cas 698-00-0, 2-BROMO-N,N-DIMETHYLANILINE | Articles data

Articles about 698-00-0Total 26 be found

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Mesoionic N-heterocyclic olefin catalysed reductive functionalization of CO2for consecutiveN-methylation of amines
A mesoionic N-heterocyclic olefin (mNHO) was introduced as a metal-free catalyst for the reductive functionalization of CO2leading to consecutive doubleN-methylation of primary amines in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN). A wide range of secondary amines and primary amines were successfully methylated under mild conditions. The catalyst sustained over six successive cycles ofN-methylation of secondary amines without compromising its activity, which encouraged us to check its efficacy towards doubleN-methylation of primary amines. Moreover, this method was utilized for the synthesis of two commercially available drug molecules. A detailed mechanistic cycle was proposed by performing a series of control reactions along with the successful characterisation of active catalytic intermediates either by single-crystal X-ray study or by NMR spectroscopic studies in association with DFT calculations.
Das, Arpan,Maji, Subir,Mandal, Swadhin K.
p. 12174 - 12180
(2021/09/28)

Dirhodium-Catalyzed Chemo-and Site-Selective C-H Amidation of N, N-Dialkylanilines
A method for dirhodium-catalyzed C(sp 3)-H amidation of N, N-dimethylanilines was developed. Chemoselective C(sp 3)-H amidation of N-methyl group proceeded exclusively in the presence of C(sp 2)-H bonds of the electron-rich aromatic ring. Site-selective C(sp 3)-H amidation proceeded exclusively at the N-methyl group of N-methyl-N-Alkylaniline derivatives with secondary, tertiary, and benzylic C(sp 3)-H bonds α to a nitrogen atom.
Chen, Gong,Arai, Kenta,Morisaki, Kazuhiro,Kawabata, Takeo,Ueda, Yoshihiro
supporting information
p. 728 - 732
(2021/01/18)

Synergistic catalysis of Cu+/Cu0 for efficient and selective N-methylation of nitroarenes with para-formaldehyde
In this paper, an inexpensive heterogeneous copper nanoparticles catalyst derived from CuAl-layered double hydroxide via an in situ topotactic transformation process was developed. Cu nanoparticles with uniform size were homogeneously dispersed on amorphous Al2O3 with strong metal-support interaction. Characterization results reveals that the Cu0 and Cu+ were simultaneously formed with Cu+ species as the dominant sites on the surface during the reduction process. The resultant catalyst Cu/Al2O3 demonstrates high catalytic activity, selectivity and durability for the reductive N-methylation of easily available nitroarenes in a cost-efficient, environmentally friendly and cascade manner. A broad spectrum of nitroarenes could be efficiently N-methylated to their corresponding N,N-dimethyl amines with good compatibility of various functional groups. The protocol is also applicable for the late-stage functionalization of biologically and pharmaceutically active nitro molecules. A structure-function relationship discloses that Cu0 and Cu+ sites on the surface pronouncedly boosts the reaction efficiency in a synergistic manner, in which Cu0 could facilitate H2 production and N-methylation of anilines, while Cu+ is considerably more active and participates in the overall process of the selective N-methylation of nitroarenes. Moreover, the catalyst also showed a strong stability and could be easily separated for successive reuses without an appreciable loss in activity and selectivity.
Dong, Xiaosu,Wang, Zhaozhan,Yuan, Youzhu,Yang, Yong
p. 304 - 313
(2019/07/02)

Atom-Economic Electron Donors for Photobiocatalytic Halogenations
In vitro cofactor supply and regeneration have been a major obstacle for biocatalytic processes, in particular on a large scale. Peroxidases often suffer from inactivation by their oxidative co-factor. Combining photocatalysis and biocatalysis offers an innovative solution to this problem, but lacks atom economy due to the sacrificial electron donors needed. Herein, we show that redox-active buffers or even water alone can serve as efficient, biocompatible electron sources, when combined with photocatalysis. Mechanistic investigations revealed first insights into the possibilities and limitations of this approach and allowed adjusting the reaction conditions to the specific needs of biocatalytic transformations. Proof-of-concept for the applicability of this photobiocatalytic reaction setup was given by enzymatic halogenations.
Seel, Catharina Julia,Králík, Antonín,Hacker, Melanie,Frank, Annika,K?nig, Burkhard,Gulder, Tanja
p. 3960 - 3963
(2018/09/25)

Expedient Synthesis of N-Methyl- and N-Alkylamines by Reductive Amination using Reusable Cobalt Oxide Nanoparticles
N-Methyl- and N-alkylamines represent important fine and bulk chemicals that are extensively used in both academic research and industrial production. Notably, these structural motifs are found in a large number of life-science molecules and play vital roles in regulating their activities. Therefore, the development of convenient and cost-effective methods for the synthesis and functionalization of amines by using earth-abundant metal-based catalysts is of scientific interest. In this regard, herein we report an expedient reductive amination process for the selective synthesis of N-methylated and N-alkylated amines by using nitrogen-doped, graphene-activated nanoscale Co3O4-based catalysts. Starting from inexpensive and easily accessible nitroarenes or amines and aqueous formaldehyde or aldehydes in the presence of formic acid, this cost-efficient reductive amination protocol allows the synthesis of various N-methyl- and N-alkylamines, amino acid derivatives, and existing drug molecules.
Senthamarai, Thirusangumurugan,Murugesan, Kathiravan,Natte, Kishore,Kalevaru, Narayana V.,Neumann, Helfried,Kamer, Paul C. J.,Jagadeesh, Rajenahally V.
p. 1235 - 1240
(2018/02/09)

2-[(2-dimethylaminophenyl)(phenyl)phosphino]-N,N-dimethylaniline copper iodide complex and synthesis method thereof
The invention relates to a 2-[(2-dimethylaminophenyl)(phenyl)phosphino]-N,N-dimethylaniline copper iodide complex and a synthesis method and the application thereof. The synthesis method comprises thefollowing steps: firstly, enabling 2-bromoaniline and m
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Paragraph 0011-0012; 0034-0036; 0038

(2018/10/11)

Gold-Catalyzed Reductive Transformation of Nitro Compounds Using Formic Acid: Mild, Efficient, and Versatile
Developing new efficient catalytic systems to convert abundant and renewable feedstocks into valuable products in a compact, flexible, and target-specific manner is of high importance in modern synthetic chemistry. Here, we describe a versatile set of mild catalytic conditions utilizing a single gold-based solid catalyst that enables the direct and additive-free preparation of four distinct and important amine derivatives (amines, formamides, benzimidazoles, and dimethlyated amines) from readily available formic acid (FA) and nitro starting materials with high level of chemoselectivity. By controlling the stoichiometry of the employed FA, which has attracted considerable interest in the area of sustainable chemistry because of its potential as an entirely renewable hydrogen carrier and as a versatile C1 source, a facile atom- and step-efficient transformation of nitro compounds can be realized in a modular fashion. Renewable formic acid as a flexible feedstock: A versatile heterogeneous gold-based catalytic system has been developed for the controlled, flexible, and target-specific reductive transformation of nitro compounds using stoichiometric equivalents of formic acid as a key starting material under mild and convenient conditions. The overall operational simplicity, high chemoselectivity, functional-group tolerance, and reusability of the catalyst make this approach an attractive and reliable tool for organic and process chemists.
Yu, Lei,Zhang, Qi,Li, Shu-Shuang,Huang, Jun,Liu, Yong-Mei,He, He-Yong,Cao, Yong
p. 3029 - 3035
(2015/09/28)

Sono-bromination of aromatic compounds based on the ultrasonic advanced oxidation processes
A novel, mild "sono-halogenation" of various aromatic compounds with potassium halide was investigated under ultrasound in a biphasic carbon tetrachloride/water medium. The feasibility study was first undertaken with the potassium bromide and then extended to chloride and iodide analogues. This methodology could be considered as a new expansion of the ultrasonic advanced oxidation processes (UAOPs) into a synthetic aspect as the developed methodology is linked to the sonolytic disappearance of carbon tetrachloride. Advantages of the present method are not only that the manipulation of the bromination is simple and green, but also that the halogenating agents used are readily available, inexpensive, and easy-handling.
Fujita, Mitsue,Lévêque, Jean-Marc,Komatsu, Naoki,Kimura, Takahide
p. 247 - 251
(2015/06/08)

Direct oxidative cyanation of tertiary amines promoted by in situ generated hypervalent iodine(III)-CN intermediate
An environmentally benign and metal-free cyanation method of tertiary amines oxidated by hypervalent iodine(III) intermediate generated in situ from PIFA (or DIB) and TMSCN has been developed. A variety of substituent groups on amines are tolerated to the oxidation of α-C-H bond to form C-C bond in the absence of metal catalysts with yields of up to 74%.
Shen, Hang,Zhang, Xiaohui,Liu, Qing,Pan, Jing,Hu, Wen,Xiong, Yan,Zhu, Xiangming
supporting information
p. 5628 - 5631
(2015/09/21)

Metal-free protodeboronation of electron-rich arene boronic acids and its application to ortho -functionalization of electron-rich arenes using a boronic acid as a blocking group
The metal-free thermal protodeboronation of various electron-rich arene boronic acids was studied. Several reaction parameters controlling this protodeboronation, such as solvent, temperature, and a proton source, have been investigated. On the basis of these studies, suitable reaction conditions for protodeboronation of several types of electron-rich arene boronic acids were provided. On the basis of this protodeboronation, a new protocol for the synthesis of ortho-functionalized electron-rich arenes from these boronic acids was developed using the boronic acid moiety as a blocking group in the electrophilic aromatic substitution reaction, followed by the removal of the boronic acid moiety via thermal protodeboronation. Mechanistic studies suggested that this protodeboronation might proceed via the complex formation of a boronic acid with a proton source, followed by the carbon-boron bond fission through σ-bond metathesis, to afford the corresponding arene compound and boric acid.
Ahn, Su-Jin,Lee, Chun-Young,Kim, Nak-Kyoon,Cheon, Cheol-Hong
p. 7277 - 7285
(2014/11/27)

Metal-free functionalization of N, N-dialkylanilines via temporary oxidation to N, N-dialkylaniline N-oxides and group transfer
A simple set of protocols for the controlled elaboration of anilines is reported allowing access to a diverse array of aminophenols, aminoarylsulfonates, alkylated anilines, and aminoanilines in 29-95% yield in a single laboratory operation from easily isolable, bench-stable N,N-dialkylaniline N-oxides. The introduction of new C-O, C-C, and C-N bonds on the aromatic ring is made possible by a temporary increase in oxidation level and excision of a weak N-O bond.
Lewis, Robert S.,Wisthoff, Michael F.,Grissmerson,Chain, William J.
supporting information
p. 3832 - 3835
(2014/08/05)

PROCESS FOR PRODUCTION OF OXIDATION REACTION PRODUCT OF AROMATIC COMPOUND
The present invention provides a process for producing an oxidation reaction product of an aromatic compound, having excellent environmental load reduction performance, cost reduction performance, etc. Provided is a process for producing an oxidation reaction product of a raw material aromatic compound by reacting the raw material aromatic compound with an oxidizing agent. The process further uses an electron donor-acceptor linked molecule. The process includes the step of: reacting the electron donor-acceptor linked molecule in an electron-transfer state, the oxidizing agent, and the raw material aromatic compound, thereby generating an oxidation reaction product resulting from oxidation of the raw material aromatic compound.
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Page/Page column 19

(2012/07/14)

Pd, Pt, and Ru complexes of a pincer bis(amino)amide ligand
An improved synthesis of pincer ligand bis[(2-dimethylamino)phenyl]amine (MeN2NH) was reported. Reaction of the Li complex of MeN2N with suitable Pd, Pt, and Ru precursors gave the corresponding metal complexes. The structures of the Pd, Pt, and Ru complexes were determined. The Ru complex showed activity in catalytic transfer hydrogenation of aryl and alkyl ketones. The Royal Society of Chemistry 2011.
Ren, Peng,Vechorkin, Oleg,Csok, Zsolt,Salihu, Isuf,Scopelliti, Rosario,Hu, Xile
scheme or table
p. 8906 - 8911
(2011/10/30)

Axial chirality control during suzuki-miyaura cross-coupling reactions: The tert-Butylsulfinyl group as an efficient chiral auxiliary
An efficient route to a new family of axially chiral biaryl ligands by a Suzuki-Miyaura cross-coupling reaction between ortho,ortho'-disubstituted aryl iodides bearing in ortho position a tert-butyl or p-tolylsulfinyl group and ortho-substituted phenyl boronic acids or esters is described. The comparison between the t-BuSO and p-TolSO groups as chiral controllers is reported. The modularity of the approach is demonstrated by the preparation of a variety of enantiopure axially chiral mixed S/N and S/P ligands.
Colobert, Francoise,Valdivia, Victoria,Choppin, Sabine,Leroux, Frederic R.,Fernandez, Inmaculada,Alvarez, Eleuterio,Khiar, Noureddine
supporting information; experimental part
p. 5130 - 5133
(2009/12/28)

Probing the importance of the hemilabile site of bis(phosphine) monoxide ligands in the copper-catalyzed addition of diethylzinc to N-phosphinoylimines: Discovery of new effective chiral ligands
(Chemical Equation Presented) The hemilabile ligand Me-DuPHOS(O) 2 has proven to be a successful ligand for the copper-catalyzed addition of diethylzinc to N-phosphinoylimines. The corresponding α-chiral amines were obtained in high yields (80-98%) and enantiomeric ratios (19.0:1 to 99.0:1 er). Furthermore, this Cu?2 catalytic system has been shown to be effective in the addition of diethylzinc to nitroalkenes and in the reduction of β,β-disubstituted vinyl phenyl sulfones. This paper describes a general structure/selectivity study in which the three ligand subunits (chiral phospholane-linker-labile coordinating group (Z)) are systematically modified and tested in the copper-catalyzed addition of diethylzinc to the N-phosphinoylimine 1 derived from benzaldehyde. This study led to the discovery of a new class of effective chiral ligands that combine a chiral phospholane unit and an achiral phosphine oxide.
Bonnaventure, Isabelle,Charette, Andre B.
p. 6330 - 6340
(2008/12/22)

LIGANDS
A radioactive compound having the formula (I), where R1 and Ar are as defined in the specification, pharmaceutically-acceptable salts thereof, compositions containing such compounds and uses thereof in diagnosis of conditions wherein the α7 nicotinic rece
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Page/Page column 15-16

(2008/06/13)

Novel bromination method for anilines and anisoles using NH 4Br/H2O2 in CH3COOH
A simple, efficient, regioselective, environmentally safe, and economical method for the oxybromination of anilines and anisoles without catalyst is reported. The electrophilic substitution of bromine generated in situ from ammonium bromide as a bromine source and hydrogen peroxide as an oxidant for the first time.
Krishna Mohan,Narender,Srinivasu,Kulkarni,Raghavan
p. 2143 - 2152
(2007/10/03)

An efficient chemo and regioselective oxidative nuclear bromination of activated aromatic compounds using lithium bromide and ceric ammonium nitrate
A mild, efficient and highly chemo- and regioselective method for the bromination of electron rich aromatic molecules has been developed by electrophilic substitution of Br+, which was generated in situ from LiBr using ceric ammonium nitrate as the oxidant. Free aromatic amines remained unaffected under the reaction conditions.
Roy, Subhas Chandra,Guin, Chandrani,Rana, Kalyan Kumar,Maiti, Gourhari
p. 6941 - 6942
(2007/10/03)

Liquid phase regioselective bromination of aromatic compounds over HZSM-5 catalyst
A simple, efficient, regioselective and environmentally safe method for oxybromination of activated aromatics catalyzed by HZSM-5 is reported. The electrophilic substitution of bromine generated from KBr using HZSM-5 as a catalyst and H2O2 as an oxidant.
Narender,Srinivasu,Kulkarni,Raghavan
p. 3669 - 3675
(2007/10/03)

Chiral β-amino sulfoxides as chiral ligands in palladium-catalyzed asymmetric allylations
New chiral β-amino sulfoxide ligands bearing chiral sulfmyl functionality as a sole chiral source have been deviced and palladium-catalyzed asymmetric allylations of acetoacetate with these ligands have been examined. The highest enantioselectivity (50%)
Hiroi, Kunio,Suzuki, Yoshio
p. 77 - 81
(2007/10/03)

Surfactant control of the ortho/para ratio in the bromination of anilines. 3
We report the bromination of N,N-dimethylaniline in aqueous suspension of cetylpyridinium tribromide, cetylquinuclidinium tribromide, laurylquinuclidinium tribromide, cetyltributylammonium tribromide, cetyldimethyl-2-hydroxyethylammonium tribromide, 1,2-bis(cetyl-N,N-dimethylammonium)ethane tribromide, 1,3-bis(cetyl-N,N-dimethylammonium)propane tribromide, 1,4-bis(cetyl-N,N-dimethylammonium)butane tribromide, (2S,3S)-2,3-dimethoxy-1,4-bis(N-cetyl-N,N-dimethylammonium)butane tribromide. The nature of the head groups of the surfactant, as well as the length of the hydrophobic chain, influence the regioselectivity of the reaction and permits a hypothesis on the structure of the aggregates.
Cerichelli, Giorgio,Luchetti, Luciana,Mancini, Giovanna
p. 2465 - 2470
(2007/10/03)

Regioselective bromination of activated aromatic substrates with N-bromosuccinimide over HZSM-5
The nuclear as well as side-chain bromination of activated aromatic substrates has been achieved in high yields and substantial regioselectivity wiht N-Bromosuccinimide (NBS) over HZSM-5.
Paul, Vincent,Sudalai,Daniel, Thomas,Srinivasan
p. 7055 - 7056
(2007/10/02)

Synthesis of Isobenzofuran Derivatives as Heterocyclic Analogues of the Herbicide Sindone B
The target compounds 21-27 were synthesized via bromination of the N,N,1,1-tetramethylisobenzofuranamines 13, 15 and 16, subsequent bromine-lithium exchange and reaction with propanal or propanoyl chloride, respectively.In the course of some model reactions undertaken to test a synthetic strategy based on directed ortho-lithiation governed by the dimethylamino-group a useful synthesis of the ketone 3 was developed.
Stanetty, Peter,Rodler, Inge K.,Krumpak, Barbara
p. 333 - 339
(2007/10/02)

DNA Binding Compounds. VI. Synthesis and Characterization of 2,5'-Disubstituted Bibenzimidazoles Related to the DNA Minor Groove Hoechst 33258
A series of compounds have been synthesized in which the basic 2-phenylbibenzimidazole structure of Hoechst 33258 has been modified to include various combinations of bromo, iodo, methoxy, amino, alkylamino and nitro groups in the terminal phenyl ring.Both sequential and convergent synthetic routs have been followed using coupling reactions of both imino ethers and aldehydes to 1,2-diamines.All these compounds were characterized by a combination of f.a.b. mass spectrometry and 1H and 13C n.m.r. spectroscopy including inverse detection of long-range heteronuclear CH correlations (HMBC).
Kelly, David P.,Bateman, Stuart A.,Hook, Robert J.,Martin, Roger F.,Reum, Monica E.,et al.
p. 1751 - 1770
(2007/10/02)

SURFACTANT CONTROL OF THE ORTHO/PARA RATIO IN THE BROMINATION OF ANILINES
Products of the bromination reaction of a family of anilines have been examined both in homogeneous solution and in presence of cethyltrimethylammonium bromide (CTAB).The presence of the surfactant induces a high regioselectivity that is opposite to that observed under homogeneous conditions: a high ortho/para ratio has been observed which increases with greater steric hindrance in the ortho position.
Cerichelli, Giorgio,Luchetti, Luciana,Mancini, Giovanna
p. 6209 - 6210
(2007/10/02)

Carbon-Carbon Bond-Forming Reactions of Zinc Homoenolate of Esters. A Novel Three-Carbon Nucleophile with General Synthetic Utility
In the presence of suitable catalysts and additives, the zinc homoenolate of alkyl propionate and its congeners undergo a variety of carbon-carbon bond-forming reactions, e.g., addition onto carbonyl compounds, allylation, arylation, vinylation, and acylation, to produce diverse kinds of alkanoates and cyclopropane derivatives.The moderately reactive zinc homoenolate exhibited a very high degree of chemoselectivity in these reactions.Me3SiCl has been found to greatly accelerate 1,2- or 1,4-addition and the allylation reaction of the zinc reagent.
Nakamura, Eiichi,Aoki, Satoshi,Sekiya, Kouichi,Oshino, Hiroji,Kuwajima, Isao
p. 8056 - 8066
(2007/10/02)