共查询到20条相似文献,搜索用时 46 毫秒
1.
2.
用原位穆斯堡尔谱考察了不同担载量的Fe/AC催化剂的氮化以及随后的碳化行为。Fe/AC催化剂经500℃H预还原后,于350℃流动态氨气中氮化5小时可生成ε-氮化铁,其穆斯堡尔谱呈双峰(δ~0.42mm/s,△~0.32mm/s)。再在合成气(2H2/CO)中进行碳化处理,ε-氮化铁中的氮原子可逐渐被碳原子取代而转化为氮碳化铁和碳化铁,但铁的担载量越高,这种取代越困难。8%Fe/AC催化剂在250℃ 相似文献
3.
两相体系中钌膦配合物催化4—苯基—3—丁烯—2—酮加氢反应的研究 总被引:7,自引:0,他引:7
研究了水和有机物组成的两相催化体系中,由RuCl3-TPPTS(TPPTS:P(m-C6H4SO3Na)3)原位反应生成的催化活性物种对4-苯基-3-丁烯-2-酮(又名苄叉丙酮)的催化加氢反应.考察了钌浓度(1.0×10-3~6.0×10-3mol/L)、氢压(1.0~6.0MPa)、反应温度(30~70℃)、配体浓度(1.2~7.2×10-2mol/L)、阳离子表面活性剂(CTAB:十六烷基三甲基溴化铵)及反应时间等对加氢反应活性和选择性的影响,并与以配合物RuCl2(TPPTS)3为催化剂前体生成的催化活性物种对加氢反应的活性及选择性进行了比较.结果表明,分别由配合物RuCl2(TPPTS)3及RuCl3-TPPTS原位反应生成的催化活性物种,都只催化4-苯基-3-丁烯-2-酮的C=C键选择加氢.由配合物RuCl2(TPPTS)3形成的催化体系的加氢活性及选择性均优于RuCl3-TPPTS原位反应生成的催化活性物种.阳离子表面活性剂的加入,使加氢反应活性下降,选择性略有提高 相似文献
4.
芳胺常压气相N—烷基化反应研究 总被引:1,自引:0,他引:1
在固定床催化反应器中常压下研究了芳胺和醇的气相法N-烷基化反应。考察了γ-Al2O3系列催化剂的反应性能,筛选出了两种适用于苯胺N-甲基化反应且性能较好的催化剂。反应条件为:在甲醇和苯胺的摩尔比为3:1时,反应温度为280℃,液时空速为0.3h^-1的条件下,苯胺转化率为99%,生成N,N-二甲基苯胺(DMA)的选择性为92%。研究了甲醇和芳环上不同位置取代的甲基苯胺的反应规律,其转化率顺序:苯胺 相似文献
5.
芳胺常压气相N-烷基化反应研究 总被引:1,自引:0,他引:1
在固定床催化反应器中常压下研究了芳胺和醇的气相法N-烷基化反应。考察了γ-Al2O3系列催化剂的反应性能,筛选出了两种适用于苯胺N-甲基化反应且性能较好的催化剂。反应条件为:在甲醇和苯胺的摩尔比为31时,反应温度为280℃,液时空速为0.3h-1的条件下,苯胺转化率为99%,生成N,N-二甲基苯胺(DMA)的选择性为92%。研究了甲醇和芳环上不同位置取代的甲基苯胺的反应规律,其转化率顺序:苯胺≈对一甲苯胺≈间-甲苯胺>邻-甲苯胺。从C1到C4不同结构的醇和苯胺反应的规律研究,证明随醇中碳原子数目的增加,醇的反应活性降低,正构醇和苯胺反应和异构醇与苯胺反应随温度升高的变化趋势相反。 相似文献
6.
7.
8.
本文研究了两种水溶性钌-膦配合物RuCl_2(TPPTS)_3和Rucl_2(CO)_2(TPPTS)_2[TPPTS为:P(m-C_6H_4SO_3Na)_3]的合成,在水相和有机相组成的两相催化体系中,考察了它们衍生出的活性物种和以RuCl3-TPPTS原位合成的活性物种对肉桂醛的选择加氢性能,并对反应温度(20—80℃),氢压(2—6MPa),催化剂浓度(1.12×10~(-3)~4.50×10~(-3)mol/L),配体TPPTS浓度(9.0×10~(-3)~5.4×10~(-2)mol/L),表面活性剂浓度和反应时间的变化对选择加氢反应的影响进行了详细研究。实验结果表明,RuCl_3-TPPTS原位合成配合物的催化加氢活性最高,而在金属Ru上羰基的配位将使加氢活性降低,表面活性剂CTAB是有效的促进剂,它的加入可大大提高加氢活性,选择适当的CTAB浓度,在反应结束后水相与有机相分层迅速,有利于Ru催化剂的分离,在所考察的反应条件下,肉桂醛选择加氢生成肉桂醇的转化率大于80%,选择性达96%以上。 相似文献
9.
系统地研究了在4.0MPa氢压下,反应温度、催化剂浓度、溶剂等对丙醛均相加氢制正丙醇反应的影响,得出最佳反应条件为:氢压4.0MPa、温度80℃,RuCl3·3H2O为催化剂前体,用量98mg(0.35mmol),PPh3为393mg(1.5mmol),Ru/P摩尔比为1/4,DMF为溶剂.在此条件下,丙醛转化率和正丙醇选择性可分别达99%和95%以上.求出了不同反应温度下的反应速度常数.以RuCl3-PPh3为催化剂体系,丙醛加氢的活化能为77.62kJ/mol 相似文献
10.
11.
用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%. 相似文献
12.
Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields. 相似文献
13.
A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL. 相似文献
14.
Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction
Laurent Gavara Thomas Boisse Jean-Pierre Hénichart Adam Daïch Philippe Gautret 《Tetrahedron》2010,66(38):7544-5571
In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments. 相似文献
15.
A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions. 相似文献
16.
Uroš Grošelj Mojca Žorž Amalija Golobič Branko Stanovnik Jurij Svete 《Tetrahedron》2013,69(52):11092-11108
A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives. 相似文献
17.
The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp3)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp2)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp2)?H and aliphatic 1,5- and 1,6-C(sp3)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp3)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp2)?H insertion. 相似文献
18.
The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula. 相似文献
19.
KMnO4-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields. 相似文献
20.
Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular SN2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively. 相似文献