2, 3-二氯-5-取代-5, 8-二氢-8-氧-吡啶并[2, 3-b)吡嗪-7-羧酸乙酯的合成

3, 5, 6-哌嗪三酮-2-甲酰胺(5)经与PCl5-POCl3反应制得3, 5, 6-三氯-2-氰基吡嗪(6)。6经转化为甲酯(7)再水解为3, 5, 6-三氯-2-吡嗪甲酸(8)。由8出发合成了两个2, 3-二氯-5-取代-5, 8-二氢-8-氧-吡啶并[2, 3-b]吡嗪-7-羧酸乙酯(11a~b)。其中5, 7~11均为新化合物, 其组成和结构经元素分析、IR、^1H NMR、MS证实。     

钴(Ⅱ)催化2-乙基-3-甲基吡嗪绿色氧化方法

以过氧化叔丁醇为氧化剂,以钴(Ⅱ)与含N配体为催化体系催化氧化2-乙基-3-甲基吡嗪(EMP),提出一种具有放大应用前景的2-乙酰基-3-甲基吡嗪绿色制备方法.考察了过渡金属催化剂的种类、配体种类、溶剂、温度等反应条件对催化氧化过程的影响,在最优反应条件下EMP转化率可达58.8%, 2-乙酰基-3-甲基吡嗪(AMP)选择性92.2%.研究了该反应体系催化氧化EMP的反应机理,建立了该反应的拟均相反应动力学模型.在以上实验基础上,对该反应体系进行了放大实验研究,结果表明该新方法具有较好的工业放大前景,但反应温度的控制是放大过程的关键因素.     

6-卤代咪唑并[1,2-a]吡嗪-3-甲酰胺的简便合成

6-卤代咪唑并[1,2-a]吡嗪-3-甲酰胺是一类重要的抗癌新药中间体,广泛应用于淋巴癌、肺癌、皮肤癌等癌症新药的研发。以2-氨基吡嗪为起始原料,与N-卤代丁二酰亚胺发生卤代反应,与N,N-二甲基甲酰胺二甲基缩醛制备亚胺化合物,再和溴乙酸乙酯缩合成环制备6-卤代咪唑并[1,2-a]吡嗪-3-甲酸乙酯,再与氨水氨解共4步反应合成6-卤代咪唑并[1,2-a]吡嗪-3-甲酰胺,总收率为50.7～54.2%。产物结构经IR、~1H NMR、~(13)C NMR、元素分析进行了表征。此合成路线具有原料易得、操作简单、成本低廉、产率较高、避免柱层析分离纯化、更适合工业化放大生产的特点。     

3-取代苯基吡咯吡嗪酮的合成

以2-甲基-3-对氨基苯基吡咯并[1,2-a]吡嗪-1(2H)-酮为母体,分别经酰基化(或磺酰基化,烷基化)反应合成了一系列新型的吡咯并吡嗪酮类化合物,其结构经1H NMR,IR和MS表征。     

吡嗪类葡萄糖激酶激动剂中间体5-氯吡嗪-2-羧酸的合成

以2-乙酰基呋喃为原料,经二氧化硒氧化、与甘氨酰胺环合、三氯氧磷氯化、高锰酸钾氧化等步骤合成了吡嗪类葡萄糖激酶激动剂中间体5-氯吡嗪-2-羧酸。考察了环合反应中反应温度、反应时间等反应影响因素,并对通过正交试验法进行了优化,结果表明当反应时间3 h、温度10℃、甘氨酰胺盐酸盐与氢氧化钠的摩尔比为1∶2.5时环合收率最佳,较文献提高23.1%。最后一步合成得到5-氯吡嗪-2-羧酸中,采用盐酸酸化乙酸乙酯提取法代替使用价格昂贵的阳离子交换柱,收率74.8%与文献值相当,操作简单,价格低廉。     

2，6-二氨基-3，5-二硝基-1-氧吡嗪合成中的氧化方法改进

以磁性Fe3O4负载质子化过氧钨酸盐为催化剂,在不用三氟乙酸的情况下,以双氧水为氧化剂,将2,6-二甲氧基吡嗪、2,6-二氯吡嗪和2-氯-6-甲氧基吡嗪高效地氧化为其相应的氮氧化物2,6-二氨基-3,5-二硝基-1-氧吡嗪(LLM-105)。 典型条件为：底物10 mmol,CH3CN 30 mL,催化剂Fe3O4/CS/HWO 0.1 g(约0.1 mmol),60 ℃分5次逐滴加入30%双氧水5 mL。 反应混合物溶液经萃取和柱色谱法提纯,得产物,收率一般为60%~73%。 使用高斯03量化计算程序对氧化过程进行了理论计算,结果与实验数据相符。     

新型[(吡嗪-3-基)甲氧基]芳酸衍生物的合成及其抗血小板聚集活性

以具有活血化瘀作用的中药有效成分阿魏酸为先导物，利用基于受体结构的理性药物设计方法，设计并合成了6个新化合物[(吡嗪-3-基)甲氧基]芳酸衍生物（6a~6f）。以2-甲基吡嗪和不同取代的芳香酸甲酯为起始原料，经自由基卤代反应、醚化反应和水解反应合成6a~6f，其结构经¹H NMR， ¹³C NMR， IR和MS表征。体外药效筛选结果显示：6a~6f具有明显的抗血小板聚集活性，其中(E)-3-甲氧基-4-(吡嗪-2-甲氧基) 苯丙烯酸(6a)和3-(2-吡嗪甲氧基)-4-甲氧基-苯甲酸(6e)的活性优于奥扎格雷和阿魏酸。(E)-3-甲氧基-4-(吡嗪-2-甲氧基)-苯丙烯酸(6a)的抗血小板聚集活性，优于化合物(E)-3-(4-(吡啶-3-基)甲氧基)-3-甲氧基苯基)丙烯酸。     

电化学合成乙酰基吡嗪北大核心CSCD

本文以吡嗪和丙酮酸为原料,在铅电极上电化学活化过硫酸铵得到的硫酸根自由基为氧化剂,首次采用电化学方法合成了乙酰基吡嗪。探究了电流密度、反应物摩尔比、反应物浓度、过硫酸铵、pH值对乙酰基吡嗪收率的影响,同时在外加硫酸亚铁的条件下探究复合活化法对收率的影响。在最优条件下(电流密度100 A·m^(-2),丙酮酸浓度0.33 mol·L^(-1),吡嗪浓度1.00 mol·L^(-1)),该反应的收率为44.12%。该工艺反应条件温和,简单易控,利用“清洁能源”电子代替了过渡金属盐以活化过硫酸铵,因而是一种环境友好的乙酰基吡嗪制备方法,具有广阔的工业化应用前景。     

柱前衍生-高效液相色谱法测定2,3-吡嗪二羧酸酐有关物质的含量北大核心CSCD

由于原料药2,3-吡嗪二羧酸酐易水解为有关物质2,3-吡嗪二羧酸,不能直接用高效液相色谱法测定.基于此,以甲醇衍生化2,3-吡嗪二羧酸酐后再采用高效液相色谱法测定2,3-吡嗪二羧酸酐中主成分和杂质2,3-吡嗪二羧酸、2-吡嗪甲酸的含量.按照质量体积比(mg∶mL)10∶7加入供试品和甲醇,超声衍生20 min,稀释后用高效液相色谱法分析.以YMC Triart C_(18)色谱柱为固定相,以不同体积比的0.5%(体积分数)三氟乙酸溶液和甲醇的混合溶液进行梯度洗脱,在270 nm处检测.结果显示:2,3-吡嗪二羧酸、2-吡嗪甲酸、2,3-吡嗪二羧酸酐之间的分离度均大于1.5,其质量浓度均在一定范围内与其对应的峰面积呈线性关系,检出限分别为0.0575,0.0548,0.0102 mg·L^(-1);对混合对照品溶液和供试品溶液连续分析6次,测定值的相对标准偏差均小于2.0%;2,3-吡嗪二羧酸、2-吡嗪甲酸的加标回收率分别为95.2%,98.3%;方法用于3批实际样品的分析,检出的2,3-吡嗪二羧酸酐的质量分数为97.83%~97.93%,2,3-吡嗪二羧酸的质量分数为2.07%~2.17%,而2-吡嗪甲酸未检出.     

单缩和双缩二氨基硫脲类化合物的合成与表征

合成了2乙酰基吡嗪单缩二氨基硫脲(1)、2乙酰基吡嗪缩二氨基硫脲缩5溴水杨醛(2a)、2乙酰基吡嗪缩二氨基硫脲缩5氯水杨醛(2b)、2乙酰基吡嗪缩二氨基硫脲缩5硝基水杨醛(2c)四种化合物,并通过红外光谱、核磁共振、质谱、元素分析等进行了结构表征。化合物1形成的晶体为单斜晶系,具有C2c空间群。a=2.3057(14)nm,b=0.7297(4)nm,c=1.1940(7)nm,V=1.909(2)nm3,Z=8,Dc=1.463gcm3,μ=0.309mm-1,F(000)=880,R1=0.0866,wR2=0.2072。     

一种2-乙酰基吡嗪-罗丹明B衍生物的合成及其对Ni~(2+)的识别

分子光谱法具有灵敏度高、操作简单等优点,发展简便、快捷、对镍离子(Ni~(2+))具有高度选择性的探针具有非常重要的意义。本文以金属离子诱导罗丹明酰胺衍生物反应开环的策略,设计并合成了对Ni~(2+)检测具有单一选择性识别的紫外吸收探针。同时,该探针可对水溶液中的Ni~(2+)实现"裸眼"识别。此外,该探针对Ni~(2+)具有较高的灵敏度,其对水溶液中Ni~(2+)的检测限为0.5μmol/L,表明该探针可用于Ni~(2+)的检测分析。     

Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(2)·2H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(3))(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO(2)] moieties connected by [CH(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO(3)(CH(3)SO(3)) (P1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2)°, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO(2)]-O-[ReO(2)]-O chains is formed. Each [ReO(2)]-O-[ReO(2)] unit is coordinated by two bidentate [CH(3)SO(3)] ions. V(2)O(3)(CH(3)SO(3))(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(3)] groups along [001]. Thermal decomposition of the compounds was monitored under N(2) and O(2) atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N(2) the decomposition proceeds with reduction of the metal leading to the oxides MoO(2), U(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(3))(2), a small amount of MoS(2) is formed. If the thermal decomposition is carried out in a atmosphere of O(2) the oxides MoO(3) and V(2)O(5) are formed.     

Novel neutral hexacoordinate benzamidinatosilicon(IV) complexes with SiN3OF2, SiN3OCl2, SiN3OBr2, SiN5O and SiN3O3 skeletons

The neutral pentacoordinate monoamidinatosilicon(IV) complex 1 (SiN(2)Cl(3) skeleton) and the neutral hexacoordinate monoamidinatosilicon(IV) complexes 2-9 (SiN(3)OF(2), SiN(3)OCl(2), SiN(3)OBr(2), SiN(5)O and SiN(3)O(3) skeletons) were synthesised and characterised by elemental analyses, single-crystal X-ray diffraction (except for 1) and NMR spectroscopy in the solid state and in solution. Compounds 2-9 contain one bidentate monoanionic N,N'-diisopropylbenzamidinato ligand, one bidentate monoanionic ligand derived from 8-hydroxyquinoline and (i) two identical monoanionic ligands (F, Cl, Br, N(3), NCO, NCS, OSO(2)CF(3)) or (ii) one bidentate dianionic benzene-1,2-diolato ligand. The dynamic behavior of 2-4 (SiN(3)OX(2) skeleton; X = F, Cl, Br) and 9 (SiN(3)O(3)) in solution was studied by multinuclear variable-temperature NMR experiments. Compound 1 was synthesised by reaction of SiCl(4) with the corresponding lithium amidinate, and compound 2 was obtained by reaction of 1 with 8-hydroxyquinoline and triethylamine. Compound 2 served as the starting material in the syntheses of 3-9, in which the two chloro ligands of 2 were substituted by two identical (pseudo)halogeno ligands, two trifluoromethanesulfonato ligands or one benzene-1,2-diolato ligand. Compounds 3 and 4 contain the novel SiN(3)OBr(2) and SiN(3)OF(2) skeletons, while compounds 5-7 are the first neutral hexacoordinate silicon(IV) complexes with an SiN(5)O skeleton.     

Diorganotin(IV) complexes with 2-benzoylpyridine and 2-acetylpyrazine N(4)-phenylthiosemicarbazones: Synthesis, crystal structures and biological activities

Four diorganotin(IV) complexes [(Me)₂Sn(L¹)(CH₃COO)]·CH₃CH₂OH (1), [(Ph)₂Sn(L¹)(CH₃COO)]·CH₃CH₂OH (2), [(Me)₂Sn(L²)Cl] (3) and [(Ph)₂Sn(L²)(CH₃COO)] (4) where HL¹ = 2-benzoylpyridine N(4)-phenylthiosemicarbazone and HL² = 2-acetylpyrazine N(4)-phenylthiosemicarbazone have been synthesized and characterized by elemental analysis, IR MS, ¹H NMR and single-crystal X-ray diffraction studies. Schiff bases in their deprotonated forms coordinate to tin(IV) via pyridine/pyrazine nitrogen atom and the nitrogen atom and sulfur atoms of the thiosemicarbazone moiety. The tin atom is seven-coordinated in 1, 2 and 4 containing one acetato group, respectively, and six-coordinated in 3 containing one chloride ion. Biological studies, carried out in vitro against selected bacteria and K562 leukaemia cells, respectively, have shown that different substituted groups attached at the thiosemicarbazone moieties and different diorganotin(IV) groups showed distinctive differences in the biological property.     

2-乙氧羰基-3-甲基-4,5-四亚甲基吡咯的合成

以乙酰乙酸乙酯(1)为原料,在醋酸中与亚硝酸钠通过肟化反应制得N-羟基亚胺乙酰乙酸乙酯(2);2在醋酸缓冲溶液中经锌粉还原后与环己酮加成环化合成了2-乙氧羰基-3-甲基-4,5-四亚甲基吡咯(3),其结构经1H NMR,IR和元素分析表征。较适宜的反应条件为:1100 mmol,n(Zn)∶n(1)=2.9∶1.0,在醋酸中回流反应,总收率39%;以多步反应的最佳反应条件进行"一锅煮"合成3,收率50%。     

3-乙基-2-乙酰吡嗪缩N(4)-(对甲苯)氨基硫脲Ga(Ⅲ)、In(Ⅲ)配合物的合成、晶体结构和DNA结合性质

以3-乙基-2-乙酰吡嗪N（4）-（对甲苯）氨基硫脲（HL）为原料,合成了[Ga（L）₂]NO₃·4CH₃OH（1）和[In（L）₂]NO₃·1.75CH₃OH（2）两种新型配合物,并进行了X射线衍射分析表征。结果表明,配合物1和配合物2同构但具有不同数目的结晶甲醇分子。每个配合物的金属中心被2个拥有[N₂S]供体的配体阴离子包围,采取扭曲的八面体配位几何。此外,荧光光谱表明配合物与DNA的相互作用强于配体。     

The butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 and its oxidative cleavage to (tBu3SiO)2Cr(=N-N=CPh2)2 and (tBu3SiO)2Cr=N(2,6-Ph2-C6H3)

Treatment of CrCl2(THF)2 with NaOSitBu3 afforded the butterfly dimer [(tBu3SiO)Cr]2(mu-OSitBu3)2 (1(2)), whose d(CrCr) of 2.658(31) A and magnetism were indicative of strong antiferromagnetic coupling. A Boltzmann distribution of low-energy 1A1, 3B1, 5A1, 7B1, and 9A1 states obtained from calculations on [(HO)2Cr]2(muOH)2 (1'(2)) were used to provide a reasonable fit of the mu(eff) vs T data. Cleavage of 1(2) with various L (L = 4-picoline, p-tolunitrile, tBuCN, tBuNC, Ph2CO, and PMe3) generated (tBu3SiO)2CrL2 (1-L2). The dimer was oxidatively severed by Ph2CN2 to give (tBu3SiO)2Cr(N2CPh2)2 (2) and by RN3 at 23 degrees C to afford (silox)2Cr=NR (3-R) for bulky R (adamantyl (Ad), 2,6-iPr2-C6H3, 2,4,6-Me3-C6H2 = Mes, 2,6-Ph2-C6H3) and (tBu3SiO)2Cr(=NR)2 (4-R) for smaller substituents (R = 1-Naph, 2-Anth). X-ray structural studies were conducted on 1(2), square planar 1-(OCPh2)2, pseudo-Td 2 and pseudo-trigonal 3-(2,6-Ph2-C6H3), whose S = 1 ground state was discussed on the basis of calculations of (H3SiO)2Cr=NPh (3' '-Ph).     

Syntheses and Characterizations of （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 and （NH3CH2CH2NH3）2Bi2I10

The title compounds have been respectively synthesized by solution process and solvothermal reaction, and their crystal structures were determined by X-ray diffraction method. For （CH3CH2CH2CH2NH3）6（BiI6）（I）2I3 1, it crystallizes in tficlinic, space group P1^- with Mr = 2049.76, a = 8.5719（1）, b = 11.7461（3）, c = 15.700（1）A, V = 1451.4（1）A^3, Z = 1, Dc = 2.345 g/cm^3, F（000） = 924, μ（MoKα） = 8.907 mm^-1, T = 293（2） K, the final R = 0.0655 and wR = 0.0804 for 2399 observed reflections with I 〉 2σ（I）. For （NH3CH2CH2NH3）2Bi2I10 2, it crystallizes in monoclinic, space group P21/n with Mr= 1811.20, a = 8.434（4）, b = 13.862（6）, c = 13.362（6）A, V = 1499.9（12）A^3, Z = 2, Dc = 4.010 g/cm^3, F（000） = 1536,μ（MoKα） = 22.007 mm^-1, T = 293（2） K, the final R = 0.0584 and wR = 0.1451 for 1798 observed reflections with I 〉 2σ（I）. The structures of 1 and 2 contain halobismuthate monomer and dimers, respectively. It is noteworthy that the dimers and their organic counters in 2 connect each other by N…I hydrogen bonds to form a layered structure, and the electrostatic interactions and crystal packing forces between layers give rise to the packing of the crystal. The optical absorption spectra of 1 and 2 reveal the appearance of sharp optical gaps of 2.13 and 2.01 eV, respectively.     

3-亚甲基六氢苯并呋喃-2(3H)-酮的简便合成

以氧化环己烯为原料,在正丁基锂作用下与乙腈经开环反应制得2-羟基环己基乙腈(2);2依次经水解、内酯化、二甲胺甲基化、甲基化和Hofmann降解反应合成了α-亚甲基-γ-丁内酯类化合物--3-亚甲基六氢苯并呋喃-2(3H)-酮,总收率30.4%,其结构经¹H NMR,¹³C NMR和HR-MS(EI)确证。     

七配位二聚体配合物{(PhCH2)2Sn·[2,6-(O2C)2C5H3N](CH3OH)}2的合成及结构

在三乙胺存在下利用三苄基氯化锡和2,6-吡啶二甲酸,以1:1摩尔比反应,合成了七配位二聚体{(PhCH2)2Sn[2,6-(O2C)2C5H3N](CH3OH)}2.通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征.用X射线单晶衍射法测定了该化合物的晶体结构.化合物为三斜晶系,P1空间群,晶胞参数a=0.9625(6)nm,b=1.0947(9)nm,c=1.996(3)nm,α=90.00(2)°,β=87.69(3)°,γ=90.00(3)°,Z=2,V=2.102(6)nm3,μ=1.248mm-1,F(000)=1000,R1=0.0476,wR2=0.0782.化合物中2个锡原子呈七配位畸变五角双锥构型.生物活性测试结果表明,该化合物具有较强的体外抗肿瘤活性.