70531-24-7Relevant academic research and scientific papers
Acid-catalyzed chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines
Guo, Luxia,Chen, Zihao,Zhu, Hongmei,Li, Minghao,Gu, Yanlong
supporting information, p. 1419 - 1422 (2020/11/12)
Chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines were described, which were established on the basis of either a C[sbnd]C bond cleavage or a rearrangement process of a reaction intermediate. These reactions proceeded in a condition-determined manner with good functional group tolerance. In the first model, 2,2-dimethoxyacetaldehyde reacted with aniline to form a new C[sbnd]N bond, in the presence of O2, via a C[sbnd]C bond cleavage reaction. However, in the second model, by performing the reaction in the absence of O2, Heyns rearrangement occurred and generated a new C[sbnd]O bond to form methyl phenylglycinate. Such condition-determined reactions not only offered the new way for value-added conversion of biomass-derived platform molecule, 2, 2-dimethoxyacetaldehyde, but also provided efficient methods for the synthesis of N-arylformamides and methyl phenylglycinates.
A green, efficient, and rapid procedure for the hydrogenation of nitroarenes to formanilides in water
Wang, Yingying,Zhan, Zhajun,Zhou, Yang,Lei, Min,Hu, Lihong
, p. 527 - 533 (2018/01/27)
Abstract: A green, efficient, and rapid procedure for the hydrogenation of nitroarenes to formanilides in Pd(TFA)2/HCOOH system in water is described. Under optimized conditions, the reaction of most substrates is complete within 30?min with yields of 30–93%. Furthermore, this procedure is applied successfully for the modification of natural products, such as arctigenin, vindoline, and estrone. Graphical abstract: [Figure not available: see fulltext.].
Chemoselective Schwartz Reagent Mediated Reduction of Isocyanates to Formamides
Pace, Vittorio,De La Vega-Hernández, Karen,Urban, Ernst,Langer, Thierry
supporting information, p. 2750 - 2753 (2016/06/15)
Addition of the in situ generated Schwartz reagent to widely available isocyanates constitutes a chemoselective, high-yielding, and versatile approach to the synthesis of variously functionalized formamides. Steric and electronic factors or the presence of sensitive functionalities (esters, nitro groups, nitriles, alkenes) do not compromise the potential of the method. Full preservation of the stereochemical information contained in the starting materials is observed. The use of formamides in the nucleophilic addition of organometallic reagents (Chida-Sato allylation, Charette-Huang addition to imidoyl triflate activated amides, Matteson homologation of boronic esters) is briefly investigated.
Copper-catalyzed formamidation of arylboronic acids: Direct access to formanilides
Srivastava, Vishnu P.,Yadav, Deepak K.,Yadav, Arvind K.,Watal, Geeta,Yadav, Lal Dhar S.
, p. 1423 - 1427 (2013/07/26)
A new approach for direct synthesis of formanilides starting from structurally varied arylboronic acids is reported. The protocol involves a copper-catalyzed Chan-Lam coupling reaction between arylboronic acids and formamide in the presence of a base at room temperature. The strategy offers a valid and practical alternative to existing transformations of amino, nitro, and azido arenes to formanilides, especially in terms of executing arylboronic acids as easily accessible, stable, and diversified substrates, under mild reaction conditions, and in a simple operation with high efficiency. Georg Thieme Verlag Stuttgart · New York.
Synthesis of new Fe(II) and Ru(II) η5-monocyclopentadienyl compounds showing significant second order NLO properties
Valente, Andreia,Royer, Sophie,Narendra, Milan,Silva, Tiago J.L.,Mendes, Paulo J.G.,Robalo, M. Paula,Abreu, Manuel,Heck, Jürgen,Garcia, M. Helena
, p. 42 - 49 (2013/06/27)
A series of new ruthenium(II) complexes of the general formula [Ru(η5-C5H5)(PP)(L)][PF6] (PP = DPPE or 2PPh3, L = 4-butoxybenzonitrile or N-(3-cyanophenyl) formamide) and the binuclear iron(II) comple
Mn-promoted aerobic oxidative C-C bond cleavage of aldehydes with dioxygen activation: A simple synthetic approach to formamides
Zhang, Chun,Xu, Zejun,Shen, Tao,Wu, Guolin,Zhang, Liangren,Jiao, Ning
supporting information; experimental part, p. 2362 - 2365 (2012/06/29)
A novel Mn-promoted aerobic oxidative C-C bond cleavage of aldehydes with dioxygen activation has been developed. The usage of molecular oxygen (1 atm) as oxidant, reactant, and an initiator to trigger this transformation makes this transformation very green and practical. A plausible radical process is proposed on the basis of mechanistic studies. Furthermore, this method provides a practical, neutral, and mild synthetic approach to formamides, which are important units in biologically active molecules.
ZnO as a new catalyst for N-formylation of amines under solvent-free conditions
Hosseini-Sarvari, Mona,Sharghi, Hashem
, p. 6652 - 6654 (2007/10/03)
The treatment of amines with formic acid in the presence of ZnO under solvent-free conditions brings about highly and efficient N-formylation to give the corresponding formamides in excellent yields. The N-formylation reaction not only involves mild conditions, simple operation, and high yields but also high chemoselectivity.
Lifetimes of imidinium ions in aqueous solution
Dalby, Kevin N.,Jencks, William P.
, p. 7271 - 7280 (2007/10/03)
Imidinium ions, ArN=CNR2+, were generated in aqueous solution from the solvolysis of fluoro and chloro formamidines at pH 9.3 and 25°C. Rate constants for the hydration of five imidinium ions were determined from a kinetic analysis of their trapping by thiolacetate anion, CH3COS-, in the presence of a pool of competing fluoride anion, and a rate constant of k(AcS)- = 5 x 109 M-1 S-1 for diffusion-controlled trapping of the carbocations with thiolacetate anion. The rate constants, k(s), for hydration of the imidinium ions, XArN=CNC4H8O+ are 3.6 x 105, 5.8 x 105, 1.5 x 106, 1.6 x 106, and 1.8 x 106 s-1 for X = H, 4-Cl, 3-CN, 4-CN, and 3-NO2, respectively. In a similar experiment a rate constant of k(s) = 3.3 x 107 s-1 was obtained for hydration of the imidinium ion 4-NO2-ArN=CNCH3(OCH3)+, by using azide anion to trap the cation and a rate constant of k(az) = 5 x 109 M-1 s-1 for diffusion-controlled trapping of the imidinium ion with azide ion. The partitioning rate constant ratio k(AcS)-/k(s) for 4-ClArN=CNC4H8O+ decreases by approximately 6-fold in 45% v/v glycerol/water in contrast to k(az)/k(s), which remains almost constant, showing that thiolacetate, but not azide anion, combines with the imidinium ion at a diffusion-limited rate. The reactivity of the imidinium ions deviate from behavior predicted by the N+ scale in a manner that may be explained by a difference in the selectivity of the cation when compared to the more stable N+ carbocations.
