4-氨基安替比林双酰胺化合物的合成

利用4-氨基安替比林分别与2,6-吡啶二甲酰氯或2,5-噻吩二甲酰氯反应,合成了两个新型双酰胺化合物。产物结构通过IR,1H NMR进行表征。最佳反应条件为:反应温度80℃,n(2,6-吡啶二甲酰氯):n(4-氨基安替比林)=1.0:2.4,反应时间2 h,产率82.6%。     

N’-羟基吲哚-3-甲脒类化合物的合成

以取代吲哚为原料,经Vilsmeier-Hacck甲酰化反应在吲哚3位引入甲酰基,再将甲酰基转化为氰基后与羟氨反应得到了一系列N’-羟基-1H-吲哚-3-甲脒类化合物。其中4c,4i未见文献报道,目标产物经过1HNMR,1C-MS确认。研究了温度、溶剂及缚酸剂的碱性对目标化合物合成的影响。     

4-氮杂吲哚-3-羧酸的合成

以丙二酸二乙酯和2-氯-3-硝基吡啶为原料,经亲核取代、脱羧、缩合、环合以及水解等五步反应制备了4-氮杂吲哚-3-羧酸。并对其中影响收率的取代、脱羧和环合三步反应的工艺条件进行了优化,从而得到了一条操作简单、收率高的4-氮杂吲哚-3-竣酸合成工艺路线。     

铜催化的分子内环化合成2,3-二芳基吲哚

吲哚类结构单元广泛存在许多生物活性天然产物及药物分子中，并作为重要的合成砌块在复杂天然产物合成中得到广泛应用，因而高效高选择性地合成吲哚及其衍生物受到了有机合成化学家们关注。阐述在铜与配体、碱的作用下，(E)-2-(2-(亚苄基氨基)苯基)-2-(吡啶-2-基)乙酸甲酯发生分子内环化得到二氢吲哚，再通过脱去一分子甲酸甲酯合成2,3-二芳基吲哚类化合物。该方法能高区域选择性得到2,3-二芳基吲哚，且操作简单、条件温和。     

2,6-二甲基-4-苯基-3,5-吡啶二甲酸的合成

为了制备2,6-二甲基-4-苯基-3,5-吡啶二甲酸,首先采取Hantzsch合成法,以0.10 mol苯甲醛、0.125 mol碳酸氢铵和0.25 mol乙酰乙酸乙酯为原料,在40 mL甲醇溶剂中回流0.5 h,合成了1,4-二氢-2,6-二甲基-4-苯基-3,5-吡啶二甲酸二乙酯,产率为45.9%;取0.01 mol 1,4-二氢-2,6-二甲基-4-苯基-3,5-吡啶二甲酸二乙酯在0.02mmol六水三氯化铁的醋酸水溶液中回流反应1 h进行芳构化合成了2,6-二甲基-4-苯基-3,5-吡啶二甲酸二乙酯,产率为50.2%;最后,2,6-二甲基-4-苯基-3,5-吡啶二甲酸二乙酯进行水解合成目标产物,产率为62.7%。     

2,6-二甲基-4-氨基吡啶的合成研究和表征

2,6-二甲基吡啶为重要的吡啶类起始原料。以2,6-二甲基吡啶为起始原料,经双氧水氧化、混酸硝化、Pd/C-H2还原的方法制备2,6-二甲基-4-氨基吡啶,该合成工艺适合工业化生产。     

新型3-甲基吲哚衍生物的合成

2-甲酰基(乙酰基)-3-甲基吲哚衍生物是合成吲哚取代俘精酸酐类光致变色染料的重要中间体.以3-甲基吲哚为原料,先在NaH存在下,以碘甲烷和2-溴乙基甲基醚为亲电试剂发生Ⅳ-烷基化反应,再通过Vilsmeier-Haack反应在3-甲基吲哚的2位引入甲酰基,制备出两种N-取代基-2-甲酰基-3-甲基吲哚衍生物,产率分别为55％和35％;选择ZnCl2作催化剂,3-甲基吲哚与乙酰氯发生Friedal-Crafts反应选择性生成2-乙酰基-3-甲基吲哚,再发生Ⅳ-烷基化反应,合成一系列N-取代基-2-乙酰基-3-甲基吲哚衍生物,产率为34％～89％.其中4种新化合物的结构经1HNMR、13CNMR、元素分析和MS光谱表征确定.     

N-取代吲哚-3-甲醇的合成

首先由吲哚、三氯氧磷和N,N-二甲基甲酰胺通过Vilsmeier-Haack反应合成吲哚-3-甲醛,产率为97%;进而选择二甲亚砜-氢氧化钠反应体系,室温下由碘甲烷、烯丙基溴、溴化苄和甲苯-4-磺酰氯分别对吲哚-3-甲醛进行N-取代,合成4种N-取代吲哚-3-甲醛——N-甲基吲哚-3-甲醛、N-烯丙基吲哚-3-甲醛、N-苄基吲哚-3-甲醛和N-对甲苯磺酰基吲哚-3-甲醛,产率分别为89%、95%、83%和81%;最后选择硼氢化钠为还原剂,室温下通过还原反应合成吲哚-3-甲醇以及4种N-取代吲哚-3-甲醇——N-甲基吲哚-3-甲醇、N-烯丙基吲哚-3-甲醇、N-苄基吲哚-3-甲醇和N-对甲苯磺酰基吲哚-3-甲醇,产率分别为80%、90%、81%、63%和53%。中间产物及终产物的结构经由1HNMR、IR和元素分析证实。     

(2,6-二氯-5-氟-吡啶-3-羰基)-乙酸乙酯的合成

(2,6-二氯-5-氟-吡啶-3-羰基)-乙酸乙酯是合成沙星类药物和其他喹诺酮类抗菌药的关键中间体。以2,6-二氯-5-氟-吡啶-3-羧酸,二氯亚砜为原料发生亲核取代反应制得2,6-二氯-5-氟-吡啶-3-酰氯;以β二羰基化合物丙二酸二乙酯与乙醇镁反应生成强亲核试剂[C2H(COOC2H5)2]-碳负离子;它再与2,6-二氯-5-氟-吡啶-3-酰氯发生亲核取代反应制得(2,6-二氯-5-氟-吡啶-3-羰基)丙二酸乙酸乙酯;在对甲苯磺酸的作用下经过酯的水解和β-二酸的脱羧得目的产物(2,6-二氯-5-氟-吡啶-3-羰基)-乙酸乙酯。对反应条件进行了改进,选用了比较廉价的原料,并对重结晶试剂进行了深入的筛选,得到具有良好晶形的目的产物。     

自由基酰化反应合成4-氯-2,6-二酰基吡啶

由4-氯吡啶通过自由基酰化反应合成4-氯-2,6-二乙酰基吡啶和4-氯-2,6-二丙酰基吡啶,方法简单,产率较文献方法高,分别达到25.7%和51.7%。     

合成环氧柏木烷的新方法

以三氯化钌和2,6-二羧基吡啶为催化剂,双氧水为氧化剂,对α-柏木烯进行环氧化反应合成环氧柏木烷。本合成方法在国内外尚未见报道。当三氯化钌的用量为1.90%,2,6-二羧基吡啶的用量为12.28%,双氧水的用量为8 倍于α-柏木烯的用量,反应时间为20 h,反应温度为23℃时,环氧柏木烷的得率最高。该方法不仅具有操作简单,反应条件温和的特点,而且实现了α-柏木烯的百分百转化,使目标产物的选择性达到84%以上。     

两个新型联吡啶类化合物的合成以及表征

我们利用固相合成法,氢氧化钠存在的情况下,分别研磨4-乙酰吡啶和对甲基苯甲醛,对甲基苯乙酮和4-吡啶甲醛,然后再利用醋酸铵合环,高锰酸钾氧化,分别得到了两个新型刚性配体名称4'-(4-羧苯基)-2,4':6',4"-三联吡啶(L<,1>)和2,6-二(4-羧苯基)-4,4'-二联吡啶(L<,2>),产率分别为:35.8...     

Synthesis, structure and catalytic activities for the hydrogen transfer reactions of the ruthenium(II) carbonyl chloride complexes with pyridine-2,6-diimine

Two Ru(II) carbonyl chloride complexes with pyridine-2,6-diimine, (L)Ru(CO)Cl₂ (L = 2,6-diacetylpyridinebis(2,4,6-trimethylanil), 1; L = 2,6-diacetylpyridinebis(2,6-diisopropylanil), 2) have been synthesized and characterized. The structure of compound 1 has been determined by X-ray crystallography, which show the distorted octahedral geometry around Ru(II). Complexes 1 and 2 have been proved to be active in the transfer hydrogenation of acetophenone by propan-2-ol.     

4-氨基-3,5-二氯-6-氟吡啶-2-酚的合成及机理探讨

在由3,5-二氯-2,4,6-三氟吡啶经氨取代、羟基取代得到4-氨基-3,5-二氯-6-氟吡啶-2-酚的过程中,我们发现4-氨基-3,5-二氯-2,6-二氟吡啶和2-氨基-3,5-二氯-4,6-二氟吡啶均可以转化为4-氨基-3,5-二氯-6-氟吡啶-2-酚,且收率和产物纯度均较高,我们对机理进行探讨,提出该现象的原因是在碱性水溶液中存在2-羟基吡啶的酮-醇异构互变。     

Obtaining of high surface roughness copper deposits by electroless plating technique

The use of pyridine-2,6-dicarboxylic and 4-hydroxypyridine-2,6-dicarboxylic acids as copper(II) ligands in formaldehyde-containing alkaline electroless copper plating solutions allowed to obtain copper layers with extremely high surface roughness factor reaching approximately 120. The Cu deposits of higher surface area were formed at highly negative open-circuit (mixed) potentials; the correlation between copper electrode overpotential and roughness of the deposit was found and discussed. The copper films obtained demonstrate a high electrocatalytic activity in anodic formaldehyde oxidation process, the oxidation rate reaches 40 mA cm⁻² and exceeds considerably that for other copper surfaces.     

Crystal and molecular structure of copper(II)(pyridine-2,6-dicarboxylato)(2,6-dimethanolpyridine)

Copper(II)(pyridine-2,6-dicarboxylato)(2,6-dimethanolpyridine) has been prepared and studied by the single crystal X-ray diffraction methods at 293(2) K. The compound crystallises in an orthorhombic system, space group Pbcn with a=8.196(2), b=13.124(3), c=25.612(5) Å, and Z=8 (R=0.0374 for 3175 independent reflections with I>2σ(I)). Crystal structure analysis revealed that the copper(II) atom is surrounded by two non-equivalent terdentate ligands making up an ‘all-trans’ elongated octahedral arrangement. In consequence of Jahn–Teller distortion, considerable differences are found between the ligands for the pyridine-2,6-dicarboxylate anion with the values Cu–N 1.892(3), Cu–O 2.033(2) and 2.063(2) Å, while for the 2,6-dimethanolpyridine ligand the values are 1.943(3), 2.341(3) and 2.433(2) Å. There is a relationship between the Cu–L bond distances and the five-membered metallocyclic rings (O–Cu–N). The data are compared and discussed with those found in familiar CuL₂ compounds with the CuO₄N₂ chromophore. Based on the molecular structure, the electronic, IR and EPR spectra are discussed.     

A water-soluble D–π–A chromophore based on dipicolinic acid: Synthesis, pH-dependent spectral properties and two-photon fluorescence cell imaging

The presence of two carboxylic acid groups and two hydroxyl groups within the novel dye, (E)-4-(4-bis(2-hydroxyethyl)amino)styryl)pyridine-2,6-dicarboxylic acid, resulted in good water solubility. The compound's UV absorption and photoluminescence spectra were each highly pH sensitive in acidic solutions and two isobestic points were observed. The TPA cross-section coefficient and two-photon fluorescence cell imaging of the dye were investigated.     

Highly efficient oxidation of diphenylmethane to benzophenone employing a novel ruthenium catalyst with tert-butylhydroperoxide under mild conditions

The ruthenium complex Ru(bpbp)(pydic) (bpbp = 2,6-bis(1-phenylbenzimidazol-2-yl), pydic = pyridine-2,6-dicarboxy acid) has been synthesized and tested in the selective oxidation of diphenylmethane to benzophenone utilizing tert-butylhydroperoxide as the terminal oxidant. The influence of various reaction parameters such as temperature, catalyst amount and nature of solvent on the activity and selectivity was evaluated. Diphenylmethane was converted with 94% conversion and 100% selectivity to benzophenone under the optimized reaction conditions, in which the turnover number (TON) of catalyst reached 94,000. Moreover, a plausible reaction mechanism through redox ruthenium species was proposed.     

A water-soluble D–π–A chromophore based on dipicolinic acid: Synthesis,pH-dependent spectral properties and two-photon fluorescence cell imaging

The presence of two carboxylic acid groups and two hydroxyl groups within the novel dye, (E)-4-(4-bis(2-hydroxyethyl)amino)styryl)pyridine-2,6-dicarboxylic acid, resulted in good water solubility. The compound's UV absorption and photoluminescence spectra were each highly pH sensitive in acidic solutions and two isobestic points were observed. The TPA cross-section coefficient and two-photon fluorescence cell imaging of the dye were investigated.     

吡啶二甲酸的合成及其应用

在含硫酸铜的酸性水溶液中,用氯酸钠作氧化剂,氧化喹啉得到2,3-吡啶二甲酸,产率为56·4%;以硫酸铜为催化剂,用浓硝酸在高温氧化异喹啉得到3,4-吡啶二甲酸,产率为71·4%,并讨论了影响合成的因素。在钼酸铵存在下,采用固相烘焙法,2,3-吡啶二甲酸和3,4-吡啶二甲酸分别与尿素和氯化亚铜作用得到了氮杂铜酞菁。实验发现,以3,4-吡啶二甲酸合成的氮杂铜酞菁在吡啶中具有较大的溶解度,最大吸收波长为673nm。