives 1a-d and α-estradiol (1e) underwent sulfuric acid-catalysed transformations to furnish the steroids 2–6. The processes involved in the reaction sequence are regioselective sulfonation and, above all, the Wagner-Meerwein rearrangement of the methyl group at C-13. With the objective of obtaining further information on the course of the Kober colour reaction of estrogens, some UV/VIS and ESR spectroscopic investigations were also carried out. Protonenkatalysierte Transformationen von Estrogen-Derivaten: Neue Ergebnisse und einige mechanistische Aspekte der Kober-Farbreaktion Die O-methylierten Estrogenderivate 1a-d und α-Estradiol (1e) reagieren in Schwe…
1-methil-3H-pyrazolo[1-2-a]benzo[1-2-3-4]tetrazin-3-ones, design synthesis and biological activity of new antitumoral agents
2005
1-Methylpyrazolo[1,2-a]benzo[1,2,3,4]tetrazin-3-ones 4, synthesized in good to excellent yields, were designed as novel alkylating agents because of their peculiar chemical behavior. All derivatives showed antiproliferative activity against more than 50 types of tumor cell lines with GI50 reaching sub-micromolar values. SAR studies revealed that the presence of a chlorine atom is well-tolerated in both positions 8 and 9, whereas in the case of the methyl group, switching from the 8 to the 9 position gives rise to the most active compound of the series, 4g, either for the number of cell lines inhibited and for selectivity against leukaemia and renal cancer subpanels. COMPARE and 3D-MIND comp…
Molecular structures and vibrations of m-methylaniline in the S0 and S1 states studied by laser induced fluorescence spectroscopy and ab initio calcu…
2000
Abstract The UV fluorescence excitation and dispersed fluorescence spectra of a jet-cooled m-methylaniline have been obtained for the S1←S0 transition, in which some of the bands have been observed for the first time. The main spectral bands have been assigned by comparison with those of other relevant substituted benzenes. It was found that the spectra exhibit an important feature which is the internal rotation of the methyl group in the electronic ground and excited states. Ab initio calculations at MP2/6-31G* and CIS/6-31G* show that the optimized structure of m-methylaniline in the ground state is not planar with the amino group having sp3 hybridation-like character due to the existence…
ortho-Metalation of aromatic ethers by yttrium alkyl complexes that contain a linked amido-cyclopentadienyl ligand
2003
Abstract The reaction of the half-sandwich alkyl complex [Y(η5:η1-C5Me4CH2SiMe2NtBu)(CH2SiMe3)(THF)] (1) with anisole smoothly gives the ortho-metalation product [Y(η5:η1-C5Me4CH2SiMe2NtBu)(2-C6H4OMe)(THF)] (2). 3- and 4-Methylanisole as well as phenetole analogously undergo ortho-metalation, whereas thioanisole, N,N′-dimethylaniline, fluorobenzene, and trifluorobenzene do not react with yttrium complex 1. 2-Methylanisole reacts with 1 under activation of the ring methyl group to give the 2-methoxybenzyl complex [Y(η5:η1-C5Me4CH2SiMe2NtBu)(CH2C6H4OMe-2)(THF)] (6). A single-crystal X-ray structure analysis of the 2-anisyl complex 2 revealed a four-legged piano-stool configuration with the me…
FT-IR and nuclear overhauser enhancement study of the state of urea confined in AOT-reversed micelles
2003
Abstract The system urea/sodium-bis(2-ethylhexyl)sulfosuccinate (AOT) dispersed in CCl 4 and benzene-d6 was investigated by viscosimetry, FT-IR and high-resolution 1 H NMR spectroscopy, as a function of urea/AOT molar ratio ( R urea ) at fixed AOT molal concentration (0.3467 mol kg −1 ) and as a function of AOT concentration at fixed R urea (0.5) at 25 °C. The experimental data are consistent with the hypothesis that urea is encapsulated as small-size hydrogen-bonded cluster in the hydrophilic micellar core of the AOT-reversed micelles and that this structure is maintained well above the volume fraction of the dispersed phase, where a percolative transition occurs. Intermolecular nuclear ov…
Alcoholysis of Aluminum Alkyls Supported by Bulky Phenoxide Ligands: Synthesis, Characterization, and ε-Caprolactone Polymerization Activity of Two D…
2000
Reaction of trialkylaluminum Al2R6 (R = Me, Et) with 2,2′-methylenebis(6-tert-butyl-4-methylphenol) (mbmpH2) gives the dimeric mono(alkyl) complex [Al(mbmp)R]2 with bridging oxygen atoms. Reaction of [Al(mbmp)R]2 with one equiv. of 2-propanol results in the formation of the dimeric isopropoxide [Al(mbmp)(μ-OiPr)]2. Single-crystal X-ray analysis shows a C2h-symmetric structure with a planar Al2O2 core. Monomeric methylbis(2,6-di-tert-butyl-4-methylphenolato)aluminum, AlMe(OC6H2-2,6-tBu2-4-Me)2 (MAD), was found to react with one equiv. of 2-propanol to give a dimeric isopropoxide [AlMe(OC6H2-2,6-tBu2-4-Me)(μ-OiPr)]2 in which the bulky phenolate, instead of the methyl group, has been displaced…
Kristallisation und schmelzverhalten von fraktionen verzweigten polyethylens, 1. Darstellung und charakterisierung der fraktionen
1983
A branched polyethylene with broad molecular weight distribution was separated into a series of fractions by fractional precipitation from dilute solution. The fractions were characterized by viscometric and density measurements, IR-spectroscopy and calorimetry. The methyl group content and the density turned out as largely constant. Molecular weight effects show up in the melting behaviour. The main range of melting and the end of the melting curve shift to lower temperatures with decreasing molecular weight. Compared to the overall extension of the melting range these shifts are small. One has to conclude that polydispersity gives only a minor contribution to the broadening of the melting…
Quantum-chemistry calculations of surface complex and orbital control in para/ortho toluene alkylation catalyzed by big pore zeolites
1994
Summary By means of MNDO-PM3 semiempirical quantum-chemistry calculations, the mechanism for alkylation of toluene by methanol on two zeolite clusters with Al and Ga as T III has been studied. The process variables controlled through the hypersurface of the reaction were: the distances of methyl group to the cluster of zeolite and to the toluene molecule; and the distances of the hydrogen atom of the toluene to be transfered to the zeolite cluster and to the toluene. The energetic factor associated with the electronic interaction between the molecular orbitals (LUMO of the zeolite-methoxy and HOMO of toluene) have been calculated by a PMO analysis for two geometries: the transition state an…
Effect of structural parameters on the polarizabilities of methanol clusters: a hirshfeld study
2008
The polarizabilities of fifty methanol clusters (CH3OH)n, n = 1 to 12, were calculated at the B3LYP/6-311++G** level of theory and partitioned into molecular contributions using the Hirshfeld-I method. The resulting molecular polarizabilities were found to be determined by the polarizabilities of the two parts of the molecule, the hydrophilic hydroxyl group and the hydrophobic methyl group, each exhibiting a different dependency upon the local environment. The polarizability of the hydroxyl group was found to be dependent on the number, type, and strength of the hydrogen bonds a methanol molecule makes, whereas the polarizability of the methyl groups is mostly influenced by sterical hindran…