2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐的合成及其光致变色性能研究

在氢化钠和甲苯存在下, 1-苄基-3-甲基吲哚-2-甲醛与亚异丙基丁二酸二乙酯发生Stobbe缩合反应, 经过碱性水解和酸化得到二酸化合物, 接着在乙酰氯存在下脱水, 合成2-(1-苄基-3-甲基-2-吲哚亚甲基)-3-亚异丙基丁二酸酐. 研究了该俘精酸酐在不同溶剂中的光致变色性能.     

(E)-2,5-二甲基-3-呋喃乙叉(异丙叉)-丁二酸酐的光发色和光消色反应过程

淡黄色的(E)-2,5-二甲基-3-呋喃乙叉(异丙叉)-丁二酸酐,1,在紫外光作用下同旋闭环生成深红色的闭环体,7,7,a-二氢苯骈呋喃-5,6-二羧酸酐,2,在Ar⁺激光(515nm)作用下,2同旋开环成1,由于在2的分子中无1-位氢,因此不发生与光消色反应相竞争的1,5氢迁移反应。用Fischer的方法测定了光化学反应1→2的光化学转化率,发现转化率是100%,证明光发色反应是定量的。对于用Ar⁺激光引起的光消色反应进行稳态的光化学分析处理,结果揭示在2的激发态和1的基态之间的某一个能级处有一个过渡态X,X分别以22.43ms^-1和1.11ms^-1的速率常数转变成化合物2和1,提出一个一般性的反应能量座标以解释俘精酸酐的光致色变过程,化合物1的光发色和光消色反应遵循两条不同的反应路线。     

3,3-二甲基-2-(3-甲基薁乙烯基)-3H-吲哚衍生物的合成

1-甲酰基薁-3-甲酸甲酯和2,3,3-三甲基-3H-吲哚衍生物发生缩合反应,合成了一系列3,3-二甲基-2-(3-甲基薁乙烯基)-3H-吲哚衍生物,收率48%～64%,其结构经~1H NMR,IR和元素分析表征.     

“一锅串联法”合成2-[(E)-2-2-氯-1-甲基-3-吲哚基)乙烯基]喹啉-3-羧酸(英文)

设计了以2-(溴甲基)喹啉-3-甲酸乙酯(4)与2-氯-1-甲基-3-吲哚醛(5)为起始化合物,通过简便有效的"一锅法"反应,首次将吲哚环引入2-苯乙烯基喹啉骨架模型,从而得到一新颖结构的双杂环化合物,即(E)-2-(2-(2-氯-1-甲基-1H-3-吲哚基)乙烯基)喹啉-3-羧酸(3),其结构通过波谱数据和元素分析得以证实。     

2-(p-取代苯乙烯基)-3,3-二甲基-3 H-吲哚盐的合成及性能研究

2,3,3-三甲基-3 H-吲哚氢溴酸盐分别与五种取代苯甲醛在乙醇介质中反应,可得到五种新的2-(p-取代苯乙烯基)-3,3-二甲基-3H-吲哚氢溴酸盐(R=H(3a);Br(3b);MeO(3c);HO(3d);Me_2N(3e)]。研究了化合物3a-e的紫外光谱和Hammett常数的定量关系。以位移增量△λ_p,对△σ(△σ=σ_p-σ_m)作图可得到一条直线,说明它们紫外光谱的取代基效应遵守Hammett方程,即随着取代基给电子能力的增强,吸收带向红移。五个化合物以3e的光谱增感性能最好。     

在微波作用、无催化剂的条件下合成3-芳基亚甲基-1，3-二氢-2H-吲哚-2-酮类化合物

用DMF作溶剂，无催化剂、微波辐射的条件下，使吲哚-2-酮(1)和醛、酮(2)发 生缩合反应，合成了3-芳基亚甲基-1，3-二氢-2H-吲哚-2-酮类化合物，时间短、 收率高。     

1,2-双(4-溴苯基)-6,7-二氢-3-甲氧基-6,6-二甲基-1H-吲哚-4(5H)-酮的简便合成和结构表征

以1-(4-溴苯基)-2,2-二羟基-乙酮、3-((4-溴苯基)氨基)-5,5-二甲基环己-2-烯酮为原料,甲醇既为醚化试剂也是反应介质,采用对-甲基苯磺酸(p-TsOH)为催化剂,通过多组分的多米诺反应微波辐射下合成多取代的四氢吲哚类衍生物--1,2-双(4-溴苯基)-6,7-二氢-3-甲氧基-6,6-二甲基-1H-吲哚-4(5H)-酮.其结构通过单晶X射线衍射法确定,晶体属三斜晶系,空间群P-1,相对分子质量Mr=503.23,晶胞参数a=0.884 19(9)nm,b=0.969 36(11)nm,c=1.348 97(13)nm,V=1.070 96(19)nm3,Z=2,晶胞密度Dc=1.561g/cm3,吸收系数μ=3.803mm-1,单胞中电子的数目F(000)=504.晶体结构用直接法解出,经全矩阵最小二乘法对原子参数进行修正,最终的偏离因子为.R=0.058 4,wR=0.107 8.在晶体结构中新形成的吡咯杂环近似于平面结构.     

2-(P-取代基苯乙烯基)-3,3-二甲基-3 H-吲哚盐的合成及性能研究

2,3,3-三甲基-3H-吲哚氢溴酸盐分别与五种取代苯甲醛在乙醇介质中反应,可得 到五种新的2-(P-取代苯乙烯基)-3,3-二甲基-3H-吲哚氢溴酸盐(R=H(3a);Br(3b);MeO(3c);HO(3d);Me~2N(3e)].研究了化合物3a-e的紫外光谱和Hammett常数的定量关系.以位移增量△λ~p对△σ(△σ=α~p-σ~m)作图可得到一条直线,说明它们紫外光谱的取代基效应遵守Hammett方程,即随着取代基给电子能力的增强,吸收带向红移.五个化合物以3e的光谱增感性能最好.     

5-(3-吲哚基)亚甲基噻唑烷-2,4-二酮衍生物的合成及体外抗肿瘤活性探索

将N-取代吲哚-3-甲醛和2,4-噻唑烷二酮通过亚甲基键合,再对噻唑烷二酮氮取代,合成了一系列5-(3-吲哚基)亚甲基噻唑烷-2,4-二酮衍生物(e1-e9).采用IR,1H NMR和HRMS对其结构进行了表征;采用MTT法对目标物抑制5种癌细胞增殖活性进行了测试.结果表明,所有目标物对A549、HCT116和PC-9表现出抑制活性,其中吲哚氮被苄基取代的化合物e1和e3对测定的癌细胞增殖抑制活性与5-氟尿嘧啶(5-FU)相近,并且对A549和HCT116表现出中等的抑制活性(IC50<30μM)。     

1,5-双(5′-甲氧基吲哚-3-亚甲基)硫代二氨基脲的合成与晶体结构

以5-甲氧基吲哚-3-甲醛和硫代对称二氨基脲为原料,经缩合反应合成了1,5-双(5ˊ-甲氧基吲哚-3-亚甲基)硫代二氨基脲,产物经IR,~1H NMR及X-射线单晶衍射法进行了结构表征,并研究了化合物的固体荧光性能。该化合物属于单斜晶系,P 2(1)/c空间群,晶胞参数a=16.548(7),b=10.063(4),c=13.078(6)~3,β=112.057(5)°,V=2018.6(3)3,Dc=1.384g/cm~3,Z=4,μ=0.192 mm~(-1),F(000)=880,最终残差因子R_1=0.0472,wR_2=0.1313。     

1,2-二甲基-3-吲哚甲叉(异丙叉)丁二酸酐(1)和1,2-二甲基-3-吲哚乙叉(异丙叉)丁二酸酐(2)的晶体结构

The crystal structures of 1,2-dimethyl-3-indolylmethylidene succinic fulgide anhydride (1) and 1,2-dimethyl-3-indolylethylidene succinic fulgide anhydride(2) were determined by singe crystal X-ray diffraction analysis. The crystal data are C_(18)H_(17)NO_3(1), orthogonal space group Pbca, with a=1.0084(3) nm, b=1.3966(4) nm, c=2.0945(6) nm, V=2.9498(15) nm, Z=8; C_(19)H_(19)NO_3 (2), orthogonal space group Pbca, with a=0.7988(3) nm, b=2.5782(10) nm, c=1.5664(5) nm, V=3.2259(22) nm, Z=8. R values are 0. 047 for (1) and 0.059 for (2) respectively.The photochemical properties of (1) and (2) were reported. Compound (1) is nonphotochromic, compound (2) changed from pale yellow to blue or green on irradiation at 365 nm or on exposure to indoor UV light either in crystal state or in solution (liquid or rigid plastic matrix).The differences in photochromic properties of compound (1) and (2) were discussed.     

Syntheses and Crystal Structures of （PySe）2 and Bi2（PySe）6（HPySe=2-Pyridineselenol N-Oxide）

The title compounds(PySe)2 1(HPySe=2-pyridineselenol N-oxide,(PySe)2= bis(2-pyridine-N-oxide) diselenide) and Bi2(PySe)6 2 were prepared by the reaction of 2-bromine-N-oxide with NaHSe and Bi(NO3)3·5H2O with HPySe,and the crystal structure of 2 was studied.Compound 2 crystallizes in the monoclinic space group P21/n with a=9.840(2),b=10.204(2),c=18.395(2),β=102.926(2)°,V=1800.0(5)3,Dc=2.2687 g/cm3,Z=2,the final R=0.0319 and wR=0.0646.The Bi atoms are coordinated by four selenium and four oxygen atoms from four PySe ligands to form a slightly distorted four-column geometry.     

Synthesis and Crystal Structure of a Chiral Manganese(Ⅲ) Schiff Base Complex

A chiral salency complex,[Mn(Salency)(H2O)2](PF6)·2H2O 1(Salency =(R,R)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine),has been prepared by the reaction of Mn(CH3COO)3·2H2O with Salency and NH4PF6,and was established by X-ray diffraction techniques.The complex crystallizes in triclinic,space group P1 with a=9.299(8),b=10.012(8),c=13.461(11),α=92.037(15),β=92.974(12),γ=93.530(18)°,V=1248.3(18)3,C20H28F6MnN2O6P,Mr = 592.35,Z=2,Dc=1.038 g/cm3,F(000)=608,μ=0.676 mm-1,the final R=0.0651 and wR=0.1880 for 5260 observed reflections with I 2σ(I).     

[Co(Phen)2(H2O)2](HL)NO3·3H2O的合成及晶体结构

在水溶液中,以邻菲咯啉、丁二酸与硝酸钴为原料合成了一个新的超分子化合物[Co(Phen)2(H2O)2].(HL).(NO3).3H2O,并经元素分析、IR、X射线单晶衍射分析进行了结构表征.结构分析表明,晶体属三斜晶系,P1-空间群,a=0.968 0(2)nm,b=1.370(3)nm,c=1.394 9(3)nm,α=61.714(3)°,β=71.495(4)°,γ=79.575(4)°,V=1.543 7 nm3,Z=2,ρ=1.481 g/cm3,C28H31CoN5O12,Mr=688.51,F(000)=714 andμ=0.627 mm-1,7 754个独立衍射点中,5 428个可观察点满足I≥2σ(I),R1=0.074 5,wR2=0.210 7.晶体中[Co(Phen)2(H2O)2]2+通过π-π相互作用堆积成二维层状结构,层间通过氢键作用构成三维超分子.     

Syntheses and Crystal Structures of Two New Compounds:[Zn(2,2'-bipy)(L)CI]_2 and [Zn(phen)(L_2)]_2(HL-3-Methylbenzoic Acid)

Compounds [Zn(2,2'-bipy)(L)CI]_2 1 and [Zn(phen)(L_2)] _2 2 (2,2'-bipy = 2,2'-bipy-ridine, HL = 3-methylbenzoic acid, phen = 1,10-phenanthroline) have been synthesized under hy-drothermal conditions. 1: monoclinic, space group C2/c, α = 20.240(4), b = 9.2960(19), c = 17.904(4) A, β = 92.63(3)°, V= 3365.1(12) A3, C_(36)H_(30)Cl_2)N_4O_4Zn_2, M_r = 784.32, Z = 4, D_c = 1.548 g/cm~3,μ = 1.631 mm~(-1), F(000) = 1600, the final R= 0.0367 and wR = 0.1289 for 3867 observed reflections (I > 2σ(I). 2: monoclinic, space group C2/c, α = 23.035(5), b = 9.0395(18), c = 23.799(5)A, β = 98.55(3)°, V= 4900.6(17) A~3, C_(56)H_(44)N_4O_8Zn_2, M_r = 1031.73, Z = 4, D_c = 1.398 g/cm~3, μ= 1.039 mm~(-1), F(000) = 2128, the final R= 0.0540 and wR = 0.1287 for 5002 observed reflections (I> 2σ(I). The two compounds have the same space group and similar isolated dinuclear structure, but different space packing structures are formed by different weak intermolecular interactions. Mo-reover, IR and luminescence spectra are also employed to study the crystal structures and pro-perties of these two compounds.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co(4,4'-bipy)_2(H_2O)_4]· [Co_2(4,4'-bipy)3O(H_2O)_8]·2TST·2(4,4'-bipy)·4H_2 and [Co(4,4'-bipy)_2(H_2O)_4]DSNT'4,4'-bipy

Two new cobalt(Ⅱ) supramolecular complexes [Co(4,4'-bipy)_2(H_2O) _4]·[Co_2(4,4'-bipy)3-(H_2O) _8]·2TST-2(4,4'-bipy)·4H_2O 1 and [Co(4,4'-bipy) _2(H_2O) _4]DSNT·4,4'-bipy 2 based upon the assembly of Co(Ⅱ), 4,4'-bipyridine (4,4'-bipy) and two new multifunctional organic ligands, 2,4,6-tris(4-sulfophenyl-amino)-1,3,5-triazine (H_3TST) and 2,4-bis(p-sulfanilato)-6-diethylamino-1,3,5-triazine (H_2DSNT), have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P2_(1/n) with α= 13.599(4), b = 18.988(6), c = 22.995(7) A, β = 90.273(6)°, V= 5938(3) A~3, Z = 4, C_(56)H_(59)CO_(1.5)N_(13)O_(17)S_3, M_r = 1370.74, D_c = 1.533 g/cm~3,μ = 0.613 mm~(-1), F(000) = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I > 2o(I). The crystal structure of 2 belongs to the monoclinic system, space group C2/c with α = 18.864(6), b = 14.283(5), c = 20.246(7) A, β = 107.799(6)°, V = 5194(3) A~3, Z = 4, C_(49)H_(52)CoN_(12)O_(10)S_2, M_r = 1092.08, D_c = 1.397 g/cm~3, μ= 0.480 mm~(-1), F(000) = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I> 2σ(I). The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

Syntheses and Crystal Structures of 1,5-Disubstituted 1,3,5-Hexahydro-triazine-2-（N-nitro）imines

The title compounds,C9H13ClN6O2S 1 and C15H17ClN6O2S 2,were synthesized and structurally characterized by elemental analysis,IR,1H NMR spectra and single-crystal X-ray diffraction.Compound 1 is in the monoclinic system,space group P21/c with a=13.7711(5),b=10.3883(4),c=9.7623(2),V=1344.47(8)3,Dc=1.506 g/cm3,C9H13ClN6O2S,Mr=304.76,F(000)=632,μ=0.448 mm-1,Z=4,S=1.084,R=0.0497 and wR=0.1328 for 2640 unique reflections(Rint=0.0787) with 2089 observed ones(I2σ(I)).Compound 2 belongs to the monoclinic system,space group P21/n with a=8.3828(5),b=14.5285(7),c=14.2456(4),V=1729.74(14)3,Dc=1.462 g/cm3,C15H17ClN6O2S,Mr=380.86,F(000)=792,μ=0.364 mm-1,Z=4,S=1.057,R=0.0598 and wR=0.1582 for 3384 unique reflections(Rint=0.0469) with 2833 observed ones(I2σ(I)).Compounds 1 and 2 are homologues and stabilized by intermolecular and intramolecular hydrogen bonds.Moreover,compound 2 containing C(2)-H(2)…π(thiazole) interaction is more stable than 1.     

夹心型杂多化合物Na_9[CeW_(10)O_(36)]·34H_2O的合成及晶体结构

在pH≈6.5及NaAsO_2和Co(NO_3)_3·6H_2O存在下,Na_2WO_4·2H_2O 与Ce (NO_3)_3·6H_2O反应,得到了Na_9[CeW_(10)-O_(36)]·34H_2单晶。用元素分析 及X射线单晶衍射法确定了其组成与结构,晶体学数据为：a = 1.3010(5) nm, b = 1.3072(5) nm, c = 1.9962(8) nm, α= 101.073(7) °, β = 104.411(5) ° γ = 90.473(4) °, V = 3.221(2) nm~3,空间群P1,V=3.211(2)nm~3, Z = 4, 最终R因子[1>2σ(I)]R_1=0.0424, wR_2 = 0.0549, R因子（全部数据）R_1=0. 1357, wR_2 = 0.0808.[CeW_(10)O(36)]~(9-)具有D_(4d)对称性。     

A Novel 2D Architecture from Bismuth and Flexible Ligand N,N'-Diacetic Acid Imidazolium Chloride

A new compound {[Bi（trans-DAM）（cis-DAM）（H2O）]NO3·H2O}n 1 derived from bismuth and the flexible ligand N,N＇-diacetic acid imidazolium chloride （H2DAMCl） was obtained by hydrothermal synthesis and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the monoclinic P21/c space group with a = 9.2298（18）, b = 13.339（3）, c = 17.090（3） , β = 105.38（2）°, V = 2028.7（7）A^3, Z = 4, C14H18N5O13Bi, Mr = 673.31, Dc = 2.204 g/cm^3, F（000） = 1296, μ = 8.772 mm-1, the final R = 0.0472 and wR = 0.1441 for 4129 observed reflections （I 〉 2σ（I））. In 1, the carboxylic groups from DAM- ligands adopt a cheating mode to link bismuth ions to form a 2D sheet network. These sheets are further connected by hydrogen bonding interactions to give an interesting 3D supramolecular framework. 2D correlation analysis of IR of 1 with thermal and magnetic perturbation was introduced to ascertain the characteristic adsorption of the groups overlapped in the 1D IR spectrum. Additionally, compound 1 exhibits fluorescent emission at room temperature.     

Alternate Array of Zigzag（PbO5）n and（PbO6）n Polynuclear Chains in a 2-D Coordination Polymer with Diverse Coordinate Modes of Nitrate（NO3^-）

A novel metal-organic coordination polymer,[Pb2(NO3)3(Hmppdc)(CH3OH)2]n(1,H2mppdc=2,6-dimethyl-4-phenylpyridine-3,5-dicarboxylic acid),was synthesized from the reaction of H2mppdc,Pb(NO3)2 and CH3OH under solvothermal conditions.X-ray single-crystal diffraction reveals that 1 crystallizes in monoclinic,space group P21/n,with a=10.9883(13),b=7.3603(10),c=31.165(3),β=96.918(2),V=2502.2(5)3,Z=4,Mr=934.75,Dc=2.481 Mg/m3,F(000)=1736,the final R=0.0676 and wR=0.1310(I2σ(I)).Compound 1 contains two distinct 1-D polynuclear metal-oxygen chains((PbO5)n and(PbO6)n),which are bridged by ligands to build up 2-D metal-organic layers,and such layers are further connected to form a 3-D supramolecular network.The new compound exhibits strong photoluminescence in the solid state at room temperature.