Vegetable fats such as rapeseed oil, sunflower oil, palm oil or coconut oil consisting of triglycerides offer different carbon chain distributions. The use of these raw materials for the production of industrial chemicals as well as for fuel (biodiesel), which is finally a substitution for mineral oil, is a political discussion with various facets. The basic products such as fatty acids, fatty alcohols, and esters have different physical properties and lead to various areas of application depending on the carbon chain distribution. While the chain length range of C 12 represents important raw materials for detergents, chain lengths of C 18 are used mainly in industrial applications, e.g. as lubricants. Natural fatty alcohols are produced by the heterogeneous catalyzed high-pressure hydrogenation of methyl esters or fatty acids. The unsaturated fats and oils can be derivatized catalytically by functionalization, oligomerization, oxidation or metathesis. Thereby, new functional groups are introduced into the oleochemical substrate. The carbon chain length can be increased or reduced respectively, or a branching in the fatty chain is introduced. Products with completely new properties and areas of applications are available due to these catalytic variations of fats and oils.

During the last years, the industrial significance of renewable resources has highly increased. The ever‐growing use of fossil resources for energy consumption, polymers, fine chemicals and pharmaceuticals and the therefore steadily increasing price favour the substitution of oil and gas by renewable resources. Here, especially products of catalytic functionalisations of vegetable fats and oils such as rapeseed oil, sunflower oil, palm oil or coconut oil play a decisive role. The present article gives a survey of several important catalytic functionalisations of fatty compounds and glycerol resulting in new attractive products. With their emerging properties, they could find a rapid introduction into the chemical market. Particularly the functionalisations via heterogeneous and homogeneous catalysis, like additions, reductions, oxidations and metathesis reactions, will be presented.

An efficient synthetic protocol involving reactions between the free carbene and [RuCl(2)(PPh(3))(2)(Ind)] followed by addition of pyridine leads to the isolation of olefin metathesis active [RuCl(2)(L)(Py)(Ind)] (L = SIMes and SIPr) complexes. This novel approach circumvents the use of costly tricyclohexylphosphine.

Summary Background: α,ω-Difunctional substrates are useful intermediates for polymer synthesis. An attractive, sustainable and selective (but as yet unused) method in the chemical industry is the oleochemical cross-metathesis with preferably symmetric functionalised substrates. The current study explores the cross-metathesis of methyl oleate (1) with cis-2-butene-1,4-diyl diacetate (2) starting from renewable resources and quite inexpensive base chemicals. Results: This cross-metathesis reaction was carried out with several phosphine and N-heterocyclic carbene ruthenium catalysts. The reaction conditions were optimised for high conversions in combination with high cross-metathesis selectivity. The influence of protecting groups present in the substrates on the necessary catalyst loading was also investigated. Conclusions: The value-added methyl 11-acetoxyundec-9-enoate (3) and undec-2-enyl acetate (4) are accessed with nearly quantitative oleochemical conversions and high cross-metathesis selectivity under mild reaction conditions. These two cross-metathesis products can be potentially used as functional monomers for diverse sustainable polymers.

Cross-metathesis of methyl 10-undecenoate with diethyl maleate: Formation of an a,v-diester via a metathesis reaction network Arno Behr, Jessica Pé rez Gomes and Zeynep Bayrak Department of Biochemical and Chemical Engineering, Technische Universitä t Dortmund, Dortmund, GermanyThe cross-metathesis of methyl 10-undecenoate 1 derived from castor oil as a renewable raw material with diethyl maleate 2 was investigated. These reactions were carried out with several phosphine and Nheterocyclic carbene ruthenium catalysts. The reaction conditions were optimised for high conversions in combination with high cross-metathesis selectivity. This single-step and atom-economic synthetic method illustrates an efficient and selective preparation procedure of linear a,v-dicarboxylic acid esters starting from renewable resources and comparatively inexpensive base chemicals. Further byproducts are hardly obtained due to their consumption in secondary metathesis reactions. Hence, a sustainable alternative for polyamide and polyester monomers is presented.