Novel immobilized calixarenes and related compounds and process for their production

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.

1 . A process for the immobilization of a calixarene or a calixarene-related compound to a substrate comprising either: 
 (a) contacting the calixarene 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 said substrate with a calixarene or a calixarene-related compound that has been previously modified or derivatized by reaction with said one or more polyhalides and/or polyalkoxides.    
   
   
       2 . A process according to  claim 1  in which the element capable of forming a stable aryloxide species with the substrate is one or more elements selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum and iron, and another elements that form a stable aryloxide with the substrate.  
   
   
       3 . A process according to  claim 2  in which the element is one or more elements selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum and iron.  
   
   
       4 . A process according to  claim 2  in which the element is silicon.  
   
   
       5 . A process for immobilizing a calixarene or a calixarene-related compound on a substrate containing one or more metallic or non-metallic oxides comprising; 
 (a) reacting a polyhalide or polyalkoxide of one or more elements selected from one or more elements selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum or iron, or another element that forms a stable aryloxide with the substrate, forming a modified substrate; and    (b) contacting the modified substrate with a calixarene so as to immobilize the calixarene to the substrate through at least one phenolic oxygen linkage.    
   
   
       6 . A process according to  claim 5  in which the one or more elements are selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum and iron.  
   
   
       7 . A process according to  claim 5  for immobilizing a calixarene to a substrate.  
   
   
       8 . A process according to  claim 5  for immobilizing a calixarene-related compound to a substrate.  
   
   
       9 . A process according to  claim 8  in which the calixarene-related compound is an oxacalixarene, an azacalixarene, a silicacalixarene, a thiacalixarene, a homocalixarene, or a calixarene-related compound comprising furan or thiophene residues.  
   
   
       10 . A process according to  claim 5  in which the one or more elements is silicon.  
   
   
       11 . A process for immobilizing a calixarene or a calixarene-related compound on a substrate containing one or more metallic or non-metallic oxides comprising; 
 (a) reacting a polyhalide or polyalkoxide of one or more elements selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum and iron with the calixarene or calixarene-related compound, forming a modified calixarene or calixarene-related compound; and    (b) contacting the modified calixarene or calixarene-related compound with the substrate so as to immobilize the calixarene or calixarene-related compound to the substrate through at least one phenolic oxygen linkage.    
   
   
       12 . A process according to  claim 11  in which the one or more elements are selected from silicon, tungsten, niobium, titanium, zirconium, manganese, vanadium, chromium, tantalum, aluminum, phosphorus, boron, rhodium, molybdenum, germanium, copper, platinum and iron.  
   
   
       13 . A process according to  claim 11  for immobilizing a calixarene to a substrate.  
   
   
       14 . A process according to  claim 11  for immobilizing a calixarene-related compound to a substrate.  
   
   
       15 . A process according to  claim 14  in which the calixarene-related compound is an oxacalixarene, an azacalixarene, a silicacalixarene, a thiacalixarene, a homocalixarene, or a calixarene-related compound comprising furan or thiophene residues.  
   
   
       16 . A process according to  claim 11  in which the one or more elements is silicon.  
   
   
       17 - 22 . (canceled)  
   
   
       23 . A catalytic process selected from olefin rearrangement, cycloaddition of a terminal alkane, hydroformylation of a water-insoluble olefin, cleavage of a phosphate diester, an oxidation process, a hydrogenation process, a hydroformylation process, or an acid-catalyzed process wherein the catalyst comprises a composition according to claim  17 .