The mission of addition and fission – catalytic functionalization of oleochemicals

Abstract

Oleochemicals are used in the chemical industry in numerous processes and applications, having the largest share among all other renewable resources. Besides the well‐known transformations performed at the carboxylic moiety of the alkyl chain, many natural occurring fatty compounds offer a further opportunity for refinement, that is: catalytic functionalization of the CC double bond. In the present review, the authors describe the mission of the scientific work that is performed at the chair of Technical Chemistry at the TU Dortmund towards selective and atom economic functionalization of oleochemicals. Special emphasis lays on homogenous transition metal catalysis towards potential applications of the resulting products and their continuous production in miniplant scale. The given examples are discussed in the context of the work of other groups and summarize recent developments in the field of addition and fission reactions of oleochemicals. The Mission of Addition and Fission—The functionalization of oleochemicals using homogeneous transition metal catalysis is a very elegant way for producing valuable chemicals via many possible pathways. In this review, recent contributions to e.g. addition or cleavage reactions by Behr's group at the TU Dortmund are presented and discussed in the context of relevant literature, highlighting their significance in this important field of oleochemistry.

From Oleo Chemicals to Polymer: Bis‐hydroaminomethylation as a Tool for the Preparation of a Synthetic Polymer from Renewables

“…Their general chemical structure consisting of a long linear alkyl chain and additional functional groups makes these particularly interesting for polycondensates . Furthermore, a major part of these types of substrates is unsaturated and offers potential for further functionalization, which in principle makes linear bifunctional molecules easily accessible. Especially promising in the context of green chemistry are sustainable concepts, which allow for the direct use of commodity oleo chemicals in atom‐economic transition‐metal‐catalyzed reactions, as shown, for example, in isomerizing methoxycarbonylation…”

Acrylate Esters by Ethenolysis of Maleate Esters with Ru Metathesis Catalysts: an HTE and a Technoeconomic Study

“…Ethenolysis, that involves the cross‐metathesis reaction between ethylene and another olefin, has recently emerged as a powerful methodology for the production of α ‐olefins and in particular the catalytic upgrading of biomass‐derived feedstocks, e. g ., the conversion of long‐chain esters such as oleates to the corresponding terminal olefins . The research focus has revolved around oleates and related esters owing to their abundance in vegetable oils and the high value of terminal olefins produced from those substrates and ethylene.…”

Improving Aqueous Biphasic Hydroformylation of Unsaturated Oleochemicals Using a Jet‐Loop‐Reactor

“…Homogeneous catalysts possess a huge potential for functionalizing unsaturated oleochemicals, such as unsaturated fatty acids and derivatives thereof. [1][2][3] As presented in Figure 1, aldehydes are accessible by rhodium-catalysed hydroformylation, which can undergo numerous subsequent reactions, to carboxylic acids, alcohols, or amines. [4,5] Bifunctional molecules are thus formed potentially having very interesting applications as precursors for polycondensates, lulbricants, or surfactants.…”