Halogenated calixpyrroles, calixpyridinopyrroles and calixpyridines, and uses thereof

• US 20020115566A1
• Filed: 08/24/2001
• Published: 08/22/2002
• Est. Priority Date: 04/05/1996
• Status: Active Grant

• Current Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Sessler, Jonathan L., Marquez, Manuel, Shriver, James A., Anzenbacher, Pavel Jr.
• Granted Patent: US 7,041,819 B2
• Time in Patent Office: Days
• US Class Current: 504/218
• CPC Class Codes: B01D 15/26 characterised by the separation mechanism
• CPC Class Codes: B01J 20/22 comprising organic material
• CPC Class Codes: B01J 20/281 Sorbents specially adapted for preparative, analytical or investigative chromatography
• CPC Class Codes: B01J 20/286 Phases chemically bonded to a substrate, e.g. to silica or to polymers
• CPC Class Codes: B01J 20/288 Polar phases
• CPC Class Codes: B01J 20/3208 Polymeric carriers, supports or substrates
• CPC Class Codes: B01J 20/3255 comprising a cyclic structure containing at least one of the heteroatoms nitrogen, oxygen or sulfur, e.g. heterocyclic or heteroaromatic structures
• CPC Class Codes: B01J 2220/54 Sorbents specially adapted for analytical or investigative chromatography
• CPC Class Codes: B01J 45/00 Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties ion-exchange chromatography processes B01D15/36
• CPC Class Codes: C07D 487/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07D 495/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07D 498/22 in which the condensed system contains four or more hetero rings
• CPC Class Codes: C07F 17/02 of metals of Groups 8, 9 or 10 of the Periodic Table
• CPC Class Codes: G01N 30/02 Column chromatography
• CPC Class Codes: G01N 30/88 Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
• CPC Class Codes: G21F 9/06 Processing separating different isotopes of the same chemical element B01D59/00
• CPC Class Codes: G21F 9/12 by absorption; by adsorption; by ion-exchange

Abstract

The present invention provides halogenated calixpyrrole, calixpyridinopyrrole, and calixpyridine macrocycles having 4-12 pyrrolic rings with greater stability, enhanced anion and neutral molecule binding affinity, and different binding selectivites as compared to their nonhalogenated congeners as judged from ¹H NMR, ¹⁹F NMR and fluorescence emission spectroscopic analyses.

Claims

1. A compound comprising a β

-substituted calix[n]pyrrole macrocycle having structure I;

2. The compound of claim 1 wherein n is 4 and p=q=r=s=0.

3. The compound of claim 1 wherein at least two R substituents are coupled to form a bridged structure, the two R substituents selected from the group consisting of an odd numbered R substituent and a pyrrole R substituent, and when coupled to form a bridged structure, nonbridged substituents are as defined.

5. A composition comprising the compound of claim 1 incorporated into a polymer matrix.

6. A composition comprising the compound of claim 1 incorporated into a membrane.

7. A composition comprising the compound of claim 1 incorporated into a liposome.

9. The compound of claim 1 wherein n is 5.

10. The compound of claim 1 wherein n is 6 or 7.

11. The compound of claim 1 wherein n is 8.

13. The method of claim 12 wherein the halogenated calix[n]pyrrole is a fluorinated calix[n]pyrrole and the 3,4-dihalopyrrole is a 3,4-difluoropyrrole.

15. The method of claim 14 wherein the anion is an environmental pollutant.

16. The method of claim 14 wherein the anion is fluoride, chloride, or phosphate.

17. The method of claim 14 wherein the anion is pertechnetate.

19. The method of claim 18 wherein the calix[n]pyrrole is a halogenated calix[n]pyrrole.

20. The method of claim 18 wherein the calix[n]pyrrole is a fluorinated calix[n]pyrrole.

21. The method of claim 18 wherein the ion pair is an environmental pollutant.

22. The method of claim 18 wherein the cation coextractant is a crown ether, a cryptand, a calixarene, a calixarene-crown ether cryptand, or a calixarene-crown ether conjugate.

23. The method of claim 18 wherein the cation coextractant is a cation exchanger.

25. The method of claim 24 wherein the calix[n]pyrrole is a halogenated calix[n]pyrrole.

26. The method of claim 24 wherein the calix[n]pyrrole is a fluorinated calix[n]pyrrole.

27. The method of claim 24 wherein the substrate is gasoline or jet fuel and the anion is a chloride anion.

29. The method of claim 18 wherein the cation is cesium.

4. A compound comprising a β

-substituted calix[n]pyrrole macrocycle having structure I;

8. A compound comprising a fluorinated calix[n]pyrrole where n is 9, 10, 11, or 12.

12. A method of making a halogenated calix[n]pyrrole where n is 4, 5, 6, 7, 8, 9, 10, 11, or 12 comprising

reacting 3,4-dihalopyrrole and a ketone molecule for a time sufficient to produce the halogenated calix[n]pyrrole.

14. A method of removing an anion from an environment containing the anion comprising contacting the environment with a halogenated calix[n]pyrrole where n is 4, 5, 6, 7, or 8 wherein the halogenated calix[n]pyrrole binds the anion thereby removing the anion from the environment.

18. A method for extracting an ion pair having a cation associated with an anion from an environment containing said ion pair, the method comprising contacting the environment with an anion coextractant and a cation coextractant, wherein the anion coextractant is a calix[n]pyrrole where n is 4, 5, 6, 7, or 8, and wherein the calix[n]pyrrole binds the anion and the cation coextractant binds the cation thereby allowing for removal of the ion pair from the environment.

24. A method for reducing or preventing corrosion on a substrate susceptible to corrosion in the presence of a corrosion-promoting anion, comprising contacting the substrate with a calix[n]pyrrole where n is 4, 5, 6, 7, or 8 wherein the calix[n]pyrrole binds the corrosion-promoting anion, thereby reducing or preventing corrosion of the substrate.

28. A method for producing a naked cation in a solution containing said cation paired with an anion, the method comprising contacting a calix[n]pyrrole where n is 4, 5, 6, 7, or 8 with the solution, wherein the calix[n]pyrrole binds the anion thereby providing the naked cation.

30. A compound selected from the group consisting of compounds 44, 46, 48, 50, and 52.