1-(4-硝基苯基)-3-(5-硝基-2-吡啶)-三氮烯的合成及其与汞(Ⅱ)的显色反应研究

合成了 1 -(4 -硝基苯基 ) -3 -(5-硝基 -2 -吡啶 ) -三氮烯 ,并研究了它与汞(Ⅱ )的显色反应。在TritonX -1 0 0的存在下 ,pH1 1 2的Na2 B4 O7-NaOH缓冲溶液中 ,试剂与汞生成 2∶1型桔黄色配合物 ,在 4 3 8nm和 52 5nm处分别有一正一负两个吸收波峰 ,用双峰双波长测定 ,其表观摩尔吸光系数为 2 1× 1 0 5L·mo1 1·cm 1,Hg2 +的浓度在 0～ 2 80 μg/L范围内符合比耳定律。成功地测定了人发和尿液中微量的汞。     

Enamine Configuration of 5-Methyl-2-phenyl-4-[（Z）-3-tolylamino-phenylmethylene]pyrazol-3（2H）-one

1 INTRODUCTION In contrast to the old-line academic and practical studies of 1-phenyl-3-methyl-4-benzoyl-5-pyrazo- lone (PMBP) on the metal coordination chemistry[1], the complexes of β-ketoamines derivated from PMBP received little attention due to its complicated com- plexation. However, in recent years, there has a sudden growth of this area as a result of its timely interest in biological activities[2]. Recently, a series of β-ketoamines[3] containing PMBP have been prepared fro…     

Reaction of 2-(2-oxoethylidene)furan-3(2H)-ones with isopropylidenehydrazides of aromatic carboxylic acids: Synthesis of 3-hydroxy-3-(2-oxoethyl)-2,3-dihydropyridazin-4(1H)-ones

3-Hydroxy-3-(2-oxoethyl)-6-phenyl-2,3-dihydropyridazin-4(1H)-ones were obtained by the reaction of methyl 3-oxo-5-phenylfuran-2(3H)-ylideneacetate or 2-[2-(4-chlorophenyl)-2-oxoethylidene]-5-phenylfuran-3(2H)-one with benzoic or p-nitrobenzoic isopropylidenehydrazides. Equilibrium C₍₅₎H and C₍₅₎H₂ tautomeric forms were detected in solutions of the 4-chlorophenyl derivatives in DMSO-d₆. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1156–1158, August, 2007.     

The Synthesis of 3-(2'-Hydroxybutyl) isobenzofuran-1 (3H)-one

l（3H】．Isobenzoturans（Dhthalldes】werereDortedtoexhibitawiderangeofbiologicalactivities．Forexample,3－n－butylphthallde（NB）exhibitsantlasthmatlc’,antlconvuls－ant“actlvltles．PenEandZhouhavestudiedonthemetabolismofNBPInrats‘．Theyfoundthat...     

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins

3-(2-Quinolyl)- and 3-(5-carbethoxyfuryl-2)coumarins were prepared by reaction of substituted salicylaldehydes and hetarylacetonitriles. Alkylation and acylation of 3-hetaryl-7-hydroxycoumarins were studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 432–434, September–October, 2005.     

Synthesis and Crystal Structure of (Z)-Ethyl 5-(phenylamino)-3-(phenylimino)-3H-1,2-dithiole-4-carboxylate

The compound (Z)-ethyl 5-(phenylamino)-3-(phenylimino)-3H-1,2-dithiole-4-carboxylate 3 has been synthesized by the reaction of ethylacetoacetate 1 and phenylisothiocyanate 2. Its structure has been established by ¹H NMR, ¹³C NMR, infrared, mass spectra, and x-ray crystallography.      

Synthesis and Crystal Structure of （Z）-Methyl-3-methoxy-2-{2-[（4-（E-3-p-tolylacryloyl）phenoxy）methyl]phenyl}acrylate

The title compound,(Z)-methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)-methyl]phenyl}acrylate,was synthesized and determined by X-ray single-crystal diffraction. The crystal belongs to the triclinic system,space group P1 with a = 8.0157(8),b = 12.5748(13),c = 13.3768(14) ,α = 64.770(2),β = 75.720 (2),γ = 89.784(2)°,μ = 0.085 mm-1,Mr = 442.49,V = 1174.1(2) 3,Z = 2,Dc = 1.252 g/cm3,F(000) = 468,T = 294(2) K,R = 0.0603 and wR = 0.1498 for 2644 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the single crystal contains strong non-classical hydrogen bonds. The preliminary bioassay showed that the title compound exhibits inhibitory activity against the Pseudoperoniospora cubensis and Rhizoctonia solani at the test concentration of 200 mg/L.     

1-(6-硝基-2-苯并噻唑)-3-(5-溴-8-喹啉)-三氮烯与Co(Ⅱ)的高灵敏显色反应及其应用

报道了在CPB 存在下,新试剂1-(6-硝基-2-苯并噻唑)-3-(5-溴-8-喹啉)-三氮烯(NBTBQT)与钴的显色反应.在pH 9.5的硼砂-NaOH缓冲介质中,试剂与钴形成2:1 深蓝色络合物,其最大吸收波长位于655 nm处,表观摩尔吸光系数为1.94×105 L·mol-1·cm-1,钴的质量浓度在0～0.24 mg/L 的范围内符合比尔定律.方法应用于维生素B12注射液和水系沉积物的测定.     

Straightforward Preparation of (2E,4Z)-2,4-Heptadien-1-ol and (2E,4Z)-2,4-Heptadienal

Abstract

A concise synthesis of (2E,4Z)-2,4-heptadien-1-ol and (2E,4Z)-2,4-heptadienal is presented. Commercially available (Z)-2-penten-1-ol was converted to ethyl-(2E,4Z)-2,4-heptadienoate by reaction with activated MnO₂ and (carboethoxymethylene)triphenylphosphorane in the presence of benzoic acid as a catalyst. Ethyl-(2E,4Z)-2,4-heptadienoate was converted to (2E,4Z)-2,4-heptadien-1-ol with LiAlH₄. The alcohol was partially oxidized to (2E,4Z)-2,4-heptadienal with MnO₂. The title compounds are male-specific, antennally active volatile compounds from the Saltcedar leaf beetle, Diorhabda elongata Brulle (Coleoptera: Chrysomelidae) and have potential use in the biological control of the invasive weed saltcedar (Tamarix spp).     

2-(3’,5’-二硝基苯)-4-硝基-1,2,3-三唑-1-氧化物的合成与量子化学研究

以乙二醛、苯肼和盐酸羟胺为起始原料,经缩合和肟化反应制得肟基苯腙(1)。在硫酸铜-吡啶-水体系中,1经缩合环化得2-苯基-1,2,3-三唑-1-氧化物(2);2被混酸硝化合成了新化合物2-(3’,5’-二硝基苯)-4-硝基-1,2,3-三唑-1-氧化物(3),纯度99%,总收率45%,其结构经1H NMR,IR,MS和元素分析表征。在B3LYP/aug-cc-pVDZ基组水平上对3的结构进行了优化,获得稳定的几何构型。     

3-(2-Pyridyl)coumarins

3-(2-Pyridyl)coumarins were prepared by reaction of substituted salicylaldehydes and 2-pyridylacetonitrile. Benzylation, acylation, and aminomethylation of 7-hydroxy-3-(2-pyridyl)coumarin was studied. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 428–431, September–October, 2005.     

DIASTEREOSELECTIVE SYNTHESIS AND STEREOCHEMISTRY OF (Z)-1-[3-ARYL-2-(PHENYLSULFANYL)-2-OXIRANYL]-1-ETHANONES

Diastereoselective synthesis of a series of (Z)-1-[3-aryl-2-(phenylsulfanyl)-2-oxiranyl]-1-ethanones was effected from the reaction of (Z)-4-aryl-3-(phenylsulfanyl)-3-buten-2-ones with alkaline hydrogen peroxide in tetrahydrofuran. The stereochemistry of the oxiranes has been deduced from two-dimensional NOESY spectrum.     

(Z)-2-羟基-3-苯甲酰丙烯酸甲酯的合成及晶体结构

标题化合物C11H10O4的晶体结构用X-射线单晶衍射法测定。晶体属单斜晶系, P21/c空间群, 晶胞参数a = 12.136(1), b = 5.559(1), c = 14.615(2) ? b = 96.758(3), V = 979.1(3) ?, Z = 4, Mr = 206.19, Dc = 1.399 g/cm3, F(000) = 432, m(MoKa) = 0.107 mm-1。晶体结构用直接法解出, 经全矩阵最小二乘法对原子参数进行修正, 最终的偏离因子为R = 0.0453, wR = 0.0990。标题化合物形成了1个大的共轭体系, 含有1个稳定的烯醇结构。结构测定表明还存在着1个分子内氢键的结构, 它使烯醇结构更加稳定。     

Synthese und Reaktionsverhalten von 3-(Bis(alkylthio)methylen)-3H-isobenzofuran-1-on-und 2-(Bis(alkylthio)methylen)-3(2H)-benzofuranon-Derivaten

Summary 3(Bis(alkylthio)methylene)-3H-isobenzofuran-1-ones2a–e and 2-(bis(alkylthio)methylene)-3(2H)-benzofuranone derivatives4a–c are obtained by reaction of phthalides1a–d or 3(2H)-benzofuranone (coumaranone3), respectively, with carbon disulfide under basic conditions followed by alkylation. The reaction behaviour of the new compounds2 and4 is investigated. 2-((2-Dimethylthio-1-oxo)ethyl)benzoic acid N,N-dimethylamide (7a) and 2-((2-dimethylthio-1-oxo)ethyl)-benzoic acid 2-methylpiperidide (7b) are surprisingly formed instead of the methylthio substitution products by treatment of2a with the corresponding amine in the presence of aluminum chloride.

Herrn Professor Dr. Dr. h. c.Waldemar Adam zum 60. Geburtstag gewidmet     

2-R-7-Hydroxy-8-methyl-3-(2-quinolyl)chromones

By condensation of 2-methyl resorcinol with 2-quinolyl acetonitrile, we have synthesized α-(2-quinolyl)-2,4-dihydroxy-3-methylacetophenone, which when reacted with carboxylic acid anhydrides followed by hydrolysis yields 2-R-7-hydroxy-8-methyl-3-(2-quinolyl)chromones.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 407–415, March, 2005.     

Synthesis of Gingerenone C and 5-Hydroxy-1-(4'-hydroxy- 3'-methoxyphenyl)-7-(4"-hydroxyphenyl)-3-heptanone

The two diarylheptanoids (E)-1-(4'-hydroxy-3'-methoxyphenyl)-7-(4"-hydroxyphenyl) hept-4-en-3-one 1 (Gingerenone C) and (±)-5-hydroxy-1-(4'-hydroxy-3'-methoxyphenyl)-7-(4"-hydroxyphenyl)-3-heptanone 2 were synthesized from vanillin 3 and 4-hydroxybenzaldehyde 9.     

New Fluoromanganate(III) Hydrates: Mn3F8 · 12H2O and AgMnF4 · 4H2O

Single crystals of fluoride hydrates Mn₃F₈ · 12 H₂O and AgMnF₄ · 4 H₂O have been prepared and characterized by X-ray methods. Mn₃F₈ · 12 H₂O crystallizes in the space group P1 (a = 623.0(3), b = 896.7(4), c = 931.8(4) pm, α = 110.07(2)°, β = 103.18(2)°, γ = 107.54(2)°, Z = 1); AgMnF₄ · 4 H₂O crystallizes in the space group P2₁/m (a = 700.9(2), b = 726.1(1), c = 749.4(3) pm, β = 107.17(3)°, Z = 2). Both structures contain Jahn-Teller-distorted [Mn(H₂O)₂F₄]^? anions as well as crystal water molecules and exhibit a complex hydrogen bond network between anions and cations, i. e. [Mn(H₂O)₆]²⁺ for the first and a polymeric [Ag(H₂O)₂]^? cation for the second compound.     

One-pot synthesis of 3-(2-cyanophenyl)quinazolin-4(3H)-one

Anthranilonitrile reacting with formic acid at room temperature for three days gave 64% of 3-(2-cyanophenyl)quinazolin-4(3H)-one. Under similar conditions anthranilic acid. 4-nitroaniline, and 2,5-dichloroaniline were N-formylated in good yields.Institute of Organic Chemistry and Technology, Silesian Technical University, Krzywoustego, 4, 44–100 Gliwice, Poland; e-mail: wojtex@zeus.polsl.gliwice.pl. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 922–924, July, 2000.     

6-(3-氨基苯基)-4, 5-二氢哒嗪-3(2H)-酮的合成

以苯、丁二酸酐为原料,经傅克酰基化,硝化,与水合肼反应三步反应合成6-(3-氨基苯基)-4,5-二氢哒嗪-3(2H)-酮(1),总收率为58.3%。由3-(3-硝基苯甲酰基)丙酸(3)合成化合物1的过程中,在雷尼镍(Raney Ni)的催化下与水合肼反应,一步完成了苯环上硝基的还原和成环。重点考察了该步反应的物料配比、反应时间对产率的影响。结果表明,水合肼与化合物3的摩尔比11.7∶1,回流反应4 h,产率为82.7%。     

Total synthesis of (3Z,9Z,6S,7R) and (3Z,9Z,6R,7S)-6,7-epoxy-3,9-octadecadienes

(3Z,9Z,6S,7R)-6,7-epoxy-3,9-octadecadiene (1) and (3Z,9Z,6R,7S)-6,7-epoxy-3,9-octadecadiene (2) have been stereoselectively synthesized in eight steps from 2-pentyn-1-ol with an overall yield of 8%. The key steps involved the Sharpless asymmetric dihydroxylation of (2E)-oct-2-en-5-yn-1-ol (6). The new synthetic method is suitable for multigram-scale preparation of 1 and 2 and might be used for producing sufficient quantities of the sex pheromone components for management of the pest of tea plantations.