cas 698-01-1, 2-Chloro-N,N-dimethylaniline

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Additive-free selective methylation of secondary amines with formic acid over a Pd/In2O3 catalyst
Formic acid is used as the sole carbon and hydrogen source in the methylation of aromatic and aliphatic amines to methylamines. The reaction proceeds via a formylation/transfer hydrogenation pathway over a solid Pd/In2O3 catalyst without the need for any additive.
Benaissa, Idir,Cantat, Thibault,Genre, Caroline,Godou, Timothé,Pinault, Mathieu
p. 57 - 61
(2022/01/19)

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)

Utilization of renewable formic acid from lignocellulosic biomass for the selective hydrogenation and/or N-methylation
Lignocellulosic biomass is one of the most abundant renewable sources in nature. Herein, we have developed the utilization of renewable formic acid from lignocellulosic biomass as a hydrogen source and a carbon source for the selective hydrogenation and further N-methylation of various quinolines and the derivatives, various indoles under mild conditions in high efficiencies. N-methylation of various anilines is also developed. Mechanistic studies indicate that the hydrogenation occurs via a transfer hydrogenation pathway.
Zhou, Chao-Zheng,Zhao, Yu-Rou,Tan, Fang-Fang,Guo, Yan-Jun,Li, Yang
p. 4724 - 4728
(2021/09/06)

Additive-freeN-methylation of amines with methanol over supported iridium catalyst
An efficient and versatile zinc oxide-supported iridium (Ir/ZnO) catalyst was developed to catalyze the additive-freeN-methylation of amines with methanol. Mechanistic studies suggested that the high catalytic reactivity is rooted in the small sizes (1.4 nm) of Ir nanoparticles and the high ratio (93%) of oxidized iridium species (IrOx, Ir3+and Ir4+) on the catalyst. Moreover, the delicate cooperation between the IrOxand ZnO support also promoted its high reactivity. The selectivity of this catalyticN-methylation was controllable between dimethylation and monomethylation by carefully tuning the catalyst loading and reaction solvent. Specifically, neat methanol with high catalyst loading (2 mol% Ir) favored the formation ofN,N-dimethylated amine, while the mesitylene/methanol mixture with low catalyst loading (0.5 mol% Ir) was prone to producing mono-N-methylated amines. An environmentally benign continuous flow system with a recycled mode was also developed for the efficient production ofN-methylated amines. With optimal flow rates and amine concentrations, a variety ofN-methylamines were produced with good to excellent yields in this Ir/ZnO-based flow system, providing a starting point for the clean and efficient production ofN-methylamines with this cost-effective chemical process.
Liu, Xiang,Loh, Teck-Peng,Qiang, Wenwen,Wang, Jing,Ye, Sen,Zhu, Longfei
p. 3364 - 3375
(2021/06/06)

Photocatalytic Water-Splitting Coupled with Alkanol Oxidation for Selective N-alkylation Reactions over Carbon Nitride
Photocatalytic water splitting technology (PWST) enables the direct use of water as appealing “liquid hydrogen source” for transfer hydrogenation reactions. Currently, the development of PWST-based transfer hydrogenations is still in an embryonic stage. Previous reports generally centered on the rational utilization of the in situ generated H-source (electrons) for hydrogenations, in which photogenerated holes were quenched by sacrificial reagents. Herein, the fully-utilization of the liquid H-source and holes during water splitting is presented for photo-reductive N-alkylation of nitro-aromatic compounds. In this integrate system, H-species in situ generated from water splitting were designed for nitroarenes reduction to produce amines, while alkanols were oxidized by holes for cascade alkylating of anilines as well as the generated secondary amines. More than 50 examples achieved with a broad range scope validate the universal applicability of this mild and sustainable coupling approach. The synthetic utility of this protocol was further demonstrated by the synthesis of existing pharmaceuticals via selective N-alkylation of amines. This strategy based on the sustainable water splitting technology highlights a significant and promising route for selective synthesis of valuable N-alkylated fine chemicals and pharmaceuticals from nitroarenes and amines with water and alkanols.
Xu, Yangsen,Zhang, Zhaofei,Qiu, Chuntian,Chen, Shaoqin,Ling, Xiang,Su, Chenliang
p. 582 - 589
(2020/12/09)

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)

Synthesis of Halogenated Anilines by Treatment of N, N-Dialkylaniline N-Oxides with Thionyl Halides
The special reactivity of N,N-dialkylaniline N-oxides allows practical and convenient access to electron-rich aryl halides. A complementary pair of reaction protocols allow for the selective para-bromination or ortho-chlorination of N,N-dialkylanilines in up to 69% isolated yield. The generation of a diverse array of halogenated anilines is made possible by a temporary oxidation level increase of N,N-dialkylanilines to the corresponding N,N-dialkylaniline N-oxides and the excision of the resultant weak N-O bond via treatment with thionyl bromide or thionyl chloride at low temperature.
Reed, Hayley,Paul, Tyler R.,Chain, William J.
p. 11359 - 11368
(2018/08/06)

Efficient and Selective N-Methylation of Nitroarenes under Mild Reaction Conditions
Herein, we report a straightforward protocol for the preparation of N,N-dimethylated amines from readily available nitro starting materials using formic acid as a renewable C1 source and silanes as reducing agents. This tandem process is efficiently accomplished in the presence of a cubane-type Mo3PtS4 catalyst. For the preparation of the novel [Mo3Pt(PPh3)S4Cl3(dmen)3]+ (3+) (dmen: N,N′-dimethylethylenediamine) compound we have followed a [3+1] building block strategy starting from the trinuclear [Mo3S4Cl3(dmen)3]+ (1+) and Pt(PPh3)4 (2) complexes. The heterobimetallic 3+ cation preserves the main structural features of its 1+ cluster precursor. Interestingly, this catalytic protocol operates at room temperature with high chemoselectivity when the 3+ catalyst co-exists with its trinuclear 1+ precursor. N-heterocyclic arenes, double bonds, ketones, cyanides and ester functional groups are well retained after N-methylation of the corresponding functionalized nitroarenes. In addition, benzylic-type as well as aliphatic nitro compounds can also be methylated following this protocol.
Pedrajas, Elena,Sorribes, Iván,Guillamón, Eva,Junge, Kathrin,Beller, Matthias,Llusar, Rosa
p. 13205 - 13212
(2017/09/12)

Deoxygenation of tertiary amine N-oxides under metal free condition using phenylboronic acid
A simple and efficient method for the deoxygenation of amine N-oxides to corresponding amines is reported using the green and economical reagent phenylboronic acid. Deoxygenation of N,N-dialkylaniline N-oxides, trialkylamine N-oxides and pyridine N-oxides were achieved in good to excellent yields. The reduction susceptible functional groups such as ketone, amide, ester and nitro groups are well tolerated with phenylboronic acid during the deoxygenation process even at high temperature. In addition, an indirect method for identification and quantification of tert-amine N-oxide is demonstrated using UV–Vis spectrometry which may be useful for drug metabolism studies.
Gupta, Surabhi,Sureshbabu, Popuri,Singh, Adesh Kumar,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
supporting information
p. 909 - 913
(2017/02/15)

B(C6F5)3-Catalyzed Deoxygenation of Sulfoxides and Amine N-Oxides with Hydrosilanes
An efficient strategy for the deoxygenation of sulfoxides and amine N-oxides by using B(C6F5)3 and hydrosilanes was developed. This method provided the corresponding aromatic and aliphatic products in good to high yields and showed good functional-group tolerance under mild conditions.
Ding, Fangwei,Jiang, Yanqiu,Gan, Shaoyan,Bao, Robert Li-Yuan,Lin, Kaifeng,Shi, Lei
p. 3427 - 3430
(2017/07/04)

N, N -Dimethylation of nitrobenzenes with CO2 and water by electrocatalysis
We have proposed a strategy for the synthesis of N,N-dimethylanilines from nitrobenzene and its derivatives, CO2, and water via an electrochemical reaction under ambient conditions. H+ generated from H2O was used as the hydrogen source. Pd/Co-N/carbon, in which the Pd nanoparticles were supported on Co-N/carbon, was designed and used as the electrocatalyst. It was found that the electrocatalyst was very efficient for the reaction in MeCN solution with 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim]Tf2N) as the supporting electrolyte and 1-amino-methylphosphonic acid (AMPA) as the thermal co-catalyst. A series of control experiments showed that Pd/Co-N/carbon and AMPA cooperated very well in accelerating the reaction. This synthetic route has some obvious advantages, such as using CO2 and water as the reactants, ambient reaction conditions, and high yields of the desired products. This opens up a way to synthesize chemicals by the combination of an electrocatalyst and a thermal catalyst with organic compounds, CO2, and water as the reactants.
Sun, Xiaofu,Zhu, Qinggong,Hu, Jiayin,Kang, Xinchen,Ma, Jun,Liu, Huizhen,Han, Buxing
p. 5669 - 5674
(2017/08/01)

Photocatalytic activation of N-chloro compounds for the chlorination of arenes
Photoredox catalysis activates N-chloramines and N-chloro-succinimide (NCS) for the electrophilic chlorination of arenes. The photooxidation of the nitrogen atom to a radical cation induces a positive polarization on the chlorine atom, which results in a higher reactivity in electrophilic aromatic chlorination reactions.
Hering, Thea,K?nig, Burkhard
p. 7821 - 7825
(2016/11/16)

Halogenase-Inspired Oxidative Chlorination Using Flavin Photocatalysis
Chlorine gas or electropositive chlorine reagents are used to prepare chlorinated aromatic compounds, which are found in pharmaceuticals, agrochemicals, and polymers, and serve as synthetic precursors for metal-catalyzed cross-couplings. Nature chlorinates with chloride anions, FAD-dependent halogenases, and O2 as the oxidant. A photocatalytic oxidative chlorination is described based on the organic dye riboflavin tetraacetate mimicking the enzymatic process. The chemical process allows within the suitable arene redox potential window a broader substrate scope compared to the specific activation in the enzymatic binding pocket. Chlorination of arenes with chloride anions: The photochemical analogue of the enzymatic chlorination of Flavin-adenine dinucleotide (FAD)-dependent halogenases is possible in the presence of riboflavin, air, acetic acid, and blue light (see scheme; RFT=riboflavin tetraacetate).
Hering, Thea,Mühldorf, Bernd,Wolf, Robert,K?nig, Burkhard
supporting information
p. 5342 - 5345
(2016/04/26)

Methylation of aniline and its derivatives with dimethyl carbonate in the presence of binder-free micro-, meso-, and macroporous zeolites KNaX, NaY, and HY
Aniline and its derivatives undergo methylation when treated with dimethyl carbonate in the presence of binder-free micro-, meso-, and macroporous zeolites KNaX, NaY, and HY leading to the formation of N-methyl- and N,N-dimethylanilines.
Khusnutdinov,Shchadneva,Mayakova, Yu. Yu.,Ardieva,Khazipova,Kutepov
p. 1565 - 1570
(2017/01/28)

Imidazolium Salt Catalyzed para -Selective Halogenation of Electron-Rich Arenes
A highly para-selective halogenation of arenes bearing coordinating groups in the presence of a dimidazolium salt as a catalyst is reported. A series of electron-rich p-haloarenes were prepared in good yields and good to excellent selectivities. We also propose a plausible mechanism for the catalytic reaction.
Chen, Jie,Xiong, Xiaoyu,Chen, Zenghua,Huang, Jianhui
supporting information
p. 2831 - 2834
(2015/12/18)

Light-promoted N,N-dimethylation of amine and nitro compound with methanol catalyzed by Pd/TiO2 at room temperature
A series of TiO2 supported nano-Pd catalysts (Pd/TiO2) were prepared and used for the N,N-dimethylation of different amines and nitro compounds with methanol under UV irradiation at room temperature. A wide range of N,N-dimethyl amines were one-pot synthesized with up to 98% by applying aliphatic secondary amines, aromatic primary amines, aliphatic primary amines and aromatic nitro compounds as starting materials. It is noteworthy that up to 90% yield of 4-chloro-N,N-dimethylaniline was obtained by adjusting the Pd loadings on the TiO2 and the dehalogenation reaction was inhibited. Finally, a reaction mechanism is discussed, involving PhN = CH2 and PhNHCH3 as reaction intermediates.
Zhang, Lina,Zhang, Yan,Deng, Youquan,Shi, Feng
p. 14514 - 14521
(2015/03/05)

Convenient Reductive Methylation of Amines with Carbonates at Room Temperature
Methylation of amines is a fundamental and commonly used reaction in organic synthesis. Many methods are known including various reductive methylations using formaldehyde, formic acid, or carbon dioxide in the presence of reductants. However, several of these methods suffer from limited substrate scope and chemoselectivity because of the different nucleophilicities of substrates. In this respect, the combination of carbonates and hydrosilanes is a valuable methylation source in the presence of Pt-based catalysts. This highly tunable method allows for methylation of both aromatic and aliphatic amines, and chemoselective methylation of aminoalcohols and diamines. Notably, the in situ-formed catalyst can also be used for the reduction of carbonates to methanol at room temperature. Mechanistic insights on intermediates formed during the reaction pathway were obtained by using ESI mass spectrometry.
Li, Yuehui,Sorribes, Iván,Vicent, Cristian,Junge, Kathrin,Beller, Matthias
p. 16759 - 16763
(2015/11/16)

Azo-functionalized microporous organic polymers: Synthesis and applications in CO2 capture and conversion
Azo-functionalized MOPs (Azo-MOPs) were synthesized via oxidative polymerization of aromatic amines catalyzed by t-BuOCl/NaI (25 °C, 1 h, yield: >95%), which displayed an excellent coordinating ability with a Ru complex. The resulting Ru-coordinated Azo-MOPs displayed high CO2 capacity and high performances for catalyzing the methylation of amines with CO2 under low pressure (0.5 MPa).
Yang, Zhenzhen,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Ma, Zhishuang,Ji, Guipeng,Han, Buxing,Liu, Zhimin
supporting information
p. 11576 - 11579
(2015/07/15)

B(C6F5)3-catalyzed methylation of amines using CO2 as a C1 building block
B(C6F5)3 was proven to be an efficient metal-free catalyst for the methylation of amines using CO2 as a C1 building block in the presence of hydrosilanes under easy-handling conditions. A broad range of N-alkylanilines, dialkylamines and primary anilines all proceeded well under the catalytic conditions.
Yang, Zhenzhen,Yu, Bo,Zhang, Hongye,Zhao, Yanfei,Ji, Guipeng,Ma, Zhishuang,Gao, Xiang,Liu, Zhimin
supporting information
p. 4189 - 4193
(2015/08/11)

General catalytic methylation of amines with formic acid under mild reaction conditions
A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C1 building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines including [N-13C]-labelled drugs in good to excellent yields under mild conditions. Methylation made easy: A general catalytic protocol for the methylation of amines has been developed applying, for the first time, formic acid as the C1 building block and silanes as reducing agents. A broad range of aromatic and aliphatic, both primary and secondary, amines has been converted to the corresponding tertiary amines, including [N-13C]-labelled drugs, in good to excellent yields at mild conditions (see scheme; dppp=(1,3-bis(diphenylphosphino)propane)).
Sorribes, Ivan,Junge, Kathrin,Beller, Matthias
supporting information
p. 7879 - 7883
(2014/07/07)

Electrophilic fluorination of N,N-dimethylaniline, N,N-dimethylnaphthalen- 1-amine and 1,8-bis(dimethylamino)naphthalene with N-F reagents
Reaction of N,N-dimethylaniline, N,N-dimethylnaphthalen-1-amine and 1,8-bis(dimethylamino)- naphthalene (proton sponge) with 1-chloromethyl-4- fluorodiazonia-bicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) and N-fluorobenzenesulfonimide (NFSI) h
Sorokin, Vladimir I.,Pozharskii, Alexander F.,Ozeryanskii, Valery A.
p. 67 - 72
(2013/11/06)

One-pot synthesis of N,N-dimethylanilines from nitroarenes with skeletal Cu as chemoselective catalyst
A range of N,N-dimethylanilines were synthesized with excellent yields in one-pot by the hydrogenation and alkylation of nitroarenes with H2 and HCHO over quenched skeletal Cu catalyst, which provides a facile, economical, and environmentally benign alternative methodology for C-N bonds formation.
Rong, Zeming,Zhang, Wenjun,Zhang, Peng,Sun, Zhuohua,Lv, Jinkun,Du, Wenqiang,Wang, Yue
p. 115 - 118
(2013/09/02)

Metal organic frameworks as heterogeneous catalysts for the selective N-methylation of aromatic primary amines with dimethyl carbonate
Metal organic frameworks (MOFs) with aluminium, copper and iron as central metal atoms with 1,4-benzenedicarboxylic acid (aluminium) and 1,3,5-benzenetricarboxylic acid (copper and iron) as ligands are selective and active catalysts in promoting the polymethylation of aromatic amines with dimethyl carbonate (DMC). N-methylation prevails over carbamoylation even though they are competing parallel processes. The present N-methylation protocol using DMC enjoys advantages such as convenient reaction conditions, benign, reusable, cost-effective catalyst, avoids the use of additional solvent and uses a safe, green methylating agent that only produces CO2 and methanol as by-products.
Dhakshinamoorthy, Amarajothi,Alvaro, Mercedes,Garcia, Hermenegildo
experimental part
p. 19 - 25
(2010/08/20)

Safe and efficient reductive methylation of primary and secondary amines using N-methylpyrrolidine zinc borohydride
An efficient, general procedure for reductive methylation of primary and secondary amines with 37% formaldehyde using N-methylpyrrolidine zinc borohydride (ZBHNMP) as a reducing agent gave the corresponding tertiary amines in excellent yields. The reaction was carried out in tetrahydrofuran under neutral conditions at 0-10°C. Copyright Taylor & Francis Group, LLC.
Alinezhad, Heshmatollah,Tajbakhsh, Mahmood,Salehian, Fatemeh,Fazli, Kazem
scheme or table
p. 2415 - 2420
(2010/09/08)

Industrial-scale palladium-catalyzed coupling of aryl halides and amines - A personal account
The palladium-catalyzed coupling of amines and aryl halides or aryl alcohol derivatives has matured from an exotic small-scale transformation into a very general, efficient and robust reaction during the last ten years. This article reports several applications of this method from an industrial vantage point, including ligand synthesis, synthesis of arylpiperazines, arylhydrazines and diarylamines. Much emphasis in placed on issues of scale-up and safety to underline the potential of C-N couplings as solutions for industrial-scale synthetic problems.
Buchwald, Stephen L.,Mauger, Christelle,Mignani, Gerard,Scholz, Ulrich
p. 23 - 39
(2007/10/03)

Dichlorobis(1,4-diazabicyclo[2.2.2]octane)(tetrahydroborato)zirco- nium(IV), [Zr(BH4)2Cl2(dabco)2](ZrBDC), as a new, stable, and versatile bench top reducing agent: Reduction of imines and enamines, reductive amination of aldehydes and ketones and reductive methylation of amines
The reducing agent is easily prepared in an almost quantitative yield from commercially available starting materials. This compound is stable under mild aqueous acidic conditions (pH 4-6) and survives in H2O for several days without losing its reducing abilities. ZrBDC has been successfully used for the reduction of imines and enamines, reductive amination of aldehydes and ketones, and reductive methylation of amines.
Firouzabadi, Habib,Iranpoor, Nasser,Alinezhad, Heshmatollah
p. 143 - 151
(2007/10/03)

Highly Selective Aromatic Chlorinations. Part 2. The Chlorination of Substituted Phenols, Anisoles, Anilines, and Related Compounds with N-Chloroamines in Acidic Solution
Phenols, anisoles, anilines, and related compounds are chlorinated in trifluoroacetic acid at room temperature by N-chlorodialkylamines and N-chlorotrialkylammonium salts.With monsubstituted compounds and their 2- and 3-substituted derivatives the reaction occurs efficiently and selectively at the 4-position.The reactivity of these substrates and the selectivity of their chlorinations are determined by electronic rather than steric effects of the substituent.Blocking the reaction with a substituent at the 4-position generally leads to only poor or moderate yields of the 2-chlorinated product.Evidence for radical and cation radical intermediates has been obtained in the reactions of some of the 4-substituted reactants and the mechanism of chlorination is discussed in the light of these findings.The reactions of selected substrates have been scaled up to give laboratory syntheses.
Smith, John R. Lindsay,McKeer, Linda C.,Taylor, Jonathan M.
p. 385 - 392
(2007/10/02)

The Chlorination of Some N,N-Dimethylanilines with 1,3,5-Trichloro-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (Trichloroisocyanuric Acid)
The reaction of some representative N,N-dimethylanilines and of Fischer's base (1,3,3-trimethyl-2-methyleneindoline) with trichloroisocyanuric acid in concetrated sulfuric acid has been investigated.In many cases mixtures of chlorinated products were obtained; these mixtures were examined both by gas-liquid chromatography and by proton magnetic resonance spectroscopy.The reaction of N,N-dimethylaniline with dichloroisocyanuric acid was also studied.A feature of these chlorinations is the marked tendency for substitution to occur ortho to the dimethylamino group.This behaviour therefore differs from that reported for the corresponding brominations involving dibromoisocyanuric acid, where meta-substitution was observed.
Rosevear, Judi,Wilshire, John F. K.
p. 843 - 852
(2007/10/02)