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1.
环上取代基对苯乙酮和苯甲醛缩合反应的影响 总被引:9,自引:0,他引:9
苯乙酮衍生物与苯甲醛衍生物缩合制备各种查尔酮,报道了4种苯乙酮衍生物与9种苯甲醛之间相互缩合的结果,讨论了环上取代基对缩合反应的影响。苯甲醛环上取代基,除羟基外无论是吸电子基还是给电子基对缩合反应收率影响都不大;羟基处于醛基邻位和对位的苯甲醛与几种苯乙酮衍生物的缩合,多数没有得到预期的产物,或收率极低;苯乙酮环上的羟基对缩合反应影响很大,羟基超多,缩合越困难。提出了一种假设,试图解释羟基对缩合反应 相似文献
2.
The surface silanol groups on faujasite type zeolites, which were formed by hydrothermal and acid treatments and considered to be lattice defect, were characterized. IR measurements of silanol groups were made in situ and thermogravimetic analysis was conducted under vacuum so as to quantify their content. It was thus possible to quantify separately the concentration of silanol groups forming hydroxy nests and the concentration of terminal silanol groups present on the secondary pores and crystal external surfaces. As the evacuation temperature increased, silanol groups forming hydroxy nests were found to decrease as a result of dehydroxylation condensation. The number of terminal silanol groups on the secondary pores and external surface remained virtually unchanged. The concentration of terminal silanol groups agreed well with the value calculated according to the proposed destruction model of the zeolite framework. This justified the model that there remained the double 6-ring structure on the secondary pore surfaces after the sodalite cage was collapsed as a result of the treatments. The effect of silanol groups forming hydroxy nests on the zeolite surface polarity was examined by measuring immersional heats in various solvents. It turned out that the extremely localized silanol groups forming hydroxy nests in the framework were linked via hydrogen bond to each other and showed nonpolar behavior. Copyright 1999 Academic Press. 相似文献
3.
脂肪型超支化聚酯的端基改性研究 总被引:16,自引:0,他引:16
近年来 ,超支化聚合物以其独特的结构和性能而受到广泛的重视 ,已成为 2 1世纪高分子科学研究的重要方向[1~ 4 ] .超支化聚合物通常是通过 AB2 型单体的缩聚来合成的 ,由于超支化聚酯的单体容易合成 ,因此 ,有关超支化聚酯的研究最为深入 .目前所报道的脂肪型超支化聚酯都是以 2 ,2 -二甲醇基丙酸为原料来合成的 ,Malstrom等 [5~ 7]系统研究了该聚合物的合成及结构 .最近 ,Johansson[8]采用丙烯酰氯对该聚合物端基改性 ,获得了可用于紫外光固化的涂料 ,但是所采用的合成及提纯方法都很复杂 ,并且需要很长的反应时间 .本文采用一种新的… 相似文献
4.
Linxian Li Junsheng Li Xin Du Dr. Alexander Welle Prof. Dr. Michael Grunze Prof. Dr. Oliver Trapp Dr. Pavel A. Levkin 《Angewandte Chemie (International ed. in English)》2014,53(15):3835-3839
A novel UV‐initiated surface modification method for the direct functionalization of surface hydroxy groups with thiol‐containing molecules (termed “thiol–ol” modification) is described. This method is based on the oxidative conjugation of thiols to hydroxy groups. We demonstrate that different thiol‐containing molecules, such as fluorophores, thiol‐terminated poly(ethylene glycol) (PEG‐SH), and a cysteine‐containing peptide, can be attached onto the surface of porous poly(2‐hydroxyethyl methacrylate‐co‐ethylene dimethacrylate). Direct functionalization of other hydroxy‐group‐bearing surfaces, fabrication of micropatterns, and double patterning have been also demonstrated using the thiol–ol method. 相似文献
5.
Tairin Kawasaki Naoki Ishida Masahiro Murakami 《Angewandte Chemie (International ed. in English)》2020,59(41):18267-18271
A convenient method is reported to specifically acylate phenolic hydroxyl groups through a radical pathway. When a mixture of an aldehyde and a phenol in ethyl acetate is irradiated with blue light in the presence of iridium and nickel bromide catalysts at ambient temperature, phenoxyl and acyl radicals are transiently generated in situ and cross‐couple to furnish an ester. Aliphatic hydroxy groups remain untouched under the reaction conditions. 相似文献
6.
The Functionality of Surface Hydroxy Groups on the Selectivity and Activity of Carbon Dioxide Reduction over Cuprous Oxide in Aqueous Solutions 下载免费PDF全文
Piaoping Yang Dr. Zhi‐Jian Zhao Xiaoxia Chang Dr. Rentao Mu Shenjun Zha Gong Zhang Prof. Dr. Jinlong Gong 《Angewandte Chemie (International ed. in English)》2018,57(26):7724-7728
Carbon dioxide (CO2) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu2O) is a promising catalyst for CO2 reduction as it can convert CO2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu2O remains under debate because of the complex surface structure of Cu2O under reducing conditions, leading to limited guidance in designing improved Cu2O catalysts. This paper describes the functionality of surface‐bonded hydroxy groups on partially reduced Cu2O(111) for the CO2 reduction reaction (CO2RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO2RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO2RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination‐unsaturated Cu (CuCUS) sites stabilizes surface‐adsorbed COOH*, which is a key intermediate during the CO2RR. Moreover, the CO2RR was evaluated over Cu2O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu2O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO2RR and suppress the HER. 相似文献
7.
Polymers containing intact lactone groups are a new class of macromolecules with reactive groups, which are relatively easy to obtain by polymerization, polycondensation and polyaddition, as well as by reactions on existing macromolecules. Polymers with β-lactone Groups in particular can enter into numerous addition reactions, which can be used, for example, to obtain macromolecules containing hydroxy acid or amino acid groupings. The reactions proceed under mild conditions, and can even be carried out in aqueous media, frequently giving water-soluble polymers. The polymers can be cross-linked at low temperatures, even from the aqueous phase, by the addition of bifunctional or oligofunctional reagents. Polymers containing β-lactone groups can also be used as a basis for graft co-polymers; polyester or polyether branches can be grafted on, depending on whether monomeric lactones or monomeric epoxides are used. 相似文献
8.
Enzo Santaniello Patrizia Ferraboschi Shahrzad Reza-Elahi 《Monatshefte für Chemie / Chemical Monthly》2000,11(2):617-622
Lipase from Pseudomonas cepacia (PCL) catalyzes the regio- and stereoselective acylation of primary and secondary hydroxy groups in steroid side chains under irreversible transesterification conditions with vinyl acetate in organic solvents. 相似文献
9.
Graphene‐related materials contain chemically bonded oxygen atoms in the form of epoxy, hydroxy, carboxy, and carbonyl groups. It is important to determine the quantity of oxygen atoms and to understand their position on the graphene sheet. However, visualization of these groups by standard methods is a challenge. Here, we utilize europium(III) as a selective label for oxygen‐containing groups. We studied three different graphene‐related materials: 1) graphene oxide, 2) chemically reduced graphene oxide, and 3) thermally reduced graphene oxide (the number of oxygen containing groups decreases from material 1 to 3). We show that it is possible to efficiently use Eu as a label of oxygen‐containing groups. This Eu label could be applied to determine the precise location of oxygen‐containing groups on graphene sheets and also induce novel optical, electrochemical, and catalytic properties. 相似文献
10.
Enzo Santaniello Patrizia Ferraboschi Shahrzad Reza-Elahi 《Monatshefte für Chemie / Chemical Monthly》2000,131(6):617-622
Summary. Lipase from Pseudomonas cepacia (PCL) catalyzes the regio- and stereoselective acylation of primary and secondary hydroxy groups in steroid side chains under
irreversible transesterification conditions with vinyl acetate in organic solvents.
Received December 20, 1999. Accepted December 31, 1999 相似文献
11.
Zn(bipy)3Cl2, Fe(bipy)Cl3, and Fe(tpp)Cl are effective catalysts for silylation of hydroxy groups with HMDS at room temperature in dry CH3CN. High selectivity is observed between primary and secondary hydroxy functional groups. This method absolutely discriminates other functional groups containing labile hydrogen atoms. 相似文献
12.
Tsao L. Dou Kh. Sun' G. Lyu Yu. Koroteev A. M. Krasnov G. B. 《Russian Journal of Organic Chemistry》2003,39(3):384-391
The reactivity of melezitose hydroxy groups was studied by tritylation in pyridine with subsequent acetylation. After partial detritylation of the products, acetyl group transfer from position 4 to 6 was observed. The structure of the prepared melezitose derivatives was established on the basis of their IR, 1H, 13C, and 1H-1H COSY NMR, and mass spectra (fast atom bombardment), as well as from the results of model calculations performed with the aid of SGI Indigo Molecule-Pattern-Work-Station software package (Biosym) where the potential energy function was approximated with the CVFF potential. The reactivity of primary hydroxy groups in melezitose was found to decrease in the following order: 6' > 6 6' > 1'. 相似文献
13.
14.
Rosemary J. Goodwin Andrew Docker Hugo I. MacDermott-Opeskin Heather M. Aitken Assoc. Prof. Megan L. O'Mara Prof. Paul D. Beer Assoc. Prof. Nicholas G. White 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(28):e202200389
We report the synthesis of two [2]rotaxanes containing an interlocked three dimensional binding cavity formed from a pyridinium bis(amide) axle component containing two phenol donors, and an isophthalamide based macrocycle. In the competitive solvent mixture 1 : 1 CDCl3 : CD3OD, one of the receptors exhibits a much higher selectivity preference for chloride than an analogous rotaxane without the hydroxy groups. X-ray crystal structures reveal the chloride anion guest encapsulated within the interlocked binding cavity, though not all of the hydrogen bond donors are utilised. Computational semi-empirical simulations indicate that secondary intermolecular interactions occur between the axle hydroxy hydrogen bond donors and the [2]rotaxane macrocycle components, contributing to a more preorganised binding pocket, which may be responsible for the observed enhanced selectivity. 相似文献
15.
Direct Spectroscopic Detection of the Orientation of Free OH Groups in Methyl Lactate–(Water)1,2 Clusters: Hydration of a Chiral Hydroxy Ester 下载免费PDF全文
Javix Thomas Dr. Oleksandr Sukhorukov Prof. Dr. Wolfgang Jäger Prof. Dr. Yunjie Xu 《Angewandte Chemie (International ed. in English)》2014,53(4):1156-1159
Hydration of chiral molecules is a subject of significant current interest in light of recent experimental observations of chirality transfer from chiral solutes to water in solution and the important roles which water plays in biological events. Using a broadband chirped pulse and a cavity based microwave spectrometer, we detected spectroscopic signatures of the mono‐ and dihydrates of methyl lactate, a chiral hydroxy ester. Surprisingly, these small hydration clusters show highly specific binding preferences. Not only do they strongly prefer the insertion H‐bonding topology, but they also favor specific pointing direction(s) for their non‐H‐bonded hydroxy group(s). We observed that the particular dihydrate conformer identified is not the most stable one predicted. This work highlights the superior capability of high‐resolution spectroscopy to identify specific water binding topologies, and provides quantitative data to test state‐of‐the‐art theory. 相似文献
16.
乙酸基和羟基对固化的环氧树脂吸水性能的影响 总被引:1,自引:0,他引:1
应用称重法、差示扫描量热法和腐蚀测试法研究固化的环氧树脂的吸水行为。实验结果表明,该树脂中的羟基改为乙酸基后可降低树脂的饱和吸水率,并增大水在树脂中的扩散能力。邻甲酚环氧树脂用乙酸线型酚醛酯树脂固化后所得的树脂(EPA)在30℃时饱和吸水率为0.84%(质量分数),而用线型酚醛树脂固化所得的树脂(EP)的则为1.97%;水在EPA和EP中的扩散活化能分别为40和48kJ.mol-1.这可归因于乙酸基中的甲基的憎水性,降低了吸水率,却因乙酸基的弱相互作用增强了链的柔顺性,而有利于水在链空间中的扩散。EPA涂层/金属铝界面的特殊结构降低了该界面的吸水率,从而提高了该涂层的防护性能。 相似文献
17.
相转移催化法制备侧链带有醛基的聚苯乙烯交联微球 总被引:1,自引:0,他引:1
首先使氯甲基聚苯乙烯交联微球(CCMPSt)在有机相中充分溶服,然后通过相转移催化剂(季铵盐)的作用,将水相中对羟基苯甲醛所产生的负氧离子转移至有机相,使之与CCMPSt微球表面的苄氯基团发生亲核取代反应,从而将CCMPSt微球转变为侧链带有醛基的聚苯乙烯交联微球(Aldehyde—CPSt).本研究重点考察了各种因素对液-液-固三相体系中相转移催化过程及取代反应的影响规律,较深入地探讨了反应机理.研究结果表明,通过相转移催化剂的作用,可将亲核取代试剂对羟基苯甲醛负氧离子不断地从水相转移至有机相,在有机相与交联微球CCMPSt的界面发生取代反应,从而将CCMPSt微球顺利地转变为功能微球Aldehyde—CPSt.有机溶剂的极性越强,对CCMPSt微球的溶服性能越好,取代反应速率越快;相转移催化剂季铵离子上的碳链对称性越好及碳链越长,相转移催化的效果越好;有机相与水相的比例对相转移催化效果也有较大的影响. 相似文献
18.
应用红外光谱和NH3-TPD法对LaDAlY型沸石的表面羟基和酸性进行了研究,从将La3+离子引入NH4Y和DAlY后表面羟基的变化中探讨了La3+离子在NH4Y和DAlY中的分布,吡啶吸附及脱附的红外光谱表明,在DAlY中引入La3+后B酸和L中心数均减少;NH3-TPD的结果表明,在DAlY中引入La3+离子后,其弱酸中心的强度稍有增加,而强酸中心的强度基本不变,酸中心数一般减少,其结果与吡啶-IR结果一致。 相似文献
19.
A thermometric method in which the heat of reaction is used as a quantitative measure of terminal OH groups in polymers has been in routine use. We use DDIE to determine the terminal OH groups in polyglycol and telechelic polybutadienes by the acetylation reaction of perchloric acid with acetic anhydride. The result is in good agreement with that of chemical titration, thus showing high reliability of DDIE in polymer end-group determination.
The method takes less than 5 minutes to carry out. The advantages of DDIE are simplicity, speed and also a repeatability is good. 相似文献
The method takes less than 5 minutes to carry out. The advantages of DDIE are simplicity, speed and also a repeatability is good. 相似文献
20.
Ribot F Martinez-Ferrero E Boubekeur K Hendrickx PM Martins JC Van Lokeren L Willem R Biesemans M 《Inorganic chemistry》2008,47(13):5831-5840
A tin(IV) oxoalkoxo cluster with unprecedented architecture has been prepared and characterized by single-crystal X-ray diffraction. The cluster obeys the formula Sn 12O 8(OH) 4(OEt) 28(HOEt) 4 (1) and is based on an elongated centrosymmetric assembly of 12 six-coordinate tin centers, 28 peripheral ethoxy groups (terminal and bridging), 8 oxo bridges (mu2 and mu3), 4 hydroxy bridges (mu2), and 4 ethanol molecules that are all bound to tin atoms and interact strongly, through hydrogen bonds, with an ethoxy group located on a vicinal tin atom. This compound has also been fully characterized in solution by multinuclear 1D and 2D NMR, with all of its (119)Sn, (1)H, and (13)C NMR resonances assigned with respect to the structure. Altogether, the data allowed unambiguous location of the hydroxy groups. Information on the exchange of the ethoxy groups is also presented. 相似文献