Synthesis and Characterization of Some Monoazo Disperse Dyestuffs Based on Naphthalimide Derivatives for Dyeing of Polyester Fabrics

A series of monoazo disperse dyestuffs derived from naphthalimide were prepared. 4‐Amino‐N‐methyl (alternatively N‐ethyl, N‐propyl, N‐butyl) derivatives of naphthalimide were utilised as the diazo components and β‐naphthol, N,N‐diethyl‐m‐toluidine, and p‐aminoacetophenone constituted the coupling components. To this end, acenaphthene was nitrated and then various unit processes such as oxidation, amination, reduction, diazotization, and coupling were carried out. The synthesized monoazo disperse dyestuffs were applied to a locally manufactured polyester fabric and their optical properties were investigated. Characterisation of the various intermediates as well as the dyestuffs were carried out by DSC, FTIR, H‐NMR and UV‐vis analytical techniques.     

Synthesis and Characterization of Novel Monoazo Naphthalimide Disperse Dyes Containing Carboxylic Acid Group with High Heat Fastness Properties

A group of novel monoazo disperse dyes containing carboxylic acid‐1,8‐naphthalimide group has been synthesized. All intermediates and dyes were purified by recrystalization and the column chromatography method. The purified products were characterized by ¹H NMR, ¹³C NMR, FTIR, DSC, UV‐VIS and Elemental Analysis. Spectrophotometric investigations of the synthesized dyes in different solvents were carried out in order to obtain their absorption maxima, molar extinction coefficients and solvatochromic effects. The absorption maxima of the synthesized dyes in acetone varied (513‐549 nm) and the molar extinction coefficient was (17405‐38939 l/mol cm). By changing the media from chloroform to DMF, the solvatochromism effect for all dyes increased. Dispersion of the synthesized dyes was prepared in water containing dispersing agent and applied to polyester fabrics. The dyed fabrics showed that all of the synthesized dyes were suitable for coloring polyester fibers, producing deep red to bluish red with very good fastness properties.     

1,8—萘酐和1,8—萘酰亚胺中硝基和卤素基团的亲核取代反应

研究了１，８－萘酐和１，８－萘酰亚胺萘环上硝基和卤素原子的亲核取代反应，讨论了影响亲核取代反应的因素，根据２，４－二硝基苯酚与脂胺肪的亲核取代机理，提出了４－硝基－１，８－萘酐及４－硝基－１，８－萘酰亚胺与脂肪胺发生亲核取代反应可能的反应机理。     

The improved synthesis,Diels‐Alder reactions,and desulfuration of trithio‐1,8‐naphthalic anhydride

In the presence of a strong Lewis base, such as Et₃N, trithio‐1,8‐naphthalic anhydride (3) is easily oxidized. Two improved syntheses of trithio‐1,8‐naphthalic anhydride (3) are described. Trithio‐1,8‐naphthalic anhydride (3) undergoes Diels‐Alder reactions with electron‐deficient alkenes to give novel fused heterocyclic compounds (6–11) that then can undergo a novel, gradual desulfuration dimerization with triethyl phosphite to afford 12 and its analogs 13 and 14. The structures of 6–14 are confirmed by microanalysis, IR, and NMR spectroscopy, and MS. © 1999 John Wiley & Sons, Inc. Heteroatom Chem 10: 141–146, 1999     

Mild and Efficient Synthesis of 1,8‐Naphthalide and 1,8‐Naphthalenedimethanol

Abstract

Mild and efficient procedures have been developed for synthesis of 1,8‐naphthalide and 1,8‐naphthalenedimethanol. In an ice‐water bath, 1,8‐naphthalide was prepared from 1,8‐naphthlic anhydride using LiAlH₄ as reducing agent. 1,8‐Naphthalenedimethanol was obtained with good yield from reduction of 1,8‐naphthalic anhydride by LiAlH₄ and Lewis acids at room temperature. The effects of various factors on the reduction of 1,8‐naphthalic anhydride with LiAlH₄ were investigated.     

Synthesis of novel poly(thioether‐naphthalimide)s that utilize hydrazine as the diamine

A series of bis(4‐thio‐1,8‐naphthalic anhydride)s and the corresponding bis(N‐amino naphthalimide) derivatives were synthesized from readily available compounds in high yield. A series of novel poly(thioether‐naphthalimide)s, which utilized hydrazine as the diamine, were synthesized by a one‐step polymerization reaction in m‐cresol. Poly(thioether‐naphthalimide)s with inherent viscosities of 0.57–1.73 dL/g were obtained. The polymers were soluble in CHCl₃ and were determined to have high molecular weights by means of gel permeation chromatographic analysis. They were soluble in m‐cresol and could be cast into tough films from m‐cresol solution. The glass‐transition temperature (T_g) values of the polyimides ranged from 320 to 353 °C. Polyimides from the bisphenol dianhydride, derived from 9,9‐bis(4‐hydroxyphenyl)fluorene, did not show a clear transition in the DSC analysis. Degradation temperatures for 5% weight loss all occurred above 430 °C in nitrogen. The series of monomers were successfully copolymerized with each other. Monomers 6a and 7a , containing the bisphenol A moiety, could also be copolymerized with perylenetetracarboxylic dianhydride. These copolymers had high T_g's and were thermally stable. The UV–vis absorption properties of the polymers were also examined. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1040–1050, 2001     

Synthesis and Application of Some Alkali‐Clearable Azo Disperse Dyes Based on Naphthalimide Derivatives

A series of naphthalimide‐based alkali‐clearable azo disperse dyes containing a fluorosulfonyl group was synthesized. 4‐Fluorosulfonylaniline, 4‐fluorosulfonyl‐2‐nitroaniline and 6‐chloro‐4‐fluorosulfonyl‐2‐nitroaniline as the diazo components were prepared from N‐acetylsulfanilyl chloride and were subsequently coupled with 4‐hydroxy‐N‐3‐methoxypropyl‐1, 8‐naphthalimide. The synthesized dyes and their intermediates were characterized by the use of DSC, FTIR, ¹H NMR, ¹³C NMR, Mass spectroscopy and UV‐visible spectroscopic techniques. Spectrophotometric investigations of prepared dyes in different solvents were carried out in order to obtain their absorption maxima, molar extinction coefficients and solvatochromic effects. The obtained dyes were applied to polyester fabric by the HT method and exhibited good leveling, wash and sublimation fastnesses and moderate light fastness. The synthesized dyes showed that incorporated fluorosulfonyl group to these dyes can be converted to the dyes containing a water soluble sulfonate group in the relatively mild alkaline conditions.     

Synthesis of a novel high sensitive photo‐radical initiator with good thermal stability based on naphthalic‐1,8‐N‐alkylimide derivatives

A new high‐sensitive photo‐radical initiator, N‐[2‐(2‐acryloyloxyethoxy)ethyl]‐1,8‐naphthalimide (NI6), with good thermal stability based on naphthylimide derivative was developed. NI6 was prepared by the condensation of N‐[2‐(2‐hydroxyethoxy)ethyl]‐1,8‐naphthalimide and acryloyl chloride in the presence of 4‐dimethylaminopyridine. The film consisting of NI6 and pentaerythritol triacrylate (PETA) showed higher photosensitivity than those containing conventional photo‐radical initiators such as acrylic acid 2‐(2‐{2‐[2‐(4‐benzoyl‐phenoxy)‐ethoxy]‐ethoxy}‐ethoxy)‐ethyl ester, cyclohexylmaleimide, and the resulting film exhibited very high transmittance over 400 nm. The thermal stability of NI6 was very high and no decomposed residues were observed from the film consisting of NI 6 after heating at 250 °C for 1 h. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5571–5580, 2005     

A TD‐DFT Study on the Effect of Intermolecular Hydrogen Bonding on the Photophysical Properties of N‐Methyl‐1,8‐naphthalimide

The effect of intermolecular hydrogen bonding on the photophysical properties of N‐methyl‐1,8‐naphthalimide ( 2 ) has been investigated by time‐dependent density functional theory (TD‐DFT) method. The UV and IR spectra of 2 monomer and its hydrogen‐bonded complexes formed with 2,2,2‐trifluoroethanol (TFE) 2 +TFE and 2 +2TFE have been calculated, which confirm the presence of intermolecular hydrogen bonding interactions between the carbonyl groups of the aromatic imide and the hydroxyl group of the polyfluorinated alcohol. The absorption and fluorescence intensities going from 2 monomer via hydrogen‐bonded complex 2 +TFE to 2 +2TFE were found to be gradually enhanced with the wavelength gradually red‐shifted. The enhancements of the fluorescence intensities from 2 monomer to hydrogen‐bonded complexes 2 +TFE and 2 +2TFE were attributed to the decrease of the intersystem crossing (ISC) efficiency from the first excited singlet state S₁ ¹(ππ*) to the second excited triplet state T₂ ³(nπ*), whose energy was increased relative to its ground state due to the intermolecular hydrogen bonding interactions.     

Synthesis of Novel Heterocyclic Compounds with Expected Antibacterial Activities from 4‐(4‐Bromophenyl)‐4‐oxobut‐2‐enoic Acid

This research describes the utility of 4‐(4‐bromophenyl)‐4‐oxobut‐2‐enoic acid as a key starting material for preparation of a novel series of aroylacrylic acids, pyridazinones, and furanones derivatives. These heterocyclic compounds were synthesized by reaction of 4‐(4‐bromophenyl)‐4‐oxobut‐2‐enoic acid with benzimidazole, ethyl glycinate hydrochloride, anthranilic acid and o‐phenylenediamine under Aza–Michael addition conditions. Every Aza–Michael adduct was allowed to react with haydrazine hydrate and acetic anhydride to form pyridazinones and furanones derivatives, respectively. In further step, some pyridazinones were allowed to react with ethyl acetoacetate, acetyl acetone, acetyl chloride, and aromatic aldehydes to form novel heterocylces. Finally, studying antibacterial activities of these compounds was performed.     

N‐(2‐Bromoethyl)‐4‐piperidino‐1,8‐naphthalimide and N‐(3‐bromopropyl)‐4‐piperidino‐1,8‐naphthalimide

N‐(2‐Bromoethyl)‐4‐piperidino‐1,8‐naphthalimide, C₁₉H₁₉BrN₂O₂, (I), and N‐(3‐bromopropyl)‐4‐piperidino‐1,8‐naphthalimide, C₂₀H₂₁BrN₂O₂, (II), are an homologous pair of 1,8‐naphthalimide derivatives. The naphthalimide units are planar and each piperidine substituent adopts a chair conformation. This study emphasizes the importance of π‐stacking interactions, often augmented by other contacts, in determining the crystal structures of 1,8‐naphthalimide derivatives.     

含三苯胺的1,8-萘酰亚胺衍生物的合成及光谱和电化学性能研究

通过Suzuki偶联反应合成了一系列含三苯胺的1,8-萘酰亚胺衍生物，并进行了表征及光谱和电化学性能研究。研究表明该类化合物的荧光波长在584~610nm，位于橙色区。三苯胺的引入降低了化合物的HOMO值，有利于空穴的注入。     

A New,Highly Potent 1,8‐Naphthalimide‐based Fluorescence “Turn off” Chemosensor Capable of Cu2+ Detection in China's Yellow River Water Samples

A new 1,8‐naphthalimide‐based fluorescence “turn off” chemosensor, N‐phenyl‐4‐(3,3′‐((2‐aminoethyl)azanediyl)dipropanoic acid)‐1,8‐naphthalimide ( MAST ), for the detection of Cu²⁺ was synthesized. Upon treatment with Cu²⁺, in coexistence with various competitive metal ions in HEPES‐buffered dimethylsulfoxide (DMSO) solution (v/v, 1:1; pH 7.4), MAST displayed a high selectivity toward Cu²⁺ with a fluorescence quenching of 83.67%. Additionally, a good linear response of MAST for the detection of Cu²⁺ was obtained in the concentration range of 10 × 10⁻⁶ to 50 × 10⁻⁶ M. A 1:1 stoichiometric interaction of MAST with Cu²⁺ was observed, and the association constant and detection limit were calculated to be 1.37 × 10⁶ and 0.69 × 10⁻⁸ M, respectively. The sensing mechanism of the chemosensor toward Cu²⁺ was proposed due to the effect of the paramagnetic nature of Cu²⁺ and reverse‐photo‐induced electron transfer (PET) process. Ultimately, the proposed chemosensor was applied to quantify Cu²⁺ in real‐world water samples, with excellent recovery rates of 98.00–109.80% observed.     

Conjugated Donor‐Acceptor‐Acceptor (D‐A‐A) Molecule for Organic Nonvolatile Resistor Memory

A new donor‐acceptor‐acceptor (D‐A‐A) type of conjugated molecule, N‐(4‐(N′,N′‐diphenyl)phenylamine)‐4‐(4′‐(2,2‐dicyanovinyl)phenyl) naphthalene‐1,8‐dicarboxylic monoimide ( TPA‐NI‐DCN ), consisting of triphenylamine (TPA) donors and naphthalimide (NI)/dicyanovinylene (DCN) acceptors was synthesized and characterized. In conjunction with previously reported D ‐A based materials, the additional DCN moiety attached as end group in the D‐A‐A configuration can result in a stable charge transfer (CT) and charge‐separated state to maintain the ON state current. The vacuum‐deposited TPA‐NI‐DCN device fabricated as an active memory layer was demonstrated to exhibit write‐once‐read‐many (WORM) switching characteristics of organic nonvolatile memory due to the strong polarity of the TPA‐NI‐DCN moiety.     

Synthesis of 5‐chloro‐2‐methyl‐3‐(5‐methylthiazol‐2‐yl)‐4(3H)‐quinazolinone and related compounds with potential biological activity

Eight new 2‐methyl‐4(3H)‐quinazolinones (8a‐8d, 9c, 9d, 10c, 10d) with one or two chlorine atoms in the benzene ring and a 5‐methyl‐1,3‐thiazol‐2‐yl, 4‐methyl‐1,3‐thiazol‐2‐yl, and 5‐ethyl‐1,3,4‐thiadiazol‐2‐yl substituent in position 3 of the heterocyclic ring were synthesized and characterized. The two step procedure (Scheme 1) utilizes chlorosubstituted anthranilic acids (3a‐3d) and acetic anhydride as the starting materials, with the respective chlorosubstituted 2‐methyl‐4H‐3,1‐benzoxazin‐4‐ones (4a‐4d) as the intermediates. The quinazoline derivatives were characterized by their melting points, elemental analyses and the mass, ultraviolet, infrared, and ¹H and ¹³C nmr spectra. The new compounds are expected to be biologically active.     

Four‐, five‐ and six‐coordinated transition metal complexes based on naphthalimide Schiff base ligands: Synthesis,crystal structure and properties

Two bidentate Schiff base ligands (HL¹ = N‐n‐butyl‐4‐[(E)‐2‐(((2‐aminoethyl)imino)methyl)phenol]‐1,8‐naphthalimide; and HL² = N‐n‐butyl‐4‐[(E)‐2‐(((2‐aminoethyl)imino)methyl)‐6‐methoxyphenol]‐1,8‐naphthalimide) with their metal complexes [Cu(L¹)₂] ( 1 ), [Zn(L¹)₂(Py)]₂?H₂O ( 2 ) and [Ni(L²)₂(DMF)₂] ( 3 ) have been synthesized and characterized. Single‐crystal X‐ray structure analysis reveals that complex 1 has a four‐coordinated square geometry, while complex 2 is a five‐coordinated square pyramidal structure and complex 3 is a distorted six‐coordinated octahedral structure. Cyclic voltammograms of 1 indicate an irreversible Cu²⁺/Cu⁺ couple. In vitro antioxidant activity assay demonstrates that the ligands and the two complexes 1 and 3 display high scavenging activity against hydroxyl (HO^?) and superoxide (O₂^??) radicals. Moreover, the fluorescence properties of the ligands and complexes 1 – 3 were studied in the solid state. Metal‐mediated enhancement is observed in 2 , whereas metal‐mediated fluorescence quenching occurs with 1 and 3 .     

A New Fluorescent Chemosensor for Metal Ions Based upon 1,8‐Naphthalimide and 8‐Hydroxyquinoline

A new fluorescent chemosensor based upon 1,8‐naphthalimide and 8‐hydroxyquinoline was synthesized, and its fluorescent properties in the presence of different metal cations (Hg²⁺, Ag⁺, Zn²⁺, Fe²⁺, Cd²⁺, Pb²⁺, Ca²⁺, Cu²⁺, Mg²⁺, and Ba²⁺) were investigated. It displayed fluorescence quenching with some heavy and transition metal (HTM) ions, and the quenching strongly depended on the nature of HTM ions.     

Synthesis of 2,4‐diaminothieno‐ and pyrrolo[2,3‐d]pyrimidine‐6‐carboxylic acid derivatives

A series of new 2,4‐diaminothieno[2,3‐d]‐ and 2,4‐diaminopyrrolo[2,3‐d]pyrimidine derivatives were synthesised. Reaction of 2‐amino‐4,6‐dichloropyrimidine‐5‐carbaldehyde ( 1 ) with ethyl mercaptoacetate, methyl N‐methylglycinate or ethyl glycinate afforded ethyl (2‐amino‐4‐chloro‐5‐formylpyrimidin‐6‐yl)thioacetate ( 2a ), methyl N‐(2‐amino‐4‐chloro‐5‐formylpyrimidin‐6‐yl)‐N‐methylglycinate ( 2b ) and ethyl N‐(2‐amino‐4‐chloro‐5‐formylpyrimidin‐6‐yl)glycinate ( 2c ), respectively. Compounds 2a,b by treatment with bases cyclised to the corresponding 2‐amino‐4‐chlorothieno‐ and pyrrolo[2,3‐d]pyrimidine‐6‐carboxylates ( 3a,b ). Heating 2,4‐diamino‐6‐chloropyrimidine‐5‐carbaldehyde ( 5 ) with ethyl mercaptoacetate or methyl N‐methylglycinate gave 2,4‐diaminothieno[2,3‐d]‐ and 2,4‐diaminopyrrolo[2,3‐d]‐pyrimidine‐6‐carboxylates ( 6a,b ), whereas compound 5 with ethyl glycinate under the same reaction conditions afforded ethyl N‐(2,4‐diamino‐5‐formylpyrimidin‐6‐yl)glycinate ( 7 ). Treatment of 2,4‐diaminothieno[2,3‐d]pyrimidine‐6‐carboxylic acid ( 8a ) with 4‐methoxy‐, 3,4,5‐trimethoxyanilines or ethyl N‐(4‐aminobenzoyl)‐L‐glutamate in the presence of dicyclohexylcarbodiimide and 1‐hydroxybenzotriazole furnished the corresponding N‐arylamides 9‐11.     

Synthesis and Heterocyclization of 1‐Aryl‐2‐methyl‐4‐oxo‐1,4,5,6‐tetrahydropyridine‐3‐carboxylates

A series of novel isoxazole, dihydropyrazolone, and tetrahydropyridine derivatives were synthesized by the reaction of corresponding ethyl 1‐substituted aryl‐2‐methyl‐4‐oxo‐1,4,5,6‐tetrahydropyridine‐3‐carboxylates with different hydrazines and hydroxylamine. Reaction of tetrahydropyridone with N ,N‐dimethylformamide dimethyl acetal provided 1‐(5‐chloro‐2‐methylphenyl)‐2‐[2‐(dimethylamino)ethenyl]‐4‐oxo‐1,4,5,6‐tetrahydropyridine‐3‐carboxylate, which was cyclized into a bicyclic compound on treatment with ammonium acetate. The structures of all synthesized compounds were confirmed by IR, ¹H NMR, and ¹³C NMR spectroscopy data. The structure of 5‐(5‐chloro‐2‐methylphenyl)‐4‐methyl‐2‐phenyl‐2,5,6,7‐tetrahydro‐3H‐pyrazolo[4,3‐c]pyridin‐3‐one was unambiguously assigned by means of X‐ray analysis data.     

Anchoring of 1,8-naphthalimide derivative into mesoporous MCM-41 molecular sieves

The fluorescent dye molecules, 4-piperidine-1,8-naphthalimide, were successfully fixed into the amino modified pore channel of mesoporous MCM-41 type materials by in situ reaction of 4-piperidinyl-1,8-naphthalic anhydride with the amino group. The formation of amide bonds on the pore surface was verified by infrared spectra. The maximum fluorescence emission peak of this hybrid material has a red shift of 13 nm compared to that of a naphthalimide derivative in ethanol solution. Moreover, the fluorescence intensity of dye molecules grafted into Ce-doped MCM-41 is higher than that in pure silica MCM-41. This phenomenon is attributed to the inhibited internal electron transfer from piperidine to naphthalimide groups by Ce⁴⁺, thus improving the fluorescence intensity of the naphthalimide group. The unique fluorescence behavior of the 1,8-naphthalimide derivative doped hybrid mesoporous material makes it a good candidate for the metal ions microdetection.