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61.
A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2',5'-dimethoxyphenyl)pentadienyl]Fe(CO)(3)(+) cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)(3). Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)(3) along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl(2), affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane. 相似文献
62.
Yann K. Petit Christian Leypold Nika Mahne Elonore Mourad Lukas Schafzahl Christian Slugovc Sergey M. Borisov Stefan A. Freunberger 《Angewandte Chemie (International ed. in English)》2019,58(20):6535-6539
Singlet oxygen (1O2) causes a major fraction of the parasitic chemistry during the cycling of non‐aqueous alkali metal‐O2 batteries and also contributes to interfacial reactivity of transition‐metal oxide intercalation compounds. We introduce DABCOnium, the mono alkylated form of 1,4‐diazabicyclo[2.2.2]octane (DABCO), as an efficient 1O2 quencher with an unusually high oxidative stability of ca. 4.2 V vs. Li/Li+. Previous quenchers are strongly Lewis basic amines with too low oxidative stability. DABCOnium is an ionic liquid, non‐volatile, highly soluble in the electrolyte, stable against superoxide and peroxide, and compatible with lithium metal. The electrochemical stability covers the required range for metal–O2 batteries and greatly reduces 1O2 related parasitic chemistry as demonstrated for the Li–O2 cell. 相似文献
63.
Sergey Miltsov Julian Alonso-Chamarro Mar Puyol 《Journal of heterocyclic chemistry》2020,57(8):3193-3201
New symmetrical and unsymmetrical near-infrared absorbing ketocyanine-type dyes are synthesized and their optical characterization is done. The relationships between their structure and optical properties are discussed. The synthesized ketocyanine dyes show a positive solvatochromism and are poorly fluorescent. A new procedure for the preparation of N,N,N′,N′-tetramethylvinamidinium perchlorate, which was a very useful reagent for the synthesis of various heterocyclic compounds as well as for the preparation of cyanine dyes is developed. 相似文献
64.
The AIE luminogen tetrakis(2-naphthalenyl)ethene (2-NA 4 E) was synthesized by Barton’s double extrusion diazo-thione coupling method from 2,2′-dinaphthyl thioketone and 2,2′-(diazomethylene)bisnaphthylene in 77 % yield. The structure of 2-NA 4 E was confirmed by its 1H NMR and 13C NMR spectra with full assignments. 2-NA 4 E and its parent tetraphenylethene (Ph 4 E) have been subjected to a comprehensive computational DFT study, in search of their conformational spaces. Seven conformers and two transition states of 2-NA 4 E have been located. Four conformers and one transition state of Ph 4 E have been located. The conformers of 2-NA 4 E and Ph 4 E are not overcrowded, as indicated by the contact distances in the fjord and cove regions. The relative free energies (ΔG 298) of the six most stable conformers of 2-NA 4 E are in the narrow range of 2.3 kJ/mol; they make comparable contributions (12–29 %) to the equilibrium mixture. The energy barriers for the diastereomerization D 2-Z,Z,Z,Z $ \rightleftharpoons $ ? D 2-E,E,E,E via the transition state C 1-Z,E,E,Z and for the enantiomerization C 2-Z,Z,E,E $ \rightleftharpoons $ ? C 2-E,E,Z,Z via the transition state C i -Z,E,Z,E are only 29.8 and 29.0 kJ/mol, respectively, indicating very rapid rates of diastereomerization and enantiomerization at room temperature. The values of naphthalenyl torsion angles and ethenic twist angles in 2-NA 4 E are almost identical to those in the parent Ph 4 E. The previously proposed “bulkiness” of the naphthalenyl substituents and the validity of the restriction of naphthalenyl rotation are challenged. The analysis of the AIE effect in 2-NA 4 E should take into account the intermolecular homochiral and heterochiral interactions between the conformers. 相似文献
65.
A synthetic route to a series of 4-alkyl- or arylquinolines, bearing in 2- and 3-position fluorinated and phosphonate functions at the same time, is reported for the first time. These compounds are synthesized via regioselective heterocyclization of XCF2-alkynylphosphonates (X=F, Cl, Br, H, CF3) with ortho-aminoaryl ketones (R=CH3, CF3, Ph) in the presence of K2CO3 or Li2CO3/TMEDA as mediators. 2-Fluoro- and 3-phosphorus-containing 4-Me, 4-CF3 or 4-Ph quinolines are obtained in good to excellent yields. The influence of substituents in the aromatic ketone, the XCF2-group in the alkyne as well as mediators and the reaction medium on the reactivity and specificity of the reaction is also investigated. 相似文献
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68.
EV Tretyakov SE Tolstikov AO Suvorova AV Polushkin GV Romanenko AS Bogomyakov SL Veber MV Fedin DV Stass E Reijerse W Lubitz EM Zueva VI Ovcharenko 《Inorganic chemistry》2012,51(17):9385-9394
Breathing crystals based on polymer-chain complexes of Cu(hfac)(2) with nitroxides exhibit thermally and light-induced magnetostructural anomalies in many aspects similar to a spin crossover. In the present work, we report the synthesis and investigation of a new family of Cu(hfac)(2) complexes with tert-butylpyrazolylnitroxides and their nonradical structural analogues. The complexes with paramagnetic ligands clearly exhibit structural rearrangements in the copper(II) coordination units and accompanying magnetic phenomena characteristic for breathing crystals. Contrary to that, their structural analogues with diamagnetic ligands do not undergo rearrangements in the copper(II) coordination environments. This confirms experimentally the crucial role of paramagnetic ligands and exchange interactions between them and copper(II) ions for the origin of magnetostructural anomalies in this family of molecular magnets. 相似文献
69.
Anastasia S. Kondrateva Maxim V. Mishin Sergey E. Alexandrov 《Journal of the American Society for Mass Spectrometry》2017,28(11):2352-2360
NiO layers were deposited by metal-organic chemical vapor deposition using bis-(ethylcyclopentadienyl) nickel (EtCp)2Ni and oxygen or ozone. As a continuation of kinetic study of NiO MOCVD the gas-phase, transformations of (EtCp)2Ni were studied in the temperature range of 380–830 K. Time of reactions corresponding to the residence time of the gas stream in hot zone of the reactor was about 0.1 s under conditions studied. The interaction of (EtCp)2Ni with oxygen started at 450 K and its conversion rate reached the maximum at 700 K. The interaction of (EtCp)2Ni with ozone started at 400 K and its conversion rate reached the maximum at 600 K. Transformations of the gas phase with the temperature in the reaction zone were studied, the model reaction schemes illustrating (EtCp)2Ni transformations in the reaction systems containing oxygen and ozone have developed. In the reaction system (EtCp)2Ni–O2–Ar the main gas-phase products at 380–500 K were CO, CO2, HCO, C2H5OH, CpCOOH, and CpO. Formation of the C2H2O, C3H4O, and C5H8O was found at 630–830 K. The same gas-phase species, (C4H3O)2Ni and dialdehydes was formed in the reaction system (EtCp)2Ni–O3–O2–Ar. 相似文献
70.
Structures of Chlorinated Fullerenes,IPR C96Cl20 and Non‐classical C94Cl28 and C92Cl32: Evidence of the Existence of Three New Isomers of C96 下载免费PDF全文
Prof. Dr. Shangfeng Yang Tao Wei Song Wang Dr. Ilya N. Ioffe Prof. Dr. Erhard Kemnitz Prof. Dr. Sergey I. Troyanov 《化学:亚洲杂志》2014,9(11):3102-3105
Chlorination of various HPLC fractions of C96 with a mixture of VCl4 and SbCl5 at 340–360 °C and single‐crystal X‐ray diffraction study of the products led to the identification of three new IPR isomers of C96. The C96(175) isomer forms a stable chloride, C96(175)Cl20, while chlorides of two other new isomers, C96(114) and C96(80), undergo cage shrinkage yielding C94(NC1)Cl28 and C96(NC2)Cl32 with non‐classical (NC) cages. These two NC chlorides contain, respectively, one and two heptagons flanked by pairs of fused pentagons and are stabilized by chlorine attachment to the emerging pentagon–pentagon junctions. Thus, the number of the experimentally confirmed C96 isomers has reached nine, which corroborates the empirical rule that the C6n fullerenes exhibit particularly rich isomerism. 相似文献