Synthesis and functionalization of Poly[5,5′‐(silylene)‐2,2′‐dithienylene]s using silyl triflate intermediates†

Treatment of 5,5′‐dilithio‐2,2′‐dithiophene with (dimethylamino)methylsily bis(triflate)‐ or α, ω‐bis(triflate)‐substituted trisilanes gave poly[5,5′‐(silylene)‐2,2′‐dithienylene]s in high yields. The amino–silyl bond was cleaved selectively by triflic acid, leading to triflate‐substituted derivatives. Conversion of these compounds with nucleophiles gave other functionalized polymers. Platinum‐catalyzed hydrosilylation reactions between silicon–vinyl and silicon–hydrogen derivatives result in polymer networks which may serve as interesting preceramic materials. The structures of the polymers were proven by NMR spectroscopy (²⁹Si, ¹³C, ¹H). Results of thermal gravimetric analysis (TGA), UV spectrometry and conductivity measurements are given. Copyright © 1999 John Wiley & Sons, Ltd.     

Synthesis and characterization of thermally stable poly-N, N′-arylenebismaleimide

Three N,N′-arylenebismaleimides, viz. N,N′-m-phenylenebismaleimide, N,N′-p-phenylenebismaleimide and N,N′-benzidinebismaleimide, were prepared and polymerized in toluene using benzoyl peroxide (BPO) as initiator. The polymers obtained were characterized on the basis of elemental analysis and IR spectra. The polymers are insoluble in common organic solvents. The thermal behaviour of these polymers was studied by DTA and TG methods and the kinetic parameters order of reaction and activation energy were estimated.     

Molten salt ionic liquid-assisted synthesis of nano-structured poly(amide imide)s based on 4,4′-methylenebis(3-chloro-2,6-diethyl trimellit imidobenzene) via microwave process as an environmentally friendly methodology

In this paper, for the first time, 4,4′-methylene-bis(3-chloro-2,6-diethyl trimellit imidobenzene) was prepared by the condensation reaction of 4,4′-methylene-bis(3-chloro-2,6-diethylaniline) and trimellitic anhydride. A series of novel poly(amide imide)s was prepared by the direct polycondensation of the synthesized diimide diacid and various commercial diamines using tetra-n-butylammonium bromide and triphenyl phosphite as a condensing agent under microwave irradiation. Tetra-n-butylammonium bromide acts both as a solvent and a catalyst to mediate clean polymerization reactions to yield the desired polymers. The obtained polymers were characterized with FTIR, ¹H NMR, X-ray diffraction, field emission scanning electron microscopy, elemental and thermogravimetric analysis. The poly(amide imide)s were generally soluble in polar organic solvents, such as N,N′-dimethyl acetamide, N,N′-dimethylformamide, N-methyl-2-pyrrolidone and sulfuric acid at room temperature, and are insoluble in methylene chloride, cyclohexane and water. Morphology probes showed these macromolecules were non-crystalline and nano-structured polymers. The effect of ultrasonic irradiation on the surface morphology of polymers was studied and the results demonstrated that the morphology of macromolecules after ultrasonication became more homogenous than it is before ultrasonic radiation. On the basis of thermogravimetric analysis data, such polymers are thermally stable and can be classified as self-extinguishing polymers.     

Magnetic circular dichroism of some benzene derivatives

The MCD spectra of phloroglucin, 1,3,5-trimethoxybenzene, 1,3,5-tricyanobenzene, 1,3,5-trinitrobenzene, 1,3,5-benzenetricarboxylic acid and 1,3,5-benzenetricarbonyl chloride were measured. For the ¹E′ ← ¹A′₁ transition of phloroglucin or 1,3,5-tricyanobenzene and the ¹E′ ← ¹A′ transition of 1,3,5-trimethoxybenzene, the Faraday A term was observed and the A/D value was extracted. However, 1,3,5-trinitrobenzene, 1,3,5-benzenetricarboxylic acid and 1,3,5-benzenetricarbonyl chloride showed no magnetic circular dichroism in this spectral region. The magnetic moments in the ¹E′ states of these molecules seem to be quenched by the effects of substituents. The magnetic moments in the ¹E′ states of benzene derivatives are sensitive to substitution in the benzene ring.     

Synthesis and stabilization mechanism of novel stabilizers for fullerene-malonamide derivatives in nitrocellulose-based propellants

Nitrocellulose (NC)-based propellants require stabilizers to avoid early decomposition or even explosion during storage. A series of novel fullerene-malonamide derivatives with different carbon chain lengths on the p-position of the benzene ring was synthesized as stabilizers for NC-based propellants through the Bingel reaction because of the excellent thermal stability and strong ability of these derivatives to eliminate free radicals. The molecular structures of these fullerene-malonamide derivatives were verified via ¹H nuclear magnetic resonance (NMR) spectroscopy, ¹³C NMR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, ultraviolet–visible spectroscopy, and high-resolution mass spectrometry. Meanwhile, their stability was investigated using methyl violet, vacuum stability, and weight loss tests. Results indicated that the stability of the novel fullerene-malonamide derivatives was considerably better than that of traditional stabilizers, such as N,N′-dimethyl-N,N′-diphenylurea and diphenylamine. Moreover, these derivatives exhibited excellent thermal stability at high temperatures. The stability of the fullerene-malonamide derivatives also improved as the carbon chain length on the p-position of the benzene ring on C₆₀ increased. In addition, the stability mechanism of the fullerene-malonamide derivatives was studied through electron paramagnetic resonance spectroscopy, FT-IR spectroscopy, and liquid chromatography-mass spectrometry. Results turned out that the fullerene-malonamide derivatives could react with nitroxide radicals released from the pyrolysis of NC. Hence, these novel fullerene-malonamide derivatives can be used as promising stabilizers for NC-based propellants.     

Chemical transformations of N-morpholinylacetic acid hydrazide and steric structure of its derivatives

The reaction of N-morpholinylacetic acid hydrazide with various isothiocyanates and potassium thiocyanate resulted in the corresponding potentially biologically active thiosemicarbazide derivatives. Potassium N′-(2-morpholin-4-ylacetyl)hydrazinocarbothioate was synthesized and involved into heterocyclization in acidic environment to yield cyclic 5-(morpholinomethyl)-1,3,4-thiadiazole-2-thione. The structure of the synthesized compounds was established by IR, ¹H NMR spectroscopy, mass spectrometry, and XRD analysis.     

Mono-, di-, and tetra-aurated derivatives of barbituric acid,including a new type of polynuclear gold compound. Crystal structure of 1,3-bis(triphenylphosphinegold)-5,5-diethylbarbituric acid

Reaction of barbituric acid (2,4,6-pyrimidinetrione) or its derivatives with LAuCl (L = triphenylphosphine) gave 3-LAu-5,5-diethyl-, 1,3-(L'Au)₂-5,5-diethyl- (L′ = L or L′ = Cy₃P), 1,3-dimethyl-5,5-bis(LAu)-, or 1,3,5,5-tetrakis-(LAu)barbituric acid, which were characterized as N-, N,N′-, C,C′-, or N,N′,C,C-gold derivative,s respectively, by IR, ¹H, ¹³C and ³¹P NMR spectroscopy. In the case of 1,3-(LM)(L″M)-5,5-diethylbarbituric acid compounds with M = gold and L″ either Cy₃P, Ph₃As, or (4-tolyl)₃P, or ML = ML″ = HgMe were prepared. An X-ray diffraction study of 1,3-(LAu)₂-5,5-Et₂-pyrimidin-2,4,6-trione · 3C₆H₆ revealed that (a) the heterocyclic ring is planar, (b) there is no inter- or intra-molecular Au ⋯ Au interaction, and (c) the coordination around each gold atom is approximately linear (PAuN 178.3(4)°, with AuN 2.022(12) and AuP 2.233(5) Å. The molecular parameters are compared with those for barbituric acid and other barbiturates.     

Synthesis and characterization of optically active poly(amide-imide)s based on [N,N′-(4,4′-carbonyldiphtaloyl)-bis-lamino diacid]s and 1,5-bis(4-aminophenyl)penta-1,4-dien-3-one

Six dicarboxylic acids 3a-3f were synthesized by the reaction of 3,3’,4,4’-benzophenonetetracarboxylic dianhydride 1 with L-aminoacids 2a-2f in a solution of glacial acetic acid/pyridine(Py) at refluxing temperature.Then six new poly(amide-imide)s PAIs were synthesized from the direct polycondensation reaction of[N,N’-(4,4’- carbonyldiphtaloyl)-bis-L-amino diacid]s with 1,5-bis(4-aminophenyl)penta-1,4-dien-3-one(APPD).The polymerization reactions produced a series of new optically active PAIs with high yield and good inherent viscosity.Also these PAIs are optically active and soluble in various organic solvents.These resulting new polymers can be used in column chromatography for the separation of enantiomeric mixtures.The resulted polymers were fully characterized by means of FTIR and ~1H-NMR spectroscopy,elemental analyses,inherent viscosity measurements,solubility tests and thermogravimetric analysis(TGA).     

New Poly(Bismaleimide-Ether)s Containing Functional Pendant Carboxylic Groups

Abstract

New poly(bismaleimide-ether)s with functional pendant groups were synthesized by Michael addition polymerization of two monomers with functionality f > 2 (DL tartaric acid and methylene-5,5′disalicylic acid) to various bismaleimides with flexible groups (N,N'-4,4′-diphenyl-methanebismaleimide, N,N'-4,4′-diphenyletherbismaleimide and N,N'-4,4′-dibenzylbismaleimide). The polymerization occurred in solution, through the addition of the OH groups to the C[dbnd]C double bond of the maleimide rings. The polymers were obtained in good yields and they were characterized by elemental analysis, IR and ¹H NMR spectra, thermogravimetric analysis and viscozimetry.     

Preparation of phosphorus-containing polymers—XVI. Synthesis of phosphorus-containing polyanhydride-imides

Phosphorus-containing polyanhydride-imides were synthesized from N,N-bis(4-carboxyphthalimido)-3,3′-diphenylalkylphosphine oxide, 3,3′-[N,N′-bis(4-carboxyphthalimido)]benzophenone and their mixtures in two steps via the diacetyl derivatives of the bisimide-carboxylic acids. The resulting polymers have reduced viscosities of 0.06–0.14 dl/g and are soluble in polar aprotic solvents such as DMA, DMF and DMSO, and conc. H₂SO₄ etc. They have good hydrolytic stability for moisture and water. Phosphorus-containing polymers have little heat-resistance and poor flame-retardance. The benefit of incorporating phosphorus in the polymers is small.     

A New Conformation of a Water Hexamer Chain and its Reversible Formation/Removal in the Host Channel by Gas–Solid Reaction

Crystal structure determinations of, in most cases, hydrated, alkali metal derivatives of the dicarboxylic acids, 2,2′-bipyridine-3,3′-dicarboxylic acid (H²BDC) and chelidamic acid (4-hydroxypyridine-2,6-dicarboxylic acid, H²CHEL) show numerous similarities, such as in the predominance of O-coordination in generating solid state polymers in which parallel arrays of the essentially planar ligand ring units are apparent, though not necessarily indicative of conventional π-stacking interactions, and some unanticipated differences. In particular, all species derived from chelidamic acid, including its diammonium compound, appear to be complexes of the partially deprotonated pyridone form of this ligand. In both systems, close contacts between atoms constituting the aromatic entities take a variety of forms depending upon the associated metal.     

Metallocene monomers and polymers. Ferrocenyl and ferrocenylene derivatives

The synthesis and study of some polyenes, polýiminoimides and Schiff polybases with ferrocene obtained by either polymerization or polycondensation are reported.The following monomers were used: ethynylferrocene, 1-chloro-1′-ethynyl-ferrocene, α-chloro-β-formyl-p-ferrocenylstyrene, p-ferrocenylphenylacetylene, p-ferrocenylacetophenone, 1,1′-diacetylferrocene and 1,1′-bis[β-(2-furyl)acryloyl]ferrocene which were characterized by spectral and thermodifferential analyses and Hückel MO calculations. The polymerization was performed in the presence of benzoyl and lauroyl peroxides, triisopropylboron and complex catalysts of [P(C₆H₅)₃]₂ NiX₂ type. The ferrocene derivatives were polycondensed with biuret, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl thioether, 4,4′-diamino-2,2′-dinitrodiphenyl disulphide in the presence of metallic salts and p-toluene sulphonic acid as catalysts.Polymers with either linear or tridimensional structure showing good thermal stability and semiconducting properties have been obtained. Some polymers show catalytical activity in the polymerization of chloroformylated vinylic derivatives.     

The Equally Important Role of Adenine Derivatives to That of Pyrimidine Derivatives in Near‐0 eV Electron‐Induced DNA Lesions

The role of adenine (A) derivatives in DNA damage is scarcely studied due to the low electron affinity of base A. Experimental studies demonstrate that low‐energy electron (LEE) attachment to adenine derivatives complexed with amino acids induces barrier‐free proton transfer producing the neutral N₇‐hydrogenated adenine radicals rather than conventional anionic species. To explore possible DNA lesions at the A sites under physiological conditions, probable bond ruptures in two models—N₇‐hydrogenated 2′‐deoxyadenosine‐3′‐monophosphate (3′‐dA(N7H)MPH) and 2′‐deoxyadenosine‐5′‐monophosphate (5′‐dA(N7H)MPH), without and with LEE attachment—are studied by DFT. In the neutral cases, DNA backbone breakage and base release resulting from C_3′?O_3′ and N₉?C_1′ bond ruptures, respectively, by an intramolecular hydrogen‐transfer mechanism are impossible due to the ultrahigh activation energies. On LEE attachment, the respective C_3′?O_3′ and N₉?C_1′ bond ruptures in [3′‐dA(N7H)MPH]^? and [5′‐dA(N7H)MPH]^? anions via a pathway of intramolecular proton transfer (PT) from the C_2′ site of 2′‐deoxyribose to the C₈ atom of the base moiety become effective, and this indicates that substantial DNA backbone breaks and base release can occur at non‐3′‐end A sites and the 3′‐end A site of a single‐stranded DNA in the physiological environment, respectively. In particular, compared to the results of previous theoretical studies, not only are the electron affinities of 3′‐dA(N7H)MPH and 5′‐dA(N7H)MPH comparable to those of hydrogenated pyrimidine derivatives, but also the lowest energy requirements for the C_3′?O_3′ and N₉‐glycosidic bond ruptures in [3′‐dA(N7H)MPH]^? and [5′‐dA(N7H)MPH]^? anions, respectively, are comparable to those for the C_3′?O_3′ and N₁‐glycosidic bond cleavages in corresponding anionic hydrogenated pyrimidine derivatives. Thus, it can be concluded that the role of adenine derivatives in single‐stranded DNA damage is equally important to that of pyrimidine derivatives in an irradiated cellular environment.     

Synthesis of endo,exo-7,8,9,10-tetrachlorobicyclo[4.4.0]deca-7,9-diene-3,4-dicarboxylic acid N,N′-bisimides

A one-stage synthesis was developed of N,N′-(3,3′-dimethoxy-4,4′-diphenylmethane)- and N,N′-(1,2-ethane)-endo,exo-7,8,9,10-tetrachlorobicyclo[4.4.0]deca-7,9-diene-3,4-dicarboxylic acids bisimides by reaction of a bisadduct of 1,8,9,10,11,11-hexachlorotricyclo[6.2.1.0^5,10]-undec-9-ene-4,5-dicarboxylic acid N,N′-R-bisimide with pyridine in DMF. The spatial structure of compounds obtained was established.     

Structural Dependence of the Selectivity of Fluorescent Chemosensors to Mg2+ from Alkali Earth Metal Ions

A series of novel 2,2′‐bipyridylene‐containing conjugated polymers are synthesized through the Wittig reaction. Some of these polymers show a highly selective affinity toward Mg²⁺ in a mixture of alkaline earth metal ions, which is different from the 2,2′‐bipyridylene‐containing poly(phenylene vinylene) derivatives reported previously. This is the first case to demonstrate that some materials show a selectivity toward Mg²⁺. The structures of the polymers may play a crucial role for this selectivity.     

Anthradithiophene–thiophene copolymers with broad UV–vis absorption for organic solar cells and field‐effect transistors

New semiconducting copolymers, poly((TIPS‐ADT)‐(4,4′‐didodecyl‐2,2′‐bithiophene)) (PTADT2) and poly((TIPS‐ADT)‐(2,2′‐(4,4′‐didodecyl‐2,2′‐bithiophene)dithiophene)) (PTADT4) , produced by incorporating 5,11‐bis(triisopropylsilylethynyl) anthra[2,3‐b:7,6‐b']dithiophene (TIPS‐ADT) and alkyl‐thiophene derivatives were synthesized via Stille coupling polymerization. The optical, electrochemical, structural, field‐effect transistor, and solar cell properties of the polymers were investigated. The polymers showed good solubility at room temperature in common organic solvents due to their abundant side groups including TIPS and dodecyl side chains. Both polymers showed very broad UV absorption spectra covering the spectral range from 300 to 750 nm as a result of the combination of the different absorption ranges of the TIPS‐ADT unit (short wavelength region) and thiophene derivatives (long wavelength region). The FET device fabricated using PTADT4 containing additional unsubstituted thiophene rings as a spacer between TIPS‐ADT and thiophene derivatives showed a higher hole mobility (5.7 × 10^?4 cm²/V s) than the PTADT2 device (2.8 × 10^?5 cm²/V s), due to the improved intermolecular ordering caused by the reduced steric hindrance between bulky side chain groups. In addition, the PTADT4 :(6,6)‐phenyl‐C₇₀‐butyric acid methyl ester (PC₇₀BM) device showed an enhanced power conversion efficiency (PCE) of 1.30% compared with the PTADT2 :PC₇₀BM device (PCE of 0.55%) under AM 1.5G irradiation (100 mW/cm²). © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Semiconducting polymers from triphenylamine derivatives‐benzaldehyde polymers by oxidization with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ)

4‐Tolyldiphenylamine (TDPA) and N,N′‐diphenyl‐N,N′‐bis(4‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine (TPD), were reacted with benzaldehyde (BA) using p‐toluenesulfonic acid as a catalyst to yield linear polymers. The polymers were reacted with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) in tetrahydrofuran (THF) at room temperature. ¹H‐NMR showed that all the methine protons in the residue of BA were completely removed at the mole ratio of repeating unit : DDQ, 2 : 1. The resulting polymers showed good solubility in chloroform or THF. The reacted TDPA‐BA and TPD‐BA polymers gave new UV absorption peaks at 697.0 and 722.5 nm and showed reversible redox potentials about 0.994 and 1.021 V, respectively. Direct current (d.c.) conductivity of the reacted polymers was in the range of 10^?11 S/cm, which is more than two orders higher than the unreacted polymers. The polymer showed pentad split electron spin resonance (ESR) signal, whose concentration was one in 670 or 230 repeating unit for TDPA‐BA and TPD‐BA polymers, respectively. Copyright © 2001 John Wiley & Sons, Ltd.     

Zur Kenntnis der Indolreaktion nach Fischer. II. Thermische und säurekatalysierte Indolisierung von 1′-Alkenyl-2′-methyl-2′-phenylacetohydraziden

On the Fischer-Indole Reaction. II. Thermal and Acid Catalysed Indolization of 1′-Alkenyl-2′-methyl-2′-phenylacetohydrazides Seven different 1′-alkenyl-2′-methyl-2′-phenylacetohydrazides, 6a-g , have been prepared by treatment of the methylphenylhydrazones 7 of appropriate ketones and aldehydes with acetyl chloride in pyridine. At 170° 6a-g are transformed into the N-methylindoles 3a-g and acetamide in moderate yield. N-Methylaniline is the other major reaction product indicating that homolytic cleavage of the weak N, N-bond in 6 is a major primary reaction step. It is likely but not proven that the N-methylindoles 3 are formed in a reaction sequence initiated by an uncatalysed concerted [3, 3]-sigmatropic rearrangement. Upon treatment of 6 with 0.5N dichloroacetic acid in anhydrous acetonitrile at room temperature a quantitative conversion to 3 is observed, interpreted as proceeding by a charge induced [3, 3]-sigmatropic rearrangement of protonated 6 in the rate determining step. The ketone derivatives 6a-e (R¹ = alkyl) react 40-1000 times faster with acid than the aldehyde derivatives 6f and 6g (R¹ = H). This is rationalized as a consequence of the increased basicity of 6a-e relative to 6f and 6g caused by a steric effect.     

Etude de la complexation des lanthanides trivalents par les isomères de l'acide diaminocyclohexanetétraacétique: Partie 2. Les Constantes d'Acidité et les Constantes de Formation des Complexes 1:1 avec l'Acide trans-1,4-Diaminocyclohexane-N,N,N′,N′-Tétraacétique

(Study of the complexation of trivalent lanthanides by the six isomers of diaminocyclohexanetetraacetic acid. Part 2. Acidity constants and formation constants of the 1:1 complexes of trans-1,4-diaminocyclohexane-N,N,N′,N′-tetraacetic acid)Potentiometric measurements of the acidity constants of trans-1,4-diaminocyclohexane-N,N,N′,N′-tetraacetic acid (trans-1,4-DCTA) and of the stability constants of its 1:1 complexes with the trivalent lanthanides are reported for an ionic strength of 1 (KCl) at 25°C. The behaviour of this ligand is similar to that of monoaminodiacetic acids, suggesting that only one N(CH₂COO^?)₂ group participates in chelation. The selectivity of trans-1,4-DCTA for the lanthanides is better than that reported for the monoaminodiacetic acids.     

Synthesis of chiral linear and macrocyclic candidates: VI. Synthesis and antibacterial activity of some macrocyclic tripeptides and linear dipeptide Schiff bases

A series of macrocyclic tripeptides and linear dipeptide Schiff base derivatives has been synthesized using pyridine-3,5-dicarboxylic acid and L-phenyalanine methyl ester as starting materials. Treatment of pyridine-3,5-dicarbonyl dichloride with L-phenylalanine methyl ester gave N,N′-(pyridine-3,5-diyldicarbonyl)bis(L-phenyalanine methyl ester) which was hydrolyzed with 1N sodium hydroxide to the corresponding bis-acid, and the latter was cyclized with diamino acids to afford macrocyclic tripeptide derivatives. The reaction of the bis ester with hydrazine hydrate gave bis-hydrazide, which was condensed with aldehydes to obtain the corresponding Schiff base derivatives. The structures of the newly synthesized compounds were confirmed by IR, ¹H and ¹³C NMR, and MS spectral data and elemental analyses. The antimicrobial activities of some of the newly synthesized compounds were comparable with that of Streptomycin used as control.