取代苯氧乙酸(3-氟-4-氰基)苯酯的合成及表征

从取代苯酚出发,经醚化和酰化,制得取代苯氧乙酰氯,再与3-氟-4-氰基苯酚作用,合成了5种新的取代苯氧乙酸(3-氟-4-氰基)苯酯类化合物。经元素分析、IR、1H NMR及MS确定了新化合物的结构。     

2-(3-氟-4-氰基苯氧基)-N-取代芳香基乙酰胺的合成及表征

以3-氟-4-氰基苯酚为基本原料,合成了6种新的2-(3-氟-4-氰基苯氧基)-N-取代芳香基乙酰胺,用IR、1H NMR及元素分析对化合物结构进行了表征,结果表明,化合物的结构与预期的目标相一致。     

4-（2＇-氟-4＇-氰基苯氧基）苯酚的合成新方法

4-（2＇-氟-4＇-氰基苯氧基）苯酚是合成苯氧丙酸类高效除草剂的重要中间体。研究了4-（2＇-氟-4＇-氰基苯氧基）苯酚合成的新方法。该方法以3,4-二氟苯腈和对羟基苯甲醚为主要原料,首先合成4-（2＇-氟-4＇-氰基苯氧基）苯甲醚,再经三溴化硼还原得到4-（2＇-氟-4＇-氰基苯氧基）苯酚。通过红外、核磁及质谱等分析手段对其化学结构进行了鉴定,两步反应总收率为64%,产品纯度95.2%,克服了文献报道的合成方法产量小、收率低的缺点。     

3-氟-4-硝基苯酚的合成

研究了含氟中间体3-氟-4-硝基苯酚(FNP)的合成,由间氟苯胺经重氮化、水解、硝化及异构体分离制得。间氟苯胺重氮盐在CuSO4和硫酸介质中,用反应蒸馏技术,水解制得间氟苯酚,收率85%,质量分数95%;间氟苯酚硝化后采用水蒸气蒸馏法,把副产物3-氟-6-硝基苯酚有效除去,再经乙醚萃取、饱和NaCl水溶液洗涤、饱和NaHCO3水溶液洗涤、Na2CO3水溶液中和成盐、酸化、乙醚萃取等后处理,得到质量分数99.6%的FNP,收率23%。     

2-氟-3-三氟甲基苯甲酸的合成

2-氟-3-三氟甲基苯甲酸是一个重要的药物中间体,同时又是制备含氟液晶的一个重要化合物,对其合成方法进行了研究：以邻氟三氟甲基苯、丁基锂、二氧化碳为原料来合成,该合成方法操作简便,收率高达86．5％。     

3,4,5-三氟-2-甲基苯类液晶化合物的合成与性能

以3,4,5-三氟苯酚、3,5-二氟-4'-烷基联苯为原料,经酚羟基保护反应、丁基锂/碘甲烷上甲基反应、Williamson醚化反应等5步反应最终合成4-[二氟(3,4,5-三氟-2-甲基-苯氧基)甲基]-3,5-二氟-4'-烷基联苯类化合物。纯化后目标产物的气相色谱纯度≥99.5%,总收率约为47%,结构经~1HNMR及GC-MS确证。其中,合成2-(3,4,5-三氟-2-甲基-苯氧基)四氢吡喃适宜的物质的量比为n(2-(3,4,5-三氟苯氧基)四氢吡喃)∶n(丁基锂)=1∶1.2,3,4,5-三氟-2-甲基苯酚和4-溴二氟甲基-3,5-二氟-4'-烷基联苯醚化反应的最优化条件为在DMSO中反应4 h。将该化合物添加到液晶的基础配方中,能降低旋转粘度(γ1),提高液晶的响应速度,增加介电各向异性(Δε),降低阈值电压。     

保险粉还原制备3-氟-4-氨基苯酚的研究

以间氟苯酚为原料通过重氮化,然后用廉价的保险粉为还原剂,合成了3-氟-4-氨基苯酚,用元素分析、IR和1HNMR对其结构进行了表征。     

N-[4-氰基-3-(三氟甲基)苯基]-2-甲基-2-环氧丙酰胺合成工艺改进研究

4-氰基-2-三氟甲基苯胺与甲基丙烯酰氯反应生成N-[4-氰基-3-(三氟甲基)苯基]-2-甲基丙烯酰胺,在钼酸钠催化下,经过氧乙酸氧化,制得N-[4-氰基-3-(三氟甲基)苯基]-2-甲基-2-环氧丙酰胺。优化条件下,二步反应总收率为92%。改进后的方法收率高,操作简单,适于工业化生产。     

高效液相色谱法监控3-氟-4-溴苯酚的合成

本文主要研究通过高效液相色谱法(HPLC)监控3-氟-4-溴苯酚的合成反应过程。首次建立了以HPLC监测3-氟-4-溴苯酚的分析方法。色谱条件:YMC-Pack PRO C18(4.6 mm×150 mm×5μm)反相色谱柱,流动相为V(乙腈)∶V(水)=75∶25的混合溶液,柱温为室温,流速为1.0 m L/min,检测波长为284 nm。使用外标法对3-氟-4-溴苯酚进行定量分析,3-氟-4-溴苯酚峰面积与进样浓度呈线性关系,反应液浓度在0.02～0.20 mg/m L范围内线性关系良好(线性相关系数r=0.9984),加标回收率为97.60%～99.26%,重复进样的平均RSD为0.42%。本文为化合物3-氟-4-溴苯酚建立了一种高效、便捷、准确的分析方法,为3-氟-4-溴苯酚合成工艺的开发奠定了基础。     

液晶中间体3,4,5-三氟苯酚的纯化方法

介绍了一种液晶中间体3,4,5-三氟苯酚的纯化方法,采用了惰性溶剂共沸精馏的方法分离了液晶中间体3,4,5-三氟苯酚中近沸点杂质。结果表明,该纯化方法能使3,4,5-三氟苯酚的纯度达到99.95%以上。     

向列型含氟侧链高分子液晶的合成与表征

合成了4-(丙烯酸乙氧基酯)苯甲酸,4-(丙烯酸乙氧基酯)苯甲酰氧基苯甲酸等系列液晶中间体.首次合成了4-(丙烯酸乙氧基酯)苯甲酰氧基苯甲酸基元的含氟侧链高分子液晶,采用IR,1HNMR和19FNMR表征了其分子结构.通过DSC分析和偏光显微镜研究了含氟侧链高分子液晶的织构形态.结果表明,4-(丙烯酸乙氧基酯)苯甲酰氧基苯甲酸基元含氟侧链高分子液晶具有向列型液晶的织构形态.4-(丙烯酸乙氧基酯)苯甲酰氧基苯甲酸基元含氟侧链高分子液晶,其液晶温度范围较宽,随着液晶基元成分的降低,含氟侧链成分的增加,高分子液晶玻璃化温度略有降低.     

Reaction of 3-methyl phenol with tung oil

The aromatic ring substitution reaction of 3-methyl phenol with tung oil under acidic conditions was carried out. The product was analyzed to find out if 3-methyl phenol was subjected to the ring substitution reaction with tung oil at its conjugated double bonds. Up to two molecules of 3-methyl phenol were addition-reacted with the conjugated triene of one eleostearyl group of triglyceride of α-eleostearic acid which is the major component of tung oil. The 4-position of 3-methyl phenol was preferentially subjected to the cresol's ring substitution. Therefore, up to 6 mol of 3-methyl phenol was added to 1 mol of tung oil, most of which was bonded to 3-methyl phenol at its 4-position. When 3-methyl phenol was reacted with a relatively large amount of tung oil, the substitution reaction occurred at the 6-as well as 4-position of 3-methyl phenol to yield a tung oil dimer having 3-methyl phenol units in its molecule. The above results were confirmed by infrared (IR), nuclear magnetic resonance (NMR), and high-speed liquid chromatographic (HLC) analyses.     

Reaction of 3-methyl phenol with methyl α-eleostearate

The aromatic ring substitution reaction of 3-methyl phenol with methyl α-eleostearate under acidic conditions was carried out. The product was analyzed to find out if 3-methyl phenol was subjected to the ring substitution reaction with methyl α-eleostearate at its conjugated double bonds. Up to two molecules of 3-methyl phenol were addition-reacted with the conjugated triene of the eleostearyl group of methyl α-eleostearate. The 4-position of 3-methyl phenol was preferentially subjected to the cresol's ring substitution. When 3-methyl phenol was reacted with a relatively large amount of methyl α-eleostearate, the substitution reaction occurred at the 6- as well as 4-position of 3-methyl phenol, to yield a methyl α-eleostearate dimer having 3-methyl phenol units in its molecule. The above results were confirmed by infrared (IR), nuclear magnetic resonance (NMR), and high-speed liquid chromatographic (HLC) analyses, and the results of a previous paper connected with reaction of 3-methyl phenol were supported by the results of this paper.     

催化剂形态与酚类化合物加氢反应活性构效关系的研究进展

木质素是一种重要的生物质可再生资源,其降解后得到的酚类物质加氢后可得大量高附加值化学品,在环境治理和原料利用方面都有着十分重要的影响。本文综述了近年来国内外木质素酚类加氢反应催化剂的研究进展,总结了液相酚类催化加氢催化剂的种类、反应机理及结构敏感性因素对酚类催化加氢反应活性的影响,阐述了催化剂颗粒尺寸对液相酚类加氢反应活性影响,并以木质素液相酚类加氢反应催化剂的活性金属和载体为体系,对现有的结构敏感性反应中催化剂存在的形貌效应、晶相效应进行了讨论。提出未来可通过控制催化剂形貌和晶相来研究催化剂形态与催化活性之间的构效关系,为今后设计高活性木质素液相酚类加氢催化剂提供借鉴和参考。     

Effects of phenol on the properties of pitch produced thermally from the petroleum vacuum residue

A petroleum vacuum residue was thermally treated at 430 °C, with continuous addition of phenol to either the vapour phase or the liquid phase of the reacting system. Addition of phenol to the vapour phase increased the yield of the cracked oil and the fixed carbon of the residual pitch. When phenol was charged to the liquid phase, the yield of the oil remained unchanged, but the amount of the benzeneinsoluble matter in the pitch decreased, probably owing to the inhibition by phenol of the polymerization-condensation reactions of aromatic compounds. In both additions the cracked oil had a higher boiling point than that produced without phenol. Substitution of phenol with methyl groups increased the extent of cracking and coking properties (Roga Index) of the pitch. The effective order of phenol and its derivatives is: Phenol < m-Cresol < o-Cresol < p-Cresol < 2, 4-Dimethylphenol < 2, 6-Dimethylphenol < 2, 4, 6-Trimethylphenol Polyhydric phenol, e.g. catechol, and naphthol also enhanced the cracking reactivity of the residue.     

Determination of the concentration of silicon dioxide in crystal by potentiometric titration with a fluoride-selective electrode

The possibility of using the reaction of fluoride ions and fluoride complexes with aluminum complexonate in the presence of an excess of complexone III was investigated for determining the concentration of silicon dioxide in crystal after rapid decomposition of the sample with a mixture of sodium fluoride and nitric acid in precisely measured quantities. A method was developed for determining the concentration of silicon dioxide in crystal by potentiometric titration with a fluoride-selective electrode.Translated from Steklo i Keramika, Nos. 3–4, pp. 37–39, March–April, 1994.     

Microwave-assisted synthesis of CdF2 nanoflakes in ionic liquid

Cadmium fluoride (CdF₂) nanoflakes have been successfully synthesized using an ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate, [BMIM]BF₄) under microwave heating for 10 min. Not only did the ionic liquid act as the reaction medium in this route but also as an efficient fluridizer for the formation of CdF₂ species. The crystal phase, size and morphology of as-prepared nanomaterials were characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM).     

Reaction of Zirconium Fluoride Monohydrate and Ammonium Bifluoride: Its Effect on Fluoride Glass Preparation and Quality

The products obtained from the roomtemperature reaction of ammonium bifluoride and zirconium fluoride monohydrate are ammonium heptafluorozirconate ((NH₄)₃ZrF₂), liquid water, and hydrogen fluoride. Ammonium bifluoride and zirconium fluoride monohydrate were reacted prior to glass batching, producing dry ammonium heptafluorozirconate which was used to prepare a high-quality ZBLAN fluoride glass.     

3-氟-4-(1H-四唑-5-基)苯酚的合成及其性能表征

四唑化合物因其具有许多独特的性质,所以在化学的多个领域都有广泛的应用,所以本文以三氟四氰基苯酚为原料,以三乙胺和33%的盐酸为催化剂,在苯溶液中反应,得到3-氟-4-(1H-四唑-5-基)苯酚,产率为80%,产物为白色的针状晶体,并对其进行了核磁表征。     

Fe3O4 @ SPC类芬顿氧化降解苯酚

以钙基蒙脱石（Ca-MMT）为原料，采用一步层间模板法制备了四氧化三铁@硅柱撑蒙脱石催化材料（Fe3O4@SPC），通过XRD、FTIR、BET、SEM对材料的形貌、结构进行表征显示，Fe3O4@SPC具有d001=3.30 nm的晶面间距和4.47 nm的介孔，Fe3O4颗粒主要分散在SPC的外表面。以苯酚为降解目标污染物，考察了Fe3O4@SPC的催化活性和稳定性。结果表明，当苯酚质量浓度为100 mg/L，pH值为2.5，催化剂质量浓度为0.5 g/L，H2O2投加量为0.2 mL，反应时间为120 min时，苯酚的去除率为100％；催化剂经过5次循环使用后，苯酚的降解率依然保持在90%以上。通过GC-MS分析苯酚降解生成的中间体，结合叔丁醇淬灭实验，发现?OH氧化在非均相类芬顿催化氧化降解苯酚体系中起主导作用，推测了苯酚可能的降解路径。