Bleach catalysts and formulations containing them

Details Bleach catalysts and formulations containing them Bleach catalysts and formulations containing them

2001-07-12

2003-11-18

Delcotto, Gregory (Department: 1751)

Cleaning compositions for solid surfaces, auxiliary compositions

Cleaning compositions or processes of preparing

With oxygen or halogen containing chemical bleach or oxidant...

C510S311000, C252S186330, C502S207000, C502S325000, C502S338000, C008S111000

Reexamination Certificate

active

06649582

ABSTRACT:

TECHNICAL FIELD
The present invention relates to new macrocyclic bleach catalysts, to formulations comprising these catalysts, as well as bleaching processes which employ these catalysts.
BACKGROUND OF THE INVENTION
Metal ion catalysis of oxygen bleaches, particularly in fabric washing processes, is well known. In these systems, a metal such as manganese, generally attached to a suitable ligand is exposed to the fabric together with an oxygen bleach such as hydrogen peroxide. A known disadvantage of such systems is that the metal species can be abstracted from the ligand and oxidised to form an insoluble oxide precipitate which deposits at the fabric surface.
Two mechanisms have been proposed for catalysed bleaching, in one the oxygen bleach is decomposed in the presence of the catalyst to a short-lived but highly active species such as the hydroxyl radical. In the other proposed mechanism, the oxygen bleach reacts with the catalyst to form an intermediate species which either transfers oxygen or abstracts hydrogen atoms or electrons to the substrate. As will be appreciated, the first type of reaction is relatively non-specific as regards the substrate while the second is likely to be influenced strongly by the nature of the substrate and its reactivity with the intermediate.
While the non-specific reaction is likely to attack most materials which are susceptible to bleaching, it is not suitable for many applications. There is a need for electron or oxygen transfer systems which are capable of reacting with structures such as catechols, and curcumin etc., which are found in the components of, for example, wine and tea stains (catechol) or curry stains (curcumin). It is important that the components of such electron or oxygen transfer systems are hydrolytically stable so as avoid the disadvantages mentioned above.
Bottino et al (
J. Org. Chem
. 1988, 53, 3521-3529) disclose the synthesis of symetrical N-tosyl aza macrocycles. Kruger (
Chem. Ber
. 1995, 128, 531-539) discloses the N,N-Dimethyl-2,11-diazo[3.3](2,6)pyridinophane (NNDDP) complexes of copper, nickel and cobalt. The corresponding vanadium complex is disclosed in Inorg. Chem. (1996), 35, 3533. NNDDP is a macrocyclic ligand. Other manganese macrocyclic ligand complexes are known as mimics of superoxide dismutase form Riley et. al. (
J. Am. Chem. Soc
., 1994, 116, 387-388). However, these are not aryl ligands.
Koch et. al. (
Angew. Chem. Its. Ed Engl
., 1995, 34, No 23/24 p 2671-2674) (hereinafter called the “First Koch Reference”) disclose that certain Iron III complexes of NNDDP are capable of mimicking the biological activity of intradiol-cleaving catechol dioxygenases and converting catechols, in the presence of oxygen to the corresponding muconic acid. The synthesis of certain eight-co-ordinate iron II and iron III complexes of bis(2,11-diaza[3.3](2,6)pyridinophane, i.e. certain non-methylated analogues of NNDDP is described by Koch et. al. in
Angew. Chem., Int. Ed Engl
., (1996), 35(4), 422-4 (hereinafter called the “Second Koch Reference”). However, there is no disclosure of the suitability of such materials as bleach catalysts for detergent products, nor any description of corresponding iron complexes having a lower co-ordination number.
BRIEF DESCRIPTION OF THE INVENTION
It has now been discovered that certain novel ligands which are NNDDP analogues have novel activities in themselves and furthermore in complex with various metals, also have better activity than known iron III NNDDP complexes. They exhibit unexpected hydrolytic stability, as well as stability against metal abstraction by metal abstracting agents. Furthermore, these new materials show unexpected activity with air, or molecular oxygen or other oxygenated bleaching materials such as peroxides, persalts or peracids, against catechol and catechol-like materials which form a significant component of several common laundry stains. They could also find application in a wide range of other uses where a bleaching effect is desired.
In general, the invention is based upon a macrocyclic ligand of formula (I):
wherein Z
1
and Z
2
are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring structure being optionally substituted by one or more substituents
Y
1
and Y
2
are independently selected from C, N, O, Si, P and S atoms
A
1
and A
2
are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, suphonate, phosphate, groups of formulae (G
1
)(G
2
)N—G
3
OC(O)—, G
3
O— and G
3
C(O)—, wherein each of G
1
, G
2
and G
3
is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups in addition to any amongst the foregoing), electron donating groups and electron withdrawing groups;
i and j are selected from 0, 1 and 2 to complete the valency of the groups Y
1
and Y
2
each of Q
1
-Q
4
is independently selected from groups of formula
wherein 10>a+b+c+d>=2;
each Y
3
is independently selected from O, S, SO, SO
2
, (G
1
)(G
2
)N— (wherein G
1
and G
2
are as hereinbefore defined), C(O), monocyclic or polycyclic aryl, monocyclic or polycyclic heteroaryl, P and P(O);
each of A
3
-A
6
is independently selected from the groups hereinbefore defined for A
1
and A
2
; and
wherein any two or more of A
1
-A
6
together may optionally form a bridging group, provided that if A
1
and A2 are linked without simultaneous linking also to any of A3-A6, then the bridging group linking A
1
and A
2
must contain at least one carbonyl group.
For the avoidance of doubt, throughout this specification, “=<” means “less than or equal to” and “>=” means “greater than or equal to”.
Thus, a first aspect of the present invention provides a novel ligand of formula (I) as hereinbefore defined.
In formula (I), Z
1
and Z
2
are preferably the same. Preferably Z
1
and/or Z
2
are selected from nitrogen-containing monocyclic aryl groups, for example linkages constituted by pyridine, pyrrole, imidazole and pyrazine rings. Of these, pyridine is the most preferred. Any of the foregoing is optionally substituted, e.g. by one or more electron withdrawing and/or electron donating groups.
Y
1
and Y2 are preferably both the same. In any event, preferably Y
1
and/or Y2 is selected from nitrogen and carbon atoms.
In the definitions of A
1
and A
2
, alkyl groups preferably have from 1 to 6 carbon atoms, alkenyl groups preferably have from 2-6 carbon atoms, cycloalkyl groups preferably have from 5 to 9 carbon atoms and aryl and heteroaryl groups are preferably monocyclic and have from 5 to 9 carbon atoms or carbon+heteroatoms respectively. Wherever else alkyl, akenyl, cycloalkyl, aryl and heteroaryl moieties are mentioned in this specification, they preferably have the same number of (carbon) atoms as in this definition of A
1
and A
2
, unless explicitly recited to the contrary.
In the definition of Q
1
-Q
4
, d is preferably 1 or 2, most preferably 1. It is also preferred that a+b+c=1, 2 or 3. Y
3
(when present) is preferably —NH
2
— or —NHCO—. It is especially preferred that any of Q
1
-Q
4
is —CH
2
—. Preferably, Q
1
-Q
4
are all the same.
Throughout this specification, any reference to electron donating or withdrawing groups refers to any such group or groups known to those skilled in the art. However, typical electron withdrawing groups are halo (e.g. chloro or fluoro), C
1-6
alkoxy (e.g. methoxy), hydroxy, hydroxyalkyl, (optionally mono-or di-substituted) amine groups, (optionally mono- or di-substitued) thiol groups, carboxyl, ester, amide, substituted carbonyl groups in general, nitrile, nitro (optionally substituted) sulphonyl, alkenyl e.g. vinyl, ethynyl, phenyl, quarternary ammonium (+) and sulphonium (+) groups. Aryl groups in general may also be used.
Typical electron donating groups include C
1-6
alkyl (especial

Affiliated with

Also associated with

Rating

Bleach catalysts and formulations containing them does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Bleach catalysts and formulations containing them, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Bleach catalysts and formulations containing them will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3116165