The synthesis of [2,3,4-C3]glycitein

Glycitein is one of the soy isoflavones which have attracted considerable interest in recent years due to their possible beneficial effects on human health. However, glycitein has been much less studied than other members of this family due to the lack of good methods for its synthesis. Herein we report a short high yielding synthesis of a multiply ¹³C-labelled glycitein derivative, [2,3,4-¹³C₃]glycitein, which has been employed as an internal standard in LC–MS analysis. A key feature is a rapid and efficient synthesis of 2,4-dihydroxy-5-methoxy-[1′,2′-¹³C₂]acetophenone via acetylation of isovanillin with [¹³C₂]acetyl chloride followed by a Baeyer–Villiger reaction, selective hydrolysis and finally a BF₃ catalysed Fries rearrangement. An aldol reaction using 4-benzyloxy-[carbonyl-¹³C]benzaldehyde gave a chalcone and then thallium(III) mediated oxidative rearrangement, deprotection and cyclisation provided the [2,3,4-¹³C₃]glycitein. The overall yield for the 8 step reaction sequence, based on [¹³C₂]acetyl chloride, was 57%.     

Hydrothermal synthesis, crystal structure, and characterization of a new pseudo-two-dimensional uranyl oxyfluoride, [N(C2H5)4]2[(UO2)4(OH2)3F10]

A new uranyl oxyfluoride, [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] has been synthesized by a hydrothermal reaction technique using (C₂H₅)₄NBr, UO₂(OCOCH₃)₂·2H₂O, and HF as reagents. The structure of [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] has been determined by a single-crystal X-ray diffraction technique. [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] crystallizes in the monoclinic space group P2₁/n (No. 14), with , , , β=98.88(3)°, , and Z=4. [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] reveals a novel pseudo-two-dimensional crystal structure that is composed of UO₂F₅, UO₃F₄, and UO₄F₃ pentagonal bipyramids. Each uranyl pentagonal bipyramid shares edges and corners through F atoms to form a six-membered ring. The rings are further interconnected to generate infinite strips running along the b-axis. [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] has been further characterized by elemental analysis, bond valence calculations, Infrared and Raman spectroscopy, and thermogravimetric analysis.     

FeCo2(CO)7(μ3-S)(O[P(SCH2)2]2)的合成与晶体结构

许多化学工作者对单齿膦配体（ＰＰｈ３,ＰＢｕｎ３,ＰＥｔ２Ｐｈ,Ｐ（ＯＥｔ）３,Ｐ（ＯＣ６Ｈ５）３）与母体簇合物ＦｅＣｏ２（ＣＯ）９（μ３－Ｓ）的取代反应进行过详细研究［１－３］,但对双齿膦配体与母体簇合物的取代反应研究报导较少．Ａｉｍｅ［４］合成了含双齿膦配体的簇合物ＦｅＣｏ２（ＣＯ）７（μ３－Ｓ）（Ｐｈ２ＰＣＨ２ＰＰｈ２）,并用１３ＣＮＭＲ和ＩＲ光谱方法对其结构进行了表征．到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导．ＲｏｓａｎｎａＲｏｓｓｅｔｔｉ［２］通过研究母体簇合物与…     

Synthesis and X-ray crystallographic structures of [HGa(NMe2)2]2 and [PhGa(NHNMe2)2]2, and room-temperature conversions of [HGa(NMe2)2]2 to (HGaNH)n and (HGaNMe)n

The reactivity of bis(dimethylamido) complexes of phenyl- and hydridogallium with ammonia, dimethylamine and 1,1-dimethylhydrazine is described. Synthesis of the starting gallium hydride, [HGa(NMe₂)₂]₂, was achieved in nearly quantitative yield from the reaction of HGaCl₂(quinuclidine) with LiNMe₂. In neat ammonia or methylamine at room temperature both dimethylamido ligands in [HGa(NMe₂)₂]₂ were substituted by a single equivalent of NH₃ or MeNH₂ to produce amorphous (HGaNH)_n or (HGaNMe)_n, respectively. In contrast, the reaction of [PhGa(NMe₂)₂]₂ with neat Me₂NNH₂, at room temperature consumed two equivalents of the substituted hydrazine to form [PhGa(NHNMe₂)₂]₂ in a 73% yield. Single crystal X-ray crystallographic analyses of [HGa(NMe₂)₂]₂ and [PhGa(NHNMe₂)₂]₂ establish that in the solid state both compounds adopt a cyclic Ga-N-Ga-N structure with a crystallographic center of symmetry located at the center of the ring.     

Platination of [3-X-7,8-Ph2-7,8-nido-C2B9H8] (X=Et, F): Synthesis and characterisation of slipped and 1,2→1,7 isomerised products

The reaction of the labelled carborane ligand [3-Et-7,8-Ph₂-7,8-nido-C₂B₉H₈]²⁻ with a source of {Pt(PMe₂Ph)₂}²⁺ affords non-isomerised 1,2-Ph₂-3,3-(PMe₂Ph)₂-6-Et-3,1,2-closo-PtC₂B₉H₈ (1). The analogous reaction between [3-F-7,8-Ph₂-7,8-nido-C₂B₉H₈]²⁻ and {Pt(PMe₂Ph)₂}²⁺ yields 1,8-Ph₂-2,2-(PMe₂Ph)₂-4-F-2,1,8-closo-PtC₂B₉H₈ (3). Compound 1 has a heavily slipped structure (Δ 0.72 Å), which to some degree obviates the need for C atom isomerisation. However, that it is a kinetic product of the reaction is evident from the fact that it reverts to isomerised 1,8-Ph₂-2,2-(PMe₂Ph)₂-4-Et-2,1,8-closo-PtC₂B₉H₈ (2) slowly at room temperature but more rapidly with gentle warming. The heteroatom and labelled-B atom positions in the isomerised compounds 2 and 3 may be explained most simply by the rotation of a CB₂ face of an intermediate based on the structure of 1. Compounds 1–3 were characterised by a combination of spectroscopic and crystallographic techniques.     

In[NC5H3(CO2)2](OH2)F: A new layered indium-organic framework material (NC5H3(CO2)2=2,6-pyridinedicarboxylate)

A new layered indium-organic framework material, In[NC₅H₃(CO₂)₂](OH₂)F has been synthesized by a hydrothermal reaction using In₂O₃, NH₄F, 2,6-NC₅H₃(CO₂H)₂ (2,6-pyridinedicarboxylic acid), HF, and water at 200 °C. Single-crystal X-ray diffraction was used to determine the structure of the reported material. In[NC₅H₃(CO₂)₂](OH₂)F has a novel layered structure consisting of InO₅NF polyhedra and the pyridinedicarboxylate organic linker. Detailed structural analyses with full characterization including infrared spectrum, thermogravimetric analysis, elemental analysis, exchange reactions for the coordinated water molecule, and gas adsorption experiments are reported.     

New binuclear vanadium(III) and (IV) squarate species: synthesis, structure and characterization of [V(OH)(H2O)2(C4O4)]2·2H2O and (NH4)[(VO)2(OH)(C4O4)2(H2O)3]·3H2O

Two new vanadium squarates have been synthesized, characterized by infrared and thermal behavior and their structures determined by single crystal X-ray diffraction. Both structures are made of discrete, binuclear vanadium entity but in 1, [V(OH)(H₂O)₂(C₄O₄)]₂·2H₂O the vanadium atom is trivalent and the entity is neutral while in 2, (NH₄)[(VO)₂(OH)(C₄O₄)₂(H₂O)₃]·3H₂O, the vanadium atom is tetravalent and the entity is negatively charged, balanced by the presence of one ammonium ion. Both molecular anions are bridged by two terminal μ₂ squarate ligands. 1 crystallizes in the triclinic system, space group P-1, with lattice constants a=7.5112(10) Å, b=7.5603(8) Å, c=8.2185(8) Å, α=106.904(8)°, β=94.510(10)°, γ=113.984(9)° while 2 crystallizes in the monoclinic system, space group C2/c, with a=14.9340(15) Å, b=6.4900(9) Å, c=17.9590(19) Å and β=97.927(12)°. From the magnetic point of view, V(III) binuclear species show ferromagnetic interactions at low temperatures. However, no anomalies pointing to magnetic ordering are observed down to 2 K.     

First chemical synthesis of triglucosylated tetradecasaccharide (Glc3Man9GlcNAc2), a common precursor of asparagine-linked oligosaccharides

Triglucosylated high-mannose-type tetradecasaccharide (Glc₃Man₉GlcNAc₂), the oligosaccharide part of the donor substrate of oligosaccharyl transferase (OST) complex, and diglucosylated tridecasaccharide (Glc₂Man₉GlcNAc₂) were synthesized. These oligosaccharides were assembled in a convergent and stereoselective manner. Undecasaccharide 5 was employed as the common intermediate, and coupling with trisaccharide (4) and disaccharide (3) donor afforded fully protected tetradeca-(17) and tridecasaccharide (16), respectively. These oligosaccharides were deprotected to give Glc₃Man₉GlcNAc₂ and Glc₂Man₉GlcNAc₂, respectively.     

[H3N(CH2)4NH3]2[Al4(C2O4)(H2PO4)2(PO4)4]·4[H2O]: A new layered aluminum phosphate-oxalate

A new layered inorganic-organic hybrid aluminum phosphate-oxalate [H₃N(CH₂)₄NH₃]₂[Al₄(C₂O₄)(H₂PO₄)₂(PO₄)₄]·4[H₂O](AlPO-CJ25) has been synthesized hydrothermally, by using 1,4-diaminobutane (DAB) as structure-directing agent. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by IR, ³¹P MAS NMR, TG-DTA as well as compositional analyses. Crystal data: the triclinic space group P-1, a=8.0484(7) Å, b=8.8608(8) Å, c=13.2224(11) Å, α=80.830(6)°, β=74.965(5)°, γ=78.782(6)°, Z=2, R_1[I>2σ(I)]=0.0511 and wR_{2(all data)}=0.1423. The alternation of AlO₄ tetrahedra and PO₄ tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO₆ octahedra to form the layered structure with 4,6-net sheet. Interestingly, oxalate ions are bis-bidentately bonded by participating in the coordination of AlO₆, and bridging the adjacent AlO₆ octahedra. The layers are held with each other through strong H-bondings between the terminal oxygens. The organic ammonium cations and water molecules are located in the large cavities between the interlayer regions.     

Synthesis and structure of ansa-cyclopentadienyl pyrrolyl titanium complexes: [(η-C5H4)CH2(2-C4H3N)]Ti(NMe2)2 and [1,3-{CH2(2-C4H3N)}2(η-C5H3)]Ti(NMe2)

Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C₅H₅)CH₂(2-C₄H₃NH) (2) with Ti(NMe₂)₄ affords bis(dimethylamido)titanium complex [(η⁵-C₅H₄)CH₂(2-C₄H₃N)]Ti(NMe₂)₂ (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH₂(2-C₄H₃NH)}₂C₅H₄ (4), undergoes an analogous reaction with Ti(NMe₂)₄ to give [1,3-{CH₂(2-C₄H₃N)}₂(η⁵-C₅H₃)]Ti(NMe₂) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies.     

A convenient route to carbon-substituted derivatives of nido-5,6-C2B8H12

An alternative route to the parent nido-5,6-C₂B₈H₁₂ dicarbaborane is reported together with a convenient synthesis of its carbon-substituted derivatives. The method is based on reactions between 4-(Me₂S)-arachno-B₉H₁₃ and alkynes R¹R²C₂ (where R¹R²=H,H; Me, Me; Ph,H, and Ph,Ph) in toluene at reflux. The characteristic reaction mode is a dicarbon insertion into the 9-vertex arachno cluster to produce a series of the 5,6-R¹R²-nido-5,6-C₂B₈H₁₀ species combined with concomitant elimination of one {BH} vertex. The products were characterised by high-field ¹H and ¹¹B NMR spectroscopy and mass spectrometry associated with [¹¹B–¹¹B]-COSY and ¹H{¹¹B(selective)} measurements that permitted complete assignments of all resonances to individual cluster {BH} units.     

Synthesis and Anti-inflammatory Action of （η-C5H5 ）2Ti（ Sal）2 and （η-C5H5 ）2Ti（Clo）2

IntroductionSince K pf[1]discovered that dicyclopenta die-nyltitanium dichloride possesses antitumour action in1979,a large number of cyclopentadienyltitanium com-plexes with different substituents have been synthe-sized[2,3].The experimental data reveal …     

Photoinitiated reactions of (η-C5H5)2MH3 (M  Nb,Ta) with Mn2(CO)10: structure of (η-C5H5)2(CO)Ta(μ-H)Mn2(CO)9

The photoreaction of (η-C₅H₅)₂TaH₃ with Mn₂(CO)₁₀ gives, inter alia, (η-C₅H₅)₂(CO)Ta(μ-H)Mn₂(CO)₉, whose crystal structure reveals an open, bent trimetallic framework. Preliminary mechanistic studies show that this and the analogous niobium reaction proceed via a complex sequence of thermal steps following photoinitiation.     

Darstellung,struktur und eigenschaften des dreikernigen titankomplexes (π-C2H5)2TiClOTi(π-C5H5)ClOTiCl(π-C5H5)2·CHCl3

The trinuclear titanium(IV) complex (π-C₅H₅)₂TiClOTi(π-C₅H₅)ClOTiCl(π-C₅H₅)₂ · CHCl₃ is formed by hydrolysis of (π-C₅H₅)₂TiCl₂ at pH > 3.5 and can be isolated in the crystalline state from the reaction of (π-C₅H₅)₂TiCl₂ with Ag₂O and water in chloroform. Its structure is determined by X-ray analysis.     

Synthesis of functional derivatives of the [3,3′-Co(1,2-C2B9H11)2] anion

A series of various functional derivatives of the cobalt bis(1,2-dicarbollide) anion [8-XCH₂CH₂OCH₂CH₂O-3,3′-Co(1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)]⁻ (X=OH, NH₂, and CH(NH₂)COOH) were prepared by the ring-opening reactions of [8-O(CH₂CH₂)₂O-3,3′-Co(1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)] with different nucleophiles followed by functional group interconversion reactions. Acidic hydrolysis of [8-NCCH₂CH₂OCH₂CH₂O-3,3′-Co(1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)]⁻ resulted in the shorter-chain alcohol [8-HOCH₂CH₂O-3,3′-Co(1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)]⁻. Structures of (Bu₄N)[8-AcNHC(COOEt)₂CH₂CH₂OCH₂CH₂O-3,3′-Co(1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)] and [8-(1-C₅H₅N)CH₂CH₂OCH₂CH₂O-3,3′-Co(1,2-C₂B₉H₁₀)(1′,2′-C₂B₉H₁₁)] were determined by the single crystal X-ray diffraction method. Perspectives of application of functionalized cobalt bis(1,2-dicarbolide) derivatives in nuclear medicine are discussed.     

Synthesis and crystal and molecular structure of CdPhen( iso -C4H9OCS2)2 and CdPhen( n -C4H9OCS2)2 mixed-ligand complexes

Mixed-ligand complexes CdPhen(i-BuOCS₂)₂ (I) and CdPhen(n-BuOCS₂)₂ (II) have been synthesized. Their structures were solved using X-ray diffraction data (X8 APEX diffractometer, MoK _α radiation, 1641 and 2497 F _hkl , R = 0.0359 and 0.0389). Crystals I are orthorhombic with unit cell parameters a = 6.5883(3) Å, b = 19.7123(10) Å, c = 20.1936(11) Å, V = 2622.6(2) ų; Z = 4, space group Pbcn; crystals II are monoclinic, a = 6.5845(2) Å, b = 19.1522(6) Å, c = 20.7091(7) Å, β = 97.106(1), V = 2591.5(1) ų, Z = 4, space group C2/c. The structures consist of discrete mononuclear molecules in which the coordination polyhedron of the Cd atom is a distorted N₂S₄ octahedron. Molecular packing and interactions in the structures are discussed. Original Russian Text Copyright ? 2007 by R. F. Klevtsova, T. G. Leonova, L. A. Glinskaya, and S. V. Larionov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 2, pp. 274–281, March–April, 2007.     

An electrochemical study of (η-C5H5)2Ti(NCS)2

The reduction of titanocene dithiocyanate in various solvents has been examined using the techniques of polarography, voltammetry, controlled potential electrolysis and cyclic voltammetry. In THF and CH₂Cl₂, Cp₂Ti(NCS)₂ undergoes successive one-electron transfer reactions, and by using a combination of electrochemical and EPR techniques it has been possible to confirm the stability of [Cp₂Ti(NCS)₂]^? in these solvents. In DMF, however, an irreversible dimerization follows the first electron transfer.     

Synthesis and characterization of ionic organotin compounds [R2SnCl2(2-quin)](HNEt3) and crystal structures of [(2,4-Cl2-C6H3CH2)2SnCl2(2-quin)](HNEt3)

Eight ionic organotin compounds [R₂SnCl₂(2-quin)]⁻(HNEt₃)⁺ have been synthesized by reactions of 2-quinH with R₂SnCl₂ (R = PhCH₂1, 2-Cl-C₆H₄CH₂2, 4-Cl-C₆H₄CH₂3, 2-F-C₆H₄CH₂4, 4-F-C₆H₄CH₂5, 4-CN-C₆H₄CH₂6, Ph 7, 2,4-Cl₂-C₆H₃CH₂8) in the presence of organic base NEt₃, and their structures have been characterized by elemental analysis, IR and multinuclear NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. The structure of [(2,4-Cl₂-C₆H₃CH₂)₂SnCl₂(2-quin)]⁻(NEt₃)⁺ (8) has been determined by X-ray diffraction study. Studies show that compound 8 has a monomeric structure with the central tin atom six-coordinate in a distorted octahedral configuration and the nitrogen atoms of the 2-quin ligands are coordinating to the tin atom in all the eight compounds.     

Synthesis of [3,4,8-C3]daidzein

The biological effects of the soy isoflavones have attracted considerable interest in recent years leading to numerous studies on dietary intake and epidemiology. Such studies require accurate and reproducible analytical methods. Herein we report the first synthesis of a multiply ¹³C-labelled daidzein derivative, [3,4,8-¹³C₃]daidzein, which has been employed as an internal standard in LC-MS and GC-MS analysis. The synthesis includes an improved three-step method for the synthesis of [2-¹³C]resorcinol as one building block.     

Layered metal phosphonates containing pyridyl groups: Syntheses and characterization of Mn2(2-C5H4NPO3)2(H2O) and Zn(6-Me-2-C5H4NPO3)

This paper reports the syntheses and characterization of two phosphonate compounds with layered structures, namely, Mn₂(2-C₅H₄NPO₃)₂(H₂O) (1) and Zn(6-Me-2-C₅H₄NPO₃) (2). In compound 1, double chains are found in which the {Mn₂O₂} dimers are linked by both aqua and O-P-O bridges. These double chains are connected through corner-sharing of {MnO₅N} octahedra and {CPO₃} tetrahedra, forming an inorganic layer. The pyridyl groups fill the inter-layer spaces. In compound 2, each {ZnO₃N} tetrahedron is vertex-shared with three {CPO₃} tetrahedra and vice versa, hence forming an inorganic honeycomb layer. The pyridyl groups reside between the layers. Magnetic studies show that weak antiferromagnetic interactions are mediated between the manganese ions in compound 1. Crystal data for 1: monoclinic, space group C2/c, , , , β=107.3(1)°. For 2: orthorhombic, space group Pbca, , , .