6-yl-hex-1-ene自由基环合成反应机理的理论研究

应用密度泛函理论对6-yl-hex-1-ene自由基环合成反应做了详细的理论研究。通过对随反应坐标变化几个关键变量变化的讨论,揭示了6-yl-hex-1-ene自由基在进行环合成反应时区域选择性的高低;同时,也分析了在6-endo-trig和5-exo-trig反应途径中的热力学和动力学势垒的变化,以及六元环产物和五元环产物的环张力对热力学过程和动力学过程可能产生的影响。结果表明在6-yl-hex-1-ene自由基环合成过程中,经过5-exo-trig反应途径生成环应力较大的五元环产物具有动力学优势,是主要的动力学产物。同时分析结果也表明,可以利用在反应过程中进攻角变量的变化来定性地判断反应选择性的优势通道,并用以定性地解释Baldwin规则的结论。

A Three-dimensional Porous Metal-organic Framework Based on Cyano Unit and 1,4-Bis(1,2,4-triazol-1-yl)butane(btb):{[Cu_8(btb)_2(CN)_8].3H_2O}_n

The title coordination polymer 1,{[Cu8（btb）2（CN）8].3H2O}n（btb = 1,4-bis（1,2,4-triazol-1-yl）butane）,has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Complex 1 crystallizes in monoclinic,space group C2/c with a = 1.2938（3）,b = 1.9422（5）,c = 0.9406（2） nm,β = 121.891（4）°,V = 2.0066（9） nm3,C24H30Cu8N20O3,Mr = 1155.00,Dc = 1.912 g/cm3,μ（MoKα） = 4.209 mm？1,F（000） = 1140,GOF = 1.184,Z = 2,the final R = 0.0634 and wR = 0.1503 for I 2σ（I）.In complex 1,one-dimensional CuCN zigzag chains are linked by triazolyl groups of btb ligands to form two-dimensional networks,which are further bridged by 1,4-butyl moieties of btb ligands to fabricate a three-dimensional order framework,in which one-dimensional ellipsoid-like channels are observed.

Syntheses, Structures and Characteristics of Two New Cu(II) Coordination Polymers Based on 4-tert-butyl-phthalate and Different Bis(1,2,4-triazol-1-yl) Co-Ligands

Two new Cu（Ⅱ） coordination polymers, [Cu2（tbph）2（btb）2]n （1） and {[Cu2（tbph）2- （bth）2]·H2O}n （2）, （H2tbph = 4-tert-butyl-phthalic acid, btb = 1,4-bis（1,2,4-triazol-1- yl）butane, bth = 1,6-bis（1,2,4-triazol-l-yl）hexane）, have been synthesized and characterized by elemental analysis, FT-IR and X-ray single-crystal diffraction. Complex 1 has a 2D sql layer. Complex 2 shows a （3,4）-connected 2D sheet with a （4.6^4.8）（4.8^2） topology. The thermal behavior of the two cor- responding complexes has briefly been investigated.

Synthesis, Crystal Structure and Fungicidal Activity of (Z)-3,3-Dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one O-2-Chlorobenzyl Oxime Nitrate

The title compound has been synthesized by the reaction of 3,3-dimethyl-1-（1H-1,2,4-triazol-1-yl）butan-2-one oxime with 2-chlorobenzyl chloride, and then treated with 65～68% HNO3. Its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 14.5481（8）, b = 9.3351（5）, c = 13.1911（7） , β = 98.9450（10）°, Z = 4, V = 1769.67（17） 3, Mr = 369.81, Dc = 1.388 g/cm3, S = 1.06, μ = 0.247 mm-1, F（000） = 776, the final R = 0.0352 and wR = 0.0960 for 3069 observed reflections （I 2σ（I））. X-ray crystal structure presents the intramolecular N–H…O hydrogen bond. The packing is nearly parallel without π-π stacking interactions between two adjacent phenyl rings and stabilized by Van der Waals force. The preliminary bioassay shows that the title compound possesses fungicidal activity against Gibberella zeae at the dosage of 25 mg/L.

An efficient synthesis of 2,2-bis(1H-indol-3-yl)-2H-acenaphthen-1-one catalyzed by recyclable solid superacid SO_4^(2-)/TiO_2 under grinding condition

An efficient synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one is achieved via a reaction of acenaphthe-nequinone and indoles catalyzed by solid superacid SO4^2-/TiO2 under solvent-free conditions at room temperature by grinding, which provides an efficient route to the synthesis of symmetrical 2,2-bis（1H-indol-3-yl）-2H-acenaphthen-1-one.This procedure offers several advantages including solvent-free conditions,excellent yields of products,simple work-up as well as reuse of catalysts which makes it a useful and attractive protocol for the synthesis of these compounds.

Synthesis, Crystal Structure and Antitumor Activity of (E)-4-tert-Butyl-N-(2,4-dichlorobenzylidene)-5-(1,2,4-triazol-1-yl)-thiazol-2-amine

The title compound （E）-4-tert-butyl-N-（2,4-dichlorobenzylidene）-5-（1,2,4-triazol-1-yl）-thiazol-2-amine was synthesized by the reaction of 4-tert-butyl-5-（1,2,4-triazol-1-yl）-thiazol-2-amine with 2,4-dichlorobenzaldehyde, and its crystal structure was determined by singlecrystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.9748（4）, b = 10.1803（5）, c = 11.4603（6）, α = 102.882（1）, β = 100.253（1）, γ = 104.457（1）°, V = 850.95（7）3, Z = 2, F（000） = 392, C16H15Cl2N5S, Mr = 380.29, Dc = 1.484 g/cm3, S = 1.095, μ = 0.512 mm-1, the final R = 0.0301 and wR = 0.0965 for 3334 observed reflections （I 〉 2σ（I））. The preliminary antitumor activity shows that for the title compound the IC50 of Hela is 0.175 μmol/mL and that of Bel7402 is 0.156 μmol/mL.

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?

A New Zn(Ⅱ) Coordination Polymer Constructed from 4-(1H-pyrazol-3-yl)pyridine as Fluorescent Sensor for Fe^(3+)

A new Zn(Ⅱ) coordination polymer, [Zn(4-PP)(1,4-BDC)?(H_2O)]_n(1, 4-PP = 4-(1 H-pyrazol-3-yl)pyridine, 1,4-H_2BDC = 1,4-benzenedicarboxylic acid), has been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis, IR spectra, XRPD and TG. Structural analysis reveals that Zn(Ⅱ) ions are bridged by COO-from 1,4-BDC^(2-)to form a binuclear structure as the second building units(SBUs). Zn_2 clusters can be clarified as 4-connected nodes, so the framework of 1 can be considered as a 2 D(44?62)-sql sheet. Fluorescence measurements show that 1 has highly selective and sensitive detection of Fe^(3+) in water medium.

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Construction of a New Two-fold Interpenetrated Three-dimensional Cobalt(Ⅱ)Coordination Polymer Based on 2,5-Thiophenedicarboxylic Acid and Bis(imidazol-1-yl)methane

A cobalt coordination polymer, {[Co2（tdc）2（bimm）2]·（3 DMF）}n, was synthesized based on 2,5-thiophenedicarboxylic acid（H2 tdc） and bis（imidazol-1-yl）methane（bimm） mixed ligands. The asymmetric unit of the complex contains two Co2＋） cations, two tdc2-dianions, two neutral bimm ligands, and three free DMF molecules. In the complex, deprotonated tdc2-dianions alternately bridge the adjacent Co2＋ cations to generate chains, which are further connected by the flexible bimm ligands to form a 3 D structure containing adamantanoid-like subunits. In topology, the structure of 1 represents a 4-connected uninodal two-fold interpenetrated dia（66） topology. Moreover, the solid UV-Vis absorption spectra of the complex have also been investigated.

Synthesis and Crystal Structure of 5,5-Dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexene-1-one

The title compound 5,5-dimethyl-2-（4-chlorophenyl）（3-hydroxy-5,5-dimethyl- 2-cyclohexen-1-one-2-yl）methyl-3-（4-methoxyphenylamino）-2-cyclohexen-1-one has been synthesized, and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/c with a = 9.4193（13）, b = 26.915（4）, c= 21.188（3） A, β = 101.906（3）°, V = 5256.2（13） A3, Z = 4, C60H68C12N2O8, Mr =1016.06, Dc = 1.284 g/cm3, F（000） = 2160, λ（MoKα） = 0.71073 A, μ = 0.182 mm^-1, R = 0.0530 and wR = 0.1131 for 4128 observed reflections （1 〉 2α（Ⅰ））. X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition, there are four intramolecular hydrogen bonds in the title molecule.

Synthesis, Crystal Structure and Antitumor Activity of 4-tert-Butyl-N-(2-fluorophenyl)-5- (1H-1,2,4-triazol-1-yl)-thiazol-2-amine

The title compound has been synthesized by the reaction of 1-bromo-3,3-dime- thyl- 1 - （1 H- 1,2,4-triazol- 1 -yl）butan-2-one with 1 -（2-fluorophenyl）thiourea, and its crystal struc- ture was determined by single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system, space group Pbca with a = 15.2568（6）, b = 12.1533（5）, c = 16.7307（7） A, Z = 8, V = 3102.2（2） A3, Mr = 317.39, Dc = 1.359 g/cm3, S = 1.05, μ = 0.223 mm-1, F（000） = 1328, the final R = 0.034 and wR = 0.097 for 2590 observed reflections （I 〉 2σ（I））. X-ray crystal structure presents the intramolecular N-H…N hydrogen bond, which plays an important role in stabilizing the crystal structure. In addition, the preliminary biological test on the title compound shows good antitumor activity, with IC50 of 0.122 μmol/mL against the Hela cell line.

The First Example of a Supramolecular Structure Containing [2-(1H-Pyrazol-3-yl)-pyridine] Complex and both α-and β-Octamolybdates

The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.

Synthesis, Crystal Structure and Antitumor Activities of N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline

The title compound, N-(2-(1H-indol-3-yl)ethyl)-2-nitroaniline(C16H15N3O2, Mr = 281.31), has been synthesized by the multicomponent reaction of milder Ullmann, and its structure was characterized by 1H NMR, 13 C NMR, IR, H RMS(ESI) and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group I2/c with a = 15.0212(10), b = 9.4911(6), c = 20.3075(13) A, β = 100.776(7)o, V = 2844.1(3)A3, Z = 8, Dc = 1.314 g/cm3, F(000) = 1184.0, μ = 0.089 mm-1, the final R = 0.0574 and w R = 0.1688 for 1701 observed reflections(I 】 2σ(I)). X-ray analysis indicates three major N(2)–H(2)···O(2), C(13)–H(13)···O(2), N(2)–H(2)···N(3) hydrogen bonds and π-π stacking interactions in the crystal structure. The preliminary biological test shows that the title compound has a good antitumor activity against A549 in vitro with the IC50 value of 35 μmol/L.

Synthesis,Crystal Structure and Properties of a Zinc(Ⅱ) Complex Based on 5-(1H-Tetrazol-5-yl)isophthalic Acid Ligand

A novel polymeric zinc（II） complex {[Zn2（TIA）（H2O）3]·（NO3）}n（1, H3TIA = 5-（1H-tetrazol-5-yl）isophthalic acid） has been synthesized in mixed solvents under solvothermal conditions and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. Complex 1 crystallizes in orthorhombic, space group Cmcm with a = 10.4210（6）, b =23.3526（14）, c = 6.9214（4）A, V = 1684.37（17）A^3, Z = 4, C9H4N5O（10）Zn2, Mr = 472.91, Dc = 1.865g/cm^3, F（000） = 932, λ（MoK α） = 2.909 mm^-1, R = 0.0423 and wR = 0.1287. The complex has good thermal stability and excellent photoluminescent property.

Synthesis,Structure,and Surface Photo-electric Properties of a New Zn(Ⅱ)Coordination Complex Constructed from 2-(1H-benzotriazol-1-yl)acetic Acid and 1,10-Phenanthroline Ligands

A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental,and photoluminescent analysis.Complex 1 crystallizes in triclinic system,space group P1 with a = 9.3040（19）,b = 10.694（2）,c =16.841（3） A°,α = 101.18（3）,β = 105.77（3）,γ = 91.72（3）°,V= 1575.8（5） A°3,C（32）H（22）Zn2Cl3N7O2,Mr =773.66,Dc = 1.631 g/cm^3,Z = 2,F（000） = 780,μ = 1.820 mm^-1,the final R = 0.1238 and wR =0.1131.X-ray diffraction analyses indicate that 1 displays two crystallographic independent Zn^Ⅱmetal centers with a distorted tetragonal pyramidal（ZnN4O） and a tetrahedral（ZnNCl3） geometries,respectively.The phen serves as a common N,N＇-bidentate ligand,and the bta^- as a unique N,O-bridged ligand in 1.In the crystal,1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…C1 interactions and C-H…π,π…π stacking.1 showed photo-electric conversion properties.

Synthesis and Crystal Structure of Ethyl 3-(4-Chlorophenyl)-3,4-dihydro-6-methyl-4-oxo-2-(pyrrolidin-1-yl)furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.

A One-dimensional Cd(Ⅱ)Coordination Polymer Constructed from 1,4-Benzene-dicarboxylic Acid and 3-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)-1H-indole:Synthesis,Structure and Photoluminescence

A new coordination polymer {[Cd（C_（21）H_（14）N_6）（C_8H_4O_4）]·H_2O}_n（1） was synthesized by an elaborate design via the reaction of 3-（2,6-di（pyrazin-2-yl）pyridin-4-yl）-1H-indole（bppi）,1,4-benzene-dicarboxylic acid（H2bdc） and cadmium（Ⅱ） nitrate in CH_3OH/H_2O mixed solvents. Complex 1 crystallizes in orthorhombic,space group Ccca with a = 20.012（4）,b = 31.881（6）,c = 19.808（4） ？,V = 12638（4） ？~3,Z = 16,C_（29）H_（20）CdN_6O_5,M_r = 644.91,D_c = 1.356 g·cm^（-3）,μ = 0.735 mm^（-1）,F（000） = 5184,GOOF = 1.046,the final R = 0.0405 and wR = 0.1063 for 6870 observed reflections（I 〉 2σ（I））. The Cd（Ⅱ） centre is hepta-coordinated by three N and four O atoms from one bppi terminal ligand and two bdc2– ligands,respectively,displaying a capped trigonal prism geometry. Structure extension gives coordination polymeric chains,in which the bdc2– linkers connect Cd（Ⅱ） cations into a one-dimensional（1D） coordination polymer along the c axis,giving zigzag chains with the Cd···Cd separation of 11.178（1） ？. The adjacent bppi terminal ligands in the chains are anti-periplanar conformation. The three-dimensional（3D） structure is stabilized by π···π stacking and hydrogen-bonding interactions to form a supramolecular self-penetrating network with 1D channels. In 1,there are voids 2999.7 ？~3 with 23.7% of per unit cell volume. Thermal analysis indicates that the framework of 1 is stable until 651 K and the photoluminescence of 1 in the solid shows very weak fluorescence at 382 and 560 nm upon excitation at 310 nm.

An Exploratory Study of Tridentate Amine Extractants: Solvent Extraction and Coordination Chemistry of Base Metals with <i>Bis</i>((1<i>R</i>-benzimidazol-2-yl)methyl)amine

Solvent extraction of base metals using bis((1-decylbenzimidazol-2-yl)methyl)amine (BDNNN) showed a lack of pH-metric separation of the metals. The extraction system was described quantitatively using the equilibria involved to derive the mathematical explanation for the two linear log D vs pHe plots for each metal ion extraction curve, and coordination numbers could also be extracted from the two slopes. The lack of separation was attributed to the absence of stereochemical “tailor making” since the complexes isolated from the reaction of the ligand, bis((1H-benzimidazol- 2-yl)methyl)amine (NNN), with base metals suggested the formation of similar octahedral complex species from spectral and crystal structure evidence. The bis tridentate coordination observed was in agreement with information extracted from the extraction data. This investigation opens up an opportunity and an approach for the evaluation of amines as extractants but cautions against tridentate ligands.