Direct synthesis of polyureas from the dehydrogenative coupling of diamines and methanol

Kumar, Amit; Armstrong, D. P.; Peters, Gavin; Nagala, Manjula; Shirran, Sally L.

doi:10.1039/d1cc01121a

Cited by 30 publications

(34 citation statements)

References 44 publications

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“…As an important building block platform, 5-hydroxymethylfurfural (5-HMF) can be transformed into various valued derivatives by the selective tailoring of its active C=O, À OH, and furan ring functional groups, such as 2,5-dimethylfuran, [1][2][3] 2,5dihydroxymethylfuran, [4][5][6] 2,5-bis(aminomethyl)furan (BAMF), [7][8][9] 2,5-diformylfuran, [10][11][12] 2,5-furandicarboxylic acid, [13,14] and other ring-opened compounds. [15,16] Among them, BAMF is considered as a promising bio-based monomer and utilized in the production of several kinds of bio-based polymers, such as polyurethane, polyamine, and polyurea, [17][18][19] with advantages in the gas barrier performance, miscibility, and processability. [20][21][22][23] Besides, the furan-based amine is also a promising intermediate in the pharmaceutical and food industry.…”

Section: Introductionmentioning

confidence: 99%

Reductive Amination of 5‐Hydroxymethylfurfural to 2,5‐Bis(aminomethyl)furan over Alumina‐Supported Ni‐Based Catalytic Systems

Wei

Cheng

et al. 2022

ChemSusChem

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Mono-and bimetallic Ni-based catalysts were prepared by screening 6 supports and 14 secondary metals for reductive amination of 5-hydroxymethylfurfural (5-HMF) into 2,5bis(aminomethyl)furan (BAMF), among which γ-Al 2 O 3 and Mn were the best candidates. By further optimization of the reaction conditions at 0.4 g catalyst loading for 0.5 g substrate of 5-HMF and 160 °C of reaction temperature, 10Ni/γ-Al 2 O 3 and 10NiMn(4 : 1)/γ-Al 2 O 3 achieved the highest BAMF yields of 86.3 and 82.1 %, respectively. Although the BAMF yield values were comparable with that over Raney Ni, the turnover frequencies based on the initial BAMF yield and unit weight of Ni for 10NiMn(4 : 1)/γ-Al 2 O 3 , 10Ni/γ-Al 2 O 3 , and Raney Ni were calculated as 0.41, 0.09, and 0.04 h À 1 , respectively. X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy showed that the existence of MnO x well dispersed on the γ-Al 2 O 3 support and its electron transfer effect with Ni particles on the surface of the support contributed to the high efficiency and better recyclability for the five-time reused 10NiMn(4 : 1)/γ-Al 2 O 3 catalyst.

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Section: Introductionmentioning

confidence: 99%

Reductive Amination of 5‐Hydroxymethylfurfural to 2,5‐Bis(aminomethyl)furan over Alumina‐Supported Ni‐Based Catalytic Systems

Wei

Cheng

et al. 2022

ChemSusChem

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“…We have recently discovered a new method for the synthesis of polyureas from the dehydrogenative coupling of diamines and methanol using pincer catalysts of ruthenium 35 or manganese. 36 The polyureas of moderate molecular weight (Mn = 3,000 -11,000) and various functionalities from aromatic, aliphatic, and cyclic diamines can be accessed using this methodology.…”

Section: Introductionmentioning

confidence: 99%

“…Considering this hypothesis, we synthesized a polyurea/oligourea from the ruthenium/manganese catalysed dehydrogenative coupling of a diamine poly(ethylene glycol) bis(3-aminopropyl) terminated (Mn = 1,500) and methanol as per the method reported by us recently. 35,36 Some of its characteristic details e. g. molecular weight (estimated by 1 H NMR spectroscopy) and physical properties (estimated by TGA and DSC analysis) are listed in Table 1. The use of this polyurea (PU1) as an SEI-forming additive resulted in a slightly higher coulombic efficiency of 10%.…”

Section: Introductionmentioning

confidence: 99%

Polyureas as SEI-forming Additives for Li Metal Anodes

Haas

Kaufer

Gao

et al. 2022

Preprint

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We report here the first example of the use of an organic “polyurea” polymer as a SEI-forming additive for the lithium metal anode for lithium oxygen batteries. The presence of a suitable polyurea can significantly increase the coulombic efficiency and cycling of the anode in the presence of oxygen in the liquid electrolyte. The findings demonstrate proof of concept for the application of polyureas and other organic polymers for next-generation type batteries with metal anode.

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“…The concept of the dehydrogenative synthesis of ureas has been recently expanded by us for the synthesis of polyureas from the dehydrogenative coupling of diamines and methanol using the ruthenium-Macho complex D with a TON of up to 100 (Figure 1). 35 Table 1. Optimization of catalytic conditions for the dehydrogenative coupling of octylamine and methanol.…”

Section: Introductionmentioning

confidence: 99%

“…Role of bases such as KO t Bu in lowering the barrier of (de)hydrogenation reactions has been suggested before. 35 Upon optimization of catalytic conditions, we turned our attention to utilize this protocol to synthesize a broad variety of urea derivatives. Gratifyingly, using 0.5 mol% of complex 1, and 2 mol% KO t Bu (THF, 150 o C, 24 h) a variety of symmetrical ureas were synthesized in moderate to excellent yields (Figure 2).…”

Section: Introductionmentioning

confidence: 99%

Manganese Catalysed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

Owen

Preiss

McLuskie

et al. 2021

Preprint

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Urea derivatives are prevalent intermediates in the synthesis of resin precursors, dyes, agrochemicals, and pharmaceutical drugs. Furthermore, polyureas are useful plastics with applications in coating, adhesive, and biomedical industries and have a current annual market of USD 885 million. However, the conventional methods for the synthesis of urea derivatives and polyureas involve toxic reagents such as (di)isocyanates, phosgene, CO, and azides. We present here the synthesis of (poly)ureas using much less toxic reagents - (di)amines, and methanol via a catalytic dehydrogenative coupling process. The reaction is catalyzed by a pincer complex of an earth-abundant metal, manganese, and liberates H2 gas, valuable by itself, as the only by-product making the overall process atom-economic, and sustainable. A broad variety of symmetrical, and unsymmetrical urea derivatives and polyureas have been synthesized in moderate to quantitative yields using this catalytic protocol. Mechanistic insights have also been provided using experiments and DFT computation suggesting that the reaction proceeds via an isocyanate intermediate.

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Direct synthesis of polyureas from the dehydrogenative coupling of diamines and methanol

Abstract: We report here the first example of the direct synthesis of polyureas from the dehydrogenative coupling of diamines and methanol using a ruthenium pincer catalyst. The present methodology replaces the...

Cited by 30 publications

References 44 publications

Reductive Amination of 5‐Hydroxymethylfurfural to 2,5‐Bis(aminomethyl)furan over Alumina‐Supported Ni‐Based Catalytic Systems

Reductive Amination of 5‐Hydroxymethylfurfural to 2,5‐Bis(aminomethyl)furan over Alumina‐Supported Ni‐Based Catalytic Systems

Polyureas as SEI-forming Additives for Li Metal Anodes

Manganese Catalysed Dehydrogenative Synthesis of Urea Derivatives and Polyureas

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