Synthesis of polysiltrimethylenes with trimethylsilyl groups in the branch of the main chain

The thermally initiated and platinum-catalyzed polymerization of 1-silacyclobutanes with substitutents containing a trimethylsilyl group was carried out. Soluble, high-molecular-weight, heterochain siltrimethylene polymers were obtained, containing trimethylsilyl groups removed from the main chain by various bridges.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 223–225, January, 1992.     

Darstellung und Molekülstrukturen von oligofunktionalen Dirheniumcarbonylderivaten aus Dirheniumnonacarbonylphosphan

Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re₂(CO)₉NCCH₃ was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re₂(CO)₉PH₃, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re₂(CO)₉PH₃ led to the new bi- and trinuclear complexes Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈, Re₂(μ-PH₂)₂(CO)₈ and Re₂(μ-H) · (μ-PH₂)(CO)₈, which were characterized by IR-, ¹H- and ³¹P-NMR spectroscopy. The structures of ax-Re₂(CO)₉PH₃, Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈ and Re₂(μ-PH₂)₂(CO)₈ were confirmed by single-crystal X-ray analysis. ax-Re₂(CO)₉PH₃ has a very short Re? P bond length of 228(2) pm.     

Use of Silicon Substituents in the Syntheses of Natural and Non-natural Molecules

Trimethylsilyl groups have been used in our research as a director as well as a bulky and lipophilic group in our quest for natural and non-natural molecules.     

The use of Nafion-H® as an efficient catalyst for the direct conversion of primary and secondary trimethylsilyl ethers to their corresponding ethers under mild and heterogeneous conditions

Primary and secondary trimethylsilyl ethers were converted to their corresponding ethers in the presence Nafion-H® with good to excellent yields under mild and heterogeneous conditions.     

Bis(trimethylsilyl)diimine: Preparation,Structure, and Reactivity

The highly reactive compound bis(trimethylsilyl)diimine (BSD), which was first prepared by oxidation of lithium tris(trimethylsilyl)hydrazide, is light blue, sensitive to thermolysis and hydrolysis, and ignites spontaneously in air. On the basis of electron transfer, acid-base, or free-radical reactions, it acts in particular as a (preparatively useful) redox system and as an agent for the introduction of azo groups. Redox reactions lead by oxidation or reduction of the other reactant through two oxidation stages to hydrazine derivatives or molecular nitrogen, and in the case of electrochemical reduction, to BSD radical-anions. Azo-group transfers, on the other hand, yield new inorganic azo compounds with no change in the oxidation state of the diimine group.     

Carbofunctional silacyclobutanes

A four-step synthesis of 1-(-ydroxyalkyl)- and 1-(4-hydroxyphenyl)silacyclobutanes was carried out. The influence of the structure of the initial compounds and the reaction conditions on the ratio of the reaction products formed was studied. The stability of the silacyclobutane alcohols and the hydrolysis of their trimethylsilyl ethers were investigated.For preliminary communication, see Ref. 6.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 946–954, April, 1996.     

Silyl stabilized azanes: reactions of lithiumbis(trimethylsilyl)hydrazine with trialkyltin halides

Lithium 1,2-bis(trimethylsilyl)hydrazine (1a) reacts with Me₃SnCl, Et₃SnBr and Bu₃SnCl to form bis(trimethylsilyl)(trimethylstannyl)hydrazine (2a), (triethylstannyl)bis(trimethyl silyl)hydrazine (2b) and (tributylstannyl)bis(trimethylsilyl)hydrazine (2c), respectively. Compounds 2a and 2b undergo disproportionation at room temperature to form bis(trimethylsilyl)bis(trimethylstannyl)hydrazine (3a) and bis(triethylstannyl)bis(trimethylsilyl)hydrazine (3b). In contrast, 2c is highly stable and can withstand such a reaction up to 150 °C. The monostannylated products, 2a, 2b and 2c do not get lithiated at NH and instead undergo transmetallation in their reaction with RLi or Li to form lithiumbis(trimethylsilyl)hydrazine (1a).     

Synthesis of the fungal natural product (−)-xylariamide A

The first synthesis of the fungal natural product (−)-xylariamide A 1 is reported. N,O-Bis(trimethylsilyl)acetamide induced coupling of d-tyrosine with (E)-but-2-enedioic acid 2,5-dioxo-pyrrolidin-1-yl ester methyl ester 5 produced the dechloro natural product 6, which was subsequently monochlorinated using oxone and KCl to yield synthetic 1. (−)-Xylariamide A 1, (+)-xylariamide A 2 and (−)-dechloroxylariamide A 6 displayed no cytotoxic or antimicrobial activity.     

XPS STUDIES ON SURFACE MODIFIED POLY [1-(TRIMETHYLSILYL)-1-PROPYNE] MEMBRANES Ⅱ SURFACE MODIFICATION BY BROMINE VAPOR*

Surface modification of poly [1-(trimethylsilyl)-1-propyne] (PTMSP) membranes bybromine vapor has been studied. It is shown that Br/C atomic ratio at the surfaces increased withthe time of bromination until about 60 min, then it reached a plateau. The results of XPS and IRstudies indicated that the addition of bromine to double bonds and the replacement of H on CH_3 bybromine had taken place so that a new peak at 286.0 eV (C--Br)in C_(1s) spectra and some newbands, e. g. at 1220 and 580cm~(-1) in IR spectra were formed. The fact,t Po_2, permeability ofoxygen, decreased and α_(O_2/N_2), separation factor of oxygen relative to nitrogen, increased withbromination time, shows that surface modification of PTMSP by bromine may be an efficient approach to prepare PTMSP membranes used for practical gas separations.