Preparation and biocidal properties of mixed butyl/cyclohexyl trialkyltin carboxylates

Two series of trialkyltin carboxylates containing butyl and cyclohexyl groups on tin, Bu_nCy_3-nSnO₂CR (n = 1, 2; R = n-Pr, Ph, 4-CIC₆H₄, 4-NO₂C₆H₄) have been synthesized and their structures characterized by IR, and ¹¹⁹Sn and ¹³C NMR spectroscopies. The compounds are five-coordinate, carboxylate-bridged polymers when R = n-Pr, while the other aromatic carboxylates are four coordinate. The compounds were also tested for their fungicidal, insecticidal and acaricidal activities.     

Syntheses and bioactivities of tricyclic pyrones

In search of compounds that ameliorate the toxicity of amyloid-β (Aβ) peptides, new derivatives of tricyclic pyrones (1-7) were synthesized and their biological activities evaluated. The carboxylic ester and amide derivatives 1-4 were synthesized from a selective carboxylation of C3 methyl of (5aS,7S)-{7-Isopropenyl-3-methyl-1H,7H-5a,6,8,9-tetrahydro-1-oxopyrano[4,3-b][1]benzopyran (8) with LDA followed by benzyl chloroformate or carbon dioxide to provide ester 1 and carboxylic acid 9, respectively. Three isomeric tricyclic pyrone, 5-7, containing adenine moiety at C7 side chain were synthesized from the alkylation of mesylate 13 with adenine, and displacement of chloropurine 15 with amine 14. Although C3-benzyloxycarbonylmethyl analogs 1-3 have marginal ACAT and CETP activities, their modified aspartate analog 4 and C3-methyl-C7-(N3-adeninyl)-2-propyl analog 6 show a significant effect in protecting against neuron-cell death from the toxicity of intracellular accumulation of Aβ or Aβ-containing C-terminal fragments (CTF) of amyloid β precursor protein (APP). N9-Adenine analog 5 is 20-fold less effective than N3-adenine derivative 6 in the protection of neuron-cell death induced by Aβ, while N10-adenine analog 7 was inactive. As a result of this study, compounds 4 and 6 will well serve as lead compounds for further studies of the mechanism of action of Aβ-and CTF-induced neuron-cell death, studies which should enhance the future development of new drugs for the prevention and treatment of AD.     

Cyclotrimerization of butyl and cyclohexyl isocyanate—catalysis and kinetics

The cyclotrimerization of model aliphatic and cycloaliphatic isocyanates (butyl and cyclohexyl isocyanate) was carried out using an ammonium carboxylate and a salicylaldehyde-potassium complex as catalysts. The kinetics of the cyclotrimerization of butyl isocyanate in both 2-ethoxyethyl acetate and dimethylformamide (DMF) using the 2-ethylhexanoate salt of trimethylaminopropanol-2 was found to be of first order with respect to the isocyanate and also of first order with respect to the catalyst. The reaction rate in DMF was considerably greater than in 2-ethoxyethyl acetate, as could be expected. Employing the salicylaldehyde-potassium catalyst, the cyclotrimerization of butyl isocyanate followed second-order kinetics with respect to the isocyanate and first order with regard to the catalyst. Due to the fact that the cyclotrimerization of cyclohexyl isocyanate was found to be slower than that of butyl isocyanate, the cyclotrimerization of this isocyanate was carried out only in DMF using the 2-ethylhexanoate salt of trimethylaminopropanol-2 as the catalyst. The kinetics of this reaction was found to follow second order with respect to the isocyanate and first order with regard to the catalyst. The products of the reactions were identified by IR, ¹H-NMR, and mass spectrometry.     

Photoluminescent metal-organic polymer constructed from trimetallic clusters and mixed carboxylates

The solvothermal reaction of zinc acetate dihydrate with a mixture of benzene-1,4-dicarboxylic acid (H(2)BDC) and benzene-1,3,5-tricarboxylic acid (H(3)BTC) in a solution containing N,N'-dimethylformamide (DMF), absolute ethanol, and chlorobenzene gave rise to a metal-organic polymer, Zn(3).BDC.2BTC.2NH(CH(3))(2).2NH(2)(CH(3))(2). The structure of this polymer possesses a unique three-dimensional framework with tri-zinc clusters, and BDC and BTC units colinking the clusters. Moreover, this metal-organic polymer exhibits strong photoluminescence at room temperature, and the main emission band is at about 430 nm (lambda(ex) = 325 nm). Crystal data for this compound (C(17)H(20)N(2)O(8)Zn(1.5)): monoclinic, space group P2(1)/n, cell dimensions a = 11.6171(3) A, b = 14.2456(4) A, c = 12.6426(3) A, beta = 107.030(2) degrees, V = 2000.51(9) A(3), and Z = 4.     

三(3,5-二氟苄基)氯化锡和四(邻氯苄基)锡的合成、晶体结构及量子化学

3,5-二氟苄基氯和邻氯基苄基氯在适当的溶剂中与锡粉反应,合成了三(3,5-二氟苄基)氯化锡(1)和四(邻氯苄基)锡(2),经X射线衍射方法测定了新化合物的晶体结构。化合物1属单斜晶系,空间群为C2/c,晶体学参数:a=1.858 33(11)nm,b=1.140 98(7)nm,c=2.690 06(16)nm,β=109.288(10)°,V=5.383 6(6)nm3,Z=8,Dc=1.532 g·cm~(-3),μ(Mo Kα)=13.61 cm~(-1),F(000)=2 480,R1=0.085 1,wR~2=0.168 1。化合物2属单斜晶系,空间群为P21/m,晶体学参数:a=0.585 54(5)nm,b=1.969 74(18)nm,c=0.857 86(8)nm,β=95.204 0(10)°,V=0.985 34(15)nm3,Z=2,Dc=1.805 g·cm~(-3),μ(Mo Kα)=14.91 cm-1,F(000)=524,R1=0.054 0,wR_2=0.163 9;中心锡原子为畸变四面体构型。对其结构进行量子化学从头计算,探讨了化合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了化合物的热稳定性。     

Subtle factors are important: radical formation and transmetallation in reactions of butyl cuprates with cyclohexyl iodide

The reactions of Bu(2)CuLi[middle dot]LiI and Bu(2)CuLi.LiCN with cyclohexyl iodide are critically dependent upon subtle factors such as the surface properties of the reaction vessel, nature of the solvent still and lot of 'ultrapure' copper salt in addition to major effects such as the Li counterion.     

三(三烃硅基亚甲基)锡吡啶甲酸酯的合成和结构表征

三(三烃硅基亚甲基)锡吡啶甲酸酯的合成和结构表征;含硅有机锡化合物;合成;结构表征;生物活性     

Depolymerization kinetics of di(4‐tert‐butyl cyclohexyl) itaconate and Mark‐Houwink‐Kuhn‐Sakurada parameters of di(4‐tert‐butyl cyclohexyl) itaconate and di‐n‐butyl itaconate

Multipulse pulsed laser polymerization coupled with size exclusion chromatography (MP‐PLP‐SEC) has been employed to study the depropagation kinetics of the sterically demanding 1,1‐disubstituted monomer di(4‐tert‐butylcyclohexyl) itaconate (DBCHI). The effective rate coefficient of propagation, k, was determined for a solution of monomer in anisole at concentrations, c, 0.72 and 0.88 mol L^?1 in the temperature range 0 ≤ T ≤ 70 °C. The resulting Arrhenius plot (i.e., ln k vs. 1/RT) displayed a subtle curvature in the higher temperature regime and was analyzed in the linear part to yield the activation parameters of the forward reaction. In the temperature region where no depropagation was observed (0 ≤ T ≤ 50 °C), the following Arrhenius parameters for k_p were obtained (DBCHI, E_p = 35.5 ± 1.2 kJ mol^?1, ln A_p = 14.8 ± 0.5 L mol^?1 s^?1). In addition, the k data was analyzed in the depropagatation regime for DBCHI, resulting in estimates for the associated entropy (?ΔS = 150 J mol^?1 K^?1) of polymerization. With decreasing monomer concentration and increasing temperature, it is increasingly more difficult to obtain well structured molecular weight distributions. The Mark Houwink Kuhn Sakurada (MHKS) parameters for di‐n‐butyl itaconate (DBI) and DBCHI were determined using a triple detection GPC system incorporating online viscometry and multi‐angle laser light scattering in THF at 40 °C. The MHKS for poly‐DBI and poly‐DBCHI in the molecular weight range 35–256 kDa and 36.5–250 kDa, respectively, were determined to be K_DBI = 24.9 (10³ mL g^?1), α_DBI = 0.58, K_DBCHI = 12.8 (10³ mL g^?1), and α_DBCHI = 0.63. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1931–1943, 2007     

Syntheses, structures and bioactivities of fluorine-containing phenylimino-thia(oxa)zolidine derivatives as agricultural bioregulators

From insight into the structure of trehazolin as trehalase inhibitor, six series of fluorine-containing phenylimino-thiazolidines (oxazolidines) derivatives were designed and prepared through a convenient synthesis of fluoroaryl isothiocyanate and a one-pot facile synthesis in high yield of fluorophenyl aminobenzoxazoles by cyclodesulfurization. The structures of the target compounds were confirmed with using IR, NMR, MS and elemental analysis. Their X-ray crystal analysis suggested that there were novel intermolecular (sp²CF?H₃C) and intramolecular (sp²CF?HN) hydrogen bonds between the fluorine atom on benzene ring and hydrogen atom of methyl group or amino group on five-membered heterocycle. Their fungicidal activities against Rhizoctonia solani and Pyricuraria oryzae at 100 ppm were determined.     

Preparation and structure of mixed tungsten bronzes containing tin and europium

An isothermal section has been established for the system Eu_xWO₃Sn_yWO₃ at 1000°C from X-ray powder and single-crystal data and Mössbauer spectroscopy and chemical analyses. A single-phase region with the (12 × 3) tetragonal structure has been established. Single-crystal X-ray analysis shows that the Sn and Eu occupy pentagonal tunnel sites. Mössbauer spectroscopy shows that both Sn(II) and Eu(II) are present. The extent of the single-phase field is controlled by two factors: First, the ratio $\text{Eu}\text{Sn}$ must be <1, and second, the supernumerary electron concentration per WO₃ must be <0.6.     

三(3,5-二甲基苄基)氯化锡和四(间氰基苄基)锡的合成、晶体结构和量子化学研究

以3,5-二甲基苄基氯和间氰基苄基氯在适当的溶剂中与锡粉反应,合成了三(3,5-二甲基苄基)氯化锡(1)和四(间氰基苄基)锡(2),经X射线衍射方法测定了化合物的晶体结构。化合物1属单斜晶系,空间群为P2₁/m,晶体学参数:a=0.584 03(4) nm,b=1.966 37(14) nm,c=0.856 46 (5) nm, β=95.138(3), V=0.979 62(11) nm³,Z=2,D_c=1.735 g·cm^-3,μ(Mo Kα)=14.53 cm^-1,F(000)=524,R₁=0.043 7,wR₂=0.1232。化合物2属单斜晶系,空间群为C2/c,晶体学参数:a=1.692 21(12) nm,b=1.167 41(8) nm,c= 1.539 41(11) nm,β=116.615(10)°,V=2.718 9(3) nm³,Z=4,D_c=1.424 g·cm^-3,μ(Mo Kα)=9.67cm^-1,F(000)=1 176,R₁=0.017 5,wR₂=0.046 1;中心锡原子为畸变四面体构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。     

二(对氯苄基)锡双吗啉氨荒酸酯和二(对氯苄基)氯化锡N,N-二乙基氨荒酸酯的合成、表征及晶体结构

利用二(对氯苄基)二氯化锡和吗啉氨荒酸钠、N, N-二乙基氨荒酸钠反应, 合成了二(对氯苄基)锡双吗啉氨荒酸酯C24H28Cl2N2O2S4Sn (Mr = 694.31) 1和二(对氯苄基)氯化锡N, N-二乙基氨荒酸酯C19H22Cl3N2S4Sn (Mr = 553.54) 2。用X-射线单晶衍射测定了这2个化合物的晶体结构, 测试结果表明:化合物1的晶体为单斜晶系, 空间群C2/c, a = 21.998(9), b = 6.469(3), c = 20.204(8) ,β= 94.444(6)o, Z = 4, V = 2866.3(19) 3, Dc = 1.609 g/cm3, m(MoKa) = 1.394 mm-1, F(000) = 1400, S = 0.955, (D/s)max = 0.000, R = 0.0389, wR = 0.0817。化合物2的晶体为单斜晶系, 空间群P21/c, a = 13.088(10), b = 9.304(7), c = 19.593(14) ,β=107.158(10)o, Z = 4, V = 2280(3) 3, Dc = 1.613 g/cm3, m(MoKa) = 1.660 mm-1, F(000) = 1104, S = 1.010, (D/s)max = 0.001, R = 0.0290, wR = 0.0651。在化合物1中, 锡原子呈六配位畸变八面体构型, 化合物2的锡原子则是五配位畸变三角双锥构型。     

三(3,5-二氟苄基)氯化锡和四(邻氯苄基)锡的合成、晶体结构及量子化学

3,5-二氟苄基氯和邻氯基苄基氯在适当的溶剂中与锡粉反应,合成了三（3,5-二氟苄基）氯化锡（1）和四（邻氯苄基）锡（2）,经X射线衍射方法测定了新化合物的晶体结构。化合物1属单斜晶系,空间群为C2/c,晶体学参数：a=1.858 33（11）nm,b=1.140 98（7）nm,c=2.690 06（16）nm,β=109.288（10）°,V=5.383 6（6）nm³,Z=8,D_c=1.532 g·cm^-3,μ（Mo Kα）=13.61 cm^-1,F（000）=2 480,R₁=0.085 1,wR₂=0.168 1。化合物2属单斜晶系,空间群为P2₁/m,晶体学参数：a=0.585 54（5）nm,b=1.969 74（18）nm,c=0.857 86（8）nm,β=95.204 0（10）°,V=0.985 34（15）nm³,Z=2,D_c=1.805 g·cm^-3,μ（Mo Kα）=14.91 cm^-1,F（000）=524,R₁=0.054 0,wR₂=0.163 9;中心锡原子为畸变四面体构型。对其结构进行量子化学从头计算,探讨了化合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了化合物的热稳定性。     

Syntheses,Structures and Antitumor Activities of Tri(o-bromobenzyl)tin Diethyldithiocarbamate and Tri(m-fluorobenzyl)tin Pyrrolidine Dithiocarbamate

Tri(o-bromobenzyl)tin diethyldithiocarbamate(1) and tri(m-fluorobenzyl)tin pyrrolidine dithiocarbamate(2) have been synthesized and characterized by elemental analysis, IR spectroscopy, NMR(~1 H, ¹³C and ¹¹⁹Sn), thermogravimetric analysis and single-crystal X-ray diffraction. The two complexes crystallize in the triclinic system space group P1. For complex 1, a = 0.9770(1), b = 1.1011(1), c = 1.4583(1) nm, α = 78.431(1)°, β = 86.307(1)°, γ = 69.712(1)°, V = 1.4417(2) nm^3, Z = 2, Dc = 1.790 g/cm^3, m(Mo Kα) = 52.04 cm–1, F(000) = 756, R = 0.0434 and wR = 0.0593. For complex 2, a = 0.7055(1), b = 1.3349(3), c = 1.3782(3) nm, α = 89.216(2)°, β = 82.044(2)°, γ = 84.637(2)°, V = 1.2799(5) nm^3, Z = 2, Dc = 1.537 g/cm^3, m(Mo Kα) = 11.98 cm^–1, F(000) = 596, R = 0.0313 and wR = 0.0333. The two complexes represent mononuclear structures with five-coordinated [SnC3S2] cores forming a distorted trigonal bipyramid. The quantum chemical calculations of 1 and 2 have been investigated. The antitumor activity shows that 1 and 2 have higher activities than cisplatinum against Colo205, HepG2, MCF-7, Hela and H460 cell line in vitro.     

三(3,5-二甲基苄基)氯化锡和四(间氰基苄基)锡的合成、晶体结构和量子化学研究

以3,5-二甲基苄基氯和间氰基苄基氯在适当的溶剂中与锡粉反应,合成了三(3,5-二甲基苄基)氯化锡(1)和四(间氰基苄基)锡(2),经X射线衍射方法测定了化合物的晶体结构。化合物1属单斜晶系,空间群为P21/m,晶体学参数:a=0.584 03(4)nm,b=1.966 37(14)nm,c=0.856 46(5)nm,β=95.138(3),V=0.979 62(11)nm3,Z=2,Dc=1.735 g·cm-3,μ(Mo Kα)=14.53 cm-1,F(000)=524,R1=0.043 7,w R2=0.123 2。化合物2属单斜晶系,空间群为C2/c,晶体学参数:a=1.692 21(12)nm,b=1.167 41(8)nm,c=1.539 41(11)nm,β=116.615(10)°,V=2.718 9(3)nm3,Z=4,Dc=1.424 g·cm-3,μ(Mo Kα)=9.67cm-1,F(000)=1 176,R1=0.017 5,w R2=0.046 1;中心锡原子为畸变四面体构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。     

Bismuth and mixed bismuth-lanthanide carboxylates as precursors for pure and Ln-promoted bismuth molybdate catalysts

Several bismuth(III) carboxylates (formate, acetate, propionate, oxalate, lactate) and the analogous tervalent lanthanum, samarium and praseodymium formates and acetates were synthesized and characterized in view of their use as precursors for the formation of bismuth- or lanthanide-based molybdate catalysts upon controlled thermal decomposition on MoO₃ support. Mixed Bi-Ln carboxylates were prepared and used in parallel as precursors for Ln-promoted bismuth molybdate catalysts. Both the nature of the lanthanide element and the calcination temperature were found to determine the formation of specific molybdate-type phases on the support. Detailed examination of these catalysts by X-ray diffraction and FTIR spectroscopy identified -M₂Mo₃O₁₂ phases in Bi- and Pr-containing samples calcined at 823 K, and hexamolybdate phases M₂Mo₆O₂₁ in La- or Sm-containing catalysts calcined at 973 K.     

2-(N-三氟乙酰-N-三甲基硅烷基)氨基-3-三甲基硅烷氧基-羧酸三甲基硅烷酯和2-(N-三氟乙酰)-2,3-脱氢氨基酸的合成

利用三氟甲基磺酸三甲基硅烷酯, 我们合成了一种新的、化学活性很高的合成中间产物2-(N-三氟乙酰-N-三甲基硅烷基)氨基-1, 1-二(三甲基硅烷氧基)乙烯。脂肪醛或芳香醛发生碳碳成键的加成反应, 生成β碳原子上带有易离去基团三甲基硅烷氧基、N原子上带有保护基团三氟乙酰基的α氨基酸三甲基硅烷酯。消除反应得到了一个合成α、β脱氢氨基酸的可行途径。这类化合物是合成复杂多肽和肽生物碱的基元物。     

Syntheses,structures and bioactivities of silver(I) complexes with a tridentate heterocyclic N- and S-ligand

Three silver(I) complexes of the asymmetric tridentate ligand 8-((pyridin-3-yl)methylthio)quinoline (TQMP3), namely [Ag₂(TQMP3)₂(NO₃)₂] (1), [Ag₂(TQMP3)₂(CF₃CO₂)₂] (2) and {[Ag₂(TQMP3)₂](CF₃SO₃)₂(H₂O)}_n (3), have been prepared by the method of layering and diffusing of diethyl ether. The structures of the complexes have been identified by elemental analysis (EA), infrared spectra (IR) and single-crystal diffraction, and are composed of discrete binuclear rings in complexes 1 and 2, with π–π interactions or H-bonds further extending the structures into 2D nets, while in complex 3, Ag?Ag interactions between the rings result in a 1D polymer chain. The antibacterial, antifungal and pesticide activities of the three complexes were tested.     

Determination of tin in canned foods by UV/visible spectrophotometric technique using mixed surfactants

The complex of tin(IV) with bromopyrogallol red (BPR) in the presence of nonyl phenoxy polyethoxyethanol (OP) and cetyltrimethylammonium bromide (CTAB) has a sensitive absorption peak at 304 nm. Under the optimal conditions, Beer's law is obeyed over the range 0.1-2.5 mug ml(-1) Sn(IV) with molar absorptivity being 8.2 x 10(4) l mol(-1) cm(-1) and detection limit 0.018 mug ml(-1). As compared with the visible method which also uses BPR as chromogenic reagent (lambda(max) = 550 nm), our method is sensitive and selective because of the complex's high, sharp absorption peak. In addition, the present method is simple and rapid, no heating or standing is needed. By means of the mixed surfactants the precipitation caused by the ion association of cetyltrimethylammonium cation and I(-)(3) anion is avoided if iodide is used for separating micro amounts of tin(IV) from a sample matrix. An application of the proposed method to the determination of Sn(IV) in a canned food was made with satisfactory results.     

氢键构筑网络结构的三正丁基锡羧酸酯的合成、结构及抗癌活性

微波辐射条件下,μ-氧-双(三正丁基锡)分别与二苯乙醇酸、2-氯烟酸反应,合成了三正丁基锡羧酸酯(n-Bu)₃SnO₂CR(H₂O)[R:C(OH)Ph₂(1),C₅NH₃Cl(2)]。经IR、¹H和¹³C NMR、元素分析及X-射线单晶衍射表征结构。配合物1、2均属正交晶系,空间群分别为Pbca和P2₁2₁2₁,配基与中心锡原子均构成五配位畸变三角双锥构型。1和2晶体中,存在着多种氢键作用,分别连接扩展成二维和三维超分子网络。初步测试表明:1和2对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460增殖均有较强的抑制作用,尤其对MCF-7、Hela、NCI-H460的抑制作用均大大优于卡铂,且1的抗肿瘤活性更优于2。