Theoretical study of anion carriers based on trifluoroacetophenone

Model calculations on anion carrier ligands related to trifluoroacetophenone were carried out using the semiempirical AM 1 method in order to investigate the factors involved in such anion-ligand complexation. The reaction of halogen derivatives of acetophenone with various nucleophiles such as water, carbonic acid, and bicarbonate anion was studied. By this means, the effect of various structural changes, such as variation of the ring substituents and variation of the degree and type of halogen atom substitution, could be determined. It is shown that in terms of relative stability, fluorine derivatives are preferable to chlorine derivatives for the binding of water and carbonic acid. Monosubstitution of a methoxy group in the ortho position of the trifluoroacetophenone ring also brought about stability in the case of the hydration reaction. An electron-withdrawing ester group in the para position on the trifluoroacetophenone ring brings about stabilization also.     

Aluminum(III) complexes containing O,O chelating ligand

The stoichiometric reactions of trimethylaluminum with 2,6‐(MeOCH₂)₂C₆H₃OH (LH) revealed compounds L₃Al ( 1 ) and L₂AlMe ( 2 ). On the other hand reaction of 1 equiv. of LH with trimethylaluminum did not lead to the formation of complex LAlMe₂ ( 3 ), rather 2 together with Me₃Al were observed as a result of a disproportionation of 3 . Compounds 1 and 2 were characterized by elemental analysis, ¹H and ¹³C NMR spectroscopy and in the case of 1 by X‐ray diffraction. Derivative 2 underwent transmetalation with Ph₃SnOH, giving LSnPh₃ ( 4 ) as the result of a migration of ligand L from the aluminum to the tin atom. The identity of 4 was established by elemental analysis, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy and ¹H, ¹¹⁹Sn HMBC experiments. The system 2 and B(C₆F₅)₃ in a 1:1 molar ratio was shown to be active in the polymerization of propylene oxide and ε‐caprolactone. Copyright © 2007 John Wiley & Sons, Ltd.     

N-烷基化手性氨基醇配体的合成

本实验制备了不同构型的两种N-单烷基和N-双烷基的新的手性氨醇配体。     

ESR study of products of transformation of 3,6-tert-butylpyrocatechol on alumina, zinca, silica, and titania

The formation of semiquinone and phenoxazyl radicals and metallocomplexes with semiquinone ligands was observed by ESR during the interaction of di-tert-butylpyrocatechol with Al₂O₃, ZnO, SiO₂, and TiO₂. In the case of different modifications of SiO₂, admixtures of TiO₂ exhibit a higher reactivity in complex formation with the organic substrate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1975–1978, October, 1998.     

Triorganotin 4-isopropylbenzoates as model transesterification catalysts for triorganotin carboxylates grafted to cross-linked polystyrene

Starting from 4-isopropylbenzoic acid, three new triorganotin carboxylates bearing methyl, butyl and phenyl substituents at tin, respectively, were prepared and fully characterized by spectroscopic and thermal techniques, with particular regard to the coordination number of tin atom, in solution as well as in the solid state. The triorganotin compounds, tested as transesterification catalysts in the reaction between ethyl acetate and primary, secondary or tertiary alcohol, respectively, displayed, as expected, a strong decrease of activity on passing from the primary to the tertiary alcohol reactant. Different activities by the tin carboxylates were also observed in the reaction between primary alcohol and ethyl acetate. The reaction mechanism, as elucidated by Sn NMR, involves coordination of both ester substrate and alcohol reactant to the triorganotin compound, the reaction conversion appearing related not only to the Lewis acidity of the tin atom, but also to the nature of the reactants. Preliminary catalytic tests were also carried out in the reaction between glyceryl tridodecanoate (as a model of natural triglyceride) and ethanol, mimicking the preparation of biodiesel fuel. Although in this case lower conversions were obtained with respect to the reactions on ethyl acetate, the catalytic activity of organotin derivatives appears considerable.     

Chiral diphosphine ligands based on camphor: synthesis and applications in asymmetric hydrogenations

The synthesis of a novel class of atropisomer chiral diphosphine ligands with a bornene framework is described. The new ligands showed in Rh catalyzed asymmetric hydrogenation of α- and β-enamides very high ee’s (more than 99%).