Hydrogen peroxide catalyzed process for the preparation of sterically hindered N-hydrocarbyloxyamines

• US 20050014948A1
• Filed: 07/12/2004
• Published: 01/20/2005
• Est. Priority Date: 07/14/2003
• Status: Active Grant

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Galbo, James P., Detlefsen, Robert E.
• Granted Patent: US 7,390,904 B2
• Time in Patent Office: Days
• US Class Current: 546/184
• CPC Class Codes: C07D 211/94 Oxygen atom, e.g. piperidine N-oxide

Abstract

Sterically hindered N-hydrocarbyloxyamines are prepared from hindered amine N-oxyl compounds by a process which uses hydrogen peroxide or a hydrogen peroxide equivalent, a catalytic amount of a peroxide decomposing transition metal salt, metal oxide, or metal-ligand complex, a hydrocarbon solvent containing no activated hydrogen atoms, and a relatively inert cosolvent. These compounds are useful as thermal and light stabilizers for a variety of organic substrates.

Claims

1. A process for preparing sterically hindered N-hydrocarbyloxyamines of formula (I)

2. A process according to claim 1 for preparing sterically hindered N-hydrocarbyloxyamines of formula Ia

3. A process according to claim 1 for preparing sterically hindered N-hydrocarbyloxyamines of formula Ib

4. A process according to claim 1 for preparing sterically hindered N-hydrocarbyloxyamines of formula Ic

5. A process according to claim 1 wherein the sterically hindered N-hydrocarbyloxyamine is

Bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;

1-Cyclohexyloxy-4-methoxy-2,2,6,6-tetramethylpiperidine;

Bis(1-heptyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;

1-Hexyloxy-4-methoxy-2,2,6,6-tetramethylpiperidine;

Bis[1-(2-methyl-2-phenylpropyloxy)-2,2,6,6-tetramethylpiperidin-4-yl] adipate;

1-(2-methyl-2-phenylpropyloxy)-4-benzoyloxy-2,2,6,6-tetramethylpiperidine;

2-Chloro-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine;

2,4,6-Tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine;

Bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;

1-Cyclooctyloxy-2,2,6,6-tetramethylpiperidin-4-ol;

Reaction product of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and methylcyclohexane;

Reaction product of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate and norbornane;

Reaction product of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol and decahydronaphthalene;

Reaction product of bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-y) adipate and isooctane;

Reaction product of 1-oxyl-4-benzoyloxy-2,2,6,6-tetramethylpiperidine and isooctane;

Bis[1-(2,2-diphenylpropyloxy)-2,2,6,6-tetramethylpiperidin-4-yl] sebacate;

1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidine;

Bis(1-octadecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate;

1-Cyclohexyloxy-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;

1-Octyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine;

1-Cyclohexyloxy-4-benzoyloxy-2,2,6,6-tetramethylpiperidine;

1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-ol;

or

1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-one.

6. A process according to claim 1 wherein the relatively inert cosolvent is methanol or acetonitrile.

7. A process according to claim 6 wherein the relatively inert cosolvent is acetonitrile.

8. A process according to claim 1 wherein the hydrogen peroxide equivalent is urea hydrogen peroxide.

9. A process according to claim 1 wherein the peroxide decomposing transition metal, metal salt or oxide is iron powder, nanosized activated iron powder, iron(II) chloride, iron(III) chloride, iron(III) acetylacetonate, iron(II) sulfate, iron(III) sulfate, iron(II) acetate, iron(II)oxide, iron(III)oxide, iron(II,III) oxide, iron(III) citrate, iron(II) oxalate, iron(III) oxalate, iron(III) nitrate, iron(II) perchlorate, iron(III) perchlorate, iron(II) trifluoroacetate, iron(II) tetrafluoroborate, iron(II) ethylenediammonium sulfate, iron(III) para-toluenesulfonate, ferrocenium hexafluorophosphate, ferrocenium tetrafluoroborate, copper powder, nanosized activated copper powder, copper(I) chloride, copper(II) chloride, copper (I) oxide, copper(II) oxide, copper(II) sulfate, copper(II) trifluoromethanesulfonate, or copper(II) trifluoroacetate.

10. A process according to claim 9 wherein the peroxide decomposing transition metal, metal salt or oxide is copper(I) chloride, copper(II) chloride, copper(II) sulfate, iron(II) chloride, iron(II) sulfate, iron(III) sulfate, iron(III) chloride, iron (II) oxide, iron (III) oxide, iron(II,III) oxide, copper(I) oxide, copper(II) oxide, copper powder, nanosized activated copper powder, iron powder, or nanosized activated iron powder.

11. A process according to claim 1 wherein the metal of the peroxide decomposing transition metal-ligand complex is vanadium(II), vanadium (III), tin(IV), copper(I), copper(II), titanium(III), titanium(IV), manganese(II), manganese(III), iron(II), iron(III), cerium (III), cobalt(II), or ruthenium(I).

12. A process according to claim 11 wherein the metal of the peroxide decomposing transition metal-ligand complex is iron(II) or iron (III).

13. A process according to claim 1 wherein the ligand of the peroxide decomposing transition metal-ligand complex is 2,2′

-dipyridyl, 2,2′

;

6,2″

-terpyridine, 2,3-bis(2-pyridyl)pyrazine, 1,10-phenanthroline, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, triphenylphosphine oxide, pyridine, picolinic acid, 2-pyrazinecarboxylic acid, diimines formed from the reaction of aniline or substituted anilines with 1,2-diketones, diimines such as N,N′

-bis(salicylidene)ethylenediamine or N,N′

-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamine, or cyclopentadiene.

14. A process according to claim 13 wherein the ligand of the peroxide decomposing transition metal-ligand complex is 2,2′

-dipyridyl.

15. A process according to claim 1 where in the temperature is about 0 degrees to about 100 degrees Celsius.

16. A process according to claim 15 where in the temperature is about 20 degrees to about 100 degrees Celsius.

17. A process according to claim 16 where in the temperature is about 50 degrees to about 100 degrees Celsius.

18. A process according to claim 1 wherein additionally an acid is added.

19. A process according to claim 18 wherein the acid is hydrochloric acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, tetrafluoroboric acid, acetic acid, boric acid, citric acid, or methanesulfonic acid.

20. A process according to claim 19 wherein the amount of acid is about 0.005 to about 1 mole per mole of N-oxyl moiety contained in the compound of formula (IIa).

21. A process according to claim 20 wherein the amount of acid is about 0.02 to about 0.25 moles of acid per mole of N-oxyl moiety contained in the compound of formula (IIa).

22. A process according to claim 6 wherein the amount of cosolvent is about 0.5 to about 2 parts by volume to 1 part hydrocarbon.

23. A process according to claim 1 wherein the amount of peroxide decomposing transition metal salt, metal oxide, or metal-ligand complex is about 0.001 to about 0.1 moles per mole of N-oxyl moiety.

24. A process according to claim 23 wherein the amount of peroxide decomposing transition metal salt, metal oxide, or metal-ligand complex is about 0.002 to about 0.05 moles per mole of N-oxyl moiety.

25. A process according to claim 1 wherein the amount of hydrocarbon is about 1 to about 15 moles of hydrocarbon per mole of N-oxyl moiety.

26. A process according to claim 25 wherein the amount of hydrocarbon is about 2 to about 10 moles of hydrocarbon per mole of N-oxyl moiety.

27. A process according to claim 26 wherein the amount of hydrocarbon is about 5 to about 10 moles of hydrocarbon per mole of N-oxyl moiety.

28. A process according to claim 1 wherein the amount of hydrogen peroxide or hydrogen peroxide equivalent is about 1 to about 10 moles per mole of N-oxyl moiety.

29. A process according to claim 28 wherein the amount of hydrogen peroxide or hydrogen peroxide equivalent is about 2 to about 5 moles per mole of N-oxyl moiety.

30. A process according to claim 1 wherein the concentration of hydrogen peroxide or hydrogen peroxide equivalent employed is about 15 to about 50% aqueous solution based on weight.

31. A process according to claim 30 wherein the concentration of hydrogen peroxide or hydrogen peroxide equivalent employed is about 30 to about 50% aqueous solution based on weight.

32. A process according to claim 31 wherein the concentration of hydrogen peroxide or hydrogen peroxide equivalent employed is about 50% aqueous solution based on weight.