- Two-step continuous flow synthesis of amide via oxidative amidation of methylarene
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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.
- Fang, Zheng,Guo, Kai,He, Wei,Liu, Chengkou,Shi, Tingting,Yang, Yuhang,Yang, Zhao,Zhang, Zhimin
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supporting information
(2020/02/28)
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- Copper-catalyzed one-pot oxidative amidation between methylarenes and amines
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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.
- Yang, Yuhang,Gu, Jiajia,Fang, Zheng,Yang, Zhao,Wei, Ping,Guo, Kai
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p. 22797 - 22801
(2017/07/10)
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- Copper-catalyzed one-pot oxidative amidation of alcohol to amide via C-H activation
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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.
- Gu, Jiajia,Fang, Zheng,Yang, Yuhang,Yang, Zhao,Wan, Li,Li, Xin,Wei, Ping,Guo, Kai
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p. 89413 - 89416
(2016/10/03)
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- Iodine-catalyzed efficient amide formation from aldehydes and amines
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An efficient iodine-catalyzed radical oxidative amidation of aldehydes with amines has been developed. This methodology was employed to prepare amides in good to excellent yields with the advantages of wide functional group tolerance and operational simplicity.
- Wang, Peng,Xia, Jiaxuan,Gu, Yueqing
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supporting information
p. 7120 - 7123
(2015/12/01)
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- AIBN-initiated metal free amidation of aldehydes using N-chloroamines
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An efficient and environmentally benign amidation of aldehydes with N-chloroamines has been developed using AIBN as an initiator. This methodology offers a metal free and base free approach and is endowed with mild reaction conditions, high yields, and good functional group tolerance.
- Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
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supporting information
p. 351 - 356
(2014/01/06)
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- Kinetic study of the formation of N-chloro compounds using N-chlorosuccinimide
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Second-order rate constants were determined for the chlorination reaction of 2,2,2-trifluoethylamine and benzylamine with N-chlorosuccinimide at 25 °C and an ionic strength of 0.5 M. These reactions were found to be of first order in both reagents. According to the experimental results, a mechanism reaction was proposed in which a chlorine atom is transferred between both nitrogenous compounds. Kinetics studies demonstrate that the hydrolysis process of the chlorinating agent does not interfere in the chlorination process, under the experimental conditions used in the present work. Free-energy relationships were established using the results obtained in the present work and others available in the literature for chlorination reactions with N-chlorosuccinimide, being the pKa range included between 5.7 and 11.22. Copyright
- Pastoriza, Cristina,Antelo, Juan Manuel,Crugeiras, Juan,Pena-Gallego, Angeles
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supporting information
p. 407 - 418
(2014/05/06)
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- Reactions of chlorination with tert-butyl hypochlorite (TBuOCl)
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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.
- Pastoriza, Cristina,Antelo, Juan Manuel,Crugeiras, Juan
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supporting information
p. 952 - 959
(2015/02/19)
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- Reactions of chlorination with tert-butyl hypochlorite (TBuOCl)
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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.
- Pastoriza, Cristina,Antelo, Juan Manuel,Crugeiras, Juan
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supporting information
p. 952 - 959
(2015/08/25)
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- Cobalt-catalyzed electrophilic amination of arylzincs with N-chloroamines
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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
- Qian, Xin,Yu, Zailu,Auffrant, Audrey,Gosmini, Corinne
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supporting information
p. 6225 - 6229
(2013/07/05)
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- Iron-catalysed oxidative amidation of alcohols with amines
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A new iron-catalysed oxidative amidation of differently substituted benzylic alcohols with mono- and di-substituted amines was developed. The Royal Society of Chemistry 2013.
- Gaspa, Silvia,Porcheddu, Andrea,De Luca, Lidia
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supporting information
p. 3803 - 3807
(2013/07/26)
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- MnO2 promoted sequential C-O and C-N bond formation via C-H activation of methylarenes: A new approach to amides
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A novel and efficient approach for the synthesis of amides has been developed through manganese dioxide promoted nondirected C-H activation of methylarenes under mild reaction conditions employing N-chloroamines as effective coupling partners.
- Vanjari, Rajeshwer,Guntreddi, Tirumaleswararao,Singh, Krishna Nand
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supporting information
p. 4908 - 4911
(2013/10/08)
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- Use of N-chloro-N-methyl-p-toluenesulfonamide in N-chlorination reactions
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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
- Pastoriza, Cristina,Antelo, Juan Manuel,Crugeiras, Juan
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supporting information
p. 551 - 559
(2013/07/26)
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- Kinetic and thermodynamic barriers to chlorine transfer between amines in aqueous solution
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(Chemical Equation Presented) Third-order rate constants for the acid-catalyzed reversible reaction of N-chlorotaurine with benzylamine and dimethylamine were determined in water at 25°C and I = 0.5 (NaClO 4). The reaction with benzylamine shows inverse solvent deuterium isotope effects of kH/kD = 0.57 and 0.47 in the forward and reverse directions, respectively. These isotope effects, together with the absence of detectable general acid catalysis for this reaction, provide evidence for a stepwise mechanism involving fast equilibrium protonation of N-chlorotaurine followed by rate-determining chlorine transfer from the protonated chloramine to benzylamine. The observation of strong catalysis by general acids of the reaction of dimethylamine with N-chlorotaurine suggests a change to a concerted mechanism with proton and chlorine transfer occurring in a single step. This change in mechanism is enforced by the absence of a significant lifetime for protonated chlorotaurine in contact with this strongly nucleophilic amine. The kinetic and thermodynamic parameters for the reaction between protonated chlorotaurine and benzylamine are used to estimate a Marcus intrinsic reaction barrier of ΔG0? = 4.1 kcal/mol for chlorine transfer between amines. Comparison of this intrinsic barrier with those reported previously for bromine transfer between carbanions points to the existence of certain similarities between halogen and proton transfer reactions.
- Calvo, Paula,Crugeiras, Juan,Rios, Ana
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supporting information; experimental part
p. 5381 - 5389
(2009/12/03)
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- Oxidation of benzylamine by CIOH and N-chlorosuccinimide: A kinetic study
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The reaction of benzylamine with N-chlorosuccinimide involves addition of the amine to electrophilic chlorine to yield N-chlorobenzylamine and not hydride abstraction at the α-carbon of the amine by the oxidant as proposed in the literature.
- Antelo,Arce,Crugeiras,Pastoriza,Rios
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- Catalytic asymmetric hydroboration/amination and alkylamination with rhodium complexes of 1,1′-(2-diarylphosphino-1-naphthyl)isoquinoline
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Catecholboronate esters formed by asymmetric hydroboration of arylalkenes are not directly converted to amines by reaction with hydroxylamine-O-sulfonic acid. Prior conversion to a trialkylborane by reaction with ZnEt2 or MeMgCl permits a subsequent amination reaction to occur with essentially complete retention of configuration, leading to a range of primary α-arylalkylamines in up to 97% enantiomeric excess (ee). Secondary, but not tertiary amines may be formed by a related pathway when in situ generated alkylchloramines are employed as the aminating agent. The catalytic asymmetric hydroboration, β-alkylation and amination steps may be combined in a single stage. Overall, this provides a practical procedure for the synthesis of enantiomerically enriched arylamines, exemplified inter alia by the synthesis of (S)-1,2,3,4-tetrahydro-1-naphthylamine in 95-97% ee and of (R)-N-(cyclohexyl)-1′-(4-methoxyphenyl)ethylamine in 93 % ee.
- Fernandez, Elena,Maeda, Kenji,Hooper, Mark W.,Brown, John M.
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p. 1840 - 1846
(2007/10/03)
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- Preparation of esters of phosphorus acids
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Esters of phosphorus acids are prepared by an improved process whereby aromatic alcohols and phosphorus halides are reacted at specified temperatures in the presence of amine catalysts thereby providing high yields of substantially pure esters and allowing preparation of selected halogen-containing mono- and di-esters of phosphorus acids wherein halogen is directly bonded to phosphorus having substantially no side reactant contamination. The phosphorus esters are useful as intermediates in the preparation of plasticizers, oil additives and functional fluids.
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