T:Toxic;
127-19-5Relevant articles and documents
Lewis Acidic Boranes, Lewis Bases, and Equilibrium Constants: A Reliable Scaffold for a Quantitative Lewis Acidity/Basicity Scale
Mayer, Robert J.,Hampel, Nathalie,Ofial, Armin R.
supporting information, p. 4070 - 4080 (2021/01/29)
A quantitative Lewis acidity/basicity scale toward boron-centered Lewis acids has been developed based on a set of 90 experimental equilibrium constants for the reactions of triarylboranes with various O-, N-, S-, and P-centered Lewis bases in dichloromethane at 20 °C. Analysis with the linear free energy relationship log KB=LAB+LBB allows equilibrium constants, KB, to be calculated for any type of borane/Lewis base combination through the sum of two descriptors, one for Lewis acidity (LAB) and one for Lewis basicity (LBB). The resulting Lewis acidity/basicity scale is independent of fixed reference acids/bases and valid for various types of trivalent boron-centered Lewis acids. It is demonstrated that the newly developed Lewis acidity/basicity scale is easily extendable through linear relationships with quantum-chemically calculated or common physical–organic descriptors and known thermodynamic data (ΔH (Formula presented.)). Furthermore, this experimental platform can be utilized for the rational development of borane-catalyzed reactions.
PRODUCTION METHOD OF N,N-DIMETHYLAMIDE
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Paragraph 0037-0042; 0046-0054, (2020/08/26)
PROBLEM TO BE SOLVED: To provide a production method with which N,N-dimethylamide can be produced by making a nitrile and methanol react with each other in gas phase. SOLUTION: A production method of N,N-dimethylamide for producing N,N-dimethylamide by making a nitrile and methanol react with each other in gas phase in the presence of a catalyst is disclosed, in which the nitrile is acetonitrile or propionitrile and the catalyst is an alloy containing copper and aluminum. Preferably acetonitrile is used as the nitrile. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
METHOD FOR PRODUCING N,N-DISUBSTITUTED AMIDE AND CATALYST FOR PRODUCING N,N-DISUBSTITUTED AMIDE
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Page/Page column 0055-0079, (2020/04/01)
To provide a method for producing an N, N-disubstituted amide in which an N,N-disubstituted amide can be obtained by a reaction of a nitrile and an alcohol even by a liquid phase reaction and a gas phase reaction and the object product obtained after the reaction and a catalyst can be easily separated.SOLUTION: There is provided a method for producing an N,N-disubstituted amide by reacting a nitrile and an alcohol in the presence of a catalyst, wherein the catalyst is a heterogeneous catalyst composed of a carrier and a metal oxide carried on the carrier, the carrier is at least one selected from zeolite, silica and alumina and a metal included in the metal oxide includes at least one selected from copper and molybdenum.SELECTED DRAWING: None
A scalable continuous photochemical process for the generation of aminopropylsulfones
Baumann, Marcus,Bonciolini, Stefano,Di Filippo, Mara
supporting information, p. 9428 - 9432 (2020/12/15)
An efficient continuous photochemical process is presented that delivers a series of novel γ-aminopropylsulfones via a tetrabutylammonium decatungstate (TBADT) catalysed HAT-process. Crucial to this success is the exploitation of a new high-power LED emitting at 365 nm that was found to be superior to an alternative medium-pressure Hg lamp. The resulting flow process enabled the scale-up of this transformation reaching throughputs of 20 mmol h-1 at substrate concentrations up to 500 mM. Additionally, the substrate scope of this transformation was evaluated demonstrating the straightforward incorporation of different amine substituents as well as alkyl appendages next to the sulfone moiety. It is anticipated that this methodology will allow for further exploitations of these underrepresented γ-aminopropylsulfone scaffolds in the future. This journal is
Synthesis of acetamides using CO2, methanol, H2 and amines
Zhang, Jingjing,Qian, Qingli,Wang, Ying,Asare Bediako, Bernard Baffour,Cui, Meng,Yang, Guanying,Han, Buxing
supporting information, p. 233 - 237 (2019/01/28)
Herein, we report the synthesis of acetamides from CO2, methanol, H2 and corresponding amines, which is a new route used to synthesize acetamides. It was found that the Rh catalyst with LiI/LiCl as promoters could effectively catalyze this reaction. Interestingly, no ligand was required and amine substrates played a role in accelerating the reaction.
Formation of carbon–nitrogen bonds in carbon monoxide electrolysis
Jouny, Matthew,Lv, Jing-Jing,Cheng, Tao,Ko, Byung Hee,Zhu, Jun-Jie,Goddard, William A.,Jiao, Feng
, p. 846 - 851 (2019/09/03)
The electroreduction of CO2 is a promising technology for carbon utilization. Although electrolysis of CO2 or CO2-derived CO can generate important industrial multicarbon feedstocks such as ethylene, ethanol, n-propanol and acetate, most efforts have been devoted to promoting C–C bond formation. Here, we demonstrate that C–N bonds can be formed through co-electrolysis of CO and NH3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH3 to a surface-bound ketene intermediate, a step that is in competition with OH– addition, which leads to acetate. The C–N formation mechanism was successfully extended to a series of amide products through amine nucleophilic attack on the ketene intermediate. This strategy enables us to form carbon–heteroatom bonds through the electroreduction of CO, expanding the scope of products available from CO2 reduction.
Ozone and ozone/vacuum-UV degradation of diethyl dithiocarbamate collector: Kinetics, mineralization, byproducts and pathways
Fu, Pingfeng,Ma, Yanhong,Yang, Huifen,Li, Gen,Lin, Xiaofeng
, p. 23579 - 23588 (2019/08/12)
The diethyl dithiocarbamate (DDC) collector, a precursor of toxic N-nitrosamines, is detected in flotation wastewaters usually at the ppm level. In this study, the O3 and O3/Vacuum-UV (O3/VUV) processes were compared to investigate the efficient removal of DDC with a low risk of N-nitrosamine formation. The results showed that 99.55% of DDC was removed at 20 min by O3/VUV, and the degradation rate constant was 3.99 times higher than that using O3-alone. The C, S and N mineralization extents of DDC using O3/VUV reached 36.36%, 62.69% and 79.76% at 90 min, respectively. O3/VUV achieved a much higher mineralization extent of DDC than O3-alone. After 90 min of degradation, O3/VUV achieved lower residual concentrations of CS2 and H2S, and released lower amounts of gaseous sulfur byproducts compared to O3-alone. The solid phase extraction and gas chromatography-mass spectrometry (SPE/GC-MS) analysis indicated that the main byproducts in O3/VUV degradation of DDC were amide compounds without the detection of N-nitrosamines. The avoidance of N-nitrosamine formation might be attributed to exposure of UV irradiation and enhanced formation of OH radicals in the O3/VUV system. The degradation pathways of DDC were proposed. This work indicated that O3/VUV was an efficient alternative treatment technique for the removal of DDC flotation collector with low risk of N-nitrosamine formation.
Direct Observation of Acyl Nitroso Compounds in Aqueous Solution and the Kinetics of Their Reactions with Amines, Thiols, and Hydroxamic Acids
Maimon, Eric,Lerner, Ana,Samuni, Amram,Goldstein, Sara
, p. 7006 - 7013 (2018/09/06)
Acyl nitroso compounds or nitrosocarhonyls (RC(O)N=O) are reactive short-lived electrophiles, and their hydrolysis and reactions with nucleophiles produce HNO. Previously, direct detection of acyl nitroso species in nonaqueous media has been provided by time-resolved infrared spectroscopy demonstrating that its half-life is about 1 ms. In the present study hydroxamic acids (RC(O)NHOH) are oxidized electrochemically in buffered aqueous solutions (pH 5.9-10.2) yielding transient species characterized by their maximal absorption at 314-330 nm. These transient species decompose via a first-order reaction yielding mainly HNO and the respective carboxylic acid and therefore are ascribed to RC(O)N=O. The sufficiently long half-life of RC(O)N=O in aqueous solution allows for the first time the study of the kinetics of its reactions with various nucleophiles demonstrating that the nucleophilic reactivity follows the order thiolate > hydroxamate > amine. Metal chelates of CH3C(O)NHOH catalyze the hydrolysis of CH3C(O)N=O at the efficacy order of CuII > ZnII > NiII > CoII where only CuII catalyzes the hydrolysis also in the absence of the hydroxamate. Finally, oxidation of hydroxamic acids generates HNO, and the rate of this process is determined by the half-life of the respective acyl nitroso compound.
Cu(II)-Mediated keto C(sp3)-H bond α-acyloxylation of N, N-dialkylamides with aromatic carboxylic acids
Li, Wenjing,Yin, Changzhen,Yang, Xiao,Liu, Hailong,Zheng, Xueli,Yuan, Maolin,Li, Ruixiang,Fu, Haiyan,Chen, Hua
supporting information, p. 7594 - 7599 (2017/09/27)
The selective oxidative coupling of aromatic carboxylic acids with the C(sp3)-H bond adjacent to the keto group of alkylamides has been developed by employing a low cost copper source. This provides an efficient approach for synthesis of O-benzoylglycolamides. The protocol displayed good functional group tolerance. A broad range of benzoic acids directly coupled with alkylamides to afford a variety of O-benzoylglycolamides in moderate to good yields. In addition, a reasonable radical mechanism was proposed based on EPR experiments.
Process for synthesizing N,N-dimethylacetamide
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Paragraph 0008, (2017/09/01)
The invention discloses a process for synthesizing N,N-dimethylacetamide. The N,N-dimethylacetamide is prepared through operation means of ultrasonic oscillation, magnetic stirring and infrared treatment of the raw materials such as dimethylamine, acetylchloride, a home-made zirconium-modified nanoscale solid alkali catalyst.
