Structure and physical properties of 1D magnetic chalcogenide, jamesonite (FePb4Sb6S14)

Monoclinic FePb(4)Sb(6)S(14) phase, jamesonite, which is a candidate material as a S = 2 Haldane compound, has been synthesized by the direct reaction of elements under dry conditions with sealed evacuated quartz tubes. The congruent melting point was determined at 592 degrees C by DTA measurements. Shiny metallic gray needle crystals grow on the surface of bulk heated at 550 degrees C. The elongated direction of each needle crystal is parallel to the c-axis. The crystal structure refinement (P2(1)/a, a = 15.750(6) A, b = 19.125(3) A, c = 4.030(4) A, beta = 91.68(8) degrees, V = 1213(1) A(3), Z = 2, D(c) = 5.651 g/cm(3), R(1) = 3.16%) reveals the presence of two rod substructures elongated parallel to the c-axis. One is the lozenge-shaped Bi(2)Te(3)-type (or called SnS archetype), [Pb(4)Sb(6)S(13)]. The other is the novel single magnetic one-dimensional (1D) straight chain, [FeS(6)]. This compound shows intrinsic semiconductor behavior in the electric conductivity measurements. The optical band gap, 0.48 eV, is estimated by near-IR diffuse reflectance measurements. In the magnetic susceptibility measurements, this compound shows 1D-Heisenberg antiferromagnetic behavior with a broad peak at approximately 33.5 K, where Fe(2+) takes the high-spin state, t(2g)(4)e(g)(2). A possibility for the S = 2 Haldane system is discussed.     

d-生物素的不对称全合成研究(Ⅴ)

以二异丁基氢化铝使(3aS,6aR)-1,3-二苄基-四氢-4H-噻吩并[3,4-d]-咪唑-2,4(1H)-二酮(1)高立体选择性地还原成(3aS,4S,6aR)-1,3-二苄基-4-羟基-四氢-1H-噻吩并[3,4-d]-咪唑-2(3H)-酮(2),再经缩合,Witting烯化成(3aS,6aR)-1,3-二苄基-四氢-1H-噻吩并[3,4-d]咪唑-2(3)-酮-4-烯戊酸(4),后者经催化氢转移还原、脱苄即得d-生物素,以化合物1计算总产率为42%.     

A cytotoxic and apoptosis-inducing sesquiterpenoid isolated from the aerial parts of Artemisia princeps PAMPANINI (Sajabalssuk)

Repeated silica gel and octadecyl silica gel (ODS) column chromatography of the aerial parts of Artemisia princeps PAMPANINI (Sajabalssuk) led to the isolation of a new sesquiterpenoid, 3-((S)-2-methylbutyryloxy)-costu-1(10),4(5)-dien-12,6 alpha-olide (2), along with two previously reported sesquiterpenoids: 8 alpha-angeloyloxy-3beta,4 beta-epoxy-6 beta H,7 alpha H,8 beta H-guaia-1(10),11(13)-dien-12,6 alpha-olide (1, carlaolide B) and 3beta,4 beta-epoxy-8 alpha-isobutyryloxy-6 beta H,7 alpha H,8 beta H-guaia-1(10),11(13)-dien-12,6 alpha-olide (3, carlaolide A). The structure of compound 2 was elucidated by spectroscopic data analysis, including one dimensional (1D) and two dimensional (2D) nuclear magnetic resonance (NMR) experiments. Of the isolates, compound 2 exhibited potent cytotoxicity against human cervix adenocarcinoma cells and induced apoptosis.     

Isolation of a novel flavanone 6-glucoside from the flowers of Carthamus tinctorium (Honghua) by high-speed counter-current chromatography

A novel flavanone glycoside, (2S)-4',5,6,7-tetrahydroxyflavavone 6-O-beta-D-glucopyranoside was isolated from the ethyl acetate extract of the flowers of Carthamus tinctorium by high-speed counter-current chromatography (HSCCC). Using an optimized two-phase solvent system composed of ethyl acetate-methanol-water (5:1:5, v/v), target compound (52 mg) with purity of 98.0% was obtained from 2.0 g of sample by HSCCC in seven times run. The structure of the target compound was elucidated by means of spectroscopic methods including IR, MS, 1D and 2D NMR techniques.     

Synthesis and Crystal Structure ofα-Mo_4 X S_3( μ-dtp)_3(dtp)_3( X= 0 .6S + 0 .4O)

１　ＩＮＴＲＯＤＵＣＴＩＯＮＯｗｉｎｇｔｏｔｈｅｉｒｐｏｓｓｉｂｌｅｉｍｐｏｒｔａｎｔｒｏｌｅｓｉｎｌｉｆｅｐｒｏｃｅｓｓｅｓ,ｃｕｂａｎｅｔｙｐｅｔｅｔｒａｎｕｃｌｅａｒｍｏｌｙｂｄｅｎｕｍｃｌｕｓｔｅｒｓｈａｖｅｂｅｅｎｅｘｔｅｎｓｉｖｅｌｙｅｘｐｌｏｒｅｄｄｕｒｉｎｇｔｈｅｐａｓｔｔｗｏｄｅｃａｄｅｓ,ｏｆｗｈｉｃｈｔｈｅｃｌｕｓｔｅｒｃｏｍｐｏｕｎｄｓｔｈａｔｃｏｎｔａｉｎ〔Ｍｏ４ＸＳ３〕（Ｘ＝ＳｏｒＯ）ｃｏｒｅｈａｖｅａｔｔｒａｃｔｅｄｓｐｅｃｉａｌａｔｔｅｎｔｉｏｎ〔１７〕．Ａｓｐ…     

New 3',8'-linked biflavonoids from Selaginella uncinata displaying protective effect against anoxia

Seven 3',8'-linked bioflavonoids, including one new compound, (2'S)-2', 3'-dihydroamentoflavone-4'-methyl ether and six known compounds: (2S)-2,3- dihydroamentoflavone-4'-methyl ether, (2S,2'S)-2,3,2',3'-tetrahydroamento- flavone-4'-methyl ether, (2S,2'S)-tetrahydroamentoflavone, (2S)-2,3-dihydro- amentoflavone and (2'S)-2',3'-dihydroamentoflavone (6) and amentoflavone, were isolated from the 60% ethanolic extract of Selaginella uncinata (Desv.) Spring. The structures of these compounds were elucidated mainly by analysis of their 1D and 2D NMR spectroscopic data, and their absolute configurations were determined by circular-dichroism (CD) spectroscopy. All the seven compounds showed protective effect against anoxia in the anoxic PC12 cells assay, in which compound 6 displayed particularly potent activity.     

Role of the NH2 functionality and solvent in terdentate CNN alkoxide ruthenium complexes for the fast transfer hydrogenation of ketones in 2-propanol

The reaction of [RuCl(CNN)(dppb)] (1; HCNN=6-(4-methylphenyl)-2-pyridylmethylamine) with NaOiPr in 2-propanol/C6D6 affords the alcohol adduct alkoxide [Ru(OiPr)(CNN)(dppb)].n iPrOH (5), containing the Ru-NH2 linkage. The alkoxide [Ru(OiPr)(CNN)(dppb)] (4) is formed by treatment of the hydride [Ru(H)(CNN)(dppb)] (2) with acetone in C6D6. Complex 5 in 2-propanol/C6D6 equilibrates quickly with hydride 2 and acetone with an exchange rate of (5.4+/-0.2) s(-1) at 25 degrees C, higher than that found between 4 and 2 ((2.9+/-0.4) s(-1)). This fast process, involving a beta-hydrogen elimination versus ketone insertion into the Ru-H bond, occurs within a hydrogen-bonding network favored by the Ru-NH2 motif. The cationic alcohol complex [Ru(CNN)(dppb)(iPrOH)](BAr(f)4) (6; Ar(f)=3,5-C6H3(CF3)2), obtained from 1, Na[BAr(f)4], and 2-propanol, reacts with NaOiPr to afford 5. Complex 5 reacts with either 4,4'-difluorobenzophenone through hydride 2 or with 4,4'-difluorobenzhydrol through protonation, affording the alkoxide [Ru(OCH(4-C6H4F)2)(CNN)(dppb)] (7) in 90 and 85 % yield of the isolated product. The chiral CNN-ruthenium compound [RuCl(CNN)((S,S)-Skewphos)] (8), obtained by the reaction of [RuCl2(PPh3)3] with (S,S)-Skewphos and orthometalation of HCNN in the presence of NEt3, is a highly active catalyst for the enantioselective transfer hydrogenation of methylaryl ketones (turnover frequencies (TOFs) of up to 1.4 x 10(6) h(-1) at reflux were obtained) with up to 89% ee. Also the ketone CF3CO(4-C6H4F), containing the strong electron-withdrawing CF3 group, is reduced to the R alcohol with 64% ee and a TOF of 1.5 x 10(4) h(-1). The chiral alkoxide [Ru(OiPr)(CNN)((S,S)-Skewphos)]n iPrOH (9), obtained from 8 and NaOiPr in the presence of 2-propanol, reacts with CF3CO(4-C6H4F) to afford a mixture of the diastereomer alkoxides [Ru(OCH(CF3)(4-C6H4F))(CNN)((S,S)-Skewphos)] (10/11; 74% yield) with 67% de. This value is very close to the enantiomeric excess of the alcohol (R)-CF3CH(OH)(4-C6H4F) formed in catalysis, thus suggesting that diastereoisomeric alkoxides with the Ru-NH2 linkage are key species in the catalytic asymmetric transfer hydrogenation reaction.     

Dinuclear Copper（Ⅱ） Complex with a New Polycarboxylate Ligand：Syntheses,Characterization and Crystal Structure

A dinuclear copper(Ⅱ) complex,[Cu2(HL)2(H2O)6] 1(H3L = 2,4,6-tri(3-carboxy-phenylthio)-1,3,5-triazine),was synthesized hydrothermally and characterized by single-crystal X-ray diffraction,IR and thermal analysis.Single-crystal X-ray diffraction reveals that complex 1 is a dinuclear copper(Ⅱ) complex,which is further extended to a 3D network by weak interactions such as O…H-O hydrogen bonds and noncovalent S...S interactions.The crystal of compound 1 belongs to monoclinic,space group C2/c,with a = 50.15(2),b = 6.789(3),c =15.667(8) ,β = 90.588(9)o,V = 5334(4) 3,Z = 4,C48H38Cu2N6O18S6,Mr = 1306.28,Dc = 1.627 g/cm3,F(000) = 2664,Rint = 0.0631,T = 293(2) K,μ = 1.112 mm-1,the final R = 0.0661 and wR = 0.1850 for 3782 observed reflections with I > 2σ(I).     

One new diphenylmethane glycoside from the leaves of Psidium guajava L

To investigate the chemical constituents of Psidium guajava L, the EtOH/H(2)O extract of the fresh leaves was subjected to various chromatography. One diphenylmethane, one benzophenone, and eight flavonoids were isolated and elucidated as 2,6-dihydroxy-3-formaldehyde-5-methyl-4-O-(6″-O-galloyl-β-D-glucopyranosyl)-diphenylmethane (1), 2,6-dihydroxy-3,5-dimethyl-4-O-(6″-O-galloyl-β-D-glucopyranosyl)-benzophenone (2), kaempferol (3), quercetin (4), quercitrin (5), isoquercitrin (6), guaijaverin (7), avicularin (8), hyperoside (9), reynoutrin (10) by spectroscopic methods, including 1D and 2D NMR and HR-ESI-MS spectrometry as well as by comparison with published data. Compounds 5 and 10 are obtained from P. guajava for the first time, and compound 1 is a new diphenylmethane compound.     

Solvothermal syntheses, crystal structures, and thermal properties of new manganese thioantimonates(III): The first example of the thermal transformation of an amine-rich thioantimonate into an amine-poorer thioantimonate

Two new neutral thioantimonates(III) were first prepared by the reaction of elemental manganese, antimony, and sulfur in tren (tren = tris(2-aminoethyl)amine, C6H18N4) at 140 degrees C. In the amine-rich compound [Mn(tren)]2Sb2S5 (1) the trigonal SbS3 pyramids are connected via common corners (S(3)) into the tetradentate [Sb2S4]4- anion. Four S atoms have bonds to the manganese atoms of the [Mn(tren)2+] cations. A special structural feature is the large Sb-S(3)-Sb(a) angle of 134 degrees. Density functional calculations clearly demonstrate that this large angle results from the steric interactions between the two Mn(tren) subunits. In the crystal structure of the amine-poorer compound [Mn(tren)]2Mn2Sb4S10 (2), MnS4 tetrahedra and SbS3 pyramids are linked via common corners and edges to form a new heterometallic [Mn2Sb4S10] core. The [Mn(C6H18N4)2+] cations are located at the periphery of the core and are bound to the [Mn2Sb4S10] unit via two S atoms. The thermal behavior of both compounds was investigated using simultaneous thermogravimetry (TG), differential thermoanalysis, and mass spectroscopy. The amine-richer compound 1 decomposes in three steps upon heating. After the first TG step an intermediate phase is formed, which was identified as the amine-poorer compound 2 by X-ray diffraction. Reaction of compound 2 at 140 degrees C with an excess of tren forms the amine-rich compound 1.     

Biotransformation of isoflavones by the larvae of the common cutworm (Spodoptera litura)

Biotransformation of the 5,7,4'-trimethoxyisoflavone (1), 6,7,4'-trimethoxyisoflavone (2), and 7,4'-dimethoxyisoflavone (3) by insects, Spodoptera litura was investigated. Compound 1 was transformed to 5-hydroxy-7,4'-dimethoxyisoflavone (4), 7-hydroxy-5,4'-dimethoxyisoflavone (5) and 4'-hydroxy-5,7-dimethoxyisoflavone (6) by S. litura. Compounds 2 and 3 were hardly metabolized by S. litura. This suggested that compound 1 was converted to compounds 4, 5 and 6 by demethylation at the C-5, C-7 and C-4' position, respectively.     

A New Phenylpropanoid Glycoside from Dragon's Blood of Dracaena cambodiana

A new phenylpropanoid glycoside, named cambodianin F(1), together with three known compounds, 1-O-β-D-glucopyranosyl-2-hydroxy-4-allylbenzene(2), 1-O-(6-O-α-L-rhamnopyranosyl-β-D-glucopyranosyl)-2-hydroxy-4-allylbenzene(3) and 1,2-di-O-β-D-glucopyranosyl-4-allylbenzene(4) was isolated from the dragon's blood of Dracaena cambodiana. The new compound was elucidated by HR-ESI-MS and spectroscopic techniques(UV, IR, 1D and 2D NMR).     

Synthesis,Crystal Structure and Luminescence of a Novel Cadmium（Ⅱ） Coordination Polymer with 5-Connected nov Net

A novel interesting coordination polymer,[Cd(HSSA)(2-bimb)2].3H2O(1,H3SSA = 5-sulfosalicylic acid,2-bimb = 1,2-bis(imidazol-1-ylmethyl)-benzene),has been synthesized and structurally characterized.Compound 1 crystallizes in the monoclinic system,space group P21/n with a = 10.8653(10),b = 19.4100(17),c = 17.4414(17) ,β = 91.944(2)°,V = 3676.2(6) 3,Z = 4,C35H38CdN8O9S,Mr = 859.19,Dc = 1.552 g/cm3,μ = 0.717 mm-1,S = 0.999,F(000) = 1760,R = 0.0531 and wR = 0.1078.The compound features a rare three-dimensional(3D) 5-connected nov topology.In addition,compound 1 exhibits strong photoluminescent emission at room temperature.     

Magneto-structural correlations in dinuclear Mn(III) compounds with formula [{Mn(L)(NN)}(μ-O)(μ-2-RC6H4COO)2{Mn(L')(NN)}]n+

Three dinuclear Mn(III) compounds with oxo and carboxylato bridges have been synthesized and characterized by X-ray diffraction: [{Mn(L)(NN)}(μ-2-ClC(6)H(4)COO)(2)(μ-O){Mn(L')(NN)}](n+) with NN = 2,2'-bipyridine (1 and 2) or 1,10-phenanthroline (3). The counteranion is either NO(3)(-) (1 and 3) or ClO(4)(-) (2) and the monodentate positions (L, L') could be occupied by molecules of water or the counteranion. For compound 1, L = H(2)O and L' = NO(3)(-); compound 2 shows two different dinuclear units and L and L' could be H(2)O or ClO(4)(-), and for compound 3 both monodentate positions are occupied by nitrate anions. The magnetic properties of the three compounds have been analyzed using the Hamiltonian H = -JS(1)·S(2). Compound 1 exhibits a dominant ferromagnetic behavior, with J = 3.0 cm(-1), |D(Mn)| = 1.79 cm(-1), |E(Mn)| = 0.60 cm(-1) with intermolecular interactions zJ' = -0.18 cm(-1). Due to the anisotropy of the Mn(III) ions, the ground state S = 4 shows ZFS with |D(4)| = 0.58 cm(-1). Compounds 2 and 3 show antiferromagnetic couplings, with J = -10.9 and -0.3 cm(-1), respectively. The magnetic interaction in this kind of compound depends on several structural factors. In the present work, the distortion around manganese ions, the torsion angle between the phenyl ring and the carboxylate group and the relative disposition of the coordination octahedra have been analyzed.     

Isolation and biological activity of new and known isolation and biological activity of new and known diterpenoids from Sideritis stricta Boiss. & Heldr

Nine known and one new ent-kaurene diterpenoid were isolated from the acetone extract of Sideritis stricta Boiss & Heldr. The new compound, identified as ent-1 beta-hydroxy-7 alpha-acetyl-15 beta,16 beta-epoxykaurane (1) by IR, 1D and 2D NMR techniques and mass spectra, was isolated along with sideroxol (2), 7-acetyl sideroxol (3), 7-epicandicandiol (4), linearol (5), ent-7 alpha,15 beta,18-trihydroxy-kaur-16-ene (6), ent-7 alpha-acetyl,15,18-dihydroxy-kaur-16-ene (7), foliol (8), sideridiol (9) and siderol (10). The antibacterial and antifungal activities of these compounds and the whole crude acetone extract were evaluated against E. coli, S. aureus, K. pneumeonia and C. albicans.     

Syntheses and Crystal Structures of Molybdenum-Sulfur Clusters Mo_3S_4 (dtp)_3(o-CH_3OC_6H_4COO)(Py) and Mo_3S_4 (dtp)_3(p-HOC_6H_4COO)(DMF)·EtOH

1 INTRODUCTION Recent years have seen a drastic increase of compounds containing the Mo3S4 core. A major synthetic route to these compounds is by the reaction of the aqua ion [Mo3S4(H2O)9]4+ with different kinds of ligands replacing some or all of the water molecules. In this way, Mo3S4(dtp)4(H2O), which was synthesized by the spontaneous- assembly method in 1986[1] and its structural characterization and chemical reactivity have been well recognized [2], can be rationally synthesize…     

Patavine, a new arylnaphthalene lignan glycoside from shoot cultures of Haplophyllum patavinum

A new arylnaphthalene lignan glycoside, patavine (1), together with five known lignans, justicidin B (2), diphyllin (3), tuberculatin (4), majidine (5), and arabelline (6) were isolated from shoot cultures of Haplophyllum patavinum. The structure of the new compound was elucidated by extensive one-dimensional (1D) and two-dimensional (2D) NMR experiments and mass spectrometry. The cytotoxicity of compounds 1, and 3-6 against LoVo human colon carcinoma cells was investigated.     

Antioxidant xanthones from Cratoxylum cochinchinense

A new xanthone named cratoxylumxanthone A (1), together with five known compounds: dulcisxanthone B (2), alpha-mangostin (3), beta-mangostin (4), 2-geranyl-1,3,7-trihydroxy-4-(3-methylbut-2-enyl)xanthone (5) and tectochrystin (6), was isolated from Cratoxylum cochinchinense stems. The structure of new compound was characterized by 1D and 2D NMR techniques. The isolated compounds showed free radical scavenging against DPPH and lipid peroxidation inhibition.     

Synthesis and Structure of Dinuclear Molybdenum Carbonyl Thiolate Compound 〔Et_4N〕_2〔Mo_2(CO)_8(SC_6H_4-OCH_3-p)_2〕

１　ＩＮＴＲＯＤＵＣＴＩＯＮＩｎｏｕｒｅｆｆｏｒｔｓｔｏｄｅｖｅｌｏｐｔｈｅｌｏｗ－ｖａｌｅｎｃｅＭｏ－ＳＲｃｏｍｐｏｕｎｄｓ,ｗｅｈａｖｅｆｏｕｎｄａｎＭｏ（０）－ｃｏｍｐｏｕｎｄ,〔Ｍｏ２（ＳＲ）２（ＣＯ）８〕２－,ｗｈｉｃｈｉｓｏｂｔａｉｎｅｄｆｒｏｍｔｈｅｒｅａｃｔｉｏｎｏｆＭｏ（ＣＯ）６ｗｉｔｈＲＳ－ｉｎｈｉｇｈｙｉｅｌｄ,ｐｏｓｓｅｓｓｅｓａｎｉｎｔｅｒｅｓｔｉｎｇｔｗｏ－ｅｌｅｃｔｒｏｎｔｒａｎｓｆｅｒｐｒｏｐｅｒｔｙ．Ｎｕｍｅｒｏｕｓｋｉｎｄｓｏｆｄｉｎｕｃｌｅａｒｍｏｌｙｂｄｅ…     

Puckered-boat conformation hexameric water clusters stabilized in a 2D metal-organic framework structure built from CuII and 1,2,4,5-benzenetetracarboxylic acid

1,2,4,5-Benzenetetracarboxylic acid (btcH(4)) reacts with Cu(NO(3))(2).6H(2)O to form 2D coordination polymeric structure [[Cu(2)(btc)(Py)(4).2H(2)O].4H(2)O](n), 1, in the presence of pyridine from water at room temperature. Puckered-boat-shaped hexameric water clusters resulting from four free water molecules and two water molecules coordinating to metal ions join these sheets to make a 3D network. These water clusters behave as pillars to join those sheets which is the key factor stabilizing the 3D network. Thermal analysis, X-ray powder diffraction, and X-ray structure analysis have been used to characterize this compound. Crystal data for 1 follow: triclinic space group P1, a = 8.905(3) A, b = 11.137(4) A, c = 17.484(2) A, alpha = 82.342(6) degrees, beta = 81.312(3) degrees, gamma = 82.361(4) degrees V= 1687.5(1)A(3), Z = 2, R1 = 0.0331, wR2 = 0.0886, S =1.066.