Lewis酸催化高区域选择合成对位柑菁醛的研究

Ｌｅｗｉｓ酸催化高区域选择合成对位柑菁醛的研究尹笃林，银董红，李谦和（湖南师范大学精细催化合成研究所，长沙４１００８１）关键词月桂烯，丙烯醛，对位柑菁醛，Ｄｉｅｌｓ－Ａｌｄｅｒ反应，Ｌｅｗｉｓ酸，络合催化。１．前言可从松节油资源中制取的月桂烯（ｍｙｒ...     

三羟甲基十一烷的合成与表征

三羟甲基烷烃是用于醇酸树脂、聚氨酯树脂、表面活性剂、合成润滑油等的原料[1-3].三羟甲基十一烷(化学结构见图1)作为三羟甲基烷烃中直碳链最长的一员,不仅具有亲水性(分子中含三个亲水基),而且具有疏水性(含一个长直碳链亲油基),因此可用作表面活性剂.不仅如此,与同样用作乳化剂的一般高级脂肪醇(如十六烷醇)相比,可以在化妆品用的乳液中加入三羟甲基十一烷作乳化剂,以降低乳液的黏度,防止乳液中由于大量加入高级脂肪醇而导致产品黏度过高以至不能在皮肤上被充分涂抹开的状况发生[4].为制备智能芳香缓释型聚氨酯微胶囊壳材[5],需要设计聚氨酯的分子结构中含有能与相变石腊和油溶性香料有良好相容性的疏水链(三羟甲基十一烷与六亚甲基二异氰酸酯的加成物).因此,本文合成并表征了三羟甲基十一烷.     

乳状液膜分离肌酐的研究

以液体石蜡为膜相、以氧化环糊精为内相捕捉剂制备一种新的乳状液膜，尝试运用其清除分离肌酐。实验发现当外相肌酐溶液浓度为1．3g/L，载体月桂醛含量为5％，内相氧化环糊精浓度为10％时，乳状液膜吸附容量为22．5mg／g。内相氧化环糊精的浓度对单位吸附量起决定作用。此种吸附剂对氨基酸吸附量仅为肌酐的1／10，这为其在含大量氨基酸的人体环境中有效的清除肌酐提供了优良的选择性。     

不饱和醛的新合成法

不饱和醛的新合成法史真，顾焕（西北大学化学系，西安７１００６９）不饱和醛是一类结构特殊的醛，常由醛缩合或不饱和醇氧化制得。本文在研究咪唑啉还原反应的基础上，提出了不饱和醛的一种未见文献报道的合成方法。这一新合成方法，突破了传统的制备方法，以不饱和羧酸...     

微波固相法制备ZnCl2／NaY催化剂

比较了微波固相法，普通加热法和简单混合法制备的ＺｎＣｌ２／ＮａＹ及溶液离子交换法制备的ＺｎＮａＹ在月桂烯与丙烯醛Ｄｉｅｌｓ－Ａｌｄｅｒ反应中的催化性能，发现微波固相法制备的催化剂表现出最高的环加成选择性和区域选择性。     

月桂烯环加成合成不饱和的环状硫醚

由二苯甲酮合成二苯甲硫酮，再使它与月佳烯发生环加成反应，合成了两种不饱和环状硫醚，总产率７４．６％。     

稀土(镧)硫醇盐的合成与表征

以三氧化二镧为原料, 经过醇化, 制备了三(月桂硫醇)镧及三(巯基乙酸异辛酯)镧, 并对合成方法进行了优化. 采用热失重分析、FTIR光谱、感应耦合等离子色谱、元素分析和1H NMR对目标产物进行了表征. 确定合成稀土异丙醇盐最佳反应条件为: 反应温度80 ℃, 反应时间2 h; 合成三(月桂硫醇)镧的反应条件为反应温度110 ℃, 反应时间2 h, 月桂硫醇的摩尔分数过量24％; 合成三(巯基乙酸异辛酯)镧的反应条件为反应温度60 ℃, 反应时间2 h, 月桂硫醇过量32％.     

ZnCl2离子液体中高区域选择性合成对位柑菁醛

 二烷基咪唑或烷基吡啶卤化物与ZnCl2构成一类新型的具有Lewis酸性的离子液体,以其为催化剂和反应介质,通过月桂烯与丙烯醛的Diels-Alder反应高区域选择性地合成了对位柑菁醛. 结果表明,与常规有机溶剂-ZnCl2催化体系相比,该体系不仅显著地加快了反应速率,而且明显提高了对位柑菁醛的区域选择性. 当ZnCl2与二烷基咪唑或烷基吡啶卤化物的摩尔比为2∶1,温度为15 ℃时月桂烯几乎可完全转化为柑菁醛,且对位柑菁醛的区域选择性p/m＞18. 与氯铝酸盐离子液体相比,该离子液体对水和空气不敏感. 反应结束后,产物与离子液体自动分层,解决了传统均相催化体系中催化剂与产物不易分离的问题. 分离后的离子液体用正己烷清洗提纯后,重复使用4次,其催化活性和区域选择性基本保持不变.     

由香茅醛合成羟基香茅醛的研究

羟基香茅醛具有玲兰样香气,是一种传统的合成香料,主要用于调配各种花系列香精、食品香精、化妆品香精等。我们对它的合成方法进行了改进研究,用二乙醇胺与香茅醛缩合生成噁唑烷衍生物,将醛基保护,再用硫酸加助催化剂将其双键水合,进而将缩合物水解得握基香茅醛。     

Palladium-Catalyzed Oxidation of Dihydromyrcene to Citronellal in Supercritical Carbon Dioxide

Citronellal was the major product of catalytic oxidation of dihydromyrcene with oxygen using the catalyst comprised of (MeCN)2PdC1NO2 and CuC12 in a tertiary alcohol in supercritical carbon dioxide. It was found that the chemoselectivity of the reaction and the yield of citronellal were greatly affected by the pressure of carbon dioxide, the reaction temperature and the molar ratio of Pd/Cu.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

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%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

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.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

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.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

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.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

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.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

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.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

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.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

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.