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合成双酚AF的新方法 总被引:5,自引:1,他引:4
由六氟丙酮三水合物和苯胺,经缩合、重氮化、水解、Friedel-Crafts烷基化等4步反应在常压下合成了双酚 AF。首先,以五氧化二铌为催化剂,在 n (HFA•3H2O) : n (aniline) : n (Nb2O5) = 2 : 1 : 0.1,回流 6 h 条件下,合成出中间体(Ⅰ),收率高达96.3%。然后在重氮化温度为 ﹣2 ~ 2 ℃,硫酸质量分数为 14.7%,n (Ⅰ) : n (H2SO4) : n (NaNO2) = 1 : 4.1 : 1.1,及水解时硫酸质量分数为 50%,n (H2SO4) : n (Ⅰ) = 11.0 : 1、108~112 ℃反应 1.5 ~ 2 h 的优化条件下,化合物Ⅰ经重氮化、水解后以 92.7%的高收率得到中间体 2-(4-羟基苯)六氟异丙醇(Ⅱ);再在甲磺酸存在下,化合物Ⅱ与苯酚经Friedel-Crafts烷基化反应以 72.4% 的收率合成了目标产物双酚 AF(Ⅲ),总收率为 64.6%(以苯胺为基准计算)。 相似文献
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微波辐射下,在水溶液中以KOH催化苯酚与六氟丙酮三水合物(HFA·3H2O)的缩合反应,制备了2-(4-羟-基苯基)六氟异丙醇的异构体混合物;目标产物结构经IR、1H NMR和MS确认。 结果表明,与传统加热法相比,微波辐射法可明显缩短反应时间。 在n(苯酚)∶n(HFA·3H2O)∶n(KOH)=3.0∶1.0∶0.3及微波功率为300 W条件下,反应时间可由常规加热法的35 h缩短至6 h,总收率由87%提高到90%,目标物产物选择性为94%。 相似文献
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以固体酸为催化剂,4,4’-二氟二苯甲酮与苯胺脱水缩合,合成了N-(双(4-氟苯基)亚甲基)苯胺.比较了不同固体酸催化剂H型ZSM-5、Na型ZSM-5、介孔分子筛MCM-41(Al)及强酸型离子交换树脂Amberlyst 15的催化效果.使用比表面、NH3-TPD对催化剂进行了表征,并与催化效果关联.考察了催化剂用量、原料摩尔比、浓度及溶剂等反应条件对产物收率的影响.产物通过熔点、核磁共振谱进行了表征.结果表明,HZSM-5固体酸催化剂具有优异的催化作用.在优化条件下,以对二甲苯为反应溶剂和脱水剂,4,4’-二氟二苯甲酮0.1 mol,苯胺0.2 mol,催化剂用量2.0 g,反应24 h,产物收率达91%.此外,催化剂易于分离,能够重复使用多次. 相似文献
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利用氯甲基吡啶与咪唑反应制备了一系列含吡啶取代咪唑L1~L5,考察了所得咪唑衍生物与钌化合物在碱性条件下原位形成的氮杂卡宾钌络合物对苯胺与醇氢转移反应的催化活性.研究了碱的种类、钌前体、温度等对反应的影响,结果表明RuCl3 H2O/1-(2-吡啶甲基)-3-甲基碘化咪唑(L3)/KOH催化体系在185℃时对苯胺与乙二醇反应的催化活性较高,选择性生成N-羟乙基苯胺,TON(单位活性转化的底物分数)可达2130.此外,还考察了RuCl3 H2O/L3/KOH催化体系对苯胺与丁醇、环己醇、异丙醇、苯甲醇反应的催化性能.在催化剂作用下,醇与苯胺可形成亚胺及仲胺,伯醇可以自氢转移反应形成酯,反应产物的结构及选择性取决于醇的结构及反应条件. 相似文献
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The delamination and intercalation of a layered microporous aluminophosphate, [Al3P4O16](3-).3[CH3(CH2)NH3]+ (AlP), with aromatic amine have been carried out and were followed by XRD and SEM measurements. The basicity of the amine plays an important role in this process, as do the dielectric constant of the solution and the amount of amine added. A saturated benzylamine (pKa of 9.34) intercalate of the aluminophosphate are obtained in solutions with dielectric constant of 50-70 and an amine concentration of 10 mmol/g AlP, while no aniline (pKa of 4.60) intercalates are formed under similar conditions. The remarkable effect of basicity of the amine can be explained by a metathetical balanced reaction model, which was proved by the results of the intercalation processes of 4-methylpiridine (pKa = 6.00) and 4-methylimidazole (pKa = 7.55). 相似文献
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设计并制备了Ni-V/γ-Al2O3催化剂, 研究了其上苯用过氧化氢氧化氨化一步直接合成苯胺的性能和不同氨基源对合成苯胺的影响. 实验结果显示:在本文条件下, Ni/γ-Al2O3和V/γ-Al2O3催化剂均能活化苯环上C—H键, 使苯一步氧化羟基化为苯酚. Ni、V双组分催化剂则表现出较好的合成苯胺活性和选择性, 催化剂中Ni/V摩尔比在5.5时催化活性和选择性最好,目标产物苯胺的选择性达到85%, 远远高于主要副产物苯酚的选择性. 反应时间宜控制在2 h左右, 反应最佳温度为333 K. 尿素在碱性条件下可作为氨基化试剂, 在Ni-V/γ-Al2O3催化剂作用下使苯直接氧化氨化为苯胺, 尿素和氨水作为共氨化剂表现出对生成苯胺有利的协同效应. 相似文献
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以有机过氧化氢物叔丁基过氧化氢(TBH)或异丙苯过氧化氢(CHP)与芳叔胺N,N-二甲基苯胺(DMA)或其衍生物组成的体系引发甲基丙烯酸甲酯(MMA)聚合。研究有机过氧化氢物与芳叔胺结构对聚合的影响,测定了TBH-胺与CHP-胺体系引发MMA聚合的总活化能分别为50-57KJ/mol与39-62KJ/mol,并对CHP-DMT(N,N-二甲基对甲苯胺)引发MMA聚合动力学以及有关引发聚合机理进行了研究。 相似文献
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以H3PW12O40和AlCl3·6H2O为原料合成AlPW12O40,以此为催化剂研究苯甲醚与乙酸酐的酰基化反应,其主要产物为对甲氧基苯乙酮.采用正交试验确定酰化反应的适宜条件为:苯甲醚0.1 mol,苯甲醚与乙酸酐物质的量比为1∶1.5,催化剂用量1 g,反应时间4h,反应温度100℃,在此条件下,产品收率达到69.80%.考察了不同反应底物及不同酰化试剂对反应的影响和不同磷钨酸盐的催化效果,比较了不同加热方式对催化反应的影响.结果表明,磷钨酸铝的催化活性最好,微波加热合成目标产物效果更好. 相似文献
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Trissa Joseph G.V. Shanbhag D.P. Sawant S.B. Halligudi 《Journal of molecular catalysis. A, Chemical》2006,250(1-2):210-217
The catalytic activity of montmorillonite clays as a catalyst for the hydroamination of α,β-ethylenic compounds with amines was tested. Aniline and substituted anilines reacted with α,β-ethylenic compounds in the presence of catalytic amount of commercially available clay to afford exclusively anti-Markovnikov adduct in excellent yields. Aniline reacted with ethyl acrylate to yield only anti-Markovnikov adduct N-[2-(ethoxycarbonyl)ethyl]aniline (mono-addition product). No Markovnikov adduct (N-[1-(ethoxycarbonyl)ethyl]aniline and double addition product N,N-bis[2-(ethoxycarbonyl)ethyl]aniline were formed under selected reaction conditions. For a better exploitation of the catalytic activity in terms of increased activity and improved selectivity for the mono-addition product, the reaction parameters were optimized in terms of temperature, solvent, reactant mole ratio. Under optimized reaction conditions, montmorillonite clay K-10 showed a superior catalytic performance in the hydroamination of ethyl acrylate with aniline with a conversion of aniline to mono-addition product (almost 100% chemoselectivity) with a high rate constant 0.3414 min−1 compared to the reported protocols. The dependence of conversion of aniline over different types of montmorillonite clays (K-10, K-20, K-30, Al-Pillared clay and untreated clay) has also been discussed. The activities of clay for the hydroamination of different aromatic and aliphatic amines have also been investigated. Under harsh reaction conditions (increased temperature and long reaction time) small amounts of di-addition products were observed. The kinetics data has been interpreted using the initial rate approach model. 相似文献
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降解水中有机毒物的新型反应体系研究 总被引:6,自引:0,他引:6
利用空气中的氧电化学合成H2O2,制备具有较高电流效率的空气电极.将空气电极用于构成降解有机毒物的新型反应体系电化学氧化体系、光激发氧化剂氧化体系和光电-Fenton氧化体系.实验测量了H2O2在不同体系不同条件下的分解速率,并与相应的传统式体系作了比较.实验测量了苯胺在新型体系中的矿化反应速率,发现H2O2的分解速率与苯胺的矿化速率有良好的平行关系,其中H2O2分解速率最快的光电-Fenton体系是氧化降解有机分子的最佳体系.通过光电-Fenton体系和光-Fenton体系的比较,揭示了空气电极/溶液界面在光电-Fenton体系中所起的重要作用.初步讨论了苯胺分子在光电-Fenton体系中矿化反应的机制. 相似文献
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Kinetics of the additive reaction of aniline with dicyandiamide resulting in phenylbiguanide production was studied based
on the analysis of reaction rate by high performance liquid chromatography. It is a second-order reaction on the condition
of the constant temperature and acidity. It is first-order for both aniline and dicyandiamide. The reaction rate is influenced
evidently by acidity. It reaches its maximum at pH 2.6. The mechanism for this reaction was suggested that aniline is nucleophilic
reagents additive with the protonated cyano-group in dicyandiamide. The rate equation derived from the mechanism can describe
the experimental results well. The reaction rate calculated from the rate equation reaches its maximum at pH 2.5, which is
close to the experimental result. For different aromatic amine adding to dicyandiamide have the same reaction order, the mechanism
ought to be the same.
Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 3, pp. 379–385.
The article is published in the original. 相似文献