Synthesis and Characterization of a Novel Phosph(V)azane-Platinum(II) Complex

The substitution reaction of bis(anilino)phosphine oxide (C ₆ H ₅ NH) ₂ P(O)H (1) with trans-PtCl ₂ (SEt ₂ ) ₂ yields the novel unprecedented phosph(V)azane-platinum complex cis-Pt(SEt ₂ ) ₂ Cl[HNPhP(O)NPh(HNEt ₃ )] (3). In this reaction, the bis(anilino)phosphine oxide undergoes P–H activation and a Pt(II)–P(V) bond instead of Pt–N bond forms. ³¹ P NMR spectra readily distinguish between the “N” and “P” bonding modes. The reaction requires the presence of triethylamine (TEA) as a base in order to deprotonate the phosphazane ligand and is separated as Et ₃ NH⁺Cl^?, whereas HTEA⁺ exists in the final product 3 and is acting as charge balancing and H-bond structure directing agent. The products have been fully characterized by means of IR; MS; UV-Vis; and ¹ H, ¹³ C, and ³¹ P NMR spectroscopy.     

界面缩聚法合成双(烯基环戊二烯基)钛(锆)聚醚的研究

本文通过界面缩聚法利用双(烯基环戊二烯基)钛(锆)二氯化物与二酚反应,制成了16个新的高分子化合物,对它们进行了IR、TGA和分子量的测定。文中还对反应条件与分子量的关系进行了讨论。     

二苄基二茂钛的羰基化反应

用取代的二苄基二茂钛与一氧化碳在正庚烷中反应,生成二羰基二茂钛和二苄基甲酮。通过光谱监测,发现1摩尔一氧化碳插入碳钛键,得到取代的苯乙酰基苄基二茂钛。反应随着取代基给电子能力的增加而加快(Me>t-Bu≈H>F>Cl)。中间体Cp_2Ti[C(O)CH_2Ph]CH_2Ph很活泼,迅速发生分子内消除,消除的苄基和苯乙酰基生成二苄基酮。     

Synthesis of Some Novel Class of Bis(isoxazoline) and Bis(aziridine) Derivatives

Synthesis of some new bis(isoxazoline) derivatives has been described from terepthaldehyde derived bis(nitrones) using microwave irradiation via 1,3‐dipolar cycloaddition reaction. Bis(isoxazoline) derivatives in turn successfully converted into new bis(aziridine) derivatives via Baldwin rearrangement. Simple reaction methodology, non involvement of catalysts, and good to excellent yields are the important features noticed in this synthesis.     

Synthesis of 2-Indolyl-1-nitroalkane Derivatives Using Nanocrystalline Titanium(IV) Oxide

The catalytic Friedel–Crafts alkylation of indoles with nitroalkenes to furnish 2-indolyl-1-nitroalkane derivatives at room temperature with moderate to excellent yields is reported using nanocrystalline titanium(IV) oxide (nano-TiO₂) catalyst. In all cases, a single regioisomer was obtained. After completion of the reaction, the catalyst was recovered by centrifugation and activated under a nitrogen flow for 1 h at 250°C for further reuse. The nano-TiO₂ can be reused for four cycles with a slight decrease of activity under the same reaction conditions.     

Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

A Novel Synthesis of AlCl[(NPh)2P(O)H] and SiCl2[(NPh)2P(O)H]: Two New Phosph(V)azane Derivatives

Reactions of phosph(V)azane derivatives of bis(anilino)phosphine oxide (PhNH)₂P(O)H (1) with AlCl₃ and SiCl₄ produce two new phosph(V)azane complexes, AlCl[(NPh)₂P(O)H] (2) and SiCl₂[(NPh)₂P(O)H] (3). In these reactions, an HCl elimination occurs and M─N bonds (M = Si, Al) form directly between a bis(anilino)phosphine oxide ligand with aluminum and silicon halides. The reactions do not require any base to deprotonate the phosphazane ligand. The final products have been fully characterized by means of elemental analysis and IR, MS, and multinuclear NMR (¹H, ¹³C, ³¹P, ²⁷Al, and ²⁹Si) spectroscopy.     

Synthesis and Characterization of Aminophosphines,Bis(amino)phosphine Derivatives,and Their Molybdenum(0) Complexes

Functionalized bis(amino)phosphines of the type PhP(NHR)₂ ( 1a–c ) and aminophosphines of the type Ph₂PNHR ( 2a–c ) have been synthesized by treating PhPCl₂ or Ph₂PCl with corresponding primary amines of H₂N-R where R = -CH₂SO₃H, -C₆H₄SO₃H, and benzo-15-crown-5. The molybdenum(0) complex of the aminophosphine ( 3 ) has been obtained by reacting cis-[Mo(CO)₄(bipy)] with aminophosphine ( 2c ). The synthesized aminophosphines, bis(amino)phosphines, and the molybdenum(0) complex have been characterized by IR, ¹H NMR, ³¹P NMR, and MS spectroscopic techniques and by elemental analysis.     

间二苄胍衍生物的合成

通过间二苄氯衍生物和二甲酰胺钠的亲核取代及水解方便地制备了相应的间二苄胺. 后者与甲基异硫脲作用生成间二苄胍硫酸盐,经离子交换得到相应的间二苄胍盐酸盐.     

Reactions of Bis(Trifluoromethyl)Phosphine and Tetrakis(Trifluoromethyl)Phosphine with Ruthenium Carbonyl Clusters

Abstract

The reaction of (CF₃)₂P-P(CF₃)₂ with [Ru₃(CO)₁₂] yielded compounds : [Ru₁₄(CO)₁₃{μ-P(CF₃)₂)₂] (1), [Ru₄(CO)₁₄{μ-P(CF₃)₂}₂] (2), and [Ru₄(CO)₁₁{μ-P(CF₃)₂}₄] (3); reaction with [μ-H)₄Ru₄(CO)₁₂] yielded (1) and [(μ-H)₃Ru₄(CO)₁₂{μ-P(CF₃)₂}] (4). The reaction of (CF₃)₂PH with [Ru₃(CO)₁₂] yielded compounds (1) and (4) and compounds (1) and (2) using cluster : ligand ratios of 1:1 and 1:2 respectively. All the compounds have been characterised by X-ray crystallography; a schematic diagram of their structures is shown in Figure 1. The fluxional behaviour of the hydrides in (4) was studied using variable temperature ¹H NMR spectroscopy (see Figure 2). The result of this study was used in the assignment of hydride positions of (4) in the solid state.     

Convenient Synthesis of Bis（oxazoline） Dicarboxylate Derivatives

The synthesis of bis(oxazoline) dicarboxylate derivatives was investigated.Diethyl-aminosulfur trifluoride (DAST) was used as a convenient cyclization reagent in the synthesis of bis(oxazoline) dicarboxylate derivatives,which can not be obtained by the general method using MsC1 and Et3N as dehydrating cyclization reagent.     

Synthesis and Thermal Rearrangement of Tetramethyldisilane-bridged Bis(cyclopentadienyl) Diiron Complexes with Bis(phosphine)Substitution

Photolysis of [Me2SiSiMe2)[C5H4Fe(CO2)]2with a series of bis(phosphine)ligands Ph2P(CH2)n PPh2(n=1-4) leads to the formation of the corresponding diiron complexes with intramolecular and intermolecular bis(phosphine) substitution.When these complexes were heated in refluxing xylene.only in the complexes with intermolecular bis(phosphine )substitution the thermal rearrangement reaction occurred.     

二(4-溴苯基)氧化膦的改进合成及其在水溶性膦化合物合成中的应用

选择适当的反应条件实现对环境无害的有机及催化反应是 2 1世纪化学家所面临的重要挑战 [1～ 3 ] .Kuntz研究组 1 975年开展民含水两相催化反应的研究 [4 ] ,水溶性膦配体与过渡金属 (如铑、钯和镍等 )所形成的配合物可在水 /有机两相催化体系中实现不对称氢化、烯丙型烷基化、     

Synthesis and Structural Characterization of Bis(tetrahydro­pyran)calcium Bis[bis(trimethylsilyl)amide]

Transmetalation of Sn[N(SiMe₃)₂]₂ with calcium granules in tetrahydropyran (thp) yields colorless [(thp)₂Ca{N(SiMe₃)₂}₂] ( 1 ) which is soluble in common organic solvents. The calcium center is in a distorted tetrahedral environment with Ca–N and Ca–O bond lengths of 231.08(11) and 240.23(9) pm, respectively. The molecular structure is dominated by steric factors leading to a NCaN bond angle of 119.43(6)°.     

Synthesis and Characterization of Bis(Isopropenylphenoxy)Alkanes and Bis(Vinylphenoxy)Alkanes: Two Classes of Highly Reactive,Photopolymerizable Monomers

Abstract

A novel and facile synthesis of difunctional, aromatic vinyl ether analogs is reported. These materials, which are conveniently prepared by the condensation of 4-acetoxystyrene or 4-isopropenylphenyl acetate with α, ω-dihaloalkanes in the presence of base, can be cationically polymerized using diaryliodonium or triarylsulfonium salts as photoinitiators to produce crosslinked polymers. Relative reactivities of the monomers toward cationic polymerization were studied using differential scanning photocalorimetry. The thermal stabilities of the polymers resulting from the photopolymerization of the difunctional, aromatic vinyl ether analogs were studied using thermogravimetric analysis.     

Synthesis and Characterization of a Novel Phosph(V)azane-Tin(IV) Complex

Abstract

The reaction of bis(anilino)phosphine oxide (C₆H₅NH)₂P(O)H, 1 with Bu₂ ⁿSnCl₂ in the presence of an excess of triethylamine (TEA) in dry tetrahydrofurane (THF) yields the novel N,O-bonded tin complex Bu₂ ⁿSn[NPh(O)P(H)NPh(HNEt₃)]₂, 2. TEA is used as a base to deprotonate the phosphazane ligand and is separated as Et₃NH⁺Cl^?, whereas HTEA⁺ exists in the final product 2 and act as a charge balancing and H-bond structure–directing agent. This new compound has been fully characterized by means of IR, MS, and multinuclear (¹H, ³¹P, and ¹¹⁹Sn NMR) spectroscopy.     

Synthesis and Crystal Structures of Antimony(III) Complexes With a Bis(amino)silane Ligand

Bis(amino)silane bearing bulky substituents on nitrogen, LH₂ [L = Me₂Si(NDipp)₂, Dipp = 2, 6‐diisopropylphenyl] was reacted with nBuLi (ratio 1:1 and 1:2) in toluene. The Me₂Si(LiNDipp)₂ was treated with SbCl₃ in a 1:1 ratio to yield the four‐membered SiN₂Sb ring compound of composition [η²(N,N)‐Me₂Si(NDipp)₂SbCl] ( 1 ). The mono lithiated bis(amino)silane was used to synthesize the monodentate heterotetraatomic complex [(η¹‐Me₂SiNDipp)NHDippSbCl₂] ( 2 ) by the reaction with SbCl₃. The complexes were characterized by ¹H and ¹³C NMR, elemental analysis, IR, and single‐crystal X‐ray structural analysis.     

含三苯基氧磷结构聚芳醚醚酮酮的合成与表征

以苯酚、对二溴苯及苯基磷酰二氯为原料合成出二(4-苯氧基苯基)苯基氧磷(BPOPPO)。 三氯化铝(AlCl₃)为催化剂,通过缩聚反应,BPOPPO与对苯二甲酰氯(TPC)反应制备出一种含有三苯基氧磷结构的聚醚醚酮酮(P-PEEKK)树脂。 采用傅里叶变换红外光谱仪(FT-IR)、差示扫描量热仪(DSC)、热重分析仪(TGA)和广角X射线衍射(WAXD)等技术手段对P-PEEKK树脂的结构和性能进行表征。 结果表明,P-PEEKK树脂属于非晶聚合物,玻璃化转变温度(T_g)较高,为190.5 ℃;热分解温度(T_5%)为515 ℃,耐热性能较好;极限氧指数(LOI)为42,阻燃性能好,为难燃材料;易溶解于氯仿、1,2-二氯乙烷、N,N-二甲基乙酰胺等有机溶剂中,溶解性能较好,便于涂膜加工;拉伸强度为62 MPa,力学性能较好。     

双（1—乙酰基—4—取代苯甲酰基氨基硫脲）及其衍生物的合成

由丁二酰肼Ⅰ与取代苯甲酰基异硫氰酯在无水CaCl_2处理过的乙腈溶剂中亲核加成,制得一系列未知的双(1-乙酰基-4-取代苯甲酰基氨基硫脲)衍生物Ⅱ,Ⅱ在碱性条件下环化为未知的双(3-亚甲基-4-取代苯甲酰基-1,2,4-三唑啉-5-硫酮)Ⅲ ,所有化合物结构均经鉴定,部分化合物对枯草芽孢杆菌和大肠杆菌有抑制作用。     

Synthesis and Characterization of Bis(undeca-tungstoferrate) Lanthanates of Potassium

A series of novel rare earth complexes with 11-tungstoferrate as ligand, K15Ln(FeW11 O39)2 .xH2O(Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Er or Yb) were prepared and characterized by elemental analyses, IR, UV-vis, polarograms, magnetic susceptibility and thermal measurement.Keywords Heteropoly complex, Rare earth complex, Synthesis, Bis(undecatungstoferrate) lanthanates of potassium