三稠环系三唑磷茂啉的化学——Ⅳ.2-苯基-3-苯氧基苯并噻唑并(2,3,d)-2,3-二氢-1,2,4,3-三唑磷茂啉的晶体结构

5-甲基-1,2,4-三唑-(3,4,b)-苯并噻唑-1,简称三环唑,是一种新型的水稻杀菌剂,对稻瘟病有特效,为了合成含磷的新型农药,我     

六乙基亚磷酰三胺的反应性——六乙基亚磷酰三胺、苯甲醛、卤仿三元体系的反应

六烷基亚磷酰三胺(Ⅰ)是有机磷化学中较为基本的试剂,作为磷氮化合物的代表,由于其特殊的结构和电子性质,表现出许多特殊的反应性。作者曾发现并研究过六乙基亚磷酰三胺(1a)与卤仿的反应,为判断反应机理,将苯甲醛加入到反应体系中,以期得到关于自由基机理的判据,但实际上出现了新的反应现象,检索C。A。等文献,未发现类似的报道,为此我们进行了较深入的研究。     

三稠环系三唑磷茂啉的化学 II. 2-苯基-3-N,N-二烷基氨基苯并噻唑并[2,3,d]-2,3-二氢-1,2,4,3-三唑磷茂啉与酚和醇的反应

本文通过2-苯基-3-N,N-二烷基氨基苯噻唑并[2,3,d]-2,3-二氢-1,2,4,3-三唑磷茂啉(1)与酚和醇的反应合成了三稠环系三唑磷茂啉的两个新的系列化合物2a～2f和3a～3j.测定了这十六个新磷杂环化合物的IR, ^3^1P, ^1^3C和^1H NMR以及2a的MS和X-ray数据,初步解析了它们的结构。     

腺苷环甘油磷脂缀合物的合成及性质研究

以碘活化的六乙基亚磷酰三胺为磷酰化及环化试剂,经一锅法合成并分离得到硫代环磷酸酯的两个非对映异构体,并对这两个非对映异构体的性质进行了研究.     

1,3-偶极环加成合成新型含2-苯基-1,2,3-三唑基的1,2,4-噁二唑啉衍生物

Schiff碱 3和肟或氯代肟在三乙胺作用下通过 1,3 偶极环加成生成一系列含 2 苯基 1,2 ,3 三唑基的 1,2 ,4 二唑啉类化合物 4a～ 4g ,5a～ 5g和 6a～ 6g .2 1个新化合物的结构经元素分析 ,1 HNMR ,IR和MS谱确证 .     

三组分反应高效合成螺[环戊烷-1,3'-吲哚啉]衍生物

烷基异氰酸酯、丁炔二酸二酯(丙炔酸酯)和3-苯甲酰亚甲基-2-吲哚酮在甲苯中回流反应,高产率地生成螺[环戊烷-1,3'-吲哚啉]衍生物.然而,含有游离氨基的3-苯甲酰亚甲基-2-吲哚酮参加反应时,未取代的氨基可与另一分子丁炔二酸二酯及烷基异氰酸酯继续反应形成含有氨基取代的氮杂-1,3-二烯支链的螺[环戊烷-1,3'-吲...     

含三芳胺基的吡啶甲酸衍生物及其环金属铱配合物的合成与性能

通过Ullmann反应和Negishi偶联反应, 合成了一种含三芳胺功能基的吡啶-2-甲酸衍生物; 并以此为辅助配体、1-苯基异喹啉为环金属配体, 设计合成了一种新型环金属铱配合物. 该配合物的二氯甲烷溶液, 在391～461 nm范围呈现了强烈的金属-配体电荷转移(MLCT)电子跃迁吸收带; 其最大发光波长为609 nm. 与传统的二(1-苯基异喹啉)(吡啶-2-甲酸)合铱配合物相比, 设计的环金属铱配合物具有增强的MLCT电子跃迁吸收和低的氧化电位, 是一种有发展潜力的红色磷光材料.     

环三磷腈类阻燃剂的合成及应用研究进展

简要介绍了制备环三磷腈类阻燃剂所需起始原料六氯环三磷腈的合成方法、合成及取代反应机理;介绍了环三磷腈阻燃剂的阻燃机理;着重阐述了近20年间反应型的羟基/氨基环三磷腈、环氧基环三磷腈、含不饱和双键的环三磷腈、羧基环三磷腈阻燃剂,以及添加型烷氧基环三磷腈、芳氧基环三磷腈的合成及阻燃应用,同时综述了其应用材料的热稳定性能和阻燃性能,并对其发展趋势作了总结和展望。     

Reactions of polyfluoroaromatic compounds with electrophilic agents in the presence of tris(dialkylamino)phosphines

When reacted with P(NEt₂)₃ and a proton donor, pentafluoropyridine, 3-chlorotetrafluoropyridine, pentafluorobenzonitrile, and octafluorotoluene yield products of replacement of the fluorine atom by hydrogen at position 4. This process is accompanied by the side reaction of aminodefluorination. In the case of 3-H-heptafluorotoluene and octafluoronaphthalene, aminodefluorination is the main reaction. Reactions of perfluoro-4-isopropyltoluene, 4-H-heptafluorotoluene, and 4-methylheptafluorotoluene do not occur under the above-mentioned conditions. For Part 7, see Ref. I. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1498–1500, August, 1997.     

Reactions of polyfluoroaromatic compounds with electrophilic agents in the presence of tris(dialkylamino)phosphine

The rate of replacement of the halogen atom in isomers of RC₆F₄X (X=Cl, Br, or I) by the SiMe₃ group under the action of Me₃SiCl and P(NEt₂)₃ depends on the nature and the mutural arrangement of the substituents X and R. In addition to silyldehalogenation, compounds C₆HF₄X (X=Br or I) undergo silyldeprotonation and reduction to tetrafluorobenzenes. For Part 5, see Ref. 1 Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 813–818, April, 1997.     

Synthesis of New Potential NMDA Antagonist Based on Acylphosphonate Derivatives

Abstract

In recent years intensive pharmacological research is focused on the N-methyl-D-aspartate (NMDA) receptor, which has been implicated in normal neuronal hnctioning, including excitatory synaptic transmission, as well as in the pathologies of the central nervous system such epilepsy, Alzheimer and Parkinson's disease, and neurodegeneration following a stroke.     

Reactions of 4-ethoxy-l,l,l-trifluoro-3-buten-2-one with phosphorous nucleophiles: Diethyl phosphite, tributyl phosphine and tris(diethylamino) phosphine

The reaction of (E)-4-ethoxy-l,l,l-trifluoro-3-buten-2-one EtOCHCHCOCF₃1 with diethyl phosphite (EtO)₂P(O)H 2 afforded a 1:1 cis- and trans-mixture of diethyl(l-trifluomethyl-3-ethoxy)allyl-phosphate EtO-CHCH-CH(CF₃)OP(O)(OEt)₂3 via the 1,2-λ⁵-oxaphosphol-4-ene intermediate. While tributyl phosphine Bu₃P added to 1 giving the double addition product Bu₃P⁺CH₂-C⁻(COCF₃)-CHCH-COCF₃5. Its resonance structure was fully identified by spectral methods and single crystal X-ray diffraction analysis. More strong phosphorous nucleophile tris(diethylamino) phosphine (Et₂N)₃P reacted with 1 to give the known compound (E)-4-(diethylamino)-l,l,l-trifluoro-3-buten-2-one Et₂N-CHCH-COCF₃10 in good yield.     

Application of a New Dehydroascorbic Acid Reducing Agent in the Analysis of Vitamin C Content in Food

The analysis of total vitamin C content in food is most frequently performed by reducing dehydroascorbic acid to ascorbic acid, which is then assayed with the technique of high-performance liquid chromatography combined with spectrophotometric detection. Tris(2-carboxyethyl)phosphine is currently the only agent in use that efficiently reduces dehydroascorbic acid at pH < 2. Therefore, there is a continued need to search for new reducing agents that will display a high reactivity and stability in acidic solutions. The objective of the study was to verify the applicability of unithiol and tris(hydroxypropyl)phosphine for a reducing dehydroascorbic acid in an extraction medium with pH < 2. The conducted validation of the newly developed method of determining the total content of vitamin C using tris(hydroxypropyl)phosphine indicates its applicability for food analysis. The method allows obtaining equivalent results compared to the method based on the use of tris(2-carboxyethyl)phosphine. The low efficiency of dehydroascorbic acid reduction with the use of unithiol does not allow its application as a new reducing agent in vitamin C analysis.     

Facile Synthesis of Tris(alkoxydimethylsilyl)methane Derivatives via Alcoholysis Under Open-Flask and Mild Conditions

The reactions between a variety of functionalized alcohols and tris(dimethylsilyl)methane, (HMe₂Si)₃CH, are described. Alcohols such as ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, triethylene glycol monomethyl ether, 2-chloroethanol, 1-octanol, benzyl alcohol, glycidol, and allyl alcohol were converted in the presence of Karstedt's catalyst into the corresponding tris(alkoxydimethylsilyl)methanes, (ROMe₂Si)₃CH, in a convenient one-pot operation under aerobic conditions. The appearance of the products coincides with the generation of colloidal Pt(0) species. Moreover, poly(4-chloromethyl)styrene containing tris(dimethylsilyl)methyl groups reacts with benzyl alcohol or 2-chloroethanol in the presence of Karstedt's catalyst to give new macromolecules bearing tris(alkoxydimethylsilyl)methyl groups. The reaction rate is greatly influenced by the concentration of catalyst.     

Synthesis and Biological Screening of New Cyano-Substituted Pyrrole Fused (Iso)Quinoline Derivatives

Several new cyano-substituted derivatives with pyrrolo[1,2-a]quinoline and pyrrolo[2,1-a]isoquinoline scaffolds were synthesized by the [3 + 2] cycloaddition of (iso)quinolinium ylides to fumaronitrile. The cycloimmonium ylides reacted in situ as 1,3-dipoles with fumaronitrile to selectively form distinct final compounds, depending on the structure of the (iso)quinolinium salt. Eleven compounds were evaluated for their anticancer activity against a panel of 60 human cancer cell lines. The most potent compound 9a showed a broad spectrum of antiproliferative activity against cancer cell lines representing leukemia, melanoma and cancer of lung, colon, central nervous system, ovary, kidney, breast and prostate cancer. In vitro assays and molecular docking revealed tubulin interaction properties of compound 9a.     

Study on the Precursor Phase Composition of Fused Iron Catalyst for Fischer-Tropsch Synthesis

The effect of the precursor composition of fused iron catalyst on the performance of Fischer-Tropsch synthesis was investigated. XRD, BET and CO2 adsorption experiments were carried out to provide better insight into the relationship therein. The results showed that the selectivity of C5＋ hydrocarbon products was dependent on the mole ratio of Fe^2＋/Fe^3＋, which was represented by a hump-shaped curve. Catalysts with precursors containing Fe3O4 phase favored the magnetite spinal formation during F-T reaction, while Fe（1-x）O-based catalysts were more likely to favor the formation and growth of the iron carbide crystals.     

Ambidentate coordination of the tripyridyl ligands 2,2′:6′,2″-terpyridyl,tris(2-pyridyl)-amine,tris(2-pyridyl)methane and tris(2-pyridyl)phosphine to carbonylrhenium centres: Structural and spectroscopic studies

The reactions of [Re(CO)₅Cl] with the ligands tpy (2,2′:6′,2″-terpyridine), py₃N {tris(2-pyridyl)-amine}, py₃CH {tris(2-pyridyl)methane}, and py₃P {tris(2-pyridyl)phosphine} in toluene solution realize compounds with the general formulation [Re(ligand)(CO)₃Cl] in which the tripyridyl ligands are bidentate. X-ray structural determinations of fac-[Re(typ)(CO)₃Cl].H₂O and fac-[Re(py₃N)(CO)₃Cl] confirm these assignments. [Re(tpy)(CO)₃Cl].H₂O (C₁₈H₁₃ClN₃O₄Re) is monoclinic, space group P2₁/n, with cell dimensions a = 7.432(2) Å, b = 17.016(4) Å, c = 14.466(2) Å, β = 93.51(2)°, and Z = 4; full-matrix least-squares refinement on 2435 reflections with I ? 2.5σ(I) converged to a final R = 0.028 and R_w = 0.029. [Re(py₃N)(CO)₃Cl] (C₁₈H₁₂ClN₄O₃Re) is triclinic, space group P1 with cell dimensions a = 13.761(2) Å, b = 14.636(6)Å, c = 11.110(2) Å, α = 110.70(2)°, β = 102.45(2)°, γ = 107.48(2)°, and Z = 4; full-matrix least-squares refinement on 3459 reflections with I ? 2.5σ(I) converged to a final R = 0.038 and R_w = 0.039. If the synthetic procedure is undertaken under irradiation by visible light, for the ligand py₃N a species [Re(py₃N)(CO)₂Cl] (characterized by infrared spectroscopy and conductance measurements) is also formed, in which the ligand py₃N is tridentate. No analogous tridentate species is formed with the ligands tpy or py₃P, although there is evidence that it also forms for py₃CH.