Calix[4]azulene

Azulene reacts with paraformaldehyde in the presence of florisil to give excellent yields of calix[4]azulene.     

Calix[4]resorcinarene macrocycles

Supramolecular chemistry is an interdisciplinary scientific field, including chemical, physical and biological properties of more complex chemical species than the molecules themselves. Calixarenes/calixresorcinarenes are macrocyclic compounds, consisting of ‘n’ phenolic/resorcinolic units linked together by methylene bridges; these macrocycles are often used for molecular recognition. Thus, different modifications can be made to both the lower and upper rim, allowing the construction of well-defined multivalent buildings. In this work, three calix[4]resorcinarene macrocycles were synthesized, namely C-dec-9-en-1-ylcalix[4]resorcinarene (CAL 11U), C-trans-2, cis-6-octa-1,5-dien-1-ylcalix[4]resorcinarene (CAL 9U) and C-nonylcalix[4]resorcinarene (CAL 10) by a simple condensation reaction. The compounds CAL 11U and CAL 10 have been already synthesized by researchers, while the CAL 9U has been synthesized for the first time. Their structures were confirmed using ATR-FTIR, ¹H NMR and ¹³C NMR. Thermal analysis combined with mass spectrometric evolved analysis of the vapors was used to study the thermal behavior of the different synthesized molecules, and they were the subject of characterization by X-ray powder diffraction in order to analyze their degree of crystallinity.

     

Oxacalix[3]arene-supported supertetrahedron

The initial use of oxacalix[3]arene in manganese chemistry affords an unusual [Mn(10)] supertetrahedron with an even more unusual oxidation state distribution.     

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.     

Calix[4]arene based dendrimers

The synthesis of calix[4]arene based dendrimers containing up to seven calix[4]arene moieties is described, including the X-ray crystal structure of a tris-calix[4]arene branching derivative.     

Synthesis and reactivity of calix[4]arene-supported group 4 imido complexes

New mononuclear titanium and zirconium imido complexes [M(NR)(R'(2)calix)] [M=Ti, R'=Me, R=tBu (1), R=2,6-C(6)H(3)Me(2) (2), R=2,6-C(6)H(3)iPr(2) (3), R=2,4,6-C(6)H(2)Me(3) (4); M=Ti, R'=Bz, R=tBu (5), R=2,6-C(6)H(3)Me(2) (6), R=2,6-C(6)H(3)iPr(2) (7); M=Zr, R'=Me, R=2,6-C(6)H(3)iPr(2) (8)] supported by 1,3-diorganyl ether p-tert-butylcalix[4]arenes (R'(2)calix) were prepared in good yield from the readily available complexes [MCl(2)(Me(2)calix)], [Ti(NR)Cl(2)(py)(3)], and [Ti(NR)Cl(2)(NHMe(2))(2)]. The crystallographically characterised complex [Ti(NtBu)(Me(2)calix)] (1) reacts readily with CO(2), CS(2), and p-tolyl-isocyanate to give the isolated complexes [Ti[N(tBu)C(O)O](Me(2)calix)] (10), [[Ti(mu-O)(Me(2)calix)](2)] (11), [[Ti(mu-S)(Me(2)calix)](2)] (12), and [Ti[N(tBu)C(O)N(-4-C(6)H(4)Me)](Me(2)calix)] (13). In the case of CO(2) and CS(2), the addition of the heterocumulene to the Ti-N multiple bond is followed by a cycloreversion reaction to give the dinuclear complexes 11 and 12. The X-ray structure of 13.4(C(7)H(8)) clearly establishes the N,N'-coordination mode of the ureate ligand in this compound. Complex 1 undergoes tert-butyl/arylamine exchange reactions to form 2, 3, [Ti(N-4-C(6)H(4)Me)(Me(2)calix)] (14), [Ti(N-4-C(6)H(4)Fc)(Me(2)calix)] (15) [Fc=Fe(eta(5)-C(5)H(5))(eta(5)-C(5)H(4))], and [[Ti(Me(2)calix)](2)[mu-(N-4-C(6)H(4))(2)CH(2)]] (16). Reaction of 1 with H(2)O, H(2)S and HCl afforded the compounds [[Ti(mu-O)(Me(2)calix)](2)] (11), [[Ti(mu-S)(Me(2)calix)](2)] (12), and [TiCl(2)(Me(2)calix)] in excellent yields. Furthermore, treatment of 1 with two equivalents of phenols results in the formation of [Ti(O-4-C(6)H(4)R)(2)(Me(2)calix)] (R=Me 17 or tBu 18), [Ti(O-2,6-C(6)H(3)Me(2))(2)(Me(2)calix)] (19) and [Ti(mbmp)(Me(2)calix)] (20; H(2)mbmp=2,2'-methylene-bis(4-methyl-6-tert-butylphenol) or CH(2)([CH(3)][C(4)H(9)]C(6)H(2)-OH)(2)). The bis(phenolate) compounds 17 and 18 with para-substituted phenolate ligands undergo elimination and/or rearrangement reactions in the nonpolar solvents pentane or hexane. The metal-containing products of the elimination reactions are dinuclear complexes [[Ti(O-4-C(6)H(4)R)(Mecalix)](2)] [R=Me (23) or tBu (24)] where Mecalix=monomethyl ether of p-tert-butylcalix[4]arene. The products of the rearrangement reaction are [Ti(O-4-C(6)H(4)Me)(2) (paco-Me(2)calix)] (25) and [Ti(O-4-C(6)H(4)tBu)(2)(paco-Me(2)calix)] (26), in which the metallated calix[4]arene ligand is coordinated in a form reminiscent of the partial cone (paco) conformation of calix[4]arene. In these compounds, one of the methoxy groups is located inside the cavity of the calix[4]arene ligand. The complexes 24, 25 and 26 have been crystallographically characterised. Complexes with sterically more demanding phenolate ligands, namely 19 and 20 and the analogous zirconium complexes [Zr(O-4-C(6)H(4)Me)(2)(Me(2)calix)] (21) and [Zr(O-2,6-C(6)H(3)Me(2))(2)(Me(2)calix)] (22) do not rearrange. Density functional calculations for the model complexes [M(OC(6)H(5))(2)(Me(2)calix)] with the calixarene possessing either cone or partial cone conformations are briefly presented.     

Synthesis of p-Formylphenylazo Calix [ 4 ]arenes

Calixarenes are a versatile class of macrocyclic compounds, which have attracted extensive interest due to their ability to form host-guest complexes and act as enzyme mimic. Moreover, a number of calixarenes with D-π-A units have been synthesized, and their second-order nonlinear optical (NLO) properties investigated.     

Mono Halogen Substituted Calix[4]pyrroles: Fine-tuning the Anion Binding Properties of Calix[4]pyrrole

Abstract

Single halogen atom (i. e. I, Br, Cl and F) substituted calix[4]pyrroles, compounds 2, 3, 4 and 5, were synthesized. Studies of these systems reveal that replacement of a single β-pyrrolic hydrogen atom can increase the anion binding ability of calix[4]pyrroles for a variety of anions (e. g. Cl^?, Br^?, H₂PO₄ ^? and HSO^? ₄) relative to normal non-halogen substituted calix[4]pyrrole 1. In the case of chloride anion, the expected relative affinity sequence of 5 > 4 > 3 > 2 was observed. This was not found to be true for Br^?, H²PO^? ₄, and HSO^? ₄. Here, the chlorine substituted calix[4]pyrrole 4 was found to display a slightly higher affinity in the case of each anion than the fluorine-bearing derivative 5. This was rationalized in terms of intermolecular NH … F hydrogen bonding interactions being present in CD₂Cl₂ solutions of 5. Support for this latter conclusion came from concentration and temperature-dependent NMR spectroscopic studies.

A matched set of mono halogen substituted calix[4]pyrroles was used to study in detail, the extent to which halogen substituents may be used to fine-tune the anion binding properties of calix[4]pyrroles.     

Chlorination of Calix[4]arene Derivatives

New convenient method for synthesis of p-chlorinated calix[4]arenes is reported. The sulfuryl chloride was used for chlorination of unsubstituted at the lower rim calix[4]arenes. The products of this reaction were very suitable for further O-alkylation.     

Hydrophosphoryl Derivatives of Calix[4]resorcinolarenes

Russian Journal of General Chemistry -     

Novel Calix[4]arene Azacrown Ether

1,3-diproyloxycalix[4]arene azacrown ether was successfully synthesized in the fixed 1,3-alternate conformation which was confirmed by a solid state structure.     

杯[4]单硫(硒)杂冠-5的合成及其对金属离子的识别性能研究

从简单无机硫、硒化合物直接合成冠醚环上含硫、硒杂原子的杯[4]单硫杂冠-5及杯[4]单硒杂冠-5;化合物的结构经¹HNMR、MS及元素分析确证.并研究了它们对Na⁺,K⁺,NH⁴⁺,Co²⁺,Ni²⁺,Ag⁺及Hg²⁺的两相萃取性能,发现其对Ag⁺、Hg²⁺有较好的识别能力.     

Preferred Conformations of Calix[4]- and Calix[6]arenes,Calculated ab initio

Ab initio STO-2G calculations showed that the preferred conformation of a series of calix[6]arenes substituted at the upper rim is a compressed cone stabilized by a pseudo-ring of six hydrogen bonds with close characteristics. The endocyclic dihedral angles between the benzene ring planes, characterizing the molecular shape of the above macrocyclic compounds in this conformation, were calculated. The calculation results are consistent with the conformational data obtained by other theoretical methods and describe the characteristics of hydrogen bonds more adequately, in agreement with the experimental data and with the existing concepts of the hydrogen bonding efficiency.     

Ultramacrocycle with Four Calix[4]arenes: Synthesis and X-Ray Crystal Structure of A Quadruple Calix[4]arene

A quadruple calix[4]arene has been synthesized efficiently from the known diaminocalix[4]arene and 4,4′-biphenyldisulfonyl chloride in just one step (38% yield). The compound has been fully characterized including the determination of the X-ray crystal structure.