共查询到20条相似文献,搜索用时 156 毫秒
1.
2.
自由基氟烷基化是向有机分子中引入氟烷基的一类非常重要的方法,也是目前有机化学研究的热点之一.近几年来,由于广泛的官能团兼容性和温和的反应条件等优点,可见光促进的氧化还原催化反应得到了长足的发展,已经成为化学键的构建和活化的有力工具.因此,光氧化还原催化的自由基氟烷基化反应,作为向有机化合物中引入氟烷基的有效途径,受到了广泛关注.本文报道了我们发展的氟烷基砜作为一类方便易得的新型氟烷基自由基前体,在可见光氧化还原催化下实现对烯烃的自由基氟烷基化反应.该反应可以高效地向芳基烯烃中引入三氟甲基、二氟甲基、1,1-二氟乙基、苯基二氟甲基等各种含氟烷基基团,并实现对芳基烯烃的双官能团化转化. 相似文献
3.
4.
以胺和醇为原料,在Ni-Sn/Al2O3催化下液相合成氮烷基胺类化合物。反应工艺为连续式反应,醇既是烷基化试剂,又是供氢体和溶剂。考察了180 ℃下不同的胺与各类醇在Ni-Sn/Al2O3催化作用下的氮烷基化反应。研究表明该烷基化反应具有普遍的适用性,多数胺与甲醇、乙醇、正丁醇反应,具有较高的氮烷基化总产率。一些胺与醇反应产率甚至在99%以上。本文作了催化剂稳定性测试,并通过XRD和TEM对催化剂进行了表征,分析了催化剂失活的原因。研究表明,该催化剂具有很高的稳定性可保持高活性超过480 h,Lewis酸中心是氮烷基化反应的活性中心,随着反应进行,Lewis酸中心转化为Brφnested酸中心,致使催化剂活性降低。 相似文献
5.
6.
离子液体的酸性测定及其催化的异丁烷/丁烯烷基化反应 总被引:17,自引:3,他引:17
初次采用吡啶红外光谱探针法测定了离子液体的酸性.该方法能鉴别离子液体的Br¨onsted/Lewis酸类型,并可以粗略指示离子液体的Lewis酸强度.将[bmim]Cl/AlCl3类离子液体用于催化异丁烷与丁烯的烷基化反应,考察了酸强度、反应温度、压力和时间对产物分布的影响,并在最优操作条件下与传统的H2SO4催化剂进行了比较.结果表明,离子液体对烷基化反应的催化活性和选择性与H2SO4可比,而且它更容易与产物分离,不经任何处理可循环利用10次. 相似文献
7.
8.
9.
过渡金属催化醇与胺有氧脱水反应及相关研究进展 总被引:1,自引:0,他引:1
与其他胺和酰胺衍生物的合成方法相比,过渡金属催化醇与各类胺和酰胺的脱水N-烷基化反应是一种相对绿色、原子经济性较高的方法,一般被称为"借氢"或"氢自动转移"反应及其方法学.近年来,在空气氛围下过渡金属催化醇与胺和酰胺的有氧脱水N-烷基化反应,可使用更稳定的金属催化剂、可在无配体、空气等更温和简单的条件下进行,也引起了人们的极大关注.主要介绍近年来过渡金属催化下醇与胺和酰胺在空气或者氧化剂作用下构建C—N,C=N键合成胺和酰胺衍生物以及亚胺类化合物的有氧脱水反应进展情况,同时也对相关有氧脱水C-烷基化反应进行简单介绍.相关反应的机理研究也将作适当讨论. 相似文献
10.
利用同位素取代法考察了[Bmim]Br-AlCl3催化苯与1-十二烯烃烷基化反应机理. 首先进行了[Bmim]Br-AlCl3催化氘代苯与1-十二烯烃的反应, 通过GC-MS及NMR分析产物十二烷基苯同分异构体的结构, 验证了氘原子与产物侧链1-位碳相连的结论. 示踪氘原子推导了烷基化反应机理, 结果表明: [Bmim]Br-AlCl3催化苯与长链烯烃的烷基化反应是由[Al2Cl6Br]-发生平衡移动, 生成Lewis酸AlCl3引发的; AlCl3吸电子作用使1-十二烯烃的π电子向1-碳转移, 在烯烃的2-碳上形成正电荷中心, 碳正离子与苯发生亲电反应生成不稳定的σ络合物, 与σ络合物环上的σ-C相连的D+转移到负电的侧链1-C上形成C—D键, AlCl3离去, 生成产物2-十二烷基苯. Lewis酸催化机理为离子液体催化苯与长链烯烃的反应中, 2-十二烷基苯选择性高于H质子催化产物提供了理论依据. 相似文献
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.
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
14.
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
15.
Rebecca J. Burton Mandy L. CrowtherNeal J. Fazakerley Shaun M. FilleryBarry M. Hayter Jason G. KettleCaroline A. McMillan Paula PerkinsPeter Robins Peter M. SmithEmma J. Williams Gail L. Wrigley 《Tetrahedron letters》2013
The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines. 相似文献
16.
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
17.
N. A. Nedolya 《Chemistry of Heterocyclic Compounds》2008,44(10):1165-1219
The review contains a concise historical account and information on the most significant researches undertaken by the staff
at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry
of Heterocyclic Compounds.
Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008. 相似文献
18.
Regiospecific and direct imidation of the methyl C(sp3)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products. 相似文献
19.
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
20.
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