哒嗪酮类α1-肾上腺素受体拮抗剂的合成和生物活性研究

将苯(氧)乙胺和苯氧烷胺类α₁-肾上腺素受体拮抗剂中的苯(氧)乙胺、苯氧烷胺片段引入哒嗪酮类化合物中, 设计、合成了30个新的含哒嗪酮环的α₁-肾上腺素受体拮抗剂. 所有新化合物的结构均经¹H NMR, IR, HRMS确证. 生物活性测试表明28个目标物对α₁-肾上腺素受体有较好的拮抗作用(pA₂＞6.00), 化合物6o, 6p, 6q, 6v, 6x, 6y, 10c, 10d的pA₂值＞7.00.     

含能富勒烯吡咯烷衍生物的合成及工艺研究

利用Prato反应合成分离出了新型含硝基富勒烯吡咯烷衍生物1, 并对其工艺条件进行了研究, 探讨了反应物计量比、温度及时间对产物1产率的影响, 得到了合成产物1的最佳工艺条件: C₆₀, 间硝基苯甲醛和N-甲基甘氨酸的物质的量比为1∶1∶2, 温度为100 ℃, 反应时间为16 h, 此时产物1产率达到94.8%(以消耗的C₆₀计). 同时用UV-Vis, FT-IR, ¹H NMR, ¹³C NMR and MS spectra等光谱手段确定了产物1的分子结构.     

具有C2对称的氮磷-氧磷配体双噁唑啉磷乙烷的合成及在不对称催化加氢中的应用

利用易得的光学纯N-甲基氨基醇与1,2-双(二氯磷)乙烷缩合合成了一类新的具有C₂对称轴的氮磷-氧磷配体(R,R)-双噁唑啉磷乙烷(BOAPE) 1～4. 该类配体不仅具有C₂对称结构和刚性五元环, 还具有富电子特性, 利用500 MHz进行了¹H NMR, ³¹P NMR, ¹³C NMR表征. 与这些配体配位形成的Rh配合物用于N-苯甲酰基脱氢丙氨酸衍生物和α-功能化酮不对称加氢, 分别可以得到99%和98%的ee. 这类配体比它们相对应的非C₂对称的氮磷-氧磷化合物(AMPP)配体具有更高的对映选择性. 在这四个新的配体中配体(R,R)-Ph-BOAPE (2)的催化性能最优. 催化剂[Rh(COD)(R,R)-Ph-BOAPE]BF₄的半反应周期t_1/2和周转频率(TOF)在N-苯甲酰基肉桂酸甲酯的不对称加氢反应中分别为12 min和6.5 min^－1.     

不同加成数C60精氨酸衍生物的合成及其清除活性氧自由基的性能

通过控制反应配比, 首次合成了三种具有不同加成数目的水溶性C₆₀精氨酸衍生物, C₆₀[HNC(NH)NH(CH₂)₃CH(NH₂)COOH]_nH_n (n＝2, 6, 8). 采用FT-IR, UV, RF, ¹H NMR, ¹³C NMR, LC-MS, EA, 粒径分析, 透射电镜等手段对其结构进行了表征. 同时采用化学发光法考察了三种具有不同加成数目的C₆₀精氨酸衍生物对活性氧自由基(超氧阴离子O₂^－.及羟自由基•OH)清除能力, 结果表明, C₆₀精氨酸衍生物对活性氧自由基具有优良的清除能力, 且清除能力与加成基团供电效应、空间位阻及C₆₀精氨酸衍生物在水中的聚集形态等因素密切相关.     

α-取代氨基氟代苯基膦酸酯衍生物的合成、晶体结构与抗癌活性

利用席夫碱与亚磷酸酯反应, 合成了新型O,O'-二烷基-α-(6-甲氧苯并噻唑-2-基氨基)-4-氟苯基膦酸酯化合物, 结构经元素分析, IR, ¹H NMR, ¹³C NMR和X单晶衍射确认. X单晶衍射测试结果表明: 化合物3d分子属于四面体晶系, 空间群I4(1)/a, a＝2.1055(3) nm, b＝2.1055(3) nm, c＝2.0521(5) nm, α＝90.00°, β＝90.00°, γ＝90.00°, V＝0.9098(3) nm³, Z＝16, D_c＝1.321 mg/m³, ＝0.250 mm^－1, F(000)＝3808. 化合物还存在着1个分子内氢键[N(2)—H(2)…O(1)]. 生物测定表明化合物3f在20 g/mL浓度下对PC3细胞的抑制率为84.3%.     

还原法制备二配位β-二亚胺镓卡宾及其结构表征

侧链无活性位点的β-二亚胺配体具有对低价金属中心良好的电子稳定效应和侧基保护作用。金属K能够还原β-二亚胺二氯合镓(Ⅲ)化合物PhC （PhCN-Dip）₂GaCl₂（2,Dip=2,6-ⁱPr₂C₆H₃）,以较高产率得到新一例β-二亚胺稳定的分子态Ga(Ⅰ)卡宾单体PhC （PhCN-Dip）₂Ga：（3）。化合物2和3的结构与组成通过X射线单晶衍射与NMR进行表征。单体镓卡宾3中心Ga(Ⅰ)离子处于平面六元氮杂环的一个顶角,具有弯曲二配位的几何构型。理论计算结果显示,3的HOMO能级较低,被Ga的孤对电子占据,LUMO+1对应Ga的空p轨道,但是能级比HOMO要高601.0 kJ·mol^-1,这表明3是一个与氮杂环碳卡宾同构的镓卡宾分子,且Ga(Ⅰ)离子的孤对电子具有较好的热稳定性。     

基于β-二亚胺配体的铝氧硼六元环化合物和其中间体的合成、表征及其反应性研究

LAlH₂（L=（Z）-4-[（2,6-二异丙基苯基）氨基]戊-3-烯-2-亚基-2,6-二异丙基苯胺）分别与2-噻吩苯硼酸和2-苯并噻吩硼酸反应,合成含铝氧硼六元环的化合物LAl[OB（2-thiophen）]₂（μ-O）（2）和LAl[OB（2-benzo[b]thiophen）]₂（μ-O）（3）。LAlH₂与2,6-二甲基苯硼酸反应生成了LAl[OB（2,6-CH₃C₆H₄）OH]₂（4）。化合物4是化合物2和3的中间体。所有化合物都进行了IR、¹H NMR和元素分析等表征。并通过X射线单晶衍射测定了化合物2和4的单晶结构。     

柔荑软珊瑚Nephthea sp.中两种具有细胞毒活性的甾醇化合物

采用抗肿瘤活性追踪法对采自中国南海西沙群岛永兴岛柔荑软珊瑚Nephthea sp.中抗肿瘤活性成分进行研究, 报道了两种具有细胞毒活性的甾醇化合物, 经过MS, IR, ¹H NMR, ¹³C NMR (DEPT), HSQC 和HMBC等光谱技术鉴定为: 24-甲基胆甾-5-烯-3β,8β-二醇(1)和24-亚甲基胆甾-4-烯-3β,6β-二醇(2), 化合物1为新化合物, 利用X-ray单晶衍射技术验证化合物2的立体结构. 化合物1对肝癌细胞(BEL-7402), 小鼠白血瘤细胞(P₃₈₈)和人结肠癌细胞(LOVO)作用的IC₅₀值分别为18.0, 25.5和20.6 μg/mL; 化合物2对肿瘤细胞P₃₈₈和人乳腺癌细胞(MCF)作用的IC₅₀值分别为1.0和2.5 μg/mL.     

一维链状钴(Ⅱ)和锰(Ⅱ)配合物的合成及结构表征

本文以乙酰丙酮和1R,2R-环己二胺进行缩合得到N,N′-双(乙酰丙酮)-1R,2R-环己二胺的Schiff碱配体L,再分别同CoCl₂·6H₂O和MnCl₂·4H₂O进行配位反应,得到了2个配合物[CoLCl₂]_n (1)和[MnLCl₂(C₂H₅OH)·H₂O]_n(2),并用元素分析,FTIR和X-射线单晶结构分析进行了表征。配合物1和2的晶体均属于正交晶系,空间群分别是Fddd和P2₁2₁2₁。在化合物1中,每个Co(Ⅱ)的配位环境均为扭曲四面体,在化合物2中,每个Mn(Ⅱ)的配位环境都是三角双锥。2个配合物中每个配体L通过其两臂乙酰丙酮亚胺单元的端基氧原子同2个金属离子配位桥联形成一维螺旋链结构。     

超声辐射下N-苄基-α,α-二苯基-2-吡咯烷甲醇衍生物的制备及其杀虫活性测定

在无水无氧、超声辐射下, N-取代苄基脯氨酸苄基酯与取代苯基溴化镁反应合成了7个未见文献报道的N-苄 基-α,α-二苯基-2-吡咯烷甲醇衍生物, 其结构经IR, ¹H NMR和元素分析测试确证, 并且初步生物活性测定结果表明目标化合物均有较好的杀虫活性.     

Divergent Synthesis of Chelating Aziridines and Cyclic(Alkyl)(Amino)Carbenes (CAACs) from Pyridyl-Tethered Robust Azomethine Ylides

Azomethine ylides are typically in situ generated synthons for making N-heterocycles through cycloaddition reactions. But an offbeat aspect about them is the isomeric nature of aldiminium-based azomethine ylides and (alkyl/aryl)(amino)carbenes, interconvertible by a formal 1,3-H⁺ transfer. Herein, two thermally robust azomethine ylides with a N-appended picolyl sidearm are isolated, which cyclize to ^pyaziridines at 80 °C but unprecedentedly result ^N−picoCAAC-CuCl (CAAC=cyclic(alkyl)(amino)carbene) complexes when heated with CuCl at merely 60 °C. The pendant N_py, as revealed by computational analysis, plays a crucial role in this unusual 1,3-H⁺ shift using a deprotonation-protonation sequence, as well as in placing the CuCl at the carbenic site in tandem. The softer nature of Cu^(I) is also critical. Chelating CAACs are rare and one with a N-tethered additional donor is priorly unknown. Both ^N-picoCAAC and ^pyaziridine are bidentate chelators giving highly active cationic Rh^(I) catalysts for hydrosilylating unactivated olefins by Et₃SiH. Notably, the ^pyaziridine-Rh^(I) is superior than the ^N-picoCAAC-Rh^(I) catalyst.     

An Efficient Synthesis of New Dispiropyrrolidine Derivatives via Three‐Component 1,3‐Dipolar Cycloaddition Reaction

A series of new dispiropyrrolidine derivatives were synthesized via the three‐component 1,3‐dipolar cycloaddition reaction of azomethine ylides generated in situ by the decarboxylative condensation of acenaphthenequinone and sarcosine or l ‐thioproline with 5‐benzylidene‐1,3‐dimethylpyrimidine‐2,4,6‐trione. The structures of the products were identified by IR, ¹H‐NMR, and HRMS spectra.     

HEXACOORDINATE ORGANOSILICON(IV) COMPOUNDS WITH A TETRADENTATE AZOMETHINE LIGAND

ABSTRACT

Hexacoordinate silicon compounds with the tetradentate azomethine ligand N,N′-ethylenebis(2-hydroxyacetophenoneimine) have been prepared and characterized by elemental analyses, molecular weight determinations and spectral (IR, ¹H, ¹³C and ²⁹Si NMR) studies. The data clearly demonstrate the octahedral geometry around the silicon atom.     

Synthesis,structural, and spectral studies of diorganotin(IV) complexes with 2–hydroxy-5-methylbenzaldehyde-N(4)-cyclohexylthiosemicarbazone

Three new diorganotin(IV) complexes, [Me₂Sn(L)] (2), [Bu₂Sn(L)] (3), and [Ph₂Sn(L)] (4) [where H₂L (1) = 2-hydroxy-5-methylbenzaldehyde-N(4)-cyclohexylthiosemicarbazone] have been synthesized by reacting the corresponding diorganotin(IV) dichloride with H₂L (1) in absolute methanol in the presence of potassium hydroxide. All the compounds have been characterized by CHN analyses, UV–vis, FT-IR, ¹H, ¹³C, and ¹¹⁹Sn NMR spectroscopy. The molecular structures of H₂L (1) and 2 have been confirmed by single crystal X-ray diffraction analysis. H₂L (1) is found to be in the thiol tautomeric form. The X-ray structure of 2 showed that H₂L is a tridentate ligand and binds to the tin(IV) atom via the phenolic oxygen, azomethine nitrogen, and thiolate sulfur. Complex 2 has a triclinic structure and the coordination geometry of tin(IV) is distorted trigonal bipyramidal. The sulfur and oxygen are in axial positions while the azomethine nitrogen of 1 and two methyl groups occupy the equatorial positions. The C-Sn-C angles determined from ¹J(¹¹⁹Sn, ¹³C) for 2, 3, and 4 are 124.35°, 123.11°, and 123.82°, respectively. The values of δ(¹¹⁹Sn) for 2, 3, and 4 are ?153.4, ?180.59, and ?158.3 ppm, respectively, indicating five-coordinate tin(IV). From NMR data a distorted trigonal-bipyramidal configuration at each tin is proposed.     

Synthesis of fulleropyrrolidine dicarboxylic acid and its scavenging activity to superoxide radicals (O_2 ^{\bar \cdot } )

Photochemical reaction of C60 with iminodiacetic ester (NH(CH₂COOR)₂, R=Me, Et, t-Bu) produced fulleropyrrolidine derivatives 2 in a 55%–36% yield (based on consumed C60). The reaction activity correlated with the steric hindrance of R groups. The order of the reaction rates decreased from Me to t-Bu (R=Me>Et>t-Bu). Fulleropyrrolidine derivative 2 (R=Me) were hydrolyzed with NaH and methanol in toluene, and then acidified with HCl to result in the corresponding fulleropyrrolidine dicarboxylic acid 3 in a 65% yield (relative to fulleropyrrolidine derivative 2). C60 derivatives 2 and 3 were structurally characterized by ¹H NMR, ¹³C NMR, IR, and elementary analysis, MS. A chemiluminescence technique was applied to study the effects of their scavenging superoxide radicals generated by pyrogallol autoxidation. The results show fulleropyrrolidine dicarboxylic acid 3 had scavenging activity and the efficiencies were dependent on their concentrations. At the concentration of 3.0×10⁻⁴ mol·L⁻¹, fulleropyrrolidine dicarboxylic acid 3 showed a radical scavenging efficiency of approximately 70%. Finally, the influence of structure factor on the scavenging activity was discussed. The results show that the monoadduct of C60, owing to keeping almost intact double bands in C60 moiety, had obvious scavenging activity for superoxide radicals . __________ Translated from Chinese Journal of Applied Chemistry, 2006, 23(1) (in Chinese)     

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,structural characterization,oxygen sensitivity,and antimicrobial activity of ruthenium(II) carbonyl complexes with thiosemicarbazones

[Ru(CO)(PPh₃)₂(η³-O,N³,S-TSC¹)] (1), [Ru(Cl)(CO)(PPh₃)₂(η²-N³,S-TSC²)] (2), and [Ru(Cl)(CO)(PPh₃)₂(η²-N³,S-TSC³)] (3) have been prepared by reacting [Ru(H)(Cl)(CO)(PPh₃)₃] with the respective thiosemicarbazones TSC¹ (2-hydroxy-3-methoxybenzaldehyde thiosemicarbazone), TSC² (3-hydroxybenzaldehyde thiosemicarbazone), and TSC³ (3,4-dihydroxybenzaldehyde thiosemicarbazone) in a 1?:?1 M ratio in toluene and all of the complexes have been characterized by UV–vis, FT-IR, and ¹H and ³¹P NMR spectroscopy. The spectroscopic studies showed that TSC¹ is coordinated to the central metal as a tridendate ligand coordinating via the azomethine nitrogen (C=N), phenolic oxygen, and sulfur to ruthenium in 1, whereas TSC² and TSC³ are coordinated to ruthenium as a bidentate ligand through azomethine nitrogen (C=N) and sulfur in 2 and 3. Oxygen sensitivities of 1–3 and [Ru(Cl)(CO)(PPh₃)₂(η²-N³,S-TSC⁴)] (4), and antimicrobial activities of 1–3 have been determined.     

Photochemical reactions of metal carbonyls [M(CO)6 (M=Cr,Mo, W)] with N,N′ -bis(salicylidene)-1,2-bis- ( o -aminophenoxy)ethane

The complexes [M(CO)₄(η²-H₂L)] [M?=?Cr; 1, Mo; 2, W; 3] have been synthesized by photochemical reactions of VIB metal carbonyls [M(CO)₆] [M?=?Cr,?Mo,?W] with N,N′-bis(salicylidene)-1,2-bis-(o-aminophenoxy)ethane (H₂L) in THF and characterized by elemental analyses, FTIR, ¹H?NMR and mass spectra. The H₂L ligand is coordinated to the central metal as a bidentate ligand via the central azomethine nitrogen atoms in 1–3.     

三苯基咪唑类化合物的合成及其紫外、荧光性质研究

设计合成了四种三苯基咪唑类化合物:4,5-二苯基-2-对甲酰基苯基咪唑(2a),4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2b),N-苄基-4,5-二苯基-2-对甲酰基苯基咪唑(2c)和N-苄基-4,5-二(2-硝基苯基)-2-对甲酰基苯基咪唑(2d),并用FT-IR,NMR和MS进行结构表征.在乙酸乙酯-石油醚溶液中获得了2c的单晶,用X射线单晶衍射法测定了其晶体结构,晶体属于三斜晶系,空间群P1,晶胞参数a=0.73796(15)nm,b=0.90136(18)nm,c=1.6644(3)nm,α=86.87(3)°,β=78.25(3)°,γ=89.94(3)°,V=1.0822(4)nm3,Dc=1.272g/cm3,Z=2,F(000)=436,μ=0.077mm-1,R1=0.0459,wR2=0.1303.研究了四种化合物的紫外与荧光性质,发现官能团硝基与苄基的引入,对其吸收峰和发射峰均有不同程度的影响:在紫外光谱中两种官能团均使吸收峰蓝移;在荧光光谱中苄基使发射峰蓝移而硝基使发射峰红移.测定了2a和2c在不同溶剂中的荧光寿命,其中2a在DMSO中寿命最长,为3.18ns.这些光谱性质为研究其双光子吸收、双光子荧光和非线性光学性质奠定了理论和实验基础.     

Synthesis,Characterization, and Antimicrobial Evaluation of Quinoline-Oxadiazole–Based Azetidinone Derivatives

A series of 3-chloro-1-(aryl)-4-(2-(2-chloroquinolin-3-yl)-5-(pyridin-4-yl)-1,3,4-oxadiazol-3(2H)-yl)-4-ethyl-azetidin-2-ones (5a–l) have been synthesized and characterized by IR, ¹H NMR, and¹³C NMR. Synthesized compounds were screened for their antimicrobial activity against different strains of bacteria (E. coli, P. aeruginosa, S. aureus, S. pyogenes, C. albicans, A. niger, and A. clavatus). On the basis of statistical analysis, it has been observed that compounds had significant correlations.