镧系金属杂—2,3,4,5—四苯基环戊二烯环状化合物的合成及其表征

二苯乙炔和金属锂在乙醚中反应得到1,4-二锂四苯基丁二烯,再与无水氧化希土反应得到了两种系金属条-2,3,4,5-四苯基环戊二烯环状化合物。通过元素分析、红外光谱、核磁共振谱、热失重及电子能谱的分析,对所合成的化合物进行了表征;并对化合物的水解产物作了红外光谱、质谱和核磁共振谱分析,确认下列两种化合物的存在:     

1-叔丁胺基-3-[(5-苯基-1,3,4-噻二唑-2-基)氧]-2-丙醇顺丁烯二酸盐的合成研究

以硫代氨基脲为起始原料,通过缩合、环化、取代等反应合成了1-叔丁胺基-3-[(5-苯基-1,3,4-噻二唑-2-基)氧]-2-丙醇顺丁烯二酸盐.所得中间体及目标化合物结构经测定熔点、热重分析、红外光谱、质谱和核磁共振氢谱等得到确认.     

1-苯基-5-芳基-1,2-二氢-1,2,4-三唑-3-硫酮的合成

将取代苯甲酰氯1a～1f与硫氰酸钾反应, 得到的中间体不需纯化直接与苯肼反应, 成功地合成了1-苯基-5-芳 基-1,2-二氢-1,2,4-三唑-3-硫酮(2a～2f). 化合物2的结构通过红外光谱、核磁共振光谱和高分辨质谱进行了表征.     

稀土杂-2-苯基-3-正丁基茚环状化合物的合成及其对丁二烯聚合的催化活性

二苯乙炔和正丁基锂在乙醚中反应得到中间体,使之进一步与无水氯化稀土反应得到了化合物（I），将化合物（I）与环戊二烯钠在四氢映喃(THF)中反应得到了化合物(I).通过元素分析、红外光谱、核磁共振谱和热重分析对所合成的化合物进行了鉴定,并对水解产物做了红外光谱、质谱、核磁共振谱分析.研究了铃化合物(I)与AIEt3组成的催化体系引发丁二烯聚合的反应活性,结果表明,该催化体系对丁二烯聚合有较高活性,并且溶剂和铝比对聚合活性有较大影响。     

2-苯基噻唑-香豆素衍生物的合成与抗肿瘤活性研究

以对羟基硫代苯甲酰胺和3-溴丙酮酸乙酯为原料,经过缩合、烷基化、皂化反应得到2-((4-甲氧基)苯基)噻唑-4-甲酸,再与二溴代烷烃反应得到溴取代的2-((4-甲氧基)苯基)噻唑-4-羧酸酯,最后与4-羟基香豆素反应得到4个2-苯基噻唑-香豆素衍生物。目标化合物的结构经过红外光谱、核磁共振光谱、质谱以及单晶X-射线衍射对结构进行确证。采用CCK8法评价目标化合物对人乳腺癌细胞MCF-7、人乳腺癌顺铂耐药性细胞MCF-7/DDP细胞增殖活性的影响,结果显示当浓度为50μM时,四个化合物都具有一定的抗肿瘤活性,其中化合物5c对两种癌细胞的抑制活性最强,分别为32.44%和17.99%。     

手性含氟α-氨基膦酸酯新化合物的合成与杀菌活性

一系列手性含氟α-氨基膦酸酯新化合物通过芳香醛、或者苯基乙基胺以及二烷基亚磷酸酯在微波辐射和BF₃·Et₂O催化下反应得到。所有新化合物结构通过元素分析、红外光谱、核磁共振氢谱、核磁共振碳谱等予以确认，生物活性测试表明部分化合物具有很好的抗菌活性.     

3-(2-羟基-4,6-二甲氧基苯基)-5-芳基异噁唑啉的合成及抑菌活性

以查尔酮衍生物为前体, 与盐酸羟胺在碱性条件下反应制得7个3-(2-羟基-4,6-二甲氧基苯基)-5-芳基异噁唑啉化合物(2a~2g), 产物经红外光谱、核磁共振谱、质谱和元素分析表征. 抑菌活性研究结果表明, 化合物2d和2e对大肠杆菌、金黄色葡萄球菌、枯草杆菌和绿脓杆菌均有一定抑制作用, 其中化合物2e对大肠杆菌、金黄色葡萄球菌表现出极好的抑菌活性.     

重氮苯基β-二酮的合成及互变异构体研究

在NaOAc弱碱性条件下,进行偶合反应把重氮基引入到β-二酮分子中,合成了一种新的含重氮苯基β-二酮化合物——重氮苯基[1-(4-对苄氧基苯基)-1,3-二酮],通过红外光谱、紫外光谱、核磁共振氢谱、质谱和元素分析对其结构进行了确证.结构分析表明,这种β-二酮化合物(Ⅰ)在氯仿溶液中是以腙式结构存在,同时存在互变异构,且腙式结构(Ⅲ)与腙式结构(Ⅱ)的物质的量比n(Ⅲ)∶n(Ⅱ)=1∶2.     

N-(2, 5-二甲氧基苯基)N-对甲苯磺酰基-β-氨酸甲酯在多聚磷酸中反应产物的结构测定

发现N-(2,5二甲氧基苯基)N-对甲苯磺酰基-β-丙氨酸甲酯(1)在多聚磷酸作用下,产生了两个新化合物。经过核磁共振、质谱、红外光谱、紫外光谱和化学性质的研究,证实了两个化合物的结构分别为N-(2,5二甲氧基-4-对甲苯基砜基苯基)β-丙氨酸甲酯(2)和N,N'-[4,4'-(2,2',5,5'-四甲氧基)-联苯亚基]双丙氨酸甲酯(4)。在多聚磷酸作用下,发生这样的反应是很少见的。     

1-取代-4,5-二(4-氯苯基)咪唑的合成和结构表征

合成了6种1-取代-4,5-二(4-氯苯基)咪唑.以对氯苯乙酸和氯苯为原料,经Friedel-Crafts酰基化反应、二氧化锡氧化、与多聚甲醛和乙酸铵环合制备了中间体4,5-二(4-氯苯基)咪唑(5),5再经取代得到3个1-取代-4,5-二-(4-氯苯基)咪唑类化合物6a-c.6a再分别与液体胺经亲核取代反应得到3个1-取代乙酰胺类-4,5-二-(4-氯苯基)咪唑类化合物7a-c.目标化合物结构用核磁共振氢谱和红外光谱进行了表征.     

二茂铁甲酰丙酮缩水杨酰肼的d-过渡、ⅡB族及主族金属配合物研究

将二茂铁甲酰丙酮与水杨酰肼缩合,得含二茂铁基的多齿配体C₅H₅FeC₅H₄C(OH)=CHC(CH₃)=NNHCOC₆H₄OH(简记作FcacacshH₂),该配体分别与d-过渡、ⅡB族及主族金属乙酸盐反应,合成了几个中性固体配合物。经元素分析、红外光谱、紫外—可见光谱、氢核磁共振谱、穆斯堡尔谱、摩尔电导测定对配合物进行表征并研究其性质。     

希土硼氢化物的研究 Ⅹ.含[B10H9NH2COCH=CH2]-的双苯甲酰丙酮缩1,3-丙二胺希土(Ⅲ)配合物的研究

将闭式+氢+硼酸阴离子酰胺衍生物[B₁₀H₉NH₂COCH=CH₂]^-、双苯甲酰丙酮缩1,3-丙二胺C₆H₅C(OH)=CHC(CH₃)=N(CH₃)CH=C(OH)C₆H₅(Bapn)及希土氯化物在丙酮-乙醇混合溶剂中进行反应,得到分子式为Ln(Bapn)₃[B₁₀H₉NH₂COCH=CH₂]₃(Ln=La,Nd,Sm,Eu,Gd,Dy)的混式配体希土配合物。通过元素分析、IR、¹H NMR及摩尔电导率的测定对配合物进行了表征,还通过DTA-TG方法研究了它们的热性质。     

Facile Synthesis of Pentacarbonyltungsten(0) Complexes with Oxaphosphirane Ligands

Facile synthesis of tungsten(0) complexes of the type 7a – g (R¹ = C₅Me₅) and 8a – g (R¹ = CH(SiMe₃)₂) using transient Li/Cl phosphanylidenoid tungsten(0) complexes 4 , 5 and carbonyl derivatives 6a – g is reported; furthermore, for all complexes NMR, IR spectroscopic, mass spectrometric investigations and, in addition, single‐crystal X‐ray structures of complexes 7b , d – g and 8b , d are presented.     

Syntheses and structural characterization of novel heteroannular cyclopalladated ferrocenylimine

A new heteroannular cyclopalladated ferrocene derivative [PdCl{C₅H₄FeC₅H₄CH₂NCH–C₄H₃S}(PPh₃)] (6) was synthesized and characterized by IR, ¹H NMR, ¹³C NMR, high resolution mass spectroscopy, and its molecular structure was further confirmed by X-ray crystal structure determination. According to the crystal structure, the palladium atom is bound to the unsubstituted Cp ring, showing the four-coordinate structure typical of palladium complexes. A preliminary application of these novel cyclopalladated complexes in Mizoroki–Heck reaction is also to be demonstrated in this paper.     

Catalytic oxidation of diorganotin(IV) carboxylates to mixed-ligand monoalkyltin(IV) carboxylates by Ag and structure characterization of the mixed-ligand monoalkyltin(IV) 2-pyridinecarboxylate (2-ClPhCH2)Sn(2-ClPhCO2)(O2CC5H4N-2)2

The complexes of the type (ArCH₂)₂SnO were catalytic-oxygenated by Ag⁺ and yielded mixed-ligand organotin(IV) complexes (ArCH₂)(2-C₅H₄NCO₂)₂(ArCOO)tin(IV) (Ar = C₆H₅ (1), 2-ClC₆H₄ (2), 2-CNC₆H₄ (3), 4-ClC₆H₄ (4), 4-CNC₆H₄ (5), 2-FC₆H₄ (6)). The complexes 1-6 are characterized by elemental analyses, IR and NMR (¹H, ¹³C, ¹¹⁹Sn) spectroscopies. Single X-ray crystal structure analysis has been determined, which reveals that the center tin atom of complex 2 is seven-coordinated geometry.     

Synthesis, characterization and crystal structures of a new 2-ferrocenylnaphthoxazole and its mercurated derivatives

A new ferrocenylnaphthoxazole [(η⁵-C₅H₅)Fe{(η⁵-C₅H₄)C(O)N(C₁₀H₆)}] (1) was synthesized under mild conditions. Two mercurated derivatives: ortho-mercurated product [HgCl{(η⁵-C₅H₅)Fe[(η⁵-C₅H₃)C(O)N(C₁₀H₆)]}] (2) and the product mercurated on the unsubstituted Cp ring [HgCl{(η⁵-C₅H₄)Fe[(η⁵-C₅H₄)C(O)N(C₁₀H₆)]}] (3) were obtained by the reaction of 1 with mercuric acetate. All the new compounds 1, 2 and 3 were characterized by elemental analyses, IR, NMR, MS spectra and X-ray crystal structure analysis. The crystal structure of 1 extended into a 2D supramolecular network through the intermolecular π-π stacking interaction between the Cp ring and naphthoxazole ring. In the crystal of 2, there exist bridged Cl-Hg bonds, CH(Cp) ? Cl and CH? Hg hydrogen bonds, π-π stacking interactions, which facilitate construction of this complex into a 3D supramolecular structure.     

Reaction of <Emphasis Type="Italic">o</Emphasis>-aminophenol and <Emphasis Type="Italic">o</Emphasis>-aminobenzyl alcohol with palladium(II) bis(isocyanide) complexes

Reactions of palladium(II) bis-isocyanide complexes cis-[PdCl₂(CNR)₂] (R = 2,6-Me₂C₆H₃, 2-Me-6-ClC₆H₃) with an equimolar amount of chelating N,O-binucleophiles, 2-aminophenol and (2-aminophenyl)-methanol, in acetonitrile at room temperature in 24 h selectively afforded the corresponding open-chain monocarbene complexes. The complexation involved one isocyanide ligand and amino group of the aromatic amine. Neither bis(carbene) complexes (in the reactions with 4 equiv of the nucleophile under harsh conditions) nor C,O-chelate structures were detected. The isolated complexes were characterized by elemental analyses, IR, NMR, and mass spectra, and X-ray diffraction data.     

Synthesis and crystal structure of isomerized butadiene(dicarbonyl)(ethoxyarylcarbene)iron complexes

Reaction of π-butadienetricarbonyliron(I) with aryllithium ArLi (Ar = phenyl, substituted phenyl, 1-naphthyl and 2-thienyl) in ether at low temperature, followed by the alkylation of the acylmetallate obtained with triethyloxonium tretrafluoroborate [(C₂H₅)₃OBF₄] in water solution at 0°C 10 orange-red crystalline complexes with the composition C₄H₆(CO)₂FeC(OC₂H₅)Ar. On the basis of elemental analyses, IR, ¹H NMR and mass spectra, as well as single crystal X-ray structure determination, it is corroborated that these new compounds were isomers of butadienyldicarbonyl(ethoxyarylcarbene)iron complexes with two types of structure. A possible reaction mechanism is tentatively proposed and discussed in this paper.