Naphthylamine Derivatives Research Articles

Palladium-Catalyzed Cascade Decarboxylative Amination/6-endo-dig Benzannulation of o-Alkynylarylketones with N-Hydroxyamides To Access Diverse 1-Naphthylamine Derivatives.

An efficient and practical one-pot strategy to produce highly substituted 1-naphthylamines via sequential palladium-catalyzed decarboxylative amination/intramolecular 6-endo-dig benzannulation reactions has been described. In this reaction, a broad range of electron-rich, electron-neutral, and electron-deficient o-alkynylarylketones react well with N-hydroxyl aryl/alkylamides to give a diversity of 1-naphthylamines in good to excellent yields under mild reaction conditions. The gram-scale synthesis, with benefits such as undiminished product yield and easy transformation, illustrated the practicality of this method.

Palladium-catalyzed C8-H alkoxycarbonylation of 1-naphthylamines with alkyl chloroformates.

A simple and efficient protocol for palladium-catalyzed C8-H alkoxycarbonylation of 1-naphthylamine derivatives with alkyl chloroformates has been developed, exhibiting broad functional group tolerance, high regioselectivity, and oxidant-free conditions. Furthermore, the reaction features its ease of further functionalization and transformation. For example, the concise synthesis of one BET bromodomain inhibitor was accomplished via benz[cd]indol-2(1H)-one after multistep transformations from the obtained alkoxycarbonylation product. In addition, the control experiments suggest that the reaction might involve a radical process and the C-H bond cleavage might not be involved in the rate-determining step.

Palladium-Catalyzed C8-H Acylation of 1-Naphthylamines with Acyl Chlorides.

A facile and efficient protocol for palladium-catalyzed regioselective C8-H acylation of 1-naphthylamine derivatives with acyl chlorides has been developed. The reaction exhibits broad functional group tolerance, and both aromatic and α,β-unsaturated acyl chlorides can be effectively coupled with 1-naphthylamines. Moreover, the picolinamide moiety as a bidentate directing likely plays a key role in this regioselective transformation.

Cobalt(II)–catalyzed C8[sbnd]H alkoxylation of 1-naphthylamine derivatives with alcohols

An efficient protocol for cobalt (II)-catalyzed regioselective aryl C8H bond alkoxylation of 1-naphthylamine derivatives with readily available alcohols has been developed, demonstrating an efficient approach to 8-alkoxy-1-naphthylamine derivatives with good functional group tolerance. Note that the picolinamide moiety as a bidentate directing group may play a key role in this regioselective transformation.

Cu(I)-Catalyzed 6- endo-dig Cyclization of Terminal Alkynes, 2-Bromoaryl Ketones, and Amides toward 1-Naphthylamines: Applications and Photophysical Properties.

Functional group substituted 1-naphthylamines, especially N-methylated ones, play important roles in numerous chemical and biological processes. However, these compounds' general and step-economic syntheses are highly limited, which seriously restricts efforts to improve the properties and develop new functions for this kind of compound. In this report, we describe the development of an efficient, convenient, and general method for the synthesis of valuable functionalized 1-naphthylamines directly from readily available terminal alkynes, 2-bromoaryl ketones, and amides via Cu(I)-catalyzed benzannulation in a green solvent (i.e., water) under Pd- and ligand-free conditions. A total of 82 functionalized 1-naphthylamines, especially synthetically and biologically useful N-methylated compounds, are synthesized in isolated yields up to 95%. Some unique features of the reaction are as follows: (1) exclusive 6 -endo-dig selectivity, (2) ready incorporation of a broad range of functional groups directly from easily available substrates, and (3) amides that can be used as aminating agents and that are excellent alternatives to toxic and/or odorous amines. Due to facile tuning of functional groups for the reaction, the products possess good electronic donor-acceptor structures and exhibit intriguing photophysical properties, such as tunable and polarity-sensitive fluorescence emission and large Stokes shifts (up to 258 nm). Utilizing the products' unique polarity-sensitive fluorescence response, we successfully applied the 1-naphthylamine derivatives, such as compound 91, to image lipid droplets (LDs) and monitor cellular LDs growth. The previously mentioned advantages of this methodology, along with the mild conditions, simple operation, and scalable synthesis, may allow this novel reaction to be extended to varied applications in chemistry, biology, and materials science.

An intermolecular C-H oxidizing strategy to access highly fused carbazole skeletons from simple naphthylamines.

Highly π-extended hetero-cyclic/aromatic skeletons are of great importance as they can be utilized in many organic material based technologies. Therefore, developing efficient, pre-activation-free, synthetic procedures for the rapid build-up of these complex structures remains a high priority objective. The herein presented approach delivers highly fused carbazole skeletons from simple naphthylamine derivatives.

COMPUTATIONAL STUDY OF BUTYL AND NAPHTHYL AMINE DERIVATIVE OF PERYLENE DIIMIDES TARGETTING TELOMERASE ENZYME FOR ANTICANCER ACTIVITY

Objective: Telomeres are protective caps present at the end of the chromosomes and it contains genetic information. From the literature survey, we selected perylene diimides which interact with the telomerase enzyme and possess anticancer activity. Telomestatin a macrocyclic chemical compound that inhibits telomerase activity as well it induces the formation of G-Quadruplex structures in the telomeric region. The main objective of the study was to find the binding affinity of butyl and naphthyl amine derivative of perylene ligands targeting telomerase enzyme for anticancer activity. Telomerase enzyme is responsible for maintaining the length of telomeres and keeping the chromosomes intact longer. Telomeres will become increasingly common with age. Perylene diimides and its derivatives show good biological activity and also in vitro studies possess efficient anticancer agent. The butyl and naphthyl amine derivatives are screened by computational techniques to study regarding binding energy and ligand interactions with respect to the targets.Methods: Butyl and naphthyl amine derivative of perylene diimides is drawn using Accelrys Draw. The structures are retrieved from the previous study. The structures are converted to pdb formats using Discovery Studio Visualizer 4.1. The study was to investigate the binding energy values of butyl and naphthyl amine derivatives of perylene diimides. Auto Dock 4.2 was used to dock the ligand with the targets. The target selected for docking was 3CE5 and 4B18. The results are visualized by Discovery Studio Visualizer 4.1. The results are compared with the standard drug N,N’-bis-(2-(1- piperidino)ethyl)-3,4,9,10-perylene tetracarboxylic acid diimide (PIPER).Results: From the results, butylamine derivative of perylene diimide possesses good binding energy when compared with standard drug PIPER. This result shows that the butylamine will be effective for anticancer therapy. In future, in vivo studies of butylamine derivative of perylene diimide will be carried out.

Cobalt-catalyzed peri-selective alkoxylation of 1-naphthylamine derivatives.

A cobalt-catalyzed C(sp2)–H alkoxylation of 1-naphthylamine derivatives has been disclosed, which represents an efficient approach to synthesize aryl ethers with broad functional group tolerance. It is noteworthy that secondary alcohols, such as hexafluoroisopropanol, isopropanol, isobutanol, and isopentanol, were well tolerated under the current catalytic system. Moreover, a series of biologically relevant fluorine-aryl ethers were easily obtained under mild reaction conditions after the removal of the directing group.

Silver(I)-Catalyzed C4-H Amination of 1-Naphthylamine Derivatives with Azodicarboxylates.

A simple and efficient protocol for silver(I)-catalyzed picolinamide directed C4-H amination of 1-naphthylamine derivatives with readily available azodicarboxylates has been developed, demonstrating a new approach to 1,4-naphthalenediamine derivatives in high yields. Note that this reaction system could proceed under external-oxidant- and additive-free conditions (only requires 5 mol % of AgOAc as the catalyst in acetone).

Ru/Cu Photoredox or Cu/Ag Catalyzed C4-H Sulfonylation of 1-Naphthylamides at Room Temperature.

A mild and efficient protocol for C4-H sulfonylation of 1-naphthylamine derivatives with sodium sulfinates has been described. This C4 sulfonylation proceeded smoothly at room temperature under Ru/Cu photoredox catalysis or Cu/Ag cocatalysis and could tolerate various functional groups. In addition, control experiments suggested that this C4-H sulfonylation reaction might proceed via a single-electron-transfer process.

Palladium-Catalyzed Regioselective C8-H Amination of 1-Naphthylamine Derivatives with Aliphatic Amines.

A simple and facile protocol for palladium-catalyzed picolinamide-directed C8-H amination of 1-naphthylamine derivatives with simple secondary aliphatic amines was developed, thereby providing a new route to 1,8-naphthalenediamine derivatives. It is noteworthy that the picolinamide moiety as a bidentate directing group may play a key role in this regioselective transformation.

Palladium-Catalyzed peri-Selective Chalcogenation of Naphthylamines with Diaryl Disulfides and Diselenides via C–H Bond Cleavage

A palladium-catalyzed and picolinamide-directed C-H thiolation of naphthylamine derivatives with diaryl disulfides has been developed to provide a convenient route to 8-sulfenyl-1-naphthylamines. The reaction proceeds via a 5-membered palladacycle intermediates to afford the peri-thiolated products exclusively, in contrast to the conventional ortho-functionalization. Moreover, the related direct selenation was also achieved with diaryl diselenides, giving the corresponding selenated products with perfect site-selectivity.

Photochemical Electron Transfer Mediated Addition of Naphthylamine Derivatives to Electron-Deficient Alkenes

Using photochemical electron transfer, N,N-dimethylnaphthylamine derivatives are added to α,β-unsaturated carboxylates. The addition takes place exclusively in the α-position of electron-deficient alkenes and mainly in the 4-position of N,N-dimethylnaphthalen-1-amine. A minor regioisomer results from the addition in the 5-position of this naphthylamine. A physicochemical study reveals that the fluorescence quenching of N,N-dimethylnaphthalen-1-amine is diffusion-controlled and that the back electron transfer is highly efficient. Therefore no transformation is observed at lower concentrations. To overcome this limitation and to induce an efficient transformation, minor amounts of water or another proton donor as well as an excess of the naphthylamine derivative are necessary. A mechanism involving a contact radical ion pair is discussed. Isotopic labeling experiments reveal that no hydrogen is directly transferred between the substrates. The hydrogen transfer to the furanone moiety observed in the overall reaction therefore results from an exchange with the reaction medium. An electrophilic oxoallyl radical generated from the furanone reacts with the naphthylamine used in excess. Concerning some mechanistic details, the reaction is compared with radical and electrophilic aromatic substitutions. The transformation was carried out with a variety of electron-deficient alkenes. Sterically hindered furanone derivatives are less reactive under standard conditions. In a first experiment, such a compound was transformed using heterogeneous electron transfer photocatalysis with TiO(2).

Synthesis and Antimicrobial Properties of Naphthylamine Derivatives Having a Thiazolidinone Moiety

The aim of this study was to evaluate the influence of pharmacophores having naphthylamine and nitro groups on the antimicrobial (antibacterial and antifungal) activity of thiazolidinone derivatives. The initial 5-substituted-2-methylmercaptothiazolidin-4-ones were subjected to S-demethylation to yield 2-amino-substituted thiazolidinones. 4-Nitro-1-naphthylamine, nitrofuran aldehydes, and nitrobenzene aldehydes were used as pharmacophoric compounds having amino or aldehyde groups. Antimicrobial (antibacterial and antifungal) activity of the new compounds was tested in vitro against bacterial cultures - Staphylococcus aureus, Escherichia coli, Bacillus subtilis, Klebsiella pneumoniae - and fungal cultures - Candida albicans, Candida glabrata, Candida krusei, Candida kefyr, Candida tropicalis, and Candida parapsilosis. Microbiological analysis showed that all new thiazolidinone derivatives with nitronaphthylamine substituent possessed antibacterial and antifungal properties. New compounds 2a-b showed similar antibacterial activity in vitro against S. aureus and B. subtilis as aminopenicillins. The lowest antibacterial activity of all newly synthesized compounds was against capsule-forming bacteria K. pneumoniae and against gram-negative bacteria E. coli (minimum inhibitory concentration range, 500-1000 μg/mL). The minimum inhibitory concentration of naphthylamine derivatives varied in the range of 0.4-1000 μg/mL, and activity of some newly synthesized compounds was similar to the activity of aminopenicillins and fluconazole, an antifungal preparation. Based on the results, it is possible to separate the perspective group of potential antimicrobial compounds.

Pd(0)-Catalyzed [1,5]-Sigmatropic Hydrogen Shift of Propargylic Esters toward Substituent Naphthylamines

A novel and convenient carboannulation method for the synthesis of highly substituted naphthylamine derivatives has been developed though a Pd(0)-catalyzed [1,5]-sigmatropic hydrogen shift and cyclization reaction of propargyl esters.

Synthesis and Antibacterial Activities of Some Schiff Bases

Schiff bases p‐hydroxybenzylidene‐2‐carboxyaniline, p‐nitrobenz‐ylidene‐2‐carboxyaniline, p‐(N, N‐dimethyl)aminobenzylidene‐2‐carboxyaniline, N‐(4‐hydroxybezylidene)‐benzene‐1,2‐diamine, N-‐(4‐nitrobezylidene)benzene‐1,2‐diamine, N‐(4‐(N, N‐dimethylaminobezylidene)benzene‐1,2‐diamine, N‐(4‐(N,N‐dimethylamino)benzylidene)naphthalen‐1‐amine,N‐(4‐nitrobenzylidene)naphthalen‐1‐amine,N-‐(4‐chlorobenzylidene)naphthalen‐1‐amine,sodium‐4‐(4‐(N,N‐dimethyl amino)benzylideneamino)naphthalene‐1‐sulfonate,sodium ‐4‐(4‐nitrobenzylidene‐amino)naphthalene‐1‐sulfonate and sodium‐4‐(4‐chlorobenzylideneamino) naphthalene‐1‐sulfonate obtained by condensation of aniline and naphthyl‐amine derivatives with some aromatic aldehydes were characterized by physical and spectral methods. The biological activity of these products were as antibacterial agents against three species of human pathogenic bacteria such as Escherichia coli, Staphylococcus aureus and Klebsiella sp. Nearly 50% of these compounds showed reasonable activity against the bacterial species investigated and we found that the antibacterial activity is dependent on the molecular structure of the compounds.

Differentiation induction of mouse embryonic stem cells into sinus node-like cells by suramin

Embryonic stem (ES) cells differentiate into cardiac phenotypes representing early pacemaker-, atrial-, ventricular-, and sinus node-like cells, however, ES-derived specification into sinus nodal cells is not yet known. By using the naphthylamine derivative of urea, suramin, we were able to follow the process of cardiac specialization into sinus node-like cells. Differentiating mouse ES cells were treated with suramin (500 µM) from day 5 to 7 of embryoid body formation, and cells were analysed for their differentiation potential via morphological analysis, flow cytometry, RT-PCR, immunohistochemistry and patch clamp analysis. Application of suramin resulted in an increased number of cardiac cells, but inhibition of neuronal, skeletal muscle and definitive endoderm differentiation. Immediately after suramin treatment, a decreased mesendoderm differentiation was found. Brachyury, FGF10, Wnt8 and Wnt3a transcript levels were significantly down-regulated, followed by a decrease in mesoderm- and cardiac progenitor-specific markers BMP2, GATA4/5, Wnt11, Isl1, Nkx2.5 and Tbx5 immediately after removal of the substance. With continued differentiation, a significant up-regulation of Brachyury, FGF10 and GATA5 transcript levels was observed, whereas Nkx2.5, Isl1, Tbx5, BMP2 and Wnt11 levels were normalized to control levels. At advanced differentiation stages, sinus node-specific HCN4, Tbx2 and Tbx3 transcript levels were significantly up-regulated. Immunofluorescence and patch-clamp analysis confirmed the increased number of sinus node-like cells, and electrophysiological analysis revealed a lower number of atrial- and ventricular-like cardiomyocytes following suramin treatment. We conclude that the interference of suramin with the cardiac differentiation process modified mesoderm- and cardiac-specific gene expression resulting in enhanced formation of sinus node-like cells.

Simple Triarylamine-Based Dyes Containing Fluorene and Biphenyl Linkers for Efficient Dye-Sensitized Solar Cells

New dipolar dyes featuring arylamine donors, fluorene or biphenyl conjugation, and cyanoacetic acid acceptor units have been synthesized and characterized by spectral, optical, and electrochemical measurements. Absorption measurements indicate that the fluorene conjugation is beneficial for red shifting the charge transfer transition and increasing the optical density. On the contrary, the biphenyl linker leads to a blue-shifted hypochromic charge-transfer transition due to the inefficiency in the π-conjugation. For a particular linker, the diphenylamine unit acts as an efficient donor when compared to the 1-naphthylphenylamine moiety. However, the red shift observed in the absorption profile for the diphenylamine-containing dyes is compensated for by a reduction in the molar extinction coefficient, that is, the naphthylamine derivatives are beneficial for increasing the molar extinction coefficient. Electrochemical investigations show that the fluorene-based dyes are more redox stable than the correspond...

Highly Efficient Synthesis of Optically Pure 5,5‘,6,6‘,7,7‘,8,8‘-Octahydro-1,1‘-bi-2-naphthol and -naphthylamine Derivatives by Partial Hydrogenation of 1,1‘-Binaphthyls with Carbon Nanofiber Supported Ruthenium Nanoparticles

Use of Ru/CNF-P, nanoruthenium particles dispersed on a nanocarbon fiber support, realizes highly efficient catalytic partial hydrogenation of 1,1'-bi-2-naphthol and -naphthyl-amine derivatives. The reactions proceed in high turnover numbers without racemization of the axial chirality, offering a practical procedure for the production of optically pure 5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyls in good to high yields.

Photovoltaic Characteristics of a Naphthylamine Derivative

AbstractOrganic photovoltaic (OPV) cells were fabricated via vacuum vapor deposition with {4‐[2‐(3‐dicyanomethylidene‐5,5‐dimethylcyclohexenyl)vinyl]phenyl}di(1‐naphthyl)amine (DNP‐2CN) as the electron donor, and fullerene (C60) as the electron acceptor. A thin film (10 nm) of tris(8‐quinolinolato)aluminum (Alq3) was adopted as the buffer layer. A device based on this DNP‐2CN exhibited an open circuit voltage (Voc) of 370 mV, a short‐circuit current density (Jsc) of 0.61 mA·cm−2, and a white‐light power conversion efficiency (() of 0.09% (AM1.5, 75 mW·cm−2).