Novel immobilized calixarenes and related compounds and process for their production

a technology of immobilized calixarene and calixarene, which is applied in the direction of physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, other chemical processes, etc., can solve the problems of weak binding, requiring rather laborious calixarene synthesis, and poor solubility of calixarene in these solvents

Inactive Publication Date: 2005-11-17
RGT UNIV OF CALIFORNIA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although protic solvents such as water and alcohols offer an optimum environment for host-guest interactions in this case, calixarenes have generally poor solubility in these solvents, which has required the use of organic solvents in studies of adsorption.
However, use of these solvents tends to result in relatively weak binding.
Immobilization of calixarenes and related compounds offers a route to circumvent host solubility limitations, but thus far it has required rather laborious syntheses of calixarene derivatives that contain reactive functional groups for polymerization to a surface (e.g. capable of sol-gel hydrolysis and condensation) or other type of surface binding (e.g. via a thiol or sulfide for anchoring on a gold surface).
These tethers, however, tend to decrease the conformational rigidity of the anchored binding site and limit the maximum attainable site density for the calixarenes.

Method used

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  • Novel immobilized calixarenes and related compounds and process for their production
  • Novel immobilized calixarenes and related compounds and process for their production
  • Novel immobilized calixarenes and related compounds and process for their production

Examples

Experimental program
Comparison scheme
Effect test

example 1

Immobilization of t-buytlcalix[4]arene Using Silica

[0048] Synthesis: t-Butylcalix[4]arene immobilized on a silica substrate (1) was prepared starting with 1.5 g of silica, which was dehydrated at 300° C. under a vacuum of at least 50 mtorr for 24 hours in a Schlenk tube. After cooling under nitrogen to room temperature, a solution of SiCl4 in dichloromethane (1M, 6.8 mL) was added via dry syringe, followed by the addition of triethylamine (0.69 g, 6.8 mmol). The resulting cloudy solution was kept at room temperature for at least 12 h, and the solvent was subsequently evaporated in vacuo to yield a dry white powder. A solution of the macrocyclep-tert-butyl-calix-[4]-arene (0.3 g, 0.46 mmol) in toluene (20 mL) was freshly prepared, and the white powder was added by repeated rinsings of the Schlenk tube with toluene (30 mL). Finally triethylamine (1.75 g, 17.3 mmol) was added to this mixture, and the resulting solution was refluxed under nitrogen for a period of 24 h, with the condens...

example 2

Adsorption of NO Using Immobilized Calixarene

[0057] The gas-phase adsorption of NO to 1 was also investigated, since it is known that NO strongly adsorbs into the lipophilic cavity ofp-tert-butylcalix-[4]-arene via cofacial interaction with the aromatic groups. Experiments were conducted by first pretreating 1 in helium flow at 150° C. for 90 minutes. Results are shown in FIG. 5. By performing thermal desorption spectroscopy during pretreatment, some removal of water was observed, which is consistent with the weight loss observed using thermogravimetric analysis. The first cycle of NO adsorption was then performed at 50° C., by treating 1 with a helium flow containing a fixed amount of NO and monitoring the amount of NO adsorbed by mass spectrometry on the effluent stream. The amount of NO adsorbed during this first cycle corresponded to 78 μmol / g or 38% of the possible number of sites. Temperature ramping up to 250° C. was subsequently performed on this sample, with the sample mai...

example 3

Vapor Phase Adsorption of Benzene and Cyclohexane

[0059] Since immobilized calixarenes on silica are known to form complexes with neutral molecules, we explored the vapor-phase adsorption of guest to 1. The adsorption of benzene and cyclohexane was performed from the vapor phase, by contacting 1 with benzene and cyclohexane gas and measuring the uptake from the consequent decrease in the pressure of the contacting gas phase. FIG. 6 shows the amount of benzene and cyclohexane adsorbed onto 1 at 70° C. as the driving force for adsorption, measured by the relative pressure (pressure divided by the vapor pressure Po at the adsorption temperature), is varied. These data show that cyclohexane adsorption uptakes are significantly smaller than those of benzene on 1. This may reflect in part the aromatic character of benzene molecules and their ability to interact specifically with the π-electrons in the aromatic environment provided by the immobilized calixarenes. The total amount adsorbed ...

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Abstract

Immobilized calixarenes and calixarene-related compounds are produced by a process comprising either: (a) contacting the calixarene or calixarene-related compound with a substrate containing one or more metallic or non-metallic oxides that has been surface modified by reaction with one or more polyhalides and / or polyalkoxides of an element capable of forming a stable aryloxide species with the substrate, or (b) reaction of such a substrate with a calixarene or calixarene-related compound that has been previously modified or derivatized by reaction with said polyhalides and / or polyalkoxides.

Description

BACKGROUND OF THE INVENTION [0001] This invention relates to calixarenes and related compounds immobilized onto the surface of a substrate and to a novel method for the production of such products. The substrate may be silica or another inorganic oxide substrate. [0002] Calixarenes are cyclic oligomers of phenol and substituted phenols with formaldehyde, and are characterized by the general structure [0003] in which n is a value of 3-16, preferably 3 or an even number, most preferably 3, 4, 6 or 8. General information about such molecules can be found, for example in Bauer et al., JACS 107, 6053 (1985) and the texts “Calixarenes” by C. David Gutsche, which is part of the Monographs in Supramolecular Chemistry (J. Fraser Stoddart, ed.; Royal Society of Chemistry, 1989) and “Calixarenes Revisited” by the same author (1998). [0004] Calixarenes are in the form of a cyclical oligomer having a “basket” shape, where the cavity can serve as a binding site for numerous guest species, includ...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): B01J20/32B01J31/06B01J31/16B01J31/22C07C45/50
CPCB01J20/32B01J20/3204B01J31/066B01J31/1633B01J2531/16B01J2231/321B01J2231/50B01J2231/60B01J31/2295B01J20/3219B01J20/3248B01J20/3253Y10T428/31663Y10T428/31942
Inventor KATZ, ALEXANDERIGLESIA, ENRIQUENOTESTEIN, JUSTIN M.
Owner RGT UNIV OF CALIFORNIA
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