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1.
Nikolay Tyutyulkov Fritz Dietz Jürgen Fabian Achim Melhorn Alia Tadjer 《Theoretical chemistry accounts》1981,60(2):185-200
The analysis of the experimental data for the energy of the longest wavelength optical transitions
n,opt of substituted polymethines X
(CH)2n+1
X shows that in the asymptotic case (n) ,opt does not tend to zero, as it follows from the empirically established correlations, but has a finite, non-zero value. It is shown that the energy gap of odd polymethines is the same as that of the even polymethines - the polyenes (E
2 eV). The substituents (X N, O, B) are responsible for the appearance of levels in the gap. These, depending on the substituent character, are vacant (X B) or occupied (X N, O). The transition from or to such a level determines the longest wavelength optical transition energy of polymethines. 相似文献
2.
A. A. El-Barbary A. I. Khodair E. B. Pedersen C. Nielsen 《Monatshefte für Chemie / Chemical Monthly》1994,125(8-9):1017-1025
Summary Methyl 3-benzoylthio-5-O-tert-butyldiphenylsilyl-2,3-dideoxy--D-erythro-pentofuranoside (4) and its corresponding anomer5 were synthesized in four steps from 2-deoxy-D-ribose and used as substrates for the synthesis of nucleosides by condensation with silylated thymidine and N6-isobutyryladenine. The nucleosides were deprotected by treatment with Bu4NF inTHF followed by reaction with MeONa in MeOH to give 3-deoxy-3-mercaptothymidine (8), 2,3-dideoxy-3-mercaptoadenosine (15) and its corresponding anomer16. In the latter reactions it was important to use degassed solvents to minimize formation of the corresponding disulfides of purine nucleosides. Using Bu4NF, without subsequent reaction with MeONa in the deprotection reaction, resulted in intermolecular transesterification reactions.On leave from Chemistry Department, Faculties of Science and Education, Tanta University, Tanta, Egypt 相似文献
3.
Giorgio Tosi Pierluigi Stipa Gabriele Bocelli 《Monatshefte für Chemie / Chemical Monthly》1988,119(4):487-494
The Dinitrone 2,2-diphenyl-3,3-bi-3H-indole-1,1-dioxide acts as a demethylating and dehydrogenating agent. The mechanism of interaction of the dinitrone with donors and acceptors does not involve intermediate charge-transfer complexes probably due to a self association between dinitrone molecules (as supported by X-ray determinations). The crystal structure of the dinitrone was obtained by direct methods;a=9.967 (2),b=19.817 (3),c=10.875 (2) Å, =111.2 (2)°, space group P21/n. The finalR andR
w
were 0.089 and 0.063 for all measured reflexes.
2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid: Molekulare Wechselwirkungen und Kristallstruktur
Zusammenfassung Das Dinitron 2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid wirkt als Demethylierungs- und Oxydationsmittel. Die Wechselwirkung des Dinitrons mit Elektronen-Acceptoren und Elektronen-Donatoren geht wegen der Selbstassoziation zwischen den Dinitron-Molekülen ohne die dazwischenliegende Bildung eines Charge-Transfer-Komplexes vor sich; das wird auch von Röntgenstrukturuntersuchungen gestützt. Die Kristallstruktur wurde mit direkten Methoden ermittelt:a=9.967 (2),b=19.817 (3),c=10.875 (2) Å; =111.2 (2)°. P21/n. Die endgültigen WerteR undR w waren 0.089 und 0.063 für alle gemessenen Reflexe.相似文献
4.
3-Chloro-5,7-dibromo-6-ketosteroids 5a and 5b are synthesized from -sitosterol (1a) and cholesterol (1b). Dehydrohalogenation of these forms 7-bromo-2,4-dien-6-ones (6a-b), 2,4-dien-6-ones (7a-b), and 14-hydroperoxy-2,4,7-trien-6-ones (8a-b). Woodward hydroxylation of dienone 6a produces 2-iodo-7-bromo-3-acetoxy-4-6-ketone 9 and 7-bromo-2,3-diacetoxy-4-6-ketone 10. 2-Iodo-3-acetoxy-4,7,14-trien-6-one 11 is prepared analogously from trienone 8a. 相似文献
5.
Self-consistent-field and configuration-interaction studies were performed on borazine, using a double-zeta basis set augmented by six diffuse -functions. Low-lying singlet and triplet states of the A
1
, A
2
and E species were calculated, corresponding to * excited valence and Rydberg states. A selection out of singly and doubly excited configurations relative to a set of reference configurations was made for each species. Calculated vertical excitation energies (in eV) are 7.12 for 1
A
2(V), 8.45 for 1
E (3p-R), 8.57 for 1
A
1(V), 8.9 for 1
E(V-R), 9.55 for 1
E(3d-R), 6.98 for 3
A
1(V), 7.27 for 3
E(V), 7.82 for 3
A
2(V), 8.30 for 3
E(3p-R), and 9.5 for 3
E(3d-R), where V and R refer to valence or Rydberg character. The results are compared with experimental excitation energies, previous ab initio studies of borazine, and with recent ab initio studies of benzene.Dedicated to Professor Dr. H. Hartmann on the occasion of his 65th birthday. 相似文献
6.
Paolo Bruni Carla Conti Giorgio Tosi 《Monatshefte für Chemie / Chemical Monthly》1988,119(11):1311-1316
Competitive demethylation and redox reactions induced by 2,2-diphenyl-3,3-bi-3H-indole-1,1-dioxide,1 (dinitrone) on several nitrogen bearing compounds (pyridines, amides, indoles, hydrazones and amines) are reported.Es wird über kompetitive Demethylierungen und Redoxreaktionen an stickstoffhaltigen Verbindungen (Pyridine, Amide, Indole, Hydrazone und Amine) berichtet, die durch das Dinitron 2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid induziert werden.
2,2-Diphenyl-3,3t-bi-3H-indol-1,1t-dioxid: Kompetitive Demethylierung und Redoxreaktionen相似文献
7.
Abdel Moneim El-Torgoman Mohammed S. Motawia Ulla Kjærsgaard Erik B. Pedersen 《Monatshefte für Chemie / Chemical Monthly》1992,123(4):355-361
Summary Reaction of 3-azido-5-O-tert-butyldiphenylsilyl-2,3-dideoxy-D-erythro-pentofuranoside (5) with silylated 2-thiouracil and 5-alkoxy-2-thiouracils in the presence of trimethylsilyl trifluoromethanesulfonate afforded an anomeric mixture of the corresponding 3-azido-2,3-dideoxy-2-thiouridine derivatives with the -anomer as the main product. Deprotected nucleosides were obtained by treatment with tetrabutylammonium fluoride.
Ein neuer Weg zur Synthese von 2-Thiouracil-Analogen von 3-Azido-2,3-dideoxy-Nucleosiden
Zusammenfassung Die Reaktion von 3-Azido-5-O-tert-butyldiphenylsilyl-2,3-dideoxy-D-erythro-pentofuranosid (5) mit silyliertem 2-Thiouracil und 5-Alkoxy-2-thiouracil in Gegenwart von Trimethylsilyltrifluormethansulfonat ergab eine anomere Mischung der entsprechenden 3-Azido-2,3-dideoxy-2-thiouridin-Derivate, wobei das -Anomer das Hauptprodukt darstellte. Die ungeschützten Nucleoside wurden mittels Behandlung mit Tetrabutylammoniumfluorid erhalten.相似文献
8.
T. G. Edwards 《Theoretical chemistry accounts》1973,30(3):267-274
Assignments of the 1* electronic transitions in large carbonyl compounds have been carried out using the molecules-in-molecules method. 相似文献
9.
The — complexes of metal tetraphenylporphinates with benzene, toluene, and xylenes were characterized by means of thermogravimetry. The ability of metalloporphyrins to form — complexes with certain -donor molecules depends largely on the -acceptor capacity of the macroheterocycle, and on the peculiarities of the metal—porphyrin coordinative linkage. Stoichiometry, energy parameters, and thermal stability of the - complexes of metalloporphyrins with various aromatic ligands are determined to a great extent by the molecular structure of solvents.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp.850–853, May, 1993. 相似文献
10.
The formation and transformations of blue silver (
max 700 nm) during -irradiation of a weakly alkaline (pH 9) aqueous solution containing AgClO4, polyacrylic acid (PAA), and isopropanol were studied. We believe that blue silver is a linear silver cluster stabilized on a polymeric molecule. During radiation-chemical reduction the cluster is transformed into new clusters (
max = 365 and 460 nm). When all of the Ag+ ions present in the solution have been reduced, clusters coalesce and a new phase,i.e., colloidal silver particles, forms. The mechanism of the radiation-chemical transformations is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–37, January, 1995. 相似文献
11.
Thermodynamics of Binding of α:-Cyclodextrin to Straight-Chain Alkyl Derivatives in Aqueous Solution
Magnus Stödeman Isabel Gómez-Orellana Dan Hallén 《Journal of inclusion phenomena and macrocyclic chemistry》2003,46(3-4):125-132
Apparent standard Gibbs energy, enthalpy, entropy, and heatcapacity data of the interactions of -cyclodextrin (CD) to some n-carboxylatesH(CH2)nCOO- (n = 4–6), are determined by isothermal titration microcalorimetryat different temperatures in phosphate buffer, pH 9.0, assuming a 1 : 1 model indilute solution. Modelling of contributions of the thermodynamic properties of the solutionindicates that CD undergoes conformational change upon binding to homologousseries of n-carboxylates, n-alcohols, ,-alkane dicarboxylates and ,-alkane diols. 相似文献
12.
The condensation of aminals of -dimethylaminoacrolein and 5-dimethylaminopenta-2,4-dienal with cyclic and acyclic 1,2-, 1,3-, 1,4-, 1,5-, and 1,6-diketones was studied. A series of previously unknown bis(,-dimethylaminopolyenyl)diketones was synthesized; their structures were established by means of1H and13C NMR spectroscopies. The electron absorption spectra were employed to study the mutual influence of -aminopolyene chromophores separated by two C=O groups.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1235–1241, July, 1993. 相似文献
13.
A. Jaumà A. Escuer J.-A. Farrera J. M. Ribó 《Monatshefte für Chemie / Chemical Monthly》1996,127(10):1051-1062
Summary Several Mn, Cu, and Zn chelates of etiobiliverdin-IV-, mesobiliverdin-IX, and its dimethyl ester are studied. The results show that the chemical constitution of the Cu biliverdin chelate corresponds to a formal metal oxidation state of (II) coordinated to a neutral radical of the NH trideprotonated biliverdin. The reactivity of the Cu(II) bilindione chelates in nucleophilic solvents agrees with that expected for a neutral radical structure of the ligand; in CH3OH, they undergo oxidation towards dimethoxybilipurpurins. The magnetic behaviour of Cu(II) etiobiliverdinate-IV- in the solid state shows an intramolecular weak antiferromagnetic coupling d9Cu-to--radical (J=–23 cm–1) and an intermolecular weak antiferromagnetic coupling -radical-to--radical (J=–45 cm–1). The analogy of this magnetic behaviour to that of the cation radical of metalloporphyrins is discussed.
Reaktivität von Pyrrolpigmenten, 21. Mitt.: Struktur und Reaktivität von Cu(II)- und Zn(II)-Chelaten von Bilindionen
Zusammenfassung Einige Mn, Cu and Zn Chelate von Etiobiliverdin-IV-, Mesobiliverdin-IX und seinem Dimethylester werden untersucht. Im Komplex koordiniert ein Metallatom (mit der Formalladung II) mit einem Neutralradikal des dreifach NH-deprotonierten Bilindions. Die Reaktivität des Komplexes gegenüber nukleophilen Lösungmitteln entspricht erwartungsgemäß dem eines neutralen -Radikals; in CH3OH wird er zu Dimethoxybilipurpurin oxidiert. Bei Cu(II)-Etiobiliverdinat-IV beobachtet man im festen Zustand neben schwacher, antiferromagnetischer Kupplung zwischen d9Cu und -Radikal (J=–23 cm–1) auch eine schwache, intermolekulare, antiferromagnetische Wechselwirkung zwischen zwei -Radikalen (J=–45 cm–1). Dieses magnetische Verhalten wird dem des -Kationradikals von Metalloporphyrinen gegenübergestellt.相似文献
14.
Aki Hayashi Hirokazu Nakayama Mitsutomo Tsuhako Taro Eguchi Nobuo Nakamura 《Journal of inclusion phenomena and macrocyclic chemistry》1999,34(4):401-412
Intercalation of ,-alkanediamines, NH2(CH2)
n
NH2 (n = 3–10), into layered aluminium dihydrogen triphosphate dihydrate, AlH2(P3(O10... 2H2O, was investigated by XRD, DTA-TG, elemental analysis, and solid-state 31P, 13C and 27Al NMR. ,-Alkanediamines are intercalated to form a monomolecular layer in the interlayer region, in which the alkanediamines incline at 57 ± 5° to the phosphate layers, whereas n-alkylamines form a bilayer structure with the same inclination angle. Two amino groups in an ,-alkanediamine molecule bridge the layered sheets of phosphates. 相似文献
15.
H. M. Abdel-Bary A. A-H Abdel-Rahman E. B. Pedersen C. Nielsen 《Monatshefte für Chemie / Chemical Monthly》1995,126(6-7):811-817
Summary 2-O-Ethyluracil and 2-O-ethylthymine were silylated with 1,1,1,3,3,3-hexamethyldisilazane and condensed in the presence ofTMS triflate with 2,3-dideoxy-3-fluoro-D-erythro-pentofuranoside, 3-azido-2,3-dideoxy-D-erythro-pentofuranoside, and 2,3-dideoxy-3-phthalimido--D-erythro-pentofuranose derivatives to give the corresponding 2-O-ethyl nucleosides. Deprotection with saturated methanolic ammonia afforded the 2,3-dideoxy-3-fluoro-2-O-ethyluridines, whereas 3-azido-2,3-dideoxy-3-O-ethyluridine was obtained by deprotection with tetrabutylammonium fluoride in tetrahydrofuran. 3-Amino-2,3-dideoxy-3-O-ethyluridine could be obtained only by treatment of the corresponding 3-azido nucleoside with triphenylphosphine in pyridine. 3-Deoxy-2-O-ethyl-3-fluorothymidine (6b) showed moderate activity against HIV-1.
Synthese von 2-O-Ethyl-Analogen von 3-Azido- und 3-Fluor-23-dideoxyuridinen und Bestimmung ihrer biologischen Aktivität gegenüber HIV
Zusammenfassung 2-O-Ethyluracil und 2-O-Ethylthymin wurden mit 1,1,1,3,3,3-Hexamethyldisilazan silyliert und in Gegenwart vonTMS-triflat mit 2,3-Dideoxy-3-fluoro-D-erythro-pentofuranosid, 3-Azido-2,3-dideoxy-D-erythro-pentofuranosid und 2,3-Dideoxy-3-phthalimido--D-erythro-pentofuranosederivaten zu den entsprechenden 2-O-Ethyl-Nucleosiden umgesetzt. Entfernung der Schutzgruppe mit gesättigter methanolischer Ammoniaklösung lieferte 2,3-Dideoxy-3-fluor-2-O-ethyluridin; 3-Azido-2,3-dideoxy-3-O-ethyl-uridin wurde durch Entschützung mit Tetrabutylammoniumfluorid in Tetrahydrofuran erhalten. 3-Amino-2,3-dideoxy-3-O-ethyl-uridin konnte nur durch Behandeln des entsprechenden 3-Azido-Nucleosids mit Triphenylphosphin in Pyridin hergestellt werden. 3-Deoxy-2-O-ethyl-3-fluor-thymidin (6b) zeigt geringe Aktivität gegenüber HIV-1.相似文献
16.
Elisabeth Csöregi Thomas Laurell Ionis Katakis Adam Heller Lo Gorton 《Mikrochimica acta》1995,121(1-4):31-40
In-vitro on-line glucose monitoring is described, based on microdialysis sampling and amperometric detection operated in a flow-injection system. Samples were injected into a two-electrode microcell containing an Ag/AgCl quasi-reference electrode and a glucose enzyme electrode as the working electrode, operated at + 0.15 Vvs. Ag/AgCl. The enzyme electrode is constructed by mixing the wired glucose oxidase into carbon paste. {Poly[1-vinylimidazole osmium(4,4-dimethylbipyridine)2Cl)]}+/2+ was used to wire the enzyme. The non-coated electrodes, cross-linked with poly(ethylene glycol) diglycidyl ether, responded linearly to glucose concentrations up to 60 mM, and were characterized by a sensitivity of 0.23 A mM–1 cm–2, when operated in flow injection mode and of 5.4 AmM
–1 cm–2 in steady-state conditions. This sensitivity of the resulting enzyme electrode was 50% lower than that of similarly prepared but non-cross-linked electrodes. However, the cross-linked electrodes showed superior operational and storage stabilities, which were further improved by coating the electrodes with a negatively charged Eastman AQ film. An in-house designed microdialysis probe, equipped with a polysulphone cylindrical dialysis membrane, yielded a relative recovery of 50–60% at a perfusion rate of 2.5 l/min–1 in a well stirred glucose solution. The on-line set up effectively rejected common interferences such as ascorbic acid and 4-acetaminophen when present at their physiological concentrations. 相似文献
17.
Amir Reza Jassbi Pahup Singh Vivek Krishna Pradeep K. Gupta Satoshi Tahara 《Chemistry of Natural Compounds》2004,40(3):250-253
The NMR spectral data including high resolution 1H, 13C and 2D NMR for butrin, 3,4,7-trihydroxyflavanone 3,7-di-O--D-glucopyranoside, isolated from flowers of Butea monosperma, are reported here for the first time. Butrin was hydrolyzed using b-glucosidase to butin in high yield. They were subjected to free radical scavenging test using 2,2-diphenyl-1-picrylhydrazyl (DPPH) spectrophotometric assay. At a dose of 4 × 10-8 mol of tested compounds, the percentage of reduced DPPH for butin was 14.5% while no reduction was observed for butrin (0%). 相似文献
18.
R. M. Zolotar' A. I. Bykhovets S. N. Sokolov N. V. Kovganko 《Chemistry of Natural Compounds》2002,38(1):70-73
The toxicity of 3-chlorosteroids 1-8 for colorado beetle (Leptinotarsa decemlineata Say.) larvae was studied by a contact-intestinal method. The most active insect growth and development regulators of the studied compounds are 3-chlorocholest-5-ene (1a), 3-chloro-5,6-diol 6-formate (3b), 3-chloro-7-hydroxy-6-ketone (4a), and 3-chloro-5-bromo-4-6-ketone (8). 相似文献
19.
Dinaphthyldiquinhydrone (4) first obtained byStenhouse andGroves
2 reacts as well as 4,4-bi-(1,2-naphthoquinone)1 with aniline and substituted anilines to give anilinoquinones2 a-h. However, yields of2 are considerable higher if4 is used. The IR-Spectrum of4 is very similar to that of 2,11-dihydroxy-3,10-perylenquinone, therefore we suggest for4 a the structure of a 3,3-dihydroxy-4,4-dioxo-1,1, 4,4-tetrahydro-1,1-binaphthylidene, at least in the solid state.
Herrn Prof. Dr.G. Zigeuner in traditionsverbundener Freundschaft zum 60. Geburtstag gewidmet. 相似文献
20.
In an attempt to clarify the origin of the dual phosphorescence in phenyl alkyl ketones, we have made some calculation (within the C.I.P.S.I. method in an excitonic scheme) to elucidate the conformation of both ground states and excited states of propiophenone. Our calculations have shown the presence of two stable isomers in the ground state, first n * state, and first * singlet and triplet states. So our work suggests that the origin of the dual phosphorescence of propiophenone could be related to the conformational change of the molecule in the n * state, because the most stable conformations in the n * state and in the ground state are different. 相似文献