Naphthalic Anhydrides Research Articles

Palladium-Catalyzed Double Decarboxylative [3 + 2] Annulation of Naphthalic Anhydrides with Internal Alkynes.

A palladium-catalyzed [3 + 2] annulation of naphthalic anhydrides with internal alkynes has been developed. The present protocol offers an efficient and convenient route to access a series of 1,2-disubstituted acenaphthylenes with excellent functional group compatibility. The reaction is proposed to proceed through a double decarboxylation sequence. The reported synthetic protocols can be extended to napthalene- and perylenedicarboximide-containing substrates. The molecular structures, photophysical properties, and frontier molecular orbitals of the obtained adducts were investigated by X-ray crystallography, UV-vis and fluorescence spectroscopy, and DFT calculations.

N-Fluorobenzamide-Directed Formal [4+2] Cycloaddition Reaction with Maleic Anhydride: Access to Fluorescent Aminonaphthalic Anhydrides.

We have developed a formal [4+2] cycloaddition reaction of N-fluorobenzamides and maleic anhydride in the presence of CuI and LiOH, and a series of fluorescent 1-amino-2,3-naphthalic anhydrides were produced in good yields. This reaction proceeded via a multistep process involving nitrogen-centered radical generation, 1,5-hydrogen atom transfer, and benzylic radical addition to the amide carbonyl oxygen to generate an N-(tert-butyl) isobenzofuran-1(3H)-imine intermediate, which isomerized to an N-(tert-butyl) isobenzofuran-1-amine via deprotonation and protonation with the aid of LiOH; finally, the amine underwent a [4+2] cycloaddition reaction with maleic anhydride to give the 1-amino-2,3-naphthalic anhydride product upon dehydrating aromatization. Notably, the corresponding naphthalic anhydride products could be transformed into a diverse array of naphthalimides. Both the naphthalic anhydrides and the naphthalimides exhibited similar fluorescent features.

New polynaphthylimides based on 3,3'-diamino-4,4'-dichloroarylenes and aroylene-bis(naphthalic anhydrides) with improved solubility, thermal and fire resistance

Soluble polynaphthylimides not previously described were obtained by reacting 3,3'-diamino-4,4'-dichloroarylenes with aroylene-bis(naphthalic anhydrides) containing dichloroethylene, ether, and carbonyl groups. The infl uence of introduced chlorine atoms into aromatic nuclei, dichloroethylene, carbonyl and methylene groups between the phenyl nuclei of the central fragments of macromolecules on the solubility, thermal and strength properties of the synthesized polymers has been studied.

SYNTHESIS AND PROPERTIES OF IMIDATION PRODUCTS OF MONOSUBSTITUTED AND DISUBSTITUTED NAPHTHALIC ANHYDRIDES WITH P-AMINOBENZOIC ACID

4-Monosubstituted and 4,5-disubstituted halogeno- and nitro- N-(4-carboxyphenylnaphthalimides) were synthesized by imidation of the corresponding 4-monosubstituted and 4,5-disubstituted naphthalic anhydrides with para-aminobenzoic acid using acetic acid as solvent with 75-85% yields. 4-Amino-N- (4-carboxyphenyl)naphthalimide and 4,5-diamino-N-(4-carboxyphenyl)naphthalimide were obtained by reduction of corresponding nitrosubstituted N-(4-carboxyphenyl)naphthalimides using sodium dithionite as reducing agent in mixed ethanol-water solvent. The completion of reaction was monitored by thin layer chromatography with disappearance of the spot of the corresponding starting naphthalic anhydride. Starting 4-monosubstituted and 4,5-disubstituted naphthalic anhydrides were obtained by oxidation of corresponding substituted acenaphthenes with sodium dichromate in acetic acid. The synthesized N-carboxyphenylnaphthalimides with chlorine and bromine in positions 4 or 4 and 5 are yellow crystal substances with blue fluorescence; 4-nitro- and 4,5-dinitro-N-carboxyphenylnaphthalimides are orange crystal substances without fluorescence; 4-amino-, 4-dimethylamino and 4,5-diamino-N-carboxyphenylnaphthalimides are orange crystal substances with orange fluorescence. The structure of all the synthesized products was confirmed by IR and NMR 1H spectroscopy. The results of computer screening of the synthesized compounds using the PASS Online Internet service confirm a wide range of biological activity of N-carboxyphenylnaphthalimides, which makes them promising substances for further biological testing.

Ring-Opening Copolymerization of Cyclohexene Oxide and Cyclic Anhydrides Catalyzed by Bimetallic Scorpionate Zinc Catalysts.

The catalytic activity and high selectivity reported by bimetallic heteroscorpionate acetate zinc complexes in ring-opening copolymerization (ROCOP) reactions involving CO2 as substrate encouraged us to expand their use as catalysts for ROCOP of cyclohexene oxide (CHO) and cyclic anhydrides. Among the catalysts tested for the ROCOP of CHO and phthalic anhydride at different reaction conditions, the most active catalytic system was the combination of complex 3 with bis(triphenylphosphine)iminium as cocatalyst in toluene at 80 °C. Once the optimal catalytic system was determined, the scope in terms of other cyclic anhydrides was broadened. The catalytic system was capable of copolymerizing selectively and efficiently CHO with phthalic, maleic, succinic and naphthalic anhydrides to afford the corresponding polyester materials. The polyesters obtained were characterized by spectroscopic, spectrometric, and calorimetric techniques. Finally, the reaction mechanism of the catalytic system was proposed based on stoichiometric reactions.

Design, Synthesis, and Evaluation of Novel 3-Carboranyl-1,8-Naphthalimide Derivatives as Potential Anticancer Agents

We synthesized a series of novel 3-carboranyl-1,8-naphthalimide derivatives, mitonafide and pinafide analogs, using click chemistry, reductive amination and amidation reactions and investigated their in vitro effects on cytotoxicity, cell death, cell cycle, and the production of reactive oxygen species in a HepG2 cancer cell line. The analyses showed that modified naphthalic anhydrides and naphthalimides bearing ortho- or meta-carboranes exhibited diversified activity. Naphthalimides were more cytotoxic than naphthalic anhydrides, with the highest IC50 value determined for compound 9 (3.10 µM). These compounds were capable of inducing cell cycle arrest at G0/G1 or G2M phase and promoting apoptosis, autophagy or ferroptosis. The most promising conjugate 35 caused strong apoptosis and induced ROS production, which was proven by the increased level of 2′-deoxy-8-oxoguanosine in DNA. The tested conjugates were found to be weak topoisomerase II inhibitors and classical DNA intercalators. Compounds 33, 34, and 36 fluorescently stained lysosomes in HepG2 cells. Additionally, we performed a similarity-based assessment of the property profile of the conjugates using the principal component analysis. The creation of an inhibitory profile and descriptor-based plane allowed forming a structure–activity landscape. Finally, a ligand-based comparative molecular field analysis was carried out to specify the (un)favorable structural modifications (pharmacophoric pattern) that are potentially important for the quantitative structure–activity relationship modeling of the carborane–naphthalimide conjugates.

Metalloenzyme mimic: diironhexacarbonyl cluster coupled to redox-active 4-mercapto-1,8-naphthalic anhydride ligands

The non-innocent redox-active ligand, 4-mercapto-1,8-naphthalic anhydride (HS-NAH), has been used in the design and synthesis of a diironhexacarbonyl complex, [μ-(S-NAH)2Fe2(CO)6]. [μ-(S-NAH)2Fe2(CO)6] has been characterized by spectroscopic methods and cyclic voltammetry. Infrared spectrum of [μ-(S-NAH)2Fe2(CO)6] displays peaks corresponding to terminal metal CO groups (2081, 2044, 2006 cm−1) and peaks assigned to C=O of the naphthalic anhydrides (1780, 1740 cm−1). Electrochemical measurements of [μ-(S-NAH)2Fe2(CO)6] feature redox events that are metal-based (irreversible, Epc: − 1.13 V, − 1.60 V vs Fc/Fc+) and naphthalic anhydride centered (partially chemically reversible, Epc: − 1.99 V; Epa: − 1.90 V vs Fc/Fc+). Cyclic voltammetric analysis of [μ-(S-NAH)2Fe2(CO)6] in the presence of acetic acid show that the complex mimics the active site of [Fe–Fe]-hydrogenase by catalyzing the electrochemical reduction of protons to hydrogen with an overpotential of − 0.67 V. The bi-functional model, [μ-(S-NAH)2Fe2(CO)6], exhibits electronic coupling with synergistic metal–ligand interactions leading to transformation of protons to molecular hydrogen.

SYNTHETIC METHODS, PROPERTIES AND APPLICATION OF CONDENSATION PRODUCTS OF 1,8-NAPHTHALIC ANHYDRIDES WITH 1,2-DIAMINES (A REVIEW)

The literary data concerning preparation methods and spectral properties of cyclocondensation products of 1,8-naphthalic anhydrides with aromatic and aliphatic 1,2-diamines and their use as luminescent materials have been summarized. The reaction of 1,8-naphthalic anhydrides with ortho-phenylenediamine results in the formation of 1,8-naphthoylene-1’,2’-benzimidazoles, which are widely used as materials for luminescent flaw detection, for synthesis of polymers with luminescent color, in organic light emitting diodes, as luminescent sensors for cations of various metals. Moreover, their cytotoxic activity is studied in relation to cells of various tumors. Acenaphthoquinone or 8-formyl-1-naphthoic acid can also be used as starting materials for synthesis of 1,8-naphthoylene-1’,2’-benzimidazoles. The spectral properties of 1,8-naphthoylene-1’,2’-benzimidazoles can be varied by the substituent introduction to naphthalene or/and phenyl moieties leading to luminescent materials with blue, green-yellow or red luminescence. Reaction of 4-substituted naphthalic anhydrides with o-phenylenediamine results in mixture of two constitutional isomers due to nonequivalence of two carbonyl groups in starting anhydride. The isomer ratio remains unchanged provided that syntheses are carried out under the same conditions, therefore the luminescent properties of such isomer mixtures are constant. 1,8-Naphthoylene-1’,2’-benzimidazoles with electron donating groups in positions 4 or 5 of naphthalene ring can be successfully obtained by nucleophilic aromatic substitution of halogen by amine or alcoholate. The introduction of electron donating substituents to positions 4 or 5 of naphthalene ring results in bathochromic shift of absorption and emission maxima compared to unsubstituted 1,8-naphthoylene-1’,2’-benzimidazole, corresponding shift is 10-20 nm larger for 5-isomer than for 4-isomer. There are few examples of applying amines other than o-phenylenediamine for cyclocondensation with naphthalic anhydrides, for instance naphthalene-2,3-diamine and ethylenediamine were used as starting materials.

SYNTHESIS OF N-CARBOXYETHYLNAPHTHALIMIDES WITH FRAGMENTS OF PRIMARY AND SECONDARY AMINES IN POSITIONS 4 AND 5

New N-carboxyethyl-1,8-naphthalimides with fragments of morpholine and piperidine in positions 4 and 5 of naphthalene ring were synthesized by acylation of β-alanine with 4,5-dimorpholino- and 4,5-dipiperidino-1,8-naphthalic anhydrides in acetic acid. Corresponding 4,5-disubstituted naphthalic anhydrides were obtained by nucleophilic substitution of chlorine atoms in 4,5-dichloro-1,8-naphthalic anhydride on corresponding electron donating amino substitutients using dimethyl sulfoxide as solvent. Starting 4,5-dichloro-1,8-naphthalic anhydride was obtained by oxidation of 4,5-disubstituted acenaphthene with sodium dichromate in acetic acid. The same sequence of reactions can not be used for synthesis of N-carboxyethyl-1,8-naphthalimides with 2-hydroxyethylamino groups in positions 4 and 5 as the main product of reaction of 4,5-dichloro-1,8-naphthalic anhydride with ethanolamine is the product of nucleophilic addition of primary amine to carbonyl group of anhydride cycle but not the product of chlorine atoms substitution. Thus N-carboxyethyl-4,5-di(2-hydroxyethylamino)-1,8-naphthalimide was obtained by acylation of β-alanine with 4,5-dichloro-1,8-naphthalic anhydride followed by chlorine atoms substitution in N-carboxyethyl-4,5-dichloro-1,8- naphthalimide. The synthesized N-carboxyethylnaphthalimides with morpholino-, piperidino and 2-hydroxyethylamino groups in positions 4 and 5 are orange crystal substances with yellow fluorescence. Their structure was confirmed by IR and NMR 1H spectroscopy. The obtained fluorophores have weak fluorescence in aqueous solutions but their fluorescence increases 14-22 times by addition of albumin, so they can be considered as perspective substances for their further research as fluorescent probes for proteins.

SYNTHESIS OF 3,5-DIBROMO- AND 2,4,5-TRIBROMO-1,8-NAPHTHALIMIDES

3,5-Dibromo-1,8-naphthalic acid and 2,4,5-tribromo-1,8-naphthalic acid were synthesized by oxidation of 1,5,7-tribromoacenaphthylene and 3,5,6-tribromoacenaphthylene by sodium dichromate in anhydrous acetic acid. The obtained naphthalic acids were heated for 2 hours at 110 °C, at which the acids were completely converted to corresponding naphthalic anhydrides with the overall yields of 53% and 45% respectively. Anhydrides were crystallized from acetic anhydride to form white needle crystals with melting points 207.5-208 °C and 222-223 °C for 3,5-dibromo-1,8-naphthalic anhydride and 2,4,5-tribromo-1,8-naphthalic anhydride respectively. 3,5-Dibromo-1,8-naphthalimide and 2,4,5-tribromo-1,8-naphthalimide were obtained by ammonolysis of corresponding anhydrides with aqueous ammonia solution. Formation of naphthalimide cycle takes place in several stages. At the first step ammonia molecule attacks the electrophilic carbon atom of carbonyl group with opening of the anhydride cycle following with proton migration from nitrogen to oxygen atom to form the monoamide of 1,8-naphthalenedicarboxylic acid. Further, the nitrogen atom of the amide group attacks the carbon atom of the carboxylic group to form a six-membered imide ring with cleaving the water molecule. Thus, the first stage of ammonolysis was carried out at room temperature to avoid the ammonia evaporation, the further cyclization reaction was carried out at 80 оC. 3,5-Dibromo-1,8-naphthalimide has been obtained by this procedure with the yield of 90 % as light yellow crystals with melting point 292-293 °C. In case of 2,4,5-tribromo-1,8-naphthalimide the product contained some unreacted 2,4,5-tribromo-1,8-naphthalic anhydride as impurity. The reaction mixture was treated with a 2% aqueous solution of sodium hydroxide to remove anhydride impurity. Target 2,4,5-tribromo-1,8-naphthalimide was obtained with the yield of 67 % as light yellow crystals with melting point > 300 °C. The structure of the synthesized naphthalimide derivatives has been confirmed by IR and NMR 1Н spectroscopy.

Catalytic Properties of V–Ti–O Catalysts in the Oxidation and Ammoxidation of o-xylene, Acenaphthene and β-picoline

<p>Catalytic properties of vanadium–titanium oxide catalysts in the oxidation and ammoxidation of o-xylene, acenaphthene and β-picoline have been studied. Methods of preparation of catalysts with varying amounts contents of V<sub>2</sub>O<sub>5</sub> have been described. It has been shown that activity and selectivity in oxidation of organic compounds of different nature depends on the V2O5 content and the ratio of the oxides in the solid solution. Maximum selectivity in relation to phthalic and naphthalic anhydrides, naphthalimide and nitrile of nicotinic acid with the maximum conversion is observed with the catalysts having 4–6 wt.% of V<sub>2</sub>O<sub>5</sub>. Catalysts with other compositions showed lesser conversion of the initial substance. A catalyst, representing VO<sub>2</sub>–TiO<sub>2</sub> solid solution, exhibits the least activity and selectivity among the tested samples for oxidation of o-xylene and ammoxidation of β-picoline. For oxidation and ammoxidation of acenaphthene, the least activity and selectivity are exhibited by a catalyst, containing alongside with the solid solution no more than 3% by weight of V<sub>2</sub>O<sub>5</sub>. Catalysts with an equal V<sub>2</sub>O<sub>5</sub> amount, but differing one from the other by a composition of a solid solution, display different catalytic activity in o-xylene oxidation and β-picoline ammoxidation. Enrichment of solid solution with VO<sub>2</sub> or a decrease in the amount of the latter in the content decrease activity and selectivity of a catalyst.</p>

Surface maleylation and naphthaloylation of chitin nanofibers for property enhancement

Surface N-maleylation and N-naphthaloylation of chitin nanofiber (NF) were achieved by reaction with maleic and naphthalic anhydrides in water, respectively. Maleyl and naphthaloyl groups were sufficiently introduced to an amino group on a surface-deacetylated chitin NF. The characteristic nanofiber morphology was maintained after maleylation and naphthaloylation. These NFs were homogeneously dispersed in several organic solvents. Especially, naphthaloyl chitin NF was dispersed even in aromatic solvents, owing to the high level of solvation interactions with the naphthaloyl group. The NF dispersions in those aromatic solvents exhibited a dispersive-to-precipitate transition response at approximately 29°C. Moreover, the naphthaloyl chitin NF dispersion cut harmful ultraviolet light. The maleyl chitin NF formed a self-standing gel after cross-linking polymerization.

Enhanced hydrolytic stability of sulfonated polyimide ionomers using bis(naphthalic anhydrides) with low electron affinity

In the pursuit of hydrolytically stable sulfonated polyimide (SPI) membranes as promising candidates for proton exchange membranes, usable at elevated temperature, a series of novel SPI ionomers based on the low electron affinity bis(naphthalic anhydrides), 4,4′-sulfide-bis(naphthalic anhydride) (SBNA) and benzophenone-4,4′-bis(4-thio-1,8-naphthalic anhydride) (BPBTNA), were prepared. Tough, flexible, and transparent membranes were obtained from these polymers, although their inherent viscosities ranged from 0.41 to 0.59 dL g−1. The SPI membranes were thermally stable with the decomposition of sulfonic acid groups over 300 °C, and exhibited good mechanical properties with 65 MPa of tensile strength at 25 °C and 50% RH. The proton conductivities of the SPI membranes increases with increasing temperature and ion exchange capability (IEC), and the S–O(80) with 2.23 mequiv. g−1 of IEC showed a higher proton conductivity than Nafion® 212 at 100% RH. For the high IEC membranes, microscopic analyses revealed the hydrophilic clusters were well-dispersed and connected to each other. The accelerated water stability tests demonstrated that the SPI ionomers based on SBNA and BPBTNA maintained a high mechanical strength after being aged in water for 24 h at 140 °C, which was much more stable than the SPI membranes based on 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA). The improved hydrolytic stability of polymers could be well correlated with the results of the electron affinity (Ea) of the dianhydride calculated by the theoretical calculation. This investigation illustrated that this strategy will benefit the further development of hydrolytically stable SPIs applied to high temperature PEFCs.

New thermally stable and organosoluble heterocyclic poly(naphthaleneimide)s

AbstractAs majority of polyheteroarylenes based on bis(naphthalic anhydrides), are difficult to process due to their infusiblity and insolubility in common organic solvents and solubility only in strong acids, this study is concerned with the synthesis and properties of new, easily processable polyimides and copolyimides containing naphthalene and oxadiazole rings. These polymers have been synthesized and their properties have been compared with regard to the influence of oxadiazole and naphthalene units on their physical properties. The polyimides were prepared by polycondensation reaction in solution of the aromatic diamines containing preformed oxadiazole ring with two dianhydrides having naphthalene units, at high temperature. Also, copolyimides were prepared by using a mixture of each naphthalene‐containing dianhydride, with hexafluoroisopropylidene‐dianhydride in the polycondensation reaction with the same diamino‐oxadiazoles. Most of the resulting polyimides and copolyimides were soluble in polar amidic solvents and in less polar solvents, and their solutions gave flexible films when spread onto glass plates. The thermal stability and glass transition temperature of these polyimides and copolyimides were measured and compared. The quality and the roughness of the spin‐coated films of these polymers were investigated by atomic force microscopy. The photoluminescence properties of the polymers in solution were studied to determine the color of emission. The UV absorption was also studied to determine the Stokes shift, and hence the possible reabsorption effects. The properties of the present polyimides make them attractive for applications in advanced optoelectronics and other related fields. Copyright © 2009 John Wiley & Sons, Ltd.

Hydrolytic degradation and thermal stability of poly(naphthylimides) based on naphthalene-1,4,5,8-tetracarboxylic dianhydride and bis(naphthalic anhydrides)

The molecular properties of a number of new poly(naphthylimides) derived from naphthalene-1,4,5,8-tetracarboxylic dianhydride and bis(naphthalic anhydrides) have been studied. On the basis of hydrodynamic studies of the polymers at various stages of their thermal degradation in 96% H2SO4 and thermogravimetric measurements, the hydrolytic stability and thermooxidative resistance of the polymers have been compared. A correlation between the experimental data and the chemical structure of molecular chains has been established.

New monomers and polymers via Diels‐Alder cycloaddition

AbstractThe series of new bis(naphthalic anhydrides) was prepared through Diels‐Alder cycloaddition. The Diels‐Alder cycloaddition was used as a synthetic route to new phenylated monomers as well as to polymers. All polymers synthesized revealed to be soluble in a wide range of organic solvents such as toluene, THF, chloroform, and displayed high thermostability. Therefore, they can be processed easily and are promising candidates for advanced coating systems as well as for electrooptical applications.

Synthesis of Polyheteroarylenes Based on Bis(naphthalic) Anhydrides with Acetylene and Substituted Phenylene Groups

Synthesis of Polyheteroarylenes Based on Bis(naphthalic) Anhydrides with Acetylene and Substituted Phenylene Groups

N-Ferrocenyl Naphthalimides: Synthesis, Structure, and Redox Chemistry

A family of N-ferrocenyl-1,8- and N-ferrocenyl-2,3-naphthalimide and N,N-diferrocenyl-1,4,5,8-naphthaldiimide complexes has been prepared by reaction of naphthalic anhydrides or naphthalimide anions with a ferrocenylamine. The N-ferrocenyl substituents are 1,8 (Fc, FcCH2, FcCHMe, Fc(CH2)11), 1,4,5,8 (Fc, FcCH2, FcCHMe, Fc(CH2)11), 3-NO2-1,8- (FcCH2, FcCHMe), 4-NO2-1,8 (Fc, FcCH2, FcCHMe, Fc(CH2)11, 1,1‘-BrFcCH2), 4-Br-1,8 (FcCH2, Fc(CH2)11), and 2,3 (Fc, FcCH2, FcCHMe, Fc(CH2)11). A novel stacking aggregation occurs with the 1,4,5,8-Fc and -FcCH2 derivatives, and intramolecular donor−acceptor charge transfer is evident in the aggregate. Steric hindrance precludes this aggregation in other 1,4,5,8 analogues. An X-ray structure of the 3-NO2-1,8 derivative shows an L-shaped molecule which packs in a columnar array. Micelle formation occurs with long-chain derivatives. The electronic spectra and electrochemistry show that the N-ferrocenyl substituents do not perturb the energy levels of the fluorophore, altho...

Bis(1,8-naphthylimides) and bis(1?,8?-naphthoylene-1,2-benzimidazoles) based on new bis(naphthalic anhydrides)

The reaction of bis(naphthalic anhydrides) with aniline and o-phenylenediamine under conditions of hightemperature cyclocondensation in m-cresol in the presence of a catalyst (benzoic acid) gives bis(1,8-naphthylimides) and bis(1′,8′-naphthoylene-1,2-benzimidazoles) which model the elementary units of polyimides and polynaphthoylenebenzimidazoles, respectively.

ChemInform Abstract: Syntheses Starting with Dimethylpyrazoles. Part 9. Synthesis and Spectral Characteristics of Isomeric Pyrazolo(3′,4′‐5,6)‐ and (5′,4′‐5,6)pyrimido(1,2‐h)benzo(d,e)isoquinoline‐4,12‐diones.

AbstractThe 4‐aminopyrazole‐3‐carboxamide (I) reacts with the naphthalic anhydrides (II) to give the naphthalimides (III) which are cyclized in sulfuric acid, producing the fused system (IV).