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溴苄类化合物在医药、农药和染料等领域有广泛的应用, 在以往的报道中由甲基芳烃制备溴苄类化合物的方法都是采用自由基的历程进行的. 报道了一种以甲基芳烃与三溴化硼直接反应采用非自由基的历程制备系列溴甲基芳烃的新方法. 该方法反应条件温和、收率高、选择性好. 在考察电子效应和位阻效应时发现: 该方法对不同取代基的底物适应范围广, 带推电子取代基对反应有利; 取代基位阻有一定影响但是没有吸电子基团显著, 吸电子基团降低产率. 同时, 在研究溶剂、温度、三溴化硼用量和时间对反应的影响时找到了最佳反应条件. 相似文献
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评价了一种碳水化合物衍生的具有较大立体位阻及较三苯基膦更富电子的膦配体(甲基3-脱氧-3-二苯膦基-4,6-氧-苯次甲基-α-D-吡喃阿卓糖苷,3-MBPA)在Pd催化的Heck反应中的性能.发现在N,N-二甲基乙酰胺溶刺中K2CO3是该催化体系较适合的碱;在该配体的支持下催化剂中钯的用量可低至0.5 mo1%;可催化苯乙烯与带给电子基团的溴代芳烃及带吸电子基团的氯代芳烃发生反应,高产率地生成相应的偶联产物;反应区域选择性表明,Pd(OAc)2/3-MBPA体系在催化苯乙烯与卤代芳烃的Heck反心中并存阳离子催化途径,说明3-MBPA中的氧原了可能也参与配位;同时发现,加入助配体四丁基溴化胺(TBAB)后,可能是Br-参与配位有利于增加中性催化途径的机会而提高了反应区域选择性. 相似文献
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报道了室温超声辐射下, 水相中通过乙酰乙酸甲酯、盐酸羟胺和芳香醛的三组分一锅反应, 合成了一系列3-甲基-4-芳亚甲基-异噁唑-5(4H)-酮衍生物. 在超声波辐射下, 参与反应的醛无论芳环上连有吸电子基或供电子基, 该一锅反应在室温下都能较好地进行; 对于α,β-不饱和醛、杂环芳醛以及二元芳醛与乙酰乙酸甲酯、盐酸羟胺的一锅反应也能在室温下顺利进行, 获得中等以上的收率. 产物的结构通过元素分析, IR, 1H NMR及单晶解析表征. 该方法具有操作简单和环境友好等优点. 相似文献
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三氯偶氮氯膦树脂相光度法测定铁矿中的稀土总量 总被引:4,自引:0,他引:4
1 引 言均三氯偶氮氯膦 (TCCPA) [2 (4 氯 2 膦酸基苯偶氮 ) 7 (2 ,4 ,6 三氯偶氮 ) 1,8 二羟基 3,6 二磺酸萘 ]是一种紫色结晶粉末 ,易溶于水 ,醇 ,不溶于苯 ,乙酸乙酯。在中性或碱性水溶液中呈紫红色 ,与稀土形成兰紫色络合物。三氯偶氮氯膦能在强酸性 0 2~ 0 .4mol LHCl介质中与稀土元素发生极灵敏的显色反应 ,摩尔吸光系数ε =8.6 2×10 4 ~ 11.7× 10 4 ,是目前变色偶氮膦类试剂中灵敏度较高的。由于可在强酸性中显色 ,其选择性也比较好。常见的共存元素允许量大都在mg级以上 ,是一种性能优良的显色稀土… 相似文献
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由于聚硅烷具有一些特殊的性质及用途,近年来引起了人们的注意。文献报道的多是主链连有烷基、芳基或芳烷基的聚硅烷,而主链连有活性基团的聚硅烷很少。我们曾合成了主链连有硅氢基团的聚硅烷,并研究了其交联反应。通过硅氢键的反应,可在硅一硅主链上引入一些活性基团,赋予聚硅烷新的特性。本文则报道不同反应条件对甲基二氯硅烷缩合的影响。 相似文献
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〗通过超临界萃取方法对大港减压渣油进行深度窄馏分切割,利用钌离子催化氧化(RICO)对其抽余残渣进行选择性降解,对降解生成的混合物进行分离,其中非挥发性羧酸进行甲酯化处理,挥发性羧酸进行苯甲酰甲酯化,最后分别利用GC-MS等方法进行定性定量分析。结果表明,大港减压渣油超临界萃取萃余残渣分子中含有大量与芳环相连的正构烷基侧链和桥接芳环的聚亚甲基链,芳环的缩合程度小于利用结构族组成等分析方法分析大港减压渣油沥青质得到的结果。大港减压渣油超临界萃取萃余残渣的共价结构信息可对该原料的加工和优化利用提供指导。 相似文献
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Surface grafting of β-cyclodextrin onto aminopropylsilica has been carried out under mild conditions using 1,1'-carbonyldiimidazole as an activator. The obtained β-cyclodextrin-silica has been characterized by means of chemical and IR spectral analysis. Adsorption of para-aminobenzoic and para-aminosalicylic acids onto the surface of hydroxylated silica, aminopropylsilica, and silica with chemically attached β-cyclodextrin moieties has been studied in relation to duration of contact, equilibrium concentration, and solution pH. Chemical immobilization of β-cyclodextrin onto silica surface improves adsorption parameters for aromatic amino acids. The well-known mathematical models for the kinetic and equilibrium adsorption processes have been used, and the main adsorption parameters have been calculated. Kinetic curves of aromatic amino acids adsorption correspond to the model of pseudo-second order reaction. The major contribution to the equilibrium adsorption of para-aminobenzoic and para-aminosalicylic acids onto β-cyclodextrin-containing silica is due to the formation of surface inclusion complexes between grafted oligosaccharide molecules and aromatic amino acids. 相似文献
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Fukuji Higashi Atsushi Hoshio Yukiharu Yamada Michihide Ozawa 《Journal of polymer science. Part A, Polymer chemistry》1985,23(1):69-75
The diphenyl chlorophosphate (DPCP)-promoted polycondensation reaction between aromatic dicarboxylic acids and bisphenols was largely improved by carrying out the reaction in the presence of lithium halides to give high molecular weight aromatic polyesters. Among the halides LiBr, which is capable of forming a complex with hexamethylphosphoramide, was most effective, suggesting that a similar complexation of DPCP with LiBr in pyridine facilitates the complete reaction of DPCP with carboxyl groups. The complex could selectively activate carboxyl groups of hydroxybenzoic acids to give high molecular weight copolyesters from several combinations of aromatic hydroxy acids. The reaction could also be adaptable to the copolycondensations of a mixture of the dicarboxylic acids, bisphenols, and hydroxybenzoic acids. 相似文献
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The macrocyclic antibiotic thiostrepton has been structurally modified with achiral reagents containing aromatic groups and isocyanate or isothiocyanate-terminated linkages to improve its selectivity in the LC resolution of aromatic enantiomers in polar–organic mode. The enantiomer resolutions achieved could not be reproduced either with underivatized thiostrepton or with the rifamycin SV stationary phase prepared by use of the same reaction procedures. Maximum enantioselectivity was achieved by optimizing the number of achiral derivatizing groups attached to thiostrepton. Chromatographic data for resolution of enantiomers containing aromatic groups suggest that the enhanced resolution is highly dependent on the π–π interaction between the analyte and the chiral selector. A mechanistic study entailing resolution of amino acid derivatives also indicated that analyte structure affects the strength of the π–π interaction and is crucial for chiral recognition to be possible. Other effects, for example steric hindrance, dipole–dipole interaction, and hydrogen bonding with the isocyanate and isothiocyanate functional groups of reagents also facilitate resolution. 相似文献
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Selective Oxidation of Alkyl‐Substituted Polyaromatics Using Ruthenium‐Ion‐Catalyzed Oxidation 下载免费PDF全文
Ewa Nowicka Meenakshisundaram Sankar Robert L. Jenkins David W. Knight David J. Willock Graham J. Hutchings Manuel Francisco Stuart H. Taylor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(11):4285-4293
Ruthenium‐ion‐catalyzed oxidation of a range of alkylated polyaromatics has been studied. 2‐Ethylnaphthalene was used as a model substrate, and oxidation can be performed in either a conventional biphasic or in a monophasic solvent system. In either case the reaction rates and product selectivity are identical. The reaction products indicate that the aromatic ring system is oxidized in preference to the alkyl chain. This analysis is possible due to the development of a quantitative NMR protocol to determine the relative amounts of aliphatic and aromatic protons. From a systematic set of substrates we show that as the length of the alkyl chain substituent on a polyaromatic increases, the proportion of products in which the chain remains attached to the aromatic system increases. Larger polyaromatic systems, based on pyrene and phenanthrene, show greater reactivity than those with fewer aromatic rings, and the alkyl chains are more stable to oxidation. 相似文献
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Alpha-alkyl amino acids can be efficiently prepared in high yields from the respective amino acids themselves. The key step is the oxidation of the amine function to create the corresponding alpha-nitro acid in a fast and very high yield reaction followed by phase-transfer alkylation and finally reduction to the desired alpha-alkyl amino acid. Several such acids containing aromatic rings or additional carboxylic groups and acids with steric hindrance at the alpha-position are suitable substrates. Several alkyl halides were examined as alkylating agents. 相似文献
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钌离子催化氧化法研究大港减压渣油组分化学结构 总被引:1,自引:0,他引:1
利用钌离子催化氧化方法对大港减压渣油芳香分、胶质和庚烷沥青质进行了选择性降解,通过GC、GC-MS等分析手段对降解反应产物中一元正构脂肪酸、α,ω-二元正构脂肪酸和苯二~六元羧酸的含量和分布分别进行了定量分析。结果表明,芳香分、胶质和庚烷沥青质中的芳香结构上都存在大量烷基取代基和桥接不同芳碳的聚亚甲基桥。烷基取代基碳数最大约为33,聚亚甲基桥最大碳数约为24,而且这两种结构单元的含量均随碳数的增加而减少,并呈现出了偶碳优势。庚烷沥青质C12以下侧链相对较多而C16+较少,与芳香分的分布相反;正构烷基侧链的浓度按庚烷沥青质、胶质和芳香分的顺序递减。降解产物中都检测到了苯二甲酸到苯六甲酸等一系列的苯多酸,表明三个组分中都存在稠环芳香结构。庚烷沥青质中缩合程度较高的迫位缩合结构含量最高,芳香分渺位缩合结构最多,胶质介于两者之间。 相似文献
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Mio Kubota 《Tetrahedron letters》2004,45(29):5755-5758
A novel thymidine-methyl red conjugate was synthesized and incorporated into oligodeoxyribonucleotides (ODNs). The ODNs containing the conjugate formed a novel nucleic acid-based structural motif, the aromatic zipper, which fastens via the stacking interactions of aromatic residues that are attached to DNA strands. The aromatic zipper can be used to stabilize structural motifs in nucleic acids and their analogues, such as hairpin structures, by fastening their ends. 相似文献
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The condensation reaction of 1,3-dimethylbarbituric acid with aromatic aldehydes in ethanol has been investigated spectrophotometrically at 25–35°C. The reaction follows overall second-order kinetics, first-order each in reactant. From the dependence of the rate constants on temperature, activation parameters have been calculated. The rate of condensation increases with the presence of electron donating groups on the aromatic ring of the aldehyde. The rate-determining step involves dehydration of the aldol intermediate. The reaction was found to be catalyzed by HCl solutions. Based on this reaction, determination of 10 aromatic aldehydes in a concentration range of 0.13–70.25 μg/ml is proposed. The method was applied for determination of barbituric and 1,3-dimethylbarbituric acids also. 相似文献
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If phenylhydrazine or its salts are heated with arsenic acid or with one of its organic derivatives (aliphatic or aromatic arsonic acids) phenol results. The latter can easily be detected in the gas phase by the indophenol reaction with 2:6-dichloroquinone-4-chloroimine. This has been made the basis of characteristic tests for phenylhydrazine (also phenylhydrazones and osazones) as well as for arsonic acids. When conducted within the bounds of spot test analysis, the limits of detection are microanalytical. 相似文献