Search results for "Silylation"
showing 10 items of 97 documents
Dimesogenic ferroelectric polysiloxanes
1994
Dimesogenic polysiloxane [Si(Me) 2 O] m [Si(Me)(R)O] n (R= (CH 2 ) 3 CH(COO[CH 2 ] 11 OPhPhOCOPh(NO 2 )OC * H(Me)C 6 H 13 ) 2 are synthesized by hydrosilylation. The phase transition temperaturs are determined and the ferroelectric properties are investigated
Identification of indigoid compounds present in archaeological Maya blue by pyrolysis-silylation-gas chromatography–mass spectrometry
2014
Abstract A study based on the use of pyrolysis-silylation-gas chromatograpy–mass spectrometry (Py-GC–MS), which aimed to identify indigoid compounds and to clarify the multicomponent composition of Maya blue (MB) pigment, has been carried out. A series of reference compounds and synthetic MB specimens prepared in the laboratory have been analysed by this technique. An analysis of archaeological MB samples from 14 Maya archaeological sites from Mexico and Guatemala has also been performed. The obtained results demonstrate that, in addition to indigo, oxidised species such as dehydroindigo, which is formed as a result of redox processes taking place while preparing the pigment, are present in…
Amphiphilic Linear-Hyperbranched Block Copolymers with Linear Poly(ethylene oxide) and Hyperbranched Poly(carbosilane) Block
2008
The synthesis of amphiphilic linear-hyperbranched block copolymers with a linear poly(ethylene oxide) (PEO) segment and a hyperbranched poly(carbosilane)s (PCS) block in a rapid three-step strategy is described, combining oxyanionic polymerization with carbosilane chemistry. A linear precursor block copolymer was synthesized via anionic polymerization of allyl glycidyl ether onto a commercial hydroxyl-terminated PEO, using its cesium alkoxide as macro-initiator. The resulting linear AB or ABA-type di- or triblock copolymers serve as polymer cores for the subsequent hydrosilylation polyaddition of an AB2-type carbosilane monomer. Di(allyl)methylsilane or methyldi(undec-10-enylsilane) were em…
Modular Construction of Neutral and Anionic Carboranyl-Containing Carbosilane-Based Dendrimers
2007
A modular construction of new carbosilane dendrimers, which contain four and eight peripheral carborane derivatives and propyl linkages between the C cluster and the Si atoms, has been developed using different methodologies. Regiospecific hydrosilylation of 1-C 6 H 5 -2-(CH 2 CH=CH 2 )-1,2-closo-C 2 B 10 H 10 (1) and 1-CH 3 -2-(CH 2 CH=CH 2 )-1,2-closo-C 2 B 10 H 10 (2) offers an efficient route to molecular precursors and building blocks that can provide both divergent and convergent strategies for dendritic growth. First generations of neutral carboranyl-containing dendrimers were constructed by two approaches: (a) a divergent approach via hydrosilylation of 1 and 2 with the first genera…
Rotational spectra of isotopic species of silyl fluoride. Part I: Lamb-dip measurements and quantum-chemical calculations
2010
The Lamb-dip technique has been employed for recording the rotational spectra of three isotopic species of silyl fluoride, namely (28)SiH3F, (29)SiH3F, and (30)SiH3F, in order to improve the knowledge of their spectro- scopic parameters as well as to try to resolve their hyperfine structure. High-level quantum-chemical computations using state-of-the-art coupled-cluster techniques together with core-polarized correla- tion-consistent basis sets have been employed to provide reliable reference values for the hyperfine parameters involved and have been used to guide the experimental investigation. Analysis of the exper- imental spectra allowed to improve the accuracy of the known spectroscopi…
Pd/C-Catalyzed Hydrosilylation of Enals and Enones with Triethylsilane: Conformer Populations Control the Stereoselectivity
2016
The palladium-on-charcoal-catalyzed chemo-, regio-, and stereoselective 1,4-hydrosilylation and transfer hydrogenation reactions of α,β-unsaturated aldehydes and ketones with triethylsilane have been investigated with a combination of experimental and theoretical methods. The reaction mechanism has been studied experimentally by monitoring the reactions by 1H NMR from aliquots withdrawn from the stirred reaction mixtures, labeling experiments, and control experiments. Our density functional theory results indicate that both aforementioned reactions are initiated with a dissociative adsorption of the triethylsilane on the palladium catalyst. In the hydrosilylation reaction, the α,β-unsaturat…
Cyclic metal(oid) clusters control platinum-catalysed hydrosilylation reactions : from soluble to zeolite and MOF catalysts
2020
The Pt-catalysed addition of silanes to functional groups such as alkenes, alkynes, carbonyls and alcohols, i.e. the hydrosilylation reaction, is a fundamental transformation in industrial and academic chemistry, often claimed as the most important application of Pt catalysts in solution. However, the exact nature of the Pt active species and its mechanism of action is not well understood yet, particularly regarding regioselectivity. Here, experimental and computational studies together with an ad hoc graphical method show that the hydroaddition of alkynes proceeds through Pt-Si-H clusters of 3-5 atoms (metal(oid) association) in parts per million amounts (ppm), which decrease the energy of…
Fluoreszierende silane als OH-selektive schutzgruppen
1985
Abstract Fluorescent tertiary silanes are synthesized which, under cesium fluoride/ imidazole activation, discriminate between primary and secondary OH groups. Serine n-butylamide reacts with [5-dimethylamino(1-naphthyl)]dimethylsilane ( 1 ) and diisopropyl[5-dimethylamino(1-naphthyl)]silane ( 2 ) to form the silyl ethers (−)- l -3-[5-dimethylamino(1-naphthyl)]-dimethylsilyloxy]serine n-butylamid ( 14 ) and (−)- l -3-[diisopropyl[5-dimethylamino(1-naphthyl)]silyloxy]serine n-butylamid ( 15 ) exclusively. The silyl ethers are cleaved on treatment with H 2 F 2 , forming the corresponding fluorescent silyl fluorides. Absorption and fluorescence data as well as stability data for the hydrolysis…
Alkoxysilyl substituted oligo(phenylenevinylene)s: chromophores with reactive side chains
2003
The synthesis and properties of highly luminescent oligo(phenylenevinylene)s (OPV) with curable alkoxysilyl groups are described. Two diethoxymethylsilane moieties are connected directly or through flexible spacers to monodisperse alkoxy-substituted OPVs via hydrosilylation of alkinyl and allyloxy groups, Heck reaction with silylstyrene or condensation of aldehydes with aminopropyl silanes. Hydrolysis of the alkoxysilanes yields silanols condensing to curable three-dimensional networks, thus allowing the transformation of small molecules to transparent and fluorescent films with well-defined chromophores.
Palladium on Charcoal as a Catalyst for Stoichiometric Chemo- and Stereoselective Hydrosilylations and Hydrogenations with Triethylsilane
2014
Stoichiometric quantities of triethylsilane in the presence of activated Pd/C as the catalyst can be used to effect chemo-, regio-, and stereoselective hydrosilylation and transfer hydrogenation reactions. α,β-Unsaturated aldehydes and ketones are selectively hydrosilylated to give the corresponding enol silanes or transfer hydrogenated to give the saturated carbonyl compounds in the presence of other reducible functional groups.