Catalyst recycling in the hydroaminomethylation of methyl oleate: A route to novel polyamide monomers

Abstract

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.

Plant‐Oil‐Based Polyamides and Polyurethanes: Toward Sustainable Nitrogen‐Containing Thermoplastic Materials

“…Generally, the presence of longer “dangling” aliphatic chains in the polymer structure lowered the glass transition temperature, as it was also observed earlier . Another potential route to such monomers is hydroaminomethylation, but polymers from such structures were not reported yet. Also based on the abovementioned oxyfunctionalization and reductive amination strategy, 1 – 3 can be functionalized to obtain branched monomers for polyamide synthesis .…”

Thermomorphic Multiphase Systems: Switchable Solvent Mixtures for the Recovery of Homogeneous Catalysts in Batch and Flow Processes

“…The formed amine esters can be potentially used as monomers for polyamides. [22] In general, the examples show that HAMr epresents av ery complex reactions ystem.T wo fluidic substrates and two different gases in nonequivalenta mountsa re used. In addition, water is formed as ac oproduct.…”

“…Behr [19,22,82,83] pp / -hydroamination 2010 Behr [21,24,84,85] pppp esterh ydrolysis(enzymatic)2011Behr [86,87] pp -cyclopropanation 2011Chiba [38] p --metathesis 2012 Behr [88] pp --Fischmeister [25] methoxycarbonylation2013…”

“…A closer look into the mechanism for these thermoregulated properties is explained in Section2 of this review.D ifferent terms and definitions for TMSs can be found in the literature. Amongo thers, thesem ixtures have been referred to as thermomorphic solvent systems, [7,8,[9][10][11][12][13][14][15] thermomorphic multicomponent solvent systems, [16][17][18][19][20][21][22][23][24][25] thermomorphic solvent mix-Jonas Biangas tudiedc hemistry at TU Dortmund from 2011t o2 017. His bachelor thesis was on the hydroformylation of 10-undecenoate in thermomorphic multiphase systems.…”

Synthesis of Industrial Primary Diamines via Intermediate Diols – Combining Hydroformylation, Hydrogenation and Amination

“…The compatibility of the different reaction parameters required for each individual reaction step poses a significant challenge when it comes to developing new tandem catalysis reactions. Tandem reactions such as hydroaminomethylation, hydrohydroxymethylation,, aldol condensation or epoxidation all include a hydroformylation step to obtain the intermediate aldehyde, which then undergoes further conversions to achieve the desired product. Recent investigations using a rhodium and ruthenium catalyst have combined dcpd hydroaminomethylation with the dealkylation of the resulting secondary amines with ammonia to obtain TCD‐diamine.…”