Synthesis and self-assembly of novel calix[4]arenocrowns: formation of calix[4]areno[2]catenanes

A series of novel calix[4]arenocrowns 1a-c were efficiently synthesized by a one-pot reaction of calix[4]monohydroquinone diacetate 5 with ditosylate 6 and its analogues in the presence of sodium hydroxide. It was found that the calix[4]arenocrowns could form stable pseudorotaxane-type complexes 2a-c with paraquat, and further self-assemble into calix[4]areno[2]catenanes 3a-c with dicationic salt 8 and p-bis(bromomethyl)benzene.     

Spectrophotometric study of the supramolecular complexes of [60]- and [70]Fullerenes with biscalix[6]arene and crown[4]calix[6]arene

[60]- and [70]Fullerenes have been shown to form 1:1 supramolecular complexes with bis[2-(5,11,17,23,29,35-hexa-tert-butyl-37,38,39,40,41-pentahydroxycalix[6]arenyl-oxy ethyl ether) (1) and 5,11,17,23,29,35-hexa-tert-butyl-37,38,40,41-tetra hydroxyl-39,42-(crown-4)calix[6]arene (2) in CHCl3 medium by electronic absorption spectroscopy. Formation constants (K) of the complexes of [60]- and [70]fullerenes with 1 and 2 have been determined at room temperature from which free energy of formation values of the complexes have been estimated. The very high formation constant value of [60]fullerene/1 complex (5900 dm3 mol-1) in indicative of formation of inclusion complex. Moreover, PM3 calculations reveal that intermolecular interaction between [60]fullerene and 1 proceeds through quite deep energy molecular orbital.     

一锅法合成含两种桥联链的杯[4]双冠醚和双杯[4]冠醚

报道了"一锅法"合成含两种桥联链的新型杯[4]双冠醚和双杯[4]冠醚.杯[4]芳烃先与N,N’-乙撑基-二(2-氯乙酰胺)发生"1+1"缩合反应,然后直接加入三甘醇双对甲苯磺酸酯继续进行"2+2"缩合反应,合成了含两种桥联链的新型双杯[4]冠醚4.按照相似程序,杯[4]芳烃先后与N,N’-乙撑基-二(2-氯乙酰胺)、溴乙酸乙酯和二乙烯三胺反应,得到含两种桥联链的新型杯[4]双冠醚5.化合物5进一步与异硫氰酸苯酯反应合成带硫脲支链的杯[4]双冠醚6.所有新化合物的结构与构象经元素分析、质谱、核磁共振谱等表征证实.     

N-硫脲基套索杯[4]冠醚与四硫脲基杯[4]芳烃的合成

控制反应物的物质的量比, 杯式对叔丁基杯[4]-1,3-二乙酸乙酯衍生物1与5或50倍二乙烯三胺反应, 分别得到杯[4]氮杂冠醚2和开链的氮杂杯[4]芳烃衍生物3. 化合物2和3进一步与异硫氰酸苯酯反应得到首例侧链含硫脲基的套索杯[4]氮杂冠醚4和含4个硫脲基的杯[4]芳烃衍生物5, 产率为92%和87%. 新化合物的结构与构象经元素分析、红外、质谱、核磁共振谱等表征证实.     

Synthesis and structure of N-methylated azacalix[4]pyridines and azacalix[1]arene[3]pyridines

Reaction of azacalix[4]pyridine and azacalix[1]arene[3]pyridine with methyl iodide afforded N-methylated products selectively and highly efficiently. Crystal structures revealed that the modified electronic nature of the pyridines could change the conjugation between the bridging nitrogen and the neighbouring aromatics.     

苄连氮桥联双硫杂杯[4]芳烃的合成

硫杂杯[4]二醛基衍生物(1)在水合肼中肼解,合成了新化合物硫杂杯[4]二醛腙基衍生物(2);1和2在弱酸的催化下反应合成了新的具有对称结构的苄连氮双硫杂杯[4]芳烃(3);2和3的结构经1H NMR,IR,ESI-MS和元素分析表征.     

Synthesis of （p-Formylphenyl）azo Calix[4]arenes

Five novel azo calix[4]arenes were reported. The p-aminobenzaldehyde was diazotized with sodium nitrite in aqueous hydrochloride solution. Mono-, bis-, tris- and tetrakis(p-formylphenyl)azo calix[4]arenes (including proximal and distal isomers) were obtained respectively by diazo-coupling in different molar ratio to calix[4]arene(1) under pH=7.5--8.5 at 0-5℃. All (p-formylphenyl)azo calix[4]arenes were characterized by ^1H NMR, ^13C NMR, IR, MS (ESIMS) spectroscopies and elemental analysis.     

苄连氮基桥联的双杯[4]芳烃的合成

对叔丁基杯[4]芳烃-1, 3-二醛基衍生物1分别与水杨醛腙、水合肼进行“1＋2”和“2＋2”缩合反应, 方便地合成了苄连氮基取代或桥联的新型杯[4]芳烃衍生物2和双杯[4]芳烃衍生物3, 产率分别为84%和81%. 新化合物的结构与构象经元素分析、质谱、核磁共振谱和1H-1H COSY谱图等表征证实, 双杯[4]芳烃衍生物3为空间结构完全对称的具有管状三维空腔的杯式构象.     

Synthesis of New Calix[4]arenes Functionalizated by Acetylhydrazide Groups

A series of new calix[4]phenols, calix[4]resorcinols and calix[4]pyrogallols with acetylhydrazide substitutes has been␣synthesized with high yields by hydrazinolysis of ester group containing calix[4]arenes. The synthesized calix[4]phenols adopt the cone conformation while the calix[4]resorcinol and calix[4]pyrogallol derivatives prefer the boat conformation. The amide fragment of the hydrazide groups predominantly exists in the trans-conformation. The binding ability of synthesized calix[4]arenes toward transition and alkali metals by solvent extraction has been investigated.     

A NOVEL SYNTHESIS OF 2-SUBSTITUTED-4H-THIENO [2,3-d][1,3] OXAZIN-4-ONE AND 2,3-DISUBSTITUTED THIENO [2,3-d]PYRIMIDIN-4(3H)-ONE DERIVATIVES

Abstract

The synthesis of acetic 2-{[1-methyl-2-(4-oxo-5,6,7,8-tetrahydro-4H-benzo [4,5]-thieno [2,3-d] [1,3-oxazin-2-yl)ethylidene]amino}-4,5,6,7-tetrahydrohenzo[b]thiophene ?3-carboxylic acid anhydride 5 and 2-(oxopropyl)-5,6,7,8-tetrahydro-4H-benzo-[4,5] thieno[2,3-d][1,3]oxazin-4-one 7, has been achieved in three steps from ethyl 2-amino-4,5,6,7-tetrahydrobenzo(b]thiophene-3-carboxlate 1 via the reaction with ethyl acetoacetate followed by hydrolysis and acetic anhydride-induced cyclization. The 2-substituent in compound 5 has two functional groups i.e. active methylene and acid anhydride which are suitably located for intramolecular transformation. Thermal and/or base catalyzed intramolecular cyclization of 5 afforded 2-(4-acetoxy-(hydroxyl)-2-methyl-5,6,7,8-tetrahydrobenzo[4,5] thieno[2,3-b]pyridin-3-yl)-5,6,7,8- tetrahydro-4H-benzo[4,5]thieno[2,3-d] [1,3]oxazin-4-one 10 and 9 respectively. Treatment of 5 with hydrazine hydrate, aromatic and/or heterocyclic amines induced the same intramolecular cyclization with a concomitant oxazine-pyrimidine interconversion to give 3-amino(aryl or heteryl)-2-(4-hydroxy-5,6,7,8-tetrdhydrobenzo-[4,5]thieno[2,3-b]pyridin-3-yl)-3,4,5,6,7,8-hexahydrobenzo[4,5] thieno[2,3-d] pyrimid in-4-one 11–14 respectively.     

Alkoxide-Accelerated [1,3] Sigmatropic Shift of Bicyclo[3.2.1]oct-6-en-2-ols to 8-endo-Hydroxybicyclo[3.3.0]oct-2-en-4-ones

Bicyclo[3.2.1]oct-6-en-2-ols 6 are shown to undergo [1,3] sigmatropic shift to afford 8-endo-hydroxy-bicyclo[3.3.0]oct-2-en-4-ones 8 under the influence of potassium hydride.     

A Facile Method to Synthesize Spiro-calix[4]arenes

Calixarenes have absorbed considerable interests for their outstanding abilities of recognition for cations, anions and organic molecules1. In order to include larger and more complex molecules, polytopic receptors were designed from two or more host macrocycles linked by one or several links. Therefore, double-calixarenes and oligocalixarenes have been synthesized and reviewed2. Among these polytopic receptors, double-calixarenes can be used as the mimic of ion channel or to self-organize koi…     

Unprecedented cyclisations of calix[4]arenes under the Mitsunobu protocol. Part 3: Thiacalix[4]crowns versus dimers

Intermolecular couplings versus intramolecular ring closures were observed in the reaction of p-tert-butylthiacalix[4]arene and diethylene glycols affording dimers 2 and/or the inherently chiral 1,2-thiacalix[4]crown-3 derivatives 5 under the Mitsunobu protocol. The enantiomeric separation of 5a was achieved by chiral HPLC. The reaction of thiacalix[4]monocrowns 1 with diethylene glycols failed to give crowned thiacalix-tubes 7, instead biscrowns 8 were formed. Partially alkylated double thiacalix[4]arenes 10, 11 were obtained via the base promoted alkylations of a thiacalixarene dimer 2a containing diethyleneoxy linkers.     

Synthesis of conformationally diverse tetrathiacalix[4]arene(amido)crowns and tetrathiacalix[4]arene amides with pendant amine functions

A series of conformationally diverse novel tetrathiacalix[4]arene(amido)crowns and amides from tetrakis((ethoxycarbonyl)methoxy)p-tert-butyl tetrathiacalix[4]arene and its debutylated analog have been prepared by their reaction with diamines [H₂N(CH₂)_nNH₂; n=2,3,4, and 6] and polyamines. It has been determined that the length of the alkyl spacer in diamines is pivotal for the formation of either the tetrathiacalix[4]arene bis(amido)crowns or tetrathiacalix[4]arene amides with pendant amine functions. The synthesized compounds represent potential building blocks for achieving sophisticated molecular assemblies for molecular organization and recognition. Single crystal X-ray analysis of tetrathiacalix[4]arene bis(amido)crown 6a revealed that it has a 1,3-alternate conformation, which forms supramolecular complexes with chloroform.     

Synthesis of Macrocyclic Lactones Building on Double Calix[4]arenes

Naturalmacrocycliclactonesandlactamsastheionophoreshaveabsorbedextensiveinterestsbecauseoftheirveryhighselectiverecognitionforalkalimetals.rorexample,nactinslandvalinomycin'havethehighestselectivityforpotassiumamongalltheionopohores.Artificialmacrocycliclactonesalsoshowedselectivityforcanons,althoughthebindingstrengthwaslowerthanthatofcommoncrownethers3.Calixareneswereaveryimportantkindofartificialreceptors,whosederivativeshaveshowedthehighestselectivityforNa ,K andCs amongthesynthesizedmacro…     

Synthesis of a functionalised calix[4]arene and its interactions with hemicucurbit[6,7]urils and cucurbit[8]uril

In the present work, we synthesised a functionalised calix[4]arene with 5,11-di(N-methyl-E-(4-pyridylethylene) moiety (CX[4]), and investigated interactions of it with HemiMeQ[6], HemiMeQ[7], and Q[8]) in both water and DMSO using fluorescence spectrophotometry and ¹H NMR spectroscopy. Titration ¹H NMR spectra revealed that Q[n]s prefers to include the N-methyl-E-(4-pyridylethylene) moiety. In particular, the interaction of CX[4] with Q[8] in water resulted in intense fluorescence emission, and this interaction system can respond to compounds such as amantadine.     

单炔基桥联双杯[4]芳烃的合成与对溶剂分子的包合性能

对叔丁基杯[4]芳烃直接与1,4-二氯-2-丁炔反应,一步制备了单炔基单桥联双杯[4]芳烃和单炔基双桥联双杯[4]芳烃,并证实单桥联双杯[4]芳烃是双桥联双杯[4]芳烃的中间产物.经¹HNMR,¹³CNMR和ESI-MS分析证实了产物的结构.ESI-MS结果表明两种产物对DMF和H₂O有不同的包合能力.     

Synthesis of Flavin–Calix[4]arene Conjugate Derivatives

The synthesis of two new flavin substituted calix[4]arene derivatives, 9 and 10 , is described. The first flavin substituted calix[4]arene derivative 9 was synthesized by the reaction of 3‐methylalloxazine ( 5 ) with 25,27‐bis(3‐bromopropoxy)‐26,28‐dihydroxy‐5,11,17,23‐tetra(tert‐butyl)calix[4]arene ( 4 ) in high yield (92%). The other derivative 10 was prepared from 3‐methylalloxazine‐1‐acetic acid ( 7 ) and 25,27‐bis(3‐cyanopropoxy)calix[4]arene ( 3 ). All new compounds were characterized by a combination of FT‐IR and ¹H‐NMR spectroscopy, and elemental‐analysis techniques.     

Calix[4]quinones III: The Synthesis of p‐Hydroxycalix[4]arenes by Wolff‐Kishner Reduction

The Wolff‐Kishner reduction of the half‐protected ketal calix[4]monoquinone 3 and its basic hydrolysis product 4 produced a partially reducing product 5 . When the same reduction conditions were applied to the calix[4]quinone benzoates 1 and 2 , the corresponding title compounds, p‐hydroxycalix[4]arenes ( 6 and 7 ), were afforded in one step.     

25-[(乙氧基羰基)甲氧基]-26,27,28-三丁氧基对叔丁基杯[4]芳烃的合成

以对叔丁基杯[4]芳烃为起始原料,合成了25-羟基-26,27,28-三丁氧基对叔丁基杯[4]芳烃(2)和25-[(乙氧基羰基)甲氧基]-26,27,28-三丁氧基对叔丁基杯[4]芳烃(3),2和3的结构经1HNMR和IR表征。通过正交实验[L16(45)和L9(33)]优化了实验条件,使3的总收率提高到60%。