共查询到20条相似文献,搜索用时 161 毫秒
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以天然大茴香醛和发酵丙酮为起始原料,通过Claisen-Schmidt反应、选择性加氢、脱甲基实验得到天然级覆盆子酮。通过单因素实验和正交实验研究了三步反应的较佳工艺条件为:第一步,在氢氧化钠的作用下,氢氧化钠、大茴香醛以及丙酮的投料比为0.28:1:3,40℃反应1.5 h;第二步,催化剂雷尼镍的用量为1%,氢气压力为0.3 MPa,30℃反应14 h;第三步,以48%的氢溴酸做为催化剂,冰醋酸为溶剂,130℃,反应4h,得到天然级覆盆子酮,总收率:75.75%(以大茴香醛计),含量:98.65%,香气纯正。通过熔点、IR和~1H NMR对最终产物进行了结构表征。此工艺的研究为类似结构不饱和酮的选择性加氢提供了实验依据,且产品总收率较高,成本低,适合工业化生产。 相似文献
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以五甲基二乙烯三胺(PMDETA)、脂肪醇聚氧乙烯醚(FAPOE)和环氧氯丙烷(ECP)为原料,分两步合成了一种含聚氧乙烯醚链三头季铵盐的表面活性剂。对反应影响因素、产物结构与部分性能进行了分析与表征。结果表明:第一步反应n(ECP):n(FAPOE)为2.5~3:1,溶剂为正己烷,四丁基溴化铵作相转移催化剂,无水K2CO3作缚酸剂,时间6~8h。第二步反应n(中间体):n(PMDETA)为3.5—4.0:1,溶剂为正丁醇,时间40-45h;溶剂与时间是主要影响因素。定性表征符合产物结构:定量表征n(Cl^-):n(阳离子部分)为3.4:1,略高于理论值。产物的表面活性高,1.0×10^-4mol/L水溶液的表面张力可降至6.65mN/m。 相似文献
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A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selectivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied. 相似文献
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Kajsa Stridsberg Ann-Christine Albertsson 《Journal of polymer science. Part A, Polymer chemistry》1999,37(16):3407-3417
Ring-opening polymerization of 1,5-dioxepan-2-one initiated by 1,1,6,6-tetra-n-butyl-1,6-distanna-2,5,7,10-tetraoxacyclodecane was carried out in chloroform, dichloromethane, or 1,2-dichloroethane. Effects of reaction temperature, solvent, and monomer-to-initiator ratio were investigated. Polymerization kinetics showed a first-order dependence on the monomer for polymerization in chloroform and dichloromethane at 40°C. The kinetic order with respect to the initiator were a first order when dichloromethane was used as the solvent, the order in initiator changed, depending on the initiator concentration when chloroform was used. A maximum in molecular weight was observed at 40°C when chloroform was used as the solvent. The change of solvent did not markedly alter the polymerization rate or the molecular weight of the polymers prepared, as expected from the coordination insertion mechanism. Depolymerization of the polymers formed was observed when the reaction was allowed to continue after complete monomer conversion in chloroform as reaction medium at 40°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3407–3417, 1999 相似文献
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A study into the effect of reaction variables on the quaternization of REM resin-bound tertiary amines was undertaken. The influence of resin matrix, solvent, reaction time, temperature, and amount of quaternization agent on the outcome of reaction was evaluated by reaction monitoring using (19)F NMR. The highest yields of tertiary amine products were seen when DMSO was used as reaction solvent in conjunction with a reaction time of 18 h at room temperature. The use of heating for extended reaction times tended to depress yields, indicating product cleavage during quaternization. Quaternization on PS-DVB resin was found to be more robust than reaction on PS-PEG matrices where yields were generally considerably lower than the observed conversions. DMSO was the most efficient reaction solvent for both resins despite poor swelling of the quaternization starting material. 相似文献
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H Castejon K B Wiberg S Sklenak W Hinz 《Journal of the American Chemical Society》2001,123(25):6092-6097
The reaction of ammonia and pyridine with trimethylsulfonium ion has been studied in gas phase and solution. Density functional theory at the B3LYP/6-31+G level was used to describe the energy changes along the reaction coordinate in the gas phase, and the self-consistent isodensity polarizable continuum model (SCI-PCM) was used to calculate the effect of cyclohexane and dimethyl sulfoxide as the solvent on the energy changes. The effect of water as the solvent was studied using the Monte Carlo free energy perturbation method. The reaction with both ammonia and pyridine follows a similar rather convoluted path in gas phase, with the formation of several reaction complexes before and after the formation of the transition state. All the species found in gas phase persist in cyclohexane, yielding a reaction path very similar to that in gas phase but with significant differences in the relative energy of the critical points. In DMSO, the energy profile is greatly simplified by the disappearance of several of the species found in gas phase and in cyclohexane. The activation free energy increases with the polarity of the solvent in both reactions. Increasing the polarity of the solvent also increases the exothermicity of the reaction of trimethylsulfonium ion with ammonia and reduces it in the reaction with pyridine. In water, the free energy profile follows the same trend as found for DMSO, and free energy of activation is calculated to be larger by about 2-3 kcal/mol. This is in good agreement with an experimental measurement of the effect of solvent on the rate of reaction. 相似文献
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The production of monovinylacetylene (MVA) through Cu(I)-catalyzed acetylene dimerization reaction was performed in different reaction media. Based on the analyses of crystals precipitated from the catalyst solution and UV-Vis spectra of the catalysts, the reaction mechanism and solvent dependence were studied. The highest yield of MVA can be obtained when dimethylformamide is used as solvent because of its strong coordination ability to Cu(I). The activation of C≡C bond is presumed to be improved when the catalytic metal ion is coordinated by a solvent with less steric hindrance and electron-rich coordination atom. The results of the present study provide a possible way to accelerate the metal-catalyzed homogeneous reaction of alkyne substrates through careful selection of a solvent. 相似文献
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The reaction free energy curves for a model phenol-amine proton-transfer system in a confined CH3Cl solvent have been calculated by Monte Carlo simulations. The free energy curves, as a function of a collective solvent coordinate, have been obtained for several fixed reaction complex radial positions (based on the center-of-mass). A smooth, hydrophobic spherical cavity was used to confine the solvent, and radii of 10 and 15 A have been considered. Quantum effects associated with the transferring proton have been included by adding the proton zero-point energy to the classical free energy. The results indicate the reaction complex position can be an important component of the reaction coordinate for proton-transfer reactions in nanoconfined solvents. 相似文献
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采用放射性同位素3H标记的四氢萘溶剂进行了先锋褐煤与低密度聚乙烯(LDPE)的共液化示踪试验,并考察了钼灰(FAMo)和Fe2O3+S催化剂的影响。应用液体闪烁计数器测量了各液化产物中的放射性活度,以研究煤与废塑料共液化中的氢转移。结果表明:在先锋褐煤与LDPE塑料共液化反应的初始阶段,存在着四氢萘溶剂的供氢作用,而且这种供氢作用不受催化剂的影响,只是热力作用的结果。使用加氢蒽油(HAO)和四氢萘(THN)溶剂混和物作为共液化溶剂时,先锋褐煤与LDPE共液化反应初期的溶剂供氢还存在着竞争转移,其主要取决于溶剂的脱氢能力。 相似文献
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Serdakowski AL Munir IZ Dordick JS 《Journal of the American Chemical Society》2006,128(44):14272-14273
Enzymes are shown to function in nonaqueous media; however, relatively little information is available on the influence of the organic solvent as well as its associated water content on the properties of the enzymatic transition states. A better understanding of these effects will be useful in developing kinetic models that can then be used to predict optimal solvent and substrate choices for enzymatic reactions in organic media. The influence of the reaction media on soybean peroxidase-catalyzed oxidation of para-substituted phenols was studied using Hammett analysis for several organic solvent systems. The catalytic activity and substrate specificity of the enzyme are influenced by the nature of the solvent and its associated hydration. These findings may allow one to draw conclusions about the reaction mechanism and the roles of solvent and solvent hydration on enzyme function. 相似文献
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LIU Yu-Gang FEI Chang-PeiInstitute of Chemistry Chinese Academy of Sciences Beijing ChinaCHAN Tak-HangDepartment of Chemistry McGill University Montreal PQ Canada HA K 《中国化学》1994,12(1):85-94
The alkylation reaction of guanine and N-acetylguanine with model compounds such as isopropyl bromide or 4-heptyl tosylate were studied. The reaction conditions such as temperature, solvent, base, and catalyst were examined for their effects on the reaction rate, and the yield and regioselectivity of the coupling reaction. The highest yield was obtained by using DMSO as the solvent. The reaction proceeded in a homogenous manner to give higher yield of 9-N and 7-N substituted product in a mole ratio of 1:1. The ratio could be raised to 2:1 if dibenzo-18-crown-6 was used as a catalyst. Using the above procedure, three carba-DHPG analogues bearing different 1'-C alkyl side chains were synthesized. 相似文献
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溶剂对固相反应法制备H7PW12O42掺杂聚苯胺的影响 总被引:6,自引:0,他引:6
利用固相反应法,分别以微量的水和乙腈作为溶剂,制备了磷钨酸(H7PW12O42)掺杂聚苯胺,并以红外光谱(FTIR),电子扫描显微镜(SEM),X射线衍射(XRD),循环伏安(cyclic voltamogram)等测试方法对聚苯胺进行了表征。结果表明,固相反应法合成的聚苯胺分子链排列有序,晶化率较好,并且表现出有较好的电化学稳定性。而以微量的乙腈作为溶剂通过固相反应法得到的磷钨酸掺杂聚苯胺在颗粒形貌、结晶性、导电率等方面均优于相同条件微量的水作为溶剂时的掺杂聚苯胺。 相似文献