A Practical Enantioselective Synthesis of (-)-NS-49 #

Asymmetric synthesis of (-)-NS-49 (1) was achieved by a convenient and short route.

     

火试金法测定铜硫矿中的金和银量的研究

本文针对铜硫矿中铜含量较高的特性,建立了适合该试样的配料比、高温熔融,金、银与铅形成合金,利用其比重悬殊与熔渣分离,将铅扣灰吹得金、银合粒,用硝酸分金,用重量法测定金量,用容量法测定银量。方法的相对标准偏差0.66%到4.78%,加标回收率96.5%到100.6%。     

Vapor-phase processable novel nonplanar donor-acceptor quateraryls for blue OLEDs(#)

A novel series of thermally stable blue light emitting quateraryls with a piperidine donor and a nitrile acceptor was prepared from a ketene- S, S-acetal under mild conditions without using an organometal catalyst. The performance of a blue quateraryl 6e was investigated by fabricating a multilayer OLED with a configuration of ITO/PEDOT:PSS (40 nm)/quateraryl (60 nm)/BCP (6 nm)/Alq(3) (20 nm)/LiF (0.5 nm)/Al (200 nm), which exhibited blue emission with a low turn on voltage of 4 V at a brightness of 0.22 cd/m(2).     

Capturing the antiaromatic (#6094) C68 carbon cage in the radio-frequency furnace

Although all fullerenes do not satisfy the classical aromaticity condition, as a result of their nonplanar nature, they experience effective stabilization due to extensive cyclic π-electron delocalization and exhibit pronounced "spherical aromaticity". This feature has raised the question of the opposite phenomenon, that is, the existence of antiaromatic carbon cages. Here the first experimental evidence of the existence of antiaromatic fullerenes is reported. The elusive (#6094)C(68) was effectively captured as C(68)Cl(8) by in situ chlorination in the gas phase during radio-frequency synthesis. The chlorinated cage was separated by means of multistage HPLC, and its connectivity unambiguously determined by single-crystal X-ray analysis. Halogen-stripped pristine (#6094)C(68) was monitored by mass spectrometry of the chlorinated C(68)Cl(8) cage. Quantum chemical calculations reveal the highly antiaromatic character of (#6094)C(68), in accordance with all geometric, energetic, and magnetic criteria of aromaticity. Chlorine addition leads to substantial stabilization of the cage owing to aromatization in the resulting C(68)Cl(8), which explains its high abundance in the primary fullerene soot. This work provides new insights into the process of fullerene formation and better understanding of aromaticity phenomena in general.     

Epoxidation in ionic liquids: A comparison of rhenium(VII) and molybdenum(VI) catalysts

Complexes of the type (dimethyl-bpy)MoO₂Cl₂ and Schiff/Lewis-base complexes of methyltrioxorhenium (MTO), being efficient homogeneous catalysts for the epoxidation of olefins, have been examined with respect to their catalytic performance at 55 and 25 °C in systems employing room temperature ionic liquids (RTILs) of composition [BMIM]NTf₂, [BMIM]PF₆, [BMIM]BF₄ and [C₈MIM]PF₆ as solvents. The performance in the cyclooctene epoxidation was observed to be strongly dependent on the water content of the system and the catalyst solubility in the RTIL. MTO based systems prove to be superior with respect to lower energy consumption, higher stability and higher product yields compared to the investigated Mo(VI) system under the conditions applied.     

Structurally modulated magnetic properties in the A(3)MnRu(2)O(9) phases (A = Ba, Ca): the role of metal-metal bonding in perovskite-related oxides

Ca(3)MnRu(2)O(9) and Ba(3)MnRu(2)O(9) were synthesized from transition metal dioxides and alkaline earth metal carbonates at 1100-1300 degrees C. Ca(3)MnRu(2)O(9) adopts the prototypical GdFeO(3)-type perovskite structure with Mn and Ru statistically disordered over the single metal atom site. The susceptibility shows Curie-Weiss behavior above 240 K with mu(eff) = 3.14 micro(B)/metal atom, which is in excellent agreement with the expected spin-only moment of 3.20 micro(B). Below 150 K, the compound shows spin-glass-like short-range ferrimagnetic correlations. The high-temperature region of the electrical resistivity reveals a small activation energy of 17(1) meV whereas the low-temperature region is nonlinear and does not fit a variable range hopping model. Ba(3)MnRu(2)O(9) crystallizes in the 9-layer BaRuO(3)-type structure containing M(3)O(12) face-shared trioctahedral clusters in which Mn and Ru are statistically disordered. Ba(3)MnRu(2)O(9) shows nonlinear reciprocal susceptibility at all temperatures and is described by a variable-spin cluster model with an S = (1)/(2) ground state with thermally populated excited states. The low spin value of this system (S = (1)/(2)) is attributed to direct metal-metal bonding. Below 30 K, the compound shows short-range magnetic correlations and spin-glass-like behavior. The high-temperature region of the electrical resistivity indicates a small activation energy of 8.8(1) meV whereas the low-temperature region is nonlinear. The importance of metal-metal bonding and the relationships to other related compounds are discussed.     

Modified synthesis of deoxyadenosine-5'-(35S)-thiomonophosphate [dAMP (35S)] with high specific activity: An important starting material for the synthesis of deoxyadenosine-5'-(&;#945;-35S)-thiotriphosphate [dATP (&;#945;-35S)]

Deoxyadenosine-5'-monophosphite was treated with excess of trimethylsilyl chloride. One equivalent of trimethylsilyl chloride treated phosphite in pyridine and one equivalent of elemental ³⁵S in toluene solution (specific activity > 1000 Ci/mmol) were stirred together with gradual removal of solvents under vacuum, over a period of one hour, to give deoxyadenosine-5'-(³⁵S)-thiomonophosphate [dAMP(³⁵S)] in high yields.     

Structural Control of (1)A(2u)-to-(3)A(2u) Intersystem Crossing in Diplatinum(II,II) Complexes

Analysis of variable-temperature fluorescence quantum yield and lifetime data for per(difluoroboro)tetrakis(pyrophosphito)diplatinate(II) ([Pt(2)(μ-P(2)O(5)(BF(2))(2))(4)](4-), abbreviated Pt(pop-BF(2))), yields a radiative decay rate (k(r) = 1.7 × 10(8) s(-1)) an order of magnitude greater than that of the parent complex, Pt(pop). Its temperature-independent and activated intersystem crossing (ISC) pathways are at least 18 and 142 times slower than those of Pt(pop) [ISC activation energies: 2230 cm(-1) for Pt(pop-BF(2)); 1190 cm(-1) for Pt(pop)]. The slowdown in the temperature-independent ISC channel is attributed to two factors: (1) reduced spin-orbit coupling between the (1)A(2u) state and the mediating triplet(s), owing to increases of LMCT energies relative to the excited singlet; and (2) diminished access to solvent, which for Pt(pop) facilitates dissipation of the excess energy into solvent vibrational modes. The dramatic increase in E(a) is attributed to increased P-O-P framework rigidity, which impedes symmetry-lowering distortions, in particular asymmetric vibrations in the Pt(2)(P-O-P)(4) core that would allow direct (1)A(2u)-(3)A(2u) spin-orbit coupling.     

A new isochroman from the marine endophytic fungus 1893#

A new isochroman, 6-hydroxy-3-methylisochroman-5-carboxylic acid, and six known compounds were isolated from the culture of marine-derived mangrove fungus 1893#. Their structures were elucidated by analysis of spectroscopic data. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 114–116, March–April, 2006.     

RNAA in metrology: A highly accurate (definitive) method

The idea of highly accurate (definitive) methods by radiochemical neutron activation analysis (RNAA) is presented and illustrated with several examples of methods worked out in this Laboratory over the past several years. Definitive methods by RNAA are constructed by combining reactor neutron activation with very selective and quantitative post-irradiation separation of the indicator radionuclide by column chromatography followed by γ-ray spectrometric measurement. All conditions for the determination of the individual element are optimized and uncertainties associated with every step of the analytical procedure are minimized. Even after the method has been thoroughly elaborated and validated through the analysis of appropriate certified reference materials (CRMs), the results obtained in each series of measurements are acknowledged as obtained by definitive method only when a series of previously formulated criteria is simultaneously fulfilled. The examples of definitive methods for the determination of cadmium, cobalt and molybdenum, respectively, in biological materials are presented. Each of these methods has detection limit of the order of ng g⁻¹ or better, and yields accurate and precise results. The expanded standard uncertainty is of the order of 2.6% for the case of single-element determination (Co) and 3.4-5.2% for the less favourable case (Mo) where there is necessity for simultaneous determination of uranium to correct for interference due to fission reaction. Definitive methods by RNAA may constitute an option or alternative with respect to ID-MS as methods of “guaranteed accuracy” being also a perspective solution in the case of monoisotopic elements, for which ID-MS cannot be used.     

A packaging contaminant: isopropylthioxanthone (ITX) in dairy products

A fast, simple and very selective liquid chromatography-mass spectrometry (LC-MS) method for the detection of isopropylthioxanthone (ITX) in dairy products has been developed and validated. After addition of an ITX-d(3) as internal standard and a simple extraction from the sample with acetonitrile, the extract was centrifuged and directly injected into the LC-MS system. Chromatographic separation was achieved by means of a Gemini C18 column (100 mm x 2.0 mm i.d. 5 microm) using a gradient of aqueous 20 mM ammonium formiate at pH 4.5 and methanol as the mobile phase, at a flow rate of 0.25 mL min(-1). The method was validated according to the guidelines laid down by the Commission Decision 2002/657/EC using the parent ion [M+H](+) (m/z 255) as quantification ion, and the fragment ion (m/z 213) obtained by in-source collision-induced dissociation (IS-CID) as confirmation ion. Absolute and relative recoveries rates were verified at 5, 10, 15 microg kg(-1) in yoghurt samples and at 5 microg kg(-1) in milk and pudding: mean absolute recoveries were 77% in yoghurt, 50% in pudding and 67% in milk; relative recoveries (after internal standard correction) were always >97% in each matrix. The detection limit (CCalpha) and the detection capability (CCbeta) of method were 6.2 and 7.2 microg kg(-1), respectively.     

Rh(I) Complexes in Catalysis: A Five-Year Trend

Rhodium is one of the most used metals in catalysis both in laboratory reactions and industrial processes. Despite the extensive exploration on “classical” ligands carried out during the past decades in the field of rhodium-catalyzed reactions, such as phosphines, and other common types of ligands including N-heterocyclic carbenes, ferrocenes, cyclopentadienyl anion and pentamethylcyclopentadienyl derivatives, etc., there is still lively research activity on this topic, with considerable efforts being made toward the synthesis of new preformed rhodium catalysts that can be both efficient and selective. Although the “golden age” of homogeneous catalysis might seem over, there is still plenty of room for improvement, especially from the point of view of a more sustainable chemistry. In this review, temporally restricted to the analysis of literature during the past five years (2015–2020), the latest findings and trends in the synthesis and applications of Rh(I) complexes to catalysis will be presented. From the analysis of the most recent literature, it seems clear that rhodium-catalyzed processes still represent a stimulating challenge for the metalloorganic chemist that is far from being over.     

N-Formylsaccharin: A Sweet(able) Formylating Agent in Mechanochemistry

The acylation of amines has always attracted a deep interest as a synthetic route due to its high versatility in organic chemistry and biochemical processes. The purpose of this article is to present a mechanochemical acylation procedure based on the use of acyl-saccharin derivatives, namely N-formylsaccharin, N-acetylsaccharin, and N-propionylsaccharin. This protocol furnishes a valuable solvent-free alternative to the existing processes and aims to be highly beneficial in multi-step procedures due to its rapid and user-friendly workup.     

A New Class of Nucleoside Analogues. Synthesis of N. -Pyrimidinyl-and N9-Purinyl-4′-hydrqxy-3-(Hydsoxymethyl)butanes1 # 2

Interest in non-glycosidic derivatives of the nucleo-bases uracil, theymine, cytosine, adenine and guanine stems from their status as nucleoside analogues. It is noteworty in this connection that the anti-biotics aristeromycin³ and eritadenine⁴ consist of an adenine moiety linked, via N₉ -, to a cyclopentyl or a butiric acid derivative, respectively, in place of the conventional nucleoside sugars. A non-glycoaidic 5-fluorouracil derivative⁵ has been recently reported to be clinically effective in the treatment of Gastrointestinal cancer. In this communication the ficile synthesis of 4-hydroxy-3-(hydroxymethyl)butyl derivatives of the nucleobases (1) is described. These nucleoside analogues are characterized by the special feature that they incorporate two hydroxyl functions in a relationship corresponding to the 3′-and 5′-hydroxy groups of the 2-deodyribose Doiety. Phosphorylationj of the hydroxyl groups or their linkage via phosphodiester of the hydroxyl groups or their linkage via phosphodiester bridges should give nucleotide analogues or novel nucleic acid models. The latter molecular systems constitute a new class of potential anti-mitotic or anti-viral agents. One principle synthetic approach to compounds of general structure 1 was visualized via the intermediacy of 2-(hydroxymethyl) - 4-aminobutanol (2, ReH) which, acting as a common precursor, could be elaborated to the desired pyrimidine or purine derivative, via its amine function. The synthesis of amine 2 was achieved according to the reaction sequence described in Scheme I. Diethyl malonate was coupled with 2,2-dimethoxybromoethane, in presence of sodium ethoxide (EthoH, 170°, autoclave). The resulting diester (3) was reduced with LialH₄ to the corresponding diol (4), which was benzylated (NaH, C₆H₅CH₂Cl) to 5. When 5 was refluxed with NH₂OH.HCl in methanol for 30 min., a mixture of oximes 6a,b (syn- and anti-) and nitrile 7 was isolated. The latter mixture could be directly reduced with LiAlH₄ to amine 2,⁶ in high yield.     

Poly(difluorophosphazene): A New Intermediate for the Synthesis of Poly(organophosphazenes)

Although many poly(organophosphazenes) have been synthesized, new preparative pathways are needed, especially for polymers that contain alkyl side groups. A new development involves the use of poly(difluorophosphazene), (NPC1₂) instead of poly-(dichlorophosphazene), (NPC1²)_n, as a substrate for reactions with organometallic reagents. This approach has allowed the preparation of a new class of poly(organophosphazenes) that possess substituent groups linked to the skeleton through direct phosphorus-carbon bonds. The synthesis of uncrosslinked poly-(difluorophosphazene) and its reactions with alkoxides and amines are also reviewed.     

Very-low-pressure pyrolysis (VLPP) of group IV (A) tetramethyls: Neopentane and tetramethyltin

The decomposition of neopentane was studied using the very-low-pressure pyrolysis (VLPP) technique at temperatures from 1000 to 1260 K. The derived Arrhenius parameters are consistent with δH_f⁰(t-butyl) = 8.4 kcal/mol. Using the above A factor, data on the decomposition of tetramethyltin yield DH⁰(Sn(CH₃)₃ - CH₃) = 69 ± 2 kcal/mol.