1585-74-6Relevant articles and documents
Use of N-chloro-N-methyl-p-toluenesulfonamide in N-chlorination reactions
Pastoriza, Cristina,Antelo, Juan Manuel,Crugeiras, Juan
, p. 551 - 559 (2013)
Second-order rate constants (k2) were determined for the addition of ten nitrogenous organic compounds (benzylamine, 2,2,2- trifluoethylamine chlorhidrate, methylamine chlorhidrate, glycine ethyl ester chlorhidrate, glycine, glycylglycine chlorhidrate, morpholine, pyperidine, pyperazine and dimethylamine) to the N-chloro-N-methyl-p-toluenesulfonamide (NCNMPT) in the formation reaction of N-chloramines in aqueous solution at 25 °C and ionic strength 0.5 M. The series of nucleophiles considered is structurally very varied and covers five pKa units. The kinetic behaviour is similar for all compounds, being the elementary step the transfer of chlorine from the NCNMPT molecule to the nitrogen of the free amino group. These reactions were found first order in both reagents. The values of the rate constants indicate that the more basic amines produce N-chloramines more readily. Rate constants for the nucleophilic attack are shown to correlate with literature data for some of these nitrogenous organic compounds in their reaction with N-methyl-N-nitroso-p-toluenesulfonamide. Both reactions involve that the rate determining step is the attack of nitrogenous compounds upon electrophilic centre (Cl or else NO group). NCNMPT is a particularly interesting substrate, for which has not hitherto been published kinetic information, that allows us to assess the efficiency and the competitiveness of this reaction and compare it with other agents with a Cl+ atom. Copyright 2013 John Wiley & Sons, Ltd. N-chloro-N-methyl-p-toluensulfonamide is a particularly chlorinating agent. The kinetic behaviour has been studied in the formation reaction of N-chloramines using ten nitrogenous compounds. Copyright
Infrared and Raman Spectra, Vibrational Assignment, Normal Coordinate Analysis, and Barrier to Internal Rotation of N-Chloro-N-methylmethanamine
Durig, J. R.,Lindsay, N. E.,Hizer, T. J.
, p. 5027 - 5035 (1987)
The infrared (3200-80 cm-1) and Raman (3200-10 cm-1) spectra have been recorded of gaseous and solid N-chloro-N-methylmethanamine (dimethylchloroamine), (CH3)2NCl, and the corresponding deuterium molecules, CH3(CD3)NCl and (CD3)2NCl.Additionally, the Raman spectra of the liquids have been recorded and qualitative depolarization values have been obtained.A complete vibrational assignment is proposed, based on the infrared band contours, Raman depolarization values, group frequencies, and isotopic shifts.The assignment is supported by a normal coordinate analysis which was carried out by utilizing a modified valence force field to calculate the frequencies and the potential energy distribution.The A' and A" methyl torsional fundamentals were observed in the infrared spectrum in the gas phase of the d0 molecule at 281 and 261 cm-1, respectively, from which the threefold barrier to internal rotation is calculated to be 1658 cm-1 (4.74 kcal/mol).From the number of lattice modes observed in the Raman spectrum of the solid, it is concluded that there are at least two molecules per permitive cell.All of these results are compared to similar quantities of some corresponding molecules.
Oxidation of aliphatic amines by aqueous chlorine
Abia,Armesto,Canle L.,Garcia,Santaballa
, p. 521 - 530 (1998)
The oxidation of aliphatic amines by aqueous chlorine has been studied. The kinetic behaviour is similar for primary, secondary and tertiary aliphatic amines the elementary stop being the transfer of chlorine from the hypochlorous acid molecule to the nitrogen of the free amine group. Chlorination of aliphatic primary and secondary amines involves some water molecules in the transition state. Inductive effects are also discussed.
Allenstein
, p. 3 (1961)
Two-step continuous flow synthesis of amide via oxidative amidation of methylarene
Fang, Zheng,Guo, Kai,He, Wei,Liu, Chengkou,Shi, Tingting,Yang, Yuhang,Yang, Zhao,Zhang, Zhimin
supporting information, (2020/02/28)
A green and efficient method for the synthesis of amides has been developed through oxidative amidation between methylarenes with amines in a two-step continuous flow system. This method integrates methylarene oxidation and amide formation into a single operation which is usually accomplished separately. Oxidation with tert-butyl hydroperoxide (TBHP) as “green” oxidant, the synthesis of amides under mild reaction conditions in continuous flow system and the utilization of methylarenes as starting material make this methodology novel and environment friendly. The practical value of this method is highlighted through the synthesis of high-profile pharmaceutical agents, acetylprocainamide.
Practical and regioselective amination of arenes using alkyl amines
Ruffoni, Alessandro,Juliá, Fabio,Svejstrup, Thomas D.,McMillan, Alastair J.,Douglas, James J.,Leonori, Daniele
, p. 426 - 433 (2019/05/01)
The formation of carbon–nitrogen bonds for the preparation of aromatic amines is among the top five reactions carried out globally for the production of high-value materials, ranging from from bulk chemicals to pharmaceuticals and polymers. As a result of this ubiquity and diversity, methods for their preparation impact the full spectrum of chemical syntheses in academia and industry. In general, these molecules are assembled through the stepwise introduction of a reactivity handle in place of an aromatic C–H bond (that is, a nitro group, halogen or boronic acid) and a subsequent functionalization or cross-coupling. Here we show that aromatic amines can be constructed by direct reaction of arenes and alkyl amines using photocatalysis, without the need for pre-functionalization. The process enables the easy preparation of advanced building blocks, tolerates a broad range of functionalities, and multigram scale can be achieved via a batch-to-flow protocol. The merit of this strategy as a late-stage functionalization platform has been demonstrated by the modification of several drugs, agrochemicals, peptides, chiral catalysts, polymers and organometallic complexes.
Reactions of chlorination with tert-butyl hypochlorite (TBuOCl)
Pastoriza, Cristina,Antelo, Juan Manuel,Crugeiras, Juan
supporting information, p. 952 - 959 (2015/08/25)
The chlorination reactions of nitrogenous organic compounds (2,2,2-trifluoroethylamine, benzylamine, glycine, and dimethylamine) by tert-butyl hypochlorite (tBuOCl) were studied at 25°C, ionic strength 0.5 M and under isolation conditions. The kinetic results obtained in the formation processes of the corresponding N-chloramines in acid medium (pH = 5-7) are summarized in this paper. Kinetic studies showed a first order with respect to tBuOCl concentration. The chlorination reactions involving benzylamine, glycine and dimethylamine were all first order with respect to nitrogenous compound concentration and approximately -1 order with respect to proton concentration. The reaction with 2,2,2-trifluoroethylamine was more complex, and the order of reaction with respect to the amine varied with pH.
