4—叔丁基—2—巯基吡啶的合成

以４－叔丁基吡啶为原料，与碘甲烷成盐后经铁氰化物氧化，在吡啶环上引入酮基，再经溴代，巯基化得标题化合物，由原料到溴代物的合成总收率达８０％。     

溴化-1，4／1，6-二（a-辛基吡啶）丁烷／己烷的合成及表征

以吡啶和1-溴代正辛烷为原料，制得中间产物a-辛基吡啶，再分别与l，4-二溴丁烷和1，6-二溴己烷反应，得到两种含氮杂环的双子季铵盐表面活性剂，通过定性实验和波谱方法鉴定了其结构，并表征了这两种表面活性剂的表面活性和杀菌活性．结果表明：这两种化合物均有一定的降低水表面张力的能力，以及杀菌活性．     

4-二甲氨基吡啶催化合成含氟苯甲酸糖酯

以4－二甲氨基吡啶为催化剂由含氟苯甲酸与溴代乙酰糖催化酯化合成了4个新的含氟苯甲酸糖酯。其结构经IR，^1H NMR和MS确认，多数还作了^13C NMR测定。     

一锅法Kumada偶联反应合成烷基吡啶化合物

以溴代吡啶为原料,用简单结构的镍化合物(Py4NiCl2)作为催化剂,经过一锅法Kumada偶联反应合成一系列甲基、烯丙基或苄基取代的吡啶化合物,收率在中等以上.     

3－［取代苯胺基甲叉］－6－甲基－α，γ－哟喃酮的酸性成环反应

研究了３－［取代苯胺基甲叉］－６－甲基－α，γ－吡喃酮在酸性条件下的成环反应，所得７种产物经元素分析及核磁共振分析证实了相应的氧代吡啶羧酸衍生物。     

新型溴化烷基取代吡啶类季铵盐的合成

以烟酰胺(1)为原料,分别与1-溴代辛烷(2a)和1-溴代癸烷经烷基化反应合成了两个新型的溴化烷基取代吡啶类季铵盐(3a和3b),其结构经1H NMR,13C NMR,IR和HR-MS(MALDI)表征。在最佳反应条件[乙醇为溶剂,1 10 mmol,n(2a)∶n(1)=1.2,于78℃反应4 h]下,3a收率69%。     

吡啶高三蝶烯的合成

2-溴-4-甲基吡啶（1）经氯代和碘代反应合成了2-溴-4-碘甲基吡啶（3）,3和蒽酮（4）反应生成10,10-二（2-溴-4-吡啶甲基）-9（10H）蒽酮（5）,5在3 MPa下与NaOCH3反应得到10,10-二（2-甲氧基-4-吡啶甲基）-9（10H）蒽酮（6）,6经硼氢化钠还原得到蒽醇（7）,7在对甲苯磺酸催化...     

β－环糊精交联聚合物包结5－Br－PADAP配合物富集铜和镍的研究

β－环糊精交联聚合物包结有机显色剂２－（５－溴－２－吡啶偶氮）－５－二乙氨基苯酚所形成的配合物树脂可与多种金属离子反应生成吸附配合物。本文报道了以这种包结配合物树脂吸附富集铜与镍的有关实验条件、反应机理以及用分光光度法进行测定的研究。结果表明，在ｐＨ＝４～６的弱酸性介质中，包结树脂可以分别从稀溶液中定量吸附铜与镍。富集倍数达到５０倍（铜）与２００倍（镍）。     

一个新的制备咪唑并[1，5－α]吡啶衍生物的串联反应

发现5－咪唑甲醛（1）与γ－溴代巴豆酸酯（2）在弱碱条件下首先进行亲核 取代反应生成3，继而生成γ－碳负离子并转移到α－位，然后进行了分子内亲核 进攻成环，脱水生成4的串联反应，提供了一个合成咪唑并[1，5－α]吡啶－7－羧 酸酯衍生物的新方法。     

镍（Ⅱ）与2－（5－溴－2－吡啶偶氮）－5－二甲氨基苯胺显色反应的研究及铝合金中镍的测定

本文研究了新显色剂２－（５－溴－２－吡啶偶氮）－５－二甲氨基苯胺与镍（Ⅱ）的反应条件。试验结果发现，在阴离子表面活性剂十二烷基硫酸钠存在下，在ｐＨ５．２～６．５范围内，试剂与镍（Ⅱ）形成稳定的２∶１配合物。其最大吸收波长在５７０ｎｍ处，表观摩尔吸光系数为１．２４×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。镍（Ⅱ）浓度在０～０．４μｇ·ｍＬ￣（－１）之间符合比尔定律。以硫脲和氟化按作掩蔽剂，可消除Ｃｕ￣（２＋）、Ｐｄ￣（２＋）、Ｆｅ￣（３＋）等离子的干扰。所拟方法用于铝合金中微量镍的测定，结果满意。     

Synthesis of New Multibranch Chromophores with Strong Light-emitting in Solution and in PMMA Film

Three new chromophores with triphenylamine as molecular focal point bearing one,two, or three 4-(n-butyloxystyryl) group(s) at the periphery respectively, (named as T1, T2, and T3) have been synthesized and characterized. It is interesting to find that the fluorescence quantum yield increases from T1 (0.489), to T3 (0.535), and to T2 (0.628) in cyclohexane, meanwhile the lifetime for T3 is shorter than T1 and T2, which is an important characteristic for applications in light emitting diode. Also PMMA (polymethyl methacrylate) film doped with T3 gives stronger fluorescence than T1, and T2. Cyclic voltammetry showed that T3 exhibited lowest oxidation potential of-0.52 V vs SCE, suggesting its better hole-transport property.     

4,4′-二乙炔二苯甲烷与苯乙炔的共聚及共聚物的表征研究

本文做了4,4′-二乙炔二苯甲烷的本体热均聚和催化均聚,并用(Ph_3P)_2PdCl_2为催化剂做了4,4′-二乙炔二苯甲烷与苯乙炔的共聚,对均聚和共聚物中的不溶不熔组分测定了密度、溶胀度、Huggins参数以及交联点间的平均分子量(?)_c。实验表明,该交联聚合物的最良溶剂是四氢呋喃,溶度参数为9.9ca1~0.5。cm~(-1.5),当用四氢呋喃为溶剂时的Huggins参数为0.34,并且在单体摩尔比中4,4′-二乙炔二苯甲烷用量越多,溶胀度越小,交联度越大。红外光谱分析表明,所有均聚及共聚物都为反式结构。     

1,4-丁炔二醇与4,4′-二乙炔联苯共聚物的合成及表征研究

本文用(Ph_3P)_2PdCl_2为催化剂,合成了1,4-丁炔二醇(BD)与4,4-二乙炔联苯(DEBP)共聚物。对用不同比例的两种单体得到的共聚物测定了比重(d_4~(25)、溶胀度(θ_D)、最良溶剂及相邻两交联点之间的平均分子量(M_c)。实验表明,在两种单体摩尔比中,DEBP用量越多,共聚物中泡状微孔越多,颜色越淡,溶胀度和比重越小,交联度越大;DEBP/BD(摩尔比)大于1/5时,共聚物的最良溶剂为苯,溶度参数为9.15卡~(0.5)·cm~(-1.5),是1/10时,其最良溶剂为乙醇,溶度参数是12.7卡~0.5·cm~(-1.5)。对共聚物还做了红外光谱表征。     

具有梯形结构钴(Ⅱ)配位聚合物的合成及晶体结构

Co(NO₃)₂, N-carbazolyacetic acid and 4,4′-bipyridyl can give rise to a novel coordination polymer [CO₂(Cabo)₂(NO₃)₂(4,4′-bipy)₂]_n using a fritted U-tube. Single crystal X-ray diffraction displays in the complex, each Co(Ⅱ) is six-coordinated by two N atoms from different 4,4′-bipyridyl ligands, two O atoms of the bridge from two N-carbazolyacetic acid and two O atoms of one nitrate anion to form a distorted octahedral. Two O atoms of the carboxyl group act as bridge to link two Co(Ⅱ) atoms. The resulting structure is a ladder polymer. CCDC: 211713.     

1H NMR Study on the Isomerization of 2,4,6-Triphenyl-4H-Seleno(Thio)Pyrans

It is shown using ¹H NMR spectroscopy that 2,4,6-triphenyl-4H-seleno(thio)pyrans can be isomerized into 2H-isomers by the action of lithium perchlorate or lithium chloride in DMF or only by DMF. The reaction time is found to depend on the Lewis acidity of used salt. It is supposed that isomerization in presence of Lewis acids proceeds as endocyclic 1,3-proton transfer or as a series of two 1,2-hydride shifts.     

Synthesis and Crystal Structure Analysis of 4-Dibenzaldehydeamino-4H-1,2,4-triazole Diacetate

The new title compound 4-dibenzaldehydeamino-4H-1,2,4-triazole diacetate （C16H18N8O4,Mr = 386.38） has been prepared and its crystal structure was determined by single- crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 8.1371（17）,b = 7.1237（12）,c = 16.325 （2）A,β = 100.366（2）°,V = 930.9（3） A^3,Z = 2,Dc = 1.378,F（000） = 404,μ = 0.104 mm^-1,MoKa radiation （λ = 0.71073 ）,R = 0.0307 and wR = 0.1196 for 4632 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the molecule is not flat and the crystal structure is stabilized mainly by van der Waals interactions.     

Crystal Structure of a 4-Methyl-phenylacetylide-bridged PtⅡCuⅠ2 Heterotrinuclear Organometallic Complex

The heterotrinuclear complex [PtCu2(μ-dppm)2(dmbpy)2(μ-η1,(2 C ≡ CPhCH3-4)2] (ClO4)2·1.5CH2Cl2 1 (dmbpy = 4,4‘-dimethyl-2,2'-bipyridine, dppm = bis(diphenylphosphino)meth- ane) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic system, space group Pī with a = 12.9359(3), b = 14.3908(2), c = 15.2121(3) (A), α = 107.370(1), β = 93.539(1), γ = 108.207(1)o, V = 2529.59(8) (A)3, Mr = 2015.96, Z = 1, Dc = 1.323 g/cm3, F(000) = 1019, ((MoKα) = 2.042 mm-1, the final R = 0.0604 and wR = 0.1529 for 8002 observed reflections with I > 2σ(I). The 4-methylphenylacetylides are bonded to the PtII and CuI centers in η1 (σ) and η2 (π) coordination modes, respectively. The PtII atom is linked by one dppm bridge to adopt a square planar environment and CuI by one alkynyl ligand to assume a distorted tetrahedral geometry.     

A New 3D Layered-pillared Cobalt（II）-organic Framework Constructed by Imidazole-4,5-dicarboxylic Acid （H_3IDC） and 4,4＇-Bipyridine （bipy）

A new 3D metal-organic framework of {[Co3(IDC)2(bipy)2(py)2]·7H2O}n (1) was obtained by the hydrothermal reaction of Co(NO3)2·6H2O, imidazole-4,5-dicarboxylic acid (H3IDC), 4,4'-bipyridine (bipy), and pyridine (py), and structurally characterized by elemental analysis, infrared spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction crystal structural analysis reveals that it crystallizes in orthorhombic system, space group Pccn with a = 11.1040(3), b = 19.8834(5), c = 21.3025(5), V = 4703.3(2)3, Mr = 1079.63, Z = 4, Dc = 1.525 Mg·m-3, F(000) = 2212, μ(CuKα) = 8.855 mm-1, the final R = 0.0331 and wR = 0.0713 for 2525 observed reflections with I ≥ 2σ(I). In compound 1, each cobalt(II) ion is six-coordinated with a slightly distorted octahedral coordination geometry, and each μ3-IDC3- acts as a bridge to bond three neighboring Co(II) ions, leading to an infinite 2D network layer structure of [Co3(IDC)2]n with Kagomé lattice. The adjacent layers are further linked by μ2-bipy to form an infinite 3D layered-pillared framework architecture of [Co3(IDC)2(bipy)2(py)2]n.     

On synthesis, structure, and thermal stability of mercury and lead sulfates and oxide sulfates

Reactions between HgO, PbO, or PbO₂ and 2.5–95 wt.% H₂SO₄ are studied at temperatures up to the boiling point of the acid. Depending on the oxide reactant, the H₂SO₄ concentration, and synthesis temperature, HgSO₄, Hg₃O₂(SO₄), PbSO₄ and Pb₂O(SO₄) are obtained as identified reaction products. The thermal stability of HgSO₄, Hg₃O₂(SO₄), PbSO₄, Pb₂O(SO₄), and PbO₂ is examined and the results supplement and modify earlier findings. The redetermined crystal structure of Hg₃O₂(SO₄) on the basis of powder neutron diffraction data shows that its space group (P3₁) is of lower symmetry than earlier reported (P3₁2₁).     

NH4VO3在NH4H2PO4-H2O和(NH4)3PO4-H2O体系中的溶解度

采用等温溶解法测定了偏钒酸铵(NH₄VO₃)在NH₄H₂PO₄-H₂O和(NH₄)₃PO₄-H₂O体系中T = 298.15-328.15 K时的溶解度以及溶液的密度和pH值。结果表明, NH₄VO₃的溶解度随着(NH₄)₃PO₄或NH₄H₂PO₄溶液浓度的增大,先降低后升高,这是由于同离子效应、化学反应平衡及离子活度的共同作用。比较T = 298.15K时, NH₄VO₃分别在NH₄H₂PO₄-H₂O、(NH₄)₂HPO₄-H₂O和(NH₄)₃PO₄-H₂O体系中溶解度,发现在相同的磷酸盐浓度下, NH₄VO₃的溶解度在NH₄H₂PO₄-H₂O体系中最大,在(NH₄)₃PO₄-H₂O体系中居中,在(NH₄)₂HPO₄-H₂O体系中最小。进一步地,在T = 298.15 K和磷酸盐浓度C = 0.5 mol·kg^-1时,结合pH值和反应溶度积常数K_SP等计算三个体系中的平均离子活度系数(γ_±),发现γ_±值在(NH₄)₂HPO₄-H₂O体系中最大,在(NH₄)₃PO₄-H₂O体系中居中,在NH₄H₂PO₄-H₂O体系中最小,与溶解度规律一致。