含氮芥基查尔酮类衍生物的合成、晶体结构及抗肿瘤活性

根据拼药原理,将氮芥类抗肿瘤药物的药效基团N,N-二(2-氯乙基)氨基拼接到查尔酮结构中,合成出了一系列新型含氮芥基的查尔酮衍生物3a～3r,并用1H NMR,IR,HRMS-ESI及X射线对其结构进行了确证.采用MTT法对所合成的化合物进行了体外抗肿瘤活性测试,结果表明部分化合物对所选肿瘤细胞的增殖有较强的抑制作用,其中,化合物3j和3l对K562的IC50值分别为20.01和18.6μmol/L;对HepG2的IC50值分别为43.46和21.39μmol/L.实验培养并得到了目标产物3e和3l的晶体结构,X射线分析表明化合物3e和3l都属三斜晶系,P-1空间群.     

5,10,15,20-四(4-(4-吡啶)酮基)苯基卟啉的合成、表征及晶体结构

利用丙酸法合成了一种新的化合物5,10,15,20-四(4-(4-吡啶)酮基)苯基卟啉,并进行了IR,UV-Vis,MS及EA表征,探讨了试剂4-羟基吡啶的异构现象及合成方法。采用溶液结晶法得到了该卟啉分子的晶体,对其进行了X-射线单晶衍射及粉末衍射测定。结果表明:该晶体属于正交晶系,空间群为Fddd。相邻的卟啉分子通过吡啶环之间的π…π作用与其他卟啉分子相连形成二维层状结构。层与层之间进一步通过吡啶环与卟啉环之间的π…π作用而形成三维超分子结构。该化合物可以作为构建金属卟啉框架新材料(MPF)的良好配体。     

2,6-双(1-苄基-2-苯并咪唑基)吡啶的合成、晶体结构、光谱及抗氧化活性

合成了化合物2,6-双(1-苄基-2-苯并咪唑基)吡啶,通过元素分析、红外光谱、核磁共振氢谱和X-射线单晶衍射方法对其结构进行了表征.结构分析表明,该晶体属于单斜晶系,C2/c空间群,晶胞参数a=2.989 30(15) nm,b=1.093 74(5) nm,c=1.578 86(7) nm, β=103.555(5)o,V=5.018 32(42) nm3,Z=8,Dc=1.301 g/cm3,μ(Mo-Kα)=0.079 mm-1,F(000)=2 064,S=1.038,R1=0.046 0,w R2=0.127 9,化合物分子间存在的C—Hπ和苯环ππ堆积作用,使得其沿b轴方向形成了一维链状结构.通过紫外-可见吸收和荧光光谱研究了化合物的光谱性质及其对DPPH自由基的抗氧化活性.     

3-苯基喹唑啉-4(3H)-酮的合成及晶体结构

标题化合物C14H10ON2是由邻硝基苯甲酰苯胺与原甲酸三乙酯在低价钛试剂作用下反应而得。结构通过单晶X-射线衍射分析确定, 其晶体属于单斜晶系, 空间群P21/c, a = 12.080(2), b = 7.793(1), c = 11.599(1) ? b = 97.56(1), Mr = 222.24, V = 1082.4(2) ?, Dc = 1.364 g/cm3, Z = 4, m(MoKa) = 0.88 mm-1, F(000) = 464, R = 0.0385, wR = 0.0851。X-衍射分析表明: 平面I (C(1)~C(6))与平面II (C(9)~C(14))之间的夹角为124.38; 平面I与平面III (ON(1)?N(2)C(7)C(8)C(9)C(14))之间的两面角为125.47; 平面II与平面III之间的两面角为2.76。     

μ-氧-双[三(对氟苄基)锡]的合成、表征及晶体结构

The μ-oxygen-bis[tri(p-fluorobenzyl)tin] was synthesized. The structure were characterized by elementary analysis, IR and ¹H NMR and the crystal structure were determined by X-ray single crystal diffraction. The crystal of the title compound belongs to rhombohedral with space group R, a=1.346 4(4), b=1.346 4(4), c=1.772 9(7) nm, α=90°, β=90°, γ=120°, Z=3, V=2.783 2(15) nm³, D_c=1.625 g·cm^-3, μ(Mo Kα)=1.408 mm^-1, S=1.088, F(000)=1 350, R₁=0.027 5, wR₂=0.065 9. In compound, the tin atom has a distorted tetrahedral coordination configuration. CCDC: 257079.     

含氮芥和蒽环的新型α,β-不饱和酮的合成、表征与抗肿瘤活性

为获得含氮芥和蒽环的α,β-不饱和酮衍生物及其体外抗肿瘤效果,结合Vilsmeier-Haack反应和羟醛缩合反应合成了两种新型含氮芥和蒽环的α,β-不饱和酮(1a和1b),其结构经¹H NMR、¹³C NMR、 MS(ESI)和紫外和荧光光谱表征。采用MTT法检测了1a和1b对肺癌细胞A549、肾癌细胞786-O、宫颈癌细胞Hela和乳腺癌细胞MDA-MB-231增殖的抑制活性;采用细胞划痕实验检测了1a对Hela细胞转移的影响;采用流式细胞仪(PI染色)检测了1a对Hela细胞周期的影响。结果表明：1a和1b对4种肿瘤细胞均有良好的抗增殖活性,其中1a的活性略高于1b;1a能有效抑制Hela细胞转移,并使Hela细胞周期阻滞在S期。     

微波辐射相转移催化下水相合成α，α′-双亚苄基环烷酮

芳醛与环戊酮或环己酮在碳酸钠水溶液中，用微波辐射-相转移催化法合成α，α′-双亚苄基环烷酮。反应在0．5～7min内完成，产率高达80％～99％，后处理极为简便，是一种环境友好的绿色合成．     

二苄基锡双(四氢吡咯荒酸酯)的合成、表征和晶体结构

Dibenzyltin bis(dithiotetrahydropyrrolocarbamate) was synthesized by the reaction of dibenzyltin dichloride with dithiotetrahydropyrrolocarbamate. The compound was characterized by elemental analysis, IR, ¹H NMR and MS. and the crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to or-thorhombic with space group Pccn, a=2.1665(6)nm, b=0.9932(3)nm, c=1.1979(3)nm,α=90°,β=90°,γ=90°,Z=2,V=2.5777(12)nm³,D_c=1.529g·cm^-3,μ(MoKα)=1.330mm^-1,F(000)=1208,R₁=0.0341, wR₂=0.0627. In the crystals, the structures consist of discrete molecules in which the tin atom is six-coordinate in a distorted octahedron configuration. CCDC: 179919.     

3-(2-羟基苯基)-5-苯基-6-乙氧羰基-2-环己烯酮的合成与晶体结构

合成了3-(2-羟基苯基)-5-苯基-6-乙氧羰基-2-环己烯酮.通过元素分析、红外光谱、紫外光谱、核磁共振氢谱和质谱对其组成和结构进行了表征.利用X射线衍射分析方法测定了它的晶体结构.该化合物的晶体属单斜晶系,空间群P21/c,a=1.41946(17)nm,b=0.58445(7)nm,c=2.1756(3)nm,β=104.795(2)°,V=1.7450(4)nm3,Z=4,Dc=1.280 g·cm-3,F(000)=712,μ=0.088mm-1,R1[I＞2σ(I)]=0.0627,wR2[I＞2σ(I)]=0.1484.晶体结构测定结果表明化合物分子中的环己烯部分为半椅式构象,分子间通过氢键形成具有16元环的二聚体.     

含有4,5-二氮芴-9-酮锌(Ⅱ)、钴(Ⅱ)化合物的合成和晶体结构

Two compound crystals of (Hdafo)₂[ZnCl₄]·2H₂O (1) and (Hdafo)₂[CoCl₄]·2H₂O (2) were obtained when we tried synthesizing the mixed ligand compounds of Zinc (Ⅱ) and Cobalt(Ⅱ) with 4,5-diazafluorene-9-one(dafo) and o-phthalic acid, respectively. Their structure was determined by single crystal X-ray diffraction. The crystals all belong to monoclinic system, C2/c space group with crystallographic data:(Hdafo)₂[ZnCl₄]·2H₂O, a=1.6768(5)nm, b=1.2052(3)nm, c=1.3888(4)nm, β=116.793(3), V=2.5053(12)nm³, Z=4, F(000)=1232, M_r=609.57, D_c=1.616g·cm^-3, μ(MoKα)=1.444mm^-1, R₁=0.0373, wR₂=0.0765; (Hdafo)₂[CoCl₄]·2H₂O, a=1.6787(4)nm, b=1.2078(3)nm, c=1.3911(4)nm, β=116.665(3)°, V=2.5204(11)nm³, Z=4, F(000)=1220, M_r=603.13, D_c=1.589g·cm^-3, μ(MoKα)=1.142mm^-1, R₁=0.0257, wR₂=0.0654. The constitutes of the two compounds were proved by elemental, IR Spectra and thermal analyses. CCDC: 1, 198516; 2, 198517.     

二(对-氯苄基)二氯化锡的合成及晶体结构

用 X射线方法测定了二 (对氯苄基 )二氯化锡的晶体结构,该化合物晶体属单斜晶系,空间群为 C2/c,晶体学参数： a=2.8010(3), b=0.4882(2), c=1.2174(3)nm,β =111.71(1)°, V=1.5467(7) nm3, Z=4, Dx=1.893g· cm－ 3,μ (MoKα )=23.24cm－ 1, F(000)=856.00, R=0.025, Rw=0.038, Sn C键长为 0.2148(3)nm, Sn Cl键长为 0.23754(9)nm。空间构型为畸变四面体构型的单分子有机锡化合物。     

微波辐射相转移催化下水相合成α,α'-双亚苄基环烷酮

芳醛与环戊酮或环己酮在碳酸钠水溶液中, 用微波辐射-相转移催化法合成 α,α'-双亚苄基环烷酮, 反应在0.5～7 min内完成, 产率高达80%～99%, 后处理极为简便, 是一种环境友好的绿色合成.     

Synthesis and Crystal Structure of a Tetranuclear Silver Complex with Bis（diphenylphosphino） amine-dioxide as a Tridentate Ligand

1 INTRODUCTION The coordination chemistry of the nitrogen-contai- ning diphosphine ligand bis(diphenylphosphino)ami- ne (Ph2PNHPPh2) has recently received much atten- tion because the P atoms can bridge metal centers in μ-bonding mode to form bi- or polynuclear complex- es[1~10]. It has been shown that the acidity of N–H proton would promote functionalization on the ligand backbone[4, 5, 11]. Although a few complexes contain- ing deprotonated tridentate Ph2PNPPh2 have been synthesi…     

梯形结构二(对甲基苄基)锡氧(氯)簇合物的合成、结构及量子化学研究

二(对甲基苄基)二氯化锡和氢氧化钠溶液反应,合成了梯形结构二(对甲基苄基)锡氧(氯)簇合物,经X-射线衍射测定了其晶体结构。属三斜晶系,空间群为P1,晶体学参数a=0.979 52(16) nm,b=1.313 8(2) nm,c=1.419 5(2) nm,α=62.965(10)°,β=88.551(12)°,γ=73.709(11)°,V=1.550 5(5) nm³,Z=1,D_c=1.563 g·cm^-3,μ(Mo Kα)=17.38 cm^-1,F(000)=727,R=0.024 2,wR=0.057 9。簇合物为由Sn₂O₂构成的平面四元环形成的1个中心内环和2个由Sn₂OCl(O)构成的平面四元外环组成的梯形结构。锡原子均为五配位三角双锥构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及一些前沿分子轨道的组成特征。     

Synthesis and Crystal Structure of Bis[a-chloro-(o-chloro-benzylidene)] Hydrazine

1 INTRODUCTION The azine derivatives are useful compounds because of their special properties. On the one hand, the azines and ,-dichloro-azines are very impor- tant intermediates[1, 2] for synthesizing s-tetrazines which have some peculiar properties, s…     

Studies on the Synthesis,Crystal Structure and Quantum Chemistry of Di(o-cyanobenzyl)tin Bis(quinoline-2-carboxylate)

Di(o-cyanobenzyl)tin bis(quinoline-2-carboxylate)was synthesized by the reaction of tri(o-cyanobenzyl)tin chloride with quinoline-2-carboxylic acid.The molecular structure of the compound Was characterized by elemental analysis,IR,1H NMR and X-ray diffraction.Crystal data for the compound:triclinic,space group P1,a=0.80734(7),b=1.00681(9),c=1.04811(9)nm,α=81.7570(10),β=7.7240(10),γ=81.2850(10)°,V=0.77581(12)nm3,Z=1,Dc=1.488 g/cm3,μ(MoKa)=0.870 mm-1 and F(000)=350.1 The final R=0.0204 and wR=0.0530 for 2677 observed reflections with I＞2σ(I),and R=0.0208 and wR=0.0532 for all reflections.The molecular structure adopts a distorted octahedral geometry around the Sn atom.The title compound molecules are connected via hydrogen bonding interactions to form a 3D network structure.Quantum chemistry calculation study on the title compound has been performed by means of G98W package at the Lanl2dz basis set.The stability of the compound,orbital energies and some frontier molecular orbital composition characteristics have also been investigated.     

Studies on the Synthesis,Crystal Structure and Quantum Chemistry of Di（o-cyanobenzyl）tin Bis（quinoline-2-carboxylate）

Di（o-cyanobenzyl）tin bis（quinoline-2-carboxylate） was synthesized by the reaction of tri（o-cyanobenzyl）tin chloride with quinoline-2-carboxylic acid. The molecular structure of the compound was characterized by elemental analysis, IR, 1H NMR and X-ray diffraction. Crystal data for the compound： tficlinic, space group P1, a = 0.80734（7）, b = 1.00681（9）, c = 1.04811（9） nm, a = 81.7570（10）, β = 7.7240（10）,γ = 81.2850（10）°, V = 0.77581（12） nm3, Z = 1, Dc = 1.488 g/cm3, μ（MoKa） = 0.870 mm^-1 and F（000） = 350. The final R= 0.0204 and wR= 0.0530 for 2677 observed reflections with I 〉2σ（I）, and R = 0.0208 and wR = 0.0532 for all reflections. The molecular structure adopts a distorted octahedral geometry around the Sn atom. The title compound molecules are connected via hydrogen bonding interactions to form a 3D network structure. Quantum chemistry calculation study on the title compound has been performed by means of G98W package at the Lanl2dz basis set. The stability of the compound, orbital energies and some frontier molecular orbital composition characteristics have also been investigated.     

N,N′‐Bis(arylmethylidene)arylmethanediamines: Suitable Precursors for the Synthesis of 1‐Pyrroline Derivatives

A simple and appropriate procedure for the synthesis of 4,5‐dihydro‐5‐hydroxy‐3H‐pyrrole‐3,3‐dicarbonitrile derivatives is reported. The advantages of this method are one‐pot conditions, high yield of products, short reaction times, and no need of metal catalyst. The structures are confirmed spectroscopically (IR, ¹H‐ and ¹³C‐NMR, and EI‐MS) and by elemental analyses. A plausible mechanism for this reaction is proposed (Scheme 2).     

Synthesis,Crystal Structure and Thermal Decomposition of a New Energetic Potassium Salt of Bis（dinitromethyl）difurazanyl Ether

A new energetic organic potassium salt bis(dinitromethyl)difurazanyl ether potassium salt [K2(BDFE)] was synthesized, and structurally characterized by elemental analysis, IR spectra, 13 C NMR and single-crystal X-ray diffraction. K2(BDFE) crystallizes in monoclinic system, space group C2/c with a = 17.342(3), b = 12.6943(17), c = 8.0972(11), β = 110.630(2)°, V = 1668.3(4)3, Z = 4, Dc = 2.000 g/cm3, F(000) = 1000, μ = 0.675 mm-1, S = 1.058, the final R = 0.0499 and wR = 0.1452. The K ion is eight-coordinated with eight O atoms from one water molecule and four bis(dinitromethyl)difurazanyl ethers(BDFE), forming a distorted dodecahedral structure. Thermal decomposition of the title complex was studied by using DSC and TG-DTG. There are primarily two exothermic decomposition processes between 200 and 370 ℃.     

四氯合镉酸正十一烷铵的合成、晶体结构及低温热容

合成了四氯合镉酸正十一烷铵配合物(C₁₁H₂₃NH₃)₂CdCl₄(s)[简写: C₁₁Cd(s)]. 用X 射线单晶衍射技术、化学分析和元素分析确定其晶体结构和化学组成. 利用其晶体学数据计算出晶格能为: U_POT＝908.18 kJ·mol^-1. 利用精密自动绝热热量计测定了它在78～395 K 温区的低温热容, 结果表明, 该配合物在此温区出现两次连续的固-固相转变, 计算出两次相变的峰温、摩尔焓及摩尔熵分别为: T_trs,1＝(321.88±0.07) K, Δ_trsH_m,1＝(37.59±0.17) kJ·mol^-1, Δ_trsS_m,1＝(117.24±0.12) J·K^-1·mol^-1, T_trs,2＝(323.81±0.30) K, Δ_trsH_m,2＝(12.42±0.02) kJ·mol^-1 和Δ_trsS_m,2＝(38.36±0.09) J·K^-1·mol^-1. 用最小二乘法将实验摩尔热容对温度进行拟合, 得到热容随温度变化的多项式方程. 用此方程进行数值积分,得到此温区每隔5 K 的舒平热容值和相对于298.15 K 时的热力学函数值.