Optimized reaction conditions for the cross-metathesis of methyl oleate and oleylamine with ethyl acrylate

Abstract

The cross-metathesis of methyl oleate and oleylamine with ethyl acrylate has been studied using three different ruthenium-based second-generation catalysts. Emphasis was on determining the smallest amount of catalyst necessary for full conversion of technical grade educts. Conversion of methyl oleate is best performed in the presence of 10 equiv. ethyl acrylate without use of additional solvent whereas oleylamine cannot be used directly and protection of the amino group is necessary. An easy protection procedure for oleylamine with acetic anhydride was developed and the best results for crossmetathesis of N-acetyloleylamine were obtained in toluene solution.

Transforming colloidal Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octadecene) into stable CsPbBr3 perovskite emitters through intermediate heterostructures

“…Thus neutral oleylamine is always available in the NC solution. Neutral oleylamine is a nucleophile with a documented reactivity towards linear and cyclic anhydrides, 37,38 and polymaleic anhydride derivatives. 39,40 The reaction between neutral oleylamine and PMAO in the absence of NCs causes broadening of the vinyl hydrogen resonance of the oleyl chain in the 1 H NMR spectrum due to the attachment of small oleylamine molecules to PMAO macromolecules (the specied M w of PMAO is $30 000-50 000 g mol À1 , which roughly corresponds to $80-150 succinic anhydride-octadecene subunits) ( Fig.…”

Olefin cross-metathesis as a valuable tool for the preparation of renewable polyesters and polyamides from unsaturated fatty acid esters and carbamates

“…However, cross-metathesis reactions of compounds having an amine moiety are still quite challenging and usually the amine function is protected. 26 In this context, Bruneau and colleagues reported the cross-metathesis of 10-undecenenitrile with methyl acrylate. 28 Subsequent hydrogenation of the crossmetathesis product yielded the desired AB-type monomer as a polyamide precursor.…”

“…Usually, either the amine function is protected prior to the metathesis reaction or the metathesis reaction is performed in acetic media in order to in situ protonate the amine and prevent catalyst deactivation. 26,27 Robinson and coworkers reported the SM of undecenylamine to prepare the corresponding diamine, a valuable and renewable AA-type monomer for the preparation of polyamides. Bruneau et al reported the cross-metathesis of 10-undecenenitrile or acrylonitrile with methyl 10-undecenoate or methyl acrylate, respectively.…”

On the isomerization of a trans-dichloro to a cis-dichloro amide-chelated ruthenium benzylidene complex and the catalytic scope of these species in olefin metathesis

“…This feature can be of particular interest in industrial processes where regulation of the initiation is crucial for the operational control [15,16], e.g., in reactive injection molding (RIM) of strained cyclic olefins which are polymerized by ring-opening metathesis polymerization (ROMP) [17,18]. Also, cis-dichloro catalysts outperform their trans-dichloro counterparts in several metathesis transformations which demand high temperature [14,19,20]. The latency is believed to be reasoned in the general inability of such cis-dichloro species to perform olefin metathesis; hence, an isomerization step to the respective trans-dichloro isomer has to precede olefin metathesis [21,22].…”