US4330642A
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Polymer bound multidentate complexes
Assignee: University of Illinois Foundation
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Filing: 1981-03-20
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Granted: 1982-05-18
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Expires: 2001-03-20
Abstract
Abstract Polymer bound multidentate complexes are prepared by reacting pendant benzyl chloride and benzyl iodide groups on a variety of polymer supports, including crosslinked polystyrene, with 3,3'-iminodiproprionitrile and reducing the nitrile groups by treatment with, for example, a boron hydride-tetrahydrofuran complex to form the amine. The amine is a precursor for other ligand systems; for example, the primary amine groups formed condense with an aldehyde or ketone to yield five coordinate Schiff base ligands. The polydentate amine ligand systems are useful for synthesis of chelating agents for sequestering metal ions from solution for purification or concentration purposes. Metal complexes of these ligands with manganese, iron, cobalt, nickel, copper, and zinc can be prepared which are useful as heterogeneous oxidation catalysts.
Inventors
- 👤 John H. Gaul, Jr.
- 👤 Russell S. Drago
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 00:59
CPC Classifications
C; C08; C08F; C08F8/00; C08F8/28; C08F2810/00; C08F2810/20
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
74 words
A process for preparing a polymer bound multidentate polyamine ligand system comprising the steps of (a) condensing a nitrile compound having the formula HX(CH 2 CH 2 CN) 2 where X is nitrogen or phosphorus with an insoluble crosslinked polymer possessing at least one pendant benzyl chloride or benzyl iodide function; and (b) converting the nitrile groups of the condensation product of step (a) to primary amino groups by reduction with BH 3 .
Claim 2
Dependent Claim
74 words
A process for preparing a polymer bound multidentate polyamine ligand system comprising the steps of (a) condensing a nitrile compound having the formula HX(CH 2 CH 2 CN) 2 where X is nitrogen or phosphorus with an insoluble crosslinked polymer possessing at least one pendant benzyl chloride or benzyl iodide function; and (b) converting the nitrile groups of the condensation product of step (a) to primary amino groups by reduction with BH 3 .
Claim 3
Dependent Claim
43 words
The process of claim 1 wherein X is nitrogen and the insoluble polymer is crosslinked polystyrene, and the condensation step of (a) is effected in an inert atmosphere under reflux in a solvent selected from the group consisting of dioxane, DMF, and THF.
Claim 4
Dependent Claim
43 words
The process of claim 1 wherein X is phosphorus and the insoluble polymer is crosslinked polystyrene, and the condensation of step (a) is effected in an inert atmosphere under reflux in a solvent selected from the group consisting of dioxane, DMF, and THF.
Claim 5
Dependent Claim
44 words
The process of claim 2 wherein the reduction of step (b) is effected in an inert atmosphere under reflux with an excess of BH 3 .THF solution, followed by neutralization of excess BH 3 with an alcohol, and separation of the reduction product therefrom.
Claim 6
Dependent Claim
111 words
A process for preparing a polymer bound multidentate Schiff base ligand system comprising the steps of (a) condensing a nitrile compound having the formula HX(CH 2 CH 2 CN) 2 where X is nitrogen or phosphorus with an insoluble crosslinked polymer possessing at least one pendant benzyl chloride or benzyl iodide function; (b) converting the nitrile groups of the condensation product of step (a) to primary amino groups by reduction with BH 3 ; and (c) condensing the primary amino groups of the product of step (b) with a carbonyl compound selected from the group consisting of aldehydes and ketones, the carbonyl compound being capable of forming the Schiff base ligands.
Claim 7
Dependent Claim
111 words
A process for preparing a polymer bound multidentate Schiff base ligand system comprising the steps of (a) condensing a nitrile compound having the formula HX(CH 2 CH 2 CN) 2 where X is nitrogen or phosphorus with an insoluble crosslinked polymer possessing at least one pendant benzyl chloride or benzyl iodide function; (b) converting the nitrile groups of the condensation product of step (a) to primary amino groups by reduction with BH 3 ; and (c) condensing the primary amino groups of the product of step (b) with a carbonyl compound selected from the group consisting of aldehydes and ketones, the carbonyl compound being capable of forming the Schiff base ligands.
Claim 8
Dependent Claim
99 words
The process of claim 5 wherein X is nitrogen and the insoluble polymer is crosslinked polystyrene, and the condensation of step (a) is effected in an inert atmosphere under reflux in a solvent selected from the group consisting of dioxane, DMF, and THF; the reduction of step (b) is effected in an inert atmosphere under reflux with an excess of BH 3 .THF solution, followed by neutralization of excess BH 3 with an alcohol; and the condensation of step (c) is effected by refluxing a benzene slurry of the reduction product of step (b) with an excess of salicylaldehyde.
Claim 9
Dependent Claim
155 words
A process for preparing a metal complex of a polymer bound multidentate Schiff base ligand system, the metal being selected from the group consisting of Co(II), Mn(II), Ni(II), Cu(II), Zn(II), Fe(II), and Fe(III), which process comprises the steps of (a) condensing a nitrile compound having the formula HX(CH 2 CH 2 CN) 2 where X is nitrogen or phosphorus with an insoluble crosslinked polymer possessing at least one pendant benzyl chloride or benzyl iodide function; (b) converting the nitrile groups of the condensation product of step (a) to primary amino groups by reduction with BH 3 ; (c) condensing the primary amino groups of the product of step (b) with a carbonyl compound selected from the group consisting of aldehydes and ketones, the carbonyl compound being capable of forming the Schiff base ligands; and (d) forming the metal complex by slurrying a solution of a salt of the metal with the product of step (c).
Claim 10
Dependent Claim
155 words
A process for preparing a metal complex of a polymer bound multidentate Schiff base ligand system, the metal being selected from the group consisting of Co(II), Mn(II), Ni(II), Cu(II), Zn(II), Fe(II), and Fe(III), which process comprises the steps of (a) condensing a nitrile compound having the formula HX(CH 2 CH 2 CN) 2 where X is nitrogen or phosphorus with an insoluble crosslinked polymer possessing at least one pendant benzyl chloride or benzyl iodide function; (b) converting the nitrile groups of the condensation product of step (a) to primary amino groups by reduction with BH 3 ; (c) condensing the primary amino groups of the product of step (b) with a carbonyl compound selected from the group consisting of aldehydes and ketones, the carbonyl compound being capable of forming the Schiff base ligands; and (d) forming the metal complex by slurrying a solution of a salt of the metal with the product of step (c).
Claim 11
Dependent Claim
123 words
The process of claim 7 wherein X is nitrogen and the insoluble polymer is crosslinked polystyrene, and the condensation of step (a) is effected in an inert atmosphere under reflux in a solvent selected from the group consisting of dioxane, DMF, and THF; the reduction of step (b) is effected in an inert atmosphere under reflux with an excess of BH 3 .THF solution followed by neutralization of excess BH 3 with an alcohol; the condensation of step (c) is effected by refluxing a benzene slurry of the reduction product of step (b) with an excess of salicylaldehyde; and the metal complex formation of step (d) is effected by slurrying a solution of cobalt acetate in DMF with the product of step (c).
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-05-17 | 1985-11-16 | 1986-05-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-05-17 | 1989-11-16 | 1990-05-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-05-17 | 1993-11-16 | 1994-05-18 | $7700.00 | Window Closed / Lapsed |