Bleaching system containing Bis-and-Tris-(mu-oxo)-di-manganese complex salts

Bleaches that release active oxygen are an essential part of modern washing and cleaning agents. Its main task is to remove stubborn stains such as tea, coffee, red wine or fruit juices from textile fibers or solid surfaces. This is done by oxidative destruction of the chromophore system; At the same time, adhering microorganisms are killed and odorants neutralized.

Hydrogen peroxide, organic or inorganic peracid are mostly used as bleaching agents. A persalt is usually used as a source of active oxygen in powdery products. Typical examples are sodium perborates or percarbonates or urea adducts.

In order to increase the effectiveness of these per-compounds in the temperature range from 40 to 60 ° C, bleach activators are often added. Examples include tetraacetylethylenediamine (TAED), diacetyldioxohexahydrotriazine (DADHT), pentaacetylglycose (PAG), benzoyloxibenzenesulfonate (BOBS) and nonanoyloxibenzenesulfonate (NOBS). In the presence of the activator, the corresponding peracids are released from the persalts, which usually have a broader activity spectrum than hydrogen peroxide.

In many cases, however, the combination of a persalt with an activator does not yet lead to the optimal bleaching properties. A particular problem is the limited effectiveness of such bleaching systems at low application temperatures and their lack of reactivity to certain types of soiling.

Systems with further increased performance are therefore desirable. For economic and ecological reasons, catalytically active additives are preferred. However, there is also a need for catalysts which react directly with hydrogen peroxide or caroates and which significantly reduce or eliminate the activator concentration.

It has been known for many years that transition metals in free or complex form catalyze the decomposition of hydrogen peroxides. The effectiveness of the compounds described so far is unsatisfactory in most cases. In many cases, the addition of metal salts leads to catalytic decomposition of the hydrogen peroxide, but no bleaching effect is observed. This is usually associated with damage to the textile fabric. The occurrence of free transition metals during the washing and cleaning process is therefore undesirable. If, on the other hand, the metal salt is used in complexed form, the corresponding complex must be stable to hydrolysis and oxidation during storage and under conditions of use in order to suppress these side effects.

Complexes of copper or cobalt with pyridinecarboxylic acid or dicarboxylic acid are described in US 3,156,654. US 3,532,634 teaches the use of picolinic acids, pyrrolidine carboxylic acids or phenanthroline. US 4,430,243 claims EDTA and EDTMP complexes of copper, iron and manganese as bleaching catalysts; US 4,478,733 successfully uses manganese salts in detergent formulations based on zeolite / ortophosphate. Hydroxyarboxylic acids (EP A 237 111), porphine systems (EP A 306 089), 2,2'-bispyridylamines (EP A 392 592), salen derivatives (EP A 408 131), macrocyclic polyamines (EP A 439 387) or polyols such as sorbitol (EP A 443 651). For ecological reasons, manganese is usually chosen as the central atom, but complexes of iron, copper and cobalt are also known.

EP A 458 397 and 458 398 describes the use of macrocyclic polyamines as complex ligands in multinuclear, oxygen-bridged manganese complexes. In combination with oxidizing agents, especially on tea stains, these complexes show good bleaching properties. However, the difficult to access complex ligand of the triazacyclononane type has a disadvantage. It is only accessible in a multi-stage, by-product-rich manufacturing process. Similar complexes are described in EP 544 519, again the synthesis of the complex ligand is very complex and difficult to implement on an industrial scale.

There is therefore still a need for easy-to-produce, effective bleaching catalysts with a broad spectrum of activity for use in detergents and cleaning agents.

Surprisingly, it has now been found that the manganese complex salts described below are excellently suitable for use in detergents and cleaning agents and increase the effectiveness of hydrogen peroxide, peracetic acid and other bleaching systems by a multiple even in catalytic amounts. The easy accessibility of these catalysts has proven to be particularly advantageous over the prior art.

The invention relates to bleaching systems containing bis- and tris (μ-oxo) -di-manganese complex salts of the formula I.         [LMn (µ-O)_a(µ-OAc)_bMnL]^xA_y     (I) wherein<dl id="dl0001" compact="compact"><dt>Ac</dt><dd>a C₂-C₈-Acyl group,</dd><dt>a</dt><dd>is 1, 2 or 3,</dd><dt>b</dt><dd>is 0 if a is 2 or 3, or b is 2 if a is 1,</dd><dt>x</dt><dd>denotes the number of positive charges and is 2 or 3,</dd><dt>A</dt><dd>is a single or double negatively charged anion,</dd><dt>y</dt><dd>means the equivalent amount of anion A and required to balance the positive charges</dd><dt>L</dt><dd>means a ligand of formula II or III</dd></dl><chemistry id="chem0001" num="0001"><img file="EP0783035A2_D0001.tif" /></chemistry> where RC₁-C₁₂-Alkyl, C₅-C₁₀-Cycloalkyl, phenyl, NH₂, NHR², NO²)₂, OH, OR² or COOH, R¹ Hydrogen, C₁-C₁₂-Alkyl, C₅-C₁₀-Cycloalkyl, NH₂, NHR², NO²)₂, OH, OR², COOH, COOR², Cl, Br, F or CN, R² C.₁-C₁₂-Alkyl or C₅-C₁₀Cycloalkyl, g is 2 or 3 and m and n is zero or an integer from 1 to 4.

Ligands of the formulas II and III in which all the substituents R¹ in the ligands L are hydrogen and n = 1. For the case a = 3 and b = 0, L is preferably a ligand of the formula II. Also preferred are complex salts of the formula I, in which a = 1 and b = 2 and L is a ligand of the formula II. In the case of compounds of the formula I in which L is a ligand of the formula II, R is preferably C₁-C₄-Alkyl, especially methyl. As anion A come into question Cl^-, Br^-, J^-, NO₃^-, ClO₄^-, NCS^-, PF₆^-, RSO₃^-, RSO₄^-, SO₄^2-, BPh₄^-, OAc^-. Preferred anions are PF₆^-, ClO₄^-, Tosylate.

The ligands of the formula III contained in these manganese complex salts are prepared by reacting 2- (chloromethyl) pyridinium chloride with an alkylenediamine in the presence of a phase transfer catalyst (see Synthesis, June 1992, p. 539-540) or in an analogous manner for the substituted other ligands of formula III. In the same way, the ligands of the formula II are prepared by reacting 2- (chloromethyl) pyridinium chloride or of analogous pyridinium compounds with an amine R-NH₂. The manganese complex salts of the formula I are prepared in accordance with the information in Inorg. Chem. 1989, 28, 3606-3608 by using an aqueous solution, the MnCl₂ and contains the ligand with H₂O₂ oxidized or analogous to that in Inorg. Chem. 1994, 33, 4105-4111 described method, in which the oxidation is carried out with ammonium peroxodisulfate.

Examples of particularly preferred complex ligands are:<ul id="ul0001" list-style="none" compact="compact"><li>N, N'-bis (2-pyridylmethyl) -N-methylamine</li><li>N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine</li><li>N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,3-propylenediamine</li><li>N, N, N ', N'-tetrakis (2-pyridylethyl) -1,3-propylenediamine</li><li>N, N, N ', N'-tetrakis (2-pyridylethyl) -1,4-butylenediamine</li></ul>

The metal complexes can either be added to the washing and cleaning agent in prefabricated form or generated in situ from the ligand and transition metal during the washing process.

Examples of complex salts to be used according to the invention are:<ul id="ul0002" list-style="none" compact="compact"><li>Bis (µ-oxo) bis [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangan (III, IV) perchlorate</li><li>Tris (µ-oxo) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] dimangane (IV, IV) hexafluorophosphate</li><li>(µ-Oxo) to (µ-OAc) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangane (III, III) perchlorate</li><li>(µ-Oxo) to (µ-OBu) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine] -dimangane (III, III) perchlorate</li><li>Tris (µ-oxo) to [N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,3-propylenediamine] dimangane (IV, IV) hexafluorophosphate</li><li>Bis (µ-oxo) bis [N, N'-bis (2-pyridylmethyl) -N-methylamine] -dimangan (III, IV) perchlorate</li><li>Tris (µ-oxo) bis [N, N'-bis (2-pyridylmethyl) -N-methylamine] dimangane (IV, IV) hexafluorophosphate</li><li>(µ-Oxo) to (µ-OBu) to [N, N'-bis (2-pyridylmethyl) -N-methylamine] dimangane (IV, IV) hexafluorophosphate</li></ul>

These complex salts have catalytic properties and are able to considerably increase the bleaching performance of peracids, persalts or hydrogen peroxide in the washing and cleaning process.

In the bleaching agent systems according to the invention, the bleaching catalysts are used in combination with an oxidizing agent. Examples of such oxidizing agents that can be used are hydrogen peroxide, alkali metal perborates, percarbonates, perphosphates or persulfates. If the catalysts are used in powdery products, sodium perborate mono- or tetrahydrate, caroate in the form of the triple salt and sodium percarbonate, the latter in particular in coated form, are particularly preferred. These compounds can be used either with the catalysts alone or, in a preferred embodiment, additionally together with a bleach activator. This extends the range of applications and strengthens the germicidal properties of the formulation.

Bleach activators are known from numerous patent applications. Examples of these are reactive esters and amides such as in GB 836,988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 284,292, 331,229, 303,520, 185,522, 174,132, 120,591 and US 1,246,339, 3,332,882, 4,128,494, 4,412,934, 4,675,393, 4,751,015 and 4,397,757. Tetraacetylethylenediamine, nonanoyloxibenzenesulfonate, benzoyloxibenzenesulfonate, nonanoyl and benzoylcaprolactam, isatoic acid, maleic, succinic and citric acid anhydrides and acylated sugar or sugar derivatives, in addition alkyl or aryl nitriles, are particularly preferred.

Instead of the activator system (persalt plus bleach activator), certain organic peroxycarboxylic acids can also be used directly as oxidizing agents. Typical representatives are peroxibenzoic acid and substituted derivatives, aliphatic mono- and dicarboxylic acids such as pernonanoic acid, perlauric acid, 1,9-diperoxiazeldic acid and 1,12-dodecanediperic acid. Further examples are N, N'-phthaloylaminoperoxicarboxylic acids such as N, N'-phthaloylaminoperoxihexanoic acid (PAP), 6-octylamino-6-oxoperoxihexanoic acid, monoperoxiphthalic acid and its salts, 2-alkylperoxi-1,4-butanedioic acids or 4,4'-sulphonylbisperoxiboesoes.

The composition of the bleaching agent system according to the invention can vary within wide limits and is generally between 0.0005 to 2% by weight, preferably 0.001 to 0.5% by weight of the bleaching catalyst described and 1 to 99.9995%, preferably 5 to 99.999 % of an oxidizing agent from the group of inorganic or organic peracids or persalt, and optionally 0 to 70%, preferably 10 to 60% of a bleach activator.

The bleaching systems according to the invention are used in heavy-duty detergents, multi-component detergents (modular systems), stain salts, stain pretreatment agents, machine dishwashing detergents, cleaning agents for hard surfaces, disinfectants and denture cleaners. In addition to bleaching, the catalysts also act as dye transfer inhibitors. The catalysts are normally added to the washing and cleaning agent in granular form. Inorganic salts such as sodium sulfate, chloride, phosphate or silicates can be used as granulation aids. In a preferred application form, they are incorporated into the activator granulate. According to the state of the art, inorganic or organic auxiliaries can be used for granulation, film-forming materials such as surfactants, fatty acids, celulose derivatives or polymers are preferred. The granules can additionally be provided with a coating, which on the one hand increases their storage stability and interactions with other detergent ingredients can be prevented during storage, but on the other hand their release kinetics can also be influenced.

The bleaching agent systems according to the invention, consisting of catalyst and oxidizing agent and optionally activator, are usually used in the washing and cleaning agents in the following concentrations:<ul id="ul0003" list-style="none" compact="compact"><li>Heavy duty detergent: 2 to 40% by weight</li><li>Stain salts and laundry pretreatment agents: 20 to 100% by weight</li><li>Dishwasher detergent: 1 to 30% by weight</li><li>Hard surface cleaner and disinfectant cleaner: 2 to 50% by weight</li><li>Denture cleaner: 2 to 20% by weight</li></ul>

The bleach system according to the invention can be added to the washing and cleaning agents in the form of a powder or as granules.

In addition to the bleach system, the detergents and cleaning agents normally also contain surface-active compounds such as anionic, nonionic, zwitterionic, amphoteric or cationic surfactants, builders, enzymes and additives.

Surfactants can be of natural or synthetic origin and are described, for example, in "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch. Examples are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alpha-sulfofatty acid methyl esters, soaps and alkyl ether sulfonates. Nonionic surfactants such as alkyl polyglycol ethers, alkyl polyglucosides, glucamides, sugar esters and amine oxides can also be used.

Important builder and cobuilder substances which can be used in combination with the bleaching system according to the invention are phosphates such as sodium tripolyphosphate, zeolites of the types A, X and P, alkali metal carbonates and bicarbonates, amorphous and crystalline silicates, in particular layered silicates such as SKS-6, 7, 9 or 10 from Hoechst AG or disilicates such as those from Akzo under the trade name Britesil^® to be expelled. Organic carboxylic acids such as citric acid or amino acids can be used as co-builders, but also polymers of the polyacrylic acid type or copolymers of acrylic acid and maleic acid or their derivatives. Phosphonate or other complexing agents can also be added.

Amylase, proteases, lipases, cellulases and peroxidases can be used as enzymes, cellulose ethers, silicones, bentonites, optical brighteners and perfume as further additives.

Examples of the preparation of the catalysts.

example 1

(µ-oxo) to (µ-acetato) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,2-ethylenediamine] -di-manganese IV, IV-perchlorate (catalyst K1)

A mixture of 25.5 ml of ethanol and 4.5 ml of water was degassed by applying a vacuum three times and treated with argon to remove any residual oxygen which would otherwise cause oxidation of MnII to MnIV. 2.47 g (5.82 mmol) of N, N, N ', N'-tetrakis (2-pyridylmethyl) ethylenediamine were added to this mixture. A yellow solution with a pH of 8.8 was obtained. Then 0.96 g (3.6 mmol) of manganese triacetate (Mn (OAc)₃· 2H₂O) added. The solution turned brown and had a pH of 6.2. Then 2 g (14.58 mmol) of sodium acetate were added (pH 6.5), then perchloric acid (55 drops) to a pH of 5. After addition of 3 g (24.48 mmol) of sodium perchlorate, the pH dropped to 6 , 1 a precipitation. The reaction mixture was stirred for 4 hours. The precipitated crystals were filtered off and dried under nitrogen. 3.08 g of crude product of the compound (μ-oxo) bis (μ-acetato) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,2-ethylenediamine-] di-manganese were obtained -IV, IV perchlorate. <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="7" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="22.50mm" /><colspec colnum="2" colname="col2" colwidth="22.50mm" /><colspec colnum="3" colname="col3" colwidth="22.50mm" /><colspec colnum="4" colname="col4" colwidth="22.50mm" /><colspec colnum="5" colname="col5" colwidth="22.50mm" /><colspec colnum="6" colname="col6" colwidth="22.50mm" /><colspec colnum="7" colname="col7" colwidth="22.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left">Analysis:</entry><entry namest="col2" nameend="col2" align="left">calc .:</entry><entry namest="col3" nameend="col3" align="char" char=",">Mn 8.39%</entry><entry namest="col4" nameend="col4" align="char" char=",">C 51.35%</entry><entry namest="col5" nameend="col5" align="char" char=",">H 4.92%</entry><entry namest="col6" nameend="col6" align="char" char=",">N 12.83%</entry><entry namest="col7" nameend="col7" align="char" char=",">O 17.1%</entry></row><row rowsep="1"><entry namest="col2" nameend="col2" align="left">found:</entry><entry namest="col3" nameend="col3" align="char" char=",">Mn 8.4%</entry><entry namest="col4" nameend="col4" align="char" char=",">C 48.0%</entry><entry namest="col5" nameend="col5" align="char" char=",">H 4.9%</entry><entry namest="col6" nameend="col6" align="char" char=",">N 12.7%</entry><entry namest="col7" nameend="col7" align="char" char=",">O 17.9%</entry></row></tbody></tgroup></table></tables>

Example 2

(µ-oxo) to (µ-butyrato) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,2-ethylene-di-amine] dimangan III, IV perchlorate (catalyst K2)

2.47 (5.82 mmol) N, N, N ', N'-tetrakis (2-pyridylmethyl) -1,2-ethylenediamine were dissolved in 30 ml of a mixture of ethanol and water (5: 1) and then Mn (acetate)₃· 2H₂O (0.96 g; 3.6 mmol) added. Then 2.2 g (20 mmol) sodium butyrate was added and then 2 ml HClO₄ (70%). A pH of 7.5 was established. Then 3 g (24.48 mmol) of NaClO₄ added and this mixture was stirred for 4 hours at room temperature. A precipitate formed which was filtered off with an ethanol / water mixture (85% EtOH / 15% H₂O) washed and dried. Crude yield 2.3 g. The solid was treated with 70 ml of acetone and the acetone solution was filtered off from the insoluble inorganic salts. After distilling off the acetone and recrystallization with ethanol / water 5: 1, the above-mentioned complex salt was obtained.<tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="6" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left">Analysis:</entry><entry namest="col2" nameend="col2" align="left">calc .:</entry><entry namest="col3" nameend="col3" align="char" char=",">Mn 7.5%</entry><entry namest="col4" nameend="col4" align="char" char=",">C 49.17%</entry><entry namest="col5" nameend="col5" align="char" char=",">H 4.95%</entry><entry namest="col6" nameend="col6" align="char" char=",">N 11.47%</entry></row><row rowsep="1"><entry namest="col2" nameend="col2" align="left">found:</entry><entry namest="col3" nameend="col3" align="char" char=",">Mn 8.0%</entry><entry namest="col4" nameend="col4" align="char" char=",">C 44.8%</entry><entry namest="col5" nameend="col5" align="char" char=",">H 4.5%</entry><entry namest="col6" nameend="col6" align="char" char=",">N 12.1%</entry></row></tbody></tgroup></table></tables>

Example 3

Tris (µ-oxo) to [N, N, N ', N'-tetrakis (2-pyridylmethyl-] 1,3-diaminopropane-di-manganese-IV, IV-hexafluorophosphate (catalyst K3)

3.5 g (19 mmol) KPF₆ and 3.86 g (8.8 mmol) of N, N, N ', N'-tetrakis (2-pyridylmethyl-) 1,3-diaminopropane were added to 120 ml of an ethanol / water mixture at 5 ° C ( 5: 1) added and stirred. The solution turned yellow and 3.48 g (17.6 mmol) of MnCl became₂4H₂O added. 20 ml of H were then added to the pale yellow solution₂O₂ (3%) and 5.2 ml NaOH (20%) added. The temperature rose to 12 ° C and the reaction mixture turned brown. The reaction mixture was then cooled to 5 ° C for 1 hour and then kept at room temperature for 2 hours. The solvents were distilled off in vacuo and the resulting crude product was treated with acetone to remove excess manganese dioxide.<tables id="tabl0003" num="0003"><table frame="all"><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left">Analysis:</entry><entry namest="col2" nameend="col2" align="left">calc .:</entry><entry namest="col3" nameend="col3" align="char" char=",">C 35.86%</entry><entry namest="col4" nameend="col4" align="char" char=",">H 3.75%</entry><entry namest="col5" nameend="col5" align="char" char=",">N 9.29%</entry></row><row rowsep="1"><entry namest="col2" nameend="col2" align="left">found:</entry><entry namest="col3" nameend="col3" align="char" char=",">C 33.8%</entry><entry namest="col4" nameend="col4" align="char" char=",">H 3.2%</entry><entry namest="col5" nameend="col5" align="char" char=",">N 8.3%</entry></row></tbody></tgroup></table></tables>

Example 4

Tris (µ-oxo) bis [N, N'-bis (2-pyridylmethyl-) N-methylamine] dimangane IV, IV hexafluorophosphate (catalyst K4)

1.74 g (8.8 mmol) MnCl₂4H₂O, 1.88 g (8.8 mmol) N, N'-bis (2-pyridylmethyl) -N-methylamine and 1.75 g (9.5 mmol) KPF₆ were dissolved in 600 ml of a mixture of ethanol and water (2: 1). The solution was stirred at room temperature for 20 minutes and then cooled to 5 ° C. in an ice bath. Then 10 ml of H₂O₂ (3%) and 2.6 ml of a 20% aqueous NaOH solution were added, the temperature rising to 10 ° C. and a precipitate falling out. This mixture was stirred at 5 ° C for 1 hour and at 20 ° C for an additional hour. The precipitate was filtered off and washed with water. Crude yield 6.1 g. After drying, the solid was treated with acetone, MnO₂ remained as a solid. The acetone solution was removed from the insoluble MnO₂ filtered off and the acetone distilled off. 1.25 g of a gray-green solid were obtained.<tables id="tabl0004" num="0004"><table frame="all"><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left">Analysis:</entry><entry namest="col2" nameend="col2" align="left">calc .:</entry><entry namest="col3" nameend="col3" align="char" char=",">C 40.9%</entry><entry namest="col4" nameend="col4" align="char" char=",">H 3.8%</entry><entry namest="col5" nameend="col5" align="char" char=",">N 10.9%</entry></row><row rowsep="1"><entry namest="col2" nameend="col2" align="left">found:</entry><entry namest="col3" nameend="col3" align="char" char=",">C 35.0%</entry><entry namest="col4" nameend="col4" align="char" char=",">H 3.6%</entry><entry namest="col5" nameend="col5" align="char" char=",">N 9.42%</entry></row></tbody></tgroup></table></tables>

Example 5

(µ-oxo) to (µ-butyrato) to [N, N'-bis (2-pyridylmethyl-) N-methylamine] -di-manganese-IV, IV-perchlorate (catalyst K5)

A mixture of 25.5 ml of ethanol and 4.5 ml of water was made free of oxygen by applying a vacuum three times and introducing argon. To this mixture was added 1.25 g (5.82 mmol) of N, N'-bis (2-pyridylmethyl) -N-methylamine in the form of a solution in 25.5 ml of ethanol and 4.5 ml of water. The reaction mixture turned brown. Then 0.96 g (3.6 mmol) of Mn (acetate)₃· 2H₂O was added and after the reaction mixture had turned dark brown, 2.2 g (20 mmol) of sodium butyrate were added. Then 1.8 ml of HClO₄ (70%) was added, the pH having reached 5.0, and then 3.0 g (24.48 mmol) NaClO₄. After 4 hours, the precipitate obtained was filtered off to remove excess manganese dioxide. The solvent was distilled off from the filtrate and after recrystallization with 20 ml of isopropanol, the title compound was obtained as a white solid.

Manganese (II) sulfate and the 4-toothed manganese complex bis (µ-oxo) bis [N, N'-bis (2-pyridylmethyl) -N, N'-dimethyl-1,2-ethylenediamine] -dimangan ( III, IV) perchlorate (catalyst V1) used.

Application engineering examples

Example 1: Stability of hydrogen peroxide in the presence of the catalysts

0.5 g of sodium perborate monohydrate was dissolved in 1 l of water (15 ° dH) and heated to 20 ° C. After adding 4 mg of a manganese compound, the hydrogen peroxide concentration was monitored as a function of time by iodometric titration.

Hydrogen peroxide content in the solution

<tables id="tabl0005" num="0005"><img file="EP0783035A2_D0002.tif" /></tables>

The results show that, in contrast to free manganese ions, the catalysts according to the invention do not decompose hydrogen peroxide in an uncontrolled manner.

Example 2: Stability of peracetic acid in the presence of the catalysts

1 g of sodium percarbonate and 0.5 g of TAED powder (TAED: tetraacetylethylenediamine) are added together with 0.01 g of the manganese compound in 1 l of water (15 ° dH) which is heated to 40 ° C. The amount of peracetic acid released is determined as a function of time by iodometric titration.

Peracetic acid content in the solution

<tables id="tabl0006" num="0006"><img file="EP0783035A2_D0003.tif" /></tables>

The results show that neither the release of the peracid nor its stability in aqueous solution are significantly influenced by the catalysts according to the invention. There is no uncontrolled decomposition due to metal traces.

Example 3: Washing tests in the Linitest device

2nd g / l test detergent (P-free, WMP, laundry research Krefeld) was dissolved in 200 ml water (15 ° dH). Then 1 g / L sodium percarbonate and 0.5 g / L TAED and 4 rags each of a test soil (tea on cotton, BC-1, laundry research Krefeld) were added. The washing tests were carried out at 40 ° C. in a Linitest device from Haraeus, Hanau, washing time 30 minutes. The whiteness of the laundry was then determined using an Elrepho device (from Datacolor). In a second series of experiments, the experiments were carried out with the addition of 10 mg / L of a catalyst. The remission differences (washing with catalyst) - (washing without catalyst) are listed in the results table.<tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="2" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">catalyst</entry><entry namest="col2" nameend="col2" align="center">ΔRE</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">without</entry><entry namest="col2" nameend="col2" align="center">0</entry></row><row><entry namest="col1" nameend="col1" align="left">K1</entry><entry namest="col2" nameend="col2" align="center">+ 5,9</entry></row><row><entry namest="col1" nameend="col1" align="left">K2</entry><entry namest="col2" nameend="col2" align="center">+ 6,5</entry></row><row><entry namest="col1" nameend="col1" align="left">K3</entry><entry namest="col2" nameend="col2" align="center">+ 5,5</entry></row><row><entry namest="col1" nameend="col1" align="left">K4</entry><entry namest="col2" nameend="col2" align="center">+ 5,8</entry></row><row><entry namest="col1" nameend="col1" align="left">K5</entry><entry namest="col2" nameend="col2" align="center">+ 5,2</entry></row><row><entry namest="col1" nameend="col1" align="left">Mn₂SO₄</entry><entry namest="col2" nameend="col2" align="center">+ 4,3</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">V1</entry><entry namest="col2" nameend="col2" align="center">+ 5,0</entry></row></tbody></tgroup></table></tables>

The results show the superiority of the catalysts according to the invention based on 3- and 6-dentate complex ligands over free manganese ions and the catalyst V1 not according to the invention.

Example 4: Washing tests in the Linitest device

The tests were carried out as described in Example 3. Instead of the test soil tea (BC-1), beetroot and curry on cotton (manufacturer laundry research Krefeld) were used.<tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" align="center">catalyst</entry><entry namest="col2" nameend="col2" align="center">Beetroot ΔRE</entry><entry namest="col3" nameend="col3" align="center">Curry ΔRE</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">without</entry><entry namest="col2" nameend="col2" align="center">0</entry><entry namest="col3" nameend="col3" align="center">0</entry></row><row><entry namest="col1" nameend="col1" align="left">K1</entry><entry namest="col2" nameend="col2" align="center">+ 2,0</entry><entry namest="col3" nameend="col3" align="center">+ 0,6</entry></row><row><entry namest="col1" nameend="col1" align="left">K4</entry><entry namest="col2" nameend="col2" align="center">+ 1,1</entry><entry namest="col3" nameend="col3" align="center">+ 0,1</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">K2</entry><entry namest="col2" nameend="col2" align="center">+ 4,0</entry><entry namest="col3" nameend="col3" align="center">+ 0,9</entry></row></tbody></tgroup></table></tables>

By using the catalysts according to the invention, the bleaching results on the test soils beetroot and curry can also be significantly increased.

Example 5: Concentration dependence of the catalyzed hydrogen peroxide bleach

The washing tests were carried out in the Linitestgerät at 40 ° C; Washing time 30 min. 1.5 g / l WMP were pre-dissolved in 200 ml water (15 ° dH) and 0.5 g / l sodium perborate monohydrate was added. Before the start of the washing tests, 0; 1.5; 3; 6; 12; 25 mg / l of the catalysts added. The washing tests were carried out analogously to Example 3. The table shows the reflectance differences ΔRE of the washes with and without a catalyst.<tables id="tabl0009" num="0009"><table frame="all"><tgroup cols="7" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="22.50mm" /><colspec colnum="2" colname="col2" colwidth="22.50mm" /><colspec colnum="3" colname="col3" colwidth="22.50mm" /><colspec colnum="4" colname="col4" colwidth="22.50mm" /><colspec colnum="5" colname="col5" colwidth="22.50mm" /><colspec colnum="6" colname="col6" colwidth="22.50mm" /><colspec colnum="7" colname="col7" colwidth="22.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" rowsep="0" align="center">catalyst</entry><entry namest="col2" nameend="col7" align="center">Catalyst concentration [mg / l]</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">0</entry><entry namest="col3" nameend="col3" align="center">1,5</entry><entry namest="col4" nameend="col4" align="center">3</entry><entry namest="col5" nameend="col5" align="center">6</entry><entry namest="col6" nameend="col6" align="center">12</entry><entry namest="col7" nameend="col7" align="center">25</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">K1</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 2,0</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 2,0</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 3,2</entry><entry namest="col6" nameend="col6" align="char" char=",">+ 2,6</entry><entry namest="col7" nameend="col7" align="char" char=",">+ 2,7</entry></row><row><entry namest="col1" nameend="col1" align="left">K4</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 2,7</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 3,0</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 3,7</entry><entry namest="col6" nameend="col6" align="char" char=",">+ 5,8</entry><entry namest="col7" nameend="col7" align="char" char=",">+ 4,6</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">K2</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 1,6</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 2,3</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 3,2</entry><entry namest="col6" nameend="col6" align="char" char=",">+ 4,8</entry><entry namest="col7" nameend="col7" align="char" char=",">+ 5,1</entry></row></tbody></tgroup></table></tables>

The results show that the catalysts according to the invention bring about a significant increase in the bleaching performance of hydrogen peroxide even in the lowest concentrations.

Example 6: Concentration dependence of the catalyzed peracetic acid bleach

The tests were carried out analogously to Example 5. In addition, 0.25 g / l TAED was added to the wash liquor. The following table shows the reflectance differences ΔRE of the washes with and without a catalyst.<tables id="tabl0010" num="0010"><table frame="all"><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" rowsep="0" align="center">catalyst</entry><entry namest="col2" nameend="col6" align="center">Catalyst concentration [mg / l]</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">0</entry><entry namest="col3" nameend="col3" align="center">1,5</entry><entry namest="col4" nameend="col4" align="center">3</entry><entry namest="col5" nameend="col5" align="center">6</entry><entry namest="col6" nameend="col6" align="center">12</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">K1</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 1,6</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 2,2</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 3,0</entry><entry namest="col6" nameend="col6" align="char" char=",">+ 3,3</entry></row><row><entry namest="col1" nameend="col1" align="left">K4</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 1,6</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 2,6</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 1,5</entry><entry namest="col6" nameend="col6" align="char" char=",">+ 0,7</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">K2</entry><entry namest="col2" nameend="col2" align="right">0</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 2,4</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 2,8</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 4,5</entry><entry namest="col6" nameend="col6" align="char" char=",">+ 5,4</entry></row></tbody></tgroup></table></tables>

The results show that the catalysts of the invention bring about a significant increase in the bleaching performance of peracetic acid even in the lowest concentrations.

Example 7: Influence of various oxidizing agents on the bleaching result

The washing tests were carried out in the Linitest at 20 ° C.<dl id="dl0002" compact="compact"><dt>Water hardness:</dt><dd>15 ° dH</dd><dt>Washing time:</dt><dd>30th min</dd><dt>Soiling:</dt><dd>Tea on cotton (BC-1)</dd><dt>Laundry detergent:</dt><dd>1.5 g / l WMP detergent</dd></dl>

Oxidation systems:<dl id="dl0003" compact="compact"><dt>PAP:</dt><dd>Phthalimidoperoxicaproic acid (0.5 g / l)</dd><dt>BOBS:</dt><dd>Benzoyloxybenzenesulfonate sodium (0.25 g / l) in combination with 0.5 g / l sodium perborate monohydrate</dd><dt>Caroat:</dt><dd>Potassium peroxomonosulfate (0.5 g / l)</dd></dl>

The following table shows the reflectance differences ΔRE of the washes with and without a catalyst. <tables id="tabl0011" num="0011"><table frame="all"><tgroup cols="5" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" rowsep="0" align="center">catalyst</entry><entry namest="col2" nameend="col2" rowsep="0" /><entry namest="col3" nameend="col5" align="center">Oxidizing agent</entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" align="center">PAP</entry><entry namest="col4" nameend="col4" align="center">BOBS</entry><entry namest="col5" nameend="col5" align="center">Caroat</entry></row></thead><tbody valign="top"><row rowsep="0"><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left">K1</entry><entry namest="col2" nameend="col2" align="center">without</entry><entry namest="col3" nameend="col3" align="char" char=",">+7,1</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 6,0</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 3,2</entry></row><row><entry namest="col2" nameend="col2" align="center">With</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 9,2</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 6,5</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 5,8</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left">K4</entry><entry namest="col2" nameend="col2" align="center">without</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 7,6</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 6,5</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 3,7</entry></row><row><entry namest="col2" nameend="col2" align="center">With</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 9,1</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 7,2</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 5,6</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left">K2</entry><entry namest="col2" nameend="col2" align="center">without</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 7,0</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 5,9</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 3,1</entry></row><row rowsep="1"><entry namest="col2" nameend="col2" align="center">With</entry><entry namest="col3" nameend="col3" align="char" char=",">+ 9,0</entry><entry namest="col4" nameend="col4" align="char" char=",">+ 8,8</entry><entry namest="col5" nameend="col5" align="char" char=",">+ 6,7</entry></row></tbody></tgroup></table></tables>

The results show that the catalysts are able to increase the bleaching performance of various types of oxidizing agents at 20 ° C even in the smallest concentrations.