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1.
A new, highly efficient allylation reagent—lithium allyldibutylmagnesate (allylBu2MgLi)—was obtained by mixing allyl-magnesium chloride (1 equiv) and n-BuLi (2 equiv). N-Lithiated and N-methyl substituted 1H-pyridine-2-thiones and -ones were successfully and regioselectively allylated by treatment with allylBu2MgLi yielding 6-allyl-3,6-dihydro-1H-pyridine-2-(thio)ones and 4-allyl-3,4-di-hydro-1H-pyridine-2-(thio)ones. The latter were formed by a 3,3-sigmatropic Cope rearrangement of the former.  相似文献   

2.
A method for the determination of isocyanates as di-n-butyl amine (DBA) derivatives using tandem mass spectrometry (MS/MS) and electrospray ionisation (ESI) is presented. Multiple-reaction monitoring (MRM) of the protonated molecular ions and corresponding deuterium-labelled d9-DBA derivatives resulted in selective quantifications with correlation coefficients >0.998 for the DBA derivatives of isocyanic acid (ICA), methyl isocyanate (MIC), ethyl isocyanate (EIC), propyl isocyanate (PIC), phenyl isocyanate (PhI), 1,6-hexamethylene diisocyanate (HDI), 2,4-, 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), 4,4′-methylenediphenyl diisocyanate (MDI), 3-ring MDI, 4-ring MDI, HDI-isocyanurate, HDI-diisocyanurate, HDI-biuret and HDI-dibiuret. The instrumental precision for 10 repeated injections of a solution containing 0.1 μg ml−1 of the studied derivatives was <2%. Performing MRM of the product ion [DBA + H]+ (m/z = 130) from the protonated molecular ion resulted in the lowest detection limits, down to 10 amol (for TDI). Quantification of concentrations below 10−6 of the occupational exposure limit (OEL) for TDI during 10 min of air sampling was made possible. In an effort to control the formation of alkali adducts, addition of lithium acetate to the mobile phase and monitoring of lithium adducts was evaluated. Having lithium present in the mobile phase resulted in complete domination of [M + Li]+ adducts, but detection limits for the studied compounds were not improved. Different deuterium-labelled derivatives as internal standards were evaluated. (1) DBA derivatives of deuterium-labelled isocyanates (d4-HDI, d3-2,4-TDI, d3-2,6-TDI and d2-MDI), (2) d9-DBA derivatives of the corresponding isocyanates and (3) d18-DBA derivatives of the corresponding isocyanates. An increase in number of deuterium in the molecule of the internal standard resulted in an increase in instrumental precision and a decrease in correlation within calibration series.  相似文献   

3.
The non-vicinal methyl-phenyl-substituted zirconocene dichlorides meso-and rac-[Zr{η5-(1-Ph-3-Me-C5H3)}2Cl2] and [Zr(η5-C5H5){η5-(1-Ph-3-Me-C5H3)}Cl2] have been isolated by transmetallation of the lithium salt Li(1-Ph-3-Me-C5H3) to ZrCl4(THF)2 and [Zr(η5-C5H5)Cl3 · DME] (DME = dimethoxyethane), respectively. Similar transmetallation of the lithium salt Li2[(Me-Ph-C5H2SiMe2)2O] to MCl4 gave the ansa-metallocenes [M{η5-(Me-Ph-C5H2SiMe2)2O}Cl2] (M = Zr, Hf) for which the meso- and rac-diastereomers were separated. The dimethyl and dibenzyl derivatives of these metallocenes were also prepared and the structure of all of these compounds determined by NMR spectroscopy. The molecular structure of rac-[Zr{η5-(2-Me-4-Ph-C5H2SiMe2)2O}Cl2] was determined by single crystal X-ray diffraction methods. The activity of the dichlorometallocenes/MAO catalysts for ethene and propene polymerization was evaluated.  相似文献   

4.
The addition of LiBun to a toluene solution of Ph2P(O)N(CH2Ph)CH31 and 2,6-di-tert-butyl-4-methylphenol 5 leads to the formation of the mixed dimer [(Ph2P(O)N(CH2Ph)CH3) · LiOC6H2-2,6-{C(CH3)3}2-4-CH3) · C7H8]26. The single crystal X-ray structure shows that two lithium aryloxide moieties dimerize giving rise to a Li2O2 core in which each lithium atom is additionally coordinated to a phosphinamide 1 ligand. The multinuclear magnetic resonance study (1H, 7Li, 13C, 31P) indicates that the solid-state structure is preserved in toluene solution. Complex 6 may be considered as a model for the pre-complexation step preceding the metalation of phosphinamides by an organolithium base.  相似文献   

5.
Pyrazine (Pz) bridged benzyl dicobaloximes [ArCH2Co(dioxime)2]2-μ-Pz [dioxime = dmgH, dpgH] have been synthesized and characterized with 1H and 13C NMR. The complexes have been synthesized by a simple procedure in one-pot directly from the corresponding benzyl aqua cobaloxime. In the crystal structure of [PhCH2Co(dpgH)2]2-μ-Pz, two cobaloxime units are in eclipsed form whereas they were completely staggered in the reported [EtCo(dpgH)2]2-μ-Pz. This is due to the π-π interaction between the axial benzyl group and phenyl ring of the equatorial dpgH group. Both cis and trans isomer crystallized together in the crystal structure of [PhCH2Co(dpgH)(dmgH)]2-μ-Pz. The cyclic voltammetry study in [PhCH2Co(dioxime)2]2-μ-Pz [dioxime = dmgH, dpgH] shows two cobalt center mixed together due to electron delocalization through pyrazine and behaves like a monocobaloxime and the reduction potentials are much higher than the monocobaloximes.  相似文献   

6.
A novel catalyst system of Pd(OAc)2-HFIP induces double-bond migration of allylbenzenes under mild conditions with low catalytic loading to afford 1-propenylbenzenes. The reaction shows a unique substituent effect that is highly dependent on the distance of substituents from the allylic moiety. Thus, the reactivity of substrates bearing a methyl group is ordered in para > meta > ortho, whereas it is entirely reversed as ortho > meta > para for methoxy and chloro substituents.  相似文献   

7.
A novel conjugation-elongated bis(ethylenedithio)tetraselenafulvalene (BETS) type donor, 2,5-bis(4,5-ethylenedithio-1,3-diselenol-2-ylidene)-2,3,4,5-tetrahydrothiophene (BEDT-HBDST) and its magnetic and non-magnetic anion salts, (BEDT-HBDST)2MX4 (MX4=FeCl4, GaCl4, FeBr4 and GaBr4), were prepared. These four salts are isostructural and belong to the space group of P2/c. They showed semiconducting behavior with small activation energies (59-64 meV). The band structures of these salts are quasi one-dimensional and there is a midgap between the upper band and the lower band, since the degree of dimerization is significant in the stacking direction. The MX4 ions are located between the donor columns and near to the ethylenedithio moieties of the donor molecules. The magnetic susceptibilities of the FeCl4 and FeBr4 salts follow the Curie-Weiss law with Curie constants of 4.6 and 4.8 emu K mol−1 (sum of the spins of S=5/2 and S=1/2) and negative Weiss temperatures of θ=−1.2 and −4.9 K, respectively, revealing a weak antiferromagnetic interaction of 3d spins of the FeCl4 and FeBr4 anions. The Fe?Fe (6.66-7.60 Å), Cl?Cl (4.81-4.82 Å) and Br?Br (4.74-4.77 Å) distances in the crystal structures of these salts are significantly long. Therefore, the direct magnetic interaction between the 3d spins of the nearest neighboring Fe3+ ions appears to be not readily accessible.  相似文献   

8.
Orthorhombic lithium zinc molybdate was first chosen and explored as a candidate for double beta decay experiments with 100Mo. The phase equilibria in the system Li2MoO4-ZnMoO4 were reinvestigated, the intermediate compound Li2Zn2(MoO4)3 of the α-Cu3Fe4(VO4)6 (lyonsite) type was found to be nonstoichiometric: Li2−2xZn2+x(MoO4)3 (0≤x≤0.28) at 600 °C. The eutectic point corresponds to 650 °C and 23 mol% ZnMoO4, the peritectic point is at 885 °C and 67 mol% ZnMoO4. Single crystals of the compound were prepared by spontaneous crystallization from the melts and fluxes. In the structures of four Li2−2xZn2+x(MoO4)3 crystals (x=0; 0.03; 0.21; 0.23), the cationic sites in the face-shared octahedral columns were found to be partially filled and responsible for the compound nonstoichiometry. It was first showed that with increasing the x value and the number of vacancies in M3 site, the average M3-O distance grows and the lithium content in this site decreases almost linearly. Using the low-thermal-gradient Czochralski technique, optically homogeneous large crystals of lithium zinc molybdate were grown and their optical, luminescent and scintillating properties were explored.  相似文献   

9.
D.W Slocum 《Tetrahedron》2003,59(41):8275-8284
The methoxy-substituted aromatic reagents 1,2- and 1,3-dimethoxybenzene (1,2-DMB and 1,3-DMB) and 1,2,4-trimethoxybenzene (1,2,4-TMB) each undergo directed ortho-metalation in high yield in n-BuLi/hydrocarbon media without the aid of a catalyst. These reactions, coined ‘substrate-promoted ortho-metalations’, proceed with the methoxy aromatic substrate functioning as both the directing metalation group (DMG) and as the deoligomerization agent. Evidence that the substrates themselves serve to deoligomerize n-BuLi comes from 13C NMR. The relative extent of metalated product formed as a function of time for each of the three aromatics directly correlates with the substrate's time-dependent ability to coordinate to n-BuLi as measured by 13C NMR. The interpretation of NMR results from experiments involving 1,2,4-TMB is consistent with the metalation proceeding via the activated complex [(1,2,4-TMB)2·(n-BuLi)2]. Finally, conclusions from solubility experiments are that for every substrate-promoted metalation investigated, a precipitate forms in the hydrocarbon solvent, and this precipitate mostly contains the ortho-lithiated aryl intermediate.  相似文献   

10.
For a series of benzaldehydes only with a leaving group or with both a leaving group and a single methoxy substituent 18F-fluorination via nucleophilic aromatic substitution (SNAr) was studied in DMF and Me2SO. In general, the radiochemical yields were clearly higher in DMF than in Me2SO. In the fluorodehalogenation reaction (leaving group: halogen = Br, Cl), extremely low radiochemical yields were observed in Me2SO (<1%). By monitoring labeling reactions using HPLC, oxidation of the aldehyde function of the precursor was detected. Especially, 2-bromobenzaldehyde was oxidized fastest in Me2SO (within 3 min reaction time, 90% of the precursor was consumed; radiochemical yield = 1.0 ± 0.5%); however, in DMF oxidation was always kept at a low level during the entire reaction (<5% of the precursor was oxidized; radiochemical yield = 73.0 ± 0.2%). In DMF, nitrobenzaldehydes with a methoxy substituent (methoxy group in meta-position to the nitro group) were labeled with good radiochemical yields (4-methoxy-2-nitrobenzaldehyde: 87 ± 3%; 2-methoxy-4-nitrobenzaldehyde: 83 ± 3%; 2-methoxy-6-nitrobenzaldehyde: 79 ± 4%) comparable to the non-substituted nitrobenzaldehydes (2-nitrobenzaldehyde: 84 ± 3%; 4-nitrobenzaldehyde: 81 ± 5%). Moreover, for structurally similar compounds, radiochemical yields showed a good correlation with 13C-NMR ppm values of the aromatic carbon atom bearing the leaving group.  相似文献   

11.
The reaction of Os3(CO)12 with an excess of 1-hydroxypyridine-2-thione and Me3NO gives three mononuclear osmium complexes Os(CO)22-SC5H4N(O))2 (1), Os(CO)22-SC5H4N(O))(η2-SC5H4N) (2), and Os(CO)22-SC5H4N)2 (3). The results of single-crystal X-ray analyses reveal that complex 1 contains two O,S-chelate pyridine-2-thione N-oxide (PyOS) ligands, whereas complex 2 contains one O,S-chelate PyOS and one N,S-chelate pyridine-2-thiolate group. The unique structure of 2 provides evidence of the pathway for this transformation. When this reaction was monitored by 1H NMR spectroscopy the triosmium complexes Os3(CO)10(μ-H)(μ-η1-S-C5H4N(O)) (4) and Os3(CO)9(μ-H)(μ-η12-SC5H4N(O)) (5) were identified as intermediates in the formation of the mononuclear final products 1-3. The proposed pathway is further supported by the observation of several dinuclear osmium intermediates by electrospray ionization mass spectrometry. In addition, the reaction of Os3(CO)12 with 1-hydroxypyridine-2-thione in the absence of Me3NO at 90 °C generated mononuclear complex 2 as the major product along with smaller amounts of complexes 1 and 3. These results suggest that the N-oxide facilitates the decarbonylation reaction. Crystal data for 1: monoclinic, space group C2/c, a = 26.9990(5) Å, b = 7.6230(7) Å, c = 14.2980(13) Å, β = 101.620(2)°, V = 2882.4(4) Å3, Z = 8. Crystal data for 2: monoclinic, space group C2/c, a = 5.7884(3) Å, b = 13.9667(7) Å, c = 17.2575(9) Å, β = 96.686(1)°, V = 1385.69(12) Å3, Z = 4.  相似文献   

12.
Lithium insertion in αI-VOPO4 and αII-VOPO4, either by chemical or electrochemical route, leads to the same new compound: αI-LiVOPO4 (space group P4/nmm). The structure, resolved by neutron and synchrotron diffraction, is made up of planes of corner-connected PO4 and VO5 polyhedra, whereas lithium atoms are located between the layers. The reversal of the short vanadyl bond that corresponds to the insertion-induced αII-αI transition finds an explanation in terms of lattice energy. It favors the migration of lithium ions in the (0 0 1) interlayer planes, a key parameter for the electrochemical performance as electrode material in Li-ion batteries.  相似文献   

13.
Deprotonation of a (−)-quinic acid-derived ketone {(2S,3S,4aR,8R,8aS)-8-[(tert-butyl(dimethyl)silyl)oxy]-2,3-dimethoxy-2,3-dimethylhexahydro-1,4-benzodioxin-6(5H)-one} using lithium hexamethyldisilazide (LHMDS) at −78 °C gave one regioisomeric enolate. The regiocontrol is governed by the axial β-silyloxy substituent and the resulting lithium enolate is stable towards β-elimination at temperatures up to −40 °C. It was found that the axial β-silyloxy group could be conveniently eliminated using 2.1 equiv of LHMDS at 0 °C for 1 h and that an equatorial β-alkoxy group was much more resistant to β-elimination. A chiral lithium amide base was used to overturn the inherent regioselectivity of ketone deprotonation with LHMDS.  相似文献   

14.
A new zinc(II) complex of the mycobactericidal drug isoniazid (complex 1) was synthesized and characterized by XRD, vibrational spectroscopy (IR, Raman) and thermogravimetric analysis. The complex is constituted by two isoniazid (INH) molecules, six hydration water molecules and two perchlorate counter-ions for each metal center (C12H26N6Cl2O16Zn). Zinc(II) adopts a distorted octahedral geometry, where two INH molecules coordinate in a bidentate manner through the hydrazide group (N, O) and the other two isoniazid residues complete the coordination sphere of zinc(II) through their aromatic nitrogen atoms. This coordination pattern gives rise to a 2-D coordination polymer. Complex 1 belongs to the monoclinic system [a = 8.1190(2) Å, b = 17.977(4) Å, c = 9.1051(2) Å and β = 100.87(3)°], space group P21. A biological assay with Artemia salina was also performed. Complex 1 is almost 8.5 times more active than the free ligand. Its toxicity against A. salina correlates well with the cytotoxic activity for some human solid tumors. Therefore, antitumoral properties could be expected from complex 1.  相似文献   

15.
A series of imidzoalium salt, L · HCl, for the potentially bidentate pyrazole/N-heterocyclic carbene was synthesized. Reactions of a 2:1 mixture between L · HCl bearing bulky N-substitution and Ag2O produced Ag(L)Cl, whereas a novel compound with unique stoichiometry AgL2(AgCl)0.5Cl was produced from L · HCl bearing N-methyl group under identical condition. Reactions of L · HCl with PdCl2 produced zwitterionic PdIICl3L · H. Selected structural determinations on L · HCl, Ag(L)Cl, AgL2(AgCl)0.5Cl, and PdIICl3L · H revealed intriguing crystal chemistry in which the less-stable gauche rotamers were obtained exclusively. A preliminary application of the zwitterionic complexes, PdIICl3L · H, in Heck coupling reaction of aryl bromide with n-butyl acrylate shows effective activity.  相似文献   

16.
In this study the development, validation and application of a new chromatographic method for the determination of glutathione (GSH) in wine samples is presented. The separation of the GSH was carried out using a sulfobetaine-based hydrophilic interaction chromatography (HILIC) analytical column whereas its detection was carried out spectrofluorimetrically (λext/λem = 340/455 nm) after post-column derivatization with o-phthalaldehyde. GSH was separated efficiently from matrix endogenous compounds of wines by using a mobile phase of 15 mmol L−1 CH3COONH4 (pH = 2.5)/CH3CN, 35/65% (v/v). The parameters of the post-column reaction (pH, amount concentration of the reagent and buffer solution, flow rate, length of the reaction coil) were investigated. The linear determination range for GSH was 0.25–5.0 μmol L−1 and the LOD was 19 nmol L−1. No matrix effect was observed, while the accuracy was evaluated with recovery experiments and was ranged between 89% and 108%.  相似文献   

17.
Manuela Kim 《Talanta》2007,72(3):1054-1058
A simple and sensitive HPLC post-derivatization method with colorimetric detection has been developed for the determination of N-nitroso glyphosate in samples of technical glyphosate. Separation of the analyte was accomplished using an anionic exchange resin (2.50 mm × 4.00 mm i.d., 15 μm particle size, functional group: quaternary ammonium salt) with Na2SO4 0.0075 M (pH 11.5) (flow rate: 1.0 mL min−1) as mobile phase. After separation, the eluate was derivatized with a colorimetric reagent containing sulfanilamide 0.3% (w/v), [N-(1-naphtil)ethilendiamine] 0.03% (w/v) and HCl 4.5 M in a thermostatized bath at 95 °C. Detection was performed at 546 nm. All stages of the analytical procedure were optimized taking into account the concept of analytical minimalism: less operation times and costs; lower sample, reagents and energy consumption and minimal waste. The limit of detection (k = 3) calculated for 10 blank replicates was 0.04 mg L−1 (0.8 mg kg−1) in the solid sample which is lower than the maximum tolerable accepted by the Food and Agriculture Organization of the United Nations.  相似文献   

18.
Single-component molecular conductors [M(tmdt)2] (tmdt = trimethylenetetrathiafulvalenedithiolate; M = Ni, Au, Pt, Cu), exhibit a variety of electromagnetic properties, which originate from the differences of the metal’s d-orbitals role in the band structure formation. The [Au(tmdt)2] crystal undergoes an antiferromagnetic transition at 110 K, while maintaining a metallic state at lower temperatures. The Au analog has a high magnetic transition temperature as compared to traditional magnetic molecular conductors due to the strong three-dimensional (3-D) structure and the contribution of the metal d-orbitals. The single-component molecular conductor, [Cu(tmdt)2], with π- and d-like frontier orbitals is isostructural with other metallic [M(tmdt)2] systems (M = Ni, Pt, Au). The Cu(tmdt)2 molecule is planar, which strikingly contrasts the tetrahedral coordination of Cu(dmdt)2 (dmdt = dimethyltetrathiafulvalenedithiolate) with similarly extended TTF type ligands. Interestingly, unlike other [M(tmdt)2] with metallic behavior, [Cu(tmdt)2] shows semiconducting behavior at room temperature (σ(RT) = ∼7 S cm−1). The RT conductivity increased linearly with increased pressure to 110 S cm−1 at 15 kbar despite the compressed pellet sample. The magnetic susceptibility indicates one-dimensional (1-D) Heisenberg behavior with J = 117 cm−1 and shows antiferromagnetic ordering at 13 K. The [Cu(tmdt)2] is a new multi-frontier π-d system, which introduces a d(σ)-type frontier orbital around the Fermi level of the π-like metal bands.  相似文献   

19.
cis-(η5-MeC5H4)W(CO)2P(OiPr)3I (1) was converted to the trans isomer 2 in the solid state (90-110 °C). The reaction was monitored by heating 1 in NMR tubes for periods of time (2-60 min), cooling the tubes to room temperature and determining the conversion by solution 31P and 1H NMR spectroscopy. The data were consistent with a first-order reaction and yielded an activation energy of 59 ± 3 kJ mol−1. Comparative kinetic data were obtained from an in situ analysis of a powder-XRD study of 1. The powder-XRD study was conducted at 80-100 °C (10-60 min), yielding an activation energy of 52 ± 2 kJ mol−1 (first-order reaction). The reaction could not be monitored by single crystal X-ray diffraction as the crystal disintegrated over time on heating. This disintegration process was monitored by optical microscopy and revealed that while the bulk crystal morphology was retained the crystal surface roughened with time. The compounds 1 and 2 were also structurally characterised by X-ray crystallographic techniques.  相似文献   

20.
A-site substituted cerium orthovanadates, Ce1−xSrxVO4, were synthesised by solid-state reactions. It was found that the solid solution limit in Ce1−xSrxVO4 is at x=0.175. The crystal structure was analysed by X-ray diffraction and it exhibits a tetragonal zircon structure of space group I41/amd (1 4 1) with a=7.3670 (3) and c=6.4894 (1) Å for Ce0.825Sr0.175VO4. The UV-vis absorption spectra indicated that the compounds have band gaps at room temperature in the range 4.5-4.6 eV. Conductivity measurements were performed for the first time up to the strontium solid solution limit in air and in dry 5% H2/Ar with conductivity values at 600 °C ranging from 0.3 to 30 mS cm−1 in air to 30-45 mS cm−1 in reduced atmosphere. Sample Ce0.825Sr0.175VO4 is redox stable at a temperature below 600 °C although the conductivity is not high enough to be used as an electrode for solid oxide fuel cells.  相似文献   

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