卤代芳烃的氰基化反应

以亚铁氰化钾为氰基化试剂,以醋酸钯为催化剂制备了芳香族氰基化合物。考察了原料比、时间、反应温度、催化剂的用量等反应条件对反应的影响,确定了较佳的反应条件。在n(K4[Fe(CN)6].3H2O):n(PhBr):n(Pd(OAc)2)=200:1000:1,反应温度130℃,反应1.5h条件下,溴苯转化率达99%,产物氰基苯收率为95%。氰基化试剂亚铁氰化钾与传统的氰基化试剂相比无毒,无需经过复杂的预处理,而且廉价易得。这种氰基化反应催化体系简单,无需添加昂贵的催化剂配体,催化剂的用量少,并且反应的后处理简单,对环境污染小,是一种效益明显的氰化芳烃的制备方法。同时进一步考察了其它卤代芳烃的氰基化反应,活泼的溴代芳烃和碘代芳烃均能得到很好得率:91%～96%。     

6-氰基吲哚-3-甲醛的合成

6-氰基吲哚-3-甲醛的合成;氰基吲哚;氰基吲哚甲醛;合成     

4-氨基-4'-氰基联苯的合成

氨基氰基联苯;4-氨基-4'-氰基联苯的合成     

气相色谱-串联质谱法测定2-氰基溴苄中3-氰基溴苄和4-氰基溴苄的含量

建立了气相色谱-串联质谱法测定苯甲酸阿格列汀关键起始物料2-氰基溴苄中基因毒性杂质3-氰基溴苄和4-氰基溴苄含量的分析方法。采用50%苯基-50%二甲基聚硅氧烷为固定液的VF-17MS毛细管柱(30m×0.25mm,0.25μm)进行程序升温;进样口温度260℃;以多反应监测(MRM)模式检测。2种待测物均具有较好的线性关系,相关系数均大于0.998 0;检出限(3S/N)均为2.0μg·L^-1;3-氰基溴苄的回收率为92.1%~97.0%;4-氰基溴苄的回收率为102%~109%;供试品溶液、杂质对照品溶液和系统适用性溶液在室温(25℃)下放置18h内稳定。三批生产规模样品中均未检出3-氰基溴苄和4-氰基溴苄。建立的分析方法灵敏度高、分离度好、结果准确,可有效分离并测定2-氰基溴苄中的3-氰基溴苄和4-氰基溴苄含量,为苯甲酸阿格列汀的安全性提供了保障。     

氰基在药物分子设计中的应用

含氰基药物在临床治疗药物中占有相当比重.将氰基基团引入到小分子药物中是药物化学结构改造的重要研究策略之一.综述了氰基在药物分子设计中的应用,氰基的引入可以调节小分子药物的物理化学特性,改变小分子的药代动力学性质,提高药物的生物利用度;通过氢键相互作用、共价相互作用、偶极相互作用以及π-π相互作用增强配体与靶标蛋白的相互结合能力以及对其它靶标蛋白的选择性;同时,氰基是羰基、卤素等多种官能团的生物电子等排体;将氰基引入到药物小分子当中,可以通过阻断易代谢位点进而提高药物代谢稳定性等.     

双对苯氰基系列分子气相HeI紫外光电子能谱和量子化学研究

测定了4,4′-二氰基联苯(1),4,4′-二氰基二苯醚(2),4,4′-二氰基二苯甲烷(3),4,4′-二氰基二苯酮(4),4,4′-二氰基二苯砜(5)的气相HeI紫外光电子能谱,借助于Gauss-94采用RHF/6-31G方法对其几何构型作全优化,计算分子轨道及能级,对其低电离能区的谱带给予指认,得到通过空间和通过键作用的相对强弱直接影响分子轨道次序的结论. 将立体效应和电子效应分开讨论,得到该系列分子电离能的变化规律.     

含氰基的酚醛树脂及其碳纤维复合材料

含氰基的酚醛树脂，具有优异的耐高温性能和高温下的机械强度，在３１５℃下性能变化甚小；不着火，发烟量低，有良好的加工成型性能。热固化过程中氰基成三嗪环而交联，没有小分子脱出，是一类具有广泛发展前景的新型热固性树脂。     

氰基化合物非均相加氢制备有机胺的研究进展

介绍了不同结构的氰基化合物加氢还原制备有机胺的研究工作,重点对用非均相催化剂的氰基化合物加氢研究现状进行了综述,指出高性能催化剂的开发仍是今后研究的主要方向。     

高效液相色谱法测定邻氰基苄基膦酸二乙酯

高效液相色谱法测定邻氰基苄基膦酸二乙酯＊许峰何大森宋跃群张禹应玲（浙江师范大学化学系浙江金华３２１００４）关键词高效液相色谱邻氰基苄基膦酸二乙酯邻氰基苄基膦酸二乙酯（ＤＣＰ）是生产荧光增白剂ＥＲ的重要中间体［１］。它由邻氰基甲苯光氯化，邻氰基氯苄酯化...     

含氰基高性能聚芳醚材料的合成与表征

将合成的含氰基的双二氮杂萘酮单体与二氟芳香单体进行亲核取代反应, 制备了三种含氰基的新型聚芳醚, 并用TGA, DSC和GPC等分析手段对其综合性能进行表征. 结果表明, 含氰基聚芳醚具有优异的热稳定性(T5%>492 ℃)、较高的玻璃化转变温度(Tg=262~320 ℃)和良好的溶解性能, 易溶于氯代烷烃(如氯仿)和极性非质子性溶剂(如DMAc, DMF, NMP等).     

One-Pot Synthesis and Applications of N-Heteroaryl Iodonium Salts

An efficient one-pot synthesis of N-heteroaryl iodonium triflates from the corresponding N-heteroaryl iodide and arene has been developed. The reaction conditions resemble our previous one-pot syntheses, with suitable modifications to allow N-heteroaryl groups. The reaction time is only 30 min, and no anion exchange is required. The obtained iodonium salts were isolated in a protonated form, these salts can either be employed directly in applications or be deprotonated prior to use. The aryl groups were chosen to induce chemoselective transfer of the heteroaryl moiety to various nucleophiles. The reactivity and chemoselectivity of these iodonium salts were demonstrated by selectively introducing a pyridyl moiety onto both oxygen and carbon nucleophiles in good yields.     

New boryl radicals derived from N-heteroaryl boranes: generation and reactivity

Recently, boryl radicals have been the subject of revived interest. These structures were generated by hydrogen-abstraction reactions from the corresponding boranes (i.e., from amine or phosphine boranes). However, the classical issue remains their high B--H bond-dissociation energy (BDE), thereby preventing a very efficient hydrogen-abstraction process. In the present paper, new N-heteroaryl boranes that exhibiting low B--H BDE are presented; excellent hydrogen-transfer properties have been found. Both the generation and the reactivity of the associated boryl radicals have been investigated through their direct observation in laser flash photolysis. The boryl radical interactions with double bonds, oxygen, oxidizing agent, and alkyl halides have been studied. Some selected applications of N-heteroaryl boryl radicals as new polymerization-initiating structures are proposed to evidence their high intrinsic reactivity.     

Novel N-aryl and N-heteroaryl sulfamide synthesis via palladium cross coupling

A novel and efficient synthesis of N-aryl and N-heteroaryl sulfamides via an intermolecular palladium-catalyzed coupling process has been developed. The reactions proceeded with good to excellent yields and were tolerant of a wide range of functional groups. [reaction: see text]     

Palladium-catalyzed intramolecular vinylarylation of alkene: Access to spirocyclic scaffold

A Pd(0)-catalyzed cascade reaction of (Z)-1-iodo-1,6-diene bearing a N-heteroaryl ring, including indole, pyrrole as well as imidazole, is reported. The reaction proceeds via Heck-type carbopalladation, which is followed by C-H activation of the attached N-hetero ring, thus delivering 6,5-spirocycles in moderate to good yields. Furthermore, the preliminary attempt at asymmetric version was also conducted.     

N-aryl pyrazoles: DFT calculations of CH acidity and deprotonative metallation using a combination of lithium and zinc amides

A series of N-aryl and N-heteroaryl pyrazoles have been deproto-metallated using a 2,2,6,6-tetramethylpiperidino-based mixed lithium-zinc combination. Mono-, di-, and tri-iodides have been obtained after subsequent trapping with iodine, depending on the substrate and on the quantity of base used. The results have been discussed in the light of the CH acidities of the substrates, determined both in the gas phase and in THF solution using the DFT B3LYP method.     

Crystallographic report: Dibenzyltin(IV) bis(N,N‐dibenzyldithiocarbamate)

A distorted octahedron C₂S₄ geometry is found for the tin atom in the title compound; C? Sn? C is 136.61(19)°. Copyright © 2004 John Wiley & Sons, Ltd.     

N,N-二乙基氨荒酸铋化合物(Et2NCS2)2(NO3)Bi(NO3)-Bi(S2CNEt2)2(HOCH3)的合成及晶体结构

利用硝酸铋和N,N-二乙基氨荒酸盐反应,合成了新型铋的N,N-二乙基氨荒酸衍生物(Et2NCS2)2(NO3)Bi(NO3)Bi-(S2CNEt2)2(HOCH3).通过元素分析和红外光谱对其结构进行了表征.用X射线单晶衍射测定了该化合物的分子和晶体结构.结果表明,化合物的晶体为三斜晶系空间群P1,晶胞参数:a=0.9880(3)nm,b=1.2778(3)nm,c=3.1993(9)nm,α=89.888(4)°,β=85.728(4)°,γ=89.824(4)°,Z=4,V=4.0277(19)nm3,Dc=1.925 g/m3,μ=9.183 mm-1,F(000)=2248,R1=0.0525,wR2=0.0546.该化合物中存在2个不同的铋原子,它们分别为配位数7和8的畸变五角双锥和十二面体构型.在晶体中,通过相邻分子间的S…S弱相互作用和氢键作用,形成了一维链状结构.     

N,N′-二(十二烷基)乙二胺二乙酸萃取分离铜

研究了N,N′-二(十二烷基)乙二胺二乙酸的氯仿溶液对铜的萃取行为,考察了初始水相酸度、萃取剂浓度及温度对Cu(Ⅱ)萃取率的影响. 结果表明,在pH≥6条件下对Cu(Ⅱ)有很高的萃取率,且在一定范围内随萃取剂浓度增大和温度升高萃取率均增大;用摩尔比法和电导法测得萃合物中Cu2+与萃取剂的摩尔比为1∶1;控制pH=6能使Cu(Ⅱ)与常见过渡金属离子Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、 Zn(Ⅱ)、Mn(Ⅱ)得到分离.     

Synthesis and Crystal Structure of N, N'''''''',N''''''''-Tris-(2-oxynaphthalidene)-tris-(2-iminoethyl) Amine

1 INTRODUCTION Schiff’s bases are well known ligands representedby many bi-, tri-, tetra-, and hexa-dentate example-es[1], but heptadentate ligands are relatively rare[2, . 3]We have reported a copper complex of tetradentateSchiff’s bases[4]…