Synthesis and Complexation Properties of Novel Biscalixarene Composed of Calix[4]arene and Thiacalix[4]arene Subunits

Biscalixarenes, as examples of higher order molecular architectures than normal calixarene derivatives, were studied extensively in the recent years due to they possess two calixarene cavities which have the potential for complexing with two guests in two…     

Synthesis,Crystal Structure and Biological Activity of 25,27-Di(α,γ-diketo-p-methylphenylbutoxy)-26,28-dihydroxy p-tert-butylcalix[4]arene

The title complex(C66H76O8·CH3CN) was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 22.384(13), b = 13.413(7), c = 21.867(12), β = 112.257(7)°, C68H78NO8, Mr = 1037.31, Dc = 1.133 g/cm3, V = 6076(6) 3, Z = 4, F(000) = 2224, μ(MoKa) = 0.073 mm-1, T = 296(2) K, 10276 independent reflections with 5469 observed ones(I 2σ(I)), R = 0.0797 and wR = 0.2316 with GOF = 1.027(R = 0.1442 and wR = 0.2689 for all data). The calixarene moiety maintains the symmetric cone conformation through intramolecular O–H···O hydrogen bonds. The inhibition of the strand transfer process of HIV-1 integrase of the title compound was also evaluated. Preliminary bioassays indicated that it has a low inhibition ratio(24.85%) at the concentration of 50 μM.     

Synthesis and Crystal Structure of a Novel Calix [8] arene Ester Derivative

The synthesis and crystal structure of a novel calix[8] arene ester are reported herein. The calix [8] arene ester derivative has been characterized by IR,NMR and X-ray crystal analysis. The X-ray structure analysis revealed that the 8 phenolic hydroxy groups of the calix [8] arene have been substituted by 4 diethyl dibromomalonate molecules with each two adjacent hydroxy oxygen atoms attached to a bridge diethyl malonate.     

Complexation of Calix[4]arene With Alkali Metal Cations: Conformational Binding Selectivity and Cation-π Driven Inclusion

Hartree-Fock, second order Møller-Plesset perturbation theory, and density functional theory calculations were carried out to analyse the complexation of calix[4]arene with cationic species including H + and the alkali metal cations (Li + , Na + , K + , Rb + , and Cs + ). Special emphasis has been placed on conformational binding selectivity, and on the structural characterization of the complexes. Li + and Na + cations are located in the calix[4]arene lower rim. The larger cations (K + , Rb + , and Cs + ) complex preferentially with the calix[4]arene cone conformer, and their endo (inclusive) complexation is driven by cation- ~ interactions, leading in the case of K + to a structure that reflects a preferential interaction with two phenol rings. The endo complexation of Cs + with calix[4]arene is in agreement with X-ray diffraction data.     

Yttrium complexes derived from 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-dimethoxycalix[4]arene (LH2). Synthesis,properties, and structures of the [LY(thf)(μ-Cl)]2 and [LY(thf)3]+[L2Y]– complexes

5,11,17,23-Tetra-tert-butyl-25,27-dihydroxy-26,28-dimethoxycalix[4]arene (1, LH₂) was deprotonated with two equivalents of potassium naphthalenide in THF at room temperature. The reaction of a dipotassium derivative of 1 prepared in situ with anhydrous YCl₃ in a THF medium afforded the corresponding yttrium alkoxychloride [LY(thf)(-Cl)]₂·4thf (2·4thf) in 71% yield. According to the X-ray diffraction data, complex 2 has a dimeric structure. The reaction of equimolar amounts of [(Me₃Si)₂N]₃Y and compound 1 in a THF—toluene mixture at 60 °C was accompanied by the complete replacement of the bis(trimethylsilyl)amide ligands to form the homoligand ionic complex [LY(thf)₃]⁺[L₂Y]^– (3). The structure of the latter was established by X-ray diffraction analysis.     

Synthesis of Coumarin-functionalized Calix[4]arene and Selective Recognition for L-Tryptophan

We report a novel calixarene derivative using 4-bromomethyl-7-methoxycoumarin as the pre-organized unit and apply it to investigate selectively discriminate L-tryptophan from other amino acids in DMF-acetonitrile. 5, 11, 17, 23-Tetra-tert-butyl-25,27-bis-…     

Synthesis and Crystal Structure of 5,17-Diformyl-11,23-di（tert-butyl）25,26,27,28-tetrapropoxy-calix[4]arene

The title compound 5,17-diformyl-11,23-di（tert-butyl）-25,26,27,28-tetrapropoxycalix[4]arene has been synthesized by selective formylation of 5,11,17,23-tetra（tert-butyl）25,26,27,28-tetrahydroxycalix[4]arene in three steps and characterized by1H NMR and X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group C2/c with a = 25.760（3）,b = 10.9952（10）,c = 18.630（2）,β = 119.985（4）°,V = 4570.4（9）3,Z = 4,Dc = 1.106 g/cm3,Mr = 761.01,F（000） = 1648,μ = 0.071 mm-1,MoKa radiation（λ = 0.71073）,R = 0.0710 and wR = 0.2411 for 3234 observed reflections with I 2σ（I）.X-ray analysis reveals that the title compound adopts a pinched cone conformation which leads to an open cavity.Intermolecular C–H O weak interactions link the molecules along the bc plane,which are effective in the stabilization of the crystal structure.     

Erratum to: “Asymmetric Calix[4]-thiacalix[4]arene Tubes: Synthesis and Ionophore Properties”

Russian Journal of Organic Chemistry -     

Synthesis and Conformational Properties of Bis（calix [4] arene）

The bis(calix [4] arene)3 was synthesized in moderate yield by the reaction of p-tert-butylcalix [4] arene (1) with 1,4-bis(chloromethyl) benzene (2). The conformation of all alkylated product 4 was investigated by the variable-temperature ^1H-NMR.     

Synthesis,Crystal Structure and Anti-integrase Activity of 25,27-Bis[（Z）- 4-（p-methoxyphenyl）-4-hydroxybut-3-en- 2-one-l-methyl]-26,28-dihydroxycalix[4]arene

The title compound （C50H.44010） was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 16.713（4）, b --- 13.189（3）, c = 19.434（5） A, β = 104.411（4）°, Mr = 804.85, Dc = 1.288 g/cm3, V = 4149.2（17） A3, Z = 4, F（000） = 1696, #（MoKa） = 0.089 mm-1T = 296（2） K, 7279 independent reflections with 3172 observed ones （I 〉 2δ（/））, R = 0.0520 and wR = 0.1203 with GOF = 0.928 （R = 0.1464 and wR = 0.1657 for all data）. The calixarene moiety maintains the symmetric cone conformation through intramolecular O-H…O hydrogen bonds. Preliminary bioassays indicated that the title compound has a potent inhibitory activity against the strand transfer process of HIV-1 integrase.     

Synthesis and Crystal Structure of Calix[4]arene Bearing a 1,8-Bis（propoxy）anthracene-9,10-dione

The title complex （C50H44C14O8） was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/n with a = 19.7768（4）, b =10.2085（2）, c = 21.2721（4）A,β= 97.153（1）°, V = 4261.23（14）A^3, Z = 4, Mr = 914.65, F（000） = 1904, Dc = 1.426 g/cm^3,μ = 0.336, the final R = 0.0550 and wR = 0.1647. The compound was structurally characterized by IR and ^1H NMR. The molecules are stacked through C-H...π interactions and intermolecular C-H...O hydrogen bonds.     

Synthesis and crystal structure of 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles

In the presence of methanesulfonic acid as catalyst, the condensation reactions of 5,5′-dialkyldipyrromethanes with p-hydroxyacetophenone in methanol resulted in a mixture of the unexpected polysubstituted 15α,20α-di(4-hydroxylphenyl)calix[4]pyrroles and the expected 10α,20β-di(4-hydroxylphenyl)calix[4]pyrroles in comparable lower yields. The crystal structures of the new calix[4]pyrroles and their oxyacetate derivatives were successfully determined by X-ray diffraction and the intermolecular interactions in the solid state is briefly discussed.     

Synthesis, Structure and Magnetic Properties of a Diphenoxo-bridged Binuclear Copper(II) Complex

ＩｎｔｒｏｄｕｃｔｉｏｎＥｘｃｈａｎｇｅ ｃｏｕｐｌｅｄｐｏｌｙｎｕｃｌｅａｒｃｏｐｐｅｒ(ＩＩ)ｃｏｍｐｌｅｘ ｅｓａｒｅｏｆｓｐｅｃｉａｌｉｎｔｅｒｅｓｔｄｕｅｔｏｔｈｅｉｒｉｎｖｏｌｖｅｍｅｎｔｉｎｂｉｏ ｌｏｇｉｃａｌｐｒｏｃｅｓｓｅｓａｎｄｉｎｉｎｏｒｇａｎｉｃｍａｔｅｒｉａｌｓ .1,2 Ｔｈｅｉｎｔｉ ｍａｔｅｒｅｌａｔｉｏｎｓｈｉｐｂｅｔｗｅｅｎｔｈｅｓｐｉｎｃｏｕｐｌｉｎｇａｎｄｔｈｅｍｏｌｅｃｕｌａｒｓｔｒｕｃｔｕｒｅｈａｓｆｏｓｔｅｒｅｄｔｈｅｅｍｅｒｇｅｎｃｅｏｆｍｏｌｅｃ ｕｌａｒ…     

[Bu4N]2[Fe2(μ-S2O3)2(NO)4]: Synthesis,Structure, Redox Properties,and EPR Study

The [n-Bu₄N]₂[Fe₂(-S₂O₃)₂(NO)₄] complex was studied using X-ray diffraction analysis, cyclic voltammetry, and EPR spectroscopy, and its crystal structure was determined. The redox properties of the [Fe₂(-S₂O₃)₂(NO)₄]^2–anion in CH₃CN and CH₂Cl₂solutions were studied. An addition of excess reducer (sodium thiosulfate) to the thiosulfate complex was shown to produce an EPR signal with g= 2.03 typical of the mononuclear iron dinitrosyl complexes. The mechanism for [Fe₂(-S₂O₃)₂(NO)₄]^2–reduction was suggested.     

Synthesis,Crystal Structure and Properties of a 3-Fold Interpenetrating 3D Cd(Ⅱ) Complex Derived from 4-(2-Methyl-1H-imidazol-1-yl)benzoic Acid

A new Cd~Ⅱ coordination complex,namely [Cd(iba)_2]_n(1),was prepared by the hydrothermal reaction of Cd(NO_3)_2·4H_2O with 4-imidazol-1-yl-benzoic acid(Hiba). Single-crystal X-ray diffraction analysis shows that compound 1 crystallizes in monoclinic system,space group Cc with a = 11.403(4),b = 30.480(9),c = 7.732(3) ?,β = 130.189(4)o,V = 2503.0(1) ?~3,Z = 4,C_(22)H_(18)CdN_4O_4,Mr = 514.80,Dc = 1.666 g/cm~3,F(000) = 1032 and μ(Mo Kα) = 1.101 mm-1. The final R and wR are 0.0573 and 0.1823 for 4421 observed reflections with I 2σ(I). Each iba-ligand coordinates in a bidentate fashion,connecting the Cd(Ⅱ) atoms to form a 2D wave-shape layer structure,which can be simplified as a four-connected topological net. Interestingly,the 2D layers are further extended into a 3-fold interpenetrating 3D architecture. Compound 1 displays an emissive maximum at 455 nm in the solid state at room temperature and a response of the second harmonic generation(SHG) activity is approximately 0.8 times that of KDP.     

Synthesis and C70 complexation studies of a fluorescent 5,5’-bi-p-tert-butylcalix[4]arene scaffold

Abstract

In this paper, we report the synthesis and C70 complexation studies of a new fluorescent 5,5′-bi-p-tert-butylcalix[4]arene capsule with an extended hydrophobic cavity. The synthetic route required development of a series of selective protection and de-protection reactions, such as esterification and ester cleavage, as well as a cross-coupling reaction at the lower rim. The resulting 5,5′-bi-p-tert-butylcalixarene was fully characterised, including by X-ray crystallography. In the solid state, the compound exists in an ‘open-capsule’ orientation, with a perfectly planar bridging biphenylene unit resulting in high fluorescence with a maximum emission peak at 390 nm. Preliminary fluorescence-based complexation experiments with C70 fullerene did not provide conclusive evidence for formation of inclusion complexes.     

Does Chiral Sensitivity of a Structure Depend on the Metal Core? Alkali Ion Complexes of Cyclo(Tyr-Tyr)

Alkali metal complexes of cyclic dipeptide cyclo Tyr-Tyr have been studied under cryogenic ion trap conditions. Their structure was obtained by combining Infra-Red Photo-Dissociation (IRPD) and quantum chemical calculations. The structural motif strongly depends on the relative chirality of the tyrosine residues. For residues of identical chirality, the cation interacts with one amide oxygen and one of the aromatic rings only; the distance between the aromatic rings does not change with the nature of the metal. In contrast, for residues of opposite chirality, the metal cation is located in between the two aromatic rings and interacts with both of them. The distance between the two aromatic rings strongly depends on the metal. Electronic spectra obtained by Ultra Violet Photodissociation (UVPD) spectroscopy and analysis of the UV photo-fragments shed light on the excited state deactivation processes, which depend on both the chirality of the residue and that of the metal ion core. Na⁺ stands out by the presence of low-lying charge transfer states resulting in the broadening of the electronic spectrum.     

Synthesis, Structure and Properties of Nqvel Dicopper( Ⅱ ) Complex [Cu(oxpn)Cu(tmen)_2]·(ClO_4)_2

The copper( Ⅱ ) complex, [Cu(oxpn)Cu(tmen)2](ClO4)2 was synthesized, where oxpn is N, N' -bis ( 3-aminopropyl) oxamido and tmen is N, N, N' N' -tetram-ethylethylenediamine. The crystal is triclinic, space group P 1, a=1-2349(2), b = 1.3093(2), c=1. 3855(2) nm, α=61-88(1), β=69.49(1), γ=57.91(1)°? V = 1. 6589 nm3, Z = 2. Both copper( Ⅱ ) ions are in a square pyramidal coordination environment , and linked by oxamido bridge. The distance between them is 0. 526 nm. Variable temperature (4. 2-300 K) magnetic susceptibility data for this complex show that there exists a relatively large antiferromagnetic exchange interaction between the two copper( Ⅱ ) ions with a J value of-740. 40 cm-1.     

Synthesis and Crystal Structure of a Copper(Ⅱ)Complex with Funnel-like Ligand Based on Calix[6]arene

The preparation method of a funnel like ligand derived from calix[6]arene and tris(2-pyridyl-methyl)anime has been improved.The Cu(Ⅱ)complex was obtained and ch...     

Synthesis and Properties of Dinuclear Cu( Ⅱ ) Complexes Derived from Oxamidobis(propionato)cuprate( Ⅱ )

Three dinuclear complexes were synthesized and designated as Cu(obp)CuL where obp =oxamidobis(propionato), L=2,2' -bipyridyl(bpy) (1), 1 , 10-phenathroline(phen)(2) and 5-nitro-1, 10-phenathroline(NO2-phen)(3). The complexes were characterized by elemental analyses, in fared and electronic spectra, magnetic susceptibilities and ESR spectra, indicating antiferromagnetic spin exchange interactions between metal ions.