Consecutive reactions of diethoxydimethylsilane and triethoxymethylsilane with methoxide ions in methanol solution

The consecutive reactions of (CH₃)₂Si(OC₂H₅)₂ and CH₃Si(OC₂H₅)₃ with methoxide ions were investigated in methanol solutions. The reverse transesterification reactions with ethoxide ions could be neglected in both cases since the concentration of ethoxide in methanol solution was assumed to be low due to the fast equilibrium reaction C₂H₅O^? + CH₃OH ? C₂H₅OH + CH₃O^?. The progress of the reactions was followed by monitoring the formation of ethanol with a Fourier-transform infrared spectrometer. All rate constants were determined at 295 K. The reactions between the dialkoxydimethylsilanes and methoxide ions were assumed to consist of two consecutive steps that can be represented by the net reaction; (CH₃)₂Si(OC₂H₅)₂ + 2CH₃O^? → (CH₃)₂Si(OCH₃)₂ + 2C₂H₅O^?. The two consecutive rate constants were established as 1.93 ± 0.12M^?1s^?1 and 1.00 ± 0.12M^?1s^?1, respectively. The consecutive rate constants for the reactions between the trialkoxymethylsilanes and methoxide ions can be written according to the total reaction; CH₃Si(OC₂H₅)₃ + 3CH₃O^? → CH₃Si(OCH₃)₃ + 3C₂H₅O^?. The three rate constants corresponding to each consecutive step were established as 1.12 ± 0.09 M^?1s^?1, 0.82 ± 0.10 M^?1s^?1, and 0.51 ± 0.06 M^?1s^?1, respectively. © 1995 John Wiley & Sons, Inc.     

Diels-Alder-Reaktionen von Vinylindolen mit Arin und 1,4-Benzochinonen: Neue potentielle DNA-Interkalatoren

Summary Diels-Alder reactions of 2- and 3-vinylindoles with aryne, 1,4-benzo- and 1,4-naphtho-quinone lead to new six-ring annellated carbazoles. Molecular modeling studies predict that the compounds with coplanar framework are able to intercalate with the B-DNA.

     

Multicenter ligand transformations of thioureas on ruthenium clusters

The reaction of trirutheniumdodecacarbonyl with various thioureas was found to give, depending upon the substituents and the reaction conditions, a large variety of tri-, tetra-, penta-, and hexanuclear ruthenium clusters. The ligand systems observed in the products are derived from the thioureas employed; the fragmentation of the thiourea molecules involve N-H, C-S, C-H, and C-N activation processes.     

Chain “stationary” insertion mechanism and production of isotactic polypropylene with C 1 symmetric catalyst systems

In this contribution, the stereochemistry of propylene insertion/propagation reactions with a variety of C ₁ symmetric metallocene catalysts, containing bridged cyclopentadienyl-fluorenyl ligand for the preparation of highly stereoregular polypropylene is presented. The impact of the distal substitutent’s size and composition and changes that the catalytic sites undergo upon such substitution is elaborated. A comprehensive mechanism is proposed to explain the resulting catalytic changes that bring about the irreversible C _s/C ₁ site transformation and tactic behavior inversion. Furthermore the cyclopentadienyl’s combined distal/proximal and fluorenyl’s frontal substituent effects on molecular weight, regio-, and stereoregularity of the final polymers are discussed. Finally, stereoselectivities of C ₂ and C ₁ symmetric catalyst systems are compared. It is shown that current high performance C ₁ symmetric catalyst systems with central site chirality can be isotactic selective as well or even better in certain aspects than the C ₂ symmetric bridged bisindenyl-based metallocene catalysts. The text was submitted by the authors in English.     

The first encapsulation of hydroxynitrile lyase from Hevea brasiliensis in a sol-gel matrix

A straightforward process for the encapsulation of HbHNL under low methanol conditions has been developed. By adding a sol, prepared by hydrolysis of TMOS/MTMS at pH 2.8 with continuous removal of methanol, to a stirred solution of the enzyme in a buffer at pH 6.5, at least 65% of the activity of the free enzyme could be recovered after the encapsulation. The aquagels were successfully used in the synthesis of (S)-cyanohydrins.