KR20080099255A - Use of metal complex compounds as oxidation catatlysts - Google Patents

Abstract

The present invention relates to the use, as oxidation catalysts, of metal complex compounds having tetradentate ligands of formula (2) wherein all subsitutents have the meanings as defined in Claim 1. The present invention relates also to formulations comprising such metal complex compounds, to novel metal complex compounds and to novel ligands.

Description

Use of metal complex compounds as oxidation catatlysts

The present invention relates to the use as a catalyst for oxidation of tetradentate ligands or metal complex compounds having mixtures of such ligands. The present invention relates to formulations, novel metal complex compounds and novel ligands comprising such metal complex compounds.

Metal complex compounds are used to enhance the action of peroxides in the treatment of textile materials without causing any recognizable damage to the fibers or dyeing. If these metal complexes are used in combination with enzymes or mixtures of enzymes, there is no appreciable damage to the fibers and the dyeing.

Metal complex compounds can be used as catalysts for oxidation with molecular oxygen and / or air free of peroxide compounds and / or peroxide forming materials. Bleaching of the fabric may occur during and / or after treating the fibers with the blend comprising the metal complex.

Peroxide-containing bleaches have long been used in cleaning and cleaning processes. They have an excellent action at liquid temperatures above 90 ° C., but their performance is significantly reduced at low temperatures. Various transition metal ions and coordination compounds containing such cations added to the formation of suitable salts are known to activate H ₂ O ₂ . In this way, the bleaching effect of precursors and other peroxo compounds that release H ₂ O ₂ or H ₂ O ₂ which was insufficient at low temperatures can be improved. In this respect it is important that combinations of transition metal ions and ligands with predominant peroxide activation have an increased tendency for oxidation and catalase-like disproportionate to the substrate. The latter activation, which tends to be undesirable in the case of the present invention, can impair the bleaching effect of H ₂ O ₂ and its derivatives which are inappropriate at low temperatures.

In terms of H ₂ O ₂ activation with an effective bleaching action, mononuclear complexes of manganese complexes with various ligands, in particular 1,4,7-trimethyl-1,4,7-triazacyclononane and optionally oxygen-containing bridge ligands And multinuclear variants are currently considered to be particularly effective. Such catalysts are suitably stable under practical conditions and contain ecologically acceptable metal cations with Mn ^{n +} , but their use is unfortunately associated with significant damage to dyeing and fibers.

It was an object of the present invention to provide an improved metal complex catalyst for an oxidation process that satisfies the above requirements and in particular enhances the action of peroxide compounds in various applications without causing recognizable damage.

The present invention therefore relates to the use as a catalyst for the oxidation of at least one metal complex of formula (1):

In the formula,

Me is manganese, titanium, iron, cobalt, nickel or copper,

X is a coordination radical or a bridge radical,

n and m are each independently an integer having a value of 1 to 8,

p is an integer having a value from 0 to 32,

z is the charge of the metal complex,

Y is a large ion,

q is z / (charge of Y), and

L is the following formula (2)

의 리간드이고,

Is a ligand of

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen; Unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉

Wherein R ₉ is hydrogen, cation or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively;

SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ ,

Wherein R ₁₀ is hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively;

-NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ^® R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N [(C ₁ -C ₆ alkylene) -NR ₁₁ R _{12] 2;} -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ^® R ₁₁ R ₁₂ R ₁₃ ; -N [(C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13] 2; -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ^® R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is as defined above and

R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, or

R ₁₁ and R ₁₂ combine with the nitrogen atom connecting them to form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain additional hetero atoms,

Q is N or CR ₈ Wherein R ₈ has the same meaning as defined for R ₁ -R ₇ or

를 형성하며, R ₈ is combined with A

Form the

Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 are independently of each other H, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,

Q ₁ Is N or CR ' ₈ Wherein R ' ₈ has the same meaning as defined in R ₁ -R ₇ ,

A has _one of the meanings as defined in R ₁ -R ₇ , or

A is combined with R ₈

를 형성하며,

Form the

Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 have the same meaning as defined above and b and c are independently 1, 2 or 3 of each other.

Suitable substituents for the alkyl group, aryl group, alkylene group or 5-, 6- or 7-membered ring are in particular C ₁ -C ₄ alkyl; C ₁ -C ₄ alkoxy; Hydroxy; Sulfo; Sulfato; halogen; Cyano; Nitro; Carboxy; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxy at the alkyl moiety; N-phenylamino; N-naphthylamino; Phenyl; Phenoxy or naphthyloxy.

C ₁ -C ₁₈ mentioned in compounds of formula (2) Alkyl radicals are for example straight or branched chain alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl or straight or branched pentyl, hexyl, heptyl or octyl . C ₁ -C ₁₂ alkyl radicals, in particular C ₁ -C ₈ alkyl radicals and preferably C ₁ -C ₄ alkyl radicals. The alkyl radicals mentioned above may be unsubstituted or substituted, for example by hydroxy, C ₁ -C ₄ alkoxy, sulfo or by sulfato, in particular by hydroxy. Corresponding unsubstituted alkyl radicals are preferred. Very particular preference is given to methyl and ethyl, especially methyl.

Examples of aryl radicals to be considered for compounds of formula (2) are unsubstituted or substituted, respectively, or C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, N-mono- or N, N-di-C ₁ -C ₄ alkylamino, N-phenylamino, phenyl or naphthyl substituted by hydroxy at an unsubstituted or alkyl moiety and In this case, the amino group may be quaternized phenyl, phenoxy or naphthyloxy. Preferred substituents are C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl and hydroxy. Especially preferred are the corresponding phenyl radicals.

The C ₁ -C ₆ alkylene groups mentioned for formula (2) are, for example, straight or branched alkylene radicals, such as methylene, ethylene, n-propylene or n-butylene. Preferred are C ₁ -C ₄ alkylene groups. The alkylene radicals mentioned above may be unsubstituted or substituted, such as by hydroxy or C ₁ -C ₄ alkoxy.

In the compounds of the formulas (1) and (2), the halogen is preferably chlorine, bromine or fluorine, with chlorine being particularly preferred.

Examples of cations that may be considered for the compounds of formulas (1) and (2) include alkali metal cations such as lithium, potassium and especially sodium, alkaline earth metal cations such as magnesium and calcium, and ammonium cations. Alkali metal cations, in particular sodium, are preferred.

Suitable metal ions for Me of the compound of formula (1) are, for example, manganese in oxidation state II-V, titanium in oxidation states III and IV, iron in oxidation states I to IV, cobalt in oxidation states I to III, oxidation state I Nickel of the formula (III) to (III) and copper of the oxidation states (I) to (III), and manganese, in particular manganese of the oxidation states II to IV, preferably manganese in the oxidation state II Titanium IV, iron II-IV, cobalt II-III, nickel II-III and copper II-III, in particular iron II-IV, are also important.

With regard to the radical X of the compound of formula (1), one can consider, for example, CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; R ₁₆ O ^-; LMeO ^— and LMeOO ^— wherein R ₁₆ is hydrogen, —SO ₃ C ₁ -C ₄ alkyl or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, and C ₁ -C ₁₈ alkyl , Aryl, L and Me may have the above definitions and the preferred definitions above and below. Especially preferably, R ₁₆ is hydrogen; C ₁ -C ₄ alkyl; Sulfophenyl or phenyl, especially hydrogen.

Examples of counterions Y for the compound of formula (1) include, for example, R ₁₇ COO ⁻ ; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ⁻ and I ⁻ may be considered where R ₁₇ is hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl. R ₁₇ as C ₁ -C ₁₈ alkyl or aryl has the above definitions and the preferred meanings above and below. Particularly preferably R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl or sulfophenyl, in particular hydrogen or 4-sulfophenyl. The charge of the counterion Y is therefore preferably 1- or 2-, in particular 1-.

Y is a conventional organic counterion such as citrate, oxalate or tartrate. In the compound of the formula (1), n is preferably an integer of 1 to 4, preferably 1 or 2, especially 1.

In the compounds of the formula (1), m is preferably an integer having a value of 1 or 2, in particular 1.

In the compounds of the formula (1), p is preferably an integer, in particular 2, having a value from 0 to 4.

In the compounds of formula (1), z is preferably an integer having a value of 8- to 8+, in particular 4- to 4+, particularly preferably 0 to 4+. z is more particularly zero.

In the compounds of formula (1), q is an integer from 0 to 8, in particular an integer from 0 to 4, particularly preferably 0.

R ₉ in the compound of formula (2) is hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above. Especially preferably, R ₉ is hydrogen, alkali metal cation, alkaline earth metal cation or ammonium cation, C ₁ -C ₄ alkyl or phenyl, in particular hydrogen or alkali metal cation, alkaline earth metal cation or ammonium cation.

R ₁₀ in formula (2) is preferably hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above. Especially preferably, R ₁₀ is hydrogen, C ₁ -C ₄ alkyl or phenyl, more particularly hydrogen or C ₁ -C ₄ alkyl, preferably hydrogen. Examples of radicals of the formula -OR ₁₀ which may be mentioned are C ₁ -C ₄ alkoxy such as hydroxy and methoxy and especially ethoxy.

When R ₁₁ and R ₁₂ in formula (2) combine with the nitrogen atom connecting them to form a 5-, 6- or 7-membered ring, the ring is preferably unsubstituted or C ₁ -C ₄ alkyl-substituted Imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan ring, wherein the amino group may be quaternized, in which case it is preferably not directly attached to the pyridine or pyrimidine ring The nitrogen atom is quaternized. The piperazine ring may be substituted at the nitrogen atom which is not bound to the pyridine ring, for example by one or two unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C ₄ alkyl. In addition, R ₁₁ , R ₁₂ and R ₁₃ are preferably hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, unsubstituted phenyl or phenyl substituted as above. Especially preferred are hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₄ alkyl or unsubstituted or hydroxy-substituted phenyl, in particular hydrogen or unsubstituted or hydroxy-substituted C ₁ -C ₄ alkyl, preferably Is hydrogen.

R ₃ in formula (2) is preferably C ₁ -C ₁₂ alkyl; Phenyl unsubstituted or N-mono-substituted by hydroxy at C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, unsubstituted or alkyl moieties Or phenyl substituted by N, N-di-C ₁ -C ₄ alkylamino, N-phenyl-amino, N-naphthylamino, phenyl, phenoxy or naphthyloxy; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ , wherein R ₉ in each case is hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ wherein R ₁₀ in each case is hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N + R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ has one of the above meanings and R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, unsubstituted phenyl Or substituted phenyl as indicated above, or R ₁₁ and R _12, in combination with the nitrogen atom connecting them, are unsubstituted or one or more unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C ₄ alkyl To form an imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan ring substituted by the nitrogen atom, which may be quaternized.

R ₃ in L of formula (2) is particularly preferably unsubstituted phenyl or phenyl substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, phenyl or hydroxy; Cyano; Nitro; -COOR ₉ or -SO ₃ R _{9 wherein} R ₉ is in each case hydrogen, cation, C ₁ -C ₄ alkyl or phenyl; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ wherein R ₁₀ in each case is hydrogen, C ₁ -C ₄ alkyl or phenyl; -N (R ₁₀ ) -CH ₂ CH ₂ -R _α wherein R ₁₀ is as defined above and R _α is unsubstituted or at least one unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C ₄ Imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan rings substituted by alkyl, wherein the nitrogen atom may be quaternized; -N (CH ₃ ) -NH ₂ or -NH-NH ₂ ; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxy at the alkyl moiety; Or an unsubstituted or C ₁ -C ₄ alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepan ring.

R ₃ in L of formula (2) is very particularly preferably C ₁ -C ₄ alkoxy; Hydroxy; Unsubstituted phenyl or phenyl substituted by C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, phenyl or hydroxy; -N (R ₁₀ ) -CH ₂ CH ₂ -R _α , wherein R ₁₀ is H or C ₁ -C ₂ alkyl and R _α is unsubstituted or substituted by _one or more unsubstituted C ₁ -C ₂ alkyl Imidazole or pyrazole, and the nitrogen atom is quaternized; Hydrazine; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxy at the alkyl moiety; Or an unsubstituted or C ₁ -C ₄ alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepan ring.

Of particular importance as radical R ₃ in L of Formula (2) are C ₁ -C ₄ alkoxy; Hydroxy; -N (R ₁₀ ) -CH ₂ CH ₂ -R _α , wherein R ₁₀ is H or C ₁ -C ₂ alkyl and R _α is unsubstituted or substituted by one or more unsubstituted C ₁ -C ₂ alkyl Imidazole or pyrazole ring, wherein the nitrogen atom may be quaternized; Hydrazine; Amino; N-mono- or N, N-di-C ₁ -C ₄ alkylamino unsubstituted or substituted by hydroxy at the alkyl moiety; Unsubstituted or C ₁ -C ₄ alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepan rings.

Most particularly important as the radical R ₃ in L of Formula (2) are C ₁ -C ₄ alkoxy; Hydroxy; -N (R ₁₀ ) -CH ₂ CH ₂ -R _α , wherein R ₁₀ is H or C ₁ -C ₂ alkyl and R _α is unsubstituted or substituted by one or more unsubstituted C ₁ -C ₂ alkyl Imidazole or pyrazole ring, wherein the nitrogen atom may be quaternized; N-mono- or N, N-di-C ₁ -C ₂ alkylamino substituted by hydroxy at alkyl moiety; Unsubstituted or C ₁ -C ₂ alkyl-substituted pyrrolidine, piperidine, piperazine, morpholine or azepan rings. Of these, hydroxy is particularly important.

Preferred meanings given above for R ₃ are R ₁ , R ₂ , R ₄ , R ₅ , R ₆ and R ₇ in L of formula (2), but these radicals may additionally be hydrogen.

Q ₁ is preferably N; CH; Or CR ' _8, wherein R' ₈ Is preferably C ₁ -C ₁₂ alkyl; Unsubstituted phenyl or N-mono-substituted by hydroxy at C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, unsubstituted or alkyl moieties Or phenyl substituted by N, N-di-C ₁ -C ₄ alkylamino, N-phenylamino, N-naphthylamino, phenyl, phenoxy or naphthyloxy; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ , wherein R ₉ is in each case hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or phenyl substituted as above; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , wherein R ₁₀ is in each case hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or phenyl substituted as above; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N + R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is one of the meanings given above and R ₁₁ , R ₁₂ and R ₁₃ are each independently of one another hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, unsubstituted phenyl or Or phenyl substituted as above, or R ₁₁ and R ₁₂ are combined with the nitrogen atom connecting them to be substituted by unsubstituted or one or more unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C ₄ alkyl Imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan ring, wherein the nitrogen atom may be quaternized.

Q is preferably N; CH; Or CR ₈ , wherein R ₈ is preferably C ₁ -C ₁₂ alkyl; Unsubstituted phenyl or N-mono-substituted by hydroxy at C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, unsubstituted or alkyl moieties Or phenyl substituted by N, N-di-C ₁ -C ₄ alkylamino, N-phenyl-amino, N-naphthylamino, phenyl, phenoxy or naphthyloxy; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ , wherein R ₉ is in each case hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or phenyl substituted as above; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , wherein R ₁₀ in each case is hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N + R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is one of the meanings given above and R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, unsubstituted phenyl or Substituted phenyl as shown, or R ₁₁ and R ₁₂ Is combined with the nitrogen atom connecting them to be substituted by unsubstituted or one or more unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C ₄ alkyl imidazole, pyrazole, pyrrolidine, piperi Dean, piperazine, form a morpholine or azepane ring, wherein the nitrogen atom is quaternized, or Q and a is -CH ₂ -CH ₂ with _{-, -CH 2 -CHR "15 -} , -CH 2 -CR _{"15 R"'15 -,} -CHR 15 -CH 2 -, -CHR 15 -CHR "15 -, -CHR 15 -CR" 15 R "' 15 -, -CR 15 R '15 -CH 2 -, - _{CR 15 R '15 -CHR "15} -, -CR 15 R' 15 -CR" 15 R "'15 -, -CH = CH-, -CR 14 = CR' 14 -, -CH = CR '14 - or -CR ₁₄ = CH- to form a bridge, wherein _{R 14, R '14, R} 15, R' 15, R "15 and R"_'15 are each independently C ₁ -C ₂ - alkyl.

A is preferably C ₁ -C ₁₂ alkyl; Unsubstituted phenyl or N-mono-substituted by hydroxy at C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, unsubstituted or alkyl moieties Or phenyl substituted by N, N-di-C ₁ -C ₄ alkylamino, N-phenylamino, N-naphthylamino, phenyl, phenoxy or naphthyloxy; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ , wherein R ₉ is in each case hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , wherein R ₁₀ in each case is hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N + R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -NR ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ may have one of the meanings indicated above and R ₁₁ , R ₁₂ and R ₁₃ are each independently of each other hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, unsubstituted phenyl or Substituted phenyl as indicated above, or R ₁₁ and R ₁₂ are combined with the nitrogen atom connecting them and unsubstituted or substituted with one or more unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C ₄ alkyl Form a substituted imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan ring, wherein the nitrogen atom is quaternized or

A is combined with Q

를 형성하며, 이때 R₁₄, R'₁₄, R₁₅, R'₁₅, R"₁₅ 및 R"'₁₅ 는 독립적으로 서로 C₁-C₂-알킬이다. or

Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 are independently of each other C ₁ -C ₂ -alkyl.

Preferred embodiments of the invention relate to the use as a catalyst for the oxidation reaction of one or more metal complexes of formula (1 '):

In the formula,

Me 'is manganese, titanium, iron, cobalt, nickel or copper,

X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And is, at this time, R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O

n 'is an integer with a value of 1 or 2,

m 'is an integer having a value of 1 or 2, preferably 1,

p 'is an integer having a value from 0 to 4, in particular 2,

z 'is an integer having a value of 8- 8+, preferably of 4--4 +, more preferably of 0-4 +, in particular of 0,

Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate and tartrate, or, wherein R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl or sulfophenyl,

q 'is an integer from 0 to 8, preferably 0 to 4, more preferably 0,

L 'is formula (2a), (2b) or (2c)

Is a ligand of which all substituents have the same meanings as defined in formula (2).

A more preferred aspect of the invention relates to the use as a catalyst for the oxidation reaction of one or more metal complexes of formula (1 '):

In the formula,

Me 'is manganese, titanium, iron, cobalt, nickel or copper,

X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And a, wherein R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O

n 'is an integer with a value of 1 or 2,

m 'is an integer with a value of 1,

p 'is an integer with a value of 2,

z 'is an integer having a value of 4 to 4+, preferably 0 to 4+, particularly preferably 0,

Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate and tartrate, or, wherein R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl, or sulfophenyl,

q is an integer from 0 to 4, preferably 0,

L 'is the following formula (2a), (2b) or (2d)

Is a ligand of

Where R ₁ , R ₂ , R ₄ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ' ₈ and A are each independently hydrogen; Unsubstituted C ₁ -C ₁₂ alkyl; C ₁ -C ₁₂ alkyl substituted by one or more substituents selected from the group consisting of —OH, —CN, —NH ₂ , COOH and COOC ₁ -C ₂ alkyl; Unsubstituted phenyl or N-mono-substituted by hydroxy at C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, unsubstituted or alkyl moieties Or phenyl substituted by N, N-di-C ₁ -C ₄ alkylamino, N-phenyl-amino, N-naphthylamino, phenyl, phenoxy or naphthyloxy; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ , wherein R ₉ is in each case hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or phenyl substituted as above; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , wherein R ₁₀ in each case is hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N + R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is hydrogen, C ₁ -C ₄ alkyl or phenyl and R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, Unsubstituted phenyl or substituted phenyl as indicated above, or R ₁₁ and R ₁₂ , combined with the nitrogen atom connecting them, are unsubstituted or one or more unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C _An imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan ring substituted by ₄ alkyl, wherein the nitrogen atom is quaternized.

As examples of the radical R ₃ in L ′ of the formulas (2a), (2b), (2c) and (2d), the following can be exemplified: -CH ₃ ; -Cl; -OH; -OCH ₃ ; -CH ₂ CN; -CH ₂ CH ₂ CN; -CH ₂ COOH; -CH ₂ CH ₂ COOH;

 Of these, hydroxy is particularly important.

The preferred meanings given for R ₃ in L 'of formulas (2a) and (2b) also apply to R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R' ₈ and A, These radicals may additionally be hydrogen.

Particularly preferred embodiments of the present invention relate to the use as a catalyst for the oxidation of at least one metal complex of formula (1 '):

In the formula,

Me 'is manganese or iron,

X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And a, R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O

n 'is an integer with a value of 1 or 2,

m 'is an integer with a value of 1,

p 'is an integer with a value of 2,

z 'is an integer having a value of 0 to 4+, preferably 0,

Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate or tartrate, R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl or sulfophenyl,

q 'is an integer having a value of 0 to 4, preferably 0,

L 'is the following formula (2'a), (2'b) or (2'd)

Is a ligand of

Wherein R ₁ and R ₄ are independently of each other H; -CH ₃ ; -Cl; -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ;

ego,

A and R ₂ are independently of each other H or -CH ₃ ,

이고, R ₃ is -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ );

ego,

R ₈ and R ₆ are each independently hydrogen; -CH ₃ ; -Cl; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ ); -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₂ CH ₃ ) (CH ₂ CH ₂ OH) or -N (CH ₃ ) CH ₂ CH ₂ OH, and

R ₇ is H; -CH ₃ ; -CH ₂ COOH; -CH ₂ CH ₂ COOH; -CH ₂ CN or -CH ₂ CH ₂ CN.

The metal complex compound of formula (1) is a peroxide or peroxide-forming material, O ₂ And / or as a catalyst with air. Examples that may be mentioned in this regard include the following uses:

a) bleaching blotches or stains on textile materials in connection with cleaning processes or by direct application of decontaminants;

b) cleaning hard surfaces, in particular wall tiles or floor tiles, to remove contaminants formed as a result of fungal action (“fungal contamination”); Uses in automatic dishwashing compositions are also preferred applications;

c) bleaching blots or stains on fabric materials by atmospheric oxygen, said bleaching being facilitated during and / or after treatment of the fabric in the wash liquor;

d) preventing the redeposition of mobile dyes during washing of the fabric material;

e) use in cleaning and cleaning solutions having antimicrobial action;

f) use as a pretreatment for bleaching fabrics;

g) use as a catalyst in selective oxidation in connection with organic synthesis;

h) use as catalyst for wastewater treatment.

i) as a catalyst for peroxy compounds for decolorization in papermaking. This is particularly concerned with the delignination of cellulose and the decolorization of pulp, which can be carried out according to conventional procedures. The use of the metal complex compound of formula (1) is also important as a catalyst for reaction with a peroxy compound for bleaching waste paper.

j) sterile and

k) Disinfecting contact lenses.

Preference is given to decolorizing stains or stains on textile materials, for cleaning hard surfaces, especially kitchen surfaces, wall tiles or floor tiles, as well as for use in automatic dishwasher formulations; For bleaching blots or dirt on textile materials with atmospheric oxygen, which promotes bleaching during and / or after treatment of the fabric in the wash liquor; Alternatively, it is used to prevent redeposition of the dye dye during the washing process. Preferred metals in this case are manganese and / or iron.

It should be emphasized that the use of metal complex compounds in the decolorization of textile materials or hard surfaces does not cause significant damage to hard surface materials such as utensils and cooking utensils and tiles as well as fibers and dyeing.

The process of bleaching contamination in the wash liquor comprises one or more metal complexes of formula (1) or (1 ′) in the wash liquor (including H ₂ O ₂ or H ₂ O ₂ precursor with peroxy acid or their precursors) By adding a compound. Alternatively, detergents already containing one or two metal complex compounds can be added. In this application as well as in other applications, the metal complex compounds of formula (1) or (1 ′) may be prepared from metal salts such as manganese (II) chloride (eg manganese (II) salts) and / or iron such as iron (II) chloride ( II) salts and ligands can be formed in place by addition in the desired molar ratio.

The present invention relates to detergents, cleaners, disinfectants or bleach compositions containing the following materials:

I) 0-50% by weight, preferably 0-30% by weight of A) at least one anionic surfactant and / or B) at least one nonionic surfactant,

II) 0 to 70% by weight, preferably 0 to 50% by weight of C) at least one builder material,

III) 1 to 99% by weight, preferably 1 to 50% by weight of D) at least one peroxide or peroxide forming material, O ₂ and / or air,

IV) When adding 0.5 to 50 g / l of detergent, cleaner, disinfectant or bleach to the wash liquor, a concentration of 0.5 to 100 mg / liter of wash liquor, preferably 1 to 50 mg / liter of wash liquor An amount having E) at least one metal complex compound of formula (1) or (1 '), and

V) 0-20% by weight of one or more additional additives, and

VI) 100% by weight of water.

All weight percents are based on the total weight of the detergent, cleaner, disinfectant or bleach composition.

Detergent, detergent, disinfectant or bleach compositions can be industrial, household cleaning, disinfecting or bleach formulations.

For example, it can be used in compositions for use on textile materials as well as compositions for use on hard surfaces such as hard surface materials such as utensils and cooking utensils and tiles.

Such preferred hard surface cleaning compositions are dishwashing formulations, more preferably automatic dishwasher detergent formulations.

The percentage is weight percent based on the total weight of the composition. The composition preferably contains 0.005 to 2% by weight, in particular 0.01 to 1% by weight, preferably 0.05 to 1% by weight, of at least one metal complex compound of the formula (1) or (1 ').

Accordingly, another aspect of the present invention relates to a detergent, cleaner, disinfectant or bleach composition containing the following materials:

I) 0-50% by weight, preferably 0-30% by weight of A) at least one anionic surfactant and / or B) at least one nonionic surfactant,

II) 0 to 70% by weight, preferably 0 to 50% by weight of C) at least one builder material,

III) 1 to 99% by weight, preferably 1 to 50% by weight of D) at least one peroxide or peroxide forming material, O ₂ and / or air,

IV) 0.005 to 2% by weight, preferably 0.01 to 1% by weight, most preferably 0.05 to 1% by weight of E) at least one metal complex compound of formula (1) or (1 '), and

V) 0-20% by weight of one or more additional additives, and

VI) 100% by weight of water.

All weight percents are based on the total weight of the detergent, cleaner, disinfectant or bleach composition.

If the composition according to the invention comprises components A) and / or B), its amount is from 1 to 50% by weight, in particular from 1 to 30% by weight.

Accordingly, the present invention relates to detergents, cleaners, disinfectants or bleach compositions containing the following materials:

I) 1 to 50% by weight, preferably 1 to 30% by weight of A) at least one anionic surfactant and / or B) at least one nonionic surfactant,

II) 0 to 70% by weight, preferably 0 to 50% by weight of C) at least one builder material,

III) 1 to 99% by weight, preferably 1 to 50% by weight of D) at least one peroxide or peroxide forming material, O ₂ and / or air,

IV) 0.005 to 2% by weight, preferably 0.01 to 1% by weight, most preferably 0.05 to 1% by weight of E) at least one metal complex compound of formula (1) or (1 '), and

V) 0-20% by weight of one or more additional additives, and

VI) 100% by weight of water.

All weight percents are based on the total weight of the detergent, cleaner, disinfectant or bleach composition.

If the composition according to the invention comprises component C), its amount is from 1 to 70% by weight, in particular from 1 to 50% by weight. Especially preferably the amount is from 5 to 50% by weight, in particular from 10 to 50% by weight.

Accordingly, the present invention relates to detergents, cleaners, disinfectants or bleach compositions containing the following materials:

I) 1 to 50% by weight, preferably 1 to 30% by weight of A) at least one anionic surfactant and / or B) at least one nonionic surfactant,

II) 1 to 70% by weight, preferably 1 to 50% by weight of C) at least one builder material,

III) 1 to 99% by weight, preferably 1 to 50% by weight of D) at least one peroxide or peroxide forming material, O ₂ and / or air,

IV) 0.005 to 2% by weight, preferably 0.01 to 1% by weight, most preferably 0.05 to 1% by weight of E) at least one metal complex compound of formula (1) or (1 '), and

V) 0-20% by weight of one or more additional additives, and

VI) 100% by weight of water.

All weight percents are based on the total weight of the detergent, cleaner, disinfectant or bleach composition.

Corresponding washing, washing, disinfecting or bleaching methods are carried out by using an aqueous solution containing 0.1 to 200 mg of at least one compound of formula (1) per liter of wash liquor. The wash liquor contains 1 to 50 mg of at least one compound of formula (1) per liter of wash liquor.

The composition according to the invention can be for example a peroxide-containing heavy-duty detergent or a separate bleach additive, or a decontamination agent to be applied directly. Bleach additives are used to remove colored contamination on fabrics in a separate liquid before washing the garment with a bleach-free detergent. Bleach additives can be used in liquids with bleach-free detergents. Decontamination agents can be applied directly to the fabric of interest and are used for pretreatment in case of local heavy contamination.

Decontamination agents may be applied in liquid form by spraying or in the form of solid substances, such as powders, in particular granules.

Granules can be prepared, for example, by first preparing an initial powder by spray drying an aqueous suspension comprising all of the above components except component E) and then adding the dry component E) and mixing everything together. Component E) may also be added to an aqueous suspension containing components A), B), C) and D) followed by spray drying.

It may also be disclosed as an aqueous suspension containing components A) and C) and without or containing a small amount. This suspension is spray dried and component E) is then mixed with component B) and added and then component D) is mixed in a dry state. All components may be mixed in a dry state.

Anionic surfactants A) are for example sulfate, sulfonate or carboxylate surfactants or mixtures thereof. Preference is given to alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or α-sulfon fatty acid salts or esters thereof.

Preferred sulfonates are, for example, alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl radical, alkyl sulfates having 8 to 18 carbon atoms in the alkyl radical, alkyl ether sulfates having 8 to 18 carbon atoms in the alkyl radical, and alkyl residues Fatty acids salts having from 8 to 18 carbon atoms derived from palm oil or tallow. The average mole number of ethylene oxide units added to the alkyl ether sulfate is 1 to 20, preferably 1 to 10. The cation in the anionic surfactant is preferably an alkali metal cation, in particular sodium or potassium, more particularly sodium. Preferred carboxylates are alkali metal sarcosinates of the formula R ₁₉ -CO-N (R ₂₀ ) -CH ₂ COOM ₁ , wherein R ₁₉ is alkyl or alkenyl having 8 to 18 carbon atoms in the alkyl or alkenyl radical R ₂₀ is C ₁ -C ₄ alkyl; And M ₁ is an alkali metal, in particular sodium.

Nonionic surfactants B) are for example primary or secondary alcohol ethoxylates, especially ethoxylated C ₈ -C ₂₀ with an average of 1 to 20 moles of ethylene oxide per alcohol group Aliphatic alcohol. Ethoxylated primary and secondary C ₁₀ -C _{15 with an} average of 1 to 10 moles of ethylene oxide per alcohol group Aliphatic alcohols are preferred. Nonethoxylated nonionic surfactants can be used, for example, alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamides).

The total amount of anionic and nonionic surfactants is preferably 5 to 50% by weight, in particular 5 to 40% by weight and more particularly 5 to 30% by weight. The minimum of these especially preferable surfactant is 10 weight%.

In addition to anionic and / or nonionic surfactants, the composition may contain cationic surfactants. Possible cationic surfactants include all common cationic surfactant compounds, especially surfactants having a fabric softening effect.

Non-limiting examples of cationic surfactants are represented by the formula:

In the formula,

Each radical R _α is independently of _one another C ₁ -C ₆ -alkyl, -alkenyl- or -hydroxyalkyl;

Each radical R _β is independently of each other C ₈ -C ₂₈ -alkyl- or -alkenyl;

R _γ is R _α or (CH ₂ ) _n -TR _β ;

R _δ is R _α or R _β or (CH ₂ ) _n -TR _β ; T = -CH _2- , -O-CO- or -CO-O-; In addition

n is 0-5.

Preferred cationic surface active agent present in the compositions according to the present invention is a hydroxy-alkyl-trialkyl-ammonium-compounds, in particular C _{12 -18-alkyl} (hydroxyethyl) dimethylammonium compounds, especially preferred is the corresponding chloride salt. The compositions of the present invention may contain from 0.5% to 15% by weight cationic surfactant based on the total weight of the composition.

Builder components C) are for example alkali metal phosphates, in particular tripolyphosphates, carbonates or hydrogen carbonates, in particular their sodium salts, silicates, aluminosilicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepolys (Alkylene phosphonates) or mixtures of these compounds may be considered.

Particularly suitable silicates are crystals of the formula NaHSi _t O _{2t +1} .pH ₂ O or Na ₂ Si _t O _{wt +1} .pH ₂ O (where t is a number from 1.9 to 4 and p is a number from 0 to 20). Sodium salt of layered silicates.

Of the aluminum silicates, mixtures which are sold under the trade names zeolite A, B, X and HS and which comprise at least two of the aforementioned components are preferred. Zeolite A is preferred.

Among the polycarboxylates, polyhydroxycarboxylates, in particular citrate and acrylates, and also copolymers of these with maleic anhydride are preferred. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate in racemic form or in enantiomerically pure (S, S) form.

Particularly suitable phosphonates or aminoalkylenepoly (alkylenephosphonates) are 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, hexamethylene Alkali metal salts of diamines N, N, N ', N'-tetrakisethanephosphonic acid and diethylenetriaminepentamethylenephosphonic acid, as well as salts thereof. Preferred polyphosphonates also have the formula:

In the formula,

R ₁₈ is CH ₂ PO ₃ H ₂ or a water soluble salt thereof; In addition

d is an integer of 0, 1, 2 or 3.

Especially preferred are polyphosphonates where b is an integer having a value of 1.

The amount of peroxide or peroxide-forming material is 0.5 to 30% by weight, more preferably 1 to 20% by weight, particularly preferably 1 to 15% by weight.

As the peroxide component D), all compounds capable of obtaining hydrogen peroxide in aqueous solution, such as organic and inorganic peroxides known in the literature capable of bleaching textile materials at normal washing temperatures, such as 10 to 95 ° C., are contemplated.

However, preferably, inorganic peroxides such as persulfate, perborate, percarbonate and / or persilicate can be used.

Examples of suitable inorganic peroxides are sodium perborate tetrahydrate or sodium percarbonate monohydrate, sodium percarbonate, inorganic peroxyacid compounds, eg potassium monopersulfate (MPS). If organic or inorganic peroxy acid is used as the peroxygen compound, its amount will usually range from about 2 to 80% by weight, preferably 4 to 30% by weight.

Organic peroxides are, for example, mono- or poly-peroxides, urea peroxides, C ₁ -C ₄ alkanol oxidases and C ₁ -C ₄ Combinations of alkanols (such as methanol oxidase and ethanol as described in WO 95/07972), alkylhydroxy peroxides such as cumene hydroperoxide and t-butyl hydroperoxide.

Peroxides can be in various crystalline forms and can have different water contents and they can be used with other inorganic or organic compounds to improve storage stability.

All these peroxy compounds may be used alone or in combination with organic bleach catalysts that do not contain a peroxy acid bleaching precursor and / or a transition metal. In general, the bleaching compositions of the invention may be suitably formulated to contain 2 to 80% by weight, preferably 4 to 30% by weight of peroxy bleach.

As the oxidizing agent, peroxo acid can be used. One example is organic mono peracid of the formula:

In the formula,

M means hydrogen or cation,

R ₁₉ is unsubstituted C ₁ -C ₁₈ Alkyl; Substituted C ₁ -C ₁₈ Alkyl; Unsubstituted aryl; Substituted aryl; -(C ₁ -C ₆ alkylene) -aryl, wherein the alkylene and / or alkyl group may be substituted; Another phthalimido C ₁ -C ₈ Alkylene, where a phthalimido and / or alkylene group can be substituted.

Preferred mono organic peroxy acids and salts thereof are of the formula:

In the formula,

M is hydrogen or an alkali metal, and

R _'19 is unsubstituted C ₁ -C ₄ Alkyl; Phenyl; -C ₁ -C ₂ Alkylene-phenyl or phthalimido C ₁ -C ₈ Alkylene, where a phthalimido and / or alkylene group can be substituted.

Especially preferred are CH ₃ COOOH and its alkali salts.

Especially preferred are ε-phthalimido peroxy hexanoic acid and its alkali salts.

Also suitable are diperoxy acids, such as 1,12-diperoxydodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrasyl acid, diperoxysebacic acid, diperoxyisophthalic acid, 2-decyldiperoxy Butane-1,4-dioctic acid and 4,4'-sulfonylbisperoxybenzoic acid.

Instead of peroxy acid, organic peroxy acid precursors and H ₂ O ₂ can be used. Such precursors are the corresponding carboxylic acids or the corresponding carboxylic acid anhydrides or the corresponding carbonylchlorides, amides, or esters which can form peroxy acids upon perhydrolysis. Such reactions are usually known.

Peroxy acid bleaching precursors are known and are further described in British Patent 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522 EP-A-0174132; EP-A-0120591; And US Patent No. 1,246,339; 3,332,882; 4,128,494; Many are described in documents such as 4,412,934 and 4,675,393.

Peroxy acid precursors are often referred to as bleach activators. Suitable bleach activators include bleach activators having O- and / or N-acyl groups and / or unsubstituted or substituted benzoyl groups. Polyacrylated alkylenediamines, in particular tetraacetylethylenediamine (TAED); Acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N, N-diacetyl-N, N-dimethylurea (DDU); Sodium-4-benzoyloxy benzene sulfonate (SBOBS); Sodium-1-methyl-2-benzoyloxy benzene-4-sulfonate; Sodium-4-methyl-3-benzoloxy benzoate; Trimethyl ammonium toluyloxy-benzene sulfonate; Acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); A compound of formula (6)

Wherein R ₂₂ is a sulfonate group, a carboxylic acid group or a carboxylate group and R ₂₁ is a straight or branched (C ₇ -C ₁₅ ) alkyl), in particular an activator known under the trade names SNOSS, SLOBS and DOBA; Acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran; And acetylated sorbitol and mannitol and acylated sugar derivatives, in particular pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, as well as acetylated, If desired, N-alkylated glucamine and gluconolactone are preferred. Combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used. Nitrile compounds that form perimine acids with peroxides can also be considered bleach activators.

Another useful class of peroxy acid bleaching precursors is cationic, ie, as described in US Pat. Nos. 4,751,015 and 4,397,757, EP-A-0284292 and EP-A-331,229. Examples of peroxy acid bleaching precursors of this kind are 2- (N, N, N-trimethyl ammonium) ethyl sodium-4-sulfonphenyl carbonate chloride- (SPCC), N-octyl, N, N-dimethyl-N10 Carbophenoxy decyl ammonium chloride-(ODC), 3- (N, N, N-trimethyl ammonium) propyl sodium-4-sulfophenyl carboxylate and N, N, N-trimethyl ammonium toluyloxy benzene sulfonate to be.

Another particular kind of bleaching precursor is formed by cationic nitriles as described in EP-A-303,520, WO 96/40661 and European Patent Nos. 458,396, 790244 and 464,880. These cationic nitriles, known as nitrile quats, have the formula:

In the formula,

R ₃₀ is C ₁ -C ₂₄ alkyl; a C ₁ -C ₂₄ alkenyl; Alkaryl having C ₁ -C ₂₄ alkyl; Substituted C ₁ -C ₂₄ alkyl; Substituted C ₁ -C ₂₄ alkenyl; Substituted aryl;

R ₃₁ and R ₃₂ are independently C ₁ -C ₃ alkyl; Hydroxyalkyl having 1 to 3 carbon atoms,-(C ₂ H ₄ O) _n H, wherein n is 1 to 6; -CH ₂ -CN;

R ₃₃ is C ₁ -C ₂₀ alkyl; C ₁ -C ₂₀ Alkenyl; Substituted C ₁ -C ₂₀ alkyl; Substituted C ₁ -C ₂₀ Alkenyl; Alkaryl having C ₁ -C ₂₄ alkyl and at least one substituent;

R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ and R ₃₈ are each independently of the other hydrogen, C ₁ -C ₁₀ alkyl, C ₁ -C ₁₀ alkenyl, substituted C ₁ -C ₁₀ alkyl, substituted C ₁ -C ₁₀ alkenyl, carboxyl, sulfonyl or cyano;

R ₃₈ , R ₃₉ , R ₄₀ and R ₄₁ are independently of each other C ₁ -C ₆ alkyl;

n 'is an integer from 1 to 3;

n "is an integer from 1 to 16; and

X is an anion.

Other nitrile quartzes have the following formula:

In the formula,

R ₄₂ and R ₄₃ combine with the nitrogen atom to which they are attached to form a ring containing 4 to 6 carbon atoms, which ring is C ₁ -C ₅ -alkyl, C ₁ -C ₅ -alkoxy, C ₁ -C ₅ -May be substituted by alkanoyl, phenyl, amino, ammonium, cyano, cyanamino or chloro and one or two carbon atoms of the ring are selected from a nitrogen atom, an oxygen atom, an NR ₄₇ group and / or Which may be substituted by a group R ₄₄ -NR ₄₇ -wherein R ₄₇ is hydrogen, C ₁ -C ₅ -alkyl, C ₂ -C ₅ -alkenyl, C ₂ -C ₅ -alkynyl, phenyl, C _7- C ₉ -aralkyl, C ₅ -C ₇ -cycloalkyl, C ₁ -C ₅ -alkanoyl, cyanomethyl or cyano,

R ₄₄ is C ₁ -C _24- , preferably C ₁ -C ₄ -alkyl; C ₂ -C ₂₄ -alkenyl, preferably C ₂ -C ₄ -alkenyl, cyanomethyl or C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl,

R ₄₅ and R ₄₆ are each independently hydrogen; C ₁ -C ₄ -alkyl; C ₁ -C ₄ -alkenyl; C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl; Phenyl or C ₁ -C ₃ -alkylphenyl, preferably hydrogen, methyl or phenyl, preferably residue R ₄₅ means hydrogen unless R ₄₆ is hydrogen, and

X ^- is an anion.

Suitable examples of nitrile quartz of formula (ε) are as follows:

Other nitrile quartzes have the following formula:

In the formula,

A is a saturated ring formed by a plurality of atoms in addition to the N ₁ atom, the saturated ring atom comprising at least one carbon atom and at least one heteroatom in addition to the N ₁ atom, wherein the heteroatom is a group consisting of O, S and N atoms is selected from the substituents bonded to the N ₁ atom of the formula (φ) structure R ₄₇ is (a) C ₁ -C ₈ - alkyl or alkoxylated alkyl, wherein the alkoxy is _{C 2 -4, (b) C} 4 -C ₂₄ cycloalkyl, (c) C ₇ -C ₂₄ alkaryl, (d) a repeating or non-repeating alkoxy or alkoxylated alcohol, wherein the alkoxy unit is C _24, or (e) -CR ₅₀ R ₅₁ -C = N, where R ₅₀ and R ₅₁ are H, C ₁ -C ₂₄ alkyl, cycloalkyl, or alkaryl, or a repeating or non-repeating alkoxyl or alkoxylated alcohol, wherein the alkoxy unit is C ₂ -C _4, and, at least one of R ₄₈ and R ₄₉ substituents in the formula (φ) is H and also R ₄₈ and R ₄₉ substituents rest is H, C ₁ -C ₂₄ alkyl, when the Roal kill, or Al keuah a reel, or repeating or non-repeating alkoxyl or alkoxylated alcohol, wherein the alkoxy unit is C _{2 - 4} and being also Y is one or more counter ion.

The precursor may be used in an amount of up to 12% by weight, preferably 2 to 10% by weight, based on the total weight of the composition.

In general, further known bleaching catalysts can be used, such as transition metal complexes as described in EP 1194514, EP 1383857 or WO04 / 007657.

H ₂ O ₂ , O ₂ , air, peroxy containing compounds, peroxy acids as well as their precursors, further bleach catalysts and bleach actives can be used in combination with the metal complexes of the invention.

The composition comprises at least one optical brightener, bis-triazinylamino-stilbendisulfonic acid, bis-triazolyl-stilbendisulfonic acid, bis-styryl-biphenyl or bis-benzofuranyl ratio in addition to the combinations according to the invention. It may further include a phenyl, bis-benzooxalyl derivative, bis-benzimidazolyl derivative or coumarin derivative or pyrazoline derivative.

The composition may also include one or more additional additives. Such additives include, for example, dirt suspending agents such as sodium carboxymethylcellulose; pH adjusting agents such as alkali or alkaline earth metal silicates; Bubble control agents such as soaps; Salts for adjusting spray drying and granulation properties such as sodium sulfate; perfume; And, if necessary, antistatic agents and softeners; Smectic clay; Photobleach; Pigments; And / or light-shielding agents. These ingredients must be stable to any bleach system used. If the detergent composition is used in an automatic dishwasher, silver corrosion inhibitors may be used together.

Such adjuvants may be present in amounts of, for example, 0.1 to 20% by weight, preferably 0.5 to 10% by weight, in particular 0.5 to 5% by weight, based on the total weight of the detergent formulation.

In addition, the detergent may optionally contain an enzyme. The enzyme can be added to the detergent for decontamination. These enzymes usually improve the performance against contamination of protein- or starch-based, such as caused by blood, milk, grass or fruit juice. Preferred enzymes are cellulases, proteases, amylases and lipases. Preferred enzymes are cellulases and proteases, in particular proteases. Cellulase is an enzyme that acts on cellulose and its derivatives and hydrolyzes them to glucose, cellobiose, and cell oligosaccharides. Cellulase has the effect of removing dust and reducing the rough feel. Examples of enzymes that can be used include, but are not limited to:

Proteases described in US-B-6,242,405, column 14, lines 21-32;

Lipases described in US-B-6,242,405, columns 14, lines 33-46;

Amylases described in US-B-6,242,405, column 14, lines 47-56; And

Cellulase as described in US-B-6,242,405, column 14, lines 57-64.

^{Alcalase ®, Esperase ®, Everlase ®} , a commercially available detergent proteases, such as Savinase ^®, Kannase ^®, Durazym ^®, and is for example commercially available by NOVOZYMES A / S.

Commercially available detergent amylases such as Termamyl ^® , Duramyl ^® , Stainzyme ^® , Natalase ^® , Ban ^® , and Fungamyl ^® are sold by NOVOZYMES A / S.

Commercial detergent cellulase such as Celluzyme ^® , Carezyme ^® , and Endolase ^® are commercially available from NOVOZYMES A / S.

Commercial detergent lipases such as Lipolase ^® , Lipolase Ultra ^® , and Lipoprime ^® are commercially available from NOVOZYMES A / S.

Suitable mannases such as Mannanaway ^® are commercially available from NOVOZYMES A / S.

In addition to laundry products in hard surface cleaners, especially in compositions used in automatic dishwashers, the following enzymes are generally used: proteases, amylases, flulanases, cutinases and lipases such as BLAP ^® , Optimase ^® , Opticlean Proteases such as ^® , Maxacal ^® , Maxapem ^® , Esperase ^® , and / or Savinase ^® ; Amylases such as Termamyl ^® , Amylase-LT ^® , Maxamyl ^® , and / or Duramyl ^® ; Lipases such as Lipolase ^® , Lipomax ^® , Lumafast ^® , and / or Lipozym ^® . Enzymes that may be used as described in international patent applications WO 92/11347 and WO 94/23005 are embedded in materials adsorbed and / or encapsulated on a carrier to protect them from premature inactivation. They are present in the cleaning formulations according to the invention in amounts not exceeding 5% by weight, in particular in amounts of 0.1% to 1.2% by weight.

Amylase: The present invention preferably uses amylases with improved stability in detergents, in particular with improved oxidative stability. Such amylases are shown without limitation by: (a) the ratio known as TERMAMLY ^® . WO 94/02597, Novo Nordisk A / S, which can be represented by a mutation that has been substituted with alanine or threonine (preferably threonine) of a methionine residue located at position 197 of B. licheniformis alpha-amylase Amylases, or B. amyloliquesfaciens according to the present invention, b. B. subtilis or b. Homologous positional variants of similar parent amylases such as B. stearothermophilus ; (b) Stability-enhanced amylase as described by Genencor Interantional in the article "Oxidatively Resistant α-Amylases" presented at C207 Mitchinson, 207th American Chemical Society National Meeting, March 13-17 1994. Bleach in automatic dishwashing detergents inactivates alpha-amylase but does not. It was found that enhanced oxidative stability amylase was produced by Genencor from B. licheniformis NCIB8061. Other oxidative stability-enhanced amylases may also be used.

Protease: Protease enzymes are present in preferred embodiments of the present invention in amounts of 0.001% to 5% by weight. This proteolytic enzyme may be of animal, plant or microbial (desirable) origin. More preferably, it is a serine proteolytic enzyme of bacterial origin. Purified or crude forms of the enzyme can be used. Proteolytic enzymes produced by chemically or genetically modified mutations are included in the definition because they are closely structural enzyme variants. Suitable commercial proteolytic enzymes include Alcalase ^® , Esperase ^® , Everlase ^® , Durazyme ^® , Savinase ^® , Maxatase ^® , Kannase ^® , Maxacal ^® , and Maxapem ^® 15 (protein-treated Maxacal). Purafect ^® and subtilizing BPN and BPN 'are commercially available.

If lipase is present, the lipase comprises from about 0.001% to about 0.01% by weight of the composition of the present invention and optionally contains about 1 surfactant, such as alkyldimethylamine N-oxide or sulfobetaine, having a lime soap dispersion property. In combination with weight percent to about 5 weight percent. Lipases suitable for use herein include lipases of bacterial, animal and fungal origin, which also include chemical or genetically modified mutants. Commercial detergent lipases such as Lipolase ^® , Lipolase Ultra ^® and Lipoprime ^® can be purchased from NOVOZYMES A / S. When incorporating lipases into the compositions of the present invention, stability and efficacy can be improved by combining them with small amounts (such as less than 0.5% by weight of the composition) of an oily but non-hydrolyzable material.

When an enzyme is used, the enzyme may be present in an amount of from 0.01 to 5% by weight, in particular from 0.05 to 5% by weight, more particularly from 0.1 to 4% by weight, based on the weight of the total detergent formulation.

If the detergent formulation is a hard surface cleaning composition, preferably a dish washing detergent formulation, more preferably an automatic dish washing detergent formulation, from about 0.001% to about 10% by weight, preferably from about 0.005% to about 8% by weight, Most preferably, from about 0.01% to about 6% by weight of an enzyme stabilization system. The enzyme stabilization system may be a stabilization system compatible with detergent enzymes. Such systems may inherently have other formulation actives or may be added separately by the formulator or manufacturer of the detergent-preparing enzyme. Such stabilization systems may include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof, and are designed to solve different stabilization problems depending on the type and physical form of the detergent composition.

In order to increase the bleaching action, the composition comprises a photocatalyst in addition to the catalyst described herein, the action being based on the generation of singlet oxygen.

Particularly preferred additives to the compositions according to the invention are dye fixatives and / or polymers, which prevent staining with dyes in the wash liquor released from the fabric under washing conditions during washing of the fabric. Such polymers are in particular polyvinylpyrrolidone, polyvinylimidazole or polyvinylpyridine-N-oxides, in particular in the range from 5000 to 60 000, more particularly 10 000, which may be modified by incorporation of anionic or cationic substituents. To a molecular weight ranging from 50 000. Such polymers are usually used in amounts of 0.01 to 5% by weight, in particular 0.05 to 5% by weight and more particularly 0.1 to 2% by weight, based on the total weight of the detergent formulation. Preferred polymers are mentioned in WO-A-02 / 02865 (see especially page 1, last paragraph and page 2, first paragraph).

When the detergent compositions of the present invention are used as hard surface cleaners, especially if the compositions are used in automatic dishwasher formulations, they tend to be deposited on the tableware, thus avoiding the use of simple calcium precipitation soaps as antifoams in the compositions of the present invention. Has been found to be preferred. Indeed, the phosphate esters are not completely free from this problem, so the formulator will generally choose to minimize the degree of deposition of the antifoam in the compositions of the present invention. Other examples of foam inhibitors are paraffins, paraffin / alcohol combinations, or bisfatty acid amides.

Hard surface cleaning compositions, preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations, may optionally contain one or more heavy metal chelating agents, such as hydroxyethyldiphosphonate (HEDP). More generally, chelating agents suitable for use may be selected from the group consisting of amino carboxylates, amino phosphonates, multifunctional substituted aromatic chelating agents, and mixtures thereof. Other chelating agents suitable for use are the commercially available DEQUEST series and chelants manufactured by Nalco, Inc. Aminocarboxylates useful as any chelating agent include ethylenediaminetetraacetate, N-hydroxyethylethylenediamine triacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriamine-penta Acetates, and ethanol diglycine, alkali metals, ammonium, and substituted ammonium salts and mixtures thereof.

Aminophosphonates are suitable for use as chelating agents in the compositions of the present invention when at least a minimum amount of total phosphorus is acceptable in the detergent composition, and also includes ethylenediaminetetrakis (methylenephosphonate). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having about 6 carbon atoms.

Particularly preferred biodegradable chelates for use herein are ethylenediamine disuccinate ("EDDS").

If used, these chelating agents or transition metal selective sequestrants are generally from about 0.001% to about 10% by weight, more preferably from about 0.05% to about 1% by weight of the hard surface cleaning composition, preferably Dishwashing detergent formulations, more preferably aromatic dishwashing detergent formulations.

Preferred hard surface cleaning compositions, preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations may additionally contain a dispersant polymer. When present, dispersant polymers typically range from 0% to about 25%, preferably from about 0.5% to about 20%, more preferably from about 1% to about 8% by weight of the detergent composition. exist. Dispersant polymers are useful for improving film performance of the dishwasher detergent compositions of the present invention, especially in higher pH embodiments, the washing pH is greater than about 9.5. Especially preferred are polymers which inhibit the deposition of calcium carbonate or magnesium silicate on tableware.

Suitable polymers are preferably partially neutralized or alkali metal, ammonium or substituted ammonium (eg mono-, di- or triethololammonium) salts of polycarboxylic acids. Most preferred are alkali metals, especially sodium salts. The molecular weight of the polymer can be in a variety of ranges, but is preferably about 1,000 to about 500,000, more preferably about 1,000 to about 250,000.

Unsaturated monomeric acids that can be polymerized to form suitable dispersant polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments that do not contain carboxylate radicals, such as methyl vinyl ether, styrene, ethylene, etc., are provided such that these segments do not constitute up to about 50% by weight of the dispersant polymer.

Copolymers of acrylamide and acrylate having a molecular weight of about 3,000 to about 100,000, preferably about 4,000 to about 20,000, and an acrylamide content of less than about 50%, preferably less than about 20% by weight of the dispersant polymer can be used. have. Most preferably, such dispersant polymers have a molecular weight of about 4,000 to about 20,000 and the acrylamide content is from about 0% to about 15% by weight based on the total weight of the polymer.

Particularly preferred dispersant polymers are low molecular weight modified polyacrylate copolymers. Such copolymers comprise a) about 90% to about 10% by weight, preferably about 80% to about 20% by weight of acrylic acid or a salt thereof and b) about 10% to about 90% by weight, as monomer units. Preferably containing from about 20% to about 80% by weight of substituted acrylic monomers or salts thereof and has the following general formula:-[(C (R _a ) C (R _b ) (C (O) OR _c ) Wherein, the seemingly unfilled valence is actually occupied by hydrogen and at least one of the substituents R _a , R _b , or R _c , preferably R _a or R _b is 1-4 carbon alkyl or Substituted hydroxyalkyl group R _a or R _b is hydrogen and R _c is hydrogen or an alkali metal salt Most preferred are substituted acrylics in which R _a is methyl, R _b is hydrogen and R _c is sodium Monomer.

Suitable low molecular weight polyacrylate dispersant polymers preferably have a molecular weight of less than about 15,000, preferably about 500 to about 10,000, most preferably about 1,000 to about 5,000. Most preferred polyacrylate copolymers for use herein are sufficiently neutralized forms of polymers having a molecular weight of about 3,500 and comprising about 70% by weight acrylic acid and about 30% by weight methacrylic acid.

Other dispersant polymers useful herein include polyethylene glycol and polypropylene glycol having a molecular weight of about 950 to about 30,000.

Other dispersant polymers useful herein include cellulose sulfate esters such as cellulose acetate, cellulose sulfate, hydroxyethyl cellulose sulfate, methylcellulose sulfate and hydroxypropylcellulose sulfate. Sodium cellulose sulfate is the most preferred polymer of this group.

Other suitable dispersant polymers are carboxylate polysaccharides, in particular starch, cellulose and alginate.

Another group of acceptable dispersants is organic dispersant polymers such as polyaspartate.

Depending on whether some degree of compressibility is required, the filler material may be present in the hard surface cleaning composition, preferably in the dishwashing detergent formulation, more preferably in the automatic dishwashing detergent formulation. These include sucrose, sucrose esters, sodium sulfate, potassium sulfate and the like and are up to about 70% by weight of the hard surface cleaning composition, preferably the dishwashing detergent formulation, more preferably the automatic dishwashing cleaning formulation, preferably 0 It is present in an amount from about 40% by weight. Preferred fillers may be good grades with sodium sulfate, especially trace impurities.

The sodium sulfate used preferably has sufficient purity to be nonreactive with the bleach; It may also be treated with small amounts of sequestrants such as phosphonates or EDDS in magnesium-salt form. The same applies to pH adjusting components, including silicates, in terms of purity sufficient to avoid bleach degradation.

Organic solvents which can be used in the cleaning formulations according to the invention are alcohols having 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol and t-butanol, 2 to 4 carbon sources, especially when the latter are used in liquid or paste form Diols having a ruler, in particular ethylene glycol and propylene glycol, and mixtures thereof, and ethers which can be derived from compounds of the abovementioned types. Such water miscible solvents are present in the cleaning formulations according to the invention in amounts not exceeding 20% by weight, in particular in amounts of 1% to 15% by weight.

Many hard surface cleaning compositions, preferably dishwashing detergent formulations, and more preferably automatic dishwashing detergent formulations, can be buffered, ie they are relatively resistant to pH drops in the presence of acidic soils. However, other components may or may not have a significantly low buffering capacity. Techniques for controlling or changing the pH in the recommended range of uses include the use of buffers as well as additional alkalis, acids, pH jump systems, dual component vessels, and the like, which are well known to those skilled in the art. Certain hard surface cleaning compositions, preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations, comprise a pH adjusting component selected from a water soluble alkaline inorganic salt and a water soluble organic or inorganic builder. The pH adjusting component has a pH of at least about 8, preferably about 9.5, when the hard surface cleaning composition, preferably the dish washing detergent formulation, more preferably the automatic dish washing detergent formulation is dissolved in water at a concentration of 1,000 to 5,000 ppm. To about 11 in the range. Preferred non-phosphate pH adjusting components can be selected from the following groups:

(i) sodium carbonate or sesquicarbonate;

(ii) sodium silicate, preferably aqueous sodium silicate having SiO ₂ : Na ₂ O in a ratio of about 1: 1 to about 2: 1, and mixtures thereof with a limited amount of sodium metasilicate;

(iii) sodium citrate;

(iv) citric acid;

(v) sodium bicarbonate;

(vi) sodium borate, preferably borax;

(vii) sodium hydroxide; And

(viii) a mixture of (i)-(vii).

Preferred embodiments contain small amounts of silicates (ie, about 3 wt% to about 10 wt% SiO ₂ ).

Examples of this particular type of highly preferred pH control system are binary mixtures of granular sodium citrate and anhydrous sodium carbonate, and tricomponent mixtures of granular sodium citrate trihydrate, citric acid monohydrate and anhydrous sodium carbonate.

The amount of pH adjusting component in the composition used for automatic dish washing is from about 1% to about 50% by weight of the composition. In a preferred embodiment, the pH adjusting component is in an amount of about 5% to about 40% by weight, preferably about 10% to about 30% by weight in the composition. For compositions having a pH of about 9.5 to about 11 of the initial wash solution, particularly preferred automatic dishwashing detergent formulation embodiments are from about 5% to about 40% by weight, preferably about about, based on the weight of the automatic dishwashing detergent formulation. 10 wt% to about 30 wt%, most preferably about 15 wt% to about 20 wt% sodium citrate, preferably about 5 wt% to about 30 wt%, preferably about 7 wt% to 25 wt% Most preferably about 8% to about 20% by weight sodium carbonate.

The essential pH control system is selected from other optional detergent builders selected from the non-phosphate detergent builders known in the art, namely various water soluble, alkali metal, ammonium or substituted ammonium borate, hydroxylsulfonates, polyacetates and polycarboxylates. do. Alkali metals, in particular sodium, salts of these materials are preferred. Alternatively, water soluble, non-phosphorus organic builders can be used for their sequestration properties. Examples of polyacetate and polycarboxylate builders include ethylenediamine tetraacetic acid; Nitrilotriacetic acid, tartrate monosuccinic acid, tartrate dissuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, sodium, potassium, lithium, ammonium and substituted ammonium salts of melic acid, and sodium benzene polycarboxylate salts.

Detergent compositions can take a variety of physical forms, including powder, granule, tablet, and liquid forms. Examples thereof are tablets such as conventional powdered heavy detergents, compressed and ultra-compressed heavy detergents and heavy detergent tablets. One important physical form is in the form of so-called concentrated granules modified to be added to the washing machine.

So-called compressed or ultra-compressed detergents are also important. In the field of detergent manufacture, there is a trend towards the production of compressed detergents containing increased amounts of active substances. In order to minimize energy consumption during the cleaning process, compressed detergents need to work effectively at temperatures as low as 40 ° C or at room temperature as high as 25 ° C. Such detergents usually contain small amounts of fillers or processing aids such as sodium sulfate or sodium chloride. The amount of such fillers is usually from 0 to 10% by weight, preferably from 0 to 5% by weight, in particular from 0 to 1% by weight, based on the total amount of detergent. The bulk density of such detergents is 650-1000 g / l, preferably 700-1000 g / l, in particular 750-1000 g / l.

Detergents may also be in tablet form. Related features of tablets are ease of dispensing and ease of handling. Tablets are the most compressed delivery form of solid detergents and have a bulk density of 0.9 to 1.3 kg / liter. In order to enable rapid degradation, these tablets generally contain the following special dissolution aids:

Boiling agents such as carbonate / hydrocarbonate / citric acid;

Disintegrants such as cellulose, carboxymethyl cellulose, crosslinked poly (N-vinylpyrrolidone);

Rapidly dissolving substances such as Na (K) acetate or Na (K) citrate;

Fast dissolving water-soluble hard coatings such as dicarboxylic acids.

Tablets may also contain combinations of the dissolution aids described above.

The detergent may also be formulated as an aqueous liquid containing 5-50% by weight, preferably 10-35% water or as a non-aqueous liquid detergent containing 5% or less, preferably 0-1% by weight of water. . The non-aqueous liquid detergent composition may contain other solvents as a carrier. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol and isopropanol are suitable for this purpose. The solubilizing surfactants used are monohydric alcohols, but polyols containing 2 to about 6 carbon atoms and polyols containing 2 to about 6 hydroxy groups (eg 1,3-propanediol, ethylene glycol, glycerin and 1,2). Propanediol) may also be used. The composition may contain 5% to 90%, typically 10% to 50% of the carrier. Detergents may be present in so-called "unit liquid dosage forms".

The invention also relates to granules comprising the catalyst according to the invention and is suitable for incorporation into powder- or granule-type washing, washing or bleaching agents. Such granules preferably include:

a) 1 to 99% by weight, preferably 1 to 40% by weight, in particular 1 to 30% by weight, of at least one metal complex compound of formula (1) and at least one peroxide

b) from 1 to 99% by weight of at least one builder, preferably from 10 to 99% by weight, in particular from 20 to 80% by weight,

c) 0 to 20% by weight of at least one encapsulating material, in particular 1 to 20% by weight,

d) 0-20% by weight of one or more additional additives, and

e) 0-20% by weight of water.

All weight percentages are based on the total weight of the granules.

Or alternative granules may include:

a) 1 to 99% by weight, preferably 1 to 40% by weight, in particular 1 to 30% by weight, of at least one metal complex compound of formula (1) and at least one peroxide forming material,

b) from 1 to 99% by weight of at least one builder, preferably from 10 to 99% by weight, in particular from 20 to 80% by weight,

c) 0 to 20% by weight of at least one encapsulating material, in particular 1 to 20% by weight,

d) 0-20% by weight of one or more additional additives, and

e) 0-20% by weight of water.

All weight percentages are based on the total weight of the granules.

In the case of the metal complex compound of formula (1) and the peroxide or peroxide-forming material [component a) as described above, all the preferences given for the granules apply. The catalyst can be granulated as a suitable granulation material.

As binder (b), anionic dispersants, nonionic dispersants, polymers and waxes which are water soluble, dispersible or emulsifiable in water can be considered.

Anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes, pigments and the like. The following products can be considered: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenylene or diphenyl oxide and optionally formaldehyde, (mono- / di-) Alkyl naphthalene sulfonate, sodium salt of polymerized organic sulfonic acid, sodium salt of polymerized alkylnaphthalenesulfonic acid, sodium salt of polymerized alkylbenzenesulfonic acid, alkylarylsulfonate, sodium salt of alkyl polyglycol ether sulfate, polyalkylation Polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids, sodium salts of alkyl diglycol ether sulfates, sodium salts of polynaphthalenemethanesulfonates, lig Nosulfonates or oxylignosulfonates or heterocyclic polysulfonic acids.

Particularly suitable anionic dispersants include condensation products of naphthalenesulfonic acid with formaldehyde, sodium salts of polymerized organic sulfonic acids, (mono-di-) alkylnaphthalenesulfonates, polyalkylated polynuclear arylsulfonates, polymerized alkylbenzenesulfonic acids Sodium salt, lignosulfonate, oxylignosulfonate and condensation products of naphthalenesulfonic acid and polychloromethyldiphenyl.

Suitable nonionic dispersants are especially compounds which have a melting point of at least 35 ° C. and are emulsifiable, dispersible or soluble, for example

1. fatty alcohols having 8 to 22 carbon atoms, in particular cetyl alcohol;

2. Preferably 2 to 80 moles of alkylene oxide, especially ethylene oxide (some of the ethylene oxide units may be substituted by substituted epoxides such as styrene oxide and / or propylene oxide) and 8 to 22 carbon sources Adducts with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides thereof, or with benzyl alcohol, phenyl phenol, benzyl phenol or alkyl phenols, wherein the alkyl radical has 4 or more carbon atoms;

3. alkylene oxides, in particular propylene oxide, condensation products (block polymers);

4. diamines, in particular ethylenediamine and ethylene oxide / propylene oxide adducts;

5. Reaction products of fatty acids having 8 to 22 carbon atoms and primary or secondary amines having at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group, or alkylene oxides of such hydroxyalkyl-group-containing reaction products Addition product;

6. Ethoxylation, such as sorbitan esters with long chain ester groups, or polyoxyethylene sorbitan monolaurate with 4 to 10 ethylene oxide units or polyoxyethylene sorbitan trioleate with 4 to 20 ethylene oxide units Sorbitan esters;

7. Adducts of trihydric or hexavalent aliphatic alcohols having 3 to 6 carbon atoms, such as glycerol or pentaerythritol with propylene oxide; And

8. Fatty alcohol polyglycol mixed ethers with aliphatic monoalcohols, especially addition products having 8 to 30 moles of ethylene oxide and 3 to 30 moles of propylene oxide with 8 to 22 carbon atoms.

Particularly suitable nonionic dispersants are surfactants of the formula (7):

R ₂₃ -O- (alkylene-O) _n -R ₂₄

In the food,

R ₂₃ is C ₈ -C ₂₂ alkyl or C ₈ -C ₁₈ alkenyl;

R ₂₄ is hydrogen; C ₁ -C ₄ alkyl; Cycloaliphatic radicals having 6 or more carbon atoms; Or benzyl;

"Alkylene" is an alkylene radical having 2 to 4 carbon atoms; In addition

n is a number from 1 to 60.

Substituents R ₂₃ and R ₂₄ in formula (7) are each hydrocarbon radicals of unsaturated or preferably saturated aliphatic monoalcohols having 8 to 22 carbon atoms. Hydrocarbon radicals can be straight or branched. R ₂₃ and R ₂₄ are preferably alkyl radicals having 9 to 14 carbon atoms independently of one another.

Aliphatic saturated monoalcohols that may be considered include natural alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol; synthetic alcohols such as 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, Octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C ₉ -C ₁₁ oxo-alcohol, tridecyl alcohol, isotridecyl alcohol and straight primary alcohols having 8 to 22 carbon atoms ( Alfol). Some examples of such Alfol are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) and Alfol (16-18). ("Alfol" is a registered trademark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol and oleyl alcohol.

The alcohol radicals may be present alone or in the form of a mixture of two or more components, such as a mixture of alkyl and / or alkenyl groups derived from soy fatty acid, palm kernel oil fatty acid or tallow oil.

The (alkylene-O) chain is preferably a divalent radical of the formula:

Examples of cycloaliphatic radicals are cycloheptyl, cyclooctyl and preferably cyclohexyl.

As nonionic dispersants, surfactants of formula (8) can be considered:

In the food,

R ₂₅ is C ₈ -C ₂₂ alkyl;

R ₂₆ is hydrogen or C ₁ -C ₄ alkyl;

Y ₁ , Y ₂ , Y ₃ and Y ₄ are independently of each other hydrogen, methyl or ethyl;

n ₂ is a number from 0 to 8; In addition

n ₃ is a number from 2 to 40.

More important nonionic dispersants correspond to formula (9):

In the food,

R ₂₇ is C ₉ -C ₁₄ alkyl;

R ₂₈ is C ₁ -C ₄ alkyl;

Y ₅ , Y ₆ , Y ₇ and Y ₈ are independently of each other hydrogen, methyl or ethyl, one of the radicals Y ₅ , Y ₆ and one of the radicals Y ₇ and Y ₈ are always hydrogen; In addition

n ₄ And n ₅ Are independently of each other an integer of 4 to 8.

Nonionic dispersants of formulas (7) to (9) may be used in the form of a mixture. For example, the surfactant mixture may be a non-terminal group terminating fatty alcohol ethoxylate of formula (7), such as a compound of formula (7) wherein R ₂₃ is C ₈ -C ₂₂ alkyl; R ₂₄ is hydrogen and alkyl The lene-O chain is a radical-(CH ₂ CH ₂ -O)-and end group terminating fatty alcohol ethoxylates of formula (9) can be considered.

Examples of nonionic dispersants of formulas (7), (8) and (9) include C ₁₀ -C ₁₃ fatty alcohols such as C ₁₃ oxo-alcohol and 3 to 10 moles of ethylene oxide, propylene oxide and / or butylene oxide Reaction product or a reaction product of 1 mole of C ₁₃ fatty alcohol with 6 moles of ethylene oxide and 1 mole butylene oxide, the addition product being selected from C ₁ -C ₄ alkyl, preferably methyl or butyl The end group can be terminated.

Such dispersants may be used alone or in the form of a mixture of two or more dispersants. In place of or in addition to anionic or nonionic dispersants, the granules according to the invention may comprise a water soluble organic polymer as a binder. Such polymers may be used alone or in the form of mixtures of two or more polymers.

Water soluble polymers that may be considered are, for example, polyethylene glycol, copolymers of ethylene oxide and propylene oxide, gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidone, vinylpyrrolidone, vinyl acetate, polyvinylimidazole , Polyvinylpyridine-N-oxide, copolymer of vinylpyrrolidone and long chain α-olefin, copolymer of vinylpyrrolidone and vinylimidazole, poly (vinylpyrrolidone / dimethylaminoethyl methacrylate), Copolymer of vinylpyrrolidone / dimethylaminopropyl methacrylate, copolymer of vinylpyrrolidone / dimethylaminopropyl / acrylamide, quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate, vinylcapro Terpolymers of lactam / vinylpyrrolidone / dimethylaminoethyl methacrylate, vinylpyrrolidone and methacrylamidopropyl-trimethylammonium chlora Copolymers, terpolymers of caprolactam / vinylpyrrolidone / dimethylaminoethyl methacrylate, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl Alcohols, polyvinyl acetate, hydrolyzed polyvinyl acetate, copolymers of ethyl acrylate and methacrylate and methacrylic acid, copolymers of maleic acid and unsaturated hydrocarbons, and mixed polymerization products of the aforementioned polymers.

Among the organic polymers, particularly preferred are polyethylene glycol, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, copolymers of hydrolyzed polyvinyl acetate, vinylpyrrolidone and vinyl acetate, and poly Acrylates and copolymers of ethyl acrylate and methacrylate and methacrylic acid, and polymethacrylates.

Suitable water emulsifiable or water dispersible binders include paraffin wax.

Encapsulation material (c) comprises water soluble and water dispersible polymers and waxes. Among these materials, polyethylene glycol, polyamide, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, hydrolyzed polyvinyl acetate, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates Preference is given to paraffins, fatty acids, copolymers of ethyl acrylate and methacrylate and methacrylic acid, and polymethacrylates.

Additives (d) that can be considered are, for example, wetting agents, dust removers, water insoluble or water soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestrants.

The preparation of granules according to the invention can be carried out, for example, from:

a) dissolution or suspension followed by drying / molding steps or

b) Suspending the active ingredient in the melt followed by shaping and solidifying.

a) First anionic or nonionic dispersant and / or polymer and optionally further additives are dissolved in water and stirred if necessary until heating to obtain a homogeneous solution. The catalyst according to the present invention is dissolved or suspended in the resulting aqueous solution. The solids content of the solution should preferably be at least 30% by weight, in particular 40 to 50% by weight, based on the total weight of the solution. The viscosity of the solution is preferably less than 200 mPas.

The aqueous solution according to the invention, prepared as described above, comprising the catalyst according to the invention is subjected to a drying step to remove all water except the residual amount, and at the same time to form solid particles (granules). Known methods are suitable for preparing granules from aqueous solutions. In principle, both continuous and discontinuous methods are suitable. Continuous methods are preferred, in particular spray-dried fluidized bed granulation processes.

Particularly suitable are spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air. The atomization of the solution is carried out using a unitary nozzle or binary nozzle or by the spinning effect of a rapidly rotating disk. To increase the particle size, the spray-drying process can be combined with further agglomeration of liquid particles with solid nuclei in the fluidized bed forming the integral part of the chamber (so-called fluid spray). Particulates (<100 μm) obtained by a conventional spray-drying process are separated from the off-gas flow rate if necessary and then atomized with a spray-dryer for flocculation with liquid droplets of the active ingredient without further treatment. Is supplied as a nucleus to the atomization cone.

During the granulation step, water can be immediately removed from the solution comprising the catalyst, binder and further additives according to the invention. It is also clearly intended that agglomeration of droplet formation in atomizing cones or agglomeration of droplets with solid particles occur.

If necessary, the granules formed in the spray-dryer are removed in a continuous process, such as a sieving process. Particulates and large particles are either directly reused (no need to be redissolved) in the process or dissolved in liquid active ingredient formulations and then granulated again.

The production process according to a) is a process of mixing a polymer with water and then dissolving / suspending the catalyst in the polymer solution to form an aqueous phase, wherein the catalyst according to the invention is uniformly distributed in said phase. At the same time or subsequently, the aqueous phase is dispersed in a liquid which is not mixed with water in the presence of a dispersion stabilizer to form a stable dispersion. Water is then removed from the dispersion by distillation to form substantially dry particles. In these particles, the catalyst is evenly distributed in the polymer matrix.

The granules according to the invention are abrasion resistant, dust free, pourable and easily weighed. They can be added to the preparations, such as detergent preparations, at the desired concentrations of the catalysts according to the invention.

If it is necessary to suppress the pigmented appearance of the granules in the cleaning agent, it is necessary to insert the granules into droplets of a white, soluble material ("water-soluble wax") or to add a white pigment (such as TiO ₂ ) to the granule formulation, or Preferably by encapsulating the granules in a melt composed of a water soluble wax, as described in EP-A-0 323 407 (which can add white solids to the melt to enhance the masking effect of the capsule).

b) The catalyst according to the invention is dried in a separate step before melt granulation and, if necessary, dry-milled in the mill so that all solid particles have a size of <50 μm. The drying can be carried out in conventional apparatus for this purpose, such as paddle dryers, vacuum cabinets or freeze-dryers.

Fine particulate catalyst is suspended and homogenized in the melt carrier material. The desired granules are prepared from the suspension in a molding step with simultaneous solidification of the melt. The selection of a suitable melt-granulation process is made according to the desired granule size. In principle, processes that can be used to produce granules with a particle size of 0.1 to 4 mm are suitable. This process is a flake formation with a droplet process (while solidifying on a cooling belt or free-falling in a cooling air stream), melt-prilling (cooling medium gas / liquid) and subsequent milling steps, the granulating apparatus being continuously or It is operated discontinuously.

If the coloring appearance of the granules produced from the melt is to be suppressed in the cleaning agent, in addition to the catalyst, white or colored pigments (such as titanium dioxide) can be suspended in the melt which give the granules the desired colored appearance after solidification.

If necessary, the granules can be coated or encapsulated with encapsulating material. Suitable methods for such encapsulation include conventional methods and include encapsulation of the granules by melts consisting of water soluble waxes, core cellulose, composite coacervation and surface polymerization as described in EP-A-0 323 407. do.

Encapsulating material (c) comprises, for example, water soluble, water dispersible or water soluble polymers and waxes.

Additional additives (d) include, for example, wetting agents, dust removal agents, water insoluble or water soluble dyes or pigments, and also dissolution accelerators, optical brighteners and sequestrants.

Other products of the invention include novel form forms specially developed for industrial and laboratory cleaning, such as powders or granules that can be administered in a liquid bleaching of the catalyst in water or organic solvents or in separate bleaching steps for cleaning applications. Solid forms such as;

Surprisingly, the metal complex compounds of formula (1) exhibit markedly enhanced bleach promoting action against pigmented contamination in walls or floor tiles.

It is particularly important to use the metal complex compound of the formula (1) as a catalyst for reacting with the peroxy compound in the hard surface, especially the cleaning solution of the wall or floor tile.

The metal complex compounds of formula (1), together with the peroxy compounds, also exhibit excellent antimicrobial activity. Also of interest is the use of the metal complex compound of formula (1) for sterile use or for protection against bacterial attack.

The invention also relates to novel metal complexes of the general formula (1):

(1)

(One)

In the formula,

Me is manganese, titanium, iron, cobalt, nickel or copper,

X is a coordination radical or a bridge radical,

n and m are each independently an integer having a value of 1 to 8,

p is an integer having a value from 0 to 32,

z is the charge of the metal complex,

Y is a large ion,

q is z / (charge of Y), and

L is the following formula (2)

(2)의 리간드이고,

Is a ligand of (2),

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen; Unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉

Wherein R ₉ is hydrogen, cation or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively;

SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ ,

Wherein R ₁₀ is hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively;

-NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ^® R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N [(C ₁ -C ₆ alkylene) -NR ₁₁ R _{12] 2;} -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ^® R ₁₁ R ₁₂ R ₁₃ ; -N [(C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13] 2; -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ^® R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is as defined above and

R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, or

R ₁₁ and R ₁₂ combine with the nitrogen atom connecting them to form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain additional hetero atoms,

Q is N or CR ₈ Wherein R ₈ has the same meaning as defined for R ₁ -R ₇ or

를 형성하며, R ₈ is combined with A

Form the

Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 are independently of each other H, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,

Q ₁ Is N or CR ' ₈ Wherein R ' ₈ has the same meaning as defined in R ₁ -R ₇ ,

A has _one of the meanings as defined in R ₁ -R ₇ , or

A is combined with R ₈

를 형성하며,

Form the

Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 have the same meaning as defined above and b and c are independently 1, 2 or 3 of each other.

All the above preferred contents (in the case of use) also apply to the metal complex as it is.

Preferred embodiments of the invention relate to novel metal complexes of the general formula (1 '):

In the formula,

Me 'is manganese, titanium, iron, cobalt, nickel or copper,

X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And a, wherein R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O

n 'is an integer with a value of 1 or 2,

m 'is an integer with a value of 1,

p 'is an integer with a value of 2,

z 'is an integer having a value of 4 to 4+, preferably 0 to 4+, particularly preferably 0,

Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate and tartrate, or, wherein R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl, or sulfophenyl,

q 'is an integer from 0 to 4, preferably 0,

L 'is formula (2a), (2b) or (2d)

Is a ligand of

R ₁ , R ₂ , R ₄ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ' ₈ and A are each independently hydrogen; Unsubstituted C ₁ -C ₁₂ alkyl; C ₁ -C ₁₂ alkyl substituted by one or more substituents selected from the group consisting of —OH, —CN, —NH ₂ , COOH and COOC ₁ -C ₂ alkyl; Unsubstituted phenyl or N-mono-substituted by hydroxy at C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, unsubstituted or alkyl moieties Or phenyl substituted by N, N-di-C ₁ -C ₄ alkylamino, N-phenyl-amino, N-naphthylamino, phenyl, phenoxy or naphthyloxy; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ , wherein R ₉ is in each case hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or phenyl substituted as above; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , wherein R ₁₀ in each case is hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N + R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is hydrogen, C ₁ -C ₄ alkyl or phenyl and R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, Unsubstituted phenyl or substituted phenyl as indicated above, or R ₁₁ and R ₁₂ , combined with the nitrogen atom connecting them, are unsubstituted or one or more unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C _An imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan ring substituted by ₄ alkyl, wherein the nitrogen atom is quaternized.

Particularly preferred embodiments of the invention relate to novel metal complexes of the general formula (1 '):

In the formula,

Me 'is manganese or iron,

X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And a, R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O

n 'is an integer with a value of 1 or 2,

m 'is an integer with a value of 1,

p 'is an integer with a value of 2,

z 'is an integer having a value of 0 to 4+, preferably 0,

Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate or tartrate, R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl or sulfophenyl,

q 'is an integer having a value of 0 to 4, preferably 0,

L 'is the following formula (2'a), (2'b) or (2'd)

Is a ligand of

Wherein R ₁ and R ₄ are independently of each other H; -CH ₃ ; -Cl; -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ;

ego,

A and R ₂ are independently of each other H or -CH ₃ ,

이고, R ₃ is -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ );

ego,

R ₈ and R ₆ are each independently hydrogen; -CH ₃ ; -Cl; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ ); -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₂ CH ₃ ) (CH ₂ CH ₂ OH) or -N (CH ₃ ) CH ₂ CH ₂ OH, and

R ₇ is H; -CH ₃ ; -CH ₂ COOH; -CH ₂ CH ₂ COOH; -CH ₂ CN or -CH ₂ CH ₂ CN.

The invention also relates to novel ligands of formula (2)

(2)

(2)

In the formula,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen; Unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉

Wherein R ₉ is hydrogen, cation or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively;

SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ ,

Wherein R ₁₀ is hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively;

-NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ^® R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N [(C ₁ -C ₆ alkylene) -NR ₁₁ R _{12] 2;} -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ^® R ₁₁ R ₁₂ R ₁₃ ; -N [(C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13] 2; -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ^® R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is as defined above and

R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, or

R ₁₁ and R ₁₂ combine with the nitrogen atom connecting them to form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain additional hetero atoms,

Q is N or CR ₈ Wherein R ₈ has the same meaning as defined for R ₁ -R ₇ or

를 형성하며, R ₈ is combined with A

Form the

Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 are independently of each other H, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy,

Q ₁ Is N or CR ' ₈ Wherein R ' ₈ has the same meaning as defined in R ₁ -R ₇ ,

A has _one of the meanings as defined in R ₁ -R ₇ , or

A is combined with R ₈

를 형성하며,

Form the

Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 have the same meaning as defined above and b and c are independently 1, 2 or 3 of each other.

All of the above-mentioned preferences (for use and metal complex) apply to the metal complex itself.

Preferred embodiments of the invention also relate to novel ligands of formula (2a), (2b) or (2d):

In the formula,

R ₁ , R ₂ , R ₄ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ' ₈ and A are each independently hydrogen; Unsubstituted C ₁ -C ₁₂ alkyl; C ₁ -C ₁₂ alkyl substituted by one or more substituents selected from the group consisting of —OH, —CN, —NH ₂ , COOH and COOC ₁ -C ₂ alkyl; Unsubstituted phenyl or N-mono-substituted by hydroxy at C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano, nitro, carboxy, sulfo, hydroxy, amino, unsubstituted or alkyl moieties Or phenyl substituted by N, N-di-C ₁ -C ₄ alkylamino, N-phenyl-amino, N-naphthylamino, phenyl, phenoxy or naphthyloxy; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ , wherein R ₉ is in each case hydrogen, cation, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or phenyl substituted as above; -SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , wherein R ₁₀ in each case is hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted phenyl or substituted phenyl as indicated above; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ⁺ R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N + R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ⁺ R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is hydrogen, C ₁ -C ₄ alkyl or phenyl and R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen, unsubstituted or hydroxy-substituted C ₁ -C ₁₂ alkyl, Unsubstituted phenyl or substituted phenyl as indicated above, or R ₁₁ and R ₁₂ , combined with the nitrogen atom connecting them, are unsubstituted or one or more unsubstituted C ₁ -C ₄ alkyl and / or substituted C ₁ -C _An imidazole, pyrazole, pyrrolidine, piperidine, piperazine, morpholine or azepan ring substituted by ₄ alkyl, wherein the nitrogen atom is quaternized.

Particularly preferred embodiments of the invention relate to novel ligands of the formulas (2'a), (2'b) and (2'd):

In the formula,

R ₁ and R ₄ are independently of each other H; -CH ₃ ; -Cl; -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ;

ego,

A and R ₂ are independently of each other H or -CH ₃ ,

이고, R ₃ is -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ );

ego,

R ₈ and R ₆ are each independently hydrogen; -CH ₃ ; -Cl; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ ); -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₂ CH ₃ ) (CH ₂ CH ₂ OH) or -N (CH ₃ ) CH ₂ CH ₂ OH, and

R ₇ is H; -CH ₃ ; -CH ₂ COOH; -CH ₂ CH ₂ COOH; -CH ₂ CN or -CH ₂ CH ₂ CN.

Another aspect of the present invention is a method for preparing a compound of formula (2). Suitable methods are, for example, condensation reactions according to the following schemes:

Wherein all substituents have the meaning as defined above.

Starting materials are known or can be prepared according to known methods.

Metal complexes of formula (1) are prepared according to the general method. A suitable method is to react the ligand of formula (2) with a suitable metal salt in the desired molar ratio.

The reactions of formulas (2e) and (2f) are carried out in a suitable solvent such as THF in the presence of a base such as triethylamine. The reaction temperature is 20 ° C to 180 ° C.

The following examples are intended to illustrate the invention and do not limit the invention. Parts and percentages are by weight unless otherwise indicated. Temperatures are in degrees Celsius unless otherwise noted.

Secondary amine base block ( building block ) Synthesis

Example 1 Methyl-pyridin-2-ylmethyl-amine

Anhydrous methylamine solution (300 ml, 40% w / w) in isopropanol (300 ml) was added to 2-chloromethyl-pyridine hydrochloride (8 g, 48.8 mmol). This solution was stirred for 2 days at room temperature. After evaporation, an aqueous carbonate solution (80 ml) was added and the aqueous layer was extracted with dichloromethane (4 x 100 ml each). The combined organic phases were dried over sodium sulfate, filtered and evaporated. After distillation on Cuperol apparatus, methyl-pyridin-2-ylmethyl-amine was obtained as a yellow oil.

Example 2 : (4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amine

Methylamine aqueous solution (180 ml, 40% w / w) was added to a solution of 2-chloromethyl-3,5-dimethyl-4-methoxypyridine hydrochloride (6.0 g, 27 mmol) dissolved in isopropanol (180 ml). Was added and the mixture was stirred at room temperature for 2 days. After evaporation, an aqueous carbonate solution (40 ml) was added and the aqueous layer was extracted with dichloromethane (5 × 100 ml each). The combined organic layers were dried over sodium sulfate, filtered and evaporated to afford (4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methylamine as a yellow solid.

Example 3 : ethyl 4-chloropicolinate

N, N'-dimethylformamide (10.0 ml, 130 mmol) was added carefully to thionyl chloride (295 ml, 4.06 mol) at 40 ° C with stirring. After 30 minutes, finely powdered picolinic acid (100 g, 812 mmol) was added in 10 equal portions over 30 minutes and the temperature was maintained at 38-42 ° C. The temperature was raised to 70 ° C. over 2 hours (sudden generation of SO ₂ / HCl) and the mixture was stirred at this temperature for 1 day. A portion of the volatiles (about 150 ml) was distilled off and replaced with toluene (about 150 ml) and removal of the volatiles (again about 150 ml) was repeated once more. Toluene was added to a total volume of about 450 ml and the resulting solution was poured into ethanol-toluene solution (1: 1 (v / v), 240 ml) and cooled in an ice bath. The resulting suspension was stirred overnight and concentrated to 1/2 of volume on a rotary evaporator. The mixture was filtered at 0 ° C. and washed with toluene (250 ml). After drying in vacuo, ethyl 4-chloropicolinate hydrochloride was obtained as a beige solid.

The hydrochloride was partitioned between ethyl acetate (300 ml) and water (200 ml) and quickly neutralized with aqueous sodium hydroxide (125 ml, 4M). The aqueous layer was separated and extracted twice with ethyl acetate (200 ml each). The combined organic layers were dried over sodium sulfate (50 g), filtered and concentrated to dryness. After evaporation in vacuo (0.2 millibar, 65-70 ° C.), ethyl 4-chloropicolinate was obtained as a colorless semisolid.

Example 4 (4-Chloro-pyridin-2-yl) -methanol

To a solution of ethyl 4-chloropicolinate (11.14 g, 60 mmol) in anhydrous ethanol (450 ml) was added sodium borohydride (3.63 g, 96 mmol) with stirring at 0 ° C. The mixture was stirred for 1 hour and then further stirred at room temperature for 30 minutes. After heating to 70 ° C. for 1 hour, water was added carefully at room temperature. The pH value was adjusted to 5.5 using aqueous HCl (4M). After stirring for 14 hours, the volatiles were removed in vacuo. Water was added and the mixture was extracted with dichloromethane (2 x 200 ml each). The organic phase was dried over sodium sulphate, filtered and evaporated to afford (4-chloropyridin-2-yl) -methanol as a clear yellow oil.

Example 5 4-Chloro-2-chloromethyl-pyridine

To a solution of (4-chloro-pyridin-2-yl) -methanol (7.70 g, 53.6 mmol) in dichloromethane (350 ml) was added thionyl chloride (8.16 g, 68.6 mmol) with stirring at room temperature. . Water was extracted using dichloromethane (2 × 150 ml each) and the pH value was adjusted to 8. The aqueous layer was extracted with dichloromethane (2 x 150 ml each). The combined organic phases were dried over sodium sulphate, filtered and evaporated to afford 4-chloro-2-chloromethyl-pyridine as a yellow oil.

Example 6 : (4-Chloro-pyridin-2-ylmethyl) -methyl-amine

To a solution of 4-chloro-2-chloromethyl-pyridine (8.9 g, 55 mmol) in isopropanol (150 ml) was added aqueous methylamine (100 ml, 40% w / w) and the mixture was allowed to come to room temperature. Stir for 16 hours. After evaporation, the residue was partitioned between water and chloroform at pH 9. The combined organic extracts were dried over sodium sulfate, filtered and evaporated to afford (4-chloro-pyridin-2-ylmethyl) -methyl-amine as a yellow solid.

Example 7 (4-Dimethylamino-pyridin-2-yl) -methanol

A solution of (4-chloro-pyridin-2-yl) -methanol (6.68 g, 47 mmol) in aqueous dimethylamine (30 ml, 7.9 M, 5 equiv) was heated to 155 ° C. in a pressurized reactor for 14 hours. . After evaporating the volatiles, the residue was dissolved in water and the pH value was adjusted to 8.5 using sodium hydroxide (4M in water). The mixture was concentrated on a rotary evaporator and the beige solid was extracted for 16 hours with chloroform in a Soxhlet apparatus. The extract was evaporated and the crude product was recrystallized from methanol / diethyl ether.

Example 8 (2-Chloromethyl-pyridin-4-yl) -dimethyl-amine

To a solution of (4-dimethylamino-pyridin-2-yl) -methanol (4.50 g, 29.6 mmol) in dichloromethane (350 ml) was added thionyl chloride (4.50 g, 37.9 mmol) at room temperature. After stirring for 1.5 hours water (150 ml) was added and the pH value was adjusted to 8.5. The aqueous phase was extracted with dichloromethane (2 x 100 ml). The combined organic phases were dried over sodium sulfate, filtered and evaporated to afford (2-chloromethyl-pyridin-4-yl) -dimethyl-amine as a brownish semisolid.

Example 9 : Dimethyl- (2-methylaminomethyl-pyridin-4-yl) -amine

A mixture containing (2-chloromethyl-pyridin-4-yl) -dimethyl-amine (3.67 g, 21.5 mmol), aqueous methylamine (50 ml, 40% w / w) and isopropanol (100 ml) was prepared at room temperature Stir for 20 hours. The volatiles were removed in vacuo and dimethyl- (2-methylaminomethyl-pyridin-4-yl) -amine containing HCl was isolated as a beige solid.

Example 9a : (4-Pyrrole-1-yl-pyridin-2-yl) -methanol

(4-Chloro-pyridin-2-yl) -methanol (1.71 g, 11.9 mmol) was suspended in 20 ml 1,3-dimethyl-2-imidazolidinone (DMEU) at 0 ° C. under inert atmosphere. Pyrrole (1.97 ml, 28.4 mmol) and potassium t-butylate (3.2 g, 28.5 mmol) were added and the mixture was stirred at 105 ° C. for 6 hours. After cooling to rt, the reaction mixture was further stirred at rt for 12 h. After evaporation of the volatiles, the residue was partitioned at pH 9 between water and diethyl ether. The combined organic extracts were dried over sodium sulfate, filtered and evaporated to afford the crude product. After column chromatography (silica gel, hexane / ethyl acetate 1: 2), (4-pyrrole-1-yl-pyridin-2-yl) -methanol was obtained as a brownish powder.

Example 9b 2-Chloromethyl-4-pyrrole-1-yl-pyridine

To a solution of (4-pyrrole-1-yl-pyridin-2-yl) -methanol (130 mg, 0.746 mmol) in dichloromethane (10 ml) was added thionyl chloride (70 μl, 0.955 mol) at room temperature. It was. After stirring for 2 hours, water (10 ml) was added and the pH value was adjusted to 8.5. The aqueous layer was extracted using dichloromethane (2 x 50 ml). The combined organic phases were dried over sodium sulfate, filtered and evaporated to give 2-chloromethyl-4-pyrrole-1-yl-pyridine as a brownish oil. The crude product thus obtained was used for next step without further purification.

Example 9c Methyl- (4-pyrrole-1-yl-pyridin-2-ylmethyl) -amine

A solution containing 2-chloromethyl-4-pyrrole-1-yl-pyridine (86 mmg, 0.446 mmol), aqueous methylamine (1.2 ml, 40% w / w) and isopropanol (3 ml) was added at room temperature for 16 hours. Was stirred. The volatiles were removed in vacuo and crude methyl- (4-pyrrole-1-yl-pyridin-2-ylmethyl) -amine was obtained as a brown oil which was used in the next step without purification.

Chloromethyl  Synthesis of basic blocks

Example 10 6-Chloromethyl-2-pyridin-2-yl-pyrimidin-4-ol

Of pyridine-2-carboxamidine hydrochloride (3.15 g, 20 mmol), potassium t-butoxide (2.24 g, 20 mmol) and methyl 4-chloroacetoacetate (7.05 ml, 60 mmol) in ethanol (90 ml) The mixture was refluxed for 17 hours. After evaporation, the crude mixture was partitioned between chloroform and water (pH = 7). The organic layer was dried over sodium sulfate, filtered and evaporated. The crude material was recrystallized from isopropanol to give 6-chloromethyl-2-pyridin-2-yl-pyrimidin-4-ol as a white solid.

Example 11 6-Chloromethyl-2- (4-chloro-pyridin-2-yl) -pyrimidin-4-ol

A solution of pyridine-2-carboxamidine hydrochloride (192 mg, 1 mmol) and DBU (298 μl, 2 mmol) in methanol (10 ml) was dissolved in methyl 4-chloroacetoacetate (585) in methanol (20 ml). Μl, 5 mmol) was added at 60 ° C. over 1.5 hours. The volatiles were removed in vacuo and the mixture was dissolved in water (pH = 7). The crude product was isolated by filtration and crystallized from isopropanol to give 6-chloromethyl-2- (4-chloro-pyridin-2-yl) -pyrimidin-4-ol as a white solid.

Example 12 1-pyridin-2-yl-butane-1,3-dione

A solution of anhydrous acetone (8.71 g, 150 mmol) dissolved in anhydrous tetrahydrofuran (100 ml) was added under argon to a solution of sodium ethoxide (20.42 g, 300 mmol) in anhydrous tetrahydrofuran (300 ml). A solution of ethyl pyridine-2-carboxylate (22.68 g, 150 mmol) dissolved in anhydrous tetrahydrofuran (100 ml) was added dropwise over 20 minutes. The mixture was stirred at room temperature for 15 hours and at reflux for 4 hours. This mixture was evaporated on a rotary evaporator, mixed with water (150 ml) and neutralized with glacial acetic acid. Extract twice with diethyl ether, organic extracts were combined, dried (sodium sulfate) and evaporated on a rotary evaporator to give 1-pyridin-2-ylbutane-1,3-dione as an orange oil.

Ketotomer: CH ₂ group at 4.20 ppm (ratio of enol / keto form = 87: 13).

Example 13 : 2,4,6-trioxo-6-pyridin-2-yl-hexanoic acid ethyl ester

1-pyridin-2-yl in 100 ml 1,2-dimethoxyethane refluxed into a stirred suspension of sodium hydroxide (16.7 g, 60% pure, 417 mmol) in anhydrous 1,2-dimethoxyethane (200 ml) A solution of butane-1,3-dione (22.7 g, 139 mmol) and diethyl oxalate (40.6 g, 276 mmol) was added over 1 hour. The reaction mixture was refluxed for 3 hours and then evaporated and treated carefully with hydrochloric acid (2M, 150 ml). After stirring for 10 minutes, the precipitate was filtered, washed with water and dried to give 2,4,6-trioxo-6-pyridin-2-yl-hexanoic acid ethyl ester as a yellow solid.

Example 14 4-hydroxy- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester

2,4,6-trioxo-6-pyridin-2-yl-hexanoic acid ethyl ester (12 g, 49 mmol) was suspended in ethanol (300 ml). After addition of ammonium acetate (25 g, 324 mmol), the mixture was heated to reflux for 4 hours. After evaporating the volatiles, the residue was triturated with aqueous sodium hydroxide solution to achieve pH = 7. After extraction with chloroform (3 x 300 ml), the organic layers were combined, dried over sodium sulfate and evaporated. The crude material was purified by column chromatography on silica gel (chloroform / methanol / aqueous ammonia 95: 4: 1) to give 4-hydroxy- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester as a brown solid. .

Example 15 6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol

4-hydroxy- [2,2 in anhydrous tetrahydrofuran (20 ml) over 45 minutes at 0 ° C. in a stirred suspension of lithium aluminum hydride (912 mg, 24 mmol) in anhydrous tetrahydrofuran (30 ml). '] Bipyridinyl-6-carboxylic acid ethyl ester (1.46 g, 6 mmol) solution was added under argon. The mixture was stirred at rt for 2 h. The resulting suspension was cooled to 0 ° C. and treated with dilute hydrochloric acid to achieve pH = 7. After filtration through celite, the filtrate was evaporated and the pure product was isolated as a beige solid by column chromatography (silica gel, chloroform / methanol / aqueous ammonia 9: 1: 0.1).

Example 16 : 6-chloromethyl- [2,2 '] bipyridinyl-4-ol

6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol (100 mg, 0.5 mmol) was suspended in anhydrous dichloromethane at 0 ° C. under inert atmosphere. Thionyl chloride (154 mg, 1.14 mmol, 2.28 equiv) was added dropwise with stirring. After 15 minutes, the cooling bath was removed and the mixture was stirred for 40 minutes at room temperature. After cooling to 0 ° C., water (10 ml) was added and the pH value of the mixture was adjusted to 7 with sodium carbonate solution. The organic layer was separated and the aqueous layer was extracted using dichloromethane (2 x 100 ml). The combined organic extracts were dried over sodium sulfate, filtered and evaporated at 30 ° C. to give 6-chloromethyl- [2,2 ′] bipyridinyl-4-ol as a white, semisolid.

Example 17 6- (4-Chloro-pyridin-2-yl) -2,4,6-trioxo-hexanoic acid ethyl ester

Of the three flasks, under argon, sodium hydride (60% in inorganic oil, 10.0 g, 0.25 mol, 2.5 equiv) was washed twice with n-hexane (100 ml each). Anhydrous tetrahydrofuran (140 ml) was added and the mixture was heated to 62 ° C. A solution in which ethyl 4-chloropicolinate (18.6 g, 0.1 mol) and ethyl acetopyrubeninib (15.8 g, 0.1 mol) was dissolved in anhydrous tetrahydrofuran (30 ml) was added with stirring over 1 hour. During the addition, strong hydrogen gas evolution indicates the progress of the reaction. The reddish suspension was further stirred at 62 ° C. for 15 minutes and then cooled to 0 ° C. in an ice / water bath. Water (100 ml) was added carefully. Aqueous HCl was added to the orange suspension (4M, about 50 ml; final pH value = 7). The resulting yellow suspension was filtered and dried. The crude product thus obtained was used without further purification.

Example 18 4'-Chloro-4-hydroxy- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester

6- (4-Chloro-pyridin-2-yl) -2,4,6-trioxo-hexanoic acid ethyl ester (30.65 g, 0.103 mol) was suspended in isopropanol (300 ml). After addition of ammonium acetate (15.87 g, 0.206 mol), the mixture was heated to reflux for 4 hours. After evaporation of the volatiles, the residue was triturated with water (250 ml). Aqueous sodium hydroxide solution was added with stirring to achieve pH = 8 (from 4-5). After extraction using chloroform (3 x 300 ml), the combined organic layers were dried over sodium sulfate and evaporated to give 4'-chloro-4-hydroxy- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester. Obtained as a brownish solid.

Example 19 4'-Chloro-6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol

4'-Chloro-4-hydroxy- [2,2 '] bipyridinyl-6-carboxylic acid ester ester (11.15 g, 40 mmol) and sodium borohydride (9.08 g, 240 in anhydrous dimethoxyethane (220 ml) Mmol) was heated to reflux. Anhydrous methanol (37 ml) was added carefully over 3 hours. The brown suspension was cooled to room temperature. Aqueous HCl (4M) was added to achieve pH = 5. Sodium hydroxide solution (4M) was added with stirring to pH 7-8 and volatiles were removed in vacuo. The residue was chromatographed on silica gel using ethyl acetate / methanol / aqueous ammonia 4: 1: 0.05 (v / v). 4'-Chloro-6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol was obtained as a yellowish powder.

Example 20 4'-chloro-6-chloromethyl- [2,2 '] bipyridinyl-4-ol

4'-Chloro-6-chloromethyl- [2,2 '] bipyridinyl-4-ol (2.73 g, 11.5 mmol) was suspended in anhydrous dichloromethane at 0 ° C under inert atmosphere. Thionyl chloride (1.91 ml, 2.28 equiv) was added dropwise. After 10 minutes, the cooling bath was removed and the mixture was stirred at room temperature for 30 minutes. After cooling to 0 ° C., water (40 ml) was added and the pH value of the mixture was adjusted to 7 with sodium carbonate solution. The organic layer was separated and the aqueous layer was extracted with dichloromethane (2 x 150 ml). The combined organic extracts were dried over sodium sulfate, filtered and evaporated at 30 ° C. to give 4'-chloro-6-chloromethyl- [2,2 '] bipyridinyl-4-ol as a white solid semisolid.

Example 20a : 4'-dimethylamino-6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol

A solution of 4'-chloro-6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol (1.17 g, 4.96 mmol) in aqueous dimethylamine (60 ml, 7.9 M) was dissolved in a pressure reactor. Heated to 155 ° C. for 5 h. After cooling to room temperature, the mixture was further stirred at this temperature for 14 hours. The volatiles were removed in vacuo and 4'-dimethylamino-6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol containing HCl was isolated as a beige solid.

Example 20b 6-chloromethyl-4'-dimethylamino- [2,2 '] bipyridinyl-4-ol

4'-dimethylamino-6-hydroxymethyl- [2,2 '] bipyridinyl-4-ol (2.6 g, 10.6 mmol) was suspended in anhydrous dichloromethane at 0 ° C under inert atmosphere. Thionyl chloride (1.75 ml, 24.2 mmol, 2.28 equiv) was added dropwise with stirring. After 15 minutes, the cooling bath was removed and the mixture was stirred at room temperature for 2.5 hours. After cooling to 0 ° C., water (100 ml) was added and the pH value was adjusted to 7 using sodium carbonate solution. The organic layer was separated and the aqueous layer was extracted using chloroform (4 x 200 ml). The combined organic extracts were dried over sodium sulfate, filtered and evaporated to afford 6-chloromethyl-4'-dimethylamino- [2,2 '] bipyridinyl-4-ol as a colorless powder. This crude product is used in the next step without further purification.

Example 20c 4,4'-Dichloro- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester

4'-Chloro-4-hydroxy- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester (836) in a solution of phosphorus pentachloride (1.5 g, 7.2 mmol) dissolved in phosphoric trichloride (38 ml) mg, 3.0 mmol) was added in small portions at room temperature. This mixture was heated to reflux for 3 hours. After cooling to room temperature, the volatiles were evaporated and the residue was partitioned between dichloromethane and saturated aqueous sodium carbonate solution. The combined organic extracts were dried over sodium sulfate and evaporated to give 4,4'-dichloro- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester as a brownish powder.

Example 20d : (4,4'-dichloro- [2,2 '] bipyridinyl-6-yl) -methanol

Of 4,4'-dichloro- [2,2 '] bipyridinyl-6-carboxylic acid ethyl ester (462 mg, 1.56 mmol) and sodium borohydride (353 mg, 9.34 mmol) in anhydrous dimethoxyethane (15 ml) The mixture was heated to reflux. A solution of anhydrous methanol (3 ml) in dimethoxyethane (15 ml) was carefully added over 4 hours. After cooling to room temperature, an aqueous solution of hydrochloric acid (4 M) was added to bring the pH to 5. This mixture was stirred for 4 days at room temperature. Sodium hydroxide solution (2 M) was added to adjust pH to 8 and then the volatiles were removed in vacuo. The residue was chromatographed on silica gel using hexane / ethyl acetate 1: 1. (4,4'-Dichloro- [2,2 '] bipyridinyl-6-yl) -methanol was obtained as a brownish powder.

Example 20e : (4,4'-dimethylamino- [2,2 '] bipyridinyl-6-yl) -methanol

A solution of (4,4'-dichloro- [2,2 '] bipyridinyl-6-yl) -methanol (235 mg, 0.921 mmol) in aqueous dimethylamine (25 ml, 7.9M) was dissolved for 2 hours. Heated to 160 ° C. and left for 16 hours at room temperature in a pressure reactor. After evaporating the volatiles, 4,4'-bis-dimethylamino- [2,2 '] bipyridinyl-6-yl) -methanol was obtained as a beige solid.

Example 20f : 6-Chloromethyl-N, N, N ', N'-tetramethyl- [2,2'] bipyridinyl-4,4'-diamine

(4,4'-bis-dimethylamino- [2,2 '] bipyridinyl-6-yl) -methanol (250 mg, 0.918 mmol) was suspended in anhydrous dichloromethane at 0 ° C. under inert atmosphere. Thionyl chloride (0.152 ml, 2.1 mmol, 2.28 equiv) was added dropwise with stirring. After 15 minutes, the cooling bath was removed and the mixture was stirred at room temperature for 2 hours. After cooling to 0 ° C., water (10 ml) was added and the pH value of the mixture was adjusted to 8 using sodium carbonate solution. The organic layer was separated and the aqueous layer was extracted using dichloromethane (3 x 50 ml). The combined organic extracts were dried over sodium sulfate, filtered and evaporated to afford 6-chloromethyl-N, N, N ', N'-tetramethyl- [2,2'] bipyridinyl-4,4'-diamine. Obtained as a brown oil. This compound was used in the next step without purification.

Ligand  And Complex  synthesis

Example 21 6-{[methyl- (2-pyridin-2-yl-ethyl) -amino] -methyl} -2-pyridin-2-yl-pyrimidin-4-ol

6-Chloromethyl-2-pyridin-2-yl-pyrimidin-4-ol (222 mg, 1 mmol), methyl- (2-pyridin-2-yl-ethyl) -amine in tetrahydrofuran (35 ml) (136 mg, 1 mmol) and triethylamine (202 mg, 2 mmol) were refluxed for 3 days. After filtration from the white precipitate, the mother liquor was concentrated in vacuo. Pure product was obtained as a brownish oil via column chromatography (RP 18, acetonitrile / water 4: 1).

Example 22 6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amino] -methyl} -2-pyridin-2-yl-pyrimidin-4-ol

In tetrahydrofuran (10 ml) 6-chloromethyl-2-pyridin-2-yl-pyrimidin-4-ol (280 mg, 1.3 mmol), (4-methoxy-3,5-dimethyl-pyridine-2 A mixture containing -ylmethyl) -methyl-amine (234 mg, 1.3 mmol) and triethylamine (360 μl, 4 mmol) was refluxed for 3 days. After evaporation of the volatiles, the pure product was isolated via column chromatography (RP 18, acetonitrile / water 7: 5) as a white solid.

Example 23 6-{[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2 '] bipyridinyl-4-ol

6-chloromethyl- [2,2 '] bipyridinyl-4-ol (100 mg, 0.4 mmol), potassium carbonate (373 mg, 2.7 mmol) and methyl-pyridin-2-ylmethyl-amine (67 mg, 0.54 mmol) was refluxed for 16 h. After filtration and evaporation of the volatiles, the product was isolated as a beige semisolid by chromatography (silica gel, chloroform / methanol).

Example 24 4'-Chloro-6-{[methyl- (2-pyridin-2-yl-ethyl) -amino] -methyl}-[2,2 '] bipyridinyl-4-ol

In tetrahydrofuran (25 ml) 4'-chloro-6-chloromethyl- [2,2 '] bipyridinyl-4-ol (252 mg, 0.99 mmol), methyl- (2-pyridin-2-yl- The mixture containing ethyl) -amine (137 μl, 0.99 mmol) and triethylamine (550 μl, 1.99 mmol) was refluxed for 3 days. After evaporation of the volatiles, the residue was dissolved in water and extracted using chloroform (3 × 100 ml) with pH = 7.5. The organic phase was dried over sodium sulfate and evaporated. The pure product was isolated via column chromatography (RP 18, acetonitrile / water 7: 3) as a brownish oil.

Example 25 6-{[methyl- (2-pyridin-2-yl-ethyl) -amino] -methyl} -4'-pyrrolidin-1-yl- [2,2 '] bipyridinyl-4 -All

4'-chloro-6-{[methyl- (2-pyridin-2-yl-ethyl) -amino] -methyl}-[2,2 '] bipyridinyl-4-ol (138 mg, 0.39 mmol), A mixture of pyrrolidine (643 μL, 7.8 mmol) and chlorobenzene (10 ml) was heated to 90 ° C. for 1 day in the presence of traces of zinc chloride (II). After evaporation of the volatiles, the residue was adjusted to 8 in water and extracted using chloroform (2 × 100 ml). The organic phase was dried over sodium sulphate, filtered and evaporated. The pure product was chromatographed on aluminum oxide (chloroform) and then obtained as a yellow oil.

Example 26 4'-Chloro-6-{[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2 '] bipyridinyl-4-ol

In tetrahydrofuran (200 ml) 4'-chloro-6-chloromethyl- [2,2 '] bipyridinyl-4-ol (2.26 g, 8.9 mmol), methylpyridin-2-ylmethyl-amine (1.19 g, 9.75 mmol) and triethylamine (4.9 ml, 35 mmol) were refluxed for 2 days. After evaporation of the volatiles, the residue was dissolved in water and extracted with dichloromethane (pH = 8) (2 x 250 ml). The organic phase was dried over sodium sulfate and evaporated. Pure product was isolated via column chromatography (RP 18, methanol / water 4: 1) as a brownish oil.

Example 27 6-[(methyl-pyridin-2-ylmethyl-amino) -methyl] -4'-pyrrolidin-1-yl- [2,2 '] bipyridinyl-4-ol

4'-Chloro-6-[(methyl-pyridin-2-ylmethyl-amino-methyl]-[2,2 '] bipyridinyl-4-ol (574 mg, 1.68 mmol), pyrrolidine (2.79 ml , 33.7 mmol) and chlorobenzene (45 ml) were heated under reflux in the presence of traces of zinc chloride (II) for 2 days, after evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water and And extracted using chloroform (2 × 100 ml) The organic phase was dried over sodium sulfate, filtered and evaporated The pure product was chromatographed on aluminum oxide (chloroform) and then obtained as a yellow oil.

Example 28 : 4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2'] bipyridinyl -4-ol

4'-Chloro-6-[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2 '] bipyridinyl-4-ol (485 mg, 1.42 mmol), N-methylamino ethanol (2.13 g, 28.4 mmol), and a mixture of chlorobenzene (40 ml) were heated for 2 days under reflux in the presence of traces of zinc chloride (II). After evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water and extracted using chloroform (3 x 200 ml). The organic phase was dried over sodium sulfate, filtered and evaporated. The pure product was chromatographed on aluminum oxide (chloroform / methanol 95: 5) and then obtained as a beige solid.

Example 29 4 '-(4-Methyl-piperazin-1-yl) -6-[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2'] bipyridinyl-4 -All

4'-Chloro-6-[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2 '] bipyridinyl-4-ol (1.31 g, 3.84 mmol), N-methyl piperazine (8.54 ml, 77 mmol) and chlorobenzene (40 ml) were heated for 1 day under reflux in the presence of zinc (II) chloride. After evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water. The pure product was chromatographed on aluminum oxide (chloroform) and then obtained as a beige oil.

Example 30 4- {4'-hydroxy-6 '-[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2'] bipyridinyl-4-yl} -1, 1-dimethyl-piperazine-1- 윰 iodide

4 '-(4-methyl-piperazin-1-yl) -6-[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2'] bipyridi in acetonitrile (1 ml) A stirred solution of nile-4-ol (283 mg, 0.7 myrmol) was treated with 1 equivalent of methyl iodide solution in acetonitrile at 0 ° C. The resulting suspension was diluted with acetonitrile (1 ml) and stirred overnight at room temperature. The product was isolated by filtration and washing with acetonitrile (2 ml) and then as a white solid.

Example 31 4'-Chloro-6-{[(4-dimethylamino-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol

Tetrahydrofuran (25 ml) 4'-chloro-6-chloromethyl- [2,2 '] bipyridinyl-4-ol (280 mg, 1.1 mmol), dimethyl- (2-methylaminomethyl-pyridine- A mixture containing 4-yl) -amine (209 mg, 1.26 mmol) and triethylamine (610 μL, 4.4 mmol) was refluxed for 2 days. After evaporation, the pure product was isolated as a beige solid via column chromatography (RP18, methanol / water 9: 1).

Example 32 : 6-{[(4-Dimethylamino-pyridin-2-ylmethyl) -methyl-amino] -methyl} -4'-pyrrolidin-1-yl- [2,2 '] bipyridinyl -4-ol

4'-Chloro-6-{[(4-dimethylamino-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol (113 mg, 294 μ Mole), pyrrolidine (487 μl, 5.9 mmol) and chlorobenzene (10 ml) were heated for 18 hours under reflux in the presence of traces of zinc chloride (II). After evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water. Pure product was obtained after chromatography on aluminum oxide (chloroform / methanol 20: 1).

Example 33 : 6-{[(4-Dimethylamino-pyridin-2-ylmethyl) -methyl-amino] -methyl} -4 '-[(2-hydroxyethyl) -methyl-amino]-[2, 2 '] bipyridinyl-4-ol

4'-Chloro-6-{[(4-dimethylamino-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol (128 mg, 33 μ Mole), N-methylamino ethanol (533 μl, 6.66 mmol) and chlorobenzene (10 ml) were heated under reflux for 18 hours in the presence of traces of zinc chloride (II). After evaporation of the volatiles, the residue was neutralized by the addition of dilute hydrochloric acid in water. The pure product was obtained as a yellow oil after chromatography on aluminum oxide (chloroform / methanol 10: 1).

Example 34 : 4'-Chloro-6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-aminomino] -methyl}-[2,2 '] bipyridi Nil-4-ol

6-chloromethyl-2-pyridin-2-yl-pyrimidin-4-ol (983 mg, 3.85 mmol) in tetrahydrofuran (100 ml), (4-methoxy-3,5-dimethyl-pyridine-2 A mixture containing -ylmethyl) -methyl-amine hydrochloride (764 mg, 4.24 mmol) and triethylamine (2.15 ml, 15.4 mmol) was refluxed for 2 days. The volatiles were removed in vacuo and water (50 ml) was added. After extraction with dichloromethane (2 x 200 ml), the organic layer was collected, dried over sodium sulphate and evaporated. The pure product was isolated as a yellowish solid via column chromatography (RP 18, methanol / water 4: 1).

Example 35 : 4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amino] -Methyl}-[2,2 '] bipyridinyl-4-ol

4'-Chloro-6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol (250 mg, 0.627 mmol), a mixture of N-methylamino ethanol (1.0 ml, 12.5 mmol) and chlorobenzene (15 ml) was heated for 2 days under reflux in the presence of zinc (II) chloride (4 mg). After evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water and extracted with chloroform (2 x 200 ml). The organic phase was dried over sodium sulphate and evaporated. The pure product was chromatographed on aluminum oxide (chloroform / methanol 9: 1) and obtained as a brownish semisolid.

Example 36 6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amino] -methyl} -4′-pyrrolidin-1-yl- [2, 2 '] bipyridinyl-4-ol

4'-Chloro-6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol (250 mg, 0.627 mmol), a mixture of N-methylamino ethanol (1.0 ml, 12.5 mmol) and chlorobenzene (15 ml) was heated for 1 day under reflux in the presence of zinc (II) chloride (4 mg). After evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water and extracted with chloroform (2 x 150 ml). The organic phase was dried over sodium sulphate and evaporated. The pure product was chromatographed on chloroform and obtained as a beige semisolid.

Example 37 6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amino] -methyl} -4 '-(4-methyl-piperazin-1-yl )-[2,2 '] bipyridinyl-4-ol

4'-Chloro-6-{[(4-methoxy-3,5-dimethyl-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol (294 mg, 0.737 mmol), a mixture of N-methylamino piperazine (1.64 ml, 14.7 mmol) and chlorobenzene (18 ml) was heated under reflux for 1 day in the presence of zinc (II) chloride (5 mg). After evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water and extracted with chloroform (3 x 100 ml). The organic phase was dried over sodium sulphate and evaporated. The pure product was chromatographed on chloroform and obtained as a beige semisolid.

Example 38 : 4'-Chloro-6-{[(4-chloro-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol

Tetrahydrofuran (200 ml) 6-chloromethyl-2-pyridin-2-yl-pyrimidin-4-ol (4.0 g, 15.7 mmol), (4-chloro-pyridin-2-ylmethyl) -methyl- The mixture containing amine (2.70 g, 17.3 mmol) and triethylamine (8.73 ml, 63 mmol) was refluxed for 1.5 days. After evaporation, the aqueous product was isolated as a brownish solid via column chromatography (RP18, methanol / water 4: 1).

Example 39 6-{[methyl-4-pyrrolidin-1-yl-pyridin-2-ylmethyl) -amino] -methyl} -4'-pyrrolidin-1-yl- [2,2 ' ] Bipyridinyl-4-ol

4'-Chloro-6-{[(4-chloro-pyridin-2-ylmethyl) -methyl-amino] -methyl]-[2,2 '] bipyridinyl-4-ol (750 mg, 2 mmol) A mixture of, pyrrolidine (5.0 ml, 60 mmol) and chlorobenzene (50 ml) was heated for 1 day under reflux in the presence of zinc (II) chloride (14 mg). After evaporation of the volatiles, the residue was neutralized by addition of dilute hydrochloric acid in water and extracted with chloroform (3 x 100 ml). The organic phase was dried over sodium sulfate, filtered and evaporated. Pure product was chromatographed on aluminum oxide (dichloromethane / methanol 15: 1) and then obtained as a beige semisolid.

Example 40 : 4 '-[(2-hydroxyethyl) -methyl-amino] -6-[[{4-[(2-hydroxy-ethyl) -methyl-amino] -pyridin-2-ylmethyl} -Methyl-amino) -methyl]-[2,2 '] bipyridinyl-4-ol

4'-Chloro-6-{[(4-chloro-pyridin-2-ylmethyl) -methyl-amino] -methyl]-[2,2 '] bipyridinyl-4-ol (1.12 g, 3 mmol) , A mixture of N-methylamino ethanol (0.96 ml, 12 mmol) and water (5 ml) was heated under reflux in a pressure reactor for 1 day. After evaporation of the volatiles, the residue was obtained via chromatography on aluminum oxide (chloroform / methanol 4: 1) as a gray semisolid.

Example 40a : 4'-dimethylamino-6-{[(4-dimethylamino-pyridin-2-ylmethyl) -methyl-amino] -methyl}-[2,2 '] bipyridinyl-4-ol

In tetrahydrofuran (110 ml) 6-chloromethyl-4'-dimethylamino [2,2 '] bipyridinyl-4-ol (1.06 g, 4.01 mmol) and dimethyl- (2-methylaminomethyl-pyridine- The mixture containing 4-yl) -amine (0.80 g, 4.82 mmol) and triethylamine (3.35 ml, 24.1 mmol) was refluxed for 2 days. After filtration, the filtrate was evaporated and the pure product was isolated by column chromatography on aluminum oxide (chloroform / methanol 9: 1) and then yellowish powder.

Example 40b 6-{[(4-Dimethylamino-pyridin-2-ylmethyl) -methyl-amino] -methyl} -N, N, N ', N'-tetramethyl- [2,2'] BP Ridinyl-4,4'-diamine

In tetrahydrofuran (15 ml) 6-chloromethyl-N, N, N ', N'-tetramethyl- [2,2'] bipyridinyl-4,4'-diamine (170 mg, 0.585 mmol) and A mixture containing dimethyl- (2-methylaminomethyl-pyridin-4-yl) -amine (116 mg, 0.702 mmol) and triethylamine (0.49 ml, 3.51 mmol) was refluxed for 20 hours. After evaporation, the pure product was isolated as a brownish oil after column chromatography on aluminum oxide (chloroform / methanol 9: 1).

Example 40c 4'-dimethylamino-6-{[methyl- (4-pyrrole-1-yl-pyridin-2-ylmethyl) -amino] -methyl}-[2,2 '] bipyridinyl-4 -All

6-chloromethyl-4'-dimethylamino- [2,2 '] bipyridinyl-4-ol (117 mg, 0.446 mmol) and methyl- (4-pyrrole-1-yl) in tetrahydrofuran (14 ml) A mixture containing pyridin-2-ylmethyl) -amine (83 mg, 0.446 mmol) and triethylamine (0.37 ml, 2.66 mmol) was refluxed for 2.5 days. After filtration, the filtrate was evaporated and the pure product was isolated by column chromatography on aluminum oxide (chloroform / methanol 9: 1) and then as a brownish powder.

Example 41 4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-[({4-[(2-hydroxy-ethyl) -methyl-amino] -pyridin-2-ylmethyl } -Methyl-amino) -methyl]-[2,2 '] bipyridinyl-4-ol

과의 망간 착물

Manganese complexes with

착물을 황색 기포로서 얻었다. 4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-[({4-[(2-hydroxy-ethyl) -methyl-amino] -pyridin-2-ylmethyl} -methyl- A solution of amino) -methyl]-[2,2 '] bipyridinyl-4-ol (36 mg, 0.079 mmol) and manganese (II) chloride tetrahydrate (15 mg, 1 equiv) was lyophilized

The complex was obtained as a yellow bubble.

Example 42 4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-[(methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2'] bipyridinyl -4-ol

과의 망간 착물

Manganese complexes with

착물을 황색 기포로서 얻었다. 4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-[({4-[(2-hydroxy-ethyl) -methyl-amino] -pyridin-2-ylmethyl} -methyl- A solution of amino) -methyl]-[2,2 '] bipyridinyl-4-ol (43 mg, 0.112 mmol) and manganese (II) chloride tetrahydrate (22 mg, 1 equiv) was lyophilized

The complex was obtained as a yellow bubble.

Example 43 : 4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-[({methyl-pyridin-2-ylmethyl-amino) -methyl]-[2,2'] bipyridi Nil-4-ol

과의 철 착물

Iron complex with

4 '-[(2-hydroxy-ethyl) -methyl-amino] -6-[(methyl-pyridin-2-ylmethyl- by mixing the components in an Ellenmeyer flask and then diluting them to a final concentration of 50 μM An aqueous 1.6 mM solution of amino) -methyl]-[2,2 '] bipyridinyl-4-ol and iron (II) chloride (1 equiv) was prepared.

apply Example

Application Example 1 : (Bleaching Contamination in Laundry at Ambient Temperature)

로 나타내며, 이것은 촉매 존재하 및 부재하에서 세탁된 직물의 휘도 사이의 차이를 지칭한다. 1 g of circular contamination (BC01 tea, CFT; WFK10.0 carrot juice, WFK; CS20 / 2 tomatoes, CFT; BC04 curry, CFT) was added to a vial with 3 ml wash solution. The wash solution contained a standard detergent (IEC 60456 ^* ) at a concentration of 7.5 g / l. The hydrogen peroxide concentration was 10 mmol / liter. The catalyst concentration (1: 1 complex in situ of the ligand with manganese (II) chloride tetrahydrate or iron (II) chloride in methanol solution) was 25 μmol / liter. The vial was shaken for 50 minutes at ambient temperature using a shaker. The fabric was carefully rinsed and ironed after the treatment. The luminance Y according to the CIE standard procedure of the contaminated test fabric was measured before and after the test using the Gretag SPM 100 instrument, respectively.

This refers to the difference between the brightness of the washed fabric in the presence and absence of a catalyst.

=0)의 표백 성능을 현저하게 향상시킴을 알 수 있다. From the table above, the presence of the complexes of the present invention is characterized by the presence of hydrogen peroxide on various

It can be seen that the bleaching performance of = 0) is significantly improved.

Application Example 2 : (contamination bleaching during washing at 40 ° C.)

의 증가(CIE에 따른 휘도)는 분광광도계적으로 측정하였다. 7.5 g white cotton fabric and 2.5 g tea contaminated cotton fabric were treated in 80 ml of wash liquor. The wash contained a standard detergent (IEC 60456 A ^* ) at a concentration of 7.5 g / l. The hydrogen peroxide concentration was 10 mmol / liter. The catalyst concentration (1: 1 complex in situ of the ligand with manganese (II) chloride tetrahydrate in the methanolic solution) was 20 μmol / liter. The washing process was carried out at 40 ° C. for 30 minutes in a steel beaker in the LINITEST apparatus. In order to evaluate the bleaching results, the luminance of the contamination against the reference experiment without addition of catalyst

The increase of (luminance according to CIE) was measured spectrophotometrically.

=0)과 비교한 휘도에서 현저한 증가가 관찰되었다. As shown in the table above, the catalyst-free washing process (

A significant increase in brightness compared to = 0) was observed.

Application Example 3 : (Contaminated Bleaching in Washing with Peracetic Acid as Oxidizer)

로 나타내며, 이것은 촉매 존재하 및 부재하에서 세탁된 직물의 휘도 사이의 차이를 지칭한다. 1 g of circular contamination (BC01 tea, CFT; WFK10.0 carrot juice, WFK; CS20 / 2 tomatoes, CFT; BC04 curry, CFT) was added to a vial with 3 ml wash solution. The wash solution contained a standard detergent (IEC 60456 ^* ) at a concentration of 7.5 g / l. The peracetic acid concentration was 3 mmol / liter. The catalyst concentration (1: 1 complex in situ of the ligand with manganese (II) chloride tetrahydrate or iron (II) chloride in methanol solution) was 10 μmol / liter. The vial was shaken for 50 minutes at ambient temperature using a shaker. The fabric was carefully rinsed and ironed after the treatment. The luminance Y according to the CIE standard procedure of the contaminated test fabric was measured before and after the test using the Gretag SPM 100 instrument, respectively.

This refers to the difference between the brightness of the washed fabric in the presence and absence of a catalyst.

The table shows that the presence of the complexes of the present invention significantly improves the bleaching performance of peracetic acid on different bleachable contaminants.

Good results can also be obtained by using a combination of H ₂ O ₂ instead of TEAD and peracetic acid.

Application Example 4 : (Bleaching Contamination in Laundry with Oxygen from Air as an Oxidizer)

로 나타내는 표백 효과, 즉 촉매 존재하 및 부재하에서 세탁된 직물의 휘도의 차를 지칭한다. 1 g of circular contamination (WFK 10SG Tomato-Beef Sauce, WFK) was added to a vial containing 3 ml of 10 mM carbonate buffer (pH 10). The buffer contained 0.6% linear alkylbenzenesulfonate. The catalyst concentration (1: 1 complex in situ of manganese (II) chloride tetrahydrate and ligand in methanol solution) was 20 μmol / liter. The vial was shaken for 30 minutes at ambient temperature using a shaker. The fabric was carefully rinsed and ironed after the treatment. The luminance Y according to the CIE standard procedure of the contaminated test fabric was measured before and after the test (0h) using the Gretag SPM 100 instrument, respectively. The dirt was stored in the cow for 24 hours and the luminance value was measured once more. .

Bleaching effect, i.e., the difference in luminance of the washed fabric in the presence and absence of a catalyst.

It can be seen that the complexes of the present invention can effectively bleach contamination on the fabric even in the absence of added peroxides.

Application Example 5 (Dish washing)

Tea contaminated cups were prepared according to the IKW method (IKW-Arbeitskreis Maschienenspulmittel, “Methoden zurBestimmung der Rginigungsleistung von maschinellen Geschirrspulmitteln (Part A and B)”, SOFW, 11 + 14, 1998). The primary contaminated cup contained 44 mM hydrogen peroxide and 20 μM catalyst (1: 1 complex in situ of manganese (II) chloride hydrate and ligand in methanol solution). After 15 minutes the solution was removed and the cup was rinsed with water. Removal of secondary deposits was visually assessed on a criteria of 0 (ie no change, very strong deposits) to 10 (ie no deposits). A rating of 4.5 was observed in the reference diet without catalyst.

The table shows that the grade obtained by the experiment with the catalyst of the present invention is significantly better than the reference value.

Application Example 6 : (Delignification of Pulp)

5 g (dry weight) of softwood cellulose with kappa number 30 were placed in a plastic bag with 71 ml carbonate buffer, pH 10 (0.4% sodium bicarbonate and 0.5% sodium carbonate) and 13.3 ml 30% hydrogen peroxide solution. The catalyst solution (from ligand 28-Mn) was prepared in situ by dissolving an equimolar amount of ligand and manganese (II) chloride tetrahydrate in methanol. 52.8 ppm of catalyst was added to the pulp. The pulp thus obtained was vigorously kneaded and then maintained for 90 minutes in a 40 ° C. water bath under constant temperature control. Filtration was carried out and the pulp was washed three times with warm water (60 ° C.). The kappa number of the pulp after the treatment was κ = 20.6 as measured according to TAPPI T236 om-99. The kappa number of the pulp in the control experiment was κ = 23.9. The use of the catalyst of the present invention resulted in significant delignification of the pulp as compared to the control experiment without the catalyst.

Claims (17)

Use as a catalyst for oxidation of at least one metal complex of formula (1) (One) In the formula, Me is manganese, titanium, iron, cobalt, nickel or copper, X is a coordination radical or a bridge radical, n and m are each independently an integer having a value of 1 to 8, p is an integer having a value from 0 to 32, z is the charge of the metal complex, Y is a large ion, q is z / (charge of Y), and L is the following formula (2)

Is a ligand of (2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen; Unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ Wherein R ₉ is hydrogen, cation or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively; SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , Wherein R ₁₀ is hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ^® R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N [(C ₁ -C ₆ alkylene) -NR ₁₁ R _{12] 2;} -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ^® R ₁₁ R ₁₂ R ₁₃ ; -N [(C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13] 2; -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ^® R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is as defined above and R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, or R ₁₁ and R ₁₂ combine with the nitrogen atom connecting them to form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain additional hetero atoms, Q is N or CR ₈ Wherein R ₈ has the same meaning as defined for R ₁ -R ₇ or R ₈ is combined with A

Form the Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 are independently of each other H, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, Q ₁ Is N or CR ' ₈ Wherein R ' ₈ has the same meaning as defined in R ₁ -R ₇ , A has _one of the meanings as defined in R ₁ -R ₇ , or A is combined with R ₈

Form the Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 have the same meaning as defined above and b and c are independently 1, 2 or 3 of each other. The use of claim 1, wherein at least one metal complex of formula (1 ') is used:

In the formula, Me 'is manganese, titanium, iron, cobalt, nickel or copper, X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And a, wherein R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O n 'is an integer with a value of 1 or 2, m 'is an integer having a value of 1 or 2, preferably 1, p 'is an integer having a value from 0 to 4, in particular 2, z 'is an integer having a value of 8- 8+, preferably of 4--4 +, more preferably of 0-4 +, in particular of 0, Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate and tartrate, or, wherein R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl or sulfophenyl, q 'is an integer from 0 to 8, preferably 0 to 4, more preferably 0, L 'is formula (2a), (2b) or (2c)

Is a ligand of which all substituents have the same meanings as defined in claim 1. The use of claim 1, wherein at least one metal complex of formula (1 ') is used:

In the formula, Me 'is manganese or iron, X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And a, R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O n 'is an integer with a value of 1 or 2, m 'is an integer with a value of 1, p 'is an integer with a value of 2, z 'is an integer having a value of 0 to 4+, preferably 0, Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate or tartrate, R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl or sulfophenyl, q 'is an integer having a value of 0 to 4, preferably 0, L 'is the following formula (2'a), (2'b) or (2'd)

Is a ligand of Wherein R ₁ and R ₄ are independently of each other H; -CH ₃ ; -Cl; -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ;

ego, A and R ₂ are independently of each other H or -CH ₃ , R ₃ is -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ );

ego, R ₈ and R ₆ are each independently hydrogen; -CH ₃ ; -Cl; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ ); -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₂ CH ₃ ) (CH ₂ CH ₂ OH) or -N (CH ₃ ) CH ₂ CH ₂ OH, and R ₇ is H; -CH ₃ ; -CH ₂ COOH; -CH ₂ CH ₂ COOH; -CH ₂ CN or -CH ₂ CH ₂ CN. The metal complex compound of any one of claims 1 to 3, wherein the metal complex compound of formula (1) is used for bleaching spots or stains on textile materials in connection with a washing process or by direct application of a decontaminant; For cleaning hard surfaces, in particular wall tiles or floor tiles; For use in automated dishwashing compositions; To bleach spots or stains on textile materials by atmospheric oxygen, wherein the bleaching is promoted during and / or after treatment of the fabric in a wash liquor; To prevent redeposition of mobile dyes during washing of the fabric material; For use in washing and cleaning liquids having antibacterial action; For use as a pretreatment for bleaching fabrics; For use as a catalyst in selective oxidation in connection with organic synthesis; For use as a catalyst for wastewater treatment; For use as a catalyst for peroxy compounds for decolorization in papermaking; For sterilization; And peroxide or peroxide-forming materials, for contact lens disinfection, O ₂ And / or use as a catalyst with air. Detergents, cleaners, disinfectants or bleach compositions containing the following materials: I) 0-50% by weight of A) at least one anionic surfactant and / or B) at least one nonionic surfactant based on the total weight of the composition, II) 0 to 70% by weight of C) at least one builder material, based on the total weight of the composition, III) 1 to 99% by weight of D) at least one peroxide or peroxide forming material, O ₂ and / or air, based on the total weight of the composition, IV) When adding 0.5 to 50 g / l of detergent, cleaner, disinfectant or bleach to the wash liquor, any of claims 1 to 3 in an amount having a concentration of 0.5 to 100 mg / liter of wash liquor. E) at least one metal complex compound of formula (1) or (1 ') as defined in claim 1, and V) 0 to 20% by weight of one or more additional additives, based on the total weight of the composition, and VI) 100% by weight of water, based on the total weight of the composition. The method of claim 5, I) 0-50% by weight of A) at least one anionic surfactant and / or B) at least one nonionic surfactant based on the total weight of the composition, II) 0 to 70% by weight of C) at least one builder material, based on the total weight of the composition, III) 1 to 99% by weight of D) at least one peroxide or peroxide forming material, O ₂ and / or air, based on the total weight of the composition, IV) An amount having a concentration of 1 to 50 mg / liter of washing liquid when adding 0.5 to 50 g / l of detergent, cleaning agent, disinfectant or bleaching agent to the washing liquid. E) at least one metal complex compound of formula (1) or (1 '), as defined in claim 1, and V) 0 to 20% by weight of one or more additional additives, based on the total weight of the composition, and VI) 100% by weight of water, based on the total weight of the composition. The method of claim 6,  I) from 1 to 50% by weight of A) at least one anionic surfactant and / or B) at least one nonionic surfactant, based on the total weight of the composition, II) 1 to 70% by weight of C) at least one builder material, based on the total weight of the composition, III) 1 to 99% by weight of D) at least one peroxide or peroxide forming material, O ₂ and / or air, based on the total weight of the composition, IV) 0.005 to 2% by weight, based on the total weight of the composition, E) at least one metal complex compound of formula (1) or (1 ') as defined in claims 1 to 3, and V) 0 to 20% by weight of one or more additional additives, based on the total weight of the composition, and VI) 100% by weight of water, based on the total weight of the composition. 8. A composition according to any one of claims 5 to 7, which is used for textile materials or hard surface materials. 8. A composition according to any one of claims 5 to 7, which is a dishwashing detergent formulation. The composition of claim 9 which is an automatic dishwashing detergent formulation. a) from 1 to 99% by weight, based on the total weight of the granules, of at least one metal complex compound of formula (1) and at least one peroxide, as defined in any one of claims 1 to 3, b) from 1 to 99% by weight of one or more builders, based on the total weight of the granules, c) 0 to 20% by weight of one or more encapsulating materials, based on the total weight of the granules, d) 0 to 20% by weight of one or more additional additives, based on the total weight of the granules, and e) granules comprising 0 to 20% by weight of water, based on the total weight of the granules. a) from 1 to 99% by weight of at least one metal complex compound of formula (1) and at least one peroxide forming material, based on the total weight of the granules, b) from 1 to 99% by weight of one or more builders, based on the total weight of the granules, c) 0 to 20% by weight of one or more encapsulating materials, based on the total weight of the granules, d) 0 to 20% by weight of one or more additional additives, based on the total weight of the granules, and e) granules comprising 0 to 20% by weight of water, based on the total weight of the granules. A metal complex of formula (1)

In the formula, Me is manganese, titanium, iron, cobalt, nickel or copper, X is a coordination radical or a bridge radical, n and m are each independently an integer having a value of 1 to 8, p is an integer having a value from 0 to 32, z is the charge of the metal complex, Y is a large ion, q is z / (charge of Y), and L is the following formula (2)

Is a ligand of (2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen; Unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ Wherein R ₉ is hydrogen, cation or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively; SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , Wherein R ₁₀ is hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ^® R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N [(C ₁ -C ₆ alkylene) -NR ₁₁ R _{12] 2;} -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ^® R ₁₁ R ₁₂ R ₁₃ ; -N [(C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13] 2; -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ^® R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is as defined above and R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, or R ₁₁ and R ₁₂ combine with the nitrogen atom connecting them to form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain additional hetero atoms, Q is N or CR ₈ Wherein R ₈ has the same meaning as defined for R ₁ -R ₇ or R ₈ is combined with A

Form the Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 are independently of each other H, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, Q ₁ Is N or CR ' ₈ Wherein R ' ₈ has the same meaning as defined in R ₁ -R ₇ , A has _one of the meanings as defined in R ₁ -R ₇ , or A is combined with R ₈

Form the Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 have the same meaning as defined above and b and c are independently 1, 2 or 3 of each other. The metal complex of claim 13, wherein the metal complex of formula

In the formula, Me 'is manganese or iron, X 'is CH ₃ CN; H ₂ O; F ^-; Cl ^-; Br ^-; HOO ^-; O _{² 2} ^-; O ^{2 -;} R ₁₆ COO ^-; And a, R ₁₆ is hydrogen, C ₁ -C ₄ alkyl, phenyl or sulfophenyl, ^- or R ₁₆ O n 'is an integer with a value of 1 or 2, m 'is an integer with a value of 1, p 'is an integer with a value of 2, z 'is an integer having a value of 0 to 4+, preferably 0, Y 'is R ₁₇ COO ^-; ClO ₄ ^-; BF ₄ ^-; PF ₆ ^-; R ₁₇ SO ₃ ^-; R ₁₇ SO ₄ ^-; SO ₄ ^{2 -;} NO ₃ ^-; F ^-; Cl ^-; Br ^-, I ^-, citrate, oxalate or tartrate, R ₁₇ is hydrogen; C ₁ -C ₄ alkyl; Phenyl or sulfophenyl, q 'is an integer having a value of 0 to 4, preferably 0, L 'is the following formula (2'a), (2'b) or (2'd)

Is a ligand of Wherein R ₁ and R ₄ are independently of each other H; -CH ₃ ; -Cl; -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ;

ego, A and R ₂ are independently of each other H or -CH ₃ , R ₃ is -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ );

ego, R ₈ and R ₆ are each independently hydrogen; -CH ₃ ; -Cl; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ ); -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₂ CH ₃ ) (CH ₂ CH ₂ OH) or -N (CH ₃ ) CH ₂ CH ₂ OH, and R ₇ is H; -CH ₃ ; -CH ₂ COOH; -CH ₂ CH ₂ COOH; -CH ₂ CN or -CH ₂ CH ₂ CN. Ligands of Formula (2)

(2) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ are each independently hydrogen; Unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl; Cyano; halogen; Nitro; -COOR ₉ or -SO ₃ R ₉ Wherein R ₉ is hydrogen, cation or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively; SR ₁₀ , -SO ₂ R ₁₀ or -OR ₁₀ , Wherein R ₁₀ is hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, respectively; -NR ₁₁ R ₁₂ ; - (C ₁ -C ₆ alkylene) -NR ₁₁ R _12; -N ^® R ₁₁ R ₁₂ R ₁₃ ; - (C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ; -N [(C ₁ -C ₆ alkylene) -NR ₁₁ R ₁₂ ] ₂ ; -N (R ₁₀ )-(C ₁ -C ₆ alkylene) -N ^® R ₁₁ R ₁₂ R ₁₃ ; -N [(C ₁ -C _{6 ^{alkylene) -N ® R 11 R 12 R}} 13] 2; -N (R ₁₀ ) -NR ₁₁ R ₁₂ or -N (R ₁₀ ) -N ^® R ₁₁ R ₁₂ R ₁₃ , wherein R ₁₀ is as defined above; In addition R ₁₁ , R ₁₂ and R ₁₃ are each independently hydrogen or unsubstituted or substituted C ₁ -C ₁₈ alkyl or unsubstituted or substituted aryl, or R ₁₁ and R ₁₂ combine with the nitrogen atom connecting them to form an unsubstituted or substituted 5-, 6- or 7-membered ring which may contain additional hetero atoms, Q is N or CR ₈ Wherein R ₈ has the same meaning as defined for R ₁ -R ₇ or R ₈ is combined with A

Form the Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 are independently of each other H, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy, Q ₁ Is N or CR ' ₈ , wherein R' ₈ has the same meaning as defined in R ₁ -R ₇ , A has _one of the meanings as defined in R ₁ -R ₇ , or A is combined with R ₈

Form the Wherein R ₁₄ , R _'14 , R ₁₅ , R' ₁₅ , R " ₁₅ and R"_'15 have the same meaning as defined above and b and c are independently 1, 2 or 3 of each other. 16. The ligand of claim 15, wherein the ligand of formula (2'a), (2'b) or (2'd):

In the formula, R ₁ and R ₄ are independently of each other H; -CH ₃ ; -Cl; -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ;

ego, A and R ₂ are independently of each other H or -CH ₃ , R ₃ is -OH; -OCH ₃ ; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ );

ego, R ₈ and R ₆ are each independently hydrogen; -CH ₃ ; -Cl; -NH ₂ ; -N (CH ₃ ) ₂ ; -N (CH ₂ CH ₃ ) ₂ ; -N (CH ₃ ) (CH ₂ CH ₃ ); -N (CH ₂ CH ₂ OH) ₂ ; -N (CH ₂ CH ₃ ) (CH ₂ CH ₂ OH) or -N (CH ₃ ) CH ₂ CH ₂ OH, and R ₇ is H; -CH ₃ ; -CH ₂ COOH; -CH ₂ CH ₂ COOH; -CH ₂ CN or -CH ₂ CH ₂ CN. Process for preparing a compound of formula (2) according to the following scheme:

Wherein all substituents have the meaning as defined in claim 1.