A Novel Entry into a New Class of Spiro Heterocyclic Framework: A Facile Synthesis of Dispiro[oxindole-1,2,3,4-tetrahydro-naphthalen-1-one]pyrrolidines and Spiro[1,2,3,4-tetrahydro-naphthalen-1-one]pyrrolidines

Abstract

2-Arylidene-1,2,3,4-tetrahydro-naphthalen-1-ones undergo regioselective 1,3-dipolar cycloaddition reaction with the azomethine ylide derived from isatin and sarcosine by decarboxylative route affording a series of 1-N-methyl-spiro[2.3¹]oxindole-spiro[3.2¹¹]1¹¹, 2¹¹,3¹¹,4¹¹, -tetrahydro-naphthalen-1¹¹-one-4-aryl-pyrrolidines. 2-Arylidene-1,2,3,4-tetrahydro-naphthalen-1-ones also undergo cycloaddition reaction with azomethine ylide derived from paraformaldehyde and sarcosine affording a series of 1-N-methyl-spiro[3.2¹]1¹,2¹,3¹,4¹-tetrahydro-naphthalen-1¹-one-4-aryl-pyrrolidines. The structures of the compounds were established by spectroscopic techniques.     

Synthetic [FeFe]-H2ase models bearing phosphino thioether chelating ligands

Through the oxidation-reduction combination procedure, the neutral tri-substituted {2Fe3S} complex 2 was synthesized by replacing the CO ligand in 1 with phosphine. This substitution leads to the Fe-Fe bonds in 1 and 2 with large Lewis basicity difference, i.e. △pK_a^MeCN~10.     

Reactions of 3,10-epoxycyclo[10.2.2.0.0]hexadeca-4,6,8,13-tetraene: a new intramolecular 1,5-oxygen migration

Bromination of 3,10-epoxycyclo[10.2.2.0^2,11.0^4,9]hexadeca-4,6,8,13-tetraene gave 13-bromo-11-oxapentacyclo[8.7.0.0^2,4.0^12,17]heptadeca-4,6,8-triene-3-ol, 12-bromo-1,2,3,4-tetrahydro-1,4-ethano-antracen-11-ol, 13-hydroxy-3,14-dibromotetracyclo[10.2.2.0^2,11.0^4,9]hexadeca-2,4,6,8,10-pentaene, and 13-hydroxy-3,10,14-tribromotetracyclo[10.2.2.0^2,11.0^4,9]hexadeca-2,4,6,8,10-pentaene by cleavage of the carbon–oxygen bonds and intramolecular 1,5-migration of the oxygen atom of 1,4-epoxide. Reactions of epoxide 14,18-dioxahexacyclo[10.3.2.1^3,10.0^2,11.0^4,9.0^13,15]octadeca-4,6,8-triene obtained from 3,10-epoxycyclo[10.2.2.0^2,11.0^4,9]hexadeca-4,6,8,13-tetraene gave also similar products, in acidic media. Compound 3,10-epoxycyclo[10.2.2.0^2,11.0^4,9]hexadeca-4,6,8,13-tetraene was converted into tetracyclo[10.2.2.0^2,11.0^4,9]hexadeca-2(11),3,9-triene in two ways. The reactions, especially intramolecular oxygen migration, are discussed.     

Involvement of unusual noncovalent interactions in the self-assembly of cucurbit[6]uril with[CdCl4]2- anions

The [CdCl_4]~(2-) anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of the structure inducer in Q[n] systems, we report herein the self-assembly of Q[6] solely in the presence of[CdCl_4]~(2-)anions and in the presence of both a linear cationic organic guest and [CdCl_4]~(2-)anions. X-ray diffraction analysis revealed that 1D Q[6] porous channels were formed by the noncovalent interactions between Q[6] and [CdCl_4]~(2-)anions, but the ‘‘honeycomb effect' was not observed in the present study.However, it seems that the ‘‘honeycomb effect' and the self-assembly of Q[6] with [CdCl_4]~(2-)anions can be significantly modified and switched in the presence of a linear cationic dibutylamine guest through some unusual noncovalent interactions.     

Synthesis and structure of a novel molybdenum imido calix[6]arene

Treatment of p-tert-butylcalix[6]areneH₆ (H₆L) with [Mo(OBu^t)₂{[2,2′-(N)-C₆H₄]₂(CH₂CH₂)}] in refluxing toluene affords, after work-up, the complex [Mo(2-NC₆H₄CH₂CH₂C₆H₄NHC(Me)NH-2^/)LH₂]·4MeCN (1), which contains an 11-membered metallocyclic ring as characterised by Synchrotron X-radiation.     

Synthesis and insecticidal evaluation of tetrahydroimidazo[1,2-a]pyridin-5(1H)-one derivatives

A series of novel tetrahydroimidazo[1,2-a]pyridine-5(1H)-one derivatives containing a electronegative pharmacophore(=CNO₂) were synthesized via practical aza-ene reaction and characterized by ¹H NMR, ¹³C NMR, ¹⁹F NMR and HRMS. Preliminary bioassays showed that some of the target compounds exhibited good insecticidal activity against brown planthopper(Nilaparvata lugens) and cowpea aphids(Aphis craccivora) at 500 mg L^-1. Among them, compound 11h was active against brown planthopper at 100 mg L^-1. The insecticidal activities varied significantly depending on the types and patterns of the substituents, which provided guidance for further investigation on structure modifications.     

Design and Synthesis of Calix[4] arene-Constrained Cyclopeptide

There have been great continuing interests in cyclic peptides in the past two decades. Apart from being useful tools for identifying the functional conformations of bioactive peptides, and guiding the rational design of peptidomimetic drugs, cyclic peptides serve as templates in the de novo design^[1] of artificial proteins and as models^[2] for the study of prepefence in protein secondary structure. They also play an important role in ion transport across biological membranes,^[3] and can self-assemble size-adjustable nanotubes.^[4] However, study on their molecular recognitions for ions^[5] and neutral molecules, especially for organic compounds,^[6,7] which are believed to be one of the most attractive properties, were hampered by their considerable large degree of the freedom of the cavities.     

Halide abstraction as a route to cationic molybdenum(IV) compounds: Crystal and molecular structure of [CpMoCI(MeCN)4][SbCl6]2 · MeCN

Treatment of CpMoC1₃(MeCN)₂ with SbCl₅ in acetonitrile solution provides the solvated cationic series [CpMoCl₂(MeCN)₃]⁺, [CpMoCl(MeCN)₄]²⁺ and [CpMo(MeCN)₆]³⁺ as hexachloroantimon(V)ate salts following sequential halide abstraction. Characterization follows from microanalytical and spectroscopic (IR, and ¹H NMR) data and, in the case of [CpMoCl(MeCN)₄][SbCl₆]₂ · MeCN, by X-ray crystallographic studies. The structure is disordered but individual cations contain a six coordinated pseudo-octahedral metal geometry in which the cyclopentadienyl ligand (regarded as unidentate) and the chlorine atom occupy axial positions with an equatorial array of four acetonitrile ligands.     

Copper thioether chemistry: Synthesis and X-ray crystal structures of binuclear copper(I) complexes [Cu2(L)] {L = [24]aneS8, [28]aneS8} incorporating octathia macrocycles

Reaction of L {L = [24]aneS₈, [28]aneS₈} with two molar equivalents of [Cu(NCMe)₄]X (X⁻ = ClO₄⁻, BF₄⁻, PF₆⁻) in MeCN affords the white binuclear copper(I) complexes [Cu₂(L)]²⁺. A single crystal X-ray structure determination of [CU₂([24]aneS₈)](BF₄)₂ shows two tetrahedral copper(I) centres, each of which is coordinated to four thioether sulphur-donors, Cu---S(1) = 2.263(3), Cu---S(4) = 2.363(3), Cu---S(7) = 2.349(3), Cu---S(10) = 2.261(3) Å. The Cu … Cu distance is 5.172(3) Å. A single crystal X-ray structure determination Of [CU₂([28]aneS₈)](ClO₄)₂ shows that this complex also contain two tetrahedral copper(I) centres, each coordinated to four thioether sulphur-donors, Cu---S(1) = 2.278(5), Cu---S(4) = 2.333(5), Cu---S(8) = 2.328(5), CU---S(11) = 2.268(5) Å. The Cu … Cu distance of 6.454(3) Å is greater than in [CU₂([24]aneS₈)]²⁺ , reflecting the greater cavity size in [CU₂([28]aneS₈)]²⁺. Cyclic voltammetry of [CU₂([24]aneS₈)]²⁺ and [CU₂([28]aneS₈)]²⁺ at platinum electrodes in MeCN (0.1 M ⁿBU₄NPF₆) shows irreversible oxidations at E_pa, = +0.88 V, +0.92 V vs Fc/Fc⁺, respectively, at a scan rate of 200 mV s⁻¹. Coulometric measurements in MeCN confirm these oxidations to be two-electron (one electron per copper) processes to give binuclear copper(II) species. Oxidation of the binuclear copper(I) precursors with H₂SO₄ or HNO₃ affords ESR-active copper(II) species which presumably incorporate SO₄²⁻ and NO₃⁻ bridges.     

1,3,2-Diazastanna-[3]ferrocenophanes bearing alkyn-1-yl groups at tin and their 1,1-organoboration with triethylborane—molecular structure of a novel spirotin compound

2,2-Dichloro-1,3-bis(trimethylsilyl)-1,3,2-diazastanna-[3]ferrocenophane (3) reacts with lithium alkynides LiCCR¹ to give the corresponding di(alkyn-1-yl)tin derivatives 4a (R¹=^tBu) and 4b (R¹=SiMe₃). 1,1-Organoboration of 4 with triethylborane affords the spirotin compounds 5 which contain both a ferrocenophane and a stannacyclopentadiene ring. The crystal structure of 5b was determined by X-ray analysis. The compounds 4 and 5 were characterised in solution by multinuclear magnetic resonance (¹H-, ¹¹B-, ¹³C-, ¹⁵N-, ²⁹Si-, ¹¹⁹Sn-NMR), using pulsed field gradients in HMBC experiments for the ¹H detected ¹⁵N- and ¹¹⁹Sn-NMR signals. The compound 5b was also studied by solid-state ¹³C, ²⁹Si and ¹¹⁹Sn MAS NMR in order to correlate liquid and solid-state NMR data with the structural evidence.     

[NHN] and [OHO] hydrogen bonding in the adduct of 1,8-bis(dimethylamino)naphthalene (DMAN) with 1,8-dihydroxy-2,4-dinitronaphthalene (DHDNN)

X-Ray diffraction, IR and ¹H NMR studies were performed on the 1:1 adduct of 1,8-bis(dimethylamino)naphthalene (DMAN) with 1,8-dihydroxy-2,4-dinitronaphthalene (DHDNN). The adduct crystallizes in the triclinic system, space group , a = 9.911(2) Å, b = 11.212(2) Å, c = 11.194(2) Å, = 68.95(2)°, β = 79.72(2)°, γ = 73.78(2)°, Z = 2. Both [NHN]⁺ and [OHO]⁻ hydrogen bonds formed in the ion pairs are asymmetrical with lengths equal to 2.574(2) Å and 2.466(4) Å respectively. The [NHN]⁺ bridge shows a typical behaviour in the IR spectrum, i.e. a low-frequency absorption between 300 and 700 cm⁻¹. The coupling of [OHO]⁻ hydrogen bonds with the naphthalene π-electron system is so strong that no absorption related to the proton stretching vibrations can be detected in the high- and low-frequency regions. The ¹H NMR chemical shifts for the [NHN]⁺ and [OHO]⁻ bridge protons of 18.63 and 15.81 ppm respectively confirm the strong hydrogen bonds.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Theoretical study of tricyclo[3,3,1,1]decane, tricyclo[3,3,1,1]decsilane molecules and their halogen derivatives, C10H12X4 and Si10H12X4 (X=F, Cl, Br, I)

The B3LYP/3-21G* ab initio molecular orbital method from the program package was applied to study tricyclo[3,3,1,1^3,7]decane and tricyclo[3,3,1,1^3,7]decsilane molecules and their halogen derivatives (1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane, C₁₀H₁₂X₄ and Si₁₀H₁₂X₄ respectively). The optimized structures of these compounds were obtained. Ionization potentials, HOMO and LUMO energies, energy gaps, heats of formation, atomization energies and vibration frequencies were calculated. The calculations indicate that these molecules are stable and have T_d symmetry. Tricyclo[3,3,1,1^3,7]decsilane and its halogen derivatives (Si₁₀H₁₂X₄) are found to have higher conductivity than tricyclo[3,3,1,1^3,7]decane and its halogen derivatives (C₁₀H₁₂X₄). 1,3,5,7-Tetrafluorotricyclo[3,3,1,1^3,7]decane (C₁₀H₁₂F₄) and 1,3,5,7-tetrafluorotricyclo[3,3,1,1^3,7]decsilane (Si₁₀H₁₂F₄) were found to be the easiest compounds to form and the most difficult to dissociate of all 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane compounds, respectively.     

邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性能研究

杯芳烃是继冠醚、环糊精之后的第三代主体分子[1].据文献[2,3]报道,在杯[4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对Na+有很高的选择性,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对Na+的配位,而且配位基团所形成的包络空间大小与钠离子相匹配.一般认为,随着包络空间改变,对金属离子的识别作用会有所变化[4].但目前对这方面的工作并没有给予更多的重视.我们发现,用2-溴甲基苯甲酸甲酯与杯[4]芳烃反应,得到了一种新的四取代杯[4]芳烃衍生物[2]萃取研究结果表明,该化合物对钾离子有较好的选择性.此外,在合成该衍生物的过程中,还得到了另一新的二取代衍生物(3).     

溶液中杯[4]芳烃双冠-6与Cs~+配位化学研究

研究了溶液中杯[4]芳烃双冠-6(BisC₆)与Cs⁺配位行为.常温下,BisC₆/NPME(邻硝基苯甲醚)体系单级萃铯百分率达99.36%,模拟料液中,Cs⁺/Na⁺和Cs⁺/K²⁺分离系数分别为3.92×10⁴和2.21×10⁴.局域结构模型实验表明,配合物分子中可能存在水或(和)硝酸(根).ESI-MS谱表明,NPME体系中,铯离子与BisC₆同时形成1:1(单核)和2:1(双核)的配合物,并且存在[BisC₆·H₂O],[BisC₆·Cs⁺]⁺,[BisC₆·2Cs⁺·H₂O]₂+和[BisC₆·2Cs₁₀⁺·No₁₀^-3]10⁺等多种配合物分子.EXAFS实验表明,溶液中铯离子的配位数为7,形成7个氧配位的稳定结构,ADF计算验证了EXAFS实验结果.     

Das Reaktionsverhalten von Cp2NbCl2 gegenüber WF6—Struktur von [Cp2NbCl2]4[WF6]2[WCl6]

The oxidation of Cp₂NbCl₂ with pure WF₆ in SO₂ solution yielded the cationic metallocene species [Cp₂NbCl₂]⁺[WF₆]⁻ essentially in quantitative yield. The same reaction carried out in the presence of either equimolar amounts or a two-fold excess of HCN led to the preparation of the new niobocenium salt [Cp₂NbCl₂]₄⁺[WF₆]²⁻ which was studied by single crystal X-ray diffraction. This compound represents the first example of a structurally characterized metallocene-WF₆⁻ complex, and crystallizes in the tetragonal system: space group, P4₁2₁2(No. 92), a = 11.083(8) Å, c = 48.285 (9) Å; Z = 8; R = 0.0759, R_W = 0.0841. ab]Die Oxidation von Cp₂NbCl₂ mit reinem WF₆ führt in SO₂-Lösung zur Synthese von [Cp₂NbCl₂ ]⁺[WF₆]⁻ in nahezu quantitativer Ausbeute. Die analoge Reaktion führt unter Anwesenheit der äquimolaren Menge oder eines zweifachen Überschusses an HCN zur Ausbildung des Niobocenium-Komplexsalzes [Cp₂NbCl₂]₄⁺ [WF₆]₂⁻[WCl₆]²⁻, von dem eine Röntgenstrukturanalyse angefertigt wurde. Diese Verbindung repräsentiert den ersten structurell charakterisierten Vertreter eines Metallocen-WF₆⁻-Komplexes und kristallisiert im tetragonalen System: Raumgruppe P4₁2₁2 (Nr. 92), a = 11.083(8) Å, c = 48.285(9) Å; Z = 8; R = 0.0759, R_W = 0.0841. kw]Niobium; X-ray diffraction; Oxidation; Metallocenes     

Synthesis of tricyclo[6.2.2.0]dpdecane and tricyclo[6.3.1.0]dodecane ring systems involving intramolecular cyclisation of diazomethyl ketones

2,8-Dimethyltricyclo[6.2.2.0^1,6]dodeca-2,5-diene-4,9-dione ( ), 2,9-dimethyltricyclo [6.3.1.0^1,6]dodeca-2,5-diene-4,10-dione ( ) and 2-methyltricyclo[6.3.1.0^1,6]dodeca-2,5-diene-4,10-dione ( ) have been synthesised for entry into the ring systems of a few tetracyclic diterpenes.     

Temperature-dependent structural changes of[Bmim]FeCl4 magnetic ionic liquid characterized by an in-situ X-ray absorption fine structure

The temperature-dependent structural changes in 1-butyl-3-methylimidazolium tetrafluoride([Bmim]FeCl4)magnetic ionic liquid(MIL)were investigated by using in-situ X-ray absorption fine structure(XAFS)combined with Raman spectroscopy and DFT calculations.XAFS re sults revealed that the coordination number and bond length of Fe-Cl in the anion of[Bmim]FeCl4 MIL decreased with increments in temperature.These results directly reflected the dissociation of tetrahedral structure[FeCl4]^-,and the formation of bridge-chain[Fe2 Cl5]^+,and[FeCl2]^+species in the anion of[Bmim]FeCl4 MIL.These behaviors indicated that[FeCl4]^-dissociation was endothermic,and was promoted by increased temperature.The results obtained through XAFS were in agreement with those obtained through Raman spectroscopy and DFT calculations.     

[C3mim][NTf2]/DEC/[Li][NTf2]体系的基础性质

The hydrophobic ionic liquid (IL) 1-propyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C₃mim][NTf₂]) was synthesized according to traditional methods. By adding different amounts of diethyl carbonate (DEC) solvent and lithium bis[(trifluoromethyl)sulfonyl]imide ([Li][NTf₂]) salt to [C₃mim][NTf₂] IL, eight solution systems were prepared. First, the thermodynamic properties of the eight solution systems were characterized by differential scanning calorimetry (DSC). The semi-stable temperature of the system gradually disappeared with increasing lithium salt content, but the melting point temperature was not apparent in the experiment. These results indicate that DEC and lithium salts can dissolve in ILs within the tested temperature range. The basic properties of the eight systems, including thermodynamic and dynamic properties, were systematically studied at different temperatures. The variation in the self-diffusion coefficient of lithium ion ([Li]⁺) as a function of DEC concentration, density changes, viscosity, conductivity, and the viscosity/conductivity activation energy of the eight systems was calculated by the Vogel Fulcher Taman (VFT), Final Vogel Fulcher Taman (FVFT), and Arrhenius equations. The effect of temperature on the properties of the system was studied in detail. Within the temperature range measured herein, the deviation between the fitting equation and experimental value was small. Consequently, these equations were successfully used to calculate the properties of the system at various temperatures. All fitting parameters of the corresponding equations are provided herein. The viscosity for all systems decreased rapidly with increasing temperature, which increased the conductivity. Based on these experiments, the influence of DEC on the system microstructure was discussed in the context of the molecular dynamics simulation results. In particular, the interaction between [Li]⁺ and [NTf₂]^-/DEC was examined. In all solution systems, [NTf₂]^- coordinates to [Li]⁺ through only the O atom and not the N atom. Radial distribution function (RDF) analysis showed that the interaction between [Li]⁺ and [NTf₂]^- weakened with increasing DEC concentration. DEC molecules were observed in the first solvation layer of [Li]⁺ coordinating to [Li]⁺ through the carbonyl O atom. Although the interaction between [Li]⁺ and DEC was weakened, competition between [NTf₂]^- and DEC in the first solvation layer of [Li]⁺ was observed by the coordination number analysis of the O atom around [Li]⁺. Therefore, the introduction of DEC is beneficial for Li⁺ diffusion, which is consistent with the experimental results.     

瓜环与喹啉衍生物包结配合行为研究

利用¹H NMR以及荧光技术研究了六、七、八元瓜环与2-苯基喹啉、N-正丙基溴化异喹啉、3-氨基喹啉及7,8-苯并喹啉的相互作用.两种方法的考察结果均表明,2-苯基喹啉能与这3种瓜环发生相互作用,其中六、七元瓜环与2-苯基喹啉形成1∶1的稳定包结配合物,包结常数分别为1.6×10⁴和3.2×10³L/mol.八元瓜环能与2-苯基喹啉形成1∶2包结物.¹H NMR结果还表明,3种瓜环均能与N-正丙基溴化异喹啉相互作用,其化学计量比均为1∶2;七元瓜环与7,8-苯并喹啉相互作用,化学计量比约为1∶1.荧光法也表明八元瓜环能与N-正丙基溴化异喹啉、3-氨基喹啉及7,8-苯并喹啉发生相互作用,并且荧光强度随瓜环浓度增加而下降,其化学计量比为1∶2.同时,讨论了上述主客体包结配合物的作用模式.