The One Step Synthesis of 2-(2-Bromo-5- methoxyphenyl)-5-(3-arylidene)-1,3-thiazolo[3,2-b]- 1,2,4-triazol-6-(5H)-ones and the Evaluation of the Anticonvulsant Activity

A smooth one-step synthesis of 2-(2-bromo-5-methoxyphenyl)-5-(3-arylidene)-1,3-thiazolo[3,2-b]-1,2,4-triazol-6-(5H)-ones (4a–n) is described. The newly prepared compounds are characterized by analytical and IR, ¹ H NMR, ¹³ C NMR, and FABMS spectral analysis. A few compounds are screened for anticonvulsant activity. Compounds 4i and 4n exhibit promising anticonvulsant activity and are recommended for further studies.     

Synthesis, spectroscopic and DFT investigation of dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate

Dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate has been synthesized and characterized by elemental analysis, FT-IR and ¹H, ¹³C and ³¹P NMR. The vibrational wavenumbers, gauge including atomic orbital (GIAO) ¹H and ¹³C chemical shift values of title compound in the ground state have been computed with density functional theory method (DFT) and the B3LYP functional. The basis sets used are 6-311G(d,p) and 6-31G(d). The harmonic vibrational wavenumbers have been computed and the scaled values have been compared with the experimental FT-IR spectra. The complete assignments have been performed on basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Most of the computed wavenumbers are found to be in good agreement with the observed spectrum.     

Carbon-13 NMR Studies of 3-Aryl-4-(5-aryl-Δ 2-1,2,4-oxadiazolin-3-yl)sydnones and 3-Aryl-4-(5-aryl-1,2,4-oxadiazol-3-yl)sydnones

The ¹³C NMR spectra of twelve 3-aryl-4-(5-aryl-Δ²-l,2,4-oxadiazolin-3-yl)sydnones and twelve 3-aryl-4-(5-aryl-l,2,4-oxadiazol-3-yl)sydnones have been measured and assigned by means of proton-noise decoupling and DEPT-experiments. The coupling constants were determined by means of gated decoupling, and NOE effects were observed by comparison of proton-decoupled and inverse-gated decoupled spectra. Differences shown by the oxadiazoline and the oxadiazole rings and the substitution effects are discussed.     

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.      

N-{4-{N-甲基-N-[2-羟基-3-(2,4-二氧代-1,2,3,4-四氢嘧啶-5-基)氨基]丙基}氨基-3-溴}苯甲酰基-L-谷氨酸二乙酯及其衍生物的合成

报道了N-{4-{N-甲基-N-[2-羟基-3-(2,4-二氧代-1,2,3,4-四氢嘧啶-5-基)氨基]丙基}氨基-3-溴}苯甲酰基-L-谷氨酸二乙酯及其衍生物的简便合成方法. 分别以4-氨基苯甲酸乙酯和4-氨基苯甲酰基-L-谷氨酸二乙酯为起始物, 经甲基化、烯丙基化、溴羟基化、环氧化、开环、脱保护等反应首次合成了6个新型5-取代氨基嘧啶类化合物, 并通过¹H NMR, ¹³C NMR 和MS对其化学结构进行了表征. 初步生物活性结果表明, 苯环侧链的L-谷氨酸酯部分是此类化合物抑制人重组二氢叶酸还原酶的必需结构.     

2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-5-(取代苯基亚甲基)-4- 噻唑啉酮的合成

以2-氨基-5-取代苯氧甲基-1,3,4-噻二唑(1)为起始原料, 合成了中间体2-氯乙酰氨基-5-取代苯氧甲基-1,3,4-噻二唑)-2-乙酰亚胺(2)和2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-4-噻唑啉酮(3), 化合物3进一步与取代苯甲醛发生类Knoevenagle缩合反应, 得到了一系列2-(5-取代苯氧甲基-1,3,4-噻二唑-2-亚胺基)-5-(取代苯基亚甲基)-4-噻唑啉酮类化合物4a～4p. 目标化合物4a～4p的结构经IR, ¹H NMR和元素分析确证.     

微波作用下1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑的合成及生物活性

采用微波和相转移催化法通过1-苯基-5-(4-苯基-1,2,4-三唑-5-巯基-3-甲硫基)四唑(2)与2-氯乙酰芳胺(3)反应高效、快速地合成了10种尚未见文献报道的1-苯基-5-[5-(芳胺羰基甲硫基)-4-苯基-1,2,4-三唑-3-甲硫基]四唑. 其结构经 IR, ¹H NMR, ¹³C NMR 和元素分析表征. 生物活性实验结果表明, 该类化合物在较低浓度下部分化合物对小麦芽有很好的促进作用.     

N-取代芳酰氨基-5-氟代苯基-2-呋喃甲酰硫脲的合成与生物活性测定

从5-氟代苯基-2-呋喃甲酸出发, 经酰化、异硫氰酸酯化, 再与取代芳酰肼反应合成了20个未见文献报道的N-取代芳酰氨基-5-氟代苯基-2-呋喃甲酰硫脲. 目标产物的结构经IR, ¹H NMR和元素分析测定确证. 初步生物活性测试表明, 部分化合物对棉花枯萎病、黄瓜灰霉病、苹果轮纹病和棉花炭疽病有较好的选择性杀菌活性; 部分目标化合物有较好的除草活性.     

Functionalization of 5-(4-alkoxybenzyl)-4-R-4<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole-3-thiols. Synthesis of novel DNA methylation inhibitors

Aminomethylation and cyanoethylation reactions of 5-(4-alkoxybenzyl)-4-methyl(phenyl, allyl)-4H-1,2,4-triazole-3-thiols have been investigated. According to NMR spectroscopy data, the reactions occur at the nitrogen atom Ν². The effect of the synthesized compounds on cancer DNA methylation has been evaluated.     

Zn(II) and Cu(II) complexes of 2-(2-hydroxy-5-methylphenyl)-1<Emphasis Type="Italic">H</Emphasis>-benzimidazole and crystal structure of 2-(2-hydroxy-5-methylphenyl)-1<Emphasis Type="Italic">H</Emphasis>-benzimidazolium chloride

2-(2-Hydroxy-5-methylphenyl)-1H-benzimidazole ligand (HL) and its complexes with Cu(NO₃)₂, Zn(NO₃)₂ have been synthesized and characterized. The structures of the compounds were confirmed on the basis of elemental analysis, molar conductivity, magnetic moment, FT-IR, ¹H- and ¹³C NMR. Cu(II) complex has 1: 2 metal: ligand ratio, while Zn(II) complex is 1: 1. Crystal structure of 2-(2-hydroxy-5-methylphenyl)-1H-benzimidazolium chloride (HL · HC1) was determined by single-crystal X-ray diffraction. It crystallizes in the orthorombic, space group P2₁2₁2₁and Z = 4.     

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.     

Dibenzyltin(IV) complexes of the 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-olates: Synthesis and an investigation of structures by X-ray diffraction, solution and solid-state tin NMR, Sn Mössbauer and electrospray ionization MS

A series of cis-bis{5-[(E)-2-(aryl)-1-diazenyl]quinolinolato}dibenzyltin(IV) complexes have been synthesized by reacting sodium salts of 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-ol (LH) and dibenzyltin dichloride. These complexes have been characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS in solution and by IR and ^119mSn Mössbauer, ¹¹⁷Sn CP-MAS NMR spectroscopy in solid state. In addition, the structures of three of the dibenzyltin(IV) complexes, viz., Bz₂Sn(L²)₂ (2), Bz₂Sn(L³)₂ (3), and Bz₂Sn(L⁵)₂ (5) (L = 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-ol: aryl = 4′-methylphenyl- (L²H), 4′-methoxylphenyl- (L³H) and 4′-bromophenyl- (L⁵H)) were determined by single-crystal X-ray diffraction. In general, the complexes were found to adopt a distorted cis-octahedral arrangement around the tin atom in both solution and solid state.     

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.     

Synthesis,Structure, and Anti-influenza Activity of 2-(Adamantan-1-yl)-5-aryl-1,3,4-oxadiazoles and 2-(Adamantan-1-yl)-5-aryltetrazoles

Two series of new adamantyl derivatives of polynitrogen heterocycles, 2-(adamantan-1-yl)-5-aryl- 1,3,4-oxadiazoles and 2-(adamantan-1-yl)-5-aryl-2H-tetrazoles, have been synthesized, and their structure has been determined by NMR spectroscopy, mass spectrometry, and X-ray analysis. Biological studies in vitro have revealed high inhibitory activity of some of the synthesized 2-(adamantan-1-yl)-5-aryl-2H-tetrazoles against H1N1 influenza A viruses in combination with a relatively low selectivity.     

Asymmetric synthesis,stereochemistry, and absolute configuration of 1,2-5-trimethyl-5-(2-cyanoethyl)- and 1,2,5-trimethyl-4-piperidinones

The asymmetric Michael alkylation of (–)-1,2,5-trimethyl-4-(1S-phenylethylimino)piperidine by electrondeficient alkenes proceeds with the formation of(+)-cis-(2S,5S)- and (–)-trans-(2R,5S) diastereomers of 1,2,5-trimethyl-5-(2-cyanoethyl)- and 1,2,5-trimethyl-5-(2-methoxycarbonylethyl)-4-piperidinones containing a chiral quaternary center C(₅). The spatial structure of these new chiral 4-piperidinones has been established on the basis of ¹H and ¹³C NMR spectroscopic data. The absolute configuration of the C(₂) and c(₅) chiral centers in the diastereomers has been determined by stereochemical correlation on the basis of circular dichroism data.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1369–1378, October, 1992.     

New chiral tin compounds containing the 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand

A series of tri- and tetraorganotin compounds containing the optically active 2-(4-isopropyl-2-oxazolinyl)-5-phenyl ligand and tert-butyl, methyl and/or phenyl groups on the tin has been synthesized. All the novel compounds have been characterized, especially by means of the multinuclear NMR investigation, the results of which are discussed. The tin halides, as pairs of diastereoisomers in solution, crystallize in the form of one diastereoisomer. The single-crystal X-ray analysis of tin iodide 10a revealed pseudo-equatorial position of the tert-butyl group opposite to the isopropyl group. In the corresponding diastereomeric tin hydrides values of ¹J(¹H-^117/119Sn) differ significantly, suggesting a different pseudo-axial/equatorial position of the hydrogen atom.     

Synthesis and biological activity of ethyl 2-(5-methyl-3-arylisoxazole-4-carboxamido)-4-alkylthiazole-5-carboxylate

A series of novel ethyl 2-(5-methyl-3-arylisoxazole-4-carboxamido)-4-alkylthiazole-5-carboxylates I-1-6 were synthesized. The structures of all target compounds were characterized by ¹H NMR, ¹³C NMR, IR, MS and elemental analyses. Their fungicidal and herbicidal activities were evaluated. The results of preliminary bioassays show that the title compounds I-4 possess 20–50% inhibition against most of the tested plants at the dosage of 150 g ai/ha, while the title compounds I-1-5 possess 32–58% inhibition against FusaHum graminearum, Thanatephorus cucumeris, Botrytis cinereapers and Fusarium oxysporum in vitro at the concentration of 100 mg/L.     

Synthesis and tautomerism of 2-[3(5)-aryl(methyl)pyrazol-4-yl]-1-benzimidazoles

An efficient method has been developed for the synthesis of 2-[3(5)-aryl(methyl)pyrazol-4-yl]-1H-benzimidazoles by cyclocondensation of 2-acylmethyl-1H-benzimidazoles benzoylhydrazones with DMF dimethylacetal. The tautomerism of the compounds obtained via migrations of a proton between the pyrazole nitrogen atoms has been studied by ¹H NMR. The more stable tautomers have electron acceptor aryl substituents placed at position 3 of the pyrazole ring and electron donor aryl substituents or a methyl at position 5. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1370–1377, September, 2006.     

Synthesis and characterization of novel poly(2-methoxy-(5-(6′-dimethylphosphonate)-hexyloxy)-1,4-phenylenevinylene-ran-2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene)s (MEH-PO-PPVs) and their tunable emission colors

Poly(2-methoxy-(5-(6′-dimethylphosphonate)-hexyloxy)-1,4-phenylenevinylene-ran-2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PO-PPV) was synthesized via Heck coupling reaction of MPOHOB-2Br (1) (1-methoxy-(4-(6-dimethylphosphonate)-hexyloxy)-2,5-dibromobenzene), MEHOB-2Br (2) (1-methoxy-4-(6-bromohexyloxy)-2,5-dibromobenzene), and MEHOB-DV (4) (1-methoxy-4-(2′-ethylhexyloxy)-2,5-divinylbenzene) by varying the molar ratios of monomers. The monomers and their intermediates were characterized by ¹H NMR, FT-IR, and melting point and elemental analyzer, and subsequent polymers by FT-IR, ¹H NMR, GPC, DSC, TGA, and solubility test. The optical (UV-vis, PL) and electrical properties (CV) of polymers were also evaluated. MEH-PO-PPV, containing phosphine oxide groups, exhibited better solubility, lower HOMO and LUMO levels, and larger band gaps. In addition, the PL emission gradually shifted to shorter wavelength, providing 570 (MEH-10PO-PPV), 519 (MEH-30PO-PPV), and of 465 nm (MEH-50PO-PPV) as the PO content increased, compared with 598 nm (MEH-PPV).     

Diphenyltin(IV) complexes of the 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-olates: Synthesis and multinuclear NMR, Sn Mössbauer, electrospray ionization MS, X-ray characterization and assessment of in vitro cytotoxicity

A series of cis-bis{5-[(E)-2-(aryl)-1-diazenyl]quinolinolato}diphenyltin(IV) complexes have been synthesized and characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, ESI-MS, IR and ^119mSn Mössbauer spectroscopic techniques in combination with elemental analysis. The structures of a ligand L⁶H (i.e., 5-[(E)-2-(4-ethoxyphenyl)-1-diazenyl]quinolin-8-ol) and three diphenyltin(IV) complexes, viz., Ph₂Sn(L¹)₂ · (CH₃)₂CO (1), Ph₂Sn(L⁴)₂ (4) and Ph₂Sn(L⁵)₂ (5) (L = 5-[(E)-2-(aryl)-1-diazenyl]quinolin-8-ol: aryl = phenyl - (L¹H); 4′-methylphenyl - (L⁴H) and 4′-bromophenyl - (L⁵H)) were determined by single crystal X-ray diffraction. In general, the complexes were found to adopt a distorted cis-octahedral arrangement around the tin atom. These complexes retain their solid-state structure in non-coordinating solvent as evidenced by ¹¹⁹Sn NMR spectroscopic results. The in vitro cytotoxicity of 1 is reported and compared with Ph₂Sn(Ox)₂ (Ox = deprotonated quinolin-8-ol) against seven well characterized human tumor cell lines.