71958-71-9Relevant academic research and scientific papers
Isosteric Compounds according to the Hydride Principle of Grimm in the Range of Linalool Scents
Wannagat, U.,Damrath, V.,Harder, U.
, p. 1159 - 1170 (2007/10/02)
Substitution of the (CH3)2CH=CH group by (CH3)2C=N in linalool as well as by the (CH3)2CH-CH2 group in linalool and in sila-linalool does not lead to noticeable changes of their scent qualities.On the contrary, substitution of the OH group at the tertiary C atom by NH2 or CH3 - hydride isosteric to OH according to Grimm - affords fishy or etheric instead of the original flowery smells thus indicating a transition to different basic classes of odor.Similar results were obtained with the linalool-like scents of benzyldimethylcarbinol and phenylethyldimethylcarbinol.Therefor the theory of Amoore, after which only shape and size of molecules are ruling their odor qualities, must be called in question. - Keywords: Perfumes; Sila Perfumes; Isosteric Compounds; Silazanes; Olfactoric Theories.
Esters of (Hydroxymethyl)diorganylsilanes: Synthesis and Thermally Induced Rearrangement
Tacke, Reinhold,Wiesenberger, Frank,Becker, Beate,Rohr-Aehle, Regine,Schneider, Petra B.,et al.
, p. 591 - 606 (2007/10/02)
Twenty silanes of the type R1R2Si(H)CH3OR3 (A) were synthesized 1,R2 = Me, Ph, 1-naphthyl, PhCH2, Me3SiCH2; OR3 = OC(O)Me, OC(O)CF3, OS(O)CF3, OP(O)Ph2, OC(O)Cl> and studied for their thermal behaviour.The silanes A undergo a thermally induced rearrangement to give the corresponding silanes R1R2Si(OR3)Me (B).For compounds with OR3 = OC(O)Cl, an additional decarboxylation takes place to yield the chlorosilanes R1R2Si(Cl)Me.Except for the derivatives with OR3 = OC(O)Cl, the energetic (reaction enthalpy) and kinetic data (reaction order, frequency factor, enthalpy and entropy of activation) of these reactions were studied by means of differential scanning calorimetry (DSC).In addition the kinetics of all reactions were investigated by 1H-NMR spectroscopy.The transition state of the rearrangement was investigated by an ab initio study based on the model compound H3SiCH2OC(O)H MeH2SiOC(O)H>.The theoretical data and the experimentally obtained energetic and kinetic data are discussed in terms of mechanistic aspects of the rearrangement reaction A -> B.
