94-69-9Relevant academic research and scientific papers
NMR detection of isomers arising from restricted rotation of the C-N amide bond of N-formyl-o-toluidine and N,N′-bis-formyl-o-tolidine
Quintanilla-Licea, Ramiro,Colunga-Valladares, Juan F.,Caballero-Quintero, Adolfo,Rodriguez-Padilla, Cristina,Tamez-Guerra, Reyes,Gomez-Flores, Ricardo,Waksman, Noemi
, p. 662 - 673 (2002)
Full and unambiguous assignment of all 1H- and 13C-NMR resonances of the isomers due to restricted C-N amide bond rotation of N-formyl-o-toluidine and N,N′-bis-formyl-o-tolidine in DMSO-d6 is reported. The cis-isomer predominates in the equilibrium mixture of both compounds as 1D-NOE difference experiments show.
Method for synthesizing P-chloroO-toluidine
-
Paragraph 0094-0095, (2021/10/05)
The invention discloses a method for synthesizing p-chloroo-toluidine, which comprises the following steps: synthesizing o-toluidine and a protective agent in an organic solvent to obtain an amino-protected intermediate. The amino protected intermediate is added into hydrochloric acid, an oxidant is added for chlorination reaction, and a chlorination product is obtained. The chlorinated product is removed and the amino protecting group is removed to give p-chloroo-toluidine. The method for synthesizing p-chloroo-toluidine provided by the invention is high in yield, simple to operate, less in three wastes, high in product content and good in quality, and can be suitable for industrial mass production.
Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd&at;MCP) for chemoselective N-formylation and N-acylation of amines
Amirsoleimani, Mina,Khalilzadeh, Mohammad A.,Zareyee, Daryoush
, (2020/08/22)
Novel palladium nanoparticles stabilized by clinoptilolite as a natural inexpensive zeolite prepared and used for N-formylation and N-acylation of amines at room temperature at environmentally benign reaction conditions in good to excellent yields. Pd (II) was immobilized on the surface of clinoptilolite via facile multi-step amine functionalization to obtain a sustainable, recoverable, and highly active nano-catalyst. The structural and morphological characterizations of the catalyst carried out using XRD, FT-IR, BET and TEM techniques. Moreover, the catalyst is easily recovered using simple filtration and reused for 7 consecutive runs without any loss in activity.
Copper-Catalyzed Cascade N-Dealkylation/N-Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants
Li, Dianjun,Wang, Shihaozhi,Yang, Jiale,Yang, Jinhui
supporting information, p. 6768 - 6772 (2021/12/31)
A novel tandem N-dealkylation and N-methyl aerobic oxidation of tertiary aromatic amines to N-arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N-methylarylamines to N-arylformamides.
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.
Supported CuII Single-Ion Catalyst for Total Carbon Utilization of C2 and C3 Biomass-Based Platform Molecules in the N-Formylation of Amines
Brückner, Angelika,Dai, Xingchao,Kreyenschulte, Carsten,Rabeah, Jabor,Shi, Feng,Wang, Xinzhi
, p. 16889 - 16895 (2021/09/25)
The shift from fossil carbon sources to renewable ones is vital for developing sustainable chemical processes to produce valuable chemicals. In this work, value-added formamides were synthesized in good yields by the reaction of amines with C2 and C3 biomass-based platform molecules such as glycolic acid, 1,3-dihydroxyacetone and glyceraldehyde. These feedstocks were selectively converted by catalysts based on Cu-containing zeolite 5A through the in situ formation of carbonyl-containing intermediates. To the best of our knowledge, this is the first example in which all the carbon atoms in biomass-based feedstocks could be amidated to produce formamide. Combined catalyst characterization results revealed preferably single CuII sites on the surface of Cu/5A, some of which form small clusters, but without direct linking via oxygen bridges. By combining the results of electron paramagnetic resonance (EPR) spin-trapping, operando attenuated total reflection (ATR) IR spectroscopy and control experiments, it was found that the formation of formamides might involve a HCOOH-like intermediate and .NHPh radicals, in which the selective formation of .OOH radicals might play a key role.
N-Formylation of amines using arylhydrazones of malononitrile and a Cu(II) complex under eco-friendly conditions at room temperature
Nasrollahzadeh, Mahmoud,Bidgoli, Nayyereh Sadat Soheili,Rocha, Bruno G.M.,Pombeiro, Armando J.L.,Mahmudov, Kamran T.
, (2020/08/14)
In this work, we report the synthesis of formamides via solvent free N-formylation of amines using known arylhydrazones of malononitrile including sodium 2-(2-(dicyanomethylene)hydrazinyl)benzenesulfonate (I), 2-(2-(dicyanomethylene)hydrazinyl) benzoic acid (II) and its Cu(II) complex (III) as catalysts at room temperature. These catalysts are highly active and the scope of the method was investigated using several heterocyclic, aromatic and aliphatic amines as substrates, which produced the corresponding formamides in high yields. The remarkable advantages of this method are the elimination of toxic solvents, operational simplicity, easy workup procedure, excellent yields and avoidance of column chromatography.
Copper promoted aerobic oxidative c(sp3)-c(sp3) bond cleavage of n-(2-(pyridin-2-yl)-ethyl)anilines
Yu, Yang,Zhang, Yong,Sun, Chengyu,Shi, Lei,Wang, Wei,Li, Hao
, p. 2725 - 2732 (2020/03/11)
A strategy of aerobic oxidative C(sp3)-C(sp3) bond cleavage of N-ethylaniline derivatives bearing azaarenes for the synthesis of N-aryl formamides has been developed. This approach was carried out smoothly with the CuI/TEMPO/air system to give N-aryl formamides in yields of 50-90%. With this methodology, a mutagenically active compound was constructed in 90% yield. Moreover, the reaction also provided a one-pot synthetic tool for accessing a promoter of hematopoietic stem cells by difunctionalization in 61% yield.
Effective and selective direct aminoformylation of nitroarenes utilizing palladium nanoparticles assisted by fibrous-structured silica nanospheres
Jaseer, E. A.,Qureshi, Ziyauddin S.
, (2020/07/09)
Abstract: Palladium nanoparticles (~ 1–3?nm, 0.4?wtpercent Pd) were uniformly distributed over the surface of fibrous silica nanospheres (KCC-1) modified via aminopropyltriethoxysilane using a fast and cost-effective palladium (II) chloride reduction process. The Pd nanoparticles (Pd NPs) distribution over the ensuing catalyst Pd/KCC-1-NH2 showed much more uniform distribution, and smaller size compared with the tedious hydrothermal reduction method. The morphological, chemical, and size analyses of Pd/KCC-1-NH2 by BET, UV–Vis spectra, XRD, HR-TEM, EDS and XPS analysis revealed that the succeeding material consist of a distinct fibrous silica nanospheres support adorn with Pd NPs. The resultant nanocatalyst was tested for the one-step reductive aminoformylation of aromatic nitro compounds using formic acid. A wide range of substituted nitroarenes including electron withdrawing, releasing, sterically hindered and multifunctional groups have been converted to corresponding aryl formamide in quantitative yields (yields up to 98percent) at moderate temperature (70?°C). Optimization study has proved that the 6 equivalent of formic acid is required and toluene was found to be the better solvent. The established practice is beneficial due to the use of formic acid as H2 source and formylating agent, easiness in handling of the catalyst and simple workup procedure with efficient catalyst reusability. Graphic abstract: [Figure not available: see fulltext.].
A Practical Approach for the Transamidation of N, N-Dimethyl Amides with Primary Amines Promoted by Sodium tert-Butoxide under Solvent-Free Conditions
Zhang, Rui,Zhang, Jun-Chao,Zhang, Wei-Yi,He, Yu-Qing,Cheng, Hua,Chen, Cheng,Gu, Yu-Cheng
, p. 3286 - 3294 (2020/09/23)
A practical sodium tert-butoxide (NaO t Bu)-mediated protocol is disclosed for the transamidation of various N, N-dimethyl amides with primary amines to afford the corresponding amides in moderate to good yields at room temperature under solvent-free conditions. This protocol features a facile work-up procedure and good functional group compatibility, especially for N, N-dimethyl amides with long-chain alkyl groups and heteroatom-containing amines. Notably, a few representative gram-scale reactions proceed smoothly to furnish the desired amides in high yields, which demonstrates the potential of this process for further practical applications. Several control experiments are carried out and a plausible mechanism is provided.
