A new route to the synthesis of thieno[2,3-d]pyrimidin-4(3H)-one derivatives catalyzed by 12-tungstophosphoric acid (H_3PW_(12)O_(40))

Heteropoly acid H3PW12040 （PW） has been used as an effective catalyst for the synthesis of thieno[2,3-d]pyrimidin-4（3H）-one derivatives. The present methodology offers several advantages, such as high yields, short reaction times, mild reaction condition and a recyclable catalyst with a very easy work up.

Improved Synthesis and Structure of 3-Carboxy-2-pyrazinecarbohydroxamic Acid

3-Carboxy-2-pyrazinehydroxamic acid was prepared by a one pot reaction starting from pyrazine-2,3-dicarboxylic anhydride with a high yield, and characterized by IR, Mass spectrum, 1H NMR and 13C NMR spectra and single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with a=4.8659（10）, b=7.4233（15）, c=11.602（2）, α=96.904（2）, β=92.422（3）, γ=107.454（2）°, V=395.51（14）3 , Z=2, Dc=1.689g/cm3 , F（000）=208, μ（MoKα）=0.149 mm-1 , the final R=0.0473 and wR=0.1306 for 2853 observed reflections （I〉2σ （I））. A three-dimensional framework was assembled through intermolecular hydrogen bonding between water and 3-carboxy-2-pyrazine-carbohydroxamic acid molecules.

2,3-二氯-1,4-萘醌的合成工艺

研究了以1,4-萘醌为原料,催化氯化制备2,3-二氯-1,4-萘醌的反应机理及合成工艺优化。研究发现该氯化反应为酸催化反应机理,氯化氢为有效的1,4-萘醌氯化催化剂。通过工艺优化确定了最佳合成条件为:反应温度75℃,催化剂用量1.5mL,溶剂用量80 mL,原料加入量为7.5 g,通氯速度为15mL·min^(-1),反应时间为1.5~2 h,产品纯度大于99.5%。母液经多次套用后产品收率达到91%~93%,产品纯度均达到优等品级别(≥99.0%)。

噻吩-2,3-二羧酸的电合成

以3-甲基噻吩为原料,通过电卤化、格氏反应、间接电氧化三步合成目标产物噻吩-2,3-二羧酸。考察了电卤化过程中电流密度、温度对2-溴-3-甲基噻吩收率的影响。在此过程中电卤化试剂采用溴化钠,产品收率可达85.5%且能够更好的满足格氏反应中底物活泼性的考究。通过格氏反应合成了3-甲基-2-噻吩羧酸,主要对其反应时间与收率的关系进行了考察,较优反应时间为6 h,产品收率最高达87.8%。以间接电氧化法合成噻吩-2,3-二羧酸,分别考察了电流密度、电解温度、基质氧化温度、投料比、反应时间等因素对反应的影响,较优工艺下收率为87.6%。噻吩-2,3-二羧酸的整个电合成的过程中均无采用传统有毒有害的卤化剂与氧化剂,对环境友好,三废排放少,且过程简单,产物易分离,能够获得较高的产品收率。

Improved One-pot Synthesis of 4,6-Dihydroxyisophthalic Acid and 2,3-Dihydroxyterephthalic Acid

An improved method for the large-scale preparation of 4,6-dihydroxyisophthalic acid and 2,3-dihydroxyterephthalic acid has been developed.Compared to the previous procedures,this new process-requires much lower CO2 pressure of 0.3 Mpa and shorter reaction time.thus providing a convenient access for large-scale synthesis.The yield is high （93% and 65%,respectively）, and the oxidation of phenol is nearly inhibited,neither decolorization nor further chromatographic purification is required.

Synthesis,Crystal Structure and Magnetic Behavior of a New Manganese(Ⅱ) Coordination Polymer [Mn(DPPZ)(PZDC)(H_2O)] (DPPZ=Dipyrido[3,2-a:2',3'-c]-phenazine and H_2PZDC=Pyrazine-2,3-dicarboxylic Acid)

The title complex, [Mn（DPPZ）（PZDC）（H2O）] 1 （DPPZ = dipyrido[3,2 -a：2＇,3＇- c]phenazine and H2PZDC = pyrazine-2,3-dicarboxylic acid）, has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analyses, IR, TG- DTA and magnetic susceptibility measurement. It crystallizes in triclinic, space group P1^- with a = 6.6842（5）, b = 7.5741（6）, c = 20.5755（15）A, α = 90.1160（10）, β = 97.0560（10）, γ = 97.3350（10）°, V= 1025.16（13）A^3, Z = 2, MnC24H14N6O5, Mr= 521.35, Dc= 1.689 g/cm^3, F（000） = 530, μ（MoKa） = 0.699 mm^-1, R = 0.0366 and wR = 0.0810. Compound 1 contains one- dimensional chains which are further stacked through π-π interactions to form a 3D supramolecular architecture. The water molecule O（1W） is involved in hydrogen bonding interactions with symmetric carboxylate oxygen atom 0（4） at （x＋ 1, y＋1, z） and symmetric PZDC nitrogen atom N（6） at （1-x, 1-y, 1-z）, which completes the structure of 1. Magnetic susceptibility measurement indicates that the compound behaves a weak antiferromagnetic exchange interaction.

Synthesis, Crystal Structure and Properties of a New Zn(II) Coordination Polymer Constructed from 2,3-Pyridine Dicarboxylic Acid and 1,1′-(1,4-Butanediyl)bis(imidazole)

A new coordination polymer, namely [Zn（pdc）（bbi）]n {H2 pdc = 2,3-pyridine dicar- boxylic acid, bbi = 1,1-（1,4-butanediyl）bis（imidazole）}, has been prepared under hydrothermal conditions and characterized by elemental analysis, IR, and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21 /n with a = 8.436（3）, b = 16.988（5）, c = 12.106（4）, β = 92.204（5）°, V = 1733.6（9）3, Z = 4, C17 H17 N5 O4 Zn, Mr = 420.73, Dc = 1.612 g/cm3, F（000） = 864, μ（MoKa） = 0.452 mm-1, the R = 0.0672 and wR = 0.1645. In the mononuclear complex, each Zn（II） is five-coordinated by one carboxylate O and one pyridyl N atoms from one pdc anion, one carboxylate O atom from another pdc anion, and two N atoms from two bib ligands. The Zn（II） ions are connected by pdc ligands to form skeleton chains, and bbi ligands further link them to construct a 2D framework. The thermal and luminescence properties of the complex were also investigated.

Hydrothermal Synthesis and Crystal Structure of a New Three-dimensional Co(Ⅱ) Coordination Polymer Based on 2,3-Thiophenedicarboxylic Acid

A new Co（ll） polymer [Co（tdc）（l,4-bimb）]n 1 （H2tdc = thiophene-2,3-dicarboxy- lic acid, 1,4-bimb -- 1,4-bis（imidazol-1 ＇-yl）butane） was synthesized under hydrothermal conditions The compound crystallizes in the monoclinic system, space group C2/c with a = 15.643（9）, b = 8.839（5）, c=12.952（7） A, β = 105.964（6）°, V= 1721.8（16） A3, Z = 4, Mr = 419.32, Dc= 1.618 Mg/m3,μ = 1.149 mm-1, F（000） = 860, the final R = 0.0243 and wR =0.0613 for 1460 observed reflections with I 〉 2σ（I）. The compound presents a three-dimensional （3D） network extended by both tdc2- anions and 1,4-bimb ligands in which the tdc2- anions employ a chelating coordination mode. From the topology point of view, the structure could be described as a 3D 4-connected 65.8 CdSO4-type net. Infrared spectroscopy, elemental analyses, thermogravimetric analysis and powder X-ray diffraction properties of 1 are also investigated.

2,3-Dimercaptosuccinic acid self-assembled gold electrode for the simultaneous determination of epinephrine and dopamine

Simultaneous determination of epinephrine （EP） and dopamine （DA） at 2,3-dimercaptosuccinic acid （DMSA） modified electrode was studied. The oxidation peaks of the mixture of EP and DA appeared at the same potential, but the cathodic peak currents were only linear to the concentration of DA, whereas the anodic peak currents were equal to the sum of individual anodic peak currents of EP and DA. Therefore, a novel electrochemical method for the simultaneous determination of EP and DA at a DMSA modified electrode （DMSA/Au electrode） by cyclic voltammetry was established. The DMSA self-assembled electrode showed good sensitivity, selectivity and stability and could be used to determine DA and EP, simultaneously, in the real application with satisfactory results.

A Benzimidazole-pyridine-2,3-dicarboxylic Acid Bridged Zinc(Ⅱ)Coordination Complex–crystal Structure,Quantum Chemistry and Luminescence

The structure of a zinc（Ⅱ） coordination complex（1）, [C14 H10 N3 O5 Zn1.5]n or [Zn1.5（bzim）（pydc）（H2 O）]n（H2 pydc = pyridine-2,3-dicarboxylic acid, Hbzim = benzimidazole）, has been determined by X-ray crystallography and characterized by elemental analysis, IR spectrum and luminescence. Chemical formula： C14 H10 N3 O5 Zn1.5. It crystallizes in the monoclinic system, space group P21/c with a = 12.303（4）, b = 12.052（4）, c = 10.212（3） ？, β = 104.147（4）, V = 1468.3（8） ？3, Z = 4, Mr = 398.30, Dc = 1.802 g/cm3, F（000） = 800, μ = 2.501 mm-1 and S = 1.000. The 2-D network architecture of 1 is constructed from benzimidazole, zinc and pyridine-2,3-dicarboxylic acid. The quantum-chemical calculations have been performed on ‘molecular fragments’ extracted from the crystal structure using the B3 LYP method in Gaussian 09. The luminescence spectrum shows that complex 1 emits blue luminescence.

Hydrothermal Synthesis, Crystal Structure and Thermal Analyses of Pyrazine-2,3-dicarboxylic Acid Bridged Co(II) Coordination Polymer of _∞~2[Co(phen)(μ-L)_(3/3)]·H_2O (H_2L = Pyrazine-2,3-dicarboxylic Acid)

A novel pyrazine-2,3-dicarboxylic acid bridged Co(II) phen complex 2 ∞ [Co- (phen)(μ-L)3/3]?H2O (H2L = pyrazine-2,3-dicarboxylic acid) has been hydrothermally synthesized, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group P21/n with a = 11.480(2), b = 11.885(2), c = 12.939(3) ?, β = 110.55(3)°, V = 1653.1(6) ?3, Mr = 423.25, Dc = 0.425 g/cm3, Z = 4, R = 0.0361 and wR = 0.1011. The title complex consists of 2D 2 ∞ [Co(phen)(μ-L)3/3] layers and crystal water molecules. Each Co atom is octahedrally coordinated by three N atoms and three O atoms to form 2D 2 ∞ [Co(phen)(μ-L)3/3] polymeric layers. Furthermore, such 2D layers are stacked into 3D supramolecular frameworks via Van der Waals’ intermolecular forces, strong and weak hydrogen-bond interactions. The coordination phen and crystal water molecules are resided into cavities of the frameworks.

右佐匹克隆片中吡嗪-2,3羧酸测定方法的优化

目的优化高效液相色谱测定右佐匹克隆片中吡嗪-2,3羧酸的方法,解决同一标准对不同厂家右佐匹克隆片中吡嗪-2,3羧酸峰判断和扣除的问题。方法采用高效液相色谱法对多个辅料进行初筛,确定杂质来源后,优化色谱条件,最终采用Venusil MP C18柱(4.6 mm×250 mm,5μm);以水[用磷酸调节pH值至(1.5±0.02)]为流动相A,甲醇为流动相B,梯度洗脱(0~10 min,3%B;10~16 min,3%~80%B;16~25 min,80%B;25.1~35 min,3%B);流速为1.0 mL·min-1;检测波长为270 nm;柱温为30℃;进样量为5μL。结果通过方法学考察,吡嗪-2,3羧酸在0.07975~15.95μg·mL^(-1)内与峰面积线性关系良好,专属性、重复性、稳定性及准确度良好。结论该方法操作简单,结果准确,适用于右佐匹克隆片中吡嗪-2,3羧酸的测定。

Synthesis,Crystal Structure and Theoretical Calculations of a Zinc(Ⅱ) Coordination Polymer Assembled by Pyrazine-2,3-dicarboxylic Acid and Bis(imidazol) Ligands

A new metal-organic coordination polymer [Zn（pzdc）（mbix）]n·nH2O（H2pzdc = pyrazine-2,3- dicarboxylic acid, mbix = 1,3-bis（imidazol-1-ylmethyl）-benzene） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG, fluorescence spectrum and single-crystal X-ray diffraction. Yellow crystals crystallize in monoclinic system, space group P21/n with a = 8.5519（6）, b = 14.8764（10）, c = 16.4108（11） A, β = 103.4520（10）o, V = 2030.5（2）A^3, C（20）H（18）N6O5Zn, Mr = 487.77, Dc = 1.596 g/cm^3, F（000） = 1000, Z = 4, μ（MoK α） = 1.257 mm^-1, the final R = 0.0260 and w R = 0.0706 for 3445 observed reflections（I 〉 2σ（I））. The structure of 1 exhibits a one-dimensional chain-like structure. In addition, natural bond orbital（NBO） analysis was performed by the PBE0/LANL2DZ method in Gaussian 03 Program. The calculation results show obvious covalent interaction between the coordinated atoms and Zn（Ⅱ） ion.

2,3-二氯苯甲酸的合成新方法

探索了一条合成抗癫痫药拉莫三嗪(Lamotrig-ine)的关键中间体2,3-二氯苯甲酸的新路线.以邻氯苯胺为原料,与水合三氯乙醛、盐酸羟胺反应先制得邻氯基(N-肟基乙酰)苯胺,用浓硫酸关环生成3-氯靛红.再用过氧化氢氧化,制得2-氨基-3-氯苯甲酸;然后再经过酯化、重氮化、Sandmeyer氯代和水解,得到了目标产物2,3-二氯苯甲酸,反应总收率为49%.其结构经1H NMR、13C NMR和IR表征.

4-单取代-1,2,3-三氮唑的合成进展(Ⅰ)——通过环加成反应

1,2,3-三氮唑衍生物是近些年研究热点化合物之一,随着4-单取代型衍生物在医药、农药、材料等领域的广泛应用,该类化合物的合成及应用近些年引起了广大研究者的关注并获得了可喜进展。本文阐述了4-单取代-1,2,3-三氮唑衍生物的合成发展历史,着重综述了近十年来该类唑衍生物的合成发展情况。内容主要包括末端炔的环加成反应、由取代烯烃合成法及由3-芳基-2,3-二溴丙酸合成法。文章还包括一些合成方法及其产物的应用,并对一些重要的反应机理做了分析。文章最后对该类化合物的合成做了总结并展望了未来发展方向。

2,3-二氯吡啶的合成新工艺

为满足市场需求,对2 ,3-二氯吡啶的合成工艺进行了研究.以2-氯烟酸为起始原料,经酰胺化、霍夫曼（Hofm ann）酰胺降解、重氮化和Sandmeyer 4 步反应,得到2 ,3-二氯吡啶,对影响产率的因素（如PC13 用量、NaOH 浓度、反应温度、催化剂用量）进行了优化.结果表明：酰胺化中,n（2 -氯烟酸）：w（PCl3） = l ： 0.45 ;霍夫曼降解反应中,NaOH 质量分数为18% ,反应温度为75？80°C;Sandmeyer反应中,n （2-氯-3-氨基p比咬）：n （氧化铜）= 1 ： 0. 3.在此优化条件下,反应总收率为70. 33% （以2-氯烟酸计）,纯度达98. 5% ,通过1 H -N M R 进行了结构表征.此法产品纯度高,操作简便,原料易得.

2,3-二氯苯甲酸的合成研究

2,3-二氯苯甲酸是合成特效抗癫痫药拉莫三嗪及其它治疗中枢神经紊乱药物的重要中间体。笔者用2,3-二氯苯胺经重氮化、迈尔瓦音反应制得2,3-二氯苯甲醛,再经高锰酸钾氧化制得2,3-二氯苯甲酸,总收率45%。对各步反应的操作及产品的纯化方法进行了研究。

2,3-吡啶羧酸酐的合成

研究了2,3-吡啶二羧酸与亚硫酰氯反应制备2,3-吡啶羧酸酐的方法,考察了物料配比、反应温度、反应时间等因素对反应收率的影响,确定了适宜的合成工艺条件:反应温度60℃,反应时间6h,2,3-吡啶羧酸与氯化亚砜(SOCl2)的摩尔比为1∶1.05。在此条件下产品收率超过95%,纯度达96%。

高纯度2,3-二氯吡啶的简便合成方法

标题化合物是重要的精细化工中间体,对其合成工艺进行优化。以2-氯烟酸和固体光气为原料,氯化、氨化得到2-氯烟酰胺,2-氯烟酰胺在次氯酸钠溶液和氢氧化钠溶液中霍夫曼酰胺降解得到2-氯-3-氨基吡啶,其经过自由基取代得标题化合物。在优化的反应条件下,收率达75.6%,纯度99%。该法操作简便、适合工业化生产,其化学结构经1HNMR分析得到确证。

4-乙基-2,3双氧代哌嗪-1-甲酰胺基-对羟基苯乙酰氯的合成

以双三氯甲基碳酸酯(三光气,简称BTC)代替三氯氧磷与D(-)-α-(4-乙基-2,3-双氧代哌嗪-1-甲酰胺基)对羟基苯乙酸(OH-EPCP)发生酰氯化反应制备4-乙基-2,3-双氧代哌嗪-1-甲酰胺基-对羟基苯乙酰氯(OH-EPCP氯化物)。当酰氯化条件为:n(OH—EPCP)／n(BTC)=3／1,三乙胺(TEA)为引发剂,反应温度为0～5℃,反应时间2．5 h时,目标产物收率达97.6％。产品为淡黄色粉末,用高效液相色谱仪测得w(OH—EPCP氯化物)=98．14％。用红外光谱仪分析产品主要官能团(cm-1):3431,1789,1716,1682,1614、1517、1472,1188,790～860,683。1H NMR(CDCl3)分析结果(δH):11．716,7．196,6．890,5．314,4．021,3．518-3．541,3．073,1．369。