ZA200201602B

ZA200201602B - Composition and method for bleaching a substrate.

Info

Publication number: ZA200201602B
Application number: ZA200201602A
Authority: ZA
Inventors: Ronald Hage; Simon Marinus Veerman
Original assignee: Unilever Plc
Priority date: 1999-09-01
Filing date: 2002-02-26
Publication date: 2003-02-26

Description

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COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE .

FIELD OF INVENTION

This invention relates to compositions and methods for catalytically bleaching substrates with atmospheric oxygen, using a metal-ligand complex as catalyst, which compositions are formulated as liquids. This invention also relates to a method of treating textiles, such as laundry fabrics, using a metal-ligand complex as catalyst whereby bleaching with atmospheric oxygen is catalysed after the treatment, wherein "the treatment composition is formulated as a liquid.

BACKGROUND OF INVENTION

: 15

Peroxygen bleaches are well known for their ability to remove stains from substrates. Traditionally, the substrate ; is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or - organic peroxides. Generally, these systems must be activated. One method of activation is to employ wash temperatures of 60°C or higher. However, these high temperatures often lead to inefficient cleaning, and can also cause premature damage to the substrate.

A preferred approach to generating hydroperoxyl bleach species is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various

European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United

States laundry bleach products are typically based on sodium nonanoyloxybenzenesulphonate (SNOBS) as the organic precursor coupled with sodium perborate. — 5 nY Precursor systems are generally effective but still exhibit several disadvantages. For example, organic precursors are : . moderately sophisticated molecules requiring multi-step ~ manufacturing processes resulting in high capital costs. pa 10 Also, precursor systems have large formulation space requirements so that a significant proportion of a laundry powder must be devoted to the bleach components, leaving less room for other active ingredients and complicating the development of concentrated powders. Moreover, precursor ~~ 15 systems do not bleach very efficiently in countries where ” consumers have wash habits entailing low dosage, short wash . times, cold temperatures and low wash liquor to substrate ratios.

Alternatively, or additionally, hydrogen peroxide and peroxy systems can be activated by bleach catalysts, such as by complexes of iron and the ligand N4Py (i.e. N, N- bis (pyridin-2-yl-methyl) -bis (pyridin-2-yl) methylamine) disclosed in W095/34628, or the ligand Tpen (i.e. N, N, N’,

N’-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in

WOS7/48787. These publications do not foresee a role in providing storage stable liquid bleaching compositions even if, according to these publications, molecular oxygen may be used as the oxidant as an alternative to peroxide generating systems.

As discussed by N.J. Milne in J. of surfactants and

Detergents, Vol 1, no 2, 253-261 (1998), it has long been thought desirable to be able to use atmospheric oxygen (air) as the source for a bleaching species. The use of atmospheric oxygen (air) as the source for a bleaching species would avoid the need for costly hydroperoxyl generating systems. Unfortunately, air as such is kinetically inert towards bleaching substrates and exhibits no bleaching ability. Recently some progress has been made in this area. For example, WO 97/38074 reports the use of air for oxidising stains on fabrics by bubbling air through an aqueous solution containing an aldehyde and a radical initiator. A broad range of aliphatic, aromatic and heterocyclic aldehydes is reported to be useful, particularly para-substituted aldehydes such as 4-methyl-, 4-ethyl- and 4-isopropyl benzaldehyde, whereas the range of initiators disclosed includes N-hydroxysuccinimide, various - peroxides and transition metal coordination complexes.

However, although this system employs molecular oxygen from the air, the aldehyde component and radical initiators such "7777 as peroxides are consumed during the bleaching process. CT

These components must therefore be included in the composition in relatively high amounts so as not to become depleted before completion of the bleaching process in the wash cycle. Moreover, the spent components represent a waste of resources as they can no longer participate in the bleaching process.

Accordingly, it would be desirable to be able to provide a bleaching system based on atmospheric oxygen or air that oC does not rely primarily on hydrogen peroxide or a = hydroperoxyl generating system, and that does not require i the presence of organic components such as aldehydes that are consumed in the process. Moreover, it would be - 5 desirable to provide such a bleaching system that is

Ea effective in aqueous medium.

It may also be noted that the known art teaches a bleaching : effect only as long as the substrate is being subjected to : 10 the bleaching treatment. Thus, there is no expectation that - hydrogen peroxide or peroxy bleach systems could continue to ; provide a bleaching effect on a treated substrate, such as a laundry fabric after washing and drying, since the bleaching . = species themselves or any activators necessary for the bleaching systems would be assumed to be removed from the substrate, or consumed or deactivated, on completing the - wash cycle and drying. : It would be therefore also be desirable to be able to treat a textile such that, after the treatment is completed, a bleaching effect is observed on the textile. Furthermore, it would be desirable to be able to provide a bleach treatment for textiles such as laundry fabrics whereby residual bleaching occurs in the presence of air when the treated fabric has been treated and is dry. It would be desirable for the residual bleaching of dry textiles to be conducted irrespective of exposure to light.

A further disadvantage associated with conventional bleaching compositions based on hydrogen peroxide or peroxy systems such those containing organic peroxyacids is that the compositions tend to be chemically or physically unstable in the presence of liquid solvents, carriers or : other liquid components such as surfactants, particularly when formulated as aqueous compositions. Consequently, when formulated as liquids, these bleaching compositions on the ) one hand do not exhibit satisfactory storage stability, - resulting in a rapid loss of bleaching activity or in a loss of structural integrity, for example phase separation, or require the incorporation of additional stabilising systems to minimise these effects with attendant disadvantages in terms of cost or processing. Decomposition of a hydrogen peroxide or peroxy liquid bleaching composition in a sealed container leads to an increase in the internal pressure of the sealed container. The increase in the internal pressure leads to the possibility of the sealed container rupturing in a dangerous manner. In the presence of surfactants, decomposition of the hydrogen peroxide or - peroxy liquid bleaching composition leads to foaming of the composition. On the other hand, liquid bleaching } compositions are conveniently dosed into containers for storage or for use, or otherwise handled, and are desired by ~- + the consumer; particularly im the United States of America. —

It would therefore also be desirable to be able to provide a bleaching composition in the form of a liquid, which is chemically and physically stable, without at least some of the disadvantages hitherto associated with liquid bleaching compositions. It would furthermore be desirable to be able to provide chemically and physically storage stable detergent bleaching compositions or rinse conditioning bleach compositions in the form of a liquid.

. + WO 01/16271 PCT/EP00/08076

Application W000/29537, filed 9 November 1999, was published fe after the filing date of the present application disclosing = theoretical examples of compositions for bleaching with a “ transition metal complex in the absence of an added peroxygen bleach. Application W000/29537 has no evidence of oo efficacy and includes two classes of ligands: some cross- . - bridged macrocyclic ligands and some macrocyclic ligands. : The macrocyclic ligands are disclosed as manganese complexes and are not found in the priority document of WO00/29537; namely US serial number 60/108,292 filed 13 November 1998.

The theoretical examples given are for a heavy-duty granular laundry detergent and heavy-duty liquid laundry detergent.

In both these examples the exemplified bleach catalyst is 5,12-dimethyl-1,5,8,12-tetra-bicyclo[6.6.2.]hexadecane manganese (II) chloride. There are no examples : demonstrating any bleaching effect. The use of manganese

X complexes in laundry applications is less preferred because

Bh of dye/textile damage under specific conditions.

SUMMARY OF INVENTION

We have now found that it is possible to achieve a chemically and physically stable bleaching composition in the form of a liquid, by using an organic substance that forms a complex which catalyses the bleaching of substrates using atmospheric oxygen or air, and formulating the organic substance in a liquid that is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system. Moreover, we have found that these organic substances can be formulated together with detergent or rinse conditioning agents, in a liquid that is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, to provide chemically and physically stable detergent bleaching compositions or rinse conditioning bleach compositions, in the form of a liquid.

Accordingly, in a first aspect, the present invention a liquid bleaching composition comprising an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by atmospheric oxygen, and a liquid carrier or solvent, wherein the composition is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system. The composition is therefore preferably insensitive or stable to catalase, which acts on peroxy species.

In a second aspect, the present invention provides a method of bleaching a substrate comprising applying to the substrate a liquid bleaching composition that comprises an ] organic substance which forms a complex with a transition i metal, the complex catalysing bleaching of the substrate by atmospheric oxygen, and a liquid carrier or solvent, wherein --- ihe vumpusition is substantially deveid sf pemsyygen bleach or a peroxy-based or -generating bleach system.

Furthermore, in a third aspect, the present invention provides the use of an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by the atmospheric oxygen, as a catalytic bleaching agent in a liquid bleaching composition substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.

on “Wo 01716271 PCT/EP00/08076

We have also found that the liquid bleaching compositions in. - accordance with the present invention are surprisingly - effective in catalysing bleaching of substrates by atmospheric oxygen after treatment of the substrate.

Accordingly, in a fourth aspect, the present invention

N provides a method of treating a textile by contacting the textile with a liquid bleaching composition that comprises an organic substance which forms a complex with a transition metal, the complex catalysing bleaching by atmospheric } oxygen, and a liquid carrier or solvent, wherein the composition is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment. . ~ The present invention requires all or the majority of the ) bleaching species in the liquid bleaching composition (on an co equivalent weight basis) to be derived from atmospheric oxygen. Thus, the liquid composition will be made wholly or substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system. The organic substance is a catalyst for the bleaching process and, as such, is not consumed but can continue to participate in the bleaching process. Since the bleaching system of the type used in the liquid bleaching composition is catalytically activated and the bleaching species is derived from atmospheric oxygen, the present invention is advantageous in that it provides a bleaching composition which is not only convenient to handle by virtue of being in the form of a liquid, but which also is both cost-effective and environmentally friendly.

The liquid bleaching composition may be formulated as a i. concentrated bleaching liquid for direct application to a } substrate, or for application to a substrate following dilution, such as dilution before or during use of the liquid composition by the consumer or in washing apparatus.

The liquid bleaching composition can for example be formulated as an aqueous medium, or so as to be dispersable into an aqueous medium, and is therefore particularly applicable to bleaching of laundry fabrics. Therefore, whilst the composition and method according to the present invention may be used for bleaching any suitable substrate, : the preferred substrate is a laundry fabric. Bleaching may : be carried out by simply leaving the substrate in contact for a sufficient period of time with a bleach medium : constituted by or prepared from the liquid bleaching composition. Preferably, however, the bleach medium on or : containing the substrate is agitated.

An advantage of the method according to the fourth aspect of the invention is that, by enabling a bleaching effect even == = afteY The textile has been tredted, the benefits of ee bleaching can be prolonged on the textile. Furthermore, since a bleaching effect is conferred to the.textile after the treatment, the treatment itself, such as a laundry wash cycle, may for example be shortened.

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

J © WO 01/16271 PCT/EP00/08076

The present invention also extends to use of a ligand or . complex as defined below in the manufacture of a liquid : bleaching composition, the bleaching composition substantially devoid of peroxygen bleach or a peroxy-based or peroxy-generating bleach system.

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 : 15 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. It is preferred that the catalyst is a pentadentate ligand or complex = thereof.

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, 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: [MaLlyXnl Yn

. in which:

M represents a metal selected from Mn(II)-(III)-(IV)- (V), Cu(I)-(I1)-(III), Fe (II)-(III)-(IV)-(V), Col(I)-(II)- (III), Ti(II)-(III)- (IV), V(II)-(III)-(IV)-(V), Mo(II)- (III) - (IV) -(V)-(VI) and W(IV)-(V)-(VI), preferably from - Fe (IT)-(ITII)-(IV)-(V);

L represents the ligand, preferably N,N-bis (pyridin-2- yl-methyl) -1,1-bis(pyridin-2-yl)-1-aminoethane, or its : : 10 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; . 15 Y represents any non-coordinated counter ion; a represents an integer from 1 to 10; k represents an integer from 1 to 10; N n represents zero or an integer from 1 to 10; m represents zero or an integer from 1 to 20. -

Preferably, the complex is an iron complex comprising the ligand ¥,N-bis{pyridin-Z-yl-wethylj=L, 1=-bis (pyridin=2=9ij-1- — —— aminoethane. However, it will be appreciated that the pretreatment method of the present invention may instead, or additionally, 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: (A) Ligands of the general formula (IA):

z=

T—C—@—U

Z1—@Q1) (IA) wherein

Z1 groups independently represent a coordinating group : selected from hydroxy, amino, -NHR or -N(R). (wherein R=C;.¢- alkyl), carboxylate, amido, -NH-C(NH)NH;, hydroxyphenyl, a heterocyclic ring optionally substituted by one or more functional groups E or a heteroaromatic ring optionally co 10 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;

X 15

Q1 and Q3 independently represent a group of the - formula:

I rbd

CC

R6 R8 wherein

> 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 -0-, - 5 §-, -80-, -80,-, -C(0)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(0)- and -{(G)N- , 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, N 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,.¢-alkylene optionally substituted by C;.,-alkyl, -F, -Cl, -Br or -I;

To © I represents a non-coérdinated group selected trom 02 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= -H, -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):

~', "wWoonemn PCT/EP00/08076 : - 14 -~

SQ

Q@—z4 (IIA)

Ca . [2 (IIIA)

Q)—z1

QT CT

Q)—zi oo . (IVA) * wherein - 02 and Q4 are independently defined as for Q1 and Q3;

Q represents -N(T)- (wherein T is independently defined as above), or an optionally substituted heterocyclic ring ox an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; 722 is independently defined as for 21;

Z3 groups independently represent -N(T)- (wherein T is independently defined as above);

Z4 represents a coordinating or non-coordinating group selected from hydrogen, hydroxyl, halogen, -NH-C(NH)NH,, -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): 2—®@ QZ

N— T / RA i) (I1Aa) and l <3 <4. :

Preferably, Zl, Z2 and Z4 independently represent an - optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, ~—-- 20 © pyrimidine, pyrazine, pyrazole, imidazule, benzimidazole; Sem quinoline, quinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole. More preferably,

Zl, 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-1-yl, and optionally substituted quinolin-2-yl. Most preferred is that 21, Z2 and 24 each represent optionally substituted pyridin-2-yl.

. The groups Z1, Z2 and Z4 if substituted, are preferably substituted by a group selected from C;.,-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl. Preferred is that 21, 22 and 5S 24 are each substituted by a methyl group. Also, we prefer that the Z1 groups represent identical groups. : Each Q1 preferably represents a covalent bond or Cl-C4- alkylene, more preferably a covalent bond, methylene or ethylene, most preferably a covalent bond.

Group Q preferably represents a covalent bond or Cl-C4- alkylene, more preferably a covalent bond.

The groups R5, R6, R7, R8 preferably independently represent a group selected from -H, hydroxy-Co-Czo-alkyl, halo-Cy-Cio- ; alkyl, nitroso, formyl-Cy-Czo-alkyl, carboxyl-C,-C-alkyl and esters and salts thereof, carbamoyl-Co-Cze-alkyl, sulfo-C,- wo Czo-alkyl and esters and salts thereof, sulfamoyl-Cy-Czo- alkyl, amino-Cys-Cio-alkyl, aryl-Co-Caio-alkyl, Co-Cao-alkyl, alkoxy-Co-Cs-alkyl, carbonyl-Co-Cs-alkoxy, and Co-Cazo- 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):

,Q@2

Nev (IIR)

According to this aspect, it is preferred that 22 represents

S 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, iN indole, isoindole, oxazole and thiazole, more preferably optionally substituted pyridin-2-yl, or an non-coordinating 26 group selected from hydrsgen; hydreiny; alkoxy, 2lk¥y, 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-2- ylmethyl) methylamine; 1,1-bis(pyridin-2-yl)-N,N-bis(6-methyl-pyridin-2- ylmethyl) methylamine;

on "WO 0116271 PCT/EP00/08076 1,1-bis(pyridin-2-yl) -N,N-bis (5-carboxymethyl-pyridin-2- ylmethyl)methylamine; 1,1-bis(pyridin-2-yl) -1-benzyl-N,N-bis (pyridin-2- ylmethyl)methylamine; and : 1,1-bis(pyridin-2yl)-N,N-bis(benzimidazol-2- ylmethyl) methylamine.

In a variant of this aspect, the group 24 in formula (IIA) represents a group of the general formula (IIAa): zZ2—@ Qt

N—@ GT / . Q)—z1 (IIRa)

In this variant, Q4 preferably represents optionally * 15 substituted alkylene, preferably -CH;-CHOH-CH,- or -CH.-CH,-

CHz-. In a preferred embodiment of this variant, the ligand ” is:

Py Py hil r 1 Lo

NN \ 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):

Ca [Q@-Z3} (IIIA) wherein j is 1 or 2, preferably 1.

According to this aspect, each Q2 preferably represents - (CH) o- (n=2-4), and each Z3 preferably represents -N(R)- wherein R = -H or C;.4-alkyl, preferably methyl.

In preferred embodiments of this aspect, the ligand is selected from: ) Py Py / N Me / \ M

H—C—N N~ Me—Cc—N NT

K u ) i CL ) i )

Me Me ] wherein -Py represents pyridin-2-yl. ~~ in yet another aspect; the group VY im fewmala IN - oo —— represents a coordinating group of the general formula (IVA) :

Q)—zi —Q—@ CT

Q)—2z1 (IVA)

) + WO 01/16271 PCT/EP00/08076

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

In preferred embodiments of this aspect, the ligand is selected from:

P H P P P

Nol 77 \ /Y

Me—C—N—C—Me MeO—C—Q —C—OMe / \ / \

Py Py Py Py

P P

HO AN Lon

Za

Py Py wherein -Py represents pyridin-2-yl, and -Q- represents pyridin-2,6-diyl. . (B) Ligands of the general formula (IB):

R—Qn_

N-fQ—NT-QR,

Re—Q5” [=n he

Ra (IB) wherein n =1 or 2, whereby if n = 2, then each -Q;-R; group is independently defined;

Ri, Raz, Ri, Ri independently represent a group selected - from hydrogen, hydroxyl, halogen, -NH-C(NH)NH,, -R and -OR, wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R being

S optionally substituted by one or more functional groups E,

Qi, Qz, Qi, Q and Q independently represent a group of the formula:

Y

THE ak)

R6 R8 . : } wherein i} . 5 > a+b+c > 1; a=0-5; b=0-5; ¢=0-5; n=1 or 2;

Y independently represents a group selected from -O-, - 8-, -80-, -80;-, -CIi0OY-, arylens, alkylene, heternarviene, ll heterocycloalkylene, -(G)P-, -P(0)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E;

RS, R6, R7, R8 independently represent a group selected from hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cycloalkyl, heterocycloalkyl,

: v WO 01/16271 PCT/EP00/08076 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,.¢-alkylene optionally substituted by C;.4-alkyl, -F, -Cl, -Br or -I, provided that at least two of Ri), Rz, Ri, Rs 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 Ri, Raz, Ri, Ry independently represent a group selected from carboxylate, amido, -NH-C(NH)NH,, hydroxyphenyl, an optionally substituted

N 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, substituents for groups R,, Ra, Ri, Rs, when representing a heterocyclic or heteroaromatic ring, are selected from C;.4-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl.

The groups Qi, Q., Qi, Qi preferably independently represent a group selected from -CH;- and -CH;CH,-.

~ Group Q is preferably a group selected from - (CH;),.4-, -

CH,CH (OH) CH, -, 7 ~ optionally substituted by methyl or ethyl, eal vere

R on ‘ N , and wherein R represents -H or C;4-alkyl.

Preferably, Qi, Q:, Qi, Q; are defined such that a=b=0, c=1 and n=1, and Q is defined such that a=b=0, c¢=2 and n=1.

The groups R5, R6, R7, R8 preferably independently represent a a group selected from -H, hydroxy-Co-Cyo-alkyl, halo-Co¢-Cze- : alkyl, nitroso, formyl-Cy-Cao-alkyl, carboxyl-Co-Cie-alkyl and esters and salts thereof, carbamoyl-Co-Czo-alkyl, sulfo-Co-

C20-alkyl and esters and salts thereof, sulfamoyl-Ce-Cao- - alkyl, amino-Cy-Cio-alkyl, aryl-Co,-Cze-alkyl, Co-Czo-alkyl, alkoxy-Co-Cs-alkyl, carbonyl-Co-Cs-alkoxy, and Co-Cap- h alkylamide. Preferably, none of R5-R8 is linked together.

In a preferred aspect, the ligand is of the general formula - (IIB): .

Ri—Qq Qi—Ry

N—Q—N :

R—Q2 QR; (IIB) wherein oh ". WO 01/16271 PCT/EP00/08076

Q:, Q2, Qi, Qs are defined such that a=b=0, c=1 or 2 and n=1;

Q is defined such that a=b=0, ¢=2,3 or 4 and n=l; and

Ri, Ra, Ri, Rs, R7, R8 are independently defined as for formula (I).

Preferred classes of ligands according to this aspect, as represented by formula (IIB) above, are as follows: (i) ligands of the general formula (IIB) wherein:

Ri, Ra, Ri, Rs each independently represent a coordinating group selected from carboxylate, amido, -NH-

C(NH)NH,, 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:

Q is defined such that a=b=0, c=2 or 3 and n=1;

Ri, Rz, Ri, Rs 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:

Ri, R;, Ri each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH;, hydroxyphenyl, an optionally substituted heterocyclic ring

LL 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; represents a group selected from hydrogen, C;.z optionally substituted alkyl, Ci;.2o optionally substituted arylalkyl, aryl, and C,.z optionally substituted NRj’ (wherein R=C;.g-alkyl).

L: 10

In this class, we prefer that:

Q is defined such that a=b=0, c=2 or 3 and n=1; : _ R;, R;, Ri each independently represent a coordinating : group selected from optionally substituted pyridin-2-yl, - 15 optionally substituted imidazol-2-yl, optionally substituted imidazol-4-yl, optionally substituted pyrazol-1-yl, and optionally substituted quinolin-2-yl; and N

R, represents a group selected from hydrogen, Ci.io optionally substituted alkyl, Ci;.s-furanyl, Ci.s optionally ~ substituted benzylalkyl, benzyl, Ci.s optionally substituted alkoxy, and Cj. optionally substituted N*Mes. (iii) ligands of the general formula (IIB) wherein:

R;, R; each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH, : hydroxyphenyl, an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrazole, imidazole, benzimidazole, quinoline, gquinoxaline, triazole, isoquinoline, carbazole, indole, isoindole, oxazole and thiazole; and oN *. WO 01/16271 PCT/EP00/08076

Ra, R; each independently represent a group selected from hydrogen, Ci.zo optionally substituted alkyl, Ci.ae optionally substituted arylalkyl, aryl, and C;.2o optionally substituted NR;* (wherein R=C;.g-alkyl).

In this class, we prefer that: } Q is defined such that a=b=0, c¢=2 or 3 and n=1;

Ri, Rs 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:, Ri each independently represent a group selected from hydrogen, C;.;0 optionally substituted alkyl, Ci;.s- oo 15 furanyl, C,.s optionally substituted benzylalkyl, benzyl, Ci.s optionally substituted alkoxy, and C;-20 optionally . substituted N*Me;.

LA Examples of preferred ligands in their simplest forms are:

N,N',N'-tris(3-methyl-pyridin-2-ylmethyl) -ethylenediamine;

N-trimethylammoniumpropyl-N,N’',N'-tris(pyridin-2-ylmethyl) - ethylenediamine;

N- (2-hydroxyethylene) -N,N' ,N'-tris(pyridin-2-ylmethyl) - ethylenediamine;

N,N,N',N'-tetrakis(3-methyl-pyridin-2-ylmethyl) -ethylene- diamine;

N,N'-dimethyl-N,N'-bis(pyridin-2-ylmethyl) -cyclohexane-1,2- diamine;

N- (2-hydroxyethylene) -N,N',N'-tris (3-methyl-pyridin-2- ylmethyl) ~ethylenediamine;

N-methyl-N,N',N'-tris(pyridin-2-ylmethyl) -ethylenediamine;

N-methyl-N,N',N'-tris(5-ethyl-pyridin-2-ylmethyl) - - ethylenediamine;

N-methyl-N,N',N'-tris(5-methyl-pyridin-2-ylmethyl) - - 5 ethylenediamine;

N-methyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl) - ethylenediamine;

N-benzyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl) - ethylenediamine;

N-ethyl-N,N',N'-tris(3-methyl-pyridin-2-ylmethyl) - ethylenediamine;

N,N,N'-tris(3-methyl-pyridin-2-ylmethyl) -N' (2'-methoxy- ethyl-1) -ethylenediamine; » N,N,N'-tris(1-methyl-benzimidazol-2-yl)-N'-methyl- - 15 ethylenediamine;

N- (furan-2-yl) -N,N',N'-tris(3-methyl-pyridin-2-ylmethyl) - ethylenediamine; -

N- (2-hydroxyethylene) -N,N',N'-tris(3-ethyl-pyridin-2- ) ylmethyl) -ethylenediamine;

N-methyl-N,N’,N’-tris(3-methyl-pyridin-2-ylmethyl)ethylene-

Ra i1,Z-giamine; : Co So

N-ethyl-N,N’,N’-tris(3-methyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-benzyl-N,N’,N’-tris(3-methyl-pyridin-2-ylmethyl)ethylene- 1l,2-diamine;

N- (2-hydroxyethyl) -N,N’ ,N’ -tris (3-methyl -pyridin-2- ylmethyl) ethylene-1,2-diamine;

N- (2-methoxyethyl) -N,N’ ,N’ -tris(3-methyl-pyridin-2- ylmethyl) ethylene-1,2-diamine; :

N-methyl-N,N’ ,N’ -tris(5-methyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-ethyl-N,N’,N’-tris (5-methyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-benzyl-N,N’,N’-tris(5-methyl-pyridin-2-ylmethyl)ethylene- 1l,2-diamine;

N- (2-hydroxyethyl) -N,N’ ,N’ -tris(5-methyl-pyridin-2- ylmethyl)ethylene-1,2-diamine;

N- (2-methoxyethyl) -N,N’ ,N’ -tris(5-methyl-pyridin-2- ylmethyl)ethylene-1,2-diamine;

N-methyl-N,N’ ,N’-tris(3-ethyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-ethyl-N,N’,N’-tris(3-ethyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-benzyl-N,N’ ,N’-tris(3-ethyl-pyridin-2-ylmethyl)ethylene- . 1,2-diamine;

N- (2-hydroxyethyl) -N,N’ ,N’ -tris(3-ethyl-pyridin-2- ” ylmethyl)ethylene-1,2-diamine;

N- (2-methoxyethyl)-N,N’ ,N’-tris(3-ethyl-pyridin-2- ylmethyl)ethylene-1,2-diamine;

N-methyl-N,N‘,N’-tris(5-ethyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-ethyl-N,N’,N’-tris(5-ethyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-benzyl-N,N’ ,N’-tris(5-ethyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine; and

N- (2-methoxyethyl) -N,N’ ,N’ -tris(5-ethyl-pyridin-2- ylmethyl)ethylene-1,2-diamine. ‘

More preferred ligands are:

N-methyl-N,N’ ,N’-tris(3-methyl-pyridin-2-ylmethyl)ethylene- . 1,2-diamine;

N-ethyl-N,N’ ,N’-tris (3-methyl-pyridin-2-ylmethyl)ethylene- 1,2-diamine;

N-benzyl-N,N’,N’-tris(3-methyl-pyridin-2-ylmethyl)ethylene- - 1,2-diamine;

N- (2-hydroxyethyl) -N,N’ ,N’ -tris (3-methyl-pyridin-2- ylmethyl)ethylene-1,2-diamine; and

N-(2-methoxyethyl)-N,N’,N’-tris(3-methyl-pyridin-2- ylmethyl) ethylene-1,2-diamine. (C) Ligands of the general formula (IC): { “~Ng IN lk “2 ~ (IC) wherein

I Z,, 2, and 2, independently represent a coordidating TTT group selected from carboxylate, amido, -NH-C(NH)NH-, 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;

Q:, Qz, and Qs; independently represent a group of the formula:

I b c ”

R6 R8 wherein 5 > a+b+c > 1; a=0-5; b=0-5; c=0-5; n=1 or 2;

Y independently represents a group selected from -0-, -

S-, -80-, -80,-, -C(0)-, arylene, alkylene, heterocarylene, heterocycloalkylene, -(G)P-, -P(O)- and -(G)N- , wherein G “. is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; and

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 C,.¢-alkylene optionally substituted by C;.4-alkyl, -F, -Cl, -Br or -I.

Z,, 2, and Z; 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-1l-yl, and optionally substituted quinolin-2-yl. Preferably, 2,, Z. and

Z; each represent optionally substituted pyridin-2-yl.

Optional substituents for the groups Z,, Z, and Z; are preferably selected from C,4-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl, preferably methyl.

Also preferred is that Q,, Q; and Q; are defined such that a=b=0, c=1 or 2, and n=1. 5

Preferably, each Qi, Q: and Qi: independently represent Cj-4- - alkylene, more preferably a group selected from -CHz- and -

CH,CH,-.

The groups R5, R6, R7, R8 preferably independently represent a group selected from -H, hydroxy-Cy-Cz-alkyl, halo-C¢-Czo- alkyl, nitroso, formyl-Cy-Cy-alkyl, carboxyl-Ce-Czo-alkyl and esters and salts thereof, carbamoyl-Cy-Cio-alkyl, sulfo-Cy-

Cz0-alkyl and esters and salts thereof, sulfamoyl-Cg-Cio- alkyl, amino-Cy-Czo-alkyl, aryl-Co,-Czo-alkyl, Co~Czo-alkyl, alkoxy-Cy-Cg-alkyl, carbonyl-Cy-Cs-alkoxy, and Cy-Cio- alkylamide. Preferably, none of R5-R8 is linked together.

t *, WO 01/16271 PCT/EP00/08076

Preferably, the ligand is selected from tris (pyridin-2- ylmethyl)amine, tris (3-methyl-pyridin-2-ylmethyl)amine, tris (5-methyl-pyridin-2-ylmethyl) amine, and tris(6-methyl- pyridin-2-ylmethyl) amine. (D) Ligands of the general formula (ID):

Ry

Q Q QR; oN NT on AQ

Qs

RY

(ID) : wherein

S _ Ri, Rz, and R; independently represent a group selected from hydrogen, hydroxyl, halogen, -NH-C(NH)NH;, -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;

Q independently represent a group selected from Ci.3- alkylene optionally substituted by H, benzyl or C;.g-alkyl;

Q:, Q. and Q; independently represent a group of the formula:

R6 R8 wherein 5 > a+b+c > 1; a=0-5; b=0-5; c=0-5; n=1 or 2; ’ Y independently represents a group selected from -O-, -

S-, -80-, -802-, -C(0)-, arylene, alkylene, heterocarylene, heterocycloalkylene, -(G)P-, -P(0)- and -(G)N- , wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, each except hydrogen being optionally substituted by one or more functional groups E; and ) ) RS, R6, R7, RS independently represent a group selected

E£rom hydrogen, hydroxyl, halogen, -R and -OR, wherein R represents alkyl, alkenyl, cyrioalkyl, heternrycloalkyl, ee aryl, heteroaryl or a carbonyl derivative group, R being optionally substituted by one or more functional groups E, or RS 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;.g-alkylene optionally substituted by C;.4-alkyl, -F, -Cl, -Br or -I,

oN "Wo 0116271 PCT/EP00/08076 provided that at least one, preferably at least two, of

Ri, R; and R; is a coordinating group.

At least two, and preferably at least three, of R;, R; and Rj; independently represent a group selected from carboxylate, amido, -NH-C(NH)NH,, 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 R:, Ra, Rj; 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.

Preferably, substituents for groups Ri, R:, R;, when - representing a heterocyclic or heteroaromatic ring, are selected from C;.,-alkyl, aryl, arylalkyl, heteroaryl, methoxy, hydroxy, nitro, amino, carboxyl, halo, and carbonyl.

Preferably, Q:, Q. and Q; are defined such that a=b=0, ¢=1,2,3 or 4 and n=1. Preferably, the groups Qi, Q: and Q, " 25 independently represent a group selected from -CH,- and -

CH,CH,-.

Group Q is preferably a group selected from -CH,CH,- and -

CH,CH,CH;-.

] The groups R5, R6, R7, R8 preferably independently represent ~ a group selected from -H, hydroxy-Co-Czo-alkyl, halo-Cy-Cjqo- alkyl, nitroso, formyl-Co-Czo-alkyl, carboxyl-Co-Czo-alkyl and esters and salts thereof, carbamoyl-Co-Czo-alkyl, sulfo-C,-

Czo-alkyl and esters and salts thereof, sulfamoyl-Cg¢-Cyo- alkyl, amino-Co-Czo-alkyl, aryl-Cyo-Cio-alkyl, Co-Cao-alkyl, alkoxy-Cy,-Cg-alkyl, carbonyl-C,-Cs-alkoxy, and Cy-Cazo- alkylamide. Preferably, none of R5-R8 is linked together.

In a preferred aspect, the ligand is of the general formula (IID):

N N—u ,

R1I—a;7 NN XR

R3 - | (IID) oo wherein Rl, R2, R3 are as defined previously for Ri, Rz, Rs, and Q;, Q, Q3 are as defined previously. ;

Preferred classes of ligands according to this preferred aspect, as represented by formula (IID) above, are as follows: (i) ligands of the general formula (IID) wherein:

Rl, R2, R3 each independently represent a coordinating group selected from carboxylate, amido, -NH-C(NH)NH,

ERA *. WO 01/16271 PCT/EP00/0S076 : 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:

Rl, 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-1l-yl, and optionally substituted quinolin-2-yl. (ii) ligands of the general formula (IID) wherein: two of Rl, R2, R3 each independently represent a . coordinating group selected from carboxylate, amido, -NH- 'C(NH)NH;, 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 Rl, R2, R3 represents a group selected from hydrogen, C;-2¢ optionally substituted alkyl, Ci-zo optionally substituted arylalkyl, aryl, and C;.;p optionally substituted

NR;* (wherein R=C;.g-alkyl).

In this class, we prefer that: two of Rl, 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-1l-yl, and optionally substituted quinolin-2-yl; and one of Rl, R2, R3 represents a group selected from hydrogen, Ci.;o optionally substituted alkyl, Ci.s-furanyl, C;.s optionally substituted benzylalkyl, benzyl, C;.s optionally substituted alkoxy, and C;.;, optionally substituted N*Me,.

In especially preferred embodiments, the ligand is selected ) 10 from: : Pz3 \

Ny No P23 a, -~

Pzl TN Qu u x NN Pz \ N SQ _/ / ] ) - Pp Et } ] Co o CT oC rag .

Py Pann Pzl Pam \ N Nh AN. NO Pzl

Et . Et wherein -Et represents ethyl, -Py represents pyridin-2-yl,

Pz3 represents pyrazol-3-yl, Pzl represents pyrazol-1l-yl, and Qu represents quinolin-2-yl.

oT wooen PCT/EP00/08076 . - 38 =~ (E) Ligands of the general formula (IE):

T1— [2 (Q1) r=] oN (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;

Q1 and Q2 independently represent a group of the formula:

R6 R8 — =e) [YI] = [CT . R7 RY ol wherein =) > d+e+f > 1; d=0-5; e=0-5; £f=0-5; each Y1 independently represents a group selected from -0-, -S-, -80-, -S80,-, -C(0)-, arylene, alkylene, heteroarylene, heterocycloalkylene, -(G)P-, -P(O)- and - (G)N- , 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>1, each -[-N(R1)-(Ql),-]1- group is independently defined;

E Rl, R2, R6, R7, R8, RY 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 3 10 with R9, or R6 together with R9 and/or independently R7 together with R8, represent Cj.¢-alkylene optionally substituted by C;.4-alkyl, -F, -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 R5, wherein R4 and R5 are as defined for R1-R9, and if g=0 and . 8>0, Rl together with R4, and/or R2 together with R5, may } optionally independently represent =CH-R10, wherein R10 is nN as defined for R1-R9, or

Tl and T2 may together (-T2-Tl-) represent a covalent - bond linkagc when ss and gO Co if T1 and T2 together represent a single bond linkage,

Q1 and/or Q2 may independently represent a group of the formula: =CH—[—Y1—].—CH= provided Rl and/or R2 are absent, and Rl and/or R2 may be absent provided Q1 and/or Q2 independently represent a group of the formula: =CH—[—Y1—] CH=.

° *. WO 01/16271 PCT/EP00/08076 : The groups R1-R9 are preferably independently selected from

E -H, hydroxy-Co-Czo-alkyl, halo-Cy-Czp-alkyl, nitroso, formyl- : Co-Cao-alkyl, carboxyl-Co-Czo-alkyl and esters and salts thereof, carbamoyl-Co-Czo-alkyl, sulpho-Cy-Cio-alkyl and esters and salts thereof, sulphamoyl-Co-Cio-alkyl, amino-Cop-

Cao-alkyl, aryl-Cy-Cao-alkyl, heteroaryl-Co-Cao-alkyl, Co-Cao- alkyl, alkoxy-Co-Cg-alkyl, carbonyl-Co-Ce¢-alkoxy, and aryl-Co-

Ce-alkyl and Co-Cyo-alkylamide.

One of R1-R9 may be a bridging group which links the ligand moiety to a second ligand moiety of preferably the same 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 heterocaryl-containing bridge, more preferably C,.s-alkylene optionally substituted by C;.,-alkyl, -F, -Cl, -Br or -I. "In a first variant according to formula (IE), the groups Tl 5 "and T2 together form a single bond linkage and s>1, according to general formula (IIE): @ 1

N——@]

Ri 8 (IIE)

wherein R3 independently represents a group as defined for

R1-R9; Q3 independently represents a group as defined for

Ql, Q2; h represents zero or an integer from 1 to 6; and s=s8-1.

In a first embodiment of the first variant, in general formula (IIE), s=1, 2 or 3; r=g=h=1; d=2 or 3; e=f=0;

R6=R7=H, preferably such that the ligand has a general formula selected from:

Claims

Women PCT/EP00/08076 a. CLAIMS:

B 1. A liquid bleaching composition comprising an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by atmospheric oxygen, and a liquid carrier or solvent, wherein the composition is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.

2. A liquid bleaching composition according to claim 1, wherein the organic substance comprises a pentadentate ligand of the general formula (B): T i

“ . Rl R2 (B) wherein each R* , R? independently represents -R‘-R°, R® represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R*-R®, each R® independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R® independently represents an optionally N- substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl,

- pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, ow pyrimidinyl, triazolyl and thiazolyl.

3. A liquid bleaching composition according to claim 2, wherein the ligand is N,N-bis(pyridin-2-yl-methyl)-1,1- oe bis (pyridin-2-yl) -l1-amincethane.

4. A liquid bleaching composition according to any of claims 1 to 3, wherein the medium has a pH value in the range from pH 6 to 11.

: 5. A liquid bleaching composition according to claim 4, . wherein the medium has a pH value in the range from pH 7 to

10. ol 15

6. A liquid bleaching composition according to any of claims 1 to 5, wherein the medium is substantially devoid of ) a: transition metal sequestrant.

7. A liquid bleaching composition according to any of claims 1 to 6, wherein the medium further comprises a surfactant. oT

8. A liquid bleaching composition according to any of claims 1 to 7, wherein the medium further comprises a builder.

9. A liquid bleaching composition according to any of claims 1 to 8, wherein the crganic substance comprises a preformed complex of a ligand and a transition metal.

10. A liquid bleaching composition according to any of claims 1 to 8, wherein the organic substance comprises a free ligand that complexes with a transition metal present in the water.

11. A liquid bleaching composition according to any of claims 1 to 8, wherein the organic substance comprises a free ligand that complexes with a transition metal present in the substrate.

12. A liquid bleaching composition according to any of claims 1 to 8, wherein the organic substance comprises a composition of a free ligand or a transition metal- substitutable metal-ligand complex, and a source of transition metal. ~ 13. A method of bleaching a substrate comprising applying to the substrate a liquid bleaching composition that . comprises an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by atmospheric oxygen, and a liquid carrier or solvent, wherein the composition is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.

14. A method to claim 13, wherein the organic substance comprises a pentadentate ligand of the general formula (B):

} : T if Rl R2 - (B) wherein each R' , R? independently represents -R‘-R%, = R?® represents hydrogen, optionally substituted alkyl, . aryl or arylalkyl, or -R*-RS5, . each R' independently represents a single bond or } optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or . carboxylic amide, and . each R®° independently represents an optionally N- substituted aminoalkyl group or an optionally substituted . heteroaryl group selected from pyridinyl, pyrazinyl, ~ pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, i pyrimidinyl, triazolyl and thiazolyl. = 15: #& method acesrding to claim 14, wherein the ligand is oo N,N-bis (pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1- aminoethane.

16. A method according to any of claims 13 to 15, wherein the medium is as defined in any of claims 4 to 8.

17. Use of an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by the atmospheric oxygen, as a catalytic os ‘ - 96 -~- bleaching agent in a liquid bleaching composition substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system.

18. A method of treating a textile by contacting the textile with a liquid bleaching composition that comprises an organic substance which forms a complex with a transition metal, the complex catalysing bleaching by atmospheric oxygen, and a liquid carrier or solvent, wherein the composition is substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment.

19. A liquid bleaching composition according to claim 1, wherein the organic substance comprises a pentadentate hn ligand. A 20. A liquid bleaching composition according to claim 19, wherein the pentadentate ligand is in the form of an iron complex.