Phosphite Ligand Modified Supported Rhodium Catalyst for Hydroformylation of Internal Olefins to Linear Aldehydes

A phosphite ligand modified heterogeneous catalyst was developed for the hydroformylation of internal olefins to linear aldehydes, which showed a high activity and high regioselectivity and could be separated easily by filtration after reaction in an autoclave. Three nanoporous silica sieves were used to investigate the influence of pore structure and shape selective performance of support on the regioselectivity to the linear products.

Metabolomics Profile of Potato Tubers after Phosphite Treatment

Phosphite (Phi)-based fungicides are used to control the oomycete Phytophthora infestans which causes late blight disease, the most devastating disease in potatoes. In order to examine the effects of Phi-based fungicides on potato tubers through foliar or post-harvest application, a metabolite profiling approach based on gas chromatography coupled to mass spectrometry (GC-MS) has been established. A total of 132 metabolites were detected using the GC-MS approach. Among these, 34 metabolites were identified after normalization and annotated with a compound name with standard mass spectral library. Metabolomic analysis of Phi-treated plants showed significant differences in the levels of many metabolites especially amino acids. Multivariate statistical approaches, such as principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA), were employed to explore the relationships between metabolites to detect group differences. A good discrimination between the control and the Phi-treated plants was observed, which demonstrated that significant changes in the metabolite profile have been caused by the two different Phi applications (foliar or post-harvest). This finding suggests that the alteration of specific metabolite levels by accumulation of Phi can lead to resistance against the pathogen.

Synthesis and Characterization of Two New Organically Templated Open-framework Uranium Phosphites

Two organically templated uranium phosphites, （C4H12N）（UO2）（HPO3）（NO3） （Mr = 486.16） 1 and （C16H36N）2（UO2）2（H2PO3）2（HPO3）（NO3）2 （Mr= 1390.95） 2, were prepared by evaporation from aqueous solution of uranyl nitrate, phosphite acid and their respective organic ammonium hydroxids. Their structures were determined by single-crystal X-ray diffraction and further characterized by infrared and fluorescence spectroscopy. In 1, pentagonal [UO7] bipyramids share comers with three [HPO3]2- tetrahedra and one edge with a [NO3]- anion to form [（UO2）- （HPO3）（NO3）]^- ladder-like chains parallel to the b axis. The structure of 2 is also based upon one-dimensional anionic [（UO2）2（H2PO3）2（HPO3）（NO3）2]2-chains of comer-sharing penta- gonal [UOT] bipyramids with [H2PO3]- and [HPO3] tetrahedra, which is still unknown in structural chemistry of uranium so far. Crystal data for 1： monoclinic, space group C2/m, a = 21.808（7）, b = 6.9605（15）, c = 8.357（2） A, β = 98.327（15）°, V= 1255.2（6） A^3, Z = 4, Dc = 2.573 g/cm^3, F（000） = 888, μ = 13.086 mm^-1 the final R = 0.0418 and wR = 0.0906 （I 〉 2σ（I））; and those for 2： monoclinic, space group C2/c, a = 36.4549（8）, b = 14.5296（11）, c = 20.8253（11） A, β = 101.7440（8）°, V= 10799.7（10） A3, Z = 8, Dc= 1.711 g/cm^3, F（000） = 5424,μ = 6.144 mm^-1, the final R= 0.0368 and wR= 0.0865 （I〉 2σ（I））.

Syntheses, Structures, and Luminescence Properties of Two New Open-framework Zinc Phosphites Based on 1,2,4-Triazole Derivatives

With 1,2,4-triazole derivatives as structure directing agents, two new openframework zinc phosphites, [Zn（atrz）（HPO3）]n（1） and [Zn（dmatrz）（HPO3）]n（2）（atrz = 4-amino-1,2,4-triazole, dmatrz = 4-amino-3,5-dimethyl-1,2,4-triazole） have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, powder and single-crystal X-ray diffractions. Both compounds are isostructure and crystallize in the P21/c space group of monoclinic system. Compound 1： a = 9.629（1）, b = 7.384（1）, c = 10.274（1） A, β = 110.729（3）°, V = 683.26（2） A^3, Z = 4, Mr = 229.44, Dc = 2.230 g/cm^3, F（000） = 456, S = 1.10, μ = 3.79 mm^（–1）, R = 0.0181 and w R = 0.0466 for 1121 observed reflections（（40） 〉 2s（（40）））. Compound 2： a = 10.786（2）, b = 8.921（1）, c = 9.749（1） A, β = 107.3°, V = 895.6（3） A^3, Z = 4, Mr = 257.49, Dc = 1.910 g/cm^3, F（000） = 520, S = 1.00, μ = 2.90 mm^（–1）, R = 0.018 and wR = 0.051 for 1581 observed reflections（（40） 〉 2s（（40）））. Both compounds are built up into 4.8-net 2D open-frameworks of vertex-linked Zn O4 and HPO3 units（3.57 × 4.53 A^2 for 1 and 4.43 × 5.90 A^2 for 2）. The structures consist of left-, right-handed helical chains that are connected through oxygen atoms to form an undulated 2D sheet stack, which can be topologically regarded as 4.8~2 nets. Solid-state luminescence properties and thermo gravimetric analyses of these two compounds were investigated, respectively.

Synthesis and Structure of an Organo-templated Oxouranium Phosphite

A novel layered oxouranium phosphite open-structure [（C10H24N2）（H2O）][（UO2）2（HPO3）3]（denoted as TJPU-8,TJPU=Tianjin Polytechnic University） was hydrothermally synthesized with isophorondiamine（IPDA） as the template.Single crystal structure refinement disclosed that TJPU-8 crystallized in the monoclinic space group P21c with cell parameters a=1.8346（9） nm,b=0.6734（1） nm,c=2.0639（0） nm,β=114.61（5）°,V=2.3182（8） nm3,Z=2.TJPU-8 was constructed by UO7 monomer,U2O12 dimer and HPO3 groups.The monomeric UO7 or dimeric U2O12 was connected by HPO3 groups to form two types of 4-ring chains.An undulating sheet was then generated by connecting these two types of chains via HPO3 bridges.The layer structure formed by stacking the sheets along the a direction via the strong H-bonds of organoamine cations and water molecules intercalated in the interlayer spaces with the framework oxygen atoms.Although a mixture of cis-and trans-IPDA was used,only cis-IPDA served as the template.A typical green light emission of TJPU-8 is observed when excited by 266 nm laser.

New 3D Framework Vanadium(Ⅲ) Phosphite with One-dimensional 4,12-Member Ring Channels

A new vanadium（Ⅲ） phosphite,V2（HPO3）3（1）,was synthesized hydrothermally with V2O5,H3PO3 as reactants,1,6-diaminopropane（1,6-HAD） as the structure-directing agent and characterized by single crystal X-ray diffraction,powder X-ray diffraction,IR spectroscopy,TGA,ICP-AES and elemental analyses.Single-crystal X-ray diffraction analysis reveals that compound 1 crystallized in the P6（3）/m hexagonal space group with the unit-cell parameters：a=0.80436（10） nm,c=0.73972（2） nm,V=0.41447（13） nm^3,Z=4.The construction of 3D framework structure of compound 1 may be viewed as the assembly of V2O9 dimers and HPO3 pseudo-pyramids which lead to form the one-dimensional 4,12-member ring channels along the [001] direction.

The Synthesis of Glycosyl Phosphite-Pt(II) Complexes

Ethylene glycol phosphorochloridite 1 or catechol phosphorochloridite 2 reacted with isopropylidene derivatives of D-glucose, D-galactose, D-mannose and D-fructose, a series of glycosyl phosphites were obtained. These glycosyl phosphites form optically active complexes with simple Pt (膊) salts. Pt (II) is coordinated to the phosphorus atom, most of the metal complexes are quite stable.

Synthesis and Diastereomeric Analysis of Uridine 2’,3’-Cyclic Phosphite

Uridine 2’,3’-cyclic phosphite has been synthesized and the diastereomers were analysed by 2D NMR technique to assign the configuration

Synthesis,Characterization and Magnetic Properties of a New Manganese(Ⅱ) Phosphite

A new manganese（Ⅱ） phosphite,Mn 2 F2（HPO3）（1）,was synthesized with tetraethylene pentamine as structure directing agent under hydrothermal conditions.The as-synthesized product was characterized by single crystal X-ray diffraction,powder X-ray diffraction,infrared（IR）,UV-Vis spectrum,thermogravimetric analysis（TGA）,inductive coupled plasma-atomic emission spectroscopy（ICP-AES）,elemental analyses and magnetic susceptibility measurement.Single crystal X-ray diffraction analysis reveals that compound 1 crystallized in the orthorhombic space group Pnma,with a=0.75667（15） nm,b=1.0247（2） nm,c=0.55432（11） nm,V=0.42980（15） nm ^3,Z=4.The 3D compact framework of compound 1 was built up by the Mn2O6F4 dimers and HPO3 pseudo-pyramids.Compound 1,a new metal-rich manganese phosphite,shows a high thermal stability limit of 550 ℃.Magnetic measurement indicates that compound 1 exhibits the global antiferromagnetic interactions with a ferromagnetic transition at 28 K.

A Novel Synthesis of Methyl 4, 6-O-Benzylidene-α-D-Glucopyranoside 2, 3-Cyclic Phosphite Ethyl Ester

A new compound. methyl 4. 6-O-benzylidene-a-D-glucopyranoside 2. 3-cyclicphosphite ethyl ester was synthesized via the reaction of methyl 4. 6-O-benzylidene-a-D-glucopyranoside and ethyl dichlorophosphite. Its structure was confirmed by NMR and MSspectral methods.

ONE'POT REACTION OF TRIVALENTPHOSPHORUS COMPOUNDS (Ⅰ)——A NOVEL ONE-STEP REACTION OF ADDITION,REDUCTION AND CYCLIZATION OF SUBSTITUTED β-NITROSTYRENE WITH O,O-DIALKYL PHOSPHITES

In this paper the reaction of substituted β-nitrostyrene with O,O-dialkyl phosphite under cocatalysis of trimethylsilyl chloride （TMS-C1） and triethylamine （or other acidbinding agent） has been first studied and the new cyclization reaction leading to the formation of product Ⅱ, as a new class of derivatives of 1-hydroxyindoles, difficultly accessible or inaccessible with usual methods has been observed. In the related reaction it is surprising that when the Arbuzov rearrangement occurs under mild conditions, the addition, reduction and cyclization as a one-pot reaction take place simultaneously with the formation of products Ⅰ, Ⅱ, Ⅲ. By controlling the reaction conditions the products were formed almost in specificity, and thus the most interesting cyclic products Ⅱa-h containing phosphorus-carbon bond were obtained. Their structures were confirmed by elemental analysis, IR, 1H or 31p NMR and MS spectra. The crystal structure of representative compound Ⅱh was determined by X-ray

Asymmetric Pudovik Reaction of Chiral Fluoroalkyl α,β-Unsaturated Ketimines and Diphenyl Phosphite

The asymmetric Pudovik reaction of chiral fluoroalkyl α,β-unsaturated ketimines derivated from(R)-tert-butanesulfinamide and diphenyl phosphite was achieved in the presence of Rb2CO3 at room temperature.A series of fluoroalkylated α-amino phosphonates were prepared in good yields with high diastereoselectivities.

Synthesis of novel cyclohexanediol-derived chiral phosphite ligands and their application in the Cu-catalyzed conjugate addition of organozinc to cyclic enones

A series of novel chiral diphosphite ligands have been synthesized from（1R,2R）-trans-1,2-cyclohexanediol,（1S,2S）-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[（R）-1,10-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand（1R,2R）-bis[（R）-1,1＇-binaphthyl-2,2＇-diyl]phosphitecyclohexanediol 6a＇ derived from enantiopure starting material. A significant dependence of stereoselectivity on the type of enone and the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones.

Hydrothermal Synthesis of a New Zinc Phosphite （CsH7N2）2·[Zn3（HPO3）4] with Intersecting 8- and 12-Ring Channels

Using 4-aminopyridine as the structure-directing agent（SDA）, a new open-framework zinc phosphite, （CsH7N2）2·[Zna（HPO3）4]（ZnHPO-CJ70）, was synthesized under hydrothermal condition. Single-crystal X-ray diffraction analysis reveals that ZnHPO-CJ70 is constructed by the strictly alternating ZnO4 tetrahedra and HPO3 pseudo-pyramids, with their vertexes linked to generate a three-dimensional（3D） open framework with intersecting 8- and 12-ring channels. Further characterizations of ZnHPO-CJ70 were performed by means of X-ray powder diffraction（XRD）, elemental analysis（ICP, CHN）, infrared spectroscopy（IR） and thermogravimetric（TG） analyses. The results of luminescent test shows that ZnI-IPO-CJ70 exhibits strong fluorescence emissions in the solid state at room temperature.

Consecutive Reaction of Bis[2,2,2-trifluoroethyl]phosphite.Onepot Synthesis of Substituted 3-Cyano-β,γ-unsaturated Nitriles with Exclusive or Predominant E-Selectivity

The consecutive reaction of bis [2,2,2-trifluoroethyl ] phosphite and its application to the one-pot synthesis of 3-cyano-β,γ-un-saturated nitriles with exclusive or predominant E-selectivity (E:Z = 100-85:0-15) and excellent yields (94%-99%) are described.

A Novel Catenarian Cyano（triphenyl phosphite） Copper（I） Complex： Synthesis, Crystal Structure, Thermal, Voltammetric and Spectral Properties

Quantitative reaction between copper（I） cyanide and triphenyl phosphite forms copper（I） complex [（P（OPh）3）gCug（CN）4] （1）. X-Ray crystal structure shows a catenarian polymer of tandem interconnected copper cyanide, with C and N connecting to proximal Cu atoms. The Cu atoms adopt two different conformations： one exhibits linear construction, while the other exhibits distorted tetrahedral geometry through coordinating to two cyano groups and the P donors of triphenyl phosphite molecules. The feature of 1 is the propagation pattern of two- and four-coordination along with the chain. IR and electronic absorption spectra also confirm the established single crystal structure. Thermal analysis indicates that 1 has a high thermal stability. 3-D fluorescence result shows the middle absorption peaks with the maximum excitement and emission wavelength 342 and 350 nm, respectively. Cyclic voltammogram in DMSO, DMF and MeCN gives a midpoint voltage of --0.003, 0.061 and 0.137 V versus SCE, respectively, showing the different solvent virtue on reduction potential.

Hydrothermal Syntheses, Crystal Structures and Thermal Properties of Two New Organically Templated Open-framework Gallium Phosphites

Two new open-framework gallium phosphites formulated as （C2N2HI0）o.sGa2（OH）（H20）（HPO3）3（I） and （C3N2Hs）2（C3N2H6）Gas（H20）6（HPO3）14（2） were hydrothermally synthesized in the presence of ethylenediamine（en） and imidazole as structure directing agents（SDA）, respectively. Structural analyses reveal that the 3D structures of compounds I and 2 are both built up from the linkage ofGaO6, GaOs（H20） and HPO32 units by sharing vertices. The structure of compound 2 is constructed from well-known 4.6.12-net connecting layers in the AAAA stacking se- quence, which are oenetrated bv the 1D Ga--O--P chains to form a 3D pillared-layered structure.

Synthesis of Novel Tartaric Acid-derived Chiral Phosphite Ligands and Their Application in the Cu-catalyzed Conjugate Addition of Diethylzinc to Cyclic Enones

Five novel tropos （3R,4R）- and/or （3S,4S）-N-benzyltartarimide-derived biphenylphosphite ligands were synthesized and applied in the Cu-catalyzed asymmetric conjugate addition of diethylzinc to cyclic enones with up to 75% e.e. Compared with the reported ligand 1-N-benzylpyrrolidine-3,4-bis[（R）-1,1＇-binaphthyl-2,2＇-diyl]phosphite- L-tartaric acid, the issue that L-（＋）-tartaric acid backbone and （R）-binaphthyl showed strong matched/mismatched character was solved with these tropos ligands. It was found that the enantioselectivity was mainly controlled by the absolute configuration of N-benzyltartarimide backbone, and both enantiomers of the addition products can be obtained by simply changing the configuration of N-benzyltartarimide substituent.

气相色谱-质谱法对水中亚磷酸三乙酯测定方法研究

Triethyl Phosphite is the intermediate of producing nervous toxin of organic phosphate,which is involved in the chemicals of schedule 3. in Convention On The Prohibition Of The Development,Production,Stockpiling And Use Of Chemical Weapons And On Their Destruction.A method for the determination of triethyl phosphate was established by GC-MS/SIM.Average recovery was 96.3%-111.5% with linear range between concentration and peak area varying from 0.546-10.928 mg/L and the detection limits were 0.011 ng.