A Facile One-Step Synthesis of New Types of 8-Thiazolyl and 8-Thiadiazinyl Coumarins

N-[4-(7-Methoxy-4-methyl-2-oxo-2H-chromen-8-yl)-thiazol-2-yl]-guanidine ( 2 ) has been prepared by the condensation of 4-methyl-7-methoxy-8-(2-bromoacetyl)coumarin ( 1 ) with guanylthiourea. 4-Methyl-7-methoxy-8-[2-(N′-(1-phenyl-ethylideneisopropylidene)-hydrazino]-thiazol-4-yl]chromen-2-ones ( 3 , 4 , and 5 ) have been prepared by reaction of 4-methyl-7-methoxy-8-(2-bromoacetyl) coumarin ( 1 ) and thiosemicarbazide in presence of acetophenone or acetone without any solvent. The formation of these compounds was further confirmed by the condensation of acetophenone/acetone thiosemicarbazones with 4-methyl-7-methoxy-8-(2-bromoacetyl)coumarin ( 1 ) in anhydrous ethanol in a two-step process. Similarly 8-[2-[N′-(benzylidene)hydrazine]-thiazol-4-yl]-7-methoxy-4-methyl-chromen-2-ones ( 6 , 7 , and 8 ) have been prepared by the condensation of 4-methyl-7-methoxy-8-(2-bromoacetyl)chromen-2-one with thiosemicarbazide and various aromatic aldehydes in a single step without any solvent. The formation of these compounds was further confirmed by the condensation of appropriately substituted benzaldehyde thiosemicarbazones with 4-methyl-7-methoxy-8-(2-bromoacetyl)coumarin in anhydrous ethanol. 4-Methyl-7-methoxy-8-(2-bromoacetyl) chromen-2-one (1) upon condensation with 3,5-dimercapto-4-amino-s-triazole in anhydrous ethanol resulted in the formation of 8-(3-mercapto-3H-[1,2,4]triazolo[3,4-b]thiadiazin-6-yl)-7-methoxy-4-methyl chromen-2-one (9). This compound ( 9 ) on reaction with various alkyl and phenacyl halides in anhydrous ethanol gave corresponding 4-methyl-7-methoxy-8-[3-(2-oxo-substituted sulphanyl)-7H-[1,2,4]triazolo[3,4-b]thiadiazin-6-yl]chromen-2-ones ( 10 to 18 ). The structures of newly prepared compounds have been confirmed from analytical and spectral data.     

含噁二唑肟醚取代的均三唑水杨醛席夫碱的合成及抗菌活性

4-氨基-5-(4-甲氧苯基)-3-巯基-均三唑(2)在无水乙酸钠作用下与β-氯苯丙酮(3)缩合得氨基三唑硫代苯丙酮(4). 化合物4与盐酸羟胺肟化得羰基肟化物5, 接着与水杨醛缩合得到席夫碱肟6, 用氯甲基噁二唑7a～7e对化合物6的肟羟基醚化得到目标物均三唑噁二唑肟醚1a～1e. 所合成的新化合物结构由元素分析和光谱数据表征, 体外抗菌活性也被试验.     

2-[3-(Trifluoromethyl)phenyl]furo[3,2-b]pyrroles: synthesis and reactions

The synthesis and reactions of methyl 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole-5-carboxylate (1a) are described. Upon reaction with methyl iodide, benzyl chloride, or acetic anhydride, this compound gave N-substituted products 1b-d. By hydrolysis of compounds 1a-c, the corresponding acids 2a-c were formed, or by reaction with hydrazine-hydrate, the corresponding carbohydrazides 3a-c were formed. By heating 2-[3-(trifluoromethyl)phenly]-4H-furo[3,2-b]pyrrole-5-carboxylic acid (2a) in acetic anhydride, 4-acetyl-2-[3-(trifluoromethyl)phenyl]furo[3,2-b]pyrrole (4) was formed. By hydrolysis of 4, 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole (5a) was formed, and reactions with methyl iodide or benzyl chloride gave N-substituted products 5b-c. The reaction of 4 with dimethyl butynedioate gave substituted benzo[b]furan 6. Compound 3a reacted with triethyl orthoesters giving 7a-c, which afforded with phosphorus (V) sulphide the corresponding thiones 8a-c. The thiones 8a-c reacted with hydrazine hydrate to form hydrazine derivatives 9a-c. The reaction of triethyl orthoformiate with compounds 9a-c led to furo[2′,3′: 4,5]pyrrolo[1,2-d][1,2,4]triazolo[3,4-f][1,2,4]triazines 10a-c. Hydrazones 11a-c were formed from 3a-c and 5-[3-(trifluoromethyl)phenyl]furan-2-carboxaldehyde. The effect of microwave irradiation on some condensation reactions was compared with “classical” conditions. The results showed that microwave irradiation shortens the reaction time while affording comparable yields.     

Synthesis and Properties of New Thiacalixarene Derivatives with Palladium Ion

Three new thiacalix[4]arene derivatives, 5,11,17,23-tetra-tert-butyl-25,27-di(2-hydroxyethoxy)-26,28-dihydroxythiacalix-{}[4]arene (2), 5,11,17,23-tetra-tert-25, 26,27,28-tetrakis[(methylcarboxyl)methoxy]thiacalix[4]arene (3),5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrakis(2-hydroxy-1-propanoxy)thiacalix[4]arene (4), were synthesized for the first time. The coordination properties of thiacalix[4]arene(1) and its derivatives (2 and 4) were investigated by detecting the interactions betweenthese compounds and two palladium complexes, cis-[Pd(en)(H₂O)₂]²⁺ and cis-[Pd(dtco-3-OH)(H₂O)₂]²⁺, by means of electrospray ionization mass spectrometry (ESI-MS) technique.     

Synthesis and antimicrobial activity of new derivatives of pyrano[4',3':4',5']pyrido[3',2':4,5]thieno[3,2-d]pyrimidine and new heterocyclic systems

Taking into account previously obtained biological results on some polyheterocyclic compounds (containing different heteroatoms) and in particular on several 8-amino-5-isopropyl-2,2-dimethyl-10-(methylthio)-1,4-dihydro-2H-pyrano[4’’,3’’:4’,5’]pyrido[3’,2’:4,5]thieno[3,2-d]pyrimidines Ia-v we have carried out the synthesis of twentyone 8-amino-5-isobutyl-2,2-dimethyl-10-(methylthio)-1,4-dihydro-2H-pyrano[4’’,3’’:4’,5’]pyrido[3’,2’:4,5]thieno[3,2-d]pyrimidines 6. Therefore we have slightly modified the structure of the previously studied I introducing at C-5 an isobutyl group instead of the previously examined isopropyl ones in order to see if this variation (changing a little the lipophilicity) will affect the biological activity. Furthermore thieno[3,2-d]pyrimidine-8-thione 7 and their S-alkylated 8 were synthesized. Finally by alkylation of 5-isobutyl-2,2-dimethyl-10-thioxo-1,4,10,11-tetrahydro-2H-pyrano[4'',3'':4',5']pyrido[3',2':4,5]thieno[3,2-d]pyrimidin-8(9H)-one 3 with alkyl dichlorides (bifunctional reagents) we realized the cyclization of a thiazole or thiazine ring on the [b] side of the pyrimidine ring with formation of the new condensed pentaheterocyclic systems: pyrano[4'',3'':4',5']pyrido[3',2':4,5]thieno[3,2-d][1,3]thiazolo[3,2-a]pyrimidin-8-one 11 and pyrano[4''',3''':4'',5'']pyrido[3'',2'':4',5']thieno[3',2':4,5]pyrimido[2,1-b][1,3]thiazin-8-one 12. It was found that some of the synthesized compounds showed interesting antimicrobial activity (by agar diffusion method) against some gram-positive and gram-negative bacilli strains.     

Some thermophysical properties of several solid aldehydes

The present study reports a differential scanning calorimetry (DSC) study of the solid aldehydes: 4-hydroxybenzaldehyde [123-08-0] 1; 4-hydroxy-3-methoxybenzaldehyde (vanillin) [121-33-5] 2; 3-ethoxy-4-hydroxybenzaldehyde (ethyl vanillin) [121-32-4] 3; 3,4-dimethoxybenzaldehyde (veratraldehyde) [120-14-9] 4 and 4-methoxycinnamaldehyde [1963-36-6] 5, in the temperature interval from T=268 K to their respective melting temperatures. Temperatures, enthalpies and entropies of fusion and the heat capacities of the compounds as a function of temperature are reported.     

Synthesis of novel 1,2,3-thiadizoles and 1,2,3-selenadiazoles as new antimicrobial agents

Abstract

A series of novel 1,2,3-thiadiazoles and 1,2,3-selenadiazoles having a long alkyl chain were synthesized by reacting semicarbazones with SOCl₂ and SeO₂, respectively. The structures of the target compounds 5–12 were confirmed by spectroscopy (IR, ¹H NMR, ¹³C NMR, and MS) and elemental analysis. Their antibacterial and antifungal activities were evaluated against six bacteria (Pseudomonas aeruginosa, Escherichia coli, Klebsiella pneumoniae, Proteus mirabilis, Enterococcus faecalis, Staphylococcus epidermidis, Staphylococcus aureus) and three fungi (Candida albicans, Candida parapsilosis, Candida tropicalis). The results of bioassays indicated that the compounds 5-Dodecyl-4-(4-methoxy-phenyl)-[1-3]selenadiazole (7), 4-Methyl-5-tetradecyl-[1-3]selenadiazole (8) and 5-Dodecyl-4-(4-methoxy-phenyl)-[1-3]thiadiazole (11) displayed moderate antibacterial activity against S. Epidermidis. On the other hand, according to antifungal screening results, compounds 5-Dodecyl-4-phenyl-[1-3]selenadiazole (5), 4-p-Tolyl-5-undecyl-[1-3]selenadiazole (6), and 5-Dodecyl-4-(4-methoxy-phenyl)-[1-3]selenadiazole (7) exhibited significant antifungal activities studied yeast strains.     

Synthesis and selected transformations of 1-(5-methyl-1-aryl-1H-1,2,3-triazol-4-yl)ethanones and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl]ethanones

By cycloaddition of arylazides to acetylacetone are obtained derivatives of 1,2,3-triazole. In the reaction of 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) and 1-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] ethanones (VIIa-VIIe) with isatin are obtained 2-[1-(R-phenyl)-5-methyl-1H-1,2,3-triazol-4-yl]-4-quinolinecarboxylic acids (IIIa–IIIe) and 2-[4-(4-R-5-methyl-1H-1,2,3-triazol-1-yl)phenyl] -4-quinolinecarboxylic acids (IXa, IXb), respectively. We found that 1-[5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] ethanones (IIa–IIe) readily transform into [5-methyl-1-(R-phenyl)-1H-1,2,3-triazol-4-yl] acetic acids (IVa–IVc) by the method of Wilgerodt-Kindler. The (5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl)acetic acid reacts with 5-phenyl-4-amino-4H-1,2,4-triazol-3-thiol affording 6-[(5-methyl-1-phenyl-1H-1,2,3-triazol-4-yl) methyl]-3-phenyl[1,2,4] triazolo[3,4-b] [1,3,4] thiadiazole (VI). Original Russian Text ? N.T. Pokhodylo, R.D. Savka, V.S. Matiichuk, N.D. Obushak, 2009, published in Zhurnal Obshchei Khimii, 2009, vol. 79, no. 2, pp. 320–325.     

Intramolecular Radical,Knoevenagel, or SN2′ Cyclization of Carbohydrate Derivatives for Access to Enantiomerically Pure 2-Oxospiroalkanes

Abstract

Intramolecular radical cyclization of D-glucose-derived substrate, (2R,3R,4R,5S)-2, 3-(isopropylidenedioxy)-5-[(1R)-l, 2-(isopropylidenedioxy)ethyl]-4-[3-bromo-3, 3-bis(methoxycarbonyl)propyl]-4-vinyltetrahydrofuran, 7 proceeded in a 6-endo-trig mode to give a derivative of 2-oxaspiro[4.5]decane 8 exclusively. Intramolecular Knoevenagel-like reaction of substrate 9 afforded derivatives of 2-oxaspiro-[4.4]nonane 10 as a 3:1 diastereomeric mixture. Intramolecular SN²′ displacement of substrate 22 proceeded highly stereoselectively giving a derivative of 2-oxaspiro-[4.4]decane 23.     

Acetylenchemie, 33. Mitt.: Synthese von 2-substituierten Dihydrofuro[2,3-b]chinolinen

Summary The reaction of 3-iodo-4-methoxy-2(1H)-quinolinone (1) and 3-iodo-4,6,8-trimethoxy-2(1H)-quinolinone (2) with 2-methyl-3-butyn-2-ol under modified Heck-conditions gave the 2-substituted derivatives 2-(1-hydroxy-1-methylethyl)-4-methoxyfuro[2,3-b]-quinoline (3) and 2-(1-hydroxy-1-methylethyl-4,6,8-trimethoxyfuro[2,3-b]-quinoline (4). By a subsequent hydrogenation-reaction with a homogeneous catalyst (PtO₂/Rh₂O₃), the furoquinoline-derivatives yielded the dihydrofuro-[2,3-b]quinolines, identified as 2-(1-hydroxy-1-methylethyl-4-methoxy-2,3-dihydrofuro[2,3-b]quinoline (5) (racemic platydesmine) and 2-(1-hydroxy-1-methylethyl)-4,6,8-trimethoxy-2,3-dihydrofuro-[2,3-b]quinoline (6) (racemic precursor of O⁴-methylptelefolonium salt).

     

CHEMICAL BEHAVIOR OF SOME BENZ[b] INDENO[1,2-e] [1,4] THIAZINE DERIVATIVES

Abstract

The study of the chemical behavior of some benz[b] indeno[1,2-e] [1,4] thiazine derivatives was accomplished. Different reactivities were observed for 4b,5-dihydrobenz[b]-indeno[1,2-e] [1,4] thiazine-10α(11H)-ol (3) and 5-ethyl-4b,5-dihydrobenz[b] indeno[1,2-e]-[1,4] thiazine-10α(11H)-ol (5); 3 is reoxidated to benz[b] indeno[1,2-e] [1,4] thiazine-10α(11H)-ol (2), while 5 undergoes transposition and oxidation to spiro[3-ethylbenzo-thiazol-2(3H), 1′-indan-2′-one] (6). Possible pathways for these transformations are discussed.     

水溶性稠杂环均三唑并噻二唑体系的合成及生物活性(I): 哌嗪取代衍生物

4-氨基-5-吡啶-4-基-均三唑硫醇(1)在复合催化剂DMAP和TBAB作用下与对卤代苯甲酸经环缩合反应以高收率得到中间体6-(5-氯-3-甲基-1-取代苯基-1H-吡唑-4-基)-3-吡啶-3-基-均三唑并[3,4-b][1,3,4]噻二唑(2a～2c), 接着苯环卤原子与取代哌嗪在聚乙二醇催化作用下发生亲核取代反应得到相应的哌嗪游离碱(3a～3c). 其中, 单取代哌嗪游离碱3a与含功能基的卤代物缩合得到功能基取代的哌嗪衍生物(4a～4g). 这些产生的游离碱与盐酸反应得到相应的水溶性盐酸盐. 所合成新化合物的结构经元素分析和光谱数据表征, 并评价了它们的体外抗菌活性及构效关系.     

New approaches to synthesis of tris[1,2,4]triazolo[1,3,5]triazines

Thermal cyclization of 3-R-5-chloro-1,2,4-triazoles (R = Cl, Ph) afforded 2,6,10-tri-R- tris[1,2,4]triazolo[1,5-a:1′,5′c:1″,5″-e][1,3,5]triazines 5 (R = Ph) and 7 (R = Cl). These compounds are first representatives of this class of heterocycles, whose structures were unambiguously established. Treatment of these compounds with nucleophiles (H₂O/NaOH, NH₃) results in the triazine ring opening to give compounds consisting of three 1,2,4-triazole rings linked in a chain. For example, treatment of cyclic compound 5 with aqueous alkali affords 3-phenyl-1-3-phenyl-1-(3-phenyl-1H-1,2,4-triazol-5-yl)-1,2,4-triazol-5-yl-1H-1,2,4-triazol-5-one. Treatment of 3,7,11-triphenyltris[1,2,4]triazolo[4,3-a:4′,3′c:4″,3″-e][1,3,5]triazine (2) with HCl/SbCl₅ leads to the triazine ring opening giving rise to 5-(3-chloro-5-phenyl-1,2,4-triazol-4-yl)-3-phenyl-4-(5-phenyl-1H-1,2,4-triazol-3-yl)-1,2,4-triazole. Thermal cyclization of the latter produces 3,7,10-triphenyltris[1,2,4]triazolo[1,5-a:4′,3′c:4″,3″-e][1,3,5]triazine (13). Thermolysis of both cyclic compound 2 and cyclic compound 13 is accompanied by the Dimroth rearrangement to yield 3,6,10-triphenyl-tris[1,2,4]triazolo[1,5-a:1′, 5′-c:4″,3″-e][1,3,5]triazine (14). Compounds 13 and 14 are the first representatives of cyclic compounds with this skeleton. ¹³C NMR spectroscopy allows the determination of the isomer type in a series of tris[1,2,4]triazolo[1,3,5]triazines.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 706–712, March, 2005.     

Studies on DNA binding behavior of biologically active Cu(II) complexes of Schiff bases containing acyl pyrazolones and 2-ethanolamine

Pyrazolone derivatives (Z)-4-((2-hydroxyethylimino)(p-tolyl)methyl)-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one [PMP-EA] (1), (Z)-1-(3-chlorophenyl)-4-((2-hydroxyethylimino)(p-tolyl)methyl)-3-methyl-1H-pyrazol-5(4H)-one [MCPMP-EA] (2), and (Z)-4-((2-hydroxyethylimino)(p-tolyl)methyl)-3-methyl-1-p-tolyl-1H-pyrazol-5(4H)-one [PTPMP-EA] (3) have been synthesized and characterized. The molecular geometry of 2 has been determined by single-crystal X-ray study. These ligands exist in amine-one tautomeric form in the solid state. Three copper(II) complexes, [Cu(PMP-EA)(H₂O)₂] (4), [Cu(MCPMP-EA)(H₂O)₂] (5), and [Cu(PTPMP-EA)(H₂O)₂] (6), respectively, have been synthesized using these ligands and characterized by microanalytical data, molar conductivity, IR, UV–Visible, FAB-Mass, magnetic measurement, TG-DTA studies, and ESR spectral studies; Cu(II) is five-coordinated with [ML(H₂O)₂] composition. The interaction of the complexes with CT-DNA (calfthymus) was investigated using different methods. The results suggest that the copper complexes bind to DNA via intercalation and can quench the fluorescence intensity of EB bound to DNA.     

Azocalixarenes. 6: Synthesis, complexation, extraction and thermal behaviour of four new azocalix[4]arenes

Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (1–4) were treated with three transition metal salts (e.g., CuCl₂·2H₂O, NiCl₂·6H₂O or CoCl₂·6H₂O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR, ¹H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the organic phase was carried out by using azocalix[4]arenes (1–4). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag⁺, Hg⁺ and Hg²⁺. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported. Dedicated to Prof. Dr. Mustafa Yılmaz on the occasion of his 50th birthday     

α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5] 十一烷基]}苯基卟啉星形化合物的合成

以对苯二甲醛、丙二腈、季戊四醇和吡咯为原料, 合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4). 4与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5), 5与3的反应产物经10% NaOH 处理后, 再与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(6), 6与乙酐、丙酐、苯甲酰氯反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3- (9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(7), α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物. 中间体1～6和星形化合物7～9均进行了IR, ¹H NMR, MS和元素分析等结构表征. 对影响反应的诸因素进行了讨论.      

Acetylene chemistry,part 32: Alkinylation and cyclic rearrangement of theophylline with unsaturated alcohols by Mitsunobu reaction

Summary The reaction of theophylline (1) with 2-methyl-3-butyn-2-ol and 1-butyn-3-ol under Mitsunobu conditions gave the respective 9-substituted derivatives 9-[2-(2-methyl-3-butynyl)]-theophylline (2) and 9-[2-(3-butynyl)]-theophylline (3). On reaction with 2-methyl-3-buten-2-ol, theophylline yielded in addition to the 9-[2-(2-methyl-3-butenyl)]-theophylline (4), two more cyclic products, identified as 1,5,5a,8-tetrahydro-1,3,8,8-tetramethyl-2H-pyrrolo[1,2-e]purine-2,4(3H)-dione (5) and 8a,9-dihydro-1,3,6,6-tetramethyl-1H-pyrrolo[2,1-f]purine-2,4(3H,6H)-dione (7).

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Acetylenchemie, 32. Mitt.: Alkinylierung und cyclische Umlagerung von Theophyllin mit ungesättigten Alkoholen mittels Mitsunobu-Reaktion

Zusammenfassung Die Reaktion von Theophyllin (1) mit 2-Methyl-3-butin-2-ol und 1-Butin-2-ol unter Mitsunobu-Bedingungen führte zu den 9-substituierten Derivaten 9-[2-(2-Methyl-3-butinyl)]-theophyllin (2) bzw. 9-[2-(3-Butinyl)]-theophyllin (3). Bei der Reaktion mit 2-Methyl-3-buten-2-ol ergab Theophyllin außer 9-[2-(2-Methyl-3-butenyl)]-theophyllin (4) noch zwei weitere cyclisierte Produkte, die als 1,3,8,8-Tetramethyl-1,5,5a,8-tetrahydro-pyrrolo[1,2-e]purin-2,4(3H)-dion (5) und 1,3,6,6-Tetramethyl-8a,9-dihydro-1H,6H-pyrrolo[2,1-f]purin-2,4-dion (7) identifiziert wurden.

     

Synthesis and Biological Activities of Novel Seleno epi-Daunomycin Derivatives

Abstract

3′-[2-(Selenoaryl)acetamido]epi-daunomycin derivatives 2a–d and 4′-[2-(selenoaryl)acetoxy]-N-(trifluoroacetyl)epi-daunomycin derivatives 4a–e were synthesized from epi-daunomycin 1d and N-trifluoroacetyl epi-daunomycin 3, respectively. These new compounds were assayed against human stomach cancer SGC-7901 and human leukaemia HL60.     

Coordination behavior of chromone Schiff bases towards the [ReVO]3+ and [ReI(CO)3]+ cores

Herein, we describe the coordination behavior of chromone Schiff bases towards [Re^VO]³⁺ and [Re^I(CO)₃]⁺. The reaction between 2-(2-thiolphenyliminomethyl)-4H-chromen-4-one (Htch) and [Re(CO)₅Cl] led to fac-[Re(CO)₃(bsch)Cl] (1) (bsch = 2-benzothiazole-4H-chromen-4-one). The square pyramidal [ReO(Hns)] (2) {H₂ns=bis-[(2-phenylthiolate)iminomethyl]-methyl-1-(2-hydroxyphenyl)prop-2-en-1-one} and octahedral [ReO(OCH₃)(PPh₃)(Huch)] (3) complexes were isolated from reactions of trans-[Re^VOBr₃(PPh₃)₂] with Htch and H₃uch [(5Z)-5-((4-hydroxy-2-methoxy-2H-chromen-3-yl)methyleneamino)-6-amino-1,3-dimethylpyrimidine-2,4(1H, 3H)-dione], respectively. The chromone Schiff bases and their metal complexes were fully characterized via NMR-, IR- and UV–Vis spectroscopy, single crystal XRD analysis and conductivity measurements. In addition, DFT studies were conducted to compare selected optimized and experimental parameters of the complexes.     

Synthesis of novel azabicyclo derivatives containing a thiazole moiety and their biological activity against pine-wood nematodes

Abstract

To explore a new skeleton with nematicidal activity, a series of novel azabicyclo derivatives containing a thiazole moiety were designed, synthesized and evaluated for their nematicidal activities. The bioassay results against pine-wood nematodes (Bursaphelenchus xylophilus) showed that most of the title compounds displayed nematicidal activity at a concentration of 40?mg/L. Especially, the title compounds2-((8-methyl-8-azabicyclo[3.2.1]octan-3-yl)oxy)-4-(4-chlorophenyl)thiazole (7e), 2-((8-methyl-8-azabicyclo[3.2.1]octan-3-yl)thio)-4-phenylthiazole (10a) and 2-((8-methyl-8-azabicyclo [3.2.1]octan-3-yl)thio)-4-(4-chlorophenyl)thiazole (10e) exhibited more than 90% mortality against Bursaphelenchus xylophilus.