苯并噻吩并[3′,2′:2,3]吡啶并[4,5-d]噻唑并[3,2-a]嘧啶酮类衍生物的有效合成

报道了氨基磺酸作用下,通过Pictet-Spengler反应合成苯并噻吩并[3′,2′:2,3]吡啶并[4,5-d]噻唑并[3,2-a]嘧啶酮衍生物的有效合成方法.其中,该反应关键中间体7-(3-氨基苯并噻吩-2-基)噻唑并[3,2-a]嘧啶-5-酮,经由7-氯甲基噻唑并[3,2-a]嘧啶-5-酮与2-巯基苯甲腈的烷基化及Thorpe-Ziegler环化制得.该合成过程原料易得,反应条件温和,收率高,为新型稠杂环嘧啶类化合物的合成提供了简便的新途径.     

离散型框架模板诱导的[2+2]光化学反应

利用[2+2]光化学反应合成环丁烷及其衍生物具有非常重要的意义,但实现其高效光化学转化比较困难.近年来的研究结果表明,该类反应在固相中,尤其是在晶态条件下,靠模板分子的帮助会显著提高效率.本文主要归纳和总结了离散型框架模板诱导[2+2]光化学反应的研究进展,并对其研究前景进行了展望.     

碘-二甲基亚砜促进新型四环噻唑并[3',2':2,3]吡啶并[4,5-d]吡啶并[1,2-a]嘧啶酮类衍生物的合成（英文）

介绍了在碘-二甲基亚砜(I_2-DMSO)促进作用下,通过Pictet-Spengler反应合成噻唑并[3',2':2,3]吡啶并[4,5-d]吡啶并[1,2-a]嘧啶酮(5)衍生物的合成方法.该反应的关键中间体2-(3-氨基-5-苯氨基噻唑-2-基)-4H-吡啶[1,2-a]嘧啶-4-酮(3),由2-氯甲基-4H-吡啶[1,2-a]嘧啶-4-酮(1)与N-苯基-N'-氰基-咪唑硫代碳酸钾(2)通过Thorpe-Ziegler异构化反应制得.该合成方法反应条件温和,操作简单,收率高.     

微波法合成2-羟乙基苯并[d]异噻唑-3(2H)-酮

以苯并异噻唑-3(2H)-酮(BIT)及氯乙醇为原料微波法合成了2-羟乙基苯并[d]异噻唑-3(2H)酮。考察了氢氧化钠量,氯乙醇用量,反应时间,反应温度对反应的影响,经正交实验设计得到了最佳反应条件,最佳反应条件下收率为83.3%。结果表明,与传统工艺相比,微波技术合成2-羟乙基苯并[d]异噻唑-3(2H)-酮的方法具有操作方便、收率高等特点,具有一定的应用价值。     

Cs2CO3催化下多组分一锅法合成螺吲哚-三唑并[1,5-a] 嘧啶及螺吲哚-苯并咪唑并[1,2-a]嘧啶类化合物

以3-氨基-1,2,4-三唑(或2-氨基苯并咪唑)、靛红和丙二腈为原料,经三组分一锅法合成了7种新型的螺吲哚-三唑并[1,5-a]嘧啶类化合物（1a~1g）和5种新型的螺吲哚 苯并咪唑并[1,2-a]嘧啶类化合物（2a, 2c, 2d, 2e, 2g）,其结构经¹H NMR, IR和HR-MS（ESI）表征。以1a和2a的合成为例,优化了合成反应条件。结果表明：在最优条件（Cs₂CO₃ 20 mol%, EtOH为溶剂,于80 ℃反应120 min）下,1a和2a收率分别为90%和87%。     

新型杯[4]芳烃衍生物的合成

以对叔丁基杯[4]芳烃为起始原料,通过一步或两步取代反应合成了对叔丁基杯[4]芳烃的衍生物(1和2),其结构经FT-IR,^1H NMR,FAB-MS表征．     

无金属催化快速合成2-芳酰氨基萘并[1,2-d]噻唑

报道了在室温条件下,二醋酸碘苯促进3-[1-(4-取代萘基)]-1-芳酰基硫脲自身关环得到一系列2-芳酰氨基萘并[1,2-d]噻唑衍生物.该方法具有反应条件温和,反应迅速,操作简单,原子利用率高,无需金属催化以及底物范围广等优点.该方法也为萘并[1,2-d]噻唑衍生物的合成提供了新的高效途径.     

卤素官能团化的[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物的合成（英文）

本文利用各种卤代的靛红为底物,与氨基硫脲在水-二氧六环(V/V,5∶1)混合溶剂为反应介质,K_2CO_3为碱条件下,进行缩合反应,有效合成了一系列卤素官能团化的[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物。所合成的目标化合物未见文献报道,其结构均已通过谱图(~1H-NMR、~(13)C-NMR和MS)数据和元素分析得以确认。     

由N-苯基[1,3]苯并噁嗪正离子与烯烃[4+2]反应合成喹啉并[1,2-c][1,3]苯并噁嗪-6-酮衍生物

以BF3·OEt2 为催化剂, 在室温下通过4-羟基-N-苯基[1,3]苯并噁嗪-2-酮的脱羟基产生N-苯基[1,3]苯并噁嗪正离子, 然后与富电子烯烃发生Diels-Alder反应, 合成出了一系列喹啉并[1,2-c][1,3]苯并噁嗪-6-酮和喹啉并[1,2-c][1,3]萘并噁嗪-6-酮衍生物.     

6-碘-5H-[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物的合成（英文）

利用各种碘代的靛红为底物,与氨基硫脲在水-二氧六环(体积比为5∶1)混合溶剂为反应介质,K_2CO_3为碱条件下,进行缩合反应,有效合成了一系列结构新型的碘官能团化的[1,2,4]三嗪并[5,6-b]吲哚-3-硫醇类化合物。所合成的目标化合物结构均通过波谱数据和元素分析得以确认。     

Synthesis and structure of upper-rim 1,3-alternate tetraoxacalix[2]arene[2]triazine azacrowns and change of cavity in response to fluoride anion

The upper-rim 1,3-alternate tetraoxacalix[2]arene[2]triazine azacrowns were constructed effectively by macrocyclic condensation reaction of diamines with dichlorinated tetraoxacalix[2]arene[2]triazine intermediates that were synthesized from the stepwise fragment coupling reactions of 3,5-dihydroxybenzoic acid esters with cyanuric chlorides. Because of the formation of conjugation of amino groups with triazine rings, tetraoxacalix[2]arene[2]triazine azacrowns existed in a mixture of syn- and anti-isomeric forms. Both fluorescence titration and 1H NMR spectroscopic study showed that tetraoxacalix[2]arene[2]triazine azacrowns interacted with fluoride anion, leading to cavity changes of the host molecules.     

Synthesis of tetraazacalix[2]arene[2]triazines: tuning the cavity by the substituents on the bridging nitrogen atoms

[Structure: see text] A number of tetraazacalix[2]arene[2]triazines bearing different substituents on the bridging nitrogen atoms were synthesized efficiently using a fragment coupling strategy. The N-arylation of the parent azacalix[2]arene]2]triazine afforded tetra(arylaza)calix[2]arene[2]triazine in 91% yield. The introduction of different substituents on the bridging positions led to the regulation of the cavity of the resulting macrocyclic molecules.     

Efficient functionalizations of heteroatom-bridged calix[2]arene[2]triazines on the larger rim

Heteroatom-bridged dichlorinated calix[2]arene[2]triazines, which were synthesized from the fragment coupling reactions of cyanuric chloride and various aromatic dinucleophiles, are a unique type of platform for the construction of functional macrocyclic host molecules. Utilizing a very convenient and straightforward nucleophilic displacement reaction of dichlorinated tetraoxacalix[2]arene[2]triazine by various chelating group-containing amines, a number of functionalized tetraoxacalix[2]arene[2]triazines on the larger rim were efficiently synthesized in good yields. The resulting tetraoxacalix[2]arene[2]triazines armed with two 2,2'-bi(pyridinyl)amino or two bis(2-pyridinemethyl)amino groups selectively formed 1:1 complexes with Cu2+ ion through most probably a chelating interaction effect.     

Chiral tetraoxacalix[2]arene[2]triazine-based organocatalysts for Enantioselective Aldol reactions

Novel efficient chiral tetraoxacalix[2]arene[2]triazine-based organocatalysts have been designed and synthesized from the reaction of tetraoxacalix[2]arene[2]triazine with R/S-phenylethylamine or R/S-1-naphthylethylamine for the Aldol reaction of acetone with aromatic aldehydes to furnish the Aldol adducts in 71–92% yields with excellent enantioselectivities (78–99%).     

En route to inherently chiral tetraoxacalix[2]arene[2]triazines

This paper describes our attempts to synthesize inherently chiral heteroatom-bridged calixaromatics. Based on a stepwise fragment-coupling approach using a chiral 3,5-dihydroxybenzamide or benzoate, 2,4-dihydroxyacetophenone, and cyanuric chloride as reactants, chiral tetraoxacalix[2]arene[2]triazine derivatives 16 and 17 were synthesized in good yields. Subsequent macrocyclic condensation with a diamine 6 furnished efficiently the pairs of diastereomers of inherently chiral tetraoxacalix[2]arene[2]triazine azacrowns 18 and 19.     

Synthesis and self-assembly of novel oxacalix[2]arene[2]triazine amphiphiles

Heteracalixaromatics are an emerging generation of macrocyclic host molecules in supramolecular chemistry. As a typical example of heteracalixaromatics, oxacalix[2]arene[2]triazine adopts a shape-persistent 1,3-alternate conformation and can be easily functionalized. Taking it as a platform, a series of oxacalix[2]arene[2]triazine-based amphiphiles bearing long alkyl chains were synthesized through post-macrocyclization functionalization or 3+1 fragment coupling protocols. The self-assembly behavior of these amphiphiles in a mixture of tetrahydrofuran (THF) and water was investigated. Dynamic light scattering (DLS) measurements revealed that the size of the self-assembled aggregates is dependent on the structure of the amphiphiles. The long alkyl chain substituents and/or intermolecular hydrogen bonds were found to promote the self-assembly.     

Design,structure and anion recognition of larger-rim functionalized oxacalix[2]arene[2]triazine hosts

Larger-rim functionalized tetraoxacalix[2]arene[2]triazine host molecules were efficiently synthesized through a fragment coupling followed by AlCl₃-mediated deprotection/arylation protocol. Substituent effects, functions of counter cations on anion recognition in solution were systematically studied by means of fluorescence and NMR titrations.     

One-pot synthesis of oxygen and nitrogen-bridged calix[2]arene[2]triazines

A simple and powerful one-pot reaction method was developed for the synthesis of heteracalixaromatics. In the presence of a base, one-pot macrocyclic condensation reaction between cyanuric chloride and 1,3-phenylene diols and diamines proceeded effectively under very mild conditions to afford a number of functionalised oxygen and nitrogen-bridged calix[2]arene[2]triazines in 33–54% yields. The method was applied in a multigram-scale (14.4 g) preparation of tetraoxacalix[2]arene[2]triazine.     

Facial one-pot synthesis of D3h symmetric bicyclocalix[2]arene[2]triazines and their layered comb self-assembly

A number of D_3h symmetric bicyclocalix[2]arene[2]triazine core compounds were synthesized via a general and good-yielding (43–48% yield) facile protocol starting from cyanuric halides, phloroglucinol and K₂CO₃ under very mild reaction conditions. These cage-like compounds are tolerante with different reaction conditions and can be derived with other functional groups in high yields. The X-ray crystal structures show these compounds have slightly distorted D_3h symmetric structures. Due to the unique molecular topological structure, bicyclocalix[2]arene[2]triazine molecules form unique layered comb networks when hydrogen bond groups exist (such as CO₂H, B(OH)₂), which represent a new kind of building block unit for supramolecular architectures.     

Syntheses and conformational structures of functionalized tetraoxacalix[2]arene[2]triazines

The syntheses and conformational structures of various functionalized tetraoxacalix[2]arene[2]triazines were studied. Applying the fragment coupling approach and the post-macrocyclization chemical manipulations, a number of tetraoxacalix[2]arene[2]triazines that contain, on the lower rim, one or two aldehyde, ester, carboxylic acid, hydroxymethyl, and aminomethyl functional groups were prepared in moderate to high chemical yields from cheap and commercially available materials. On the basis of X-ray crystallography and NMR spectroscopy, all tetraoxacalix[2]arene[2]triazines containing electron-withdrawing group(s) adopted 1,3-alternate conformation both in solution and in the solid state, while tetraoxacalix[2]arene[2]triazines bearing hydroxymethyl and aminomethyl substituent(s) existed as pinched or distorted partial cone conformers due to the formation of intramolecular hydrogen bond between hydroxyl or amino group and triazine ring.