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131.
Braulio Insuasty Jairo Quiroga Juan Carlos Argoti Samuel Gmez Roberto Martínez Enrique Angeles Rubn Gabio Manuel Nogueras Adolfo Snchez 《Journal of heterocyclic chemistry》1998,35(6):1397-1399
The reaction of 1-aryl-3-(dimethylamino)-1-propanones 1 with one equivalent of 4,5-diamino-1H-pyrimidin-6-ones 2 , in acidic medium, leads to the formation of 4-aryl-2,3,6,7-tetrahydro-1H-pyrimido[4,5-b]-[1,4]diazepin-6-ones 3 . The structure elucidation of the products is based on detail nmr analysis of experiments such as 13C, 1H and DEPT including selective 13C{1H} decoupling experiments. 相似文献
132.
Ernesto Carmona Jose M. Marin Manuel L. Poveda Robin D. Rogers Jerry L. Atwood 《Journal of organometallic chemistry》1982,238(4):C63-C66
The reduction of [WCl4(PMe3)3] with dispersed sodium, under dinitrogen, gives cis-[W(N2)2(PMe3)4], while under ethylene trans-[W(C2H4)2(PMe3)4] is obtained. The ethylene complex can also be prepared by displacement of the dinitrogen molecules in cis-[W(N2)2(PMe3)4] by ethylene at room temperature and pressure. Interaction of cis-[M(N2)2(PMe3)4] complexes (M = Mo, W), with PMe3, under helium or argon, yields [M(N2)(PMe3)5]. The molybdenum complex crystallizes in the orthorhombic space group Pnma, with a 22.063(6), b 12.106(4), c 9.745(4) Å. The Mo—P distance trans to the dinitrogen ligand (2.483(7) Å) is slightly longer than the average of the other four Mo—P bonds (2.460(5) Å). 相似文献
133.
Reactions of 6-amino-3,4-dihydro-2-methoxy-4-oxopyrimidine 1 and its 3-methyl derivative 2 , with diethyl ethoxymethylenemalonate (EMME) are discussed in this paper. These reactions have been carried out in the following media: under fusion, ethanol, sodium methoxide/methanol, sodium ethoxide:ethanol and acetic acid media. In acetic medium, mixtures of products proceeding from C-alkylation and N-alkylation were obtained, while in the remaining conditions only products of N-alkylation were obtained. 相似文献
134.
Manuel Cano Beatriz Palenzuela J. Luis Ávila Rafael Rodríguez‐Amaro 《Electroanalysis》2007,19(9):973-977
A PVC/TTF‐TCNQ composite electrode has been employed as detector in a flow injection system. The proposed method allows the simultaneous detection of ascorbic acid (AA) and uric acid (UA) in mixtures by using a FIA system in a simple manner, without pre‐treatment or modified electrode. This method is based on the amperometric determination of (a) ascorbic acid at 0.15 V and (b) both analytes at 0.35 V, being the response linear in the range 1×10?2–4×10?4 M for both analytes with detection limits (S/N=3) of 1.2×10?4 M and 8.1×10?5 M for AA and UA, respectively. 相似文献
135.
Jenny?ZevallosEmail author Alejandro?Toro-Labbé Otilia?Mó Manuel?Yá?ez 《Structural chemistry》2005,16(3):295-303
High level ab initio and density functional theory calculations have been carried out to investigate the relative stability of the different conformers of hyponitrous acid and its mono- and dithio-derivatives. Geometries and vibrational frequencies were obtained at the B3LYP/6-311+G(d,p) level and final energies through B3LYP/6-311++G(3df,2pd) single point calculations. The reliability of this theoretical scheme has been assessed by comparing these DFT results with those obtained at the G3 level of theory, for some suitable cases. The cis conformers of hyponitrous acid and its mono- and dithio-derivatives are systematically more stable than the
trans ones because in the cis conformation a dative interaction between the nitrogen-lone pairs and the σNX^* antibonding orbital is significantly favored. Quite interestingly, in general, the conformers presenting an intramolecular hydrogen bond (IHB) are not the global minima of the corresponding potential energy surfaces and only for hyponitrous acid the conformer with a OH ⋅s O IHB is slightly more stable than the cis conformer without IHB. The low stability of the tautomers with IHB is closely related with another weak intramolecular interaction which involves the lone-pairs of the chalcogen atoms and the πNN* antibondig orbital, and which is significantly perturbed when the IHB is formed. 相似文献
136.
Carabias-Martínez R Rodríguez-Gonzalo E Domínguez-Alvarez J García Pinto C Hernández-Méndez J 《Journal of chromatography. A》2003,1005(1-2):23-34
A preconcentration study based on the cloud point phenomenon was carried out for a set of triazine herbicides, three of them chloro-substituted and three of them methylthio-substituted. Concentration factors and recoveries were calculated as function of the percentage of the non-ionic surfactant Triton X-114 employed. From these values, obtained from a cloud point extraction (CPE) procedure, the distribution coefficient between the Triton X-114 micelles and water, Kc, prior to CPE was calculated for each triazine and related to the corresponding octanol-water partition coefficient, Kow. In order to confirm the results obtained with the triazine herbicides, two sets of data from chemically different organic pollutants--organophosporous and chlorophenols--obtained from the literature were assessed, concluding that they display a similar behaviour to that of the triazine herbicides. This can be used to predict the CPE behaviour of other organic pollutants from their octanol-water partition coefficients. The Kc values were compared with the analyte concentration ratio in the surfactant-rich phase and aqueous phase (Ksa) with a view to obtaining a link between the analyte behaviour prior to and after cloud point extraction procedures. 相似文献
137.
138.
139.
A very sensitive flow system for the direct determination of copper in natural waters based on spectrophotometric detection 总被引:1,自引:0,他引:1
A very sensitive flow injection method with spectrophotometric detection has been developed for the on-line determination of copper in natural waters. The method exhibits a limit of detection three times lower than the most sensitive direct spectrophotometric method previously described and then allows the direct and simple in situ determination of copper in most natural waters.The method was based on the measurement of the absorbance of the coloured complex formed by copper with the chromogenic reagent di-2-pyridyl ketone benzoylhydrazone (dPKBH) in an alkaline medium. This complex presents stoichiometry 1:2 (Cu:dPKBH), and exhibits maximum absorbance at 370 nm. The manifold used was very simple, and consisted of two channels. The first one contained the sample while the second one contained the colorimetric reagent (3.3×10−4 M dPKBH in 10% ethanol), in a 1.6×10−2 M phosphate buffer solution at pH 8. The performance of the system was optimised by using both univariate and modified simplex methodologies. When modified simplex was used, the best signal was obtained for a sample injection volume of 529 μl, a reaction coil length of 1.29 m, and a reagent flow rate of 4.8 ml min−1. Under optimum conditions, the response was linear up to 3 mg l−1 copper, the equation of the straight line being y=0.314x+5.2×10−4 (r2=0.998). The method allowed a sampling frequency of 40 samples per hour and exhibited a precision of 2.11% (as R.S.D., n=11). The limit of detection was 4.6 μg l−1 (calculated as 3sb/m, where sb is the standard deviation of the y-intercept and m represents the slope of the straight line), and was therefore more sensitive than all the direct continuous methods reported previously.The method was successfully applied to the analysis of real water samples, with an average relative error of 5.32%. 相似文献
140.
Abstract The retinal Schiff base of bacteriorhodopsin, in the purple membrane from Halobacterium halobium , can be cleaved by hydroxylamine in the presence of light. We have further investigated this reaction with a series of O -substituted hydroxylamines, RONH2 , where R = -H (HA), -CH3 (MHA), -SO3 − (HAS), benzyl- (BHA), p -nitrobenzyl- (NBHA), and pentafluorobenzyl- (FBHA). All except MHA caused light-induced bleaching of the purple membrane and the chromophore could be regenerated from apomembrane and all- trans retinal. Relative bleaching rate constants were obtained from V = QI a k 0 X /( k r + k 0 X ), where V = bleaching rate, Q = quantum yield, I a = absorbed light intensity, X = hydroxylamine concentration, k 0 = rate constant for bleaching and k r = rate constant for return of photoexcited bacteriorhodopsin to the initial state. This equation fits the time-, concentration- and intensity-dependences of the bleaching reactions in 0.02 M phosphate, pH 7.0. The rate constants k 0 relative to HA were: MHA: 0; HAS: 0.3; HA: 1.0; BHA: 1.8; FBHA: 10.1; NBHA: 10.8. The relative rate constants do not correlate with the basicity of the derivatives. Instead, the results suggest that the retinal Schiff base is near a non-polar cavity into which an aromatic group can be inserted. 相似文献