18889-09-3Relevant articles and documents
Function-oriented ionic polymers having high-density active sites for sustainable carbon dioxide conversion
Chen, Yaju,Luo, Rongchang,Bao, Junhui,Xu, Qihang,Jiang, Jun,Zhou, Xiantai,Ji, Hongbing
, p. 9172 - 9182 (2018)
On the basis of the development of function-oriented synthesis (FOS), we presented for the first time an efficient and one-pot construction of functional ionic polymers (FIPs) through the phenol-formaldehyde condensation process (pre-synthetic approach); FIPs had high density of Br?nsted acidic and ionic sites. Considering the electrophilic-nucleophilic dual activation of phenolic hydroxyl groups and bromide anions, the imidazolium-based FIP-Im exhibited high activity for metal-, solvent- and additive-free synthesis of cyclic carbonates from CO2 and epoxides under mild conditions. Then, to obtain higher ionic density and a more flexible skeleton, FIP-Im@QA was also prepared by implanting quaternary ammonium (QA) in the framework of FIP-IMvia the Williamson ether synthesis (post-synthetic modification), which demonstrated high efficiency in the N-formylation reaction of multitudinous secondary amines with CO2 and PhSiH3 at ambient temperature. More interestingly, these function-oriented catalysts were compatible with the target transformation under low CO2 concentration (15% in 85% N2, v/v) and were also reused for more than six times without a significant loss of activity and selectivity. Therefore, this study could not only facilitate the design and construction of FIPs, but also provide sustainable protocols for efficient production of value-added chemicals from CO2 under mild conditions.
Novel clamp metal complex and application thereof
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Paragraph 0240; 0241; 0242; 0321-0325, (2019/04/26)
The invention discloses a method for preparing a novel clamp-shaped complex and application of the novel clamp-shaped complex in the reaction of catalytic hydrogenation of carboxylic acid ester compounds to produce corresponding alcohols and reaction of carbon dioxide catalytic hydrogenation to form formamide compounds. Carboxylic acid esters and hydrogen as raw materials or carbon dioxide, hydrogen and amine compounds as raw materials are reacted in an organic solvent condition or a solvent-free condition in the presence of a transition metal complex as a catalyst to respectively form the corresponding alcohol compounds and/or corresponding formamide compounds. The method has the advantages of being high in reaction efficiency, good in selectivity, mild in conditions, economical, environmentally-friendly, and simple in operation, and has good promotion and application prospects.
Synthesis of formamides containing unsaturated groups by: N -formylation of amines using CO2 with H2
Liu, Hangyu,Mei, Qingqing,Xu, Qingling,Song, Jinliang,Liu, Huizhen,Han, Buxing
supporting information, p. 196 - 201 (2017/08/15)
Formamides have wide applications in the industry and have been synthesized using CO2 as a carbon source and H2 as a reducing agent. However, previous systems required a noble catalyst and high temperature to achieve high efficiency, and the substrate scope was mostly limited to saturated amines. The selective N-formylation of amines containing unsaturated groups using CO2 and H2 is challenging because the efficient catalysts for the N-formylation are usually very active for hydrogenation of the unsaturated groups. Herein, we achieved for the first time a selective and efficient N-formylation of amines containing unsaturated groups using CO2 and H2 with a Cu(OAc)2-4-dimethylaminopyridine (DMAP) catalytic system. The substrates were converted to the desired formamides, while the unsaturated groups, such as the carbonyl group, the CC bond, CN bond and the ester group remained. The main reason for the excellent selectivity of the Cu(OAc)2-DMAP catalytic system was that it was very active for the N-formylation reaction, but was not active for the hydrogenation of the unsaturated groups.
