- Redox-Selective Iron Catalysis for α-Amino C-H Bond Functionalization via Aerobic Oxidation
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Single-electron oxidation and α-deprotonation of tertiary anilines using Fe(phen)3(PF6)3 afford α-aminoalkyl radicals, which can be coupled with electrophilic partners to afford various tetrahydroquinolines. Mechanistically, the Fe(phen)n 2+/3+ catalytic cycle is maintained by O2 or a TBHP oxidant, and the presence of the oxygen bound iron complex, Fe(III)-OO(H), was elucidated by electron paramagnetic resonance and electrospray ionization mass spectrometry. This redox-selective nonheme iron catalyst behaves similarly to bioinspired heme iron catalysts.
- Hwang, Joon Young,Ji, A. Young,Lee, Sang Hyeok,Kang, Eun Joo
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supporting information
p. 16 - 21
(2019/11/11)
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- Direct benzylation of amines with benzylic alcohols catalyzed by palladium/phosphine-borane catalyst system
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Direct catalytic benzylation of amines with benzylic alcohols to give benzylamines has been newly developed by using palladium/phosphine-borane catalyst system. In this catalytic reaction, the linking between both phosphine and borane moieties in the ligand is very important. Hydroxy group of benzylic alcohols is activated by Lewis acidic borane to form a benzylpalladium intermediate which is attacked by amines to give benzylamine products.
- Onodera, Gen,Kumagae, Hidenobu,Nakamura, Daiki,Hayasaki, Takuto,Fukuda, Tsutomu,Kimura, Masanari
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supporting information
(2020/11/04)
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- Method for efficiently realizing N-alkylation reaction by using cyclic iridium catalyst
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The invention discloses a method for efficiently realizing N-alkylation reaction by using a cyclic iridium catalyst, and belongs to the technical field of pharmaceutical and chemical synthesis. The preparation method comprises the following steps of: taking amines and alcohol compounds as raw materials, a cyclic iridium complex as a catalyst and water or an organic solvent as a reaction medium, heating, stirring and reacting for 12-24 hours under the protection of inert gas, cooling to room temperature after the reaction is finished, carrying out reduced pressure distillation and concentrationto obtain a crude product, and carrying out column chromatography purification to obtain a series of amine compounds. The synthesis method of the amine compound is simple to operate, easily availablein raw materials and low in price; the method is high in reaction efficiency, good in N-alkylation selectivity, good in adaptability to various functional groups, wide in substrate universality and environmentally friendly, is carried out at the gram level, shows the potential of industrially synthesizing the N-alkylamine compound, and has wide application prospects in the fields of medicines, organic synthesis and the like.
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Paragraph 0227-0233
(2020/11/10)
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- NEW METHOD FOR THE SYNTHESIS OF UNSYMMETRICAL TERTIARY AMINES
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Disclosed is a new method for the synthesis of unsymmetrical tertiary amines using alcohol and an imine, and to new tertiary amines.
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Paragraph 0092
(2020/08/25)
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- Catalyst-free photodecarbonylation ofortho-amino benzaldehyde
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It is almost a consensus that decarbonylation of the aldehyde group (-CHO) needs to not only be mediated by transition metal catalysts, but also requires severe reaction conditions (high temperature and long reaction time). In this work, inspired by the “conformational-selectivity-based” design strategy, we broke this consensus and discovered a catalyst-free photodecarbonylation of the aldehyde group. It revealed that decarbonylation can be easily achieved with visible light irradiation by introducing a tertiary amine into theortho-position of the aldehyde group. A diverse array of tertiary amines is tolerated by our photodecarbonylation under mild conditions. Furthermore, the (QM) computations of the mechanism and the experiments on well-designed special substrates revealed that our photodecarbonylation depends on the conformational specificity of the aldehyde group and tertiary amine, and occurs through an unusual [1,4]-H shift and a subsequent [1,3]-H shift.
- Li, Lamei,Wang, Songping,Wei, Wentao,Yan, Ming,Zhou, Jingwei
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supporting information
p. 3421 - 3426
(2020/06/25)
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- Transition-Metal-Free Three-Component Synthesis of Tertiary Aryl Amines from Nitro Compounds, Boronic Acids, and Trialkyl Phosphites
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The synthesis of aromatic amines is of continuous interest in chemistry. An exceptionally versatile three-component reaction that directly transforms inexpensive nitro compounds, boronic acids, and trialkyl phosphites into tertiary aromatic amines has been realized. The reaction tolerates alkyl and aryl substituents on the nitro and boronic acid moieties, as well as functionalized phosphites. No transition-metal catalysis is required. The method is orthogonal to other classical metal-catalyzed syntheses since it tolerates the presence of halogens, and also permits the synthesis of functionalized compounds such as α-amino ester derivatives. (Figure presented.).
- Roscales, Silvia,Csáky, Aurelio G.
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p. 111 - 117
(2019/11/16)
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- Photo-induced dealdehyding method
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The invention provides a photo-induced dealdehyding method, and belongs to the technical field of organic synthesis. The photo-induced dealdehyding method comprises the following steps that a mixtureof a compound shown in the formula I and a solvent are reacted under an inert gas atmosphere and visible light irradiation, a dealdehyding product is obtained, and no photocatalyst is used in the whole process; wherein the structural formula of the formula I shown in the specification, R is a functional group and is selected from hydrogen, methyl, methoxyl, cyano, chlorine, bromine or fluorine. According to the photo-induced dealdehyding method, in the inert gas atmosphere, the compound shown in the formula (I) can be excited to generate carbon-oxygen bond homogeneous cracking through visiblelight irradiation, then free radical migration and double bond displacement are conducted, finally carbon monoxide is removed, aldehyde group removal is completed, no photocatalyst is needed in the whole process, operation is easy and convenient, and conditions are mild.
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Paragraph 0048-0053; 0156-0161
(2020/06/16)
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- Selective Synthesis of Secondary Amines from Nitriles by a User-Friendly Cobalt Catalyst
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Selective hydrogenation/reductive amination of nitriles to secondary amines catalyzed by an inexpensive and user-friendly cobalt complex, (Xantphos)CoCl2, is reported. The use of (Xantphos)CoCl2 and ammonia borane (NH3?BH3) combination affords the selective reduction of nitriles to symmetrical secondary amines, whereas the employment of (Xantphos)CoCl2 and dimethylamine borane (Me2NH?BH3) along with external amines produce unsymmetrical secondary amines and tertiary amines. The general applicability of this methodology is demonstrated by the synthesis of 43 symmetrical and unsymmetrical secondary and tertiary amines bearing diverse functionalities. (Figure presented.).
- Sharma, Dipesh M.,Punji, Benudhar
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supporting information
p. 3930 - 3936
(2019/07/12)
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- Manganese(III) Porphyrin-Catalyzed Dehydrogenation of Alcohols to form Imines, Tertiary Amines and Quinolines
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Manganese(III) porphyrin chloride complexes have been developed for the first time as catalysts for the acceptorless dehydrogenative coupling of alcohols and amines. The reaction has been applied to the direct synthesis of imines, tertiary amines and quinolines where only hydrogen gas and/or water are formed as the by-product(s). The mechanism is believed to involve the formation of a manganese(III) alkoxide complex which degrades into the aldehyde and a manganese(III) hydride species. The latter reacts with the alcohol to form hydrogen gas and thereby regenerates the alkoxide complex.
- Azizi, Kobra,Akrami, Sedigheh,Madsen, Robert
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p. 6439 - 6446
(2019/04/26)
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- Iron-Catalyzed Reductive Ethylation of Imines with Ethanol
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The borrowing hydrogen strategy has been applied to the ethylation of imines with an air-stable iron complex as precatalyst. This approach opens new perspectives in this area as it enables the synthesis of unsymmetric tertiary amines from readily available substrates and ethanol as a C2 building block. A variety of imines bearing electron-rich aryl or alkyl groups at the nitrogen atom could be efficiently reductively alkylated without the need for molecular hydrogen. The mechanism of this reaction, which shows complete selectivity for ethanol over other alcohols, has been studied experimentally and by means of DFT computations.
- Vayer, Marie,Morcillo, Sara P.,Dupont, Jennifer,Gandon, Vincent,Bour, Christophe
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supporting information
p. 3228 - 3232
(2018/03/13)
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- Electrophilic Amination with Nitroarenes
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An exceptionally general electrophilic amination, which directly transforms commercially available nitroarenes into alkylated aromatic aminoboranes with zinc organyl compounds was developed. The reaction starts with a two-step partial reduction of the nitro group to a nitrenoid, which is used in situ as the electrophilic amination reagent. To facilitate isolation, the resulting air- and moisture-sensitive aminoboranes were reacted with a range of electrophiles. The method not only represents a direct transformation of nitro compounds into electrophilic amination reagents but also provides an elegant alternative to dehydrocoupling methods for the generation of aminoboranes.
- Rauser, Marian,Ascheberg, Christoph,Niggemann, Meike
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supporting information
p. 11570 - 11574
(2017/09/11)
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- n-Butyllithium-mediated synthesis of N-aryl tertiary amines by reactions of fluoroarenes with secondary amines at room temperature
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A simple and facile method for the synthesis of aromatic tertiary amines by amination of fluoroarenes with secondary amines in the presence of n-butyllithium at room temperature was reported.
- Lin, Yingyin,Li, Meng,Ji, Xinfei,Wu, Jingjing,Cao, Song
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p. 1466 - 1472
(2017/02/18)
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- General Reductive Amination of Aldehydes and Ketones with Amines and Nitroaromatics under H2 by Recyclable Iridium Catalysts
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Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaromatics and amines using H2. The iridium catalysts were prepared by pyrolysis of ionic liquid 1-methyl-3-cyanomethylimidazoulium chloride ([MCNI]Cl) with iridium chloride (IrCl3) in activated carbons. Iridium particles were well dispersed and stable in the N-doped carbon materials from [MCNI]Cl with activated carbon. The Ir@NC(600-2h) catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H2 and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC(600-2h) catalyst can be reusable several times without evident deactivation.
- Sui, Dejun,Mao, Fei,Fan, Haipeng,Qi, Zhengliang,Huang, Jun
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supporting information
p. 1371 - 137
(2017/10/05)
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- Heterogeneous cobalt catalysts for reductive amination with H2: General synthesis of secondary and tertiary amines
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Heterogeneous Co@NC catalysts were prepared, characterized and applied for the reductive amination of aldehydes and ketones with H2 gas. The Co catalyst Co@NC (800-2 h) was found to be active and selective for the reductive amination of aldehydes and ketones using H2 gas. Thus, general synthesis of secondary and tertiary amines was developed by the Co-catalyzed reductive amination with H2 gas, and various secondary and tertiary amines can be obtained in high yields. Moreover, a practical synthesis of N-substituted isoindolinones was also presented by a one step process with the Co@NC (800-2 h) catalyst. The Co@NC (800-2 h) catalyst is reusable at least five times without evident loss of activity.
- Mao, Fei,Sui, Dejun,Qi, Zhengliang,Fan, Haipeng,Chen, Rizhi,Huang, Jun
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p. 94068 - 94073
(2016/10/22)
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- Synthesis of unsymmetric tertiary amines via alcohol amination
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The first one-pot selective synthesis of unsymmetric tertiary amines is reported by the amination of two types of alcohols with primary amines via the development of a simple CuAlOx-HT catalyst and enables the synthesis of unsymmetric amines in a wide variety of primary amines and alcohols.
- Pang, Shaofeng,Deng, Youquan,Shi, Feng
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supporting information
p. 9471 - 9474
(2015/06/08)
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- Cobalt carbonyl-based catalyst for hydrosilylation of carboxamides
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The cobalt carbonyl [Co2(CO)8] complex is employed as a useful catalyst for the reduction of tertiary amides to the corresponding tertiary amines using 1,1,3,3-tetramethyldisiloxane (TMDS) and poly(methylhydrosiloxane) (PMHS) as silane reagents under thermal (100 °C) or photo-assisted conditions (UV, 350 nm at room temperature). Of particular interest, a low catalytic amount (0.5 mol%) of [Co2(CO)8] is used to perform the reaction with 2.2 equiv. of PMHS at 100 °C for 3 h. This reaction is the first example of a cobalt-catalyzed hydrosilylation of amides. Copyright
- Dombray, Thomas,Helleu, Camille,Darcel, Christophe,Sortais, Jean-Baptiste
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supporting information
p. 3358 - 3362
(2013/12/04)
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- Palladium catalyzed N-alkylation of amines with alcohols
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An iron oxide immobilized palladium catalyst was prepared for the N-alkylation of amines with alcohols under base and organic ligand free conditions. Applying the optimized reaction conditions, the coupling reactions of amines and alcohols with various structures could be realized with up to 99% isolated yields. The catalysts were studied by XRD, BET, and XPS and the mechanism was studied by DFT calculations.
- Zhang, Yan,Qi, Xiujuan,Cui, Xinjiang,Shi, Feng,Deng, Youquan
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supporting information; experimental part
p. 1334 - 1338
(2011/03/22)
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- Copper(II) triflate catalyzed intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters
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The intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters is achieved under mild conditions in the presence of a catalytic amount of copper(II) triflate (up to 89 % yield). The scope and limitations regarding substrates, diazo esters, and ligands in this reaction are described. The intermolecular aromatic substitution of N,N-disubstituted anilines with diazo esters is shown to proceed under mild conditions in the presence of a catalytic amount of copper(II) triflate/ligand complex(up to 89 % yield). The scope and limitations regarding substrates, diazoesters, and ligands in this reaction are described. Copyright
- Tayama, Eiji,Yanaki, Tomoyo,Iwamoto, Hajime,Hasegawa, Eietsu
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supporting information; experimental part
p. 6719 - 6721
(2011/02/28)
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- ROMP-derived oligomeric phosphates for application in facile benzylation
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The development of new ROMP-based oligomeric benzyl phosphates (OBP n) is reported for use as soluble, stable benzylating reagents. These oligomeric reagents are readily synthesized from commercially available materials and conveniently polymerized and purified in a one-pot process, affording bench-stable, pure white, free-flowing solids on multigram scale. Utilization in benzylation reactions with a variety of nucleophiles is reported.
- Long, Toby R.,Maity, Pradip K.,Samarakoon, Thiwanka B.,Hanson, Paul R.
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supporting information; experimental part
p. 2904 - 2907
(2010/09/30)
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- Selective mono- and di-N-alkylation of aromatic amines with alcohols and acylation of aromatic amines using Ph3P/DDQ
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Selective N-monoalkylation of aromatic amines with 1° and 2° alcohols and conversion of aromatic amines to amides are performed immediately and in excellent yields using triphenylphosphine (PPh3) and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in dichloromethane at room temperature. Symmetrical and unsymmetrical N,N-dialkylation of aromatic amines are also carried out in modest yield at room temperature by this reagent system.
- Iranpoor, Nasser,Firouzabadi, Habib,Nowrouzi, Najmeh,Khalili, Dariush
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experimental part
p. 3893 - 3899
(2009/09/08)
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- Correlation analysis in the reactions of benzyl bromide with N-substituted anilines
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The nucleophilic substitution reaction between benzyl bromide and N-substituted anilines in methanol medium suggests that the reactivity of the nucleophiles increases with their pkb values. A linear relationship exists between the rate and the Computed values of the dipole moment and electronegativity of the nucleophiles. The frontier orbital interactions and correlation of rate with HOMO-LUMO gap of the two reactants suggest that the reaction is not orbital controlled but is controlled by the electrostatic interactions between the reactants.
- Reddy, S. Ranga,Rao, B. Rajeswara,Manikyamba
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p. 436 - 439
(2008/02/12)
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- The titanocene-catalyzed reduction of acetamides to tertiary amines by PhMeSiH2
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A variety of acetamide derivatives are reduced in excellent yields to tertiary amines by PhMeSiH2 in the presence of Cp2TiX 2 (X = F or Me) catalysts. The reactions are very clean at 80 °C. At room temperature a secondary reaction, hydrogenolysis of the C(O)-N bond, intervenes and reduces the chemoselectivity. Nevertheless, this chemistry provides a simple methodology for the amide/alkylamine transformation using inexpensive, commercially available reagents.
- Selvakumar, Kumaravel,Rangareddy, Kesamreddy,Harrod, John F.
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p. 1244 - 1248
(2007/10/03)
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- Syntheses of long-chain quaternary ammonium salts from fatty alcohols by microwave irradiation
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The phase-transfer catalysts, long-chain quaternary ammonium salts, were rapidly synthesized from fatty alcohols by the reactions with hydrogen halides in the presence of trialkyl amines under microwave irradiation. The catalysts could be widely applied in a variety of quick and new organic reactions, whether by conventional heating or under microwave irradiation. The reaction efficiencies under microwave irradiation were higher than those obtained with conventional heating.
- Jiang,Hu,Pang,Yuan
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p. 847 - 850
(2007/10/03)
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- A new phase transfer catalyst (PTC) for N-alkylation reactions
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Hexamethylene tetramine bromide HMTA+ Br- - a new phase transfer catalyst is reported for N-Alkylation reactions of industrially important anilides.
- Bisarya,Rao
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p. 3305 - 3313
(2007/10/02)
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- Antibacterial water-soluble cutting fluids resistant to yeast-like fungi
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A bactericide is added to conventional water-soluble cutting fluids to suppress deterioration by micro-organisms. Such fluids are however accompanied by the drawbacks that the bactericide has a narrow antibacterial spectrum and moreover its effects last a short time. It is the object of the present invention to offers water--soluble cutting fluids which remain resistant to a wide variety of microorganisms for a long time. The present invention therefore offers water-soluble cutting fluids to which has been added a specific amine selected from amines known to date.
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- Diphenylamino and indolyl substituted pyromellitides
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This invention relates to 3,7-bis(disubstituted aminophenyl- or indolyl)-3,7-bis(diphenylamino)pyromellitides, 3,5-bis(disubstituted aminophenyl- or indolyl)-3,5-bis(diphenylamino)pyromellitides and mixtures thereof useful as color formers, particularly in carbonless duplicating and thermal marking systems, which are prepared by the interaction of 2,5-bis(disubstituted aminophenyl- or indolyl)carbonyl-1,4-benzenedicarboxylic acids or 2,4-bis(disubstituted aminophenyl- or indolyl)carbonyl-1,5-benzenedicarboxylic acids and mixtures thereof with diphenylamines.
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- Indolyl phthalide compounds
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3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
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- Alkylation of Benzothiazolines and the Stevens Rearrangement of the Resulting 2,3,3-Trisubstituted Benzothiazolinium Salts
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Alkylation of 2-substituted 3-methyl- or 3-ethylbenzothiazolines with Meerwein reagents gave 2-substituted 3,3-dialkylbenzothiazolinium tetrafluoroborates (3).The configuration of two alkyl groups on the nitrogen was assigned by NMR spectra and NOE measurement.In the Stevens rearrangement of 3 with lithium diisopropylamide ethyl group showed a much larger migratory aptitude (Et:Me>20:1) than methyl group irrespective of the configuration of 3, and cyclic ammonium ylide with planar ?-type carbanion was proposed as an intermediate. 3 suffered nucleophilic attack at the ring sulfur atom by butyllithium to afford a ring-opened ammonium ylide, which collapses to a radical pair to give unusual Stevens rearrangement product, where o-alkylthiophenyl group migrated selectively in preference to alkyl group, because of stabilization by participation of o-alkylthio group.
- Akiba, Kin-ya,Ohara, Yoshio,Inamoto, Naoki
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p. 2976 - 2983
(2007/10/02)
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- Heteroarylphthalides
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3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)-phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
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- Phthalide compounds, processes and marking systems
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3-Aryl-3-indolylphthalides, 3-aryl-3-pyrrolylphthalides and 3-aryl-3-carbazolylphthalides prepared by interaction of the appropriate 2-(heteroaryl)carbonylbenzoic acid and the appropriate phenylamine, and 3,3-bis(indolyl)phthalides prepared by the interaction of the appropriate 2-(indolyl)carbonylbenzoic acid and the appropriate indole are useful as color formers in pressure-sensitive carbonless duplicating systems, thermal marking systems and hectographic copying systems.
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- Rubine disazo acid dyes for polyamides
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Dyes of the formula STR1 wherein B and D are each independently 1,4-phenylene or 1,4-naphthylene; M is hydrogen, lithium, sodium, potassium or ammonium; A1 is hydrogen, C1-4 alkoxy, C1-4 alkyl, trifluoromethyl, nitro, chloro, bromo, cyano, or hydroxy; B1 and B2 are each hydrogen, C1-3 alkoxy, C1-3 alkyl, chloro or bromo; D1 is hydrogen, C1-4 alkoxy, C1-4 alkyl, or chloro; D2 is hydrogen, C1-4 alkoxy, C1-4 alkyl, chloro, bromo, fluoro, or acylamino, acyl being C1-5 alkanoyl, C1-5 alkylsulfonyl, benzoyl or benzenesulfonyl, each acyl unsubstituted or substituted with 1 to 3 of C1-2 alkyl, C1-2 alkoxy, chloro, bromo, cyano, or hydroxy; and R1 and R2 are each C1-6 alkyl, C1-6 chloro or bromoalkyl, C2-6 hydroxy- or dihydroxyalkyl, C2-6 alkoxyalkyl, C1-6 cyanoalkyl, or phenyl-C1-2 alkyl (phenyl unsubstituted or substituted with 1 to 3 of C1-2 alkyl, C1-2 alkoxy, chloro, bromo, cyano or hydroxy) are useful in dyeing natural and synthetic polyamide fibers in deep and level shades of red to blue.
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- Manufacture of arylamines
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Arylamines are manufactured by reacting alcohols with amines in the presence of phosphorus-III compounds. The arylamines I manufactured by the process of the invention are intermediates for the manufacture of crop protection agents, optical brighteners, especially amino-coumarin derivatives, and dyes, especially of the xanthene, pyronine, rhodamine, oxazine, azo, triphenylmethane and diphenylmethane series.
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