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Synthesis of Schiff Base Calix [4] arene Crowns 总被引:2,自引:0,他引:2
This letter reports the synthesis of Schiff base calix [4] arene crowns containing m-xylylene phenol subunit, in which calix [4] arene Schiff base crowns 2a,2b and 2c were formed by 1:1 condensation of calix [4] arene diamine 1 with dialdehydes (2,6-diformyl-4-chlorophenol 3a,2,6-diformyl-4-methylphenol 3b,2,6-diformyl-4-tert-butylphenol 3c)under high dilute condition in refluxing anhydrous ethanol in 65-70% yield. 相似文献
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Salmon L Thuéry P Ephritikhine M 《Dalton transactions (Cambridge, England : 2003)》2006,(30):3629-3637
Reactions of UCl4 with calix[n]arenes (n = 4, 6) in THF gave the mononuclear [UCl2(calix[4]arene - 2H)(THF)2].2THF (.2THF) and the bis-dinuclear [U2Cl2(calix[6]arene - 6H)(THF)3]2.6THF (.6THF) complexes, respectively, while the mono-, di- and trinuclear compounds [Hpy]2[UCl3(calix[4]arene - 3H)].py (.py), [Hpy](4)[U2Cl6(calix[6]arene - 6H)].3py (.3py), [Hpy]3[U2Cl5(calix[6]arene - 6H)(py)].py (.py) and [Hpy]6[U3Cl11(calix[8]arene - 7H)].3py (.3py) were obtained by treatment of UCl4 with calix[n]arenes (n = 4, 6, 8) in pyridine. The sodium salt of calix[8]arene reacted with UCl4 to give the pentanuclear complex [U{U2Cl3(calix[8]arene - 7H)(py)5}2].8py (.8py). Reaction of U(acac)4 (acac = MeCOCHCOMe) with calix[4]arene in pyridine afforded the mononuclear complex [U(acac)2(calix[4]arene - 2H)].4py (.4py) and its treatment with the sodium salt of calix[8]arene led to the formation of the 1D polymer [U2(acac)6(calix[8]arene - 6H)(py)4Na4]n. The sandwich complex [Hpy]2[U(calix[4]arene - 3H)2][OTf].4py (.4py) was obtained by treatment of U(OTf)4 (OTf = OSO2CF3) with calix[4]arene in pyridine. All the complexes have been characterized by X-ray diffraction analysis. 相似文献
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Bhattacharya S Nayak SK Semwal A Banerjee M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(4):595-606
Equilibria for the formation of supramolecular complexes of [60]fullerene with a series of mono O-substituted calix[6]arenes, namely: (i) 37-methoxy-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (1), (ii) 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (2), (iii) 37-phenacyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (3), (iv) 37-ethylester-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (4) and (v) 37-benzyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert-butyl)calix[6]arene (5) have been studied in CCl4 medium by absorption spectroscopic technique. The stoichiometry has been found to be 1:1 ([60]fullerene:calix[6]arene) in each case. An absorption band due to charge transfer (CT) transition is observed in each case in the visible region. The vertical ionisation potentials (I(D)(v)) of all the calix[6]arenes under study have been estimated utilising CT transition energy. The experimental I(D)(v) values also yield a good estimate of the electron affinity of [60]fullerene. The degrees of CT in the ground state of the complexes have been found to be very low (about 0.15%). Resonance energy of the complexes have been estimated. Thermodynamic parameters for the supramolecular complex formation of [60]fullerene with mono O-substituted calix[6]arene receptors are reported. It is observed that among the calix[6]arenes under the present study, only 1 and 4 form inclusion complexes with [60]fullerene. This has also been substantiated by theoretical calculation using PM3 method. Thus presence of one substituent group (of different types) on the lower rim of the calix[6]arene molecule has been shown to govern the host-guest complexation process. 相似文献
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杯芳烃与NO2硝化反应的研究 总被引:1,自引:0,他引:1
系统地研究了羟基杯[n]芳烃、甲氧基杯[n]芳烃和对特丁基杯[n]芳烃(n=4, 6, 8)与NO2气体的硝化反应, 发现可以成功地得到25,26,27,28-四羟基杯[4]芳烃、37,38,39,40,41,42-六羟基杯[6]芳烃以及25,26,27,28-四甲氧基杯[4]芳烃的对位全硝化产物, 产率分别为90%, 70%和40%; 尤其是25,26,27,28-四羟基杯[4]芳烃与NO2的反应20 min即可完成. 认为共振式酚氧负离子结构是影响该类硝化反应的关键, 并对反应机理进行了探讨. 相似文献
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The preparation of an 1,3-alternate calix[4]arene tetraphosphane ligand, 25,26,27,28-tetrakis{2-(diphenylphosphino)ethoxy}calix[4]arene (4), is described. Ligand 4 is obtained in four steps in 17% overall yield. Reaction of 4 with AgBF4 produced the encapsulated two silver complex [Ag2{(P,P,P,P)-tetraphencalix[4]arene}](BF4)2. The solid-state structure shows that the encapsulated silver undergoes a substantial pi-interaction by two opposite arene rings. Rhodation of 4 employing [Rh(cot)2]BF4 yielded the encapsulated complex with a bent coordination mode. Two organometallic fragments inclusioned inside a 1,3-alternate calix[4]arene tetraphosphane was also achieved by the reaction of 4 with [PtH(PPh3)2 (thf)]+. Full characterization includes X-ray structural studies of compounds 4-6. 相似文献
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A. N. Novikov V. A. Bacherikov Yu. E. Shapiro A. I. Gren 《Journal of Structural Chemistry》2006,47(6):1003-1015
The cone conformation of C 4 symmetry is shown by the Hartree-Fock method (3-21G basis) to be the predominant conformer of calix[4]arene; the compressed cone of C 2 symmetry is the major conformer of calix[6]arene. Using quantum chemical methods we calculated hydrogen bond cleavage energies for calix[4]-(ab initio and density functional methods) and calix[6]arene (ab initio), and also for the complex of calix[4]arene with carbon disulfide. These energies along with structural data point to the cooperative effect of hydrogen bonds. The results of these studies provided an explanation to the greater conformational lability of calix[6]arene compared with calix[4]arene molecules. It is also predicted that the nucleophilic substitution reaction involving calix[6]arene in the presence of weak bases and in aprotic solvents, as well as in the gas phase, will occur via diastereomeric transition states. 相似文献
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Hasalettin Deligöz 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):285-289
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 相似文献
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With a variation in reaction conditions, 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐calix[6]arene (3) and l,3,5‐tris(2‐(2‐chloroethoxy) ethoxy)‐calix [6] arene (4) or 4 and 4‐chloroethoxyethoxy‐calix[6]crown‐3 (5) were selectively synthesized from p‐tert‐butyl‐calix [6] arene and 2‐(2‐chloroethoxy)ethyltosylate. l,3–4,6‐p‐tert‐butylcalix[6]‐bis‐crown‐3 (6) with (u,u,u,d,d,d) conformation and 1,3–4,5‐p‐tert‐butylcalix[6]‐biscrown‐3 (7) with self‐anchored (u,u, u, u, u, d) conformation were synthesized through an intramolecularly ring‐closing condensation of 1, 4‐bis (2‐(2‐chloroethoxy)ethoxy)‐p‐tert‐butyl‐calix[6]arene (3) in 25% and 15% yield, respectively. Using 5 instead of 3, only 7 was obtained in 65% high yield. 6 and 7 show different complexation properties toward alkali metal and ammonium ions. 相似文献
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通过对杯[4]芳烃以及杯[6]芳烃上缘进行烯丙基化和硅氢加成2步衍生化反应得到硅氢化杯[4]芳烃以及硅氢化杯[6]芳烃,再将这2种硅氢化杯芳烃衍生物分别接枝到超细SiO2上。在不同的pH值条件下,就2种杯芳烃接枝超细SiO2衍生物对水合Cu2+及Ag+的萃取性能进行了研究。结果表明,与对叔丁基杯芳烃相比较,杯芳烃接枝超细SiO2衍生物对Cu2+和Ag+的萃取率都有所提高,其中杯[4]芳烃接枝超细SiO2对Ag+的最高萃取率达到98.78%,杯[6]芳烃接枝超细SiO2对Cu2+的最高萃取率达到67.74%。 相似文献
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Wetherby AE Goeller LR DiPasquale AG Rheingold AL Weinert CS 《Inorganic chemistry》2007,46(18):7579-7586
The protonolysis reaction of the germanium(II) amide Ge[N(SiMe3)2]2 with calix[4]arene and calix[8]arene furnishes the two germanium(II) calixarene complexes {calix[4]}Ge2 and {calix[8]}Ge4, respectively, which have been crystallographically characterized. The calix[4]arene complex contains a Ge2O2 rhombus at the center of the molecule and is one of the only four germanium(II) calix[4]arenes that have been structurally characterized. The calix[8]arene species is the first reported germanium calix[8]arene complex, and it exhibits an overall bowl-shaped structure which contains two Ge2O2 fragments. The latter complex reacts with Fe2(CO)9 to yield an octairon compound, which has also been structurally characterized and contains four GeFe2 triangles arranged around the macrocyclic ring. The germanium(II) centers are oxidized to germanium(IV) in this process, with concomitant reduction of the neutral diiron species to Fe2(CO)(8)2- anions. 相似文献
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Tatsuya Oshima Kaoru Oishi Keisuke Ohto Katsutoshi Inoue 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):79-85
Extraction behaviors of catecholamines with a series of calixarene carboxylic acid derivatives were investigated. Relatively large calix[6]arene and calix[8]arene extract catecholamines into the organic solution, while smaller calix[4]arene and the monomer analog do not. The calix[6]arene, which has a cavity that fits a protonated amino group well, selectively extracts a primary amino compound dopamine over other catecholamines. Slope analysis and Job’s method confirmed formation of a 1:1 complex between the calix[6]arene and dopamine. On the other hand, the calix[8]arene extracts both dopamine and adrenaline, due to the large cavity for induced-fit recognition. Dopamine extracted with the calixarene is quantitatively stripped by contacting the organic solution with a fresh acidic solution. 相似文献
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Nano CaCO3 was used as a condensation agent in the ring-opening reaction of p-tert-butylcalix[4] arene with epichlorohydrin to afford 5,11,17,23-tetra-tert-butyl1-26,27,28-trihydroxy-25-(1′-chloro-2′-hydroxy-3′-propyl)calix(4] arene regioselectively in 52% yield,The yield was less than 2% by using normal CaCO3 instead of nano one under the same conditions. 相似文献
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Wenzhan Yang Rahul Manek William M. Kolling Marius Brits Wilna Liebenberg 《Supramolecular chemistry》2013,25(6):485-496
In this study, the thermal behavior of three hydrated water-soluble 4-sulphonato calix[n]arenes was investigated. The melting points, heats of fusion, and heats of solution of the calix[4]arene, calix[6]arene and calix[8]arene were 277, 262, and 270°C; 192, 242 and 351 kJ/mol; and 30, 58 and 63 kJ/mol, respectively. Lower heat of fusion, smaller increase in entropy and smaller heat of solution of the calix[4]arene compared to the calix[6]arene and calix[8]arene showed that less heat was required to break up the crystal lattice of the smaller macromolecule. This apparent anomaly is rationalized in terms of smaller cooperativity of interaction between the molecules of calix[4]arene in the crystal lattice, although the strength of the individual interactions is stronger as evidenced by the higher melting point. TGA analysis indicated that about 17–20% of water was associated with the calix[n]arenes. Both TGA and hot stage microscopy results indicated that upon heating these molecules underwent stepwise water loss. TGA kinetics showed that the 4-sulphonato-calix[8]arene lost water easier than the other two calixarenes. The moisture adsorption behavior of all calixarenes followed type II isotherms. For the same amount of material, the calix[6]arene adsorbed more moisture than the calix[4]arene and the calix[8]arene. Moreover, dehydrated less crystalline 4-sulphonic-calix[n]arenes powders are hydroscopic. 相似文献
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[reaction: see text] Two new calix[6]arene derivatives 3 and 4 in a 1,4-anti conformation and one calix[8]arene derivative 5 were synthesized. SAMs of calix[n]arene (n = 4, 6, 8) derivatives 1-5 were formed on gold bead electrodes. Cyclic voltammetry with Ru(NH3)6(3+/2+) as a redox probe, together with impedance spectroscopy and reductive desorption, indicates that SAMs of 5 have a higher coverage than those of 3 and 4 due to the presence of hydrogen bonding and possibly its conformation. Noncovalent immobilization of C60 on gold surfaces was achieved with SAMs of calix[8]arene derivative 5 but not with those of 1-4. 相似文献
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[structure: see text]. The first examples of selectively functionalized calix[7]arenes have been obtained by weak-base promoted O-alkylation or O-benzoylation of p-tert-butylcalix[7]arene. Mono-, 1,3- and 1,4-disubstituted calix[7]arenes have been obtained in workable yields, while the 1,2,4,6-tetrasubstitution was achieved with surprisingly high selectivity (50-88% yield) by using K2CO3 as base. A rationale for this finding is proposed. 相似文献
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New calix[5]arene trivalent phosphorus derivatives have been synthesized which should be excellent ligands with which to study and control the interaction of a ligand atom with a metal. The larger cavity of the calix[5]arene (compared to calix[4]arene) provides a good balance between constraint and flexibility. Treatment of p-tert-butylcalix[5]arene with 2 equiv of either tris(dimethylamino)phosphine or dichlorophenylphosphine inserts two RP moieties into the calix[5]arene framework to give calix[5](PR)2(OH) (1, R = Me2N; 2, R = Ph). Further treatment of 1 with 4 equiv of HCl gives calix[5](PCl)2(OH) (3). Heating a solution of the monophosphorus compound calix[5](PNMe2)(OH)3 (4) releases dimethylamine to yield both monomeric calix[5](P)(OH)2 (6) and dimeric [calix[5](P)(OH)2](2) (7), the latter having a tubelike geometry. X-ray crystallographic studies confirm the structures and show that 1 and 2 have approximate cone conformations while 3 has an approximate 1,2-alternate conformation. The orientations of the phosphorus lone pairs and oxygen atoms in all derivatives provide a framework for both soft and hard ligand interactions within the calix[5]arene. 相似文献