WO2011066934A1

WO2011066934A1 - Nonhygroscopic transition metal complexes, process for preparation thereof and use thereof

Info

Publication number: WO2011066934A1
Application number: PCT/EP2010/007234
Authority: WO
Inventors: Gerd Reinhardt; Michael Best
Original assignee: Clariant International Ltd
Priority date: 2009-12-05
Filing date: 2010-11-30
Publication date: 2011-06-09
Also published as: DE102009057220A1

Abstract

The invention relates to manganese complexes of the general formula (1) in which M is independently selected from manganese in the III or IV oxidation state, X is independently a coordinating or bridging species selected from H₂O, O₂ ^2-, O^2-, O₂ ^-, OH^-, HO₂ ^-, SH^-, S^2-, SO, Cl^-, N^3-, SCN^-, N₃ ^-, RCOO^-, NH₂ ^- and NR₃, where R is a radical selected from H, C₁-C₄ alkyl and C₆H₅, L are independently organic ligands which each contain at least two nitrogen atoms coordinated to manganese, z is an integer from ‑4 to +4, Y is a counterion of the formula R'-C₆H₄-SO₃ ^- which leads to charge neutrality of the complex, where R' is CH₃, C₂H₅ or i-C₃H₇, and q is an integer from 1 to 4. The invention also relates to processes for preparation of the manganese complexes of general formula (1) and to the use of one or more manganese complexes of the general formula (1) as oxidation or bleaching catalysts, especially in detergents and cleaning agents.

Description

Non-hygroscopic transition metal complexes, process for their preparation and their use

The invention relates to transition metal complex compounds with

Alkylbenzenesulfonate counterions having 1 to 3 carbon atoms in the alkyl group, in particular tosylate or cumene sulfonate counterions, processes for their preparation and their use as oxidation or bleaching catalysts, in particular in detergents and cleaners.

In European powder detergents, the bleaching component has long been based on bleaching agents that release peroxide compounds during washing. These strongly oxidizing compounds very effectively remove the

various types of stains, such as tea, wine and fruits, without polluting the environment, as it was with other countries

Chlorine bleach is the case. Depending on the peroxide compound used, usually perborates or percarbonates, which are necessary for effective bleaching

Washing temperatures between 60 and 95 ° C. At temperatures below 60 ° C, however, the effectiveness of oxygen bleaching drops sharply. For economic and ecological reasons, efforts are therefore made to find compounds that allow oxygen bleaching even at low temperatures. While to improve the bleaching performance of detergents on textile fabrics at low temperatures usually bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate sodium (NOBS) or

Decanoyloxybenzoic acid (DOBA), find for cleaning hard surfaces, such. As in dishwashing detergents, in addition to bleach activators bleach catalysts reinforced use. This is especially a good

Cleaning performance on stubborn tea stains expected. More recently, bleach catalysts are also being used to a greater extent in textile and paper bleaching as well as in chemical synthesis (oxidation reactions).

These bleach catalysts are usually metal-containing

Compounds of iron, cobalt or manganese. On the one hand, they are relatively simple Compounds such as metal salts (eg Manganacetate) or

On the other hand, transition-metal complexes with open-chain or cyclic ligands are of particular interest, since they greatly exceed the bleaching performance of simple systems by a number of coordination compounds such as cobalt pentamine acetates in use. In particular, manganese or iron complexes containing ligands based on triazacyclononane and derivatives thereof have particular bleach-active activity or high oxidizing power from the series of the latter catalysts. Examples of preparation and use of such metal complexes are

for example in US 2009/0126121, WO 2008/086937, US 2002/0066542, US 2001/0044402, US 2001/0025695, US 5,516,738, WO 2000/088063 and EP 0 530 870. For their ease of handling during manufacture, processing and application, it is often necessary to use solid, less hygroscopic compounds. In particular, bleaching and oxidation catalysts have proven useful here, the large-volume counterions such

Hexafluorophosphat, perchlorate or tetraphenylborate included. Such

Complexes are z. In EP 0458 397, EP 0 458 398 and WO 96/06154.

For the synthesis of such transition metal complexes of the triazacydone and its derivatives, a number of manufacturing methods are known. So z. In

WO 93/25562 describes a process for the preparation of active manganese complex catalysts comprising the following steps:

i) reaction of a manganese (II) salt with a triazacyclononane derivative such as 1, 4,7-trimethyl-1, 4,7-triazacyclononane in the presence of a counterion salt such as KPF ₆ in an aqueous-alcoholic medium to form a manganese coordination compound

ii) subsequent oxidation of the manganese coordination compound with an oxidizing agent while maintaining a pH of at least 12, to form the desired manganese complex, wherein the manganese is preferably in the +3 and / or +4 oxidation state, iii) the reaction mixture obtained in step ii) is adjusted to a pH of 7 to 9, then the manganese oxides formed are filtered off and the manganese complex is isolated by evaporation of the solvent mixture. The yields achieved are 59 to 73%.

The counterion significantly affects the physical properties of the metal complex. US 5,274,147 discloses that small counterions such as

Chloride, sulfate or acetate anions lead to oily products. These are highly hygroscopic and not in powder form in this form

Applications suitable. They are therefore mostly as an aqueous solution

used, such. As described in WO 2006/125517. Large-volume counterions, such as hexafluorophosphate, perchlorate or tetrafluoroborate anions, lead to crystalline metal complexes which precipitate out of the reaction mixture and are therefore easy to isolate. They are not or only slightly hygroscopic and can therefore be easily incorporated into consumer products such as detergents and cleaners, where they are characterized by good storage stability.

However, perchlorate salts are potentially explosive, which greatly limits their use in consumer products. Hexafluorophosphate, however, are usually poorly soluble in water, which has a negative impact on their performance in some applications.

Other large-volume counterions such as alkylbenzenesulfonates, alkyl sulfates,

Alkyl sulfonates or tosylates are mentioned as possible counterions in US Pat. No. 5,274,147, but there are no data on the properties of the compounds in the literature.

There is therefore a need for good water-soluble, not or little

hygroscopic transition metal complexes based on manganese and industrially feasible process for their preparation.

It has now surprisingly been found that manganese complexes with organic ligands which coordinate at least two to manganese Contain nitrogen atoms, in particular with ligands based on triazacyclononane and its derivatives, have no hygroscopic properties, if they have an alkylbenzenesulfonate group having 1 to 3 carbon atoms in the alkyl group, in particular a tosylate or cumene sulfonate group

Having counterion. In contrast, compounds prove to be

Alkyibenzenesulfonate, alkyl sulfonate and alkyl sulfate containing more than 8 carbon atoms in the alkyl group as counterions as water attractive, resulting in open storage to bonds and caking. This will be her

Manageability in consumer products such as powdered or tableted detergents and cleaners significantly limited.

The present invention relates to manganese complex compounds of the general formula (1)

is independently selected from manganese in the III or IV oxidation state,

is independently a coordinating or bridging species selected from H ₂ 0, 0 ₂ ^{2 ",} O ^{2 ~,} 0 _^2", OH ^", HO _^2" SH ^", S ^2", SO, Cl ^", N ^3" , SCN ^" , N ₃ ^" , RCOO ^" , NH ₂ ^" and NR ₃ , wherein R is a radical selected from H, C ₁ -C 4 alkyl and C ₆ H ₅ (phenyl),

are independently organic ligands each containing at least two manganese-coordinated nitrogen atoms,

is an integer from -4 to +4,

is a counterion of the formula R ^' -C 6 H ₄ -SO ₃ ^" , which results in charge neutrality of the complex where R ^{' is} CH ₃ , C ₂ H ₅ or iC ₃ H ₇ , and

is an integer from 1 to 4. As the organic ligand L, preferred is one which is an at least nine-membered ring in which at least two, preferably three or four, nitrogen atoms are involved in the ring and coordinate with the manganese. Examples include: 1, 4,7-triazacyclononane (TACN), 1, 4,7-trimethyl-l, 4,7-triazacyclononane (1, 4,7-Me ₃ -TACN), 1, 5,9- Triazacyclododecane (TACD),

1, 5,9-trimethyl-1, 5,9-triazacyclododecane (1, 5,9-Me ₃ -TACD),

1, 4,7,10-tetrazacyclododecane (cyclam), 1, 4,7,10-tetramethyl-1, 4,7, 10-tetrazacyclododecane (1, 4,7,10-Me_rCyclam), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacylononane (2-Me-1, 4,7-Me ₃ -TACN), 2-methyl-1,4,7-triazacyclononane

(2-Me-TACN) or 1, 2-bis (4,7-dimethyl-1, 4,7-triazacyclonon-1-yl) -ethane

(Me ₄ -DTNE). Particularly preferred from this group are 1, 4,7-trimethyl-1, 4,7-triazacyclononane (1, 4,7-Me ₃ -TACN) and 1, 2-bis (4,7-dimethyl-1, 4 , 7-triazacyclonon-1-yl) ethane (Me ₄ -DTNE). Particularly preferred

1, 4,7-Trimethyl-1, 4,7-triazacyclononane (1, 4,7-Me ₃ -TACN).

Preferably, Y is a counter-ion of the formula R ^'-C6H ₄ -S0 ₃ ^", wherein ^R' is _CH3 (tosylate) or 1-C3H7 (cumene sulfonate). Particularly preferred is Y tosylate.

Particularly preferred manganese complex compounds of the general formula (1) according to the invention are

[Mn ^(l, ₂ (μ-O) ₃ (1, 4,7-Me ₃ -TACN) ₂ ] 2 CH ₃ -C ₆ H ₄ -SO ₃ (1 a) [Mn ^(IV) ₂ (μ-)] 0) ₃ (1, 4,7-Me ₃ -TACN) ₂ ] 2 iC ₃ H ₇ -C ₆ H ₄ -SO ₃ (1 b) [Mn ^{(, V)} ₂ (μ-Ο) (M-OAC ) ₂ (1, 4,7-Me ₃ -TACN) ₂ ] 2 CH ₃ -C ₆ H ₄ -SO ₃ (1c) [Mn ^(IV) Mn ^(III) (μ-O) ₃ (Me ₄ -DTNE )] 2 CH ₃ -C ₆ H ₄ -SO ₃ (1d)

In the above formula (1c), "OAc" stands for "acetate".

A particularly preferred manganese complex compound of the general formula (1) according to the invention is tri-oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV)] bis-tosylate (1 a), where this is

Compound preferably in turn is the dihydrate. Another object of the present invention are methods for preparing the manganese complex compounds of the invention of the general

Formula 1). For the preparation of the manganese complex compounds of the general formula (1) according to the invention, different reaction routes are possible. Particularly preferred is the method of partial or complete

Anion exchange. The process according to the invention for preparing the manganese complex compounds of the general formula (1) according to the invention comprises the following steps:

a) reaction of a divalent manganese salt with a ligand L in water as solvent to form a coordination compound of the manganese (II) salt and the ligand L,

b) subsequent oxidation of the manganese (II) - coordination compound formed from step a) with an oxidizing agent, wherein at the same time a pH of 11 to 14, preferably 12 to 13, held for the conversion of the manganese from the dihydric to the drei- and / or tetravalent level,

c) Adjusting the pH to a value <9 by adding a

organic or inorganic acid and separation of the manganese oxides / hydroxides formed and

d) adding an organic sulfonic acid of the formula R'-C6H4-S0 ₃ H, wherein R ^'is CH3, C2H5 or 1-C3H7, or a corresponding salt thereof

Sulfonic acid, preferably of the corresponding sodium or

Potassium salt, after step b) or optionally after step c).

The addition "optionally after step c)" in step d) means, in particular, that step d) can then be carried out but does not have to be run through additionally if a sulfonic acid of the formula R ^'is already present in step c) as organic acid. C ^ U-SOsH wherein R 'is CH3, C2H5 or 1-C3H7. Preferably, at the added in step d) substance is a salt of a sulfonic acid of formula R ^'-C ₆ H 4 S0 ₃ H, wherein ^R' is CH _3> C ₂ H ₅ or iC ₃ H _7, and particularly preferably to the sodium or potassium salt.

The process according to the invention therefore preferably comprises the following steps: a) reaction of a divalent manganese salt with a ligand L in

Water as a solvent to form a coordination compound of the manganese (II) salt and the ligand L,

b) subsequent oxidation of the manganese (II) formed -

Coordination compound from step a) with an oxidizing agent, wherein at the same time a pH of 11 to 14, preferably 12 to 13, is maintained for the conversion of the manganese from the bivalent to the trivalent and / or tetravalent stage,

c) Adjusting the pH to a value <9 by adding a

organic or inorganic acid and separation of the formed

Manganese oxides / hydroxides and

d) adding a salt of an organic sulfonic acid of the formula

R ^'-C6H ₄ -S0 ₃ H, wherein ^R' is CH _3l C2H5 or iC ₃ H _7, preferably a corresponding sodium or potassium salt, after step b) or after

Step c).

In a particularly preferred embodiment of the process according to the invention, it contains the 4 process steps a) to d), their sequence being as follows: first step a), then step b), then step c) and then step d).

In particular, in this particularly preferred embodiment of the

The process according to the invention can also take place after step c) and before step d) a change of the solvent. In this case, the solvent used initially, preferably water by low molecular weight

Alcohols, preferably methanol, ethanol or i-propanol and more preferably be replaced by ethanol. For this purpose, for example, the Filtrate obtained after separation of the manganese oxides / hydroxides, for example by filtration, are completely concentrated, z. B. by evaporation, and the residue are then taken up in the low molecular weight alcohol. In this case, at the same time inorganic by-products such. B.

inorganic salts are separated.

In a further particularly preferred embodiment of the

The process according to the invention comprises the four process steps a) to d), their sequence being as follows: first step a), then step b), then step d) and then step c).

Subsequently, the reaction mixture worked up and the

manganese complex compound of the general formula (1) according to the invention are isolated. For this purpose, the procedure may preferably be as follows: The reaction mixture is concentrated to dryness and then the

Manganese complex compound of general formula (1) having a

low molecular weight alcohol, preferably with methanol, ethanol or i-propanol, extracted. By evaporation of the alcohol, the manganese complex compound of the general formula (1), in particular the corresponding compound with the tosylate counterion, is isolated in solid form.

In step a) of the process according to the invention, a water-soluble

Manganese (II) salt, preferably from the group of acetates, carbonates,

Halides, nitrates and sulfates, and more preferably manganese diacetate, manganese dichloride, manganese dibromide, manganese sulfate or manganese nitrate reacted with a ligand compound L, preferably in a molar ratio of 4: 1 to 1: 2, more preferably in a molar ratio of 2: 1 to 1: 1 and particularly preferably in the molar ratio of 1.5: 1 to 1: 1. As the organic ligand L, preferred is one which is an at least nine-membered ring in which at least two, preferably three or four, nitrogen atoms are involved in the ring and with the manganese coordinate. Examples include: 1, 4,7-triazacyclononane (TACN), 1, 4,7-trimethyl-1, 4,7- triazacyclononane (1, 4,7-Me3-TACN), 1, 5,9-triazacyclododecane (TACD),

1, 5,9-trimethyl-l, 5,9-triazacyclododecane (1, 5,9-Me ₃ -TACD),

1, 4,7,10-tetrazacyclododecane (cyclam), 1 A7,10-tetramethyl-1, 4,7,1 () - tetrazacyclododecane (1, 4,7,10-Me ₄ -cyclam), 2-ethyl- 1, 4,7-trimethyl-1, 4,7-triazacylononan (2-Me-1, 4,7-Me ₃ -TACN), 2-methyl-1,4,7-triazacyclononane (2-Me-TACN) or 1, 2-bis (4 ₎ 7-dimethyl-1, 4,7-triazacyclonon-1-yl) -ethane (Me ₄ -DTNE). Particularly preferred from this group are 1, 4,7-trimethyl-1, 4,7-triazacyclononane (1, 4,7-Me ₃ -TACN) and 1, 2-bis (4,7-dimethyl-1, 4 , 7-triazacyclonon-1-yl) ethane (Me ₄ -DTNE). Particularly preferred

1, 4,7-Trimethyl-1, 4,7-triazacyclononane (1, 4,7-Me ₃ -TACN).

The reaction of the manganese (II) salt with the ligand L is carried out according to the invention in water as the sole solvent. It is preferably used only so much water that per 100 parts by weight of water at least

15 parts by weight of manganese (II) salt plus ligand compound present. The upper limit of the concentration of manganese (II) salt and ligand compound can be very high, because these and the other reactions can be carried out both in solution and in suspension (dispersion). The upper

Concentration limit is thus essentially due to the stirrability of

Reaction mixtures given (the stirrability is also the limiting factor for the space-time yield). The manganese (II) salt and the ligand are accordingly used together in an amount of preferably 15 to 500 parts by weight, and more preferably 20 to 200 parts by weight, per 100 parts by weight of water. The reaction of the manganese (II) salt with the ligand L in water is preferably carried out at a temperature of 10 to 30 ° C, particularly preferably 15 to 25 ° C (room temperature), and atmospheric pressure. Step a) of the process according to the invention leads to the formation of an im

Solvent mixture dissolved coordination compound of the manganese (II) salt and the ligand compound.

In step b) of the process according to the invention the manganese (II) is - coordination compound at a pH value of 11 to 14, preferably 12 to 13, oxidizes in the obtained in step a) solution, the Ox ^y dationsmittel and the base to adjust the specified pH preferably be introduced simultaneously. The oxidation is preferably by

simultaneous mixing of an oxidizing agent from the group air, pure oxygen, hydrogen peroxide, alkali metal peroxide and alkali metal permanganate and an alkali metal hydroxide in the solution obtained in step a)

Maintaining the specified pH. Preferably, the oxidation by mixing a (prepared) mixture consisting of a 0.5 to 35 wt .-%, preferably 3 to 20 wt .-%, aqueous

Hydrogen peroxide solution and a 5 to 40 wt .-%, preferably 10 to 30 wt .-%, aqueous alkali metal (sodium or potassium) hydroxide solution performed. As for the temperature and the pressure, the oxidation is preferably at 3 to 15 ° C, more preferably at 5 to 10 ° C, and

Atmospheric pressure carried out. Here, the used is bivalent

Manganese oxidized to the trivalent or to the preferred tetravalent step.

In step c), the pH of the reaction mixture after oxidation with an organic acid, preferably with R'-CÖH-I-SOSH, wherein R ^'is CH3, C2H5 or 1-C3H7, or an inorganic acid, preferably with hydrochloric acid or sulfuric acid, to a value <9, preferably 5 to 9 and particularly preferably 6 to 7, and the formed in the oxidation step

Manganese oxides / hydroxides separated.

In a particularly preferred embodiment of the process according to the invention, in a step d) following step c), a salt of a sulfonic acid R ^' -C ₆ H 4 -SO ₃ H, in which R ^{' is} CH ₃ , C ₂ H ₅ or 1-C ₃ H 7, preferably a corresponding sodium salt, and more preferably the p-toluenesulfonic acid sodium salt added. Preferably, this addition is carried out in equimolar amount. As already mentioned, especially in this particularly preferred

Embodiment of the method according to the invention after step c) and before step d) a change of the solvent take place. If the solvent is changed, the new solvents are preferably low molecular weight Alcohols, more preferably methanol, ethanol or i-propanol and

especially preferably ethanol used.

The workup may then take place after step d) preferably as follows: The reaction mixture is concentrated to dryness. For the separation of formed salts (eg sodium chloride) the inventive

Manganese complex compound of general formula (1) by extraction with an organic solvent, preferably with a low molecular weight alcohol, of which in turn methanol, ethanol and i-propanol are preferred, or isolated with acetone. By evaporation of the solvent is the

manganese complex compound of the general formula (1) according to the invention isolated in crystalline form.

In a further particularly preferred embodiment of the

Alternatively, step d) may also be carried out prior to step c), in which case first a salt of a sulfonic acid R ^' -CeFU-SOaH, wherein R ^{' is} CH 3, C 2 H 5 or

is, preferably a corresponding sodium salt and more preferably the p-toluenesulfonic acid sodium salt is added after the oxidation step to the reaction mixture, preferably in equimolar amount, and only then the pH is adjusted to a value <9 and in the oxidation step formed manganese oxides / hydroxides are separated.

Also in this further particularly preferred embodiment of the

The process according to the invention may preferably take place as follows: The reaction mixture is concentrated to dryness. to

Separation of formed salts (eg sodium chloride) becomes the

manganese complex compound of the general formula (1) according to the invention by extraction with an organic solvent, preferably with a

low molecular weight alcohol, of which in turn methanol, ethanol and i-propanol are preferred, or isolated with acetone. By evaporation of the solvent, the manganese complex compound of the general formula (1) according to the invention is isolated in crystalline form. The manganese complex compounds of the general formula (1) according to the invention can also be prepared by exchanging the counterion from the corresponding

Chlorides by reaction, preferably in aqueous medium, with silver salts of the sulfonic acids R ^' -C6H ₄ -S0 ₃ H, wherein R ^{' is} CH ₃ , C ₂ H ₅ or iC ₃ H ₇ , and preferably with silver bosylate, are obtained.

Preferably, this process for preparing the manganese complex compounds of the general formula (1) is carried out such that a

Compound of the formula (A)

wherein M, X, L, z and q have the meanings given in claim 1 and YA denotes CI ^" , with a silver salt of a sulfonic acid R ^' -C ₆ H ₄ -SO ₃ H, wherein

R 'is CH ₃ , C ₂ H ₅ or iC ₃ H _7, is reacted, preferably in aqueous medium.

Particularly preferred in this method is a first

Manganese oxide / hydroxide-free complex analogous to the formula (1), but containing instead of the counterion Y chloride as the counterion prepared, for example, as described above. This is then treated with a silver salt of a sulfonic acid R ^' -C ₆ H ₄ -SO ₃ H, where R ^{' is} CH ₃ , C ₂ H 5 or iC ₃ H ₇ , and preferably with

Silver bosylate, preferably in aqueous medium, reacted. Particularly preferably, the just mentioned invention contains

Proceed as follows:

a) Reaction of manganese dichloride with a ligand L in water as

Solvent for forming a coordination compound from the

Manganese (II) chloride and a ligand L,

b) subsequent oxidation of the manganese (II) formed -

Coordination compound from step a) with an oxidizing agent, wherein at the same time a pH of 11 to 14 is maintained to transfer the

Manganese from the bivalent to the trivalent and / or tetravalent stage, c) subsequent adjustment of the pH to a value <9

Addition of an organic or inorganic acid and separation of the manganese oxides / hydroxides formed and

e) subsequent reaction of the reaction product from step c) with a

Silver salt of a sulfonic acid R ^' -C ₆ H 4 -SO ₃ H, wherein R' is CH ₃ , C ₂ H ₅ or 1-C3H7. The work-up can then preferably be carried out as follows: After separation of the silver chloride formed, preferably by filtration, the manganese complex compound of the general formula (1), preferably the tosylate complex, is isolated by evaporation of the water in pure form. For further separation of excess silver salts of sulfonic acid

R'-C ₆ H 4 -SO ₃ H, where R ^'is CH ₃ , C ₂ H 5 or 1-C ₃ H 7, preferably of the silver tosylate, the product may be dissolved in a suitable solvent,

preferably in chloroform, and the insoluble silver salt is separated, preferably filtered off. From the filtrate, the desired product can be isolated, preferably crystallized.

The manganese complex compounds of the general formula (1) prepared by the process according to the invention can be used as oxidation catalysts, in particular use as bleaching component in washing and

Detergents in the household or in commercial laundries, in addition to textile and paper bleaching and in industrial oxidation reactions.

The manganese complex compounds of the general formula (1) according to the invention and in particular the tosylate complexes of the formula (1) are not or only slightly hygroscopic, have good storage stability and are distinguished

Hexafluorophosphat complexes by their better water solubility. They are therefore particularly suitable for use in powdery or tableted products such as machine dishwashing detergents, where they are used in combination with a Peroxide source such as hydrogen peroxide, percarbonate or perborates are used in aqueous applications.

Another object of the present invention is therefore also the use of one or more manganese complex compounds of general formula (1) as oxidation or bleaching catalysts, especially in washing and

Detergents.

The invention is explained in more detail below using examples and comparative examples, but these are not to be understood as limiting.

example 1

19.8 g of manganese dichloride 4-hydrate (0.1 mol) are initially charged in 90 g of water and treated with 17.1 g of 1,4,7-trimethyl-1,4,7-triazacyclononane (purity 96%) (0, 1 mol). After it has been cooled to 5 ° C, a mixture of 30.1 g (0.15 mol) of 20 wt .-% sodium hydroxide solution and 113.4 g (0.1 mol) of 3 wt .-% hydrogen peroxide solution under Temperature control (10 to 12 ° C)

added. After completion of the addition, the reaction mixture (pH> 12.5) with 19.4 g (0.1 mol) of toluene-4-sulfonic acid sodium salt in 40 ml of water and the pH by addition of 5.8 g (0 , 03 mol) of toluene-4-sulfonic acid to a pH of 8. The deposited brown-black solids are filtered off with suction and the resulting filtrate is concentrated to dryness. The dark red solid (44.7 g) is taken up in ethanol and so from

separated inorganic ingredients and salts. The organic phase gives after evaporation 40.0 g of red solid (91% yield) tri-p-oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV)] - tosylate dihydrate. The product is free of ligand salt (measurement limit <0.1% by weight) and manganese dioxide (measurement limit <0.1% by weight).

Elemental analysis for dihydrate:

Calculated: C 43.7%; H 6.9%; N 9.6%; Mn 12.5%

Found: C 43.3% H 7.0% N 9.9%; Mn 12.7% Mass Spectrum:

m / z 671, 2182 [C ₁₈ H42 6 Mn 2 ⁺ C ₇ H ₇ O 3 S] ⁺

m / z 250.2182 [C ₁₈ H ₄ 2 6 Mn ₂ ] ²⁺

The product has a water solubility of> 30 wt .-% at 20 ° C.

Example 2 step A): Preparation of the complex with chloride as counterion

97.9 g of manganese dichloride 4-hydrate (1 mol) are initially charged in 800 g of water in a 1 liter flask and treated with 175.7 g of 1, 4,7-trimethyl-1, 4,7-triazacyclononane (1 mol). added. The solution is cooled and with a mixture of 301 g (1, 505 mol) of 20 wt .-% sodium hydroxide solution and 1133.7 g (1 mol) 3 wt .-% iger

Hydrogen peroxide solution at 10 to 15 ° C added. When the addition is complete, the reaction mixture (pH> 12.5) is adjusted to a pH of 6 with 60.1 g of 50% strength by weight sulfuric acid. The solids (manganese oxides / hydroxides) of the reaction mixture are filtered off with suction, the filtrate obtained is completely concentrated and the red-brown residue is dissolved in ethanol.

Step B): Exchange of the counterion

88.4 g (0.15 mol) of dichloride in 200 g of ethanol from step A) are mixed with 58.3 g (0.3 mol) of toluene-4-sulfonic acid sodium and then to

Dry evaporated. The residue is taken up to remove NaCl in ethanol, filtered and then evaporated. After drying in a vacuum oven, 117.2 g (92.7% yield) of orange-red tri-μ-oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV )] - bis-tosylate dihydrate. In the product no ligand salt and manganese dioxide (measuring limit

<0.1% by weight). Example 3

7.4 g (12.5 mmol) of tri-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] dichloride from Example 2, step A) dissolved as a solid after removal of the ethanol in 50 g of water and with 7.3 g of silver tosylate, prepared according to K. Akhbar et. al., Journal of Organometallic Chemistry 693, 257-262, (2008). The formed silver chloride is filtered off and the filtrate is concentrated to dryness. The product is taken up in chloroform and filtered off excess silver tosylate. Tri-oxo-bis [(1,4,7-trimethyl-1,4,7-triazacyclononane) -manganese (IV)} bis-tosylate crystallizes from the filtrate in the form of dark red crystals. Yield: 4.7 g.

Example 4

Tri-p-oxo-bisKi ^ J-trimethyl-1-yl-triazacyclononane-manganilV1-bis-cumene sulphonate is prepared analogously to Example 2 by reacting tri-p-oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononane) -manganese (IV)] dichloride with cumenesulfonate sodium instead of toluene sulfonate sodium (equimolar exchange of

Toluenesulfonate sodium by cumene sulfonate sodium in the reaction). After working up and purification, a red-brown powder is obtained.

Comparative Example 1

Tri-p-oxo-bis [(i, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV)] bis-hexafluorophosphate monohydrate was prepared as described in WO 93/25562. The ruby red complex has a room temperature

Water solubility of <2 wt .-% to.

Comparative Example 2

Tri-p-oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV)] dichloride is prepared according to Example 2, step A). After separation of the manganese oxides, the water is evaporated and the product taken up in ethanol to

separate inorganic by-products. The ethanol phase is subsequently evaporated to dryness and 280.2 g (95%) of tri-p-oxo-bis [(1, 4, 7-trimethyl-1, 4,7-triazacyclononan) manganese (IV)] - dichloride as a highly hygroscopic , reddish brown powder.

Comparative Example 3

Tris-oxo-bis [(1, 4,7-trimethyl-1,4,7-triazacyclononane) manganese (IV)] bis-dodecylbenzenesulfonate is prepared analogously to Example 2 by reaction of tri-μ-οχο to [( 1, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV)] - dichloride with

Dodecylbenzene sulfonate sodium instead of toluene sulfonate sodium (equimolar exchange of toluenesulfonate sodium with dodecylbenzenesulfonate sodium in the reaction). After working up and purification, a red-brown powder is obtained.

Example 5 (storage test)

Each 100 g of manganese complexes in open shells at

Stored at room temperature. Water absorption and flowability of the powders are investigated at certain intervals (see Table 1).

Table 1 Results of storage tests

Complex according to storage time Water absorption Free-flowing

[Wt .-%]

Example 1 (invention) 5 days <0.1 very good free-flowing

Example 2 (invention) 5 days <0.1 very good free-flowing

Example 4 (invention) 5 days 3 free-flowing

Comparative Example 1 5 days <0.1 very free-flowing

Comparative Example 2 1 hour> 17 liquefied

Comparative Example 3 5 days 9 glued The results demonstrate the physical storage stability of the complexes according to the invention tri-oxo-bis [(1, 4,7-trimethyl, 4,7-triazacyclononane) manganese (IV)] bis-tosylate dihydrate and tri-oxo-bis [ (1, 4,7-trimethyl-1, 4,7-triazacyclononane) - manganese (IV)] - bis-cumene sulfonate dihydrate, while the comparison products tri-μ-oxo-bis [(1, 4,7-trimethyl-1 , 4,7-triazacyclononane) -manganese (IV)] - dichloride

(Comparative Example 2) and tri-p-oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV)] bis-dodecylbenzenesulfonate (Comparative Example 3) for a

Handling in powdery or tableted products are unsuitable. In particular, the tosylate salt is in its handling the standard complex tri -oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononan) manganese (IV)] - bis-hexafluorophosphate monohydrate (Comparative Example 1 ) quite comparable.

Claims

claims

1. Manganese complex compound of the general formula (1)

wherein

M is independently selected from manganese in the III or

IV oxidation state;

X is independently a coordinating or bridging species selected from H ₂ 0, 0 ₂ ^{2 ',} O ^2', 0 ₂ ^', ^OH', H0 ₂ ^{^"SH",} S ^{2 ',} SO, Cl \ N ^3' , SCN ^" , N ₃ ^" , RCOO ^" , NH ₂ ^" and NR ₃ , wherein R is a radical selected from H, dC ₄ alkyl and C ₆ H ₅ ,

L are independently organic ligands each containing at least two manganese-coordinated nitrogen atoms,

z is an integer from -4 to +4,

Y is a counter ion of the formula R ^'-C6H4-SO ₃ ^", which for charge neutrality of the

Complex results where R ^'is CH ₃ , C ₂ H ₅ or iC ₃ H ₇ , and

q is an integer from 1 to 4.

2. Manganese complex compound according to claim 1, characterized in that L is an organic ligand which represents an at least nine-membered ring in which at least two, preferably three or four, nitrogen atoms are involved in the ring and coordinate with the manganese.

3. manganese complex compound according to claim 1 or 2, characterized

characterized in that L is 1, 4,7-trimethyl-1, 4,7-triazacyclononane.

4. manganese complex compound according to one or more of claims 1 to 3, characterized in that Y is tosylate.

5. Manganese complex compound according to one or more of claims 1 to 4, characterized in that it is tri -oxo-bis [(1, 4,7-trimethyl-1, 4,7-triazacyclononane) manganese (IV )] bis-tosylate and preferably the dihydrate.

6. A process for preparing a manganese complex compound of general formula (1) according to one or more of claims 1 to 5, characterized in that it comprises the following process steps:

a) reaction of a divalent manganese salt with the ligand L in water as solvent to form a coordination compound of the manganese (II) salt and the ligand L,

b) subsequent oxidation of the resulting manganese (II) coordination compound from step a) with an oxidizing agent while maintaining a pH of 11 to 14 to convert the manganese from the divalent to the trivalent and / or tetravalent step, c ) Adjust the pH value to a value <9 by adding a

d) adding an organic sulfonic acid of the formula R ^' -C6H ₄ -SO ₃ H, wherein R ^{' is} CH ₃ , C ₂ H 5 or 1-C ₃ H 7, or a corresponding salt thereof

Sulfonic acid after step b) or optionally after step c).

7. The method according to claim 6, characterized in that it contains the following method steps:

a) Reaction of a divalent manganese salt with a ligand L in

b) subsequent oxidation of the manganese (II) formed -

Manganese from the bivalent to the tri- and / or tetravalent level, c) adjustment of the pH to a value <9 by addition of an organic or inorganic acid and separation of the manganese oxides / hydroxides formed and

d) adding a salt of an organic sulfonic acid of the formula

R ^' -C ₆ H ₄ -SO ₃ H, wherein R ^{' is} CH ₃ , C ₂ H ₅ or iC ₃ H ₇ , after step b) or after step c).

8. Use of one or more manganese complex compounds of the general formula (1) according to one or more of claims 1 to 5 as oxidation or bleaching catalysts, in particular in washing and

Detergents.