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    Crosslinking of Cellulose by Olefin Metathesis
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    Abstract:
    New crosslinked microcrystalline cellulose plastic films were made by olefin metathesis. Cellulose was first acylated under microwave irradiation by 10‐undecenoyl chloride in lithium chloride/N,N‐dimethylacetamide homogeneous solution to yield unsaturated fatty acid cellulose esters with a degree of substitution (DS) varying from 1 to 2. After studying the variation of cellulose DS vs. microwave irradiation time, the unsaturated fatty acid cellulose esters were subjected to olefin metathesis using Grubbs's catalyst. Crosslinking ratio T (0% < T < 90%) and gel formation during cross metathesis of cellulose esters with different DS are discussed. Structure elucidation was mainly achieved from IR and 1H NMR spectroscopic data.
    Keywords:
    Lithium chloride
    Grubbs' catalyst
    Olefin Metathesis
    Acyclic diene metathesis
    Salt metathesis reaction
    A series of four-coordinate RuII alkylidenes (see scheme for an example) has been prepared as analogues of the proposed olefin metathesis intermediate [(PCy3)Cl2Ru=CHPh]. These complexes exhibit unusual trigonal-pyramidal solid-state geometries, and are rendered highly active for ring-closing metathesis by the addition of HCl.
    Olefin Metathesis
    Acyclic diene metathesis
    Ring-Closing Metathesis
    Salt metathesis reaction
    Ring-opening metathesis polymerisation
    Trigonal crystal system
    Seven novel Hoveyda-Grubbs precatalysts bearing an aminosulfonyl function are reported. Kinetic studies indicate an activity enhancement compared to Hoveyda's precatalyst. A selection of these catalysts was investigated with various substrates in ring-closing metathesis of dienes or enynes and cross metathesis. The results demonstrate that these catalysts show a good tolerance to various chemical functions.
    Olefin Metathesis
    Acyclic diene metathesis
    Ring-opening metathesis polymerisation
    Grubbs' catalyst
    Salt metathesis reaction
    Citations (8)
    The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords "1(st) generation" cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands.
    Olefin Metathesis
    Reactivity
    Salt metathesis reaction
    Grubbs' catalyst
    Acyclic diene metathesis
    Citations (6)
    Olefin Metathesis
    Acyclic diene metathesis
    Salt metathesis reaction
    Ring-opening metathesis polymerisation
    Grubbs' catalyst
    Citations (0)
    We describe the development of a mechanochemical approach for Ru-catalyzed olefin metathesis, including cross-metathesis and ring-closing metathesis. The method uses commercially available catalysts to achieve high-yielding, rapid, room-temperature metathesis of solid or liquid olefins on a multigram scale using either no or only a catalytic amount of a liquid.
    Olefin Metathesis
    Ring-opening metathesis polymerisation
    Acyclic diene metathesis
    Salt metathesis reaction
    Ring-Closing Metathesis
    Citations (154)
    The cross-metathesis of internal olefins is applied for the combinatorial synthesis of small organic molecules; this reaction is conveniently carried out in neat olefin (oleic-acid derivatives) and requires only 0.001 equiv. of [Ru(CHPh)Cl2(PCy3)2] as catalyst (Cy = cyclohexyl).
    Olefin Metathesis
    Salt metathesis reaction
    Acyclic diene metathesis
    Grubbs' catalyst
    Ring-opening metathesis polymerisation
    Abstract Using various cellulose samples, the conditions of cellulose dissolution in N,N‐dimethylformamide with added lithium chloride were established. The way of activation of cellulose influences decisively the dissolution. Complete dissolution of microcrystalline cellulose can only be achieved after treating with liquid ammonia. The required salt concentration amounts to approximately 10 wt‐%. Degree of polymerization and crystallinity of the cellulose influence significantly the solubility behaviour.
    Lithium chloride
    Degree of polymerization
    Dimethyl formamide
    Regenerated cellulose
    Citations (23)
    New ruthenium olefin metathesis initiators bearing sulfoxide moieties are described. The complexes were synthesized by the reaction of indenylidene ruthenium complexes Ind-II and Ind-II′ with different (2-vinyl)phenyl sulfoxides. These compounds show no catalytic activity at room temperature, but exhibit increased activity at elevated temperature. Preliminary studies on the influence of electronic and steric factors on the catalytic activity are presented.
    Olefin Metathesis
    Sulfoxide
    Grubbs' catalyst
    Acyclic diene metathesis
    Citations (63)