AU777434B2

AU777434B2 - Method of pretreating and bleaching stained fabrics

Info

Publication number: AU777434B2
Application number: AU64400/00A
Authority: AU
Inventors: Michel Gilbert Jose Delroisse; David Andrew Ross Jones; Richard George Smith; John Francis Wells
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1999-09-01
Filing date: 2000-08-04
Publication date: 2004-10-14
Anticipated expiration: 2020-08-04
Also published as: EP1208184A1; CN1384869A; WO2001016268A1; AU6440000A; CA2382114A1

Description

WO 01/16268 PCT/EP00/07561 1 METHOD OF PRETREATING AND BLEACHING STAINED FABRICS FIELD OF INVENTION This invention relates to a method for bleaching stained fabrics, more particularly by pretreating the stained fabric, before washing, with a pretreatment composition that comprises an organic ligand that forms a transition metal complex as bleach catalyst. The invention further relates to the use of the ligand or complex in a pretreatment composition for applying to stained fabrics prior to washing in an aqueous wash liquor.

BACKGROUND OF INVENTION EP-A-0909809 discloses a class of iron coordination complexes useful as catalysts for the bleach activation of peroxy compounds, including iron complexes comprising the ligand N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-1aminoethane, also referred to as MeN4Py. These catalysts are said to be useful in bleaching systems comprising a peroxy compound or a precursor thereof, such as in the washing and bleaching of substrates including laundry, dishwashing and hard surface cleaning, or for bleaching in the textile, paper and woodpulp industries, and in waste water treatment.

In our co-pending application PCT/GB99/02876, we describe methods for catalytically bleaching substrates with atmospheric oxygen in aqueous medium, using metal ligand complexes as catalytic bleaching agents. These methods are said to be particularly applicable to bleaching of laundry fabrics, suitably in detergent formulations, but also may be WO 01/16268 pCT/EPOO/07561 -2used for hard surface cleaning, waste-water treatment, pulp bleaching in paper manufacture, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact lens disinfection.

However, there remains a need for improved methods of bleaching stained laundry fabrics. Thus, it would be desirable to be able to effect improved bleaching of particular stain types. It would also be desirable to be able to bleach a broader profile of stain types more effectively.

SUMMARY OF INVENTION We have now found that improved or broader stain profile bleaching can be achieved in accordance with the present invention, by using a specified ligand or transition metal complex bleach catalyst to pretreat stained fabrics prior to washing.

Accordingly, in a first aspect, the present invention provides a method of bleaching fabric stains comprising applying a pretreatment composition to a stained fabric, and subsequently washing the pretreated fabric in an aqueous wash liquor, wherein: the pretreatment composition comprises a ligand which forms a complex with a transition metal, the complex catalysing bleaching of stains by atmospheric oxygen; and one or both of the pretreatment composition and the wash liquor are substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.

WO 01/16268 PCITEP00/07561 3 In a second aspect, the present invention provides the use of a ligand which forms a complex with a transition metal, the complex catalysing bleaching of stains by atmospheric oxygen, in a pretreatment composition for applying to stained fabrics prior to stain bleaching by washing the pretreated fabric in an aqueous wash liquor.

Preferably, the ligand is N,N-bis(pyridin-2-yl-methyl)-1,1bis(pyridin-2-yl)-1-aminoethane, and the complex is an iron complex.

We have found that certain stain types can be more effectively bleached on stained fabrics by the pretreatment.

Thus, the bleaching of oily stains such as tomato stain can be improved by the pretreatment. For stains of this type, a peroxygen bleach such as hydrogen peroxide, or a peroxybased or -generating bleach system, may be present or absent in the pretreatment composition, but preferably is absent.

Bleaching of tea stains may also be improved by the pretreatment. For stains of this type, a peroxygen bleach such as hydrogen peroxide, or a peroxy-based or -generating bleach system, should be present in the pretreatment composition.

In order to provide a more effective bleaching performance over a range of different stain types, it is preferred that one of the pretreatment composition and the wash liquor comprises a peroxygen bleach such as hydrogen peroxide or a peroxy-based or -generating bleach system. Thus, the other of the pretreatment composition and the wash liquor is free WO 01/16268 PCTIEP00/07561 4 of peroxygen bleach or a peroxy-based or -generating bleach system. Since the specificity of catalytic bleaching for particular stain types may be altered according to the presence or absence of peroxygen bleach or a peroxy-based or -generating bleach systems, a broader stain profile may be bleached more effectively by ensuring that either the pretreatment or the wash liquor, but not both, comprise peroxy bleach.

For example, it may be postulated that catalytic bleaching with atmospheric oxygen will predominate in the wash liquor during the wash cycle when the wash liquor is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, so as to favour bleaching of tomato stain types over tea stain types, whereas peroxy bleach catalysis will predominate during the pretreatment if the pretreatment composition comprises peroxygen bleach or a peroxy-based or -generating bleach system, so as to favour bleaching of tea stain types over tomato stain types.

Alternatively, the peroxygen bleach or peroxy-based or generating bleach system could absent from the pretreatment composition and present only in the wash liquor so as to favour the bleaching of tomato stain types during the pretreatment and the bleaching of tea stain types during the main wash cycle. By altering the specificity of bleaching for particular stain types between the pretreatment step and the main wash step, a broad stain profile bleaching can be effected.

WO 01/16268 PCTIEP00/07561 In a preferred embodiment, therefore, the pretreatment composition comprises peroxygen bleach or a peroxy-based or -generating bleach system and the wash liquor is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system. In this embodiment, preferably the stained fabric comprises a tea stain.

In an alternative embodiment, the pretreatment composition is substantially devoid of peroxygen bleach or a peroxybased or -generating bleach system and the wash liquor comprises peroxygen bleach or a peroxy-based or -generating bleach system. In this embodiment, preferably the stained fabric comprises a tomato, oil or tomato/oil stain.

We have also found that the bleaching effect on certain stain types, for example tomato/oil stain types, may be enhanced by the presence of unsaturated fatty acids, such as oleic acid, or esters thereof, preferably unsaturated fatty acid oils, in the pretreatment composition. Therefore, in a preferred embodiment, the pretreatment composition comprises an unsaturated fatty acid oil in combination with the ligand or complex. The unsaturated fatty oils are relatively inexpensive and it is postulated that similar materials will serve to provide a similar bleach enhancing activity.

Enhancement of the bleaching process will likely be found in compounds having a hydrogen that is relatively prone to abstraction by a free radical. Other examples of compounds that are likely suitable as bleach enhancers are found in compounds containing an allylic hydrogen, a hydrogen alpha to an ether (anomeric effect), a hydrogen alpha to an amine, a benzylic hydrogen etc.

WO 01116268 PCT/EP00/07561 6 Any suitable fabric that is susceptible to stain bleaching or one that one might wish to subject to bleaching may be used. Preferably the fabric is a laundry fabric or garment.

In a preferred embodiment, the method according to the present invention is carried out on a laundry fabric using an aqueous pretreatment composition. In particular, the treatment may be effected prior to a conventional wash cycle.

The pretreatment composition will comprise at least the ligand or complex in combination with a suitable medium, such as an aqueous or nonaqueous solvent, or an inert carrier such as a filler. It will be appreciated that the composition may take any suitable form, such as a solid, powder, paste, gel or liquid. Preferably, the pretreatment composition is in the form of a liquid.

The pretreatment composition may be applied to the stained fabric by any suitable delivery method, for example by spraying as a liquid or dry powder, from a liquid, gel or paste applicator, or from a bar. Preferably, the pretreated fabric is left for at least 5 minutes, preferably at least minutes, more preferably at least 50 minutes, before washing.

The pretreatment composition may be contacted to the textile fabric in any suitable manner. For example, it may be applied in dry form, such as in powder form, particularly to wetted fabrics, or in a liquor, for example as an aqueous spray-on fabric treatment fluid, or a non-aqueous dry WO 01/16268 PCT/EPOO/07561 7 cleaning fluid or spray-on aerosol fluid, to dry or wet fabrics.

Suitable pretreatment means for application of the ligand or complex to the textile material prior to the main wash include sprays, pens, roller-ball devices, bars, soft solid applicator sticks and impregnated cloths or cloths containing microcapsules. Such means are well known in the analogous art of deodorant application and/or in spot treatment of textiles.

The present invention also extends to a commercial package comprising a ligand or complex preferably as defined below together with instructions for its use.

DETAILED DESCRIPTION OF THE INVENTION The catalyst may comprise a preformed complex of a ligand and a transition metal. Alternatively, the catalyst may comprise a free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate. The catalyst may also be included in the form of a composition of a free ligand or a transition metal-substitutable metal-ligand complex, and a source of transition metal, whereby the complex is formed in situ in the medium.

The ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex. Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V, copper I-III, WO 01/16268 PCT/EP00/07561 8 cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.

The transition metal complex preferably is of the general formula: [MaLkXn] Ym in which: M represents a metal selected from Mn(II)-(III)-(IV)- Fe Co(I)-(II)- (III), Ti(II)-(III)-(IV), Mo(II)and preferably from L represents the ligand, preferably N,N-bis(pyridin-2yl-methyl)-l,l-bis(pyridin-2-yl)-1-aminoethane, or its protonated or deprotonated analogue; 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 k represents an integer from 1 to n represents zero or an integer from 1 to m represents zero or an integer from 1 to Preferably, the complex is an iron complex comprising the ligand N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-1aminoethane. However, it will be appreciated that the pretreatment method of the present invention may instead, or WO 01/16268 PCT/EPOO/07561 9additionally, use other ligands and transition metal complexes, provided that the complex formed is capable of catalysing stain bleaching by atmospheric oxygen. Suitable classes of ligands are described below: Ligands of the general formula (IA): Zl-(Q1) T- C-(Q3)-U Z--(Q1)

(IA)

wherein Z1 groups independently represent a coordinating group selected from hydroxy, amino, -NHR or -N(R) 2 (wherein R=Ci- 6 alkyl), carboxylate, amido, -NH-C(NH)NH 2 hydroxyphenyl, a heterocyclic ring optionally substituted by one or more functional groups E or a heteroaromatic ring optionally substituted by one or more functional groups E, the heteroaromatic ring being selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; Q1 and Q3 independently represent a group of the formula: WO 01/16268 pCT/EP00/07561 10 b c R6 R8 wherein 5 a+b+c 1; a=0-5; b=0-5; c=0-5; n=0 or 1 (preferably n=0); Y independently represents a group selected from

-SO

2 arylene, alkylene, heteroarylene, heterocycloalkylene, and wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; R5, R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6, or R7 together with R8, or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8, or R5 together with R8 and/or independently R6 together with R7, represent Ci,--alkylene optionally substituted by C-.4-alkyl, -Cl, -Br or -I; WO 01/16268 PCT/EP00/07561 11 T represents a non-coordinated group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, arylalkyl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E (preferably T= -OH, methyl, methoxy or benzyl); U represents either a non-coordinated group T independently defined as above or a coordinating group of the general formula (IIA), (IIIA) or (IVA): (Q)-22 -Ei (Q--Z4

(IIA)

Z

3 -]j

(IIIA)

pQ1)-Z1 -Q

(IVA)

wherein Q2 and Q4 are independently defined as for Q1 and Q3; WO 01/16268 PCT/EP00/07561 12 Q represents (wherein T is independently defined as above), or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; Z2 is independently defined as for Z1; Z3 groups independently represent (wherein T is independently defined as above); Z4 represents a coordinating or non-coordinating group selected from hydrogen, hydroxyl, halogen, -NH-C(NH)NH 2

-R

and -OR, wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or Z4 represents a group of the general formula (IIAa): Z2-(Q) /(QI)-Z1 /N

T

(Q)-Z1 (IIAa) and 1 j 4.

Preferably, Zl, Z2 and Z4 independently represent an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, WO 01/16268 PCT/EP00/07561 13 pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole. More preferably, Z1, Z2 and Z4 independently represent groups selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-l-yl, and optionally substituted quinolin-2-yl. Most preferred is that Zl, Z2 and Z4 each represent optionally substituted pyridin-2-yl.

The groups Zl, Z2 and Z4 if substituted, are preferably substituted by a group selected from C 1 -4-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl. Preferred is that Z1, Z2 and Z4 are each substituted by a methyl group. Also, we prefer that the Zl groups represent identical groups.

Each Q1 preferably represents a covalent bond or C1-C4alkylene, more preferably a covalent bond, methylene or ethylene, most preferably a covalent bond.

Group Q preferably represents a covalent bond or C1-C4alkylene, more preferably a covalent bond.

The groups R5, R6, R7, R8 preferably independently represent a group selected from hydroxy-Co-C 20 -alkyl, halo-Co-C 20 alkyl, nitroso, formyl-Co-C 20 -alkyl, carboxyl-Co-C20-alkyl and esters and salts thereof, carbamoyl-Co-C 20 -alkyl, sulfo-Co-

C

20 -alkyl and esters and salts thereof, alkyl, amino-Co-C 20 -alkyl, aryl-Co-C 20 -alkyl, Co-C 20 -alkyl, WO 01/16268 PCTIEPOO/07561 14 alkoxy-Co-Cs-alkyl, carbonyl-Co-C 6 -alkoxy, and Co-C 20 alkylamide. Preferably, none of R5-R8 is linked together.

Non-coordinated group T preferably represents hydrogen, hydroxy, methyl, ethyl, benzyl, or methoxy.

In one aspect, the group U in formula (IA) represents a coordinating group of the general formula (IIA): (0-22 (QF--z4

(IIA)

According to this aspect, it is preferred that Z2 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole, more preferably optionally substituted pyridin-2-yl or optionally substituted benzimidazol-2-yl.

It is also preferred, in this aspect, that Z4 represents an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole, more preferably optionally substituted pyridin-2-yl, or an non-coordinating WO 01/16268 WO 016268CT/EPOO/07561 15 group selected from hydrogen, hydroxy, alkoxy, alkyl, alkenyl, cycloalkyl, aryl, or benzyl.

in preferred embodiments of this aspect, the ligand is selected from: 1, 1-bis (pyridin-2-yl) -N-methyl-N- (pyridin-2ylmethyl) methylamifle; 1,1-bis(pyridin-2-yl) -N,N-bis(6-methyl-pyridin-2ylmethyl) methylamine; 1,1-bis(pyridin-2-yl) -N,N-bis(5-carboxymethyl-pyridifl 2 ylmethyl) methylamine; 1,l-bis(pyridin-2-yl) -1-benzyl-N,N-bis(pyridifl2ylmethyl) methylamine; and 1, 1-bis (pyridin-2y1) -N,N-bis (benzimidazol-2ylmethyl) methylamine.

In a variant of this aspect, the group Z4 in formula (IIA) represents a group of the general formula (IIAa): (I IAa) In this variant, 04 preferably represents optionally substituted alkylene, preferably -CH 2

-CHOH-CH

2 or -CH 2

-CH

2

CH

2 In a preferred embodiment of this variant, the ligand is: W001/16268 WO 0116268PCTIEP00IO756I 16 Py Py Py r /Py H-C-NN-

H

Py Py wherein -Py represents pyridin-2-yl.

In another aspect, the group U in formula (IA) represents a coordinating group of the general formula (IIIA):

(IIIA)

wherein j is 1 or 2, preferably 1.

According to this aspect, each Q2 preferably represents

(CH

2 and each Z3 preferably represents -NCR)wherein R -H or C 14 -alkyl, preferably methyl.

In preferred embodiments of this aspect, the ligand is selected from: Py\ 1M H-C-N N M e PY M e Me-C-N N PyJ MeC wherein -Py represents pyridin-2-yl.

WO 01/16268 WOOI/6268PCr/EPOOIO7561 17 In yet another aspect, the group U in formula (IA) represents a coordinating group of the general formula

(IVA):

p-Zi -Q -T

(IVA)

In this aspect, Q preferably represents (wherein T=- H, methyl, or benzyl) or pyridin-diyl.

In preferred embodiments of this aspect, the ligand is selected from: Py H Py Py Py Me-C-N-C-Me CeOC -c 7 Me Py Py Py Py Py Py Py Py wherein -Py represents pyridin-2-yl, and represents pyridin-2, 6-diyl.

Ligands of the general formula (IB): WO 01/16268 WO 0116268PCIEPOO/07561 18-

R

3

(IB)

where in n 1 or 2, whereby if n 2, then each -Q 3

-R

3 group i s independently defined; RI, R 2

R

3

R

4 independently represent a group selected from hydrogen, hydroxyl, halogen, -NH-C(NH)N1 2 -R and -OR, wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkYl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, Q1, Q2, Q3, Q 4 and Q independently represent a group of the formula: bc R6 B8 wherein a+b+c a=0-5; b=0-5; c=0-5; n=1 or 2; WO 01/16268 PCT/EP00/07561 19 Y independently represents a group selected from -S02-, arylene, alkylene, heteroarylene, heterocycloalkylene, and wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6, or R7 together with R8, or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8, or R5 together with R8 and/or independently R6 together with R7, represent C 1 6 -alkylene optionally substituted by C 1 -4-alkyl, -Cl, -Br or -I, provided that at least two of R 1

R

2

R

3

R

4 comprise coordinating heteroatoms and no more than six heteroatoms are coordinated to the same transition metal atom.

At least two, and preferably at least three, of R 1

R

2

R

3

R

4 independently represent a group selected from carboxylate, amido, -NH-C(NH)NH 2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, WO 01/16268 WO 0116268PCT/EPOO/07561 20 quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.

Preferably, substituents for groups R 1

R

2

R

3

R

4 when representing a heterocyclic or heteroaromatic ring, are selected from C 1 .4-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl- The groups Q1, Q2, Q3, Q 4 preferably independently represent a group selected from -CH 2 and -CH 2

CH

2 Group Q is preferably a group selected from -(CM 2 2 4

CH

2 CH (OH) CH 2 optionally substituted by methyl or ethyl, OH Nan wherein R represents -H or C 14 -alkyl.

Preferably, Q 1

Q

2

Q

3 are defined such that a=b=0, c=1 and n=l, and Q is defined such that a=b=o, c=2 and n=1.

The groups R5, R6, R7, RB preferably independently represent a group selected from hydroxy-Co-C 2 o-alkyl, halo-CO-C 2 0 alkyl, nitroso, formyl-CO-C 20 -alkyl, carboxyl-CO-C20-alkyl and esters and salts thereof, carbamoyl-CO-C 2 0-alkyl, sulfo-Co-

C

20 -alkyl and esters and salts thereof, sulfamoyl-CO-C2oalkyl, amino-CO-C 20 -alkyl, aryl-C 0

-C

2 0 -alkyl, CO-C 20 -alkyl, WO 01/16268 PCT/EP0O/07561 21 alkoxy-Co-C 8 -alkyl, carbonyl-Co-C 6 -alkoxy, and Co-C 2 0 alkylamide. Preferably, none of R5-R8 is linked together.

In a preferred aspect, the ligand is of the general formula

(IIB):

RI-Qk Q4-R4

/N-Q-N,

R2-Q2 Q3-R3

(IIB)

wherein Qi, Q2, Q3, Q4 are defined such that a=b=0, c=l or 2 and n=l; Q is defined such that a=b=O, c=2,3 or 4 and n=l; and Ri, R 2

R

3

R

4 R7, R8 are independently defined as for formula Preferred classes of ligands according to this aspect, as represented by formula (IIB) above, are as follows: ligands of the general formula (IIB) wherein:

R

1

R

2

R

3

R

4 each independently represent a coordinating group selected from carboxylate, amido, -NH-

C(NH)NH

2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.

WO 01/16268 PCT/EP00/07561 22 In this class, we prefer that: Q is defined such that a=b=0, c=2 or 3 and n=l;

R

1

R

2

R

3

R

4 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl.

(ii) ligands of the general formula (IIB) wherein:

R

1

R

2

R

3 each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH 2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; and

R

4 represents a group selected from hydrogen, Ci- 20 optionally substituted alkyl, C 1 -2 0 optionally substituted arylalkyl, aryl, and C 1 -20 optionally substituted NR3* (wherein R=C1_B-alkyl).

In this class, we prefer that: Q is defined such that a=b=0, c=2 or 3 and n=l;

R

1

R

2

R

3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-l-yl, and optionally substituted quinolin-2-yl; and WO 01/16268 PCT/EP00/07561 23

R

4 represents a group selected from hydrogen, Ci- 10 optionally substituted alkyl, C 1 -s-furanyl, C 1 i- optionally substituted benzylalkyl, benzyl, C1-s optionally substituted alkoxy, and CI-20 optionally substituted N+Me 3 (iii) ligands of the general formula (IIB) wherein: RI, R 4 each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH 2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; and

R

2

R

3 each independently represent a group selected from hydrogen, Ci- 20 optionally substituted alkyl, C 1 -2 0 optionally substituted arylalkyl, aryl, and Ci- 20 optionally substituted NR3' (wherein R=Ci-8-alkyl) In this class, we prefer that: Q is defined such that a=b=0, c=2 or 3 and n=l;

R

1

R

4 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-l-yl, and optionally substituted quinolin-2-yl; and

R

2

R

3 each independently represent a group selected from hydrogen, Ci-io optionally substituted alkyl, C 1 -sfuranyl, C1-s optionally substituted benzylalkyl, benzyl, C1-s optionally substituted alkoxy, and CI- 20 optionally substituted N+Me 3 WO 01(6268 PcT/EPOO/07561 24 Examples of preferred ligands in their simplest forms are: N,N' -tris (3-methyl-pyridir2-ylmethyl) -ethylenediamile; N-trimethylammofliumpropyl-N,N' -tris (pyridin-2-ylmethYl) ethylenediamifle; N- (2-hydroxyethylele) -tris (pyridin-2-ylmlethyl) ethylenediamnie; N,N,N' -tetrakis(3-mfethyPpyridifl2-ylmethyl) -ethylenediamine; NN' -dimethyl-N,N' -bis (pyridin-2-ylmethyl) -cyclohexane- 1 2diamine; N- C2-hydroxyethylele) -tris (3-methyl-pyridil-2ylmethyl) -ethylenediamine; N-methyl-N,N' -tris(pyridin-2-ylmfethyl) -ethylenediamile; N-methyl-N,N' ,Nl-tris(5-ethyl-pyridifl-2-ylmethyl) ethyl enedi amine; N-methyl-N,N' ,NI-tris (5-methyl-pyridiri-2-ylmfethyl) ethyl enediamine; N-methyl-N,N' lti(3mty-prdn2 lehlethylenediamile; N-benzyl-N,N' ,Nl-tris(3-methyl-pyridifl2-ylmethyl) ethyl enediamine; N-ethyl-N,N' ,Nl-tris(3-mfethyl-pyridin-2-ylmethyl) ethylenediamnie; N,N,N' -tris (3-methyl-pyridin-2-ylnethyl) -methoxyethyl-i) -ethylenediamine; N,N,NI-tris(1lTfethylbefzinidazol2yl)N'methylethyl enedi amine; N-(furan-2-yl) lti(3mty-prdn2 lehlethylenediamine; WO 01/16269 WO 011626pCT/EPOO/07561 25 N- (2-hydroxyethylele) -tris (3-ethyl-pyridil-2yimethyl) -ethylenediamine; N-methyl-N,N' -tris (3-methyi-pyridifl>-ylmethyl)ethylene- 1,2-diamine; N-ethyl-N,N' -tris C3-methyl-pyridifl-2-ylmethyl) ethylene- 1, 2-diamine; N-benzyl-N,N' -tris (3-methyl-pyridil-2-ylmfethyl) ethylene- 1,2-diamile; N- (2-hydroxyethyl) ,N'-tris(3-mfethyl-pyridil- 2 ylmethyi) ethylene-i, 2-diamine; N- (2-methoxyethyl) -tris (3-methyl -pyridin-2ylmethyl) ethylene-i, 2-diamine; N-methyl-N,N' -tris (5-methyl-pyridif-2-ylmethyl) ethylene- 1,2-diamile; N-ethyl-N,N' -tris (5-methyl-pyridil-2ylmfethyl) ethylene- 1,2 -diamine; N-benzyl-N,N' -tris (5-rethyl-pyridifl2-ylmethyl) ethylene- 1,2-diamile; N- (2-hydroxyethyl) -tris(5-methyl-pyridifl 2 ylmethyl) ethylene- 1,2 -di amine; N- (2-methoxyethyl) -tris(5-methyl-pyridin- 2 ylmethyl) ethylene-i, 2-diamine; N-methyl-N,N' lti(-ehlprdi--lehy~tyee 1,2-diamine; N-ethyl-N,N',N-rs3ehl yii--lety~tyee 1, 2-diamine; N-benzyi-N,N' rs3ehl-yii--lety~tyee 1, 2-diJamine; WO 01116268 WO 0116268PCT/EPOO/07561 26 N- (2-hydroxyethyl) ,N'-tris (3-ethyl-pyridifl-2ylmethyl) ethylene- 1,2 -diamine; N- (2-methoxyethyl) -tris(3-ethyl-pyridin-2ylmethyl) ethylene-i, 2-diamine; N-methyl-N,N' -tris (5-ethyl-pyridin-2-ylmethyl) ethylene- 1, 2-diamifle; N-ethyl-N,N' ,NI-tris(5-ethyl-pyridifl2-ylmethyl)ethylene- 1, 2-diamine; N-benzyl-N,N' -tris(5-ethyl-pyridif-2-ylmethyl)ethylene- 1,2-diamine; and N- (2-methoxyethyl) -tris (5-ethyl -pyridin-2ylmethyl) ethylene-i, 2-diamine.

More preferred ligands are: N-methyl-N,N' -tris(3-methyl-pyridifl2>ylmethyl)ethylene- 1, 2-diamine; N-ethyl-N,N' -tris(3-methyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine; N-benzyl-N,N' lti(-ehy-yii--lmty~tyee 1,2-diamine; N- (2-hydroxyethyl) -tris (3-methyl-pyridil-2ylmethyl) ethylene-i, 2-diamine; and N- (2-methoxyethyl) -tris(3-methyl-pyridifl2ylmethyl)ethylene-1, 2-diamine.

Ligands of the general formula (IC): WO OV16269 WO 0116268PCT/EPOO/07561 27z 2

(IC)

wherein Z1, Z 2 and Z 3 independently represent a coordinating group selected from carboxylate, amido, -Nli-C(NH)NH 2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; Q1, Q2, and Q3 independently represent a group of the formula: +b ]a R6 R8 wherein a+b+c 1; a=0-5; b=0-5; c=0-5; n=1 or 2; WO 01/16268 PCT/EP00/07561 28 Y independently represents a group selected from -SO2-, arylene, alkylene, heteroarylene, heterocycloalkylene, and wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; and R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6, or R7 together with R8, or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8, or R5 together with R8 and/or independently R6 together with R7, represent Ci_--alkylene optionally substituted by C1-4-alkyl, -Cl, -Br or -I.

Zi, Z 2 and Z 3 each represent a coordinating group, preferably selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl. Preferably, Z 1

Z

2 and

Z

3 each represent optionally substituted pyridin-2-yl.

Optional substituents for the groups Z 1

Z

2 and Z 3 are preferably selected from C1_ 4 -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl, preferably methyl.

WO 01/16268 WO 0116268PCT/EPOO/07561 29 Also preferred is that Q1, Q2 and Q3 are defined such that a=b=0, c=1 or 2, and n=1.

Preferably, each Q1, 02 and 03 independently represent C 1 4 alkylene, more preferably a group selected from -CH 2 and

CH

2

CH

2 The groups R5, R6, R7, R8 preferably independently represent a group selected from hydroxy-CO-C 20 -alkyl, halo-CO-C 2 0 alkyl, nitroso, formyl-C 0

-C

2 0 -alkyl, carboxyl-Co-C 2 o-alkyl and esters and salts thereof, carbamoyl-CO-C 20 -alkyl, sulfo-Co-

C

2 0 -alkyl and esters and salts thereof, sulfamoyl-Co-C2oalkyl, amino-CO-C 2 0 -alkyl, aryl-CO-C 20 -alkyl, C 0

-C

20 -alkyl, alkoxy-Co-CB-alkyl, carbonyl-C 0

-C

6 -alkoxy, and CO-C 2 0 alkylamide. Preferably, none of R5-R8 is linked together.

Preferably, the ligand is selected from tris~pyridin-2ylmethyl) amine, tris (3-methyl-pyridin-2-ylmethyl) amine, tris (5-methyl-pyridin-2-ylmethyl) amine, and tris (6-methylpyridin-2-ylmethyl) amine.

Ligands of the general formula (ID):

RN

N

R

(ID)

WO 01/16268 PCT/EPOO/07561 30 wherein RI, R 2 and R 3 independently represent a group selected from hydrogen, hydroxyl, halogen, -NH-C(NH)NH 2 -R and -OR, wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E; .0 Q independently represent a group selected from C 2 3 alkylene optionally substituted by H, benzyl or CI-e-alkyl; Qi, Q2 and Q3 independently represent a group of the formula: wherein a+b+c 1; a=0-5; b=0-5; c=0-5; n=l or 2; Y independently represents a group selected from

-SO

2 arylene, alkylene, heteroarylene, heterocycloalkylene, and wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, WO 01/16268 PCT/EP00/07561 31 cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; and R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R5 together with R6, or R7 together with R8, or both, represent oxygen, or R5 together with R7 and/or independently R6 together with R8, or R5 together with R8 and/or independently R6 together with R7, represent C 1 s_-alkylene optionally substituted by C 1 -4-alkyl, -Cl, -Br or -I, provided that at least one, preferably at least two, of

R

1

R

2 and R 3 is a coordinating group.

At least two, and preferably at least three, of RI, R 2 and R 3 independently represent a group selected from carboxylate, amido, -NH-C(NH)NH 2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole. Preferably, at least two of RI, R 2

R

3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-l-yl, and optionally substituted quinolin-2-yl.

WO 01/16268 WO 0116268PCT/EPOO/07561 32 Preferably, substituents for groups R 1

R

2

R

3 when representing a heterocyclic or heteroaromatic ring, are selected from C 1 4 -alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl.

Preferably, Q3., Q2 and Q3 are defined such that a=b=C, c=1,2,3 or 4 and n=1. Preferably, the groups Q 1 Q2 and Q3 independently represent a group selected from -CH 2 and-

CH

2

CH

2 Group Q is preferably a group selected from -CH 2

CH

2 and-

CH

2

CH

2

CH

2 1s The groups R5, R6, R7, R8 preferably independently represent a group selected from hydroxy-CO-C 2 0-alkyl, halo-CO-C 2 0 alkyl, nitroso, formyl-CO-C 20 alkyl, carboxyl-Ca-C 2 0-alkyl and esters and salts thereof, carbamoyl-CO-C 20 -alkyl, sulfo-Co-

C

20 -alkyl and esters and salts thereof, sulfamoyl-CO-C 20 alkyl, amino-C 0

-C

20 -alkyl, aryl-CO-C 20 -alkyl, C 0

-C

20 -alkyl, alkoxy-C 0 -Ca-alkyl, carbonyl-CO-C 6 -alkoxy, and CO-C 2 0 alkylamide. Preferably, none of R5-R8 is linked together.

In a preferred aspect, the ligand is of the general formula

(IID):

WO 01/16268 PCr/EPOO/07561 33 aQ--R2 2 N N R1-0-1 R3

(IID)

wherein R1, R2, R3 are as defined previously for R1, R 2

R

3 and Q 1 Q2, Q3 are as defined previously.

Preferred classes of ligands according to this preferred aspect, as represented by formula (IID) above, are as follows: ligands of the general formula (IID) wherein: R1, R2, R3 each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH 2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole.

In this class, we prefer that: R1, R2, R3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-l-yl, and optionally substituted quinolin-2-yl.

WO 01/16268 PCT/EPOO/07561 34 (ii) ligands of the general formula (IID) wherein: two of R1, R2, R3 each independently represent a coordinating group selected from carboxylate, amido, -NH-

C(NH)NH

2 hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; and one of R1, R2, R3 represents a group selected from hydrogen, Ci- 20 optionally substituted alkyl, C 1 -2 0 optionally substituted arylalkyl, aryl, and Ci- 20 optionally substituted

NR

3 (wherein R=C-_ 8 -alkyl) In this class, we prefer that: two of R1, R2, R3 each independently represent a coordinating group selected from optionally substituted pyridin-2-yl, optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-l-yl, and optionally substituted quinolin-2-yl; and one of R1, R2, R3 represents a group selected from hydrogen, C 1 -io optionally substituted alkyl, C1-s-furanyl, C 1 ioptionally substituted benzylalkyl, benzyl, C 1 i- optionally substituted alkoxy, and Ci- 20 optionally substituted N+Me 3 In especially preferred embodiments, the ligand is selected from: WO 01/16268 WO 0116268PcT/EPOO/07561 35 -N j PO Pzl

N

I

Qu Nj

I

Pz\~ N NX~Et

PZN

Et wherein -Et represents ethyl, -Py represents pyridin-2-y., Pz3 represents pyrazol-3-yl, Pzl represents pyrazol-1-yl, and Qu represents quinolin-2-yl.

Ligands of the general formula (IE): T1- (Q1) rI 5 (Q2) g-T2 R1 R2

(IE)

wherein g represents zero or an integer from 1 to 6; r represents an integer from 1 to 6; s represents zero or an integer from 1 to 6; WO 01/16268 PCT/EPOO/07561 36 Q1 and Q2 independently represent a group of the formula: R6 R8 d- e- R7 R9 wherein 5 d+e+f 1; d=0-5; e=0-5; each Y1 independently represents a group selected from

-SO

2 arylene, alkylene, heteroarylene, heterocycloalkylene, and wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; if s>l, each group is independently defined; R1, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R6 together with R7, or R8 together with R9, or both, represent oxygen, or R6 together with R8 and/or independently R7 together with R9, or R6 together with R9 and/or independently R7 WO 01/16268 PCT/EPOO/07561 37 together with R8, represent C-1_-alkylene optionally substituted by C 1 4 -alkyl, -C1, -Br or -I; or one of R1-R9 is a bridging group bound to another moiety of the same general formula; T1 and T2 independently represent groups R4 and wherein R4 and R5 are as defined for R1-R9, and if g=0 and s>0, R1 together with R4, and/or R2 together with R5, may optionally independently represent =CH-R10, wherein R10 is as defined for R1-R9, or Tl and T2 may together represent a covalent bond linkage when s>l and g>0; if T1 and T2 together represent a single bond linkage, Q1 and/or Q2 may independently represent a group of the formula: provided R1 and/or R2 are absent, and R1 and/or R2 may be absent provided Q1 and/or Q2 independently represent a group of the formula: =CH- e-CH=.

The groups R1-R9 are preferably independently selected from hydroxy-Co-C 20 -alkyl, halo-Co-C 20 -alkyl, nitroso, formyl- Co-C 20 -alkyl, carboxyl-Co-C 20 -alkyl and esters and salts thereof, carbamoyl-Co-C 20 -alkyl, sulpho-Co-C 20 -alkyl and esters and salts thereof, sulphamoyl-Co-C 20 -alkyl, amino-Co-

C

20 -alkyl, aryl-Co-C 20 -alkyl, heteroaryl-Co-C 20 -alkyl, Co-C 20 alkyl, alkoxy-Co-Cs-alkyl, carbonyl-Co-C 6 -alkoxy, and aryl-Co- Cs-alkyl and Co-C 20 -alkylamide.

One of R1-R9 may be a bridging group which links the ligand moiety to a second ligand moiety of preferably the same WO 01/16268 PCT/EPOO/07561 38 general structure. In this case the bridging group is independently defined according to the formula for Q1, Q2, preferably being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge, more preferably C 1 6 -alkylene optionally substituted by C 1 -4-alkyl, -Cl, -Br or -I.

In a first variant according to formula the groups T1 and T2 together form a single bond linkage and s>l, according to general formula (IIE): Ql)r

R\

Y I-

RI

(IIE)

wherein R3 independently represents a group as defined for R1-R9; Q3 independently represents a group as defined for Q1, Q2; h represents zero or an integer from 1 to 6; and s=s-l.

In a first embodiment of the first variant, in general formula (IIE), s=l, 2 or 3; r=g=h=l; d=2 or 3; e=f=0; R6=R7=H, preferably such that the ligand has a general formula selected from: WO 01/16268 PCT/EP0O/07561 39 R1\ R1 R1 N N

N

N-R3 N-R3 R3 R2 R2 R2 R1N R1, N R2 R,R2 -IN N N N N-R3N N N

N

RN R R4' N R3 R4 I 1'R 3 R1\ R 2 -N

N

R5 N NR3 R4 In these preferred examples, R1, R2, R3 and R4 are preferably independently selected from alkyl, aryl, heteroaryl, and/or one of R1-R4 represents a bridging group bound to another moiety of the same general formula and/or two or more of R1-R4 together represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene or hydroxy-alkylene or a heteroarylcontaining bridge, preferably heteroarylene. More preferably, R1, R2, R3 and R4 are independently selected from methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxyalkylene.

WO 01/16268 PCT/EP00/07561 40 In a second embodiment of the first variant, in general formula (IIE), s=2 and r=g=h=l, according to the general formula:

RI

represent -CH2- [-Y1-]-CH 2 Thus, preferably the ligand has the general formula: SjA /N NQ R3 wherein A represents optionally substituted alkylene.

optionally interrupted by a heteroatom; and n is zero or an integer from 1 to Preferably, R1-R6 represent hydrogen, n=1 and A= -CH 2 CHOH-, -CH 2

N(R)CH

2 or -CH 2

CH

2

N(R)CH

2

CH

2 wherein R represents hydrogen or alkyl, more preferably A= -CH 2 -CHOH- or

CH

2

CH

2

NHCH

2

CH

2 CH2CH2NHCHCH2- WO 01/16268 PCTIEP00/07561 41 In a second variant according to formula T1 and T2 independently represent groups R4, R5 as defined for R1-R9, according to the general formula (IIIE): R4- (Q1) (Q2) 9 R1 R2

(IIIE)

In a first embodiment of the second variant, in general formula (IIIE), s=l; r=l; g=0; d=f=l; e=0-4; Yl= -CH 2 and R1 together with R4, and/or R2 together with independently represent =CH-R10, wherein R10 is as defined for R1-R9. In one example, R2 together with R5 represents with R1 and R4 being two separate groups.

Alternatively, both R1 together with R4, and R2 together with R5 may independently represent =CH-R10. Thus, preferred ligands may for example have a structure selected from: R2 R3 R2 R3 Re CH 2 Rs R CH 2

R

N R7-N N-\

R

1 R4 RR wherein n 0-4.

Preferably, the ligand is selected from: R N R-N N\R RR 1 WO 01/16268 PCT/EP0/07561 42 wherein Rland R2 are selected from optionally substituted phenols, heteroaryl-Co-C20-alkyls, R3 and R4 are selected from alkyl, aryl, optionally substituted phenols, heteroaryl-Co-C 2 o-alkyls, alkylaryl, aminoalkyl, alkoxy, more preferably R1 and R2 being selected from optionally substituted phenols, heteroaryl-Co-C 2 -alkyls, R3 and R4 are selected from alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-Co-C 2 -alkyls.

In a second embodiment of the second variant, in general formula (IIIE), s=l; r=l; g=0; d=f=l; e=l-4; Y1= wherein R' and R" are independently as defined for R1-R9.

Preferably, the ligand has the general formula: RI R 2 R5 R3 R1 R 4 I J"\ R7-N R6 N-R9 8

R

10 The groups R1, R2, R3, R4, R5 in this formula are preferably -H or Co-C 20 -alkyl, n=0 or 1, R6 is alkyl, -OH or -SH, and R7, R8, R9, R10 are preferably each independently selected from Co-C 20 -alkyl, alkoxy-Co-Ce-alkyl and amino-Co-C 20 -alkyl.

In a third embodiment of the second variant, in general formula (IIIE), s=0; g=l; d=e=0; f=l-4. Preferably, the ligand has the general formula: WO 01/16268 pCTEPOO/07561 43 R2 R1 R3 R4 This class of ligand is particularly preferred according to the invention.

More preferably, the ligand has the general formula: I R1 N N R2 NR3 wherein R1, R2, R3 are as defined for R2, R4, In a fourth embodiment of the second variant, the ligand is a pentadentate ligand of the general formula (IVE):

R

3

C--N

R1 R 2

(IVE)

wherein each R 1

R

2 independently represents -R-R 5

R

3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R 4

-R

5 each R 4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, WO 01/16268 PCT/EPOO/07561 44 aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R 5 independently represents an optionally Nsubstituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.

Ligands of the class represented by general formula (IVE) are also particularly preferred according to the invention.

The ligand having the general formula (IVE), as defined above, is a pentadentate ligand. By 'pentadentate' herein is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex.

In formula (IVE), one coordinating hetero atom is provided by the nitrogen atom in the methylamine backbone, and preferably one coordinating hetero atom is contained in each of the four R 1 and R 2 side groups. Preferably, all the coordinating hetero atoms are nitrogen atoms.

The ligand of formula (IVE) preferably comprises at least two substituted or unsubstituted heteroaryl groups in the four side groups. The heteroaryl group is preferably a pyridin-2-yl group and, if substituted, preferably a methylor ethyl-substituted pyridin-2-yl group. More preferably, the heteroaryl group is an unsubstituted pyridin-2-yl group.

Preferably, the heteroaryl group is linked to methylamine, and preferably to the N atom thereof, via a methylene group.

Preferably, the ligand of formula (IVE) contains at least one optionally substituted amino-alkyl side group, more WO OV16268 WO 0116268PCT/EPOO/07561 45 preferably two amino-ethyl side groups, in particular 2-(Nalkyl)amino-ethyl or 2- (N,N-dialkyl) amino-ethyl.

Thus, in formula (lyE) preferably R 1 represents pyridin-2-yl or R 2 represents pyridin-2-yl-methyl. Preferably R 2 or R represents 2-amino-ethyl, 2- ethyl) amino-ethyl or 2- (N,N-di (in)ethyl)amino-ethyl. If substituted, R 5 preferably represents 3-methyl pyridin-2-yl. R 3 preferably represents hydrogen, benzyl or methyl.

Examples of preferred ligands of formula (lyE) in their simplest forms are: pyridin-2-yl containing ligands such as: N,N-bis (pyridin-2-yl-methyl) -bis(pyridin-2-yl)nethylamine; N,N-bis(pyrazol-1-yl-methyl) -bis(pyridin-2-yl)methylamfine; N,N-bis (imidazol-2-yl-methyl) -bis(pyridin-2-yl)methylamine; yl) methylamine; N,N-bis(pyridin-2-yl-nethyl) -bis(pyrazol--yl)methylaile; N,N-bis (pyridin-2-yl-methyl) -bis (imidazol-2-yl)methylamile; N,N-bis(pyridin-2-yl-methyl) -bis(l,2,4-triazol-lyl) methyl amine; N,N-bis Cpyridin-2-yl-methyl) 1-bis (pyridin-2-yl) -1aminoethane; N,N-bis(pyridin-2-yl-methyl) -l,1-bis(pyridin-2-y1) -2-phenyl- 1-aminoethane; N,N-bis(pyrazol-1-yl-nethyl) -l,l-bis(pyridin-2-yl) -1aminoethane; N,N-bis(pyrazol-l-yl-methyl) -1,1-bis (pyridin-2-yl) -2-phenyl- 1 -aminoethane; WO 01116268 WO 0116268PCI7IEPOOIO7561 46 N,N-bis (imidazol-2-yl-methyl) 1-bis (pyridin-2-yl) -1aminoethane; N,N-bis (imidazol-2-yl-methyl) 1-bis (pyriciin-2-yl) -2phenyl -1-aminoethane; N,-i 1 ,-rao--lmty)-,1bs(yii--l

I

aminoethane; phenyl -1-aminoethane; N,N-bis (pyridin-2-yl-methyl) 1-bis (pyrazol-1-yl) -1aminoethane; N,N-bis(pyridin-2-y1-methyl)-1,1-bis(pyrazol-1-yl) -2-phenyl- 1- aminoethane; N,N-bis (pyridin-2-yl-methyl) 1-bis (imidazol-2-yl) -1aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1-bis~imidazol-2-yl) -2pheny.- i-aniinoethane; aminoethane; N,N-bis (pyridin-2-yl-methyl) 1-bis (pyrid-i2-l-1-y)aminoethaie; N,N-bis(pyridin-2-yl-methyl) -i,1-bis(pyridin-2-yl) -1aminoehane; N,N-bis(pyridin-2-yl-methyl) -i,1-bis(pyridifl-2-yl) -2-phn 1 aminoetane; NN-bis(pyridin-2-y1-mfethy)-1,1-bis(pyridifl2-yl) (4suiphonic acid-phenyl) -1-aminoethane; N,N-bis (pyridin-2-yl-methyl) 1-bis (pyridin-2-yl) -2- (pyridin-2-yl) -1-aminoethane; WO 01/16268 WO 0116268PCT/EPOO/07561 47 N,N-bis(pyridifl-2-yl-methyl) -1,l-bis(pyridil-2-yl) -2- (pyridin-3-yl) -1-aminoethane; N,N-bis (pyridin-2-yl-methyl) 1-bis (pyridin-2-yl) -2- (pyridin-4 -yl) -aminoethale; N,N-bis(pyridifl2-ylrfethyl)-1,1-bis(pyridin-2-yl)-2-(lalkyl-pyridiflium-4-yl) -aminoethane; N,N-bis (pyridin-2-yl-methyl) 1-bis (pyridin-2-yl) (1alkyl-pyridiflium-3-yl) -1-aminoethane; N,N-bis (pyridin-2-yl-methyl) 1-bis (pyridin-2-yl) (1alkyl-pyridinium-2-yl) -1-aminoethane; (ii) 2-amino-ethyl containing ligands such as: N,N-bis (N-alkyl) amino-ethyl) -bis (pyridin-2yl) met hylamine; N,N-bis(2- (N-alkyl)amiflo-ethyl) -bis(pyrazol-lyl) methylamine; N,N-bis(2- CN-alkyl)amino-ethyl) -bis(imidazol-2yl) methylamine; N,N-bis(2-CN-alkyl)amfiflo-ethylbi(,2,4triazol yl)methylamine; N,N-bis(2- (N,N-dialkyl)amino-ethyl) -bis(pyridin-2yl) methylamine; N,N-bis (N,N-dialkyl)amino-ethyl) -bis(pyrazol-1yl) methyl amine; N,N-bis(2-(N,N-dialky1)amino-ethyl)-bis(imidazol- 2 yl) methylamine; N,N-bis(2-(N,N-dialky1)amifoethyl)-bis1,2,4triazol-l yl) methylamine; N,N-bis (pyridin-2-yl-methyl) -bis (2-amino-ethyl)methylamine; N,N-bis~pyrazol-1-yl-methyl) -bis(2-amino-ethyl)methylamine; N,N-bis(imidazol-2-yl-methyl) -bis(2-amino-ethyi)methylamine; b WOO01/16268 FCTEPOO/07561 48 ethyl) methylamine.

More preferred ligands are: N,M-bis (pyridin-2-yl-methyl) -bis (pyridin-2-yl)methylaile, hereafter referred to as N4Py.

N,M-bis (pyridin-2-yl-methyl) 1-bis (pyridin-2-yl) -1aminoethane, hereafter referred to as MeN4Py, N,N-bis (pyridin-2-yl-methyl) 1-bis (pyridin-2-yl) -2-phenyl- 1-aminoethane, hereafter referred to as BzN4Py.

In a fifth embodiment of the second variant, the ligand represents a pentadentate or hexadentate ligand of general formula (yE):

R'R'N-W-NR

1

R'

(VE)

wherein each R' independently represents -R 3 in which R 3 represents optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; W represents an optionally substituted alkylene bridging group selected from

-CH

2

CH-

2

-CH

2

CH

2

CH-

2

-CH

2

CH

2

CH

2

CH

2

-CH

2

-C

6

H,-CH

2

-CH

2

-C

6

H

1 0

CH

2 and -CH 2 -Cl 0

I-I-CH

2 and WO 01/16268 PCT/EPOO/07561 49

R

2 represents a group selected from R 1 and alkyl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N*(R 4 3 wherein R 4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether and alkenyl ether.

The ligand having the general formula as defined above, is a pentadentate ligand or, if R'=R 2 can be a hexadentate ligand. As mentioned above, by 'pentadentate' is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex. Similarly, by 'hexadentate' is meant that six hetero atoms can in principle coordinate to the metal M ion. However, in this case it is believed that one of the arms will not be bound in the complex, so that the hexadentate ligand will be penta coordinating.

In the formula two hetero atoms are linked by the bridging group W and one coordinating hetero atom is contained in each of the three R 1 groups. Preferably, the coordinating hetero atoms are nitrogen atoms.

The ligand of formula (VE) comprises at least one optionally substituted heteroaryl group in each of the three R 1 groups.

Preferably, the heteroaryl group is a pyridin-2-yl group, in particular a methyl- or ethyl-substituted pyridin-2-yl group. The heteroaryl group is linked to an N atom in formula preferably via an alkylene group, more preferably a methylene group. Most preferably, the WO 01/16268 PCT/EP0O/07561 50 heteroaryl group is a 3-methyl-pyridin-2-yl group linked to an N atom via methylene.

The group R 2 in formula (VE) is a substituted or unsubstituted alkyl, aryl or arylalkyl group, or a group R 1 However, preferably R 2 is different from each of the groups

R

I in the formula above. Preferably, R 2 is methyl, ethyl, benzyl, 2-hydroxyethyl or 2-methoxyethyl. More preferably,

R

2 is methyl or ethyl.

The bridging group W may be a substituted or unsubstituted alkylene group selected from -CH 2

CH

2

-CH

2

CH

2

CH

2

-CH

2

CH

2

CH-

2

CH

2

-CH

2

-C

6

H

4

-CH

2

-CH

2

-C

6 Hio-CH2-, and -CH 2

-C

1 oHs-CH 2 (wherein -CgH 4

-C

6

HI

0 -CoH 6 can be ortho-, para-, or meta-C 6

H

4

-C

6 HIo-, -C 1 oH 6 Preferably, the bridging group W is an ethylene or 1,4-butylene group, more preferably an ethylene group.

Preferably, V represents substituted pyridin-2-yl, especially methyl-substituted or ethyl-substituted pyridin- 2-yl, and most preferably V represents 3-methyl pyridin-2yl.

Ligands of the classes disclosed in WO-A-98/39098 and WO-A-98/39406.

The counter ions Y in formula (Al) balance the charge z on the complex formed by the ligand L, metal M and coordinating species X. Thus, if the charge z is positive, Y may be an anion such as RCOO-, BPh4-, C104-, BF4-, PFg-, RS0 3 RS0 4

SO

4 2 N0 3 O, Cl, Br-, or with R being hydrogen, WO 01/16268 PCT/EP00/07561 51 optionally substituted alkyl or optionally substituted aryl.

If z is negative, Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation.

Suitable counter ions Y include those which give rise to the formation of storage-stable solids. Preferred counter ions for the preferred metal complexes are selected from R 7

COO,

C104-, BF4-, PF 6 e, RSO3- (in particular CF 3 S0 3 RSO4-, SO 4 2 N0 3 Cl-, Br-, and wherein R represents hydrogen or optionally substituted phenyl, naphthyl or C 1

-C

4 alkyl.

It will be appreciated that the complex (Al) can be formed by any appropriate means, including in situ formation whereby precursors of the complex are transformed into the active complex of general formula (Al) under conditions of storage or use. Preferably, the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species. Alternatively, the catalyst may be formed in situ from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials.

In one such example, the active catalyst may be formed in situ in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent. Thus, for example, if M is iron, an iron salt such as FeSO 4 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex.

Thus, for example, the composition may formed from a mixture of the ligand L and a metal salt MX, in which preferably n=l- 5, more preferably 1-3. In another such example, the ligand L, or a ligand L-generating species, can be mixed with metal WO 01/16268 pCT/EP00/07561 52 M ions present in the substrate or wash liquor to form the active catalyst in situ. Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that comprise the ligand L and can be substituted by metal M ions to form the active complex according the formula (Al).

In typical washing compositions the level of the catalyst is such that the in-use level is from 1pM to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 MM.

Preferably, the pretreatment medium or wash liquor has a pH in the range from pH 6 to 13, more preferably from pH 6 to 11, still more preferably from pH 8 to 11, and most preferably from pH 8 to 10, in particular from pH 9 to In the context of the present invention bleaching should be understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate. However, it is envisaged that the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate. Furthermore, in the context of the present invention bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light. Thus, photobleaching compositions and processes relying on the use of photobleach catalysts or WO 01/16268 PCT/EPO0/07561 53 photobleach activators and the presence of light are excluded from the present invention.

According to the present invention, one or both of the pretreatment composition and the wash liquor are substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, whereby the catalytic bleaching by atmospheric oxygen or air will predominate.

However, in this case it will be appreciated that small amounts of hydrogen peroxide or peroxy-based or -generating systems may be included in the composition, if desired.

Therefore, by "substantially devoid of peroxygen bleach or peroxy-based or -generating bleach systems" is meant that the composition contains from 0 to 50 preferably from 0 to 10 more preferably from 0 to 5 and optimally from 0 to 2 by molar weight on an oxygen basis, of peroxygen bleach or peroxy-based or -generating bleach systems.

Preferably, however, the composition will be wholly devoid of peroxygen bleach or peroxy-based or -generating bleach systems.

Thus, at least 10 preferably at least 50 and optimally at least 90 of any bleaching of the stain substrate is effected by oxygen sourced from the air.

According to the present invention, preferably one of the pretreatment composition and the wash liquor contains a peroxygen bleach or a peroxy-based or -generating system.

The peroxy bleach may be a compound which is capable of yielding hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxides such as urea WO 01/16268 PCT/EPOO/07561 54 peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates. Mixtures of two or more such compounds may also be suitable.

Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because of its high active oxygen content. Sodium percarbonate may also be preferred for environmental reasons. The amount thereof in the composition of the invention usually will be within the range of about 5-35 by weight, preferably from 10-25 by weight.

Another suitable hydrogen peroxide generating system is a combination of a C 1

-C

4 alkanol oxidase and a CI-C 4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Such combinations are disclosed in WO-A-9507972, which is incorporated herein by reference.

Alkylhydroxy peroxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.

Organic peroxyacids may also be suitable as the peroxy bleaching compound. Such materials normally have the general formula: 0

II

Y-R-C-O-OH

WO 01/16268 PCT/EP00/07561 55 wherein R is an alkyl- or alkylidene- or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or -COOOH group or a quaternary ammonium group.

Typical monoperoxy acids useful herein include, for example: peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-a-naphthoic acid; (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP); and (iii) 6-octylamino-6-oxo-peroxyhexanoic acid.

Typical diperoxyacids useful herein include, for example: (iv) 1,12-diperoxydodecanedioic acid (DPDA); 1,9-diperoxyazelaic acid; (vi) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid; (vii) 2-decyldiperoxybutane-l,4-dioic acid; and (viii) 4,4'-sulphonylbisperoxybenzoic acid.

Also inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10 by weight, preferably from 4-8 by weight.

WO 01/16268 WO 0116268PCFIEPOO/07561 56 All these peroxy compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst not containing a transition metal.

Generally, the pretreatment composition can be suitably formulated to contain from 2 to 35%, preferably from 5 to by weight, of the peroxy bleaching agent.

Peroxyacid bleach precursors are known and amply described in literature, such as in GB-A-836988; GB-A-864,798; GB-A- 907,356; GB-A-l,003,310 and GB-A-1,519,351; DE-A-3,337,921; EP-A-O,185,522; EP-A-0,174,132; EP-A-0,120,591; and US-A- 1,246,339; US-A-3,332,882; US-A-4,128,494; TS-A-4,412,934 and US-A-4,675,393.

Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US-A-4,751,015 and US- A-4,397,757, in EP-A-0,284..292 and EP-A-331,229. Examples of peroxyacid bleach precursors of this class are: 2- (N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride (SPCC); N-octyl,N,N-dimethyl-NO-carbopheloxy decyl ammonium chloride

(ODC);

3- (N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.

A further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520; EP-A- 458,396 and EP-A-464,880.

WO 01/16268 PCT/EP00/07561 57 Any one of these peroxyacid bleach precursors can be used in the present invention, although some may be more preferred than others.

Of the above classes of bleach precursors, the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.

Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethylene diamine (TAED); sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4methyl-3-benzoloxy benzoate; 2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphophenyl carbonate chloride (SPCC); trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5trimethyl hexanoyl-oxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.

The precursors may be used in an amount of up to 12 preferably from 2-10 by weight, of the pretreatment composition.

The method of the present invention has particular application as a pretreatment in detergent bleaching, especially for laundry cleaning. Accordingly, the method preferably uses a wash liquor that contains a surface-active material, optionally together with detergency builder.

WO 01/16268 PCT/EP00/07561 58 Optionally, the pretreatment composition may also include a surface-active material, optionally together with detergency builder. The pretreatment composition may contain a surface-active material in an amount, for example, of from 10 to 50% by weight.

The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

Typical synthetic anionic surface-actives are usually watersoluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher aryl groups. Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C 8 -Ce 8 alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C 9

C

20 benzene sulphonates, particularly sodium linear secondary alkyl (Cio-C 1 s) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C 9 -Cie) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such WO 01/16268 pCT/EP0O/07561 59 as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alphaolefins (C 8

-C

20 with sodium bisulphite and those derived by reacting paraffins with SO 2 and Cl 2 and then hydrolysing with a base to produce a random sulphonate; sodium and ammonium

(C

7

-C

12 dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe material made by reacting olefins, particularly (C 10

-C

20 alpha-olefins, with SO3 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (Clo-Cis) alkylbenzene sulphonates, and sodium (C16-Cle) alkyl ether sulphates.

Examples of suitable nonionic surface-active compounds which may be used, preferably together with the anionic surfaceactive compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6

-C

22 phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (C 8

-C

18 primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO. Other socalled nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.

Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If WO 01/16268 PCT/EP00/07561 60 any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.

The pretreatment composition will preferably comprise from 1 to 15 wt of anionic surfactant and from 10 to 40 by weight of nonionic surfactant. In a further preferred embodiment, the detergent active system is free from C 16

-C

12 fatty acid soaps.

The pretreatment composition may also contain a detergency builder, for example in an amount of from about 5 to 80 by weight, preferably from about 10 to 60 by weight.

Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its watersoluble salts; the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and polyacetal carboxylates as disclosed in US-A-4,144,226 and US-A-4,146,495.

Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.

WO 01/16268 PCT/EPOO/07561 61 Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.

In particular, the pretreatment composition or wash liquor may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts. Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate and water-insoluble crystalline or amorphous aluminosilicate builder materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder.

It is preferred that the pretreatment composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, more preferably not more than 2.5 by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to Apart from the components already mentioned, the pretreatment composition or wash liquor can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers WO 01/16268 PCT/EP00/07561 62 such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives Dequest® types); fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate and sodium silicate; and, usually in very small amounts, fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants.

Transition metal sequestrants such as EDTA, and phosphonic acid derivatives such as EDTMP (ethylene diamine tetra(methylene phosphonate)) may also be included, in addition to the catalyst ligand specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided the composition remains bleaching effective. However, the pretreatment composition containing the catalyst, is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the catalyst ligand).

Throughout the description and claims generic groups have been used, for example alkyl, alkoxy, aryl. Unless otherwise specified the following are preferred group restrictions that may be applied to generic groups found within compounds disclosed herein: WO 01/16268 WO 0116268PCT/EPOO/07561 63 alkyl: linear and branched Cl-C8-alkyl, alkenyl: C2-C6-alkenyl, cycloalkyl: C3-C8-cycloalkyl, alkoxy: Cl-C6-alkoxy, alkylene: selected from the group consisting of: methylene; 1,1-ethylene; 1,2-ethylene; 1,1-propylidene; 1,2-propylene; 1,3-propylene; 2,2-propylidene; butan-2-ol-1,4-diyl; propan- 2-ol-l,3-diyl; l,4-blutylene; cyclohexane-1,1-diyl; cyclohexan-1,2-diyl; cyclohexan-1,3-diyl; cyclohexan-l, 4 diyl; cyclopentane-l, l-diyl; cyclopentan-1, 2-diyl; and cyclopentan-1,3-diyl, aryl: selected from homoaromatic compounds having a molecular weight under 300, arylene: selected from the group consisting of: 1,2phenylene; 1, 3-phenylene; 1, 4-phenylene; l,2-naphtalenylele; 1, 3-naphtalenylene; l,4-naphtalenylene; 2, 3-naphtalenylene; 1-hydroxy-2, 3-phenylene; 1-hydroxy-2,4-phenylele; 1-hydroxy- 2, 5-phenylene; and l-hydroxy-2, 6-phenylene, heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3, 5-triazirlyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, WO 01116268 WO 0116268PCTEPOO/07561 64 wherein the heteroary. may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridindiyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazindiyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroarylene, more specifically preferred are: pyridin-2,3-diyl; pyridin-2.,4-diyl; pyridin- 2,5-diyl; pyridin-2,6-diyl; pyridin-3,4-diyl; diyl; quinolin-2,3-diyl; quinolin-2,4-diyl; quinolin-2,8diyl; isoquinolin-l, 3-diyl; isoquinolin-1,4-diyl; pyrazol- 1,3-diyl; pyrazol-3,5-diyl; triazole-3,5-diyl; triazole-1,3diyl; pyrazin-2,5-diyl; and imidazole-2,4-diyl, heterocycloalkyl: selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7triazacyclononanyl; 1,4,8, il-tetraazacyclotetradecanyl; 1,4, 7,10, 13-pentaazacyclopentadecanyl; 1, 4-diaza-7-thiacyclononanyl; 1,4-diaza-7-oxa-cycloflofanyl; 1,4,7,10tetraazacyclododecanyl; 1, 4-dioxanyl; 1,4, 7-trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of: piperidin-1,2-ylene; piperidin-2,6-ylene; piperidin-4,4ylidene; l,4-piperazin-l,4-ylene; l,4-piperazin-2,3-ylele; l,4-piperazin-2,5-ylene; 1,4-piperazin-2,6-ylene; 1,4- WO 01/16268 WO 0116268PCTIEPOO7561 65 piperazin-1,2--ylene; 1,4-piperazin-1,3-ylele; 1,4-piperazin- 1, 4-ylene; tetrahydrothiophen-2, 5-ylene; tetrahydrothiophen- 3, 4-ylene; tetrahydrothiophen-2 ,3-ylene; tetrahydrofuran- 2, 5-ylene; tetrahydrofuran-3,4-ylene; tetrahydrofuran-2,3ylene; pyrrolidin-2, 5-ylene; pyrrolidin-3,4-ylele; pyrrolidin-2,3-ylene; pyrrolidin-1,2-ylene; pyrrolidin-1,3ylene; pyrrolidin-2,2-ylidene; 1,4,7-triazacycloflof-1, 4 ylene; 1,4,7-triazacyclonon-2,3-ylele; 1,4,7-triazacyCloflon- 2,9-ylene; 1,4,7-triazacyclonon-3,8-ylele; 1,4,7triazacyclonon-2, 2-ylidene; 1,4,8, ii-tetraazacyclotetradec- 1,4-ylene; 1,4,8,11-tetraazacyclotetradec-1,8-ylele; 1,4,8,11-tetraazacyclotetradeC-2,3-ylele; 1,4,8,11tetraazacyclotetradec-2, 5-ylene; 1,4,8,11tetraazacyclotetradec-1,2-ylene; 1,4,8,11- .tetraazacyclotetradec-2,2-ylidene; 1,4,7,10tetraazacyclododec-1, 4-ylene; 1,4,7, iO-tetraazacyclododec- 1,7-ylene; 1,4,7,10-tetraazacyclododec-1,2-ylele; 1,4,7,10tetraazacyclododec-2, 3-ylene; 1,4,7, io-tetraazacyclododec- 2,2-yliciene; 1,4,7,10,13-pentaazacycopeltadec-1,4-ylele; 1,4,7,10,13-pentaazacyclopentadec-1,7-ylele; 1,4,7,10, 13pentaazacyclopentadec-2,3-ylene; 1,4,7,10,13pentaazacyclopentadec-1,2-ylene; 1,4,7,10,13pentaazacyclopentadec-2, 2-ylidene; 1,4-diaza-7--thiacyclonon-1,4-ylene; 1,4-diaza-7-thia-cycloflof-1,2-ylele; 1,4-diaza-7-thia-cyclolof-2,3-ylele; 1,4-diaza-7-thiacyclonon-6,8-ylene; 1,4-diaza-7-thia-cycloflof-2,2-ylidele 1,4-diaza-7-oxa-cyclonofl-1,4-ylele; 1,4-diaza-7-oxacyclonon-1,2-ylene; 1,4-diaza-7-oxa-cyclonon-2,3-ylele; 1,4diaza-7-oxa-cyclonon-6,8-ylele; 1,4-diaza-7-oxa-cycloflof- 2,2-ylidene; 1,4-dioxan-2,3-ylene; 1,4-dioxan-2,6-ylele; 1,4-dioxan--2,2-ylideie; tetraliydropyran-24,3-ylele; WO 01/16268 WO 01/ 6268PCT/EPOO756 66 tetrahydropyran-2, 6-ylene; tetrahydropyran-2, tetrahydropyran-2 ,2-ylidene; l,4,7-trithia-cyclonofl- 2 3 ylene; l,4,7-trithia-cycloflof-2,9-ylele; and 1,4,7-trithiacyclonon-2, 2-ylidene, amine: the group -NCR) 2 wherein each R is independently selected from: hydrogen; C1-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R are C1-C6-alkyl both R together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl. substituent to the heterocyclic ring, halogen: selected from the group consisting of: F; Cl; Br and I, sulfonate: the group -S(O) 2 0R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-CGH5; Li; Na; K; Cs; Mg; and Ca, sulfate: the group -OS(O) 2 0R, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; C1-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, sulfone: the group -S(O) 2 R, wherein R is selected from: hydrogen; Cl-CE-alkyl; phenyl; Cl-C6-alkyl-C6H5 and amine (to give sulfonamide) selected from the group: -NR'2, wherein each RI is independently selected from: hydrogen; C1-C6-alkyl; Cl-C6-alkyl-C615; and phenyl, wherein when both RI are Cl-C6-alkyl both RI together may form an -NC3 to an NC5 heterocyclic ring with any remaining alkyl chain forming an alkvl substituent to the heterocyclic ring, WO 01/16268 PCT/EP00/07561 67 carboxylate derivative: the group -C(O)OR, wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl- Li; Na; K; Cs; Mg; and Ca, carbonyl derivative: the group wherein R is selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyland amine (to give amide) selected from the group: NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; Cl-C6-alkyl-C6H5; and phenyl, wherein when both R' are C1-C6-alkyl both R' together may form an NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, phosphonate: the group (OR) 2 wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphate: the group -OP(O)(OR) 2 wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; Cl-C6-alkyl-C6H5; Li; Na; K; Cs; Mg; and Ca, phosphine: the group -P(R) 2 wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5, phosphine oxide: the group -P(O)R 2 wherein R is independently selected from: hydrogen; Cl-C6-alkyl; phenyl; and Cl-C6-alkyl-C6H5; and amine (to give phosphonamidate) selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; C1-C6-alkyl; C1-C6- WO 01/16268 WO 01/6268 CT/EPOO/07561 68 and phenyl, wherein when both R, are Cl-C6-alkyl both R' together may form an -NC3 to an -NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring.

Unless otherwise specified the following are more preferred group restrictions that may be applied to groups found within compounds disclosed herein: alkyl: linear and branched Cl-C6-alkyl, alkenyl: C3-C6-alkenyl, cycloalkyl: C6-C8-cycloalkyl, alkoxy: Cl-C4-alkoxy, alkylene: selected from the group consisting of: methylene; 1,2-ethylene; 1,3-propylene; butan-2-ol1.4-diyl; 1,4butylene; cyclohexane-l, l-diyl; cyclohexan-l, 2-diyl; cyclohexan-l, 4-diyl; cyclopentane-l, l-diyl; and cyclopentan- 1, 2-diyl, aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl, arylene: selected from the group consisting of: 1,2phenylene; 1, 3-phenylene; 1,4-phenylene; 1,2-naphtalenylene; l,4-naphtalenylene; 2, 3-naphtalenylene and l-hydroxy-2, 6phenylene, WO 01/16268 WO 0116268PCrIEP00107561 -69 heteroaryl: selected from the group consisting of: pyridinyl; pyrimidirlyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, heteroarylene: selected from the group consisting of: pyridin-2, 3-diyl; pyridin-2,4-diyl; pyridin-2,6-diyl; quinolin-2,3-diyl; quinolin-2,4-diyl; isoquinolin-1,3-diyl; isoquinolin-l,4-diyl; diyl; and imidazole-2,4-diyl, heterocycloalkyl: selected from the group consisting of: pyrrolidinyl; morpholinyl; piperidinyl; piperidinyl; 1,4piperazinyl; tetrahydrofuraiyl; 1,4, 7-triazacyclonolanyl; l,4,8,ll-tetraazacyclotetradecanyl; 1,4,7,10,13pentaazacyclopentadecanyl; 1,4,7, io-tetraazacyclododecanyl; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, heterocycloalkylene: selected from the group consisting of: piperidin-2, 6-ylene; piperidin-4,4-ylidene; 1,4piperazin-1,4-ylene; l,4-piperazin-2,3-ylene; 1,4-piperazii- 2, 6-ylene; tetrahydrothiophen-2, 5-ylene; tetrahydrothiophen- 3,4-ylene; tetrahydrofuran-2, 5-ylene; tetrahydrofuran-3,4ylene; pyrrolidin-2,5-ylene; pyrrolidin-2,2-ylidene; 1,4,7triazacycloflon-l,4-ylene; 1,4,7-triazacyclonon-2,3-ylene; l,4,7-triazacyclonon-2,2-ylidele; 1,4,8,11tetraazacyclotetradec-l, 4-ylene; 1,4,8,11tetraazacyclotetradec-l, 8-ylene; WO 01/16268 WO O11626SPCTIEP00IO7561 1,4,8,ll-tetraazacyclotetradec-2,3-ylene; 1,4,8,11tetraazacyclotetradec-2, 2-ylidene; l.4,7,l0-tetraazacyclododec-l,4-ylene; 1,4,7,10tetraazacyclododec-1, 7-ylene; 1,4,7,l0-tetraazacyclododec-2,3-ylene; 1,4,7,10tetraazacyclododec-2,2-ylidene; 1,4,7,10,13pentaazacyclopentadec-l,4-ylene; 1,4,7,10,13pentaazacyclopentadec-l, 7-ylene; l,4-diaza-7-thia-cyclonon- 1,4-ylene; 1,4-diaza-7-thia-cyclonon-2,3-ylele; l,4-diaza-7thia-cyclonon-2,2-ylidene; 1,4-diaza-7-oxa-cyclonon-1,4ylene; l,4-diaza-7-oxa-cyclonon-2,3-ylefle;1,4-diaza-7-oxacyclonon-2,2-ylidene; l,4-dioxan-2,6-ylele; 1,4-dioxan-2,2ylidene; tetrahydropyran-2, 6-ylene; tetrahydropyran-2, ylene; and tetrahydropyran-2, 2-ylidene, amine: the group -N(R) 2 wherein each R is independently selected from: hydrogen; C1-C6-alkyl; and benzyl, halogen: selected from the group consisting of: F and Cl, sulfonate: the group -S(O) 2 0R, wherein R is selected from: hydrogen; C1-C6-alkyl; Na; K; Mg; and Ca, sulfate: the group -OS(O) 2 0R, wherein R is selected from: hydrogen; Cl-C6-alky1; Na; K; Mg; and Ca, sulfone: the group -S(O) 2 R, wherein R is selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR12, wherein each RI is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, WO 01/16268 pCT/EPOO/07561 71 carboxylate derivative: the group -C(O)OR, wherein R is selected from hydrogen; Na; K; Mg; Ca; Cl-C6-alkyl; and benzyl, carbonyl derivative: the group: wherein R is selected from: hydrogen; Ci-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, phosphonate: the group (OR) 2 wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphate: the group -OP(O) (OR) 2 wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl; Na; K; Mg; and Ca, phosphine: the group -P(R) 2 wherein each R is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl, phosphine oxide: the group -P(O)R 2 wherein R is independently selected from: hydrogen; Cl-C6-alkyl; benzyl and amine selected from the group: -NR'2, wherein each R' is independently selected from: hydrogen; Cl-C6-alkyl; and benzyl.

The invention will now be further illustrated by way of the following non-limiting examples: WO 01/16268 PCT/EP00/07561 72

EXAMPLES

Example 1 In Example 1 the iron perchlorate complex of MeN4Py [(MeN4Py)Fe(CH 3 CN)] (C10 4 2 was used. The iron perchlorate complex of MeN4Py was obtained according to the procedure found in EP-A-0909809 A. Pre-treatment systems were tested as follows: A pre-treatment system, 2 ml of each, were added to either BC-1 or Pomarola/soya oil stains on cotton fabric, and left for either 0 or 60 minutes prior to washing in 1.75 g/l detergent base in 150 FH (all Ca 2 water at 25 OC in a tergotometer (80 opm).

The detergent base powder composition is given below: Component Parts by weight LAS (linear alkylbenzene 28 sulfonate) Sodium sulphate 10.258 STP 28 Alkaline silicate 9.9778 Fluorescer 0.24 EDTA 0.009 SCMC (Na 1.12 carboxymethylcellulose) Water 10.222 TOTAL 87.627 The following pretreatment compositions were used: WO 01/16268 PCT/EP00/07561 73 'no pretreat' (main wash only) 'water' (blank): aqueous solution 0.2 STP and 0.05 Dequest, pH 9.6 '8cat': 8 pM catalyst in aqueous solution 0.2 STP and 0.05 Dequest, pH 9.6 '8cat/perox': 8 pM catalyst in aqueous solution 7

H

2 0 2 0.2 STP and 0.05 Dequest, pH 9.6 '20cat': 20 pM catalyst in aqueous solution, 0.2 STP, 0.05 Dequest, pH 9.6 '20cat/perox' 20 4M catalyst in aqueous solution 7

H

2 0 2 0.2 STP and 0.05 Dequest, pH 9.6 'perox' (blank): aqueous solution 7 H 2 0 2 'oil'(blank): oleic acid 'oil-8cat': 8 pM catalyst in oleic acid 'oil-20cat': 20 pM catalyst in oleic acid AEaw (aw after wash) values were measured as follows: After the wash, the cloths were rinsed with water and subsequently dried at ambient temperature in the dark and the change in colour was measured after leaving the cloths for 24 h in the dark with an Ultrascan XE spectrophotometer (ex Hunterlab). The change in colour (including bleaching) is expressed as the AEaw value relative to clean white cotton. The measured colour difference (AEaw) between the washed cloth and the clean white cotton cloth is defined as follows: AEaw 2 +(Aa) 2 +(Ab) 2 ]1/2 WO 01/16268 PCT/EP00/07561 74 wherein AL is a measure for the difference in darkness between the washed and clean white cloth; Aa and Ab are measures for the difference in redness and yellowness respectively between both cloths. With regard to this colour measurement technique, reference is made to Commission International de 1'Eclairage (CIE); Recommendation on Uniform Colour Spaces, colour difference equations, psychometric colour terms, supplement no 2 to CIE Publication, no 15, Colormetry, Bureau Central de la CIE, Paris 1978.

The results are shown in Tables 1 and 2 below.

Table 1. Tea (BC1) catalyst stain effect of pre-treatment with Fe- Eaw Omin pre-treat 60min pre-treat No pre-treat 20.3 20.3 Water 20.7 20.4 8cat 20.7 20.7 8cat/perox 15.1 20.9 20.6 14.2 6.7 Perox 16.0 Oil 21.0 21.1 Oil-8cat 20.3 20.4 20.2 20.3 Table 2. Pomarola/oil stain effect of pre-treatment with Fe-catalyst WO 01/16268 PCT/EPOO/07561 75 Eaw Omin pre-treat 60min pre-treat No pre-treat 15.1 14.9 Water 11.5 11.8 8cat 5.5 4.3 8cat/perox 11.6 11.2 3.7 2.9 7.1 6.8 Perox 16 15.5 Oil 5.6 3.4 Oil-8cat 3.0 2.2 2.7 Example 2 In Example 2 the iron chloride complex of MeN4py [FeMeN4pyCl 2 was used. The iron chloride complex of MeN4py was prepared as follows from the MeN4py ligand synthesised as in EP 0909809. MeN4Py ligand (33.7 g; 88.5mmoles) was dissolved in 500ml dry methanol. Small portions of FeCl 2 .4H 2 0 (0.95eq; 16.7g; 84.0 mmoles) were added, yielding a clear red solution. After addition, the solution was stirred for minutes at room temperature, after which the methanol was removed (rotary-evaporator). The dry solid was ground and 150 ml of ethylacetate was added and the mixture was stirred until a fine red powder was obtained. This powder was washed twice with ethyl acetate, dried in the air and further dried under vacuum (40 OC). El. Anal. Calc. for [Fe(MeN4py)Cl]C1.2H20: C 53.03; H 5.16; N 12.89; C1 13.07; Fe 10.01%. Found C 52.29/ 52.03; H 5.05/5.03; N 12.55/12.61; Cl: 12.73/12.69; Fe: 10.06/10.01%.

Oils were applied on the BC-1 cloth by the following procedure. First an oil was dissolved in a heptane solution WO 01/16268 PCT/EPOO/07561 76 mg liquid per ml heptane solution), then 0.72 ml of this solution was applied to a BC-1 (tea) cloth of 6x6 cm, yielding 5% oil on the cloth. The two oils employed were medium chain triglyceride oil (fully saturated oil) and sunflower oil (SF) (poly-unsaturated oil containing a high quantity of 2 or 3 double bonds in the esterified fatty acid chains). Subsequently the cloths were brought into contact with a 10 mM carbonate buffer solution (pH 10) containing microM of FeMeN4pyCl 2 in and mixed for 30 minutes at 30 °C (liquor-to-cloth ratio of 40:1). In comparative experiments the same cloths were treated without the iron catalyst in the buffer solution.

After incubation, the cloths were washed three times with demin-water, then dried in a tumble drier and stored in the dark (wrapped in aluminum foil). The bleach results of the cloths, obtained after various periods of times are given in the table below. The reflectance of the cloths was measured with a MinoltaTM 3700d spectrophotometer at 460 nm. The difference in reflectance before and after the wash/storage is defined as a AR460 value; a higher value indicates a better bleaching of the BC-1 stain. The bleaching values were determined immediately after the wash, after 4, 10, 17 and 24 days storage.

Table 3: bleaching performance of the iron catalyst on BC-1 in the absence of oil, in the presence of MCT oil and Sunflower oil. The bleaching activity is expressed as a AR460 value (a higher value indicates a cleaner cloth).

77 No oil No oil MCT oil MCT oil SF oil SF oil -Fecat +Fecat -Fecat +Fecat -Fecat +Fecat T=0 day 1.4 0.7 -0.6 -1.6 -0.5 T=4 days 1.7 1.0 -0.3 -1.5 -0.5 1.2 days 1.9 1.2 -0.1 -1.2 -0.1 3.6 T=17 days 2.2 1.8 0.6 -0.5 0.6 T=24 days 2.5 2.4 1.2 -0.1 1.3 The results given in Table 3 are indicative of that the presence of unsaturated oil in treatment gives an increased BC-1 bleaching upon storage in the air (last column). Thus the pre-treatment of the stain with unsaturated oil yields as detailed above provides improved air bleaching.

Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

The reference to any prior art in this specification is not, and should not be taken as, an acknowledgment or any form of suggestion that the prior art forms part of the common general knowledge in Australia.

Claims

2. A method according to claim 1, wherein one of the pretreatment composition and the wash liquor comprises peroxygen bleach or a peroxy-based or -generating bleach oooe system, preferably hydrogen peroxide, and the other of the 20 pretreatment composition and the wash liquor is substantially devoid of peroxygen bleach or a peroxy-based o ~or -generating bleach system.
3. A method according to claim 2, wherein the pretreatment composition comprises the peroxygen bleach or peroxy-based or -generating bleach system. ••co
4. A method according to claim 2, wherein the pretreatment composition is substantially devoid of peroxygen bleach or a O peroxy-based or -generating bleach system. 79 A method according to claim 1 or 2, wherein the pretreatment composition comprises unsaturated fatty acid oil.
6. A method according to any preceding claim, wherein the pretreatment composition is applied to the stained fabric at least 5 minutes, preferably at least 15 minutes, more preferably at least 50 minutes, before washing.
7. A method according to any preceding claim, wherein the pretreatment composition is in the form of a liquid.
8. A method according to any preceding claim, wherein the ligand forms a complex of the general formula: [MaLkXn] Ym in which: M represents a metal selected from Mn(II)-(III)-(IV)- 20 Fe Co(I)-(II)- (III), Ti(II)-(III)-(IV), Mo(II)- and preferably from Fe L represents the ligand, or its protonated or deprotonated analogue; X represents a coordinating species selected from any S 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 80 k represents an integer from 1 to n represents zero or an integer from 1 to m represents zero or an integer from 1 to
9. A method according to any preceding claim, wherein the ligand is a pentadentate ligand of the general formula (IVE): R1 R 2 R 3 C--N R 1 R 2 (IVE) wherein each R 1 R 2 independently represents -R-R 5 R 3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R 4 -R 5 each R 4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R 5 independently represents an optionally N- substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl. 25 10. A method according to any preceding claim, wherein the ligand is N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2- yl)-1-aminoethane. 81
11. A method according to any one of claims 1 to 8, wherein ligands of the general formula (IE): Tl- (Q1) s-N- (Q2) g-T 2 R1 R2 (IE) wherein g represents zero or an integer from 1 to 6; r represents an integer from 1 to 6; s represents zero or an integer from 1 to 6; Q1 and Q2 independently represent a group of the formula: R6 R8 d- e f- R7 R9 20 wherein 5 d+e+f 1; d=0-5; e=0-5; each Y1 independently represents a group selected from -SO 2 arylene, alkylene, heteroarylene, heterocycloalkylene, and wherein G is selected from hydrogen, alkyl, aryl, S arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; if s>l, each group is independently 30 defined; 0 82 R1, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or R6 together with R7, or R8 together with R9, or both, represent oxygen, or R6 together with R8 and/or independently R7 together with R9, or R6 together with R9 and/or independently R7 together with R8, represent C 1 6 -alkylene optionally substituted by C 1 4 -alkyl, -Cl, -Br or -I; or one of R1-R9 is a bridging group bound to another moiety of the same general formula; Tl and T2 independently represent groups R4 and wherein R4 and RS are as defined for R1-R9, and if g=0 and S s>0, R1 together with R4, and/or R2 together with R5, may optionally independently represent =CH-R10, wherein R10 is 20 as defined for R1-R9, or T1 and T2 may together represent a covalent bond linkage when s>l and g>0; if T1 and T2 together represent a single bond linkage, Q1 and/or Q2 may independently represent a group of the formula: =CH- provided R1 and/or R2 are absent, and R1 and/or R2 may be absent provided Q1 and/or Q2 independently represent a group of the formula: =CH- e-CH=. o 83
12. A method according to any of claims 1 to 11, wherein the pretreatment composition comprises a preformed complex of the ligand and the transition metal.
13. A method according to any of claims 1 to 12, wherein the pretreatment composition comprises free ligand that complexes with transition metal present in the wash liquor.
14. A method according to any of claims 1 to 12, wherein the pretreatment composition comprises free ligand that complexes with transition metal present in the stain. A method according to any of claims 1 to 12, wherein the pretreatment composition comprises free ligand or a transition metal-substitutable metal-ligand complex, and a source of transition metal.
16. A method of bleaching fabric stains substantially as hereinbefore described with reference to the examples. DATED THIS 30th day of September, 2003. UNILEVER PLC By Its Patent Attorneys S DAVIES COLLISON CAVE ego•