- Some properties of 1-(nitrophenyl)-aminobenzimidazoles
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The chemical properties of previously synthesized 1-[2(4)-nitrophenyl]aminobenzimidazoles, in particular, alkylation at the NH group, thiolation, and reduction were studied.
- Dyablo,Pozharskii,Shkurupii
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- Unusual Rate-limiting Proton Transfer in the Acid-catalysed Reactions of N-Nitroso Compounds
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For both N-methyl-N-nitrosoaniline and N-nitrosodiphenylamine, the catalytic effect of halide ion, thiocyanate ion, and thiourea in the denitrosation reaction in acid solution disappears at high nucleophile concentrations.This suggests a change to an earlier rate-limiting step.The data, including the variation of rate constant with acidity, are quantitatively in accord with a reaction mechanism involving protonation of the nitosamine followed by nucleophilic attack, either stage being rate limiting, depending on the reactivity and concentration of the nucleophile.The kinetic solvent isotope effect kH2O/kD2O decreases from 1.59 at 0.43M-thiourea to 0.71 at 0.015M-thiourea, which is consistent with a change from general acid catalysis at high to specific hydrogen ion catalysis at low .Substituent effects at the amino-nitrogen atom and also in the 4-position of a phenyl substituent are very amall, the largest effect being a three-fold reduction in rate constant effected by a 4-NO2 group.These results are in accord with the known dipolar nature of nitrosamines.There is a close analogy between this system and the acid-catalysed cleavage reaction of carbamate derivatives.A similar mechanism is proposed involving a pre-association of the reactants forming a hydrogen-bonded intermediate.
- Al-Kaabi, Sharifa S.,Hallett, Geoffrey,Meyer, Thomas A.,Williams, D. Lyn H.
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- Methanolysis of thioamide promoted by a simple palladacycle is accelerated by 108 over the methoxide-catalyzed reaction
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Palladacycle 1 catalyzes the methanolytic cleavage of N-methyl-N-(4- nitrophenyl)thiobenzamide (4) via a mechanism involving formation of a Pd-bound tetrahedral intermediate (TI). The rate constant for decomposition of the complex formed between 1, methox
- Liu, C. Tony,Maxwell, Christopher I.,Pipe, Stephanie G.,Neverov, Alexei A.,Mosey, Nicholas J.,Brown, R. Stan
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- The Reaction of Benzenesulfenanilides with Lewis Acids: Involvement of Radical Cation Intermediates.
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The 4'-substituted N-methylbenzenesulfenanilides 1a-c react with Lewis acids, including BF3, AlCl3 and GaCl3, to afford the radical cation intermediates 9a-c, some of which could be detected by e.p.r. spectroscopy.Thus, the 4'-methoxy substituted compound 1a gave the fairly persistent radical cation 9a.In contrast, the radical cation 9b, derived from the 4'-nitro substituted compound 4b, was not detected apparently because it decayed too rapidly forming the very stable radical cation 11b, intermediate in the formation of the rearranged sulfide 10b.The radical intermediates 9a-c react with cyclohexene to give the 1,2-adducts 4a-c, 5 and 6 which are believed to be formed from either the thiiranium ion 7b or the sulfurane 8a,c.
- Grossi, Loris,Montevecchi, Carlo
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- Cleavage of alkoxycarbonyl protecting groups from carbamates by t-BuNH2
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An efficient, simple protocol for the selective cleavage of a variety of N-alkoxycarbonyl protecting groups by t-BuNH2/MeOH is described. The scope of the procedure was explored for a series of indole, aniline and pyrrolidine carbamate derivatives containing other potentially reactive functional groups affording a clean cleavage of the carbamate group.
- Suárez-Castillo, Oscar R.,Montiel-Ortega, Luis Alberto,Meléndez-Rodríguez, Myriam,Sánchez-Zavala, Maricruz
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- Oxidative N-demethylation of N,N-dimethylanilines catalysed by lignin peroxidase: A mechanistic insight by a kinetic deuterium isotope effect study
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Lignin peroxidase can catalyse the N-demethylation of N,N- dimethylanilines by an electron transfer mechanism, where the deprotonation of the intermediate radical cation is also an enzymatic process.
- Baciocchi, Enrico,Gerini, Maria Francesca,Lanzalunga, Osvaldo,Lapi, Andrea,Mancinelli, Simona,Mencarelli, Paolo
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- Synthesis of some heterocycle containing urea derivatives and their anti-viral activity
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Some new isoindol heterocyclic ureas (6a-6i) have been synthesized using N-aminophthalimide (2) and ethyl N-monosubstituted/ethyl N,N-disubstituted carbamate (5a-5i). All the newly synthesized final compounds have been evaluated for their anti-viral activities against a variety of viruses. The compound (6f) with the methoxy substituent showed reasonably better activity as compared to the standard drugs against all the viruses (cf. Tables 1, 2 and 3). Further, all the products (6a-6i) were found to be active against Vesicular stomatitis virus, Coxsackie virus B4 and Respiratory syncytical virus (cf. Table 2) and the compounds (6h) and (6i) displayed better antiviral activity in comparison to Brivudin and (S)-DHPA (cf. Table 3).
- Verma, Majusha,Singh, Krishna N.,Clercq, Erik D.
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- Highly selective hydrogenation of amides catalysed by a molybdenum pincer complex: Scope and mechanism
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A series of molybdenum pincer complexes has been shown for the first time to be active in the catalytic hydrogenation of amides. Among the tested catalysts, Mo-1a proved to be particularly well suited for the selective C-N hydrogenolysis of N-methylated formanilides. Notably, high chemoselectivity was observed in the presence of certain reducible groups including even other amides. The general catalytic performance as well as selectivity issues could be rationalized taking an anionic Mo(0) as the active species. The interplay between the amide CO reduction and the catalyst poisoning by primary amides accounts for the selective hydrogenation of N-methylated formanilides. The catalyst resting state was found to be a Mo-alkoxo complex formed by reaction with the alcohol product. This species plays two opposed roles-it facilitates the protolytic cleavage of the C-N bond but it encumbers the activation of hydrogen.
- Leischner, Thomas,Artús Suarez, Lluis,Spannenberg, Anke,Junge, Kathrin,Nova, Ainara,Beller, Matthias
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- Methylation of aniline and its derivatives with dimethyl carbonate in the presence of binder-free micro-, meso-, and macroporous zeolites KNaX, NaY, and HY
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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
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- Synergistic effect of cyclodextrin-based binuclear complexes in the hydrolysis of amide
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Novel cyclodextrin-based binuclear metal complexes have been prepared and proved to be far more efficient than their mononuclear complexes in promoting amide hydrolysis. (C) 2000 Elsevier Science Ltd.
- Yan, Jia-Ming,Atsumi, Masato,Yuan, De-Qi,Fujita, Kahee
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- Kinetic deuterium isotope effect profiles and substituent effects in the oxidative N-demethylation of N,N-dimethylanilines catalyzed by tetrakis(pentafluorophenyl)porphyrin iron(III) chloride
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The mechanistic dichotomy (hydrogen atom transfer or electron-transfer mechanism) in the oxidative N-dealkylation of a series 4-X-N,N- dimethylanilines (X = MeO, Me, H, Br, CF3, CN, NO2) by PhIO, catalyzed by tetrakis(pentafluorophen
- Baciocchi, Enrico,Lanzalunga, Osvaldo,Lapi, Andrea,Manduchi, Laura
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- Efficient and versatile catalytic systems for the n-methylation of primary amines with methanol catalyzed by n-heterocyclic carbene complexes of iridium
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Efficient and versatile catalytic systems were developed for the N-methylation of both aliphatic and aromatic primary amines using methanol as the methylating agent. Iridium complexes bearing an Nheterocyclic carbene (NHC) ligand exhibited high catalytic performance for this type of transformation. For aliphatic amines, selective N,N-dimethylation was achieved at low temperatures (50-90 °C). For aromatic amines, selective N-monomethylation and selective N,N-dimethylation were accomplished by simply changing the reaction conditions (presence or absence of a base with an appropriate catalyst). These findings can be used to develop methods for synthesizing useful amine compounds having N-methyl or N,N-dimethyl moieties.
- Toyooka, Genki,Tuji, Akiko,Fujita, Ken-Ichi
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- A facile protocol for the synthesis of mono-N-methyl anilines via formimidate intermediates
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A general procedure for the preparation of mono-N-methyl anilines has been developed with excellent yields. This protocol relies on a NaBH3(OAc) reduction of formimidate intermediates that are quantitatively generated by treatment of primary substituted anilines with triethyl orthoformate under the catalysis of MCM-41-SO3H mesoporous zeolite. The newly developed procedure was facile, efficient, and environmentally benign.
- Sun, Nan,Wang, Shuai,Mo, Weimin,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
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- Facile method for the monomethylation of anilines
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The monomethylation of anilines was achieved in high yield from the reaction of 1,3,5-triphenylhexahydro-1,3,5-triazines with BH3·S(CH3)2 followed by hydrolysis.
- Ha, Hyun-Joon,Ahn, Young-Gil
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- Methoxycarbonylation of Alkyl-, Cycloalkyl-, and Arylamines with Dimethyl Carbonate in the Presence of Binder-Free Zeolite
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Abstract: Methyl N-alkyl-, N-cycloalkyl-, and N-arylcarbamates were synthesized by reaction of the correspondingamines with dimethyl carbonate in the presence of binder-free FeHY zeolite. Theoptimal conditions (reactant ratio, amount of the catalyst, temperature,reaction time) were found to afford the target products with high yields.
- Khazipova, A. N.,Khusnutdinov, R. I.,Mayakova, Yu. Yu.,Shchadneva, N. A.
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- Formation of anilines from 5-nitro-2-phenylpyrimidine, amines, and acetone
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The reaction of 5-nitro-2-phenylpyrimidine with aliphatic amines and acetone gave N-substituted 4-nitroanilines.In addition, 2-methyl-5-nitropyridine was also obtained from ethylamine. - Key words: pyrimidine; transformation of cyclic intermediates; anilines; pyridine.
- Gromov, S. P.
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- Construction of interconnected acidity functions based on ortho substituted anilines and N-methylanilines as indicators
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The log I values of 15 mainly ortho substituted derivatives of aniline and N-methylaniline have been measured spectrophotometrically in sulfuric, perchloric, and methanesulfonic acids. A new algorithm has been suggested for construction of acidity functions enabling simultaneous and independent construction of acidity functions in various media under the condition of equal values of pKa of the same indicators in the given media. The so-called interconnected acidity functions have been constructed with using this algorithm and the log I values measured in the above media, and the pKa values have been calculated. The resulting acidity functions and pKa values agree well with the corresponding literature data.
- Pytela, Oldrich,Kulhanek, Jiri,Jiraskova, Eva,Nevecna, Tatjana
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- N-Methylation of poorly nucleophilic aromatic amines with dimethyl carbonate
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Abstract: Dimethyl carbonate (DMC), an environmentally friendly methylation agent, is a substitute for traditional methylation agents such as methyl halides (CH3X, X?=?I, Br, Cl) or dimethyl sulfate. An efficient, convenient, and green method has been developed for N-methylation of poorly nucleophilic aromatic amines with DMC. It was found that the couple PEG400/K2CO3 provides good selectivity for the N-methylation product. Finally, the mechanism for reaction of amines with DMC was investigated, and a plausible multistep mechanism proposed and verified. Graphical Abstract: [Figure not available: see fulltext.]
- Yan, Huidong,Zeng, Liufang,Xie, Yaqiang,Cui, Yu,Ye, Liyi,Tu, Song
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- Tandem Transformation of Nitro Compounds into N-Methylated Amines: Greener Strategy for the Utilization of Methanol as a Methylating Agent
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A simple air- and moisture-stable, highly efficient ruthenium NNN pincer complex is reported for the first time to catalyze the tandem transformation of various aromatic and aliphatic nitro compounds into the corresponding N-methylated amines in up to 98 % yield by using methanol as a green methylating agent. Gram-scale reactions of challenging nitro substrates demonstrated the practical application aspects of this catalytic system. Importantly, the N-methylamine moiety could be smoothly introduced to various complex molecular structures without using any expensive palladium/phosphine/amine-based cross-coupling reactions.
- Paul, Bhaskar,Shee, Sujan,Chakrabarti, Kaushik,Kundu, Sabuj
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- Room-temperature copper-catalyzed arylation of dimethylamine and methylamine in neat water
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The first room-temperature copper-catalyzed arylations of dimethylamine and methylamine in neat water have been developed. Using a combination of CuI and 6,7-dihydroquinolin-8(5 H)-one oxime as catalyst, dimethylamine is arylated with various aryl halides to give the corresponding products in good to excellent yields. Further, this catalysis enables the selective arylation of methylamine to afford the high yields of monoarylated methylamines as the sole products.
- Wang, Deping,Kuang, Daizhi,Zhang, Fuxing,Yang, Chunlin,Zhu, Xiaoming
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- Reaction of primary aromatic amines with alkyl carbonates over NaY faujasite: A convenient and selective access to mono-N-alkyl anilines
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At atmospheric pressure and at 130-160°C, primary aromatic amines (p-XC6H4NH2, X = H, Cl, NO2) are mono-N-alkylated in a single step, with symmetrical and asymmetrical dialkyl carbonates [ROCOOR′, R = Me, R′ = MeO(CH2)2O(CH2)2; R = R′ = Et; R = R′ = benzyl; R = R′ = allyl; R = Et, R′ = MeO(CH2)2O(CH2)2], in the presence of a commercially available NaY faujasite. No solvents are required. Mono-N-alkyl anilines are obtained with a very high selectivity (90-97%), in good to excellent yields (68-94%), on a preparative scale. In the presence of triglyme as a solvent, the mono-N-alkyl selectivity is independent of concentration and polarity factors. The reaction probably takes place within the polar zeolite cavities, and through the combined effect of the dual acid-base properties of the catalyst.
- Selva,Tundo,Perosa
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- By-products in the rearrangement of N-methyl-N-phenylnitramine
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N-Methyl-N-phenylnitramine was rearranged in the aqueous dioxane- sulphuric acid mixture to 2-nitro- and 4-nitro-N-methylanilines. The isomer ratio was independent of the acidity within the range of -0.3 > H(o) > -2.8. Some by-products were isolated and i
- Daszkiewicz, Zdzislaw,Nowakowska, Ewa,Kyziol, Janusz B.
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- N-Alkylation of Aniline Derivatives by Use of Potassium Cation-exchanged Y-Type Zeolite
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Zeolite K-Y is effective as a promoter in the N-alkylation of aniline derivatives in comparison with γ-alumina.
- Onaka, Makoto,Umezono, Akihiro,Kawai, Motomitsu,Izumi, Yusuke
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- A very convenient dimethylamination of activated aromatic halides using N,N-dimethylformamide and ethanolamines
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A very convenient dimethylamination of activated aromatic halides was achieved by using N,N-dimethylformamide(DMF) and ethanolamines. p- Nitrochlorobenzene, 2-halopyridines, 2-chloroquinoline and 2-chloropyrimidine gave the corresponding dimethylamino substituted products when treated with DMF and diethanolamine in 80-92% yield.
- Cho, Yoon Hwan,Park, Jae Chan
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- A convenient one pot procedure for N-methylation of aromatic amines using trimethyl orthoformate
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Aromatic amines react with trimethyl orthoformate in the presence of concentrated sulfuric acid followed by acid hydrolysis to afford mono methylated amines in moderate to good yields.
- Padmanabhan, Seetharamaiyer,Reddy, N. Laxma,Durant, Graham J.
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- To what extent can a conjugation between two pairs of peri-nitro and peri-amino groups be realized through the naphthalene core?
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Through-conjugation for a wide range of 1,8-diamino-4,5-dinitronaphthalenes (N-acylated, N-alkylated, N,N′-bridged, N-heterocyclic, and N-deprotonated compounds) was for the first time quantified in solution by means of ultraviolet-visible and proton nucl
- Ozeryanskii, Valery A.,Filatova, Ekaterina A.,Pozharskii, Alexander F.,Shevchuk, Dmitrii A.,Sorokin, Vladimir I.
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- INTERVENTION OF N,N-DIMETHYLANILINIUM CATION RADICAL IN THE POLONONOVSKI TYPE REACTION OF N,N-DIMETHYLANILINE N-OXIDE CATALYZED BY MESO-TETRAPHENYLPORPHINATOIRON/IMIDAZOLE
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Meso-tetraphenylporphinatoiron(III)/imidazole catalyzes the Polonovski type reaction of substituted N,N-dimethylaniline N-oxides to give mixtures of N-demethylated and N-deoxygenated products.Effect of substituent on the turnover number and the ratio of the demethylation to the deoxygenation, and other observations suggest that the Polonovski type N-demethylation reaction takes place via the rate determining N,N-dimethylanilinium cation radical formation.
- Fujimori, Ken,Takata, Toshikazu,Fujiwara, Seiichi,Kikuchi, Osamu,Oae, Shigeru
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- Methanol dehydrogenation by iridium N-heterocyclic carbene complexes
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A series of homogeneous iridium bis(N-heterocyclic carbene) catalysts are active for three transformations involving dehydrogenative methanol activation: acceptorless dehydrogenation, transfer hydrogenation, and amine monoalkylation. The acceptorless dehydrogenation reaction requires base, yielding formate and carbonate, as well as 2-3 equivalents of H2. Of the few homogeneous systems known for this reaction, our catalysts tolerate air and employ simple ligands. Transfer hydrogenation of ketones and imines from methanol is also possible. Finally, N-monomethylation of anilines occurs through a borrowing hydrogen reaction. Notably, this reaction is highly selective for the monomethylated product.
- Campos, Jesús,Sharninghausen, Liam S.,Manas, Michael G.,Crabtree, Robert H.
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- Efficient methylation of anilines with methanol catalysed by cyclometalated ruthenium complexes
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Cyclometalated ruthenium complexes4-10allow the effective methylation of anilines with methanol to selectively giveN-methylanilines. This hydrogen autotransfer procedure proceeds under mild conditions (60 °C) in a practical manner (NaOH as base). Mechanistic investigations suggest an active homogenous ruthenium complex and β-hydride elimination of methanol as the rate determining step.
- Piehl, Patrick,Amuso, Roberta,Spannenberg, Anke,Gabriele, Bartolo,Neumann, Helfried,Beller, Matthias
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- CO2-tuned highly selective reduction of formamides to the corresponding methylamines
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We herein describe an efficient, CO2-tuned and highly selective C-O bond cleavage of N-methylated formanilides. With easy-to-handle and commercially available NaBH4 as the reductant, a variety of formanilides could be turned into the desired tertiary amines in moderate to excellent yields. The role of CO2 has been investigated in detail, and the mechanism is proposed on the basis of experiments.
- Chao, Jianbin,Guo, Zhiqiang,Pang, Tengfei,Wei, Xuehong,Xi, Chanjuan,Yan, Leilei
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supporting information
p. 7534 - 7538
(2021/10/12)
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- Self-Immolative System for Disclosure of Reactive Electrophilic Alkylating Agents: Understanding the Role of the Reporter Group
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The development of stable, efficient chemoselective self-immolative systems, for use in applications such as sensors, requires the optimization of the reactivity and degradation characteristics of the self-immolative unit. In this paper, we describe the effect that the structure of the reporter group has upon the self-immolative efficacy of a prototype system designed for the disclosure of electrophilic alkylating agents. The amine of the reporter group (a nitroaniline unit) was a constituent part of a carbamate that functioned as the self-immolative unit. The number and position of substituents on the nitroaniline unit were found to play a key role in the rate of self-immolative degradation and release of the reporter group. The position of the nitro substituent (meta- vs para-) and the methyl groups in the ortho-position relative to the carbamate exhibited an influence on the rate of elimination and stability of the self-immolative system. The ortho-methyl substituents imparted a twist on the N-C (aromatic) bond leading to increased resonance of the amine nitrogen's lone pair into the carbonyl moiety and a decrease of the leaving character of the carbamate group; concomitantly, this may also make it a less electron-withdrawing group and lead to less acidification of the eliminated β-hydrogen.
- Chippindale, Ann M.,Gavriel, Alexander G.,Hayes, Wayne,Khurana, Gurjeet S.,Leroux, Flavien,Lewis, Viliyana G.,Russell, Andrew T.,Sambrook, Mark R.
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p. 10263 - 10279
(2021/08/16)
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- Borane-Trimethylamine Complex as a Reducing Agent for Selective Methylation and Formylation of Amines with CO2
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We report herein that a borane-trimethylamine complex worked as an efficient reducing agent for the selective methylation and formylation of amines with 1 atm CO2 under metal-free conditions. 6-Amino-2-picoline serves as a highly efficient catalyst for the methylation of various secondary amines, whereas in its absence, the formylation of primary and secondary amines was achieved in high yield with high chemoselectivity. Mechanistic studies suggest that the 6-amino-2-picoline-borane catalytic system operates like an intramolecular frustrated Lewis pair to activate CO2.
- Zhang, Yanmeng,Zhang, He,Gao, Ke
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supporting information
p. 8282 - 8286
(2021/10/25)
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- SELF-IMMOLATIVE SYSTEMS
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The present invention is concerned with self-immolative recognition and/or responsive systems for electrophilic compounds, especially alkylating agents, which systems may comprise disclosure or detection of the alkylating agent. The present invention is especially concerned with non-protic triggered self-immolative systems, molecules, and methods, and in particular for detection of non- protic electrophilic agents, and especially alkylating agents, for example alkyl or benzylic halides, which may be found in pesticides or fumigants, or chemical warfare agents.
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- INDOLINONE COMPOUNDS FOR USE AS MAP4K1 INHIBITORS
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The present disclosure is directed to compounds of formula (I) and pharmaceutically acceptable salts thereof, wherein ring A, ring C, X1, X2, L1, R1, R2, R3, R4, R5, R6, R7, m and n are as defined herein, which are useful as MAP4K1 inhibitors, processes for their preparation, pharmaceutical compositions comprising the compounds, and the use of the compounds or the compositions in the treatment or prevention of various diseases, conditions and/or disorders mediated by MAP4K1.
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Page/Page column 66
(2020/05/15)
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- Self-immolative systems for the disclosure of reactive electrophilic alkylating agents
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In this paper we report the design, synthesis and assessment of the first examples of self-immolative systems triggered by non-acidic electrophilic agents such as methyl, allyl or benzylic halides. These systems provide a visual colorimetric disclosure response upon exposure to these electrophilic reagents under mild, basic conditions without the need for the use of analytical instrumentation.
- Acton, Aaron L.,Leroux, Flavien,Feula, Antonio,Melia, Kelly,Sambrook, Mark R.,Hayes, Wayne,Russell, Andrew T.
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p. 5219 - 5222
(2019/05/07)
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- Binuclear rhodium complex containing ortho-carborane structure and preparation and application thereof
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The invention relates to a binuclear rhodium complex containing an ortho-carborane structure and preparation and application thereof. The preparation method of the rhodium complex comprises the following steps: 1) adding an n-BuLi solution into an ortho-carborane solution, and then reacting for 30-60 min at room temperature; 2) adding selenium and reacting for 1-2h at room temperature; 3) adding [Cp*RhCl2]2, reacting at room temperature for 3-6h, and performing post-treating to obtain the rhodium complex; and the rhodium complex is used to catalyze arylamine N-methylation reaction to prepare arylamine N-methylated derivatives. Compared with the prior art, the preparation method of the binuclear semi-sandwich rhodium complex containing the ortho-carborane structure is simple and green, has excellent selectivity and higher yield, and the prepared rhodium complex has higher catalytic activity at room temperature, can be used for catalyzing aromatic amine N-methylation reaction to prepare the aromatic amine N-methylation derivatives, has high catalytic reaction yield, and has wide industrial application prospect.
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Paragraph 0051-0054
(2019/10/01)
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- Iron-Catalyzed Selective N-Methylation and N-Formylation of Amines with CO2
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We herein describe an efficient iron-catalyzed selective N-methylation and N-formylation of amines with CO2 and silane using mono-phosphine as ligand. With commercially available [CpFe(CO)2]2 as catalyst, Fe-catalyzed methylation of amines was achieved with triphenylphosphine as a ligand. Using tributylphosphine as a ligand, Fe-catalyzed formylation of amines was realized at a lower temperature. The method was successfully applied in the late-stage methylation and formylation of drug molecules containing amine moiety. (Figure presented.).
- Li, Wen-Duo,Zhu, Dao-Yong,Li, Gang,Chen, Jie,Xia, Ji-Bao
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supporting information
p. 5098 - 5104
(2019/11/03)
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- Amination of Aromatic Halides and Exploration of the Reactivity Sequence of Aromatic Halides
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A base-promoted amination of aromatic halides has been developed using a limited amount of dimethylformamide (DMF) or amine as an amino source. Various aryl halides, including F, Cl, Br, and I, have been successfully aminated in good to excellent yields. Although the amination of aromatic halides with amines or DMF is usually considered as an aromatic nucleophilic substitution (SNAr) process, and the reactivity of an aromatic halide is F > Cl > Br > I, the reactivity of aromatic halides in this system was found to be I > Br a‰ F > Cl. This protocol also showed a good regioselectivity for multihalogenated aromatics. This protocol is valuable for industrial application due to the simplicity of operation, the unrestricted availability of amino sources and aromatic halides, transition metal-free conditions, no requirement for solvent, and scalability.
- Yang, Chu,Zhang, Feng,Deng, Guo-Jun,Gong, Hang
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p. 181 - 190
(2019/01/10)
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- Synthesis method of N-methylamine compound
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The invention discloses a synthesis method of an N-methylamine compound. The synthesis method is characterized in that a carbamyl imidazole compound is used as a raw material; a NaBH4/I2 is used for performing backflow in tetrahydrofuran to prepare an N-methyl structure compound. The used reduction system NaBH4/I2 has the advantages of environment-friendly effect, performance stability, high conversion rate and the like. The synthesis method has the beneficial effects that (1) the synthesis method has wide applicability; amine can be used as the raw material; carboxylic acid can also be used as the raw material; (2) the product yield is high and reaches as high as 82 percent; (3) a synthetic agent is simple and can be easily obtained; the cost is low; the process is simple; the reaction conditions are mild; the synthesis method is suitable for industrial production. A concrete reaction formula is shown in the description, wherein R1 and R2 are identical or different atoms or groups, and are respectively and independently selected from one of hydrogen atoms, C1-C20 straight-chain or branch-chain alkane, C5-C10 naphthenic groups, aryl groups and substituted aryl groups; monosubstitution or multi-substitution is performed on aromatic rings of the substituted aryl groups. In addition, KBH4 is also applicable to the reaction.
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Paragraph 0064-0067
(2018/09/08)
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- Acetic Acid Accelerated Visible-Light Photoredox Catalyzed N-Demethylation of N,N-Dimethylaminophenyl Derivatives
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N,N-Dimethylaminophenyl moiety is a common fragment in medicinal chemistry as several pharmaceuticals bearing this privileged motif are on the market and under clinical evaluation. Oxidative N-demethylation is generally regarded as the major metabolic pathway. However, pharmacokinetics, metabolites studies as well as the further structural modification are precluded by the impracticality of chemical synthesis. Here we report that acetic acid can significantly accelerate visible-light photoredox catalyzed N-demethylation of N,N-dimethylaminophenyl derivatives. This approach is easy for large scale reaction and even for potential industrial manufacture. (Figure presented.).
- Wu, Guolin,Li, Yazhen,Yu, Xuemei,Gao, Yu,Chen, Haijun
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supporting information
p. 687 - 692
(2017/02/23)
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- Stereospecific copper-catalyzed domino ring opening and sp3 C-H functionalization of activated aziridines with N-alkylanilines
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Copper efficiently catalyzed nucleophilic ring opening, sp3 C-H functionalization, and C-N bond formation in the presence of tert-butyl hydroperoxide to afford functionalized imidazolidines starting from N-sulfonylaziridines and Nalkylanilines. The products were obtained in high optical purities (95 → 99% ee) with excellent functional group tolerance.
- Sengoden, Mani,Bhowmick, Abhisikta,Punniyamurthy, Tharmalingam
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supporting information
p. 158 - 161
(2017/11/27)
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- Highly selective sp3 C-N bond activation of tertiary anilines modulated by steric and thermodynamic factors
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A highly selective sp3 C-N cleavage of tertiary anilines was achieved using the TBN/TEMPO catalyst system. When N,N-diaklylanilines (alkyl, benzyl) were employed, the N-CH3 bond was selectively cleaved via radical C-H activation. Moreover, when the allyl group was installed, totally reverse selectivity was observed. It is worth noting that the solvent effect is also crucial to obtain high reaction efficiency and selectivity.
- Jia, Xiaodong,Li, Pengfei,Shao, Yu,Yuan, Yu,Ji, Honghe,Hou, Wentao,Liu, Xiaofei,Zhang, Xuewen
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supporting information
p. 5568 - 5574
(2017/12/06)
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- Mono-N-methylation of anilines with methanol catalyzed by a manganese pincer-complex
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The selective mono-N-methylation of anilines derivatives was achieved under mild conditions using inexpensive methanol as C1 source. Under hydrogen borrowing conditions, using a tridentate PN3P manganese pre-catalyst (5?mol%), a catalytic amount of base (20?mol%), for 24?h at 120?°C, a large variety of anilines derivatives was methylated in good to excellent yield. Mechanistic investigations allowed us to isolate and characterize by X-ray diffraction studies a de-aromatized manganese intermediate.
- Bruneau-Voisine, Antoine,Wang, Ding,Dorcet, Vincent,Roisnel, Thierry,Darcel, Christophe,Sortais, Jean-Baptiste
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- Pd(II)/Ag(I)-Promoted One-Pot Synthesis of Cyclic Ureas from (Hetero)Aromatic Amines and Isocyanates
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A simple and facile one-pot reaction has been developed to afford a diverse range of N,N′-disubstituted benzimidazolones and imidazopyridinones containing two differently substituted N atoms. A cooperative Pd(II)/Ag(I) system promotes the sequential addition/intramolecular C-H amidation reaction of (hetero)aromatic amines and isocyanates, leading to the formation of two C-N bonds. A mechanism involving radical intermediates generated by single-electron transfer (SET) in the presence of a Ag2CO3 oxidant and Pd(OAc)2 Lewis acid is proposed. This protocol offers an operationally easy, simple, and robust approach with the use of readily available starting materials, good functional group tolerance, and high efficiency.
- Youn, So Won,Kim, Yi Hyun
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p. 6140 - 6143
(2016/12/09)
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- INHIBITORS OF NECROPTOSIS
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The invention relates to novel heterocyclic compounds of Formula (I) which inhibit necroptosis and methods for their use. The compounds may be useful in the treatment of conditions associated with deregulated necroptosis.
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Page/Page column 40
(2016/09/22)
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- Functional ion liquid method for catalytic synthesis of amine compounds
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The invention discloses a method for synthesizing an amine compound catalyzed by functionalized ionic liquid. According to the method, functionalized ionic liquid is used as a catalyst to catalyze N-alkylation of amine and alcohol to synthesize corresponding compound derivatives. Acid functionalized ionic liquid is used as the catalyst to synthesize a series of compounds of amine. The method has the following advantages: a catalytic system is a metal-free system; the usage amount of the catalyst is small, and the catalyst has high catalytic activity, good stability and low corrosivity; operation is simple, and reaction is mild; post-treatment is easy, and the catalyst can be cyclically used.
- -
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Paragraph 0171; 0172; 0173
(2016/10/07)
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- Isotope effect profiles in the N-demethylation of N,N-dimethylanilines: A key to determine the pKa of nonheme Fe(III)-OH complexes
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N-demethylation of N,N-dimethylanilines promoted by [(N4Py)FeIVO]2+ occurs by an electron transfer-proton transfer (ET-PT) mechanism with a rate determining PT step. From the bell-shaped curve of the KDIE profile it has been estimated that the pKa of [(N4Py)FeIII-OH]2+ is 9.7.
- Barbieri, Alessia,De Gennaro, Martina,Di Stefano, Stefano,Lanzalunga, Osvaldo,Lapi, Andrea,Mazzonna, Marco,Olivo, Giorgio,Ticconi, Barbara
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p. 5032 - 5035
(2015/03/30)
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- METHODS FOR INHIBITING NECROPTOSIS
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The present invention relates to methods for inhibiting necroptosis; screening methods for identifying compounds which inhibit necroptosis; and compounds for the inhibition of necroptosis, which may be useful in the treatment of conditions associated with deregulated necroptosis.
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Page/Page column 68
(2015/12/30)
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- Copper(II)-catalyzed oxidative N-nitrosation of secondary and tertiary amines with nitromethane under an oxygen atmosphere
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The combination of a catalytic amount of Cu(OTf)2 and less than a stoichiometric amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under an O2 atmosphere effectively promoted the N-nitrosation of both secondary aromatic/aliphatic amines and tertiary aromatic amines with nitromethane (CH3NO2) leading to the preparation of N-nitrosamine derivatives.
- Sakai, Norio,Sasaki, Minoru,Ogiwara, Yohei
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supporting information
p. 11638 - 11641
(2015/07/15)
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- Pd(OAc)2-catalyzed dinitration reaction of aromatic amines
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Taking advantage of Pd(OAc)2-catalyzed dinitration reactions with Bi(NO3)3·5H2O in trifluoroethanol (TFE) and trifluoroacetic acid (TFA), we have developed an efficient and practical method for the synthesis of secondary dinitro-aromatic amines. The products could be applied to the preparation of 5-amine-N-methyl-benzimidazolone, the azo-dyes, economic advantages. The method has also been expanded to the dinitration reaction of some tertiary aromatic amines.
- Feng, Yi-Si,Mao, Long,Bu, Xiao-Song,Dai, Jian-Jun,Xu, Hua-Jian
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p. 3827 - 3832
(2015/06/02)
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- OXINDOLE INHIBITORS OF TYROSINE KINASE
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The present invention relates to new oxindole inhibitors of tyrosine kinase, pharmaceutical compositions thereof, and methods of use thereof.
- -
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Paragraph 0169; 0170
(2015/11/02)
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- Efficient synthesis of N-methylamides and amines via 4-(alkylamino)benzyl- N-methylamine as a new protecting group
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4-(Alkylamino)benzyl-N-methylamine is a good protecting group for the synthesis of N-methylamides and amines. The N-debenzylation of N-methylamides and amines can be carried out selectively and efficiently under condition using trifluoroacetic acid (TFA).
- Lee, Sang-Hak,Mu, Yu,Kim, Gun-Woo,Kim, Jin-Seok,Park, Seok-Hwi,Jin, Tian,Lee, Kee-Young,Ham, Won-Hun
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p. 1749 - 1764
(2013/09/12)
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- A ligand-free and base-free copper catalyzed reaction: Arylation of ammonia and primary amines as their acetate salts
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A ligand-free, base-free copper catalyzed arylation of ammonia and primary amines as their corresponding acetate salts are established. The Carboxylate group is believed to be catalyzing the arylation of ammonia. This reaction is specific for primary amines.
- Siddegowda, Maravanahalli S.,Yathirajan, Hemmige S.,Ramakrishna, Ramesha A.
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supporting information
p. 5219 - 5222
(2012/11/07)
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- Discovery of 1-[4-(N-benzylamino)phenyl]-3-phenylurea derivatives as non-peptidic selective SUMO-sentrin specific protease (SENP)1 inhibitors
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We developed 1-[4-(N-benzylamino)phenyl]-3-phenylurea derivative 4 (GN6958) as a non-peptidic selective SUMO-sentrin specific protease (SENP)1 protease inhibitor based on the hypoxia inducible factor (HIF)-1α inhibitor 1 (GN6767). The direct interaction of compound 1 with SENP1 protein in cells was observed by the pull-down experiments using the biotin-tagged compound 2 coated on the streptavidin affinity column. Among the various 1-[4-(N-benzylamino) phenyl]-3-phenylurea derivatives tested, compounds 3 and 4 suppressed HIF-1α accumulation in a concentration-dependent manner without affecting the expression level of tubulin protein in HeLa cells. Both compounds inhibited SENP1 protease activity in a concentration-dependent manner, and compound 4 exhibited more potent inhibition than compound 3. Compound 4 exhibited selective inhibition against SENP1 protease activity without inhibiting other protease enzyme activities in vitro.
- Uno, Masaharu,Koma, Yosuke,Ban, Hyun Seung,Nakamura, Hiroyuki
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supporting information; experimental part
p. 5169 - 5173
(2012/09/07)
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- Sulfonic acid-functionalized ionic liquids as metal-free, efficient and reusable catalysts for direct amination of alcohols
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A series of sulfonic acid-functionalized (SO3H-functionalized) ionic liquids was synthesized and used as metal-free, highly selective and efficient catalysts for the direct amination of alcohols. Notably, the activities of the series of SO3H-functionalized ionic liquids were compared and a 92% isolated yield was obtained using 3-tetradecyl-1-(butyl-4- sulfonyl)imidazolium trifluoromethanesulfonate ([BsTdIM][OTf]) as the catalyst. Importantly, the catalytic system has wide substrate scope including benzylic, allyl, propargylic, aliphatic alcohols with sulfonamide, amide, carbamate, aromatic amine and N-heterocyclic compounds. Interestingly, the system was also suitable for a multi-gram scale direct amination of alcohols. Additionally, the reusable nature of [BsTdIM][OTf] makes this protocol more attractive and avoids the disposal and neutralization of acidic catalysts. Moreover, preliminary experiments indicated that this reaction should proceed via an SN1 pathway. Copyright
- Han, Feng,Yang, Lei,Li, Zhen,Xia, Chungu
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experimental part
p. 1052 - 1060
(2012/05/21)
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- A facile and practical copper powder-catalyzed, organic solvent-and ligand-free ullmann amination of aryl halides
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A facile and practical method that the copper powder-catalyzed Ullmann amination of aryl halides with aqueous methylamine under organic solvent-and ligand-free condition at 100 °C and in air gave N-arylamines as sole products in good to excellent yields. The presence of a small amount of air is essential. Other aliphatic primary amines show good to very high reactivity. Secondary amines and aniline are not reactive. Sensitive substituents (i.e., CHO, MeCO, CN and Cl) are tolerable in the reaction.
- Jiao, Jiao,Zhang, Xi-Ru,Chang, Ning-Hui,Wang, Jie,Wei, Jun-Fa,Shi, Xian-Ying,Chen, Zhan-Guo
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supporting information; experimental part
p. 1180 - 1183
(2011/04/24)
-
- Detection of explosives via photolytic cleavage of nitroesters and nitramines
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The nitramine-containing explosive RDX and the nitroester-containing explosive PETN are shown to be susceptible to photofragmentation upon exposure to sunlight. Model compounds containing nitroester and nitramine moieties are also shown to fragment upon exposure to UV irradiation. The products of this photofragmentation are reactive, electrophilic NOx species, such as nitrous and nitric acid, nitric oxide, and nitrogen dioxide. N,N-Dimethylaniline is capable of being nitrated by the reactive, electrophilic NOx photofragmentation products of RDX and PETN. A series of 9,9-disubstituted 9,10-dihydroacridines (DHAs) are synthesized from either N-phenylanthranilic acid methyl ester or a diphenylamine derivative and are similarly shown to be rapidly nitrated by the photofragmentation products of RDX and PETN. A new (turn-on) emission signal at 550 nm is observed upon nitration of DHAs due to the generation of fluorescent donor-acceptor chromophores. Using fluorescence spectroscopy, the presence of ca. 1.2 ng of RDX and 320 pg of PETN can be detected by DHA indicators in the solid state upon exposure to sunlight. The nitration of aromatic amines by the photofragmentation products of RDX and PETN is presented as a unique, highly selective detection mechanism for nitroester- and nitramine-containing explosives and DHAs are presented as inexpensive and impermanent fluorogenic indicators for the selective, standoff/remote identification of RDX and PETN.
- Andrew, Trisha L.,Swager, Timothy M.
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experimental part
p. 2976 - 2993
(2011/06/21)
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- Decomplexation-nitroso Diels-Alder (NDA) approach to C,D-ring functionalisation for hippeastrine
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A tandem decomplexation-nitroso Diels-Alder (decomplexation-NDA) procedure has been shown to give the regiocontrol and stereocontrol needed for application in an organoiron-mediated synthesis of the alkaloid hippeastrine, using a selection of nitrosoarene
- Stephenson, G. Richard,Balfe, Andrew M.,Hughes, David L.,Kelsey, Richard D.
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p. 6806 - 6809
(2011/03/18)
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- Metal organic frameworks as heterogeneous catalysts for the selective N-methylation of aromatic primary amines with dimethyl carbonate
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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
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experimental part
p. 19 - 25
(2010/08/20)
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- 2- [ (2-SUBSTITUTED) -IND0LIZIN-3-YL] -2-OXO-ACETAMIDE DERIVATIVES AS ANTIFUNGAL AGENTS
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The invention provides compounds of formula (I), and pharmaceutically acceptable salts thereof wherein: Rl, R2, R3, R4, R5, R6, R7, X and X1 are as defined herein. These compounds are useful in the manufacture of medicaments for use in the prevention or treatment of a fungal disease. Compounds of formula (I), and agriculturally acceptable salts thereof, may also be used as agricultural fungicides.
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Page/Page column 123
(2008/12/05)
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- Microwave-assisted deformylation of N-aryl formamide by KF on basic Al2O3
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The formyl group was successfully removed from N-aryl formamide by KF on a solid support of basic Al2O3 in 4-20 min with microwave irradiation. The conditions mimic base-catalyzed hydrolysis of formamide and are compatible with carbamates and t-butyl esters, but not methyl, ethyl, and benzyl esters.
- Ge, Yiyu,Hu, Longqin
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p. 4585 - 4588
(2008/02/06)
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- Highly specific N-monomethylation of primary aromatic amines
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A synthetic methodology for the specific conversion of primary aromatic amines into their N-monomethyl derivatives under very mild conditions is presented. Anilines are treated with 4-nitrobenzenesulfonyl (nosyl) chloride to generate the corresponding sulfonamides 2 in high yields. The subsequent N-methylation reaction of the sulfonamides 2 with a solution of diazomethane is rapid and quantitative. Removal of the nosyl protecting group is readily carried out using the reagent system mercaptoacetic acid/1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) affording the N-monomethylated aromatic amines 4. The procedure is convenient, efficient, and gives rise to the N-monomethyl-anilines exclusively.
- Le Pera, Adolfo,Leggio, Antonella,Liguori, Angelo
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p. 6100 - 6106
(2007/10/03)
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- Highly chemoselective nitration of aromatic amines using the Ph3P/Br2/AgNO3 system
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The use of PPh3/Br2/AgNO3 provides a new reagent system for the novel and highly chemoselective nitration of aromatic amines under mild reaction conditions.
- Iranpoor, Nasser,Firouzabadi, Habib,Nowrouzi, Najmeh,Firouzabadi, Dena
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p. 6879 - 6881
(2007/10/03)
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- The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines
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The regioselectivity of the nitrous acid mediated dealkylation of 4-substituted-N-ethyl-N-methylanilines is a function of the acidity of the reaction mixture. At high acidity deethylation predominates, whereas demethylation is the predominant reaction in nitrosamine formation at pH 2 and above. In some cases the regioselectivity of nitrosative dealkylation changes as the run proceeds. Through the use of the corresponding 4-nitroaniline as the primary substrate, CIDNP, kinetics, kinetic deuterium isotope effects and other transformations involving nitrosations with NO2 or NOBF4 in aprotic solvents, a new mechanism of tertiary amine nitrosation has been deduced and proposed to explain regioselective deethylation. The mechanism involves the oxidation of the substrate to the amine radical cation by NO +. This is followed by the abstraction of a hydrogen atom from the carbon adjacent to the amine nitrogen by NO2 to produce an iminium ion which reacts further to produce the corresponding aldehyde and the nitrosamine. Depending upon the acidity, this process competes with three other mechanistic pathways, two of which give the nitrosamine through the iminium ion, and one leads to the formation of C-nitro compounds. The competing pathways to nitrosamine formation involve NOH elimination from a nitrosammonium ion and deprotonation of the radical cation to give an α-amino radical which rapidly oxidized to the iminium ion. Predominant, but not highly regioselective demethylation occurs by these pathways. Nitro compound formation principally arises from the reaction of NO2 with the radical cation followed by deprotonation, but also occurs by para C-nitrosation followed by oxidation. The Royal Society of Chemistry 2005.
- Teuten, Emma L.,Loeppky, Richard N.
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p. 1097 - 1108
(2007/10/03)
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