2,6-二(对氨基苯)苯并[1,2-d;5,4-d′]二噁唑的合成和纯化

1 ,2 ,3 三氯苯经过硝化、水解、催化加氢、缩合等四步反应 ,合成了 2 ,6 二 (对氨基苯 )苯并 [1,2 d ;5 ,4 d′]二唑 ,总产率为 70 % .同时 ,研究了一种有效的重结晶 2 ,6 二 (对氨基苯 )苯并 [1,2 d ;5 ,4 d′]二唑的方法 .与其他方法相比 ,该法原料便宜易得 ,产物可作为聚合反应的单体原料 .     

Pyrido[2,3-d]dipyrimidines 8. Synthesis of pyrrolo(2′,3′∶4,5)pyrido[2,3-d]pyrimidines

The reaction of 1,3-dimethyl-5-chloro-6-nitropyrido[2,3-d]pyrimidine-2,4-dione with CH-acids yielded 5-substituted pyridol[2,3-d]pyrimidines which were used in the synthesis of pyrrolo(2,34,5)pyrido[2,3-d]pyrimidines.For Communication 7, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 800–803, June, 1993.     

化合物[2,6-bis(benzo[1,2-d:4,5-d′]diimidazole-2′-yl)pyridine] 的合成、晶体结构和光物理性质

A new tridentate benzimidazole derivative, 2,6-bis (benzo[1,2-d:4,5-d′]diimidazole-2′-yl) -pyridine (Bzdiimpy),was prepared from o-phenylenediamine in five steps with improved methods according to the literature in good yield.The crystal structure was determined by X-ray diffraction analysis. It crystallized in monoclinic, space group P21/c,with a=1.1708(4) nm, b=2.4796(9) nm, c=1.215 9(4) nm,β=114.641(7)°, Z=1, R=0.035 0, wR2=0.0890. The bzdiimp molecule displayed an almost planar structure and formed a zig-zag chain through weak interactions between imidazole-N and [SnCl6]2--Cl. Its electronic absorption and emission spectra were measured and compared with the reported analogue 2,6-bis (benz[1,2-d:4,5-d′]imidazole-2′-yl)-pyridine (Bzp).     

化合物[2，6-bis(benzo[1，2-d：4，5-d′]diimidazole-2′-yl)pyridine]的合成、晶体结构和光物理性质(英)

A new tridentate benzimidazole derivative, 2,6-bis (benzo[1,2-d:4,5-d′]diimidazole-2′-yl) -pyridine (Bzdiimpy), was prepared from o-phenylenediamine in five steps with improved methods according to the literature in good yield. The crystal structure was determined by X-ray diffraction analysis. It crystallized in monoclinic, space group P2₁/c, with a=1.170 8(4) nm, b=2.479 6(9) nm, c=1.215 9(4) nm, β=114.641(7)°, Z=1, R=0.035 0, wR₂=0.089 0. The bzdiimp molecule displayed an almost planar structure and formed a zig-zag chain through weak interactions between imidazole-N and [SnCl₆]^2--Cl. Its electronic absorption and emission spectra were measured and compared with the reported analogue 2,6-bis (benz[1,2-d:4,5-d′]imidazole-2′-yl)-pyridine (Bzp). CCDC: 239203.     

超导相YBa_2Cu_3O_(7-d)的制备与结构研究

本文按计量式Y_(0.334)Ba_(0.666)CuO_(3-y)制备和得到了题目超导物相的样品。实验中使用柠檬酸为复合剂显著改善了金属氧化物的分散性和超导物相的均匀性。我们发现制备所得样品中,偏离四方晶格愈甚者,其超导性能愈佳。由X射线粉晶衍射数据测定了晶体结构,确认了金属离子的化学计量比和给出了氧原子的位置。正交或假四方晶胞的晶胞参数为a=3.893,b=3.813和c=11.867。晶胞由铜原子占据顶点位置的三个钙钛矿型立方体所组成,二个钡原子居于上层和底层的两个体心位置,而钇原子则占据居中立方体的体心位置。氧原子均占据诸立方体的稜心位置,但001/2处为空位,而01/20处的空位则导致晶格对称性由四方畸变为正交,这一畸变对超导相有深远的影响。钇和钡原子的配位多面体系由立方-八面体所派生的八配位和十配位的多面体,两者分别与移去晶胞中001/2和01/20处的氧原子后的氧多面体相对应。根据键价理论,以Y—O,Ba—O和Cu—O键长为基础,我们合理地论述了,即使在001/2及01/20处氧缺位的情况下,1/200处氧原子的占有率亦将低于1,与晶胞对应的该物相化学式为YBa_2Cu_bO_(7-d),0.2相似文献   

Complexation of the antibiotic daunomycin with desoxytetraribonucleoside triphosphate 5’-d(CpGpCpG) in aqueous solution

This paper presents the results of our study of the complexation of the antibiotic daunomycin with desoxytetranucleotide 5’-d(CpGpCpG) in aqueous salt solution by one- and two-dimensional (2D-TOCSY and 2D-NOESY)¹H NMR spectroscopy (500 MHz). The concentration and temperature dependences of the proton chemical shifts of molecules were measured and used to calculate the equilibrium reaction constants, the relative contents of different types of complex as functions of concentration and temperature, the limiting values of the proton chemical shifts of daunomycin in various complexes, and the thermodynamic parameters of complexation δH and δS. It is concluded that the triplet nucleotide sequences are the preferable sites at which daunomycin is attached. The binding of the second daunomycin molecule to both single-stranded and duplex forms of tetramer is markedly anticooperative. This is explained by the presence in the antibiotic of a positively charged amino sugar residue creating steric hindrances for the attachment of the second antibiotic molecule to the short tetranucleotide sequence. The most plausible spatial structure of the 1:2 complex of antibiotic with desoxytetranucleotide is constructed using the calculated values of the induced proton chemical shifts of daunomycin and 2D-NOE data. Translated fromZhurnal Strukturnoi Khimii, Vol.40, No. 2, pp. 276–286, March–April, 1999.     

PREPARATIVE AND STRUCTURAL STUDIES ON THE SUPERCONDUCTING PHASE YBa_2Cu_3O_(7-d)

Reasonably homogeneous samples were obtained by following the formula Y_(0.334)Ba_(0.666)CuO_(3-y) andusing citric acid as a complex-forming agent to improve the dispersion of the metal oxides. We havealso found that the variant condition in preparative procedure leads to variant deviation from tetrago-nality and that more pronounced deviation gives better superconducting properties. The crystal structure determined from X-ray powder diffraction diagrams confirms the stoichiom-etry of the metal ions and gives the positions of the oxygen atoms. The orthorhombic or pseudo-tetragonal unit cell with a=3.893, b= 3.813 and c= 11.687 A contains YBa_2Cu_3O_7. It is composed ofthree perovskite cubes with three copper atoms at their corners, the two barium atoms at the centers ofthe top and bottom cubes, and the yttrium at the center of the unit cell. The oxygen atoms sit on centersof cube edges. The positions (0 0 1/2) are vacant. The vacancies represented by (0(1/2)0) cause the ar-rangement of atoms to lose tetragonal symmetry, and have far-reaching effect for this phase. The yttriumand barium atoms are coordinated in a cuboctahedron respectively with four equatoria oxygen atoms at(0 0 1/2) and two at (0 1/2 0) removed. In the light of bond valence theory we can infer from the in-teratomic distances Y-O, Ba-O and Cu-O that the occupancy of the oxygen atoms at (1/2 0 0) is wellbelow unity while the positions (0 0 1/2) are vacant, the formula of the phase is YBa_2Cu_3O_(7-d), thefraction of Cu(Ⅱ) and (Ⅲ) for the set of copper at (0 0 0) is respectively d/0.5 and (1-d/0.5), and0.2相似文献   

Synthesis of 1,6-dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole, 4- and 5-nitro-1,6-dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole and 4,7-dihydro-1,4,7-trihydroxy-1H-benzo-[1,2-d:3,4-d′:5,6-d″]tris[1,2,3]triazole

1,6-Dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole and 4- and 5-nitro-1,6-dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole were synthesized starting from 2,4-dinitrosore-sorcinol, whereas 4,7-dihydro-1,4,7-trihydroxy-1H-benzo[1,2-d:3,4-d′:5,6-d″]tris[1,2,3]-triazole was synthesized starting from phloroglucinol. The reaction of trinitrosophloroglucinol with hydrazine hydrate in acetic acid led to 2,4,6-tridiazocyclohexane-1,3,5-trione.     

Pyrido[2,3-d]pyrimidines 7. Reactions of 1,3-dimethyl-5,7-dichloro-6-nitropyrido-[2,3-d]pyrimidine-2,4-dione with amines. Synthesis of derivatives of triazolo(4′,5′:4,5)pyrido[2,3-d]pyrimidine

The reaction of 5,7-dichloro-6-nitropyrido[2,3-d]-pyrimidine-2,4-dione with amines gave products of the substitution of one or two chlorine atoms by ammo groups. The catalytic reduction of 6-nitro-5,7-disubstituted pyrido[2,3-d]pyrimidines with hydrogen over palladium oxide on carbon leads to 5,6-diamino- and 5,6,7-triaminopyridopyrimidines, the reaction of which with amyl nitrite in acetic acid gives triazolo(4,5:4,5) pyrido[2,3-d]pyrimidines.For communication 6 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 398–401, March, 1993.     

化合物[2,6-bis(benzo[1,2-d:4,5-d']diimidazole-2'-yl)pyridine]的合成、晶体结构和光物理性质(英文)

0IntroductionBenzimidazoleanditsderivativeshaveattractedagreatattentionintherecentyearsduenotonlytotheirbiologicalactivities[1,2],butalsostrongcoordina鄄tionabilitiesasmultidentateligandsandtheirmetalcomplexeshavingabroadscopeofproperties.Forex鄄ample,pyr…     

2-烷(芳)氧基苯并呋喃并[3,2-d]嘧啶-4(3H)-酮衍生物的合成及杀菌活性

应用膦亚胺3与芳基异氰酸酯的氮杂Wittig反应, 生成碳二亚胺4, 4再分别与酚、醇作用, 在碳酸钾或醇钠催化下关环, 以72%～88%的产率合成了2-烷(芳)氧基取代-苯并呋喃并[3,2-d]嘧啶-4(3H)-酮衍生物5和6, 其结构经IR, 1H NMR, MS和元素分析证实. 初步生物活性测试表明该类化合物表现出温和的杀菌活性. 如5f在50 mg/L浓度时, 对黄瓜灰霉菌的抑制率为55%.     

选择性合成双[噻吩并[2,3-d]嘧啶-4(3H)-酮]

以2-氨基-4-三氟甲基-5-甲基-噻吩-3-羧酸乙酯(1)为起始原料制得膦亚胺2.在碳酸钾的催化下,膦亚胺2与芳基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上2,2’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]3;膦亚胺2与烷基异氰酸酯和伯二胺的氮杂Wittig反应制得嘧啶环上3,3’取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮]4.化合物3的核磁共振氢谱表明关环反应在嘧啶环的2,2’位;化合物4的核磁共振氢谱表明关环反应在嘧啶环的3,3’位.对合成反应机理的推导及目标产物核磁共振氢谱数据的分析解释了此合成反应的选择性.     

1,4-二(萘[2,1-d]并(噁)唑-2’)苯为敏感试剂的荧光光纤传感器测定甲硝唑的研究

将1,4-二(萘[2,1-d]并(口恶)唑-2’)苯(BNOB)包埋在增塑的聚氯乙烯膜中,基于甲硝唑对BNOB的可逆猝灭,研制了一种甲硝唑荧光光纤传感器,传感器可逆性好,响应时间小于40s,响应线性范围为8.0×1O~(-6)～1.0×10~(-(?))mol·L~(-1),检出限为4.O×10~(-6)mol·L~(-1),常见的无机离子、药物不干扰甲硝唑的测定,传感器用于药品制剂中甲硝唑的测定,结果与药典法一致.     

(E)-(5-(4-(二苯基胺)苯乙烯基)二噻吩并[2,3-b∶3′,2′-d]噻吩基)-2-亚甲基丙二腈的聚集态发光现象的研究

本文报道了对一种电子给体-受体化合物(E)-(5-(4-(二苯基胺)苯乙烯基)二噻吩并[2,3-b∶3′,2′-d]噻吩基)-2-亚甲基丙二腈(TPA-DCST)的合成与光谱学行为的研究。化合物TPA-DCST的分子结构中含有强电子给体(三苯胺)与强电子受体(二氰基乙烯)两个部分,并由二噻吩并[2,3-b∶3′,2′-d]噻吩作为共轭桥将电子给体与受体相连接。在合成方面,采用Wittig反应将三苯胺通过双键与二噻吩并[2,3-b∶3′,2′-d]噻吩相连接、醛基化,并与并二腈经Knoevenagel缩合反应合成目标产物。产物通过了核磁氢谱、碳谱、红外以及高分辨率质谱的确认。光谱方面,主要考察了该化合物的吸收与荧光行为。其最大吸收峰位在412nm左右,归属于π-π*跃迁。在非极性溶剂正己烷中表现出来自分子间聚集而形成的聚集态荧光(550nm),并通过了单分子在CTAB胶束([c]=1.02×10-2 mol/L)的发光(460nm)试验得到验证。溶剂效应表明,该化合物没有出现典型的ICT态的发光现象,其原因在于电子给体与受体相连的共轭桥单元,即二噻吩并[2,3-b∶3′,2′-d]噻吩不具有有效的共轭效应。浓度效应与温度效应进一步表明TPA-DCST分子易于产生分子间聚集态的发光。在THF-H_2O二元溶剂体系中呈现典型的聚集诱导(AIE)发光现象,发光峰位为692nm。随着TPA-DCST分子间的聚集程度的增加,聚集态的荧光出现大范围的红移,直至固体发光红移到710nm。TPA-DCST分子的聚集因素可能来自于疏脂作用、偶极-偶极相互作用等。     

Synthesis and Structure of 5-Amino-6-(4-fluorophenylamino)-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one

The title compound (C18H15FN6OS) has been synthesized and its crystal structure was determined by X-ray analysis. The crystal belongs to monoclinic system, space group P21/n with a = 13.983(10), b = 7.337(5), c = 16.702(12) (A), α = 90, β = 98.277(12), γ = 90°, V = 1696(2)(A)3, Z = 4, Dc= 1.498 g/cm3, Mr = 382.42,μ = 0.224 mm-1, F(000) = 792, the final R = 0.0362 and wR = 0.0878 for 2579 observed reflections with I ＞ 2σ(Ⅰ). In the title compound, the atoms of C(1),C(2), C(3), C(4), C(5), N(1), N(2), N(3), N(4), N(5), N(6), O(1) and S(1) form a fully delocalized system with the average deviation of 0.0307(A). There exists a part of electron delocalization over the planes of Ⅰ (pyrazolo[3,4-d]pyrimidin-4-one moiety), Ⅱ (phenyl moiety) and Ⅲ (p-fluorophenylamine moiety). In the molecule, intermolecular hydrogen bonds between N(6)-H(6)…O(1)and C( 15)-H( 15)…O( 1 ) are observed.     

Thermodynamic analysis of the interaction of proflavin with the deoxytetraribonucleotide 5′-d(GpCpGpC) according to proton magnetic resonance data

The temperature dependences of the chemical shifts of the proflavin protons in a mixture with the deoxytetraribonucleoside diphosphate 5-d(GpCpGpC) in aqueous solution were investigated on a pulse NMR spectrometer (500 MHz). A procedure is proposed for calculating the mole fractions of various associates in solution as a function of the temperature. The Gibbs free energies, enthalpies, and entropies of the reactions forming the 11, 12, 21, and 22 complexes of proflavin with the tetranucleotide were determined. The results are evidence of a vital role of hydrophobic interactions in the formation of complexes of the dye with the duplex of the tetramer.Translated from Teoreticheskaya i Éksperimental' naya Khimiya, Vol. 28, Nos. 5–6, pp. 430–435, September–December, 1992.     

2,6-二(对氨基苯)苯并[1,2-d;5,4-d']二噁唑的合成

以4,6-二氨基间苯二酚二磷酸盐和对氨基苯甲酸为原料,在多聚磷酸中,添加还原剂SnCl_2·2H_2O,经缩聚反应合成了有机二胺单体——2,6-二(对氨基苯)苯并[1,2-d;5,4-d']二噁唑(DIABO),其结构经~1H NMR和FT-IR确证。最佳反应条件为:1 0.01 mol,PPA中P_2O_5质量分数为84%,SnCl_2·2H_2O用量为8 wt%,在氮气保护下于200℃反应4 h,产率97%。TG研究结果表明:DIABO的起始分解温度为401.0℃。     

手性5-l-(艹孟)氧基丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物的合成

研究了手性元5-(R)-(l-(艹孟)氧基)-2(5H)-呋喃酮与取代苯甲醛肟以次氯酸钙作为氧化剂进行的区域选择性原位1,3-偶极环加成反应,同步生成两个新的手性中心,得到了一系列光学纯丁内酯并[3,4-d]-3-取代基-异(口恶)唑啉类化合物;应用波谱学手段及X射线单晶衍射法确证了产物的绝对构型,并对产物的核磁共振氢谱规律性加以总结.     

Formation of a three-dimensional bispyridyl based metal-organic architecture containing unique Ag···Ag (d10-d10) interactions

A novel co-ordination polymer based on IB metal thiocyanates, [Ag2(NCS)2(4,4'-bipy)]<,n (1)(4,4'-bipy = 4,4'-bispyridine), hasbeen synthesized by the pre-assembly method and characterized by X-ray crystallography. The complex exists as a three-dimensional network consisting of (AgSCN)<,n undulating layers linked by 4,4'-bipy bridges.2008 Yun Yin Niu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

Polyethylene glycol (PEG) mediated synthesis of pyrrolo-[2,3-d]isoxazoles by using NaOCl reagent – a green chemistry approach

Abstract

Polyethylene glycol (PEG) is found to be an inexpensive, non-toxic, environmentally friendly reaction media for the synthesis of pyrrolo[2,3-d] isoxazoles by using NaOCl reagent in excellent yields under mild conditions.

1