带荧光基团蒽的正庚醛和正丁醛Resorcinarenes母体衍生物的合成研究

合成正庚醛、正丁醛 Resorcinarenes母体 ,经生成酯衍生物后同 9-蒽甲醇反应 ,合成了带荧光基团蒽的正庚醛、正丁醛 Resorcinarenes母体衍生物。考察了各种因素对产物产率的影响 ,并给出了产物的 IR,1 H NMR,MS及

Resorcinarenes的研究及其进展

综述了国内外对 Resorcinarenes化学的研究历史、Resorcinarenes的合成及应用新进展。目前 Resor-cinarenes化学的研究已超越了有机化学和无机化学的范畴 ,正向新技术方向发展。

Resorcinarenes的合成及其边缘化学修饰(Ⅱ)

探讨了烷基醛类 (丁醛、戊醛、异丁醛 )的 Resorcinarenes的合成及其边缘化学修饰 (乙酰化、甲基化 ) ,研究了烷基取代基对合成的影响。并用 IR,1 H NMR,MS和 UV对这些化合物进行了表征。

Resorcinarenes的合成及其边缘化学修饰(Ⅰ)

探讨了烷基醛类（乙醛、丙醛）的Ｒｅｓｏｒｃｉｎａｒｅｎｅｓ的合成及其边缘化学修饰（乙酸化、甲基化），研究了各种因素对Ｒｅｓｏｒｃｉｎａｒｅｎｅｓ的影响。确定了较佳反应条件。

带荧光基团蒽的异丁醛、正庚醛、正丁醛Resorcinarenes母体衍生物的合成研究

合成了异丁醛、正庚醛、正丁醛 Resorcinarenes母体 ,经酯衍生化后 ,分别同 9-蒽甲醇反应 ,合成了带荧光基团蒽的异丁醛、正庚醛、正丁醛 Resorcinarenes母体衍生物。

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

Calix resorcinarenes bearing four hydrophobic side chains ( Ar-Rn, Ar-Ph, and Ar-N) orient stably on water oil interface and show high solubilization capacities for organic compounds, such as long chain alcohols, benzene, toluene and dyes. The capacities are high even near the cmc of polyalkylated calix resorcinarenes, but the solubilities of organic compounds(solubilizates) decrease with the increase of the size of the solubilizates. Ar-R 6, with a chain length of six carbons, is the most effective among Ar-R n , Ar-Ph, and Ar-N; 11 fold mol of hexanol is dissolved in 2×10 -3 mol/L Ar-R 6. Moreover, Ar-R n bearing four alkyl side chains solubilizes the chain alcohols of the same chain length mostly. The solubilization capacities are presumably brought by inclusion in a large cavity of the polyalkylated calix resorcinarenes and by an efficient orientation of the solubilizates.

Syntheses and Crystal Structures of Functionalized Tetramethyl Resorcinarenes

Tetramethyl resorcinarene, which was obtained by acidic condensation of resorcinol with paraacetoalde- hyde, was chemically modified to the functionalized O-acyl, O-tosyl and O-acetate derivatives by corresponding acylation, p-toluenesulfonylation and alkylation reactions. The single crystal structures of these functionalized resor- cinarenes and the complex of tetramethyl resorcinarene with 2,2＇-hipyridine were determined by X-ray diffraction method. All these resorcinarenes adopt the all-cis configuration with four methyl groups stretching to the down rim and form 1D or 2D structures through H-bonds.

高残炭率酚醛树脂的耐热性能研究

采用无水乙醇、水杨醛和水杨醛+Resorcinarenes杯芳烃分别对自制氨酚醛树脂进行改性处理,得到3种改性酚醛树脂A、B、C。通过傅立叶变换红外光谱、差示扫描量热法和热重法对3种改性酚醛树脂的分子结构、固化行为和耐热性能进行了对比分析,运用Ozawa等转化率法对改性酚醛树脂C进行了热降解动力学分析。结果表明,与改性酚醛树脂A、B相比,改性酚醛树脂C具有更好的热稳定性和更高的残炭率,它在700℃氮气气氛下的残炭率大于73%;水杨醛、Resorcinarenes杯芳烃与氨酚醛树脂相互作用,形成的芳环含量更高的共轭结构使改性酚醛树脂C的热解表观活化能大幅度提高,这是其具有优良耐热性能和高残炭率的主要原因。

Co-crystallization of Resorcin[4]arene Tetracarboxylic Acid with Triethylamine:Synthesis and Crystal Structure

Treatment of resorcin[4]arene tetracarboxylic acid 1 with triethylamine in the presence of Co（CH3COO）2·4H2O and 4,4 -bipyridine gave a co-crystallization 14-·4Et3NH＋（C32H20O164-·4Et3NH＋,Mr=1069.27） from ethanol and water.The compound was structurally determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n,with a=8.1763（18）,b=12.913（3）,c=28.724（7） ,β=97.574（4）o,V=3006.3（12） 3,Z=2,Dc=1.181 g/cm3,F（000）=1152,Rint=0.0275,T=293（2） K,μ=0.086 mm-1,the final R=0.0634 and wR = 0.1752 for 5082 observed reflections with I 〉 2σ（I）. The co-crystallization is very stable at room temperature. Possibly, a network of N-H…O（=C） plays an important role in the structure. Meanwhile, the compound emits a weak cyan luminescence with peak maximum band at 458 nm.

The removal of Cr(Ⅵ) through polymeric supported liquid membrane by using calix[4]arene as a carrier

In this work, the transport and removal of Cr(Ⅵ) were achieved through supported liquid membrane(SLM) by using a 5,17, di-tert-butyl-11,23-bis[(1,4-dioxa-8-azaspiro [4,5]decanyl)methyl]-25,26,27,28-tetrahydroxy calix[4]arene carrier, dissolved in 2-nitrophenyl octyl ether dichloromethane.The studied parameters are the solvent effect in the membrane phase, the effect of carrier concentration, and the acid type in the donor phase.The Celgard 2500 was used as a membrane support.We used the Danesi mass transfer model to calculate the permeability coefficients for each studied parameter.In addition, AFM and SEM techniques were used to characterize the surface morphology of the prepared Celgard 2500 membrane that included the calix[4]arene carrier.

Synthesis of Calix[4]resorcinarene Core Dendrimers with Peripheral Salicylideneimine Functional Groups

First to third-generation calix[4] resorcinarene core dendrimers, compounds 4a, 4b, 7a, 7b, 10a and 10b, were prepared via the divergent method in seven steps with the corresponding tetraphenyl- and tetra （hydroxyphenyl） calix[4] resorcinarenes （compounds 1a, 1b） as the starting material. The repeat units of the polyamidoamines of these dendrimers were obtained by the ammonolysis of ethyl calixarylacetates 2a and 2b with 1,3-diaminopropane, that is, amide derivatives with terminal amino groups, which in turn reacted with ethyl acrylate to give a higher generation of ester derivatives. The structures of these dendrimers were characterized by IR, ^1H and ^13C NMR spoctrometries. The crystal structure of compound 2b with 12 ethoxycarbonylmethoxy groups was determined by X-ray analysis.

Synthesis and Molecular Structure of a C-iso-Butyl-cavitand Bowl with Trimethyl and Methylol Groups

A C-iso-butyl-cavitand bowl with trimethyl and methylol groups was isolated from the acetoxymethyl hydrolysis of mono-methylbromo-cavitand in THF. The molecular structure of the present cavitand compound was determined by single-crystal X-ray diffraction. The compound (C56H70N2O9) crystallizes in orthorhombic, space group Pnma with a = 19.5060(15), b = 19.8136(15), c = 12.9508(10) ?, V = 5005.3(7) ?3, Z = 4, Mr = 915.14, Dc = 1.214 g/cm3, F(000) = 1968, μ = 0.081 mm?1, S = 1.012, the final R = 0.0789 and wR = 0.1488 for 2298 observed reflections with I > 2σ(I) and 322 variable parameters. The structure exhibits a rigid bowl-cavity with an available functional hydroxyl group. The bowl of cavitand contains a CH3CN solvent molecule, and the depth of the bowl-shaped cavity is ca. 2.42 ?.

Synthesis and Structure of an Octopus-like Octapropargyl Tetra-iso-butyl-resorcin[4]arene

Treatment of tetra-iso-butyl-resorcin[4]arene 1 with propargyl bromide in the presence of K2CO3 as base gave an octopus-like octapropargyl tetra-iso-butyl-resorcin[4]arene 2 （C68H72O8, Mr = 1017.26） in a quantitative yield. Single-crystal structure of 2 was determined by X-ray crystallography. 2 crystallizes in the monoclinic system, space group P21/n with a =13.3247（6）, b = 24.7929（11）, c = 19.1810（9）A°, β = 109.272（1）°, V= 5981.5（5） A°^3, Dc = 1.130g/cm^3,μ = 0.073 mm^-1, F（000） = 2176 and Z = 4. Overall structure of 2 reveals an octopus-like resorcinarene with eight propargyl groups in different directions. The resorcinarene adopts the boat conformation where the iso-butyl residues act as four-legged piano stool. The two opposite aryl rings of the macrocyclic framework are almost coplanar, and the two others facing each other are perpendicular to this plane.

Hydrogen-bonded 1D and 2D Assemblies of Tetraiso-butyl-resorcin[4]arene in the Crystalline State

X-ray crystal structures of co-crystals involving tetra-iso-butyl-resorcin[4]arene 1 with both acetone and acetonitrile solvents were reported. The component 1?2(CH3)2CO 2 assembles such that the resorcin[4]arene adopts a C2v conformation and the acetone serves as hydrogen bond acceptors, forming a 1D hydrogen-bonded polymer. 2 (C50H68O10) crystallizes in the triclinic, space group P1 with a = 10.0440(7), b = 13.7498(9), c = 17.6374(12) ?, α = 77.726(2), β = 86.733(2), γ = 88.634(2)o, V = 2376.1(3) ?3, Dc = 1.159 g/cm3, and Z = 2. The assembly process of component 1?2CH3CN?H2O 3 yields a 2D hydrogen-bonded polymer formed by intermolecular hydrogen bonds between resorcin[4]arene and water molecules. In the case of component 3, the acetonitrile molecule serves as guest inside the bowl of resorcin[4]arene host. 3 (C48H64N2O9) crystallizes in the monoclinic, space group P2/n with a = 13.7570(18), b = 9.0961(12), c = 19.453(3) ?, β = 103.017(3)o, V = 2371.7(5) ?3, Dc = 1.138 g/cm3, and Z = 2.

Effect of C-Tetramethyl Calix[4]resorcinarene Acrylate on Curing Behavior and Film Properties of Thiol-acrylate Coating System

An octa-functional acrylate of C-tetramethyl calix[4]resorcinarene（CMC-4-RA） was facilely synthesized and characterized with ^1H NMR, ^13C NMR and FTIR spectroscopy. The CMC-4-RA was added to a thiol-acrylate system with different mass ratios, and exposed to a middle pressure mercury lamp. The maximum photopolymerization rate and final vinyl group conversion in the cured film increased greatly along with CMC-4-RA addition that was monitored with Photo-DSC. The tensile strength and pendulum hardness were improved significantly after the addition of CMC-4-RA. With increasing the content of CMC-4-RA to 60%（mass fraction）, the glass transition temperature increased from 34.2 ℃ to 84.1 ℃; the cross-link density was calculated to be increased from 23.83 mmol/cm^3 to 82.40 mmol/cm^3 according to dynamic mechanical thermal analysis; the thermostability was greatly improved.

Synthesis of Calix[4]resorcinarene Amide Derivatives

Three different synthetic routes were developed to introduce carbamoyloxy functional groups at the upper periphery of two calix[4]resorcinarenes. By treating activated esters 2a-b with excess corresponding amine such as 3-(dimethylamino)propylamine 3, -phenethylamine 4 and triethylenetetramine 5, six amide derivatives 6a^8b were obtained in high yield (Route 1). The pyridine-linked amide derivatives 9a-b were prepared by using acid chloride intermediate (Route 2). The amide derivatives 10a-b were obtained in moderate yields by direct alkylation of phenolic hydroxyl groups of 1a-b with N,N-dipropylchloroacetoamide in the presence of K2CO3/KI in acetone (Route 3).

One-dimensional Hydrogen-bonded Polymer Based on Tetra-iso-butyl-resorcin[4]arene and 2,6-Diacetylpyridine

The co-crystallization of tetra-iso-butyl-resorcin[4]arene 1 and 2,6-diacetyl- pyridine (Ac2py) from MeCN/CH2Cl2 yielded a multi-component complex 1?Ac2py?2H2O?0.5Me- CN 2, in which the upper rim of 1 is extended supramolecularly by way of hydrogen bonds. Complex 2 (C52H66.5N1.5O14) crystallizes in monoclinic, space group P21/m with a = 10.845(9), b = 20.805(17), c = 12.881(11) ?, β = 103.884(19)o, V = 2821(4) ?3, Dc = 1.102 g/cm3 and Z = 2. The molecular structure shows that the two adjacent double-stranded arrays as well as linear and zigzag chains generated from Ac2py and water bridging to two resorcin[4] arene molecules, respectively, facilitate self-inclusion of one-dimensional hydrogen-bonded polymer.

Methyl Cholate and Resorcinarene New Carriers for the Recovery of Cr(Ⅲ) Ions by Supported Liquid Membranes (SLM)s

The technique of supported liquid membranes was used to achieve the facilitated transport of Cr(III) ions, using tow amphiphilic carriers, the methyl cholate and resorcinarene. For prepared SLMs, toluene as organic phase and film of polyvinylidene difluoride, as hydrophobic polymer support with 100 μm in thickness and 0.45 μm as the diameter of the pores. The macroscopic parameters (P and J0) on the transport of these ions were determined for different medium temperatures. For these different environments, the prepared SLMs were highly permeable and a clear evolution of these parameters was observed. The parameter J0 depended on the temperature according to the Arrhenius equation. The activation parameters, Ea, ΔH≠ and ΔS≠, for the transition state on the reaction of complex formation (ST) , were determined. To explain these results for this phenomenon, and achieve a better extraction of the substrate, a model based on the substrate complexation by the carrier and the diffusion of the formed complex (ST) was developed. The experimental results verify this model and determine the microscopic parameters (Kass and D*). These studies show that these parameters Kass and D* are specific to facilitated transport of Cr(III) ions by each of the carriers and they are changing significantly with temperature.