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To study the synthesis of 3,4-dihydro-2H-3-phenyl-1,3-benzoxazine (benzoxazine), the reaction paths of phenol, aniline and formaldehyde were investigated by analyzing the synthesis crude products. With the aid of high-performance liquid chromatography (HPLC), chromatographic column and preparative HPLC, seven compounds originated from the crude products were obtained and their chemical structures were elucidated. Possible reaction paths are proposed based on these compounds. Results show that Nhydroxymethyl aniline (HMA) derived from the reaction of formaldehyde and aniline is probably the key intermediate during the reaction. HMA can react with itself or other reactants to form other intermediates, such as 1,3,5-triphenyl-1,3,5-triazinane and 2-((phenylamino)methyl)phenol, and further form benzoxazine and byproducts. 相似文献
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The radiation-induced decomposition of 4-chloroaniline (4-ClA) was studied under steady-state conditions using aqueous solutions saturated with air, pure oxygen, N2O, argon and argon in the presence of t-Butanol. Using HPLC-method, the initial G-values of the substrate degradation as well as of a number of radiolytic products were determined. The formation of aminophenols, chlorophenols, aniline and phenol in addition to chloride, ammonia, formaldehyde and mixture of aldehydes as well as carboxylic acids was studied as a function of absorbed dose. Based on the experimental data, probable reaction mechanisms for the degradation of 4-ClA by γ-rays and the formation of the identified products are presented. 相似文献
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The stereocontrol steps of the (S)-proline catalyzed Mannich reaction of cyclohexanone, formaldehyde, and aniline were theoretically investigated. The geometries of reactants, products, and transition states were optimized using density functional theory using the B3LYP functional with the 6-31++G(d,p) basis set. The energies of these compounds were then more accurately determined at the MP2 level, and the effect of DMSO as the solvent was included using a polarizable continuum model (PCM). The reaction was modeled from the previously proposed mechanism that cyclohexanone reacts with (S)-proline to generate an enamine, while formaldehyde reacts with aniline to produce an imine, and that the conformation around the C-N bond of the enamine 1 is crucial for the further enantioselective step. The formation of two conformations of the enamine via a proton transfer process was examined, revealing activation barriers for syn- and anti-enamine proton transfer of 10.2 and 17.9 kcal/mol, respectively. The transformation of syn- to anti-enamine through C-N bond rotation, however, was predicted to require only 4.2 kcal/mol, while the (S)- and (R)-intermediates could be obtained from subsequent reactions between enamine and imine with energy barriers of 8.5 and 12.4 kcal/mol, respectively. The difference between these barriers, but not the C-N rotation energy, becomes larger at the MP2 level and when DMSO as a solvent is included. This predicted enantioselective reaction, through the kinetic and thermodynamic favoring of the (S)-pathway, is in agreement with experimental results, which have reported the (S)-configuration as the major product. 相似文献
5.
N.G. Grigorieva S.A. Kostyleva S.V. Bubennov V.R. Bikbaeva A.R. Gataulin N.A. Filippova A.N. Khazipova T.R. Prosochkina B.I. Kutepov Narender Nama 《Journal of Saudi Chemical Society》2019,23(4):452-460
High activity and selectivity of the hierarchical H-Ymmm zeolite in the synthesis of practically important pyridines (by interaction of C2–C4 alcohols with formaldehyde and ammonia, cyclocondensation of acetaldehyde and propanal with ammonia), dialkyl quinolines (by reaction of aniline with aldehydes) and alkyl dihydroquinolines (by reaction of aniline with ketones- acetone, acetophenone) were revealed in the research.The advantages of the micro-meso-macroporous H-Ymmm zeolite over the microporous H-Y zeolite in the synthesis of pyridines and quinolines were demonstrated. In the products formed by the reaction of ethanol with formaldehyde and ammonia, picolines (up to 63%) and lutidine are predominant in H-Ymmm, Pb-H-Ymmm and Fe-H-Ymmm zeolites. The interaction of n-propanol (n-butanol) with formaldehyde and ammonia in the presence of H-Ymmm zeolite with high selectivity produced 3,5-lutidine (up to 90%) or 3,5-diethylpyridine (85%). H-Ymmm zeolite makes it possible to prepare 2-methyl-5-ethylpyridine with 87% selectivity (reaction of acetaldehyde with ammonia) and 2-ethyl-3,5-dimethylpyridine with 58% selectivity (reaction of propanal with ammonia).The synthesis of dialkylquinolines and dialkyltetrahydroquinolines with a total selectivity of 65–73% by the interaction of aniline with C3–C5 aldehydes has been carried out. The dihydroquinoline derivatives with the selectivity of up to 70% have been synthesized by the reaction of aniline with ketones (acetone, acetophenone). 相似文献
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Composite of conducting polyaniline-isobutylated urea formaldehyde: Preparation and characterization
Bakhshali Massoumi Raheleh Magssoudi Elmira Kashani Ali Akbar Entezami 《Polymer Science Series A》2011,53(8):727-732
Composite of conductive polyaniline-isobutylated urea formaldehyde have been prepared by chemical oxidative emulsion polymerization
of aniline in the presence of isobutylated urea formaldehyde resin (BUFR) in toluene-water solvents at room temperature. The
mass loading of polyaniline was controlled by varying the BUFR/aniline charging ratio as well as oxidant (ammonium persulfate)/aniline
molar ratio. Some factors capable of affecting the yield and conductivity of composite, such as amount of the oxidant, type
of the dispersants (span-80 and span-20), and amount of resin and organic acid (para-toluene sulfonic acid) were investigated.
The prepared composites were characterized by FTIR spectroscopy and scanning electron microscopy (SEM). 相似文献
8.
Magda F. Fathalla 《中国化学》2012,30(1):109-114
Kinetics of the reaction of 2‐chloro‐3,5‐dinitrobenzotriflouride with aniline were studied in toluene, methanol‐toluene binary solvents, benzene and chloroform. The reaction in toluene exhibits third‐order kinetics consistent with aggregates of aniline. Thermodynamic parameters (H#, (S# and (G#are calculated and discussed for the reaction of 2‐chloro‐3,5‐dinitrobenzotriflouride with aniline in methanol‐toluene. Molecular complexes between aniline and the substrate are rejected spectrophotometricaly. The mechanism is studied and compared with the reaction in presence of pyridine. It shows an amine dependence and formation of homo and/or hetero mixed aggregates between aniline and pyridine i.e. dimer mechanism. 相似文献
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Chun Yang WANG Tong ZHAO* Center for Molecular Science Institute of Chemistry the Chinese Academy of Science Beijing 《中国化学快报》2001,(10)
Thermally resistant structural materials play a key role in the progress of the electronics and aerospace industries. Polybenzoxazine, a novel ring-opening phenolic resin, with superior properties such as no volatile emission when curing, near zero shrinkage and high mechanical performance, can be deemed as alternatives of traditional phenolics. Layered clays dispersed in a polymer matrix on nanoscale reinforced the thermal resistance and mechanical performance of the composite. The prepara… 相似文献
10.
邻氯硝基苯在Pd/C催化剂上加氢反应机理及添加Cu对邻氯苯胺选择性的影响 总被引:2,自引:0,他引:2
本文研究了邻氯硝基苯在5%Pd/C催化剂上加氢为邻氯苯胺和苯胺的反应机理。结果表明,在常压下,邻氯苯胺和苯胺的选择性分别为~70%和~30%,且不随转化率增加而变化。在加压(1.0 Mpa)条件下,也有类似规律。因此,说明邻氯苯胺和苯胺分别是两个平行反应的产物。通过测定该反应各步骤的初始反应速率,进一步证实了这一结论。在认识反应机理的基础上,制备出可有效抑制脱氯的Cu-Pd/C双金属催化剂,在不加脱氯抑制剂的情况下,可使邻氯硝基苯加氢制备邻氯苯胺的选择性提高到96%以上。 相似文献
11.
Mechanistic investigations were pursued to determine a plausible mechanism in the cascade reaction involving tetronic acid with aldehydes and anilines to generate the 4-aza-2,3-dehydropodophyllotoxin core structure. The mechanistic driven hypothesis paved the way for a new reaction design using for the first time a sacrificial electron deficient aniline leading to an optimized cascade protocol (up to threefold yield improvement) for the synthesis of novel 4-aza-2,3-dehydropodophyllotoxin analogues. 相似文献
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Lingaiah Nagarapu Hanmanth Reddy Vulupala Ch. Venkatanarsimhaji Rajashaker Bantu A. Ramakrishna Reddy 《合成通讯》2013,43(14):2131-2138
A short and simple synthesis of tetrahydropyrimidine derivatives were accomplished in good to excellect yields at room temperature by the reaction of dimethylacetalynedicarboxylate, aniline, and formaldehyde in the presence of 5 mol% of molecular iodine at room temperature in ethanol for 5 min. 相似文献
13.
《Tetrahedron letters》1986,27(17):1887-1890
Contrary to earlier reports, the formation of bis(aminophenyl) methanes in the acid-catalyzed condensation of aniline and formaldehyde can result in carbon—carbon bond cleavage proceeding via an ipso protodealkylation mechanism. 相似文献
14.
Ivanova I. I. Pomakhina E. B. Rebrov A. I. Wang W. Hunger M. Weitkamp J. 《Kinetics and Catalysis》2003,44(5):701-709
The alkylation reaction of aniline with methanol on zeolites HY and CsOH/CsNaY was studied by in situ
13C NMR spectroscopy under flow and batch conditions. Attention was focused on the identification of intermediates and on the determination of the formation mechanisms of N-methylaniline, N,N-dimethylaniline, and toluidines. To refine the main steps of the reaction, the transformations of the following individual compounds and intermediates, which were detected in the course of alkylation, were studied: dimethyl ether, surface methoxy groups, methylanilinium ions, formaldehyde, and N-methyleneaniline. It was found that N-methylaniline and N,N-dimethylaniline were formed as a result of aniline methylation by methanol dehydration products (methoxy groups or dimethyl ether) on acidic zeolites or as a result of alkylation by formaldehyde or methoxy groups on basic zeolites. Toluidines were formed by the isomerization ofN-methylanilinium ions, which were produced only on acidic zeolites, rather than by the direct alkylation of aniline. 相似文献
15.
高效液相色谱直接测定甲醛衍生物反应条件的研究 总被引:23,自引:0,他引:23
研究了直接用于液相色谱测定甲醛与2,4-二硝基苯肼的反应条件,使反应在弱酸性和50%的乙腈条件下进行,反应产物甲醛衍生物不需要有机溶剂萃取,可直接用于液相色谱分析,避免了萃取过程的损失。该反应条件与传统的在强酸性条件下的反应进行比较。本实验所研究的反应条件用于液相色谱测定甲醛具有操作方便、准确和应用范围广等特点。在样品中添加5.14,10.28和51.4mg/kg,回收率分别为108%、93.1%和86.2%相对标准偏差(n=10)分别为1.13%、1.34%和1.29%。 相似文献
16.
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
17.
在氧化铝模板中制备了HPA/PANI纳米线列阵,SEM、TEM表明列阵中纳米线直径约为80 nm;XRD与FT-IR证明形成了有效掺杂;单根纳米线的导电率为16.2 S.cm-1;材料的TG-DTA表明PANI纳米线材料有三步失重过程,失去吸附水过程,多酸失去结晶水和PANI结构持续分解过程,多酸结构分解过程;在氧化聚合过程中H4PMo11VO40即为质子酸又为氧化剂和掺杂剂;聚合反应采用自由基机理进行,掺杂反应发生在形成醌二亚胺式自由基正离子和双苯胺式自由基正离子和醌二亚胺式自由基正离子偶联聚合成链结构时. 相似文献
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In this report, synthesis of julolidines via one-pot cascade reaction of aniline derivatives with a mixture of styrene and formaldehyde in the presence of silica sulfuric acid as an efficient catalyst has been studied under aerobic condition. By presented method, various julolidines are obtained under mild and transition metal-free conditions. The reaction is proceeded with imine formation and followed by an Aza-Diels-Alder cycloaddition with styrene gave julolidine derivatives. The catalyst can be recycled and reused multiple times to catalyze the reaction. 相似文献
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Synthesis of 3-Phenyl-6-formyl-3, 4-dihydro-2H-1, 3-benzoxazine 总被引:2,自引:0,他引:2
Qi Chao RAN Qiao TIAN Yi GU 《中国化学快报》2006,17(10):1305-1308
Benzoxazine is a novel class of thermosetting resins, which possesses lots of outstanding properties such as no by-products and near-zero shrinkage during polymerization as well as good molecular design flexibility1-2. Furthermore, polybenzoxazines (PBZs)… 相似文献
20.
The reaction between urea and formaldehyde in water solution was theoretically investigated by using B3LYP and MP2 methods.It was found that the addition of the nitrogen atom in urea to the carbonyl group in formaldehyde precedes the proton transfer and the proton migration from water to the carbonyl group occurs before the proton abstraction from the nitrogen.With one or two water molecules involved in the TS.the activation energy barrier is lowered compared to the TS of the mechanism with no water participation.The energy change along the reaction coordinate clearly shows that a zwitterionic-like intermediate does not exist on the PES.The reaction between urea and formaldehyde occurs in a concerted mechanism but with asynchronous characters.This is different from the stepwise mechanism recently found for the amination reactions of formaldehyde. 相似文献