The relative reactivity of 2,3‐dicarbomethoxy‐5‐norbornenes in metathesis polymerization using the original n‐chelating ruthenium carbene complex

Abstract

1 H NMR spectroscopy is used to study the kinetics of metathesis copolymerization of three isomeric 2,3-dicarbomethoxy-5-norbornenes using the original N-chelating ruthenium carbene complex. Based on the experimental data the copolymerization constants of isomeric 2,3-dicarbomethoxy-5-norbornenes are calculated. It is shown that the relative reactivity of endic acid dimethyl ester-(1R,2S,3R,4S)-dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate is almost two times lower than the corresponding values for (1R,2R,3S,4S)-dimethyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, which confirms earlier findings of steric hindrance in the orientation of the monomer due to the carbene catalyst.

Ion Conducting ROMP Monomers Based on (Oxa)norbornenes with Pendant Imidazolium Salts Connected via Oligo(oxyethylene) Units and with Oligo(ethyleneoxy) Terminal Moieties

“…Scheme shows the syntheses of imidazole precursors. The exo -norbornene isomer was specifically selected over the endo isomer for its ability to more readily undergo ROMP; − stereo purity of anhydride 1 was achieved through repeated recrystallizations and maintained throughout the synthetic pathways. Although previous results indicated longer ethyleneoxy chains would be advantageous, with the addition of every ethyleneoxy unit, the overall charge density of the molecule is diluted, so obviously there is a limit and the optimal length was not easily predicted.…”

“…Consequently, this product was isomerized and hydrolyzed in a single process, according to the work by Kanao et al., to provide an exo isomer rich norbornene carboxylic acid. The exo isomer is desirable for polymerizations as it has less steric hindrance and polymerizes more readily. − , The exo isomer 13 was isolated by selectively lactonizing the endo isomer in the presence of iodine. The exo acid 13 was converted into the acid chloride, in the presence of magnesium to preserve the alkene, and then esterified with tetra­(ethylene glycol) monotosylate.…”

Ring Opening Metathesis Polymerization

“…The presence of a substituent for the monomer molecule in endo-position reduces reaction capacity of this monomer [46]. Activation parameters are directly depended on the ability of monomer to form intramolecular complex with active form of ruthenium.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…73) [320]; (9) 5-ethylidenenorbornene (68) [321], including its use as a part of a self-healing system [322]; (10) vinylnorbornene [323]; (11) tetracyclododecene (69) [324]; (12) norbornadienes connected to various hydrophobic groups, including a steroid system [325]; (13) dicyclopentadiene [326,327,328,329,330,331,332,333,334,335,336], including polymerizations performed in the presence zinc oxide nanoparticles [337], urea formaldehyde microcapsules [338],mildly oxidized graphene oxide [339], barium titanate [340], and high internal phase emulsions [341,342]; (14) the norbornadiene-anthracene Diels-Alder adduct (76) [343,344]; (15) norbornenedicarboxylate esters connected to cyanobiphenyl groups [345], to anthracene groups [346], and to nitroxide groups (e.g. 79) [347]; (16) the three stereoisomeric dimethyl norbornenedicarboxylates (determination of the relative rates of ROMP) [348]; (17) norbornenecarboxamides [349]; (18) norbornenesuccinimides [350], including those A c c e p t e d M a n u s c r i p t …”