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31.
Micha? K. Cyrański Paul von Ragué Schleyer Tadeusz M. KrygowskiHaijun Jiao Georg Hohlneicher 《Tetrahedron》2003,59(10):1657-1665
The stability of a set of 105 five-membered π-electron systems (involving aromatic, non-aromatic and anti-aromatic species) was evaluated using six isodesmic reactions of which two belong to the subclass of homodesmotic reactions, which are based on cyclic and acyclic reference systems. We demonstrate that the ‘Resonance Energies’ derived from isodesmotic schemes have obvious flaws and do not correct or cancel other contributions to the energy, such as the changes of hybridization, homoconjugation of heterosubstituted cyclopentadienes, conjugative interactions of CC or CX (X=N or P) with a π or pseudo π orbital at Y (Y=O, S, NH, PH), strain, etc. as effectively as possible. Likewise, ‘aromatic stabilization energies (ASE)’ derived from homodesmotic schemes based on the acyclic reference compounds do not give satisfactory results. We strongly recommend that only cyclic reference compounds should be used for ASE and other aromaticity evaluations. The analysis is based on ab initio optimized geometries at B3LYP/6-311+G∗∗. 相似文献
32.
V. V. Yanilkin V. I. Morozov F. F. Nigmadzyanov T. V. Gryaznova A. M. Kibardin 《Russian Chemical Bulletin》1998,47(8):1478-1480
Electrooxidation of 2-R-1,3-dibutyl-4,5-dimethyl-2,3-dihydro-1H-1,3,2-diazaphospholes with tri- and tetracoordinated phosphorus atoms were studied. Reversible one-electron oxidation gives
radical cations at potentials of −0.37 to +0.36 V. Magnetic parameters of the radical cations were measured.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1522–1524, August, 1998. 相似文献
33.
Constable EC Handel RW Housecroft CE Farràn Morales A Ventura B Flamigni L Barigelletti F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(13):4024-4034
A new series of V-shaped trinuclear metallorods and X-shaped pentanuclear metallostars has been prepared by the reaction of metal complexes bearing pendant phenolic functionalities with complexes containing electrophilic ligands. Specifically, {M(tpy)2} motifs (M=Ru or Os; tpy=2,2':6',2'-terpyridine) bearing one or two pendant 3,5-dihydroxyphenyl substituents at the 4-position of the central ring of the tpy have been reacted with the complexes [Ru(tpy)(Xtpy)]2+ (X=Cl or Br) to form new ether-linked species. The energy transfer from ruthenium to osmium in these complexes has been investigated in detail and the efficiency of transfer shown to be highly temperature dependent; the energy transfer is highly efficient at low temperature, whereas at room temperature nonradiative and nontransfer deactivation of the excited {Ru(tpy)2}* domains is most significant. 相似文献
34.
Baumgartner T Bergmans W Kárpáti T Neumann T Nieger M Nyulászi L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4687-4699
To explore their suitability for applications in molecular optoelectronics and as sensory materials, novel dithieno[3,2-b:2',3'-d]phospholes have been synthesized and their reactivity and properties investigated. An efficient two-step synthesis allowed for a modular assembly of differently functionalized compounds. The dithieno[3,2-b:2',3'-d]phosphole system exhibits extraordinary optoelectronic properties with respect to wavelength, intensity, and tunability. Owing to the nucleophilic nature of the central phosphorus atom, its significant electronic influence on the conjugated pi system can be altered selectively by chemically facile modifications such as oxidation or complexation with Lewis acids or transition metals. All the dithienophosphole species presented show very strong blue photoluminescence with excellent quantum yield efficiencies supporting their potential utility as blue-light emitting components in organic light emitting diodes (OLEDs). Furthermore, depending on the electronic nature of the phosphorus center, the materials exhibit distinctive optoelectronic properties suggesting that the dithieno[3,2-b:2',3'-d]phosphole system may be useful as sensory material. Theoretical calculations, including time-dependent DFT methods, revealed the excellent predictability of the structures and optoelectronic properties of the functionalized dithienophospholes allowing the design of future dithieno[3,2-b:2',3'-d]phosphole-based materials to be "stream-lined". By using tin-functionalized dithienophosphole monomers, a strategy, which involves Stille coupling, towards extended pi-conjugated materials with significantly redshifted optoelectronic properties is also presented. 相似文献
35.
Jo Sakurada 《Tetrahedron》2007,63(18):3806-3817
Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with N-lithio nitrogen-containing heterocycles gave N-alkenylated products in moderate to good yields. Also, the reaction of C-lithio indoles, which were generated from N-protected indoles, with magnesium alkylidene carbenoids gave C-2 or C-3 alkenylated products, corresponding to the protective group. The intermediate of these reactions were found to be the alkenyl anion, which could be trapped with electrophiles to give the heterocycles having fully substituted alkenes. 相似文献
36.
G. A. Tolstikov I. V. Kresteleva A. Yu. Spivak A. A. Fatykhov V. R. Sultanmuratova 《Russian Chemical Bulletin》1993,42(3):557-563
Aluminum and manganese derivatives of lithiated bis-lactim ethers of cyclo-(L-Ala-L-Ala) were used for the enantioselective synthesis of -hydroxy and polyhydroxy -amino acids of the 2-methyIserine series. A new variant of the synthesis of these acids via 3-acyl-2, 5-dialkoxy-3, 6-dimethyl-3, 6-dihydropyrazines is proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 590–595, March, 1993. 相似文献
37.
David M. Dastrup Steven M. Weinreb James R. Henry Andrew J. Lechleiter 《Tetrahedron》2004,60(4):901-906
β-Tosylethylhydrazine (6) can be prepared efficiently in one step from commercially available p-tolyl vinyl sulfone (7) and hydrazine hydrate. This hydrazine reacts with both 1,3-diketones and conjugated ynones in glacial acetic acid to provide a variety of N-tosylethyl-protected (TSE) pyrazoles in good yields. The TSE group can be removed from the pyrazoles using potassium t-butoxide in THF at −30 °C-rt. In addition, hydrazine 6 condenses with β-ketonitriles and β-aminoacrylonitriles to afford 5-aminopyrazoles, which can be deprotected by brief treatment with NaOEt in EtOH/DMSO at 45 °C. 相似文献
38.
39.
Summary 2-Chloroquinoline-3-carbaldehyde and 2-chloro-4-methylquinoline-3-carbaldehyde have been prepared from acetanilide and acetoacetanilidevia a Vilsmeier-Haack reaction. Upon reaction with phenyl hydrazine, hydroxylamine, urea, and thiourea in presence of acetic acid, these chloroaldehydes afforded the title compounds which exhibit a several times higher analgesic activity than noramidopyrine (NAP).
Synthese einiger neuer substituierter Chinoline als stark analgetisch wirkende Substanzen
Zusammenfassung 2-Chlorchinolin-3-carbaldehyd und 2-Chlor-4-methylchinolin-3-carbaldehyd wurden, ausgehend von Acetanilid und Acetylacetanilid, über eineVilsmeier-Haack-Reaktion hergestellt. Reaktion dieser chlorsubstituierten Aldehyde mit Phenylhydrazin, Hydroxylamin, Harnstoff und Thioharnstoff ergab die Titelverbindungen, deren analgetische Aktivität jene von Noramidopyrin (NAP) um ein Mehrfaches übertrifft.相似文献
40.
Reduction of enantiopure N-p-toluenesulfinyl ketimines derived from 2-pyridyl ketones affords N-p-toluenesulfinyl amines with good yields and diastereoselectivities. 相似文献