31608-53-4Relevant academic research and scientific papers
Comparative analysis of the olfactory properties of silicon/germanium/tin analogues of the lily-of-the-valley odorants lilial and bourgeonal
D?rrich, Steffen,Gelis, Lian,Wolf, Steffen,Sunderk?tter, Astrid,Mahler, Christoph,Guschina, Elena,Tacke, Reinhold,Hatt, Hanns,Kraft, Philip
, p. 1747 - 1752 (2015/02/02)
The silicon/germanium/tin analogues of the lily-of-the-valley odorants lilial (rac-1a), compounds rac-1b, rac-1c, and rac-1d, and bourgeonal (2a), compounds 2b, 2c, and 2d, were synthesized and characterized for their olfactory properties, including GC-olfactometry studies. Compounds rac-1a-c and 2a-c possess a typical lily-of-the-valley odor, whereas the stanna-analogues rac-1d and 2d, despite some floral aspects, clearly no longer belong to the lily-of-the-valley family. In both series of the carbon/silicon/germanium/tin analogues studied, the lily-of-the-valley odor decreases in the order of carbon2+ imaging. Bourgeonal (2a) showed the highest activation potency, whereas lilial (rac-1a) and sila-bourgeonal (2b) exhibited lower activation potencies. Sila-lilial (rac-1b), germa-lilial (rac-1c), and stanna-lilial (rac-1d), as well as germabourgeonal (2c) and stanna-bourgeonal (2d), did not activate heterologously expressed hOR17-4 at the concentrations tested. The carbon/silicon/germanium/tin switch strategy thus showed that the stanna-derivatives clearly exceeded the molecular dimensions of the odorant receptor(s) responsible for the recognition of lily-of-the-valley odorants, although the receptor affinity was already affected with the sila- and germaanalogues. These data could later be used in the qualitative and quantitative evaluation of computational receptor models.
Gas phase germylation of simple aromatics by Me3Ge+ ions
Chiavarino, Barbara,Crestoni, Maria Elisa,Fornarini, Simonetta
, p. 53 - 59 (2007/10/03)
The germylation of simple aromatic hydrocarbons has been studied by two different techniques. The Fourier Transform Ion Cyclotron Resonance (FTICR) technique allowed the study of Me3Ge+ transfer equilibria between aromatics and H2O at 300 K. The ion-molecule reaction of [Me3Ge+· arene] ions with selected neutrals are accounted for by a σ-complex species, retaining the primary ipso structure, where the germyl group and the former aromatic hydrogen are bound to the same tetrahedral carbon. The free energies of binding of Me3Ge+ to the selected aromatic compounds correlate linearly with the values of the corresponding Me3Si+ reaction with a slope of 0.93. The combined information from the FTICR and radiolytic technique has revealed a mechanistic pattern for the electrophilic aromatic substitution by Me3Ge+ that closely reproduces the corresponding Me3Si+ reaction, the major difference lying in the greater ease of detachment of Me3Ge+ by nucleophilic assistance.
Generation and reactions of metal-free trialkylgermyl anions from silylgermane and digermane
Mochida, Kunio,Suzuki, Hiroyasu,Nanba, Michihiko,Kugita, Tsuyoshi,Yokoyama, Yasuo
, p. 83 - 88 (2007/10/02)
Metal-free trimethylgermy) anions were prepared by cleavage of the Ge-Si bond of (trimethylsilyl)trimethylgermane and the Ge-Ge bond of hexamethyldigermane with tetrabutylammonium fluoride (TBAF) in hexamethylphosphoric triamide (HMPA).The reactions of metal-free germyl anions produced by a catalytic or one-equivalent amount of TBAF with organic halides carbonyl compounds, and α,β-unsaturated ketones were examined.Keywords: Silicon; Germanium; Germyl anions; Tetrabutylammonium fluoride; Organic halides; Group 14
SYNTHESIS AND SPECTROSCOPIC CHARACTERISTICS OF ARYLTRIMETHYL-SILICON, -GERMANIUM, AND -TIN COMPOUNDS
Moerlein, S. M.
, p. 29 - 40 (2007/10/02)
The synthesis and spectroscopic characteristics of 28 para-substituted aryltrimethyl-silicon, -germanium, and -tin compounds are described.The infrared spectra show characteristic bands at 1245-1165 (methyl bend), 840-765 (methyl rock), and 1105-1020 (in-plane aromatic H bend) cm-1; the frequency of the last band was found to depend on the sum of the aromatic substituent masses, the presence or absence of metallic constituents in the substituent having little influence.The mass spectral fragmentation patterns are interpreted in terms of localization of positive charge on the metal atom, with subsequent bond cleavage behavior which obeys the rules for mass spectra of carbon compounds.
