Syntheses and Properties of Two Heterocyclically Substituted Hypericin Derivatives: 10,11-Dibenzothiazolyl-10,11-didemethylhypericin and 10,11-Dibenzoxazolyl-10,11-didemethylhypericin

Summary. The syntheses of the two heterocyclically substituted title hypericin derivatives were achieved starting either from 6-benzothiazolyl-tri-O-methyl-6-demethylemodin or 6-benzoxazolyl-tri-O-methyl-6-demethylemodin. The use of microwave assisted synthesis for the preparation of these anthraquinone synthons and the chemical as well as photochemical properties of the corresponding unique hypericin derivatives, which might constitute new photodynamic therapy agents, are reported. The tautomeric and stereochemical aspects of these hypericin derivatives were investigated by means of semiempirical calculations (AM1).     

9,12-Dibenzothiazolylhypericin and 10,11-Dibenzothiazolyl-10,11-didemethylhypericin: Photochemical Properties of Hypericin Derivatives Depending on the Substitution Site

Investigating the properties of similar but regioselectively differently substituted hypericin derivatives, 9,12-dibenzothiazolylhypericin was synthesized and compared with the recently prepared 10,11-analogue. A significant difference in the ability to generate singlet oxygen and/or reactive oxygen species and different absorption spectra of these two derivatives were observed.     

9,12-Dibenzothiazolylhypericin and 10,11-Dibenzothiazolyl-10,11-didemethylhypericin: Photochemical Properties of Hypericin Derivatives Depending on the Substitution Site

Summary. Investigating the properties of similar but regioselectively differently substituted hypericin derivatives, 9,12-dibenzothiazolylhypericin was synthesized and compared with the recently prepared 10,11-analogue. A significant difference in the ability to generate singlet oxygen and/or reactive oxygen species and different absorption spectra of these two derivatives were observed.     

Synthesis and Properties of 10,11-Dibenz-imidazolyl-10,11-didesmethyl-hypericin – The First Heterocyclically Substituted Hypericin Derivative

The synthesis of the first heterocyclically substituted title hypericin derivative was achieved starting from 6-benzimidazolyl-tri-O-methyl-6-desmethylemodin. The chemical as well as photochemical properties of this unique hypericin derivative, which might constitute a new photodynamic therapy agent, are reported.     

Syntheses, Photochemical Properties, and Tautomerism of Intramolecularly Friedel-Crafts Acylated Hypericin Derivatives

Intramolecularly Friedel-Crafts acylation carried out on the hypericin moiety provided a new class of 9,12-dicarbonyl substituted hypericin derivatives as potential candidates for photodynamic therapy (PDT). Focusing on cyclopentanone and cyclohexanone condensed derivatives, investigations concerning the chemical and photochemical properties as well as the tautomerism of these compounds were performed.     

炔桥联不对称苯基取代双二茂铁衍生物的设计合成和电化学性质

以四苯基环戊二烯酮为起始原料,经过八步连续反应,成功地合成了3个炔桥联不对称五苯基取代双二茂铁衍生物Fc′-C≡C-Fc(1)、Fc′-C≡C-C≡C-Fc(2)和Fc′-C≡C-C≡C-Fc′(3)(Fc′=五苯基二茂铁基,Fc=二茂铁基)。在设计合成双二茂铁衍生物的过程中,首先经过4步反应,制备出已知化合物Fc′-H(4),再连续进行3步反应,分别得到3个中间化合物Fc′-COCH_3(5),Fc′-CCl=CHCHO(6)和Fc′-C≡CH(7),最后利用偶联反应,得到目标化合物1~3。利用X射线单晶衍射和循环伏安法,测定了化合物1、2和5、7的晶体结构,研究了化合物1~7的电化学性质。研究结果表明,分子的C-H…π键相互作用和空间位阻是导致化合物1和2分子中Fc′和Fc基空间排布取向不同的主要原因。当二茂铁的一个环戊二烯环上引入5个苯取代基时,铁中心的氧化还原电位将升高(E_p~a(Fc′-H)=0.658 V,E_p~a(Fc-H)=0.511 V)。与已知化合物Fc-C≡C-Fc(ΔE=0.215 V)和Fc-C≡C-C≡C-Fc(ΔE=0.134 V)相比,化合物1~3的氧化电位差值(ΔE)均有不同程度地提高(ΔE_1=0.236 V;ΔE_2=0.170 V;ΔE_3=0.146 V)。将1与Fc-C≡C-Fc,2与Fc-C≡C-C≡C-Fc和3进行比较发现,当炔桥两端连接不同的基团Fc′和Fc时,其氧化电位差值(ΔE)将明显提高。     

炔桥联不对称苯基取代双二茂铁衍生物的设计合成和电化学性质

以四苯基环戊二烯酮为起始原料,经过八步连续反应,成功地合成了3个炔桥联不对称五苯基取代双二茂铁衍生物Fc''-C≡C-Fc（1）、Fc''-C≡C-C≡C-Fc（2）和Fc''-C≡C-C≡C-Fc''（3）（Fc''=五苯基二茂铁基,Fc=二茂铁基）。在设计合成双二茂铁衍生物的过程中,首先经过4步反应,制备出已知化合物Fc''-H（4）,再连续进行3步反应,分别得到3个中间化合物Fc''-COCH₃（5）,Fc''-CCl=CHCHO（6）和Fc''-C≡CH（7）,最后利用偶联反应,得到目标化合物1~3。利用X射线单晶衍射和循环伏安法,测定了化合物1、2和5、7的晶体结构,研究了化合物1~7的电化学性质。研究结果表明,分子的C-H…π键相互作用和空间位阻是导致化合物1和2分子中Fc''和Fc基空间排布取向不同的主要原因。当二茂铁的一个环戊二烯环上引入5个苯取代基时,铁中心的氧化还原电位将升高（E_p^a（Fc''-H）=0.658 V,E_p^a（Fc-H）=0.511 V）。与已知化合物Fc-C≡C-Fc（ΔE=0.215 V）和Fc-C≡C-C≡C-Fc（ΔE=0.134 V）相比,化合物1~3的氧化电位差值（ΔE）均有不同程度地提高（ΔE₁=0.236 V;ΔE₂=0.170 V;ΔE₃=0.146 V）。将1与Fc-C≡C-Fc,2与Fc-C≡C-C≡C-Fc和3进行比较发现,当炔桥两端连接不同的基团Fc''和Fc时,其氧化电位差值（ΔE）将明显提高。     

取代甲基亚磺酰基苯并咪唑类化合物的合成

合成了一系列取代甲基硫代苯并咪唑类化合物，并在过氧乙酸的氧化下得到了 取代甲基亚磺酰基苯并咪唑类化合物，收率较好(79%～97%)，代替了用间氯过氧苯 甲酸进行氧化，反应过程稳定，降低了成本。     

Microwave-assistant Syntheses,Crystal Structures and Safener Activities of Two Substituted Phenyl Isoxazole Derivatives

Two novel substituted phenyl isoxazole benzoxazine formamide derivatives were designed and synthesized with substituted o-aminophenol,1,2-dibromoethane and different phenyl substituted isoxazole formyl chloride as the raw materials via microwave assistant synthesis.The target compounds were characterized by IR,~1H NMR,~(13)C NMR and HRMS.Both single-crystal structures were further determined by X-ray diffraction.3-(2'-Chloro-6'-fluoro-phenyl)-4-(2',3'-dihydro-1',4'-benzoxazine)-5-methyl-isoxazole formamide (4a) crystallizes in orthorhombic system,P2_1 space group with a=8.9414(18),b=10.834(2),c=17.706(4)?,V=1715.1(6)?~3,D_c=1.444 Mg/m~3,Z=4,F(000)=768,μ(Mo Kα)=0.255 mm~(-1),R=0.0406 and w R=0.1171.3-Phenyl-4-(6-methyl-2',3'-dihydro-1',4'-benzoxazine)-5-methyl-isoxazole formamide (4b) is of triclinic system,space group P■ with a=7.7659(16),b=8.3626(17),c=13.484(3)?,α=76.04(3)°,β=100.63(3)°,γ=82.01(3)°,V=841.6(3)?~3,D_c=1.319 Mg/m~3,Z=2,F(000)=352,μ(Mo Kα)=0.090 mm~(-1),R=0.0672 and w R=0.2671.Both crystals are packed through C–H···O hydrogen bonding interaction.There is C–H···F hydrogen bond between 4a molecules,and C–H···N between 4b molecules.Bioassay results showed that compounds 4a and 4b exhibited detoxification on maize and restored maize growth index.     

两种苯并二氢吡喃-4-酮衍生物的合成

分别以间甲氧基苯酚与间苯二酚为原料,经过3步合成了(E)-7-甲氧基-3(4-甲氧基苯哑甲基)与(E)-7-羟基-3-(3',4',5'-三甲氧基苯哑甲基)取代的苯并二氢吡喃-4-酮.合成路线简单,易于操作,两者的最终收率分别为20.1%和15.3%.     

Syntheses,Crystal Structures and Magnetic Properties of Two Nitrophenyl Substituted Nitronyl Nitroxide Radical-lanthanide Complexes

Syntheses, structures and magnetic properties of two nitrophenyl substituted nitronyl nitroxide radical-lanthanide complexes [Ln(hfac)3(NITmNO_2)2](Ln = Sm(ⅡI)(1), Tb(ⅡI)(2), hfac = hexafluoroacetylacetonate, NITmNO_2 = 2-(3-nitrophenyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-3-oxide) have been described in this paper. X-ray analysis shows that the two complexes have similar mononuclear trispin radical-Ln(ⅡI)-radical structures, in which the central Ln(ⅡI) ions are all eight coordinated in D2 d dodecahedral(DD) geometry formed by six oxygen atoms from three hfac and two oxygen atoms from nitronyl nitroxide. The magnetic study indicates the antiferromagnetic interaction between Sm(ⅡI) ion and NITmNO_2 in complex 1, while weak ferromagnetic interaction between Tb(ⅡI) ion and NITmNO_2 in complex 2.     

Syntheses,Structures and Photocurrent Response Properties of Two Crystals Based on Tetrathiafulvalene Derivatives

In this paper, two compounds [Zn_2~(2+)(2,6-bis(4'-pyridyl)-TTF)(TPA)_2~(2-)](1) and [Cd~(2+)(2,6(7)-bis(4'-pyridyl)-TTF)(TPA)~(2-)(H_2O)_2](TTF = tetrathiafulvalene, TPA = terephthalic acid)(2) were synthesized by using solvothermal method and characterized by single-crystal X-ray. The purity of the two compounds was confirmed by their PXRD data. We also tested the photocurrent responses of these two compounds, and found they could generate photocurrent signal when exposed to light, but the photocurrent intensity of compound 2 is significantly greater than that of 1. From the crystal structure analysis, the possible reason for this phenomenon is that 2 has a more compact ligand arrangement than 1, leading to a higher carrier density and easier excitation.     

Syntheses, Crystal Structures and Fluorescence Properties of Two Triazolyl Derivatives with Biphenyl Links

Two novel triazolyl derivatives with biphenyl links, namely 4,4-bis（1,2,4-triazol-1-ylmethyl）biphenylene 1 and 4,4-bis（3,5-dimethyl-1,2,4-triazol-1-ylmethyl）biphenylene 2, have been synthesized and structurally characterized by single-crystal X-ray diffraction. Compounds 1·H2O·HCl and 2·2H2O·2HCl crystallize in the monoclinic system with space group C2/c and P21/c, respectively. The dihedral angles of the two phenyl rings are 30.26（6）° in 1·H2O·HCl, while co-planar （0.00（7）°） in 2·2H2O·2HCl. In 1·H2O·HCl, the N-H…O hydrogen bonds link 1 to form chain-like structures which are further connected by O-H…Cl, C-H…Cl, C-H…O and π-π supramolecular interactions. The hydrogen bonds of O-H…Cl in 2·2H2O·2HCl provide distinguishing P/M helical chains along the b axis, and these chains are further connected by N-H…O hydrogen bonds to generate a 2D structure. Compounds 1 and 2 in methanol solution show much stronger emission bands at 319 nm than biphenyl at 316 nm under excitation at 260 nm.     

Syntheses,Electrochemical Behaviors,Spectral Properties and DFT Calculations of Two 1,3-Dithiole Derivatives

Two new 1,3-dithiole derivatives, 4,4＇-{9-[4,5-bis（methylthio）-1,3-dithiol-2-ylidene]-9H-fluorene-2,7- diyl} dipyridine（2a） and 3,3＇-{9-[4,5-bis（methylthio）-1,3-dithiol-2-ylidene]-9H-fluorene-2,7-diyl} dipyridine（2b） were synthesized and characterized by Fourier transform infrared（FTIR）, 1H NMR, 13C NMR and mass spectroscopies. The crystal structure of compound 2b was also studied. The optimized conformations and molecular orbital diagrams of compounds 2a and 2b were illustrated via density functional theory（DFT）. By the time-dependent DFT（TD-DFT） method, electronic absorption spectra of compounds 2a and 2b were predicted and the results achieved were in good agreement with the experimental data. The formation of the cationic radical during the electrochemical oxidation process was also proposed.     

Syntheses,Crystal Structures and Bioactivities of Two Isatin Derivatives

The title compounds(Z)-3-(2-(3-chloropyridin-2-yl)hydrazono)indolin-2-one(A) and 7-bromo-(Z)-3-((4-pyridinyl)carboxlichydrazono)-2-indolinone(B) have been synthesized and structurally determined by elemental analysis and single-crystal X-ray diffraction studies.Compound A(C13H8ClN4O) belongs to the orthorhombic crystal system,space group Pca21 with a = 20.799(4),b = 4.9312(10),c = 11.764(2),V = 1206.6(4)3,Mr = 271.68,Dc = 1.496 g/cm3,μ = 0.313 mm-1,F(000) = 556,Z = 4,the final R = 0.0346 and wR = 0.0831 for 2683 observed reflections with I > 2σ(I).Compound B(C14H9BrN4O2) belongs to the triclinic crystal system,space group P1 with a = 6.6834(13),b = 7.0727(14),c = 14.285(3),α = 95.56(3),β = 99.00(3),γ = 102.95(3)°,V = 643.8(2)3,Mr = 345.16,Dc = 1.780 g/cm3,μ = 3.203 mm-1,F(000) = 344,Z = 2,the final R = 0.0487 and wR = 0.1167 for 2334 observed reflections with I > 2σ(I).The preliminary herbicidal bioassay reveals that compounds A and B have some inhibition both in vivo and in vitro against AHAS.     

取代苄基吡啶类季铵盐的制备及其杀菌活性

采用吡啶或2-氨基吡啶与取代苄基衍生物反应获得3种苄基吡啶类季铵盐．即：溴化苄基吡啶盐（[Bz—Py]Br）,溴化苄基-2-氨基吡啶盐（[Bz-2-NH2Py]Br）和溴化对硝基苄基吡啶盐（[NO2Bzpy]Br]）．通过元素分析,红外光谱和电子喷雾质谱等手段进行了组成分析和结构表征,并以绿脓杆菌和金葡萄球菌为致病菌体测定了3种盐的杀菌活性．实验结果表明,所制备的3种吡啶类季铵盐具有良好的杀菌性能．