New long-chain-substituted polymeric metal-free and metallophthalocyanines by microwave irradiation: Synthesis and characterization

A tetranitrile monomer N,N-bis{2-[2-(3,4-dicyanophenoxy)ethoxy]ethyl}-4-methylbenzenesulfonamide (3) was synthesized by nucleophilic aromatic substitution of N,N-bis[2-(2-hydroxyethoxy)ethyl]-4-methylbenzenesulfonamide (1) onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile monomer 3 in 2-(dimethylamino)ethanol. Ni(II), Co(II) and Cu(II) phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the chlorides of Ni(II), Co(II) and Cu(II) in 2-(dimethylamino)ethanol (DMAE). The Zn(II)-phthalocyanine polymer was prepared by the reaction of the tetranitrile compound with the acetate of Zn(II) in DMAE. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV–Vis, elemental analysis and MS spectral data.     

A novel metal-free and metallophthalocyanines containing four 19-membered dithiadiazadioxa macrocycles by microwave irradiation: Synthesis and characterization

The novel tetrasubstituted metal-free phthalocyanine (5) and metallophtalocyanines (6, 7 and 8) bearing four 19-membered dithiadiazadioxa macrocyclic moieties on peripheral positions have been synthesized by cyclotetramerization reaction of phthalonitrile derivative (4) in a multi-step reaction sequence. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectral data.     

The synthesis, using microwave irradiation and characterization of novel, metal-free and metallophthalocyanines

The synthesis of novel metal-free (4) and metallophthalocyanines (5, 6, 7 and 8) were prepared by cyclotetramerization of a novel 4-[2-(1-naphthyloxy)ethoxy]phthalonitrile (3). New substitute phthalocyanines showed the enhanced solubility in organic solvents. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis and MS spectral data.     

Improvement in the synthesis of metallophthalocyanines using microwave irradiation

A successful application of microwave irradiation, in which phthalocyanines were synthesized under solventless conditions from 1,2-phthalonitrile or phthalic anhydride and urea in the presence of metal templates is described. It was found that in comparison with conventional heating, the microwave process is a very useful alternative for cyclotetramerization processes because of reduction of the reaction time, better yield, and easy-to-perform procedure.     

Synthesis and characterization of soluble tetra(2‐methoxyethoxy)metallophthalocyanines

Four soluble tetra(2‐methoxyethoxy)metallophthalocyanines 4a‐4d were, in two steps, synthesized from phthalonitrile 1 and 2‐methoxyethanol 2 , and characterized by MS, ¹H NMR, UV‐vis, IR and elemental analysis, as well as Cyclic voltammetry.     

Synthesis and characterization of benzothiazolyl‐substituted anils

New Schiff bases containing a hydroxynaphthyl ring and substituted benzothiazolyl groups have been synthesized. High‐resolution NMR spectra confirmed that these anils exist as enol–keto tautomers in solution. The results from NMR data demonstrated that the proportion of enol tautomer exceeded 90% in these substituted anils. Some compounds exhibited thermochromism in solid state. Copyright © 2010 John Wiley & Sons, Ltd.     

新型水溶性金属酞菁化合物的合成与表征

以含有咪唑阳离子的邻苯二腈为前驱体,通过环合反应分别合成了四咪唑阳离子取代的锌酞菁和铜酞菁,它们的结构均通过了红外光谱、核磁氢谱、元素分析和紫外-可见吸收光谱的表征.这2种酞菁化合物在水、DMF、DMSO及甲醇中均呈现出良好的溶解性.利用紫外-可见吸收光谱法考察了它们在不同种溶剂中、不同浓度下的聚集行为,并利用循环伏安法和方波伏安法测试了它们的电化学性质.     

Synthesis and characterization of N‐substituted hyperbranched polyureas

N,N′‐disubstituted hyperbranched polyureas with methyl, benzyl, and allyl substitutents were synthesized starting from AB₂ monomers based on 3,5‐diamino benzoic acid. Carbonyl azide approach, which generates isocyanate group in situ on thermal decomposition, was used for the protection of isocyanate functional groups. The N‐substituted hyperbranched polymers can be considered as the new class of internally functionalized hyperbranched polyureas wherein the substituent can function either as receptor or as a chemical entity for selective transformations as a tool to tailor the properties. The chain‐ends were also modified by attaching long chain aliphatic groups to fully realize the interior functionalization. This approach opens up a possible synthetic route wherein different functional substituents can be used to generate a library of internally functionalized hyperbranched polymers. All the hyperbranched polyureas were characterized by FTIR, ¹H‐NMR, DSC, TGA, and size exclusion chromatography. Degree of branching in these N,N′‐disubstituted hyperbranched polyureas, as calculated by ¹H‐NMR spectroscopy using model compounds, was found to be lower than the unsubstituted hyperbranched polyurea and is attributed to the lower reactivity of N‐substituted amines compared to that of unsubstituted amines. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5134–5145, 2004     

Synthesis and characterization of thiophene‐substituted N‐phenyl maleimide polymers by photoinduced radical polymerization

Two types of novel functionalized N‐[4‐(4′‐hydroxyphenyloxycarbonyl)phenyl]maleimide and N‐(4‐{[2‐(3‐thienyl)acetyl]oxyphenyl}oxycarbonylphenyl)maleimide (MIThi) were synthesized starting from 4‐maleimido benzoic acid. Photoinduced radical homopolymerization of MIThi and its copolymerization with styrene were performed at room temperature to give linear polymers containing pendant thienyl moieties using ω,ω‐dimethoxy‐ω‐phenylacetophenone as an initiator. Copolymers' compositions and the equilibrium constant (K) for electron donor–acceptor complex formation suggest an alternating nature of the copolymerization. The monomer reactivity ratios and Alfrey–Price Q,e values were also determined. The thermal behavior of the new synthesized monomers and polymers was investigated by differential scanning calorimetry and thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 995–1004, 2002     

Synthesis, characterization and nonlinear absorption of novel octakis-POSS substituted metallophthalocyanines and strong optical limiting property of CuPc

In this study, the preparation of some novel metallophthalocyanine (MPcs) complexes substituted with octakis(mercaptopropylisobutyl-POSS) functional group was achieved. By the reaction of [1-(3-mercapto)propyl-3,5,7,9,11,13,15-isobutylpentacyclo[9.5.1.1(3,9).1(5,15).1(7,13)]octasiloxane 1 with 4,5-dichloro-1,2-dicyanobenzene 2 in THF as the solvent in the presence of K2CO3 as the base, the phthalonitrile derivative 3 was synthesized. Compound 3 reacted with CoCl2 x 6H2O in ethylene glycol to furnish a novel cobalt(II) phthalocyanine . The tetramerization of 3 with urea and CuCl in the absence of solvent gave the novel Cu(II) phthalocyanine 4; while with Zn(OAc)2 x 2H2O in dry DMF gave the novel zinc(ii) phthalocyanine 6. The structures of the target compounds were confirmed by elemental analysis, UV/VIS, IR, MALDI-TOF MS and 1H NMR spectra. Nonlinear absorptions of MPcs in chloroform solution were investigated by using Z-scan measurement technique with 4 ns pulses at 532 nm wavelength. While CuPc 5 showed very high nonlinear absorption, MPcs 4 and 6 did not show considerable nonlinear absorption. Investigations of optical limiting properties of 5 revealed that this material is a very good candidate for optical limiting applications.     

Synthesis, characterization and some properties of novel bis(pentafluorophenyl)methoxyl substituted metal free and metallophthalocyanines

The preparation of some new tetrakis[bis(pentafluorophenyl)methoxyl] substituted metal free and metallophthalocyanine (MPcs) complexes were achieved by the tetramerization of 4-[bis(pentafluorophenyl)methoxy]phthalonitrile with Li metal in pentan-1-ol or metal [Co(II) or Zn(II)] acetates in DMAE, respectively. The structures of the target compounds were confirmed by elemental analysis, IR, UV–vis, ¹H NMR, ¹⁹F NMR and mass spectroscopic methods. MPcs are soluble only in strong and medium polar solvents while the metal free one is soluble in weakly, medium and strong polar solvents. The temperature and frequency dependence of the electrical conductivities were studied on spin coated films of the compounds using dc and impedance spectroscopy techniques in the frequency range from 40 to 10⁵ Hz and within the temperature range from 290 to 440 K. The temperature dependence of the exponent s and conductivity, σ_ac, were completely in agreement with the prediction of the hopping model. The redox properties of the complexes were determined by cyclic voltammetry. The nature of the redox processes was also confirmed using spectroelectrochemical measurements.     

Synthesis of new pterocarpans and rapid O‐alkylation under microwave irradiation

Herein, it is described five new pterocarpans. Pterocarpans 8 and 9 were synthesized by classical [3 + 2] cycloaddition reaction of 2H‐chromene 7a and 7b with 2‐methoxy‐1,4‐benzoquinone. Pterocarpan 8 was O‐alkylated in the absence of solvents using a domestic microwave oven as a heat source and a classical O‐alkylation method with traditional heating. In this way three more new pterocarpans were obtained. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:239–244, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20175     

Synthesis and characterization of N‐substituted polyaniline with mesogen molecules

The N‐substituted polyaniline (PANi) was synthesized by incorporation of bromine‐terminated mesogens onto the emeraldine form of polyaniline. Firsty three liquid crystalline molecules containing biphenyl units were synthesized. These mesogenic molecules are named as: 6‐bromo‐ (4‐hexyloxy‐biphenyl‐4′‐oxy) hexane (C₆? C₆Br), 5‐bromo‐(4‐hexyloxy‐biphenyl‐4′‐oxy) pentane (C₆? C₅Br), 6‐bromo‐(4‐octyloxy‐biphenyl‐4′‐oxy) hexane (C₈? C₆Br). Differential scanning calorimetry (DSC) in combination with polarizing optical microscopy (POM) were used to investigate the thermal properties of them. Optical microscopy showed focal conic texture characteristic of the Smectic A phase for (C₆? C₅Br) and (C₈? C₆Br). For (C₆? C₆? Br) smectic phase was determined. DSC experiments were also found in accord with mesophase formation. For the synthesis of N‐substituted polyaniline with these mesogen molecules, the emeraldine base polyaniline was reacted with BuLi to produce the N‐anionic polyaniline and then deprotonated polyaniline was reacted with bromine‐end mesogen to prepare mesogen‐substituted polyaniline through N‐substitution reaction. The degree of N‐substitution can be controlled by adjusting the molar feed ratio of mesogen to the number of repeat units of PANi. The microstructure and compositions of obtained polymers were characterized by FT‐IR, elemental analysis, DSC, and scanning electron microscopy (SEM). The cyclicvoltammetry show that the electroactivity of N‐substituted polyaniline is strongly dependent on the degree of N‐grafting. The solubility of mesogen‐substituted polyaniline in common organic solvents such as THF and chloroform was improved by increasing the degree of N‐substitution and also the samples are partially soluble in xylene. Liquid crystalline behavior of mesogen‐substituted polyanilines was investigated via POM, but no mesophase was observed. Copyright © 2008 John Wiley & Sons, Ltd.     

New Method for Synthesis of Multi‐substituted Imidazoles

Here, we reported two methods for the synthesis of multi‐substituted imidazoles, firstly via four‐component cyclocondensation reaction of benzil, aliphatic amines (allylamine or pentylamine), and aromatic aldehyde and ammonium acetate. Using an ionic liquid catalyst namely, diethyl ammonium hydrogen sulfate, and under solvent‐free conditions. Secondly, via the alkylation of synthesized NH imidazoles with alkyl halide (allyl bromide and pentyl bromide) gave 8a–c in high yield (average 90%), the products can be purified by a non‐chromatographic method, and these newly synthesized compounds have been characterized by spectral data: FTIR, IR, ¹H, ¹³C nuclear magnetic resonance, the elemental analysis, and the X‐ray structure.     

Syntheses of new unsymmetrically dodecakis(trifluoroethoxy)‐substituted metallophthalocyanines by a palladium‐catalyzed cross‐coupling reaction

Novel unsymmetrical vanadyl and zinc dodecakis(2,2,2‐trifluoroethoxy)phthalocyaninates with an iodo group were synthesized by a statistical condensation route. The palladium‐catalyzed coupling reaction between such monoiodinated metallophthalocyanines and terminal acetylenic derivatives gave various new unsymmetrically dodecakis(2,2,2‐trifluoroethoxy)‐substituted metallophthalocyanines with extended exocyclic π‐conjugation. Unsymmetrical zinc dodecakis(2,2,2‐trifluoroethoxy)phthalocyaninate with a nitro group was also prepared for comparison. All the target phthalocyanines were separated by common col umn chromatography and characterized by elemental analysis, ir and ¹H‐nmr, uv‐visible and fast‐atombombardment mass spectroscopy.     

An efficient synthesis of 5‐benzoyloxazolines by regio‐ and stereo‐controlled reaction of N‐substituted 2‐benzoylaziridines under microwave irradiation

Several N‐acyl‐2‐benzoylaziridines were prepared conveniently in good to high yields (71‐93%) and used in the preparation of 5‐benzoyloxazolines (76‐91%) by a regio‐ and stereo‐controlled reaction in the presence of Nal as an efficient catalyst under microwave irradiation in short reaction times (5‐10 mins). The structure of the regioisomeric product was confirmed by X‐ray analysis.     

Synthesis and spectral properties of the metallophthalocyanines with the fragments of substituted pyrazoles

By the reaction of 4-bromphthalonitrile with corresponding 1-phenyl-3-methyl-5-hydroxy- and 1-p-sulfophenyl-3-methyl-5-oxypyrazolaes the substituted phthalonitriles were synthesized and converted into metallophthalocyanines with the fragments of substituted pyrazoles. The compounds obtained were identified using the data of elemental analysis, gas chromatography-mass spectrometry, IR, ¹H NMR, and electronic spectroscopy. The influence of the peripheral environment of the phthalocyanine ligand in the resulting metal complexes on the spectral and other properties of the latter was revealed.     

Synthesis and characterization of stereoregular AABB‐type polymannaramides

The condensation of D ‐mannaro‐1,4:6,3‐dilactone ( 2 ) with even‐numbered alkylenediamines (C₂, C₆–C₁₂) in a methanol solution and in the presence of triethylamine afforded polymannaramides 3 – 7 , which were isolated directly as white solids with various hydrophobic–hydrophilic characters. Because all the stereocenters in 2 possessed an S configuration, the random polymerization led to optically active, stereoregular polyhydroxypolyamides. The polymers were characterized by elemental analysis and IR, ¹H NMR, and ¹³C NMR spectroscopy. Their number‐average molecular weights were estimated by ¹H NMR spectral integration analysis. Thermal and powder X‐ray diffraction studies revealed that compounds 3 – 7 were poorly crystalline. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1024–1030, 2001     

A new polymeric phthalocyanine containing 16-membered tetrathia macrocyclic moieties by microwave irradiation: Synthesis and characterization

Tetranitrile monomer (3) was synthesized by nucleophilic aromatic substitution of 1,5,9,13-tetrathiacyclohexadecane-3,11-diol (1) onto 4-nitrophthalonitrile (2). The metal-free phthalocyanine polymer (4) was prepared by the reaction of a tetranitrile monomer with 4-({11-[3-cyano-4-(cyanomethyl)phenoxy]-1,5,9,13-tetrathiacyclohexadecan-3-yl}oxy)phthalonitrile in 2-(dimethylamino)ethanol. Ni(II), Co(II), Cu(I)-phthalocyanine polymers were prepared by the reaction of the tetranitrile compound with the chlorides of Ni(II), Co(II) and Cu(I) in DMAE. Zn(II)-phthalocyanine polymer was prepared by the reaction of the tetranitrile compound with the acetates of Zn(II) in DMAE. The new compounds were characterized by a combination of IR, ¹H NMR, ¹³C NMR, UV-Vis, elemental analysis and MS spectral data.