Study of regioselectivity of intramolecular cyclization of N-(m-R-phenyl)- and N-(α-naphthyl)-2-allyl(methallyl)-6-carboxy-4-oxo-3-aza-10-oxatricyclo[5.2.1.01,5]dec-8-enes

Regioselectivity of the intramolecular electrophilic substitution in a series of N-(m-R-phenyl)- and N-(-naphthyl)-2-allyl(methallyl)-6-carboxy-4-oxo-3-aza-10-oxatricyclo[5.2.1.0^1,5]dec-8-enes in reactions with phosphoric acid was studied. The reactions of N-(m-R-phenyl)-substituted derivatives proceed nonregioselectively to form mixtures of 2-R- and 4-R-substituted isoindolo[2,1-a]quinolines, whereas the reactions of N-(-naphthyl)-substituted derivatives occur regioselectively at the position of the naphthyl fragment.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2703–2714, December, 2004.     

The synthesis, characterization and antimicrobial activity of N,N′-bis(2-thiophenecarboxamido)-1,3-diaminopropane and N,N′-bis (2-furancarboxamido)-1,3-diaminopropane and their Cu(II), Zn(II), Co(III) complexes

Metal complexes derived from amides; N,N′-bis(2-thiophenecarboxamido)-1,3-diamino propane (1) and N,N′-bis(2-furancarboxamido)-1,3-diaminopropane (2) were characterized by elemental analysis, spectral (NMR, FT-IR, LC-MS) methods, magnetic moment, molar conductance, and TGA/DTA studies. The complexes were dimeric and have the general formula [ML.Cl_m.(H₂O)_n]2Cl₂ where M=Cu(II), Zn(II), Co(III); m = 1, 2; n = 0, 1. The antimicrobial activities of the amides and their complexes were studied against the bacteria; Escherichia coli (ATCC 11230), Yersinia enterocolitica (ATCC 1501), Bacillus magaterium (RSKK 5117), Bacillus cereus (RSKK 863), Bacillus subtilis (RSKK 863) and yeast; Candida albicans (ATCC 10239).     

Cu(Ⅱ)与N-(2-羟苄基)-DL-丙氨酸、4，4′-联吡啶三元配合物的合成与晶体结构

近年来，基于金属和有机配体间的配位键合作用来设计和构筑具有多孔结构的超分子体系已成为现代化学、材料科学领域内非常活跃和充满前景的研究主题之一。为实现这目标，探求决定配合物配位几何构型的因素及通过配体的设计来控制配合物的结构已引起化学家们广泛的兴趣。     

Synthesis, Spectral and Structural Study of N-[1-(N,N,N′,N′-Tetramethylphosphoramidoyl)- 1H-Benzimidazol-2-yl]-Propionimidic Ethyl Ether

The preparation of N-[1-(N,N,N,N-tetramethylphosphoramidoyl)-1H-benzimidazol-2-yl]-proponimidic ethyl ester 2 has been achieved by the reaction of N-(1H-benzimidazol-2-yl)-proponimidic acid ethyl ester 1 with N,N,N,N-tetramethylchlorophosphoramide. The structure of compound 2 has been determined by X-ray diffraction. The results of (¹H, ¹³C, ³¹P) NMR, IR, EI-MS spectral data are consistent with those obtained from the X-ray diffraction. The compound crystallizes in the triclinic system, following the EsZ conformation. In the crystal, there are two weak C3–H3s1 and C15–H15sO1 intermolecular hydrogen bonds.     

2-nitroguanidine derivatives: VIII. Synthesis and cyclizations of N′1,N′2-bis(N2- nitrocarbamimidoyl) dicarboxylic acid dihydrazides and ethyl [2-(N2-nitrocarbamimidoyl)-hydrazino](oxo)acetate

New methods of synthesis of N¹,N²-bis(N ²-nitrocarbamimidoyl) dicarboxylic acid dihydrazides and ethyl [2-(N ²-nitrocarbamimidoyl)hydrazino](oxo)acetate from 1-methyl-2-nitro-1-nitrosoguanidine and dicarboxylic acid hydrazides were proposed. Cyclization of N¹, N²-bis(N ²-nitrocarbamimidoyl) dihydrazides derived from malonic and succinic acids afforded the corresponding bis(3-nitroamino-1,2,4-triazol-5-yl)-alkanes, while N¹,N ²-bis(N ²-nitrocarbamimidoyl)oxalohydrazide gave rise to previously unknown 5,5-bi-(3-nitroamino-1,2,4-triazole) salts. Heating of ethyl [2-(N ²-nitrocarbamimidoyl)hydrazino](oxo)acetate in water in the presence of alkali metal hydroxides or carbonates resulted in intramolecular ring closure with formation of 5(3)-nitroamino-1,2,4-triazole-3(5)-carboxylic acid or ethyl 5(3)-nitroamino-1,2,4-triazole-3(5)-carboxylate, respectively. Depending on the conditions, ethyl [2-(N ²-nitrocarbamimidoyl)hydrazino](oxo)-acetate reacted with nitrogen-containing nucleophiles (ammonia, hydrazine hydrate, aniline, and phenylhydrazine) to give linear of cyclic products.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1787–1793.Original Russian Text Copyright © 2004 by Metelkina, Novikova.For communication VII, see [1].     

Asymmetric synthesis of the natural erythro-(1R,2S)-8-O-4′-neolignan myrislignan

Abstract  

An efficient and practical asymmetric synthesis of erythro-(1R,2S)-8-O-4′-neolignan myrislignan was achieved by using vanillin and pyrogallic acid as the starting materials. Two key steps are involved: preparation of an enantiopure threo alcohol of predictable stereochemistry by dihydroxylation with AD-mix-β, and inversion of the absolute configuration from the threo to the erythro isomer using a Mitsunobu reaction. The route illustrates a new methodology for the synthesis of erythro-8-O-4′-neolignan.     

Synthesis of α-[2-(2, 4-Dichlorophenoxy) Propionyloxy] Alkyl Phosphonates

Somenewphosphonatederivativeshaveshownexcellentbiologicalactivityandthusdrewourincreasingattention.DUringpastfewyears,wehavesynthesizedandstudiedseveralseriesofthiskindofcompoundswhichhaveherbicidalactivity.['1Amongthem,astriesofsubstitutedphenoxyacetoxyalkylphosphonatesisatypicalone,andsomecompoundsexhibitbetterherbicidalactivities.Inordertoexaminefurtherintotheher-bicidalactivitiesofnewphosphonatederivatives,wedesignedanothernewcompoundsQ-L2-(2,4-dichlorophenoxypropionyloxy)Jalkylphosphona…     

正辛烷为稀释剂不对称N-甲基-N-辛基烷基酰胺萃取铀(Ⅵ)的研究(英)

The extraction of uranyl nitrate was studied with newly synthesized unsymmetrical alkylamides, Nmethyl-N-octyloctylamide (MOOA), N-methyl-N-octyldecanamide (MODA), and N-methyl-N-octyldodecanamide (MODOA), employing n-octane as diluent. The effect of the concentrations of nitric acid, sodium nitrate and extractants on the extraction was investigated and the extraction mechanism was suggested. The effect of temperature on the extraction was also studied and the related thermodynamic functions were calculated. The extracted species were characterized by FTIR spectrometry。     

Stabilities and coordination modes of glycinephosphonic acid in copper(II) heteroligand complexes with ethylenediamine, diethylenetriamine or N,N,N′,N′,N″-pentamethyldiethylene triamine in aqueous solution

Solution equilibrium studies on the Cu(II)-polyamine-(aminomethyl)phosphonic acid (glycinephosphonic acid) ternary systems (polyamine: ethylenediamine (en), diethylenetriamine (dien), N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me₅dien)) have been performed by pH-potentiometry, UV–vis spectrophotometry and EPR methods. The obtained results suggest the formation of the heteroligand complexes with [Cu(A)(Gly(P))] stoichiometry in all studied systems. Additionally, in the systems with dien the protonated [Cu(dien)(H–Gly(P))]⁺ species also exists in acid solution and in the system with en the [Cu(en)(Gly(P))H_-1]⁻ species is formed in the basic solution. Our spectroscopic results indicate the tetragonal geometry for the [Cu(en)(Gly(P))] species, the geometry slightly deviated from square pyramidal for the [Cu(dien)(Gly(P))] complex and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me₅dien)(Gly(P))] species. The coordination modes in these heteroligand complexes are discussed.     

以N-(2-羟苄基)-DL-缬氨酸及4，4′-联吡啶为配体的铜(Ⅱ)配合物的合成、晶体结构及抑菌活性

合成了一个化合物[Cu(sval)(4,4′-bipy)](sval=N-(2-羟苄基)-DL-缬氨酸阴离子,4,4′-bipy=4,4′-联吡啶),通过元素分析、红外光谱、X-射线单晶衍射及热重分析对其进行了结构表征。晶体属单斜晶系,空间群P21/c,晶胞参数:a=1.08723(19)nm,b=1.360 1(2)nm,c=1.359 6(2)nm,β=105.433(2)°,Z=2,V=1.938 0(6)nm3,μ=1.157 mm-1,Dc=1.511 g.cm-3,F(000)=916,R1=0.033 2,wR2=0.089 1。配合物中Cu(Ⅱ)为四配位的平面四边形配位构型,该配合物通过π-π堆积和Cu…N弱相互作用形成双核结构单元,相邻双核结构单元通过Cu…O弱相互作用形成了一个一维链状结构。初步的生物活性实验表明配合物与配体相比,配合物的抑菌活性显著提高。     

Synthesis and properties of α, α′ -bis -(p-benzylphenyl)xylene

Summary ,-bis-(p-Benzylphenyl)xylene was synthesized for the first time and its UV and infrared spectra determined.     

N-(2-丙酸)-芳甲酰腙二对甲基苄基锡配合物的合成、晶体结构及生物活性

二对甲基苄基二氯化锡分别与N-（2-丙酸）-对硝基苯甲酰腙及N-（2-丙酸）-对叔丁基苯甲酰腙反应,合成了2个取代二苄基锡配合物（C1、C2）,通过元素分析、IR、UV-Vis、¹H NMR、¹³C NMR、¹¹⁹Sn NMR、X射线单晶衍射以及热重分析等表征了配合物结构。测试了配合物对癌细胞H460、HepG2、MCF7以及正常人体肝细胞HL7702的体外抑制活性;在Tris-HCl缓冲溶液中,以EB作为荧光探针,用荧光光谱法初步研究了配合物与小牛胸腺DNA的相互作用。结果表明：配合物C1、C2对3种癌细胞都有较好的抑制作用,配合物C2对HL7702的细胞毒性远小于C1;配合物C1、C2与小牛胸腺DNA作用均是插入结合作用所致。     

Studies on the radiolytic stability of N,N,N′,N′-tetra-2-ethylhexyl diglycolamide in n-dodecane solution containing different phase modifiers

The radiolytic stability of a branched diglycolamide extractant, namely N,N,N′,N′-tetra-2-ethylhexyl diglycolamide (T2EHDGA) dissolved in n-dodecane containing several phase modifiers, viz. N,N-dihexyloctanamide (DHOA), tri-n-butyl phosphate (TBP), 1-decanol and iso-decanol has been investigated. The distribution ratio of Am(III) decreased with increased radiation dose studied up to 1000 kGy. Nevertheless, all the composition of extractants showed satisfactory results up to 500 kGy, beyond which the extractants degraded drastically. The stripping behaviour of Am(III) with 0.2 M HNO₃ was found to be unaffected even with the ligand solution irradiated up to 1000 kGy. Extraction of fission product and structural elements was also investigated using the irradiated solvents and was found to be not significantly affected with increasing absorbed dose with the exception of Mo which showed sharp rise in the distribution coefficient values. Loading of Nd in the organic phase decreased with the irradiated solvent due to degradation of the carrier. The effect of the absorbed dose on physical parameters such as density, viscosity and interfacial tension of the solvents has also been investigated.     

Synthesis of β-chloro α-amino acids: (2S,3R)- and (2S,3S)-3-chloroleucine

The first syntheses of (2S,3R)- and (2S,3S)-3-chloroleucine (3-chloro-d-leucines 1 and 2) have been achieved from d-3-hydroxyleucine and allo-d-3-hydroxyleucine, respectively, through the formation of the corresponding N-Cbz β-lactones, followed by a ring opening promoted by lithium chloride and a debenzylation process.     

N-(2-氧乙酸-3-甲氧基)苄叉二胺合锌(Ⅱ)配合物的合成、晶体结构及光学性质研究

本文通过修饰邻香草醛芳环上羟基的方法,得到两种Schiff碱配体:N,N'-二(2-氧乙酸-3-甲氧基)苄叉乙二胺(H₂L¹)和N,N′-二(2-氧乙酸-3-甲氧基)苄叉1,3-丙二胺(H₂L₂),利用水热合成方法以新合成的配体为基点设计合成了2个新的六配位Schiff碱锌(Ⅱ)配合物[Zn(L¹)]·7H₂O(1)和[Zn(L²)]·7H₂O(2),通过元素分析、红外光谱和核磁共振光谱等测试手段对配合物进行了表征,并用X射线单晶衍射测得Zn(Ⅱ)配合物的晶体结构。X射线晶体学研究表明两种配合物晶体结构中都包含多个溶剂水分子,配合物1是以Zn(Ⅱ)为中心扭曲的三方棱柱构型,配合物2构型是以Zn(Ⅱ)为中心扭曲的八面体构型。初步研究了两种配合物的固体发光性,结果表明这两种配合物具有良好的光致发光的性能,有望在光学材料方面得到应用。     

N-(2-氧乙酸-3-甲氧基)苄叉二胺合锌(Ⅱ)配合物的合成、晶体结构及光学性质研究

本文通过修饰邻香草醛芳环上羟基的方法,得到两种Schiff碱配体:N,N′-二(2-氧乙酸-3-甲氧基)苄叉乙二胺(H2L1)和N,N′-二(2-氧乙酸-3-甲氧基)苄叉1,3-丙二胺(H2L2),利用水热合成方法以新合成的配体为基点设计合成了2个新的六配位Schiff碱锌(Ⅱ)配合物[Zn(L1)]·7H2O(1)和[Zn(L2)]·7H2O(2),通过元素分析、红外光谱和核磁共振光谱等测试手段对配合物进行了表征,并用X射线单晶衍射测得Zn(Ⅱ)配合物的晶体结构。X射线晶体学研究表明两种配合物晶体结构中都包含多个溶剂水分子,配合物1是以Zn(Ⅱ)为中心扭曲的三方棱柱构型,配合物2是以Zn(Ⅱ)为中心扭曲的八面体构型。初步研究了两种配合物的固体发光性,结果表明这两种配合物具有良好的光致发光的性能,有望在光学材料方面得到应用。     

Stabilities and Coordination Modes of α-Alaninephosphonic Acid in Copper(II) Heteroligand Complexes with Ethylenediamine, Diethylenetriamine or N,N,N′,N′,N″-Pentamethyldiethylene Triamine in Aqueous Solution

Solution equilibrium studies on Cu²⁺–L₁–L₂ ternary systems have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods (L₁ corresponds to polyamines such as ethylenediamine (en), diethylenetriamine (dien), or N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me₅dien) and L₂ represents 1-aminoethylphosphonic acid (α-alaninephosphonic acid)). The obtained results suggest the formation of heteroligand complexes with [Cu(L₁)(α-Ala(P))] stoichiometry in all studied systems. Additionally, in the system with en the [Cu(en)(α-Ala(P))H₋₁]⁻ species is formed in basic solution. Our spectroscopic results indicate tetragonal geometry for the [Cu(en)(α-Ala(P))] species, geometry slightly deviated from square pyramidal for the [Cu(dien)(α-Ala(P))] complex and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me₅dien)(α-Ala(P))] species. The coordination modes in these heteroligand complexes are discussed.     

N-(1-亚氨基乙基)乙脒铂配合物合成、结构和性质

四氯合铂酸钾分别与邻、间、对磺基苯甲酸在乙腈和水中利用水热合成获得了3个铂的N-(1-亚氨基乙基)乙脒配合物:[Pt(NIA)_2]·(2-sb)·2H_2O(1),[Pt(NIA)_2]·(3-sb)·3H_2O(2)和[Pt(NIA)_2]·(1,4-dsb)·2H_2O(3)(NIA=N-(1-亚氨基乙基)乙脒,2-sb~2-=2-磺基苯甲酸二价阴离子、3-sb~2-=3-磺基苯甲酸二价阴离子、1,4-dsb~2-=1,4-二磺基苯二价阴离子)。合成过程中发生了乙氰三聚以及4-sb~2-转变为1,4-dsb~2-的反应。对配合物进行了元素分析、红外、紫外、荧光、热重和粉末X射线衍射表征,并利用单晶X射线衍射测定了配合物的晶体结构。3个配合物为阳离子-阴离子物种,阳离子为[Pt(NIA)_2]~(2+),中心金属离子四配位平面构型;阴离子与阳离子、水形成氢键,组成一个三维网络结构,但3个配合物的氢键模式不同。配合物在热稳定性、荧光性质上有一定差异。     

N-(1-亚氨基乙基)乙脒铂配合物合成、结构和性质

四氯合铂酸钾分别与邻、间、对磺基苯甲酸在乙腈和水中利用水热合成获得了3个铂的N-(1-亚氨基乙基)乙脒配合物:[Pt(NIA)₂]·(2-sb)·2H₂O(1),[Pt(NIA)₂]·(3-sb)·3H₂O(2)和[Pt(NIA)₂]·(1,4-dsb)·2H₂O(3)(NIA=N-(1-亚氨基乙基)乙脒,2-sb^2-=2-磺基苯甲酸二价阴离子、3-sb^2-=3-磺基苯甲酸二价阴离子、1,4-dsb^2-=1,4-二磺基苯二价阴离子)。合成过程中发生了乙氰三聚以及4-sb^2-转变为1,4-dsb^2-的反应。对配合物进行了元素分析、红外、紫外、荧光、热重和粉末X射线衍射表征,并利用单晶X射线衍射测定了配合物的晶体结构。3个配合物为阳离子-阴离子物种,阳离子为[Pt(NIA)₂]²⁺,中心金属离子四配位平面构型;阴离子与阳离子、水形成氢键,组成一个三维网络结构,但3个配合物的氢键模式不同。配合物在热稳定性、荧光性质上有一定差异。     

4,5-Dihydroxyimidazolidin-2-ones in the reaction of α-ureidoalkylation of N-(carboxyalkyl)-, N-(hydroxyalkyl)-, and N-(aminoalkyl)ureas

Russian Chemical Bulletin - It was found for the first time that the reaction of N-(carboxyalkyl)ureas (ureido acids) with 4,5-dihydroxy-1,3-dimethyl-4,5-diphenylimidazolidin-2-one in methyl or...