25,27-Dipropoxy-p-tert-butylcalix[4]crown-9 cone conformer 5 was readily synthesized via an intramolecular cyclization strategy in good yields. The structures of all the new compounds involved were confirmed by NMR, E...25,27-Dipropoxy-p-tert-butylcalix[4]crown-9 cone conformer 5 was readily synthesized via an intramolecular cyclization strategy in good yields. The structures of all the new compounds involved were confirmed by NMR, ESI-MS and elemental analyses. All of them were proved to be in the cone conformation.展开更多
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 diam...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.展开更多
A novel series of calix[4]azacrown derivatives with the reaction between calix[4]azacrown and the different fluorophore derivatives,which may be useful fluorescent receptors,have been synthesized and structurally char...A novel series of calix[4]azacrown derivatives with the reaction between calix[4]azacrown and the different fluorophore derivatives,which may be useful fluorescent receptors,have been synthesized and structurally characterized by IR,~1H NMR,^(13)C NMR and MS.From their analysis data,it was found those compounds adopted a cone conformation.展开更多
Refluxing calix[4]-1,3-substituted benzaldehyde derivative(4) with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative(5) via "1+2" condensation in a yield of 78%. In the reacti...Refluxing calix[4]-1,3-substituted benzaldehyde derivative(4) with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative(5) via "1+2" condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown(6) with chiral amino acid group as branched chain was synthesized via "1+ 1" addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.展开更多
Calix[4]-crown-5-sulfonyl cyclothiourea derivatives 6 and 7 were synthesized from calix[4]-crown-5-monosulfonylethylenediamine derivatives 4 and 5 and carbon disulfide through nucleophilic addition and subsequent cycl...Calix[4]-crown-5-sulfonyl cyclothiourea derivatives 6 and 7 were synthesized from calix[4]-crown-5-monosulfonylethylenediamine derivatives 4 and 5 and carbon disulfide through nucleophilic addition and subsequent cyclization of intramolecule at room temperature in aqueous solution. The advantages of the novel protocol are the mild reaction condition, free organic solvent, simple final treatment, easy isolation of products and excellent yields.展开更多
A diester-calix[4]crown-4-ether bearing mono (azophenol) moiety shows a larger spectral change toward Ca2+ than other alkali and alkaline eafth cations.
Three novel calix[4](aza)crown deravatives have been synthesized, including a new [2]pseudorotaxane in which calix[4]- azacrown behaves as a stopper, a novel 'tren' type calix[4]azacrown and a novel 'spiro' type...Three novel calix[4](aza)crown deravatives have been synthesized, including a new [2]pseudorotaxane in which calix[4]- azacrown behaves as a stopper, a novel 'tren' type calix[4]azacrown and a novel 'spiro' type calix[4]azacrown containing moroholine unit. The structures of these compounds have been confirmed by NMR and MS.展开更多
A one-step procedure is developed to synthesize inherently chiral p-tert-butylcalix[4]azacrown 1 through etherification between p-tert-butylcalix[4]arene and compound 3, which can be amplifed to efficiently prepare mo...A one-step procedure is developed to synthesize inherently chiral p-tert-butylcalix[4]azacrown 1 through etherification between p-tert-butylcalix[4]arene and compound 3, which can be amplifed to efficiently prepare more inherently cbiral calix[4]arenes in ABHH substitution pattern.展开更多
The article comprises synthesis of calyx[4]-oxa-crown, and calix[4]-thia-crown compounds containing nitrile groups (3a, 3b) and amino groups (4a, 4b) and their corresponding oxime derivatives (5a, 5b) and liquid-liqui...The article comprises synthesis of calyx[4]-oxa-crown, and calix[4]-thia-crown compounds containing nitrile groups (3a, 3b) and amino groups (4a, 4b) and their corresponding oxime derivatives (5a, 5b) and liquid-liquid extraction studies of these compounds. The oxime derivatives of compounds (5a, 5b) have been synthesized by reacting of di-n-butylamino derivatives of calix[4]-oxa-crown, and calix[4]-thia-crown compounds (4a, 4b) with amphi-chloroglyoxime in methanol-THF. Their cation and anion transfer studies were performed by using liquid-liquid extraction procedure. It has been concluded from the observations that the compound 3a shows a good extraction behavior toward Na+ ion in the presence of other metal cations. Whereas, its oxime derivatives transfers all of the metal cations used in the liquid-liquid extraction studies.展开更多
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...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.展开更多
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...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.展开更多
Salbutamol,which increases the muscle mass and decreases the adipose tissue,is misused as nutrient repartitioning agent in the livestock.The novelty of this work is the determination of salbutamol in the livestock mea...Salbutamol,which increases the muscle mass and decreases the adipose tissue,is misused as nutrient repartitioning agent in the livestock.The novelty of this work is the determination of salbutamol in the livestock meat via new bonded-phases bearing eight derivatives of p-tert-calix[4]arene in partial-cone conformation.The new synthesized bonded-phases were characterized and optimized.The bonding interactions of solute and stationary-phases were examined and the main interactions were reported.The salbutamol levels in six samples of livestock meat were analyzed and the results reveal that for the best bonded-phases,the limit of detection(LOD) and limit of quantitation(LOQ) were 0.02 and 0.06 μg/mL,respectively.展开更多
Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the...Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry.展开更多
New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was e...New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was examined.For K+ ion transfer,preserving phenolic hydroxyl in the lower rim of calix[4]arene could enhance its transport ability.When benzoyl replaced phenolic hydroxyl,the transport would fall off,because benzoyl caused steric hindrance on the K+ transfer.The study also revealed that the group having the electron-withdrawing conjugative effect on phenolic hydroxyl,-NO2 in the upper rim of calix[4]arene,made transport ability of calix[4]arene fall off.On the contrary,-NH2 that had electron-repulsive conjugative effect enhanced the transport ability of the compound.For Hg2+ ion,only -NH2 in the upper rim of calix[4]arenes had high affinity for it and contributed to Hg2+ transfer.Transport amount of Hg2+ ion increased with increasing calix[4]arene5 concentration and ΔpH in BLM.展开更多
A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described. The compound is an useful intermediates for the introduction of other functional groups to obtain N containi...A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described. The compound is an useful intermediates for the introduction of other functional groups to obtain N containing substituted calix[4]arene. The reaction mechanism is briefly discussed.展开更多
Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg^(2+)and Pb^(2+),calix[4]arene derivatives containing hydroxyl,bro...Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg^(2+)and Pb^(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg^(2+)and Pb^(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg^(2+)by promoting the formation of the negative oxygen ions that could bind with Hg^(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb^(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb^(2+)with higher charge-to-radius ratio than Hg^(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg^(2+)and Pb^(2+))increased with the increase of pH value in acidic aqueous system(pH<7).展开更多
Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole mac...Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole macrocycles were synthesised and characterized.展开更多
基金the Research Foundation of Tongji Medical College,Huazhong University of Science and Technology(No.25514107)Project Chenguang of Wuhan City(No.200750731267)for financial support.
文摘25,27-Dipropoxy-p-tert-butylcalix[4]crown-9 cone conformer 5 was readily synthesized via an intramolecular cyclization strategy in good yields. The structures of all the new compounds involved were confirmed by NMR, ESI-MS and elemental analyses. All of them were proved to be in the cone conformation.
文摘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.
基金the National High Technology Research and Development Program 863(No. 2008AA03A315)The Research Fund for the Doctoral Program of High Education(No.20060056017).
文摘A novel series of calix[4]azacrown derivatives with the reaction between calix[4]azacrown and the different fluorophore derivatives,which may be useful fluorescent receptors,have been synthesized and structurally characterized by IR,~1H NMR,^(13)C NMR and MS.From their analysis data,it was found those compounds adopted a cone conformation.
基金Supported by the National Natural Science Foundation of China(No.20402002)Natural Science Foundation of Fujian Province,China(No.2009J01019)
文摘Refluxing calix[4]-1,3-substituted benzaldehyde derivative(4) with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative(5) via "1+2" condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown(6) with chiral amino acid group as branched chain was synthesized via "1+ 1" addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.
基金Financial support from the National Natural Science Foundation of China(No.20802049) and Program for New Century Excellent Talents in University of Tianjin City
文摘Calix[4]-crown-5-sulfonyl cyclothiourea derivatives 6 and 7 were synthesized from calix[4]-crown-5-monosulfonylethylenediamine derivatives 4 and 5 and carbon disulfide through nucleophilic addition and subsequent cyclization of intramolecule at room temperature in aqueous solution. The advantages of the novel protocol are the mild reaction condition, free organic solvent, simple final treatment, easy isolation of products and excellent yields.
文摘A diester-calix[4]crown-4-ether bearing mono (azophenol) moiety shows a larger spectral change toward Ca2+ than other alkali and alkaline eafth cations.
基金Thanks for the support of the National Natural Science Foundation of China (No. 20376059).
文摘Three novel calix[4](aza)crown deravatives have been synthesized, including a new [2]pseudorotaxane in which calix[4]- azacrown behaves as a stopper, a novel 'tren' type calix[4]azacrown and a novel 'spiro' type calix[4]azacrown containing moroholine unit. The structures of these compounds have been confirmed by NMR and MS.
基金Foundation of Tianjin Medical University(No.2006x9d2)the National Natural ScienceFoundation of Chinathe Major State Basic Research Development Program of China(No.20502008) for financialsupport
文摘A one-step procedure is developed to synthesize inherently chiral p-tert-butylcalix[4]azacrown 1 through etherification between p-tert-butylcalix[4]arene and compound 3, which can be amplifed to efficiently prepare more inherently cbiral calix[4]arenes in ABHH substitution pattern.
基金We thank the Scientific and Technical Research Council of Turkey(TUBITAK-Number TBAG 105T433)for financial support of this work.
文摘The article comprises synthesis of calyx[4]-oxa-crown, and calix[4]-thia-crown compounds containing nitrile groups (3a, 3b) and amino groups (4a, 4b) and their corresponding oxime derivatives (5a, 5b) and liquid-liquid extraction studies of these compounds. The oxime derivatives of compounds (5a, 5b) have been synthesized by reacting of di-n-butylamino derivatives of calix[4]-oxa-crown, and calix[4]-thia-crown compounds (4a, 4b) with amphi-chloroglyoxime in methanol-THF. Their cation and anion transfer studies were performed by using liquid-liquid extraction procedure. It has been concluded from the observations that the compound 3a shows a good extraction behavior toward Na+ ion in the presence of other metal cations. Whereas, its oxime derivatives transfers all of the metal cations used in the liquid-liquid extraction studies.
基金the Scientific Research Fund Projects of China West Normal University(No.06B003)the Youth Fund Projects of Sichuan Educational Department(No.2006B039)
文摘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.
文摘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.
基金Supported by the Project of Islamic Azad University(Shahreza Branch)the Iran Nanotechnology Initiative Council
文摘Salbutamol,which increases the muscle mass and decreases the adipose tissue,is misused as nutrient repartitioning agent in the livestock.The novelty of this work is the determination of salbutamol in the livestock meat via new bonded-phases bearing eight derivatives of p-tert-calix[4]arene in partial-cone conformation.The new synthesized bonded-phases were characterized and optimized.The bonding interactions of solute and stationary-phases were examined and the main interactions were reported.The salbutamol levels in six samples of livestock meat were analyzed and the results reveal that for the best bonded-phases,the limit of detection(LOD) and limit of quantitation(LOQ) were 0.02 and 0.06 μg/mL,respectively.
基金Supported by the National Natural Science Foundation of China(No. 20402002) Natural Science Foundation of FujianProvince, China(Nos. E0220002 and 2006J0155).
文摘Introduction Calixarenes are one of the most important supra- molecular building blocks, which can be modified by introducing different functional and/or structural groups to create a specific interaction between the host and the target molecules, such as metal cations and small organic molecules. In particular, the recognition of amino acids is an interesting theme in biomimetic chemistry.
基金Natural Science Foundation of Education Department of Anhui Province,China(No. KJ2011B021)
文摘New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was examined.For K+ ion transfer,preserving phenolic hydroxyl in the lower rim of calix[4]arene could enhance its transport ability.When benzoyl replaced phenolic hydroxyl,the transport would fall off,because benzoyl caused steric hindrance on the K+ transfer.The study also revealed that the group having the electron-withdrawing conjugative effect on phenolic hydroxyl,-NO2 in the upper rim of calix[4]arene,made transport ability of calix[4]arene fall off.On the contrary,-NH2 that had electron-repulsive conjugative effect enhanced the transport ability of the compound.For Hg2+ ion,only -NH2 in the upper rim of calix[4]arenes had high affinity for it and contributed to Hg2+ transfer.Transport amount of Hg2+ ion increased with increasing calix[4]arene5 concentration and ΔpH in BLM.
文摘A new efficient synthesis of p-nitrocalix[4]arene from calix[4]arene by using nitrogen dioxide is described. The compound is an useful intermediates for the introduction of other functional groups to obtain N containing substituted calix[4]arene. The reaction mechanism is briefly discussed.
基金Natural Science Foundation of Education Department of Anhui Province,China(No.KJ2013B028)Textile Science and Technology Key Discipline in Anhui Polytechnic University,China
文摘Calix[4]arene derivatives have been reported to possess high selectivity for metal ions.In order to analyze the extraction effect of substituents on Hg^(2+)and Pb^(2+),calix[4]arene derivatives containing hydroxyl,bromoethoxy and 1,11-dioxa-4,8-dithiahendecene were successfully synthesized,with their extraction effectiveness towards Hg^(2+)and Pb^(2+)were evaluated respectively.The results indicated that the phenolic hydroxyl in calix[4]arene improved the extraction ability on Hg^(2+)by promoting the formation of the negative oxygen ions that could bind with Hg^(2+)by coordination and ionic bonds.The extraction ability of 5,17-dinitro-26,28-(1’,11’-dioxa-4’,8’-dithiahendecene)-calix[4]arene(calix[4]arene thia derivative)was improved slightly due to the better coordination capacity for metal ions after introduction of 1,11-dioxa-4,8-dithiahendecene,which was a chelate-binding centre.Regarding to Pb^(2+),only 1,11-dioxa-4,8-dithiahendecene on molecule contributed to extraction due to the coordination bond.Since the metal ion with higher charge-to-radius ratio could coordinate with one ligand more stably,Pb^(2+)with higher charge-to-radius ratio than Hg^(2+)was coordinated and extracted by the calix[4]arene thia derivative more easily.Furthermore,extraction rates of the calix[4]arene thia derivative on both ions(Hg^(2+)and Pb^(2+))increased with the increase of pH value in acidic aqueous system(pH<7).
文摘Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole macrocycles were synthesised and characterized.