646-25-3Relevant articles and documents
A cobalt phosphide catalyst for the hydrogenation of nitriles
Jitsukawa, Koichiro,Mitsudome, Takato,Mizugaki, Tomoo,Nakata, Ayako,Sheng, Min,Yamasaki, Jun
, p. 6682 - 6689 (2020/08/24)
The study of metal phosphide catalysts for organic synthesis is rare. We present, for the first time, a well-defined nano-cobalt phosphide (nano-Co2P) that can serve as a new class of catalysts for the hydrogenation of nitriles to primary amines. While earth-abundant metal catalysts for nitrile hydrogenation generally suffer from air-instability (pyrophoricity), low activity and the need for harsh reaction conditions, nano-Co2P shows both air-stability and remarkably high activity for the hydrogenation of valeronitrile with an excellent turnover number exceeding 58000, which is over 20- to 500-fold greater than that of those previously reported. Moreover, nano-Co2P efficiently promotes the hydrogenation of a wide range of nitriles, which include di- and tetra-nitriles, to the corresponding primary amines even under just 1 bar of H2 pressure, far milder than the conventional reaction conditions. Detailed spectroscopic studies reveal that the high performance of nano-Co2P is attributed to its air-stable metallic nature and the increase of the d-electron density of Co near the Fermi level by the phosphidation of Co, which thus leads to the accelerated activation of both nitrile and H2. Such a phosphidation provides a promising method for the design of an advanced catalyst with high activity and stability in highly efficient and environmentally benign hydrogenations. This journal is
Sustainable hydrogenation of aliphatic acyclic primary amides to primary amines with recyclable heterogeneous ruthenium-tungsten catalysts
Coeck, Robin,Berden, Sarah,De Vos, Dirk E.
supporting information, p. 5326 - 5335 (2019/10/11)
The hydrogenation of amides is a straightforward method to produce (possibly bio-based) amines. However current amide hydrogenation catalysts have only been validated in a rather limited range of toxic solvents and the hydrogenation of aliphatic (acyclic) primary amides has rarely been investigated. Here, we report the use of a new and relatively cheap ruthenium-tungsten bimetallic catalyst in the green and benign solvent cyclopentyl methyl ether (CPME). Besides the effect of the Lewis acid promotor, NH3 partial pressure is identified as the key parameter leading to high primary amine yields. In our model reaction with hexanamide, yields of up to 83% hexylamine could be achieved. Beside the NH3 partial pressure, we investigated the effect of the catalyst support, PGM-Lewis acid ratio, H2 pressure, temperature, solvent tolerance and product stability. Finally, the catalyst was characterized and proven to be very stable and highly suitable for the hydrogenation of a broad range of amides.
High-carbon alkane diamine, and preparation method and application thereof
-
Paragraph 0077; 0080-0082, (2019/03/28)
The invention relates to the field of high-carbon alkane diamine preparation, and discloses high-carbon alkane diamine, and a preparation method and application thereof. The preparation method of thehigh-carbon alkane diamine disclosed by the invention is characterized in that the structure of the high-carbon alkane diamine is as shown in the formula NH2-(CH2)m-NH2; the method comprises the following steps: (1) under amideation reaction conditions, reacting high-carbon alkane diacid which is as shown in the formula COOH-(CH2)n-COOH with an ammonia-containing compound to obtain high-carbon chain diamide which is as shown in the formula CONH2-(CH2)n-CONH2; (2) under an alkaline condition, enabling the high-carbon chain diamide which is as shown in the formula CONH2-(CH2)n-CONH2 to perform rearrangement degradation in the existence of water, sodium hypochlorite and/or sodium hypobromite to obtain the high-carbon alkane diamine which is as shown in the formula NH2-(CH2)m-NH2, wherein n=11to 15, and m=9 to 13. The method provided by the invention is a safe, convenient, simple and feasible preparation method for the high-carbon alkane diamine.
