Synthesis of 5-[2-(Phenoxy)ethyl] Derivatives of 6-Methyluracil, 6-Methyl-2-thioxo-2,3-dihydro-1H-pyrimidin-4-one,and 2-Imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one

A synthesis of novel derivatives of 6-methyluracil, 6-methyl-2-thioxo-, and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one containing a 2-(phenoxy)ethyl substituent at position 5 of the pyrimidine ring has been carried out. It was found that 5-[2-(phenoxy)ethyl] derivatives of 6-methyl-2-thioxo- and 2-imino-6-methyl-2,3-dihydro-1H-pyrimidin-4-one are obtained by the condensation of the corresponding ethyl 3-oxo-2-(2-phenoxyethyl)butanoates with thiourea or guanidine. 6-Methyl-5-[2-(phenoxy)ethyl]uracils can be prepared by treating 6-methyl-5-[2-(phenoxy)ethyl]-2-thioxo-2,3-dihydro-1H-pyrimidin-4-ones with an excess of aqueous monochloroacetic acid solution. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1213–1217, August, 2005.     

2,2'-联吡啶参与的分子梭合成与1H NMR研究

2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙醇磺酸酯(1)与4,4'-联吡啶在乙腈中回流36 h, 随后通过阴离子交换得到N-{2-{2-[4-苯基-二(4-特丁基苯基)甲基]苯氧基}乙氧乙基}-4,4'-联吡啶六氟磷酸盐(3), 产率为93.4%. 3与4,4'-二(溴甲基)-2,2'-联吡啶在乙腈中、70 ℃下反应72 h, 生成哑铃型化合物5, 产率为45%. 5与冠醚BPP34C10在55 ℃下搅拌5 d, 得到分子梭6和7, 产率分别为42.3%和27.3%. ¹H NMR数据表明, 富电子冠醚BPP34C10与哑铃型组分上贫电子4,4'-联吡啶的非键作用使4,4'-联吡啶上氢的化学位移向高场有较大移动.     

Synthesis of 2-{2-hydroxy-3-[2-(vinyloxy)ethoxy]propoxy}-benzaldehyde and Schiff bases derived therefrom

Base-catalyzed reaction of 2-hydroxybenzaldehyde with 2-{[2-(vinyloxy)ethoxy]methyl}oxirane gave 2-{2-hydroxy-3-[2-(vinyloxy)ethoxy]propoxy}benzaldehyde in 42% yield, and subsequent condensations of the product with thiosemicarbazide and primary aliphatic amines afforded the corresponding thiosemicarbazone (yield 86%) and 1-{2-[(alkylimino)methyl]phenoxy}-3-[2-(vinyloxy)ethoxy]propan-2-ols (74–81%).     

New metallomesogenic polymers built by self-assembly of non-mesomorphic stilbazole dimers and CF3SO3Ag through coordination bonds

Supramolecular liquid-crystalline main-chain polymers have been obtained by self-assembly of non-mesomorphic bifunctional ligands and a transition metal ion. Stibazole dimers, bis[2-(2-{4-[2-(4-pyridyl)vinyl]phenoxy}ethoxy)ethyl] ether (1) and 1,2-bis[2-(2-{4-[2-(4-pyridyl)vinyl]phenoxy}ethoxy)ethoxy]benzene (2) have been synthesized and complexed with silver trifluoromethanesulfonate (CF₃SO₃Ag). The metallomesogenic polymeric complexes formed by coordination bonds between the pyridyl groups of the stilbazole dimers and the silver ion exhibit smectic phases.     

Synthesis and characterization of novel 1-[(2-hydroxyethoxy)methyl]-6-(phenylthio)thymine (HEPT) and dihydro-alkylthio-benzyloxopyrimidine (S-DABO) analogs containing a benzo[<Emphasis Type="Italic">d</Emphasis>]thiazol moiety

A series of novel dihydro-alkylthio-benzyloxopyrimidine (S-DABO) and 1-[(2-hydroxyethoxy) methyl]-6-(phenylthio)thymine (HEPT) analogs bearing a (benzo[d]thiazol-2-yl)methyl moiety at the C⁶ position of the pyrimidine core have been synthesized. 5-Allyl-6-{(benzo[d]thiazol-2-yl)methyl}-2-thiouracil and 5-allyl-6-{(benzo-[d]thiazol-2-yl)methyl}uracil were alkylated to give, respectively, S²- and N¹- ethoxymethyl and -methylthiomethyl uracil derivatives. 5-Allyl-6-[(benzo[d]thiazol-2-yl)methyl]-2-thiouracil was also alkylated by S² with methyl bromoacetate and hydrolyzed to the corresponding acid.     

Reaction of 2-{[2-(ethenyloxy)ethoxy]methyl}oxirane with oxazolidin-2-ones

Reactions of 2-{[2-(ethenyloxy)ethoxy]methyl}oxirane with N-unsubstituted oxazolidin-2-ones give mixtures of isomeric 3-{3-[2-(ethenyloxy)ethoxy]-2-hydroxypropyl}- and 5-{[2-(ethenyloxy)ethoxy]- methyl}-3-(2-hydroxyalkyl)oxazolidin-2-ones. If the initial oxazolidin-2-one contains two alkyl groups on C⁴, 3-{3-[2-(ethenyloxy)ethoxy]-2-hydroxypropyl}oxazolidin-2-ones are selectively formed.     

Ergebnisse der Verfahrensforschung,I. Synthese von o-{(+)-D-2-[4-(4-(Trifluormethyl)phenoxy)phenoxy]propionyl}-aceton-oxim

Results of process Research I. Synthesis of O-{(+)-D-2-[4-(4-(triluoromethyl)phenoxy)phenoxy]propionyl}-acetone oxime Efficient and simple procedures for the preparation of O-{L-[(sulfonyl)oxy]-propionyl}-oxime derivatives 7b-e have been developed. The alleviation of 4-[4-(trifluoromethyl)phenoxy]phenol ( 11 ) with 7d , the final step of a technical synthesis of 1 , has been studied in detail.     

阿佐昔芬的合成

以4-溴苯乙酮为起始原料,经溴化、与3-甲氧基苯硫酚缩合、分子内环合得6-甲氧基-2-(4-溴苯基)苯并[b]噻吩(5);5经溴化、氧化反应后,与4-[2-(1-哌啶基)乙氧基]苯酚缩合制得关键中间体3-{4-[2-(1-哌啶基)乙氧基]苯氧基}-6-甲氧基-2-(4-溴苯基)苯并[b]噻吩亚砜(7);7再经还原、脱甲...     

The Silyl Method for the Synthesis of 1[-2(Phenoxy)ethyl]uracils

A modification of the method for the synthesis of N₍₁₎-substituted derivatives of uracil is proposed using the Gilbert-Johnson reaction, which consists of the alkylation of 5-substituted 2,4-bis(trimethylsiloxy)pyrimidines with 1-bromo-2-(phenoxy)ethanes of low reactivity at 180-185° without solvent. The corresponding 1-[2-(phenoxy)ethyl]uracils, which were obtained in 55-74% yield, contained no impurities of the N₍₁₎, N₍₃₎-disubstituted compounds. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, 1071–1075, July, 2005. cf E. Ya. Lukevics and A. E. Zablotskaya. The Silyl Method for the Synthesis of Nucleosides [in Russian], Zinatne, Riga, 1985, 440 p. (Editor's note).     

Reactions of 5-[3-(trifluoromethyl)-phenyl]furan-2-carbaldehyde

The Knoevenagel condensations of 5-[3-(trifluoromethyl)phenyl]furan-2-carbaldehyde with seven compounds containing an active methyl or methylene group have been studied. The compounds used were: methyl 2-cyanoacetate, malononitrile, 2-furylacetonitrile, acetophenone, 2-thioxo-1,3-thiazolidin-4-one (rhodanine), 5,5-dimethylcyclohexane-1,3-dione (dimedone), and methyl 2-azidoacetate. The effect of microwave irradiation on the condensation reactions was studied and compared with “’classical”’ conditions. Thermolysis of methyl 2-azido-3-{5-[3-(trifluoromethyl)phenyl]-2-furyl}propenoate afforded methyl 2-[3-(trifluoromethyl)phenyl)]-4H-furo[3,2-b]pyrrole-5-carboxylate. (2E)-3-{ 5-[3-(Trifluoromethyl)phenyl]-2-furyl}propenoic acid was converted to the corresponding azide, which was cyclized on heating into 2-[3-(trifluoromethyl)phenyl)]-4,5-dihydrofuro[3,2-c]pyridin-4-one. The latter after successive action of POCl₃ and NH₂NH₂-Pd/C gave 2-[3-(trifluoromethyl)-phenyl]furo[3,2-c]pyridine. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 825–831, June, 2006.     

EPR studies on H-abstraction from methylbenzenes by “magic blue” reagent

After mixing a methylbenzene 4 with “magic blue” solution in F113 (CClF₂CCl₂F) containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl}nitroxide 2 and perfluoro-1-nitroso-1-[1-(2-fluorosulfonyl)ethoxy]ethane 3 at room temperature, benzylic H-atom of 4 could be selectively abstracted by 2, and benzyl radical 5 thus generated was immediately trapped by 3. Based on hyper-fine splitting constants (hfsc), the structure of the spin adducts perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl benzyl nitroxides 6 derived from seven methylbenzenes have been identified. The mechanism of the H-abstraction/spin trapping process is also discussed.     

1-乙酰基-5-取代吲哚啉类化合物的合成及生物活性

根据拼合原理, 以1-乙酰基吲哚啉为起始原料, 设计合成了1-乙酰基-5-{2-[4-(取代苯氧基乙基)-1-哌嗪基]烷基}吲哚啉和1-乙酰基-5-[2-(4-取代苯基-1-哌嗪基)烷基]吲哚啉两类化合物, 所有目标化合物结构均经核磁共振氢谱、元素分析、红外光谱及质谱确证. 初步生物活性测试结果表明, 所有目标化合物均具有一定的α₁-AR拮抗活性.     

一种新型Ni(Ⅱ)配位聚合物的合成、晶体结构和性质研究

溶剂热法合成了1个新配位聚合物{[Ni(C18H18N4O5)(DMF)]·(DMF}n.通过元素分析、红外光谱、热重以及X-射线单晶洐射对其进行了表征.该晶体为正交晶系,Pna21空间群.该化合物中,C18H18N4O5配体通过5个配位原子以及相邻的溶剂分子DMF上的1个配位原子与Ni(Ⅱ)原子配位,形成了1个扭曲的八面体配位构型.热重分析表明该化合物在140℃开始发生分解.     

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.     

Synthesis and ion-selective properties of 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy)ethoxy]cyclohexane (L) and its structural analogs. Crystal structure of L

Potentially hexadentate phosphoryl podands 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy) ethoxy]cyclohexane (L), 1,2-bis[2-((2-diphenylphosphoryl)phenoxy)ethoxy]cyclohexane (L¹), and 1,2-bis[2-((2-diphenylphosphorylmethyl)phenoxy)ethoxy]benzene (L²) are synthesized. Stability constants of complexes formed by L, L¹, and L² with alkali-metal 2,4-dinitrophenolates in mixed THF—CHCl₃ solutions (4: 1 by volume) are determined. Electroanalytical characteristics of ion-selective electrodes with hexadentate phosphoryl podands having different structures used as active components of their plasticized membranes are compared for cations of alkali and alkaline-earth metals. The IR spectra are described. The crystal structure of L is studied by X-ray diffraction.     

New N1-(4-aryloxybenzyl)uracils containing N3-positioned 4-(trimethyleneoxy)benzoic acid moiety,and study of their antiviral activity against SARS-CoV-2 and influenza virus

New title uracil derivatives, 4-{3-[2,6-dioxo-3-(4-aryl-oxybenzyl)-3,6-dihydropyrimidin-1(2H)-yl]propoxy}benzoic acids and their butoxy homologues, were obtained in three steps using 2,4-bis(trimethylsilyloxy)pyrimidine, 4-aryloxy-benzyl bromides and methyl 4-(ω-bromoalkoxy)benzoates as the key reactants. The compounds were studied as inhibitors of H1N1 influenza virus and SARS-CoV-2 R replication in MDCK and Vero E6 cell cultures, respectively, which revealed that the tested compounds had high levels of anti-SARS-CoV-2 activity.     

Synthesis of 6-[4-(allyl/phenyl)-5-thioxo-1,2,4-triazol-3-yl]pyrimidine-2,4-diones and their reaction with electrophiles

Cyclization of 1-(2,4-dioxo-1,2,3,4-tetrahydropyrimidin-6-yl)carbonyl-4-R-thiosemicarbazides in basic medium gave 6-(4-R-5-thioxo-1,2,4-triazol-3-yl)pyrimidine-2,4-diones (R = Allyl, Ph). Alkylation of the latter with iodomethane occurred at the sulphur atom to give the corresponding methylsulfanyl derivatives. Acetylation using acetyl chloride occurred at the N₍₁₎ atom of the triazole ring to the corresponding acetyl derivative when R = Ph but for R = Allyl the acetylation did not occur under the same conditions. In the presence of bromine in refluxing methanol the indicated allyl-substituted compound cyclizes to 6-bromomethyl-3-(2,4-dioxo-1,2,3,4-tetrahydropyrimidin-6-yl)-5,6-dihydrothiazolo[2,3-c]-1,2,4-triazole. Under Mannich and bromination conditions the methylsulfanyl derivatives prepared form derivatives at the 5 position of the uracil ring: 5-methylmorpholino-(piperidino)-and 5-bromo-(4-R-5-thioxo-1,2,4-triazol-3-yl)pyrimidine-2,4-diones respectively. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 906–912, June, 2006.     

2-{2-[3-(取代苯基)-3-氧代-2-1,2,4-三唑-1-基-丙基]-苯基}-2-甲氧亚氨基乙酸甲酯和乙酰甲胺类衍生物的合成与杀菌活性研究

以2-甲基苯甲酰甲酸甲酯为起始原料, 通过与甲氧基胺的盐酸盐、甲胺、N-溴代丁二酰亚胺(NBS)和1H-1,2,4-三氮唑钠反应合成了两个系列共计22个2-{2-[3-(取代苯基)-3-氧代-2-1,2,4-三唑-1-基-丙基]-苯基}-2-甲氧亚氨基乙酸甲酯和乙酰甲胺类的衍生物. 经IR, 1H NMR和MS对目标化合物进行了结构表征. 用浓度为 10 µg&#8226;mL－1的目标化合物进行了初步离体杀菌活性试验, 结果表明: Ha4, Ha5, Ha7对油菜菌核病有杀菌活性; Ha2, Hb8对小麦纹枯病有杀菌活性; Hb4对蔬菜灰霉病有杀菌活性; Hb4, Hb5对小麦赤霉病和小麦纹枯病均有杀菌活性.     

Syntheses of some new 1,5‐benzothiazepine derivatives and their ribofuranosides as antimicrobial agents

(±)‐cis‐2‐(4‐Methoxyphenyl)‐3‐hydroxy/methoxy‐6‐ethoxy/phenoxy‐2,3‐dihydro‐1,5‐benzothiazepin‐4‐[5H/5‐chloroacetyl/5‐(4′‐methylpiperazino‐1′)acetyl]‐ones have been synthesized by the condensation of 2‐amino‐3‐ethoxy/phenoxybenzenethiol with methyl‐(±)‐trans‐3‐(4‐methoxyphenyl)glycidate in xylene. Ribofuranosides, viz. (±)‐cis‐2‐(4‐methoxyphenyl)‐3‐methoxy‐6‐ethoxy/phenoxy‐2,3‐dihydro‐1,5‐benzothiazepin‐4‐[5‐(2′,3′,5′‐tri‐O‐benzoyl‐β‐D ‐ribofuranosyl)]‐ones, have been synthesized by the treatment of 3‐methoxy derivatives of 1,5‐benzothiazepines with a derivative, sugar, viz. β‐D ‐ribofuranose‐1‐acetate‐2,3,5‐tribenzoate, in toluene in vacuo. The structures of all the synthesized ribofuranosides and their precursors have been characterized on the basis of elemental analyses and IR, ¹H NMR, and ¹³C NMR spectral data. These compounds were screened for their antimicrobial activity. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:620–625, 2002; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10051     

2-(Tributylstannyl)-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-indole: Synthesis and use as a 1H-indol-2-yl-anion equivalent

Pd-Catalyzed reaction of 2-(tributylstannyl)-1-{[2-(trimethylsilyl)ethoxy]methyl}-1H-indole ( 5 ) with a variety of aryl, heteroaryl, vinyl, and allyl halides provides an efficient entry to the corresponding cross-coupled products (see Table).