Direct amination of dodecanol with NH3 over heterogeneous catalysts. Catalyst screening and kinetic modelling

Ruiz, Dóris; Aho, Atte; Saloranta, Tiina; Eränen, Kari; Wärnå, Johan; Leino, Reko; Murzin, Dmitry Yu.

doi:10.1016/j.cej.2016.08.083

Cited by 60 publications

(63 citation statements)

References 30 publications

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“…As previously mentioned, the formation of the ester 4 could produce ammonia as a coproduct. This reactive compound could be benzylated by benzyl alcohol through a borrowing hydrogen mechanism, as reported in the literature, thus leading to the formation of benzylamine . This primary amine was successfully alkylated by benzyl alcohol in the optimized conditions, affording dibenzylamine (54 % GC ratio) and N ‐benzylidene‐1‐phenylmethanamine (46 % GC ratio) (Scheme , A).…”

Section: Base Screening For the N‐alkylation Of Phenylacetamide 1a Wimentioning

confidence: 81%

Solvent‐Free N‐Alkylation of Amides with Alcohols Catalyzed by Nickel on Silica–Alumina

et al. 2019

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The N‐alkylation of phenylacetamide with benzyl alcohol has been studied using Ni/SiO2–Al2O3. In the optimized conditions, the desired product was isolated in an excellent 98 % yield. The reaction could advantageously be performed in neat conditions, with a slight excess of amide and a catalytic amount of base. These conditions were tested on a large range of amides and alcohols, affording 24 compounds in 13 to 99 % isolated yields.

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Section: Base Screening For the N‐alkylation Of Phenylacetamide 1a Wimentioning

confidence: 81%

Solvent‐Free N‐Alkylation of Amides with Alcohols Catalyzed by Nickel on Silica–Alumina

et al. 2019

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“…35 The second reaction can be assumed to be at equilibrium with the gas phase on the guidance of recent experimental findings. 36,37,38 O atom, N atom) can be linked by scaling relations to the adsorption energy of atomic C (resp. O, N).…”

Section: Resultsmentioning

confidence: 99%

“…This coupling is often proposed to occur in the homogeneous phase. 37,38 However, the observed selectivity is clearly metal-dependent, 19 which suggests that a surface reaction step is also at play for the selectivity loss. A first possibility is the C-N coupling between the hydroxymethyl CH 2 OH and the aminyl CH 3 NH intermediates into the aminoalcohol CH 3 NHCH 2 OH.…”

Section: Resultsmentioning

confidence: 99%

Rational design of selective metal catalysts for alcohol amination with ammonia

et al. 2019

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The lack of selectivity for the direct amination of alcohols with ammonia, a modern and clean route for the synthesis of primary amines, is an unsolved challenge. Here, we combine first-principles calculations, scaling relations, kinetic simulations and catalysis experiments to unveil the key factors governing the activity and selectivity of metal catalysts for this reaction. We show that the loss of selectivity towards primary amines is linked to a surface-mediated C-N bond coupling between two N-containing intermediates: CH 3 NH and CH 2 NH. The barrier for this step is low enough to compete with the main surface hydrogenation reactions and can be used as a descriptor for selectivity. The combination of activity and selectivity maps using the C and O adsorption energies as descriptors is used for the computational screening of 348 dilute bimetallic catalysts. Among the best theoretical candidates, Co 98.5 Ag 1.5 and Co 98.5 Ru 1.5 (5 wt% Co) are identified as the most promising catalysts from experiments.

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“…Interestingly, the authors found that the presence of an extra supply of hydrogen gas was beneficial to reach a high conversion as well as a high dodecylamine selectivity. 332 As it has been already shown in the previous section devoted to homogeneous catalysis, ammonia has been successfully replaced in numerous examples by other alternative chemical sources, and these concerns have also reached to heterogeneous catalysis. In this case, one of the first examples reported by the group of Mizuno studied the synthesis of both secondary and tertiary amines (218,219) from alcohols (13a, 26a) and urea (217), albeit this time in the presence of a recoverable heterogeneous ruthenium catalyst.…”

Section: Activation Of Alcoholsmentioning

confidence: 93%

Advances in One-Pot Synthesis through Borrowing Hydrogen Catalysis

2018

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The borrowing hydrogen (BH) principle, also called hydrogen auto-transfer, is a powerful approach which combines transfer hydrogenation (avoiding the direct use of molecular hydrogen) with one or more intermediate reactions to synthesize more complex molecules without the need for tedious separation or isolation processes. The strategy which usually relies on three steps, (i) dehydrogenation, (ii) intermediate reaction, and (iii) hydrogenation, is an excellent and well-recognized process from the synthetic, economic, and environmental point of view. In this context, the objective of the present review is to give a global overview on the topic starting from those contributions published prior to the emergence of the BH concept to the most recent and current research under the term of BH catalysis. Two main subareas of the topic (homogeneous and heterogeneous catalysis) have been identified, from which three subheadings based on the source of the electrophile (alkanes, alcohols, and amines) have been considered. Then the type of bond being formed (carbon-carbon and carbon heteroatom) has been taken into account to end-up with the intermediate reaction working in tandem with the metal-catalyzed hydrogenation/dehydrogenation step. The review has been completed with the more recent advances in asymmetric catalysis using the BH strategy.

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Direct amination of dodecanol with NH3 over heterogeneous catalysts. Catalyst screening and kinetic modelling

Cited by 60 publications

References 30 publications

Solvent‐Free N‐Alkylation of Amides with Alcohols Catalyzed by Nickel on Silica–Alumina

Solvent‐Free N‐Alkylation of Amides with Alcohols Catalyzed by Nickel on Silica–Alumina

Rational design of selective metal catalysts for alcohol amination with ammonia

Advances in One-Pot Synthesis through Borrowing Hydrogen Catalysis

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