5,7-二取代-2-(2,4-二氯苯氧乙酰亚胺基)-2H-1,2,4-噻二唑并[2,3-α]嘧啶衍生物的合成、晶体结构及除草活性

设计并合成了5种5,7-二取代-2-(2,4-二氯苯氧乙酰亚胺基)-2H-1,2,4-噻二唑并[2,3-a]嘧啶类化合物5,均为未见文献报道的新化合物.利用1H NMR、元素分析等确定了产物的结构.初步除草活性测定结果表明,化合物5对阔叶植物有优良的除草活性,且有一定的选择性.为了进一步了解该类化合物的结构,也为设计新的除草剂分子提供帮助,对其中一种化合物5b进行了X射线单晶衍射.     

5,7-二取代-2-(2,4-二氯苯氧乙酰亚胺基)-2H-1,2,4-噻二唑并[2,3-a]嘧啶衍生物的合成、晶体结构及除草活性

设计并合成了 5种 5 ,7 二取代 2 ( 2 ,4 二氯苯氧乙酰亚胺基 ) 2H 1,2 ,4 噻二唑并 [2 ,3 a]嘧啶类化合物 5 ,均为未见文献报道的新化合物 .利用1HNMR、元素分析等确定了产物的结构 .初步除草活性测定结果表明 ,化合物 5对阔叶植物有优良的除草活性 ,且有一定的选择性 .为了进一步了解该类化合物的结构 ,也为设计新的除草剂分子提供帮助 ,对其中一种化合物 5b进行了X射线单晶衍射     

4-氧-3-氮杂-三环[5.3.1.02,5]十一烷-9-甲酸甲酯的合成及晶体结构

以2-金刚烷酮为起始原料,通过烯烃与氯磺酰异氰酸酯的[2+2]环加成等5步反应合成了新型双环β-内酰胺类化合物5.采用1H NMR,IR和MS等手段对所得化合物的结构进行了表征.此外,还通过将化合物5酰化并采用X射线单晶衍射分析方法进一步测定了化合物5的空间立体结构.结果表明,烯烃3与氯磺酰异氰酸酯的[2+2]环加成反...     

3-取代-6-吡唑基-1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类衍生物的合成及生物活性

将5-取代吡唑-3-甲酸乙酯1位甲基化,经水解反应得到3种中间体1-甲基-5-取代1H-吡唑-3-甲酸（2a~2c）;以不同取代的羧酸为原料经一系列反应合成6种中间体3-取代4-氨基-5-巯基-1,2,4-均三唑（3a~3f）;将中间体（2a~2c）和（3a~3f）在三氯氧磷条件下反应,合成出18种1,2,4-三唑并[3,4-b]-1,3,4-噻二唑类化合物(4a~4r),均未见文献报道。 通过IR、1H NMR、13C NMR和元素分析表征了化合物结构。 初步的生物活性测试结果显示,所合成的化合物均表现出不同程度的生长素活性和抑菌活性。 并选取抑菌活性较好的两个化合物进行抗菌药物最低抑菌浓度(MIC)的测定。     

含1,2,4-三唑-5-硫酮席夫碱的新型1,2,4-三唑并[1,5-a]嘧啶衍生物的合成及生物活性研究

以2-苄硫基-5-甲基-7-羟基-1,2,4-三唑并[1,5-a]嘧啶为原料,经醚化、肼解、成盐、关环和席夫碱反应合成了20个新型的含1,2,4-三唑-5-硫酮席夫碱的1,2,4-三唑并[1,5-a]嘧啶类化合物,通过IR,1H NMR,MS和元素分析对所合成的化合物进行了结构表征.初步生物活性测试结果表明,部分化合物表现出一定的抑菌或较好的抗烟草花叶病毒(TMV)活性.在500μg/mL浓度下,化合物6b,6f和6p对TMV的抑制率分别为41%,43%和40%.     

4-甲氧基-6-甲基-7a-苯基苯并吡喃并[2,3-b]氮丙啶-7-酮的合成及晶体结构研究

通过5-甲基-7-甲氧基异黄酮与盐酸羟胺的缩合制得中间产物4-苯基-5-（2-羟基-4-甲氧基-6-甲基苯基）异恶唑,然后经过光异构化反应合成了4-甲氧基-6-甲基-7a-苯基苯并吡喃并[2,3-b]氮丙啶-7-酮,并采用IR,NMR,HRMS和单晶X-衍射分析对其结构进行了表征.单晶X-衍射分析结果表明：标题化合物属于单斜晶系,空间群P2（1）/n.在其晶体结构中,存在着氢键及芳香堆积作用,这些作用将标题化合物分子组装成了三维网络结构.     

新型1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂-2-酮的合成

取代苯并二氢吡喃 4 酮 ( 1)的芳腙在冰醋酸中与KNCO发生 [3 2 ]环加成反应 ,加成产物经KMnO4氧化开环得偕偶氮异氰酸酯 ( 3 ) .3在HBF4的催化下发生环化 -重排反应 ,合成得到一系列新型 6 7 5三环系 1,2 ,4 三唑并 [3 ,2 d] [1,5 ]苯并氧氮杂 2 酮 ( 5a～ 5g) .由X单晶衍射测定了化合物 5a的晶体结构     

新型三环系稠杂环[1,2,4]-三唑并[1,5-a][1]-苯并氮杂及[1,2,4]-三唑并[1,5-a]-喹啉的合成

α-四氢萘酮的乙氧羰基腙(1)经LTA氧化,得到α-偶氮-α-乙酰氧基化合物2.在A lC l3作用下,化合物2脱去乙酰氧基产生重氮正离子中间体3,再经与腈的1,3-偶极环加成、[1,2]-迁移扩环、碱性水解和与苦味酸作用,得到新型[1,2,4]-三唑并[1,5-a][1]苯并氮杂苦味酸盐6a~6c.以2,3-二氢-1-茚酮为底物,采用相同的合成路线,合成了1,2,4-三唑并[1,5-a]-二氢喹啉苦味酸盐12a~12c.     

含有1H-1,2,4-三唑咪唑[2,1-b]-1,3,4-噻二唑、S-三唑[3,4-b]-1,3,4-噻二唑衍生物的合成及生物活性

合成了18个含有1H-1,2,4-三唑的咪唑[2,1-b]-1,3,4-噻二唑以及S-三唑[3,4-b]-1,3,4-噻二唑的稠杂环衍生物,经元素分析及谱学表征,探讨2,5,6-三取代咪唑[2,1-b]-1,3,4-噻二唑的可能生成机制.对大肠杆菌、绿脓杆菌、枯草杆菌等初步抑菌试验证明,多数化合物表现了较好的抑菌活性.     

2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基丙烯腈衍生物的合成及生物活性

为了寻找生物活性良好的噻唑基丙烯腈类化合物, 利用2-[4-(2,6-二氟苯基)噻唑-2-基]乙腈(3)分别与取代氯甲酸酯4和取代苯基异氰酸酯6在碱存在下反应, 合成了8个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-烃氧基丙烯腈化合物5和7个2-[4-(2,6-二氟苯基)噻唑-2-基]-3-羟基-3-取代苯胺基丙烯腈化合物7, 均为首次报道的丙烯腈类化合物. 化合物结构经1H NMR, IR, MS和元素分析表征. 初步生物活性测定结果表明, 在试验浓度下, 目标化合物均具有一定的杀虫和抑菌活性, 其中化合物5f和5h在100 mg/L浓度下对炭疽病菌的抑制率达95%; 化合物5g和7d在250 mg/L浓度下对棉红蜘蛛的致死率达85%.     

Synthesis and self-assembly of novel calix[4]arenocrowns: formation of calix[4]areno[2]catenanes

A series of novel calix[4]arenocrowns 1a-c were efficiently synthesized by a one-pot reaction of calix[4]monohydroquinone diacetate 5 with ditosylate 6 and its analogues in the presence of sodium hydroxide. It was found that the calix[4]arenocrowns could form stable pseudorotaxane-type complexes 2a-c with paraquat, and further self-assemble into calix[4]areno[2]catenanes 3a-c with dicationic salt 8 and p-bis(bromomethyl)benzene.     

7-氯-[1，2，3，4]-四氢吩嗪-[2，3]-并富勒烯[60]的合成

60富勒烯及其衍生物因其结构的特殊性,在有机超导、分子磁性、有机发光材料、分子器件、非线性光学活性、能量代谢和生物活性等[1]方面表现出独特的性能和潜在的应用前景,是非常活跃的研究领域之一.     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.     

Synthesis and binding studies of novel bisthiacalix[4]arenes with diimime linkages

A series of novel bisthiacalix[4]arenes with diimine linkages of different aromatic or heteroaromatic dialdehydes have been synthesized. The structure of one of the bisthiacalixarene has been analyzed by X-ray crystallography. These molecules quantitatively extract silver ion from aqueous into organic phase under neutral conditions.     

25,26,27,28-羟乙氧基-杯[4]芳烃的合成

以对叔丁基苯酚为原料,经4步反应合成了新的杯[4]芳烃衍生物--25,26,27,28-羟乙氧基-杯[4]芳烃,其结构经~1H NMR和MS表征.     

Synthesis of novel mono- and diaryl-substituted [2.2]paracyclophanes

The cross-coupling reactions of 4-bromo[2.2]paracyclophane withp-tolylmagnesium bromide in the presence of various palladium and nickel complexes have been studied. It was found that [1,1 -bis(diphenylphosphinoferrocene)]palladium dichloride (PdCl₂ · dppf) shows the highest catalitic activity in this reaction. A series of new mono- and diaryl [2.2]paracyclophane derivatives with various substituents in the arene ring have been synthesized using this catalyst. It was shown that it is possible to cross-couple organozinc [2.2]paracyclophane derivatives with aromatic bromides. The composition and structure of the compounds obtained have been established on the basis of elemental analysis and spectral data. Some correlations between the structure and spectral parameters of mono- and diarylsubstituted [2.2]paracyclophanes have been found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1081–1085, June, 1994.The present work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5246).The authors wish to express their gratitude to Prof. N. A. Bumagin for his scientific interest and helpful discussions.     

簇合物[Et4N]2[Mo2S4(SCH2CH2S)2]的合成及其结构研究

以(NH4)2MoS4,Et4NBr,HSCH2CH2SH为原料,合成出[Et4N]2[Mo2S4(SCH23CH2S)2]簇合物,用X射线衍射法测定了晶胞结构.其晶胞参数为a=1.0304(8)nm,b=1.4158(8)nm,c=1.1417(1)nm,V=1.63801nm3,Z=4,晶体属单斜晶系,晶体结构经块状矩阵最小二乘法修正后,最终偏离因子R=0.089.此外还进行了红外光谱,紫外可见光谱的测定.     

Evidence of Hydrogen Bonding in Stabilizing the Cone Conformation of a Monoalkylated Calix[4]arene. X-ray Structure of 25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene

The synthesis of25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene3 as a byproduct of the preparation of 1,3-dialkylated25,27-di-[2-(ethoxy-1p-toluene-sulfonate)phenyl]-26,28-dihydroxy calix[4]arene 2 is reported. Compound 3 is a monoalkylatedcalix[4]arene in the cone conformation. The X-ray structure of 3 showed that this conformation is stabilized by intramolecular hydrogen bonding.     

单炔基桥联双杯[4]芳烃的合成与对溶剂分子的包合性能

对叔丁基杯[4]芳烃直接与1,4-二氯-2-丁炔反应,一步制备了单炔基单桥联双杯[4]芳烃和单炔基双桥联双杯[4]芳烃,并证实单桥联双杯[4]芳烃是双桥联双杯[4]芳烃的中间产物.经¹HNMR,¹³CNMR和ESI-MS分析证实了产物的结构.ESI-MS结果表明两种产物对DMF和H₂O有不同的包合能力.