Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

Behr, Arno; Wintzer, Andreas

doi:10.1002/ceat.201500466

Cited by 16 publications

(15 citation statements)

References 42 publications

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“…So far, there are only a few examples that use a recycling method to recover the precious homogeneous rhodium catalyst in hydroaminomethylation and that use a renewable starting material . Because the products and catalysts form one homogeneous phase, simply removing the homogeneous catalyst from the product mixture is not possible.…”

Section: Introductionmentioning

confidence: 99%

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

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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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.

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Section: Introductionmentioning

confidence: 99%

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

Vorholt

Immohr

Ostrowski

et al. 2016

Euro J Lipid Sci & Tech

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“…Although hydroaminomethylation is a well‐known conversion that is applied to several unsaturated compounds, there are only few examples of hydroaminomethylations with terpenes, in particular pinene, camphene, and limonene, and naturally occurring allyl benzenes such as eugenol and estragole . None of the hydroaminomethylations mentioned above consist of a hydroformylation of conjugated 1,3‐dienes but rather isolated terminal double bonds.…”

Section: Methodsmentioning

confidence: 99%

Renewable Surfactants through the Hydroaminomethylation of Terpenes

et al. 2017

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A catalytic system was developed to enable the use of industrially available terpenes (e.g., β‐myrcene, β‐farnesene) in hydroaminomethylation to obtain renewable building blocks for surfactants in two steps. This homogeneously catalyzed tandem reaction includes both hydroformylation and enamine condensation steps, followed by hydrogenation. Under the optimized conditions, the Rh/1,2‐bis(diphenylphosphino)ethane catalytic system delivers products in high yields (70 %) after short reaction times (3 h) with unprecedentedly high turnover frequency (TOF) values for the hydroformylation of 1,3‐dienes of over 739 mol mol−1 h−1. This is the highest TOF reported to date for the hydroformylation of a 1,3‐diene. Furthermore, regioselectivities of 97 % and above were observed in the hydroformylation step, which is extraordinarily high for the conversion of 1,3‐dienes. The terpene‐derived amines obtained were further functionalized to quaternary ammonium compounds that were found to show surface activity quite similar to that of industrially available quaternary ammonium compounds. The hydroaminomethylation of terpenes achieves higher step efficiency than industrial means and makes use of an alternative, renewable feedstock to synthesize more environmentally friendly surfactants.

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“…A few examples of hydroaminomethylation reaction with terpenes were reported including α-pinene [75], β-pinene [74], camphene [74], limonene [74,76,77], β-myrcene and β-farnesene [78] and naturally occurring allyl benzenes such as eugenol [79] and estragole [80]. Hydroformylation of the internal double bonds is much more difficult than the terminal bonds, thus it is not surprising that the examples mentioned above are related to isolated terminal double bonds.…”

Section: Hydroaminomethylation Of Olefin Bonds In Terpenesmentioning

confidence: 99%

“…Amination of aldehydes is more difficult with ammonia than with primary amines. Nevertheless Behr et al [77] applied ammonia in HAM of limonene (1) ( Figure 9). The reaction proceeds through hydroformylation of limonene (1) to the corresponding aldehyde (2) in the first step followed by condensation with ammonia giving an aldehyde observed experimentally and subsequent hydrogenation of the latter to a primary amine (3).…”

Section: Hydroaminomethylation Of Olefin Bonds In Terpenesmentioning

confidence: 99%

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Valorization of Biomass Derived Terpene Compounds by Catalytic Amination

2018

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This review fills an apparent gap existing in the literature by providing an overview of the readily available terpenes and existing catalytic protocols for preparation of terpene-derived amines. To address the role of solid catalysts in amination of terpenes the same reactions with homogeneous counterparts are also discussed. Such catalysts can be considered as a benchmark, which solid catalysts should match. Although catalytic systems based on transition metal complexes have been developed for synthesis of amines to a larger extent, there is an apparent need to reduce the production costs. Subsequently, homogenous systems based on cheaper metals operating by nucleophilic substitution (e.g., Ni, Co, Cu, Fe) with a possibility of easy recycling, as well as metal nanoparticles (e.g., Pd, Au) supported on amphoteric oxides should be developed. These catalysts will allow synthesis of amine derivatives of terpenes which have a broad range of applications as specialty chemicals (e.g., pesticides, surfactants, etc.) and pharmaceuticals. The review will be useful in selection and design of appropriate solid materials with tailored properties as efficient catalysts for amination of terpenes.

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Hydroaminomethylation of the Renewable Limonene with Ammonia in an Aqueous Biphasic Solvent System

Cited by 16 publications

References 42 publications

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

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

Renewable Surfactants through the Hydroaminomethylation of Terpenes

Valorization of Biomass Derived Terpene Compounds by Catalytic Amination

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