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Abdolhassen Talebian Alem Ghiorghis Charles F. Hammer Evelyn A. Murril Frank Pallas 《Journal of heterocyclic chemistry》1992,29(4):979-984
The syntheses and spectroscopic properties (ir, 1H nmr, 13C nmr, uv and ms) of pure samples of 2-chloro-4,6-bis(dimethylamino)-s-triazine 1 , 4,6-dichloro-2-dimethylamino-s-triazine 2 , 4,6-bis(dimethylamino)-s-triazin-2(lH)-one 3 , 4-chloro-6-dimethylamino-s-triazin-2(1H)-one 4 , 6-dimethylamino-s-triazine-2,4(1H,3H)-dione 5 , and 2,4,6-tris(dimethylamino)-s-triazine (altretamine, HMM) are reported. Evidence for enol-keto equilibria are also presented for 3 , in which the enol form exhibits as an H-bonded dimer structure similar to the dimer of organic carboxylic acids. 相似文献
3.
In order to analyse metal complexation with polyfunctional phenolic compounds as ligand models of natural substances, a detailed examination is described for five simple binary complexes and three ternary mixed ligand complexes at 25°C (μ = 0.1 M NaClO4). The ligands are tyrosine, 4,5-dihydroxy-1,3-benzene disulfonic acid, disodium salt (tiron), 3,4-dihydroxycinnamic acid (caffeic acid), 3,4,5-trihydroxy-1 -cyclohexene-1 -carboxylic acid (shikimic acid) and 1,3,4,5-tetrahydroxycyclohexanecarboxylic acid 3-(3,4-dihydroxycinnamate) (chlorogenic acid). The ternary systems are Cu(II)/HqA/tiron, where HqA is tyrosine, caffeic or chlorogenic acids. Potentiometric data were used successively to evaluate the protonation of each individual ligand, to detect simple and mixed complexes (including protonated species) and to determine their stability constants (a set of 33 values of constants with several original data is provided). The calculated distribution (speciation) of each species as a function of pH is indicated. Mixed coordination enhances the stability of complexes and the stabilization is expressed in terms of various parameters. The results emphasize that mixed ligand complex formation is essential to studies of multiple equilibria. 相似文献
4.
Potentiometric measurements were used to characterize the complexing properties of (a) a mixture of five monomeric ligands, (b) a synthetic humic-like substance and (c) fulvic acids extracted from soils, with copper (II). In order to compare the binding strengths involved, the same mathematical treatments of the data were used for all measurements. Calculations of the total ligand concentration with the Gran function give underestimated values for the multiligand mixture because of the known presence in the mixture of functional groups with pKH ; 11 which > cannot be titrated and are revealed only by complexation phenomena. The acid-base properties of the humic substances are better described with a continuous model than with the descrete Henderson-Hasselbach model, because of the inability to distinguish properly between equivalent and independent types of functional groups. In the presence of copper (II), the formation functions show that a mixture of different kinds of complexes with different stability constants is probably formed. Extra protons released during the titration of the various copper (II) systems with alkali are attributed to untitrated functional groups with extremely low protonation constants in the case of the multiligand mixture, but ambiguity remains with the humic substances because their chemical structure is not known. Comparison of binding strengths can be made in terms of global conditional stability constants, by taking into account the three parameters, pH, concentrations of metal and of ligand. It is shown that the mechanisms of complexation are different for monomers and for polymers. 相似文献
5.
Takaaki Horaguchi Takako Oyanagi Evelyn Cuevas Creencia Kiyoshi Tanemura Tsuneo Suzuki 《Journal of heterocyclic chemistry》2004,41(1):1-6
A variety of nitrogen‐containing heterocycles were synthesized by passing vapors of aromatic amines over calcium oxide at 450–650 °C under nitrogen carrier gas. Reaction of 2‐aminobiphenyl 3a at 560 °C gave carbazole 4 in 80% yield. Reaction of 2, 2′‐diaminobiphenyl 3b afforded a mixture of carbazole 4 and 4‐aminocarbozole 6b. In the case of 2‐amino‐2′‐nitrobiphenyl 3c, benzo[c]cinnoline 7 was obtained along with carbazole 4. Reaction of 2‐amino‐2′‐methoxybiphenyl 3d gave four products of carbazole 4,4‐hydroxycarbazole 6e, phenanthridine 8 and dibenzofuran 9. Reaction of 2‐aminodiphenylmethane 5a afforded acridine 10. In the case of 2‐aminobenzophenone 5b, acridone 11 was obtained as a major product. Reaction of 2‐aminobenzhydrol 5c gave acridine 10. When 2‐aminodiphenylamine 5d was reacted, phenazine 12 was obtained in good yield. In contrast, reaction of 2‐aminodiphenyl ether 5e produced only 2‐hydroxydiphenylamine 13. Reaction of 4‐aminophenanthrene 14 produced 4H‐benzo[def]carbazole 15 in 61% yield. 相似文献
6.
The electrochemical behaviour of iron phthalocyanine (FeIIPc) films, supported on gold substrates, was studied in 3.5 M NaOH solution, using cyclic voltammetry and coupled “in situ” ESR and UV-visible spectroscopic techniques. Two types of electron transfer were observed in the potential range from −0.45 to −1.0 V vs. Hg/HgO. According to the “in situ” spectroscopy investigations, these two processes were assigned respectively to electron transfers involving first the ligand ring, and then the centre iron ion. 相似文献
7.
8.
Mann DL Ware GM Bonnin E Eitenmiller RR Barna E Christiansen S De Borde JL DeVries J Gilliland P Hemmer J Kalman A Konings E Levin D Salvati L Woollard D 《Journal of AOAC International》2005,88(1):30-37
A liquid chromatographic (LC) method was validated for the determination of total vitamin B6 in infant formula. Total vitamin B6 was quantified by converting the phosphorylated and free vitamers into pyridoxine. Pyridoxine was determined by ion pair reversed-phase LC with fluorescence detection. The method was subjected to an AOAC collaborative study involving a factory-manufactured, milk- and soy-based infant formula. Each was spiked at 3 concentrations in the range of 0-1 microg/g and sent as blind duplicate to participant laboratories. Nine laboratories returned valid data which were statistically analyzed for outliers and precision parameters. The repeatability relative standard deviation (RSD(r)) ranges were 2.0-4.0 and 3.5-5.9% for fortified milk- and soy-based formulas, respectively. The reproducibility relative standard deviation (RSD(R)) ranges were 8.2-8.4 and 6.7-11.2% for fortified milk- and soy-based formulas, respectively. HORRAT values ranged from 0.42 to 0.53, indicating that the precision of the method is acceptable. The mean RSD(r):RSD(R) values were 0.60 and 0.55 for milk- and soy-based formulas, respectively. As expected, RSDs for the unfortified samples were higher, but their HORRAT values (0.81 and 2.06) helped define a realistic limit of quantitation as 0.05 microg/g. Recovery data were quantitative and varied between 81.4 and 98.0% (mean = 89.8%) for each of 6 spiked materials. 相似文献
9.
Wendt-Pienkowski E Huang Y Zhang J Li B Jiang H Kwon H Hutchinson CR Shen B 《Journal of the American Chemical Society》2005,127(47):16442-16452
Fredericamycin (FDM) A, a pentadecaketide featuring two sets of peri-hydroxy tricyclic aromatic moieties connected through a unique chiral spiro carbon center, exhibits potent cytotoxicity and has been studied as a new type of anticancer drug lead because of its novel molecular architecture. The fdm gene cluster was localized to 33-kb DNA segment of Streptomyces griseus ATCC 49344, and its involvement in FDM A biosynthesis was proven by gene inactivation, complementation, and heterologous expression experiments. The fdm cluster consists of 28 open reading frames (ORFs), encoding a type II polyketide synthase (PKS) and tailoring enzymes as well as several regulatory and resistance proteins. The FDM PKS features a KSalpha subunit with heretofore unseen tandem cysteines at its active site, a KSbeta subunit that is distinct phylogenetically from KSbeta of hexa-, octa-, or decaketide PKSs, and a dedicated phosphopantetheinyl transferase. Further study of the FDM PKS could provide new insight into how a type II PKS controls chain length in aromatic polyketide biosynthesis. The availability of the fdm genes, in vivo characterization of the fdm cluster in S. griseus, and heterologous expression of the fdm cluster in Streptomyces albus set the stage to investigate FDM A biosynthesis and engineer the FDM biosynthetic machinery for the production of novel FDM A analogues. 相似文献
10.