超声辐射下合成1-[(未)取代苯酰基-3-[5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑-2-基]-硫脲

1-苯基-3-甲基-5-氯吡唑-4-甲酸与氨基硫脲在三氯氧磷中反应得到2-氨基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑(1), 然后分别采用超声辐射法和常规加热法与(未)取代苯甲酰基异硫氰酸酯(2)反应合成了一系列未见报到的1-[(未)取代苯酰基-3-[5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑-2-基]-硫脲(3a～3j). 化合物的结构经元素分析, IR, ¹H NMR确证.     

新型3-取代-6-(4-氯苯基)-7-(1H-1,2,4-三唑-1-基)-1',2',4'-三唑[3,4-b]-1",3",4"-噻二嗪衍生物的合成及抗菌活性

通过3-取代-4-氨基-5-巯基-1,2,4-三唑(3a～3m)和2-溴-2-(1H–1,2,4-三唑-1-基)-4′-氯代苯乙酮(2)的缩合反应, 合成了13个新型3-取代-6-(4-氯苯基)-7-(1H-1,2,4-三唑-1-基)-1',2',4'-三唑[3,4-b]-1",3",4"-噻二嗪衍生物4a～4m. 化合物结构经元素分析, ¹H NMR, IR和MS进行了表征. 抗菌试验表明所合成的化合物对细菌表现出中等程度的抑制活性.     

Synthesis of Some 2-(3-Alkyl/aryl-5-trifluoromethylpyrazol-1-yl)-4-(coumarin-3-yl)thiazoles as Novel Antibacterial Agents

Abstract

Herein, we describe a one-pot synthesis of some novel 2-(3-alkyl/aryl-5-trifluoromethylpyrazol-1-yl)-4-(coumarin-3-yl)thiazoles (6) involving the reaction of 3-alkyl/aryl-5-hydroxy-5-trifluoromethyl-4,5-dihydropyrazole-1-thiocarboxamides (3) with 3-bromoacetylcoumarins (5) in the presence of sodium carbonate in ethanol. Reaction of 3 with 5 in the absence of sodium carbonate, however, resulted in the formation of 2-(3-alkyl/aryl-5-hydroxy-5-trifluoromethyl-4,5-dihydropyrazol-1-yl)-4-(coumarin-3-yl)thiazoles, which were subsequently dehydrated to 6 by refluxing in ethanol in the presence of sodium carbonate. The structure of the synthesized compounds (6) was confirmed by infrared (IR), mass, ¹H NMR, and ¹³C NMR spectra and elemental analysis data. Newly synthesized compounds (6) showed moderate to good activity against Gram-positive bacteria.     

Ultrasound- and microwave-assisted synthesis of (E)-1-aryl-3-[2-(piperidin-1-yl)quinolin-3-yl]prop-2-en-1-ones and (E)-1-aryl-3-[2-(pyrrolidin-1-yl)quinolin-3-yl]prop-2-en-1-ones,and their antimicrobial activity

Series of new (E)-1-aryl-3-[2-(piperidin-1-yl)quinolin-3-yl]prop-2-en-1-ones and (E)-1-aryl-3-[2-(pyrrolidin-1-yl)quinolin-3-yl]prop-2-en-1-ones have been efficiently prepared via the Claisen-Schmidt condensation of 2-(piperidin-1-yl)quinoline-3-carbaldehyde and 2-(pyrrolidin-1-yl)quinoline-3-carbaldehyde, respectively, with aryl methyl ketones under conditions of ultrasound and microwave irradiation. Structures of the products have been confirmed by IR, ¹H NMR, ¹³C NMR, and mass spectroscopy, as well as by elemental analysis. Evaluation of the in vitro antibacterial activity against bacterial (Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli) and fungal (Aspergillus niger and Candida metapsilosis) strains has revealed good antimicrobial activity of some of the tested compounds.     

Synthesis of 3-[4-(1-Benzofuran-2-yl)-1,3-thiazol-2-yl]-2-(4-aryl)-1,3-thiazolidin-4-one Derivatives as Biological Agents

A protocol for the synthesis of 3-[4-(1-benzofuran-2-yl)-1,3-thiazol-2-yl]-2-(4-aryl)-1,3-thiazolidin-4-one derivatives (5a–e) has been developed from 1-(1-benzofuran-2-yl)-2-bromoethanone (2),which served as a key intermediate for the synthesis of the title compounds. The reaction of compound 2 with thiourea furnished 4-(1-benzofuran-2-yl)-1,3-thiazol-2-amine 3, which upon further reaction with various aromatic aldehydes, gave Schiff bases 4a–e. These Schiff bases, when treated with thioacetic acid in the presence of catalytic amount of anhydrous ZnCl₂, yielded thiazolidinone derivatives 5a–e. All the newly synthesized compounds have been characterized by analytical and spectral data and screened for their antimicrobial and analgesic activity.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis and insecticidal activities of O,O-dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy] (aryl) methylphosphonates

A series of novel O,O-Dialkyl-2-[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carbonyloxy](aryl) methy-lphosphonates I-1–14 were designed and synthesized. The structures of all the title compounds were confirmed by ¹H-NMR, ¹³C-NMR, ³¹P-NMR, IR and elemental analysis. Their insecticidal activities against Mythimna separata and Plutella xylostella were evaluated. The results of bioassays indicated that the title compounds exhibited 20–80% larvicidal activity against Mythimna separata at 1000 mg/L.     

Facile and Green Syntheses of 2-(N-Methylindole-3-carbonyl)-3-(N-methylpyrrol-2-yl)acrylonitriles and a Study of Their Antimicrobial Activities

Facile and green syntheses of substituted-2-(N-methylindole-3-carbonyl)-3-(N-methyl pyrrol-2-yl) acrylonitriles 6a–d are being reported. L-Proline has been utilized as an efficient and ecofriendly catalyst in aqueous medium for Knoevenagel condensation of pyrrole-2-carboxyaldehyde (1) and its N-methyl derivative (2) with the active methylene compounds 3-cyanoacetylindoles 3a–d at room temperature to afford substituted-2-(1H-indole-3-carbonyl)-3-(1H-pyrrol-2-yl)acrylonitriles 4a–d and substituted-2-(1H-indole-3-carbonyl)-3-(N-methylpyrrol-2-yl) acrylonitriles 5a–d respectively. Subsequently these products were treated with dimethyl sulfate (DMS) in polythylene glycol (PEG)–600 as an efficient and green solvent to afford the corresponding substituted-2-(N-methylindole-3-carbonyl)-3-(N-methylpyrrol-2-yl)acrylonitriles 6a–d. The antibacterial and antifungal activities of 4a–d, 5a–d, and 6a–d have been studied.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

2-(1-苯基/取代苯基-3-甲基-5-氯-1H-4-吡唑基)-3-芳酰胺-4-噻唑啉酮的合成及生物活性

利用1-芳基-3-甲基-5-氯-1H-4-吡唑醛(2)分别与取代苯甲酰肼反应, 进一步与巯基乙酸关环, 合成了11个新的2-(1-芳基-3-甲基-5-氯-1H-4-吡唑基)-3-芳酰胺-4-噻唑啉酮类化合物 3a～3k, 并利用元素分析, IR, ¹H NMR和X-ray晶体衍射确定了其结构. 初步生物活性表明: 3e具有杀菌活性, 3e和3k具有除草活性.     

Synthesis,characterisation and structural aspects of some symmetrical organotellurium halides based on Bis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)telluride

Bis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)telluride (2) has been synthesised in good yield by reacting 1-(2-chloroethyl)-3,5-dimethylpyrazole with in situ prepared sodium telluride, Na₂Te in an aqueous solution. A number of new organotellurium halides from bis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)telluride have been synthesised by using different halogenating reagents. Reaction of 2 with bromine gave bis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)telluride dibromide (5a) in addition to unexpected product bis(2-(4-bromo-3,5-dimethyl-1H-pyrazol-1-yl)ethyl)telluride dibromide (5b). All compounds were characterized by different spectroscopic techniques viz., ¹H, ¹³C, ¹²⁵Te NMR, Mass spectroscopy, IR and CHN analysis. EDXRF studies have also been employed to confirm the identity of 5a and 5b. Thermal gravimetric analysis of bis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)telluride (IV) chloride (4) and bis(2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)telluride (IV) iodide (5c) reveals the thermal stability of these molecules above 100°C. The X-ray studies of 5c shows trigonal bipyramidal geometry around tellurium atom and intermolecular secondary interaction viz., C-H π stacking between H23A and C22 showing a supramolecular packing between two molecules.     

4-(取代嘧啶-2-基)-1-芳磺酰基氨基脲化合物的合成与表征

以取代的苯磺酰肼与(取代嘧啶-2-基)-氨基甲酸苯酯在非亲核性碱存在下合成了12个4-(取代嘧啶-2-基)-1-芳磺酰基氨基脲化合物5和3个5与碱形成的有机盐5as, 5bs和5cs. 所有合成化合物均经过元素分析和¹H NMR的结构确证. ¹H NMR数据证明, 在5as～5cs中, 磺酰氨基脲起到提供质子的作用.     

Facile Synthesis of Some 3-(Benzimidazol-2-yl)- and 3,6-Di(Benzimidazol-2-yl)-9-ethyl-9H-carbazoles

A simple and efficient synthesis of novel 3-(benzimidazol-2-yl)- and 3,6-di(benzimidazol-2-yl)-9-ethyl-9H-carbazoles is described. The synthetic approach for the preparation of 2-substituted benzimidazoles 4–8 and bis-benzimidazoles 9–12 was achieved by the condensation of carbazole-3-carbaldehyde 2 and carbazole-3,6-dicarbaldehyde 3 with o-phenyldiamines in dimethylformamide or dimethylsulfoxide in moderate to excellent yield. The identities of synthesized compounds were confirmed using ¹H NMR, ¹³C NMR, infrared (IR), and high-resolution mass spectrometry (HRMS).     

5-(N-Arylnortropan-3-yl)- and 5-(N-Arylpiperidin-4-yl)-2,4-diaminopyrimidines. Novel Inhibitors of Dihydrofolate Reductase

Based on a computer-assisted analysis of the three-dimensional structure of the binary complex of E.coli dihydrofolate reductase (DHFR) with methotrexate, 5-(N-arylnortropan-3-yl)- and 5-(N-arylpiperidin-4-yl)-2,4-diaminopyrimidines 2 and 4 were designed as inhibitors of DHFR. Syntheses of the designed compounds have been carried out. The most potent compound 2a inhibited E. coli DHFR with K_i = 0.49.10^?9M. The activities within the series of compounds synthesized could be rationalized by molecular-modelling experiments which served as the basis of this work. Several compounds within the presented series exhibit antimalarial activities in vitro and in vivo.     

Synthesis of elastomeric polypropylene in bulk using C 1-symmetric ansa-metallocenes. New aspects of the synthesis of 1-(fluoren-9-yl)-2-(2-methyl-5,6-dihydrocyclopenta [f]-1H-inden-1-yl)ethane and complexes of zirconium and hafnium with this ligand

Isomeric 1-(fluoren-9-yl)-2-(2-methyl-5, 6-dihydrocyclopenta [f]-1 H-indenyl) ethanes 1a,b and C ₁-symmetric metallocenes, viz., rac-1-(η⁵-fluoren-9-yl)-2-(2-methyl-5, 6-dihydrocyclopenta [f]-η⁵-inden-1-yl) ethanezirconium dichloride (9) and rac-1-(η⁵-fluoren-9-yl)- 2-(2-methyl-5, 6-dihydrocyclopenta [f]η⁵-inden-1-yl)ethanehafnium dichloride (10), with these ligands were synthesized by modified procedures. The structures of compounds 1b (two crystalline modifications) and 10 were established by X-ray diffraction analysis. The synthesis of polypropylene (PP) in bulk was studied in the presence of polymethylalumoxane-activated metallocenes 9 and 10 in the temperature range of 30–70°C. It was demonstrated that triisobutylaluminum can be used as a cocatalyst. In this case, the molecular weight of PP increases by a factor of ∼2. An increase in the reaction temperature leads to an increase in stereoregularity and crystallinity of PP. The polymer synthesized at high temperatures crystallizes in the γ form. The resulting PP is characterized by a wide range of properties from rigid crystalline thermoplastic to amorphous elastomeric. Samples, which have a high molecular weight and moderate isotacticity, exhibit high elastomeric and durability properties.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 400–413, February, 2005.     

Synthesis of Some Novel 5-(Arylidene)-2-imino-3(pyridin-2-yl)thiazolidin-4-one Derivatives

Treatment of 2-aminopyridine ( 1 ) with chloroacetyl chloride in dry benzene gave 2-chloro-N-(pyridin-2-yl)acetamide ( 3 ), which on further reaction with potassium thiocyanate gave 2-imino-3-(pyridin-2-yl)thiazolidin-4-one ( 4 ) as an intermediate compound for the synthesis of pyridin-2-yl substituted 2-imino-thiazolidine-4-one derivatives. Cyclocondensation reaction of ( 4 ) with a series of aromatic aldehydes gave 5-arylidene derivatives of pyridin-2-yl substituted 2-imino-thiazolidine-4-ones 5a–j . ¹ H and ¹³C NMR spectroscopy, as well as elemental analyses, were used for the identification of these new compounds.     

2,2-二甲基-5-取代苯基-3-(1,2,4-三唑-1/4-甲基)-3-戊醇类化合物的合成、表征及生物活性

取代苯甲醛经缩合、催化氢化、环氧化和开环反应合成了9种2,2-二甲基-5-取代苯基-3-(1,2,4-三唑-1-基甲基)-3-戊醇类化合物和2种2,2-二甲基-5-取代苯基-3-(1,2,4-三唑-4-基甲基)-3-戊醇类新化合物. 并对1,2,4-三唑-1-基衍生物和1,2,4-三唑-4-基衍生物的选择性合成进行了研究; 新化合物结构经质谱, ¹H NMR, 元素分析等确证, 并用单晶X射线衍射测定了化合物1a的晶体结构. 生物活性测试结果表明, 部分化合物具有强杀菌活性.     

Synthesis and Herbicidal Activity of O,O-Dialkyl(phenyl)-N-{1-[(6-chloropyridin-3-yl)methyl]-4-cyano-1H-1,2,3-triazol-5-yl}-1-amino-1-substitutedbenzyl-phosphonates

Abstract

A series of novel α-amino phosphonate derivatives containing both pyridine and 1,2,3-triazole moieties 4 were synthesized via a multi-step reaction. First, the condensation of 5-amino-1-[(6-chloropyridin-3-yl) methyl]-4-cyano-1H-1,2,3-triazole with various aromatic aldehydes in the presence of magnesium perchlorate afforded imines 3 in moderate yields; second, imines 3 reacted with dialkyl phosphites or triphenyl phosphite to give the title compounds 4 in moderate to good yields. Their structures were elucidated by spectroscopic data (IR, ¹H NMR, ³¹P NMR, ESI-MS) and elemental analysis. The preliminary bioassay (in vitro) indicated that some of the title compounds 4 possessed moderate herbicidal activities against dicotyledonous plants (Brassica campestris L) at a concentration of 100 mg/L. However, compounds 4 did not exhibit herbicidal activities against Brassica campestris L at a concentration of 10 mg/L.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

A Convenient Synthesis of Novel 4-(1,2,4-Triazol-1-yl)-2-pyrazolines and Their Derivatives

Abstract

Upon the study of powerful insecticidal and fungicidal properties of 1-phenylcarbamoyl-2-pyrazolines and 1,2,4-triazoles compounds, a variety of novel 4-(1,2,4-triazol-1-yl)-pyrazolines and their derivatives were prepared in good yields. The structures of these compounds were confirmed with ¹H NMR, MS, IR and elemental analyses.     

N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类新化合物的合成及生物活性

以N-吡啶基吡唑甲酸和2-氨基-3-甲基苯甲酸为起始原料,经由亲核加成、环化和酰化等多步反应合成了一系列结构新颖的N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)酰胺类化合物.测试了所合成化合物的杀虫及抑菌活性,结果表明,新化合物大多化合物在200 mg·L^-1浓度下对东方粘虫(Mythimna separataWalker)具有一定的杀虫活性,尤其是N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)乙酰胺(8a)和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3-氯-2,2-二甲基丙酰胺(8e)致死率可达70%;部分化合物在50 mg·L^-1浓度下对油菜菌核病菌的抑菌活性相对较好(54.5%~63.6%),优于triadimefon和chlorantraniliprole;部分化合物如N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-3,3-二甲基丁酰胺80和N-(2-(5-(3-溴-1-(3-氯吡啶-2-基)-1H-吡唑-5-基)-1,3,4-噁二唑-2-基)-4-氯-6-甲基苯基)-4-氟苯甲酰胺(8h)对苹果轮纹病菌具有中等抑菌活性.值得注意的是,化合物8e的杀粘虫活性和对油菜菌核病菌的抑菌活性都较为突出,可用作新农药创制研究的新型参考结构.     

Crystallographic characterization of three cathinone hydrochlorides new on the NPS market: 1-(4-methylphenyl)-2-(pyrrolidin-1-yl)hexan-1-one (4-MPHP), 4-methyl-1-phenyl-2-(pyrrolidin-1-yl)pentan-1-one (α-PiHP) and 2-(methylamino)-1-(4-methylphenyl)pentan-1-one (4-MPD)

Cathinones belong to a group of compounds of great interest in the new psychoactive substances (NPS) market. Constant changes to the chemical structure made by the producers of these compounds require a quick reaction from analytical laboratories in ascertaining their characteristics. In this article, three cathinone derivatives were characterized by X-ray crystallography. The investigated compounds were confirmed as: 1-[1-(4-methylphenyl)-1-oxohexan-2-yl]pyrrolidin-1-ium chloride ( 1 , C₁₇H₂₆NO⁺·Cl^?, the hydrochloride of 4-MPHP), 1-(4-methyl-1-oxo-1-phenylpentan-2-yl)pyrrolidin-1-ium chloride ( 2 ; C₁₆H₂₄NO⁺·Cl^?, the hydrochloride of α-PiHP) and methyl[1-(4-methylphenyl)-1-oxopentan-2-yl]azanium chloride ( 3 ; C₁₃H₂₀NO⁺·Cl^?, the hydrochloride of 4-MPD). All the salts crystallize in a monoclinic space group: 1 and 2 in P2₁/c, and 3 in P2₁/n. To the best of our knowledge, this study provides the first detailed and comprehensive crystallographic data on salts 1 – 3 .     

Synthesis of 1-aryl-3-（3,4-dihydro-2H-chromen-5-yl） ureas as TNF-α inhibitors

A new series of compounds,1-aryl-3-(3,4-dihydro-2H-chromen-5-yl) ureas,have been synthesized and their structures were confirmed by FAB-MS and ~1H NMR.The preliminary pharmacological screening showed that these compounds inhibited TNF-αproduction in lipopolysaccharide (LPS)-stimulated THP-1 cells.