O,O-二甲基-S-(N-取代氨基甲酰甲基)二硫代磷酸酯的合成

采用两种不同方法(A与B法)制备十五种O,O-二甲基-S-(N-取代氨基甲酰甲基)二硫代磷酸酯. 方法A是用O,O-二甲基二硫代磷酸酯与N-取代α-氯代乙酰胺在碳酸钠的存在下及在丙酮溶剂中进行反应.方法B是利用O,O-二甲基二硫代磷酸酯的钠盐与N-取代α-氯代乙酰胺的反应.产率在21-78%之间.     

S-[N-取代氨基甲酰甲基]-O,O-二烷基二硫代磷酸酯类化合物的合成及其对植物的抑制活性

用O,O-二烷基二硫代磷酸酯与α-卤代乙酰胺在丙酮或氯仿/水体系中反应,合成了40余种标题化合物,确定其结构;研究了酰胺分子中不同取代基对反应的影响.测定它们对植物的抑制活性发现,引入磷酰基可保持原来卤代酰胺的生物活性,但选择性却有明显提高,初步讨论了这类化合物结构与活性的规律。     

有机磷化合物的研究Ⅲ.O-烷基-S-(N-取代氨基甲酰甲基)乙基二硫代膦酸酯的合成

我们曾合成O-烷基-O-取代苯基乙基硫代膦酸酯类化合物,证明有较好的杀虫效果.但碳磷键结构的膦酸酯一般毒性较大.本文合成一系列乙基二硫代膦酸酯类化合物,目的是寻求高效低毒有机磷农药.     

有机磷杀虫剂的研究Ⅱ. O,O-二烷基S-烴基(取代烴基)硫甲基二硫代磷酸酯的合成

本文报告型二硫代磷酸酯十种,和它们的一些物理常数。初步昆虫试验结果说明它们对四龄蚊幼虫的触杀作用及对刺吸口器害虫的内吸毒效均较低。     

选择性有机磷杀虫剂 O,O-二烷基 S-烷基酯基烷基二硫代磷酸酯的合成

O'Brien等根据馬拉硫磷(Malathion,Ⅰ)的解毒作用机理設計阿賽昂(Acethion,Ⅱ),也具高度选择毒性。各国学者曾先后合成多种同类化合物,其中某些具优越的杀虫效能。     

(硫代)磷酰脲衍生物的研究 V: N-[O,O-二烷基(硫代)磷酰基]-N''-(4-氯苯甲酰基)脲的合成和性质

本文采用二烷氧基(硫代)磷酸胺酯与4-氯苯甲酰基异氰酸酯, 通过亲核加成反应合成了两个系列共16个未见文献报导的磷酰脲衍生物。     

(硫代)磷酰脲衍生物的研究——Ⅴ.N-[O,O-二烷基(硫代)磷酰基]-N＇-(4-氯苯甲酰基)脲的合成和性质

Nikonorov等人曾报道N＇-烃基磷酰脲类化合物具有良好的除草活性,但对N＇-芳酰基磷酰脲类衍生物尚未见报道。前文曾报道此类化合物的先导母体化合物[(RO)_2P(X)-NHCONHCOC_6H_5]的合成和对乙酰胆碱酯酶(AChE)的抑制活性。为了进一步研究这类化     

三[(苯基二甲硅基)亚甲基]锡 O,O-二芳基二硫代磷酸酯的研究

本文合成了十五个新的[苯基二甲硅基]锡O,O-二芳基二硫代磷酸酯。测定了它们的IR, ^1H, ^1^3C, ^1^1^9Sn NMR及MS, ^1^1^9Sn NMR的化学位移δ和芳环对位取代基的Hammett常数σ之间存在良好的线性关系。     

有机磷杀虫剂的研究Ⅰ. O,O-二烷基 S-烃基(取代烃基)硫(氧)甲基(取代甲基)二硫代磷酸酯的合成

本文报告下列三类型化合物的合成:(?)(X=硫或氧)Ⅰ.R=甲基或乙基,R′=氢,R″=脂烃基,共十三种Ⅱ.R=甲基或乙基,R′=氢,R″=烷氧代乙基或烷硫代乙基,共六种Ⅲ.R=甲基或乙基,R′=甲基,R″=脂烃基或烷氧代乙基,共八种这些化合物是用相当的 O,O-二烷基二硫代磷酸酯,醛,与硫醇或醇缩合制得。并测定了各化合物的一些物理常数。初步昆虫试验结果说明 P_2,P_7,P_(11),P_(20),P_(27),P_(154)等对四龄蚊幼虫有显著的触杀作用,并对刺吸口器害虫有内吸毒效。此外 P_1,P_5,P_(32),P_(47),等虽触杀效率较差,但均具良好的内吸效率,其中大部分化合物的内吸效能相当于目前常用的内吸剂 E1059。     

A New Type of Methacrylate-Substituted Oxozirconium Clusters: [Zr3O(OR)5(OMc)5]2 and [Zr3O(OR)3(OMc)7]2

Summary.  The new clusters Zr₆O₂(OBu)₁₀(OMc)₁₀ and Zr₆O₂(OMe)₄(OBu)₂(OMc)₁₄ were prepared from Zr(OBu)₄ and methacrylic acid. For the preparation of Zr₆O₂(OMe)₄(OBu)₂(OMc)₁₄, partial exchange of the butoxy groups is necessary. The clusters consist of two Zr₃ subunits that dimerize via alkoxide bridges. The structures are of the same type, except that four terminal butoxy ligands in Zr₆O₂(OBu)₁₀(OMc)₁₀ are exchanged for chelating methacrylate ligands in Zr₆O₂(OMe)₄(OBu)₂(OMc)₁₄. Received March 26, 2001. Accepted April 17, 2001     

2'-O-[2-[N,N-(dialkyl)aminooxy]ethyl]-modified antisense oligonucleotides

[structure] Oligonucleotides with two novel modifications, 2'-O-?2-[N, N-(dimethyl)aminooxy]ethyl? (2'-O-DMAOE) and 2'-O-?2-[N, N-(diethyl)aminooxy]ethyl? (2'-O-DEAOE), have been synthesized. These modifications exhibit high binding affinity to target RNA (and not to DNA) and enhance the nuclease stability of oligonucleotides considerably with t(1/2) > 24 h as a phosphodiester.     

The reaction of Li[Al(OR)4] R = OC(CF3)2Ph, OC(CF3)3 with NO/NO2 giving NO[Al(OR)4], Li[NO3] and N2O. The synthesis of NO[Al(OR)4] from Li[Al(OR)4] and NO[SbF6] in sulfur dioxide solution

NO[Al(OC(CF(3))(2)Ph)(4)] 1 and NO[Al(OC(CF(3))(3))(4)] 2 were obtained by the metathesis reaction of NO[SbF(6)] and the corresponding Li[Al(OR)(4)] salts in liquid sulfur dioxide solution in ca 40% (1) and 85% (2) isolated yield. 1 and 2, as well as Li[NO(3)] and N(2)O, were also given by the reaction of an excess of mixture of (90 mol%) NO, (10 mol%) NO(2) with Li[Al(OR)(4)] followed by extraction with SO(2). The unfavourable disproportionation reaction of 2NO(2)(g) to [NO](+)(g) and [NO(3)](-)(g)[DeltaH degrees = +616.2 kJ mol(-1)] is more than compensated by the disproportionation energy of 3NO(g) to N(2)O(g) and NO(2)(g)[DeltaH degrees =-155.4 kJ mol(-1)] and the lattice energy of Li[NO(3)](s)[U(POT)= 862 kJ mol(-1)]. Evidence is presented that the reaction proceeds via a complex of [Li](+) with NO, NO(2)(or their dimers) and N(2)O. NO(2) and Li[Al(OC(CF(3))(3))(4)] gave [NO(3)(NO)(3)][Al(OC(CF(3))(3))(4)](2), NO[Al(OC(CF(3))(3))(4)] and (NO(2))[Al(OC(CF(3))(3))(4)] products. The aluminium complex [Li[AlF(OC(CF(3))(2)Ph)(3)]](2) 3 was prepared by the thermal decomposition of Li[Al(OC(CF(3))(2)Ph)(4)]. Compounds 1 and 3 were characterized by single crystal X-ray structural analyses, 1-3 by elemental analyses, NMR, IR, Raman and mass spectra. Solid 1 contains [Al(OC(CF(3))(2)Ph)(4)](-) and [NO](+) weakly linked via donor acceptor interactions, while in the SO(2) solution there is an equilibrium between the associated [NO](+)[Al(OC(CF(3))(2)Ph)(4)](-) and separated solvated ions. Solid 2 contains essentially ionic [NO](+) and [Al(OC(CF(3))(3))(4)](-). Complex 3 consists of two [Li[AlF(OC(CF(3))(2)Ph)(3)]] units linked via fluorine lithium contacts. Compound 1 is unstable in the SO(2) solution and decomposes to yield [AlF(OC(CF(3))(2)Ph)(3)](-), [(PhC(CF(3))(2)O)(3)Al(mu-F)Al(OC(CF(3))(2)Ph)(3)](-) anions as well as (NO)C(6)H(4)C(CF(3))(2)OH, while compound 2 is stable in liquid SO(2). The [small nu](NO(+)) in 1 and [NO](+)(toluene)[SbCl(6)] are similar, implying similar basicities of [Al(OC(CF(3))(2)Ph)(4)](-) and toluene.     

新树型配体 TBOAA 与钴配合物的研究

研究了新配体N，N’，N”－（三苯甲酰）－三乙氨基胺（TOBAA）与二价钴离子生成配合物的光度特征和电化学特征。在较宽的pH范围内，新试剂和钴离子形成2：1的配合物，并且在一定范围内其吸光度与浓度具有良好的线性关系。