Facile Syntheses of (±)-Curcuphenol, (±)-Curcudiol, (±)-Curcuhydroquinone,and (±)-Curcuquinone

The syntheses of (±)-curcuphenol 1, (±)-curcudiol 2, (±)-curcuhydroquinone 3, and (±)-curcuquinone 4 have been achieved. The key steps involved in the syntheses were the Reformatsky reaction and hydrogenation reaction.     

Total synthesis of (±)-maistemonine, (±)-stemonamide, and (±)-isomaistemonine

A full account of the total synthesis of (±)-maistemonine, (±)-stemonamide, and (±)-isomaistemonine is presented. Two approaches have been developed to construct the basic pyrrolo[1,2-a]azepine core of the Stemona alkaloids, featuring a tandem semipinacol/Schmidt rearrangement of a secondary azide and a highly stereoselectively desymmetrizing intramolecular Schmidt reaction, respectively. To build the common spiro-γ-butyrolactone, a new protocol was carried out by utilizing an intramolecular ketone-ester condensation as the key transformation. The vicinal butyrolactone moiety of (±)-maistemonine was stereoselectively introduced via a one-pot procedure involving the epimerization at C-3 and carbonyl allylation/lactonization. Moreover, (±)-stemonamide was divergently synthesized from a common intermediate, and (±)-isomaistemonine was obtained via the epimerization of (±)-maistemonine at C-12.     

Syntheses, structure, and a Mössbauer and magnetic study of Ba(4)Fe(2)I(5)S(4)

The compound Ba4Fe2I5S4 has been prepared at 1223-1123 K by the "U-assisted" reaction of FeS, BaS, S, and U with BaI2 as a flux. A more rational synthesis was also found; however, the presence of U appears to be essential for the formation of single crystals suitable for X-ray diffraction studies. Ba4Fe2I5S4 crystallizes in a new structure type with two formula units in space group I4/m of the tetragonal system. The structure consists of a Ba-I network penetrated by (1)infinity[Fe2S4] chains. Each Fe atom, which is located on a site with 4 symmetry, is tetrahedrally coordinated to four S atoms. The FeS4 tetrahedra edge-share to form linear (1)infinity[Fe2S4] chains in the [001] direction. The Fe-Fe interatomic distance in these chains is 2.5630(4) A, only about 3% longer than the shortest Fe-Fe distance in -Fe metal. Charge balance dictates that the average formal oxidation state of Fe in these chains is +2.5. The M?ssbauer spectra obtained at 85 and 270 K comprise a single quadrupole doublet that has hyperfine parameters consistent with an average Fe oxidation state of +2.5. The M?ssbauer spectrum obtained at 4.2 K consists of a single magnetic sextet with a small hyperfine field of -15.5 T. This spectrum is also consistent with rapid electron delocalization and an average Fe oxidation state of +2.5. The molar magnetic susceptibility of Ba4Fe2I5S4, obtained between 3.4 and 300 K, qualitatively indicates the presence of weak pseudo-one-dimensional ferromagnetic exchange within a linear chain above 100 K and weak three-dimensional ordering between the chains at lower temperatures.     

184(m,g)Re cross sections and isomeric ratios in181Ta(α, n) and W(α, pxn) reactions

Excitation functions and isomeric ratios for¹⁸⁴Re, from -induced reactions on¹⁸¹Ta and natural W have been measured using the stacked-foil method. The data are compared with the theoretical predictions provided by the equilibrium and pre-equilibrium reaction model; for this propose we used the code INDEX development by ERNST.     

Complexes of Cu(I) and Pd(II) with (+)-camphor and (–)-cavrone thiosemicarbazones: Synthesis,structure, and cytotoxicity of the Pd(II) complex

CuLCl, CuL¹Cl, PdLCl₂, and PdL¹Cl₂ complexes [L and L¹ being (+)-camphor and (–)-carvone thiosemicarbazones, respectively] have been synthesized. The structure of binuclear [Pd₂L²²Cl₄] complex has been determined by means of X-ray diffraction. The L² ligand (dehydrogenated (–)-carvone thiosemicarbazone) is coordinated via the bridging S atom to two Pd atoms. The complexes of Cu(I) and Pd(II) presumably have polynuclear and binuclear structure, respectively. These facts are in good agreement with IR and NMR spectroscopy as well as mass spectrometry data which indicate the coordination of L and L¹ ligands via the S atom. The influence of L¹ and PdL¹Cl₂ on viability of the Hep2 cell line has been studied. The PdL¹Cl₂ complex is more cytotoxic than L¹ ligand.     

Trichloro- and triisopropoxy-niobium(V) and tantalum(V) bis -( O,O ′-alkylene dithiophosphates): synthesis and characterization

Trichloro- and triisopropoxy-niobium(V) and tantalum(V) alkylene dithiophosphates, (M = Nb(V) or Ta(V); G =–CHMeCHMe–,–CMe₂CMe₂–,–CH₂CMe₂CH₂–,–CH₂CEt₂CH₂–or–CMe₂CH₂CHMe–and X = Cl or OPrⁱ) have been synthesized by reaction of metal(V) chloride, MCl₅, or triisopropoxymetal(V) dichloride, (PrⁱO)₃MCl₂, with the sodium salts of O,O′-alkylene dithiophosphoric acids, in 1 : 2 molar ratio in THF under anhydrous conditions. These pink-purple or light-yellow compounds are viscous, semi-solid or solid, hydrolyzable and soluble in common organic solvents. These compounds have been characterized by elemental analyses, molecular weight determinations and spectral studies like IR and heteronuclear NMR (¹H, ¹³C and ³¹P), which indicated a bidentate mode of chelation of dithio ligands, leading to a pentagonal bipyramidal geometry around the niobium(V) or tantalum(V) centers.     

Preparation and polymerization mechanism of dihydroxy-capped PCL,poly(CL-b-PEG-b-CL) and poly(DTC-b-CL-b-DTC)

PCL possesses a wide range of medical applications, such as tissue engineering and controlled drug release, because of its good biodegradability and miscibility. In order to extend the use of PCL, researchers have been exploring its structural and chemica…     

Synthesis and Characterization of Chlorobis(cyclopentadienyl) Titanium(IV) and Zirconium(IV) O,O’-Dialkyl and Alkylene Dithiophosphates

Abstract

Reactions of O,O′-dialkyl and alkylene dithiophosphoric acids with bis (cyclopentadienyl) titanium(IV) and zirconium (IV) dichloride in a 1:1 molar ratio in refluxing benzene proceeds with elimination of HCl and formation of the substituted derivatives, Cp₂MCl[S₂P(OR)₂] (where R = Et, Pr-n, Pr-i, Bu-i and Ph), Cp₂MCl[S₂POGO] (where G = ?CH₂CMe₂CH₂?, ?CH₂CEt₂CH₂? and ?CMe₂CMe₂?), (M = Ti and Zr). The complexes are dark red and yellow solids, soluble in common organic solvents and monomeric in nature. These have been characterized on the basis of elemental analyses, molecular weight determinations, IR, and NMR (¹H, ¹³C, and ³¹P).

GRAPHICAL ABSTRACT      

Spectroscopic,electrocatalytic, and photoelectrochemical characteristics of mixed-ligand bis(β-dicarbonylato) phthalocyanine complexes of zirconium(IV) and hafnium(IV)

The electronic absorption (EAS) and fluorescence spectra and electrocatalytic and photoelectrochemical characteristics of mixed-ligand complexes of zirconium(IV) and hafnium(IV) based on phthalocyanines in solutions and in thin films were investigated. It was established that a significant bathochromic shift of the Q band and redistribution of the intensities in the absorption bands are observed in the electronic absorption spectra. It was shown that films of the synthesized compounds are promising for use as photosensitizers and electrochemical sensors for oxygen in solution. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 133–137, May–June, 2008.     

Nickel(II) and copper(II) – l-cysteine,l-methionine,l-tryptophan-nucleotide ternary complexes

Four new ternary complexes of Cu^II with l-methionine and the nucleotides 5AMP (adenosine 5-phosphate), 5GMP (guanosine 5-phosphate) and 5IMP (inosine 5-phosphate), and with l-tryptophan and 5AMP, were synthesized and characterized by elemental analysis and i.r. spectroscopy. One ternary complex of N^II with l-cysteine and 5IMP was also prepared and characterized. The study of the three ternary compounds of Cu^II, of general formulae Cu-5NMP-l-methionine, indicates coordination of the phosphate group and of N(7) of the purinic ring. l-Methionine is bound by the carboxylic and amino groups. The ternary complex obtained from a mixture of Cu-5AMP and l-tryptophan is a dimer in which the nucleotide bridges the two copper atoms. In the complex of Ni-5IMP and l-cysteine, the nucleotide seems to bind the metal through the N(7) of the heterocyclic ring, and the l-cysteine is coordinated as a bidentate chelate by the carboxyl and thiol groups. E.s.r. spectra of the copper complexes are in good agreement with the low symmetry structure proposed. The one-electron reduction potentials E_c(Fc⁺/Fc) (V) of Cu^II to Cu^I were established for the four copper complexes from cyclic voltammetry studies. The one-electron oxidation potential E_a(Fc⁺/Fc⁺) (V) of Ni^II to Ni^III was also measured for the nickel complex.     

(Dicarbonyl)(π-cyclohexadienyl)iron iodide,trichlorostannate, and tris(cymantrenecarboxylato)stannate: Synthesis and molecular structures

A reaction of [(η⁵-C₆H₇)Fe(CO)₃]BF₄ with KI in acetone gave brown crystals of the complex [(η⁵-C₆H₇)Fe(CO)₂]I (I), which was treated with SnCl₂ in THF to form orange crystals of the complex [(η⁵-C₆H₇)Fe(CO)₂]SnCl₃ (II). A reaction of complex II with potassium cymantrenecarboxylate ((CO)₃MnC₅H₄COOK, or CymCOOK) in THF yielded yellow crystals of the complex [(η⁵-C₆H₇)Fe(CO)₂]Sn(CymCOO)₃ (III). Structures I–III were identified using X-ray diffraction. The fragment (η⁵-C₆H₇)Fe(CO)₂ in complexes I–III remains virtually unchanged. The Fe-I bonds in complex I (2.6407(3) Å) and the Fe-Sn bonds in complexes II and III (2.4854(3) and 2.4787(4) Å, respectively) are appreciably shorter than the sum of the covalent radii of the corresponding elements, probably because of an additional dative interaction of the d electrons of iron with the vacant d orbitals of iodine or tin.     

Synthesis and Crystal Structure of Bis(nitrate)- bis(N,N''''-dimethyl-N,N''''-dibenzenyl-urea)uranyl(Ⅱ)

1 INTRODUCTION Tri-butyl phosphate (TBP) has been widely used as the extraction reagent in U-Th fuel to separate uranium from thorium. But di-butyl phos- phate (DBP) and butyl phosphate (MBP), the radio- lytic products of TBP, exhibit some coordinated ability to the fission elements, such as Zr and Nb. The substitutes for TBP have being studied for several decades[1～4]. The physical and chemical properties of amides are similar to those of TBP and they selectively extract U(Ⅵ…     

μ-Oxo-Bis(Tetraphenylantimony): Synthesis,Structure, and Reactions

Heating of a solution of pentaphenylantimony in toluene in atmospheric oxygen affords -oxo-bis(tetraphenylantimony) (I) in a 63% yield. The latter compound can be converted to bis(tetraphenylantimony) carbonate or phthalate by the action of carbon dioxide or phthalic anhydride, respectively. According to X-ray diffraction data, the antimony atoms in compound Ihave a distorted trigonal-bipyramidal coordination (Sb–O 2.0050(4) Å, the SbOSb angle 151.71(9)°). The molecule of bis(tetraphenylantimony) phthalate is composed of two equal fragments, and its Sb atoms also have trigonal-bipyramidal coordination (Sb–O 2.2421(8) Å; Sb–C 2.176(1), 2.115(1), 2.130(1), and 2.137(1) Å).     

Synthesis,Crystal and Molecular Structure of Mono- and Diaquadi(acetato-O)-Bis(2,4′-Bipyridyl) Copper(II)

The title compound has been synthesized and characterized by elemental analysis and conductivity studies. The crystal and molecular structure has been determined. There are two different types of molecules in the crystal: mono- and diaquadi(acetato-O)-bis(2,4'-bipyridyl) copper (II). Both copper atoms occupy special positions. The copper atoms show almost ideal square pyramidal (4 + 1) and square bipyramidal (4 + 2) coordination. Due to the Jahn-Teller effect, the axial Cu-O(water) bond distances are longer than respective equatorial Cu-O(acetate) bond distances. The bond valences of the copper were computed. An intramolecular strong hydrogen bond linking O(water) and O(acetate) atoms exists in the molecule. The differences of geometrical environment for copper in mono- and diaquadi(acetato-O)-bis(2,4'-bipyridyl) copper(II) are imposed by strong intermolecular hydrogen bonds creating a linear infinite chain structure along crystallographic x axis. Also weak intramolecular hydrogen bonds are present in the molecule.     

Synthesis,crystal structure,thermal decomposition,and XPS studies of homo and heterotrinuclear Cu(II)–Cu(II)–Cu(II) and Cu(II)–Ni(II)–Cu(II) complexes obtained from salpn type ligands

In this study, a mononuclear CuL complex was prepared by the use of bis-N,N′-(salicylidene)-1, 3-propanediamine (LH₂) and Cu²⁺ ion. NiCl₂ and NiBr₂ salt were treated with this complex in dioxanewater medium and two new complexes [(CuL)₂NiCl₂(H₂O)₂] and [(CuL)₂NiBr₂(H₂O)₂)] with Cu(II)–Ni(II)–Cu(II) nucleus structure were obtained. In addition to this bis-N,N′-(2-hydroxybenzyl)-1,3-diaminopropane (L^HH₂) was prepared by the reduction of LH₂ with NaBH₄ in MeOH medium. The treatment of this reduced complex with Cu²⁺ ion resulted a complex [(CuL^H)₂CuCl₂] with a structure of Cu(II)–Cu(II)–Cu(II). The complexes prepared were characterized by the use of elemental analysis, IR spectroscopy, thermogravimetric and X-ray diffraction methods. The crystal structures of [(CuL)₂NiBr₂(H₂O)₂] (СIF file CCDC 1448402) and [(CuL^H)₂CuCl₂] (СIF file CCDC 1448401) complexes were elucidated. It was found that halogen ions are coordinated to terminal Cu²⁺ ions which are in a distorted square pyramid coordination sphere. It was determined that the central Cu(II), which joins terminal square pyramidal Cu(II), was coordinated only by the phenolic oxygens of the ligand while the central Ni(II) was coordinated by two phenolic oxygens of the organic ligand and two water molecules. These complexes were investigated by XPS and it was found that the terminal and central Cu²⁺ ions were different in Cu(II)–Cu(II)–Cu(II) complex. Also, the thermal degradation of the CuLH complex unit was observed to exothermic in contrast to the expectations.

     

Isolation,purification, and characterization of cyclomaltodecaose (ε-CD)

-Cyclodextrin (-CD) is a cyclic oligosaccharide, composed of ten -1,4-linked D-glucoses reported by Frenchet al. in 1965¹⁾, but has not been studied because of the difficulty in the preparation and purification of large-ring CDs composed of more than nine -1,4-linked D-glucose units. This report describes the purification and characterization of -CD. Furthermore, the crystal and molecular structure of -CD hydrate -CD 19H₂O) was elucidated by X-ray analysis.     

Preparation and Characterization of the Solid Inclusion Compounds of α-, β-Cyclodextrin with Phenylalanine (D-, L- and DL-Phe) and Tryptophan (D-, L- and DL-Trp)

The solid cyclodextrin (α-, β-CD) inclusion compounds of phenylalanine (D-, L- and DL-Phe) and tryptophan (D-, L-?and DL-Trp) were prepared and the stoichiometry of host and guest in the supermolecules was determined to be 1:1 based on elemental analyses. β-CD formed inclusion compounds with α-aromatic amino acid (α-AAA) in higher yield in contradistinction to α-CD. The yields of the α- or β-CD inclusion compounds of a pair of optical isomers of chiral aromatic amino acids and their racemic modification decreased in the order L->DL->D-form. The complexation between CD and α-AAA caused a change in shape, location and diffracted intensity of the X-ray diffraction peaks of both host and guest. The decomposition temperature of the inclusion compounds was not only slightly higher than that of a pure host but also remarkably higher than that of a pure guest. Upon inclusion the signals of CD protons inside the cavity shifted to upfield while those of the protons outside the cavity had only smaller changes, and the proton signals of the aromatic ring of guest shifted to a certain extent. The chemical shift changes of 4-H and 5-H located in small end side of cavity were a bit bigger than those of 2-H and 3-H located in large one, suggesting that aromatic ring of a guest molecule within a host cavity might be kept near small end side of?cavity. An ESI-MS experiment has proved the formation and stability of the 1:1 CD inclusion compounds of α-AAA in aqueous solution.     

Phosphato, chromato, and perrhenato complexes of titanium(IV) and zirconium(IV) containing Kläui's tripodal ligand

Treatment of titanyl sulfate in dilute sulfuric acid with 1 equiv of NaL(OEt) (L(OEt)(-) = [(eta(5)-C(5)H(5))Co{P(O)(OEt)(2)](3)](-)) in the presence of Na(3)PO(4) and Na(4)P(2)O(7) led to isolation of [(L(OEt)Ti)(3)(mu-O)(3)(mu(3-)PO(4))] (1) and [(L(OEt)Ti)(2)(mu-O)(mu-P(2)O(7))] (2), respectively. The structure of 1 consists of a Ti(3)O(3) core capped by a mu(3)-phosphato group. In 2, the [P(2)O(7)](4-) ligands binds to the two Ti's in a mu:eta(2),eta(2) fashion. Treatment of titanyl sulfate in dilute sulfuric acid with NaL(OEt) and 1.5 equiv of Na(2)Cr(2)O(7) gave [(L(OEt)Ti)(2)(mu-CrO(4))(3)] (3) that contains two L(OEt)Ti(3+) fragments bridged by three mu-CrO(4)(2-)-O,O' ligands. Complex 3 can act as a 6-electron oxidant and oxidize benzyl alcohol to give ca. 3 equiv of benzaldehyde. Treatment of [L(OEt)Ti(OTf)(3)] (OTf(-) = triflate) with [n-Bu(4)N][ReO(4)] afforded [[L(OEt)Ti(ReO(4))(2)](2)(mu-O)] (4). Treatment of [L(OEt)MF(3)] (M = Ti and Zr) with 3 equiv of [ReO(3)(OSiMe(3))] afforded [L(OEt)Ti(ReO(4))(3)] (5) and [L(OEt)Zr(ReO(4))(3)(H(2)O)] (6), respectively. Treatment of [L(OEt)MF(3)] with 2 equiv of [ReO(3)(OSiMe(3))] afforded [L(OEt)Ti(ReO(4))(2)F] (7) and [[L(OEt)Zr(ReO(4))(2)](2)(mu-F)(2)] (8), respectively, which reacted with Me(3)SiOTf to give [L(OEt)M(ReO(4))(2)(OTf)] (M = Ti (9), Zr (10)). Hydrolysis of [L(OEt)Zr(OTf)(3)] (11) with Na(2)WO(4).xH(2)O and wet CH(2)Cl(2) afforded the hydroxo-bridged complexes [[L(OEt)Zr(H(2)O)](3)(mu-OH)(3)(mu(3)-O)][OTf](4) (12) and [[L(OEt)Zr(H(2)O)(2)](2)(mu-OH)(2)][OTf](4) (13), respectively. The solid-state structures of 1-3, 6, and 11-13 have been established by X-ray crystallography. The L(OEt)Ti(IV) complexes can catalyze oxidation of methyl p-tolyl sulfide with tert-butyl hydroperoxide. The bimetallic Ti/ Re complexes 5 and 9 were found to be more active catalysts for the sulfide oxidation than other Ti(IV) complexes presumably because Re alkylperoxo species are involved as the reactive intermediates.     

Manganese(II) and silver(Ι) complexes based on the V-shaped ligand,bis(2-benzimidazolylmethyl)amine: synthesis,crystal structures,DNA-binding properties,and antioxidant activities

Two Mn(II) and Ag(I) complexes, [Mn(IDB)₂](pic)₂ (pic?=?picrate) (1) and [Ag₂(IDB)₂](pic)₂ (2) (IDB?=?bis(2-benzimidazolylmethyl)amine), have been synthesized and characterized by elemental analysis, IR, UV–vis spectral measurements, and X-ray single-crystal diffraction. Single-crystal X-ray diffraction revealed that Mn(II) is six-coordinate by six nitrogens from two IDB as a distorted octahedron, and the Ag(I) complex revealed two Ag(I) ions bonded to two IDB ligands through six nitrogens, resulting in an asymmetric binuclear structure. The complexes can bind to DNA through an intercalative mode, and the affinity for DNA is stronger for the Mn(II) complex than the Ag(I) complex; the Mn(II) complex exhibits excellent antioxidative activity.