Synthesis of 2,5-bis[(3,4-ethylenedioxy)thien-2-yl]- 3-substituted thiophenes

[reaction: see text] Synthesis of 2,5-bis[(3,4-ethylenedioxy)thien-2-yl]-3-substituted thiophene monomers afforded compounds with blue emission characteristics and having a quantum yield of 3-5%. Cyclic voltammetry was employed to investigate the electrochemical behavior of the four monomers reported here. Polymer films were deposited by repeated potential cycling. These materials are considered for use in tailoring properties in optoelectronic device applications.     

Naturally Occurring5-[(2-Thienyl)Ethynyl] Thiophene-2-Carbal-Dehyde Through a Short Synthesis of Diarylacetylenes

Title compound and related diarylacetylenes were synthesized via a one-pot procedure starting from aryliodide and trimethylsilylacetylene.     

Crystal and Molecular Structure of Ethyl 2-[（4-Hydroxy-phenyl）hydrazono]-3-oxobutanoate

The title compound,C 12 N 2 O 4 H 14 (M r=250.3),crystallizes in triclinic P1 space group with a=7.7709(9),b=8.7534(11),c=9.6958(12),α=77.103(2),β=80.496(2),γ=86.726(2)o,V=633.9(1) 3,Z=2,F(000)=264,D c=1.311 Mg/m 3,μ(MoKα)=0.1 mm-1,the final R=0.056,and wR=0.15 for 2239 observed reflections (I > 2σ(Ⅰ)).The molecules in the crystal are linked through O-H···O type of hydrogen bonding interaction forming an infinite chainlike structure.The phenylhydrazone ring and oxobutanoate groups are almost planar.The keto hydrazo group adopts a Z-configuration in the molecule and the torsion angle is-177.6(2)°.     

2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉类化合物的合成

在冰醋酸存在下, 4-取代苯乙酮和溴素容易进行溴代反应, 得到α-溴-4-取代苯乙酮; 将其和1,2,4-三唑在丙酮中反应, 得到α-(1,2,4-三唑-1-基)-4-取代苯乙酮2; 在冰醋酸催化下, 2和4-取代苯甲酰肼1进行缩合, 得到相应酰腙衍生物3; 化合物3在乙酸酐的作用下环化生成一系列2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉4. 化合物4的结构经IR, 1H NMR, MS, 元素分析和单晶衍射确证.     

2,5-二甲氧基-4-[(1E)-2-(1H-苯并咪唑-2-基)乙烯基]苯甲醛的合成

以2-甲基苯并咪唑(1)和2,5-二甲氧基-1,4-对苯二甲醛(3)为原料,经缩合反应合成了新化合物——2,5-二甲氧基-4-[(1E) -2-( 1H-苯并咪唑-2-基)乙烯基]苯甲醛(4),其结构经1H NMR,IR和ESI-MS表征.较佳缩合反应条件为:1 11 mol,n(1)∶n(3)=1.1∶1.0,回流反应6h,收率75.2％.     

Synthesis of Ethyl 2-Hydroxy-3-[aryl(2-naphthylamino)methyl]-2-cyclopentenecarboxylates and Ethyl 3-Arylmethylene-2-(2-naphthylamino)-1-cyclopentenecarboxylates

Condensation of N-arylmethylene-2-naphthylamines with ethyl 2-oxocycopentanecarboxylate in the presence of HCl or CH₃COOH yields ethyl 2-hydroxy-3-[aryl(2-naphthylamino)methyl]-2-cyclopentenecarboxylates and ethyl 3-arylmethylene-2-(2-naphthylamino)-1-cyclopentenecarboxylates, respectively.     

Synthesis of azoles from 3-[(3-hydrazino-3-oxopropyl)anilino]-and 3-[(3-hydrazino-3-oxopropyl)-4-methylanilino]propane hydrazides

Condensation of 3-[(3-hydrazino-3-oxopropyl)anilino]-and 3-[(3-hydrazino-3-oxopropyl)-4-methylanilino]propane hydrazides with 2,4-pentanedione, phenyl isocyanate or phenyl isothiocyanate (with subsequent work up of the semicarbazides obtained by base), and carbon disulfide gave respectively: 1-(3,5-dimethyl-1H-1-pyrazolyl)-3-[3-(3,5-dimethyl-1H-1-pyrazolyl)-3-oxopropylanilino]-1-propanone, 3-(2-{[2-(5-oxo-4-phenyl-4,5-dihydro-1H-1,2,4-triazol-3-yl)ethyl]anilino}ethyl)-4-phenyl-4,5-dihydro-1H-1,2,4-triazol-5-one and its thio analog, and 5-(2-{[2-(2-thioxo-2,3-dihydro-1,3,4-oxadiazol-5-yl)ethyl]anilino}ethyl)-2,3-dihydro-1,3,4-oxadiazole-2(3H)-thione plus their methyl derivatives. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1353–1358, September, 2007.     

Synthesis and structure of 4-[(4-Nitro-1,2,5-oxadiazol-3-yl)-NNO-azoxyl]-1, 2,5-oxadiazol-3-amine

The synthesis of the energetic compound 4-[(4-nitro-1,2,5-oxadiazol-3-yl)-NNO-azoxyl]-1,2,5-oxadiazol-3-amine (3) was achieved in two steps from diaminofurazan (1). Compound 3 was characterized by X-ray diffraction. From the X-ray structure a bifurcated intramolecular H bond between O(2)-H(2)-N(4) was observed. In addition, intramolecular H bonding was observed between H(1) and N(7) of an adjacent molecule. One molecule of ethanol and one-half molecule of water per molecule of3 was observed in the crystal lattice. However, no H bonding was observed between the solvent molecules and3 in the crystal lattice. Despite the presence of solvent in the crystal lattice,3 was found to have a high crystal density (d=1.856 g/cm³).     

Synthesis of N-methyl-N-[(1S)-1-[(3R)-pyrrolidin-3-yl]ethyl]amine

N-Methyl-N-[(1S)-1-[(3R)-pyrrolidin-3-yl]ethyl]amine (1)(1) is a key intermediate in the preparation of premafloxacin (2), which was under development as an antibiotic for use against pathogens of veterinary importance. This paper describes the development of a practical, efficient, and stereoselective process for the preparation of 1 from isobutyl (3S)-3-[methyl[(1S)-1-phenylethyl]amino]butanoate (5c). The key steps in the synthetic sequence are an asymmetric Michael addition, which yields 5c, and a stereoselective alkylation, which yields (3S,4S)-3-allyl-1,4-dimethylazetidin-2-one (17).     

Synthesis and electrocatalytic properties of a dinuclear palladium(I) 1-[(2-bromo)benzene]-3-[(2-carboxymethyl)benzene]triazenide complex

The reaction of 1-[(2-bromo)benzene]-3-[(2-carboxymethyl)benzene]triazene and [Pd(CH₃CN)₄]Cl₂ gave a new dinuclear triazenido complex [Pd₂L₂] 1, which has been characterized by NMR spectra and X-ray crystallography. Electrochemical studies showed that complex 1 is capable of generating hydrogen from acetic acid in CH₂Cl₂.     

Synthesis of 2-Deoxy-2-[(3R)-3-Hydroxyacyl]Amino-4-O-Phosphono-3-O-[(3R)-3-Tetradecanoyloxytetradecanoyl]-D-Glucopyranose Derivatives Related to Bacterial Lipid A

ABSTRACT

Lipid A subunit analogs, the 4-O-phosphono-D-glucosamine derivatives (14-16: GLA 93-95) which carry 2-N-linked 3-hydroxyacyl groups, were synthesized. 2-(Trimethylsilyl)ethyl 2-amino-2-deoxy-4,6-O-isopropylidene-ß-D-glucopyranoside (1) was transformed into 2-(trimethylsilyl)ethyl 2-amino-6-O-tert-butyldimethylsilyl-2-deoxy-4-O-diphenylphosphono-3-O-[(3R)-3-tetradecanoyloxytetradecanoyl]-ß-D-glucopyranoside (7) through several steps. N-Acylation of 7 with 3-hydroxyl fatty acids gave the corresponding 8-10, which were converted, via the cleavage of protecting groups, into a series of desired compounds.     

Synthesis of 1-[(1,2-dithiol-3-ylidene)methyl]pyrrolo[1,2-a]pyrazines and 2-[(1,2-dithiol-3-ylidene)methyl]pyridines from 1,2-dithiole-3-thiones

Benzo- and pyridoannulated 1,2-dithiole-3-thiones react with compounds containing an activated methyl group such as 1-methyl-3,4-dihydropyrrolo[1,2-a]pyrazine and 2-methylpyridines to furnish substituted 1,2-dithiol-3-ylidenes.     

2-氰基-3-取代胺基-3-[2-(4-氟苯基)-乙胺基]丙烯酸乙酯类化合物的合成及生物活性研究

以氰基乙酸乙酯为原料,经与二硫化碳、硫酸二甲酯反应合成了2-氰基-3,3-二甲硫基丙烯酸乙酯(1),然后引入对氟苯乙胺得到化合物(3),其与脂肪胺反应合成了新型含对氟苯乙氨基的2-氰基丙烯酸乙酯类化合物5a～5h,其结构经元素分析,IR1H NMR和13C NMR等确证.初步生物活性试验表明,部分化合物具有一定抗烟草花叶病毒活性.     

Synthesis and Characterization of 2-[(3-Aminophenyl)sulfonyl] ethanol Hydrogen Sulfate

2-[(3-Aminophenyl)sulfonyl] ethanol hydrogen sulfate (APSES) is an important intermediate for reactive dyes.It can be used to synthesize KN type reactive dyes, which have broad colour spectra,good water solubility, excellent adaptability for different dye technique,etc. Synthesis of APSES were currently developed by Kato Kuniok et al^[1] and Sanki^[2].Kato had attempted to synthesize of APSES by reaction of sodium benzenesulfinate as raw material with ethylene oxide to obtain 2-phenylsulfonyl ethanol(PSE). The PSE could further be nitrated and hydrogenated to obtain 2-[(3-aminophenyl)sulfonyl]ethanol (APSE). Finally,APSE was reacted with oleum to obtain 2-[(3-aminophenyl) sulfonyl] ethanol hydrogen sulfate (APSES). Sanki had discoved a new synthetic method for the PSE. The PSE was prepared by first reaction of thiophenol as raw material with chloroethanol, and then by oxidation with hydrogen peroxide.The above mentioned two methods are not easily be adopted in industries at home. The shortage and cost of the thiophenol and sodium benzenesulfinate are mainly limited. We modificated a new synthetic pathway for APSES by five steps. The experimental procedures are shown the following.     

Synthesis and biological activity of new 2-[(3-aminopropyl)dimethyl-silyl]-5-trialkylgermylfurans

New highly cytotoxic 3-aminopropyl derivatives of 2-dimethylsilyl-5-trialkylgermylfuran (IC₅₀ 1−3 μg⋅ml⁻¹) have been prepared by hydrosilylation of heterocyclic N-allylamines with the corresponding hydrosilane in the presence of Speier’s catalyst. The influence of the amine structure and alkyl substituent at the germanium atom on the cytotoxicity has been investigated.