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.
Facile access to: N-formyl imide as an N-formylating agent for the direct synthesis of N-formamides, benzimidazoles and quinazolinones
Huang, Hsin-Yi,Liang, Chien-Fu,Lin, Xiu-Yi,Yen, Shih-Yao
supporting information, p. 5726 - 5733 (2020/08/21)
N-Formamide synthesis using N-formyl imide with primary and secondary amines with catalytic amounts of p-toluenesulfonic acid monohydrate (TsOH·H2O) is described. This reaction is performed in water without the use of surfactants. Moreover, N-formyl imide is efficiently synthesized using acylamidines with TsOH·H2O in water. In addition, N-formyl imide was successfully used as a carbonyl source in the synthesis of benzimidazole and quinazolinone derivatives. Notable features of N-formylation of amines by using N-formyl imide include operational simplicity, oxidant- A nd metal-free conditions, structurally diverse products, and easy applicability to gram-scale operation.
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.
A tertiary amine oxidation cracking method of preparing carboxamide
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Paragraph 0014; 0023, (2017/08/26)
The invention provides a method for preparing formamide through tertiary amine oxicracking. According to the method, tertiary amine serves as a substrate, air or oxygen serves as an oxygen source, and oxicracking occurs on the tertiary amine under the action of a catalyst to generate the formamide. The method is high in oxidation efficiency and product yield and economical and environmentally friendly by taking the air or oxygen as the oxygen source and has a very good application prospect.
Formyloxyacetoxyphenylmethane as an N-Formylating Reagent for Amines, Amino Acids, and Peptides
Chapman, Robert S. L.,Lawrence, Ruth,Williams, Jonathan M. J.,Bull, Steven D.
supporting information, p. 4908 - 4911 (2017/09/23)
Formyloxyacetoxyphenylmethane is a stable, water-tolerant, N-formylating reagent for primary and secondary amines that can be used under solvent-free conditions at room temperature to prepare a range of N-formamides, N-formylanilines, N-formyl-α-amino acids, N-formylpeptides, and an isocyanide.
Cooperative Catalytic Activation of Si?H Bonds: CO2-Based Synthesis of Formamides from Amines and Hydrosilanes under Mild Conditions
Luo, Rongchang,Lin, Xiaowei,Chen, Yaju,Zhang, Wuying,Zhou, Xiantai,Ji, Hongbing
, p. 1224 - 1232 (2017/03/29)
A simple cooperative catalytic system was successfully developed for the solvent-free N-formylation of amines with CO2 and hydrosilanes under ambient conditions, which was composed of a Zn(salen) catalyst and quaternary ammonium salt. These commercially available binary components activated the Si?H bonds effectively, owing to the intermolecular synergistic effect between Lewis base and transition metal center (LB–TM), and subsequently facilitated the insertion of CO2 to form the active silyl formats, thereby leading to excellent catalytic performance at a low catalyst loading. Furthermore, the bifunctional Zn(salen) complexes, with two imidazolium-based ionic-liquid (IL) units at the 3,3′-position of salen ligand, acted as intramolecularly cooperative catalysts, and the solvent-regulated separation resulted in facile catalyst recycling and reuse.
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.
An Efficient Protocol for Formylation of Amines Using Carbon Dioxide and PMHS under Transition-Metal-Free Conditions
Nale, Deepak B.,Bhanage, Bhalchandra M.
, p. 1413 - 1417 (2016/05/24)
A highly efficient, green and simple base catalytic system was investigated for the formylation of amines using CO2 and PMHS [poly(methylhydrosiloxane)] under mild reaction conditions. This reaction proceeds smoothly without additives and furnishes the corresponding N-formylated products from both the 1° and the 2° aliphatic as well as aromatic amines in good to excellent yields.
Amine modified mesoporous Al2O3@MCM-41: An efficient, synergetic and recyclable catalyst for the formylation of amines using carbon dioxide and DMAB under mild reaction conditions
Nale, Deepak B.,Rath, Dharitri,Parida,Gajengi, Aravind,Bhanage, Bhalchandra M.
, p. 4872 - 4881 (2016/07/07)
This work reports an amine modified meso Al2O3@MCM-41, particularly the ordered mesoporous silica, as a catalyst for the formylation of amines with carbon dioxide (CO2) and with dimethylamine-borane (DMAB) as a green reducing source. This newly developed catalytic system represents a heterogeneous and environmentally benign protocol. Besides this, the catalyst could be reused for five consecutive cycles without any significant loss in its catalytic activity towards the synthesis of formamides. The amine modified meso Al2O3@MCM-41 catalysts were well characterized by high and low angle XRD, temperature programmed desorption (TPD), BET-surface area, TGA/DTA and FT-IR analysis techniques. The effect of various reaction parameters such as temperature, CO2 pressure, time and the ratio of substrates to DMAB for the synthesis of formamides has been investigated. The developed protocol can be applicable for the synthesis of most important key intermediates like formoterol, orlistat, leucovarin and iguratimod in biologically active compounds.
Synthesis of Amino-β-lactams by the Photolytic Reaction of Imines with Pentacarbonylchromium(0)
Borel, Christian,Hegedues, Louis S.,Krebs, Jurg,Satoh, Yoshitaka
, p. 1101 - 1105 (2007/10/02)
Chromium-carbene complexes containing the group were synthesized by the reaction of Vilsmeir's salts with Cr(CO)52-.These carbenes were remarkably air stable and resistant to attack by nucleophiles.Photolytic reaction of these complexes with imines, oxazines, oxazolines, imidates, thiazines, and thiazolines produced β-lactams in fair to good yield.In most cases trans stereochemistry was observed.Representative dibenzylamino-β-lacatms were debenzylated to produce β-lactams having a free NH2 group α to the lactam carbonyl group.
