新型螺{二氢吲哚-3,2'-[1,3,4]噁二唑}-2-酮类似物的合成

靛红及其衍生物与丙二腈缩合得中间体2-(2-氧代吲哚-3-叉基)丙二腈及其衍生物(2l~2t);苯甲酸及其衍生物与水合肼缩合得苯甲酰肼及其衍生物(4a~4l);2和4分别经环合反应合成了20个螺{二氢吲哚-3,2'-[1,3,4]噁二唑}-2-酮类似物(5a~5t),其中5b~5t为新化合物,其结构经1H NMR和ESI-MS表征。     

5H-[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物的简便合成

报道了以2-甲(乙)基苯胺1a,1b为原料经Sandmeyer反应得到7-甲(乙)基靛红2a,2b;再以环境友好的聚乙二醇-400为溶剂,N-溴代丁二酰亚胺(NBS)为绿色溴代试剂对2a,2b进行5位溴代,得到5-溴-7-甲(乙)基靛红3a,3b;2a,2b,3a,3b进一步氮烃基化得到1-烃基-7-甲(乙)基靛红4a~4j和1-烃基-5-溴-7-甲(乙)基靛红5a~5j.2a,2b,3a,3b,4a~4j,5a~5j分别与硫代氨基脲,在以二氧六环为溶剂,碳酸钾存在的条件下回流反应,简便地合成了24种5H-[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类杂环化合物6a~6x.大部分化合物未见文献报道,其结构经红外光谱、质谱、核磁氢谱(碳谱)和元素分析确认.     

6-溴(氯)-2-氯甲基-3-喹啉甲酸乙酯的合成方法研究

以邻硝基苯甲醛为起始原料,经还原和氨基保护合成2-乙酰胺基苯甲醛(1)。应用环境友好的聚乙二醇-400为溶剂,以N-卤代丁二酰亚胺为卤代试剂对化合物2-乙酰胺基苯甲醛(1)进行卤代,制备了5-溴(氯)-2-乙酰胺基苯甲醛(2a,2b)。在三甲基氯硅烷(TMSCl)催化作用下,5-溴(氯)-2-乙酰胺基苯甲醛(2a,2b)与4-氯乙酰乙酸乙酯发生Friedlnder缩合反应,合成目标产物6-溴(氯)-2-氯甲基-3-喹啉甲酸乙酯(3a,3b)。其中2a,2b,3a,3b的结构经IR、1H NMR、13C NMR、MS得以确定。     

TMSCl促进的分子内亲核取代反应合成α-亚烷基-哌啶酮

以烯基碘代物为底物,丁基锂为锂代试剂,THF为溶剂,在TMSCl促进下通过分子内亲核取代反应合成了4个α-亚烷基-哌啶酮(2a~2d),其结构经~1H NMR,~(13)C NMR和HR-MS(ESI)确证。在最优反应条件(1 2 mmol,n-Bu Li 2.4 mmol,TMSCl 3 mmol,THF 20 m L,于170℃反应1 h)下,2a~2d收率68%~84%。     

新型双环吡啶类化合物的合成及其抗血小板活性

以卤代物(1a~1d、 5a~5j)为起始原料,经硫脲盐酸盐(2a~2d)、磺酸钠(6a~6e)或磺酸(6f~6j)的氯代和氨解反应,制得相应的磺酰胺片段(4a~4d、 8a~8j)。 1-Boc-4-甲基-4-哌啶甲酸(9)脱保护基后与吡啶类化合物(11)发生亲核取代反应制得中间体1-（3-氰基-5-氧代-5,7-二氢呋喃[3,4-b]吡啶-2-基）-4-甲基哌啶-4-羧酸(12); 12与磺酰胺片段发生缩合反应合成了相应的双环吡啶类化合物(13a～13n),其结构经¹H NMR, ¹³C NMR和MS(ESI)表征。采用比浊法血小板聚集试验研究了13a～13n对人源血小板聚集的抑制作用。结果表明：13c和13g具有一定的抗血小板聚集活性,其中化合物13g的IC₅₀值为44.08 μM。      

Amberlyst-15催化C(sp~3)—H对靛红类化合物的加成反应

以Amberlyst-15为催化剂,甲基吡啶类化合物中的C(sp~3)—H键对靛红类化合物经加成反应合成了24个3-羟基-2-吲哚酮类化合物(3a~3x),其中3u~3x为新化合物,其结构经1H NMR,13C NMR,IR和HR-MS(ESI)表征。催化剂Amberlyst-15循环使用8次,不影响反应收率。     

N-(4-吗啉甲基)靛红-3-缩氨基硫脲及其Mn(Ⅱ)配合物的合成

以靛红为原料经Mannich反应和缩合反应合成了N-(4-吗啉甲基)靛红-3-缩氨基硫脲(L);L与MnCl2作用得到配位化合物[MnLH2O]Cl2,其结构经1H NMR, IR, MS和元素分析表征.     

5-(2-苯基-1,2,3-三唑基)-3-芳基吡唑啉衍生物的合成及其荧光性能

以2-苯基-1, 2, 3-三唑基-4-甲醛为原料, 与苯乙酮［或取代苯乙酮(1a~1d)］发生羟醛缩合, 生成相应的查尔酮(2a~2d), 再与不同的肼反应, 合成了12种新的5位含2-苯基-1, 2, 3-三唑基的吡唑啉衍生物3a~3d, 4a~4d, 5a~5d. 化合物的结构经元素分析、 IR光谱和1 H NMR谱确认, 并测定了化合物的荧光光谱. 结果显示所合成的目标化合物有荧光, 是一类新型的荧光化合物.     

糖苷合成研究(ⅩⅩⅠ)2-N-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)-3-哒嗪酮的合成

在相转移催化条件下,2,3,4,6-四-O-乙酰基-1-溴-1-脱氧-α-D-吡喃葡萄糖1与6-(4-卤代苯基)-3(2H)-哒嗪酮2反应,合成了4种新的哒嗪酮葡萄糖苷3;然后用干燥的氨气在0～-5 ℃下处理,得相应的2-N-(β-D-吡喃葡萄糖-1-基)-6-(4-卤代苯基)-3-哒嗪酮4. 这些化合物的结构经IR、1H NMR、13C NMR及元素分析所证实.     

2-[(Z)-2-氯-2-二茂铁乙烯基]-4,5-二取代-1H-咪唑类化合物的合成及其对金属离子的识别性能

以二茂铁为原料,经乙酰化和Vilsmeier-Haack反应制得1-氯-1-二茂铁基丙烯醛(1);1与二酮经环合反应合成了4个新型的2-[(Z)-2-氯-2-二茂铁乙烯基]-4,5-二取代-1H-咪唑类化合物(3a~3d),其结构经1H NMR,IR和ESI-MS表征(其中3d经XRD表征)。3d为三斜晶系,空间群P-1,晶胞参数a=13.434 7(4),b=13.511 3(5),c=13.654 2(4),α=73.32(0)°,β=68.19(0)°,γ=82.6(0)°,V=2 203.52(12)3,Z=2,Dc=1.422 g·cm-1,R1=0.073,wR2=0.237 7。用UV-Vis研究了3a~3d对金属离子(Sn4+,Cr3+,Fe3+和Cu2+)的识别性能。结果表明:3a~3d对其均有选择性识别性能,其中3d对Sn4+的识别性能最佳。     

Darstellung und Kristallstruktur von K6[Al2O6] und Rb6[Al2O6]

Preparation of Crystal Structure of K₆[Al₂O₆] and Rb₆[Al₂O₆] Colourless single crystals of K₆[Al₂O₆] have been prepared from intimate mixtures of KAlO₂ and K₂O (550°C, 90 d). The structure determination from four-circle diffractometer data (MoKα , 742 I_o(hkl), R = 2.2%, R_w = 2.1%) confirms the space group C2/m with Z = 2; a = 698.25 pm, b = 1 103.54 pm, c = 646.49 pm, β = 102.49°. Colourless single crystals of hitherto unknown Rb₆[Al₂O₆] have been prepared from intimate mixtures of RbAlO₂ and Rb₂O (520°C, 120 d). The structure determination from four-circle diffractometer data (MoKα , 1 240 I_o(hkl)) results in the residual values R = 7.2%, R_w = 4.9%; space group C2/m; a = 725.92 pm, b = 1 143.33 pm, c = 678.06 pm, β = 104.05°; Z = 2. K₆[Al₂O₆] and Rb₆[Al₂O₆] are isostructural with K₆[Fe₂O₆]. A characteristic structure unit is the anion [Al₂O₆]^6? consisting of two edge-sharing [AlO₄] tetrahedra. Effective Coordination Numbers (ECoN), Mean Fictive Ionic Radii (MEFIR), the Madelung Part of Lattice Energy (MAPLE) and the Charge Distribution (CHARDI) are calculated and discussed.     

A New Synthetic Route for Preparation of 2-Chloro-6-fluoro-benzonitrile and 2-Chloro-6-fluorobenzoic Acid

An effective synthetic route for preparation of 2-chloro-6-fluorobenzonitrile, 2-chloro-6-fluorobenzamide and 2-chloro-6-fluorobenzoic acid has been described. It includes diazotization,fluorination, ammoxidation and hydrolysis reactions.     

Total synthesis of four naturally occurring 2-azaanthraquinone antibiotics, 6-deoxy-8-methylbostrycoidin, 6-deoxybostrycoidin, 7-O-demethyl-6-deoxybostrycoidin and scorpinone

A total synthesis of four natural 2-azaanthraquinones, 6-deoxy-8-methylbostrycoidin, 6-deoxybostrycoidin, 7-O-demethyl-6-deoxybostrycoidin and scorpinone was accomplished using an optimized procedure for 2-azaanthraquinone synthesis, involving a [4+2]-cycloaddition protocol, of a polyoxygenated diene with a suitably functionalized benzoquinone, acetonylation with pyridinium ylids, cyclisation with ammonia and O-demethylation with boron(III) bromide. 2-Azaanthraquinones are rarely found in nature and reveal interesting physiological properties.     

CO2-activation and enhanced capture by C6Li6: A density functional approach

In this study, we propose a simple and yet effective approach for capture and storage of CO₂ by C₆Li₆. C₆Li₆ possesses a planar star-like structure, whose ionization energy is lower than that of Li atom and hence, it behaves as a superalkali. We have systematically studied the interaction of successive CO₂ molecules with C₆Li₆ using long-range dispersion corrected density functional ωB97xD/6-311 + G(d) calculations. We notice that these interactions lead to stable C₆Li₆-nCO₂ complexes (n = 1-6) in which the structure of CO₂ moieties is bent appreciably (122-125°) due to electron transfer from C₆Li₆, whose planarity is distorted only slightly (≤7°). This clearly suggests that the CO₂ molecules can successfully be activated and captured by C₆Li₆. It has been also noticed that the bond-length of CO₂ in C₆Li₆-nCO₂ complexes increases monotonically whereas adsorption energy decreases, ranging 3.18-2.79 eV per CO₂ with the increase in n. These findings establish the potential of C₆Li₆ for capture and storage of CO₂ molecules.     

浇铸尼龙－6的结晶与熔融

用ＤＳＣ法研究了Ｌａ＿２Ｏ＿３和Ｙ＿２Ｏ＿３对浇铸尼龙－６（ＭＣ尼龙－６）结晶与熔融的影响。二者都使ＭＣ尼龙－６熔体等速降温的结晶温度Ｔ＿ｃ升高、等速升温的溶点Ｔ＿ｍ降低、结晶度Ｘ＿ｃ降低，拉伸过程的断裂能密度及断裂伸长率提高。Ｌａ＿２Ｏ＿３使ＭＣ尼龙－６平衡熔点只降低，结晶速率增加，结晶完善程度变差。Ｙ＿２Ｏ＿３使ＭＣ尼龙－６的升高，它可显著改善ＭＣ尼龙－６的耐热性。     

Kristallstruktur und Eigenschaften von Calcium- und Strontiumhexathiodiphosphat(IV), Ca2P2S6 und Sr2P2S6, mit einem Beitrag zu Ca5P8 und Pb2P2S6

Crystal Structure and Properties of Calcium and Strontium Hexathiodiphosphate(IV), Ca₂P₂S₆ and Sr₂P₂S₆, with a Contribution on Ca₅P₈ and Pb₂P₂S₆ Ca₂P₂S₆ and Sr₂P₂S₆ were prepared from metal and a mixture of red phosphorus and sulfur (molar ratio M:P:S = 1:1:3) in 2 corundum crucibles inserted in quartz ampullae under vacuum (20 d 900°C). The compounds were obtained as colourless, crystalline powders containing single crystals. They crystallize in the Sn₂P₂S₆ (high temperature form) type structure (P2₁/c, Z = 2): Ca₂P₂S₆ a = 653.2(2)pm, b = 728.1(2)pm, c = 1110.1(4)pm, β = 124.00(4)°, d = 2.50(2); Sr₂P₂S₆ a = 664.3(2)pm, b = 755.7(3)pm, c = 1139.7(3)pm, β = 124.07(2)°, d = 2.97(2). The anions P₂S have staggered confirmation and are arranged with the motif of a cubic close-packing. Sr²⁺ is coordinated by 8S which form a twofold face-capped trigonal prism and belong to 4P₂S. Structure calculations clearly show that Pb₂P₂S₆ also crystallizes in P2₁/c and not in Pc [1]. Also, Raman- and IR-spectra of Ca₅P₈ were recorded at 20°C. The stretching vibrations of P were assigned in analogy to those of P₂S in alkaline earth hexathiodiphosphates(IV). The range of their frequencies (480 to 340 cm^?1) is essentially smaller and shifted to smaller values compared with P₂S in Ca₂P₂S₆ and Sr₂P₂S₆ (620 to 390 cm^?1). The symmetry of P is not D_3d but C_2h as in the case of P₂S.     

One-pot syntheses of 6-mercaptopurines (6MP) from 4,5-diamino-6-chloro-pyrimidines

A one-pot synthesis of 6-mercaptopurines from 4,5-diamino-6-chloro-pyrimidine, an aldehyde and elemental sulfur is presented. The key advantage of this procedure is that it utilizes the in situ generated H₂S to convert the chloro to a mercapto group.     

浇铸尼龙—6的结晶与熔融

用ＤＳＣ法研究了Ｌａ２Ｏ３和Ｙ２Ｏ３对浇铸尼龙－６（ＭＣ尼龙－６）结晶与熔融的影响，二者都使ＭＣ尼龙－６熔体等速降温的结晶温度Ｔｅ升高，等速升温的溶点Ｔｍ降低，结晶度Ｘｃ降低，拉伸过程的断裂能密度及断裂伸长率提高，Ｌａ２Ｏ３使ＭＣ尼龙－６平衡熔点Ｔｍ降低，结晶速率增加，结晶完善程度变差，Ｙ２Ｏ３使ＭＣ尼龙－６的Ｔｍ升高，它可显著改善ＭＣ尼龙－６的耐热性。     

(1R,6R)-(+)-鱼腥藻毒素的合成

鱼腥藻毒素(Anatoxin-a)是自兰藻类水华鱼腥藻(Anabaena flos-aquae)中分离的一种氮杂双环胺类生物碱,其化学结构及绝对构型经X光晶体衍射法测定分析为:(1R,6R)(+)-2-乙酰基-9-氮双环[4.2.1]壬-2-烯,简称为AnTX-a。