Synthesis and structure of tris(4-fluorophenyl)antimony dicarboxylates

The interaction of tris(4-fluorophenyl)antimony with chloroacetic, 4-nitrophenylacetic, and benzoic acids in diethyl ether in the presence of tert-butyl hydroperoxide has yielded tris(4-fluorophenyl)antimony dicarboxylates, their Sb atoms bearing distorted trigonal bipyramid coordination with the carboxylate ligands in the axial positions. The intramolecular contacts between Sb atom and carbonyl O atom are formed in the molecules of the products. Their crystal packing is determined by weak intermolecular hydrogen bonds of the H···F and H···O=C types.     

Synthesis, structure and luminescent properties of yttrium benzene dicarboxylates with one- and three-dimensional structure

The synthesis and structure of two yttrium benzene dicarboxylates, 1 is proportional to [[Y2(C12N2H8)2(C8H4O4)3].H2O], I and 3 is proportional to [[Y2(C12N2H8)2(C8H4O4)3]], II with one- and three-dimensional structure has been accomplished employing hydrothermal methods in the presence of 1,10-phenanthroline. While I is formed with phthalic aid (1,2-BDC), II is formed using isophthalic acid (1,3-BDC). Both the structures appear to have comparable building units, an eight-membered ring and a paddle-wheel arrangement, connected through the carboxylic acid. The 1,10-phenanthroline, connected to Y as a secondary ligand, occupies the inter-chain spaces in I, and projects into the channels in II. The channels in II are inter-connected. Photoluminescence studies indicate that both I and II exhibit a bathochromic shift with respect to the acids (1,2-BDC and 1,3-BDC) and a hypsochromic shift with respect to 1,10-phenanthroline. Both the compounds exhibit reasonable pi...pi interactions.     

Synthesis of novel aminothiopyran dicarboxylates

A one step synthesis of previously unknown aminothiopyran dicarboxylates from readily available starting materials is described. The yields range from 33–74%.     

双(三苯基锗)二元羧酸酯的合成和性质

通过三苯基氯化锗与二元羧酸钠反应合成了12种新的双(三苯基锗)二元羧酸酯。利用元素分析、红外光谱、核磁共振氢谱表征了这些化合物的结构,红外光谱测试表明,所有化合物中羧基是以单齿形式与锗原子配位。生物活性测试结构表明,该类化合物对MCF-7和WiDr癌细胞具有较高的体外抑制活性。     

双(三苄基锡)二元羧酸酯的合成及生物活性

以三苄基氧化锡和相应的二元羧酸反应,合成了14种新的双(三苄基锡)二元羧酸酯。利用元素分析、IR、^1HNMR和MS表征了这些化合物的结构。生物活性测试表明,该类化合物具有较好的杀菌活性。     

双(三烃基锡)二元羧酸酯的合成、结构和农药活性普筛

合成了一系列双(三烃基锡)二元羧酸酯类化合物,表征了这些化合物的结构,并进行了农药活性普筛。结果表明,三环己基锡系列大多具有很好的杀螨和杀虫活性,三苯基锡系列则在除草和植物生物刺激方面有一定效果。同时,还发现农药活性同二元羧酸酯的骨架有关,邻苯二甲酸和丁烯二酸衍生物的效果优于脂肪二酸衍生物。     

Synthesis and biological evaluation of nucleoside dicarboxylates as potential mimics of nucleoside diphosphates

A series of nucleotide analogues wherein the diphosphate moiety has been replaced by a dicarboxylate were synthesized and tested for inhibitory activity against nucleoside diphosphate (NDP) kinase as well as several pathogenic bacterial strains.     

Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony dicarboxylates

Tris(5-bromo-2-methoxyphenyl)antimony bis(4-nitrophenylacetate) (I), tris(5-bromo-2-methoxyphenyl)antimony bis(2-methoxybenzoate) (II), and tris(5-bromo-2-methoxyphenyl)antimony bis(phenylpropiolate) (III) have been synthesized via the reaction between tris(5-bromo-2-methoxyphenyl) antimony and 4-nitrophenylacetic acid, 2-methoxybenzoic acid, and phenylpropiolic acid, respectively, in the presence of hydrogen peroxide (molar ratio: 1: 2: 1). According to X-ray diffraction data, the antimony atom in molecules of complexes I–III has a distorted trigonal bipyramidal coordination. The OSbO axial angles and the CSbC bond angles in the equatorial plane are 173.27(15)°, 172.96(11)°, 172.99(10)°, and 115.5(2)°–123.3(2)°, 108.81(16)°–129.32(17)°, and 110.66(17)°–127.91(17)°, respectively. The Sb-O bond lengths are 2.092(4) and 2.115(4)Å in I, 2.088(3) and 2.097(2) Å in II, and 2.096(3) and 2.120(3) Å in III. The Sb-C bonds range within 2.095(6)–2.123(6) Å in I, 2.107(4)–2.117(4) Å in II, and 2.097(4)–2.116(4) Å in III. Complexes I, II, and III are observed to have intramolecular Sb…OCH₃ contacts (3.169–3.226, 3.134–3.174, and 3.147–3.196 Å, respectively) in addition to Sb…O=C interactions (3.121, 3.139Å; 2.944, 3.038 A0; 3.111, 3.120 Å).     

Structures of triphenylbismuth dicarboxylates

Tripheylbismuth bis(trichloroacetate) (I), triphenylbismuth bis(chloroacetate) (II), and triphenylbismuth bis(bromoacetate) (III) were synthesized by the reaction of triphenylbismuth with carboxylic acid. The Bi atoms of the synthesized compounds have a distorted trigonal-bipyramidal coordination with phenyl ligands in equatorial positions. The Bi-C bond lengths lie within intervals 2.194(2)–2.201(2), 2.193(8)–2.223(7), 2.191(4)–2.220(3) Å, the distances Bi-O and Bi···O(=C) are equal 2.308(2), 2.315(2), and 2.896(2), 2.931(2); 2.289(6), 2.302(6), and 2.891(6), 2.910(6); 2.295(3), 2.312(3), and 2.893(3), 2.920(3) Å in I, II, and III, respectively. Molecules of triphenylbismuth dicarboxylates show linear dependence between the maximum equatorial angle CBiC (on the side of a contact) and intramolecular distance Bi···O(=C).     

Synthesis of dimethyl heterocyclic‐o‐dicarboxylates using dimethyl acetylenedicarboxylate

Dimethyl acetylenedicarboxylate (DMAD) is a very important and useful reagent for the preparation of dimethyl heterocyclic‐o‐dicarboxylates, which are key intermediates in the synthesis of fused pyridazine derivatives. The synthesis of thiopyranes by the Diels‐Alder reaction of dithiocarboxylate derivatives, synthesis of various cyclazines by [2 + 8] cycloaddition reactions, and synthesis of dimethyl pyrazolo[3,4‐b]pyridine‐5,6‐dicarboxylates and polycyclic heterocycles containing the 1,6‐naphthyridine ring system by the reaction of o‐aminonitrile compounds with DMAD are described here.     

Synthesis and thermal conversions of unsaturated nickel(II) dicarboxylates as precursors of metallopolymer nanocomposites

Nickel(II) dicarboxylates of unsaturated carboxylic acids (maleic (MalA), itaconic (ItA), acetylenedicarboxylic (ADCA), allylmalonic (AlMalA), glutaconic (GlutA), cis,cis-muconic (MucA) acids) were synthesized and characterized by thermal analysis and IR spectroscopy. The synthesized dicarboxylates were subjected to thermolysis, and the obtained nanocomposites were studied by transmission and scanning electron microscopy and X-ray diffraction. The synthesized metallopolymer nanocomposites were NiO and metallic Ni nanoparticles distributed over a stabilizing matrix. The formation enthalpy of dicarboxylates (ΔН_r^°) was calculated by the PM3 semi-empirical quantum-chemical method. The nanoparticle size was determined, and a relationship between the average nanoparticle diameter (d_avg) and ΔН_r^° was established. The microstructure and magnetic characteristics of the obtained nanocomposites, namely, the maximum and residual magnetization and the coercive force, were studied.     

Clathrate hydrates of tetrabutylammonium carboxylates and dicarboxylates

Phase diagrams of the binary aqueous systems with tetra-n-butylammonium (TBA) carboxylates ((C₄H₉)₄NC_nH_{2 n+1}CO₂, where n=0÷5) and dicarboxylates ([(C₄H₉)₄N]₂(CH₂)_nC₂O₄, where n=1÷3) including some branched carboxylate anions, have been studied in the field of crystallization of clathrate hydrates. Monocrystals of many hydrates have been prepared and their composition, densities, melting points and X-ray data have been determined. In the set of TBA carboxylate hydrates the stability increases towards TBA propionate or butyrate hydrates (for different structures) and then it decreases as sizes of anions grow, This is explained by additional stabilization of the framework caused by small cavities being occupied until the hydrophobic part of the anion is able to go in the cavity. In the set of hydrates of TBA dicarboxylates the change of the stability is easily accounted for by the modelling of the inclusion of dicarboxylate ions in the cavities, within known structures, different ways of hydrophilic inclusion being taken into account.     

Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

Palladium-catalyzed carbonylative cross-coupling reaction of triarylantimony dicarboxylates with arylboronic acids: Synthesis of biaryl ketones

A novel palladium-catalyzed three-component carbonylative coupling reaction by use of triarylantimony diacetate, arylboronic acid and carbon monoxide (1 atm) could be attained under mild reaction conditions without any base as an additive. The reaction can be applied to a wide range of triarylantimony diacetates and boronic acids to afford the corresponding unsymmetrical biaryl ketones in good yields.     

Anthracene-based ureidopyridyl fluororeceptor for dicarboxylates

Anthracene-labelled ureidopyridyl sensor 1 was designed and synthesized. The emission of the sensor increased in presence of dicarboxylates. The binding properties were studied using ¹H NMR, fluorescence and UV-vis spectroscopic methods. The sensor 1 shows modest selectivity for 1,4-phenylenediacetate.     

Block copolymerization. VII. Kinetic studies on the polymerization of pivalolactone with polystyrene dicarboxylates and polyacrylonitrile dicarboxylates

The rate of anionic polymerization of pivalolactone with polystyrene dicarboxylates decreased with conversion, suggesting deactivation of the propagating chain end by precipitation of the polymer during polymerization. The presence of unreacted initiator was explained by slow initiation for formation of a living polymer of pivalolactone. Various factors affecting block efficiency were discussed, and high efficiency was obtained for the preparation of block copolymers containing a long pivalolactone segment by using more nucleophilic polystyrene dicarboxylates. Block copolymer of acrylonitrile and pivalolactone was prepared from polyacrylonitrile dicarboxylates.     

Metallacycles of cadmium, mercury dicarboxylates

A series of linear coordination polymers, metallacycles of cadmium(II) and mercury(II) of flexible carboxylic acid ligands, RCH{3-CH(3)-,5-CH(3)-,6-(-OCH(2)CO(2)H)C(6)H(2)}(2), (when R = C(6)H(5), (H(2)L(1)); 2-NO(2)C(6)H(4)- (H(2)L(2)) and 3-NO(2)C(6)H(4)- (H(2)L(3))) are synthesized and characterized. [CdL(1) (py)(3)](n)·3nH(2)O (py = pyridine) is a linear coordination polymer, whereas [CdL(2)(py)(CH(3)OH)](2)·CH(3)OH is a dinuclear complex of cadmium with a Cd(2)O(2) type of core. The latter is obtained from reaction of cadmium(II) acetate with H(2)L(2) in methanol followed by reaction with pyridine. A similar reaction of cadmium(II) acetate with H(2)L(2) in dimethylformamide results in the formation of a cadmium metallacycle, namely [CdL(2) (py)(2)(H(2)O)](2)·H(2)O. The H(2)L(3) reacted with cadmium(II) acetate in the presence of pyridine to form a metallacycle [CdL(3)(py)(2)(H(2)O)](2)·3H(2)O. The ligand H(2)L(2) form mercury(II) metallacycle [HgL(2)(4-mepy)(2)](2) in the presence of 4-methylpyridine (4-mepy) and the ligand H(2)L(3) forms metallacycle [HgL(3)(3-mepy)(2)](2)·DMF in the presence of 3-methylpyridine (3-mepy). The potassium salts of H(2)L(1) and H(2)L(2) were found to be coordination polymers and these potassium coordination polymers were structurally characterized.