Reaction Of Primary Aromatic Amines Research Articles

Copper-Catalyzed Multicomponent Coupling Reaction of Primary Aromatic Amines, Rongalite, and Alkynes: Access to N-Aryl Propargylamines.

In this work, a practical copper-catalyzed multicomponent coupling reaction of primary aromatic amines, rongalite, and alkynes for the direct synthesis of N-aryl propargylamines has been developed. This method could overcome the substrate limitation in A3 coupling reactions of primary aromatic amines, formaldehyde, and alkynes. Mechanistic studies revealed that rongalite acts as not only the active C1 unit but also the accelerator to activate the in situ-generated N-arylmethanimines for the coupling reaction with alkynes. This coupling reaction is highly efficient and features a broad substrate scope, as well as utility with scale-up synthesis and converting the corresponding product N-aryl propargylamines into useful heterocyclic skeletons.

Immobilization and DFT studies of Tin chloride on UiO-66 metal–organic frameworks as active catalyst for enamination of acetylacetone

An efficient synthetic method for the preparation of β-enaminones catalyzed by immobilization of SnCl2 on Zr-metal–organic frameworks (UiO-66 MOF) and designated as SnUiO66 is described. Also the prepared catalyst was characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy and N2 adsorption and desorption techniques. XPS and DFT studies on Sn UiO66 were consistent with the immobilization of Sn chloride as SnIV on MOF. A variety of β-enaminones were synthesized via reaction of primary aromatic amines with acetylacetone. It was found that SnUiO66 shows moderate-to-high catalytic activity for enamination reactions. The catalyst was found to be reusable up to four catalytic cycles without any appreciable loss in activity.

ChemInform Abstract: Cyanoacetic Acid as a Masked Electrophile: Transition‐Metal‐Free Cyanomethylation of Amines and Carboxylic Acids.

AbstractA novel cyanomethylation reaction of primary aromatic amines, secondary, and even tertiary amines as well as of carboxylic acids is described.

Natural Acid Catalyzed Synthesis of Schiff under Solvent-Free Condition: As a Green Approach

The reaction of primary aromatic amines with aryl aldehydes is found to be catalyzed by lemon juice as natural acid under solvent-free conditions to give the corresponding Schiff bases in good yields. This eco-friendly reaction has many advantages like economical, environmental, mild reaction conditions and simple work-up with high product yield.

Cerium(III)-Catalyzed Synthesis of Schiff Bases: A Green Approach

The reaction of primary aromatic amines with aryl aldehydes is found to be catalyzed by cerium chloride heptahydrate under solvent-free conditions to give the corresponding Schiff bases in good yields.

ChemInform Abstract: Novel Syntheses of Heterocycles with N-(1-Haloalkyl)azinium Halides. Part 3. Preparation of 2-Aryl-1-arylimino-2,3-dihydro-1H-isoindoles.

The title compounds can be synthesized readily by reaction of primary aromatic amines with the azinium salt obtained from thionyl chloride, pyridine, and 1,2-benzenedicarboxaldehyde.

The reaction of primary aromatic amines with alkylene carbonates for the selective synthesis of bis-N-(2-hydroxy)alkylanilines: the catalytic effect of phosphonium-based ionic liquids

At T≥ 140 °C, different primary aromatic amines (pX-C(6)H(4)NH(2); X = H, OCH(3), CH(3), Cl) react with both ethylene- and propylene-carbonates to yield a chemoselective N-alkylation process: bis-N-(2-hydroxyalkyl)anilines [pX-C(6)H(4)N(CH(2)CH(R)OH)(2); R = H, CH(3)] are the major products and the competitive formation of carbamates is substantially ruled out. At 140 °C, under solventless conditions, the model reaction of aniline with ethylene carbonate goes to completion by simply mixing stoichiometric amounts of the reagents. However, a class of phosphonium ionic liquids (PILs) such as tetraalkylphosphonium halides and tosylates turn out to be active organocatalysts for both aniline and other primary aromatic amines. A kinetic analysis monitored by (13)C NMR spectroscopy, shows that bromide exchanged PILs are the most efficient systems, able to impart a more than 8-fold acceleration to the reaction. The reactions of propylene carbonate take place at a higher temperature than those of ethylene carbonate, and only in the presence of PIL catalysts. A mechanism based on the Lewis acidity of tetraalkylphosphonium cations and the nucleophilicity of halide anions has been proposed to account for both the reaction chemoselectivity and the function of the catalysts.

ChemInform Abstract: CuCl‐Catalyzed Aerobic Oxidative Reaction of Primary Aromatic Amines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

CuCl-catalyzed aerobic oxidative reaction of primary aromatic amines

The oxidations of primary aromatic amines were investigated. Cuprous chloride-air system can catalyze the oxidation of primary aromatic amines to azo derivatives, anils, and/or quinone anils. The experimental procedure is simple and the products could be easily isolated in high yields.

A new palladium-mediated approach to 4- N-arylamino-1-butanols from peroxidic tetrahydrofuran and primary aromatic amines

Reaction of primary aromatic amines with peroxidic tetrahydrofuran (THF) in the presence of hydrogen and 10% palladium on carbon catalyst results in THF ring opening to give 4- N-arylamino-1-butanols in a good yield. The reaction mechanism is believed to involve a free-radical sequence resulting in an imino alcohol subsequently reduced to product.

4-Dimethylaminocinnamaldehyde As a Photometric Reagent for Primary Aromatic Amines

The interaction of primary aromatic amines (PAAs) with 4-dimethylaminocinnamaldehyde (DMACA) is studied in various media by UV, IR, and 1H NMR spectroscopy. The optimum conditions for these reactions have been found, and the reasons for better analytical effects in the condensation reaction of PAAs with this reagent have been revealed. The physicochemical properties of the analytical form are studied using the aniline–DMACA model system as an example. A correlation has been found between the pHopt of the reactions under study and the pKa values of arylamines.

Mono-N-methylation of primary amines with alkyl methyl carbonates over Y faujasites. 2. Kinetics and selectivity.

In the presence of a Na-exchanged Y faujasite, the reaction of primary aromatic amines 1 with 2-(2-methoxyethoxy)methylethyl carbonate [MeO(CH(2))(2)O(CH(2))(2)OCO(2)Me, 2a] yields the corresponding mono-N-methyl derivatives ArNHMe with selectivity up to 95%, at substantially quantitative conversions. At 130 degrees C, the reaction can be run under diffusion-free conditions and is strongly affected by the solvent polarity: for instance, in going from xylene (epsilon(r) = 2.40) to triglyme (epsilon(r) = 7.62) as the solvent, the pseudo-first-order rate constant for the aniline (1a) disappearance shows a 5-fold decrease. In DMF (epsilon(r) = 38.25), the same reaction does not occur at all. Competitive adsorption of the solvent and the substrate onto the catalytic sites accounts for this result. The behavior of alkyl-substituted anilines ZC(6)H(4)NH(2) [Z = p-Me, p-Et, p-Pr, p-(n-Bu) (1b-e); Z = 3,5-di-tert-butyl- and 2,4,6-tri-tert-butylanilines (1f,g)] and p-alkoxyanilines p-ZC(6)H(4)NH(2) [Z = OMe, OEt, OPr, O-n-Bu (1b'-e')] clearly indicates a steric effect of ring substituents: as diffusion of the amine into the catalytic pores is hindered, the reaction hardly proceeds and the mono-N-methyl selectivity (S(M/D)) drops as well. Moreover, the strength of adsorption of the amine onto the catalyst influences the rate and the selectivity as well: the reaction of p-anisidine and p-toluidine-despite the higher nucleophilicity of these compounds-is slower and even less selective with respect to aniline. From a mechanistic viewpoint, the intermediacy of carbamates ArN(Me)CO(2)R [R = MeO(CH(2))(2)O(CH(2))(2)] is suggested. At 90 degrees C, the reaction of benzylamine (7)-a model for aliphatic amines-with dimethyl carbonate shows that the reaction outcome can be improved by tuning the amphoteric properties of the catalyst: in going from CsY to the more acidic LiY zeolite, methylation is not only more selective (S(M/D) ratio increases from 77% to 84%) but even much faster (CsY, conversion of 36% after 22 h; LiY, conversion of 43% after 7 h).

ChemInform Abstract: Reaction of Primary Aromatic Amines with Alkyl Carbonates over NaY Faujasite: A Convenient and Selective Access to Mono‐N‐alkyl Anilines.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Reaction of primary aromatic amines with alkyl carbonates over NaY faujasite: a convenient and selective access to mono-N-alkyl anilines.

At atmospheric pressure and at 130-160 degrees 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.

Reaction of 2,5-substituted 3,3,4,4-tetracyanopyrrolidines with anilines

The ambiguity of the reaction of primary aromatic amines with 2,5-substituted 3,3,4,4-tetracyanopyrrolidines depending on conditions was shown: At room temperature 2-amino-1-R1-5-R-3,4,4-tricyano-2-pyrrolines are formed, while on heating-2-aryl-amino-1,1,-dicyanoethylenes are obtained.

Novel Syntheses of Heterocycles with N‐(1‐Haloalkyl)Azinium Halides. Part 3. Preparation of 2‐Aryl‐1‐Arylimino‐2,3‐Dihydro‐1H‐Isoindoles

AbstractThe title compounds can be synthesized readily by reaction of primary aromatic amines with the azinium salt obtained from thionyl chloride, pyridine, and 1,2‐benzenedicarboxaldehyde.

Difunctionalization of primary aromatic amines with ethylene; synthesis of μ-arylnitrilobis(ethane-2,1-diyl)dimercury(II) complexes. Crystal structure of 2,4,6-Me 3C 6H 2N-(CH 2CH 2HgCl) 2

Reaction of primary aromatic amines, mercuric acetate, and ethylene in tetrahydrofuran under pressure (ca. 40 atm) yields the organomercurials ArN(CH 2CH 2-HgOAc) 2 (Ar = Ph, 2-ClC 6H 4, 3-ClC 6H 4, or 4-ClC 6H 4) or, after treatment of the crude products with sodium halide, ArN(CH 2CH 2HgX) 2 (Ar = 4-MeC 6H 4, 4-MeOC 6H 4, or 2,4,6-Me 3C 6H 2, X = Cl; Ar = 2,4-Cl 2C 6H 3, 2,6-Cl 2C 6H 3, or 2,4,6-Br 3C 6H 2, X = Br). The X-ray diffraction study of 2,4,6-Me 3C 6H 2N(CH 2CH 2HgCl) 2 shows the molecules to have near linear C-Hg-Cl stereochemistry, and to be arranged in centrosymmetric dimers with weak Hg ··· Cl intermolecular bonding.

β-Arylaminoacrolein誘導体の研究(第3報)Malonaldehyde Dianil誘導体の合成とその反応

Reaction of primary aromatic amines (I) with malonaldehyde bis(diethyl acetal) derivatives (II, V) in ethanol gave malonaldehyde dianil derivatives (III, IV). Treatment of III with bromine afforded bromomalonaldehyde dianil (IV). III reacted with acetic anhydride to give β-(N-acetylamino)acrolein (VII) and acetylamine (VIII). Acetylation of III with acetyl chloride afforded N-acetates (VI), which reacted with acetic anhydride to give VIIb and VIIIb.

The chemistry of ortho-benzoquinones. Part VI. The reaction of primary aromatic amines with alkyl substituted 1,2-benzoquinones: the displacement of alkyl groups in the 4- and 5-positions

The reaction of primary aromatic amines with alkyl substituted 1,2-benzoquinones has been investigated. An alkyl Substituent in the 3-position has no effect on the course of the reaction which proceeds as with 1,2-benzoquinone itself (see Part IV),2 but primary alkyl groups in the 4(5)-position are displaced by an arylamino-group. If there are methyl groups in both the 4- and the 5-positions only one is displaced. The methyl group in 4-methyl-1,2-naphthoquinone is likewise displaced. With ortho-phenylenediamine no alkyl displacement occurs but alkyl phenazines are formed. The mechanism of the displacement has been elucidated.

Quinone Imides. XXII. The Reaction of Primary Aromatic Amines with 2,3,5,6-Tetrachloro-p-quinonedibenzenesulfonimide1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTQuinone Imides. XXII. The Reaction of Primary Aromatic Amines with 2,3,5,6-Tetrachloro-p-quinonedibenzenesulfonimide1Roger Adams and B. H. BraunCite this: J. Am. Chem. Soc. 1952, 74, 23, 5869–5871Publication Date (Print):December 1, 1952Publication History Published online1 May 2002Published inissue 1 December 1952https://doi.org/10.1021/ja01143a014RIGHTS & PERMISSIONSArticle Views73Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (442 KB) Get e-Alerts Get e-Alerts