MXPA99003156A - Method of treatment of textiles - Google Patents

Abstract

Prevention of the uptake of migrating dyes in wash liquors containing a peroxide-containing washing agent by adding 0.5-150 mg/l of a non-symmetrical Mn complex (I) is claimed, as are also:(i) some the compounds (I) which are novel;(ii) (ii) novel bisphenol ligands (II) for preparation of (I);(iii) preparation of (II);(iv) 2 specific compounds of type (I);and (v) wash liquors containing (I). The Mn complexes (I) used in the wash liquors:n=0, 1, 2 or 3;m=1, 2 or 3;A=an anion;Y=(a) an alkylene group of formula -(C(R5)2)r;(b) -CX:CX-;(c) -(CH2)q-NR4-CH2)q-;or (d) 1,2-cyclohexylene or -phenylene, each optionally substituted by R9 as per formula (III) or (IV);r=1-8;R4 and R5=H or 1-4C alkyl;X=cyano, 1-8C alkyl or di(1-8C alky)amino;q=1, 2, 3 or 4;R9=SO3H, CH2OH or CH2NH2;R and R1=cyano, halogen, OR5, COOR5, nitro, 1-8C alkyl (optionally partially or fully fluorinated), NHR6, NR6R7, 1-8C alkyl-R8, or N<+>R4R6R7, with the proviso that R and R1 are not the same when n=m;R6 and R7=1-12C alkyl or together and with the bonded N atom form a 5-, 6- or 7-membered ring optionally containing further heteroatoms;R8=OR5, COOR5, NR6R7 or NH2;R2 and R3=H, 1-4C alkyl, aryl (optionally substituted by cyano, halogen, OR5 or COOR5), nitro, 1-8C alkyl, NHR6, 1-8C alkyl-R8 or N<+>R4R6R7 The Independent claims cover (i) novel compounds (IA) as per formula (I) but in which R2 and R3 are both H and the case in which one of these is H and the other is phenyl is excluded;(ii) novel ligands of formula (II);(iii) preparation of (II);(iv) the 2 specific compounds of type (I) as shown by formulae (IB) and (IC) under SPECIFIC COMPOUNDS below;and (v) wash liquors comprising by wt. (a) 5-90%anionic and/or nonionic surfactants;5-70%builder;0.1-30%peroxide;and 0.005-2%(I);or (b) 5-70%anionic and/or nonionic surfactants;5-40%builder;1-12%peroxide;and 0.1-0.5%(I).

Description

PROCESS FOR TREATMENT OF TEXTILE MATERIALS This invention relates to a process for preventing the re-deposition of dyes that migrate in washing liquids comprising a peroxide and a manganese catalyst suitable for the process, and to the detergent formulations comprising these catalysts. . It is already known that some manganese complexes of the "out" type are suitable catalysts for oxidations with the peroxygen compounds, especially as part of a washing process. The "come out" complexes included are exclusively symmetrical. It has also been previously described that certain manganese complexes have a pronounced bleaching effect on dirt and dyes in the washing liquid. It has now been discovered that certain asymmetric manganese complexes of the type exhibit a much greater specific action as catalysts to prevent the redeposition of the dyes migrating in the washing liquid, without noticeably damaging both the dye or the fiber. The complexes are classified as asymmetric when they arise through the reaction of 2 moles of two differently modified salicylaldehydes or o-hydroxyphenyl ketones with 1 mole of ethylenediamine or another modified diamine-forming block and thus have two substituted aromatic radicals ^ in a different way. The present invention therefore provides a process for preventing the redeposition of dyes migrating in the washing liquid, comprising the addition to the washing liquid, comprising a peroxide-containing detergent, between 0.5 and 150 mg, preferably between 1, 5 and 75 mg and, in particular, between 7.5 and 40 mg per liter of the washing liquid of one or more compounds of the formula: where n is 0, 1, 2 or 3, m is 1, 2 or 3, A is an anion; Y is a linear or branched alkylene radical of the formula - [(R2) 2] -, where r is an integer between 1 and 8 and the radicals Rs independently of one another are hydrogen or C 1 -C 4 alkyl; -CX = CX, where X is cyano, linear or branched Ci-Cs alkyl or di (linear or branched Ci-Cß alkyl) -amino, - (CH2) q-NR4- (CH2) q-, where R4 is hydrogen or straight or branched C1-C4 alkyl and q is 1, 2, 3 or 4 or a 1,2-cyclohexylene radical of the formula: Or a 1,2-aryl radical of the formula: / \ Where R9 is SO H, CH2OH or CH NH2l R and Ri independently are cyano, halogen, ORs or COOR5, where R5 is hydrogen or a linear or branched C1-C4 alkyl or are nitro, linear Ci-Cs alkyl or branched, linear or branched, partially perfluorinated or perfluorinated d-Cβ alkyl, NHRe or NR6R7 where Re and R are identical and are each linear or branched C? -C? 2 alkyl or where Re and R together with the nitrogen atom which connects them form a 5-, 6- or 7-membered ring which can include other heteroatoms, or they are linear or branched Ci-Cβ-Rβ alkyl, where Re is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2 or are -N + R RßR7, where R4, Re and R7 are as above, R2 and R3 independently of one another are hydrogen, straight or branched C1-C4 alkyl or unsubstituted aryl or, aryl substituted with cyano, halogen , OR 5 or COOR 5 where R 5 is hydrogen or straight or branched C 1 -C 4 alkyl, or by nitro, C 1 -C 8 alkyl neal or branched, NHRß or NR6R7 where R6 and R7 are identical or different and are as defined above, or by straight or branched alkyl Ci-Cβ-Rβ, where Rs is a radical OR5, COOR5 or NRßR7 with the above definitions or is NH2, or by -N + R4ReR7, where R4, R6 and R7 are as defined above, with the proviso that R and Ri do not have the same definition if n and m are identical. In the compounds of the formula (1) wherein n is 2 or 3, the radicals R may have the same or different definitions. With respect to the radicals R, the same applies to the compounds of the formula (1) wherein m is 2 or 3. When Y cs a 1, 2-cyclohexylene radical can be present in each of its cis-stereoisometric forms /after. Preferably Y is a radical of the formula - (CH2) r-, where r is an integer between 1 and 8, or of the formula -C (R5) 2- (CH2) pC (Rs) 2- where p is a number between 0 and 6 and R5 is hydrogen or C1-C4 alkyl.

In the particularly preferred compounds of the formula (1) Y is a radical of the formula - (CH 2) r, wherein r is an integer between 1 and 4, or of the formula - (CR 5) 2- (CRs) 2-, where Rs independently each time it appears is hydrogen or methyl. Halogen is preferably chlorine, bromine or fluorine, with chlorine being preferred.

If n or m is 1 of the groups R and Ri are preferably at the 4-position of the respective benzene ring except when R or Ri, respectively, is nitro or COOR5. In this case the group R or R1, respectively, is preferably in the position 5. If nom is 2, the two group R or the groups R1 are preferably in positions 4 and 6 of the respective benzene ring when R or R (l respectively they are nitro or COOR 5. In this case the two groups R or groups R1, respectively, are preferably in positions 3 and 5. If R or Rt is di (alkylC? -Ci2) amino, the alkyl group can be straight chain or branched preferably contains between 1 and 8, in particular between 1 and 4 and, especially, 1 or 2 carbon atoms The radicals R and R1 are preferably hydrogen, nitro, OR5, COOR5 or N (Rs) 2 with R5 being hydrogen or C 1 -C 4 alkyl, especially methyl or ethyl radicals R 2 and R 3 are especially hydrogen, methyl, ethyl or unsubstituted phenyl Aryl is, for example naphthyl or especially phenyl, SI Re and R 7 together with the nitrogen atom connects them form a ring of 5-, 6-, or 7-members, this ring is especially a pyrrolidine, piperidine, morpholine or piperazine ring. The piperazine ring may be substituted by alkyl, for example, on the nitrogen atom which is not attached to the phenyl radical.

Examples of suitable anions are halide, such as, for example, chloride, perchlorate, sulfate, nitrate, hydroxide, BF 4", PFe", carboxylate, acetate, tosylate and triflate. Chloride, acetate and carboxylate are preferred among them. The present invention also provides the compounds of the formula where N is O, 1, 2 or 3, M is 1, 2, or 3, A is an anion; Y is a linear or branched alkylene radical of the formula - [C (R5) 2] r-, where r is an integer between 1 and 8 and the radicals R5 independently of each other are hydrogen or C1-C4 alkyl; -CX = CX-, where X is cyano, straight or branched Ci-Cß alkyl or di (straight or branched Ci-Cß alkyl) -amino, - (CH2) q-NR4- (CH2) q-, where R4 is as we defined earlier and q is 1, 2, 3 or 4; or a 1,2-cyclohexylene radical of the formula: Or a 1,2-aryl radical of the formula: wherein R 9 is SO 3 H, CH 2 OH or CH 2 NH 2, R and Ri independently of each other are cyano, halogen, OR 5 or COOR 5, where R 5 is hydrogen or straight or branched C 1 -C 4 alkyl, or are nitro, linear or branched Ci-Cβ alkyl, linear or branched, partially fluorinated or perfluorinated Ci-Cß alkyl, NHRe or NR6R7 where Re and R7 are identical or different and each is C? -C? 2 alkyl? or where R6 and R7, together with the nitrogen atom connecting them, form a 5-, 6- or 7-membered ring which may include other heteroatoms, or are d-Cß-Rs alkyl, where Rs is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2, or are -N + R4R5R7, where R4, Rs and R7 are as defined above, R2 and R3 independently of one another are hydrogen, straight or branched C1-C4 alkyl or unsubstituted aryl, or aryl substituted by cyano, halogen, OR 5 or COOR 5, wherein R 5 is hydrogen or straight or branched C 1 -C 4 alkyl, or nitro, linear or branched Ci-Cs alkyl, NHR6 or where Re and R7, together with the nitrogen atom connecting them, form a 5-, 6- or 7-membered ring which may include other heteroatoms, or -Cß-Rβ linear or branched, where R8 is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2 or -N + R4ReR7, where R4, Re and R7 are as defined above, with the proviso that R and Ri they do not have the same definition if n and m are identical and R2 and R3 are both hydrogen and that, of the radicals R2 and R3, it is not the case that one is hydrogen and the other is phenyl.

Preferred definitions indicated below the manganese complexes of the formula (1) for n, m, Y, A, R, Ri, R2 and R3 are also preferred for the compounds of the formula (1a). The compounds of formula (1) and (1a) were prepared, for example, in a conventional manner from the corresponding ligands and a manganese compound. Preparation processes of this type are described, for example, in U.S. Patent Nos. 5,281,578 and 4,066,459. All the manganese complexes mentioned here, however, have symmetrically substituted ligands. Surprisingly, the manganese complexes of the invention, which have asymmetric ligands, characterize an increased specific action as catalysts for oxidations with the peroxides. The ligands of the formula: Where R; R1, R2, R3, Y, n and m are as defined in formula (1 a) they are also new. They were prepared in a conventional manner by means of, for example, the reaction of a diamine of the formula H2N-Y-NH2 first with an aldehyde or ketone of the formula: and then with an aldehyde or ketone of the formula: In the formulas (3) and (4) R, Ri, R2, R3, n and m are as defined with the formula (1), with the proviso that R and Ri do not have the same definition if n and m are identical. The compounds of the formula are of particular interest for using in the process of the invention Y It is also possible to use the compounds of the formula (1) together with the corresponding analogous symmetrical manganese complexes, that is, with compounds of the formula (1) wherein (R) n and (R?) M are identical. These mixtures are obtained, for example, by reacting a diamine of the formula H2N-Y-NH2 with a mixture of two different compounds of the formula (3) in the above synthesis of ligands of the formula (2) and converting the resulting mixture comprising an asymmetric ligand and two symmetric ligands of the formula (2) in the corresponding Mn complexes. The present invention further provides a detergent comprising: I) 5-90%, preferably 5-70% of A) an anionic surfactant and / or B) of a nonionic surfactant; II) 5-70%, preferably 5-50% and, in particular, 5-40% C) of a forming substance III) 0.1-30%, preferably 1-12% D) of a peroxide, and IV ) 0.005% - 2%, preferably 0.02 - 1% and, in particular, 0.1 - 0.5% of E) of a compound of the formula defined above (1), where the percentages are in each case weight based on the total weight of the detergent. The detergent may have the solid or liquid form such as, for example, a non-aqueous liquid detergent comprising not more than 5 and preferably between 0 and 1% by weight of water and, as its base may have a suspension of water. a forming substance in a non-ionic surfactant, as described, for example in GB-A-2,158,454. Preferably, however, the detergent is in the form of a powder or granule. This detergent can be prepared, for example, by first preparing an initial powder by spray drying an aqueous paste comprising all the aforementioned components with the exception of D) and E) and then adding the dry components D) and D) and mixing all the components together. Alternatively, component E) can be added to an aqueous paste comprising components A), B) and C) which are then spray dried, then component D) can be mixed with the dry mass. Even another option is to start with an aqueous paste comprising components A) and C) but not, not all, component B). The aqueous paste is spray dried, then component E) is mixed with component B and added, subsequently component D is mixed in dry form. The anionic surfactant A) can be, for example, a sulfate, sulfonate or carboxylate surfactant or mixtures thereof. Preferred sulphates are those with 12-22 carbon atoms in the alkyl radical, alone or in combination with the alkyl ethoxy sulfates whose alkyl radical has between 10-20 carbon atoms. Preferred sulfonates are, for example, alkylbenzene sulfonates with 9-15 carbon atoms in the alkyl radical. The cation in the anionic surfactants is preferably an alkali metal cation, especially sodium. The preferred carboxylates are the alkali metal sarcosinates of the formula R-CO-N (R 1) - CH 2 COOM 1, where R is an alkyl or alkenyl having 8 to 18 carbon atoms in the alkyl or alkenyl radical, R 1 is an alkyl of C1-C4 and M1 is an alkali metal. The nonionic surfactant B) can be, for example, the product of the condensation of 3-8 mol of ethylene oxide with 1 mol of primary alcohol having between 9-15 carbon atoms. Examples of the suitable forming substances C) are alkali metal phosphates, especially tripolyphosphates, carbonates or bicarbonates, especially their sodium salts, silicates, aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylene poly (alkylene phosphonates), or mixtures thereof. these compounds. Particularly suitable silicates are the sodium salts of the crystalline phyllosilicates of the formula NaHSITOa + i.pFbO or Na2SitO2t +? PH2O, where t is a number between 1, 9 and 4 and p is a number between 0 and 20. Of the silicates aluminum, preference is given to those obtained commercially under the names A; B, X and HS and mixtures comprising two or more of these components. Among polycarboxylates, it is preferred to polyhydrocarboxylates, especially citrates and acrylates and also to their copolymers with maleic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid, and ethylenediamineadisuccinate, both in the racemic form and in the enantiomerically pure S, S form. Particularly suitable phosphonates or aminoalkylene poly (alkylene phosphonates) are the alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid) and diethylenetriamine-pentamethylene phosphonic acid.

Suitable peroxide components D are, for example, referred to in the literature and are the commercially available organic and inorganic peroxides that bleach textiles at normal wash temperatures: for example, between 10 and 95 ° C. Organic peroxides are, for example, mono- or polyperoxides, especially organic peracids or their salts, such as, for example, phthalimidoperoxycaproic acid, diperoxydecanedioic acid, diperoxynonanedioic acid, diperoxydecanoidoic acid, diperoxyphthalic acid or their salts.

It is preferred, however, to use inorganic peroxide, examples being persulfates, perborates, percarbonates and persilicates. Of course, it is also possible to use mixtures of inorganic and / or organic peroxides. The peroxides can be present in different crystal forms and with a variable water content and can also be used together with other organic or inorganic compounds to increase their storage stability. The addition of the peroxides in the detergent preferably takes place by mixing the components with the aid, for example of a screw measuring system and / or a fluidized bed mixer. In addition to the combination of the invention, the detergents may comprise one or more fluorescent whitening agents of the kinds, for example as, bistriazinylaminostylenebenodisulfonic acid, bistriazolyl-benzylbenodisulfonic acid, a bis-styrylbiphenyl derivative or bisbenzofurylbiphenyl or bibenzoxalyl, coumarin derivative or pyrazoline derivative. In addition, the detergents may comprise soil anti-redeposition agents, such as for example sodium carboxymethyl cellulose, pH regulators, such as, for example, alkali metal silicates or alkaline earth metal silicates, foam regulators, such as soaps, salts for regulating spray drying and granulating properties, such as, for example, sodium sulfate, fragrances and, if desired, antistatics and softeners for fabrics, enzymes, such as, for example, amylase, bleaches, pigments and / or matting agents. These constituents must, of course, be stable with respect to the bleach used. Preferred aggregates for the detergents of the invention are polymers that prevent stains because, when the fabrics are washed, the dyes in the washing liquid have been separated from the fabrics under the washing conditions. These are preferably polyvinyl pyrrolidones, which are not modified or modified by means of the incorporation of anionic or cationic substituents, and especially those having a molecular weight in the range between 5,000 and 60,000, in particular between 10,000 and 50,000. These polymers are preferably used in an amount between about 0.05 and 5% by weight, in particular between 0.2 and 1.7% by weight, based on the total weight of the detergent.

In addition, the detergents of the invention may also include what are known as perborate activators, for example TAED or TAGU, for example. It is preferred to TAED; which is preferably used in an amount between 0.05% and 5% by weight, in particular between 0.2 and 1.7% by weight, based on the total weight of the detergent. The following examples serve to illustrate the invention without restricting it. The parts and percentages are by weight unless otherwise specified. Example 1: N-Mono [4- (diethylamino) salicylidene] -2-methylpropane-1,2-diamine A solution of 4.56 g (0.0517 mol) of 1,2-diamino-2-methylpropane in 50 ml of ethanol was introduced as initial charge. A solution of 10.0 g (0.0517 mol) of 4-N-diethylaminosylcylaldehyde in 50 ml of ethanol was added dropwise at room temperature over the course of 2 hours with stirring. After stirring for 2 hours (TLC monitoring, acetonitrile / water 9: 1) the reaction was completed. The reaction solution was carefully concentrated and the residue was dried under high vacuum. The obtained crude product comprises 13.6 g of a dark red oil which was subsequently used without further purification. Example 2: N-Mono [4- (dimethylamino) salicyldene] -2-methylpropane-1,2-diamine A solution of 0.0 g (60.53 mmol) of 4-N-dimethylaminosalicylaldehyde in 100 ml of ethanol was added dropwise at room temperature over the course of 2 hours with stirring at 6.4 ml (5.3 ml). g, 60.5 mmol) of 1,2-diamino-2-methylpropane. After stirring for 2 hours (TLC monitoring, acetonitrile / water 9: 1) at room temperature, the reaction was completed. The reaction solution was carefully concentrated and the residue was dried under high vacuum. The crude product obtained was formed by 14 g of a dark red oil which was subsequently reacted without further purification. Example 3: N-1 - [4- (diethylamino) salicylyl] -N'-2- (4-methoxysalicylidene) -2-methylpropane-1,2-diamine (structure I) and N-2- [4- (diethylamino ) salicylidene] -N'-1- (4-methoxysalicylidene) -2-methylpropane-1,2-diamine (structure lí) A suspension of 13.6 g (0.0517 mol) of N-Mono [4- (diethylamino) salicylidene] -2-methylpropane-1,2-diamine from Example 1 in 50 ml of ethanol was heated with stirring at 50 ° C. C until a clear solution is obtained. 7.87 g (0.0517 mol) and 4-methoxysalicylic acid (solid) were added and the mixture was heated to reflux for 2 hours. After completing the reaction time (TLC monitoring, ethyl acetate / methanol): 1). Then the reaction solution was carefully concentrated and the residue was dried under high vacuum. The crude product obtained comprises 20 g of a dark red oil, which solidifies slowly. Purification is by column chromatography (eluent: ethyl acetate / methanol 9: 1). The derivative "salen" substituted asymmetrically was isolated as a mixture of diastereomer (structure I and II). Product: 7 g, reddish oil (34%). The product was characterized by 1H and 13C NMR spectroscopy. 13C NMR (CDCfe): d = 12.7 (CH3CH2N), 25.3, 25.4 ((CH3) 2C-), 44.5 (NCH2CH3), 55.3 (OCH3), 58.5, 59.3 (C cuat, (CH ^ sC-), 68.7, 69.3 (NCH2 =, 98.0, 98.5, 101, 2, 101, 5, 103.0, 103.1 106.2, 106.3, 133.0, 133.1 (tere aril-C), 108.3 108.4, 112.1, 112, 3, 151, 6, 151, 9, 163.7, 163.9, 166.0 166.7, 167.4, 168.4 (aril-C cuat), 159 , 2, 160.2 164.8, 165.5 (C = N). MS (EI-MS) m / z: 397.3 (M) +, 205, 192 (isomer I), 233 (isomer II).

Example 4: N-1 - [4- (diethylamino) salicylodene] -N'-2- (4-hydroxysalicylic) -2-methylpropane-1,2-diamine (structure I) and N-2- [4- (diethylamine) salicylyl] -N'-1- (4-methoxysalicylidene) -2-methylpropane-1,2-diamine (structure II) A solution of 1.36 g (5.17 mmol) of N-Mono [4- (diethylamino) salicylidene] -2-methylpropane-1,2-diamine from Example 1 in 5 ml of ethanol was mixed with 715 mg (5 mg). , 17 mmol) of 4-hydroxysalicylaldehyde and the solution was heated at 60 ° C for 3 hours. After the end of the reaction (TLC monitoring, ethyl acetate / methanol 9: 1) the mixture. The reaction was carefully concentrated and the residue was purified by column chromatography (250 g of silica gel, ethyl acetate / methanol 9: 1). Product: 244 mg (12%, isomeric mixture .13C NMR (CD3OD): d = 12.3 (CH3CH2N), 24.1, 24.5 ((CH3) 2C-), 44.6 (NCH2CH3), 57, 3, 58.6 (C cuat), 63.0, 66.3 (= NCH2), 98.9, 99.4 100.1, 104.1, 104.3, 107.7, 134.6, 135 , 2, 135.8 (Tere aril-C), 108.2, 111, 3, 111, 6, 154.6, 155.1, 164.2, 165.0, 173.9, 175.9 (Cuat aryl-C), 158.3, 161, 4 163.5, 166.6 (C = N) Example 5: N-1- [4- (diethylamino) salicyldene] -N'-2- ( salicylidene) -2-methylopropane-1,2-d-amines (structure I) and N-2- [4- (diethylamino) salicylidene] -N'-1- (salicylidene) -2-methylpropanol, 2-diamine (structure II).

II A solution of 13.62 g (0.0517 mol) of N-mono [4- (diethylamino) salicylidene] -2-methylpropane-1,2-diamine from Example 1 in 50 ml of ethanol was heated to 50 ° C. and 5.5 ml (6.31 g, 0.0517 mol) of salicylaldehyde were added in the form of drops over the course of three minutes. During this addition the temperature of the solution was raised to 5 ° C. The reaction solution was heated to reflux for three hours, allowed to cool and concentrated on a rotary evaporator. This gives 19, 31 g of a crude mixture comprising the diastereomers I and II. The crude mixture was resolved by column chromatography (ethyl acetate / methanol 9: 1). Product: 4.01 g (21%) I, light brown solid, 1.55 g (8%) II, light brown oil. NMR data I 13 C NMR (CD 3 OD): d = 12.2 (CH 3 CH 2 N), 23.9 ((CH 3) 2 C-), 44.5 (NCH 2 CH 3), 60.1, (C cuat (CH 3) 2), 62 , 0 (= NCH2), 99.4, 104.3, 1 17.0, 118.6, 132.4, 132.8, 135.6 (tere aril-C), 108.3, 119.1, 155.2, 162.2 (quat aryl-C), 162.8, 163.5 (C = N). Example 6: N- [4- (dimethylamino) salicylidene] -N '- (salicylidene) -1,2-ethylenediamine .83 g (35.3 mmol) of 4-N- (dimethylamino) salicylaldehyde and 4.36 g (35.3 mmol) of salicylaldehyde were introduced into 30 ml of ethanol and the mixture was heated to 50 ° C. 2.27 ml (2.03 g, 33.6 mmol) of ethylenediamine were added over the course of 2 minutes. During the aggregate, the temperature of the reaction rose by about 15 ° C. The suspension was heated to 65 CC for 4 hours. After cooling the mass of the reaction solidified to give 14.2 g of a dark brown solid. 100 ml of a 9: 1 ethyl acetate / methanol mixture was added to this solid and the resulting mixture was stirred for 2 hours. The solid was filtered and resuspended twice. The remaining solid was filtered and the filtrate was concentrated. The residue was purified by column chromatography (450 g of silica gel, ethyl acetate / methanol 9: 1). Product: 1, 3 g (12%). 13 C NMR (CD 3 OD): d = (= NCH 3) 53.3, 60.7, (NCH 2) 104.3, 1 17.01, 131, 9, 132.1, 132.8, 132.9, 135, 0, 135.2, 163.7, 167.3 (tere aril-C), 118.5, 157.3, 161, 6, 162.3 (cuat aryl-C), 163.0, 168.0 ( C = N). Example 7: N-1- [4- (dimethylamino) salicylaldene] -N'-2- (salicyldene) -2-methylpropane-1,2-diamine (structure I) and N-2- [ 4- (dimethylammono) salicylidene] -N'-1- (salicylic) -2-methylpropane-1,2-diamine (structure II) I II A solution of 7.67 g (30.3 mmol) of N-mono [4- (dimethylamino) salicylidene] -2-methylpropane-1,2-diamine from Example 2 in 50 ml was heated to 50 ° C. of ethanol. Drops of this temperature were added in 3.70 g of salicylaldehyde (30.3 mol). The reaction solution was encouraged to reflux for 1 hour. The dark brown suspension was concentrated. This gives 10.3 g of the crude product which was purified by column chromatography (1 kg of silica gel, eluent: ethyl acetate / methanol 9: 1). Product: 1.7 g (16%) I of a yellowish solid, 0.81 g (8%) II, of a brownish solid. 2.9 g (28%) of an isomeric mixture was also isolated (composition according to 1 H NMR, 75 g of I, 1.17 g of II). Isomeric structure I: 13C NMR (CD3OD): d = 1.40 (s, 6H, CH3), 3.00 (s, 6H, NCH3), 3.60 (m, 2H, = NCH22), 6.12, 6.18, 6.83, 6.90, 6.98, 7.21, 7.25, (m, every 1 H, tere aril-H), 8.03, 8.32 (s, every 1 H , CH = N). 13 C NMR (CD3Cl3): d = 25.0 ((CH3) 2C-), 40.1 (NCH3), 60.2 (cuat C (CH3) 2), 68.9 (NCH2), 98.8, 103 , 5, 117.1, 131, 4-132, 1 (tere aryl-C), 108.8, 153.7 (quat aryl-C), 118.8 (C = N and quat aryl-C), 165 , 0 (C = N and cuat aryl-C). Structure of isomer II 13C NMR (CD3CI3): d = 25.5 ((CH3) 2C-), 40.1 (NCH3), 58.8 (C cuat), 70.7 (NCH2), 99.2, 103 , 4, 117.0, 1 18.6, 131, 6, 132.3, 132.9 (tere aryl-C), 108.9, 154.0, 161.6 (cuat aryl-C), 159, 5, 166.5 (C = N). Example 8: N-1- [4- (dimethylamino) salicylyl] -N'-2- (4-hydroxyalalylidene) -2-methylpropane-1,2-diamine (structure I) and N-2- [ 4- (dimethylamino) salicylidenoj-N'-1- (4-hydroxysalidyl) -2-methylpropane-1,2-diamine (structure II) A solution of 7.67 g (30.3 mmol) of N-mono [4- (dimethylamino) salicyloidene] -2-methylpropane-1,2-diamine from Example 2 in 50 ml of ethanol was heated to 55 ° C. At this temperature, 4.18 g (30.3 mmol) of 2,4-dihydroxybenzaldehyde (solid) was introduced. The reaction mixture was subsequently heated to reflux until the starting material disappeared (TLC monitoring, ethyl acetate / methanol 9: 1). The grayish brown suspension was concentrated and the residue was dried under high vacuum. This gives 10.8 g of the crude product which was suspended in 50 ml of 9: 1 ethyl acetate / methanol. The suspension was filtered, concentrated (1.38 g of the crude product) and separated by column chromatography (ethyl acetate / methanol 9: 1). Product: 290 mg (3%), mixture of isomer I and II. 13 C NMR (DMSO-de): d = 26.0, 26.1 ((CH3) 2C-), 40.3 (NCH3), 59.2, 59.7 (C cuat, C (CH3) 2), 68.5, 68.9 (NCH2), 99.0, 99.2, 103.4, 103.6, 104.1, 104.3, 107.4, 107.7, 133.6, 134.0, 134.3-134.6 (tere aril-C), 109.2 109.4, 112.1, 154.4, 154.5, 162.7, 165.2, 165.5 (aryl C cuat), 161, 3, 162.0, 166.3, 166.7 (C = N). Example 9: N-1 - [4- (dimethylamino) salicylidene] -N'-2- (4-methoxysalidylidene) -2-methylpropane-1,2-diamine (structure I) and N-2 - [4- (dimethylamino) salicylyl] -N'-1- (4-methoxysalicylidene) -2-methylpropane-1,2-diamine (structure II).

I A solution of 7.67 g (30.27 mmol) of N-mono [4- (dimethylamino) salicylidene] -2-methylpropane-1,2-diamine from Example 2 in 50 ml of ethanol was heated to 50 ° C. . At this temperature, 4.6 g (30.27 mmol) of 4-methoxysalicylaldehyde were introduced. The mixture was heated to reflux for 2 hours and cooled, and the reaction solution was concentrated. The obtained brown solid (12.2 g) was purified by column chromatography (1 kg of silica gel, ethyl acetate / methanol 9: 1). Product: 4.69 g (42%), isomer mixture. 13 C NMR (CD3Cl3): d = 25.3 ((CH3) 2C), 40.3 (NCH3), 55.3 (OCH3), 58.6, 59.2 (C cuat, C (CH3) 2), 68.8, 69.2 (= NCH2), 98.9, 99.2, 101, 2, 101, 4, 103.4, 103.5, 106.2, 106.4, 132.8, 133, 1 (tere aril-C), 108.7, 108.8, 112.1, 112.3, 153.8, 154.1, 163.7, 164.0, 166.8, 167.5 (aril- C cuat), 159.5, 160.2, 165.0, 165.5 (C = N). Example 10: N- [4- (diethylamino) salicylidene] -N '- (4-methoxysalicylidene) -1,2-ethylene diamine A solution of 3.87 g (0.0644 mol) of ethylene diamine in 300 ml of ethanol was introduced as initial charge and at room temperature, a solution of 12.45 g (0.0644 mol) of 4-N- (diethylamino) salicylaldehyde in 60 ml of ethanol, added slowly < - n shape of drops with agitation. The solution was heated to reflux for 2 hours. After cooling to room temperature, a solution of 9.8 g (0.0644 mol) of 4-methoxysalicylaldehyde in 25 ml of ethanol was slowly added in the form of drops. The reaction solution was subsequently heated to reflux temperature for 1 hour. Allow to cool slowly and stir at room temperature for 8 hours. The resulting yellow suspension was worked up by concentration in vacuo and purified by column chromatography on silica gel (eluent: ethyl acetate / methanol 9: 1). The asymmetric ligand was isolated as an orange oil. Product: 4.00 g (17%). 13 C NMR (CD3Cl3): d = 12.7 ((CH3CH2N), 44.4 (NCH2CH3), 55.3 (OCH3), 58.1, 58.7 (NCH2), 98.0, 101, 2, 103 , 1, 106.3, 132.9, 133.0 (aryl-C tere), 108.3, 1 12.3, 151, 5, 163.5 (aryl-C cuat), 164.5, 165, 4 (C = N) Example 1 1: N- [4- (diethylamino) salicylidene] -N '- (4-hydroxysalicylidene) -1,2-ethylene diamine 6.09 g (31.5 mmol) of 4-N- (diethylamino) salicylaldehyde and 4.35 g (31.5 mmol) of 2,4-dihydroxybenzaldehyde were introduced into 30 ml of ethanol and the mixture was heated, until 50 ° C. 2 ml of (1.80 g, 30 mmol) of ethylenediamine were added over the course of two minutes. During the addition, the reaction temperature rose to about 10 ° C: The reaction solution was heated to 65 ° C for 4 hours. After cooling, the solution was concentrated to give 14.2 g of a dark brown oil. This oil was mixed with 100 ml of a mixture of ethyl acetate / methanol) 9: 1 and the resulting mixture was stirred for 2 hours. The solution was filtered and concentrated. The residue was purified by column chromatography (450 g of silica gel, ethyl acetate / methanol 9: 1). Product: 1, 18 g (11%), orange oil. 13 C NMR (DMSO-d 6): d = 13.4 ((CH 3 CH 2 N), 44.6 (NCH 2 CH 3), 57.9, 58.6 (= NCH 2), 98.2, 103.5, 103.7, 107 , 8, 132.0, 134.0, 134.3 (tere aryl-C), 108.6, 112.0, 126.3, 152.0, 162.8, 166.2 (aryl-C cuat) 165.7, 166.6 (C = N).

Example 12: N- [4- (diethylamino) salicylidene] -N '- (salicylidene) -1,2-ethylenediamine g (51.7 mmol) of 4-N-diethylaminosylylaldehyde and 6.31 g (51.7 mmol) of salicylaldehyde were dissolved in 50 ml of ethanol. 3.1 g (51.7 mmol) of ethylenediamine were added at room temperature. During this addition, the solution was heated to 40 ° C. It was heated to 70 ° C for 2 hours and allowed to cool. The reaction solution was concentrated to leave 21.6 g of a reddish-brown oil. The crude product was purified by column chromatography (1 kg of silica gel, ethyl acetate / methanol 20: 1). i3c NMR (CD3OD): d = 13.5 (CH3CH2N), 46.0 (NCH2CH3), 53.3, 60.7 (= NCH2), 100.5, 105.7, 118.5, 120.3, 132.8, 133.5, 137.0 (aril-C tere), 109.6, 156.6 164.5, 177.2 (aromatic quat), 163.0, 169.5 (C = N). Example 13: (R, R) -N- [4- (d-ethalamino) salicyldene] -N '- (salicyldene) -1,2-cyclohexanediamimide 0.2 g (0.916 mmol) of (R, R) -N-mono (salicylidene) -1,2-cyclohexanediamine prepared according to Tetrahedron Letters 39 (1998) 4199-4202 was dissolved in 20 ml of ethanol to give an clear yellow solution. At room temperature, 17 mg (0.916 mmol) of 4-N- (diethylamino) salicylaldehyde dissolved in 20 ml of ethanol was added as drops. The solution of the dark red reaction was heated to 60 ° C for 4 hours, then allowed to cool to room temperature and carefully concentrated on a rotary evaporator. This gives 386 mg of a red solid. This crude product was purified by column chromatography (30 g of silica gel, eluent: ethyl acetate). Product: 124.0 mg (34%) honey-colored honeycomb crystals. 13 C NMR (CDCl 3): d = 21.7 (CH 3 CH 2 N), 24.2, 24.4, 33.2 (CH 2 CI), 44.4 (CH 3 CH 2 N), 70.9, 72.9 (CH tere cid) ), 97.9, 103.0, 116.7, 1 18.5, 131, 5, 132.0, 132.9 (aril-C tere), 108.2, 118.8, 151, 3, 164 , 6, 165.3 (aryl-C cuat), 161, 1, 162.8 (C = N). Example 14: (R, R) -N- [4- (dimethylamino) salicylidene] -N '- (salicylidene) -1,2-cyclohexanediamine 0.5 g (2.29 mmol) of (R, R) -N-mono (salicylidene) -1,2-cyclohexanediamine was reacted with 0.378 g (2.29 mmol) of 4-N- (dimethylamino) ) salicylaldehyde as described in the preceding example. Analogous workup gave a yellow solid as a crude product (829 mg) which was purified by separation on a chromatography column (silica gel, ethyl acetate / methanol 9: 1). Product: 318 mg (38%), pale yellow solid. 13C NMR (CDCb): d = 24.2, 24.4, 33.2 (CH2, cid.), 40.0 (N-CH3), 71.1 (CH tere cid), 98.7, 103, 4, 116.7, 118.5, 131, 5, 132.0, 132.6 (aryl-C tere), 108.7, 118.7, 153.6, 161.1 (aryl-C cuat), 163.2, 164.7 (C = N). Example 15: (R, R) -N- [2-hydroxyacetophenone] -N '- (salicylaldehyde) -1,2-cyclohexanediimine To a solution of 0.5 g (2.29 mmol) of (R, R) -N-mono (salicylidene) -1,2-cyclohexanediamine in 50 ml of ethanol was added dropwise 0.32 g (2 g). , 29 mmol) of 2-hydroxyacetophenone dissolved in 50 ml of ethanol. The mixture was heated to reflux temperature for 8 hours. Cooling and concentration of the reaction solution gives 714 mg of a brown solid. This crude product was purified by column chromatography (eluent: toluene / ethyl acetate 3: 1). Product: 215.6 mg (28%), yellowish syrup. Example 16: (R, R) -N-mono [4- (diethylamino) salicylidene] -1, 2-cyclohexanediamine A solution of 3.95 g (34.55 mmol) of trans-1,2-diaminohexane in 770 ml of chloroform was mixed with 50 g of a molecular sieve (4 A) and cooled to -3 ° C. At this temperature, 6.68 g (34.55 mmol) of 4-N- (diethylamino) salicylaldehyde dissolved in 250 ml of chloroform were added dropwise over the course of 5 hours. After the addition, the solution was allowed to warm to room temperature and was stirred for 8 hours. During the course of the reaction, it was monitored by TLC (mobile phase: ethyl acetate / methanol 9: 1). After the end of the reaction, the solution was filtered and concentrated to give 9.9 g (100%) of the crude product which was subsequently used without further purification. Example 17: (R, R) -N- [4- (d.ethylamino) -salzylidene] -N '- (4-hydroxysalidylidene) -1,2-cyclohexanediamine To a suspension of 2.5 g (8.64 mmol) of (R, R) -N-mono [4- (diethylamino) salicylidene] -1,2-cyclohexanediamine in 200 ml of ethanol was added as drops to ambient temperature over the course of 45 minutes to a solution of 1.19 g (8.64 mmol) 2,4-dihydroxybenzaldehyde. The suspension was heated at 60 ° C for 4 hours. After cooling to room temperature, the orange-brown solution was concentrated to dryness. The crude product (3.5 g) was resolved by column chromatography (ethyl acetate / methanol 9: 1). Product: 570 mg (16%), yellowish orange solid. 13 C NMR (CDCl 2): d = 12.4 (CH 3 CH 2 N), 23.8, 32.7, 32.8, (-CH2 cid.), 43.7 (CH3CH2), 70.2, 70.6 (CH tere cid), 97.1, 102.3, 102.7, 106.7, 132.8, 133.1 (aril-C tere), 107.6, 111, 1, 150.7, 161, 4, 163.9 (aril-C cuat), 163.1, 163.8 (C = N). EXAMPLE 18: (R, R) -N- [4- (dimethylamine) salicylyl] -N '- (4-methoxysalicylidene) -1,2-cyclohexanediamine To a suspension of 2.5 g (8.64 mol) of (R, R) -N-mono [4- (diethylamino) salicylaldene] -1,2-cyclohexanedimine in 200 ml of ethanol was added in drop form over the course of 45 minutes at room temperature to a solution of 1.3 g (8.64 mmol) of 4-methoxysalicylaldehyde in 200 ml of ethanol. The reaction solution was heated at 60 ° C for 4 hours. After cooling to the reaction solution at room temperature, it was concentrated to dryness. The obtained crude product was purified by column chromatography (ethyl acetate / methanol 9: 1). Product: 500 mg (14%), reddish orange oil, which crystallizes slowly. 13 C NMR (CDCl 3): d = 12.7, (CH 3 CH 2 N), 24.3, 33.2 (-CH 2 CI), 44.4 (CH 3 CH 2 N), 55.3 (OCH 3), 70.9, 71, 5, 71, 6 (CH tere cid), 98.0, 101, 1, 103.0, 106.1, 106.2, 132.9 (aril-C tere), 108.2, 112.3, 151 , 3, 165.5 (aril-C cuat), 162.9 163.7 (C = N). Synthesis of manganese complexes: Example 19: Chloride of [N- [4- (Diethylamine?) Salicylicidene] -N '- (4-methoxysalicylidene) -1,2-ethylenediamine] - manganese (III) Procedure: 200 mg (0.541 mmol) of the ligand of Example 10 was dissolved in 11 ml of ethanol. 133 mg (0.541 mmol) of tetrahydrate manganese acetate (II) were introduced into this clear orange solution. A change of color to dark red occurs, and the precipitate forms. The mixture was heated to 70 ° C for 4 hours, during which time the precipitate enters the solution. The reaction solution was subsequently concentrated to dry on a rotary evaporator. This gives 306 mg of a solid which was dissolved in 11 ml of distilled water. The product was precipitated with 0.54 g of sodium chloride. It was purified by stirring for 10 minutes, filtered and dried under vacuum at 50 ° C. Product: 220 mg (89%), solid reddish black. Example 20: [N-2- [4- (diethylamino) salicyloiden] -N'-1- (salicylidene) -2-methylpropane-1,2-diamine]] manganese chloride (III) 1.2 g (3.25 mmol) of ligand II from Example 5 was dissolved in 65 ml of ethanol. 0.80 g (3.25 mmol) of manganese (II) acetate was added at room temperature to this yellowish orange solution. A red color change occurs. Mix the reaction at 65-70 ° C for 4 hours. The reaction mixture was concentrated to dryness, the residue was taken with 65 ml of distilled water, and the complex was precipitated with 3.25 g of sodium chloride, isolated by filtration and dried to a constant mass under a vacuum elevated at 50 ° C. Product: 1, 1 g (74%), solid reddish brown. Example 21: Chloride of [N-1- [4- (dimethylamino) salicylidene] -N'-2- (salicylidene) -2-methylpropane-1,2-diamine] manganese (lll) A suspension of 1 g (2.95 mmol) of ligand I of Example 7 in 60 ml ethanol was mixed with 0.72 g (2.95 mmol) of manganese acetate tetrahydrate (II). The machine for reaction and work up (precipitation with 6 g of sodium chloride) are analogous to those of Example 20. Product: 924 mg (73%), reddish brown solid. Example 22: 529 mg (1.56 mmol) of ligand II of Example 7 was reacted in 30 ml of ethanol with 380 mg (1.56 mmol) of manganese acetate (II) tetrahydrate and the product was precipitated with 3.1 g. of sodium chloride as described in Example 20. Product: 929 mg. The metal complex still contains sodium chloride and was used without further purification. Example 23: [N- [4- (diethylamino) salicylidene] -N '- (4-hydroxysalidylidene) -1,2-ethylenediamineto-manganese (III) 300 mg (0.844 mmol) of the ligand of Example 11 was suspended in 17 ml of ethanol, and 207 mg (0.844 mmol) of manganese acetate tetrahydrate (II) was added to the suspension. There was a change of color towards red. The reaction mixture was heated to reflux for 30 minutes and then maintained at 65-70 ° C for 3 hours. The solution was concentrated to give 419 mg of a solid which was taken in 17 ml of distilled water. The complex was precipitated by introducing 0.84 g of sodium chloride, isolated by filtration and dried.

Product: 314 mg (84%), dark red solid. Example 24: Chloride of [N-1- [4- (diethylamine) salicylidene] -N '- (4-methoxysalicylidene) -2-methyl-propane-1,2-diamine] manganese (III) (structure I) and chloride [ N-2- [4- (diethylamino) sacylicidene] -N'-1- (4-methoxysalicylidene) -2-methylpropane-1,2-diamine] -manganese (III) (structure II) 3 g (7.5 mmol) of the ligand (mixture of isomers) of Example 3 were dissolved in 150 ml of ethanol. To this light brown solution, which is yellow at high levels of dilution, 1.85 g (7.5 mmol) of manganese acetate tetrahydrate (II) was added. An intermediate color change towards red occurs. The clear solution was heated to 65-70 ° C for 4 hours, and after cooling, it was concentrated. The dark red oil (4.33 g) obtained (4.33 g) was taken in 150 ml of distilled water. The complex was precipitated with 7.5 g of sodium chloride, isolated by filtration and dried. Product: 2.68 g (73%), dark red solid, mixture of isomers. Example 25: [N- [4- (diethylamino) -salicylicidene-N- (salicyloid) -1, 2-ethylenediamineto-manganese (III) chloride A solution of 194 mg (0.57 mmol) of the ligand of Example 12 in 10 ml of ethanol was mixed with 140 mg (0.57 mmol) of manganese acetate (II) tetrahydrate. There was a change in color from reddish brown to blood red. The reaction solution was boiled under reflux for 3 hours, left overnight with stirring and heated for another 3 hours. After cooling, it was concentrated to dryness and the residue was extracted with 10 ml of distilled water, precipitated with 1.5 g of sodium chloride, isolated by filtration and dried under high vacuum. The product still contained sodium chloride and was used without further purification. Example 26: [N-1- [4- (diethylamino) -salzylidene] -N'-2- (salicylaldene) -2-methylpropane-1,2-d-amininate] manganese (III) chloride : 1.0 g (4.08 mmol) of manganese acetate tetrahydrate (II) was introduced into a solution of 1.5 g (4.08 mmol) of ligand I of Example 5 in 80 ml of ethanol. The resulting solution was heated at 65 ° C for 2 hours. After cooling, it was concentrated to dryness and the residue was taken up in 80 ml of distilled water, after which time the product was precipitated with 4.1 g of sodium chloride, isolated by filtration and dried under high vacuum. Product: 1.51 g (81%). Example 27: [N- [4- (dimethylamino) salicylyl] -N '- (salicylidene) -1, 2-ethylenediamine-isosmanganese (III) chloride: 86.5 mg (0.353 mmol) of manganese acetate tetrahydrate (II) were introduced into a solution of 110 mg (0.353 mmol) of the ligand of Example 6 in 5 ml of ethanol. The reddish brown solution obtained was heated at 65 ° C for 2 hours. After cooling, the solution was concentrated to dryness, the residue was extracted in 5 ml of distilled water, and the product was precipitated with 200 mg of sodium chloride, isolated by filtration and dried under high vacuum. Product: 61 mg (43%). Example 28: It was added in the form of drops to a solution of 2.5 g (9.56 mmol) (R, R) -N-mono (4-dimethylaminosyl-cyanidene) -1,2-cyclohexanedi amine in 225 ml of ethanol, a solution of 1. 321 g (9.56 mmol) of 2,4-dihydrobenzaldehyde in 225 ml of ethanol at room temperature over the course of 45 minutes. The reaction solution was heated to 60 ° C for 4 hours. After cooling to room temperature, it was concentrated until the resulting reddish brown solution dried. The crude product (ca. 5 g) was resolved by column chromatography (ethyl acetate / methanol 9: 1). Product: 1, 09 g (30%), yellowish orange solid. 13 C NMR (DMSO-de): d = 23.7, 32.7, 32.8 (CH2 ci), 40.0 (NCH3), 70.3, 70.7 (CH tere.Ci), 97.9 , 102, 103.2, 106.7, 132.5, 133.1 (aryl-C tere), 108.1, 11.1.1, 153.1, 161.4 (aril-C cuat), 163, 4, 163.9 (C = N). Example 29: (R, R) -N- [4- (dimethylamino) salicylaldehyde] -N '- (2-hydroxy acetophenone) -1,2-cyclohexanediimine S a solution of 2.5 g (9.56 mmol) of (R, R) -N-mono (4-dimethylaminosalicilidene) -1 (2-cyclohexanediamine in 225 ml of ethanol was added dropwise a solution of 1 g., 30 g (9.56 mmol) of 2-hydroxyacetophenone in 225 ml of ethanol. The reaction solution was heated at 60 ° C for 8 hours. The resulting clear reddish brown solution was stirred for a further 4 hours at room temperature and concentrated to dry at high vacuum. The crude product (3.6 g, dark red oil) was resolved by column chromatography (ethyl acetate / methanol 9: 1). Product: 1, 60 g (44%), reddish orange foam. 13 C NMR (CDCfe): d = 14.7 (CH3), 24.2, 24.3, 32.4, 33.2 (CH2 cid), 40.0 (NCH3), 62.3, 72.2 ( CH tere cid), 98.6, 103.4, 116.8, 118.6, 128.3, 132.3, 132.7 (aril-C tere), 108.6, 119.1, 153.6 , 164.3, 170.9 (aril-C cuat), 163.2 (C = N). Example 30: N-Mono [4- (d-ethylamino) salicyldene] -1,2-phenylenediamine 3,479 g (17.64 mmol) of 4- (N, N-diethylamino) -salicylaldehyde were added at 5 ° C in portions to a solution of 1.927 g (17.64 mmol) of 1,2-phenylenediamine. in 18 ml of ethanol, the temperature was kept below 10 ° C. The resulting dark red suspension was stirred for 8 hours at room temperature and concentrated to dryness in vacuo. The crude product (6.34 g) was resolved by column chromatography (n-hexane / ethyl acetate 65:35). Product: 1, 27 g (26%), golden yellow crystals. 13 C NMR (CDCl 3): d = 12.7 (CH 3), 44.6 (CH 2), 97.6, 103.7, 115.4, 118.2, 118.8, 126.6, 133.7 ( aryl-C tere), 109.3, 136.4, 140.4, 151.6, 163.2 (aryl-C cuat), 160.9 (C = N). Example 31: N- [4- (diethylamino) salicylidene] -N '- (salicylic) -1, 2-phenylenediamine To a yellowish brown suspension of 0.3 g (1.06 mmol) of N-Mono [4- (diethylamino) -salicyldene] -1,2-phenylenediamine of Example 30 in 2 ml of ethanol was added in a of drops at 60 ° C 129 mg (112 μl, 106 μmol) of salicylaldehyde. The reaction solution was stirred for 5 hours at 75 ° C and after cooling to room temperature it was concentrated to dryness. The crude product was resolved by column chromatography (n-hexane / ethyl acetate 65:35). Product: 139 mg (34%), colorless oil. 1 C NMR (CDCl 3): d = 11, 7 (CH 3 CH 2 N), 44.4 (CH 3 CH 2 N), 97.0, 102.4 (aryl-H tere), 116.5-119.0, 125.1, 126 , 6, 130.0-132.0 (aryl-C tere), 108.3, 118.3, 141, 1, 141, 4, 151, 2, 160.2 (aril-C cuat), 159.5 162.4 (C = N). Example 32: Preparation of a mixture of asymmetric and symmetrical manganese (III) -salene complexes The asymmetric "come out" complexes can also be used, without complicated purification as a mixture of different metal complexes. 4.74 g of the crude mixture of Example 5 were diluted with 250 ml of ethanol to give a light brown solution. 3.17 g (12.9 mmol) of manganese acetate tetrahydrate (II) were added, accompanied by a change in color towards red. The mixture was reacted at 65-70 ° C for 4 hours and then concentrated to dryness. The resulting solid was taken in 250 ml of distilled water, precipitated by adding 26 g of sodium chloride and dried under vacuum. The crude mixture was applied directly. The crude product comprises asymmetric metal complexes of Examples 20 and 26 and also metal complexes of the asymmetric ligand of the structure: Example 33: To investigate the effectiveness of the catalysts, the DTI efficiency was measured. DTI efficacy (inhibition of dye transfer) was defined as the following percentage: A = ([Y (E) - Y (A)] / [Y (W) - Y (A)] * 100 where Y (W), Y (A) and Y (E) are the CIÉ luminosities of the white material, of the material treated without added catalyst and of the material treated with the aggregate catalyst, in the order mentioned, a = 0 characterizes a product completely useless whose addition to the washing liquid gives a free moderation with respect to the dye transfer. On the other hand, a = 100% corresponds to a perfect catalyst that completely suppresses the staining of the white material. The test data was determined using the following test system: 7.5 g of a white cotton cloth was treated in 80 ml of the washing liquid. The liquid contains the standard detergent ECE phosphate free (456 IEC) EMPA; Switzerland, at a concentration of 7.5 g / l, 8.6 mmol / l H2O2 and a solution of the test dye. The washing process takes place in a bowl on a LINITEST device at 40 ° C for 30 minutes. In this test, the catalysts were used according to the standard at the established concentrations.

The following commercially available dyes are used as test dyes: Dye (F1) Natural brown 172 Dye 4 (F4) Blue reagent 238 T Tiinnttuurra 66 ((FF66)) Reactive black 5 Dye 8 (F8) Natural blue 71 Dye 9 (F9) Natural black 22 Dye 10 (F10) Anionic blue 133 Dye 13 (F 3) Violet dispersed 1 T Tiinnttuurraa 1144 ((FF1144)) Reactive blue 19 The reflection spectrum of the samples was measured with SPECTRAFLASH 2000 and became luminosity (D65 / 10) by means of the standard procedure according to CIÉ. The following table shows the results with the catalyst obtained according to Example 24 (Mn complex). This shows that the DTI (a) effects as a function of the catalyst concentration under the service conditions described above.

Table 1 The following table shows that the catalyst obtained according to Example 24 effectively prevents the redeposition of dyes of various kinds. The values indicated here refer to a catalyst concentration of 50 μmol / l and to the experimental conditions described above. Table 2 The catalyst has another caraderística that is that, even to a temperature of service of only 20 ° C, retained great part of the protective effect observed to 40 ° C.

Table 3: The catalyst characterizes an acceptable balance of damage with respect to the washing of colored fabrics. In terms of the damage of the dye, even when using dyes that are highly sensitive, the degradation is only the same order of magnitude as those observed with the TAED-activated bleaching system. In the oxygen bleaches sector, the latter are considered of the prior art with an acceptable harm / benefit balance. When used in the manner described above, there is the following loss of percentage dye after a fivefold treatment. Table 4 In terms of the damage of the fiber on the dyed materials, the catalyst exhibits a better balance than the aforementioned TAED system. When used in the manner described above, the following relative DP decrease is found after a fivefold treatment.

Table 5 Example 34: By carrying out the DTI classification with the following isolated ligands, which were converted into the manganese complexes immediately before classification by means of an in situ process, the results illustrated in Table 6 were obtained. Table 6: Table 7 shows the results obtained when the DT classification is performed with the isolated Mn complexes.

Table 7: Example 35: The asymmetric "come out" complexes described exhibit excellent action even at a reduced peroxide concentration. If the peroxide concentration is reduced from 8.6 mM to 0.17 mM; the DTI effect is completely retained. Table 8 below demonstrates the effect of the metal complex of Example 20 with a reduced amount of peroxide.

Claims (23)

CLAIMS Having thus specially described and determined the nature of the present invention and the way it has to be put into practice, it is claimed to claim as property and exclusive right:

1. A process for preventing redeposition of dyes migrating in a washing liquid, comprising adding to the washing liquid comprising a detergent containing peroxide, between 0.5 and 150 mg per liter of the washing liquid of one or more compounds of the formula: where n is 0, 1, 2 or 3, m is 1, 2 or 3, A is an anion; Y is a linear or branched alkylene radical of the formula - [(R2) 2] -, where r is an integer between 1 and 8 and the radicals Rs independently of one another are hydrogen or C1-C4 alkyl; -CX = CX, where X is cyano, linear or branched Ci-Cs alkyl or di (linear or branched Ci-Cß alkyl) -amino, - (CH2) q-NR4- (CH2) q-, where R is hydrogen or straight or branched C1-C4 alkyl and q is 1, 2, 3 or 4 or a 1,2-cyclohexylene radical of the formula: Or a 1,2-aryl radical of the formula: Where R9 is SO4H, CH2OH or CH2NH2, R and Ri independently are cyano, halogen, OR5 or COOR5, where R5 is hydrogen or a straight or branched C1-C4 alkyl or are nitro, straight or branched dCS alkyl linear or branched, partially perfluorinated or perfluorinated d-Cs alkyl, NHR6 or NR6R where R6 and R are identical and are each linear or branched C? -C? 2 alkyl or where Re and R7 together with the nitrogen atom connects them to form a 5-, 6- or 7-membered ring which may include other heteroatoms, or they are straight or branched alkyl-Cs-Rs, where Rs is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2 or are -N + R4R6R7, where R4, Re and R7 are as defined above, R2 and R3 independently of one another are hydrogen, straight or branched C1-C4 alkyl or unsubstituted aryl or, aryl substituted with cyano, halogen, OR5 or COOR5 wherein R5 is hydrogen or straight or branched C1-C4 alkyl, or by nitro, linear C? -C8 alkyl or branched, NHRß or NR6R7 where R6 and R7 are identical or different and are as defined above, or by straight or branched alkyl Ci-Cβ-Rβ, where Rs is a radical OR5, COOR5 or NRdR? with the above definitions or is NH2, or by -N + R4RßR7, where R4, Re and R7 are as defined above, with the proviso that R and RT do not have the same definition if n and m are identical.

2. A process according to Claim 1, wherein between 1.5 and 7.5 mg per liter of the washing liquid of one or more compounds of the formula (1) is added.

3. A process according to Claim 2, wherein between 7.5 and 40 mg per liter of the washing liquid of one or more compounds of the formula (1) is added.

4. A process according to Claims 1 to 3, wherein the anion A is halide, perchlorate, sulfate, nitrate, hydroxide, BF ", PF6", carboxylate, triflate or tosylate.

5. A process according to Claim 4, wherein the anion A is chloride or acetate.

6. A process according to one of Claims 1 to 5, wherein Y is a radical of the formula (CH2) r-, wherein r is an integer between 1 and 8, or of the formula -C (R5) 2- (CH2) PC (R5) 2-. where p is a number between 0 and 6 and Rs is hydrogen or C1-C4 alkyl.

7. A process according to Claim 6, wherein Y is a radical of the formula - (CH2) r-, where r is an integer between 1 and 4, or of the formula - (CRs) 2- (CRs) 2 -, where R5 independently each time it appears is hydrogen or methyl.

8. A process according to one of Claims 1 to 7, wherein the halogen is chlorine, bromine, or fluorine, especially chlorine.

9. A process according to one of Claims 1 to 8, wherein n and / or m is 1 and R and / or R1 are nitro or COOR5 and are located at the 4-position of the respective benzene ring.

10. A process according to one of claim 1 to 8, wherein ny / om is 1, R and / or R1 are nitro or COOR5 and are located at the 4-position of the respective benzene ring, and R5 is hydrogen or a linear or branched C1-C4 alkyl.

11. A process according to any of Claims 1 to 10, wherein n and / or m is 2 and R and / or Ri are as defined with the exception of nitro and COORs and are located at positions 4 and 6 of the respective benzene ring.

12. A process according to Claims 1 to 10, wherein n and / or m is 2 and R and / or R1 are nitro or COOR5 and are located at positions 3 and 5 of the respective benzene ring. 13. A process according to one of Claims 1 to 12, wherein R and R1 are nitro, OR5, COOR5 or N (R5) 2, wherein R5 is hydrogen or C1-C4 alkyl, especially methyl or ethyl. 14. A compound of the formula where n is 0, 1, 2 or 3, m is 1, 2 or 3, A is an anion; Y is a linear or branched alkylene radical of the formula - [(R2) 2] -, where r is an integer between 1 and 8 and the radicals R5 independently of one another are hydrogen or C1-C4 alkyl; -CX = CX, where X is cyano, linear or branched CI-CB alkyl or di (linear or branched C1-Cs alkyl) -amino, - (CH2) q-NR4- (CH2) q-, where R4 is hydrogen or straight or branched C1-C4 alkyl and q is 1, 2, 3 or 4 or a 1,2-cyclohexylene radical of the formula:

Or a 1,2-aryl radical of the formula:

Where R9 is SO4H, CH2OH or CH2NH2, R and Ri independently are cyano, halogen, OR5 or COORs, where R5 is hydrogen or a linear or branched C1-C4 alkyl or are nitro, linear or branched Ci-Cs alkyl linear or branched, partially perfluorinated or perfluorinated Ci-Cs alkyl, NHRβ or NR6R7 where R6 and R7 are identical and are each linear or branched C? -C? 2 alkyl or where R6 and R7 together with the nitrogen atom connects them to form a 5-, 6- or 7-membered ring which may include other heteroatoms, or is linear or branched Ci-Cs-Rs alkyl, where Rs is a radical OR5, COOR5 or NR6R7 with the above definitions or is NH2 or are -N ^ RTR where R4, R6 and R7 are as defined above, R2 and R3 independently of one another are hydrogen, straight or branched C1-C4 alkyl or unsubstituted aryl or, aryl substituted with cyano, halogen, OR5 or COOR5 wherein R5 is hydrogen or linear C1-C4 alkyl or < mified, or by nitro, straight or branched d-C8 alkyl, NHRβ or NR6R7 where R6 and R7 are identical or different and are as defined above, or by straight or branched alkyl Ci-Cs-Rs, where R8 is a radical OR5, COOR5 or NRβ 7 with the above definitions or is NH2, or by -N + R ReR7, where R4, R6 and R7 are as defined above, with the proviso that R and Ri do not have the same definition if n and m are identical. 15. A compound according to claim 14, wherein n and m are in each case independently 1, 2 or 3, A is chloride, acetate, triflate or tosylate, and is a radical of the formula - (CH2) r-, where r is an integer between 1 and 8, or He has the formula -C (Rs) 2- (CH2) pC (R5) 2-, where p is a number between 0 and 6 and Rs is hydrogen or C1-C4 alkyl, R and R1 are nitro, OR5, COOR5 or N (Rs) 2 where R5 is hydrogen or

R and R1 are nitro, OR5, COOR5 or N (Rs) 2 where R5 is hydrogen or C1-C4 alkyl, especially methyl or ethyl.

16. A compound of the formula R2 F Where R, R1, R2, Rs, Y, n and m are as defined above for formula (1 a).

17. A process for preparing a compound of the formula (2) according to claim 16, which comprises reacting a diamine of the formula H2N-Y-NH2 first with an aldehyde or ketone of the formula R, and then with a aldehyde or ketone of the formula Where R, R ^ R2, R3, n and m are as previously defined for the formula).

18. A compound of the formula OR

19. A detergent comprising I) 5-90% of A) of an anionic surfactant and / or B) of a non-ionic surfactant; II) 5 - 70% C of a forming substance; III) 0.1-30% of D) of a peroxide, and IV) 0.005-2% of E of a compound of the formula (1) according to Claim 1, the percentages are by weight based on the total weight of the detergent.

20. A detergent according to Claim 19 comprising V) 5-70% of A) of an anionic surfactant and / or B) of a non-ionic surfactant; VI) 5 - 50% C of a forming substance; VII) 1 - 12% of D) of a peroxide, and VIII) 0.1 - 0.5% of E of a compound of the formula (1) as defined above, the percentages are by weight based on the total weight of the Detergent.

21. A detergent comprising IX) 5-70% of A) of an anionic surfactant and / or B) of a nonionic surfactant; X) 5 - 40% C of a forming substance; XI) 1-12% of D) of a peroxide, and XII) 0.1-0.5% of E) of a compound of the formula (a) as defined above, the percentages are by weight based on the total weight of the detergent.

22. A detergent according to one of Claims 19 to 21 further comprising between 0.05% and 5% by weight, especially between 0.2 and 1.7% by weight, of polyvinylpyrrolidone.

23. A process according to Claim 1, wherein a compound of the formula (1) is used together with a corresponding analogous symmetrical manganese complex, ie with a compound of the formula (1) wherein (R) n and (R?) m are identical.