Bispidon-derivated ligands and complexes thereof for catalytically bleaching a substrate

• US 7,501,389 B2
• Filed: 10/18/2004
• Issued: 03/10/2009
• Est. Priority Date: 10/31/2003
• Status: Active Grant

• Current Assignee: Conopco (Unilever PLC)
• Original Assignee: Conopco (Unilever PLC)
• Inventors: Hage, Ronald, Lienke, Joachim, Veerman-Petersen, Patricia
• Primary Examiner(s): DELCOTTO, GREGORY R
• Application Number:
  US10/576,647
• Publication Number:
  US 20080035885A1
• Time in Patent Office: 1,604 Days
• Field of Search: 510/312, 510/372, 510/376, 510/500, 252/186.39, 502/200, 502/324, 502/325
• US Class Current: 510/376
• CPC Class Codes: C07D 471/08 Bridged systems
• CPC Class Codes: C11D 3/168 Organometallic compounds or orgometallic complexes
• CPC Class Codes: C11D 3/3932 Inorganic compounds or complexes

Abstract

The present invention provides a bleaching composition comprising a [3.3.1] bicycle compound of formula (I) carrying at least one C8-C22-alkyl chain, the bleaching composition being substantially devoid of a peroxygen source.

Claims

1. A bleaching composition comprising:

a) a monomer ligand, L, or transition metal catalyst thereof of a ligand having the formula (I);

2. A bleaching composition according to claim 1, wherein the group containing a heteroatom capable of coordinating to a transition metal is selected from the group consisting of:

an optionally substituted tertiary amine of the form —

C2-C4-alkyl-NR7R8, in which R7 and R8 are independently selected from the group consisting of straight chain, branched or cyclo C1-C12 alkyl, benzyl, the —

C2-C4-alkyl- of the —

C2-C4-alkyl-NR7R8 may be substituted by 1 to 4 C1-C2-alkyl, or may form part of a C3 to C6 alkyl ring, and in which R7 and R8 may together form a saturated ring containing one or more other heteroatoms;

a heterocycloalkyl;

selected from the group consisting of;

pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethylene imine, 1,4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be connected to the ligand via any atom in the ring of the selected heterocycloalkyl;

a —

C1-C6-alkyl-heterocycloalkyl, wherein the heterocycloalkyl of the —

C1-C6-alkyl-heterocycloalkyl is selected from the group consisting of;

piperidinyl, piperidine, 1,4-piperazine, tetrahydrothiophene, tetrahydrofuran, pyrrolidine, and tetrahydropyran, wherein the heterocycloalkyl may be connected to the —

C1-C6-alkyl via any atom in the ring of the selected heterocycloalkyl; and

,

a —

C1-C6-alkyl-heteroaryl, wherein the heteroaryl of the —

C1-C6-alkyl-heteroaryl is selected from the group consisting of;

pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl may be connected to the —

C1-C6-alkyl via any atom in the ring of the selected heteroaryl and the selected heteroaryl is optionally substituted by a group selected from the group consisting of a —

C1-C4-alkyl, —

C0-C6-alkyl-phenol, —

C0-C6-alkyl-thiophenol, —

C2-C4-alkyl-thiol, —

C2-C4-alkyl-thioether, —

C2-C4-alkyl-alcohol, —

C2-C4-alkyl-amine, and a —

C2-C4-alkyl-carboxylate.

3. A bleaching composition according to claim 1, wherein z groups are same heteroaromatic groups of the form:

4. A bleaching composition according to claim 3, wherein z is pyridinyl optionally substituted by —

C0-C4-alkyl.

5. A bleaching composition according to claim 1, wherein at least one of R1 and R2 is a non-aromatic hydrocarbon group, the non-aromatic hydrocarbon group being a C10-C20 alkyl chain.

6. A bleaching composition according claim 1, wherein one of R1 and R2 is selected from the group consisting of:

Me, CH2-C6H5, and pyridin-2-ylmethyl, wherein the pyridin-2-ylmethyl is optionally substituted by C1-C4-alkyl.

7. A bleaching composition according to claim 6, wherein one of R1 and R2 is a pyridin-2-ylmethyl that is optionally substituted by C1-C4-alkyl.

8. A bleaching composition according claim 1, wherein one of R1 and R2 is selected from the group consisting of:

an optionally substituted tertiary amine of the form —

C2-C4-alkyl-NR7R8, in which P7 and R8 are independently selected from the group consisting of straight chain, branched or cyclo C1-C12 alkyl, —

CH2-C6H5, wherein the C6H5 is optionally substituted by —

C1-C4-alkyl or —

O—

C1-C4-alkyl, and pyridin-2-ylmethyl wherein the pyridine is optionally substituted by C1-C4-alkyl, the —

C2-C4-alkyl- of the —

C2-C4-alkyl-NR7R8 may be substituted by 1 to 4 C1-C2-alkyl, or may form part of a C3 to C6 alkyl ring, and in which R7 and R8 may together form a saturated ring containing one or more other heteroatoms.

9. A bleaching composition according to claim 8, wherein the optionally substituted tertiary amine of the form —

C3-alkyl-NR7R8.

10. A bleaching composition according to claim 9, wherein the —

C3-alkyl-NR7R8 is

11. A bleaching composition according to claim 8, wherein the optionally substituted tertiary amine of the form —

C2-alkyl-NR7R8.

12. A bleaching composition according to claim 8, wherein —

NR7R8 is selected from group consisting of;

—

NMe2, —

NEt2, —

N(i—

Pr)2,

13. A bleaching composition according to claim 1, wherein R3 and R4 are selected from the group consisting of:

—

C(O)O—

C1-C24-alkyl, —

C(O)—

O—

C1-C24-aryl —

CH2OC(O)C1-C20-alkyl, benzyl ester, phenyl, benzyl, CN, hydrogen, methyl, and C1-C4-OR wherein R is selected from the group consisting of H, C1-C24-alkyl or C(O)—

C1-C24-alkyl.

14. A bleaching composition according to claim 13, wherein R3 and R4 are selected from the group consisting of —

CH2OH, —

C(O)—

O—

CH2C6H5 and —

C(O)O—

C1-C6-alkyl.

15. A bleaching composition according to claim 14, wherein R3 and R4 are selected from the group consisting of:

—

C(O)—

O—

CH3, —

C(O)—

O—

CH2CH3, —

C(O)—

O—

CH2C6H5 and CH2OH.

16. A bleaching composition according to claim 1, wherein:

R3═

R4.

17. A bleaching composition according to claim 1, wherein X selected from the group consisting of:

C═

O, CH2, C(OH)2, syn-CHOR and anti-CHOR, wherein R is H, C1-C24-alkyl or C(O)—

C1-C24-alkyl.

18. A bleaching composition according to claim 17, wherein X is C═

O or C(OH)2.

19. A bleaching composition according to claim 18, wherein X is C═

O.

20. A bleaching composition according to claim 1, wherein the complex is of the general formula (A1):

[M_aL_kX_n]Y_m 

 

(A1)

in which;

M represents a metal selected from Mn(II)-(III)-(IV)-(V), Cu(I)-(II)-(III), Fe(II)-(III)-(IV)-(V), Co(I)-(II)-(III), Ti(II)-(III)-(IV), V(II)-(III)-(IV)-(V), Mo(II)-(III)-(IV)-(V)-(VI) and W(IV)-(V)-(VI);

X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner;

Y represents any non-coordinated counter ion;

a represents an integer from 1 to 10;

k represents an integer from 1 to 10;

n represents an integer from 0 to 10;

m represents zero or an integer from 1 to 20; and

L represents a ligand as defined in claims 1 to 19, or its protonated or deprotonated analogue.

21. A bleaching composition according to claim 20, wherein M represents a metal selected from Fe(II)-(III)-(IV)-(V).

22. A bleaching composition according to claim 21, wherein M represents a metal selected from Fe(II) and Fe(III).

23. A bleaching composition according to claim 22, wherein the ligand is present in the form selected from the group consisting of [FeLCl]Cl;

[FeL(H2O)](PF6)2;

[FeLCl]PF6 and [FeL(H2O)](BF4)2.