Whitening composition and method for bleaching a substrate

 

(57) Abstract:

The invention relates to catalytic bleaching of substrates, for example, subjected to washing fabrics, atmospheric oxygen or air. Whitening composition comprising in an aqueous medium, an organic substance of the formula L, which forms a complex with the transition metal, whereby the complex catalyses bleaching of the substrate by atmospheric oxygen, and water environment essentially does not contain peroxygen bleach or based on peroxide or forming its whitening system, where L is a ligand that forms a complex with the General formula [MandLkXn]Ymin which M is a metal selected from Mn, Fe, Co, Ni and Ru; X - coordinate product selected from any mono-, bi - or three-charged anions and any neutral molecules able to coordinate the metal mono-, bi - or tridentate way; Y is any uncoordinated counterion; a=1-10; k=1-10; n=0 or 1-10; and m=0 or 1 to 20; L is a ligand of General formula (BI), or equivalent with an attached or remote proton:

where g=0 or 1-6; r=1-6; s=0 or 1-6; Z1 and Z2 independently from each other represent a heteroatom or a heterocyclic or heteroatom, is within the following values; Q1 and Q2 independently of one another represent a group of the formula:

where d=0-9; e=0-9; f=0-9; each Y1 is independently selected from -(G1)N-, -(G1)(G2)N- (where G1and G2have the following values), -C(O)-, arylene, alkylene; R1, R2, R6, R7, R8, R9 independently of one another represent a group selected from hydrogen, hydroxyl, -OR (where R=alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl or carbonylation group), -OAr, alkyl, alkenyl, cycloalkyl, geterotsiklicheskie, aryl, heteroaryl and carbamylphosphate groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl and carbamylphosphate groups optionally substituted by one or more functional groups E; E is chosen from the functional groups containing nitrogen, as well as any electrondonor and/or acceptor groups; T1 and T2 independently of one another represent groups of R4 and R5, where R4 and R5 have the meanings indicated for R1-R9. The described method of bleaching a substrate comprising applying to it the whitening composition in the aqueous medium. The technical result - the use of atmospheric oxygen (air) as the East is"ptx2">

This invention relates to materials and methods of catalytic bleaching of the substrate by atmospheric oxygen.

Peroxygen brighteners are well known for their ability to remove stains from substrates. Typically, the substrate is exposed to hydrogen peroxide or substances capable of forming hydroperoxyl radicals, such as inorganic or organic peroxides. Typically, these systems require activation. One of the activation methods is the use for washing temperatures, the components 60 and above. However, such high temperatures often do not provide sufficient purity, and may cause premature damage to the substrate.

The preferred approach to education hydroperoxyl bleaching radicals includes the use of inorganic peroxides, combined with organic compounds predecessors. Such systems are used for many industrial washing powders. For example, various European system based on the use of tetraacetyl-Ethylenediamine (TAED) as the organic precursor connected with perborate or percarbonate sodium, while used for washing otbelivanie the ka, United with perborate sodium.

Normally, the predecessor effective, however they have several drawbacks. For example, organic precursors consist of moderately complex molecules that require multi-stage production processes, leading to high capital cost. System predecessors also occupy a lot of space in the composition, so that a substantial part of washing powder should be bleaching components, leaving less space for other active ingredients and complicating the use of concentrated powders. Moreover, the system predecessors do not have enough effective whitening action in countries where consumers are used to apply a small amount, short wash, low temperature and low concentration of the washing solution relative to the volume of the substrate.

Alternative or additional hydrogen peroxide and peroxy-system can be activated bleaching catalysts, such as iron complexes and ligand N4Py (i.e. N,N-bis(pyridin-2-yl-methyl)-bis(pyridine-2-yl)methylamine described in WO 95/34628, or ligand Chatter (i.e., N,N,N',N'-Tetra(pyridin-2-yl-methyl)Ethylenediamine), described in WO 97/487 and alternative forming peroxide systems. However, so far not described the role of atmospheric oxygen in catalysis bleaching in the aquatic environment.

For a long period of time was desirable the ability to use atmospheric oxygen (air) as the source for bleach, as it eliminates the use of expensive hydroperoxidase systems. Unfortunately, the air, as such, kinetically inert with respect to bleaching substrates and does not show the whitening activity. Recently in this area there has been some progress. For example, WO 97/38074 describes the application of air to oxidize stains on fabrics as a result of its ozonation through an aqueous solution containing the aldehyde and the radical initiator. Described the use of a wide range of aliphatic, aromatic and heterocyclic aldehydes, particularly para-substituted aldehydes such as 4-methyl-, 4-ethyl - and 4-isopropyl benzaldehyde, while the range described initiators include N-hydroxysuccinimide, various peroxides and coordination complexes of the transition metal.

However, although this system involves the use of molecular oxygen from the air during the process toatoa these components should be included in the composition in relatively large quantities for not to be spent until the completion of the bleaching process in the cycle of washing. Moreover, the spent components are a waste because they can no longer participate in the bleaching process.

Accordingly, it would be desirable to have whitening system on the basis of atmospheric oxygen or air, initially not involving the use of hydrogen peroxide or hydroperoxide system and does not require the presence of organic components, such as aldehydes, consumed during the process. In addition, it would be desirable to have a whitening system that is effective in the aquatic environment.

To our surprise, we discovered that existed for a long time the desire to use atmospheric oxygen or air for bleaching substrates can be carried out without the above disadvantages. This was achieved through the application of organic matter, catalysing bleaching of the substrate by atmospheric oxygen by applying a composition and method in accordance with this invention.

Therefore, in accordance with the first aspect of the invention provides a whitening composition is a metal, while this complex catalyses bleaching of the substrate by atmospheric oxygen, and the aqueous medium essentially devoid peroxygen bleach, based on peroxide or forming its whitening system. Therefore, this environment is preferably insensitive or resistant to the catalase effect at peroxiredoxin.

In accordance with the second aspect of the invention provides a method of bleaching a substrate comprising applying to the specified substrate, in an aqueous medium, an organic substance that forms a complex with the transition metal, with the specified complex catalyses bleaching of the substrate by atmospheric oxygen.

Further, in accordance with the third aspect of this invention involves the application of organic matter, forming a complex with a transition metal as a catalytic bleaching agent to the substrate in the aquatic environment, essentially not containing peroxygen bleach or based on peroxide or forming its whitening system, with the specified complex catalyses bleaching of the substrate by atmospheric oxygen.

The advantage of the method in accordance with the e (per equivalent weight) of atmospheric oxygen. Thus, the environment can be completely or essentially devoid peroxygen bleach or based on peroxide or forming its whitening system. Moreover, the organic substance is a catalyst for the bleaching process and, as such, is not consumed completely, and may continue to participate in the bleaching process. Therefore catalytically activated whitening system of the type which corresponds to this invention, i.e., based on atmospheric oxygen, economical and safe for the environment.

In addition, this whitening system is applicable in harsh washing conditions, such as low temperature, short contact time and a small dose.

Moreover, this method is effective in the aquatic environment and therefore is particularly suitable for bleaching subjected to washing. Therefore, despite the fact that the substance and method in accordance with this invention can be used for whitening of any suitable substrate, the preferred substrate is subjected to washing linen.

The whitening method is carried out, just leaving the substrate in contact with the environment for DOS and containing, was subjected to stirring.

Organic matter may include pre-obtained complex of the ligand and the transition metal. Alternatively, the organic material may include a free ligand that forms a complex with the transition metal already present in the water, or forming a complex with a transition metal present in the substrate. Organic matter can also be included in a composition of a free ligand or a complex of the metal-ligand, substituted transition metal, and a source of transition metal, the complex is formed in the environment in situ.

The organic compound forms a complex with one or more transition metals, in the latter case, such as, for example, a dual-core 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, Titan II-IV, tungsten IV-VI, palladium II, ruthenium II-V, vanadium II-V and molybdenum II-VI.

In a preferred embodiment of the present invention the organic substance forms a complex of the General formula (A1):

[MandLkXn]Ym,

where:

M - metal, Mo(II)-(III) (IV) (V) (VI), W(IV) (V) (VI), Pd(II), Ru(II)-(III) (IV) (V) and Ag(I)-(II), preferably selected from Mn(II)-(III) (IV) (V), Cu(I)-(II), Fe(II)-(III)-(IV) and Co(I)-(II)-(III);

L - described ligand or its equivalent attached or remote proton;

X - coordinating product selected from any mono-, bi - or three-charged anions and any neutral molecules able to coordinate the metal mono-, bi - or Trekhgorny way, preferably selected from O2-, RBO2-2, RCOO-, RCONR-HE-, NR-3NO-2, NO, CO, S2-RS-, RHO4-3derived from STP-anions (anions of sodium tripolyphosphate (Na5P3O10)) PO3OR3-H2O,2-3HCO-3, ROH, NRR'R’, RCN, Cl-, Br-, OCN-, SCN-CN-N-3, F-I-, RO-, ClO-4SO2-4, HSO-4, SO2-3and RS-3more preferably selected from OH2-, RBO2-2, RCOO-HE-, NR-3NO-2, NO, CO, CN-S2-RS-, RHO4-3N2OH, WITH2-3HCO-3, ROH, NRR'R’, CL-, Br-, OCN-, SCN-, RCN, N-3, F-UB> (preferably CF3SO-3);

Y - any disorderly a counterion, preferably selected from ClO-4, VG-4, [FeCl4]-PF-6, RCOO-, NR-3NO-2, RO-N+RR'R’R’’, CL-, Br-, F-I-, RS-3, S2ABOUT2-6, OCN-, SCN-Li+, Ba2+, Na+, Mg2+, K+Ca2+Cs+PR+4, RBO2-2SO2-4, HSO-4, SO2-3, SbCl-6, CuCl2-4, CN, PO2-4, HPO2-4H2PO-4derived from STP-anions, WITH2-3HCO-3and BF-4more preferably selected from ClO-4, VG-4, [Fl4]-, F-6, RCOO-, NR-3NO-2, RO-N+RR'R’R’’, CL-, Br-, F-I-, RS-3(preferably CF3SO-3), S2O2-6, OCN-, SCN-Li+BA2+, Na+MD2+TO+, CA2+PR+4SO2-4, HSO-4, SO2-3xila, -OR (where R=alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl or carbonylation group), the OAS, alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl and carbamylphosphate group, each of R, AG, alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl and carbamylphosphate groups optionally substituted by one or more functional groups E, or R6together with R7and independent R8together with R9represent oxygen, where E is chosen from the functional groups containing oxygen, sulfur, phosphorus, nitrogen, selenium, halogen, and any electron-giver and/or removes group, preferably R, R’, R’, R’’ represent hydrogen, optionally substituted alkyl or aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or C1-4-alkyl;

and is an integer from 1 to 10, preferably from 1 to 4;

k is an integer from 1 to 10;

n=0 or an integer from 1 to 10, preferably from 1 to 4;

m=0 or an integer from 1 to 20, preferably from 1 to 8.

The ligand L is preferably has the General formula (BI):

where

g=0 or an integer from 1 to 6;

r - Euroatom or heterocyclic or heteroaromatic ring, thus Z1 and/or Z2 is optionally substituted by one or more functional groups E, described below;

Q1 and Q2 independently represent a group of the formula:

where

10>d+e+f>1; d=0-9; e=0-9; f=0-9;

each Y1 is independently selected from-O-, -S-, -SO-, -SO2-, -(G1)N-, -(G1)(G2)N- (where G1and G2have the following values), -C(O)-, arylene, alkylene, heteroaryl, -P - and-P(O)-;

if s>1, each - [-Z1(R1)-(Q1)r-]-a group determined independently from each other;

R1, R2, R6, R7, R8, R9 independently of one another represent a group selected from hydrogen, hydroxyl, -OR (where R=alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl or carbonylation group), the OAS, alkyl, alkenyl, cycloalkyl, geterotsiklicheskie, aryl, heteroaryl and carbamylphosphate groups, each of R, AG, alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl and carbamylphosphate groups optionally substituted by one or more functional groups E, or R6 together with R7 and R8 independently together with R9 represent oxygen;

E is chosen from the functional groups containing oxygen, sulfur, phosphorus, azuki-, mono - or polycarboxylate derivatives, aryl, heteroaryl, sulfonate, thiol (-RSH), simple thioethers (-R-S-R'), disulfides (-RSSR'), dithiolane, mono - or poly-phosphonates, mono - or polyphosphates, electron-giver groups and electron-removing groups and groups of formula (G1)(G2)N-, (G1)(G2)(G3)N-, (G1)(G2)N-C(O)-, G3O - and G3C(O)-, where each of G1, G2and G3independently from each other selected from hydrogen, alkyl, electron-giver and electron-removing groups (in addition to the above);

either one of R1-R9 is a bridge group associated with another residue, having the same General formula;

T1 and T2 independently of one another represent groups of R4 and R5, where R4 and R5 have the meanings indicated for R1-R9, and if g=0, a s>0, then R1 together with R4 and/or R2 together with R5 may optionally independently from each other represent =CH-R10, where R10 has the meanings indicated for R1-9 or

T1 and T2 together (-T2-T1) can be a covalent bond when s>1, and g>0;

if Z1 and/or Z2 represents N, T1 and T2 together constitute a simple bond, and R1 and/or R2 are absent, Q1 and/or Q2 independently of one another may represent the FDS is, 8, R9 independently of one another are linked together by covalent linkage;

if Z1 and/or Z2 are O, then R1 and/or R2 does not exist;

if Z1 and/or Z2 are S, N, P, b or Si, R1 and/or R2 may be absent;

if Z1 and/or Z2 represent a heteroatom, substituted functional group, R1 and/or R2 and/or R4 and/or R5 may be absent.

The groups Z1 and Z2 are preferably independently of one another represent an optionally substituted heteroatom selected from N, P, O, S, and Si, or an optionally substituted heterocyclic ring, or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrimidine, pyrazole, pyrrole, imidazole, benzimidazole, chinoline, isoquinoline, carbazole, indole, isoindole, furan, thiophene, oxazole and thiazole.

Groups R1-R9 are preferably independently from each other selected from-H, hydroxy-C0-C20-alkyl, halo-C0-C20-alkyl, nitroso, formyl-C0-C20-alkyl, carboxyl-C0-C20-alkyl, their esters and salts, carbarnoyl-C0-C20-alkyl, sulfo-C0-C20-alkyl, their esters and salts, sulfamoyl-C0-SW>-alkyl, C0-C20-alkyl, alkoxy-C0-C8-alkyl, carbonyl-C0-C6-alkoxy, aryl-C0-C6-alkyl and C0-C20-alkylamide.

One of R1-R9 can be a bridging group linking the rest of the ligand with the second residue of the ligand, preferably having the same General structure. In this case, the bridging group can have the formula

-Cn’(R11)(R12)-(D)p-Cm’(R11)(R12)-

connected between the two residues, where p=0 or 1, D is selected from a heteroatom or heteroaromatics group, or D is part of an aromatic or saturated govedarova and heteronuclear ring, n’ is an integer from 1 to 4, m’ is an integer from 1 to 4, provided that n’+m’<=4, R11 and R12 each, independently of one another preferably chosen from N, NR13, and OR14, alkyl, aryl, optionally substituted, and R13 and R14 each independently of one another, optionally substituted, selected from-H, alkyl, aryl. Alternative or additionally, two or more of R1-R9 together represent a bridging group linking atoms, preferably the heteroatoms in the same residue, thus bridging group preferably represents alkalinity, ocuppy T1 and T2 together form a simple link, and s>1 in accordance with the General formula (BII):

where Z3 independently represents a group specified for Z1 or Z2; R3 independently represents a group specified for R1-R9; Q3 independently represents a group specified for Q1, Q2; h=0 or an integer from 1 to 6; a s’=s-1.

In the first specific implementation of the first variant

of General formula (BII), s’=1, 2, or 3; r=g=h=1; d=2 or 3; e=f=0; R6=R7=H, and the ligand preferably has a General formula selected from:

and more preferably chosen from:

In these preferred examples of R1, R2, R3 and R4 are preferably independently from each other selected from-H, alkyl, aryl, heteroaryl, and/or one of R1-R4 is a bridging group associated with another residue, having the same General formula, and/or two or more of R1-R4 together represent a bridging group linking the N atoms in the same residue, thus bridging group is alkilinity, hydroxy-alkalinity or heteroaryl-containing bridge, preferably heteroaryl. More preferably, R1, R2, R3 and R4 independently from each other selected from-H, methyl, ethyl, isopropyl, nitrogen heteroaryl the same residue, when this bridge group is alkylene or hydroxyalkyl.

In accordance with this first variant of the complex [MaLkXn]Ympreferably:

M=Mn(II)-(IV), Cu(I)-(III), Fe(II)-(III), Co(II)-(III);

X=CH3JV, OH2, CL-, Br-, OCN-N-3, SCN-HE-ABOUT2-, RHO3-4C6H5BO2-2, RCOO-;

Y=ClO-4, BPh-4, Br-, CL-, [FeCl4]-PF-6NO-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 specific implementation of the first variant, in General formula (BII) s’=2; r=g=h=1; d=f=0; e=1; and each Y1 independently from each other represents alkylene or heteroaryl. The ligand preferably has the General formula:

where

A1, A2AND3AND4independently from each other selected from C1-9-alkilinity or heteroarylboronic groups; and

N1and N2independently from each other represent a heteroatom or heteroarenes group.

In a second preferred implementation of the first variant, R4 independently of one another represent H, alkyl, aryl or heteroaryl, a a1AND2AND3AND4each independently represents-CH2-.

One of R1-R4 can be a bridging group associated with another residue, having the same General formula, and/or two or more of R1-R4 together may represent a bridging group linking the N atoms in the same residue, thus bridging group is alkilinity, hydroxyalkyloxy or heteroarylboronic bridge. Preferably, R1, R2, R3 and R4 independently from each other selected from-H, methyl, ethyl, isopropyl, nitrogen heteroaryl or bridging group linked to another residue, having the same General formula, or connecting the N atoms in the same residue, thus bridging group is alkylene or hydroxyalkyl.

Particularly preferably, the ligand has the General formula:

where each of R1 and R2 independently from each other represents-H, alkyl, aryl or heteroaryl.

In accordance with this second implementation of the first version of the complex [MaLkXn]Ympreferably:

M=Fe(II)-(III), Mn(II) HE-ABOUT2-, RHO3-4,

WITH6HBO2-2, RCOO-;

Y=ClO-4, BPh-4, Br-, CL-, [FeCl4]-PF-6NO-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 the third specific implementation of the first variant, in General formula (BII) s’=2, a r=g=h=1, in accordance with the General formula:

In this third implementation of the first variant, each of Z1-Z4 preferably represents a heteroaromatic ring; e=f=0; d=1; a R7 is absent, while preferably R1=R2=R3=R4=2,4,6-trimethyl-3-SO3Na-phenyl, 2,6-l-3(or 4)-SO3Na-phenyl.

Alternatively, each of Z1-Z4 represents N; R1-R4 are absent; both Q1 and Q3 are =CH-[-Y1-]e-CH=; and both Q2 and Q4 represents-CH2-[-Y1-]n-CH2-.

Thus, preferably, the ligand has the General formula:

where a represents an optionally substituted alkylene, optionally interrupted by a heteroatom; and n=0 or an integer from 1 to 5.

Preferably, R1-R6 are hydrogen, n=1 and A=-CH2-, -SNON-, -CH2N(R)CH2o, A=-CH2-, -SNON - or-CH2CH2NHCH2CH2-.

In accordance with this third implementation of the first version of the complex [MaLkXn]Ympreferably:

M=Mn(II)-(IV), Co(II)-(III); Fe(II)-(III);

X=CH3JV, HE2, CL-, Br-, OCN-N-3, SCN-HE-ABOUT2-, RHO3-4WITH6H5IN2-2, RCOO-;

Y=lO-4, BPh-4, Br-, Cl-, [FeCl4]-, F-6, NR-3;

and=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 the second embodiment in accordance with the formula (BI), T1 and T2 independently of one another represent a group R4, R5, having the values shown for R1-R9, in accordance with the General formula (BIII):

In the first specific implementation of the second variant, in General formula (BIII), s=1; r=1; g=0; d=f=1; e=1-4; Y1=-CH2-; R1 together with R4, and/or together with R5 independently of one another represent =CH-R10, where R10 has the meanings indicated for R1-R9. In one of the examples of R2 together with R5 represents =CH-R10, when R1 and R4 represent two distinct groups. Alternatively, both R1 wilnie ligands, for example, can have the formula:

The ligand is preferably selected from:

where R1 and R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-Akilov, R3 and R4 are selected from-H, alkyl, aryl, optionally substituted phenols, heteroaryl-C0-C20-Akilov, alkylaryl, aminoalkyl, alkoxy, while R1 and R2 are more preferably selected from optionally substituted phenols, heteroaryl-C0-C2-Akilov, R3 and R4 are selected from-H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-C0-C2-Akilov.

According to this first specific implementation of the second variant in the complex [MaLkXn]Ympreferably:

M=Mn(II)-(IV), Co(II)-(III), Fe(II)-(III);

X=CH3JV, OH2, CL-, Br-, OCN-N-3, SCN-HE-ABOUT2-, RHO3-4C6H5BO2-2, RCOO-;

Y=ClO-4, BPh-4, Br-, CL-, [FeCl4]-PF-6NO-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 the second specific osushestvliayut values, listed for R1-R9. The ligand preferably has the General formula:

Groups R1, R2, R3, R4, R5 in the formula preferably represent-H or C0-C20-alkyl, n=0 or 1, R6 represents-H, alkyl, -HE or-SH, a R7, R8, R9, R10, each preferably, independently of each other selected from-H, C0-C20-alkyl, heteroaryl-C0-C20-alkyl, alkoxy-C0-C8-alkyl, amino-C0-C20-alkyl.

According to this second specific implementation of the second variant, in the complex [MaLkXn]Ympreferably:

M=Mn(II)-(IV), Fe(II)-(III), Cu(II), Co(II)-(III);

X=CH3JV, OH2, Cl-, Br-, OCN-N-3, SCN-HE-ABOUT2-, RHO3-4C6H5BO2-2, RCOO-;

Y=ClO-4, BPh-4, Br-, Cl-, [FeCl4]-PF-6NO-3;

a=1, 2, 3, 4;

n=0, 1, 2, 3, 4;

m=0, 1, 2, 3, 4, 5, 6, 7, 8;

k=1, 2, 3, 4.

In the third specific implementation of the second variant, in General formula (BIII) s=0; g=1; d=e=0; f=1-4. The ligand preferably has the General formula:

Preferably ASS="ptx2">

where R1, R2, R3 have the values listed for R2, R4, R5.

In accordance with this third specific implementation of the second variant, in the complex [MaLkXn]Ympreferably:

M=Mn(II)-(IV), Fe(II)-(III), Cu(II), Co(II)-(III);

X=CH3JV, HE2, CL-, Br-, OCN-N-3, SCN-HE-ABOUT2-, RHO3-4WITH6H5IN2-2, RCOO-;

Y=ClO4-, BPh-4, Br-, Cl-, [FeCl4]-PF-6, NR-3;

and=1, 2, 3, 4;

n=0, 1, 2, 3, 4;

m=0, 1, 2, 3, 4, 5, 6, 7, 8;

k=1, 2, 3, 4.

In the fourth specific implementation of the second variant of the organic substance forms a complex with the General formula (A):

[LMXn]zYq

in which

M represents iron in oxidation state II, III, IV or V, manganese in oxidation States II, III, IV, VI or VII, copper in oxidation state I, II or III, cobalt in oxidation state II, III or IV, or chromium in the oxidation state II-VI;

X represents a coordinating product;

n=0 or an integer from 0 to 3;

z represents the charge of the complex is Aion, type of which depends on the charge of the complex;

q=z/[charge Y]; and

L represents Patsany ligand of General formula (I):

where

each of R1and R2independently from each other represents-R4-R5-,

R3represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or R4-R5,

each of R4independently from each other represents a simple bond or optionally substituted alkylene, albaniles, oxyalkylene, aminoalkyl, simple alkilinity ether, ester of carboxylic acid or carboxylic acid amide, and

each of R5independently from each other represents an optionally N-substituted aminoalkyl group or optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.

The ligand L having the above General formula (V), is Patsany ligand. The term “Patsany” in this description means that five heteroatoms can be coordinated with a metal ion M in the metal complex.

The ligand L of the formula (V) preferably includes at least two substituted or unsubstituted heteroaryl group in four of the side groups. Heteroaryl group preferably represents pyridin-2-yl group, and being substituted, preferably methyl - or ethyl-substituted pyridine-2-yl group. More preferably, the heteroaryl group is unsubstituted pyridin-2-yl group. Preferably, the heteroaryl group is associated with methylamine and, preferably, with its N-atom through a methylene group. The ligand L of the formula (B) preferably 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,N-dialkyl)amino-ethyl.

Thus, in the formula (I) R1preferably represents pyridin-2-yl, or R2represents pyridin-2-yl-methyl. R2or R1preferably represents 2-amino-ethyl, 2-(N-methyl(ethyl) amino-ethyl or 2-(N,N-dimethyl(ethyl) amino-ethyl. Being replaced, R5predel or methyl.

Examples of preferred ligands L of the formula (V) in their simplest form include:

(i) pyridin-2-yl-containing ligands, such as:

N,N-bis(pyridin-2-yl-methyl)-bis(pyridine-2-yl)methylamine;

N,N-bis(pyrazole-1-yl-methyl)-bis(pyridine-2-yl)methylamine;

N,N-bis(imidazol-2-yl-methyl)-bis(pyridine-2-yl)methylamine;

N,N-bis(1,2,4-triazole-1-yl-methyl)-bis(pyridine-2-yl)methylamine

N,N-bis(pyridin-2-yl-methyl)-bis(pyrazole-1-yl)methylamine;

N,N-bis(pyridin-2-yl-methyl)-bis(imidazol-2-yl)methylamine;

N,N-bis(pyridin-2-yl-methyl)-bis(1,2,4-triazole-1-yl)methylamine

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;

N,N-bis(pyrazole-1-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane;

N,N-bis(pyrazole-1-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;

N,N-bis(imidazol-2-yl-methyl}-1,1-bis(pyridin-2-yl)-1-aminoethane;

N,N-bis(imidazol-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;

N,N-bis(1,2,4-triazole-1-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane;

N,N-bis(1,2,4-triazole-1-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(feast of the IP(pyridin-2-yl-methyl)-1,1-bis(imidazol-2-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(imidazol-2-yl)-2-phenyl-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(1,2,4-triazole-1-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(1,2,4-triazole-1-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminohexyl;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(4-sulfonic acid-phenyl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(pyridin-2-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(pyridin-3-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(pyridin-4-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(1-alkyl-pyridine-4-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(1-alkyl-pyridine-3-yl)-1-aminoethane;

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-2-(1-alkyl-pyridine-2-yl)-1-aminoethane;

(ii) 2-amino-ethyl-containing ligands, such as:

N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyridine-2-yl)methylamine;

N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyrazole-1-yl)methyl) - Rev. IP(1,2,4-triazole-1-yl)methylamine;

N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(pyridine-2-yl)methylamine;

N,N-bis(2-N,N-dialkyl)amino-ethyl)-bis(pyrazole-1-yl)methylamine

N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(imidazol-2-yl)methylamine;

N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(1,2,4-triazole-1-yl)methylamine;

N,N-bis(pyridin-2-yl-methyl)-bis(2-amino-ethyl)methylamine;

N,N-bis(pyrazole-1-yl-methyl)-bis(2-amino-ethyl)methylamine;

N,N-bis(imidazol-2-yl-methyl)-bis(2-amino-ethyl)methylamine;

N,N-bis(1,2,4-triazole-1-yl-methyl)-bis(2-amino-ethyl)methylamine

Preferred ligands are:

N,N-bis(pyridin-2-yl-methyl)-bis(pyridine-2-yl)methylamine, hereafter referred to as N4Py.

N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane, hereafter referred to as MeN4P;

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

In an alternative fourth specific implementation of the second variant of the organic substance forms a complex with the General formula (A), including the above-mentioned ligand (B), provided that R3does not represent hydrogen.

In the fifth specific implementation of the second variant of the organic substance of the ligand of General formula (C):

R1R1N-W-NR1R2,

where

each of R1independently from each other represents-R3-V, in which R3is optionally substituted alkylene, albaniles, oxyalkylene, aminoalkyl or simple alkilinity ether, and V represents optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;

W represents an optionally substituted alkylenes bridging group selected from-CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2- and-CH2-C10H6-CH2-; and

R2represents a group selected from R1and the alkyl, aryl and arylalkyl, optionally substituted Deputy selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, ester of carboxylic acid, sulfonate, amine, alkylamine and N+(R4)3in which R4selected from hydrogen, alkenyl, alkenyl, arylalkyl, arylalkyl, oxyalkyl, axiale is nnow General formula (C), represents Patsany ligand or, if R1=R2, - setsunai ligand. As stated above, “Patsany” means that five heteroatoms can be coordinated with a metal ion M in the metal complex. Similarly “setsunai” means that six heteroatoms may in principle be coordinated with a metal ion M But in this case I believe that one of the “shoulders” in the complex is not connected, so setsunai ligand is petticoating.

In the formula (C) two heteroatoms linked bridging group W, with each of the three R1groups contains one coordinating heteroatom. Preferably coordinating heteroatoms are nitrogen atoms.

The ligand L of the formula (C) includes at least one optionally substituted heteroaryl group in each of the three R1-groups. Heteroaryl group preferably represents pyridin-2-yl group, in particular methyl - or ethyl-substituted pyridine-2-yl group. Heteroaryl group is linked to the N atom in the formula (C), preferably through alkylenes group, more preferably a methylene group. Most preferably, the heteroaryl group represents 3-methyl-piou substituted or unsubstituted alkyl, aryl or arylalkyl group or the group R1. However, in the above formula, R2preferably different from each of the groups R1. Preferably, R2represents methyl, ethyl, benzyl, 2-hydroxyethyl or 2-methoxyethyl. More preferably, R2represents methyl or ethyl.

Bridge group W may represent a substituted or unsubstituted alkylenes group selected from-CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2- and-CH2-C10H6-CH2- (where-C6H4-, -C6H10-, -C10H6- can be an ortho-, para - or meta-C6H4-, -C6H10- WITH10H6-). Bridge group W preferably represents ethylene or 1,4-butylene group, more preferably, the ethylene group.

V preferably represents a substituted pyridin-2-yl, especially methyl-substituted or ethyl-substituted pyridine-2-yl, most preferably V is a 3-methyl-pyridine-2-yl.

Examples of preferred ligands of the formula (C)">

N-ethyl-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-benzyl-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-(2-hydroxyethyl)-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)-ethylene-1,2-diamine;

N-(2-methoxyethyl)-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-methyl-N,N’,N’-Tris(5-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-ethyl-N,N’,N’-Tris(5-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-benzyl-N,N’,N’-Tris(5-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-(2-hydroxyethyl)-N,N’,N’-Tris(5-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-(2-methoxyethyl)-N,N’,N’-Tris(5-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-methyl-N,N’,N’-Tris(3-ethyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-ethyl-N,N’,N’-Tris(3-ethyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-benzyl-N,N’,N’-Tris(3-ethyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-(2-hydroxyethyl)-N,N’,N’-Tris(3-ethyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-(2-methoxyethyl)-N,N’,N’-Tris(3-ethyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-methyl-N,N’,N’-Tris(5-ethyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-ethyl-N,N’,N’-Tris(5-ethyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-benzoylmethyl)ethylene-1,2-diamine.

The preferred ligands are:

N-methyl-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-ethyl-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-benzyl-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine;

N-(2-hydroxyethyl)-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine and

N-(2-methoxyethyl)-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine.

The most preferred ligands are:

N-methyl-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine and N-ethyl-N,N’,N’-Tris(3-methyl-pyridine-2-ylmethyl)-ethylene-1,2-diamine.

The metal M in the formula (A) preferably represents Fe or MP, more preferably Fe.

Coordinating product X in the formula (A) can be preferably selected from R6OH, NR63, R6CN, R6OO-, R6S-, R6O-, R6COO-, OCN-, SCN-N-3CN-, F-, Cl-, Br-I-, O2-NO-3NO-2SO2-4SO2-3, PO3-4and aromatic donors N selected from pyridines, pyrazines, pyrazoles, pyrrole, imidazoles, Ben the military alkyl and optionally substituted aryl. X may also be an LMO or LMOO-the product, where M represents a transition metal, L represents the above-described ligand. Coordinating product X is preferably selected from CH3JV, N2O, F-, CL-, VG-THE UN-, R6COO-, R6O-, LMO-and LMOO-where R6represents hydrogen or optionally substituted phenyl, naphthyl or C1-C4alkyl.

The counterions in the formula (A) balance the charge z on the complex formed by the ligand L, metal M and coordinating product X. Therefore, if the charge z is positive, Y may be an anion, such as R7COO-, BPh-4, lO-4BF-4PF-6, R7SO-3, R7SO-4SO2-4, NR-3, F-, CL-, VG-or I-while R7represents hydrogen, optionally substituted alkyl or optionally substituted aryl. If z is negative, Y may be a conventional cation, such as alkali metal, alkaline earth metal or (alkyl)ammonium cation.

Suitable counterions Y include ions, contribute to the metal complexes are selected from R7COO-, ClO-4BF-4PF-6, R7SO-3(in particular, CF3SO-3), R7SO-4SO2-4NO-3, F-, Cl-, Br-or I-where R7represents hydrogen or optionally substituted phenyl, naphthyl or C1-C4alkyl.

The essential point is the formation of the complex (A) by any appropriate means, including the formation in situ, with the precursor complex is transformed into an active complex of General formula (A) in the conditions of storage or use. The complex is preferably formed in the form of a well-defined complex or in a mixture solvent including a salt of the metal M and the ligand L or ligand L-forming product. Alternatively, the catalyst may be formed in situ from suitable for complex precursors, for example, in solution or dispersion containing materials predecessor. In accordance with one example, the active catalyst may be formed in situ in the mixture comprising the salt of the metal M and the ligand L or ligand L-formed product in a suitable solvent. Thus, for example, if M represents iron, then it is UYa active complex. In accordance with another example, the ligand L or ligand L-formed product can be mixed with ions of the metal M present in the substrate or washer fluid, forming an active catalyst in situ. Suitable ligand L-form products include free of metal compounds or metal coordination complexes comprising a ligand L, and can be substituted by metal ions M, forming an active complex according to formula (A).

Therefore, in an alternative fourth and fifth specific implementation of the second variant of the organic substance is a compound of the General formula (D):

[{M’aL}bXc]zYq,

in which

M’ represents hydrogen or a metal selected from Ti, V, Co, Zn, Mg, CA, Sr, Ba, Na, K and Li.

X represents a coordinating product;

and is an integer from 1 to 5;

b is an integer from 1 to 4;

with 0 or an integer from 0 to 5;

z represents the charge of the compound and is an integer which can be positive, 0 or negative;

Y is a counterion, the type of which depends on the charge connection;

q=z/[charge Y]; and

where

Z1and Z2independently from each other selected from structures monocyclic or polycyclic aromatic ring, optionally containing one or more heteroatoms, each structure of the aromatic ring substituted by one or more substituents;

Y1and Y2independently from each other selected from C, N, O, Si, P and S atoms;

AND1and2independently from each other selected from hydrogen, alkyl, alkenyl and cycloalkyl, the latter three compounds optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulfonate, phosphate, electron-giver and electron-removing groups and groups of formula (G1)(G2)N-, G3OC(O)-, G3O - and G3C(O)-, where each of G1, G2and G3independently from each other selected from hydrogen, alkyl, and an electron-giver and/or removing groups (in addition to the groups contained in the above compounds);

i and j are selected from 0, 1 and 2, completing the valence of the groups Y1and Y2;

each of Q1-Q4independently from each other selected from groups of the formula

where 10>a+b+c>SUP>)N- (where G1and G2have the above values), -C(O)-, arylene, heteroaryl, -P - and-P(O)-;

each AND3-AND6independently from each other selected from the groups specified above for AND1and2; and

where any two or more of the A1-AND6together form a bridging group, provided that if a1and2bound without the simultaneous binding with any of the3-AND6then the bridging group linking AND1and2must contain at least one carbonyl group.

In the ligands of formula (E), unless otherwise stated, all the alkyl, hydroxyalkyloxy and alkeneamine groups preferably have from 1 to 6, more preferably from 1 to 4 carbon atoms.

Moreover, the preferred electron-giver groups include alkyl (e.g. methyl), alkoxy (e.g. methoxy), phenoxy and unsubstituted, monosubstituted and disubstituted amino groups. Preferred electron-removing groups include nitro, carboxy, sulfonyl and geograpy.

The ligands of formula (E) can be used in the form of complexes with the corresponding metal or, in some cases, not in the form of complexes. In the latter case, about which osili, specially introduced for the presence of such a metal, or the formation of a complex with the metal, present as trace elements in tap water. However, when the ligand as such or in the form of a complex carries a positive charge, requires the presence of the counterion. The ligand or the complex can be obtained in the form of a neutral product, but often for reasons of stability or ease of synthesis it is advisable to have the charged product with the corresponding anion.

Therefore, in a fourth alternative implementation of the first variant of the ligand of formula (E) is paired with a counterion that is represented by the formula (F):

[HxL]zYq,

where

N - hydrogen atom;

Y is a counterion, the type of which depends on the charge of the complex;

x is an integer, so that L is the protonation of one or more nitrogen atoms;

z represents the charge of the complex and is an integer which can be positive or equal to 0;

q=z/[charge Y]; and

L is a ligand of the above formula (E).

In a further alternative of the fourth implementation of the first variant of the organic substance forms a metal is P>zYq,

where L, Y, x, z and q have the meanings indicated above for formula (F), and M is a metal selected from manganese in oxidation States II-V, iron II-V, copper I-III, cobalt I-III, Nickel I-III, chromium II-VI, tungsten IV-VI, V palladium, ruthenium II-IV, V III-IV and molybdenum IV-VI.

Especially preferred are complexes of the formula (G), where M is manganese, cobalt, iron or copper.

In the fourth preferred specific implementation of the first variant of the organic substance forms a complex of the formula (H):

where M represents an iron atom in oxidation steps II or III, the manganese atom in oxidation steps II, III, IV or V, the copper atom in oxidation steps I, II or III, or a cobalt atom in oxidation state II, III or IV, X - group, serving or not serving as a bridge between the iron atoms, Y is a counterion, while the x-and y>=1, 0=<=n<3, z is the charge of the metal complex, and p=z/charge Y; R1and R2independently of one another, one or more ring substituents selected from hydrogen, electron-giving and removing groups, R3-R8independently from each other hydrogen, alkyl, hydroxyalkyl, alkenyl or their variants with substitution of one or more electron-give the “>=” means “greater or equal”.

In the complex of formula (H) M is an iron atom in oxidation state II or III, or the manganese atom in oxidation state II, III, IV or V oxidation State M is preferably III.

When M represents iron, the complex of the formula (H) is preferably in the form of a salt of iron (oxidized state) dihalo-2,11-diazo[3.3](2,6)peridinian, dihalo-4-methoxy-2,11-diazo[3.3](2,6)peridinian and their mixtures, especially in the form of a chloride salt.

When M represents manganese, the complex of the formula (H) is preferably in the form of a salt of manganese (the oxidized state) N,N’-dimethyl-2,11-diazo[3.3](2,6)peridinian, especially in the form of salts managerservlet.

X is preferably selected from H2O, HE-ABOUT2-SH-S2-SO2-4, NR9R-10, RCOO-, NR9R10R11, Cl-, Br-, F-N-3and combinations thereof, where R9, R10and R11independently from each other selected from-H, C1-4of alkyl and aryl, optionally substituted by one or more electron-removing and/or giving groups. More preferably, X represents a Gal is, Ino selected from CL-, Br-I-NO-3, ClO-4, SCN-, F-6, RSO-3, RSO-4, CF3SO-3, BPh-4and SLA-. Cationic protivominniy equivalent preferably absent.

In the formula (H) R1and R2preferably represent hydrogen. R3and R4preferably represents C1-C4alkyl, especially methyl. Each of R5-R8preferably represents hydrogen.

In accordance with the values x and y of the above-mentioned preferred iron or manganese catalysts of formula (N) can be in the form of a monomer, dimer or oligomer. Without being bound to any theory, it has been suggested that in the raw material or the composition of the detergent catalyst exists primarily or only in the form of a monomer, however, it can be converted into a dimer or oligomer in the washing solution.

Bleaching compositions in accordance with this invention can be used for cleaning with the use of washing and cleaning hard surfaces (including cleaning toilets, kitchen work surfaces, floors, wash mechanical products Ibuki waste paper bleaching of the pulp in the process of getting the paper, not skin, for inhibition of molting dyes, food processing, bleaching starch, sterilization, bleaching items to care for your mouth and/or disinfecting contact lenses. In the context of the present invention under the bleaching refers to the bleaching of stains or other materials on the substrate or related. However, it is envisaged that the invention can also be applied to remove and/or neutralize in the reaction of oxidative bleaching of unpleasant odors or other adverse events associated with the substrate.

In conventional detergent compositions, the level of organic matter is such that the level of its use is from 1 μm to 50 mm, with a preferred level of use at home washing is preferably from 10 to 100 μm. Industrial methods of teeth whitening, such as the bleaching of textiles and paper pulp, may require higher level.

The aqueous medium preferably has a pH in the range from 6 to 13, more preferably from 6 to 11, more preferably from 8 to 11 and most predpochtitaemye particular application in detergent compositions, especially when cleaning with washing. Accordingly, in another preferred variant of its implementation, the invention provides whitening detergent composition containing the above-mentioned whitening composition and, optionally, surface-active material, optionally together with the component of the detergent.

Whitening composition in accordance with this invention may, for example, contain surface-active material in a quantity of 10 to 50 wt.%. Surface-active material may be derived from natural substances, such as soap or synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic active substances and mixtures thereof. Many suitable active substances produced for industrial purposes described in the literature, for example in “Surface Active Agents and Detergents”, Volumes I and II, by Schwartz, Perry and Berch.

Typical synthetic anionic surfactants are usually water-soluble alkali-metal salts of organic sulfates and sulfonates having alkyl groups containing from about 8 to 22 carbon atoms, the term “alkyl” used for Wallpaper include sodium and ammonium the alkyl sulphates, especially the sulfates obtained by the sulfation of higher (C8-C18) alcohols produced for example from tallow or coconut oil; sodium and ammonium alkyl (C9-C20) benzosulfimide, particularly sodium linear secondary alkyl (C10-C15) benzosulfimide; sodium alkyl of glyceryl ethersulfate, especially those ethers of higher alcohols derived from sulfates and sulfonates of monoglyceride fatty acids of tallow or coconut oil; reaction products of sodium salts and ammonium esters of sulfuric acid oxide alkylene higher (C9-C18) fatty alcohol, especially of ethylene oxide; the reaction products of fatty acids such as coconut fatty acids esterified isetionate acid and neutralized with sodium hydroxide; sodium and ammonium fatty acid amides methyltaurine; alanmoorefan, for example, resulting from the reaction of alphaolefins (C8-C20) with sodium bisulfite and the resulting reaction of paraffins with SO2and Cl2and then hydrolysis with a base to obtain a random sulfonate; sodium and ammonium (C7-C12) dialkyl sulfosuccinate; and reincorporate; this term is used to describe the 3 and then neutralization and hydrolysis of the reaction product. The preferred anionic detergent compounds are sodium (C10-C15) alkylbenzenesulfonate and sodium (C16-C18) alkylarylsulfonate.

Examples of suitable nonionic surface-active compounds, preferably applicable together with anionic surface-active compounds include, in particular, the reaction products of oxides alkylene, usually ethylene oxide, with alkyl(C6-C22) Fanelli, generally 5-25 EO, i.e. 5-25 units of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18), primary or secondary, linear or branched alcohols with ethylene oxide, generally 2-30 EO. Other so-called nonionic surfactants include alkylpolyglycoside, esters of sugar, long-chain tertiary amine oxides, long chain tertiary phosphine oxides and diallylsulfide.

In the compositions in accordance with this invention can also be used amphoteric or zwitterionic surface-active compounds, however, this is usually undesirable because of their relatively high cost. When using amphoteric or cvit is often used synthetic anionic and non-ionic active substances.

Detergent bleach in accordance with this invention preferably contains from 1 to 15 wt.% anionic surfactant and from 10 to 40 wt.% non-ionic surfactants. In accordance with a further preferred embodiment of the present invention active detergent-free soap from C16-C12of fatty acids.

Bleach, in accordance with this invention may also contain a component of detergent, e.g., in the amount of approximately from 5 to 80 wt.%, preferably from about 10 to 60 wt.%.

Components can be selected from: 1) isolating the calcium materials (sequestrants), 2) precipitating materials, 3) calcium ion-exchange materials, and (4) mixtures thereof.

Examples of calcium-insulating materials include alkali metal polyphosphates, such as sodium tripolyphosphate, nitrilotriacetic acid and its water soluble salts; salts of alkaline metals carboxymethylcysteine acid, ethylenediaminetetraacetic acid, oxydiethanol acid, Melitopol acid, benzoldicarbonic acid, citric acid; and politicalstability, opican">

Examples of calcium ion exchange materials include various kinds of water-insoluble crystalline or amorphous aluminosilicates, the best-known representatives of which are zeolites, such as zeolite A, zeolite B (also known as zeolite R, zeolite S, zeolite X, zeolite Y, and zeolite P-type described in EP-A-0384070.

In particular, the substance in accordance with this invention can contain any of the organic and inorganic components, despite the fact that the phosphate components preferably do not apply or apply only in very small quantities due to pollution. Typical components that are applicable in this invention include, for example, sodium carbonate, calcite/carbonate, sodium salt nitryltriacetic acid, sodium citrate, carboxymethyloxime, carboxymethyloxysuccinic and water-insoluble crystalline or amorphous aluminosilicate components, each of which can be used as a main component separately or in a mixture with small amounts of other polymers or as acomponent.

The composition preferably contains not more than 5 wt.% component carbonate, virili is alkaline in the lower range, up to 10.

In addition to the aforementioned components, the bleaching composition in accordance with this invention can contain any of the known additives in amounts commonly used in compositions for washing fabrics. Examples of such additives include buffers, such as carbonates, accelerators, foaming, such as alkanolamides, especially monoethanolamide derived from palm and coconut fatty acids; extinguishers foaming, such as alkylphosphate and silicones; agents that prevent re-deposition, such as carboxymethylcellulose and alkyl or substituted alkyl cellulose ethers; stabilizers, such as derivatives of phosphonic acid (for example, type Dequest ); fabric softening agents, inorganic salts and alkaline buffering agents such as ferrous sulfate and sodium silicate; and usually in very small amounts, fluorescent agents; perfumes; enzymes, such as protease, cellulase, lipase, amylase and oxidase; germicide and dyes.

In addition to the above organic substances, may also be included airing of transition metals, such as EDTA and derivatives of phosphonic acids, such as ethylenediaminetetra-(methylenephosphonic), for example, to improve the stability of the whitening action of the composition. However, the composition in accordance with this invention, containing organic matter, preferably essentially and more preferably completely, devoid of airing transition metals (other than organic matter).

Although this invention is based on the catalytic bleaching of the substrate by atmospheric oxygen or air, if desired, the composition can be incorporated small amounts of hydrogen peroxide or based on peroxide or form of its system. However, preferably the composition is devoid of peroxide bleach or based on peroxide or its forming bleaching systems.

Further, this invention is illustrated by the following non-limiting examples:

Examples

Example 1

This example describes the synthesis of the catalyst in accordance with the formula (A):

(i) Obtaining ligand MeN4Py:

Predecessor N4Py HClO4get as follows:

To pyridylketone the oxime (3 g, 15.1 mmol) are added ethanol (15 ml), concentrated ammonia solution (15 ml) and NH4OAc (1,21 g, 15.8 mmol). The solution is heated to reflux distilled. To this solution in small portions add with 4.64 g Zn. After the market. The solution is filtered and added to it water (15 ml). Add solid NaOH to obtain a pH>>10 and the solution extracted with CH2Cl2(3 20 ml). The organic layers dried over Na2SO4and evaporated to dryness. Receive bis(pyridine-2-yl)methylamine (2,39 g, 12.9 mmol) as a colourless oil with a yield amounting to 86% and having the following analytical characteristics:

1H NMR (360 MHz, Dl3): of 2.64 (s, 2H, NH2), is 5.18 (s, 1H, CH), 6,93 (m, 2H, pyridine), 7,22 (m, 2H, pyridine), 7,41 (m, 2H, pyridine), 8,32 (m, 2H, pyridine);

13C-NMR (Dl3) 62,19 (CH), 121,73 (CH), 122,01 (CH), 136,56 (CH), 149,03 (CH), 162,64 (Cq).

To picolylamine add hydrochloride (4,06 g of 24.8 mmol) at 0 C, and 4.9 ml of 5N NaOH solution. This emulsion at 0 C using a syringe add to bis(pyridine-2-yl)methylamine (2.3 g, 12.4 mmol). To this mixture again, add 5N NaOH solution. After warming to ambient temperature the mixture is subjected to vigorous stirring for 40 hours. The mixture is placed in an ice bath and add to it lO4to obtain a pH<1, the sediment falls hard brown substance which is collected by filtration and recrystallized out of the water. With stirring, the mixture is cooled to ambient temperature, and dried in air (1.47 g).

From 0.5 g of the salt of perchlorate N4Py received in accordance with the above description, get free amine, precipitating salt 2N NaOH, and then extragere CH2Cl2. To the free amine in an argon atmosphere add 20 ml of dry tetrahydrofuran, freshly distilled from LiAlH4. The mixture is stirred and cooled to -70 With using baths of alcohol/dry ice. Then add 1 ml of 2.5 N solution of utility in hexane, immediately coloring mixture of dark-red color. The mixture is left to heat up to -20 ° C, then add 0.1 ml under the conditions. The temperature of the support at the level of -10 C for 1 hour. Then add 0.5 g of ammonium chloride and the mixture is evaporated in vacuum. To the residue water is added, extragere aqueous layer with dichloromethane. The dichloromethane layer is dried on sodium sulfate, filtered and evaporated, getting the balance weight of 0.4, the Residue is purified by crystallization from ethyl acetate and hexane, obtaining 0.2 g white powder (yield = 50%) having the following analytical characteristics:

1H NMR (400 MHz, Dl3): (M. D.) was 2.05 (s, 3H, CH3), to 4.01 (s, 4H, CH2), 6,92 (m, 2H, pyridine), was 7.08 (m, 2H, pyridine), 7,39 (m, 4H, pyridine), 7,60 (m, 2H, pyridine), 7,98 (d, 2H, pyridine), to 8.41 (m, 2H, pyridine), to 8.57 (m, 2H, pyridine is), 123,6 (CH), 136,0 (CH), 148,2 (Cq), Of 148.6 (Cq), 160,1 (Cq), 163,8 (Cq).

(ii) Synthesis of the complex [(MeN4Py)Fe(CH3CN)](ClO4)2, Fe(MeN4Py):

To a solution of 0.27 g MeN4Py in 12 ml of a mixture of 6 ml of acetonitrile and 6 ml of methanol add 350 mg Fe(ClO4)26N2Oh, after which the mixture immediately becomes dark red. Then to this mixture, 0.5 g of sodium perchlorate, causing immediate formation of an orange-red precipitate. After five minutes of stirring and ultrasonic treatment, the precipitate was separated by filtration and dried in vacuum at 50 C. Thus obtain 350 mg of an orange-red powder with a yield amounting to 70% and having the following analytical characteristics:

1H NMR (400 MHz, CD3CN): (M. D.) 2,15 (CH3JV), of 2.28 (s, 3H, CH3), 4.2V (ab, 4H, CH2), 7,05 (d, 2H, pyridine), 7,38 (m, 4H, pyridine), 7,71 (2T, 4H, pyridine), 7,98 (t, 2H, pyridine), 8,96 (d, 2H, pyridine), 9,06 (m, 2H, pyridine).

UV/Vis (acetonitrile) [ max, nm( , M-1cm-1)]: 381 (8400), 458 nm (6400).

Elemental analysis for C25H26Cl2FeN6O8: C, 46,11; N, A 3.87; N, 12,41; Cl, 10,47; Fe, 8,25.

Found: C, 45,49; N, Of 3.95; N, 12,5; Cl, 10,7; Fe, 8,12.

Macc-ESP (cone voltage 17V in CH3CN): m/z of 218.6 [MeN4PyFe]2+; 239,1 [N4F3SP]

(i) Synthesis of ligand BzN4Py:

To 1 g of the ligand N4Py received in accordance with the above description, in an argon atmosphere add 20 ml of dry tetrahydrofuran, freshly distilled from LiAlH4. The mixture is stirred and cooled to -70 With using baths of alcohol/dry ice. Then add 2 ml of 2.5 N solution of utility in hexane, immediately coloring mixture of dark-red color. The mixture is left to heat up to -20 ° C, then add 0.4 ml of benzylbromide. Mixture was allowed to warm to 25 C, and stirring is continued over night. Then add 0.5 g of ammonium chloride and the mixture is evaporated in vacuum. To the residue water is added, extragere aqueous layer with dichloromethane. The dichloromethane layer is dried on sodium sulfate, filtered and evaporated, getting a brown oil residue mass 1, In accordance with the data of NMR spectroscopy, the product is not pure, but contains no original material (N4Py). The residue is used without further purification.

(ii) Synthesis of the complex [(BzN4Py)Fe(CH3JV)](CL4)2, Fe(BzN4Py):

To a solution of 0.2 g of the residue, the resulting visheopisannie procedure, 10 ml of a mixture of 5 ml of acetonitrile and 5 ml of methanol was added 100 mg of Fe(ClO4

1H NMR (400 MHz, CD3CN): (M. D.) a 2.12 (s, 3H, CH3JV), 3,65+4,1 (ab, 4H, CH2), was 4.42 (s, 2H, CH2-benzyl), at 6.84 (d, 2H, pyridine), 7,35 (m, 4H, pyridine), was 7.45 (m, 3H, benzene), the 7.65 (m, 4H benzene + pyridine), 8,08 (m, 4H, pyridine), of 8.95 (m, 4H, pyridine).

UV/Vis (acetonitrile) ( max, nm( , M-1cm-1)]: 380 (7400), 458 nm (5500).

Macc-ESP (cone voltage 17V in CH3SP): m/z figure of € 256.4 [BzN4Py]2+; 612 [BzN4PyFeClO4]+.

Example 3

This example describes the synthesis of catalysts in accordance with the formula (C):

Unless otherwise noted, all reactions carried out in nitrogen atmosphere. Unless otherwise noted, all reagents and solvents receive from Aldrich or Across and apply in finished form. Before using as a solvent for elution of petroleum ether 40-60 subjected to distillation using a rotary evaporator. Column flash chromatography carried out using Merck silica gel 60, or aluminum oxide 90 (activity II-III according to Brockmann). If not stated otherwise, the1H NMR (300 MHz) and13With NMR (75 MHz) LASS="ptx2">

Synthesis of starting materials for the synthesis of ligand:

Synthesis of N-benzylaminocarbonyl

N-benzylamine (5.35 g, 50 mmol) dissolved in a mixture of water:methanol (50 ml, 1:4). Add hydrochloric acid (aq., 30%) up until the pH reaches of 7.0. Added NaCN (2,45 g, 50 mmol). After cooling to 0 added formalin (aq., 35%, of 4.00 g, 50 mmol). The reaction is controlled by using thin-layer chromatography (TLC) (aluminium oxide; EtOAc:Et3N=9:1) to detect benzylamine. Then the methanol is evaporated in vacuum and the remaining oil dissolved in water. The aqueous phase is extracted with methylene chloride (3 50 ml). The organic layers are collected, and the solvent is removed in vacuum. The residue is purified by Kugelrohr distillation (p=20 mm Od, T=120 s), receiving N-benzylaminocarbonyl (4,39 g, 30 mmol, 60%) as a colourless oil.

1H NMR: 7,37-7,30 (m, 5H), of 3.94 (s, 2H), only 3.57 (s, 2H), 1,67 (Shir.s, 1H);

13WITH NMR: 137,74, 128,58, 128,46, 128,37, 127,98, 127,62, 117,60, 52,24, 36,19.

Synthesis of N-ethylaminoethanol

This synthesis is carried out analogously to the synthesis described for N-benzylaminocarbonyl, the detection is conducted by dipping the TLC plate placed in the solution KMPO4and heating it until the bright spots. Using ethylamine (2.25 ATAGO oil.

1H NMR: of 3.60 (s, 2H), 2,78 (kV, J=7,1, 2H), 1,22 (Shir.s, 1H), 1.14 in (t, J=7,2, 3H);

13WITH NMR 117,78, 43,08, 37,01, 14,53.

Synthesis of N-ethylethylene-1,2-diamine

This synthesis is carried out in accordance with Hageman; J. Org.Chem.; 14; 1949; 616, 634, using N-ethylaminoethanol as the original product.

Synthesis of N-benzylation-1,2-diamine

Sodium hydroxide (890 mg, of 22.4 mmol) is dissolved in ethanol (96%, 20 ml), and the dissolution process lasts almost 2 hours. To the solution was added N-benzylaminocarbonyl (4, of 2.92 g, 20 mmol) and Raney Nickel (approx. 0.5 g). The hydrogen pressure (p=3.0 ATM) used up until its absorption will not stop. The mixture is filtered through celite, washing the residue with ethanol, and the filter should not dry, since the Raney Nickel is relatively pyrophoric. Celite containing Raney Nickel, decompose, adding the mixture to dilute the acid and causing the formation of gas. The ethanol is evaporated in vacuo, and the residue is dissolved in water. After adding the base (aq. NaOH 5N) the product is released in the form of oil, is extracted with chloroform (3 20 ml). After evaporation of the solvent in vacuum1H NMR shows the presence of benzylamine. The separation is carried out using column chromatography (silica compound is carried out, using alumina as the solid phase in TLC, while receiving pure N-benzylation-1,2-diamine (2,04 g of 13.6 mmol, 69%).

1H NMR: 7,33-of 7.24 (m, 5H), 3,80 (s, 2H), 2,82 (t, J=5,7, 2H), 2,69 (t, J=5,7, 2H), 1,46 (Shir.s, 3H);

13WITH NMR 140,37, 128,22, 127,93, 126,73, 53,73, 51,88, 41,66.

Synthesis of 2-acetoxymethyl-5-methylpyridine

2,5-Lutidine (31.0 g, 290 mmol), acetic acid (180 ml) and hydrogen peroxide (30 ml, 30%) heated at 70-80 C for three hours. Add hydrogen peroxide (24 ml, 30%) and the resulting mixture is heated for 16 hours at 60-70 C. the Most part a mixture of (probably) from hydrogen peroxide, water, acetic acid and peracetic acid are removed under vacuum (rotary evaporator, water bath at 50 C to p=20 mbar). The resulting mixture containing N-oxide, are added dropwise to acetic anhydride is heated at reflux distilled. This vysokoekonomichny reaction control, reducing the rate. After heating at reflux distilled for one hour added dropwise methanol. This reaction vysokoekonomichny. The resulting mixture is heated at reflux distilled for another 30 minutes. After evaporation of methanol (rotary evaporator, 50 With up to p=20 mbar) and the resulting mixture was purified by Kugelrohr distillation (p=20 mm Hg, T=150 C). Get transparent the (feast upon.)), getting clean acetate 2-acetoxymethyl-5-methylpyridine (34,35 g, 208 mmol, 72%) as a yellowish oil.

1H NMR: 8,43 (s, 1H), 7,52 (DD, J=7,8, J=1,7, 1H), 7,26 (d, J=7,2, 1H), 5,18 (s, 2H), 2,34 (s, 3H), of 2.15 (s, 3H);

13WITH NMR: 170,09, 152,32, 149,39, 136,74, 131,98, 121,14, 66,31, 20,39, 17,66.

Synthesis of 2-acetoxymethyl-5-ethylpyridine

This synthesis is carried out analogously to the synthesis described for 2-acetoxymethyl-5-methylpyridine. Using 5-ethyl-2-methylpyridine (35,10 g, 290 mmol) as starting product, get pure 2-acetoxymethyl-5-ethylpyridine (46,19 g, 258 mmol, 89%) as a yellowish oil.

1H NMR: of 8.47 (s, 1H), 7,55 (d, J=7,8, 1H), 7,29 (d, J=8,1, 1H), 2,67 (kV, J=7,8, 2H), and 2.14 (s, 3H), of 1.26 (t, J=TO 7.77, 3H);

13WITH NMR: 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-methylpyridine

This synthesis is carried out analogously to the synthesis described for 2-acetoxymethyl-5-methylpyridine. The only difference is the reverse Kugelrohr distillation and extraction. In accordance with1H NMR receive a mixture of acetate and the corresponding alcohol. Using 2,3-picoline (31.0 g, 290 mmol) as starting product, get pure 2-acetoxymethyl-3-methylpyridine (46,19 g, 258 mmol, 89%, in terms of pure acetate) in the form of yellow is ptx2">

Synthesis of 2-hydroxymethyl-5-methylpyridine

2-Acetoxymethyl-5-methylpyridine (30 g, 182 mmol) was dissolved in hydrochloric acid (100 ml, 4N). The mixture is heated at reflux distilled up until TLC (silica gel; triethylamine:ethyl acetate:petroleum ether 40-60=1:9:19) will not show the complete absence of acetate (usually within 1 hour). The mixture is cooled, the pH adjusted to pH>11, extracted with dichloromethane (3 50 ml) and the solvent is removed in vacuum. Pure 2-hydroxymethyl-5-methylpyridin (18,80 g, 152 mmol, 84%) is obtained Kugelrohr distillation (p=20 mm Od, T=130) in the form of a yellowish oil.

1H NMR: 8,39 (s, 1H), 7,50 (DD, J=7,8, J=1,8, 1H), 7,15 (d, J=8,1, 1H), to 4.73 (s, 2H), 3,83 (Shir.s, 1H), 2,34 (s, 3H);

13WITH NMR: 156,67, 148,66, 137,32, 131,62, 120,24, 64,12, 17,98.

Synthesis of 2-hydroxymethyl-5-ethylpyridine

This synthesis is carried out analogously to the synthesis described for 2-hydroxymethyl-5-methylpyridine. Using 2-acetoxymethyl-5-ethylpyridine (40 g, 223 mmol) as starting product, get pure 2-hydroxymethyl-5-ethylpyridine (to 26.02 g, 189 mmol, 85%) as a yellowish oil.

1H NMR: 8,40 (d, J=1,2, 1H), 7,52 (DD, J=8,0, J=2,0, 1H), 7,18 (d, J=8,1, 1H), 4,74 (s, 2H), 3,93 (Shir.s, 1H), 2,66 (kV, J=7,6, 2H), 1.26 in (t, J=7,5, 3H);

13WITH NMR: 156,67, 148,00, 137,87, 136,13, 120,27, 64,07, 25,67, 15,28.

hydroxymethyl-5-methylpyridine. Using 2-acetoxymethyl-3-methylpyridine (25 g (restated for the mixture), 152 mmol), get pure 2-hydroxymethyl-3-methylpyridine (15,51 g, 126 mmol, 83%) as a yellowish oil.

1H NMR: 8,40 (d, J=4,5, 1H), 7,47 (d, J=7,2, 1H), 7,15 (DD, J=7,5, J=5,1, 1H), 4,85 (Shir.s, 1H), 4,69 (s, 1H), 2,22 (s, 3H);

13WITH NMR: 156,06, 144,97, 137,38, 129,53, 121,91, 61,38, 16,30.

(i) Synthesis of ligands:

Synthesis of N-methyl-N,N’,N-Tris(pyridine-2-ylmethyl)ethylene-1,2-diamine (L1)

The ligand L1 (comparative) receive in accordance with the description Bernal, Ivan; Jensen, Inge Margrethe; Jensen, Kenneth C.; McKenzie, Christine I.; Toftlund, Hans; Tuchagues, Jean-Pierre; J. Chem. Soc.Dalton Trans.; 22; 1995; 3667-3676.

Synthesis of N-methyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L2, Matrilin)

2-Hydroxymethyl-3-methylpyridine (5,00 g of 40.7 mmol) dissolved in dichloromethane (30 ml). Dropwise with cooling (ice bath) is added thionyl chloride (30 ml). The resulting mixture was stirred for 1 hour and the solvents removed in vacuo (rotary evaporator, up to R=20 mm Od, T=50). To the resulting mixture are added dichloromethane (25 ml). Then added dropwise NaOH (5N, aq.) up until the pH reaches a pH (water) 11. The start of the reaction is quite rapid, as part of the thionyl chloride is still present. Add N-methylation-1,2-diami is their 45 hours. The mixture was poured into water (200 ml) and check the pH (if pH does not correspond to 14, then add NaOH (aq., 5N). The reaction mixture was extracted with dichloromethane (3 or 4 50 ml up until TLC shows the absence of the product). The combined organic phases are dried and the solvent is removed in vacuum. Cleaning is performed in accordance with the above description, receiving N-methyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine as a yellowish oil. Cleaning is carried out using column chromatography (aluminium oxide 90 (activity II-III according to Brockmann); triethylamine:ethyl acetate:petroleum ether 40-60=1:9:10) as long as the impurities are not removed in accordance with TLC (alumina, the same solvent for elution, Rf of 0.9). The connection is subjected to chromatography using ethyl acetate:triethylamine 9:1 and receiving N-methyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L2, 1,743 g, 4.30 mmol, 63%).

1H NMR: at 8.36 (d, J=3,0, 3H), 7,40-7,37 (m, 3H), 7,11-7,06 (m, 3H), 3,76 (s, 4H), of 3.48 (s, 2H), was 2.76-2.71 to (m, 2H), 2,53-2,48 (m, 2H), 2,30 (s, 3H), 2,12 (C, 6N), was 2.05 (s, 3H);

13WITH NMR: 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-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L3, t)

This synthesis piperidin (25,00 g, 203 mmol) and N-ethylethylene-1,2-diamine (2,99 g 34,0 mmol), receive N-ethyl-N,N’,N’-Tris(methyl-pyridine-2-ylmethyl)ethylene-1,2-diamine (L3, 11,49 g, 28.5 mmol, 84%). Hold column chromatography (oxide Alcmene; Et3N:EtOAc: petroleum ether 40-60=1:9:30, and then Et3N:EtOAc=1:9).

1H NMR: a 8.34-8.30 to (m, 3H), 7,40-7,34 (m, 3H), to 7.09-7.03 is (m, 3H), 3,71 (s, 4H), to 3.58 (s, 2H), 2,64 at 2.59 (m, 2H), 2,52-2,47 (m, 2H), 2,43-of 2.36 (m, 2H), 2,31 (s, 3H), 2,10 (C, 6N), of 0.87 (t, J=7,2, 3H);

13WITH NMR: 157,35, 156,92, 145,65, 137,61, 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-benzyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L4, z)

This synthesis is carried out analogously to the synthesis described for L2. Using as starting materials 2-hydroxymethyl-3-methylpyridine (3.00 g, 24.4 mmol) and N-benzylation-1,2-diamine (610 mg, 4.07 mmol) receive N-benzyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L4, 1,363 g of 2.93 mmol, 72%). Hold column chromatography (aluminium oxide; Et3N:tO:petroleum ether 40-60=1:9:10).

1H NMR: 8,33-8,29 (m, 3H), 7,37-7,33 (m, 3H), 7,21-7,03 (m, 8H), 3,66 (s, 4H), of 3.60 (s, 2H), 3,42 (s, 2H), 2,72-to 2.67 (m, 2H), 2,50 at 2.45 (m, 2H), of 2.23 (s, 3H), 2,03 (C, 6N);

13H NMR: 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 is a rule synthesis, described for L6. Using as starting materials 2-hydroxymethyl-3-methylpyridine (3,49 g, 28.4 mmol) and N-hydroxyethylamino-1,2-diamine (656 mg, 6,30 mmol), after 7 days of receive N-hydroxyethyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L5, 379 mg, 0.97 mmol, 14%).

1H NMR: 8,31-of 8.28 (m, 3H), 7,35-7,33 (m, 3H), 7,06-7,00 (m, 3H), 4,71 (Shir.s, 1H), of 3.73 (s, 4H), 3,61 (s, 2H), 3,44 (t, J=5,1, 2H), 2,68 (s, 4H), to 2.57 (t, J=5,0, 2H), 2,19 (s, 3H), 2,10 (C, 6N);

13WITH NMR: 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.

Synthesis of N-methyl-N,N’,N’-Tris(5-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L6)

2-hydroxymethyl-5-methylpyridin (2.70 g, 21.9 mmol) dissolved in dichloromethane (25 ml). Dropwise with cooling (ice bath) is added thionyl chloride (25 ml). The resulting mixture was stirred for 1 hour and the solvents removed in vacuo (rotary evaporator, up to R=20 mm Od, T 35). The remaining oil is used directly in the synthesis of ligands, since it is known from literature that the free picolylamine somewhat unstable and wisecrackery. To the resulting mixture are added dichloromethane (25 ml) and N-methylation-1,2-diamine (360 mg, a 4.86 mmol). Then added dropwise NaOH (5N, aq.). The start of the reaction is quite rapid, as part of ,38 ml). The reaction mixture is stirred until then, until the sample shows complete conversion (7 days). The reaction mixture was extracted with dichloromethane (3 25 ml). The combined organic phases are dried and the solvent is removed in vacuum. Cleaning is carried out using column chromatography (aluminium oxide 90 (activity II-III according to Brockmann); triethylamine:ethyl acetate:petroleum ether 40-60=1:9:10) as long as the impurities are not removed in accordance with TLC (alumina, the same solvent for elution, Rf of 0.9).

The connection is subjected to chromatography using ethyl acetate:triethylamine = 9:1, receiving N-methyl-N,N’,N’-Tris (5-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L6, 685 mg of 1.76 mmol, 36%) as a yellowish oil.

1H NMR: 8,31 (s, 3H), 7,43-to 7.35 (m, 5H), 7,21 (d, J=7,8, 1H), 3,76 (s, 4H), of 3.56 (s, 2H), 2,74-2,69 (m, 2H), 2,63-of 2.58 (m, 2H), and 2.27 (s, 6N), of 2.16 (s, 3H);

13WITH NMR: 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-N,N’,N’-Tris(5-ethylpyridine-2-ylmethyl)ethylene-1,2-diamine (L7)

This synthesis is carried out analogously to the synthesis described for L6. Using as starting materials 2-hydroxymethyl-5-ethylpyridine (3.00 g, 21.9 mmol) and N-methylation-1,2-diamine (360 mg, a 4.86 mmol), after 7 days of receive N-methyl-N,N’,N is 7,26 (d, J=6,6, 1H), 3,80 (s, 4H) and 3.59 (s, 2H), 2.77-to of 2.72 (m, 2H), 2,66-to 2.57 (m, 8H), to 2.18 (s, 3H), of 1.23 (t, J=7,5, 9H);

13WITH NMR: 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.

(ii) Synthesis of complexes the metal-ligand

Synthesis of chloride N-methyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine iron (II). PF6([L2Fe(II)Cl]PF6)

FeCl24H2O (a 51.2 mg, 257 mmol) dissolved in Meon:N2O=1:1 (2.5 ml). The solution is heated to 50 C and add to it the N-methyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L2, 100 mg, 257 mmol) in the Meon:N2O=1:1 (2.0 ml). Then added dropwise NaPF6(to 86.4 mg, 514 mmol) in H2O (2.5 ml). After cooling to room temperature, filtering and drying in vacuum (p=0.05 mm Od, T = room temperature) are complex [L2Fe(II)Cl]PF6(149 mg, 239 mmol, 93%) as a yellow solid substance.

1H NMR (CD3CN, paramagnetic): 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, -1,25, -4,82, -18,97, -23,46.

Synthesis of chloride N-ethyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine iron (II). PF6([L2Fe(II)Cl]PF6)

This synthesis is carried out similarly, the synth is in 2-ylmethyl)ethylene-1,2-diamine (L3, 104 mg, 257 mmol), get complex [L3Fe(II)Cl]PF6) (146 mg, 229 mmol, 89%) as a yellow solid substance.

1H NMR (CD3CN, paramagnetic): 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 chloride N-benzyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine iron (II). PF6([L4Fe(II)Cl]PF6)

This synthesis is carried out analogously to the synthesis described for L2Fe(II)CL]F6). Using as a starting material N-benzyl-N,N’,N’-Tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L4, 119,5 mg, 257 mmol receive complex (172 mg, 229 mmol, 95%) as a yellow solid substance.

1H NMR (CD3CN, paramagnetic): 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 the synthesis of the catalyst of formula (N), where:

R2-R8=H; R1=4-MeO; x=1; y=1; z=1; X=Cl, n=2; Y=Cl-p=1.

(i) Synthesis of ligand 2,11-diaza[3.3]-(4-methoxy)(2,6)peridinian ((4OMe)LN1H2):

4-Chloro-2,6-pyridylmethylamine ether (2)

A mixture of 4-hydroxy-2,6-pyridine diabolou acid (12.2 g, 60 mmol), and PCl

1H NMR (200 MHz, N2O) 7,60 (2H, s), 4,05 (6N, C).

4-Methoxy-2,6-pyridinedimethanol (4)

Metallic sodium (1 g, 44 mmol) is dissolved in 200 ml of dry methanol. Then add dimethyl ether 4-chloro-2,6-pyridyl (of 9.2 g, 40 mmol) and the mixture refluxed for 3 hours, getting pure dimethyl ether 4-methoxy-2,6-pyridyl. To this solution at room temperature in small portions add NaBH4(9,1 g, 240 mmol) and the mixture refluxed for 16 hours. Then add acetone (30 ml) and the solution refluxed for 1 hour. After removal of all volatiles the residue is heated with 60 ml of a saturated solution of NaHCO3/Na2CO3. After dilution with 80 ml of water, the product is subjected to continuous extraction l3within 2-3 days. Viparita l3get 83% 4-methoxy-2,6-pyridinedimethanol.

1H NMR (200 MHz, H2O) 6,83 (2H, s), and 5.30 (2H, s), 4,43 (4H, s), 3,82 (3H, s).

4-Methoxy-2,6-dichlorethylene (5)

This synthesis is carried out in accordance with the description, Primadonna procedure, described in the literature. The resulting crude product is practically pure (yield = 95%).

1H NMR (CDCl3, 250 MHz): 7,72 (4H, d, J=7 Hz), and 7.4 (1H, t, J=6 Hz), 7,35 (4H, d, J=7 Hz), and 7.1 (1H, d, J=6 Hz), to 6.57 (2H, s), of 4.45 (4H, s), 4,35 (4H, s), the 3.65 (3H, s), 2,4 (6N, C).

2,11-diaza[3.3]-(4-methoxy)(2,6) peridinian

This procedure is similar to the procedure described above. The resulting crude product was then purified by chromatography (alumina, CH2Cl2)MeOH 95:5), yield = 65%.

1H NMR (Dl3, 250 MHz): to 7.15 (1H, t, J=6 Hz), 6,55 (1H, d, J=6 Hz), equal to 6.05 (2H, s), of 3.95 (4H, s), a 3.87 (4H, s), the 3.65 (3H, s).

Mass spectrum (EI):M+=270 (100%)

(ii) Synthesis of the complex [Fe(4OMeLN4H2)Cl2]Cl:

270 mg 2,11-diaza[3.3]-(4-methoxy)(2,6) pyridinoline (1 mmol) is dissolved in 15 ml of dry tetrahydrofuran. To this solution was added a solution of 270 mg Fl36N2Oh (1 mmol) in 5 ml of Meon. The resulting mixture is evaporated to dryness and the solid product is dissolved in 10 ml of AcN with a minimum number of Meon. Slow diffusion of tetrahydrofuran leads to obtain 300 mg of brown crystals, yield = 70%.

Elemental analysis for C15H18N4Cl3OFe 0.5 in MeOH (found/].): C=41,5/41,61, N=4,46/TO 4.52, N=12,5/12,08.

IR (KBr pellets, cm-1): 3545, 3414, 3235, is ormula (N)

where

R1-R8=H; x=1; y=1; z=1; X=CL; n=2; Y=CL-p=1.

Synthesis of complex [Fe(LN4H2)Cl2]Cl:

240 mg, LN4H2(1 mmol) is dissolved in 15 ml of dry tetrahydrofuran. To this solution was added a solution of 270 mg FeCl36H2O (1 mmol) in 5 ml of Meon. The resulting mixture is stirred, getting directly 340 mg of yellow powder, yield = 85%.

IR (KBR pellets, cm-1): 3445, 3031, 2851, 1629, 1062, 1473, 1427, 1335, 1157, 1118, 1045, 936, 796, 340, 318.

Example 6

This example describes the synthesis of the catalyst of formula (N), where:

R1=R2=R5-8=H; R3=R4=Me; x=1; y=1; n=2; z=1; X=F-; m=2; Y=PF-6; p=1.

Debtor [N,N’-dimethyl-2,11-diaza[3.3](2,6)pyridinium] manganese (III) hexaphosphate

(i) Synthesis of the ligand N’,N’-dimethyl-2,11-diaza[3.3](2,6) peridinian:

2,6-Dichloromaleimide

A mixture of 2,6-diethanolamine (5 g, 36 mmol) and 75 ml SOCl2refluxed for 4 hours. The mixture is concentrated to half its volume and add toluene (50 ml). Then the solid formed after cooling, subjected to filtration and dissolved in water and the solution neutralized Panso3. J=7 Hz), the 4.7 (4H, s).

Sodium p - toluensulfonate

To a mixture of Na in dry EtOH (0.7 g, 29 mmol) is added p-toluensulfonate (5 g, 29 mmol) and the solution refluxed for 2 hours. After cooling, the resulting solid substance was filtered, washed with EtOH and dried (quantitative yield).

N,N’-detail-2,11-diaza[3.3](2,6) peridinian

To a solution of sodium p-toluensulfonate (of 1.93 g, 10 mmol) in 200 ml of dry dimethylformamide at 80 added slowly With 2,6-dichlorethylene (1,76 g, 10 mmol). After an hour add a new batch of sodium p-toluensulfonate (1,93 g) and the resulting mixture was stirred at 80 C for 4 hours. Then the solution is evaporated to dryness. The obtained solid is washed with water, then EtOH and finally subjected to crystallization in a mixture l3/Meon. The obtained solid is filtered and dried. Output (15) is 55%.

1H NMR (200 MHz, CDCl3) for 7.78 (4H, d, J=6 Hz), 7,45 (6N, m), to 7.15 (4H, d, J=6 Hz), 4,4 (8H, s), 2,4 (6N, C).

2,11-diaza[3.3] (2,6) peridinian

A mixture of N,N’-detail-2,11-diaza[3.3](2,6)pyridinoline (1,53 g, 2.8 mmol) and 14 ml of H2SO490% is heated at 110 C for 2 hours. The solution was cooled and diluted with 14 ml of water, then carefully poured into saturated tea 85% 2,11-diaza[3.3](2,6)peridinian.

1H NMR (200 MHz, CDCl3) and 7.1 (2H, t, J=7 Hz), 6,5 (4H, d, J=7 Hz), a 3.9 (8H, s).

N,N’-dimethyl-2,11-diaza[3.3](2,6) peridinian

The mixture 2,11-diaza[3.3](2,6) pyridinoline (or 0.57 g, 2.4 mmol), 120 ml of formic acid and 32 ml of formaldehyde (32% in water) is refluxed for 24 hours. Add concentrated Hcl (10 ml) and the solution is evaporated to dryness. The solid is dissolved in water, turn into the base, using 5M NaOH, and the resulting solution was extracted with l3. The obtained solid is purified by chromatography on alox (CH2Cl2+1% Meon), receiving 51% of N,N’-dimethyl-2,11-diaza[3.3](2,6) peridinian.

1H NMR (200 MHz, CDCl3) to 7.15 (2H, t, J=7 Hz), 6,8 (4H, d, J=7 Hz), a 3.9 (8H, s), 2,73 (6N, C).

(ii) Synthesis of the complex:

nF3(41,8 mg, 373 mmol) was dissolved in 5 ml Meon and to the solution was added N,N’-dimethyl-2,11-diaza[3.3](2,6) pyridinoline (0.1 g, 373 mmol) with 5 ml of tetrahydrofuran. After 30 minutes stirring at room temperature, add 4 ml of tetrahydrofuran saturated in Nbu4PF6and the solution is kept without stirring, until the end of crystallization. The product is collected by filtration, receiving 80% of the complex.

Elemental analysis found (theoretically):

% (38,35, 37,94), %N (11,32, 11/P>UV-Vis (CH3CN, nm, ): 500, 110; 850, 30;

(CH3SP/N2About:1/1, nm, ): 465, 168; 850, 30.

Example 7

Whitening spots tomato oil on fabric with added without the addition of [Fe(MeN4Py)(CH3CN)](ClO4)2immediately after washing (t=0) and after 24 hours (t=1 day)

In an aqueous solution containing 10 mm carbonate buffer (pH 10) without and with 0.6 g/l line Las (LAS) or containing 10 mm borate buffer (pH 8) without and with 0.6 g/l LAS, immerse napkins (6 of 6 cm) with spots of tomato and soybean oil and stirred for 30 minutes at 30 C. In the second series of experiments, the same test is carried out in the presence of 10 mm [Fe(MeN4Py)(CH3JV)](lO4)2indicated in table 1 as Fe(MeN4PY).

After washing, the cloth is dried in a drum dryer and measured reflectance using a spectrophotometer Minolta 3700d at 460 nm. The difference between the Reflectances before washing and after it is designated as the value R460.

The reflection coefficient napkins measure directly after washing (t=0) and after 24 hours of their stay in a dark room at ambient conditions (t=1 day). The results obtained are listed in table 1.

Example 8

Omoe directly after drying

In an aqueous solution containing 10 mm carbonate buffer (pH 10) without and with 0.6 g/l line Las (LAS) or containing 10 mm borate buffer (pH 8) without and with 0.6 g/l LAS, bring wipes with spots of tomato and soybean oil, which are in the solution under stirring for 30 minutes at 30 C. In the comparative experiments are conducted the same tests by adding 5 μm denuclearise or 10 μm mononuclear complex indicated in table 2.

After washing cloths rinsed with water, then dried at 30 C and directly after drying scanner Linotype-Hell (formerly Linotype) measure the color change. This change (including bleaching) is expressed as the value that is Measured color difference ( E) between the washed and nepotianus cloth is determined as follows:

E=[( L)2+( a)2+( b)2]1/2,

where L is a measure of the difference in darkness between the washed and nepotianus investigated tissues; a and b are measures of the difference in redness and yellowness between the two tissues, respectively. This method of color measurement described Commission International de l'éclairage (CIE); Recommendation on Uniform Colour Spaces, colour difference equations, psychometric color terms, supplement No. 2 to CIE Publication no 15, Colormetry. Bureau Central de la CIE, Paris, 1978.

Apply follow(1)

Synthesized in accordance with EP-B-458397;

ii) [Mn(LN4Me2)](=debtor [N,N’-dimethyl-2,11-diaza[3.3]-(2,6)-pyridinium]manganese(III)hexaphosphate) (2)

Synthesized as described previously;

iii) [Fe(OMe)LN4H2)Cl2](=Fe(2,11-diaza[3.3]-(4-methoxy)-(2,6) peridinian) Cl2) (3)

Synthesized as described previously;

iv) C12-CoCo (4)

Synthesized in accordance with EP-A-408131;

v) Mesosa (5)

Synthesized in accordance with EP-A-408131;

vi) [Fe(tpen)](ClO4)2(6)

Synthesized according to WO-A-9748787;

vii) [Fe (N,N,N’-Tris(pyridine-2-ylmethyl)-N-methyl-1,2-Ethylenediamine)CL](PF6)2(7)

Synthesized according to I. Bernal et al., J. Chem. Soc., Dalton Trans, 22, 3667 (1995);

viii) [Fe2(N,N,N’,N’-tetrakis(benzimidazole-2-ylmethyl)propan-2-ol-1,3-diamine) (ál-IT) (NO3)2]NO3)2(8)

Synthesized according to Brennan et al., Inorg. Chem., 30, 1937 (1991);

ix) [Mn2(tpen)( -O)( -SLA)](ClO4)2(9)

Synthesized according to Toftlund, H; Markiewicz, A.; Murray, K. S.; Acta Chem. Scamd., 44, 443 (1990);

x) [Mn (N,N,N’-Tris(pyridine-2-ylmethyl)-N’-methyl-1,2-Ethylenediamine)C1] (F6) (10)

Synthesized as follows:

-1) as a white solid (0,499 g, 86%). ESMS (m/z): 437 ([LMnCl]+).

xi) [MP2(N,N’-bis(pyridine-2-ylmethyl)-1,2-Ethylenediamine)2-( -O)2] (lO4)3(11)

Synthesized in accordance with Glerup, J.; Goodson, R. A.; Hazell, A.; Hazell, R.; Hodgson, D. J.; McKenzie, C. J.; Michelsen, K.; Rychlewska, U.; Toftlund, H. Inorg. Chem. (1994), 33(18), 4105-11;

xii) [MP(N,N’-bis(pyridine-2-ylmethyl)-N,N’-dimethyl-1, 2-these-Indiamen)2CL2] (12)

Synthesized as follows:

The triethylamine (0,405 g, 4 mmol) is a solution of the salt of the ligand bispicen (NMe) (0,416 g, 1 mmol) in anhydrous tetrahydrofuran (10 ml) (ligand for comparison: C. Li et al., J. Chem. Soc., Dalton Trans. (1991), 1909-14). The mixture is stirred at room temperature for 30 minutes. Add a few drops of methanol. The mixture is filtered and add it to the chloride manganese (0,198 g, 1 mmol) dissolved in tetrahydrofuran (1 t dry ether and dried in vacuum, getting 0,093 g complex (yield = 23%).

xiii) [Mn2(N,N,N’,N’-tetrakis(pyridine-2-ylmethyl) propane-1,3-diamine)( -O)( -SLA)2](lO4)2(13)

Synthesized as follows:

To mix the solution 6,56 g of 2-chloro-methylpyridine (40 mmol) and 0.75 ml of 1,3-propandiamine (9 mmol) in 40 ml of water slowly over 10 minutes at 70 With add 8 ml of 10 M NaOH solution. The color of the reaction changed from yellow to dark red. The solution is stirred for 30 minutes at 70 C, then cooled to room temperature. The reaction mixture was extracted with dichloromethane (total 200 ml), after which the red organic layer is dried over gSO4, filtered and evaporated under reduced pressure, getting 4,51 g of red-brown oil. After scraping the residue from the bottom of spatulas, it becomes hard; after you try washing the crude product with water, it becomes dirty, so cleaning cease immediately and dry the product with ether. For product analysis using NMR spectroscopy a sample is taken, after which the residue is immediately subjected to reaction with MP(SLA)3(see the formation of the complex).

1H NMR (400 MHz) (CDCl3); d (M. D.): 1,65 (kV-5, propane, 2H), 2.40 a (t, propane, 4H), 3,60 (s, N-CH2-feast, 8H), to 6.95 (t, PIR H4, 4 is of methanol at room temperature (22 C) added 2.76 g MP(SLA)3(0,0103 mol). The color of the reaction changed from orange to dark brown; after the addition the mixture is stirred for 30 minutes at room temperature and subjected to filtration. To the filtrate at room temperature add 1.44 g of NaClO4(0,0103 mmol) and the reaction mixture is subjected to stirring for another hour, filtered and dried with nitrogen, getting 0.73 g of a bright brown crystals (8%).

1H NMR (400 MHz) (CD3SP); d (M. D.): -42,66 (C), -15,43 (s) -4,8 (s, W), 0-10 (m, W), 13,81 (C), 45,82 (C), 49,28 (C), 60 (C, W), 79 (C, W), 96 (C, W)

IR/(cm-1): 3426, 1608 (C=C), 1563 (C=N), 1487, 1430 (M), 1090 (lO4), 1030, 767, 623.

UV/Vis (nm (l mol-1cm-1): 260 (2,4 104), 290 (sh), 370 (sh), 490 (5,1 102), 530 (sh; 3,4 102), 567 (sh), 715 (1,4 102).

Mass spectrum: (ESP+) m/z 782 [TPTN Mn(II)Mn(III) ( -OH)( -OAc)2(ClO4)-]+

SR(CH3SP): the complex does not lend itself ESR, which confirms the presence of Mn(II) Mn(III).

Elemental analysis: found (expected for MP2WITH31H38N6ABOUT14CL2(MW=899): 41,14 (41,4), N 4,1 (4,2), N 9,23 (9,34), O 24,8 (24,9), CL 7,72 (7,9), Mn 12,1 (12,2).

xiv) [Mn2(tpa)2(O2] (F6)3(14)

Synthesized according to D. K. TowIe, C. A. Botsford, D. J. Hodgso WO-A-9534628;

xvi) [Fe(MeN4Py)(CH3JV)](lO4)2(16)

Synthesized in accordance with EP-A-0909809.

The results:

Table 2: bleaching stains from tomato oil, expressed in E, obtained for different metal complexes, measured after 24 hours.

1. Whitening composition comprising in an aqueous medium, an organic substance of the formula L, which forms a complex with the transition metal, with the specified complex catalyses bleaching of the substrate by atmospheric oxygen, and water, in essence, does not contain peroxygen bleach or based on peroxide or forming its whitening system, where L is a ligand forming a complex of the General formula (A1)

in which M is a metal selected from MP(II) (III) (IV) (V), Fe(I)-(II)-(III)-(IV), Co(I)-(II)-(III), Ni(I)-(II)-(III), Ru(II)-(III) (IV) (V);

X - coordinating product selected from any mono-, bi - or triturating anions and any neutral molecules able to coordinate the metal mono-, bi - or tridentate way,

Y - any uncoordinated counterion;

and is an integer from 1 to 10;

k is an integer from 1 to 10;

n=0 or an integer from 1 to 10;

United or remote proton;

where g=0 or an integer from 1 to 6;

r is an integer from 1 to 6;

s=0 or an integer from 1 to 6;

Z1 and Z2 independently from each other represent a heteroatom or a heterocyclic or heteroaromatic ring, with Z1 and/or Z2 is optionally substituted by one or more functional groups E, with the following values;

Q1 and Q2 independently of one another represent a group of the formula

where 10 > (d+e+f) > 1; d=0-9; e=0-9; f=0-9;

each Y1 is independently selected from -(G1)N-, -(G1)(G2)N- (where G1and G2have the following values), -C(O)-, arylene, alkylene;

if s>1, each -[-Z1(R1)-(Q1)r-]- the group has a specific value;

R1, R2, R6-R9 independently of one another represent a group selected from hydrogen, hydroxyl, -OR (where R = alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl or carbonylation group), the OAS, alkyl, alkenyl, cycloalkyl, geterotsiklicheskie, aryl, heteroaryl, and carbamylphosphate groups, each of R, AG, alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl and carbamylphosphate groups optionally substituted by one or oxygen;

E is chosen from the functional groups containing nitrogen, and any electron-donor and/or acceptor groups (E. preferably selected from hydroxy-, mono - or polycarboxylate derivatives, aryl, electron-donating groups and electroncapture groups and groups of formula (G1)(G2)N-, (G1)(G2)(G3)N-, (G1)(G2)N-C(O)-, G3O - and G3C(O)-, where each of G1, G2and G3independently from each other selected from hydrogen, alkyl, electron-donating and electron-withdrawing groups (in addition to any among the above groups);

either one of R1-R9 is a bridge group associated with another residue, having the same General formula;

T1 and T2 independently of one another represent groups of R4 and R5, where R4 and R5 have the meanings indicated for R1-R9, and if g=0, a s>0, then R1 together with R4 and/or R2 together with R5 may optionally independently from each other represent =CH-R10, where R10 has the meanings indicated for R1-R9, or T1 and T2 together (-T2-T1) can be a covalent bond when s>1 and g>0;

if Z1 and/or Z2 represents N, T1 and T2 together represent a simple bond, and R1 and/or R2 are absent, Q1 and/or Q2 may independently on the e from R1, R2, R6-R9 are independently from each other are linked together by covalent linkage;

if Z1 and/or Z2 represents N, then R1 and/or R2 may be absent;

if Z1 and/or Z2 represent a heteroatom, substituted functional group, then R1 and/or R2 and/or R4 and/or R5 may be absent.

2. Whitening composition under item 1, in which Z1 and Z2 independently of one another represent an optionally substituted heteroatom selected from N, P, O, S, and Si, or optionally substituted heterocyclic or optionally substituted heteroaromatic ring selected from pyridine, pyrimidine, pyrazine, pyrimidine, pyrazole, pyrrole, imidazole, benzimidazole, chinoline, isoquinoline, carbazole, indole, isoindole, furan, thiophene, oxazole and thiazole.

3. Whitening composition under item 1 or 2, in which R1 to R9 independently from each other selected from-H, hydroxy-C0-C20-alkyl, halo-C0-C20-alkyl, nitroso, formyl-C0-C20-alkyl, carboxy-C0-C20-alkyl, their esters and salts, carbarnoyl-C0-C20-alkyl, as well as their esters and salts, amino-C0-C20-alkyl, aryl-C0-C20-alkyl, heteroaryl-C0cocci, aryl-C0-C6-alkyl and C0-C20-alkylamide; or one of R1-R9 is a bridging group,- Cn’(R11)(R12)-(D)p-Cm’ (R11)(R12) - associated with another remnant of the same General formula, where p=0 or 1, D is selected from a heteroatom or heteroaromatics group or is part of an aromatic or saturated homonuclear or heteronuclear ring, n’ is an integer from 1 to 4, m’ is an integer from 1 to 4, provided that each of the n’+m’ 4, R11 and R12 independently from each other preferably selected from N, NR13, and OR14, alkyl, aryl, optionally substituted, and each of R13 and R14 independently from each other selected from-H, alkyl, aryl, both they are not necessarily replaced.

4. Whitening composition according to any one of paragraphs.1-3, in which T1 and T2 together form a simple link, a s>1 in accordance with the General formula (BII)

where Z3 independently represents a group having the values specified for Z1 or Z2;

R3 independently represents a group having the values shown for R1-R9;

Q3 independently represents a group having the values specified for Q1, Q2;

h=0 or an integer from 1 to 6;

s’=s-1.

5. Whitening composition on p. 4, which the ligand has the General formula, select from

7. Whitening composition on p. 6, in which the ligand has the General formula selected from

8. Whitening composition on p. 7, in which R1-R4 independently from each other selected from-H, alkyl, heteroaryl or represent a bridging group associated with a different balance of the same General formula, thus bridging group is alkylene, or hydroxyalkyl or heteroarylboronic bridge.

9. Whitening composition under item 8, in which R1-R4 independently from each other selected from-H, methyl, ethyl, isopropyl, nitrogen heteroaryl or bridging group linked to another remnant of the same General formula, thus bridging group is alkylene or hydroxyalkyl.

10. Whitening composition on p. 4, in which in the General formula (BII), s’=2; r=g=h=1; d=f=0; f=1, and each Y1 is independently from each other represents alkylene or heteroaryl.

11. Whitening composition according to p. 10, in which the ligand has General formula

where A1AND2AND3AND4independently of each other represent a heteroatom or heteroarenes group.

12. Whitening composition on p. 11, where N1represents an aliphatic nitrogen; N2represents vegerarian group; each of R1-R4 independently of one another represent H, alkyl, aryl or heteroaryl and each AND1AND2AND3AND4represents-CH2-.

13. Whitening composition according to p. 12, in which the ligand has General formula

where each of R1 and R2 independently from each other represents-H, alkyl, aryl or heteroaryl.

14. Whitening composition on p. 4, in which in the General formula (BII) s’=2, a r=g=h=1, in accordance with the General formula

15. Whitening composition according to p. 14, in which Z1=Z2=Z3=Z4=heteroaromatic ring; e=f=0; d=1; a R7 is absent.

16. Whitening composition according to p. 14, in which each of Z1-Z4 represents N; R1-R4 are absent; both Q1 and Q3 are =CH-[-Y1-]e-CH=; and both Q2 and Q4 represents-CH2-[-Y1-]n-CH2-.

17. Whitening composition according to p. 16, in which the ligand has General formula

where a represents an optionally substituted alkylene, optionally interrupted by a heteroatom; n=0 or an integer B>-, -CHOH-, -CH2N(R)CH2- or-CH2CH2N(R)CH2CH2- where R represents hydrogen or alkyl.

19. Whitening composition on p. 18, in which A=-CH2-, -CHOH - or-CH2CH2NHCH2CH2-.

20. Whitening composition according to any one of paragraphs.1-3, in which T1 and T2 independently of one another represent groups of R4 and R5 has the values listed for R1-R9, in accordance with the General formula (BIII)

21. Whitening composition according to p. 20, in which in the General formula (BIII) s=1; r=1; g=0; d=f=1; e=1-4; Y1=-CH2-; R1 together with R4 and/or R2 together with R5 independently of one another represent =CH-R10, where R10 has the meanings indicated for R1-R9.

22. Whitening composition according to p. 21, in which R2 together with R5 represents =CH-R10.

23. Whitening composition under item 21 or 22, in which the ligand is chosen from

24. Whitening composition on p. 23, in which the ligand is chosen from

where R1 and R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-Akilov;

R3 and R4 are selected from-H, alkyl, aryl, optionally substituted phenols, heteroaryl-C0-C20-Akilov, alkylaryl, aminoalkyl, alkoxy.

26. Whitening composition according to p. 20, in which in the General formula (BIII) s=1; r=1; g=0; d=f=1; e=1-4; Y1=-C(R’)(R’) where R’ and R’ independently of one another have the meanings indicated for R1-R9.

27. Whitening composition on p. 26, in which the ligand has General formula

28. Whitening composition according to p. 27, in which R1-R5 are-H or C0-C20-alkyl, n=0 or 1, R6 represents-H, alkyl, -HE, and each of R7-R10, independently from each other selected from-H0-C20-alkyl, heteroaryl-C0-C20-alkyl, alkoxy-C0-C8-alkyl, amino-C0-C20-alkyl.

29. Whitening composition according to p. 20, in which in the General formula (BIII) s=0; g=1; d=e=0; f=1-4.

30. Whitening composition according to p. 29, in which the ligand has General formula

31. Whitening composition on p. 30, provided that none of R1-R3 is not a hydrogen.

32. Whitening composition on p. 30 or 31, in which the ligand has the General formula:

where R1, R2, R3 have the values listed for R2, R4, R5.

uly (IN)

where each of R1, R2 independently from each other represents-R4-R5;

R3represents hydrogen, optionally substituted alkyl, aryl, or arylalkyl, or R4-R5;

each of R4independently from each other represents a simple bond or optionally substituted alkylene, albaniles, oxyalkylene, aminoalkyl, alkalinity ether, ester or carboxylic acid amide and

each of R5independently represents an optionally N-substituted aminoalkyl or optional substituted heteroaryl selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.

34. Whitening composition on p. 33, provided that R3does not represent hydrogen.

35. Whitening composition according to any one of paragraphs.1-3, in which L represents pentadentate or hexadentate ligand of General formula (C):

R1R1N-W-NR1R2

where each of R1independently represents-R3-V, in which R3is optionally substituted alkylene, albaniles, oxyalkyl is from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;

W represents an optionally substituted alkylenes bridging group selected from-CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2-, -CH2-C10H6-CH2-;

R2represents a group selected from R1and the alkyl, aryl and arylalkyl, optionally substituted Deputy selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, ester of carboxylic acid, amine, alkylamine and N+(R4)3where R4selected from hydrogen, alkenyl, alkenyl, arylalkyl, arylalkyl, oxyalkyl, oxyalkyl, aminoalkyl, aminoalkyl, alonelove and alkenilovyh ether.

36. Whitening composition according to any one of paragraphs.1-3, in which L represents a macrocyclic ligand of formula (E)

where Z1and Z2independently from each other selected from monocyclic or polycyclic aromatic ring structure, optionally containing od the deputies;

Y1and Y2independently from each other selected from the atoms C, N, O;

AND1and2independently from each other selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of the last three compounds are optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, electron-donating and elektronoaktseptornymi groups and groups of formula (G1)(G2)N-, G3OC(O)-, G3O - and G3C(O)-, where each of G1, G2and G3independently from each other selected from hydrogen and alkyl, and electron-donating and/or electron-withdrawing groups (in addition to the groups contained in the above compounds);

i and j are selected from 0, 1 and 2, completing the valence of the groups Y1and Y2;

each of Q1-Q4independently from each other selected from groups of the formula

where 10 > (a+b+C) > 2;

each of the Y3independently selected from (G1)(G2)N-, -(G1)N- (where G1and G2have the above values), -C(O)-, aryl, heteroaryl;

each AND3-AND6independently from each other selected from groups having the above values for a AND1and2; and

2bound without the simultaneous binding with any of the3-AND6then the bridging group linking AND1and2must contain at least one carbonyl group.

37. Whitening composition according to any one of paragraphs.1-36, in which in the formula (A1) X - coordinating product selected from O2-, RBO2-2, RCOO-, RCONR-HE-NO-3NO-2, NO, CO, S2-RS-, RHO4-3derived from anions of sodium tripolyphosphate (STP-anions), RHO3OR SIG3-N2OH, WITH2-3HCO-3, ROH, NRR'R’, RCN, Cl-, VG-, OCN-, SCN-CN-N-3, F-I-, RO-, ClO-4SO2-4, HSO-4, SO2-3, RS-3; and Y is a counterion selected from ClO-4, VG-4, [FeCl4]-PF-6, RCOO-NO-3NO-2, RO-N+RR'R’R’’, CL-, Br-, F-I-, RS-3, S2ABOUT2-6, OCN-, SCN-Li+, Ba2+, Na+, Mg2+, K+Ca2+Cs+PR+4, RBO2-2SO2-4, HSO-2
PO-4obtained from S anions, WITH2-3HCO-3and BF-4where R, R’, R’, R’’ independently of one another represent a group selected from hydrogen, hydroxyl, -OR (where R = alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl or carbonylation group), the OAS, alkyl, alkenyl, cycloalkyl, geterotsiklicheskie, aryl, heteroaryl and carbamylphosphate groups, each of R, AG, alkyl, alkenyl, cycloalkyl, heteroseksualci, aryl, heteroaryl and carbamylphosphate groups optionally substituted by one or more functional groups E, or R6 together with R7 and R8 independently together with R9 represent oxygen; E is chosen from the functional groups containing nitrogen, and any electron-donor and/or acceptor groups.

38. Whitening composition on PP.1-37, in which in the formula (A1) M is a metal selected from MP(II) (III) (IV) (V), Fe(II)-(III)-(IV) and Co(I)-(II)-(III); X - coordinate product selected from O2-, RBO2-2, RCOO-HE-, NR-3NO-2, NO, CO, CN-S2-RS-, RHO4-3N2O,2-3HCO-3, ROH, NRR'R’, Cl-, Br-, OCN-, SCN-, SO2-3and RSO-3; Y is a counterion selected from lO-4, VG-4, [FeCl4]-PF-6, RCOO-NO-3NO-2, RO-N+RR'R’R’’, Cl-, Br-, F-I-, RSO-3, S2O2-6, OCN-, SCN-Li+, Ba2+, Na+, Mg2+, K+Ca2+PR+4SO2-4, HSO-4, SO2-3and BF-4where R, R’, R’, R’’ represent hydrogen, optionally substituted alkyl or optionally substituted aryl; and a is an integer from 1 to 4; k is an integer from 1 to 10; n=0 or an integer from 1 to 4, and m=0 or an integer from 1 to 8.

39. Whitening composition according to any one of paragraphs.1-36, in which the complex [MaLkXn]Ym: M = Mn (II)-(IV), Fe (II)-(III), Co (II)-(III); X = CH3CN, OH2, Cl-, Br-, OCN-N-3, SCN-HE-ABOUT2-, RHO3-4C6H5BO2-2, RCOO-; Y = ClO-4, BPh-4, Br-, Cl-, [FeCl4]-PF-6NO-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.

40. Whitening composition according to any one of PR is CLASS="ptx2">

41. Whitening composition according to p. 40, which once added to the water environment provides a pH in the range from 8 to 10.

42. Whitening composition according to any one of the preceding paragraphs, which once added to the aqueous medium leads to the production environment, essentially, not containing sequestrant transition metal.

43. Whitening composition according to any one of the preceding paragraphs, which once added to the aqueous medium leads to the production environment, including surface-active substance.

44. Whitening composition according to any one of the preceding paragraphs, which once added to the aqueous medium leads to the production environment, including modifying additive.

45. Whitening composition according to any one of the preceding paragraphs, in which the organic substance includes a pre-formed complex of the ligand and the transition metal.

46. Whitening composition according to any one of the preceding paragraphs, in which the organic substance includes free ligand forming a complex with a transition metal present in the water.

47. Whitening composition according to any one of the preceding paragraphs, in which organic substances

48. Whitening composition according to any one of the preceding paragraphs, in which the organic substance comprises a composition of a free ligand or a complex of the metal - ligand, substituted transition metal, and a source of transition metal.

49. Method of bleaching a substrate comprising applying to it the whitening composition in the aqueous medium according to any one of paragraphs.1-48.

50. The method according to p. 49, in which a large part of bleach in the environment (based on equivalent weight) is obtained from atmospheric oxygen.

51. The method according to p. 49, in which the environment is, in essence, does not contain peroxygen bleach or based on peroxide or forming its whitening system.

52. The method according to any of paragraphs.49-51, in which the aqueous medium is stirred.

 

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