一种新型钌(Ⅱ)-组氨酸配合物[RuCl(Me_2SO)_2(L-His)]·H_2O的合成及其结构表征(英文)

本文通过将抗癌活性化合物cisRuCl2Me2SO4与L组氨酸在乙醇溶液中或在溶剂热条件下反应均得到了配合物RuClMe2SO2LHis1。X射线单晶结构分析表明该配合物的晶体属变形八面体,空间群P3121a=b=14.057516c=15.6373分子中含一个结晶水。该配合物中L组氨酸配体分别通过氨基氮、咪唑氮、羧基氧与中心原子钌配位。     

[Co(en)3]2(Zr2F12)(ZrF6H2O)·H2O的合成、 结构及表面光电压性质

采用常温晶化法合成了1个新的金属配合物与氟化锆的复合物[Co(en)3]2(Zr2F12)(ZrF6H2O)·H2O(1), 并对其单晶结构进行了解析. 该化合物属单斜晶系, C2/c 空间群, a=3.06110(17) nm, b=0.877680(5) nm, c=1.50811(9) nm, β=118.897(4)°, V =3.547(4) nm3, Z=8. 该化合物由双核氟化锆阴离子簇 [Zr2F12]4-和单核氟化锆阴离子簇 [ZrF6H2O]2-与钴胺配合物阳离子 [Co(en)3]3+ 及水分子组成, 氟化锆与钴胺配合物之间存在大量的氢键. 该化合物的表面光电压谱在339 nm处出现了光电信号. 这种特殊的光电现象有可能归因于该化合物的钴胺配合物阳离子与氟化锆阴离子簇之间存在的协同作用.     

四聚体手性配合物｛［Cu(C20H26N4O2)Cl］Cl·4H2O｝4的合成及晶体结构

将L-苯丙氨酸与乙二胺通过一定反应双缩得到具有手性结构的N,N′-双(L-苯丙氨酸)缩乙二胺, 此配体与氯化铜发生配位, 生成一种四聚体手性Cu(Ⅱ)配合物, 将此配合物溶在甲醇中培养出单晶. 通过X射线衍射分析测得其分子结构. 此配合物单晶属于四方晶系, 空间群I4. 晶胞参数为a=2.504 4(4) nm, b=2.504 4(4) nm, c=0.870 7(3) nm, V=5.461(2) nm 3, Dc=1365 g/cm3, Z=8.     

含草酰胺桥的Cu(Ⅱ)-Fe(Ⅱ)和Cu(Ⅱ)-Zn(Ⅱ)双核配合物的合成、磁性及生物活性

以N,N'-双（3－氨基－2,2－二甲基丙基）草酰胺根阴离子（Me2oxpn)为桥联配体,分别端接N,N,N',N'-四甲基乙二胺（tmen)和2,9－二甲基－1,10－邻菲甲啉（Me2-phen);合成和表征了3种新的异双核配合和物[Cu(Me2oxpn)Fe(tmen)2]SO4(a),[Cu(Me2oxpn)Zn(tmen)2]SO4(b)和[Cu(Me2oxpn)Zn(Me2-phen)2]SO4(c)。经元素分析、红外光谱、电子光谱、电导及磁性测量等方法推定了这些配合物的结构。测定并研究了（a)的变温磁化率（4－300K）,求得交换参数J＝－12．96cm^-1,表明双核配合物中Cu(Ⅱ）-Fe(Ⅱ)离子间存在反铁磁超交换作用。测试了3个双核配合物的杀菌作用。     

(2-(2’-吡啶)苯并咪唑)(L-丙氨酸根)铜(Ⅱ)配合物结构、抗菌活性及DNA断裂作用

设计合成了新的(2-(2’-吡啶)苯并咪唑)(L-丙氨酸根)铜(II)配合物:[Cu(HPB)(L-Ala)(ClO4)(H2O)]2 H2O[HPB=2-(2’-吡啶)苯并咪唑,L-Ala=L-丙氨酸根].应用元素分析、红外光谱、紫外可见光谱、摩尔电导率、电喷雾质谱及X射线单晶衍射等方法对配合物的组成及结构进行了表征.该配合物晶体属单斜晶系,P21空间群,晶胞参数:a=1.1900(2)nm,b=0.80500(16)nm,c=1.9700(4)nm,β=94.78(3)°,Z=2,Dc=1.672 g cm-3,F(000)=968,残差因子R1=0.0427,wR2=0.1106[I>2σ(I)],S=0.999.在配合物分子中,2-(2’-吡啶)苯并咪唑和L-丙氨酸根以双齿配位方式在分子平面上与中心铜(II)离子配位,而水分子及高氯酸根单齿弱配位于分子轴向上,构成了一拉长的八面体结构.利用二倍试管稀释法测定了配合物的抗菌活性,并且研究了配合物对pBR 322 DNA的断裂作用.结果表明,该配合物对枯草杆菌(B.subtilis,G+),金黄色葡萄球菌(S.aureus,G+),大肠杆菌(E.coil,G-)和沙门氏杆菌(Salmonella,G-)具有良好的抑制活性,最小抑菌浓度为50～80μg mL-1,在维生素C存在下能够通过羟基自由基OH氧化断裂pBR 322 DNA双螺旋结构.     

新型的双阴离子型镱(Ⅲ)胺化物{[Me_2Si(NPh)_2]_2Yb[(N~iPr)_2CN(SiMe_3)_2]}{Li(THF)_2}_2的合成及晶体结构

结构新颖的双阴离子型桥联胺基胍基镱(Ⅲ)配合物{[Me2Si(NPh)2]2Yb[(NiPr)2CN(SiMe3)2]}{Li(THF)2}2是通过二胍基镱氯化物[(SiMe2)2NC(N'Pr)2]2Yb(μ-Cl)2Li(THF)2和桥联胺基锂盐PhLiNSiMe2NLiPh反应制得,该配合物经过了IR、元素分析和X-ray晶体结构的测定.该晶体为单斜晶系,P 21/c空间群,a=14.0001(8),b=17.6808(9),c=24.9565(16)A,B=95.994(3),V=6143.8(6)A3,Dc=1.287g/cm3,Z=4.     

α氨基酸乙酯卤根合铂(Ⅱ)的合成和构型研究

合成和鉴定了十六种新的含卤根的氨基酸乙酯的二价铂配合物。其中八种含碘配合物[PtA_2I_2](A=DL-α-AlaOEt,L-α-AlaOEt,DL-α-PheOEt,L-α-PheOEt,DL-α-AspOEt,L-α-AspOEt,DL-α-SerOEt)和[PtAI_2](A=L-α-LysOEt)以及部分含氯配合物[PtA_2Cl_2](A=DL-α-PheOEt,DL-α-ASpOEt,L-α-AspOEt)和(DL-α-PheHOEt)_2[PtCl_4]由K_2[PtX_4](X=I~-,Cl~-)与相应酯在水中作用而得。易水解的其它含氯氨基酸乙酯配合物[PtA_2Cl_2](A=DL-α-AlaOEt,L-α-AlaOEt,L-α-pheOEt,DL-α-serOEt)通过相应的含碘配合物[PtA_2I_2]与AgCl在非水体系(丙酮)中交换而成。摩尔电导率表明,除(DL-α-pheHOEt)_2[PtCl_4]外,所得配合物均为电中性。分子偶极矩测定和改良的硫脲反应确定了七种含碘配合物:三种含氯配合物[Pt(L-α-AlaOEt)_2Cl_2],[Pt(DL-α-AlaOEt)_2Cl_2]和[Pt(DL-α-SerOEt)_2Cl_2]为顺式构型,其余四种为反式构型的含氯苯丙氨酸乙酯或含氯天冬氨酸乙酯配合物。对决定配合物构型的主要因素进行了讨论。     

(NO2Ql)2[Ni(mnt)2]的合成和晶体结构((NO2Ql)+=1-(4-nitrobenzyl)-quilorinium;mnt2-=maleonitriledithiolate)

合成了离子对配合物(NO2Q1)2[Ni(mnt)2],并用元素分析和红外光谱进行了表征.单晶结构分析结果表明三斜晶系,空间群p-1.晶胞参数a=8.2240(16)A,6=10.777(2)A,c=12.137(2)A,α=72.58(3).,β=72.82(3)°,γ=68.78(3)°,V=935.4(3)A3,Z=1.(NO2Ql)+和[Ni(mnt)2]2-分别形成了完全分立的柱状堆积结构.在阴离子堆积柱内,Ni(Ⅱ)离子形成了一维均匀链.阳离子间,比邻的芳环间存在弱的π…π作用.     

(LaCl)(THF)2(μ-Cl)4[Li(THF)2]2配合物的合成及晶体结构

LaCl_3和LiCl在THF中于室温反应,以已烷为沉淀剂,在-78℃得到晶体,经色谱、元素分析及X射线晶体结构测定,得到了组成为(LaCl)(THF)_2(μ-Cl)_4[Li(THF)_2]_2的配合物.在约-80℃收集该配合物晶体的衍射强度数据,计算结果表明属于单斜晶系,P2_1/c空间群,其晶胞常数a=10.542(4)(?),b=32.236(14)(?),c=11.182(6)(?);β=113.50(3)°,最后R值为0.0477.四个氯桥键构成了分子的基本骨架,表明桥键在小配体轻希土双金属配合物结构中具有稳定作用.     

[Ni(qina)2(H2O)2]·2DMSO配合物的合成、结构及其催化性能

在常温下, 通过溶剂置换法制备了[Ni(qina)2(H2O)2]·2DMSO单晶, 其中qina-为喹哪啶酸根, DMSO为二甲亚砜. 配合物属于单斜晶系, C2/m空间群. 2个qina-配体以氮原子和氧原子与Ni(Ⅱ)离子反式螯合配位, 2个H2O分子则以氧原子与Ni(Ⅱ)离子轴向配位, 形成八面体配合物. 配合物分子之间通过氢键和π-π堆积等弱相互作用构筑成三维超分子结构. 该配合物能显著提高乙酸-1-萘酯的水解反应速率, 当配合物浓度为1.0×10-4 mol/L时, 在pH=8.44的乙酸-1-奈酯体系中, 酯的水解速率提高了365倍.     

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.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.