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以取代苯酚、多聚甲醛和取代苯胺为原料,在无催化剂的条件下,通过Mannich缩合反应合成了一系列新型3,6(8)-二取代-2,4-二氢-1,3-苯并(口恶)嗪类化合物.结果表明,取代苯酚和取代苯胺的取代基为供电子基时,合成产物的产率高于吸电子取代基的.产物的结构用1H NMR、13C NMR、IR和MS等进行了表征.初步测试了目标化合物的杀菌活性,部分化合物具有较好的杀菌活性.当浓度为25 mg/L时,化合物4j和4d对菌核病菌的抑制率分别为86.1%和81.5%,化合物4i对灰霉病菌的抑制率为81.6%. 相似文献
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基于氯过氧化物酶(CPO)催化氧化苯酚衍生物单体,建立了一个聚酚的绿色合成体系.以对苯基苯酚、对甲基苯酚、4-乙基苯酚、对羟基肉桂酸、对异丙基苯酚和邻甲基苯酚等6种底物为考察对象,以聚合物的产率、聚合度及热稳定性为评价指标,研究了体系中引入离子液体(ILs)或季铵盐(QAS)以及底物结构和反应微环境等对聚合反应和聚合物性质的影响.结果表明,引入少量咪唑类ILs或QAS可有效提高产物收率,其中ILs/QAS的阳离子基团越大和疏水链越短,越有利于酶催化聚合反应的进行;而ILs/QAS添加量的影响则呈现"钟罩"型规律.同时,苯酚对位取代远比邻位取代有利于聚合反应进行;而对位取代基中烷基类给电子基团比芳香基取代更有优势,所得聚合物的聚合度和热稳定性相对增大,但随着取代基团的增大,其空间位阻不利于聚合物产率的提高;反应体系的p H应控制在弱酸性至近中性,以避免竞争性的副反应的发生;而氧化剂H_2O_2则需要采用间歇式加入以抑制瞬时过浓导致CPO活性中心卟啉环的氧化损伤.基于CPO的活性中心结构分析了聚合机理. 相似文献
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研究以二种基于磺酸基官能团的Brфnsted酸性功能化离子液体:1-(4-磺酸基)苄基-3-甲基咪唑硫酸氢盐(a),N-(4-磺酸基)苄基吡啶硫酸氢根盐(b)作为反应介质与催化剂,2-氨基苯甲酸、原甲酸酯或甲酸、芳香胺或脂肪胺三组分为原料,在微波辐射下实现了3-取代-4(3H)-喹唑啉酮的一锅法快速合成.离子液体加入量10 mo1%,反应时间4~6min,目标化合物产率74%~94%.离子液体可循环使用3次,催化活性基本保持不变.此合成方法通用性强,3-位可引入芳基或烷基取代基,取代基电性效应小,拉电子取代基底物也可顺利反应.另外,反应可直接以85%甲酸作为C-2引入单元,目标化合物产率72%~91%. 相似文献
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以取代苯酚、多聚甲醛和取代苯胺为原料,在无催化剂的条件下,通过Mannich缩合反应合成了一系列新型3,6(8)-二取代-2,4-二氢-1,3-苯并噁嗪类化合物。 结果表明,取代苯酚和取代苯胺的取代基为供电子基时,合成产物的产率高于吸电子取代基的。 产物的结构用1H NMR、13C NMR、IR和MS等进行了表征。 初步测试了目标化合物的杀菌活性,部分化合物具有较好的杀菌活性。 当浓度为25 mg/L时,化合物4j和4d对菌核病菌的抑制率分别为86.1%和81.5%,化合物4i对灰霉病菌的抑制率为81.6%。 相似文献
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用紫外-可见分光光度分析法测定了PhIO氧化系列新型Schiff碱双核配合物的反应动力学及取代基效应.结果表明,这些配合物与PhIO的反应在动力学上为一级反应;这些配合物的环外苯基及环上亚苯基上吸电子取代基均能提高抗氧化稳定性,而给电子取代基的作用则相反;环上亚苯基上的取代基效应比环外苯基上的取代基效应更明显;氧化反应速率常数k与环外苯基上的取代基特性常数σ(σm或σp)及环上亚苯基上的取代基特性常数(σm+σp)呈良好的线性关系:-lgk=0.5215σ+1.326;-lgk=0.8271[(σm+σp)/2]+1.506. 相似文献
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合成了数个新手性双-(三氟甲磺酰)亚胺基二硫代缩酮基硅路易斯酸2~4, 并研究了它们对环戊二烯和丙烯酸衍生物11a~11c的Diels-Alder反应的催化活性. 结果表明催化剂活性高, 环加成反应的产率高达89%~96%, 并且获得较高的非对映选择性和中等对映选择性, 当催化剂为2b时, 反应的对映选择性达到最高, 为48% ee. 相似文献
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Gary W. Breton 《Tetrahedron letters》2011,52(6):733-735
The reaction of 4-methyl-1,2,4-triazoline-3,5-dione (MeTAD) with substituted benzenes under the influence of trifluoroacetic acid catalysis was investigated. Generally, good-to-high yields of 1-arylurazoles resulting from aromatic substitution were obtained. Successful reaction required moderately electron-rich aromatics with proper substitution patterns. The reaction was tolerant of functionality on the aromatic ring. 相似文献
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Rahim Hekmatshoar Sanaz Souri Mahshid Rahimifard Farnoosh Faridbod 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):2827-2833
Protonation of the highly reactive 1:1 intermediates produced in the reaction between triphenylphosphine and dimethyl acetylenedicarboxylate(DMAD) by substituted phenols lead to vinyl triphenylphosphonium salts, which undergo aromatic electrophilic substitution reaction with a phenolate conjugate base to produce 4-carboxymethyl coumarins in fairly highly yields. 相似文献
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Gerald F. Bauerle Jennifer S. Brodbelt 《Journal of the American Society for Mass Spectrometry》1995,6(8):627-633
Competitive reactions of dimethyl ether ions are used to probe the steric and substituent effects of substituted phenols and anisoles in a quadrupole ion trap. The relative percentages of protonation and methylene substitution from the reactions of dimethyl ether ions show a correlation with size, location, and number of subsrituents on the aromatic ring. Although gas-phase basicity measurements of the phenols show no discernible correlation with the percentages of competitive reactions, semiempirical calculations show a good correlation between the trend in heats of formation and the trend in methylene substitution percentage. Reactions with deuterated compounds show that the methylene substitution reaction occurs on the ring. 相似文献
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Hassan Valizadeh F. Mahmoodi Kordi Hamid Gholipur Mohammad Amiri 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):3075-3081
Phosphoric acid imidazolium dihydrogenphosphate was found to work well as a catalyst and excellent reaction medium in the Pechmann condensation of substituted phenols or α-naphthol with ethyl acetoacetate to give 4-methyl coumarins under microwave irradiation. This method is simple, cost effective, requires short reaction times, and gives very good to excellent yields. 相似文献
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Adisak Thanetchaiyakup Hassayaporn Rattanarat Nutthawat Chuanopparat Paiboon Ngernmeesri 《Tetrahedron letters》2018,59(11):1014-1018
A simple and efficient one-pot synthesis of substituted indolo[1,2-a]quinolines under transition-metal-free conditions has been developed. When 2-fluorobenzaldehyde was treated with substituted 2-methylindoles in the presence of Cs2CO3, the desired products were typically obtained in good to excellent yields. This reaction sequence involves a nucleophilic aromatic substitution and a Knoevenagel condensation reaction. Our mechanistic investigation revealed that both reactions could proceed as an intermolecular reaction in the first step. 相似文献
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An aromatic nucleophilic substitution reaction of phenylethers with primary amines is described. This reaction, promoted by electron-attracting groups on the benzene ring, fast and simple to perform, leads to substituted anilines in high yields. 相似文献
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将金鸡纳碱衍生物双功能催化剂用于有机催化羟基吲哚与靛红的不对称Friedel-Crafts反应, 筛选出最佳反应条件: 催化剂为5%(摩尔分数)6′-脱甲基奎尼丁(1b), 溶剂为四氢呋喃, 反应温度 0 ℃. 以67%~91%的产率和最高达97%的对映选择性获得了苯环上取代的羟基烷基化产品. 拓宽了该反应的催化剂类型和底物范围. 相似文献
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Liquid ammonia is a useful solvent for many organic reactions including aliphatic and aromatic nucleophilic substitution and metal-ion catalysed reactions. The acidity of acids is modified in liquid ammonia giving rise to differences from conventional solvents. The ionisation constants of phenols and carbon acids are the product of those for ion-pair formation and dissociation to the free ions. There is a linear relationship between the pK(a) of phenols and carbon acids in liquid ammonia and those in water of slope 1.68 and 0.7, respectively. Aminium ions exist in their unprotonated free base form in liquid ammonia. The rates of solvolysis and aminolysis by neutral amines of substituted benzyl chlorides in liquid ammonia show little or no dependence upon ring substituents, in stark contrast with the hydrolysis rates of substituted benzyl halides in water which vary 10(7) fold. However, the rates of the reaction of phenoxide ions and amine anions with 4-substituted benzyl chlorides gives a Hammett ρ = 1.1 and 0.93, respectively. The second order rate constants for the substitution of benzyl chlorides by neutral and anionic amines show a single Br?nsted β(nuc) = 0.21 whereas those for substituted phenoxide ions generate a Br?nsted β(nuc) = 0.40. The rates of aromatic nucleophilic substitution reactions in liquid ammonia are much faster than those in protic solvents indicating that liquid ammonia behaves like a typical dipolar aprotic solvent in its solvent effects on organic reactions. Nitrofluorobenzenes (NFB) readily undergo solvolysis in liquid ammonia but oxygen nucleophiles, such as alkoxide and phenoxide ions, displace the fluorine of 4-NFB in liquid ammonia to give the corresponding substitution product with little or no competing solvolysis product. The Br?nsted β(nuc) for the reaction of 4-NFB with para-substituted phenoxides is 0.91, indicative that the decomposition of the Meisenheimer σ-intermediate is rate limiting. The aminolysis of 4-NFB occurs without general base catalysis by the amine and the second order rate constants generate a Br?nsted β(nuc) of 0.36, which is also interpreted in terms of rate limiting breakdown of the Meisenheimer σ-intermediate. 相似文献
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Jan M. Bakke 《Journal of heterocyclic chemistry》2005,42(3):463-474
Reaction of pyridine and substituted pyridines with N2O5 in an organic solvent gives the N‐nitropyridinium ion. When this is reacted with SO2/HSO3‐ in water, 3‐nitropyridine is obtained (77 % yield). With substituted pyridines the method gives good yields for 4‐substituted and moderate yields for 3‐substituted pyridines. The reaction mechanism is not an electrophilic aromatic substitution but one in which the nitro group migrates from the 1‐position to the 3‐position by a [1,5] sigmatropic shift. From 3‐nitropyridine, 5‐nitropyridine‐2‐sulfonic acid is formed in a two step reaction. From this, a series of 2‐substituted‐5‐nitropyridines has been synthesized. 3‐Nitropyridine and 4‐substituted‐3‐nitropyridines have been substituted with ammonia and amines by the vicarious nucleophilic substitution (VNS) method with ammonia and amines and by the oxidative substitution method in the position para to the nitro group. High regioselectivities and yields have been obtained in both cases to afford a series of 4‐substituted‐2‐alkylamino‐5‐nitropyridines. The VNS method has also been used in alkylation reactions with 3‐nitropyridines to form dichloromethyl‐and alkoxycarbomethyl‐β‐nitropyridines. From the appropriate substituted nitropyridines imidazopyridines and azaindoles have been formed. 相似文献