Di- and triphenylated cation radical polymers and their use as Diels-Alder catalysts

• US 4,552,928 A
• Filed: 09/17/1984
• Issued: 11/12/1985
• Est. Priority Date: 11/02/1981
• Status: Expired due to Term

• 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: Bellville, Dennis J., Bauld, Nathan L.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Lipman, Bernard
• Application Number:
  US06/651,059
• Time in Patent Office: 421 Days
• Field of Search: 525/333.4, 525/333.6, 525/340, 525/359.1, 525/379, 525/326.2, 525/333.1, 525/331.5, 525/333.7, 525/452, 525/534, 536/30, 536/56, 536/101
• US Class Current: 525/326.2
• CPC Class Codes: B01J 2231/326 Diels-Alder or other [4+2] cycloadditions, e.g. hetero-analogues
• CPC Class Codes: B01J 31/006 comprising organic radicals, e.g. TEMPO
• CPC Class Codes: B01J 31/0235 Nitrogen containing compounds
• CPC Class Codes: B01J 31/08 Ion-exchange resins
• CPC Class Codes: B01J 31/122 Metal aryl or alkyl compounds
• CPC Class Codes: B01J 31/1658 immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
• CPC Class Codes: B01J 31/26 containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
• CPC Class Codes: B01J 31/4007 of catalysts containing polymers
• CPC Class Codes: C08F 2/60 Polymerisation by the diene synthesis
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: Y02P 20/584 Recycling of catalysts

Abstract

A regenerative catalyst composition is provided comprising polymer supported covalently bound di- or triphenylated cation radical salts, wherein the cation radical is a Group VA element and the complementing anion is a Lewis acid anion or other anion, such as perhalo acid or acid metal halide. The phenylated cation radical salts, either polymer supported or unsupported, are useful catalytic agents facilitating the versatile Diels-Alder organic synthetic reactions to form cyclohexene compounds including the more intricate terpenoids, steroids, alkaloids, and prostaglandinoids.

Claims

1. A catalyst composition comprising an insoluble, solid polymer substrate having covalently attached thereon a plurality of diphenylated cation radical units of the formula:

##STR6## wherein Z⁺ represents a monovalent cation radical selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and bismuth;

each X independently represents hydrogen or a substituted functional group selected from the group consisting of lower alkyl, halogen, hydroxy, alkyl halide, carbonyl, cyano, nitrile, and nitro groups; and

Y^- represents a monovalent anion;

said diphenylated cation radical covalently attached through one or more of its phenyl groups to the polymer substrate.

2. The composition of claim 1 wherein Z.⁺ is a nitrogen, phosphorus or arsenic cation radical.

3. The composition of claim 1 wherein Z.⁺ is a nitrogen cation radical.

4. The composition of claim 1 wherein X is a halogen or hydrogen.

5. The composition of claim 1 wherein Y^- is selected from the group consisting of perchlorate anion and monovalent anion halide salts of antimony, aluminum, boron or iron.

6. The composition of claim 1 wherein Y^- is a monovalent anion halide salt of antimony.

7. The catalyst composition of claim 1 wherein the polymer support is cellulose, polyisoprene, nylon, rayon, polyvinylchloride, polyethylene, polypropylene, fluorocarbon resin, polystyrene, polyurethane, polyester or acrylate resin.

8. The catalyst composition of claim 1 wherein the polymer support is a polystyrene.

9. The catalyst composition of claim 1 wherein the functional group X is in a para position relative to Z.⁺.