2906-10-7Relevant articles and documents
Simplified preparation of a graphene-co-shelled Ni/NiO@C nano-catalyst and its application in theN-dimethylation synthesis of amines under mild conditions
Liu, Jianguo,Ma, Longlong,Song, Yanpei,Zhang, Mingyue,Zhuang, Xiuzheng
supporting information, p. 4604 - 4617 (2021/06/30)
The development of Earth-abundant, reusable and non-toxic heterogeneous catalysts to be applied in the pharmaceutical industry for bio-active relevant compound synthesis remains an important goal of general chemical research.N-methylated compounds, as one of the most essential bioactive compounds, have been widely used in the fine and bulk chemical industries for the production of high-value chemicals. Herein, an environmentally friendly and simplified method for the preparation of graphene encapsulated Ni/NiO nanoalloy catalysts (Ni/NiO@C) was developed for the first time, for the highly selective synthesis ofN-methylated compounds using various functional amines and aldehydes under easy to handle, and industrially applicable conditions. A large number of primary and secondary amines (more than 70 examples) could be converted to the correspondingN,N-dimethylamines with the participation of different functional aldehydes, with an average yield of over 95%. A gram-scale synthesis also demonstrated a similar yield when compared with the benchmark test. In addition, it was further proved that the catalyst could easily be recycled because of its intrinsic magnetism and reused up to 10 times without losing its activity and selectivity. Also, for the first time, the tandem synthesis ofN,N-dimethylamine products in a one-pot process, using only a single earth-abundant metal catalyst, whose activity and selectivity were more than 99% and 94%, respectively, for all tested substrates, was developed. Overall, the advantages of this newly developed method include operational simplicity, high stability, easy recyclability, cost-effectiveness of the catalyst, and good functional group compatibility for the synthesis ofN-methylation products as well as the industrially applicable tandem synthesis process.
Molecular Addition Compounds. 16. New, Highly Reactive Borane Adducts with N,N-Dialkyl-tert-alkylamines for Hydroboration
Brown, Herbert C.,Kanth, Josyula V. B.,Dalvi, Pramod V.,Zaidlewicz, Marek
, p. 4655 - 4661 (2007/10/03)
Several N,N-diethyl-tert-alkylamines, such as N,N-diethyl-2-methyl-2-butylamine (1, t-PentNEt2), N,N-diethyl-2,3-dimethyl-2-butylamine (2, t-HexNEt2), N,N-diethyl-2,3,3-trimethyl-2-butylamine (3, t-HeptNEt2), and N,N-diethyl-1,1,3,3-tetramethylbutylamine (4, t-OctNEt2) with varying steric bulk around nitrogen (by changing the ter-alkyl group) have been prepared and examined as borane carriers. The complexing ability of these N,N-diethyl-tert-alkylamines with borane decreases in the order: t-BuNEt2 > t-PentNEt2 > t-HeptNEt2 > t-HexNEt2 ≥ t-OctNEt2. From these preliminary studies, the more promising tert-octyldialkylamines were selected for detailed studies. The optimum steric bulk around the nitrogen atom was established by comparing various tert-octyldialkylamines containing variable steric requirements for both the alkyl groups. The complexing ability of these amines with borane decreases in the order shown: t-OctNMe2 (5) > t-OctNEtMe (6) > t-OctN-(CH2CH2)2O (7) > t-OctNEt2 (4) > t-OctNBuiMe (8) > t-OctNPrn2 (9). The reactivity of the corresponding borane adducts toward 1-octene increases in the reverse order. Among the various tert-octyldialkylamine-boranes prepared and examined, only t-OctNEt2 (4) forms a highly reactive liquid borane adduct, which hydroborates 1-octene in tetrahydrofuran rapidly at room temperature. Accordingly, detailed hydroboration studies with this new, highly reactive amine-borane adduct, t-OctEt2N:BH3 (10) and representative mono-, di-, tri-, and tetra-substituted olefins were carried out at room temperature (22 ± 3°C) in selected solvents, tetrahydrofuran, dioxane, tert-butyl methyl ether, n-pentane and dichloromethane. Simple unhindered olefins were hydroborated to the trialkylborane stage, whereas hindered olefins were partially hydroborated to the mono or dialkylborane stage. The hydroborations can be carried out conveniently in a variety of solvents. The amine-borane adduct showed enhanced reactivity in dioxane but low reactivity in dichloromethane. The alkylboranes obtained after hydroboration were oxidized with hydrogen peroxide/ sodium hydroxide and the product alcohols were obtained in quantitative yields, as established by GC analysis. The carrier amine was recovered by simple acid-base manipulations in good yield and can be readily recycled back to the borane adduct.
