N-(取代对三氟甲基苯基)-N'-(1,3,5-三取代)吡唑-4-羰基硫脲的合成与生物活性

为了寻找高效低毒的农药, 从3-甲基-1-取代苯基-5-吡唑酮出发, 经过几步反应得到5-氯-3-甲基-1-取代苯基-4-吡唑羰基异硫氰酸酯. 5-氯-3-甲基-1-取代苯基-4-吡唑羰基异硫氰酸酯分别与对三氟甲基苯胺和2,6-二氯-4-三氟甲基苯胺反应得到10个未见文献报道的N-(取代对三氟甲基苯基)-N'-(1,3,5-三取代)吡唑-4-羰基硫脲类化合物, 其结构经元素分析, IR, ¹H NMR确证. 初步生物活性测试结果表明部分化合物有一定的杀菌活性.     

Reactions with pyrrolidine-2,4-diones,II: New approaches to the synthesis of substituted 5,6-dihydropyrrolo[3,4-d][1,2,3]triazol-4(2H,4H)ones

Summary Approaches leading to 5,6-dihydro-5,6-diphenyl-2-substituted-pyrrolo[3,4-d][1,2,3]-triazol-4(2H,4H)-ones (10) are described. The first approach consists of cyclodehydrating 3(or 4)-hydroxyimino-1,5-diphenyl-4(or 3)-(4-substituted phenylhydrazono)pyrrolidin-2-ones (4,7) with boiling acetic anhydride. The second approach involves cyclization of 3(or 4)-acetoxyimino-1,5-diphenyl-4(or 3)-(4-substituted phenylhydrazono)pyrrolidin-2-ones (8,9) with elimination of acetic acid upon treatment with sodium hydroxide.Part of the work has been presented at the 8^th International Congress of Heterocyclic Chemistry (August 1981), Graz, Austria     

A 17O NMR study. On the correlation of ionization potentials and 17O chemical shifts in 4-substituted pyridine-N-oxides and 4-substituted N-(benzylidene)phenylamine-N-oxides

The approximate linear correlation between first ionization potentials and ¹⁷O chemical shifts for 4-substituted pyridine-N-oxides and 4-substituted N-(benzylidene)phenylamine-N-oxides is presented. The obtained results are used to estimate the ¹⁷O chemical shift in 4-N,N-dimethyl pyridine-N-oxide. The obtained results are discussed in relation to similar correlations in substituted benzenes and pyridines. The linear correlation between oxygen atomic net charge and ¹⁷O chemical shift for 4-substituted pyridine-N-oxides and 4-substituted N-(benzylidene)phenylamine-N-oxides is also presented.     

1,3,4-THIADIAZOLES. REGIOSELECTIVE O-DEMETHYLATION ON DEHYDRATIVE CYCLIZATION OF 1-(3,4,5-TRIMETHOXYBENZOYL)4-SUBSTITUTED THIOSEMICARBAZIDES WITH SULPHURIC ACID

Cyclization of 1-(3,4,5-trimethoxybenzoyl)-4-substituted thiosemicarbazides 2a–g with sulphuric acid at ambient temperature afforded the selectively demethylated products 2-(4-hydroxy-3,5-dimethoxyphenyl)-5-substituted amino-1,3,4-thiadiazoles 4a–g. Meanwhile, dehydrative cyclization of 1-(3,4,5-trimethoxybenzoyl)-4-(benzyl or t-butyl)thiosemi- carbazides 2h, i with sulphuric acid yielded 2-(4-hydroxy-3,5-dimetho xyphenyl)-5-amino-1,3,4-thiadiazole 5. On the other hand, dehydration of 2h, i by heating with phosphorus oxychloride yielded 2-(3,4,5-trimethoxyphenyl)-5-amino-1,3,4-thiadiazole 6.     

A Convenient Reduction Of N-(2-Substituted-1-cyanoethenyl) Acetamides with NaTeH

N-(1-cyano-2-substituted phenylethyl) acetamides (4a-h) were synthesized by reduction of corresponding titled compounds 3a-h with NaTeH. The procedure was general and convenient for preparation of benzyl substituted acyclic Reissert compounds without using phenylacetaldehydes as starting materials.     

[1,3]Dioxolo[5,6][1]benzothieno[2,3-c]-quinolin-6(5H)-ones

Summary The reaction of 3,4-methylenedioxycinnamic acid (1) with thionyl chloride resulted in the formation of 7-chlorothieno[2,3-f]-1,3-benzodioxole-6-carbonyl chloride (2) and cinnamoyl chloride (3). Subsequent reaction of the former withp-substituted anilines led to the formation of 7-chloro-N-(p-substituted phenyl)-thieno[2,3-f]-1,3-benzodioxole-6-carboxamides (4a–c) which on photocyclization afforded 2-substituted [1,3]dioxolo[5,6][1]benzothieno[2,3-c]quinolin-6(5H)-ones (5a–c) in fairly good yields and high purity. The structures have been confirmed by IR,¹H NMR, and analytical methods.Accepted for presentation at the Hong Kong International Symposium on Heterocyclic Chemistry (August 13–16, 1995)     

3-(4-吡啶基)-4-(6-取代色酮-3-基-亚甲氨基)-5-芳氨基-1,2,4-三唑的合成

N-芳基-N'-[(4-吡啶基)羰基]氨基硫脲用85%的水合肼环化, 得到3-(4-吡啶基)-4-氨基-5-芳氨基-1,2,4-三唑(2a～2c). 然后再与3-甲酰基色酮(3a～3d)反应, 制备得到了一系列新化合物: 3-(4-吡啶基)-4-(6-取代色酮-3-基亚甲氨基)-5-芳氨基-1,2,4-三唑(4a～4c, 5a～5c, 6a～6c, 7a～7c). 化合物的结构经元素分析, IR, ¹H NMR和MS确证.     

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.     

1-(Phenylsulfonyl)indol-2-yl Triflate: A Versatile Reagent for the Synthesis of 2-Substituted Indoles

The palladium-catalysed reaction of 1-(phenylsulfonyl)indol-2-yl triflate 1, with a variety of aryl and heteroaryl boronic acids 2 or vinyl tributylstannane 3 provides a general and an efficient method for the synthesis of 2-substituted indoles 4.     

Synthesis of Diazadi(and tri)thiacrown Ethers Containing Two 5-Substituent(or 2-methyl)-8-hydroxyquinoline Side Arms

Abstract

Sixteen new diazadi(or tri)thiacrown ethers containing two 5-substituent(or 2-methyl)-8-hydroxyquino-lin-2-ylmethyl side arms have been prepared by a three-step process. First, the appropriate bis(α-chloroamide)s were treated with five dimercaptans in base to form macrocyclic di(or tri)thiadiamides. The macrocyclic diamides were reduced by BH₃-THF to form 1,7-diaza-4-oxa-10,13-dithia-cyclopentadecane (11); 1,7-diaza-4,13-dioxa-10,16-dithiacyclooctadecane (12); 1,7-diaza-4-oxa-10,13,16-trithiacyclooctadecane (13); 1,7-diaza-4,13,16-trioxa-10,19-dithiacycloheneicosane (14); and 1,10-diaza-4,7-dioxa-13,16-dithiacyclooctadecane (15). The diazadi(or tri)thiacrown ethers were then treated with 8-hydroxyquinoline, 8-hydroxy-5-methylquinoline, 5-chloro-8-hydroxyquinoline, and 8-hydroxyquinaldine in the presence of paraformal-delyde in refluxing benzene to form the bis(8-hydroxy-5-substituent(or 2-methyl)quinolin-7-ymethy)-substituted diazadi(or tri)thiacrown ethers 16-31. The crown ethers containing two 8-hydroxyquinoline or 8-hydroxyquinaldine side arms proved to be mixtures of about 90% bis(8-hydroxyquinolin-7-ylmethyl)-substituted crown ethers; 9% mixed (8-hydroxyquinolin-7-ymethyl)-substituted and (8-hydroxyquinolin-5-ylmethyl)-substituted crown ethers; and 1% bis(8-hydroxyquinolin-5-ylmethyl)-substituted crown ethers.     

Competition of Different Addition and Cycloaddition Processes During Reaction of Phosphorus(II) and (III) Halides with Alkynes

Abstract

Addition of P-halogenophosphaalkenes to I-alkoxyalkynes provides either 2-phosphabutadienes 2 or P(II1)-substituted allenes 3. The reaction o f P-halogenophosphaalkenes I with I-aminoalkynes leads to the phosphetines 4 wa 5 - the product of 1,2-addition reaction.     

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).     

Total Synthesis of (±)-Armepavines and (±)-Nuciferines From (2-Nitroethenyl)benzene Derivatives

A concise route to armepavine 1 and nuciferine 2 and 3, which can be isolated from the leaves of Nelumbo nucifera (Nymphaceae), has been achieved in which the longest linear sequence is only six steps from commercially available benzaldehyde in 28%, 21%, and 20% overall yield, respectively. The key transformations in the synthesis are the radical cyclization of aryl bromide with Bu₃SnH and the Pictet–Spengler reaction of N-substituted amine with aldehyde.     

N-(6-氯吡啶-3-基)羰基-2-取代芳基磺酰胺的合成、结构及除草活性研究

通过6-氯吡啶-3-甲酸与2-取代芳基磺酰胺的缩合反应合成了5个N-(6-氯吡啶-3-基)羰基-2-取代芳基磺酰胺化合物3a～3e, 产物结构经元素分析, ¹H NMR, IR确证. 由X射线衍射法测定了化合物3a的晶体结构, 该晶体属于三斜晶系, 空间群为 . 以测试除草活性常用的植物玉米、黄瓜和油菜为试材测定了目标化合物的除草活性, 初步试验表明3a～3d有较好的活性, 而且它们对双子叶植物的抑制作用优于对单子叶植物.     

Base-mediated one-pot synthesis of 3,4,5,6-tetrahydro-4-substituted benzo[h]quinazoline-2(1H)-thione derivatives and evaluation of their antioxidant activity

One-pot three-component Beginelli-like reactions of a ketone 1, an aryl aldehyde 2, and thiourea 3 in the presence of sodium hydroxide are described. In this reaction, 3,4,5,6-tertrahydro-4-substituted quinazoline-2(1H)-thione derivatives 4a–h were obtained in good yields (73–85%). The compound 4a has been characterized by single crystal X-ray analysis. All the synthesized compounds 4a–h and 5a–b were screened for their in vitro antioxidant activity. Compounds 4c, 4e, and 4h have exhibited an excellent than the standard ascorbic acid. Compounds 4d, 4f, and 4g have also shown good activity. Remaining compounds show moderate antioxidant activity.     

Synthesis of thiiranylmethylamides from N(S)-allylthiooxamides

Abstract

The first representative of N¹-substituted N²-thiiranylmethylethaneamides has been synthesized from N¹-substituted N²-allylethaneamides. The formation of thiiranylmethylamides passes through bromine-induced cyclization of N-allylthioamide moiety followed by hydrolysis of 5-bromomethyl-1,3-thiazoline ring.     

A Convenient Synthesis of 4-(2-Furyl)-2-substituted Thiazoles Utilising [Hydroxy(tosyloxy)iodo]benzene

A facile synthesis of 4-(2-furyl)-2-substituted thiazoles by hypervalent iodine oxidation of 2-acetylfuran (1) using [hydroxy(tosy-loxy)iodo]benzene, followed by treatment of the reaction mixture with appropriate thioureas/thioamides is described.     

Synthesis and Antimicrobial Evaluation of Novel N-Substituted β-Hydroxy Benzimidazole Sulfone Fluoroquinolones by Selective Oxidation Using Ticl4-H2O2

Abstract

The synthesis of N-substituted β-hydroxy benzimidazole sulfones containing 8-methoxy fluoroquinolone has been described and they were evaluated for antimicrobial activities. The compounds of N-substituted β-hydroxy benzimidazole sulfides (4a–e) and N-substituted β-hydroxy benzimidazole sulfones (5a–e) at C-7 of fluoroquinoline exhibited superior activity in vitro. 8-Methoxy fluoroquinolone carboxylic acid (1), reaction with piperizine in acetonitrile in presence of triethylamine under reflux gives 7-piperazinyl-8-methoxyfluoroquinolone (2). The latter is reacted with epichlorohydrine in presence of NaOH in acetone yielded N-substituted epoxide (3), which on treatment with 5-substituted-2-mercaptobenzimidazoles gives N-substituted β-hydroxy benzimidazole sulfides (4). Further, 4 on treatment with TiCl₄-H₂O₂ and in DCM yielded the corresponding N-substituted β-hydroxy benzimidazole sulfone (5).     

Phosphorus (III) - and Phosphorus (IV)-Substituted Alkoxyacetylenes as New Synthons in Phosphororganic Synthesis

Abstract

The diheterosubstituted acetylenes of EC=COR type, where E is Si, Ge, Sn, B, possessing an increased react-ivity both in reactions with electrophilic reagents and fragmentation processes, are extensively investigated in the Moscow University. At the same time phosphorylated alkoxyacetylenes have gained less attention. The main purpose of this work was the synthesis of previously unknown phosphorus (III)-substituted alkoxyacetylenes (I), investigation of their stability, properties and applications in phosphororganic syntheses.     

Synthesis of β-d-(1→4)-Substituted Trehalose Oligosaccharides

Abstract

Glycosylation of 2,3,6-tri-O-benzyl-α-D-glucopyranosyl 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranoside (5) with α-D-glucopyranosyl, α-maltosyl, and α-maltotriosyl bromides 4, 7, and 8 afforded the β-D-(1→4)-substituted trehalose tri-, tetra-, and pentasaccharides 6, 9, and 10 which were fully characterized by ¹H NMR spectroscopy. Deprotection gave the free oligosaccharides 1, 2, and 3.