Reactions of P(III)-Halides with Calix[4]Resorcinarenes

Abstract

Reactions of calix[4]resorcinarenes, bearing aliphatic radicals of different length, with P(III)-halides results in the formation of cyclic chlorophosphites and chlorophosphates.     

Functional modification,self-assembly and application of calix[4]resorcinarenes

As a special subset of calix[4]arene, calix[4]resorcinarene is an excellent molecular platform which could be modified by introducing functional groups to multiple sites at the upper and lower rims. There are mainly three ways to build functionalized calix[4]resorcinarene derivatives: (1) modification on the C-2 sites of calix[4]resorcinarenes; (2) modification on the phenolic hydroxyl groups of calix[4]resorcinarenes; (3) modification on the bridging methylenes at lower rim of calix[4]resorcinarenes. Functionalized calix[4]resorcinarene derivatives play an important role in the development of self-assembly chemistry, among which hydrogen bonding and metal coordination are the two most common interactions to obtain multicomponent structures. Moreover, due to the excellent topological structures and various active substituents of functionalized calix[4]resorcinarene derivatives, their applications in various fields, such as nanoparticles, catalysts, fluorescent materials, and sensors, have been briefly presented in this paper.

     

无溶剂法合成杯[4]芳烯星形化合物

以对苯二甲醛、乙酸酐为原料合成对苯二甲醛单缩醛, 接着与间苯二酚反应, 制备了含醛基杯[4]芳烯. 利用季戊四醇与含醛基杯[4]芳烯反应, 进而再与3-[4-(2,5-二氧杂环戊基)苯基]-9-[4-二(甲羰氧基)甲基苯基]-2,4,8,10-四氧杂螺环[5.5]十一烷反应, 合成了杯[4]芳烯星形化合物, 收率为65.2%. 产品结构经 IR, ¹H NMR, MS 和元素分析进行了表征.     

Stereoselective Synthesis and Structure of New Types of Calix[4]resorcinarenes. Complexation of Tetrakis(O,O‐Phosphorus)Bridged‐Calix[4]resorcinarenes with Heavy Metal Atoms

The acid‐catalyzed (with HCl) condensation reactions of resorcinol ( 1 ) with 1‐naphthaldehyde ( 2 ) and isobutyraldehyde ( 3 ) furnished the tetrameric macrocyclic compounds 4 and 6 . Detailed NMR‐investigations of the acetylated tetrameric species 5 surprisingly support a structure not in agreement with the expected all‐cis conformation. The chair conformation (C_2h symmetry) of the acetylated derivative 5 was established through a crystal X‐ray diffraction study. The naphthyl substituents are arranged in trans position above and below the plane made up by the resorcinol units. The reaction of resorcinol 1 with isobutyraldehyde, in accord with expectation, led to the calix[4]resorcinaren ( 6 ). The ¹H NMR spectra of compound 6 and 7 appeared at room temperature as broad signals, indicating a conformation of C_2v symmetry. The reaction of the C‐methyl‐tetrakis‐P‐(chlorodioxaphosphocin)‐calix[4]resorcinarenes ( 8 ) and ( 10 ) with suitable N‐trimethylsilyl organic amines were conducted in tetrahydrofuran suspension, furnishing the P–N‐substituted calix[4]resorcinarenes ( 9 ) and ( 11 ). While in the complexation of C‐methyl‐tetrabromotetrakis‐P‐(dimethylaminodioxaphosphocin)‐calix[4]resorcinarene ( 13 ) with (tht)AuCl (tht = tetrahydrothiophene) the expected, neutral tetra‐substituted complex 15 was formed, the reaction of 13 with moist acetonitrile led to the anionic atomic framework 14 . X‐ray structure determinations of the complexes 14 and 15 show that both possess the cone conformation. In the gold complex 15 , the Au–Cl groups form a loose aggregate, with three Au…Cl contacts of 316–340 pm; one of the groups points towards the centre of the cone. The copper(I) complex 14 displays crystallographic mirror symmetry, with a central Cu₄Cl₅ unit involving tetrahedrally coordinated copper.     

Phosphorylation of oxyethylated resorcinol and calix[4]resorcinarene with P(III) acid amides

Abstract

Phosphorylation of 1,3-bis(2-hydroxyethoxy)benzene and octa(2-hydroxyethyl) calix[4]-resorcinarenes with P(III) acid amides and chloramides has been studied. It has been determined that the nature of phosphorous acid amides affects significantly the synthetic result of the reaction.     

无溶剂法合成4,6,10,12,16,18,22,24-八羟基-2,8,14,20-四-{(联三-(3-苯基-2,4,8,10-四氧杂螺[5.5]十一烷基))-(4-(2-(4,6,10,12,16,18,22,24-八羟基)杯芳基)苯基)}杯芳烃螺环树形大分子化合物

以对苯二甲醛、丙二腈为原料, 合成对苯二甲醛单缩醛, 再与季戊四醇反应得到了2,4,8,10-四氧杂-2,9-二(4-二氰基乙烯基苯基)螺[5.5]十一烷, 经水解, 与丙二腈反应, 制备了中间体2,4,8,10-四氧杂-2-(4-二氰基乙烯基苯基)-9-(4-甲酰基苯基)螺[5.5]十一烷(3). 用乙酸酐保护的对苯二甲醛单缩醛与间苯二酚反应, 制备了杯芳烯中间体(6). 将化合物6与过量的化合物3反应, 得到中间体7, 经水解后与过量的化合物6反应, 得到了4,6,10,12,16,18,22,24-八羟基-2,8,14,20-四-{(联三-(3-苯基-2,4,8,10-四氧杂螺[5.5]十一烷基))-(4-(2-(4,6,10,12,16,18,22,24-八羟基)杯芳基)苯基)}杯芳烃螺环树形大分子化合物(9). 总收率为12.7%. 产物结构用IR, 1H NMR, 13C NMR, MS 和元素分析进行了表征, 对影响反应的因素进行了讨论.     

Aggregation of amphiphilic aminomethylated calix[4]resorcinarenes and the nonionic surfactant Triton-X-100 in organic solvents

Aggregation and intermolecular interactions of amphiphilic calix[4]resorcinarene (1), aminomethylated calix[4]resorcinarenes (AMC 2—7) with different structures of the upper rim (including the oxazine structure in 6 and 7) and hydrophobic substituents on the lower (2—5), upper (6), or both rims (7) in the absence and in the presence of the nonionic surfactant Triton-X-100 (8) and p-nitrophenol (9) in chloroform and 1,4-dioxane were studied by permittivity measurements and 2D ROESY ¹H NMR technique. The tendency of amphiphilic derivatives 1—7 toward self-aggregation and mixed aggregation with surfactant 8 primarily depends on the nature of both the solvent and the polar groups on the upper rim of calixarenes. In chloroform, AMC—8 aggregates show interactions of the methyl and methylene groups of the hydrophobic substituents of AMC with the ethyleneoxy fragments of surfactant 8, while in stable intermolecular complexes of 5 and 6 with compound 9, the methylene groups of the long-chain radicals of the AMC strongly interact with the aromatic protons ortho to the hydroxy group of 9. In 1,4-dioxane, calix[4]resorcinarenes 1 and 5 are bound in stable solvates, which prevents them from forming aggregates and mixed micelles.     

Complexation of dirhodium(II) with N-functionalized calix[4]resorcinarenes

Russian Chemical Bulletin - Some features of the complexation of [Rh2(OAc)4?2H2O] with calix[4]resorcinarenes functionalized by aminoalkyl groups in the upper or lower rims in EtOH and Me2CO...     

Synthesis of calix[4]resorcinarenes with phosphorylaryl substituents at the lower rim of the molecule

Reaction of resorcinarenes with 4-phosphorylbenzaldehydes afforded calix[4]resorcinarenes, bearing phosphorylaryl substituents at the lower rim of the molecule. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2269–2271, November, 2007.     

New salt structures based on aminomethylated calix[4]-resorcinarenes and (1-hydroxyethane-1,1-diyl)bisphosphonic acid

Russian Journal of Organic Chemistry - Aminomethylation of calix[4]resorcinarenes with (1-hydroxyethane-1,1-diyl)bisphosphonic acid afforded a series of new water soluble onium salts.     

Octacis(2-hydroxyethylated) Calix[4]resorcinarenes Phosphorochloridates as Precursors in Production of Water-Soluble Calix[4]resorcinarene and Phosphoramidates

Russian Journal of General Chemistry - The reactions of organosilicon derivatives of octacis(2-hydroxyethylated) calix[4]resorcinarenes with phosphoryl trichloride and subsequent hydrolysis of the...     

Synthesis and Properties of a Series of Novel Calix[6]arene Diazo Derivatives

In this study, seven new compounds p-(4-butyl-phenylazo)calix[6]arene(1), p-(4-(phenylazo)phenylazo)calix[6]arene (2),p-(4-hydroxyphenylazo)calix[6]arene (3),p-{4-[N-(thiazol-2-yl)sulfamoyl]phenylazo\}calix[6]arene(4), p-(4-acetamidophenylazo)calix[6]arene (5),p-(thiazol-2-ylazo)calix[6]arene (6) andp-(2-sulfanylphenylazo)calix[6]arene (7) have been synthesizedfrom calix[6]arene by diazo coupling with the corresponding aromaticamines. UV-Vis, IR, ¹H and ¹³C NMR spectral data have been used to elucidate the structures of the compounds elemental analyses     

Aggregation behavior and catalytic activity of systems based on calix[4]resorcinarene derivatives and surfactants. 1. Mixed micellization of aminomethylated calix[4]resorcinarenes with cetyltrimethylammonium bromide in aqueous dimethylformamide

Mixed micellization of amphiphilic aminomethylated calix[4]resorcinarenes and phenols, which are their structural units, with the cationic surfactant cetyltrimethylammonium bromide (CTAB) in aqueous 10—70 vol % DMF decreases the critical micelle concentration; the resulting aggregates are larger than those in the CTAB—DMF—water systems. The micellization of CTAB with aminomethylated calix[4]resorcinarenes proceeds in two steps, while its micellization with phenols is a single-step process. The micellization characteristics depend on the structure and hydrophobicity of the amphiphilic compound and the concentration of DMF.     

Microwave‐Assisted Synthesis of Calix[4]resorcinarene Hydroxamic Acids

New calix[4]resorcinarenes bearing hydroxamic acid groups, calix[4]resorcinarene hydroxamic acids (CRAHAs), have been synthesized.     

Complexes of dirhodium(II) carboxylates with calix[4]resorcinarenes functionalized at the upper and lower rim of the molecule with P,N-containing Fragments

The features of the reaction between dirhodium(II) carboxylate and calix[4]resorcinarenes modified with various type functional groups at the upper and lower rim of the molecule in protic anhydrous solvent (ethanol) under inert atmosphere were investigated. Neutral complex compounds were isolated formed as a result of substitution of a water molecule by the macroligand in the axial position with respect to the R $ \tilde h The features of the reaction between dirhodium(II) carboxylate and calix[4]resorcinarenes modified with various type functional groups at the upper and lower rim of the molecule in protic anhydrous solvent (ethanol) under inert atmosphere were investigated. Neutral complex compounds were isolated formed as a result of substitution of a water molecule by the macroligand in the axial position with respect to the RRh bond occurring with the conservation of the latter. The compounds were characterized by 31P NMR, UV, IR, Raman, and ESR spectroscopy. Their composition was confirmed by elemental analysis. Original Russian Text ? E.V. Guseva, E.L. Gavrilova, A.A. Naumova, V.I. Morozov, N.I. Shatalova, D.T. Karimova, V.K. Polovnyak, 2008, published in Zhurnal Obshchei Khimii, 2008, Vol. 78, No. 12, pp. 1963–1971.     

Calixarenes and calix[4]resorcinarenes as chiral NMR solvating agents

Calixarenes (CAs) and calix[4]resorcinarenes are cavity compounds, chiral analogues of which have the potential to be used as reagents for the differentiation of enantiomers in NMR spectroscopy. The nature of the substituent groups attached to the cavity permits the preparation of organic- or water-soluble analogues. In NMR applications, chirality of the CAs or calix[4]resorcinarene is usually achieved through the attachment of enantiomerically pure substituent groups. The use of inherently chiral analogues for chiral differentiation is less common. The range of CAs and calix[4]resorcinarenes that have been used for chiral analysis in NMR spectroscopy is reviewed.     

Surface Activities of Calix[4] resorcinarenes Bearing Four Hydrophobic Chains and Its Sol ubilization for Organic Compounds

ＩｎｔｒｏｄｕｃｔｉｏｎＩｎｃｌｕｓｉｏｎｃｏｍｐｏｕｎｄｓｈａｖｅｂｅｅｎｎｏｔｅｄｉｎｒｅｃｅｎｔｙｅａｒｓａｎｄｒｅｓｏｒｃｉｎｏｌ ｔｙｐｅｃａｌｉｘ [4 ]ａｒｅｎｅｈａｓｂｅｅｎｓｔｕｄｉｅｄｆｏｒｔｈｅｉｒｉｎｃｌｕｓｉｏｎａｂｉｌｉｔｉｅｓｂｙＳｃｈｅｉｄｅｒａｎｄＢｕｇｌｅｒｅｔａｌ[1— 3] .Ｔｈｅｐｏｌｙｏｌｍｏｉｅｔｉｅｓｉｎｃａｌｉｘ[4 ]ｒｅ ｓｏｒｃｉｎａｒｅｎｅｆｏｒｍｒｉｇｉｄｈｙｄｒｏｇｅｎ ｂｏｎｄｉｎｇｎｅｔｗｏｒｋｓ[4 ] ,ａｎｄｃａｌｉｘ [4 ]ｒｅｓｏｒｃｉｎａｒｅ…     

Evidence of Hydrogen Bonding in Stabilizing the Cone Conformation of a Monoalkylated Calix[4]arene. X-ray Structure of 25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene

The synthesis of25-[2-(ethoxy-1-p-toluene-sulfonate)phenyl]-26,27,28-trihydroxy calix[4]arene3 as a byproduct of the preparation of 1,3-dialkylated25,27-di-[2-(ethoxy-1p-toluene-sulfonate)phenyl]-26,28-dihydroxy calix[4]arene 2 is reported. Compound 3 is a monoalkylatedcalix[4]arene in the cone conformation. The X-ray structure of 3 showed that this conformation is stabilized by intramolecular hydrogen bonding.     

Water-soluble calix[4]resorcinarenes with hydroxyproline groups as chiral NMR solvating agents

Water-soluble calix[4]resorcinarenes containing 3- and 4-hydroxyproline, d-nipecotic acid, (S)-2-(methoxymethyl)pyrrolidine, (S)-2-pyrrolidine methanol, and (S,S)-(+)-2,4-bis(methoxymethyl)pyrrolidine substituents are synthesized and evaluated as chiral NMR solvating agents. The derivatives with the hydroxyproline groups are especially effective at causing enantiomeric discrimination in the spectra of water-soluble cationic and anionic compounds with pyridyl, phenyl, and bicyclic aromatic rings. Binding studies show that mono- and ortho-substituted phenyl rings associate within the cavity of the calix[4]resorcinarenes, as do naphthyl rings with mono-, 2,3-, and 1,8-substitution patterns. Anthracene derivatives with an amino or sulfonyl group at the 1-position bind within the cavity, as well. Aromatic resonances of the substrates exhibit substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcinarene. The effectiveness of the reagents at producing chiral recognition in 1H NMR spectra is demonstrated with sodium mandelate, the sodium salt of tryptophan, and doxylamine succinate. While no one reagent is consistently the most effective, the calix[4]resorcinarenes with trans-4-hydroxyproline and trans-3-hydroxyproline moieties generally produce the largest nonequivalence in the 1H NMR spectra of the substrates.     

Calix[4]arenes with 1,2- and 1,3-upper rim tetrathiafulvalene bridges

Herein we report the synthesis of several calix[4]arene derivatives with tetrathiafulvalene bridges at the upper rim. Calix[4]arene-tetrathiafulvalene (TTF) conjugates 4a–d, fixed in cone conformation and comprising two smaller 1,2-bridges, were prepared by cyclisation of tetrakis-chloromethylated calix[4]arene 1 with 2,3-dithiolates of TTFs. Larger calix[4]arene-TTF macrocycles 14 and 15, also in cone conformation, contain 1,3-bridges and were synthesised by cyclisation of 2,6- and 2,7-dithiolates of TTFs with bis-bromomethylated calix[4]arene 7. Redox properties of new calix[4]arene-TTF conjugates were characterised using cyclic voltammetry.