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51.
A new strategy for the synthesis of some aporphinoid alkaloids is described. It is based on the intermolecular Diels-Alder cyclization between benzyne and an appropriate methylene isoquinoline derivative. 相似文献
52.
Prof. Dr. Enrique J. Baran 《Monatshefte für Chemie / Chemical Monthly》1975,106(1):121-126
Mean amplitudes of vibration of a series of tetrahedralXY 4 molecules and ions (hydrides, halides, oxides and oxoanions) have been calculated using the “Method of the Characteristic Vibrations” ofA. Müller. The results indicate that this method leads to very good values for most of the investigated species, and especially in the cases of highM X/MY mass ratio. 相似文献
53.
Chadim M Díaz P García-España E Hodacová J Latorre J Liu-González M Luis SV Llinares JM Závada J 《Inorganic chemistry》2005,44(21):7503-7510
Three crystal structures of a ditopic cyclophane ligand (L) in which two 1,5,8,12-tetraamine molecules have been attached through methylene spacers to the ortho positions of a benzene ring are reported. The first one (1) corresponds to the tetraprotonated free macrocycle (H4L4+) having two tetrachlorozincate(II) counteranions (C24H54O2N8Cl8Zn2, a = 9.1890(2) A, b = 14.0120(3) A, c = 15.3180(3) A, alpha = 89.2320(7) degrees , beta = 82.0740(6) degrees , gamma = 83.017(1) degrees , Z = 2.00, triclinic, P); the second one (2) is of a binuclear Cu2+ complex having coordinated chloride anions and perchlorate counteranions (C24H58O14N8Cl4Cu2 a = 9.9380(2) A, b = 30.2470(6) A, c = 53.143(1) A, orthorhombic, F2dd, Z = 18), and the third one (3) corresponds to an analogous Zn2+ complex that has been crystallized using triflate as counteranion (C26H(51.2)O(6.6)N8Cl2F6S2Zn2 a = 8.472(5) A, b = 9.310(5), c = 13.745(5) A, alpha = 84.262(5) degrees , beta = 77.490(5) degrees , gamma = 73.557(5) degrees , triclinic, P, Z = 2). The analysis of the crystallographic data clearly shows that the conformation of the macrocycle and, in consequence, the overall architecture of the crystals are controlled by the anions present in the moiety, pi-pi-stacking associations, and hydrogen bonding interactions. The protonation and stability constants for the formation of the Cu2+ and Zn2+ complexes in aqueous solution have been determined potentiometrically in 0.15 mol dm(-3) NaClO4 at 298.1 K. Intramolecular hydrogen bonding defines the protonation behavior of the compound. Positive cooperativity is observed in the formation of the Cu2+ complexes. 相似文献
54.
Manuel Snchez‐Chaves Gerardo Martínez Enrique Lpez Madruga Carmen Fernndez‐Monreal 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1192-1199
Free‐radical copolymerization of glycidyl methacrylate (GMA) with N‐vinylpyrrolidone (VPD) was carried out at 50 °C using 3.0 mol · L?1 of N,N′‐dimethylformamide solution and 9.0 · 10?3 mol · L?1 of 2,2′‐azobisisobutyronitrile as an initiator. The modification reaction of GMA‐VPD copolymers with a model bioactive carboxylic acid, 6‐methoxy‐α‐methyl‐2‐naphthaleneacetic acid (naproxen), was studied in the homogeneous phase using basic catalysts. The influence of the type of catalyst and the GMA content was evaluated. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1192–1199, 2002 相似文献
55.
Cabaleiro-Lago EM Rodríguez-Otero J García-López RM Peña-Gallego A Hermida-Ramón JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5966-5974
A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth. 相似文献
56.
Biener J Farfan-Arribas E Biener M Friend CM Madix RJ 《The Journal of chemical physics》2005,123(9):94705
The growth of titanium oxide nanoparticles on reconstructed Au(111) was investigated by scanning tunneling microscopy and x-ray photoelectron spectroscopy. Ti was deposited by physical-vapor deposition at 300 K. Regular arrays of titanium nanoparticles form by preferential nucleation of Ti at the elbow sites of the herringbone reconstruction. The titanium oxide nanoclusters were synthesized by subsequent exposure to O(2) at 300 K. Two-and three-dimensional titanium oxide nanocrystallites form during annealing in the temperature range from 600 to 900 K. At the same time, the Au(111) surface assumes a serrated 110-oriented step-edge morphology suggesting step-edge pinning by titanium oxide nanoparticles. The oxidation state of the titanium oxide nanoparticles varies with annealing temperature. Specifically, annealing to 900 K results in the formation of stoichiometric TiO(2) nanocrystals as judged by the Ti(2p) binding energies measured in the x-ray photoelectron data. The nanodispersed TiO(2) on Au(111) is an ideal system to test the various models proposed for the enhanced catalytic reactivity of supported Au nanoparticles. 相似文献
57.
BIOLOGICAL CHEMILUMINESCENCE 总被引:4,自引:0,他引:4
Abstract
The nucleobase 5-methylcytosine ( I ) is a minor component of eukaryotic DNA thought to be important in regulation of gene expression. The photochemical reactions of this nucleobase and its 2'-deoxyribonucleoside, 5-methyl-2'-deoxycytidine ( II ), in water have been studied. These reactions lead, respectively, to 3-amino-2-methylacrylamidine ( Ib ) and 3-(2- erythro - d -pentopyranos-1-yl) amino-2-methylacrylamidine ( IIb ) as the main photoproducts. The structure of the photoproducts was established by spectroscopic methods (1 H and 13 C NMR, UV spectroscopy, electron impact and liquid secondary ion mass spectrometry); in the case of Ib , confirmatory evidence was obtained by chemical methods (photolysis of 5-methyl[2–13 C]cytosine, hydrolysis of N -carbomethoxy-3-amino-2-methylacryl-amidine and reaction of Ib with 1,1'-carbonyldiimidazole to give I ). The quantum yield for formation of Ib was determined to be 1.8 × 10-3 at pH 7.5 while the quantum yield for formation of IIb has a lower value of 0.2 × 10-3 at pH 7.5. These quantum yields depend strongly on pH and reach maximum values of 2.0 × 10-3 at pH 7.0 ( Ib ) and 0.6 × 10-3 at pH 5.0 ( IIb ). The mechanism of formation of Ib (or IIb ) is proposed to involve nucleophilic attack of water on the C-2 position of photoexcited I (or II ), followed by ring opening and decarboxylation of an intermediate carbamic acid. 相似文献
The nucleobase 5-methylcytosine ( I ) is a minor component of eukaryotic DNA thought to be important in regulation of gene expression. The photochemical reactions of this nucleobase and its 2'-deoxyribonucleoside, 5-methyl-2'-deoxycytidine ( II ), in water have been studied. These reactions lead, respectively, to 3-amino-2-methylacrylamidine ( Ib ) and 3-(2- erythro - d -pentopyranos-1-yl) amino-2-methylacrylamidine ( IIb ) as the main photoproducts. The structure of the photoproducts was established by spectroscopic methods (
58.
The nature and properties of the low-lying singlet and triplet valence excited states of 2,2':5',2'-terthiophene (terthiophene) and 2,2':5',2':5',2'-quaterthiophene (tetrathiophene) are discussed on the basis of high-level ab initio computations. The spectroscopic features determined experimentally for short alpha-oligothiophenes are rationalised on theoretical grounds. Special attention is devoted to the nonradiative decay process through intersystem crossing (ISC) from the singlet to the triplet manifold, which is known to be relatively less efficient in tetrathiophene. Along the geometry relaxation of the S1 state of terthiophene, the S1 and T2 states become degenerate, which leads to a favourable situation for the occurrence of ISC. The parallel process is expected to be less favoured in tetrathiophene because of the less efficient spin-orbit coupling and the increase of the S1-T2 energy gap. 相似文献
59.
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
60.
The reactions of S-4-nitrophenyl 4-X-substituted thiobenzoates (X = H, Cl, and NO(2): 1, 2, and 3, respectively) with a series of secondary alicyclic amines (SAA) were subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0 degrees C and an ionic strength of 0.2 M (KCl). The reactions were followed spectrophotometrically by monitoring the release of 4-nitrobenzenethiolate anion at 420-425 nm. Under excess amine, pseudo-first-order rate constants (k(obsd)) are obtained for all reactions. The plots of k(obsd) vs [SAA] at constant pH are linear with the slope (k(N)) independent of pH. The statistically corrected Br?nsted-type plots (log k(N)/q vs pK(a) + log p/q) for the reactions of 1 and 2 are nonlinear with slopes at high pK(a), beta(1) = 0.27 and 0.10, respectively, and slopes at low pK(a), beta(2) = 0.86 and 0.84, respectively. The Br?nsted curvature is centered at pK(a) (pK(a)(0)) 10.0 and 10.4, respectively. The reactions of SAA with 3 exhibit a linear Br?nsted-type plot of slope 0.81. These results are consistent with a stepwise mechanism, through a zwitterionic tetrahedral intermediate (T(+/-)). For the reactions of 1 and 2, there is a change in rate-determining step with amine basicity, from T(+/-) breakdown to products at low pK(a), to T(+/-) formation at high pK(a). For the reactions of 3, breakdown to products of T(+/-) is rate limiting for all the SAA series (pK(a)(0) > 11). The increasing pK(a)(0) value as the substituent in the acyl group becomes more electron withdrawing is attributed to an increasing nucleofugality of SAA from T(+/-). The greater pK(a)(0) value for the reactions of SAA with 1, relative to that found in the pyridinolysis of 2,4-dinitrophenyl benzoate (pK(a)(0) = 9.5), is explained by the greater nucleofugality from T(+/-) of the former amines, compared to isobasic pyridines, and the greater leaving ability from T(+/-) of 2,4-dinitrophenoxide relative to 4-nitrobenzenethiolate. 相似文献