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.     

Synthesis and Characterization of Novel Monoazo N‐Ester‐1,8‐Naphthalimide Disperse Dyestuffs

Five novel monoazo disperse dyestuffs based on N‐ester‐1,8‐naphthalimide were synthesized. Acenaphthene was nitrated, then oxidized to 4‐nitro‐1,8‐naphthalic anhydride. 4‐Nitro‐1,8‐naphthalic anhydride was reacted with methyl and ethyl glycinate in alcoholic media, followed with reduction. 4‐Amino‐N‐methyl and ethyl glycinate‐1,8‐naphthalimide were obtained. These products were diazotized and coupled with appropriate aromatic amines to give bluish‐red or violet dyestuffs. All intermediates and dyestuffs were purified and characterized by ¹H‐NMR, FTIR, DSC, UV‐VIS and Elemental Analysis. Dispersion of dyestuffs was prepared in water and applied to polyester fabrics. The dyed fabrics showed that four of the synthesized dyestuffs were suitable for coloring polyester fibers, producing deep bluish red with very good build up properties.     

Synthesis,Absorption Spectra Studies and Biological Activity of Some Novel Conjugated Dyes

Novel monomethine 2a‐f , dimethine 4a‐f and tetramethine 6a‐h cyanine dyes were prepared as conjugated dyes. Such dyes incorporating coumarin and/or quinoline derivatives 1a‐d . These dyes were synthesized to study their spectral behavior, solvatochromism and biological activity. These dyes are characterized by elemental analysis, IR, ¹H NMR and mass‐spectra.     

Synthesis and Evaluation of Technical Properties of Novel Cationic Mono‐s‐chloro Triazinyl (MCT) Reactive Dyes on Cotton

Two novel cationic mono‐s‐chloro triazinyl (MCT) reactive dyes together with their analogues were synthesized via reacting an N,N‐dimethyl dodecylamine with p‐nitrobenzyl bromide. The resultant was reduced using stannous chloride and hydrochloric acid to produce the primary amine. The quaternary ammonium salt containing primary amine was then diazotized and coupled to H‐acid/J‐acid reacted with cyanuric chloride and sulfanilic acid. The analogue dyes were prepared via the same route without quaternary ammonium salt making stage. The dyes were characterized using FTIR, ¹H NMR, UV‐Vis spectroscopy and elemental analysis. The substantivity, exhaustion and fixation of the dyes were investigated on cotton fabric. It was found that these functional dyes could be effectively introduced to cotton for achieving simultaneous coloration and functional finishing effects. All the dyed fabrics exhibited softening efficacy. The washing and light fastness of the dyed samples were further studied.     

Synthesis and Antimicrobial Activity of 2-Methyl-5-nitroaniline Derivatives:A Structure-Activity Relationship Study

A series of 2‐methyl‐5‐nitroaniline derivatives, 5a – 5k and 6a – 6f , were synthesized in order to determine their in vitro antimicrobial activity. The chemical structures of the synthesized compounds were confirmed by elemental analyses, UV‐visible, FT‐IR, ¹H NMR and ¹³C NMR spectral studies. The structure‐activity relationships of the synthesized compounds were also discussed. Among the synthesized compounds, 5f , 5d , 6b and 6e showed good antimicrobial activity compared to standard drugs.     

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 γ‐Heteroaryl‐substituted Pentamethine Cyanine Dyes with Carboxy or Methoxycarbonyl Substituents at the Two Heterocyclic End Groups

Seven novel pentamethine cyanine dyes with 3,5‐dimethylpyridinium‐1‐yl, pyridinium‐1‐yl, and 1‐quinolinum‐1‐yl substituents in the γ position of the methine chain containing ester or carboxylic acid groups in the ring of the dyes were synthesized via a three‐step procedure. The visible spectral behavior of the pentamethine cyanine dyes was examined in DMSO. Elemental analysis, IR, ¹H‐NMR, ¹³C‐NMR, and mass spectral (MS) data confirmed the molecular structure of the newly synthesized compounds.     

Synthesis and Spectral Behaviour of Some New Uninuclear Pyrimidine 2[2(4)]‐Mono(Tri)‐Methine Cyanine Dyes

New unsymmetrical 2[2(4)]‐mono‐and tri (substituted tri)‐methine cyanine dyes incorporating 1,2,5,6‐tetrahydro‐4,6‐diaryl pyrimidine (pyrimidinium‐1‐yl salt)‐2‐one were prepared. Structural determination was carried out by elemental analysis, IR and ¹H NMR spectral data. The spectral behaviour of all the synthesized cyanines was examined in 95% ethanol.     

Synthesis and characterization of tributyltin derivatives from 4‐oxo‐4‐(arylamino)butanoic acids and their in vitro biological activity against cervical cancer cell lines

Uterine (cervix and corpus) cancer is one of the major causes of mortality in women in Mexico. Organotin carboxylated derivatives have shown high cytotoxic activity against various cell lines of human origin. We describe the synthesis of three new tri‐n‐butyltin derivatives from 4‐oxo‐4‐(arylamino)butanoic acids; their structures were confirmed using spectral data (¹H NMR, ¹³C NMR, ¹¹⁹Sn NMR and infrared), elemental analyses, mass spectrometry and X‐ray diffraction. All the tri‐n‐butyltin carboxylates exhibit ¹ J (^119/117Sn–¹³C) coupling satellites in solution and lie in the range 357 to 339 Hz, suggesting a tetrahedral geometry around the tin atom. The polymeric structures of two of the derivatives and the monomeric structure of another were confirmed using X‐ray crystallography. Using succinic anhydride as raw material, five N‐substituted succinamic acid compounds were synthesized by the acylation reaction with aniline, 4‐nitroaniline, 4‐nitro‐3‐(trifluoromethyl)aniline, 2‐amino‐5‐nitrothiazole and 4‐aminoantipyrine. From these compounds, five tin derivatives were prepared and their in vitro anti‐proliferative effect on HeLa, CaSki and ViBo cell lines was screened. All of the compounds showed potency against all three strains and null or low cytotoxic activity (necrotic) as well. The most potent of our derivatives as an anti‐proliferative agent against the three cell lines was tributylstannyl 4‐oxo‐4‐[(3‐trifluoromethyl‐4‐nitrophen‐1‐yl)amino]butanoate, exhibiting an IC₅₀ value of 0.43 μM against the HeLa cell line. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis of Some Novel Arylazo Disperse Dyes Derived from 5‐Amino‐tetrazolo[1,5‐a]pyrimidin‐7‐ol as Coupling Component and Investigation of Their Absorption Spectra

5‐amino‐tetrazolo[1,5‐a]pyrimidin‐7‐ol ( I ) was synthesized by reaction of 5‐amino‐tetrazole with ethyl cyanoacetate in excellent yield. A series of novel 5‐amino‐6‐arylazotetrazolo[1,5‐a]pyrimidin‐7‐ol dyes were prepared by linking o‐, m‐, p‐anisidine, o‐, m‐, p‐chloroaniline, o‐, m‐, p‐nitroaniline, o‐, m‐, p‐toluidine and aniline to 5‐amino‐tetrazolo[1,5‐a]pyrimidin‐7‐ol ( I ). The structure of these dyes were confirmed by UV‐vis, FTIR and ¹H NMR spectroscopic techniques and elemental analysis. The effect of varying pH and solvent upon the absorption ability of 5‐amino‐6‐arylazotetrazolo[1,5‐a]pyrimidin‐7‐ol sudstituted with electron‐withdrawing and electron‐donating groups at their o‐, m‐, p‐position was examined.     

Synthesis and Visible Spectral Behaviour of Some New N‐Bridgehead Heterocyclic Cyanine Dyes Incorporating Pyrazolo (4,5‐b) Indolizine (Benzoindolizine)

The new unsymmetrical N‐bridgehead, apo (zeromethine), mono‐methine, dimethine, meso substituted tetramethine and styryl cyanine dyes incorporating pyrazolo (4,5‐b) indolizine (benzoindolizine) nuclei were prepared. Structural confirmation was carried out by elemental analyses, IR, H‐NMR, mass spectra and ¹³C‐NMR with the aid of carbon DEPT spectral data. The visible absorption spectra for the newly synthesized cyanines were examined in 95% ethanol.     

Multinuclear magnetic resonance study of the structure and tautomerism of azide and iminophosphorane derivatives of chloropyridazines

Some azido‐ and iminophosphorane derivatives of 3,6‐dichloro‐ and 3,4,5,6‐tetrachloropyridazine were synthesized and studied by means of NMR measurements. Based on multinuclear data (chemical shifts, coupling constants) for compounds containing the azide group, no potentially possible tetrazole–azide equilibrium can be observed, even under acidic conditions. An unusual substitution of a chlorine atom (in position 4) of tetrachloropyridazine in the reaction with hydrazine was demonstrated by NMR measurements of two newly synthesized compounds containing azido‐ and iminophosphorane groups. Using multinuclear magnetic resonance data, the sites of ethylation and protonation of azido‐ and iminophosphorane derivatives of chloropyridazines were established. In the case of the tetrazolopyridazines, ethylation occurs at the N1′ and N2′ atoms, whereas for monocyclic compounds it takes place at the N1 and/or N2 atoms of the pyridazine ring. Preferred sites of protonation are the N1′ atom of the tetrazole ring and the N1 atom of the pyridazine ring. Moreover, the structures of potassium salts of 6‐(3‐cyano‐1‐triazeno)tetrazolo[1,5‐b] pyridazine and its amido derivative were established using NMR data, especially ¹⁵N NMR chemical shifts. Copyright © 2002 John Wiley & Sons, Ltd.     

Photophysics,Electrochemistry, Morphology,and Bioimaging Applications of New 1,8‐Naphthalimide Derivatives Containing Different Chromophores

A series of 1,8‐naphthalimide‐based fluorophores containing different chromophores with varying conjugation and electron richness at the imidic nitrogen atom are synthesized and characterized. These amine‐functionalized naphthalimides are bipolar in nature and exhibit interesting optical and morphological variations attributable to the nature of the N substituents. Despite the fact that the dyes are structurally different owing to variation of the substituent on the imidic nitrogen atom, their electronic characteristics are similar and originate from the 4‐aminonaphthalimide segment. Nevertheless, they exhibit variations in morphology in the microscopic domain, and this is attributable to structural differences. Further, these fluorescent dyes display biocompatibility and are used in the bioimaging of cells.     

Synthesis,Structure, Spectroscopic Studies,and Complexation of Novel Crown Ether Butadienyl Dyes

Butadienyl dyes of the benzothiazole series with various fragments of benzocrown ethers 1a – c were synthesized for the first time. The structures and spectral properties of crown‐containing butadienyl dyes and their complexes with alkali and alkaline‐earth metal cations were studied by X‐ray diffraction analysis and ¹H‐NMR, UV/VIS, and resonance Raman spectroscopy. To interpret the experimental results, quantum‐chemical calculations were performed. In the case of Sr²⁺ and Ba²⁺ ions, the formation of strong sandwich complexes [M( 1b )₂]²⁺ of an unusual structure involving stacking interactions was established; the dye molecules are arranged one above another in the complex according to the ‘head‐to‐head' pattern.     

Synthesis and Antimicrobial Activity of Some Novel Hydrazide,Pyrazole, Triazine,Isoxazole, and Pyrimidine Derivatives

In continuation of our efforts to find a new class of antimicrobial agents, a series of pyrazole, 1,2,4‐triazine, isoxazole, pyrimidine, and other related products containing a hydrazide moiety were prepared via the reaction of 2‐cyano‐N‐((2‐methoxynaphthalen‐1‐yl)methylene) acetohydrazide ( 1 ) with appropriate chemical reagents. These compounds were evaluated for their antimicrobial activities, and also their minimum inhibitory concentration against most of test organisms was performed. Among the tested compounds 4 , 5 , 6 , and 16 displayed excellent antimicrobial activity. All the synthesized products were confirmed by elemental analysis, IR, ¹H‐NMR, ¹³C‐NMR, and mass spectral data.     

An Unprecedented Blueshifted Naphthalimide AIEEgen for Ultrasensitive Detection of 4‐Nitroaniline in Water via “Receptor‐Free” IFE Mechanism

The development of a new naphthalene appended naphthalimide derivative ( NMI ) with aggregation‐induced enhanced emission (AIEE) property for the sensitive detection of 4‐nitroaniline (4‐NA) in aqueous media is presented here. The newly designed naphthalimide AIEEgen has an exceptional blue‐shifted condensed state emission that is devoid of any receptor site, accomplished ultrasensitive detection of 4‐NA, which is one of the broad‐spectrum pesticides that belong to the class III toxic chemical, at parts per billion level (LOD/36 ppb, K_sv=4.1×10⁴ m ^?1) in water with excellent selectivity even in the presence of potentially competing aliphatic and aromatic amines. The reported probe is the first of its kind, demonstrating major advantages of receptor‐free inner filter effect (IFE) mechanism for the sensitive detection of 4‐NA using an AIEEgenic probe. Excellent sensitivity for 4‐NA is also achieved on paper‐based test‐strip for low‐cost on‐site detection.     

Temperature and pH sensitive ionic hydrogels based on new crosslinkers

New crosslinkers were synthesized from reaction of melamine with acryloyl and methacryloyl chloride in the presence of 1‐methyl‐2‐pyrrolidone as a solvent and triethyl amine as acid acceptor. The chemical structures of the prepared crosslinkers were elucidated from FT‐IR, ¹H‐NMR and ¹³C‐NMR analyses. Linear 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid and methacrylic acid (AMPS/MAA) copolymers were prepared and their viscometric properties in aqueous solution were investigated. Different weight percentages of the prepared crosslinkers were used as crosslinking agent (AMPS/MAA) to prepare ionic copolymers using ammonium persulfate as initiator. The percentage of crosslinkers was varied from 0.5 to 4 wt%. The swelling behaviors of crosslinked AMPS/MAA gels in deionized water were measured at different pH and temperatures. All AMPS/MAA copolymers exhibit faster deswelling rate at 50°C except for the copolymer containing 0.9 (mol ratio) AMPS. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis and Cytotoxicity of Arene‐Ru Compounds Containing 4‐Nitroaniline or 2‐Halogenated 4‐Nitroaniline

The compounds [(η⁶‐p‐cymene)RuCl₂(4‐nitroaniline)] and [(η⁶‐p‐cymene)RuCl₂(2‐halogen‐4‐nitroaniline)] were synthesized and characterized by various means. The [(η⁶‐p‐cymene)RuCl₂(4‐nitroaniline)] and [(η⁶‐p‐cymene)RuCl₂(2‐fluoro‐4‐nitroaniline)] compounds were determined by X‐ray diffraction, appearing in a distorted piano‐stool type of arrangement with similar bond lengths and angles around the ruthenium. The compounds exhibited moderate to strong in vitro cytotoxicity against A549 and MCF‐7 human cancer cells. Substitution of heavy halogen atom on the ortho position of para‐nitroaniline weakened the cytotoxicity against both of MCF‐7 and A549, except the cases of fluorine substitution for hydrogen atom regarding A549 and bromine substitution for chlorine atom regarding MCF‐7, which showed minor deviation.     

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。     

Vinylic and ring‐opening metathesis polymerization of norbornene with bis(β‐ketoamine) cobalt complexes

Cobalt complexes 1 – 4 bearing N,O‐chelate ligands based on condensation products of 1‐phenyl‐3‐methyl‐4‐benzoyl‐5‐pyrazolone with aniline, o‐methylaniline, α‐naphthylamine, and p‐nitroaniline, respectively, were synthesized, and the structures of 1 and 4 were characterized by single‐crystal X‐ray diffraction analyses. The bis(β‐ketoamine) cobalt complexes could act as moderately active catalyst precursors for norbornene polymerization with the activation of methylaluminoxane. This catalytic reaction proceeded mainly through a vinyl‐type polymerization mechanism. ¹H NMR and IR showed that in all cases, a small amount of double bonds raised from ring‐opening metathesis polymerization (ROMP) was present in the polymerization products. The variation of the polymerization conditions affected the ROMP unit ratio in the polynorbornenes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5535–5544, 2005