AU2003204301B8 - Method of treating a textile - Google Patents

Description

AUSTRALIA

PATENTS ACT 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT TITLE OF INVENTION METHOD OF TREATING A TEXTILE Name and Address of Applicant: UNILEVER PLC of Unilever House, Blackfriars, London EC4P 4BQ, England The following statement is a full description of this invention, including the best method of performing it known to me:- WO 00/12808 PCT/GB99/02878 METHOD OF TREATING A TEXTILE This invention relates to a method of treating textiles such as laundry fabrics, more specifically to a method whereby bleaching by atmospheric oxygen is catalysed after the treatment. This invention also relates to textiles thus treated.

In a conventional bleaching treatment, a substrate such as a laundry fabric or other textile is contacted is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides.

A preferred approach to generating hydroperoxyl bleach radicals 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. Alternatively, or additionally, hydrogen peroxide and peroxy systems can be activated by bleach catalysts, such as by complexes 20 of iron and the ligand N4Py N, N-bis(pyridin-2-yl-methyl)-bis(pyridin-2yl)methylamine) disclosed in W095/34628, or the ligand Tpen N, N, N'tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in W097/48787. It has long been thought desirable to be able to use atmospheric oxygen (air) as the source for a bleaching species, as this 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, whereas according to W095/34628 and W097/48787 referred to above, molecular oxygen may WO 00/12808 PCT/GB99/02878 2 be used as the oxidant with the iron catalysts, as an alternative to peroxide generating systems.

However, the known art teaches a bleaching effect only as long as the substrate is being subjected to 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 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 when the treated fabric has been treated and is dry.

We have now found this can be achieved by a treatment method in accordance with the present invention, by catalysing bleaching of the substrate by atmospheric oxygen after treatment of the substrate.

Accordingly, the present invention provides a method of treating a textile by contacting the textile with an organic substance which forms a complex with a transition metal, whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment.

The present invention further provides a dry textile having an organic substance as defined above applied or deposited thereon, whereby bleaching by atmospheric oxygen is catalysed on the textile.

3 a' Advantageously, by enabling a bleaching effect even after the textile has been treated, the benefits of 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. Moreover, since a bleaching C 5 effect is achieved by atmospheric oxygen after treatment of the textile, hydrogen peroxide or peroxy-based bleach systems can be omitted from the treatment substance.

C)As now claimed, according to one aspect, the present invention provides a method of treating a textile by contacting the textile with an organic substance which forme a complex with a transition metal, the treatment providing the organic substance in a form that is substantially devoid ofperoxygen bleach or a peroxy-based or -generating bleach system whereby the complex catalyses bleaching of the textile by atmospheric oxygen after the treatment, wherein the treated textile is dried and bleaching is catalysed on the dry textile.

The organic substance may be contacted to the textile fabric in any suitable manner. For example, it may be applied in dry form, such as in powder form, or in a liquor that is then dried, for example as 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.

Other suitable means of contacting the organic substance to the textile may be used, as further explained below.

Any suitable textile that is susceptible to bleaching or one that one mighi'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.

-3a- Ln a preferred embodiment, the treated textile is dried, by allowing it to dry under ambient temperature or at elevated temperatures.

The bleaching method may be carried out by simply leaving the substrate in contact with the organic substance for a sufficient period of time. Preferably, however, the organic substance is in an aqueous medium, and the aqueous medium on or containing the substrate is agitated.

WO 00/12808 PCT/GB99/02878 4 The organic substance can be contacted to 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 preferred embodiment, the treated textile is dried, by allowing it to dry under ambient temperature or at elevated temperatures.

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.

It is particularly advantageous that the organic substance used in the method of the present invention makes use of atmospheric oxygen in its bleaching activity. This avoids the requirement that peroxygen bleaches and/or other relatively large quantities of reactive substances need be used in the treatment process. Consequently, only a relatively small quantity of bleach active substance need be employed and this allows dosage routes to be exploited which could previously not be used. Thus, while it is preferable to include the organic substance in a composition that is normally used in a washing process, such as a pre-treatment, main-wash, conditioning composition or ironing aid, other means for ensuring that the organic substance is present in the wash liquor may be envisaged.

WO 00/12808 PCT/GB99/02878 For example, it is envisaged that the organic substance can be presented in the form of a body from which it is slowly released.during the whole or part of the laundry process.

Such release can occur over the course of a single wash or over the course of a plurality of washes. In the latter case it is envisaged that the organic substance can be released from a carrier substrate used in association with the wash process, e.g. from a body placed in the dispenser drawer of a washing machine, elsewhere in the delivery system or in the drum of the washing machine. When used in the drum of the washing machine the carrier can be freely moving or fixed relative to the drum. Such fixing can be achieved by.mechanical means, for example by barbs that interact with the drum wall, or employ other forces, for example a magnetic force. The modification of a washing machine to provide for means.to hold and retain such a carrier is envisaged similar means being known from the analogous art of toilet block manufacture. Freely moving carriers such as shuttles for dosage of surfactant materials and/or other detergent ingredients into the wash can comprise means for the release of the organic substance into the wash.

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 j 20 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.

WO 00/12808 PCT/GB99/02878 6 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.

The organic substance may comprise a preformed complex of a ligand and a transition metal. Alternatively, the organic substance 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 organic substance may also be included in the form of a composition of a free ligand or a transition metal-substitutable metal-ligand complex, and a source of transition metal, whereby the complex is formed in situ in the medium.

The organic substance 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 I-IV, copper I-III, cobalt I-III, nickel I-III, chromium II-VII, silver I-II, titanium II-IV, tungsten IV-VI, palladium II, ruthenium II-V, vanadium II-V and molybdenum II-VI.

In a preferred embodiment, the organic substance forms a complex of the general formula (A1): WO 00/12808 PCT/GB99/02878 [MaLkXnIyrn in which: M represents a met al selected from Fe(I)and and preferably selected from Cu(l)- 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 02., RB0 2 2 RCOO,. RCONR-, 0H', N03', N0 2

NO,

CO, S2-, Rs-, P03'-, STP-derived anions, P0 3 0R 3

H

2 0, C0 3 HC0 3 IZOH, NRR'R", RCN, Cl-, Bf, OCN-, SCN, CN, N 3 F, R0-, C104-, S0 4 HS0 4 S03'- and RS03-, and more preferably selected from 02-, RB2 2- RCOO-, Off, N0 3 N02-, NO, CO, CN S2-, RS-, p0 3 4

H

2 0, C0 3 2 HC0 3 ROH, NRR'R", Cl-, Br-, OCN-, SCN, RCN, N 3 F, R0, C10 4 S04 2, HS0 4 ,1 S0 3 2 and RS0 3 (preferably CF 3 S0 3 Y represents any non-coordinated counter ion, preferably selected from' C 0 4 BRI', [FeC1 4

PF

6 RCOO-, N0 3 N0 2 RO-, N 4 CE-, Bf, F, F, RS0 3

S

2 0 6 OCN, SCN, Li+, Ba 24 Na 4 Mg 2 Ca 24 Cs 4 PR4, RB0 2 S04 HS0 4 S0 2 SbIJ CuCL 4 2 CN, ,H0 4 2

H

2 P0 4 STP-derived anion', C0 3 2

C

and BF 4 and more preferably selected from C10 4 BR4, [FeC1 4

PF

6 RCOO-, N0 3 N02% R0-, N 4 CE Bf, F, r, RS0 3 (preferably CF 3 S0 3

S

2 0 6

OCN,

SCN, Li+, Ba 24 Na 4 Mg 24 Ca 24 pR4A S042-, HS0 4 S03 2, and BF 4 R, independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl., heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, WO 00/12808 PCT/GB99/02878 8 heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen, wherein E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups, and preferably R, R', represent hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or C 1 i 4 -alkyl; a represents an integer from I to 10, preferably from 1 to 4; k represents an integer from 1 to 10; n represents zero or an integer from 1 to 10, preferably from I to 4; m represents zero or an integer from 1 to 20, preferably from 1 to 8.

Preferably, the ligand L is of the general formula (BI): TI-[-Zl-(Q1)r]s-Z2-(Q2)g-T2 I I RI R2 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 i to 6; Zl and Z2 independently represent a heteroatom or a heterocyclic or heteroaromatic ring, Zl and/or Z2 being optionally substituted by one or more functional groups E as defined below; Q1 and Q2 independently represent a group of the formula: R6 R8 I I I I R7 R9 WO 00/12808 PCT/GB99/02878 9 wherein d=0-9; e=0-9; f-0-9; each YI is independently selected from -S02-, 2 (wherein G' and G 2 are as defined below), arylene, alkylene, heteroarylene, and if s>1, each group is independently defined; RI, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups ,being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen; E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from hydroxy, mono- or polycarboxylate derivatives, aryl, 20 heteroaryl, sulphonate, thiol thioethers disulphides (-RSSR'), dithiolenes, mono- or polyphosphonates, mono- or polyphosphates, electron donating groups and electron withdrawing groups, and groups of formulae (G )(G 2 2

(G

3 2 G'O- and wherein each of G 2 and G 3 is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoing)); or one of R1-R9 is a bridging group bound to another moiety of the same general formula; TI and T2 independently represent groups R4 and R5, wherein R4 and R5 are as defined for RI -R9, and if g=0 and s>0, RI together with R4, and/or R2 together with WO 00/12808 PCT/GB99/02878 may optionally independently represent =CH-RIO, wherein RIO is as defined for R1-R9, or TI and T2 may together represent a covalent bond linkage when s>I and g>O; ifZl and/or Z2 represent N and TI and T2 together represent a single bond linkage and RI and/or R2 are absent, Ql and/or Q2 may independently represent a group of the formula: optionally any two or more of RI, R2, R6, R7, R8, R9 independently are linked together by a covalent bond; if ZI and/or Z2 represents O, then RI and/or R2 do not exist; if Z1 and/or Z2 represents S, N P, B or Si then RI and/or R2 may be absent; if ZI and/or Z2 represents a heteroatom substituted by a functional group E then RI and/or R2 and/or R4 and/or R5 may be absent.

The groups Z1 and Z2 preferably independently represent an optionally substituted heteroatom selected from N, P, O, S, B and Si or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidines, pyrazine, pyramidine, pyrazole, pyrrole, imidazole, benzimidazole, quinoleine, isoquinoline, carbazole, indole, isoindole, furane, thiophene, oxazole and thiazole.

The groups RI-R9 are preferably independently selected from hydroxy-Co-C 20 -alkyl, halo-Co-C 2 o-alkyl, nitroso, formyl-Co-C20-alkyl, carboxyl-Co-C20-alkyl and esters and salts thereof, carbamoyl-Co-C20-alkyl, sulpho-Co-C20-alkyl and esters and salts thereof, amino-Co-C20-alkyl, aryl-Co-C 2 o-alkyl, heteroaryl-Co-C 2 0oalkyl; Co-C 20 -alkyl, alkoxy-Co-Cs-alkyl, carbonyl-Co-C 6 -alkoxy, and aryl-Co-Cs-alkyl and Co-C 20 -alkylamide.

WO 00/12808 PCT/GB99/02878 11 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 may have the formula -Cn,(R1 l)(R12)-(D)p-C,(RI 1)(R12)- bound between the two moieties, wherein p is zero or one, D is selected from a heteroatom or a heteroatomcontaining group, or is part of an aromatic or saturated homonuclear and heteronuclear ring, n' is an integer from 1 to 4, m' is an integer from 1 to 4, with the proviso that R11 and R12 are each independently preferably selected from NR13 and OR14, alkyl, aryl, optionally substituted, and R13 and R14 are each independently selected from alkyl, aryl, both optionally substituted. Alternatively, or additionally, two or more of R1-R9 together represent a bridging group linking atoms, preferably hetero atoms, in the same moiety, with the bridging group preferably being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge.

In a first variant according to formula the groups TI and T2 together form a single bond linkage and s>l, according to general formula (BII): R3

Z

3 (Q2)g (Q3)h Z2- R2

R)

wherein Z3 independently represents a group as defined for Zl or Z2; R3 independently represents a group as defined for R -R9; Q3 independently represents a group as defined for Q1, Q2; h represents zero or an integer from 1 to 6; and s'=s-1.

WO 00/12808 PCT/GB99/02878 12 In a first embodiment of the first variant, in general formula (B3I1), 2 6r 3; rrr-g=h=1; d=2 or 3; R6=R7=H, preferably such that the ligand has a general formula selected from:

RI

(N

.N NR3

/NJ

R2

N

CN-R3

/NJ

R2 RI N N

,R

R4' R3 R1 C: N-R3 R2/ j R1 F- ,R2 N N R4' /I R3

/R

N N N R3 R4 and more preferably selected from: RI 1 /R2 NZ N R4' N 9 3 R4K "R3 R1, /,R2 N N CN N3- R4' LdR3

N

C N-R3 R2 In these preferred examples, RI, R2, R3 and R4 are preferably independently'selected, from alkyl, aryl, heteroaryl, and/or one of RI -R4 represents a bridging group bound to another moiety of the same general formula and/or two or more of Rl -R4 together WO 00/12808 PCT/GB99/02878 13 represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene.or hydroxy-alkylene or a heteroaryl-containing bridge, preferably heteroarylene. More preferably, R1, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxy-alkylene.

According to this first embodiment, in the complex [MaLkXn]Ym preferably: M= Mn(II)-(IV), Cu(I)-(III), Fe(II)-(III), Co(II)-(III); X= CH 3 CN, OH 2 CF, Br, OCN', N 3 SCN', OH', O 2 P043-, C 6

H

5 B022,

RCOO';

Y= C10 4 BPh 4 Br Cl [FeC14], PF 6

NO

3 a= 1,2,3,4; n= 0, 1, 2, 3, 4, 5, 6,7, 8, 9; m= 1, 2, 3, 4; and k= 1,2,4.

In a second embodiment of the first variant, in general formula (BII), r=g=h=1; d=f-0; e=l; and each Yl is independently alkylene or heteroarylene. The ligand 20 preferably has the general formula: R1 R4 N2

N

1

A

2 Al I A4 N1-R2 N2-'-A3 R3 wherein A, A 2

A

3 A4 are independently selected from Ci.9-alkylene or heteroarylene groups; and Ni and N 2 independently represent a hetero atom or a heteroarylene group.

I

WO 00/12808 PCT/GB99/02878 14 In a preferred second embodiment, N1 represents an aliphatic nitrogen, N 2 represents a heteroarylene group, RI, R2, R3, R4 each independently represent alkyl, aryl or heteroaryl, and Al, A 2

A

3

A

4 each represent -CH2-.

One of Rl-R4 may represent a bridging group bound to another moiety of the same general formula and/or two or more of RI-R4 may together represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene or hydroxyalkylene or a heteroaryl-containing bridge. Preferably, RI, R2, R3 and R4 are independently selected from methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, i or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxy-alkylene.

Particularly preferably, the ligand has the general formula:

N

NR

1

NR

2

N

wherein Ri, R2 each independently represent alkyl, aryl or heteroaryl.

According to this second embodiment, in the complex [MaLkXn]Y, preferably: M= Fe(II)-(III), Mn(II)-(IV), Cu(II), Co(II)-(III); X= CH3CN, OH 2 CI-, Br, OCN', N 3 SCN OH', PO 4

C

6

H

5

BO

2 2

RCOO';

Y= C10 4 BPh4, Br', Cl [FeCl4], PF 6 N0 3 a 1,2,3,4; n= 0, 1, 2, 3, 4, 5, 6,7, 8, 9; WO 00/12808 PTG9I27 PCr/GB99/02878 i=1, 2, 3, 4; and k= 2, 4.

In a third embodiment of the first variant, in general formula (1311), s'=2 and r--g=h=1, according to the general formula: RZ4 Q z Q2 Q4 R2

ZI-QI

In this third embodiment, preferably each Z I -Z4 represents a heteroarornatic ring; e~f4O; d= 1; and R7 is absent,"with preferably R I R2=R3=R4= 2,4,6-trirnethyl-3

SO

3 Na-phenyl, 2,6-diCl-3 (or 4)-SO 3 Na-phenyl.

Alternatively, each Z I -Z4 represents N; R I -R4 are absent; both Q 1 and Q3 represent =CH[-YI ]e-CH and both Q2 and.Q4 represent -CH 2 I CH 2 Thius, preferably the Iigand.has the general formula: WO 00/12808 WO 00/ 2808PCT/GB99/02878

\+AW

wherein A represents optionally substituted'alkylene optionally interrupted by a heteroatom; and n is zero or an integer from I to Preferably, R I -R6 represent hydrogen, n=1 and A= -CH 2 -CHOHW. -CI1N(R)CH 2 or

CH

2

CH

2

N(R)CH

2

CH

2 wherein R represents hydrogen or alkyl., more preferably A=

CH

2 -CHOH- or -CH 2

CH

2

NHCH

2

CH

2 According to this third embodiment, in the complex [MaLkXn]Ym preferably: X= CH 3 CN, OH4 2 C1, Bf, OCN-, N 3 SCN', OH P04, C 6 14 5 B30 2 2%

RCOO";

Y= C104-, BPhK,, Br Cl [FeCI 4

PF

6 N0 3 1, 2,3, 4; n=0, 1, 2, 3, 4, 5, 6,7, 8, 9; m= 1, 2,3, 4;and k= 1, 2, 4.

WO 00/12808 PCT/GB99/0878 17 In a second variant according to formula TI and T2 independently represent groups R4, R5 as defined for R1-R9, according to the general formula (BIII): R4-[-Z1 1),-]n-Z2-(Q2)g-R5 RI R2 In a first embodiment of thesecond variant, in general formula (BIII), s=l: g=0; YI -CH 2 and RI together with R4, and/or R2 together with independently represent =CH-RI0, wherein R10 is as defined for RI-R9. In one example, R2 together with R5 represents =CH-R10, with RI and R4 being two separate groups. Alternatively, both RI together with R4, and R2 together with R5 may independently represent =CH-RI 0. Thus, preferred ligands may for example have a R3 R2-N 2 N- RI R4 Preferably, the ligand is selected from: /N N=\ R1 R2 R4-N N=- R3 R1 WO 00/12808 PCT/GB99/02878 18 wherein R1land R2 are selected from optionally substituted phenols, heteroaryl-CO-C 20 alkyls, R3 and R4 are selected from alkyl, aryl. optionally substituted phenols, heteroaryl-Co-CM-alkyls, alkylaryl, aininoalkyl,, alkoxy, more preferably RI and R2 being selected from optionally substituted phenols, heteroaryl-CO-C 2 -alkyls, R3 and R4 are selected from alkyl, aryl, option ally substituted phenols, nitrogen-heteroaryl-Co-

C

2 -alkyls.

According to this first embodiment, in the complex [M.LkXn,]Ym preferably: X= CH 3 CN, OH 2 CI;, Bf, OCN-, N 3 SCN, Off, 02 P04 3 C 6 14 5 302

RCOO;

Y= C104', BPh 4 Br, CI .[FeCI4]f, PF 6 ,N0 3 1, 2,3, 4; n=0, 1, 2,3, 4, 5,6,7, 8, 9; l= 2, 3, 4;and k= 1, 2, 4.

In a second embodiment of the second variant, in general formula (B3111), s1I; g=0; dI-fl-1; e=1 YI= wherein R' and R" are independently as defined for RI-R9., Preferably, the ligand has the general formula: RI

R

2 R5 R3 4 j4~R4 R7-N R6 N-R9 R8 U The groups RI1, R2, R3, R4, R5 in this formula are preferably -HoPr CO-C 20 -alkyl, n=0 or 1, R6 is -alkyl, -OH4 or -SH, and R7, R8, R9, RIO0 are preferably each independently selected from CO-C 2 o-alkyl, heteroaryl-CO-C 20 -alkyl, alkoxy-CO-Cs-alkyl and amino-

CO-C

2 0-alkYl.

WO 00/12808 WO 0012808PCT/GB99/02878 According to this second embodiment,.in the complex [MSLkXnIYm' preferably: M= Mnall)-(JV), Fe(II)-(III), Cu(II), Co(II)-(II); X= CH 3 CN, OH 2 C1, Br-, OCN-, N 3 SCN-, OfH, 02-p P 4 3 CHB0 2 2

RCOOU;

Y= C10 4 BPh4', Br', [FeC14, PF 6 -,N0 3 1, 2,3, 4; n=0, 1, 2,3, 4; m=0, 1, 2, 3, 4, 5, 6, 7, 8; and k= 1,2, 3,4.

In a third embodiment of the second variant, in general formula (BIll), s=0; g1l; d=e=0; f-4. Preferably, the ligand has the general formula: R2 RI R3

N%

R4'* More preferably, the ligand has the general formula:.

wherein R I, R2, R3 are as defined for R2, R4, According to this third embodiment, in the complex [MLkXn]Ym preferably: WO 00/12808 PCT/GB99/02878 X= CH 3 CN, OH 2 CF, Br, OCN-, N 3 SCN', OH', O 2

PO

4 3

C

6

HBO

2 2

RCOO';

Y= C1O 4 BPh4, Br Cl', [FeC4], PF 6 NO3; a= 1,2,3,4; n= 0, 1, 2,3,4; m= 0, 1, 2, 3, 4, 5, 6, 7, 8; and k= 1,2,3,4.

In a fourth embodiment of the second variant, the organic substance forms a complex of the general formula [LMX,]ZYq in which M represents iron in the II, HII,IV or V oxidation state, manganese in the II, III, IV, VI or VII oxidation state, copper in the I, II or III oxidation state, cobalt in the II, III or IV oxidation state, or chromium in the II-VI oxidation state; X represents a coordinating species; n represents zero or an integer in the range from 0 to 3; z represents the charge of the complex and is an integer which can be positive, zero or negative; Y represents a counter ion, the type of which is dependent on the charge of the complex; q z/[charge and L represents a pentadentate ligand of the general formula R1 R 2

R

1

R

2 WO 00/12808 PCT/GB99/02878 21 wherein each R' R 2 independently represents -R4R 5

R

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

-R

5 each R 4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R 5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.

The ligand L having the general formula as defined above, is a pentadentate ligand.

By 'pentadentate' herein is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex.

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

The ligand L of formula preferably comprises at least two substituted or unsubstituted heteroaryl groups in the four side groups. The heteroaryl group is preferably a pyridin-2-yl group and, if substituted, preferably a methyl- or ethylsubstituted pyridin-2-yl group. More preferably, the heteroaryl group is an unsubstituted pyridin-2-yl group. Preferably, the heteroaryl group is linked to methylamine, and preferably to the N atom thereof, via a methylene group.- Preferably, the ligand L of formula contains at least one optionally substituted amino-alkyl side group, more preferably two amino-ethyl side groups, in particular 2-(N-alkyl)amino-ethyl or 2-(N,Ndialkyl)amino-ethyl.

WO 00/1 2808 PCT/GB99/02878 22 Thus, in formula preferably R' represents pyridin-2-yl or R 2 represents pyridin-2-ylmethyl. Preferably (2 or R' represents 2-amino-ethyl, 2-(N-(mn)ethyl)axnino-ethyl or 2- (N,N-di(m)ethyl)arnino-ethyl. -If substituted, R 5 preferably represents 3-methyl pyridin- 2-yl. R 3 preferably represents hydrogen, benzyl or methyl.

Examples of preferred ligands L of formula in their simplest forms are: pyridin-2-yl containing ligands-such as: N,N-bis(pyridin-2-yI-methyl)-bis(pyridin-2-yl)methylamine; NN-bis(pyrazol-I -yl-methyl)-bis(pyridin-2-yl)methylamine;D N,N-bis(imidazol-2-yl-methyl)-bis(pyridin-2-yI)methylamine; N,N-bis(1I,2,4-triazol- I -yl-methyl)-bis(pyridin-2-yl)methylamine; N,N-bis(pyridin-2-yl-methyl)-bis(pyrazol- I -yl)methylamine; N,N-bis(pyridin-2-yl-methyl)-bis(imidazol-2-yl)methylaminew NN-bis(pyridin-2-yl-methyl)-bis(1I,2,4-triazol- 1 -yl)methylamine; N,N-bis(pyridin-2-y]-methyl)- 1, 1 -bis(pyridin-2-yl)- I -aminoethane; N,N-bis(pyridin-2-yl-methyl)- 1, 1 -bis(pyridin-2-yl).-2-phenyl- I -aminoethane; N,N-bis(pyrazol- I -yl -methyl)-, 1I -bis(pyridin-2-yl)- I -amninoethane;- N,N-bis(pyrazol- I -yI-methyl)- 1, 1 -bis(pyridin-2-yl)-2-phenyl- I -aminoethane; NN-bis(imidazol-2-yl-methyl)- 1, 1 -bis(pyridin-2-yi)- I -aminoethane;) N,N-bis(imidazol-2-yl-methyl)- 1,91 -bis(pyridin-2-yl)-2-phehyl- I -aminoethane;4 N,N-bis(.I ,2,4-triazol- I -yl-methyl)- 1, 1 -bis~pyridin-2-yl)- I -aminoethane; N,N-bvis(1 ,2,4-triazol- I -yl-metLhyl)-l I -bis(pyridin-2-yl)-2-phenyl- I -amninoethani&; N,N-bis(pyi-idin-2-yI-methyl)- 1, 1 -bis(pyrazol- I I -aminoethane; N,N-bis(pyridin-2-yl-methyl)- 1,1-bis(pyrazol-1I-yl)-2-phenyl-lI-aniinoethanie; N,N-bis(pyridin-2-yI-methyl)-l I I-bis(imidazol-2-yl)-lI-aininoethane; N,N-bis(pyridin-2-yl-nethyl)- 1,1-bis(imidazol-2-yl)-2-phenyl-l1-aminoethane; N,N-bis(pyridin-2-yl-methyl)- 1, 1 -bis( 1,2,4-triazol- I I -aminoethane; N,N-bis(pyridin-2-yl-methyl)- 1, 1 -bis(1I,2,4-triazol- I I -aminoethane; NN-bis(pyridin-2-yl-methyl)- 1,1-bis(pyridin-2-yl)-l1-aminoethane;.

wo 00/12808 PCT/GB99/02878 23 N,N-bis(pyridil-2-YI-methyl)4 I -bis(pyridin-2-yl)- I -arninohexane; NN-bis(pyridin-2-yI-methyl)-] 1, -bis(pyridin-2-yl)-2-phenyl- 1 -aininoethane; NN-bis(pyridin-2-yl-methyl)-1 I -bis(pyridin-2-yl)-2-(4-sulphonic acid-phenyl)- I1amninoethane; N;N-bis(pyridin-2-yI-methyl)-1 I -bis(pyridin-2-yl)-2-(pyridin-2-yl)- 1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)- 1, 1 -bis(pyridin-2-yI)-2-(pyridin-3-yl)- 1 -aminoethane; N,N-bis(pyridin-2-y-methyl)- 1, 1 -bis(pyridin-2-yl)-2-(pyridin-4-yI)- I -aminoethane; NN-bis(pyridin-2-yl-methyl)- 1, 1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-4-yl)- I1aniinoethane; NN-bis(pyridin-2-yl-methyl)- 1, 1 -bis(pyridin-2-yl)-2-( I -alkyl-pyridinium-3-yl)- I amninoethane; NN-bis(pyridin-2-yl-n'ethyl)- 1, 1 -bis(,pyridin-2-yl)-2-( I -alkyl-pyridinium-2-yi)- 1aminoethane; (ii) 2-amino-ethyl containing ligands such as: N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyridin-2-yl)methylamine; N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyrazol- I -yl)methylamnine; NN-bis(2-(N-alkyl)amino-ethyl)-bis(imidazol-2-yI)methylamine; NN-bis(2-(N-alkyl)amnino-ethyl)-bis(1I,2,4-triazol- I -yI)mrethylamine; N4,N-bis(2-(NN-dialkyl)amino-ethyl)-bis(pyridin-2-yI)methylamine; N,N-bis(2-(N,'N-dialkyl)ainino-ethyl)-bis(pyrazol- I -yI)methylamine; N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(imidazol-2-yl)mhethylamine; N,N-bis(2-(N,N -dialkyl)amino-ethyl)-bis(l1,2-,4-tr-iazol-1I-yl)rnethylam-ine; N,N-bis(pyridin-2-yl-methyl)-bis(2-amnino-ethyl)methylamine; NN-bis(pyrazol- I -yl-methyl)-bis(2-amino-ethyl)methylamine; NN-bis(imidazol-2-yl-methyl)-bis(2-amino-ethyl)mnethylamine; N,N-bis(1I,2,4-triazol-1 -yI-methyl)-bis(2,-amino-ethyl)methylamine.

More preferred ligands are: WO 00/12808 PCT/GB99/02878 24 NN-bis(pyridin-2-yI-methyl)-bis(pyridin-2-yl)methylamine, hereafter referred. to as N4Py.

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

In an alternative fourth embodiment, the organic substance forms a complex of the general formula including a ligand as defined above, but with the proviso that R' does not represent hydrogen.

In a fifth embodiment of the second variant, the organic substance forms a complex of the general formula as defined above, but wherein L represents a pentadentate or hexadentate, ligand of general formula

R'RN-W-NR'

wherein each R' independently represents -R 3 in which R 3 represents optionally substituted alkylene, alkenylene, oxyalkylene, arninoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl,9 pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; W represents an optionally substituted alkylene bridging group selected from

-CH

2

CH

2

-CH

2

CH

2

CH

2

-CH

2

CH

2

CH

2

CH

2

-CH

2

-C

6

H

4

-CH

2

-CH

2

-C

6

H

1 0

-CH

2 and -CH 2 -CioH 6

-CH

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

WO 00/12808 PCT/GB99/02878 The ligand L having the general formula as defined above, is a pentadentate ligand or, if R'=R 2 can be a hexadentate ligand. As mentioned above, by 'pentadentate' is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex.

Similarly, by 'hexadentate' is meant that six hetero atoms can in principle coordinate to the metal M ion. However, in this case it is believed that one of the arms will not be bound in the complex, so that the hexadentate ligand will be penta coordinating.

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

6 The ligand L of formula comprises at least one optionally substituted heteroaryl group in each of the three R' groups. Preferably, the heteroaryl group is a pyridin-2-yl group, in particular a methyl- or ethyl-substituted pyridin-2-yl group. The heteroaryl group is linked to an N atom in formula preferably via an alkylene group, more preferably a methylene group. Most preferably, the heteroaryl group is a 3-methylpyridin-2-yl group linked to an N atom via methylene.

20 The group R 2 in formula is a substituted or unsubstituted alkyl, aryl or arylalkyl group, or a group However, preferably R 2 is different from each of the groups R' in the formula above. Preferably, R 2 is methyl, ethyl, benzyl, 2-hydroxyethyl or 2methoxyethyl. More preferably, R 2 is methyl or ethyl.

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

CH

2 -CH2CH2CH2H2CH2- 2

CH

2

CH

2

CH

2

-CH

2

-C

6

H

4

-CH

2

-CH

2

-C

6

H

1 o-

CH

2 and -CH 2

-C

1 oH 6

-CH

2 (wherein -CsH 4

-C

6

H

0 -CloH 6 can be ortho-, para-, or meta-C 6 H4-, -C 6

H

1 0 -CoH 6 Preferably, the bridging group W is an ethylene or 1,4butylene group, more preferably an ethylene group.

*WO 00/1 2808 PCT/GB99/02878 26 Preferably, V represents substituted pyridin-2-yl, especially methyl-substituted or ethylsubstituted pyridin-2-yl, and most preferably V represents 3-methyl pyridin-2-yl.

Examples of preferred ligands of formula in their simplest forms are: N-methyl-N,N',N'-tris(3-methypyridin-2-ylmethyl)ethylene I ,2-diamine; N-ethyl-N,N' ,N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1I.2-diamine; N-benzyl-N,N',N'-tris(3-methy-pyridin-2-ylmethyl)ethylene. I,2-diamine; N-(2-hydroxyethyl)-N,N',N'-tris(3-methyl-pyridin2-ylmethyl)ethyene-.1 ,2-diaxnine;

N-(

2 -methoxyethyl)-NN'N'tris(3-methyl-pyridin2-ylmethyl)ethylene. I,2-diarnine;) N-methyl-NN',N'-tris(5-methylpyridin2-ylmethyl)ethylene I ,2-diamine; N-ethyl-N,N',N'-tri(5-methyl-pyridin-2-ylmethyl)thylene I ,2-diamine; N-benzyI-N,N',N'-tris(5-methy-pyridin;.2-yl'methyl)ethylene-I ,2-diamine; N-(2-hydroxyethyl)-NN',N'-tris(5-methyl-pyridin-2-ylmethyl)ethylene. I,2-diamine;

N-(

2 -methoxyethyl)-N,N',N'-tris(5-methy-pyridi-2-ylmethyl)ethylene. I,2-diamine; N-methyl-N,N' ,N'-tris(3-ethyl-pyridin-2-ylmethyl)ethylene I ,2-diamine; N-ethyl-N,N',N'-tris(3-ethyl-pyridin-2-ylmethyl)ethylene. 1 .2-diamine; N-benzyl-NN ',N'-tris(3-ethyl-pyridin-2-ylmethyl)ethylene'-1I,2-diami'ne;) N-2hdoyty)NN,'ti(-6hlprdn2ymty~t~ee 1 .2-dianiine;

N-(

2 -methoxyethyl)-NN',N'-tris(3-ethyl-pyridin-2-ylmethyI)ethyle'ne I .2-diamine; N-methyl-N,N',N'-tis(5-ethyl-pyridin-2-ylmethyl)ethylene. I,2-diamine; N-ethyl-N,N' ,N'-tris(5-ethyl-pyridii-2-ylmethyl)ethylene-1I,2-dianiine; N-benzyl-N,N' ,N'-tris(5-ethyl-pyridin-2-ylmethyI)ethylene-1 ,2-diamine; and N-(2-methoxyethyl)-N4,N',N'-tris(5-ethyI-pyridin-2ylmethy)ethylene I ,2-dianine.

More preferred ligands are: N-ehlNN,'ti(-ehlprdn2ymty~tyee I ,2-dianiine; WO 00/12808 PCT/GB99/02878 27 N-ethyl-N,N',N'-tris(3-methyl-pyridifl-2-ylmethyl)ethylefle- 1 ,2-diamine; N-benzyl-N,N' ,N'-tris(3-methyl-pyridin-2-ylmethyl)ethylefle-1I,2-diamnine; N-(2-hydroxyethyl)-N,N',N'-tri(3-methyl-pyridil-2-ylmethyl)ethylele-1I,2-diamine; and N-(2-methoxyethyl)-NN' ,N'-tris(3-methyl-pyridin-2-ylmethyl)ethylene- 1.2-diamine.

The most preferred ligands are: N-methyl-N,N' ,N'-tris(3-methyl-pyridin-2-ylmethyl)ethylefle-1I,2-diamine; and N-ethyl-NN',N'-tris(3-methyl-pyridil-2-ylmethyl)ethylefle-1I,2-diamine.

Preferably, the metal M in formula is Fe or Mn, more preferably Fe., Preferred coordinating species X in formula may be selected from R 6 OH, NR 6 3 R 6 CN, R 6 00-, R 6 R 6 0,f R 6 CO0 OCN-, SCN-, N 3 CN; F, Cl-, Bf, 02-, N0 3 N02-, S0 4 S0 3 P0 4 3 and aromatic N donors selected from pyridines, pyrazines, pyrazoles, pyrroles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, with R 6being selected from hydrogen, optionally substituted alkyl and optionally substituted aryl. X may also be the species LMO'or LMOO., wherein M is a transition metal and L is a ligand as defined above. The coordinating species X is preferably- 3 20 selected from CH 3 CN, H 2 0, F, Cl-, Bf, OOH-, R 6 C00, R 6 LMO-, and LMOOwherein R 6 represents hydrogen or optionally substituted phenyl, naphthyl, orCI-4 alkyl.

The counter ions. Y in formula 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 R 7 CO, BPh4-, C10 4

BF

4 PF6-, R 7 S0 3 R 7 S0 4 s2-, N0 3 CF, Bf, or F, with R 7 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)ammoniumn cation.

WO 00/12808 PCT/GB99/02878 28 Suitable counter ions Y include those which give rise to the formation of storage-stable solids. Preferred counter ions for the preferred metal complexes are selected from

R

7 COO C10 4

BF

4 PF6', R 7 SO3' (in particular CF 3

SO

3

R

7 SO4', S0 4 2 NO3, F', Br, and wherein R 7 represents hydrogen or optionally substituted phenyl, naphthyl or C 1

-C

4 alkyl.

It will be appreciated that the complex 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 under conditions of storage or use. Preferably, the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species. Alternatively, the catalyst may be formed in situ from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials. In one such example, the active catalyst may be formed in situ in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent. Thus, for example, ifM is iron, an iron salt such as FeSO 4 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex. 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 situ. Suitable ligand Lgenerating 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 Therefore, in alternative fourth and fifth embodiments, the organic substance is a compound of the general formula [{M'aL)bXc]ZYq in which WO 00/12808 PCT/GB99/02878 29 M' represents hydrogen or a metal selected from Ti, V, Co, Zn, Mg, Ca, Sr, Ba, Na, K, and Li; X represents a coordinating species; a represents an integer in the range from 1 to b represents an integer in the range from 1 to 4; c represents zero or an integer in the range from 0 to z represents the charge of the compound and is an integer which can be positive, zero or negative; Y represents a counter ion, the type of which is dependent on the charge of the compound; q z/[charge and L represents a pentadentate ligand of general formula or as defined above.

In a fourth embodiment of the first:variant, the organic substance comprises a smacrocyclic ligand of formula 1 Z 2 Q Q.

wherein Z' and Z 2 are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring structure being substituted by one or more substituents; Y' and Y 2 are independently selected from C, N, O, Si, P and S atoms; A' and A 2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl) being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulphonate, phosphate, electron donating groups and electron withdrawing groups, and groups of formulae 2 WO 00/12808 PCT/GB99/02878

G

3

G

3 0- and G 3 wherein each of G 2 and G 3 is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups (in addition to any amongst the foregoing); i and j are selected from 0, 1 and 2 to complete the valency of the groups Y' and

Y

2 each of Q'-Q 4 is independently selected from groups of formula

A

3 A Y

A

4 b _A6 .d wherein I0>a+b+c>2 and d>=1; each Y 3 is independently selected from -SO2-, (wherein G' is hereinbefore defined), arylene, heteroarylene, and each ofA 3

-A

6 is independently selected from the groups hereinbefore defined for A' and A 2 and wherein any two or more ofA'-A 6 together form a bridging group, provided that if A' and A 2 are linked without simultaneous linking also to any of A 3

-A

6 then the bridging group linking A' and A 2 must contain at least one carbonyl group. In the ligands of formula unless specifically stated to the contrary, all alkyl, hydroxyalkyl alkoxy, and aikenyl groups preferably have from I to 6, more preferably from 1 to 4 carbon atoms.

Moreover, preferred electron donating groups include alkyl methyl), alkoxy (e.g.

methoxy), phenoxy, and unsubstituted, monosubstituted and disubstituted amine groups.

Preferred electron withdrawing groups include nitro, carboxy, sulphonyl and halo groups.

WO 00/12808 PCT/GB99/02878 31 The ligands of formula may be used in the form of complexes with an appropriate metal or, in some cases, in non-complexed form. In the non-complexed form; they rely upon complexing with a metal supplied in the form of a separate ingredient in the composition, specifically provided for supplying that metal, or upon complexing with a metal found as a trace element in tap water. However, where the ligand alone or in complex form carries a (positive) charge, a counter anion is necessary. The ligand or complex may be formed as a neutral species but it is often advantageous, for reasons of stability or ease of synthesis, to have a charged species with appropriate anion.

Therefore, in an alternative fourth embodiment, the ligand of formula is ion-paired with a counter ion, which ion-pairing is denoted by formula [HxL]ZYq wherein H is an hydrogen atom; Y is a counter anion, the type of which is dependent on the charge of the complex; x is an integer such that one or more nitrogen atoms in L is protonated; 20 z represents the charge of the complex and is an integer which can be positive or zero; q=z/[charge of and L is a ligand of formula as defined above.

In a further alternative fourth embodiment, the organic substance forms a metal complex of formula based on the ion pairing of formula thus: [MxL]ZYq WO 00/12808 PCT/GB99/02878 wherein L, Y, x, z and q are as defined for formula above and M is a metal selected from manganese in oxidation states II-V, iron II-V, copper I-Il, cobalt I-III, nickel I-III, chromium II-VI, tungsten IV-VI, palladium V, ruthenium II-IV, vanadium III-IV and molybdenum IV-VI.

Especially preferred are the complexes of formula wherein M represents manganese, cobalt, iron or copper.

In a preferred fourth embodiment, the organic substance forms a complex of the formula

R

3 -N N--R M X( Y)

R

2 wherein M represents an iron atom in oxidation state II or III, a manganese atom in oxidation state 11, III, IV or V, a copper atom in oxidation state I, II or III or a cobalt atom in oxidation state II, III or IV, X is a group which is either a bridge or is not a bridge between iron atoms, Y is a counter ion, x and y being and z being the charge of the metal complex, and p=z/ charge of Y; RI and R 2 being independently one or more ring substituents selected from hydrogen and electron donating and withdrawing groups, R 3 to Rs being independently hydrogen, alkyl, hydroxyalkyl, alkenyl or variants of any of these when substituted by one or more electron donating or withdrawing groups.

WO 00/12808 PCT/GB99/02878 33 For the avoidance of doubt, means "less than or equal to" and means "greater than or equal to".

Preferably, in the complex of formula M represents an iron atom in oxidation state II or Ill or a manganese atom in oxidation state II, III, IV, or V. Preferably the oxidation state of M is III.

When M is iron, preferably the complex of formula is in the form of a salt of iron (in oxidised state) dihalo-2,11 -diazo[3.3](2,6)pyridinophane, dihalo-4-methoxy-2,1 diazo[3.3] pyridinophane and mixtures thereof, especially in the form of the chloride salt.

When M is manganese, preferably the complex of formula is in the form of a salt of manganese (in oxidised state) N, N'-dimethyl-2,11 -diazo[3.3](2,6)pyridnophane, especially in the form of the monohexafluorophosphate salt.

Preferably, X is selected from H 2 0, OH', O 2 SH', S 2

S

4 2

NR

9 Rio', RCOO',

NR

9 RioR i, CF, Br', F, N 3 and combinations thereof, wherein R 9 Rio and Ri1 are 20 independently selected from C 1 -4 alkyl and aryl optionally substituted by one or more electron withdrawing and/or donating groups. More preferably, X is a halogen, especially a fluoride ion.

In the formulae and the anionic counter ion equivalent Y is preferably selected from C1', Br', NO3', C104', SCN, PF 6 RSO3', RSO4', CF 3 S0 3 BPh4-, and OAc'. A cationic counter ion equivalent is preferably absent.

In formula Ri and R 2 are preferably both hydrogen. R 3 and R 4 are preferably C-4 alkyl, especially methyl. Rs-Rs are each preferably hydrogen.

WO 00/12808 PCT/GB99/02878 34 According to the values ofx and y, the aforementioned preferred iron or manganese catalysts of formula may be in the form of a monomer, dimer or oligomer. Without being bound by any theory, it has been conjectured that in the raw material or detergent composition state, the catalyst exists mainly or solely in monomer form but could be converted to dimer, or even oligomeric form, in the wash solution.

In typical washing compositions the level of the organic substance is such that the in-use level is from 1 pM to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 pM. Higher levels may be desired and applied in industrial textile bleaching processes.

Preferably, the aqueous medium has a pH in the range from pH 6 to 13, more preferably from pH 6 to 11, still more preferably from pH 8 to 11, and most preferably from pH 8 to 10, in particular from pH 9 to The method of the present invention has particular application in detergent bleaching, especially for laundry cleaning. Accordingly, in another preferred embodiment, the method uses the organic substance in a liquor that additionally contains a surface-active material, optionally together with detergency builder.

The bleach liquor may for example contain a surface-active material in an amount of from 10 to 50% by weight. The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher aryl WO 00/12808 PCT/GB99/02878 groups. Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (Cs-Cls) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (C9-C 2 o) benzene sulphonates, particularly sodium linear secondary alkyl (Clo-Cis) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (Cg-Cig) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (Cs-C 20 with sodium bisulphite and those derived by reacting paraffins with SO 2 and Cl 2 and then hydrolysing with a base to produce a random sulphonate; sodium and ammonium (C 7

-C

12 dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe material made by reacting olefins, particularly (C 0

-C

2 o) alpha-olefins, with SO 3 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (Clo-C 15 alkylbenzene sulphonates, and sodium (Ci 6 -C18) alkyl ether sulphates.

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

-C

22 phenols, generally 5-25 EO, i.e. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (Cs-Cis) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO. Other so-called nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.

Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively WO 00/12808 PCT/GB99/02878 36 high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.

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

-C

1 2 fatty acid soaps.

The bleach liquor may also contains a detergency builder, for example in an amount of from about 5 to 80 by weight, preferably from about 10 to 60 by weight. Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.

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

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

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

In particular, the bleach liquor may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted WO 00/12808 PCT/GB99/02878 37 or only used in very small amounts. Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate and waterinsoluble crystalline or amorphous aluminosilicate builder materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder.

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

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

WO 00/12808 PCT/GB99/02878 38 Whilst the present invention is based on the catalytic bleaching of a substrate by atmospheric oxygen or air, it will be appreciated that small amounts of hydrogen peroxide or peroxy-based or -generating systems may be included in the treatment composition, if desired. Preferably, however, the composition will be devoid of peroxygen bleach or peroxy-based or -generating bleach systems.

The invention will now be further illustrated by way of the following non-limiting examples: WO 00/12808 PCT/GB99/02878 39

EXAMPLES

Example 1 This example describes a synthesis of a catalyst according to formula Preparation of MeN4Py ligand: The precursor N4Py.HCIO 4 was prepared as follows: To pyridyl ketone oxim (3 g, 15.1 mmol) was added ethanol (15 ml), concentrated ammonia solution (15 mL) and NH4OAc (1.21 g, 15.8 mmol). The solution was warmed until reflux. To this solution was added 4.64 g Zn in small portions. After the addition of all Zn, the mixture was refluxed for 1 hour and allowed to cool to ambient temperature. The solution was filtered and water (15 ml) was added. Solid NaOH was added until pH>>10 and the solution was extracted with CH 2 C2 (3 x 20 ml). The organic layers were dried over Na 2

SO

4 and evaporated until dryness. Bis(pyridin-2yl)methylamine (2.39 g, 12.9 mmol) was obtained as a colourless oil in 86% yield, showing the following analytical characteristics: 'H NMR (360 MHz, CDCI 3 8 2.64 2H, NH 2 5.18 1H, CH), 6.93 2H, 20 pyridine), 7.22 2H, pyridine), 7.41 2H, pyridine), 8.32 2H, pyridine); 1 3

C

NMR (CDCl 3 62.19 121.73 122.01 136.56 149.03 (CH), 162.64 (Cq).

To picolylchloride hydrochloride (4.06 g, 24.8 mmol) was added, at 0°C, 4.9 ml of a NaOH solution. This emulsion was added by means of a syringe to bis(pyridin-2yl)methylamine (2.3 g, 12.4 mmol) at 0°C. Another 5 ml of a 5N NaOH solution was added to this mixture. After warming to ambient temperature, the mixture was stirred vigorously for 40 hrs. The mixture was put in an ice bath and HC10 4 was added until pH<l, whereupon a brown solid precipitated. The brown precipitate was collected by filtration and recrystallized from water. While stirring, this mixture was allowed to cool

I

WO 00/12808 PCT/B9902878 to ambient temperature, whereupon a light-brown solid precipitated which was collected by filtration and washed with cold water and air-dried (1.47 g).

From 0.5 g of the perchlorate salt of N4Py prepared as described above, the free amine was obtained by precipitating the salt with 2N NaOH and subsequently by extraction with CH 2 C1 2 To the free amine was added under argon 20 ml of dry tetrahydrofuran freshly distilled from LiAlH 4 The mixture was stirred and cooled to -70 OC by an alcohol dry ice bath. Now 1 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mixture was allowed to warm to -20 oC and now 0.1 ml of methyl iodide was added. The temperature was kept to -10 oC for 1 hour. Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue water was added and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried on sodium sulphate, filtered and evaporated giving 0.4 g residue. The residue was purified by crystallisation from ethyl acetate and hexane giving 0.2 g of creamish powder (50% yield) showing the following analytical characteristics: 'H NMR (400 MHz, CDC13): 5 (ppm) 2.05 3H, CH 3 4.01 4H, CH 2 6.92 (m, 2H, pyridine), 7.08 2H, pyridine), 7.39 4H pyridine), 7.60 (m'2H, pyridine), 7.98 2H, pyridine), 8.41 2H pyridine), 8.57 2H, pyridine). 3 C NMR (100.55 MHz, CDCI 3 6 (ppm) 21.7 (CH 3 58.2 (CH 2 73.2 121.4 121.7 123.4 123.6 136.0 148.2 148.6 160.1 163.8 (Cq).

(ii) Synthesis of the complex I(McN4Py)Fe(CH 3 CN)I(CI0 4 2 Fe(MeN4Py): To a solution of 0.27 g of MeN4Py in 12 ml of a mixture of 6 ml acetonitrile and 6 ml methanol was added 350 mg Fe(C10 4 2 .6H 2 0 immediately a dark red colour formed. To the mix was added now 0.5 g of sodium perchlorate and a orange red precipitate formed immediately. After 5 minutes stirring and ultrasonic treatment the precipitate was isolated by filtration and dried in vacuo at 50 0 C. In this way 350 mg of an orange red powder was obtained in 70%/ yield showing the following analytical characteristics: WO 00/12808 PCT/GB99/02878 41 'H NMR (400 MHz, CD3CN): 6 (ppm) 2.15, (CH 3 CN), 2.28 3H, CH 3 4.2 (ab, 4H,

CH

2 7.05 2H, pyridine), 7.38 4H, pyridine), 7.71 (2t, 4H pyridine), 7.98 2H, pyridine), 8.96 2H pyridine), 9.06 2H, pyridine).

UV/Vis (acetonitrile) [Xmax, nm M 381 (8400), 458 nm (6400).

Anal.Calcd for C 25

H

2 6 Cl 2 FeN 6 08: C, 46.11; H, 3.87; N, 12.41; Cl, 10.47; Fe, 8.25.

Found: C, 45.49; H, 3.95; N; 12.5; Cl, 10.7; Fe, 8.12.

Mass-ESP (cone voltage 17V in CH 3 CN): m/z 218.6 [MeN4PyFe] 2 239.1 [MeN4PyFeCH 3

CN]

2 Example 2 This example describes a synthesis of a catalyst according to formula Synthesis of BzN4Py ligand: To 1 g of the N4Py ligand prepared as described above, 20 ml of dry tetrahydrofuran freshly distilled from LiAIH 4 was added under argon. The mixture was stirred and cooled to -70 OC by an alcohol dry ice bath. Now 2 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mix was allowed to warm 20 to -20 0 C and now 0.4 ml of benzyl bromidide was added. The mixture was allowed to warm up to 25 oC and stirring was continued over night. Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue Swater was added and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried on sodium sulphate, filtered and evaporated giving 1 g brown oily residue. According to NMR spectroscopy, the product was not pure but contained no starting material (N4Py). The residue was used without further purification.

(ii) Synthesis of the complex [(BzN4Py)Fe(CH 3 CN)](CO04)2. Fe(BzN4Py): WO 00/12808 PCT/GB99/02878 42 To a solution of 0.2 g of the residue obtained by the previous described procedure in ml of a mixture:of 5 ml acetonitrile and 5 ml methanol was added 100 mg 4 2 .6H 2 0 immediately a dark red colour formed. To the mix was added now 0.25 g of sodium perchlorate and ethylacetate was allowed to diffuse into the mixture overnight. Some red crystals were formed which were isolated by filtration and washed with methanol. In this way 70 mg of a red powder was obtained showing the following analytical characteristics: 1H NMR (400 MHz, CD3CN): 8 (ppm) 2.12, 3H, CH 3 CN), 3.65'+ 4.1 (ab, 4H, CH2), 4.42 2H, CH 2 -benzyl), 6.84 2H, pyridine), 7.35 4H, pyridine), 7.45 3 H, benzene) 7.65 4H benzene pryidine), 8.08(m, 4H, pyridine), 8.95 4H pyridine).

UV/Vis (acetonitrile) nm M 380 (7400), 458 nm (5500).

Mass-ESP (cone voltage 17V in CH3CN): m/z 256.4 [BzN4Py]2+; 612 [BzN4PyFeCIO 4 Example 3: This example describes syntheses of catalysts according to formula All reactions were performed under a nitrogen atmosphere, unless indicated otherwise.

All reagents and solvents were obtained from Aldrich or Across and used as received, unless stated otherwise. Petroleum ether 40-60 was distilled using a rotavapor before using it as eluent. Flash column chromatography was performed using Merck silica gel or aluminium oxide 90 (activity II-III according to Brockmann). 'H NMR (300 MHz) and 3 C NMR (75 MHz) were recorded in CDCI 3 unless stated otherwise.

Multiplicities were addressed with the normal abbreviations using p for quintet.

Synthesis of starting materials for ligand synthesis: Synthesis of N-benzyl amino acetonitrile. N-benzyl amine (5.35 g, 50 mmol) was dissolved in a water: methanol mixture (50 mL, Hydrochloric acid 30 WO 00/12808 PCT/GB99/02878 43 was added until the pH reached 7.0. Added was NaCN (2.45 g, 50 mmol). After cooling to 0 OC, formaline (aq. 35 4.00 g, 50 mmol) was added. The reaction was followed by TLC (aluminium oxide; EtOAc Et 3 N until benzylamine could be detected. Subsequently the methanol was evaporated in vacuo and the remaining oil "dissolved" in water. The aqueous phase was extracted with methylene chloride (3 x mL). The organic layers were collected and the solvent removed in vacuo. The residue was purified by Kugelrohr distillation (p 20 mm Hg, T 120 OC) giving N-benzyl amino acetonitrile (4.39 g, 30 mmol, 60 as a colourless oil.

'H NMR: 8 7.37 7.30 5H), 3.94 2H), 3.57 2H), 1.67 (br s, 1H); 3 C NMR: 8 137.74, 128.58, 128.46, 128.37, 127.98, 127.62, 117.60, 52.24, 36.19.

Synthesis of N-ethyl amino acetonitrile. This synthesis was performed analogously to the synthesis reported for N-benzyl amino acetonitrile. However, detection was done by dipping the TLC plate in a solution of KMnO 4 and heating the plate until bright spots appeared. Starting from ethylamine (2.25 g, 50 mmol), pure N-ethyl amino acetonitrile (0.68 g, 8.1 mmol, 16 was obtained as a slightly yellow oil.

'H NMR: 83.60(s, 2H),2.78(q,J=7.1,2H), 1.22(br s, 1H), 1.14 J= 7.2, 3H); 3 C NMR: 8 117.78, 43.08, 37.01, 14.53.

S 20 Synthesis of N-ethyl ethylene-1,2-diamine. The synthesis was performed according to Hageman; J.Org.Chem.; 14; 1949; 616, 634, starting from N-ethyl amino acetonitrile.

Synthesis of N-benzyl ethylene-i,2-diamine. Sodium hydroxide (890 mg; 22.4 mmol) was dissolved in ethanol (96 20 mL), the process taking the better part of 2 hours.

Added was N-benzyl amino acetonitrile 2.92 g, 20 mmol) and Raney Nickel (approx.

Hydrogen pressure was applied (p 3.0 atm.) until hydrogen uptake ceased.

The mixture was filtered over Cellite, washing the residue with ethanol. The filter should not run dry since Raney Nickel is relatively pyrophoric. The Cellite containing the Raney Nickel was destroyed by putting the mixture in dilute acid, causing gas formation). The ethanol was evaporated in in vacuo and the residue dissolved in water.

I

WO 00/12808 PCTIGB99/02878 44 Upon addition of base (aq. NaOH, 5N) the product oiled out and was extracted with chloroform (3 x 20 mL). After evaporation of the solvent in vacuo the 'H NMR showed the presence of benzylamine. Separation was enforced by column chromatography (silica gel; MeOH EtOAc: Et 3 N 1:8:1) yielding the benzyl amine, followed by the solvent mixture MeOH EtOAc Et 3 N 5:4:1. Detection was done by using aluminium oxide as a solid phase in TLC, yielding pure N-benzyl ethylene-1,2-diamine (2.04 g, 13.6 mmol, 69%).

'H NMR: 8 7.33 7.24 5H), 3.80 2H), 2.82 J= 5.7, 2H), 2.69 J= 5.7, 2H), 1.46 (br s, 3H); 13C NMR: 8 140.37, 128.22, 127.93, 126.73, 53.73, 51.88, 41.66.

Synthesis of 2-acetoxymethyl-5-methyl pyridine. 2,5-Lutidine (31.0 g, 290 mmol), acetic acid (180 mL) and hydrogen peroxide (30 mL, 30 were heated at 70-80 °C for 3hours. Hydrogen peroxide (24 mL, 30 was added and the subsequent mixture heated for 16 hours at 60-70 OC. Most of the mixture of (probably) hydrogen peroxide, water, acetic acid, and peracetic acid was removed in vacuo (rotavap, water bath 50 °C until p 20 mbar). The resulting mixture containing the N-oxide was added dropwise to acetic anhydride heated under reflux. This reaction was highly exothermic, and was controlled by the dropping speed. After heating under reflux for an hour, methanol was added dropwise. This reaction was highly exothermic. The resulting mixture was heated under reflux for another 30 minutes. After evaporation of the methanol (rotavap, *C until p 20 mbar), the resulting mixture was purified by Kugelrohr distillation (p 20 mm Hg, T 150 The clear oil that was obtained still contained acetic acid.

This was removed by extraction (CH 2 C2, NaHCO 3 yielding the pure acetate of 2acetoxymethyl-5-methyl pyridine (34.35 g, 208 mmol, 72 as a slightly yellow oil.

'H NMR:. 8.43 1H), 7.52 (dd, J= 7.8, J= 1.7, 1H), 7.26 J= 7.2, 1H), 5.18 2H), 2.34 2.15 3H); 3 C NMR: 8 170.09, 152.32, 149.39, 136.74, 131.98, 121.14, 66.31, 20.39, 17.66.

WO 00/12808 PCT/GB99/02878 Synthesis of 2-acetoxymethyl-5-ethyl pyridine. This synthesis was performed analogously to the synthesis reported for 2-acetoxymethyl-5-methyl pyridine. Starting from 5-ethyl-2-methyl pyridine (35.10 g, 290 mmol), pure pyridine (46.19 g, 258 mmol, 89%) was obtained as a slightly yellow oil.

'H NMR: 8 8.47 1H), 7.55 J= 7.8, 1H), 7.29 J= 8.1, 1H), 2.67 J= 7.8, 2H), 2.14 3H), 1.26 J= 7.77, 3H); 'C NMR: 8 170.56, 152.80, 149.11, 138.47, 135.89, 121.67, 66.72, 25.65, 20.78, 15.13.

Synthesis of 2-acetoxymethyl-3-methyl pyridine. This synthesis was performed analogously to'the synthesis reported for 2-acetoxymethyl-5-methyl pyridine. The only difference was the reversal of the Kugelrohr distillation and the extraction. According to 'H NMR a mixture of the acetate and the corresponding alcohol was obtained.

Starting from 2,3-picoline (31.0 g, 290 mmol), pure 2-acetoxymethyl-3-methyl pyridine (46.19 g, 258 mmol, 89%, calculated for pure acetate) was obtained as a slightly yellow oil, 'H NMR: 6 8.45 J= 3.9, 1H), 7.50 8.4, 1H), 7.17 (dd, J= 7.8,J= 4.8, 1H), 5.24 2H), 2.37 3H), 2.14 3H).

Synthesis of 2-hydroxymethyl-5-methyl pyridine. pyridine (30 g, 182 mmol) was dissolved in hydrochloric acid (100 mL, 4 The mixture was heated under reflux, until TLC (silica gel; triethylamine:ethyl acetate:petroleum ether 40-60 1:9:19) showed complete absence of the acetate (normally 1 hour). The mixture was cooled, brought to pH 11, extracted with dichloromethane (3 x 50 mL) and the solvent removed in vacuo. Pure 2pyridine (18.80 g, 152 mmol, 84 was obtained by Kugelrohr distillation (p 20 mm Hg, T 130 as a slightly yellow oil.

'HNMR: 6 8.39 1H), 7.50 (dd, J= 7.8, J= 1.8, 1H), 7.15 J= 8.1, 1H), 4.73 2H), 3.83 (br s, 1H), 2.34 3H); 3 C NMR: 6 156.67, 148.66, 137.32, 131.62, 120.24, 64.12, 17.98.

WO 00/12808 PCT/GB99/02878 46 Synthesis of 2-hydroxymethyl-5-ethyl pyridine. This synthesis was performed analogously to the synthesis reported for 2-;hydroxymethyl-5-methyl pyridine. Starting from 2-acetoxymnethyl-5-ethyl pyridine (40 g, 223 rnmol), pure 2-hydroxymethyl -5 -ethyl pyridine (26.02 g, 189 mniol, 85 was obtained as a slightly yellow oil.

'H NMR: 8 8.40 J 1 H),-7.52 (dd, J= J 2.0, 11H), 7.18 J 8. 1, 1H), 4.74 2H), 3.93 (br s, I 2.66'(q, J 2H), 1.26 J 7.5, 3H); 1 3 CNMR: '8 156.67, 148.00, 137.87, 136.13, 120.27, 64.07, 25.67, 15.28.

Synthesis of 2-hydroxymethyl-3-inethyl pyridinie. -This synthesis was performed analogously to the synthesis reported for 2-hydrokcymethyl-5-methyl pyridine. Starting from 2-acetoxymethyl-3-methyl pyridine (25g (recalculated for the mixture), 152 mmol), pure 2-hydroxymethyl-3-methyl pyridine (15.51 g, 126 mmol,. 83 O/)was obtained as a slightly yellow oil.

'HNMR: 5 8.40 (d,J 1 7.47 IH), 7.15 (dd, J J 5. 1, I 4.85 (br s, I 4.69 I 2.22 3 H); 1 3 C NMR: 6 156.06, 144.97, 137.38, 129.53, 121.91, 61.38, 16.30.

6i) Synthesis of ligzands: Synthesis of N-methyl-NN'.N-tris(pyridin-2-ylniethyl)'ethylene-1,2-diami~ie (Mi).

The 1ig.nd LI (comparative) was -prepared according to Bernal, Ivan; Jensen, Inge Margrethe; Jensen, Kenneth McKenzie, Christine Toftlund. Hains; Tuchagues, Jean-Pierre; J.Chem.Soc.Dalton Trans.; 2-2; 1995; 3667-3676.

Synthesis of N-methyI-NNVN-tris(3-m ethyl' ridin-2-Imethy1)ethyene.I,2.

diamine (L2, MeTrilen). 2-Hydroxymethyl-3-methyl pyridine (5.00 g, 40.7 mmol) was dissolved in dichioromethane (30 mL). Thionyl chloride (30 mL) was adde d dropwise under cooling (ice bath). The resulting mixture was stirred for I hour and the solvents removed in vacuo (rotavap, until p 20 mm. Hg, T 50 TC). To the resultant mixture WO 00/12808 PCT/GB99/02878 47 was added dichloromethane (25 mL). Subsequently NaOH (5 N, aq.) was added dropwise until the pH (aqua) 11. The reaction was quite vigorous in the beginning, since part of the thionyl chloride was still present. N-methyl ethylene-1,2-diamine (502 mg, 6.8 mmol) and additional NaOH (5 N, 10 mL) were added. The reaction mixture was stirred at room temperature for 45 hours. The mixture was poured into water (200 mL), and the pH checked 14, otherwise addition of NaOH (aq. The reaction mixture was extracted with dichloromethane (3 or 4 x 50 mL, until no product could be detected by TLC). The combined organic phases were dried and the solvent removed in vacuo. Purification was enforced as described before, yielding N-methyl- N,N',-tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine as a slightly yellow oil.

Purification was enforced by column chromatography (aluminium oxide 90 (activity II- III according to Brockmann); triethylamine ethyl acetate petroleum ether 40-60 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf The compound was eluted using ethylacetate triethyl amine 9:1.

N-methyl-N,N',N-tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L2, 1.743 g, 4.30 mmol, 63 was obtained.

'H NMR: 8 8.36 J 3.0, 3H), 7.40 7.37 3H), 7.11-7.06 3H), 3.76 (s, 4H), 3.48 2H), 2.76 2.71 2H), 2.53 2.48 2H), 2.30 3H), 2.12 6H), 2.05 3H); "C NMR: 8 156.82, 156.77, 145.83, 145.67, 137.61, 133.14, 132.72, 122.10, 121.88, 62.32, 59.73, 55.19, 51.87, 42.37, 18.22, 17.80.

Synthesis of N-ethyl-N,N ,N'-tris(3-methyipyridin-2-ylmethyl)ethylene- ,2-diamine (L3, EtTrilen). This synthesis is performed analogously to the synthesis for L2.

Starting from 2-hydroxymethyl-3-methyl pyridine (25.00 g, 203 mmol) and N-ethyl ethylene-1,2-diamine (2.99 g, 34.0 mmol), N-ethyl-N,N,N-tris(methylpyridin-2ylmethyl)ethylene-l,2-diamine (L3, 11.49 g, 28.5 mmol, 84 was obtained. Column chromatography (aluminium oxide; Et 3 N EtOAc petroleum ether 40-60 1:9:30, followed by Et 3 N EtOAc 1:9).

I WO 00/12808 PCT/GB99/02878 48 'H*NMR: 5 8.34 8.30 (mn, 311), 7.40 7.34 (mn, 3H), 7.09 7.03 (mn, 3H). 3.71 (s, 411), 3.58 2H), 2.64 2.59 (i;211), 2.52 2.47 (mn, 2H1), 2.43 2.36 (in, 2H), 2.31 (s, 3H), 2.10 611), 0.87 (t,1J 7.2;3H); 3 CNMR: 5 157.35, 156.92, 145.65, 137.6-1, 133.14, 132.97, 122.09,121.85, 59.81, 59.28,51.98, 50.75, 48.02, 18.27, 17.-80, 11.36.

Synthesis of N-benzy]-N,N',N'-tris(3-methypyridin-2-ylmethy)ethylene-1 ,2diamine (L4, BzTrilcn). This synthesis is performed analogouslytio the synthesis for L2. Starting from 2-hydrox'ymethyl-3-mhethylpyridine (3.00 g 24.4 mrmol), and N-benzyl ethylene- 1,2-diainine (610 mg, 4.07 mmol), N-benzy]-l-.NN-tris(3-methylpyridin-2yhrbethyl)ethylene-1,2-diamine (L4, 1.363 g, 2.93 mmcl. 72 was obtained. Column chromatography (aluminium oxide; EI 3 N: EtOAc: petroleum ether 40-60 1:9:10).

'H NMR: 5 8.33 8.29 (in, 3H), 7.37 7.33 3H), 7.21 7.03 (in, 8H), 3.66 (s, 411), 3.60 2H), 3.42 2H),2.72 2.67 (in, 2H), 2.50 2.45 (mn, 2H); 2.23 311), 2.03 (s,.6H1); 1 3 CNMR: 8 157.17, 156.96, 145.83, 145.78, 139.29,* 137.91, 137.80,,133.45, 133.30, 128.98, 127.85, 126.62, 122.28, 122.22, 59.99, 58.83, 51.92, 51.54, 18.40, 17.95.

Synthesis of N-hydroxyehyl-NN'JV-tis(3-methylpyridin-2-vmethyl)etbhylene-1,2diamine This synthesis is performed analogously to the synthesis for L6. Starting from 2-hydroxyinethyl-3-methyl pyridine (3.49 g, 28.4 innol), and N-hydroxyethyl ethylene-1,2-diamine (656 mng 6.30 m'mol), after 7 days N-hydroxyethyl-N,,X-'tris(3inethylpyridin-2-ylinethyl)ethylene-1,2-diainine 379 nmg, 0.97 minol, 14 was obtained.

'H1NMR: 5 8.31 8.28 (in, 311), 7.35 7.33 (in, 311), 7.06 7.00 (mn, 311), 4.71 (br s, 111), 3.73 411), 3.61 2H), 3.44 J 2H), 2.6 8 411), 2.57 J 211), 2. 19 311), 2.10 611); 1 3 C NMR: 8 157.01, 156.88, 145.91, 145..80, 137.90, 137.83, 133.30, 131.89, 122.30, 121.97, 59.60, 59.39, 57.95, 56.67, 51.95, 51.22. 18.14, 17.95.

WO 00/12808 PCT/GB99/0878 49 Synthesis of N-methyl-N,N',N'-tris(5-methylpyridin-2-ylmethyl)ethylene-1,2diamine 2-hydroxymethyl-5-methyl pyridine (2.70 g, 21.9 mmol) was dissolved in dichloromethane (25 mL). Thionyl chloride (25 mL) was added dropwise under cooling (ice bath). The resulting mixture was stirred for 1 hour and the solvents removed in vacuo (rotavap, until p 20 mm Hg, T 35 0 The remaining oil was used directly in the synthesis of the ligands, since it was known from the literature that the free picolyl chlorides are somewhat unstable and are highly lachrymatory. To the resultant mixture was added dichloromethane (25 mL) and N-methyl ethylene-1,2diamine (360 mg, 4.86 mmol). Subsequently NaOH (5 N, aq.) was added dropwise.

The reaction was quite vigorous in the beginning, since part of the thionyl chloride was still present. The aqueous layer was brought to pH 10, and additional NaOH (5 N, 4.38 mL) was added. The reaction mixture was stirred until a sample indicated complete conversion (7 days). The reaction mixture was extracted with dichloromethane (3 x 25 mL). The combined organic phases were dried and the solvent removed in vacuo. Purification was enforced by column chromatography (aluminium oxide 90 (activity II-III according to Brockmann); triethylamine ethyl acetate petroleum ether 40-60 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf= The compound was eluted using ethyl acetate triethyl amine 9:1, yielding N-methyl-N,NN'-tris(5-methylpyridin-2ylmethyl)ethylene-l,2-diamine (L6, 685 mg, 1.76 mmol, 36 as a slightly yellow oil.

'H NMR: 8 8.31 3H) 7.43 7.35 5H), 7.21 J= 7.8, 1H), 3.76 4H), 3.56 2H), 2.74 2.69 2H), 2.63 2.58 2H), 2.27 6H), 2.16 3H); "C NMR: 8 156.83, 156.43, 149.23, 149.18, 136.85, 136.81, 131.02, 122.41, 122.30, 63.83, 60.38, 55.53, 52.00, 42.76, 18.03.

Synthesis of N-methyl-NN',N-tris(5-ethylpyridin-2-ylmethyl)ethylene-1,2-diamine This synthesis is performed analogously to the synthesis for L6. Starting from 2pyridine (3.00 g, 21.9 mmol), and N-methyl ethylene-1,2- WO 00/12808,.

PCT/GB99/02878 diamine (360 mg, 4.86 nimol), after 7 days N-methyl-N-,',APtris(-ethypyridin-2 ylmethyl)ethylene-1,2-diamine (L7, 545 mg, 1.26 mmol, 26 was obta-ined.

'H NMR: 6 8.34 3H), 7.44 7.39'(m, 5H),,7.26 J1 6.6, INH), 3.80 4H), 3.59 2H), 2.77 -2.72 (in, 2H), 2.66 2.57 (in, 8H), 2.18 3H), 1.23 J= 7.5, 9H); 1 3 C NMR: 8 157.14, 156.70, 148.60, 148.53, 137.25, 135.70, 122.59, 122.43, 63.91, 60.48, 55.65, 52.11, 42.82,25.73, 15.36.

6ii) Synthesis of metal-lirand complexes:) Synthesis of N-methyl-NN'ZV-tris(3-methylpyridin-2-ylm ethyl)eth yiene-1 ,2diAmine iron(II)chloride.PF 6 ([L2 Fe(II)CI]PF 6 FeCI 2 .4H 2 0 (51.2 mg,257 g.mol) was dissolv ed in MeOH :H 2 0 1(2.5 mL). The solution was heated to 50 OC.

Added was N-eblN M rs3mtyprdn2y M~ty~ty e1 ,2-diamrine (L2, 100 mg, ;257 pimol) in MeOH :'H 2 b 1: 1(2.0 mL). Subsequently NaPF 6 (86.4 mng, 514 imol) iniH 2 0 (2.5 mL) wasadded dropwise. Cooling to room temperature, filtration and drying in i'acuo (p 0.05 mm Hg, T =room temperature) yielded the complex [L2 Fe(II)CIJPF 6 (149 mg, 239 prnol,'93 as a yellow solid.

'H NMR (CD 3 CN, paramagnetic): 8 167.17, 142.18, 117.01, 113.34, 104.79, 98.62, 70.77, 67.04, 66.63, 58.86, 57.56, 54.49, 51.68, 48.56, 45.90, 27.99,.27.36, 22.89, 20.57, 14.79, 12.14, 8.41, 8.16, 7.18, 6.32, 5.78, 5.07, 4.29, 3.82, 3.43, 2.91, 2.05, 1.75, 1.58, 0.94, 0.53, -0.28, -4.82, -18.97, -23.46.

Synthesis ofN-ethyl-N,N',N'Y-tris(3-methylpyridin-2-ylmetjiyl)ethylene-1,2-diamine iron(II)chloride.PF 6 (1L3 Fe(II)CI]PF 6 This synthesis was performed analogously to the synthesis for [L2 Fe(II)CIJPF 6 Starting from N-ethyl-N,',-tris(3-methylpyridin- 2-ylmethyl)&thylene- 1,2-diamine (L3, 104 mg, 257 pmol) gave the complex [L3 Fe(II)CIJPF 6 (146 mng, 229 giol, 89%) as a yellow solid.

I

j WO 00/12808 PCT/GB99/02878 51 'H NMR (CD 3 CN, paramagnetic): 5 165.61, 147.20, 119.23, 112.67, 92.92, 63.14, 57.44, 53.20, 50.43, 47.80, 28.59, 27.09, 22.48, 8.55, 7.40, 3.63, 2.95, 2.75, 2.56, 2.26, 1.75, 1.58, 0.92, 0.74, -0.28, -1.68, -2.68, -12.36, -28.75.

Synthesis of N-benzyl-NN 'N-tris(3-methylpyridin-2-ylmethyl)ethylene-1,2diamine iron(II)chloride.PF6 ([L4 Fe(II)C1]PF 6 This synthesis was performed analogously to the synthesis for JL2 Fe(II)CIIPF 6 Starting from N-benzyl-N,Ntris(3-methylpyridin-2-ylmethyl)ethylene-1, 2 -diamine (L4, 119.5 mg, 257 pmol) gave the complex (172 mg, 229 jimol, 95 as a yellow solid.

'H NMR (CD 3 CN, paramagnetic): 8 166.33, 145.09, 119.80, 109.45, 92.94, 57.59, 52.83, 47.31, 28.40, 27.89, 16.28, 11.05, 8.70, 8.45, 7.69, 6.99, 6.01, 4.12, 2.89, 2.71, 1.93, 1.56, -0.28, -1.68, -2.58, -11.40, -25.32.

Example 4 This example describes a synthesis of a catalyst of formula wherein:- OMe

N

Ill H-N N-H FeCI 2 (Clj)

R

2 -Rg=H; RI=4-MeO; x=l; y-l; z=1; X=CI, n=2; Y=Cl', p=l.

WO 00/1 2808 PTG9/27 52 PTG9/27 0i) Svnthesis of the ligand 2 ,lJ-diazal.31-(4-metho)v)(2,6)yvridinoplane ((4OMe)LN

H

4-chloro-2 6.-PYHYrId dimethyl ester A mixture of 4 -hydroxy-2.6-pyridine dicarboxylic acid (12.2 g, 60 minoles) and PCI 5 4 1.8g, 200 mmoles) in 100 ml of CC1 4 was refluxed until the evolution of HCI ceased. Absolute methanol (50m1) was slowly added. After cooling, all the volatile material was removed. The mixture was then poured into 200'ml of water and ice. The diester crystallised immediately and was collected by filtration 'H NMR (200MHz, H-20) 5 7.60 4.05 (6H, s).

4-methoxv-2, 6-pyridine dimethanol Metallic sodium (1 g, 44 mmoles) was dissolved into 200 ml of dry methanol. 4 -chloro-2,6-pyridyl dimethyl ester (9.2 g, 40 mmoles) was then added and the mixture was refluxed for 3 hours to obtain pure 4-methoxy-2,6pyridyl dimethyl ester. To this solution, at RT, NaBH 4 (9.1 g, 240 mrnoles) was added in small portions and the mixture was refluxed for 16 hours. Acetone (30 ml) Was then added and the solution refluxed for an additional I hour. After all the volatile material was removed, the residue was heated with 60 ml of a saturated NaHCO 3 /Na 2

CO

3 solution. After dilution with 80 ml of water, the product was continuously extracted with CHCI 3 for 2-3 days. Evaporation of the CHCIJ yielded 83 of 4-meth oxy-2,6-) pyridine dimethanol. 'H NMR (200MHz, 1H20) 8 6.83 5.30 4.43 (4H,s), 3.82 (314, s).

4-metho) i-2, 6 -dichloromethyl~yridin This synthesis is carried out according literature.

NN I-loy-Z J-diaza3. 3 7-(4 -methoxy) 6 )-vridinophane. the procedure is similar to that described in the literature. The crude product obtained is practically pure WO 00/12808 PCT/GB99/02878 53 I H-NMR (CDCI 3 250 MHz): 7.72 d, J= 7Hz), 7.4 (111, t, J= 6Hz), 7,3 5 (4H, d, J= 7Hz), 7.1 (JH, d, J= 6Hz), 6.57 (2H, 4.45 (4H, 4.35 (4H, 3.65 (3H. 2.4 (6H, s).

2, Ji-diazaO[.3 7-(4-melhoxv)(2, 6hpvridinophane. The procedure is similar to the one described previously. The crude product obtained is purified by chromatography (alumina, CH 2

CI

2 /MeOH 95:5), yield 'H-NMR (CDCI 3 250 MHz): 7.15 (1H, t, J= 6Hz), 6.55 (JH, d, J= 6Hz), 6.05 (2H, S), 3.95 (4H, 3.87 (4H, 3.65 (3H, s).

Mass spectrum M+ 270 (100%) Synthesis of the complex [Fe(4OMeLNH,7 CI-1Cl: 270 mg of 2,1 1-diaza[3.3]-(4-methoxy)(2,6)pyridiflophafle (I mmole) were dissolved in 15 ml of dry THE. To this solution was added a solution of 270 mg of FeCl 3 *6H 2 0 (1 mnioles) in 5 ml of MeOH. The resulting mixture is evaporated to dryness and the solid product is dissolved in 10 ml of AcN with a Iminimum of MeGH. Slow diffusion of THE give 300 mg of brown crystals, yield 70%. Elemental analysis for 8

N

4

C

3 OFe0,5MeOH (found/theoretical): C=41.5/41.61 H=4.46/4.52 N=12.5/12.08 JR (KBr pellets, cm- 1 3545, 3414, 3235, 3075, 2883, 1615, 1477, 1437, 1340,1157, 1049, 883, 628, 338.

Example This example describes a synthesis of a catalyst of formula wherein:- WO 00/12808 PCT/G.B99/02878 54

N

R I-R 8 x=1; yI X=C 1, n=2; Y=C I p= I Synthesis of the complex [Fe(LN 4

H

2

)CI

2

ICI:

240 mg of LN4-1 2 0I mmoles) were dissolved in 15 ml of dry TI-F. To this solution was added a solution of 270 mg of FeC3y6-)O (I nimole) in 5 ml of MeGH. The resulting mixture is stirred and gives spontaneously 340 mg of yellow powder, yield IR (KBr pellets, cm-1): 3445, 3031, 2851, 1629, 1062, 1473, 1427, 1335, 1157, 11 18, 1045,936, 796,340,318) Example 6: This Example describes a synthesis of a catalyst of formula wherein:- WO 00/12808 PCT/GB99/02878 N- (F) 2

(PF

6

N

R,=R

2

=R

5 8

R

3 =R4=Me; x1l; y=1; n=2; z1-; X=F; m=2; Y=PF- 6 P=l difluorofN,N'dimetvl-2,11-diaza3.31( 2 6)pyridinophlielmanganese(III) h ewafluorophosih ate.

Synthesis of the ligand NN'dimelhivl-2,11-diazaf3.31(2, 6)pyridinophane: 2, 6-dichloromethvlipvridine. A mixture of 2,6-dimethanolpyridine (5g, 36 rnmoles) and MI Of SOC12 was refluxed for 4 hours. The mixture was concentrated (half volume).

Toluene was added (50 ml). The solid. fonned after cooling was then -filtered and dissolved in water and the solution neutralised with NaHCO 3 The solid obtained is filtered and dried 'H NMR (200MHz. CDCI 3 5 7.8 (1H,t, J=7H4z), 7.45 (2H,d, J=7 Hz)? 4.7 (414, s).

Sodium p-toluenesulphonamidure. To a mixture of Na 0 in dry EtOH (0.7 g, 29 mmoles) was added p-toluenesu lphonamide (5 g, 29 mmoles) and the solution was refluxed for 2 hours. After cooling, the solid obtained was filtered, washed with EtOH and dried (quantitative yield).

N.N -ditosyl-2,1I -diaza[3. 31(2. 6)rpvridinophane. To a solution of sodium ptoluenesulphonaniidure (1.93 g, 10 mmoles) in 200 ml of dry DMF at 80'C was slowly added 2,6-dichlorome thylpyridine (1.76 g& 10 mmoles). After 1 hour a new portion of a.

WO 00/12808 PCT/GB99/02878 56 sodium p-toluenesulphonamidure was added (1.93 g) and the final mixture stirred at 0 C for an addition 4 hours. The solution was then evaporated to dryness. The solid obtained was washed with water and then with EtOH and finally crystallised in an CHCI3/MeOH mixture. The solid obtained is filtered and dried. The yield of (15) was 55 'H NMR (200MHz, CDCl3) 8 7.78 (4H,d, J=6Hz), 7.45 7.15 (4H,d, J=6Hz), 4.4 (8H, 2.4 (6H,s) 2,11-diaza[3.31(2.6)pvridinophane. A mixture of N,N'-ditosyl-2,11-diaza[3.3] (2,6)pyridinophane (1.53 g, 2.8 mmoles) and 14 ml of H 2

SO

4 90 was heated at 110°C for 2 hours. The solution, cooled and diluted with 14 ml of water, was then carefully poured into a saturated NaOH-solution. The solid formed is extracted with chloroform.

The organic layer is evaporated to dryness to yield of 2,11-diaza[3.3](2,6)pyridinophane. 'H NMR (200MHz, CDCI 3 8 7.1 (2H,t, J=7Hz), 6.5 (4H,d, J=7 Hz), 3.9 (8H, s).

N,N'-dimethyl-2,11 -diazaf3.31(2,6)pvridinophane. A mixture of 2,11-diaza[3.3] (2,6)pyridinophane (0.57 g, 2.4 mmoles), 120 ml of formic acid and 32 'ml of formaldehyde (32% in water) was refluxed for 24 hours. Concentrated HCI (10 ml) were added and the solution evaporated to dryness. The solid was dissolved in water and basified with NaOH 5M, and the resulting solution was extracted with CHCI 3 The solid obtained was purified by chromatography on alox (CH 2

C

2 1% MeOH) to yield 51 of N,N'-dimethyl-2,11-diaza[3.3](2,6)pyridinophane. 'H NMR (200MHz, CDCI 3 5 7.15 (2H,t, J=7Hz), 6.8 (4H,d, J=7 Hz), 3.9 (8H, 2.73 (6H,s).

(ii) Synthesis of the complex: MnF 3 (41.8 mg, 373 mmoles) was dissolved in 5 ml of MeOH, and N,N'-dimethyl-2,11diaza[3.3](2,6)pyridinophane (0.1 g, 373 mmoles) was added with 5 ml of THF. After minutes of stirring at RT, 4 ml of THF saturated in NBu 4

PF

6 were added, and the solution left without stirring until the crystallisation was finished. The product was 4 WO 00/12808 PCT/GB99/02878 57 collected by filtration to yield 80% of complex. Elemental analysis (found, theoretical): %C (38.35, 37.94), %N (11.32, 11.1), %H (3.75, 3.95). IR (KBr pellet, 3086, 2965, 2930, 2821, 1607, 1478, 1444, 1425, 1174, 1034, 1019, 844, 796, 603, 574, 555.

UV-Vis (CH 3 CN, X in nm, 500, 110; 850, 30; (CH 3

CN/H

2 0:1/1, X in nm, 465.

168; 850,30.

Example 7: Bleaching of tomato-oil stained cloths without and with addition of [Fe(MeN4P)(CHCN)1(ClO4) 2 immediately after the wash and after 24 h storage (t=l day).

In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/l LAS (linear alkylbenzene sulphonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/1 LAS, tomato-soya oil stained cloths (6x6 cm) were added and stirred for minutes at 30 In a second series of experiments, the same tests were done in the presence of 10 pM [Fe(MeN4Py)(CH 3 CN)](C10 4 2 referred to in the table below as Fe(MeN4Py).

After the wash, the cloths were dried in a tumble drier and the reflectance was measured with a Minolta 3700d spectrophotometer at 460 nm. The difference in reflectance before and after the wash is defined as AR460 value.

The cloths were measured immediately after the wash and after 24 h storage in a dark room under ambient conditions The results obtained are listed in the table below: AR value AR value AR value (t=ld) AR value (t=ld) blank (no cat) Fe(MeN4Py) blank Fe(MeN4Py) pH 8 no LAS 11.5 23 11.5 44 pH 8 with LAS 12.5 19 12.5 36 WO 00/12808 PCT/GB99/02878 58.

pH 10 no LAS ,10.5 30 11.5 43 pH 10 with LAS 12.5 30 14 39 A clear bleaching effect can thus be observed after the treated fabric cloths were dried and stored.

Example 8: Bleaching of tomato-oil stained cloths without and with addition of various metal catalysts measured after 24 hours storage in the dark under ambient conditions.

In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/l LAS (linear alkylbenzene sulphonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/1 LAS, tomato-soya oil stained cloths were added and kept in contact with the solution under agitation for 30 minutes at 30 In comparative experiments, the same experiments were done by addition of 5 pM of dinuclear or pLM mononuclear complex, referred to in the table below.

After the wash, the cloths were rinsed with water and subsequently dried at 30 OC and the change in colour was measured after leaving the cloths for 24 h in the dark with a Linotype-Hell scanner (ex Linotype). The change in colour (including bleaching) is expressed as the AE value. The measured colour difference (AE) between the washed cloth and the unwashed cloth is defined as follows: AE +(Ab) 2 ]1/2 wherein AL is a measure for the difference in darkness between the washed and unwashed test cloth; Aa and Ab are measures for the difference in redness and yellowness respectively between both cloths. With regard to this colour measurement technique, reference is made to Commission International de 1'Eclairage (CIE); Recommendation on Uniform Colour Spaces, colour difference equations, psychometric WO 00/12808 PCT/GB99/02878 59 colour terms, supplement no 2 to GIE Publication, no 15, Colormetry, Bureau Central de la CEE, Paris 1978.

The following complexes were used: i) [Mn 2 1,4,7-trimethyl-1I,4,7-triazacyclononane) 2 (t-O) 3

(PF

6 2 Synthesised according to EP-B-4S839 7; )ii) [Mn(LN4Me2)] &=difluoro[N,N'dimethyl-2, I1 -diaza[3 .3](2,6)pyridinophane] manganese(III)hexafluorophosphate) (2) Synthesised as described previously, iii) [Fe(OMe)LN4H2)C1 I1 -diaza[3 .3]-(4-methoxy)(2,6)pyridinophane)C 2 Synthesised as described previouisly; iv) C12-CoCo (4) Synthesis ed according to EP-A -408131; v) Me2CoCo Synthesised according to EP-A -40813],' vi) [Fe(tpen)](CI0 4 2 (6) Synthesised according to WO-A-9 748787; vii) [Fe(NNN'-tris(pyridin-2yhnethyl)-N-methyl- 1,2-ethylenediamine)CI](PF 6 2 (7) Synthesised according to 1. Bernal, et al., J. Chem. Soc., Dalton Trans, 22, 3667 (1995); WO 00/12808 PCT/GB99/02878 viii) [Fe2(N,N,N'N'-tetrakis(benzimidazol-2-ylmethyl)-propan.2-ol. I 3-ciamine)(p-

OH)XNO

3 2 ](N0 3 2 (8) Synt hesised according to Brennan, et1a., lnorg. Chem., 30, 193 7 (1991); ix) [Mn 2 (tpen)(pi-O) 2 (-OAc)(CO 4 2 (9) Synthesised according to Toftiund, H; Markiewicz, Murray, KS.; Acta Chem. Scamd, 44, 443 (1990); x) [Mn(NNN'-tris(pyridin-2-ylmethyl)-N'-methyl- 1,2-ethylenediamine)Cl](PF 6 Synthesised as follows: To a solution of manganese chloride tetrahydrate in tetrahydrofuran 90g, I nimol of MnCI 2 .4H1 2 0 in 10,ml, of THF) ligand trispicen(NMe) (0.347, 1 nimol) was added to give a brown precipitate (reference ligand: I Bernal, el J Chem. Soc., Dalton Trans, 22, 3667 (1995)). The mixture was stirred for 10 minutes and anmmonium hexafluorophosphate 1 63g, I mmol) dissolved in THF was added to give a cream coloured precipitate. The mixture was filtered, the filtrate was washed with THF and dried under vacuum to furnish the complex (FW=522.2 lg.mor'1) as a white solid (0.499g, ESMS (mlz): 437 ([LMnCl]]) xi) [Mn2(N,N'-bis(pyridin-2-ylmethyl)-1I,2-ethylenediamine) 2 (ti-O) 2

](CO

4 3 (11) Synthesised according to Glerup, Goodson, P. Hazel!, Hazell, R.; Hodgson, D. McKenzie, C. Michelsen, K; Rychlewska, U; Tofillund, H Inorg.

Chem. (1994), 33(18), 4105-1]; xii) [Mn(N,N'-bis(pyridin-2-ylmethyl)-N,N'-dimethyl. I,2-ethylenediamine) 2 C1] (12) Synthesised asfollows.

Triethylamine (0.405g, 4 mmol) was a solution of salt of the ligand bispicen(NMe) (0.41 6g, I mmol) in tetrahydrofuran anhydrous (10 mL) (ref ligand C.

Li, et al, J. Chem. Soc., Dalton Trans. (1991), 1909-14). The mixture was stirred at WO 00/12808 PCT/GB99/02878 61 room temperature for 30 minutes. A few drops of methanol were added. The mixture was filtered. Manganese chloride (0.198g, 1 mmol) dissolved in.THF (1 mL) was added to the mixture to give, after a stirring of 30 minutes, a white precipitate. The solution was filtered, the filtrate was washed twice with dry ether and dried under vacuum. This gave 0.093g of complex (23% yield).

xiii) [Mn 2 (N,N,N'N'-tetrakis(pyridin-2-ylmethyl)-propan- 1,3-diamine)(p-O)( OAc) 2 ](C104)2 (13) Synthesised asfollows: To a stirred solution of 6.56 g 2-chloro-methylpyridine (40 mmol) and 0.75 ml 1,3-propanediamine (9 mmol) in 40 ml water, is added slowly at 70 0 C over a period of minutes, 8 ml 10M NaOH-solution. The colour of the reaction turned from yellow to deep red. The reaction was stirred for an additional 30 minutes at 70 0 C, after which the reaction was cooled to room temperature. The reaction mixture was extracted with dichloromethane (totally 200 ml), after which the red organic layer was dried over MgSO 4 filtered and evaporated under reduced pressure, to yield 4.51 g of a red/brown oil. After scratching the bottom with a spatula the residue turned solid, trying to purify the crude product by washing it with water the product became messy, so immediately the purification was stopped and dried with ether. A sample was taken to analyse the product by NMR, while the rest was immediately reacted with Mn(OAc) 3 (see complexation).

'H-NMR (400MHz) (CDCI 3 d (ppm): 1.65 propane-A, 2H), 2.40 propane-B, 4H), 3.60 N-CH 2 -pyr, 8H), 6.95 pyr-H4, 4H), 7.30 pyr-H3, 4H), 7.45 pyr- 4H), 8.35 pyr-H6, 4H).

To a stirred solution of 4.51 g TPTN (0.0103 mol) in 40 ml methanol is added at room temperature (22 0 C) 2.76 g Mn(OAc) 3 (0.0103 mol) The colour of the reaction turned from orange to dark brown, after the addition the mixture was stirred for minutes at room temperature and filtered. To the filtrate was added at room temperature 1.44 g NaC10 4 (0.0103 mmol) and the reaction mixture was stirred for another hour, filtered and nitrogen dried, yielding 0.73 g bright brown crystals WO 00/1 2808 PCT/GB99/02878 62 'H-NMR'(400M~z) (CD 3 CN); d (ppm): -42.66 -15.43 br.),.0-10 (in, 13.81 45.82 49.28 60 79 96 br.) IR/ 3426, 1608 1563 1487 ,1430 10'90 (00 4 1030, 767, 623.

UTVNis nrn(e, Pmol'cm'): 260 (2.4 X10 4 290 370 490 (5.1 x10 2 530 (sh; 3.4 X 10 2 567 7 15 (1.4 x 102).

Mass spect rum: (ESP+) mlz 782 [TPTN Mn(II)Mn(11I) (p-OH) (p-OAc) 2 (ClO 4 ESR (CH 3 CN): The complex is ESR silent supporting the presence, of a Mn(III)Mn(II1) species.

Elemental analysis: found (expected for Mn 2

C

3 1

H

3 8N 6

O

14

C]

2 (MW=899): C 41.14) H 4.1 N 9.23 0 24.8 Cl 7.72 Mn 12.1 (12.2).

xiv) [Mn 2 (tpa) 2 (9-O) 2

](PF

6 3 (14) Synihesised according to D.K Towle, CA. Botsford, DJ Hodgson, ICA, 141, .167 (1988); xv) [Fe(N4Py)(CH 3 CN) (CdO 4 2 Synthesised according to WO-A -9534628; xvi) [Fe(MeN4Py)(CH 3 CN)](C10 4 2 (16) Synihesised according to EP-A -0909809.

xvii) [Mn 2 (2,6-bis {(bis(2-pyridylniethyl)amino)methyl)}-4-methylphenol))(p- OAc) 2 ])(C10 4 2 (17).

Synthesised according to H Dirt? et J.Am. Chem.Soc., 111, -5102 (1989); xviii) [Mn2(NNNN'-tetrakis(benzimidazol-2-ylmethyl)-propan-2-oate-1 ,3-diarnine)] (p-OAc) 2 ](C10 4 2 (18) Synthesised according to P. Marthur et J.Am. Chem.Soc, 109, 5227 (1987).

63 Results: Table: bleach activity on Tomato Oil stains expressed in AE values obtained for various metal complexes measured after 24 h.

BL: Reference: no catalyst added, only buffer with and without LAS Compound 16 with 10 mM hydrogen peroxide Performing the experiment under argon (compound 16 at pH 10 with LAS) showed that the bleaching effect upon storage is absent, thus showing that dioxygen is involved in the bleaching process.

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

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

Claims (37)

1. A method of trea~ting a textile by cont~cting the textile with an organic substance which forma a-complex with a transition metal, the treatment providling the org2anic Pubstance in a form that is substantially devoid of peroxygen bleach or a peroxy- based or -generating bleach system whereby the complex catalyses bleaching of the textile by atmiospheric oxygen after the treatment',-wherein the-treated textile is dried and bleaching in catalysed-on the dry textile.

2. A method accor ding to claim 1, wherein the treatment comprises contacting the textile with the organic substatce in dry form.

3. A method according to claim 1, wherein the treatmnent comiprises contacting the textile with a liquor containing the organic oubstance and then drying.

4. A method according to'claim 3, wherein the liquor is an aqueous liquor. A method according to claim 4, wherein the-liquor is a spr-ay-on fabric treatment fluid.

6. A method according to claim 4, wherein the liquor is a wash liquor for launidry cleaning.

7. A method according to claim 3, wherein the liquor is a non-aqueous liquor. AMENDED SHEET *17011-20,00 GB 009902878 W0AT (C) Amended 17 November 2000 S. A met'ho d according to claim 7, wherein the liquor is a dry cleaning fluid, A method according to claim 7, wherein the liquor is a spray-on aerosol fluid. io. A method according to claim 3, wherein the medium has a pij value in the range from pR 6 to 11. 11, A method OiOording to claim 10, wherein the liquor has a pH~ value in the range from pX{ 8 to

12. A method according to any of claims 3 to 11,' wherein the liquor is substantially devoid of a transition metal seguestrant.

13. A method according to any of claims 3 to 12, wherein the liquor further comprises a surfactant. 3.4. A method according to any of claims 3 to 13, wherein the liquor further comprises a builder. A method according to any of claims~ 1 to 14, wherein the organic substance comprises a preformed complex of a ligand and a transition metal.

16. A method according to any of claims 3 to 14, wherein the organic substance comprises a free liqand that cormlexes. with a transition metal present in the liquor. AMENDED SHEET

17-1 1-2000 GB 0099028t" C38,3,/2,WO (C) A mended 17 Novemb~er 2000 17. A method according to any of claimsl tolA,1 Wherein the organic substance comprises a free ligand that- complexes with a transition metal present in the textile. S' 1G. A method according to any of claims 1 to 14, wherein the organic substance comprises a composition of a -free Jligand or a transition meta1-substitutable'metal'-ligand complex, and a oource of transition mecal. 1.9. A method accordiLng to any of claims 1 to 1i, wherein the organic substance forms a comrplex'of the general f ormul a (Al): IMaL4Xn] YM IAl) in which; M, represents a metal selected from Mn (lI) -(III) xII) (ZI) CV()-I WX)-(v)-(ZPIuX)(X)(V-V n As (11); L represents a ligand,* or its protonated or deprotonated analogude; X represents a coordinating specie's selected from any mrono, bi or tri charged anions and any neutral molecules *able to coordinate the metal in a mono, bi or tridentate *manner; Y represe-nts any non-coordinated counter ion; a represents an integer from 2 to k represents an integer from I to 1q; AMENDED SHEET 1:200 GB 009902878 c~~if2No (C) Amended 1.7 NOVember 2000 6 7- n represents zero or an integrer f rQm 1 to 10; and m represents zero or an integer from 1 to A method according to claim 19, wherein in formula (Al): X represents-a coordinating species selected from 02-, RB0 2 2 Rcoo-, RCONz-1 OH-, N03-1, KC:, ~Co, S2 RS,l po34 STP-derived anione, P03OR I H 2 0, Rl 2 CORE JR1h, RCN, CY, Br, OCN, SCN, CW~, N, Fr, PR0, C10 4 1 S0 4 HS,1 S032 and RS0 3 and Y repr'esents a counter. ion selected from C10 4 BR, [FeC1 4 J PFd-, RCOO, N0 3 NO.R0, N+RRIRI1RSII, C1-, Br, F' R20 3 S 2 0 6 I OCN', SC- Li+, Ra Na Mg IC*' Ca, Cs 4 PR', RB022?, S0 4 2 HS0 4 ,1 S032, SbC1(-, CUC1,2-, CN, P0 4 l- HFw12_, H 2 P0 4 ESTP-derived anions, C0 3 2 I CO3 and BY 4 ,1 wherein R. RI, Rill independently represent a group selected from hydrogen, hydroxyl, -OR .(wherein R= alkyl, alkenyl, cycloalkyl, heterocycloa3.kyl, azyl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, 2 heterocycloalkyl, aryl, heteroaryl and carbonyl. derivative groups, each of, R, AX, alkyl, alkenyl, cycloalkyl, heterocycloa.kyl, aryl, heteroaryl-and carbonyl derivative groups being optionally substituted by one or more- functional grou.ps E, or R6 together with R7? and independently R8 together with R9 represent oxygen; E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium,' halogens, and any electron donating an.d/or withdrawing groupp. AMENDED SHEET 17-1 1-2090 GB OO2 87A C38,'2WO (C) Amended 17 November 2000

21. A method according to claim 19 or claim 20, wherein in formulja WA): M represents a mnetal. selected fromn Mn(II)-(ii1)-(IV)- V)*Cu Fe (II) (111) (IV) and Co (UXT) X represents a coordinating species selected fromu 0, RB2' 'RCOOf OR'# N0 3 N02-, NO, CO, CN-, S2-. RS-, P0 3 4, C03 HC0 3 ROH, NRIR", Cl-, Br-, OCR-, SUN-, ROJN,N 3 I- R0, 10 4 ,SO 4 HS0 4 S0, 2 and RSO.-; Y represents a counter lon selected from C104., BR4.- [FeCl 4 1 -d Fj-, RCOO-, N0 3 N0 2 KNARR'R", C2 Br-f RS2 S 2 0 2 Q)MN, SCWN, Li", Ba 2 Na 4 Mg 2 K% Ca 2 PR 4 S04, HSO,1, S03' and PP. 4 wherein R, Rv', R111 reprezent.represent hydrogen, optionally aubstituted alky'l or optionally substituted aryl;- a r-epresents an- integer from 1 to 41 k1 rpreptent an integer from 1 to n represents zero or an inte!ger from 1 to 4; and m represents zero or an integer from 1 to a. .22. A method according to any of claims 19 to 21, wherein L represents a ligand of the general formula (BI): wherei~n 9 represente zero or an integer from 1 to 6l represents an integer from I to 6; represents zero or an integer from 1 to 6; AMENDED SHEET 1741 1-2000 GB 009902878 lk.,oo4/_2 WO (C) Amended 17 Novemfber 2000 Za. and Z2 independently- repr'esent a heteroe-tom or a heterocyclic or heteroarornatic ring, Zi and/or Z2 being optionally- substituted by one or more functional. groups B as dlef inedl below; Q1 and Q2, indepenidently represent a group of the formula;. R6 R8 11 -3 1 Y I k7 wherein 1O~de~fz; f=-_9i each Ylis independently selected from -so-, N- (G3 1 (G; 2 (wherein G1 and G 2 are as defined below) -C arylene, alkylene, heteroaxylene, and- P(O) if each (C1) I group is independently definedi R1, R21 RG, R71-RO, R9 independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, 'cyclcalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl. derivative group), -OAr, alkyl, alkeny., cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivativre groups being optionally substituted by one or AMENDED SHEET -17,11'2000 GB 009902878 1,5b.~2 Wo (C) Amendled 17 November 2000 more functional groups or R6 together with R7 and independently R8 together wi~th R9 represen-t oxygen;- F is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from h:idroxy, mono- or- polycarboxylate derivatives, aryl, heteroaryl, sulphonatej, dithioJlenes, mono- or polyphcsphonatee, mono- or polyphosphates, electron donating Sroups and electron withdrawing groups, and groups of for-mulae (G 2 WG)N1-, (Gl) (G 2 N- C G30- and G 2 C -wherein each of G 2 and G' is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoingj)); or one of R1-R9 is, a bridging group bound to another moiety of the same general formula; and T2, independently repre sent' groups R~4 and RS, wherein A4 and. R5 are as defined for R1-R.9, and if 9-0 and. S,0, RI together with R4, and/or R2 together with R5, my optionally independently represent =CF-RIl,wherein RIO is as defined for Rl-R9, cr Ti and T2 may together represent a covalent bond linkage when s .1 and if 21 anid/or Z2 repreeent X and T1 and T2 together represent a single-bond :linkage anld Ri and/or R2 are absent, QiL and/or Q2 may independently represent a group of the AMENDED SHEET 1M 17;1120P0 GB 009902878 Amended 17 November 2000' optionally. any tw9 or 'more Of RI, R21 R6, R7, R8, R.9 independently :re linked toge therbyacalnbnd if zi and/or Z2 represents 0, then RI and/or R2 do not exist:; if ZI and/or Z2 represents S, N B or*Si then R2 aad/or R2 mray be absent; if 21 and/or Z2 represents a heteroatom substituted by a functional group B then RI and/or A.2 and/or R4 and/or may be absent.

23. A method according to claim 22, wherein ZI an d Z2 independently represent an optionally substituted heteroatom sel~ected from N, P, 0, S, B and Si or an optionally oubctituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrirnidines, pyrazine, pyramidiae, pyrazole, pyrrole, imidazole, benzimidazole, quirioleine, isoquinoline, carbazole, indole,- isoindole, furane, thiophene, oxazole and thiazole.

24. 'A method, accor-ding to claim 22 or claim 23, wherein.RiL- iz9 are independentiy' selected from -Hi, haflo-Cc-C 2 0-alkyl, nitroso, formyl-CO-C.70-alkyl, carboxyl-Co- C,,-alkyl and esters and salts thereof, carbarnoyl-CO-C2- alkyl, aulpho-Co-C 2 0 -alkyl and estara and salts thereof, su2,phamfoyl-CO-02c0-alkyl, amino -Cq-Cgq-alkyl, aryl-CO-C 2 0 -alkyl, heteroaryl-CO-CID-alkyl, Cc-CZ 9 -alkyl, alkoxy-CO-CII-alkyl, carbonyl-CO-C 6 ,-aJlkoxy, and aryl-CO-Ce-alkyl and Cg-C2 0 alkyl ami de, ~or one of RI-R9 is a bridging group -C.(Rl1) -R:L2) (R11) (R.12) boiamd to another moiety of the same general AMENDED SHEET 17,"11-200 GB 00990287-8 C386/2 WOQ.(C) Amen~ded 17 November 2000 -72- formula, wherein p irs zero or one, D is selected from a heteroatom or a heteroatom-containing group 1 or is part of an aromatic or saturated homonuclear and heteronucjlear ring, n' is an integer from 1 to is an integer from 1 to 4,. with the proviso that Ril and R12 are each independently preferably selecued from -Hi, NR.13 and 0R14, aJ~kyl, aryl, optionally substituted, and R13 and R24 are each independently selected from Calkyl,. aryl, both Optionally Substituted. AL method according to any of claims 22 to 24, wherein T2 and T2 together form a single bond linkage and m>l, according to general formula (BYI): wherein 3- independently represents a group as defined for Zi or Z2,- R3 independently repres ents a group as defined for R1-R9 03 independently represents a group as defined for Q1, 02; h r-epresents zero or an integer from 1 to 6; and 26, A method according to claim 25,*whe-rein in general formula (EII), se'=I, 2 or 3; r=g=h=l; d=2 or 3; e=fE=0; AMENDED SHEET 17 1 ObGB 009902878 C386/2 WO (C) Amended 17 November 2000 73

27. A method according to claim 26, wherein the ligand has a general formula selected from: R1 RI\l R N-R3 R3 R2 R2 R2 R2 RI\ R1 RI ~r]R2 CN R2 R4 'R3 R4 Li R3 C N R3 R4

28. A method accordihg to claim 27, wherein the ligand has a general formula selected from; RIK /R2 RI m,R2 RI NNr (NNR CN NP N ND NR3 R4L~JRS R4L.1IR 3 R

29. A method according to claim 28, wherein RI, R2, R3 and R4 are independently selected from alkyl, heteroazyl, or represents a bridging group bound to another moiety cf the same general formula with the bridging group being alkylene or hydoxy-alkylene or a heteroayl-containiflg bridge. AMENDED SHEET 17-.11-2000 GB 0O9O287b Amended 17 November 2000 -74 A method according to claim .29, wherein R1, R21 R3 and R4 are independentl~y selected from methyl, ethyl, isopropyl., nitrogen- containing. heteroary2, or a bridging group bound to another moiety of the same gener-al forimula with the bridging grcu.p being alkylezie or hydroxy-alkylene.

32. A method according to any of claims 26 to 30, wherein in the complex LMaL'jXjYm X= CH 3 aZN, OH2, Cl-, Br-, OCN-, SCINr, 0HI, 02, .PO3- CgHsB0 2 2 RZCOO; Y= C10 4 -1 BPht 4 Er -,Cl FeCl 4 PF'g- NO,' a= 1, 2, 3, 4; 2, 3, 4; and k W 1, 2, 4. 32. A method according to claim 25, wherein'in general formula (BiI), s1=2; d=f=0; e=1; and each Y1. ia independently alkylene or heteroarylene.*

33. A method according to claim, 32, wherein the ligan~d has the general formula: R4, 1A 2N N1 Al R3 wherein AMENDED SHEET 17!12000GB 009902878 Ub- 1 No Amnded 17 November 2000 A 21 A3, A 4 are independently selected from alkylenje or heteroarylele gro-ups; and NI-and N 2 inaependently represent a hetero atom or a heteroarlele group.

34. A method according to claim 33, wherein N, represents an aliphatic nitrogen; iu represents a heteroarylele group: RI, p.2, R3, R4 each independently represent alkyl, aryl. or heteroaryl;- and A3,, A2, A3, A4 each represent -CH 2 A mnethod according to claim 34, wherein the ligand has the general. formula: N NRI "R 2 N wherein RI, R2 each independently represent alkyl, aryl or heteroary-.

36. A method according to any of claimo 32 to 35, wherein in the complex [M.LxX0c]Ym M= F(I(IIMn(iI)-(IV), Cu(II), o)-Z) X- CH3CN, OH 2 Cl-, N3, SCN, 0H", 0 2- P043- CGHSBOz2, RCOO'; Y' C.104-1 BPh,- Br -I C2 -1 [FeC1 4 PP 6 N03-; a= 1 2, 3j 4; n- 0, 11 2, 3, 41 5, 6,7, 8, 9; AMENDED SHEET 17,11-2000 1~ sbi12 YWO (C) GB 00900O876 Amended 17 November 2000 76 tn= 1, 2, 3, 4 and 1, 2, 4.

37. A method according to claim 25, wherein in general formnula (PI s 1 =2 and according to the general f oznula:

38- A method according to claim 37, wherein Z1=Z2=Z$=Z4=a heteroaromatic ring; e=f=0; d=l; and,R7 is absent.

39. A method according to claim 37, wherein Zl-Z4 each z-epregent N; R1-R4 are absent; bothQi and 03 represent i c- -i-j I-CH= j and both Q2 and Q4 represent A method according to claim 39, wherein the ligand has the general formula:~ AMENDED SHEET Amended 17 November 2000 GB 009902878 77 -R2 wherein A represents optionally substituted optionall~y interupted by a heteroatom;an integer from 1 to S. alkylene n is zero or an1

41. 'A method according to claim 40 wherein RI.-1R represent hydrogen, n=1 and A= -CH 2 -CHiOH-, -CH2N(R)CH2- or '-H 2 CH 2 N(R)OC2CK- wherein R represents hydrogen or alkyl.

42. A method according to claim 41, wherein A= -C-I 2 -CHOi- or -CH 2 C 2 NCRCI2-.

43. A method according to any of claims 37 to 42 wherein in the complex [MaIjk~XL] m1 M- Mn(f) Cc (21) Fe X= CWN OR21 Cl-, Br-, OCN-I N SCNf 01, 0 2 PO 4 3 C 6 HB02-, RCOOI YM C10O(, BPh 4 Br C1 [FeC1 4 F~ 903NO; a~1, 2, 3,r 4; AMENDED SHEET 17-11-20.00 GB 0099087 iCJ, 2 WO (C) Amended 17 November 2000 78 n= 0, 1, 2, 3, 4, 5, 6,7, 8, 9; m= 1, 2, 3, 4r and k= 1, 2, 4.

44. A method according. to any of claims 22.to 24, wherein T1 and T2 independently represent groups R4, R5 as defined for R1-R9, according to the general formula (BIII)- R4- (QI) e-22-(Q2) g-RS h2 A method according to claim 44, wherein in general formula (BIII), s=l; r=1; g=0; d=f=l; e=l-4; Yn1 -CH2-; and R1 together with. R4, and/or R2 together with independently represent =CH-S-1O, wherein Ri0 is as defined for RI-R9.

46. A method according to claim 45, wherein R2 together with R5 represents

47. A method according to claim 45 or claim 46, wherein the ligand is selected from: R2 R3 R5 R3 R 6 C R5 CH R==N R2-N N R R4 RI., R4

48. A method according to claim 47, wherein the ligand in selected from: AMENDED SHEET 174i0~0,GB 009902878 Amended 17 November 2000 -79 N R4-N\ N R1 R2 R3 R1 wherein Riand R2 are selected from optionally substitvted phenols, heteroaryl-CC-C20-alkylo, R3 and R4 are selected from alkyl, aryl, optionally eubstituted. phenols, alkylaryl, aminoalkyl, alkoxcy.

49. A method according to claim 48 wherein R3. and R2 are selected from optionally substituted phenols, beteroary.-Co- C.-aJlkyls, R3 and R4 are selected From alkyl, aryl, optionally substituted phenols, ntrogen-heterorlj-CO-Ca- SO. A method according to any of claims 45 to 49 wherein. irn the COmpleX [MaLkXnJ M': X= cH3CtI, OH2 C1-, ~RX, OCNW, N 3 ,1 ON, 04, 02, po 43 C 6 H.SBO?, RCOO,; Y- C1OJ,1 B:?h 4 r -,Cl-1 IFeCl 4 V, PV6- N03-; a= 1, 4; mi= 1, 2, 3, 4; and k= 1, 2, 4.

51. A method according to claim 44, *wherein in general formula (Bll), s=1; r=1; S=O; d=f=l; e=1-4; TI- C CR'1) wherein RI and Rr I are independently as defined for Rl-R9. AMENDED SHEET 17-1 1-2OPO GB OO9b0A8 2 WO (C) An~nded 17 November 2000 BO0

52. A method according to claim '51, wherein the ligand has the general formula: FR 2 R5 R3 R1 Jri 1 R4 R7'-N R6 N-R9

53. A method according to claim 52, wherein RIj R21 R31 R4, RS5 are -Hi or Co-Cza-alkcyl, n=0 or it RC io -Ri, alkyl, -ORI or -SH, and R71 R8 1 RP, RIO are each independently selected fromn CO-C20-alkYl, heteroaryl-C 0 -C21-alkyl, alkoxcy-CO-C 5 alkyl and amino-

54. A method according to any of claims 51 to 53 wherein in the complex [MajkX,]J X= CHaCN, Br-, 00N-, N 3 SCKN, OH-1 PO43-1 5 B0,22-, RCOO,1 Y= C2 0 4 BPh 4 Br -,Cl t FeCl 4 P, PP 5 N0 3 a= 1, 2, 3, 4; n= 2, 3, 4; m= 0, 1, 2, 3, 4, 5, 6, 7, 8; and k- 1, 2, 3, 4.

59. A method according to claim 4-4, wherein in general. formula (2111), d~e=o; f=1-4. AMENDED SHEET I ,2Q1 0 GB 009902878 Amended 1.7 November

2000. 56. A met hod according to claim 55t Whevein the ligand h&.o the general formula:- RI4 R3 R4 57. A method according to claim 56, with the proviso that none of RI to RT3 represents hydrogen. 5e. A method according to claim 56 or cldim 57, wherein the Jigand has the general formula; IR1% N-N R.2,N R3 wherein R2, R2, R3 are as defined for R2, R4, 59. A method according to aniy of claims 55 to 58., wherein in the complex [MaLkXJ]Ym: M= Mn (IT) (TV) Fe (I1) (III), Cu (II) Co (11) (III); X= cuacx, O74, Rr, OCNr, N 3 SCN-, OH-, 0, P0 4 3 CEHSBO,2 2 VCOO Y= C204-1 3Ph 4 ,1 Br -1 'U (FeCl 4 FF-, M03-; a= 1, 2, 3, 4;, n= 0, 1, 2, 3, 41 m= 0, 1, 2, 3, 4, 5, 6, 7, 8; and k= 1, 2, 3, 4. AMENDED SHEET -1-7-11-2000 G 0~27 YOW (C)GB0928 Amended 17 November 2000 A method according to any of claims 2.9 to 24i wherei.n L represents a pentadentate ligand of the greneral formula pR 3 C-N RI R 2 where in each A' ,R 2 ind ependenly- represents -R 4 -R, R R 3 represents hydrogen, optionall~y substituted alkyl, aryl or ary].alkyl, or R-, each R' independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, arninoalkylenie, alkylene ether, carboxyl~ic ester or carbox~ylic amide, and each R5~ independently repreeents an opti.onally N- substituted aminoalkyl group or an optionally substituted beteroaryl group selected from pyrdidinyl, pyrazinyl, pyrazoJlyl, pyrrolylJ imidazoly2., benzimidazolyl, pyrimidinyl, triazoJlyl and thiazoJlyl. 61. A method according to claim'60, with the pro-Viso that R 3 does flat zepxresent hydrogen.. 62. A method according to any of claims 19 to 24, wherein L' represents a pentadentate or hexadentaze ligand of the general formula RR'-K-W-XR:R' wherein AMENDED SHEET GB 009902878 wa(C) Amendepd 2.7 November 2000 -83 each R2- independently- represents -R 3 in which R' represenlts optionally substituted alkylene, alkenylele, oxyalkylenle, aminoalkylele or alkylene ether, and V represents an optionally substituced heteroary-.1 group selectedl from pyridiny., pyrazinyl, pyrazolyl, pyrrolylt ixnidazolyl, benzimidazolyl, pyrimidinlyl, triazolyl and thiazolyl; W4 represents an optional~ly substituted alkyloefl bridging group selected from -CII2CHi2- CH 2 CH2CH2- -CH 2 C 2 HCH2-, -C.H2C 6 H 4 0H 2 -CH;-Ci-MO CHi 2 an~d -CE 2 -COH6-C2- and R'2 represents a group selected from and alkyl, aryl and arylalkyl groups optionally substituted with a substitueit selected from hydroxcy, a2.koxy, phenoxy, carboxylate, carboxamide, carboylc ester, suiphonate, amine, alkylarnine and N* 3 wherein R' selected f rom hydrogen, alkanyl, alkenyl,.arylalkanyl, arylalkey-, oxyalkanyl,' oxcya1)~eny2, aminoalkwaiyl, atiroalkenyl, alkanyl. ether and alkeny. ether. 63. A method according to any of claims 19 to 24, wherein L represents a macrocyclic ligand of formula (E).a 2 Q2 A- jY9,1 A~j (E) wherein arnd Z2 are independently selected from monocyclic or polycyclic aromatic ring structures optiona2ly containing AMENDED SHEET "7 11 000 wo GB Amended 17 November 2000 -84 one or more heteroatons, each aromatic ri±n7 Structure bei ng substituted by one or more substituents; Y1 and Y 2 are independently se].ected from' N, 0, si, P and S atoms; A' and A 2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of al.kyl, alkeny. and cycloalkyl) being optional~ly substituted by one or more groups selected from hydroxy, aryl, heteroaryl, oulphoriate, phosphate, 'electron donating groups and electron withdrawing groups, and groups of forumulae (01) (G 2 )N-f 0'0- and whereina each of C71, 7 2 and G 3 is independently selected from hydrogen and alkyl., and electron donating and/or withdrawing groups:(i-n addition to any amon5st the foregoing); i and j- are selected from 0, 1 and 2 to complete the valency of the groups Y'.and..Y: each of Q'-Q 4 Is independently selected from groups of formula UA3I FAs 1 wherein 1o>a+b+c+d>21 each Y 3 0 isinepndontly selected from -8-1 -SO-, S0 2 W(G) (GL)NX- (wherein G1 and G are as herainbefore defined), C aryl,. heterocaryl, and- each of A3-A6 is independently selected from the groups herein-before defined for AL and A 2 and AMENDED SHEET 85 wherein any two or more of A' A6 together form a bridging group, provided that if A' and A 2 are linked without simultaneous linking also to any of A 3 A 6 then the bridging group linking A' and A 2 must contain at least one carbonyl group. 64. A method of treating a textile by contacting the textile with an organic substance N which forms a complex with a transition metal substantially as hereinbefore described with reference to the examples. DATED THIS 22nd day of July, 2005. UNILEVER PLC By Its Patent Attorneys DAVIES COLLISON CAVE