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941.
The reaction of 1,2-diamino-4,5-diphenylimidazole with 1,3-diarylpropenones and 1,3-diaryl-2,3-dibromopropenones gives dihydro- and heteroaromatic derivatives of 6-hydroxyimidazopyrimidines and also imidazopyrimidines which do not contain the 6-hydroxy group. It was found that the structure of the products depended on the conditions for carrying it the reaction. 相似文献
942.
Silica gel-loaded (E)-N-(1-thien-2'-ylethylidene)-1,2-phenylenediamine (TEPDA) phase was synthesized based on physical adsorption approaches. The stability of a chemically modified TEPDA especially in concentrated hydrochloric acid that was then used as a recycling and preconcentration reagent allowed the further uses of silica gel-loaded immobilized TEPDA phase. The application of this silica gel-loaded phase to sorption of a series of metal ions was performed by using different controlling factors such as the pH of the metal ion solution and the equilibration shaking time by the static technique. This difference was interpreted on the basis of selectivity incorporated in these sulfur containing silica gel-loaded TEPDA phases. Hg(Ⅱ) was found to exhibit the highest affinity towards extraction by these silica gel-loaded TEPDA phases. The pronounced selectivity was also confirmed by the determined distribution coefficients (Kd) of all the metal ions, showing the highest value reported for mercury(Ⅱ) extraction by the silica gel immobilized TEPDA phase. The potential applications of the silica gel immobilized TEPDA phase to selective extraction of mercury(Ⅱ) from aqueous solution were successfully accomplished and preconcentration of low concentration of Hg(Ⅱ) (30 pg·mL^-1) from natural tap water with a preconcentration factor of 200 for Hg(Ⅱ) off-line analysis was conducted by cold vapor atomic absorption analysis. 相似文献
943.
Polycyclic ‘cage’ ketones, such as pentacyclo[5.4.0.02,6.03,10.05,9]undecan‐8‐one ( 10 ), pentacyclo[5.4.0.02,6.03,10.05,9]undecane‐8,11‐dione ( 11 ), and adamantan‐2‐one ( 16 ) were treated with the nucleophilic dimethoxycarbene (DMC; 1 ), which was generated thermally from 2,5‐dihydro‐2,2‐dimethoxy‐5,5‐dimethyl‐1,3,4‐oxadiazole ( 4a ) in boiling toluene. In this ‘one‐pot’ procedure, the α‐hydroxycarboxylic acid ester 12 or a corresponding derivative 15 or 17 was obtained (Schemes 4–7). Additionally, ‘cage’ thione 21 was treated with DMC under the same conditions yielding dimethoxythiirane 22 (Scheme 8). Subsequent hydrolysis or desulfurization (followed by hydrolysis on silica gel) of 22 gave α‐mercaptocarboxylate 25 and the corresponding desulfurized ester 24 , respectively. In all cases, the addition of DMC occurred stereoselectively, and the addition from the exo‐face is postulated to explain the structures of the isolated products. 相似文献
944.
Wang‐Ting Wu Feng‐Ying Chen Shui‐Yang He Huai‐Ming Hu Meng‐Lin Yang Yao‐Yu Wang 《中国化学》2006,24(5):711-713
The binuclear praseodymium(III) complex with N‐(1‐carboxyethylidene)‐salicylhydrazide (C10H10N2O4, H2L) was prepared in H2O‐C2H5OH mixed solution, and the crystal structure of [Pr2L2(HL)2(H2O)4]·3H2O·C6H6 was determined by X‐ray single crystal diffraction. The crystal complex crystallizes in the triclinic system with space group P‐1, and in the structure each Pr atom is 9‐coordinated by carboxyl O and acyl O and azomethine N atoms of two tridentate ligands to form two stable five‐membered rings sharing one side in keto‐mode and two water molecules. The coordination polyhedron around Pr3+ was described as a monocapped square antiprism geometry. In an individual molecule, four tridentate ligands were coordinated by two negative univalent (HL) and two bivalent forms (L) respectively. Two negative univalent ligands were coordinated via μ2‐bridging mode. 相似文献
945.
Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme. 相似文献
946.
Eva Schneiderman Bruno Perly Elwood Brooks Apryll M. Stalcup 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(1-2):43-50
The characterization of binary and ternary complexes of benzoate, lauryl hexaoxyethylene (C12E6) and -CD is presented. The complexation equilibrium was characterized by UV-Vis spectrophotometry, titration microcalorimetry, capillary electrophoresis, and 2D ROESY 1H-NMR. Results suggested that -CD forms one complex with C12E6in the stoichiometric ratio of -CD : C12E61.5 : 1, with a stability constant 1.3 × 105 M-1.5. The 2-D ROESY 1H-NMR spectrum indicated that C12E6is included inside the -CD cavity. The primary binding site of C12E6 is on the lauryl subunit of this molecule. Analogous to a previously reported study of -CD, the combination of -CD and C12E6precipitated from the solution. Addition of benzoate seemed to dissolve the precipitate and nearly doubled the apparent stability constant of the complex. Results from the various techniques supported formation of ternary complexes between -CD, C12E6, and benzoate. 相似文献
947.
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step. 相似文献
948.
Tarun Ghosh 《Tetrahedron letters》2004,45(32):6169-6172
C-(4-Oxo-4H-1-benzopyran-3-yl)-N-alkyl-/aryl-nitrones derived from 4-oxo-4H-1-benzopyran-3-carboxaldehyde, rearrange to 2-alkyl-/aryl-amino-3-formylchromone and/or 3-(alkyl-/aryl-aminomethylene)chroman-2,4-dione depending upon the reaction medium. 3-(Alkylaminomethylene)chroman-2,4-dione has been utilized in the synthesis of 1-benzopyrano[3,4-d]isoxazole-4-one. 相似文献
949.
New organohalogermanes RGe(OCH2CH2NMe2)2X (R = Ph, X = I (5); R = Me, X = Cl (6) or I (7)) with an intramolecular N→Ge coordination bond were synthesized. According
to the 1H and 13C NMR spectroscopic data, iodides 5 and 7 exist in solution as ionic compounds with the pentacoordinated germanium atom. In
solution of compound 4 (R = Ph, X = Cl), there is an equilibrium between the ionic and covalent forms. The equilibrium shifts
toward the ionic form with increasing solvent polarity or temperature. In solution, chloride 6 is a covalent compound. The
structures and relative stabilities of different isomers of compounds 4–7 were studied by quantum chemical calculations at
the density functional level of theory.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 892–900, May, 2007. 相似文献
950.
E. Lukevics L. Ignatovich I. Sleiksha V. Romanov S. Grinberga J. Popelis I. Shestakova 《Chemistry of Heterocyclic Compounds》2007,43(2):143-150
A new method was developed for the synthesis of silicon-and germanium-containing acetylfurans and acetylthiophene by metallation
of 2-acetylfuran or 2-acetylthiophene with n-BuLi at low temperature after protection of the carbonyl group with lithium N-methylpiperazide
and reaction of the lithium derivative with various trialkyl-, alkylphenyl-, and cycloalkylchlorosilanes or trialkylchloro(bromo)germanes.
The cytotoxic activity of the new compounds was studied, and it was established that the silicon-and germanium-containing
acetylfurans and acetylthiophenes are substances with low toxicity (LD50 312->2000 mg/kg) and have low cytotoxicity toward HT-1080 and MG-22A tumor cells.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 192–199, February, 2007. 相似文献