Methods of making cross-bridged macropolycycles

• US 6,225,464 B1
• Filed: 09/07/1999
• Issued: 05/01/2001
• Est. Priority Date: 03/07/1997
• Status: Expired due to Term

• Current Assignee: The Procter & Gamble Company
• Original Assignee: The Procter & Gamble Company
• Inventors: Hiler, George Douglas II, Perkins, Christopher Mark
• Primary Examiner(s): Shah, Mukund J.
• Assistant Examiner(s): Sripada, Pavanaram K
• Application Number:
  US09/380,675
• Time in Patent Office: 602 Days
• Field of Search: 540/471, 540/450, 540/470, 544/247
• US Class Current: 540/450
• CPC Class Codes: C07D 487/08 Bridged systems

Abstract

Improved synthesis of a macropolycycle, more particularly, of a cross-bridged tetraazamacrocycle.

Claims

1. A method for preparing a cross-bridged macropolycycle comprising a series of steps of derivatizing N,N′

-bis-(2-aminoethyl)-1,3-propanediamine, wherein said series of steps is carried out using one solvent system.

2. A method according to claim 1 wherein said solvent system is an alcoholic solvent system.

3. A method according to claim 1 wherein said solvent system comprises from about 60% to 100% of a C1-C4 alcohol or mixtures thereof.

4. A method according to claim 1 wherein said solvent system is ethanol or mixtures of ethanol with water.

5. A method according to claim 1 wherein said series of steps are all carried out in one reaction vessel.

10. A method for preparing a cross-bridged macropolycycle according to claim 1 comprising a series of steps of derivatizing cyclam or N,N′

-bis-(2-aminoethyl)-1,3-propanediamine including a step of reducing a diquaternized intermediate, wherein said step is carried out using an amount of less than about fifteen-fold of reducing agent.

6. A method for preparing a cross-bridged macropolycycle comprising a series of steps of derivatizing N,N′

-bis-(2-aminoethyl)-1,3-propanediamine, including a step of quaternizing an intermediate using a quaternizing agent, wherein said step is carried out using less than about fifteen-fold of said quaternizing agent.

7. A method according to claim 6 wherein said step is carried out using using less than about ten-fold of said quaternizing agent.

8. A method according to claim 6 wherein said step is carried out using from about five-fold to about ten-fold of said quaternizing agent.

9. A method according to claim 8 wherein said quaternizing agent is selected from methyl iodide, methyl tosylate, and dimethyl sulfate.

11. A method for preparing a cross-bridged macropolycycle comprising a series of steps of derivatizing cyclam or a particular acyclic tetraamine including a step of reducing a diquaternized intermediate, wherein said step is carried out using an amount of less than about fifteen-fold of reducing agent.

12. A method according to claim 11 wherein said reducing agent is a non-catalytic reducing agent.

13. A method according to claim 12 wherein said reducing agent is a hydride compound.

14. A method according to claim 13 wherein said hydride compound is a borohydride.

15. A method according to claim 14 wherein said borohydride compound is selected from sodium borohydride and potassium borohydride.

16. A method according to claim 15 wherein said borohydride compound is potassium borohydride.

18. A method according to claim 14 in which sodium ion is substantially absent.

17. A method for preparing a cross-bridged macropolycycle said method comprising derivatizing N,N′

-bis-(2-aminoethyl)-1,3-propanediamine, by a series of steps including;

quaternizing an intermediate using a quaternizing agent, wherein said step is carried out using less than about fifteen-fold of said quaternizing agent; and

reducing a diquaternized intermediate, wherein said step is carried out using an amount of less than about fifteen-fold of reducing agent; and

wherein further said series of steps is carried out using one solvent system.

19. A method for producing a complex of Mn and a cross-bridged macropolycyclic ligand, said method comprising reacting with manganous chloride a cross-bridged macropolycycle.

20. A method for producing a complex of Mn and a cross-bridged macropolycyclic ligand, said method comprising reacting a cross-bridged macropolycycle with MnCl₂ which has been produced by an anhydrous reaction of manganese metal with a chlorinating agent.

21. A method according to claim 20 which is conducted in a nonaqueous solvent.

22. A method for preparing a transition metal complex of a cross-bridged macropolycycle comprising

a series of steps of

(A) forming a bisaminal from an acrylic amine;

(B) forming a diquat derivative of said bisaminal;

(C) reducing said diquat derivative;

(D) separating reducing agent and solvent from the product of step (C) in one or more operations;

(E) removing residual hydride from the product of (D);

(F) isolating a cross-bridged tetraazamacrocycle product of steps (A)-(E); and

(G) reacting the product of step (F) with a transition-metal, thereby forming a transition-metal complex useful as a catalyst in detergent compositions.

23. A method for preparing a complex of manganese and a cross-bridged macrocyclic ligand comprising reacting a manganous containing compound with a cross-bridged macropolycyle wherein the cross-bridged macropolycylce is prepared by a process comprising a series of steps of derivatizing cyclam or N,N′

-bis-(2-aminoethyl)-1,3-propanediamine, wherein said series of steps is carried out using one solvent system.

24. A method for preparing a complex of manganese and a cross-bridged macrocyclic ligand comprising reacting a manganous containing compound with a cross-bridged macropolycyle wherein the cross-bridged macropolycylce is prepared by a process comprising a series of steps of derivatizing cyclam or N,N′

-bis-(2-aminoethyl)-1,3-propanediamine, including a step of quaternizing an intermediate using a quaternizing agent, wherein said step is carried out using less than about fifteen-fold of said quaternizing agent.

25. A method for preparing a complex of manganese and a cross-bridged macropolycycle comprising the steps of:

(A) forming a bisaminal from an acyclic amine;

(B) forming a diquat derivative of said bisaminal;

(C) reducing said diquat derivative;

(D) separating reducing agent and solvent from the product step of (C) in one or more operations;

(E) removing residual hydride from the product of (D);

(F) isolating a cross-bridged tetraazamacrocycle product of steps (A)-(E); and

(G) reacting the product of step (F) with a manganous containing compound, thereby forming a manganese complex.