14704-14-4Relevant articles and documents
Photoelektronen-Spektren und Molekueleigenschaften. CXLVIII. Die niedrigen ersten Ionisierungsenergien β-trimethylsilyl-substituierter Ether RO-CH3-nn und RO-Si3
Bock, Hans,Meuret, Jochen
, p. 43 - 54 (1993)
The first vertical ionization energies of dialkylethers are lowered up to 3 eV (!) by β-trimethylsilyl substituents and, therefore, further confirm the powerful electron donor effect of -CH3-nn and -Si3 groups.The gas-phase photoelectron spectra are assigned based on geometry-optimized MNDO calculations and the substituent effects are discussed in terms of conformationally dependent hyperconjugative second order perturbations.
Nucleophilic Substitution Reactions of Trimethylsilylmethyl Arenesulfonates with Anilines and Benzylamines in Acetonitrile
Oh, Hyuck Keun,Shin, Chul Ho,Lee, Ikchoon
, p. 2411 - 2414 (2007/10/02)
The results of kinetic studies on the reactions of trimethylsilylmethyl arenesulfonates, 1 (Me3SiCH2OSO2C6H4Z), with anilines and benzylamines in acetonitrile at 65.0 deg C are reported.The relatively large positive value of the cross-interaction constant between substituents in the nucleophile (X) and leaving group (Z), ρxz, indicates that the reaction proceeds by a SN2 process with a relatively tight transition state.The enhanced rate of 1 compared with the rates for other corresponding carbon analogues leads us to conclude that the destabilizing effect of the α-silyl group on the ground state of 1 due to geminal interaction is important not only for SN1 but also for SN22 reactivities.
Alcoxymethyltributyletains precurseurs d'alcoxymethyllithiums: application a la synthese de monoethers d'α-glycols et a l'homologation de cetones en aldehydes
Duchene, Alain,Mouko-Mpegna, David,Quintard, Jean-Paul
, p. 787 - 793 (2007/10/02)
Ethoxymethyltributyltin (obtained from diethoxymethyltributyltin, acetyl chloride and tributyltin hydride) and methoxymethyltributyltin (obtained from chloromethyl-methyl ether and tributylstannylmagnesium chloride) have been transmetallated with butyllithium to give the corresponding alkoxymethyl lithium reagents.This reaction, although usually performed in ether, is possible in a variety of other solvents thus simplifying some of the problems encountered during isolation of the products.The alkoxymethyllithiums obtained react with aldehydes and ketones to give cleanly the corresponding monoprotected α-glycols.Stereochemical trends were observed for hydratropaldehyde and 4-tertiarybutylcyclohexanone, while regiochemical trends were evaluated in the case of cyclohexen-2-one.Syntheis of aldehydes has been achieved in good yields from tertiary monoprotected α-glycols using conventional methods.
