Dicarboxylic Anhydrides Research Articles

Asymmetric Synthesis of cis-4a,5,8,8a-Tetrahydrophthalazin-1(2H)-one Derivatives Based on Organocatalytic Alcoholysis of Cyclic Dicarboxylic Anhydride

Asymmetric synthesis of optically active cis-4-phenyl-4a,5,8,8a-tetrahydrophthalazin-1(2H)-one and its N-alkylated derivatives based on an organocatalytic enantioselective alcoholysis of cyclic dicarboxylic anhydride was described.

신규 Phthaloperinone 색소의 합성과 특성에 대한 연구

New series of phthaloperinone dyes were synthesized by the condensation reaction between tetrachloro-phthalic anhydride, 2,3-naphthalene dicarboxylic anhydride and o-phenylenediamine, 1,8-diaminonaphthalene, 1,2-diaminoanthraquinone. These dyes absorb at around 370-490nm. It was found that introduction of naphthalene and anthraquinone moiety on the perinone system produces a large bathochromic shift of 100nm. The synthesized dye 7 containing anthraquinone moiety in perinone chromophoric system exhibited superior heat stability and bright color as yellow chromophore. New dye 7 have been investigated in terms of interacting with volatile organic compound(VOC) <TEX>$EtNH_2$</TEX>. The sensing behaviour of the dye 7 toward <TEX>$EtNH_2$</TEX> was studied by UV-vis absorption spectroscopy. Sensing mechanism of dye 7 to <TEX>$EtNH_2$</TEX> was supported by theoretical calculations based on DFT method.

Influence of norbornene dicarboxylic anhydride on the copolymerization of carbon dioxide and propylene oxide

Propylene oxide (PO) and CO2 are terpolymerized with 5-norbornene-2,3-dicarboxylic anhydride (NA) or tetrahydrophthalic anhydride (THPA) under the action of a zinc glutarate catalyst. NMR analysis confirms that the anhydrides are comonomers and are inserted to give ester entities. It was observed that the molecular mass of the terpolymers is higher and the content of the backbiting product cyclic propylene carbonate (cPC) is lower in comparison to PO/CO2 copolymerizations, and that they correlate with each other. Especially NA is suited to decrease the amount of byproduct cPC at initial concentrations lower than 0.5mol% anhydride (relative to PO). The reactivity ratios of CO2 and maleic anhydride (MA), phthalic anhydride (PA), THPA and NA are 0.72, 0.23, 0.041 and 0.027 resp., showing that NA is not readily incorporated. The reduction of backbiting is thus related to the observed increase in molecular mass resulting from a lower rate of termination which, in turn, would result from an interaction of anhydride with the catalyst surface. The higher molecular mass and lower cPC content results in materials with a higher glass transition temperature, higher yield strength, elastic modulus and stress at break.

Renewable production of phthalic anhydride from biomass-derived furan and maleic anhydride

A route to renewable phthalic anhydride (2-benzofuran-1,3-dione) from biomass-derived furan and maleic anhydride (furan-2,5-dione) is investigated. Furan and maleic anhydride were converted to phthalic anhydride in two reaction steps: Diels–Alder cycloaddition followed by dehydration. Excellent yields for the Diels–Alder reaction between furan and maleic-anhydride were obtained at room temperature and solvent-free conditions (SFC) yielding 96% exo-4,10-dioxa-tricyclo[5.2.1.0]dec-8-ene-3,5-dione (oxanorbornene dicarboxylic anhydride) after 4 h of reaction. It is shown that this reaction is resistant to thermal runaway because of its reversibility and exothermicity. The dehydration of the oxanorbornene was investigated using mixed-sulfonic carboxylic anhydrides in methanesulfonic acid (MSA). An 80% selectivity to phthalic anhydride (87% selectivity to phthalic anhydride and phthalic acid) was obtained after running the reaction for 2 h at 298 K to form a stable intermediate followed by 4 h at 353 K to drive the reaction to completion. The structure of the intermediate was determined. This result is much better than the 11% selectivity obtained in neat MSA using similar reaction conditions.

Observation of allylic rearrangement in water-rich reaction

Allylic rearrangement or the migration of a double bond from its original position in the carbon skeleton to an adjacent site was observed when 3,4,5,6-tetrahydrophthalate was hydrolyzed in a basic solution and in the presence of Co(ii) and Mn(ii) under hydrothermal conditions.

Meso-Tetraphenylbenzoporphyrin-22,23-dicarboxylic Anhydride: A Platform to Benzoporphyrin Derivatives

A method to synthesize meso-tetraphenylbenzoporphyrin-2(2),2(3)-dicarboxylic anhydride is reported. This compound reacts with alkylamines and arylamines to afford the corresponding "phthalimides" in moderate to excellent yields. The reaction of the title compound with benzene-1,4-diamine or with benzene-1,3-diamine yields the corresponding N,N'-(phenylene)bisphthalimides, whereas with benzene-1,2-diamine or naphthalene-1,8-diamine it affords heterocyclic-fused porphyrins. Molecular mechanics simulations elucidates the multiplicity of signals observed in the NMR spectra of the N,N'-(1,4-phenylene)bisphthalimide 11. This molecule exhibits two preferential conformations corresponding to a coplanar and an almost perpendicular arrangement of the benzoporphyrin units relative to the central benzenic ring.

Synthesis, characterization, and cytotoxic activity of tricyclohexyltin(IV) carboxylates derived from cyclic dicarboxylic anhydrides

Some tricyclohexyltin(IV) carboxylates, HOOC–R–COOSn(c-C6H11)3 (1) and (c-C6H11)3SnOOC–R–COOSn(c-C6H11)3 (2) [R = 1,2-C6H4 (a), 1,2-C6F4 (b), (Z)-CH=CH (c), CH2CH2 (d)], have been synthesized from reaction of tricyclohexyltin hydroxide with cyclic dicarboxylic anhydrides under microwave irradiation in 1 : 1 and 2 : 1 M ratio, respectively, and characterized by elemental analysis, IR and NMR (1H, 13C, and 119Sn) spectra. Crystal structures of 1a–1c and 2d are determined by X-ray single crystal diffraction. The carboxylate in each compound is monodentate to tin. Compounds 1a and 1c possess a trans-C3SnO2 trigonal bipyramidal geometry with axial positions occupied by carboxylate and carbonyl oxygen of carboxylate of an adjacent molecule forming a one-dimensional chain. Compound 1b is tetrahedral and forms R 2 2(8) hydrogen-bonded dimers by pairs of intermolecular O–HO hydrogen bonds between two carboxylic acid groups. Compound 2d is dinuclear with tin possessing distorted tetrahedral geometry; a trimer supramolecular structure is formed by weak intermolecular SnO interactions. The compounds have potent in vitro cytotoxic activity against two human tumor cell lines, A549 and HeLa.

Advantages of polycarboxylic over dicarboxylic anhydrides in the melt modification of PPC

We present an alternative polymer modification of poly (propylene carbonate) (PPC). A conventional practice for PPC melt processing is the melt - modification with maleic anhydride (MAH) - a di-carboxylic anhydride -. In our work, PPC is melt-modified with pyromellitic di-anhydride (PDAH) - a tetra-carboxylic dianhydride -. Using MAH modified PPC as reference, the polymer degradation and the thermal and viscoelastic properties of the materials are studied. Both anhydrides after their melt compounding have similar efficiency in the conservation of the molecular weight. Strikingly, the use of PDAH is advantageous over MAH considering the improvement of the thermal stability, the decrease of the complex melt viscosity and higher storage modulus (stiffness) of the modified PPC. It is speculated that the changes in the material performance arise from the occurrence of long chain branching and non-covalent interactions from the PDAH modifier.

Synthesis and characterization of a renewable polyester containing oxabicyclic dicarboxylate derived from furfural

Techniques using biomass-based materials have become important to reduce the impacts of global warming and the depletion of petroleum resources. Changing biomass from edible to inedible is essential to solve global food issues. Furan derivatives are ideal chemicals for green chemistry because they are produced from inedible biomass resources. Here, we report the preparation of a biomass-based oxabicyclic dicarboxylic anhydride derived from furan derivatives and its polymerization with several α,ω-diols to polyoxabicyclates. 1H NMR spectra and MALDI-TOF MS measurements verified the chemical structure of the polyoxabicyclates. Polyoxabicyclates prepared using 1,3-propanediol or 1,4-butanediol could be moulded into elastic films by melt pressing. Tensile strength testing of the films indicated that they were highly elastic. Furthermore, the films had good transparency in the visible region.

Synthesis and antitumor activity of 2-N- and 3-S-substituted 5-[2-(4-)benzyloxyphenyl]-1,2,4-triazoles and acylhydrazides

3-Thio-4-phenyl-5-[2-(4-)benzyloxyphenyl]-1,2,4-triazoles were prepared by cyclization of the corresponding thiosemicarbazides in alkaline medium. The 2-N-substituted derivatives of the aforementioned triazoles were obtained via aminomethylation, cyanethylation, and alkylation of α-epoxides. 3-S-Substituted 1,2,4-triazoles were synthesized by alkylation with various aliphatic and aromatic halides. Acylhydrazides were prepared via reaction of 2-(4-)benzyloxybenzoic acid hydrazides with dicarboxylic acid anhydrides. The antitumor activity of the synthesized compounds was studied.

Fluorosilica/sepiolite hybrids for hydrophobic coating

Fluorosilica/sepiolite hybrid composite materials for hydrophobic coating were prepared by the solution dispersion method. At first, sepiolite was dispersed in N,N-dimethyl acetamide (DMAc). Then, tridecafluoro-1,1,2,2,-tetrahydroctyl triethoxysilane was added to the solution. For large-area coating, polynorbornene dicarboxylic anhydride was also added. The surface morphology and hydrophobicity of the hybrid composites were controlled by the fluorosilane contents. The hybrids were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS), water contact angles and pencil hardness test. The maximum value of the water contact angle of the hybrids was 152o. The hardness of the hybrid films was enhanced to 4H with increasing the fluorosilica and PNA contents. The hybrid composites showed good antistaining properties in the writing and erasing test on a glass substrate up to eight times.

Polynorbornene/fluorosilica hybrids for hydrophobic and oleophobic coatings

Polynorbornene dicarboxylic anhydride (PNA)/fluorosilica hybrid coating materials with good hydrophobicity, oleophobicity, transparency, thermal stability, and hardness were synthesised using a sol–gel method. The surface structure, transparency, hydrophobicity, oleophobicity, and surface free energy of the coating could be controlled by adjusting the fluorosilane ratio. The maximum static water and oil contact angles of films were 112° and 87°, respectively. The PNA/fluorosilica hybrid films exhibited good transparency and colourlessness. The marks written using water and oil-based pens on the films could be erased with a tissue even after eight times. In addition, the hardness of the hybrid films was enhanced to 4H with increasing fluorosilane content.

Thermodynamic and kinetic evaluation of the polymerization process of epoxidized biodiesel with dicarboxylic anhydride

This paper reports on a polymerization study of the epoxidized methyl esters (EME) obtained from soybean oil, with phthalic anhydride (PA) and 2‐methyl‐imidazole in the presence of soybean oil biodiesel (BD) as solvent. The gelation region for the system EME/PA/2MI without BD was determined using the Flory's theory occurring between X EME = 0.33 to 0.54. The evaluation of the polymerization enthalpy (ΔH) indicates that the experimental stoichiometric composition of the system EME/PA/2MI without solvent is near to X EME = X PA = 0.5. ΔH values higher than 76 J/g were observed for samples located in the theoretical gelation region. Different polymers were produced using the stoichiometric composition and varying only the amount of BD. Kinetics and thermodynamics of the polymerization reaction, using solvent, were evaluated by DSC technique. The results show that BD acts as solvent in the polymerization reaction and a compensation effect between activation energy and logarithm of pre‐exponential factor was observed. Thermogravimetric analysis indicated that the degradations of the products include two well‐defined processes. The compensation effect was observed in the thermal degradation kinetics too.

Synthesis and properties of iridium polymer complexes based on novel bipyridyl ligands

A novel monomer, viz., bipyridyl-containing dicarboxylic acid, was synthesized from 6-pyridyl-3,4-pyridine dicarboxylic acid anhydride and 5-aminoisophthalic acid. Novel polymer macroligands, viz., copolyamides containing 5, 15, 30, and 45% of the bipyridyl side groups, were obtained based on this monomer by low-temperature polycondensation. Metal polymer complexes (MPC) with different Ir(ppy)2 content were synthesized by the reaction of the polymer ligand with the binuclear complex [Ir(ppy)2Cl]2 (ppy is 2-phenylpyridine) and their properties were studied.

Study of Konjac Glucomannan Esterification with Dicarboxylic Anhydride and Effect of Degree of Esterification on Water Absorbency

Dicarboxylic anhydride esterified Konjac glucomannan (DCKGM) was prepared to reduce the unusual water absorbency of native Konjac Glucomannan (KGM). The dependence of degree of substitution (DS) on the reaction conditions and influence of the DS on water absorbency were studied. The esterification was conducted using refluxing KGM in hot acetic acid which contains phthalic anhydride and pyridine catalyst. The chemical structure and characteristic of DCKGM were analyzed by GPC-MALLS and FI-IR. The results showed that the water absorbency for DCKGM is inversely proportional to DS increase. DCKGM may be a promising biomaterial in application of drug carrier, heavy metal ion adsorption and functional packing materials.

Influence of the structure of organic peroxides on the efficiency of modification of SKI-3 rubber with dicarboxylic acid anhydrides in solution

The efficiency of modification of synthetic isoprene rubber with maleic and endic anhydrides in solution was examined as influenced by a number of initiator systems: dicumyl, dibenzoyl, and dilauroyl peroxides.

Novel DCPD-modified polyester containing epoxy groups: thermal, viscoelastic, and mechanical properties of their wood flour filled copolymers

In this article, the synthesis of novel DCPD-modified polyesters containing epoxy groups and their possible utilization as polar matrices for wood flour filled copolymers have been studied. The novel DCPD-modified polyester containing epoxy groups was prepared during three-step process. First, the addition reaction of maleic acid to DCPD norbonenyl double bond has been performed. Then, the polyesterification of acidic ester of DCPD, cyclohex-4-ene dicarboxylic anhydride, and ethylene glycol (ethane-1,2-diol, EG) or neopentyl glycol (2,2-dimethyl-1,3-propanediol, NP) in the presence of catalyst was carried out using melt condensation technique. Finally, the oxidation process of prepared DCPD-modified polyesters led to obtain DCPD-modified polyesters containing epoxy groups. The structural characterization of prepared DCPD-modified polyesters containing epoxy functionality has been carried out using FTIR and HNMR spectroscopic methods. The thermal, viscoelastic, and mechanical properties of their unfilled and wood flour filled copolymers have been studied by DSC, DMA, TGA analyses, three-point bending test, and Brinell’s hardness. The performed investigations indicated that novel DCPD-modified polyesters containing epoxy groups can be successfully applied as polar matrices for preparation wood flour filled copolymers due to their “compatibility” with hydrophilic wood flour surface which resulted with stronger interactions between wood and polymer surface and thus producing copolymers which were characterized by improved thermo-mechanical properties compared to unfilled copolymers.

Tuning the thermoresponsive properties of hyperbranched poly(ester amide)s based on diisopropanolamine and cyclic dicarboxylic anhydrides

AbstractA range of water‐soluble hyperbranched poly(ester amide)s has been synthesized with a view to studying their thermoresponsive behavior in water. Poly(ester amide)s with lower critical solution temperature (LCST) values around physiological temperatures are of interest for biological and medical applications, whereas poly(ester amide)s with high LCST values may be useful as kinetic hydrate inhibitors for high salinity produced fluids in the oil and gas industry. The LCST of these polymers was measured as the optical cloud point. The LCST can be tuned in various ways for these applications, for example, by varying the hydrophobicity of the groups on the cyclic anhydride monomer or by adjusting the hydrophilicity of the imine used to make the peripheral groups of the polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Synthesis of first row transition metal carboxylate complexes by ring opening reactions of cyclic anhydrides

Hydrolytic and solvolytic ring opening reactions of phthalic anhydride, pyromellitic dianhydride and 2,3-pyridine dicarboxylic anhydride in the presence of various transition metal salts with or without a ancillary ligands were studied. The reactions were found to be dependent on stoichiometry of ligand and types of anhydride used. In the case of pyromellitic dianhydride selective ring opening reaction by cobalt(II) ions gave 1,3-benzene dicarboxylate derivatives, whereas use of copper(II) ions gave 1,4-benzene dicarboxylate derivatives. Preference for methanolysis was seen in the case of copper (II) promoted reactions of pyromellitic dianhydride in the presence of 1:1 metal to 1,10-phenanthroline ratio. Ring opening reactions of phthalic anhydride, pyromellitic dianhydride and 2,3- pyridine dicarboxylic anhydride to prepare various transition metal complexes are discussed. The selectivity on methanolysis is controlled by stoichiometry of nitrogen donor ligands, and position of ring opening is governed by metal ions.

Synthesis of Some Biologically Active 4(3H)-Quinazolinones Derived from 2,3-Pyridine Dicarboxylic Anhydride

A novel 3-amino-4(3H)-quinazolinone was synthesized via two routes. The first route involved interaction of 2,3-pyridine dicarboxylic anhydride with anthranilic acid in acetic acid under reflux to give the amide derivative which was subjected to cyclodehydration and treatment with hydrazine hydrate. The second route involved preparation of amide by treatment of 2,3-pyridine dicarboxylic anhydride with methyl anthranilate in glacial acetic acid under reflux, then treated with hydrazine hydrate. Treatment of 3-amino-4(3H)-quinazolinone with isocyanate, isothiocyanate,ethyl chloroacetate and diethyl malonate gave urea, thiourea, thiazole and pyrimidine derivatives, respectively. In addition, some bisquinazolines were synthesized. Antimicrobial activities of some selected compounds were screened.