WO2003104378A1 - Ligand and complex for catalytically bleaching a substrate - Google Patents

Abstract

The present invention provides a bleaching composition comprising a [3.3.1] bicyclo compound carrying at least one tertiary amine group together with a peroxygen source.

Description

LIGAND AND COMPLEX FOR CATALYTICALLY BLEACHING A SUBSTRATE

FIELD OF INVENTION

This invention relates to a class of ligand or complex thereof useful as catalysts for catalytically bleaching substrates .

BACKGROUND OF INVENTION

The use of bleaching catalysts for stain removal has been developed over recent years.

The search for new classes of compounds that are suitable as peroxyl catalysts is ongoing.

Various [3.3.1] bicyclo compounds and complexes thereof are discussed in the literature, see for example: Co ba P. et al., J. Chem. Soc. Dalton Trans, 1998, (23) 3997-4001; Bόrzel et al. Chem. Eur. J. 1999, 5, No. 6, 1716 to 1721 and review by P. Comba in Coordination Chemistry Reviews 2000, 200-202, 217 to 245, entitled "Coordination compounds in the Entactic State" . These compounds are discussed in terms of their physical properties.

O0060045 discloses a bleaching system comprising: a) from about lppb, by weight of a transition metal catalyst comprising: i) a transition metal; ii) a ligand having formula (I) :

wherein each R is independently hydrogen, hydroxyl, C1-C4 alkyl, and mixtures thereof; Rl is C1-C4 alkyl, C6-C10 aryl, and mixtures thereof; R2 is C1-C4 alkyl, C6-C10 aryl, and mixtures thereof; R3 and R4 are each independently hydrogen, C1-C8 alkyl, C1-C8 hydroxyalkyl, -(CH₂)_XC0₂R5 wherein R5 is C1-C4 alkyl, x is from 0 to 4, and mixtures thereof; X is carbonyl, -C(R6)2- wherein each R6 is independently hydrogen, hydroxyl, C1-C4 alkyl, and mixtures thereof; b) optionally a source of hydrogen peroxide; and c) the balance carriers and adjunct ingredients. However, the teaching of O0060045 limits substituents at the nitrogens (3 and 7 positions) of bicyclostructure to homoaromatic carbon groups, namely alkyl and aryl. The general structure of Formula (I) is referred to as a bispidon.

SUMMARY OF INVENTION

Our earlier filed application PCT/EP01/13314 , filed 15 November 2002, which claims priority from GB0030673.8, filed 15 December 2000, discloses the use of various bispidon compounds. Referring to the structure above, PCT/EP01/13314 teaches that there is an advantage to be secured by having at least one of Rl and R2 as group containing a heteroatom capable of coordinating to a transition metal. We have now found that by having at least one of Rl and R2 as a group that is a tertiary amine linked to one or more of the nitrogen atoms of the bicyclo structure by a C2 to C4 alkyl chain further advantages are secured. In addition, we have also found that heterocycles other than pyridyl may be used at the 2 and 4 positions.

Accordingly, in a first aspect, the present invention provides a bleaching composition comprising:

A bleaching composition comprising:

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

wherein at least one of Rl and R2 is an optionally substituted tertiary amine of the form -C2-C4-alkyl-NR7R8, in which R7 and R8 are independently selected from the group consisting of straight chain, branched or cyclo C1-C12 alkyl, benzyl, the -C2-C4-alkyl- of the -C2-C4-alkyl-NR7R8 may be substituted by 1 to 4 Cl-C2-alkyl, or may form part of a C3 to C6 alkyl ring, and in which R7 and R8 may together form a saturated ring containing one or more other heteroatoms, the other of Rl and R2 being independently selected from: -C2-C4-alkyl-NR7R8 as defined above, -C1-C24-optionally subsituted-alkyl, -C6-C10-aryl, -Cl-C4-alkyl-C6-C10-aryl, a heterocycloalkyl: selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethylene imine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be connected to the ligand via any atom in the ring of the selected heterocycloalkyl, a -Cl-C6-alkyl-heterocycloalkyl, wherein the heterocycloalkyl of the -Cl-C6-heterocycloalkyl is selected from the group consisting of: piperidinyl, piperidine, 1,4- piperazine, tetrahydrothiophene, tetrahydrofuran, pyrrolidine, and tetrahydropyran, wherein the heterocycloalkyl may be connected to the -Cl-C6-alkyl via any atom in the ring of the selected heterocycloalkyl, a -Cl-C6-alkyl-heteroaryl, wherein the heteroaryl of the - Cl-C6-alkylheteroaryl is selected from the group consisting of: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1, 3, 5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl may be connected to the - Cl-C6-alkyl via any atom in the ring of the selected heteroaryl and the selected heteroaryl is optionally substituted by -Cl-C4-alkyl, -C0-C6-alkyl-phenol, -C0-C6- alkyl-thiophenol, -C2-C4-alkyl-thiol, -C2-C4-alkyl- thioether, -C2-C4-alkyl-alcohol, -C2-C4-alkyl-amine, and a -C2-C4-alkyl-carboxylate; R3 and R4 are independently selected from hydrogen, C1-C4- alkyl, phenyl, electron withdrawing groups and reduced products and derivatives thereof;

X is selected from: C=0, a ketal derivative of C=0, a thioketal of derivative of C=0, and -[C(R6)₂]_y- wherein y takes a value 0 or 1; each R6 is independently selected from hydrogen, hydroxyl, 0-Cl-C24-alkyl, O-benzyl, 0- (C=0) Cl-C24-alkyl, Cl-C24-alkyl;

z groups are same heteroaromatic groups, selected from the group consisting of: pyridinyl; pyri idinyl; pyrazinyl; triazolyl; pyridazinyl; 1, 3, 5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, and the selected Z is optionally substituted by -Cl-C4-alkyl;

b) the balance carriers and adjunct ingredients, together with at least 2 % wt/wt, most preferably at least 5% wt/wt, of a peroxygen bleach or source thereof.

It is most preferred that the peroxygen bleach or source thereof is other than that of an alkyl hydroperoxide.

In a second aspect, the present invention provides a bleaching composition comprising, in an aqueous medium, the bicyclo ligand of the general Formula (I) which forms a complex with a transition metal, the complex catalysing bleaching of a substrate, wherein the aqueous medium contains a peroxide other than an alkyl peroxide. It is preferred that the medium has a pH value in the range from pH 6 to 12 and most preferably from pH 8 to 11.

Catalysts of the present invention may be incorporated into a composition together with a peroxyl species or source thereof. For a discussion of acceptable ranges of a peroxyl species or source thereof and other adjuvants that may be present the reader is directed to United States Patent 6,022,490, the contents of which are incorporated by reference.

The present invention extends to a method of bleaching a substrate comprising applying to the substrate, in an aqueous medium, the bleaching composition according to the present invention.

The present invention extends to a commercial package comprising the bleaching composition according to the present invention together with instructions for its use.

Any suitable textile that is susceptible to bleaching or one that one might wish to subject to bleaching may be used. Preferably the textile 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 treatment liquor. In particular, the treatment may be effected in a wash cycle for cleaning laundry. More preferably, the treatment is carried out in an aqueous detergent bleach wash liquid. The organic substance can be contacted with the textile fabric in any conventional manner. For example it may be applied in dry form, such as in powder form, or in a liquor that is then dried, for example in an aqueous spray-on fabric treatment fluid or a wash liquor for laundry cleaning, or a non-aqueous dry cleaning fluid or spray-on aerosol fluid.

In a particularly preferred embodiment the method according to the present invention is carried out on a laundry fabric using aqueous treatment liquor. In particular the treatment may be effected in, or as an adjunct to, an essentially conventional wash cycle for cleaning laundry. More preferably, the treatment is carried out in an aqueous detergent wash liquor. The organic substance can be delivered into the wash liquor from a powder, granule, pellet, tablet, block, bar or other such solid form. The solid form can comprise a carrier, which can be particulate, sheet-like or comprise a three-dimensional object. The carrier can be dispersible or soluble in the wash liquor or may remain substantially intact. In other embodiments, the organic substance can be delivered into the wash liquor from a paste, gel or liquid concentrate.

In the alternative, the organic substance can be presented in the form of a wash additive that preferably is soluble. The additive can take any of the physical forms used for wash additives, including powder, granule, pellet, sheet, tablet, block, bar or other such solid form or take the form of a paste, gel or liquid. Dosage of the additive can be unitary or in a quantity determined by the user. While it is envisaged that such additives can be used in the main washing cycle, the use of them in the conditioning or drying cycle is not hereby excluded.

The present invention is not limited to those circumstances in which a washing machine is employed, but can be applied where washing is performed in some alternative vessel. In these circumstances it is envisaged that the organic substance can be delivered by means of slow release from the bowl, bucket or other vessel which is being employed, or from any implement which is being employed, such as a brush, bat or dolly, or from any suitable applicator.

Suitable pre-treatment means for application of the organic substance 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. Similar means for application are employed in those embodiments where the organic substance is applied after the main washing and/or conditioning steps have been performed, e.g. prior to or after ironing or drying of the cloth. For example, the organic substance may be applied using tapes, sheets or sticking plasters coated or impregnated with the substance, or containing microcapsules of the substance. The organic substance may for example be incorporated into a drier sheet so as to be activated or released during a tumble-drier cycle, or the substance can be provided in an impregnated or microcapsule- containing sheet so as to be delivered to the textile when ironed.

DETAILED DESCRIPTION OF THE INVENTION The ligand as described herein is capable of dynamic inversion. The ability of the ligand to chelate to a TM depends upon the stereochemistry of the substituents . It is preferred that substituents are endo-endo, but it is likely that stereochemical conversion takes place by retro-Mannich conversion. Retro-Mannich may be prevented by changing the groups present such that retro-Mannich reactions are unfavoured. Nevertheless, it is likely that endo-exo and exo-exo ligands as described herein coordinate to transition metal ions in many instances and are capable of functioning as air bleaching catalysts.

Referring to ligands and complexes thereof and bleaching compositions derived therefrom with respect to Formula (I), it is preferred that each z is the same; and R3 = R4. Preferred Z groups are pyridine, benzimidazole, thiazole, imidazole. Most preferred z groups are of the form

, wherein R is independently selected from: hydrogen, F, CI, Br, hydroxyl, Cl-C4-alkyl-, -NH-CO-H, -NH- CO-Cl-C4-alkyl, -NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl. Of the R groups it is preferred that R is H or -Cl-C4-alkyl .

It is preferred that R3 and R4 are selected from the group consisting of: -CH20H, -CH20C (0) Cl-C20-alkyl, -C (0) 0-C1-C6- alkyl, benzyl ester, -CN, Cl-C6-alkyl, benzyl, phenyl, and C1-C4-OR wherein R is selected from the group consisting of H, Cl-C24-alkyl or C (0) -Cl-C24-alkyl . Most preferred R3 and R4 groups are: -C(0)-0-CH3, -C (0) -0-CH2CH3, benzyl ester and CH20H. Notwithstanding the above, R3 and R4 are initially important such that synthesis proceeds to provide the core structure of Formula (I), namely the [3.3.1] bicyclo structure. After the core structure of Formula (I) is formed reduction or other synthetic methods may change R3 and R4. Whilst R3 and R4 may participate in influencing the activity of the catalyst in the broadest aspect R3 and R4 may be independently selected from electron withdrawing groups and reduced products and derivatives thereof. The R3 and R4 substituents do not have a substantial influence on the catalyst per se except to change the hydrophobisity/solubility of the ligand or transition metal catalyst formed therefrom.

It is preferred that the -C2-C4-alkyl-NR7R8 is selected from the group consisting of: -CH2CH2-NR7R8, -CH2CMe2-NR7R8, - CMe2CH2-NR7R8, -CMeHCH2-NR7R8, -CMeHCMeH-NR7R8, -CH2CMeH- NR7R8, -CH2CH2CH2-NR7R8, -CH2CH2CMe2-NR7R8, -CH2CMe2CH2-

NR7R8, -CH2CH2-NEt2, -CH2CH2-N ( i-Pr) 2 ,

, and

,

. Preferred groups for R7 and R8 are CH3, -C2H5,

-C3H7, -C4H9, -C5H11, -C6H13, and -CH2C6H5. It is most preferred that at least one of R7 and R8 is an optionally substituted alkyl chain of at least five carbon atoms. Other preferred groups for R7 and R8 are -CH3, -CH2CH3, - CH(CH3)2 or where R7 and R8 together with the N form a optionally substituted cyclic structure selected from the

group consisting of:

Rl and R2 it is most preferred that Rl is a C2-C4-alkyl- NR7R8 and most preferably both Rl and R2 are independently C2-C4-alkyl-NR7R8. It is preferred that the -C2-C4-alkyl- NR7R8 is a C2-alkyl-NR7R8.

It is preferred that X is selected from: C=0, and -[C(R6)₂] wherein each R6 is independently selected from hydrogen, hydroxyl, Cl-C24-alkoxy and Cl-C24-alkyl . In particular X is preferred in the form C(OH)₂, syn-CH(OH) and anti-CH (OH) . One skilled in the art will be aware that when X = C(OH)2 a solvent adduct may exist, e.g., when present in methanol the C(OMe)2 adduct will be formed. This adduct will exchange in water such that X = C(OH)2 which again is equilibrium with X = C=0.

Particularly preferred ligands are exemplified below :

wherein -NR6R7 is selected from the group consisting of

NMe2, NEt2, -N(i-Pr)2,

The catalyst may be used as a preformed complex of the ligand and a transition metal. Alternatively, the catalyst may be formed from the 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 composition may also be formulated as a composition of the free ligand or a transition metal-substitutable metal- ligand complex, and a source of transition metal, whereby the complex is formed in si tu 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, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI.

The ligand forms a complex of the general formula (Al) : [M_aL_kX_n] Y_ffi (Al )

in which :

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

L represents a ligand as herein defined, 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, preferably selected from O^2", RB0₂ ^2", RCOO^", RCONR^", OH^", N0₃ ^", NO, S^2", RS^", P0₄ ^3", P0₃OR^3", H₂0, C0₃ ^2~, HC0₃ ^", ROH, N(R)₃, ROO^", 0₂ ^2", 0₂ ^", RCN, CI^", Br^", OCN^", SCN^", CN^", N₃ ^", F^", I^", RO^", C10^", and CF₃S0₃ ^", and more preferably selected from O^2", RB0₂ ^2", RCOO^", OH^", N0₃ ^", S^2", RS^", P0₃ ^4", H₂0, C0₃ ^2", HC0₃ ^", ROH, N(R)₃, CI^" , Br^", OCN^", SCN^", RCN, N₃ ^", F^", I^", RO^", C10₄ ^", and CF₃S0₃ ^";

Y represents any non-coordinated counter ion, preferably selected from C10₄ ^", BR₄ ^", [MX₄]^", [MX₄]^2", PF₆ ^", RCOO^", N0₃ ^", RO^", N⁺(R)₄, ROO^", 0₂ ^2", 0₂ ^", CI^" , Br^", F^", I^", CF₃S0₃ ^", S₂0₆ ^2~ , OCN^", SCN^", H₂0, RB0₂ ^2", BF₄ ^" and BPh₄ ^", and more preferably selected from C10₄ ^", BR₄ ^" , [FeCl₄] ^", PF₆ ^~, RCOO^", N0₃ ^", RO^", N⁺(R)₄, CI^" , Br^", F^", I^", CF₃S0₃ ^", S₂0₆ ^2" , OCN^", SCN^", H₂0 and BF₄ ^"; a represents an integer from 1 to 10, preferably from 1 to 4; k represents an integer from 1 to 10; n represents an integer from 1 to 10, preferably from 1 to 4; m represents zero or an integer from 1 to 20, preferably from 1 to 8; and each R independently represents a group selected from hydrogen, hydroxyl, -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, wherein E independently represents a functional group selected from -F, -CI, -Br, -I, -OH, -OR', -NH₂, -NHR', -N(R')₂, -N(R')₃ ⁺, -C(0)R', -OC(0)R', -COOH, -COO^" (Na⁺, K⁺) , -COOR', -C(0)NH₂, -C(0)NHR', -C(0)N(R')₂, heteroaryl, -R', -SR', -SH, -P(R')₂, -P(0)(R')₂, -P(0)(OH)₂, - P(0)(OR')₂, -N0₂, -S0₃H, -S0₃ ^"(Na⁺, K⁺) , -S(0)₂R', -NHC(0)R', and -N (R') C (0) R', wherein R' represents cycloalkyl, aryl, arylalkyl, or alkyl optionally substituted by -F, -CI, -Br, -I, -NH₃ ⁺, -S0₃H, -S0₃ ^"(Na⁺, K⁺) , -COOH, -COO^" (Na⁺, K⁺) , - P(O) (OH) ₂, or -P(O) (0^"(Na⁺, K⁺))₂, and preferably each R independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or Cι_₄- alkyl.

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 ^", PF₆ ^", RS0₃ ^", RS0₄ ^", S0₄ ^2", N0₃ ^", F^", CI^", Br^", or I^", with R being hydrogen, 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 R⁷COO^", C10₄ ^", BF₄ ^", PF₆ ^", RS0₃ ^" (in particular CF₃S0₃ ^") , RS0₄ ^", S0₄ ^2", N0₃ ^", F^", Cl^~, Br^", and I^~, wherein R represents hydrogen or optionally substituted phenyl, naphthyl or Cι-C alkyl.

The novel compounds of Formula (I) as provided by the present invention also extend to their various transition metal complexes, the transition metal complexes are as discussed above with reference to (Al) .

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 si tu 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 si tu 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 FeΞ0₄ 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_n 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 M ions present in the substrate or wash liquor to form the active catalyst in si tu. 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) .

The catalysts according to the present invention may be used for laundry cleaning, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.). As is generally known in the art, bleaching compositions are also employed in waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact lens disinfection.

In typical washing compositions the level of the organic substance is such that the in-use level is from lμM to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 μM. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching. These levels reflect the amount of catalyst that may be present in a wash dose of a detergent composition. The bleaching composition comprises at least 1 ppb of the ligand or complex thereof. 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.

Synthesis In addition to the utility of the ligands and complexes of the present invention as catalysts another advantage is that the ligands are generally relatively easy to synthesize in comparison to other ligands. The following is one example of a strategic synthetic approach; it will be evident to one skilled in the art of synthetic organic chemistry that many approaches may be taken to obtain ligands and complexes for use in the present invention. The ease of synthesis of the ligand of Formula (I) is dependent upon the nature of substituents about the structure. The ligands of Formula (I) are most preferably symmetric. Synthesis of these types of molecules are found in articles by U. Holzgrabe et al. in Arch. Pharm. (Weinheim, Ger.) 1992, 325, 657 and A. Samhammer et al . Arch. Pharm. (Weinheim, Ger.) 1984, 322, 557. Below is given a schematic example illustrating the ease of synthesis. The synthesis is shown in a two step synthesis, Scheme 1 and Scheme 2, but in some cases may be conducted as a "one-pot" synthesis depending upon the nature of the substituents. Nevertheless, where substituents at positions 7 and 3 are different a two step synthesis is preferred. The product of reaction as found in Scheme 1 is referred to as dimethyl 2, 6-di- (2-pyridyl) -1-methyl-piperid- 4-one-3, 5-dicarboxylate (NPy2), which can easily tautomerize to the enol. The synthesis is exemplified in R. Haller, K.W. Merz, Pharm . Acta Helv. , 1963, 442.

Scheme 1

NPy2

Scheme 2

Another intermediate that may be produced according to the general teachings of Scheme 1 wherein MeNH₂ is replaced by Me₂NCH₂CH₂NH₂ such that a product referred to as dimethyl-2, 6- di- (2-pyridyl) -1- (N,N-dimethylamino) ethylene-piperid-4-one- 3, 5-dicarboxylate is produced, the structure of which is given below.

One skilled in the art will appreciate that whilst Ac [- CO(0)Me] is an electron withdrawing group and electron withdrawing groups are generally preferred to facilitate synthesis other groups will also allow the reaction to proceed. Examples of suitable electron withdrawing groups are given above and will be evident to one skilled in the art. The reaction is also driven by precipitation of the product from solution.

In instances, depending upon the nature of the substituents, for example a phenolic group, it will be necessary to protect certain functional groups. The choice of protecting groups during synthesis to prevent undesirable reactions will be evident to one skilled in the art. For a discussion of protecting groups in organic synthesis the reader is directed to T. W. Green and P. G. M. Wuts, Protective Groups In Organic Synthesis 3nd Ed.; J. Wiley and Sons, 1999.

It will be evident that if a diamine is substituted for methylamine in the reaction illustrated in Scheme 2 two structures may be linked together via the 7 positions as found in the structure below.

In addition, if a diamine is substituted for methylamine in the reaction illustrated in Scheme 1 a NPy2 structure is formed that is linked at the 3 positions. Obviously, this dimer would serve as a precursor to other dimer and polymer type structures. The present invention is confined to "monomer" ligands and not the dimer and polymer units linked by a covalent bond as described above. The term "monomer" as used herein is used to exclude these products in which covalently linked polyligand type structures are formed.

The Detergent Composition

The air bleach catalyst and may be used in a detergent composition specifically suited for stain bleaching purposes, and this constitutes a second aspect of the invention. To that extent, the composition comprises a surfactant and optionally other conventional detergent ingredients. The invention in its second aspect provides an enzymatic detergent composition which comprises from 0.1 -

50 % by weight, based on the total detergent composition, of one or more surfactants. This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight of one or more nonionic surfactants. The surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in not normally desired owing to their relatively high cost. The enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2%.

The condition of "the balance carriers and adjunct ingredients" should be taken to be at least 1% wt/wt of a surfactant, preferably at least 5% wt/wt.

In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981.

Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C_δ-C₂₂ alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs~ Cis primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO. Suitable anionic detergent compounds which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Cs-Cι₈ alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C₉-C₂o benzene sulphonates, particularly sodium linear secondary alkyl C₁₀-C₁₅ benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium Cu-Cι₅ alkyl benzene sulphonates and sodium Cι₂-Cι_a alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides .

Preferred surfactant systems are mixtures of anionic with^' nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever) . Especially preferred is surfactant system that is a mixture of an alkali metal salt of a C1₆-C₁₈ primary alcohol sulphate together with a Cι₂-C₁₅ primary alcohol 3-7 EO ethoxylate.

The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25-90% by weight of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40% by weight of the surfactant system.

The detergent composition may take any suitable physical form, such as a powder, granular composition, tablets, a paste or an anhydrous gel.

Peroxygen Bleach or Source Thereof In a peroxyl bleaching mode the composition of the present invention uses a peroxyl species to bleach a substrate. The peroxy bleaching species 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 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 1-35% by weight, preferably from 5-25% by weight. One skilled in the art will appreciate that these amounts may be reduced in the presence of a bleach precursor e.g., N,N,N'N'-tetraacetyl ethylene diamine (TAED) . Another suitable hydrogen peroxide generating system is a combination of a C1-C4 alkanol oxidase and a C1-C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Such combinations are disclosed in International Application PCT/EP 94/03003 (Unilever), 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 :

wherein R is an alkylene 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

group or a quaternary ammonium group.

Typical monoperoxy acids useful herein include, for example: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy- . alpha. -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) ;

(v) 1, 9-diperoxyazelaic acid;

(vi) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-l, 4-diotic 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.

Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988;

864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and U.S. Pat. Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 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 Pat. Nos. 4,751,015 and 4,397,757, in EP-A0284292 and EP-A-331, 229. Examples of peroxyacid bleach precursors of this class are:

2- (N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride (SPCC) ;

N-octyl-N, -dimethyl-NlO-carbophenoxy 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 and in European Patent Specification No.'s 458,396 and 464,880.

Any one of these peroxyacid bleach precursors can be used in the present invention, though 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-4- methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3, 5, 5-trimethyl hexanoyl- oxybenzene sulphonate (STHOBS) ; and the substituted cationic nitriles.

Other classes of bleach precursors for use with the present invention are found in WO0015750, for example 6- (nonanamidocaproyl) oxybenzene sulphonate .

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

Enzymes

The detergent compositions of the present invention may additionally comprise one or more enzymes, which provide cleaning performance, fabric care and/or sanitation benefits .

Said enzymes include oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. Suitable members of these enzyme classes are described in Enzyme nomenclature 1992: recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology on the nomenclature and classification of enzymes, 1992, ISBN 0-12-227165-3, Academic Press.

Examples of the hydrolases are carboxylic ester hydrolase, thiolester hydrolase, phosphoric monoester hydrolase, and phosphoric diester hydrolase which act on the ester bond; glycosidase which acts on O-glycosyl compounds; glycosylase hydrolysing N-glycosyl compounds; thioether hydrolase which acts on the ether bond; and exopeptidases and endopeptidases which act on the peptide bond. Preferable among them are carboxylic ester hydrolase, glycosidase and exo- and endopeptidases. Specific examples of suitable hydrolases include (1) exopeptidases such as aminopeptidase and carboxypeptidase A and B and endopeptidases such as pepsin, pepsin B, chymosin, trypsin, chymotrypsin, elastase, enteropeptidase, cathepsin B, papain, chymopapain, ficain, thrombin, plasmin, renin, subtilisin, aspergillopepsin, collagenase, clostripain, kallikrein, gastricsin, cathepsin D, bromelain, chymotrypsin C, urokinase, cucumisin, oryzin, proteinase K, thermomycolin, thermitase, lactocepin, thermolysin, bacillolysin. Preferred among them is subtilisin; (2) glycosidases such as α-amylase, β-amylase, glucoamylase, isoamylase, cellulase, endo-1, 3 (4) -β-glucanase (β-glucanase), xylanase, dextranase, polygalacturonase (pectinase) , lysozyme, invertase, hyaluronidase, pullulanase, neopullulanase, chitinase, arabinosidase, exocellobiohydrolase, hexosaminidase, mycodextranase, endo- 1, 4-β-mannanase (hemicellulase) , xyloglucanase, endo-β- galactosidase (keratanase), mannanase and other saccharide gum degrading enzymes as described in WO-A-99/09127. Preferred among them are -amylase and cellulase; (3) carboxylic ester hydrolase including carboxylesterase, lipase, phospholipase, pectinesterase, cholesterol esterase, chlorophyllase, tannase and wax-ester hydrolase. Preferred among them is lipase.

Examples of transferases and ligases are glutathione S- transferase and acid-thiol ligase as described in WO-A-98/59028 and xyloglycan endotransglycosylase as described in WO-A-98/38288.

Examples of lyases are hyaluronate lyase, pectate lyase, lipex, chondroitinase, pectin lyase, alginase II. Especially preferred is pectolyase, which is a mixture of pectinase and pectin lyase.

Examples of the oxidoreductases are oxidases such as glucose oxidase, methanol oxidase, bilirubin oxidase, catechol oxidase, laccase, peroxidases such as ligninase and those described in WO-A-97/31090, monooxygenase, dioxygenase such as lipoxygenase and other oxygenases as described in WO-A-99/02632, WO-A-99/02638, WO-A-99/02639 and the cytochrome based enzymatic bleaching systems described in WO-A-99/02641.

The activity of oxidoreductases, in particular the phenol oxidising enzymes in a process for bleaching stains on fabrics and/or dyes in solution and/or antimicrobial treatment can be enhanced by adding certain organic compounds, called enhancers. Examples of enhancers are 2,2'- azo-bis- (3-ethylbenzo-thiazoline-6-sulphonate (ABTS) and Phenothiazine-10-propionate (PTP) . More enhancers are described in WO-A-94/12619, WO-A-94/12620 , WO-A-94/12621, WO-A-97/11217, WO-A-99/23887. Enhancers are generally added at a level of 0.01% to 5% by weight of detergent composition.

Builders, polymers and other enzymes as optional ingredients may also be present as found in WO0060045.

Suitable detergency builders as optional ingredients may also be present as found in WO0034427.

The invention will now be further illustrated by way of the following non-limiting examples:

EXAMPLES

The ligand N,N-bis (pyridin- 2-yl-methyl) -1, 1-bis (pyridin-2- yl) -1-aminoethane (MeN4py) was prepared as described in EP 0 909 809 A2. The synthesis of the iron complex, [ (MeN4Py)FeCl]Cl, has been described elsewhere (WO 0116271.

Procedure for bispidone synthesis :

A suspension of 7.15 g (16.3 mmol) of piperidone (Npy2) (synthesis exemplified in R. Haller, K.W. Merz, Pharm . Act Helv. , 1963, 442) in 40 ml ethanol is treated with 1.72 g (19.6 mmol) of N, N-dimethylethylendiamine and 3.5 ml of formaldehyde (37% in water) - 36.1 mmol) and is refluxed for 30 min. The resulting clear, slight yellow to dark brown reaction solution is evaporated to half of its volume and left at 5°C for 24 h. The yellow precipitate formed is filtered, washed with little EtOH until the precipitate is white and dried under high vacuum. If no precipitate is obtained, the reaction mixture is evaporated to dryness, dissolved in as little EtOH as possible and left at 5°C for 72 h until a precipitate is formed.

Analytical data :

Melting point: 147 °C.

CH analysis: calc. (%) C 63.02 H 6.71 N 14.13 found (%) C 62.69 H 6.76 N 13.79

FAB^Sf BA) : 496.3 (MH⁺) ; C₂₆H₃₃N₅θ₅ M = 495.25 g/mol

¹H-NMR (300.133 MHz, CDC1₃) : δ = 1.98 (s, 3H, N-CH₃) , 2.32 (bs, 6H, N-(CH₃)₂), 2.49 (bs, 4H, N-CH₂-) , 2.61 (d, 2H, ²J_HH = 12.1 Hz, -CH₂-), 3.12 (d, 2H, ²J_HH = 9.5 Hz, -CH₂-) , 3.79 (s, 6H, OCH₃) , 4.66 (s, 2H, CH-Py) , 7.20 (dt, 2H, ³J_m = 4.8 Hz, ⁴J_HH = 1.1 Hz, Py-H), 7.73 (dt, 2H, ³J_HH = 7.7 Hz, ⁴J_HH = 1.8 Hz, Py-H), 8.11 (bd, 2H, ³J_HH = 7.7 Hz, Py-H) , 8.47 (dd, 2H, ³J_HH = 8.5 Hz, ⁴J_HH = 1.1 Hz, Py-H) .

Preparation of complex 1 2 mmol of metal salt (FeC12) dissolved in 1 ml methanol is added to 2 mmol of ligand dissolved in 1 ml acetotrile. After 24 h stirring at RT the solution is concentrated to 0.5 ml total volumne and treated with 5 mL of ethylacetate. The solution is sonicated in an ultrasonic bath. The resulting solid is filtered in dried in high vacuum. FeCl (N2Py2EtNMe2 ) ] CI C₂₆H₃₅Cl₂FeN₅0₆ - H₂0 M = 640.34 g/mol

Analytical data:

CHN Analysis calc. (%) C 48.77 H 5.51 N 10.94 found (%) C 49.15 H 5.79 N 10.61

FABMS( BA): 604.2 [FeCl (N2Py2EtNMe2 ^■ H₂0) ] H

Dimethyl 2 , 4-di- (2-pyridyl) -3-methyl-7- (pyridin-2- ylmethyl) -3, 7-diaza-bicyclo[3.3. l]nonan-9-one-l,5- dicarboxylate (N2Py3o) (MW: 515.22 g/mol) 2-Aminomethyl-pyridine (4.3 g, 39.7 mmol) and formaldehyde (37% in water) (6.5 mL, 79.4 mmol) were added to a suspension of NPy2 (12.71 g, 33.1 mmol) in 200 mL ethanol. The suspension was stirred under reflux for 30 minutes resulting in a clear brown solution. The solvent was removed under reduced pressure and the remaining solid was crystallised from ethanol to yield the title compound as a white solid (4.2 g, 25 %).

^-NMR (300 MHz, CDC1₃) : 1.94 (s, 3H, N-Me) , 2.68 (d, 2H, J=12Hz, bisHδax, bisH8ax-) ; 3.14 (d, 2H, J=12Hz, bisHδeq, bisHδeq) : 3.57 (s, 2H, CH₂-Py) , 3.76 (s, 6H, OMe) , 4.66 (s, 2H, bisH2, bisH4), 7.09 (t, 2H, J=1.5Hz, Py-H), 7.21 (t, IH, J=6.0Hz, Py-H), 7.33 (d, IH, J=7.6Hz, Py-H), 7.50 (t, 2H, J=1.7Hz, Py-H), 7.66 (t, IH, J=7.5Hz, Py-H), 7.92 (d, 2H, J=7.8Hz, Py-H), 8.45 (d, 2H, J=4.0Hz, Py-H), 8.62 (d, IH, J=4.8Hz, Py-H) . [FeCl(N2Py3o)]Cl

Chloro (dimethyl 2, 4-di- (2-pyridyl) -3-methyl-7- (pyridin-2- ylmethyl) -3, 7-diaza-bicyclo [3.3.1] nonan-9-one-l, 5- dicarboxylate) iron (II) - chloride hydrate Anal. Calcd for C₂₈H29Cl₂FeN₅0₅:C 49.58, H 4.90, N 10.45; found +2H₂0: C 49.45, H 4.79, N 10.00. FAB⁺MS (nitrobenzylalcohol) : 624.1 [FeCl(N2Py3o) -H₂0]

BLEACHING EXPERIMENTS (peroxide mode) In an aqueous solution containing 10 mM carbonate buffer (pH 10) with 0.6 g/1 NaLAS (linear alkylbenzene sulphonate) and 10 mM hydrogen peroxide tomato-soya oil stained, curry-soya oil stained or BC-1 (tea) - ex CFT- cloths were added and kept in contact with the solution whilst agitating for 30 minutes at 30 °C. Comparative experiments were performed using 10 μM of the metal complex referred to in the table below.

After the wash, the cloths were rinsed with water and subsequently dried at 30 °C and the change in colour was measured immediately after drying with a Linotype-Hell scanner (ex Linotype) (t=0 in the table) . The tomato stains were left for 24 h in the dark and measured again (t=l in the table) . The change in colour (including bleaching) is expressed as the ΔE value versus white; a lower ΔE value means a cleaner cloth. The measured colour difference (ΔE) between the washed cloth and the unwashed cloth is defined as follows:

ΔE = [ (ΔL)² +(Δa)² +(Δb)² ]^{1 2} wherein ΔL is a measure for the difference in darkness between the washed and unwashed test cloth; Δa and Δb 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 l'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 below in the tables.

Tomato oil (TOL) /pHIO with 0.6 g/1 NaLAS and 10 mM H₂0₂

Curry oil (COL) /pHIO with 0.6 g/1 NaLAS and 10 mM H₂0₂

BC-1/pHlO with 0.6 g/1 NaLAS and 10 mM (H₂0₂;

The experiments presented in the tables above show that the iron complex containing the dimethylamine-bispidon ligand defined herein gives bleach enhancement using hydrogen peroxide. In addition, the comparative example with Fe (N2py3o) C12 shows an advantage of having a tert-amine moiety present over a pyridyl group.

Claims

CLAIMS :

A bleaching composition comprising:

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

wherein at least one of Rl and R2 is an optionally substituted tertiary amine of the form -C2-C4-alkyl-NR7R8, in which R7 and R8 are independently selected from the group consisting of straight chain, branched or cyclo C1-C12 alkyl, benzyl, the -C2-C4-alkyl- of the -C2-C4-alkyl-NR7R8 may be substituted by 1 to 4 Cl-C2-alkyl, or may form part of a C3 to C6 alkyl ring, and in which R7 and R8 may together form a saturated ring containing one or more other heteroatoms, the other of Rl and R2 being independently selected from: -C2-C4-alkyl-NR7R8 as defined above, -C1-C2 -optionally subsituted-alkyl, -C6-C10-aryl, -Cl-C4-alkyl-C6-C10-aryl, a heterocycloalkyl: selected from the group consisting of: pyrrolinyl, pyrrolidinyl, morpholinyl, piperidinyl, piperazinyl, hexamethylene imine, 1, 4-piperazinyl, tetrahydrothiophenyl, tetrahydrofuranyl, tetrahydropyranyl, and oxazolidinyl, wherein the heterocycloalkyl may be connected to the ligand via any atom in the ring of the selected heterocycloalkyl, a -Cl-C6-alkyl-heterocycloalkyl, wherein the heterocycloalkyl of the -Cl-C6-heterocycloalkyl is selected from the group consisting of: piperidinyl, piperidine, 1,4- piperazine, tetrahydrothiophene, tetrahydrofuran, pyrrolidine, and tetrahydropyran, wherein the heterocycloalkyl may be connected to the -Cl-C6-alkyl via any atom in the ring of the selected heterocycloalkyl, a -Cl-C6-alkyl-heteroaryl, wherein the heteroaryl of the - Cl-C6-alkylheteroaryl is selected from the group consisting of: pyridinyl, pyrimidinyl, pyrazinyl, triazolyl, pyridazinyl, 1, 3, 5-triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl, thiazolyl, oxazolidinyl, pyrrolyl, carbazolyl, indolyl, and isoindolyl, wherein the heteroaryl may be connected to the - Cl-C6-alkyl via any atom in the ring of the selected heteroaryl and the selected heteroaryl is optionally substituted by -Cl-C4-alkyl, -C0-C6-alkyl-phenol, -C0-C6- alkyl-thiophenol, -C2-C4-alkyl-thiol, -C2-C4-alkyl- thioether, -C2-C4-alkyl-alcohol, -C2-C4-alkyl-amine, and a -C2-C4-alkyl-carboxylate;

R3 and R4 are independently selected from hydrogen, C1-C4- alkyl, phenyl, electron withdrawing groups and reduced products and derivatives thereof;

X is selected from: C=0, a ketal derivative of C=0, a thioketal of derivative of C=0, and -[C(R6)₂]_y- wherein y takes a value 0 or 1; each R6 is independently selected from hydrogen, hydroxyl, 0-Cl-C24-alkyl, O-benzyl, 0-(C=0)- Cl-C24-alkyl, Cl-C24-alkyl;

z groups are same heteroaromatic groups, selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1, 3, 5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, and the selected Z is optionally substituted by -Cl-C4-alkyl;

b) the balance carriers and adjunct ingredients, together with at least 2 % wt/wt of a peroxygen bleach or source thereof.

A bleaching composition according to claim 1, wherein z

is

, wherein R is independently selected from: hydrogen, F, CI, Br, hydroxyl, Cl-C4-alkyl-, -NH-CO-H, -NH- CO-Cl-C4-alkyl, -NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl.

3. A bleaching composition according to claim 2, wherein R is H or -Cl-C4-alkyl.

4. A bleaching composition according to claim 3, wherein R is H.

5. A bleaching composition according to claim 1, wherein z is selected from the group consisting of: benzimidazole, thiazole, and imidazole.

6. A bleaching composition according to any preceding claim, wherein one of Rl and R2 is -CH3.

7. A bleaching composition according to any preceding claim, wherein the -C2-C4-alkyl-NR7R8 is selected from the group consisting of: -CH2CH2-NR7R8, -CH2CMe2-NR7R8, - CMe2CH2-NR7R8, -CMeHCH2-NR7R8, -CMeHCMeH-NR7R8 , -CH2CMeH- NR7R8, -CH2CH2CH2-NR7R8, -CH2CH2CMe2-NR7R8, -CH2CMe2CH2-

NR7R8, -CH2CH2-NEt2, -CH2CH2-N (i-Pr) 2,

, and

8. A bleaching composition according to any preceding claim, wherein X is selected from: C=0, and -[C(R6)₂] wherein each R6 is independently selected from hydrogen, hydroxyl, Cl-C24-alkoxy and Cl-C24-alkyl .

9. A bleaching composition according to any preceding claim, wherein X, is selected from C=0, C(OH)₂, syn-CH(OH) and anti-CH(OH) .

10. A bleaching composition according to any preceding claim, wherein R7 and R8 are independently selected from the group consisting of -CH3, -C2H5, -C3H7, -C4H9, -C5H11, - C6H13, and -CH2C6H5.

11. A bleaching composition according according to any preceding claim, wherein at least one of R7 and R8 is an optionally substituted alkyl chain of at least five carbon atoms .

12. A bleaching composition according to according to claim 7, wherein R7 and R8 are -CH3, -CH2CH3, -CH(CH3)2 or together form a optionally substituted cyclic structure

selected from the group consisting of:

and

/ \

N 0

\ /

13. A bleaching composition according to any preceding claim, wherein Rl is a C2-C4-alkyl-NR7R8.

14. A bleaching composition according to any preceding claim, wherein Rl and R2 are independently C2-C4-alkyl- NR7R8.

15. A bleaching composition according to any preceding claim, wherein -NR7R8 is selected from group consisting

16. A bleaching composition according to any preceding claim, wherein R3 and R4 are selected from the group consisting of: -C (0) 0-Cl-C24-alkyl, -CH20C (0) Cl-C20-alkyl, benzyl ester, phenyl, benzyl, CN, hydrogen, methyl, and Cl- C4-0R wherein R is selected from the group consisting of H, Cl-C24-alkyl or C (0) -Cl-C24-alkyl .

17. A bleaching composition according to any preceding claim, wherein: R3 = R4.

18. A bleaching composition according to any preceding claim, wherein R3 and R4 are selected from the group consisting of -CH20H, benzyl ester, and -C (0) 0-Cl-C6-alkyl .

19. A bleaching composition according to any preceding claim, wherein R3 and R4 are selected from the group consisting of: -C(0)-0-CH3, -C (0) -0-CH2CH3, and CH20H.

20. A bleaching composition according to any preceding claim, wherein Y = 1.

21. A bleaching composition according to any preceding claim, wherein X selected from the group consisting of: C=0, CH2, C(0H)2, syn-CHOR and anti-CHOR, wherein R is H, C1-C24- alkyl or C (0) -Cl-C24-alkyl .

22. A bleaching composition according to any preceding claim, wherein X is C=0 or C(0H)2.

23. A bleaching composition according to claim 1, wherein the ligand is:

wherein -NR6R7 is selected from the group consisting of -

NMe2, NEt2, -N(i-Pr)2,

24. A bleaching composition according to claims 1 to 23, wherein the complex is of the general formula (Al) :

[M_aL_kX_n] Y_π (Al;

in which:

M represents a metal selected from Mn (II) - (III) - (IV) - (V), Cu(I)-(II)-(III), Fe(II)-(III)-(IV)-(V), Co(I)-(II)- (III), Ti(II)-(III)-(IV), V(II)-(III)-(IV)-(V) , Mo(II)- (III)-(IV)-(V)-(VI) and W (IV) - (V) - (VI) ; X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner;

Y represents any non-coordinated counter ion; a represents an integer from 1 to 10, k represents an integer from 1 to 10, n represents an integer from 0 to 10, m represents zero or an integer from 1 to 20; and L represents a ligand as defined in claims 1 to 22, or its protonated or deprotonated analogue.

25. A bleaching composition according to claim 24, wherein M represents a metal selected from Fe (II) - (III) - (IV) - (V) .

26. A bleaching composition according to claim 25, wherein M represents a metal selected from Fe(II) and Fe(III).

27. A bleaching composition according to claim 26, wherein the ligand is present in the form selected from the group consisting of [FeLCl]Cl and [FeL (H20) ] (BF4 ) 2.