新的二苯并环状溴Wong盐的合成及性质研究

以４，４′－二取代联苯（或４，４′－二取代二苯甲烷）为原料合成了几种新的３，７－二取代二苯并环状溴翁盐。对几种溴翁盐与ＫＢＨ４及与ＮａＮ３的反应进行了研究。结果表明，前一反应主产物为２－溴－４－４′－二聚代联苯（或２－溴－４，４′－二取代二苯甲烷），后一反应的主产物为２－叠氮基－２′－溴－４，４′－二取代联苯（２０ａ－２０ｄ）。通过２０ａ－２０ｄ的热反应合成几种新的多取代咔唑（２１ａ－２１ｄ）。     

3,7-二硝基二苯并溴五环盐与亲核试剂的反应及新环状卤鎓盐的合成

本文研究了3,7- 二硝基二苯并溴五环硫酸氢盐与十种亲核试剂的反应,分离出主要产物2-溴-2＇-Nu-4,4＇-二硝基联苯(3a～j),并以3e～g为原料在浓硫酸中用过二硫酸钾氧化关环合成了多种新的环状卤鎓盐.     

几种新的3,7-二取代二苯并五元环状溴嗡盐的合成

4,4'-二硝基联苯在浓硫酸中与溴化钠及过硫酸钾反应,直接生成3,7-二硝基二苯并溴五环盐(5).5经SnCI~2-HCI还原得到3,7-二氨基二苯并溴五环盐(6),由6制得重氮盐溶液分别与氯化亚铜,溴化亚铜及碘化钾反应得到3,7-二氯二苯并溴五环盐(7),3,7-二溴二苯并溴五环盐(8)及3,7-二碘二苯并溴五环盐(9).5-9均匀新化合物,其结构经^1HNMR.MS.IR证实.     

几种新的3,7-二取代二苯并五元环状溴嗡盐的合成

4,4'-二硝基联苯在浓硫酸中与溴化钠及过硫酸钾反应,直接生成3,7-二硝基二苯并溴五环盐(5).5经SnCI~2-HCI还原得到3,7-二氨基二苯并溴五环盐(6),由6制得重氮盐溶液分别与氯化亚铜,溴化亚铜及碘化钾反应得到3,7-二氯二苯并溴五环盐(7),3,7-二溴二苯并溴五环盐(8)及3,7-二碘二苯并溴五环盐(9).5-9均匀新化合物,其结构经^1HNMR.MS.IR证实.     

2-溴-4,4'-二硝基-3'-二甲基锍-2'-联苯酚内盐的合成、结构及性质的研究

在胺存在下,3,7-二硝基二苯并溴五环硫酸氢盐与二甲基亚砜反应生成2-溴-4,4'-二硝基-3'-二甲基锍-2'-联苯酚内盐(3).3的X射线晶体结构分析数据表明其分子具有内盐结构但酚氧负离子的负电荷是部分离域的,分子内两苯环所成的两面角为117.3°.3在熔解时发生重排及热分解分别生成2-溴-2'-甲氧基-3'-甲硫基-4,4'-二硝基联苯(6)及3,7-二硝基-4-甲硫基-二苯并呋喃(7).3与盐酸反应生成相应的锍盐(8).     

3,7-二硝基二苯并环状卤鎓盐在碱性条件下的反应机理研究

研究了3,7-二硝基二苯并溴五环盐(1a)与一些伯胺及仲胺的反应,其主要产物6(2-溴-2′-烷氨基-4,4′-二硝基联苯)与次要产物7(2-溴-3′-烷氨基-4,4′-二硝基联苯)互为位置异构体,这一结果支持一个以苯炔类化合物(4)为中间体的反应机理．进而用蒽成功地捕获了一系列3,7-二硝基二苯并环状卤鎓盐(1a～1c)在碱性条件下形成的苯炔类中间体,为上述机理提供了强有力的证明．     

4,4''''-二苯甲烷二胺与碳酸二甲酯合成4,4''''-二苯甲烷二氨基甲酸甲酯反应过程分析

对碳酸二甲酯(DMC)与4,4'-二苯甲烷二胺(MDA)合成4,4'-二苯甲烷二氨基甲酸甲酯(MDC)的反应过程进行了研究,采用质谱、元素分析、红外光谱以及核磁共振氢谱等手段,对反应中间产物和最终产物进行了分离、组成结构分析和确认.研究结果表明,该反应是一个经过中间产物的串联反应,主产物为MDC,中间产物结构为4-(4'-氨苯基)苯甲烷氨基甲酸甲酯.     

3,7-二硝基二苯并溴五环盐与亲核试剂的反应及新环状卤翁盐的合成

本文研究了3,7-二硝基二苯并溴五环硫酸氢盐与十种亲核试剂的反应, 分离出主要产物2-溴-2'-Nu-4,4'-二硝基联苯(3a-j), 并以3e~g为原料在浓硫酸中用过二硫酸钾氧化关环合成了多种新的环状卤翁盐。     

3,7-二硝基二苯并溴五环盐与亲核试剂的反应及新环状卤翁盐的合成

本文研究了3,7-二硝基二苯并溴五环硫酸氢盐与十种亲核试剂的反应, 分离出主要产物2-溴-2'-Nu-4,4'-二硝基联苯(3a-j), 并以3e~g为原料在浓硫酸中用过二硫酸钾氧化关环合成了多种新的环状卤翁盐。     

几种新的3,7-二取代二苯并五元环状溴鎓盐的合成

4,4′-二硝基联苯在浓硫酸中与嗅化钠及过硫酸钾反应,直接生成3,7-二硝基二苯并溴五环盐(5).5经SnCl_2-HCl还原得到3,7-二氨基二苯并溴五环盐(6).由6制得的重氮盐溶液分别与氯化亚铜、溴化亚铜及碘化钾反应得到3,7-二氯二苯并溴五环盐(7),3,7-二溴二苯并溴五环盐(8)及 3,7-二碘二苯并溴五环盐(9).5～9均为新化合物,其结构经~1HNMR、MS、IR证实.     

The molecular and crystal structures of a homologous series of bipolar, mesogenic biphenyls-HO(CH2)nOC6H4.C6H4CN

The crystal and molecular structures of eight 4,4'-disubstituted biphenyls of the general formula HO-(CH₂)_n-O-C₆H₄-C₆H₄-CN (n=3-5, 7-11) (HnCBPs) have been determined. All compounds investigated have a nearly parallel molecular arrangement in the crystalline state, with dipole-dipole interactions between the molecules. For n≥7, isomorphic layered structures are observed. The inter-molecular packing is different for odd and even numbers of methylene units in the spacer.     

Effect of connectivity and terminal functionality on mesophase behaviour of thermotropic liquid crystals containing biphenyl units

A series of 4,4'-disubstituted biphenyls, designated as series HBC, in which, one substituent is an ester group linked directly to the ring and the other is the hydroxy-containing group O(CH₂)_nOH, have been prepared and analysed by differential scanning Calorimetry, polarizing optical microscopy and X-ray diffraction. The introduction of a trimethylene unit between the ester functional group and the biphenyl moiety of the HBC series gives rise to the HBB series, which did not exhibit liquid crystalline behaviour. Interestingly, mesophase behaviour could be restored by replacing the methylene group (of the trimethylene unit) that was directly attached to the biphenyl ring by a keto group (HBOB series). When the terminal hydroxy group of these three series was substituted by a group such as acetoxy or hydrogen, the transition temperatures were reduced, and the disappearance of mesophase behaviour was observed in some cases. However, this could be recovered by the replacement of the ester group by a carboxylic acid group.     

间位基团激发态取代基常数的扩展及应用

合成了七个系列含间位取代基X的二苯乙烯m-XArCH=CHArY-p(简称m-XSBY-p),其中X为NO_2、I、CHCH_2、Ph、Et、NMe_2和CCH。在无水乙醇中测定它们的紫外(UV)吸收光谱,得到紫外吸收最大波长λ_(max)(nm)。对λ_(max)的波数ν_(max)(cm~(-1))进行定量相关,采用曲线拟合方法,得到上述7个间位基团的激发态取代基常数σ_(CC(m))~(ex)。将对位基团和间位基团的σ_(CC)~(ex)与Hammett常数σ进行对比,表明σx_(CC)~(ex)与σ分别表达取代基不同的电子效应。另外,合成了含上述间位基团的二芳基希夫碱(10个)和二苯乙烯(14个),用所得σ_(CC(m))~(ex)预测它们的λ_(max),并用实验测定它们的λ_(max),结果表明预测值与实验值相吻合,验证了所得σ_(CC(m))~(ex)常数的可靠性。收集了225个化合物(涉及二取代苯及二苯乙烯)的ν_(max),建立了一个统一的定量方程来表达这些化合物ν_(max)的变化规律。     

Reactions of 2-phenylpyrrole with bromobenzoylacetylene on metal oxides active surfaces

The solvent-free interaction of 2-phenylpyrrole with bromobenzoylacetylene (room temperature) upon their grinding with solid metal oxides (MgO, CaO, ZnO, BaO, Al₂O₃, TiO₂, ZrO₂) and salts (CaCO₃, ZrSiO₄) leads to either the cross-coupling product or the adduct of pyrrole addition to the riple bond of acetylene. The ethynylation is accompanied by the formation of intermediate and side products: E-2-(1-bromo-2-benzoylethenyl)-5-phenylpyrrole and 1,1-di(5-phenylpyrrol-2-yl)-2-benzoylethene. The activity of the metal oxides in the ethynylation reaction falls in the order (in the brackets, the content of 2-benzoylethynyl-5-phenylpyrrole in the reaction mixture is given): ZnO (81%), BaO (73%), Al₂O₃ (71%), MgO (69%), CaO (50%). The oxides, SiO₂, TiO₂, ZrO₂, and the salts, CaCO₃ and ZrSiO₄, are inactive in the ethynylation reaction affording only the intermediate adduct, with ZrO₂ the isolated yield of the bromoethenylpyrrole reaching 60%. ESR monitoring shows the reaction to start from one electron transfer from pyrrole to acetylene mediated by the oxide surface. The adduct is readily converted on Al₂O₃ to 2-(benzoylethynyl)-5-phenylpyrrole crystallized mostly as cis-rotamer (X-ray data).     

由有机硼烷立体选择合成(Z)、(E)链烯-1-醇乙酸酯类昆虫性信息素

等摩尔的甲硼烷甲硫醚(H₃B·SMe₂)与四溴化碳在60℃下反应20h,定量得到一溴硼烷甲硫醚。从链端烯烃、一卤硼烷甲硫醚和2-[7-辛炔-1-氧基]四氢吡喃及其8-溴代衍生物出发,经硼氢化反应和Zweifel的顺-,反-烯烃合成法,立体选择地合成了鳞翅目昆虫性信息素:(Z)-7-十四烯-1-醇乙酸酯9a、(Z)-7-十六烯-1-醇乙酸酯9b、(E)-7-十四烯-1-醇乙酸酯12及其相应的醇13。产物经GC分析和MS、¹H及¹³C NMR数据证实了它们的纯度和几何构型。     

Computational studies of inclusion phenomena and synthesis of a novel and selective molecular receptor for 1,4-disubstituted benzenes and 4,4'-disubstituted biphenyls

A new tetracationic molecular receptor has been synthesized and studied by semiempirical molecular orbital theory. This novel macrocycle, 1(4+), derived from pentacyclo[5.0.0.0.(2,6)0.(3,10)0(5,9)]undecane-8,11-dione (PCU-8,11-dione), structurally resembles cyclobis(paraquat-p-phenylene), 2(4+), in which a xylyl group has been replaced by a PCU unit. This derivatization effectively increases the size and flexibility of 1(4+) and changes its electronic, dynamical, and binding properties. A conformational search using Osawa's corner flapping technique and the PM3 semiempirical method identifies eight unique and low-energy 1(4+) conformers. The principal regions of structural variation occur in the bipyridinium torsion and in the ethylene bridges between PCU and the tetracationic unit. The inclusion complexes of 1(4+) with 1,4-disubstituted benzenes and 4,4'-disubstituted biphenyls have been studied by PM3. The first shell of solvation is approximated by the explicit inclusion of 12 acetonitriles in the computed supramolecular complexes. Binding of 1,4-disubstituted benzenes and 4,4'-biphenol is shifted from the 1(4+) geometric center. From the computations, host 1(4+) is predicted to have an enhanced binding preference for benzidine over 4,4'-biphenol, as compared to 2(4+). For all guests computed, 1(4+) binds more strongly than 2(4+). These properties can be exploited in the future design of supramolecular systems with potential applications as nanoscale devices.     

9-亚胺二苯并型环状碘鎓盐的合成

二苯并型环状碘鎓盐(结构通式如1)是一类人工合成的化合物,近30年的研究表明,某些二苯并型环状碘鎓盐具有抑菌、降血压,抗辐射及抗心律失常^[1-4]等生理活性.     

Theoretical investigations of the substituent effect on the absorption and emission properties for a series of platinum (II) complexes supported by tetradentate N2O2 chelates

The photophysical properties, which vary as R is varied, of a series of [Pt(N₂O₂)] complexes bearing bis(phenoxy)bipyridine auxiliaries with different substituents R=H (Pt-H) (1), 4,4′-2NH₂ (Pt-NH₂) (2), 4,4′-2tBu (Pt-tBu) (3), 4,4′-2CN (Pt-CN) (4), and 4,4′-2NO₂ (Pt-NO₂) (5) are investigated using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The solvent effects are discussed in CH₂Cl₂, CH₃CN and CH₃OH solutions, respectively, by polarizable continuum model (PCM). It is anticipated that compared with σ-donor substituents, π-acceptors have more dramatic effects on the electronic and optical properties in this series of complexes. Introduction of π-electron withdrawing substituents on bipyridine ligand will benefit the LLCT (or MLCT) and prohibit the non-radiative pathways via d–d transitions by increasing the energy gap between the HOMO–LUMO and d–d transitions. The results also reveal that the lowest-energy excitations of all complexes show blue-shifts in the polarized solution and when the polarity of the solvent increases from CH₂Cl₂, CH₃CN and CH₃OH, the low-energy broad absorption band exhibit blue-shifts. The lowest-energy excitations and photoluminescence of all complexes are dominated by π(phenoxy)→π^*(bpy/NO₂) (LLCT) excited state mixed with some energetically dπ (Pt)→π^*(bpy/NO₂) (MLCT) transition.     

Theoretical study of tricyclo[3,3,1,1]decane, tricyclo[3,3,1,1]decsilane molecules and their halogen derivatives, C10H12X4 and Si10H12X4 (X=F, Cl, Br, I)

The B3LYP/3-21G* ab initio molecular orbital method from the program package was applied to study tricyclo[3,3,1,1^3,7]decane and tricyclo[3,3,1,1^3,7]decsilane molecules and their halogen derivatives (1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane, C₁₀H₁₂X₄ and Si₁₀H₁₂X₄ respectively). The optimized structures of these compounds were obtained. Ionization potentials, HOMO and LUMO energies, energy gaps, heats of formation, atomization energies and vibration frequencies were calculated. The calculations indicate that these molecules are stable and have T_d symmetry. Tricyclo[3,3,1,1^3,7]decsilane and its halogen derivatives (Si₁₀H₁₂X₄) are found to have higher conductivity than tricyclo[3,3,1,1^3,7]decane and its halogen derivatives (C₁₀H₁₂X₄). 1,3,5,7-Tetrafluorotricyclo[3,3,1,1^3,7]decane (C₁₀H₁₂F₄) and 1,3,5,7-tetrafluorotricyclo[3,3,1,1^3,7]decsilane (Si₁₀H₁₂F₄) were found to be the easiest compounds to form and the most difficult to dissociate of all 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decane and 1,3,5,7-tetrahalotricyclo[3,3,1,1^3,7]decsilane compounds, respectively.