3,4-二氢-1H-2-苯并吡喃衍生物化合成

3,4-二氢-1 H-2-苯并吡喃也俗称异色满(isochroman)。近年来,将该类化合物引入到药物合成中的研兖引起了人们的兴趣。虽然,已经合成出许多具有镇痛、降血压、抗组胺。和抗肿瘤等药理活性的3,4-二氢-1 H-2-苯并吡喃类化物,合但大都为异色满环上的1,3,4位取代衍生物或者螺环化合物,关于并杂环合成方面的研究至今不多见,作者前     

异色满酮-4及其衍生物的合成(Ⅰ)

在异色满酮-4的合成中改变了介质,合成了异色满酮-4的五种O-酰基肟、六种Mannich碱、四种3-位亚甲基取代物和六种同嘧啶及吡唑并合的衍生物,并对于部分异色满酮-4的Mannich碱进行了药理试验。     

异色满并三氮杂酮化合物的合成

异色满(isochroman)是自然界中某些抗菌素和毒菌的基本骨架组成。例如,卡拉真菌素(kalafugin),七尾霉素(nanaomycin)和桔霉素(citrinin)等都是带有异色满环结构的杂环醌。近年来,人们合成了许多具有各种药理活性的异色满类化合物,其中引入异色满环的(艹卓)酚酮具有抑制肿瘤细胞的功能。为了合成类似活性的异色满类化合物,本文选择[1.2.4]三氮杂(艹卓)酮类的七员环系与异色满并环,旨在寻找抗癌新药。     

2－杂萘满并喹啉衍生物的合成及其抑菌活性

２－杂萘满并喹啉衍生物的合成及其抑菌活性刘永军，刘英（曲阜师范大学化学系曲阜２７３１６５）关键词杂萘满酮，合成，抑菌活性在２－杂萘满酮的化学结构，最常见的杂原子为Ｏ、Ｓ、Ｎ，分别俗称异色满酮、硫代异色满酮、异喹啉酮．自然界中的许多天然或代谢产物如卡拉...     

异色满并含氮杂环类衍生物的合成

以异色满酮-4为起始原料，利用4-位羰基和α-位氢的缩合反应，合成出异色 满并吡啶、异色满并嘧啶、异色满并喹啉和异色满并萘啶类化合物，所合成的新化 合物均经核磁共振光谱、红外光谱及元素分析证明其结构．     

异色满并[4,3—d]嘧啶类衍生物的合成

利用异色满酮－４合成了一系列新的异色满并嘧啶类衍生物４ａ－ｔｆ，其结构均经元素分析，ＩＲ和ＨＮＭＲ分析予以证实。     

新型咪唑-查尔酮衍生物的设计、合成及抗宫颈癌和顺铂耐药活性研究

摘要 目的 以甘草查尔酮母核为先导化合物骨架,设计、合成一系列新型咪唑-查尔酮衍生物并进行抗宫颈癌活性研究。方法 在查尔酮骨架的B环引入4种咪唑环,在A环分别引入甲氧基、氨基、羟基等活性基团;采用Claisen-Schmidt反应合成系列新型咪唑-查尔酮衍生物,其结构经1H-NMR、13C-NMR和HRMS进行表征。通过MTT、Transwell、流式细胞仪和分子对接实验方法,初步探索目标化合物的抗宫颈癌活性及作用机制。结果 大部分化合物具有一定的抗宫颈癌活性,其中2i较为显著,且对正常细胞的毒性较小。此外,化合物2i能够显著抑制HeLa和HeLa/DDP细胞的迁移和侵袭能力,能够诱导其凋亡,并阻滞HeLa和HeLa/DDP细胞于G2/M期;分子对接模拟显示2i与查尔酮母核和原配体秋水仙碱相比,2i与微管蛋白秋水仙碱结合位点具有较好的结合能力,并能够产生氢键相互作用力。结论 化合物2i具有较显著的抗宫颈癌和抗宫颈癌顺铂耐药活性作用,这可能与其抑制了微管蛋白靶点有关。     

7,10—二芳基—六氢（四氢）苯并[C]吖啶—8—酮的合成

吖啶及吖啶酮类化合物具有广泛的药理活性,其中许多化合物具有明显的杀菌、抗炎、增强记忆、镇痛和抗癌等活性。如早年开发的抗癌药物山柚柑碱(Acronycine)就具有显著的抗癌作用,且抗瘤谱较广。近年来抗癌新药安吖啶(Amsacrime)在临床上用于治疗急性白血病收到疗效后,对吖啶及吖啶酮衍生物的合成及抗癌活性研究日渐增多。已测定了一些化合物     

异色满酮-4及其衍生物的合成(Ⅳ)——辛可宁酸类似物的合成

由异色满酮-4(1)与邻氨基苯甲醛或邻氨基胡椒醛进行Friedlender缩合反应得到异色满并喹啉衍生物异色满并[4,3-b]喹啉(2)和9,10-亚甲二氧基异色满并[4,3-b]喹啉(3).     

色胺酮衍生物设计、合成及抗肿瘤活性构效关系研究

首先合成吲哚醌衍生4a~4f,氧化水解得到邻氨基苯甲酸衍生物5a~5d.以这两者为原料设计合成A和/或D环取代的色胺酮衍生物1a~1q.然后,以色胺酮6位酮羰基分别与水合肼、盐酸羟胺反应生成C环席夫碱结构.最后,以哌嗪结构取代B环嘧啶酮合成茚(1,2-b)喹喔啉-11-酮.共设计合成20个化合物,其中新化合物13个.对所合成化合物的结构经红外光谱、核磁氢谱、元素分析确证.测定所合成化合物对肿瘤细胞A549的体外抑制活性.结果表明化合物1b,1c,1i,1j,1p和1q表现出较强的肿瘤细胞抑制活性,IC50值分别为3.58,0.99,1.03,2.10,0.51和0.43μmol·L-1.构效关系研究表明:D环卤素取代提高抗肿瘤活性,而取代基团在A环时则减弱抗肿瘤活性;B环(嘧啶环)被哌嗪环取代后抗肿瘤活性消失(IC50100μmol·L-1);而C环酮羰基生成席夫碱结构抗肿瘤活性与色胺酮相当.     

5-取代苯氨基-6-苯基-1,2,4-三嗪-3-酮的合成

苯甲铣基-N-取代茜基硫代甲酰胺与氨基脲缩合后,环化可何成4,6-二取代-5-硫酮-1,2,4-三嗪-3-酮.本文报道将其缩氨基脲中硫甲基化,然后在碱性条件下, 改变成环方式,合成九个5-取代苯氨基-6-苯基-1,1,4-三嗪1-3-酮.它们的结构经元素分析,红外,核磁,质谱等予以证实.探讨了两种不同成环原因.     

SYNTHESIS AND CHARACTERIZATION OF SIDE CHAIN LIQUID CRYSTATALLINE POLYSILOXANES CONTAINING BENZYL ETHER LINKING UNITS

Side chain liquid crystalline polysiloxanes containing benzyl ether linkingunits were synthesized by the hydrosilylation of poly (methylhydrosiloxane) with a series of4-(4-alkoxybenzyloxy)-4'-allyloxybiphenyl monomers [4-(4-methoxybenzyloxy )-4'-allyloxy-biphenyl(M_1), 4-(4-ethoxybenzyloxy)-4'-allyloxybiphenyl (M_2), 4-(4-propoxybenzyloxy)-4'-allyloxybiphenyl (M_3), 4-(4-butoxybenzyloxy)-4'-allylox(M_4), 4-(4-pentoxy-benzyloxy)-4'-allyloxybiphenyl (M_5), 4-benzyloxy-4'-allyloxybiphenyl (M_6)]. The phasebehavior of monomeric and polymeric liquid crystals was characterized by differential scan-ning calorimetry and optical polarization microscopy where the groups are ranged frommethoxy to pentoxy Both the monomeric and polymeric liquid crystals exhibit 1iquidcrystal behaviors.     

Theoretical study on tetranuclear boron clusters: B4X4 (X = H, F, Cl, Br, I)

The molecular orbitals for B4H4, B4F4, B4Cl4, B4Br4 and B4I4 have been calculated by using all-electron or effective core potential ab initio method at the self-consistent field level using basis sets with diffuse and polarization functions. The boron-boron and boron-halide (-hydrogen) distances of these cage compounds are optimized with three kinds of basis sets constrained to a tetrahedral symmetry. According to the localization scheme of Boys, four three-centered two-electron (3c2e) B-B-B bonds localized on each of the faces of the B4 tetrahedron are derived for B4X4 clusters. The HOMO-LUMO energy gaps, atomization energies and Mulliken overlap populations of these compounds indicate that the stabilities of the clusters decrease in the sequence of B4F4 > B4Cl4, B4H4 > B4Br4 > B4I4.     

NiTi过渡金属团簇的结构和芳香性的理论研究

在B3PW91/6-311+G(d)计算水平上, 计算并讨论了Ni₄Ti₂, [Ni₄Ti₂]²⁺, [Ni₄Ti₂]^2-与Ni₄Ti₄, [Ni₄Ti₄]²⁺, [Ni₄Ti₄]^2-团簇的几何结构和芳香性. 在构型优化过程中得到了Ni₄Ti₂(D_4h), [Ni₄Ti₂]²⁺(D_4h), [Ni₄Ti₂]^2-(D_4h)和Ni₄Ti₄(D_2h)4个稳定构型, 发现当引入上下2个Ti原子后, Ni₄环成为了平面正方形构型. 核无关化学位移(NICS)计算结果表明, Ni₄Ti₂(D_4h)与Ni₄Ti₄(D_2h)的NICS值为正, 而[Ni₄Ti₂]²⁺(D_4h)和[Ni₄Ti₂]^2-(D_4h)的NICS值为负, 且[Ni₄Ti₂]^2-(D_4h)的NICS值更负. 同时还发现, 由s与d轨道参与形成的反磁性环流是引起[Ni₄Ti₂]²⁺(D_4h)和[Ni₄Ti₂]^2-(D_4h)具有较大芳香性的主要原因; 其中Ti原子主要提供d_z²与s轨道, 而Ni原子主要利用其d_z²与d_x²-y²轨道形成正方形环, 它们之间构成了球状的d轨道环流, 且[Ni₄Ti₂]²⁺(D_4h)和[Ni₄Ti₂]^2-(D_4h)中还有非常明显的π轨道环流.     

2-[4-取代苯基-2-氧-3-酰氨基-1-吖丁啶基]-2-苯基乙酸类化合物的合成

用叠氮钠和D-苯基甘氨酸为原料合成了2-[4-取代苯基-2-氧-3-酰氨基-1-吖啶基]-2-苯基乙酸类化合物. 在叠氮乙酰氯和亚胺化合物在三乙胺存在下在-78℃时进行环缩合反应, 可导致立体专一性合成顺-甲基-2-(4-取代苯基-2-酮-3-叠氮-1-吖啶基)-2-苯基乙酸, 催化氢化或硫化氢可减少叠氮基和得到氨基β-内酰胺后者被酰化生成α-酰氨基-β-内酰胺, 在温和碱性条件下选择性地氢化酯基既不会影响β-内酰胺环, 又不全影响酰胺侧链. 合成了二十个标题化合物, 其中九个被表明对β-内酰胺酶有抑制活性.     

单个离子标准迁移自由能的测定

本文采用活化分析法测定参考解质Ph4AsPh4B晶体在水和有机溶剂中的溶解度和计算了它从水迁移到有机溶剂中的标准迁移Gibbs自由能△^s^wG^0t.根据Ph4AsPh4B假定,求得参考正负离子Ph4As^+和Ph4B^-的标准迁移Gibbs自由能.又通过测定Ph4AsTcO4,CsPh4B,KPh4B和CsTCO4等晶体在水和有机溶剂站的溶解度,求得TcO4^-,K^+,Cs^+等离子的标准迁移自由能,并对结果进行了讨论.     

Eight-vertex tetrametallic structures derived from cubanes: a close relationship between bisdisphenoidal metallaborane and organometallic clusters

The metallaborane Cp4Co4B4H4 and the organometallic cluster Cp4Fe4C4H4 (Cp = eta5-cyclopentadienyl) not only are isoelectronic but also exhibit completely analogous eight-vertex bisdisphenoidal structures. Such structures, as well as the tetracapped tetrahedral structure of the Cp4Fe4(mu3-CO)4 precursor to Cp4Fe4C4H4, can be derived from a cube by insertion of diagonals in each of the six faces. Furthermore, the formation of Cp4Fe4C4H4 from Cp4Fe4(mu3-CO)4 can be described as a double diamond-square-diamond process preserving D2d symmetry throughout the process.     

Synthesis and α‐glucosidase inhibitory,DPPH scavenging activity of substituted 2‐oxo‐2H‐chromen‐7‐yl‐dihydrogen phosphate derivatives

Series of phosphorylated coumarin derivatives ( 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j ) were synthesized by Pechmann condensation, phosphorylation, and debenzylation reactions in very good yields. Thus, synthesized compounds ( 4a , 4b , 4c , 4d , 4e , 4f , 4g , 4h , 4i , 4j ) were evaluated for their α‐glucosidase and 1,1‐diphenyl‐2‐picrylhydrazyl scavenging activities; few compounds showed moderate to good activity. J. Heterocyclic Chem., 00 , 00 (2011).     

C4Sm-4相对稳定性的从头算研究

从五十年代至今，对用通式C；；0：－…＝3，45，6n表征的氧碳化合物（OXOCCbollS）已进行了大显的理论和实验研究，认为它们是一类新的芳香化合物山．用硫、硒等取代氧的类似化合物（一般称为类氧碳化合物或假氧碳化合物，ps。11。10－OX。。CCI．b0118）的研究也有许多报导［     

Generation and collision-induced dissociation of ammonium tetrafluoroborate cluster ions

Singly and doubly charged cluster ions of ammonium tetrafluoroborate (NH4BF4) with general formula [(NH4BF4)nNH4]+ and [(NH4BF4)m(NH4)2]2+, respectively, were generated by electrospray ionization (ESI) and their fragmentation examined using collision-induced dissociation (CID) and ion-trap tandem mass spectrometry. CID of [(NH4BF4)nNH4]+ caused the loss of one or more neutral NH4BF4 units. The n = 2 cluster, [(NH4BF4)2NH4]+, was unique in that it also exhibited a dissociation pathway in which HBF4 was eliminated to create [(NH4BF4)(NH3)NH4]+. Dissociation of [(NH4BF4)m(NH4)2]2+ occurred through two general pathways: (a) 'fission' to produce singly charged cluster ions and (b) elimination of one or more neutral NH4BF4 units to leave doubly charged product ions. CID profiles, and measurements of changing precursor and product ion signal intensity as a function of applied collision voltage, were collected for [(NH4BF4)nNH4]+ and compared with those for analogous [(NaBF4)nNa]+ and [(KBF4)nK]+ ions to determine the influence of the cation on the relative stability of cluster ions. In general, the [(NH4BF4)nNH4]+ clusters were found to be easier to dissociate than both the sodium and potassium clusters of comparable size, with [(KBF4)nK]+ ions the most difficult to dissociate.