Tetraphosphorus Trisulfide in the Synthesis of Organothiophosphorus Compounds

Abstract

The investigations of the reactions of lower phosphorus sulfides with organic substances can result in novel non-traditional methods of the synthesis of organophosphorus compounds. Tetraphosphorus trisulfide was proved to react with thioacetals, to give addition products of the a-alkyl-thioalkyl thionphosphonate structure and tetrathiophosphates.     

Synthesis,Characterization, and Thermal and Antibacterial Studies of Diorganotin(Iv) Derivatives of Amino Acids

Abstract

Six diorganotin(IV) derivatives of α-aminoacids with general formulae [(CH₃)₂ SnAACl]₂ and [(CH₃CH₂CH₂CH₂)₂SnAACl]₂, where AA = L-alaninate, L-phenylalaninate, and L-isoleucinate, have been synthesized by reacting dimethyltin(IV) dichloride (M) and dibutyltin(IV) dichloride (B) with L-alanine (A) or L-phenylalanine (PA) or L-isoleucine (I) using acetonitrile as the solvent and designated as MA, MPA, MI, BA, BPA, and BI. These complexes have been characterized by elemental analysis, infrared (IR), ¹H NMR, ¹³C NMR, and ¹¹⁹Sn NMR spectroscopy. Thermal studies of all of the synthesized complexes were also carried out using thermogravimetric (TG) and differential scanning calorimetry (DSC) techniques. The thermal decomposition mechanisms were similar for MA, BA, MI, and BI and occurred in one step, while in compounds MPA and BPA, it occurred in two consecutive steps. The TG curves of MPA and BPA suggest the loss of the ligand (AA) in the first step, with probable formation of a tin oxide R₂SnO as an intermediate, and in the second step, free tin is obtained, similar to MA, BA, MI, and BI, in accordance with the stoichiometry of the related derivatives. The diorganotin(IV) complexes have also been screened for their antibacterial activity against Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis, and Pseudomonas aeruginosa. The minimum inhibitory concentration values of these complexes show enhanced activity.     

新型meso位芘取代氟硼二吡咯衍生物的合成及光敏活性

以1-芘甲醛为原料分别与2,4-二甲基吡咯和吡咯进行缩合反应,经由2,3-二氯-5,6-二氰对苯醌氧化脱氢、三氟化硼乙醚络合物配位后得到两种meso位芘取代的氟硼二吡咯（BODIPY）染料1和2。1和2经Vilsmeier-Haack反应引入醛基后分别与2,4-二甲基吡咯和吡咯反应得到四种meso位芘取代的BODIPY二聚体（1a, 1b,2a, 2b）;将染料1通过碘化反应生成单碘代产物1c和二碘代产物1d。经¹H NMR, ¹³C NMR和HR-MS（APCI）表征,以1,3-二苯基异苯并呋喃（DPBF）为单线态氧捕获剂测试了各衍生物的光敏氧化性能。结果表明：1a~1d的光敏氧化活性均高于母体1,碘代产物1c的光敏活性提升最大,对DPBF的光敏降解速率可达1的12.0倍,半数降解时间仅为29 s;2的光敏降解速率是1的4.9倍,光照72 s即可实现半数降解。      

磷、砷、硅钼杂多酸-罗丹明6G荧光猝灭法连续测定磷、砷、硅的研究

本文报道了在非离子表面活性剂PVA存在下,磷、硅、砷钼杂多酸-罗丹明6G形成离子缔合物,使罗丹明6G荧光猝灭。研究了罗丹明6G-磷、砷、硅钼杂多酸体系荧光光谱,形成条件和配合物组成。试验了共存离子的干扰。应用此方法对铜合金中磷、砷、硅进行同时测定,结果满意。     

Design,Synthesis, and Bioassay of Novel Compounds of Isolongifolenone Oxime Derivatives

A succession of new isolongifolenone oxime derivatives have been designed and synthesized. The structures of these compounds were identified by IR, ¹H‐NMR, ¹³C‐NMR, mass spectra, and elemental analysis. The bioassays of antibacterial, antifungal, and insecticidal activity were carried out. The in vitro antibacterial and antifungal activities were evaluated by the disk diffusion method, and the minimum inhibitory concentration was determined by the microdilution method, while the insecticidal activity was tested by the spraying method or the straw impregnation method. The results of bioassays showed that compound 3f was more active in resisting all the tested bacterial and fungal organisms when compared to the standard drug amoxicillin at the lowest concentration of 31.3 μg/ml. Compound 4 , synthesized by Beckmann rearrangement reaction of isolongifone oxime, exerted moderate insecticidal activity against soybean aphid. Furthermore, compound 3m exhibited more activity in killing armyworms than the standard drug flucycloxuron at the concentration of 0.5 mg/l.     

Synthesis,Fluorescence and Dielectric Properties of Two Novel Compounds Based on Triethylenediamine Derivatives

Two compounds C_8H_(18)N_2Br_3Mn_(0.5)(1) and C_(12)H_(26)N_2Cl_4Mn(2) based on triethylenediamine derivatives were synthesized by solution method and were characterized by elemental analysis, infrared spectroscopy, single-crystal X-ray structure analysis, fluorescence test, circular dichroism(CD) analysis and dielectric measurement, respectively. According to single-crystal X-ray determination, compound 1 crystallizes in the cubic system, space group Pa3 with a = b = c = 13.7246(5) ?, Z = 24, V = 2585.2(3) ?~3; and compound 2 crystallizes in the orthorhombic system, space group P212121 with a = 7.9716(13), b = 15.309(3), c = 15.804(3) ?, Z = 4 and V = 1928.7(6) ?3. Fluorescent analysis of compound 1 showed an intense emission band at 670 nm when the exciting radiation was set at 378 nm and fluorescent analysis of compound 2 showed an intense emission band at 515 nm when the exciting radiation was set at 363 nm. Dielectric constants of compounds 1 and 2 were measured at different frequencies with temperature variation.     

Catalytic Dearomatization of N-Heteroarenes with Silicon and Boron Compounds

Dearomatized N-heterocycles are an important class of structural motifs for organic synthesis and chemical biology. The catalytic dearomative reduction of unactivated N-heteroarenes using silicon and/or boron-containing compounds as a reductant is one of the most straightforward alternatives to hydrogenation. However, thus far, there are few reported examples on the catalytic reduction of N-heteroaromatic compounds with silane or borane reducing agents. This Review presents recent advances in the catalytic reduction of unactivated N-heteroarenes by hydrosilanes, hydroboranes, silaboranes, and diboranes. The focus is on the chemical reactivity and selectivity of transition-metal or metal-free organocatalyst systems. In addition, the working modes of these catalysis will be described primarily on the basis of experimental mechanistic insight.     

Synthesis of Heterocyclic Pentavalent Phosphorus Compounds from Phosphite Derivatives and Indane-1,2,3-Trione

Reaction of trialkylphosphite derivatives with indane-1,2,3-trione proceeds smoothly at room temperature to afford the corresponding heterocyclic pentavalent [P(V)] phosphorus compounds via an intermolecular [4+1] cycloaddition reaction in excellent yields under solvent-free conditions. We also used dimethylphosphite and diethylphosphite instead of trialkylphosphites in this reaction, but the corresponding pentavalent phosphorus compounds were not isolated, and in both cases phosphate derivatives were obtained. The structures of the products were deduced from their IR, ¹H NMR, ¹³C NMR, and ³¹P NMR spectra, and mass spectrometry.     

Phosphorus(III)-Nitrogen-Sulphur Compounds: Synthesis and Metal Complexes

Abstract

The preparation and X-ray structure (M=Mo) of complexes of the type M(CO)₅(Ph₂PNSO) (M=Cr,Mo) are described. These complexes are used in the synthesis of homo- and hetero-dinuclear complexes of Ph₂PNSNPPh₂. A ³¹P DNMR study of these dinuclear complexes indicates a cis, trans → trans, cis isomerization in solution. The preparation and X-ray structure (M=Cr) of the mononuclear complexes, cis-M(CO)₄(P(Ph)₂NSN(Ph)₂P), (M=Cr,Mo) are also described.     

Synthesis and Spectroscopic Properties of Mixed Aryloxide-Glycolate Derivatives of Arsenic(III)

The reaction in 1:1 molar ratio of {gg4}OGOAsCl , where G = CH 2 CH 2 , CHMeCHMe, CMe 2 CMe 2 , CHMeCH 2 CMe 2 , and CMe 2 CH 2 CH 2 CMe 2 , and substituted phenols ArOH (Ar = C 6 H 3 Me 2 -2,6; C 6 H 3 Pr i -5-Me-2; C 6 H 3 Pr i -2-Me-5 and C 6 H 3 Pr i 2 -2,6), in the presence of one equivalent of triethylamine in benzene afford volatile colorless liquids of the type {gg4}OGOAsOAr . All these derivatives have been characterized by elemental analyses, molecular weight measurements, and spectroscopic [IR, NMR( 1 H and 13 C)] studies.     

动力学分光光度法同时测定微量磷、硅、砷

依据磷、硅、砷和钼酸盐形成的杂多酸被还原剂还原的反应速率不同,建立了同时测定此3个元素的动力学分光光度法.本法成功地应用于生铁样中微量磷、砷、硅的同时测定,结果满意.     

三氟甲磺酸铜催化新型苯并恶唑烷衍生物的合成

以三氟甲磺酸铜［Cu(OTf)₂］为催化剂,取代邻氨基苯酚(1a~1g)和取代联苯甲酰(2a~2g)为原料,合成了7个苯并恶唑烷衍生物（3a~3g,其中3b~3g为新化合物）,其结构经¹H NMR, ¹³C NMR, IR和HR-MS(ESI)表征。以3a的合成为例,研究了催化剂、溶剂、催化剂用量、物料比γ［n(1) : n(2)］和反应温度对3产率的影响。结果表明：在最佳反应条件［8 mmol%Cu(OTf)₂, 1,2-二氯乙烷为溶剂,1a~1g1.5 mmol, γ=3:1,于70 ℃反应10 h］下,3a~3g产率62%~91%。     

Synthesis,Structures and Reactivities of Dicoordinated Phosphorus Compounds

Abstract

The results of experimental investigations by the authors in the area of the chemistry of two–coordinate phosphorus compounds are discussed. Main attention is devoted to a consideration of the new methods for the synthesis of compounds with P=N, P=P, P=As, P=Sb bonds and their conversions.     

新型类卟啉手性双噁唑啉化合物的合成

以对硝基苯甲醛与3,4-二甲基吡咯-2-甲酸乙酯缩合,然后将缩合产物的酯基水解成羧基得二元酸,由羧酸与手性氨基醇一步法合成了6个具有C2对称的类卟啉手性双噁唑啉化合物。     

Divalent Silicon(0) Compounds

Bridge of Si's : Quantum‐chemical calculations suggest that the bonding situation in the recently synthesized “trisilaallene” is better described in terms of donor–acceptor interactions between two silylene ligands L and a naked silicon atom Si, which carries two lone‐pair orbitals, yielding the silylone SiL₂. Further silylones SiL₂ with different donor ligands Si have also been calculated, which might be possible to synthesize.

     

Complex Chemical Synthesis of Unstable Sulfinyl- and Sulfonyl Derivatives of Phosphorus(III)

Abstract

The phosphorus(III) homologues of sulfonamides, R′₂P-S(O)₂R, are hitherto unknown. This is also in the case of phosphorus(V) derivatives: sulfinylphosphinates undergo symmetrization reactions to the homogeneous anhydrides. Sulfinylphosphinites, the O-isomers of sulfonylphosphanes, can only be built up as unstable ligands in the coordination sphere of transition metals, where the Br(CO)₄Mn-fragment seems to be more stable than the (CO)₅M-fragment (M=Cr, Mo, W). Thus, we now synthesized the iodo complexes I(CO)₄Mn[P(C₆H₅)₂X] (X=H, SiMe₃) as suitable starting material for the synthesis of SO-, SO₂-, RSO- and RSO₂-derivatives of coordinated phosphorus(III). Because of the surprising cis-position of the iodo and silyl group (x-ray structure analysis) the silyl-phosphane complex 2 is also of high interest to 1,2-elimination reactions to give metal-phosphorus double bonds.