有机锡9-芴酮-4-甲酸酯的合成、结构及抗癌活性

合成了3个有机锡9-芴酮-4-甲酸酯:三苯基锡9-芴酮-4-甲酸酯[(C₆H₅)₃Sn(C₁₄H₇O₃)](1)、三环己基锡9-芴酮-4-甲酸酯[(C₆H₁₁)₃Sn(C₁₄H₇O₃)](2)和三(2-甲基-2-苯基丙基)锡9-芴酮-4-甲酸酯[(C₆H₅C(CH₃)₂CH₂)₃Sn(C₁₄H₇O₃)](3)。通过元素分析、红外光谱、核磁共振谱(¹H、¹³C和¹¹⁹Sn)、热重分析进行了表征;用单晶X射线衍射方法测定了化合物的晶体结构,并对其进行了量子化学计算和体外抗...     

碳锗双桥连二环戊二烯与羰基铁的反应

碳锗双桥连二环戊二烯(Me₂C)(Me₂Ge)(C₅H₄)₂(1)与五羰基铁在回流甲苯及二甲苯中的反应,得到正常的Fe-Fe键化合物(Me₂C)(Me₂Ge)[(η⁵-C₅H₃)Fe(CO)]₂(μ-CO)₂(3)和脱锗桥产物(Me₂C)[(η⁵-C₅H₄)Fe(CO)]₂(μ-CO)₂(4)以及一个结构新颖的化合物(Me₂C)[(η⁵-C₅H₃)[(Me₂Ge)Fe(CO)₂](η¹,η⁵-C₅H₃)[Fe(CO)₂](2).用X射线衍射分析測定了化合物3的晶体结构,并提出了可能的生成机理.     

硅宾/有机铝的Lewis酸碱对体系及其丙烯酸酯聚合的引发性能

研究了硅宾/有机铝组成的Lewis酸碱对(LP)体系引发丙烯酸酯类单体聚合的性能,合成了4种硅宾:L(Ph₂P)Si(Si-1, L=Ph C(N^tBu)₂)、L[4-MeC₆H₄(Ph₂P)N]Si (Si-2)、L[2,6-ⁱPr₂C₆H₃(1,5-C₈H₁₄B)N]Si (Si-3)、L(LSi)Si (Si-4)和6种有机铝:Al(C₆F₅)₃、AlMe(BHT)₂、AlⁱBu(BHT)₂、AlⁱBu₂(BHT)、AlⁱBu(BHT*)₂、AlⁱBu₂(BHT...     

含有酯基及酰胺基柔链的苯并菲盘状液晶的合成、分子间氢键对柱状介晶性的影响

合成了三个系列, 共二十四个有两种不同软链的对称和非对称苯并菲盘状液晶化合物, C₁₈H₆(OR)₃- (OCH₂COOEt)₃, C₁₈H₆(OR)₃(OCH₂COOBu)₃, C₁₈H₆(OR)₃(OCH₂CONHBu)₃, 其中R＝C₅H₁₁, C₆H₁₃, C₇H₁₅, C₈H₁₇. 化合物通过柱层析纯化, 结构通过¹H NMR, IR, 元素分析等确证. 化合物热稳定性通过TGA测定, 并显示出较高的热稳定性. 通过偏光显微镜和差视扫描量热法对这些化合物的热致液晶性进行了研究. 结果显示: 对于苯并菲液晶化合物C₁₈H₆(OR)₃(OCH₂COOEt)₃, 非对称性化合物较之对称异构体化合物有更低的熔点和更高的清亮点, 因而非对称性化合物有更宽的介晶温度范围. 对于分子中含有酰胺基的苯并菲液晶化合物C₁₈H₆(OR)₃(OCH₂CONHBu)₃, 对称化合物有比非对称异构体更高的清亮点和更有序的六方柱状介晶相, 且其与具有同样软链长度的分子中不含酰胺基的化合物系列C₁₈H₆(OR)₃(OCH₂COOBu)₃相比较, 由于柱内分子间氢键的形成, 不仅有更高的熔点和清亮点, 而且有更丰富的柱状介晶相.     

新型桥联双四面体簇合物的合成与表征

利用(μ₃-CCO₂Et)Co₃(CO)₉与单阴离子试剂[Mo(CO)₃(η⁵-C₅H₄R)]-[R=H,C(O)Me]的反应合成了2个新的含CCo₂Mo骨架的簇合物(μ₃-CCO₂Et)Co₂Mo(CO)₈(η⁵-C₅H₄R)[R=H(1);R=C(O)Me(2)],进而用其与双阴离子试剂{-M(CO)₃[η⁵-C₅H₄C(O)]}₂-1,4-C₆H₄[M=Mo,W]反应合成了4个双四面体簇合物{(μ₃-CCO₂Et)CoMoM(CO)₇(η⁵-C₅H₄R)[η⁵-C₅H₄C(O)]}₂-1,4-C₆H₄[M=Mo,R=H(3);M=Mo,R=C(O)Me(4);M=W,R=H(5);M=W,R=C(O)Me(6)].这6个化合物的C和H元素分析,IR,¹HNMR等表征都与其结构一致.晶体X射线衍射分析表明,化合物2属单斜晶系,C₂/c空间群,晶胞参数a=1.1264(3)nm,b=1.1879(3)nm,c=3.3565(10)nm,β=93.320(5)°,V=4.484(2)nm₃,Z=8,D_c=1.867g·cm^-3,F(000)=2480,R=0.0369,wR=0.1150.     

新型双四面体过渡金属簇合物的合成与表征

利用Co₂(CO)₈与[Cl₃CC(O)OCH₂]₂的反应合成了以C(O)OCH₂CH₂OC(O)桥联两个Co₃C四面体骨架为特征的新型双四面体簇合物[(CO)₉Co₃(μ₃-C)C(O)OCH₂]₂(1);1与不同物质的量比的Na[M(CO)₃C₅H₄R](M=Mo,W;R=H,C(O)Me)反应,得到一步交换的产物(CO)₉Co₃(μ₃-C)C(O)OCH₂CH₂OC(O)(μ₃-C)Co₂M(CO)₈(C₅H₄R)[M=Mo,R=H(2);M=Mo,R=C(O)Me(3);M=W,R=H(4);M=W,R=C(O)Me(5)]或两步交换的产物[(C₅H₄R)(CO)₈Co₂M(μ₃-C)C(O)OCH₂]₂[M=Mo,R=H(6);M=Mo,R=C(O)Me(7);M=W,R=H(8);M=W,R=C(O)Me(9)].5或9分别与Na[Mo(CO)₃C₅H₅]以12的物质的量比反应得到含一个手性四面体骨架(CoMoWC)的(C₅H₅)(CO)₈Co₂Mo(μ₃-C)C(O)OCH₂CH₂O·C(O)(μ₃-C)CoMoW(CO)₇(C₅H₄C(O)Me)(C₅H₅)(10)或含两个手性四面体骨架(CoMoWC)的[(C₅H₅)(C₅H₄C(O)Me)(CO)₇CoMoW(μ₃-C)C(O)OCH₂]₂(11);对化合物1_11进行了CH元素分析、IR和¹HNMR等表征.结果表明,在金属交换反应中处于不同簇环境下的Co(CO)₃基团反应活性不同.对化合物1进行了晶体X射线衍射分析.化合物1的晶体属单斜晶系,P2₁/n(#14)空间群,晶胞参数a=0.933 0(2)nm,b=1.519 7(4)nm,c=1.178 3(4)nm,=91.16(2)°,Z=2,F(000)=972.分子结构呈中心对称.     

1,3-双取代吲哚基稀土金属配合物的合成及催化异戊二烯聚合研究

本文设计合成了新型的1,3-双取代吲哚基配体,并得到了一系列新型相应稀土金属配合物。该配合物经过了X-单晶衍射、核磁、红外和元素分析表征。配合物的结构表明,配体与配合物以NCN三齿形式配位,加上两个烃基辅助配体,形成单核五配位构型。该类型配合物在助催化剂(AlMe₃和[Ph₃C][B(C₆F₅)₄])作用下,能高效,高选择性催化异戊二烯聚合反应得到1,4-顺式产物。     

二环戊二烯基二芳基铪化合物的研究

Rausch等报道由二环戊二烯基二氯化铪与五氟苯基锂在低温、乙醚中按下式反应,得到含σ-碳-铪键的二环戊二烯基二(五氟苯基)铪:(η⁵-C₅H₅)₂HfCl₂+2C₆F₅Li→(η⁵-C₅H₅)₂Hf(C₆F₅)₂+2LiClSamuel等用同样反应合成了二环戊二烯基二苯基铪.     

含邻位-碳硼烷与二茂铁基的新型半夹心式钌化合物的合成

以邻位-碳硼烷、正丁基锂、硫粉和[(p-cymene)RuCl₂]₂为原料,参考文献方法制得化合物(p-cymene)Ru(S₂C₂B₁₀H₁₀)(1)和(p-cymene)Ru₂(μ-S₂)(S₂C₂B₁₀H₁₀)₂(2)(p-cymene=对甲基异丙基苯基); HC≡CC(O)Fc(Fc=二茂铁基)分别与1和2反应合成了新化合物(p-cymene)Ru(S₂C₂B₁₀H₉)(H₂C=CC(O)Fc)(3)和(p-cymene)Ru₂(μ-S₂)(S₂C₂B₁₀H₁₀)₂(R¹C=CR₂)[R¹=FcCO, R²=H(4); R1=H, R2=FcCO(〖STHZ〗5〖STBZ〗)\],其结构经¹H NMR, ¹³C NMR, ¹¹B{¹H} NMR, IR, MALDI-TOF-MS和元素分析表征。     

二(β-羟亚胺)二氯化钛配合物的合成及催化乙烯聚合

报道了3个β-羟亚胺配体(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂CH(Ph)OH(1a), (2,6-^emPr₂C₆H₃)N＝C·(Ph)CH₂C(Ph)₂OH(1b)和(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂C(C₁₂H₈)OH(1c)及其二(β-羟亚胺)二氯化钛配合物[(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂CH(Ph)O]₂TiCl₂(2a), [(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂C(Ph)₂O]₂·TiCl₂(2b)和[(2,6-^emPr₂C₆H₃)N＝C(Ph)CH₂C(C₁₂H₈)O]₂TiCl₂(2c)的合成, 并对其结构进行了表征. 在助催化剂甲基铝氧烷(MAO)作用下, 以化合物2b为主催化剂, 研究了Al/Ti摩尔比、 反应时间、 温度和聚合压力等对乙烯聚合的影响, 发现该催化体系在较宽的反应条件下均可得到很高分子量的聚乙烯, 熔点均在140℃左右. 以化合物2a~2c为主催化剂对乙烯进行催化聚合, 发现在β碳位上取代基的立体位阻对催化剂活性有很大影响. 当化合物2b上引入2个苯基取代基时, 催化剂显示出最佳催化活性.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).