10017-37-5Relevant articles and documents
Conversion of Aliphatic Amides into Amines with benzene. Scope of the Reaction
Loudon, G. Marc,Radhakrishna, A. S.,Almond, Merrick R.,Blodgett, James K.,Boutin, Raymond H.
, p. 4272 - 4276 (1984)
The reagent benzene, PIFA, brings about the facile oxidative rearrangement of aliphatic amides to amines in mildly acidic (pH 1-3) mixed aqueous-organic solvents.Aromatic amines are further oxidized by the reagent and therefore cannot be prepared by this method.The rearrangement, which is in effect an "Hofmann rearrangement", occurs with complete retention of configuration in the migrating group, and the rate of the reaction follows approximately the migratory aptitudes of the migrating groups determined for other similar reactions.Isocyanates are intermediates in the rearrangement but are rapidly hydrolyzed to the product amines under the mildly acidic conditions.The acidic conditions protect the product amines from reacting with the isocyanate intermediates and forming ureas.The reaction is accelerated by addition of pyridine to a pH of approximately 3.The scope of the reaction is discussed.
Direct Preparation of Amides from Amine Hydrochloride Salts and Orthoesters: A Synthetic and Mechanistic Perspective
Di Grandi, Martin J.,Bennett, Caitlin,Cagino, Kristen,Muccini, Arnold,Suraci, Corey,Saba, Shahrokh
, p. 2601 - 2607 (2015)
The conversion of a wide range of primary and secondary aliphatic and a few arylamine hydrochloride salts to their corresponding acetamides with trimethyl orthoacetate is described. Mechanistic studies using NMR and gas chromatography-mass spectrometry techniques indicate these reactions proceed via an O-methylimidate intermediate that undergoes in situ demethylation by chloride, affording the corresponding acetamides. Synthetically, this reaction represents a practical, high-yielding protocol with a simple workup for the rapid conversion of amine hydrochloride salts to acetamides.
Hydrazine-mediated reduction of nitro and azide functionalities catalyzed by highly active and reusable magnetic iron oxide nanocrystals
Cantillo, David,Moghaddam, Mojtaba Mirhosseini,Kappe, C. Oliver
, p. 4530 - 4542 (2013)
Iron oxide (Fe3O4) nanocrystals generated in situ from an inexpensive and readily available iron source catalyze the reduction of nitroarenes to anilines with unparalleled efficiency. The procedure is chemoselective, avoids the use of precious metals, and can be applied under mild reflux conditions (65 or 80 C) or using sealed vessel microwave heating in an elevated temperature regime (150 C). Utilizing microwave conditions, a variety of functionalized anilines have been prepared in nearly quantitative yields within 2-8 min at 150 C, in a procedure also successfully applied to the reduction of aliphatic nitro compounds and azides. The iron oxide nanoparticles are generated in a colloidal form, resulting in homogeneous solutions suitable for continuous flow processing. Selected examples of anilines of industrial importance have been prepared in a continuous regime using this protocol.
Preventing thermolysis: Precursor design for volatile copper compounds
Coyle, Jason P.,Kurek, Agnieszka,Pallister, Peter J.,Sirianni, Eric R.,Yap, Glenn P. A.,Barry, Sean T.
, p. 10440 - 10442 (2012)
A copper(i) iminopyrrolidinate was synthesized and evaluated by thermal gravimetric analysis (TGA), solution based 1H NMR studies and surface chemistry to determine its thermal stability and decomposition mechanism. Copper(i) tert-butyl-imino-2
Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
supporting information, p. 1618 - 1629 (2021/01/25)
Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
Green method for catalyzing reduction reaction of aliphatic nitro derivative
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Paragraph 0005-0006; 0037-0040, (2021/07/31)
The invention relates to a green method for catalyzing reduction reaction of aliphatic nitro derivatives. According to the method, non-transition metal compounds, namely triethyl boron and potassium tert-butoxide, are used as a catalytic system for the first time, an aliphatic nitro derivative and pinacolborane which is low in price and easy to obtain are catalyzed to be subjected to a reduction reaction under mild conditions, and an aliphatic amine hydrochloride product is synthesized after acidification with a hydrochloric acid aqueous solution. Compared with a traditional method, the method generally has the advantages that the catalyst is cheap and easy to obtain, operation is convenient, and reaction is safe. The selective reduction reaction of the aliphatic nitro derivative catalyzed by the non-transition metal catalyst and pinacol borane is realized for the first time, and the aliphatic amine hydrochloride product is synthesized through acidification treatment of the hydrochloric acid aqueous solution, so that a practical new reaction strategy is provided for laboratory preparation or industrial production.
A catalytic version of hypervalent aryl-λ3-iodane-induced Hofmann rearrangement of primary carboxamides: Iodobenzene as an organocatalyst and m-chloroperbenzoic acid as a terminal oxidant
Miyamoto, Kazunori,Sakai, Yuuta,Goda, Shunsuke,Ochiai, Masahito
supporting information; experimental part, p. 982 - 984 (2012/02/04)
The first catalytic version of hypervalent aryl-λ3- iodane-induced Hofmann rearrangement of primary carboxamides, which probably involves in situ generation of a tetracoordinated bis(aqua)(hydroxy)phenyl- λ3-iodane complex as an active oxidant from a catalytic amount of iodobenzene by the reaction with m-chloroperbenzoic acid in the presence of HBF4 in dichloromethane-water under mild conditions, was developed.
General multicomponent strategy for the synthesis of 2-Amino-l,4- diazaheterocycles: Scope, limitations, and utility
Kysil, Volodymyr,Khvat, Alexander,Tsirulnikov, Sergey,Tkachenko, Sergey,Williams, Caroline,Churakova, Marina,Ivachtchenko, Alexandre
experimental part, p. 1525 - 1543 (2010/06/16)
Multicomponent reactions of primary 1,2- and 1,3-diamines with carbonyl compounds and isocyanides resulting in the formation of diverse 2-amino-l,4-diazaheterocycles are described. Lewis acids (LAs) promote the reactions effectively, and chlorotrimethylsi
Synthesis of indolylindolines mediated by t-BuNH2
Suarez-Castillo, Oscar R.,Melendez-Rodriguez, Myriam,Morales-Garcia, Ana L.,Cano-Escudero, Indira C.,Contreras-Martinez, Yaneth M.A.,Morales-Rios, Martha S.,Joseph-Nathan, Pedro
experimental part, p. 1463 - 1476 (2009/12/24)
An improved synthesis of N1-carbomethoxylated indolylindolines 2 from 5-substituted indoles 1, by replacing the previously employed strong acids or toxic metals with t-BuNH2/MeOCOCl in CH2Cl2/H2O, is described.
Process for the production and purification of bis(tertiary-butylamino)silane
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Page 4, (2008/06/13)
A process for synthesizing an aminosilane compound such as bis(tertiarybutylamino)silane is provided. In one aspect of the present invention, there is provided a process for making bis(tertiarybutylamino)silane comprising reacting a stoichiometric excess
