Silicon-29 NMR Spectra of tert-Butyldimethylsilyl and Trimethylsilyl Derivatives of Some Non-Rigid Diols

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Title:Silicon-29 NMR Spectra of tert-Butyldimethylsilyl and Trimethylsilyl Derivatives of Some Non-Rigid Diols
Creators:
Kvíčalová, Magdalena
Blechta, Vratislav
Kobylczyk, Krzysztof
Piekos, Ryszard
Schraml, Jan
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 62, 5, pp. 761-768
Uncontrolled Keywords:Trimethylsilyl derivatives, Silicon-29 NMR, Diols, <i>tert</i>-Butyldimethylsilyl derivatives, NMR

Abstract

<sup>29</sup>Si NMR spectra of trimethylsilyl (TMS) and <i>tert</i>-butyldimethylsilyl (TBDMS) derivatives of selected diols were measured under standardized conditions (<i>i.e.</i>, in diluted CDCl<sub>3</sub> solutions). Application of the recently reported correlation between the chemical shifts in TMS and TBDMS derivatives revealed considerable and systematic deviations which exceeded experimental errors and error estimates from the correlation. Two possible explanations of the deviations are considered: interaction between the two bulky substituent groups and invalidity of the reported correlation for simple hydroxy derivatives. An independent study of analogous derivatives of monohydroxy compounds has shown that the linear correlation holds but the slope and intercept are significantly different from those reported previously on the basis of a study of amino acid derivatives. The data obtained for the diol derivatives fit the new correlation very well and no indication of an interaction between the bulky TBDMS groups was noticed. However, deviations do occur in branched diol derivatives in which branching reduces accessibility of the oxygen atoms surface to associate with proton donors. The largest deviation was found when intramolecular hydrogen bond was formed.

Title:Silicon-29 NMR Spectra of tert-Butyldimethylsilyl and Trimethylsilyl Derivatives of Some Non-Rigid Diols
Creators:
Kvíčalová, Magdalena
Blechta, Vratislav
Kobylczyk, Krzysztof
Piekos, Ryszard
Schraml, Jan
Uncontrolled Keywords:Trimethylsilyl derivatives, Silicon-29 NMR, Diols, <i>tert</i>-Butyldimethylsilyl derivatives, NMR
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:62
Number:5
Page Range:pp. 761-768
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19970761UNSPECIFIED
ID Code:1157
Item Type:Article
Deposited On:06 Feb 2009 17:07
Last Modified:06 Feb 2009 16:07

Citation

Kvíčalová, Magdalena; Blechta, Vratislav; Kobylczyk, Krzysztof; Piekos, Ryszard; Schraml, Jan (1997) Silicon-29 NMR Spectra of tert-Butyldimethylsilyl and Trimethylsilyl Derivatives of Some Non-Rigid Diols. Collection of Czechoslovak Chemical Communications, 62 (5). pp. 761-768. ISSN 0010-0765

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