16741-46-1Relevant articles and documents
Efficient isonitrile hydration through encapsulation within a hexameric self-assembled capsule and selective inhibition by a photo-controllable competitive guest
Bianchini, Giulio,Sorella, Giorgio La,Canever, Nicolo,Scarso, Alessandro,Strukul, Giorgio
, p. 5322 - 5324 (2013)
Catalytic hydration of neutral isonitriles to yield the corresponding N-formylamides was achieved by reversible encapsulation in a self-assembled hexameric resorcin[4]arene capsule. Encapsulation of a photochromic dithienylethene bis-cation provides different levels of competitive inhibition depending on the geometry assumed by the cationic inhibitor. The Royal Society of Chemistry 2013.
SOME APPROACHES TO THE SYNTHESIS OF FLUORINATED ALCOHOLS AND ESTERS. III. SYNTHESIS OF 2-(F-ALKYL)ETHANOLS FROM 2-(F-ALKYL)-1-IODOETHANES AND AMIDES
Brace, Neal O.
, p. 151 - 174 (1986)
1-iodo-2-(F-alkyl)ethanes, RFCH2CH2I, when heated with a large excess of N-methylformamide (NMF) give in high yield, mixtures of predominately RFCH2CH2OH, some formate ester and a little RFCH=CH2.In a study of this process, significant variables were examined, including solvent, reactant ratio, effect of water, and alternative amide reactants.The coproduct from NMF is the amidine salt, (1+)*I(1-).By contrast, RFCH2CH2I with N,N-dimethylformamide (DMF) and water (one or two mols) gives chiefly the formate ester; the coproduct is Me2NH2(1+)*I(1-).A mechanistic scheme is proposed: in the first step, an alkyl imidate salt, e.g., F>(1+)*I(1-) is formed by O-alkylation of NMF; reaction of the imidate with more NMF gives a tetrahedral intermediate that breaks down rapidly to RFCH2CH2OH, and HC(=NHMe)NMeCHO(1+)*I(1-).The formate ester is derived from the alcohol and this N-formyl acylating agent, in a subsequent step.Analogously, the alkyl imidate salt from DMF and RFCH2CH2I reacts with water as nucleophile (but not with DMF) to give a tetrahedral intermediate that cleaves under stereoelectronic control to formate ester and amine salt, but not to alcohol.Quantitative isolation of amine salt and amidine salt, and observed rates of reaction give solid support to this proposed mechanism.
A substituent- And temperature-controllable NHC-derived zwitterionic catalyst enables CO2upgrading for high-efficiency construction of formamides and benzimidazoles
Li, Hu,Li, Zhengyi,Wu, Hongguo,Yang, Song,Yu, Zhaozhuo,Zhang, Lilong,Zhu, Kaixun
supporting information, p. 5759 - 5765 (2021/08/23)
Chemocatalytic upgrading of the greenhouse gas CO2 to valuable chemicals and biofuels has attracted broad attention in recent years. Among the reported approaches, N-formylation of CO2 with an amine is of great significance due to its versatility in the construction of N-containing linear and cyclic skeletons. Herein, a stable N-heterocyclic carbene-carboxyl adduct (NHC-CO2) was facilely prepared and could be used as a recyclable zwitterionic catalyst for efficient CO2 reductive upgrading via either N-formylation or further coupling with cyclization under mild conditions (25 °C, 1 atm CO2) using hydrosilane as a hydrogen source. More than 30 different alkyl and aromatic amines could be transformed into the corresponding formamides or benzimidazoles with remarkable yields (74%-98%). The electronic effect of the introduced substituent on NHC-CO2 was found to evidently affect the thermostability and nucleophilicity of the zwitterionic catalyst, which is directly correlated with its catalytic activity. Moreover, NHC-CO2 could supply CO2 by in situ decarboxylation at a specific temperature that is dependent on the introduced substituent type. Experimental and computational studies showed that the carboxyl species on NHC-CO2 was not only a nucleophilic center, but also a C1 source which rapidly captures or substitutes ambient CO2 during hydrosilylation. In addition, a simple and green conceptual process was designed for the product purification and catalyst recycling, with a good feasibility for small-scale production.
Sustainable Co-Synthesis of Glycolic Acid, Formamides and Formates from 1,3-Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites
Dai, Xingchao,Adomeit, Sven,Rabeah, Jabor,Kreyenschulte, Carsten,Brückner, Angelika,Wang, Hongli,Shi, Feng
supporting information, p. 5251 - 5255 (2019/03/07)
Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3-dihyroxyacetone (DHA) using a cheap supported Cu/Al2O3 catalyst with single active CuII species. By combining EPR spin-trapping and operando ATR-IR experiments, different mechanisms for the co-synthesis of GA, formates, and formamides have been derived, in which .OH radicals formed from H2O2 by a Fenton-like reaction play a key role.
