With the reactions ystem [Rh(octanoate) 2 ] 2 and triethylamine, diols are produced in ah igh yields of up to 79 %w ith full conversion of intermediate aldehyde and no evidence of olefin hydrogenation. The scopeo ft he reaction was evaluated and the optimised reaction conditions were successfully scaled up to a2 Lr eactor.F inally,t he Rh/amine catalystc omplex was recycled by asimple water extraction of the diol-product.Scheme1.Industrialapproach from dcpd 1 to TCD-diol 6 vs. new route.[a] S.

This article describes the development of an effective thermomorphic multicomponent solvent (TMS) system for the production of branched polyamide monomers. In this system, methyl oleate, a renewable from fats and oils, and a functionalized amine are used as starting materials in a tandem catalytic reaction, which merges different reaction steps into a single preparative step. This particular TMS system consisted of a heptane/acetonitrile solvent mixture and made reusing the precious rhodium catalyst possible in three recycle runs. A constant yield of 61–65% was obtained for each run due to low‐catalyst leaching. Fortunately, the catalyst system does not require any additional phosphorous ligands and allows high yields. A scale‐up for the production of 10–11 g of the desired product in each run was realized. Subsequent hydrogenation of the product directly provided an amine ester, which is a valuable polyamide monomer. Practical applications: A method was developed to enable access to primary amines via hydroaminomethylation and hydrogenation. The product, a nitrile ester, is a valuable intermediate for polyamide monomers. This nitrile ester was successfully hydrogenated to an amine ester, which features a potential polyamide monomer directly. A catalyst recycle of the homogeneous rhodium complex within the hydroaminomethylation of methyl oleate and an amino nitrile was successfully carried out, enabling constant homogeneous catalyst activity over the course of three recycle runs. A scale‐up to obtain 10–11 g of the hydroaminomethylation product was realized. A general method is described for the conversion of methyl oleate within a hydroaminomethylation reaction. The catalyst can be recovered and reused. Valuable polyamide intermediates were obtained.

Die homogene Katalyse zeichnet sich gegenüber der heterogenen Katalyse durch höhere Selektivität und Aktivität bei gleichzeitig milderen Reaktionsbedingungen aus; die Abtrennung der teuren Übergangsmetallkatalysatoren von den Reaktionsprodukten ist jedoch schwierig. Temperaturgesteuerte Lösungsmittelsysteme, die bei geringer Temperatur in zwei Phasen vorliegen und bei Temperaturerhöhung ein homogenes, einphasiges Lösungsmittelsystem ausbilden, ermöglichen eine Reaktionsführung ohne Stofftransportlimitierungen. Durch Abkühlung bildet sich erneut ein Zweiphasensystem aus, bei dem im Idealfall eine Phase das Produkt und die andere den Katalysator enthält.

In contrast to monoolefins, diene hydroformylation is still a demanding task. Some dienes like butadiene and isoprene have been investigated more intensively, however, 1,3-pentadiene ( piperylene) has been rarely investigated. Here, we present a systematic investigation of the hydroformylation of piperylene, using Rh(CO) 2 acac/Xantphos as an active catalyst which can be easily recycled in the green solvent propylene carbonate. Under the chosen conditions aldehyde yields of up to 82% have been obtained, while catalyst recycling was possible for up to six runs.Scheme 1 Hydroformylation of a terminal olefin.