Synthesis and Rh(I)‐catalyzed polymerization of 1,3‐diphenylyne–calix[4]arene compounds: Novel conjugated,calixarene‐based polymers

The synthesis of two 1,3‐bis(4‐ethynylbenzyloxy)calix[4]arenes, 5,11,17,23‐tetrakis(1,1‐dimethylethyl)‐25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene ( 1 ) and 25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene ( 2 ), was accomplished through Sonogashira coupling of appropriate calixarene derivatives. Methods for the polymerization of these bifunctional building blocks with Rh(I) as a catalyst, leading ultimately to conjugated polymers having calix[4]arene units incorporated into the main chain, were explored. Calixarenes 1 and 2 were efficiently polymerized with rhodium‐based initiators and afforded the conjugated polymers poly{5,11,17,23‐tetrakis(1,1‐dimethylethyl)‐25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene} ( poly 1 ) and poly{25,27‐bis(4‐ethynylbenzyloxy)‐26,28‐dihydroxycalix[4]arene}. Depending on the conditions, high conversions and good yields were obtained. The effects of adding cocatalysts (NHEt₂ and/or PPh₃) were studied in connection with the number‐average molecular weight and the molecular weight distribution of the resultant polymer ( poly 1 ) and tentatively correlated with the formation of low‐molecular‐weight materials. A catalytic system containing triphenylphosphine as the sole additive ([Rh(nbd)Cl]₂; [Rh]/[PPh₃] = 0.5) proved to be the best for the polymerization of p‐tert‐butylcalixarene compound 1 . Linear polymers having high number‐average molecular weights (up to 1.1 × 10⁵ g mol^?1) with low polydispersities were produced under these conditions. For debutylated homologue 2 , its polymerization was best carried out in the absence of any added cocatalyst. A cyclopolymerization route, comprising the intramolecular ring closing of the calix[4]arene pendant ethynyl groups followed by an intermolecular propagation step, is advanced to explain the results. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7054–7070, 2006     

一对含有苯甲醛基修饰的杯芳烃异构体的晶体结构以及它们与铽离子配位的光物理性质

Two calix[4]arene isomers with benzaldehyde moieties, i.e., 5,11,17,23-tetra-tert-butyl-25,27-bis[2-(o-formyl-phenoxy)ethoxy]-26,28-dihydroxycalix[4]arene (3) and 5,11,17,23-tetra-tert-butyl-25,27-bis[2-(p-formylphenoxy)-ethoxy]-26,28-dihydroxycalix[4]arene (4), were synthesized according to a newly designed route in high yields, and their crystal structures have been determined by X-ray crystallographic study. The photophysical behavior on complexation of calix[4]arene derivatives 3 and 4 with terbium(Ⅲ) nitrate was investigated in anhydrous acetonitrile at 25℃ by UV-Vis and fluorescence spectroscopies. The crystallographic structure of 3 indicated that the eight oxygen atoms formed a preorganized ionophoric cavity due to intramolecular π-π stacking, which could encapsulate lanthanide ions tightly. In sharp contrast, the compound 4 formed a linear array by intermolecular π-π stacking, hence the oxygen atoms of pendant arms could not coordinate with metal ions, giving a poor binding ability to Tb^3 . The absorption spectra of 3 with Tb^3 showed clearly a new broad intense absorption at 385nm. Interestingly, the narrow emission line spectrum has also been observed for compound 3 with Tb^3 , and the results obtained were discussed from the viewpoint of energy transfer mechanism between host structures and the properties of lanthanide ions.     

Influences of Hard Donor on Cation Selectivities Closing to Soft Selenium Donor in Tweezer-like Calix[4]arene Receptors

Three novel 25,27-dihydroxy-26,28-bis(3-benzylselenopropoxy)-5,11,17,23-tetra-tert-butylcalix[4]-arene (2),25,27-dihydroxy-26,28-bis[3-(2-hydroxyethylseleno)propoxy]-5,11,17,23-tetra-tert-butyl-calix[4]arene (3) and 25,27-dihydroxy-26,28-bis(3-propylselenoproppxy)-5,11,17,23-tetra-tert-butyl-calix[4]arene (4) were synthesized for the comparison of their ion-selectivity in ion-selective electrodes (ISE). X-ray structure of the CH/π complex of 4.CH2Cl2 was elucidated. ISEs based on 2-4 as neutral ionophores were prepared, and their selectivity coefficients for Ag (logKAg,M^pot) were investigated against some main group metal ions and transition metal ones using the fixed interference method (FIM). These ISEs showed excellent Ag^ selectivity over most of the interfering cations examined. It is evident that the stronger Hg^2 interference may not be produced while hard donors (hydroxy) are close to the soft selenium donors.     

Oligomeric calix[4]arene‐thiacrown ether for toxic heavy metals

A new oligomeric calix[4]arene‐thiacrown‐4 ( 5 ) was synthesized via a condensation reaction of 5,11,17,23‐tetra‐tert‐butyl‐25,27‐bis‐(4‐aminobenzyloxy)‐calix[4]arene‐thiacrown‐4 ( 4 ) with adipoyl dichloride. In this oligomerization reaction only five/six calix[4]arene‐thiacrown‐4 units were linked in the oligomeric chain. The complexation studies of 5 were made with liquid–liquid‐ extraction and solid–liquid‐sorption procedures. For comparison, the extraction efficiencies of monomers 1 , 3 , and 4 to selected transition metals are reported. The selectivity of monomers 3 and 4 toward Cu²⁺, Hg²⁺, and Pb²⁺ was lost after oligomerization in the two‐phase extraction systems. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 186–193, 2004     

下缘芳香取代结构对杯[4]芳烃Langmuir膜的影响

The Langmuir monolayer properties of lower rim aromatically substituted calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis（2-naphth-1＇-ylacetylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BNAEC）, 5,11,17,23-tetra-tert- butyl-25,27-bis（2-benzoylamino ethoxy）-26,28-dihydroxylcalix[4]arene （BBAEC） and 5,11,17,23-tetra-tert-butyl- 25,27-bis（2-cinnamoylaminoethoxy）-26,28-dihydroxylcalix[4]arene （BCAEC）, have been studied. Film balance measurements and Brewster angle microscopy （BAM） observation demonstrate that all the compounds can form Langmuir monolayers with different molecular limiting areas. BNAEC or BBAEC monolayer is able to form condensed domains during compression, while BCAEC monolayer can never form condensed domain. BNAEC monolayer is more readily to form condensed domain than BBAEC monolayer. Moreover, BNAEC monolayer can form the total condensed phase during compression even when T=28℃, while BBAEC monolayer can not when T 〉 10 ℃. The results imply that different lower rim aromatic substitutions affect essentially the intermolecular interaction and molecular packing in the monolayer at air/water interface.     

Synthesis of a calix[4]crown modified with germanium‐containing side chains

A germacalix‐crown, 25,27‐bis[1‐(3‐trimethylgermylpropyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1a ), and its carbon analog, 25,27‐bis‐[1‐(4,4‐dimethylpentyl)oxy]calix[4]arene‐crown‐6, 1,3‐alternate ( 1b ), were prepared and their structures were confirmed by elemental analysis and ¹H and ¹³C NMR spectroscopy. A cation transport test indicated that both compounds exhibited much the same cation transport ability, so that the role of the germanium moiety in capturing and transporting counteranions is not yet clear. Copyright © 2005 John Wiley & Sons, Ltd.     

Synthesis of a Tweezer—like Bis（Phenylthiapropoxy）calix[4]—arene as a Cation／π Enhanced Sensor for Ion—Selective Electrodes

Two novel 25,27-dihydroxy-26,28-bis(3-phenylthiapropxy)-calix[4]arene(3) and 25,27-dihydroxy-26,28-bis(3-phenylthiapropoxy)-5,11,17,23-tetra-tert-butylcalix[4] arene (4) were synthesized for the evaluation of their ion-selectivity in ion-selective electrodes(ISEs).ISEs based on 3 and 4 as neutral ionophores were prepared,and their selectivity coefficients for Ag^ (lg KAg,M^pot)were investigated against other alkali metal,alkaline-earth metal,aluminum,thallium(Ⅰ）,Lead and some transition metal ions using the separate solution method (SSM).These ISEs showed excellent Ag^ seletivity over most of the interfering cations examined,except for Hg^2 and Fe^2 having relative smaller interference(lg KAg,M^pot≤-2.1).     

Liquid chromatographic behavior of two alanine‐substituted calix[4]arene‐bonded silica gel stationary phases

Two new kinds of alanine‐substituted calix[4]arene stationary phases of 5,11,17,23‐p‐tert‐butyl‐25,27‐bis(l ‐alanine‐methylester‐N‐carbonyl‐methoxy)‐26,28‐dihyroxycalix[4]arene‐bonded silica gel stationary phase (BABS4) and 5, 11, 17, 23‐p‐tert‐butyl‐25,26,27,28‐tetra(l ‐alanine‐methylester‐N‐carbonyl‐methoxy)‐calix[4]arene‐bonded silica gel stationary phase (TABS4) were prepared and characterized in the present study. They were compared with each other and investigated in terms of their chromatographic performance by using polycyclic aromatic hydrocarbons, disubstituted benzene isomers, and mono‐substituted benzenes as solute probes. The results indicated that both BABS4 and TABS4 exhibited multiple interactions with analytes. In addition, the commonly used Tanaka characterization protocol for the evaluation of commercially available stationary phases was applied to evaluate the properties of these two new functionalized calixarene stationary phases. The Tanaka test results were compared with Zorbax Eclipse XDB C₁₈ and Kromasil phenyl columns, respectively. BABS4 has stronger hydrogen‐bonding capacity and ion‐exchange capacity than TABS4, and features weaker hydrophobicity and hydrophobic selectivity. Both of them behave similarly in stereoselectivity. Both BABS4 and TABS4 are weaker than C₁₈ and phenyl stationary phases in hydrophobicity and hydrophobic selectivity.     

Synthesis and Characterization of Partially Substituted at Lower Rim Phosphorus Containing Calix(4)arenes

The synthesis and characterization of several new phosphorus-containing partially lower rim substituted derivatives of 5,11,17,23-tetra(t-butyl) calix(4)arene (I) and 5,11,17,23-tetra(t-octyl)calix(4)arene (II), namely 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(diphenylphosphinoyl-oxy) calix(4)arene (IV); 5,11,17,23-tetra(t-butyl)-25-hydroxy-26,27,28-tris(tetramethyldiamido-phosphinoyl-oxy) calix(4)arene (Vb); 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VI); 5,11,17,23-tetra (t-octyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene (VII) are reported. The structure of the synthesized calix(4)arene derivatives are identified and confirmed by elemental analysis, IR, ¹H, ¹³C, ³¹P{¹H} NMR spectroscopy and mass spectrometry as and X-ray crystallographic analysis of 5,11,17,23-tetra(t-butyl)-25,27-dihydroxy-26,28-bis(dimethyl-phosphinoyl-methoxy) calix(4)arene VI. According to the NMR spectra, all calix(4)arenes are in cone conformation.     

Utilization of transport efficacy of novel calix[4]arene-embedded polymer inclusion membrane towards trace metals

In this study, 25,27-bis(3-mercaptopropoxyl)-26,28-dihydroxy calix[4]arene was successfully synthesized from the reaction of calix[4]arene-dialkylbromide derivative with thiourea. The structure of 25,27-bis(3-mercaptopropoxyl)-26,28-dihydroxy calix[4]arene was fully characterized using ¹HNMR, ¹³CNMR and elemental analysis techniques. The obtained mercapto-substituted calix[4]arene derivative was employed as an additive material along with cellulose triacetate (CTA) and 2-nitrophenyl octyl ether (o-NPOE) for the preparation of a novel polymer inclusion membrane (C@PIM). The structure and surface morphology of mercapto-substituted calix[4]arene-embedded polymer inclusion membrane was determined using thermogravimetric analysis, scanning electron microscopy and elemental analysis techniques. Donnan dialysis system was also used to assess the transport efficacy of C@PIM towards Pb(II), Zn(II), Cu(II), Ni(II), Cd(II) and Co(II) ions. The results show that new C@PIM exhibited 99% transport efficacy but also selectivity toward Ni(II) and other ions.     

Synthesis of novel chiral Schiff base and amino alcohol derivatives of calix[4]arene and chiral recognition properties

In the present study, the synthesis and liquid phase extraction properties towards some amino acid methylesters and amino alcohols of Schiff base and amino alcohol substituted calix[4]arene are reported. The Schiff base substituted calix[4]arene 5 has been synthesized via condensation reaction involving 5,17-diformyl-11,23-di-tert-butyl-25,27-di[3-(4-formylphenoxy)propoxy]-26,28 dihydroxycalix[4]arene 4 and (R)-(?)-2-phenylglycine methyl ester in CHCl₃:MeOH. To give the amino alcohol substituted calix[4]arene 6, the synthesized chiral compound 5 was reduced by LiAlH₄. The new chiral Schiff base and amino alcohol derivatives of calix[4]arene have been characterized by a combination of FT-IR, ¹H NMR, ¹³C NMR, FAB-MS and elemental analysis. Also, the extraction behaviors of 5 and 6 towards some selected amino acid methylesters and amino alcohols have been studied by liquid–liquid extraction.     

单氧代-二硒烷基-1, w-二氧取代杯[4]衍生物的合成,结构及萃取性能研究

Novel macrocyclic monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a were synthesized by the reaction of calix[4]arene dibromides 1-5 with the disodium salt of bis（2-selenylethyl）ether in the yields between 28% and 64%. Their structures were characterized by proton and carbon NMR spectra. X-Ray structure analysis of la further confirmed the cone conformation of compounds 1a-5a. An interesting host-guest complex of la with dichloromethane via CH/π and C1/π interactions was elucidated. Extraction experiments showed that these novel monooxa-diselkylene-1,ω-dioxy substituted calix[4]arene derivatives 1a-5a had strong extraction ability towards mercury ion. The interaction of Hg^2＋with the calix ligand has also been investigated by 1^H NMR titration.     

Synthesis and Structure of Novel Double Flexible Spacer Bridged Biscalix[4]arenes

25, 25′, 27, 27′‐Bis(1,3‐dioxypropane)‐bis(5, 11, 17, 23‐tetra‐tert‐butylcalix[4]arene‐26,28‐diol) (4) and 25, 25′, 27, 27′‐bis(1, 4‐dioxybutane)‐bis (5, 11, 17, 23‐tetra‐tert‐butylcalix‐[4]arene‐26, 28‐diol) (5) were synthesized by the reaction of p‐tert‐butylcalix[4]arene (1) with preorganized 25, 27‐bis(3‐bromoproxyl)calix[4]arene‐26, 27‐diol (2) and 25, 27‐bis(3‐bromobutoxyl)calix[4]arene‐26, 27‐diol (3) in the presence of K₂CO₃ and KI. Compounds 4 and 5 were characterized with X‐ray analysis and the selectivity of 4 and 5 toward K⁺ over other alkali metal ions, alkaline metal ions as well as NH₄⁺ were investigated with an ion‐selective electrode.     

Density functional theory study of calix[4]arene‐N‐azacrown‐5, calix[4]arene‐N‐phenyl‐azacrown‐5, and their complexes with alkali‐metal cations: Na+, K+, and Rb+

Theoretical studies of 1,3‐alternate‐25,27‐bis(1‐methoxyethyl)calix[4]arene‐azacrown‐5 ( L₁ ), 1,3‐alternate‐25,27‐bis(1‐methoxyethyl)calix[4]arene‐N‐phenyl‐azacrown‐5 ( L₂ ), and the corresponding complexes M⁺/ L of L₁ and L₂ with the alkali‐metal cations: Na⁺, K⁺, and Rb⁺ have been performed using density functional theory (DFT) at B3LYP/6‐31G* level. The optimized geometric structures obtained from DFT calculations are used to perform natural bond orbital (NBO) analysis. The two main types of driving force metal–ligand and cation–π interactions are investigated. The results indicate that intermolecular electrostatic interactions are dominant and the electron‐donating oxygen offer lone pair electrons to the contacting RY* (1‐center Rydberg) or LP* (1‐center valence antibond lone pair) orbitals of M⁺ (Na⁺, K⁺, and Rb⁺). What's more, the cation–π interactions between the metal ion and π‐orbitals of the two rotated benzene rings play a minor role. For all the structures, the most pronounced changes in geometric parameters upon interaction are observed in the calix[4]arene molecule. In addition, an extra pendant phenyl group attached to nitrogen can promote metal complexation by 3D encapsulation greatly. In addition, the enthalpies of complexation reaction and hydrated cation exchange reaction had been studied by the calculated thermodynamic data. The calculated results of hydrated cation exchange reaction are in a good agreement with the experimental data for the complexes. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Mono‐ and Binuclear Rhodium and Platinum Complexes of 1, 3, 5‐Trimethyl‐1, 3, 5‐triaza‐2σ3λ3‐phosphorin‐4, 6‐dionyloxy‐substituted Calix[4]arenes

The reaction behaviour of 1, 3, 5‐triaza‐2σ³λ³‐phosphorin‐4, 6‐dionyloxy‐substituted calix[4]arenes towards mono‐ and binuclear rhodium and platinum complexes was investigated. Special attention was directed to structure and dynamic behaviour of the products in solution and in the solid state. Depending on the molar ratio of the reactands, the reaction of the tetrakis(triazaphosphorindionyloxy)‐substituted calix[4]arene ( 4 ) and its tert‐butyl‐derivative ( 1 ) with [(cod)RhCl]₂ yielded the mono‐ and disubstituted binuclear rhodium complexes 2 , 3 , and 5 . In all cases, a C₂‐symmetrical structure was proved in solution, apparently caused by a fast intramolecular exchange process between cone conformation and 1, 3‐alternating conformation. The X‐ray crystal structure determination of 5 confirmed [(calixarene)RhCl]₂‐coordination through two opposite phosphorus atoms with a P ⃜P separation of 345 pm. The complex displays crystallographic inversion symmetry, and the Rh₂Cl₂ core is thus exactly planar. Reaction of 1 and of the bis(triazaphosphorindionyloxy)‐bis(methoxy)‐substituted tert‐butyl‐calix‐[4]arene ( 7 ) with (cod)Rh(acac) in equimolar ratio and subsequent reaction with HBF₄ led to the expected cationic monorhodium complexes 5 and 8 , involving 1, 3‐alternating P‐Rh‐P‐coordination. The cone conformation in solution was proved by NMR spectroscopy and characteristic values of the ¹J(PRh) coupling constants in the ³¹P‐NMR‐spectra. Reaction of equimolar amounts of 4 with (cod)Rh(acac) or (nbd)Rh(acac) led, by substitution of the labile coordinated acetylacetonato and after addition of HBF₄, to the corresponding mononuclear cationic complexes 9 and 10 . Only two of the four phosphorus atoms in 9 and 10 are coordinated to the central metal atom. Displacement of either cycloocta‐1, 5‐diene or norbornadiene was not observed. For both compounds, the cone conformation was proved by NMR spectroscopy. Reaction of 4 with (cod)PtCl₂ led to the PtCl₂‐complex ( 11 ). As for all compounds mentioned above, only two phosphorus atoms of the ligand coordinate to platinum, while two phosphorus atoms remain uncoordinated (proved by δ³¹P and characteristic values of ¹J(PPt)). NMR‐spectroscopic evidence was found for the existence of the cone conformation in the cis‐configuration of 11 .     

Synthesis of Oligomer and Styrene Polymer-supported Calix[4]arene Derivatives and Selective Extraction of Fe3+

Five new polymeric compounds containing more than one calix[4]arene have been synthesized by reacting an oligomer with 5,11,17,23-tetrakis[(diethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (L1), 25,27-dimethyl-26,28-dihydroxy-p-tert-butylcalix[4]arene diketone (L2), and p-nitrocalix[4]arene (L3), and chloromethylated polystyrene with 25,27-dimethyl-26,28-dihydroxy-p-tert-butylcalix[4]arene diketone (L4) and p-nitrocalix[4]arene (L5). These compounds were studied by the selective extraction of Fe³⁺ cation from the aqueous phase into the organic phase and was carried out by using compounds L1–L5. It was observed that the polymer support attached to the lower rim of p-nitrocalix[4]arene was the most efficient carrier of Fe³⁺ in the extraction process.     

Calix[4]arene‐based Bis‐phosphonites,Bis‐phosphites,and Bis‐O‐acyl‐phosphites as Ligands in the Rhodium(I)‐catalyzed Hydroformylation of 1‐Octene

New calix[4]arene‐based bis‐phosphonites, bis‐phosphites and bis‐O‐acylphosphites were synthesized and characterized. Treatment of these P‐ligands with selected rhodium and platinum precursors led to mononuclear complexes that were satisfactorily characterized. The solid state structure of the dirhodium(I) complex 14 has been determined by X‐ray diffraction. The two rhodium centres are bridged by two chloro ligands; one rhodium atom is further coordinated by calix[4]arene phosphorus atoms and the other by cyclooctadiene. The new calix[4]arene P‐ligands were tested in the Rh(I) catalyzed hydroformylation of 1‐octene. All Rh(I) complexes catalyzed the reaction leading to high chemoselectivity with regard to the formation of aldehydes. Yields and n/iso‐selectivities depended on the reaction conditions. Average yields of 80 % and n/iso‐ratios of about 1.3 to 1.5 were observed. High yields of aldehydes can be achieved using the methoxy substituted P‐ligands at low Rh:ligand ratios.     

含氮手性杯[4]芳烃对羧酸的手性识别

Chiral nitrogen-containing calix[4]arene was easily synthesized by the reaction of 25,27-di（2-bromoethoxy）- 26,28-dihydroxy-5,11,17,23-tetrakis（t-butyl）calix[4]arene with S-（-）-1-phenylethylamine in excellent yield, and showed good ability to recognize the enantiomers of mandelic acid and 2,3-dibenzoyltartaric acid. This finding has potential application to assay and separation of enantiomers of the carboxylic acids.     

Synthesis of p‐tert‐Butyl‐calix[6] ‐biscrown‐3 via Intramolecular Ring‐closure of 1,4‐Bis (2‐(2‐chloroethoxy) ethoxy) ‐p‐tert‐butyl‐calix[6]arene

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.     

Novel Triphenylamine Appended 1,3-Alternate-Calix[4]arenes: Synthesis and Characterization

In the present study, two novel calix[4]arene receptors containing triphenylamine units in 1,3-alternate conformation have been synthesized and characterized in detail. First, the 25,27-dipropoxy-26,28-bis[(3-aminopropyl)oxy]-calix[4]arene 4 and 25,26,27,28-tetra[(3-aminopropyl)oxy]-calix[4]arene 7 were prepared by using convenient reagents. Then, these amino derivatives of calix[4]arene were converted to Schiff base derivatives appended to triphenylamine of calix[4]arene (5 and 8) using 4-formyltriphenylamine via condensation. The 1,3-alternate conformation of the synthesized calix[4]arenes was determined by ¹H and ¹³C NMR analyses. Also, their structures have been characterized by using ¹H and ¹³C NMR, infrared, and elemental analyses.

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