Telomerization of Butadiene with Starch under Mild Conditions

Abstract

The design of industrial products based on bioresources is a challenging issue. Modification of starch, by hydrophobic chemical substituents, results in an innovative hydrophobic material. Herein, the hydrophobic part of the derivative, comprised of octadienyl chains, is introduced through catalytic butadiene telomerization. The process is efficiently conducted on starch in its granular form in an aqueous medium using hydrosoluble palladium complexes. After optimization, a turnover number (TON) of up to 550 was achieved in the presence of [(pi-allyl)PdCl](2) catalyst and, unusually, by using dimethylisosorbide as a cosolvent.

The Telomerization of 1,3‐Dienes – A Reaction Grows Up

“…The other option is the use of co‐solvents, especially short‐chain alcohols. Once more, iso ‐propanol was shown to be a suitable phase‐mediating agent for the purpose of the telomerization of 1,3‐dienes with highly polar compounds in water, but in this case with Na 2 SO 4 added to maintain the physical properties of starch …”

Efficient Telomerization of Butadiene with Starch in Water: The Role of the Surfactant

“…The solid was then filtered, washed with distilled water (2 9 100 mL) and dried to give a white powder (97 wt%/starting starch). DS (degree of substitution) was determined by NMR analysis and corresponded to the average number of substituted hydroxyl group/glucoside unit [4]. 1 …”

“…Among several homogeneous hydrosoluble catalysts, isolated [(p-allyl)Pd(TPPTS) 2 ]Cl catalyst was shown to be the most efficient in the telomerization of methanol in the presence of water as well as for the telomerization of starch in a water/iPrOH mixture [3]. The presence of a cosolvent in this reaction is essential to assure the solubility of butadiene in the medium and it was shown that the conversion decreased with the amount of organic co-solvent [4]. We studied the reaction in pure water but in the presence of surfactants to keep good contacts between the different constituents of the transformation.…”

Pd-Catalyzed Telomerization of 1,3-Dienes with Multifunctional Renewable Substrates: Versatile Routes for the Valorization of Biomass-Derived Platform Molecules

“…Two major improvements were subsequently discovered: the addition of 12.5 wt% of sodium sulphate (Na 2 SO 4 ) stabilizes the starch sufficiently to allow reaction at 50 C without degradation [109]. Dimethyl isosorbide was used as an unconventional green co-solvent.…”