1,4-吡啶硫内鎓盐在有机合成中的研究与应用

1,4-吡啶硫内鎓盐是一类重要的氮硫杂合成子,其中的吡啶片段既可以作为离去基团,也可以作为亲电反应位点参与反应,构建多种类型的氮硫杂骨架.因此,近年来1,4-吡啶硫内鎓盐在含氮、含硫杂环化合物的合成应用中受到了极大的关注.基于此,系统综述了1,4-吡啶硫内鎓盐在两种反应模式([3+m]和[5+m]环合反应)下构建氮硫杂环的研究进展,总结了其在环合反应及杂环化学中的应用,并对该领域的研究前景进行了展望.     

含中氮茚环的二甲川菁的合成

硫代甲酰基中氮茚;碘化二甲基喹啉鎓盐;荧光;含中氮茚环的二甲川菁的合成     

以缺电子炔烃为原料经1,3-偶极环加成反应合成3-芳基中氮茚的新方法

报道了一种简便有效地合成3-芳基中氮茚的方法.反应需要的吡啶鎓盐可以用吡啶和苄卤很容易制得,然后以1,4-二氧六环为溶剂,在碳酸铯存在的条件下与缺电子炔烃经1,3-偶极环加成和芳构化反应即可得到3-芳基中氮茚,产率34%~81%.该方法具有原料易得、操作简便、反应条件温和、选择性好等优点.     

一种新型芳基硫鎓盐光引发剂的合成及应用

将二苯二硫醚作为硫源与1-甲基-2-苯基吲哚反应合成了含杂原子环的硫醚类化合物,然后再与二芳基碘三氟甲磺酸鎓盐反应,合成了一种新的芳基硫鎓盐。采用1 HNMR、MS等技术对目标化合物进行了表征,并确定了最佳反应条件。在硫醚类化合物与二芳基碘三氟甲磺酸鎓盐的摩尔比为1∶1.2,催化剂为CuI/Cu,溶剂为1,1,2,2-四氯乙烷的反应条件下,目标化合物的产率达到了62.0%。同时,对这类结构的芳基硫鎓盐进行了紫外光固化性能测试,发现其能够在紫外光固化体系中作为阳离子光引发剂得到应用。     

新型水溶性中氮茚衍生物的合成及铜离子荧光探针行为

设计合成了2个新型水溶性中氮茚季铵盐化合物4a{氯化2-[N'-(3-氰基-中氮茚-1-甲酰基)肼基]酰乙基-1-吡啶鎓盐}和4b{氯化2-[N'-(3-氰基-中氮茚-1-甲酰基)肼基]酰乙基-1-(2-甲基吡啶)鎓盐},采用红外光谱、核磁共振、质谱和元素分析对其进行了结构表征,并研究了它们的光谱性质.选取Cu2+,Zn2+,Ca2+,Cr3+,Co2+,Al3+,Mn2+,Ni2+,Ba2+,Hg2+,Fe3+,Cd2+,Mg2+,Pb2+,Li+和Ag+等16种常见金属离子,对2个化合物进行了离子识别实验.结果表明,化合物4a和4b在一定浓度范围内对铜离子均具有良好的选择性识别能力,受常见离子干扰小.由于空间位阻的影响,化合物4a具有比4b更高的灵敏性.     

含1-[4-二-(4-氟苯)甲基]哌嗪官能团的硫代酰胺的合成及生物活性

以1-[二-(4-氟苯)甲基]哌嗪、端炔及单质硫为原料,应用吡啶为催化剂和溶剂,在80℃反应24h以18～84％的收率制得了17个含有1-[4-二-(4-氟苯)甲基哌嗪官能团的硫代酰胺衍生物3(a～q).合成的17个目标化合物通过熔点测定和质谱、红外光谱及氢(碳)核磁共振谱分析对其结构进行确证.并进行了体外抗肿瘤及抗菌...     

3-甲基-4-氨基-5-[二-(4-氟苯基)]甲硫基-1,2,4-三氮唑席夫碱的微波合成及表征

微波辐射下,二氨基硫脲与乙酸反应制得3-甲基-4-氨基-1,2,4-三氮唑-5-硫酮(1),在无水乙醇中以三乙胺作为反应的缚酸剂,1与[二-(4-氟苯基)]甲基氯经微波辐射制得中间体3-甲基-4-氨基-5-[二-(4-氟苯基)]甲硫基-1,2,4-三氮唑(2),然后中间体2与芳香醛经缩合反应制得了10个Schiff碱3a～3j.合成的10个目标化合物通过熔点测定和质谱、红外光谱、核磁共振氢谱分析、元素分析对其结构进行确证.     

10,10-二吡啶甲基-9,10-二氢蒽的合成研究

蒽酮1和氯甲基吡啶盐酸盐2在甲苯中回流反应生成10,10-二吡啶甲基-9(10H)蒽酮(3),收率63％～68％;3用硼氢化钠还原生成10,10-二吡啶甲基-9,l0-二氢蒽-9-醇(4),收率87％～90％;蒽醇4在酸催化下发生歧化反应,得到还原产物10,10-二吡啶甲基-9,10-二氢蒽(5)和氧化产物蒽酮3.该歧化反应受催化剂、溶剂和反应温度等影响.当蒽醇4用三氟化硼为催化剂、甲苯为溶剂、回流反应,5的收率达到74％.所合成的新化合物都经1H NMR,13C NMR,MS和元素分析表征确认.     

2-(1,2-亚乙/1,3-亚丙二硫)亚甲基-3-羰基丁酰氯的制备及其与芳烃的酰化反应

制备了较稳定的2-(1,2-亚乙/1,3-亚丙二硫)亚甲基-3-羰基丁酰氯,并实现了其与芳烃的酰化反应,为1-芳基-2-(1,2-亚乙/1,3-亚丙二硫)亚甲基-1,3-丁二酮的合成提供了一条新途径.     

α-羰基硫代甲酰胺与溴的反应研究

报道了α 羰基硫代甲酰胺与溴在三乙胺存在下的反应 ,合成了二 [( 1 芳基亚胺基 1 苯甲酰基 )甲基 ]二硫醚类化合物 ,产率为 60 %～ 65 %.它们的结构经元素分析、红外光谱、核磁共振光谱和质谱分析得到确证     

A theoretical study of the mechanisms and regiochemistry of the reactions of 5-alkoxyoxazole with thioaldehydes,nitroso compounds,and aldehydes

A theoretical study based on B3LYP/6-31G calculations has been applied to the mechanisms and regiochemistry of reactions of 5-alkoxyoxazole with thioaldehydes, nitroso compounds, and aldehydes. All three reactions adopt similar mechanisms, which start with Diels-Alder (DA) reactions, followed by either a novel, concerted ring-opening-ring-closing (RORC) step to transfer the DA adduct to 2-alkoxycarbonyl-3-thiazoline and 2-alkoxycarbonyl-3-oxazoline for thioaldehydes and aldehydes, respectively, or stepwise ring-opening and ring-closing steps to generate 1,2,4-oxadiazoline for nitroso compounds. The reactions of 5-alkoxyoxazole with thioaldehydes and nitroso compounds can be conducted under thermal reaction conditions due to the 10 kcal/mol activation barriers for their rate-determining DA reactions. By contrast, the reaction of 5-alkoxyoxazole with aldehydes cannot take place under thermal conditions, since this bimolecular reaction has the rate-determining RORC transition state higher than the reactants by 30.5 kcal/mol.     

Mesomerically stabilized thioaldehydes. 3-Thioformylindole and its alkyl and phenyl derivatives

3-Thioformylindole and its previously unknown 2-methyl-, 2 -phenyl-, and 1-ethyl substituted derivatives have been synthesized by the thiolysis of the corresponding indolylmethylenimmonium perchlorates. The thioaldehydes containing no substitutdt at the nitrogen atom were isolated as crystalline solvates with DMSO and DMF. Monitoring of 3-thioformylindole formation was effected by polarography and spectrophotometry.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 493–496, April, 1996.     

Intramolecular Diels-Alder Reaction of Thioaldehydes

Intramolecular Diels-Alder reaction of thioaldehydes which were generated from bis(trimethylsilyl) sulfide and dienals gave the corresponding bicyclic adducts.     

新型含芳氧乙酸酯基三唑酮类化合物的合成及生物活性研究

通过芳氧乙酸与2-溴-4,4-二甲基-1-(1H-1,2,4-三唑-1-基)-3-戊酮反应, 合成了14个新型含芳氧乙酸酯基三唑酮类化合物. 所有化合物均经核磁、元素分析确证, 部分化合物进行了红外和质谱的测定. 生物活性测试表明部分化合物具有良好的生物活性.     

Visible‐Light‐Induced Passerini Multicomponent Polymerization

Herein, we introduce an additive‐free visible‐light‐induced Passerini multicomponent polymerization (MCP) for the generation of high molar mass chains. In place of classical aldehydes (or ketones), highly reactive, in situ photogenerated thioaldehydes are exploited along with isocyanides and carboxylic acids. Prone to side reactions, the thioaldehyde moieties create a complex reaction environment which can be tamed by optimizing the synthetic conditions utilizing stochastic reaction path analysis, highlighting the potential of semi‐batch procedures. Once the complex MCP environment is understood, step‐growth polymers can be synthesized under mild reaction conditions which—after a Mumm rearrangement—result in the incorporation of thioester moieties directly into the polymer backbone, leading to soft matter materials that can be degraded by straightforward aminolysis or chain expanded by thiirane insertion.     

Polymeric ionic liquid as novel catalyst for the Prins reaction

A series of micro-mesoporous polymeric ionic liquids (PILs) have been successfully synthesized by the method of anion and cation copolymerization. Then use FT-IR, N₂ adsorption–desorption isotherms, SEM, and TG to characterize them. Furthermore, the catalytic performance of the synthesized PILs was investigated for the Prins reaction of propylene with 1, 3, 5-trioxane. Among the four PILs synthesized, VIMBs-DVB-SSA has better catalytic activities for the Prins reaction. Under the optimal conditions, 100 °C, 8 wt%, 4 h and n (propylene)/n (1, 3, 5-trioxane) = 4:1, the conversion of formaldehyde (99.8%) and selectivity (81.7%) for 4-methyl-1, 3-dioxane. In addition, the effects of reaction time, catalyst dosage, and reaction temperature and mole ratio of reaction substrates on the reaction were also investigated. The prepared catalyst had good thermal stability and can be reused easily.     

Heteroatom Tuning of Bimolecular Criegee Reactions and Its Implications

High‐level quantum‐chemical calculations have been performed to understand the key reactivity determinants of bimolecular reactions of Criegee intermediates and H₂X (X=O, S, Se, and Te). Criegee intermediates are implicated as key intermediates in atmospheric, synthetic organic, and enzymatic chemistry. Generally, it is believed that the nature and location of substituents at the carbon of the Criegee intermediate play a key role in determing the reactivity. However, the present work suggests that it is not only the substitution of the Criegee intermediate, but the nature of the heteroatom in H₂X that also plays a crucial role in determining the reactivity of the interaction between the Criegee intermediate and H₂X. The barriers for the reactions of Criegee intermediates and H₂X satisfy an inverse correlation with the bond strength of X−H in H₂X, and a direct correlation with the first pK_a of H₂X. This heteroatom tuning causes a substantial barrier lowering of 8–11 kcal mol⁻¹ in the Criegee reaction barrier in going from H₂O to H₂Te. An important implication of these results is that the reaction of the Criegee intermediate and H₂S could be a source of thioaldehydes, which are important in plantery atmospheres and synthetic organic chemistry. By performing the reaction of Criegee intermediates and H₂S under water or acid catalysis, thioladehydes could be detected in a hydrogen‐bonded complexed state, which is significantly more stable than their uncomplexed form. As a result, simpler aliphatic thioaldehydes could be selectively synthesized in the laboratory, which, otherwise, has been a significant synthetic challenge because of their ability to oligomerize.     

Novel Schiff bases–based thiophenes: Design,synthesis and biological evaluation

2-amino-5-(3-fluoro-4-methoxyphenyl)thiophene-3-carbonitrile derivatives have been synthesized from 1-(3-fluoro-4-methoxyphenyl)ethanone, malononitrile, mild base, and sulfur powder using the Gewald method through a multistep reaction sequence. The structures of newly synthesized compounds were established on the basis of their elemental analyses, IR, ¹H NMR, ¹³C NMR, and mass spectral data, and then synthesized compounds were screened for their in vitro antimicrobial activity. Among them, derivatives 3b (thiphene), 3f (pyrazole), and 3d (halogen) showed good activity and remaining derivatives exhibited moderate activity.     

π-Face-selective hetero Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide. An excellent trapping reagent for thioaldehydes and thioketones

Hetero Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide (1) with thioaldehydes and thioketones take place exclusively, except the reaction with thiobenzophenone, at the syn-π-face of 1 with respect to the SO bond. The π-face selectivity was explained in terms of the extent of conformational changes of 1 that are brought about in the process to the transition states.     

Reaction of 1,2,3,4-Tetrahydropyrimido[1,2-a]indol-10-ylmethyleniminium salts with certain nucleophilic agent

Summary The reaction of iminium salts of 1,2,3,4-tetrahydropyrimido[1,2-a]indole-10-carbaldehydes with sodium hydrosulfide, amines, formation of the corresponding and thioaldehydes, azomethines, and nitrovinyl derivatives, existing predominantly in the enamidine form.M. V. Lomonosov Moscow State University, Moscow 119899. Translated from Khimiya Geterotsiklicheskikh Soedinenii No. 3. pp. 381–387. March, 1995. Original article submitted February 8, 1995