吡唑类化合物的合成研究进展

吡唑类化合物是一类重要的药物合成中间体,在抗肿瘤、抗病毒、抗抑郁等领域发挥着重要作用。本文综述了吡唑类衍生物的合成方法,包括1,3-亲电化合物与肼类的环化、1,3-偶极体系的环加成等。     

4-甲基-4-氮杂-21E-苯亚甲基-5-孕烯-3,20-二酮类化合物的合成

报道了一种以KF/Al_2O_3催化合成4-甲基-4-氮杂-21E-苯亚甲基-5-孕烯-3,20-二酮类化合物的方法。以黄体酮为原料,经NaIO_4/KMnO_4氧化裂解、胺解关环得到重要中间体4-甲基-4-氮杂-5-孕烯-3,20-二酮,后者在KF/Al_2O_3催化下经克莱森缩合得到目标产物。考察了不同的催化剂、反应温度、催化剂用量对目标产物的影响。条件优化的结果为:n(3)∶n(KF/Al_2O_3)=1∶1,回流状态下反应4 h,产率为56%~68%。此方法适用性好,为4-氮杂甾体苯亚甲基衍生物的合成提供了一种方便而有效的方法。     

L-苯丙氨酸衍生物的一锅法合成及其抗/促凝活性

氨基酸及其衍生物在止血/抗凝活性方面有一定的应用。以L-苯丙氨酸为起始原料,经磺化引入磺酸基,再与甲醇、乙醇、丙醇、异丙醇和正丁醇脱水酯化,一锅法合成了6种未见报道的L-苯丙氨酸的磺酸酯类衍生物(L1~L6),以期获得具有的较强血液生理活性的潜在药物。实验中采用了质谱、核磁共振进行结构表征。该合成方法产率高(78%~95%),后处理简单,不失为合成该类衍生物的好方法。衍生物的凝血四项实验表明:抗促凝效果是内源性和外源性凝血途径共同作用的结果。血浆复钙实验表明:衍生物均具有一定的抗凝活性,其抗凝效果随浓度变化而变化,但是随R链的长度增加,抗凝效果并未见规律性。衍生物的抗凝活性主要受磺酸基及酯基的影响,因此在设计合成抗血栓化合物时可以考虑引入磺酸基及酯类基团。     

High‐order compact schemes for fractional differential equations with mixed derivatives

In this article, we consider two‐dimensional fractional subdiffusion equations with mixed derivatives. A high‐order compact scheme is proposed to solve the problem. We establish a sufficient condition and show that the scheme converges with fourth order in space and second order in time under this condition.© 2017 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 2141–2158, 2017     

One-pot facile synthesis of polysubstituted pyridines via tandem reaction of the Blaise reaction intermediates and 3-formylchromones

A novel tandem one-pot method for the synthesis of polysubstituted pyridine derivatives has been developed via Knoevenagel-type reaction and subsequent 6π electrocyclization of the Blaise reaction intermediates and 3-formylchromones. Short reaction time, moderate to good yields and excellent functional group tolerance have been accomplished in this protocol.     

Facile synthesis of novel dihydroquinoline-3,3-dicarbonitriles in the presence of glacial acetic acid as a catalyst under solvent-free conditions

A series of novel dihydroquinoline derivatives were synthesized using malononitrile, 2-aminobenzoic acid, and benzaldehydes in the presence of a catalytic amount of acetic acid, without the use of any additional cocatalyst, under solvent-free conditions. The reaction is characterized by high efficiency, easy workup, simple purification of the products, and availability of catalyst.     

Synthesis and antimicrobial evaluation of some novel dithiolane,thiophene, coumarin,and 2-pyridone derivatives

Novel 2-cyano-N-[1-(naphtha-2-yl)ethylidene] acetohydrazide 1 was utilized as key intermediate for the synthesis of some new dithiolane, thiophene, coumarin, 2-pyridone, and other related products containing a hydrazide moiety. Newly synthesized compounds were characterized by elemental analyses and spectral data (IR, ¹H NMR and mass spectra). The antimicrobial activity of the synthesized compounds was evaluated.     

Synthesis of 4,8-dimethoxy-1-naphthol via an acetyl migration

Based on acetyl migration, an efficient synthesis of 4,8-dimethoxy-1-naphthol (1) has been achieved with high overall yield. Compared with the reported method, there were several advantages. First, the reaction conditions were mild. Second, the workup of each step was much simpler. Third, juglone as the starting material in the synthesis was readily available. The solvent and reaction temperature greatly influenced the migration process.     

Novel phosphorescent neutral iridium(III) complex with the steric hindrance for highly efficient red organic light-emitting diodes

A novel and highly efficient thiophenquinolone-based red iridium(III) complex bearing a bulky fluorophenyl moiety is designed and synthesized. The complex shows intensive red phosphorescence (596 nm with shoulder at 642 nm), high photoluminescence efficiency (0.62) and broad full width at half maximum (81 nm). The bulky fluorophenyl moiety introduced into the complex could improve the efficiency of electroluminescence with the maximum current efficiency, power efficiency and the external quantum efficiency up to 29.0 cd/A, 30.4 lm/W and 17.6% due to the effective steric hindrance in solid states.     

E-Stilbene derivatives synthesized by stereoselective reductive coupling of benzylic gem-dibromide promoted by Cu/polyamine

Stereoselective reductive coupling reaction of benzylic gem-dibromide promoted by Cu/polyamine produces E-stilbene derivatives with high yield under mild conditions. It provides a short pathway to synthesize symmetrical and asymmetrical E-stilbene derivatives using cheap reagents and alkenyl-free starting material together with easy workup.