19733-68-7Relevant articles and documents
Electron-gain and Electron-loss Centres derived from Chloro Amines
Chandra, Harish,Bathgate, Antoinette,Malpass, John R.,Moss, Richard E.,Symons, Martyn C. R.
, p. 1329 - 1332 (1988)
Exposure of dilute solutions of various dialkyl and cyclic N-chloro amines in trichlorofluoromethane to (60)Co γ-rays at 77 K gave the corresponding cations, R2N.Cl, characterised by (14)N, (35)Cl, and (1)H hyperfine coupling.The results suggest that these radicals are essentially planar at nitrogen, the SOMO being the N-Cl ?* orbital.Similar treatment of dilute solutions in methanol or methyltetrahydrofuran gave the corresponding amino radicals, R2N., also characterised by their e.s.r. spectra.There was no evidence for the formation of the parent radical anions.These results are contrasted with those for N-halogeno imides and the formation of ?* radicals from the cations R3N. and halide ions.
Kinetic study of the chlorine transfer from n-chlorosuccinimide to amino compounds
Antelo,Arce,Crugeiras,Parajo
, p. 631 - 636 (1997)
A kinetic study of the reactions of N-chlorosuccinimide (NCS) with glycine (GIy), sarcosine (Sar), 2-methylalanine (2MA), proline (Pro) and pyrrolidine (Pyr) was carried out. The reactions were found to be first order with respect to both NCS and the amine or amino acid and order - 1 in proton concentration. In order to calculate the experimental activation parameters, the effect of temperature on the reaction rates was studied. The ionic strength and buffer concentration were found to have no effect on the rate constant. A reaction mechanism involving Cl+ transfer from NCS to the amine or amino acid to form an N-chloro compound is proposed.
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.
Synthesis and application of novel s-guaiazulene sesquiterpenoid alkaloids
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Paragraph 0084; 0085, (2019/08/06)
The invention belongs to the field of synthetic pharmacochemistry and particularly relates to chemical synthesis and an application of a new framework of s-guaiazulene sesquiterpenoid alkaloids from Muriceides collaris. Muriceidine A is successfully designed and synthesized from s-guaiazulene and piperidine acid as raw materials with a chemical method. In order to verify the universality of the synthesis method, azulene aldehyde is linked with piperidine, methylpiperidine, pyrrole, piperidinemethanol, 4-hydroxypiperidine and other N-heterocycle fragments. Screening of antitumor activity in vitro finds that the IC50 values of structure optimized products 2 and 3 for 14 tumor cell strains including 231, MCF-7, K562, HCT-116, Hela, A549, H1975, HUVEC, MGC-803, SH-SY5Y, HO8910, Siha, PC-3 andBEL7402 are smaller than 10 mu M, and therefore, the new framework of s-guaiazulene sesquiterpenoid alkaloids can be used for research and development of antitumor drugs.
Preparation method of 2-(2,5-difluorophenyl) pyrrolidine
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Paragraph 0037; 0039, (2018/07/30)
The invention provides a preparation method of 2-(2,5-difluorophenyl) pyrrolidine. The preparation method comprises the following steps: (1) tetrahydropyrrole reacts with N-chlorosuccinimide to generate 1-chloropyrrolidine; (2) the 1-chloropyrrolidine generated in the step (1) carries out elimination reaction in sodium methylate solution to generate 3,4-dihydro-2H-pyrrole; (3) the 3,4-dihydro-2H-pyrrole generated in the step (2) reacts with a 2,5-difluorobromobenzene Grignard reagent to obtain the 2-(2,5-difluorophenyl) pyrrolidine. The preparation method of the 2-(2,5-difluorophenyl) pyrrolidine provided by the invention has the beneficial effects that the synthetic process is reasonably designed, the reagent is cheap, the purchase is convenient, no heavy metal pollution is caused, the reaction conditions are mild, the cost of raw materials is low, no special equipment is needed, the operation is simple and convenient, and the energy consumption is low, so that the preparation methodis sutiable for industrial production.
Copper-catalyzed one-pot oxidative amidation between methylarenes and amines
Yang, Yuhang,Gu, Jiajia,Fang, Zheng,Yang, Zhao,Wei, Ping,Guo, Kai
, p. 22797 - 22801 (2017/07/10)
A new method for the direct one-pot oxidative amidation between methylarenes and amines catalyzed by copper has been developed. This method integrates methylarene oxidation and amide bond formation, which are usually accomplished separately, into a single operation. In addition, the reaction provides a relatively high yield and has a wide substrate scope. Moreover, the starting reagents are abundant and available in a convenient way at a cheaper price.
N-Chlorination rate of five-membered heterocyclic nitrogen compounds
Pastoriza, Cristina,Antelo, Juan Manuel,Amoedo, Francisco Andrés,Parajó, Mercedes
, p. 382 - 393 (2016/07/28)
The kinetics of N-chlorination reaction of pyrrolidine, pyrrolidone, succinimide, 5,5,-dimethyloxazolidine-2,4-dione, 5,5-dimethylhydantoin and 1-hydroximethyl-5,5-dimethylhydantoin with HOCl in aqueous solution were studied at 25 °C, constant ionic strength and under isolation conditions in a wide pH range. The set of compounds studied in this paper is characterized by having different functional groups and the same cyclic structure, consisting of a five-member ring with a nitrogen atom in the ring, which is susceptible to be chlorinated. This series of compounds covers nine pKa units, and the kinetic studies allow us to know, like, the presence of an amino, amide or imide group modify the reactivity of nitrogenous compound. Experimental data were fitted to the first-order kinetic equation. All reactions were found to be of first order in both HOCl and nitrogenous compound concentration. Kinetics studies demonstrate that some of these compounds are hydrolyzed in alkaline medium. In each case, reaction mechanism in agreement with the experimental results is proposed. The results were compared with other compounds with similar cyclic structure (2-oxazolidinone and proline). Copyright
Copper-catalyzed one-pot oxidative amidation of alcohol to amide via C-H activation
Gu, Jiajia,Fang, Zheng,Yang, Yuhang,Yang, Zhao,Wan, Li,Li, Xin,Wei, Ping,Guo, Kai
, p. 89413 - 89416 (2016/10/03)
A one-pot oxidative amidation of both aliphatic and aromatic alcohols with N-chloramines, prepared in situ from many types of primary and secondary amines, was developed. This cross-coupling reaction integrates alcohol oxidation and amide bond formation, which are usually accomplished separately, into a single operation. And it was green, simple and convenient, which has a wide substrate scope and makes use of cheap, abundant, and easily available reagents. The practical value of this method is highlighted through the synthesis of a high-profile pharmaceutical agent, acetylprocainamide.
Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines
Qian, Xin,Yu, Zailu,Auffrant, Audrey,Gosmini, Corinne
supporting information, p. 6225 - 6229 (2013/07/05)
Roles reversed: An efficient cobalt-catalyzed electrophilic amination of arylzinc reagents has been achieved. A variety of functionalized arylzincs and N-chloroamines were coupled under mild conditions (see scheme). Both secondary and tertiary arylamines were obtained in moderate to excellent yields. Copyright
