4-溴-5-甲基靛红的Baeyer-Villiger氧化反应

Baeyer-Viliger反应是由酮制备酯的重要方法^[1].氧化剂通常有两类:(1)有机过酸;(2)过硫酸钾/硫酸(Caro酸).由于靛红结构特殊,我们分别以单过邻苯二甲酸^[2]和过硫酸钾/硫酸^[3]为氧化剂氧化4-溴-5-甲基靛红(1).     

meso-四-(3-N-甲基吡啶)卟啉与钴反应的分光光度研究

水溶性卟啉衍生物作为光度试剂在分析化学中已得到广泛的应用。在测定某些过渡金属元素时具有极高的灵敏度(ε值为2-5×10⁵)^[1]。meso-四-(3-N-甲基吡啶)卟啉[T(3-MPy)P]与铜^[2]、锌^[3]、铅^[4]的反应都已进行研究。本文对T(3-MPy)P与钴的反应进行了初步的研究。T(3-MPy)P的结构如右图。     

吸收液采样-高效液相色谱法测定室内空气中甲醛的含量

<正>甲醛是一种无色有刺激性气味的气体，被世界卫生组织(WHO)定为致畸和致癌的物质之一^[1]。我国规定室内空气甲醛的限值为0.10 mg·m-3^[2]。目前监测环境中甲醛的国家标准测定方法很多^[3],常用的有4-氨基-3-联氨-5-巯基-1,2,4-三氮杂茂(Ⅰ)(AHMT)分光光度法^[4]、3-甲基-2-苯并噻唑啉酮腙盐酸盐水合物(MBTH)酚试剂分光光度法^[5]、乙酰丙酮分光光度法^[6]、气相色谱法(GC)^[7]、     

杂环光化学Ⅴ.烯类与1,3-二甲基-6-氮杂胸腺嘧啶的光环合加成反应

1974年Sweeton等人首先报道了这一反应^[1]。1981年樊美公等报道了1,3-二甲基-6-氮杂胸腺嘧啶(A)与庚烯-1的反应^[2],1986年又相继报道了含有极性基团的烯类与A的反应。本文通过这类反应合成了新化合物:1,2,4-三氮杂-2,4,6,7-四甲基-3,5-二氧-8-正丁基双环[4,2,0]辛烷(Ⅰ)和1,2,4-三氮杂-2,4,6-三甲基-3,5-二氧叁环[6,4,0,0^7,12]十二烷甲基衍生物(Ⅱ)。     

一系列Ru(II)配合物电致化学发光性质的比较研究

比较研究了以C₂O₄^2－为共反应物时5个结构相关的Ru(II)配合物[Ru(bpy)₂L¹]^2＋, [Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋, [Ru(phen)₂L¹]^2＋和[Ru(phen)₂L²]^2＋(其中bpy＝2,2′-联吡啶, phen＝1,10-邻菲啰啉, L¹＝4-羧基苯基咪唑[4,5-f][1,10]邻菲啰啉, L²＝3-羧基-4-羟基苯基咪唑[4,5-f][1,10]邻菲啰啉, L³＝3,4-二羟基苯基咪唑[4,5-f][1,10]邻菲啰啉)的电致化学发光(ECL)性质. 结果表明, 酚羟基的存在能有效地淬灭Ru(II)配合物[Ru(bpy)₂L²]^2＋, [Ru(bpy)₂L³]^2＋和[Ru(phen)₂L²]^2＋的ECL, 其它Ru(II)配合物的ECL量子效率与[Ru(bpy)₃]^2＋相差不大.     

4-甲酰基4-苯乙烯基吡啶分子聚集行为的光谱研究

苯乙烯基吡啶化合物,由于它可能在医学方面^[1]和光电子功能材料^[2]方面有实际应用前景,已引起人们的兴趣。苯乙烯吡啶化合物的光化学性质类似于二苯乙烯化合物,在光照下可以发生顺-反异构反应^[3]、加成反应和二聚反应^[4]等不同的光化学反应。     

碱金属离子与三肽复合物的气相裂解反应

为了探索侧链R基团对碱金属离子与多肽复合物气相裂解反应的影响, 采用电喷雾电离质谱法研究了碱金属离子Li⁺, Na⁺和K⁺分别与甘氨酸三肽(GGG)、 甘氨酰-苯丙氨酰-甘氨酸三肽(GFG)和甘氨酰-甘氨酰-苯丙氨酸三肽(GGF)形成的复合物的气相裂解反应. 质谱定性实验结果表明, Li⁺, Na⁺和K⁺与GGG, GFG或GGF在气相中可以形成稳定的复合物, 配合比为1∶1或2∶1. 竞争反应质谱图显示, GGG, GFG或GGF与碱金属离子形成的复合物的质谱峰丰度按Li⁺, Na⁺, K⁺顺序依次下降, 表明随着碱金属离子半径的增加, 它们与三肽的结合强度依次减弱. 碰撞诱导解离显示, 母体离子[GGG+Na]⁺, [GGF+Na]⁺和[GFG+Na]⁺ 的质心碰撞能量E(CM)₅₀数值分别为1.94, 1.76和1.63 eV. 通过质谱滴定法测得[GGG+Na]⁺, [GFG+ Na]⁺和[GGF+Na]⁺ 的结合常数lg\begin{array}{c}{K}_{a_1}\end{array}分别为5.30, 5.25和5.17. 质谱法定量结果进一步确认复合物的稳定性顺序为[GGG+Na]⁺>[GGF+Na]⁺>[GFG+Na]⁺, 表明由于空间位阻的影响, 侧链R基团含有苄基的GFG或 GGF与Na⁺的键合强度要小于侧链R全部为H的GGG. 串级质谱分析结果显示, 碱金属化的GGG断裂位点较多, 可解离出丰富的金属化a₂, b和y型碎片离子, 而碱金属化的GGF和GFG解离出的金属化y型离子较多, b型离子其次, 金属化a型离子几乎没有. 此外, 双碱金属化的GGF可解离出较多金属化y型离子. 复合物[GGF+Na]⁺的裂解曲线显示, 当碰撞能量为25 eV时, [y₂+Na-H]⁺ 和[b₂+Na+OH]⁺为主要碎片离子, 当碰撞能量>40 eV时, 只有[b₂+Na+OH]⁺ 碎片离子占有优势数量. 根据质子化三肽裂解机理可以推测, 钠化GFG裂解后生成含噁唑酮的[b₂+Na]⁺离子, 该离子经过一系列过渡态生成[a₂+Na]⁺(2-苄基-4-咪唑酮), 而不是常见的亚胺离子.     

α-甲氧基萘的电子转移光氧化反应

近年来芳烃和杂环化合物的电子转移光氧化反应受到日益的注意^[1-5]。电子转移光氧化反应不仅可应用于很多对¹O₂为惰性的烯烃和芳烃^[1-7],而且对某些¹O₂活性化合物,也可给出与¹O₂反应不同的产物。     

均相时间分辨免疫分析铕穴状螯合剂的合成

以2,6-二（溴甲基）吡啶-3,5-二甲酸二乙酯为起始原料,经溴化、取代、加成及酸化反应合成了两种铕穴状荧光螯合剂Eu³⁺ 2,6-{N,N′,N,N′-[二（2,2′-联吡啶-6,6′-二甲基）]二（氨甲基）}-吡啶-二羧酸[Eu³⁺ bpy.bpy.py(CO₂H)₂, 1]和Eu³⁺2,6-{N,N′,N,N′-[二（2,2′ 联吡啶-6,6′-二甲基）]二（氨甲基）}-吡啶-二[N-(2-氨基乙基)酰胺]{Eu³⁺bpy.bpy.py[CONH(CH₂)₂NH₂]₂, 2},其结构和性能经¹H NMR, MS(ESI)和荧光光谱表征。结果表明：1的最佳激发波长为312 nm,发射特征峰位于598和615 nm,荧光寿命为1 064 μs,量子产量为10%。 2的最佳激发波长为311 nm,发射特征峰位于597和616 nm,荧光寿命为398 μs,量子产率为12.1%。     

含噁二唑大环冠醚的合成、 结构及金属离子识别性能

合成了含有1,3,4-噁二唑基团的大环冠醚: 2,3,11,12-二苯并-4,7,10,16-四氧-14,15-二氮杂双环[11.2.1]-十六烷-13,15-二烯(2)、 2,3,14,15-二苯并-4,7,10,13,19-五氧-17,18-二氮杂双环[14.2.1]-十九烷-16,18-二烯(3)和2,3,17,18-二苯并-4,7,10,13,16,22-六氧-20,21-二氮杂双环[17.2.1]-二十二烷-19,21-二烯(4), 并培养得到其单晶; 通过核磁共振波谱、 高分辨质谱及X射线单晶衍射对其结构进行了表征. 结果表明, 冠醚2属正交晶系, Pna2₁空间群; 冠醚3属于单斜晶系, C2/c空间群; 冠醚4属正交晶系, Pbca空间群. 在3个主体化合物中均存在分子间氢键和π-π相互作用将分子连接成三维空间结构. 采用荧光光谱测定了开链冠醚2,5-二[2-(2-甲氧乙氧基)苯基]-1,3,4-噁二唑(1)和不同环空腔大小的噁二唑冠醚(2~4)对金属离子Li ⁺, Na ⁺, K ⁺, Rb ⁺, Mg ²⁺和Ca ²⁺的键合行为. 研究结果表明, 开链冠醚1和冠醚4对碱土金属Mg ²⁺和Ca ²⁺表现出荧光猝灭行为, 且对Ca ²⁺表现出良好的键合能力和选择性; 而冠醚2对Na ⁺和K ⁺表现出良好的键合能力, 但其Na ⁺/K ⁺的选择性较差.     

Nitrogen bridgehead compounds,part 68. Studies on quinolizine derivatives. Part 2. Synthesis of 1,3-disubstituted-4H-quinolizine derivatives

Quinolizine compounds 1 and 2 or their monocyclic tautomers 3 and 4 have been synthesized using 2-pyri-dineacetic acid derivatives 6a, b, A, B and ethoxymethylenemalonic acid derivatives 7a, b, c in base catalyzed or thermic reaction. In the 6-unsubstituted series, both the 4-oxo and 4-imino derivatives could have been obtained, in the 6-substituted series, however the 4-oxo ones only, whereas instead of the 4-imino derivatives, their monocyclic tautomers 3, 4 have been isolated. In the 6-unsubstituted series, the primarily formed 4-imino compounds have been rearranged into 4-oxo ones under stronger conditions. The structure of the isolated compounds have been proved by ultraviolet, infrared and ¹H nmr spectra, that of 3B=C by X-ray analysis as well.     

Synthesis and characterization of high nuclearity iron(III) phosphonate molecular clusters

Three new phosphonic acid ligands (4- (t)butylphenyl phosphonic acid, 3,5-dimethylphenyl phosphonic acid, and diphenylmethylphosphonic acid) have been synthesized and employed in search of high molecularity iron(III) clusters. The cluster compounds are characterized by single crystal X-ray diffraction and magnetic measurements. The solvothermal reaction of FeCl 3.6H 2O with diphenylacetic acid and p- (t)butylphenyl phosphonic acid resulted in an unprecedented dodecanuclear cluster [Fe 12(mu 2-O) 4(mu 3-O) 4(O 2CCHPh 2) 14(4- (t)buPhPO 3H) 6]( 1) having a double butterfly like core structure. [Fe 12(mu 2-O) 4(mu 3-O) 4(O 2CPh) 14(C 10H 17PO 3H) 6]( 2), another dodecanuclear cluster having core structure similar to 1, has been synthesized in a reaction between [Fe 3O(O 2CPh) 6(H 2O) 3]Cl and camphylphosphonic acid in the presence of triethylamine at ambient condition. 3,5-Dimethylphenyl phosphonic acid on reacting solvothermally with an oxo-centered iron triangle [Fe 3O(O 2CCMe 3) 6(H 2O) 3]Cl gives a nonanuclear cluster [Fe 9(mu 3-O) 4(O 3PPh(Me) 2) 3(O 2CCMe 3) 13]( 3) having icosahedral type core structure where three positions of the iron atoms have been replaced by phosphorus. Another nonanuclear [Fe 9(O) 3(OH) 3(O 3PCHPh 2) 6(O 2CCMe 3) 6(H 2O) 9] ( 4), having a distorted cylindrical core structure, has been synthesized in a similar solvothermal reaction between [Fe 3O(O 2CCMe 3) 6(H 2O) 3]Cl and biphenylmethyl phosphonic acid. All compounds are characterized by IR spectra, elemental analysis, as well as single crystal X-ray analysis. Magnetic measurements for all the compounds reveal that there are antiferromagnetic interactions between the metal centers.     

Synthesis of the metabolites of oxapadol,a new non-narcotic analgesic agent

Different metabolites (2-7) of oxapadol 1 were carried out from 3 by known methods. Their acidic hydrolysis provided compounds 4 in which the dioxolane moiety was opened. The reaction of glycerol with compounds 3 gave the dioxolane derivatives 5 which have a hydroxymethyl group and which (R = H) gave by oxidation the carboxylic acid 7. From 3 (R = H), the hydroxy acid 6 has been also prepared.     

用色谱-质谱和质量色谱研究苯甲酸钐热分解反应

为合成某些芳香族有机化合物提供一种新途径，用色谱－质谱联用技术和质量色谱法研究了苯甲酸钐的热分解反应产物。其热分解产物溶入丙酮后有大量９，１０－蒽醌析出，其丙酮溶液中还含有１，２－二苯甲酰基苯（２５６％）、苯甲酸（１８７％）、二苯酮（１４４％）、９－芴酮（８２％）、９－苯基芴（４９％）、联苯（３６％）、二苯甲烷（２３％）、３－甲酰苯基联苯（２１％）、二苯基乙二酮（１９％）、４－甲酰苯基联苯（１８％）、芴（１７％）、ｍ－二苯甲酰基苯（１１％）和ｐ－二苯甲酰基苯（０２％）等５５种化合物。讨论了苯甲酸盐的热分解反应机理。     

3-(N-取代苯基-2-乙酰胺基)硫基-4-N-取代邻羟苯基亚胺基-5-甲基-1,2,4-三唑类化合物的合成及生物活性研究

以对称二氨基硫脲为原料,与冰醋酸反应生成5-甲基-4-氨基-1,2,4-三唑-3-硫酮(1);在弱酸性条件下,1与取代水杨醛反应生成席夫碱中间体5-甲基-4-(N-取代邻羟苯基)亚胺基-1,2,4-三唑-3-硫酮(2a～2c);最后在碱性条件下分别与N-取代苯基-2-氯乙酰胺发生烷基化反应生成15种未见报道的目标化合物3-(N-取代苯基-2-乙酰胺基)硫基-4-(N-取代邻羟苯基)亚胺基-5-甲基-1,2,4-三唑(3a～3o),其结构经IR,1H NMR,13C NMR确证.初步生物测试表明,质量分数为0.01%时,3a～3o对白色念珠菌的抑菌率均达90%以上,具有很强的抑菌活性;对金黄色葡萄球菌、大肠杆菌的抑菌率达80%以上,具有较强的抑菌活性.     

Organostannoxane-supported multiferrocenyl assemblies: synthesis, novel supramolecular structures, and electrochemistry

Organostannoxane-based multiredox assemblies containing ferrocenyl peripheries have been readily synthesized by a simple one-pot synthesis, either by a solution method or by room-temperature solid-state synthesis, in nearly quantitative yields. The number of ferrocenyl units in the multiredox assembly is readily varied by stoichiometric control as well as by the choice of the organotin precursors. Thus, the reaction of the diorganotin oxides, R2SnO (R = Ph, nBu and tBu) with ferrocene carboxylic acid affords tetra-, di-, and mononuclear derivatives [{Ph2Sn[OC(O)Fc]2}2] (1), [{[nBu2SnOC(O)Fc]2O}2] (2), [nBu2Sn{OC(O)Fc}2] (3), [{tBu2Sn(OH)OC(O)Fc}2] (4), and [tBu2Sn{OC(O)Fc}2] (5) (Fc = eta(5)C5H4-Fe-eta(5)C5H5). The reaction of triorganotin oxides, R3SnOSnR3 (R = nBu and Ph) with ferrocene carboxylic acid leads to the formation of the mono-nuclear derivatives [Ph3SnOC(O)Fc] (6) and [{nBu3SnOC(O)Fc}(n)] (7). Molecular structures of the compounds 1-4 and 6 have been determined by single-crystal X-ray analysis. The molecular structure of compound 1 is new among organotin carboxylates. In this compound, ferrocenyl carboxylates are involved in both chelating and bridging coordination modes to the tin atoms to form an eight-membered cyclic structure. In all of these compounds, the acidic protons of the cyclopentadienyl groups are hydrogen bonded to the carboxylate oxygens (C-HO) to form rich supramolecular assemblies. In addition to this, pi-pi, T-shaped, L-shaped, and side-to-face stacking interactions involving ferrocenyl groups also occur. Compound 6 shows an interesting and novel intermolecular CO2-pi stacking interaction. Electrochemical analysis of the compounds 1-4, 6, and 7 shows a single, quasi-reversible oxidation peak corresponding to the simultaneous oxidation of four, two, and one ferrocenyl substituents, respectively. Compound 5 shows two quasi-reversible oxidation peaks. This is attributed to the positional difference among the ferrocenyl substituents on the tin atom. Additionally, while compounds 2 and 4 are electrochemically quite robust and do not decompose even after ten continuous CV cycles, compounds 1, and 3, 5-7 start to show decomposition after five cycles.     

计算机辅助设计新型人脂肪酸合酶抑制剂及其抗肿瘤活性

以Orlistat为先导化合物,利用AutoDock进行计算机模拟对接,在对接结果中选择能量较低的6个结构进行合成与抗肿瘤活性筛选。以orlistat为原料,经2步反应制得苄基(2S,3S,5S)-2-己基-3,5-二羟基十六酸酯(2); 再经4步反应获得(3S,4S)-3-己基-4-［(S)-2-羟基十三烷基］氧杂环丁烷-2-酮(5); 5在EDCI作用下与酸经缩合反应合成了4个计新型人脂肪酸合酶抑制剂（6a~6d）,其中6b~6d为新化合物,其结构经¹H NMR, ¹³C NMR 和HR-MS（ESI）表征。体外初步活性测试表明：(S)-1-［(1S,2S)-3-己基-4-氧代氧杂环丁烷-2-基］十三烷-2-烟酸酯（6a）对MDA-MB-231细胞有较好的抑制作用,其IC₅₀为11.72 μmol·mL^-1,优于Orlistat(21.5 μmol·mL^-1)。     

S-烃基-1-烃基-3-[4-(苯并咪唑-2-巯基)苯基]异硫脲的合成及其iNOS抑制活性

以2-巯基苯并咪唑(1)为原料,经缩合和还原得到2-(4-氨基苯硫基)苯并咪唑(3),再与异硫氰酸苯甲酰酯或异硫氰酸烃基酯反应得到取代硫脲(5和7),最后与卤代烃反应得到20个新的S-烃基-1-烃基-3-[4-(苯并咪唑-2-巯基)苯基]异硫脲化合物(6和8),其结构经IR,¹HNMR,MS及元素分析确证.初步的药理试验表明,20个目标化合物均有不同程度的iNOS抑制活性,其中化合物6b,8d和8f的iNOS抑制活性与阳性对照药氨基胍相当.     

Comparative study on the preparation of C(3)-hydroxy-1,3-dihydro-2H-1,4-benzodiazepin-2-ones

C(3)-Hydroxy-1,4-benzodiazepin-2-ones 1–3 have been prepared in high yields using a new, two step approach. In the first step, the 3-deoxy-precursors 4–6 were acetylated at C(3) using the redox-system lead tetraacetate and iodine, or potassium iodide, in acetic acid. The intermediary acetates 9–11 were quantitatively hydrolyzed into 1–3 in non-aqueous conditions, i.e. in a methanol-methylene chloride solvent mixture in the presence of sodium methoxide. Another route to the title compounds has been improved as follows. The yields of C(3)-bromination of compounds 4–6 has been significantly augmented in relation to the known methods using the strong trifluoroacetic acid in very dilute carbon tetrachloride solutions as a catalyst for NBS mediated bromination. The intermediary C(3)-bromo derivatives have been acetoxylated in situ, and compounds 9–11 have been isolated in over 80% yield. These compounds were solvolyzed into 1–3 as described above. The third part of this paper describes the search for feasible reaction conditions in the synthesis of 3 according to a known method (Scheme 1.); optimization of the yields in all steps was performed.     

Structural motifs in (t-butoxy) zirconium phosphinates,arsinates, and phosphates

Reaction of zirconium tetrakis(tert-butoxide) (1) with dicylohexylphosphinic acid in toluene leads to the dinuclear compound [Zr(mu,mu'-O(2)P(cycl-C(6)H(11))(2))(O-t-Bu)(3)](2) (2) in which the zirconium is pentacoordinated. An analogous reaction using diphenylphosphinic acid in tetrahydrofuran also leads to a dinuclear complex [Zr(mu,mu'-O(2)PPh(2))(THF)((O-t-Bu)(3)](2).C(6)H(5)CH(3) (3.C(6)H(5)CH(3)), in which zirconium is hexacoordinated. A novel exchange of tert-butoxy and phenoxy groups occurs when 1 is treated with diphenyl phosphate [(PhO)(2)PO(2)H] leading to the isolation of the exchange product [Zr(mu,mu'-O(2)P(O-t-Bu)(OPh))(mu-OPh)(O-t-Bu)(2)](2) (4). In contrast to the above, trinuclear zirconium compounds Zr(3(mu,mu'-O(2)AsMe(2))(2)(mu2,mu'-O(2)AsMe(2))(O-t-Bu)(7)(mu-O-t-Bu)(2) (5) and Zr(3(mu,mu'-O(2)P(O-t-Bu)(2))(5)(O-t-Bu)(7).(1)/(2)C(6)H(5)CH(3) (6.(1)/(2)C(6)H(5)CH(3)) have been isolated from the reaction of 1 with cacodylic acid and di-tert-butyl phosphate, respectively. The X-ray structures of 2, 3, 5, and 6 have been determined; although the X-ray structural analysis of 4 could not be satisfactorily finished, it reveals the disposition of the substituents. The solution state NMR data suggest that these compounds undergo structural changes in solution. Possible relationships among the various structures are discussed.