54735-58-9Relevant articles and documents
Use of a Sacrificial Aluminum Anode in the Acylation of Some Olefins
Vukicevic, Rastko D.,Joksovic, Ljubinka,Konstantinovic, Stanimir,Markovic, Zoran,Mihailovic, Mihailo Lj.
, p. 899 - 904 (2007/10/03)
The acylation of some alicyclic and aliphatic alkenes by the electrochemical generation of a catalyst using a sacrificial aluminum anode was investigated. Substrates were electrolyzed in a dichloromethane solution of an appropriate electrolyte (tetraalkylammonium salts) in the presence of an acylating agent (acetyl chloride or anhydride). Thus, unsubstituted cycloalkenes, namely cyclohexene and cycloheptene, gave by that reaction conjugated ketones, i.e. the corresponding 1-acetylcycloalkenes, as the only unsaturated carbonyl compounds in moderate-to-good yields. Under the same reaction conditions their 1-methyl derivatives gave mixtures of the corresponding conjugated and β,γ-unsaturated isomeric ketones in which unconjugated compounds predominate. In both cases unsaturated ketones were accompanied by different amounts of side products. Terminal aliphatic alkenes (1-hexene, 1-heptene, and 1-dodecene) afforded only conjugated a ketone with a normal skeleton, but in lower yields. The acylation of cyclohexene was studied in more detail, altering the reaction conditions by changing the reaction temperature, the supporting electrolyte, the acylating agent and the electrochemical cell. Mechanistic considerations were made on the basis of the products distribution and some theoretical calculations being made by the MOPAC program package (version 7.0).
Electrochemical Acylation of Some Cyclic Olefins by Using Aluminium Anode
Vukicevic, Rastko,Konstantinovic, Stanimir,Joksovic, Ljubinka,Ponticelli, Gustavo,Mihailovic, Mihailo Lj.
, p. 275 - 276 (2007/10/02)
The electrochemical acylation of cyclohexene, cycloheptene and their 1-methyl derivatives produces alkyl-cycloalkenyl ketones in good yields.The unsubstituted cycloalkenes give α,β-unsaturated ketones, whereas the 1-substituted derivatives yield mixtures of α,β- and β,γ-unsaturated ketones in which the latter products are predominant.
Acetylation de trimethylsilyl bicyclo(n,1,0)alcanes : nouvelles syntheses de l'acetyl cyclohexene-2 et d'acetyl bicyclo(n,1,0)alcanes
Ahra, M.,Grignon-Dubois, M.
, p. 820 - 824 (2007/10/02)
Acetylation of trimethylsilyl bicyclo(n,1,0)alkanes was studied using the CH3COCl/AlCl3 complex.The results showed that both larger cycle size (n = 3, 4 or 6) and stereochemistry of the substrate (SiMe3 group in endo or exo position) played a prominent role in the orientation of the reaction : depending upon the starting products, either bicyclic or ethylenic and/or chloro ketones were formed.The results can be rationalized in terms of steric hindrance considerations.They allowed us to propose a new convenient synthesis of acetyl bicyclo(n,1,0)alkanes and also of 1-acetyl 2-cyclohexene.
Influence de la taille du cycle sur la substitution electrophile des cycloalkyltrimethylsilanes. Synthese de cycloalkyldimethylfluorosilanes
Grignon-Dubois, M.,Dunogues, J.,Calas, R.
, p. 291 - 295 (2007/10/02)
Cycloalkyltrimethylsilanes, excepting cyclopropyl-, react with electrophiles by Si - Me bond splitting.Consequently silicon can be functionalized by this route.We also propose a new synthesis of cycloalkyldimethylfluoro(or chloro-)silanes.In the case of five or six member ring derivates, the observed results are interpreted by a mechanism involving initial abstraction of hydride ion from the silicon substrate.
