Naphthalene Dicarboxylic Acid Research Articles

Hydrothermal Conversion of Poly(ethylene naphthalate) to Naphthalene Dicarboxylic Acid and Ethylene Glycol in the Presence of Trimethylamine

Hydrothermal Conversion of Poly(ethylene naphthalate) to Naphthalene Dicarboxylic Acid and Ethylene Glycol in the Presence of Trimethylamine

Dual-ligand approach to synthesize a new 3-D heterometallic framework consisting of dysprosium–carboxyl belt and inorganic copper–iodine chain

A novel three-dimensional (3-D) Dy(III)–Cu(I) heterometallic polymer, [Dy 2 (pca) 2 (npa) 2 (H 2 O) 3 ](Cu 2 I 2 ) ( 1 , pca = 2-pyrazinecarboxylic acid, npa = 1,8- naphthalenedicarboxylic acid), has been synthesized by hydrothermal reactions of Dy 2 O 3 , CuI, 2-pyrazinecarboxylic acid, 1,8-naphthalene anhydride in water in the presence of HClO 4 . Compound 1 has been characterized by elemental analysis, infrared spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis, respectively. The thermal stability and luminescence property of compound 1 have also been studied. Single crystal X-ray diffraction analysis reveals that compound 1 contains two distinct units of 1-D Dy–carboxyl belt and Cu–I chain. The two types of 1-D units are further linked via pca ligands to give a heterometallic Dy–Cu framework. A novel three-dimensional (3-D) Dy–Cu heterometallic polymer 1 contains two distinct units of 1-D Dy–carboxyl belt and Cu–I chain. The two types of 1-D units are further linked via pca ligands to give a heterometallic Dy–Cu framework. The two different types of 1-D building units are rarely observed in the reported heterometallic framework. • Compound 1 is a 3-D Dy–Cu heterometallic framework. • Compound 1 contains two distinct units of 1-D Dy–carboxyl belt and Cu–I chain. • Compound 1 is synthesized by dual-ligand approach.

Synthesis and crystal structure of the porous metal-organic coordination polymer [Zn4(Ndc)4(Oxdz)2] · 2H2O

New metal-organic coordination polymer [Zn4(Ndc)4(Oxdz)2] · 2H2O (H2Ndc = 2,6-naphthalenedicarboxylic acid, Oxdz = 1,3,4-oxadiazole) was prepared by heating a solution of zinc nitrate, naphthalenedicarboxylic acid, and 4-aminotriazole in DMF. Of particular interest is the in situ transformation of 4-aminotriazole into 1,3,4-oxadiazole. The structure and the composition of the obtained compounds were established by X-ray diffraction, IR spectroscopy, and elemental analysis. The metal-organic framework is electrically neutral and forms a channel structure with the pore diameter of 9 A.

Synthesis, Structures, and Luminescent Properties of Uranyl Terpyridine Aromatic Carboxylate Coordination Polymers

Six novel uranyl terpyridine aromatic carboxylate coordination polymers, [UO(2)(C(6)H(2)O(4)S)(C(15)H(11)N(3))] (1), [UO(2)(C(6)H(2)O(4)S)(C(15)H(10)N(3)Cl)]·H(2)O (2), [UO(2)(C(8)H(4)O(4))(C(15)H(11)N(3))] (3), [UO(2)(C(8)H(4)O(4))(C(15)H(10)N(3)Cl)] (4), [UO(2)(C(12)H(6)O(4))(C(15)H(11)N(3))] (5), and [UO(2)(C(12)H(6)O(4))(C(15)H(10)N(3)Cl)] (6), were synthesized under solvothermal conditions and characterized by single-crystal and powder X-ray diffraction and luminescence and UV-vis spectroscopy. Compounds 1, 2, and 5 crystallize as molecular uranyl dimers, whereas compounds 3, 4, and 6 contain ladder motifs of uranyl centers. Fluorescence spectra of 1-4 show characteristic UO(2)(2+) emission, wherein bathochromic and hypsochromic shifts are noted as a function of organic species. In contrast, uranyl emission from 5 and 6 is quenched by the naphthalene dicarboxylic acid linker molecules.

New anticorrosive coating compositions incorporated ilmenite ore

Objective of the research relates to corrosion-resistant coating capable of being lied to various substrates, particularly metal surfaces, as a single coat characterized as having high-gloss, good adhesion and a high degree of flexibility. Long oil alkyds were first modified with naphthalene dicarboxylic acid and then introduced in primer formulations containing an effective amount of corrosion-resisting pigment ilmenite ore. The results indicated substantial corrosion inhibiting properties.

Structures of new phenylphenalene-related compounds from Eichhornia crassipes (water hyacinth)

Two new compounds identified as methyl derivatives of phenyl naphthalenedicarboxylic acid and phenyl naphthalenecarboxylic acid linked to a phenylphenalene unit were isolated from the extract of Eichhornia crassipes (water hyacinth). The structures have been determined on the basis of spectroscopic analyses, mainly using 2D NMR techniques.

Ligand-controlled assembly of Cd(II) coordination polymers based on mixed ligands of naphthalene-dicarboxylate and dipyrido[3,2-d:2′,3′-f]quinoxaline: From 0D+1D cocrystal, 2D rectangular network (4,4), to 3D PtS-type architecture

Three novel Cd(II) coordination polymers, namely, [Cd(Dpq)(1,8-NDC)(H 2O) 2][Cd(Dpq)(1,8-NDC)]·2H 2O ( 1), [Cd(Dpq)(1,4-NDC)(H 2O)] ( 2), and [Cd(Dpq)(2,6-NDC)] ( 3) have been obtained from hydrothermal reactions of cadmium(II) nitrate with the mixed ligands dipyrido [3,2-d:2′,3′-f]quinoxaline (Dpq) and three structurally related naphthalene-dicarboxylate ligands [1,8-naphthalene-dicarboxylic acid (1,8-H 2NDC), 1,4-naphthalene-dicarboxylic acid (1,4-H 2NDC), and 2,6-naphthalene-dicarboxylic acid (2,6-H 2NDC)]. Single-crystal X-ray diffraction analysis reveals that the three polymers exhibit novel structures due to different naphthalene-dicarboxylic acid. Compound 1 is a novel cocrystal of left- and right-handed helical chains and binuclear complexes and ultimately packed into a 3D supramolecular structure through hydrogen bonds and π– π stacking interactions. Compound 2 shows a 2D rectangular network (4,4) bridged by 1,4-NDC with two kinds of coordination modes and ultimately packed into a 3D supramolecular structure through inter-layer π– π stacking interactions. Compound 3 is a new 3D coordination polymer with distorted PtS-type network. In addition, the title compounds exhibit blue/green emission in solid state at room temperature.

Facile Route to Supramolecular Structures: Self‐Assembly of Dendrimers and Naphthalene Dicarboxylic Acids

Cylinders and spheres can be formed by simple self-assembly of cationic dendrimers and oppositely charged small divalent organic ions in methanol (see graphic). The counterion not only controls the morphology of the nanosized assembly, but also provides functionality, such as fluorescence. The concept may lead to versatile functional supramolecular architectures.

A Convenient and Efficient Method for the Preparation of Unique Fluorophores of Lariat Naphtho‐Aza‐Crown Ethers

AbstractNew naphtho‐aza‐crown ethers containing different phenolic side‐arms attached through the ortho‐position of the phenol have been prepared under solvent‐free conditions. The starting macrocyclic naphtho‐aza‐crown ether 2 was obtained by treatment of naphthalene dicarboxylic acid diester 1 with diethylenetriamine in EtOH at room temperature for two days without stirring in 77% yield (Scheme 1). Phenolic ligands (3–14) were synthesized by the Mannich reaction of the secondary macrocyclic amine 2 with the substituted phenols using nontoxic and inexpensive CaCl2. This procedure was applied successfully for the synthesis of Mannich bases from simple secondary amines. The CaCl2 powder can be reused up to three times after simple washing with dry acetone.

Comparison of the structure and thermal properties of a poly(aryl ether ketone ether ketone naphthyl ketone) with those of poly(aryl ether ketone ether ketone ketone)

AbstractPoly(oxy-1,4-phenylene carbonyl-1,4-phenylene oxy-1,4-phenylene carbonyl-2,6-naphthalene carbonyl-1,4-phenylene) or 2,6-PEKEKNK is a polymer of the poly(aryl ether ketone) family differing from PEKEKK by the presence of a naphthyl group linked at positions 2 and 6 to the two ketone groups. It is synthesized by electrophilic precipitation polycondensation of 2,6- naphthalenedicarboxylic acid chloride with 4,4’-bis-(4-phenoxy) benzophenone in the presence of aluminium chloride. The dimensions of the orthorhombic unit cell determined from an initially amorphous, stretched film are: a = 0.778 nm, b = 0.613 nm, c = 5.52 nm. In contrast with PEKEKK no signs of polymorphism were found for 2,6 PEKEKNK. Its glass transition and melting temperatures are 20 °C and 2 °C above those of PEKEKK, respectively.

Influence of Ligand Geometry on the Formation of In−O Chains in Metal-Oxide Organic Frameworks (MOOFs)

Three indium-oxide organic frameworks, In(2)O(1,3-BDC)(2), 1; In(OH)(2,6-NDC)(H(2)O), 2; and In(OH)(2,7-NDC)(H(2)O), 3 (BDC = benzene dicarboxylic acid and NDC = naphthalene dicarboxylic acid), were synthesized and characterized by thermogravimetric analysis, infrared spectroscopy, and single-crystal X-ray diffraction. Previously, we reported the structure of In(OH)(1,4-BDC).(0.75H(2)BDC), 0, where the framework is built by interconnecting In-OH-In chains with the BDC anions to form large diamond-shaped one-dimensional channels filled with guest molecules. Compounds 0-3 all contain In-O(H) chains, but the coordination and geometry depend on the nature of the dicarboxylate ligand. Compound 0 contains In-O octahedral centers that connect to form a single trans octahedral chain, while in compound 1, they connect to form a more complex double chain of octahedra. Both compounds 2 and 3 contain chains of connected pentagonal bipyramidal InO(6)(OH(2)) units. In 2, these units share trans vertices that are cross-linked by chelating 2,6-NDC anions, whereas in compound 3, cis vertices are shared to form chains that are linked by the 2,7-NDC anions.

β-Cyclodextrin as a Catalyst in Organic Synthesis

This mini-review outlines recent (until the end of 2006) key developments in the use of β-cyclodextrin as a catalyst in organic synthesis. β-cyclodextrin is a water soluble supramolecular catalyst especially useful for transformations such as oxirane ring-opening, aziridine oxidation of alcohols, hydrolysis of phosphate esters and amidation of acids. It has been used for the selective synthesis of 2,6- naphthalene dicarboxylic acid, introduction of protecting groups and for ester cleavage. Interestingly, it has also been used in the aza- Michael addition of amines to conjugated alkenes, in photo-Reimer-Tiemann reactions and as a phase transfer catalyst.

The potential role of redox reactions for the distribution of alkyl naphthalenes and their oxygenated analogues in terrestrial organic matter of Late Palaeozoic age

The occurrence and distribution of alkyl naphthalenes and alkyl phenanthrenes in 39 Late Palaeozoic coal and sediment samples, containing predominantly terrestrial organic matter, is related to thermal maturity and biological source input. This study investigates the relationship between aromatic hydrocarbons and the corresponding aldehydes, ketones, carboxylic acids and dicarboxylic acids based on the naphthalene skeleton. It is suggested that alkyl naphthalenes are oxygenated in the sediments. The behaviour of alkyl phenanthrenes and their oxygenated analogues is discussed in this context. Alkyl naphthalenes and phenanthrenes were abundant in all samples. The low polarity nitrogen, sulfur and oxygen compound fraction was characterised by the presence of alkyl naphthaldehydes and naphthyl ketones for the majority of the samples. The presence of naphthalene carboxylic acids and anthracene/phenanthrene carboxylic acids was restricted to samples of relatively enhanced maturity (vitrinite reflectance, R r, 0.67–1.26%), with one exception. The correlations between the different classes of compounds based on the naphthalene skeleton led to the hypothesis that, within the maturity range investigated, aldehydes and ketones were readily formed from the corresponding aromatic hydrocarbons, while the carboxylic acids were formed at elevated maturity. For alkyl naphthalene dicarboxylic acids, two formation pathways are suggested, because of two different distribution patterns. A direct correlation of these dicarboxylic acids with the occurrence of other compounds having a naphthalene skeleton was not apparent.

Synthesis, Structure Determination, and Hydrogen Sorption Studies of New Metal−Organic Frameworks Using Triazole and Naphthalenedicarboxylic Acid

Two new metal−organic framework compounds were synthesized under solvothermal conditions using Zn2+ ion, 1,2,4-triazole (TRZ), and 1,4- and 2,6-naphthalenedicarboxylic acids (NDC): Zn4(TRZ)4(1,4-NDC)2·2DMF·2H2O (1) and Zn4(TRZ)4(2,6-NDC)2·2DMF·4H2O (2). Their crystal structures were characterized by single-crystal X-ray diffraction. Structure 1 crystallizes in the P21/n space group with a = 13.609(2) Å, b = 27.181(5) Å, c = 13.617(3) Å, β = 92.46(1) °, V = 5032.4(16) Å3, and Z = 4. Structure 2 crystallizes in orthorhombic Pna21 space group with a = 30.978(6) Å, b = 12.620(3) Å, c = 13.339(3) Å, V = 5215(2) Å3, and Z = 4. Both structures are analogues of the previously reported Zn4(TRZ)4(1,4-BDC)2·16H2O where the layers of Zn−triazole moieties are pillared by aromatic dicarboxylates to create 3-D open frameworks. Nitrogen sorption studies revealed that these structures have Brunaer−Emmett−Teller (BET) surface areas of 362.1−584.1 m2/g. Hydrogen sorption experiments showed they can store 0.84−1.09 wt % of H2 at 77 K and 1 atm. Although they do not contain large pores or surface areas, they possess the hydrogen sorption capacities comparable to those of highly porous metal−organic frameworks.

FORMATION OF OXYGENATED-POLYCYCLIC AROMATIC COMPOUNDS IN AEROSOL FROM THE PHOTO-OXIDATION OF o-TOLUALDEHYDE

The secondary organic aerosol formed during the photo-oxidation of o-tolualdehyde in a large smog reaction chamber has been studied using comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry. The separation and detection system was coupled directly to an aerosol thermal desorption stage, providing the ability to resolve all gas chromatography amenable species in a single experimental procedure. The organic content of aerosol formed from the photo-oxidation of o-tolualdehyde contained a diverse range of chemical functionalities including mono-aromatic, carboxylic acid and carbonyl which were predicted as photochemical by-products by a comprehensive chemical mechanism. Around 3% of the organic aerosol content resolved was polycyclic-aromatic in nature. This has indicated that the formation of relatively low volatility by-products was possible via the ring-retained channel from a mono-aromatic precursor. Species found included 2,3 naphthalene dicarboxylic acid, and anthraquinone quantitatively accounting for 0.40% (24.78 ng) and 0.075% (4.64 ng) respectively of the total aerosol (6181.4 ng).

The synthesis, characterization, and crystal structures of poly(2,6‐naphthalenebenzobisoxazole) and poly(1,5‐naphthalenebenzobisoxazole)

AbstractThe rigid‐rod polymers, poly(2,6‐naphthalenebenzobisoxazole) (Naph‐2,6‐PBO) and poly(1,5‐naphthalenebenzobisoxazole) (Naph‐1,5‐PBO) were synthesized by high temperature polycondensation of isomeric naphthalene dicarboxylic acids with 4,6‐diaminoresorcinol dihydrochloride in polyphosphoric acid. Expectedly, these polymers were found to have high thermal as well as thermooxidative stabilities, similar to what has been reported for other polymers of this class. The chain conformations of Naph‐2,6‐PBO and Naph‐1,5‐PBO were trans and the crystal structures of Naph‐2,6‐PBO and Naph‐1,5‐PBO had the three‐dimensional order, although the axial disorder existed for both Naph‐2,6‐PBO and Naph‐1,5‐PBO. Naph‐2,6‐PBO exhibited a more pronounced axial disorder than Naph‐1,5‐PBO because of its more linear shape. The repeat unit distance for Naph‐2,6‐PBO (14.15 Å) was found to be larger compared with that of Naph‐1,5‐PBO (12.45 Å) because of the more kinked structure of the latter. The extents of staggering between the adjacent chains in the ac projection of the crystal structure were 0.25c and 0.23c for Naph‐2,6‐PBO and Naph‐1,5‐PBO, respectively. Naph‐1,5‐PBO has a more kinked and twisted chain structure relative to Naph‐2,6‐PBO. The kinked and twisted chain structure of Naph‐1,5‐PBO in the crystal seems to prevent slippage between adjacent chains in the crystal structure. The more perfect crystal structure of Naph‐1,5‐PBO may be due to this difficulty in the occurrence of the slippage. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1948–1957, 2006

Degradation of aromatic hydrocarbons by Sphingomonas paucimobilis strain EPA505.

To determine the substrate range capability of Sphingomonas paucimobilis strain EPA505, a number of aromatic compounds were tested as potential growth substrates. Strain EPA505 grew on phenanthrene, naphthalene, fluoranthene, toluene, benzoic acid, 2,3- and 3,4-dihydroxybenzoic acids, 1-chloro-2,4-dinitrobenzene, anthracene, 2-hydroxy-3-naphthoic acid and 1-hydroxy- 2-naphthoic acid, salicylic acid, and catechol. Strain EPA505 was unable to grow on coumarine 3-carboxylic acid, naphthalene dicarboxylic acid, acenaphthene, chrysene, pyrene, benzo[b]fluoranthene, and fluorene. Catabolic products were not detected or identified when the bacterium was incubated with coumarine 3-carboxylic acid, naphthalene dicarboxylic acid, acenaphthene, chrysene, or benzo[b]fluoranthene. Dihydroxypyrene, the ortho ring fission product of pyrene, and 10-hydroxy-1- phenanthroic acid were detected when the bacterium was incubated with pyrene. The open rings of benzo[b]fluoranthene, hydroxyacephenanthroic acid, hydroxyacephenanthrene, and phenanthrene anhydride, catabolites of benzo[b]fluoranthene degradation, were detected with Tn5 mutants of EPA505. With strain EPA505, both 9-fluorenone and an open ring fission product accumulated during incubation with fluorene. Other catabolites beyond the open ring of fluorene were detected, specifically dihydroxyfluorene, hydroxy-9-fluorenone, dihydroxy-9-fluorenone, hydroxyindane, and a putative glutathione-conjugated benzylanhydride. Benzylanhydride appeared to be a final end product of fluorene degradation by strain EPA505.

Application of a Second-Order Kinetic Model to a Complex Melt Polymerization Reaction

A novel copolymer system has been synthesized using methyl hydroquinone diacetate (MHQDA), 1,4 naphthalene dicarboxylic acid (1,4 NDCA), and polybutylene terephthalate (PBT) using the melt polymerization technique. The optimum kinetic parameters pertinent to this system are reported in this study. A simple second-order reaction sequence summarizes catalyzed and uncatalyzed reactions between MHQDA, 1,4 NDCA, and PBT. The kinetic parameters for the copolymerization reaction were determined using a new second-order model. This technique was used to compute the moles of acetic acid generated in the polymerization process. The model was compared to that of the experimentally determined data. Close comparison (percentage error of less than 5%) was obtained between the experimental and theoretical data. The kinetic data support block copolyester formation. The thermal data also supports formation of block polymers.

Comparative degradation by micro-organisms of terephthalic acid, 2,6-naphthalene dicarboxylic acid, their esters and polyesters

Various derivatives of terephthalic acid (TA) and 2,6-naphthalene dicarboxylic acid (NDA) have been degraded in the presence of various strains of micro-organisms. These compounds include the dimethylesters (TME and NDME), the ethylene glycoldiesters (TGE and NDGE) and the corresponding ethylene glycol polyesters (PET and PEN). The terephthalic acid derivatives were shown not to be degraded by a pure strain of nonsporulating gram-positive bacteria isolated from an industrial compost for household refuse although this micro-organism efficiently mineralizes aliphatic polyesters. The naphthalene dicarboxylic acid and derivatives did not allow growth of various Pseudomonas strains which assimilate naphthalene and some of its simple derived compounds. Therefore, isolation of micro-organisms degrading these aromatic acids and ester derivatives was performed using an enrichment technique. Garden soil or compost was used as sources of micro-organisms. Six strains efficiently degrading TA, TME and TGE were isolated while only two strains assimilating NDA and NDME slowly, inefficiently and with a bad reproductibility were obtained. PET and PEN were degraded by none of these strains.

Molecular Recognition of Naphthalenedicarboxylic Acid Regioisomers by Cyclodextrins

Abstract Complexation of cyclodextrins (CD’s) with some regioisomers of naphthalenedicarboxylic acid (NDC) was examined in 0.1 mol dm−3 NaHCO3 at 25 °C by means of 1H NMR spectroscopy, together with the measurement of induced circular dichroism spectra of NDC’s with the addition of CD’s. The 1H NMR spectra of 2,6- and 2,7-NDC’s showed characteristic AB-type patterns, which changed continuously with increasing CD concentration in accord with the Pople theory. The binding constants (Ka) for β-CD complexes with NDC’s increased in the order of: 1,4-NDC ≈ 1,5-NDC < 1,3-NDC < 1,6-NDC < 2,3-NDC < 2,7-NDC ≤ 2,6-NDC, indicating that β-CD is able to recognize the molecular structures of NDC’s. On the other hand, interactions of α- and γ-CD’s with NDC’s were very weak and nonspecific to NDC’s. The molecular structures of β-CD complexes with some NDC’s were estimated based on the ROESY spectra of the systems. Column chromatography of NDC’s using a β-CD-(2-chloromethyloxirane) polymer column showed that the retention volumes for NDC’s increased in the order of: 1,4-NDC < 1,6-NDC < 2,3-NDC < 2,7-NDC < 2,6-NDC, which agreed with the order the Ka values.